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1 PLANT ANALYSIS AND SOIL TESTING AS TOOLS TO DEVELOP A SULFUR RECOMMENDATION FOR FRESH MARKET TOMATO (Solanum lycopersicum L.) By CAMILLE ELIZABETH ESMEL 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 2011

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Page 1: PLANT ANALYSIS AND SOIL TESTING AS TOOLS TO DEVELOP A

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PLANT ANALYSIS AND SOIL TESTING AS TOOLS TO DEVELOP A SULFUR RECOMMENDATION FOR FRESH MARKET TOMATO (Solanum lycopersicum L.)

By

CAMILLE ELIZABETH ESMEL

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

2011

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© 2011 Camille Elizabeth Esmel

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To my family and friends for their unwavering support during this gritty and sometimes

crazy process

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ACKNOWLEDGMENTS

Many people assisted me during my graduate studies. I would like to express my

appreciation to them in this dissertation. First, I wish to express my appreciation to the

chair of my supervisory committee, Dr. Bielinski M. Santos for his support and

suggestion in the pursuit of this research topic. I also recognize my co-chair, Dr. Eric H.

Simonne for his extraordinary patience and literary advice. I wish to express my

deepest appreciation to both Dr. Joseph W. Noling and Dr. Jack E. Rechcigl. Dr. Noling

for his support and sticking with me through the changes in research topics and Dr.

Rechcigl for his suggestion of pursuing analytical methodologies comparison as part of

my research. I would also like to thank Dr. James P. Gilreath for seeing potential in me

as a Master‟s student and his continual mentoring through my Ph.D.

For technical support and laboratory assistance at the Gulf Coast Research and

Education Center in Wimauma, FL, I would like to thank Elizabeth Golden, Butch

Bradley, Silvia Slamova, Victor Alifonso, Humberto Moratinos, Jose Moreno, Tim Davis,

Gitta Shurberg and Myriam Siham. I wish to express my thanks to Dr. Gurpal Toor, and

Dr. Amy Shober for their expert advice in soil science. Their assistance in completing

the analytical methodology portion of this dissertation cannot be understated.

Finally, I would like to thank my family and friends, and especially my parents,

George and Lydia Fortier, Theodore McAvoy, Aparna Gazula, Joshua Adkins, Jennifer

Bonina-Noseworthy, Kristine Hoffman, and Elizabeth Thomas.

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TABLE OF CONTENTS page

ACKNOWLEDGMENTS .................................................................................................. 4

LIST OF TABLES ............................................................................................................ 7

LIST OF FIGURES .......................................................................................................... 9

ABSTRACT ................................................................................................................... 11

CHAPTER

1 INTRODUCTION .................................................................................................... 13

Sulfur the Forgotten Essential Plant Nutrient .......................................................... 13

Why is Sulfur so Important? .................................................................................... 14

Difficulty of Predicting Crop S Nutrient Status Using Soil S Levels ......................... 15

2 SULFUR IN CROP PRODUCTION AND SOIL DETERMINATION ........................ 17

Introduction ............................................................................................................. 17

Timing and Placement ............................................................................................ 17

Source and Rate ..................................................................................................... 19

Fertilizer Sources and Rates ............................................................................ 19

Irrigation Water ................................................................................................. 21

Soil ................................................................................................................... 21

Soil Testing and Plant Analysis ............................................................................... 22

Analytical Instruments ...................................................................................... 22

Nutrient Extraction ............................................................................................ 27

Calibration of Soil Testing ................................................................................. 33

Rationale and Justification ...................................................................................... 36

3 INFLUENCE OF NITROGEN AND SULFUR SOURCES AND APPLICATION RATES ON FRESH MARKET TOMATO ................................................................ 39

Introduction ............................................................................................................. 39

Materials and Methods ............................................................................................ 43

Results and Discussion ........................................................................................... 46

4 SULFUR FERTILIZATION RATES AND IRRIGATION PROGRAMS ON TOMATO GROWTH AND YIELD ........................................................................... 53

Introduction ............................................................................................................. 53

Materials and Methods ............................................................................................ 54

Results and Discussion ........................................................................................... 56

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5 COMPARISON OF ANALYTICAL METHODS FOR DETERMINE S AND SO4-S PRESENT IN FLORIDA SANDY SOILS ................................................................. 64

Introduction ............................................................................................................. 64

Materials and Methods ............................................................................................ 69

Results and Discussion ........................................................................................... 70

6 COMPARISON OF EXTRACTANTS FOR DETERMINING SULFUR IN SOIL AND PLANT TISSUE .............................................................................................. 84

Introduction ............................................................................................................. 84

Materials and Methods ............................................................................................ 90

Results and Discussion ........................................................................................... 95

7 CALIBRATION AND DIAGNOSTIC TOOLS OF SOIL AND TOMATO TISSUE SULFUR FOR PRODUCTION ON FLORIDA SANDY SOILS .............................. 105

Introduction ........................................................................................................... 105

Materials and Methods .......................................................................................... 107

Results and Discussion ......................................................................................... 111

8 SUMMMARY AND CONCLUSIONS ..................................................................... 120

LIST OF REFERENCES ............................................................................................. 122

BIOGRAPHICAL SKETCH .......................................................................................... 133

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LIST OF TABLES

Table page 2-1 Sulfur containing fertilizers, formulas, and percent S and companion nutrients

for materials used in crop production. ................................................................. 37

2-2 Chemical reagents and concentrations for extracting available S from soil and references in which extractants were used. ................................................. 38

3-1 Nitrogen, K, and S sources, rates applied and placement used to create treatments for determining the influence of N and S fertilization on „Florida 47‟ tomato for Fall 2006 and Spring 2007 at Gulf Coast Research and Education Center in Balm, FL. ............................................................................ 49

3-2 Influence of N and S sources and applied rates on total marketable yield of tomato for Fall 2006 and Spring 2007 at Gulf Coast Research and Education Center in Balm, FL. ............................................................................................. 50

3-3 Marketable yield quality as influenced by N and S fertilization sources and applied rates for Fall 2006 and Spring 2007 at Gulf Coast Research and Education Center-Balm ...................................................................................... 51

3-4 Effects of N and S sources and applied rates on tomato foliar S concentration as percent S for Fall 2006 and Spring 2007 at Gulf Coast Research and Education Center in Balm, FL. ............................................................................ 52

4-1 Plant height and vigor ratings for tomatoes grown under differing irrigation regimes and applied S rates during Spring and Fall 2008 at Gulf Coast Research and Education Center in Balm, FL. .................................................... 59

4-2 Estimated chlorophyll content for tomatoes grown under differing irrigation regimes and applied S rates for Spring and Fall 2008 at Gulf Coast Research and Education Center in Balm, FL. ..................................................................... 60

4-3 Mid season and end of season soil pH and soil S content for soil samples collected from tomato production under differing irrigation regimes and applied S rates during Spring and Fall 2008 at Gulf Coast Research and Education Center in Balm, FL. ............................................................................ 61

4-4 Influence of irrigation regime and applied elemental S rates on tomato leaf S concentrations for seasonal pooled samples for Spring and Fall 2008 at Gulf Coast Research and Education Center in Balm, FL. .......................................... 62

5-1 Advantages and disadvantages of selected analytical instruments for determining S or SO4-S. ..................................................................................... 76

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5-2 Instrumental details for comparison between sulfur and sulfate determination for selected samples obtained at the Gulf Coast Research and Education Center in Balm, FL. ............................................................................................. 77

5-3 Salts and their solubility as potential interfering ions when determining SO4-S by turbidmetric methods. .................................................................................... 78

5-4 Potential interfering ions for determining SO4-S by turbidmetric methods, their reported thresholds in solution, and reference ............................................ 79

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LIST OF FIGURES

Figure page 4-1 Influence of rates of applied elemental S on first harvest of fresh market

tomato for Spring and Fall 2008 at Gulf Coast Research and Education Center in Balm, FL. ............................................................................................. 63

5-1 Comparison between dry combustion total S and 0.025 M KCl turbidimetric SO4-S for selected soil samples from fields at the Gulf Coast Research and Education Center in Balm, FL ............................................................................. 80

5-2 Comparison between dry combustion procedure for total S and de-ionized water turbidimetric SO4-S for selected soil samples from the fields at the Gulf Coast Research and Education Center in Balm, FL. .......................................... 81

5-3 Comparison between dry combustion procedure for total S and 0.025 M KCl Inductively Coupled Plasma total S for selected soil samples obtained from the fields at the Gulf Coast Research and Education Center in Balm, FL .......... 82

5-4 Comparison and regression analysis of dry combustion procedure for total S and Inductively Coupled Plasma de-ionized water total S for soil samples obtained from the fields at the Gulf Coast Research and Education Center in Balm, FL ............................................................................................................. 83

6-1 Diagram of Gulf Coast Research and Education Center buildings, field layout, and nomenclature system for identifying production fields. ..................... 99

6-2 Comparison of Modified Blair SO4-S with Standard Reference (H2O) SO4-S for selected soil samples from the Gulf Coast Research and Education Center in Balm, FL. ........................................................................................... 100

6-3 Comparison of Mehlich-3 S with de-ionized water S for selected soil samples from the Gulf Coast Research and Education Center in Balm, FL. ................... 101

6-4 Comparison of Mehlich-3 S with Modified Blair S for selected soil samples collected at the Gulf Coast Research and Education Center in Balm, FL. ........ 102

6-5 Comparison of total plant tissue S by wet oxidation and by dry combustion total S procedure for selected soil samples collected at the Gulf Coast Research and Education Center in Balm, FL. .................................................. 103

6-6 Distribution of the deviation between total plant tissue S by wet oxidation and dry combustion total S for selected soil samples collected at the Gulf Coast Research and Education Center in Balm, FL ................................................... 104

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7-1 Relationship between dry combustion total plant S and tomato yield for selected tissue samples from the Gulf Coast Research and Education Center in Balm, FL ....................................................................................................... 113

7-2 Relationship between total plant S and tomato yield for selected tissue samples from the Gulf Coast Research and Education Center in Balm, FL. .... 114

7-3 Relationship between dry combustion total soil S and tomato yield for selected soil samples from the Gulf Coast Research and Education Center in Balm, FL. .......................................................................................................... 115

7-4 Relationship between Modified Blair (0.025 M KCl) soil S and tomato yield for selected soil samples from Gulf Coast Research and Education Center in Balm, FL. .......................................................................................................... 116

7-5 Relationship between de-ionized water soil S and tomato yield for selected soil samples from Gulf Coast Research and Education Center in Balm, FL. .... 117

7-6 Relationship between Mehlich-3 soil S and tomato yield for selected soil samples from Gulf Coast Research and Education Center in Balm, FL. .......... 118

7-7 Possible main fractions of soil S and analytical methods for S determination. . 119

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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

PLANT ANALYSIS AND SOIL TESTING AS TOOLS TO DEVELOP A SULFUR

RECOMMENDATION FOR FRESH MARKET TOMATO (Solanum lycopersicum L.)

By

Camille Elizabeth Esmel

May 2011

Chair: Bielinski M Santos Cochair: Eric H. Simonne Major: Horticultural Sciences

Sulfur is one of the essential elements for plant growth and development. Current

trend in fertilizer formulations is to use high analysis fertilizer sources, which exclude

sulfur (S). In the past, anthropologic and environmental sources have met plant‟s S

requirement, but implementation of clean air referenda have reduced atmospheric S.

Therefore, studies were conducted to determine, if a S response in tomato exists, 1)

differences in sources of S and rates of S with nitrogen (N) on tomato production 2) if

irrigation regime and S rates could influence tomato production, 3) the appropriate soil

testing method for S and sulfate-sulfur (SO4-S), and 4) if a relationship could be

established between tomato yield, tissue S, and soil testing results. Two field studies

and one laboratory experiment were conducted at the Gulf Coast Research and

Education Center in Balm, Florida to ascertain these objectives.

The first field study used ammonium nitrate ((NH4)2NO3), potassium sulfate

(K2SO4), ammonium sulfate nitrate (NH4NO3 + (NH4)2SO4), ammonium sulfate

((NH4)2SO4) as fertilizer sources. Muriate of potash was used to balance total

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potassium amounts. Tomato yields increased with the inclusion of S into the fertilizer

program for Fall 2006 season. Sulfur sources were found to be similar and different

from the non-treated control and NH4NO3 treatment for Fall 2006 season. The second

field study utilized a split-plot design with three irrigation regimes (5,406, 8,109, and

10,812 L·ha-1·d-1) and six S rates (0, 28, 56, 112, 168, and 224 kg S·ha-1). Irrigation

regimes chosen for this study did not influence tomato production. Only early tomato

harvest was influenced by S rate for both seasons. The rate of 28 kg S·ha-1 increased

yield over the non-treated control and beyond this level early yield did not increase.

For the laboratory study, soil and tissue samples were collected and extracted for

S or SO4-S. A suitable soil test was not found to relate soil S or SO4-S to crop S on

sandy soils. It is recommended when S deficiency is diagnosed based upon tissue

testing. An application rate of 28 to 37 kg S·ha-1 should be used in tomato.

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CHAPTER 1 INTRODUCTION

Sulfur the Forgotten Essential Plant Nutrient

Sulfur (S) is the 16th most abundant element in the earth‟s crust, with

concentrations ranging from 0.06% to 0.10% (Ceccotti et al., 1998; Havlin et al., 2005),

is essential for plant production of S containing amino acids cysteine, and methionine

(Leustek, 2002). Although animals are unable to reduce sulfate (SO4), they rely upon

their diet to attain S through S-containing proteins. Therefore, if deficiencies exist in

forage, grain, and vegetable crops this reduced level of S then carries over to both

animals and humans. Deficiencies have begun to be widely reported in various crops

(such as Brassica spp.) and crop by-products (e.g. flour) (Duke and Reisenauer, 1986;

Hagel, 2005; Sawyer and Baker, 2002). It has been suggested that deficiencies are the

result of decreased S being put into the environment and the increased use of low-S

fertilizers.

Clean air referenda across the world have caused reduction on world sulfur

dioxide (SO2) emissions with estimates ranging from 55.2 to 68 Tg·yr-1 S (De Kok et al.,

2007; Smith et al., 2001; Stern, 2005). It is predicted that future plant-available S from

atmospheric depositions will be less than 10 kg S·ha-1 per yr (Dägmmgen et al., 1998).

Sulfur deficiency has become recognized as a limiting factor for crop production

(Schere, 2001) and more apparent where increased agricultural intensification of arable

land and the use of low S fertilizer has occurred (Ceccotti et al., 1998). Low S

fertilizers, commonly referred to as high analysis fertilizers, are a common fertilizer

choice in vegetable production.

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Why is Sulfur so Important?

Unlike animals that have a dietary requirement for S amino acids, plants are able

to assimilate inorganic sulfate-S (SO4-S), which is reduced to sulfide (H2S) and is then

incorporated into cysteine (Leustek et al., 2000). As humans we rely directly or indirectly

upon plants for S-based amino acids for our diet. Sulfur is the least abundant of the

macroelements found in plants, with an approximate concentration of 1,000 mg S·kg-1

of dry matter (Leustek et al., 2000). Additionally, the S cycle is a biological and

chemically-mediated cycle. The majority of soil S is in organic S form and not readily

available for plant uptake. Thus, the process of mineralization is an important

consideration when choosing fertilizer sources (i.e. elemental S versus SO4 salts). In

addition to these issues, SO4-S, the form plants uptake from the soil, is an anion. As an

anion, SO4-S can be leached from the soil profile and this is influenced by the presence

of other anions (Eriksen and Askegaard, 2000). Adsorption refers to the ability of an

object to attract and hold particles to its surface. All soils, especially clays and organic

matter, have the ability to adsorb water, nutrients, and other chemicals. The order of

adsorption of strength of anions in soils is as follows: phosphate > sulfate > nitrate >

chloride, where as phosphates are the primary anion adsorbed (Havlin et al., 2005).

Eriksen and Askegaard (2000) found an average of 20 kg S·ha-1 was leached from a

crop rotation over three years in sandy soils. This amounted to approximately 60% of

the total S input into the system. It is possible; because of the sandy soils dominate in

Florida, to leach SO4-S out of the soil profile and into waterways. However, there is a

lack of scientific information supporting this hypothesis.

The potential of SO4-S to leach may cause future pollution problems as S under

anoxic conditions (aquatic systems) has been suggested to enhance the methylation of

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mercury (Ullrich et al., 2001; Bates et al., 2002). When Hg has been methylated, it may

be bio-accumulated by fish and stored in lipid tissues (Ullirch et al., 2001). Mercury

accumulation in fish poses a health risk for humans as well as other invertebrates when

consumed. In Florida, it has been reported that P and S run off from the Everglades

Agricultural Area (EAA) have the potential to shift native vegetation population species

as well as the microbial population in the Everglades (Brix et al., 2010; Castro et al.,

2005; Li et al., 2009). Therefore, the effects of excess nutrients in balance with the

knowledge of proper fertilizer management strategies should be developed for S in

Florida to maximize crop growth and yield while maintain environmental quality.

Difficulty of Predicting Crop S Nutrient Status Using Soil S Levels

To develop fertilizer recommendations for any crop a robust relationship between

crop response and soil testing needs to be established. This association is the back

bone of interpretation of a soil test, the requirement of an established relationship

between soil, plant tissue content, and relative yield (Bloem et al., 2001). Crop

responses to S and SO4-S applications have been established worldwide (Scherer,

2001; Tabatabai, 1984). In Florida, Susila (2001) found that timing and form of S did

not influence tomato (Solanum lycopersicum L.), but increased yields occurred with the

inclusion of S into the fertilizer program. It is possible given that a response to S has

been found for tomato to establish a relationship between crop response and soil S.

Currently, a relationship between crop response and soil testing has not been

conclusively established, because of the factors influencing the soil S cycle. Seasonal

fluctuation of inorganic S concentration in the soil solution occurs because of changes in

the balance between microbial activity, soil drying, leaching, surface runoff, atmospheric

inputs, plant uptake, plant senescence, and fertilizer inputs (Blair et al., 1993; Williams,

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1968). These factors add to the difficulty of determining a relationship between soil S,

tissue S, and plant yield. Furthermore, S and SO4-S soil testing lacks a universal

reference method making it apart of routine soil testing, and many extracting solutions

have been employed for testing soil S and SO4-S (Lewis, 1999; Lisle et al., 1994;

Matula, 1999; Rao and Sharma, 1997). A wide range of soil analytical methods will still

be employed for S and SO4-S determination until an established relationship between

soil S and crop yield or S content.

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CHAPTER 2 SULFUR IN CROP PRODUCTION AND SOIL DETERMINATION

Introduction

If S deficiencies are diagnosed for vegetable crops grown in Florida, it is

recommended to apply 28 to 37 kg S·ha-1 (Simonne and Hochmuth, 2009). Yet, this

recommendation for S in crop production has often been empirical in nature than based

upon previous research. And positive yield and growth results have been found when S

has been applied to vegetable crops (Pavlista, 2005; Rhoads and Olson, 2000; Susila,

2001). The objectives of the of this review are to review (1) existing S fertilizer research

on vegetable crops for developing S fertilizer recommendations and (2) review the

methodology currently used to measure S fractions in plant and soil samples.

A fertilizer recommendation for any nutrient consists of four fundamental

components: timing, placement, rate, and source of the fertilizer. Timing refers to at

what point in the crop growth cycle the fertilizer is applied (i.e. pre-plant or at planting).

Placement refers to where the fertilizer is placed (i.e. banded or broadcasted). Rate

refers to the amount of nutrient applied per unit of land. Source refers to the particular

fertilizer salt used to supply the nutrient to the crop. Each component is essential when

developing a fertilizer recommendation.

Timing and Placement

Timing of S application depends largely on whether the S fertilizer is a sulfate form

that is immediately usable or an elemental S that must be first oxidized before the plant

can utilize it, and also the formulation (solution, suspension, granules, or prills) (Malhi et

al., 2005). In the case of elemental S as granules or prills, soil moisture can be the

dominant factor in dispersion/oxidation. Soil temperature also factors into the

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dispersion/oxidation of elemental S via soil microbial action. However, Nuttall et al.

(1990) found that external force was required to dispersion of elemental S prills.

Elemental S fertilizers applied annually for several years are expected to produce a

cumulative residual effect on plant available S in soil and subsequently on seed yield

and quality of canola (Brassica napus L.) (Malhi et al., 2005). Further research by Malhi

et al. (2009) found that timing did not influence wheat (Triticum aestivum L.) yield

parameters in a canola-wheat rotation, but the residual effects from previous year‟s

application did improved wheat seed yield into 2006 and 2007 seasons. These authors

suggested that fall applications of sulfur in this system were superior to spring

applications. In contrast, Solberg et al. (2003) found that early broadcast applications of

S fertilizers resulted in an increased recovery by soil testing for SO4-S from fallow fields.

Very little information exists on only timing of S fertilizer applications for vegetable

production.

Since in vegetable production often the timing of fertilizer applications is directly

linked to the placement (i.e. pre-plant broadcast, pre-plant banded, season long drip

injections of fertilizer). It is difficult to separate the two topics and often they are

discussed together as method of application. Susila (2001) found that methods of S

application (pre-plant, split application, and drip injection) did not influence yield or

growth parameters of tomato, but did positively influence leaf S concentrations 6 weeks

after transplanting. Drip injection of S had the highest level of leaf S content at 6 weeks

after field planting. Other studies by Susila (2001) revealed that pepper (Capsicum

annuum L.) was not influenced by the method of S fertilizer application. Yet, studies

conducted on cabbage (Brassica oleracea L.) by Susila (2001) found method of S

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fertilizer application as a drip injection increased cabbage yield. This is not a surprising

result for cabbage, since this vegetable crop has a high S requirement (Scherer, 2001).

Source and Rate

Crop plants fulfill their S requirement from a number of sources; including crop

residues, manures, rainfall, the atmosphere, soil amendments, fertilizers, irrigation

water, and soil (Tabatabai, 1984). In vegetable cropping systems, the number one

source of nutrients is fertilizer, but often environmental sources are not accounted (i.e.

irrigation water and soil levels). The goal of this section is to discuss not only fertilizer

sources and rates, but also irrigation water and soil levels of S available for plant

uptake.

Fertilizer Sources and Rates

Elemental S is the least expensive S fertilizer source when compared to other

sources of S that contain N ((NH4)2SO4), ammonium thiosulfate (NH4)2S2O3), and

NH4NO3 + (NH4)2SO4). Elemental S can be an ideal S source for crop growth and yield

because it is 1) high analysis of S and insoluble in water; 2) stable in damp and humid

conditions 3) has to be oxidized to SO4-S for plant uptake (Solberg et al., 2003). The

slow release of elemental S via oxidation to SO4 would be considered a disadvantage in

certain cropping systems, such as annual vegetable production. Information on

elemental S as a S source in vegetable production is needed.

Other sources of S that contain N or K have been studied. Susila (2001) found

tomato yield response to S sources ((NH4)2SO4 versus (NH4)2S2O3) was similar,

regardless of application method (broadcast versus drip injected). Sulfur sources

((NH4)2SO4·NH4NO3, K2SO4, CaSO4·7H2O, K2SO4·2MgSO4) have been found not to

influence cabbage yield (Rhoads and Olson, 2000). Heeb et al. (2006) found that the

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inclusion of S into the fertilizer regime for greenhouse grown tomato increased yield and

growth than when compared to fertilizer regime without S. This further supports Rhoads

and Olson (2000), in which cabbage yield did not respond to treatments where S was

not included.

Fertilizer application rates are an important factor in creating a fertilizer

recommendation in any cropping system and should be on the basis of available soil S

and crop nutrient requirements (Scherer, 2001). Crop nutrient requirement is defined as

the total amount (kg·ha-1) of an element required by the crop to produce optimal yield

(Simonne and Hochmuth, 2009). Crop nutrient requirements are determined by studies

conducted with the inclusion of nutrient into the fertilizer program with different

increasing rates of the nutrient on land in which there is no history of S applications or S

present.

Limited information is available on vegetable crop S requirements, but some

studies have explored S rates and the inclusion of S into the fertilizer program. Suslia

(2001) found linear increases in tomato yield when S fertilizer rates increased from 0 to

102 kg S·ha-1, but no one rate was recommended for tomato production. Susila (2001)

also found that 34 kg S·ha-1 was the critical level for S applications on cabbage. After

this rate, cabbage yield (in heads) was reduced. These results are in agreement with

Rhoads and Olson (2001) in which 45 kg S·ha-1 was found to be excessive and

consistent higher yields resulted from 22 kg S·ha-1. While fertilizer may be the primary

source of nutrients for crops, other sources of nutrients must be explored and

accounted for when creating a fertilizer recommendation. Irrigation water and soil may

also be sources of S in crop production.

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Irrigation Water

Field sites without access to mineral bound S sources may have insufficient S

dissolved in soil water and shallow ground water bodies to move available S to plant

roots (Eriksen et al. 1998). The concentration of S in irrigation waters used throughout

North American is unknown, and little research is available related to the S content of

irrigation waters to S requirement in a fertilizer program (Olson and Rehm, 1986).

Studies on high sulfate irrigation waters utilized water with 175, 646, 862, and 1,743 mg

SO4·L-1 (Drost et al., 1997) and 15.0 and 38.8 mol SO4·L

-1 (Papadopoulos, 1986) have

found mixed results in improving yield of broccoli and tomato. In Florida, SO4 levels in

drinking water wells can range from 0.2 to 1400 mg SO4·L-1 with higher concentrations

coming from deeper wells (Sacks, 1996). While these values cover drinking water, the

levels of SO4 or S within irrigation water in Florida are unknown. It has been suggested

that water pumped from the aquifer as well as surface waters, has a rotten-egg smell

commonly associated with sulfide (H2S) levels. This may often leads to the belief that S

in the irrigation water is an S source for crop production. Little scientific information

exists to support this claim.

Soil

Most Florida surface soils are low in plant-available S, and additional sources are

necessary to maintain optimum production despite the lack of actual cases of S

deficiencies among crops (Mitchell and Blue, 1981). These authors also suggested that

4 kg S·ha-1 as SO4 derived from SO2 from summer rainfall based upon calculations and

estimations by Brezonik et al. (1980) would remain in the surface soil for plant uptake.

They also suggested that 0.8 kg S·ha-1 of the initial 4.8 kg S·ha-1 estimate would be

leached or immobilized.

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Mitchell and Blue (1981) stated that Spodosols and Entisols, two of the major soil

orders in Florida, lack large reserves of available S in the subsurface horizons. Ultisols,

another predominate soil order in Florida, may provide S via the argillic horizon in the

subsurface. Florida sandy soils (Spodosols and Entisols) were found to not have

enough available S reserves for tomato crop growth (Susila, 2001). Both surface and

subsoil horizons were inefficient in supplying enough S for six weeks of growth without

the addition of pre-plant application of S as (NH4)2SO4. Although, this study utilized an

Arredondo fine sand soil (loamy, siliceous, hypertherimic, Grossarenic Paleudult), an

Ultisol, growth of tomato on this soil required S applications. These results are in

conflict with those of Mitchell and Blue (1981) stating that Ultisols may have enough

reserve S in the subsoil for plant growth. It may be possible that crops with large deep

root systems would benefit from reserve S in the subsoil. Vegetable crops, such as

tomato and cabbage, often have shallow root systems in compared to row crops (i.e

corn (Zea mays L.) and alfalfa (Medicago sativa L.)).

Soil Testing and Plant Analysis

Analytical Instruments

Current assessment of S and SO4-S in agricultural soils for the development of

fertilizer recommendations has been fraught with difficulties. The major difficulties that

researchers confront are inherent variability in analytical results, lack of consistent

associations between soil S, plant S, and crop yield, and S in soils and plant tissues is

often a separate method adding time and costs in an analytical laboratory.

Ideal characteristics for S determination would be low cost, rapid, accurate,

precise, with low interference, and potentially offer multiple element determination

options. Soil chemical analysis or “soil testing” is the cheapest and most widely used

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chemical analysis employed in agriculture (Van Raij et al., 2002) and is often under

utilized by many (Jones, 1993). It is primarily the cost of labor to operate analytical

instrument that determines the underlying cost of each soil sample.

In terms of speed, many instruments (i.e. elemental analyzer, inductively coupled

plasma-atomic emission spectrometer or inductively coupled plasma-optical emission

spectrometer (ICP-AES/ICP-OES), ion-exchange chromatograph (IC), and discrete

analyzer) have been automated to allow sample loading time to be reduced. This can

essentially cut labor and time for the laboratory worker spent supervising instrument

status. In the past, S and SO4-S determination were labor intensive and required

reagents have a finite shelf life for use. Such example is methylene blue, which is the

color reagent for estimating the reduction of sulfate to sulfide (Tabatabai, 1996). The

color of this reagent is important to the determination of S by spectrometric means; if

kept away from direct sunlight the color can remain stable for 24 h or more (Tabatabai,

1996). This would be considered to be a time limitation or shelf-life restriction for this

method. Not properly understanding and identifying limitations in a method can lead to

data quality issues.

Quality control and assurance plans are implemented to maintain result quality.

Quality control consists of using the following: proper calibration, blanks, duplication of

samples, spiked samples and the use of certified standards (Shampine, 1993). Quality

assurance usually consists of validation of methods (characteristics and limits). Both of

these are extremely important to S determination, because of the inherent variability in

determining S and SO4-S. It has been reported by Crosland et al. (2001) that the

coefficient of variation from an inter-laboratory study on soil S was between 36 to 45%.

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This means up to 45% of the variation in soil S values was due to random error and the

decision to apply fertilizer based upon this data could be faulty. This random error can

be attributed to operator error, loss of calibration during analysis or interferences from

other elements within the aliquot.

Interferences from other elements or ions are the most encountered error when

determining S or SO4-S. With the advent of newer technologies, such as ICP-OES,

claims that less interference would be encountered were publicized (Kola et al., 2002).

Multi-element determinations are limited to those instruments with the ability to

determine multiple elements. These include, but are not limited to the following:

elemental analyzers, ICP-OES/ICP-AES, and IC. Instruments with multiple element

determination capabilities are viewed as a versatile economic investment. These types

of instruments reduce labor, because more than one element can be analyzed within a

single sample.

Currently seven analytical instruments are capable of determining total S or SO4-

S. These instruments are ICP-AES or ICP-OES (S), inductively coupled plasma mass

spectrophotometer (ICP-MS) (S), elemental analyzer (S) by infrared radiation

cell/spectrometer (IR) or titration of SO2, IC (SO4-S), and turbidimeter (SO4-S). Of these

six instruments, the three most commonly used to determine S or SO4-S are ICP-

AES/ICP-OES, elemental analyzer via IR or titration, and colorimetrically with a

spectrometer (turbidimeter).

The principle behind ICP-AES/ICP-OES is based in chemistry and physics. More

specifically, it involves particle collision, excitement of out shell electrons,

adsorption/emission of a wavelength, and separation/detection of spectral lines of

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interest. A comprehensive discussion of the theory will not be provided here, but

several reviews and sources explain in detail such theory and mechanics of ICP-

AES/ICP-OES (Boss and Fredeen, 1997; Lajunen and Perämäki, 2004; Manning and

Grow, 1997; Welz et al., 2009). Several advantages for determining S with ICP-

AES/ICP-OES are after initial costs, it is cost effective, rapid sample analysis, multiple

element, low level of interferences, wide linear dynamic range and detection limits at the

μg·L-1 level (Kola et al., 2002, Mermet and Poussel, 1995). One disadvantaged for

determining S with ICP-AES/ICP-OES is that a vacuum line is required within the

instrument as S is considered a non-metal element. This is required, because emission

lines for S lie in the ultraviolet range so that the lines are not absorbed by O2

(Soltanpour et al., 1996). A range of emissions are used for S on ICP-AES/ICP-OES.

In general, the range of wavelengths used is from 180.04 to 182.63 nm, and the three

strongest emission lines of S in the vacuum ultraviolet spectrum are at 180.73, 182.04,

and 182.63 nm (Wu et al., 2009). Two significant spectral overlaps occur around the

180.73 nm S line; 180.361 nm Ca and 180.74 nm Mg lines (Eames and Cosstick, 1992).

Therefore, corrections or adjustments must be made to ensure interfering spectral lines

are not distorting results for S.

The principle behind an elemental analyzer, often called by brand name LECO or

by the method name Dumas, is titration via colorimetric determination or infrared

radiation (IR) determination of total S. The Dumas method is the combustion of

samples a high temperatures (<1000° C) and the evolution of S as SO2 and subsequent

capture for determination. Earlier Dumas models use a photocell with SO2 collected by

HCl containing KI, starch, and a trace amount of KIO3, approximately 0.22 M KIO3

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(Tabatabai, 1996; Tiedemann and Anderson, 1971) or 1N NaOH (Tabatabai, 1996) with

colorimetrically determining total S by methylene blue similar to Johnson and Nishita

(1952). For IR determination of S, after combustion, a stream of gas is directed into a

ballast tank, homogenized before a sample is trapped for infrared detection of S

(Kowalenko, 2001). The infrared source consists of nichrome wire, which is resistance-

heated to 850° C, SO2 absorbs infrared energy at 3.98 and 7.35 μm (Gong et al., 2006),

with a band-pass filter to prevent further infrared energy reaching the IR detector

(LECO, 2006).

The advantages of an elemental analyzer are that it is designed for simplicity,

speed, convenience, carbon (C), N can also be determined by some models

(Tabatabai, 1996), and capable of measuring total S in soils including those with high

organic matter content is possible unlike with wet digestion methods such as NaBrO

(Kowalenko, 2001). Some disadvantages of elemental analyzers are the following:

initial cost of the instrument, the built in flow conditions for S restrict the scope for

optimizing the combustion cycle for organic and total C determinations when analyzing

C and S simultaneously (Wright and Bailey, 2001), and without an automated sample

loader this process consumes time and labor to load each sample individually.

The principle behind SO4-S determination by turbidity is the Beer-Lambert‟s law in

which a reduction in the intensity of light passing through a solution containing

suspended particles of barium sulfate (BaSO4) (Beaton et al., 1968). The advantages

of determining SO4-S by turbidimetry are less time consuming, in some cases sensitive,

and the most commonly used method for determining SO4-S. Therefore many

modifications are available to adjust for its short comings including exchange resins,

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addition of charcoal filters, and flow injection analysis (Morais et al., 2006). The

disadvantages to turbidimetric measurement of SO4-S are insensitivity at low

concentrations (less than 10 mg·L-1), multiple cation interferences (Na, K, Ca, Mg, NO3,

PO4, and SiO2), cation co-precipitations with Ba, high organic matter co-precipitation,

and difficulty of reproducible BaSO4 suspensions under uniform precipitating conditions

(Beaton et al., 1968; Tabatabai, 1996).

Nutrient Extraction

Assessing relationships between a newly proposed soil or plant extractant and a

standard extractant is a useful first-step technique in the evaluation a new extractant for

the development of a soil testing program (Van Erp and Van Beusichem, 1998). This

useful first-step technique seems to be lacking for soil S and SO4 extractants in many

soil testing programs that have been developed. Many studies have been conducted

upon comparing determination methods of S (Ajwa and Tabatabai, 1993; Crosland et al.

2001; Palomino et al., 2005; Reisman et al., 2007; Soon et al., 1996), but only few

separate extraction solution comparison from the determination step. This may be a

mistake made by many investigators trying to determine optimal soil extraction solutions

for the development of a soil testing program.

Soil tests for N and S, as well as for the micronutrients, are either limited in their

applications to a narrow range of soil-crop conditions or are nonexistent (Jones, 1985).

The application of a soil test for S may be narrow in range, because soil S is in constant

flux due to environmental influences via microbial activity on soil S (Spencer and

Glendinning, 1980). Environmental influences such as soil disturbance, rainfall,

temperature, and organic matter input could all cause fluxes in soil S. Therefore, land

history would be an important factor in the amount of soil S available to plants.

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Some of the most widely used solutions to extract soil S to predict plant availability

and fertilizer applications are water (H2O), calcium chloride (CaCl2), and phosphate

based solutions (Anderson et al., 1992; Tan et al., 1994a). Water extractable S is

primarily soil S readily leached out of the soil and is mostly likely in the inorganic SO4-S

form. Several solutions are often used and labeled as „water-extractable S‟ when they

are truly slightly saline solutions. These solutions include, but are not limited to sodium

(Na), calcium (Ca) or lithium chloride (LiCl) solutions (Palomino et al., 2005). These

solutions extract the soluble fraction of sulfate in soils (Santoso et al., 1995). The

calculated difference between „water extractable S‟ and a phosphate solution is related

to the amount of sulfate adsorbed by the soil, but this does not always hold true

(Santoso et al., 1995). Often and depending upon soil organic matter and exchange

sites, water extractable S as H2O can significantly dissolute more SO4-S than salt

solutions (Maynard et al., 1987; Santoso et al., 1995; Tan et al., 1994a ) or in some

cases similar amounts (Anderson et al., 1998; Tan et al., 1994b; Zhao and McGrath,

1994).

Many studies employ monocalcium phosphate (Ca(H2PO4)2) extraction solution at

0.01 M or 500 mg·L-1 P. This is one of the recommended soil SO4-S extraction

solutions for northeastern US (Singh et al., 1995) and extracts more soil SO4-S than

water via dissolution of SO4-S off exchange sites on soil particles. Yet, this solution can

cause interferences when using turbidimetric measurement of SO4-S when 0.04 M

solution is used for some soils (Searle, 1998). The other issue with Ca based extraction

solutions is that Ca may cause spectral interference of S when using ICP-AES (Zhao

and McGrath, 1994). In addition, various studies using Ca(H2PO4)2 have had variable

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results for extracted S correlating significantly to other parameters (Anderson et al.,

1998a; Anderson et al., 1998b; Blair et al., 1991; Blair et al., 1993; Chinoim et al., 1997;

Palomino et al., 2005; Pandey and Girish, 2006; Spencer and Glendinning, 1980;

Vendrell et al., 1990).

Blair et al. (1991) developed a soil extraction solution of 0.25 M potassium chloride

(KCl) as a potential replacement to Ca(H2PO4)2 extraction solution as a response to

poor performance of Ca(H2PO4)2 as a soil extractant. Potassium chloride was originally

investigated by Gianello and Bremner (1986) to measure inorganic N and potential

mineralized N. Yet, concerns raised for this potential replacement have been centered

on the parameters involved in the methodology. This method has a long incubation

time (3h) and requires the maintenance of 40° C for this time period while shaking.

Modifications of this procedure have been made to improve time and detection limits.

Bloem et al. (2002) examined six modifications of the 0.25M KCl extracting solution for

SO4-S. This study found that using 0.025 M KCl, 1 to 5 ratio of soil to extracting

solution, shaking for 3 hr at room temperature was the fastest, precise method for SO4-

S extraction of agricultural soils (Bloem et al., 2002). While this optimizes soil testing for

SO4-S alone, another possibility is the inclusion of soil SO4 and S determination in

extraction solutions already accepted by laboratories. An example is the Mehlich 3

extracting solution.

The Mehlich 3 extraction solution excludes H2SO4, which is a component of the

Mehlich 1 extraction solution, therefore makes it ideal chemically for the determination

of S. Mehlich 3 extractant was designed to replace the Mehlich 1 and Bray 1 P

extractant (Jones, 1998) and is suitable for use on neutral to acidic soils. The benefit of

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using an extracting solution such as Mehlich 3 is that it allows for S to be determined as

part of a multi-element (including micronutrients) extraction step. This saves time,

labor, and money, because separate chemicals and analysis do not need to be

performed as has been described in a diagram by Jones et al. (1991). Few studies

have examined Mehlich 3 for S extraction in soils, because the general belief that S is

analyzed separately from all other nutrients. This is either due to the determination of

SO4-S by turibidimetry or ion chromatography instead of using ICP technology.

Rao and Sharma (1997) found strong relationships between Mehlich 3 and other

extracting solutions commonly used to determine SO4-S in soils. This was the first

reported effort of using Mehlich 3 as an extractant for S in soils. Zbíral (1999) found

Mehlich 3 extraction correlated well to water extraction of SO4-S. Also Zbíral and

Nĕmec (2000) found that Mehlich 3 would be suitable for multi-element determination in

Czech agricultural soils. Further support of Mehlich 3 being used to include S in its

multiple element extraction was by Pandey and Girish (2006). Yet, this study did not

compare ability of each extracting solution to dissolute SO4-S or S from the soil

samples. Instead, the study focused upon correlation between extractants chosen and

various plant growth and total S within tissue.

Total S in plant tissues are most commonly extracted by two methods: dry

combustion (also known as dry ash procedure) or wet oxidation (also known as acid

digestion). While each has their own advantages and disadvantages, the focus here is

on which ones commonly used in S research and suitability for S determination. For dry

combustion, two methods are often used. The first is the Association of Analytical

Communities (AOAC) Official Methods of Analysis for sulfur in plants in which organic

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matter can be destroyed by two different chemicals, sodium peroxide (Na2O2) or

magnesium nitrate (MgNO3) (AOAC-OM-920.10 or AOAC-OM-923.01) (AOAC, 2000).

The AOAC Official Methods of Analysis are considered to be the reference methods in

the analytical chemistry domain, but often these methods are not used by research

scientists in agricultural fields. This is primarily due to the chemical hazards, time, and

labor involved in AOAC Official Methods of Analysis. The other dry combustion

technique for total S in plant tissues is an automated procedure commonly termed

LECO. This procedure has two steps within one piece of equipment: organic matter

destruction and total S determination step. The LECO procedure combusts samples at

temperatures up to 1400° C and measures S as SO2 evolved by titration or infra-red

cell. In some cases, an accelerator or catalyst is added to the sample such as tungsten

trioxide (WO3) or vanadium pentoxide (V2O5). Kowalenko (2001) suggested that

tungsten trioxide be added when simultaneously measuring C, N, and S with a LECO

automated dry combustion instrument. Whether or not a catalyst was used (Etheridge

et al., 1998) or one case the type of catalysis used (David et al., 1989) have not been

reported when LECO automated dry combustion instrument is used for total S. While

this may seem just a minor error, the lack of this information creates difficulties in

repeating the analytical research. In contrast, the automated dry ash procedure, wet

oxidation for the extraction of S from plant tissues is time consuming.

The most common wet oxidation procedure for total S is nitric acid with perchloric

acid (HClO4). The number one difficulty with acid mixture for wet oxidation is the

tendency of hot HClO4 in the presence of easily oxidizable organic matter to be

explosive (Jones, 1985). This in conjunction with the need for a special hood when

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using HClO4 rules it out for many laboratories when choosing a wet oxidation method.

Therefore, it is not surprising that many studies have been conducted on comparing

acid mixtures which include or exclude HClO4 for the suitability as a matrix for metals

and non-metals (Havlin and Soltanpour, 1980; Hoenig et al., 1998; Huang et al., 2004;

Ippolito and Barbarick, 2000; Oliva et al., 2003; Pöykiö et al., 2000; Soon et al., 1996).

Two studies in particular (Pöykiö et al., 2000; Soon et al., 1996) compared methods for

the determination of total S in plant tissues. Pöykiö et al., (2000) compared five

different wet oxidation methods and dry combustion for total S and six other elements

(Al, Ca, K, Mg, Mn, and Zn) against the certified value. This study found that out of all

wet oxidation methods nitric acid (HNO3) + hydrogen peroxide (H2O2) or HNO3 alone

were the most suitable for S determination using ICP. Also the HNO3 + HClO4 digestion

procedure in almost every case gave the lowest results compared to other acid

digestion procedures (Pöykiö et al., 2000). The authors also stated that the combustion

technique combined with infrared detection (LECO) also gave relative good

reproducibility for sulfur determination. In contrast, Soon et al. (1996) compared six

total S methods with reference values. These methods were dry ashing with sodium

bicarbonate (NaHCO3) + silver oxide (Ag2O), oxygen flask combustion with

determination on two different analytical equipment, LECO, microwave digestion with

HNO3 + HClO4, and microwave digestion with HNO3 + H2O2 + hydrochloric acid (HCl).

Both dry ashing with NaHCO3 + Ag2O, and oxygen flask combustion can be time

consuming for regular laboratory use when compared to microwave digestion. In

addition, precipitation of AgCl2 may occur in the case of dry ashing as well as poor

recovery of S from certain plant tissues. Microwave digestion, while rapid, has a high

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initial cost with the investment of the equipment and may not be in used in commercial

laboratories. Despite these concerns, Soon et al. (1996) suggested that HNO3 + H2O2 +

HCl was suitable for multi-element analysis using microwave digestion in conjunction

with ICP spectrometry and that LECO results for total S in plant tissues were similar to

this method.

Calibration of Soil Testing

The results of soil tests can be used to diagnose and guide the correction of

nutrient deficiencies, to diagnose and avoid nutrient and non-nutrient toxicities, to

assess the need for soil amendments and to monitor the effects through time of fertilizer

rates and other management practices (Helyar and Price, 1999). Interpretation of soil

test results requires a correlation between yield and soil test values. Typically, the

interpretation has been established for a crop, soil type, and area. In the case of S and

tomato, this relationship has not been established. While it is important to note that

seldom does interpretation become established based upon a single carefully designed

experiment; rather it requires hundreds of fertility trials and resulting in thousands of

plant analyses (Melsted et al., 1969). An initial study must be conducted to establish a

nutrient calibration curve.

Nutrient calibration based upon mineral concentration in dry matter versus plant

growth or yield has been described by Smith (1962). This nutrient calibration curve is

the basis of plant nutrition. It is a relationship often attempted to be established for many

nutrients for interpretation of nutrient research results. Both total and relative yield can

be used, but it is not recommended to use relative yield as a variable. Using relative

yield can lead to erroneous conclusions due to the standardization of yield over several

locations or seasons. Different locations and multiple seasons often have variability in

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practices and environmental factors making standardization (i.e. dividing all yields by

one yield from a certain location or an average across all) misleading. Standardization

does not accurately reflect the variability in yield response.

It has been suggested by Jackson (2000) that thorough evaluations of SO4-S

extraction procedures, along with more S response data are needed to create an S

fertilization recommendation. Strong relationships between soil S and plant S are

difficult to achieve and are the current focus of many S researchers throughout the

world. Only calibration of soil test values against yield, S concentrations in plants or S

uptake by plants make them suitable for judgment about the S nutritional status of a site

(Schnug and Haneklaus, 1998).

Since an official method of analysis is lacking (due to variability) for soil S, a

standard reference method for determining SO4-S or total S in soil is used. Examining

the literature about SO4-S or total S determination in soil resulted in many studies

recommending different soil extraction and determination methods (Table 2-2). Beaton

and Burns (1968) cite two methods for determining extractable SO4 from soils: by

calcium phosphate (CaHPO4) and LiCl. The first determines SO4 by turbidimetry and

the second by methylene blue. Jones and Jones (2001) have the determination of

extractable SO4-S as Ca(H2PO4)2, 0.5 M ammonium acetate (CH3COONH4) – 0.25 M

acetic acid (CH3COOH) and 0.01 M CaCl2.

Blair et al. (1993) developed an extraction method for SO4-S for humid

environments. Based upon the author‟s previous research on evaluating range of

extractants as predictors of S status of pastures, they found that 0.25 M KCl extraction

solutions shaken at 40° C had the highest significant coefficient of determination (Blair

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et al., 1991). More recently, Bloem et al. (2002) investigated this method for extracting

soil S and compared it to modified versions of Blair‟s method. These extraction

procedures can be used in conjunction with turbidimetry, inductively coupled plasma

emission spectrometry, and ion chromatography.

An important theme throughout S research is the wide spread variability for

different methods when determining S and even laboratory to laboratory methodological

differences in determining S and SO4-S. An inter-laboratory comparison of S in plant

tissue and SO4-S in soil found that variability [higher than 36% coefficient of variation

(CV)] was large and that determination of S is a complex and difficult procedure

(Crosland et al., 2001). This study made several recommendations that are applicable

beyond the United Kingdom, where the study was conducted. Some suggestions

advanced by Crosland et al., (2001) were 1) laboratories should standardize extraction

and digestion procedures for S, 2) reference materials should be utilized (none currently

exist for soils), 3) analytical methods must be capable of determining low concentrations

of S in soil extracts, and 4) methods must be calibrated for diagnostic purposes so that

results obtained are comparable with those from other methods. The first

recommendation is important, because until a standardization of extractions and

digestions is created. Many more studies will be conducted with different extraction and

digestion procedures and variability will continue to be an issue with S research.

Yield responses to S application were not related to soil S test values for samples

0 to 30 cm deep in the soil profile (Jackson, 2000). Nitrogen and S sources for this

study were as follows: urea, ammonium sulfate, and potassium sulfate and were all

applied as a pre-plant broadcast. Jackson (2000) recommended that for canola about

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20 kg S·ha-1 should be applied to satisfy canola‟s high S requirement when ammonium

acetate-acetic acid-extractable S soil test results are <70 kg S·ha-1. Soil testing for

evaluating S of soils has been suggested as a tool for determining if S fertilizers should

be recommended (Lewis, 1999).

Rationale and Justification

Tomato growers typically use high analysis fertilizers which are low in S content.

This in combination with reduced S emissions from combustion has lowered S input to

agricultural systems. Preliminary studies conducted suggest that S is a limiting factor in

fresh market tomato yield. Therefore, unless the characterization of S in the crop

production system is identified, an increasing trend in S deficiency in all crops will

become apparent.

The overall objective of this study is to explore, determine and apply soil SO4-S

extraction methods in Florida sandy soils to achieve optimal tomato growth and

development. Therefore the specific objectives are:

to determine whether, a response to different sources and rates of SO4 on tomato plant growth, development, tomato yield, and S content exists.

to determine the influence of irrigation rate and rate of applied S on tomato growth, development, and yield.

to compare extraction methods and analytical methods for SO4 and S determination in soil samples.

to establish and interpret the relationship between soil SO4-S, tomato tissue S concentrations or tomato yield.

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Table 2-1. Sulfur containing fertilizers, formulas, and percent S and companion nutrients for materials used in crop production.

Materialz Formula

Plant Nutrient Content (%)

S Other

Ammonium nitrate sulfate

NH4NO3 + (NH4)2SO4 14 26% N

Ammonium polysulfide

NH4Sx 45 20% N

Ammonium phosphate sulfate

[(NH4)2HPO4 + (NH4)H2PO4] + (NH4)2SO4

12-17 11-16% N, 13-48% P2O5

Ammonium sulfate (NH4)2SO4 24 21 N Ammonium thiosulfate (NH4)2S2O3 26 12 N Calcium polysulfide CaSx 22 6 Ca Calcium sulfate CaSO4 16-23 29 Ca Calcium thiosulfate CaS2O3 10 6 Ca Elemental S S or S0 100 Ferric sulfate Fe2(SO4)3·9H2O 18-30 20-35 Fe Ferrous sulfate Fe2(SO4)3·7H2O 16-30 20-35 Fe Gypsum CaSO4·2H2O 19 24 Ca Magnesium sulfate MgSO4 13 10 Mg Potassium polysulfide KSx 23 22 K2O Potassium Mg-sulfate or Sulfate potash of magnesia

K2SO4·MgSO4 22 22-26 K2O, 11 Mg

Potassium sulfate K2SO4 18 50 K2O Potassium thiosulfate K2S2O3 17 25 K2O Sulfuric acid H2SO4 33 S coated triple superphosphate

Ca(H2PO4)2·CaSO4·2H2O + (NH4)2SO4 + S0

10-20 38-43 P2O5, 14-16 Ca

Single super-phosphate

Ca(H2PO4)2·CaSO4·2H2O 14 20 P2O5, 18-20 Ca

Triple super-phosphate

Ca(H2PO4)2·CaSO4·2H2O 1.5 46 P2O5, 15-16 Ca

Urea-S CO(NH2)2 + S 10-20 38 N Urea-sulfuric acid CO(NH2)2 + H2SO4 9-18 10-28 N Zinc sulfate ZnSO4·H2O 18 36 Zn

zAdapted from Bixby and Beaton (1970) and Maynard and Hochmuth (2007)

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Table 2-2. Chemical reagents and concentrations for extracting available S from soil and references in which extractants were used.

Reagent Referencez

H2O Bansal et al., 1979 HCl (0.001 M) Bansal et al., 1979 HCl (0.05 M) Islam and Ponnamperuma,

1982 LiCl (0.1 M) Islam and Ponnamperuma,

1982 LiCl (0.01 M) Maynard et al., 1987 NaCl (10 g L-1) Bansal et al., 1979 KCl (0.01 M) Maynard et al., 1987 KCl (0.25 M) Blair et al., 1993 KCl (0.025 M) Bloem et al., 2002 CaCl2 (0.01 M) Yli-Halla, 1987 NH4OAc(0.5 M) Islam and Ponnamperuma,

1982 NH4OAc (0.003 M) Maynard et al., 1987 NH4Cl (0.003 M) Maynard et al., 1987 NH4Cl (0.01 M) Maynard et al., 1987 NaHCO3 (0.5 M NaHCO3) Tiwari et al., 1983 NaOAc (0.073 M) + HOAc (0.52 M) + DTPA (to pH 4.8) Wolf, 1982 NaOAc (1.0 M) + HOAc (to pH 4.8) Bansal and Pal, 1987 NH4OAc (0.5 M) + HOAc (0.5 M) Yli-Halla, 1987 KH2PO4 (500 mg L-1 P) Bansal et al, 1983 Ca(H2PO4)2 (500 mg L-1 P) Islam and Bhuiyan, 1988 Ca(H2PO4)2 (500 mg L-1 P + 2 M HOAc) Hoeft et al., 1973 NaCl (0.1 M) + KCl (0.25 M) + MgCl2 (1 M) + CaCl2 (2 M) KH2PO4 (0.01M)

Baker, 1973

zadapted from Johnson and Fixen (1990)

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CHAPTER 3 INFLUENCE OF NITROGEN AND SULFUR SOURCES AND APPLICATION RATES

ON FRESH MARKET TOMATO

Introduction

Excess nutrients, particularly nitrate-nitrogen (NO3-N) and phosphate (PO4), are

subject to environmental losses through surface runoff and leaching (Sato et al., 2009).

In vegetable production in sandy soils, NO3-N is of concern because it has the potential

to leach out of the soil profile and into waterways. Best Management Practices (BMP)

are practices or compilation of practices, which are scientific based, field tested,

reviewed, voluntary, and incentive driven to improve water quality in agricultural and

urban discharges (Bartnick et al., 2005). Sulfur has also been subjected to legislative

control, because of acid rain development from SO2 emissions.

„Hidden hunger‟ is a term generally applied to describe micronutrient malnutrition

in humans (Welch and Graham, 1999), but can also be used to describe nutrient levels

below optimum in plants (Bould, 1968; Dwivedi and Randhawa, 1974; Smith, 1962).

This is an old term used to describe sub-adequate levels in which nutrient deficiency

systems may not be evident, yet growth and yield are below the optimum. Positive yield

and growth results have been shown when S has been applied to vegetable crops

(Pavlista, 2005; Rhoads and Olson, 2000; Susila, 2001). Sulfur deficiencies are often

confused with N deficiency in plants as N and S assimilation are closely coordinated

(Schere, 2001; Tabatabai, 1984; Zhao et al., 1997) and yellowing of plant tissues is

generally upon first observation considered to be N deficiency. In addition, NO3

reduction or protein synthesis is inhibited by S deprivation (Duke and Reisenauer, 1986)

and this can be considered an antagonistic relationship between excess N and deficient

S (Eriksen et al., 2001; Eriksen and Mortensen, 2002). It has been stated by Haneklaus

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et al. (2008) for a 1 kg shortfall of S, 15 kg of N are loss to the environment due to

volatilization and leaching, because N utilization efficiency has been reduced (Schnug,

1999). Eriksen et al. (2001) found that increasing N application at low S supply caused

S deficiency symptoms to become more pronounced and resulted in a serious

retardation of plant growth, suggesting that high N levels decreased the redistribution of

S from older leaves. Yet, no connection to barley (Hordeum vulgare L.) yield was made

in this study to determine if S deficiency resulted in lower yield of barley. Eriksen and

Mortensen (2002) also examined the impact of N and S on barley yields. An interaction

with N application and the relative yield increase with S applications were much higher

at high N levels than at the lower N application rates. The later the S application in time

with high levels of N, the decrease in yield was more pronounced for grain than yield of

S amino acids (Eriksen and Mortensen (2002). These studies did not focus upon the N

to S ratio, which is often used as an index for methionine and cystine concentrations, as

well as for general plant growth (Radford et al., 1977; Sexton et al., 1998).

The N to S ratio has been used as an indicator of S deficiency, but it has some

problems with the determination of each element being separately and not concurrent

(Blake-Klaff et al., 2001). Although, this ratio has been stated as being less variable

during plant growth and development (Maynard et al., 1983; Spencer and Freney,

1980), and like all ratios, the magnitude of the individual elements must be taken into

account. An N to S ratio threshold of 15:1 has been suggested by Mills and Jones

(1996). Yet, even this ratio has been subjected to some debate. For winter wheat

(Triticale aestivum L.), it has been indicated that lower than 19:1 would be suitable for

some growth stages (Spencer and Freney, 1980). Calvo et al. (2008) showed that only

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early growth stages of red wheat had N to S ratios below the 15:1 threshold level, but

advanced growth stages were above this N to S ratio threshold. The authors suggested

that N to S ratio should be used in advanced stages of wheat growth to correct S

deficiencies. Thus using N to S ratio could be a tool for diagnosing S deficiencies in

strawberry (Fragaria х ananassa Duch.). As strawberries production season is

approximately 6 months long.

Most Florida surface soils are low in plant-available S, and additional sources are

necessary to maintain optimum production despite the lack of actual cases of S

deficiencies among crops (Mitchell and Blue, 1981). These authors also suggested that

4 kg S·ha-1 as SO4 derived from SO2 from summer rainfall based upon calculations and

estimations by Brezonik et al. (1980) would remain in the soil surface for plant uptake.

They also suggested that 0.8 kg S·ha-1 of the initial 4.8 kg S·ha-1 estimate would be

either leached or immobilized.

Mitchell and Blue (1981) also stated that Spodosols and Entisols lack large

reserves of available S in the subsurface horizons in contrast with that provided by the

agrillic horizon of the Ultic soils. The lack of available S reserves for crop growth in

Florida sandy soils was further supported by Susila (2001). Both surface and subsoil

horizons were inefficient in supplying enough S for six weeks of growth without the

addition of pre-plant application of S as (NH4)2SO4. Although, this study utilized an

Arredondo fine sand soil (loamy, siliceous, hypertherimic, Grossarenic Paleudult), an

Ultisol, growth of tomato on this soil required S applications. These results are in

conflict with Mitchell and Blue (1981) who stated that Ultisols may have enough reserve

S in the subsoil for plant growth.

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It is recommended that if S deficiencies are diagnosed for vegetable crops grown

in Florida, applications of 28 to 37 kg S·ha-1 should be provided (Simonne and

Hochmuth, 2009). Yet, recommendations for S in crop production have often been

empirical in nature rather than based upon previous research. These recommendations

might not accurately reflect the current S status of the soil since the reduction in

atmospheric S has occurred over the past 20 years. This has been a recurring problem

in S research, namely soil recommendations not accurately reflecting the current status

of S in soils and therefore crops.

Limited information exists on tomato response to concurrent N and S applications

as either different sources or rates. Information does exist for N applications as

different sources or rates as NO3 movement in soils is an important issue for Florida

tomato growers. Hochmuth and Cordasco (2000) summarized that yield of tomato

occasionally increased when N is applied over 224 kg N·ha-1 and yield responses were

similar when using drip or subsurface irrigation in Florida. Regardless of the differences

in soil type within the major tomato growing areas of Florida, this finding led to the

implementation of a recommendation of 224 kg N·ha-1 on tomato. Supplemental N

application of 34 kg N·ha-1 is recommended 1) after a leaching rain, (7.3 cm in 3 d, or

9.8 cm in 7 d), 2) measured „low‟ plant nutrient content or 3) extended harvest season

(Olson et al., 2009). Ozores-Hampton et al. (2006) suggested that the actual rate of N

needs to be adjusted based upon planting date and irrigation method. This adjustment

of the current recommendation is based upon the differences in fertilizer salt movement

with temperature (planting date) and water application (drip versus subsurface

irrigation).

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Similarly to concurrent N and S research, S leaf sufficiency range, source and

rates studies in field grown tomato are lacking. Those studies conducted involve

greenhouse grown tomato and hydroponic culture, which does not involve the soil S

cycle, but solution pH. Susila (2001) found that tomato yield responses to different S

sources ((NH4)2SO4 versus NH4S2O3) were similar, regardless of application method

(broadcast versus drip injected). Heeb et al. (2006) found that the inclusion of S into the

fertilizer program for greenhouse-grown tomato increased yield and growth in

comparison with fertilizer program without S. This study also found that tomatoes with

S in the fertilizer program had preferred taste when compared to similar treatment

programs without S.

For field-grown tomato, the sufficiency range within leaf tissue is 3,000 and 8,000

mg S·kg-1 on a dry weight basis (Olson et al., 2009). Despite previous studies finding

positive results for tomato within this range (Susila, 2001); it is possible that this range

of S sufficiency is too broad for field grown tomato. Therefore, the objective of this study

was to compare sources and rates of N and S fertilizers on field-grown fresh market

tomato and tomato leaf S concentrations.

Materials and Methods

Two separate field trials were conducted in the fall 2006 and spring 2007 at the

University of Florida (UF) Gulf Coast Research and Education Center (GCREC),

Institute of Food and Agriculture Sciences (IFAS), University of Florida in Balm, FL on a

sandy, siliceous, hyperthermic Oxyaquic Alorthod soil with 1.5% organic matter and a

soil pH of 7.3. The soil was very low in SO4 content (<30 mg S·kg-1) as revealed by

BaSO4 turbidimetry and soil test interpretation performed 4 weeks before transplanting

by a commercial laboratory. Fertilizer sources for treatment applications were

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ammonium nitrate (NH4NO3), potassium sulfate (K2SO4), ammonium sulfate

((NH4)2SO4), and ammonium sulfate nitrate (NH4NO3 + (NH4)2SO4) at rates 0 and 186

kg N·ha-1 with 0 and 213 kg S·ha-1. Fertilizer sources were chosen based upon S

content and likelihood of being used in a „hot mix‟ fertilizer by tomato growers. „Hot mix‟

refers to fertilizer that is banded on top of a raised bed. This fertilizer blend has a high

salinity and thus termed „hot‟. Over time, this „hot mix‟ is dissolved via the movement of

irrigation water in a subsurface irrigation system. Therefore, the fertilizers (salts) are

diluted via subsurface irrigation. Muriate of potash (KCl) (60% K) was used to balance

total K amounts in those treatments using NH4NO3 or (NH4)2SO4 as a fertilizer source to

ensure that this nutrient was under similar non-limiting conditions (Table 3-1).

The plots were arranged in a randomized complete block design with four

replications. Experimental plots were 8.8-m long with a 2.9-m long non-treated buffer

zone at the end of each plot. Fertilizer treatments were applied 21 d before

transplanting within two 7.6-cm deep bands separated 34 cm apart centered on the bed

top as „hot mix‟. Planting beds were 78 cm wide at the base, 68.6-cm wide at the top,

19.6-cm high, and spaced 1.47 m apart on centers. Pressed beds were fumigated with

methyl bromide plus chloropicrin (67:33 v/v) at a rate of 196 kg·ha-1 to eliminate

soilborne diseases, nematodes, and weeds on 1 Aug. 2006 and 23 Feb. 2007.

Simultaneously, planting beds were covered with 1.5-μm thick silver on black mulch.

„Florida-47‟ tomato transplants were established 59 cm apart on single rows on the

center of each bed on 17 Aug. 2006 and for the second experiment on 12 Mar. 2007.

Irrigation was supplied as subsurface irrigation at an approximate rate of 61,983 L·ha-1

per day in Fall 2006. Irrigation was supplied as a hybrid irrigation system in Spring

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2007. A hybrid irrigation system uses both subsurface and drip irrigation and employed

by those growers transitioning from all subsurface to drip irrigation. Irrigation supplied

as subsurface was at the approximate rate of 21,035 L·ha-1 per day. Drip irrigation

tubing (T-Tape Systems International, San Diego, CA) was buried to a depth of 2.5 cm

in the center of the raised bed with a flow rate of 0.058 L·m-1·min-1. The irrigation rate

using drip system was at an approximate rate of 39,095 L·ha-1 per d. Therefore, the

total water applied via irrigation for Spring 2007 was 60,130 L·ha-1 per d. The water

table was maintained between 46 and 61 cm deep and constantly monitored with

piezometers located in the fields. Phosphorus (P) was not added, because soil analysis

revealed 108 mg P·kg-1 and this is considered as a concentration „high‟ for tomato

production (Simonne and Hochmuth, 2009). Tomato plants were staked and tied as

described by Csizinszky et al. (2005) and weekly spray applications to maintain pest

and disease control based upon weekly field scouting results.

Newly mature leaves were randomly collected from each plot at 12 wk after

transplanting (WAT) to determine foliar S concentration in Fall 2006 and Spring 2007.

These samples were dried at 109 °C and ground to pass through a 0.853 mm sieve

aperture (20-mesh screen). Samples were sent to a commercial lab for total S

determination by ICP-OES. Tomato fruit were harvested twice (8 and 10 WAT in Fall

2006, 10 and 12 WAT in Spring 2007) and graded as marketable and non-marketable

based upon size. Marketable tomato fruits were graded according to the current

industry standards for size categories (Brown, 2009; Sargent and Moretti, 2004). The

sizes were 5X6 (7.0 cm), 6X6 (7.06 to 6.32 cm), 6X7 (6.43 to 5.72 cm), and cull (<5.4

cm). Cull fruit were those smaller than 5.4 cm in diameter, which is below the minimum

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diameter for a 6x7 tomato fruit. All data were analyzed using ANOVA to determine

treatments effects (P<0.05) and treatment means were separated using Waller-Duncan

mean separation procedure and orthogonal contrasts (SAS Institute, 2000). Single

degree-of-freedom orthogonal contrasts were used to compare individual treatments.

All contrasts were checked to ascertain that they were stochastically independent, and

coefficients equal to zero.

Results and Discussion

Total marketable yield and quality of tomato were both significantly influenced by S

applications (Table 3-2 and Table 3-3) for Fall 2006 only. In Fall 2006, both NH4NO3 +

K2SO4 + KCl and NH4NO3 + (NH4)2SO4 + K2SO4 had higher total yield than the non-

treated control, NH4NO3 + KCl and (NH4)2SO4 + KCl with an average total yield of

42,099 kg·ha-1. Any treatment that included S as either K2SO4 or NH4NO3 + (NH4)2SO4

were significant when compared to NH4NO3+ KCl. Also the comparison between

(NH4)2SO4 + KCl against NH4NO3 + K2SO4 + KCl and NH4NO3 + (NH4)2SO4 + K2SO4

were significant.

For Spring 2007, all treatments had higher yields when compared to the non-

treated control with a total average marketable yield of 72,741 kg·ha-1. None of the

single degree of freedom orthogonal contrasts were significant suggesting that

temperature, rainfall, and possibly the hybrid irrigation system used in the second

season influenced yield response. The differences between total marketable yield and

quality of yield could be due to the inherent season temperature and rainfall patterns

that occur in Florida. The average rainfall and temperatures for each season were 27.9

and 17.9 cm with minimum temperatures of 18 and 14.5 °C, and maximum

temperatures 30.9, and 28.7 °C, Fall 2006 and Spring 2007, respectively. It is also

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possible that even though the irrigation water amount was similar in both seasons. The

differences in the irrigation systems could have influenced the increased total yield in

Spring 2007.

For Fall 2006, both 5x6 and 6x6 grade tomato followed the same pattern as total

marketable yield for the season (Table 3-3). Both NH4NO3 + K2SO4 +KCl and NH4NO3

+ (NH4)2SO4 + K2SO4 had higher quality yield than those treatments receiving no S and

(NH4)2SO4 + KCl. The yield by tomato size (grade) for 5x6 and 6x6 were 17,647 and

13,223 kg·ha-1 for NH4NO3 + K2SO4 +KCl and NH4NO3 + (NH4)2SO4 + K2SO4,

respectively. Tomato yield for 6x7 size was similar to both 5x6 and 6x6 in respect to

mean separation, but NH4NO3 + KCl was also similar to NH4NO3 + K2SO4 + KCl for all

sizes of tomato. The single degree of freedom orthogonal contrasts were significant for

NH4NO3 + KCl compared to NH4NO3 + K2SO4 + KCl and NH4NO3 + (NH4)2SO4 + K2SO4

for this size. Plus (NH4)2SO4 + KCl compared to NH4NO3 + K2SO4 + KCl and NH4NO3 +

(NH4)2SO4 + K2SO4 contrasts were significant. This suggested that those treatments

receiving NH4NO3 + K2SO4 + KCl or NH4NO3 + (NH4)2SO4 + K2SO4 were superior in

quality of tomato yield. For Spring 2007, only 5x6 and 6x6 grades were significant for

yield of tomato size (grade) and then only 6x6 had significant single degree of freedom

orthogonal contrasts. The non-treated control was the lowest yielding treatment for 5x6

tomatoes in Spring 2007. All other treatments responded similarly with a total average

yield at 57,437 kg·ha-1. For 6x6 grade tomato in Spring 2007, (NH4)2SO4 + KCl and

NH4NO3 + (NH4)2SO4 + K2SO4 were similar, yet NH4NO3 + (NH4)2SO4 + K2SO4 was not

different from all the other treatments, including the non-treated control. This was

unexpected and the contrasts further reveal that (NH4)2SO4 + KCl was the superior

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treatment when compared to NH4NO3 + K2SO4 + KCl, NH4NO3 + (NH4)2SO4 + K2SO4

and NH4NO3 + KCl.

Only Spring 2007 was foliar S concentrations within tomato leaves significant

(Table 3-4). All treatments were similar except for NH4NO3 + KCl which had the lowest

S leaf concentration at 6,500 mg S·kg-1. This amount is still within the recommended

range (3,000 to 8,000 mg S·kg-1) as stated by Olson et al. (2009). Three single degree

of freedom orthogonal contrasts were significant; NH4NO3 + KCl versus (NH4)2SO4 +

KCl, NH4NO3 + KCl versus NH4NO3 + K2SO4 + KCl; NH4NO3 + KCl versus NH4NO3 +

(NH4)2SO4 + K2SO4.

Adding S to the fertilization programs as part of the „hot mix‟ increased tomato

uptake of this nutrient only in Spring 2007. Yet, the quality (i.e. size increase) of tomato

harvested was higher in Fall 2006 with the same treatments. This suggests that

although S increases total yield and quality of tomato, seasonal impacts in terms of

temperature and rainfall will influence how much S will improve quality.

In this case, positive tomato yield response was found as concentration increased

from about 6,737 and 9,612 mg·kg-1 in Fall 2006 and Spring 2007, respectively when S

was included in the fertilizer regime. This demonstrated that application of S in tomato

fertilization programs is essential to increase marketable yields. These results agree

with those presented by Pavlista (2005), Rhoads and Olson (2000) and Susila (2001), in

which S sources did not cause differential responses to crop growth or development for

cabbage, tomato, or pepper.

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Table 3-1. Nitrogen, K, and S sources, rates applied and placement used to create treatments for determining the influence of N and S fertilization on „Florida 47‟ tomato for Fall 2006 and Spring 2007 at Gulf Coast Research and Education Center in Balm, FL.

Treatment Sources Pre-plant Drip-Injected Total

N K S N K S N K S kg·ha-1

1 Non-treated control 0 270 0 0 0 0 0 270 0 2 NH4NO3 + KCl 186 270 0 0 0 0 186 270 0 3 (NH4)2SO4 + KCl 186 270 213 0 0 0 186 270 213 4 NH4NO3 + K2SO4 + KCl 186 270 213 0 0 0 186 270 213 5 NH4NO3 + (NH4)2SO4 + K2SO4 186 270 213 0 0 0 186 270 213

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Table 3-2. Influence of N and S sources and applied rates on total marketable yield of tomato for Fall 2006 and Spring 2007 at Gulf Coast Research and Education Center in Balm, FL.

Fertilizer sources N Rate K Rate S Rate Yieldz

Fall 2006 Spring 2007 (kg·ha-1)

Non-treated control 0 270 0 13,123b 42,384b NH4NO3 + KCl 186 270 0 19,154b 68,773a (NH4)2SO4 + KCl 186 270 213 15,079b 78,758a NH4NO3 + K2SO4 + KCl 186 270 213 44,096a 66,735a NH4NO3 + (NH4)2SO4 + K2SO4 186 270 213 40,102a 76,699a

P-Values <0.01 <0.01 CV 25 13

Single degree of freedom orthogonal contrasts P-values

NH4NO3 + KCl vs (NH4)2SO4 + KCl 0.40 0.12 NH4NO3 + KCl vs NH4NO3 + K2SO4 + KCl <0.01 0.74 NH4NO3 + KCl vs NH4NO3 + (NH4)2SO4 + K2SO4 <0.01 0.21 (NH4)2SO4 + KCl vs NH4NO3 + K2SO4 + KCl <0.01 0.07 (NH4)2SO4 + KCl vs NH4NO3 + (NH4)2SO4 + K2SO4 <0.01 0.74 NH4NO3 + K2SO4 + KCl vs NH4NO3 + (NH4)2SO4 + K2SO4 0.41 0.12 zmean separation of total yield by Waller-Duncan with α = 0.05

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Table 3-3. Marketable yield quality as influenced by N and S fertilization sources and applied rates for Fall 2006 and Spring 2007 at Gulf Coast Research and Education Center-Balm

Fertilizer sources N

Rate K

Rate S

Rate Grade Distribution (kg·ha-1)z

(kg·ha-1) 5 x 6 6 x 6 6 x 7 Fall 2006 Spring

2007 Fall 2006 Spring

2007 Fall 2006 Spring

2007

Non-treated control 0 270 0 3,505b 29,791b 3,394b 9,598b 5,624c 2,995a NH4NO3 + KCl 186 270 0 4,238b 55,731a 6,358b 10,881b 8,559bc 2,159a (NH4)2SO4 + KCl 186 270 213 4,535b 57,565a 4,238b 19,032a 6,276c 2,160a NH4NO3 + K2SO4 + KCl

186 270 213 19,562a 54,407a 13,530a 10,311b 11,004ab 2,017a

NH4NO3 + (NH4)2SO4 + K2SO4

186 270 213 15,731a 61,946a 12,715a 12,634ab 11,656a 2,119a

P-Values <0.01 <0.01 <0.01 0.03 <0.01 0.81 CV 52 14 30 32 23 56

Single degree of freedom orthogonal contrasts

P-values

NH4NO3 + KCl vs (NH4)2SO4 + KCl 0.92 0.72 0.24 0.01 0.12 0.99 NH4NO3 + KCl vs NH4NO3 + K2SO4 + KCl <0.01 0.24 <0.01 0.54 0.04 0.97 NH4NO3 + KCl vs NH4NO3 + (NH4)2SO4 + K2SO4

<0.01 0.24 <0.01 0.54 0.04 0.97

(NH4)2SO4 + KCl vs NH4NO3 + K2SO4 + KCl <0.01 0.54 <0.01 <0.01 <0.01 0.88 (NH4)2SO4 + KCl vs NH4NO3 + (NH4)2SO4 + K2SO4

<0.01 0.40 <0.01 0.04 <0.01 0.96

NH4NO3 + K2SO4 + KCl vs NH4NO3 + (NH4)2SO4 + K2SO4

0.29 0.16 0.64 0.42 0.64 0.91

zmean separation of yield quality by Waller-Duncan with α = 0.05

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Table 3-4. Effects of N and S sources and applied rates on tomato foliar S concentration as percent S for Fall 2006 and Spring 2007 at Gulf Coast Research and Education Center in Balm, FL.

Fertilizer sources N Rate K Rate S Rate Foliar S concentrationz

(kg·ha-1) (mg·kg-1) Fall 2006 Spring 2007

Non-treated control 0 270 0 5,333a 8,725a NH4NO3 + KCl 186 270 0 4,550a 6,500b (NH4)2SO4 + KCl 186 270 213 5,450a 9,400a NH4NO3 + K2SO4 + KCl

186 270 213 6,900a 8,625a

NH4NO3 + (NH4)2SO4 + K2SO4

186 270 213 6,450a 9,725a

P-Values 0.16 0.02 CV 23 15

Single degree of freedom orthogonal contrasts P-value

NH4NO3 + KCl vs (NH4)2SO4 + KCl 0.35 <0.01 NH4NO3 + KCl vs NH4NO3 + K2SO4 + KCl 0.02 <0.01 NH4NO3 + KCl vs NH4NO3 + (NH4)2SO4 + K2SO4 0.06 <0.01 (NH4)2SO4 + KCl vs NH4NO3 + K2SO4 + KCl 0.15 0.40 (NH4)2SO4 + KCl vs NH4NO3 + (NH4)2SO4 + K2SO4 0.30 0.72 NH4NO3 + K2SO4 + KCl vs NH4NO3 + (NH4)2SO4 + K2SO4

0.64 0.24

zFoliar S concentration data means separated with Waller-Duncan with α = 0.05

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CHAPTER 4 SULFUR FERTILIZATION RATES AND IRRIGATION PROGRAMS ON TOMATO

GROWTH AND YIELD

Introduction

Crop plants obtain their S requirement from a number of sources; including soil,

crop residues, manures, irrigation waters, rainfall, the atmosphere, and soil

amendments and fertilizers (Tabatabai, 1984). Field sites without access to mineral

bound S sources may have insufficient S dissolved in soil water and shallow ground

water bodies to move available S to plant roots (Eriksen et al. 1998). The concentration

of S in irrigation waters used throughout North American is unknown, and little research

is available related to the S content of irrigation waters to S requirement in a fertilizer

program (Olson and Rehm, 1986). Studies on high sulfate irrigation waters utilized

water with 175, 646, 862, and 1743 mg·L-1 SO4 (Drost et al., 1997) and 15.0 and 38.8

mol SO4·L-1 (Papadopoulos, 1986) have found mixed results in improving yield of

broccoli and tomato. In Florida, SO4 levels in drinking water wells can range from 0.2 to

1400 mg·L-1 with higher concentrations coming from deeper wells (Sacks, 1996). While

these values cover drinking water, the levels of SO4 or S within irrigation water in Florida

is unknown. It has been suggested that water pumped from the aquifer as well as

surface waters, has a rotten-egg smell commonly associated with S. This may often

leads to the belief that S in the irrigation water is an S source for crop production.

Tomato production in Florida often occurs on deep Spodosols (fine sandy soils)

with low organic matter (>2%) and therefore inherently low in organic and inorganic S.

Previous studies on tomato and S has found that S sources ((NH4)2SO4, NH4S2O3,

NH4NO3 + (NH4)2SO4, K2SO4) affected tomato yields similarly (Susila, 2001; Santos et

al., 2007). Elemental S is a less expensive S fertilizer source when compared to other

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sources of S that contain N. Yet, limited information exists on using elemental S with

irrigation programs to improve tomato S content and yield in Florida. Elemental S can

be an ideal S source for crop growth and yield because it is 1) high analysis of S and

insoluble in water; 2) stable in damp and humid conditions 3) has to be oxidized to SO4-

S for plant uptake (Solberg et al., 2003). In order to achieve high yields and to minimize

S leaching, rates of fertilizer S should be recommended on the basis of available soil S

and crop requirement (Scherer, 2001). Therefore, the goal of this study was to

investigate whether or not irrigation water in conjunction with S applications can supply

the necessary S for tomato production. The objective of this study was to determine the

influence of irrigation program and S rates on fresh market tomato growth and yield.

Materials and Methods

Two field studies were conducted at GCREC on a Myakka fine sand (sandy

siliceous hyperthermic Aeric Alaquods) for two seasons, Spring 2008 (Mar. to July

2008) and Fall 2008 (Aug. to Dec. 2008). All crop management was conducted

according to current recommendations for tomato (Olson et al., 2008). Soil was

fumigated with 50:50 (v:v) methyl bromide to chloropicrin mixture at 190 kg·ha-1 using

metalized polyethylene mulch on 14 Feb. and 5 Aug. 2008. „Tygress‟ tomato seedlings

were transplanted on 6 Mar. 2008 and 28 Aug. 2008, 21 d after soil fumigation into

raised beds (19.6 cm high and 68.6 cm wide). The experimental design was a split-plot

with six replications. This design allows for more precision to be given to factors within

sub-plots. Main plots were drip irrigation volumes of 5,406, 8,109, and 10,812 L·ha-1·d-1

while sub-plots were S rate at 0, 28, 56, 112, 168, and 224 kg S·ha-1. Irrigation rates

were based upon the historical Penman method for central Florida (Simonne et al.,

2009). Irrigation rates were created by changing times and frequencies of drip irrigation

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events. Water levels of SO4-S at GCREC was found to be 57.8 mg·L-1. Sulfur rates

were applied pre-fumigation as elemental S (0-0-0-90S). All other nutrients were applied

at recommended rates base on soil test results (Olson et al., 2008) using a 6-2-8 (N-

P2O5-K2O) liquid fertilizer.

The following variables were collected: soil samples at 5 and 13 WAT in Spring

2008 and 4 and 15 WAT in Fall 2008 for soil S, and pH. Dried soil samples were

submitted to Waters Agricultural Laboratory in Camilla, GA for SO4 determination by the

turbidimetric method. Plant tissue samples for S were collected 5 and 13 WAT in

Spring 2008 and 4 and 11 WAT in Fall Season 2008. Dried and ground tissue samples

were also submitted to Waters Agricultural Laboratory in Camilla, GA for total S

determination by ICP-OES. Soil samples were held at 4.4° C and tissue samples at 0°

C until shipment to the lab for analysis.

Soil moisture was monitored every other week for 5 d using a time domain

reflectometry probe (TDR) (FieldScout TDR 200 Soil Moisture Meter, Spectrum

Technologies, Inc., Plainfield, IL). Plant vigor was assessed on 5, 8, and 12 WAT in

Spring 2008. Plant vigor was a subjective visual assessment on a scale from 0 to 100;

where 0 indicates a dead plant and 100 was a very healthy green plant. Plant height

was collected on 5 and 13 WAT in Spring 2008. For Fall 2008, plant height was

collected as an alternative to the subjective plant vigor rating at 5 WAT. Estimated

chlorophyll was collected as leaf greenness using a Minolta SPAD-502 meter at 4, 6,

and 11 WAT in Spring 2008 and at 7 and 11 WAT in Fall 2008. Tomato fruit were

harvested during 12 and 13 WAT in Spring 2008 and 11 and 14 WAT in Fall 2008.

Harvested fruit were then separated as marketable and non-marketable based upon

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size. Marketable tomato fruits were graded according to the current standards for size

categories (Brown, 2009; Sargent and Moretti, 2004). The sizes were 5X6 (7.0 cm),

6X6 (7.06 to 6.32 cm), 6X7 (6.43 to 5.72 cm), and cull (<5.4 cm). These sizes are

based upon the number of horizontal rows and columns of fruit fitted into an 11.3-kg

tomato box. Cull fruit were those smaller than 5.40 cm in diameter which were below

the minimum diameter for a 6X7 marketable tomato fruit. Data were subjected to an

analysis of variance to determine treatment significance using a general linear model

(SAS Institute, 2000). Regression models were also fit to significant data using

SigmaPlot (Systat, 2008). Treatment means were separated by standard errors.

Results and Discussion

No interactions were observed between irrigation volumes and S rates for any

collected plant variable. Irrigation volumes were found to influence early season plant

vigor in Spring 2008, but was not evident at the end of the season. An increase in vigor

was observed when irrigation volumes were increased from the lowest rate to the

highest rate, although a linear contrast was not significant (Table 4-1). Plant height was

not influenced by either irrigation or S rates in either growing season (Table 4-1).

Estimated chlorophyll was also not influence by either irrigation volumes or S rates for

Spring 2008 growing season (Table 4-2). However, late in Fall 2008, estimated

chlorophyll was influenced by applied S rates and both linear and quadratic contrasts

were significant for this observation (Table 4-2). Mid-season soil SO4-S and soil pH

were not influenced by either irrigation program or S rate for both Spring and Fall 2008

(Table 4-3). End of season soil SO4-S and soil pH were not influenced by irrigation

regime and applied S rates for Fall 2008. However, Spring 2008, end of season pH

were influenced by applied S rates and a significant linear contrast was found. It is

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possible that season temperature and rainfall differences between cropping seasons

may be responsible for the pH differences within the soil, because oxidation of S is

highly dependent upon environmental factors. Solberg et al. (2003) has suggested

elemental S fertilizers require oxidation time to become plant-available SO4-S which

may help explain the lack of differences in S. The oxidation of elemental S is highly

dependent upon soil conditions particularly to those soil microbes involved in the S

cycle. Unexpectedly, an increase in irrigation rate did not influence soil SO4-S or soil

pH. Increased soil moisture is believed to increase elemental S oxidation in the soil.

This suggests that soil C or soil substrates may be the limiting factor of S oxidation in

Florida sandy soils.

A seasonality effect of S applications on leaf S concentration was found to exist

(Table 4-4). After separation of the two seasons, S leaf concentrations were no longer

influenced by applied S rates. For Spring 2008, S leaf concentrations ranged from

5,456 to 5,714 mg S·kg-1. Despite these results for Spring 2008, irrigation was found to

influence Fall 2008 S leaf concentration and a significant linear contrast was found.

Leaf S concentration decreased with increasing irrigation regime, possibly indicating

that as applied S oxidized into SO4 form it was leached from the root zone. All the leaf

S concentrations were within acceptable range for leaf S for tomatoes (Olson et al.,

2008; Susila, 2001), regardless of season.

Early tomato yield was influenced by S rates (P < 0.05), but not irrigation (data not

shown). Yields were observed to increase (Figure 4-1) in a linear plateau fashion

described by the following equation (y = 10,851/ (1 + e (-(x+1.15)/1.16)))). This curve

was also used by Blake-Kalff et al. (2000) to describe S fertilization influence on yield of

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wheat. Increasing S applications from 0 to 28 kg S·ha-1 improved early yield by over

3,500 kg·ha-1. Adding 28 kg S·ha-1 is equivalent to increasing tomato yield by one

hundred 11.3-kg boxes per hectare. These results were similar to tomato yield

increases reported by Susila (2001).

Irrigation program did not influence soil S concentration, soil pH, leaf S

concentrations or early tomato yield. This suggested that irrigation water may not have

met the S needs of tomatoes when grown with drip irrigation. It is possible that the form

of S present within the irrigation water needs to be oxidized by microbes. An increase

in tomato leaf S and early yield were found with the addition of elemental S to the

fertilizer regime. Based upon these results, at least a minimal amount of S should be

incorporated into the fertilizer regime to maximize early yield of fresh market tomato in

Florida.

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Table 4-1. Plant height and vigor ratings for tomatoes grown under differing irrigation regimes and applied S rates during Spring and Fall 2008 at Gulf Coast Research and Education Center in Balm, FL.

Plant Heightz (cm) Plant Vigorz (%) Spring 2008 Fall 2008 Spring 2008

5 WAT 13 WAT 5 WAT 5 WAT 8 WAT 12 WAT

Irrigation Regime (L·ha-1·d-1) 5,406 39a 79a 32a 52b 64a 64b 8,109 39a 77a 32a 58ab 65a 70a

10,812 39a 78a 32a 60a 60a 70a P-Value 0.70 0.48 0.57 0.03 0.48 0.35

Linear Contrast Irrigation 0.61 0.31 0.45 0.65 0.16 0.90

Soil S (kg·ha-1)

0 38a 78a 32a 54a 58a 66a 28 39a 78a 32a 56a 60a 69a

56 39a 78a 31a 57a 63a 71a 112 39a 79a 31a 60a 66a 66a

168 39a 78a 33a 56a 66a 67a 224 38a 76a 33a 60a 65a 69a

P-Value 0.54 0.62 0.26 0.70 0.22 0.59 Orthogonal Contrasts

Linear 0.20 0.24 0.11 0.22 0.01 0.76 Quadratic 0.96 0.24 0.41 0.66 0.28 0.63

Cubic 0.18 0.47 0.66 0.57 0.74 0.10 CV 6 6 8 22 20 14

zmeans separation by Waller-Duncan with α = 0.05

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Table 4-2. Estimated chlorophyll content for tomatoes grown under differing irrigation regimes and applied S rates for Spring and Fall 2008 at Gulf Coast Research and Education Center in Balm, FL.

Estimated Chlorophyllz (%) Spring 2008 Fall 2008

4 WAT 6 WAT 11 WAT 7 WAT 11 WAT

Irrigation Regime (L·ha-1·d-1) 5,406 51a 48a 48a 45a 48a 8,109 51a 48a 44a 44a 43c 10,812 51a 46b 83a 44a 44b P-Value 0.75 0.17 0.40 0.84 0.37 Linear Contrast Irrigation 0.38 0.03 0.22 0.93 0.04

Soil S (kg·ha-1)

0 50a 47a 46a 46a 45b 28 50a 48a 46a 45a 48a 56 51a 46a 44a 44a 45b 112 52a 48a 45a 42a 46ab 168 51a 47a 47a 44a 44bc 224 51a 47a 129a 46a 42c P-Value 0.78 0.38 0.50 0.11 <0.01 Orthogonal Contrasts Linear 0.34 0.32 0.16 0.68 <0.01 Quadratic 0.56 0.83 0.21 <0.01 0.02 Cubic 0.74 0.90 0.36 0.50 0.40 CV 15 17 517 09 15

zmeans separation by Waller-Duncan with α = 0.05

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Table 4-3. Mid season and end of season soil pH and soil S content for soil samples collected from tomato production under differing irrigation regimes and applied S rates during Spring and Fall 2008 at Gulf Coast Research and Education Center in Balm, FL.

Soil pH Soil S (kg·ha-1) Spring Fall Spring Fall

Irrigation Regime (L·ha-1·d-1) 5 WAT 13 WAT 4 WAT 15 WAT 5 WAT 4 WAT 15 WAT 5,406 6.7a 6.3a 6.8a 6.7a 25.2a 34.3a 31.9a 8,109 6.6a 6.3a 6.7a 6.7a 25.6a 35.4a 33.1a 10,812 6.6a 6.1a 6.7a 6.8a 24.6a 34.2a 30.0a P-Value 0.91 0.51 0.79 0.21 0.91 0.22 0.49 Linear Contrast Irrigation 0.73 0.33 0.62 0.48 0.60 0.49 0.37

Soil S (kg·ha-1)

0 6.7a 6.8a 6.7a 6.7a 22.6a 33.2a 34.9a 28 6.6a 6.6a 6.7a 6.8a 25.8a 36.0a 27.3a 56 6.6a 6.2b 6.7a 6.7a 22.9a 33.6a 30.8a 112 6.6a 6.2a 6.7a 6.8a 22.8a 34.8a 31.7a 168 6.6a 6.0bc 6.8a 6.8a 27.3a 35.3a 31.2a 224 6.6a 5.8c 6.8a 6.8a 29.5a 39.1a 34.8 P-Value 0.27 <0.01 0.85 0.71 0.12 0.81 0.62 Orthogonal Contrasts Linear 0.12 <0.01 0.53 0.15 0.03 0.61 0.67 Quadratic 0.68 0.49 0.30 0.59 0.23 0.71 0.20 Cubic 0.59 0.50 0.89 0.97 0.39 0.70 0.48 CV 2 9 3 3 35 19 37

zmeans separation by Waller-Duncan with α = 0.05

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Table 4-4. Influence of irrigation regime and applied elemental S rates on tomato leaf S concentrations for seasonal pooled samples for Spring and Fall 2008 at Gulf Coast Research and Education Center in Balm, FL.

S Leaf Concentration (mg·kg-1)z

Spring 2008 Fall 2008

Irrigation Regime (L·ha-1·d-1) 5,406 5,539a 6,079b 8,109 5,711a 6,642a 10,812 5,714a 5,900b P-Value 0.19 0.02 Linear Contrast Irrigation 0.90 <0.01

Soil S (kg·ha-1)

0 5,456a 6,429a 28 5,622a 5,958b 56 5,589a 6,079ab 112 5,686a 6,308ab 168 5,584a 6,275ab 224 5,680a 6,192ab P-Value 0.40 0.11 Orthogonal Contrasts Linear 0.08 0.99 Quadratic 0.46 0.24 Cubic 0.58 0.01 CV 10 7

zmeans separation by Waller-Duncan with α = 0.05

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·

Applied S Rate (kg·ha-1

)

0 50 100 150 200 250

Yie

ld (

kg·h

a-1

)

6000

7000

8000

9000

10000

11000

12000

13000

tomato yield

y = 10,851/(1+exp(-(x+1.15)/1.16)), R2 = 0.88, P = 0.03

Figure 4-1. Influence of rates of applied elemental S on first harvest of fresh market tomato for Spring and Fall 2008 at Gulf Coast Research and Education Center in Balm, FL.

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CHAPTER 5 COMPARISON OF ANALYTICAL METHODS FOR DETERMINE S AND SO4-S

PRESENT IN FLORIDA SANDY SOILS

Introduction

Current assessment of S and SO4-S in agricultural soils for the development of

fertilizer recommendations has been difficult. The major difficulties that researchers

confront are inherent variability in analytical results, lack of consistent associations

between crop yield, and S in soils or plant tissues. In addition to these difficulties, soil or

plant S determination is often a separate method adding time and costs in an analytical

laboratory.

Ideal characteristics for S determination would be low cost, rapid, accurate,

precise, with low interference, and potentially offer multi-element determination options

(Table 5-1). Soil chemical analysis or „soil testing‟ is the cheapest and most-widely

used chemical analysis employed in agriculture (Van Raij et al., 2002) and is often

underutilized by many (Jones, 1993). It is primarily the cost of labor to operate

analytical instrument that determines the underlying cost of each soil sample.

In terms of speed, many instruments (i.e. elemental analyzer, inductively coupled

plasma-atomic emission spectrometer or inductively coupled plasma-optical emission

spectrometer (ICP-AES/ICP-OES), ion-exchange chromatograph (IC), and discrete

analyzer) have been automated to allow sample loading time to be reduced. This can

essentially cut labor and time for the laboratory worker spent supervising instrument

status. In the past, S and SO4-S determination were labor intensive and required

reagents have a finite shelf life for use. Such example is methylene blue, which is the

color reagent for estimating the reduction of sulfate to sulfide (Tabatabai, 1996). The

color of this reagent is important to the determination of S by spectrometric means; if

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kept away from direct sunlight the color can remain stable for 24 h or more (Tabatabai,

1996). This would be considered to be a time limitation or shelf-life restriction for this

method. Not properly understanding and identifying limitations in a method can lead to

data quality issues.

Quality control and assurance plans are implemented to maintain result quality.

Quality control consists of using the following: proper calibration, blanks, duplication of

samples, spiked samples and the use of certified standards (Shampine, 1993). Quality

assurance usually consists of validation of methods (characteristics and limits). Both of

these are extremely important to S determination, because of the inherent variability in

determining S and SO4-S. It has been reported by Crosland et al. (2001) that the

coefficient of variation from an inter-laboratory study on soil S was between 36 to 45%.

This means up to 45% of the variation in soil S values was due to random error and the

decision to apply fertilizer based upon this data could be faulty. This random error can

be attributed to operator error, loss of calibration during analysis or interferences from

other elements within the aliquot.

Interferences from other elements or ions are the most common error encountered

when determining S or SO4-S. With the advent of newer technologies, such as ICP-

OES, claims that less interference would be encountered were publicized (Kola et al.,

2002). Multi-element determinations are limited to those instruments with the ability to

determine multiple elements. These include, but are not limited to the following:

elemental analyzers, ICP-AES/ICP-OES, and IC. Instruments with multiple element

determination capabilities are viewed as a versatile economic investment. These types

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of instruments reduce labor, because more than one element can be analyzed within a

single sample.

Currently five analytical instruments are capable of determining total S or SO4-S.

These instruments are ICP-AES or ICP-OES, inductively coupled plasma mass

spectrophotometer (ICP-MS), elemental analyzer by infrared radiation cell/spectrometer

(IR) or titration of SO2, IC, and turbidimeter. Of these five instruments, the three most

commonly used to determine S or SO4-S are ICP-AES/ICP-OES, elemental analyzer via

IR or titration, and colorimetrically with a spectrometer (turbidimeter).

The principle behind ICP-AES/ICP-OES is based in chemistry and physics. More

specifically, it involves particle collision, excitement of outer shell electrons,

adsorption/emission of a wavelength, and separation/detection of spectral lines of

interest. An extended review of the theory will not be presented here, but several

reviews and sources explain in detail such theory and mechanics of ICP-AES/ICP-OES

(Boss and Fredeen, 1997; Lajunen and Perämäki, 2004; Manning and Grow, 1997;

Welz et al., 2009). Several advantages for determining S with ICP-AES/ICP-OES are

after initial costs: cost effectiveness, rapid sample analysis, multiple element, low level

of interferences, wide linear dynamic range and detection limits at the μg·L-1 level (Kola

et al., 2002 Mermet and Poussel, 1995). One disadvantage for determining S with ICP-

AES/ICP-OES is that a vacuum is required within the instrument as S is considered a

non-metal element. This is required because emission lines for S lie in the ultraviolet

range so that the lines are not absorbed by O2 (Soltanpour et al., 1996). A range of

emissions are used for S on ICP-AES/ICP-OES. In general, the range of wavelengths

used is from 180.04 to 182.63 nm, and the three strongest emission lines of S in the

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vacuum ultraviolet spectrum are at 180.73, 182.04, and 182.63 nm (Wu et al., 2009).

Two significant spectral overlaps occur around the 180.73 nm S line; 180.361 nm Ca

and 180.74 nm Mg lines (Eames and Cosstick, 1992). Therefore, corrections or

adjustments must be made to ensure interfering spectral lines are not distorting results

for S.

The principle behind an elemental analyzer, often called by brand name LECO or

by the method name Dumas, is titration via colorimetric determination or IR

determination of total S. The Dumas method involves the combustion of samples at

high temperatures (<1000° C) and the evolution of S as SO2 and subsequent capture

for determination. Earlier Dumas models use a photocell with SO2 collected by HCl

containing KI, starch, and a trace amount of KIO3, approximately 0.22 M KIO3

(Tabatabai, 1996; Tiedemann and Anderson, 1971) or 1N NaOH (Tabatabai, 1996) with

colorimetrically determining total S by methylene blue similar to Johnson and Nishita

(1952). For IR determination of S, after combustion, a stream of gas is directed into a

ballast tank, homogenized before a sample is trapped for infrared detection of S

(Kowalenko, 2001). The infrared source consists of nichrome wire, which was

resistance-heated to 850° C, SO2 absorbs infrared energy at 3.98 and 7.35 μm (Gong et

al., 2006), with a band-pass filter to prevent further infrared energy reaching the IR

detector (LECO, 2006).

The advantages of an elemental analyzer were that it was designed for simplicity,

speed, convenience, C and N could also be determined with some models (Tabatabai,

1996), and capable of measuring total S in soils including those with high organic matter

content is possible unlike with wet digestion methods such as sodium hypobromite

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(NaBrO) (Kowalenko, 2001). Some disadvantages of elemental analyzers are the

following: initial cost of the instrument, the built in flow conditions for S restrict the

scope for optimizing the combustion cycle for organic and total C determinations when

analyzing C and S simultaneously (Wright and Bailey, 2001), and without an automated

sample loader this process consumes time and labor to load each sample individually.

The principle behind SO4-S determination by turbidity was the Beer-Lambert‟s law

in which a reduction in the intensity of light passing through a solution containing

suspended particles of BaSO4 (Beaton et al., 1968). The Beer-Lambert law was written

as A = εbc. This equations states that absorbance (A) is directly proportional to molar

absorbtivity (ε) multiplied by path length of cuvette (b), and the concentration (c) of the

solution within the cuvette. Absorbance was used instead of percent transmission

because absorbance follows a linear line when plotted against concentration. This

relationship or law is not obeyed at higher concentrations. The advantages of

determining SO4-S by turbidimetry are that the determination is rapid, in some cases

sensitive, most commonly used for determining SO4-S in soils. Therefore many

modifications are available to adjust for its short comings including exchange resins,

addition of charcoal filters, and flow injection analysis (Morais et al., 2006). The

disadvantages to turbidimetric measurement of SO4-S are insensitivity at low

concentrations (less than 10 mg·L-1), multiple cation interferences (Na, K, Ca, Mg, NO3,

PO4, and SiO2), cation co-precipitations with Ba, high organic matter co-precipitation,

and difficulty of reproducible BaSO4 suspensions under uniform precipitating conditions

(Beaton et al., 1968; Tabatabai, 1996).

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While these are the most commonly available methods in the US for the

determination of S and SO4-S, it is unknown if a relationship can be established

between them. The goal of this study was to find the ideal analytical equipment that

would accurately determine S as either total S or SO4-S. The objective of this study

was to compare analytical equipment used to determine soil S and SO4-S for Florida

sandy soils.

Materials and Methods

Soil samples were collected on 16 May 2007 from tomato fields at Gulf Coast

Research and Education Center in Balm, Florida. Fifty-two soil samples were randomly

taken from within an 8.8 m linear plot of the raised bed (78 cm wide at base, 19.6 cm

high and 68.6 cm wide at the top, spaced 1.47 m apart) between tomato plants and

were approximately 15 to 20 cm deep of surface soil. After collection, soil samples

were air dried, sieved, and stored at 4.4° C until analysis was conducted. Soil SO4-S

status was characterized by extractions with de-ionized water, and 0.025 M KCl (Table

5-2) using a spectrophotometer (Spectronmic 100, Bausch & Lomb, Rochester, NY) on

16 Sept. 2009 at a commercial laboratory. The standard method for determining SO4 in

water by turbidimetry (AOAC-OM-973.57, ASTM D 516-02) (AOAC, 2000; ASTM, 2006)

was considered to be the standard reference method for SO4-S determination and used

for comparison with other methods at Waters Agricultural Laboratory in Camilla, GA.

Total soil S status was characterized by de-ionized water, and 0.025 M KCl, using ICP-

OES (Optima 2100 DV, Perkin-Elmer, Waltham, MA) with Eschelle grading and under a

constant vacuum (Table 5-2) at GCREC Analytical Lab in Balm, FL on 19, 20 and 21

Dec. 2008, 8, 9 and 21 July 2009. The LECO ( LECO Corp., St. Joseph, MI) method

with SO2 measurement by infrared radiation (CNS 2000, LECO Corp., St. Joseph, MI)

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(Table 5-2) was conducted on 16 June 2009 at a MicroMacro International Laboratory in

Athens, GA.

All data were analyzed using a linear regression model (yij = αi + βixij + εij) with test

slope = 1 and test intercept = 0 statements with P<0.05 (SAS Institute, 2000). These

parameters of the regression line were tested to determine if plotted regression lines

were similar to the ideal relationship between analytical instruments. This ideal

relationship is a regression line with a slope of 1 (1 rise to 1 run or 1:1) with an intercept

of 0. Therefore, if the test slope statement test H0: βi = 1 is not significant (P>0.05) then

the slope is not significantly different from 1 and if the test intercept = 0 statement test

H0: αi = 0 is not significant (P>0.05) then the intercept is not significantly different from

0. This comparison against a 1:1 line is a similar relationship tested as Sikora et al.

(2005) used for comparing methods for the determination of P. The R2 values have

been reported to show the variability within the chosen regression model. Regression

lines were plotted with significant data using Sigma Plot software program (Systat

Software, 2008).

Results and Discussion

The regression relationships between LECO total S and 0.025 M KCl SO4-S and

LECO total S and de-ionized water total S were the only significant regression lines

(P<0.01). The range in LECO total S values were 0.30 to 636.10 mg SO4·kg-1 where as

the range in 0.025 M KCl SO4-S values were 12.41 to 276.99 mg S·kg-1. The deviation

between LECO total S and 0.025 M KCl SO4-S was not normally distributed around 0

with a slight left skewediness (negative numbers) (data not shown). As both the

distribution and range in values depicts, 50% of the time LECO total S values were

higher in concentration than 0.025 M KCl SO4-S and the rest of time they were not

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higher. In addition, a large clumping of points between 0 and 100 mg SO4-S·kg-1 on the

y-axis represents points between 0 and 50 mg S·kg-1, which indicates that LECO total S

does not accurately predict turbidimetric SO4-S. Further more, the calculated organic S

content of the soil (total S – SO4-S) for samples extracted with 0.025M KCl are all

negative, except for four samples (data not shown).

The regression line plotted for LECO total S and 0.025 M KCl SO4-S was y = 73.2 +

0.29x with an R2 of 0.26 (Figure 5-1). Both the test slope =1 and intercept = 0 were

significant and therefore the test hypotheses of H0: βi = 1, and H0: αi = 0 were rejected.

This relationship does not meet the requirements of the ideal 1:1 relationship. Given

that Florida sandy soils are low in organic matter (<2%), it is most likely that the relative

insensitivity (i.e. interferences occurring) of the turbidimetric method to accurately

determine SO4-S. This interference could be from various other ions extracted, co-

precipitated, and present in the solution matrix as „cloudiness‟ or turbidity.

The second significant relationship between two methods was for LECO and de-

ionized water SO4-S (Figure 5-2). This relationship has two major clusters close to 0

mg·kg-1. The first cluster is between 0 and 50 mg S·kg-1 total S and 0 and 100 mg

SO4·kg-1 de-ionized water SO4-S. The second cluster is above the first cluster, located

between 0 and 100 mg S·kg-1 total S and 120 to 200 mg SO4·kg-1 de-ionized water SO4-

S. The range in LECO values were 0.30 to 636.1 mg S·kg-1. The range in de-ionized

water SO4-S were 8.79 to 232.65 mg SO4-S ·kg-1. In addition, the deviation between

LECO and de-ionized water SO4-S was found to be not normally distributed around zero

and skewed to the left (data not presented). The calculated organic S for de-ionized

water SO4-S for all samples was negative, except for two (data not shown). This

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demonstrates that turbidimetric SO4-S is not an accurate method for determining SO4-S

and should not be used without modifications.

The regression line plotted between was y = 88.6 + 0.17x with an R2 = 0.13. Both

the test slope = 1 and test intercept = 0 were significant and the test hypotheses of H0:

βi = 1, and H0: αi = 0 were rejected. This means that both the slope and intercept are

different from the ideal 1:1 relationship tested. Regardless of extraction solution,

turbidimetric determination of SO4-S appears to not accurately reflect SO4 within the

solution. Interfering ions, co-precipitation of other insoluble products, and occlusions

(Kolthoff and Sandell, 1952) during the extraction process and determination of SO4-S

are possible reason for this insensitivity (Table 5-3).

It has been stated by Beaton et al. (1968) that interferences can occur with high

concentrations of Na, K, Ca, Mg, PO4, NO3 and SiO2 in solution when determining

turbidimetric SO4-S. The 0.025 M KCl solution should be well below the threshold of

interference at 0.013 M K. Also, Cl is below the 5000 mg·L-1 threshold (Table 5-4) for

causing negative interference at 0.012 M Cl. Calcium, PO4, or SiO2 could be interfering

with the determination of SO4 by forming other Ba salts (Table 5-4). Florida sandy soils

tend to be high in Ca, but also are categorized as phosphatic soils. Yet, the dissolution

of PO4 from soil colloids is highly unlikely given the pH requirement for any of the ortho-

phosphates to be in solution (pH <4). Plus, polyphosphates as low as 1 mg·L-1 will

inhibit BaSO4 precipitation causing a negative interference (Table 5-4) (ASTM, 2006).

Nitrate and SiO2 are also possible for interference when determining SO4 turbimetircally,

but NO3 is readily leached from sandy soils as it is an anion. Silicates can possibly

interfere positively by co-precipitating with BaSO4 ion as it has a relatively low threshold,

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500 mg·L-1 (Table 5-4) (ASTM, 2006). However, it is not known how much silicates

were present in the extraction solutions for turbidimetric procedures in this study. It also

possible for organic matter colloids interfere via co-precipitation. This is often resolved

by using cation-exchange resins in conjunction with turbidimetric determination of SO4

or by filtering, and treating the solution with activated carbon. These measures often

add time and labor to the determination of SO4-S by turbidimetric procedures.

Both relationships between LECO total S and ICP total S were not significant. For

the relationship plotted between LECO and 0.025 M KCl total S had only one large

cluster of points between 0 and 100 mg S·kg-1 of LECO and 0 and 40 mg S·kg-1 0.025

M KCl ICP total S (Figure 5-3). Also the range in LECO was 0.30 to 636.1 mg S·kg-1

and the range in 0.025 M KCl ICP total S was 0 to 173 mg S·kg-1. For a large change in

LECO, the corresponding change in 0.025 M KCl ICP total S is small. The ICP

procedure is not as precise compared to the LECO procedure. Therefore, it is not

surprising that the deviation between LECO and 0.025 M KCl ICP total S was not

normally distributed around zero and bimodal (data not shown).

The regression relationship found was y = 25.9 – 0.02x with an R2 of 0.007. As

this regression relationship was not significant (P= 0.55) and the random error

explaining most of the model plotted (small R2). Both the test slope = 1 and test

intercept = 0 were significant and the test hypotheses of H0: βi = 1, and H0: αi = 0 were

rejected at P<0.05. This relationship does not meet the requirements for the ideal 1:1

as both slope was not equal to 1 and intercept is not 0.

For the plotted relationship between LECO and de-ionized water ICP total S, a

large cluster was located between 0 and 150 mg S·kg-1 LECO total S and 0 and 20 mg

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S·kg-1 de-ionized water ICP total S. This cluster is only a small portion of the total S

from LECO. The range in LECO total S was 0 to 636.1 mg S·kg-1, where as de-ionized

water ICP total S ranged from 0 to 63.27 mg S·kg-1. The regression line plotted for this

data was y = 12.3 + 0.02x with an R2 of 0.04 (P = 0.17). Only the test slope = 1

statement was significant, meaning βi ≠ 1 and the test intercept = 0 was not significant,

meaning αi = 0. Therefore, this comparison between LECO total S and de-ionized water

ICP total S doesn‟t completely meet the requirements of the ideal 1:1 regression

relationship, but it met one of the two requirements. Regardless of meeting one of the

requirements, de-ionized water ICP total S would not be recommended, because the R2

value is small and random error explains a large extent of the regression model.

An issue with ICP determination of S is that Ca may cause spectral interference of

S when using inductively coupled plasma adsorption emission spectroscopy (ICP-AES)

(Zhao and McGrath, 1994). In Florida, sandy soils can be high in Ca (Simonne and

Hochmuth, 2009) and previous research has found levels >400 mg Ca·kg-1 in Florida

Spodosols (Esmel, 2005). There are two suggested methods for correcting spectral

interferences of Ca on S when using ICP-OES: 1) calibrating with pure S standards,

running a series of Ca standards as samples and fitting a regression line using S

concentration as a function of Ca concentration and 2) inter-element correction method

(IEC) (Kola et al., 2002). For IEC, the interfering element is measured (in this case Ca)

at another wavelength and applying a predetermined correction factor to the results

(Boss and Fredeen, 1997). Both of these correction methods require additional labor

and time to correct the interference, but these methods do not correct matrix Ca

interferences (Kola, et al., 2002). Without correction, erroneous results will occur when

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high levels of Ca are present within the aqueous sample. It has been described by

Knauthe et al. (2000) and supported by Knauthe and Otto (2001) that a weighted

compromise conditions be used when determining S using ICP-OES to maximize

operating conditions. In addition, Kola et al. (2002) used multiple linear regressions to

correct for matrix interferences of Ca on S determination by ICP-OES. This method

reduces labor and time by eliminating 6 of the original 12 calibration standards used to

correct for Ca matrix interferences with an improvement in accuracy. Therefore, if no

adjustments for Ca are conducted by any of the above suggested means, the results

should be similar to this study.

If a choice is possible between all the analytical equipment used in this study, Ca

levels within samples are suspected to be high, and it is unknown if corrections for

spectral or matrix interferences. Based upon the results from this study, it is suggested

that LECO dry combustion total S be used for the determination of S for all samples.

For this method, the possibility of interfering ions, co-precipitation of other Ba salts or

organic matter, and spectral interferences are virtually eliminated.

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Table 5-1. Advantages and disadvantages of selected analytical instruments for determining S or SO4-S.

Instrument ICP-OES Elemental Analyzer Turbidimeter

Cost (per sample) < $10 $20 $12 Speed (min./sample)

2 to 3 min. 4 min. 4 min.

Precise/accurate Yes Yes Noy

Multiple element Yes Yes No Hazardous waste No No Yesz ywithout modifications zBarium salts are classified as a health hazard

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Table 5-2. Instrumental details for comparison between sulfur and sulfate determination for selected samples obtained at the Gulf Coast Research and Education Center in Balm, FL.

Analytical Equipment Specification and Settings

ICP-OES

Instrumentation Perkin-Elmer Optima 2100 DV Generator 750 to 1500 W Wavelength 181.975 nm Readout mg·L-1 Frequency 40 MHz Forward power RF 1350 W Nebulizer Gemtip cross flow Internal standard Yttrium Sample volume 10 mL Auxiliary coolant Liquid Argon Auxiliary coolant flow rate 15 L·min-1

Auxiliary gas 0.2 L·min-1

Liquid uptake rate 1.5 mL·min-1

Carrier gas rate 0.85 L·min-1

Grating Eschelle Calibration curve 5-point linear, 0, 0.1, 1.0, 10, and 50 mg·L-1 S Optical view Axial Dilution ratio 1:10 Dry combustion S

Instrumentation LECO CNS 2000 Wavelength Infrared Radiation Catalyst none Carrier gas O2 Reaction time 4 to 6 min Standard reference material Orchard Turbidimetric

Spectrophotometer Bausch Lomb Spectromic 100 Wavelength 420 nm Conditioning reagent Glycerol, HCl, H2O, 95% ethyl alcohol, and NaCl Reagent BaCl Sample volume 15 mL Dilution ratio 1:7 Standard reference Na2SO4 at 100 mg·L-1

Reaction time 4 min

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Table 5-3. Salts and their solubility as potential interfering ions when determining SO4-S by turbidmetric methods.

Salt Solubility (mg·L-1)z

Cold Water Hot Water

Ba(NO3)2 8.7 X 1024 342000 X 10100 BaPO3 sl s -- BaHPO4 100 to 200 -- Ba(H2PO4)2 d d Ba3(PO4)2 i i Ba2P4O7 100 sl s BaCl α 3.75 X1031 5.9 X 10105 BaSO4 2.66 4.13 Ca(CO3)2 1.4 X 1026 1.8 X 1076 Ca(H2PO4)2 1.8 X 1034 d CaSO4·2H2O (Gypsum) 2.41 X 10-3 sl s CaSO4·½H2O (Plaster of Paris) sl s sl s CaSO4 6.94 X 102

2.09X1033 1619 X 10100

CaNO3 1.212 X 1024 3760000 X 10100 CaCl2 7.45 X 1025 1590000 X 10100 KNO3 2.8 X 106 4130000 X 10100 K2SO4 3.63 X 105 1216000 X 10100 MgSO4·7H2O (Espsom salt) 1.0 X 1037 2.0 X 1080 z notation i = insoluble, sl = slightly soluble, s = soluble, d = decomposes

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Table 5-4. Potential interfering ions for determining SO4-S by turbidmetric methods, their reported thresholds in solution, and reference

Interfering ion threshold (mg·L-1) Reference

AsO4 > 10 ppm Iwasaki et al., 1957 Na+ 200 ppm (no interference) van Staden and Taljaard, 1996 K+ > 5000 ppm

200 ppm (no interference) Iwasaki et al., 1957 van Staden and Taljaard, 1996

Ca+2 > 100 ppm 50 ppm

Baban et al., 1980 van Staden and Taljaard, 1996

Cl- > 5000 mg/L 200 ppm

ASTM, 2006 van Staden and Taljaard, 1996

CO3-2 & HCO3

- > 100 ppm > 1000 mg·L-1

Iwasaki et al, 1957 Morais et al., 2003

Mg+2 no interference 100 ppm

Morais et al., 2003 van Staden and Taljaard, 1996

MoO4 > 10 ppm Iwasaki et al., 1957 Mn+2 10 ppm van Staden and Taljaard, 1996 NH4

+ > 5000 ppm Iwasaki et al., 1957 NO3

- > 50ppm > 100 mg/L

Iwasaki et al., 1957 Reisman et al., 2007

PO4 H3PO4

1 > 25 ppm

ASTM, 2006 Dasgupta et al., 1978

S2O3 > 10 ppm Iwasaki et al., 1957 SeO4 > 10 ppm Iwasaki et al., 1957 SiO2 > 500 mg/L ASTM, 2006 Zn+2 200 ppm van Staden and Taljaard, 1996

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Total Soil S (mg·kg-1

)

0 200 400 600

Mo

difie

d B

lair (

0.0

25

M K

Cl) S

oil

SO

4-S

(m

g·k

g-1

)

0

100

200

300

400

500

600

700

Total Soil S versus 0.025 M KCl SO4-S

y = 73.2 + 0.29x, R2 = 0.26, P<0.01

Ideal 1:1 line

Figure 5-1. Comparison between dry combustion total S and 0.025 M KCl turbidimetric

SO4-S for selected soil samples from fields at the Gulf Coast Research and Education Center in Balm, FL

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Total Soil S (mg·kg-1

)

0 200 400 600

Sta

nd

ard

Re

fere

nce

So

il S

O4-S

(m

g·k

g-1

)

0

100

200

300

400

500

600

700

Total S versus SO4-S

y = 88.6 + 0.17x, R2 = 0.13, P<0.01

Ideal 1:1 line

Figure 5-2. Comparison between dry combustion procedure for total S and de-ionized water turbidimetric SO4-S for selected soil samples from the fields at the Gulf Coast Research and Education Center in Balm, FL.

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Total Soil S (mg·kg-1

)

0 200 400 600

Mo

difie

d B

lair (

0.0

25

M K

Cl) S

oil

S (

mg·k

g-1

)

Total Soil S versus 0.025 M KCl Soil S

y = 25.9 - 0.02x, R2 = 0.007, P = 0.55

Ideal 1:1 line

Figure 5-3. Comparison between dry combustion procedure for total S and 0.025 M KCl Inductively Coupled Plasma total S for selected soil samples obtained from the fields at the Gulf Coast Research and Education Center in Balm, FL

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Total Soil S (mg·kg-1

)

0 200 400 600

De

-io

niz

ed

Wa

ter

So

il E

xtr

acta

ble

S (

mg·k

g-1

)

0

100

200

300

400

500

600

700

Total Soil S versus diH2O Soil S

y = 12.3 + 0.02x, R2 = 0.04, P = 0.17

Ideal 1:1 line

Figure 5-4. Comparison and regression analysis of dry combustion procedure for total

S and Inductively Coupled Plasma de-ionized water total S for soil samples obtained from the fields at the Gulf Coast Research and Education Center in Balm, FL

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CHAPTER 6 COMPARISON OF EXTRACTANTS FOR DETERMINING SULFUR IN SOIL AND

PLANT TISSUE

Introduction

Assessing relationships between a newly proposed soil or plant extractant and a

standard extractant is a first-step technique in the evaluation a new extractant for the

development of a soil testing program (Van Erp and Van Beusichem, 1998). This useful

first-step technique seems to be lacking for soil S and SO4 extractants in many soil

testing programs that have been developed. Many studies have been conducted

comparing determination methods of S (Ajwa and Tabatabai, 1993; Crosland et al.

2001; Palomino et al., 2005; Reisman et al., 2007; Soon et al., 1996), but only a few

separate extraction solution comparison from the determination step.

Some of the most widely used solutions to extract soil S to predict plant availability

and fertilizer applications are water, CaCl2, and PO4 solutions (Anderson et al., 1992;

Tan et al., 1994a). Water extractable S is primarily soil S readily leached out of the soil

and is mostly likely in the inorganic SO4-S form. Several solutions are often used and

labeled as „water-extractable S‟. These solutions include Na, Ca or LiCl solutions

(Palomino et al., 2005), because it is accepted that these solutions extract the soluble

fraction of SO4 in soils (Santoso et al., 1995) as the solutions contain the chloride ion

which can easily replace SO4 ion in solution chemistry. It is believed that the difference

between water extractable S and a phosphate solution is related to the amount of SO4

adsorbed by the soil, but this does not always hold true (Santoso et al., 1995). Often

and depending upon soil organic matter and exchange sites, water extractable S as

H2O can significantly dissolute more SO4-S than salt solutions (Maynard et al., 1987;

Santoso et al., 1995; Tan et al., 1994a ) or in some cases similar amounts (Anderson et

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al., 1998; Tan et al., 1994b; Zhao and McGrath, 1994). It may be possible just to use

H2O as an extracting solution instead of a salt solution if water soluble SO4 was desired.

Many studies employ Ca(H2PO4)2 extraction solution at 0.01M or 500 mg P·L-1.

This is one of the recommended soil SO4-S extraction solutions for northeastern US

(Singh et al., 1995) and extracts more soil SO4-S than water via dissolution of SO4-S off

exchange sites on soil particles. The Ca(H2PO4)2 solution can cause interferences

when using turbidimetric measurement of SO4-S when 0.04 M solution is used for some

soils (Searle, 1998). The other issue with Ca based extraction solutions is that Ca may

cause spectral interference of S when using ICP-AES (Zhao and McGrath, 1994). In

addition, various studies using Ca(H2PO4)2 have had variable results for extracted S

correlating significantly to other parameters (Anderson et al., 1998a; Anderson et al.,

1998b; Blair et al., 1991; Blair et al., 1993; Chinoim et al., 1997; Palomino et al., 2005;

Pandey and Girish, 2006; Spencer and Glendinning, 1980; Vendrell et al., 1990).

In response to the variability found with extracting S with Ca(H2PO4)2 and to the

poor performance of soil S testing with Ca(H2PO4)2 to estimate soil SO4 supplying

capacity from the organic S pool, Blair et al. (1991) developed a soil extraction solution

of 0.25 M KCl as a potential replacement to Ca(H2PO4)2 extraction solution. Potassium

chloride was originally investigated by Gianello and Bremner (1986) to measure

inorganic N and potential mineralized N. Yet, concerns raised for this potential

replacement have been centered on the parameters involved in the methodology. This

method has a long incubation time (3h) and requires the maintenance of 40° C for this

time period while shaking. Therefore, it is not surprising that modifications to improve

time and detection limits of this extraction solution have been made. Bloem et al.

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(2002) examined six modifications of the 0.25 M KCl extracting solution for SO4-S. This

study found that using 0.025 M KCl, 1 to 5 ratio of soil to extracting solution, shaking for

3 h at room temperature was the fastest, precise method for SO4-S extraction of

agricultural soils (Bloem et al., 2002). While this optimizes soil testing for SO4-S alone,

another possibility is the inclusion of soil SO4 and S determination in extraction solutions

already accepted by laboratories.

An example of a widely accepted soil extracting solution is the Mehlich 3. This

extracting solution excludes H2SO4, which is a component of the Mehlich 1 extraction

solution. Mehlich 3 extractant was designed to replace the Mehlich 1 and Bray 1 P

extractants (Jones, 1998) and is suitable for use on neutral to acidic soils. The benefit

of using an extracting solution such as Mehlich 3 is that it allows for S to be determined

as part of a multiple element (including micronutrients) extraction step. This saves time,

labor, and money, because separate chemicals and analysis do not need to be

performed as has been described in a diagram by Jones et al. (1991). Few studies

have examined Mehlich 3 for S extraction in soils, because the general belief that S is

analyzed separately from all other nutrients. This is either due to the determination of

SO4-S by turibidimetry or ion chromatography instead of using ICP technology.

Rao and Sharma (1997) found strong relationships between Mehlich 3 and other

extracting solutions commonly used to determine SO4-S in soils. This was the first

reported effort of using Mehlich 3 as an extractant for S in soils. Zbíral (1999) found

Mehlich 3 extraction correlated well to water extraction of SO4-S. Also Zbíral and

Nĕmec (2000) found that Mehlich 3 would be suitable for multi-element determination in

Czech agricultural soils. Further support of Mehlich 3 being used to include S in its

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multiple element extraction was showed by Pandey and Girish (2006). Yet, this study

did not compare ability of each extracting solution to dissolute SO4-S or S from the soil

samples. Instead, the study focused on correlation between extractants chosen and

various plant growth and total S within tissue as a way to calibrate the soil test.

Total S in plant tissues are most commonly quantified by two methods: dry

combustion (also known as dry ash procedure) or wet oxidation (also known as acid

digestion). While each has their own advantages and disadvantages, the focus here is

on which ones commonly used in S research and their suitability for S determination.

For dry combustion, two procedures are often used. The first is the Association of

Analytical Chemists (AOAC) Official Methods of Analysis for S in plants in which organic

matter can be destroyed by two different chemicals, Na2O2 or MgNO3 (AOAC-OM-

920.10 or AOAC-OM-923.01) (AOAC, 2000). The AOAC Official Methods of Analysis

are the reference methods in the analytical chemistry domain, but often these methods

are not used by research scientists in agricultural fields. This is primarily due to the

chemical hazards, time, and labor involved in AOAC Official Methods of Analysis.

The other dry combustion technique for total S in plant tissues is an automated

procedure commonly termed LECO. This procedure has two steps within one piece of

equipment: organic matter destruction and total S determination step. The LECO

procedure combusts samples at temperatures up to 1400° C and measures S as SO2

evolved by titration or infrared cell. In some cases, an accelerator or catalyst WO3 or

V2O5 is added to the sample. Kowalenko (2001) suggested that WO3 be added when

simultaneously measuring C, N, and S with a LECO automated dry combustion

instrument. Whether or not a catalyst was used (Etheridge et al., 1998) or one case the

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type of catalysis used (David et al., 1989) have not been reported when LECO

automated dry combustion instrument is used for total S. While this may seem just a

minor error, the lack of this information creates difficulties in repeating the analytical

research. In contrast the automated dry ash procedure, wet oxidation for the extraction

of S from plant tissues is time consuming.

The most common wet oxidation procedure for total S is HNO3 with HClO4. The

number one difficulty with acid mixture for wet oxidation is the tendency of hot HClO4 in

the presence of easily oxidized organic matter to be explosive (Jones, 1985). This in

conjunction with the need for a special hood when using HClO4 rules it out for many

laboratories when choosing a wet oxidation method. Therefore, it is not surprising that

many studies have been conducted on comparing acid mixtures which include or

exclude HClO4 for the suitability as a matrix for metals and non-metals (Havlin and

Soltanpour, 1980; Hoenig et al., 1998; Huang et al., 2004; Ippolito and Barbarick, 2000;

Oliva et al., 2003; Pöykiö et al., 2000; Soon et al., 1996). Two studies in particular

(Pöykiö et al., 2000; Soon et al., 1996) compared methods for the determination of total

sulfur in plant tissues. Pöykiö et al., (2000) compared five different wet oxidation

methods and dry combustion for total S and six other elements (Al, Ca, K, Mg, Mn, and

Zn) against the certified value. This study found that out of all wet oxidation methods,

HNO3 + H2O2 or HNO3 alone were the most suitable for S determination using ICP.

Also the HNO3 + HClO4 digestion procedure in almost every case gave the lowest

results compared to other acid digestion procedures (Pöykiö et al., 2000). The authors

stated that the combustion technique combined with infrared detection (also known as

LECO) provided relative good reproducibility for sulfur determination. In contrast, Soon

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et al. (1996) compared six total S methods with reference values. These methods were

dry ashing with NaHCO3 + Ag2O, oxygen flask combustion with determination on two

different analytical equipment, LECO, microwave digestion with HNO3 + HClO4, and

microwave digestion with HNO3 + H2O2 + HCl. Both dry ashing with NaHCO3 + Ag2O,

and oxygen flask combustion can be time consuming for regular laboratory use when

compared to microwave digestion. In addition, precipitation of AgCl2 may occur in the

case of dry ashing as well as poor recovery of S for certain plant tissues. Microwave

digestion, while rapid, has a high initial cost with the investment of the equipment and

may not be in used in commercial laboratories. Despite these concerns, Soon et al.

(1996) suggested that HNO3 + H2O2 + HCl was suitable for multi-element analysis and

that LECO gave equivalent total S determination as this method.

Currently, there was no soil test in Florida for determining recommended

applications of S for Florida vegetable production. The recommendation for an S

application is empirical based and uses S ranges within plant tissues. Previous

research on tomato and S applications in Florida have found positive results in yield

when plant tissue S are within and outside of the current S recommended range.

Therefore, the goal of this study was to find an extractant for soil S or SO4 in Florida

sandy soils to base recommended S applications, and a total S plant tissue method that

represents total S in tomato tissue. The objectives of this study were to compare soil

extractants (de-ionized water, 0.025 M KCl, and Mehlich 3) for soil S and SO4, compare

plant analysis for total S, and determine the relationship between each extractant and

total plant S digestion method.

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Materials and Methods

Florida has a humid sub-tropical climate with an average temperature high of 32°

C, minimum of 0° C, and average temperature range of 16° to 28° C. Average annual

rainfall is typically in the range of 130 to 150 cm. Florida tomato production occurs

predominately in the soil order of Spodosol, which has an impermeable spodic horizon

capable of perching water table for subsurface irrigation. The soil types at the location

tested were Myakka fine sand (sandy siliceous hyperthermic Aeric Haplaquods), and

Zolfo fine sand (sandy siliceous hyperthermic Grossarenic Entic Haplohumods).

The land was located at the Gulf Coast Research and Education Center (GCREC),

IFAS, University of Florida, in Hillsborough County, Balm, FL. This land was a former

citrus grove renovated to vegetable production in May 2005. Field renovations began in

October 2003 when the citrus trees were pushed over, piled up, and burned. The ashes

and remnants of the burned citrus trees were then spread out over the fields. All fields

were left in fallow until January 2005 in which some were put into vegetable and

ornamental plant production. Vegetable production uses row and raised bed culture.

These rows were orientated directly perpendicular to the orientation of the previous

citrus grove rows in each field. The two areas of land, which were utilized for this study,

are identified as R3 and R4 (Figure 6-1). These areas were chosen because of their

individual land history differences after renovation and possible potential for differences

in soil S. In addition, these areas were also both in tomato production at the time of

sample collection.

For the R3 parcel, okra (Abelmoschus esculentus L. (Moench.)) variety „Clemson

Spineless 80‟ was grown as a cover crop from July 2005 to December 2005. A 15-0-30

(N-P2O5-K2O) dry fertilizer was applied as a broadcast rate of 112 kg N·ha-1. After cover

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crop destruction, the R3 parcel was disked three times, harrowed, packed, leveled, and

irrigation ditches pulled before bed preparation. At raised bed preparation, the field was

subsurface irrigated two weeks in advance of pre-bedding, polyethylene mulch, and

fumigant applications. Raised beds (78 cm wide at base, 19.6 cm high, and 68.6 cm

wide at the top) spaced 1.47 m apart were formed and fumigated with 1,3-

dichloropropene (372 L·ha-1), methyl bromide:chloropicrin (66:33, 393 kg·ha-1) or

chloropicrin alone (168 kg·ha-1) as a shank application, or one of various fosthiazate

rates (O-ethyl S-(1-methylpropyl)(2-oxo-3-thiazolidinyl)phosphonothioate) (0, 2.3, 3.5,

and 5.6 L·ha-1) with or with out metam sodium (701 L·ha-1) as a drip application on 16

Feb. 2006. Land where cucurbits were grown were treated with propenal (449 kg·ha-1),

propylene oxide (92 L·ha-1) applied through the drip tape on 6 Mar. 2006 and methyl

bromide: chloropicrin (66:33, 393 kg·ha-1) as a shank applications on 16 Feb. 2006.

„Florida-47‟ tomato variety was transplanted on 11 Mar. 2006 and „Cobra F1‟ cucumber

variety was direct seeded into raised beds on 21 Mar. 2006. Subsurface irrigation was

utilized for tomato plant establishment (2 wk) and drip irrigation was used for the

remainder of the season (12 wk) starting on 21 Mar. 2006 at (T-Tape, 1.7 L·min-1·340

m-1, 1 tube) 7,358 L·ha-1 per d. A pre-plant broadcast application of fertilizer at 45 kg

N·ha-1 was applied using 4-8-4 (N-P2O5-K2O). Banded applications of fertilizer 10-0-20

(N-P2O5-K2O) at a rate of 336 kg N·ha-1 were made. Okra was seeded as a cover crop

on 18 Apr. 2006 into R3 in areas were tomato and cucurbits not being grown during

spring season (approximately 2.5 ha). On 8 June 2006, okra was fertilized with 15-0-30

(N-P2O5-K2O) at a rate of 89.8 kg N·ha-1. In December 2006, the okra cover crop was

incorporated into the soil.

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In January 2007, R3 was prepared for tomato production as described above. On

23 Feb. 2007, fertilizer was banded into the raised beds before fumigation. Raised

beds were fumigated with methyl bromide plus chloropicrin (67:33 v/v) at a rate of 196

kg·ha-1 to eliminate soilborne diseases, nematodes and weeds. Fertilizer rates applied

in the bands were 0, 186 or 279 kg N·ha-1, 270 or 404 kg K·ha-1, and 0, 213, or 319 kg

S·ha-1. On 12 March 2007, „Florida 47‟ tomato plants were transplanted 59 cm apart on

single rows into raised beds. The irrigation system was a hybrid system which included

subsurface irrigation and drip irrigation. Subsurface was applied at the approximate

rate of 21,035 L·ha-1 per d. Drip irrigation tubing (T-Tape, 1.7 L·min-1·340 m-1, 1 tube)

was buried to a depth of 2.5 cm in the center of the raised bed. The irrigation rate using

drip system was at an approximate rate of 39,095 L·ha-1 per d. Therefore, the total

water applied via irrigation for the tomato crop in Spring 2007 was 60,130 L·ha-1 per d.

For the R4 parcel, the land was in fallow (no fumigation, tillage, cover crop,

fertilizer or irrigation applications) until January 2006. In 2006, R4 was tilled, harrowed,

leveled and allowed to go fallow until January 2007. In January 2007, R4 was prepared

as described above for tomato production. The soil was treated with and without

fumigation prior to vegetable production (0 and 257 kg·ha-1 with fumigation) on Feb.

2007. Variety „Florida-47‟ tomatoes were transplanted on 12 March 2007. All N and K

was applied via fertigation at 0, 224, or 336 kg N·ha-1. Drip irrigation was utilized in R3

for tomato crop production. Drip tubing (T-Tape, 1.7 L·min-1·340 m-1, 1 tube) was buried

to a depth of 2.5 cm in the center of the raised bed. The irrigation rate using drip

system was at an approximate rate of 39,095 L·ha-1 per d.

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Soil and plant tissue samples were collected on 16 May 2007 from the described

fields at GCREC. The area of tomato fields where both soil and tomato plant tissue

samples were marked so as to be clearly identified for sampling. Fifty-two soil samples

were randomly taken from within an 8.8 m linear plot of the raised bed, between tomato

plants and were approximately 15 to 20 cm of surface soil. After collection soil samples

were air dried, sieved, and stored at 4.4° C until analysis was conducted. Tomato plant

tissue samples were randomly collected within the same 8.8 m linear plot to be paired

exactly with soil samples. Each tomato plant tissue sample consisted of 10 recently

matured leaves adjacent to an inflorescence as described by Mills and Jones (1991).

Tomato plant tissue samples were dried at 43° C, ground with a Wiley mill to pass

through 0.853 mm sieve aperture (20-mesh screen) and stored at 0° C until analysis

was conducted. Paired sampling was used to establish the strongest relationship

possible between two variables.

Soil SO4-S status was characterized by extractions with de-ionized water, and

0.025 M KCl (Table 5-1) using a spectrophotometer (Spectronmic 100, Bausch & Lomb,

Rochester, NY) on 16 Sept. 2009 at Waters Agricultural Laboratory in Camilla, GA. The

standard method for determining SO4 in water by turbidimetry (AOAC-OM-973.57,

ASTM D 516-02) (AOAC, 2000; ASTM, 2006) was considered to be the standard

reference method for SO4-S determination (ASTM D 516-02) and used for comparison

with other methods.

Total soil S status was characterized by de-ionized water, 0.025 M KCl, and

Mehlich 3 using ICP-OES with Eschelle grading (Optima 2100 DV, Perkin-Elmer,

Waltham, MA) at GCREC Analytical Lab in Balm, FL on 19, 20 and 21 Dec. 2008, 8, 9

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and 21 July 2009. Mehlich 1 is the standard calibrated soil extractant for mineral soils in

Florida. For this study, Mehlich 3 was chosen over Mehlich 1 as an extractant, because

Mehlich 3 excludes H2SO4 which is a component of Mehlich 1. The H2SO4 included in

the Mehlich 1 extracting solution could artificially and non-uniformly increase S levels

during extraction. In addition, Mehlich 3 has been found to improved estimation of P,

Cu, Mn, and B in Florida sandy soils over that of Mehlich 1 (Mylavarapu et al., 2002).

LECO total S (CNS 2000, LECO, St. Joseph, MI) with SO2 measurement by infrared

radiation was conducted on 16 June 2009 at MicroMacro International Laboratory in

Athens, GA.

Plant tissue samples were digested with HNO3 and 30% H2O2 (HNO3 + H2O2) as

described by Mills and Jones (1991). One gram of dried plant material was weighed

directly into a 100 mL glass test tube. Eight milliliters of concentrated nitric acid were

added, covered, and left overnight to predigest. Tubes were then placed into an

aluminum heating block capable of holding 50 tubes at 120° C and held for 1 h at this

temperature and allowed to cool. Eight milliliters of 30% H2O2 were then added to each

tube and the block was re-heated to 95° C. Solutions were diluted to 20 mL with nano-

pure water after cooling to room temperature (approximately 22° C) and filtered with

Whatman No. 44 filter paper (20-25 μm particle retention). Only soil samples extracted

with Mehlich 3 and tissue samples digested with HNO3 plus 30% H2O2 were diluted to

1:10 ratio for ICP-OES to prevent salting of the plasma torch (which reduces quality

control and assurance). All data were converted from % or mg·L-1 to mg·kg-1 for data

analysis.

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All data were analyzed using SAS system using proc reg and linear regression

model (yij = αi + βixij + εij) with test slope = 1 and test intercept = 0 statements with

P<0.05 (SAS Institute, 2000). The test slope statement test H0: βi = 1, if this test

hypothesis is false (P<0.05) then the slope is significantly different from 1. The test

intercept = 0 statement test H0: αi = 0, if this test hypothesis is false (P<0.05) then the

intercept is significantly different from 0. These parameters of the regression line were

tested to determine regression lines were similar to the ideal relationship between two

soil extractants. This ideal relationship is a regression line with a slope of 1 (1 rise to 1

run or 1:1) with an intercept of 0. Therefore, for every incremental increase in one

variable there is the same corresponding incremental increase in the second variable

(i.e. 1 to 1). This comparison against a 1:1 line is a similar relationship tested as Sikora

et al. (2005) used for comparing methods for the determination of P. The R2 values

have been reported to show the variability. Regression lines were plotted with

significant data using Sigma Plot software program (Systat Software, 2008).

Results and Discussion

The regression relationship between the standard reference method (SRM) for soil

sulfate and modified Blair (0.025 M KCl) for soil sulfate was the only significant

regression line (P<0.05) (Figure 6-2). The regression model found was y = 51.6 + 0.53x

with a R2 = 0.38. The test statistics for test slope = 1 and test intercept = 0 were both

significant (P<0.05). The deviation between SRM and 0.025 M KCl was plotted and

found to be normally distributed around 0 (data not shown). Despite, the wide range of

x values (12.41 to 276.99 mg SO4·kg-1), y values (8.79 to 232.65 mg SO4·kg-1), lack of

large clustering of points; this relationship is not similar to the ideal 1:1 relationship and

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interpretation of results would have to occur if 0.025 M KCl was used in replacement of

the SRM for soil SO4.

The regression relationship between de-ionized water and Mehlich-3 for soil S was

not significant (P=0.65) (Figure 6-3). The regression model found was y = 11.8 + 0.09x

with a R2 = 0.004. The test statistics for test slope = 1 and test intercept = 0 were both

significant (P<0.05). For this relationship, the range of x was 12.02 to 60.99 mg S·kg-1

and the range in y was 0 to 63.27 mg S·kg-1. Therefore, it is not surprising that a large

cluster is centered around 20 mg S·kg-1. The deviation between de-ionized water and

Mehlich-3 for soil S was plotted and found not to be normally distributed or centered

around 0 (data not shown). This relationship does not fit the ideal relationship between

two soil extraction methods and meets none of the statistical requirements for use (i.e.

slope = 1, intercept = 0, R2>0.70). These results are in direct contrast to Zbíral (1999)

in which water extraction and Mehlich 3 were found to have a significant linear

relationship for total S (y = 6.94 + 0.742x, R2 = 0.62). This study also found that 70% of

soil S extracted was in the sulfate form.

The regression relationship between 0.025 M KCl and Mehlich-3 for soil S was not

significant (P=0.38) (Figure 6-4). The regression model was found to be y = 11.2 +

0.47x with a R2 = 0.01. The test statistics for test slope =1 and test intercept = 0 were

significant (P<0.05). For this relationship, the range in x was 12.02 to 60.99 mg S·kg-1

and the range in y was 0 to 173 mg S·kg-1. It is not surprising based upon these ranges

that a cluster exists between 20 and 40 mg S·kg-1 for Mehlich-3. The deviation between

modified Blair and Mehlich-3 was normally disturbed but not centered around 0 (data

not shown). This relationship also does not fit the ideal relationship between two soil

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extraction methods and meets none of the statistical requirements for use (i.e. slope =

1, intercept = 0, R2>0.70).

The regression relationship between total plant tissue S by wet digestion with

HNO3 + 30% H2O2 and total plant tissue S by LECO was not significant (P=0.19)

(Figure 6-5). The regression model was to be y = 3637.8 + 0.04x with a R2 = 0.03. The

test statistics for test slope = 1 and test intercept = 0 were significant (P<0.05). For this

relationship, the range in x was 5274 to 11896 mg S·kg-1 and the range in y was 3261

to 4965 mg S·kg-1. Based upon this relationship there is a large change in the value for

HNO3 + H2O2 plant tissue S for a small change in LECO plant tissue S. Even though

this relationship is not significant and does not meet the ideal statistical requirements

(i.e. slope = 1, intercept = 0, R2>0.70). This comparison between total plant tissue S

methods has a deviation relationship.

The HNO3 + H2O2 plant tissue S was systematically higher than the LECO plant

tissue S. This was evident by the plotting of the deviation between HNO3 + H2O2 plant

tissue S and LECO plant tissue S (Figure 6-6). The deviation is normally disturbed, but

not centered around 0. These differences may be due to the inherent errors with in the

ICP-OES or LECO combustion S, because the CV was 9 for this comparison and

internal quality control and assurance was met for each extraction method. When

comparing this study results to a study conducted Pöykiö et al. (2000) on comparison of

dissolution methods. Pöykiö et al. (2000) had two out of five S analyses higher in S

concentration for HNO3 + H2O2 than LECO. One of these two was an unknown S

content leaf sample. It becomes apparent that our results are possibly unique since all

of the samples with wet oxidation by HNO3 + H2O2 had higher S concentrations.

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These results suggested that the predictability of any soil extractant with tomato

plant tissue S or yield is low, thereby rendering a soil test based on these extractions

unpractical. While HNO3 + H2O2 consistently had higher S concentrations than LECO

without further information within this study on spectral interferences, the true reason

can not be elucidated. Hence, the current Florida recommendation for S using plant

analysis should continue to be utilized, regardless of current S responses being shown

with the addition of S to the fertilizer regime. It is also recommended that total S in plant

tissues be determined by LECO as this is the absolute total S within plant tissues.

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Figure 6-1. Diagram of Gulf Coast Research and Education Center buildings, field

layout, and nomenclature system for identifying production fields.

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Modified Blair (0.025M KCl) Soil SO4-S (mg·kg

-1)

0 50 100 150 200 250 300

De-io

niz

ed

Wate

r fo

r S

oil

SO

4-S

(m

g·k

g-1

)

0

50

100

150

200

250

300

0.025 M KCl Soil SO4-S versus diH2O SO4-S

y = 51.6 + 0.53x, R2 = 0.38, P<0.01

Ideal 1:1 line

Figure 6-2. Comparison of Modified Blair SO4-S with Standard Reference (H2O) SO4-S

for selected soil samples from the Gulf Coast Research and Education Center in Balm, FL.

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Mehlich-3 Soil S (mg·kg-1

)

0 20 40 60 80

De-ioniz

ed W

ate

r S

oil

S (

mg·k

g-1

)

0

20

40

60

80

Mehlich-3 Soil S versus diH2O Soil S

y = 11.8 + 0.09x, R2 = 0.004, P = 0.65

Ideal 1:1 line

Figure 6-3. Comparison of Mehlich-3 S with de-ionized water S for selected soil

samples from the Gulf Coast Research and Education Center in Balm, FL.

0 50 100 150 200 250 300

0

50

100

150

200

250

300

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Mehlich-3 Soil S ( mg·kg-1

)

0 20 40 60 80

Mo

difie

d B

lair (

0.0

25

M K

Cl) S

oil

S (

mg·k

g-1

)

0

20

40

60

80

Mehlich-3 Soil S versus 0.025 M KCl Soil S

y = 11.2 + 0.47x, R2

= 0.01, P = 0.38

Ideal 1:1 line

Figure 6-4. Comparison of Mehlich-3 S with Modified Blair S for selected soil samples

collected at the Gulf Coast Research and Education Center in Balm, FL.

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Total Plant Tissue S by Wet Digestion with HNO3 + H

2O

2 (mg·kg

-1)

2000 4000 6000 8000 10000 12000 14000

To

tal P

lan

t T

issu

e S

by D

ry C

om

bu

stio

n (

mg·k

g-1

)

2000

4000

6000

8000

10000

12000

14000

Total Plant S by HNO3 + H2O2 versus Total Plant

y = 3637.8 + 0.04x, R2 = 0.03, P = 0.19

Ideal 1:1 line

Figure 6-5. Comparison of total plant tissue S by wet oxidation and by dry combustion

total S procedure for selected soil samples collected at the Gulf Coast Research and Education Center in Balm, FL.

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Categories of Deviation Between LECO and HNO3 + H

2O

2 Plant Tissue S (mg·kg

-1)

0 to

500

501

to 1

000

1001

to 1

500

1501

to 2

000

2001

to 2

500

2501

to 3

000

3001

to 3

500

3501

to 4

000

4001

to 4

500

4501

to 5

000

5001

to 5

500

5501

to 6

000

6001

to 6

500

6501

to 7

000

7001

to 7

500

7501

to 8

000

8001

to 8

500

8501

to 9

000

Dis

trib

ution (

coun

t)

0

2

4

6

8

10

12

Figure 6-6. Distribution of the deviation between total plant tissue S by wet oxidation

and dry combustion total S for selected soil samples collected at the Gulf Coast Research and Education Center in Balm, FL

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CHAPTER 7 CALIBRATION AND DIAGNOSTIC TOOLS OF SOIL AND TOMATO TISSUE SULFUR

FOR PRODUCTION ON FLORIDA SANDY SOILS

Introduction

The results of soil tests can be used to diagnose and guide the correction of

nutrient deficiencies, to diagnose and avoid nutrient and non-nutrient toxicities, to

assess the need for soil amendments and to monitor the effects through time of fertilizer

rates and other management practices (Helyar and Price, 1999). Interpretation of soil

test results requires the use of correlation between yield and soil test values. Typically,

the interpretation has been established for a crop, soil type, and area. In the case of S

and tomato, this relationship has not been established. This study is attempting to

determine if a relationship exists between tomato yield, soil S and tissue S. While it is

important to note that seldom does interpretation become established based upon a

single carefully designed experiment; rather it requires hundreds of fertility trials and

resulting in thousands of plant analyses (Melsted et al., 1969). An initial study must be

conducted to establish a nutrient calibration curve.

Nutrient calibration based upon mineral concentration in dry matter versus plant

growth or yield has been described by Smith (1962). This nutrient calibration curve is

the basis of plant nutrition. It is a relationship often attempted to be established for many

nutrients for interpretation of nutrient research results. Both total and relative yield can

be used to establish nutrient calibration curves. It is not recommended to use relative

yield as a variable, because the standardization of yield can lead to erroneous

conclusions.

It has been suggested by Jackson (2000) that thorough evaluations of SO4-S

extraction procedures, along with more S response data are needed to create an S

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fertilization recommendation. Strong relationships between soil S and plant S are

difficult to achieve and are the current focus of many S researchers throughout the

world. Only calibration of soil test values against yield, S concentrations in plants or S

uptake by plants make them suitable for judgment about the S nutritional status of a site

(Schnug and Haneklaus, 1998).

Since an official method of analysis is lacking for soil S, a standard reference

method for determining SO4-S or total S in soil is used. Examining the literature about

SO4-S or total S determination in soil resulted in many studies recommending different

soil extraction and determination methods (Table 2-2). Beaton and Burns (1968) cite

two methods for determining extractable SO4 from soils: by CaHPO4 and LiCl. The first

determines SO4 by turbidimetry and the second by methylene blue. Jones and Jones

(2001) have the determination of extractable SO4-S as Ca(H2PO4)2, 0.5 M CH3COONH4

– 0.25 M CH3COOH and 0.01 M CaCl2.

Blair et al. (1993) developed an exaction method for SO4-S for humid

environments. Based upon the author‟s previous research on evaluating range of

extractants as predictors of S status of pastures, they found that 0.25 M KCl extraction

solutions shaken at 40° C had the highest coefficient of determination (Blair et al.,

1991). More recently, Bloem et al. (2002) investigated this method for extracting soil S

and compared it to modified versions of Blair‟s method. These extraction procedures

can be used in conjunction with turbidimetry, ICP emission spectrometry, and IC.

An important theme throughout S research is the wide spread variability for

different methods when determining S and even laboratory to laboratory methodological

differences in determining S and SO4-S. A multiple laboratory comparison of S in plant

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tissue and SO4-S in soil found that variability (higher than 36% CV) was large and that

determination of S is a complex and difficult procedure (Crosland et al., 2001). This

study made several recommendations that are applicable beyond the United Kingdom,

where the study was conducted. Some of these suggestions by Crosland et al., (2001)

were 1) laboratories should standardize extraction and digestion procedures for S, 2)

reference materials should be utilized (none currently exist for soils), 3) analytical

methods must be capable of determining low concentrations of S in soil extracts, and 4)

methods must be calibrated for diagnostic purposes so that results obtained are

comparable with those from other methods. The first recommendation is important,

because until a standardization of extractions and digestions is created many more

studies will be conducted with different extraction and digestion procedures and

variability will continue to be an issue with S research.

Sulfur research needs to include reference material in analytical studies. This

would establish the consistency in measurements, which in turn would aid in

interpretation and quantification. Currently and most importantly, no reference materials

have been developed and this has to be determined and established for S research as

a whole. The determination of low concentrations of S allows for establishment of lower

limits of determination. The calibration of methods will assist in increasing the

consistency and continuity of S research world wide. The object of this study was to

determine if a relationship exists between soil S or tomato leaf S with tomato yield.

Materials and Methods

A study was conducted at the Gulf Coast Research and Education Center

(GCREC) in Balm, FL. The soil was a sandy, siliceous, hyperthermic Oxyaquic Alorthod

soil with 1.5% organic matter and a water pH of 7.3. Plant nutrients, other than N and S,

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were supplied under non-limiting conditions through drip irrigation following current

UF/IFAS recommendations (Olson et al., 2008). Phosphorus was not added, because

soil analysis revealed 108 mg P·kg-1 and this is considered high by interpretations

(Simonne and Hochmuth, 2009). Pressed beds were fumigated with methyl bromide

plus chloropicrin (67:33 v/v) at a rate of 196 kg·ha-1 to eliminate soilborne diseases,

nematodes and weeds on 23 Feb. 2007. Simultaneously, planting beds were covered

with 1.5 μm thick silver on black mulch.

Experimental plots were 8.8-m long with a 2.9-m long non-treated buffer zone at

the end of each plot. Fertilizer sources for N and S applications were NH4NO3, K2SO4,

(NH4)2SO4, and NH4NO3 + (NH4)2SO4 at rates 0 and 186 kg N·ha-1 with 0 and 213 kg

S·ha-1. These fertilizer sources and rates were applied pre-fumigation in grooves

located on the top of the bed. These grooves were two 7.6-cm deep bands separated

34 cm apart centered on the bed top as „hot mix‟. Planting beds were 78 cm wide at the

base, 68.6-cm wide at the top, 19.6-cm high, and spaced 1.47 m apart on centers.

Fertilizer sources were chosen based upon S content and likelihood of being used

in a „hot mix‟ fertilizer by tomato growers. „Hot mix‟ refers to fertilizer that is banded on

top of a raised bed. This fertilizer blend has a high salinity and thus termed „hot‟. Over

time, this „hot mix‟ is dissolved via the movement of irrigation water in a subsurface

irrigation system. Therefore, the fertilizers (salts) are diluted via subsurface irrigation.

Muriate of potash (KCl) (60% K) was used to balance total K amounts in those

treatments using NH4NO3 or (NH4)2SO4 as a fertilizer source to ensure that K was under

similar and non-limiting conditions.

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A hybrid system uses both subsurface and drip irrigation and employed by those

growers transitioning from all subsurface to drip irrigation. Irrigation supplied as

subsurface was at the approximate rate of 21,035 L·ha-1 per d. Drip irrigation tubing (T-

Tape Systems International, San Diego, CA) was buried to a depth of 2.5 cm in the

center of the raised bed with a flow rate of 0.058 L·m-1·min-1. The irrigation rate using

drip system was at an approximate rate of 39,095 L·ha-1 per day. Therefore, the total

water applied via irrigation was 60,130 L·ha-1 per day. The water table was maintained

between 46 and 61 cm deep and constantly monitored with piezometers located in the

fields. „Florida-47‟ tomato transplants were established 59 cm apart on single rows on

center of each bed on 12 Mar. 2007. Tomato plants were staked and tied as described

by (Csizinszky et al., 2005) and weekly spray applications to maintain pest and disease

control based upon weekly field scouting results.

Tomato fruits were harvested twice on 10 and 12 WAT, and graded as marketable

and non-marketable based upon size. Marketable tomato fruits were graded according

to the Florida Tomato Committee regulations for size categories (Brown, 2009; Sargent

and Moretti, 2004). The sizes were 5X6 (7.0 cm), 6X6 (7.06 to 6.32 cm), 6X7 (6.43 to

5.72 cm), and cull (<5.4 cm). Cull fruits were those smaller than 5.4 cm in diameter

which below the minimum diameter for a 6x7 tomato fruit.

Twenty-four tomato leaf and soil samples were randomly taken from within an 8.8

m linear plot of the raised bed. Ten leaf samples were taken from the most recently

matured leaf adjacent to an inflorescence as described by Mills and Jones (1991) within

a plot. Leaf samples were dried at 43° C, ground with a Wiley mill to pass through at

0.853 mm sieve aperture (20-mesh screen) and stored at 0° C until analysis was

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conducted. Soil samples collected from between tomato plants and were approximately

15 to 20 cm of surface soil within plots. After collection soil samples were air dried,

sieved, and stored at 4.4° C until analysis was conducted.

Plant tissue samples were digested were HNO3 and 30% H2O2 as described by

Mills and Jones (1991). One gram of dried plant material was weighed directly into a

100 mL glass test tube. Eight milliliters of concentrated nitric acid was added, covered,

and left overnight to predigest. Tubes were then placed into an aluminum heating block

capable of holding 50 tubes. The heating block was ramped to 120° C and held for 1 h

at this temperature and allowed to cool. Eight milliliters of 30% H2O2 was then added

and the block re-heated to 95° C. Solutions were diluted to 20 mL with nano-pure water

after cooled to room temperature (approximately 22° C) and filtered with Whatman No.

44 filter paper (20-25 μm particle retention).

Soil SO4-S status was characterized by extractions with de-ionized water, and

0.025 M KCl using a spectrophotometer (Spectronmic 100, Bausch & Lomb, Rochester,

NY) on 16 Sept. 2009 at a commercial laboratory. The standard method for determining

SO4 in water by turbidimetry (AOAC-OM-973.57, ASTM D 516-02) (AOAC, 2000;

ASTM, 2006) was considered to be the standard reference method for SO4-S

determination and used for comparison with other methods. Total soil S status was

characterized by de-ionized water, and 0.025 M KCl, using ICP-OES (Optima 2100 DV,

Perkin-Elmer, Waltham, MA) with Eschelle grading and under a constant vacuum at

GCREC Analytical Lab in Balm, FL on 19, 20 and 21 Dec. 2008, 8, 9 and 21 July 2009.

Only soil samples extracted with Mehlich 3 and tissue samples digested with HNO3 plus

30% H2O2 were diluted to 1:10 ratio for ICP-OES. The Dumas method of SO2

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measurement by infrared radiation (CNS 2000, LECO, St. Joseph, MI) was conducted

on 16 June 2009 at a commercial laboratory. All data was converted from % or mg·L-1

to mg·kg-1 for data analysis. The parameters of the regression line were tested to

determine if plotted regression lines were similar to the ideal relationship between

extractants. This ideal relationship is a regression line with a slope of 1 (1 rise to 1 run

or 1:1) with an intercept of 0. This comparison against a 1:1 line is a similar relationship

tested as Sikora et al. (2005) used for comparing methods for the determination of P. If

the ideal 1:1 relationship is met, then the extractant comparisons do not require

interpretation for over or under estimation of soil S or SO4-S. Data was analyzed using

SAS system using proc reg and linear regression model (yij = αi + βixij + εij) with test

slope = 1 and test intercept = 0 statements with P<0.05 (SAS Institute, 2000). The test

slope statement test H0: βi = 1, if this test hypothesis is not significant (P>0.05) then the

slope is not significantly different from 1. The test intercept = 0 statement test H0: αi = 0,

if this test hypothesis is not significant (P>0.05) then the intercept is not significantly

different from 0. The R2 values have been reported to show the variability within the

chosen regression model. For relationships between extractants and tomato yield,

regression lines were fitted to the data to determine if each soil test could be calibrated

to tomato yield. Regression lines were plotted with significant data using Sigma Plot

software program (Systat Software, 2008).

Results and Discussion

None of the plant tissue testing methods for total plant tissue S (acid digestion and

LECO) had satisfactory relationships with total tomato yield (Figures 7-1 and 7-2).

None of the soil S or SO4-S methods related well to total tomato yield as no linear

regression relationship could be established (Figures 7-3, 7-4, 7-5, and 7-6). While

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presenting correlation coefficients may be possible; they may lead to erroneous

conclusions about the relationship between tomato yield and soil or tissue S. It is

important to note that unlike previous studies, which have used dry matter (Matula,

1999; Pandey and Girish, 2006), leaf tissue S (Anderson et al., 1998a; Rao and

Sharma, 1997), or relative yield (Anderson et al., 1992; Chinoim et al., 1997; Spencer

and Glendinning, 1980; Zhao and McGrath, 1994; this study used actual yield values for

relationship determinations. This being stated and given the lack of an ideal

relationship found between the three soil extraction methods used for soil S and SO4-S

in this study. It is possible that the fractions extracted do not relate well to plant yield

(Figure 7-7). Therefore, it is suggested that other soil extractants be investigated if a

soil test based recommendation for S is desired for vegetable production in Florida.

Based upon these results, the current recommendation of application of 28 to 37 kg

S·ha-1 based upon tissue testing should be followed until an appropriate soil test for S

can be found.

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LECO Total Plant S (mg·kg-1

)

2000 4000 6000 8000 10000 12000

Tom

ato

Yie

ld (

kg·h

a-1

)

0

10

20

30

40

50

LECO Total Plant S vs Yield

Figure 7-1. Relationship between dry combustion total plant S and tomato yield for

selected tissue samples from the Gulf Coast Research and Education Center in Balm, FL

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Total Plant S (mg·kg-1

)

4000 6000 8000 10000 12000 14000

To

ma

to Y

ield

(kg·k

g-1

)

0

10

20

30

40

50

Total Plant S vs Yield

Figure 7-2. Relationship between total plant S and tomato yield for selected tissue samples from the Gulf Coast Research and Education Center in Balm, FL.

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LECO Total Soil S (mg·kg-1

)

0 50 100 150 200

To

ma

to Y

ield

(kg·h

a-1

)

0

10

20

30

40

50

LECO Total Soil S vs Yield

Figure 7-3. Relationship between dry combustion total soil S and tomato yield for

selected soil samples from the Gulf Coast Research and Education Center in Balm, FL.

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Modified Blair Soil S (0.025 M KCl) (mg·kg-1

)

0 50 100 150 200

To

ma

to Y

ield

(kg·h

a-1

)

0

10

20

30

40

50

Modified Blair Soil S vs Yield

Figure 7-4. Relationship between Modified Blair (0.025 M KCl) soil S and tomato yield for selected soil samples from Gulf Coast Research and Education Center in Balm, FL.

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Deionized Water Soil S (mg·kg-1

)

0 50 100 150 200

To

ma

to Y

ield

(kg·h

a-1

)

0

10

20

30

40

50

Deionized Water Soil S vs Yield

Figure 7-5. Relationship between de-ionized water soil S and tomato yield for selected soil samples from Gulf Coast Research and Education Center in Balm, FL.

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Mehlich-3 Total S (mg·kg-1

)

0 50 100 150 200

To

ma

to Y

ield

(kg·h

a-1

)

0

10

20

30

40

50

Mehlich-3 ICP S vs Yield

Figure 7-6. Relationship between Mehlich-3 soil S and tomato yield for selected soil samples from Gulf Coast Research and Education Center in Balm, FL.

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Figure 7-7. Possible main fractions of soil S and analytical methods for S

determination.

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CHAPTER 8 SUMMMARY AND CONCLUSIONS

These studies on S fertilization provided information on S source, rate, and

irrigation programs on fresh market tomato growth, development and yield. Sulfur

applications, regardless of source ((NH4)2SO4, K2SO4, NH4NO3 + (NH4)2SO4) increased

tomato yields when compared to the non-treated control. Therefore, source of S was not

contributed to the yield increase. Elemental S, when applied as the only source of S,

increased early fresh market tomato yield. At approximately 5.6 kg S·ha-1 of applied S,

A yield increase of 2,919 kg·ha-1 over the non-treated control was determined. Irrigation

program did not influence soil S concentration, soil pH, S concentration within tomato

leaves or early yield. This suggests that irrigation water may not meet the S needs of

tomatoes when grown with drip irrigation. It is possible that the form of S present within

the irrigation water needs to be oxidized by microbes. An increase in tomato leaf S and

early yield were found with the addition of elemental S to the fertilizer regime.

The laboratory study provided information on S soil testing for Florida sandy soils,

which is predominate soil type that tomatoes are grown on in Florida. Based upon the

results, soil SO4-S and S are highly variable in determination which is supported by

previous studies and difficult to completely determine a relationship between soil SO4-S,

soil S, plant tissue S and tomato yield. All regression relationships between soil S and

SO4-S had low R2 values (<0.70). The relationship between soil SO4-S and plant S had

a negative slope. These were not ideal statistically to determine the relationship

between these variables.

An increase in early tomato yields were found throughout the studies when S was

included in the fertilizer regime. This suggests that S should be included in the fertilizer

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regime for fresh market tomatoes grown on Florida sandy soils. Further research to re-

evaluate the S sufficiency rates for tomato production would be helpful on determining

the appropriate leaf sufficiency range for tomato as total S in tomato tissue ranged from

4550 mg S·kg-1 to 9400 mg S·kg-1 with little correlation to yield response. It is also

apparent that irrigation water may not contribute to the total S necessary to grow a

tomato crop in Florida. From this study further support of the variability in soil testing for

S was determined. For Florida sandy soils, no one method can be recommended for

determining SO4-S or S. Therefore, when S deficiency is suspected or tissue S is

shown to be in the low range (<3, 000 mg S·kg-1) in a vegetable crop 28 to 38 kg S·ha-1

should be applied as part of the fertilizer regime.

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BIOGRAPHICAL SKETCH

Camille grew up in New Hampshire (in the heart of scenic New England),

surrounded by the majestic White Mountains National Forest, the historic Robert Frost

Farm, and the quaint colonial New England sea coast. She developed an appreciation

for nature and the outdoors from both of her parents. Her father, (Curtis R. Esmel, Sr.),

is an avid outdoorsman. Her mother, (Lydia E. Fortier), is a gardener and naturalist.

Camille attended Pinkerton Academy in Derry, New Hampshire, where she studied

horticulture through high school vocational classes and participation in the National

Future Farmers of America organization. Camille remained active in the National Future

Farmers of America organization while attending the University of New Hampshire. She

graduated from the University of New Hampshire in May 2002 with a Bachelor of

Science in environmental horticulture. Camille graduated from the University of Florida

in May 2005 with a Master of Science in Horticultural Sciences.