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Investigation of Soil Amendments for Use in Golf Course Putting Green Construction

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INVESTIGATION OF SOIL AMENDMENTS FOR USE IN GOLF COURSE PUTTING GREEN CONSTRUCTION By TRAVIS SHADDOX 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 2004

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Copyright 2004 by Travis Shaddox

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ACKNOWLEDGMENTS I give my sincere thanks and appreciation to the chairman of my supervisory committee, Dr. Jerry Sartain. Without the opportunity and his support, achieving this degree would not have been possible. I would also like to thank the other members of my committee: Dr. James Bonczek for his expertise in surfactant chemistry, Dr. Donald Graetz for his knowledge of soils and nitrogen transformations, Dr. Grady Miller for his help in the area of turfgrass and soil amendments, and Dr. Peter Nkedi-Kizza for his support during my leaching experiments. Thanks go to the Florida Turf Grass Association who sponsored this research project. I appreciate its continued support of turfgrass research at the University of Florida. Special thanks go to lab personnel, Ed Hopwood Jr., Nahid Varshovi, Shawron Weingarten, Martin Sandquist, and Brian Owens, who helped me throughout my research. Finally, I would like to thank all the members of my family in Oklahoma and in Florida for their ongoing support. iii

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TABLE OF CONTENTS page ACKNOWLEDGMENTS.................................................................................................iii LIST OF TABLES............................................................................................................vii LIST OF FIGURES...........................................................................................................ix ABSTRACT.......................................................................................................................xi CHAPTER 1 INTRODUCTION........................................................................................................1 Water Use Efficiency....................................................................................................1 Nutrient Leaching.........................................................................................................3 2 LITERATURE REVIEW.............................................................................................5 Soil Amendments..........................................................................................................5 Peats.......................................................................................................................6 Calcined Clays.......................................................................................................9 Zeolites................................................................................................................11 Diatomaceous Earths...........................................................................................14 Water Treatment Residuals.................................................................................16 Water-Use-Efficiency.................................................................................................17 Nitrogen in the Turfgrass Environment......................................................................19 N Transformations in Soil...................................................................................20 Leached N............................................................................................................22 Phosphorous in the Turfgrass Environment...............................................................23 P Reactions in Soil...............................................................................................23 Leached P............................................................................................................23 Hexadecyltrimethyammonium...................................................................................25 Bi-layer Formation..............................................................................................26 Anion Sorption....................................................................................................27 Stability................................................................................................................28 iv

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3 MATERIALS AND METHODS...............................................................................30 Characterization Studies.............................................................................................30 Cation Exchange Capacity..................................................................................30 Moisture Retention..............................................................................................30 Sorption Isotherms...............................................................................................31 Surfactant Loading..............................................................................................32 Thermal Analysis.................................................................................................32 X-Ray Diffraction................................................................................................34 Nutrient Analysis.................................................................................................34 Sand Mixes.................................................................................................................34 Water Use Efficiency Calculations.............................................................................36 Glasshouse Studies.....................................................................................................36 Year 1..................................................................................................................36 Year 2..................................................................................................................38 Nutrient Leaching Study.............................................................................................40 4 RESULTS AND DISCUSSION.................................................................................45 Amendment Characterizations....................................................................................45 Surfactant Sorption..............................................................................................45 Mineral Composition...........................................................................................46 Nutrient Composition..........................................................................................46 Nitrogen........................................................................................................47 Phosphorus...................................................................................................47 Potassium.....................................................................................................50 Calcium........................................................................................................50 pH and EC....................................................................................................51 Moisture Retention..............................................................................................51 Glasshouse 2002.........................................................................................................59 Establishment......................................................................................................59 Turf Quality.........................................................................................................61 Water Use Efficiency..........................................................................................63 Glasshouse 2003.........................................................................................................65 Establishment......................................................................................................65 Turf Quality.........................................................................................................67 Days to Wilt.........................................................................................................73 Water Use Efficiency..........................................................................................74 Nutrient Leaching Study.............................................................................................80 Nitrate..................................................................................................................80 Ammonium..........................................................................................................84 Phosphorus..........................................................................................................88 5 CONCLUSIONS........................................................................................................92 Soil Amendments........................................................................................................92 Incorporation Method.................................................................................................92 v

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Nutrient Leaching.......................................................................................................93 APPENDIX MISCELLANEOUS TABLES AND GRAPHS...........................................95 LIST OF REFERENCES.................................................................................................113 BIOGRAPHICAL SKETCH...........................................................................................123 vi

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LIST OF TABLES Table page 3-1 Sand size analysis of amendments and sand mixes..................................................35 4-1 Ion exchange capacity and surfactant sorption as influenced by soil amendment...46 4-2 Chemical properties of amendments used in glasshouse and field studies..............48 4-3 Chemical properties of 85:15 sand/amendment mixtures used in glasshouse and field studies..............................................................................................................49 4-4 Physical analysis of amendment/sand mixture at 85:15 by volume.........................53 4-5 Visual quality rating of bermudagrass as influenced by 85:15 sand/amendment rootzone during 2002 glasshouse study...................................................................62 4-6 Tissue yield, applied water, and water-use-efficiency of Tifdwarf bermudagrass as influenced by soil amendments during glasshouse 2002 study...........................64 4-7 Analysis of variance of mean squares on turf quality during 2003 study as influenced by incorporation method and amendment type......................................68 4-8 Visual quality rating of bermudagrass as influenced by 85:15 sand/amendment rootzone during 2003 glasshouse study...................................................................69 4-9 Visual quality rating of Tifdwarf bermudagrass as influenced by 4 tine aerification during 2003 glasshouse study...............................................................71 4-10 Visual quality rating of Tifdwarf bermudagrass as influenced by 9 tine aerification during 2003 glasshouse study...............................................................72 4-11 Analysis of variance of mean squares on Tifdwarf days to wilt during 2003 study as influenced by incorporation method and amendment type........................73 4-12 Days to wilt of Tifdwarf bermudagrass as influenced by 85:15 sand/amendment rootzone during 2003 glasshouse study...................................................................74 4-13 Analysis of variance of mean squares on Tifdwarf water use efficiency during 2003 study as influenced by incorporation method and amendment type...............75 vii

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4-14 Tissue yield, applied water, and water-use-efficiency of Tifdwarf bermudagrass as influenced by fully incorporated soil amendments during glasshouse 2003 study.........................................................................................................................76 4-15 Tissue yield, applied water, and water-use-efficiency of Tifdwarf bermudagrass as influenced by soil amendments after 9 tine aerification during glasshouse 2003 study.........................................................................................................................77 4-16 Tissue yield, applied water, and water-use-efficiency of Tifdwarf bermudagrass as influenced by soil amendments after 4 tine aerification during glasshouse 2003 study.........................................................................................................................79 4-17 Water use efficiency of Tifdwarf bermudagrass as influenced by incorporation method......................................................................................................................80 4-18 Total NO 3 -N leached as influenced by filter zone media.........................................83 4-18 Total NH 4 -N leached as influenced by filter zone media.........................................87 4-19 Total phosphorous leached as influenced by filter zone media................................90 A-1 Chemical properties of irrigation water used in glasshouse and field studies.......103 A-2 Phosphorous and ammonium leaching parameters for the 2-site model................112 viii

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LIST OF FIGURES Figure page 2-1 The nitrogen cycle....................................................................................................21 2-2 The P cycle...............................................................................................................24 2-3 Hexadecyltrimethylammonium................................................................................26 2-4 Schematic of HDTMA bi-layer formation...............................................................26 3-1 Schematic diagram of pot set-up used in glasshouse studies showing side and top view of amendment incorporation methods where A = 85:15 sand/amendment, B = 4 tine aerification with 50:50 sand/amendment, and C = 9 tine aerification with 50:50 sand amendment.............................................................................................39 3-2 Schematic diagram of lysimeter set-up used in leaching studies.............................41 4-1 Moisture release curve for USGA sand amended with zeolites at 85:15 by volume......................................................................................................................54 4-2 Moisture release curve for USGA sand amended with diatomaceous earths at 85:15 by volume.......................................................................................................55 4-3 Moisture release curve for USGA sand amended with calcined clays at 85:15 by volume......................................................................................................................56 4-4 Moisture release curve for USGA sand amended with peat or Fe-Humate at 85:15 by volume or with smectite at 97.5:2.5 by volume........................................58 4-5 Establishment of Tifdwarf bermudagrass during summer 2002 as influenced by (A.) zeolites, (B.) diatomaceous earths, (C.) clay and organics, and (D.) calcined clays. Vertical bars denote standard error...............................................................60 4-6 Establishment of Tifdwarf bermudagrass during summer 2003 as influenced by (A.) zeolite, (B.) diatomaceous earths, (C.) clay and organics, and (D.) calcined clays. Vertical bars denote standard error...............................................................66 4-7 Nitrate breakthrough curves as influenced by filter zone media..............................81 4-8 Ammonium breakthrough curves as influenced by filter zone media......................85 ix

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4-9 Phosphorus breakthrough curves as influenced filter zone media...........................89 A-1 Thermal gravimetry analysis of HDTMA................................................................96 A-2 Thermal gravimetry analysis of HDTMA coated calcined clay 1............................97 A-3 Thermal gravimetry analysis of HDTMA coated calcined clay 2............................98 A-4 Thermal gravimetry analysis of HDTMA coated clinoptilolite...............................99 A-5 X-ray diffractogram of diatomaceous earths in a side-packed powder mount......100 A-6 X-Ray diffractogram of calcined clays in a side-packed powder mount...............101 A-7 X-Ray diffractogram of zeolites in a side-packed powder mount.........................102 A-8 Correlation between microporosity and plant available water of amendment/sand mixture at 85:15 by volume.......................................................104 A-9 Nitrate sorption isotherm for surfactant-modified soil amendments......................105 A-10 Ammonium sorption isotherm for uncoated and HDTMA coated calcined clay 1.106 A-11 Ammonium sorption isotherm for uncoated and HDTMA coated calcined clay 2.107 A-12 Ammonium sorption isotherm for uncoated and HDTMA coated clinoptilolite...108 A-13 Phosporus sorption isotherm for uncoated and HDTMA coated calcined clay 1..109 A-14 Phosphorus sorption isotherm for uncoated and HDTMA coated calcined clay 2.110 A-15 Phosporus sorption isotherm for uncoated and HDTMA coated clinoptilolite......111 x

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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 INVESTIGATION OF SOIL AMENDMENTS FOR USE IN GOLF COURSE PUTTING GREEN CONSTRUCTION By Travis W. Shaddox December 2004 Chair: Jerry Sartain Major Department: Soil and Water Science Turfgrass, like all livings organisms, requires water for survival. Turfgrass professionals, such as golf course superintendents, sports, and athletic field managers often have a limited amount of water they can use due to consumptive use permits levied by regional regulatory agencies. Therefore, they are required to find alternate means of maintaining quality turf while using less water. Many turf professionals enlist the use of soil amendments because of their ability to increase moisture and nutrient availability. However, whether or not soil amendments actually influence the efficient use of water by turfgrass is not known. An objective of this research was to determine the influence of soil amendments and incorporation method of those amendments on water-use-efficiency (WUE) of Tifdwarf bermudagrass [Cynodon dactylon (L.) Pers. C. transvaalensis Burtt Davy]. A further objective was to determine the influence of surfactant-modified soil amendments (SMSAs) on nitrogen (N) and phosphorus (P) leaching. To determine the influence of amendments on turfgrass WUE, Tifdwarf bermudagrass was established on xi

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pots in a glasshouse at the University of Florida turfgrass Envirotron. Treatments consisted of sand, two zeolites, two calcined clays, two diatomaceous earths, Canadian sphagnum peat, iron humate, and a smectite. Treatments were arranged in a randomized complete block design with four replications. Pots were weighed, harvested, and rated weekly for turf quality for twelve weeks. To determine the influence of SMSAs on N and P leaching, soil columns were fabricated from 2.54 cm diam. polyvinyl chloride tubes. Each column was packed with a rootzone layer (30 cm) consisting of sand/peat (85:15) and a filter zone layer (5 cm) containing each treatment. Treatments were sand, zeolite, and two calcined clays. Treatments either remained unchanged or were surfactant-coated. Three replications were used for statistical analysis. In the glasshouse study, incorporation of iron humate increased turf yield, quality, and WUE above all other amendment regardless of incorporation method. This was attributed to an increase in N, Ca, and Fe availability as well as a 13% increase in plant available water which accompanied iron humate incorporation. Rootzone amended with calcined clays (CCs) produced 40% more dry matter yield and increased WUE 30% above sand/peat. However, calcined clays did not produce quality or WUE ratings above iron humate. Sand and zeolite produced quality and WUE ratings equal to that of sand/peat mixtures. Of the amendment investigated in this study, only iron humate and CCs consistently produced quality and WUE ratings above that of sand/peat rootzones. Incorporation of amendments following aerification reduced each amendments influence on yield, quality, and WUE. Therefore, in order to maximize amendment influences on turf quality and WUE, amendment should be fully incorporated into the rootzone. Surfactant-modified amendments reduced NO 3 levels in leachate to 0.0%, reduced NH 4 to 4%, and xii

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reduced P levels to 3% of that applied. Unmodified amendments had no influence on NO 3 leached, reduced NH 4 leaching, and retarded P leaching. Surfactant-modified amendments may be a plausible option to reduce N and P leaching in USGA putting greens. xiii

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CHAPTER 1 INTRODUCTION Soil modification has been used for centuries to alter certain soil properties to improve soil-plant relationships. Generally, this is achieved via the use of soil amendments. Soil amendments may be organic or inorganic and are primarily used to increase plant available water, cation exchange capacity, or nutrient availability. However, ambiguity remains regarding their indirect influence on plant water use. Furthermore, nutrient additions may lead to leaching which can cause a variety of environmental problems. Compounding the situation, some amendments have the capacity to retain potential contaminants while others may enhance leaching. Therefore, this study investigates two primary influences of soil amendment incorporation: turfgrass water-use-efficiency and nutrient retention in USGA putting greens. Water Use Efficiency Every living organism on earth is dependent upon water for survival. In plants, water is the solvent in which vital nutrients are translocated to various plant parts. Water is also the initial proton donor during the first steps of photosynthesis. Thus, without water plants could not survive. Fortunately, the earth contains vast amounts of water in oceans, lakes, rivers, and in the atmosphere. However, only 0.6% of all water on earth is considered to be usable by plants and animals (Nace, 1967). With such a small portion of usable water and such a large number of organisms requiring water, demand for water is high. 1

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2 Water used for recreational purposes is often scrutinized because it is not considered essential to sustain life. Turfgrass water use is receiving attention due to the overall quantity of water required to maintain acceptable quality turf. This attention has prompted regional regulatory agencies to impose consumptive use permits on many golf courses in many states including Florida. Superintendents are now faced with having to maintain an acceptable quality turf while using less water. To become more efficient at using water they are allotted, superintendents sometimes use soil amendments to alleviate the inherent low water retention capacity of United States Golf Association (USGA) putting greens. Numerous soil amendments are commercially available in at least four distinctly different classes. This study compared different soil amendments (organic, zeolite, calcined clay, and diatomaceous earth) to identify materials capable of maximizing water-use-efficiency (WUE) of Tifdwarf bermudagrass. Published reports reveal many researchers have investigated the influence of soil amendments on turf establishment, soil compaction and aeration, soil hydraulic properties, and turfgrass response (Biran et al., 1981; Miller, 2000; McCoy 1992; Nus and Brauen 1991). Other studies have investigated WUE of grass species as well as how WUE is influenced by fertilization (Frank et al., 1987; Hatfield et al. 2001). However, studies to determine the influence of different rootzone media on WUE of turfgrass are limited. A series of glasshouse and field experiments were conducted in Gainesville, Florida, from 2001 to 2004 to investigate WUE of Tifdwarf bermudagrass as influenced by soil amendments. The objectives of this study were (1) to determine the influence of various soil amendments (peat, Fe-humate, calcined clay, diatomaceous earth, zeolite, and smectite)

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3 on WUE and quality Tifdwarf bermudagrass in a USGA putting green; (2) to determine the influence of soil amendment incorporation method on WUE and quality of Tifdwarf bermudagrass in a USGA putting green. Nutrient Leaching For many agronomically important crops, nitrogen (N) and phosphorous (P) are the two most limiting nutrients. As such, they are typically applied via fertilizers in greater quantities than many other nutrients. Most fertilizer applied N is in the form of nitrate (NO 3 ) or is rapidly converted to nitrate via nitrification. Most fertilizer applied P is in the form of phosphate (H 2 PO 4 ). Being anions, both nitrate and phosphate are susceptible to leaching, the consequences of which are seen in the excessive algae growth in lakes and the elevated levels of P currently being detected in estuaries and in Everglades National Park (Malecki et al., 2004; White and Reddy, 2004). For this reason, N and P applied to agronomic crops and turfgrass has been closely monitored. Golf courses are often scrutinized due to their cultural practices and the unique fertilizer requirement of turfgrass, which often demand higher fertilizer application rates than many agronomic crops (Sartain, unpublished data, 1996). This scrutiny has brought about best management practices (BMP), which allow a turfgrass manager to minimize environmental impact while still being able to maintain a quality playing surface. Generally, these practices include the use of controlled-released fertilizers as well as the proper timing and rate of application. A number of studies have shown the BMPs have been beneficial at reducing the potential impact golf courses have on the environment (Rodriquez and Miller, 2000; Sartain and Gooding, 2000; Snyder et al., 1984). However, leaching of N and P does still occur during unique periods such as turf establishment or excessive rain events. During periods of high rainfall, leached N

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4 can be as much as ten times higher as during normal rainfall periods (Morton et al., 1988). This influence could be exacerbated on sand-based putting greens due to their inherently low nutrient retention capacity. Hexadecyltrimethylammonium (HDTMA) is a cationic surfactant that can be electrostatically bound to the negatively charged surface of selected soil amendments and has been shown to remove anionic compounds, such as nitrate and chromate, from solution (Li, 1999). Due to its success, a surfactant modified soil amendment (SMSA) has been used to create permeable barriers for groundwater remediation (Bowman et al., 2001). A series of lysimeters studies were conducted at the University of Florida between 2002 and 2003 to investigate the influence of SMSAs on anion leaching below the turfgrass rootzone. The objective of this study was to determine the influence of SMSAs on leached nitrate, phosphate, and ammonium in a simulated USGA putting green.

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CHAPTER 2 LITERATURE REVIEW Soil Amendments The USGA has recommended putting greens be primarily sand-based (USGA, 1993). The high sand content of USGA putting greens allows greens to maintain adequate aeration and drainage while minimizing compaction. Due to the high traffic typically imposed on USGA greens, these characteristics are crucial to maintaining a quality-playing surface. However, sand-based greens do have limitations, the most important of which are low water and nutrient retention (Bigelow et al., 2000). Soil amendments counteract the tendency of sand-based root zones to be nutrient deficient and droughty (Crawley and Zabcik, 1985). The USGA recommends putting greens be amended with peat moss at a rate of 85% sand and 15% peat by volume (Beard, 1982). The addition of peat moss increases the cation exchange capacity (CEC) as well as the water holding capacity of the growing media. However, peats are organic and are subject to microbial degradation. Many years of peat decomposition may be detrimental to putting green performance. In recent years, superintendents have shown a growing interest in inorganic soil amendments to use in place of peat. Inorganic amendments are not subject to biological degradation, and thus are considered to be more stable than organic amendments, which decompose with time. Many different types of inorganic soil amendments are currently marketed for golf green construction. These include calcined clays, zeolites, 5

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6 diatomaceous earths, and water treatment residuals. Characteristics between organic and inorganic amendments differ greatly; thus each will be considered and discussed individually. Peats The oldest and most widely used organic amendment used on golf courses is peat (Beard, 2002). Peats are typically mined from deposits located in cool, flooded environments. Low temperatures decrease microbial activity and can increase peat accumulation. Flooded conditions further increase the likelihood of peat accumulation by limiting oxygen availability. Peats can vary dramatically in their characteristics in large part due to the environment and parent material from which they formed. Peats have been classified into three types: 1) moss peat, which is from sphagnum, hypnum, and other mosses; 2) reed-sedge peat, from reeds, sedges, and other swamp plants; and 3) peat humus, peat of any form that has degraded to the point where no plant parts are identifiable (Lucas et al., 1965). When investigating six different types of peat, Carlson et al. (1998) found the pH of these peats varied from 2.9 to 6.2, water retention varied from 33 to 60% by volume, and the organic matter content varied from 63 to 95%. Despite these differences in laboratory-analyzed characteristics, no differences were observed in turf quality when these peats were used to amend putting green root zones. Benefits of adding peat to a turfgrass root zone include (a) release of soluble nutrients and gradual release of nutrients through microbial degradation, (b) increase CEC for nutrient retention and chemical buffering, and (c) increase moisture retention. Peats provide a number of plant essential nutrients. Comer (1999) reported Mehlich-I extractable P, Mg, and Ca increased by 575, 525, and 340%, respectively, by adding peat to USGA sand. Correspondingly, plant uptake of P, Mg, and Ca were higher

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7 in peat amended-sand than the control. These increased nutrients lead to an increase in total dry matter production of 7%. No differences in extractable K were observed by Comer, a trend that was also observed by Ok et al. (2003). Ok et al. investigated creeping bentgrass performance as influenced by three amended root zones and reported higher levels of P, Mg, and Ca in peat-amended root zones than the control. Peats are composed of a variety of reactive, organic compounds. Polyphenols, polyquinones, and polysaccharides are a few compounds found in peat, each of which possesses hydroxyls, carboxyls, and phenolic groups that dissociate and give rise to a CEC by weight that is often higher than most inorganic soil amendments (Carrow et al., 2001). The charge associated with peat is pH dependent and, thus, changes in relation to the pH of the soil solution. As pH increases, some H + ions are neutralized by OH ions and the CEC of the peat increases. Conversely, as pH decreases, H + ions in solution become sufficient to saturate negative charges on organic matter and the CEC decreases. Incorporating peat into a sand-based root zone can increase the root zone CEC by as much as 425% (Bigelow et al., 2001a). This increase in CEC directly influences nutrient retention. At 20% (by volume) incorporation, peat can decrease NH 4 -N leaching from 96% to 37% of applied N (Bigelow et al., 2001a). Ammoniacal-N may then become available for plant uptake or be oxidized by nitrifying bacteria (Sylvia et al., 1997). Leaching of cationic nutrients such as K, Ca, and Mg have also been shown to decrease with peat incorporation (Snyder, 2003). However, additions of peat may increase leaching of anionic nutrients. Brown and Sartain (2000) observed a 30% increase in leached P by adding peat to uncoated sand, which may have been attributed to the soluble P content of peat which effectively increases total soil P.

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8 Due to their fibrous, porous nature, peats can increase total soil porosity and thus increase soil moisture retention. Critical levels for optimum soil porosities have been suggested and range from 0.10 to 0.20 (Baver, 1956; Flocker et al., 1959, and Wesseling and van Wijk, 1957). Currently, the USGA specifies putting green root zones should have an aeration porosity of 0.15 to 0.30 (USGA, 1993). However, aeration porosity is typically not uniformly distributed throughout the 30 cm putting green root zone. Taylor et al. (1997) reported the bottom 9 cm of a sand/peat mixture had 3 to 7% air-filled porosity while the top 21 cm had 22 to 37%. Similar results were reported by Flury et al. (1999) in which the lower boundaries of experimental lysimeters were found to remain near saturation while the upper 80% of the soil columns exhibited a uniform moisture distribution. The influence peat has on porosity also affects bulk density. Bigelow et al. (2001b) found incorporating peat (10% by volume) with sand decreased bulk density from 1.66 to 1.54 g cm -3 increased total porosity from 0.41 to 0.47, and increased air-filled porosity from 0.24 to 0.28. This increase in porosity allows sand amended with peat to retain more water than sand alone. Sphagnum peat moss has been found to hold 10-14 times its own weight in water (Hummel, 2000). When incorporating peat, soil moisture contents have been found to be higher than sand amended with zeolites and calcined clays (Bigelow et al., 2001b). After saturation followed by drainage for 48 hours, sand/peat mixtures were found to retain as much as 46% more water than sand alone (Taylor et al., 1997). The organic matter associated with peat incorporation also influences plant available water (PAW). Hudson (1994) found the correlation between OM and PAW to

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9 be significant (r 2 = 0.79), and that as OM content increased from 0.5 to 3%, PAW more than doubled. However, peat incorporation may not always be beneficial to PAW. McCoy (1992) found that Canadian sphagnum peat retained water within organic matter pores beyond that available to the plant. He further suggested that much of the water retained by organic amendments with fiber contents in excess of 45% is unavailable to plants. In the same study, Canadian sphagnum peat had a fiber content of 54%. Addition of peat to sand-based root zones increases plant growth and soil productivity (Lucas et al., 1965). Incorporation of sphagnum peat to uncoated, coated, and artificially coated sand shortened turf establishment by 14 days and increased yield by 50% (Snyder, 2003). Following establishment, a 12-week maintenance study was conducted in which peat-amended pots produced 24% more dry matter than sand alone. These findings are in contrast to Smalley et al. (1962) who investigated the influence of peat and calcined clay (10% by volume) on Tifgreen bermudagrass and reported neither had any effect on dry matter yield. During this one-year study, 1022 and 484 kg of N and K ha -1 were applied, respectively. At this fertilization rate, it is likely that turf on both the control and treated plots received adequate nutrients, and the influence of peat and calcined clay (CC) was minimized thus, no differences were observed. Other researchers have reported different results. Cooper et al. (1998) investigated the influence of four humic substances including peat on root mass and nutrient uptake of creeping bentgrass. They reported little or no difference in root mass or N, K, Ca, Mg, or Fe uptake between any humic compounds or the control. Calcined Clays Mined clays, typically smectites, are heated to 800 o C to harden the amendment and increase their stability (Bigelow et al., 1999). The clay is then sieved to

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10 achieve a desired particle size and sold as calcined clays. Calcining the clay allows the amendment to maintain its beneficial characteristics such as CEC and moisture retention while eliminating shrinking and swelling, which can be detrimental to putting green performance. Calcined clay has the advantages of withstanding compaction, providing high infiltration, and allowing good aeration (Letey et al., 1966). Cation exchange capacity of calcined clays arises from isomorphic substitution of Al +3 for Mg +2 in the octahedral sheet and, thus much of the charge is independent of pH. Reported CEC values of calcined clays vary from 24-34 cmol(+)/kg (Richardson and Karcher, 2001; Carrow et al., 2001). Field plots modified with calcined clays have shown increases in CEC as well as increases in nutrient retention. Li et al. (2000) observed an 8% increase in CEC when comparing plots amended with calcined clays to a control. They also observed a 100% and 30% increase in exchangeable K and Mg, respectively. In the same study, exchangeable Ca decreased by 4%, a trend which was also observed by McCoy and Stehouwer (1998). The increase in CEC reported by Li is lower than results reported by Bigelow et al. (2001a). Exchange capacities in their study increased from 0.8 in the control to 2.4 cmol(+) kg -1 in the calcined clay amended plot. Calcined clay was further shown to increase CEC above a zeolite treatment which was reported to be 1.6 cmol(+) kg -1 Calcined clays are incorporated with sand not only to increase the CEC, but also to aid in moisture retention. When sand is mixed with CCs (15% by volume), porosity has been reported to increase by as much as 15% over sand alone (Waltz et al., 2003). Correspondingly, total water retained after drainage also increased from 19.9 to 23.1 cm in sand and CC plots, respectively. Li et al. (2000) reported sand modified with calcined

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11 clay retained 13% more water than sand alone. Li theorized that calcined clay probably provided for a more favorable ratio of macropores to micropores which equaled 3.77. Macropores play a vital role in hydraulic conductivity while micropores are more responsible for water retention (Rowell, 1994). Root zone modifications that alter pore space distribution and improve aeration and water conditions can favor turfgrass growth (Waddington, 1992). Turf establishment and growth are generally increased by incorporating CCs into a sand-based rootzone. Waltz and McCarty (2000) conducted an experiment involving the incorporation of soil amendments and their influence on turf establishment. They found plots containing sand and CC achieved 75% and 100% establishment, respectively, at 9 months after seeding. Furthermore, calcined clay treatments produced a higher visual rating of density and color than plots with sand alone. However, these findings differ from those reported by Smalley et al. (1962). They investigated the influence of CC on turf yield and quality and reported that incorporating CC decreased yield and quality. They observed this effect was particularly evident during a droughty period, and concluded the decrease in yield and quality likely resulted from excessive aeration and consequent reduction in available moisture. Zeolites Zeolites are naturally occurring minerals that can form in a variety of environments. The most common zeolite used for agricultural purposes is clinoptilolite because it is the most common zeolite found in soil parent material (Boettinger and Ming, 2002). Like quartz, zeolites are tectosilicates, thus its structure prevents any shrinking or swelling that sometimes occurs with other soil minerals. However, unlike some tectosilicates, zeolites are porous, thus they tend to have low densities (1.9-2.2 g cm -3 )

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12 (Breck, 1974). Their porous nature also increases their surface area and its cation exchange capacity. Clinoptilolite has been shown to have a void volume near 34% and a CEC as high as 220 cmol(+) kg -1 which arises from isomorphic substitution of Al 3+ for Si 4+ (Meier and Olson, 1988). The internal pores of clinoptilolite are small enough to limit the adsorption of some larger ions, thus clinoptilolite is highly selective for K + and NH 4 + relative to Na + or divalent cations such as Ca 2+ and Mg 2+ (Ming and Mumpton, 1989). Goto and Ninaki (1980) determined the ion-exchange selectivity order of natural zeolites to be K + > NH 4+ > H + > Na + > Sr 2+ > Ca 2+ > Mg 2+ > Li + The strong affinity zeolites have for K + and NH 4 + has prompted municipalities to use zeolites for the removal of NH 4 + from sewage (Mercer et al., 1970). Their high CEC is the primary reason zeolites have been used to amend putting green root zones. Addition of zeolites to sand-based root zones has been shown to increase the CEC by as much as 200 fold (Huang and Petrovic, 1994). This increase in CEC helps to buffer the soil and increase retention of nutrients such as K, NH 4 Ca, and Mg. Ferguson et al. (1986) observed that zeolite amended soils produced higher turf quality than non-amended soils. It was hypothesized that NH 4 + produced from urea applications was adsorbed by the clinoptilolite and was slowly released, which resulted in a more healthy turf. In defense of this theory, an incubation study was conducted in which NH 4 -N was mixed with clinoptilolite amended USGA sand. After 25 days of incubation, NH 4 + loss due to nitrification, denitrification, and/or volatilization was lower in clinoptilolite-amended sand than vials containing sand alone. This was attributed to the internally sorbed NH 4 + being inaccessible to denitrifying bacteria (Ferguson and Pepper, 1987).

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13 Decreased NH 4 + leaching from zeolite-amended soils has also been attributed to the increased CEC that accompanies zeolite incorporation. When mixed at a rate of 50 g kg -1 clinoptilolite has been shown to decrease NH 4 -N leached from 168 to 29 mg NH 4 -N (Mackown and Tucker, 1985). A number of studies have reported reductions in NO 3 leaching with use of clinoptilolite. Huang and Petrovic (1994) not only reported that NO 3 and NH 4 + leaching was 86 and 99% lower, respectively, in zeolite-amended sand than sand alone, they also observed the fertilizer use efficiency of creeping bentgrass increased as much as 22%. Lewis et al. (1984) reported pots containing a loamy sand soil amended with clinoptilolite reduced NO 3 leaching by 33% compared to the control when fertilized with ammonium sulfate. These reported reductions in NO 3 leaching are likely attributed to NH 4 + release from clinoptilolite being limited by diffusion and cation exchange reactions (Semmens, 1984; Allen et al., 1995). The capacity zeolite has to retain cations may not always be beneficial. Some research suggests that the energy at which NH 4 + is held by zeolite may be enough to render NH 4 + inaccessible to plants. Ferguson et al. (1986) observed better bentgrass establishment on 5% than on 10% clinoptilolite amended plots. While this observation was attributed to high sodium content, more recent research suggests that high sodium levels may not be solely responsible for the decreased establishment, but rather N removal by NH 4 + sorption which effectively reduces plant available N. Regardless, other studies have shown that the influence of zeolite on creeping bentgrass establishment compares favorably with peat (Nus and Brauen, 1991). Zeolite incorporation typically increases turf establishment. Miller (2000) reported that bermudagrass was found to establish more rapidly and had greater growth on

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14 ZeoPro-amended plots than plots containing 100% sand and other rootzone mixtures. The higher nutrient levels accompanying incorporation of zeolite have been associated with more rapid establishment and high quality ratings of creeping bentgrass (Ok et al., 2003). It should be mentioned that studies conducted by Miller (2000) and Ok et al. (2003) involved the use of zeolite which contained as much as 0.1% N. Nitrogen loaded zeolite may act as an N source instead of an N sink which may increase turf growth and establishment. Natural zeolites do not contain N, thus turf grown on natural zeolite may react differently than turf established on N-loaded zeolite. This concept was also speculated by Ok et al. (2003). Nus and Braun (1991) investigated the incorporation of sawdust, peat, zeolite on establishment of creeping bentgrass and reported peat and zeolite were equally effective at increasing turf establishment. Diatomaceous Earths Algae, predominantly of marine origin, are responsible for the formation of diatomaceous earths (DE). Diatoms are microscopic, single-cell plants, which join to form sedimentary rock composed of fossilized skeletal remains of diatoms (Fresenberg, 1999). Chemically, DEs are like silica sand in that they are about 90 percent silica (SiO 2 ) with minor amounts of alumina (Al 2 O 3 ) (Mannion, 1996). Some DEs are calcined during manufacturing. Calcined DEs are 50 percent harder and suffer one-quarter the wet attrition loss of uncalcined DEs (Mannion, 1996). DEs are porous and, thus, have low bulk densities and can retain up to 150% its weight in water. Sands amended with DEs have been reported to have higher total porosity and overall water retention than sands amended with zeolite (Bigelow et al., 2004). However, Bigelow also reported that DE amended sand possessed the same porosity and water retention as peat and calcined clay amended sand. These findings

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15 were similar to those reported by Waltz et al. (2003). Waltz investigated the hydraulic properties of several soil amendments including DE. Waltz reported that water retained at field capacity was greater in sand amended with peat than with DE. However, as plots were allowed to dry, DE and peat amended sand held more water than CC amended sand. Waltz further observed that DE and peat amended sand held more water in the top 15cm of a 30 cm profile than CC amended sand. While turf growth was not investigated, Waltz speculated that amendments that slow water movement and retain more water in the upper portion of the rootzone would result in turf with less water stress than turf grown on media that retained less water due to rapid drainage. The influence of DEs on turf growth has been shown to be most pronounced during times of drought. Wehtje et al. (2003) evaluated bermudagrass growth as influenced by DE, zeolite, and calcined clays incorporated with sand at five rates. Their investigation consisted of measuring turf yield under luxury water and nutrient application and under drought conditions. When bermudagrass was supplied with adequate water and nutrients, sand amended with DE only produced more dry matter than un-amended soil at the highest incorporation rate (100% DE). However, under drought conditions DE increased dry matter production which, in general, increased with increasing incorporation rate. Experimental conditions during this study were variable. However, Wehjte et al. concluded that improvement in bermudagrass performance in amended sand relative to soil alone was most likely related to increased water-holding capacity. This theory was not only based upon their findings, but also upon previous research conducted by Ralston and Daniel (1973). During their research, Ralston and Daniel investigated the influence of calcined clay and DE on creeping bentgrass. After two 15 day dry down periods, they

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16 found plots containing DE maintained normal growth without additional water applications while plots containing calcined clay required water after 5 days. More recent research has also shown turf grown on DE amended sand produced better coverage and more dry matter than CCs or peat during times of drought (Waltz and McCarty, 2000). Water Treatment Residuals Water treatment facilities use FeSO 4 to remove humic substances from water for human consumption. Water treatment residuals (WTRs) are products of this process. WTRs contains humic and fulvic acids as well as iron, which is a plant essential element (Salisbury and Ross, 1992). In general, WTRs have a positive influence on soil moisture. Bugbee and Frink (1985) observed increases in soil moisture retention and aeration from WTR incorporation with soil. Increases in soil moisture retention were also observed by Rengasamy et al. (1980) and were attributed, in part, to the increase in soil aggregate stability which accompanied WTR incorporation. Increasing soil structure by adding WTRs has also been shown to increase soil drainage (Scambilis, 1977) which is crucial to putting green performance. Applications of WTRs have been shown to increase plant growth. Basta et al. (2000) investigated the influence of WTRs on dry matter yield of bermudagrass. They reported bermudagrass grown on WTRs produced a yield of 26 g pot -1 while turf grown on native soil only produced 15 g pot -1 WTRs used in the Basta study contained 140 and 130 ppm NO 3 -N and NH 4 -N, respectively. High N levels along with high levels of P, K, Ca, Mg, and Fe were likely the cause of the observed increase in turf growth. A similar explanation was given by Elliott and Singer (1988) when they studied the influence of

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17 WTR on growth of tomato and observed an increase in yield following the incorporation of WTR. Ippolito et al. (1999) investigated the influence of co-application of biosolids with WTRs on biomass yield of two range grasses. They concluded that increasing the rate of WTR incorporation increased biomass production for both turf species. However, in general, turf grown on plots containing less than 150 g kg -1 WTR did not show yield increases. Lower incorporation rates were used by Heil and Barbarick (1989) when investigating WTR incorporation and its effect on the growth of sorghum-sudangrass. By increasing WTR incorporation rate from 0 to 20 g kg -1 Heil and Barbarick increased turf dry matter production from 6 to 20 g pot -1 They attributed this increase in yield to an increase in plant available Fe which was not observed in the control pots, which exhibited Fe-deficiency symptoms. Other researchers have observed limited influence of WTRs on plant growth. Geertsema et al. (1994) applied WTR at three rates of 0, 36, and 52 dry Mg ha -1 to loblolly pine (Pinus rigida Mill.) and reported no differences in plant growth between amended and unamended plots after 30 months of growth. Water-Use-Efficiency Water-use-efficiency (WUE) is defined as the quantity of dry matter produced per quantity evapotranspired water (g dry matter mL ET -1 ). WUE may be influenced by plant species, nutrient availability, water availability, or cultural management practices. Many studies have shown that water use is directly related to available soil moisture, and, to a point, WUE increases as soil moisture decreases. Youngner et al. (1981) investigated water use of two cool-season and two warm-season grasses. Soil moisture was maintained according to tensiometer readings of 0.015, 0.035, and 0.055 MPa. Regardless of turf species, water use was maximized under the highest soil moisture tension. Danielson et al. (1981) measured the water use of Kentucky bluegrass

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18 under differing soil moisture levels including 100%, 80%, and 70% field capacity. They reported irrigation of 80% field capacity reduced water consumption by 20% with only minor reductions in turf quality. Similar results were reported by Meyer et al. (1985). They also used varying irrigation rates from 100 to 60% ET estimated values and reported that when irrigation rates were dropped to 80% ET, turf quality rates dropped only 3% for cool-season and 5% for warm-season grasses. Stout et al. (1988) investigated the influences of soil and N on WUE of tall fescue and concluded that based upon the regression of WUE and soil variables, the influence of soil on WUE increases during periods of limited water availability. This indicates that when water is limited, differences in WUE between different rootzone media may be more pronounced. Differences between WUE not only exist between different plant species, but also between different cultivars or varieties within a species. C-4 plants are more efficient users of water than C-3 plants during periods of high light and temperature (Black et al., 1969). This is due to more efficient carbon assimilation in C-4 plants. C-4 plants are able to take up more CO 2 through their stomata, thus less water is lost for every CO 2 molecule assimilated (Hull, 1992). WUE of C-4 grasses has been reported to be as much as 2x higher than C-3 grasses (Schantz and Piemeisel, 1927). These results were similar to Fu et al. (2003) who reported Meyer zoysia to have a WUE more than 3x higher than Falcon II tall fescue. Cultural practices that influence WUE include: irrigation frequency, mowing height, and fertility program. Minner (1988) observed an increase in water use rate when irrigation frequency was increased. Minner also reported water use increased as mowing height increased which was attributed to an increase in leaf area index. Biran et al.

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19 (1981) increased cutting height from 3 to 6 cm and found similar results with Festuca arundinacea and Lolium perenne. They reported a permanent increase in water consumption and growth, as well as an increase in chlorophyll per unit weight in clippings. However, Biran did not find any permanent increases in water consumption or plant growth in C-4 turfgrasses. In general, the greatest single factor influencing WUE is soil fertility. Stout et al. (1988) studied the influence of 3 soils and 3 N rates on WUE of tall fescue. When N rates increased from 45 to 90 kg ha -1 WUE increased by as much as 50%. Stout reported during fall harvests, N fertility was always the major component influencing WUE of tall fescue. Feldhake et al. (1983, 1984) used two N fertilization levels to determine the influence of N on water use of Kentucky bluegrass. They reported higher ET levels from turf supplied with 4 kg of N 1000 m -2 mo -1 than from turf supplied with 4 kg of N 1000 m -2 yr -1 A more recent study investigated the influence of 4 soils, 3 N rates, and 2 turf species and concluded N fertilization increased WUE at all application rates with the highest application rate having the greatest influence on WUE (Stout, 1992). The influence of N fertility on WUE has been shown to be most pronounced when water is limited. Stout and Schnabel (1997) investigated WUE of perennial ryegrass over a two-year period. During year one, when rainfall and irrigation supplied water were considered to be adequate for turf growth, N fertility increased WUE 154%. During year two, when rainfall and irrigation were low, N fertility increased WUE 455%. Nitrogen in the Turfgrass Environment In order to limit N leaching and the environmental impact of N fertilization, one must thoroughly understand the N cycle (Fig. 2-1) and the transformations that N

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20 undergoes in a dynamic soil system. These processes include: plant uptake, soil retention and microbial immobilization, runoff and leaching, or atmospheric loss (Petrovic, 1990). N Transformations in Soil Soil N exists primarily in two forms: organic and inorganic. Organic N is present in a variety of compounds including proteins and amino acids. Forms of inorganic N include NH 4 + and NO 3 and are produced from the aerobic oxidation of organic N or from fertilizer input. From the standpoint of environmental impact and leaching, NH 4 + and NO 3 are the most important because it is these compounds that are mobile in the soil solution (Follett, 1989). Organic N is converted to NH 4 + by heterotrophic microorganisms during mineralization. N mineralization is strongly influenced by moisture and O 2 content. Maximum N mineralization occurs between 50 and 70% water-filled pore space (Havlin et al., 1999). Once in inorganic form, NH 4 + may take a variety of paths including plant uptake, mineral fixation, volatilization, or nitrification. Nitrification is the conversion of NH 4 + to NO 2 and then to NO 3 Nitrification consists of two reactions. The first reaction is mediated primarily by microorganisms belonging to the group Nitrosomonas. 2NH 4 + + 3O 2 2NO 2 + 2H 2 O + 4H + The second reaction oxidizes nitrite to nitrate and is mediated primarily by organisms in the Nitrobacter group. 2NO 2 + O 2 2 NO 3 Both reactions require O 2 thus each reaction is highly dependent upon aerification and moisture content. In aerated soils, nitrification is normally a rapid process requiring only days to convert the NH 4 + to NO 3 During a 53 week incubation study to investigate

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21 mineralization rates in a variety of Florida soils, Reddy (1982) observed low levels of NH 4 + in effluent of soil columns and found high concentrations of NO 3 These results were attributed to rapid nitrification of the mineralized NH 4 + Tate (1977) also reported rapid nitrification occurred in well-aerated soils which may result in little or no NH 4 + accumulation. Fertilizers N2O NO N2 Denitrification NH4 + Fixation Plant and Animal Residue Plant Uptake NO3 /NH4 + Leaching Immobilization Mineralization NO3 NH4 + Nitrificatio n NH4 + R-NH2 Soil Organic Matter NH3 Volatilization Figure 2-1. The Nitrogen Cycle (Havlin et al., 1999)

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22 Leached N The most common source of NO 3 pollution of ground and surface water is agriculture (Halberg, 1987; Pratt, 1984). While turfgrass is not often thought of as an agricultural crop, golf courses and home lawns are maintained according to many of the same practices and, thus they are also sources of nitrate leaching (DeRoo, 1980; Morton et al., 1988). Susceptibility of USGA putting greens to N leaching has been well documented. Snyder et al. (1984) investigated the influence of moisture-sensor irrigation on N leaching and reported 56% of applied N from ammonium nitrate was leached under a daily irrigation schedule. They also observed 85 to 98% of leached N occurred as NO 3 -N and that 75% of leached N occurred within 20 days of application. Bigelow et al. (2001a) used several laboratory studies to monitor leaching losses of N from a sand-based medium amended with 20% peat by volume and reported addition of peat decreased NO 3 -N leached from 98 to 95% of that applied, which was statistically significant. Peat had a greater influence on leached NH 4 -N dropping the percent NH 4 -N lost from 96 to 37% of that applied. Because of its positive charge, NH 4 -N can adsorb to soil particles and, thus may not leach readily. However, Sartain (1990) applied (NH 4 ) 2 SO 4 to bare soil, encouraged leaching, and found after 112 days, 80% of applied N leached with 68% being NH 4 -N. In most agricultural soils, N leaching is primarily as NO 3 -N simply due to the rapid oxidation of NH 4 -N to NO 3 -N. Because all N leaching occurs in soil solution, soil water content plays a major role in N movement through the soil profile. In general, N leaching potential increases as water application increases (Morton et al., 1988). Starrett el al. (1995) investigated two

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23 irrigation regimes on N leaching and found 30 times more N leached when irrigation rates were increased by a factor of four. Phosphorous in the Turfgrass Environment Phosphorus is a macro nutrient used by plants to produce ATP, which in turn is used as an energy source which drives many metabolic processes. Phosphorus exists in soil solution primarily in anionic form (Fig. 2-2). Additions of P to soil solution arrive via desorption from soil exchange sites, dissolution of primary and secondary minerals, and mineralization of organic matter. In most agronomic situations, plant uptake and leaching are the only process whereby P is removed from the soil system. P Reactions in Soil Total P in most surface soils varies but is generally between 0.005 and 0.15% (Havlin et al., 1999). Of the total P, only a small portion actually exists as solution P which is that portion available for plant uptake. Solution P is maintained by dissolution of primary and secondary mineral, mineralization from organic matter, and by desorption from mineral and clay surfaces (Fig. 2-2). These processes are responsible for replenishing the soil solution P that is taken up by the plant. When these processes cannot adequately supply P, fertilizers must be used to artificially increase solution P concentrations. However, when solution P exceeds the amount needed by the plant, the potential for P leaching increases. Leached P Phosphorus is considered to be a critical nutrient responsible for eutrophication of surface water bodies. Eutrophication of surface water has been identified by the USEPA as a major cause for quality degradation of surface waters which may lead to problems

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24 Plant and Animal Residue Fertilizer Plant Uptake Mineralization Immobilization Adsorption Desorption Precipitation Dissolution Dissolution Solution P H2PO4 HPO4 -2 (labile) Soil Organic Matter (Nonlabile) Adsorbed P (Labile) Secondary Minerals Fe/AlPO4 CaHPO4 (Nonlabile) Primary Minerals (Nonlabile) Leaching Figure 2-2. The P cycle (Havlin et al., 1999). with their use for fisheries, recreation, industry, or drinking water (OConnor and Sarkar, 1999). Periodic surface cyanobacteria blooms occur in drinking water and may pose a serious threat to livestock and humans (Lawtin and Codd, 1991; Martin and Cook, 1994). In recent years, a number of studies have investigated P leaching. Brown and Sartain (2000) used several P fertilizers to investigate P retention in a variety of sand/amendment mixtures. They reported P leached from an uncoated sand/peat rootzone (85:15 by volume) was less than 7% of applied P. However, they also observed

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25 twice as much P leached from peat amended sand than from sand alone. These finding are somewhat lower than that observed by Shuman (2001). Shuman investigated P leaching from a simulated USGA putting green in an environmentally controlled greenhouse and reported 27% of applied P was lost via leaching. Uncoated sands typically retain less P than coated sands. Harris et al. (1996) investigated the P sorption characteristics of coated and uncoated sands via a number of adsorption and desorption experiments. They reported the presence of sand grain coatings enhanced P adsorption and resistance to desorption. Soil amendments have been used to reduce P concentrations in ground water. Porter and Sanchez (1992) reported that P sorption in a Histosol was correlated with soil ash and CaCO 3 content. Coale et al. (1994) applied gypsum and WTR and investigated their influence on P leaching. They reported decreased leachate P concentration from both amendments with gypsum causing the greatest decrease in leached P. Hexadecyltrimethyammonium Hexadecyltrimethylammonium (HDMTA) [CH 3 (CH 2 ) 15 N(CH 3 ) 3 ] is an amphoteric compound containing both hydrophobic and hydrophilic components. Each molecule possesses a positively charged head and a 16-carbon tail. The head groups of HDTMA are similar to NH 4 + ; however, three protons in NH 4 + are replaced by three methyl groups while the fourth is replaced by the tail (Fig. 2-3) (Li and Bowman, 1997). Its unique properties allow the surfactant to bind to solid particles that possess a CEC and effectively reverse their charge, thus the particle is now capable of adsorbing many anionic compounds.

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26 H3 H3 C C Figure 2-3. Hexadecyltrimethylammonium. Bi-layer Formation Bi-layer formation involves two steps. The first step involves direct attachment of HDTMA micelles to the amendment surface via electrostatic bonding. The second step involves HDTMA surface rearrangement, which is directly related to the initial surfactant input in relation to the ECEC of the amendment. If the initial surfactant input is less than the ECEC, each micelle will dissociate to form a monolayer. If surfactant input is greater than the ECEC but less than twice the ECEC, an incomplete or patching bi-layer forms. Figure 2-4. Schematic of HDTMA bi-layer formation. N H2 H2 H2 H2 H2 H2 H2 H3 C C C C C C C C C H2 C H2 C H3 C H2 C H2 C H2 C H2 C H2 C H2 Positive Head Group + + + + 24-26 + + + + Amendment Surface ---

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27 If surfactant input is greater than twice the ECEC, a complete bi-layer will form (Fig. 2-4). The initial step is relatively fast generally requiring less than one hour. The second phase involves intraparticle diffusion, which can require as many as 48 h to achieve bi-layer formation depending upon the ECEC of the solid phase (Li, 1999). Cation exchange is responsible for retaining the lower layer while hydrophobic bonding causes formation of the upper surfactant layer (Li and Bowman, 1997). Anion Sorption Recent literature indicates HDTMA-modified solids are effective sorbents for multiple types of contaminants, such as chromate, naphthalene, perchloroethylene, and nitrate (Li and Bowman, 1997; Nzengung et al., 1996). While investigating the HDTMA counterion influence on chromate sorption, Li and Bowman (1997) observed sorption isotherms were well described by the Langmuir equation. Chromate sorption maximum was reported to be 16 mmol kg -1 More importantly, Li and Bowman found the exchange ability of the counterion on HDTMA was more influential on chromate sorption than the initial HDTMA loading concentration. Other studies investigating NO 3 sorption have found similar results. Li et al. (1998) investigated NO 3 sorption isotherms, which like CrO 4 2, were well described by the Langmuir equation. Sorption maximum for NO 3 was 100 mmol kg -1 The same study produced results that indicated NO 3 is more suitably sorbed than CrO 4 2, which seems unlikely since the divalent CrO 4 2has a higher charge density than the monovalent NO 3 and thus should be more selectively sorbed. Investigators theorized that because sorbed HDTMA onto an amendment surface does not form a rigid structure, the stability of the HDTMA-CrO 4 ion pair might be lower than the HDTMA-NO 3 ion pair, which may explain why NO 3 is more suitably sorbed than CrO 4 2.

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28 Stability The resistance of surfactant-modified soil amendments (SMSA) to biological degradation or physical weathering is crucial to their long-term effectiveness. Investigations into the influence of aqueous quaternary ammonium cations (QACs) on microbial growth have found aqueous QACs to be biocidal. Gilbert and Al-taae (1985) investigated a number of QACs with varying chain lengths with 4-22 carbons and reported bacteria strains were most sensitive to QACs containing 14 carbon tails while yeast and fungi were most sensitive to QACs containing 16 carbon tails. Microbial growth was least inhibited by QACs with shorter tails. In general, QACs with longer tails are more biocidal than those with shorter tails (Korai and Takeichi, 1970). Although QACs like HDTMA have been shown to be biocidal, they can be degraded microbially. Dean-Raymond and Alexander (1977) investigated the biodegradation of 10 QACs including HDTMA using sewage and soil as their sources for microorganisms. They reported decyltrimethylammonium and HDTMA were both metabolized by microorganisms from both sources. In the same study, Decyltrimethylammonium bromide was observed to be the sole carbon source for a mixed population of two bacteria from soil. Each of the preceding cases involved investigations on aqueous QACs. The influence of sorbed QACs on microbial growth is quite different. A study was conducted in New Mexico which involved microorganism growth on agar plates after being inoculated with a mixture of surfactant-modified zeolite (SMZ) and activated sewage sludge (Li et al., 1998). After 17 weeks of incubation, microorganism growth remained essentially the same between treated plates and the control. Toxicity from QACs is primarily from the alkyl chain (Korai and Takeichi, 1970). Surfactant-modified soil amendments which have been modified to ensure bi-layer formation have very few

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29 tails exposed to soil solution, thus toxicity of SMSA is very low or non-existent (Li et al., 1998). Investigations into the physical stability of SMSA are somewhat limited. However, Li et al. (1998) used SMZ in a series of leaching experiments to determine the extent of bi-layer removal. They used two types of water, Type I had an ionic strength of zero, and type II used K 2 CrO 4 to increase the ionic strength to 8mM. They reported HDTMA desorption to be 0.34 mmol kg -1 pore volume -1 from type I water and 0.14 mmol kg -1 pore volume -1 from type II water. Based on these observations, they predicted that 65% of sorbed HDTMA would remain after 500 pore volumes of type II water. This hypothesis was later verified in a laboratory column test.

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CHAPTER 3 MATERIALS AND METHODS This research consisted of a variety of amendment characterization studies and two glasshouse studies. Characterization Studies Characterization studies were conducted in a number of soil laboratories at the University of Florida from fall 2001 to fall 2004. Cation Exchange Capacity Cation exchange capacity for each amendment and sand/amendment mixture was determined via the ammonium acetate pH 7.0 method (Soil Survey Laboratory Staff, 1996). Five grams of soil media were placed in leaching tubes and leached with 25 mL of 1 M NH 4 OAc. Leaching tubes were then closed and an additional 25 mL 1 M NH 4 OAc were applied and soil media remained in solution for 48 h. Leaching tubes were then opened followed by two applications of 100 mL ethanol. A total of 60 mL 1 M KCl were leached through each tube, collected, brought to 100 mL volume, and analyzed for NH 4 + Moisture Retention Moisture release curves were determined for each sand mixture according to the process described by Klute (1986). Field plots were originally established with the intention of mimicking the glasshouse studies. Each plot contained rootzones corresponding to the rootzone of glasshouse pots. However, due to experimental difficulties during the first 3 months of the study, establishment was delayed. 30

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31 Furthermore, once data began to be collected from the plots, excessive rainfall from both hurricanes Frances and Jeane heavily skewed the data. Thus, no results from field plots were included in this study. However, since removing usable cores from glasshouse pots was not possible due to the rootzone depth required, cores were taken from the field plots using a brass ring (3 cm high 5.56 cm diameter). The ring was placed on a half-bar porous ceramic plate, which was then placed into a Model 1400 Tempe pressure cell (Soil Moisture Equipment, Santa Barbara, CA). Tempe cells were placed in a water bath until each cell achieved saturation. The cells were then placed on a rack and connected to a hanging-water column pressure system. Pressures applied corresponded to 0, 3.5, 10, 15, 20, 25, 30, 35, 50, 100, and 345 cm water (1 bar per 1035 cm water). After the final pressure of 15 bar (wilting point), the cell was opened, the brass ring was removed, and the soil was weighed. In order to conduct statistical analysis, two soil cores were used as replications. Sorption Isotherms All sorption isotherms followed procedures outlined by Li (1999). Nitrate-N, NH 4 -N, and P sorption isotherms were conducted on HDTMA-coated and uncoated zeolite (Zeo Inc., McKinney, Tx) and two calcined clays [Soil Master Plus (Sport Turf Supply, Inc., Midland City, Al.), Profile (Profile LLC)], which will be referred to hereafter as calcined clay 1 and calcined clay 2, respectively. Nitrate isotherms were prepared by adding 0.5 grams of each amendment to 10 mL of solution containing 0, 10, 20, 100, 200, and 500 ppm NO 3 -N to achieve loading rates of 0.2, 0.4, 2.0, 4.0, and 10.0 g kg -1 Ammonium isotherms were prepared by adding 0.25 grams of each amendment to 20 mL of solution containing 50, 100, 200, 500, and 1000 ppm NH 4 -N to achieve loading rates of 0, 4, 8, 16, 40, and 80 g kg -1 Phosphorus isotherms were prepared by adding 1.0 g of each

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32 amendment to 10 mL of solution containing 0, 10, 20, 100, 200, and 500 ppm P to achieve loading rates of 0.1, 0.2, 1.0, 2.0, and 5.0 g kg -1 Samples for each isotherm were shaken on a mechanical shaker for 48 hours to achieve equilibrium. Samples were then centrifuged for 15 minutes at 4000 rpm to yield a clear supernatant. Nitrate and NH 4 -N solutions were analyzed using an Alpkem RFA-300 auto analyzer (IRAMA Corporation, Milwaukie,OR), and P solutions were analyzed colorimetrically. Surfactant Loading Surfactant loading followed procedures outlined by Li and Bowman (1997). Previous analysis produced CEC values for each amendment, which were used to determine the ratio of solid to solution. Due to financial and equipment restraints, final solution concentration analysis of HDTMA was not possible, thus, the amount of amendment added to solution was divided by 2 to ensure bi-layer formation. The amounts of amendment used during surfactant loading were 71, 544, and 350g of zeolite, CC1, CC2, respectively. These amounts were determined to be the maximum amount of amendment, based upon each amendments CEC, that could be added to HDTMA solution while assuring bi-layer formation. Amendments were placed in 2 L Erlenmeyer flasks, which were then filled to volume with 2 L of 0.066 M HDTMA solution. Each flask was stirred for 24 h by using a magnetic star bar and plate. Following equilibrium, the supernatant was removed, amendments were washed with 5 pore volumes of deionized water, and amendments were allowed to air-dry. Thermal Analysis Thermal gravimetry (TG) analysis cannot only be used to determine OM content, but it can also be use as an indicator of particle stability. Compounds that lose little weight when subjected to increasing heat are considered to be more thermally stable than

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33 compounds that exhibit weight losses. It has been stated that the greatest strengths of inorganic amendments are their resistance to degradation and breakdown (Waltz and McCarty, 2000). Each amendment was subjected to TG on an Omnitherm Corporation instrument (Arlington Heights, IL) with a nitrogen gas purge. Temperatures ranged from 25-600 C with a ramping rate of 20 C min -1 (Amonette, 2002). HDTMA was subjected to thermal analysis to determine the temperature at which oxidation occurred (Fig. A-1). This temperature was then used when analyzing SMSA to determine the extent of surfactant coating. Surfactant coating was determined according to eq. 3.3. S = ( A / 0.85 ) 10,000 mg kg -1 eq. 3.3. Where: S = amount HDTMA sorbed (mg kg -1 ) A = weight loss due to oxidized HDTMA (%) B = amount of HDTMA that oxidizes (%) From thermal analysis, effective anion exchange capacity (EAEC) was determined according to eq. 3.4. { [ ( C S HDTMA ) / 2 ] / MW N } 100 = cmol kg -1 eq. 3.4. Where: C = MW N / FW HDTMA (MWBr)/2 ( %) S HDTMA = HDMTA sorbed (g kg -1 ) FW HDTMA = formula weight of HDTMA (g mole -1 ) MW N = molecular weight of nitrogen (g mole -1 ) MW Br = molecular weight of bromide (g mole -1 ) Assumptions made during determination of EAEC included: 1.) percent HDTMA oxidation from SMSA was equal to the percent oxidation of pure HDMTA, 2.) all

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34 surfactant sorbed by amendments was in a bi-layer formation, and 3.) after bi-layer formation, all anion exchange sites in solution equaled the total exchange sites and were occupied by Br -1 X-Ray Diffraction In order to determine mineral composition, each amendment was subjected to x-ray diffraction using a computer-controlled x-ray diffractometer equipped with a stepping motor and graphite crystal monochromator (Nicolet I2/L11 Polycrystalline X-Ray Diffraction System, Madison, WI). Amendments were crushed using a mortar and pestle then placed in a side-packed powder mount with an Al-glass holder. Samples were scanned from 2 to 40 2 at 2 2 per minute using CuK radiation (Amonette, 2002). Nutrient Analysis All amendments and sand mixes were analyzed for P, K, Ca, Mg, Fe, Mn, Zn, and Cu. Analysis followed procedures outlined by Olsen and Sommers (1982). Five grams of each amendment (3 g of peat) were extracted using 20 mL of Mehlich-I solution (0.025 M HCl and 0.0125 M H 2 SO 4 ), then shaken for five minutes on a mechanical shaker. Samples were then filtered with a Whatman no. 42 filter paper and collected in 25 mL scintillation vials. Samples were analyzed at the University of Florida analytical research laboratory using a model 61E Thermo Jarrell-Ash ICAP 9000 spectrophotometer (Franklin, MA). Sand Mixes Rooting media for each glasshouse study, the field study, and the leaching study were mixed by hand using 85% USGA sand and 15% amendment by volume with the exception of smectite, which was incorporated at 97.5% USGA sand and 2.5%

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35 Table 3-1. Sand size analysis of amendments and sand mixes. Sand Very coarse Coarse Medium Fine Very fine Silt + Clay 1.0 2.0 mm 0.5 1.0 mm 0.25 0.50 mm 0.10 0.25 mm 0.05 0.10 mm <0.05 mm Amendment ---------------------------------% by weight -----------------------------------Clinoptilolite 1 45.4 48.0 6.8 0.0 0.0 0.0 Clinoptilolite 2 31.3 67.9 0.9 0.0 0.0 0.2 Calcined Clay 1 0.3 46.6 52.9 0.7 0.0 0.0 Calcined Clay 2 0.0 50.9 49.0 0.2 0.1 0.1 Diatomaceous Earth 1 27.7 56.5 15.3 0.4 0.1 0.2 Diatomaceous Earth 2 27.0 64.6 5.1 1.2 1.0 1.2 Peat 44.7 15.3 16.4 14.3 7.8 1.7 Montmorillonite 10.2 16.5 16.8 18.2 32.5 4.8 Iron Humate 11.8 17.2 31.5 32.9 5.4 1.1 Sand Mixture Sand 7.2 41.2 35.7 15.9 0.9 0.0 Clinoptilolite 1 11.9 39.9 31.2 16.7 0.3 0.2 Clinoptilolite 2 10.1 42.6 30.3 16.2 0.5 0.1 Calcined Clay 1 7.1 40.1 35.3 16.7 0.3 0.0 Calcined Clay 2 6.0 37.8 35.0 20.2 0.8 0.1 Diatomaceous Earth 1 7.1 36.7 33.9 21.4 0.7 0.0 Diatomaceous Earth 2 7.6 38.3 33.1 19.8 0.6 0.4 Peat 4.0 22.9 54.5 17.6 0.4 0.2 Montmorillonite 7.4 39.3 35.0 17.5 0.4 0.1 Iron Humate 8.8 37.0 33.1 19.3 1.1 0.3 ------------------------------------------USGA Specifications 10% 60% 20% 5% 8% Based on USGA range of 0.25 .015 mm. 85% USGA uncoated sand plus 15% amendment by volume 2.5% by volume United States Golf Association smectite. Particle size analysis was determined for each amendment and sand/amendment mixture according to procedures described by Day (1965) (Table 3-1). Sand used in each study was found to be slightly coated. According to the United States Department of Agriculture, sands are considered to be slightly coated if they contain < 5% sand plus silt, but contain clay coatings. Harris et al. (1996) concluded the presence or absence of clay coatings can be discrete and readily observable. Upon visual

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36 inspection, coatings can be seen via their color, opacity, and rough surface texture. Sand grain coating can include Fe & Al hydroxides, kaolinite, gibbsite, or goethite. Water Use Efficiency Calculations Water-use-efficiency was determined for each glasshouse study and the field study according to eq. 3.5 as stated by Gregory et al. (2000). Dry matter yield for each week was compared to the amount of water lost during that week as determined by weighing each pot before and after each harvest. WUE = dry matter yield (mg) / evapotranspired water (g) Eq. 3.5. Estimations of water use assumed the density of water was 1 g cm -3 for each treatment, and all water not evaporated was used by the turf. Glasshouse Studies Glasshouse studies were conducted from August to December 2002 and 2003 at the University of Florida Turfgrass Envirotron in Gainesville, FL. The objectives of each study were: 1. To determine the influence of soil amendments on WUE and quality of Tifdwarf bermudagrass 2. To determine the influence of incorporation method on WUE and quality of Tifdwarf bermudagrass Year 1 The objective of this study was to determine the influence of soil amendments on WUE, turf quality, and dry matter yield of Tifdwarf bermudagrass. Tifdwarf bermudagrass [Cynodon dactylon (L.) Pers. C. transvaalensis Burtt Davy] was established during spring 2002 in a glasshouse on pots (203 mm wide at top, tapering to 175 mm at bottom, and 203 mm deep) using USGA-specified greens sand. Treatments

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37 consisted of an amendment/sand mixture and incorporation method and were arranged in a split plot design with 4 replications. Amendments included two zeolites [Ecosand (Zeo Inc., McKinney, Tx.) (clinoptilolite 1); Ecolite (Ecolite Mfg Co., Spokane, WA) (clinoptilolite 2)] which were determined to be clinoptilolite via X-ray diffraction, two calcined clays [Soil Master Plus (Sport Turf Supply, Inc., Midland City, AL) (calcined clay 1); Profile (Profile LLC) (calcined clay 2)], one calcined diatomaceous earth [Axis (Agro Tech 2000, Norristown, PA) (diatomaceous earth 1)], one diatomaceous earth [PSA (Golf Ventures, Lakeland, FL) (diatomaceous earth 2)], Canadian sphagnum peat, Fe-humate (Vigiron, Winter Haven, FL), clay (montmorillonite), and sand. Prior to establishment, each pot was saturated and allowed to drain for 24 h. Pot weight after drainage was recorded and labeled as pot capacity. An overhead mist-irrigation system was used during establishment. Percent cover ratings were taken after week one and were subsequently taken at one week intervals until full coverage was achieved. Percent coverage was considered to be that portion of the pot surface that was covered by turf. Following establishment, irrigation ceased and all further applications of water were done by hand. The primary study lasted 18 weeks and began once all pots achieved 100 percent coverage and were uniform. However, data was only collected from week 3 to week 15 due to inaccuracies during the first three weeks and decreased growth during the last 3 weeks when decreasing daylight reduced turf growth. Following establishment, all pots were uniformly fertilized with NH 4 NO 3 concentrated super phosphate (CSP), and muriate of potash (KCl) at 5 g N m -2 2.5 g P m -2 and 2.5 g K m -2 at week one and six. Micronutrients and sulfur (as sulfate) were

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38 applied together using a commercially available micronutrient solution at a rate of 11.2 kg Fe ha -1 One primary function of soil amendments is nutrient retention which, in turn, may increase turf quality. A turf quality rating is a subjective measurement of overall turf health and appearance, which is crucial when assessing turf aesthetic value and playability. During the 12 week study, visual quality ratings were recorded on a weekly basis on a scale of 1 to 9, where 9 = ideal, 5.5 acceptable, and 1 = completely dead or dormant. Twice weekly, pots were weighed and water was applied to bring each pot back to 90% pot capacity. The amount of water was recorded and labeled applied water. Weekly, clippings were harvested by hand at 3 cm height, dried at 100 C for 24 h, and weekly harvested weight was recorded and labeled as dry matter yield. Upon completion of the 12 week study, overhead irrigation was used to bring all pots back to uniformity. Water applied was then stopped and pots were allowed to dry to determine number of days to wilt. The null hypothesis for the 2002 glasshouse study was soil amendments do not influence turf quality, dry matter yield, or WUE. Year 2 All materials and methods for the 2003 glasshouse study were identical to the 2002 glasshouse study with two exceptions. First, a bacteriacide used to clean glasshouse cooling pads was unintentionally applied to one replication of the full incorporation method, thus this replication was removed, reducing the total number of pots from 120 to 110. Secondly, three incorporation methods were used (Fig. 3-1). Incorporation method one involved mixing each amendment with sand (85:15 v:v) prior to turf establishment.

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39 Incorporation method two involved incorporating each treatment into an 85:15 sand/peat rootzone after turf establishment. This was accomplished by removing 9 or 4 aerification cores (20 mm wide 100 mm deep on 50 mm centers) and back-filling each core with a 50:50 sand/amendment mixture. All procedures and sample analysis followed procedures and sample analysis from the 2002 study. The null hypotheses used during the 2003 glasshouse study were: 1. Soil amendments do not influence turf quality, dry matter yield, or WUE, and 2. Incorporation method does not influence turf quality, dry matter yield, or WUE. 203 mm 100 mm 203 mm 175 mm Dia. = 20 mm 50mm B. C. A. Figure 3-1. Schematic diagram of pot set-up used in glasshouse studies showing side and ent, and C = 9 tine aerification with 50:50 sand amendment. top view of amendment incorporation methods where A = 85:15 sand/amendment, B = 4 tine aerification with 50:50 sand/amendm

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40 Nutrient Leaching Study The objective of this study was to determine the influence of soil amendments and SMSA on NO3-N, NH4+-N, PO42leaching in a golf course putting green. Twenty-four lysimeters (2.54 cm diam. by 35 cm length) were constructed using polyvinyl chloride (PVC). The top 30 cm of each lysimeter contained a USGA sand:peat mixture (85:15 by volume) packed to a density of 1.33 g cm-3. During a preliminary study, turf grown in a mixture of SMSAs and sand did not establish which may be a result of the biocidal influences of cationic surfactants (Gilbert and Al-taae, 1985). Therefore, treatments were placed below the rootzone in the bottom 5 cm (Fig. 3-2) and included one zeolite [Ecosand (Zeo Inc., McKinney, TX] which was determined to be clinoptilolite via X-ray diffraction, two calcined clays [Profile (Profile LLC), Soil Master Plus (Sport Turf Supply, Inc., Midland City, AL)] and two controls (control 1 = top 30 cm sand/peat, bottom 5 cm sand; control 2 = top 30 cm sand, bottom 5 cm sand). Each amendment was either coated with HDTMA or remained uncoated. Surfactant coating consisted of mixing a given amount of solid phase (according to each amendments CEC) with a solution of 67 mmol HDTMA. Previous research has determined bi-layer formation occurs when HDTMA equilibrium concentration after addition of a solid phase is at least twice the CEC of the solid phase (Li and Bowman, 1997). Sorbed HDTMA was determined via thermal gravimetry (Table 4-1). Lysimeters were then capped at each end with TyparTM landscape fabric (Reemay, Inc. Old Hickory, TN) and sealed with a domed, PVC cap. A 1-cm threaded hole was installed in the middle of each cap to allow a nutrient solution tube to be added to the top and a leachate collection tube to be added to the bottom of each lysimeter. Each lysimeter was vertically secured to a stand. The

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41 nutrient solution tube attached to the top of each lysimeter was connected to a Gilson Model 302 steady-flow pump (Gilson Medical Electronics, Inc., Middleton, WI). Thepump was set to deliver 10.0 ml of deionized water per minute. A valve was installed between the pump and lysimeter to which a 10 cm3 syringe was attached to inject nutriesolution. Nutrient solution contained 2300 ppm NO3-N, 2480 ppm NH4+-N, and 4400ppm PO42-. Leaching procedure consisted of first saturating the soil column with deionized water, injecting 10 mL of nutrient solution, and collecting leachate using a model 273 fraction collector (Instrumentation Specialties nt Figure 3-2. Schematic diagram of lysimeter set-up used in leaching studies. PUMP Treatment Layer H2O 30 c m 5 c m 2.54 c m Pump Tube Solution injection valve

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42 Co.) set to take a sample every 60 seconds until four pore volumes had been collected. Each column was leached individually within each block. d for NH4-N and NO3-N using an Alpkem RFA-300 auto analyzer. Phosphorous was determined colorimetrically using a model 680 microplate reader (Bio-Rad Laboratories, Hercules, CA). Treatments were arranged in randomized complete block design with three replications, and statistical analyses were performed using SAS for analysis of variance (SAS Institute, 1987). The following transport models were used to simulate movement of NO3-N, NH4-N and P through sts. The convective-dispersive model (CD model) can be written in dimensiner, 1958). A. The Convective -Dispersive (CD) Model: R (C*/p) = (1/P) (2C*/X2) (C*/X) 3.6a P = vL/D R = (1+KD/) 3.6b X = x/L p = vt/L C* = C/C0 3.6c T = Pulse applied in pore volumes 3.6d All samples were analyze oil amendmen onless form (Bren where C* is the solute concentration in the effluent (C, g/ml) normali zed to the 0ation D initial solute concentration (C, g/ml), x is the distance along the column (cm), t is the time of flow (h), v (cm/h) is the pore water velocity, L (cm) is column length, D (cm2/h) is the hydrodynamic dispersion coefficient, P is the Peclet number, R is the retardfactor, and p is the pore volume, K (ml/g) is the sorption coefficient, is the soil bulk density, and is the volumetric water content. B. The Two Site Nonequilibrium (TSN) Model:

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43 The T S 3.7a wherehe adsorthat iswa and ckwa first order so rate coeffin S 3.8c 3.8e Other parameters (p, P, R, C* and X) in eq. 3.8a have been defined for the CD-model. The Presidert, due to sorption in the instantaneous domain, is a number that gives the degree of SN model can also be described according to (Nkedi-Kizza et al., 1989). With firstorder kinetics, the sorption occurs in two domains, such that: C S1 S2 1 = FKDC dS2/dt = k1S1-k2S2 3.7b S1(g/g) is the adsorbed concentra t ion in the instantaneous domain, S2 (g/g) is t bed concentration in the time dependent sorption domain, F is fraction of sorbent at equilibrium, k1 and k2 are the forrdbardrption cients (1/h), respectively, other parameters have been defined for the CD-model. For an adsorbing solute the one dimensional equation at steady state water flow cabe written in dimensionless form: C*/p + (R-1) C*/p + (1-)R S*/p = (1/P) (2C*/X2) (C*/X) 3.8a (1-)R S*/p = (C*-S*) 3.8b where: = S2/(1-F) KDC0 = [1+ F (KD/)]/R 3.8d = k2 (1-)RL/v eclet num b er (P) reflects the ratio of the residence time due to dispersion and the nc e time due to convection emphasizing the effect of dispersion on solute transpo the retardation factor (R) is the ratio of pore water velocity and solute velocity which represents the effect of sorption on solute transport, is the fraction of total retardation

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44 sorption nonequilibrium for the solute, it reflects the ratio of the time for solute sorptioto the residence time for the solute due to convection. n through curves (BTCs) using the non-linear least-squar1981)The p P was calculated by fitting the CD-model to the BTCs of NO3-N for a givenTSNParameters for the CD-model (R and P) and for the TSN-model (R, and ) were calculated from the measured break es optimization technique in the curve fitting program CFITIM (Van Genuchten, The parameter (T) was measured and as such was not optimized for either model. arameter amendment. The obtained value of P from the CD-model was then used in the model as a fixed parameter. The null hypotheses used during the nutrient leaching study were: 1) Soil amendments do not decrease NO3-, NH4+, or PO4-2 leaching, and 2) SMSA do not decrease NO3-, NH4+, or PO4-2 leaching.

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CHAPTER 4 t Characterizations Surfactant Sorption Via thermal analysis, greater weight loss was observed from HDTMA calcined clay 1 than from HDTMA calcined clay 2 (Fig. A-2, A-3). HDTMA clinoptilolite showed the least weight loss and thus sorbed the least HDTMA (Fig A-4). For each amendment, increased weight loss due to oxidation of HDTMA began at approximately 230 C, which corresponded well with oxidation of pure HDTMA which began at 250 C. Oxidation of HDTMA from coated amendments was nearly complete at 300 C, which also compares favorably with oxidation of pure HDTMA. Impurities inherent within SMSA likely caused the minor differences between oxidation of pure and sorbed HDTMA. These findings indicate the extent of HDTMA coating can be well described by thermal gravimetry analysis. Surfactant sorption capacity of each amendment can be seen in table 4-1. Although clinoptilolite had a CEC 4 times higher than either of the calcined clays, it retained the least amount of HDTMA. Several studies have shown the majority of CEC on clinoptilolite is internal and inaccessible to HDTMA (Li et al., 1999; Li, 1999; Li and Bowman, 1997). Following surfactant sorption, calcined clays retained approximately one-half of their original CEC. Of the SMSA, calcined clay 1 retained the greatest amount of HDTMA followed by Calcined clay 2 and Clinoptilolite 1 (Table 4-1). RESULTS AND DISCUSSION A mendmen 45

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46 Table 4-1. Ion exchange capacity and surfactant sorption as influenced by soil amendment. Solid Phase HDTMA Sorbed CEC ECEC EAEC -(g kg-1) -ol (+) kg-1 --cmol (-) kg-1 ---cm Clinoptilolite 293.3 4.1 Calcined Clay 1 79.6 11.3 Calcined Clay 2 69.7 Cation exchange capacity 7.1 97.4 3.4 20.9 2.9 21.8 12.1 Effective cation exchan ge capacity Effective anion exchange capacity alcined quartz than calcined clay 2. Mineral Composition Neither DE contained any discernable minerals (Fig. A-5). While definitive analysis of DE mineral composition via XRD is ambiguous, the broad peaks observed from both DEs around a d-spacing of 4.0691 are indicative of amorphous silica. Silica contents of DE have been reported to about 86 to 88% (Sylvia et al., 1997). X-ray diffraction analysis of calcined clays can be seen in fig. A-6. Both clays contain quartz, goethite, and small amounts of mica. The only significant difference between calcined clays is the quartz peak (d= 3.35), which is likely evidence that cclay 1 contains more Zeolites used in this study were concluded to be clinoptilolite based upon XRD analysis (Fig. A-7). No other minerals were apparent in either zeolite sample. Nutrient Composition Because soil nutrient status has been shown to positively influence WUE (Viets, 1962; Hatfield et al., 2001), the initial elemental content of each amendment and sand/amendment mixture was determined via Mehlich I and KCl extraction. Sand/amendment mixture samples were taken from before turf sprigs were applied

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47 Nitrogen Only peat and iron humate contained detectable levels of N (Table 4-2). Nitrogen ontent of iron humate was lower than that ob3) determined the N content of a commercially available hum be N content dined in this stuuld b duiffeent humWhile peat contained more TKN prior to incorporation with sand, both peat and ual amounts after incorporation (Table 4-3). Incorporation of sand t levels were obsery was found to contain low levels of P. While quartz sand is largely considered to be inert, sand grain coatings have been shown to increase P retention (Harris et al., 1996) and may be responsible for the observed P levels. After incorporation with sand, P levels were diluted for all amendments except iron humate (Table 4-3). Because samples were taken from field plots which were encouraged to settle by using daily irrigation for 10 days, P from irrigation water (Table A-1) may have been responsible for the increased P in the iron humate treatment. Smectite contained the highest level of extractable P before and after sand incorporation. Diatomaceous earths were the only amendments that did not increase extractable P levels above the sand/peat mixture. c served by previous researchers. Varshovi and Sartain (199 ate to 0.85%. Lower eterm dy co e e to d r ate sources. iron humate produced eq likely diluted any treatment influence, thus, no differences were observed. Phosphorus Extractable P did not follow any clear trends across soil amendment class. However, in general, highest P levels were found in smectite while the lowes ved in iron humate (Table 4-2). Iron-based water treatment residuals have been shown to be effective long-term P immobilizers. Furthermore, much of the P sorbed bwater treatment residuals is internal and considered to be irreversibly bound (Makris et al., 2004). As expected, the control (USGA sand)

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48le2. el pes mendmen s u iasusndld studime C pH N KCMg MC Tab 4Chmicaprortieof a tsedn glshoe a fieAendmnt CE ECTKP es. a Znn u Fe cm (+) k1 S c-1 % ------------ol gm --------------mg-1---------------------------g k --------------------------San1) 0.9 0.03.2 2.6 Peat) 114.3 7 0.53.9 3.4 Calced cy 1 ( 214 20 0.03.2 3.7 Calced cy 2 ( 216 4 0.08.2 19.9 Clintilolite 1 (4 975 814 0.05.1 4.8 Clintilolite 2 (4 353 7 0.07.1 1.5 aces ea 1 (7.9 97 0.04.2 2.1 aces ea 2 (346 18 0.08.6 1.5 tite (6 200 215 0.02.7 5.9 uma (7) 418 30 0.41.5 26.7 st: 2 *** N***NS S st: otrs *** ******** ** st: 3 *** N***NS ** st: 4 *** *****NS ** st: 5 *** *****NS ** st: 6 *** ******** S st: 7 *** *****NS ** st: 5 N* **NSNS ** st: 7 *** *****NS ** ) 15 3.4 5.6 43.1 .4 d ( 7 5.8.30 222.5 0.3.4 (2 5 7.6.95 5276403.5 10.21.1 inla3) .7 5.1.30 39976284.9 10.124.0 inla3) .5 5.8.00 51274393.9 0.102.6 op) .8 5.5.00 176238172.2 0.9.1 op) .1 6.2.20 1059184873.0 0.6.7 Diatomourth5) 8 7.9.30 21116782.3 1.233.9 Diatomourth5) .1 4.1.10 467125793.1 0.32.5 Smec) .4 6.4.00 659516291.0 0.0.1 Iron Hte .2 4.0.32 68687455.8 62.30.0 Contra1 vs. **S N***NS *N*** Contra2 vs.he *** ****NS ***** Contra2 vs. **S ****NS ***** Contra2 vs. *** ****NS ***** Contra2 vs. *** ****NS ****** Contra2 vs. *** N***NS *N*** Contra2 vs. *** ***** ****** Contra3 vs. S *** *N*** ****** Contra3 vs. *** ***NS ****** CV (% .5 1.9 4 9.1 14 31.31.1 9. 3.0 3.9 .5 9.3 8.3 6.5 5.3 7.5 3.2 6.7 1.7 4.5 2.1 6.0 .1 7.7 2.6 5.3 11.2 3.3 3.1 ** ** ** ** ** ** ** S ** .9 0.2 1 3.9 1 4.7 2 3.4 1 6.2 1 5.0 2 2.3 3 7.7 8 1.3 0 5.4 3 ** S ** ** ** ** ** S ** ** ** 32 NS, *, **ot ifi siificant t 0.0501 prb ls, respively. **, Nsigncant,gnt ahe 0., and 0.001oba ility leveect 2:1 donied watsoi Meh1 act einzer:l lich-extrable

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49se and field studies. A C Table 4-3. Chemical properties of 85:15 sand/amendment mixtures used in glasshou mendment EC pH EC TKN P K Ca Mg Zn M n Cu Fe cm ol (+) kg-1 S cm -1 % -----------------------------------------mg kg-1 -------------------------------------------Sand (1) 0.9 2225 0.2 .1 1 13 0.5 .0 7 3 0.4 .1 27 15 1.4 .1 254 6 1.0 .1 169 17 1.4 .1 5.6 5 0.9 .2 11 0 0.3 .1 13 6 0.5 .1 62 5 1.3 .0 7 N NS S *** N NS S ** S N NS N NS S ** NS NS ** 3 1 .6 .9 7 5. 8.3 0.00 3.2 .6 3.9 .5 2. 0 3.4 Peat (2) 1.8 2 7. 23.7 0.03 3.5 2.3 276.9 1 07.6 1. 0 7.4 Calcined clay 1 (3) .7 6. 22.1 0.00 10.1 85.2 91.5 54.2 1. 0 33.9 Calcined clay 2 (3) .8 6. 26.6 0.00 6.6 66.8 3 49.7 47.9 1. 0 30.5 Clinoptilolite 1 (4) .7 6. 84.7 0.00 5.7 38.1 358.0 19.7 1. 0 6.3 Clinoptilolite 2 (4) .0 6. 13.5 0.00 15.7 15.9 228.8 1 36.2 3 5. 0 4.5 Diatomaceous earth 1 (5) 3 8. 36.2 0.00 8.3 45.8 98.8 6.6 1. 0 10.4 Diatomaceous earth 2 (5) .2 7. 27.1 0.00 3.9 5.9 46.1 7.9 3. 0 22.5 1 Smectite (6) .3 6. 14.2 0.00 126.8 2 8.8 677.3 155.1 1. 0 2.4 Iron Humate (7) .4 6. 8.9 0.03 8.3 63.6 920.4 19.5 2. 1 3 99.5 Contrast: 1 vs. 2 S *** *** *** NS NS *** *** NS N NS Contrast: 2 vs. others ** *** *** *** *** *** NS *** NS ** *** Contrast: 2 vs. 3 S *** NS *** *** ** *** NS NN *** Contrast: 2 vs. 4 ** *** *** *** ** *** NS *** NS NS Contrast: 2 vs. 5 S *** *** *** NS *** *** *** NS * Contrast: 2 vs. 6 S *** *** *** *** NS *** *** NSS N NS Contrast: 2 vs. 7 *** *** NS *** *** *** *** N ** *** Contrast: 3 vs. 5 S *** *** NS NS *** NS *** N *** Contrast: 3 vs. 7 *** *** *** *** ** *** ** NS ** *** CV (%) 1.7 1.9 4.7 38.4 15.2 7.1 3.5 12.8 110. 2 15 14 6.2 NS, *, **, *** Not significant, significant at the 0.05, 0.01, and 0.001 probability levels, respectively. 2:1 deinonized water:soil Mehlich-1 extractable

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50 Potassi e ehlich-1 extractaK of the pure amendment samples (Table 4-2). Calcined clays contained higher ls of extractable K than zeolites which were followed by DEs. Sand contained thee tai ned the highest. All amendments except gher K levels than peat. l tio nd DEs. Sand and sand/peat treatments tite increased sand/peat treatment. m O pure amendment samples, highest Ca levels were found in ironmate ectiable). Oemaining amendments, sand/peat contained Ca lev in rporation, Ca levels dropped for all am endments. Both iron humate andectite ary difference between Ca levels of amendments alone and amendment/sand lites possessed lower Ca levels than pe at before sand incorporation ese results com (2003) where zeolite amended sand was found e Ca levels as at mixtur es both before and after turf establishment. d t amendment may be used when considering the pot Howeve li il um nlik ble evel st K ll K f the U P, c le ar t ren ds we re observed between amendm e nt cla sse s f or M low lev els wh ile iro n hum a te c on sand and smectite contained hi the highest levels of K followed by CCs a contained the lowest am extractable K above the Cal followed by sm hig inco con prim mixtures is that zeo while they contained sim favorably with those reported by Ok et al to have the sam With regards to initial retention of P, K, clas Ca. A eve ls d ro ppe d afte r i nco rp ora n w it h sand (Table 4-3). Zeolites contained o un t o f ex tr act abl e K All am endm ents ex c ep t sm ec ciu hu and sm pare C te (T 4-2 f th e r her els tha n z eo lite s f oll ow ed by CC s, D Es, an d s an d. Fo llow g s tinu ed to exh ibi t th e h ig he st Ca levels after sand inco rporation (Table 4-3). The ila r C a le ve ls af t er i nc orp ora tio n. Th san f C d/pe Cs an zeo Ca en tes th tial influence of plant available K and ma es y d e re ec su rea lts se sho pla w nt tha ava ses r, in co rpo ra tion o or able a.

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51 Phosphorus availability may increase with incorporation of CCs or zeolites, but it appears that inn, e amendment samples were likely leachof 5.5 A-1). Retention ided ter olite 2 ples in dividual amendments should be recommended instead of amendment classes. pH and EC Salinity levels dropped after incorporation with sand (Table 4-3). Because sand/amendment samples were taken from plots that were allowed to settle by irrigatiothe excess salts which were initially observed in the pur ed out of the soil media. Soil acidity also became more basic after sand incorporation. Acidity levels of pure amendments rose to near 6.5 after sand incorporation. This may also be due to excess leaching with water high in Ca (Table Moisture Analysis of moisture retention data revealed incorporation of amendments prova variety of beneficial physical characteristics to a sand-based rootzone. Moisture content at field capacity, moisture content at wilting point, and plant available waincreased with the addition of soil amendments (Table 4-4). These parameters were influenced primarily by the increase in total and micro porosity which accompanied amendment incorporation. Saturated hydraulic conductivity was found to be within acceptable ranges as recommended by the USGA (Table 4-4). Diatomaceous earth 1 and 2 and clinoptilreduced Ksat while all other amendments were similar to pure sand. Water flow in a saturated soil is primarily through macropores (Hillel, 1998). However, this researcher observed soils that produced the highest Ksat values also possessed the lowest macroporosities. While this seems counterintuitive, McIntyre 1974 states that soils prepared for Ksat analysis must be taken from undisturbed core samples. Core sam

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52 this analysis were taken from recently renovated soils and, thus, physical analysis may not entirely agree with analysis of undisturbed soils. Soil po rosities varied from 32.2 to 38.9% (Table 4-4). Only clinoptilolite 1 failed to incaving 4-1). Both CCs increased macroporosity above sand whileh 1 and iron humate were shown to ence, increasing microporosity from 7.7 to 15.6%. This is likely due toge arth or plant uptake. Thus, correlation between microporosity and plant was y t rved from rease total porosity above that of sand. This is likely due to clinoptilolite 1 hthe highest percentage of very course sand-sized particles (Table 3-1), and may explain why clinoptilolite 1 was the only amendment that had a lower volumetric water content at saturation than sand alone (Fig all other amendments decreased macroporosity. The greatest influence of soil amendments on porosity was observed in microporosity. All amendments increased microporosity above sand alone. Diatomaceous eart have the greatest influ iron humate having the largest percentage by weight of medium and fine sand size particles than any other amendment (Table 3-1). Diatomaceous earths contain a larnumber of internal channels which may contribute to the influence of diatomaceous e1 on microporosity. Of the water held in macro and micropores, only water held in micropores is considered to be available f available water should be high. The relation between microporosity and PAWfound to be well correlated (R2 = 0.83; Fig. A-8). As expected, amendment incorporation increased moisture held at field capacitand wilting point. Correspondingly, plant available water also increased with amendmenincorporation. The greatest increase in mo is ture held at wilting point was obsediatomaceous earth 1 where percent moisture increased by more than 8 times that of

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53Tabl-4.ysl analysif an dt/sand ------Por--e 4 Phica s ome men----mixture at 85:15 by volumee Space -------Ameentsat ToMi M #D FCP P h ------------------cm ---------------ndm K cm tal r-1 ---------cro acroPD B WP % ----------------g -3 --------------% -----AW -----Sand 0 a3.37.25bc 4 a567. 0. f Peat 2 a5.33.21d 3 b373. 1. 1b Calcicla 4 a8.92. 26b 9 a392. 2. 1de Calcicla 6 a8.2126 6 a46 1. 3. f Diatoaceous art5 c8.35.6 a 22cd 7 a405. 3. 1b Diatoaceous art5 b5.93.7 b 22d 1 c353. 2. 1bc Clinoolit 1 a2.21.4 cd 20 4 b45 1. 1d e Clinoolit 4 b5.00.9 d 24bcd4 a45 0. 1e e Smec 3 a6.23.1 b 23bcd9 a523. 2 1cd Fe-Hte 7 a6.75.5 a 21 2 a475. 1. 1a CV ( 2 5.1 4.3 7 8 4.3 12 Withlu, ms foedthee r at signif ic dentordto camule ran te. 05 61. 66. ned y 1 52. ned y 2 55. meh 1 25. meh 2 44. ptile 1 63. ptile 2 43. tite 71. uma 51. %) 17. in comnseanllow b 3 b b 3 ab 1 b 3 a 1 b 3 a 1 3 a 1 c 3 ab 1 b 3 b 1 c 3 ab 1 3 ab 1 b 3 ab 1 by samlettere no 7 e .6 a2.3 1. a 7 e 4 f 5 b .8 c2.1c 1. f 15 b 2 e 5 bc.4 a2.2b 1. ef 15 bc 4 b .2 cd .9 a 2.3 1. bcd12 cd 4 a .6 b2.2bc 1. def 16 a 5 a .1 c2.1 1. f 17 b 1 bc .7 d 2.1c 1. cde14 cd .9 bc .1 a 2.2bc 1. cde19 d .5 cd .1 a 2.3 1. ab 11 b .4 b .1 d 2.3 1. bc 15 a 4 de .1 3.0 1. .8 antlyiffer accing Dunns ltipgest (0 ). 7.3 2.3 0.0 7.8 2.1 1.6 9.4 9.3 0.6 4.1 4.4 saturated haundvit USrec e 1 (n al) 30-60 (accelerated) cm micoreoret cin water a csi maore (pores tat ain air at 3m ton) # part dey buen fieap plt wiltingpobyme plvae lume ydrlic coucti GA ommendations ar rops (ps thaonta cropshcont iclensit lk dsity ld cacity, by volume an int, volu ant ailablwater, by vo y 5-30or m and t 35m tenon) 5 censi hr-1

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54 ion Head (cm) 0608olumetric Wate 0.00.10.2 0.30.4 re release curve for USGA sa Suct 0 2 04 V Figure 4-1. Moistu nd am vo lum e. 0100r Content (%) Sand Clinoptilolite 1 Clinoptilolite 2 ended with zeolites at 85:15 by

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55 Suction Head (cm) 020406080Volumetric Water Content (%) 100 0.00.10.20.30.4 Sand Diatomaceous Earth 1 Diatomaceous Earth 2 Figure 4-2. Moisture release curve for USGA sand amended with diatomaceous earths at 85:15 by volume.

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56 Suction Head (cm) 020406080Volumetric Water Content (%) 100 0.00.10.20.30.4 Sand Calcined Clay 2 Calcined Clay 1 Figure 4-3. Moisture release curve for USGA sand amended with calcined clays at 85:15 by volume.

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57 sand. Interestingly, peat and iron humate contained two of the lowest moisture contents at wilting point but had the two highest PAW contents. This indicates that in order to have the greatest influence on PAW, amendment must not only increase water held at FC, but must also decrease water held at WP. Moisture release curves indicated incorporation of soil amendments with sand increased moisture content and moisture retention. Diatomaceous earths (Fig. 4-2), as a class, produced greater moisture retention than calcined clays (Fig. 4-3) or zeolites. Zeolites were observed to have the least influence on moisture held at saturation and moisture held against 50 cm of head (Fig. 4-1), which is likely due to zeolites also having the least influence on total pore space (Table 4-4). This relation between available water and porosity was also noted by Brown and Duble (1975). Waltz et al. (2003) observed amendments with the lowest soil porosity were also observed to retain the least amount of water against gravity. Waltz et al. further noted sand amended with peat produced more suitable physical and hydraulic properties for turfgrass growth than either calcined clay or diatomaceous earth. However, of the two inorganic amendments Waltz investigated, diatomaceous earths were found to be the most suitable replacement for peat. These observations by Waltz both agree and contradict those found during this research. When only physical and hydraulic properties are considered, diatomaceous earths increased moisture held against gravity above that of peat while providing similar or adequate PAW and conductivity. Thus, diatomaceous earths are not only the most suitable inorganics replacement for peat, but they are actually more suitable than peat. Of the amendments used, Fe-humate produced the greatest beneficial influence on the putting green rootzone physical properties. The observed increase in moisture held

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58 against gravity (Fig. 4-4) was matched only by diatomaceous earth 1. Correspondingly, Fe-humate amended sand produced the highest amount of plant available water while maintaining adequate hydraulic conductivity and bulk density (Table 4-4). Suction Head (cm) mectent ( 0.20.30 Fe-Humate 020406080100Volutri War Coten%) 0.00.1.4 Sand Peat Smectite 85:15 by volume or with smectite at 97.5:2.5 by volume. Figure 4-4. Moisture release curve for USGA sand amended with peat or Fe-Humate at

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59 Glasshouse 2002 Establishment Analysis of turfgrass establishment revealed amendment influence wa s dependent upon amendment source (Fig. 4-5). Pots containing clinoptilolite 1, diatomaceous earth 2, calcined clay 1, or calcined clay 2 did not change the establishment rating compared to pots containing sand alone. Clinoptilolite 2, diatomaceous earth 1, and Fe-humate decreased the rate of turf establishment while only peat and smectite increased turf establishment above pots containing only sand. No amendment increased the rate of turf establishment above pots containing the sand/peat mixture. The influence of the zeolite treatment on turf establishment is in contrast to finding reported by Nus and Brauen (1991). They reported plots containing zeolite were over 90% established 28 DAP while plots containing equal volumes of peat were 87% established. Furthermore, they reportedly failed to establish turf on 100% sand plots. However, Ferguson et al. (1986) reported decreased growth with the incorporation of zeolite to pure sand. Findings by Ferguson are similar to those found by this researcher. Because NH4NO3 was used as the sole source of N during establishment, and due to the did not increase with zeolite incorporation because much of the N was sorbed out of soil solution which effectively decreased the amount of plant available N. Diatomaceous earths reacted similarly to zeolites with diatomaceous earth 2 producing nearly identical establishment ratings as sand alone and diatomaceous earth 1 lowering the turf establishment rate. While DEs tend to increase soil moisture, they have low CECs which may be crucial during turf establishment. Nutrients applied during establishment may be continually leached due to excessive water applications affinity zeolites have for NH4 (Ferguson and Pepper, 1987), it is likely turf establishment

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60 Days After Planting 0100 Sand 2D Graph 2 204060 Peat 80100 Axis PSA 020 Ecosand D. 100 A. 4060 406080 Ecolite Sand B. 20406080 Soil Master Profile % Cover 080100 Montmorillonite Iron Humate Sand 020 Sand C. 714212835 by (A.) zeolites, (B.) diatomaceous earths, (C.) clay and organics, and (D.) Figure 4-5. Establishment of Tifdwarf bermudagrass during summer 2002 as influenced calcined clays. Vertical bars denote standard error. 42

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61 which are typically applied during the first weeks of establishment (Shaddox, 2001). Thus, low CEC rootzones may be more susceptible to nutrient depletions which may lead to plant deficiencies and decreased growth. Peat and smectite were the only amendments that increased the rate of turf establishment above sand alone. The influence of peat on turf establishment has been well documented and has been primarily attributed to the increase in moisture retention, CEC, and additional nutrients which are mineralized from peat during the establishment period (Bigelow et al., 2001b; Carlson et al., 1998). Smectite was found to produce high moisture retention and possessed a CEC of 20 cmol(+) kg-1. These parameters may have been sufficient to produce establishment equal to peat. Turf Quality Turf quality ratings were taken each week to assess overall turf health during the 12 week study (Table 4-5). Pots containing only sand produced the lowest quality turf while pots containing calcined clay 2 and iron humate produced the highest quality. These results correspond well with each amendments physical and chemical characteristics. Sand exhibited low moisture retention (Fig 4-4) and low nutrient content (Table 4-3) and, thus, pots containing only sand exhibit poor turf quality. Pots containing calcined clay 2 or iron humate were observed to increase soil moisture and nutrient content and, thus, pots containing these amendments produced superior turf quality. Turf quality for the inorganic amendments fit well within amendment classes. Calcined clays produced the highest quality turf followed by DEs and zeolites. The low quality rating from pots containing zeolite incorporation. The influence of soil amendments on turf growth was investigated zeolites are likely due to the low moisture retention which accompanies

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62Tabl5.suua rag oer ags aflce 85:15 d/endm nt tzdug 2 glasshe sy. ----------------------Week ----------------------------------e 4Vial qlitytinf bm udrass inuend by---------------------------------san----am erooone rin200----------------------------oustud----Treat 2 3 5 7 9 1 2Mean Sand e 5..7 de 5.04 7 f40 d5.02 d 5. ment 1 4 6 4.7 1 ef 4e 5.7 b .7 b 4. 8 10 1 .7 c 5.d 5.1 c 1 5.0 e Peat 8 bcd 6.cd .1 2 bcd 6.66c 2 c6 7 a5 bc 6.35 b6. Calcicla a 6. .8 bcd6.77b 1 a7 6 a ab7.61 a6. Calcicla a 7..3 abc7.07 7.2 a7 1 a ab7.53 a 7. Diatoeorthab5.ef .3 2 bcd 6.6 6c 6.5 b6b 5 b3 bc 6.31 c 6. Diatoeorthcd 6.de .6 cde6.56c 7.0 a6 5 6 bc 6.1 ab6. Clinolit e 5..1e 5.65 5.7 d5 1 c cd6.22 c 5 Clinolit de 5.f .5de 5.65 5.6 e5 3 c 6.31 c 5 Smec ab 6.c .3 ab 6.866.1 d6b 1 a b6.53 b6 Iron ate a 7..1 a 6.877.3 a75 a a 7.86 a7. CV() 5 9.0 7. 8.15 8. 9. 3 Withilu m followed bhee l art s ica dienrding to camule ran te. 05 5.5 ab6cd 6. a .2 b ned y 1 6.8 8 ab6abc 6.3 a .0 a ned y 2 7.1 1 a 7a 6.7 a .6 a macus ea 1 6.3 c 7 cd6bcd6. a .3 b macus ea 2 5.7 0 bc6abc 6.0 a .3 b ptiloe 1 4.8 0 f 5 e 5.2 b .6 c ptiloe 2 5.3 6 de5 de 5.8 b .8 c tite 6.6 6 ab6bcd7.0 a .0 c Hum 7.0 1 a 7ab 7.2 a .3 a % 9.0 9. 8.3 0 9.1 n comns,eansy t samettere noignif ntlyffert acco 6. 7. de .2 b6.bc 6. b b .1 a6.bc 7.1 a b .3 a7.b 7.2 a cd .6 a6.c 6. b bc .0 b6.bc 6. b e .8 b6. 5.8 b .8 b6.bc 6.1 b e .7 a7.b 6.3c b .5 a 7. 7.8 a 8.6 8.7 5 Dunns ltipgest (0 ). 6.c 3 c 7.b 9 b 7.2 ab 6.3 c 6.8c 3 c 6..6 d 6..8 d 6.c .5 c 7. 3 a 7.7 .2

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63 by W ti rporation with na soil and concluded that im provement in bermudagrass increase s in soil moisture. Overall, these findings le000) Miller (2000) i nvestigated several endments along with peat are ported turf may perform differently when o t only reported little nces d e amendments performed ly to pots amended with purnn this researchers study, all amendments a ifferences between the two are m h amendments were incorporated into the z were introduced by first aerifying and then ay have decreased the e d ne and may have decreased each amendments ce on turf growth. U o dclilde d water, or WUE were observed between nd sand/peat rootzones (Tab le 4-6). Only zeolite ame nded pots failed to increase 4NO3) and to the affinity e for NH it is likely that asch as of the applied N may have been ered e, th plant growth was hindered. Absorption of 4 by zeolite amended soils has been observed by Bigelow et al. (2000). They also with zeole re less effective duri ng turf establishment noted this apparent negative eht je e t a l. (20 03 ). Th ey in ves gat ed the influence of zeolite, DE, and CC inco perf agr inorganic am gro diff sim increased tu stu roo back-filling those holes w hom infl Wa san WUE above zeolites hav rend NH noted that rootzones am than those am tive ike orm ee wn ere ilar dies ting og uen ter N d a anc e i s m os t l ly rel ate d to wi th fin din gs re po rte d b y M il r (2 nd ver, Miller (2000) no observed som d. I The reported d tzo pli mu us, ite w in va rio us ro otz on e me dia H we be tw een a men ments, but also e sa rf quality ab ove that of s nd. lik e. ely A du me e nd to me the nts in Millers study ethod in whic on ith each am endment. This m nei ty of the am e ndm e nt/ san roo se E ffic ien cy iffe ren es i n c ppi ng yie ap that of sand/peat. Du e to the source of N used (NH 4le in acc es sib to pla nt up tak e nd ed ended with peat. Other researchers have also

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64 Table 4-6. Tissue yield, applied water, and water-use-efficiency of Tifdwarf study. bermudagrass as influenced by soil amendments during glasshouse 2002 Rootzone Mixture Clipping Yield Applied Water WUE (g) (ml) (mg g-1) Peat (2) 3.8 3628.3 1.1Calcined clay 2 (3) 5.9 4210.8 1.4 Diatomaceous earth 2 (4) 5.9 4298.3 1.4Clinoptilolite 2 (5) 4.4 3858.5 1.1 Iron Humate (7) 4.7 3215.5 1.5 Contrast: 1 vs. 2 NS NS NS Contrast: 2 vs. others *** ** *** Contrast: 2 vs. 3 *** *** *** Contrast: 2 vs. 5 NS NS NS Contrast: 2 vs. 7 *** *** Contrast: 3 vs. 7 *** *** NS CV Sand (1) 3.4 3363.3 1.0 Calcined clay 1 (3) 6.5 4453.3 1.5 Diatomaceous earth 1 (4) 5.5 4376.8 1.3 Clinoptilolite 1 (5) 4.1 3544.8 1.2 Smectite (6) 4.6 3677.3 1.3 Contrast: 2 vs. 4 *** *** *** Contrast: 2 vs. 6 ** NS *** Contrast: 3 vs. 4 NS 8.0 3.9 7.4 NS, *, **, ***, Not significant, significant at the 0.05, 0.01, and 0.001 probability levels, respectively. 85% USGA uncoated sa nd plus 15% amendment by volume Wat 2.5% by volume een er Use Efficiency = clipping yield / applied water characteristic inherent in natural zeolites and attempted to overcome them by using zeolites which have been pre-loaded with NH4. Incorporation of these products has bshown to lead to rapid establishment and high quality turf (Andrews et al., 1999; Miller2000). Therefore, it is reasonable to assume the low clipping yield and WUE producedby the zeolite treatment was due to the removal of plant available N. However, if this isthe case, it is also likely that over time, the zeolite will come to equilibrium with NH4 in

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65 soil solution and, thus, provide a buffer for plant consumption when NH4 in so il solution is low. Calcined clays and iron humate wereally effective aroduced the greatest in turf WUE (Table 4-6). This is likely due to CCs and iron humate providing plant available P and K (Table 4-3) and m retention (F-4). d in order of decrg effectivene: iron huma > zeolites = peat = sand.s that produced the greatest increase in W those ameents equate moisture retention and adequate CEC anitial ntrienttent. ncrease PAW comparable to that of inorganic ents (Table 4-4), ease CEC, available P, or ove that providy sand alone le 4-nd is also clear regarding ites. Zeolites noly increased tove all other amendments, but they also provide adequate P and the est amount of K. However, zeolites he lowest influen moisture held at According to these findings, in order to maximize turf WUE by st be able to increase moisture tention, provide adequate available nutrients, and retain those nutrients via cation increase. Iron humate was the only amendment that produced higher establishment equ nd p increase both an increase in oisture ig. 4 Rootzone mixtures ranke easin ss were te = CCs > DEs = smectite Amendment UE were ndm that provided ad nd i u con While peat did i amendm peat did not incr K ab ed b (Tab 3). A similar tre zeol t on he rootzone CEC ab high ad th nce o field capacity incorporating soil amendments, the amendment mu re exchange. Glasshouse 2003 Establishment During the 2003 establishment phase, all amendments increased turf establishmentrate above that of pots containing only sand (Fig. 4-6). Peat and iron humate produced the greatest increase in establishment while pots containing smectite produced the lo w est

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66 Days After Planting 02040 Calcined Clay 1 Calcined Clay 2 Sand % Covr 0100 Peat 406080 02040 Clinoptilolite 1 Sand A.B.D. 100 100 6080 Clinoptilolite 2 6080100 e 20406080 Smectite Fe-Humate Sand 020 Diatomaceous Earth 1 Diatomaceous Earth 2 Sand C. 7142128354249 by (A.) zeolite, (B.) diatomaceous earths, (C.) clay and organics, and (D.) Figure 4-6. Establishment of Tifdwarf bermudagrass during summer 2003 as influenced calcined clays. Vertical bars denote standard error.

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67 ratings than pots containing sand/peat. These findings are different than those found during the 2002 study in which only peat and smectite produced higher rating than pots containing only sand. While the reason for this difference is unknown, difference between irrigation manifolds between the two studies may have allowed more water to be applied during the 2002 study, thus decreasing the influence of each amendments moisture retention capabilities. No inorganic amendment produced higher establishment ratings than did pots containing sand/peat. These findings agree with those reported by Bigelow et al. (1999). They investigated the influence of CCs, DEs, and zeolites on turf establishment and also reported that no inorganic amendment produced faster establishment than peat. As in the 2002 study, differences between establishment rates of inorganic amendments were minimal. All pots containing organic or inorganic amendments were fully established at 42 days after planning (DAP). This is over 7 days longer than the 2002 study. This may also be due to the different irrigation manifolds used between the two studies. Turf Quality Upon analysis of turf quality, turf grass response was dependent upon the method treatment interaction (Table 4-7). Therefore, amendment influences were determined within each method. Analysis of turf quality as influenced by sand/amendment mixtures revealed quality was dependent upon amendment type (Table 4-8). All amendments increased turf quality above that of sand alone. However, only CCs and iron humate increased quality above pots contaig ning sand/peat. Amendments influence on turf quality in order of decreasin

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68 Table 4-7. Analysis of variance of mean squares on turf quality during 2003 study asSource of Variation df Mean Squares F value Method (M) 2 0.54 1Amendment (A) 9 2.11 66.28 *** Error (b) 72 0.03 Total 109 4.35 *** Error (a) 5 0.03 A M 18 0.40 12.60 *** *, ***, Significant at 0.05, 0.001 pr obability levels, respectively. influenced by incorporation method and amendment type. Block 3 0.10 2.79 effect. As isture has bent and 0) ster establishment for seeded bentgrass than soil amended with inorganic igelow et al. (2001b) also determined that improved turf quality of amenty. This is clearly observable in the case of DEs. Diatomaceous earths produced 30% more PAW than CCs (Table 4-4), but DEs produce quality ratings nearly 1 unit lower than CCs. Clearly available water is not the only variable dictating the influence of amendments on turf quality. It seems more likely that the combination of available water and nutrient content of amended rootzones was the primary influencing factor during this study. iveness followed: iron humate > CCs > smectite = peat = DEs > zeolites > sandobserved during 2002, iron humate produced superior turf quality above all other amendments. This is likely due to the iron humate providing background levels of P and K, but more importantly providing the greatest amount of PAW (Table 4-4). Mo een noted as being the primary limiting factor when assessing turf establishmquality. Bigelow et al. (1999) stated moisture appeared to be the main limiting factor when assessing amendments influence on turf establishment. Waltz and McCarty (200hypothesized that more moisture held near the soil surface by peat-amended soils provided a fa amendments. B ded sand rootzone was due to higher water holding capacities. However, according to findings by this researcher, moisture content may not be the primary variable influencing turf quali

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69udagrass as influenced by 85:15 sand/am enote during 2003 glasshouse study. -------------------W-------------------Table 4-8. Visual quality rating of berm endm t rozon---------------------------------------eek ----------------------------------------------Tren 1 3 6 7 Mean Sa 6 d 4.6e 5.8 f 44.84 0 e d 4. eatmt 2 4 5 8 9 nd 4.e 4.8 d 5.1 0 e 4.e 4.8.8 e e 1 0 .8 d 5. 11 1 5.0 2 8 e Pe 3 b 6.31 bcd 6.d 6 c6d 6.6c 6.5 c6 bc 6. Caed 1 1 ab6.6b 7. 0 b 7b 7.17 7.6 a7.3 ab Caed 2 0 a 7.3b 7.c 3 b7bc 7.17 7.3 abc 7.1 ab Diacs e 1 5 3 bc 6.31 bcd 6. 6 8 bcd 6cd6.6 6.3 cd 6.0 c Diacs e 2 0 0 bc 5.8cd6. 5 6 bcd 6d 6.6c 6.5 cd 6.6 bc Clinoptil 1 6 d 5.0de5.8 e 6 6.06 6.0 d 6.1 c Clinoptil 2 3 cd5.3de5.6 e 6 .16 6.3 cd 6.1 c Smectite 6 bc6.3bc6.d 0 d6cd.0 6 6.8 bcd 6.8 abc Iron Hum 3 a 7.5a 7.5 a 7.68 8.1 a 7.6 a CV (% 7.4 8.6 148 7. 8 6. 6 8.4 7.1 Within consan e same letter are not sign ican dinrcamle e test at 6.bc 6.5 b 6.6 bc6.abc 6.3de .3 c5 bcd lcinclay7.ab 6.8 ab 7.0 1 ab7.ab 7.1.3 a ab lcinclay7.ab 7.5 a 7.0 0 ab7.ab 7.0c .1 a ab atomeouarth6.abc 6. b 6.5 cd6.abc 6..6 b 3 bcd atomeouarth6.cd 6. bc 6.0 e 1 d 6. bcd 6..3 c3 bcd olite4.e 4.6 cd 5.3 5 e 5.cd 5.8.0 d d olite5.de 5.5 cd 5.6 5 e 5.de 5.8.0 d6 cd 6.abc 6.3 b 6.8 6 bc6.cd 6.1e .8 b 7 abc ate 7.a 7.5 a 7.8 3 a 7.a 8.0.8 a 7 a ) 8.0 7. .66.4 7.8 lum, mes followed by th if tlyfferet accoding to Dunns ultiprang .6 b .3 b .3 b .3 c .6 b .1 c .1 c .1 c .1 a .7 (0. 0 d b 6. 4 c 7.1 b 7.1 b 6.4 c 6.3 c 5.5 d 5.8 d 6.5 c 7.7 a 4.3 5).

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70 ality were observed between amendments when ndments were incorporated after 4 tine aerification (Table 4-9). All amendments e eptable qua lity ratings. During the aerification the r st arily of sand/peat mixture. This likely decreased the endments on turf quality, thus pots modified with sand, DEs, and zeolites only sand/peat. Only CCs, te, a ped ratinhighe r than pots modified with pure sand. t quality ratings were observed fr iron humate amended pots followed by CCs. ents were fully incorporated into the r a eans were observed when amendments rp ificatioan after 4 tine (Table 4-10). This result was ated and is most likely due to a la us the 4 tine. Only diatomaceous earth 1 to inse tulity a bove that of pots modified with only sand. As in the full e ods, humate produced the hi ghest quality turf umate can positively influence daw when ua te N is available. Sartain attributed dagrass response to the addition of iron which accompanies iron humate N, in iron humate is likely the cause of the Mi nim a l d iffe re nc es in t ur f qu ame pro stu influence of am pro sme Hig This trend was also observed when am rootzone. were inco antic each treatm fail mix followed by CCs. Sartain (1999) rep berm berm incorporation. The increase in Fe, along with observed increase in duc dy, du cti hes G ip ed tur u u d tu rf ab ov e th e mi nim al acc oo tzo ne co nsi ed pr im ced q ual ity ra tin gs eq ua l to that of pots containing nd iro n h um ate ro duc gs om ent m n th rg e portion of the rootzone being replaced by iron iron h adeq endm eat er dif fer en ce be tw een tre tm or ate d a fte r 9 ti ne aer ent in th e 9 tine aerification vers crea 4 rf er qua ifi and tin e a cat ion m eth o rted gra ss gro th an d q ua lity t urf quality.

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71taecat dg 3 she sy. --------------------------eek --------------------------Table 4-9. Visual quality rating of Ti fdwarf bermudagrass as influenced by 4 --------------------------------------W ine rifiionurin200glasoustud --------------------------------------Treatment 4 56 7 9 1 2m Sand 2 bc 6.b 6.0 b .26 5 b6.6 7 bc 6. 1 23 6.3 a 6.5 0 b 6. 6.3 a6 8 10 11 ean b .6 b6.c .3 b 6abc 6.3 d Peat 3 bc 6.b 6.5 a .3 b 6b 7 6.0 5 b6.d Calcined clay 1 ab6.b 6. 8 a .3 b 7b 2 c7 .3 0 a6. Calcined clay 2 bc6.ab 6. 5 a .8 ab 6 0 a6 .3 0 a6. Diatomaceous eart2 bc 6.b 6.2 a .2 b 6 5 6b .1 5 b6. Diatomaceous eart c 6.b 6.0 b .6 b 6 5 6b .7 0 a6. Clinoptilolite 1 bc6.b 6.6 a .3 b 6 3 b6 .5 3 b6. Clinoptilolite 2 c 6.ab 6.6 a .1 b 6 7 b6 .6 1 c 6. Smectite bc7.ab 6. 2 a .5 b 7b 7 b6 .6 7 b6. Fe-Humate a 7.a 7.1 a .5 b 7 5 a7.3 6 a7. CV (%) 6. 8.6 .2 6.5 7.6 1 Within columns, means followed bthee r at sf ic dentord to Duncamule ran te. 05 6.5 a 6.6 3 b 6.b 6.7 a6 6.7 6 a 6.5 8 ab6.b 6.3 a6 6.3 7 a 6.8 8 ab6.b 7.0 a6 h 1 6.2 a 6.5 2 b 6.b 6.8 a6 h 2 5.72 a 6.2 3 b 6. 6.6 a6 6.1 5 a 6.1 1 b 6.b 6.6 a6 6.07 a 6.7 5 b 6.b 7.1 a6 6.3 0 a 6.7 2 ab6.b 6.3 a6 7.10 a 7.5 6 a 7. 7.1 a7 6.57 7.5 1 8.7.5 7 y samlettere noigni antlyiffer accing .7 a6.bc .2 b 7ab 6.c 5 bc .0 a6. .0 ab6bc 7.b 6 bc .5 b7.b .7 ab6bc 7.b 7 b .5 b6.bc .6 a6c 6.c 4 d .3 b6.bc .7 a6abc 7.b 4 d .6 b6.c .6 ab6bc 6.c 4 d .6 b6.c .5 ab6abc 6.5 cd .1 a6.c .7 ab6abc 6.c 6 bc .5 a7. .3 a 7a 7. 3 a 7.4 7.8 6 6..8 ns ltipgest (0 ).

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72T able 4-10. Visual quality rating of Tifdwarf bermudagrass as influenced by 9 tine aerification during 2003 glasshouse study. -------------------------------------------------------------------Week -------------------------------------------------------------------reatment 9 0 1 2 3 4 5 6 7 8 1 1 1 mea f and 0 c 2 d 5.8 d 6.1 c .1 b .1 c .0 d 6.0 6.6 6. 6.5 b 6.7 b 6.2 eat 5 abc 3 d 6.5 c 6.8 bc .6 ab 8 abc .6 bc 6.5 b 7.0 6. 6.6 b 6.3 b 6.5 cb alcined clay 1 8 ab 5 bcd 6.8 b 7.0 ab .8 ab .6 bc .7 bc 6.8 aa 6.3 6.8 6.6 7.1 a 6.7 alcined clay 2 6 abc 3 a 7.2 ad 6.6 bc .5 ab .1 ab .7 bc 6.6 6.7 6.8 6.5 6.7 b 6.8 iatomaceous earth 1 5 abc 1 d 6.0 6.3 bc .2 b .8 ab .8 b 6.6 6.3 5.8 6. 6.3 b 6.3 iatomaceous earth 2 3 abc 3 cd 6.5 c 6.6 bc .2 b .5 bc .6 bc 6.3 6.6 6.7 6.6 b ab 6.7 b 6.5 linoptilolite 2 1 bc 2 d 6.3 c 6.3 bc .3 ab .0 ab .1 cd 6.5 6.8 6.1 6.8 6.8 ab 6.4 linoptilolite 1 8 c 5 bcd 5.8 d 6.2 bc .7 ab .0 ab .3 bcd 6.5 6.5 6.6 6.5 b 6.6 6.4 mectite 6 abc 0 abc 7.0 aba 6.7 bc .0 ab .5 bc .5 bcd 6.8 a a 6.8 6.8 6.6 b5 a 6.8 aa 6.7 e-Humate 1 a 1 ab 7.5 7.6 a .2 a .3 a .7 a 7.5 7.3 7. 7. 7.6 7.4 V (%) 7.7 .0 5.9 7.0 8.1 6.4 .9 8.7 6. 6. 7. 7.1 1. ithin columns, means followed by the same letter are not significantly different according to Duncans multiple range test (0.05). T 12 n S6.6. 666b b 3 bc P6.6.d 66. 6 ab 3 bc d C6.6.c 666b b b b b c C6.7.b 676b ab b b b D6.6.666ab b c 2 b ef D6.6.d 666d b b b de C6.6.d 676b ab bc b de C5.6. 676 b b bc de S6.7.c 766 b ab b b bc F7.7.777 a 7 a a C6 55 9 8 9 W

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73 Days In ord furthetine the influe nce of soil amendments on turf growth, pplication was stopped at the end of the study and days-to-wilt (DTW) was thod treatment interaction was not cant. Therefore, treatme nts effects were averaged across methods (Table 4-11). 4 f mean s quares on Tifdwarf days to wilt during 2003 na tion method and amendment type. Source of Variation Mean Squares F value to W ilt er to r de erm wat observed. U sig Ta er a nifi ble pon analysis of DTW, the m e -11 st An ud aly y a sis s i o nfl f v uen ari ce anc d b e o y i cor pordf Blo Method (M Erro Amendme A M Erro To ck r (a r ( tal 3 2 5 9 18 72 09 5.07 1.78 4.90 1.72 ) 2.84 nt (A) 3.10 0.78 5.05 1.26 b 4.00 1 ) ) am hum considered s (20 ear Mi lack of differences betw amendm versus full incorporation T endm ate and diatom 00) ths, ller urf potsng sandat was observed to wilt at 8.9 days. No ent increased DTW above sand/t (T able 4-12). While turf grown with iron llft. Thes e reported by Miller Miller observed turf grown in p iatomaceous a e reach DTW as pots containing sand/peat. observed only sand and one zeoli eatment reduced DTW be low sand/peat. The ethod in which ents were incoorated. When aments were incorporated after aerification ce of endment on dry matter yield and WUE gro wn in co nt aini /pe pea erved to extend DTW to 9.8, it was not e findings agree with thos ots containing calcined clays, d e to te tr is likely due to the m endm each am aceous earth 1 was obs ta tis tica y s igni ican nd zeo li tes re qui red th e sam tim een am endments rp the influen

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74 was reduced (T able 4-14, Table 4-15). If full incorporation were the only method 85:15 sand/amendment rootzone during 2003 glasshouse Treatment Days to Wilt analyzed, amendments may influence DTW. Table 4-12. Days to wilt of Tifdwarf bermudagrass as influenced by study. --d ---Sand (1) 9.1 8.9 Calcined clay 1 (3) 8.8 DiatomaceoDiatomac9.4 ilolite 1 (5) 9.0 2 (5) 8.0 9.0 9.8 1 vs. 2 NS st: 2 vs. others NS ontrast: 2 vs. 3 NS NS NS ContContContrast: 3 vs. 4 NS Peat (2) Calcined clay 2 (3) 9.3 us earth 1 (4) 9.8 eous earth 2 (4) Clinopt Clinoptilolite (6) Smectite Iron Humate (7) Contrast: Contra C Contrast: 2 vs. 4 Contrast: 2 vs. 5 rast: 2 vs. 6 NS rast: 2 vs. 7 NS Contrast: 3 vs. 7 NS CV (%) 21.6 Water Use Efficiency Upon analysis of WUE for the 2003 study, Tifdwarf WUE was dependent upon the method treatment interaction (Table 4-13). Therefore, amendment influences were determined within each method. As observed in the 2002 study, no differences in mean clipping yield, applied water, or WUE were observed between sand and sand/peat rootzones (Table 4-14). This was unexpected due to the greater amount of PAW retained in the peat amended rootzone versus sand alone (Table 4-4), as well as larger quantities of TKN, Ca, and Mg found in

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75 Table 4-13. Analysis of variance of mean squares on Tifdwarf water use efficienctype. y during 2003 study as influenced by incorporation method and amendment Source of Variation df Mean Squares F value Block 3 0.001 2 0.853 0.72 Method (M) 385.88 *** Error (a) 5 0.002 Amendmen9 0.287 139.13 *** M 18 0.084 41.00 *** 72 0.002 109 .05, 0.001 probability levels, respectively. t (A) A Error (b) Total *, ***, Significant at 0 eat amended pots (Table rmud eported by Come mendments with r wh p 4-3). These findings contradict those found by Snyder (2003) who reported a 32% increase in clipping yield of beagrass when peat was incorporated into an uncoated sand-based rootzone. However, similar findings were rr (1999) who investigated the incorporation of a variety of soil a and without peat into a sand-based putting green. Comer reported that pots containing amendments produced less dry matteen peat was incorporated than when peat was withheld. Similar trends were observed between the control containing only sand and the control containing sand/peat. Differences were attributed to N mobilization by microbes in the sand/peat pots which would effectively reduce plant upply of C relative to inorganic N is provided by peat, N consud/peat (Table 4-14). Explanations for this response regardon. im available N. If a large s mption by microbes will be stimulated (Pierzynski et al., 1994). Only pots amended with zeolites failed to produce clipping yields and WUE ratings above pots containing san ing NH4 immobilization by zeolites have been addressed in the preceding sectiZeoliteamended pots required 17% more water to produce essentially the same biomass as sand/peat pots. During both the 2002 and 2003 studies, zeolite amended pots did not produce quality ratings, clipping yields, or WUE ratings superior to that of peat. These

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76 Table 4-14. Tissue yield, applied water, and water-use-efficiency of Tifdwarf influenced blly incorpodments duglasshouse 2003 study. zone Mixture Clipping Yield Applied Water W bermudagrass as y fu rated soil amen ring Root UE (mL) ) and (1) 3.5 3181.8 .1 3.6 2986.1 alcined c 4.7 2745.1 alcine 5.0 iatomaceous earth 1 (4) 4.9 (g) (mg g-1 S 1Peat (2) 1.2Clay 1 (3) 1.7 Cd clay 2 (3) 3325.6 1.5 3037.5 1.6 iatomaceous earth 2 (4) 4.4 3176.2 1.4 Clinoptilolite 1 (5) 3.8 3478.8 1.1 Smectite (6) 4.5 2522.2 1.8 DD Clinoptilolite 2 (5) 4.2 3516.7 1.2 Iron Humate (7) 7.1 3925.0 1.8 Contrast: 2 vs. others *** *** **Contrast: 2 vs. 4 ** NS ** Contrast: 2 vs. 6 ** *** Contrast: 3 vs. 4 NS NS NS CV (%) 11.2 5.9 6. NS, *, **, ***, Not significant, significant at the 0.05, 0.01, and 0.001 probability levels, respectively. 85% USGA uncoated sand plus 15% amendment by volume 2.5% by volume Water Use Efficiency = clipping yield / applied water results suggest zeolite is not a suitable replacement for peat in sand-based putting greens if increasing turf quality or WUE is desired. However, zeolites may be considered as an amendment to increase putting green CEC (Table 4-3). No differences in applied water were observed between peat and CCs and peat and DEs, yet differences were observed between clipping yield and WUE (Table 4-14). Because the same amount of water and nutrients were applied to CCs, DEs, and peat Contrast: 1 vs. 2 NS NS NS Contrast: 2 vs. 3 *** NS *** Contrast: 2 vs. 5 NS ** NS Contrast: 2 vs. 7 *** *** *** Contrast: 3 vs. 7 *** *** 8

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77 Table 4-15. Tissue yield, applied water, and water-use-efficiency of Tifdwarf bermudagrass as influenced by soil amendments after 9 tine aerification Ro during glasshouse 2003 study. otzone Mixture Clipping Yield Applied Water WUE 4.1 3388.9 1.2 P .5 3531.7 1.0 Calcined c 4.0 3056.4 1.3 Calcined clay 3.8 3156.9 1.2 Diatomaceous earth 3.9 3568.2 1.1 Diatomaceous earth 4.0 3352.8 1.2 Clinoptilolite 1 (5) 3.7 3353.0 1.1 Clinoptilolite 2 (5) 3.7 3680.0 1.0 Smectite (6) 3.9 3542.4 1.1 Iron Humate (7) 6.7 4164.6 1.6 C ontrast: 1 vs. 2 NS NS ontrast: 2 vs. others NS ** NS C Contrast: 2 vs. 3 NS *** ** Contrast: 2 vs. 4 NS NS NS Contrast: 2 vs. 5 NS NS NS Contrast: 2 vs. 6 NS NS NS Contrast: 2 vs. 7 *** *** *** Contrast: 3 vs. 4 ** NS Contrast: 3 vs. 7 *** *** *** CV (%) 15.4 7.5 8.3 NS, *, **, ***, Not significant, significant at the 0.05, 0.01, and 0.001 ability levels, ely. prob respectiv 85% USGA uncoated sand plus 15% amendment by volume Water Use Efficiency = clipping yield / applied water mended pots, and CCs and DEs were found to have similar amounts of PAW as peat, it eat amended pots (Table 4-3). Thus, 2.5% by volume (g) (ml) (mg g-1) Sand (1)eat (2) 3lay 1 (3) 2 (3) 1 (4) 2 (4) a is likely nutrients applied to pots containing CCs and DEs were more plant available than that applied to pots containing peat. Mehlich I extractable levels of P, K, and Fe from CCs and DEs were found to be higher than those from p higher WUE ratings were observed from CCs and DEs than from peat. Water-use-efficiency ratings from iron-humate and smectite were identical and higher than all other amended pots (Table 4-14). These results regarding iron humate

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78 contradict those reported by Sartain and Comer (2004). They investigated WUass one year after establishment E of bermudagr and observed pots containing peat had greater UE ratings than pots containing sand/iromate or sand alone. Iron humaproduct of water treatment facilitAs such, its coy over timy organic matter and nutrient content. Iron used in thdy f N, K, Ca, and Fan iron humate used in the study by Comer ld account for the differesponses obserng this stuendments were inrporatllowing-tinetiondiffes nt means becameess appt (Table 4-15). Only iron humate, CCs, ed WUE above that of the sand/peat mixture. increase in W due to a 13% decrease in r required to min 90% field capacity. ired 17% more water thant, but produced more dry m. icative of an increase in nunt uptake by turwn in iron hue ed the ere observed from peat and ots. During 2003, incorporation of soil amendments via 9-tine an s on W n hu te is a residual ies. nsistenc e ma vary along with its humate is stu contained higher levels o e th (1999). This cou nt re ved duri dy. When am co ed fo 9 aerifica rence between treatme l aren and sand increas The UE from CCs was largely wate ainta Iron humate requ pea 90% atter This may be ind trie f gro mat amended sand. Iron humate produce 23% greater WUE than CCs which produc second highest WUE response. Lowest WUE responses w olite amended p ze aerification produced 22% lower WUE than when amendments were fully mixed into the rootzone. Fully mixing amendments with sand allows for greater consistency and homogeneity. Thus, fully-mixed amendments had a greater influence on turf growth thwhen amendments were incorporated in localized regions throughout the rootzone as wathe case in each aerification method. Incorporation of soil amendments via 4-tine aerification had a similar influence turf WUE as 9-tine aerification (Table 4-16). The only amendment that increased WUE

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79 Table 4-16. Tissue yield, applied water, and water-use-efficiency of Tifdwarf during glasshouse 2003 study. bermudagrass as influenced by soil amendments after 4 tine aerification Rootzone Mixture Clipping Yield Applied Water WUE (g) (ml) (mg g-1) Peat (2) 3.8 3193.2 1.2 Calcined clay 2 (3) 3.8 3141.7 1.2 Diatomaceous earth 2 (4) 4.3 3559.7 1.2 Clinoptilolite 2 (5) 3.8 3460.6 1.1 Sand (1) 3.8 3456.1 1.1 Calcined clay 1 (3) 3.9 3033.3 1.3 Diatomaceous earth 1 (4) 3.9 3533.3 1.1 Clinoptilolite 1 (5) 4.2 3472.2 1.2 Smectite (6) 3.9 3515.2 1.1 Iron H umate (7) 5.7 4085.7 1.4 Contrast: 1 vs. 2 NS NS NS Contrast: 2 vs. others * NS Contrast: 2 vs. 3 NS NS NS Contrast: 2 vs. 5 NS NS NS Contrast: 2 vs. 7 *** *** ** Contrast: 3 vs. 7 *** *** Contrast: 2 vs. 4 NS NS Contrast: 2 vs. 6 NS NS Contrast: 3 vs. 4 NS NS CV (%) 13.1 6.9 9.2 NS, *, **, ***, Not significant, significant at the 0.05, 0.01, and 0.001 probability levels, respectively. 85% USGA uncoated sand plus 15% amendment by volume Water Use Efficiency = clipping yield / applied water 2.5% by volume above peat was iron humate. This trend remained consistent across all incorporation methods. However, the influence of iron humate on WUE decreased in the order oincorporation > 9-tine aerification > 4-tine aerification. However, no differences were observed between the overall mean of treatments from 9-tine and 4-tine aerification (Table 4-17). According to these resu f: full lts, soil amendments may not increase WUE when incorp orated after aerification compared to full incorporation. Moreover, it seems the likelihood of producing an increase in WUE will increase as more of the rootzone is

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80 removed during aerification. However, incorporation of amendments into a sanill produce the greatest increase d-based rootzone w in turf quality, clipping yield, and WUE when e amendment is fully incorporated into totzone (Table This allon distribution of nutrients and mre for turf uptafficiency of Tifdwarf bermudagrass as influenced by poration method. r Use Efficienc th he ro 4-17) ws fo r a more eve oistu ke. Table 4-17. Water use e incor Metho d Wate y Full (1) 1.4 4 Tine (2) 1.1 9 Tine (3) 1.1 *** NS 3.5 Contrast: 1 vs. 2 Contrast: 2 vs. 3 CV (%) Nutrient Leaching Study sly mentioned, a primary concern in the golf industry is to minimze any dy retain NO3-, NH4+, and P during eriods of normal nutrient but high water applications. 3-off moved through the column with the wetting front, and the primary mode of leaching was convection. As previou i environmental impact that may arise from fertilizer applications. This phase of the stu compares 3 soil amendments and their capacity to p Nitrate No differences were observed between the NO3-N breakthrough curves of sand and sand/peat rootzones (Fig. 4-7). As desired, nitrate-N leached as a pulse. Maximum NON concentration reached 0.2 C/Co at one pore volume and quickly dropped, tapering to no detectable NO3-N at near 2.5 pore volumes. Both sand and sand/peat leaching patterns were well described by the CD model. Thus, nitrate can be assumed to have

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81 0.200.25 HDTMA Ecosand C/C 0.050.100.150.20.25 00.25 HDTMA Soil Master Ecosand CD Model Profile CD Model Soil Master CD Model 0.000.050.10 Sand/Peat Sand 0.150.20 CD Model CD Model o 0.00 0.05 0.10 0.15 0.2 0 HDTMA Profile 0.00 0.15 Effluent Volume (Pore Volume) 0123 0.000.050.10 0123 Figure 4-7. N itrate breakthrough curves as influenced by filter zone media.

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82 Both CCs were found to have similar NO3 breakthrough curves to that of sand and sand/peat (Fig. 4-7). Calcined clays, sand, and peat have effectively no anion exchange capacity, thus similar leaching patterns were expected. These findings agree with those reported by Bigelow et al., (2004) who also investigated NO3 leaching through sand amended with CCs. They reported that more than 90% of applied NO3-N leached through all rootzone mixtures, and, in general, non-amended sand and sand/amendment mixtures were similar regarding NO3-N leaching. Leaching patterns from columns containing zeolite differed from columns containing CCs or peat. Minimal retention of NO3-N was observed in columns containing zeolite (Fig. 4-7). Maximum NO3-N concentration in leachate from zeolite columns were approximately 5% lower than columns containing sand as the filter zone media. Due to the high CEC of zeolite, this result was not expected and it is unlikely that any NO3-N was retained directly. However, it is possible that as NH4 ions were absorbed into the zeolite structure, movement of the NO3 ion, previously associated with the NH4 ion, through the column was delayed via its ion pair. This ion pair hypothesis has been previously proposed by Brown (2003) when studying the movement of Ca(NO3)2 through turfgrass covered soil columns. Unfortunately, evidence of this phenomenon was not substantiated. However, these results indicate decreased leaching of one ion due to retention of its counterion may occur. When each amendment was coated with HDTMA, nitrate-N was removed from solution to the extent that the CD model did not fit the data (Fig 4-7). All NO3-N was retained by SMSA following 4 pore volumes, except calcined clay 2 in which 5% of pplied NO3-N eventually leached (Table 4-18). Columns that contained unmodified soil a

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83 amen in d (data not d Root zone media Filter zone media NO-N Leached dments leached between 94 and 102% of applied NO3-N. These results are substantially higher than those reported by previous researchers when using the same fertilizer source (Brown et al., 1982; Snyder et al., 1984). However, both Brown and Snyder conducted leaching studies over longer periods of time compared to this studywhich NO3-N remained in columns for less than 20 minutes. The longer time periowould subject NO3-N to a variety of conversion processes and potentially decrease NO3 leaching. Nitrate-N sorption isotherms may help to explain the leaching patterns and retention by SMSAs (Fig. A-9). Uncoated amendments did not sorb any NO3-Nincluded on graph). Surfactant-coated calcined clay 1 sorbed more NO3-N than calcineTable 4-18. Total NO3-N leached as influenced by filter zone media. 3 (mg) % of Applied Sand Sand (1) 21.6 96.0 Sand/Peat Clinoptilolite 1 (3) 21.5 95.5 Sand/Peat Calcined clay 1 (5) 21.3 94.6 Sand/Peat HDTMA-Clinoptilolite 1 (6) 0.0 0.0 Sand/Peat HDTMA-Calcined clay 2 (7) 1.0 4.4 Sand/Peat Sand (2) 22.1 98.2 Sand/Peat Calcined clay 2 (4) 23.1 102.6 Sand/Peat HDTMA-Calcined clay 1 (8) 0.0 0.0 Contrast: 1 vs. 2 NS Contrast: 2 vs. 7 Contrast: 2 vs. 6 *** *** Contrast: 2 vs. 8 *** CV (%) 9.8 Contrast: 3 vs. 6 *** Contrast: 4 vs. 7 *** Contrast: 5 vs. 8 *** NS, ***, Not significant, significant at 0.001 probability level respectively.

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84 clay 2 or clinoptilolite 1. Calcined clay 2 and clinoptilolite 1 produced similar isowith calcined clay 2 retaining slightly more NO3-N than clinoptilolite 1. These isothermrelate well with each amendments effective anion exchange capacity (EAEC) (Table 41). Calcined clay 1 and clinoptilolite 1 had the highest and lowest EAEC, respectively. Thus, calcined clay 1 and clinoptilolite 1 produced the highest and lowest Smax, respectively. Ammoniu therms s -m WhenC of This phenomenon was observed during analysis of NH4-N leaching. Leaching patterns of NH4-N through columns containing only sand were similar to tterns of e same columns (Fig. 4-8) and were well described e model. arameters can be seen in table A-2. Maximum centratioere obserat 1.09 porumes. This dicates that, underese experimental conditions, the movement and retention of NH4is not influenced bhese findings support previous work conducted nder similar experis (Bigelow et al., 20Addition of peat into the rootzone mixture decreaseaximum NH4oncentration in leacg. 4-8). Furthermore, peak concentrations were tor (R). However, no HDTMA is coated onto a solid phase that possesses a CEC, the effective CEthat solid may decrease (Table 4-1). This is due to a portion of the original c a tion exchange sites being occupied by HDTMA head groups. Due to this decrease in CEC, sorption or retention of cations from soil solution may also decrease. leaching pa NO3-N through th by the 2-sit The 2-site model p NH4-N con ns reached 0.21 C/CO and w ved e vol in th N y USGA sand. T u mental condition 03). d m -N c hate by 25% (Fi observed at 1.1 pore volumes which lead to a higher retardation fac

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85 0123 0.050.10 2-Site Model Effluent Volume (Pore Volume) 0123 o 0.15 HDTMA Profile Profile 0.000.25 HDTMA Soil Master Soil Master 0.050.10 2-Site Model 2-Site Model Figure 4-8. Ammonium breakthrough curves as influenced by filter zone media. 0.000.150.200.25 Sand/Peat Sand 0.20 C/C 0.200.25 2-Site Model 0.050.100.15 2-Site Model 2-Site Model 0.000.150.200.25 HDTMA Ecos an d Ecosand 0.000.050.10

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86 differences in total NH4-N leached were observed between columns containing sand and sand/peat. This indicates the CEC increase associated with peat addition (Table 4-3) is enough to delay NH4-N leaching, but will not prevent NH4-N from leaching under these conditions. These findings are in contrast to previous research. In general, past research has shown that under normal growing conditions, leaching of NH4-N is minimal due primarily to the rapid conversion of NH4-N to NO3-N in well-aerated soils that contain an adequate microbe population (Petrovic 1990; Reddy, 1982; Tate, 1977). Thus, inclusion of peat into a sand-based media has been shown to reduce NH4-N leaching by as much as 70% (Bigelow et al., 2003). However, this study was conducted under a worse-case scenario in which oxygen was limited and percolation rates were high. Therefore, nitrification was likely limited and, thus, peat did not have as great an influence on total NH4-N leached as previous research might indicate. Addition of a filter layer containing unmodified amendments reduced NH4-N leaching by 98%. (Table 4-18). No NH4-N was detected in leachate from columns containing zeolite while 6% of applied NH4-N leached through calcined clay 1. Decreased NH4-N leaching from zeolite amended sand than from CC amended sand was also observed by Bigelow et al. (2003). The removal of NH4-N from leachate in this study was likely due to two factors. First, because CCs and zeolites possess relatively high CECs (Table 4-2), they each have the capacity to remove large amounts of cations from solution. Sorption isotherms showed that CCs are capable of adsorbing between 55 and 65 mg kg-1 NH4-N, while zeolites which possess a higher CEC are capable of adsorbing 260 mg kg-1 NH-N (Fig A-10, Fig A-11, Fig A-12). Secondly, amendments were placed in each column in a 2 cm thick layer below the rootzone which forced all 4

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87 Table 4-18. Total NH4N leached as influenced by filter zone media. Root zone media Filter zone media NH4-N Leached --(mg) --% of Applie Sand/Peat Calcined clay 2 (2) 0.0 0.0 Sand/Peat HDTMA-Clinoptilolite 1 (4) 1.0 4.0 Sand/Peat HDTMA-Calcined clay 1 (6) 18.2 73.3 Sand Sand (8) 23.1 93.1 Contrast: 2 vs. 5 *** Contrast: 7 vs. 8 NS Contrast: 7 vs. 5 *** NS, ***, Not significant, significant at 0.001 probability leve d Sand/Peat Clinoptilolite 1 (1) 0.0 0.0 Sand/Peat Calcined clay 1 (3) 1.5 6.0 Sand/Peat HDTMA-Calcined clay 2 (5) 12.5 50.4 Sand/Peat Sand (7) 22.7 91.5 Contrast: 1 vs. 4 NS Contrast: 3 vs. 6 *** Contrast: 7 vs. 4 *** Contrast: 7 vs. 6 *** CV (%) 12.9 l respectively. leachate to pass through each amendment. It is probable that the thickness of this layer directly influences the retention of potential contaminants. The influence of filter layer thickness is of concern and future research in this area would be valuable. When CCs were coated with HDTMA, each amendments capacity to retain NH4-N decreased (Fig A-10, Fig A-11). Thus, more NH4-N leached through columns containing HDTMA-coated calcined clay 1 and calcined clay 2 than columns containing their unmodified counterparts (Table 4-18). Only a minor decrease in NH4-N retention was observed from HDTMA-clinoptilolite 1 (Fig A-12). Thus, columns containing clinoptilolite 1 and HDTMA-clinoptilolite 1 leached similar amounts of NH4-N (Table 4-18). The influence of SMSA on decreasing NH4-N leaching in order of decreasing effectiveness was: clinoptilolite 1 > calcined clay 2 > calcined clay 1. These results

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88 correspond well with each amendments CEC and Smax. Clinoptilolite 1 had the highest CEC and Sax and, thus, leached the least amount of NHd calcinedEC than c 1 and, thus, less Ned through ntaining Han HDTMAcined clay 1 (Tabl8). s r peak P concenere observed in leachate folumns containing sand nd sand/peat (Fig. 4-. However, a broader peak produced from sand/peat columns an from sand alone.els of P in leachate been 0.0-0.5 pore volmes dicate columns contleached P not associent solution. hen determining P leached as a percent of applied, this would artificially inflate the mount of P applied. However, columns containing sand/peat underlined with This amount seemed reasonable until leachate from columns containing only sand were analyzed. Only 88% of applied P leached from the column that contained only sand. These results indicate that a portion of P applied to sand/peat rootzones may be retained by sand, while peat may exacerbate P leaching. These findings agree with previous researcher by Brown and Sartain (2000). Brown and Sartain investigated P leaching from USGA greens from three P-source fertilizers. They reported as much as 70% more P leached from columns containing peat than from those containing only sand. Despite fertilizer source, columns in Brown and Sartains study containing sand/peat leached more P than those without peat, in all cases. m 4-N. Coate clay 2 had a higher EC oated calcined clay H4-N leach columns co DTMA-calcined clay 2 th -cal e 4-1 Phosphoru Simila trations w rom c a 9) th Background lev etw u in aining sand/peat ated with the nutri W a unmodified amendments leached 101% of applied P (Table 4-19).

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89 Effluent Volume (Pore Volume) 0123 0.020.06 C/C 0.000.040.14 HDTMA Profile 0.020.060.12 0123 Profile 0.000.060.100.14 Sand/Peat 2-Site Model Figure 4-9. Phosphorus breakthrough curves as influenced filter zone media. 0.080.12 2-Site Model Sand 0.04 0.000.040.080.100.120.14 HDTMA Ecosand 2-Site Model o 0.020.060.080.100.12 2-Site Model 0.000.040.080.100.14 HDTMA Soil Master 2-Site Model Ecosand 2-Site Model 2-Site Model Soil Master 2-Site Model 0.02

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90 Breakthrough curves produced from columns containing CCs indicate P movement was retarded (Fig 4-9). Calcined clays reduced maximum effluent concentration by as much as 30%. However, they were unable to retain P against percolate flow as indicated by the broaden peaks. This is further reinforced by the percent of applied P that was leached (Table 4-19). Since neither CCs possesses any appreciable AEC, retardation of P through CC amended columns is likely due to the Fe levels determined via Mehlich I extraction (Table 4-2). Phosphorus has been shown to be strongly sorbed by Fe-containing compounds (Makris et al., 2004; Brown and Sartain, 2000). Furthermore, sorption isotherms indicate calcined clay 1 and calcined clay 2 are capable or sorbing approximately 1600 and 700 mg P kg-1 (Fig A-13, A-14). When CCs were coated with HDTMA, maximum effluent P concentrations were Table 4-19. Total Phosphorous leached as influenced by filter zone media. Root zone media Filter zone media P Leached --(mg) --% of Applied Sand/Peat Clinoptilolite 1 (1) 44.2 100.4 Sand/Peat Calcined clay 2 (2) 44.3 100.6 Sand/Peat Calcined clay 1 (3) 44.8 101.8 Sand/Peat HDTMA-Clinoptilolite 1 (4) 23.7 53.8 Sand/Peat HDTMA-Calcined clay 2 (5) 7.2 16.3 Sand/Peat HDTMA-Calcined clay 1 (6) 1.3 2.9 Sand/Peat Sand (7) 44.5 101.1 Sand Sand (8) 38.6 87.7 Contrast: 1 vs. 4 *** Contrast: 2 vs. 5 *** Contrast: 3 vs. 6 *** Contrast: 7 vs. 8 ** Contrast: 7 vs. 4 *** Contrast: 7 vs. 5 *** Contrast: 7 vs. 6 *** CV (%) 6.9 **, ***, Significant at 0.01, 0.001 probability level respectively.

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91 reduch e 1 us, little or no differences were Sorption isotherms indicate Smax of HDTMAclinoptilolite 1 is r than tha. A-15). Ting was observed from zeolite than frs. ed by approximately 90%. Breakthrough curves for coated CCs indicated P movement was not only retarded, but P was also retained against water flow. Columns containing coated calcined clay 1 leached 3% of applied P while coated calcined clay 2 leached 16% (Table 4-19). The amount of P leached from CCs directly correlated witeach amendments EAEC (Table 4-1). Furthermore, analysis of sorption isotherms indicates that HDTMA coating can increase its capacity to sorb P by as much as 100%(Fig A-14). No differences were observed between the breakthrough curves for columns containing clinoptilolite 1 versus sand as the filter zone media (Fig. 4-9). Clinoptilolithas extractable iron levels similar to that of USGA sand, th observed. However, coated clinoptilolite 1 both retained and retarded P movement Addition of coated clinoptilolite 1 reduced P leaching by 46% (Table 4-19). 5 times lowe t of calcined clay 1 (Fig hus, greater P leach om CC

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CHAPTER 5 endments do influence turf quality, dry matter yield, and WUE low green construction. Additional research in this area would be valuable. Incorporation Method I reject Ho: incorporation method does not influence turf quality, dry matter yield, or WUE and conclude incorporation method does influence turf quality, dry matter yield, and WUE of Tifdwarf bermudagrass. Only iron humate produced superior quality, yield, and WUE than other amendments regardless of incorporation method. The influence of all other amendments was reduced upon incorporation following aerification. Therefore, it is recommended that amendments be fully incorporated into putting green rootzones in order to maximize their effectiveness. The practical implications of this research are that during periods of low moisture availability, Tifdwarf WUE can be increased while CONCLUSIONS Soil Amendments I reject Ho: soil amendments do not influence turf quality, dry matter yield, or WUE and conclude soil am of Tifdwarf bermudagrass. Iron humate, and to a lesser degree CCs, providedsuperior turf quality, dry matter yield, and WUE than all other amendments investigated. Turf grown in pure sand produced unacceptable turf quality, decreased turf yield, and WUE. Therefore, it is recommended that iron humate or CCs be used when attempting to increase turf quality or WUE of Tifdwarf bermudagrass. However, if an N-source fertilizer containing primarily NO3 instead of NH4 was used, or if zeolites were NH4-loaded prior to incorporation, zeolites may be an affective amendment for use in putting 92

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93 maintaining acceptable turf quality via the use of certain soil amendments. However, the influence of soil amendments on turf WUE and quality during periods of adequate moisture and nutrients availability remains ambiguous. It is likely that during these periods, soil amendments may not in and development. Thus, further research regarding this concern woo34te 3 3nd 44es, may have a greater affinity and capacity to re than CCs. Future research in this a344344434 fluence turf growth uld be valuable. Nutrient Leaching I fail to reject H: soil amendments do not reduce NOor PO-2 leaching. Nitrabreakthrough curves and applied NO leached show soil amendments have little or noinfluence on NO leaching. Calcined clays did slow P movement but were incapable of reducing total P leached. These results show that P movement can be slowed by incorporating CCs into a filter-zone below the rootzone of USGA putting greens. However, if water movement persists, P may not be retained and could leach to grouwater. I reject Ho: soil amendments do not reduce NH leaching, and conclude soil amendments do reduce NH leaching. Ammonium leaching was nearly eliminated via soil amendment incorporation. Higher CEC amendments, such as zeolit tain NH4 against leaching rea would b e warranted. I reject Ho: SMSA do not reduce NO-, NH+, or PO-2 leaching, and conclude soil amendments do reduce NO-, NH+, or PO-2 leaching. The influence of SMSA on reducing nutrient leaching was directly or, in the case of NH+ indirectly, related to each amendments EAEC. With the incorporation of SMSA into the filter layer, NOand PO-2 movement may not only be slowed but may be retained, effectively reducing the potential for groundwater contamination. The practical implications of this study are that during periods of normal fertilizer applications but excessive leaching, N and P

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94 movement through golf course putting greens can be reduced or eliminated via the use of surfactant-modified soil amendments. However, further research is needed prior to recommendations. Bi-layer stability and longevity in a dynamic soil system have nobeen investigated nor have any potential environmental influences. Furthermore, the influence of SMSA on turf growth and development use t is unknown and may be detrimental. Research in this area must be condrating these products in a putting green. ucted prior to incorpo

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APPENDIX MISCALLENEOUS GRAPHS AND TABLES

PAGE 109

Termperature (oC) 0100200300400500600Weight (%) 0102030405060708090100 Figure A-1. Thermal gravimetry analysis of HDTMA. 96

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97 Temperature (oC) 0100200300400500600Weight (%) 9092949698100 HDTMA Soil Master Soil Master oated calcined clay 1. Figure A-2. Thermal gravimetry analysis of HDTMA c

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98 Temperature (oC) 0100200300400500600Weight (%) 9092949698100 HDTMA Profile Profile Figure A-3. Thermal gravimetry analysis of HDTMA coated calcined clay 2.

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99 Temperature (oC) 0100200300400500600Weight (%) 889092949698100 HDTMA-Clinoptilolite Clinoptilolite Figure A-4. Thermal gravimetry analysis of HDTMA coated clinoptilolite.

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100 Figure A-5. X-ray diffractogram of diatomaceous earths in a side-packed powder mount. Axis PSA

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101 Soil Master Profile Figure A-6. X-Ray diffractogram of calcined clays in a side-packed powder mount.

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102 dcolite E Ecosan Figure A-7. X-Ray diffractogram of zeolites in a side-packed powder mount.

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103 Table A-1. Chemical properties of irrigation water used in glasshouse and field studies. Field Glasshouse pH 7.1 6.8 EC (S cm-1) 0.2 0.1 P (mg L-1) 0.2 0.1 K (mg L-1) 0.9 0.2 Ca (mg L-1) 81.9 45.2 Mg (mg L-1) 9.6 2.2 Zn (mg L-1) 0.0 0.0 Mn (mg L-1) 0.0 0.0 Cu (mg L-1) 0.0 0.0 Fe (mg L-1) 0.0 0.0

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104 Microporosity (%) 6810121416Plant Available Water (%) 61014 R = 0.8318 Figure A-8. Correlation between microporosity and plant available water of amendment/sand mixture at 85:15 by volume. 8 12 16 y = 0.8204x + 0.18692

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105 Solution NO3-N (mg L-1) 0100200300400500NO3-N Absorbed (mg kg-1) 0500100015002000250030003500 Calcined Clay 1 Calcined Clay 2 Clinoptilolite S = 265.07 C0.40 S = 121.51 C0.47 S = 145.82 C0.39 Figure A-9. Nitrate sorption isotherm for surfactant-modified soil amendmen ts.

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106 Equilibrium NH4-N Concentration (mg L-1) 020040060080010001200Amount NH4-N Sorbed (mg kg-1) -200002000400060008000 Calcined Clay 1 HDTMA Calcined Clay 1 S = 3.76 C0.72 Figure A-10. Ammonium sorption isotherm for uncoated and HDTMA coated ca lcined clay 1.

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107 Equilibrium NH4-N Concentration (mg L-1) 0200400600800100012001400Amount NH4-N Sorbed (mg kg-1) -200002000400060008000 Calcined Clay 2 HDTMA Calcined Clay 2 S = 4.69 C0.50 S = 6.31 C0.77 Figure A-11. Ammonium sorption isotherm for uncoated and HDTMA coated calcined clay 2.

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108 Equilibrium NH4-N Concentration (mg L-1) 02004006008001000Amount NH4-N Sorbed (mg kg-1) 010000200003000040000 Clinoptilolite HDTMA Clinoptilolite S = 5.59 C0.74 S = 4.95 C0.78 Figure A-12. Ammonium sorption isotherm for uncoated and HDTMA coated clinoptil olite.

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109 Equilibrium P concentration (mg L-1) -1000100200300400500Amount P Sorbed (mg kg-1) -50005001000150020002500 HDTMA Calcined 1 Calcined 1 S = 4.5 C0.54 S = -0.21 C1.17 Figure A-13. Phosporus sorption isotherm for uncoated and HDTMA coated caclay 1. lcined

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110 Equilibrium P concentration (mg L-1) -50050100150200250300350Amount P Sorbed (mg kg-1) 01000200030004000 HDTMA Calcined Clay 2 Calcined Clay 2 S = 4.86 C0.60 S = 3.81 C0.69 Figure A-14. Phosphorus sorption isotherm for uncoated and HDTMA coated calcinedclay 2.

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Equilibrium P concentration (mg L-1) -1000100200300400500600Amount P Sorbed (mg kg-1) -1000100200300400500600700 HDTMA Clinoptilolite Clinoptilolite S = 4.02 C0.39 Figure A-15. Phosporus sorption isotherm for uncoated and HDTMA coated clinopti lolite.

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112Table A-2. Phosphorous and ammonium leaching parameters for the 2-site model. --------------P --------------------------NH4 -----------------Root zone media Filter zone media R R Sand/Peat Zeolite 1 43 0.810 1.26 UD # UD UD UD 1.05 Sand/Peat CC 2 43 0. 740 1.32 1.38 UD UD UD UD Sand/Peat CC 1 43 0.700 1 1.56 43 0.030 3.22 51.8 Sand/Peat HDTMA-Zeolite 1 43 0.340 0.74 3.46 43 0.029 3.52 50.83 Sand/Peat HDTMACC 2 43 0. 012 1.84 108.04 43 0.308 1.02 4.26 Sand/Peat HDTMACC 1 43 0. 003 3.65 405.27 43 0.650 0.62 1.86 Sand/Peat Sand 43 0.820 0. 99 1.18 43 0.880 0.12 1.29 Sand Sand 43 0.680 1.45 43 0.830 0.12 1.09 Peclet number 41 0.44 fraction of instantaneous retardation Damkohler number Retardation Factor # undetermined

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113 LIST OF REFERENCES Allen, E.R., D.W. Ming, L.R. Hossner, a nd D.L. Henninger. 1995. Modeling transport kinetics in clinoptilolite-phosphate rock systems. Soil Sci. Soc. Am. J. 59:248-255. Amon, J.E tion of mineralogy and environmental In Amonette (ed.). Soil mineralogy with environmental lons. SS SSSA Madison, WI. Andrews, R.D., A.J. Koski, J.A. Murphy, and A.M. Petrovic. 1999. Zeoponic materials -in. Golf Course Manage. 67(2):68-72. BastaT., R.J. Zupa 2000. Evaluating soil tests to predict udagrass growth in drinking wate r treatment residua ls with phosphorus ilizeriron. Qual. 29:2007-2012. B, L.D. 1956. Soil physics. 3rd ed. John Wiley & Sons. New York. B, J.B82. Turf management for golf courses. Burgess publishing, Minneapolis, B. 2002. The putting green. p. 105-193. In J.T. Snow et al. (ed.) Turf or Press, Chelsea, MI. Bigelow, C.A., D.C. Bowman, and D.K. Cassel. 1999. Germination and establishment h root-zone amendments. Golf Course Manage. 67(4)62-65. BC.A. modification with rganic soil amendments and sphagnum peat moss. USGA Green Sect. Rec. 38(4):7-13. Bigelow, C.A., D.C. Bowman, and D.K. Ca ssel. 2001a. Nitrogen leaching in sand-based rootzones amended with inorganic soil am ents and sphagnum peat. J. Amer. Soc. Hort. Sci. 126(1):151-156. Bigelow, C.A., D.C. Bowm Rufty. 2001b. Creeping bentgrass response to inorganic soil aments and mechanically induced subsurface drainage and aerati 7-8 Bigelow, C.A., D.C. Bowman, and D.K. Cassel. 2003. Inorganic soil amendments limit nien leaching in newly constructed n rooting mixtures. U 2(2 ette availability. p. 153-198. app allow rapid greens grow N. berm fert 20 02. Met hod s fo r de term ina icati SA Boo k s erie s, no 7. ncic an d E .A. Day ton J. Env aver eard eard igel 19 Minn. J.B man wit ow, ino agem ent for go lf co urs es. A nn Arb D. Bo wm an, a nd K. C ass el. 2000. Sand-based rootzone endm 05. -11 a n, D.K. Cassel, and T.W n. C endm Sc o rop i. 41 :79 trog SGA T sa nd-based putting gree 4):1 urfg ras s En v. R es. On line

PAGE 127

114 Bigelow, C.A., D.C. Bowman, and D.K. Cassel. 2004. Physical properties of three sand size classes amended with inorganic materials or sphagnum peat moss for putting green rootzones. Crop Sci. 44:900-907. Biran, I., B. Bravado, I. Bushkin-Harav, and E. Rawitz. 1981. Water consumption and growth rate of 11 turfgrasheight, irrigation frequency, Black, C.C., T.M. Chen, and R.H. Brown. 1969. Biochemical basis for plant BoettA. Dick et al. (ed.) Soil mineralogy with environmental applications. SSSA, Madison, WI. Bowmn. 2001. Pilot test of a surfactant-modified zeolite permeable barrier for groundwater remediation. p. Breck, D.W. 1974. Zeolite molecular sieves: Structure, chemistry, and use. John Wiley & en construction. Agron. J. 67:647-652. itrate and 4:947-950. 117. Brusseau, M.L., R.E. Jessup, and S.C. Rao. 1991. Nonequilibrium sorption of organic Bugbee, G.J., and C.R. Frink. 1985. Alum sludge as a soil amendment: Effects on soil Carlson, M.S., C.L. Kerkman, and W.R. Kussow. 1998. Peats and supplements for root Carro1. Cation exchange capacity. p. 45-66. In Turfgrass soil fertility and chemical problems. Ann Arbor Press, Chelsea, MI. ses as affected by mowing and soil moisture. Agron. J. 73:85-90. competition. Weed Sci. 17:338-344. inger, J.L., and D.W. Ming. 2002. Zeolites. p. 585-610. In W. an, R.S., Z. Li, S.J. Roy, T. Burt, T.L. Johnson, and R.L. Johnso 161-185. In Smith and Burns (ed.) Physiochemical groundwater remediation. Kluwer academic/Plenum publishers, New York. Sons, New York, NY. Brown, K.W., and R.L. Duble. 1975. Physical characteristics of soil mixtures used for golf gre Brown, K.W., J.C. Thomas, and R.L. Duble. 1982. Nitrogen source effect on nammonium leaching and runoff losses from greens. Agron. J. 7 Brown, E.A., and J.B. Sartain. 2000. Phosphorus retention in united states golf association greens. Soil and Crop Sci. Soc. Florida Proc. 59:112Brown, E.A. 2003. Differential nitrate leaching and mass balance of 15N-labeled nitrogen sources applied to turfgrass and citrus. Ph.D. diss. Univ. of Florida, Gainesville chemicals: elucidation of rate-limiting processes. Environ. Sci. Technol. 25(1):134-142. properties and plant growth. Connecticut Agric. Exp. Stn. Bull. 823. Connecticut Agric. Exp. Stn., New Haven. zone mixes. Golf Course Manage. 66(9):70-74. w, R.N., D.V. Waddington, and P.E. Rieke. 200

PAGE 128

115 Coale, F.J., P.S. Porter, and W. Davis. 1994. Soil amendments for reducing phosphorus concentrations of drainage water from Histosols. Soil Sci. Soc. Am. J. 58:1470-1475. Comer, J. 1999. Impact of soil amendments on moisture retention and reduction of nutrients loss from a simulated USGA green profile. M.S. thesis. Univ. of Florida,Gainesville. rooting and Crop Sci. 38:1639-1644. DC. soil analysis. ASA, Madison, WI. iol. 33(5):1037-1041. and l. 19(3):345-354. Feldh Factors influencing rate in urban environments. Agron. J. 75:924-930. Feldhnse to deficit irrigation. Agron. J. 76:85-89. on Cooper, R.J., C. Liu, and D.S. Fisher. 1998. Influence of humic substances onnutrient content of creeping bentgrass Crawley, W., and D. Zabcik. 1985. Golf green construction using perlite as an amendment. Golf Course Manage. 53(7):44-52. Danielson, R.E., C.M. Feldhake, and W.E. Hart. 1981. Urban lawn irrigation and management practices for water saving with minimum effect on lawn quality. Complete Rep. Office of Water Res. and Technol. Proj. No. A-043-Colo., FortCollins, Co. U.S. Dep. of the Interior, Washington Day, P.R. 1965. Particle fractionation and particle-size analysis. p. 545-567. In C.A. Black (ed.) Methods of Dean-Raymond, D., and M. Alexander. 1977. Bacterial metabolism of quaternary ammonium compounds. Appl. Environ. Microb DeRoo, H.C. 1980. Nitrate fluctuations in groundwater as influenced by use of fertilizer. Con. Agric. Exp. Sta. Bull. 779, New Haven, Conn., p. 13. Elliott, H.A., and L.M. Singer. 1988. Effect of water treatment sludge on growthelemental composition of tomato shoots. Commun. Soil Sci. Plant Ana ake, C.M., R.E. Danielson, and J.D. Butler. 1983. Turfgrass evapotranspiration. I. ake, C.M., R.E. Danielson, and J.D. Butler. 1984. Turfgrass evapotranspiration. II. Respo Ferguson, G.A., I.L. Pepper, and W.R. Kneebone. 1986. Growth of creeping bentgrass a new medium for turfgrass growth: clinoptilolite zeolite-amended sand. Agron. J.78:1095-1098. Ferguson, G.A., and I.L. Pepper. 1987. Ammonium retention in sand amended with clinoptilolite. Soil Sci. Soc. Am. J. 51:231-234. Flocker, W.J., J.A. Vomocil, and F.D. Howard. 1959. Some growth responses of tomatoes to soil compaction. Soil Sci. Soc. Am. Proc. 23:188-191.

PAGE 129

116 Flury, M., M.V. Yates, and W.A. Jury. 1999. Numerical analysis of the effect of the lower boundary condition on solute transport in lysimeters. Soil Sci. Soc. Am. J.63:149 3-1499. Frank, A.B., R.E. Barker, and J.D. Berdahl. 1987. Water-use efficiency of grasses grown Fresenburg, B.S. 1999. Soil amendments for Missouri athletic fields: Infield soils and Missouri]. Fu, J., J. Fry, and B. Huang. 2003. Effects of deficit irrigation on photosynthesis, 2002 Geert4. Long-term effects of sludge application to land. J. AWWA. 86:11-64. Gilbe alkyltrimethylammonium bromides. Lett. Appl. Microbiol. 1:101-104. Goto,l zeolites as soil conditioners: III. Determination of the ion-exchange selectivity coefficients of Gregory, P.J., L.P. Simmonds, and C.J. Pilbeam. 2000. Soil type, climatic regime, and the Halberg, G.R. 1987. The impacts of agricultural chemicals on groundwater quality. Geo. Journal. 15:283-295. Harrihorus retention as related to morphology of sandy coastal plain soil material. Soil Sci. Hatfield, J.L., T.J. Sauer, and J.H. Prueger. 2001. Managing soils to achieve greater water Havlin, J.L., J.D. Beaton, S.L. Tisdale, and W.L. Nelson. 1999. Nitrogen. In L. Harvey (ed.) Soil fertility and fertilizers 6th ed. Prentice Hall. Upper Saddle River, NJ. Heil, t sludge influence on the growth of sorghum-sudangrass. J. Environ. Qual. 18:292-298. Hillelntal soil physics. Academic Press. San Diego, CA. Follett, R.F. (ed.). 1989. Nitrogen management and groundwater protection. In Developments in agricultural managed-forest ecology #21. Elsevier, New York. under controlled and field conditions. Agron. J. 79:541-544. topdressings. p. 7-8. In Turfgrass: 1999 Research & Information Report [ respiration, and water use efficiency of zoysiagrass and tall fescue. p. 88-93.Turfgrass Research Report, Kansas State University. sema, W.S., W.R. Knocke, J.T. Novak, and D. Dove. 199 rt, P., and A. Al-taae. 1985. Antimicrobial activity of some I., and M. Ninaki. 1980. Studies on the agriculture utilization of natura natural zeolites. J. Agric. Sci. Tokyo Nogyo Daigaku 25(2):168. response of water use efficiency to crop management. Agron. J. 92:814-820. s, W.G., R.D. Rhue, G. Kidder, R.B. Brown, and R. Littell. 1996. Phosp Soc. Am. J. 60:1513-1521. use efficiency: a review. Agron. J. 93:271-280. D.M., and K.A. Barbarick. 1989. Water treatmen D. 1998. Flow of water in saturated soil. p. 173-201. In Environme

PAGE 130

117 Huang, Z. T. and A. M. Petrovic. 1991. Clinoptilolite zeolite amendment of sand influence on water use efficiency of creeping bentgrass and nitrate leaching. Agron. Abst. 17 7. leaching 23:1190-1194. Hudsy. J. Soil and Water Cons. 49(2):189-194. Hull, In D.V. Waddington et al. (ed.) Turfgrass. Agronomy Monogr. 32. ASA, SSSA, Hummil, or compost? Golf Course Manage. 68(4)57-60. IppolCo-application effects of water treatment residuals and biosolids on two range grasses. J. Environ. Qual. 28:1644-Kirkham, R.R., G.W. Gee, and T.L. Jones. 1984. Weighing lysimeters for long-term Koraimmonium compounds. Hakko Kogaku Zasshi 48:635-640. KluteMethods of soil analysis. Part 1. Agron. Monogr. 9. ASA and SSSA, Madison, WI. Lawtin, L.A., and G.A. Codd. 1991. Cyanobacterial (blue-green algae) toxins and their significance in UK and European waters. J. Inst. Wat. Environ. Managt. 5:460:465. Letey, nd wetting agents in turfgrass management III. Effects on oxygen diffusion rate and root growth. Agron. J. 58:531-535. Lewis, M.D., F.D. Moore, III, and R.L. Goldsberry. 1984. Ammonium-exchanged clinoptilolite with urea as nitrogen fertilizer. p. 105-111. In W.G. Pond and F.A. :1121-1125. lolite. Huang, Z.T., and A.M. Petrovic. 1994. Clinoptilolite zeolite influence on nitrateand nitrogen use efficiency in simulated sand based golf greens. J. Environ. Qual on, B.D. 1994. Soil organic matter and available water capacit R.J. 1992. Energy relations and carbohydrate partitioning in turfgrasses. p. 175-205. and CSSA, Madison, WI. el, N.W. Jr. 2000. What goes best with sand: peat, so ito, J.A., K.A. Barbarick, and E.F. Redente. 1999. 1650. water balance investigations at remote sites. Soil Sci. Soc. Am. J. 48:1203-1205. H., and K. Takeichi. 1970. Antimicrobial activity of quaternary a A. 1986. Water retention: Laboratory methods. P. 635-662. In A. Klute (ed.) J., W.C. Morgan, S.J. Richards, and N Valoras. 1966. Physical soil amendmentssoil compaction, irrigation, a Mumpton (ed.) Zeo-agriculture, use of natural zeolites in agriculture and aquaculture. Westview Press, Boulder, CO. Li, D., L.K. Joo, N.E. Christians, and D.D. Minner. 2000. Inorganic soil amendment effects on sand-based sports turf media. Crop Sci. 40 Li, Z. 1999. Sorption kinetics of Hexadecyltrimethylammonium on natural clinoptiLangmuir 15:6438-6445.

PAGE 131

118 Li, Z., H.K. Jones, R.S. Bowman, and R. Helferich. 1999. Enhanced reduction of chromate and PCE by palletized surfactant-modified zeolite/ zerovalent iron. Environ. Sci. Techn33 ol. :4326-4330. Li, Z., S.J. Roy, Y. Zou, and R.S. Bowman. 1998. Long-term chemical and biological Li, Z., and R.S. Bowman. 1997. Counterion effects on the sorption of cationic surfactant Lucas, R.E., P.E. Rieke, and R.S. Farnham. 1965. Peats for soil improvement and soil mixes. Ext. Bull. 593. Mich. State Univ., East Lansing. MacKown, C.T., and T.C. Tucker. 1985. Ammonium nitrogen movement in a coarse-textured soil amended with zeolite. Soil Sci. Soc. Am. J. 49:235-238. Makrrticle phosphorus diffusion in a drinking water treatment residual at room temperature. J. Coll. and Inter. Sci. 277:417-423. Malec from Sediment in the Lower St. Johns River Estuary. J. Environ. Qual. 33:1545-Mannion, B. 1996. Topdressing and aeration strategies. California Fairways 5(4):24-30. Marti14:24-26. McCoturf rootzones mixes. Agron. J. 84:375-381. McCo zones. J. Turfgrass Manage. 2:49-69. McInarnham rth Li, Z., I, Anghel, and R.S. Bowman. 1998. Sorption of oxyanions by surfactant-modified zeolite. J. Disp. Sci. Tech. 19(6&7):843-857. stability of surfactant-modified zeolite. Environ. Sci. Technol. 32:2628-2632. and chromate on natural clinoptilolite. Environ. Sci. Technol. 31:2407-2412. is, K.C., H. El-Shall, W.G. Harris, G.A. OConnor, and T.A. Obreza. 2004. Intrapa ki, L.M., J.R. White, and K.R. Reddy. 2004. Nitrogen and Phosphorus Flux Rates 1555. n, A., and G.D. Cooke. 1994. Health risks in eutrophic water supplies. Lake Line y, E.L. 1992. Quantitative physical assessment of organic materials used in sports y, E.L., and R.C. Stehouwer. 1998. Water and nutrient retention properties of internally porous inorganic amendments in high sand content root tyre, D.S. 1974. In J. Loveday (ed.) Methods of analysis for irrigated soils. Commonwealth Agricultural Bureaux Technical Communication No 54, FRoyal, England. Meier, W.M., and D.H. Olson. 1988. Atlas of zeolite structure types. 2nd ed. Butterwoand Co. Ltd., London, UK.

PAGE 132

119 Mercer, B.W., L.L. Ames, T.J. Touhill, W.J. Van Slyke, and R.B. Dean. 1970. Amremoval from secondary effluents by selective ion exchange. J. Water Poll. CoFed. 42:R95-R107. monia nt. of water conservation: Determining crop coefficient of turfgrasses. p. 357-364. In F. Lemaire (ed.) Proc. 5th Int. ., SSA, Madison, WI. Morton, T.G., A.J. Gold, and W.M. Sullivan. 1988. Influence of over watering and 30. Nace,cular, No. C 0536. U. S. Geological Survey, Reston, VA. Nkedn during displacement of hydrophobic organic chemicals and calcium-45 through soil columns with aqueous and mixed solvents. Environ. Sci. Technol. ent of creeping bentgrass on sandy media. Hortscience 26(2):117-119. rium of hydrophobic organic chemicals by organoclays. Environ. Sci. Technol. 30(1):89-96. OCo. Final lorida Department of Environmental Protection. tems for rt 2, 2nd ed. Agronomy Monogr. 9. ASA and SSSA, Madison, WI. Meyer, J.L., V.A. Gibeault, and V.B. Younger. 1985. Irrigation of turfgrass below replacement of evapotranspiration as a means turfgrass res. conf., Avignon, France. 1-5 July. Inst. Natl. de la Recherche AgronParis. Miller, G.L. 2000. Physiological response of bermudagrass grown in soil amendments during drought stress. Hortscience 35(2):213-216. Ming, D.W., and F.A. Mumpton. 1989 Zeolites in soils. p. 874-911. In J.B. Dixon and S.B. Weed (ed.) Minerals in soil environments. 2nd ed. S Minner, D. 1988. Turfgrass culture and water use. Landscape Manage. 28(2):60-68. fertilization on nitrogen losses from home lawns. J. Environ. Qual. 17:124-1 N.L. 1967. Are we running out of water? p. 7. Cir i-Kizza, P., Brusseau, M.L.; Rao, P.S.C., Hornsby, A.G. 1989. Nonequilibrium sorptio 23:814-820. Nus, J.L., and S.E. Brauen. 1991. Clinoptilolite zeolite as an amendment for establishm Nzengung, V.A., E.A. Voudrias, P. Nkedi-Kizza, J.M. Wampler, and C.E. Weaver. 1996.Organic cosolvent effects on sorption equilib nnor, G.A., and D. Sarkar. 1999. Fate of applied residuals-bound phosphorusReport, Contract WM 661, F Ok, C., S.A. Anderson, and E.H. Ervin. 2003. Amendments and Construction SysImproving the Performance of Sand-Based Putting Greens. Agron. J. 95:1583-1590. Olsen, S.R., and L.E. Sommers. 1982. Phosphorus. p. 403-430. In A.L. Page et al. (ed.) Methods of soil analysis. pa

PAGE 133

120 Petrovic, A.M. 1990. The fate of nitrogenous fertilizers applied to turfgrass. J. Environ. Qual. 19:1-14. Pierzynshki, G.M., J.T. Sims, and G.F. Vance. 1994. Soil and Environmental Quality. Porteorption Pratt, P.F. 1984. Nitrogen use and nitrate leaching in irrigated agriculture. p. 319-333. In Ralston, D.S., and W.H. Daniel. 1973. Effect of porous rootzone materials underlined Richardson, M., and D. Karcher. 2001. Inorganic amendments and aerification recovery. ure and ge. Commun. Soil Sci. Plant Anal. 11:533-545. Rodri 27. Rowell, D.L. 1994. Soil science: methods and applications. Longman Scientific, Harlow, Salisbury, F.B., and C.W. Ross. 1992. Mineral nutrition. p. 116-135. In Plant physiology. Sartai sources. p. 77-84. In Turfgrass research in florida. T.E. Freeman. (ed.) Univ. of Fl., Gainesville, FL. Sartai. Sartain, J.B., and H.D. Gooding. 2000. Reducing nitrate leaching during green grow-in. SAS Scambilis, N.A. 1977. Land disposal of chemical sludges. Ph.D. diss., Univ. of Missouri, Columbia. Lewis Publishers, Boca Raton, FL. r, P.S., and C.A. Sanchez. 1992. The effect of soil properties on phosph o rus sby Everglades Histosols. Soil Sci. 154:387-398. R.D. Hauck (ed.) Nitrogen in crop production. Am. Soc. Agron. Madison, WI. with plastic on the growth of creeping bentgrass. Agron. J. 65:229-232. Golf Course Mange. 69(10):58-62. Reddy, K.R. 1982. Mineralization of nitrogen in organic soils. Soil Sci. Soc. Am. J.46:561-566. Rengasamy, P., J.M. Oades, and T.W. Hancock. 1980. Improvement of soil structplant growth by addition of alum slud quez, I.R., and G.L. Miller. 2000. Using near infrared reflectance spectroscopy toschedule nitrogen applications on dwarf-type bermudagrasss. Agron. J. 92:423-4 UK. 4th ed. Wadsworth Publishing Company, Belmont, CA. n, J.B. 1990. Leaching studies involving selected slow-release N n, J.B. 1999. Iron nutrition improves turfs mettle. Grounds Main. 34(8):24-28 Sartain, J.B., and J. Comer. 2004. Influence of soil amendments on water-use-efficiency, bermudagrass growth, and nutrient leaching. Fla. Turf. Dig. 21(3):8-11. Golf Course Manage. 68(4):70-73. Institute. 1987. SAS users guide: Statistics. 6th ed. SAS Inst., Cary, NC.

PAGE 134

121 Schantz, H.L., and L.N. Piemeisel. 1927. The water requirement of plants at Akron, Colorado. J. Ag ric. Res. 34:1093-1189. anic matter. p. 275-330. In Environmental organic chemistry. 2nd ed. John Wiley & Sons, Hoboken, NJ. Semmtural zeolites. p. 45-54. In W.G. Pond and F.A. Mumpton (ed.) Zeo-agriculture: use of natural zeolites in agriculture Shaddox, T.W. 2001. Fate of nitrogen during grow-in of a golf course fairway under ction Record. 39(5):17-18. on properties and on yield and quality of putting greens. Agron J. 54:393-395. Snydetion for reducing N leaching in bermudagrass turf. Agron. J. 76:964-969. tigations Report No. 42, Version 3.0. USDA-Natural Resources Conservation Service-National Soil Survey Center, Lincoln, NE. Starre nitrogen applied to turfgrass-covered soil columns. J. of Irrg. Drain. Eng. 121:390-395. Stoutaffected by soil drainage and nitrogen fertilization on two floodplain soils. J. Soil rass under humid conditions. Soil Sci. Soc. Schwarzenback, R.P., P.M. Gschwend, and D.M. Imboden. 2003. General introductionand sorption processes involving org ens, M.J. 1984. Cation-exchange properties of na and aquaculture. Westview Press, Boulder, CO. different nitrogen management practices and irrigation intensities. M.S. Thesis. Univ. of Florida, Gainesville. Shuman, L.M. 2001. Nitrogen and phosphorus loss from greens and fairways: Is there a potential problem? USGA Green Se Smalley, R.R., W.L. Pritchett, and L.C. Hammond. 1962. Effects of four amendmentssoil physical r, G.H., B.J. Augustin, and J.M. Davidson. 1984. Moisture sensor controlled irriga Snyder, R.H. 2003. Investigation of coated sands and peat for use in golf course putting green construction. Ph.D. diss. Univ. of Florida, Gainesville. Soil Survey Laboratory Staff. 1996. Soil survey laboratory manual. p. 693. Soil Survey Inves tt, S.K., N.E. Christians, and R. Al Austin. 1995. Fate of W.L., and R.R. Schnabel. 1997. Water-use efficiency of perennial ryegrass as and Water Cons. 52(3):207-211. Stout, W.L. 1992. Water-use efficiency of grasses as affected by soil, nitrogen, and temperature. Soil Sci. Soc. Am. J. 56:897-902. Stout, W.L., G.A. Jung, and J.A. Shaffer. 1988. Effects of soil and nitrogen on water useefficiency of tall fescue and switchg Am. J. 52:429-434. Sylvia, D.M., J.J. Fuhrman, P.G. Hartel, and D.A. Zuberer. 1997. Principles and applications of soil microbiology. Prentice-Hall, Inc. Englewood Cliffs, N.J.

PAGE 135

122 Tate, L.R. 1977. Nitrification in Histosols: a potential role for heterotrophic nitrifier. Appl. Environ. Microbial. 33:911-914. Taylor, D.H., C.F. Williams, and S.D. Nelson. 1997. Water retention in root-zone soil mixtures of layered profiles used for sports turf. Hortscience 32(1):82-85. United States Golf Association, Green Section Staff. 1993. Specifications for a method of Van Genuchten, M. 1981. Th. Research Report No. 119, USDA Salinity Laboratory, Riverside, CA. Varshon Plant Anal. 24(17&18):2493-2505. Waddington, D.V. 1992. Soils, soil mixtures, and soil amendments. p. 331-383. In D.V. Waltz, C., and B. McCarty. 2000. Soil amendments affect turf establishment rate. Golf Course Manage. 68(7):59-63. Waltzproperties of rootzone mixes amended with inorganics for golf putting greens. Wehtje, G.R., J.N. Shaw, R.H. Walker, and W. Williams. 2003. Bermudagrass growth in Wess relation to soils and crops. p. 461-504. In J.N. Luthin (ed.) Drainage of agricultural lands. ASA, Madison, WI. Whiteof Everglades Wetland Soils along a Phosphorus-Impacted Gradient. J. Environ. Qual. 32:2436-Younger, V.B., and A.W. Marsh, R.A. Strohman, V.A. Gibeault, and S. Spaulding. 1981. Water use and quality of warm-season and cool-season turfgrasses. p. 251-257. In 3 ll., Univ. of Guelph, Guelph, ON. putting green construction, the 1993 revision. 31(2):1-3. ovi, A., and J.B. Sartain. 1993. Chemical characteristics and microbial degradatiof humate. Commun. Soil Sci. Viets, F.G., Jr. 1962. Fertilizers and the efficient use of water. Adv. Agron. 14:223-264. Waddington et al. (ed.) Turfgrass. Agron. Monogr. 32. ASA, Madison, WI. F.C., V.L. Quisenberry, and L.B. McCarty. 2003. Physical and hydraulic Agron. J. 95:395-404. soil supplemented with inorganic amendments. Hortscience 38(4):613-617. eling, J., and W.R. van Wijk. 1957. Land drainage in J.R., and K.R. Reddy. 2004. Nitrification and Denitrification Rates 2443. R.W. Sheard (ed.) Proc. 4th Int. turfgrass res. conf., Guelph, ON, Canada. 19-2July. Int. Turfgrass Soc., and Ontario Agric. Co

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Travis Shaddox was born in Shawnee, Oklahoma, on February 10, 1976. After receivin horticulture from Oklahoma State University in 1999, accepted to the university as a graduate student with Dr. Jerry Sartain. Throughout the next two years he investigated nitrogen leaching during turfgrass establishment, and in 2001,in received Travis as his graduate student to continue his work towards a Ph.D. degree in degree, Travis would like to continue using his knowledge and skills in fertilizers and soil fertili BIOGRAPHICAL SKETCH ing his bachelors degree he moved to Gainesville with the hopes of attending the University of Florida. He was he fulfilled his requirements and was awarded a Master of Science degree. Having enjoyed his experience in Gainesville, he wished to remain there to continue working on his doctorate degree. As luck would have it, Dr. Sartain aga the Soil and Water Science Department at the University of Florida. After earning his ty at either a university or industry position. 123


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INVESTIGATION OF SOIL AMENDMENTS FOR USE IN GOLF COURSE
PUTTING GREEN CONSTRUCTION















By

TRAVIS SHADDOX


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


2004



























Copyright 2004

by

Travis Shaddox













ACKNOWLEDGMENTS
I give my sincere thanks and appreciation to the chairman of my supervisory

committee, Dr. Jerry Sartain. Without the opportunity and his support, achieving this

degree would not have been possible. I would also like to thank the other members of my

committee: Dr. James Bonczek for his expertise in surfactant chemistry, Dr. Donald

Graetz for his knowledge of soils and nitrogen transformations, Dr. Grady Miller for his

help in the area of turfgrass and soil amendments, and Dr. Peter Nkedi-Kizza for his

support during my leaching experiments.

Thanks go to the Florida Turf Grass Association who sponsored this research

project. I appreciate its continued support ofturfgrass research at the University of

Florida. Special thanks go to lab personnel, Ed Hopwood Jr., Nahid Varshovi, Shawron

Weingarten, Martin Sandquist, and Brian Owens, who helped me throughout my

research. Finally, I would like to thank all the members of my family in Oklahoma and

in Florida for their ongoing support.
















TABLE OF CONTENTS

page

A C K N O W L E D G M E N T S ................................................................................................. iii

LIST OF TA BLE S ....................................................... .. .......... ............ .. vii

LIST OF FIGURES ......... ............................... ........ ............ ix

ABSTRACT ........ .............. ............. ...... .......... .......... xi

CHAPTER

1 IN TR OD U CTION ............................................... .. ......................... ..

W after U se E efficiency ......................................................................... .......... ..
N u trient L each in g ................................................................... ...................... 3

2 LITER A TU R E R EV IEW .............................................................. ....................... 5

Soil A m endm ents .............................................. 5
P eats ..................................................................................... . 6
C alcined C lays ....................................................... 9
Z e o lite s ................................................................................................. 1 1
Diatom aceous Earths ................................. .......................... .. ........ 14
W ater Treatm ent R esiduals ....................................................... 16
W ater-Use-Efficiency ................................. ........................... ... ....... 17
Nitrogen in the Turfgrass Environment ..............................................19
N Transformations in Soil ................. .................................20
Leached N ............................................................22
Phosphorous in the Turfgrass Environment ........................................ .....23
P R actions in Soil.......................................................23
L each ed P ................................................................2 3
Hexadecyltrimethyammonium ..................................................25
B i-layer F orm ation ...........................................................26
A union Sorption ..............................................................2 7
Stability .................................................. 28









3 M ATERIALS AND M ETHOD S ........................................ ......................... 30

Characterization Studies ........................................................................30
Cation Exchange Capacity ............................................................................ 30
M oisture Retention ............................................. .. ...... .............. ... 30
S option Isoth erm s........... ............................................................. ......... .. .... 1
Surfactant L oading ........................................... .................. ............. 32
Therm al Analysis.............. ... ... .............. .... ............32
X -R ay D iffraction ........................................................................ ..................34
N utrient A naly sis............ .................................................................... .... 34
S an d M ix es ......................................................................3 4
W ater U se Efficiency C alculations.......................................................................... 36
Glasshouse Studies ............................................ ................... 36
Y e a r 1 ..........................................................................................3 6
Y e a r 2 ...........................................................3 8
N utrient L teaching Study ............................ ......... ............................ ............... 40

4 RESULTS AND DISCU SSION ........................................... .......................... 45

A m endm ent C haracterizations............................................................... ...............45
Su rfactant S option ................... .......................................... ......... ........... ......4 5
M ineral C om position ......... .......................................... ...... .. .. .............. 46
N utrient C om position .................................................. ............................ 46
N itro g en ............................................................................... 4 7
P h o sp h o ru s ............................................................................................. 4 7
P o ta ssiu m ............................................................................................... 5 0
C a lc iu m ................................................................5 0
p H an d E C ..............................................................5 1
M oisture Retention ................................. ................................... 51
G la ssh o u se 2 0 0 2 ................................................................................................... 5 9
E stab lish m ent ...............................................................59
T u rf Q u ality .........................................................................................................6 1
W ater U se Efficiency ............................................................. 63
G la ssh o u se 2 0 0 3 ................................................................................................... 6 5
E stab lish m ent ...............................................................6 5
T u rf Q u ality .........................................................................................................67
D ays to W ilt.......................................................... 73
W ater U se Efficiency ............................................................. 74
N utrient L teaching Study .................................................................................... ....... 80
N itrate ................................ ......... .. ..................................................... 8 0
A m m onium ........................ ................................................................ ........84
P h o sp h o ru s ................................................................8 8

5 C O N C L U SIO N S ................................................................92

Soil A m endm ents ............................................. 92
Incorporation M ethod ......................................92.............................


v









N u trient L each in g ................................................................. ..................... 9 3


APPENDIX MISCELLANEOUS TABLES AND GRAPHS ..........................................95

LIST OF REFEREN CES ....... ....................................................... ............... 113

BIOGRAPHICAL SKETCH ................ ............................................ ............... 123















LIST OF TABLES


Table page

3-1 Sand size analysis of amendments and sand mixes ..............................................35

4-1 Ion exchange capacity and surfactant sorption as influenced by soil amendment...46

4-2 Chemical properties of amendments used in glasshouse and field studies .............48

4-3 Chemical properties of 85:15 sand/amendment mixtures used in glasshouse and
fi eld stu dies. ....................................................... ................. 49

4-4 Physical analysis of amendment/sand mixture at 85:15 by volume......................53

4-5 Visual quality rating of bermudagrass as influenced by 85:15 sand/amendment
rootzone during 2002 glasshouse study. ...................................... ............... 62

4-6 Tissue yield, applied water, and water-use-efficiency of Tifdwarf bermudagrass
as influenced by soil amendments during glasshouse 2002 study .........................64

4-7 Analysis of variance of mean squares on turf quality during 2003 study as
influenced by incorporation method and amendment type. ....................................68

4-8 Visual quality rating of bermudagrass as influenced by 85:15 sand/amendment
rootzone during 2003 glasshouse study. ...................................... ............... 69

4-9 Visual quality rating of Tifdwarfbermudagrass as influenced by 4 tine
aerification during 2003 glasshouse study. ................................... ............... 71

4-10 Visual quality rating of Tifdwarfbermudagrass as influenced by 9 tine
aerification during 2003 glasshouse study. ................................... ............... 72

4-11 Analysis of variance of mean squares on Tifdwarf days to wilt during 2003
study as influenced by incorporation method and amendment type ......................73

4-12 Days to wilt of Tifdwarf bermudagrass as influenced by 85:15 sand/amendment
rootzone during 2003 glasshouse study. ...................................... ............... 74

4-13 Analysis of variance of mean squares on Tifdwarf water use efficiency during
2003 study as influenced by incorporation method and amendment type. ..............75









4-14 Tissue yield, applied water, and water-use-efficiency of Tifdwarf bermudagrass
as influenced by fully incorporated soil amendments during glasshouse 2003
study. ..................................................................76

4-15 Tissue yield, applied water, and water-use-efficiency of Tifdwarf bermudagrass
as influenced by soil amendments after 9 tine aerification during glasshouse 2003
study. ..................................................................77

4-16 Tissue yield, applied water, and water-use-efficiency of Tifdwarf bermudagrass
as influenced by soil amendments after 4 tine aerification during glasshouse 2003
stu dy ............................................................................... 7 9

4-17 Water use efficiency of Tifdwarf bermudagrass as influenced by incorporation
m eth o d ........................................................................... 8 0

4-18 Total N03-N leached as influenced by filter zone media ........................................83

4-18 Total NH4-N leached as influenced by filter zone media.................. ...............87

4-19 Total phosphorous leached as influenced by filter zone media.............................90

A-1 Chemical properties of irrigation water used in glasshouse and field studies. ......103

A-2 Phosphorous and ammonium leaching parameters for the 2-site model..............112
















LIST OF FIGURES


Figure page

2-1 The nitrogen cycle ............. .... .... .. .. .... ............ ............ 21

2-2 The P cycle. ..................................................................24

2-3 Hexadecyltrimethylammonium ........................................ .......................... 26

2-4 Schematic of HDTMA bi-layer formation ............................................................26

3-1 Schematic diagram of pot set-up used in glasshouse studies showing side and top
view of amendment incorporation methods where A = 85:15 sand/amendment, B =
4 tine aerification with 50:50 sand/amendment, and C = 9 tine aerification with
50:50 sand am endm ent ............................. ................................ .... ...... ...... 39

3-2 Schematic diagram of lysimeter set-up used in leaching studies...........................41

4-1 Moisture release curve for USGA sand amended with zeolites at 85:15 by
v o lu m e ........................................................................... 5 4

4-2 Moisture release curve for USGA sand amended with diatomaceous earths at
85:15 by volum e ....... .. ............... .............................................. 55

4-3 Moisture release curve for USGA sand amended with calcined clays at 85:15 by
v o lu m e ........................................................................... 5 6

4-4 Moisture release curve for USGA sand amended with peat or Fe-Humate at
85:15 by volume or with smectite at 97.5:2.5 by volume.....................................58

4-5 Establishment of Tifdwarf bermudagrass during summer 2002 as influenced by
(A.) zeolites, (B.) diatomaceous earths, (C.) clay and organic, and (D.) calcined
clays. Vertical bars denote standard error. ................................... .................60

4-6 Establishment of Tifdwarf bermudagrass during summer 2003 as influenced by
(A.) zeolite, (B.) diatomaceous earths, (C.) clay and organic, and (D.) calcined
clays. Vertical bars denote standard error. ................................... .................66

4-7 Nitrate breakthrough curves as influenced by filter zone media.............................81

4-8 Ammonium breakthrough curves as influenced by filter zone media......................85









4-9 Phosphorus breakthrough curves as influenced filter zone media .........................89

A-i Thermal gravimetry analysis of HDTMA. ................................... ............96

A-2 Thermal gravimetry analysis of HDTMA coated calcined clay 1............................97

A-3 Thermal gravimetry analysis of HDTMA coated calcined clay 2...........................98

A-4 Thermal gravimetry analysis of HDTMA coated clinoptilolite.............................99

A-5 X-ray diffractogram of diatomaceous earths in a side-packed powder mount. .....100

A-6 X-Ray diffractogram of calcined clays in a side-packed powder mount.............101

A-7 X-Ray diffractogram of zeolites in a side-packed powder mount ...................... 102

A-8 Correlation between microporosity and plant available water of
amendment/sand mixture at 85:15 by volume. ........................... .................. 104

A-9 Nitrate sorption isotherm for surfactant-modified soil amendments..................105

A-10 Ammonium sorption isotherm for uncoated and HDTMA coated calcined clay 1.106

A-11 Ammonium sorption isotherm for uncoated and HDTMA coated calcined clay 2.107

A-12 Ammonium sorption isotherm for uncoated and HDTMA coated clinoptilolite...108

A-13 Phosporus sorption isotherm for uncoated and HDTMA coated calcined clay 1.. 109

A-14 Phosphorus sorption isotherm for uncoated and HDTMA coated calcined clay 2.110

A-15 Phosporus sorption isotherm for uncoated and HDTMA coated clinoptilolite ......111















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

INVESTIGATION OF SOIL AMENDMENTS FOR USE IN GOLF COURSE
PUTTING GREEN CONSTRUCTION

By

Travis W. Shaddox

December 2004

Chair: Jerry Sartain
Major Department: Soil and Water Science

Turfgrass, like all livings organisms, requires water for survival. Turfgrass

professionals, such as golf course superintendents, sports, and athletic field managers

often have a limited amount of water they can use due to consumptive use permits levied

by regional regulatory agencies. Therefore, they are required to find alternate means of

maintaining quality turf while using less water. Many turf professionals enlist the use of

soil amendments because of their ability to increase moisture and nutrient availability.

However, whether or not soil amendments actually influence the efficient use of water by

turfgrass is not known. An objective of this research was to determine the influence of

soil amendments and incorporation method of those amendments on water-use-efficiency

(WUE) of Tifdwarf bermudagrass [Cynodon dactylon (L.) Pers. x C. transvaalensis Burtt

Davy]. A further objective was to determine the influence of surfactant-modified soil

amendments (SMSAs) on nitrogen (N) and phosphorus (P) leaching. To determine the

influence of amendments on turfgrass WUE, Tifdwarf bermudagrass was established on









pots in a glasshouse at the University of Florida turfgrass Envirotron. Treatments

consisted of sand, two zeolites, two calcined clays, two diatomaceous earths, Canadian

sphagnum peat, iron humate, and a smectite. Treatments were arranged in a randomized

complete block design with four replications. Pots were weighed, harvested, and rated

weekly for turf quality for twelve weeks. To determine the influence of SMSAs on N

and P leaching, soil columns were fabricated from 2.54 cm diam. polyvinyl chloride

tubes. Each column was packed with a rootzone layer (30 cm) consisting of sand/peat

(85:15) and a filter zone layer (5 cm) containing each treatment. Treatments were sand,

zeolite, and two calcined clays. Treatments either remained unchanged or were

surfactant-coated. Three replications were used for statistical analysis. In the glasshouse

study, incorporation of iron humate increased turf yield, quality, and WUE above all

other amendment regardless of incorporation method. This was attributed to an increase

in N, Ca, and Fe availability as well as a 13% increase in plant available water which

accompanied iron humate incorporation. Rootzone amended with calcined clays (CCs)

produced 40% more dry matter yield and increased WUE 30% above sand/peat.

However, calcined clays did not produce quality or WUE ratings above iron humate.

Sand and zeolite produced quality and WUE ratings equal to that of sand/peat mixtures.

Of the amendment investigated in this study, only iron humate and CCs consistently

produced quality and WUE ratings above that of sand/peat rootzones. Incorporation of

amendments following aerification reduced each amendment's influence on yield,

quality, and WUE. Therefore, in order to maximize amendment influences on turf

quality and WUE, amendment should be fully incorporated into the rootzone. Surfactant-

modified amendments reduced NO3 levels in leachate to 0.0%, reduced NH4 to 4%, and









reduced P levels to 3% of that applied. Unmodified amendments had no influence on

NO3 leached, reduced NH4 leaching, and retarded P leaching. Surfactant-modified

amendments may be a plausible option to reduce N and P leaching in USGA putting

greens.














CHAPTER 1
INTRODUCTION

Soil modification has been used for centuries to alter certain soil properties to

improve soil-plant relationships. Generally, this is achieved via the use of soil

amendments. Soil amendments may be organic or inorganic and are primarily used to

increase plant available water, cation exchange capacity, or nutrient availability.

However, ambiguity remains regarding their indirect influence on plant water use.

Furthermore, nutrient additions may lead to leaching which can cause a variety of

environmental problems. Compounding the situation, some amendments have the

capacity to retain potential contaminants while others may enhance leaching. Therefore,

this study investigates two primary influences of soil amendment incorporation: turfgrass

water-use-efficiency and nutrient retention in USGA putting greens.

Water Use Efficiency

Every living organism on earth is dependent upon water for survival. In plants,

water is the solvent in which vital nutrients are translocated to various plant parts. Water

is also the initial proton donor during the first steps of photosynthesis. Thus, without

water plants could not survive. Fortunately, the earth contains vast amounts of water in

oceans, lakes, rivers, and in the atmosphere. However, only 0.6% of all water on earth is

considered to be usable by plants and animals (Nace, 1967). With such a small portion of

usable water and such a large number of organisms requiring water, demand for water is

high.









Water used for recreational purposes is often scrutinized because it is not

considered essential to sustain life. Turfgrass water use is receiving attention due to the

overall quantity of water required to maintain acceptable quality turf This attention has

prompted regional regulatory agencies to impose consumptive use permits on many golf

courses in many states including Florida. Superintendents are now faced with having to

maintain an acceptable quality turf while using less water. To become more efficient at

using water they are allotted, superintendents sometimes use soil amendments to alleviate

the inherent low water retention capacity of United States Golf Association (USGA)

putting greens.

Numerous soil amendments are commercially available in at least four distinctly

different classes. This study compared different soil amendments (organic, zeolite,

calcined clay, and diatomaceous earth) to identify materials capable of maximizing

water-use-efficiency (WUE) of Tifdwarfbermudagrass. Published reports reveal many

researchers have investigated the influence of soil amendments on turf establishment, soil

compaction and aeration, soil hydraulic properties, and turfgrass response (Biran et al.,

1981; Miller, 2000; McCoy 1992; Nus and Brauen 1991). Other studies have

investigated WUE of grass species as well as how WUE is influenced by fertilization

(Frank et al., 1987; Hatfield et al. 2001). However, studies to determine the influence of

different rootzone media on WUE of turfgrass are limited. A series of glasshouse and

field experiments were conducted in Gainesville, Florida, from 2001 to 2004 to

investigate WUE of Tifdwarf bermudagrass as influenced by soil amendments.

The objectives of this study were (1) to determine the influence of various soil

amendments (peat, Fe-humate, calcined clay, diatomaceous earth, zeolite, and smectite)









on WUE and quality Tifdwarf bermudagrass in a USGA putting green; (2) to determine

the influence of soil amendment incorporation method on WUE and quality of Tifdwarf

bermudagrass in a USGA putting green.

Nutrient Leaching

For many agronomically important crops, nitrogen (N) and phosphorous (P) are the

two most limiting nutrients. As such, they are typically applied via fertilizers in greater

quantities than many other nutrients. Most fertilizer applied N is in the form of nitrate

(N03-) or is rapidly converted to nitrate via nitrification. Most fertilizer applied P is in

the form of phosphate (H2P04-). Being anions, both nitrate and phosphate are susceptible

to leaching, the consequences of which are seen in the excessive algae growth in lakes

and the elevated levels of P currently being detected in estuaries and in Everglades

National Park (Malecki et al., 2004; White and Reddy, 2004). For this reason, N and P

applied to agronomic crops and turfgrass has been closely monitored. Golf courses are

often scrutinized due to their cultural practices and the unique fertilizer requirement of

turfgrass, which often demand higher fertilizer application rates than many agronomic

crops (Sartain, unpublished data, 1996).

This scrutiny has brought about best management practices (BMP), which allow a

turfgrass manager to minimize environmental impact while still being able to maintain a

quality playing surface. Generally, these practices include the use of controlled-released

fertilizers as well as the proper timing and rate of application. A number of studies have

shown the BMPs have been beneficial at reducing the potential impact golf courses have

on the environment (Rodriquez and Miller, 2000; Sartain and Gooding, 2000; Snyder et

al., 1984). However, leaching of N and P does still occur during unique periods such as

turf establishment or excessive rain events. During periods of high rainfall, leached N









can be as much as ten times higher as during normal rainfall periods (Morton et al.,

1988). This influence could be exacerbated on sand-based putting greens due to their

inherently low nutrient retention capacity.

Hexadecyltrimethylammonium (HDTMA) is a cationic surfactant that can be

electrostatically bound to the negatively charged surface of selected soil amendments and

has been shown to remove anionic compounds, such as nitrate and chromate, from

solution (Li, 1999). Due to its success, a surfactant modified soil amendment (SMSA)

has been used to create permeable barriers for groundwater remediation (Bowman et al.,

2001).

A series of lysimeters studies were conducted at the University of Florida between

2002 and 2003 to investigate the influence of SMSAs on anion leaching below the

turfgrass rootzone. The objective of this study was to determine the influence of SMSAs

on leached nitrate, phosphate, and ammonium in a simulated USGA putting green.

















CHAPTER 2
LITERATURE REVIEW

Soil Amendments

The USGA has recommended putting greens be primarily sand-based (USGA,

1993). The high sand content of USGA putting greens allows greens to maintain

adequate aeration and drainage while minimizing compaction. Due to the high traffic

typically imposed on USGA greens, these characteristics are crucial to maintaining a

quality-playing surface. However, sand-based greens do have limitations, the most

important of which are low water and nutrient retention (Bigelow et al., 2000). Soil

amendments counteract the tendency of sand-based root zones to be nutrient deficient and

drought (Crawley and Zabcik, 1985). The USGA recommends putting greens be

amended with peat moss at a rate of 85% sand and 15% peat by volume (Beard, 1982).

The addition of peat moss increases the cation exchange capacity (CEC) as well as the

water holding capacity of the growing media. However, peats are organic and are subject

to microbial degradation. Many years of peat decomposition may be detrimental to

putting green performance.

In recent years, superintendents have shown a growing interest in inorganic soil

amendments to use in place of peat. Inorganic amendments are not subject to biological

degradation, and thus are considered to be more stable than organic amendments, which

decompose with time. Many different types of inorganic soil amendments are currently

marketed for golf green construction. These include calcined clays, zeolites,









diatomaceous earths, and water treatment residuals. Characteristics between organic and

inorganic amendments differ greatly; thus each will be considered and discussed

individually.

Peats

The oldest and most widely used organic amendment used on golf courses is peat

(Beard, 2002). Peats are typically mined from deposits located in cool, flooded

environments. Low temperatures decrease microbial activity and can increase peat

accumulation. Flooded conditions further increase the likelihood of peat accumulation by

limiting oxygen availability. Peats can vary dramatically in their characteristics in large

part due to the environment and parent material from which they formed. Peats have

been classified into three types: 1) moss peat, which is from sphagnum, hypnum, and

other mosses; 2) reed-sedge peat, from reeds, sedges, and other swamp plants; and 3) peat

humus, peat of any form that has degraded to the point where no plant parts are

identifiable (Lucas et al., 1965). When investigating six different types of peat, Carlson

et al. (1998) found the pH of these peats varied from 2.9 to 6.2, water retention varied

from 33 to 60% by volume, and the organic matter content varied from 63 to 95%.

Despite these differences in laboratory-analyzed characteristics, no differences were

observed in turf quality when these peats were used to amend putting green root zones.

Benefits of adding peat to a turfgrass root zone include (a) release of soluble

nutrients and gradual release of nutrients through microbial degradation, (b) increase

CEC for nutrient retention and chemical buffering, and (c) increase moisture retention.

Peats provide a number of plant essential nutrients. Comer (1999) reported

Mehlich-I extractable P, Mg, and Ca increased by 575, 525, and 340%, respectively, by

adding peat to USGA sand. Correspondingly, plant uptake of P, Mg, and Ca were higher









in peat amended-sand than the control. These increased nutrients lead to an increase in

total dry matter production of 7%. No differences in extractable K were observed by

Comer, a trend that was also observed by Ok et al. (2003). Ok et al. investigated

creeping bentgrass performance as influenced by three amended root zones and reported

higher levels of P, Mg, and Ca in peat-amended root zones than the control.

Peats are composed of a variety of reactive, organic compounds. Polyphenols,

polyquinones, and polysaccharides are a few compounds found in peat, each of which

possesses hydroxyls, carboxyls, and phenolic groups that dissociate and give rise to a

CEC by weight that is often higher than most inorganic soil amendments (Carrow et al.,

2001). The charge associated with peat is pH dependent and, thus, changes in relation to

the pH of the soil solution. As pH increases, some H ions are neutralized by OH- ions

and the CEC of the peat increases. Conversely, as pH decreases, H ions in solution

become sufficient to saturate negative charges on organic matter and the CEC decreases.

Incorporating peat into a sand-based root zone can increase the root zone CEC by as

much as 425% (Bigelow et al., 2001a). This increase in CEC directly influences nutrient

retention. At 20% (by volume) incorporation, peat can decrease NH4-N leaching from

96% to 37% of applied N (Bigelow et al., 2001a). Ammoniacal-N may then become

available for plant uptake or be oxidized by nitrifying bacteria (Sylvia et al., 1997).

Leaching of cationic nutrients such as K, Ca, and Mg have also been shown to decrease

with peat incorporation (Snyder, 2003). However, additions of peat may increase

leaching of anionic nutrients. Brown and Sartain (2000) observed a 30% increase in

leached P by adding peat to uncoated sand, which may have been attributed to the soluble

P content of peat which effectively increases total soil P.









Due to their fibrous, porous nature, peats can increase total soil porosity and thus

increase soil moisture retention. Critical levels for optimum soil porosities have been

suggested and range from 0.10 to 0.20 (Baver, 1956; Flocker et al., 1959, and Wesseling

and van Wijk, 1957). Currently, the USGA specifies putting green root zones should

have an aeration porosity of 0.15 to 0.30 (USGA, 1993). However, aeration porosity is

typically not uniformly distributed throughout the 30 cm putting green root zone. Taylor

et al. (1997) reported the bottom 9 cm of a sand/peat mixture had 3 to 7% air-filled

porosity while the top 21 cm had 22 to 37%. Similar results were reported by Flury et al.

(1999) in which the lower boundaries of experimental lysimeters were found to remain

near saturation while the upper 80% of the soil columns exhibited a uniform moisture

distribution.

The influence peat has on porosity also affects bulk density. Bigelow et al. (2001b)

found incorporating peat (10% by volume) with sand decreased bulk density from 1.66 to

1.54 g cm3, increased total porosity from 0.41 to 0.47, and increased air-filled porosity

from 0.24 to 0.28. This increase in porosity allows sand amended with peat to retain

more water than sand alone. Sphagnum peat moss has been found to hold 10-14 times its

own weight in water (Hummel, 2000). When incorporating peat, soil moisture contents

have been found to be higher than sand amended with zeolites and calcined clays

(Bigelow et al., 2001b). After saturation followed by drainage for 48 hours, sand/peat

mixtures were found to retain as much as 46% more water than sand alone (Taylor et al.,

1997).

The organic matter associated with peat incorporation also influences plant

available water (PAW). Hudson (1994) found the correlation between OM and PAW to









be significant (r2= 0.79), and that as OM content increased from 0.5 to 3%, PAW more

than doubled. However, peat incorporation may not always be beneficial to PAW.

McCoy (1992) found that Canadian sphagnum peat retained water within organic matter

pores beyond that available to the plant. He further suggested that much of the water

retained by organic amendments with fiber contents in excess of 45% is unavailable to

plants. In the same study, Canadian sphagnum peat had a fiber content of 54%.

Addition of peat to sand-based root zones increases plant growth and soil

productivity (Lucas et al., 1965). Incorporation of sphagnum peat to uncoated, coated,

and artificially coated sand shortened turf establishment by 14 days and increased yield

by 50% (Snyder, 2003). Following establishment, a 12-week maintenance study was

conducted in which peat-amended pots produced 24% more dry matter than sand alone.

These findings are in contrast to Smalley et al. (1962) who investigated the influence of

peat and calcined clay (10% by volume) on Tifgreen bermudagrass and reported neither

had any effect on dry matter yield. During this one-year study, 1022 and 484 kg of N and

K ha-1 were applied, respectively. At this fertilization rate, it is likely that turf on both the

control and treated plots received adequate nutrients, and the influence of peat and

calcined clay (CC) was minimized thus, no differences were observed. Other researchers

have reported different results. Cooper et al. (1998) investigated the influence of four

humic substances including peat on root mass and nutrient uptake of creeping bentgrass.

They reported little or no difference in root mass or N, K, Ca, Mg, or Fe uptake between

any humic compounds or the control.

Calcined Clays

Mined clays, typically smectites, are heated to 800 -900 C to harden the

amendment and increase their stability (Bigelow et al., 1999). The clay is then sieved to









achieve a desired particle size and sold as calcined clays. Calcining the clay allows the

amendment to maintain its beneficial characteristics such as CEC and moisture retention

while eliminating shrinking and swelling, which can be detrimental to putting green

performance. Calcined clay has the advantages of withstanding compaction, providing

high infiltration, and allowing good aeration (Letey et al., 1966).

Cation exchange capacity of calcined clays arises from isomorphic substitution of

Al+3 for Mg+2 in the octahedral sheet and, thus much of the charge is independent of pH.

Reported CEC values of calcined clays vary from 24-34 cmol(+)/kg (Richardson and

Karcher, 2001; Carrow et al., 2001). Field plots modified with calcined clays have

shown increases in CEC as well as increases in nutrient retention. Li et al. (2000)

observed an 8% increase in CEC when comparing plots amended with calcined clays to a

control. They also observed a 100% and 30% increase in exchangeable K and Mg,

respectively. In the same study, exchangeable Ca decreased by 4%, a trend which was

also observed by McCoy and Stehouwer (1998). The increase in CEC reported by Li is

lower than results reported by Bigelow et al. (2001a). Exchange capacities in their study

increased from 0.8 in the control to 2.4 cmol(+) kg-1 in the calcined clay amended plot.

Calcined clay was further shown to increase CEC above a zeolite treatment which was

reported to be 1.6 cmol(+) kg1.

Calcined clays are incorporated with sand not only to increase the CEC, but also to

aid in moisture retention. When sand is mixed with CCs (15% by volume), porosity has

been reported to increase by as much as 15% over sand alone (Waltz et al., 2003).

Correspondingly, total water retained after drainage also increased from 19.9 to 23.1 cm

in sand and CC plots, respectively. Li et al. (2000) reported sand modified with calcined









clay retained 13% more water than sand alone. Li theorized that calcined clay probably

provided for a more favorable ratio of macropores to micropores which equaled 3.77.

Macropores play a vital role in hydraulic conductivity while micropores are more

responsible for water retention (Rowell, 1994). Root zone modifications that alter pore

space distribution and improve aeration and water conditions can favor turfgrass growth

(Waddington, 1992).

Turf establishment and growth are generally increased by incorporating CCs into

a sand-based rootzone. Waltz and McCarty (2000) conducted an experiment involving

the incorporation of soil amendments and their influence on turf establishment. They

found plots containing sand and CC achieved 75% and 100% establishment, respectively,

at 9 months after seeding. Furthermore, calcined clay treatments produced a higher

visual rating of density and color than plots with sand alone. However, these findings

differ from those reported by Smalley et al. (1962). They investigated the influence of

CC on turf yield and quality and reported that incorporating CC decreased yield and

quality. They observed this effect was particularly evident during a drought period, and

concluded the decrease in yield and quality likely resulted from excessive aeration and

consequent reduction in available moisture.

Zeolites

Zeolites are naturally occurring minerals that can form in a variety of

environments. The most common zeolite used for agricultural purposes is clinoptilolite

because it is the most common zeolite found in soil parent material (Boettinger and Ming,

2002). Like quartz, zeolites are tectosilicates, thus its structure prevents any shrinking or

swelling that sometimes occurs with other soil minerals. However, unlike some

tectosilicates, zeolites are porous, thus they tend to have low densities (1.9-2.2 g cm-3)









(Breck, 1974). Their porous nature also increases their surface area and its cation

exchange capacity. Clinoptilolite has been shown to have a void volume near 34% and a

CEC as high as 220 cmol(+) kg-1 which arises from isomorphic substitution of Al3+ for

Si4+ (Meier and Olson, 1988). The internal pores of clinoptilolite are small enough to

limit the adsorption of some larger ions, thus clinoptilolite is highly selective for K+ and

NH4+ relative to Na+ or divalent cations such as Ca2+ and Mg2+ (Ming and Mumpton,

1989). Goto and Ninaki (1980) determined the ion-exchange selectivity order of natural

zeolites to be K+ > NH4+ > H+ > Na+ > Sr2+ > Ca2+ > Mg2+ > Li+. The strong affinity

zeolites have for K+ and NH4+ has prompted municipalities to use zeolites for the removal

ofNH4+ from sewage (Mercer et al., 1970).

Their high CEC is the primary reason zeolites have been used to amend putting

green root zones. Addition of zeolites to sand-based root zones has been shown to

increase the CEC by as much as 200 fold (Huang and Petrovic, 1994). This increase in

CEC helps to buffer the soil and increase retention of nutrients such as K, NH4, Ca, and

Mg. Ferguson et al. (1986) observed that zeolite amended soils produced higher turf

quality than non-amended soils. It was hypothesized that NH4 produced from urea

applications was adsorbed by the clinoptilolite and was slowly released, which resulted in

a more healthy turf. In defense of this theory, an incubation study was conducted in

which NH4-N was mixed with clinoptilolite amended USGA sand. After 25 days of

incubation, NH4+ loss due to nitrification, denitrification, and/or volatilization was lower

in clinoptilolite-amended sand than vials containing sand alone. This was attributed to

the internally sorbed NH4+ being inaccessible to denitrifying bacteria (Ferguson and

Pepper, 1987).









Decreased NH4 leaching from zeolite-amended soils has also been attributed to the

increased CEC that accompanies zeolite incorporation. When mixed at a rate of 50 g kg-

1, clinoptilolite has been shown to decrease NH4-N leached from 168 to 29 mg NH4-N

(Mackown and Tucker, 1985). A number of studies have reported reductions in NO3

leaching with use of clinoptilolite. Huang and Petrovic (1994) not only reported that

NO3- and NH4+ leaching was 86 and 99% lower, respectively, in zeolite-amended sand

than sand alone, they also observed the fertilizer use efficiency of creeping bentgrass

increased as much as 22%. Lewis et al. (1984) reported pots containing a loamy sand soil

amended with clinoptilolite reduced NO3- leaching by 33% compared to the control when

fertilized with ammonium sulfate. These reported reductions in NO3- leaching are likely

attributed to NH4+ release from clinoptilolite being limited by diffusion and cation

exchange reactions (Semmens, 1984; Allen et al., 1995).

The capacity zeolite has to retain cations may not always be beneficial. Some

research suggests that the energy at which NH4+ is held by zeolite may be enough to

render NH4+ inaccessible to plants. Ferguson et al. (1986) observed better bentgrass

establishment on 5% than on 10% clinoptilolite amended plots. While this observation

was attributed to high sodium content, more recent research suggests that high sodium

levels may not be solely responsible for the decreased establishment, but rather N

removal by NH4+ sorption which effectively reduces plant available N. Regardless, other

studies have shown that the influence of zeolite on creeping bentgrass establishment

compares favorably with peat (Nus and Brauen, 1991).

Zeolite incorporation typically increases turf establishment. Miller (2000) reported

that bermudagrass was found to establish more rapidly and had greater growth on









ZeoPro-amended plots than plots containing 100% sand and other rootzone mixtures.

The higher nutrient levels accompanying incorporation of zeolite have been associated

with more rapid establishment and high quality ratings of creeping bentgrass (Ok et al.,

2003). It should be mentioned that studies conducted by Miller (2000) and Ok et al.

(2003) involved the use of zeolite which contained as much as 0.1% N. Nitrogen loaded

zeolite may act as an N source instead of an N sink which may increase turf growth and

establishment. Natural zeolites do not contain N, thus turf grown on natural zeolite may

react differently than turf established on N-loaded zeolite. This concept was also

speculated by Ok et al. (2003). Nus and Braun (1991) investigated the incorporation of

sawdust, peat, zeolite on establishment of creeping bentgrass and reported peat and

zeolite were equally effective at increasing turf establishment.

Diatomaceous Earths

Algae, predominantly of marine origin, are responsible for the formation of

diatomaceous earths (DE). Diatoms are microscopic, single-cell plants, which join to

form sedimentary rock composed of fossilized skeletal remains of diatoms (Fresenberg,

1999). Chemically, DEs are like silica sand in that they are about 90 percent silica (SiO2)

with minor amounts of alumina (A1203) (Mannion, 1996). Some DEs are calcined during

manufacturing. Calcined DEs are 50 percent harder and suffer one-quarter the wet

attrition loss of uncalcined DEs (Mannion, 1996).

DEs are porous and, thus, have low bulk densities and can retain up to 150% its

weight in water. Sands amended with DEs have been reported to have higher total

porosity and overall water retention than sands amended with zeolite (Bigelow et al.,

2004). However, Bigelow also reported that DE amended sand possessed the same

porosity and water retention as peat and calcined clay amended sand. These findings









were similar to those reported by Waltz et al. (2003). Waltz investigated the hydraulic

properties of several soil amendments including DE. Waltz reported that water retained

at field capacity was greater in sand amended with peat than with DE. However, as plots

were allowed to dry, DE and peat amended sand held more water than CC amended sand.

Waltz further observed that DE and peat amended sand held more water in the top 15cm

of a 30 cm profile than CC amended sand. While turf growth was not investigated, Waltz

speculated that amendments that slow water movement and retain more water in the

upper portion of the rootzone would result in turf with less water stress than turf grown

on media that retained less water due to rapid drainage.

The influence of DEs on turf growth has been shown to be most pronounced during

times of drought. Wehtje et al. (2003) evaluated bermudagrass growth as influenced by

DE, zeolite, and calcined clays incorporated with sand at five rates. Their investigation

consisted of measuring turf yield under luxury water and nutrient application and under

drought conditions. When bermudagrass was supplied with adequate water and nutrients,

sand amended with DE only produced more dry matter than un-amended soil at the

highest incorporation rate (100% DE). However, under drought conditions DE increased

dry matter production which, in general, increased with increasing incorporation rate.

Experimental conditions during this study were variable. However, Wehjte et al.

concluded that improvement in bermudagrass performance in amended sand relative to

soil alone was most likely related to increased water-holding capacity. This theory was

not only based upon their findings, but also upon previous research conducted by Ralston

and Daniel (1973). During their research, Ralston and Daniel investigated the influence

of calcined clay and DE on creeping bentgrass. After two 15 day dry down periods, they









found plots containing DE maintained normal growth without additional water

applications while plots containing calcined clay required water after 5 days. More

recent research has also shown turf grown on DE amended sand produced better coverage

and more dry matter than CCs or peat during times of drought (Waltz and McCarty,

2000).

Water Treatment Residuals

Water treatment facilities use FeSO4 to remove humic substances from water for

human consumption. Water treatment residuals (WTRs) are products of this process.

WTRs contains humic and fulvic acids as well as iron, which is a plant essential element

(Salisbury and Ross, 1992).

In general, WTRs have a positive influence on soil moisture. Bugbee and Frink

(1985) observed increases in soil moisture retention and aeration from WTR

incorporation with soil. Increases in soil moisture retention were also observed by

Rengasamy et al. (1980) and were attributed, in part, to the increase in soil aggregate

stability which accompanied WTR incorporation. Increasing soil structure by adding

WTRs has also been shown to increase soil drainage (Scambilis, 1977) which is crucial to

putting green performance.

Applications of WTRs have been shown to increase plant growth. Basta et al.

(2000) investigated the influence of WTRs on dry matter yield of bermudagrass. They

reported bermudagrass grown on WTRs produced a yield of 26 g pot- while turf grown

on native soil only produced 15 g pot-f. WTRs used in the Basta study contained 140 and

130 ppm N03-N and NH4-N, respectively. High N levels along with high levels of P, K,

Ca, Mg, and Fe were likely the cause of the observed increase in turf growth. A similar

explanation was given by Elliott and Singer (1988) when they studied the influence of









WTR on growth of tomato and observed an increase in yield following the incorporation

of WTR. Ippolito et al. (1999) investigated the influence of co-application of biosolids

with WTRs on biomass yield of two range grasses. They concluded that increasing the

rate of WTR incorporation increased biomass production for both turf species. However,

in general, turf grown on plots containing less than 150 g kg-1 WTR did not show yield

increases. Lower incorporation rates were used by Heil and Barbarick (1989) when

investigating WTR incorporation and its effect on the growth of sorghum-sudangrass. By

increasing WTR incorporation rate from 0 to 20 g kg-1, Heil and Barbarick increased turf

dry matter production from 6 to 20 g pot-f. They attributed this increase in yield to an

increase in plant available Fe which was not observed in the control pots, which exhibited

Fe-deficiency symptoms. Other researchers have observed limited influence of WTRs on

plant growth. Geertsema et al. (1994) applied WTR at three rates of 0, 36, and 52 dry Mg

ha-1 to loblolly pine (Pinus rigida Mill.) and reported no differences in plant growth

between amended and unamended plots after 30 months of growth.

Water-Use-Efficiency

Water-use-efficiency (WUE) is defined as the quantity of dry matter produced per

quantity evapotranspired water (g dry matter mL ET-1). WUE may be influenced by

plant species, nutrient availability, water availability, or cultural management practices.

Many studies have shown that water use is directly related to available soil

moisture, and, to a point, WUE increases as soil moisture decreases. Youngner et al.

(1981) investigated water use of two cool-season and two warm-season grasses. Soil

moisture was maintained according to tensiometer readings of 0.015, 0.035, and 0.055

MPa. Regardless of turf species, water use was maximized under the highest soil

moisture tension. Danielson et al. (1981) measured the water use of Kentucky bluegrass









under differing soil moisture levels including 100%, 80%, and 70% field capacity. They

reported irrigation of 80% field capacity reduced water consumption by 20% with only

minor reductions in turf quality. Similar results were reported by Meyer et al. (1985).

They also used varying irrigation rates from 100 to 60% ET estimated values and

reported that when irrigation rates were dropped to 80% ET, turf quality rates dropped

only 3% for cool-season and 5% for warm-season grasses. Stout et al. (1988)

investigated the influences of soil and N on WUE of tall fescue and concluded that based

upon the regression of WUE and soil variables, the influence of soil on WUE increases

during periods of limited water availability. This indicates that when water is limited,

differences in WUE between different rootzone media may be more pronounced.

Differences between WUE not only exist between different plant species, but also

between different cultivars or varieties within a species. C-4 plants are more efficient

users of water than C-3 plants during periods of high light and temperature (Black et al.,

1969). This is due to more efficient carbon assimilation in C-4 plants. C-4 plants are

able to take up more CO2 through their stomata, thus less water is lost for every CO2

molecule assimilated (Hull, 1992). WUE of C-4 grasses has been reported to be as much

as 2x higher than C-3 grasses (Schantz and Piemeisel, 1927). These results were similar

to Fu et al. (2003) who reported 'Meyer' zoysia to have a WUE more than 3x higher than

'Falcon II' tall fescue.

Cultural practices that influence WUE include: irrigation frequency, mowing

height, and fertility program. Minner (1988) observed an increase in water use rate when

irrigation frequency was increased. Minner also reported water use increased as mowing

height increased which was attributed to an increase in leaf area index. Biran et al.









(1981) increased cutting height from 3 to 6 cm and found similar results with Festuca

arundinacea and Lolium perenne. They reported a permanent increase in water

consumption and growth, as well as an increase in chlorophyll per unit weight in

clippings. However, Biran did not find any permanent increases in water consumption or

plant growth in C-4 turfgrasses.

In general, the greatest single factor influencing WUE is soil fertility. Stout et al.

(1988) studied the influence of 3 soils and 3 N rates on WUE of tall fescue. When N

rates increased from 45 to 90 kg ha-1 WUE increased by as much as 50%. Stout reported

during fall harvests, N fertility was always the major component influencing WUE of tall

fescue. Feldhake et al. (1983, 1984) used two N fertilization levels to determine the

influence of N on water use of Kentucky bluegrass. They reported higher ET levels from

turf supplied with 4 kg of N 1000 m-2 mO-1 than from turf supplied with 4 kg of N 1000

m-2 yr1. A more recent study investigated the influence of 4 soils, 3 N rates, and 2 turf

species and concluded N fertilization increased WUE at all application rates with the

highest application rate having the greatest influence on WUE (Stout, 1992). The

influence of N fertility on WUE has been shown to be most pronounced when water is

limited. Stout and Schnabel (1997) investigated WUE of perennial ryegrass over a two-

year period. During year one, when rainfall and irrigation supplied water were

considered to be adequate for turf growth, N fertility increased WUE 154%. During year

two, when rainfall and irrigation were low, N fertility increased VWUE 455%.

Nitrogen in the Turfgrass Environment

In order to limit N leaching and the environmental impact of N fertilization, one

must thoroughly understand the N cycle (Fig. 2-1) and the transformations that N









undergoes in a dynamic soil system. These processes include: plant uptake, soil retention

and microbial immobilization, runoff and leaching, or atmospheric loss (Petrovic, 1990).

N Transformations in Soil

Soil N exists primarily in two forms: organic and inorganic. Organic N is present

in a variety of compounds including proteins and amino acids. Forms of inorganic N

include NH4+ and NO3- and are produced from the aerobic oxidation of organic N or from

fertilizer input. From the standpoint of environmental impact and leaching, NH4+ and

NO3- are the most important because it is these compounds that are mobile in the soil

solution (Follett, 1989).

Organic N is converted to NH4+ by heterotrophic microorganisms during

mineralization. N mineralization is strongly influenced by moisture and 02 content.

Maximum N mineralization occurs between 50 and 70% water-filled pore space (Havlin

et al., 1999). Once in inorganic form, NH4+ may take a variety of paths including plant

uptake, mineral fixation, volatilization, or nitrification. Nitrification is the conversion of

NH4+ to NO2- and then to NO3-. Nitrification consists of two reactions. The first reaction

is mediated primarily by microorganisms belonging to the group Nitrosomonas.

2NH4+ + 302 2N02- + 2H20 + 4H+

The second reaction oxidizes nitrite to nitrate and is mediated primarily by organisms in

the Nitrobacter group.

2NO2- + 02 2 N03

Both reactions require 02, thus each reaction is highly dependent upon aerification

and moisture content. In aerated soils, nitrification is normally a rapid process requiring

only days to convert the NH4+ to NO3-. During a 53 week incubation study to investigate










mineralization rates in a variety of Florida soils, Reddy (1982) observed low levels of

NH4+ in effluent of soil columns and found high concentrations of NO3. These results

were attributed to rapid nitrification of the mineralized NH4+. Tate (1977) also reported

rapid nitrification occurred in well-aerated soils which may result in little or no NH4

accumulation.


N20
NO
N2 Plant Uptake Plant and Animal
Fertilizers A Residue





NH3
Volatilization

Soil Organic
N03-/NH4+ Matter




S00


NH4+- R-NH2



NH4
Fixation





N03 NH4
---------------NO H4
Nitrification


Leaching

Figure 2-1. The Nitrogen Cycle (Havlin et al., 1999)









Leached N

The most common source of N03 pollution of ground and surface water is

agriculture (Halberg, 1987; Pratt, 1984). While turfgrass is not often thought of as an

agricultural crop, golf courses and home lawns are maintained according to many of the

same practices and, thus they are also sources of nitrate leaching (DeRoo, 1980; Morton

et al., 1988).

Susceptibility of USGA putting greens to N leaching has been well documented.

Snyder et al. (1984) investigated the influence of moisture-sensor irrigation on N

leaching and reported 56% of applied N from ammonium nitrate was leached under a

daily irrigation schedule. They also observed 85 to 98% of leached N occurred as N03-N

and that 75% of leached N occurred within 20 days of application. Bigelow et al. (2001a)

used several laboratory studies to monitor leaching losses of N from a sand-based

medium amended with 20% peat by volume and reported addition of peat decreased

NO3-N leached from 98 to 95% of that applied, which was statistically significant. Peat

had a greater influence on leached NH4-N dropping the percent NH4-N lost from 96 to

37% of that applied. Because of its positive charge, NH4-N can adsorb to soil particles

and, thus may not leach readily. However, Sartain (1990) applied (NH4)2SO4 to bare soil,

encouraged leaching, and found after 112 days, 80% of applied N leached with 68%

being NH4-N. In most agricultural soils, N leaching is primarily as N03-N simply due to

the rapid oxidation of NH4-N to N03-N.

Because all N leaching occurs in soil solution, soil water content plays a major role

in N movement through the soil profile. In general, N leaching potential increases as

water application increases (Morton et al., 1988). Starrett el al. (1995) investigated two









irrigation regimes on N leaching and found 30 times more N leached when irrigation

rates were increased by a factor of four.

Phosphorous in the Turfgrass Environment

Phosphorus is a macro nutrient used by plants to produce ATP, which in turn is

used as an energy source which drives many metabolic processes. Phosphorus exists in

soil solution primarily in anionic form (Fig. 2-2). Additions of P to soil solution arrive

via desorption from soil exchange sites, dissolution of primary and secondary minerals,

and mineralization of organic matter. In most agronomic situations, plant uptake and

leaching are the only process whereby P is removed from the soil system.

P Reactions in Soil

Total P in most surface soils varies but is generally between 0.005 and 0.15%

(Havlin et al., 1999). Of the total P, only a small portion actually exists as solution P

which is that portion available for plant uptake. Solution P is maintained by dissolution

of primary and secondary mineral, mineralization from organic matter, and by desorption

from mineral and clay surfaces (Fig. 2-2). These processes are responsible for

replenishing the soil solution P that is taken up by the plant. When these processes

cannot adequately supply P, fertilizers must be used to artificially increase solution P

concentrations. However, when solution P exceeds the amount needed by the plant, the

potential for P leaching increases.

Leached P

Phosphorus is considered to be a critical nutrient responsible for eutrophication of

surface water bodies. Eutrophication of surface water has been identified by the USEPA

as a major cause for quality degradation of surface waters which may lead to problems












Plant and Animal
Fertilizer Plant Uptake Residue




Adsorbed P Adsoption

(Labile) Soil
Desorption Immobilization Organic
Matter
Secondary
Minerals Solution P Mineralization
Precipitation (Nonlabile)
Fe/AlPO4 HPO42
CaHPO4 Dissolution HP04
(Nonlabile) .
(labile)
Primary 1
Minerals Dissolution

(Nonlabile)


Leaching



Figure 2-2. The P cycle (Havlin et al., 1999).

with their use for fisheries, recreation, industry, or drinking water (O'Connor and Sarkar,

1999). Periodic surface cyanobacteria blooms occur in drinking water and may pose a

serious threat to livestock and humans (Lawtin and Codd, 1991; Martin and Cook, 1994).

In recent years, a number of studies have investigated P leaching. Brown and

Sartain (2000) used several P fertilizers to investigate P retention in a variety of

sand/amendment mixtures. They reported P leached from an uncoated sand/peat

rootzone (85:15 by volume) was less than 7% of applied P. However, they also observed









twice as much P leached from peat amended sand than from sand alone. These finding

are somewhat lower than that observed by Shuman (2001). Shuman investigated P

leaching from a simulated USGA putting green in an environmentally controlled

greenhouse and reported 27% of applied P was lost via leaching. Uncoated sands

typically retain less P than coated sands. Harris et al. (1996) investigated the P sorption

characteristics of coated and uncoated sands via a number of adsorption and desorption

experiments. They reported the presence of sand grain coatings enhanced P adsorption

and resistance to desorption.

Soil amendments have been used to reduce P concentrations in ground water.

Porter and Sanchez (1992) reported that P sorption in a Histosol was correlated with soil

ash and CaCO3 content. Coale et al. (1994) applied gypsum and WTR and investigated

their influence on P leaching. They reported decreased leachate P concentration from

both amendments with gypsum causing the greatest decrease in leached P.

Hexadecyltrimethyammonium

Hexadecyltrimethylammonium (HDMTA) [CH3(CH2)15 N(CH3)3] is an amphoteric

compound containing both hydrophobic and hydrophilic components. Each molecule

possesses a positively charged head and a 16-carbon tail. The head groups of HDTMA

are similar to NH4+; however, three protons in NH4+ are replaced by three methyl groups

while the fourth is replaced by the tail (Fig. 2-3) (Li and Bowman, 1997). Its unique

properties allow the surfactant to bind to solid particles that possess a CEC and

effectively reverse their charge, thus the particle is now capable of adsorbing many

anionic compounds.











H3 H3
C C

N H2 H2 H2 H2 H2 H2 H2 H3
C C C C C C C C
/ \/\/\/\/\/\/\/\/
C C C C C C C C C
H3 H2 H2 H2 H2 H2 H2 H2 H2




Figure 2-3. Hexadecyltrimethylammonium.

Bi-layer Formation

Bi-layer formation involves two steps. The first step involves direct attachment of

HDTMA micelles to the amendment surface via electrostatic bonding. The second step

involves HDTMA surface rearrangement, which is directly related to the initial surfactant

input in relation to the ECEC of the amendment. If the initial surfactant input is less than

the ECEC, each micelle will dissociate to form a monolayer. If surfactant input is greater

than the ECEC but less than twice the ECEC, an incomplete or 'patching' bi-layer forms.






Positive Head
Group



24-26 A





SAmendment
Surface


Figure 2-4. Schematic of HDTMA bi-layer formation.









If surfactant input is greater than twice the ECEC, a complete bi-layer will form (Fig. 2-

4). The initial step is relatively fast generally requiring less than one hour. The second

phase involves intraparticle diffusion, which can require as many as 48 h to achieve bi-

layer formation depending upon the ECEC of the solid phase (Li, 1999). Cation

exchange is responsible for retaining the lower layer while hydrophobic bonding causes

formation of the upper surfactant layer (Li and Bowman, 1997).

Anion Sorption

Recent literature indicates HDTMA-modified solids are effective sorbents for

multiple types of contaminants, such as chromate, naphthalene, perchloroethylene, and

nitrate (Li and Bowman, 1997; Nzengung et al., 1996). While investigating the HDTMA

counterion influence on chromate sorption, Li and Bowman (1997) observed sorption

isotherms were well described by the Langmuir equation. Chromate sorption maximum

was reported to be 16 mmol kg-1. More importantly, Li and Bowman found the exchange

ability of the counterion on HDTMA was more influential on chromate sorption than the

initial HDTMA loading concentration. Other studies investigating NO3s sorption have

found similar results. Li et al. (1998) investigated NO3s sorption isotherms, which like

CrO42-, were well described by the Langmuir equation. Sorption maximum for NO3s was

100 mmol kg-1. The same study produced results that indicated NO3s is more suitably

sorbed than CrO42-, which seems unlikely since the divalent Cr042- has a higher charge

density than the monovalent NO3- and thus should be more selectively sorbed.

Investigators theorized that because sorbed HDTMA onto an amendment surface does

not form a rigid structure, the stability of the HDTMA-CrO4 ion pair might be lower than

the HDTMA-NO3 ion pair, which may explain why NO3s is more suitably sorbed than

Cr042-
Cr04 -









Stability

The resistance of surfactant-modified soil amendments (SMSA) to biological

degradation or physical weathering is crucial to their long-term effectiveness.

Investigations into the influence of aqueous quaternary ammonium cations (QACs) on

microbial growth have found aqueous QACs to be biocidal. Gilbert and Al-taae (1985)

investigated a number of QACs with varying chain lengths with 4-22 carbons and

reported bacteria strains were most sensitive to QACs containing 14 carbon tails while

yeast and fungi were most sensitive to QACs containing 16 carbon tails. Microbial

growth was least inhibited by QACs with shorter tails. In general, QACs with longer

tails are more biocidal than those with shorter tails (Korai and Takeichi, 1970). Although

QACs like HDTMA have been shown to be biocidal, they can be degraded microbially.

Dean-Raymond and Alexander (1977) investigated the biodegradation of 10 QACs

including HDTMA using sewage and soil as their sources for microorganisms. They

reported decyltrimethylammonium and HDTMA were both metabolized by

microorganisms from both sources. In the same study, Decyltrimethylammonium

bromide was observed to be the sole carbon source for a mixed population of two

bacteria from soil. Each of the preceding cases involved investigations on aqueous

QACs. The influence of sorbed QACs on microbial growth is quite different. A study

was conducted in New Mexico which involved microorganism growth on agar plates

after being inoculated with a mixture of surfactant-modified zeolite (SMZ) and activated

sewage sludge (Li et al., 1998). After 17 weeks of incubation, microorganism growth

remained essentially the same between treated plates and the control. Toxicity from

QACs is primarily from the alkyl chain (Korai and Takeichi, 1970). Surfactant-modified

soil amendments which have been modified to ensure bi-layer formation have very few









tails exposed to soil solution, thus toxicity of SMSA is very low or non-existent (Li et al.,

1998).

Investigations into the physical stability of SMSA are somewhat limited. However,

Li et al. (1998) used SMZ in a series of leaching experiments to determine the extent of

bi-layer removal. They used two types of water, Type I had an ionic strength of zero, and

type II used K2CrO4 to increase the ionic strength to 8mM. They reported HDTMA

desorption to be 0.34 mmol kg-1 pore volume-1 from type I water and 0.14 mmol kg-1 pore

volume-1 from type II water. Based on these observations, they predicted that 65% of

sorbed HDTMA would remain after 500 pore volumes of type II water. This hypothesis

was later verified in a laboratory column test.














CHAPTER 3
MATERIALS AND METHODS

This research consisted of a variety of amendment characterization studies and two

glasshouse studies.

Characterization Studies

Characterization studies were conducted in a number of soil laboratories at the

University of Florida from fall 2001 to fall 2004.

Cation Exchange Capacity

Cation exchange capacity for each amendment and sand/amendment mixture was

determined via the ammonium acetate pH 7.0 method (Soil Survey Laboratory Staff,

1996). Five grams of soil media were placed in leaching tubes and leached with 25 mL

of 1 M NH4OAc. Leaching tubes were then closed and an additional 25 mL 1 M

NH4OAc were applied and soil media remained in solution for 48 h. Leaching tubes

were then opened followed by two applications of 100 mL ethanol. A total of 60 mL 1 M

KC1 were leached through each tube, collected, brought to 100 mL volume, and analyzed

for NH4+.

Moisture Retention

Moisture release curves were determined for each sand mixture according to the

process described by Klute (1986). Field plots were originally established with the

intention of mimicking the glasshouse studies. Each plot contained rootzones

corresponding to the rootzone of glasshouse pots. However, due to experimental

difficulties during the first 3 months of the study, establishment was delayed.









Furthermore, once data began to be collected from the plots, excessive rainfall from both

hurricanes Frances and Jeane heavily skewed the data. Thus, no results from field plots

were included in this study. However, since removing usable cores from glasshouse pots

was not possible due to the rootzone depth required, cores were taken from the field plots

using a brass ring (3 cm high x 5.56 cm diameter). The ring was placed on a half-bar

porous ceramic plate, which was then placed into a Model 1400 Tempe pressure cell

(Soil Moisture Equipment, Santa Barbara, CA). Tempe cells were placed in a water bath

until each cell achieved saturation. The cells were then placed on a rack and connected to

a hanging-water column pressure system. Pressures applied corresponded to 0, 3.5, 10,

15, 20, 25, 30, 35, 50, 100, and 345 cm water (1 bar per 1035 cm water). After the final

pressure of 15 bar (wilting point), the cell was opened, the brass ring was removed, and

the soil was weighed. In order to conduct statistical analysis, two soil cores were used as

replications.

Sorption Isotherms

All sorption isotherms followed procedures outlined by Li (1999). Nitrate-N, NH4-N,

and P sorption isotherms were conducted on HDTMA-coated and uncoated zeolite (Zeo

Inc., McKinney, Tx) and two calcined clays [Soil Master Plus (Sport Turf Supply, Inc.,

Midland City, Al.), Profile (Profile LLC)], which will be referred to hereafter as calcined

clay 1 and calcined clay 2, respectively. Nitrate isotherms were prepared by adding 0.5

grams of each amendment to 10 mL of solution containing 0, 10, 20, 100, 200, and 500

ppm N03-N to achieve loading rates of 0.2, 0.4, 2.0, 4.0, and 10.0 g kg-1. Ammonium

isotherms were prepared by adding 0.25 grams of each amendment to 20 mL of solution

containing 50, 100, 200, 500, and 1000 ppm NH4-N to achieve loading rates of 0, 4, 8,

16, 40, and 80 g kg-1. Phosphorus isotherms were prepared by adding 1.0 g of each









amendment to 10 mL of solution containing 0, 10, 20, 100, 200, and 500 ppm P to

achieve loading rates of 0.1, 0.2, 1.0, 2.0, and 5.0 g kg1. Samples for each isotherm were

shaken on a mechanical shaker for 48 hours to achieve equilibrium. Samples were then

centrifuged for 15 minutes at 4000 rpm to yield a clear supernatant. Nitrate and NH4-N

solutions were analyzed using an Alpkem RFA-300 auto analyzer (IRAMA Corporation,

Milwaukie,OR), and P solutions were analyzed colorimetrically.

Surfactant Loading

Surfactant loading followed procedures outlined by Li and Bowman (1997).

Previous analysis produced CEC values for each amendment, which were used to

determine the ratio of solid to solution. Due to financial and equipment restraints, final

solution concentration analysis of HDTMA was not possible, thus, the amount of

amendment added to solution was divided by 2 to ensure bi-layer formation. The

amounts of amendment used during surfactant loading were 71, 544, and 350g of zeolite,

CC1, CC2, respectively. These amounts were determined to be the maximum amount of

amendment, based upon each amendment's CEC, that could be added to HDTMA

solution while assuring bi-layer formation. Amendments were placed in 2 L Erlenmeyer

flasks, which were then filled to volume with 2 L of 0.066 M HDTMA solution. Each

flask was stirred for 24 h by using a magnetic star bar and plate. Following equilibrium,

the supernatant was removed, amendments were washed with 5 pore volumes of

deionized water, and amendments were allowed to air-dry.

Thermal Analysis

Thermal gravimetry (TG) analysis cannot only be used to determine OM content,

but it can also be use as an indicator of particle stability. Compounds that lose little

weight when subjected to increasing heat are considered to be more thermally stable than









compounds that exhibit weight losses. It has been stated that the greatest strengths of

inorganic amendments are their resistance to degradation and breakdown (Waltz and

McCarty, 2000). Each amendment was subjected to TG on an Omnitherm Corporation

instrument (Arlington Heights, IL) with a nitrogen gas purge. Temperatures ranged from

25-600 C with a ramping rate of 20 C min- (Amonette, 2002).

HDTMA was subjected to thermal analysis to determine the temperature at which

oxidation occurred (Fig. A-i). This temperature was then used when analyzing SMSA to

determine the extent of surfactant coating. Surfactant coating was determined according

to eq. 3.3.

S = (A/0.85) x 10,000 mgkg-1 eq. 3.3.

Where: S = amount HDTMA sorbed (mg kg-1)
A = weight loss due to oxidized HDTMA (%)
B = amount of HDTMA that oxidizes (%)



From thermal analysis, effective anion exchange capacity (EAEC) was determined

according to eq. 3.4.

{[(C x SHDTMA) /2 ] /MWN } x 100 = cmol kg1 eq. 3.4.

Where: C =MWN / FWHDTMA-(MWBr)/2 (%)
SHDTMA = HDMTA sorbed (g kg-1)
FWHDTMA = formula weight of HDTMA (g mole1)
MWN = molecular weight of nitrogen (g mole1)
MWBr = molecular weight of bromide (g mole1)


Assumptions made during determination of EAEC included: 1.) percent HDTMA

oxidation from SMSA was equal to the percent oxidation of pure HDMTA, 2.) all









surfactant sorbed by amendments was in a bi-layer formation, and 3.) after bi-layer

formation, all anion exchange sites in solution equaled V2 the total exchange sites and

were occupied by Br1.

X-Ray Diffraction

In order to determine mineral composition, each amendment was subjected to x-ray

diffraction using a computer-controlled x-ray diffractometer equipped with a stepping

motor and graphite crystal monochromator (Nicolet I2/L11 Polycrystalline X-Ray

Diffraction System, Madison, WI). Amendments were crushed using a mortar and pestle

then placed in a side-packed powder mount with an Al-glass holder. Samples were

scanned from 2 to 400 20 at 20 20 per minute using CuKa radiation (Amonette, 2002).

Nutrient Analysis

All amendments and sand mixes were analyzed for P, K, Ca, Mg, Fe, Mn, Zn, and

Cu. Analysis followed procedures outlined by Olsen and Sommers (1982). Five grams

of each amendment (3 g of peat) were extracted using 20 mL of Mehlich-I solution

(0.025 M HC1 and 0.0125 M H2S04), then shaken for five minutes on a mechanical

shaker. Samples were then filtered with a Whatman no. 42 filter paper and collected in

25 mL scintillation vials. Samples were analyzed at the University of Florida analytical

research laboratory using a model 61E Thermo Jarrell-Ash ICAP 9000 spectrophotometer

(Franklin, MA).

Sand Mixes

Rooting media for each glasshouse study, the field study, and the leaching study

were mixed by hand using 85% USGA sand and 15% amendment by volume with the

exception of smectite, which was incorporated at 97.5% USGA sand and 2.5%










Table 3-1. Sand size analysis of amendments and sand mixes.
Sand


Very
coarse
1.0-
2.0 mm


Amendment
Clinoptilolite 1
Clinoptilolite 2
Calcined Clay 1
Calcined Clay 2
Diatomaceous Earth 1
Diatomaceous Earth 2
Peat
Montmorillonite
Iron Humate

Sand Mixture:
Sand
Clinoptilolite 1
Clinoptilolite 2
Calcined Clay 1
Calcined Clay 2
Diatomaceous Earth 1
Diatomaceous Earth 2
Peat
Montmorillonite
Iron Humate

USGA
Specifications


45.4
31.3
0.3
0.0
27.7
27.0
44.7
10.2
11.8



7.2
11.9
10.1
7.1
6.0
7.1
7.6
4.0
7.4
8.8


S10%


Coarse Medium Fine
0.5- 0.25- 0.10-
1.0 mm 0.50 mm 0.25 mm
-----------------------% by weight --------


48.0
67.9
46.6
50.9
56.5
64.6
15.3
16.5
17.2



41.2
39.9
42.6
40.1
37.8
36.7
38.3
22.9
39.3
37.0


6.8
0.9
52.9
49.0
15.3
5.1
16.4
16.8
31.5



35.7
31.2
30.3
35.3
35.0
33.9
33.1
54.5
35.0
33.1


2 60%


0.0
0.0
0.7
0.2
0.4
1.2
14.3
18.2
32.9



15.9
16.7
16.2
16.7
20.2
21.4
19.8
17.6
17.5
19.3


5 20%


t Based on USGA range of 0.25 .015 mm.
$ 85% USGA uncoated sand plus 15% amendment by volume
2.5% by volume
United States Golf Association



smectite. Particle size analysis was determined for each amendment and

sand/amendment mixture according to procedures described by Day (1965) (Table 3-1).

Sand used in each study was found to be slightly coated. According to the United States

Department of Agriculture, sands are considered to be slightly coated if they contain <

5% sand plus silt, but contain clay coatings. Harris et al. (1996) concluded the presence

or absence of clay coatings can be discrete and readily observable. Upon visual


Very
finet
0.05 -
0.10 mm


Silt +
Clay

<0.05 mm


0.0
0.0
0.0
0.1
0.1
1.0
7.8
32.5
5.4


S5%


S8%









inspection, coatings can be seen via their color, opacity, and rough surface texture. Sand

grain coating can include Fe & Al hydroxides, kaolinite, gibbsite, or goethite.



Water Use Efficiency Calculations

Water-use-efficiency was determined for each glasshouse study and the field study

according to eq. 3.5 as stated by Gregory et al. (2000). Dry matter yield for each week

was compared to the amount of water lost during that week as determined by weighing

each pot before and after each harvest.

WUE = dry matter yield (mg) / evapotranspired water (g) Eq. 3.5.

Estimations of water use assumed the density of water was 1 g cm-3 for each treatment,

and all water not evaporated was used by the turf.

Glasshouse Studies

Glasshouse studies were conducted from August to December 2002 and 2003 at the

University of Florida Turfgrass Envirotron in Gainesville, FL. The objectives of each

study were:

1. To determine the influence of soil amendments on WUE and quality of Tifdwarf
bermudagrass

2. To determine the influence of incorporation method on WUE and quality of
Tifdwarf bermudagrass

Year 1

The objective of this study was to determine the influence of soil amendments on

WUE, turf quality, and dry matter yield of Tifdwarf bermudagrass. Tifdwarf

bermudagrass [Cynodon dactylon (L.) Pers. x C. transvaalensis Burtt Davy] was

established during spring 2002 in a glasshouse on pots (203 mm wide at top, tapering to

175 mm at bottom, and 203 mm deep) using USGA-specified greens sand. Treatments









consisted of an amendment/sand mixture and incorporation method and were arranged in

a split plot design with 4 replications. Amendments included two zeolites [Ecosand (Zeo

Inc., McKinney, Tx.) (clinoptilolite 1); Ecolite (Ecolite Mfg Co., Spokane, WA)

(clinoptilolite 2)] which were determined to be clinoptilolite via X-ray diffraction, two

calcined clays [Soil Master Plus (Sport Turf Supply, Inc., Midland City, AL) calcinedd

clay 1); Profile (Profile LLC) calcinedd clay 2)], one calcined diatomaceous earth [Axis

(Agro Tech 2000, Norristown, PA) (diatomaceous earth 1)], one diatomaceous earth

[PSA (Golf Ventures, Lakeland, FL) (diatomaceous earth 2)], Canadian sphagnum peat,

Fe-humate (Vigiron, Winter Haven, FL), clay (montmorillonite), and sand.

Prior to establishment, each pot was saturated and allowed to drain for 24 h. Pot

weight after drainage was recorded and labeled as 'pot capacity'. An overhead mist-

irrigation system was used during establishment. Percent cover ratings were taken after

week one and were subsequently taken at one week intervals until full coverage was

achieved. Percent coverage was considered to be that portion of the pot surface that was

covered by turf. Following establishment, irrigation ceased and all further applications of

water were done by hand. The primary study lasted 18 weeks and began once all pots

achieved 100 percent coverage and were uniform. However, data was only collected

from week 3 to week 15 due to inaccuracies during the first three weeks and decreased

growth during the last 3 weeks when decreasing daylight reduced turf growth.

Following establishment, all pots were uniformly fertilized with NH4N03,
-2
concentrated super phosphate (CSP), and muriate of potash (KC1) at 5 g N m-2, 2.5 g P m

2, and 2.5 g K m-2 at week one and six. Micronutrients and sulfur (as sulfate) were









applied together using a commercially available micronutrient solution at a rate of 11.2

kg Fe ha1.

One primary function of soil amendments is nutrient retention which, in turn, may

increase turf quality. A turf quality rating is a subjective measurement of overall turf

health and appearance, which is crucial when assessing turf aesthetic value and

playability. During the 12 week study, visual quality ratings were recorded on a weekly

basis on a scale of 1 to 9, where 9 = ideal, 5.5 acceptable, and 1 = completely dead or

dormant.

Twice weekly, pots were weighed and water was applied to bring each pot back to

90% pot capacity. The amount of water was recorded and labeled 'applied water'.

Weekly, clippings were harvested by hand at 3 cm height, dried at 100 OC for 24 h, and

weekly harvested weight was recorded and labeled as 'dry matter yield'.

Upon completion of the 12 week study, overhead irrigation was used to bring all

pots back to uniformity. Water applied was then stopped and pots were allowed to dry to

determine number of days to wilt.

The null hypothesis for the 2002 glasshouse study was soil amendments do not

influence turf quality, dry matter yield, or WUE.

Year 2

All materials and methods for the 2003 glasshouse study were identical to the 2002

glasshouse study with two exceptions. First, a bacteriacide used to clean glasshouse

cooling pads was unintentionally applied to one replication of the full incorporation

method, thus this replication was removed, reducing the total number of pots from 120 to

110. Secondly, three incorporation methods were used (Fig. 3-1). Incorporation method

one involved mixing each amendment with sand (85:15 v:v) prior to turf establishment.









Incorporation method two involved incorporating each treatment into an 85:15 sand/peat

rootzone after turf establishment. This was accomplished by removing 9 or 4 aerification

cores (20 mm wide x 100 mm deep on 50 mm centers) and back-filling each core with a

50:50 sand/amendment mixture. All procedures and sample analysis followed

procedures and sample analysis from the 2002 study.

The null hypotheses used during the 2003 glasshouse study were: 1. Soil

amendments do not influence turf quality, dry matter yield, or WUE, and 2.

Incorporation method does not influence turf quality, dry matter yield, or WUE.


- 203 mm


100
203 mm\ /



175 mm-


A. B.


Figure 3-1. Schematic diagram of pot set-up used in glasshouse studies showing side and
top view of amendment incorporation methods where A = 85:15
sand/amendment, B = 4 tine aerification with 50:50 sand/amendment, and C =
9 tine aerification with 50:50 sand amendment.











Nutrient Leaching Study

The objective of this study was to determine the influence of soil amendments and

SMSA on NO3- N, NH4+-N, PO42- leaching in a golf course putting green. Twenty-four

lysimeters (2.54 cm diam. by 35 cm length) were constructed using polyvinyl chloride

(PVC). The top 30 cm of each lysimeter contained a USGA sand:peat mixture (85:15 by

-3
volume) packed to a density of 1.33 g cm-3. During a preliminary study, turf grown in a

mixture of SMSAs and sand did not establish which may be a result of the biocidal

influences of cationic surfactants (Gilbert and Al-taae, 1985). Therefore, treatments were

placed below the rootzone in the bottom 5 cm (Fig. 3-2) and included one zeolite

[Ecosand (Zeo Inc., McKinney, TX] which was determined to be clinoptilolite via X-ray

diffraction, two calcined clays [Profile (Profile LLC), Soil Master Plus (Sport Turf

Supply, Inc., Midland City, AL)] and two controls (control 1 = top 30 cm sand/peat,

bottom 5 cm sand; control 2 = top 30 cm sand, bottom 5 cm sand). Each amendment was

either coated with HDTMA or remained uncoated. Surfactant coating consisted of

mixing a given amount of solid phase (according to each amendments CEC) with a

solution of 67 mmol HDTMA. Previous research has determined bi-layer formation

occurs when HDTMA equilibrium concentration after addition of a solid phase is at least

twice the CEC of the solid phase (Li and Bowman, 1997). Sorbed HDTMA was

determined via thermal gravimetry (Table 4-1). Lysimeters were then capped at each end

with TyparTM landscape fabric (Reemay, Inc. Old Hickory, TN) and sealed with a domed,

PVC cap. A 1-cm threaded hole was installed in the middle of each cap to allow a

nutrient solution tube to be added to the top and a leachate collection tube to be added to

the bottom of each lysimeter. Each lysimeter was vertically secured to a stand. The









nutrient solution tube attached to the top of each lysimeter was connected to a Gilson

Model 302 steady-flow pump (Gilson Medical Electronics, Inc., Middleton, WI). The

pump was set to deliver 10.0 ml of deionized water per minute. A valve was installed

between the pump and lysimeter to which a 10 cm3 syringe was attached to inject nutrient

solution. Nutrient solution contained 2300 ppm NO3- N, 2480 ppm NH4+-N, and 4400

2-
ppm P042-. Leaching procedure consisted of first saturating the soil column with

deionized water, injecting 10 mL of nutrient solution, and collecting leachate using a

model 273 fraction collector (Instrumentation Specialties



S* .** Solution injection valve
k. 4 PUMP








30 cm




....... Pump Tube

Treatment Layer 5 cm




2.54 cm


Figure 3-2. Schematic diagram of lysimeter set-up used in leaching studies.









Co.) set to take a sample every 60 seconds until four pore volumes had been collected.

Each column was leached individually within each block. All samples were analyzed for

NH4-N and N03-N using an Alpkem RFA-300 auto analyzer. Phosphorous was

determined colorimetrically using a model 680 microplate reader (Bio-Rad Laboratories,

Hercules, CA). Treatments were arranged in randomized complete block design with

three replications, and statistical analyses were performed using SAS for analysis of

variance (SAS Institute, 1987).

The following transport models were used to simulate movement ofN03-N, NH4-

N and P through soil amendments. The convective-dispersive model (CD model) can be

written in dimensionless form (Brenner, 1958).

A. The Convective -Dispersive (CD) Model:

R ( C*/* p) = (1/P) (*C*/.K2) ( C*/. K) 3.6a

P =vL/D R = (1+pKD/9) 3.6b

X = x/L p = vt/L C* = C/Co 3.6c

T = Pulse applied in pore volumes 3.6d

where C* is the solute concentration in the effluent (C, [tg/ml) normalized to the

initial solute concentration (Co, [g/ml), x is the distance along the column (cm), t is the

time of flow (h), v (cm/h) is the pore water velocity, L (cm) is column length, D (cm2/h)

is the hydrodynamic dispersion coefficient, P is the Peclet number, R is the retardation

factor, and p is the pore volume, KD (ml/g) is the sorption coefficient, p is the soil bulk

density, and 0 is the volumetric water content.

B. The Two Site Nonequilibrium (TSN) Model:









The TSN model can also be described according to (Nkedi-Kizza et al., 1989). With first

order kinetics, the sorption occurs in two domains, such that:

C *Si* *S2

Si = FKDC 3.7a

dS2/dt = kiSi-k2S2 3.7b

where Si([tg/g) is the adsorbed concentration in the instantaneous domain, S2 ([tg/g) is the

adsorbed concentration in the time dependent sorption domain, F is fraction of sorbent

that is at equilibrium, kl and k2 are the forward and backward first order sorption rate

coefficients (1/h), respectively, other parameters have been defined for the CD-model.

For an adsorbing solute the one dimensional equation at steady state water flow can

be written in dimensionless form:

SC*/*p + (PR-1)C C*/.p + (1-P)R S*/.p = (1/P) (.*C*/.K2)- (*C*/.K) 3.8a

(1-P)R S*/p = co(C*-S*) 3.8b

where:

S*= S2/(1-F) KDCo 3.8c

0 =[1+F (pKD/0)]/R 3.8d

co =k2 (1-P)RL/v 3.8e

Other parameters (p, P, R, C* and X) in eq. 3.8a have been defined for the CD-model.

The Peclet number (P) reflects the ratio of the residence time due to dispersion and the

residence time due to convection emphasizing the effect of dispersion on solute transport,

the retardation factor (R) is the ratio of pore water velocity and solute velocity which

represents the effect of sorption on solute transport, P is the fraction of total retardation

due to sorption in the instantaneous domain, co is a number that gives the degree of









sorption nonequilibrium for the solute, it reflects the ratio of the time for solute sorption

to the residence time for the solute due to convection.

Parameters for the CD-model (R and P) and for the TSN-model (R, 0, and co) were

calculated from the measured breakthrough curves (BTCs) using the non-linear least-

squares optimization technique in the curve fitting program CFITIM (Van Genuchten,

1981). The parameter (T) was measured and as such was not optimized for either model.

The parameter P was calculated by fitting the CD-model to the BTCs ofNO3-N for a

given amendment. The obtained value of P from the CD-model was then used in the

TSN-model as a fixed parameter.

The null hypotheses used during the nutrient leaching study were: 1) Soil

amendments do not decrease NO3s, NH4+, or P04-2 leaching, and 2) SMSA do not

decrease NO3s, NH4+, or P04-2 leaching.














CHAPTER 4
RESULTS AND DISCUSSION

Amendment Characterizations

Surfactant Sorption

Via thermal analysis, greater weight loss was observed from HDTMA calcined clay

1 than from HDTMA calcined clay 2 (Fig. A-2, A-3). HDTMA clinoptilolite showed the

least weight loss and thus sorbed the least HDTMA (Fig A-4). For each amendment,

increased weight loss due to oxidation of HDTMA began at approximately 230 C, which

corresponded well with oxidation of pure HDTMA which began at 250 C. Oxidation of

HDTMA from coated amendments was nearly complete at 300 oC, which also compares

favorably with oxidation of pure HDTMA. Impurities inherent within SMSA likely

caused the minor differences between oxidation of pure and sorbed HDTMA. These

findings indicate the extent of HDTMA coating can be well described by thermal

gravimetry analysis.

Surfactant sorption capacity of each amendment can be seen in table 4-1. Although

clinoptilolite had a CEC 4 times higher than either of the calcined clays, it retained the

least amount of HDTMA. Several studies have shown the majority of CEC on

clinoptilolite is internal and inaccessible to HDTMA (Li et al., 1999; Li, 1999; Li and

Bowman, 1997). Following surfactant sorption, calcined clays retained approximately

one-half of their original CEC. Of the SMSA, calcined clay 1 retained the greatest

amount of HDTMA followed by Calcined clay 2 and Clinoptilolite 1 (Table 4-1).









Table 4-1. Ion exchange capacity and surfactant sorption as influenced by soil
amendment.

Solid Phase HDTMA Sorbed CECt ECECt EAEC
-- (g kg1) ---- cmol (+) kg1 --- cmol (-) kg-1
Clinoptilolite 27.1 97.4 93.3 4.1
Calcined Clay 1 73.4 20.9 9.6 11.3
Calcined Clay 2 62.9 21.8 12.1 9.7
t Cation exchange capacity
$ Effective cation exchange capacity
Effective anion exchange capacity


Mineral Composition

Neither DE contained any discernable minerals (Fig. A-5). While definitive

analysis of DE mineral composition via XRD is ambiguous, the broad peaks observed

from both DEs around a d-spacing of 4.0691 are indicative of amorphous silica. Silica

contents of DE have been reported to about 86 to 88% (Sylvia et al., 1997).

X-ray diffraction analysis of calcined clays can be seen in fig. A-6. Both clays

contain quartz, goethite, and small amounts of mica. The only significant difference

between calcined clays is the quartz peak (d= 3.35), which is likely evidence that calcined

clay 1 contains more quartz than calcined clay 2.

Zeolites used in this study were concluded to be clinoptilolite based upon XRD

analysis (Fig. A-7). No other minerals were apparent in either zeolite sample.

Nutrient Composition

Because soil nutrient status has been shown to positively influence WUE (Viets,

1962; Hatfield et al., 2001), the initial elemental content of each amendment and

sand/amendment mixture was determined via Mehlich I and KC1 extraction.

Sand/amendment mixture samples were taken from before turf sprigs were applied.









Nitrogen

Only peat and iron humate contained detectable levels of N (Table 4-2). Nitrogen

content of iron humate was lower than that observed by previous researchers. Varshovi

and Sartain (1993) determined the N content of a commercially available humate to be

0.85%. Lower N content determined in this study could be due to different humate

sources.

While peat contained more TKN prior to incorporation with sand, both peat and

iron humate produced equal amounts after incorporation (Table 4-3). Incorporation of

sand likely diluted any treatment influence, thus, no differences were observed.

Phosphorus

Extractable P did not follow any clear trends across soil amendment class.

However, in general, highest P levels were found in smectite while the lowest levels were

observed in iron humate (Table 4-2). Iron-based water treatment residuals have been

shown to be effective long-term P immobilizers. Furthermore, much of the P sorbed by

water treatment residuals is internal and considered to be irreversibly bound (Makris et

al., 2004). As expected, the control (USGA sand) was found to contain low levels of P.

While quartz sand is largely considered to be inert, sand grain coatings have been shown

to increase P retention (Harris et al., 1996) and may be responsible for the observed P

levels. After incorporation with sand, P levels were diluted for all amendments except

iron humate (Table 4-3). Because samples were taken from field plots which were

encouraged to settle by using daily irrigation for 10 days, P from irrigation water (Table

A-i) may have been responsible for the increased P in the iron humate treatment.

Smectite contained the highest level of extractable P before and after sand incorporation.

Diatomaceous earths were the only amendments that did not increase extractable P levels

above the sand/peat mixture.















Table 4-2. Chemical properties of amendments used in glasshouse and field studies.


Amendment


Sand (1)
Peat (2)
Calcined clay 1 (3)
Calcined clay 2 (3)
Clinoptilolite 1 (4)
Clinoptilolite 2 (4)
Diatomaceous earth 1 (5)
Diatomaceous earth 2 (5)
Smectite (6)
Iron Humate (7)


Contrast: 1 vs. 2
Contrast: 2 vs. others
Contrast: 2 vs. 3
Contrast: 2 vs. 4
Contrast: 2 vs. 5
Contrast: 2 vs. 6
Contrast: 2 vs. 7
Contrast: 3 vs. 5
Contrast: 3 vs. 7


CEC pHT
cmol
(+) kg1

0.7 5.9
114.5 7.3
21.7 5.4
21.5 5.6
97.8 5.5
35.1 6.3
7.8 7.9
34.1 4.6
20.4 6.0
41.2 4.8







*** ***
*** ***
*** ***






NS ***


iS cm1

8.3
76.9
201.3
48.0
8145.0
72.2
979.3
181.1
2154.0
300.3


TKN

%

0.00
0.55
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.42


P K CaC


Mgt Znt


Mn$


Cu Fe


mg kg-1


3.2
3.9
33.2
58.2
15.1
107.1
24.2
48.6
652.7
1.5


2.6
53.4
993.7
1129.9
764.8
591.5
112.1
671.5
95.9
2686.7


23.9
2769.3
766.5
747.5
2386.7
1844.5
166.0
1257.7
5165.3
6873.3


2.5
840.3
528.3
339.2
117.7
287.1
78.1
279.6
1129.2
345.1


0.2
13.9
14.7
3.4
6.2
5.0
2.3
7.7
1.3
65.4


3.4
21.1
124.0
102.6
9.1
6.7
233.9
32.5
0.1
30.0


NS ***
NS **
NS ***
NS ***
NS ***
NS ***
* ***
* ***
NS ***


15.5 1.9 3.4 5.6 43.1


9.1 14.9 31.3 13.1


9.2 3.0


NS, *, **, *** Not significant, significant at the 0.05, 0.01, and 0.001 probability levels, respectively.
f 2:1 deinonized water:soil
t Mehlich-1 extractable


CV (%)


*** 00
***
***
***
***
***
***
***
***


-------------------------------------------


----------------------------------------















Table 4-3. Chemical properties of 85:15 sand/amendment mixtures used in glasshouse and field studies.


Amendment


Sand (1)
Peat (2)
Calcined clay 1 (3)
Calcined clay 2 (3)
Clinoptilolite 1 (4)
Clinoptilolite 2 (4)
Diatomaceous earth 1 (5)
Diatomaceous earth 2 (5)
Smectite (6)
Iron Humate (7)


Contrast: 1 vs. 2
Contrast: 2 vs. others
Contrast: 2 vs. 3
Contrast: 2 vs. 4
Contrast: 2 vs. 5
Contrast: 2 vs. 6
Contrast: 2 vs. 7
Contrast: 3 vs. 5
Contrast: 3 vs. 7


CV (%)


CEC
cmol (+)
kg-


pHT ECT

tS cm'


0.7
1.8
2.7
2.8
25.7
16.0
5.3
1.2
1.3
6.4


TKN

%

0.00
0.03
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03


*** NS
*** ***


1.9 4.7 38.4


P K CaC


Mgj


Mn Cu Fe4


mg kg1


3.2
3.5
10.1
6.6
5.7
15.7
8.3
3.9
126.8
28.3


* +
** ++


2.6
2.3
85.2
66.8
338.1
115.9
45.8
5.9
8.8
63.6


23.9
276.9
191.5
149.7
358.0
228.8
198.8
46.1
677.3
920.4


2.5
107.6
54.2
47.9
19.7
36.2
36.6
7.9
155.1
19.5


3.4
7.4
33.9
30.5
6.3
4.5
10.4
22.5
12.4
799.5


NS



NS
*NS
NS
***
***
***


7.1 13.5


110.2


15.6 14.9 6.2


NS, *, **, *** Not significant, significant at the 0.05, 0.01,
f 2:1 deinonized water:soil
8 Mehlich-1 extractable


and 0.001 probability levels, respectively.


------------------------------------------


----------------------------------------









Potassium

Unlike P, clear trends were observed between amendment classes for Mehlich-1

extractable K of the pure amendment samples (Table 4-2). Calcined clays contained

higher levels of extractable K than zeolites which were followed by DEs. Sand contained

the lowest K levels while iron humate contained the highest. All amendments except

sand and smectite contained higher K levels than peat.

All K levels dropped after incorporation with sand (Table 4-3). Zeolites contained

the highest levels of K followed by CCs and DEs. Sand and sand/peat treatments

contained the lowest amount of extractable K. All amendments except smectite increased

extractable K above the sand/peat treatment.

Calcium

Of the pure amendment samples, highest Ca levels were found in iron humate

followed by smectite (Table 4-2). Of the remaining amendments, sand/peat contained

higher Ca levels than zeolites followed by CCs, DEs, and sand. Following sand

incorporation, Ca levels dropped for all amendments. Both iron humate and smectite

continued to exhibit the highest Ca levels after sand incorporation (Table 4-3). The

primary difference between Ca levels of amendments alone and amendment/sand

mixtures is that zeolites possessed lower Ca levels than peat before sand incorporation

while they contained similar Ca levels after incorporation. These results compare

favorably with those reported by Ok et al. (2003) where zeolite amended sand was found

to have the same Ca levels as sand/peat mixtures both before and after turf establishment.

With regards to initial retention of P, K, and Ca, these results show that amendment

classes may be used when considering the potential influence of plant available K and

Ca. However, incorporation of CCs or zeolites may decrease plant available Ca.









Phosphorus availability may increase with incorporation of CCs or zeolites, but it appears

that individual amendments should be recommended instead of amendment classes.

pH and EC

Salinity levels dropped after incorporation with sand (Table 4-3). Because

sand/amendment samples were taken from plots that were allowed to settle by irrigation,

the excess salts which were initially observed in the pure amendment samples were likely

leached out of the soil media.

Soil acidity also became more basic after sand incorporation. Acidity levels of 5.5

of pure amendments rose to near 6.5 after sand incorporation. This may also be due to

excess leaching with water high in Ca (Table A-i).

Moisture Retention

Analysis of moisture retention data revealed incorporation of amendments provided

a variety of beneficial physical characteristics to a sand-based rootzone. Moisture

content at field capacity, moisture content at wilting point, and plant available water

increased with the addition of soil amendments (Table 4-4). These parameters were

influenced primarily by the increase in total and micro porosity which accompanied

amendment incorporation.

Saturated hydraulic conductivity was found to be within acceptable ranges as

recommended by the USGA (Table 4-4). Diatomaceous earth 1 and 2 and clinoptilolite 2

reduced Ksat while all other amendments were similar to pure sand. Water flow in a

saturated soil is primarily through macropores (Hillel, 1998). However, this researcher

observed soils that produced the highest Ksat values also possessed the lowest

macroporosities. While this seems counterintuitive, McIntyre 1974 states that soils

prepared for Ksat analysis must be taken from undisturbed core samples. Core samples in









this analysis were taken from recently renovated soils and, thus, physical analysis may

not entirely agree with analysis of undisturbed soils.

Soil porosities varied from 32.2 to 38.9% (Table 4-4). Only clinoptilolite 1 failed

to increase total porosity above that of sand. This is likely due to clinoptilolite 1 having

the highest percentage of very course sand-sized particles (Table 3-1), and may explain

why clinoptilolite 1 was the only amendment that had a lower volumetric water content at

saturation than sand alone (Fig. 4-1). Both CCs increased macroporosity above sand

while all other amendments decreased macroporosity. The greatest influence of soil

amendments on porosity was observed in microporosity. All amendments increased

microporosity above sand alone. Diatomaceous earth 1 and iron humate were shown to

have the greatest influence, increasing microporosity from 7.7 to 15.6%. This is likely

due to iron humate having the largest percentage by weight of medium and fine sand size

particles than any other amendment (Table 3-1). Diatomaceous earths contain a large

number of internal channels which may contribute to the influence of diatomaceous earth

1 on microporosity.

Of the water held in macro and micropores, only water held in micropores is

considered to be available for plant uptake. Thus, correlation between microporosity and

plant available water should be high. The relation between microporosity and PAW was

found to be well correlated (R2 = 0.83; Fig. A-8).

As expected, amendment incorporation increased moisture held at field capacity

and wilting point. Correspondingly, plant available water also increased with amendment

incorporation. The greatest increase in moisture held at wilting point was observed from

diatomaceous earth 1 where percent moisture increased by more than 8 times that of













Table 4-4. Physical analysis of amendment/sand mixture at 85:15 by volume.
----------- Pore Space -----------
Amendment Ksat 1 Total Micro Macro PD # BD TfT FC PWP PAW TI
cm hr -------------- % -------------------- -------- g cm ----------------- % ------------------
Sand 61.0 ab 33.3 b 7.7 e 25.6 abc 2.34 a 1.56 a 7.7 e 0.4 f 7.3 f
Peat 66.2 ab 35.3 ab 13.5 b 21.8 cd 2.13 bc 1.37 f 13.5 b 1.2 e 12.3 b
Calcined clay 1 52.4 ab 38.9 a 12.5 bc 26.4 ab 2.29 ab 1.39 ef 12.5 bc 2.4 b 10.0 de
Calcined clay 2 55.6 ab 38.2 a 11.2 cd 26.9 a 2.36 a 1.46 bcd 11.2 cd 3.4 a 7.8 f
Diatomaceous earth 1 25.5 c 38.3 a 15.6 a 22.6 bcd 2.27 abc 1.40 def 15.6 a 3.5 a 12.1 b
Diatomaceous earth 2 44.5 bc 35.9 ab 13.7 b 22.1 cd 2.11 c 1.35 f 13.7 b 2.1 be 11.6 bc
Clinoptilolite 1 63.1 ab 32.2 b 11.4 cd 20.7 d 2.14 bc 1.45 cde 11.4 cd 1.9 bcd 9.4 e
Clinoptilolite 2 43.4 bc 35.0 ab 10.9 d 24.1 abcd 2.24 abc 1.45 cde 10.9 d 1.5 cde 9.3 e
Smectite 71.3 a 36.2 ab 13.1 b 23.1 abcd 2.39 a 1.52 ab 13.1 b 2.4 b 10.6 cd
Fe-Humate 51.7 ab 36.7 ab 15.5 a 21.1 d 2.32 a 1.47 bc 15.5 a 1.4 de 14.1 a

CV (%0) 17.2 5.1 4.3 7.1 3.0 1.8 4.3 12.8 4.4
Within columns, means followed by the same letter are not significantly different according to Duncan's multiple range test (0.05).
? saturated hydraulic conductivity
8 USGA recommendations are 15-30 (normal) and 30-60 (accelerated) cm hr-1
micropores (pores that contain water at 35 cm tension)
1 macropores (pores that contain air at 35 cm tension)
# particle density
ft bulk density
field capacity, by volume
plant wilting point, by volume
77 plant available water, by volume







54








0.4

-*- Sand
-o- Clinoptilolite 1
-v- Clinoptilolite 2
0.3

C
0

0.2




E
0.1
0




0.0
0 20 40 60 80 100

Suction Head (cm)

Figure 4-1. Moisture release curve for USGA sand amended with zeolites at 85:15 by
volume.













0.4

-*- Sand
-o- Diatomaceous Earth 1
Diatomaceous Earth 2
0.3
C

O

o
0.2 -



E
0.1





0.0 -
0 20 40 60 80 100

Suction Head (cm)

Figure 4-2. Moisture release curve for USGA sand amended with diatomaceous earths at
85:15 by volume.







56





0.4


-*- Sand
-o- Calcined Clay 2
S0.3 -v- Calcined Clay 1


C
o

0.2
-.o


E
S0.1





0.0 -
0 20 40 60 80 100

Suction Head (cm)

Figure 4-3. Moisture release curve for USGA sand amended with calcined clays at 85:15
by volume.









sand. Interestingly, peat and iron humate contained two of the lowest moisture contents

at wilting point but had the two highest PAW contents. This indicates that in order to

have the greatest influence on PAW, amendment must not only increase water held at FC,

but must also decrease water held at WP.

Moisture release curves indicated incorporation of soil amendments with sand

increased moisture content and moisture retention. Diatomaceous earths (Fig. 4-2), as a

class, produced greater moisture retention than calcined clays (Fig. 4-3) or zeolites.

Zeolites were observed to have the least influence on moisture held at saturation and

moisture held against 50 cm of head (Fig. 4-1), which is likely due to zeolites also having

the least influence on total pore space (Table 4-4). This relation between available water

and porosity was also noted by Brown and Duble (1975). Waltz et al. (2003) observed

amendments with the lowest soil porosity were also observed to retain the least amount of

water against gravity. Waltz et al. further noted sand amended with peat produced more

suitable physical and hydraulic properties for turfgrass growth than either calcined clay or

diatomaceous earth. However, of the two inorganic amendments Waltz investigated,

diatomaceous earths were found to be the most suitable replacement for peat. These

observations by Waltz both agree and contradict those found during this research. When

only physical and hydraulic properties are considered, diatomaceous earths increased

moisture held against gravity above that of peat while providing similar or adequate

PAW and conductivity. Thus, diatomaceous earths are not only the most suitable

inorganics replacement for peat, but they are actually more suitable than peat.

Of the amendments used, Fe-humate produced the greatest beneficial influence on

the putting green rootzone physical properties. The observed increase in moisture held







58


against gravity (Fig. 4-4) was matched only by diatomaceous earth 1. Correspondingly,

Fe-humate amended sand produced the highest amount of plant available water while

maintaining adequate hydraulic conductivity and bulk density (Table 4-4).




0.4 -*- Sand
-o-- Peat
-V- Smectite
Fe-Humate

0.3 -

C
o

S 0.2 -





0.1
0




0.0
0 20 40 60 80 100

Suction Head (cm)

Figure 4-4. Moisture release curve for USGA sand amended with peat or Fe-Humate at
85:15 by volume or with smectite at 97.5:2.5 by volume.









Glasshouse 2002

Establishment

Analysis of turfgrass establishment revealed amendment influence was dependent

upon amendment source (Fig. 4-5). Pots containing clinoptilolite 1, diatomaceous earth

2, calcined clay 1, or calcined clay 2 did not change the establishment rating compared to

pots containing sand alone. Clinoptilolite 2, diatomaceous earth 1, and Fe-humate

decreased the rate of turf establishment while only peat and smectite increased turf

establishment above pots containing only sand. No amendment increased the rate of turf

establishment above pots containing the sand/peat mixture.

The influence of the zeolite treatment on turf establishment is in contrast to finding

reported by Nus and Brauen (1991). They reported plots containing zeolite were over

90% established 28 DAP while plots containing equal volumes of peat were 87%

established. Furthermore, they reportedly failed to establish turf on 100% sand plots.

However, Ferguson et al. (1986) reported decreased growth with the incorporation of

zeolite to pure sand. Findings by Ferguson are similar to those found by this researcher.

Because NH4N03 was used as the sole source of N during establishment, and due to the

affinity zeolites have for NH4 (Ferguson and Pepper, 1987), it is likely turf establishment

did not increase with zeolite incorporation because much of the N was sorbed out of soil

solution which effectively decreased the amount of plant available N.

Diatomaceous earths reacted similarly to zeolites with diatomaceous earth 2

producing nearly identical establishment ratings as sand alone and diatomaceous earth 1

lowering the turf establishment rate. While DEs tend to increase soil moisture, they have

low CECs which may be crucial during turf establishment. Nutrients applied during

establishment may be continually leached due to excessive water applications







60





100 A.

80

60
-*- Ecosand
40
40 /Ecolite
2 Sand
20


108 B.

80

60

40 Axis
40

20 S-v- Sand
20






60
> 408
O(1


80

60
SMontmorillonite
40 Peat
-- Iron Humate
20 Sand




80

60

40 Soil Master
Profile
20 S Sand

0
7 14 21 28 35 42

Days After Planting


Figure 4-5. Establishment of Tifdwarf bermudagrass during summer 2002 as influenced
by (A.) zeolites, (B.) diatomaceous earths, (C.) clay and organic, and (D.)
calcined clays. Vertical bars denote standard error.









which are typically applied during the first weeks of establishment (Shaddox, 2001).

Thus, low CEC rootzones may be more susceptible to nutrient depletions which may lead

to plant deficiencies and decreased growth.

Peat and smectite were the only amendments that increased the rate of turf

establishment above sand alone. The influence of peat on turf establishment has been

well documented and has been primarily attributed to the increase in moisture retention,

CEC, and additional nutrients which are mineralized from peat during the establishment

period (Bigelow et al., 2001b; Carlson et al., 1998). Smectite was found to produce high

moisture retention and possessed a CEC of 20 cmol(+) kg-1. These parameters may have

been sufficient to produce establishment equal to peat.

Turf Quality

Turf quality ratings were taken each week to assess overall turf health during the 12

week study (Table 4-5). Pots containing only sand produced the lowest quality turf while

pots containing calcined clay 2 and iron humate produced the highest quality. These

results correspond well with each amendment's physical and chemical characteristics.

Sand exhibited low moisture retention (Fig 4-4) and low nutrient content (Table 4-3) and,

thus, pots containing only sand exhibit poor turf quality. Pots containing calcined clay 2

or iron humate were observed to increase soil moisture and nutrient content and, thus,

pots containing these amendments produced superior turf quality. Turf quality for the

inorganic amendments fit well within amendment classes. Calcined clays produced the

highest quality turf followed by DEs and zeolites. The low quality rating from pots

containing zeolites are likely due to the low moisture retention which accompanies

zeolite incorporation. The influence of soil amendments on turf growth was investigated














Table 4-5. Visual quality rating of bermudagrass as influenced by 85:15 sand/amendment rootzone during 2002 glasshouse study.
----- ----------------------------------Week-------------------------------------- ------------


Treatment
Sand
Peat
Calcined clay 1
Calcined clay 2
Diatomaceous earth 1
Diatomaceous earth 2
Clinoptilolite 1
Clinoptilolite 2
Smectite
Iron Humate


1 2 3 4 5 6 7 8 9
4.7 e 5.1 ef 4.7 e 5.7 de 5.0 b 4.7 b 4.7 f 4.7 c 5.0 d
5.8 bcd 6.5 abcd 6.1 cd 6.2 bcd 6.6 a 6.2 bc 6.2 cde 6.2 b 6.7 abc
6.8 a 6.8 ab 6.8 abc 6.3 bcd 6.7 a 7.0 ab 7.1 ab 7.1 a 6.6 abc
7.1 a 7.1 a 7.3 a 6.7 abc 7.0 a 7.6 a 7.2 ab 7.3 a 7.1 ab
6.3 abc 5.7 cdef 6.3 bcd 6.2 bcd 6.6 a 6.3 bc 6.5 bcd 6.6 ab 6.5 bc
5.7 cd 6.0 bcde 6.6 abc 6.0 cde 6.5 a 6.3 bc 7.0 abc 6.0 b 6.5 bc
4.8 e 5.0 f 5.1e 5.2 e 5.6 b 5.6 c 5.7 de 5.8 b 6.1 c
5.3 de 5.6 def 5.5 de 5.8 de 5.6 b 5.8 c 5.6 e 5.8 b 6.3 bc
6.6 ab 6.6 abc 6.3 bcd 7.0 ab 6.8 a 6.0 c 6.1 de 6.7 ab 7.1 ab
7.0 a 7.1 a 7.1 ab 7.2 a 6.8 a 7.3 a 7.3 a 7.5 a 7.5 a


10 11
5.1d 5.0 c
6.5 bc 6.3 b
7. ab 7.6 a
7.2 ab 7.5 a
6.3 bc 6.3 b
6.6 bc 6.1 b
5.8 cd 6.2 b
6.1 c 6.3 b
6.3 bc 6.5 b
7.8 a 7.8 a


CV (%0) 9.0 9.5 9.0 8.3 7.0 9.1 8.1 8.5 8.6 8.7
Within columns, means followed by the same letter are not significantly different according to Duncan's multiple range test (0.05).


9.5 7.7 3.2


12
5.2 d
6.5 bc
7.1 ab
7.3 a
6.1 c
6.8 abc
6.2 c
6.1 c
6.3 bc
7.6 a


Mean
5.0 e
6.3 c
6.9b
7.2 ab
6.3 c
6.3 c
5.6 d
5.8 d
6.5 c
7.3 a









by Wehtje et al. (2003). They investigated the influence of zeolite, DE, and CC

incorporation with native soil and concluded that improvement in bermudagrass

performance is most likely related to increases in soil moisture. Overall, these findings

agree with findings reported by Miller (2000). Miller (2000) investigated several

inorganic amendments along with peat and reported turf may perform differently when

grown in various rootzone media. However, Miller (2000) not only reported little

differences between amendments, but also observed some amendments performed

similarly to pots amended with pure sand. In this researcher's study, all amendments

increased turf quality above that of sand. The reported differences between the two

studies are likely due to the method in which amendments were incorporated into the

rooting zone. Amendments in Miller's study were introduced by first aerifying and then

back-filling those holes with each amendment. This may have decreased the

homogeneity of the amendment/sand rootzone and may have decreased each amendments

influence on turf growth.

Water Use Efficiency

No differences in clipping yield, applied water, or WUE were observed between

sand and sand/peat rootzones (Table 4-6). Only zeolite amended pots failed to increase

WUE above that of sand/peat. Due to the source of N used (NH4NO3) and to the affinity

zeolites have for NH4, it is likely that as much as /2 of the applied N may have been

rendered inaccessible to plant uptake, thus, plant growth was hindered. Absorption of

NH4 by zeolite amended soils has been observed by Bigelow et al. (2000). They also

noted that rootzones amended with zeolite were less effective during turf establishment

than those amended with peat. Other researchers have also noted this apparent negative










Table 4-6. Tissue yield, applied water, and water-use-efficiency of Tifdwarf
bermudagrass as influenced by soil amendments during glasshouse 2002
study.
Rootzone Mixturet Clippinq Yield Applied Water WUEt


Sand (1)
Peat (2)
Calcined clay 1 (3)
Calcined clay 2 (3)
Diatomaceous earth 1
Diatomaceous earth 2
Clinoptilolite 1 (5)
Clinoptilolite 2 (5)
Smectite (6)
Iron Humate (7)


(g)
3.4
3.8
6.5
5.9
5.5
5.9
4.1
4.4
4.6
4.7


(ml)
3363.3
3628.3
4453.3
4210.8
4376.8
4298.3
3544.8
3858.5
3677.3
3215.5


(mgg g1)
1.0
1.1
1.5
1.4
1.3
1.4
1.2
1.1
1.3
1.5


Contrast: 1 vs. 2 NS NS NS
Contrast: 2 vs. others
Contrast: 2 vs. 3
Contrast: 2 vs. 4
Contrast: 2 vs. 5 NS NS NS
Contrast: 2 vs. 6 ** NS
Contrast: 2 vs. 7
Contrast: 3 vs. 4 NS
Contrast: 3 vs. 7 *** *** NS

---------------------^ ------ -
CV 8.0 3.9 7.4
NS, *, **, ***, Not significant, significant at the 0.05, 0.01, and 0.001 probability levels,
respectively.
t 85% USGA uncoated sand plus 15% amendment by volume
$ Water Use Efficiency = clipping yield / applied water
2.5% by volume


characteristic inherent in natural zeolites and attempted to overcome them by using

zeolites which have been pre-loaded with NH4. Incorporation of these products has been

shown to lead to rapid establishment and high quality turf (Andrews et al., 1999; Miller,

2000). Therefore, it is reasonable to assume the low clipping yield and WUE produced

by the zeolite treatment was due to the removal of plant available N. However, if this is

the case, it is also likely that over time, the zeolite will come to equilibrium with NH4 in









soil solution and, thus, provide a buffer for plant consumption when NH4 in soil solution

is low.

Calcined clays and iron humate were equally effective and produced the greatest

increase in turfWUE (Table 4-6). This is likely due to CCs and iron humate providing

both an increase in plant available P and K (Table 4-3) and moisture retention (Fig. 4-4).

Rootzone mixtures ranked in order of decreasing effectiveness were: iron humate = CCs

> DEs = smectite > zeolites = peat = sand.

Amendments that produced the greatest increase in WUE were those amendments

that provided adequate moisture retention and adequate CEC and initial nutrient content.

While peat did increase PAW comparable to that of inorganic amendments (Table 4-4),

peat did not increase CEC, available P, or K above that provided by sand alone (Table 4-

3). A similar trend is also clear regarding zeolites. Zeolites not only increased the

rootzone CEC above all other amendments, but they also provide adequate P and the

highest amount of K. However, zeolites had the lowest influence on moisture held at

field capacity. According to these findings, in order to maximize turf WUE by

incorporating soil amendments, the amendment must be able to increase moisture

retention, provide adequate available nutrients, and retain those nutrients via cation

exchange.

Glasshouse 2003

Establishment

During the 2003 establishment phase, all amendments increased turf establishment

rate above that of pots containing only sand (Fig. 4-6). Peat and iron humate produced

the greatest increase in establishment while pots containing smectite produced the lowest

increase. Iron humate was the only amendment that produced higher establishment







66






100
A.
80 -

60

40 -O- Clinoptilolite 1
-0- Clinoptilolite 2
20 Sand

0
100
B.
80

60

40 -- Diatomaceous Earth 1
S-0- Diatomaceous Earth 2
20 Sand

> 0
o 100 -
C.
80

60

40 -0- Smectite
-- Peat
20 Fe-Humate
Dy Af PSand
0
0I III
100
D.
80

60

40 Calcined Clay 1
-0- Calcined Clay 2
20 -- Sand

0
7 14 21 28 35 42 49

Days After Planting


Figure 4-6. Establishment of Tifdwarf bermudagrass during summer 2003 as influenced
by (A.) zeolite, (B.) diatomaceous earths, (C.) clay and organic, and (D.)
calcined clays. Vertical bars denote standard error.









ratings than pots containing sand/peat. These findings are different than those found

during the 2002 study in which only peat and smectite produced higher rating than pots

containing only sand. While the reason for this difference is unknown, difference

between irrigation manifolds between the two studies may have allowed more water to be

applied during the 2002 study, thus decreasing the influence of each amendments

moisture retention capabilities.

No inorganic amendment produced higher establishment ratings than did pots

containing sand/peat. These findings agree with those reported by Bigelow et al. (1999).

They investigated the influence of CCs, DEs, and zeolites on turf establishment and also

reported that no inorganic amendment produced faster establishment than peat.

As in the 2002 study, differences between establishment rates of inorganic

amendments were minimal. All pots containing organic or inorganic amendments were

fully established at 42 days after planning (DAP). This is over 7 days longer than the

2002 study. This may also be due to the different irrigation manifolds used between the

two studies.

Turf Quality

Upon analysis of turf quality, turf grass response was dependent upon the method x

treatment interaction (Table 4-7). Therefore, amendment influences were determined

within each method.

Analysis of turf quality as influenced by sand/amendment mixtures revealed quality

was dependent upon amendment type (Table 4-8). All amendments increased turf quality

above that of sand alone. However, only CCs and iron humate increased quality above

pots containing sand/peat. Amendments influence on turf quality in order of decreasing









Table 4-7. Analysis of variance of mean squares on turf quality during 2003 study as
influenced by incorporation method and amendment type.
Source of Variation df Mean Squares F value
Block 3 0.10 2.79*
Method (M) 2 0.54 14.35***
Error (a) 5 0.03
Amendment (A) 9 2.11 66.28***
AxM 18 0.40 12.60***
Error (b) 72 0.03
Total 109
*, ***, Significant at 0.05, 0.001 probability levels, respectively.


effectiveness followed: iron humate > CCs > smectite = peat = DEs > zeolites > sand. As

observed during 2002, iron humate produced superior turf quality above all other

amendments. This is likely due to the iron humate providing background levels of P and

K, but more importantly providing the greatest amount of PAW (Table 4-4). Moisture

has been noted as being the primary limiting factor when assessing turf establishment and

quality. Bigelow et al. (1999) stated moisture appeared to be the main limiting factor

when assessing amendments influence on turf establishment. Waltz and McCarty (2000)

hypothesized that more moisture held near the soil surface by peat-amended soils

provided a faster establishment for seeded bentgrass than soil amended with inorganic

amendments. Bigelow et al. (2001b) also determined that improved turf quality of

amended sand rootzone was due to higher water holding capacities. However, according

to findings by this researcher, moisture content may not be the primary variable

influencing turf quality. This is clearly observable in the case of DEs. Diatomaceous

earths produced 30% more PAW than CCs (Table 4-4), but DEs produce quality ratings

nearly 1 unit lower than CCs. Clearly available water is not the only variable dictating

the influence of amendments on turf quality. It seems more likely that the combination of

available water and nutrient content of amended rootzones was the primary influencing

factor during this study.














Table 4-8. Visual quality rating of bermudagrass as influenced by 85:15 sand/amendment rootzone during 2003 glasshouse study.
------------------------------------- Week -----------------------------------------
Treatment 1 2 3 4 5 6 7 8 9 10 11 12 Mean
Sand 4.6 e 4.8 d 4.6 d 5.1 e 5.0 e 4.8 e 4.8 f 4.8 e 4.8 e 4.8 d 5.0 e 5.0 d 4.8 e
Peat 6.3 bc 6.5 b 6.3 b 6.1 bcd 6.6 bcd 6.6 abc 6.3 cde 6.3 cd 6.5 bcd 6.6 bc 6.5 cd 6.6 bc 6.4 c
Calcined clay 1 7.lab 6.8 ab 6.6 ab 7.0 b 7.lab 7.0 ab 7.1b 7.3 ab 7.lab 7.3 b 7.6 ab 7.3 ab 7.1b
Calcined clay 2 7.0 ab 7.5 a 7.3 a 7.0 b 7.0 abc 7.3 ab 7.0 bc 7.1 abc 7.1 ab 7.3 b 7.3 abc 7.1 ab 7.1b
Diatomaceous earth 1 6.5 abc 6.3 bc 6.3 b 6.1 bcd 6.5 cd 6.6 abc 6.8 bcd 6.6 bcd 6.3 bcd 6.3 c 6.3 cd 6.0 c 6.4 c
Diatomaceous earth 2 6.0 cd 6.0 bc 5.8 bc 6.0 cde 6.1 d 6.5 bcd 6.6 bcd 6.3 cd 6.3 bcd 6.6 bc 6.5 cd 6.6 bc 6.3 c
Clinoptilolite 1 4.6 e 4.6 d 5.0 cd 5.3 de 5.5 e 5.8 cd 5.8 e 6.0 d 6.0 d 6.1 c 6.0 d 6.1 c 5.5 d
Clinoptilolite 2 5.3 de 5.5 cd 5.3 cd 5.6 de 5.5 e 5.6 de 5.8 e 6.0 d 6.1 cd 6.1 c 6.3 cd 6.1 c 5.8 d
Smectite 6.6 abc 6.3 bc 6.3 b 6.8 bc 6.6 bcd 6.0 cd 6.1 de 6.8 bcd 7.0 abc 6.1 c 6.8 bcd 6.8 abc 6.5 c
Iron Humate 7.3 a 7.5 a 7.5 a 7.8 a 7.3 a 7.5 a 8.0 a 7.8 a 7.6 a 8.1 a 8.1 a 7.6 a 7.7 a

CV (%0) 7.4 8.0 8.6 7.1 4.8 7.6 6.4 7.8 6.8 6.7 8.4 7.1 4.3
Within columns, means followed by the same letter are not significantly different according to Duncan's multiple range test (0.05).









Minimal differences in turf quality were observed between amendments when

amendments were incorporated after 4 tine aerification (Table 4-9). All amendments

produced turf above the minimal acceptable quality ratings. During the aerification

study, the rootzone consisted primarily of sand/peat mixture. This likely decreased the

influence of amendments on turf quality, thus pots modified with sand, DEs, and zeolites

produced quality ratings equal to that of pots containing only sand/peat. Only CCs,

smectite, and iron humate produced ratings higher than pots modified with pure sand.

Highest quality ratings were observed from iron humate amended pots followed by CCs.

This trend was also observed when amendments were fully incorporated into the

rootzone.

Greater difference between treatment means were observed when amendments

were incorporated after 9 tine aerification than after 4 tine (Table 4-10). This result was

anticipated and is most likely due to a large portion of the rootzone being replaced by

each treatment in the 9 tine aerification versus the 4 tine. Only diatomaceous earth 1

failed to increase turf quality above that of pots modified with only sand. As in the full

mixture and 4 tine aerification methods, iron humate produced the highest quality turf

followed by CCs. Sartain (1999) reported iron humate can positively influence

bermudagrass growth and quality when adequate N is available. Sartain attributed

bermudagrass response to the addition of iron which accompanies iron humate

incorporation. The increase in Fe, along with N, in iron humate is likely the cause of the

observed increase in turf quality.














Table 4-9. Visual quality rating of Tifdwarf bermudagrass as influenced by 4 tine aerification during 2003 glasshouse study.
-----------------------------------Week---------------------------------- -------------
Treatment 1 2 3 4 5 6 7 8 9 10 11 12 mean
Sand 6.2 bc 6.3 a 6.5 b 6.0 b 6.0 b 6.3 a 6.2 b 6.6 b 6.5 bc 6.3 b 6.6 abc 6.7 bc 6.3 d
Peat 6.3 bc 6.5 a 6.6 b 6.3 b 6.5 ab 6.7 a 6.3 b 6.7 ab 6.7 bc 6.2 b 7.0 ab 6.5 bc 6.5 bcd
Calcined clay 1 6.7 ab 6.6 a 6.5 b 6.8 ab 6.8 ab 6.3 a 6.3 b 7.0 ab 6.2 c 7.0 ab 6.3 bc 7.0 ab 6.6 bc
Calcined clay 2 6.3 bc 6.7 a 6.8 ab 6.8 ab 6.5 ab 7.0 a 6.8 ab 6.5 b 7.0 ab 6.7 ab 6.3 bc 7.0 ab 6.7 b
Diatomaceous earth 1 6.2 bc 6.2 a 6.5 b 6.2 b 6.2 ab 6.8 a 6.2 b 6.5 b 6.5 bc 6.6 ab 6.1 c 6.5 bc 6.4 d
Diatomaceous earth 2 5.7 c 6.2 a 6.2 b 6.3 b 6.0 b 6.6 a 6.6 b 6.3 b 6.5 bc 6.7 ab 6.7 abc 7.0 ab 6.4 d
Clinoptilolite 1 6.1 bc 6.5 a 6.1 b 6.1 b 6.6 ab 6.6 a 6.3 b 6.6 b 6.3 bc 6.6 ab 6.5 bc 6.3 bc 6.4 d
Clinoptilolite 2 6.0 c 6.7 a 6.7 ab 6.5 b 6.6 ab 7.1 a 6.1 b 6.6 b 6.7 bc 6.5 ab 6.6 abc 6.1 c 6.5 cd
Smectite 6.3 bc 7.0 a 6.7 ab 6.2 ab 6.2 ab 6.3 a 6.5 b 7.1 ab 6.7 bc 6.7 ab 6.6 abc 6.7 bc 6.6 bc
Fe-Humate 7.1 a 7.0 a 7.5 a 7.6 a 7.1 a 7.1 a 7.5 b 7.5 a 7.5 a 7.3 a 7.3 a 7.6 a 7.3 a

CV (%0) 6.5 6.7 7.5 8.1 8.6 7.5 7.2 7.4 6.5 7.8 7.6 6.6 1.8
Within columns, means followed by the same letter are not significantly different according to Duncan's multiple range test (0.05).














Table 4-10. Visual quality rating of Tifdwarf bermudagrass as influenced by 9 tine aerification during 2003 glasshouse study.
----------------------------------------Week ----------------------------------------
Treatment 1 2 3 4 5 6 7 8 9 10 11 12 mean
Sand 6.0 c 6.2 d 5.8 d 6.1c 6.1b 6.1c 6.0 d 6.0 b 6.6 b 6.3 bc 6.5 b 6.7 b 6.2 f
Peat 6.5 abc 6.3 d 6.5 cd 6.8 bc 6.6 ab 6.8 abc 6.6 bc 6.5 b 7.0 ab 6.3 bc 6.6 b 6.3 b 6.5 cd
Calcined clay 1 6.8 ab 6.5 bcd 6.8 bc 7.0 ab 6.8 ab 6.6 bc 6.7 bc 6.8 ab 6.3 b 6.8 b 6.6 b 7.1 ab 6.7 bc
Calcined clay 2 6.6 abc 7.3 a 7.2 ab 6.6 bc 6.5 ab 7.1 ab 6.7 bc 6.6 ab 6.7 ab 6.8 b 6.5 b 6.7 b 6.8 b
Diatomaceous earth 1 6.5 abc 6.1 d 6.0 d 6.3 bc 6.2 b 6.8 ab 6.8 b 6.6 ab 6.3 b 5.8 c 6.2 b 6.3 b 6.3 ef
Diatomaceous earth 2 6.3 abc 6.3 cd 6.5 cd 6.6 bc 6.2 b 6.5 bc 6.6 bcd 6.3 b 6.6 b 6.7 b 6.6 b 6.7 b 6.5 de
Clinoptilolite 2 6.1 bc 6.2 d 6.3 cd 6.3 bc 6.3 ab 7.0 ab 6.1 cd 6.5 b 6.8 ab 6.1 bc 6.8 ab 6.8 ab 6.4 de
Clinoptilolite 1 5.8 c 6.5 bcd 5.8 d 6.2 bc 6.7 ab 7.0 ab 6.3 bcd 6.5 b 6.5 b 6.6 bc 6.5 b 6.6 b 6.4 de
Smectite 6.6 abc 7.0 abc 7.0 abc 6.7 bc 7.0 ab 6.5 bc 6.5 bcd 6.8 ab 6.8 ab 6.8 b 6.6 b 6.8 ab 6.7 bc
Fe-Humate 7.1 a 7.1 ab 7.5 a 7.6 a 7.2 a 7.3 a 7.7 a 7.5 a 7.3 a 7.7 a 7.5 a 7.6 a 7.4 a

CV (%0) 7.7 6.0 5.9 7.0 8.1 6.4 5.9 8.7 6.5 6.9 7.8 7.1 1.9
Within columns, means followed by the same letter are not significantly different according to Duncan's multiple range test (0.05).









Days to Wilt

In order to further determine the influence of soil amendments on turf growth,

water application was stopped at the end of the study and days-to-wilt (DTW) was

observed. Upon analysis of DTW, the method x treatment interaction was not

significant. Therefore, treatments effects were averaged across methods (Table 4-11).



Table 4-11. Analysis of variance of mean squares on Tifdwarf days to wilt during 2003
study as influenced by incorporation method and amendment type.
Source of Variation df Mean Squares F value
Block 3 5.07 1.78
Method (M) 2 4.90 1.72
Error (a) 5 2.84
Amendment (A) 9 3.10 0.78
AxM 18 5.05 1.26
Error (b) 72 4.00
Total 109



Turf grown in pots containing sand/peat was observed to wilt at 8.9 days. No

amendment increased DTW above sand/peat (Table 4-12). While turf grown with iron

humate and diatomaceous earth 1 was observed to extend DTW to 9.8, it was not

considered statistically significant. These findings agree with those reported by Miller

(2000). Miller observed turf grown in pots containing calcined clays, diatomaceous

earths, and zeolites required the same time to reach DTW as pots containing sand/peat.

Miller observed only sand and one zeolite treatment reduced DTW below sand/peat. The

lack of differences between amendments is likely due to the method in which

amendments were incorporated. When amendments were incorporated after aerification

versus full incorporation, the influence of each amendment on dry matter yield and WUE










was reduced (Table 4-14, Table 4-15). If full incorporation were the only method

analyzed, amendments may influence DTW.

Table 4-12. Days to wilt of Tifdwarfbermudagrass as influenced by
85:15 sand/amendment rootzone during 2003 glasshouse
study.
Treatment Days to Wilt
-- d ----
Sand (1) 9.1
Peat (2) 8.9
Calcined clay 1 (3) 8.8
Calcined clay 2 (3) 9.3
Diatomaceous earth 1 (4) 9.8
Diatomaceous earth 2 (4) 9.4
Clinoptilolite 1 (5) 9.0
Clinoptilolite 2 (5) 8.0
Smectite (6) 9.0
Iron Humate (7) 9.8

Contrast: 1 vs. 2 NS
Contrast: 2 vs. others NS
Contrast: 2 vs. 3 NS
Contrast: 2 vs. 4 NS
Contrast: 2 vs. 5 NS
Contrast: 2 vs. 6 NS
Contrast: 2 vs. 7 NS
Contrast: 3 vs. 4 NS
Contrast: 3 vs. 7 NS

CV (%) 21.6


Water Use Efficiency

Upon analysis of WUE for the 2003 study, Tifdwarf WUE was dependent upon the

method x treatment interaction (Table 4-13). Therefore, amendment influences were

determined within each method.

As observed in the 2002 study, no differences in mean clipping yield, applied

water, or WUE were observed between sand and sand/peat rootzones (Table 4-14). This

was unexpected due to the greater amount of PAW retained in the peat amended rootzone

versus sand alone (Table 4-4), as well as larger quantities of TKN, Ca, and Mg found in









Table 4-13. Analysis of variance of mean squares on Tifdwarf water use efficiency
during 2003 study as influenced by incorporation method and amendment
type.
Source of Variation df Mean Squares F value
Block 3 0.001 0.72
Method (M) 2 0.853 385.88 ***
Error (a) 5 0.002
Amendment (A) 9 0.287 139.13***
AxM 18 0.084 41.00***
Error (b) 72 0.002
Total 109
*, ***, Significant at 0.05, 0.001 probability levels, respectively.


peat amended pots (Table 4-3). These findings contradict those found by Snyder (2003)

who reported a 32% increase in clipping yield of bermudagrass when peat was

incorporated into an uncoated sand-based rootzone. However, similar findings were

reported by Comer (1999) who investigated the incorporation of a variety of soil

amendments with and without peat into a sand-based putting green. Comer reported that

pots containing amendments produced less dry matter when peat was incorporated than

when peat was withheld. Similar trends were observed between the control containing

only sand and the control containing sand/peat. Differences were attributed to N

immobilization by microbes in the sand/peat pots which would effectively reduce plant

available N. If a large supply of C relative to inorganic N is provided by peat, N

consumption by microbes will be stimulated (Pierzynski et al., 1994).

Only pots amended with zeolites failed to produce clipping yields and WUE

ratings above pots containing sand/peat (Table 4-14). Explanations for this response

regarding NH4 immobilization by zeolites have been addressed in the preceding section.

Zeolite- amended pots required 17% more water to produce essentially the same biomass

as sand/peat pots. During both the 2002 and 2003 studies, zeolite amended pots did not

produce quality ratings, clipping yields, or WUE ratings superior to that of peat. These












Table 4-14. Tissue yield, applied water, and water-use-efficiency of Tifdwarf
bermudagrass as influenced by fully incorporated soil amendments during
glasshouse 2003 study.
Rootzone Mixturet. Clipping Yield Applied Water WUEt
(g) (mL) (mg g-)
Sand (1) 3.5 3181.8 1.1
Peat (2) 3.6 2986.1 1.2
Calcined clay 1 (3) 4.7 2745.1 1.7
Calcined clay 2 (3) 5.0 3325.6 1.5
Diatomaceous earth 1 (4) 4.9 3037.5 1.6
Diatomaceous earth 2 (4) 4.4 3176.2 1.4
Clinoptilolite 1 (5) 3.8 3478.8 1.1
Clinoptilolite 2 (5) 4.2 3516.7 1.2
Smectite (6) 4.5 2522.2 1.8
Iron Humate (7) 7.1 3925.0 1.8


Contrast: 1 vs. 2 NS NS NS
Contrast: 2 vs. others
Contrast: 2 vs. 3 *** NS
Contrast: 2 vs. 4 ** NS
Contrast: 2 vs. 5 NS ** NS
Contrast: 2 vs. 6
Contrast: 2 vs. 7
Contrast: 3 vs. 4 NS NS NS
Contrast: 3 vs. 7 *-------
CV (%) 11.2 5.9 6.8


NS, *, **, ***, Not significant, significant at the 0.05, 0.01, and 0
respectively.
t 85% USGA uncoated sand plus 15% amendment by volume
$ Water Use Efficiency = clipping yield / applied water
2.5% by volume


.001 probability levels,


results suggest zeolite is not a suitable replacement for peat in sand-based putting greens

if increasing turf quality or WUE is desired. However, zeolites may be considered as an

amendment to increase putting green CEC (Table 4-3).

No differences in applied water were observed between peat and CCs and peat

and DEs, yet differences were observed between clipping yield and WUE (Table 4-14).

Because the same amount of water and nutrients were applied to CCs, DEs, and peat










Table 4-15. Tissue yield, applied water, and water-use-efficiency of Tifdwarf
bermudagrass as influenced by soil amendments after 9 tine aerification
during glasshouse 2003 study.
Rootzone Mixturet. Clipping Yield Applied Water WUEt
(g) (ml) (mg g-)
Sand (1) 4.1 3388.9 1.2
Peat (2) 3.5 3531.7 1.0
Calcined clay 1 (3) 4.0 3056.4 1.3
Calcined clay 2 (3) 3.8 3156.9 1.2
Diatomaceous earth 1 (4) 3.9 3568.2 1.1
Diatomaceous earth 2 (4) 4.0 3352.8 1.2
Clinoptilolite 1 (5) 3.7 3353.0 1.1
Clinoptilolite 2 (5) 3.7 3680.0 1.0
Smectite (6) 3.9 3542.4 1.1
Iron Humate (7) 6.7 4164.6 1.6


Contrast: 1 vs. 2 NS NS *
Contrast: 2 vs. others NS
Contrast: 2 vs. 3 NS
Contrast: 2 vs. 4 NS NS NS
Contrast: 2 vs. 5 NS NS NS
Contrast: 2 vs. 6 NS NS NS
Contrast: 2 vs. 7
Contrast: 3 vs. 4 NS ** NS
Contrast: 3 vs. 7*** *


CV (%) 15.4
NS, *, **, ***, Not significant, significant at the 0.05, 0.01, and 0
respectively.
t 85% USGA uncoated sand plus 15% amendment by volume
$ Water Use Efficiency = clipping yield / applied water
2.5% by volume


7.5
.001 probability levels,


amended pots, and CCs and DEs were found to have similar amounts of PAW as peat, it

is likely nutrients applied to pots containing CCs and DEs were more plant available than

that applied to pots containing peat. Mehlich I extractable levels of P, K, and Fe from

CCs and DEs were found to be higher than those from peat amended pots (Table 4-3).

Thus, higher WUE ratings were observed from CCs and DEs than from peat.

Water-use-efficiency ratings from iron-humate and smectite were identical and

higher than all other amended pots (Table 4-14). These results regarding iron humate









contradict those reported by Sartain and Comer (2004). They investigated WUE of

bermudagrass one year after establishment and observed pots containing peat had greater

WUE ratings than pots containing sand/iron humate or sand alone. Iron humate is a

residual product of water treatment facilities. As such, its consistency over time may

vary along with its organic matter and nutrient content. Iron humate used in this study

contained higher levels of N, K, Ca, and Fe than iron humate used in the study by Comer

(1999). This could account for the different responses observed during this study.

When amendments were incorporated following 9-tine aerification, differences

between treatment means became less apparent (Table 4-15). Only iron humate, CCs,

and sand increased WUE above that of the sand/peat mixture. The increase in WUE from

CCs was largely due to a 13% decrease in water required to maintain 90% field capacity.

Iron humate required 17% more water than peat, but produced 90% more dry matter.

This may be indicative of an increase in nutrient uptake by turf grown in iron humate

amended sand. Iron humate produce 23% greater WUE than CCs which produced the

second highest WUE response. Lowest WUE responses were observed from peat and

zeolite amended pots. During 2003, incorporation of soil amendments via 9-tine

aerification produced 22% lower WUE than when amendments were fully mixed into the

rootzone. Fully mixing amendments with sand allows for greater consistency and

homogeneity. Thus, fully-mixed amendments had a greater influence on turf growth than

when amendments were incorporated in localized regions throughout the rootzone as was

the case in each aerification method.

Incorporation of soil amendments via 4-tine aerification had a similar influence on

turf WUE as 9-tine aerification (Table 4-16). The only amendment that increased WUE










Table 4-16. Tissue yield, applied water, and water-use-efficiency of Tifdwarf
bermudagrass as influenced by soil amendments after 4 tine aerification
during glasshouse 2003 study.
Rootzone Mixturet. Clipping Yield Applied Water WUEt
(g) (ml) (mg g-)
Sand (1) 3.8 3456.1 1.1
Peat (2) 3.8 3193.2 1.2
Calcined clay 1 (3) 3.9 3033.3 1.3
Calcined clay 2 (3) 3.8 3141.7 1.2
Diatomaceous earth 1 (4) 3.9 3533.3 1.1
Diatomaceous earth 2 (4) 4.3 3559.7 1.2
Clinoptilolite 1 (5) 4.2 3472.2 1.2
Clinoptilolite 2 (5) 3.8 3460.6 1.1
Smectite (6) 3.9 3515.2 1.1
Iron Humate (7) 5.7 4085.7 1.4


Contrast: 1 vs. 2 NS NS NS
Contrast: 2 vs. others NS
Contrast: 2 vs. 3 NS NS NS
Contrast: 2 vs. 4 NS NS
Contrast: 2 vs. 5 NS NS NS
Contrast: 2 vs. 6 NS NS
Contrast: 2 vs. 7
Contrast: 3 vs. 4 NS NS
Contrast: 3 vs. 7 ****


CV (%) 13.1
NS, *, **, ***, Not significant, significant at the 0.05, 0.01, and 0
respectively.
t 85% USGA uncoated sand plus 15% amendment by volume
$ Water Use Efficiency = clipping yield / applied water
2.5% by volume


6.9
.001 probability levels,


above peat was iron humate. This trend remained consistent across all incorporation

methods. However, the influence of iron humate on WUE decreased in the order of: full

incorporation > 9-tine aerification > 4-tine aerification. However, no differences were

observed between the overall mean of treatments from 9-tine and 4-tine aerification

(Table 4-17). According to these results, soil amendments may not increase WUE when

incorporated after aerification compared to full incorporation. Moreover, it seems the

likelihood of producing an increase in WUE will increase as more of the rootzone is









removed during aerification. However, incorporation of amendments into a sand-based

rootzone will produce the greatest increase in turf quality, clipping yield, and WUE when

the amendment is fully incorporated into the rootzone (Table 4-17). This allows for a

more even distribution of nutrients and moisture for turf uptake.


Table 4-17. Water use efficiency of Tifdwarf bermudagrass as influenced by
incorporation method.
Method Water Use Efficiency
Full (1) 1.4
4 Tine (2) 1.1
9 Tine (3) 1.1

Contrast: 1 vs. 2
Contrast: 2 vs. 3 NS

CV (%) 3.5


Nutrient Leaching Study

As previously mentioned, a primary concern in the golf industry is to minimize any

environmental impact that may arise from fertilizer applications. This phase of the study

compares 3 soil amendments and their capacity to retain NO3s, NH4+, and P during

periods of normal nutrient but high water applications.

Nitrate

No differences were observed between the N03-N breakthrough curves of sand and

sand/peat rootzones (Fig. 4-7). As desired, nitrate-N leached as a pulse. Maximum NO3-

N concentration reached 0.2 C/Co at one pore volume and quickly dropped, tapering off

to no detectable N03-N at near 2.5 pore volumes. Both sand and sand/peat leaching

patterns were well described by the CD model. Thus, nitrate can be assumed to have

moved through the column with the wetting front, and the primary mode of leaching was

convection.









81








Sand/Peat 0 Sand
0.20 CD Model -- CD Moc


0.15


0.10


0.05


0.00 ** .. 0**
0.25


0.20 HDTMA Soil Master Soil Ma!
CD Moc
0.15


0.10


0.05


O 0.00 ************0*********0 00-6
0.25
0

0.20 0 HDTMA Profile Profile
CD Moc
0.15


0.10


0.05


0.006 0************************* ** 0
0.25


0.20 S Ecosani
HDTMA Ecosand Ecosa
CD Moc
0.15


0.10


0.05


0.00 *********************** 0000.
0 1 2 30 1 2 3


Effluent Volume (Pore Volume)


Figure 4-7. Nitrate breakthrough curves as influenced by filter zone media.









Both CCs were found to have similar NO3 breakthrough curves to that of sand and

sand/peat (Fig. 4-7). Calcined clays, sand, and peat have effectively no anion exchange

capacity, thus similar leaching patterns were expected. These findings agree with those

reported by Bigelow et al., (2004) who also investigated NO3 leaching through sand

amended with CCs. They reported that more than 90% of applied NO3-N leached

through all rootzone mixtures, and, in general, non-amended sand and sand/amendment

mixtures were similar regarding NO3-N leaching.

Leaching patterns from columns containing zeolite differed from columns

containing CCs or peat. Minimal retention of NO3-N was observed in columns

containing zeolite (Fig. 4-7). Maximum NO3-N concentration in leachate from zeolite

columns were approximately 5% lower than columns containing sand as the filter zone

media. Due to the high CEC of zeolite, this result was not expected and it is unlikely that

any NO3-N was retained directly. However, it is possible that as NH4 ions were absorbed

into the zeolite structure, movement of the NO3 ion, previously associated with the NH4

ion, through the column was delayed via its ion pair. This 'ion pair' hypothesis has been

previously proposed by Brown (2003) when studying the movement of Ca(NO3)2 through

turfgrass covered soil columns. Unfortunately, evidence of this phenomenon was not

substantiated. However, these results indicate decreased leaching of one ion due to

retention of its counterion may occur.

When each amendment was coated with HDTMA, nitrate-N was removed from

solution to the extent that the CD model did not fit the data (Fig 4-7). All NO3-N was

retained by SMSA following 4 pore volumes, except calcined clay 2 in which 5% of

applied NO3-N eventually leached (Table 4-18). Columns that contained unmodified soil










amendments leached between 94 and 102% of applied N03-N. These results are

substantially higher than those reported by previous researchers when using the same

fertilizer source (Brown et al., 1982; Snyder et al., 1984). However, both Brown and

Snyder conducted leaching studies over longer periods of time compared to this study in

which N03-N remained in columns for less than 20 minutes. The longer time period

would subject N03-N to a variety of conversion processes and potentially decrease NO3

leaching.

Nitrate-N sorption isotherms may help to explain the leaching patterns and

retention by SMSAs (Fig. A-9). Uncoated amendments did not sorb any N03-N (data not

included on graph). Surfactant-coated calcined clay 1 sorbed more N03-N than calcined

Table 4-18. Total N03-N leached as influenced by filter zone media.
Root zone media .Filter zone media N03-N Leached
(mg) % of Applied
Sand Sand (1) 21.6 96.0
Sand/Peat Sand (2) 22.1 98.2
Sand/Peat Clinoptilolite 1 (3) 21.5 95.5
Sand/Peat Calcined clay 2 (4) 23.1 102.6
Sand/Peat Calcined clay 1 (5) 21.3 94.6
Sand/Peat HDTMA-Clinoptilolite 1 (6) 0.0 0.0
Sand/Peat HDTMA-Calcined clay 2 (7) 1.0 4.4
Sand/Peat HDTMA-Calcined clay 1 (8) 0.0 0.0


Contrast: 1 vs. 2 NS
Contrast: 2 vs. 6
Contrast: 2 vs. 7
Contrast: 2 vs. 8
Contrast: 3 vs. 6
Contrast: 4 vs. 7
Contrast: 5 vs. 8 ***
CV (%) 9.8
NS, ***, Not significant, significant at 0.001 probability level respectively.









clay 2 or clinoptilolite 1. Calcined clay 2 and clinoptilolite 1 produced similar isotherms

with calcined clay 2 retaining slightly more N03-N than clinoptilolite 1. These isotherms

relate well with each amendment's effective anion exchange capacity (EAEC) (Table 4-

1). Calcined clay 1 and clinoptilolite 1 had the highest and lowest EAEC, respectively.

Thus, calcined clay 1 and clinoptilolite 1 produced the highest and lowest Smax,

respectively.

Ammonium

When HDTMA is coated onto a solid phase that possesses a CEC, the effective CEC of

that solid may decrease (Table 4-1). This is due to a portion of the original cation

exchange sites being occupied by HDTMA head groups. Due to this decrease in CEC,

sorption or retention of cations from soil solution may also decrease. This phenomenon

was observed during analysis of NH4-N leaching.

Leaching patterns of NH4-N through columns containing only sand were similar to

leaching patterns of N03-N through the same columns (Fig. 4-8) and were well described

by the 2-site model. The 2-site model parameters can be seen in table A-2. Maximum

NH4-N concentrations reached 0.21 C/Co and were observed at 1.09 pore volumes. This

indicates that, under these experimental conditions, the movement and retention of NH4-

N is not influenced by USGA sand. These findings support previous work conducted

under similar experimental conditions (Bigelow et al., 2003).

Addition of peat into the rootzone mixture decreased maximum NH4-N

concentration in leachate by 25% (Fig. 4-8). Furthermore, peak concentrations were

observed at 1.1 pore volumes which lead to a higher retardation factor (R). However, no





















* Sand/Peat
- 2-Site Model


025


020


015


010


005


000
025


020


015


010


005


0 000
0 0 25


020


015


010


005


000
025


020


015


010


005


000


* HDTMA- Profile
- 2-Site Model


* HDTMA Ecosand
- 2-Site Model


* Sand
- 2-Site Model


* Soil Master
- 2-Site Model


* Profile


* Ecosand


2 3 0 1 2


Effluent Volume (Pore Volume)


Figure 4-8. Ammonium breakthrough curves as influenced by filter zone media.


* HDTMA Soil Master
- 2-Site Model









differences in total NH4-N leached were observed between columns containing sand and

sand/peat. This indicates the CEC increase associated with peat addition (Table 4-3) is

enough to delay NH4-N leaching, but will not prevent NH4-N from leaching under these

conditions. These findings are in contrast to previous research. In general, past research

has shown that under normal growing conditions, leaching of NH4-N is minimal due

primarily to the rapid conversion of NH4-N to N03-N in well-aerated soils that contain an

adequate microbe population (Petrovic 1990; Reddy, 1982; Tate, 1977). Thus, inclusion

of peat into a sand-based media has been shown to reduce NH4-N leaching by as much as

70% (Bigelow et al., 2003). However, this study was conducted under a worse-case

scenario in which oxygen was limited and percolation rates were high. Therefore,

nitrification was likely limited and, thus, peat did not have as great an influence on total

NH4-N leached as previous research might indicate.

Addition of a filter layer containing unmodified amendments reduced NH4-N

leaching by 98%. (Table 4-18). No NH4-N was detected in leachate from columns

containing zeolite while 6% of applied NH4-N leached through calcined clay 1.

Decreased NH4-N leaching from zeolite amended sand than from CC amended sand was

also observed by Bigelow et al. (2003). The removal of NH4-N from leachate in this

study was likely due to two factors. First, because CCs and zeolites possess relatively

high CECs (Table 4-2), they each have the capacity to remove large amounts of cations

from solution. Sorption isotherms showed that CCs are capable of adsorbing between 55

and 65 mg kg-1 NH4-N, while zeolites which possess a higher CEC are capable of

adsorbing 260 mg kg-1 NH4-N (Fig A-10, Fig A-11, Fig A-12). Secondly, amendments

were placed in each column in a 2 cm thick layer below the rootzone which forced all










Table 4-18. Total NH4-N leached as influenced by filter zone media.
Root zone media Filter zone media NH4-N Leached
--- (mg) --- % of Applied
Sand/Peat Clinoptilolite 1 (1) 0.0 0.0
Sand/Peat Calcined clay 2 (2) 0.0 0.0
Sand/Peat Calcined clay 1 (3) 1.5 6.0
Sand/Peat HDTMA-Clinoptilolite 1 (4) 1.0 4.0
Sand/Peat HDTMA-Calcined clay 2 (5) 12.5 50.4
Sand/Peat HDTMA-Calcined clay 1 (6) 18.2 73.3
Sand/Peat Sand (7) 22.7 91.5
Sand Sand (8) 23.1 93.1


Contrast: 1 vs. 4 NS
Contrast: 2 vs. 5
Contrast: 3 vs. 6 ***
Contrast: 7 vs. 8 NS
Contrast: 7 vs. 4
Contrast: 7 vs. 5
Contrast: 7 vs. 6

CV (%) 12.9
NS, ***, Not significant, significant at 0.001 probability level respectively.


leachate to pass through each amendment. It is probable that the thickness of this layer

directly influences the retention of potential contaminants. The influence of filter layer

thickness is of concern and future research in this area would be valuable.

When CCs were coated with HDTMA, each amendments capacity to retain NH4-N

decreased (Fig A-10, Fig A-11). Thus, more NH4-N leached through columns containing

HDTMA-coated calcined clay 1 and calcined clay 2 than columns containing their

unmodified counterparts (Table 4-18). Only a minor decrease in NH4-N retention was

observed from HDTMA-clinoptilolite 1 (Fig A-12). Thus, columns containing

clinoptilolite 1 and HDTMA-clinoptilolite 1 leached similar amounts of NH4-N (Table 4-

18). The influence of SMSA on decreasing NH4-N leaching in order of decreasing

effectiveness was: clinoptilolite 1 > calcined clay 2 > calcined clay 1. These results