Contents

3.1 Background Information 51

3.1.1 Historical Information 51

3.1.2 Phosphorus Functions in Plants 52

3.1.3 Nature and Transformations of Soil Phosphorus 53

3.2 Diagnosing Phosphorus Deficiency 54

3.2.1 Visual Symptoms of Deficiency and Excess 54

3.2.2 Tissue Testing for Phosphorus 55

3.2.3 Soil Testing for Phosphorus 71

3.3 Factors Affecting Management of Phosphorus Fertilization 75

3.3.1 Crop Response to Phosphorus 75

3.3.2 Soil Water 76

3.3.3 Soil Temperature 78

3.3.4 Sources of Phosphorus 79

3.3.5 Timing of Application of Phosphorus Fertilizers 79

3.3.6 Placement of Phosphorus Fertilizers 79

3.3.7 Foliar-Applied Phosphorus Fertilization 81

3.3.8 Fertilization in Irrigation Water 81

References 82

3.1 BACKGROUND INFORMATION 3.1.1 Historical Information

Incidental phosphorus fertilization in the form of manures, plant and animal biomass, and other natural materials, such as bones, probably has been practiced since agriculture began. Although specific nutritional benefits were unknown, Arthur Young in the Annuals of Agriculture in the mid-nineteenth century describes experiments evaluating a wide range of products including poultry dung, gunpowder, charcoal, ashes, and various salts. The results showed positive crop responses to certain materials. Benefiting from recent developments in chemistry by Antoine Lavoisier (1743-1794) and others, Theodore de Saussure (1767-1845) was perhaps the first to advance the concept that plants absorb specific mineral elements from the soil.

The science of plant nutrition advanced considerably in the nineteenth century owing to contributions by Carl Sprengel (1787-1859), A.F. Wiegmann (1771-1853), Jean-Baptiste Boussingault (1802-1887), and Justus von Liebig (1803-1873). Based on the ubiquitous presence of phosphorus in soil and plant materials, and crop responses to phosphorus-containing products, it became apparent that phosphorus was essential for plant growth.

Liebig observed that dissolving bones in sulfuric acid enhanced phosphorus availability to plants. Familiar with Liebig's work, John Lawes in collaboration with others, evaluated several apatite-containing products as phosphorus nutritional sources for plants. Lawes performed these experiments in what ultimately became the world's most famous agricultural experiment station—his estate in Rothamsted. The limited supply of bones prompted developments in the utilization of rock phosphates where Lawes obtained the first patent concerning the utilization of acid-treated rock phosphate in 1842, The first commercial production of rock phosphate began in Suffolk, England, in 1847. Mining phosphate in the United States began in 1867. Thus began the phosphorus fertilizer industry.

Crop responses to phosphorus fertilization were widespread. For many years phosphorus fertilization practices were based on grower experience often augmented with empirical data from experiment station field tests. Although researchers and growers realized that customized phosphorus fertilizer recommendations would be invaluable, early work often focused on total element content of soils and produced disappointing results. The productivity of soil essentially showed no correlation to total content of nutrients in them.

It was during the twentieth century that the recognition that the plant itself was an excellent indicator of nutrient deficiency coupled with considerable advances in analytical methodology gave way to significant advances in the use of tissue testing. Hall (1) proposed plant analysis as a means of determining the normal nutrient contents of plants. Macy (2) proposed the basic theory that there was a critical concentration of nutrient in a plant above which there was luxury consumption and below which there was poverty adjustment, which was proportional to the deficiency until a minimum percentage was reached.

Also during the twentieth century, a greater understanding of soil chemistry of phosphorus and the observation that dilute acids seem to correlate to plant-available phosphorus in the soil gave way to the development of successful soil-testing methodologies. The early contributions of Dyer (3), Truog (4), Morgon (5), and Bray and Kutrz (6) are noteworthy. Plant tissue testing and soil testing for phosphorus are discussed in greater detail in the subsequent sections. For more detailed history on plant nutrition and soil-plant relationships, readers are referred to Kitchen (7) and Russell (8).

3.1.2 Phosphorus Functions in Plants

Phosphorus is utilized in the fully oxidized and hydrated form as orthophosphate. Plants typically absorb either H2PO4~ or HPO42 , depending on the pH of the growing medium. However, under certain conditions plants might absorb soluble organic phosphates, including nucleic acids. A portion of absorbed inorganic phosphorus is quickly combined into organic molecules upon entry into the roots or after it is transported into the shoot.

Phosphate is a trivalent resonating tetraoxyanion that serves as a linkage or binding site and is generally resistant to polarization and nucleophilic attack except in metal-enzyme complexes (9). Orthophosphate can be condensed to form oxygen-linked polyphosphates. These unique properties of phosphate produce water-stable anhydrides and esters that are important in energy storage and transfer in plant biochemical processes. Most notable are adenosine diphosphate and triphosphate (ADP and ATP). Energy is released when a terminal phosphate is split from ADP or ATP. The transfer of phosphate molecules to ATP from energy-transforming processes and from ATP to energy-requiring processes in the plants is known as phosphorylation. A portion of the energy derived from photosynthesis is conserved by phosphorylation of ADP to yield ATP in a process called photophosphorylation. Energy released during respiration is similarly harnessed in a process called oxidative phosphorylation.

Beyond their role in energy-transferring processes, phosphate bonds serve as important linkage groups. Phosphate is a structural component of phospholipids, nucleic acids, nucleotides, coenzymes, and phosphoproteins. Phospholipids are important in membrane structure. Nucleic acids of genes and chromosomes carry genetic material from cell to cell. As a monoester, phosphorus provides an essential ligand in enzymatic catalysis. Phytic acid, the hexaphosphate ester of myoinositol phosphate, is the most common phosphorus reserve in seeds. Inorganic and organic phosphates in plants also serve as buffers in the maintenance of cellular pH.

Total phosphorus in plant tissue ranges from about 0.1 to 1%. Bieleski (10) suggests that a typical plant might contain approximately 0.004% P as deoxyribonucleic acid (DNA), 0.04% P as ribonucleic acid (RNA), 0.03% as lipid P, 0.02 % as ester P, and 0.13% as inorganic P.

3.1.3 Nature and Transformations of Soil Phosphorus

Soils contain organic and inorganic phosphorus compounds. Because organic compounds are largely derived from plant residues, microbial cells, and metabolic products, components of soil organic matter are often similar to these source materials. Approximately 1% of the organic phosphorus is in the phospholipid fraction; 5 to 10% is in nucleic acids or degradation products, and up to 60% is in an inositol polyphosphate fraction (11). A significant portion of the soil organic fraction is unidentified.

Phospholipids and nucleic acids that enter the soil are degraded rapidly by soil microorganisms (12,13). The more stable, and therefore more abundant, constituents of the organic phosphorus fraction are the inositol phosphates. Inositol polyphosphates are usually associated with high-molecular-weight molecules extracted from the soil, suggesting that they are an important component of humus (14,15).

Soils normally contain a wide range of microorganisms capable of releasing inorganic orthophosphate from organic phosphates of plant and microbial origin (16,17). Conditions that favor the activities of these organisms, such as warm temperatures and near-neutral pH values also favor mineralization of organic phosphorus in soils (16,18). The enzymes involved in the cleavage of phosphate from organic substrates are collectively called phosphatases. Microorganisms produce a variety of phosphatases that mineralize organic phosphate (19).

Phosphorus released to the soil solution from the mineralization of organic matter might be taken up by the microbial population, taken up by growing plants, transferred to the soil inorganic pool, or less likely lost by leaching and runoff (Figure 3.1). Phosphorus, like nitrogen, undergoes mineralization and immobilization. The net phosphorus release depends on the phosphorus concentration of the residues undergoing decay and the phosphorus requirements of the active microbial population (16).

In addition to phosphorus mineralization and immobilization, it appears that organic matter has indirect, but sometimes inconsistent, effects on soil phosphorus reactions. Lopez-Hernandez and Burnham (20) reported a positive correlation between humification and phosphate-sorption capacity. Wild (21) concluded that the phosphorus-sorption capacity of organic matter is negligible. It is observed more commonly that organic matter hinders phosphorus sorption, thereby enhancing availability. Humic acids and other organic acids often reduce phosphorus fixation through the formation of complexes (chelates) with Fe, Al, Ca, and other cations that react with phosphorus (22-24). Studies have shown that organic phosphorus is much more mobile in soils than inorganic sources (25). The

figure 3.1 Phosphorus cycle in agricultural soils.

interaction between the organic and inorganic phosphorus fractions is understood poorly. It is generally presumed that phosphorus availability to plants is controlled by the inorganic phosphorus fraction, although the contribution of organic phosphorus to plant nutrition should not be dismissed.

Inorganic phosphorus entering the soil solution, by mineralization or fertilizer additions, is rapidly converted into less available forms. Sorption and precipitation reactions are involved. The sorption of inorganic phosphorus from solution is closely related to the presence of amorphous iron and aluminum oxides and hydrous oxides (26-30) and the amounts of calcium carbonate (CaCO3) (24,31,32).

Hydrous oxides and oxides of aluminum and iron often occur as coatings on clay mineral surfaces (27,28,33), and these coatings may account for a large portion of the phosphorus sorption associated with the clay fraction of soils. Even in calcareous soils, hydrous oxides have been demonstrated as being important in phosphorus sorption, as was demonstrated by Shukla (34) for calcareous lake sediments, Holford and Mattingly (24) for calcareous mineral soils, and Porter and Sanchez (35) for calcareous Histosols.

In calcareous soils, phosphorus (or phosphate) sorption to CaCO3 may be of equal or greater importance than sorption to aluminum and iron oxides (35). In a laboratory investigation with pure calcite, Cole (31) concluded that the reaction of phosphorus with CaCO3 consisted of initial sorption reactions followed by precipitation with increasing concentrations of phosphorus. Phosphorus sorption may occur in part as a multilayer phenomenon on specific sites of the calcite surface (24,32). As sorption proceeds, lateral interactions occur between sorbed phosphorus, eventually resulting in clusters. These clusters in turn serve as centers for the heterogeneous nucleation of calcium phosphate crystallites on the calcite surface.

Phosphorus sorption is probably limited to relatively low initial phosphorus solution concentrations and precipitation is likely a more important mechanism of phosphorus removal from the soil solutions at higher concentrations (31). Lindsay (36) identified, by x-ray crystallography, what he considered to be an incomplete list of 32 forms of phosphate compounds as reaction products from phosphorus fertilizers. The nature of the reaction products formed when phosphorus fertilizer is added to soil depends primarily on the coexisting cation, the pH of the saturated solution, the quantity of phosphorus fertilizer added, and the chemical characteristics of the soil (37). In acidic soils, aluminum and iron will generally precipitate phosphorus. In calcareous soils, an acidic fertilizer solution would dissolve calcium, and it is anticipated that most of the added phosphorus fertilizer would precipitate initially as dicalcium phosphate dihydrate (DCPD) and dicalcium phosphate (DCP) (38,39). These products are only moderately stable and undergo a slow conversion into compounds such as octacalcium phosphate, tricalcium phosphate, or one of the apatites.

As discussed above, soil transformations of phosphorus are complex and often ambiguous. Phosphorus availability has often been characterized in general terms (a) as solution phosphorus, often known as the intensity factor, (b) as readily available or labile phosphorus, often known as the quantity factor, and (c) as nonlabile phosphorus. The labile fraction might include easily mineralizable organic phosphorus, low-energy sorbed phosphorus, and soluble mineral phosphorus. The nonlabile fraction might include resistant organic phosphorus, high-energy sorbed phosphorus, and relatively insoluble phosphate minerals. As plants take up phosphorus from the solution, it is replenished from the labile fraction, which in turn is more slowly replenished by the nonlabile fraction. The soil buffer capacity, known as the capacity factor, governs the distribution of phosphorus among these pools. As will be shown in a subsequent section, although some soil tests aim to characterize only the intensity factor, most aim to characterize quantity and capacity factors as indices of phosphorus availability.

3.2 DIAGNOSING PHOSPHORUS DEFICIENCY 3.2.1 Visual Symptoms of Deficiency and Excess

Phosphorus deficiency suppresses or delays growth and maturity. Although phosphorus- deficient plants are generally stunted in appearance, they seldom exhibit the conspicuous foliar symptoms characteristic of some of the other nutrient deficiencies. Furthermore, appreciable overlap often occurs with the symptoms of other nutrient deficiencies. Plant stems or leaves are sometimes dark green, often developing red and purple colors. However, when weather is cool purpling of leaves can also be associated with nitrogen deficiency, as is often observed in Brassica species, or with phosphorus deficiency. Plants stunted by phosphorus deficiency often have small, dark-green leaves and short and slender stems. Sustained phosphorus deficiency will probably produce smaller-sized fruit and limited harvestable vegetable mass. Because phosphorus is mobile in plants, it is translocated readily from old to young leaves as deficiency occurs, and chlorosis and necrosis on older leaves is sometimes observed. Readers are referred to tables of phosphorus deficiency symptoms specific to individual crops and compiled by other authors (40-43).

Most soils readily buffer phosphorus additions, and phosphorus is seldom present in the soil solution at levels that cause direct toxicity. Perhaps the most common symptoms of phosphorus excess are phosphate-induced micronutrient deficiencies, particularly Zn or Cu deficiencies (43,44).

3.2.2 Tissue Testing for Phosphorus

As noted previously, visual indications of phosphorus deficiency are seldom conclusive; consequently, accurate diagnosis typically requires a tissue test. Most diagnostic standards are generated using the theory of Macy (2), as noted previously concerning critical levels, sufficiency ranges, and poverty adjustment. In practice, critical levels or sufficiency ranges are usually determined by plotting final relative yield against phosphorus concentration in plant tissues and interpreting the resulting curvilinear function at some specified level of maximum yield. For many agronomic crops, values of 90 to 95% maximum yield are frequently used. However, for vegetable crops, which have a higher market value and an economic optimum closer to maximum yield, values of 98% have been used (Figure 3.2). Sometimes researchers use discontinuous functions such as the "linear response and plateau" or "quadratic response and plateau" and define adequacy by the plateau line (Figure 3.3). Yet, other researchers have suggested that the correlation to final yield is less than ideal and have proposed the use of incremental growth-rate analysis in developing critical concentrations (45).

Tissue P concentration (%)

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