The nature of phosphorus in soils
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Reviewed July 2009
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Phosphorus (P) is an essential element classified as a macronutrient because of the relatively large amounts of P required by plants. Phosphorus is one of the three nutrients generally added to soils in fertilizers. One of the main roles of P in living organisms is in the transfer of energy. Organic compounds that contain P are used to transfer energy from one reaction to drive another reaction within cells. Adequate P availability for plants stimulates early plant growth and hastens maturity. Although P is essential for plant growth, mismanagement of soil P can pose a threat to water quality. The concentration of P is usually sufficiently low in fresh water so that algae growth is limited. When lakes and rivers are polluted with P, excessive growth of algae often results. High levels of algae reduce water clarity and can lead to decreases in available dissolved oxygen as the algae decays, conditions that can be very detrimental to game fish populations.
The phosphorus cycle
The P cycle is similar to several other mineral nutrient cycles in that P exists in soils and minerals, living organisms, and water. Although P is widely distributed in nature, P is not found by itself in elemental form. Elemental P is extremely reactive and will combine with oxygen when exposed to the air. In natural systems like soil and water, P will exist as phosphate, a chemical form in which each P atom is surrounded by 4 oxygen (O) atoms. Orthophosphate, the simplest phosphate, has the chemical formula PO4-3. In water, orthophosphate mostly exists as H2PO4- in acidic conditions or as HPO42- in alkaline conditions.
Figure 1. The phosphorus cycle.
Phosphate is taken up by plants from soils, utilized by animals that consume plants, and returned to soils as organic residues decay in soils (Figure 1). Much of the phosphate used by living organisms becomes incorporated into organic compounds. When plant materials are returned to the soil, this organic phosphate will slowly be released as inorganic phosphate or be incorporated into more stable organic materials and become part of the soil organic matter. The release of inorganic phosphate from organic phosphates is called mineralization and is caused by microorganisms breaking down organic compounds. The activity of microorganisms is highly influenced by soil temperature and soil moisture. The process is most rapid when soils are warm and moist but well drained. Phosphate can potentially be lost through soil erosion and to a lesser extent to water running over or through the soil.
Many phosphate compounds are not very soluble in water; therefore, most of the phosphate in natural systems exists in solid form. However, soil water and surface water (rivers and lakes) usually contain relatively low concentrations of dissolved (or soluble) phosphorus. Depending on the types of minerals in the area, bodies of water usually contain about 10 ppb or more of dissolved P as orthophosphate. Water bodies may also contain organic P and phosphate attached to small particles of sediment. Total phosphorus in water is all of the phosphorus in solution regardless of its form and is often the form reported in water quality studies. Algal available or bioavailable phosphorus is P that is estimated to be available to organisms like algae that are present in a lake or river. This is usually estimated by a chemical test which is designed to measure the dissolved P and the particulate P that are easily available. This is a measure of the P that is of immediate concern to water quality.
The word phosphorus or P refers to the element and is also used as a general term when a particular chemical form of P is not being designated. For example, the total P content of a soil or plant material is usually expressed as percent P. However, fertilizer analyses are usually reported as percent P2O5. The phosphate form (P2O5) is a chemical produced during fertilizer analysis, but does not exist in either fertilizers or soils.
Forms of phosphorus in soils
In soils P may exist in many different forms. In practical terms, however, P in soils can be thought of existing in 3 "pools":
- solution P
- active P
- fixed P
The solution P pool is very small and will usually contain only a fraction of a pound of P per acre. The solution P will usually be in the orthophosphate form, but small amounts of organic P may exist as well. Plants will only take up P in the orthophosphate form. The solution PS pool is important because it is the pool from which plants take up P and is the only pool that has any measurable mobility. Most of the P taken up by a crop during a growing season will probably have moved only an inch or less through the soil to the roots. A growing crop would quickly deplete the P in the soluble P pool if the pool was not being continuously replenished.
The active P pool is P in the solid phase which is relatively easily released to the soil solution, the water surrounding soil particles. As plants take up phosphate, the concentration of phosphate in solution is decreased and some phosphate from the active P pool is released. Because the solution P pool is very small, the active P pool is the main source of available P for crops. The ability of the active P pool to replenish the soil solution P pool in a soil is what makes a soil fertile with respect to phosphate. An acre of land may contain several pounds to a few hundred pounds of P in the active P pool. The active P pool will contain inorganic phosphate that is attached (or adsorbed) to small particles in the soil, phosphate that reacted with elements such as calcium or aluminum to form somewhat soluble solids, and organic P that is easily mineralized. Adsorbed phosphate ions are held on active sites on the surfaces of soil particles. The amount of phosphate adsorbed by soil increases as the amount of phosphate in solution increases and vice versa (Figure 2). Soil particles can act either as a source or a sink of phosphate to the surrounding water depending on conditions. Soil particles with low levels of adsorbed P that are eroded into a body of water with relatively high levels of dissolved phosphate may adsorb phosphate from the water, and vice versa.
Figure 2. Relationship between P absorbed by soil and P in solution.
The fixed P pool of phosphate will contain inorganic phosphate compounds that are very insoluble and organic compounds that are resistant to mineralization by microorganisms in the soil. Phosphate in this pool may remain in soils for years without being made available to plants and may have very little impact on the fertility of a soil. The inorganic phosphate compounds in this fixed P pool are more crystalline in their structure and less soluble than those compounds considered to be in the active P pool. Some slow conversion between the fixed P pool and the active P pool does occur in soils.
Fate of phosphorus added to soils
The phosphate in fertilizers and manure is initially quite soluble and available. Most phosphate fertilizers have been manufactured by treating rock phosphate (the phosphate-bearing mineral that is mined) with acid to make it more soluble. Manure contains soluble phosphate, organic phosphate, and inorganic phosphate compounds that are quite available. When the fertilizer or manure phosphate comes in contact with the soil, various reactions begin occurring that make the phosphate less soluble and less available. The rates and products of these reactions are dependent on such soil conditions as pH, moisture content, temperature, and the minerals already present in the soil.
As a particle of fertilizer comes in contact with the soil, moisture from the soil will begin dissolving the particle. Dissolving of the fertilizer increases the soluble phosphate in the soil solution around the particle and allows the dissolved phosphate to move a short distance away from the fertilizer particle. Movement is slow but may be increased by rainfall or irrigation water flowing through the soil. As phosphate ions in solution slowly migrate away from the fertilizer particle, most of the phosphate will react with the minerals within the soil. Phosphate ions generally react by adsorbing to soil particles or by combining with elements in the soil such as calcium (Ca), magnesium (Mg), aluminum (Al), and iron (Fe), and forming compounds that are solids. The adsorbed phosphate and the newly formed solids are relatively available to meet crop needs.
Gradually reactions occur in which the adsorbed phosphate and the easily dissolved compounds of phosphate form more insoluble compounds that cause the phosphate to be become fixed and unavailable. Over time this results in a decrease in soil test P. The mechanisms for the changes in phosphate are complex and involve a variety of compounds. In alkaline soils (soil pH greater than 7) Ca is the dominant cation (positive ion) that will react with phosphate. A general sequence of reactions in alkaline soils is the formation of dibasic calcium phosphate dihydrate, octocalcium phosphate, and hydroxyapatite. The formation of each product results in a decrease in solubility and availability of phosphate. In acidic soils (especially with soil pH less than 5.5) Al is the dominant ion that will react with phosphate. In these soils the first products formed would be amorphous Al and Fe phosphates, as well as some Ca phosphates. The amorphous Al and Fe phosphates gradually change into compounds that resemble crystalline variscite (an Al phosphate) and strengite (an Fe phosphate). Each of these reactions will result in very insoluble compounds of phosphate that are generally not available to plants. Reactions that reduce P availability occur in all ranges of soil pH but can be very pronounced in alkaline soils (pH > 7.3) and in acidic soils (pH < 5.5). Maintaining soil pH between 6 and 7 will generally result in the most efficient use of phosphate (Figure 3).
Figure 3. The availability of phosphorus is affected by soil pH.
Adding to the active P pool through fertilization will also increase the amount of fixed P. Depleting the active pool through crop uptake may cause some of the fixed P to slowly become active P. The conversion of available P to fixed P is partially the reason for the low efficiency of P fertilizers. Most of the P fertilizer applied to the soil will not be utilized by the crop in the first season. Continued application of more P than the crops utilize increases the fertility of the soil, but much of the added P becomes fixed and unavailable.
Most fine-to medium-textured soils have large capacities to hold phosphate by adsorption and precipitation. Occasionally the question of how much phosphate a soil can hold is asked, especially when high loading rates of P are expected or have occurred. Soils differ in their phosphate holding capacity. Fine-textured soils can generally hold hundreds of pounds of phosphate per acre. while coarse-textured soils can generally hold much less phosphate due to the more inert character of sand particles as compared to clay particles. In addition the subsoil of many soils often has an even greater capacity to hold phosphate than does the corresponding surface soil. However, an important aspect of the ability of a soil to hold phosphate is that a soil cannot hold increasing amounts of phosphate in the solid phase without also increasing soil solution phosphate (Figure 2). Increased amounts of phosphate in solution will potentially cause more phosphate to be lost to water running over the soil surface or leaching through the soil. Loading soils with very high levels of phosphate will generally not hurt crops but may result in increased phosphate movement to nearby bodies of water.
Predicting the availability of phosphorus in soils
Soils may contain several hundred to several thousand pounds of phosphate per acre. However, much of the phosphate in soils is not available to growing plants. Phosphate in the soil solution P pool is immediately available but the amount is very small in comparison to the total P in soils. The active P pool is phosphorus that can be released into solution but is generally small in comparison to the fixed P.
To determine the need for supplemental P, soil tests are often used to estimate how much phosphate will be available for a crop. The most common way of determining P availability is to mix a small amount of soil with an extracting solution that contains an acid and/or complexing agent that will remove some of the phosphate from the soil particles. The extracting solution and soil are separated by filtration and the amount of P extracted is determined. In alkaline soils, a basic solution may be used as the extractant because an acidic solution will be neutralized by the alkaline soil and be less effective in extracting P. Calibration studies have been done to correlate crop response to fertilizer additions in soils with various soil test levels of P. Using the calibration data, recommendations can be made as to the amounts of phosphate fertilizer that will most likely give optimum yields.
Soil phosphorus and water quality
Phosphorus is a somewhat unique pollutant in that it is an essential element, has low solubility, and is not toxic itself, but may have detrimental effects on water quality at quite low concentrations. There is considerable concern about P being lost from soils and transported to nearby streams and lakes. Several chemical properties of soil P have important implications for the potential loss of P to surface water.
- Phosphorus in soils is almost entirely associated with soil particles. When soil particles are carried to a river or lake, P will be contained in this sediment. When the sediment reaches a body of water it may act as a sink or a source of P in solution. In either case, it is a potential source of P that may eventually be released.
- Most soils have a large capacity to retain P. Even large additions of P will be mostly retained by soils provided there is adequate contact with the soil.
- Increasing the amounts of phosphate in soils results in increased levels of phosphate in soil solutions. This will generally result in small but potentially important increases in the amounts of phosphate in water that passes over or through soils.
- Phosphate in soils is associated more with fine particles than coarse particles. When soil erosion occurs, more fine particles are removed than coarse particles, causing sediment leaving a soil through erosion to be enriched in P.