14.

6 SOLUBILITY OF INORGANIC SOIL PHOSPHORUS

The particular types of reactions that fix phosphorus in relatively unavailable forms differ from soil to soil
and are closely related to soil pH (Figure 14.22). In acid soils these reactions involve mostly Al, Fe, or Mn,
either as dissolved ions, oxides, or hydrous oxides. Many soils contain such hydrous oxides as coatings on
soil particles and as interlayer precipitates in silicate clays. In alkaline and calcareous soils, the reactions
primarily involve precipitation as various calcium phosphate minerals (see Table 14.5) or adsorption to
the iron impurities on the surfaces of carbonates and clays. At moderate pH values, adsorption on the
edges of kaolinite or on the iron oxide coating on kaolinite clays plays an important role.

Precipitation by Iron, Aluminum, and Manganese Ions

Probably the easiest type of phosphorus-fixation reaction to visualize is the simple reaction of H2PO4-
ions with dissolved Fe3+, Al3+, and Mn3+ ions to form insoluble hydroxy phosphate precipitates (Figure
14.23a). In strongly acid soils, enough soluble Al, Fe, or Mn is usually present to cause the chemical
precipitation of nearly all dissolved H2PO4- ions by reactions such as the following (using the aluminum
cation as an example):

Freshly precipitated hydroxy phosphates are slightly soluble because they have a great deal of surface
area exposed to the soil solution. Therefore, the phosphorus contained in them is, initially at least,
somewhat available to plants. Over time, however, as the precipitated hydroxy phosphates age, they
become less soluble and the phosphorus in them becomes almost completely unavailable to most
plants.

Reaction with Hydrous Oxides and Silicate Clays

Most of the phosphorus fixation in acid soils probably occurs when H2PO4- ions react with, or become
adsorbed to, the surfaces of insoluble oxides of iron, aluminum, and manganese, such as gibbsite (Al2O3
· 3H2O) and goethite (Fe2O3 · 3H2O; see Figure 14.23) and with 1:1 type silicate clays. These hydrous
oxides occur as crystalline and noncrystalline particles and as coatings on the interlayer and external
surfaces of clay particles. Fixation of phosphorus by clays probably takes place over a relatively wide pH
range (see Figure 14.22). The large quantities of Fe, Al oxides and 1:1 clays present in many soils make
possible the fixation of extremely large amounts of phosphorus by these reactions.
Although all the exact mechanisms have not been identified, H2PO4- ions are known to react with iron
and aluminum mineral surfaces in several different ways, resulting in different degrees of phosphorus
fixation. Some of these reactions are shown diagrammatically in Figure 14.23.

H2PO4- anion may be attracted to positive charges that develop under acid conditions on the surfaces
of iron and aluminum oxides and the broken edges of kaolinite clays (see Figure 14.23b). The adsorbed
H2PO4- anions form outer-sphere complexes and are subject to anion exchange with certain other
anions, such as OH-, SO42-, MoO42-, or organic acids (R—COO−; see Section 8.7). Since this type of
adsorption of H2PO4- ions is reversible, the phosphorus may slowly become available to plants.
Availability of such adsorbed H2PO4- may be increased by: (1) liming the soil to increase the hydroxyl
ions, or (2) adding organic matter to increase organic acids (anions) capable of replacing H2PO4-.

phosphate ion may also replace a structural hydroxyl to form an inner-sphere complex with the oxide (or
clay) surface (see Figure 14.23c). This reaction, while reversible, binds the phosphate too tightly to allow
its ready replacement by other anions. The availability of phosphate bound in this manner is very low.
Over time, a second oxygen of the phosphate ion may replace a second hydroxyl, so that the phosphate
becomes chemically bound to two adjacent aluminum (or iron) atoms in the hydrous oxide surface (see
Figure 14.23d). With this step, the phosphate becomes an integral part of the oxide mineral, and the
likelihood of its release back to the soil solution is extremely small.

Finally, as more time passes, the precipitation of additional iron or aluminum hydrous oxide may bury
the phosphate deep inside the oxide particle (see Figure 14.21). Such phosphate is termed occluded and
is the least available form of phosphorus in most acid soils.Precipitation reactions similar to those just
described are responsible for the rapid reduction in availability of phosphorus added to soil as soluble
Ca(H2PO4)2 · H2O in fertilizers (Figure 14.24). As already mentioned, (see Box 14.2) this type of reaction
can also be used to control the solubility of phosphorus in wastewater.

Effect of Iron Reduction Under Wet Conditions

Phosphorus bound to iron oxides by the mechanisms just discussed is very insoluble under well-aerated
conditions. However, prolonged anaerobic conditions can reduce the iron in these complexes from Fe3+
to Fe2+, making the iron–phosphate complex much more soluble and causing it to release phosphorus
into solution. The release of phosphorus from iron phosphates by means of the reduction and
subsequent solubilization of iron improves the phosphorus availability in soils used for paddy rice.

These reactions are also of special relevance to water quality. Phosphorus bound to soil particles may
accumulate in underwater sediments, along with organic matter and other debris. As the sediments
become anoxic, the reducing environment may cause the gradual release of phosphorus held by hydrous
iron oxides. Thus, the phosphorus eroded from soils today may aggravate the problem of eutrophication
for years to come, even after the erosion and loss of phosphorus from the land has been brought under
control.

Reaction with Calcium and Magnesium Compounds in Alkaline Soils7

In alkaline soils (e.g., pH = 8), soluble H2PO4- quickly reacts with calcium to form a sequence of products
of decreasing solubility. For instance, highly soluble monocalcium phosphate [Ca(H2PO4)2 · H2O] added
as concentrated superphosphate fertilizer rapidly reacts with calcium carbonate in the soil to form first
dicalcium phosphate (CaHPO4 · 2H2O) and then tricalcium phosphate [Ca3(PO4)2], as follows:

The solubility of these compounds and, in turn, the plant availability of the phosphorus they contain
decrease as the phosphorus changes from the H2PO4- ion to tricalcium phosphate [Ca3(PO4)2].
Although this compound is quite insoluble, it may undergo further reactions to form even more insoluble
compounds, such as the hydroxy-, oxy-, carbonate-, and fluor-apatites shown in Table 14.5. These
compounds are thousands of times less soluble than freshly formed tricalcium phosphates. Because of
these solubility relationships powdered phosphate rock (which consists mainly of apatite minerals) may
be an effective source of phosphorus for plants in strongly acid soils, while the same material would
likely be of little utility if used on neutral or alkaline soils.Because of the various reactions with CaCO3,
phosphorus availability tends to be nearly as low in the Aridisols, Inceptisols, and Mollisols of arid
regions as in the highly acid Spodosols, Ultisols, and Oxisols of humid regions, where iron, aluminum,
and manganese limit phosphorus availability.

Biological Influences on Solubility of Inorganic Phosphorus Compounds in Soils

Certain bacteria and fungi enhance the solubility of both calcium and iron and aluminum phosphates by
releasing citric and other organic acids. These acids either dissolve the calcium phosphates or form metal
complexes that release the P from iron and aluminum phosphates (Figure 14.25). The released P is likely
used first by the microorganisms themselves, but is eventually made available to plants as well (see
Section 14.8).