Figure 14.22 Inorganic fixation of added phosphates at various soil pH values.

Average conditions are

represented and any particular soil would have a somewhat different distribution. The actual proportion
of the phosphorus remaining in an available form will depend upon contact with the soil, time for
reaction, and other factors. It should be kept in mind that some of the added phosphorus may be
changed to organic forms in which it would be temporarily unavailable but subject to mineralization.
(Diagram courtesy of N. Brady and Ray R. Weil)

Figure 14.23 Several of the reactions by which phosphate ions are removed from soil solution and fixed
by the iron and aluminum in various hydrous oxides. Freshly precipitated aluminum, iron, and
manganese phosphates (a) are relatively available, though over time they become increasingly
unavailable. In (b) the phosphate is reversibly adsorbed by anion exchange. In reactions of the type
shown in (c) a phosphate ion replaces an —OH2 or an —OH group in the surface structure of Al or Fe
hydrous oxide minerals. In (d) the phosphate further penetrates the mineral surface by forming a stable
binuclear bridge. The adsorption reactions (b–d) are shown in order from those that bind phosphate
with the least tenacity to the most tenacity (from the most to the least reversible and plantavailable).
Phosphate ions added to a soil may undergo this entire sequence of these reactions, becoming
increasingly unavailable. Note that (b) illustrates an outer-sphere complex, while (c) and (d) are examples
of inner-sphere complexes (see Figure 8.25). (Diagram courtesy of Ray R. Weil)

Figure 14.24 When a granule of soluble calcium monophosphate [Ca(H2PO4)2 · H2O] fertilizer is added
to moist soil, the following series of reactions rapidly reduces the availability of the added phosphorus:
(a) The Ca(H2PO4)2 · H2O (x) in the fertilizer granule attracts water from the soil. (b) In the moistened
granule, phosphoric acid is formed by the following reaction: Ca(H2PO4)2·H2O +H2O S CaHPO4 · 2H2O +
H3PO4. As more water is attracted, an H3PO4-laden solution with a pH of about 1.4 moves outward
from the granule. (c) This acid solution dissolves and displaces large quantities of iron, aluminum, and
manganese. These ions promptly react with the phosphate to form low-solubility compounds. (d) Later,
these compounds revert to the hydroxy phosphates of iron, aluminum, and manganese in acid soils. In
neutral to alkaline soils, equally insoluble calcium phosphates are formed. In both cases, insoluble
dicalcium phosphate (CaHPO4 · 2H2O) remains in the granule ( ). Fortunately, the phosphorus in the
freshly precipitated compounds is slightly available for plant uptake. But when these freshly precipitated
compounds are allowed to age or to revert to more insoluble forms, the phosphorus becomes almost
completely unavailable to plants in the short term. (Diagram courtesy of Ray R. Weil)

Figure 14.25 Certain soil microorganisms can increase the availability of phosphorus in minerals such as
phosphate rock and aluminum phosphates that normally hold the phosphorus in very insoluble forms.
(inset) A micrograph of a fungus growing on an aluminum phosphate soil surface. The fungus is thought
to produce organic acids that help solubilize phosphorus. (bar graph)In another experiment, phosphorus
is released from phosphate rock by a fungus (Aspergillus niger) that had been isolated from a tropical
soil. [Micrograph (inset) courtesy of Dr. Anne Taunton, University of Wisconsin; bar graph drawn from
data in Goenadi et al. (2000)]