Chemistry of Phosphorus in soil

Phosphorus is a most important element present in every living cell (Ku Smita et al, 2015). It is
one of the most important micronutrient essential for plant growth. Phosphorus most often limits
nutrients remains present in plant nuclei and act as an energy storage. In the natural environment,
phosphorus (P) is supplied through the weathering and dissolution of rocks and minerals with
very slow solubility. Therefore, P is usually the critical limiting element for plant and animal
production, and throughout the history of natural production and human agriculture, P has been
largely in short supply. Similarly, knowledge of processes controlling the transport of P from
soils to waters, and the availability of P to aquatic biota is of considerable ecological significance
because of the well known role of P in eutrophication (“...enrichment of surface waters by plants
nutrients... a form of pollution that restricts the potential uses of impacted water bodies”; Foy and
Withers, 1995).

Soil P exists in various chemical forms including inorganic P (Pi) and organic P (Po). These P
forms differ in their behavior and fate in soils (Hansen et al., 2004; Turner et al., 2007). Pi
usually accounts for 35% to 70% of total P in soil (calculation from Harrison, 1987). Primary P
minerals including apatites, strengite, and variscite are very stable, and the release of available P
from these minerals by weathering is generally too slow to meet the crop demand though direct
application of phosphate rocks (i.e. apatites) has proved relatively efficient for crop growth in
acidic soils. In contrast, secondary P minerals including calcium (Ca), iron (Fe), and aluminum
(Al) phosphates vary in their dissolution rates, depending on size of mineral particles and soil pH
(Pierzynski et al., 2005; Oelkers and Valsami-Jones, 2008). With increasing soil pH, solubility of
Fe and Al phosphates increases but solubility of Ca phosphate decreases, except for pH values
above 8 (Hinsinger, 2001). The P adsorbed on various clays and Al/Fe oxides can be released by
desorption reactions. All these P forms exist in complex equilibria with each other, representing
fromvery stable, sparingly available, to plant-available P pools such as labile P and solution P.

The major components of the soil P cycle include: dissolution–precipitation (mineral equilibria),
sorption–desorption (interactions between P in solution and soil solid phases), and
mineralization–immobilization (biologically mediated conversions of P between inorganic and
organic forms). All affect the concentration of P in the soil solution and soil solid phases and
thus the amount of P that is available for uptake by plants and microorganisms and for transport
to surface and ground waters. Phosphorus moves within soils (e.g., to plant roots) primarily by
diffusion (movement through soil pores in response to a concentration gradient) because the low
concentrations of dissolved P in the soil solution preclude significant movement by mass flow
(movement in the convective flow of water induced by evapo-transpiration). Losses of P from
soils occur mainly by erosion and surface runoff, (particulate and dissolved P) because gaseous
losses of P do not occur and leaching or subsurface runoff of P (primarily as dissolved P) are rare
in most cases.

The inorganic and organic forms of soil P are in dynamic equilibria with dissolved P in the soil
solution, which is mainly present as primary (PO 43−) or secondary (HPO42−, H2PO4−)
orthophosphates, varying in relative concentrations as a function of soil pH. Most agricultural
soils range in pH from 4.0 to 9.0. At pH 4.0 to 5.5 H 2PO4−predominates, while at pH > 8.0
HPO42− is the major orthophosphate species present. Ion pairs (e.g., CaHPO 40, MgHPO40, or
CaPO4−) may also be present in the soil solution at higher pH values (pH > 7.0), but in most
cases chemical dissolution of these soluble complexes rapidly converts them to orthophosphate.
The soil P cycle (Pierzynski et al, 2000).

P dynamics in the soil/rhizosphere-plant continuum. Source: Shen et al. (2011)

P-fixation

Soil solution P is usually quite low due to the complex interactions of phosphate with various
soil components. Sorption is considered to be the most important process controlling P
availability in soils. The dominant reactions are these with Fe-Al oxides and Ca-carbonates.
Since sorption is to some degree reversible, sorbed P is a source of plant-available P either
immediately or over a long term. It has been estimated that 25 percent or less of P applied
annually is actually taken up in the growing crop (Morgan, 1997). The remaining 75 percent
becomes bound in the soil profile or is lost to water.

The reaction between phosphate and reactive surface Fe and Al oxides is typical of acid soils. It
is highly dependent on the crystallinity and surface area of the oxides present in soils, and thus
on the mineralogy of the clays in soils. Experiments on the reversibility of P sorption have
shown that the plot of sorbed P against concentration is not retraced during desorption (Barrow,
1983), suggesting that sorbed P undergoes further transformations with time (Parfitt et al., 1989),
perhaps also changing its availability for exchange into the soil solution and thus for plant
uptake.

Organically bound P may also undergo precipitation and fixation reactions with Fe and Al. Much
of the secondary Al- and Fe-bound P remains unavailable to plants, as does the P associated with
organic matter of a molecular weight >50.000 (Goh and Williams, 1982). Mechanism of P
sorption and the strength and reversibility of sorption in medium to high pH systems can differ
substantially. Adsorption of P onto CaCO3 and the co-precipitation of Ca-P minerals is
considered to be dominate in both alkaline aquatic and terrestrial systems where carbonates are
present (Cole and Olsen, 1959). However, calcareous soils may still have significant levels of Fe
and Al oxides, either as discrete components or as coatings on other soil particles, and thus
phosphate sorption may also be controlled by the presence of metal oxides as in more acidic soils
(Lajtha and Harrisson, 1995).

In soils derived from limestone parent material, weathering decreases total CaCO 3 content, but
increases specific surface area of the smaller CaCO 3 particles (Holford and Mattingly, 1975).
Thus any relationship between CaCO3 and sorption is obscured by these opposing trends. Two
basic P-sorption reactions are distinguished with Al and Fe oxides and hydroxides, which differ
in the time scale over which they take place and the stability of products formed. The initial
adsorption appears to be a fast ligand exchange of surface hydroxyl groups with phosphate and
the formation of inner sphere surface complexes. Spectroscopic evidence for these complexes
have been presented by various researchers (Laiti et al., 1996, 1998; Nanzyo, 1984, 1986;
Nanzyo and Watanabe, 1982; Parfitt et al., 1978; Persson et al., 1996; Tejedor- Tejedor and
Anderson, 1990; Tejedor-Tejedor and Anderson, 1986).
Inherent soil properties and climate affect crop growth and how crops respond to applied P
fertilizer, and regulate processes that limit P availability. Climatic and site conditions, such as
rainfall and temperature, and moisture and soil aeration (oxygen levels), and salinity (salt
content/electrical conductivity) affect the rate of P mineralization from organic matter
decomposition. Organic matter decomposes releasing P more quickly in warm humid climates
and slower in cool dry climates. Phosphorus is released faster when soil is well aerated (higher
oxygen levels) and much slower on saturated wet soils. Soils with inherent pH values between 6
and 7.5 are ideal for P-availability, while pH values below 5.5 and between 7.5 and 8.5 limits P-
availability to plants due to fixation by aluminum, iron, or calcium, often associated with soil
parent materials.

Soil P cycles in many different forms some that are readily available and some that are not.
Phosphorus does not readily leach out of the root zone; potential for P-loss is mainly associated
with erosion and runoff. Soils and sites that are most prone to erosion and runoff, or are in close
proximity to streams, lakes and other water bodies need to be closely managed to avoid P loss.

P availability can be managed by liming acid soils, using measures that increase organic matter,
and proper placement of P fertilizer affecting how efficiently P is used by crops. Adequate P
levels encourage vigorous root and shoot growth, promote early maturity, increase water use
efficiency and grain yield. Thus, P-deficiency stunts vegetative growth and grain yield. Soil
phosphorus is relatively stable in soil, and moves very little compared to nitrogen. This lack of
mobility and low solubility reduces availability of P-fertilizer as it is fixed by soil P-compounds.
Fixed P is not lost, it becomes slowly available to crops over several years depending on soil and
P-compound type. Phosphorus deficiency symptoms appear on lower leaf tips and progress along
leaf margins until the entire leaf shows purpling. Lower leaves die when phosphorus deficiency
is severe, especially when hot, dry, windy conditions persist.