7.

Phosphorus Fertilizers

SOIL 5813
Soil-Plant Nutrient Cycling and Environmental
Quality
Department of Plant and Soil Sciences
Oklahoma State University
Stillwater, OK 74078
email: wrr@mail.pss.okstate.edu
Tel: (405) 744-6414

Phosphorus Use Efficiency ?

Rock Phosphate

Ca10(PO4)6(OH)2
Hydroxyapatite (bones, teeth) bone-meal bones in acid soils?
Ca10(PO4)6F2 or Cl2 or OH2
Fluorapatite

27-41% P2O5
Total P in soils (90 to 2000 lb /acre, avg. of 800 in the surface horizon)
Calcium Orthophosphates
P fertilizers:

water soluble
citrate soluble (dissolves more P than water)
OSP ordinary superphosphate (0-20-0)
rock phosphate + sulfuric acid

mixture of monocalcium phosphate and gypsum

16-22% P2O5 (90 % water soluble)
8-10% S as CaSO4

NH3 +

H2SO4

(NH4)2SO4
20%N
ammonium sulfate

HNO3

NH4NO3
33%N
ammonium nitrate

CO2

(NH2)2CO
urea

H3PO4

NH4H2PO4
11-18%N
ammoniated phosphates
11-48-0
18-46-0

HNO3/rock phosphate

45%N

nitric phosphates

Haber-Bosch: (Germany, 1910)

High temp (1200C)
High pressure (200-1000 atm)
(magnetite, Fe3O4) catalyst

Methane

3CH4 + 3O2 + 2N2

Anhydrous Ammonia

4NH3 + 3CO2

TSP triple or concentrated superphosphate (0-46-0)

rock phosphate + phosphoric acid

essentially all monocalcium phosphate
44 to 52% P2O5 (98% water soluble)
< 3% S

major phosphate mineral is monocalcium phosphate monohydrate (MCP)

DAP Diammonium phosphate (18-46-0)

Reacting wet process H3PO4 with NH3

46-53% P2O5

MCP
soluble)

monocalcium phosphate monohydrate Ca(H2PO4)2 2H2O (highly water

DCPD

dicalcium phosphate dihydrate CaHPO4* 2H2O - brushite

DCP

dicalcium phosphate CaHPO4, 53% P2O5 - monetite

congruent dissolution of Ca(H2PO4)2 2H2O into Ca++ and H2PO4 ions occurs at a pH of 4.68

Examples:

P deficient
S deficient
pH 5.5
anion exchange 20 meq/100g
Apply triple superphosphate with gypsum
Supersaturate the band with respect to Ca and precipitate P as DCP and or DCPD
which will be slowly available with time.

Lindsay (1979)
including NH4+, K+, Ca++ and Mg++ enables these cations to be included in the initial
reaction products.
MCP contains sufficient Ca to precipitate half of P as DCPD or DCP.
In acid soils, Fe and Al generally precipitate the additional P.
Avoid anion exchange interaction (P displacing S from the complex)

Low Soil pH (<5.5) P precipitates as Al and Fe phosphates

a. variscite (ALPO4 * 2H2O)

b. strengite (FePO4 * 2H2O)

Moderate to High pH, P precipitates as Ca phosphates (several)

a. dicalcium phosphate (CaHPO4)

b. dicalcium phosphate dihydrate (CaHPO4 * 2H2O)
c. hydroxyapatite Ca5(PO4)3OH
d. fluorapatite Ca5(PO4)3F (rock phosphate)

Precipitation - Dissolution of phosphate minerals is pH dependent:

Precipitation/Dissolution can be determined by using P solubility
diagrams.
1. Soil solution (H2PO4-) and pH above the line (precipitation)
2. Soil solution (H2PO4- and pH below the line (dissolution)

0
Ca
HP

pH 4.5

O Ca
HP
4

-1

4 .

2H

) 3F
4
PO

-3

Precipitate Formed

1. add fertilizer soluble P added

2. 1 - 2

soluble P decreases

DCP

3. 2-3

DCP dissolves

FA

4. 3-4

FA dissolves

Variscite

3
DCPD

(P
Ca 5

-4

a
C

O
(P
H

O
2
5H

)3

CP
O
P
TC

-F
ite

r
luo

Can P fertilizers be used as a

source of Lime? if enough is
applied, yes, but this will not
be economical

)2
O4
P
(

a3
-C

tite

apa
rox
Hyd

tite

-6

a
rap

,Q
(K
e
te
ci oil F
s
ri S
Va e it
ng
e
r
St

DCP

OH

-5

O 4) 3

4
)
o
Flu

log H2PO4- or HPO42-

(
Ca 5

-2

Event

-7
-8

K
Q
G

Change in solubility of P is not

an overnight process

Kaolinite
Quartz
Gibbsite

-9
3

pH