FertilizerResearch35:25-31, 1993.

© 1993KluwerAcademic Publishers. Printedin the Netherlands. 25

Phosphate rocks and partially-acidulated phosphate rocks as controlled

release P fertilizers

J. Hagin I & R. Harrison 2

1Technion-Israel Institute of Technology, Haifa, Israel; 2ADAS Soil and Water Research Centre,
Cambridge, UK

Key words: Partially acidulated phosphate rocks, phosphate rock dissolution

Abstract

Properties of phosphate rocks (PRs) and partially acidulated phosphate rocks (PAPRs) which affect the
pattern of P dissolution and thus the potential for manipulating the rate of P release are reviewed. The
effects of soil and plant properties are also considered.

Introduction physical, chemical, and biological characteris-

The reactions of phosphate rock (PR) and par-
tially-acidulated phosphate rock (PAPR) fertiliz-
ers in soils, and their use as P sources to plants,
have been the subject of considerable research,
and the results of these studies have been re-
viewed [4, 6, 10, 11, 13, 15, 24, 42, 44]. In this
review we shall attempt to explore whether
evidence in the literature indicates that, with the
correct choice of manufacturing variables and
soil conditions, it may be possible to manipulate
P dissolution characteristics of PRs and PAPRs
and hence match soil P supply to plant P de-
mand.
Much of the work on slow-, controlled-release
or controlled-availability fertilizers deals with
nitrogen. In reviewing slow-release nitrogen fer-
tilizers Hauck [19] states several basic principles.
Some of those seen to be valid for P fertilizers:
A slow-release fertilizer ideally should supply
nutrients to the soil solution at rates and
concentrations that allow the growing plant to
maintain maximum expression of its genetic
capability.
The accuracy to which the rate and pattern of
nutrient release can be predicted is determined
by the composition of the fertilizer and one's
ability to control or predict the effects of the
tics of the soil-plant system in which the
fertilizer is placed.
The release pattern of P from fertilizers is
important, from the agronomic point of view for
maintaining an adequate concentration of phos-
phate ions in solution and for minimizing P
fixation in soils [45].
Definition of the boundary between slow- and
fast-release P fertilizers is very difficult if not
impossible. For example, it is possible to con-
sider superphosphate (SP) as a slow-release
fertilizer, because the well known incongruent
dissolution of monocalcium phosphate (MCP) to
dicalcium phosphate dihydrate (DCPD) and
eventually dicalcium phosphate (DCP) results in
the formation of a number of sparingly soluble P
compounds [28, 29]. The term slow-release is
perhaps generally confined by convention to
classes of fertilizers which contain sparingly
soluble components, no consideration being
given to the properties of the reaction products
in the soil, and it is in this sense that the term is
used in this paper.
The potential for manipulating the dissolution
characteristics of PRs arises from the range in its
chemical reactivity and that for PAPRs because
they essentially consist of two P containing
components, MCP and PR, of widely differing
 26
solubilities in water. The proportions of these
two components in the final fertilizer material
can be controlled within a reasonably wide
range. These proportions are a function of the
initial PR characteristics, the acid used for acidu-
lation and the degree of acidulation. Soil en-
vironmental factors such as pH and P-fixing
capacity and plant factors related to root ac-
tivities will also have some effect on P dissolu-
tion. Proper choice of combinations of the above
parameters could lead to the development of P
fertilizers with predictable patterns of P release
and suited to a variety of farming systems.
Other P fertilizers such as magnesium and
ferrous ammonium phosphates have been pro-
posed as slow release P sources because of their
low water solubility. Additional slow-release
fertilizers are ammonium polyphosphates or
metaphosphates. The rate of dissolution in soil
solution of these materials depends on the poly-
mer structure [46]. Particle size and surface area
have a significant effect on the rate of dissolution
in all sparingly soluble fertilizers. The greater the
surface area for a given weight of material the
more rapid the release of nutrient [46].
Factors affecting dissolution of PR and PAPR
fertilizers
PR for direct application characteristics
Phosphate rocks used in PR and PAPR fertilizers
are members of the apatite group of minerals.
Significant differences in chemical and miner-
alogical properties are found within the group.
One of the properties, differentiating between
various PRs in regard to P release patterns, is
the isomorphous substitution of carbonate for
phosphate in the apatite lattice [15, 42]. Increas-
ing substitution increases the solubility product
of carbonate fluorapatites [5] and also results in a
smaller crystallite size and an increase in specific
surface area [27] (See also Bolan et al., Sale and
Mokwunye, and Chien in this issue).
Carbonate substitution is difficult to measure
on a routine base. Therefore, solubility of PRs,
often defined as reactivity, is conventionally
estimated by measuring the P brought into
solution by various extractants. A 2% formic
acid solution is quite often used for that purpose
[151.
Relative agronomic effectiveness of PRs in any
given soil has been shown to be strongly corre-
lated with extent of their carbonate substitution
[!]. In a study with seven PR materials in which
the carbonate substitution in the apatite lattices
ranged from 0.4 to 7.1%, the relative agronomic
effectiveness of the PRs was directly related to
their substituted carbonate content. In a given
acid soil substituted carbonate content accounted
for 71 to 84% of the variation in rock P released.
However, for the group of eighteen acid soils
tested substituted carbonate accounted for nearly
49% of the variation in P release. Soil charac-
teristics accounted for 54 to 75% of the variation
in P release from a given PR. This indicates that
soil factors in addition to PR characteristics
influence P release from the PRs.
PRs may contain other minerals in addition to
apatite. Whereas the presence of carbonate min-
erals, such as calcite depresses the apparent
solubility of P in the conventional extraction
solutions [2], it does not seem to influence the
reactivity of apatite minerals in soils. Other
accessory minerals, such as siliceous minerals,
may depress both PR solubility and reactivity in
soil [15].
Particle size of the PRs has a limited influence
on P dissolution. Increasing fineness of grinding
up to 100 mesh (<150/xm) often increases P
availability, but finer grinding seems not to
influence it [24].
There appears to be an interaction between
particle size and application rate, such that the
effect of decreased particle size is reduced by
high application rates [21, 22].
PRs directly applied to soil are used as P
sources to plants. Their low solubility character-
izes them as slow-release fertilizers. It is appar-
ent that the rate of P release in any given soil is
determined primarily by the reactivity, as de-
fined by the extent of carbonate substitution, of
the chosen PR. This rate of release may be
modified to a limited degree by fineness of
grinding. The appropriate choice of PR and
fineness of grinding will therefore depend on soil
type and the rate of P dissolution required for
the agronomic system in question.

PR characteristics in PAPR
PRs varying widely in their characteristics are
used for manufacturing PAPRs. The product of
partial acidulation is a mixture of unreacted PR,
MCP and small quantities of DCP and DCPD.
The highly acidic triple point solution formed in
the PAPR granule by hydrolysis of MCP reacts
with and solubilizes part of the residual PR, thus
yielding additional soluble P [9]. This mechanism
has been proposed to explain the agronomic
performance of PAPRs on calcareous soils [12].
Other studies with 30-35% phosphoric acid
PAPRs prepared from North Carolina PR have
suggested that only 4-6% of the P in the PR
component is solubilized by the triple point
solution [18, 32]. However, in the long term, the
apatitic fraction of PAPR releases some P into
the soil solution. Thus, the P-release pattern of
PAPR over time is partly influenced by the
properties of the initial PR.
In a laboratory study five PRs varying in
formic acid solubility from 18.9 to 52.7% were
acidulated with phosphoric or sulfuric acids to 0,
20%, 33% and 50% of full acidulation and
granulated. In an experiment measuring P dissi-
pation from single fertilizer granules into soil,
the amount of dissipated P was greater than the
water soluble P content of the PAPR fertilizers
indicating the dissolution of the non-acidulated
PR fraction. The amount of P dissipated was
related to the initial water soluble P content and
to the formic acid solubility (i.e. reactivity) of
PRs used for manufacturing the fertilizers [14].
Iron and aluminum oxide content of PR has an
effect on the quality of PAPR produced. PRs
from seven locations were partially acidulated
with sulfuric acid at 30% or 50% level. Water-
soluble P increased with increase in the degree of
acidulation but was inversely proportional to the
amount of iron and aluminum sesquioxides in
the rocks [33].
Nine sources of PR representing a range of
iron and aluminum oxide content from 0.7% to
12.4%, were partially acidulated with sulfuric
acid at the 30% or 50% level and granulated.
The water-soluble P content in PAPR decreased
with increasing iron and aluminum sesquioxide
content in the PR used. Apparently, their pres-
ence resulted in a reversion of some of the
27
water-soluble P to citrate-soluble P and some-
times even to citrate-insoluble P. Iron and
aluminum become active by reaction with sul-
furic acid. The agronomic effectiveness of
PAPRs decreased with increasing iron and
aluminum oxide content in PRs [17].
In another experiment partial acidulation of a
PR, containing large amounts of iron and
aluminum sesquioxides (8.8%), was less effec-
tive agronomically than its compaction with TSP.
Whereas, a moderately reactive, low sesquioxide
content PR, compacted with TSP or acidulated
into PAPR, had similar agronomic effectiveness.
This was again explained by reversion of some of
the water-soluble P formed during acidulation
into water-insoluble, even citrate-insoluble forms
[34].
The above reviewed studies show that the
characteristics of PR, such as carbonate substitu-
tion, or presence of sesquioxides, have an effect
on the P availability in the manufactured PAPR.
Thus, the conventional solubility of PR used for
manufacturing the PAPR could be utilized for
developing a predetermined residual effect and
controlled P release pattern, according to soil
and crop requirements. Present experimental
data do not allow a quantification of these effects
for practical purposes.
Degree of acidulation
The degree of acidulation of PRs and the kind
and quality of acid used have a very strong effect
on P solubility and thus on its availability in the
manufactured PAPRs.
Bolan et al. [4] concluded from an extensive
study that both the amount of acid used in PR
acidulation and the quality of acid influence the
final water soluble P content of PAPR. The
presence of Fe, A1 and Mg in the phosphoric
acid reduces the rate and extent of PR acidula-
tion. When sulfuric acid is used the presence of
impurities has an even greater effect on the final
water soluble P content.
Phosphoric acid acidulation generates relative-
ly more water soluble P than sulfuric acid acidu-
lation [13].
In four greenhouse experiments using three
soils and North Carolina phosphoric acid 20% to
 28
50% acidulated PAPR, perennial ryegrass was
grown for up to 8 months. There was a signifi-
cant positive correlation between water soluble P
of the PAPRs and P uptake by ryegrass [38].
Long- and short-term effects of degree of
acidulation should be differentiated as indicated
in the following study. In a series of glasshouse
experiments with North Carolina PAPRs, in the
long-term 20, 35 and 50% acidulated PAPRs
performed as well as TSP, although in the short-
term the 20% acidulated PAPR may be some-
what inferior [8].
Degree of acidulation and the acid used,
sulfuric or phosphoric, are crucial steps in ach-
ieving a desired pattern of fertilizer P release and
availability. A lower degree of acidulation (i.e.
20%) would give a PAPR with long term release,
whereas higher acidulation (i.e. 50%) would
produce a quicker P-release fertilizer. It seems
that there is a linear relation between water
solubility and the amount of P dissipated from
the fertilizer granule, suggesting a similar rela-
tionship between water solubility and P availabil-
ity in the short term.
Soil characteristics
Soil properties have a decisive influence on the
release of P from PRs [20]. Dissolution of PR is
favoured by low pH [37], low concentration of P
and Ca in solution [30, 31, 40], and increasing
capacity of the soil to adsorb P and Ca [31, 43].
All these factors act to reduce the concentrations
of the products of the dissolution reaction. In
addition soil organic matter [24], soil texture [22]
and moisture status of the soil [23] have all been
shown to affect PR dissolution. Increased P-
retention capacity of the soil increases P dissolu-
tion from PR, but it does not necessarily increase
its availability to crops [15, 24, 42].
In considering a PAPR fertilizer as a P source
to plants, the availability of the reaction products
of the P dissipated out of the fertilizer granule
with soil constituents, has to be taken into
account.
The acid solution moving out of the fertilizer
granule reacts in the soil bringing into solution
cations such as Fe, A1, Ca and Mg. The solution
becomes supersaturated in relation to a variety
of phosphate compounds and they precipitate in
the surrounding soil volume. In acid soils Fe-
and Al-phosphates may be expected to precipi-
tate primarily, while in neutral and calcareous
soils Ca- and Mg-phosphates are precipitated.
These reaction products have a low solubility,
but it varies from one compound to another. For
example variscite, an Al-phosphate has a
solubility constant of 10 -22 and DCPD of 2.2 x
10 -7 [41].
In PAPR the phosphoric acid in the triple
point solution, generated by hydrolysis of MCP,
is partly consumed by reaction with residual PR.
Thus less should be available for reaction with
soil components responsible for P fixation [9].
The above conclusion is exemplified in the
following experiments.
Equal amounts of water-soluble P in the form
of granulated PAPR (20% by phosphoric acid)
or PR mixed with CSP, and CSP were added to 2
Nigerian savanna soils and an Oxisol from
Colombia. The amount of water-extractable P
was higher in soils treated with PAPR or with the
PR and CSP mixture, than in those treated with
CSP. The presence of PR in PAPR or in the
mixture of CSP and PR may have slowed down
the immobilization of water-soluble P by reacting
with some of the acidity produced during MCP
hydrolysis, thus reducing the amount of acid
available to solubilize soil A1 and Fe. The
relative effectiveness of PAPR was highest in the
Oxisol, which had the highest capacity to sorb P
[35].
In a greenhouse study with maize the effect of
soil P-fixing capacity on the relative agronomic
effectiveness of PAPR was evaluated. Six soils
varying in P-fixing capacity from 5.6 to 56.1%
and a Huila PR acidulated with sulfuric acid at
50% were used. The effectiveness of PAPR
increased with increasing soil P-fixing capacity.
PAPR and SSP were equally effective in increas-
ing dry-matter yield or P uptake at P-fixing
capacities of 28% or 36%, but PAPR was found
to be more effective than SSP in soils with P-
fixing capacity higher than these values [7] (See
also Rajan and Marwaha in this issue).
In four greenhouse experiments with perennial
ryegrass, using three soils and North Carolina
20% to 50% phosphoric acid PAPRs, the in-
fluences of soil P retention and P status were

investigated. P status of soils appeared to in-
fluence the effectiveness of PAPRs to a greater
extent than P retention. In soils of low P status
the degree of acidulation required for PAPR to
be nearly or as effective as TSP was 50%,
whereas in a soil of high P status even 30%
PAPR applied as a maintenance fertilizer was
effective [38].
P release from both, PRs and PAPRs is
strongly influenced by soil characteristics. There-
fore, choice of the appropriate fertilizer will
depend not only on the desired P release pattern
but also on soil properties, such as pH and
retention capacity.
Plant related characteristics
Root excretions and selective uptake of ions by
roots may affect the P dissolution rate from PRs
and PAPRs and thus influence their relative
effectiveness.
Imbalances in the uptake of cations and anions
by plant roots, balanced by excretion of a proton
or a bicarbonate anion, are the main cause for
plant related pH changes in the rhizosphere,
influencing P dissolution from sparingly soluble
sources [25, 36]. Carbon dioxide respiration and
excretion of organic acids by roots and microor-
ganisms seem to be less important. These acids
may enhance P dissolution by chelating cationic
partners of the P ion [26]. The magnitude of the
cation-anion imbalance depends on plant charac-
teristics, such as root cation exchange capacity
and on uptake of other nutrients, specifically
anionic nitrate nitrogen versus cationic ammo-
nium nitrogen.
The above shows that when attempting to
match the P dissolution pattern of a sparingly
soluble P source to specific plant requirements,
the root and nutritional characteristics of the
plant have to be accounted for.
Residual effect of PAPRs
The residual effect of PAPRs as P sources to
plants, indicating their slow-release characteris-
tic, is reported in several papers.
In a field study with millet on a sandy soil two
29
50% sulfuric acid acidulated PAPRs were
evaluated over a period of 3 years. One initial
application of a large dose of fertilizer was more
effective for grain production than three small
annual applications [3].
In a 2-year permanent pasture field trial, on a
highly P-retentive soil, using a reactive North
Carolina PR acidulated with phosphoric acid to
20, 30, and 50%, the residual effectiveness of
fertilizers in the 2nd year ranged 97-108% of the
effectiveness of freshly added TSP. No measur-
able amount of unacidulated PR in PAPRs
dissolved in the first three months after fertilizer
addition. The rate of dissolution in the next
fifteen months was 60% per year of that initially
added [39].
P availability was measured by dry-matter
yield and P uptake in greenhouse experiments
with corn. 20% acidulation of Pesca PR with
phosphoric acid was 53-76% as effective as TSP
with a single crop and 79-90% as effective over
3 cropping periods [16].
Summary and conclusions
PRs are sparingly soluble in water, and as such
are a slow-release source of P in soils. Charac-
teristics, such as chemical reactivity, fineness of
grinding and the presence of other minerals can
be used to select materials with different rates of
P release. However, soil factors such as pH,
capacity to adsorb Ca and P fixing capacity are
also important in determining the availability of
PR-P to plants.
PAPRs have considerable potential as control-
led-release fertilizers. It has been shown that by
varying PAPR characteristics it is possible to
achieve different P-release patterns. Several fac-
tors can be manipulated to this end:
- T h e choice of PR. The chemical reactivity of
PR, resulting from carbonate substitution in the
apatite lattice and expressed in terms of solubili-
ty in chemical extractants, influences P dissolu-
tion from the fertilizer. In addition the presence
of A1- and Fe-minerals in the PR influences
reactions within the PAPR and thus P release.
- T h e degree of acidulation and acid used. This
determines the water soluble P content of the
30
P A P R a n d thus the b a l a n c e b e t w e e n short- a n d
l o n g - t e r m availability to plants.
This review has s h o w n that factors which
i n f l u e n c e the rate of d i s s o l u t i o n f r o m P R s a n d
P A P R s have b e e n identified, a n d that the effect
of t h e s e factors is k n o w n in a qualitative way. A
c e r t a i n a m o u n t of q u a n t i t a t i v e data is also avail-
a b l e , a l t h o u g h in g e n e r a l these d a t a have n o t
b e e n u s e d to q u a n t i t a t i v e l y predict P release
p a t t e r n s . T h u s , for e x a m p l e , c o m p a r i s o n s of P R s
i n t e r m s of relative a g r o n o m i c effectiveness give
i n f o r m a t i o n a b o u t the relative rates of P release
f r o m d i f f e r e n t P R s , b u t do n o t q u a n t i f y the
a m o u n t s of P r e l e a s e d with time.
It w o u l d s e e m t h a t the ability to m a n i p u l a t e
m a n u f a c t u r i n g v a r i a b l e s to p r o d u c e p r e - d e t e r -
m i n e d P release p a t t e r n s will r e q u i r e the analysis
of the available k n o w l e d g e o n fertilizer charac-
teristics, P d i s s o l u t i o n rates a n d their i n t e r a c t i o n
with soil a n d p l a n t p r o p e r t i e s , to p r o d u c e q u a n -
t i t a t i v e e s t i m a t e s of P release with time.
T h e a v a i l a b l e e v i d e n c e suggests that it s h o u l d
b e p o s s i b l e to c o n s t r u c t m u l t i - v a r i a n t c o m p u t e r
s i m u l a t i o n m o d e l s , which could lead to the
i m p r o v e d u t i l i z a t i o n of P f r o m P R s a n d P A P R s ,
a n d t h e e m e r g e n c e of these m a t e r i a l s as true
c o n t r o l l e d - r e l e a s e fertilizers.
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