Published January, 1959
Nature of the Reactions of Monocalcium Phosphate Monohydrate in Soils:
II. Dissolution and Precipitation Reactions Involving Iron, Aluminum,
Manganese, and Calcium1
W. L. LlNDSAY AND H. F. STKPHENSON2
ABSTRACT
TPS, the solution in equilibrium with monocalcium
phosphate monohydrate (MCP) and anhydrous dicalcium
phosphate, was reacted with successive increments of
Hartsells fine sandy loam (pH 4.6) and Rosebud loam
(pH 7.6). The experiments were designed to simulate
chemical conditions that may occur in soil surrounding a
dissolving granule of MCP.
Reaction of soil with TPS (pH 1.01, 4.50M P, and
1.34M Ca) resulted in the dissolution of Fe, Al, Mn, Ca,
and other constituents from the soil. As successive soil in-
crements were contacted by the solution, simulating its
movement from a fertilizer granule, the dissolution proc-
esses continued and pH of the solution increased. The
solution soon became supersaturated with respect to cer-
tain phosphate compounds that slowly began to precipitate.
During these reactions with Hartsells soil, Al in solution
reached 0.7M, Fe 0.2M, and Mn 0.009M. With Rosebud
soil, the concentrations of Fe and Al were slightly less.
TPS in contact with soil dissolved Mn more readily than
Al, and Al more readily than Fe. With time and rise in
pH, the precipitation of these cations was in the order
Fe > Al > Mn. Most of the filtrates obtained from re-
action of soil with TPS precipitated solids upon standing.
Some of these solids were identified by microscopic and
X-ray analyses as crystalline Fe, Al, or Ca phosphates,
while others were colloidal, amorphous precipitates that
were not identifiable by these methods.
T HE SOLUTION leaving a fertilizer placement of mono-
calcium phosphate monohydrate (MCP) in soil is a
highly acidic calcium-phosphate solution (2, 9). In a pre-
vious study (9) it was found that Fe, Al, Mn, and other
components were dissolved from soil in the vicinity of a
dissolving band of this fertilizer. Some of the dissolved
soil components were found to move with the fertilizer
solution away from the dissolving band. This latter obser-
vation was in agreement with the explanation of Lehr
et al. (7) that water moves into a MCP granule by vapor
movement and that the fertilizer solution moves away to
the surrounding dried soil by capillary flow. Under these
conditions, the fertilizer solution is diluted very little dur-
ing its initial reaction with soil.
The present studies were made to investigate the nature
of the reactions that may occur as fertilizer solution leaves
a dissolving granule of MCP and moves slowly away, into
the surrounding soil. The fertilizer solution used for these
studies was TPS (triple-point solution, the solution in equi-
librium with Ca(H2PO4)?-H2O and CaHPOJ, which is the
most concentrated solution resulting from the dissolution
of excess MCP in water (9).
EXPERIMENTAL MATERIALS AND METHODS
Soils used.—Acid Hartsells fine sandy loam (pH 4.6, from
Tennessee) and slightly calcareous Rosebud loam (pH 7.6,
from Nebraska) were studied. These soils were allowed to
air-dry for 2 days and were then seived through a 16-mesh
screen. Moisture content of these soils expressed on an oven-
dry basis at 110° C. was 6.78% for Hartsells and 6.12% for
Rosebud. The HCl extractable Fe, Al, Mn, Ca, and P of
these soils are given in table 1.
Preparation of TPS solution.—Solutions very near the com-
position of TPS were prepared by stirring together the follow-
ing materials at 25° G. for 3 days: 300 g. of reagent-grade
Ca(H 2 PO4) 2 -H 2 O, 25 g. of crystalline CaHPO4 (anhydrous),
90 ml. of 80% H3PO4, and 588 ml. of water. The suspension
was then filtered and the filtrate was analyzed (9) and stored
in a stoppered flask maintained at 25°. G.
Extraction of soil with HCl.—A 1-gram sample of soil
(oven-dry basis) and 40 ml. of 6N HCl were placed in a 50-
ml. centrifuge tube and immersed in a boiling water bath.
The suspension was stirred occasionally over a 1-hour period,
then centrifuged and the supernatant liquid decanted into a
500-ml. volumetric flask. The extraction and decantation
steps were repeated 3 times on the same soil sample. The
combined decantations were brought to volume and analyzed
for Fe, Al, Mn, Ca, and P.
Reaction of TPS with successive increments of soil.—To
350 g. of soil was added 700 ml. of TPS. The suspension was
shaken for 1, 5, or 16 hours, and filtered in a pressure cell
through S and S Blue Ribbon filter paper. During the final
stages of filtration a rubber diaphragm was inserted above
the soil, and N2 pressures up to 50 psi. were applied in order
to remove as much filtrate as possible. Two lO.-ml. aliquots
of the filtrate were transferred to calibrated volumetric flasks
for later analyses. The remaining filtrate was added to a
second sample of soil, maintaining the 1:2 ratio of soil (g.)
to filtrate (ml.). The second suspension was shaken as before,
filtered, sampled, and the remaining filtrate reacted with a
third sample of soil in the same manner. The sequence was
repeated for 10 soil increments, after which no filtrate re-
mained for further reaction.
Analyses of filtrates and precipitates.—Density was de-
termined by weighing one of the 10-ml. calibrated volumes
of filtrate saved for analyses. A portion of this aliquot was
Table 1—Fe, Al, Mn, P, and Ca extractable with 6N HCl
from the soils used in this study.
Soils Soil constituent dissolved (m mol/500 g. soil*)
Fe Al Mn P Ca
Hartsells 103 264 1.26 2.78
Rosebud 113 304 2.34 3.07 76
*Oven-dry basis.
 LINDSAY AND STEPHENSON: REACTIONS OF MCP IN SOILS: WITH FE, AL, MN, AND CA
used for pH measurement; the remaining portion was stored
in a stoppered flask for a period of 3 months. The solids that
precipitated during this period were then washed with water
several times, dried with acetone, and examined petro-
graphically and by X-ray methods.
Organic matter was destroyed in the second 10-ml. aliquots
of the filtrate by digestion with 6N HNO3 and 30% H2O2. The
residue was dissolved in 10 ml. of 6N HC1 and diluted to 100
ml. Fe, Al, Mn, and Ca were determined as outlined in a pre-
vious study (9). P was determined by the method of Dickman
and Bray (3).
RESULTS
The objective in the present experiments was to meas-
ure changes in the composition of TPS as it reacted with
successive increments of soil, simulating the gradual move-
ment of this fertilizer solution into the shell of soil imme-
diately surrounding a dissolving granule of MCP. The
results obtained with Hartsells soil at 1- and 5-hour reac-
tion periods, and with Rosebud soil at 1- and 16-hour
reaction periods are shown in figures 1 to 4.
pH.—The pH gradually increased upon reaction of TPS
with soil (figure 1). Increasing the time of contact of solu-
tion with each soil increment resulted in greater increases
in pH. These increases were greater for the slightly cal-
careous Rosebud soil than for the acid Hartsells soil. After
reaction with 10 soil increments, the solution was still
very acid (below pH 2.4) and reaction with the soil
undoubtedly was continuing.
NUMBER OF SOIL INCREMENTS CONTACTED
Figure 1—Changes in pH of TPS upon reaction with suc-
cessive increments of an acid and a calcareous soil as
influenced by time of contact.
NUMBER OF SOIL INCREMENTS CONTACTED
Figure 2—Fe in solution (left) and Al in solution (right) resulting from reaction of TPS with successive increments of an
acid and a calcareous soil, as influenced by time of contact.
19
lron.—Fe was dissolved from both soils by reaction with
TPS (figure 2, left). Allowing the solution to contact each
successive soil increment for 1 hour gave similar results
for the two soils. Additional Fe was dissolved from the
Hartsells soil by increasing the time of contact to 5 hours,
indicating the continued dissolution of Fe.
With Rosebud soil, increasing the reaction periods to
16 hours resulted in a lower Fe content in solution. These
results indicate that Fe was not only dissolving, but also
was precipitating, and that during the later 16-hour reac-
tion periods, the rate of precipitation of Fe exceeded its
rate of dissolution. These changes likely reflect the dis-
solution of Fe oxides from the soil and the gradual precipi-
tation of Fe phosphates. Even during reaction with the
first soil increments where the solution composition re-
mained near TPS, some precipitation of Fe had taken place.
The broken lines show the concentrations of Fe expected
in solution during reaction with TPS, if all the HC1-
extractable Fe of the soil had dissolved and remained in
solution. These concentrations were calculated from the
data in table 1 and by taking into account the effect of
dilution due to moisture present in the soils. At least /i
as much Fe was dissolved in 1 hour from these soils by
reaction with TPS as was extractable with HCl. In these
studies with TPS, the Fe concentration in solution reached
0.2M, a concentration many times that normally found
in soil solution.
Aluminum.—Greater concentration of Al than Fe resulted
from reaction of soil with TPS (figure 2, right). The flatten-
ing and descending portions of the concentration curves
reflect precipitation of Al, likely as Al phosphates. Increas-
ing the time of contact brought more Al into solution.
Upon reaction with Hartsells soil at the 5-hour extraction
periods, the concentration of Al reached approximately
0.7M. Flattening of the Al concentration curve at the
second soil increment suggests precipitation of an acid
Al phosphate. The sharp drop in Al concentration from the
sixth to the seventh soil increment probably reflects super-
saturation of the solution with respect to some Al phos-
phate that was precipitating. The pH at this point was 1.74
(figure 1). This same precipitation appears to have contin-
ued during reaction with the eighth soil increment, after
which the Al concentration again continued to rise more
rapidly. At least one-half as much Al was dissolved from
the first increment of Hartsells soil by reaction with TPS
as was extractable from the soil by HCl (broken line).
With Rosebud soil, a smaller fraction of the HC1-
extractable Al was dissolved by reaction with TPS. At the
16-hour extraction periods, the flattened portion of the
ROSEBUD SOIL
/•—HCl SOLUBLE Al
5 6 7 8 9 I O O I Z 3 4 5
NUMBER OF SOIL INCREMENTS CONTACTED
20 SOIL
10 O I 2 3 4 5
NUMBER OF SOIL INCREMENTS CONTACTED
Figure 3—Mn in solution (left) and Ca in solution (right) resulting from reaction of TPS with successive increments of an
acid and a calcareous soil, as influenced by time of contact.
ROSEBUD SOIL
O 1-33
fe
> as discussed later (table 2).
» 1.32
0 1 2 3 4 5 6 7 6 9 10 O, 1 2 3 4 5
NUMBER OF SOIL I N C R E M E N T S CONTACTED
Figure 4—Density of solution resulting from reaction of
TPS with successive increments of an acid and a calcar-
eous soil, as influenced by time of contact.
curve at soil increments 3 to 5 reflects the precipitation of
Al. The approximate correspondence in pH at these points
with that of the sixth increment of Hartsells soil at the
5-hour period (figure 1) suggests that the same compound
was precipitated. With the longer reaction time, precipita-
tion was more complete, and extensive supersaturation was
reduced. The abrupt decrease in Al beyond the eighth soil
increment reflects precipitation of another Al compound
under conditions of higher pH. The results provide evi-
dence that Al is very active in the reactions of TPS with
soil.
Manganese.—Concentration of Mn increased (figure 3,
left) as TPS reacted with successive increments of soil. The
amount dissolved increased only slightly by increasing the
reaction time. Slightly more Mn dissolved from Rosebud
than from Hartsells soil. In both soils a large fraction of
the HCl-soluble Mn (broken lines) was dissolved by TPS
and the concentration of Mn in the filtrates was < 1/10
that of either Fe or Al. The data further indicate that Mn
dissolves but does not precipitate during the initial re-
action of soil with TPS.
Calcium.—In Hartsells soil, Ca concentration (figure 3,
right) remained constant at first and then gradually de-
creased as TPS reacted with more soil. Ca dissolved from
this acid Hartsells soil did not measurably change the
concentration of Ca in solution. Ca in the HC1 extracts
SCIENCE SOCIETY PROCEEDINGS 1959
——I——I——I——I——I——I——I——I——I——T
HARTSELLS SOIL ROSEBUD SOIL
I
P 1:4
3
£ 1.2
-1——I——I——I——I——I——1_
0 I 2 3 4 9 6 7 8 9 10 O I 2 3 4 9 6 7 8 9 IO
NUMBER OF SOIL INCREMENTS CONTACTED
6 7 8 9 10
from Hartsells soil (table 1) was too low for accurate
determination by the methods used. Differences in Ca con-
centration between I- and 5-hour extractions largely reflect
differences in Ca content of the different preparations of
TPS (See Ca concentration at soil increment zero).
Reaction of TPS with Rosebud soil, which contained
an equivalent 1.5% CaCO3, resulted in a measurable in-
crease of Ca in solution, thus reflecting the dissolution of
soil Ca. The abrupt decrease in Ca at soil increments 7
and 8 most likely reflects precipitation of DCP dihydrate,
Density.—Solution density (figure 4) increased with time
of contact in all cases as TPS contacted the first 7 incre-
ments of soil. The sudden decreases during reaction with
the eighth increment of Rosebud soil were most likely
caused by removal of Ca from solution by precipitation of
DCP dihydrate. In Hartsells soil, increasing time of contact
6 7 8 9 10 resulted in a continued increase in solution density. The
latter filtrates of this series showed evidence of highly
supersaturated solutions that completely solidified after a
few days. Filtrates from the Hartsells soil were extremely
dark brown in color, reflecting in part the presence of dis-
solved organic matter. Part of the supersaturation in these
filtrates may have been due to chelation effects which kept
large quantities of Fe and Al in solution. Other dissolved
soil constituents not measured would also be expected to
increase the solution density.
Phosphorus.—The P concentration of TPS initially was
4.50M. After reaction with 10 increments of soil, the con-
centrations still were in the range of 3.5 to 4.0M. Changes
in P concentration accompanying the relatively small de-
creases in Fe, Al, and Ca concentrations observed with
variations in pH, time, and other factors could not be
measured with adequate precision. In general, P concentra-
tion of the filtrates gradually decreased with successive
soil increments. In a subsequent paper of this series,
further attention is given to the progressive behavior of P
in relation to pH changes, dilution, and other factors in the
fertilizer-affected soil zone.
Precipitation of solids from filtrates upon standing.—
Within a few days, precipitates appeared in most of the
filtrates stored in stoppered flasks. After approximately 3
months, these solids were examined by X-ray and petro-
graphic means. Some of the precipitates were colloidal,
amorphous solids that could not be identified by these
methods; others were identified as known crystalline phos-
phates of Ca or Fe and Al. Results of these examinations
are summarized in table 2.
Hydrated alkali (Fe, Al) phosphates having the general
 LINDSAY AND STEPHENSON: REACTIONS OF MCP IN SOILS: WITH FE, AL, MN, AND CA
Table 2—Petrographic and X-ray identification of solids that precipitated during a 3-month period
from filtrates obtained by reaction of soil with TPS.
Source of filtrate Identifiable
Cri rstallinephases*
Soil type Reaction, No. of soil
time (hr. ) increment
Hartsells 5 3 a. 1:3:6:20 species
Hartsells 5 4 a. 1:3:6:20 species
b. DCP dihydrate
Hartsells 5 6 a. 1:3:6:20 species
b. Unidentified phase
Hartsells 5 10 a. 1:3:6:20 species
Rosebud 1 6 a. 1:3:6:20 species
b. DCP dihydrate
Rosebud 1 10 a. DCP dihydrate
b. 1:3:6:20 species
c; K-taranakite
d. DCP anhydrous
e. Unidentified phase
Rosebud 16 4 a. 1:3:6:20 species
b. DCP anhydrous
Rosebud 16 7 a. DCP dihydrate
b. 1:3:6:20 species
*1:3:6:20 designates an isomorphous series of complex Fe and Al phosphates of the type M Z O'3(A1, Fe)2 O 3 -6P 2 O5 • 20H Z O, where the molar oxide ratios are referred to by numbers
and M stands for momovalent cations such as H, K, NH 4 , Na, etc.; K-taranakite refers to the series of compounds, 3K2 O- 5(A1, Fe)2 O3- 8P2 O5 -42 H z O, which may be designated by the
molar oxide ratios as a 3:5:8:42 isomorphous series.
formula M2O • 3(Al,Fe)2O3 • 6P2O5 • 20H2O were identi-
fied in nearly all the residues examined. In this isomor-
phous series M . stands for monovalent cations as H, K,
NH 4 , Na, etc., and Fe and Al may be substituted for
one another. Compounds of this isomorphous series
may be referred to as members of the 1:3:6:20 series,
the numbers being used to represent the respective
molar oxide ratios. In filtrates from Hartsells soil, the
1:3:6:20 compounds accounted for most of the crystalline
solids that precipitated. Microchemical tests showed that K
was the principal monovalent cation (M) in most of these
products. K-taranakite, belonging to a (3:5:8:42) iso-
morphous series of compounds and having the formula
3K2O • 5(Al,Fe)2O3 • 8P2O5 • 42H2O appeared as one of
the phases in the tenth filtrate from Rosebud soil at the
1-hour period. Beyond the fourth soil increment, DCP
dihydrate (CaHPO4 • 2H2O) appeared consistently in all
the filtrates from Rosebud soil. It was noted that with the
1-hour period more DCP dihydrate appeared in filtrates
7 and 8 than in 9, while with the 16-hour period, more
appeared in 7 and 9 than in 8 and 10. These observations
further suggest that the precipitation of DCP dihydrate
accounted for the sudden decreases of Ca concentration
shown in figure 3, right.
The filtrates from the present study consistently showed
the formation of predominantly DCP dihydrate and only
traces of anhydrous DCP. This occurred even though
anhydrous DCP is the thermodynamically stable form of
DCP in the pure CaO-P2O5-H2O system in the region of
TPS (9). In order for DCP dihydrate to form and persist
in the filtrates obtained by reaction of TPS with soil, one
or more of the following changes must have occurred: (a)
Ca dissolved from the soil caused the solution to become
supersaturated with respect to DCP dihydrate; (b) re-
moval of P from solution by precipitation with Al and Fe
dissolved from the soil caused supersaturation of the solu-
tion with respect to DCP dihydrate; or (c) the presence
of other dissolved components from the soil caused a shift
in the position of the DCP isotherms. Brown and Lehr (2)
have previously discussed some of these changes with
reference to the DCP solubility isotherms. The persistence
of DCP dihydrate over a period of several months suggests
that the environment resulting from the reaction of soil
with TPS is such that the conversion from the dihydrate to
the anhydrous form of DCP is much slower than in the
pure CaO-P2O5-H2O system.
21
Description of solids
a. Solids appeared to be all one phase as minute trigonal plates of hemimorphic form. Confirmed by X-ray
to be 1:3:6:20 salt. Microchemical tests showed predominantly K-type with both Fe and Al.
a. Some plates resolved to be trigonal 001 plates of hemimorhpic form. Confirmed by X-ray to be 1:3:6:20
salt.
b. Trace only. Agglomerates of scale-like crystals.
a. Confirmed by X-ray. Present in abundance and filtrate completely solidified. Amorphous phase also
present.
b.
a. Fine grained. Confirmed by X-ray. Microchemical tests showed K, Al, Fe, and P. Remaining filtrate
consisted of a completely solidified jell.
a. Present in abundance. Confirmed by X-ray.
b. Minor phase.
a. Predominant phase, consisted of agglomerates and a few subhedral crystals.
b. Secondary phase, predominantly the K form.
c. Minor phase, present as 10-15 micron hexagonal plate crystals having optical properties of the K-analog.
d. Traces, usually in clusters of seed crystals.
e. Clusters of colorless, grainy particles associated with DCP dihydrate but of higher refractive index.
a. Confirmed by X-ray. Primary solid, consisted of masses of interwoven needle-like, colorless crystals.
Chemical tests show K, Al, Fe, and P.
b. Traces only.
a. Predominant phase.
b. Secondary phase. Confirmed by X-ray.
In filtrates from the present study, it appears that pH,
time of reaction, and the presence of varying amounts of
dissolved soil components are some of the factors that
determined the particular compounds that formed.
Whether or not these compounds are precipitated in situ
in soil near a dissolving granule of MCP may be open to
question, since the environment of the soil surrounding
a dissolving granule would continue to change. The study,
however, does point out the nature of the chemical en-
vironment of the disolving granule and the supersaturated
nature of the solution as it reacts with the surrounding soil.
It would appear that compounds identified in this study
are very likely involved to some extent as initial fertilizer-
soil reaction products.
DISCUSSION
A 5-mesh granule of MCP (2-mm. radius) contains
approximately 10 mg. P, and upon dissolution in water,
is capable of producing 0.052 ml. TPS. This quantity of
solution is capable of wetting a soil shell approximately
2 mm. in thickness around a 5-mesh granule of MCP dur-
ing its initial dissolution. This estimate is based upon the
moisture content found in the soil-fertilizer zone found
in the previous study (9) and is further verified by the
observation of Lehr et al. (7) that a wetted soil shell of
approximately 2 mm. had formed around a 5-mesh granule
in 24 hours.
A direct measurement of the chemical changes occurring
within this 2-mm. reaction zone would require precision
microsampling and microanalytical techniques. It is pos-
sible, by the present experimental technique, to partially
simulate this chemical environment since moisture moves
into the granule as water vapor and the fertilizer solution
moves slowly away by capillary flow (7, 9). This was done
by reacting TPS successively with a series of soil incre-
ments. In the present model of a 5-mesh granule, TPS
would leave the granule and react with the first small
increment of soil; the resulting solution would then react
with the next soil increment, and, in turn, with each suc-
ceeding one. The 10 soil increments would, therefore, rep-
resent successive shells of soil surrounding the granule and
extending through the first 2-mm. shell of soil.
The results showed that within this reaction zone, Fe,
Al, Mn, and other soil constituents were dissolved by the
acidic fertilizer solution. Initially, dissolution reactions pre-
22 SOIL SCIENCE SOCIETY PROCEEDINGS 1959

dominated, but as more soil was contacted and pH of some of the possible compounds that might be expected
the solution increased, the solution .became supersaturated to form, while the study of Bouldin and Sample (1) points
with respect to certain phosphate compounds that sooner to the necessity of considering the influence of associated
or later began to precipitate. salts undoubtedly affecting the reaction and availability
The present experiment simulated the environment of of P in fertilizer granules.
the granule only as long as some of the MCP remained In conclusion, it may be said that highly soluble ferti-
undissolved. Following its disappearance, TPS could no lizers dissolve in soil to produce a chemical environment
longer form. Water movement into the soil-fertilizer reac- that has been widely overlooked. The present study has
tion zone is expected to continue, and thereby dilute the helped to define the nature of this soil-fertilizer reaction
solution of the reaction zone and enable it to extend zone in the case of MCP. A further investigation of the
farther from the granule (9). A few weeks following the compounds that can form in the chemical matrix remaining
initial dissolution, the movement of fertilizer P will likely from these initial reactions should be useful in determining
extend over a distance of approximately 1 cm. from the the chemical transformation of fertilizer P into the more
original granule site (1, 7, 8). The reactions occurring insoluble soil P.
during this dilution and expansion process will be referred
to in a later study.
The present study was made on the basis that TPS was
the solution leaving a granule of MCP, since its formation
is possible (9). These studies, therefore, represent the most
acid environment that would be imposed by dissolution
and hydrolosis of MCP in soil.
There is evidence that MCP reactions in different soils
may be quite different. In the case of the slightly calcar-
eous Rosebud soil, the dissolved Ca was sufficient to cause
DCP dihydrate to precipitate, not only at the original
placement site (2, 7), but also throughout the soil zone
contacted by the fertilizer solution. The greater the Ca
content of a soil, the greater is the possibility that Ca will
play a dominating role in precipitation of the fertilizer P
in this zone. In the present studies, Fe and Al were more
readily dissolved from the acid Hartsells than from the
calcareous soil. Under such conditions, Fe and Al will
•likely predominate in the initial precipitation of fertilizer P
leaving the granule.
The present study adds evidence for the hypothesis
that fixation of phosphate in soils involves dissolution and
precipitation reactions (4, 6). The acid environment im-
posed in soil by the dissolving MCP granule accentuates
the dissolution process. Perhaps a more careful study of
the different environments that can be found in soil sur-
rounding a dissolving MCP granule will be helpful in
determining in more detail the initial compounds and their
transformation to more stable ones as the initial acid
environment of the granule gradually disappears. The
studies of Haseman et al. (4, 5) are useful in denoting