Fertilizer Research 12:185-192 (1987)

© Martinus Nijhoff Publishers, Dordrecht--Printed in the Netherlands 185

The use of chemical solubility tests in comparing phosphate

fertilisers

A.C. B R A I T H W A I T E
Fertiliser Manufacturers" Research Association, P.O. Box 10259 Balmoral, New Zealand

Accepted 2 November 1986

Abstract. The 'standard' solubility tests as used in New Zealand for assessing single superphosphate
have been applied to alternative high analysis fertilisers such as triple superphosphate and partially
acidulated phosphate rocks using phosphoric acid. Under differing experimental conditions it has
been established that the phosphate rock component has a variable solubility in 2% citric acid at
all levels, and in neutral ammonium citrate at high levels of PR content, making comparisons
between percentages of soluble P derived from different fertilisers inappropriate for chemical or
agronomic assessment. Only water, which extracts all the monocalcium phosphate component but
none of the phosphate rock, can be used to compare the efficiencyof the acidulation process, and
neutral ammonium citrate can be used to assess the amount of phosphate rock remaining when the
acidulation level is in excess of 50%. 2% formic acid produced almost identical results to 2% citric
acid for partially acidulated materials and therefore cannot be recommended as an alternative,
improved extractant for fertilisers containing large proportions of residual phosphate rock.

Introduction

In N e w Zealand there are three solubility tests which can be used to gauge the
efficiency o f m a n u f a c t u r e and the likely effectiveness o f phosphate fertilisers
which have been based until recently almost exclusively on single superphos-
phate (SSP) products. Studies [6] have indicated that the following c o m p o n e n t s
are solubilised by the three extractants 2% citric acid (pH 2) (CA), water (W),
and neutral a m m o n i u m citrate (NAC):

(a) C A - - all the m o n o c a l c i u m phosphate (MCP), dicatcium phosphate (DCP),

a p r o p o r t i o n o f the iron (Fe) and aluminium (A1) impurity phosphate
(usually c. 20%), and a similar p r o p o r t i o n o f the residual phosphate rock
(PR).
(b) W - - only the M C P .
(c) N A C - - all the M C P and D C P , and m o s t (80 to 100%) o f the Fe a~d A1
species (but none o f the PR).

Therefore water has been used to assess the p r o p o r t i o n o f M C P p r o d u c e d

(which gives an indication o f the efficiency o f the conversion o f insoluble to
soluble P) and N A C used indirectly (by subtracting f r o m the total P) to indicate
the a m o u n t o f residual PR. H o w e v e r neither o f these tests has been as p o p u l a r
as the C A test in N e w Zealand; by usually a d o p t i n g a m i d w a y position between
the other two figures because o f the smaller percentage o f Fe and A1 extracted
186

it is considered to be the most 'accurate' figure for advisory purposes by the

Ministry of Agriculture and Fisheries in New Zealand. However this decision
has been criticised because:

(a) the test does not give a good correlation with agronomic response in pot
trials using SSP [14] or PR [7, 9], although one study using PRs indicated
that it was superior to NAC [5].
(b) the test has been said to extract more P in instances where high Fe and A1
contents are present [12, 13].
(c) the reliability of the test has been questioned [4] because it is only a 'spot
check' of a continuous dissolution procedure and PR solubilities can be
influenced by a variety of chemical factors, such as solid to solvent ratio,
temperature, shaking time and speed [1, 8, 11].
With a changing emphasis in New Zealand towards higher analysis P fertilisers,
some of which contain large quantities of unreacted PR, it has become very
important to examine the appropriateness and accuracy of the above chemical
tests with regard to these alternative fertilisers. If, for example, it is found that
they extract different proportions of different components in a comparison of
fertilisers then the figure so derived cannot be directly compared either for
chemical or agronomic purposes. Accordingly this paper investigates the
components extracted in each solubility test for a variety of fertiliser options
including triple superphosphate (TSP), partially acidulated phosphate rock
(PAPR) using phosphoric acid, and reactive North Carolina PR (NCPR) itself.
A further possibility exists in the option of choosing a completely different
extractant for assessment of partially acidulated materials. The most likely such
solvent is 2% formic acid (FA) [7, 11], which is used in European Economic
Community countries to grade PRs in order of chemical reactivity; by extracting
more P than CA when unacidulated PRs are tested it may be more appropriate
for PAPRs especially. Therefore a direct comparison between FA and CA
solubilities on a suitable set of products derived from the initial solubility test
comparisons discussed above has been undertaken.

Experimental

Two laboratory TSPs (based on Nauru (N) PR or a Nauru-Christmas (1 : 1) PR

blend (N/X), these being traditional PRs in New Zealand for making SSP) and
two PAPRs (based on ground reactive NCPR, acidulated to 20% (NC20) and
50% (NC50) of the stoichiometric amount of phosphoric acid to make TSP) and
two standards (MCP and NCPR, ground so that 70% of the material passes a
75~tm sieve) were used for solubility experiments. Preparations have been
described previously [2] with analyses in Table 1.
Because all the products contain more P than SSP per unit of material (total
P figures being c. 1.5 to 2.5 times greater than for typical SSP) the 'standard'
 187

Table 1. Analyses of test materials.

Material Total P PW+NAC PCAt Pw t PNACt PFAt

(AOAC)
MCP 24.6 24.6 (I00) 24.6 (100) 24.5 (100) 24.6(100)
N TSP 19.9 19.5 (98) 18.1 (91) 17.9 (90) 19.3 (97)
N/X TSP 22.5 21.2 (94) 19.6 (87) 19.3 (86) 20.8 (92)
NC 50 16.0 13.6 (85) 12.7 (79) 10.5 (66) 11.4 (71)
NC 20 16.5 8.4 (51) 9.8 (60) 6.4 (39) 7.9 (48)
NCPR 13.0 3.9 (30) 5.2 (40) 0 (0) 3.8 (29)
NC 35 L 16.0 11.8 (74) 11.3 (70) 8.8 (55) 10.0 (62) 11.0 (69)
NC 35 J 16.2 11.7 (72) 10.8 (66) 8.4 (52) 9.2 (57) 10,9 (67)
NC 35 AM 16.2 11.3 (70) 10.5 (64) 8.1 (50) 9.2 (57) 10.5 (64)
t figures in parentheses are percentages of soluble P.

tests using 1 g of fertiliser in 100 ml of extractant and shaking for 30 minutes at

20 °C (CA and W ) o r for 60 minutes at 65 °C (NAC) were subsequently altered
to incorporate the P-equivalent weight of fertiliser. This was again adjusted to
incorporate 1 g of solid by adding diluent sand or calcium sulphate to the
P-equivalent weight to test the efficiency of extraction. Accordingly each
product was tested:
(a) using 1 g of product
(b) using the 'equivalent P' weight - - on the assumption that SSP contains 10%
P, 0.5g of the TSPs or MCP and 0.6g of the PAPRs or N C P R were taken.
(c) using the 'equivalent P' weight with added sand or calcium sulphate (0.4 or ~
0.5 g) to make up to the same solid to solvent ratio as previously. In this way
both the effects of solid to solvent and P to solvent ratios could be assessed.
For comparison the standard AOAC sequential extraction for 'available P'
(water followed by N A C extraction on the residue) was also carried out. In a
second set of experiments the effects of the ratio of N C P R to MCP on the
dissolution of the PR component were examined. N C P R samples (0.3 to 1 g)
were shaken in either CA or NAC (PR is insoluble in W) containing predissol-
ved MCP at different solid to solvent and N C P R to MCP ratios and the relative
suppression of PR solubility by M C P assessed.
Finally the CA and FA solubilities of three PAPRs made from different
phosphoric acids (Laboratory (L), Jordan (J), and American (AM), see [3] for
analyses) at the same level of acidulation (35% of stoichiometric) were exam-
ined. Chemical analyses of these three products are described in Table 1. This
35% acidulation level was chosen in these experiments because the MCP to PR
ratio is approximately 1 : 1, which was found to be a sensitive area for study from
earlier experiments, and because a level of approximately 30 to 35 % acidulation
has dominated PAPR discussions in New Zealand. In addition to studies of
solid to solvent ratio effects, acid concentration and time of extraction were also
examined. The CA and FA solubilities of the PAPR residues were subsequently
assessed after a standard water solubility extraction had removed the MCP
fraction.
188

Results and discussion

Solid to solvent a n d P to solvent effects are d e t a i l e d in T a b l e 2. Solubilities in

w a t e r were unaffected b y these factors, a n a n t i c i p a t e d result since the M C P
c o m p o n e n t is r e a d i l y solubilised a n d no o t h e r c o m p o n e n t is e x t r a c t e d by this
solvent. F o r C A a n d N A C , however, r e d u c i n g the solid to solvent r a t i o caused
increases in the percentages o f P dissolved w h e n e v e r a significant P R c o m p o n e n t
was present, i.e. for N C 50, N C 20 a n d N C P R . I n a d d i t i o n these increases
b e c a m e greater as the p e r c e n t a g e o f P R b e c a m e higher, i n d i c a t i n g t h a t the P R
c o m p o n e n t was influencing the solubility percentage, as occurs for the P R b y
itself, either by direct P d i s s o l u t i o n o r b y c o m p l e x a t i o n o f the calcium ions in
the a p a t i t e causing P to dissolve [1, 8, 11]. I n c r e a s i n g the solid to solvent ratio
to its original figure (1 g in 100 ml solvent) b y the a d d i t i o n o f s a n d o r calcium
s u l p h a t e h a d only a m i n o r effect b y c o m p a r i s o n , suggesting t h a t P to solvent,
r a t h e r t h a n solid to solvent, r a t i o was the m o r e i m p o r t a n t factor.
I n c o m p a r i n g C A a n d N A C solubility effects it was a p p a r e n t t h a t P to solvent
effects h a d a g r e a t e r influence, with higher figures p r o d u c e d , on the former.
H o w e v e r the fact t h a t N A C solubilities were similarly influenced i n d i c a t e d t h a t

Table 2. Percentages of P soluble at different P solvent ratios.

Material Weight Percentages of P soluble in

CA W NAC
MCP 1g 100 100 100
0.5 g I00 100 100
0.5g ÷ S* 100 100 100
0.5 g + C* 100 100 100
N TSP 1g 91 90 97
0.54 g 94 90 98
0.5g ÷ S 94 90 96
0.5 g + C 93 90 98
N/X TSP 1g 87 85 92
0.5 g 90 86 92
0.5g + S 89 86 91
0.5g + C 89 86 93
NC 50 1g 79 67 71
0.6 g 85 67 74
0.6g + S 85 67 72
0.6g + C 85 67 73
NC 20 Ig 60 26 48
• 0.6g 71 26 58
0.6g + S 70 26 57
0.6g + C 70 26 58
NCPR 1g 40 0 29
0.6g 58 0 41
0.6g ÷ S 56 0 38
0.6g + C 57 0 39
*S = added sand to make total weight up to 1 g.
*C = added calcium sulphate to make total weight up to 1g.
 189

PR, certainly at low acidulation levels, had some solubility in NAC, in con-
tradiction to effects found for SSPs [6]. This was confirmed in experiments
described in Table 3 comparing the solubility of N C P R in solvents containing
varying amounts of dissolved MCP. Although the NAC solubility levels de-
creased more rapidly than the corresponding CA figures as more MCP was
added, there was still a finite solubility at a 1 : 1 PR to MCP level (representing
a PAPR acidulated to the 30 to 35% acidulation level). P to solvent ratio was
still very significant, with considerably larger percentages of P dissolving at the
lower addition level.
Therefore both P to solvent and N C P R to MCP ratios were found to affect
the PR solubility in CA and NAC determinations, making them unreliable tests
for comparing partially or unacidulated materials such as PAPR or N C P R with
SSP, and certainly removing the possibility of a correlation with agronomic
response. The failure of CA in this regard prompted the examination of FA as
an alternative extractant which may produce a consistent PR solubility under all
conditions; the results of this comparison using three NC 35 products (chosen
because of the variable PR solubility found for CA at this 1 : 1 PR to MCP level
as described above) are shown in Table 4.
It was extremely surprising to note that CA and FA solubilities for the PAPR
35 materials were identical under similar conditions and that FA solubilities
were affected in parallel with CA figures by changes in P to solvent ratio, acid
concentration and time of extraction. This result is in contradiction with the
higher FA solubilities found for N C P R itself (40% for CA and 68% for FA).
Examination of the solubility of 1 g of the PR residue (from a W extraction,

Table 3. Percentages of P soluble under different PR to MCP ratios.

Amount Amt predissolved %PR dissolved in

PR(g) MCP (g/100 ml)
CA NAC

1.0 0.0 40 29
1.0 0.2 35 17
1.0 0.3 30 10
1.0 0.8 26 7
0.3 0.3 71 66
0.6 0.6 40 20
0.8 0.8 36 16

Table 4. Percentages of P soluble in acid solutions (NC 35 products).

Acid 4% CA 4% FA 2% CA 2% FA 2% CA 2% FA 2% CA 2% FA
(60m) + (60m) + (0.6g)* (0.6g)*

L 80 79 73 73 75 75 80 80
J 76 75 70 69 72 71 76 76
AM 70 69 64 64 66 65 71 71

+ using an extraction time of 60 minutes.

" using 0.6g rather than 1 g.
190
Table 5. Percentages of P soluble using sequential extractions (lqC 35 products).

Add Pw PCA+ PFA+ Pw + PCA Pw + PFA

L 56 23 23 79 79
J 53 18 19 71 72
AM 50 18 19 68 69

+ Solubility tests performed on 1 g of residue ~ o m w a t e r extraction.

Table 5) indicated that the 'raw' PR solubility had been considerably reduced
by the acidulation process to c. 20% for both CA and FA extractions. This
suppression in PR solubility has been observed previously [10] and was said to
be due to a suppression of PR 'reactivity' after acidulation. Therefore for
partially acidulated materials such as PAPR there is no advantage in using FA
in preference to CA as extractant, since it is equally unreliable and gives almost
identical percentages.

Conclusions

CA and NAC solubility tests cannot be considered reliable or accurate tests of

the amount of P that has been converted during acidulation or to indicate how
much P has become 'available' agronomically because of the variable solubility
of the PR component in the products. This is especially true when large quan-
tities of PR are residual, as in PAPRs for example. For NAC, the PR solubility
is almost negligible at levels higher than 50% of stoichiometric, but is in-
creasingly significant at lower levels. For CA, PR solubility, whenever this
component is present, is always significant although effects become smaller as
the level of PR is reduced. The PR solubility is dependent on the P to solvent
ratio and the proportional amount of PR to MCP. In fact only W provides a
reliable guide to the amount of MCP obtained in all instances. An alternative
test using FA produces exactly the same figures and influences as CA and cannot
therefore be recommended as an alternative.
Because of the suppression of PR solubility after acidulation the effects
observed in 'model' experiments using mixtures of unprocessed NCPR and
MCP will be reduced if processed fertilisers are considered. Nevertheless the
effects have been shown to be significant in the latter instances and therefore
solubility percentages cannot be used as an absolute indicator of agronomic
performance on a pure chemical basis. As found for SSP, W solubilities can be
used to assess the level of MCPpresent (and hence the efficiency of acidulation)
and NAC to gauge the amount of PR residual (by difference from total P)
whenever the acidulation level is greater than 50% in alternative fertilisers;
otherwise chemical and agronomic comparisons with SSP based on solubility
figures alone are inappropriate.
 191
Acknowledgements

Mr C.J. Massey and Miss Z.T. Nisha are thanked for technical assistance.

References

1. Amarasiri SL and Abeyroon V (1977) Some analytical considerations in the evaluation of rock
phosphates using citric acid. Tropical Agriculturist CXXXIII: 99-104
2. Braithwaite AC (1986) A comparison of fertilisers made by partially and fully acidulating
phosphate rocks with phosphoric acid. NZ J Tech 2:37.42
3. Braithwaite AC (1987) Processing aspects of production of partially acidulated phosphate
rocks made from phosphoric acid. Fert Res (in press)
4. Braithwaite AC and Rogers DA (1985) The reliability and appropriateness of chemical
solubility tests for phosphate fertilisers, NZFMRA 9th Res Symp Proc pp 3-15
5. Caro JH and Hill WL (1956) Characteristics and fertilizer value of phosphate rock from
different fields. Agric Food Chem 4:684-687
6. Charleston AG (1984) Solubilities of single superphosphate components in water, 2% citric
acid, and neutral ammonium citrate solutions, NZ J Sci 27:269-277
7. Chien SH and Hammond LL (1978) A comparison of various laboratory methods for
predicting the agronomic potential of phosphate rock for direct application. Soil Sci Soc Am
J 42:935-939
8. Krumm HE (1969) The limitations of citric acid solubility as a measure of availability of rock
phosphate. Fert Soc South Africa J 1:41-45
9. MacKay AD, Syers JK and Gregg PEH (I 984) Ability of chemical extraction procedures to
assess the agronomic effectiveness of phosphate rock materials. NZ J Agric Res 27:219-230
I0. McSweeney G, Charleston AG, Condron LM and Campbell AS (1985) Some properties of the
residual apatite remaining in PAPR manufactured from North Carolina phosphate rock.
NZFMRA 20th Tech Conf Proc, pp 393-410
11. Peter A (1972) Solubility of calcium rock phosphate. Proc Hyperphosphate Agron Committee,
Part II; pp 5-34
12. Quin BF (1982) The quality of New Zealand superphosphate. NZ Agric Sci 16:93-100
13. Quin BF (1982) The use of citric acid soluble and water soluble phosphate to assess the
agronomic value of fertilisers. NZFMRA 7th Res Symp Proc, pp 4~54
14. Stephen RC (1982) The relationship between phosphorus solubility of single superphosphate
in different extractants and the dry matter production of ryegrass in pots. NZFMRA 7th Res
Syrup Proc pp 23-31