HAMALOVA ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 80, No.
6,1997 1151
AGRICULTURAL MATERIALS
Determination of Phosphorus, Potassium, and Magnesium in
Fertilizers by Inductively Coupled Plasma-Atomic Emission
Spectroscopy and Comparison with Other Techniques
MARTINA HAMALOVA, JIRINA HODSLAVSKA, and PAVEL JANOS 1
Research Institute of Inorganic Chemistry, Revolucni 84, CZ-400 01, Czech Republic
VIKTOR KANICKY
Masaryk University, Department of Analytical Chemistry, Kotlafska 2, CZ-611 37, Czech Republic
Phosphorus, potassium, and magnesium in 12 fer­
tilizers were determined by inductively coupled
plasma-atomic emission spectroscopy (ICP-AES),
and results were compared with those obtained by
standard gravimetry (phosphorus) and atomic ab­
sorption spectrometry (AAS) (potassium and mag­
nesium). ICP-AES and gravimetry were also used
to determine water- and citrate-soluble phospho­
rus in fertilizers. In all cases, precision and accu­
racy of the ICP-AES method were satisfactory.
Certain differences, probably not significant for
routine analyses, were observed between
ICP-AES and gravimetry in determinations of total
and citrate-soluble phosphorus when the mea­
surements were performed strictly under condi­
tions of repeatability.
ertilizer analyses are necessary not only for qual­
F
ity control of their production, but also for their
effective and environmental-friendly agrochemi-
cal applications. The major nutrients nitrogen, phos­
phorus, and potassium, are most frequently deter­
mined. However, other essential elements, such as cal­
cium, magnesium, boron, copper, iron, manganese, and
zinc, should be checked thoroughly, too (1, 2). Gravi­
metric quinolinium molybdophosphate method and
spectrophotometric molybdovanadophosphate method
are examples of official procedures for phosphate de­
termination. Flame photometry and atomic absorption
spectrometry (AAS) are most frequently used for deter­
mining potassium, magnesium, and some minor ele­
ments (3, 4). Automatic analysers and flow analysis
methods have been applied to nitrogen, phosphorus,
and potassium (3, 5). Higher concentrations of calcium
and magnesium can be determined by titration with
ethylenediaminetetraacetic acid (3, 6).
Inductively coupled plasma-atomic emission spec­
trometry (ICP-AES) can determine several elements
Received April 10, 1997. Accepted by RN June 26, 1997.
1
Author to whom correspondence should be addressed.
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simultaneously in a wide range of concentrations (7, 8).
Jones (9, 10) used ICP-AES to determine major nutri­
ents, micronutrients, and trace elements in fertilizer
standards. Aten et al. (11) compared ICP-AES deter­
minations of magnesium, iron, and zinc in fertilizers
with analysis by flame AAS. DC argon plasma emission
spectrometry was used to determine aluminum, iron,
calcium, and magnesium in wet-process phosphoric acid
(12). More recently, Matilainen and Tummavuori stud­
ied spectral and interelement effects in ICP-AES de­
terminations of boron (13), magnesium (14), iron (15),
and sulfur (16) in commercial NPK fertilizers. Masson
and Esvan (17) used ICP-AES to determine phospho­
rus, potassium, magnesium, and some metals (Ca, Cu,
Fe, Mn, and Zn) in plant samples.
We used ICP-AES to determine phosphorus, potas­
sium, and magnesium in various fertilizer and com­
pared results with those obtained by gavimetry (phos­
phorus) and AAS (potassium and magnesium). We
used both ICP-AES and gravimetry to determine
phosphorus in water and citrate extracts of fertilizers.
Experimental
Instrumentation
(a) ICP-AES spectrometer. — Optima 3000
(Perkin-Elmer, Norwalk, CT).
(b) AAS spectrometer.—AA 30 (Varian, Mulgrave
Victoria, Australia).
(c) X-ray diffractometer.—PW 1820 (Philips Analyt­
ical, Almelo, The Netherlands).
Procedures
ICP-AES determinations of phosphorus, potassium,
and magnesium were performed at emission lines
213.618, 766.491, and 279.079 nm, respectively. The
ICP spectrometer was operated at standard source
conditions: power input of 1100 W; nebulizer, auxiliary,
and plasma gas flow rates of 1.0, 1.0, and 15 L/min of
Ar, respectively; and pump flow rate of 1.0 mL/min.
1152 HAMALOVA ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 80, No. 6, 1997
The observation height was 15 mm above the load coil.
The plasma torch was provided with standard alumina
injector with 2.0 mm id. The standard gem tip cross-flow
pneumatic nebulizer was used for analyses. Back­
ground-corrected intensities were measured at normal
resolution by the area-processing mode. Spectral inter­
ferences were examined by using single-element solu­
tions of the main constituents. No interelement correc­
tions for spectral interferences were necessary. Auto­
matic sampling and integration times were used.
Gravimetric determination of phosphorus was per­
formed according to AOAC official methods (18). The
slightly modified AOAC official methods (3) were used
for the flame AAS determinations of potassium and
magnesium (procedures for preparing the working solu­
tions were taken from the flame photometric method).
Potassium was determined at 766.5 nm in air-C 2 H 2
flame in the presence of CsCl (ionization buffer). Mag­
nesium was determined at 285.2 nm in air-C 2 H 2 flame
in the presence of CsCl and lanthanum.
Standard Solutions and Reagents
Standard solution of phosphorus (0.5 g/L) was pre­
pared from KH 2 P0 4 and its concentration was checked
by the standard gravimetric procedure. Standard solu­
tions (1 g/L) of K and Mg were prepared according to
AOAC official methods (3). The same standard solu­
tions were used for ICP-AES and AAS measurements.
For ICP-AES determinations, mixed calibration solu­
tions were prepared containing 0-20 mg K/L, 0-5 mg
Mg/L, and 0-20 mg P/L in 2% HN0 3 (5 calibration
points for each element). Ammonium citrate solution
was prepared from citric acid by neutralization to
pH 7.0 with ammonium hydroxide (2): 370 g citric acid
was dissolved in 1.5 L distilled water and the pH was
30
V5
o 25
20
>>
u
15
B
> y = 0.9841x-0.0867
u 10
(3D
K10
10 15
ICP (% P2Os)
Figure 1. Determination of phosphorus in fertilizers by ICP-AES and gravimetric methods.
Table 1. Main constituents of fertilizers examined
Sample
No. Compounds identified by X-ray diffraction
K1 NH 4 H 2 P0 4 , NH4CI, K 2 S0 4
K2 NH 4 H z P0 4 ,NH 4 CI, CaS0 4
K3 NH 4 H 2 P0 4 , NH4CI, K 2 S0 4
K4 NH 4 H 2 P0 4 , NH4CI, (NH 4 ) 2 S0 4
K5 NH 4 H 2 P0 4 , NH4CI, K 2 S0 4
K6 NH 4 H 2 P0 4 , NH4CI, NH 4 N0 3 , KN0 3
K7 NH 4 H 2 P0 4 , NH4CI, KN0 3
K8 NH 4 H 2 P0 4 , NH4CI, Ca 5 (P0 4 ) 3 F
K9 NH 4 H 2 P0 4 , NH4CI, CaMg(C0 3 ) 2
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K10 Amorphous phosphates, NH4CI, KN0 3 , CaS0 4 • 0.5H20
K11 Ca 5 (P0 4 ) 3 F, CaF2, CaMg(C0 3 ) 2
K12 NH4H2P04,MgS04-H20
adjusted to 7.0 ±0.1 with ammonium hydroxide and a
pH meter with a glass electrode. The solution was
diluted to 2 L with water. All chemicals used were
reagent-grade quality, obtained from Lachema, Brno,
Czech Republic. Distilled water deionized on a mixed-
bed ion-exchange column was used to prepare the
solutions.
Samples
Commercial fertilizers as well as newly developed
ones were analyzed. Main constituents were deter­
mined by X-ray diffraction (Table 1). AOAC official
final-action methods were used for total determina­
tions of phosphorus, potassium, and magnesium (3,18).
Samples (1 g) were boiled gently with 20 mL nitric acid
(1 + 1), diluted to 100 mL, and filtered through a dry
filter. The same sample preparation was used for
ICP-AES, gravimetric, and AAS analyses. Before
K11
r = 0.9987
20 25 30
 HAMALOVA ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 80, No. 6,1997 1153

ICP-AES measurements, dissolved samples were fur­ Calculations

ther diluted 100 times.
Solutions for water-soluble phosphorus and extracts
with ammonium citrate were prepared (2). To obtain
water extracts, 10 g powdered fertilizer (grain size
< 0.5 mm) was extracted with 400 mL water for 30 min
in a rotating mixer, diluted to 500 mL, and filtered. To
obtain citrate extracts, the powdered sample was ex­
tracted with neutralized ammonium citrate (1 g fertil­
izer + 100 mL ammonium citrate) at 65° + 1°C for 1 h
in a mixing device, diluted to 500 mL, and filtered.
For ICP-AES determinations, extracts were acidi­
fied with concentrated nitric acid to a final H N 0 3
ADSTAT (TriloByte, Pardubice, Czech Republic)
and LABSTAT (QM-Service, Prague, Czech Republic)
statistical softwares were used in statistical evaluation
of the experimental data.
Results and Discussion
Two samples of every fertilizer listed in Table 1 were
dissolved in dilute nitric acid and analyzed simultane­
ously by the ICP-AES method and by the standard
gravimetric or AAS method. Results are shown in

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concentration of 2% before measurements. Figures 1-3.

y= 1.0116x- 0.322
r = 0.9994

0 5 10 15 20 25

ICP (%K20)
Figure 2. Determination of potassium in fertilizers by ICP-AES and AAS methods.

K12
y = 1.0001x +0.0098
r = 0.9997
ob
(3D

£ 4
3
GO

0 2 4 6 8 10

ICP (%MgO)
Figure 3. Determination of magnesium in fertilizers by ICP-AES and AAS methods
1154 HAMALOVA E T AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 80, No. 6, 1997

Table 2. Determination of potassium and magnesium in NPK fertilizer with dolomite

K 2 0, % MgO, %
Samplej No. ICP-AES AAS ICP-AES AAS

1 14.67 14.71 2.07 2.08

2 14.96 14.82 2.11 2.05
3 14.76 14.92 2.11 2.11
4 14.95 14.90 2.12 2.10
5 14.75 14.98 2.13 2.02
6 14.73 14.83 2.12 2.07
7 14.87 14.98 2.10 2.10

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8 14.85 14.76 2.06 2.12
9 14.68 14.70 2.08 2.10
10 14.76 14.75 2.10 2.05

Mean 14.80 14.84 2.10 2.08

Standard deviation 0.104 0.106 0.023 0.032

Analysis of variance, a == 0.05

Source of Degrees of Sum of Mean of Degrees of Sum of Mean of

variation freedom squares squares F-ratio freedom squares squares F-ratio

Between methods 1 0.0068 0.0068 0.623 1 0.0020 0.0020 2.571

Residual 18 0.1978 0.0110 18 0.0140 0.0008
Total 19 0.2047 0.0108 19 0.0160 0.0008

Table 3. Determination of phosphorus in NPK fertilizer with dolomite (total P 2 O s ) and in citrate and water
extracts of this fertilizer

Total P 2 0 5 , % Citrate-soluble P 2 0 5 , % Water-soluble P 2 0 5 , %

Sample No. ICP-AES Gravimetry ICP-AES Gravimetry ICP-AES Gravimetry

1 15.76 15.38 15.32 15.06 8.25 8.33

2 15.83 15.43 15.19 14.99 8.44 8.29
3 15.79 15.44 15.04 14.99 8.20 8.31
4 15.80 15.41 15.19 15.13 8.17 8.31
5 15.72 15.42 15.27 15.04 8.21 8.32
6 15.68 15.37 15.00 15.01 8.36 8.37
7 15.81 15.44 15.12 14.99 8.32 8.33
8 15.73 15.47 15.39 14.94 8.36 8.32
9 15.76 15.47 15.34 15.10 8.26 8.31
10 15.75 15.46 15.13 15.04 8.40 8.29
Mean 15.76 15.43 15.20 15.03 8.30 8.32
Standard deviation 0.046 0.035 0.130 0.057 0.092 0.023

Analysis of variance, a ■■
= 0.05

Degrees of Sum of Mean of Degrees of Sum of Mean of Degrees of Sum of Mean of

Source freedom squares squares F-ratio freedom squares squares F-ratio freedom squares squares F-ratio

Between
methods 1 0.5578 0.5578 338.05 1 0.1445 0.1445 14.34 1 0.0022 0.0022 0.490
Residual 18 0.0297 0.0017 18 0.1814 0.0101 18 0.0810 0.0045
Total 19 0.5875 0.0309 19 0.3259 0.0172 19 0.0832 0.0044
 HAMALOVA ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL.
Linear regression analysis of phosphate results (with
the ADSTAT statistical program) proved that the y-axis
intercept of the plot of gravimetric results versus
ICP-AES results (Figure 1) does not differ significantly
from zero and the slope of the line does not differ
significantly from unity. Thus, ICP-AES exhibits nei­
ther constant nor proportional systematic errors when
compared with the gravimetric method.
For potassium determinations, the slope of the re­
gression line (Figure 2) does not differ significantly
from unity, but the y-axis intercept is statistically signif­
icantly different from zero. These results suggest that
the ICP-AES method exhibits a positive constant sys­
tematic error in comparison with the AAS method.
This error may become important in determinations of
low contents of potassium. For common fertilizers con­
taining about 15% K 2 0 , the relative error is less than
2%.
For the regression line for magnesium analysis (Fig­
ure 3), the y-axis intercept does not differ significantly
from zero, and the slope does not differ significantly
from unity. Thus, ICP-AES determination of magne­
sium does not exhibit systematic constant and propor­
tional errors compared with the AAS method.
Precisions of potassium and magnesium determina­
tions by ICP-AES and AAS were tested by analysis of
an NPK fertilizer with dolomite. Ten sample portions
were prepared and analyzed by ICP-AES. Simultane­
ously, portions of the same sample were analyzed by
AAS. Measurements were performed under conditions
of repeatability (the same operator, the same equip­
ment, etc.) within a short time interval (one day).
Precisions for both ICP-AES and AAS determinations
are good (Table 2). Relative standard deviations (RSDs)
are < 2 % in all the cases. ICP-AES results do not
differ significantly from AAS results, as confirmed by
analysis of variance and by a nonparametric Kruskal-
Wallis test.
Precisions of phosphate determinations (total, cit­
rate-soluble, and water-soluble) also were very good
(Table 3). ICP-AES and the gravimetric methods gave
comparable precisions (RSD = 0.2-0.3%) for the de­
termination of total P 2 0 5 . For citrate- and water-solu­
ble P 2 0 5 , the ICP-AES method had a slightly lower
precision than gravimetry. Statistical analyses indicate
that differences in results of ICP-AES and gravimetric
methods for total and citrate-soluble phosphorus are
statistically significantly. The reasons are not clear.
However, the relative difference between the methods
is about 1-2%, which is still quite acceptable. Precision
achieved under conditions of reproducibility (day-to­
day, operator-to-operator, laboratory-to-laboratory,
etc.) is expected to be (maybe markedly) worse.
Conclusions
The ICP-AES method enables simultaneous deter­
minations of phosphorus, potassium, and magnesium in
fertilizers. It also allows determination of the assimi­
80, No. 6,1997 1155
lated forms of phosphorus (water-soluble and citrate-
soluble P 2 O s ). In general, the precision and accuracy of
ICP-AES determinations are comparable with those
achieved with standard methods (gravimetry and AAS).
However, a small constant systematic error was ob­
served in ICP-AES determination of potassium. This
error becomes insignificant for common fertilizers con­
taining about 15% K 2 0 . Statistically significant, but
not very large, differences were observed between the
ICP-AES and gravimetric methods in determinations
of total and citrate-soluble phosphorus when the mea­
surements were done under conditions of repeatability.
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Acknowledgments
We thank Lovochemie Ltd., Lovosice, Czech Repub­
lic, and the Synthesia Ltd., Pardubice-Semtin, Czech
Republic for providing fertilizer samples.
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