Bartos et al.: Journal of AOAC International Vol. 97, No.

3, 2014 687
SPECIAL GUEST EDITOR SECTION

Determination of Phosphorus and Potassium in Commercial

Inorganic Fertilizers by Inductively Coupled Plasma-Optical
Emission Spectrometry: Single-Laboratory Validation
James M. Bartos

Office of Indiana State Chemist, 175 South University St, West Lafayette, IN 47907

Barton L. Boggs, J. Harold Falls, and Sanford A. Siegel

CF Industries, 10608 Paul Buchman Hwy, Plant City, FL 33565

A two-part single-laboratory validation study was

conducted for determination of the P and K content
in commercial fertilizer materials by inductively
coupled plasma-optical emission spectrometry (ICPOES). While several methods exist for determination
of P and K in fertilizer products, the main focus of
this study was on ICP-OES determination, which
offers several unique advantages. Fertilizer samples
with consensus P and K values from the Magruder
and Association of Fertilizer and Phosphate
Chemists (AFPC) check sample programs were
selected for this study. Validation materials ranging
from 4.4 to 52.4% P2O5 (1.7 to 22.7% P) and 3 to 62%
K2O (2.5 to 51.5% K) were utilized. Because all P
and K compounds contained in fertilizer materials
are not available for plants to use, this study
was conducted in two parts. Part A focused on
ammonium citratedisodium EDTA as the extraction
solvent, as it estimates the pool of fertilizer P and
K that is considered available to plants. PartB
focused on hydrochloric acid as the digestion
solvent, as it estimates the total P and K content of
the fertilizer product. Selectivity studies indicated
that this method can have a high bias for fertilizer
products containing sources of phosphite or organic
P compared to gravimetric or colorimetric methods
that measure just orthophosphate. Provided the
analytical challenges outlined in this study are
addressed, this method offers the potential for a
quick, accurate, and safe alternative for determining
the P and K content of commercial inorganic
fertilizer materials.

everal AOAC methods (935.02, 949.01, 955.06, 957.02,

958.01, 958.02, 960.02, 960.03, 962.02, 969.02, 969.04,
971.01, 978.01, and 983.02) exist for the determination
of P and K in fertilizer materials(1). Historically, these methods
have worked well, but most utilize slower, more labor-intensive
methodologies, including gravimetric, titrimetric, photometric,
and colorimetric techniques. Furthermore, several of these
Guest edited as a special report from the AOAC Agricultural
Community on Collaborations in New and Improved Methods of
Analysis for Plant Food Materials by Nancy Thiex.
Corresponding authors e-mail: jbartos@purdue.edu
DOI: 10.5740/jaoacint.12-399

methods use one or more chemical reagents that have safety

concerns, including quinoline (benzopyridine), formaldehyde,
tetraphenylboron, and perchloric acid. An added benefit is that
inductively coupled plasma-optical emission spectrometry
(ICP-OES) instruments can provide simultaneous determination
of both P and K, whereas most existing methodologies require
the separate determination of each. The instrument analysis time
for this method is approximately 2 min/sample. The primary
waste generated by this method is excess sample extract
solution, which can be disposed of safely in the laboratory
environment, and only requires basic personal protective
equipment. Many laboratories engaged in fertilizer testing have
ICP-OES instrumentation; however, there is not an AOAC
approved method for P and K determination by ICP-OES.
Principle
P and K are macronutrients, or nutrients required by plants in
higher concentrations(2). Not all sources of P and K contained
in fertilizer products are considered readily available for plant
use. Differentiating between the plant available and total
nutrients requires the use of different extraction solvents.
After solubilizing the desired form of fertilizer P and K in
their respective solvents, the resulting solution is analyzed.
An ICP-OES instrument utilizes a plasma or high-temperature
energy source to ionize or excite electrons to higher energy
orbitals, which return to ground state releasing characteristic
UV or visible wavelengths that can be quantified(3). This study
is presented in two parts, A and B, which represent the two types
of fertilizer P and K commonly tested.
Part A: Ammonium CitrateDisodium EDTA-Soluble P
and K
Study Design
This portion of the single-laboratory validation (SLV) study
is applicable to the determination of the ammonium citrate
disodium EDTA-soluble P, termed direct available phosphate,
and K, termed soluble potash, by ICP-OES. A number of
method challenges were encountered. The main challenges
that the direct available phosphate and soluble potash present
are: the high carbon content in the citrateEDTA solvent that
can deposit in the torch, the carbon chains can reduce plasma
efficiency, thereby requiring a higher plasma energy for P, and
the dynamic K concentration range requires the use of multiple
wavelengths and possible sample dilution. These challenges

688 Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014
Table 1. Validation materials and their P and K content, expressed as P and P2O5 and as K and K2O
Grade

Available P,
%

Source

Available P2O5,
%

Total P,
%

Total P2O5,
%

Soluble K,
a
%

Soluble K2O,
%

34-0-0

ACS reagent grade

21-0-0

ACS reagent grade

5-5-5

Magruder 2006-05

1.93

4.42

2.45

5.60

2.62

3.16

10-10-10

Magruder 2005-10

4.34

9.93

4.38

10.04

8.63

10.39

19-19-19

Magruder 2006-03

8.38

19.20

8.27

18.94

14.98

18.05

6-24-24

Magruder 2004-06

9.77

22.38

9.89

22.64

21.19

25.53

18-46-0

Magruder 2005-01

20.34

46.60

20.47

46.88

NA

NA

11-52-0

AFPC 2006-10

22.85

52.33

22.86

52.36

NA

NA

0-0-50

Magruder 2001-10

NA

NA

NA

NA

42.33

50.99

0-0-60

Magruder 2005-12

NA

NA

NA

NA

51.58

62.13

No total K values are documented for these check sample materials.

are reduced by performing an online dilution, achieved

by using a small sample pump tube and a large ionic buffer/
internal standard pump tube, which dilutes the matrix and
sample concentration approximately four-fold. If the method
challenges listed are properly addressed, the direct available
phosphate and soluble potash content in commercial inorganic
fertilizers, in the absence of organically bound P and K and of
3
phosphite (PO3 ), in the concentration ranges of 0.06 to 53%
P2O5 (0.026 to 23% P) and 0.01 to 63% K2O (0.008 to 53% K)
can be determined.

Table 1. Some benefits of using Magruder and AFPC check

samples as validation materials are that they are preground and
homogeneous, have consensus values for multiple methods,
and are immediately ready for use after minimal mixing. Check
samples representing several common fertilizer materials
with low, medium, and high levels of P and K were chosen.
Validation materials were stored in sealed glass jars for shortterm use and in heat sealed plastic pouches at room temperature
for long-term storage. Negative control material, namely ACS
reagent grade ammonium nitrate (34-0-0) and ACS reagent
grade ammonium sulfate (21-0-0) were utilized.

Validation Materials

A. Apparatus (Part A)

Validation materials were selected from fertilizer materials

maintained by the Magruder (www.magruderchecksample.org)
(4) and Association of Fertilizer and Phosphate Chemist (AFPC;
www.afpc.net) (5) check sample programs, and are listed in

(a) Analytical balance.Readability to 0.1 mg, AT 200

(Mettler Toledo, Columbus, OH).

Table 2. ICP calibration standards from stock reagent salts for citrateEDTA-soluble P and K

Standard ID

Volume,
mL

Citrate,
mL

Stock 1,
a
mL

Stock 2,
b
mL

P concn,
g/mL

P2O5,
g/mL

P2O5
solution,
%

P2O5
sample,
%

K concn,
g/mL

K2O,
g/mL

K2 O
solution,
%

K2O
sample,
%

Blank

1000

400

250

100

10 of Std 7

NA

12

27.5

0.00275

1.4

15.15

18.25

0.00182

0.9

250

100

20 of Std 7

NA

24

55

0.00550

2.7

30.3

36.5

0.00365

1.8

250

100

NA

50

115

0.01146

5.7

63.1

76

0.00760

3.8

250

100

10

NA

100

229

0.02291

11.5

126

152

0.01521

7.6

250

100

15

NA

150

344

0.03437

17.2

189

228

0.02281

11.4

250

100

22

NA

220

504

0.05041

25.2

278

335

0.03345

16.7

250

100

30

NA

300

687

0.06874

34.4

379

456

0.04562

22.8

250

100

40

NA

400

917

0.09165

45.8

505

608

0.06083

30.4

250

100

50

NA

500

1146

0.11457

57.3

631

760

0.07603

38

10

250

100

NA

25

NA

NA

NA

NA

747

900

0.08998

45

11

250

100

NA

30

NA

NA

NA

NA

897

1081

0.10805

54

12

250

100

NA

35

NA

NA

NA

NA

1046

1260

0.12600

63

S
 tock 1 = 2500 g/mL P stock standard = 2.7461 g potassium dihydrogen phosphate (KH2PO4)/250 mL prepared in deionized water. Also, 10 of Std7
represents a serial dilution from another standard, meaning take 10 mL from standard 7.

Stock 2 = 7472 g/mL K stock standard = 3.5615 g potassium chloride or 4.8299 g potassium nitrate/250 mL in deionized water.

Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014 689
Table 3. Calibration criteria for direct-available P and soluble K by ICP-OES
Element ID

Wavelength, nm a

Calibration range, g/mL

Standards used (see Table 2)

Curve fit

Spectral deconvolution
None

177.434 (1)

0 to 100

Blank, 1, 2, 3, 4

Linear

177.434 (2)

100 to 500

4, 5, 6, 7, 8, 9

Linear

None

178.222 (1)

0 to 100

Blank, 1, 2, 3, 4

Linear

None

178.222 (2)

100 to 500

4, 5, 6, 7, 8, 9

Linear

None

213.618 (1)

0 to 100

Blank, 1, 2, 3, 4

Linear

Cu 213.598

213.618 (2)

100 to 500

4, 5, 6, 7, 8, 9

Linear

Cu 213.598

214.914 (1)

0 to 100

Blank, 1, 2, 3, 4

Linear

Cu 214.898

214.914 (2)

100 to 500

4, 5, 6, 7, 8, 9

Linear

Cu 214.898

766.485 (1)

0 to 126

Blank, 1, 2, 3, 4

Quadratic

None

766.485 (2)

50 to 379

3, 4, 5, 6, 7

Quadratic

None

769.897

126 to 505

4, 5, 6, 7, 8

Quadratic

Interference LiNO3

404.721

505 to 1046

8, 9, 10, 11, 12

Quadratic

None

(1) and (2) distinguish between the same wavelength used to cover two separate concentration ranges.

(b) pH meter.Readability to pH 7.00, Model 8005 (VWR

Scientific, Radnor, PA).
(c) pH combination electrode.Orion 9102BNWP (Thermo
Fisher Scientific, Waltham, MA).
(d) Constant temperature water bath.Capable of
maintaining bath temperatures of 652C, BK53, Yamato
Scientific, Santa Clara, CA.
(e) Heated shaking water bath.Capable of maintaining
bath temperatures of 652C, and set to approximately
200 reciprocations/min, designed internally by the Purdue
University Central Machine Shop (West Lafayette, IN).
(f) ICP-OES instrument.Vista Pro-Axial view (Agilent
Technologies, Santa Clara, CA).
(g) Gated riffle splitter.Model 16-25X (Carpco Inc.,
Jacksonville, FL).
(h) Sample grinder.Model ZM200 rotor mill (Retsch,
Haan, Germany).
B. Reagents (Part A)
(a) Ammonium
citrate,
dibasic.(NH4)2HC6H5O7,
formula weight (FW) 226.19, ACS grade, purity >98% (EMD
Chemicals, Darmstadt, Germany).
(b) EDTA, disodium salt, dihydrate.C10H14N2Na2O82H2O,
FW 372.24, purity > 99% (J.T. Baker Chemicals, Center Valley,
PA).
(c) Ammonium hydroxide.NH4OH, FW 35.05, 28.030.0%
as NH3 (Mallinckrodt Chemicals, Center Valley, PA).
(d) Nitric acid.HNO3, 6770%, OmniTrace grade (EMD
Chemicals).
(e) Potassium
dihydrogen
phosphate.KH2PO4,
certified at 22.73% P and 28.73% K, National
Institute of Standards and Technology (NIST) 200a
(Gaithersburg, MD), www.nist.gov/srm.
(f) Potassium chloride.KCl, FW 74.55, ACS grade, purity
>99% (Mallinckrodt Chemicals).
(g) Potassium nitrate.KNO3, certified at 38.66% K, NIST
193.
(h) Sodium phosphate, dibasic anhydrous.Na2HPO4, FW
141.96, ACS grade (Mallinckrodt Chemicals).

(i) Triton X-100.Octyl phenol ethoxylate (J.T. Baker

Chemicals).
(j) 10000 g/mL Be standard.In 4% HNO3, product
10M5-1 (High Purity Standards, Charleston, SC).
(k) 10000 g/mL Sc standard.In 4% HNO3, product
10M48-1 (High Purity Standards).
(l) Cesium chloride.CsCl, FW 168.36, purity > 99.999%
(Sigma-Aldrich, St. Louis, MO).
(m) Lithium nitrate.LiNO3, FW 68.95, purity > 99%, (EM
Science, Gibbstown, NJ).
(n) Ammonium nitrate.NH4NO3, FW 80.04, ACS grade,
purity > 99% (Mallinckrodt Chemicals).
(o) Ammonium sulfate.(NH4)2SO4, FW 132.14, ACS
grade, purity > 99% (Sigma-Aldrich).
(p) CitrateEDTA extraction solution.A pH neutral 0.11 M
ammonium citrate and 0.033 M disodium EDTA solution is
prepared by adding 25 g disodium EDTA and 50 g dibasic
ammonium citrate to approximately 1500 mL deionized (or
equivalent) water contained in a 2L volumetric flask. The pH is
adjusted to near neutral by adding 30mL ammonium hydroxide
water (1 + 1, v/v) solution in a fume hood. The final adjustment
to pH 7.00 (0.05) is achieved using a pH electrode and meter,
and adding the ammonium hydroxidewater (1 + 1, v/v) solution
drop-by-drop. After a stable pH of 7.00 (0.05) is achieved, the
flask is brought to volume with deionized water and mixed.
This solution can be prepared in larger volumes; however, it is
susceptible to microbial activity resulting in a maximum shelf
life of 2 weeks if stored in a dark location.
(q) 0.5% Triton-X.Add 1 mL Triton X-100 [(i) above] to
a 200 mL volumetric flask and dilute to volume with deionized
water.
(r) Internal standard/ionization buffer for citrateEDTAsoluble P and K.A solution of 10g Sc/mL in 0.018M CsCl
and 4% nitric acid was prepared by adding 1 mL 10000 g
Sc/mL stock standard [(k) above], 3 g cesium chloride [(l)
above], 20mL nitric acid [(d) above], and 1mL 0.5% Triton-X
[(q) above]/liter. If Be is used as an internal standard, add 4mL

690 Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014

Figure 1. Example of multiple wavelengths and splitting a wavelength into calibration segments to cover
the 0 to 1000 ug K/ml range.

however, this will require a secondary dilution of samples with

a high concentration of K. Diluted samples must maintain the
solvent matrix, which can be prepared by diluting 400 mL
citrateEDTA extract solution [Part A, B(n)] to 1L.
The sample extract and internal standard/ionic buffer
solutions were blended using a Y-connector (Part 30703-90;
Cole-Parmer, Bunker, CT) just prior to the nebulizer using the
conditions described in Table4.
D. Sample Preparation (Part A)

Figure 1. Example of multiple wavelengths and splitting a

wavelength into calibration segments to cover the 0 to 1000gK/mL
range.

of 10000 g/mL Be [(j) above] stock standard to obtain a

concentration of 40g/mL Be.
C. Calibration (Part A)
(a) Standard solution.Stock standards were made from
potassium dihydrogen phosphate [Part A, B(e)], potassium
chloride [Part A, B(f)], and potassium nitrate [Part A, B(g)].
Several calibration standards are required for the following
reasons: multiple ICP-OES wavelengths were utilized; some
wavelengths were split into multiple calibration segments; and
a minimum of five points/curve is recommended. The standards
used and their P and K concentrations, expressed as g/mL and
as their percentage oxide forms, are listed in Table2. An attempt
to use commercially available stock standard solutions was
made; however, these resulted in low P recoveries, possibly due
to the matrix change resulting from the acid used to preserve
the standards. Therefore, using standards prepared only from
potassium dihydrogen phosphate [Part A, B(e)], potassium
chloride [Part A, B(f)], or potassium nitrate [Part A, B(g)], as
outlined in Table2, is recommended.
(b)ICP-OES calibration.Emission intensity for each of
the calibration standards was plotted against concentration.
A minimum of five calibration standards is recommended
for each wavelength. An internal standard [Part A, B(r)] is
used to correct the concentration of the calibration standards,
as well as the samples. The wavelengths, standards used,
concentration ranges, curve fit, and neighboring wavelengths
that may have spectral overlap are listed in Table3. Whenever
possible, linear regression is preferred. Because of the dynamic
range in fertilizer K concentration, quadratic curve fit may be
necessary, provided the curvature is not excessive. Many newer
ICP software programs have algorithms to detect excessive
curvature of second order or quadratic calibration curves. An
example of the curves used for the citrateEDTA-soluble K
is shown in Figure 1. Alternatively, linear calibration can be
achieved by removal of the high concentration K standards;

The validation materials obtained from the Magruder(3) and

AFPC(4) check sample programs were prepared according to
their internal grinding and homogeneity protocols. A portion
of these materials was poured into a 9 oz. glass jar that was
thoroughly mixed by rotation prior to weighing. Additional
validation materials, used for method comparison, were
prepared internally. These materials were prepared by riffling
approximately 2300g (or 5lb) of field-collected samples down
to approximately 150g with a gated riffle splitter [Part A, A(g)],
and the subsample was ground with a rotor mill [Part A, A(h)]
to pass a 0.75mm mesh screen.
E. Extraction (Part A)
A 0.5 0.01 g fertilizer test portion was weighed and
completely transferred to a 250 mL wide-mouth class A
volumetric flask. Next, 100 mL 65 2C preheated citrate
EDTA extraction solution [Part A, B (p)] was dispensed into
each flask, followed by insertion of a rubber stopper. The test
solutions were shaken in a 65 2C preheated water bath set
to approximately 200 rpm for exactly 60 min; then removed
from the water bath, allowed to cool to room temperature (20 to
25C), brought to volume with deionized (or equivalent) water,
stoppered, and mixed. Any test solution (or extract) containing
suspended debris was filtered using P and K free filters. These
Table 4. Final ICP-OES conditions utilized for citrate
EDTA-soluble P and K validation
Factor

Setting

Power, kW

1.45

Plasma flow, L/min

19.5

Auxiliary flow, L/min

2.25

Nebulizer pressure, L/min

0.7

Nebulizer type

Seaspray

Spray chamber

Cyclonic

Sample pump tube

Buffer/internal standard pump tube
CsCl ionic buffer concn, M
Internal standard and concn, g/mL
Buffer matrix
Exposure length, s

Black/black
Gray/gray
0.018
10
4% nitric acid
10

Number of exposures

Rinse time, s

35

Total sample analysis time, min/sample

Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014 691

Figure 2. Difference in ammonium citrate-EDTA soluble % P2O5 and K2O concentration

for the validation materials as a result of changes in optimization variables

Table 5. Ruggedness factors for citrateEDTA-soluble P

and K
No.

Optimization factor

Major value

Minor value

Power, kW

A = 1.40

a = 1.50

Nebulizer flowa, L/min

B = 0.70

b = 0.80

Exposure length, s

C = 10

c = 20

Internal standard

D = Sc

d = Be

Rinse time, s

E = 30

e = 40

CsCl buffer concn, M

F = 0.018

F = 0.024

Buffer matrix

G = 4% nitric acid

g = water

Cyclonic spray chamber with concentric glass nebulizer.

test solutions (or extracts) have a very limited shelf life, so

analysis occurred within 16h of extraction.
F. ICP Conditions (Part A)
Optimization testing was conducted using the Youden
ruggedness trial (6) to determine the effects of seven variables:
power, nebulizer flow, exposure length, internal standard type,
rinse time, CsCl buffer concentration, and buffer matrix. The
major and minor criteria are listed in Table5. Because AOAC
Method993.31 addressed the citrateEDTA solvent extraction
process, extraction conditions were not included as part of the
ruggedness testing.
As a general indication of the method ruggedness, the mean
data difference in the major versus minor variables for all
validation materials is listed in Figure2. Relative to the P and
K concentration of the test samples, there was little difference
in the data between the major and minor variables, suggesting
the method is sufficiently rugged over the ranges tested.
However, there is some sensitivity to rinse time and buffer
concentration, so these conditions should be closely monitored.
The final instrument conditions used for method validation of
citrateEDTA-soluble P and K are listed in Table4.
G. Calculations (Parts A and B)
Several options exist in the software for data reporting,
including expression of standard concentrations, units, test
portion weight, test solution volume, and dilution factor. The
calibration standards are prepared as g/mL of P and K, and
the final fertilizer results reported as percentage P2O5 and K2O,
which requires the following calculation:
P2O5 ,% = [P (250/W) 142/(31 2)]/10000
where P = ICP-OES P reading in g/mL, 250 = final volume
in mL, W = test portion weight in g, 142 = MW of P2O5,
31 = MW of P, 2 = mole ratio of P2O5/P, and 10000 = conversion
of g/mL to %.
K2O, % = [K (250/W) 94.2/(39.1 2)]/10000
where K = ICP-OES K reading in g/mL, 250 = final volume in
mL, W = test portion weight in g, 94.2 = MW of K2O, 39.1 = MW
of K, 2 = mole ratio of K2O/K, and 10000 = conversion of
g/mL to %.

Figure 2. Difference in ammonium citrateEDTA-soluble P2O5 and

K2O concentration (%) for the validation materials as a result of
changes in optimization variables.

Alternatively, the standards can be entered with their

theoretical percentage P2O5 and K2O in solution values, listed
in Table1.
Method Validation: Citrate-EDTA-Soluble P and K
A. Accuracy/Bias (Part A)
Three separate extractions were analyzed on 4 different
days, resulting in a total of 12 individual accuracy readings
for each test sample. Results for accuracy are provided in
Table6. Recoveries for P ranged from 99.3 to 124.9%. A closer
examination of the high recovery for the Magruder 2006-05
test sample suggests that it contains appreciable organic P. As
a result, there is a potential for a high bias with this method
for fertilizers containing organic P. Removal of the organic
P sample improved the recovery range to 99.3 to 101.7%.
Recoveries for K ranged from 98.4 to 100.7%. With the
exception of the Magruder2006-05 test sample that contained
organic P, recoveries of the consensus or certified P values were
well within the recommended range(6).
Another indicator of method performance and potential
bias was assessed by comparing observed data with data from
other recognized methods. For P, 160 commercial inorganic
fertilizer samples, which were tested by the proposed ICP-OES
method, were also tested by AOAC 993.31 (automated
spectrophotometer). For K, 83commercial inorganic fertilizer
samples, which were tested by the proposed ICP-OES
method, were also tested by AOAC 983.02 (automated flame
photometry). The data comparisons are offered in Figure 3.
Statistical analysis by the t-test at P = 0.05 indicated the results
by all methods were not statistically different.
B. Precision (Part A)
Three separate extractions were analyzed on 4 different
days, resulting in a total of 12 individual precision readings
for each test sample. The mean, SD, RSD, Horwitz predicted
RSD (PRSD), and HorRat (r) repeatability values are listed in
Tables7 and8. In some instances, the RSD was considerably
below the PRSD, resulting in HorRat (r) values below the
suggested range of 0.3 to 1.3(7). This is possibly due to the fact
that the validation materials used were check sample materials,
which are uncharacteristically uniform, and that the high P and

692 Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014
Table 6. Recoveries of citrateEDTA-soluble P and K for all validation materials
Sample

Grade

Obs P, %a

Cons P, %a

P Rec, %
b

Obs K, %a

Cons K, %a

K Rec, %
99.7

Magruder 2006-05

5-5-5

5.52

4.42

124.9

3.15

3.16

Magruder 2005-10

10-10-10

9.93

9.93

100.0

10.30

10.39

99.1

Magruder 2006-03

19-19-19

19.21

19.20

100.1

18.18

18.05

100.7

Magruder 2004-06

6-24-24

22.76

22.38

101.7

25.13

25.53

98.4

Magruder 2005-01

18-46-0

46.62

46.60

100.0

NA

NA

NA

AFPC 2006-10

11-52-0

53.03

52.36

101.3

NA

NA

NA

Magruder 2001-10

0-0-50

NA

NA

NA

50.90

50.99

99.8

Magruder 2005-12

0-0-60

NA

NA

NA

62.26

62.13

100.2

NA

51.76

52.11

99.3

34.73

34.64

100.3

NISTd 200a KH2PO4a

P and K values listed are based on P2O5 and K2O content. Obs = observed value, Cons = consensus value, and Rec = recovery.

Magruder 2006-05 contains 58% organic matter by loss-on-ignition.

NA = Not applicable.

NIST = National Institute of Standards and Technology.

K concentration in fertilizers produce robust signals that are very

easily quantified and replicated by ICP-OES instrumentation.
C. Selectivity (Part A)
Fortified reagent blank and standard addition studies were
conducted to evaluate the matrix effect or interactions. For the
fortified blank study, four treatments were prepared: an unspiked
reagent blank, a low range concentration of 20 g P/mL and
50 g K/mL, a medium range concentration of 200 g P/mL
and 500 g K/mL, and a high range concentration of 400 g
P/mL and 1000g K/mL. The four treatments were performed
in triplicate and were measured on 4separate days. Recoveries
for the fortified blanks ranged from 99.6 to 101.2% and are
listed in Table 9. For the standard addition study, a midlevel
test sample, namely Magruder2004-06 with a value of 22.38%
P2O5 (or 195g/mL P) and 25.53% K2O (or 424g/mL K) was
spiked with 10, 30, and 130% of its P and K concentration from
sodium phosphate dibasic and potassium chloride, respectively.
These treatments were performed in triplicate and measured on
4separate days. Recoveries of P and K for the standard addition
study ranged from 98.91 to 102.44% and are listed in Table10.
Some selectivity issues were identified during method
development. The phosphate forms considered available
to plants are primary and secondary orthophosphate, or
H2PO4 and HPO42, respectively (8). The gravimetric and
spectrophotometric methods react with and specifically
measure only orthophosphate. ICP-OES, however, measures
all ionizable forms of P found in the fertilizer extract, so it
will measure orthophosphate plus any other form of P that is
soluble in the fertilizer extract solution. As a result, there are
some known instances in which this method can produce a high
P bias. Two examples are given in Figures 4 and 5, namely
phosphite, or PO33, and organic P. As a result, this method
is not suitable for organic fertilizers and fertilizers containing
phosphite. A few instances of spectral overlap or interference
are also known and are listed in Table 3, with an example
provided in Figure 6. The P wavelengths with the greatest
sensitivity are 213.618 and 214.914 nm; however, both of
these lines have a potential for Cu interference. The greatest

probability for spectral overlap occurs when the fertilizer Cu

concentration is high and the P concentration is low, which is
unusual but possible. This situation can largely be corrected
by using spectral deconvolution or interelement correction
modeling, which is found in most of the instrument software.
Wavelengths 177.434 and 178.222 nm for P are also an
option on some ICP-OES instruments, and are relatively free
from spectral interference. However, these lines are weaker
than the 213.618 and 214.914 nm wavelengths, which could
impact recovery of some of the lower P concentrations. For K,
wavelength 769.897nm showed signs of spectral interference
from lithium nitrate. The interference was too strong to correct
with spectral deconvolution or interelement correction. There
are two options available to avoid this problem: use CsCl
rather than LiNO3 as the ionic buffer, or avoid the use of the
wavelength 769.897 nm. Whenever possible, using multiple
wavelengths is encouraged for result confirmation, or so that an
unusual result can be identified and corrected.
D. LOD and LOQ (Part A)
Reagent blank test solutions were prepared separately and
measured in triplicate on 4 separate days. The mean blank
reading plus three times the SD was used to calculate the LOD,
while the mean blank reading plus 10 times the SD was used to
Figure 3. Comparison of results from 160 fertilizer samples for P2O5 content by ICP-OES and AOAC
method 993.31 and from 83 fertilizer samples for K2O by ICP-OES and AOAC method 983.02.

Figure 3. Comparison of results from 160 fertilizer samples for

P2O5 content by ICP-OES and AOAC Method 993.31, and from
83fertilizer samples for K2O by ICP-OES and AOAC Method 983.02.

Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014 693
Table 7. Repeatability precision data for citrateEDTAsoluble P by ICP-OES
Sample

Grade

Mean,
%

SD

RSD,
%

Magruder 2006-05

5-5-5

5.52

0.04

0.70

3.09

0.23

Magruder 2005-10 10-10-10

Table 8. Repeatability precision data for citrateEDTAsoluble K by ICP-OES

PRSD, HorRat
%
(r)

Sample

Grade

Mean,
%

SD

RSD,
%

PRSD,
%

HorRat
(r)

Magruder 2006-05

5-5-5

3.15

0.02

0.64

3.37

0.19

9.93

0.13

1.30

2.83

0.46

Magruder 2005-10 10-10-10

10.30

0.16

1.52

2.82

0.54

Magruder 2006-03 19-19-19 19.21

0.14

0.72

2.56

0.28

Magruder 2006-03 19-19-19

18.18

0.21

1.17

2.59

0.45

Magruder 2004-06 6-24-24

22.76

0.15

0.67

2.50

0.27

Magruder 2004-06 6-24-24

25.13

0.26

1.02

2.46

0.42

Magruder 2005-01 18-46-0

46.62

0.20

0.44

2.24

0.19

Magruder 2001-10

0-0-50

50.90

0.21

0.41

2.21

0.19

AFPC 2006-10

53.03

0.15

0.28

2.20

0.13

Magruder 2005-12

0-0-60

62.26

0.54

0.87

2.15

0.40

11-52-0

calculate the LOD(6). With these criteria, the LOD based upon
the P2O5 and K2O content in fertilizer were 0.0014 and 0.003%
respectively. The LOQ based upon the P2O5 and K2O content
in fertilizer were 0.06 and 0.01%, respectively. As a result, the
method is applicable to 0.06 to 53% P2O5 (or 0.026 to 23% P)
and 0.01 to 63% K2O (or 0.008 to 53% K).
Part B: Acid-Soluble P and K
Study Design
This portion of the SLV study is applicable to the determination
of the hydrochloric acid-soluble or the presumed total P
and K content in fertilizer materials by ICP-OES. While the
total P and K concentrations found in a fertilizer material may
not all be available for plant use, there are several reasons
why this determination is necessary. Some examples include:
determination of the P and K content of mined or processed
ores; a more productive alternative to AOAC methods957.02,
958.01, 962.02, 969.02, or 978.01 (9); and determination of
available P by the indirect method, namely AOAC960.02(9).
Hydrochloric acid may not completely digest or release all
organically bound P, so this method should be limited to
inorganic fertilizer materials. For inorganic fertilizer materials,
acid-soluble concentrations of 0.05 to 53% P2O5 (0.022 to 23%
P) and 0.3 to 63% K2O (0.25 to 53% K) can be determined by
this method.
Validation Samples
The validation samples, listed in Table 1, were also used
for Part B of this study. Common fertilizer materials with low,

medium, and high levels of P and K were selected to ensure

the method performed well over a dynamic concentration range.
A. Apparatus (Part B)
(a) Balance.Readability to 0.1 mg, Sartorius BP210S
(Gottingen, Germany).
(b) Hot plate.Model 53015, Lindburg/Blue M (Watertown,
WI).
(c) ICP-OES instrument.Thermo 6500 Duo View (Thermo
Scientific, Cambridge, UK).
(d) Gated riffle splitter.SP-177 Jones Standard Aluminum
Splitter (Gilson Co., Inc., Lewis Center, OH).
(e) Sample
grinder.Mikro-Samplemill
(Pulverizing
Machinery, Summit, NJ).
B. Reagents (Part B)
(a) Hydrochloric acid.HCl, 3538%, trace metal grade,
Cat. No. A508-500 (Fisher Scientific, Pittsburgh, PA).
(b) Ammonium dihydrogen phosphate.NH4H2PO4, FW
115.03, trace metal basis, purity >99.999%, Cat. No. 204005100G (Sigma-Aldrich).
(c) Potassium chloride.KCl, FW 74.55, trace metal basis,
purity > 99.99%, Cat. No. 204099-250G (Sigma-Aldrich).
(d) Scandium oxide.Sc2O3, FW 137.91, Item No. OX215N (Stanford Materials Corp., Irvine, CA).
(e) Nitric acid.HNO3, 69.2%, certified ACS plus grade,
Cat. No. A200 C212 (Fisher Scientific).
(f) Triton X-100.Polyethylene-glycol p-tert-octylphenyl
ether, 4-(C8H17)C6H4(OCH2CH2)nOH (n approximately 10),
FW 624, Cat. No. BP151-500 (Fisher Scientific).

Table 9. Ammonium citratedisodium EDTA matrix blank solution spiked with low, medium, and high concentrations of P
and K, and their recoveries
Sample ID

Blank + spike concn, Concn in fertilizer,

ppm
%

Replicate 1,
ppm

Replicate 2,
ppm

Replicate 3,
ppm

Mean recovery,
%

Fortified low P

20

2.3 P2O5

20.06

20.11

20.02

100.30

Fortified medium P

200

23 P2O5

202.6

202.1

202.9

101.26

Fortified high P

400

46 P2O5

401.3

400.9

404.0

100.52

Fortified low K

50

3 K2O

49.66

50.84

49.77

100.19

Fortified medium K

500

30 K2O

501.3

506.8

507.3

101.03

Fortified high K

1000

60 K2O

993.7

999.9

996.5

99.67

694 Bartos et al.: Journal of AOAC International Vol. 97,Figure

No. 3,5. 2014
Recovery of available phosphate from a fertilizer source
containing organic P by the proposed and other reference methods.

Table 10. Standard addition recoveries from a mid-level P

and K fertilizer sample spiked with 10, 30, and 130% of its P
and K concentration

Standard addition

K Recovery, %

6-24-24 + 2.4% P2O5 + 2.4% K2O

102.44

98.96

6-24-24 + 7.2% P2O5 + 7.2% K2O

101.97

98.91

6-24-24 + 31.2% P2O5 + 31.2% K2O

101.86

99.90

(g) Cesium chloride.CsCl, FW 168.36, trace metal basis,

purity >99.999%, Cat. No. 203025-50G (Sigma-Aldrich).
(h) Lithium nitrate.LiNO3 ReagentPlus grade, FW 68.95,
Cat. No. 227986-1KG (Sigma-Aldrich).
(i) 10000 g/mL Be stock standard.In 5% HNO3, Cat. No.
PLBE-10-500 (Exaxol Corp., Clearwater, FL).
(j) 10000 g/mL Sc stock standard.Weigh 15.3374 g
scandium oxide [(d) above] into a 600 mL beaker. Add 300mL
deionized water, then slowly add 100 mL nitric acid [(e) above].
Heat solution on a hotplate to a gentle boil, and continue boiling
until the solution becomes clear.
(k) 1% Triton X.Pipet 10 mL Triton X-100 solution [(f)
above] into a 1 L flask. Bring to volume with deionized water
and mix well.
(l) Internal standard/ionization buffer for total P and K.A
60 g Sc/mL in 0.035 M CsCl and 2% HNO3 solution is
prepared by adding 6mL 10000g Sc/mL stock standard [(j)
above], 6 g CsCl [(g) above], 20 mL HNO3 [(e) above], and
2mL 1% Triton X [(k) above] per L. If LiNO3 is used as the
ionic buffer, replace the CsCl with 8g LiNO3 [(h) above]. Also,
if Be is used as an internal standard, add 1mL 10000g/mL
Be stock standard solution [(i) above] to obtain a 10g/mL Be
internal standard concentration.
(m) Hydrochloric acid digestion solution.4 M. Into a 1 L
volumetric flask filled approximately half full with deionized or
equivalent water, slowly add a total of 333 mL of concentrated

Figure 4. Recovery of available phosphate from a phosphite fertilizer

source by the proposed and other reference methods.

% P2O5

P Recovery, %

Magruder 2006-05
Group Grand Average

Citrate-EDTA ICP

Figure 5. Recovery of available phosphate from a fertilizer

source containing organic P by the proposed and other reference
methods.

hydrochloric acid [Part B, B(a) above]. Bring to volume with

deionized water and mix well.
C. Calibration (Part B)
(a) Standard solution.Stock standards were made from
ammonium dihydrogen phosphate [Part B, B(b)] and potassium
chloride [Part B, B(c)]. Again, many calibration standards are
required for several reasons: multiple ICP-OES wavelengths were
utilized; some wavelengths were split into multiple calibration
segments; and a minimum of five points/curve is recommended.
The standards used and their P and K concentrations expressed as
g/mL and as their percentage oxide forms are listed in Table11.
An attempt to use commercially available stock standard
solutions was made; however, better P recoveries were obtained
using weighed salts.
Figure 6. Spectral overlap of Cu wavelength
214.898 nm into P wavelength 214.914 nm.

20
18
16

% P2O5

14
12
10
8
6
4
2
0

Magruder 2007-12B
AOAC 960.03 Gravimetric

AOAC 993.31 Spectrophotometric

Citrate-EDTA ICP

Figure 4. Recovery of available phosphate from a phosphite

fertilizer source by the proposed and other reference methods.

Figure 6. Spectral overlap of Cu wavelength 214.898 nm into P

wavelength 214.914 nm.

Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014 695
Table 11. ICP-OES calibration standards from stock reagent salts for total P and K
Weight
NH4H2PO4, g

Weight
KCl, g

K2O
sample,
%

Blank

1000

40

1000

40

40 of Standard 6

0.6305

9.8

22.4

0.00224

332

400

0.0400

20

1000

36

100 of Standard 10b

0.4748

47

108

0.01076

249

300

0.0300

15

500

12

100 of Standard 10b 100 of Standard 14b

94

215

0.02153

11

163

196

0.0196

10

1000

32

0.4539

200 of Standard 12b

122

280

0.02802

14

116

140

0.0140

1000

36

0.6810

100 of Standard 14b

184

420

0.04204

21

81

98

0.0098

245

561

0.05605

28

34.9

42

0.0042

306

701

0.07007

35

17.4

21

0.0021

1000

40

0.9079

50 of Standard 13

1000

40

1.1349

25 of Standard 13b

K2O,
g/mL

K2O
solution,
%

Acid,
a
mL

P2O5,
g/mL

P2O5,
sample, K concn,
g/mL
%

Vol.,
mL

P concn,
g/mL

P2O5,
solution,
%

Standard
ID

1000

40

1.3619

NA

367

841

0.08408

42

NA

NA

NA

NA

1000

40

1.5888

NA

428

981

0.09809

49

NA

NA

NA

NA

10

1000

40

1.7510

NA

472

1081

0.10811

54

NA

NA

NA

NA

11

1000

40

NA

0.7915

NA

NA

NA

NA

415

500

0.0500

25

12

1000

40

NA

1.1079

NA

NA

NA

NA

581

700

0.0700

35

13

1000

40

NA

1.3295

NA

NA

NA

NA

697

840

0.0840

42

14

1000

40

NA

1.5511

NA

NA

NA

NA

814

980

0.0980

49

15

1000

40

NA

1.7727

NA

NA

NA

NA

930

1120

0.1120

56

16

1000

40

NA

1.9943

NA

NA

NA

NA

1046

1260

0.1260

63

17

1000

40

0.9728

0.9497

262

601

0.06006

30

498

600

0.0600

30

Acid = Volume of 1:2 HClwater required to make standard.

Serial dilution from another standard (e.g., 40 of Standard 6 means add 40 mL of Standard 6).

NA = Not applicable.

(b) ICP-OES calibration.Emission intensity for each of

the calibration standards was plotted against concentration.
A minimum of five calibration standards is recommended for
each wavelength. An internal standard [Part B, B(l)] is used to
correct the concentration of the calibration standards as well as
the samples. The wavelengths, standards used, concentration
ranges, curve fit, and neighboring wavelengths that may require
spectral deconvolution are listed in Table 12. The data in
Table12 are based on a radial view for K. If linear regression to
1000g/mL of K is not possible, one or more of the following
may be necessary: quadratic curve fit (provided the curvature
is not excessive), utilizing wavelength 404.721nm for the five
highest K calibration standards listed in Table 11, dropping

one or more of the top K standards listed in Table 11 and/or

conducting sample dilutions using 0.16M HCl.
The sample extract and internal standard/ionic buffer
solutions were blended using a reagent T connector (Part
No.116-0522-01, Bran+Luebbe, Mequon, WI) just prior to the
nebulizer using the conditions described in Table13.
D. Sample Preparation (Part B)
The validation materials obtained from the Magruder (4) and
AFPC (5) check samples programs were prepared according to
their internal grinding and homogeneity protocols. Additional
validation materials, used for method development and data

Table 12. Calibration criteria for acid-soluble or total P and K

Wavelength, nma

Calibration range, g/mL

Standards used (see Table 2)

Curve fit

Spectral deconvolution

213.618 (1)

0 to 245

Blank, 1, 2, 3, 4, 5, 6

Linear

Cu 213.598

213.618 (2)

184 to 472

5, 6, 7, 8, 9, 10

Linear

Cu 213.598

214.914 (1)

0 to 245

Blank, 1, 2, 3, 4, 5, 6

Linear

Cu 214.898

214.914 (2)

184 to 472

5, 6, 7, 8, 9, 10

Linear

Cu 214.898

766.485 (1)

0 to 332

Blank, 1, 2, 3, 4, 5, 6, 7

Linear

None

Element ID

766.485 (2)

332 to 1046

11, 12, 13, 14, 15, 16, 17

Linear

None

769.897 (1)

0 to 332

Blank, 1, 2, 3, 4, 5, 6, 7

Linear

Possible LiNO3

769.897 (2)

332 to 1046

11, 12, 13, 14, 15, 16, 17

Linear

Possible LiNO3

(1) and (2) distinguish between the same wavelength used to cover two separate concentration ranges.

696 Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014
Table 13. Final ICP-OES conditions utilized for acid-soluble
or total P and K validation

Table 14. Optimization factors for acid-soluble or total

P and K

Factor

No.

Setting

Power, kW

Optimization factor

Major value

Minor value

1.15

Test portion weight, g

A = 0.55

a = 0.45

15

Volume 4 M HCl, mL

B = 11

b=9

Auxiliary flow, L/min

1.5

Digestion time, min

C = 17

c = 13

Nebulizer pressure, L/min

0.40

ICP power, kW

D = 1.2

d = 1.1

Nebulizer type

V-grove

Internal standard

E = Sc

e = Be

Spray chamber

Scotts (baffled)

Ionic buffer

F = Li

F = Cs

Sample pump tube

Orange/white (id = 0.64 mm)

Nebulizer flow, L/min a

G = 0.42

g = 0.38

Buffer/internal standard pump tube

Orange/white (id = 0.64 mm)

Plasma flow, L/min

CsCl concentration, M
Internal standard and concn, g/mL
Buffer matrix
Exposure length, s

V-grove nebulizer with baffled spray chamber.

0.035
6
2% nitric acid
10

Number of exposures

Rinse time, s

30

Total sample analysis time, min

2.4

comparisons, were prepared internally. These materials were

prepared by riffling [Part B, A(d)] the entire 2300g (or 5lb) fieldcollected sample three times before further splitting the sample
down to approximately 100g. The entire 100 g subsample was
then ground [Part B, A(e)] to pass a Tyler-35 mesh sieve (U.S.
Standard Sieve Size No. 40, 0.420 mm or 0.165 in. opening;
Fisherbrand, stainless steel; Fisher Scientific, Pittsburgh, PA).
E. Extraction (Part B)
For total P and K, a 0.5 0.01 g test portion was weighed
and completely transferred to a 250 mL class A volumetric
flask. Next, 30mL deionized (or equivalent) water was added,
followed by addition of 10 mL HClwater (1 + 2, v/v) acid
digestion solution [Part B, B(m)]. The samples were placed on
a preheated hotplate that resulted in a gentle boil for 15 1min.
The volumetric flasks were allowed to cool to room temperature
(20 to 25C); then brought to volume with deionized water. The
acid strength of the final digestion solution was approximately
0.04 M HCl. Any sample containing suspended debris was
filtered using P and K free filters. These samples have a limited
shelf life, so all sample analysis should occur within 2weeks
of digestion. After repeated heating and cooling cycles of the
volumetric flasks, they may lose calibration. Routinely, the
calibration of the 250mL volumetric flasks should be checked
by adding 250g deionized (or equivalent) water and verifying
the volume is at the meniscus. If a flask loses calibration, either
use the corrected volume established by water weight, or safely
discard the flask.

major and minor variables are listed in Table14. As a general

indication of method ruggedness, the mean data difference in
the major versus minor variables for all the test materials is
listed in Figure7. Lower test portion weights produced slightly
lower results, so limited deviation (0.025g) from a test portion
weight of 0.5g is recommended. Also, K is sensitive to nebulizer
pressure/flow, which should be closely monitored, as nebulizers
can deteriorate over time. Relative to the sample concentration,
there was little difference in the data between the major and
minor variables for all other parameters, suggesting the method
is sufficiently rugged. The final instrument conditions used for
method validation of acid-soluble or total P and K are listed
in Table13.
G. Calculations (Part B)
The calculations listed in Section G (Part A) also apply to
acid-soluble or total P and K.
Method Validation: Acid-Soluble P and K
A. Accuracy/Bias (Part B)
Three separate extractions were analyzed on four different
days, resulting in a total of 12 individual accuracy readings
for each test sample. Results for accuracy are provided in
Table 15. Recoveries for P ranged from 95.53 to 99.40%. A
closer examination into the recovery for the Magruder2006-05
Figure 7. Difference in acid-soluble % P2O5 and K2O concentration for the test samples as
a result of changes in optimization variables.

F. ICP-OES Conditions (Part B)

Optimization testing was conducted using the Youden
ruggedness trial (6) to determine the effects of seven variables:
test portion weight, solvent volume, digestion time, ICP power,
internal standard type, ionic buffer type, and nebulizer flow. The

Figure 7. Difference in acid-soluble P2O5 and K2O concentration

(%) for the test samples as a result of changes in optimization
variables.

Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014 697
Table 15. Acid-soluble or total P and K recoveries for the validation samples
Source
Magruder 2006-05

Grade
5-5-5

Obs P, %a

Cons P, %a

5.35

5.60

P Rec, %
95.53

Obs K, %a

Cons K, %a

K Rec, %

3.39

3.16

107.28 b

Magruder 2005-10

10-10-10

9.71

10.04

97.10

10.22

10.39

98.36

Magruder 2006-03

19-19-19

18.71

19.03

98.32

17.79

18.05

98.56

Magruder 2004-06

6-24-24

22.44

22.64

99.12

25.88

25.53

101.37

Magruder 2005-01

18-46-0

46.60

46.88

99.40

NAc

NA

NA

Magruder 2001-10

0-0-50

NA

NA

NA

50.46

50.99

98.96

Magruder 2005-12

0-0-60

NA

NA

NA

62.26

62.13

100.21

P and K values listed are based upon P2O5 and K2O content. Obs = observed, Cons = consensus value, and Rec = recovery.

Magruder 2006-05 contains 58% organic matter by loss-on-ignition.

NA = Not applicable.

test sample suggests that it contains appreciable organic P.

Hydrochloric acid may not completely digest or release all P
from organic compounds, and therefore, could result in a low
bias. Also, the types of P extracted from organic compounds may
3
be different from phosphate (PO4 ), which could create a bias
relative to methods (i.e., gravimetric and spectrophotometric)
that react solely with orthophosphate. As a result, there is a
potential for a bias with this method for fertilizers containing
organic P. Removal of the organic sample improved the
recovery range to 97.10 to 99.40%. Similarly, with removal
of the organic sample, recoveries for K ranged from 98.36 to
101.37%. With the exception of the Magruder 2006-05 test
sample that contained organic materials, recoveries of the
consensus values were within the recommended range(6).
Another indicator of method performance and potential bias
was assessed by comparing observed data with consensus data
from other recognized methods. Because the check sample
validation materials had been tested by multiple methods,
comparisons of the data recovery with other common methods
are listed in Table 16. Statistical analysis (t-test, P = 0.05)
indicated there was no statistical difference in the results
obtained for the methods listed in Table 6. However, the
recoveries listed in Table16 reinforce that the candidate method
may produce a bias for organic fertilizer materials. For common
inorganic materials, this proposed method produced recoveries

ranging from 97.10 to 100.45% for total P and 97.16 to 102.38%

for K.
B. Precision (Part B)
Three separate extractions were analyzed on 4 different
days, resulting in a total of 12 individual precision readings
for each test sample. The mean, SD, RSD, PRSD, and HorRat
(r) repeatability values are listed in Tables17 and18. In most
instances, the HorRat (r) values were in, or near, the suggested
range of 0.3 to 1.3(7).
C. Selectivity (Part B)
Fortified reagent blank and standard addition studies were
conducted to evaluate matrix effect or interactions. For the
fortified blank study, four treatments were prepared: an unspiked
reagent blank, a low range concentration of 20 g P/mL and
50g K/mL, a medium range concentration of 200g P/mL and
500g K/mL, and a high range concentration of 400gP/mL
and 1000 g K/mL. The four treatments were performed in
triplicate, and were measured on 4 separate days. Recoveries
for the fortified blanks ranged from 98.82 to 100.12% and are
listed in Table19. For the standard addition study, a midlevel
test sample, namely Magruder2004-06, with a value of 22.64%
P2O5 (or 198g/mL P) and 25.53% K2O (or 424g/mL K), was

Table 16. Comparison of acid-soluble P and K results to other recognized total P and soluble K methods
Source

Grade

P Rec, 962.02, %a

P Rec, 958.01, %a

K Rec, 958.02, %a

K Rec, 958.02, %a

Magruder 2006-05

5-5-5

117.58b

118.36b

111.51b

107.96b

Magruder 2005-10

10-10-10

97.20

97.10

97.89

97.71

Magruder 2006-03

19-19-19

98.42

98.22

98.08

97.16

Magruder 2004-06

6-24-24

100.18

100.45

100.98

100.31

Magruder 2005-01

18-46-0

99.12

100.45

NAc

NA

Magruder 2001-10

0-0-50

NA

NA

99.27

102.38

Magruder 2005-12

0-0-60

NA

NA

99.52

99.94

P and K values listed are based upon P2O5 and K2O content. 962.02 = AOAC gravimetric method; 958.01 = AOAC spectrophotometric method;
958.02 = AOAC volumetric tetraphenylboron method; and 938.02 = flame photometric method. Rec = recovery.

Magruder 2006-05 contains 58% organic matter by loss-on-ignition.

NA = Not applicable.

698 Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014
Table 17. Repeatability precision data for acid-soluble or total P by ICP-OES
Sample

Grade

Mean, %

SD, %

RSD, %

PRSD, %

HorRat (r)

Magruder 2006-05

5-5-5

5.35

0.06

1.12

3.09

0.36

Magruder 2005-10

10-10-10

9.71

0.11

1.13

2.83

0.40

Magruder 2006-03

19-19-19

18.71

0.21

1.12

2.56

0.44

Magruder 2004-06

6-24-24

22.44

0.25

1.11

2.50

0.45

Magruder 2005-01

18-46-0

46.60

0.33

0.71

2.24

0.32

spiked with 10, 30, and 130% of its P and K concentration from
ammonium dihydrogen phosphate [Part B, B(b)] and potassium
chloride [Part B, B(c)], respectively. These treatments were
performed in triplicate and measured on 4 separate days.
Recoveries of P and K for the standard addition study ranged
from 99.23 to 101.65%, and are listed in Table20.
The selectivity concerns mentioned for ammonium-citrate
disodium EDTA-soluble P and K in Section C (Part A) also apply
to acid-soluble P and K by ICP-OES. Specifically, as shown in
Tables15 and16 for the Magruder2006-05 validation sample,
this proposed method can have a bias for fertilizer materials
containing organic sources of P and K. As a result, this method
should be limited to fertilizer materials containing inorganic
sources of P and K. Likewise, as demonstrated in Figure6 and
Table12, selection of wavelengths free of spectral interference
or deconvolution modeling may be required in instances where
the fertilizer material contains Cu and/or LiNO3.
D. LOD and LOQ (Part B)
Blank solutions of 0.16 M HCl were prepared separately
and measured in triplicate on 4separate days. The mean blank
reading plus three times the SD was used to calculate the LOD,
while the mean blank reading plus 10times the SD was used to
calculate the LOQ(6). With these criteria, the LOD based upon
the P2O5 and K2O content in fertilizer were 0.012 and 0.120%,
respectively. The LOQ based upon the P2O5 and K2O content in
fertilizer were 0.05 and 0.30%, respectively.
Results and Discussion
This represents an advanced ICP-OES method, so
familiarization, practice and demonstration of proficiency before
use is strongly recommended. Also, differences in ICP-OES
instrument designs, introduction systems, plasma efficiency,
viewing orientation, radio frequency (RF) generation, etc., could
necessitate some minor modifications. Any minor modification
must be performance based, using a variety of known reference

materials over a wide range of P and K concentrations to

ensure acceptable method performance. For ammoniumcitratedisodium EDTA-soluble P and K, it is critical that
three aspects of this method be maintained, namely, a small
sample pump tube and a large ionic buffer/internal standard
pump tube as noted in Table4 to dilute the carbon content of
the sample matrix, a dilute ionic strength buffer solution to
prevent salting of the torch, and a high instrument power
setting to overcome the reduction in plasma efficiency resulting
from the carbon chains contained in the citrateEDTA solvent.
The higher power setting requires a corresponding increase in
plasma coolant and auxiliary flow settings to prevent the glass
torch from melting. Failure to maintain all the aforementioned
criteria greatly reduces the quality of the data. Any instrument
modification must not result in data variation that exceeds the
investigational allowance listed in the Association of American
Plant Food Control Officials official publication (9) for a
reference sample of known concentration. Low P recoveries
will occur if the matrix is not sufficiently diluted using the
proper pump tube ratio, the plasma power setting is too low,
or the extraction solvent and calibration standard matrix is not
properly matched. The greatest challenge with K is splitting
the dynamic K solution concentration range of 0 to 1000 g
K/mL into appropriate segments, as demonstrated in Figure1
and Tables 3 and 12. As a result, to measure the range of K
expected in fertilizer materials, one or more of the following
will be required: radial view, quadratic curve fit (provided the
curvature is not excessive), utilizing wavelength 404.721 nm
for the five highest K calibration standards listed in Tables 2
and11, dropping one or more of the top K standards listed in
Tables2 and11, and/or conducting sample dilutions. Because
the 404.721nm intensity is much weaker than the 766.485 and
769.987 nm intensities, if used, the 404.721 nm wavelength
should be closely monitored for signal strength and K recovery.
If any minor, performance-based changes are made to the
pump tube ratios listed in Tables4 and13, the corresponding
Be and Sc internal standard concentrations and ionic CsCl or
LiNO3 buffer concentrations should be modified to maintain

Table 18. Repeatability precision data for acid-soluble or total K by ICP-OES

Sample

Grade

Mean, %

SD, %

RSD, %

PRSD, %

HorRat (r)

Magruder 2006-05

5-5-5

3.39

0.04

1.18

3.36

0.35

Magruder 2005-10

10-10-10

10.22

0.08

0.80

2.81

0.29

Magruder 2006-03

19-19-19

17.79

0.07

0.39

2.59

0.15

Magruder 2004-06

6-24-24

25.88

0.17

0.66

2.45

0.27

Magruder 2001-10

0-0-50

50.46

0.33

0.65

2.22

0.29

Magruder 2005-12

0-0-60

62.26

0.56

0.90

2.15

0.42

Bartos et al.: Journal of AOAC International Vol. 97, No. 3, 2014 699
Table 19. 3 M HCl blank solution spiked with low, medium, and high concentrations of P and K, and their recoveries
Sample ID

Blank + spike concn, ppm

Concn in fertilizer, %

Replicate 1

Replicate 2

Replicate 3

Mean recovery, %

Fortified low P

20

2.3 P2O5

19.72

19.97

19.89

99.30

Fortified medium P

200

23 P2O5

197.0

199.5

196.4

98.82

Fortified high P

400

46 P2O5

396.4

401.2

397.9

99.63

Fortified low K

50

3 K 2O

49.90

50.28

50.00

100.12

Fortified medium K

500

30 K2O

498.7

500.7

498.9

99.89

Fortified high K

1000

60 K2O

997.5

1003.3

998.5

99.97

Table 20. Standard addition recoveries from a mid-level P

and K fertilizer sample spike with 10, 30, and 130% of its P
and K concentration
Standard addition
6-24-24 + 2.4% P2O5 + 2.4% K2O

P recovery, %

K recovery, %

100.80

101.65

6-24-24 + 7.2% P2O5 + 7.2% K2O

99.23

101.08

6-24-24 + 31.2% P2O5 + 31.2% K2O

100.29

101.08

the concentrations listed in reagent sections Part A [B(r)] and

PartB [B(l)].
Provided the aforementioned challenges are addressed,
this method offers several unique advantages, including an
elimination of unsafe chemicals and waste products, lower
detection capabilities, a dynamic working range, a reduction in
labor, and an increase in productivity.
Acknowledgments
We thank Connie Lehe, Sally Mullins, Natalie Newlon, and
Irene Szalasny with the Office of the Indiana State Chemist
for their dedicated assistance and support of the citrateEDTA
portion of this validation study. Valuable advice on ICP-OES

configuration and instrument conditions was also received from

Doug Shrader with Agilent Technologies.
References
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INTERNATIONAL, Gaithersburg, MD
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(accessed September 6, 2012)
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