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and mix by careful rotation and inversion. For liquid materials,
shake the laboratory sample vigorously to thoroughly mix.
Invert and rotate the container again (for solid materials) or
shake (for liquids) immediately before selecting a test portion.
Other validated sample preparation techniques that result in
a representative test portion are also acceptable. When the
analytical sample is split or the mass is reduced for any reason,
the splitting process should be validated to not introduce
unintended sampling error.
F. Extraction
Weigh a ~0.5 g test portion to the nearest 0.01 g (
see
Alternative A
, section
E
) and completely transfer to a 250 mL
wide-mouth class A volumetric flask. Dispense 100 mL
65 ± 2°C preheated citrate–EDTA extraction solution [
see
Alternative A
, section
C(m)
] into each flask and insert a
rubber stopper. Shake test solutions in a 65 ± 2°C preheated
water bath set to approximately 200 reciprocations/min for
60 ± 1 min, remove from the water bath, allow to cool to room
temperature (20–25°C), dilute to volume with deionized (or
equivalent) water, stopper, and mix. Filter any test solution
containing suspended debris using P- and K-free filters. Due
to a very limited shelf life, analyze test solutions within 16 h
of extraction. After repeated heating and cooling cycles of the
250 mL volumetric flasks, check the calibration of the flasks
by adding 250 g deionized (or equivalent) water and verify that
the volume is at the meniscus. When a flask loses calibration,
either use the corrected volume established by water weight,
or discard it.
G. ICP-OES Conditions
The optimal instrument conditions identified during method
validation of citrate–EDTA-soluble P and K are listed in
Table
2015.18D
. Monitor the rinse time and buffer concentration
closely, because they are sensitive to change (1).
ICP-OES instruments differ in their design and options, so
minor adjustment to the conditions listed in Table
2015.18D
may be necessary; however, any adjustments to these conditions
must be performance based and validated. Special attention
should be paid to the recovery of P in fertilizer concentrates or
fertilizers containing ≥40% P
2
O
5
, because these materials pose
the greatest need for optimal instrument performance.
H. Calculations
Several variables exist in the instrument software for data
reporting, including units, test portion weight, test solution
volume, and dilution factor. The calibration standards are
prepared as micrograms per milliliter P and K, and the final
fertilizer results are reported as percentage P
2
O
5
and K
2
O,
which requires the following two calculations, respectively:
P
2
O
5
, % = [P × (250/W) × 142/(31.0 × 2)]/10000
where P is the ICP-OES P reading in micrograms per milliliter,
250 is the final volume in milliliters, W is the test portion
weight in grams, 142 is the FW of P
2
O
5
, 31.0 is the FW of P,
2 is the mole ratio of P
2
O
5
to P, and 10000 is the conversion of
percentage to micrograms per milliliter; and
K
2
O, % = [K × (250/W) × 94.2/(39.1 × 2)]/10000
where K is the ICP-OES K reading in micrograms per milliliter,
250 is the final volume in milliliters, W is the test portion weight
in grams, 94.2 is the FW of K
2
O, 39.1 is the FW of K, 2 is
the mole ratio of K
2
O to K, and 10 000 is the conversion of
percentage to micrograms per milliliter.
Alternatively, the standards can be entered as equivalent
theoretical percentages of P
2
O
5
and K
2
O in solution values,
listed in Tables
2015.18A
and
2015.18B
.
When empirical calibration [
see Alternative A
, section
D(d)
]
is used, conversion of the percentage P
2
O
5
in the certified or
consensus material to milligrams per liter P in the calibration
solution is obtained by using the following equation:
P, g mL P O 10,000 W 250 31.0 2 142
2 5
(
)
(
) (
)
µ = % ×
×
×
×
where P, μg/mL is the P concentration in the extracted standard
solution; % P
2
O
5
is the certified or consensus value, 10000 is
the conversion of percentage to micrograms per milliliter, W
is the test portion weight in grams, 250 is the final volume in
milliliters, 31 is the FW of P, 2 is the mole ratio of P
2
O
5
/P, and
142 is the FW of P
2
O
5
.
I. Comments
Relative to other AOAC Methods (
960.03
,
978.01
,
and
993.01
), the ICP-OES method can produce lower P
recoveries and/or greater data variability
(http://www .magruderchecksample.org). Critical factors and common
error sources are included here. For P, three issues are critical:
addressing matrix challenges, implementing robust plasma
conditions, and utilizing proper standards. Carbon in the citrate
and EDTA will reduce the plasma efficiency, so it must be
addressed. Diluting the matrix by using a smaller sample pump
Table 2015.18D. Final ICP-OES conditions used 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
Black/black
a
Buffer/internal standard pump tube
Gray/gray
a
CsCl ionic buffer concn, M
0.018
Internal standard and concn, μg/mL
10
Buffer matrix
4% nitric acid
Exposure length, s
10
No. of exposures
3
Rinse time, s
35
Total analysis time, min
2
a
An orange/white sample pump tube and a red/red buffer/internal
standard pump tube provide approximately the same dilution factor, but
use less volume of solution. Ensure that a sufficiently large waste pump
tube is used to prevent flooding of the spray chamber.