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YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002 1241


AGRICULTURAL MATERIALS




Determination of Phosphorus in Fertilizers by Inductively
Coupled Plasma Atomic Emission Spectrometry
WEI MIN YANG, RHONDA L. BOLES, and THOMAS P. MAWHINNEY1
University of Missouri-Columbia, Experiment Station Chemical Laboratories, Rm 4, Agriculture Bldg, Columbia, MO 65211


An inductively coupled plasma atomic emission                              tion curve, the weight of the fertilizer samples is adjusted to
spectrometry (ICP-AES) method was developed for                            control final sample phosphate concentrations.
the determination of phosphorus in fertilizers. To-                           A major advantage of inductively coupled plasma atomic
tal phosphorus, direct extraction available phos-                          emission spectrometry (ICP-AES) is its ability to determine
phorus (EDTA), and water-soluble phosphorus, re-                           several elements simultaneously in a wide range of concentra-
ported as phosphorus pentoxide (P2O5), in                                  tions. For determination of phosphorus, the sensitivity of the
15 Magruder check fertilizers were measured by                             ICP-AES analysis method exceeds that of the AOAC official
ICP-AES, and the results were compared with                                methods; in addition, the ICP-AES has a calibration curve of a
those obtained by the AOAC official method.                                very wide linear range. As a result, no sample weighing adjust-
Five analytical wavelengths of phosphorus,                                 ment is required for the ICP-AES method. Because of these fea-
177.499, 178.287, 213.618, 214.914, and 253.565 nm,                        tures, the determination of phosphorus by the ICP-AES method
were tested for the determination of phosphorus in                         has attracted the attention of several scientists.
fertilizers, and their detection limits were obtained.                        Hamalova et al. (5) determined phosphorus, potassium,
Acid effects of perchloric acid and possible matrix                        and magnesium in 12 fertilizers by ICP-AES. For phosphorus,
effects of aluminum, calcium, magnesium, potas-                            the results of ICP-AES were compared with those obtained by
sium, and sodium were negligible for phosphorus                            the standard gravimetry method. Generally, precision and ac-
determination. Wavelength 213.618 nm was the                               curacy of the ICP-AES method were satisfactory. Ardis and
best analytical wavelength for phosphorus deter-                           Baker (6) used an ICP spectrometer to monitor fertilizer plant
mination by all 3 sample preparation methods for                           effluents for phosphorus, sulfur, and metals. The detection
the selected Magruder fertilizers. The results dem-                        limit for phosphorus was 0.08 µg/mL at 213.618 nm.
onstrated that the accuracy and precision of the                           Jones (7, 8) determined the concentrations of major, micro,
ICP-AES method were comparable with those of                               and trace elements by ICP-AES in fertilizer standards. It was
the official methods.                                                      determined that analysis by ICP-AES of fertilizer materials
                                                                           with wide ranges of elemental contents is a rapid technique
                                                                           that can yield results comparable with those obtained by
     n fertilizers, phosphorus is one of the major nutrients that          AOAC protocols.

I    is most commonly determined. Accurate analysis of fertil-
     izers is necessary both for the quality control of their pro-
duction and for determining their effective use in the field.
                                                                              This study was undertaken to standardize the ICP-AES
                                                                           method for determination of phosphorus in several sample
                                                                           preparation methods in the Magruder fertilizer check samples
Presently, the gravimetric determination with quimociac re-                by the use of the same calibration curve.
agent and the spectrophotometric molybdovanadophosphate
                                                                           METHOD
procedures are the AOAC official reference methods for de-
termination of phosphorus in fertilizers (1–3). The gravimetric               Apparatus
procedure is both tedious and time-consuming. The spectro-
photometric molybdovandate phosphate method, on the other                     (a) Spectrometer.—Atomic emission measurements of
hand, measures only orthophosphate (4). Because of this, fer-              phosphorus were made with an ARL 3410+ sequential ICP
tilizer samples that possess phosphate in other forms must be              spectrometer (Fisons, Dearborn, MI) with a minitorch.
converted to orthophosphate before determination. Further-                    (b) Nebulizer and pump.—The sample solutions were
more, to control the citrate interference which is used for di-            nebulized by a pneumatic nebulizer (Precision Glassblowing,
rect available extraction, appropriate matrix match is neces-              Englewood, CO) with a Gilson peristaltic pump
sary for the calibration standards. Finally, to ensure that the            (Worthington, OH). The main operating conditions are listed
measured signals fall within the working range of the calibra-             in Table 1.
                                                                              Reagents
  Received October 25, 2001. Accepted by EB June 5, 2002.
  1
    Author to whom correspondence should be addressed; e-mail:                (a) Standard solution of phosphorus(1000 mg/L).—Pre-
mawhinneyT@missouri.edu.                                                   pared from dried (2 h at 110°C) KH2PO4 (NIST Standard Ref-
1242    YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002


Table 1. ICP-AES instrumental parameters and                        previously been folded, rinsed, and dried on a
operating conditions                                                polymethylpentene filter. Insert each filter into a numbered
Instrumentation                    Operating condition              500 mL volumetric flask for collection of filtrate. Wash ac-
                                                                    tively until ca 250 mL filtrate has been collected. Bring filtrate
                                                                    to final volume and mix. The phosphorus concentration in the
Instrument                ARL 3410+ sequential ICP spectrometer
                                                                    dissolved samples of 9703 and 9504 are ca 1.0 and 4.0 ppm,
RF generator frequency                 27.12 MHz
                                                                    respectively, and run directly by ICP-AES without dilution.
Plasma torch                            Minitorch                   Dilute remaining 13 Magruder dissolved fertilizers samples
Pump                              Gilson peristaltic pump           10-fold before ICP-AES analysis. The phosphorus concentra-
Nebulizer                 Meinhard pneumatic nebulizer (Type K)     tions in these diluted solutions range from 5.5 to 41.0 ppm.
Forward power                             650 W                        Acid and Matrix Effects
Reflected power                           <3 W
                                                                        Phosphorus solutions (5 mg/L) with different concentra-
Viewing height                   9.0 mm above load coil
                                                                    tions of perchloric acid were prepared for acid effects study.
Coolant gas flow rate                   10.5 L/min
                                                                    The final concentration of perchloric acid varied from 0.0 and
Auxiliary gas flow rate                 0.8 L/min                   0.0001 mol/L to as high as 2.0 mol/L. Phosphorus solutions
Carrier gas flow rate                   0.8 L/min                   (5 mg/L), mixed with different concentrations of possible ma-
Integration time                           1s                       trix elements (Al, Ca, Mg, K, Na), were used for the matrix ef-
Sample uptake rate                     2.5 mL/min                   fects investigations. The individual concentrations of these
                                                                    5 matrix elements were 50, 100, 150, and 200 mg/L. All the
                                                                    ICP-AES measurements for acid effects and matrix effects
                                                                    were triplicate determinations, and relative standard devia-
                                                                    tions (RSD) were within ± 3.0%.
                                                                    Results and Discussion
erence Material), and 20 mL perchloric acid was added before
diluting to volume.                                                    Acid Effects
   (b) Calibration solutions.—Prepared to contain 0.0, 1.0, 5.0,
10.0, 50.0, and 100.0 mg P/L in 4% HClO4. The concentrations            After sample preparation as described in the Method sec-
of phosphorus in the samples were calculated from a linear re-      tion, the solution of total P2O5 is acidic, containing about
gression equation of the calibration curve. Required correlation    0.4 mol/L HClO4, but the solutions of direct available P2O5
coefficient of this equation was set to not less than 0.9990.       and water-soluble P2O5 are both neutral. As a result, it was
                                                                    necessary to investigate the acid effects of HClO4 on the emis-
   Sample Preparation                                               sion signal of phosphorus.
    (a) Total P2O5.—Weigh triplicate 0.50 g subsamples into             As shown in Table 2 , the emission intensities ratio for all
250 mL boiling flasks. Add 15 mL HNO3 and 10 mL HClO4.              5 phosphorus analytical wavelengths varied from 94 to 105%,
Boil gently on medium-heat hot plate for ca 1 h until solution is   while being measured in the presence of 0.0001–2.0 mol/L
colorless, or nearly so, and dense white fumes of HClO4 appear      HClO4. Because the dissolved samples were diluted 10-fold
in the flask. After digestion, cool to room temperature, add ca     before determination, 4% (v/v) HClO4 was used as the diluent
50 mL deionized water, and boil gently for ca 15 min. Remove        in all cases. As a result, the negligible influence of acid effects
sample from hot plate, cool to room temperature, dilute to vol-     on phosphorus determination was further minimized in all
ume, stir, and stopper. Dilute dissolved samples 10-fold before     ICP-AES assays.
ICP-AES determination. The phosphorus concentrations in the            Matrix Effect
diluted solutions range from 2.5 to 45.0 ppm.
    (b) Direct extraction available P2O5 (EDTA).—Weigh                 Five elements, K, Na, Mg, Al, Ca, were selected as matrix
triplicate 0.50 g subsamples into 250 mL boiling flasks. Add        elements in this investigation. Table 3 shows that the phospho-
100 mL ammonium citrate–EDTA solution that has been                 rus emission intensity ratio at various wavelengths was within
preheated to 65°C. Place flask in 65°C shaker bath. Close           the range of 99–104%, clearly demonstrating that matrix inter-
flask tightly with rubber stopper. Vigorously shake flask for       ference was minimal for analysis of phosphorus. Notably, con-
1 h at 65°C. Shaking should be vigorous enough to ensure            centrations of those elements in diluted dissolved samples were
wetting of sample and flask walls. Remove samples from              well below the matrix concentrations presented in Table 3.
bath, and immediately cool to room temperature with 4°C dis-        Therefore, matrix effects can be considered negligible from
tilled water. Dilute to volume, and mix thoroughly. Dilute dis-     these elements when phosphorus in fertilizers is determined.
solved samples 10-fold before ICP-AES determination. The
                                                                       Detection Limit
phosphorus concentrations in the diluted solutions range from
2.0 to 45.0 ppm.                                                       A blank solution (8%, v/v, HClO4) and a solution of
    (c) Water soluble P2O5.—Weigh triplicate 1.00 g                 P (5 mg/L) were used to measure the detection limit. Detection
subsamples on 11 cm Whatman No.4 filter circles that have           limit (3σ) of the wavelengths 177.499, 178.287, 213.618,
YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002 1243


Table 2. Acid effect of HClO4 on P (5 mg/L) at 5 wavelengths
                                                        Phosphorus intensity ratio at different wavelengths (nm), %a

HClO4 concn, mol/L               P177.500                P178.287                   P213.618               P214.914              P253.565


0.0                              100                     100                        100                    100                   100
0.0001                           103 ± 1.1               101 ± 1.8                  103 ± 2.1              102 ± 1.1             100 ± 0.9
0.001                            102 ± 0.3               105 ± 0.4                  105 ± 0.6              106 ± 0.4             105 ± 0.6
0.01                             100 ± 0.5               105 ± 1.0                  104 ± 1.3              106 ± 0.8             102 ± 2.3
0.05                                96 ± 1.7             102 ± 1.9                  101 ± 2.3              100 ± 0.2              98 ± 1.1
0.15                             100 ± 1.0               102 ± 1.3                  100 ± 0.2               98 ± 2.1              98 ± 0.6
0.25                                94 ± 1.2                 99 ± 0.1               101 ± 0.9              100 ± 0.7              99 ± 0.4
0.5                                 96 ± 2.2                 98 ± 1.6                99 ± 2.0               98 ± 2.0              97 ± 1.3
1.0                                 95 ± 1.7             100 ± 2.1                  100 ± 1.8               99 ± 1.5              98 ± 1.3
2.0                                 95 ± 0.8             100 ± 1.9                   98 ± 0.7               98 ± 1.1              99 ± 0.8

a
     Results are expressed as mean ± standard deviation for triplicate determinations.




Table 3. Matrix effects of Mg, Ca, K, Al, and Na on P (5 mg/L) emission signals

                                                                  Phosphorus intensity ratio at different wavelengths (nm), %a

Element                Matrix concn, mg/L        P177.500               P178.287           P213.618              P214.914         P253.565


                                —               100                     100                 100                  100              100
Mg                              50               102 ± 1.1              102 ± 0.3           101 ± 1.6            101 ± 1.1        103 ± 1.8
                               100               100 ± 2.1              102 ± 2.0           100 ± 0.2            102 ± 1.3        102 ± 1.2
                               150               102 ± 0.9              102 ± 1.5           102 ± 0.5            102 ± 1.2        104 ± 1.5
                               200               102 ± 0.6              103 ± 1.1           102 ± 0.8            103 ± 1.9        104 ± 1.0
Ca                              50               101 ± 0.7              103 ± 0.6           103 ± 0.1            102 ± 0.4        100 ± 0.5
                               100               102 ± 1.4              103 ± 0.4           102 ± 1.1            102 ± 1.1        103 ± 0.9
                               150               101 ± 2.1              102 ± 2.1           103 ± 1.4            103 ± 0.6        102 ± 1.6
                               200               103 ± 2.0              102 ± 1.7           101 ± 0.6            104 ± 0.4        103 ± 1.1
K                               50               101 ± 0.6              100 ± 1.1           102 ± 0.8            101 ± 2.1        100 ± 2.0
                               100               100 ± 0.6              102 ± 1.5           101 ± 0.2            101 ± 0.7        101 ± 1.8
                               150               100 ± 0.9              101 ± 0.7               99 ± 1.5         100 ± 0.1        101 ± 1.7
                               200               100 ± 0.3              100 ± 0.3           100 ± 1.1            102 ± 0.5         99 ± 1.6
Al                              50               102 ± 0.8              101 ± 1.3           102 ± 1.2            103 ± 0.9        100 ± 1.2
                               100               101 ± 2.1              102 ± 1.3           103 ± 0.5            102 ± 0.3        103 ± 0.2
                               150               100 ± 1.7              102 ± 1.8           103 ± 0.5            104 ± 1.8        104 ± 0.7
                               200               100 ± 1.4              103 ± 0.9           104 ± 0.9            103 ± 1.1        103 ± 1.1
Na                              50               102 ± 2.0              102 ± 0.5           101 ± 1.3            103 ± 0.3        102 ± 2.0
                               100               102 ± 2.2              102 ± 1.6           100 ± 1.1            102 ± 1.1        101 ± 2.1
                               150               102 ± 1.5              103 ± 1.1           102 ± 0.8            102 ± 0.8        104 ± 1.1
                               200               101 ± 1.1              104 ± 1.4           103 ± 0.2            102 ± 0.2        103 ± 1.5

a
     Results are expressed as mean ± standard deviation for triplicate determinations.
1244      YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002


Table 4. Linear regression analysis of ICP phosphorus results with average values of Magruder fertilizers
                                  Total P2O5                       Direct available P2O5                  Water-soluble P2O5

Wavelength, nm          Regression line             (a       Regression line           (a           Regression line            (a


177.499              y = 1.007x – 0.2529          0.9998   y = 1.010x – 0.5845       0.9994      y = 0.8678x + 0.5807      0.9022
178.287              y = 1.013x – 0.2403          0.9997   y = 1.004x + 0.0604       0.9997      y = 0.8797x + 0.3319      0.9082
213.618              y = 1.001x – 0.1247          0.9999   y = 1.002x – 0.0864       0.9999      y = 0.8872x + 0.9076      0.9084
214.914              y = 1.010x – 0.1571          0.9998   y = 1.008x – 0.3590       0.9998      y = 0.8843x + 0.6544      0.9150
253.565              y = 0.9913x – 0.0829         0.9948   y = 0.9875x – 0.5438      0.9984      y = 0.9849x + 0.3170      0.8987

a
    Linear regression correlation coefficients.



214.914, and 253.565 nm, which were calculated from the                (mono-ammonium phosphate 9803B). The NPK values in
standard deviations of 11 measurements of the blank solution,          Table 5 represent the percentages of nitrogen, available phos-
were 40, 42, 23, 55, and 88 µg/L, respectively.                        phorus (P2O5), and soluble potassium (K2O). Except for
                                                                       9811A, which is clear liquid fertilizer, the other 14 Magruder
     Magruder Fertilizer Analysis by ICP-AES
                                                                       samples are solid. Triple superphosphate sample
    In 1922, E.W. Magruder, chief chemist of the F.S. Royster          0998A (0-46-0) contains only one nutrient: phosphorus; the
Guano Co. (Norfolk, VA) began the fertilizer check sample              remaining 14 Magruder samples contain 2 or 3 nutrients: ni-
program that bears his name today. Magruder fertilizer check           trogen, phosphorus, potassium. With the 213.618 nm wave-
sample programs are widely used to ensure consistency                  length used to determine P2O5, the ICP-AES recoveries were
among laboratories and methods. The results can identify sta-          compared with the Magruder average standard values (Ta-
tistically different repeatabilities or reproducibilities among        ble 5). The recovery was defined as the ratio of the ICP results
different methods or among laboratories using the same                 to the Magruder average.
method. In this study, 15 Magruder fertilizer check samples                The values of total P2O5 and direct available P2O5 mea-
were selected to study the performance of ICP-AES for the de-          sured by ICP-AES compared closely with the reported
termination of phosphorus.                                             Magruder average. Two notable exceptions were observed,
    Generally, total P2O5, direct extraction available P2O5            both for water-soluble P2O5 analyses, where significant dis-
(EDTA), modified extraction available P2O5 (non-triple                 crepancies between the values of ICP results and Magruder
superphosphate), and water-soluble P2O5 are often deter-               average were determined. Specifically, these anomalies in-
mined in laboratories. Because the matrixes of direct extrac-          volved Magruder samples 9504 and 9811A. The remarkably
tion available P2O5 (EDTA) and modified extraction available           large standard deviation of the Magruder average on the solid
P2O5 are similar, this investigation used the sample prepara-          fertilizer sample 9504 makes the low recovery understand-
tion procedure of direct extraction available P2O5 (EDTA).             able. This is in contrast to the high recovery (329.4%) of phos-
    Table 4 summarizes the linear regression analysis of the           phorus by ICP-AES for the liquid Magruder fertilizer sam-
ICP results with the Magruder average at various wave-                 ple 9811A, which is totally water-soluble. This is reasonably
lengths. A main focus of this study was to determine which             explained by the fact that all phosphorus in the solution is
wavelength for phosphorus was suitable. For total P2O5 and             determined by the ICP spectrometer, whether it is present in its
direct available P2O5, the overall agreement for phosphorus
                                                                       ortho-, poly-, organic-, or low-oxide forms, and the Magruder
was excellent over the wide concentration range found within
                                                                       average presented in Table 5 reports only the orthophosphate
the 15 Magruder fertilizers. The intercept was small and not
                                                                       concentration in the sample. The determined total P2O5 of
significantly different from zero, and the slope was very close
                                                                       33.47% in this sample by ICP-AES is further substantiated by
to 1.0. This demonstrated that the ICP-AES method possesses
neither constant nor proportional systematic errors compared           the fact that sample 9811A’s content as determined by total
with the Magruder average. The best linearity was achieved at          P2O5 and direct available P2O5 are in agreement. If sam-
213.618 nm. In addition, 213.618 nm is the most sensitive              ple 9811A is excluded from the linear regression (Table 4), the
wavelength for phosphorus. Therefore, among the 5 analytical           regression equation of water-soluble P2O5 will be y = 0.9733x +
wavelengths tested, wavelength 213.618 nm was the optimal              0.7855 at 213.618 nm, with a correlation coefficient of 0.9983.
analytical wavelength for determining phosphorus in fertiliz-              Analysis of total phosphorus by ICP-AES is simpler and
ers by ICP-AES.                                                        faster than the traditional procedures using digestion and spec-
    To represent the assorted commercial fertilizer used in the        trophotometric determination. Significant advantages of the
agriculture, the contents of the total phosphorus (P2O5) in the        ICP-AES method are also demonstrated by its wide dynamic
selected Magruder fertilizer samples varies from several per-          range of calibration and high sensitivity. Furthermore, by the
cent, as in organic fertilizers 9703 and 9504, to as high as 52%       ICP-AES method, the same amount of fertilizer sample can be
Table 5. ICP results of P2O5 recovery on 213.618 nm compared with Magruder average values
                                                         Total P2O5, %                                      Direct available P2O5, %                             Water-soluble P2O5, %

Sample No.                NPK         Magruder value      ICP resultsa      Recovery, %         Magruder value    ICP results      Recovery, %   Magruder value       ICP results        Recovery, %


9703                     4-2-0          2.85 ± 0.30        2.96 ± 0.03         103.9             2.52 ± 0.21       2.61 ± 0.02         103.4       0.12 ± 0.05        0.12 ± 0.00           100.0
9504                     6-2-0          4.37 ± 0.44        4.80 ± 0.02         109.8             3.31 ± 0.45       3.47 ± 0.03         104.8       2.71 ± 2.48        0.47 ± 0.01            17.3
                                                                                                                                                        b
9401                    10-10-10       10.26 ± 0.09       10.10 ± 0.08          98.4            10.55 ± 0.01     10.26 ± 0.04           97.3          —                   —                  —
9808                    10-10-10        9.92 ± 0.13       10.05 ± 0.03         101.3             9.55 ± 0.32       9.97 ± 0.11         104.4       6.56 ± 0.20        6.78 ± 0.03           103.4
9309                    13-13-13       13.39 ± 0.17       13.54 ± 0.23         101.1            13.38 ± 0.16     13.40 ± 0.14          100.1          —                   —                  —
9506                    19-19-19       19.68 ± 0.32       19.82 ± 0.31         100.7            19.74 ± 0.25     19.71 ± 0.37           99.8      18.20 ± 0.25       18.34 ± 0.08           100.8
9409                     4-22-6        22.24 ± 0.25       21.87 ± 0.17          98.3            22.06 ± 0.19     22.18 ± 0.19          100.5      17.31 ± 0.34       16.55 ± 0.07            95.6
9402                    7-23-22        22.85 ± 0.16       22.98 ± 0.18         100.6            22.54 ± 0.43     22.57 ± 0.31          100.1      17.80 ± 0.27       17.75 ± 0.30            99.7
9806                    8-24-24        20.80 ± 0.19       20.83 ± 0.20         100.1            20.77 ± 0.20     20.74 ± 0.23           99.9      19.79 ± 0.33       19.89 ± 0.16           100.5
9606B                   0-32-31        36.40 ± 0.49       36.85 ± 0.20         101.2            36.41 ± 0.51     36.52 ± 0.17          100.3      12.42 ± 1.57       11.69 ± 0.37            94.1
9811A                   10-34-0        34.02 ± 0.59       34.02 ± 0.17         100              33.94 ± 0.31     33.98 ± 0.14          100.1      10.16 ± 4.21       33.47 ± 0.29           329.4




                                                                                                                                                                                                       YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002 1245
896B                                   41.75 ± 0.64       42.21 ± 0.37         101.1                 —                —                 —             —                   —                  —
9810A                   18-46-0         6.72 ± 0.59       46.88 ± 0.17          99.9            46.56 ± 0.36     46.54 ± 0.17          100        43.52 ± 1.07       43.95 ± 0.28           101.0
0998A                    0-46-0        46.31 ± 0.23       46.29 ± 0.36         100.0            46.18 ± 0.18     45.78 ± 0.20           99.1      42.74 ± 0.29       41.23 ± 0.27            96.5
9803B                   11-52-0        51.06 ± 0.55       51.02 ± 0.24          99.9            50.85 ± 0.33     51.14 ± 0.39          100.5      44.62 ± 0.94       46.33 ± 0.39           103.8

a
    ICP results are expressed as the mean ± standard deviation for triplicate determinations.
b
    — = No Magruder value provided with check sample.
1246   YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002


weighed regardless of the phosphorus concentration, and no          general, the precision and accuracy of ICP-AES determina-
spike experiment is required for low phosphorus content.            tions were close to the average values of Magruder standard
    The precision and accuracy of the methodology developed         check fertilizer samples. Care must be taken in the determina-
were tested by analyzing total P2O5 and direct available P2O5.      tion of total P2O5 in fertilizer samples in which phosphorus
For short-term precision testing (7 consecutive determinations),    may exist in several forms. By the ICP-AES method, all phos-
                                                                    phate forms are analyzed, yielding a true total P2O5 value.
the RSD of total P2O5 and direct available P2O5 were in the range
of 0.6–2.2 and 0.8–2.6%, respectively. For long-term precision
                                                                    References
testing (7 determinations over 7 consecutive days), the RSDs of
total P2O5 and direct available P2O5 were in the range of           (1) Official Methods of Analysis (1990) 15th Ed., AOAC,
0.7–3.5 and 0.8–3.9%, respectively. The precision of total P2O5         Arlington, VA, sec. 962.02
and direct available P2O5 determination was also excellent.         (2) Dahlgren, S.W. (1962) Z. Anal. Chem. 189, 243–256
                                                                    (3) Official Methods of Analysis (1990) 15th Ed., AOAC,
Conclusions                                                             Arlington, VA, secs. 958.01, 963.03(a)
                                                                    (4) Fujiwara, K., Mignardi, M.A., Petrucci, G., Smith, B.W., &
                                                                        Winefordner, J.D. (1989) Spectrosc. Lett. 22, 1125–1140
    The ICP-AES method enables the determination of total           (5) Hamalova, M., Hodslavska, J., Janos, P., & Kanicky, V.J.
P2O5, direct extraction available P2O5 (EDTA), and wa-                  (1997) J. AOAC Int. 80, 1151–1155
ter-soluble P2O5 in fertilizers by the same calibration curve.      (6) Ardis, J.D., & Baker, A.M. (1997) J. AOAC Int. 72, 857–859
Wavelength 213.618 nm proved to be the best analytical              (7) Jones, J.B. (1982) J. Assoc. Off. Anal. Chem. 65, 781–785
wavelength for phosphorus determination in fertilizers. In          (8) Jones, J.B. (1983) Spectrochim. Acta 38B, 271–276

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P2 o5 in fertilizer

  • 1. YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002 1241 AGRICULTURAL MATERIALS Determination of Phosphorus in Fertilizers by Inductively Coupled Plasma Atomic Emission Spectrometry WEI MIN YANG, RHONDA L. BOLES, and THOMAS P. MAWHINNEY1 University of Missouri-Columbia, Experiment Station Chemical Laboratories, Rm 4, Agriculture Bldg, Columbia, MO 65211 An inductively coupled plasma atomic emission tion curve, the weight of the fertilizer samples is adjusted to spectrometry (ICP-AES) method was developed for control final sample phosphate concentrations. the determination of phosphorus in fertilizers. To- A major advantage of inductively coupled plasma atomic tal phosphorus, direct extraction available phos- emission spectrometry (ICP-AES) is its ability to determine phorus (EDTA), and water-soluble phosphorus, re- several elements simultaneously in a wide range of concentra- ported as phosphorus pentoxide (P2O5), in tions. For determination of phosphorus, the sensitivity of the 15 Magruder check fertilizers were measured by ICP-AES analysis method exceeds that of the AOAC official ICP-AES, and the results were compared with methods; in addition, the ICP-AES has a calibration curve of a those obtained by the AOAC official method. very wide linear range. As a result, no sample weighing adjust- Five analytical wavelengths of phosphorus, ment is required for the ICP-AES method. Because of these fea- 177.499, 178.287, 213.618, 214.914, and 253.565 nm, tures, the determination of phosphorus by the ICP-AES method were tested for the determination of phosphorus in has attracted the attention of several scientists. fertilizers, and their detection limits were obtained. Hamalova et al. (5) determined phosphorus, potassium, Acid effects of perchloric acid and possible matrix and magnesium in 12 fertilizers by ICP-AES. For phosphorus, effects of aluminum, calcium, magnesium, potas- the results of ICP-AES were compared with those obtained by sium, and sodium were negligible for phosphorus the standard gravimetry method. Generally, precision and ac- determination. Wavelength 213.618 nm was the curacy of the ICP-AES method were satisfactory. Ardis and best analytical wavelength for phosphorus deter- Baker (6) used an ICP spectrometer to monitor fertilizer plant mination by all 3 sample preparation methods for effluents for phosphorus, sulfur, and metals. The detection the selected Magruder fertilizers. The results dem- limit for phosphorus was 0.08 µg/mL at 213.618 nm. onstrated that the accuracy and precision of the Jones (7, 8) determined the concentrations of major, micro, ICP-AES method were comparable with those of and trace elements by ICP-AES in fertilizer standards. It was the official methods. determined that analysis by ICP-AES of fertilizer materials with wide ranges of elemental contents is a rapid technique that can yield results comparable with those obtained by n fertilizers, phosphorus is one of the major nutrients that AOAC protocols. I is most commonly determined. Accurate analysis of fertil- izers is necessary both for the quality control of their pro- duction and for determining their effective use in the field. This study was undertaken to standardize the ICP-AES method for determination of phosphorus in several sample preparation methods in the Magruder fertilizer check samples Presently, the gravimetric determination with quimociac re- by the use of the same calibration curve. agent and the spectrophotometric molybdovanadophosphate METHOD procedures are the AOAC official reference methods for de- termination of phosphorus in fertilizers (1–3). The gravimetric Apparatus procedure is both tedious and time-consuming. The spectro- photometric molybdovandate phosphate method, on the other (a) Spectrometer.—Atomic emission measurements of hand, measures only orthophosphate (4). Because of this, fer- phosphorus were made with an ARL 3410+ sequential ICP tilizer samples that possess phosphate in other forms must be spectrometer (Fisons, Dearborn, MI) with a minitorch. converted to orthophosphate before determination. Further- (b) Nebulizer and pump.—The sample solutions were more, to control the citrate interference which is used for di- nebulized by a pneumatic nebulizer (Precision Glassblowing, rect available extraction, appropriate matrix match is neces- Englewood, CO) with a Gilson peristaltic pump sary for the calibration standards. Finally, to ensure that the (Worthington, OH). The main operating conditions are listed measured signals fall within the working range of the calibra- in Table 1. Reagents Received October 25, 2001. Accepted by EB June 5, 2002. 1 Author to whom correspondence should be addressed; e-mail: (a) Standard solution of phosphorus(1000 mg/L).—Pre- mawhinneyT@missouri.edu. pared from dried (2 h at 110°C) KH2PO4 (NIST Standard Ref-
  • 2. 1242 YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002 Table 1. ICP-AES instrumental parameters and previously been folded, rinsed, and dried on a operating conditions polymethylpentene filter. Insert each filter into a numbered Instrumentation Operating condition 500 mL volumetric flask for collection of filtrate. Wash ac- tively until ca 250 mL filtrate has been collected. Bring filtrate to final volume and mix. The phosphorus concentration in the Instrument ARL 3410+ sequential ICP spectrometer dissolved samples of 9703 and 9504 are ca 1.0 and 4.0 ppm, RF generator frequency 27.12 MHz respectively, and run directly by ICP-AES without dilution. Plasma torch Minitorch Dilute remaining 13 Magruder dissolved fertilizers samples Pump Gilson peristaltic pump 10-fold before ICP-AES analysis. The phosphorus concentra- Nebulizer Meinhard pneumatic nebulizer (Type K) tions in these diluted solutions range from 5.5 to 41.0 ppm. Forward power 650 W Acid and Matrix Effects Reflected power <3 W Phosphorus solutions (5 mg/L) with different concentra- Viewing height 9.0 mm above load coil tions of perchloric acid were prepared for acid effects study. Coolant gas flow rate 10.5 L/min The final concentration of perchloric acid varied from 0.0 and Auxiliary gas flow rate 0.8 L/min 0.0001 mol/L to as high as 2.0 mol/L. Phosphorus solutions Carrier gas flow rate 0.8 L/min (5 mg/L), mixed with different concentrations of possible ma- Integration time 1s trix elements (Al, Ca, Mg, K, Na), were used for the matrix ef- Sample uptake rate 2.5 mL/min fects investigations. The individual concentrations of these 5 matrix elements were 50, 100, 150, and 200 mg/L. All the ICP-AES measurements for acid effects and matrix effects were triplicate determinations, and relative standard devia- tions (RSD) were within ± 3.0%. Results and Discussion erence Material), and 20 mL perchloric acid was added before diluting to volume. Acid Effects (b) Calibration solutions.—Prepared to contain 0.0, 1.0, 5.0, 10.0, 50.0, and 100.0 mg P/L in 4% HClO4. The concentrations After sample preparation as described in the Method sec- of phosphorus in the samples were calculated from a linear re- tion, the solution of total P2O5 is acidic, containing about gression equation of the calibration curve. Required correlation 0.4 mol/L HClO4, but the solutions of direct available P2O5 coefficient of this equation was set to not less than 0.9990. and water-soluble P2O5 are both neutral. As a result, it was necessary to investigate the acid effects of HClO4 on the emis- Sample Preparation sion signal of phosphorus. (a) Total P2O5.—Weigh triplicate 0.50 g subsamples into As shown in Table 2 , the emission intensities ratio for all 250 mL boiling flasks. Add 15 mL HNO3 and 10 mL HClO4. 5 phosphorus analytical wavelengths varied from 94 to 105%, Boil gently on medium-heat hot plate for ca 1 h until solution is while being measured in the presence of 0.0001–2.0 mol/L colorless, or nearly so, and dense white fumes of HClO4 appear HClO4. Because the dissolved samples were diluted 10-fold in the flask. After digestion, cool to room temperature, add ca before determination, 4% (v/v) HClO4 was used as the diluent 50 mL deionized water, and boil gently for ca 15 min. Remove in all cases. As a result, the negligible influence of acid effects sample from hot plate, cool to room temperature, dilute to vol- on phosphorus determination was further minimized in all ume, stir, and stopper. Dilute dissolved samples 10-fold before ICP-AES assays. ICP-AES determination. The phosphorus concentrations in the Matrix Effect diluted solutions range from 2.5 to 45.0 ppm. (b) Direct extraction available P2O5 (EDTA).—Weigh Five elements, K, Na, Mg, Al, Ca, were selected as matrix triplicate 0.50 g subsamples into 250 mL boiling flasks. Add elements in this investigation. Table 3 shows that the phospho- 100 mL ammonium citrate–EDTA solution that has been rus emission intensity ratio at various wavelengths was within preheated to 65°C. Place flask in 65°C shaker bath. Close the range of 99–104%, clearly demonstrating that matrix inter- flask tightly with rubber stopper. Vigorously shake flask for ference was minimal for analysis of phosphorus. Notably, con- 1 h at 65°C. Shaking should be vigorous enough to ensure centrations of those elements in diluted dissolved samples were wetting of sample and flask walls. Remove samples from well below the matrix concentrations presented in Table 3. bath, and immediately cool to room temperature with 4°C dis- Therefore, matrix effects can be considered negligible from tilled water. Dilute to volume, and mix thoroughly. Dilute dis- these elements when phosphorus in fertilizers is determined. solved samples 10-fold before ICP-AES determination. The Detection Limit phosphorus concentrations in the diluted solutions range from 2.0 to 45.0 ppm. A blank solution (8%, v/v, HClO4) and a solution of (c) Water soluble P2O5.—Weigh triplicate 1.00 g P (5 mg/L) were used to measure the detection limit. Detection subsamples on 11 cm Whatman No.4 filter circles that have limit (3σ) of the wavelengths 177.499, 178.287, 213.618,
  • 3. YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002 1243 Table 2. Acid effect of HClO4 on P (5 mg/L) at 5 wavelengths Phosphorus intensity ratio at different wavelengths (nm), %a HClO4 concn, mol/L P177.500 P178.287 P213.618 P214.914 P253.565 0.0 100 100 100 100 100 0.0001 103 ± 1.1 101 ± 1.8 103 ± 2.1 102 ± 1.1 100 ± 0.9 0.001 102 ± 0.3 105 ± 0.4 105 ± 0.6 106 ± 0.4 105 ± 0.6 0.01 100 ± 0.5 105 ± 1.0 104 ± 1.3 106 ± 0.8 102 ± 2.3 0.05 96 ± 1.7 102 ± 1.9 101 ± 2.3 100 ± 0.2 98 ± 1.1 0.15 100 ± 1.0 102 ± 1.3 100 ± 0.2 98 ± 2.1 98 ± 0.6 0.25 94 ± 1.2 99 ± 0.1 101 ± 0.9 100 ± 0.7 99 ± 0.4 0.5 96 ± 2.2 98 ± 1.6 99 ± 2.0 98 ± 2.0 97 ± 1.3 1.0 95 ± 1.7 100 ± 2.1 100 ± 1.8 99 ± 1.5 98 ± 1.3 2.0 95 ± 0.8 100 ± 1.9 98 ± 0.7 98 ± 1.1 99 ± 0.8 a Results are expressed as mean ± standard deviation for triplicate determinations. Table 3. Matrix effects of Mg, Ca, K, Al, and Na on P (5 mg/L) emission signals Phosphorus intensity ratio at different wavelengths (nm), %a Element Matrix concn, mg/L P177.500 P178.287 P213.618 P214.914 P253.565 — 100 100 100 100 100 Mg 50 102 ± 1.1 102 ± 0.3 101 ± 1.6 101 ± 1.1 103 ± 1.8 100 100 ± 2.1 102 ± 2.0 100 ± 0.2 102 ± 1.3 102 ± 1.2 150 102 ± 0.9 102 ± 1.5 102 ± 0.5 102 ± 1.2 104 ± 1.5 200 102 ± 0.6 103 ± 1.1 102 ± 0.8 103 ± 1.9 104 ± 1.0 Ca 50 101 ± 0.7 103 ± 0.6 103 ± 0.1 102 ± 0.4 100 ± 0.5 100 102 ± 1.4 103 ± 0.4 102 ± 1.1 102 ± 1.1 103 ± 0.9 150 101 ± 2.1 102 ± 2.1 103 ± 1.4 103 ± 0.6 102 ± 1.6 200 103 ± 2.0 102 ± 1.7 101 ± 0.6 104 ± 0.4 103 ± 1.1 K 50 101 ± 0.6 100 ± 1.1 102 ± 0.8 101 ± 2.1 100 ± 2.0 100 100 ± 0.6 102 ± 1.5 101 ± 0.2 101 ± 0.7 101 ± 1.8 150 100 ± 0.9 101 ± 0.7 99 ± 1.5 100 ± 0.1 101 ± 1.7 200 100 ± 0.3 100 ± 0.3 100 ± 1.1 102 ± 0.5 99 ± 1.6 Al 50 102 ± 0.8 101 ± 1.3 102 ± 1.2 103 ± 0.9 100 ± 1.2 100 101 ± 2.1 102 ± 1.3 103 ± 0.5 102 ± 0.3 103 ± 0.2 150 100 ± 1.7 102 ± 1.8 103 ± 0.5 104 ± 1.8 104 ± 0.7 200 100 ± 1.4 103 ± 0.9 104 ± 0.9 103 ± 1.1 103 ± 1.1 Na 50 102 ± 2.0 102 ± 0.5 101 ± 1.3 103 ± 0.3 102 ± 2.0 100 102 ± 2.2 102 ± 1.6 100 ± 1.1 102 ± 1.1 101 ± 2.1 150 102 ± 1.5 103 ± 1.1 102 ± 0.8 102 ± 0.8 104 ± 1.1 200 101 ± 1.1 104 ± 1.4 103 ± 0.2 102 ± 0.2 103 ± 1.5 a Results are expressed as mean ± standard deviation for triplicate determinations.
  • 4. 1244 YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002 Table 4. Linear regression analysis of ICP phosphorus results with average values of Magruder fertilizers Total P2O5 Direct available P2O5 Water-soluble P2O5 Wavelength, nm Regression line (a Regression line (a Regression line (a 177.499 y = 1.007x – 0.2529 0.9998 y = 1.010x – 0.5845 0.9994 y = 0.8678x + 0.5807 0.9022 178.287 y = 1.013x – 0.2403 0.9997 y = 1.004x + 0.0604 0.9997 y = 0.8797x + 0.3319 0.9082 213.618 y = 1.001x – 0.1247 0.9999 y = 1.002x – 0.0864 0.9999 y = 0.8872x + 0.9076 0.9084 214.914 y = 1.010x – 0.1571 0.9998 y = 1.008x – 0.3590 0.9998 y = 0.8843x + 0.6544 0.9150 253.565 y = 0.9913x – 0.0829 0.9948 y = 0.9875x – 0.5438 0.9984 y = 0.9849x + 0.3170 0.8987 a Linear regression correlation coefficients. 214.914, and 253.565 nm, which were calculated from the (mono-ammonium phosphate 9803B). The NPK values in standard deviations of 11 measurements of the blank solution, Table 5 represent the percentages of nitrogen, available phos- were 40, 42, 23, 55, and 88 µg/L, respectively. phorus (P2O5), and soluble potassium (K2O). Except for 9811A, which is clear liquid fertilizer, the other 14 Magruder Magruder Fertilizer Analysis by ICP-AES samples are solid. Triple superphosphate sample In 1922, E.W. Magruder, chief chemist of the F.S. Royster 0998A (0-46-0) contains only one nutrient: phosphorus; the Guano Co. (Norfolk, VA) began the fertilizer check sample remaining 14 Magruder samples contain 2 or 3 nutrients: ni- program that bears his name today. Magruder fertilizer check trogen, phosphorus, potassium. With the 213.618 nm wave- sample programs are widely used to ensure consistency length used to determine P2O5, the ICP-AES recoveries were among laboratories and methods. The results can identify sta- compared with the Magruder average standard values (Ta- tistically different repeatabilities or reproducibilities among ble 5). The recovery was defined as the ratio of the ICP results different methods or among laboratories using the same to the Magruder average. method. In this study, 15 Magruder fertilizer check samples The values of total P2O5 and direct available P2O5 mea- were selected to study the performance of ICP-AES for the de- sured by ICP-AES compared closely with the reported termination of phosphorus. Magruder average. Two notable exceptions were observed, Generally, total P2O5, direct extraction available P2O5 both for water-soluble P2O5 analyses, where significant dis- (EDTA), modified extraction available P2O5 (non-triple crepancies between the values of ICP results and Magruder superphosphate), and water-soluble P2O5 are often deter- average were determined. Specifically, these anomalies in- mined in laboratories. Because the matrixes of direct extrac- volved Magruder samples 9504 and 9811A. The remarkably tion available P2O5 (EDTA) and modified extraction available large standard deviation of the Magruder average on the solid P2O5 are similar, this investigation used the sample prepara- fertilizer sample 9504 makes the low recovery understand- tion procedure of direct extraction available P2O5 (EDTA). able. This is in contrast to the high recovery (329.4%) of phos- Table 4 summarizes the linear regression analysis of the phorus by ICP-AES for the liquid Magruder fertilizer sam- ICP results with the Magruder average at various wave- ple 9811A, which is totally water-soluble. This is reasonably lengths. A main focus of this study was to determine which explained by the fact that all phosphorus in the solution is wavelength for phosphorus was suitable. For total P2O5 and determined by the ICP spectrometer, whether it is present in its direct available P2O5, the overall agreement for phosphorus ortho-, poly-, organic-, or low-oxide forms, and the Magruder was excellent over the wide concentration range found within average presented in Table 5 reports only the orthophosphate the 15 Magruder fertilizers. The intercept was small and not concentration in the sample. The determined total P2O5 of significantly different from zero, and the slope was very close 33.47% in this sample by ICP-AES is further substantiated by to 1.0. This demonstrated that the ICP-AES method possesses neither constant nor proportional systematic errors compared the fact that sample 9811A’s content as determined by total with the Magruder average. The best linearity was achieved at P2O5 and direct available P2O5 are in agreement. If sam- 213.618 nm. In addition, 213.618 nm is the most sensitive ple 9811A is excluded from the linear regression (Table 4), the wavelength for phosphorus. Therefore, among the 5 analytical regression equation of water-soluble P2O5 will be y = 0.9733x + wavelengths tested, wavelength 213.618 nm was the optimal 0.7855 at 213.618 nm, with a correlation coefficient of 0.9983. analytical wavelength for determining phosphorus in fertiliz- Analysis of total phosphorus by ICP-AES is simpler and ers by ICP-AES. faster than the traditional procedures using digestion and spec- To represent the assorted commercial fertilizer used in the trophotometric determination. Significant advantages of the agriculture, the contents of the total phosphorus (P2O5) in the ICP-AES method are also demonstrated by its wide dynamic selected Magruder fertilizer samples varies from several per- range of calibration and high sensitivity. Furthermore, by the cent, as in organic fertilizers 9703 and 9504, to as high as 52% ICP-AES method, the same amount of fertilizer sample can be
  • 5. Table 5. ICP results of P2O5 recovery on 213.618 nm compared with Magruder average values Total P2O5, % Direct available P2O5, % Water-soluble P2O5, % Sample No. NPK Magruder value ICP resultsa Recovery, % Magruder value ICP results Recovery, % Magruder value ICP results Recovery, % 9703 4-2-0 2.85 ± 0.30 2.96 ± 0.03 103.9 2.52 ± 0.21 2.61 ± 0.02 103.4 0.12 ± 0.05 0.12 ± 0.00 100.0 9504 6-2-0 4.37 ± 0.44 4.80 ± 0.02 109.8 3.31 ± 0.45 3.47 ± 0.03 104.8 2.71 ± 2.48 0.47 ± 0.01 17.3 b 9401 10-10-10 10.26 ± 0.09 10.10 ± 0.08 98.4 10.55 ± 0.01 10.26 ± 0.04 97.3 — — — 9808 10-10-10 9.92 ± 0.13 10.05 ± 0.03 101.3 9.55 ± 0.32 9.97 ± 0.11 104.4 6.56 ± 0.20 6.78 ± 0.03 103.4 9309 13-13-13 13.39 ± 0.17 13.54 ± 0.23 101.1 13.38 ± 0.16 13.40 ± 0.14 100.1 — — — 9506 19-19-19 19.68 ± 0.32 19.82 ± 0.31 100.7 19.74 ± 0.25 19.71 ± 0.37 99.8 18.20 ± 0.25 18.34 ± 0.08 100.8 9409 4-22-6 22.24 ± 0.25 21.87 ± 0.17 98.3 22.06 ± 0.19 22.18 ± 0.19 100.5 17.31 ± 0.34 16.55 ± 0.07 95.6 9402 7-23-22 22.85 ± 0.16 22.98 ± 0.18 100.6 22.54 ± 0.43 22.57 ± 0.31 100.1 17.80 ± 0.27 17.75 ± 0.30 99.7 9806 8-24-24 20.80 ± 0.19 20.83 ± 0.20 100.1 20.77 ± 0.20 20.74 ± 0.23 99.9 19.79 ± 0.33 19.89 ± 0.16 100.5 9606B 0-32-31 36.40 ± 0.49 36.85 ± 0.20 101.2 36.41 ± 0.51 36.52 ± 0.17 100.3 12.42 ± 1.57 11.69 ± 0.37 94.1 9811A 10-34-0 34.02 ± 0.59 34.02 ± 0.17 100 33.94 ± 0.31 33.98 ± 0.14 100.1 10.16 ± 4.21 33.47 ± 0.29 329.4 YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002 1245 896B 41.75 ± 0.64 42.21 ± 0.37 101.1 — — — — — — 9810A 18-46-0 6.72 ± 0.59 46.88 ± 0.17 99.9 46.56 ± 0.36 46.54 ± 0.17 100 43.52 ± 1.07 43.95 ± 0.28 101.0 0998A 0-46-0 46.31 ± 0.23 46.29 ± 0.36 100.0 46.18 ± 0.18 45.78 ± 0.20 99.1 42.74 ± 0.29 41.23 ± 0.27 96.5 9803B 11-52-0 51.06 ± 0.55 51.02 ± 0.24 99.9 50.85 ± 0.33 51.14 ± 0.39 100.5 44.62 ± 0.94 46.33 ± 0.39 103.8 a ICP results are expressed as the mean ± standard deviation for triplicate determinations. b — = No Magruder value provided with check sample.
  • 6. 1246 YANG ET AL.: JOURNAL OF AOAC INTERNATIONAL VOL. 85, NO. 6, 2002 weighed regardless of the phosphorus concentration, and no general, the precision and accuracy of ICP-AES determina- spike experiment is required for low phosphorus content. tions were close to the average values of Magruder standard The precision and accuracy of the methodology developed check fertilizer samples. Care must be taken in the determina- were tested by analyzing total P2O5 and direct available P2O5. tion of total P2O5 in fertilizer samples in which phosphorus For short-term precision testing (7 consecutive determinations), may exist in several forms. By the ICP-AES method, all phos- phate forms are analyzed, yielding a true total P2O5 value. the RSD of total P2O5 and direct available P2O5 were in the range of 0.6–2.2 and 0.8–2.6%, respectively. For long-term precision References testing (7 determinations over 7 consecutive days), the RSDs of total P2O5 and direct available P2O5 were in the range of (1) Official Methods of Analysis (1990) 15th Ed., AOAC, 0.7–3.5 and 0.8–3.9%, respectively. The precision of total P2O5 Arlington, VA, sec. 962.02 and direct available P2O5 determination was also excellent. (2) Dahlgren, S.W. (1962) Z. Anal. Chem. 189, 243–256 (3) Official Methods of Analysis (1990) 15th Ed., AOAC, Conclusions Arlington, VA, secs. 958.01, 963.03(a) (4) Fujiwara, K., Mignardi, M.A., Petrucci, G., Smith, B.W., & Winefordner, J.D. (1989) Spectrosc. Lett. 22, 1125–1140 The ICP-AES method enables the determination of total (5) Hamalova, M., Hodslavska, J., Janos, P., & Kanicky, V.J. P2O5, direct extraction available P2O5 (EDTA), and wa- (1997) J. AOAC Int. 80, 1151–1155 ter-soluble P2O5 in fertilizers by the same calibration curve. (6) Ardis, J.D., & Baker, A.M. (1997) J. AOAC Int. 72, 857–859 Wavelength 213.618 nm proved to be the best analytical (7) Jones, J.B. (1982) J. Assoc. Off. Anal. Chem. 65, 781–785 wavelength for phosphorus determination in fertilizers. In (8) Jones, J.B. (1983) Spectrochim. Acta 38B, 271–276