The Investigation of Fertilizer Analyses Using Microwave Digestion and the Agilent 720-ES

Application Note
Inductively Coupled Plasma-Optical Emission Spectrometers

Authors
Christine M. Rivera Doug Shrader

Introduction
Fertilizers play a vital role in sustaining crop yields by supplying essential plant nutrients such as macronutrients nitrogen (N), phosphorus (P2O5) and potassium (K2O). The optimum fertilizer ratio of these three elements can vary according to the type of plant material being fertilized. Secondary nutrients such as calcium, magnesium and sulfur and micronutrients boron, copper, iron, manganese, molybdenum and zinc also play important roles in plant growth. The purpose of these investigations was to evaluate microwave digestion procedures for two analyses of fertilizer samples. The experiment was divided into two phases. Phase 1 was to evaluate using microwave digestion to prepare fertilizers for the determination of As, Ca, Cd, Cu, Cr, Fe, K, Na, Mg, Mn, P, Pb, Se and Zn by simultaneous ICP-OES. Phase 2 was to evaluate using microwave digestion to prepare fertilizers for the determination of available phosphorus (P2O5) and potassium (K2O) by simultaneous ICP-OES. Traditionally, the preparation of samples for phosphorus and potassium is done by extraction with ammonium citrateEDTA. The samples are placed in a heated water bath and shaken for 1 hour. The reagents are added to warmed samples and the shaking must be continuous. The number of samples typically required for preparation is large and this process is extremely time-consuming. In this field, phosphorus is traditionally determined using an auto-analyzer, which can be tedious to set up and run. Potassium is typically determined by flame photometry. To simplify sample preparation and analysis, the CEM MARS Xpress microwave digestion system with stirring option and Agilent 720-ES simultaneous ICP-OES were used for both analysis phases.

Instrumentation
Agilent 720-ES
The Agilent 720-ES with axial torch configuration is a truly simultaneous ICP-OES with solid-state, Charge Couple Device (CCD) detection system. The custom-designed and patented CCD detector incorporates IMAP technology, whereby pixels are arranged in continuous angled arrays matched exactly to the image produced by the echelle optics. This provides true simultaneous measurement and full wavelength coverage from 167 nm to 785 nm.

Microwave Digestion System

CEM, Corp. MARSXpress is an ultra-high throughput microwave digestion system designed to make high-throughput sample preparation and research applications quick and easy. Forty high-pressure vessels, available in 55 mL or 75 mL sizes, can be processed per run with temperature control of every vessel.

Figure 1. MarsXpress digestion temperature profile.

All samples were diluted to 50.00 mL in plastic disposable tubes and filtered with 2 micron Teflon FilterMate. This high dirt trapping FilterMate is especially suitable for trace level analysis and is supplied with lot certification for trace metals. The filtered samples were transferred directly to the Agilent SPS3 autosampler for analysis on the Agilent 720-ES.

Calibration Solution Preparation

The calibration summary for Phase 1 is listed in Table 2.
Table 2. Elements As, Cd, Cr, Cu, Mn, P, Pb, Se, Zn Ca, Fe, K, Na, Mg Phase 1 Calibration Summary Concentration (mg/L) 0.5, 5, 10 and 50 5, 10, 100 and 1000

Sample Preparation
Phase 1
To verify the method, two Magruder fertilizer check standards (200204 and 200206), which form part of the association of American Plant Feed Control Officials (AAPFCO) round robin laboratory checks, and a certified reference material, Industrial Sludge (CRM-S-I) from High Purity Standards, were prepared for analysis. Approximately 0.5 g of sample was accurately weighed and transferred to 55 mL MARSXpress vessels. Then, 9 mL of HNO3 and 1 mL of HCl was added to each sample vessel. Samples were digested in duplicate. The microwave digestion method is summarized in Table 1.
Table 1. Microwave Digestion Settings Max power (W) 1200 % power 100 Ramp (min.) 15:00 Pressure Temp. (PSI) (C) 120 200 Hold (min) 15:00

Conditions
Instrument operating conditions are shown in Table 3.
Table 3. Parameter Spraychamber type Nebulizer type Nebulizer flow RF Power Plasma gas flow Auxiliary gas flow Uptake delay Stabilization delay Rinse time Internal standard Ionization buffer Integration time* Replicates Total analysis time# Instrument Operating Conditions Setting Double-pass, glass cyclonic SeaSpray 0.75 L/min 1.25 kW 15 L/min 1.5 L/min 20 s 10 s 15 s 2 mg/L yttrium 0.4% caesium 60 s 2 165 s

Stages 1

The total digestion time was 30 minutes. Figure 1 represents the average digestion temperature over time in the vessels during sample preparation.

*If Se is not required at detection limit concentrations, a 5 s integration time is adequate. # 55 s for sample sets not requiring low concentrations of Se to be measured.

Results and Discussion

Phase 1
The results for Phase 1 are summarized in Table 4. Many of the samples encountered in feed and fertilizer laboratories consist of high concentrations of nutrients. Some of these elements cause ionization interferences while others cause
Table 4. Results Summary As 188.980 mg/kg 141 2.05 5.75 Cu 327.395 % 0.0407 0.0461 1.010 Mn 294.921 % 0.51 0.036 0.014 Pb 220.353 mg/kg 6.8 1.16 1.88 Expected mg/kg 141 1.75 5.66 Expected % 0.0398 0.0307 0.976 Expected % 0.48 0.039 0.015 Expected mg/kg 5.7 2.18 2.15 Ca 370.602 % 0.0233 2.71 4.93 Fe 261.382 % 0.012 0.350 0.500 Na 589.592 % 0.94 0.31 0.57 Se 196.026 mg/kg NA 0.43 0.13

spectral overlap problems, for example, iron. The use of an ionization buffer, for example, 0.4 % caesium minimized the ionization interferences. The spectral overlap can be overcome by the advanced background correction techniques of the ICP Expert II software, such as fitted background correction and FACT (Fast Automated Curve-Fitting Technique) spectral deconvolution.

Sample labels units Sludge B Magruder 4B Magruder 6B Sample labels units Sludge B Magruder 4B Magruder 6B Sample labels units Sludge B Magruder 4B Magruder 6B Sample labels units Sludge B Magruder 4B Magruder 6B

Expected % 0.0242 2.48 5.94 Expected % 0.014 0.400 0.500 Expected % 0.94 0.29 0.58 Expected mg/kg NA 0.44 0.12

Cd 214.439 mg/kg 0.64 12.31 1.51 K2O 404.721 % NA 11.02 21.37 P 214.914 % P2O5 0.51 8.1 9.1 Zn 213.857 % 0.0244 0.043 0.003

Expected % NA NA NA Expected % K2O NA 10.54 20.54 Expected % P2O5 0.50 9.1 9.9 Expected % 0.0249 0.048 0.003

Cr 267.716 mg/kg 110 125.2 50.88 Mg 279.078 % 12.6 1.62 0.53

Expected mg/kg 111 132.6 51.08 Expected % 12.2 1.64 0.62

Phase 2 Available K2O and P2O5

The extraction reagent preparation requires 325 g EDTA and 650 g dibasic ammonium citrate dissolved in 19.5 L distilled water. With mixing, 390 mL of a 1:1 solution of NH4OH:H20 is then added. When the solution is cooled to room temperature, the pH is carefully adjusted to 7.0 with additional 1:1 solution of NH4OH:H20 and the final solution diluted to 26.0 L. The traditional method requires that 0.25 g of sample undergo extraction in 100 mL ammonium citrate reagent in a Wheaton bath stabilized to 65 C (the extraction solution is added to the warmed sample). Upon completion of the extraction procedure, the solutions are cooled and diluted to 250 mL with ammonium citrate/EDTA reagent.

The samples are then typically run on the flame photometer for available K2O and the auto-analyzer for P2O5. The first part of the Phase 2 experiment was to determine if ICPOES is a viable alternative technique for the determination of K and P. A set of ten fertilizer samples were extracted per the defined method and analyzed by the traditional techniques and ICP-OES. With the ICP-OES technique, beryllium was selected as the internal standard and 0.8% caesium as an ionization buffer. Optimum instrument conditions were found to be at a power of 1.1 kW and a nebulizer flow of 0.65 L/min. The total sample analysis time was 55 s/sample. A comparison of the results by technique for the determination of K and P are summarized in Table 5.
3

Table 5.

Traditional Methodology Verses ICPOES (1 Hour Water Bath Extraction) Results ICP-OES K2O (769.897 nm) (% w/v) 0 0.06023 0.24038 Flame photometer K2O (% w/v) ICP-OES P2O5 (214.914 nm) (% w/v) 0 0.1145 0.4581 0.68709 0.91612 1.3742 ICP-OES K2O (769.897 nm) (% w/v) 34.81 4.51 4.50 9.22 9.89 1.80 2.50 10.17 8.56 5.47 18.49 Flame photometer K2O (% w/v) 34.64 4.59 4.29, 5.11, 5.19 9.22, 9.30 9.80, 9.71 1.48, 2.46, 2.16 2.53, 3.03, 3.15 9.88 8.58 5.45 18.00 ICP-OES P2O5 (214.914 nm) (% w/v) 52.62 21.6 8.10 10.04 10.04 19.87 22.47 10.58 4.17 9.71 16.56 Auto-analyzer P2O5 (% w/v) 52.11 21.59 8.59 10.09 9.75, 9.95 20.07 22.49, 22.69 10.47 4.06 9.73 16.70, 16.45 Auto-analyzer P2O5 (% w/v)

Calibration solutions (units) Blank Std 1 Std 2 Std 3 Std 4 Std 5

Calibration solutions (units) NIST SRM 200a Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 Sample 10 Note: No internal standard for K2O.

The final step of the Phase 2 study was to mimic the extraction process using microwave digestion. The microwave is not used for total digestion of the fertilizer sample, but as a way to consistently heat the extraction to 65 C. Three Magruder fertilizers and NIST SRM 200a potassium dihydrogen phosphate (KH2PO4) were carefully weighed to

0.1 g into HP 5000 vessels. Using the 75 mL vessels, 75 mL of ammonium citrate/EDTA extraction fluid was added. Stirring bars were added to each sample to simulate the shaking process and the contents were heated to 65 C for 1 hour. Table 6 summarizes the results collected by ICP-OES for available K2O and P2O5.

Table 6.

Summary of Results for Microwave Extraction and Determination of K2O and P2O5 by ICPOES K2O 404.721 (% w/w) 0 K2O 769.897 (% w/w) 0 0.012 0.03038 0.06022 0.1223 0.2431 0.49789 K2O 404.721 (% w/w) 34.42 34.93 11.66 10.04 26.65 23.99 12.57 12.65 K2O 769.897 (% w/w) 34.58 34.34 10.45 10.48 25.41 24.88 13.66 13.66 13.00 25.42 10.54 Expected (% w/w) 34.61 P2O5 185.878 (% w/w) 52.44 52.70 20.71 20.90 22.33 22.25 14.04 14.09 P2O5 214.914 (% w/w) 52.56 52.44 20.36 20.75 22.07 22.10 13.85 13.86 13.00 22.54 20.82 Expected (% w/w) 52.11 0.06022 0.1223 0.2431 0.05785 0.11449 0.22881 0.05785 0.11449 0.22881 P2O5 185.878 (% w/w) 0 0.01139 P2O5 214.914 (% w/w) 0 0.01139

Calibration solutions(units) Blank Std 1 Std 2 Std 3 Std 4 Std 5 Std 6 Std 7

Calibration

Samples(units) NIST_SRM 200a NIST SRM duplicate MAG # 4 MAG # 4 duplicate MAG # 6 MAG # 6 duplicate MAG # 9 MAG # 9 duplicate

Conclusion
The preparation of fertilizer samples by microwave digestion/extraction for the determination of macro, secondary and micro nutrients by simultaneous ICP-OES was evaluated and found to compare well with more traditional methods. The combination of microwave and ICP-OES techniques resulted in significantly faster and simpler sample preparation and analysis, requiring only a single analytical system to measure all elements of interest.

Acknowledgements
Elaine Hasty, CEM Corporation, Matthews, NC Peter Kane, Office of Indiana State Chemist, West Lafayette, IN

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Agilent Technologies, Inc. Printed in the USA November 1, 2010 IO-037