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Soil Quality & Fertilizer Analysis

As countries worldwide pursue strategies towards more sustainable farming, soil quality and fertilizer analysis become vital in crop yields. Rapid determi-nation of the extractable elements in agricultural soil samples enables assess-ment of micronutrient content and provides an indication of possible deficien-cies. Because fertilizers have a high concentration of active ingredients, and a low concentration of contaminants, monitoring the purity is a difficult applica-tion. With MP-AES, ICP-OES and AAS, Agilent offers a comprehensive set of techniques resulting in significantly faster and simpler sample preparation and analysis, requiring only a single analytical system to measure all elements of interest.

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Determination of Mercury in aCertified Reference Sludge Materialusing the Agilent 710-ES

Author

Peter Doidge

Application Note

Inductively Coupled Plasma-Optical Emission Spectrometers

Introduction

Mercury is an element of great importance because of its toxicity. Over the last cen-tury, emissions of mercury due to human activities have resulted in a tripling of theconcentration of mercury in the atmosphere and surface oceans [1]. The main pre-sent-day sources of the additional man-made burden of environmental mercury arecoal combustion, municipal and medical waste incineration, and smelting [2].

Elucidation of the pathways resulting in human exposure to mercury remains a mat-ter of great interest. According to Liebert et al., “there is now [at the time theywrote]…” scientific consensus that “…the most prevalent source of mercury expo-sure for the general population is from dental amalgam, and chronic inhalation orswallowing of amalgam mercury vapor is the major contributor to the total bodyburden of mercury in the U.S.” [3].

Additional mercury body burdens may be derived from air, water or soils. Sewagesludges and compost from solid waste and sewage sludge often have relatively highmercury concentrations. Such organic wastes are often applied in agriculture as fer-tilizers, and although the recycling of waste is desirable, waste contamination bymercury may lead to higher concentrations of mercury in the soil to which it isapplied, compared to those found when the soil is conventionally fertilized [4, 5].

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Table 1. ICP Operating Conditions

Parameter Setting

Power 0.9 kW

Plasma gas flow 13.5 L/min

Auxiliary gas flow 1.5 L/min

Nebulizer type Glass concentric

Nebulizer pressure 240 kPa

Spraychamber type Glass cyclonic (single-pass)

Torch type Standard axial torch

Pump tubing Spraychamber waste–blue/blue

(1.65 mm ID)

Gas/Liquid separator waste–

purple/black (2.29 mm ID)

Instrument pump rate 45 rpm

Replicate read time (s) 5

Number of replicates 3

Sample delay time (s) 20

Stabilization delay time (s) 30

Fast pump Off

Table 2. VGA-77P Operating Conditions

Parameter Setting

Inert gas Argon

Pump tubing Sample–purple/black (2.29 mm ID)

Reductant–black/black (0.76 mm ID)

Acid/water–black/black (0.76 mm ID)

Solution uptake rate Sample–8 mL/min

Reductant–1 mL/min

Acid/water–1 mL/min

Determination of the levels of mercury in solid wastes is there-fore a matter of some interest. Concentrations of mercury insewage sludges are typically in the region of several parts permillion (by dry weight) [5]. A concentration of 5.6 µg/g hasbeen reported in Australian urban sewage sludge [6].

Atomic spectrochemical methods such as atomic absorptionspectrometry (AAS) and ICP-OES provide the required sensitiv-ity for the measurement of mercury at the concentrations thatare usually encountered in environmental analysis. Vapor gen-eration techniques for atomic spectrochemical analysis arewidely used because of the excellent sensitivities provided forseveral elements, including mercury. This application notedescribes a simple procedure for the determination of mercuryin a suitable solid organic reference material (NBS 2781,Domestic Sludge) by vapor generation coupled with ICP-OES.

Experimental

An Agilent VGA-77P (Vapor Generation Accessory) was usedwith an Agilent 710-ES (ICP-OES) equipped with a megapixelCCD detector. The operating conditions of the ICP instrumentand VGA are as shown in Tables 1 and 2. Vapor produced bythe VGA was injected into the plasma through the nebulizerand spraychamber. With the VGA in operation, the plasmawas run “dry”; accordingly, a lower-than-usual power was setin the method. The VGA was operated under conditions aspreviously described [7, 8]. Argon was used as the VGA carri-er gas. The use of nitrogen as the VGA carrier gas is notrecommended on ICP.

The instrument pump rate must be optimized to ensure thatthe gas-liquid separator of the VGA is pumped effectively andthe liquid level does not rise, or fill the gas-liquid separator. Apump rate of 40–45 rpm is usually sufficient for this purpose.This rate must be maintained whenever the VGA is in opera-tion with sample solution being pumped. This pump rate mustbe incorporated into the ICP method, and can be set as adefault on the Ignition page of the Instrument Setup windowin the ICP Expert II software, so that as soon as the plasma isturned on, the pump speed changes to the required value. Anautosampler was not used in this study.

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Standard Solutions and Reagents

Working solutions for mercury determination in the micro-grams-per-litre range were prepared from a mercury standard(May and Baker). All mercury solutions were stabilized with a0.01% solution of AIR potassium dichromate, as described byFeldman [9]; this procedure resulted in the stabilization of themercury solutions for many days. Calibration solutions wereprepared at concentrations of 5, 10 and 20 µg/L. Stannouschloride was used as the reducing agent, though sodiumborohydride has also been used with the VGA [7,8]. A solutionof SnCl2 was prepared as a 25% w/v solution in 20% HCl fromAlR grade SnCl2 (BDH) and AlR HCl (BDH). “Conditioning” ofthe VGA system was carried out according to advice byMoffett [10]. Before conditioning, the response for very lowHg concentrations may be variable. Conditioning of the activesites in the tubing carrying the solutions and reaction prod-ucts, can be achieved by running the highest concentrationHg calibration standard (in this case 100 µg/L) through thesystem, until the response for much lower concentrations (forexample, 1 µg/L) becomes stable.

Sample Preparation

The standard reference material NBS 2781 (Domestic sludge)was selected for analysis. 3 mL of mixed nitric and hydrochloricacids were added to approximately 0.1 g of the weighed SRM,in the volume ratio 2:1. This was digested on a hot plate forapproximately two hours, or until fuming ceased. The solutionwas cooled, filtered and diluted to 50 mL. A drop of Anti-Foam B(Sigma Chemical Co.) was added to the solution after filtering.

Results and Discussion

Detection Limits Detection limits determined for a 30-second replicate readtime on the Agilent 710-ES instrument are shown in Table 3.(Detection limits (DLs) were measured on two instrumentsand similar values were obtained for the two.) Under the oper-ating conditions used, it was found that the three lines usedgave similar DLs, with slightly better DLs for the 253 nm line.This differs from the typical behavior for Agilent ICP-OESinstruments with aqueous sample introduction, for which the185 nm and 194 nm lines both give slightly better detectionlimits than does the 253 nm line [11]. This may be a result ofthe use of lower RF power, a condition which tends to favorthe less “hard” spectral lines, as a result of the less efficientionization and excitation at the lower power.

Table 3. Detection Limits (µg/L) for Hg in Aqueous Solution

Replicate read time (s) 184.887 (nm) 194.164 (nm) 253.652 (nm)

30 0.023 0.022 0.020

Short-term precision, determined from the RSD of replicatemeasurements of a 5 µg/L standard with 5 second replicateread times, was usually 1–2% RSD.

Analysis of a Certified Reference MaterialContaining Hg Certified reference material NBS 2781 (Domestic sludge) wasanalysed by both “normal” calibration and by the method ofadditions. No difference was observed in the slopes of thegraphs determined by the two methods, indicating no chemicalinterference. As can be seen from the results in Table 4 for theanalysis of eight aliquots of the SRM, the recovery of mercuryis within the range of values encompassed by the uncertaintyin the concentration of the reference material.

Table 4. Results of Analysis of NBS 2781

Hg Concentration, mg/kg

Measured value 3.40 ± 0.13

Certified value 3.64 ± 0.25

Recovery % 93

Conclusion

An Agilent VGA-77P has been used with an Agilent 710-ES forthe analysis of a certified reference material (NBS 2781). Theresults obtained agree with certified values, within thecombined uncertainties of the two results.

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Agilent shall not be liable for errors contained herein orfor incidental or consequential damages in connectionwith the furnishing, performance, or use of this material.

Information, descriptions, and specifications in this publication are subject to change without notice.

© Agilent Technologies, Inc.Printed in the USANovember 1, 2010IO-036

References

1. R. P. Mason, W. F. Fitzgerald, and F. M. M. Morel,Geochim. Cosmochim. Acta, 58, 3191 (1994)

2. W. F. Fitzgerald and R. P. Mason, “Biogeochemical Cyclingof Mercury in the Marine Environment”, Chapter 3 in A.Sigel and H. Sigel, Metal Ions in Biological Systems, Vol.34: Mercury and its effects on Environment and Biology,(Marcel Dekker, Inc., N.Y., 1997), pp.53-111

3. C. A. Liebert, J. Wireman, T. Smith, and A. O. Summers,“The Impact of Mercury Released from Dental “Silver”Fillings on Antibiotic Resistances in the Primate Oral andIntestinal Bacterial Flora”, Chapter 15 in A. Sigel and H.Sigel, op. cit., pp.441-460

4. L. Bringmark, “Accumulation of Mercury in Soil andEffects on the Soil Biota”, Chapter 6 in A. Sigel and H.Sigel, op. cit.

5. A. Anderson, “Mercury in Soils”, Chapter 4 in J.O. Nriagu(ed.), The Biogeochemistry of Mercury in the Environment(Elsevier/North Holland, Amsterdam, 1979), pp.79-112

6. C. K. Tan, “Analysis of chromium and mercury species insewage sludges”, (unpublished thesis, Monash University(1999))

7. B. T. Sturman, Appl. Spectrosc., 39, p.48 (1985)

8. K. Brodie, B. Frary, B. T. Sturman, and L. Voth, Agilent AAInstruments At Work No. 38

9. C. Feldman, Anal. Chem., 46, 99-102 (1974)

10. J. H. Moffett, Measuring ultra-trace levels of mercury,Agilent AA Instruments At Work No. 104 (1991)

11. T. Nham (Agilent, Analytical Instruments.), unpublisheddata

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Rapid Measurement of Major, Minorand Trace Levels in Soils Using theAgilent 730-ES

Author

Vincent Calderon

Application Note


Introduction

As part of the global strategy for sustainable farming, considerable emphasis hasbeen placed on the need for fast, accurate and precise determination of elementsin agricultural soil. As a result, simultaneous ICP-OES has become a widely usedtechnique for reporting the health of soils in the agricultural industry.

This work describes the preparation and analysis of certified reference soil materialsusing the Agilent 730-ES simultaneous ICP-OES with CCD detection. The Agilent 730-ESincludes a switching valve system that improves the efficiency of sample introductionand washout, providing greater sample throughput and accuracy.

A microwave-assisted acid digestion, based on recommendations given in US EPAmethod 3051A, was used to rapidly extract the elements from the soil samples. Thismethod is not intended to accomplish total sample decomposition, and samplematrix compounds such as quartz, silicates, titanium dioxide, alumina and otheroxides are not easily dissolved. For many environmental monitoring purposes, theconcentrations of extractable elements are more important than total concentrations,as bound elements are not considered mobile in the environment [1].

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Preparation of Calibration Solutions

Calibration solutions were prepared from Inorganic VenturesInc. custom-grade multi-element solutions (VAR-CAL-1A,VAR-CAL-2A and VAR-MAJOR-1A) and from Spex CertiPrepsingle element solutions. These solutions contained the following elements:

VAR-CAL-1A (1000 mg/L): Mo, Sb, Sn, and Ti

VAR-CAL-2A (1000 mg/L): Ag, Al, As, Ba, Be, Cd, Co, Cr, Cu,Mn, Ni, Pb, Se, Th, Tl, U, V, and Zn

VAR-MAJOR-1A (5000 ng/L): Ca, Fe, K, Mg, and Na

Spex CertiPrep single element solutions: 1000 mg/L Al 1000 mg/L P 1000 mg/L Sr 1000 mg/L Ti

Tables 2 and 3 list the selected elemental wavelengths andstandard concentrations used to calibrate each element.Sensitivity, linear dynamic range and freedom from spectralinterferences were taken into consideration during wavelength selection.

Table 2. Calibration Standards for the Major and Minor Elements

Wavelength Std 1 Std2 Std 3 Std 4 Std 5 Std 6Element (nm) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

Al 396.125 2 10 20 100 200 500

Ca 317.933 1 10 20 100 200 500

Fe 234.350 1 10 20 100 200 500

Mg 285.213 1 10 20 100 200 -

K 766.491 1 10 20 100 – –

P 178.222 1 10 20 – – –

Na 588.995 1 10 20 – – –

Ti 336.122 1 10 20 – – –

Instrumentation

An Agilent 730-ES (simultaneous ICP-OES with axially viewedplasma) was used for the analysis.

The Agilent 730-ES features a custom designed CCD detector,which provides true simultaneous measurement and fullwavelength coverage from 167 to 785 nm. The patented CCDdetector contains continuous angled arrays that are matchedexactly to the two-dimensional image from the echelle optics.The thermally stabilized optical system contains no movingparts, ensuring excellent long-term stability.

The Agilent 730-ES also includes the productivity-enhancingSwitching Valve System (SVS) that provides more efficientsample introduction and washout than traditional sampleintroduction systems. The SVS consists of a software-con-trolled, 4-port switching valve that instantaneously rinses thespray chamber following sample measurement while simultaneously presenting the next sample for measurement.

A Mars % closed vessel, microwave digestion system fromCEM was used to digest the solid samples.

Solutions were presented to the spectrometer using theAgilent SPS3, Sample Preparation System.

Table 1 shows the operating parameters used in this work.

Table 1. Operating Parameters

Condition Setting

Power 1.2 kW

Plasma gas flow 15 L/min


Spray chamber type Glass cyclonic (single-pass)

Torch Standard axial torch

Nebulizer type Seaspray

Nebulizer flow 0.7 L/min

Pump tubing Sample: white-white (1.02 mm ID)Waste: blue-blue (1.65 mm ID)Buffer/Reference element: black-black (0.76 mm id)

Pump speed 15 rpm

Total sample usage 1 mL

Replicate read time 3 s


Sample delay time 20 s

Switching valve delay 17 s

Stabilization time 12 s

Rinse time 1 s

Fast pump On

Background correction Fitted

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Table 3. Calibration Standards for the Minor and Trace Elements

Wavelength Std 1 Std2 Std 3 Std 4 Std 5 Std 6Element (nm) (µg/L) (µg/L) (µg/L) (µg/L) (µg/L) (µg/L)

Cu 327.395 10 50 250 1000 10 000 100 000

Pb 220.353 10 50 250 1000 10 000 100 000

Mn 260.568 10 50 250 1000 10 000 100 000

Zn 206.200 10 50 250 1000 10 000 100 000

As 188.980 10 50 250 1000 10 000 –

Ba 455.403 10 50 250 1000 10 000 –

Cr 267.716 10 50 250 1000 10 000 –

Sr 407.771 20 50 250 1000 10 000 –

Ni 231.604 10 50 250 1000 – –

V 292.401 10 50 250 1000 – –

Cd 226.502 10 50 250 – – –

The calibration standard and blank solutions were prepared in> 18MW/cm3 deionized water supplied from a Milliporesystem and stabilized with 5% v/v HNO3 (Merck Tracepur).

A solution containing 2 mg/L yttrium and 1% w/v CsNO3 in5% v/v Tracepur HNO3 was introduced to the sample onlinevia the third channel of the peristaltic pump. Yttrium was usedfor reference element (internal standard) correction andcesium was used as an ionization buffer to eliminate ioniza-tion affects that potentially exist with such matrix types [2-3].

Sample Preparation

A closed-vessel microwave-assisted acid digestion was usedto extract the major, minor and trace elements from the soilsamples following USEPA method 3051A guidelines. Thismethod is designed to mimic extraction using conventionalheating with nitric acid (HNO3) and hydrochloric acid (HCl)and does not accomplish total decomposition of the sample.Therefore, the extracted analyte concentrations may notreflect the total content in the sample [4]. Certified referencematerials NIST SRM 2710 Montana Soil and NIST SRM 2709San Joaquin Soil were used to validate the method.

The soil samples were prepared by accurately weighing 0.25 gof sample into the microwave digestion vessels and adding 9 mL of 10M HNO3 (Merck Tracepur) and 3 mL of 10 M HCl(AnalaR). Following digestion, the solutions were cooled,then centrifuged for 30 minutes and transferred to 25.00 mLvolumetric flasks. Each solution was diluted to volume with>18MW/cm3 deionized water. Duplicate digestions werecarried out.

Table 4 shows the settings used for the temperature dependent,microwave assisted digestion.

Table 4. Settings Required for Microwave Digestion

Max. % Ramp Pressure Temp. Hold Stage power power (min) (PSI) (°C) (min)

1 600W 100 5:00 350 120 0:00

2 600 W 100 5:30 350 175 4:30

Stage 1 was added as a reflux step to remove particulatematter that adhered to the walls of the microwave vesselduring sample addition.

The moisture content of each reference material was deter-mined as the certified values are based on dry weights. Thesamples were oven dried at 110 °C for 2 hours then cooled ina desiccator for 4 hours. The data were adjusted accordingly.

Table 5. Moisture Content

Measured moisture Quoted moisturecontent content range

Montana soil (NIST SRM 2710) 2.3% 1.7%–2.3%

San Joaquin soil (NIST SRM 2709) 2.4% 1.8%– 2.5%


The measured concentrations of major, minor and trace ele-ments in the respective soil reference materials are reportedin Tables 6–10. Analyses were performed in triplicate and theerror reported for each result represents the largest variationfrom the mean value.

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Table 6. Extractable Major Elements in Soil

Al (Wt%) Ca (Wt%) Fe (Wt%) Mg (Wt%)

NIST SRM 2710 Montana soil Reference dataCertified median 1.8 0.41 2.7 0.57 Certified range 1.2–2.6 0.38–0.48 2.2–3.2 0.43–0.60

Sample data Digestion 1 2.07 ± 0.01 0.376 ± 0.003 2.50 ± 0.03 0.510 ± 0.016 Recovery 115 92 93 89

Duplicate data Digestion 2 2.05 ± 0.004 0.377 ± 0.001 2.50 ± 0.001 0.508 ± 0.005 Recovery 114 92 93 89

NIST SRM 2709 San Joaquin soil Reference data Certified median 2.6 1.5 3.0 1.4 Certified range 2.0–3.1 1.4–1.7 2.5–3.3 1.2–1.5

Sample dataDigestion 1 2.00 ± 0.01 1.38 ± 0.01 2.63 ± 0.01 1.15 ± 0.01 Recovery 77 92 88 82

Duplicate data Digestion 2 2.54 ± 0.02 1.38 ± 0.01 2.74 ± 0.01 1.21 ± 0.02 Recovery 98 92 91 86

Table 7. Extractable Major and Minor Elements in Soil

K (Wt%) P (Wt%) Na (Wt%) Ti (Wt%)

NIST SRM 2710 Montana soil Reference dataCertified median 0.45 0.11 0.054 0.10Certified range 0.37–0.50 0.106–0.11 0.049–0.062 0.092–0.11

Sample dataDigestion 1 0.497 ± 0.003 0.0677 ± 0.0008 0.0613 ± 0.0003 0.122 ± 0.001Recovery 110 62 114 122

Duplicate dataDigestion 2 0.492 ± 0.001 0.0681 ± 0.0001 0.0612 ± 0.0002 0.120 ± 0.0003Recovery 109 62 113 120

NIST SRM 2709 San Joaquin soil Reference dataCertified median 0.32 0.07 0.068 0.038Certified range 0.26–0.37 0.05–0.07 0.063–0.11 0.03–0.04

Sample dataDigestion 1 0.347 ± 0.001 0.0442 ± 0.0003 0.0636 ± 0.0005 0.0234 ± 0.0001Recovery 108 63 94 62

Duplicate dataDigestion 2 0.408 ± 0.004 0.0444 ± 0.0004 0.0684 ± 0.0003 0.0545 ± 0.0006Recovery 127 63 101 143

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Table 8. Extractable Major and Minor Elements in Soil

Zn (mg/kg) Mn (mg/kg) Cu (mg/kg) Ba (mg/kg) Sr (mg/kg)

NIST SRM 2710 Montana soil Reference data

Certified median 5900 7700 2700 360 100

Certified range 5200–6900 6200–9000 2400–3400 300–400 94–110

Sample data

Digestion 1 5815 ± 46 7054 ± 86 2426 ± 20 307 ± 4 90.9 ± 1.1

Recovery 99 92 90 85 91

Duplicate data

Digestion 2 5897 ± 18 7064 ± 10 2436 ± 5 306 ± 1 90.6 ± 0.2

Recovery 100 92 90 85 91

NIST SRM 2709 San Joaquin soil Reference data

Certified median 100 470 32 398 101

Certified range 87–120 360–600 26–40 392–400 100–112

Sample data

Digestion 1 87.2 ± 0.3 483 ± 3 29.2 ± 0.3 367 ± 1 88.7 ± 0.5

Recovery 87 103 91 92 88

Duplicate data

Digestion 2 84.2 ± 0.6 485 ± 6 29.3 ± 0.1 377 ± 3 91.4 ± 0.3

Recovery 84 103 92 95 90

Table 9. Extractable Major, Minor and Trace Elements in Soil

Pb (mg/kg) As (mg/kg) Cr (mg/kg) Ni (mg/kg) Co (mg/kg)

NIST SRM 2710 Montana soil Reference dataCertified median 5100 590 19 10.1 8.2Certified range 4300–7000 490–600 15–23 8.8–15 6.3–12

Sample dataDigestion 1 4433 ± 22 514 ± 4 19.3 ± 0.1 10.4 ± 0.1 8.90 ± 0.06Recovery 87 87 102 103 109

Duplicate dataDigestion 2 4484 ± 29 518 ± 1 19.2 ± 0.1 10.3 ± 0.2 8.99 ± 0.05Recovery 88 88 101 102 110

NIST SRM 2709 San Joaquin soil Reference dataCertified Median median 13 < 20 79 78 12Certified Rangerange 12–18 – 60–115 65–90 10–15

Sample dataDigestion 1 10.7 ± 0.1 15.3 ± 0.1 61.8 ± 0.2 67.7 ± 0.6 11.1 ± 0.1Recovery 82 – 78 87 93

Duplicate dataDigestion 2 11.0 ± 0.5 15.2 ± 0.6 72.5 ± 0.2 68.2 ± 0.3 11.5 ± 0.1Recovery 85 – 92 87 96

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Although a small amount of undissolved material wasobserved following microwave digestion, the overall mea-sured concentrations of extractable major, minor and traceelements in the soil samples were in good agreement withthe certified leach data.

The major and minor elements Al, Fe, Mg, Na and K werewithin 15% of the respective certified median values andwithin the certified range for Montana soil (NIST SRM 2710).The same can be said for San Joaquin soil (NIST SRM 2709)although variation between the original (digestion 1) andduplicate values (digestion 2) were found to be greater withthe measured value for magnesium in the original sample andpotassium in the duplicate falling just outside the certifiedrange. Good recovery was also achieved for calcium at 92%for both soil samples and duplicates, although the measuredconcentrations fell just outside the lower end of the certifiedrange. With a measured recovery of 62–63% in both soilsample types, phosphorus did not appear to undergo com-plete extraction, although the reproducibility of the extractionfor P was excellent. On the other hand, titanium producedmixed results suggesting incomplete extraction and inhomogeneity.

The majority of the remaining extractable major, minor andtrace elements (Zn, Mn, Cu, Ba, Sr, Pb, As, Cr, Ni, Cd, Co, Moand V) fell within the certified range. Those that did not fallwithin the certified ranges were within 16% of the certifiedmedian value.

Conclusion

Two certified reference soil materials, containing variablelevels of major, minor and trace elements were digested fol-lowing US EPA Method 3051A and analysed on the Agilent730-ES Simultaneous ICP-OES. Agreement between the measured and certified values was generally very good.

The switching valve, fast rinse accessory was also usedallowing more efficient introduction and washout of thesample from the sample introduction system. The determina-tion of 21 elements in a sample took less than 65 secondsand required approximately 1 mL of solution, making theAgilent 730-ES an excellent analytical tool for fast and efficient analysis of soils.

Table 10. Extractable Major, Minor and Ttrace Elements in Soil

Cd (mg/kg) Mo (mg/kg) V (mg/kg)

NIST SRM 2710 Montana soil Reference dataCertified median 20 20 43Certified range 13–26 13–27 37–50

Sample dataDigestion 1 16.4 ± 0.1 14.94 ± 0.1 48.74 ± 0.5Recovery 82 75 113

Duplicate dataDigestion 2 16.64 ± 0.1 14.4 ± 0.3 48.64 ± 0.1Recovery 83 75 113

NIST SRM 2709 San Joaquin soil Reference dataCertified Median median < 1 < 2 62Certified Rangerange – – 51–70

Sample dataDigestion 1 < 0.2 1.514 ± 0.03 60.04 ± 0.2Recovery – – 97

Duplicate dataDigestion 2 < 0.4 1.494 ± 0.05 74.24 ± 0.2Recovery – – 120

Note: < value indicates an undetected element with the < value expressed as 10 times the standard deviation of background emission.

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References

A. Ryan, “Direct analysis of milk powder on the Liberty SeriesII ICP-AES with the axially-viewed plasma”. ICP Instrumentsat work, 1997, ICP-21.

US EPA Method 3051A “Microwave Assisted Acid Digestionof Sediments, Sludges, Soils and Oils”. Revision 1, 1998.



Analysis of Soil Extracts Using theAgilent 725-ES

Author

Tran T. Nham

Application Note


Introduction

In agricultural science, soil samples are routinely analyzed for micronutrient con-tent. Analytical data permits an assessment of the nutrient levels available forplants, and provides an indication of possible nutrient deficiency.

Available metals in soil are extracted with a variety of reagents, for example, diethylenetriaminepenta-acetic acid (DTPA), EDTA, water and ammonium acetate, depending onthe soil type and the form of the element required [1–4].

Inductively coupled plasma optical emission spectrometry (ICP-OES) is a multi-ele-ment analytical technique that offers fast sample throughput, high sensitivity and awide dynamic range. Soil analysis with this technique is well established[1,3,5–7].This work describes the use of a radially-viewed simultaneous ICP-OES for theanalysis of different soil extracts.

2

1 M Ammonium Acetate Solution 77 g of ammonium acetate was weighed and dissolved in1000 mL of water. The pH was adjusted to 7.0 with ammoniaor acetic acid.

0.01 M Calcium Dihydrogen OrthophosphateSolution 1 g of calcium carbonate was weighed into a beaker and 5 mLof ultra-pure water was added. Slowly and with constant stir-ring, 1.4 mL of 85% orthophosphoric acid was added. Mixingwas continued until the calcium carbonate had dissolved. Thesolution was then made up to 1000 mL with ultra-pure water.

Preparation of Soil Sample Extracts

The soil samples were dried in a 40 °C oven for 24 hours, thenfinely ground and sieved through a 200 mesh sieve.

DTPA Extraction (for Zn, Fe, Mn, Cu) 10 g of soil sample was weighed into a 125 mL conical flask. 100 mL of 0.005 M DTPA solution was added. The flask was stoppered and shaken for half an hour at 180 oscillations/minute and the mixture was filtered.

Ammonium Acetate Extraction (for Na, K, Ca, Mg) 10 g of soil sample was weighed into a 125 mL conical flask, 100 mL of 1 M ammonium acetate solution at pH 7.0 was then added. It was shaken for half an hour at 180 oscillations/minute and the mixture was filtered.

Phosphate Extraction (for S) 10 g of soil sample was weighed into a 100 mL plastic bottle,50 mL of 0.01 M calcium dihydrogen orthophosphate solutionwas added. The bottle was stoppered and placed in a 5 rpmend-to-end tumbler for 16 hours and the mixture was filtered.


Wavelength Selection The selection of wavelengths was based on sensitivity, lineardynamic range and freedom from spectral interferences. Thewavelengths used and method detection limits for soilextracts are listed in Table 2.

The ICP Expert II software allows the simultaneous mea-surement of multiple wavelengths for a given element toextend its calibration range. This important analytical toolcalled MultiCal can also assist the analyst in confirming theanalytical results.

Instrumentation

An Agilent 725-ES with simultaneous CCD detection wasused for the measurements. The Agilent 725-ES features anechelle polychromator equipped with a custom designed andpatented CCD detector [8] producing continuous wavelengthcoverage from 167 to 784 nm. The polychromator can bepurged with either argon or nitrogen gas for measurements atlow UV wavelengths.

The sample introduction consisted of a one-piece standardquartz torch, V-groove nebuliser and a Sturman-Masters spraychamber. An Agilent SPS3 autosampler was used to introducethe solutions to the ICP.

The operating parameters are listed in Table 1.

Table 1. Instrument Operating Conditions

Condition Setting

Power 1.2 kW




Pump speed 15 rpm

Integration time 5 s

Points per peak 2


Sample delay time 35 s

Stabilization time 10 s

Background correction Fitted

Reagents and Standards

All chemicals and reagents used were of analytical reagentgrade. All standards and blanks were matrix-matched with thesamples. All reagents and standards were prepared or dilutedin ultra-pure water (resistivity >18.2 MW/cm at 25 °C) suppliedfrom a Millipore water filtration system.

Preparation of Extraction Solutions

0.005 M Diethylene Triaminepenta-Acetic Acid(DTPA) Solution 1.96 g of DTPA, 14.92 g of triethanolamine and 1.47 g ofCaCl2.2H2O were weighed into a beaker and dissolved in1000 mL of ultra-pure water. The pH was adjusted to 7.3 with concentrated HCl or triethanolamine.

3

Table 2. Wavelengths and Estimated Detection Limits Obtained at 5 sIntegration Time

Stage Wavelength Method detection limits (µg/L)

Ca 422.673 15

Ca 317.933 30

Ca 183.738 1000

Ca 220.861 5000

Cu 324.754 10

Cu 327.395 10

Fe 238.204 10

Fe 259.940 25

K 766.491 30

Mg 279.800 100

Mg 279.079 300

Mg 278.142 1000

Mn 257.610 1.5

Mn 259.372 2

Na 588.995 10

S 181.972 150

Zn 213.857 5

Zn 206.200 25

Analysis of DTPA Extract for Zn, Fe, Mn, Cu The mean results of the analysis of control soil samples 1 and2 are listed in Table 3. The measured values are in goodagreement with the certified values.

Table 3. Results of Cu, Fe, Mn and Zn in DTPA Extract

Concentration (mg/L)

Control sample 1 Control sample 2

Measured Certified Measured Certifiedconcentration range concentration range

Cu 0.23 ± 0.01 0.20–0.24 0.130 ± 0.001 0.11–0.13

Fe 13.20 ± 0.03 11.90–15.20 2.49 ± 0.01 2.10–2.60

Mn 3.03 ± 0.02 2.60–3.10 1.410 ± 0.001 1.10–1.40

Zn 0.330 ± 0.001 0.30–0.36 0.042 ± 0.001 0.03–0.04

Analysis of Ammonium Acetate Extract for Na, K,Ca, Mg The mean results of the analysis of control soil samples 1 and2 are listed in Table 4. The measured values are in goodagreement with the certified values.

Table 4. Results of Ca, K, Mg and Na in Ammonium Acetate Extract




Ca 425 ± 3 430–444 64.7 ± 0.8 67–72

K 11.7 ± 0.9 11.7–12.9 5.6 ± 0.1 5.4–6.2

Mg 76.8 ± 1.2 76–83 13.1 ± 0.5 13.4–14.4

Na 8.0 ± 0.5 7.6–8.3 22.1 ± 0.1 21.6–22.6

Analysis of Phosphate Extract for Sulfur The primary S 181.972 nm line is recommended over the sec-ondary S 180.669 nm line because of spectral interferencefrom calcium (Ca 180.672 nm) at the S 180.696 line. However,with the use of FACT [9], both lines gave similar results.

FACT is a Fast Automated Curve-fitting Technique that pro-vides real time spectral correction to solve spectral interfer-ence by deconvolution. The corrections are done in real timewith no time penalty and can be applied retrospectively.Figure 1 shows the spectrum of control soil sample 1 at S 180.669 nm with FACT.

Figure 1. Spectrum of control soil sample 1 at S 180.669 nm.A is the signal trace of the soil sample.B is the FACT model of the interference (Ca 180.672 nm).C is the FACT deconvolution of the S analyte at 180.669 nm.





The mean results of the analysis of control soil samples 1 and2 are listed in Table 5. The measured values are in good agreement with the certified values.

Table 5. Results of S in Soil Extract




S 181.972 2.63 ± 0.05 2.40–3.00 7.58 ± 0.02 6.80–8.00

S 180.669 (with FACT) 2.70 ± 0.01 2.40–3.00 7.68 ± 0.01 6.80–8.00

Acknowledgements

Many thanks to John L. Lomas of Incitec Ltd. for the supply ofsoil extracts and the review of this document.

References

1 D. J. David, “Analysis of Soils, Plants, Fertilizers and OtherAgricultural Materials”, Prog. Analyt. At. Spectrosc., 1978,1, 225

2 W. L. Lindsay, W. A. Norvell, “Development of a DTPA SoilTest for Zinc, Iron, Manganese and Copper”, Soil Sci. Soc.Amer. J., 1978, 42, 421

3 “Inductively Coupled Plasma Emission Spectroscopy. PartII : Applications and Fundamentals”, P. W. J. M. BoumansEd., John Wiley and Sons Inc., New York, 1987, Chapter 4

4 G. E. Rayment and F. R. Higginson, “AustralianLaboratory Handbook of Soil and Water ChemicalMethods”, Inkata Press, Sydney, 1992

5 R. L. Dahlquist, J. W. Knoll, “Inductively Coupled PlasmaAtomic Emission Spectrometry Analysis of BiologicalMaterials and Soils for Major, Trace and Ultra-traceElements”, Appl. Spectrosc., 1978, 32, 1.

6 D. W. Hoult, M. M. Beaty, G. F. Wallace, “Automated,Sequential, Multielement Analysis of AgriculturalSamples by Inductively Coupled Plasma EmissionSpectroscopy”, At. Spectrosc., 6, 1980, 157.

7. R. A. Issac, W. C. Johnson, “High Speed Analysis ofAgricultural Samples using Inductively Coupled PlasmaAtomic Emission Spectroscopy”, Spectrochim. Acta,1983, 38, 277.

8. A. T. Zander, R. L. Chien, C. B. Cooper, P. V. Wilson, “AnImage-Mapped detector for Simultaneous ICP-AES”,Anal. Chem., 1999, 71, 3332.

9. C. Webb, A. T. Zander, P. V. Wilson, G. Perlis, “A FastAutomated Spectral Curve Fitting Tachnique for ICP-AES”, Spectroscopy, 1999, 14(5), 58.



The Latest Advances in AxiallyViewed Simultaneous ICP-OES forElemental Analysis

Author

Michael B. Knowles

Application Note

Inductively Coupled Plasma-Optical Emmision Spectrometers

Background

Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) is a populartechnique of elemental analysis. ICP is applicable to around 73 elements and pro-vides fast multi-element analysis with superior detection limits to atomic absorptionspectrometry (AAS) for many elements.

2

restricted to upper concentration limits of just 10–100 parts-per-million. This linear dynamic range problem spurred inter-ested in "dual viewed" plasmas - a horizontal plasma viewedalternately from the end or from the side. Dual viewed sys-tems however require samples to be analyzed twice - oncewith each viewing mode, and so productivity is restricted.

The reputation of axial ICP systems has unfortunately beenundermined by these historical observations. The purpose ofthis paper, is to review the latest advances in ICP-OES detec-tors, software and sample introduction systems which lead tomodern simultaneous axially viewed ICPOES systems thatovercome these perceptions. Today’s modern axially viewedICP systems provide the productivity of a single analysis withwide dynamic range from one plasma view.

Advances in ICP-OES Detector Design

Early ICP designs used photomultiplier tubes (PMT) to detectlight emitted from the plasma. PMTs could be used in eithersimultaneous ICP systems, with multiple detectors beingplaced around a Rowland circle or coupled to a sequentialscanning monochromator such as a Czerney-Turner design.The disadvantages of each of these approaches is clear -using discrete detectors to measure each wavelength meansyou have to choose the wavelengths to measure ahead oftime - restricting future flexibility. Sequential scanningdesigns, while more flexible, require more time to completean analysis.

In the early 1990s various groups developed solid state simul-taneous detection systems either based on Charge CoupledDevices (CCD) or Charge Injection Device (CID) designs.These devices differ in the way in which they measure theelectronic charge created on the surface of the detector. Auseful review of these technologies was provided by Harnlyand Fields in 1997 [3]. With both detector types, an array oflight sensitive detectors or pixels is used to convert theincoming photons into electrons for measurement.

These detectors are generally used in conjunction with anechelle polychromator which creates a 2 dimensional spec-trum from the light emitted by the plasma. The emitted light issplit both into its component optical orders (creating a seriesof "rows" of light) and also into its component wavelengths.One CCD design implemented in the early 1990s positionedthe light sensitive pixels at the locations of preferred wave-lengths [4]. This design became known as the Segmented

Initially ICP-OES systems featured a vertically-orientedplasma. The plasma was "viewed" by the optical system fromthe side, Figure 1. This configuration is known as "radialviewing" and has the advantage of providing immediate vent-ing of exhaust gases and waste heat to an overhead extrac-tion system. In the mid 1970’s workers began to develop end-on or axially viewed plasma systems [1]. The aim of axialviewing is to observe a longer path length in the analyte-richcentral channel, while avoiding viewing the surroundingintense argon plasma [2]. This approach provides improvedsignal to noise ratio and hence better detection limits. Axiallyand radially viewed plasmas are shown schematically inFigure 1.

Axially viewed plasma systems find application where bestsensitivity is needed, particularly environmental analyses ofwaters and wastes. Axially viewed ICP-OES offers a viableand more robust alternative to more expensive ICP-MassSpectrometry systems while meeting the detection limitrequirements of most regulatory bodies. Historically, the per-formance of axially viewed ICP systems was thought to belimited by injector tube blockage and subsequent signal driftwhen solutions containing high dissolved solids are aspirated.In addition, the limitations of older ICP detector designsmeant that the linear dynamic range of axial ICP was

Figure 1. Schematic diagram of radial and axially viewed plasma systems,note the three concentric tubes of the torches, the vertical orien-tation and side viewing of the "radial" torch and the horizontalorientation and end-on viewing of the "axial" torch.

3

Array CCD detector or SCD. Pixels were created in smalllinear groups positioned to detect the preferred suite of wave-lengths. The SCD used just 6336 pixels, presumably in anattempt to minimize perceived limitations in “readout speedand photometric data quality”. The restricted number of pixelsno doubt matched the limited data processing capabilities ofthe electronics and computers then in use. The SCD is stillused today with a current ICP-OES design. The limitations ofthe SCD are clear - pixel groups are positioned only at loca-tions of preferred wavelengths - thereby imposing the samerestrictions of wavelength choice and flexibility as the multi-ple PMT based designs of the 1970s and 1980s. Barnardet. al. [4] state that the SCD provides only “5.7% coverage ofthe spectrum from 167 to 782 nm”. Because of this inherentrestriction on available wavelengths current ICP designsbased on SCD technology cannot take advantage of theimprovements in linear dynamic range that can be obtainedby using multiwavelength data. As a result, alternativeplasma viewing methods, such as the dual view systems,were developed to compensate for this lack of linear dynamicrange.

The Vista series of simultaneous ICP-OES spectrometerswere introduced in1998. In developing the Vista series,Agilent took advantage of the availability of the next genera-tion of CCD detectors [5]. The VistaChip (Figure 2) CCDfeatures over 70,000 pixels positioned to exactly match thefree spectral range of the two dimensional echellogram.Zander et. al. [5] referred to this as "image mapping", withthe pixels being positioned so as to match the exact angle

and alignment of 70 orders of light coming from the echellespectrometer. The placement of the pixels in continuousrows provides complete and continuous wavelength coverageof 96% of the analytical spectrum. This approach opens up amajor advantage of ICP-OES - using alternative wavelengthsto avoid spectral interferences and to extend linear dynamicrange by using wavelengths in combination.

In August 2000, the world’s first array CCD detector applied tosimultaneous ICP-OES with the Vista- MPX was announced.The MPX detector features over 1.1 million pixels arranged inan X-Y array - again providing up to 96% coverage of the ana-lytical spectrum from a single simultaneous reading. TheVista-MPX achieves the linear dynamic range and flexibilityadvantages of the Vista image mapped CCD, in an even moreaffordable package. Both systems provide the advantages oftrue simultaneous ICP-OES, with simultaneous backgroundcorrection and internal standardization providing more accu-rate and precise results. In addition, the systems include nomoving optical components, resulting in excellent long termstability and analysis speeds compared to sequential scan-ning systems. The grating and prism of the echelle spectrom-eter used in the Vista series are fixed and the optics ther-mostatted providing long term drift-free performance withoutthe need for correction lamps. With most axial and dual viewsystems the ICP torch is oriented horizontally and viewedend-on (Figure 1). This orientation is preferred because end-on viewing of a vertical (radially viewed) plasma is more diffi-cult due to hot, corrosive vapors travelling past the viewingoptics.

Figure 2. The Agilent VistaChips - the Vista Pro CCD (left) and the Vista-MPX CCD (right). The Vista Pro CCD image shows the continuous lines of pixels (pho-tosensitive detectors) exactly positioned to match the spectral output from the echelle spectrometer. Note the differing slopes and separations ofthese "diagonal linear arrays" of pixels. The Vista-MPX CCD (right) is an array detector with over 1.1 million pixels in an X-Y grid.

4

Advances in Axial Viewing Systems

The Horizontal, Axially Viewed Plasma

• Offers 4–10x improvement in sensitivity compared to theradial view, due to longer path length of measurement

• Is ideal for routine analysis of samples containing lessthan 5% dissolved solids. With simple modifications tothe sample introduction system Agilent axial ICP now cananalyze 25% dissolved solids solutions directly for24 hours.

• There are key differences between axially viewed plas-mas. Agilent’s Cooled Cone Interface (CCI) displaces thecooler tail flame of the plasma away from the opticalpath, resulting in greater linear dynamic range and asignificant reduction in atomization and recombinationinterferences.

• Agilent’s CCI requires only a small counter flow of argongas, 2.5 L/min. The alternative shear gas approach usedon many dual view systems requires very high volumes ofgas, from 15-20 L/min, to displace the plasma from theoptical path. This gas must be nitrogen to measure below190 nm.

• Agilent’s CCI design makes the axially viewed plasmaideal for analyzing organic solvents.

The axially viewed plasma provides the benefits of improvedsensitivity and detection limits and this performance has seenthis configuration grow in popularity in the past decade.Table 1 shows the improvement factors in detection limitsthat can be obtained using axial viewing compared to radialviewing, typically this factor is between 4–10 times. Axiallyviewed ICP systems achieve detection limits that meet themajority of requirements for drinking water, waste water andother important environmental applications. The axiallyviewed ICP easily meets the detection limit requirements ofthe US EPA [6] for example.

Table1. Comparison of 3 s Detection Limits for Radially and AxiallyViewed Vista-Pro ICP. All Data was Collected Using 30 SecondsIntegration Times [7]

3 s Detection LimitsWavelength Vista-PRO Vista-PRO Improvement

Element (nm) radial (µg/L) axial (µg/L) factor

Ag 328.068 1 0.3 3.3Al 167.016 0.9 0.2 4.5As 188.979 5 1.5 3.3Au 267.595 5 1.0 5B 249.773 0.6 0.1 6Ba 455.403 0.15 0.03 5Be 234.861 0.05 0.01 5Bi 223.061 6 2 3Ca 396.847 0.06 0.01 6Cd 214.438 0.6 0.05 12Ce 418.660 2 2 1Co 238.892 1 0.2 5Cr 267.716 0.9 0.15 6Cu 327.396 1 0.3 3.3Fe 259.940 0.8 0.1 8K 766.490 4 0.3 13.3Li 670.784 1 0.06 16.7Mg 279.553 0.04 0.01 4Mn 257.610 0.08 0.03 2.7Mo 202.030 2 0.5 4Na 589.592 2 0.15 13.3Ni 231.604 1.4 0.3 4.7P 177.432 5 2 2.5Pb 220.353 5 0.8 6.3S 181.971 10 5 2Sb 231.147 5 2 2.5Se 196.026 6 2 3Si 251.611 2.2 1.4 1.6Sr 407.771 0.05 0.01 5Ti 334.941 0.2 0.1 2Tl 190.790 6 2 3V 292.402 0.7 0.2 3.5W 207.911 3.5 2 1.8Zn 213.856 0.8 0.2 4Zr 343.823 0.9 0.3 3

5

High Solids Capabilities

The axially viewed ICP provides excellent long term stabilityfor samples containing up to 5% dissolved solids using stan-dard sample introduction systems. With normal rinsing rou-tines, these samples can be analyzed throughout the dayusing an axially viewed ICP. Most samples fall below this highdissolved solids limit. For example, if 1g of sample is digestedand diluted to 100 mL this represents 1% dissolved solids inthe sample. Figure 4 shows the long term stability of theAgilent axially viewed Vista ICP for the continuous analysis of5% sodium chloride solution [9].

The Agilent axially viewed ICP systems all share the sameviewing configuration, shown in Figure 3. The plasma isdirected at a Cooled Cone Interface (CCI), consisting of awater cooled nickel cone with a large sampling orifice cut inits tip. A small counter flow of argon gas passing through thecone ensures that the heat and vapors from the plasmacannot compromise the optical system, which is further pro-tected by a quartz window. The CCI displaces the coolerplasma tail away from the optical path of the ICP instrument.It is in this cooler region of the plasma that analyte self-absorption, vaporization and ionization interferences canoccur.. Brenner and Zander concluded [8] that “removal ofthe cool fringe reduces matrix effects due to Easily IonizableElements and Ca and extends the linear range of calibrationand determination.”

Figure 3. Photo of Agilent’s Cooled Cone Interface. The cooler red zone of the plasma can be seen displaced around the outside of the cone, while aspiratingYttrium. The large central hole in the cone allows the optical system to observe the central channel of the plasma. A counter flow of argon gas and asealed optical window behind the cone, protect the optical system.

Figure 4. The stability of a range of elements from a continuously aspirated solution of 5% NaCl using the Agilent Vista-MPX simultaneous ICP-OES. Percentstandard deviation over a period of 3.5 hours was less than 2.5% in all cases. Note this analysis was conducted without between-sample rinsingwhich would further extend operation time.

6

Recently, a range of new spraychamber, nebulizer and torchoptions has been developed for ICP-OES which allows longeranalysis periods for higher levels of dissolved solids. Theseoptions include double pass spraychambers, "v-groove" nebu-lizers, wider bore injector tubes and demountable axial torchdesigns. By simply selecting appropriate sample introductionsystem components, long term analysis of high levels of dis-solved salts is now obtainable. An example of this work isshown in Figure 5 [10]. Using a modified torch with an axiallyviewed Vista-MPX simultaneous ICP-OES, the direct analysisof 25% sodium chloride solutions was demonstrated for over24 hours of continuous aspiration. The precision over24 hours ranged from 3.3% to 5.2% relative standard devia-tion. This work shows that the high salts stability of theAgilent axially viewed ICP’s is dependent upon the choice ofsample introduction system and not on the instrument itself.In this way, the performance of a radially viewed ICP can beobtained from an axially viewed ICP without the need for dualview optics.

Linear Dynamic Range

Linear Dynamic Range (LDR) is an important performancecharacteristic of ICP spectrometers as it defines the upperand lower limits of analyte concentrations that can be accu-rately measured. The lower end of this scale is defined bydetection limits (see Table 1) or determination limits and theupper end is defined by the limits of calibration linearity. TheUS EPA [6] uses a 5% calibration accuracy definition to deter-mine this upper concentration limit. LDR limitations are oftencited as the need for dual view plasma systems - that is, it isclaimed that to measure high levels of analytes (> 100 mg/L)both the radial view and the axial view are required in the onespectrometer. Since both views cannot be measured simulta-neously, the dual view approach slows down the productivityof the analysis.

Figure 5. The continuous analysis of 25% sodium chloride solution over 24 hours using a Vista-MPX axially viewed ICP (expected concentrations 1mg/L). Thesolution was continuously aspirated without rinsing and no internal standard correction was used. The plasma torch was fitted with a high solidsinjector tube. A Sturman Masters double pass cyclonic spraychamber and v-groove nebulizer were used with an argon saturator accessory (ASA).

7

As noted earlier, many of the assumptions about the lineardynamic range of ICPOES systems may have been based upondetector and plasma interface design limitations of thatera [4]. With the introduction of Agilent’s Cooled ConeInterface (CCI) these limitations have been overcome and it ispossible to have wide linear dynamic range from one axiallyviewed plasma system without the need to analyze thesample twice. In the past, the linear dynamic range of axiallyviewed systems was limited by analyte selfabsorption due tothe longer path length of measurement. The Agilent CCI pro-vides extended linear dynamic range by optimizing the obser-vation of the central channel of the plasma and eliminatingobservation of the cooler plasma tail.

When coupled with the full wavelength coverage of theAgilent ICP-OES systems, the axially viewed configuration canbe used from parts-per-billion detection limits up to maximumconcentrations of percentage levels. This performance isshown in Table 2 [12], which shows the upper limits of lineardynamic range for elements using the axially viewed, simulta-neous Vista-MPX. Comparing these results to the detectionlimits in Table 1, it can be seen that a very wide dynamicrange can be obtained from one axially viewed ICP systemwith just one sample measurement.

Advances In Software Design

To take advantage of the full wavelength coverage ofAgilent’s CCD detector technology, the Vista simultaneousICP systems feature MultiCal, which automatically assignseach sample to the best wavelength for that result. If asample result falls within a particular concentration range it isautomatically assigned to the wavelength that is most appro-priate for that concentration. In this way the Vista series ofinstruments takes advantage of the availability of all of thewavelengths in the analytical spectrum - automatically com-bining the most sensitive wavelengths for best detectionlimits with less sensitive wavelengths for best dynamic range.

Table 2. Linear Dynamic Range Test Results on the Axially Viewed Vista-MPX with CCI, Showing Accurate Recoveries of Elements up to500 and 600 mg/L is Easily Possible. Vista CCI Provides RadialView Performance with the Benefits of Axial Sensitivity

Element LRA (mg/L) Recovery %

Ag 328.068 10 101Al 236.705 500 99Al 308.215 40 100

As 188.980 10 103Ba 585.367 200 95Be 313.042 5 101

Ca 315.887 100 99Ca 370.602 600 97Cd 226.502 5 99

Co 228.615 50 97Cr 267.716 20 100Cu 327.395 30 101

Fe 234.350 100 100Fe 258.588 500 95K 404.721 500 104

K 766.491 50 102K 769.897 200 101Mg 279.800 600 98

Mg 383.829 600 99Mn 257.610 50 97Na 330.237 600 97

Na 589.592 50 98Ni 231.604 50 97Pb 220.353 100 101

Sb 206.834 10 103Se 196.026 100 101Tl 190.794 100 101V 311.837 60 99

8

Figure 6, shows the MultiCal advantage, with a pair of calibra-tion graphs for calcium, measured on the Vista-MPX. Lowconcentration results are automatically reported from one cal-ibration graph and high concentration results reported from asecond calibration graph - extending the linear dynamic rangefor this element. Also in this example, the results from thetwo wavelengths have been mathematically combined intoone calcium result. In this case the average of the two cal-cium results from the two wavelengths has been used, how-ever users may also choose from weighted mean, minimumand median of the results. Only results that fall within thevalid calibration range of the wavelengths will be used inthese calculations – providing extra surety of data quality. Theoriginal wavelength columns can either be displayed (for fullinformation) or hidden (for simplicity and ease of use). By dis-playing all available wavelength information, the user is givenanother data quality control check, by comparing the accuracyof the results from two or more wavelengths for the sameelement.

Conclusions

In this paper we have reviewed the recent developments inthe design of axially viewed ICP-OES. Axially viewed ICP-OEShas emerged as the preferred viewing technique due to itsbenefits of enhanced sensitivity and detection. Agilent’sCooled Cone Interface is an optimized design that eliminateschemical and molecular interferences and extends the lineardynamic range of the axial ICP. This axial design combinedwith Agilent’s CCD detector technology provides simultane-ous measurement of all wavelengths and further extends thelinear dyanamic range of ICP-OES. With simple changes tothe sample introduction system, Agilent’s axially viewed ICP-OES can analyze high dissolved salt samples continuouslywith excellent long term stability.

Figure 6. The Agilent MultiCal advantage - the first column shows the mean result from two Ca wavelengths - 315.887 and 370.602 nm, automatically com-bined by the Vista-PRO software. The combined wavelengths allow calibration to 1000 mg/L from a single analysis on this axially viewed ICP. Thisextended linear dynamic range would normally only be possible with a radially viewed ICP. With MultiCal, the Vista ICP series provides both theextended linear dynamic range of a radial ICP and the excellent detection limits of an axially viewed ICP with one simple analysis. The accuracy ofthe results is established from the 50 mg/L and 500 mg/L Continuing Calibration Verification (CCV) results.

9

The unique MultiCal automates the intelligent assignment ofsample results to the most appropriate wavelength. The accu-rate measurement of high concentration matrix elements cannow be performed simultaneously with trace level detectionof other analytes of interest from one axial plasma viewingsystem and one measurement. MultiCal eliminates the needfor Dual View optics, enhances productivity and reducesargon consumption.

Agilent’s CCI and MultiCal approach offers significantadvantages that should see axially viewed ICP-OES remain apopular technique for many years to come.

Acknowledgements

The author would like to thank Tran Nham, Filippa Minnelliand Ingrid Szikla (all of Varian, Inc., Melbourne, Australia) andJean-Pierre Lener and Valerie Lecourbe (of Varian, Inc.France) for their contributions of data used in this paper.

References

1. M. H. Abdallah, J. J. Diemiaszonek, J. M. Mermet,J. Robin, C. Trassy, “Etude Spectrometrique D’un PlasmaInduit Par Haute Frequence, Partie 1: Performances anAlytiques, Analytica Chimica Acta, 1976, 84, 271-282

2. C. Dubuisson, E. Poussel, J-M. Mermet, “Comparison ofaxially and radially viewed Inductively Coupled PlasmaAtomic Emission Spectrometry in terms of signal-to-back-ground ratio and matrix effects”, Journal of AnalyticalAtomic Spectrometry, March 1997, 12, 281-286

3. J. M. Harnly, R. E. Fields, “Solid state array detectors foranalytical spectrometry” Applied Spectroscopy, 1995, 51,9, 334A-351A

4. T. W. Barnard, M. I. Crockett, J. C. Ivaldi, P. L. Lundberg,D. A. Yates, P. A. Levine, D. J. Sauer “Solid state detectorfor ICP-OES”, Anal. Chem., 1993, 65, 1231-1239

5. A. T. Zander, R-L Chien, C. B Cooper III, P. V. Wilson,“An image mapped detector for simultaneous ICP-AES”,Anal. Chem., 1999, 71, 3332-3340.

6. US EPA Contract Laboratory Program, Statement of Workfor Inorganics, Multi-media, Multi-concentration,Document Number ILM05.0, at www.epa.gov/oamsr-pod/pollard/ hq9915909/ilmo50c.pdf

7. J. P. Lener and V. Lecourbe, 2000, August, Varian InternalReport

8. I. B. Brenner, A. T. Zander, “Axially and radially viewedinductively coupled plasmas—a critical review”,Spectrochimica Acta, 2000, Part B 55 195-1240

9. F. Minnelli, 2001, January, Varian Internal Report.

10. Tran T. Nham, “Performance evaluation of a new axiallyviewed simultaneous ICP-OES using a megapixel CCDdetector for environmental applications” Paper 0-18,European Winter Conference on PlasmaSpectrochemistry, Norway, Feb, 2001.

11. I. Szikla, “Determination of 22 Elements Following USEPA Guidelines with a New Megapixel CCD ICP-OES”,Varian Instruments At Work, Number 30, Mar 2001.



Analysis of Plant Materials byVaporGeneration AA

Author

Keith G. Brodie

Application Note

Atomic Absorption

Introduction

Arsenic and antimony are widely used in modern industries although they are toxicto both man and animals. Significant levels of these elements can be found through-out our environment in such diverse sources as soils, plants, fish and animals.Selenium, on the other hand, is an essential trace element but can be toxic at higherlevels. The essential role of selenium in animal nutrition was first demonstrated in1957 [1] but man’s requirements are not yet fully defined.

The concentration of these elements in foods is dependent on the soil conditionsand ultimately on the methods of preparation of the food. The levels found in animalproducts is dependent on the plant material or other animal food source.

It is of considerable interest therefore to establish the level of these elements, aswell as other toxic metals, in soils, plants and animal tissues.

Arsenic, antimony and selenium have been determined at very low levels by atomicabsorption for many years, and vapor generation atomic absorption offers the mostsensitive means by which they can be measured.

The results of extensive collaborative studies on acid digestion techniques, andhydride generation AA for the determination of arsenic and selenium in foods havebeen reported [2,3]. Several laboratories were involved in those reports.

Sample digestion procedures have ranged from ashing in a furnace with a magne-sium nitrate solution [4], to hot digestion in acids usually comprising nitric and per-chloric mixtures [5]. Agilent instruments have been used for the vapor generationmeasurement of selenium levels in plant and biological material after suitable aciddigestion [5,6].

Many laboratories are reluctant to use perchloric acid with digestions of organicmaterials because of the potential risks involved [7,8]. For this reason a number ofdigestion procedures have been devised which have eliminated perchloric acid.Sulphuric acid increases the boiling point of an acid digestion mixture and improves

2

The digested mixture was made up to 25 mL to give a finalsolution in 7 M hydrochloric acid. This stock solution was useddirectly for the determination of selenium, but was diluted 1 in10 with 7 M hydrochloric acid for the determination of arsenicand antimony.

Some quantities of powdered orchard leaves were also spikedwith known amounts of arsenic, antimony and these sampleswere taken through the same digestion procedure. A standardadditions calibration was thus established. Replicate sampleswere taken for each. Blank reagents were also prepared.

Samples were prepared in 7 M hydrochloric acid to ensurethat any SeVI formed in the digestion procedure, was reducedto the required SeIV prior to analysis. This treatment is commonly used [5,6,9,10].

The reduction of AsV (or SbV) to AsIII (or SbIII) was achieved bythe inclusion of potassium iodide in the sodium borohydridesolution [9].


Figures 1 and 2 show chart recorder traces for the standardadditions measurement of the digests for arsenic and anti-mony respectively. Approximately 40 seconds are required forthe signal to reach an equilibrium value after introduction ofthe sample. Replicate absorbance readings were taken in theplateau region. It is apparent on Figure 2 that a spike appearson completion of the signal, and this is due to a brief intro-duction of air before the next solution is pumped. Such anoccurrence is not uncommon.

Standard additions calibrations for arsenic and antimony arefeatured in Figures 3 and 4 respectively. The meanabsorbance is shown and two values are represented by theerror bars on the Figures.

That the standard additions technique was necessary, isdemonstrated by aqueous calibrations for those elements onthe same graphs. The calibration slopes are clearly different.

Table 1 shows the results obtained for arsenic and antimonyin the orchard leaves. Agreement with the certificate wasgood.

Table 1 NBS Orchard Leaves No. 1571

Element Certificate value µg/g Found* µg/g

As 10 ± 2 11 ± 2

Sb 2.9 ± 0.3 2.7 ± 0.2

* Mean of replicate determinations.

the action of the other oxidizing acids such as nitric. The onlydisadvantage of sulphuric acid is the tendency to form insolu-ble compounds but the presence of nitric acid avoids the pre-cipitation of trace metals with major components of thesample. Digestion mixtures of sulphuric, nitric and hydrogenperoxide have been used successfully for plant materials [7].

The results of the determination of arsenic, antimony andselenium in NBS orchard leaves (No 1571) by the vapor gen-eration technique are reported here. A digestion procedurewas prepared which did not contain perchloric acid.

Instrumentation

An Agilent AA-1475 with background correction and the VGA-76 were used in this study. The background signal was exam-ined for all solutions, but no background was found.Measurements were therefore reported with the backgroundcorrector off. Hollow cathode lamps were operated at the rec-ommended conditions and an Agilent 9176 strip chartrecorder displayed the traces.

For development of this analytical technique samples werepresented manually.

Absorbance mode was used and five 3-second integrationswere taken.

The printer was an HP 82905A model. The reagents used forthe VGA-76 were as follows:

Acid channel Concentrated hydrochloricacid.

Sodium borohydride channel 0.6% NaBH4in 0.5% NaOH and10% KI.

Sample Treatment

NBS orchard leaves (No. 1571) were dried at 80 °C and approxi-mately 0.5 g samples were accurately weighed and preparedfor analysis. The digestion procedure consisted of the additionof 5 mL concentrated sulphuric with swirling in a beaker. A 5mL volume of 30% v/v hydrogen peroxide was added slowlyand the reaction allowed to proceed. This addition of hydrogenperoxide was repeated, and when the reaction had subsided,the digestion mixture was heated on a hot plate.

After cooling, 2 mL of concentrated nitric acid was added andthe mixture heated for about 2 hours to remove excess nitricacid. A further addition of nitric acid with heating may berequired until the solution is a light straw color.

3

Figure 1. Chart recorder traces for the measurement of arsenic in digestedleaves.

Figure 2. Chart recorder traces for the measurement of antimony indigested leaves.

Figure 3. Calibration for the determination of arsenic.

Figure 4. Calibration for the determination of antimony.




© Agilent Technologies, Inc., 1985Printed in the USANovember 1, 2010AA050

The level of selenium in the leaves was quite low (0.08 µg/gm) and a value of 0.05 was obtained from just onemeasurement by the standard additions technique.

No further study was made on selenium here but details ofextensive work on selenium determination in agriculturalmaterials by the VGA-76 has been recently reported [10].

An alternative digestion procedure was also attempted inwhich nitric and sulphuric acids only were used. The mixturewas heated to remove excess nitric acid and the final solutionwas a light straw color. The recoveries from some samplesanalysed by this procedure were low, and this procedure wasnot pursued further.

Summary

The VGA-76 has been used to determine the amount ofarsenic and antimony in digested orchard leaves. A digestionprocedure was adopted which avoided the use of perchloricacid and it was necessary to use the standard additions cali-bration procedure.

References

1. K. Schwarz and C. Folz, J. Amer. Chem. Soc. 79 3293(1957).

2. M. lnhat and H. Miller, J. AOAC 60 1414 (1977).

3. M. lnhat and B. Thompson, J. AOAC. 63 814 (1980).

4. B. Pahlav an pour, M. Thompson and L. Thorne, Analyst106 1467 (1981).

5. O. Clinton, Analyst 102 187 (1977).

6. R. Mailer and J. Pratley, Analyst 108 1060 (1983).

7. M. Hoenig and R. de Borger, Spectrochim. Acta 38B 873(1983).

8. M. Knight, Argonne Natl. Lab., IL, U.S.A. ANL/LRP-TM-18 1980 pp 31.

9. K. Brodie, B. Frary, B. Sturman and L. Voth, VarianInstruments at Work No. AA-38, March 1984.

10. A. Gelman, Varian Instruments at Work, No. AA-44, Feb.1985.



Nitrogen Determination in Fertilizerby ICP-OES with an Extended Torch

Author

Tran T. Nham

Application Note


For the determination of nitrogen in fertilizer, colorimetry has been widely usedbecause of its high sensitivity. However, sample preparation is very time consumingand tedious for colorimetric measurements, while the ICP-OES technique can ana-lyze the sample solution directly. The purpose of this study was to examine the fea-sibility of the ICP-OES technique for the measurement of nitrogen in fertilizer.

The emission lines of nitrogen are in the vacuum region (N 174.272 nm and N174.525 nm), and a vacuum monochromator was used. To prevent the entrainmentof air into the plasma, an extended torch was essential.

2

Standard PreparationAll chemicals and reagents used were analytical reagent grade.

Urea and ammonium sulfate were used for the preparation ofstandards for urea and ammonium sulfate analysis. Bothstandards and blank were prepared in 0.4 M HCl solution.


It was observed that a nitrogen signal was detected in theblank solution. This was because of the presence of dissolvednitrogen in water, nitrogen contamination in the argon gasand residual entrainment from the surrounding air. Figure 1shows signal traces for a 2 wt% N standard and a blank solu-tion.

However, the background nitrogen peak can be subtractedand corrected for by applying background correction.

Long Term StabilityLong term stability measurement was performed after a cali-bration with a 1.5 wt% N standard solution and a blank. Thestandard was then analyzed as a sample every 5 minutes con-tinuously for a period of 90 minutes, as shown in Figure 2.Over the 90 minute period, the reproducibility was 1.44 %RSD.

ResultsThe N 174.272 nm line, with a detection limit (2 sigma) of 50mg/L, was selected for the measurement. The results of theN determination by ICP- S together with that found by col-orimetry are listed in Table 2.

Table 2. Results for Nitrogen Determination

Sample Nitrogen concentration (wt %)ICP- S Colorimetry

Urea 46.5 ± 0.2 46.4

Ammonium sulfate 20.1 ± 0.3 20.4

The ICP values are the mean of 3 individual determinations.The precision of the ICP measurement ranged from 0.1–1 %RSD. Typical precision of the colorimetric measurement is about 0.2 %RSD.

Experimental

InstrumentalAn Agilent Liberty 220 ICP spectrometer was used for themeasurement. The extended torch featured a longer outertube compared with the standard torch and a slotted cut-outon the side. A higher plasma gas flow of 22.5 L/min was usedto form a better shield from the surrounding air.

The operating parameters of the system for the measurementof nitrogen are listed in Table 1.

Table 1. ICP Operating Parameters

Power 1.5 kW

Plasma gas flow 22.5 L/min


Nebulizer type Glass concentric

Nebulizer pressure 1 80 kPa

Pump rate 15 rpm

Sample uptake rate 1.8 mL/min

Viewing height 8 mm

PMT voltage 650 V

Integration time 3 sec

Background correction Dynamic

Snout High

Sample PreparationUrea Sample

For ICP analysis: 10 g of sample was accurately weighed andtransferred into a 500 mL volumetric flask, then distilleddeionized water was added until the mixture was totally dis-solved. 20 mL of concentrated HCl was added and made up tovolume with distilled deionized water.

For the colorimetric method: 1 g of sample was accuratelyweighed into a 125 mL Kjeldahl flask, 20 mL of concentratedH2SO4 and 2 Kjeldahl catalyst tablets were added, and thenthe mixture was digested at 400 oC for 2.5 hours. After cool-ing, the mixture was transferred to a 500 mL volumetric flaskand made up to volume with distilled deionized water.

Ammonium Sulfate Sample

25 g of a ground sample was accurately weighed and trans-ferred into a 400 mL beaker. 150 mL of distilled deionizedwater and 20 mL of concentrated HCl were added. It was thenboiled for 10 minutes, cooled, transferred to a 500 mL volu-metric flask and made up to volume with distilled deionizedwater.

3

Conclusion

Studies have shown that the ICP- S technique can beapplied to the measurement of high level of nitrogen in fertil-izer. The ICP values are in good agreement with the colorimet-ric values. The precision of the ICP measurement ranged from0.1–1 %RSD.

The sample preparation procedure for colorimetry is time con-suming and tedious, especially for the urea sample. It takesabout 2.5 hours for complete sample digestion, while a simpledissolution only is required for the ICP-OES technique.

However, the sample weight required is 10 times higher withthe ICP technique than for the conventional colorimetricmethod, although sample availability is rarely a problem. It isnoted that for urea analysis, standard solution should be pre-pared from urea, not ammonium sulfate.

In summary, the Liberty 220 ICP spectrometer with anextended torch can be used to determine nitrogen in fertilizerat wt% level in a fraction of the time taken by the conven-tional colorimetric method.

Figure 1. Spectral scan of a 2 wt% N standard solution and a blank at the N 174.272 nm line.

Figure 2. Signal stability over 90 minutes of a 1.5 wt% N standard solution.




© Agilent Technologies, Inc., 1993Printed in the USANovember 1, 2010ICPES-14

Acknowledgement

Thanks are expressed to John L. Lomas of Incitec Pty Ltd,Brisbane for the supply of fertilizer samples and for theresults of colorimetric measurements.



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The Investigation of FertilizerAnalyses Using MicrowaveDigestion and the Agilent 720-ES

Authors

Christine M. Rivera

Doug Shrader

Application Note


Introduction

Fertilizers play a vital role in sustaining crop yields by supplying essential plant nutri-ents such as macronutrients nitrogen (N), phosphorus (P2O5) and potassium (K2O).The optimum “fertilizer ratio” of these three elements can vary according to the typeof plant material being fertilized. Secondary nutrients such as calcium, magnesiumand sulfur and micronutrients boron, copper, iron, manganese, molybdenum and zincalso play important roles in plant growth.

The purpose of these investigations was to evaluate microwave digestion proce-dures for two analyses of fertilizer samples. The experiment was divided into twophases.

Phase 1 was to evaluate using microwave digestion to prepare fertilizers for the deter-mination of As, Ca, Cd, Cu, Cr, Fe, K, Na, Mg, Mn, P, Pb, Se and Zn by simultaneousICP-OES.

Phase 2 was to evaluate using microwave digestion to prepare fertilizers for thedetermination of available phosphorus (P2O5) and potassium (K2O) by simultaneousICP-OES. Traditionally, the preparation of samples for phosphorus and potassium isdone by extraction with ammonium citrate—EDTA. The samples are placed in aheated water bath and shaken for 1 hour. The reagents are added to warmed sam-ples and the shaking must be continuous. The number of samples typically requiredfor preparation is large and this process is extremely time-consuming.

In this field, phosphorus is traditionally determined using an auto-analyzer, whichcan be tedious to set up and run. Potassium is typically determined by flame pho-tometry. To simplify sample preparation and analysis, the CEM MARS Xpressmicrowave digestion system with stirring option and Agilent 720-ES simultaneousICP-OES were used for both analysis phases.

2

Figure 1. MarsXpress digestion temperature profile.

All samples were diluted to 50.00 mL in plastic disposabletubes and filtered with 2 micron Teflon FilterMate. This highdirt trapping FilterMate is especially suitable for trace levelanalysis and is supplied with lot certification for trace metals.The filtered samples were transferred directly to the AgilentSPS3 autosampler for analysis on the Agilent 720-ES.

Calibration Solution Preparation The calibration summary for Phase 1 is listed in Table 2.

Table 2. Phase 1 Calibration Summary

Elements Concentration (mg/L)

As, Cd, Cr, Cu, Mn, P, Pb, Se, Zn 0.5, 5, 10 and 50

Ca, Fe, K, Na, Mg 5, 10, 100 and 1000

Conditions Instrument operating conditions are shown in Table 3.

Table 3. Instrument Operating Conditions

Parameter Setting

Spraychamber type Double-pass, glass cyclonic

Nebulizer type SeaSpray


RF Power 1.25 kW



Uptake delay 20 s

Stabilization delay 10 s

Rinse time 15 s

Internal standard 2 mg/L yttrium

Ionization buffer 0.4% caesium

Integration time* 60 s

Replicates 2

Total analysis time# 165 s

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

Instrumentation

Agilent 720-ES The Agilent 720-ES with axial torch configuration is a trulysimultaneous ICP-OES with solid-state, Charge Couple Device(CCD) detection system. The custom-designed and patentedCCD detector incorporates IMAP technology, whereby pixelsare arranged in continuous angled arrays matched exactly tothe image produced by the echelle optics. This provides truesimultaneous measurement and full wavelength coveragefrom 167 nm to 785 nm.

Microwave Digestion System CEM, Corp. MARSXpress is an ultra-high throughputmicrowave digestion system designed to make high-through-put sample preparation and research applications quick andeasy.

Forty high-pressure vessels, available in 55 mL or 75 mL sizes,can be processed per run with temperature control of everyvessel.

Sample Preparation

Phase 1 To verify the method, two Magruder fertilizer check standards(200204 and 200206), which form part of the association ofAmerican Plant Feed Control Officials (AAPFCO) round robinlaboratory checks, and a certified reference material,Industrial Sludge (CRM-S-I) from High Purity Standards, wereprepared for analysis. Approximately 0.5 g of sample wasaccurately weighed and transferred to 55 mL MARSXpressvessels. Then, 9 mL of HNO3 and 1 mL of HCl was added toeach sample vessel. Samples were digested in duplicate.

The microwave digestion method is summarized in Table 1.

Table 1. Microwave Digestion Settings

Max % Ramp Pressure Temp. Hold Stages power (W) power (min.) (PSI) (°C) (min)

1 1200 100 15:00 120 200 15:00

The total digestion time was 30 minutes. Figure 1 representsthe average digestion temperature over time in the vesselsduring sample preparation.

3


Phase 1 The results for Phase 1 are summarized in Table 4. Many ofthe samples encountered in feed and fertilizer laboratoriesconsist of high concentrations of nutrients. Some of theseelements cause ionization interferences while others cause

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

Table 4. Results Summary

Sample labels As 188.980 Expected Ca 370.602 Expected Cd 214.439 Expected Cr 267.716 Expectedunits mg/kg mg/kg % % mg/kg % mg/kg mg/kg

Sludge B 141 141 0.0233 0.0242 0.64 NA 110 111

Magruder 4B 2.05 1.75 2.71 2.48 12.31 NA 125.2 132.6

Magruder 6B 5.75 5.66 4.93 5.94 1.51 NA 50.88 51.08

Sample labels Cu 327.395 Expected Fe 261.382 Expected K2O 404.721 Expected Mg 279.078 Expectedunits % % % % % % K2O % %

Sludge B 0.0407 0.0398 0.012 0.014 NA NA 12.6 12.2

Magruder 4B 0.0461 0.0307 0.350 0.400 11.02 10.54 1.62 1.64

Magruder 6B 1.010 0.976 0.500 0.500 21.37 20.54 0.53 0.62

Sample labels Mn 294.921 Expected Na 589.592 Expected P 214.914 Expected units % % % % % P2O5 % P2O5

Sludge B 0.51 0.48 0.94 0.94 0.51 0.50

Magruder 4B 0.036 0.039 0.31 0.29 8.1 9.1

Magruder 6B 0.014 0.015 0.57 0.58 9.1 9.9

Sample labels Pb 220.353 Expected Se 196.026 Expected Zn 213.857 Expected units mg/kg mg/kg mg/kg mg/kg % %

Sludge B 6.8 5.7 NA NA 0.0244 0.0249

Magruder 4B 1.16 2.18 0.43 0.44 0.043 0.048

Magruder 6B 1.88 2.15 0.13 0.12 0.003 0.003

Phase 2 Available K2O and P2O5

The extraction reagent preparation requires 325 g EDTA and650 g dibasic ammonium citrate dissolved in 19.5 L distilledwater. With mixing, 390 mL of a 1:1 solution of NH4OH:H20 isthen added. When the solution is cooled to room temperature,the pH is carefully adjusted to 7.0 with additional 1:1 solutionof NH4OH:H20 and the final solution diluted to 26.0 L.

The traditional method requires that 0.25 g of sample undergoextraction in 100 mL ammonium citrate reagent in a Wheatonbath stabilized to 65 °C (the extraction solution is added tothe warmed sample). Upon completion of the extraction pro-cedure, the solutions are cooled and diluted to 250 mL withammonium citrate/EDTA reagent.

The samples are then typically run on the flame photometerfor available K2O and the auto-analyzer for P2O5.

The first part of the Phase 2 experiment was to determine if ICP-OES is a viable alternative technique for the determination of K andP. A set of ten fertilizer samples were extracted per the definedmethod and analyzed by the traditional techniques and ICP-OES.

With the ICP-OES technique, beryllium was selected as theinternal standard and 0.8% caesium as an ionization buffer.Optimum instrument conditions were found to be at a powerof 1.1 kW and a nebulizer flow of 0.65 L/min. The total sampleanalysis time was 55 s/sample.

A comparison of the results by technique for the determinationof K and P are summarized in Table 5.

4

The final step of the Phase 2 study was to mimic the extrac-tion process using microwave digestion. The microwave is notused for total digestion of the fertilizer sample, but as a wayto consistently heat the extraction to 65 °C.

Three Magruder fertilizers and NIST SRM 200a potassiumdihydrogen phosphate (KH2PO4) were carefully weighed to

0.1 g into HP 5000 vessels. Using the 75 mL vessels, 75 mL ofammonium citrate/EDTA extraction fluid was added. Stirringbars were added to each sample to simulate the shakingprocess and the contents were heated to 65 °C for 1 hour.

Table 6 summarizes the results collected by ICP-OES foravailable K2O and P2O5.

Table 5. Traditional Methodology Verses ICP–OES (1 Hour Water Bath Extraction) Results

ICP-OES Flame photometer ICP-OES Auto-analyzerCalibration solutions K2O (769.897 nm) K2O P2O5 (214.914 nm) P2O5(units) (% w/v) (% w/v) (% w/v) (% w/v)

Blank 0 0

Std 1 0.1145

Std 2 0.06023 0.4581

Std 3 0.68709

Std 4 0.24038 0.91612

Std 5 1.3742

ICP-OES Flame photometer ICP-OES Auto-analyzerCalibration solutions K2O (769.897 nm) K2O P2O5 (214.914 nm) P2O5(units) (% w/v) (% w/v) (% w/v) (% w/v)

NIST SRM 200a 34.81 34.64 52.62 52.11

Sample 1 4.51 4.59 21.6 21.59

Sample 2 4.50 4.29, 5.11, 5.19 8.10 8.59

Sample 3 9.22 9.22, 9.30 10.04 10.09

Sample 4 9.89 9.80, 9.71 10.04 9.75, 9.95

Sample 5 1.80 1.48, 2.46, 2.16 19.87 20.07

Sample 6 2.50 2.53, 3.03, 3.15 22.47 22.49, 22.69

Sample 7 10.17 9.88 10.58 10.47

Sample 8 8.56 8.58 4.17 4.06

Sample 9 5.47 5.45 9.71 9.73

Sample 10 18.49 18.00 16.56 16.70, 16.45

Note: No internal standard for K2O.

5

Conclusion

The preparation of fertilizer samples by microwave diges-tion/extraction for the determination of macro, secondaryand micro nutrients by simultaneous ICP-OES was evaluatedand found to compare well with more traditional methods.The combination of microwave and ICP-OES techniquesresulted in significantly faster and simpler sample preparationand analysis, requiring only a single analytical system tomeasure all elements of interest.

Acknowledgements

Elaine Hasty, CEM Corporation, Matthews, NC

Peter Kane, Office of Indiana State Chemist, West Lafayette, IN

Table 6. Summary of Results for Microwave Extraction and Determination of K2O and P2O5 by ICP–OES

K2O 404.721 K2O 769.897 P2O5 185.878 P2O5 214.914Calibration solutions(units) (% w/w) (% w/w) (% w/w) (% w/w) Calibration

Blank 0 0 0 0

Std 1 0.01139 0.01139

Std 2 0.012

Std 3 0.03038 0.05785 0.05785

Std 4 0.06022 0.06022 0.11449 0.11449

Std 5 0.1223 0.1223 0.22881 0.22881

Std 6 0.2431 0.2431

Std 7 0.49789

K2O 404.721 K2O 769.897 Expected P2O5 185.878 P2O5 214.914 ExpectedSamples(units) (% w/w) (% w/w) (% w/w) (% w/w) (% w/w) (% w/w)

NIST_SRM 200a 34.42 34.58 34.61 52.44 52.56 52.11

NIST SRM duplicate 34.93 34.34 52.70 52.44

MAG # 4 11.66 10.45 10.54 20.71 20.36 20.82

MAG # 4 duplicate 10.04 10.48 20.90 20.75

MAG # 6 26.65 25.41 25.42 22.33 22.07 22.54

MAG # 6 duplicate 23.99 24.88 22.25 22.10

MAG # 9 12.57 13.66 13.00 14.04 13.85 13.00

MAG # 9 duplicate 12.65 13.66 14.09 13.86






For more information on our products and services, visitour Web site at www.agilent.com/chem

Nitrate analysis of water using the

quartz fiber optics dip probe on the

Cary 50/60 UV-Vis

Application Note

Environmental

Author

Jeffrey Comerford. PhD.

Agilent Technologies, Inc.

Mulgrave, Victoria 3170,

Australia

Introduction

Environmental laboratories analyze thousands of water samples a year to

determine the concentration levels of heavy metals and other ions, such as

nitrates, phosphates and fluorides. To increase sample throughput and

efficiency, optical fibers may be used to measure the absorbance of the

sample. This allows for analysis on- or off-site, which is more appealing than

a conventional cuvette. This paper presents and discusses results obtained

from measuring the nitrate content in water using the quartz dip probe on

the Cary 50 UV-Vis spectrophotometer. This experiment can also be done on

the Cary 60 UV-Vis.

Experimental

Equipment

Cary 50 (Cary 60)UV-Vis spectrophotometer

Dip probe fiber optics coupler

Quartz fiber optic dip probe

Cary WinUV software

Reagents

Potassium nitrate (A.R.)

37% m/v Hydrochloric acid (A.R.)

Chloroform (A.R.)

Water - distilled and de-ionized

2

Method

The experimental procedure was taken from Standard

Methods for the Examination of Water and

Wastewater1 and is also described in UV Instruments

At Work No. 59 2. In brief, standard solutions were

prepared in the concentration range of 0 - 7mg NO3- -

N/L and the absorbance measured at 220 and 275 nm.

The measurement at two wavelengths allows

correction for the interference due to dissolved organic

matter, by calculating the difference between both

absorbance readings (Equation 1).

Abs(220) - 2xAbs(275) Equation 1

The application used was the Cary WinUV

Concentration software which evaluates the result of

Abs(220)-2xAbs(275) dynamically as a function of

concentration. The following instrument settings were

used for data collection.

Instrument Settings

User Result = Read(220)-2*Read(275)

Ordinate Mode Abs

Ave Time (sec) 1.0000

Replicates 3

Standard/Sample averaging OFF

Weight and volume corrections OFF

Fit type Quadratic

Min R² 0.95000

Concentration units mg/L

Results

Figure 1 shows the calibration curve obtained using the

Quartz Fiber Optics Dip Probe. The Y axis, Abs, is the

resultant from Equation 1 and the X-axis is the

concentration of Nitrate Standards in mg/L.

A quadratic function, Equation 2, was fitted to 6

standards giving a correlation coefficient of 0.99931.

The raw absorbance data and statistics for the

calibration standards are shown in Table 1.

Abs = -0.00017conc2 + 0.23364conc + 0.01705 Eq. 2

Figure 1. Calibration curve with quadratic fit

Table 1. Nitrate standards data for calibration curve

Std Conc

mg/L

Mean

Abs

SD %RSD Raw Abs

Std 1 0.103 0.0443 0.0036 8.03 0.0472

0.0404

0.0454

Std 2 0.205 0.0488 0.0002 0.37 0.0488

0.0490

0.0487

Std 3 0.616 0.1856 0.0011 0.57 0.1856

0.1846

0.1867

Std 4 1.027 0.2467 0.0030 1.22 0.2475

0.2492

0.2434

Std 5 1.541 0.3748 0.0006 0.17 0.3741

0.3750

0.3753

Std 6 6.162 1.4506 0.0011 0.07 1.4503

1.4496

1.4517

Two samples of tap water from different sources, A and

B, were prepared as described in the reference 1. The

absorbance was measured and the concentration of

nitrate determined from the calibration curve. The

results are shown in Table 2.

3

Table 2. Raw data and statistics of Water samples

Std Conc

mg/L

Mean

Abs

SD %RSD Raw Abs

A 0.145 0.0510 0.0009 1.78 0.0520

0.0504

0.0506

B 0.709 0.1825 0.0025 1.36 0.1797

0.1838

0.1841

Discussion

The 3 replicates for each standard and sample, shown

in Tables 1 and 2, are reproducible within instrumental

uncertainty, which demonstrates the high precision

possible using fiber optics on the Cary 50/60. There is

negligible solution carry over between samples,

washing with only distilled water for approximately 5

seconds.

The time taken to measure 24 solutions of 6 standards

and 2 samples, each with 3 replicates, was

approximately 5 minutes. This time included washing

the probe with de-ionized water in between readings

and drying with a tissue. Measurements with the dip

probe are significantly faster and easier than using a

conventional cuvette.

Conclusion

The quartz fiber optic dip probe on the Cary 50/60 is

highly precise and efficient for measuring the nitrate

content in water. The time taken to measure 24

solutions is faster than using a cuvette, which makes

the technique an attractive alternative for routine

analytical measurements.

Reference

1. D. Eaton, L. S. Clesceri and A. E.Greenberg,

Standard Methods for the Examination of Water

and Wastewater, 19th Edition, American Public

Health Association, Washington, 1995, p4-85.

2. P. A. Liberatore, UV-Instrument At Work;

Automated nitrate analysis of water, No. 59, Agilent

Australia Pty. Ltd, Australia, 1993.

.


© Agilent Technologies, Inc., 1993, 2011

Published March, 2011

Publication Number SI-A-1116


© Agilent Technologies, Inc., 2011

Published March, 2011

Publication Number 5990-7932EN

soil quality & fertilizer analysis

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