AAS-Food - Compendium 2011 - Soil Quality and Fertilizer Analysis-AGILENT TECH

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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. Rapiddetermination of the extractable elements in agricultural soil samples enables assessment of micronutrient content and provides an indication ofpossible deficiencies. Because fertilizers have a high concentration of active ingredients, and a
low concentration of contaminants, monitoringthe purity is a difficult application. With MP-AES, ICP-OES and AAS, Agilent offers a comprehensive set of
techniques resulting in significantlyfaster 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 a
Certified Reference Sludge Material
using the Agilent 710-ES
Application Note
Inductively Coupled Plasma-Optical Emission Spectrometers
Author
Introduction
Peter Doidge
Mercury is an element of great importance because of its toxicity. Over the last century, emissions of mercury due to human activities have resulted in a tripling of the
concentration of mercury in the atmosphere and surface oceans [1]. The main present-day sources of the additional man-made burden of environmental mercury are
coal combustion, municipal and medical waste incineration, and smelting [2].
Elucidation of the pathways resulting in human exposure to mercury remains a matter of great interest. According to Liebert et al., there is now [at the time they
wrote] scientific consensus that the most prevalent source of mercury exposure for the general population is from dental amalgam, and chronic inhalation or
swallowing of amalgam mercury vapor is the major contributor to the total body
burden of mercury in the U.S. [3].
Additional mercury body burdens may be derived from air, water or soils. Sewage
sludges and compost from solid waste and sewage sludge often have relatively high
mercury concentrations. Such organic wastes are often applied in agriculture as fertilizers, and although the recycling of waste is desirable, waste contamination by
mercury may lead to higher concentrations of mercury in the soil to which it is
applied, compared to those found when the soil is conventionally fertilized [4, 5].
Table 1.
Determination of the levels of mercury in solid wastes is therefore a matter of some interest. Concentrations of mercury in
sewage sludges are typically in the region of several parts per
million (by dry weight) [5]. A concentration of 5.6 g/g has
been reported in Australian urban sewage sludge [6].
Atomic spectrochemical methods such as atomic absorption
spectrometry (AAS) and ICP-OES provide the required sensitivity for the measurement of mercury at the concentrations that
are usually encountered in environmental analysis. Vapor generation techniques for atomic spectrochemical analysis are
widely used because of the excellent sensitivities provided for
several elements, including mercury. This application note
describes a simple procedure for the determination of mercury
in a suitable solid organic reference material (NBS 2781,
Domestic Sludge) by vapor generation coupled with ICP-OES.
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 wasteblue/blue
(1.65 mm ID)
Gas/Liquid separator waste
purple/black (2.29 mm ID)
Experimental
An Agilent VGA-77P (Vapor Generation Accessory) was used
with an Agilent 710-ES (ICP-OES) equipped with a megapixel
CCD detector. The operating conditions of the ICP instrument
and VGA are as shown in Tables 1 and 2. Vapor produced by
the VGA was injected into the plasma through the nebulizer
and spraychamber. With the VGA in operation, the plasma
was run dry; accordingly, a lower-than-usual power was set
in the method. The VGA was operated under conditions as
previously described [7, 8]. Argon was used as the VGA carrier gas. The use of nitrogen as the VGA carrier gas is not
recommended on ICP.
Instrument pump rate
45 rpm
Replicate read time (s)
Number of replicates
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
Samplepurple/black (2.29 mm ID)

Reductantblack/black (0.76 mm ID)
Acid/waterblack/black (0.76 mm ID)
Solution uptake rate
The instrument pump rate must be optimized to ensure that

the gas-liquid separator of the VGA is pumped effectively and
the liquid level does not rise, or fill the gas-liquid separator. A
pump rate of 4045 rpm is usually sufficient for this purpose.
This rate must be maintained whenever the VGA is in operation with sample solution being pumped. This pump rate must
be incorporated into the ICP method, and can be set as a
default on the Ignition page of the Instrument Setup window
in the ICP Expert II software, so that as soon as the plasma is
turned on, the pump speed changes to the required value. An
autosampler was not used in this study.
Sample8 mL/min
Reductant1 mL/min
Acid/water1 mL/min
Table 3.
Standard Solutions and Reagents

Working solutions for mercury determination in the micrograms-per-litre range were prepared from a mercury standard
(May and Baker). All mercury solutions were stabilized with a
0.01% solution of AIR potassium dichromate, as described by
Feldman [9]; this procedure resulted in the stabilization of the
mercury solutions for many days. Calibration solutions were
prepared at concentrations of 5, 10 and 20 g/L. Stannous
chloride was used as the reducing agent, though sodium
borohydride has also been used with the VGA [7,8]. A solution
of SnCl2 was prepared as a 25% w/v solution in 20% HCl from
AlR grade SnCl2 (BDH) and AlR HCl (BDH). Conditioning of
the VGA system was carried out according to advice by
Moffett [10]. Before conditioning, the response for very low
Hg concentrations may be variable. Conditioning of the active
sites in the tubing carrying the solutions and reaction products, can be achieved by running the highest concentration
Hg calibration standard (in this case 100 g/L) through the
system, until the response for much lower concentrations (for
example, 1 g/L) becomes stable.
Detection Limits (g/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 replicate

measurements of a 5 g/L standard with 5 second replicate
read times, was usually 12% RSD.
Analysis of a Certified Reference Material

Containing Hg
Certified reference material NBS 2781 (Domestic sludge) was
analysed by both normal calibration and by the method of
additions. No difference was observed in the slopes of the
graphs determined by the two methods, indicating no chemical
interference. As can be seen from the results in Table 4 for the
analysis of eight aliquots of the SRM, the recovery of mercury
is within the range of values encompassed by the uncertainty
in the concentration of the reference material.
Table 4.
Results of Analysis of NBS 2781

Hg Concentration, mg/kg
Measured value
Sample Preparation
The standard reference material NBS 2781 (Domestic sludge)
was selected for analysis. 3 mL of mixed nitric and hydrochloric
acids were added to approximately 0.1 g of the weighed SRM,
in the volume ratio 2:1. This was digested on a hot plate for
approximately two hours, or until fuming ceased. The solution
was cooled, filtered and diluted to 50 mL. A drop of Anti-Foam B
(Sigma Chemical Co.) was added to the solution after filtering.
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 for
the analysis of a certified reference material (NBS 2781). The
results obtained agree with certified values, within the
combined uncertainties of the two results.
Results and Discussion

Detection Limits
Detection limits determined for a 30-second replicate read
time on the Agilent 710-ES instrument are shown in Table 3.
(Detection limits (DLs) were measured on two instruments
and similar values were obtained for the two.) Under the operating conditions used, it was found that the three lines used
gave similar DLs, with slightly better DLs for the 253 nm line.
This differs from the typical behavior for Agilent ICP-OES
instruments with aqueous sample introduction, for which the
185 nm and 194 nm lines both give slightly better detection
limits than does the 253 nm line [11]. This may be a result of
the use of lower RF power, a condition which tends to favor
the less hard spectral lines, as a result of the less efficient
ionization and excitation at the lower power.
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 Cycling

of 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 and
Intestinal Bacterial Flora, Chapter 15 in A. Sigel and H.
Sigel, op. cit., pp.441-460
4.
L. Bringmark, Accumulation of Mercury in Soil and

Effects 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 in

sewage 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 AA

Instruments 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.), unpublished
data
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Agilent Technologies, Inc.

Printed in the USA
November 1, 2010
IO-036
Rapid Measurement of Major, Minor

and Trace Levels in Soils Using the
Agilent 730-ES
Application Note
Author
Introduction
Vincent Calderon
As part of the global strategy for sustainable farming, considerable emphasis has
been placed on the need for fast, accurate and precise determination of elements
in agricultural soil. As a result, simultaneous ICP-OES has become a widely used
technique for reporting the health of soils in the agricultural industry.
This work describes the preparation and analysis of certified reference soil materials
using the Agilent 730-ES simultaneous ICP-OES with CCD detection. The Agilent 730-ES
includes a switching valve system that improves the efficiency of sample introduction
and washout, providing greater sample throughput and accuracy.
A microwave-assisted acid digestion, based on recommendations given in US EPA
method 3051A, was used to rapidly extract the elements from the soil samples. This
method is not intended to accomplish total sample decomposition, and sample
matrix compounds such as quartz, silicates, titanium dioxide, alumina and other
oxides are not easily dissolved. For many environmental monitoring purposes, the
concentrations of extractable elements are more important than total concentrations,
as bound elements are not considered mobile in the environment [1].
Instrumentation
Preparation of Calibration Solutions
An Agilent 730-ES (simultaneous ICP-OES with axially viewed

plasma) was used for the analysis.
Calibration solutions were prepared from Inorganic Ventures

Inc. custom-grade multi-element solutions (VAR-CAL-1A,
VAR-CAL-2A and VAR-MAJOR-1A) and from Spex CertiPrep
single element solutions. These solutions contained the
following elements:
The Agilent 730-ES features a custom designed CCD detector,

which provides true simultaneous measurement and full
wavelength coverage from 167 to 785 nm. The patented CCD
detector contains continuous angled arrays that are matched
exactly to the two-dimensional image from the echelle optics.
The thermally stabilized optical system contains no moving
parts, ensuring excellent long-term stability.
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
The Agilent 730-ES also includes the productivity-enhancing

Switching Valve System (SVS) that provides more efficient
sample introduction and washout than traditional sample
introduction systems. The SVS consists of a software-controlled, 4-port switching valve that instantaneously rinses the
spray chamber following sample measurement while
simultaneously presenting the next sample for measurement.
Spex CertiPrep single element solutions:
Tables 2 and 3 list the selected elemental wavelengths and

standard concentrations used to calibrate each element.
Sensitivity, linear dynamic range and freedom from spectral
interferences were taken into consideration during
wavelength selection.
A Mars % closed vessel, microwave digestion system from

CEM was used to digest the solid samples.
Solutions were presented to the spectrometer using the
Agilent SPS3, Sample Preparation System.
Table 2.
Table 1 shows the operating parameters used in this work.

Table 1.
1000 mg/L Al
1000 mg/L P
1000 mg/L Sr
1000 mg/L Ti
Calibration Standards for the Major and Minor Elements
Wavelength Std 1
Std2
Std 3 Std 4 Std 5 Std 6
Element (nm)
(mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
Operating Parameters
Al
396.125
10
20
100
200
500
Setting
Ca
317.933
10
20
100
200
500
Power
1.2 kW
Fe
234.350
10
20
100
200
500
Plasma gas flow
15 L/min
Mg
285.213
10
20
100
200
Auxiliary gas flow
1.5 L/min
766.491
10
20
100
Spray chamber type
Glass cyclonic (single-pass)
178.222
10
20
Torch
Standard axial torch
Na
588.995
10
20
Nebulizer type
Seaspray
Ti
336.122
10
20
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)
Condition
Pump speed
15 rpm
Total sample usage
1 mL
Replicate read time
3s
Sample delay time
20 s
Switching valve delay
17 s
Stabilization time
12 s
Rinse time
1s
Fast pump
On
Background correction
Fitted
Table 3.
The soil samples were prepared by accurately weighing 0.25 g

of 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 mL
volumetric flasks. Each solution was diluted to volume with
>18MW/cm3 deionized water. Duplicate digestions were
carried out.
Calibration Standards for the Minor and Trace Elements
Wavelength Std 1
Element (nm)
(g/L)
Std2
Std 3
(g/L) (g/L)
Std 4
(g/L)
Std 5 Std 6
(g/L) (g/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
292.401
10
50
250
1000
Cd
226.502
10
50
250
Table 4 shows the settings used for the temperature dependent,

microwave assisted digestion.
Table 4.
Settings Required for Microwave Digestion
Stage
Max.
power
%
power
Ramp
(min)
Pressure
(PSI)
Temp.
(C)
Hold
(min)
600W
100
5:00
350
120
0:00
600 W
100
5:30
350
175
4:30
The calibration standard and blank solutions were prepared in

> 18MW/cm3 deionized water supplied from a Millipore
system and stabilized with 5% v/v HNO3 (Merck Tracepur).
Stage 1 was added as a reflux step to remove particulate

matter that adhered to the walls of the microwave vessel
during sample addition.
A solution containing 2 mg/L yttrium and 1% w/v CsNO3 in

5% v/v Tracepur HNO3 was introduced to the sample online
via the third channel of the peristaltic pump. Yttrium was used
for reference element (internal standard) correction and
cesium was used as an ionization buffer to eliminate ionization affects that potentially exist with such matrix types [2-3].
The moisture content of each reference material was determined as the certified values are based on dry weights. The
samples were oven dried at 110 C for 2 hours then cooled in
a desiccator for 4 hours. The data were adjusted accordingly.
Table 5.
Moisture Content
Measured moisture
content
Quoted moisture
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%
Sample Preparation
A closed-vessel microwave-assisted acid digestion was used
to extract the major, minor and trace elements from the soil
samples following USEPA method 3051A guidelines. This
method is designed to mimic extraction using conventional
heating with nitric acid (HNO3) and hydrochloric acid (HCl)
and does not accomplish total decomposition of the sample.
Therefore, the extracted analyte concentrations may not
reflect the total content in the sample [4]. Certified reference
materials NIST SRM 2710 Montana Soil and NIST SRM 2709
San Joaquin Soil were used to validate the method.

The measured concentrations of major, minor and trace elements in the respective soil reference materials are reported
in Tables 610. Analyses were performed in triplicate and the
error reported for each result represents the largest variation
from the mean value.
Table 6.
Extractable Major Elements in Soil
NIST SRM 2710 Montana soil
NIST SRM 2709 San Joaquin soil
Al (Wt%)
Ca (Wt%)
Fe (Wt%)
Mg (Wt%)
Reference data
Certified median
Certified range
1.8
1.22.6
0.41
0.380.48
2.7
2.23.2
0.57
0.430.60
Sample data
Digestion 1
Recovery
2.07 0.01
115
0.376 0.003
92
2.50 0.03
93
0.510 0.016
89
Duplicate data
Digestion 2
Recovery
2.05 0.004
114
0.377 0.001
92
2.50 0.001
93
0.508 0.005
89
Reference data
Certified median
Certified range
2.6
2.03.1
1.5
1.41.7
3.0
2.53.3
1.4
1.21.5
Sample data
Digestion 1
Recovery
2.00 0.01
77
1.38 0.01
92
2.63 0.01
88
1.15 0.01
82
Duplicate data
Digestion 2
Recovery
2.54 0.02
98
1.38 0.01
92
2.74 0.01
91
1.21 0.02
86
Table 7. Extractable Major and Minor Elements in Soil
K (Wt%)
P (Wt%)
Na (Wt%)
Ti (Wt%)
Reference data
Certified median
Certified range
0.45
0.370.50
0.11
0.1060.11
0.054
0.0490.062
0.10
0.0920.11
Sample data
Digestion 1
Recovery
0.497 0.003
110
0.0677 0.0008
62
0.0613 0.0003
114
0.122 0.001
122
Duplicate data
Digestion 2
Recovery
0.492 0.001
109
0.0681 0.0001
62
0.0612 0.0002
113
0.120 0.0003
120
Reference data
Certified median
Certified range
0.32
0.260.37
0.07
0.050.07
0.068
0.0630.11
0.038
0.030.04
Sample data
Digestion 1
Recovery
0.347 0.001
108
0.0442 0.0003
63
0.0636 0.0005
94
0.0234 0.0001
62
Duplicate data
Digestion 2
Recovery
0.408 0.004
127
0.0444 0.0004
63
0.0684 0.0003
101
0.0545 0.0006
143
Table 8.
Extractable Major and Minor Elements in Soil
Zn (mg/kg)
Mn (mg/kg)
Cu (mg/kg)
Ba (mg/kg)
Sr (mg/kg)
Reference data
Certified median
Certified range
5900
52006900
7700
62009000
2700
24003400
360
300400
100
94110
Sample data
Digestion 1
Recovery
5815 46
99
7054 86
92
2426 20
90
307 4
85
90.9 1.1
91
Duplicate data
Digestion 2
Recovery
5897 18
100
7064 10
92
2436 5
90
306 1
85
90.6 0.2
91
Reference data
Certified median
Certified range
100
87120
470
360600
32
2640
398
392400
101
100112
Sample data
Digestion 1
Recovery
87.2 0.3
87
483 3
103
29.2 0.3
91
367 1
92
88.7 0.5
88
Duplicate data
Digestion 2
Recovery
84.2 0.6
84
485 6
103
29.3 0.1
92
377 3
95
91.4 0.3
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)
Reference data
Certified median
Certified range
5100
43007000
590
490600
19
1523
10.1
8.815
8.2
6.312
Sample data
Digestion 1
Recovery
4433 22
87
514 4
87
19.3 0.1
102
10.4 0.1
103
8.90 0.06
109
Duplicate data
Digestion 2
Recovery
4484 29
88
518 1
88
19.2 0.1
101
10.3 0.2
102
8.99 0.05
110
Reference data
Certified Median median
Certified Rangerange 1218
13
< 20
60115
79
6590
78 12
1015
Sample data
Digestion 1
Recovery
10.7 0.1
82
15.3 0.1
61.8 0.2
78
67.7 0.6
87
11.1 0.1
93
Duplicate data
Digestion 2
Recovery
11.0 0.5
85
15.2 0.6
72.5 0.2
92
68.2 0.3
87
11.5 0.1
96
Table 10.
Extractable Major, Minor and Ttrace Elements in Soil
Cd (mg/kg)
Mo (mg/kg)
V (mg/kg)
Reference data
Certified median
Certified range
20
1326
20
1327
43
3750
Sample data
Digestion 1
Recovery
16.4 0.1
82
14.94 0.1
75
48.74 0.5
113
Duplicate data
Digestion 2
Recovery
16.64 0.1
83
14.4 0.3
75
48.64 0.1
113
Reference data
Certified Median median
Certified Rangerange
<1
<2
62
5170
Sample data
Digestion 1
Recovery
< 0.2
1.514 0.03
60.04 0.2
97
Duplicate data
Digestion 2
Recovery
< 0.4
1.494 0.05
74.24 0.2
120
Note: < value indicates an undetected element with the < value expressed as 10 times the standard deviation of background emission.
The majority of the remaining extractable major, minor and

trace elements (Zn, Mn, Cu, Ba, Sr, Pb, As, Cr, Ni, Cd, Co, Mo
and V) fell within the certified range. Those that did not fall
within the certified ranges were within 16% of the certified
median value.
Although a small amount of undissolved material was

observed following microwave digestion, the overall measured concentrations of extractable major, minor and trace
elements in the soil samples were in good agreement with
the certified leach data.
The major and minor elements Al, Fe, Mg, Na and K were
within 15% of the respective certified median values and
within 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) and
duplicate values (digestion 2) were found to be greater with
the measured value for magnesium in the original sample and
potassium in the duplicate falling just outside the certified
range. Good recovery was also achieved for calcium at 92%
for both soil samples and duplicates, although the measured
concentrations fell just outside the lower end of the certified
range. With a measured recovery of 6263% in both soil
sample types, phosphorus did not appear to undergo complete extraction, although the reproducibility of the extraction
for P was excellent. On the other hand, titanium produced
mixed results suggesting incomplete extraction and in
homogeneity.
Conclusion
Two certified reference soil materials, containing variable
levels of major, minor and trace elements were digested following US EPA Method 3051A and analysed on the Agilent
730-ES Simultaneous ICP-OES. Agreement between the
measured and certified values was generally very good.
The switching valve, fast rinse accessory was also used
allowing more efficient introduction and washout of the
sample from the sample introduction system. The determination of 21 elements in a sample took less than 65 seconds
and required approximately 1 mL of solution, making the
Agilent 730-ES an excellent analytical tool for fast and
efficient analysis of soils.
References
A. Ryan, Direct analysis of milk powder on the Liberty Series
II ICP-AES with the axially-viewed plasma. ICP Instruments
at work, 1997, ICP-21.
US EPA Method 3051A Microwave Assisted Acid Digestion
of Sediments, Sludges, Soils and Oils. Revision 1, 1998.


Printed in the USA
November 1, 2010
IO-035
Analysis of Soil Extracts Using the

Agilent 725-ES
Application Note
Author
Introduction
Tran T. Nham
In agricultural science, soil samples are routinely analyzed for micronutrient content. Analytical data permits an assessment of the nutrient levels available for
plants, and provides an indication of possible nutrient deficiency.
Available metals in soil are extracted with a variety of reagents, for example, diethylene
triaminepenta-acetic acid (DTPA), EDTA, water and ammonium acetate, depending on
the soil type and the form of the element required [14].
Inductively coupled plasma optical emission spectrometry (ICP-OES) is a multi-element analytical technique that offers fast sample throughput, high sensitivity and a
wide dynamic range. Soil analysis with this technique is well established[1,3,57].
This work describes the use of a radially-viewed simultaneous ICP-OES for the
analysis of different soil extracts.
1 M Ammonium Acetate Solution
Instrumentation
77 g of ammonium acetate was weighed and dissolved in

1000 mL of water. The pH was adjusted to 7.0 with ammonia
or acetic acid.
An Agilent 725-ES with simultaneous CCD detection was

used for the measurements. The Agilent 725-ES features an
echelle polychromator equipped with a custom designed and
patented CCD detector [8] producing continuous wavelength
coverage from 167 to 784 nm. The polychromator can be
purged with either argon or nitrogen gas for measurements at
low UV wavelengths.
0.01 M Calcium Dihydrogen Orthophosphate

Solution
1 g of calcium carbonate was weighed into a beaker and 5 mL
of ultra-pure water was added. Slowly and with constant stirring, 1.4 mL of 85% orthophosphoric acid was added. Mixing
was continued until the calcium carbonate had dissolved. The
solution was then made up to 1000 mL with ultra-pure water.
The sample introduction consisted of a one-piece standard

quartz torch, V-groove nebuliser and a Sturman-Masters spray
chamber. An Agilent SPS3 autosampler was used to introduce
the solutions to the ICP.
Preparation of Soil Sample Extracts
The operating parameters are listed in Table 1.

Table 1.
The soil samples were dried in a 40 C oven for 24 hours, then

finely ground and sieved through a 200 mesh sieve.
Instrument Operating Conditions
Condition
Setting
Power
1.2 kW
DTPA Extraction (for Zn, Fe, Mn, Cu)
Plasma gas flow
15 L/min
Auxiliary gas flow
1.5 L/min
Nebulizer flow
0.75 L/min
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.
Pump speed
15 rpm
Integration time
5s
Points per peak
Sample delay time
35 s
Stabilization time
10 s
Fitted
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 solution
was added. The bottle was stoppered and placed in a 5 rpm
end-to-end tumbler for 16 hours and the mixture was filtered.
Reagents and Standards

All chemicals and reagents used were of analytical reagent
grade. All standards and blanks were matrix-matched with the
samples. All reagents and standards were prepared or diluted
in ultra-pure water (resistivity >18.2 MW/cm at 25 C) supplied
from a Millipore water filtration system.

Wavelength Selection
The selection of wavelengths was based on sensitivity, linear
dynamic range and freedom from spectral interferences. The
wavelengths used and method detection limits for soil
extracts are listed in Table 2.
Preparation of Extraction Solutions

0.005 M Diethylene Triaminepenta-Acetic Acid
(DTPA) Solution
The ICP Expert II software allows the simultaneous measurement of multiple wavelengths for a given element to
extend its calibration range. This important analytical tool
called MultiCal can also assist the analyst in confirming the
analytical results.
1.96 g of DTPA, 14.92 g of triethanolamine and 1.47 g of

CaCl2.2H2O were weighed into a beaker and dissolved in
1000 mL of ultra-pure water. The pH was adjusted to 7.3 with
concentrated HCl or triethanolamine.
Table 2.
Analysis of Ammonium Acetate Extract for Na, K,

Ca, Mg
Wavelengths and Estimated Detection Limits Obtained at 5 s

Integration Time
Stage
Wavelength
Ca
422.673
Method detection limits (g/L)
Ca
317.933
30
Ca
183.738
1000
Ca
220.861
5000
Cu
324.754
10
The mean results of the analysis of control soil samples 1 and

2 are listed in Table 4. The measured values are in good
agreement with the certified values.
15
Table 4.
Results of Ca, K, Mg and Na in Ammonium Acetate Extract

Concentration (mg/L)
Cu
327.395
10
Control sample 1
Fe
238.204
10
Fe
259.940
25
Measured
Certified
concentration range
Measured
concentration
Certified
range
766.491
30
Ca
425 3
430444
64.7 0.8
6772
Mg
279.800
100
11.7 0.9
11.712.9
5.6 0.1
5.46.2
Mg
279.079
300
Mg
76.8 1.2
7683
13.1 0.5
13.414.4
Mg
278.142
1000
Na
8.0 0.5
7.68.3
22.1 0.1
21.622.6
Mn
257.610
1.5
Mn
259.372
Na
588.995
10
181.972
150
Zn
213.857
Zn
206.200
25
Analysis of Phosphate Extract for Sulfur

The primary S 181.972 nm line is recommended over the secondary S 180.669 nm line because of spectral interference
from 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 provides real time spectral correction to solve spectral interference by deconvolution. The corrections are done in real time
with 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.
Analysis of DTPA Extract for Zn, Fe, Mn, Cu

Table 3.
Control sample 2
Results of Cu, Fe, Mn and Zn in DTPA Extract

Control sample 1
Control sample 2
Measured
Certified
concentration range
Measured
concentration
Certified
range
Cu
0.23 0.01
0.200.24
0.130 0.001
0.110.13
Fe
13.20 0.03
11.9015.20
2.49 0.01
2.102.60
Mn
3.03 0.02
2.603.10
1.410 0.001
1.101.40
Zn
0.330 0.001 0.300.36
0.042 0.001
0.030.04
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.

G. E. Rayment and F. R. Higginson, Australian

Laboratory Handbook of Soil and Water Chemical
Methods, Inkata Press, Sydney, 1992
Table 5.
R. L. Dahlquist, J. W. Knoll, Inductively Coupled Plasma

Atomic Emission Spectrometry Analysis of Biological
Materials and Soils for Major, Trace and Ultra-trace
Elements, Appl. Spectrosc., 1978, 32, 1.
D. W. Hoult, M. M. Beaty, G. F. Wallace, Automated,

Sequential, Multielement Analysis of Agricultural
Samples by Inductively Coupled Plasma Emission
Spectroscopy, At. Spectrosc., 6, 1980, 157.
7.
R. A. Issac, W. C. Johnson, High Speed Analysis of

Agricultural Samples using Inductively Coupled Plasma
Atomic Emission Spectroscopy, Spectrochim. Acta,
1983, 38, 277.
8.
A. T. Zander, R. L. Chien, C. B. Cooper, P. V. Wilson, An

Image-Mapped detector for Simultaneous ICP-AES,
Anal. Chem., 1999, 71, 3332.
9.
C. Webb, A. T. Zander, P. V. Wilson, G. Perlis, A Fast

Automated Spectral Curve Fitting Tachnique for ICPAES, Spectroscopy, 1999, 14(5), 58.
Results of S in Soil Extract

Control sample 1
Control sample 2
Measured
Certified
concentration range
Measured
Certified
concentration range
S 181.972
2.63 0.05
2.403.00
7.58 0.02
6.808.00
S 180.669
(with FACT)
2.70 0.01
2.403.00
7.68 0.01
6.808.00
Acknowledgements
Many thanks to John L. Lomas of Incitec Ltd. for the supply of
soil extracts and the review of this document.
References
1
D. J. David, Analysis of Soils, Plants, Fertilizers and Other

Agricultural Materials, Prog. Analyt. At. Spectrosc., 1978,
1, 225
W. L. Lindsay, W. A. Norvell, Development of a DTPA Soil

Test for Zinc, Iron, Manganese and Copper, Soil Sci. Soc.
Amer. J., 1978, 42, 421
Inductively Coupled Plasma Emission Spectroscopy. Part

II : Applications and Fundamentals, P. W. J. M. Boumans
Ed., John Wiley and Sons Inc., New York, 1987, Chapter 4


Printed in the USA
November 1, 2010
IO-034
The Latest Advances in Axially

Viewed Simultaneous ICP-OES for
Elemental Analysis
Application Note
Inductively Coupled Plasma-Optical Emmision Spectrometers
Author
Background
Michael B. Knowles
Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) is a popular

technique of elemental analysis. ICP is applicable to around 73 elements and provides fast multi-element analysis with superior detection limits to atomic absorption
spectrometry (AAS) for many elements.
Initially ICP-OES systems featured a vertically-oriented

plasma. The plasma was "viewed" by the optical system from
the side, Figure 1. This configuration is known as "radial
viewing" and has the advantage of providing immediate venting of exhaust gases and waste heat to an overhead extraction system. In the mid 1970s workers began to develop endon or axially viewed plasma systems [1]. The aim of axial
viewing is to observe a longer path length in the analyte-rich
central channel, while avoiding viewing the surrounding
intense argon plasma [2]. This approach provides improved
signal to noise ratio and hence better detection limits. Axially
and radially viewed plasmas are shown schematically in
Figure 1.
restricted to upper concentration limits of just 10100 partsper-million. This linear dynamic range problem spurred interested in "dual viewed" plasmas - a horizontal plasma viewed
alternately from the end or from the side. Dual viewed systems however require samples to be analyzed twice - once
with each viewing mode, and so productivity is restricted.
The reputation of axial ICP systems has unfortunately been
undermined by these historical observations. The purpose of
this paper, is to review the latest advances in ICP-OES detectors, software and sample introduction systems which lead to
modern simultaneous axially viewed ICPOES systems that
overcome these perceptions. Todays modern axially viewed
ICP systems provide the productivity of a single analysis with
wide dynamic range from one plasma view.
Advances in ICP-OES Detector Design

Early ICP designs used photomultiplier tubes (PMT) to detect
light emitted from the plasma. PMTs could be used in either
simultaneous ICP systems, with multiple detectors being
placed around a Rowland circle or coupled to a sequential
scanning monochromator such as a Czerney-Turner design.
The disadvantages of each of these approaches is clear using discrete detectors to measure each wavelength means
you have to choose the wavelengths to measure ahead of
time - restricting future flexibility. Sequential scanning
designs, while more flexible, require more time to complete
an analysis.
Figure 1.
In the early 1990s various groups developed solid state simultaneous detection systems either based on Charge Coupled
Devices (CCD) or Charge Injection Device (CID) designs.
These devices differ in the way in which they measure the
electronic charge created on the surface of the detector. A
useful review of these technologies was provided by Harnly
and Fields in 1997 [3]. With both detector types, an array of
light sensitive detectors or pixels is used to convert the
incoming photons into electrons for measurement.
Schematic diagram of radial and axially viewed plasma systems,

note the three concentric tubes of the torches, the vertical orientation and side viewing of the "radial" torch and the horizontal
orientation and end-on viewing of the "axial" torch.
Axially viewed plasma systems find application where best

sensitivity is needed, particularly environmental analyses of
waters and wastes. Axially viewed ICP-OES offers a viable
and more robust alternative to more expensive ICP-Mass
Spectrometry systems while meeting the detection limit
requirements of most regulatory bodies. Historically, the performance of axially viewed ICP systems was thought to be
limited by injector tube blockage and subsequent signal drift
when solutions containing high dissolved solids are aspirated.
In addition, the limitations of older ICP detector designs
meant that the linear dynamic range of axial ICP was
These detectors are generally used in conjunction with an

echelle polychromator which creates a 2 dimensional spectrum from the light emitted by the plasma. The emitted light is
split both into its component optical orders (creating a series
of "rows" of light) and also into its component wavelengths.
One CCD design implemented in the early 1990s positioned
the light sensitive pixels at the locations of preferred wavelengths [4]. This design became known as the Segmented
and alignment of 70 orders of light coming from the echelle

spectrometer. The placement of the pixels in continuous
rows provides complete and continuous wavelength coverage
of 96% of the analytical spectrum. This approach opens up a
major advantage of ICP-OES - using alternative wavelengths
to avoid spectral interferences and to extend linear dynamic
range by using wavelengths in combination.
Array CCD detector or SCD. Pixels were created in small

linear groups positioned to detect the preferred suite of wavelengths. The SCD used just 6336 pixels, presumably in an
attempt to minimize perceived limitations in readout speed
and photometric data quality. The restricted number of pixels
no doubt matched the limited data processing capabilities of
the electronics and computers then in use. The SCD is still
used today with a current ICP-OES design. The limitations of
the SCD are clear - pixel groups are positioned only at locations of preferred wavelengths - thereby imposing the same
restrictions of wavelength choice and flexibility as the multiple PMT based designs of the 1970s and 1980s. Barnard
et. al. [4] state that the SCD provides only 5.7% coverage of
the spectrum from 167 to 782 nm. Because of this inherent
restriction on available wavelengths current ICP designs
based on SCD technology cannot take advantage of the
improvements in linear dynamic range that can be obtained
by using multiwavelength data. As a result, alternative
plasma viewing methods, such as the dual view systems,
were developed to compensate for this lack of linear dynamic
range.
In August 2000, the worlds first array CCD detector applied to

simultaneous ICP-OES with the Vista- MPX was announced.
The MPX detector features over 1.1 million pixels arranged in
an X-Y array - again providing up to 96% coverage of the analytical spectrum from a single simultaneous reading. The
Vista-MPX achieves the linear dynamic range and flexibility
advantages of the Vista image mapped CCD, in an even more
affordable package. Both systems provide the advantages of
true simultaneous ICP-OES, with simultaneous background
correction and internal standardization providing more accurate and precise results. In addition, the systems include no
moving optical components, resulting in excellent long term
stability and analysis speeds compared to sequential scanning systems. The grating and prism of the echelle spectrometer used in the Vista series are fixed and the optics thermostatted providing long term drift-free performance without
the need for correction lamps. With most axial and dual view
systems the ICP torch is oriented horizontally and viewed
end-on (Figure 1). This orientation is preferred because endon viewing of a vertical (radially viewed) plasma is more difficult due to hot, corrosive vapors travelling past the viewing
optics.
The Vista series of simultaneous ICP-OES spectrometers

were introduced in1998. In developing the Vista series,
Agilent took advantage of the availability of the next generation of CCD detectors [5]. The VistaChip (Figure 2) CCD
features over 70,000 pixels positioned to exactly match the
free spectral range of the two dimensional echellogram.
Zander et. al. [5] referred to this as "image mapping", with
the pixels being positioned so as to match the exact angle
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 (photosensitive detectors) exactly positioned to match the spectral output from the echelle spectrometer. Note the differing slopes and separations of
these "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.
Advances in Axial Viewing Systems
Table1.
The Horizontal, Axially Viewed Plasma
Offers 410x improvement in sensitivity compared to the

radial view, due to longer path length of measurement
Is ideal for routine analysis of samples containing less

than 5% dissolved solids. With simple modifications to
the sample introduction system Agilent axial ICP now can
analyze 25% dissolved solids solutions directly for
24 hours.
There are key differences between axially viewed plasmas. Agilents Cooled Cone Interface (CCI) displaces the
cooler tail flame of the plasma away from the optical
path, resulting in greater linear dynamic range and a
significant reduction in atomization and recombination
interferences.
Agilents CCI requires only a small counter flow of argon

gas, 2.5 L/min. The alternative shear gas approach used
on many dual view systems requires very high volumes of
gas, from 15-20 L/min, to displace the plasma from the
optical path. This gas must be nitrogen to measure below
190 nm.
Agilents CCI design makes the axially viewed plasma

ideal for analyzing organic solvents.
The axially viewed plasma provides the benefits of improved

sensitivity and detection limits and this performance has seen
this configuration grow in popularity in the past decade.
Table 1 shows the improvement factors in detection limits
that can be obtained using axial viewing compared to radial
viewing, typically this factor is between 410 times. Axially
viewed ICP systems achieve detection limits that meet the
majority of requirements for drinking water, waste water and
other important environmental applications. The axially
viewed ICP easily meets the detection limit requirements of
the US EPA [6] for example.
Comparison of 3 s Detection Limits for Radially and Axially

Viewed Vista-Pro ICP. All Data was Collected Using 30 Seconds
Integration Times [7]
Element
Wavelength
(nm)
3 s Detection
Vista-PRO
radial (g/L)
Limits
Vista-PRO
Improvement
axial (g/L) factor
Ag
Al
As
Au
B
Ba
Be
Bi
Ca
Cd
Ce
Co
Cr
Cu
Fe
K
Li
Mg
Mn
Mo
Na
Ni
P
Pb
S
Sb
Se
Si
Sr
Ti
Tl
V
W
Zn
Zr
328.068
167.016
188.979
267.595
249.773
455.403
234.861
223.061
396.847
214.438
418.660
238.892
267.716
327.396
259.940
766.490
670.784
279.553
257.610
202.030
589.592
231.604
177.432
220.353
181.971
231.147
196.026
251.611
407.771
334.941
190.790
292.402
207.911
213.856
343.823
1
0.9
5
5
0.6
0.15
0.05
6
0.06
0.6
2
1
0.9
1
0.8
4
1
0.04
0.08
2
2
1.4
5
5
10
5
6
2.2
0.05
0.2
6
0.7
3.5
0.8
0.9
0.3
0.2
1.5
1.0
0.1
0.03
0.01
2
0.01
0.05
2
0.2
0.15
0.3
0.1
0.3
0.06
0.01
0.03
0.5
0.15
0.3
2
0.8
5
2
2
1.4
0.01
0.1
2
0.2
2
0.2
0.3
3.3
4.5
3.3
5
6
5
5
3
6
12
1
5
6
3.3
8
13.3
16.7
4
2.7
4
13.3
4.7
2.5
6.3
2
2.5
3
1.6
5
2
3
3.5
1.8
4
3
High Solids Capabilities
The Agilent axially viewed ICP systems all share the same
viewing configuration, shown in Figure 3. The plasma is
directed at a Cooled Cone Interface (CCI), consisting of a
water cooled nickel cone with a large sampling orifice cut in
its tip. A small counter flow of argon gas passing through the
cone ensures that the heat and vapors from the plasma
cannot compromise the optical system, which is further protected by a quartz window. The CCI displaces the cooler
plasma tail away from the optical path of the ICP instrument.
It is in this cooler region of the plasma that analyte selfabsorption, vaporization and ionization interferences can
occur.. Brenner and Zander concluded [8] that removal of
the cool fringe reduces matrix effects due to Easily Ionizable
Elements and Ca and extends the linear range of calibration
and determination.
The axially viewed ICP provides excellent long term stability

for samples containing up to 5% dissolved solids using standard sample introduction systems. With normal rinsing routines, these samples can be analyzed throughout the day
using an axially viewed ICP. Most samples fall below this high
dissolved solids limit. For example, if 1g of sample is digested
and diluted to 100 mL this represents 1% dissolved solids in
the sample. Figure 4 shows the long term stability of the
Agilent axially viewed Vista ICP for the continuous analysis of
5% sodium chloride solution [9].
Figure 3.
Photo of Agilents Cooled Cone Interface. The cooler red zone of the plasma can be seen displaced around the outside of the cone, while aspirating
Yttrium. 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 a
sealed 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. Percent
standard deviation over a period of 3.5 hours was less than 2.5% in all cases. Note this analysis was conducted without between-sample rinsing
which would further extend operation time.
Recently, a range of new spraychamber, nebulizer and torch

options has been developed for ICP-OES which allows longer
analysis periods for higher levels of dissolved solids. These
options include double pass spraychambers, "v-groove" nebulizers, wider bore injector tubes and demountable axial torch
designs. By simply selecting appropriate sample introduction
system components, long term analysis of high levels of dissolved salts is now obtainable. An example of this work is
shown in Figure 5 [10]. Using a modified torch with an axially
viewed Vista-MPX simultaneous ICP-OES, the direct analysis
of 25% sodium chloride solutions was demonstrated for over
24 hours of continuous aspiration. The precision over
24 hours ranged from 3.3% to 5.2% relative standard deviation. This work shows that the high salts stability of the
Agilent axially viewed ICPs is dependent upon the choice of
sample introduction system and not on the instrument itself.
In this way, the performance of a radially viewed ICP can be
obtained from an axially viewed ICP without the need for dual
view optics.
Figure 5.
Linear Dynamic Range

Linear Dynamic Range (LDR) is an important performance
characteristic of ICP spectrometers as it defines the upper
and lower limits of analyte concentrations that can be accurately measured. The lower end of this scale is defined by
detection limits (see Table 1) or determination limits and the
upper end is defined by the limits of calibration linearity. The
US EPA [6] uses a 5% calibration accuracy definition to determine this upper concentration limit. LDR limitations are often
cited as the need for dual view plasma systems - that is, it is
claimed that to measure high levels of analytes (> 100 mg/L)
both the radial view and the axial view are required in the one
spectrometer. Since both views cannot be measured simultaneously, the dual view approach slows down the productivity
of the analysis.
The continuous analysis of 25% sodium chloride solution over 24 hours using a Vista-MPX axially viewed ICP (expected concentrations 1mg/L). The
solution was continuously aspirated without rinsing and no internal standard correction was used. The plasma torch was fitted with a high solids
injector tube. A Sturman Masters double pass cyclonic spraychamber and v-groove nebulizer were used with an argon saturator accessory (ASA).
As noted earlier, many of the assumptions about the linear

dynamic range of ICPOES systems may have been based upon
detector and plasma interface design limitations of that
era [4]. With the introduction of Agilents Cooled Cone
Interface (CCI) these limitations have been overcome and it is
possible to have wide linear dynamic range from one axially
viewed plasma system without the need to analyze the
sample twice. In the past, the linear dynamic range of axially
viewed systems was limited by analyte selfabsorption due to
the longer path length of measurement. The Agilent CCI provides extended linear dynamic range by optimizing the observation of the central channel of the plasma and eliminating
observation of the cooler plasma tail.
Table 2.
When coupled with the full wavelength coverage of the

Agilent ICP-OES systems, the axially viewed configuration can
be used from parts-per-billion detection limits up to maximum
concentrations of percentage levels. This performance is
shown in Table 2 [12], which shows the upper limits of linear
dynamic range for elements using the axially viewed, simultaneous Vista-MPX. Comparing these results to the detection
limits in Table 1, it can be seen that a very wide dynamic
range can be obtained from one axially viewed ICP system
with just one sample measurement.
Linear Dynamic Range Test Results on the Axially Viewed VistaMPX with CCI, Showing Accurate Recoveries of Elements up to
500 and 600 mg/L is Easily Possible. Vista CCI Provides Radial
View Performance with the Benefits of Axial Sensitivity
Element
LRA (mg/L)
Recovery %
Ag
Al
Al
328.068
236.705
308.215
10
500
40
101
99
100
As
Ba
Be
188.980
585.367
313.042
10
200
5
103
95
101
Ca
Ca
Cd
315.887
370.602
226.502
100
600
5
99
97
99
Co
Cr
Cu
228.615
267.716
327.395
50
20
30
97
100
101
Fe
Fe
K
234.350
258.588
404.721
100
500
500
100
95
104
K
K
Mg
766.491
769.897
279.800
50
200
600
102
101
98
Mg
Mn
Na
383.829
257.610
330.237
600
50
600
99
97
97
Na
Ni
Pb
589.592
231.604
220.353
50
50
100
98
97
101
Sb
Se
Tl
V
206.834
196.026
190.794
311.837
10
100
100
60
103
101
101
99
Advances In Software Design

To take advantage of the full wavelength coverage of
Agilents CCD detector technology, the Vista simultaneous
ICP systems feature MultiCal, which automatically assigns
each sample to the best wavelength for that result. If a
sample result falls within a particular concentration range it is
automatically assigned to the wavelength that is most appropriate for that concentration. In this way the Vista series of
instruments takes advantage of the availability of all of the
wavelengths in the analytical spectrum - automatically combining the most sensitive wavelengths for best detection
limits with less sensitive wavelengths for best dynamic range.
Figure 6, shows the MultiCal advantage, with a pair of calibration graphs for calcium, measured on the Vista-MPX. Low
concentration results are automatically reported from one calibration graph and high concentration results reported from a
second calibration graph - extending the linear dynamic range
for this element. Also in this example, the results from the
two wavelengths have been mathematically combined into
one calcium result. In this case the average of the two calcium results from the two wavelengths has been used, however users may also choose from weighted mean, minimum
and median of the results. Only results that fall within the
valid calibration range of the wavelengths will be used in
these calculations providing extra surety of data quality. The
original wavelength columns can either be displayed (for full
information) or hidden (for simplicity and ease of use). By displaying all available wavelength information, the user is given
another data quality control check, by comparing the accuracy
of the results from two or more wavelengths for the same
element.
Figure 6.
Conclusions
In this paper we have reviewed the recent developments in
the design of axially viewed ICP-OES. Axially viewed ICP-OES
has emerged as the preferred viewing technique due to its
benefits of enhanced sensitivity and detection. Agilents
Cooled Cone Interface is an optimized design that eliminates
chemical and molecular interferences and extends the linear
dynamic range of the axial ICP. This axial design combined
with Agilents CCD detector technology provides simultaneous measurement of all wavelengths and further extends the
linear dyanamic range of ICP-OES. With simple changes to
the sample introduction system, Agilents axially viewed
ICP-OES can analyze high dissolved salt samples continuously
with excellent long term stability.
The Agilent MultiCal advantage - the first column shows the mean result from two Ca wavelengths - 315.887 and 370.602 nm, automatically combined by the Vista-PRO software. The combined wavelengths allow calibration to 1000 mg/L from a single analysis on this axially viewed ICP. This
extended linear dynamic range would normally only be possible with a radially viewed ICP. With MultiCal, the Vista ICP series provides both the
extended linear dynamic range of a radial ICP and the excellent detection limits of an axially viewed ICP with one simple analysis. The accuracy of
the results is established from the 50 mg/L and 500 mg/L Continuing Calibration Verification (CCV) results.
The unique MultiCal automates the intelligent assignment of

sample results to the most appropriate wavelength. The accurate measurement of high concentration matrix elements can
now be performed simultaneously with trace level detection
of other analytes of interest from one axial plasma viewing
system and one measurement. MultiCal eliminates the need
for Dual View optics, enhances productivity and reduces
argon consumption.
References
1.
M. H. Abdallah, J. J. Diemiaszonek, J. M. Mermet,

J. Robin, C. Trassy, Etude Spectrometrique Dun Plasma
Induit Par Haute Frequence, Partie 1: Performances an
Alytiques, Analytica Chimica Acta, 1976, 84, 271-282
2.
C. Dubuisson, E. Poussel, J-M. Mermet, Comparison of

axially and radially viewed Inductively Coupled Plasma
Atomic Emission Spectrometry in terms of signal-to-background ratio and matrix effects, Journal of Analytical
Atomic Spectrometry, March 1997, 12, 281-286
3.
J. M. Harnly, R. E. Fields, Solid state array detectors for

analytical 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 detector
for 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 Work

for Inorganics, Multi-media, Multi-concentration,
Document Number ILM05.0, at www.epa.gov/oamsrpod/pollard/ hq9915909/ilmo50c.pdf
7.
J. P. Lener and V. Lecourbe, 2000, August, Varian Internal

Report
8.
I. B. Brenner, A. T. Zander, Axially and radially viewed

inductively coupled plasmasa critical review,
Spectrochimica Acta, 2000, Part B 55 195-1240
9.
F. Minnelli, 2001, January, Varian Internal Report.
Agilents CCI and MultiCal approach offers significant

advantages that should see axially viewed ICP-OES remain a
popular technique for many years to come.
Acknowledgements
The author would like to thank Tran Nham, Filippa Minnelli
and Ingrid Szikla (all of Varian, Inc., Melbourne, Australia) and
Jean-Pierre Lener and Valerie Lecourbe (of Varian, Inc.
France) for their contributions of data used in this paper.
10. Tran T. Nham, Performance evaluation of a new axially

viewed simultaneous ICP-OES using a megapixel CCD
detector for environmental applications Paper 0-18,
European Winter Conference on Plasma
Spectrochemistry, Norway, Feb, 2001.
11. I. Szikla, Determination of 22 Elements Following US
EPA Guidelines with a New Megapixel CCD ICP-OES,
Varian Instruments At Work, Number 30, Mar 2001.


Printed in the USA
November 1, 2010
ICPES-01
Analysis of Plant Materials by

VaporGeneration AA
Application Note
Atomic Absorption
Author
Introduction
Keith G. Brodie
Arsenic and antimony are widely used in modern industries although they are toxic
to both man and animals. Significant levels of these elements can be found throughout 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 higher
levels. The essential role of selenium in animal nutrition was first demonstrated in
1957 [1] but mans requirements are not yet fully defined.
The concentration of these elements in foods is dependent on the soil conditions
and ultimately on the methods of preparation of the food. The levels found in animal
products is dependent on the plant material or other animal food source.
It is of considerable interest therefore to establish the level of these elements, as
well as other toxic metals, in soils, plants and animal tissues.
Arsenic, antimony and selenium have been determined at very low levels by atomic
absorption for many years, and vapor generation atomic absorption offers the most
sensitive means by which they can be measured.
The results of extensive collaborative studies on acid digestion techniques, and
hydride generation AA for the determination of arsenic and selenium in foods have
been reported [2,3]. Several laboratories were involved in those reports.
Sample digestion procedures have ranged from ashing in a furnace with a magnesium nitrate solution [4], to hot digestion in acids usually comprising nitric and perchloric mixtures [5]. Agilent instruments have been used for the vapor generation
measurement of selenium levels in plant and biological material after suitable acid
digestion [5,6].
Many laboratories are reluctant to use perchloric acid with digestions of organic
materials because of the potential risks involved [7,8]. For this reason a number of
digestion procedures have been devised which have eliminated perchloric acid.
Sulphuric acid increases the boiling point of an acid digestion mixture and improves
The digested mixture was made up to 25 mL to give a final

solution in 7 M hydrochloric acid. This stock solution was used
directly for the determination of selenium, but was diluted 1 in
10 with 7 M hydrochloric acid for the determination of arsenic
and antimony.
the action of the other oxidizing acids such as nitric. The only
disadvantage of sulphuric acid is the tendency to form insoluble compounds but the presence of nitric acid avoids the precipitation of trace metals with major components of the
sample. Digestion mixtures of sulphuric, nitric and hydrogen
peroxide have been used successfully for plant materials [7].
Some quantities of powdered orchard leaves were also spiked

with known amounts of arsenic, antimony and these samples
were taken through the same digestion procedure. A standard
additions calibration was thus established. Replicate samples
were taken for each. Blank reagents were also prepared.
The results of the determination of arsenic, antimony and

selenium in NBS orchard leaves (No 1571) by the vapor generation technique are reported here. A digestion procedure
was prepared which did not contain perchloric acid.
Samples were prepared in 7 M hydrochloric acid to ensure

that any SeVI formed in the digestion procedure, was reduced
to the required SeIV prior to analysis. This treatment is
commonly used [5,6,9,10].
Instrumentation
An Agilent AA-1475 with background correction and the VGA76 were used in this study. The background signal was examined for all solutions, but no background was found.
Measurements were therefore reported with the background
corrector off. Hollow cathode lamps were operated at the recommended conditions and an Agilent 9176 strip chart
recorder displayed the traces.
The reduction of AsV (or SbV) to AsIII (or SbIII) was achieved by
the inclusion of potassium iodide in the sodium borohydride
solution [9].
For development of this analytical technique samples were

presented manually.
Figures 1 and 2 show chart recorder traces for the standard

additions measurement of the digests for arsenic and antimony respectively. Approximately 40 seconds are required for
the signal to reach an equilibrium value after introduction of
the sample. Replicate absorbance readings were taken in the
plateau region. It is apparent on Figure 2 that a spike appears
on completion of the signal, and this is due to a brief introduction of air before the next solution is pumped. Such an
occurrence is not uncommon.
Absorbance mode was used and five 3-second integrations

were taken.
The printer was an HP 82905A model. The reagents used for
the VGA-76 were as follows:
Acid channel
Concentrated hydrochloric
acid.
Sodium borohydride channel
0.6% NaBH4in 0.5% NaOH and

10% KI.
Standard additions calibrations for arsenic and antimony are

featured in Figures 3 and 4 respectively. The mean
absorbance is shown and two values are represented by the
error bars on the Figures.
Sample Treatment
That the standard additions technique was necessary, is

demonstrated by aqueous calibrations for those elements on
the same graphs. The calibration slopes are clearly different.
NBS orchard leaves (No. 1571) were dried at 80 C and approximately 0.5 g samples were accurately weighed and prepared
for analysis. The digestion procedure consisted of the addition
of 5 mL concentrated sulphuric with swirling in a beaker. A 5
mL volume of 30% v/v hydrogen peroxide was added slowly
and the reaction allowed to proceed. This addition of hydrogen
peroxide was repeated, and when the reaction had subsided,
the digestion mixture was heated on a hot plate.
Table 1 shows the results obtained for arsenic and antimony

in the orchard leaves. Agreement with the certificate was
good.
Table 1
After cooling, 2 mL of concentrated nitric acid was added and

the mixture heated for about 2 hours to remove excess nitric
acid. A further addition of nitric acid with heating may be
required until the solution is a light straw color.
NBS Orchard Leaves No. 1571
Element
Certificate value g/g
Found* g/g
As
10 2
11 2
Sb
2.9 0.3
2.7 0.2
* Mean of replicate determinations.
Figure 1.
Figure 2.
Figure 3.
Calibration for the determination of arsenic.
Figure 4.
Calibration for the determination of antimony.
Chart recorder traces for the measurement of arsenic in digested

leaves.
Chart recorder traces for the measurement of antimony in

digested leaves.
The level of selenium in the leaves was quite low

(0.08 g/gm) and a value of 0.05 was obtained from just one
measurement by the standard additions technique.
No further study was made on selenium here but details of
extensive work on selenium determination in agricultural
materials by the VGA-76 has been recently reported [10].
An alternative digestion procedure was also attempted in
which nitric and sulphuric acids only were used. The mixture
was heated to remove excess nitric acid and the final solution
was a light straw color. The recoveries from some samples
analysed by this procedure were low, and this procedure was
not pursued further.
Summary
The VGA-76 has been used to determine the amount of
arsenic and antimony in digested orchard leaves. A digestion
procedure was adopted which avoided the use of perchloric
acid and it was necessary to use the standard additions calibration 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, Analyst

106 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-TM18 1980 pp 31.
9.
K. Brodie, B. Frary, B. Sturman and L. Voth, Varian

Instruments at Work No. AA-38, March 1984.
10. A. Gelman, Varian Instruments at Work, No. AA-44, Feb.

1985.

Agilent Technologies, Inc., 1985

Printed in the USA
November 1, 2010
AA050
Nitrogen Determination in Fertilizer

by ICP-OES with an Extended Torch
Application Note
Author
Tran T. Nham
For the determination of nitrogen in fertilizer, colorimetry has been widely used
because of its high sensitivity. However, sample preparation is very time consuming
and tedious for colorimetric measurements, while the ICP-OES technique can analyze the sample solution directly. The purpose of this study was to examine the feasibility 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 N
174.525 nm), and a vacuum monochromator was used. To prevent the entrainment
of air into the plasma, an extended torch was essential.
Experimental
Standard Preparation
All chemicals and reagents used were analytical reagent grade.
Instrumental
An Agilent Liberty 220 ICP spectrometer was used for the
measurement. The extended torch featured a longer outer
tube compared with the standard torch and a slotted cut-out
on the side. A higher plasma gas flow of 22.5 L/min was used
to form a better shield from the surrounding air.
Urea and ammonium sulfate were used for the preparation of

standards for urea and ammonium sulfate analysis. Both
standards and blank were prepared in 0.4 M HCl solution.
The operating parameters of the system for the measurement

of nitrogen are listed in Table 1.
It was observed that a nitrogen signal was detected in the

blank solution. This was because of the presence of dissolved
nitrogen in water, nitrogen contamination in the argon gas
and residual entrainment from the surrounding air. Figure 1
shows signal traces for a 2 wt% N standard and a blank solution.
Table 1.
ICP Operating Parameters
Power
1.5 kW
Plasma gas flow
22.5 L/min
Auxiliary gas flow
1.50 L/min
Nebulizer type
Glass concentric
Nebulizer pressure
1 80 kPa
Pump rate
15 rpm
Long Term Stability
Sample uptake rate
1.8 mL/min
Viewing height
8 mm
PMT voltage
650 V
Integration time
3 sec
Dynamic
Long term stability measurement was performed after a calibration with a 1.5 wt% N standard solution and a blank. The
standard was then analyzed as a sample every 5 minutes continuously for a period of 90 minutes, as shown in Figure 2.
Over the 90 minute period, the reproducibility was 1.44 %RSD.
Snout
High
However, the background nitrogen peak can be subtracted

and corrected for by applying background correction.
Results
Sample Preparation
The N 174.272 nm line, with a detection limit (2 sigma) of 50

mg/L, was selected for the measurement. The results of the
N determination by ICP-D:S together with that found by colorimetry are listed in Table 2.
Urea Sample
For ICP analysis: 10 g of sample was accurately weighed and
transferred into a 500 mL volumetric flask, then distilled
deionized water was added until the mixture was totally dissolved. 20 mL of concentrated HCl was added and made up to
volume with distilled deionized water.
Table 2.
For the colorimetric method: 1 g of sample was accurately

weighed into a 125 mL Kjeldahl flask, 20 mL of concentrated
H2SO4 and 2 Kjeldahl catalyst tablets were added, and then
the mixture was digested at 400 oC for 2.5 hours. After cooling, the mixture was transferred to a 500 mL volumetric flask
and made up to volume with distilled deionized water.
Results for Nitrogen Determination
Sample
Nitrogen concentration (wt %)

ICP-D: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
0.11 %RSD. Typical precision of the colorimetric
measurement is about 0.2 %RSD.
Ammonium Sulfate Sample

25 g of a ground sample was accurately weighed and transferred into a 400 mL beaker. 150 mL of distilled deionized
water and 20 mL of concentrated HCl were added. It was then
boiled for 10 minutes, cooled, transferred to a 500 mL volumetric flask and made up to volume with distilled deionized
water.
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.
Conclusion
However, the sample weight required is 10 times higher with

the ICP technique than for the conventional colorimetric
method, although sample availability is rarely a problem. It is
noted that for urea analysis, standard solution should be prepared from urea, not ammonium sulfate.
Studies have shown that the ICP-D:S technique can be

applied to the measurement of high level of nitrogen in fertilizer. The ICP values are in good agreement with the colorimetric values. The precision of the ICP measurement ranged from
0.11 %RSD.
In summary, the Liberty 220 ICP spectrometer with an

extended torch can be used to determine nitrogen in fertilizer
at wt% level in a fraction of the time taken by the conventional colorimetric method.
The sample preparation procedure for colorimetry is time consuming and tedious, especially for the urea sample. It takes
about 2.5 hours for complete sample digestion, while a simple
dissolution only is required for the ICP-OES technique.
Acknowledgement
Thanks are expressed to John L. Lomas of Incitec Pty Ltd,
Brisbane for the supply of fertilizer samples and for the
results of colorimetric measurements.


Printed in the USA
November 1, 2010
ICPES-14
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The Investigation of Fertilizer

Analyses Using Microwave
Digestion and the Agilent 720-ES
Application Note
Authors
Introduction
Christine M. Rivera
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.
Doug Shrader
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.
Figure 1. MarsXpress digestion temperature profile.
Microwave Digestion System
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.
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.
Calibration Solution Preparation

The calibration summary for Phase 1 is listed in Table 2.
Sample Preparation
Table 2.
Phase 1
Phase 1 Calibration Summary
Elements
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.
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
The microwave digestion method is summarized in Table 1.
Nebulizer type
SeaSpray
Nebulizer flow
0.75 L/min
Table 1. Microwave Digestion Settings
RF Power
1.25 kW
15 L/min
Max
power (W)
%
power
Ramp
(min.)
Pressure Temp.
(PSI)
(C)
Hold
(min)
Plasma gas flow
Stages
Auxiliary gas flow
1.5 L/min
1200
100
15:00
120
15:00
Uptake delay
20 s
200
The total digestion time was 30 minutes. Figure 1 represents

the average digestion temperature over time in the vessels
during sample preparation.
Stabilization delay
10 s
Rinse time
15 s
Internal standard
2 mg/L yttrium
Ionization buffer
0.4% caesium
Integration time*
60 s
Replicates
Total analysis time#
165 s
*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.
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.
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
Sample labels
units
As 188.980
mg/kg
Expected
mg/kg
Ca 370.602
%
Expected
%
Cd 214.439
mg/kg
Expected
%
Cr 267.716
mg/kg
Expected
mg/kg
Sludge B
141
141
0.0233
0.0242
Magruder 4B
2.05
1.75
2.71
2.48
0.64
NA
110
111
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
units
Cu 327.395
%
Expected
%
Fe 261.382
%
Expected
%
K2O 404.721
%
Expected
% K2O
Mg 279.078
%
Expected
%
Sludge B
0.0407
0.0398
0.012
0.014
NA
NA
12.6
12.2
Magruder 4B
Magruder 6B
0.0461
0.0307
0.350
0.400
11.02
10.54
1.62
1.64
1.010
0.976
0.500
0.500
21.37
20.54
0.53
0.62
Sample labels
units
Mn 294.921
%
Expected
%
Na 589.592
%
Expected
%
P 214.914
% P2O5
Expected
% 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
units
Pb 220.353
mg/kg
Expected
mg/kg
Se 196.026
mg/kg
Expected
mg/kg
Zn 213.857
%
Expected
%
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 samples are then typically run on the flame photometer

for available K2O and the auto-analyzer for 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 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.
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.
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
Calibration solutions
(units)
ICP-OES
K2O (769.897 nm)
(% w/v)
Blank
Flame photometer
K2O
(% w/v)
0.1145
0.06023
0.4581
Std 3
Std 4
0.68709
0.24038
0.91612
Std 5
Calibration solutions
(units)
Auto-analyzer
P2O5
(% w/v)
Std 1
Std 2
ICP-OES
P2O5 (214.914 nm)
(% w/v)
1.3742
ICP-OES
K2O (769.897 nm)
(% w/v)
Flame photometer
K2O
(% w/v)
ICP-OES
P2O5 (214.914 nm)
(% w/v)
Auto-analyzer
P2O5
(% 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.
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.
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.
Three Magruder fertilizers and NIST SRM 200a potassium

dihydrogen phosphate (KH2PO4) were carefully weighed to
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
Calibration solutions(units)
K2O 404.721
(% w/w)
K2O 769.897
(% w/w)
P2O5 185.878
(% w/w)
P2O5 214.914
(% w/w)
Blank
0.01139
0.01139
Std 1
Std 2
0.012
Std 3
0.03038
0.05785
0.05785
Calibration
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
Samples(units)
K2O 404.721
(% w/w)
K2O 769.897
(% w/w)
Expected
(% w/w)
P2O5 185.878
(% w/w)
P2O5 214.914
(% w/w)
Expected
(% 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
20.71
20.36
20.90
20.75
22.33
22.07
22.25
22.10
14.04
13.85
14.09
13.86
MAG # 4 duplicate
10.04
10.48
MAG # 6
26.65
25.41
MAG # 6 duplicate
23.99
24.88
MAG # 9
12.57
13.66
MAG # 9 duplicate
12.65
13.66
10.54
25.42
13.00
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
20.82
22.54
13.00

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


Printed in the USA
November 1, 2010
IO-037
Nitrate analysis of water using the

quartz fiber optics dip probe on the
Cary 50/60 UV-Vis
Application Note
Environmental
Author
Introduction
Jeffrey Comerford. PhD.
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.

Mulgrave, Victoria 3170,
Australia
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
Method
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.
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)
Abs = -0.00017conc2 + 0.23364conc + 0.01705
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.
Figure 1. Calibration curve with quadratic fit
Table 1. Nitrate standards data for calibration curve
Instrument Settings
User Result
Eq. 2
= Read(220)-2*Read(275)
Ordinate Mode
Abs
Ave Time (sec)
1.0000
Replicates
Standard/Sample averaging
OFF
Weight and volume corrections
OFF
Fit type
Quadratic
Min R
0.95000
Concentration units
mg/L
Results
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.
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.
Conclusion
Table 2. Raw data and statistics of Water samples

Std
Conc
mg/L
Mean
Abs
SD
%RSD
Raw Abs
0.145
0.0510
0.0009
1.78
0.0520
0.0504
0.0506
0.709
0.1825
0.0025
1.36
0.1797
0.1838
0.1841
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
Discussion
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.
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.
2. P. A. Liberatore, UV-Instrument At Work;

Automated nitrate analysis of water, No. 59, Agilent
Australia Pty. Ltd, Australia, 1993.
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.
Published March, 2011
Publication Number 5990-7932EN

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ICP Operating Conditions

Plasma gas flow

Auxiliary gas flow

Glass cyclonic (single-pass)

Standard axial torch

Instrument pump rate

Replicate read time (s)

Sample delay time (s)

Stabilization delay time (s)

VGA-77P Operating Conditions

Samplepurple/black (2.29 mm ID)

Solution uptake rate

The instrument pump rate must be optimized to ensure that

Standard Solutions and Reagents

Detection Limits (g/L) for Hg in Aqueous Solution

Replicate read time (s)

Short-term precision, determined from the RSD of replicate

Analysis of a Certified Reference Material

Results of Analysis of NBS 2781

Results and Discussion

R. P. Mason, W. F. Fitzgerald, and F. M. M. Morel,

W. F. Fitzgerald and R. P. Mason, Biogeochemical Cycling

C. A. Liebert, J. Wireman, T. Smith, and A. O. Summers,

L. Bringmark, Accumulation of Mercury in Soil and

A. Anderson, Mercury in Soils, Chapter 4 in J.O. Nriagu

C. K. Tan, Analysis of chromium and mercury species in

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

K. Brodie, B. Frary, B. T. Sturman, and L. Voth, Agilent AA

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

10. J. H. Moffett, Measuring ultra-trace levels of mercury,

For More Information

Agilent Technologies, Inc.

Rapid Measurement of Major, Minor

Preparation of Calibration Solutions

An Agilent 730-ES (simultaneous ICP-OES with axially viewed

Calibration solutions were prepared from Inorganic Ventures

The Agilent 730-ES features a custom designed CCD detector,

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

The Agilent 730-ES also includes the productivity-enhancing

Spex CertiPrep single element solutions:

Tables 2 and 3 list the selected elemental wavelengths and

A Mars % closed vessel, microwave digestion system from

Table 1 shows the operating parameters used in this work.

Calibration Standards for the Major and Minor Elements

Plasma gas flow

Auxiliary gas flow

Spray chamber type

Glass cyclonic (single-pass)

Standard axial torch

Sample: white-white (1.02 mm ID)

Total sample usage

Replicate read time

Sample delay time

Switching valve delay

The soil samples were prepared by accurately weighing 0.25 g