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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.
Parameter
Setting
Power
0.9 kW
13.5 L/min
1.5 L/min
Nebulizer type
Glass concentric
Nebulizer pressure
240 kPa
Spraychamber type
Torch type
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.
45 rpm
Number of replicates
20
30
Fast pump
Off
Table 2.
Parameter
Setting
Inert gas
Argon
Pump tubing
Sample8 mL/min
Reductant1 mL/min
Acid/water1 mL/min
Table 3.
184.887 (nm)
194.164 (nm)
253.652 (nm)
30
0.023
0.022
0.020
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.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or
for incidental or consequential damages in connection
with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this
publication are subject to change without notice.
Application Note
Inductively Coupled Plasma-Optical Emission Spectrometers
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
Table 2.
1000 mg/L Al
1000 mg/L P
1000 mg/L Sr
1000 mg/L Ti
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
15 L/min
Mg
285.213
10
20
100
200
1.5 L/min
766.491
10
20
100
178.222
10
20
Torch
Na
588.995
10
20
Nebulizer type
Seaspray
Ti
336.122
10
20
Nebulizer flow
0.7 L/min
Pump tubing
Condition
Pump speed
15 rpm
1 mL
3s
Number of replicates
20 s
17 s
Stabilization time
12 s
Rinse time
1s
Fast pump
On
Background correction
Fitted
Table 3.
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
Pb
220.353
10
50
250
1000
Mn
260.568
10
50
250
1000
Zn
206.200
10
50
250
1000
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
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 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
2.3%
1.7%2.3%
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.
Table 6.
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
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.
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
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.
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.
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.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or
for incidental or consequential damages in connection
with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this
publication are subject to change without notice.
Application Note
Inductively Coupled Plasma-Optical Emission Spectrometers
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.
Instrumentation
Condition
Setting
Power
1.2 kW
15 L/min
1.5 L/min
Nebulizer flow
0.75 L/min
Pump speed
15 rpm
Integration time
5s
Number of replicates
35 s
Stabilization time
10 s
Background correction
Fitted
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.
Table 2.
Stage
Wavelength
Ca
422.673
Ca
317.933
30
Ca
183.738
1000
Ca
220.861
5000
Cu
324.754
10
15
Table 4.
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
Control sample 2
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
0.042 0.001
0.030.04
Figure 1.
Table 5.
7.
8.
9.
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
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or
for incidental or consequential damages in connection
with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this
publication are subject to change without notice.
Author
Background
Michael B. Knowles
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.
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.
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.
Table1.
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.
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
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.
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.
Figure 5.
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).
Table 2.
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
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.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
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.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or
for incidental or consequential damages in connection
with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this
publication are subject to change without notice.
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 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].
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].
Concentrated hydrochloric
acid.
Sample Treatment
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.
Element
Found* g/g
As
10 2
11 2
Sb
2.9 0.3
2.7 0.2
Figure 1.
Figure 2.
Figure 3.
Figure 4.
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.
2.
3.
4.
5.
6.
7.
8.
9.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or
for incidental or consequential damages in connection
with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this
publication are subject to change without notice.
Application Note
Inductively Coupled Plasma-Optical Emission Spectrometers
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.
Table 1.
Power
1.5 kW
22.5 L/min
1.50 L/min
Nebulizer type
Glass concentric
Nebulizer pressure
1 80 kPa
Pump rate
15 rpm
1.8 mL/min
Viewing height
8 mm
PMT voltage
650 V
Integration time
3 sec
Background correction
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
Results
Sample Preparation
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.
Sample
Urea
46.5 0.2
46.4
Ammonium sulfate
20.1 0.3
20.4
Figure 1.
Spectral scan of a 2 wt% N standard solution and a blank at the N 174.272 nm line.
Figure 2.
Conclusion
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.
www.agilent.com/chem
Agilent shall not be liable for errors contained herein or
for incidental or consequential damages in connection
with the furnishing, performance, or use of this material.
Information, descriptions, and specifications in this
publication are subject to change without notice.
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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.
Sample Preparation
Table 2.
Phase 1
Elements
Concentration (mg/L)
0.5, 5, 10 and 50
Conditions
Instrument operating conditions are shown in Table 3.
Table 3.
Parameter
Setting
Spraychamber type
Nebulizer type
SeaSpray
Nebulizer flow
0.75 L/min
RF Power
1.25 kW
15 L/min
Max
power (W)
%
power
Ramp
(min.)
Pressure Temp.
(PSI)
(C)
Hold
(min)
Stages
1.5 L/min
1200
100
15:00
120
15:00
Uptake delay
20 s
200
Stabilization delay
10 s
Rinse time
15 s
Internal standard
2 mg/L yttrium
Ionization buffer
0.4% caesium
Integration time*
60 s
Replicates
165 s
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
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.
Table 5.
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)
34.81
34.64
52.62
52.11
Sample 1
4.51
4.59
21.6
21.59
Sample 2
4.50
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
19.87
20.07
Sample 6
2.50
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
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.
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
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
www.agilent.com/chem
Introduction
Experimental
Equipment
Reagents
Chloroform (A.R.)
Method
Equation 1
Instrument Settings
User Result
Eq. 2
= Read(220)-2*Read(275)
Ordinate Mode
Abs
1.0000
Replicates
Standard/Sample averaging
OFF
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
Conclusion
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
Reference
Discussion
www.agilent.com/chem
Agilent Technologies, Inc., 2011
Published March, 2011
Publication Number 5990-7932EN