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Determination of the Uncertainty of the Flame Atomic Absorption

Spectrometer for Copper, Cobalt, Cadmium, and Nickel

Article  in  Analytical Letters · October 2009

DOI: 10.1080/00032710903243513

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Determination of the Uncertainty of the Flame Atomic Absorption Spectrometer

for Copper, Cobalt, Cadmium, and Nickel
Alexander Petrov a; Galia Gentscheva a; Ivan Havezov a; Elisaveta Ivanova a
a
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria

Online Publication Date: 01 January 2009

To cite this Article Petrov, Alexander, Gentscheva, Galia, Havezov, Ivan and Ivanova, Elisaveta(2009)'Determination of the Uncertainty
of the Flame Atomic Absorption Spectrometer for Copper, Cobalt, Cadmium, and Nickel',Analytical Letters,42:16,2509 — 2519
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 Analytical Letters, 42: 2509–2519, 2009
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DOI: 10.1080/00032710903243513

ATOMIC SPECTROSCOPY

Determination of the Uncertainty of the Flame

Atomic Absorption Spectrometer for Copper,
Cobalt, Cadmium, and Nickel
Downloaded By: [Petrov, Alexander] At: 11:52 2 November 2009

Alexander Petrov, Galia Gentscheva, Ivan Havezov,

and Elisaveta Ivanova
Institute of General and Inorganic Chemistry, Bulgarian Academy
of Sciences, Sofia, Bulgaria

Abstract: The sources of uncertainty in the determination of copper, cobalt,

cadmium, and nickel, originating from the flame atomic absorption spectrometer,
were studied. They were identified and divided in three main groups according to
their origin—from the flame, from the light source (hollow-cathode lamp), and
from the optics. The combined uncertainty of the flame atomic absorption
determination was experimentally determined.

Keywords: Cadmium, cobalt, copper, flame atomic absorption spectrometer,

nickel, uncertainty of instrument

INTRODUCTION

Atomic absorption spectrometry (AAS) is one of the most widespread

methods for quantitative trace element determination in various samples,

Received 9 October 2008; accepted 4 August 2009.

The authors thank the Centre of Competence on Multifunctional Materials
and New Processes with Environmental Impact (MISSION), Contract
EC-INCO-CT-2005-016414, for financial support.
Address correspondence to Dr. Galia Gentscheva, Institute of General and
Inorganic Chemistry, Bulgarian Academy of Sciences, ‘‘Acad. Georgi Bontchev’’
Str. Bld.11, 1113 Sofia, Bulgaria. E-mail: gentg@svr.igic.bas.bg

2509
 2510 A. Petrov et al.

e.g., environmental, biological, clinical, and industrial. An estimation of

the uncertainty of the determination is required by EN ISO=IEC 17025
(2005) as a part of method validation. The determination of the trace ele-
ments is affected by a large number of uncertainty sources originating
from the different steps of the laboratory procedures applied and from
the AAS itself.
When building the uncertainty budget of a method, emphasis is
usually put on the sample preparation steps—digestion, dilution, precon-
centration, etc. (Kristiansen, Christensen, and Nielsen 1996; Synek,
Subrt, and Marecek 2000; Boti, Sakkas, and Albanis 2007), and the
uncertainty of the detection instrument is included in the uncertainty of
the calibration.
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It is important to estimate the uncertainity of the separate steps of

the measurement process in order to identify the critical ones.
The uncertainty of the flame atomic absorption spectrometric
(FAAS) instrument has been studied by Hirano, Imai, and Yasuda
(2005). Drift of signal, noise, and nonlinearity of the calibration
curve have been found to be the main sources of uncertainty in the
absorbance measurement, and factors affecting these sources were
evaluated using cadmium as a model element (Hirano, Imai, and
Yasuda 2005).
In the present paper the uncertainty sources of the Thermo
Electron-SOLAAR Mkll M5 series FAAS instrument were studied in
the determination of trace amounts of copper, cobalt, cadmium, and
nickel as a part of the development and validation of a method
for trace element analysis in water. Data on the overall performance
of the apparatus, as well as on the individual sources of uncertainty
which can be included in the estimation of the uncertainty, were
gathered.

EXPERIMENTAL

Instrumentation and Reagents

Thermo Electron M5 (UK) FAAS was used.

Table 1 presents the characteristics of the FAAS instrument. In
Table 2 the measurement conditions of the FAAS determination of
copper, cobalt, cadmium, and nickel are given.
The standard solutions of the analyte elements with various concen-
trations were prepared from Merck Titrisol1. Triply distilled water from
quartz still was used.
 Determination of the Uncertainty of the FAAS 2511

Table 1. Characteristics of the FAAS Thermo Electron M5 instrument

Optics Stockdale Double Beam

Monochromator Echelle type
Lamp Carousel 6 Lamp Coded, Auto-aligning
Photomultiplier Standard-range type
Flame Atomizer Universal system (uses 50 mm Ti burner)
Background Correction QuadLine deuterium system
Gas Management Automatic (binary control)
Flame Air-Acetylene

Identification of Uncertainty Sources

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The uncertainties of the standard solutions were not discussed in the

present work.
The estimation of the uncertainty of the FAAS instrument,
performed in the present study, consisted of the following steps:

1. Specification of the measurand: in estimating the uncertainty the

measurand was the absorbance value (Abs.).
2. Identification of the uncertainty sources: the sources of uncertainty
were identified and divided in three main groups according to their
origin—from the flame, from the light source (hollow-cathode lamp),
and from the optics (see Fig. 1).
3. Quantification of the identified sources: the standard uncertainity was
experimentally estimated for all sources where it was technically possible.

Noise on the FAAS signal originates in various ways throughout the

AAS:
Flame Noise arises from refractive index variations between the
different parts of the flame and from small variations in the effective path
length of the flame.

Table 2. Measurement conditions

Spectrometer parameters

Wavelength, Band width, Lamp current, Burner height, Fuel flow

nm nm % mm l min
1

Cu 324.8 0.5 75 9.0 0.9

Co 240.7 0.2 75 7.8 1.0
Ni 232.0 0.2 75 7.8 0.8
Cd 228.8 1.0 50 7.8 1.0
 2512 A. Petrov et al.
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Figure 1. Uncertainty sources in absorbance measurement by FAAS.

Nebulizer Noise is caused by fluctuations in the amount of sample

actually reaching the flame.
Both flame noise and nebulizer noise result in short-term fluctuations
of the atomic absorption signal.
Light Source Noise consists of long-term (drift and=or line broaden-
ing) and short-term is noise.
Detector Noise is short-term noise divided into dark noise and shot
noise. As the shot noise is proportional to the square root of the incident
intensity, the detector should not be operated close to its threshold inten-
sity value. Often a wider band width of the monochromator is used in
order to have sufficient light intensity at the detector.
Stray light and the effect it has on optical signal to noise ratio (S=N)
falls into one of two major categories, either (a) random scatter from mir-
rors, gratings, etc.; or (b) directional stray light such as reflections, reentry
spectra (nearby lines of the element or fill gas of the hollow-cathode lamp,
continuous flame emission), grating ghosts, and grating generated focused
stray light. Noises from stray light of the monochromator are virtually neg-
ligible in modern constructions of FAAS (Hirano, Imai, and Yasuda 2005).
Intensity of hollow-cathode lamp is an important factor in determining
the signal=noise ratio at the detector. It depends on the construction of
the hollow-cathode lamp and is proportional to the lamp current used. The
higher the lamp current, the better is the intensity and consequently the
signal=noise ratio. But, there is another problem, at higher lamp currents
self reversal of the analytical line may occur, which lowers the absorptivity
coefficient of the primary radiation. This effect decreases the analytical
sensitivity of the FAAS determination. This effect is significant for the deter-
mination of volatile elements like Cd. In that case, careful optimization of
the lamp current is needed in order to ensure an optimal signal=noise ratio
for the atomic absorption signal at the highest analytical sensitivity.
 Determination of the Uncertainty of the FAAS 2513

Flame conditions are important to ensure the highest possible

atomization efficiency. The lean air=acetylene flame is optimal for the
elements studied.
Flickering of flame is a function of the physical stability of the flame
used. The higher the stability of the flame, the better signal=noise ratio is
reached. In our case, the optimal lean flame is also the one with the high-
est stability, so the effect of flame flickering is minimized.

RESULTS AND DISCUSSION

Figure 1 depicts the identified uncertainty sources in the FAAS spectro-

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meter. They are interrelated because of their simultaneous participation

in the absorbance measurement. The procedure can be performed in
the following consecutive steps:

Step 1. Absorbance measurement at a defined wavelength and band width

without flame—assessment of the simultaneous effect of light
source noise, detector noise, stray light, and intensity of HCL.
Step 2. Absorbance measurement at a defined wavelength and band
width in the flame—assessment of the simultaneous effect of
light source noise, detector noise, stray light, intensity of HCL,
flame noise, flame conditions, and flickering of flame.
Step 3. Absorbance measurement at a defined wavelength and band
width in the flame by aspirating analyte solution – assessment
of the simultaneous effect of light source noise, detector noise,
stray light, intensity of HCL, flame noise, flame conditions, flick-
ering of flame, nebulizer noise, and sensitivity of determination.

Figure 2 visually represents the previously mentioned three steps in

uncertainty estimation.

Step 1

The hollow-cathode lamp is a gas discharge device. Therefore, after

switching on, its emission intensity changes during a certain period of
time until it stabilizes. The stabilization time of the hollow-cathode lamps
is different depending on the element.
One of the main reasons for the design of double-beam AAS instru-
ments is the necessity of compensating the intensity drift of the hollow-
cathode lamp during the measurement, thus avoiding the necessity of
often use of the autozero function. Even in double-beam AAS instru-
ments, however, not only the emission intensity, but also the line
 2514 A. Petrov et al.
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Figure 2. Three steps of uncertainty estimation.

broadening varies during the pre-heating of the hollow-cathode lamp

which affects the intensity of the radiation reaching the detector and
changes the atomic absorptivity (especially for volatile elements).
Figure 3 shows the intensity changes of the hollow-cathode lamps of
Cu, Co, Ni, and Cd during a period of 50 min after switching on. The
band width values used for Ni were 0.1 and 0.2 nm; those for Cd were
0.5 and 1.0 nm.
The stabilization of the hollow-cathode lamp intensity emission for
Cu and Co requires about 20 min after switching on (Fig. 3). Using the
band width values recommended by the manufacturer for Ni and Cd
(0.1 nm and 0.5 nm, respectively), however, the emission intensity of these
hollow-cathode lamps did not stabilize in that time; moreover, the drift of
the Cd hollow-cathode lamp displayed unusual shape (Fig. 3). The use of
band width values of 0.2 and 1.0 nm for Ni and Cd, respectively, ensured
stabilization of the hollow-cathode lamp intensity. Therefore, band width
values of 0.2 nm for Ni and 1.0 nm for Cd were used in further work.
The values of the standard uncertainty, calculated according to
(EURACHEM=CITAC Guide CG4 2000; ISO=IEC Guide 98 1995),
are presented in Table 3. These values include the influence of all factors
studied.

Step 2

The air-acetylene flame is the most widely used flame in FAAS. It is

stable, simple to operate, and possesses enough energy to produce
 Determination of the Uncertainty of the FAAS 2515
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Figure 3. Drift of hollow-cathode lamp intensity for Cu, Co, Ni and Cd: (a) Cu
band width 1.0 nm; (b) Co band width 0.5 nm; (c) Ni band width 0.1 nm; (d) Ni
band width 0.2 nm; (e) Cd band width 0.5 nm; (f) Cd band width 1.0 nm.

sufficient atomic population to enable good sensitivity and freedom from

interferences for many elements.
The flame conditions (flows of fuel and oxidant) are optimized
according to the concrete analyte and sample matrix. As the temperatures
of the flame are higher in the center and lower in the outer region, the
atomic density of the analyte in the flame is not uniform. The observation
height and the lateral position of the burner are of great importance as

Table 3. Uncertainty of the hollow-cathode lamp intensity for Cu, Co, Ni and Cd
Standard uncertainty, Abs

Element 0–10 min 10–20 min 20–30 min 30–40 min 40–50 min

Cu 0.00097 0.000170 0.000008 0.000007 0.000007

Co 0.00085 0.000032 0.000010 0.000010 0.000009
Ni band width 0.1 nm 0.00344 0.000247 0.000162 0.000086 0.000047
Ni band width 0.2 nm 0.00165 0.000084 0.000009 0.000008 0.000008
Cd band width 0.5 nm 0.00071 0.000063 0.000372 0.000306 –
Cd band width 1.0 nm 0.00067 0.000065 0.000037 0.000018 0.000016

The values are used in the uncertainty calculations.
 2516 A. Petrov et al.
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Figure 4. Flickering of flame: (a) Cu; (b) Co; (c) Ni; (d) Cd.

well. Although these factors affect the uncertainty of the AAS instru-
ment, their contribution cannot be quantified.
The flame flickers as a function of reduction=oxidation reactions in
the flame and may thus contribute to short-term, irregular fluctuations
in the signal, i.e., noise. Flame flickering is lower in lean flames.
The effect of flame flickering on the signal was followed by
measuring the signal for triply distilled water under the optimum flame
conditions for each element (see Table 2). As a result, 20 min of hollow-
cathode lamp pre-heating was used (Fig. 4).
Double-beam systems are neither capable of recognizing nor of com-
pensating for changes in the atomizer, such as flame fluctuations during
the warm-up phase of the burner. (Welz and Sperling 1998). As can be seen
from Fig. 4, approximately 10 min are required for burner stabilization.
The calculated values of the standard uncertainty after burner stabi-
lization are: Cu – 0.000009 Abs, Co – 0.000022 Abs, Ni – 0.000019 Abs
and Cd – 0.000045 Abs.
Along with the influence of flame flickering, the obtained values
include the influence of all electronic devices in the detector and the
monochromator, the intensity drift of the hollow-cathode lamp, and
the contributions of fuel and air flow deviations.

Step 3

The sensitivity drift for Cu, Co, Ni, and Cd is shown in Fig. 5. This study
was performed by introducing a solution of the analyte in the flame so
the nebulizer noise was included in the signal uncertainty.
For estimating the standard uncertainty for Cu, Co, Ni, and Cd, the
uncertainty values obtained after the stabilization of the sensitivity
 Determination of the Uncertainty of the FAAS 2517
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Figure 5. Sensitivity drifts after the beginning of the sample nebulization: (a) Cu;
(b) Co; (c) Ni; (d) Cd.

were: Cu, 0.1 mg l
1 – 0.00010 Abs, Co, 0.1 mg l
1 – 0.00013 Abs, Ni,
0.3 mg l
1 – 0.00005 Abs, Cd, 0.05 mg l
1 – 0.00017 Abs.
These values include the influence of all electronic devices in the
detector, the monochromator, the intensity drift of the hollow-cathode
lamp, the flame flickering, and the contribution of fuel and air flow
deviations, as well as the influence of the analyte. Therefore these values
may be considered as the combined uncertainty of the AAS instrument.
The combined uncertainty is given by
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uðyÞ ¼ c21 uðx1 Þ2 þ c22 uðx2 Þ2 þ c23 uðx3 Þ2

where:

u(x1) – intensity drift of HCL (Intensity of HCL);

u(x2) – flame noise, flame conditions and flickering of flame (Flame);
u(x3) – nebulizer noise and sensitivity of determination (Nebulizer); and
ci – sensitivity coefficients.

Table 4. Values of uncertainty contributions obtained for the analytes

Element Intensity of HCL Flame Nebulizer

Cu 0.000008 0.000004 0.000099

Co 0.000010 0.000020 0.000128
Ni 0.000009 0.000017 0.000046
Cd 0.000037 0.000026 0.000163
 2518 A. Petrov et al.
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Figure 6. Relative contribution of the separate components of the combined

uncertainty.

Assuming the sensitivity coefficients equal to 1, we may estimate the

influence of the three sources of uncertainty determined: step 1, step 2
and step 3.
For Cu:

uðx1 Þ ¼ 0:000008
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uðx2 Þ ¼ 0:0000092
0:0000082 ¼ 0:000004
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uðx3 Þ ¼ 0:000102
ð0:0000082 þ 0:0000042 Þ
¼ 0:000099

The values of u(x1), u(x2), and u(x3) obtained for all analytes as
presented are in Table 4.
Figure 6 illustrates the relative contribution of the separate compo-
nents of the combined uncertainty.

CONCLUSION

It follows from the obtained results that the main contribution to the
combined uncertainty of the FAAS instrument under optimum condi-
tions comes from the nebulizer: 64  89%. In second place for Cu and
Cd is the hollow cathode lamp intensity drift, whereas, for Co and Ni
these are the flame stoihiometry and the flickering of flame.
 Determination of the Uncertainty of the FAAS 2519

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