Analytical Chemistry Research 11 (2017) 9e12

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Analytical Chemistry Research

journal homepage: www.elsevier.com/locate/ancr

Enhancement of the atomic absorbance of Cr, Zn, Cd, and Pb in metal

furnace atomic absorption spectrometry using absorption tubes
Yuya Koike a, *, Kenta Hagiwara b, Toshihiro Nakamura a
a
Department of Applied Chemistry, School of Science and Technology, Meiji University, 1-1-1, Higashimita, Tama-ku, Kawasaki, Kanagawa, 214-8571, Japan
b
Organization for the Strategic Coordination of Research and Intellectual Properties, Meiji University, 1-1-1, Higashimita, Tama-ku, Kawasaki, Kanagawa,
214-8571, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Trace amounts of Cr, Zn, Cd, and Pb were determined by metal furnace atomic absorption spectrometry
Received 23 August 2016 using absorption tubes. Various absorption tubes were designed as roof- and tube-types, and fixed above
Received in revised form the metal furnace in order to extend the light path length. Aqueous standards and samples were injected
17 November 2016
in the metal furnace and atomized in a metal atomizer with an absorption tube (6 cm length, 15.5 mm
Accepted 18 November 2016
Available online 21 November 2016
diameter). The used of an absorption tube resulted in an enhancement of the atomic absorbance. The
ratios of absorbance values with and without the roof- and tube-type absorption tubes were 1.33 and 1.11
for Cr; 1.42 and 1.99 for Zn; 1.66 and 1.98 for Cd; and 1.31 and 1.16 for Pb, respectively. The use of an
Keywords:
Absorption tube
absorption tube was effective for Zn and Cd analysis, as the absorbance values for these low boiling point
Atomic absorbance enhancement metals doubled. The proposed method was successfully applied in the determination of Zn in tap water.
Heavy metal © 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
Low boiling point metal license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Metal furnace atomic absorption
spectrometry

1. Introduction [10] investigated a furnace AAS method for As determined as

The sensitivity of furnace atomic absorption spectrometry (AAS)
is still insufficient for the determination of trace elements such as
toxic heavy metals at natural background levels. Methods to
improve the sensitivity of AAS have been attempted, such as that
achieved with metal furnace atomic absorption spectrometry
(MFAAS). In 1970, Donega [1] conducted a highly sensitive analysis
of several elements with an electrically heated Ta boat, on which
MFAAS was based. Although MFAAS is used for various analyses
[2e9], its sensitivity is not sufficient for the determination of trace
metals without a previous preconcentration step.
Atomic absorbance is determined from signals corresponding to
the numbers of measured atoms, and is independent of the atomic
evolution time. The integrated absorbance is proportional to the
average residence time of the atomic vapor in the furnace. It is also
proportional to the length of the furnace according to the Beer-
Lambert law. The elongations of the residence time and the light
path length for furnace AAS enhance the atomic absorbance and,
therefore, absorption tubes have been used in the past. Chu et al.
* Corresponding author.
E-mail address: koi@meiji.ac.jp (Y. Koike).
arsine. The arsine evolved was swept into an electrically heated
absorption tube by means of a carrier gas (Ar). Goulden et al. [11]
conducted the determination of sub-mg levels of Sb, As, and Se in
natural water using a quartz tube. Stibine, arsine, and hydrogen
selenide were produced from the samples, respectively, in an
automated system, and passed through a tube furnace mounted in
the light path of the atomic absorption spectrophotometer.
Although these methods provide sensitive analysis, they are not
available for the determination of heavy metals that do not form
gaseous hydrides. A matrix modifier has often been used as at-
omization an intensifier, but it does not have the expected effect for
elements with extremely low boiling points [12,13] or high ioniz-
ability [14].
An open-type metal furnace atomizer has a W boat in the glass
container sealing to some extent. The atomic vapor instantaneously
diffuses from the measurement region without hysteresis, so that it
does not cause any pre-excitation of atoms. The flow of the atomic
vapor is prevented because the metal furnace is covered with an
absorption tube, and the carrier gas stream is evacuated through
the absorption tube. Thus, the absorption tube enhances atomic
absorbance.
This paper describes a method using MFAAS combined the use

http://dx.doi.org/10.1016/j.ancr.2016.11.004
2214-1812/© 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
10 Y. Koike et al. / Analytical Chemistry Research 11 (2017) 9e12

of absorption tubes for the determination of trace amounts of Cr,

Zn, Cd, and Pb. Owing to the diffusion of the vapor outside of the
tube at low temperatures along the optical axis, the use of an ab-
sorption tube in the metal furnace also extended the residence time
of the atomic vapor. The optimum instrumental conditions and
design of several absorption tubes are discussed. The application of
absorption tubes in the detection of several elements (Cr, Zn, Cd,
and Pb), and the quantitative analysis of Zn in tap water are also be
described. The proposed absorption tubes were successfully
applied for the enhancement of the atomic absorbance of low
boiling point metals.

2. Material and methods Fig. 1. Schematic figure of the metal atomizer head with the absorption tube.

2.1. Material
A metal furnace atomic absorption spectrometer (SEIKO SAS
760) equipped with a flameless atomizer (SEIKO SAS 715), a metal
furnace, a mono atomic hollow cathode lamp, and a data processing
module were used for the determination of Cr, Zn, Cd, and Pb in
water. A deuterium lamp was used for background correction. At-
omization was conducted in the metal furnace, and the heating
temperature of the metal atomizer was controlled by the constant
voltage (AC 200V). Pure Ar and H2 were used as the carrier gas and
the reducing gas, and these gases were supplied from the lower
part of the W metal furnace. Aqueous solutions (10 mL) were
injected into the metal furnace using an Eppendorf Model 4800
micropipette. The operation conditions are given in Table 1.
Cr, Zn, Cd, and Pb test solutions (100 mg L
1) were prepared from
1000 mg L
1 standard solutions (Junsei Chemical). The tap water
sample was collected at Kawasaki, Japan.
2.2. Methods
The absorption tubes were made of silica glass, and designed as
tube- and roof (half tube)-types, 6 cm long and 15.5 mm in diam-
eter. They were fixed above the metal furnace with two pieces of
wire and polyurethane foam packing (Fig. 1). Each measurement
was repeated five times.
3. Results and discussion
3.1. Design of absorption tubes
In this study, several absorption tubes having different shape,
length, and diameter were prepared (tube-type: 5, 6, or 7 cm
diameter and 12 or 15.5 mm diameter, roof-type: 5 or 6 cm
diameter and 12 or 15.5 mm diameter; Fig. 2). The diameter of the
absorption tubes was based on the size of the metal furnace with a
W plate of 0.2 mm thickness (5 mm height, 60 mm length, and 7 or
5, 6, 7 cm
12, 15.5 cm
A
1.5, 2.0, 2.5 cm 2 cm
5, 6 cm
B
12, 15.5 cm
Fig. 2. Schematics of the absorption tubes made of silica glass. A: tube-type, B: roof-
type.
10 mm width; Fig. 3). The absorption tubes were designed on the
basis of the size of the metal atomizer head. The absorption tubes
were disposed to cross the metal furnace, and were fixed at the top
of the furnace chamber with polyurethane foam packing.
3.2. Preheating of absorption tubes
The enhancement of the atomic absorbance with the absorption
tubes was evaluated by testing the atomic absorbance of de-
terminants in aqueous standards of Cr. The absorption tubes
needed to be preheated before the measurements to prevent
condensation of the atomic vapor. When the absorption tubes were
not preheated, a sufficient absorbance was not obtained with
specifications (6 cm length and 15.5 mm diameter) used, and the
absorbance using tube- and roof-type absorption tubes were as
follows; not preheated: 1.048 and 0.764, and preheated: 2.301 and
2.445, respectively. Cold tubes afforded lower absorbance values in
the first measurement because of the physical adsorption of the
atomic vapor inside the tube. In order to preheat the absorption

Table 1
Instrumental parameters for MFAAS of Cr, Zn, Cd, and Pb in water.

Instrumental parameters
Element Cr Zn Cd Pb
Analytical line / nm 357.9 213.9 228.8 217.0
Lamp current / mA 10 7.0 5.0 10
Slit width / nm 1.08
Ar gas flow / dm3 min
1 5.0
H2 gas flow / dm3 min
1 1.0
Absorbance Peak area
Atomization conditions
Drying step /  C 150 (ramp 20s) 150 (ramp 20s) 150 (ramp 20s) 150 (ramp 20s)
Pyrolysis step /  C 200 (hold 20 s) 400 (hold 20 s) 500 (hold 20 s) 300 (hold 20 s)
Atomization step /  C 1900 (hold 20 s) 1100 (hold 20 s) 1400 (hold 20 s) 2100 (hold 20 s)
 Y. Koike et al. / Analytical Chemistry Research 11 (2017) 9e12
Fig. 3. Schematics of the metal atomizers with a W plate of 0.2 mm thickness. A: metal atomizer for the atomization tube with 15.5 mm diameter. B: metal atomizer for the
atomization tube with 12 mm diameter.
tubes, the metal furnace was heated to the atomization tempera-
ture (20 s with 1900  C for Cr, 1100  C for Zn, 1400  C for Cd, and
2100  C for Pb) only once before the first measurement.
3.3. Optimum absorption tube size
Figure 4 shows the variation of the atomic absorbance of Cr with
the length of the absorption tube. The atomic absorbance was
enhanced in all the cases where an absorption tube was used. The
enhancement of the atomic absorbance indicates that the proposed
method with absorption tubes is effective. The maximum absor-
bance was obtained using an absorption tube of 6 cm length and
15.5 mm diameter. The enhancement of the atomic absorbance of
Cr using the roof-type absorption tube was more pronounced than
that obtained using the tube-type one. The use of absorption tubes
increases the atomic vapor population. However, there was no
much differences among the atomic absorbance values using ab-
sorption tubes having different lengths and diameters. In subse-
quent experiments, absorption tubes of 6 cm length and 15.5 mm
diameter were used for MFAAS.
3.4. Enhancement of atomic absorbance with absorption tubes
The proposed absorption tubes were applied in the analysis of
heavy metals. The absorption tubes were developed for the deter-
mination of the atomic absorbance of Cr, Zn, Cd, and Pb in aqueous
Fig. 4. Variation of the atomic absorbance of 1 ng of Cr with the length of the ab-
sorption tube.
11
standards. The ratios of the atomic absorbance with and without
the absorption tubes are shown in Table 2. The enhancement of the
absorbance obtained for Cr, Zn, Cr, and Pb using the absorption
tubes. The roof-type absorption tube resulted in enhancements of
the absorbance for every element, and the absorbance intensity
increased by 31e66% compared to that measured without the ab-
sorption tube. Meanwhile, the tube-type absorption tube was
found to be effective for low boiling point metals, and the absor-
bance intensities of Cd and Zn were double of those measured
without the absorption tube.
3.5. Calibration curve and detection limit
In order to quantify Zn in a water sample, a calibration curve of
Zn was obtained using standard solutions. Linear calibration graphs
with and without the tube-type absorption tube were obtained
using calibration standards containing determinants from 0 to 1 ng
in aqueous solutions. The calibration curves are shown in Fig. 5. The
linear regions of the calibration graphs obtained with and without
the tube-type absorption tube were in the range 0e0.6 ng. The
detection limits, defined as three times the standard deviation of
the blank values, were 0.030 ng without the tube, and 0.018 ng with
the absorption tube. The calibration graphs indicate that the pro-
posed method using absorption tubes is suitable for quantitative
analysis.
3.6. Application of proposed method
The results obtained for tap water with the tube-type absorp-
tion tube are given in Table 3. The value obtained by a standard
method without the absorption tube is also given for comparison.
The concentration of Zn obtained using the absorption tube agrees
well with the value using the method not using an absorption tube.
Table 2
Boiling points of Cr, Zn, Cd, and Pb and atomic absorbance ratios of 1 ng metals with
and without absorption tubes (6 cm length and 15.5 mm diameter).
Boiling point /  C Signal with tube / Signal without
tube
Roof-type Tube-type
Cr 2690 1.33 1.11
Zn 907 1.42 1.99
Cd 765 1.66 1.98
Pb 1751 1.31 1.16
12 Y. Koike et al. / Analytical Chemistry Research 11 (2017) 9e12
Fig. 5. Calibration curves of Zn in aqueous standard with (C) and without (-) the
absorption tube.
Table 3
Analytical results of Zn concentration determination in tap water.
Zn concentration / mg L
1 RSD, %
Tube-type absorption tube 1.24 4.1
No tube 1.16 10.3
RSD: Relative standard deviation, % (n ¼ 5).
The relative standard deviation of the proposed method was 4.1%,
and so the reproducibility also improved relative to the method not
using an absorption tube. Thus, quantitative analysis, including that
of low boiling point metals, can be conducted with the proposed
method with the tube-type absorption tube.
4. Conclusions
Metal furnace atomic absorption spectrometry assisted with an
absorption tube was used in the determination of trace amounts of
Cr, Zn, Cd, and Pb. The roof- and tube-type absorption tubes
resulted in the enhancement of the atomic absorbance of the
metals. The roof-type absorption tube was effective for Cr, Zn, Cd,
and Pb, as their absorbance intensities increased by 31e66%
compared to those measured by the system without the absorption
tube. Meanwhile, the tube-type absorption tube was effective in
the determination of low boiling point metals, and the absorbance
intensities obtained for Cd and Zn were double of those measured
without the absorption tube. The proposed method was success-
fully applied in the determination of Zn in tap water.
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