Accepted Manuscript

Enhancement of the atomic absorbance of Cr, Zn, Cd, and Pb in metal furnace atomic
absorption spectrometry using absorption tubes

Yuya Koike, Kenta Hagiwara, Toshihiro Nakamura

PII: S2214-1812(16)30029-5
DOI: 10.1016/j.ancr.2016.11.004
Reference: ANCR 58

To appear in: Analytical Chemistry Research

Received Date: 23 August 2016

Revised Date: 17 November 2016
Accepted Date: 18 November 2016

Please cite this article as: Y. Koike, K. Hagiwara, T. Nakamura, Enhancement of the atomic absorbance
of Cr, Zn, Cd, and Pb in metal furnace atomic absorption spectrometry using absorption tubes, Analytical
Chemistry Research (2016), doi: 10.1016/j.ancr.2016.11.004.

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Polyurethane foam packing Wire

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Metal atomizer

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Absorption tube

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Lamp Detector

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

atomic absorption spectrometry using absorption tubes

Yuya Koike1*, Kenta Hagiwara2 and Toshihiro Nakamura1

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Department of Applied Chemistry, School and Science and Technology, Meiji

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University, 1-1-1, Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571, Japan

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Organization for the Strategic Coordination of Research and Intellectual Properties,

Meiji University, 1-1-1, Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571, Japan

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*Corresponding author. E-mail address: koi@meiji.ac.jp
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Abstract
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Trace amounts of Cr, Zn, Cd, and Pb were determined by metal furnace atomic
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absorption spectrometry using absorption tubes. Various absorption tubes were

designed as roof- and tube-types, and fixed above the metal furnace in order to extend
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the light path length. Aqueous standards and samples were injected in the metal

furnace and atomized in a metal atomizer with an absorption tube (6 cm length, 15.5
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mm diameter). The used of an absorption tube resulted in an enhancement of the

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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 absorption tube was

effective for Zn and Cd analysis, as the absorbance values for these low boiling point

metals doubled. The proposed method was successfully applied in the determination of

Zn in tap water.
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Key words: absorption tube, atomic absorbance enhancement, heavy metal, low boiling

point metal, metal furnace atomic absorption spectrometry

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1. Introduction

The sensitivity of furnace atomic absorption spectrometry (AAS) is still

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insufficient for the determination of trace elements such as toxic heavy metals at

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natural background levels. Methods to improve the sensitivity of AAS have been

attempted, such as that achieved with metal furnace atomic absorption spectrometry

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(MFAAS). In 1970, Donega [1] conducted a highly sensitive analysis of several
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elements with an electrically heated Ta boat, on which MFAAS was based. Although

MFAAS is used for various analyses [2−9], its sensitivity is not sufficient for the
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determination of trace metals without a previous preconcentration step.

Atomic absorbance is determined from signals corresponding to the numbers of

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measured atoms, and is independent of the atomic evolution time. The integrated
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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

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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
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been used in the past. Chu et al. [10] investigated a furnace AAS method for As
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determined as 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-µg 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

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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 atomization an intensifier,

but it does not have the expected effect for elements with extremely low boiling points

[12, 13] or high ionizability [14].

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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

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without hysteresis, so that it does not cause any pre-excitation of atoms. The flow of

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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

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absorption tube enhances atomic absorbance.
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This paper describes a method using MFAAS combined the use of absorption tubes

for the determination of trace amounts of Cr, Zn, Cd, and Pb. Owing to the diffusion of
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the vapor outside of the tube at low temperatures along the optical axis, the use of an

absorption tube in the metal furnace also extended the residence time of the atomic
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vapor. The optimum instrumental conditions and design of several absorption tubes are
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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.
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The proposed absorption tubes were successfully applied for the enhancement of the

atomic absorbance of low boiling point metals.

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2. Material and methods

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,
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Cd, and Pb in water. A deuterium lamp was used for background correction.

Atomization 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

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the lower part of the W metal furnace. Aqueous solutions (10 µL) were injected into

the metal furnace using an Eppendorf Model 4800 micropipette. The operation

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conditions are given in Table 1.

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Cr, Zn, Cd, and Pb test solutions (100 µg L-1) were prepared from 1000 mg L-1

standard solutions (Junsei Chemical). The tap water sample was collected at Kawasaki,

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Japan.
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2.2. Methods
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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 diameter. They were fixed above the
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metal furnace with two pieces of wire and polyurethane foam packing (Fig. 1). Each
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measurement was repeated five times.

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3. Results and discussion

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3.1. Design of absorption tubes

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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 10 mm width; Fig. 3). The absorption

tubes were designed on the basis of the size of the metal atomizer head. The absorption
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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

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The enhancement of the atomic absorbance with the absorption tubes was

evaluated by testing the atomic absorbance of determinants in aqueous standards of Cr.

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The absorption tubes needed to be preheated before the measurements to prevent

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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

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diameter) used, and the absorbance using tube- and roof-type absorption tubes were as
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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
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physical adsorption of the atomic vapor inside the tube. In order to preheat the

absorption tubes, the metal furnace was heated to the atomization temperature (20 s
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with 1900 °C for Cr, 1100 °C for Zn, 1400 °C for Cd, and 2100 °C for Pb) only once
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before the first measurement.

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3.3. Optimum absorption tube size

Fig. 4 shows the variation of the atomic absorbance of Cr with the length of the
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absorption tube. The atomic absorbance was enhanced in all the cases where an
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absorption tube was used. The enhancement of the atomic absorbance indicates that

the proposed method with absorption tubes is effective. The maximum absorbance 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
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among the atomic absorbance values using absorption tubes having different lengths

and diameters. In subsequent experiments, absorption tubes of 6 cm length and 15.5

mm diameter were used for MFAAS.

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3.4. Enhancement of atomic absorbance with absorption tubes

The proposed absorption tubes were applied in the analysis of heavy metals. The

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absorption tubes were developed for the determination of the atomic absorbance of Cr,

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Zn, Cd, and Pb in aqueous standards. The ratios of the atomic absorbance with and

without the absorption tubes are shown in Table 2. The enhancement of the absorbance

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obtained for Cr, Zn, Cr, and Pb using the absorption tubes. The roof-type absorption
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tube resulted in enhancements of the absorbance for every element, and the absorbance

intensity increased by 31-66% compared to that measured without the absorption tube.
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Meanwhile, the tube-type absorption tube was found to be effective for low boiling

point metals, and the absorbance intensities of Cd and Zn were double of those
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measured without the absorption tube.

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3.5. Calibration curve and detection limit

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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
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absorption tube were obtained using calibration standards containing determinants

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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 0-0.6 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 proposed method

using absorption tubes is suitable for quantitative analysis.

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3.6. Application of proposed method

The results obtained for tap water with the tube-type absorption tube are given in

Table 3. The value obtained by a standard method without the absorption tube is also

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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. The relative

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standard deviation of the proposed method was 4.1%, and so the reproducibility also

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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

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proposed method with the tube-type absorption tube.
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4. Conclusions

Metal furnace atomic absorption spectrometry assisted with an absorption tube was
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used in the determination of trace amounts of Cr, Zn, Cd, and Pb. The roof- and
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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
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absorbance intensities increased by 31-66% compared to those measured by the system

without the absorption tube. Meanwhile, the tube-type absorption tube was effective in
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the determination of low boiling point metals, and the absorbance intensities obtained
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for Cd and Zn were double of those measured without the absorption tube. The

proposed method was successfully applied in the determination of Zn in tap water.

References

[1] H. M. Donega, T. E. Burgess, Atomic absorption analysis by flameless atomization

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in a controlled atmosphere, Anal. Chim. 42 (1970) 1521−1524.

[2] K. Fujita, T. Nakamura, Screening of heavy metals in soil by direct sampling/metal

furnace atomic absorption spectrometry, Bunseki Kagaku 58 (2009) 609−615.

[3] A. Komatsu, M. Kitano, T. Nakamura, Determination of hazardous metals in

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plastics by metal furnace atomic absorption spectrometry with direct solid-sampling

technic, Bunseki Kagaku 58 (2009) 785−791.

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[4] T. Inui, K. Fujita, M. Kitano, T. Nakamura, Determination of Cr(III) and Cr(VI) at

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sub-ppb levels in water with solid-phase extraction/metal furnace atomic absorption

spectrometry, Anal. Sci. 26 (2010) 1093−1098.

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[5] N. Kamakura, T. Inui, M. Kitano, T. Nakamura, Determination of chromium(III),
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chromium(VI), and chromium(III) acetylacetonate in water by ion-exchange disk

extraction/metal furnace atomic absorption spectrometry, Spectrochimi. Acta Part B 93

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(2014) 28−33.

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cobalt(II) on chitosan and its determination by tungsten metal furnace atomic

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absorption spectrometry, Analytica Chimica Acta 378 (1999) 279−285.

[7] H. Minamisawa, Y. Tatehaba, N. Arai, T. Okutani, Determination of trace amounts

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of palladium(II) in water by metal-furnace atomic absorption spectrometry after

preconcentration on chitin, Anal. Sci. 12 (1996) 947−951.

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[8] A. Uzawa, H. Minamisawa, T. Okutani, Adsorption behavior of cobalt(II) on

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chitosan and its determination by tungsten metal furnace atomic absorption

spectrometry, Anal. Sci. 16 (2000) 1085−1088.

[9] A. Uzawa, T. Nakamura, T. Okutani, Adsorption behavior of cobalt(II) on chitosan

and its determination by tungsten metal furnace atomic absorption spectrometry, Anal.

Sci. 14 (1998) 395−398.

[10] R. C. Chu, G. P. Barron, P. A. W. Baumgarner, Arsenic determination at

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sub-microgram levels by arsine evolution and flameless atomic absorption

spectrophotometric technique, Anal. Chem. 44 (1972) 1476−1479.

[11] P. D. Goulden, P. Brooksbank, Automated atomic absorption determination of

arsenic, antimony, and selenium in natural waters, Anal. Chem. 46 (1974) 1431−1436.

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[12] K. Anezaki, I. Nukatsuka, K. Ohzeki, Determination of arsenic(III) and total

arsenic(III,V) in water samples by resin suspension graphite furnace atomic absorption

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spectrometry, Anal. Sci. 15 (1999) 829−834.

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[13] K. Hagiwara, T. Inui, Y. Koike, T. Nakamura, Determination of diphenylarsinic

acid, phenylarsonic acid and inorganic arsenic in drinking water by graphite-furnace

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atomic-absorption spectrometry after simultaneous separation and preconcentration
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with solid-phase extraction disks, Anal. Sci. 29 (2013) 1153−1158.

[14] K. Miura, K. Yamamoto, A. Yonetani, T. Shirasaki, Determination of cesium in

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foods by atomic absorption spectrometry based on background-correction using

zeeman splitted spectrum, Bunseki Kagaku 62 (2013) 37−41.

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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
3 -1
Ar gas flow / dm min 5.0
3 -1
H2 gas flow / dm min 1.0
Absorbance Peak area

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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)

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Atomization step / °C 1900 (hold 20 s) 1100 (hold 20 s) 1400 (hold 20 s) 2100 (hold 20 s)

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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)
Signal with tube / Signal without tube
Boilling point / °C
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

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Table 3 Analytical results of Zn concentration determination in tap water
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Zn concentration / mg L RSD, %
Tube-type absorption tube 1.24 4.1
No tube 1.16 10.3
RSD: Relative standard deviation, % (n = 5).

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Polyurethane foam packing Wire

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Metal atomizer

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Absorption tube

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Lamp Detector

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Fig. 1 Schematic figure of the metal atomizer head with the absorption tube.
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5, 6, 7 cm

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12, 15.5 cm
A

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1.5, 2.0, 2.5 cm 2 cm

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5, 6 cm

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B
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12, 15.5 cm

Fig. 2 Schematics of the absorption tubes made of silica glass.

A: tube-type, B: roof-type.
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A B
20 mm 20 mm 20 mm 20 mm 20 mm 20 mm

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10 mm 8 mm

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5 mm 5 mm

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5 mm 5 mm

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5 mm 10 mm
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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.
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Atomic absorbance / - 2.7 2.7

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1.8 1.8

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0.9 0.9

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0 0
Not used 1 25 36 4 7
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Diameter of absorption tube / cm
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：roof-type, 12 mm diameter, : tube-type, 12 mm diameter,

：roof-type, 15.5 mm siameter, ■: tube-type, 15.5 mm diameter.
Fig. 4 Variation of the atomic absorbance of 1 ng of Cr with the length of the
absorption tube.
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Atomic absorbance / -

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12 r = 0.999

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0.0 0.2 0.4 0.6 0.8 1.0

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Amount of Zn / ng

Fig. 5 Calibration curves of Zn in aqueous standard with (●

●) and without (■
■)
the absorption tube.
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Highlights

The absorption tube achieved the enhancement of atomic absorbance in MFAAS.

The tube-type absorption tube was effective for Zn and Cd.
The intensities of Zn and Cd using the absorption tube were double of those measured

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without the tube.
The method was successfully applied in the determination of Zn in tap water.

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