Spectrochimica Acta Part B 152 (2019) 25–29

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Spectrochimica Acta Part B

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Analytical note

Determination of gallium in water samples by atomic emission spectrometry T

based on solution cathode glow discharge
⁎ ⁎
Hongwei Lia,b, Wenchuan Zuc, , Fengkui Liud, Yu Wangc, , Yin Yangc, Xiaotao Yangc, Cong Liuc
a
Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
b
Institutions of Earth Science, Chinese Academy of Sciences, Beijing 100029, China
c
Beijing Center for Physical & Chemical Analysis, Beijing 100089, China
d
Shanghai An Jie Environmental Protection Science & Technology Co., LTD, Shanghai 201906, China

A R T I C LE I N FO A B S T R A C T

Keywords: A novel and rapid method was established for gallium determination by a home-made solution cathode glow
Solution cathode glow discharge discharger coupled with a portable fiber-optic spectrometer. Plasma was generated by the discharger and the
Gallium measurement emission line at 417 nm for gallium was observed with a portable fiber-optic spectrometer, whose spectral re-
Water samples solution was 1.1 nm based on the peak width of half height using a 10 mg/L gallium standard solution. The
Portable fiber-optic spectrometer
analytical conditions and instrumental parameters were optimized. The results showed acidity turned to be
significantly influential for the emission intensity of the same sample. Therefore, acidity control of the testing
solution was crucial. Under the optimized conditions, the limit of detection (LOD) for gallium was 0.47 mg/L
calculated by 3SDblank/S. The stability was evaluated by the seven replicates of 10 mg/L gallium standard so-
lution, and the relative standard deviation (RSD) was 2.1%. This method was applied to the analysis of gallium
for river and waste water available in Beijing. The recoveries in the range of 92.0%–113.1% were acquired while
the RSD values were below 7% (n = 5), which showed this method was feasible for gallium determination of real
water samples. Moreover, only 1% HNO3 is demanded while the whole instrument is portable and works under
ordinary atmospheric pressure so that the field test demand can be satisfied.

1. Introduction somewhat time-consuming. The analytical efficiency is greatly im-

proved by the inductively coupled plasma atomic emission spectro-
Gallium is a commonly used metal element in microelectronic metry (ICP-AES) and the inductively coupled plasma mass spectrometry
components as a main component of semi-conductor material. The (ICP-MS) [5,8]. However, the instrument cost is high and hard to move
rising demand for gallium-containing products is leading to increasing due to the cumbersome size and weight and the dependence of gas
generation of effluents containing ionic species of gallium [1], which cylinders. Besides, the interferences brought from overlap of spectral
tends to enhance the risk of the gallium pollution in the gallium-asso- lines are serious for ICP-AES while high-salty samples may do harm to
ciated industrial regions [2]. Furthermore, severe harms will be done to the ICP-MS instrument, whose operation is tedious due to the demand
human health if the daily intake amount of gallium nitrate and gallium of rigorous vacuum degree. Some electrochemical methods have also
arsenide is maintained at a high level, especially for the kidneys and been reported in literature for gallium detection [9–11], which showed
hematopoietic system [3,4]. Therefore, it makes significant sense to satisfying results. However, the operation is somewhat difficult while
monitor the gallium amount for the evaluation of water quality, espe- the electrodes containing mercury is frequently adopted, which tends to
cially for the industrial effluent discharges. bring or intense mercury pollution.
Nowadays, the determination of gallium is usually carried out by Solution cathode glow discharge has already been proved to be an
atomic spectrometry [5–7], inorganic mass spectrometry [8] and elec- effective way to acquire plasma [13], where the metal elements in the
trochemical methods [9–11]. Graphite furnace atomic absorption solution cathode enter in the course of continuous gasification. There-
spectrometry technique [12] was reported as a common and sensitive fore, the metal ions are atomized and excited subsequently, and the
method to determine gallium. However, the frequent dilution operation characteristic emission spectrum can be acquired and analyzed. Up to
is demanded due to its small linear range and the analytical process is present, a series of metal elements have been reported on literature

⁎
Corresponding authors.
E-mail addresses: [email protected] (W. Zu), [email protected] (Y. Wang).

https://doi.org/10.1016/j.sab.2018.12.004
Reçu le 7 août 2018; Reçu en forme révisée le 4 décembre 2018; accepté le 6 décembre 2018
Available online 08 December 2018
0584-8547/ © 2018 Elsevier B.V. All rights reserved.
H. Li et al. Spectrochimica Acta Part B 152 (2019) 25–29

[13–20] to be determined by this solution cathode glow discharge- Table 1

atomic emission spectrometry (SCGD-AES) method with favorable Working parameters for SCGD-AES.
analytical performance, covering Pb [18], Hg [17,18], Zn [18–20], Ca SCGD-AES parameters Adopted
[16,19], In [14], Sb [15] etc. In our previous work [21], the method for
determination of thallium by SCGD-AES was established. However, the Glow discharge voltage/V 700
Inner size of the glass capillary/mm 0.3 × 0.3
study on gallium determination by SCGD-AES has never been involved.
Anode–Cathode distance/mm 3
In this work, a novel method for gallium determination was developed Analytical line for gallium/nm 417
using a homemade solution cathode glow discharger with a portable Integration time for optics/ms 100
fiber-optic spectrometer. This method offers a novel means for field Flow carrier solution 1% (V/V) HNO3
monitoring on gallium pollution of environmental water as the instru- Flow rate of the carrier solution/(mL/min) 4
Measurement mode of the fiber-optical spectrometer Peak height
mental portability is realized. The analytical cost can decrease sig-
nificantly due to the simple instrumental and independence of gas cy-
linders. Besides, less pollution is introduced as only dilute acid is our former study was adopted for the glow discharge. The diagram of
needed for the whole detection process. the SCGD cell with discharge on was shown in Fig.1. Generally, the
anode is a tungsten pin (20 mm long and 1 mm diameter) and the so-
2. Experimental lution plays the role of cathode. When in the gap between the two
electrodes a high voltage (500–1000 V) is applied with a power supply
2.1. Reagents and samples module (DW-P102-100C5D, BeijingYuan Bo Sheng Electronic Tech-
nology Co., Ltd.), the gas in the gap is ionized and the plasma is gen-
The gallium standard solutions in the concentration range of erated. The HR-4000 fiber-optic spectrometer (Ocean Optics, Inc.) was
1.0–50 mg/L were prepared by appropriate dilution of the standard adopted to acquire the emission spectrum. The working parameters are
stock solution with the concentration of 10,000 mg/L from national shown in Table 1.
standard materials research center (Beijing, China). All of the acids
were with guarantee grade from Beijing Fine Chemicals Ltd. The water 3. Results and discussion
used was ultra pure water, whose electrical resistivity was above
18.2 MΩ·cm prepared by a Millipore water purification system. All the 3.1. Optimization of operating conditions
glassy containers were immersed in 10%(V/V) nitric acid for longer
than 24 h, washed to be clean using ultra pure water and natural air 3.1.1. Spectral line selection
dried for the following use. The emission line is a crucial factor influencing the sensitivity and
The samples were constituted by river water available from Beijing spectrum interference of gallium determination. In our work, the
local river with high concentrations of mineral elements and waste UV–Vis spectrum was observed with the fiber-optic spectrometer as
water rich in heavy-metal elements. shown in Fig.2. Significant emission was presented under the wave-
length of 417 and 403 nm for gallium, and the emission intensity under
2.2. Sample preparation the two emission lines was compared with each other for gallium de-
termination.
Water samples should be distinguished and sorted in advance ac- As shown in Fig. S1 (Appendix), the 417 nm line was the relatively
cording to the cleanness degree. As for the clean water sample, 0.1 mL ideal analytical line due to the better sensitivity. Generally speaking,
nitric acid was added into each 9.9 mL water sample, i.e. HNO3, 1%, the emission line of 403 nm was a favorable alternative for the analysis
(V/V), to maintain the equivalent acidity with the standard solutions. of gallium in high amounts as the intensity under 403 nm was about
For the muddy water samples, only a filtration operation was required 35.9% compared to that under 417 nm.
using a 0.45 μm filter membranes-aquo system to avoid the block of the
6-way valve of the SCGD apparatus. The blanks and the spiked samples 3.1.2. Optimization of the acidity
were prepared in parallel. Acidity has been proved to be a notable condition influencing the
sensitivity for the SCGD-AES technique. In this paper, 10 mg/L gallium
2.3. Apparatus solutions with different acidity were adopted for validation the influ-
ence of acidity on the sensitivity under the same conditions. As shown
A home-made solution cathode glow discharger as ever reported in in Fig. S2 (Appendix), in the acidity range as we adopted, the larger

Fig. 1. Configuration and diagram of the SCGD cell with discharge on.

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H. Li et al. Spectrochimica Acta Part B 152 (2019) 25–29

Fig. 2. UV–Vis spectrum observed by SCGD-AES.

Fig. 3. Co-existing elements influences on Ga determination.

Conditions: Gallium concentration was 10 mg/L. The concentrations of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pb, Cd and Tl were 10 mg/L. The concentrations of rare earth
elements, including La, Ce, Pr, Eu, Nd, etc. were 10 mg/L. All the tests were under the same conditions.

Table 2
Results of real sample tests and recoveries (n = 3).
Samples Content/(mg/L) Spiked/(mg/L) Found/(mg/L) Recoveries/% Average recoveries/% RSDb/%

River –a 2.50 2.30 92.0 99.0 6.6

2.52 100.8
2.52 100.8
2.33 93.2
2.70 108.0
Waste water 7.6 10.0 11.31 113.1 104.9 6.5
10.70 107.0
10.78 107.8
10.15 101.5
9.52 95.2

a
The results acquired were below LOQ.
b
The values of RSD% were based on five parallel tests.

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H. Li et al. Spectrochimica Acta Part B 152 (2019) 25–29

emission intensity was acquired while using the stronger acidity. It water samples. Gallium was determined by a home-made SCGD
could be explained by the influence rules of acidity on the sensitivity of equipment coupled with a portable fiber-optical spectrometer. This
SCGD-AES reported by Cserfalvi et al. [14,22] which proved in a certain method was with lower spectrum interferences due to the favorable
acidity range as we used, the increase of acidity exhibited a positive spectral resolution performance of the fiber-optical spectrometer.
effect on the improvement of sensitivity. However, in our work, the Gallium determination was completed within less than 2 min for each
non-ideal plasma stability which resulted in the increasing error was sample, which showed this method was with high analytical perfor-
presented when the acidity exceeding 1% (V/V) HNO3 (pH = 0.85) was mance. Besides, field test is expected to be feasible as the SCGD-AES
used. Therefore, 1% (V/V) HNO3 was chosen as the acid for the cathode instrument is simple, portable and works in atmospheric air and this
solution. method is with no gas cylinder dependence, and less reagent con-
sumption.
3.2. Analytic characteristic
Appendix A. Supplementary data
3.2.1. Spectral resolution of the fiber-optical spectrometer
Spectral resolution is a critical performance parameter for the fiber- Supplementary data to this article can be found online at https://
optical spectrometer, which is closely associated with the spectrum doi.org/10.1016/j.sab.2018.12.004.
interference and the final analytical accuracy. Generally, the analytical
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