Microchemical Journal 169 (2021) 106547

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Ivy extract-assisted photochemical vapor generation for sensitive

determination of mercury by atomic fluorescence spectrometry
Yongchun Liu a, b, Jie Zou a, b, Bin Luo a, b, Hairong Yu a, b, Zhigang Zhao a, b, Hui Xia a, b, *
a
Key Laboratory of Pollution Control Chemistry and Environmental Functional Materials for Qinghai-Tibet Plateau of the National Ethnic Affairs Commission, School of
Chemistry and Environment, Southwest Minzu University, Chengdu, Sichuan 610041, China
b
Key Laboratory of General Chemistry of the National Ethnic Affairs Commission, School of Chemistry and Environment, Southwest Minzu University, Chengdu, Sichuan
610041, China

A R T I C L E I N F O A B S T R A C T

Keywords: Making use of the natural plant extract as assistant matrix or photocatalyst provides an efficient strategy to break
Photochemical vapor generation the limitation of traditional photochemical vapor generation atomic fluorescence spectrometry in efficiency,
Atomic fluorescence spectrometry sensitivity, and biocompatibility. In this work, ivy extract-assisted photochemical vapor generation was proposed
Mercury
for the determination of trace mercury in natural water by atomic fluorescence spectrometry. The influencing
Ivy rootlet
Extract
factors such as irradiation time, irradiation wavelength and concentration of extract were systematically studied.
Under the optimized experimental conditions, the limit of detection for total mercury was 0.03 ng mL− 1 which is
better than the ethanol- assisted photochemical vapor generation system. This method is green and sensitive,
reduces the biological toxicity of photocatalytic materials and secondary pollution in the reduction process, and
provides experimental basis for expanding the photochemical vapor generation system.

1. Introduction
Atomic fluorescence spectrometry (AFS) is widely used in the
detection of heavy metals in the environment. In recent years, the
development of photochemical vapor generation (PCVG) technology
with photocatalytic nanomaterials such as nano-TiO2 and nano-ZrO2
[1–5] and low molecular weight organic compounds [6–8] has greatly
improved the sampling efficiency, analytical sensitivity, and stability of
AFS. In the same time, nanomaterials have also been studied for visual
analysis of metal ions [9,10]. Although photocatalytic nanomaterials
have excellent photoelectric properties, they have relatively high cost
and potential hazards to human health and the environment [11,12].
For example, nano TiO2 can interact with metals such as lead, cadmium,
and copper to form complexes, increase bioaccumulation and absorption
of heavy metals, thereby increasing the metal toxicity to animals, plants,
and human beings [13,14]. Sturgeon’s group proposed that it is possible
for organic compounds to produce free radicals under irradiation which
could carry out the catalytic reduction of metal ions in the absence of
nanomaterials, however, the vapor generation efficiency is reduced to a
certain extent [15]. Therefore, it is necessary to find safer photoelectric
materials, optimize photochemical vapor generation conditions,
enhance photochemical vapor generation efficiency, and extend PCVG
systems. Natural plants are the ideal choice for the characteristics of low
cost, easy availability, superior biocompatibility, low toxicity, and light
absorption capacity. Effective photoelectric components extracted from
natural plants are expected to be used as assistant matrix or catalyzer of
PCVG to establish new PCVG systems. However, the properties and
potential applications of extract are still in the exploration stage. Ivy is a
common green vine. In recent years, Zhang’s group found its potential
ability in sunscreen through the detailed study on the photoelectric
properties of ivy root extract [16,17]. Research results show that the ivy
nanoparticles (ivy NPs) with an average particle size of 70–100 nm in
ivy root extract have significantly stronger absorption ability than that
of nano-TiO2 in the range of 280–400 nm [18]. At the same time, the
apoptosis percentage of HeLa cells cultured with 1 μg mL− 1 ivy root
extract was not significantly different from that of the control group and
was significantly lower than that of nano-TiO2 with the same concen­
tration [19,20]. Thus, ivy NPs not only has better UV visible absorption
capacity and photoelectric performance than nano-TiO2 and nano-ZnO,
but also has low cytotoxicity and strong biodegradability. On this basis,
the excellent photoelectric performance of ivy root extract is suitable for
improving the PCVG efficiency. In this research, making use of the
extract of ivy rootlet as assistant matrix for PCVG, a sensitive mercury
determination method was established, which is expected to provide a

* Corresponding author at: School of Chemistry and Environment, Southwest Minzu University, Chengdu, Sichuan 610041, China.
E-mail address: ivyxiahui@swun.edu.cn (H. Xia).

https://doi.org/10.1016/j.microc.2021.106547
Received 29 May 2021; Received in revised form 16 June 2021; Accepted 17 June 2021
Available online 21 June 2021
0026-265X/© 2021 Elsevier B.V. All rights reserved.
Y. Liu et al. Microchemical Journal 169 (2021) 106547

new route for the expansion of photochemical vapor generation system.
2. Experimental
2.1. Chemicals and materials
All reagents are of analytical grade or better. Ethanol (99.9%), silica
and calcium carbonate for extraction, hydrochloric acid and nitric acid
were purchased from Kelong Chemical Reagent Factory, Chengdu,
China. Mercury standard stock solution (1000 μg mL− 1) was purchased
from the National Nonferrous Metals and Electronic Materials Analysis
and Testing Center, Beijing, China. The carrier gas (Argon gas) was
purchased from Qiaoyuan Gas Co., Ltd, Chengdu, China. Ivy plants were
purchased from flower market in Shuangliu, Chengdu, China.
2.2. Apparatus and characterization
A photochemical reactor was constructed as shown in Fig. 1. The
reactor primarily consisted of a UV lamp (6 W, Philips Co., Holland) and
a quartz coil wrapped around the UV lamp, a peristaltic pump (BT100-
02, Qili Precision Pump Co., Ltd., Baoding, China), a four-way reactor,
and a gas–liquid separator (GLS). Ultraviolet and visible (UV–Vis)
spectrophotometer (UV-1800PC, Mapada Instrument Co., Ltd.,
Shanghai, China) and molecular fluorescence spectrophotometer
(970CRT, INESA Analysis Co., Ltd., Shanghai, China) were used for
investigating the absorption and fluorescence properties of the ivy root
extract. Atomic fluorescence spectrometer (AF-3100, Haiguang Instru­
ment Co., Beijing, China) was used for the detection of the trace mercury
vapor.
water sample solutions, then volume was diluted to 50 mL with ultra­
pure water for further detection.
2.5. Working procedure
The experimental process of this project is divided into four steps. In
step 1, the mercury standard or sample solution was pumped into the
quartz tube for 25 s with a sampling volume of 10 mL. Meanwhile, the
solution was irradiated with UV lamp in the same time. In step 2, the
sampling channel was shifted from the sample solution to the carrier
solution (5% hydrochloric acid) for 3 s. In step 3, the solution was
pushed into the gas/liquid separator (GLS) with the argon flow to
separate and introduce the generated mercury vapor into the AFS for
detection, and this step took 2 s. In step 4, mercury AFS signal was
recorded in peak area mode, and the detection time was 30 s. The carrier
gas flow rate was 400 mL min− 1, 5% nitric acid solution and ultrapure
water were further used for cleaning up the quartz tube after each run.
3. Results and discussion
3.1. Optimization of irradiation wavelength
In order to characterize of optical properties of the extract and select
the appropriate irradiation wavelength for the PCVG, the UV–Vis ab­
sorption spectra of the ivy extract was measured. As shown in Fig. 2, the
extract solution displays strong ultraviolet and weak visible light

2.3. Preparation of ivy root extract

The ivy root extract was prepared using the procedure reported
previously [21,22]. The roots were washed, dried and cut into small
pieces after growing several days under natural temperature, humidity,
and light availability. Then 2.2 g of the cut rootlets were mashed with
1.6 g CaCO3, SiO2 and 30 mL ethanol, followed by 10-min ultrasound to
break the cell wall. After filtering twice with ethanol by 450-nm filters,
the brown solution was sealed and refrigerated in 4 ◦ C. The ivy roots and
the extraction process are shown in Fig. 1 (pictures i - iv on the left).

2.4. Preparation of standard solution and water samples

Standard solutions of mercury were prepared by serial dilutions of a

mercury standard stock solution with ultrapure water. Water samples
collected from the Yingyue Lake and Sun Moon Lake in Southwest Minzu
University campus were filtered prior to analysis. 5% (v/v) of ivy root
Fig. 2. UV–Vis absorption spectra of ivy root extract.
extract was added into each standard solutions of mercury or 25 mL of

Fig. 1. Schematic diagram of the ivy root extract-assisted PCVG-AFS instrumentation (In the picture on the left: i, the ivy plants; ii, the ivy roots; iii, ivy roots after
grinding; and iv, sample solution with the filtered ivy root extract).

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Y. Liu et al. Microchemical Journal 169 (2021) 106547

absorption. A sharp transition edge from the ultraviolet to the visible

range and a significant absorption band around the wavelengths of 290
nm and 330 nm can be found for the samples, respectively. The results
are consistent with the previous reports [18], indicating that proteins
and amino acids are the possible components in the ivy root extract,
while photo-induced electron transfer happens between the structure of
ivy extract in the ultraviolet region.
In the atomic fluorescence detection, two common wavelengths of a
commercial portable UV lamp at 254 nm and 365 nm were chosen as the
excitation wavelengths. Therefore, the molecular fluorescence proper­
ties of ivy root extract with the two excitation wavelengths were dis­
cussed. As shown in Fig. 3, there is a maximum emission peak at 433 nm
under 365 nm excitation (a). However, no fluorescence emission signal
was found with the excitation at 254 nm (c). On the other hand, the
maximum excitation wavelength is also found to be at about 365 nm
when we determinate at the emission wavelength of 433 nm (b). The
result suggested that the composition and structure of the extract could
be destroyed under 254 nm radiation, thus affecting the photoelectric
conversion process. Therefore, 365 nm was chosen as the irradiation
wavelength to carry out the photochemical vapor generation of
mercury. Fig. 4. Effect of irradiation time (concentration of Hg2+: 5 ng mL− 1; and 5% (v/
v) ivy root extract).

3.2. Optimization of irradiation time

As an important physical factor, the effect of the irradiation time in

the flow-through quartz coil was investigated from 25 to 45 s, with the
first 25 s used to fill the quartz tube with the solution. As shown in Fig. 4,
the signal intensity significantly increased from 25 s to 30 s irradiation.
With the irradiation longer than 30 s, the signal intensity decreased with
the increasing the irradiation time, then it remained stable, probably
due to the competitive process between the PCVG and its reverse reac­
tion [23,24]. To ensure the reduction efficiency of Hg2+, a short irra­
diation time of 30 s was selected for use.

3.3. Effect of extract concentration

The concentration of ivy root extract was investigated to improve the

photochemical vapor generation efficiency of mercury. The result is
shown in Fig. 5. The higher concentration of the ivy root extract, the
stronger AFS intensity was observed, and the amount of photoactive
components is closely related to the weight of roots. Comprehensive
considering of extraction efficiency, solubility and cost, the extracted

Fig. 5. Effect of the concentration of ivy root extract (the concentration of

Hg2+: 5 ng mL− 1).

solution with original concentration of 5% (m/v) was obtained by

extracting 2.2 g ivy roots with ethanol. In order to compare with the
ethanol assisted system, 5% (v/v) of the extracted stock solution was
added into the standard solution or sample solution for further use.

3.4. Enhancement effect of atomic fluorescence by ivy root extract

In order to confirm the enhancement effect of atomic fluorescence by

ivy root extract, the AFS signal intensities of (a) 5% (v/v) ethanol, 10.0
ng mL− 1 Hg2+ constanted volume with (b) ultrapure water, (c) 5% (v/v)
ethanol and (d) 5% (v/v) ivy extract were compared in Fig. 6. In com­
parison, the atomic fluorescence intensity of Hg2+ standard solution
added with ivy root extract is significantly higher than that with aqueous
or ethanol solution. The result proved that the photoelectric active
components in ivy root extract has the potential to improve the effi­
ciency of photochemical vapor generation and the sensitivity of atomic
fluorescence.
Fig. 3. Fluorescence spectra of ivy root extract. (b) Excitation spectrum at
emission wavelength of 433 nm; and emission spectrum at excitation wave­
length of (a) 365 nm and (c) 254 nm, respectively.

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Y. Liu et al.
Fig. 6. Enhancement effect of atomic fluorescence: a, 5% (v/v) ethanol; b, 10.0
ng mL− 1 Hg2+; c, 10.0 ng mL− 1 Hg2+ with 5% (v/v) ethanol; and d, 10.0 ng
mL− 1 Hg2+ with 5% (v/v) ivy root extract.
3.5. Discussion of photochemical reduction of mercury assisted by ivy root
extract
Based on previous studies, the mechanism of photo-induced chemi­
cal vapor generation for the reduction of mercury is mainly discussed
with focus on the presence or absence of nano-TiO2 and organic com­
pounds, and the presence of nano-TiO2 can significantly improve the
efficiency of chemical vapor generation. The photogenerated electrons
and valence band holes produced by the UV radiation are helpful to
reduce Hg2+ to Hg0 during the photoadsorption and photoreduction
process [25,26]. The results show that the ivy root extract, especially the
ivy nanoparticles, also has the capability of extinction, scattering and
absorption of light from the ultraviolet to the visible range. However,
the ivy root extract exhibited a much stronger UV absorption than ZnO
nanoparticles and TiO2 nanoparticles at the same concentration.
Therefore, the photons absorbed by extract initiated a series of electron
transfer reactions, the reduction photoelectron produced by this process
led to the reduction of Hg2+, and then the enhancement of atomic
fluorescence signal. However, the mechanism of electron transfer and
reduction should be further confirmed.
3.6. Analytical characteristics
The linear relationship between atomic fluorescence signal and
mercury concentration is acceptable in the range of 0.2–10.0 ng mL− 1
with 5% ivy root extract. The standard curve equation was I (%) =
90.307 + 254.41C(Hg) (Fig. 7). The linear correlation coefficient was
better than 0.99. The LOD based on three times the standard deviation of
11 measurements of the blank signal was found to be 0.03 ng mL− 1. In
previous reports [8], the detection limits of conventional hydride
generation-AFS, PCVG-AFS with ethanol-UV and ethanol-TiO2-UV were
0.03 ng mL− 1, 0.07 ng mL− 1 and 0.02 ng mL− 1, respectively. Compar­
atively, the LOD of this method is close to that of hydride generation-AFS
and PCVG-AFS with TiO2, and is better than an ethanol assisted PCVG
system.
3.7. Sample analysis
To evaluate the accuracy of the proposed analytical method, two
natural water samples collected on campus were analyzed by standard
addition recovery method with the results listed in Table 1. 5% (v/v) ivy
root extract and 1.00 ng mL− 1 mercury standard solution mercury were
added into the certain amount of sample solution. No signal was
determined in water samples without mercury standard solution. From
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Microchemical Journal 169 (2021) 106547
Fig. 7. Standard curve of Hg2+ with 5% (v/v) ivy root extract.
Table 1
Analytical results for mercury in real water samples by the proposed method.
Sample Added (ng mL− 1) Found (ng mL− 1)
Sample 1 0 nd
1.00 1.04 ± 0.03
Sample 2 0 nd
1.00 1.02 ± 0.07
Average standard deviation (n = 3), nd = not detected.
the recovery results, the proposed method is accurate to be used for the
determination of trace Hg2+ in natural water samples.
4. Conclusions
In summary, an ivy root extract-assisted PCVG-AFS method was
successfully developed for the determination of trace mercury in water
samples. In this work: (1) the absorption and fluorescence properties of
the ivy extract were investigated; (2) the sensitivity of mercury deter­
mination was improved with the assistance of ivy root extract; (3) it is a
nontoxic and green analytical method with plant extract instead of use
of photocatalytic nanomaterials; and (4) it is expected to establish the
selection rules of assistant matrix to provide a new strategy for exploring
PCVG systems in the future.
CRediT authorship contribution statement
Yongchun Liu: Methodology, Formal analysis, Writing - original
draft. Jie Zou: Formal analysis, Investigation, Data curation, Writing -
original draft. Bin Luo: Methodology, Validation. Hairong Yu: Super­
vision, Resources, Funding acquisition. Zhigang Zhao: Project admin­
istration, Funding acquisition. Hui Xia: Conceptualization, Writing -
review & editing, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors thank the financial support from “the Fundamental
Y. Liu et al.
Research Funds for the Central Universities”, Southwest Minzu Univer­
sity (2020PTJS20005), the Sichuan Science and Technology Program
(2019YJ0254), and the Key Lab of Green and Technology of Ministry of
Education at Sichuan University.
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