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A method for rapid detection of heavy metals in soil and its application

Article · March 2015

DOI: 10.1109/WCICA.2014.7052696

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Proceeding of the 11th World Congress on Intelligent Control and Automation
Shenyang, China, June 29 - July 4 2014
A method for rapid detection of heavy metals
in soil and its application
Kai Ma and Fangfang Qu
College of Computer Science and Information Technology
University of Three Gorges
Yichang, Hubei Province, China
makai@ctgu.edu.cn
Abstract - Rapid detection of heavy metals in the soil and
getting their distribution is important for heavy metal pollution
prevention and control. This paper proposes a rapid detection
method based on energy dispersive X-ray fluorescence
spectroscopy, which uses modular components to implement the
detection system. This method has been used to measure heavy
metal levels of Cr, Zr, Zn, As, Pb in the standard materials of
several soil samples. The experimental results show that this
method has the advantage of fast analysis, simple sample
preparation, easy carrying, and non-destructive characteristics.
It is ideal to meet the requirements of timeliness and accuracy of
screening for heavy metals in soil and in-situ measurement.
Index Terms - EDXRF, heavy metals, rapid detection
I. INTRODUCTION
Currently the soil heavy metal pollution of farmland is
attracting more and more attention, and the demand for rapid
testing and screening heavy metal content of soil is increasing.
The traditional detection methods of heavy metals in soil are
atomic absorption spectrometry, atomic emission
spectrometry, atomic fluorescence spectrometry, inductively
coupled plasma mass spectrometry and spectrophotometry,
etc. Although these methods have strong specificity and high
sensitivity, they also have shortcomings, such as expensive
instruments, high cost, and unsuitable for rapid determination,
etc [1]. XRF technology, as a rapid, accurate, economical,
multi-element analytical tool, has been widely used since the
beginning of the 1950s. With the development of the
technology, the accuracy of the analysis results have been as
well as the chemical analysis [2]. According to the working
mechanism of X-ray fluorescence spectroscopy, the methods
can be divided into wavelength dispersive and energy
dispersive X-ray fluorescence spectroscopy (WDXRF and
EDXRF), total reflection X-ray fluorescence analysis (TXRF),
synchrotron radiation X-ray fluorescence spectroscopy
(SRXRF), X-ray micro-fluorescence analysis (XRMF), proton
induced X-ray fluorescence analysis (PIXF) , and scanning
nuclear microprobe analysis technique [3]. While other types
of XRF analysis methods are more suitable for laboratory
analysis, energy dispersive X-ray fluorescence analysis
technique enables the rapid non-destructive multi-element
analysis simultaneously in the field site, with the advantages
of lightweight, short analysis time, large range of analyzable
elements, and wide application areas [4]. In recent years, this
technique has also been more widely used for
109
978-1-4799-5825-2/14/$31.00 ©2014 IEEE
Zehua Chen, Xiaobo Zhu and Jinjian Hou
College of Computer Science and Information Technology
University of Three Gorges
Yichang, Hubei Province, China
quff1128@163.com
rapid screening heavy metals in the soil and in-situ
measurement [5-7]. With the development of the X-ray tube
and detector technology, to quickly build a dedicated EDXRF
equipment becomes possible [8-9].
II. WORKING PRINCIPLE
X-rays are electromagnetic radiation generated by high-
energy particles bombarding atoms. It has wave-particle
duality. X-ray fluorescence spectrometry uses the primary X-
ray photons or other microscopic particles to excite the atoms
in the test material to make a secondary X-ray fluorescence for
material composition analysis and chemical state research.
Moseley law is the basis of qualitative analysis of X-ray
spectroscopy, and the expression of energy equation is shown
in Formula (1) as below[3]:
1 1
E  Ei  E f  RhC( z   ) 2 ( 2  2 ) (1)
n f ni
where  E is the X fluorescence energy, R is the Rydberg
constant, h is Planck's constant, C is the speed of
photons, Z is the atomic number,  is the Shielding constants,
and n f , ni are energy series. For the spectrum K 1 , assume
shielding constants   1 , n f  1 , that is K-shell, and ni  2 is
L-shell, then
EK1  3 RhC ( Z  1) 2 / 4 (2)
This law reveals the relationship between the X-ray
energy and atomic number; it is the theoretical basis for the
qualitative analysis of material composition using X-ray
fluorescence. There is a positive relationship between the
count rate of characteristic X-ray and the content of an
element of the tested sample [10], as shown in Formula (3):
KI 0
Ik   Wk (3)
0  k
where I k and I 0 are the K layer characteristic X-ray of the
measured elements and the count rates of the incident X-ray,
respectively.  0 and  k are the absorption coefficient of the
tested substance to the incident X-ray and the tested element
to the layer K characteristic X-ray, respectively. K is the
constant related to the specific measurement device, and needs
to be determined by the calibration
instrument KI 0 /(  0   k ) . Wk is the measure of the content
elements. Formula (3) is the theoretical basis of quantitative
analysis of the measured elements using X-ray fluorescence.
III. EXPERIMENTAL DEVICE STRUCTURE
An important work is to construct high voltage power
module for providing the X-ray tube voltage supply. It can set
the voltage and current of X-ray tube as needed. After
irradiating the sample, the fluorescence of the sample is
detected by the detector, and is transform into voltage pulses
of different amplitudes depending on the photon energy, the
pulse is then amplified by the preamplifier and analyzed by
the process multi-channel analyzer. The results are sent to the
host computer software for further processing to obtain test
results. The experimental device consists of the following
major components: Power Module, X-ray emission module,
detection module, amplifier module, analysis module,
interface modules, PC. The system components are shown in
Figure 1.
Fig. 1 EDXRF system structure diagram
A. X Ray Tube[11]
Based on the consideration of the combination factors of
the size and power consumption, U.S. AMPTEK's MINI-X
Silver (Ag)-ray tube is selected as the X-ray tube. The
equipment is a portable integrated miniature X ray tube, and
the ray source includes a miniature sealed transmission end
window type X ray tube and the matching high voltage power
supply. The USB Port can be used to set working voltage
and working current. The light pipe technology parameters are
shown in Table I.
TABLE I
X-RAY TUBE MAIN TECHNICAL INDICATORS
Window
Work Working window Window Focal Refrigeration
target
Voltage current material thickness diameter type
material
10kV- 5μA- About Electric
Ag
50kV 200μA
Be 127
2mm refrigeration
The continuous spectrum of X-ray tube is determined by
the applied voltage, current and the target. Generally large
voltage and low current are selected for heavy elements, while
small voltage and high current are chosen for light elements.
Several working voltage output spectra curves of the X-ray
tube chosen for this system are shown in Figure 2:
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Fig. 2 Mini-X Silver (Ag) in different output voltage spectrum
B. Fluorescence Detector and Analysis Processor
The performance of the detector is the important index of
experimental precision. The half high width (FWHM) of the
energy spectrum curve is an important index to measure the
energy resolution of the energy dispersive X ray
fluorescence spectrometer, which characterizes the ability of
the detector to distinguish between different energy of the
input particles. FWHM is usually represented by the width
at the half of the maximum 55Fe line of 5.9KeV. The device
adopted for this project is silicon drift XR-100SDD probe
produced by the United States company Amptek whose
FWHM in the high resolution mode is 125 ev (corresponding
to the peak of 5.9 keV), the ratio of peak is 20000:1 (P/B
thewire 5.9 keV to 1 keV), the peaking time is 11.2 μs, and the
maximum count rate is 100000 CPS [12]. When the generated
fluorescence enters the detector, the detector will generate a
matching electrical pulse according to the energy of the
incident photon. The pulse height is proportional to the
incident photon energy. The generated pulses are amplified by
the preamplifier and then processed by
the multichannel digital pulse processor. The role of
multichannel analyzer is to record the number of pulses in
each height interval.
C. Software Design
The software is developed using Visual Basic 6.0
development tools, whose working state of the main interface
is shown in Figure 3. The main features are: 1) Work status
monitoring: Real-time monitoring of the operating voltage and
current of X-ray tube in the measurement process, the real-
time operating temperature of the detector, the total count rate,
and the current measurement time. 2) Spectra processing and
display: It is mainly responsible for the display of energy
calibration, processing the spectral lines and displaying the
results of processing, element content calculation, and the
measurement results display. 3) Soil model settings: Setting
different calibration curve parameters according to the type of
the soil so that the measurement reference model can be
quickly selected to facilitate rapid field test. 4) Port
management: Primarily responsible for the communication
between the host computer and the X ray tube and the digital
pulse processor. It also can be used to set the interface type,
with the options of RS232 serial port, USB interface, and
Ethernet interface, so that flexibly set the data rate and check
the connection status.
 Fig. 3 The main interface of software

D. Energy Scale
The horizontal axis represents the detected energy in the
fluorescence spectrum. The experimental device divides the
horizontal spectrum into 4096 channels according to different
energy scales, and different energies correspond to different
elements so that the elements in the sample can be identified
by the channel addresses of the corresponding peaks. The
vertical axis is the count rate. The value of the vertical axis of
the peak spectrum of an element is associated with the
element’s concentration. It can be seen that, while through the
horizontal axis qualitative analysis can be performed to detect
the elements in the samples, the vertical axis can be used to do
quantitative analysis to detect the concentration of an element
in the samples. The relationship between the channels and
energy can be set through the software, and also we can
choose automatic energy scale. The relationship between
the number of channels and energy can be described by the
Formula (4) :
Energy  A  chn  B (4)
Fig. 5 Composition of the sample cup and the finished sample cup
For field measurements in the field, the following steps
can be adopted[13]: remove the debris on the soil surface and
level the surface; compact soil to increase the density; the
Mylar film is spread on the soil surface and remain flat; and
make the instrument probe vertically align Mylar film for the
in-situs detection.
B. Experiment
The instrument is mainly used to test the content of the
soil heavy metal elements such as Cr, Zr, Zn, As and Pb.
According to the excitation characteristics of X ray on the
elements, the common heavy metals in the soil are stimulated
relatively fully under high voltage, low current X light pipe
illumination. The value must be set to be larger than the
potential excitation of the element. After repeated tests, the
final selection of operating voltage is 30KV and the operating
current is 30μA. In this experiment the tested elements are
shown in Table II:
TABLE II
THE ENERGY OF THE MEASURED ELEMENTS AND THE CHANNEL NUMBER

Atomic Energy value(keV)

Element
number K K L L
Cr 24 5.41 5.95 0.57 0.58
Zn 30 8.64 9.57 1.01 1.03
Fig. 4 The relation of channel and energy scale As 33 10.54 11.73 1.28 1.32
Zr 40 15.77 17.67 2.04 1.12
where Energy is the energy, A and B are the coefficients, and
Pb 82 74.96 84.92 10.55 12.61
Chn is the channel number. The system calculates the values
​ ​ of A and B using the least squares method. The time selected for the analysis is 200s. The detection
Considering the differences between the various soils, the time shoud be selected appropriately. If it is too long, the
system takes the fundamental parameter method for testing efficiency is influenced, but too short time will cause
quantitative analysis. big error. Also, with same experimental instrument,
IV. METHODS measurement of different texture samples should use different
testing time. During the experiment, the current count rate, the
A. Sample Preparation temperature of detector and the real-time operating voltage,
Pretreatment of the test soil is necessary to remove the and current of the X ray tube can be observed by the main
stones and weeds, crush chunks of soil, and sieve the soil with panel of the software. Through observation, the total count
a 200 mesh sieve. If the soil is too wet, drying is also needed. rate of actual measurement of the system is basically stable in
After preprocessing, the samples are put in unidirectional the range of 17700-17850, and the detector working
sample cups without cover; the sample cups need to be made temperature varied in the range of 18℃ to 20℃.
of uniform material, with good light transmission. The
experiment used a polyethylene sample cup, with the outer
diameter 30mm, inner diameter 20mm, and height 10mm. A
collar with Mylar film is fixed. The lid’s diameter and
thickness are 20mm and 1mm, respectively. The sample in the
cup needs compaction. The Mylar film should be nested
firmly with the sample cup. Mylar film is specially designed
for X-ray analysis. Its thickness is 6μm. To avoid the influence
on the measurement results, the bottom surface of the film
should remain flat. The sample cup is shown in Figure 5.

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 1) Precision:
Setting up the measurement parameters according to the
experimental procedure, several soil standard reference
materials numbered as GBW07404, GBW07429, GBW07444
are tested, and the typical heavy metal elements Cr, Zn, As, Pb
are measured. The comparison of the measured values and the
standard values are shown in Table III, which shows that the
precision of this method is better.
TABLE III
COMPARISON OF THE MEASURED VALUES AND THE STANDARD VALUES
GBW07404 GBW07429 GBW07444
elements standard measured standard measured standard measured
value value value value value value
(mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg)
Fig. 6 The test process
Cr 370±24 370±24 87±4 87±4 79±7 79±7
Using a USB data cable connect the PC and DP5 to Mini- Zn 210±19 210±19 94±4 94±4 342±12 342±12
X-ray tube devices. After equipment initialization and power As 58±8 58±8 21.7±1.2 21.7±1.2 300±15 300±15
on self test, put the sample into the detection area, and close
Pb 58±7 58±7 38±2 38±2 192±7 192±7
the protective cover. Open the X-ray tube, boost until the
votage reaches the preset value, then start to measure. The 2) Detection limit:
measurement time is 200s. After the measurement, the According to the definition of detection limit adopted by
measured spectra and elemental content of the data are IUPAC branch of photochemical analysis in 1976 [14], the
obtained. Once the experiment is finished, turn off the X-ray detection limit is the content of three times the standard
tube, and open the sample chamber to remove the sample, or deviation of the blank value. Because the X photon counting
continuous to measurement next sample. The test process is close to normal distribution, if blank samples are measured as
shown in Figure 6. more than three times of the standard deviation of the intensity
C. Analysis of the peak intensity, it is detected with the confidence of
When select the analysis line, the first factor should be 99.73%. Repeat the measurements of the above standard
considered is whether the line energy values is in the energy substances for 15 times, the minimum detection limit for each
range of the X ray tube excitation. For instance in Table II the element is lower than the national standard level in the soil
characteristic energy value of the Pb elements is 74.96keV , limits, the details are shown in Table IV.
TABLE IV
but the characteristic energy value is 84.92keV, which is DETECTION LIMITS OF THE METHOD
beyond the energy limits of the X ray tube excitation of this Detection limits Limited values of the first stage soila
Elements
device. , it cannot be used as the analysis line. In addition, the (mg/kg) (mg/kg)
selection of analysis line should avoid interference from other Cr 5.6 50
matrix elements in the soil samples. For example, the Zn 11.3 100
K  characteristics energy value of As is 10.54keV and the As 9.7 15
L  characteristics energy value of Pb is 10.55keV. During the Pb 7.5 35
analysis, L  line of Pb cannot be chosen as the analysis line. a
GB15618-1995(Environmental quality Standard for soils)
Intead the L  line of Pb is the ideal element analysis line.
Similarly, K  line for Cr element, K  line for Zn, and K  line V. CONCLUSION
for As should be chosen as the analysis lines. The spectrum
From the multiple measurements results of several national
and the measured results of soil standard reference material
soil references, the instrument precision is better; single
GBW07404 are shown in Figure 7.
sample detection time is shorter; the detection limits of the
elements are below the national secondary standard values of
the soil. The proposed method is suitable for rapid detection of
heavy metals in soil. The equipment used has modular
structure, and the sophisticated products are used for
secondary development. It is easy and convenient to extend
the functionality and portability based on the existing open
platform, which is suitable for quickly building the system to
perform rapid detection of heavy metals in soil.
ACKNOWLEDGMENT
Fig. 7 measurement standard substance GBW07404 spectra This work is supported in part by the Natural Science
Foundations of China (Grant No.61105025, No.41371349),

112
National science and technology support project (Grant
No.2012BAH29B00) and National High Technology Research
and Development Program of China (Grant No.
2013AA102303).
REFERENCES
[1] SU Shuai-peng, XU Fei, CAO Hui, et al. “Perspective in the rapid
methods for the detection of heavy metals”. Applied Chemical
Industry.Vol.42 No.2 .Feb.2013.pp:355-359.
[2] C. Kilbride, J. Poole, T.R. Hutchings. “A comparison of Cu, Pb, As, Cd,
Zn, Fe, Ni and Mn determined by acid extraction/ICPeOES and ex situ
field portable X-ray fluorescence analyses,” Environmental Pollution.vol.
143, no. 2006,pp. 16-23.
[3] JI Ang, Tao GuangYi, ZHUO Shang-jun and LUO Li-qiang. X-ray
fluorescence Spectral Analysis. Bei Jing: Science Press. 2003.pp:17-18.
[4] GE Liang-quan. “Research Development in in-situ X-ray Fluorescence
Analysis Techniques”. Rock and mineral analysis.Vol.32,No.2. April
2013. pp:203-212.
[5] Tanja Radu, Dermot Diamond. Comparison of soil pollution
concentrations determined using AAS and portable XRF techniques[J].
Journal of Hazardous Materials.2009,171(2009):1168-1171.
[6] ZHANG Rong, ZHANG Yu-jun, ZHANG Wei, CHEN Dong, YU Xiao-
ya, GAO Yan-wei. “Measurement and Analysis of Lead in Soil Using X-
Ray Fluorescence Spectroscopy”. Spectroscopy and Spectral Analysis.
Vol.33,No.2.February,2013.pp554-557.
[7] WANG Ji-hua, MA Zhi-hong, HAN Ping. “Review on Detection Methods
of Heavy Metals”. Journal of Beijing Technology and Business
University(Natural Science Edition) Vol.30 No.5 .Sep.2012 .pp:23-25.
[8] GU Yi, YANG Qiang, LAI Wan-chang, GE Liang-quan. “A Portable
Tube Exciting X-ray Fluorescence Analysis System”. Nuclear Electronics
& Detection Technology. May.2010.Vol.30 No.5. PP:686-689.
[9] ZHANG Yu, DENG Yu-fu, ZHANG Shu-zhi, MA Yue, SHAO Xin. “A
Design of Portable Energy Dispersive X-ray fluorescence Analyzer”.
Nuclear Electronics & Detection Technology. Vol.30 No.5. May.2010.
pp: 666-669.
[10] Zhou Jianbin. “The Research and development of low-Z elements
EDXRF Analyzer”. Chengdu University of Technology.2008.
[11] X-Ray Generators.http://www.amptek.com [EB/OL].
[12] X-Ray Detectors.http://www.amptek.com [EB/OL].
[13] HAN Ping, WANG Ji-hua, LU An-xiang, MA Zhi-hong, PAN Li-gang.
“Analysis of Heavy Metal in Soil with Portable X-Ray Fluorescence”.
Spectroscopy and Spectral Analysis.Vol.32,No.3,pp826-829. March,2012.
[14] LIANG Guo-li, DENGSai-wen, WUXiao-jun, GANLu. “Discussion on
the Detection Limit in X-Ray Fluorescence Spectrometric Analysis”,
ROCKANDMINERAL ANALYSIS, Vol.22, No.4.December, 2003.
pp:291-29.

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