Proceedings of the 2nd International Conference on Green Energy, Environment and 455
Sustainable Development (GEESD2021), D. Dobrotă and C. Cheng (Eds.)
© 2021 The authors and IOS Press.
This article is published online with Open Access by IOS Press and distributed under the terms
of the Creative Commons Attribution Non-Commercial License 4.0 (CC BY-NC 4.0).
doi:10.3233/ATDE210308
Uncertainty Evaluation for Determination
of Gold in High-Purity Gold by LA-ICP-
MS
Boling HUANGa,b,1, Xuan WANGa,b, Tingting YANGa,b, Jiani SHENa,b, Qingzheng
MAa,b, Yong ZHUa,b, Lansen LIa,b and Xihan YANGa,b
a
Chongqing Academy of Metrology and Quality Inspection, Chongqing 401123, China
b
National Jewelry Testing Center (Chongqing), Chongqing 401123, China
Abstract. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-
MS) is a new analytical method developed in recent years. The LA-ICP-MS is a
quasi-non-destructive multi-elemental analytical method with low detection limits,
high sensitivity and specificity. In this study, this method is applied to detecting
high-purity gold. The micro-region information of high-purity gold can be analysed,
and the original position information of the sample can be obtained in real time and
accurately. In this study, the content of impurity elements in high-purity gold were
determined by LA-ICP-MS, and the accuracy and reliability of the test results were
improved by calculating the uncertainty. According to the test and analysis, the gold
content of the high purity gold sample is (999.995 ± 0.003) ‰, so the gold content
of the sample is more than 999.99 ‰. The result shows that the LA-ICP-MS has the
advantages of fast, accurate and green, which is conducive to the rapid development
of jewellery industry technology, and puts forward guiding suggestions for the
production development direction, and promotes the green and healthy development
of jewellery industry.
Keywords. LA-ICP-MS, green development, jewellery industry
1. Introduction
High-purity gold means that the mass fraction of gold is not less than 999.99‰, or the
total mass fraction of impurity elements is not more than 10×10 -6 [1-2]. In the raw
materials of gold or gold alloy used for lead, target and solder in electronic industry, if
999.9‰ gold is replaced by high purity gold, the solderability, semiconductor properties
and stability of the materials will be greatly improved [2], and the high-purity gold is
widely used in energy, environment, electronics and industrial fields [3-5].
Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a
new analytical method developed in recent years. In this method, the sample surface is
eroded, sputtered and evaporated by focused laser beam to form aerosol [6-7]. The trace
elements in the sample can be obtained by mass spectrometry, and this method is widely
used in geology, biological, materials, archaeology fields [8-11].
A method for the determination of impurity elements in gold jewellery based on
laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is
1 Corresponding Author, Boling HUANG, Chongqing Academy of Metrology and Quality Inspection,
456 B. Huang et al. / Uncertainty Evaluation for Determination of Gold in High-Purity Gold
introduced. Laser ablation inductively coupled plasma mass spectrometry (ICP-MS) is a
new technology which uses focused laser scanning to excite solid samples and then
ionize them by inductively coupled plasma mass spectrometry (ICP-MS) to analysis the
content and distribution of elements in samples. It has the advantages of easy assembly,
wide range of elements (covering most of the elements in the periodic table), less samples
(only a few micrograms), high spatial resolution, high sensitivity, and it can be used to
analysis the micro area information of the sample and obtain the in-situ information of
the sample in real time and accurately.
2. Experiment
2.1. Samples
The samples of 999.99‰ high-purity gold were selected for the experiment. The surface
of the samples was smooth without obvious scratch, cavity and other defects. GSB 04-
3312-2016 series gold standard materials.
2.2. Instrument and Equipment
This research used the iCAP RQ inductively coupled plasma mass spectrometer (Thermo
Fisher) and the New Wave 213 nm Nd: YAG laser ablation system (New Wave
Research).
2.3. Methods
Samples were sampled in accordance with T/CST 2-2020 and ISO 11596-2008 [12-13].
The gold standard materials and the high-purity gold samples to be detected fixed to the
laser sample bin. Try to ensure that the samples and the standard materials have been in
the same horizontal position. The test area of samples should to be pre-detection to ensure
the flatness and clean. Under the selected operating conditions, after the baseline was
stabilized, the sample signal acquisition was started. The signal strength of the baseline
was blank, and the mass spectrometry signal strength of the trace element is detected.
The impurity elements contents of the samples were calculated according to the standard
curve, and then acquired gold content of the high purity gold samples according to the
difference. At least 3 different test points shall be selected for parallel test of each purity
gold sample, and the average value shall be taken.
3. Results
3.1. Gold Contents
In order to evaluate the uncertainty, we select a high purity gold sample for the detection.
The content detection results of the sample are shown in table 1. It can be seen from the
table that the test results of other elements are less than the detection limit except the
elements of chromium, iron, silver, tin and iridium. It will be regarded as zero in the
difference calculation if the impurity element of the test result was less than the detection
B. Huang et al. / Uncertainty Evaluation for Determination of Gold in High-Purity Gold 457
limit. The impurity elements of the samples are mainly chromium, iron, silver, tin and
iridium, and the total amount of impurity elements is 5.062 mg/kg. According to the
difference method, the gold content of the sample is 999.995‰.
3.2. Uncertainty
In order to reasonably give the measured value dispersion, the parameters associated with
the test results can measure the quality level of the test results, and improve the accuracy
and reliability of the test results. In order to calculate the uncertainty of the result, it was
needed to determine the source of the uncertainty in the process of measurement,
establish the model, and deduce the combined standard uncertainty and expanded
uncertainty. Considering the content of Cr, Fe, Ag, Sn and Ir in the sample were higher
than the detection limit, the uncertainty of these five elements should be calculated.
3.2.1. Mathematical Model
Using LA-ICP-MS to determine the content of impurity elements in high purity gold
under selected parameters, the content results of each impurity element to be tested can
be expressed by the following formula:
, D EZ (1)
Table 1. The results of the sample.
Element Results (mg/kg) Detection limit (mg/kg) Element Results (mg/kg) Detection limit (mg/kg)
Mg 0.097 0.682 Ti 0.014 1.021
Cr 0.194 0.078 Mn 0.058 0.159
Fe 2.175 0.958 Ni 0.012 0.202
Cu 0.014 0.198 Zn 0.037 0.780
As 0.030 0.454 Ru 0.001 0.031
Rh 0.000 0.005 Pd 0.019 0.061
Ag 2.284 0.140 Cd 0.026 0.036
Sn 0.401 0.192 Sb 0.006 0.021
Ir 0.008 0.003 Pt 0.002 0.009
Pb 0.017 0.109 Bi 0.000 0.007
In the formula, I stand for signal intensity, a stands for intercept of calibration curve,
b stands for slope of calibration curve, ω stands for mass fraction of elements to be
measured (mg/kg).
3.2.2. Source Analysis of Uncertainty
According to the experimental method and mathematical model, the sources of
uncertainty in the determination of high purity gold by LA-ICP-MS are as follows:
X UHO & : Relative standard uncertainty introduced by reference material.
X UHO Z& : Relative standard uncertainty introduced by standard curve.
X UHO $ : Relative standard uncertainty introduced by repeatability.
458 B. Huang et al. / Uncertainty Evaluation for Determination of Gold in High-Purity Gold
3.2.3. Relative Standard Uncertainty Introduced by Reference Material
The relative standard uncertainty of the measured element of the reference material can
be approximated by the root mean square calculation of the relative standard uncertainty
of the measured element of each standard material.
¦
L
XUHO & L
(2)
XUHO &
Q
In the formula, X UHO & L stands for relative standard uncertainty of the element to be
measured for the i standard material.
The standard uncertainty u of the five test elements of Cr, Fe, Ag, Sn and Ir in the
standard sample is checked by the standard material certificate, and the relative standard
uncertainty of each test element is calculated using the above formula. The results are
shown in table 2.
3.2.4. Relative Standard Uncertainty Introduced by Standard Curve
In this experiment, five gold standard samples were used. The signal intensity was
measured by laser ablation inductively coupled plasma mass spectrometry. Each point
was measured three times, and the samples were measured 10 times at the same time.
The least square method was used for fitting.
According to JJF 1059.1-2012 and GB/T 27418-2017, the standard uncertainty
generated by the linear fitting of the calibration curve for the determination of each
element to be measured in the sample is:
65 Z Z& (3)
X Z& Q
E 3 Q
¦
L
Z& L Z&
In the formula, 6 5 stands for residual standard deviation, Z& stands for average of
calibration contents of calibration curve, n stands for measurement times of reference
materials (n=15), P stands for measurement times of the sample (P=10).
According to the following formula, the relative standard uncertainty of calibration
curve linear fitting for the determination of each element in the sample can be obtained:
X Z&
XUHO Z&
Z
The relative standard uncertainty of each element to be measured is shown in table
3.
B. Huang et al. / Uncertainty Evaluation for Determination of Gold in High-Purity Gold 459
Table 2. Content and uncertainty of reference materials.
1 2 3 4 5
Element Content Content Content Content Content X UHO &
u u u u u
(mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg)
Cr 0.11 0.04 1 0.5 3 0.5 5 0.5 10 0.5 0.291
Fe 0.29 0.09 5 0.5 10 0.5 22 1 43 1.5 0.150
Ag 0.36 0.11 6 0.5 16 0.5 54 1.5 150 5 0.144
Sn 0.005 0.01 4 0.5 10 0.5 21 1 39 1.5 0.897
Ir 0.029 0.058 2 0.5 2 0.5 7 0.5 11 1 0.910
Table 3. Statistical parameters of the standard working curve of the five elements to be tested.
Element Content of sample (mg/kg) a b SR X Z& (mg/kg) X UHO Z&
Cr 0.193 16 851 390 0.109 0.564
Fe 2.173 1109 799 1277 0.354 0.163
Ag 2.283 5568 3790 21288 1.160 0.508
Sn 0.406 1884 1586 3286 0.491 1.209
Ir 0.007 2991 18607 13650 0.181 24.755
3.2.5. Relative Standard Uncertainty Introduced by Repeatability
Under the same conditions, the sample was repeatedly determined for 10 times, and the
signal strength and related statistical results of the five elements, including Cr, Fe, Ag,
Sn and Ir, were obtained, as shown in table 4.
The standard deviation of 10 measurements was obtained by Bessel formula. The
6$
relative standard uncertainty was obtained according to formulas X $ and
Q
8 $
XUHO $ . The calculation results were shown in table 4.
Z
3.2.6. Uncertainty Combination
The relative standard uncertainty of the standard materials, introduced by the calibration
curve, and the introduced by the repeatability of the sample were calculated to combined
relative uncertainty:
X &UHO Z X UHO & X UHO Z& XUHO $ (4)
Calculated by the above formula, the combined relative uncertainty of each element
to were obtained, and the combined standard uncertainty was calculated according to the
combined relative uncertainty, the calculation results were shown in table 5.
X& Z X&UHO Z u Z (5)
460 B. Huang et al. / Uncertainty Evaluation for Determination of Gold in High-Purity Gold
Table 4. Repeated determination content of the five elements and related statistical results.
Fe Ag
Cr (mg/kg) Sn (mg/kg) Ir (mg/kg)
(mg/kg) (mg/kg)
1 0.077 1.576 2.407 0.516 0.008
2 0.387 2.78 2.34 0.43 0.009
3 0.124 2.224 2.478 0.376 0.007
4 0.108 2.54 2.18 0.408 0.008
5 0.062 2.68 2.284 0.398 0.007
6 0.216 2.329 2.314 0.322 0.004
7 0.417 2.344 2.232 0.451 0.007
8 0.216 0.963 2.068 0.355 0.006
9 0.155 2.575 2.359 0.494 0.006
10 0.17 1.716 2.169 0.312 0.011
Ave 0.193 2.173 2.283 0.406 0.007
SD 0.122 0.578 0.123 0.068 0.002
Standard uncertainty 0.039 0.183 0.039 0.022 0.001
Related standard
0.199 0.084 0.017 0.053 0.082
uncertainty
Table 5. The combined relative uncertainty and the combined standard uncertainty of the elements to be
measured.
Content of sample Combined standard
Element Combined relative uncertainty
(mg/kg) uncertainty
Cr 0.193 0.665 0.128
Fe 2.173 0.237 0.515
Ag 2.283 0.528 1.206
Sn 0.406 1.506 0.612
Ir 0.007 24.772 0.181
Combined the standard uncertainty of Cr, Fe, Ag, Sn and Ir:
X&VXP Z PJ NJ
Taking 95% confidence level, including factor k = 2, the expanded uncertainty was
as follows:
8 VXP Z X&VXP Z u PJ NJ
3.3. Content of the High-Purity Gold
Combined the expanded uncertainty and the content of sample, the gold content in the
sample can be expressed as follows:
Z$X r ‰
B. Huang et al. / Uncertainty Evaluation for Determination of Gold in High-Purity Gold 461
4. Conclusion
In this study, the content of impurity elements in high-purity gold were determined by
LA-ICP-MS, and the accuracy and reliability of the test results were improved by
calculating the uncertainty. According to the test and analysis, the gold content of the
high purity gold sample is (999.995 ± 0.003)‰, so the gold content of the sample is more
than 999.99‰. The result shows that the LA-ICP-MS has the advantages of fast, accurate
and green, which is conducive to the rapid development of jewellery industry technology,
and puts forward guiding suggestions for the production development direction, and
promotes the green and healthy development of jewellery industry.
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