Spectrochimica Acta Part B: Atomic Spectroscopy 201 (2023) 106629

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Spectrochimica Acta Part B: Atomic Spectroscopy

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Improving the accuracy of EDXRF results in gold alloy analysis by matrix

effect correction
A.A.M. Mazuki a, b, *, M.M. Mahat a, *, S. Abdullah a, R. Ramli a, F.M. Nor b
a
Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
b
National Metrology Institute of Malaysia, SIRIM Berhad, 43900 Sepang, Malaysia

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

Keywords: Energy-Dispersive X-Ray Fluorescence (EDXRF) is a faster non-destructive analysis and demands less sample
Gold alloy preparation than the fire assay technique. This research sought to minimise the matrix effect (inter-element) by
Matrix effect studying the role of matrix-specific materials and thus improving the accuracy of EDXRF in gold alloy analysis.
Energy dispersive X-ray fluorescent
The combination of empirical calibration with standardless Fundamental Parameter (FP) was expected to fine-
tune the analysis of precious metals, such as gold (Au), silver (Ag), and copper (Cu). The acquired R2 of
0.9999 for all metals signalled an alignment between the certified value and EDXRF measurement. The technique
was validated with CRMs to determine corrective K-factors to realign systematic measurement errors due to alloy
mixture. The relative error (rel%) for all measurements was <0.1 rel%. The relative standard deviation (%rsd)
was reduced to <0.11%rsd for pure Au, 0.16%rsd for Au-Ag and Au-Cu mixture, and <0.20%rsd for Au-Ag-Cu
mixture with K-factor correction. A similarity to the fire assay might reduce bias. The null hypothesis of equal
mean values of fire assay and XRF data was confirmed by the student's t-test. This outcome showed that the XRF
provided acceptable precision and verified the null hypothesis on the equivalence between mean results.

1. Introduction
The non-destructive and rapid EDXRF is a feasible alternative to the
destructive fire assay procedure. However, EDXRF has its drawbacks.
Existing calibrations fall short of harnessing the full potential of com­
mercial EDXRF due to the manufacturer's no-tampering policy [1–4].
The default calibration from the manufacturer is not suitable for
assessing complex precious metals [1,5]. Gold alloys and their variants
in jewellery have disruptive properties in an EDXRF analysis, especially
the interelement effect (matrix) [6–8]. Outcomes from EDXRF analysis
are often employed as supporting data. On the other hand, the fire assay
has been favoured for decades as a standard reference with an accuracy
of up to 0.05 wt% [5,9–12].
EDXRF calibration curves must reflect elements of interest, such as
gold (Au) in pieces of jewellery [13–15]. The remaining alloying ele­
ments are the matrix. However, the matrix effect can disrupt analysis. If
the sample's matrix elemental composition contradicts the matrix-
specific material, the result can be disputed [16–18]. Based on empir­
ical calibration curves, EDXRF can only provide outstanding results if
the calibration material is similar to the sample. An extensive set of
calibration standards is required to calculate matrix effects correction
coefficients. Its accuracy depends on size and surface quality similarities
between samples and calibration material [19,20]. Fundamental
parameter (FP) modelling can also produce reliable results. Instead of
solely focusing on gold, this model factors all elements' results in the
matrix. According to the FP modelling, EDXRF minimally relies on
sample size and surface preparation quality. The FP calculation model­
ling offers greater statistical accuracy for irregular samples, such as gold
rings or archaeological artefacts, than the empirical calibration curve
[21,22].
Nevertheless, its accuracy can complicate FP applications in precious
metals analysis. A previous study exhibited a total absolute error of 0.5
wt% to 1.5 wt% in the gold assay of gold‑silver‑copper (Au-Ag-Cu) alloy
with the fundamental parameters (FP) in the absence of a calibration
material. When compatible calibration materials and software were
applied, the absolute error of gold assay in jewellery alloy improved to
<0.27 wt% [5].
This study combined standardless FP with empirical calibration
using matrix-specific materials. For the first step, relevant element
concentrations were computed with the standardless FP approach.
These estimated concentration values were independent of sample size
and surface quality, and the values replaced the intensities of

* Corresponding authors at: Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia.
E-mail addresses: adlan@sirim.my (A.A.M. Mazuki), mmuzamir@uitm.edu.my (M.M. Mahat).

https://doi.org/10.1016/j.sab.2023.106629
Received 31 August 2022; Received in revised form 23 January 2023; Accepted 23 January 2023
Available online 25 January 2023
0584-8547/© 2023 Elsevier B.V. All rights reserved.
A.A.M. Mazuki et al. Spectrochimica Acta Part B: Atomic Spectroscopy 201 (2023) 106629

Fig. 1. Preparation of yellow gold calibration materials. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version
of this article.)

were a mixture of gold, silver, and copper that emulated the complete
Table 1
range of yellow gold alloys in mass fraction percentages from 75.00 wt%
Calibration materials with various gold alloy compositions.
to 99.99 wt%. The materials were shaped into discs with a diameter of
Calibration Material Code Composition in mass fraction of percent (wt%) 12 mm and a thickness range of 0.25 mm to 0.30 mm. An ARL OPTIM'X
Aua Agb Cb Wavelength Dispersive X-ray Fluorescent (WDXRF) Spectrometer was
CM1 75.00 25.00 –
used to evaluate the homogeneity of the calibration materials. Random
CM2 75.00 – 25.00 measurements from the surface of each disc based on ASTM E826-14
CM3 75.00 15.00 10.00 and the materials were performed to evaluate gold content distribu­
CM4 91.80 8.20 – tion [28]. A statistical analysis ensured the consistency of materials. The
CM5 91.80 4.72 3.48
findings were acquired by measuring the intensity of XRF radiation in 10
CM6 91.80 – 8.20
CM7 99.99 – – selected areas in the front and back of each calibration material with a
a
1.0 mm collimator beam. The element purity experiment indicated that
The gold purity was evaluated with the fire assay according to ISO 11426.
b alloying elements were uniformly distributed across all calibration
Wavelength Dispersive X-ray fluorescent (WDXRF) was performed on tar­
materials.
geted silver and copper according to ISO 9516.
The gold purity was determined by fire assay according to ISO 11426
[29]. Fire assay is a quantitative analytical chemistry to evaluate
corresponding analytical lines in the calibration module [23–26]. This
precious metal concentrations with fusion extraction and dry chemical
path addressed the systematic error of the standardless FP for Au-Ag-Cu
reagent (flux). This low-cost destructive process can accurately deter­
alloy across a wide concentration range. In addition, this research
mine gold content. The fire assay has a measurement uncertainty of 0.05
investigated the roles of matrix-specific materials in EDXRF gold mea­
wt% with a high success rate for objects with 33.00 to 99.99 wt% gold.
surements. The influences on the EDXRF spectrometer were studied with
The fire assay emphasises metal characteristics under specific temper­
this selected alloy. In this study, 75.00 wt% to 99.99 wt% gold (Au) was
atures and chemical conditions [9]. Wavelength dispersive X-ray fluo­
the primary target material. The instrument calibration, which com­
rescence (WDXRF) was performed to measure the purity of silver and
bined the fundamental parameter (FP) and standard empirical tech­
copper according to ISO 9516 [30]. Table 1 shows the calibration ma­
nique, was expected to eliminate the matrix effect from silver and
terials with gold alloy.
copper in the gold alloy. Corrective K-factor values were applied to
realign measurement results for various alloy mixtures [27]. When
2.2. Calibration procedure
employed on matrix-specific materials, EDXRF provides analytical re­
sults that are on par with or better than conventional techniques. Gold
The primary analytical instrument in this study was the Thermo ARL
assayers, jewellers, gold retailers, pawnshops, and accreditation labs
Quant EDXRF spectrometer at the National Metrology Institute of
stand to benefit the most from this innovative measurement technique.
Malaysia (NMIM). A high flux 50 W rhodium anode X-ray tube with an
excitation voltage of 4 to 50 kV and an anode current of 0.8 mA was
2. Experimental
used. The tube was covered to excite the elements' energy, sufficient for
gold and other target elements such as copper and silver. The instrument
2.1. Gold calibration materials
was equipped with a Silicon Drift Detector (SDD). The detector had a
narrow window that could handle high count rates while maintaining
Non-destructive analytical techniques like EDXRF require matrix-
resolutions of <165 eV FWHM (Full width at half maximum) at Mn K-
specific calibration. A series of homogeneous gold materials that
alpha. It provided superior performance across the periodic table from
resemble actual samples were designed as calibration material (CM) to
light to heavy elements. The instrument's setup is depicted in Fig. 2.
optimise EDXRF matrix correction. Fig. 1 shows the preparation of seven
50 kV and 20 kV were sufficient to excite an electron from the K-shell
specific matrix gold calibration materials. These calibration materials
of silver and copper, and the target gold from the L-shell. Copper and

2
A.A.M. Mazuki et al. Spectrochimica Acta Part B: Atomic Spectroscopy 201 (2023) 106629

Fig. 2. Left: Thermo ARL Quant EDXRF spectrometer. Right: The instrument set up position.

Table 2
Set-up parameter of EDXRF analysis.
Filter Condition Selected Element Counting Rate Method
(s) (seconds)

Pd 20 kV, Vacuum Au, Cu 120 Combination of Fundamental Parameter (FP) and empirical calibration materials, as
Medium medium described in Section 2.1
Cu Thick 50 kV, Vacuum Ag 120 Combination of Fundamental Parameter (FP) and empirical calibration materials, as
medium described in Section 2.1

Table 3
Gold alloy composition for certified reference materials (CRMs).
Mixture Code of CRMs Composition in mass fraction of percent (wt%)

Au Ag Cu

Au SRM 685R 99.99 ± 0.05 – –

Au-Ag ERM 508 75.12 ± 0.11 24.90 ± 0.05 –
Au-Cu MyRM 22 K 91.80 ± 0.15 – 8.20 ± 0.05
Au-Ag-Cu MyRM 5.102 92.14 ± 0.16 1.93 ± 0.05 5.96 ± 0.04

Table 4
The list of commercial gold alloy samples.
Mixture Sample Gold Puritya Expanded Uncertainty, 95%
code (wt%) confident interval

Au AU1 99.9187 0.0459

AU2 99.9902 0.0452
AU3 99.9903 0.0450
AU4 99.9901 0.0451
Au-Ag AU5 83.5013 0.0482
AU6 91.7019 0.0473
AU7 87.5007 0.0484
AU8 75.1002 0.0491
Au-Cu AU9 91.8821 0.0480
AU10 91.9002 0.0471
AU11 76.1203 0.0492
AU12 83.5801 0.0484
Au-Ag- AU13 91.8901 0.0490
Cu AU14 76.3401 0.0494
AU15 75.1002 0.0489
AU16 74.5500 0.0498
a
The gold's purity have been determined with the fire assay according to ISO
11426.

Fig. 3. Four sets of certified reference materials (CRMs).
palladium filters were used to remove dominant x-rays from the x-ray
tube that may have overlapped fluorescent with the element of interest.
A thick copper filter was selected because of its ability to absorb zinc and
aluminium energy from x-ray emission lines to produce a higher-fidelity
silver peak spectrum. The palladium medium filter adsorbed silver en­
ergy from x-ray emission lines to produce higher fidelity gold and copper
peak spectrum. The filters were analysed under vacuum to eliminate the
ambient atmosphere between the sample and detector while optimising
light element sensitivity. An x-ray collimator with a diameter of 1.0 mm
was used to analyse the sample area to optimise the analysis. A smaller

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A.A.M. Mazuki et al. Spectrochimica Acta Part B: Atomic Spectroscopy 201 (2023) 106629

Fig. 4. X-ray Spectrum of Au–Ag–Cu alloy. The peak at lower energy was tagged as the Cu Kα peak with an energy of 8.041 keV and Cu Kβ at 8.907 keV. Au Lα, Au Lβ
and Au Lg peaks were visible at 9.711 keV, 11.439 keV and 13.733 keV, respectively. Meanwhile, the peak at 22.104 keV was identified as the Ag Kα peak. Ag Kβ
peak was assigned to 24.987 keV.

was purchased from the Bundesanstalt fur Materialforschung und pru­

Table 5 fung (BAM), Germany. SRM 685R was purchased from the National
The XRF measurement based on a series of Calibration Materials. Institute of Science and Technology (NIST), United States. The National
Code of Calibration sample Composition in mass fraction of percent (wt%)a Metrology Institute of Malaysia certified the compositions of MyRM
Au Ag Cu
5.102 and MyRM 22 K.
The corrective K-factor values were determined for each alloy
CM1 76.34 ± 0.15 23.66 ± 0.09 –
mixture to realign the EDXRF measurement. These CRMs were validated
CM2 75.85 ± 0.15 – 24.15 ± 0.10
CM3 74.00 ± 0.16 15.00 ± 0.08 11.00 ± 0.09 to determine the correction K-factor values. The values were applied to
CM4 91.89 ± 0.15 8.11 ± 0.06 – the computation of each analysed sample based on the similarity of the
CM5 91.67 ± 0.15 4.72 ± 0.05 3.61 ± 0.05 elements in the gold mixture. The correction factor is the quotient of the
CM6 92.02 ± 0.17 – 7.98 ± 0.06 certified value of gold measured by gravimetric m(Au, CRMgrav) against
CM7 99.90 ± 0.15
and the observation of measured by EDXRF m(Au, CRMXRF obs ). The vali­
– –
a
The element composition was determined by combining fundamental pa­ dated ratio of gold value determined the corrective K-factor with the aid
rameters (FP) and an empirical standard calibration approach. of the gravimetric method against the gold value measured with EDXRF
(Eq. (2)) [25].
collimator beam was used to reduce fluorescent signal loss while
m(Au, CRM grav )
improving measurement accuracy [22]. In this study, the Fundamental K= ( ) (2)
parameter was combined with an empirical calibration. Table 2 displays m Au, CRM XRF
obs

a summary of the setup parameters.

Eq. (1) shows the calibration model for each element.
( ) ( )
∑ ∑
Ci = a0 + ci ai + aii ci + aij cj + cj aj + ajj cj + ajk ck (1)
j k∕
=j
where Ci is the certified analyte concentration in the standard (wt%), ci
is the analyte concentration from the standardless FP module (wt%), and
cj and ck are the concentrations (%) of other elements in the standard
calculated by the standardless FP method. The best model was chosen
with the quadratic stepwise multiple regression algorithm, eliminating
statistically insignificant parameters from groups a0, ai, aii, aij, ajj, and ajk
before determining significant parameters [24].
2.3. Method validation by certified reference materials (CRM)
In Fig. 3, a set of certified gold reference materials (CRM) was
selected based on their related composition to the actual samples. As
shown in Table 3, gold and its alloy were determined with fire assay and
WDXRF with an expanded uncertainty of 95% confidence interval. The
CRM selection was critical to ensuring a homogeneous distribution of
gold in the samples that complied with ISO 17034. ERM 508 gold purity
where,
m(Au, Certified value of gold measured by the gravimetric in CRM that was
CRMgrav) close to sample material
m(Au, XRF measurement of gold in the CRM that was close to sample
CRMXRF
obs ) material
2.4. Commercial gold alloy samples
Fig. S1 displays 16 pieces of gold alloy (Carbon Worldwide Sdn Bhd)
with similar characteristics to the gold matrix specific materials to assess
the reliability of the EDXRF measurement. Eight samples were round
discs with a diameter of 30 mm, while the others were rectangular with a
dimension of 10 mm × 5 mm. The samples had a thickness of approxi­
mately 1 mm. EDXRF analysis was repeated five times on each sample
surface with a 1.0 mm collimator beam. The commercial samples had
compositions resembling a mix of Au, Au-Ag, Au-Cu, and Au-Ag-Cu
matrixes. Table 4 demonstrates a sample code with purity was
assessed with the fire assay.
The unknown composition of gold m(Au, Xobs) in the gold alloy
sample was rectified with the factor K, which led to the value of m(Au, X)

4
A.A.M. Mazuki et al. Spectrochimica Acta Part B: Atomic Spectroscopy 201 (2023) 106629

(a) Gold (Au) Content

100.00
y = 1.0046x - 0.335

Determined Value by Fire Assay, (wt%)

R² = 0.9999 CM6 CM7
95.00

90.00
CM4
CM5
85.00

80.00 CM2

75.00 CM1
CM3

70.00
70.00 75.00 80.00 85.00 90.00 95.00 100.00
Measured Value by EDXRF, (wt%)

(b) Silver (Ag) Content

30.00
y = 1.0037x - 0.0671
Determined Value by WDXRF, (wt%)

R² = 0.9999
25.00

CM1
20.00

CM3
15.00

CM4
10.00
CM5

5.00

0.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00
Measured Value by EDXRF, (wt%)

Copper (Cu) Content

(c) 30.00
y = 0.9955x - 0.0218
CM2
R² = 0.9999
Determined Value by WDXRF, (wt%)

25.00

20.00

15.00
CM3

10.00 CM6
CM5

5.00

0.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00
Measured Value by EDXRF, (wt%)

Fig. 5. a. Correlation graph between EDXRF and fire assay on gold content.
b. Correlation graph between EDXRF and WDXRF on silver content.
c. Correlation graph between EDXRF and WDXRF on copper content.

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A.A.M. Mazuki et al. Spectrochimica Acta Part B: Atomic Spectroscopy 201 (2023) 106629

Table 6
Corrective K-factor based on the compositions of gold reference materials.
Mixture CRMs Code Certified Value, wt% XRF Measurement, wt% Correction Factor, K
m(Au, Xgrav) m(Au, RMXRF
obs ) m(Au, Xgrav )
K = ( )
m Au, RMXRF
obs

Au NIST -SRM 685R 99.99 ± 0.05 99.95 ± 0.15 1.0004 ± 0.0005

Au-Ag ERM 508 75.12 ± 0.11 75.19 ± 0.18 0.9991 ± 0.0011
Au-Cu MyRM 22 K 91.80 ± 0.15 91.95 ± 0.17 0.9985 ± 0.0014
Au-Ag-Cu MyRM 5.102 92.14 ± 0.16 92.26 ± 0.18 0.9987 ± 0.0016

Table 7
Comparison of EDXRF measurements pre and post-correction against fire assay values.
Mixture Samples Composition of gold in mass fraction of percent (%)
Code
Fire Assay XRF Measurement Relative standard Relative Error XRF Measurement with Relative standard Relative Error
(wt%) A without K-Factor (wt%) deviation %rsd (rel%) (A-B)/ K-Factor (wt%) C deviation %rsd (rel%) (A-C)/
B A*100 A*100

K-factor 1.0004 ± 0.0005

Au AU1 99.92 ± 99.88 ± 0.16 0.16 0.04 99.92 ± 0.11 0.11 0.00
0.05
AU2 99.99 ± 99.94 ± 0.15 0.15 0.05 99.98 ± 0.10 0.10 0.01
0.05
AU3 99.99 ± 99.93 ± 0.15 0.15 0.06 99.97 ± 0.10 0.10 0.02
0.05
AU4 99.99 ± 99.93 ± 0.16 0.16 0.06 99.97 ± 0.11 0.11 0.02
0.05
K-factor 0.9991 ± 0.0011
Au-Ag AU5 83.50 ± 83.63 ± 0.18 0.22 − 0.13 83.52 ± 0.13 0.16 − 0.02
0.05
AU6 91.70 ± 91.86 ± 0.16 0.17 − 0.16 91.74 ± 0.11 0.12 − 0.04
0.05
AU7 87.50 ± 87.70 ± 0.17 0.19 − 0.2 87.59 ± 0.12 0.14 − 0.09
0.05
AU8 75.10 ± 75.25 ± 0.17 0.23 − 0.15 75.15 ± 0.12 0.16 − 0.05
0.05
K-factor 0.9985 ± 0.0014
Au-Cu AU9 91.88 ± 92.02 ± 0.16 0.17 − 0.14 91.94 ± 0.11 0.12 − 0.06
0.05
AU10 91.90 ± 92.03 ± 0.15 0.16 − 0.13 91.95 ± 0.10 0.11 − 0.05
0.05
AU11 76.12 ± 76.27 ± 0.16 0.21 − 0.15 76.20 ± 0.11 0.14 − 0.08
0.05
AU12 83.58 ± 83.70 ± 0.18 0.22 − 0.12 83.62 ± 0.13 0.16 − 0.04
0.05
K-factor 0.9987 ± 0.0016
Au-Ag- AU13 91.89 ± 92.03 ± 0.19 0.21 − 0.14 91.95 ± 0.14 0.15 − 0.06
Cu 0.05
AU14 76.34 ± 76.50 ± 0.18 0.24 − 0.16 76.43 ± 0.13 0.17 − 0.09
0.05
AU15 75.10 ± 75.24 ± 0.19 0.25 − 0.14 75.17 ± 0.14 0.19 − 0.07
0.05
AU16 74.55 ± 74.70 ± 0.20 0.27 − 0.15 74.63 ± 0.15 0.20 − 0.08
0.05

Table 8
Values of relevant statistical parameters from two distinct methods.
Au1 Au5 Au9 Au13

Fire Assay (wt%) XRF (wt%) Fire Assay (wt%) XRF (wt%) Fire Assay (wt%) XRF (wt%) Fire Assay (wt%) XRF (wt%)

Mean (x) 99.92 99.92 83.50 83.52 91.88 91.94 91.89 91.95
Variance (s) 0.0005 0.0033 0.0006 0.0040 0.0006 0.0031 0.0006 0.0052
Observations 10 10 10 10 10 10 10 10
Pooled Variance (Sc) 0.002 0.002 0.002 0.003
Hypothesized Mean Difference (H) 0 0 0 0
df 18 18 18 18
t Stat (95%) − 0.065 − 0.828 − 2.989 − 2.482
P(T ≤t) (95%) 0.475 0.209 0.004 0.012
t Critical (95%) 1.734 1.734 1.734 1.734

6
A.A.M. Mazuki et al.
as shown in Eq. (3) [27]:
m(Au, X) = K x m(Au, Xobs )
where,
m(Au, Xobs) EDXRF measurement of gold in the sample (before correction)
m(Au, X) Composition of gold in the sample (after correction)
3. Results and discussion
3.1. Correlation study of EDXRF with other reference methods on gold
alloy measurement
The EDXRF spectrum displayed the peaks of all the elements in the
gold alloy as shown in Fig. 4. The peaks at lower energy were tagged as
the Cu Kα peak with an energy of 8.041 keV and Cu Kβ at 8.907 keV. Au
Lα, Au Lβ and Au Lg peaks were visible at 9.711 keV, 11.439 keV and
13.733 keV, respectively. Meanwhile, the peak at 22.104 keV was
labelled as the Ag Kα peak, while the Ag Kβ peak was assigned to 24.987
keV. The measurement of alloy purity was performed by calculating the
areas of measured spectrum peaks of each element with respect to each
other, followed by calculating the analysis result by “matrix-matching”.
Matrix-matching compares the measurement of the object under study
to a measurement of calibration materials with a known elemental
composition. The purity of calibration materials measured by EDXRF
was based on Eq. (1). Table 5 lists the XRF measurements based on a
series of calibration materials.
The precision expressed as a standard deviation, s (n = 10) for gold
was <0.17 wt%, while the other alloys (silver and copper) were <0.1 wt
%. Introducing specific gold calibration materials to the FP method was
expected to improve the data accuracy and precision [5]. The data were
then plotted to form a correlation graph between the fire assay and
WDXRF as the reference methods with the EDXRF experimental values
in mass fraction (wt%), as shown in Fig. 5a–c. The regression (R2) of
0.9999 for all metals represented a good correlation between the ref­
erence's purity content and the EDXRF measurement.
3.2. Calculation of corrective factor, K
Table 6 shows the comparison between certified values and EDXRF
measurements. Eq. (2) shows the calculation for corrective K-factor from
a ratio of certified value to EDXRF experimental result. Corrective K-
factor values were identified for each alloy mixture to realign the mea­
surement. Depending on the similarity of elements in the gold mixture,
the values were applied to the calculation of each analysed sample. As
shown in Eq. (3), the corrective K-factor values were applied to EDXRF
measurement by improving the accuracy of actual samples.
According to the table, the corrective K-factor should vary depending
on the gold mixture. Unexpectedly, the corrective K-factor for pure gold
had an overestimated ratio than a gold alloy mix. This observation could
be attributed to interference or limitations with EDXRF that are common
with pure elements calibration. Therefore, corrective K-factor was
introduced to realign the measurement [27].
3.3. Application of corrective K-factor to unknown gold samples
Table 7 displays the differences between fire assay and EDXRF
measurements with two decimal places. In addition, the table lists the
values of various elements in the gold mixture with and without the
corrective K-factor. The relative error was calculated as the absolute
error of the measurement divided by the actual measurement. The
relative error implied EDXRF's accuracy with respect to fire assay values.
The relative error (rel%) was calculated with the formula, rel % = (|x1 −
x0|)/x0) * 100, where x0 is the measured value from the fire assay
Spectrochimica Acta Part B: Atomic Spectroscopy 201 (2023) 106629
method and x1 refers to the measured value from EDXR. The relative
error of method approached was consistently improved and aligned with
(3)
fire assay values for <0.1 rel% compared to post-K-factor application for
all measured metals.
The relative standard deviation (%rsd) was calculated to evaluate the
reproducibility of measurements. It was expressed as a percentage and
accomplished by dividing the standard deviation by EDXRF measure­
ment, followed by a multiplication of 100. The results indicated that the
measurements improved with <0.11%rsd for pure Au, 0.16%rsd for Au-
Ag and Au-Cu mixtures, and <0.20%rsd for mixtures of Au-Ag-Cu for
measurement with K-factor correction, instead of 0.16%rsd, 0.23%rsd,
0.22%rsd and 0.27%rsd for measurement without correction, respec­
tively. This might be due to the improve their closeness result and
reduced the bias as compared to fire assay. The corrective K-factor has
been applied to various commercial gold mixtures.
For comparison of two analysis methods, Student's t-test were per­
formed to verify the null hypothesis on absence of significant difference
in results means value for both methods, fire assay and corrected XRF
measurement were studied. The following parameters were calculated
for the Student's t-test: the mean value of measurements (x) for each
sample, the standard deviation for repeated measurements (s), and
pooled standard deviation (Sc). Au1, Au5, Au9 and Au13 samples were
selected to represent the diverse mix of gold alloys.
Table 8 shows the Student's t-test outcomes to verify the null hy­
pothesis on the equivalence between mean values of results for two
analyses in repeatability conditions. One of the following hypotheses
was investigated: H0; there is no significant difference in mean values if
tcritical > tstat; H1; there is a significant difference in mean values if tcritical
< tstat. The null hypothesis on the equivalence between mean values of
results from fire assay and XRF was confirmed. By comparing t-values
(tstat) of all four samples with critical value (tcritical) and P-value(T ≤t) >
0.05, obtained from table data for the student's t distribution for 18
degrees of freedom (df) and 95% confidence level, it was discovered that
XRF gave an acceptable precision while verifying the null hypothesis on
the equivalence between mean values of results than the fire assay.
4. Conclusion
The combination of FP with matrix-specific materials offered a
favourable estimation of precious metal purity in EDXRF. This technique
was successfully applied to gold and Au, Au-Ag, Au-Cu and Au-Ag-Cu
matrix elements in the gold mixtures. The matrix-specific calibration
materials significantly improved the calibration of EDXRF. The regres­
sion (R2) of 0.9999 for all metals represented a good correlation between
the certified value form reference with EDXRF measurement. The
method was validated with certified reference materials to identify the
corrective K-factor to realign the EDXRF measurement. The relative
error of this approach was consistently improved and aligned with fire
assay values for <0.1 rel% for all metals. The relative standard deviation
(%rsd) improved concurrently for measurements with K-factor correc­
tion. The student's t-test concluded that XRF produced an acceptable
precision while verifying the null hypothesis on the equivalence be­
tween mean values than the fire assay. This finding has shown a sig­
nificant effect of gold alloy mixtures for EDXRF measurement. Although
this study attempted to propose a non-destructive technique for a gold
assay that rivals the commonplace fire assay, the outcomes did not reach
the expected accuracy.
Author contributions
All authors contributed to the study conception and design. Material
preparation, data collection and analysis were performed by Ts. Adlan
Akram Mohamad Mazuki, Associate Professor Dr. Mohd. Muzamir
Mahat, Professor Saifollah Abdullah, Associate Professor Dr. Rosma­
muhamadani Ramli and Dr. Mohd Fazrulhisyam Mohd Nor. The
manuscript was written by Ts. Adlan Akram Mohamad Mazuki with
7
A.A.M. Mazuki et al.
Associate Professor Dr. Mohd. Muzamir Mahat and all authors read and
approved the final manuscript.
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.
Data availability
No data was used for the research described in the article.
Acknowledgements
The authors wish to thank SIRIM Berhad for the scholarship and
Universiti Teknologi MARA Malaysia for their valuable assistance in this
study.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.sab.2023.106629.
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