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DETERMINATION OF SILVER, GOLD AND COBALT IN SULFIDE ORES AND

PRODUCTS OF THEIR PROCESSING BY ICP-AES

Conference Paper · August 2017

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N. V. Pechishcheva K. Yu. Shunyaev

Russian Academy of Sciences Institute of metallurgy, Russia, Ekaterinburg
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 DETERMINATION OF SILVER, GOLD AND COBALT IN SULFIDE ORES AND
PRODUCTS OF THEIR PROCESSING BY ICP-AES

O.V. Evdokimova, N.V. Pechishcheva, P.V. Zaitceva, K.Yu. Shunyaev

IMET UrB RAS, Yekaterinburg, 620016, 101, Amundsena st., evdokimova.olgav@gmail.com

ABSTRACT

The analytical technique has been developed for the determination of valuable trace
components, namely gold, silver and cobalt in materials containing high concentrations of
sulfur, copper, iron and nickel by inductively coupled plasma atomic emission spectrometry
(ICP-AES). For this purpose, the effect of the major components on the atomic emission of
target analytes in solutions after the acid decomposition of the samples was studied. Also the
method for calibrating the spectrometer and the optimal operating parameters were chosen, as
well as the optimum wavelengths for observing the analytes emission. The quality of the
procedure was verified using certified reference materials of copper, copper-nickel, gold-
silver sulfide ores, matte and their mixtures.

INTRODUCTION

Sulfide ores are an important source of nonferrous metals, for example, copper, nickel and
cobalt. In most of them, microquantity of precious metals (including gold and silver) are
found. In the practice of the analytical chemistry laboratory of Institute of Metallurgy of UrB
RAS, it is often necessary to quickly determine the valuable microcomponents of sulfide ores
of various compositions and products of their processing. The main components of analyzed
samples are nickel, copper, iron, sulfur, and also silicon, calcium, magnesium.
The purpose of the present work was the development of a multi-element technique that
allows determining microcomponents of sulfide ores and their products, namely gold (with a
content of 0.0001-0.0015% wt.), silver (0.001-0.01% wt.) and cobalt (0.03-0.6 % wt.)
simultaneously in the presence in solution of significant quantities (up to 40% wt.) of sulfur,
copper, iron and nickel.
For the determination of gold and silver in ore materials, various types of assay analysis,
variants of photometry, atomic absorption spectrometry (including electrothermal one) and
atomic emission spectrometry (usually with preliminary extraction or sorption) are used in
laboratory practice; cobalt is also determined by photometry, atomic absorption, atomic
emission, and by a potentiometric method (1 - 5). There are some works about application of
X-ray fluorescence analysis, gamma and neutron activation method for determining these
elements (5). Most of these methods are time-consuming and allow determining only one
component at the same time; they require the separation of the matrix, which increases the
duration of analysis significantly and can lead to significant errors. All these circumstances
make it difficult to analyze a large flow of samples. Inductively coupled plasma atomic-
emission spectrometry (ICP-AES) due to the high speed of measurements and the ability to
carry out multi-element analysis could be an alternative. We did not find IСP-AES techniques
of simultaneous determination of gold, silver, and cobalt in sulfide ores and products of their
processing in the literature.

143
Taking into account the possible matrix effects from the significant amount of copper, nickel
and iron in the sulfide materials on the analytic signal of gold, silver and cobalt, it is
necessary to carefully optimize the stage of sample preparation and the operating conditions
of ICP-AES analysis. In the paper (6) preliminary experiments for the development of ICP-
AES technique of determining the components of sulfide copper and nickel ores and
concentrates were carried out. It was shown by thermodynamic simulation and
experimentally that the acid digestion by heating the samples in a mixture of HCl : HNO3
(3:1) followed by separation from the precipitate (in which silicon is main component) is
effective in determining gold, silver and cobalt. However in the mentioned work products of
processing of non-ferrous sulfide raw materials, for example, matte, were not considered.
The tasks of the present work were:
- verification of the acceptability of acid digestion of sulfide ore raw materials and products
of its processing of various compositions for the determination of gold, silver, and cobalt by
ICP-AES method;
- investigation of matrix influences from macro components on the atomic emission signal of
gold, silver, and cobalt in solutions after decomposition of samples; the choice of optimal
wavelengths, the method of calibration of the spectrometer and the optimum parameters of
the spectrometer for ICP-AES determination of target analytes.

Experimental

1. Objects
The objects of the study were reference materials of sulfide raw materials of non-ferrous
metals, with certified mass fraction of gold, silver, and cobalt, as well as their mixtures (see
Table 1).

2. Equipment
Emission measurements were performed by ICP-AES spectrometer Optima 2100 DV Perkin
Elmer with a quartz burner. Analytical spectral lines: Au I 267.595 nm, Au I 242.795 nm, Ag
I 328.068 nm, Ag I 338.289 nm, Co II 228.616 nm, Co II 230.786 nm, Co II 238.892 nm.
Optimized operational parameters for determining gold, cobalt and silver: Rf power - 1500
W; carrier argon flow rate - 0.7 L⋅min-1; auxiliary gas flow rate- 0.2 L⋅min-1; plasma gas flow
rate- 15.0 L⋅min-1; observation mode - axial; horizontal position of the plasma observation
zone - 15 mm; sample uptake rate - 1.5 ml⋅min-1; spraying time - 40 s, number of replicas - 2,
registration of peak in height, the 1-point background position for Au I 267.583 nm is
267.595 nm and for Au I 242.795 nm is 242.790 nm.
For semi quantitative X-ray fluorescence analysis S4 Explorer (Bruker) spectrometer was
used.

144
Table 1. The objects of the study. Certified reference materials of the sulfide ores and their
processing products

Certified value of mass fraction, %

Sample
Ag Au Co S Cu Ni Fe SiO2
R34а n/c n/c
0.0081 0.00047 38.6 17.21 32.9 1.92
Copper concentrate (0.08)* (n/d)
R35 n/c n/c n/c
0.00174 0.000123 26.7 1.65 35.2
Copper sulfide ore (0.05) (n/d) (18.9)
FShT-30 n/c n/c
0.00728 0.00028 0.57 22.6 33.6 38.7
Matte (2.8) (0.39)
RMO-5
n/c n/c
Copper-nickel sulfide 0.00228 0.00014 0.0383 13.7 6.9 1.26
(21.5) (22.7)
ore
SО-24 n/c
0.0094 0.00123 28.46 0.047 0.012 26.22 34.42
Gold-silver ore (0.05)
Mixture No 1
n/c n/c
RMО-5 and FShT-30 0.00478 0.00021 0.304 18.15 20.25 19.98
(12.2) (11.8)
(1:1)
Mixture No 2
n/c n/c
RMО-5 and FShT-30 0.00328 0.00017 0.1446 15.48 12.24 8.75
(17.8) (18.3)
(4:1)
Mixture No 3
n/c n/c n/c n/c
R35 and FShT-30 0.00451 0.00020 24.65 17.63
(0.3) (19.4) (10.9) (18.0)
(1:1)
* In parentheses here and in the whole table – the indicative values obtained by semi
quantitative X-ray fluorescence analysis
n/c – not certified; n/d – not detected by X-ray fluorescence

3. Reagents
Reagents of analytical purity were used for all experiments.
For the spectrometer calibration the reference materials of ions solutions were used: for gold -
GSO 8429-2003 (MSO 0623:2004), for silver - GSO 8204-2002 and for cobalt - GSO 7880-
2001, and nickeli, iron and copper solutions prepared from pure metal (not less than 99.9 %
wt.).
Synthetic mixtures were prepared for studying the matrix effect on the emission signal of the
analytes: the concentration of the analytes in solutions was kept constant (0.5 mg⋅L-1 for gold
and silver, 1.0 mg⋅L-1 for cobalt); copper, iron and nickel concentrations were varied within
the range corresponding to their possible content in solutions after decomposition of sulfide
ore materials samples - from 0.05 to 5.0 g⋅L-1. Solutions of matrix elements were obtained by
dissolving of Cu(CH3COO)2⋅H2O, FeCl3⋅6H2O, Ni(NO3)2⋅6H2O in the water.
The operating conditions of ICP-AES analysis were selected using synthetic mixtures
prepared on the basis of sulfide ore reference materials after sample preparation and fixed
addition of the gold, silver and cobalt solutions (up to their concentration of 1 mg⋅L-1).
To prepare all the solutions distilled water was refined using a PureLab UHQ (Elga) unit.

145
Results and Discussion

1. Investigation of matrix influence

Using the acid digestion solutions of the samples R34a, R35, RMO-5, FShT-30, spectra of
the most sensitive gold, silver and cobalt emission lines were obtained: Ag I 328.068 nm, Ag
I 338.289 nm, Au I 267.595 nm, Au I 242.795 nm, Co II 238.892 nm, Co II 230.786 nm and
Co II 228.616 nm. As a result, the influence of the matrix components, namely, iron, copper,
nickel, on the intensity of analyte emission lines was revealed. The examples of the influence
are demonstrated in Fig. 1: a) background effect of copper and iron on the Ag I 328.068 nm,
b) spectral overlap of iron on the Au I 267.595 nm, c) background effect of nickel on the Co
II 238.892 nm.
Therefore, it was decided to investigate the effect of these metals on the emission of analytes
in more detail. The emission intensity of all the mentioned spectral lines of analytes (Me =
Au, Ag, Co) was measured at concentration in the solution 0.5 mg⋅L-1of Au or Ag and 1.0
mg⋅L-1 of Co in the absence (I(Me)) and in the presence (I(Me)Mt) of matrix elements (Mt =
Fe, Cu, Ni) in different concentrations. For each case, the degree of matrix influence was
calculated as

γ = I(Me)Mt/I(Me).

In Fig. 2, the degree of matrix influence on silver (a), gold (b) and cobalt (c) as a function of
the matrix element concentrations is presented. As can be seen, the degree of matrix influence
remains insignificant up to 100 mg⋅L-1 of copper, nickel and iron, then it more or less sharply
increases.
Compared to the Ag I 328.068 nm line, the Ag I 338.289 nm line is less influenced by the
matrix components, the degree of the influence is decreased in the sequence Fe > Ni > Cu.
The presence of nickel does not influence on the intensity of studied Au lines. Copper
concentrations, greater than 1000 mg⋅L-1, significantly reduce the intensity of background
signal of both Au lines. As for iron, Fe II 267.622 nm and Fe I 267.528 nm overlap the Au I
267.595 nm line, Fe II 242.820 nm affects Au I 242.795 nm line. As a result, taking into
account the calculated degree of matrix influence, it is possible to recommend the use of Au I
267.595 nm for analyze of samples containing significant amounts of iron; but if the sample
contains less than 500 mg⋅L-1 of iron, Au I 242.795 nm is preferable.

146
 a)

b)

c)

Fig. 1. Spectra of the emission lines obtained by ICP-AES analysis of sulfide ore materials
after acid digestion: a) Ag I 328.068 nm (background effect of Cu, Fe), b) Au I 267.595 nm
(spectral overlap of Fe line), c) Co II 238.892 nm (background effect of Ni).

147
 3.5

a) Ag 328.068_Fe
3.0

2.5
Ag 338.289_Fe

2.0 Ag 328.068_Cu

γ(Ag)
Ag 338.289_Ni
1.5 Ag 328.068_Ni

1.0 Ag 338.289_Cu

0.5

0.0
1.5 2 2.5 3 3.5 4

Log C(Me)

1.8
Au 242.795_Fe
b) 1.6

1.4
Au 267.595_Fe
1.2
Υ(Au)

1.0 Au 242.795_Ni
Au 267.595_Ni
0.8

0.6 Au 267.595_Cu
Au 242.795_Cu
0.4

0.2

0.0
1.5 2 2.5 3 3.5 4
Log C(Me)

3.6
c) Co 228.616_Ni

3.1

2.6 Co 238.892_Fe
γ(Ag)

2.1 Co 230.786_Ni

1.6
Co 238.892_Ni_Cu

1.1 Co 230.786_Fe_Cu
Co 228.616_Fe_Cu

0.6
1.5 2 2.5 3 3.5 4
Log C(Me)

Fig. 2. The degree of matrix influence of Сu, Ni, and Fe on the intensity of Ag, Au, and Co
emission lines vs logarithm of the metal concentration (mg⋅L-1)

The cobalt line Co II 238.892 nm was partially overlapped with the Fe II 238.863 nm line.
Therefore, for samples with large quantities of iron, the use of Co II 228.616 nm and Co II
230.786 nm is recommend, in other side due to the spectral overlap of the Ni II 228.709 nm
and Ni I 231.096 nm lines on them the Co II 238.892 nm line is preferably for analyzing of
copper-nickel mattes. The background effect of copper on the cobalt lines is insignificant.
Based on the results of the studies, the matrix effect was compensated by adding 2.5 g⋅L-1 of
copper and 5 g⋅L-1 of iron to the calibration solutions for gold determination. For the silver
determination, addition of 2.5 g⋅L-1 of copper, 2.5 g⋅L-1 of nickel and 5 g⋅L-1 of iron was
148
made. As for cobalt determination, 500 mg⋅L-1 of nickel should be added. The blank for the
calibration should be a solution containing the acids used to sample pretreatment of
investigated materials.

2. ICP-AES instrumental optimization

Using the axial plasma observation, the following operating conditions were optimized: Rf
generator power (W), the position of the observation zone along the horizontal axis (h, mm),
the carrier gas (argon) flow rate (VAr, L⋅min-1). The Rf power varied in the range from 1200
to 1500 W, the position of the observation zone was from 12 to 17 mm, the carrier gas flow
rate was from 0.65 to 0.95 L⋅min-1. Maximum of the analyte emission signal at their
concentration 1 mg L⋅min-1 was selected as a criterion for optimization. It was found that the
maximum values of emission signals (number of measurements n = 5) for Au I 267.595 nm,
Au I 242.795 nm, Ag I 328.068 nm, Ag I 338.289 nm, Co II 238.892 nm, Co II 228.616 nm
and Co II 230.786 nm were observed at Rf power = 1500 W, VAr = 0.70 L⋅min-1, h = 15 mm
(see Fig. 3 and Fig. 4). These operating conditions were chosen for further work.
Similar studies were performed using radial plasma observation. It was found that the
maximum emission signals of the target trace components were observed under the following
condition: Rf = 1500 W, carrier gas flow rate 0.80 L⋅min-1, observation zone height above the
inductor 14 mm. Comparison of the emission signal RSD values obtained by using two mode
of plasma observation under optimal conditions shown that for the axial observation RSD
values are smaller. For example, for one of the synthetic mixture emission signal the RSD
with axial observation of Au I 267.595 nm, Co II 238.892 nm and Ag I 328.068 nm were 0.5
%, 0.4 %, and 0.9 % correspondingly, whereas with radial observation RSD value were 0.5
%, 1.0 % and 1.2 % (n = 5). Therefore, for the further work, the axial observation of plasma
was chosen.

3. Optimized procedure
As a result of the study the following procedure was formulated. 2.0 g of sulfide ore material
(or product of their processing) sample is heated in a mixture of HCl : HNO3 (3:1) (40 ml) in
a heat-resistant beaker on an electric stove for 15 min, then is filtered through "Blue ribbon"
filter. Precipitate is discarded. The solution is transferred into a 100 ml volumetric flask and
diluted to the mark by distilled water. A blank sample containing all reagents, except for the
material under study, is prepared.
Solutions for the calibration of the spectrometer (0.1, 0.5, 1, 2.5 mg⋅L-1 for gold and silver, 1,
5, 20 mg⋅L-1 for cobalt) are prepared by diluting reference materials of ion solutions of the
analytes. Aliquots of iron and copper solutions are added to the calibration solutions for gold,
so that 2.5 g⋅L-1 of copper and 5 g⋅L-1 of iron are contained in the final volume. For the silver
determination addition of 2.5 g⋅L-1 of copper, 2.5 g⋅L-1 of nickel and 5 g⋅L-1 of iron to the
calibration solutions is needed, for cobalt determination adding 500 mg⋅L-1 of nickel is
required. Then calibration solutions are diluted to the mark by the blank sample. The zero
point for the calibration should be the blank.

149
 Co 238.892
200000 320000

180000
Co 228.616
a) W 270000

I (Co 230.786 nm), cps

160000

140000
220000
I, cps 120000 Co 230.786

100000 170000

80000
120000
60000

40000
70000
20000

0 20000
11 12 13 14 15 16 17 18

h, mm

Ag 328.068
648000
b)
548000 Ag 338.289
W

448000
I, cps

348000

248000

148000

48000
11 12 13 14 15 16 17 18

h, mm

Au 242.795
c) 64000 85000
W Au 267.595 75000
I (Au 267.595 nm), cps

54000
65000
I (Au 242.795 nm), cps

44000 55000

45000
34000
35000

24000 25000

15000
14000
5000

4000 -5000
11 12 13 14 15 16 17 18

h, mm

Fig. 3. Dependence of the a) Co, b) Ag and c) Au emission intensity on the position of the
observation zone for different values of Rf power (from top to bottom for each emission line:
1500 W, 1400 W, 1300 W, 1200 W), VAr = 0.8 L⋅min-1.

Atomic emission of silver, gold and cobalt is measured; mass concentration (mg⋅L-1) of the
analyte according to the calibration plot is determined. The mass fraction of the analyte,
taking into account the dilution and the sample weight is calculated.
According to this developed procedure, gold, silver and cobalt were determined in the
samples indicated in Table 1. The results are given in Table 2.

150
 1 2
700000 3 70000

600000 60000
4
500000 50000

I(Au), cps
I(Co), cps 400000 40000
5
300000 30000

6
200000 20000
7

100000 10000

0 0
0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1

VAr

Fig. 4. Dependence of the emission intensity: 1 - Au I 267.595 nm, 2 - Au I 242.795 nm, 3 -

Ag I 328.068 nm, 4 - Ag I 338.289 nm, 5 - Co II 238.892 nm, 6 - Co II 228.616 nm, Co II
230.786 nm on the carrier gas flow rate VAr; Rf = 1500 W, h = 15 mm.

Table 2. Results of ICP-AES determination of Au, Ag, Co content in reference materials (n =

5, wt%)

Au Co Ag
Found Found Found
Sample Certifie Co Co Co
Certified Au Au Certified Ag Ag
d 228.61 230.78 238.89
267.595 242.795 328.068 338.289
6 6 2
RMO-5
0.00016 0.00034 0.00228 0.00237 0.00217 0.0383
Copper- 0.00014± 0.037 ± 0.037 ± 0.041 ±
± ± ± ± ± ±
nickel 0.00001 0.006 0.006 0.006
0.00002 0.00013 0.00007 0.00005 0.00011 0.0009
sulfide ore
R35 0.000123 0.00014 0.00035 0.00174 0.00179 0.00171
Not
Copper ± ± ± ± ± ± - - -
certified
sulfide ore 0.000009 0.00002 0.00008 0.00009 0.00006 0.00002
R34а
0.00047 0.00071
Copper 0.00047± 0.0081 ± 0.0082 ± 0.0081 ± Not
± ± - - -
concentrat 0.00003 0.0004 0.0003 0.0004 certified
0.00002 0.00012
e
SО-24 0.00127 0.00137
0.00123± 0.0094 ± 0.0093 ± 0.0091 ± Not
Gold- ± ± - - -
0.00008 0.0005 0.0004 0.0005 certified
silver ore 0.00002 0.00015
0.00042 0.00029
FShT-30 0.00028± 0.0073 ± 0.0066 ± 0.0067 ± 0.57 ± 0.57 ± 0.58 ± 0.57 ±
± ±
Matte 0.00002 0.0002 0.0002 0.0001 0.02 0.03 0.04 0.03
0.00006 0.00003
0.00031 0.00033 0.00478
Mixture 0.00021± 0.0046± 0.0046 ± 0.304 ± 0.29 ± 0.29 ± 0.29 ±
± ± ±
No 1 0.00001 0.0003 0.0004 0.010 0.03 0.04 0.04
0.00003 0.00005 0.00010
0.00021 0.00032 0.00328 0.00319 0.00314
Mixture 0.00017± 0.145 ± 0.141 ± 0.141 ± 0.145 ±
± ± ± ± ±
No 2 0.00001 0.004 0.006 0.010 0.009
0.00003 0.00007 0.00007 0.00017 0.00023

151
 0.00026 0.00028 0.00451 0.00428 0.00428
Mixture 0.00020± Not
± ± ± ± ±
No 3 0.00001 certified
0.00003 0.00007 0.00011 0.00009 0.00012

Conclusion
The results obtained according to the procedure developed in this paper are in good
agreement with the certified analyte contents in reference materials, but in samples with a
significant nickel content the results for silver determination are slightly underestimated and
the gold determination results are slightly overestimated. For the determination of silver and
cobalt, in general, all tested analytical lines proved to be equally suitable, whereas for gold
the best results were mainly obtained by using the Au I line of 267.595 nm.

The study is supported by Program of UB RAS, project № 15-11-3-35.

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