Received: 20 June 2019 Revised: 9 February 2020 Accepted: 10 February 2020

DOI: 10.1002/jrs.5859

RESEARCH ARTICLE

Online analysis of minerals from sulfide ore using near-

infrared Raman spectroscopy

Sanna Uusitalo1 | Tuomas Soudunsaari1 | Juha Sumen1 | Olli Haavisto2 |

Jani Kaartinen2 | Jarmo Huuskonen3 | Aki Tuikka3 |
Katariina Rahkamaa-Tolonen1 | Janne Paaso1

1
Optical Measurements, VTT Technical
Research Centre of Finland Ltd, Oulu,
Abstract
Finland Efficient recovery of minerals from bedrock ore requires precise knowledge of
2
Outotec, Automation Concept the mineral levels during enrichment processes. Froth flotation is a commonly
Development, Espoo, Finland
used method for efficient separation of different minerals from finely grinded
3
Pyhäsalmi Mine Oy, Rikastamo,
Pyhäjärvi, Finland
sulfide ore. The mineral level information is an important tool for the optimi-
zation of flotation process parameters as it is uneconomical to make mineral
Correspondence products with unacceptably low concentrations and to lose a share of the valu-
Sanna Uusitalo, Optical Measurements,
VTT Technical Research Centre of able minerals of the ore to the tailings. Online mineral control is commonly
Finland Ltd. Oulu, Finland. executed with X-ray fluorescence detection or laser-induced breakdown spec-
Email: sanna.uusitalo@vtt.fi
troscopy, which detect the elements of the minerals during flotation. Unfortu-
Funding information nately, in case of sulfide ores, the method suffers from inadequate detection of
European Union’s Horizon 2020 research lightweight materials such as sulfur and the common nature of iron, as iron is
and innovation programme project IbD
constantly present in several different minerals found in sulfide ores. Raman
Intensified by Design® for the
intensification of processes involving spectroscopy can be used to detect the minerals instead of mere elements of
solids handling, Grant/Award Number: ore. This paper presents the study of Raman spectroscopy for online detection
680565; PREIN The Flagship program on
Photonics Research and Innovation,
of enriched sulfide ore minerals from froth flotation. The Raman instrument
Grant/Award Number: 320168; CALMIN with a custom-made probe connector allowed for the recording of good quality
project; APASSI Autonomous Processes Raman spectra during froth flotation and for the identification and analysis of
Facilitated by Artificial Sensing
Intelligence Co-Innovation project
the valuable minerals levels. The comparison of Raman analysis to online
X-ray fluorescence and offline mineral liberation analysis show that Raman
spectroscopy is a suitable method for the online analysis of sulfide ores.

KEYWORDS
analysis, beneficiation, online, ore, sulfide

1 | INTRODUCTION material supply, efficient ore beneficiation is a critical

sector for material production.[1,2] Optimization of the
Raman spectroscopy (RS) is a novel analysis tool for mineral production requires optimization of the mineral
process control at mineral beneficiation facilities. As the enrichment process, which is dependent on the informa-
well-being of modern societies depend on sufficient tion of the mineral levels in the feed, concentrate, and

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2020 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons Ltd

978 wileyonlinelibrary.com/journal/jrs J Raman Spectrosc. 2020;51:978–988.

UUSITALO ET AL.
tailings. Thus, efficient ore beneficiation requires accu-
rate mineralogical online analysis. However, the current
online analysers tend to suffer from inaccuracy in deter-
mining certain mineral levels due to common material
elements such as iron (Fe) or light-weighted material ele-
ments such as sulfur (S). The current online analysers are
commonly based on X-ray fluorescence (XRF) or laser-
induced breakdown spectroscopy, which give informa-
tion on the material elements, but not on the minerals
themselves. Typically, the mineralogy of the ore has to be
analysed offline in a laboratory with mineral liberation
analysis (MLA), atomic absorption spectroscopy (AAS) or
X-ray diffraction (XRD) for periodic calibration of the
online analysers.[3] RS could be a complementary if not
substitutionary analysis method for online detection as it
has the ability to detect the minerals themselves instead
of mere elements through vibrations of the mineral
bonds. Thus, RS is able to form an individual fingerprint
spectrum for each detected mineral.[4]
The prior use of RS for mineralogical analysis shows
extensively that Raman scattering can differentiate a vari-
ety of minerals from each other.[5–11] Additionally a digi-
talization project RRUFF (http://rruff.info/) has gathered
a free access mineral spectral database containing the
Raman spectra of approximately 3,500 different mineral
species.[12] In regard of the ore beneficiation, there have
been some studies on highlighting the ability of RS on
qualitative analysis of mineral levels in ores. A manga-
nese (Mn) oxide ore study by Pani, Singh, and Mohapatra
compared the results of XRD, Fourier-transform infrared
and RS analysis of bulk manganese oxide rocks from
three Mn ore samples from four mine profiles with differ-
ent mineral compositions. The results demonstrated that
RS with support by corresponding infrared (IR) and XRD
spectral data can be used for qualitative analysis of man-
ganese (Mn) oxide ores and could be suitable as a stan-
dard procedure for qualitative assessment in a geological
set-up.[13] Furthermore, a study on drill core sample discs
by Secchi et al. showed that a quantitative determination
of mineral phase composition can be reached with a com-
bination of RS, XRF, and XRD analyses.[8] Another study
by Escarate et al. compared following three analysis tech-
niques: RS, ultraviolet fluorescence spectroscopy, and
energy-dispersive X-ray diffraction for determination of
calcite (CaCO3) concentration in copper (Cu) ore. The
study used a portable Raman spectrometer with an exter-
nal probe for the detection of Cu ore powders from a qua-
rtz cuvette. RS achieved quite similar accuracy levels as
the comparative techniques while showing considerably
faster signal recording times.[14]
In mining industry, there is a need for a fast and pre-
cise quantification method for the minerals of interest in
enrichment processes. A study focusing on stibnite
979
content on raw ore has evaluated the ability of multivari-
ate calibration models to predict the mineral concentra-
tion in filtered froth flotation powder samples obtained
from a concentrator.[15] According to the study, RS could
be used to determine the mineral content of stibnite with
sufficient accuracy from samples collected after froth flo-
tation with the help of multivariate data processing. This
could in theory improve precision in reagent chemical
dosing at the enrichment facility and improve the end-
product quality. However, the evaluation of RS was per-
formed with dry mineral powders offline, which delays
the analysis results. An evaluation of RS performance for
online process optimization for industrial mineral enrich-
ment at mining sites is still missing. In this study, the
applicability of RS for online detection of liquid flotation
froth and tailing samples was evaluated in a Pyhäsalmi
mineral beneficiation facility in synchronization with
online XRF detection. A Pyhäsalmi mine excavates sul-
fide ore from volcanogenic massive sulfide deposits. The
volcanogenic massive sulfide ore type is the most
exploited type in Fennoscandia Shield.[16] The ore of
Pyhäsalmi contains copper (Cu), zinc (Zn), iron (Fe), and
sulfur (S). In general, the mineral composition of ore
deposits varies in terms of changing ore minerals, their
quantitative ratios, and even as variation in mineral
forms. Thus, the enrichment process can suffer from vari-
ation of ore, and the enrichment efficiency can change
depending on the ore. The enriched minerals in
Pyhäsalmi are chalcopyrite, sphalerite, and pyrite, which
are sold to the manufacturing industry as minerals with
specific purity state. Higher purity can affect the price of
the product. This is why it is important for the mine to be
able to enrich the minerals with high efficiency. For min-
eral beneficiation, Pyhäsalmi utilizes flotation enrich-
ment, which has a leading position in separation of
minerals from nonferrous iron ores containing sulfides.
Globally, flotation is applied for extraction of approxi-
mately a hundred different minerals.[17]
Froth flotation utilizes rotation velocity, air input,
and prepared chemical composition to control the enrich-
ment process.[18] A graphical illustration of this technol-
ogy is presented in Figure S1 (Supporting Information).
During flotation, the hydrophobic mineral particles are
selectively separated from hydrophilic particles. The
chemicals ensure that the air bubbles bind hydrophobic
particles and carry them to the surface to form a froth
containing valuable minerals and water. The remaining
ore particles are collected from the bottom and moved to
the next mineral flotation cycle or to the waste. The
online mineral information is utilized at the plant to
guide the amount of needed chemicals, air inflow and
rotation. The aim is to ensure that the mineral yield in
the froth is at the expected level and that excess amounts
980
of this mineral are not forwarded to the next flotation
cycle or waste. The Pyhäsalmi beneficiation facility ana-
lyses the process efficiency constantly with online XRF
analysis and occasionally with offline AAS analysis for
the calibration of the XRF prediction models. The XRF
prediction can be used to analyse the cause of possible
insufficient separation. Problems in separation are usu-
ally caused by unliberated particles or poor mechanical,
reagent, or separator performance. At Pyhäsalmi, the
XRF estimation of chalcopyrite and sphalerite amounts is
direct, because the former contains all of the copper and
the latter contains all of the zinc. However, XRF estima-
tion of pyrite is only predictive due to the fact that iron is
present not only in pyrite, but also in chalcopyrite and, to
a lesser degree, the sphalerite and even one of the gangue
minerals (augite). Although periodical metallurgical AAS
analyses in laboratory offers more precise and reliable
results than predictive XRF, it cannot be used as an
online tool due to the time consumption and hands-on
process of the wet chemical analysis. RS, on the other
hand, is a valid choice for the detection of chalcopyrite,
sphalerite, and pyrite as in general the sulfide minerals
are Raman active and give characteristic spectra that can
be used for identification.[19] The aim of this study is to
determine, if the RS analysis could prove reliable mineral
quantification from liquid-immersed sulfide ore after
mineral enrichment cycles and thus in the future serve as
a tool for reaching better flotation process control in ben-
eficiation facilities.
2 | MATERIALS AND METHODS
2.1 | Mineral enrichment and online
XRF detection of enriched sulfide ore
elements
The Pyhäsalmi mineral beneficiation facility has 17 pro-
cess phases, which are analysed with an online XRF
detector (Courier 6 On-Stream XRF analyzer, Outotec,
Finland). The XRF analysis has several aims to support
the mining and mineral recovery. The first aim is to
support the ore quarry with mineral information of the
original ore and to ensure that the mineral levels are as
expected. The second aim is to detect the purity and
concentration level of the flotation froths and to ensure
that the sold mineral products meet the quality parame-
ters set by the buyers. The third aim is to analyse the
mineral tailings and final ore waste to ensure that con-
siderable amounts of valuable minerals do not end up
in the waste. Table S1 shows the analysed process
phases with description of the analysed froth samples.
The most important process samples are the sulfide ore,
UUSITALO ET AL.
the enriched mineral slurries, and their tailings. The
Pyhäsalmi beneficiation process flow from mining to
froth flotation and the order of the enrichment steps
during flotation are presented in Figure S2 . The domi-
nant ore minerals at Pyhäsalmi include pyrite, pyrrho-
tite, chalcopyrite, and sphalerite. Additionally, the ore
comprises small amounts of jordanite, bourgonite,
seligmannite, hessonite, fahlore, arsenic, wehrlite, and
molybdenite. The gangue includes quartz, barite, cal-
cite, dolomite, plagioclase, tourmaline, and talc among
other minerals with smaller quantities. The elemental
compositions of the original ore, froths and the tail
slurries can be found in Figure S3.
2.2 | Online Raman spectroscopy of
enriched sulfide ore minerals
2.2.1 | Instrumentation for online
Raman measurements with a custom
connector
In this study, a Raman spectrometer was connected to an
online XRF analyser input pipeline at a Pyhäsalmi mine
beneficiation plant with a custom designed probe connec-
tor. A depiction of the connector and the connected
Raman system are shown in Figure 1a–c. The Raman
measurements used an Immersion Optic probe designed
for reaction monitoring and a RamanRxn2™ Systems
Analyzer (Kaiser Optical Systems, Inc.) with excitation
laser wavelength of 785 nm. A near-IR wavelength was
chosen to reduce mineral fluorescence issues. Raman
spectra were recorded roughly with the same timing as
the XRF detection. The parameters for Raman spectrom-
eter were chosen to fit the automated sample intake and
washing steps of existing Courier XRF analyser. The pro-
cess froth samples were pumped into the XRF analyser in
a sequence, where sample cross-contamination was
prevented with a washing step between samples. Ana-
lyser was washed by pumping water through analyser
pipes. The XRF analyser is not recording data during
washing steps. However, because the Raman spectrome-
ter was not electrically triggered to the XRF recording,
Raman spectra were recorded also during the washing
steps. The approximate intake time for each froth sample
for the XRF analyser was 30 s with a short 20-s washing
step after each XRF sampling cycle. Because it was not
possible to synchronize the Raman signal recording with
the XRF analyser signal recording, the Raman signal was
collected continuously with 10-s integration time and 5-s
delay between recorded spectra to assure that one per-
fectly timed Raman spectra would be recorded for each
XRF input sample. The Raman system used maximum
UUSITALO ET AL.
F I G U R E 1 (a) Depiction of
the custom probe connector.
(b) Probe connector integrated to
the online X-ray fluorescence
(XRF) detector. (c) Picture of the
connected RamanRxn2™ system
to the Pyhäsalmi mine
beneficiation plant online
Courier XRF analyser [Colour
figure can be viewed at
wileyonlinelibrary.com]
excitation laser power of 400 mW. Although this is a high
laser power level for minerals, there was no laser-induced
heating and consequent modifications of the mineral
spectrums observed with the used power due to the liquid
immersion.[8] The collection optics had direct contact to
the ore slurry with 0-mm focal distance and 100-μm
beam diameter. Outlier spectrums were observed during
the measurements as the ore smudged the immersion
probe window occasionally for a short time period. In
constant online detection, it is however possible to dis-
card the outliers from the final analysis as the amount of
data is not dependent on single spectra.
2.2.2 | Sample intake for online Raman
measurements with custom connector
The intake of the XRF online analyser was directing sam-
ples of different froth phases and tailings to the analyser
in a customized sequence with emphasis on samples of
importance for the froth flotation process control. Thus,
the online XRF analyser analysed some ore slurry phases
several times and others more rarely, and during a 4-hr
online experiment, the amount of samples for process
phases differed as follows: chalcopyrite 41 samples, sphal-
erite 130 samples, and pyrite 31 samples. The mineral
levels of the XRF element data were calculated with cali-
bration formulas (1)–(4), which can be found in the
Supporting Information.
2.2.3 | MLA reference analysis of the ore
mineral samples
During the measurement campaign, the reference froth
samples were collected from the XRF analyser intake.
981
XRF analyser has an built-in valve system, which can be
used to collect samples on-demand for the calibration of
the XRF system. Samples were dried and sent to
ERZLABOR Advanced Solutions GmbH for reference
MLA analysis as compacted powder discs. The MLA
analysis gives reference information on the mineral levels
in different flotation samples. Figure S4 shows the min-
eral composition of the original ore, concentrate froths,
and their tailings obtained from the analysis. Although,
the flotation froths mainly consist of the enriched min-
erals (chalcopyrite 85, sphalerite 95 to pyrite 99 weight
percent [wt%] of the dried matter), chalcopyrite and
sphalerite froth do have small amounts of trace minerals
as well. Chalcopyrite has 7% pyrite, 2.2% pyrrhotite, and
2.5% sphalerite content. Sphalerite has 1.5% pyrrhotite
and 2% pyrite content. Pyrite froth contains mainly
pyrite, and even MLA cannot distinguish the remaining
1% content.
2.3 | Enriched mineral concentration
series and data analysis
2.3.1 | In situ sample collection
The sensitivity and accuracy of RS to detect the min-
erals of interest was studied by creating a concentra-
tion series for each enrichment mineral: chalcopyrite,
sphalerite, and pyrite. To form the concentration
series, several in situ samples were collected during
the measurement campaign at Pyhäsalmi. The in situ
samples included chalcopyrite froth (CuR1), chalcopy-
rite tailing (CuJ), sphalerite froth (ZnR), sphalerite tail-
ing (ZnJ), pyrite forth (SR1), and pyrite tailing (SJ).
Mineral concentration series were created to simulate
a situation, where the mineral levels of the process
982
samples have wider fluctuation range. During measure-
ment campaign, the froth flotation process at the
Pyhäsalmi mine beneficiation facility was stable, and it
was not possible to monitor large fluctuation ranges
online. In situ samples for laboratory measurements
were collected together with the reference samples,
which were sent to the MLA analysis. The reference
information was used to calculate the concentration
series.
2.3.2 | Mineral concentration trials in
laboratory
The sensitivity and accuracy of RS to detect the minerals
of interest was studied by creating the concentration
series for each enrichment mineral: chalcopyrite, sphaler-
ite, and pyrite. The concentration series were formulated
by mixing the dry matter of enriched mineral to 0.5 dl of
respective mineral tailing immersed in water. The min-
erals were mixed into their tailing to simulate the min-
eral variance in the original ore gangue rather than
mixing them into pure water. This ensured that the cre-
ated samples had the effect of gangue minerals present
and the solid content was more realistic than what a
water–mineral enrichment mixture would have had. The
enriched mineral dry matter was separated from water
with Buchner filtration. The mineral froths were first fil-
tered and then diluted to their equivalent tailings. The
concentration series had enrichment mass ratios of
10, 5, 1, 0.5, and 0.1%. Although the minerals were mixed
into their tailings, the original solid content of the sam-
ples did differ slightly from the original ore content, and
the concentration series can only indicate the ability of
the RS to gain quantitative information on the mineral
ratios.
2.3.3 | Raman measurements of mineral
concentration series
The laboratory study was executed with the same immer-
sion probe and Raman device as used in the online detec-
tion study at Pyhäsalmi. The Raman signal integration
time was set to 10 s, and the laser power was 400 mW.
The sample slurry was constantly mixed with a mechani-
cal rotator to prevent the gravitational sedimentation of
the enriched ore and tailing dry matter to the bottom of
the sample container. The immersion probe was fixed in
the near vicinity of the rotator. The test series consisted
of two concentration series for each mineral (total
10 samples/mineral). The concentration series were mea-
sured three times.
UUSITALO ET AL.
2.3.4 | Data analysis from RS spectra
The raw RS data had an elevated background both in the
online trial and in the laboratory trial. This elevation is
related to disturbing factors such as mineral fluorescence
created by the laser excitation. In this study, the signal
background was subtracted using baseline correction
method based on asymmetric least squares (baseline)
smoothing. The two parameters, which distinguish the
shape of the background envelope, are p for asymmetry
and λ for smoothness.[20,21] For the spectral data of this
trial, the parameters were set to be p = 0.0001 and
λ = 30000. Figure S5 presents an example of Raman spec-
trum of chalcopyrite froth and asymmetric least squares
baseline-corrected spectrum.
The spectral Raman data was transformed into signal
intensity information by utilizing area-to-area integration
with linear fit. Because the sulfide ore did not have con-
sistent peaks originating from side rock minerals, the
mineral signal was proportioned to the immersion probe
sapphire window peak. Additionally, the superimposition
of adjacent mineral peaks in case of chalcopyrite and
sphalerite was analysed with a Voigt function. It has been
shown previously that collision broadening of Raman
peaks results in a peak shape that is a combination of
both Lorentz and Gauss forms.[22,23] The Voigt function
combines the Lorentz and Gauss forms in adjustable pro-
portions. The MATLAB software environment
(MathWorks, USA) was used for this Voigt modelling of
overlapping chalcopyrite and sphalerite peaks. Because it
was not practical to perform this Voigt modelling for
every Raman spectrum produced in the inline test and in
the laboratory study, the Voigt modelling was used to
identify a shoulder region of the chalcopyrite peak that is
largely unaffected by the sphalerite peak and vice versa
for the purposes of routine mineral-proportion
estimation.
3 | RESULTS
3.1 | Laboratory analysis of in situ
samples
The Raman peaks detected from the original sulfide ore
are presented in Figure 2. Using the reference spectra
downloaded from the RRUFF database, Raman peaks
from different minerals were identified to be chalcopy-
rite, sphalerite, pyrite, augite, and barite. Table 1 shows
the minerals with detected Raman peaks and the relation
of peak intensities of single mineral peaks for each min-
eral. In addition, the sulfide ore spectrum includes three
peaks, which do not originate from the mineral
UUSITALO ET AL. 983

F I G U R E 3 The average Raman spectra of chalcopyrite froth,

F I G U R E 2 Original sulfide ore Raman spectrum with chalcopyrite tailing, sphalerite froth, sphalerite tailing, and pyrite
subtracted background. The main Raman peaks and their mineral froth calculated from 150 spectra recorded during laboratory trial
associations have been indicated with numbers [Colour figure can [Colour figure can be viewed at wileyonlinelibrary.com]
be viewed at wileyonlinelibrary.com]
The average spectra of the froths are presented in Figure 3.
Because the chalcopyrite and sphalerite have partly over-
T A B L E 1 Normalized Raman peak intensities calculated from
lapping dominant peaks 291 and 299 cm−1, the effect of
the reference spectra acquired from RRUFF database and from the
recorded ore froth spectra. The dominant Raman peaks have been
sphalerite peak has to be taken into account in
indicated with bold text chalcopyrite analysis. The superimposition of the sphaler-
ite and chalcopyrite peak was analysed by adjusting the
Normalized chalcopyrite spectrum to Voigt fit by utilizing the refer-
Normalized peak
ence spectra from RRUFF database. The analysis of the
peak intensity
intensity from
spectra superimposition is presented in Figure 4. This peak
Raman shift from detected overlapping affects signal quantification. Additionally, the
Mineral (cm−1) reference spectra main 338 cm−1 peak from pyrite has fluctuation not seen
Chalcopyrite 291 1 1
with the lower peak 374 cm−1. This could be related to
gangue mineral peaks such as augite and calcite. Gangue
Sphalerite 299 0.76 1
mineral peaks are listed in Table S2 . Other gangue min-
Pyrite 338 1 1 erals such as pyrrhotite, which is present in chalcopyrite
Pyrite 374 0.4 0.32 and sphalerite froth, can have low mineral peaks in the
Pyrite 797 0.05 0.06 spectra, but their peak wavenumbers are not disturbing
Pyrite 860 0.06 0.06 the enriched mineral Raman peak analysis.
Barite 987 1 1 The Raman mineral peaks selected for the signal
analysis were the left slope of 291 cm−1 for chalcopyrite,
Augite 1012 1 1
the right slope of 299 cm−1 for sphalerite, and 374 cm−1
Sapphire 417 1 1
for pyrite. The exact Raman peak areas used in the calcu-
Sapphire 430 0.11 0.14 lations of Raman signal intensity are shown in Figure S6.
Sapphire 448 0.03 0.12 The relation between signal intensity and mineral con-
Sapphire 576 0.07 0.26 centration in ore was studied with sample series utilizing
Sapphire 750 0.13 0.58 the in situ collected froths. In the trial, dried minerals
froth powders were mixed into their tailings to create
concentration series. It would have been possible to mix
components. These peaks originate from the sapphire the froth powders into water, but that would have been a
probe window. There are also peaks originating from the simplified simulation as the liquid immersion consistency
gangue minerals augite and barite. The rest of the peaks would have been very different with the strongest and
belong to sulfide minerals. the lowest sample concentration. The tailings of the flota-
The Raman spectra of in situ collected froth flotation tion cycles include the same gangue minerals present in
samples were studied in a laboratory to analyse the effect the original ores. The aim was to simulate the presence
of different mineral levels to their Raman peak intensities. of enriched minerals in the presence of gangue minerals
984
to simulate a situation where the enriched mineral con-
tent was low in the original ore before flotation with
changing amounts of minerals of interest, namely chalco-
pyrite, sphalerite and pyrite.
To exclude the effect of background signal coming
from water or flotation chemicals to the mineral spectra,
the Raman signal of water, Dowfroth, zinc sulfide, and
xanthate were recorded. According to the results shown
in Figure S7 , the zinc sulfide and xanthate do have
Raman peaks, but the location of the peaks does not
interfere with the froth mineral analysis. A water spec-
trum shows only the Raman probe sapphire window
peaks.
As discussed in Section 2, after background removal,
the quantification of the Raman response requires a tran-
sition of spectral data into an accountable value. In this
study, the possible variance in the optical path of the
laser beam was removed using intensity ratio between
mineral and background peak, in this case sapphire
window peak. The variance in optical path length was
compensated as the Raman signal can change due to
momentary sample consistency change between sam-
pling cycles. In addition, signal intensity fluctuations can
happen if there are changes in brightness of the excita-
tion laser and efficiency of light collection.[24]
F I G U R E 5 The average Raman signal response in function of mineral concentration for (a) chalcopyrite, (b) sphalerite, and (c) pyrite
with standard error [Colour figure can be viewed at wileyonlinelibrary.com]
UUSITALO ET AL.
F I G U R E 4 Voigt fit to the chalcopyrite
spectrum. The effect of sphalerite peak broadens
the chalcopyrite peak and shifts the
superimposed peak position to 295 cm−1. The
fitting can be applied, when the peaks and
mineral ratios distinguish from each other. If the
peak heights are similar, it is more difficult to
calculate the superposition [Colour figure can be
viewed at wileyonlinelibrary.com]
The enriched mineral concentration series were
used for the validation of linearity of the Raman signal
response to the actual mineral levels in the sulfide
slurry samples. The linearity was studied using the con-
centration series with enriched mineral content in w-%
ratios of 0.1, 0.5, 1, 5, and 10%. Results for the average
Raman signals of enriched mineral concentration series
are presented in Figure 5. The slope of the fitted linear
functions for chalcopyrite, sphalerite, and pyrite was
used to assess the current limit of detection, which was
1.5, 0.5, and 30% respectively.[25] The pyrite shows
unacceptably high variation and limit of detection even
for semiquantitative analysis. Pyrite slurry consists of
particles with larger average size than chalcopyrite and
sphalerite slurries have. As can be seen in Figure S8,
pyrite has more particles with diameter exceeding
40 μm. According to literature, the intensity of Raman
scattering can be highly dependent on particle distribu-
tion of the sample as has been shown in studies focus-
ing on pharmaceutical research.[26] Thus, the pyrite
particles are more affected by the external forces, and
the Raman signal of pyrite has larger fluctuations than
the other enriched minerals during the trial. Similar
behaviour of signal fluctuation can be observed with
online RS analysis of pyrite recorded at Pyhäsalmi
UUSITALO ET AL. 985

mine. However, the relation between concentration and
Raman signal of chalcopyrite and sphalerite in Figure 5
show that it is possible to detect minerals in sulfide ore
slurries with an average linear behaviour as long as the
average particle size is in the range of 30 μm. It seems
that for successful mineralogical analysis, the particles
of the mineral slurry need to be finely grinded to be
reliably analysed by RS. In addition, the RS analysis
should consist of numerous Raman spectra with longer
integration time in order to be able to discard occa-
sional outliers, see Figure S9, and average out Raman
peak areas for more statistically reliable data analysis.
3.2 | The online trial at Pyhäsalmi
beneficiation facility
The online Raman data measured at Pyhäsalmi mine
beneficiation facility was consistent with the spectra
acquired during the laboratory trials. For the first time,
the mineral levels of sulfide ore were recorded in an
online arrangement in a beneficiation facility. The
recorded RS data was synchronized with the simulta-
neously recorded XRF data to see the correlation of the
Raman peaks and the detected material elements. The
results are shown in Figure 6a for chalcopyrite (Raman)

F I G U R E 6 (a) Comparison of
online-detected chalcopyrite Raman
signal level to the detected X-ray
fluorescence (XRF) copper weight
percent (wt%) signal level.
(b) Comparison of online detected
sphalerite Raman signal level to the
detected XRF zinc wt% signal level.
(c) Comparison of online detected pyrite
Raman signal level to the calculated
XRF pyrite wt% signal level [Colour
figure can be viewed at
wileyonlinelibrary.com]
986
and copper (XRF) levels in ore slurry samples, in
Figure 6b for sphalerite (Raman) and zinc (XRF) levels,
and in Figure 7c for pyrite Raman intensity and XRF esti-
mation. The graphs show similar signal indications for
the same time stamps for both Raman and XRF data.
However, it can be seen that the changes in signal height
are more prominent with Raman intensity than with
XRF estimation. In addition, the noise level fluctuations
are stronger. This could be related to several things
including the changes in solid–liquid content or particle
size distributions and the partial overlapping of the chal-
copyrite and sphalerite peak.
4 | DISCUSSION
4.1 | Raman analysis of sulfide minerals
RS has been shown to be a suitable detection method
for qualitative identification of different minerals.[27]
Although sulfides such as chalcopyrite, sphalerite, and
pyrite are Raman active, they are not as strong scat-
terers as carbonate and sulfate minerals.[28] However,
this is not necessarily a restriction in mineral beneficia-
tion analysis as the mineral levels in the froths are
high, and it is possible to use high power lasers,
because the samples are a mixture of solids and water.
It should be noted that the detected mineral Raman
spectra can be dependent on the used excitation wave-
length. The colour of minerals and the effect of Raman
resonance condition can affect Raman scattering.[29,30]
As mentioned in the Section 2, this study utilized
Raman excitation wavelength of 785 nm, which is off-
resonance for sulfide mineral analysis. In this study, the
recorded mineral spectra were compared with the spec-
tra presented in RRUFF reference database using
corresponding unpolarized 785-nm laser excitation.
Thus, the peak placement and identification is based on
similar Raman conditions with both the reference spec-
tra and the detected spectra. In reference database,
sphalerite shows a wide Raman peak triplet at 299,
320, and 350 cm−1 although the detected spectra show
only one narrow peak at 299 cm−1. This could be
related to the variable composition of sphalerite (Zn,Fe)
S), which can have a zinc-replacing element in its struc-
ture, namely iron (Fe). The spectra of chalcopyrite
(CuFeS2) and pyrite (FeS2) are more in line with the
database spectra. Chalcopyrite has one main Raman
band at 290 cm−1, and pyrite has two dominant Raman
bands at 338 and 374 cm−1.[28] The RRUFF reference
spectra and their main Raman bands are presented in
Figure S10 . The associated molecular Raman band
assignments for each ore originating peak can be found
UUSITALO ET AL.
in Table S3 with molecule space groups and mineral
formula information.
4.2 | Need for accurate mineral analysis
at beneficiation facilities
The process control of Pyhäsalmi mine flotation uses a
calibrated online XRF analyser, to estimate the mineral
quantities of the sulfide slurries in a stable process situa-
tion, where the quarried ore consistency stays within the
boundaries of the XRF calibration. The XRF information
is used to control the froth flotation process. The process
control has a need for real time information on the stabil-
ity of the mineral collection and the consistency of differ-
ent process phases. The quarried ore can have different
mineral consistencies depending on the location of the
mining. Although froth flotation may sound like a simple
process with three main phases: manipulation of hydro-
phobicity, air bubble bonding of minerals and froth col-
lection, and recovery of hydrophilic gangue minerals
from tank bottom, in reality there are over 100 variables
that affect the flotation process. This is due to the subpro-
cesses such as entrainment of gangue into the froth
phase, coalescence of bubbles, deattachment of mineral
particles from bubbles, feed composition, and grinding
stages prior to flotation.[31] The beneficiation process at
Pyhäsalmi mine is quite stable in regards to the mineral
consistency of the ore. Thus, the current consistency of
froths stays inside the calibration boundaries of the XRF
analyser. This is a requirement for the online XRF ana-
lyser to give reliable results as an outcome of the elemen-
tal analysis, because the mineral estimation is a result of
mineral calibration with AAS. However, the ore situation
is not always stable in mines not even at Pyhäsalmi.
Changes in the ore consistency affect the calibration, and
finding the right algorithms for the new XRF calibration
is both time consuming and laborious. In many cases,
there is a need for an analyser, which could detect the
mineral levels instead of the elements. For mining com-
panies, the information would give input on the actual
products they sell, the quarry gravel, which has certain
mineral concentration limits it has to meet in order to be
graded as a good quality product and reach the best price
class. Mines also need to know if their product includes
trace minerals, which are listed as harmful and can cause
price penalties, when selling the product to the customer.
In an ideal case, the mine can react to unwanted changes
in flotation process and make sure that second class prod-
ucts are not produced, when they have reliable online
data on the mineral consistency of each flotation cycle.
The results of this study indicate that RS could be a
future tool for online mineral analysis of sulfide ore as
UUSITALO ET AL.
the detection of chalcopyrite, sphalerite, and pyrite is fea-
sible. RS could simplify the online analysis for mineral
quantification, as there would be no need for estimation
of different element distributions between minerals. The
uncertainties of mineral consistency would decrease in
situations, where the flotation process is not in a stable
state due to the change in the ore consistency.
4.3 | Online Raman spectroscopic
analysis
In this study, it was shown that the RS can detect the sul-
fide mineral levels as an online tool at a beneficiation
facility. Although the RS analysis gave mineral level indi-
cation with semiquantitative accuracy, it is possible in
future to optimize the online mineral detection. An
important observation was that the particle size distribu-
tion of the minerals affects the results both in laboratory
trials and during the online measurements. Additionally,
differences in solid–liquid content of the samples can
affect the Raman results. This has been previously dis-
cussed in studies concentrating on pharmaceutical analy-
sis using RS.[26] Another method for signal optimisation
could utilize a larger Raman beam in comparison with
particle size and increased integration times. The estima-
tion for optimal Raman beam diameter should consider
the effect of moving particles and light scattering from
small particles to the final Raman beam diameter. Finally,
the Raman analysis could utilize more accurate estimation
of overlapping mineral peaks with the Voigt function to
break down the recorded Raman spectra into different
mineral peaks. Such data analysis requires a classification
algorithm to assign the Raman peaks for appropriate
minerals. The fluctuations of signal levels seen during a
stable froth flotation process at Pyhäsalmi suggest that RS
analysis might need supporting information in order to
quantify the mineral levels precisely. One option would be
to create a sensor fusion utilizing both the XRF analysis
and RS. The evaluation of the Raman performance and
the need for supporting analyses to compensate for
variance in particle distribution would require long-term
online RS signal recording with continuous feedback from
XRF and AAS analysis for mineral levels and especially for
particle size fluctuations. As a summary, the RS could be a
valuable tool for the online mineralogical analysis in the
flotation process control, if the future optimisation of the
RS analysis online would solve the issues rising from
larger particle distributions and changes in solid content
of froths. The future research will reveal the final reliabil-
ity, repeatability, stability, limit of detection, and the effect
of mineral cross correlation to the Raman spectroscopic
online mineral analysis.
987
5 | CONCLUSIONS
This study used RS for online characterization of
volcanogenic massive sulfide ferrous iron ores containing
sulfide minerals at the Pyhäsalmi mine with the custom
probe connector. According to the results, RS is a suitable
online tool for the rapid identification of enriched sulfide
minerals from different flotation process phases. Compar-
ison of the online Raman and XRF data showed that RS
is a feasible analysis tool for mineral level indication from
finely grinded liquid-immersed sulfide minerals con-
taining light-weighted or common elements. The labora-
tory trials with in situ samples of chalcopyrite and
sphalerite showed linear relation between Raman signal
intensity and mineral concentration. Moreover, Raman
analysis clearly identifies different mineral spectra pro-
duced by three flotation phases: chalcopyrite, sphalerite
and pyrite.
ACKNOWLEDGEMENTS
This project has received funding from Finnish govern-
ment through VTT-funded CALMIN-project and from
the European Union's Horizon 2020 Research and
Innovation Programme under grant agreement No
680565. The work is also part of the Academy of Finland
Flagship Programme, Photonics Research and Innovation
(PREIN), decision 320168. Business Finland has
supported this publication during APASSI project.
ORCID
Sanna Uusitalo https://orcid.org/0000-0001-7224-1557
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SU PP O R TI N G I N F O RMA TI O N
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
How to cite this article: Uusitalo S,
Soudunsaari T, Sumen J, et al. Online analysis of
minerals from sulfide ore using near-infrared
Raman spectroscopy. J Raman Spectrosc. 2020;51:
978–988. https://doi.org/10.1002/jrs.5859