DISSOLUTION MADE EASY USING

PEROXIDE FUSIONS FOR ICP-OES

ANALYSES FOR CHROMITE ORES,
FERROCHROMES AND CHROMIUM
SLAGS
ICP-OES application

Introduction
Although there are more than ten known chromium minerals, only one is a source of commercial importance. This mineral is
known as chromite and has the theoretical composition FeCr2O4 containing 68 % of chromic oxide (Cr2O3), in which the
proportions of Mg2+, Fe2+ and Cr3+, Al3+, Fe3+ may vary considerably[1].

The main product generated by chromite is ferrochrome, a major player in the steel industry[2]. In particular the stainless
steel industry uses more than 90 % of the world’s chromite output. The mining and steel industries must assess the quality of
the chromite ore to optimize the grade of their stainless steel production. As a result, the chemical analyses of the chromite
ore as well as its final and waste products are mandatory. Metal analysis traditionally uses AA or ICP-OES to measure the
metal contents in the ores and industrial products. However, the traditional dissolution method for chromite and ferrochrome
is a multi-step, multi-acid digestion which requires the use of HNO3, HF and HClO4 and can take between 1 to 3 hours[3,4].

Knowing the risks associated with the use of HF and HClO4, many laboratories look for alternative methods to obtain full
dissolution of their samples while optimizing their uptime and productivity. As will be demonstrated, sodium peroxide fusions
are a quick, safe and efficient alternative for the dissolution of these specific samples.

Experimental

Sample preparation
Peroxide fusions can be performed either manually or with automated systems. Although both methods are efficient, the
automated systems have the advantage of increasing productivity, improving safety, maintaining repeatable preparation
conditions, avoiding spattering as well as cross-contamination. In this project, fusions were performed using a Claisse®
Peroxide™ Fluxer (Figure 1).

The Claisse® Peroxide™ Fluxer is a 6 position gas Fluxer specifically designed to do multiple and repetitive peroxide fusions
with excellent repeatability and reproducibility. It’s special design and finish makes it optimal to endure repetitive exposure to
the aggressive environment generated by peroxide fusions. Combined with the specially designed high-stability burners,
the Peroxide™ fluxer offers stable temperature allowing for controlled fusions.

Different samples and reference materials were used to validate the developed method (Table 1).
Table 1. List of Reference Materials and Samples Used to Validate the Developed Method

Sample Supplier

Certified Reference Material - FeCr (SRM 64c) NIST

Certified Reference Material - Chromite ore (SARM 8) Mintek

Certified Reference Material - FeCr slag (SARM 77) Mintek

FeCr sample Mining industry

Chromite ore sample Mining industry

FeCr slag sample Stainless steel industry

In a zirconium crucible, 0,2 g of finely ground sample at less than 100 μm was mixed with 0.5 g of Sodium Carbonate
(Na2CO3) and 3,0 g of Sodium peroxide (Na2O2). The crucible containing the mixture was placed on the Claisse®
Peroxide™ Fluxer, fused at 560ºC for 3,5 minutes, then cooled by the fluxer fans for 4 minutes.

The cooled zirconium crucible was then placed in a funnel over a 250 mL volumetric flask. Around 10 mL of warm (70ºC)
ultra-filtered deionized water is added to the crucible followed by 25 mL of HNO3. The dissolution reaction takes less than a
minute after which time the crucible is tipped over and rinsed out with deionized ultra-filtered water. 25 mL of HCl is then
added in the flask, then brought up to volume with diluted acid, and brought to the ICP-OES for analysis.

Instrumentation
The measurements were performed using the PerkinElmer® Optima™ 7300 DV ICP-OES instrument (Figure 2). It is
equipped with the WinLab32™ for ICP Version 4,0 software. On this particular instrument, the ICP torch is mounted in a
horizontal orientation in the instrument’s shielded torch box, but can be viewed either axially or radially.

A Scott Spray Chamber with a Gem Tip Cross Flow Nebulizer (Figure 3) was selected as an introduction system because of
its proven reliability, robustness and capability to handle high dissolved solids. The viewing mode is user-selectable on an
element-by-element basis. A shear gas flow (compressed air) eliminates the cool plasma tail and allows a direct observation
of the plasma’s normal analytical zone, thus minimizing chemical matrix effects when the axial-view mode is employed.

Figure 2. PerkinElmer® Optima™ 7300 DV ICP-OES

Figure 3. Scott Spray Chamber with Gem Tip Cross Flow Nebulizer
By combining a SCD detector and an Echelle optical system, the Optima™ 7300 DV ICP-OES can measure all the
wavelengths simultaneously. Its wavelength flexibility allows the end users to easily add new elements or wavelengths as
their program changes. Another benefit of using the Optima for fusion samples includes a 40 MHz free-running solid state RF
generator designed to operate between 750 to 1500 W in 1 W increments. High RF power is required to generate a robust
plasma, essential for precise analysis of high matrix samples such as fusion samples[4] (refer to Table 2 for detailed
Optima™ 7300 DV operating parameters).

Table 2. Optima™ 7300 DV operating parameters

Nebulizer Gem Tip Cross flow

Spray chamber Scott

Injector Alumina

RF 1500 W

Plasma: 16.0 L/min

Argon Flow rate Nebulizer: 0.8 L/min
Auxiliary: 0.4L/min

Shear gas 100 psi

Sample flow rate 1.0 mL/min

Results and discussion

The following criteria were taken into consideration in selecting the wavelength: (a) the freedom from spectral interferences;
(b) the different sensitivities and expected concentration in the samples. The most sensitive line was not always used in
order to avoid spectral interferences and to remain in the linear range. Observed interferences were compensated for by
modifying the processing parameters (e.g. adjusting the background correction points, applying multi-component spectral
fittings (MSF) or inter-elemental corrections (IEC)).

Method detection limits (MDLs) were based on ten replicate measurements of a series of low concentration or diluted sample
solutions. The MDL was calculated by multiplying the standard deviation of the ten replicate measurements by 3[5]:

MDL = 3 x S10 x CDF

Where: S10 = Std Deviation of the ten replicates

CDF = Corrected Dilution Factor

Table 3 demonstrates analytes of interest with selected wavelengths, viewing modes and method detection limits (MDL).
Table 3. Analytes of interest with selected wavelengths, method detection limits (MDL) and viewing modes

Element Wavelength Viewing mode MDL (mg/Kg)

Al 394,401 Axial 63

Ca 315,887 Axial 1000

Co 228,616 Axial 38

Cr 283,563 Radial 250

Cu 224,700 Axial 25

Fe 238,204 Radial 375

Mg 279,077 Radial 63

Mn 257,610 Radial 25

Ni 231,604 Axial 125

P 178,221 Axial 125

S 180,669 Axial 625

Si 212,412 Radial 63

Ti 334,940 Axial 63

V 290,880 Axial 5

The accuracy and precision of the method was evaluated. The accuracy were determined by calculating the elemental
recovery of certified reference materials (CRMs). The precision was determined by preparing and measuring 10 replicates of
the various CRMs. The results for each CRM are presented in Tables 4, 5 and 6. The accuracy and precision obtained
demonstrates that the developed method performed very well.
Table 4. Accuracy and precision measurements on NIST SRM 64c

Average Experimental values (%) Certified values Accuracy Precision

Element Wavelength
n=10 (%) (%) (%)

Al 394,401 BDL - - -

Ca 315,887 BDL - - -

Co 228,616 0,05 0,05 107 2

Cr 283,563 69,03 68,0 102 23

Cu 224,700 BQL 0,005 (60) (15)

Fe 238,204 25,87 24,98 104 3

Mg 279,077 BDL - - -

Mn 257,610 0,16 0,16 101 2

Ni 231,604 0,43 0,43 100 2

P 178,221 BQL 0,02 (86) (7)

S 180,669 BDL 0,07 - -

Si 212,412 1,28 1,22 105 3

Ti 334,940 BQL 0,02 (63) (5)

V 290,880 0,15 0,15 102 2

In parenthesis and italic = informative values BDL = below detection limit

Corrected dilution factor = 1250 BQL = below quantification limit
Table 5. Accuracy and precision measurements on Mintek SARM 8

Average Experimental values (%) Certified values Accuracy Precision

Element Wavelength
n=10 (%) (%) (%)

Al 394,401 5,81 5,56 105 2

Ca 315,887 BQL 0,19 (90) (18)

Co 228,616 0,03 - - 4

Cr 283,563 35,50 33,5 106 2

Cu 224,700 BDL - - -

Fe 238,204 15,20 14,13 108 2

Mg 279,077 8,98 8,86 101 2

Mn 257,610 0,21 - - 2

Ni 231,604 0,15 - - 3

P 178,221 BDL 0,004 - -

S 180,669 BDL 0,03 - -

Si 212,412 2,12 2,01 106 2

Ti 334,940 0,14 0,14 95 2

V 290,880 0,07 0,08 90 2

In parenthesis and italic = informative values BDL = below detection limit

Corrected dilution factor = 1250 BQL = below quantification limit
Table 6. Accuracy and precision measurements on Mintek SARM77

Average Experimental values (%) Certified values Accuracy Precision

Element Wavelength
n=1 (%) (%) (%)

Al 394,401 15,34 14,55 105 5

Ca 315,887 2,48 2,60 95 2

Co 228,616 BQL - - (8)

Cr 283,563 9,39 8,55 110 3

Cu 224,700 BDL - - -

Fe 238,204 5,98 5,31 113 4

Mg 279,077 13,94 13,86 101 2

Mn 257,610 0,16 - - 2

Ni 231,604 BQL - - (7)

P 178,221 BDL - - -

S 180,669 0,17 (0.32) (54) 5

Si 212,412 12,81 12,5 102 2

Ti 334,940 0,36 - - 1

V 290,880 0,06 - - 2

In parenthesis and italic = informative values BDL = below detection limit

Corrected dilution factor = 1250 BQL = below quantification limit
Table 7. Recovery results on pre-fusion spikes ( n = 5 )

Element Wavelength #771 (%) #775 (%) #784 (%) SRM 64c (%) SARM 8 (%) SARM 77 (%)

Al 394,401 101 96 109 101 99 92

Ca 315,887 96 109 99 114 97 112

Co 228,616 103 101 99 98 102 100

Cr 283,563 107 105 107 107 108 103

Cu 224,700 99 89 94 99 101 98

Fe 238,204 110 107 108 107 103 101

Mg 279,077 102 97 94 91 94 93

Mn 257,610 105 104 108 105 107 110

Ni 231,604 109 112 110 96 102 100

P 178,221 114 57 113 96 84 106

S 180,669 97 95 107 110 66 86

Si 212,412 102 53 106 91 105 91

Ti 334,940 107 105 106 105 103 102

V 290,880 105 105 105 99 103 97

Comments:
• Spike concentration = 50 to 100 % more than the concentrations in the samples and CRM solutions (Corrected dilution
factor: 2500).
• If concentrations < MDL, addition of ±10 times the MDL value.

Conclusion
Peroxide fusions combined with the simultaneous ICP-OES (Optima™ 7300 DV) have the analytical capabilities to
perform the analysis of chromite ore, ferrochrome and chromium slag samples with good accuracy, precision and speed of
analysis. The analytical method developed was robust and fulfills the requirements normally set for the analysis of high
matrix samples such as fusion samples. Metal components were measured at low and high concentrations in a variety of
samples and reference materials, demonstrating good accuracy. The sodium peroxide fusion approach to dissolution of
chromite ore, ferrochrome and chromium slag samples is an excellent alternative to other harsh, incomplete and time
consuming acid digestions.
References
1. http://minerals.usgs.gov/minerals/pubs/commodity/chromium/chrommcs06.pdf, Papp, John F. 'Mineral Commodity
Summary 2006: Chromium'. United States Geological Survey.
2. Determination of major and minor elements in ferroalloys by inductively coupled plasma atomic emission spectrometry, J.
Anal. At. Spectrom., 1988, 3, 1101-1103 Authors: M. Vaamonde, R. M. Alonso, J. García and J. Izaga
3. Analysis of Ferroalloys by Atomic Absorption Spectrometry, Applied Spectroscopy, Vol. 24, Issue 6, pp. 576-579
(1970) Authors: D. C. Smith, J. R. Johnson and G. C. Soth
4. Trace Metal Characterization of Soils using the Optima 7300DV ICP-OES, PerkinElmer® Inc., Application Note, Author:
Praveen Sarojam, PhD.

of this information and we shall not be liable for errors contained herein or for damages in connection with the use of this material. Malvern Panalytical reserves the right to change the content in this material at any time without notice.
5. Protocole pour la validation d'une méthode d'analyse en chimie, Centre d'Expertise en Analyse Environnementale du

Disclaimer: Although diligent care has been used to ensure that the information in this material is accurate, nothing herein can be construed to imply any representation or warranty as to the accuracy, correctness or completeness
Québec, Ministère de l'Environnement, Document de référence DR-12-VMC, Édition courante, 21 pages.
.

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