Determination of majors in geological samples ICP-12

July 1993
by ICP-AES

Paul A Liberatore
Varian Australia Pty Ltd
Mulgrave, Victoria, Australia

Introduction
The classical analysis of silicate rocks for the major Reagent preparation4
element constituents requires the determination of Anhydrous lithium carbonate (73.89 g) and boric
Al2O3, CaO, Fe2O3, K2O, MgO, MnO, Na2O, P2O5, acid (122.6 g) were well mixed in a porcelain dish
SiO2 and TiO2. These have traditionally been deter- and slowly heated for four hours in a muffle furnace
mined and expressed as the oxides1. at 400C. This produced a compound which was
The fusion method is applicable for the decomposi- predominantly lithium metaborate LiBO2.
tion of geological samples2,3 and for their subsequent The fused mass was ground to pass a BSS 250
analysis by ICP-AES. Lithium tetraborate or lithium mesh sieve. Lithium metaborate and lithium
metaborate is used to decompose the samples. tetraborate were mixed in a 1:1 ratio to produce the
Lithium metaborate is a better flux for highly sili- borate flux.
ceous ores and lithium tetraborate better for high
iron containing ores. The fused bead is dissolved in All reagents used were Analytical Reagent Grade.
10% nitric acid and the resultant solution analyzed Sample preparation4,5
directly.
The samples (0.5000 g) were mixed with 2.5 g of the
Experimental previously prepared borate flux in a 30 mL platinum
crucible and fused in a muffle furnace at 1000C for
Instrumentation 3045 minutes. The crucibles were removed from
A Varian Liberty Vacuum 200 Inductively Coupled the muffle furnace and the contents were carefully
Plasma Atomic Emission Spectrometer was used for swirled. If the fusion was incomplete the crucible
all measurements. The inert V groove nebulizer was returned to the muffle furnace for a further 10
was chosen because of the corrosive matrix. The minutes. When the fusion was complete the crucible
operating parameters are listed in table 1. The was removed from the furnace and allowed to cool.
instrument was controlled by an Epson EL 2 PC. The crucible was placed in a tall 150 mL beaker. A
Teflon coated stirring bar was placed in the crucible
Nebulizer and 125 mL of 1.6 M nitric acid solution was added.
Type V-groove The beaker was placed on a hotplate stirrer, heated
Pressure 195 kPa to 4060C with vigorous stirring until complete
Plasma power 1.0 kW dissolution was obtained.
Torch Demountable with alumina injector Precautions4 required during this procedure are:-
Argon flow rate
Plasma 15.0 L/min (i) The melt should be clear and not have any dark
Auxiliary 1.5 L/min spots of sample or any floating material other-
Pump rate 15 rpm wise the process should be repeated.
Integration time 3s (ii) The melt and the acid must be at ambient
Replicates 3 temperature before commencing the dissolution
Viewing height Optimized on SBR process or the silica in the sample may form
PMT voltage 650 V polymeric hydrated silicic acid.
Grating order Default
Filter position Default (iii) Excessive heating of the solution may also
Background correction Dynamic cause the same polymerization to occur.
Snout purge High (iv) If constant stirring is not maintained some of
the rock constituents may precipitate from
Table 1: Instrument Operating Conditions solution.

1
When dissolution was complete, the solutions were Ca 317.933 nm The two primary Ca lines are too
quantitatively transferred to 250 mL standard flasks sensitive for the levels of Ca
and made to volume with distilled/deionized water. found in the fusion samples.
The solutions were transferred to screwtop plastic There is a weak Fe line which
bottles until required for analysis. directly overlaps, however the
concentration of the Fe is not
Reference Rock samples high enough to cause an interfer-
Five U.S. Geological Survey Rock Standards were ence.
used. Fe 238.204 nm The structured background due
G-2, SY-2, BCR-1 and PCC-1 were presented as to NO band emission can be
unknowns. reduced by using a lower viewing
height or by using a higher
SY-3 was used as the standard for calibration plasma auxiliary flow.
purposes for this study.
K 769.869 nm This line was chosen to avoid a
Standard preparation Mg interference found with the
SY-3 was prepared according to the sample prepa- 766.490 nm K line.
ration procedure described and was used as the Mg 279.079 nm This line was chosen because it
working standard. The concentrations used for has sufficient signal while having
calibration were those values ascribed to the rock minimum interferences from
sample as shown in table 2. other elements. The only docu-
A blank solution was prepared by performing the mented interference is Mn. For
sample preparation without any sample present. the Mg/Mn ratios found in these
fusion samples the effect is
Standard SY-3 minimal.
Mn 257.610 nm This primary line has minimum
Standard values used Uncertainty interferences from other ele-
(wt%) (wt%) ments. High Al concentrations
will cause an elevated back-
ground which can be corrected
Al2O3 11.76 0.30
using Dynamic background
CaO 8.25 0.18
correction. The Fe line directly
Fe2O3 6.49 0.16
overlaps on the Mn line. For very
K2O 4.23 0.12
high Fe to Mn ratios this will
MgO 2.67 0.13
become significant. However for
MnO 0.32 0.02
these fusion samples the effect is
Na2O 4.12 0.15
minimal.
P2O5 0.54 0.03
SiO2 59.68 0.41 Na 588.995 nm This line was chosen because it
TiO2 0.15 0.02 has the maximum sensitivity
while having the minimum
TOTAL 98.21 1.87
interferences from other ele-
ments. The wing of the nearby Ar
Table 2: Standard values used for calibration lines causes a sloping back-
ground which can be minimized
Results by using a higher viewing height
and Dynamic background correc-
The V-groove nebulizer was used because it has a
tion.
lower susceptibility to degradation in comparison
with the glass concentric nebulizer particularly for P 177.495 nm There is a nearby weak Cu line
fusion samples. It is also less susceptible to clog- which overlaps the analyte peak
ging than glass concentric nebulizers. however the concentrations are
not significant to cause an
Analytical line selection interference.
Al 396.152 nm This line was chosen because it Si 288.158 nm This line was chosen because it
has the maximum sensitivity has minimum interferences from
while having the minimum other elements. A demountable
interferences from other ele- torch with an alumina injector is
ments as shown in figure 1. The recommended for Si determina-
high resolution of the Liberty ICP- tion.
AES minimizes spectral
interference from Ca. Ti 334.941 nm The structured background due
The performance is therefore to OH band emission presents no
better than the traditional problem.
308.215 nm Al line which suffers
from an OH band structure.
2
 Element Wavelength Detection limit
(nm) in rock (wt%)

Al 2O3 396.152 0.0007

CaO 317.933 0.0005
Fe 2O3 238.204 0.0007
K 2O 769.869 0.0015
MgO 279.079 0.0003
Figure 1. Wavelength scans of 10 ppm Al standard,
MnO 257.610 0.00002
blank and 1000 ppm Ca
Na 2O 588.995 0.0003
P 2O 5 177.495 0.003
Detection limit SiO 2 288.158 0.0009
The detection limit was determined as twice the TiO 2 334.941 0.00003
standard deviation of the blank solution (the borate
flux) measured 10 times with a 5 sec integration Table 3: Wavelengths used and detection limits obtained
time. The analytical wavelengths used and detection
limits obtained are listed in table 3. The results for the measurement of four US Geologi-
cal Rock standards are shown in table 4. The %RSD
typically varies from 0.1%7% depending on the
level of the element present.

Standard G-2 Standard PCC - 1

Measured value Certified Value Measured value Certified Value

(wt%) (wt%) (wt%) (wt%)

Al 2O3 15.15 15.37 0.55 Al2O3 0.60 0.590 0.02

CaO 2.02 1.94 0.06 CaO 0.57 0.518 0.017
Fe2O 3 2.66 2.71 0.06 Fe2O3 8.27 8.07 0.18
K2O 4.37 4.45 0.11 K2O 0.01 0.038 0.048
MgO 0.77 0.799 0.03 MgO 45.70 43.40 1.30
MnO 0.03 0.03 0.0001 MnO 0.12 0.092 0.003
Na 2O 3.84 4.06 0.13 Na2O 0.02 0.07 0.10
P2O5 0.03 0.135 0.005 P2O5 <0.01 0.02 0.01
SiO2 71.54 69.03 0.43 SiO2 42.33 41.94 0.37
TiO2 0.52 0.480 0.012 TiO2 <0.01 0.004 0.0002
TOTAL 100.93 99.00 1.39 TOTAL 97.64 94.74 2.05

Standard SY - 2 BCR - 1

Measured value Certified Value Measured value Certified Value

(wt%) (wt%) (wt%) (wt%)

Al2O3 11.88 12.04 0.23 Al2O3 12.86 13.49 0.49

CaO 8.92 7.96 0.15 CaO 7.36 6.67 0.22
Fe2O3 6.57 6.31 0.17 Fe2O3 13.42 13.15 0.29
K2O 4.31 4.45 0.11 K2O 1.63 1.70 0.04
MgO 2.91 2.69 0.12 MgO 3.67 3.45 0.11
MnO 0.34 0.32 0.01 MnO 0.19 0.14 0.004
Na2O 4.05 4.31 0.13 Na2O 3.09 3.34 0.11
P2O5 0.27 0.43 0.03 P2O5 0.17 0.351 0.009
SiO2 63.32 60.11 0.43 SiO2 55.64 54.23 0.67
TiO2 0.15 0.15 0.02 TiO2 2.40 2.20 0.055
TOTAL 102.72 98.77 1.40 TOTAL 100.43 99.02 2.00

Table 4: Results of the US Geological Rock standards analyses

3
Conclusion
The determination of majors in geological samples
by ICP-AES has been described. The values found
compare very well with the certified values indicating
that this methodology is totally suitable for these
geological samples.
The high resolution of the Liberty ICP-AES allows
the user to choose the desired wavelength depend-
ing on the precision and detection limits required.

References
1. Washington, H.S. 'The Chemical Analysis of
Rocks.', Wiley, New York (1930)
2. Suhr, N.H. and Ingamells, C.O. Anal. Chem.
38, 730 (1966).
3. Ingamells, C.O. Anal Chem. 38, 1228 (1966).
4. Boar, P.L. and Ingram, L.K. Analyst, 95,
124-130 (1970).
5. Australian Standard 1038, Part 14.1, Analysis
of coal ash, coke ash and mineral matter;
(1981).
6. Flanagan, F.J. Geochimica et Cosmochimica
Acta, 33, 81-120 (1969).
7. Thompson, M. and Walsh, J.N. A Handbook of
Inductively Coupled Plasma Spectrometry.
Glasgow: Blackie and Son Ltd (1983).