See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/344872980

Determination of Rare Earth Elements in Geological Samples by ICP-OES

Article  in  Atomic Spectroscopy · June 2000

CITATIONS READS
10 240

4 authors, including:

Ewa Bulska Atomic Spectroscopy

University of Warsaw Atomic Spectroscopy
201 PUBLICATIONS   3,900 CITATIONS    764 PUBLICATIONS   3,880 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Proteomic studies thermo-degradation polypeptides on the example of keratin and fibroin. View project

Matrix Reference Materials for Environmental Analysis and Research View project

All content following this page was uploaded by Atomic Spectroscopy on 25 October 2020.

The user has requested enhancement of the downloaded file.

 Determination of Rare Earth Elements in
Geological Samples by ICP-OES
Irena Jarona, Barbara Kudowskaa, and Ewa Bulskab*
Polish Geological Institute, Rakowiecka 4, 00-975 Warszawa, Poland
a
b University of Warsaw, Department of Chemistry, Pasteura 1, 02-093 Warszawa, Poland
INSTRUCTION
The determination of rare earth
elements (REEs) in geological mate-
rials is very important for geochem-
ical prospecting (1) and requires
accurate and precise measurement
of their concentrations. Most of the
analyses described in the literature
were done either by neutron activa-
tion analysis or by isotope dilution-
mass spectrometry (2).
Inductively coupled plasma opti-
cal emission spectrometry (ICP-
OES) has become a widely used
technique for trace element deter-
minations because of its good sensi-
tivity, high specificity, good
precision and accuracy, wide linear
dynamic range, low detection lim-
its, and reduced sample matrix
effects. A rapid and reliable method
for the routine determination of
REEs, especially for major and trace
elements, is of considerable benefit
in geological studies.
The sample introduction proce-
dure for ICP-OES analysis generally
requires dissolution of the sample.
For REE determination, decomposi-
tion can be achieved either by
alkali fusion or by acid digestion at
both low and high pressure. The
most widely used technique for
geological sample decomposition is
fusion with LiBO2 (lithium metabo-
rate) (3,4) or with a mixture of
Na2CO3 (sodium carbomate),
K2CO3 (kalium carbomate) and
Na2B4O7 (sodium tetraborate) (5).
However, the major disadvantages
of using procedures include the
high level of dissolved salts and the
large dilutions required to dissolve
the fused sample.
In case of rock samples with
refractory minerals, like zircon, the
*Corresponding author.
Atomic Spectroscopy
Vol. 21(3), May/June 2000
ABSTRACT
ICP-OES was used for the
determination of rare earth ele-
ments in geological materials.
The wet digestion procedure
including the use of HF was
applied for the total decomposi-
tion of geological samples. The
interference effects from matrix
components were investigated. It
was found that mainly iron and
titanium were responsible for
spectral interferences. The non-
spectral interferences were
caused by the presence of cal-
cium and magnesium. The math-
ematical correction algorithm
was used for correction of inter-
ference effects. The accuracy and
precision of the analytical
method were evaluated using
geological standard reference
materials: Andesite (AGV-1),
Basalt (BE-N), Granite (AC-E) and
Rhyolite (RGM1). Good agree-
ment with certified values of rare
earth elements was found for all
investigated materials.
acid decomposition has to be fol-
lowed by a "mini fusion" of the acid
insoluble residue with an appropri-
ate flux (6,7). Multi-step acid addi-
tion or the use of microwave
digestion in Teflon® bombs has
been applied to improve the effi-
ciency of acid decomposition of
resistant mineral (8).
Direct ICP-OES analysis of geo-
logical samples without chemical
separations has been reported for
some REEs (9,10) or for samples
containing high concentrations of
REEs (5,11,12). However, in most
cases, preconcentration was
applied in order to obtain lower
detection limits. This procedure
also reduces the interference from
matrix components for geological
samples of widely varying composi-
105
tion (13). Separation and/or pre-
concentration procedures
described in the literature for the
determination of REEs include pre-
cipitation (14), coprecipitation
(15), extraction (16) and ion
exchange (17-19).
Goechemical samples generally
consist of exceptionally complex
matrices, resulting in various inter-
ference effects that can introduce
errors in the determination of REEs.
Mutual spectral interference of
REEs has been studied by many
authors (21-23). It was found that
the choice of appropriate
wavelengths for REE determination
should be based on a compromise
between signal intensity and rela-
tive freedom from spectral interfer-
ence. Therefore, spectral profiles
and correction coefficients were
also investigated (14,18,23-25).
It was found that calcium, the
main component of geological sam-
ples, strongly influences the ICP-
OES sensitivity in trace elemental
analysis (26-29) and causes much
greater effects than other alkali
metals (30,31).
The aim of this work was opti-
mization of the ICP-OES analytical
procedure for the determination of
REEs in geological samples. The
developed procedure consists of
decomposition of the geological
materials and optimization of the
analytical conditions for the direct
measurement of REEs in digested
solutions. Interference correction
algorithms were applied for data
evaluation. An empirical method of
mathematical correction algorithm
was developed for the elimination
of matrix effect in the determina-
tion of REEs in extremely complex
samples.
EXPERIMENTAL
Instrumentation
For this study, a JY 70 Plus Geo-
plasma, a simultaneous and sequen-
tial emission spectrometer
(Jobin-Yvon, France), was used
with a Paschen-Runge polychroma-
tor with a 50-cm long Roland circle
with holographic gratings of 3600
gr/mm (linear dispersion
0.55nm/mm in the 1st order), and a
high-resolution 1-m Czerny-Tuner
monochromator. Instrumental oper-
ating conditions and parameters are
given in Table I.
TABLE I
Plasma Operating Conditions
Forward power 1.2 kW
Argon flow:
Plasma 12 L/min
Sheath 0.2 L/min
Carrier 0.35 L/min
Nebulizer Cross flow
Viewing height 15 mm
Sample uptake rate 1.2 mL/min
Reagents, Calibration Standards
and Geological Reference
Materials
The acid and other reagents used
were of analytical grade. A multiele-
ment calibration standard 100 mg/L
stock solution (TEKNOLAB A/S,
Drøbak, Norway), containing 50
mg/kg each of the investigated ele-
ments (except Pr and Sm), was pre-
pared in 16% aqua regia. Because of
significant mutual interference, Pr
and Sm calibration standards were
prepared from single-element stock
solutions containing 1.000 g/L of
the respective element (Aldrich,
Germany). All calibration standards
were found to be stable over a
period of at least two months. The
geological reference materials
andesite, basalt, granite, and rhyo-
lite used in this study are listed in
Table II.
TABLE II
Geological Reference Material With Main Components (in %)
AGV-1 BE-N AC-E RGM1
Andesit Basalt Granite Rhyolite
SiO2 58.84 38.20 70.35 73.45
Al2O3 17.15 10.07 14.70 13.72
Fe2O3 6.77 12.84 2.53 1.86
MnO 0.09 0.20 0.058 0.036
MgO 1.53 13.15 0.03 0.275
CaO 4.94 13.87 0.34 1.15
TiO2 1.05 2.61 0.11 0.267
Sample Dissolution Procedure RESULTS AND DISCUSSION
The samples were digested using As described, the dissolution
1-g sample, dried at 105ºC, and procedure was optimized in order
accurately weighted into a Teflon to guarantee a total dissolution of
vessel. Then the acids listed below the material for most samples.
were separately added. In each Hydrofluoric acid was used to
step, the sample was evaporated to remove the silica. It must be noted
near dryness before addition of the that even when some residue was
next acid. observed, this had no influence on
the analytical results. With this sam-
(a) 3 mL HNO3 was added and
ple pre-treatment procedure, the
evaporated to near dryness;
concentration of the investigated
(b) 3 mL HNO3 + 10 mL HF was elements was above the limit of
added and evaporated to near dry- detection. Additionally, in the final
ness; solution, a total dissolved solids
(TDS) content of less than 2% was
(c) 3 mL HNO3 + 5 mL HF was achieved; thus no physical effect on
added and evaporated to near dry- the sample introduction was
ness; observed.
(d) 3 mL HNO3 + 5 mL HClO4 Limit of Detection
was added and evaporated to near
dryness; In analytical routine work, the
analytical performance of the
(e) then the walls of the vessel applied methods have to be
were rinsed with double-distilled adequate for sample analysis. There-
water, the excess was evaporated; fore, the careful validation of the
(f) and 3 mL HCl + 1 mL HNO3 procedure consists of optimization
was added and evaporated to near of the instrumental parameters, as
dryness. well as defining the analytical fig-
ures of merits. In order to compare
The residue was dissolved in the concentration of REES in the
8 mL aqua regia. The solution was geological samples analyzed, the
transferred to a polyethylene vessel limit of detection for each element
of known weight and water added was calculated based on 6 , where
up to 50 g total mass of the final  is the standard deviation (SD) of
solution. Depending on the type of the signal produced by a blank solu-
the sample, the dissolution proce- tion (16% aqua regia). The data,
dure takes from 24 to 32 hours. The together with the spectral
clear solution was then used for wavelengths for each element, are
analysis by ICP-OES. given in Table III. The experimen-
tally obtained limits of detection for
106
 Vol. 21(3), May/June 2000

TABLE III TABLE IV

Limit of Detection (optimal Spectral Interference Effects (X sp.) From Fe, Ti, Nd, and Ce on the
instrumental parameters – see Analytical Line of Nd, Lu, Er, Sm, and Pr
Table I) for REEs Together With Interferent Concentration in Calculated
Spectral Wavelengths Solid Material Concentration of Analyte
Analyte Wavelength Limit of Detection Fe 7% 4 mg/kg Nd
(nm) (mg/kg)
Fe 7% 2.5 mg/kg Lu
La 408.672 1 Ti 2% 9 mg/kg Er
Ce 413.765 2 Nd 50 mg/kg 2 mg/kg Sm
Pr 390.844 3 Ce 250 mg/kg 39 mg/kg Pr
Nd 406.109 1
Sm 406.109 1
Eu 381.967 0.3
Gd 376.839 2
Tb 350.917 0.5
Dy 353.170 1
Ho 339.898 1
Er 349.910 1
Tm 346.220 0.3
Yb 328.937 0.5
Lu 261.542 0.5
Sc 424.683 0.5
Y 371.029 1

REEs were below the concentration

of REES in the geological references
materials investigated.
Interference Effects
Table II lists the main
components of the geological stan-
dard materials. Based on this infor-
mation, the interference effects
from the matrix components were
investigated. It was found that both
the spectral and non-spectral effects
influence the analytical signal for
ICP-OES analysis. Mainly iron and
titanium were found to be responsi-
ble for spectral interferences (Table
IV) and calcium + magnesium were
found to be responsible for non-
spectral interference.
Spectral Interference
It was found that Nd, Lu, Er, Sm
and Pr are most susceptible to spec-
tral interferences caused by the Fig. 1. (A,B,C). Emission spectra for the solid material containing 7% of iron
presence of iron and titanium as (._._._); 250 mg/kg of cerium (.........); 500 mg/kg of zirconium (- - - - -), at
wavelength: A – 390.844 nm (Pr); B – 406.109 nm (Nd); C – 350.917 nm (Tb).
well as Nd and Ce. Figure 1 shows The solid lines ( _____ ) are spectra of 5 mg/kg of: A – Pr; B – Nd; C – Tb.
the emission spectra for the solu- Background correction point (BCP): for Pr – at 390.896 nm; for Nd – at 406.159
tions containing 7% iron, 2% tita- nm; for Tb – at 350.292 nm.

107
nium, 250 mg/kg cerium, and 500
mg/kg zirconium, respectively, at a
wavelength corresponding to: A –
Pr 390.844 nm; B – Nd 406.109 nm;
C – Tb 350.917 nm. The concentra-
tion of Fe, Ti, Zr, and Ce, similar to
that present in geological samples,
was chosen. The effects of the con-
comitants on the analytical lines for
the elements investigated are listed
in Table IV. The calculated concen-
tration was defined as factor Xsp.
and was used for spectral interfer-
ence correction in the applied algo-
rithms. The Xsp. values for
respective analyses, without its
presence in aspirated solutions,
were subtracted from the concen-
tration obtained for the investigated
solutions of the materials analyzed.
Non-Spectral Interferences
It was found that the presence of
calcium and magnesium suppresses
the analytical signal obtained by
ICP-OES for all investigated
elements. This effect is illustrated in
Figure 2 for Lu, Yb, La, and Nd. The
concentration of both calcium and
magnesium in the sample solutions
for AGV-1 and BE-N are indicated
on the axis. It was interesting to
evaluate whether the observed
effects are correlated to the ioniza-
tion potential for the investigated
elements. Literature data show the
Fig.2. Effect of calcium and magnesium concentration on the relative signal for Nd,
La, Yb, Lu.
relative small difference between
the ionization potential of investi-
gated elements (8.64 eV for La and
8.97 for Nd up to 10.03 for Yb and
10.89 for Lu, respectively). The ion-
ization potential of Ca and Mg is
much lower, i.e., 6.11 eV for Ca. It
can therefore be concluded that the
difference in the suppression
effects (see Figure 2) for La, Nd, Yb
and Lu, are in the range of the long-
term precision of the determina-
tion. In order to correct observed
non-spectral interferences, for each
investigated element, parameters X
rot. = S / Srot. were evaluated,
where S – is a signal of analyte in
standard solution; S rot. – is a signal
of analyte in the solution containing
defined amounts of calcium and
magnesium. The X rot. values were
used for interference correction in
the algorithm. Besides most
pronounced effects described
above, all possible effects were
taken into account in the algorithm
used.
Interference Correction
To perform an accurate determi-
nation, the interference effect fac-
tors (Xsp and Xrot) were defined
and the mathematical algorithm
were used to correct for both spec-
tral (X sp.) and non-spectral (X rot.)
interferences. At first, the concen-
108
trations of the interfering
compounds in the solutions were
determined. In order to define the
spectral inteferences, the presence
of Fe, Ti, Nb, and Ce were found to
be critical. The effect of the 7% Fe,
2% Ti, 50 mg/kg Nd, and 250 mg/kg
Ce, respectively, on the resulting
signal of the analytical wavelength
of the REEs determined was evalu-
ated (Table IV).
The next step was devoted to
the determination of non-spectral
interference (X rot.) caused by the
presence of calcium and
magnesium. For the defined con-
tent of Ca and Mg in the sample
solution, the interference
coefficient X rot. was calculated.
The total interference effect caused
by the main components of the
investigated geological material
were corrected in the routine mea-
surement using the following equa-
tion:
➔ for negative error of spectral
interference
A corr. = (A + X sp.) ∑ X rot.
➔ for positive error of spectral
interference
A corr. = (A - X sp.) ∑ X rot.
where A = analytical signal from
the sample; A corr. = corrected ana-
lytical signal
The above algorithm was used
for the determination of the REES in
the geological standard reference
materials listed in Table II. The
results in Table V show good accu-
racy and precision of the described
procedure.
Precision and Accuracy
Four SRM geological samples
were analyzed and the concentra-
tion of REEs was determined by
ICP-OES. The six determinations for
each element were statistically ana-
lyzed. The mean and relative stan-
dard deviations as well as the
certified content are shown in
Table V, together with certified val-
 Vol. 21(3), May/June 2000

TABLE V
Analytical Results for the Determination of REEs, mg/kg (RSD, %)
Element AGV-1 BE-N AC-E RGM1
Mean (RSD) Reference Mean (RSD) Reference Mean (RSD) Reference Mean (RSD) Reference
value value value
La 36 (1.7) 38 81 (3.7) 82 ±1.5 59 (2.6) 59 ±2 22 (5.0) 24
Ce 64 (2.9) 67 152 (3.5) 152 ±4 154 (1.2) 154 ±4.7 43 (2.5) 47
Pr 8 (1.7) 7.6 18 (9.2) 17.5 ±0.6 22 (2.9) 22.2 ± 2.6 5.8 (4.0) 4.7
Nd 31 (2.8) 33 68 (5) 67 ± 1.5 92 (1.2) 92 ± 6 18 (6.0) 19
Sm 5.5 (4) 5.9 12 (6.7) 12.2±0.3 25 (2.7) 24.2 ± 0.8 3.9 (4.0) 4.3
Eu 1.5 (2.9) 1.64 3.2 (16) 3.6±0.18 1.9 (4.6) 2 ± 0.09 0.57 (5.4) 0.66
Gd 4.7 (2.7) 5.0 9.8 (3.3) 9.7±0.6 26 (1.9) 26 ± 1.5 3.7 (4.8) 3.7
Tb 0.8 (12) 0.70 1.4 (16) 1.3±0.1 4.9 (4.4) 4.8 ± 0.2 0.66 (6.6) 0.66
Dy 3.7 (6.0) 3.6 6.4 (6.5) 6.4±0.2 31 (3.0) 29 ± 1.5 3.9 (10) 4.08
Ho <1 0.67 1 (4.4) 1.1±0.13 6.4 (2.6) 6.5 ± 0.5 <1 0.95
Er 2 (10) 1.7 2.6 (17) 2.5±0.1 19 (2.5) 17.7 ± 1.2 2.5 (6.1) 2.6
Tm 0.37 (11) 0.34 <0.3 0.34±0.04 2.8 (3.0) 2.6 ± 0.24 0.4 (4.7) 0.37
Yb 1.7 (8.3) 1.72 1.8 (9.6) 1.8±0.2 17.7 (1.8) 17.4 ± 0.5 2.5 (3.6) 2.6
Lu 0.29 (7.4) 0.27 <0.3 0.24±0.03 2.5 (1.8) 2.45±0.11 0.4 (4.1) 0.41
Sc 11.1 (3.7) 12.2 22 (3.6) 22±1.5 < 0.5 0.11±0.05 4.2 (5.3) 4.4
Y 17 (2.3) 20 28 (2.6) 30±1.5 171 (2.3) 184 ± 5 21 (3.7) 25

ues of each SRM. The precision,
expressed as %RSD, shows good
validity of the analytical procedure.
Analytical accuracy was assessed by
comparing the results obtained
with the certified data.
CONCLUSION
In geology, the determination of
REEs is very important for petroge-
netic studies. In this work, the
accuracy and precision of the ana-
lytical procedure, consisting of the
total dissolution of the geological
samples and the use of a mathemati-
cal algorithm for interference cor-
rection, were evaluated. Applying
this approach, it was possible to
overcome the problems of spectral
as well as non-spectral interferences
in the presence of matrix compo-
nents.
The samples were dissolved by
wet digestion with mineral acid.
Several acids (HCl, HNO3, HF,
HClO4) were tested in order to find
the most effective mixture for quan-
titative sample decomposition.
Direct ICP-OES measurements were tigated. On the basis of our experi-
performed without matrix separa- ments, the described analytical pro-
tion. It must be noted that the cedure can be used for a large
simultaneous multielemental mea- variety of geological materials. The
surements need a special strategy to mathematical correction applied for
avoid matrix as well as spectral interference effects resulted in
interferences in REE determina- good precision (RSD 1%-5%),
tions. It was found that the most except in situations where
sensitive analytical lines for the ele- elements were determined at the
ments investigated were suscepti- detection limit level. The accuracy
ble to spectral interferences and of the procedure described was
background enhancements. The estimated by analysis of the refer-
most pronounced non-spectral ence materials. Satisfactory agree-
interference effects were found in ment with certified or reference
the presence of calcium and magne- values were obtained.
sium. As a consequence, the sensi-
tivity for most analytes was, in Received December 8, 1999.
some cases, suppressed up to 30%.
An empirical method of mathe-
matical correction algorithm was
developed for the elimination of
matrix effects in the determination
of REEs in extremely complex sam-
ples. The method developed was
applied successfully for samples
containing up to 30% calcium and
magnesium. The detection limits
for real samples were at or below
mg/kg levels for the elements inves-

109
REFERENCES
1. P.Henderson, Rare earth element
geochemistry, Elsevier , Amster-
dam (1984).
2. M.Thompson, J.N.Walsh, S.J.Walton
and G.E.M.Hall, Handbook of
inductively coupled plasma spec-
trometry, Blackie, Glasgow and
London (1989).
3. P.J.Watkins and J.Nolan, Geostand.
Newsl. 14, 11 (1990).
4. P.J.Watkins and J.Nolan, Chem. Geol.
95, 131 (1992).
5. M.Ochsenkühn-Petropoulou,
K.Ochsenkühn, and J.Luck, Spec-
trochim. Acta 46B, 51 (1991).
6. I.Jarvis and K.E.Jarvis, Chem. Geol.
53, 335 (1985).
7. I.Roelandts and G.Michel, Geostand.
Newsl. 10, 134 (1986).
8. M.Totland, I.Jarvis and K.E.Jarvis,
Chem. Geol. 95, 35 (1992).
9. M.S.Rathi, P.P.Khauna and
P.K.Mukherjee, Talanta 38, 329
(1991).
10. Z.Zhang, B.R.Bear and V.A.Fassel,
Spectrochim. Acta 46B, 1171
(1991).
View publication stats
11. K.Iwasaki, K.Fuwa and
H.Haraguchi, Anal. Chim. Acta
183, 239 (1986).
12. I.Roelandts, At. Spectrosc. 13, 193
(1992).
13. C.J.Kantipuly and A.D.Westland,
Talanta 35, 1 (1988).
14. M.I.Rucandio, Anal. Chim. Acta
264, 333 (1992).
15. J.R.Webster and M.S.Gilstrap, Chem.
Geol. 85, 87 (1990).
16. D.Weiss, T.Paukert and I.Rubeska, J.
Anal. At. Spectrom. 5, 371 (1990).
17. I.Roelandts, Spectrochim.Acta 46B,
79 (1991).
18. Z.Sulcek, I.Rubeska, V.Sixta and
T.Paukert, At. Spectosc. 10, 4
(1989).
19. C.Pin and J.F.Santos Zalduegui,
Anal. Chim. Acta 339, 79 (1997).
20. P.W.J.M.Boumans and A.H.M.van
Ham-Heijms, Spectrochim. Acta
46B, 1545E (1991).
21. P.W.J.M.Boumans and A.H.M.van
Ham-Heijms, Spectrochim. Acta
46B, 1863E (1991).
110
22. N.Daskalova, S.Velichkov, N.Kras-
nobaeva and P.Slavova,
Spectrochim. Acta 47B, 1595E
(1992).
23. V.Kanicky and J.Toman, ICP
Inform. Newsl. 15, 444 (1990).
24. I.Roelandts and G.Michel,
Geostand. Newsl. 10, 135 (1986).
25. W.Zhu, E. .B. De Leer, M.Kennedy,
P.Kelderman and G.J.F.R.Alaerts, J.
Anal. At. Spectrom. 12, 661
(1997).
26. J.C.Ivaldi and J.F.Tyson,
Spectrochim. Acta 50, 1207
(1995).
27. C.Dubuisson,E.Poussel and J.M.Mer-
met, J. Anal. At. Spectrom. 12, 281
(1997).
28. M.Thompson and M.H.Ramsey,
Analyst 110, 1413 (1985).
29. M.H.Ramsey and M.Thompson, J.
Anal. At. Spectrom. 1, 185 (1986).
30. I.B.Brener, M.Zischka, B.Maichin
and G.Knap, J. Anal. At. Spectrom.
13, 1257 (1998).
31. B.Budic, J. Anal. At. Spectrom. 13,
869 (1998).