Faculty of Mathematics and Science, Department of Chemistry,

P.O. Box 35, 40014, University of Jyväskylä, Finland

Determination of rubidium in difficult matrices

by inductively coupled plasma optical emission
spectrometry
Nygrén, E., Perämäki, S., Väisänen, A.,
enni.k.nygren@jyu.fi

 US EPA method 200.7 was used for determination of instrument TESTING MLR WITH REAL SAMPLES
INTRODUCTION (IDL) and method (MDL) detection limits  Real samples are from rubidium recovery tests for fly ash where
A process of reclaiming compounds and elements  Detection limits, correlation coefficients and relative standard sample treatment leads to high sodium concentrations
from anthropogenic stocks such as products, buildings deviations (RSD) for radial and axial plasma viewing are listed in
 Two real samples were tested
and waste is called urban mining [1]. Some examples table 3
Type 1 sample: low Na concentration, high other EIE
are the recovery of valuable elements from industrial
concentrations
fly ash, electronic waste, etc. Rubidium is an alkali Table 3. Wavelengths, correlation coefficients, instrument and method
metal and has high abundance in the earth’s crust, but detection limits and RSD (%) ranges for radial axial plasma viewing when Type 2 sample: very high Na concentration, low other EIE
it is usually widely spread and not found in high analyzing rubidium. elements
concentrations in any minerals [2]. This is why it is Wave-
Plasma Correlation IDL MDL
 Samples type 1 and 2 were diluted so that the concentrations of
important to look for alternative sources for this length RSD (%)
viewing coeff. mg L-1 mg L-1 MLR samples would cover concentrations of rubidium and matrix
valuable element. nm
elements in the samples (table 4)
The problem faced with ICP-OES determination of Rb Radial 780.023 0.9999 0.41 0.55 1.98-23
in waste materials is EIE (easily ionized element)  With type 2 sample, the dilution could not be done in needed
Axial 780.023 0.9998 0.011 0.052 0.31-1.17
interference and spectral interference due to argon in extend due to low concentrations of rubidium, hence Na
Rb’s main emission wavelength 780.023 nm. EIEs in concentration was over MLR area
 Argon interference and low intensities of radial viewing of
high concentrations can give a dramatic rise to the rubidium at wavelength780.023 nm can be seen in figure 1.  Rb values measured by ICP-OES and corrected using MLR were
analyzed element’s concentrations. Axial plasma compared with values measured by GFAAS (table 5)
viewing suffers interferences caused by other EIEs, but
in the determination of rubidium the required
Table 4. Concentrations of matrix elements in two samples analyzed by
sensitivity can only be obtained by axial plasma two different methods.
viewing. Multiple linear regression (MLR) method can
Concentration of interfering elements (mg L-1)
be used to correct increase of rubidium concentrations Na K Mg Ca Fe
determined by axial plasma viewing. Sample1 21 61 62 680 320
Sample2 2300 35 - 2 -
OBJECTIVE OF THE RESEARCH
Table 5. Concentrations of rubidium in two analyzed samples.
 Ionization interference of rubidium was corrected by MLR method
by creating correction equation that compensates the increase of Before After
ICP/GFAAS ICP/
the intensities measured by axial plasma viewing. correction Correction
% GFAAS %
mg L-1 mg L-1
 Correction equation was tested with two real samples and results Sample 1 7.7 201 % 4.1 106 %
were compared to Rb values determined by graphite furnace Sample 2 6.8 260 % 2.2 85 %
atomic absorption spectrometry (GFAAS) Fig. 1. Effect of the interference of argon emission on radial (left) and
axial (right) measurements of 5 mg/L of rubidium. Vertical line represents
INSTRUMENT DESCRIPTION AND OPERATING PARAMETERS rubidium’s emission wavelength 780.023 nm.

 ICP-OES PerkinElmer Optima 8300 and GFAAS PerkinElmer CONCLUSIONS

MLR METHOD
AAnalyst 800 were used for analysis of rubidium.
 19 synthetic samples were prepared at five concentration levels • MLR correction equation works well and enables
 PTFE cyclonic spray chamber with helix and GemCone Low Flow determination of Rb in difficult matrices by ICP-OES
Rubidium 1-5 mg L-1
nebulizer and Quatz torch with flate plate plasma were used with with axial plasma viewing
ICP-OES Interfering elements Na 15-1615 mg L-1, K 0.5-50.5 mg L-1, Ca
10-1010 mg L-1, Mg 5-55 mg L-1, Fe 0.2-2.2 mg L-1 • Recovery of Rb in synthetic samples before
 THGA tubes with end caps and HCL lamp and AS-800 autosampler correction was 133-296 % and after correction 84-
 The determined Rb concentrations were 133-296 % compared to
were used with GFAAS 130%
the added concentrations
 Measurement parameters are listed in Tables 1 and 2
• With two real samples recoveries of rubidiun
 From the suspected interference elements, only sodium and
compared to the values determined by GFAAS were
calcium had significant effect on the determined concentrations of
Table.1. Operating conditions for PerkinElmer Optima 8300
before correction 201 % and 260 % and after
rubidium
correction 106% and 85 %
Parameters for ICP-OES Settings  Used correction equation:
RF Power (W) 1 500
Plasma gas flow rate (L min-1) 8 y = (0.408Rb) + (-0.00083Na) + (-0.00058Ca) + 1.21
-1 ACKNOWLEDGEMENTS
Carrier gas flow rate (L min ) 0.6
 After correction, the measured and added rubidium concentrations
Auxiliary gas flow rate (L min )-1
0.2 The financial support of Department of Chemistry of University of
had no significant difference at 95% level of confidence according
Sample introduction rate (mL min-1) 1.5 Jyväskylä and Finnish energy company Jyväskylän Energia are greatly
to Student’s t-test
Replicates 3 acknowledged.
 The effect of the correction can be seen in figure 2 _______________________________
Table 2. Operating conditions for GFAAS PerkinElmer AAnalyst 800
[1] R. Cossu and I.D. Williams, Urban mining: Concepts, terminology, challenges
Parameters for GFAAS Settings 300 %
Lamp current (mA) 10 Waste Management, 2015, 45, (1–3)
Slit (nm) 0.7 250 % Recovery [2] F.S. Wagner, Rubidium and rubidium comboounds in Kirk-Othmer Encyclopedia
Temperature program (⁰C ) Drying: 110-130 before of Chemical Technology, John Wiley and Sons, Inc. 1997, 21 ed., s. 591-600.
200 % correction
Pyrolysis: 700
Atomization:1800
Cleaning: 2400 150 %
Recovery
100 % after
CALIBRATION AND DETECTION LIMITS FOR ICP-OES correction

50 %
 Four point calibration in a range of 0 – 10 mg L-1 for rubidium
 Acid backgrounds of calibration solution and samples were 0%
0 2 4 6 8 10 12 14 16 18
adjusted to 20 % Aqua Regia
Fig. 2 Recoveries of rubidium before and after MLR correction