APPLICATION NOTE 44466
Robust analysis of REE in electronic waste
High sample throughput with analysis times of less than 2 minutes
per sample with the iCAP PRO Series ICP-OES
Authors: Sukanya Sengupta1, Cristian
Cojocariu2 and Bhagyesh Surekar1
Thermo Fisher Scientific, Bremen, Germany
1
2
Thermo Fisher Scientific, Runcorn, UK
Keywords: Electronic waste, environment, high
matrix, ICP-OES, mobile phones, rare earth
elements, REE, recycling, robust, analytical
testing, WEEE
Goal
To demonstrate the capability of the Thermo Scientific™
iCAP™ PRO Series ICP-OES in axial viewing mode for high
throughput, robustness, and highly sensitive analysis of REE studies. REEs, unlike their name might suggest, are
trace and ultra-trace amounts of rare earth elements (REE) not rare in nature but the ores from which they can be
and metals in electronic waste such as mobile phones. mined in an economically viable fashion are often hard
to find. Nevertheless, REEs have important industrial
Introduction applications: Ce, La, and Y in glass and metallurgy
Rare earth elements (REEs) are 17 elements in the industries, Nd in permanent magnets, and Gd in medical
periodic table, out of which 15 belong to the lanthanide image visualization, to name just a few, and this contributes
series, found in the second last row of the periodic table to their high market demand and price. REEs are also used
– lanthanum (La) to lutecium (Lu). The remaining two in various components of electronic devices such as in
elements are scandium (Sc) and yttrium (Y), commonly magnets, screens, etc.
included in REEs because of their close geological
occurrence in ores along with the lanthanides. In nature, High demand and limited resources of REEs in the world
REEs can often also be found associated with thorium and the environmental impact of electronic waste (e-waste)
(Th), an element commonly included and reported in enforce the development of sensitive, selective, and robust
analytical technology to detect and characterize these Table 1. Instrument configuration and operating parameters
elements from e-waste and environmental samples, such
iCAP PRO XP Duo parameters
as wastewaters. The amount of electronics production as Sample Tygon™ orange/white
Pump tubing
well as generation of e-waste has increased significantly Drain Tygon white/white
in the last decades due to accelerating technological Spraychamber Glass cyclonic
advances. Thus, the recycling and management of waste Nebulizer Standard glass nebulizer
electrical and electronic equipment (WEEE) is a growing Center tube 2 mm (quartz)
problem. Old and discarded electronic waste is emerging Torch Quartz Duo torch
as an important source for recovery of valuable REEs and Pump speed 45 rpm
other metals like Fe, Ni, Ag, and Au. Flush pump speed 100 rpm
Pump stabilization time 10 s
REEs are analyzed using techniques like inductively Wash time 20 s
coupled plasma mass spectrometry (ICP-MS), ICP optical Nebulizer gas flow 0.65 L·min-1
emission spectrometry (ICP-OES) and X-ray fluorescence.1 Auxiliary gas flow 0.5 L·min-1
ICP-MS is often the technique of choice for such analyses Coolant gas flow 14.0 L·min-1
because of the high sensitivity and dynamic range of RF power 1300 W
linearity achievable. ICP-OES is a suitable, low initial cost
alternative for this kind of analyses. ICP-OES instruments
are easy to operate, require low maintenance, and can Data acquisition and data processing
provide high sample throughputs. With new age technology The Thermo Scientific™ Qtegra™ Intelligent Scientific Data
it is possible for ICP-OES techniques to deliver similar Solution™ (ISDS™) Software was used to create LabBooks
detection limits, high linearity range, and very good spectral for sample analysis and to acquire, process, and report
resolution for REEs at much lower investments. data.
In the current application note, WEEEs in the form of mobile Sample preparation
phone wastes have been inspected and analyzed for REEs Thin-film transistor (TFT) screens, printed circuit boards
and other metals using the robust and highly sensitive iCAP (PCBs), and magnets in speakers and two mobile phones
PRO series ICP-OES system, demonstrating the analytical were selected as samples representing electronic mobile
capabilities of the instrument for this kind of important phone waste (Figure 1). Sample powders were prepared
application. using a grinder; magnets were left whole. 1 to 2 g of
sample material was digested overnight in concentrated
Experimental conditions acids (HCl:HNO3 = 1:1); magnets were digested in aqua
A Thermo Scientific™ iCAP™ PRO XP ICP-OES Duo regia. Samples were filtered and final solutions contained
instrument in axial mode was used for the analyses of 10% TraceMetal™ grade HCl and HNO3 mixture. A solution
REEs and other recoverable metals in electronic waste mimicking the real samples was prepared for long term
in the current study. A standard sample introduction analysis experiments.
kit suitable for aqueous samples, consisting of a glass
cyclonic spraychamber, standard glass nebulizer, quartz A set of calibration and linearity standards were prepared in
glass duo torch, and other components listed in Table 1, 10% acid, using certified reference material (CRM) “Multi-
was used. Sample introduction was automated using a element Solution 1” (Sigma-Aldrich, Sigma-Aldrich Co., UK)
Teledyne™ CETAC™ Technologies ASX-560 Autosampler. and single element solutions (1000 mg·L-1, SPEX CertiPrep
The instrument parameters used during analysis are Group, Metuchen, NJ, US) of individual analytes. Part of the
provided in Table 1. magnet sample and laboratory prepared sample solution
was spiked with 1 and 0.8 ppm REEs, respectively, to
demonstrate analytical accuracy.
2
Table 2. Analyte wavelengths, correlation coefficient R2 (over a
calibration range of 1–10,000 µg.L-1), instrumental detection limits
(IDL, calculated by Qtegra ISDS Software) and method detection
limits for the rare earth elements and Th for the axial mode of the
iCAP PRO XP Duo instrument. The MDLs of the elements seen in the
real samples have been reported.
Elements MDL for MDL for
MDL for
and IDL TFT speaker
R 2
PCBs
wavelengths (μg·L-1) screens magnets
(μg·L-1)
(nm) (μg·L-1) (μg·L-1)
Ce 404.076 1.0000 1.3 16.6 13.3 34.0
Thin-film transistor
(TFT) screen Ce 535.353 1.0000 1.4 - - -
Dy 353.170 1.0000 0.3 - - -
Dy 400.045 0.9998 1.2 - - -
Er 337.271 1.0000 0.4 - - -
Speaker with Eu 412.970 1.0000 0.1 1.2 1.0 2.5
magnet
Printed circuit board Eu 420.505 1.0000 0.1 1.7 1.4 3.6
(PCB)
Gd 335.047 1.0000 0.8 10.9 8.7 22.3
Figure 1. Disassembled components of mobile phones that were
selected for analysis: TFT screens, magnets from within speakers, La 412.323 1.0000 0.3 - - -
and PCBs. The magnet was digested whole; the other two samples were Lu 261.542 0.9999 0.1 0.8 0.7 1.7
ground down using a kitchen grinder.
Nd 406.109 1.0000 1.3 - - -
Nd 430.358 1.0000 1.6 21.4 17.1 43.7
Pr 422.535 1.0000 0.6 7.1 5.7 14.5
Results and discussion
Pr 390.844 1.0000 1.6 - - -
The correlation coefficient R2, the limit of detection
(LOD) or instrumental detection limits (IDL), and the Pr 417.939 0.9999 2.1 27.3 21.8 55.9
method detection limits (MDL) for the different elements Sc 357.253 1.0000 0.2 - - -
along with the corresponding wavelengths are seen in Tb 367.635 1.0000 1.4 - - -
Table 2 (REEs and Th) and Table 3 (base, precious, and Th 318.019 1.0000 4.1 - - -
other metals). MDLs reported are only of analytes detected Tm 313.126 1.0000 0.3 - - -
in the samples.
Y 371.030 0.9999 0.1 4.9 3.9 10.0
Yb 289.138 1.0000 0.4 - - -
The intuitive wavelength selection tool of the Qtegra
ISDS Software, along with inspection of subarray plots
and Fullframe images, was carried out to select
interference-free wavelengths in standard solutions. Since metals like Au, Ag, etc.), interference-free wavelength
REEs emit spectral lines in similar regions of the spectrum, selection becomes more challenging. An example is shown
inter-element spectral interferences are a challenge. The in Figure 3 where Tb is interfering on the analyte of interest
Qtegra ISDS Software features simplify this task. An Gd at the wavelength 336.223 nm. The Qtegra ISDS
example of an interference-free spectrum of the REE Nd Software helps predict an interference from Tb (seen in
with background correction points set appropriately is the right panel in Figure 3). Upon running a single element
seen in Figure 2. solution of Tb, a false positive signal is obtained on this
Gd wavelength. Interference correction in Qtegra ISDS
With a complicated sample matrix, as is the case for Software can be enabled for such a wavelength, provided
electronics, enriched not only in REEs but also other the interfering analyte, in this case Tb, has at least one
elements (mainly base metals like Fe, Ni, etc. and precious wavelength itself that is clean and free of interferences.
3
Linearity Table 3. Analyte wavelength, correlation coefficient R2 (over a
calibration range of 1–100,000 µg.L-1), IDLs and method detection
The calibration curves for the different wavelengths have R2
limits (MDL) for base, precious and other metals for the axial mode
values greater than 0.9999 in the axial plasma view, over of the iCAP PRO XP Duo instrument
the calibration ranges 1 to 10,000 µg.L-1 for REEs and 1 to
Elements MDL for MDL for
100,000 µg.L-1 for the metals (Tables 2 and 3). and
LOD or
TFT
MDL for
speaker
R2 IDL PCBs
wavelengths screens magnets
(μg·L-1) (μg·L-1)
(nm) (μg·L-1) (μg·L-1)
Sensitivity
Ag 328.068 1.0000 0.4 5.6 4.5 11.4
The IDLs are all in the single digit μg·L-1 (ppb) range
(Tables 2 and 3). The IDL is calculated directly by Qtegra Al 167.079 1.0000 2.1 27.3 21.8 55.9
ISDS Software based on three times the standard deviation Au 242.795 1.0000 1.0 13.5 10.8 27.6
of a ten-replicate measurement of the calibration blank. Cr 205.560 1.0000 0.8 10.5 8.4 21.4
The R2 values are also computed in Qtegra ISDS Software Cu 324.754 1.0000 3.1 40.3 32.2 82.5
and displayed below the individual calibration curves in
Fe 259.940 1.0000 0.6 7.3 5.8 14.8
the “Concentration” tab. These values can additionally be
Ni 231.604 1.0000 1.4 18.7 15.0 38.4
exported using the “Query” option in Qtegra ISDS Software
(Figure 4). Pb 220.353 1.0000 5.9 76.4 61.0 156.4
Pd 340.458 1.0000 1.3 - - -
The analyte MDLs are sample specific and depend Pt 265.945 0.9999 2.5 - - -
upon sample preparation steps and are relevant only for Sc 357.253 1.0000 0.2 - - -
elements detected in the samples (Tables 2 and 3). MDLs
Sn 189.989 1.0000 2.5 - - -
are calculated by multiplying the IDLs with dilution factors
Zn 213.856 1.0000 1.3 16.9 13.5 34.58
for each sample. Samples like speaker magnets have
much higher concentrations of analytes and require greater
dilution factors, thereby yielding higher MDLs.
Figure 2. Clean interference free spectrum of REE- Nd at 406.109 nm in axial mode
4
Figure 3. Interference of Tb on Gd at 336.223 nm. Qtegra ISDS Software interference correction can be applied to correct for this.
Figure 4. Query function in Qtegra ISDS Software offers export of all measured and calculated parameters, e.g., concentrations,
IDL/LODs, etc.
5
Precision/spike recovery Figure 5 and Figure 6, respectively. Spike recoveries in the
The spike recoveries of a 0.8 ppm spike on a simulated ±15% range are obtained for most analytes.
sample and 1 ppm spike on magnet speaker samples
(run intermittently during the long-term tests) are shown in
Figure 5. Spike recoveries in spiked laboratory simulated solution run intermittently over a couple of hours
Figure 6. Spike recovery in speaker magnet samples, 1 ppm spike
Method performance and quantification of REEs and Robustness
other metals in real samples The two long-term stability tests show the relative
The REEs and metals found in the samples and their concentration of analytes is between 80 and 120% over
final recalculated concentrations are shown in Table 4. ~6 hours of analyses (including samples, standards,
Sample solutions were diluted as necessary. Dilution blanks, and washes), which might be a typical working
factors or sample weights and final volumes can be day in the laboratory (Figure 7, panels A and B). A short
specified in the respective Qtegra ISDS Software exposure time of 5 s was used, resulting in analysis time for
LabBooks and final dilution factors, and final analyte a single sample of <2 min, including uptake time, 3 repeats,
concentrations will be automatically calculated by the and rinse times.
software.
6
Table 4. Final calculated concentrations (µg.g-1) of REEs and metals in undiluted samples of mobile phone components – TFT screen,
PCB, and magnets from the speakers
Element and TFT screen 1 TFT screen 2 PCB 1 PCB 2 Speaker magnet 1 Speaker magnet 2
wavelength (nm) (µg.g-1) (µg.g-1) (µg.g -1) (µg.g-1) (µg.g -1) (µg.g-1)
Rare earth elements (REE)
Ce 404.076 <DL <DL 1.025 1.016 28,678.856 27,907.174
Eu 412.970 <DL 0.768 <DL <DL <DL <DL
Eu 420.505 <DL 0.765 <DL <DL <DL <DL
Gd 335.047 0.079 0.141 3.598 3.959 4047.393 5930.288
Lu 261.542 0.022 0.017 1.947 1.633 17.255 16.207
Pr 417.939 <DL <DL <DL <DL 12,802.391 14,267.827
Nd 430.358 <DL <DL <DL <DL 37,392.193 40,643.866
Y 371.030 0.015 0.020 0.833 1.132 <DL <DL
Metals
Ag 328.068 13.599 41.205 289.296 496.581 <DL <DL
Al 167.079 1085.738 1322.702 475.877 486.056 22,820.756 28,300.425
Au 242.795 5.404 1.686 2.604 0.989 29.942 31.624
Cr 205.560 252.225 183.967 1057.523 945.728 3036.511 3549.902
Cu 324.754 1364.658 5841.867 189,027.425 164,140.575 - -
Fe 259.940 877.812 677.548 2406.179 2130.731 803,015.933 840,304.409
Ni 231.604 189.522 218.559 1663.002 1647.645 1107.861 1091.483
Pb 220.353 0.074 0.171 5.111 4.025 235.458 254.557
Zn 213.856 47.018 56.269 699.394 704.884 31,947.532 35,770.742
Figure 7. Recoveries of analytes, displaying instrument stability during long-term experiments run on two
days. Each experiment constitutes at least 6 hours of continuous analysis in axial mode of the iCAP PRO XP Duo
instrument.
7
Conclusions • Recovery values within the expected (±15%) range were
This application note describes an analytical solution obtained for both real as well as laboratory simulated
that can be used for the determination of REEs, precious samples, demonstrating the accuracy of the technique.
metals, and toxic elements in electronic waste using
the iCAP PRO XP ICP-OES Duo system. The analytical • Excellent system robustness was demonstrated with no
procedure outlined in this note includes a simplified sample significant bias in the analytical results as observed for
preparation technique to handle mobile phone waste and two consecutive days of continuous data acquisition.
ensure that such complex samples are suitably prepared The vertical torch design in the Duo instruments enables
for analysis using ICP-OES. plasma stability even with complicated samples matrices.
• Fast analysis time with less than 2 min/sample allows for
The highlights are summarized below: high sample throughput and minimal downtime, making
• Various REEs and other valuable or toxic metals were it ideal for contract testing laboratories or for users
found in the analyzed e-waste samples, displaying both engaged with analyzing a high number of samples daily.
the potential value for such samples in the recycling • For applications where sample throughput is not critical,
industry as well as the need for responsible waste the iCAP PRO X ICP-OES Duo system with slightly
management. longer integration times, translated to more time per
• Excellent large linear dynamic range was obtained sample, can be used without compromising on analytical
for REE (1 to 10,000 μg·L-1) and basic metals (1 to performance.
100,000 μg·L-1), making the iCAP PRO XP ICP-OES • Using analytical advances available on the iCAP PRO
Duo system an ideal analytical tool for multi-elemental XP ICP-OES system, in combination with the Qtegra
analysis of samples such as e-waste, which have large ISDS Software tools, suitable wavelength selection
variations in concentrations of constituent elements. The and effective interference removal of target elements in
large dynamic range enables users to reliably analyze e-waste sample matrix is obtained with ease.
trace to ultra-trace levels at low concentration (Eu, Pb,
etc.) as well as accurately quantify elements like Fe, Cu,
etc. present in very high concentration. Reference
1. Zawisza, B.; Pytlakowska, K.; Feist, B.; Polowniak, M.; Kita, M.; Sitko, R. Determination
of rare earth elements by spectroscopic techniques: a review. Journal of Analytical
• Highest sensitivity (in the low ppb range) was achieved Atomic Spectrometry, 2011, 26, 2373–2390.
for all targeted analytes in the Axial viewing mode. This
is essential for detecting REEs, precious and poisonous
elements, which often are present in very small amounts
in e-waste samples.
Find out more at thermofisher.com/ICP-OES
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