Monitoring Heavy Metals by Atomic

Absorption Spectroscopy for

Compliance with RoHS and WEEE
Directives
Application Note

Semiconductor Analysis and Environmental

Author
Introduction
John Sanders
The rapid expansion in the quantity of used electronic and electrical appliances has
created a need to safely dispose of the used equipment. The European Community
has introduced regulations to enforce limits on the amount of toxic metals and
organic chemicals used in the production of material. Compliance with the
regulations will help prevent hazards for future generations when the equipment
is recycled or responsibly disposed. In electronic and electrical equipment
manufacturing, the regulations require these materials to be measured and limited.

Several analytical instrument techniques can be employed for the determination

of these hazardous substances. For example, the heavy metals Cd, Pb, Hg and Cr
can be determined by AA, ICP-OES or ICP-MS [1-2]. Hexavalent chromium can be
determined by UV-Vis [3-4], the PCB and PBDE can be determined by GC [5] and
GC-MS [6-7]. On the other hand, XRF can also be used for screening heavy metals
and total bromine [1,8]. In this article, various sample preparation methods are
evaluated for the determination of Cd, Pb, Hg and Cr in plastic by atomic absorption
spectroscopy.

In Varian ICP-OES Application Note Number 40, Tran Nahm [9] reported on the
determination of metals in plastics using ICP-OES instrumentation. In this article, they
report on the measurement of Cd, Cr, Pb and Hg in plastics using atomic absorption
and Zeeman graphite furnace using the same analytical sample
preparation processes.
Instrumentation Element Cd Pb Cr
Sample volume 20 µL 20 µL 20 µL
Volume reduction 2 2 2
All furnace measurements were performed using an Agilent factor
280Z AA spectrometer fitted with an Agilent PSD 120 Bulk concentration 5.0 µg/L 50.0 µg/L 20.0 µg/L
Programmable Sample Dispenser. Bulk vial number 51 54 51
Makeup vial 52 52 52
The mercury vapor measurements were conducted using number
Sample number 1 1 1
an Agilent 280FS AA operating in Duo mode with a VGA 76 of injections
Vapor Generation Accessory while the furnace analysis was Sample last dry 1 1 1
underway on the Agilent 280Z AA. step
Hot inject On On On
Normal coded hollow cathode lamps were used for analysis of Hot inject 80 °C 80 °C 80 °C
mercury, cadmium and chromium and an UltrAA lamp for lead. temperature
Hot inject rate 5 5 5
A microwave digestion oven (CEM, Mars 5, ESP 1500 Plus, Modifier 1 mode Co inject Co inject None
Modifier 1 volume 5 µL 5 µL
CEM Corporation, Mathews, NC) was used for the microwave
Modifier Ammonium Ammonium
digestions. dihydrogen dihydrogen
orthophosphate orthophosphate
Table 1. Instrument Operation Conditions (5 g/L) (5 g/L)
Element Cd Pb Cr Last dry step 0 0
Instrument type Zeeman Zeeman Zeeman Injection rate 1 1
Concentration units µg/L µg/L µg/L Modifier 1 position 53 53
Instrument mode Absorbance Absorbance Absorbance Number of injections 1 1

Sampling mode Autonormal Autonormal Autonormal

Calibration mode Concentration Concentration Concentration Table 2. Furnace Operating Conditions
Measurement mode Peak area Peak area Peak area
Cadmium furnace conditions
Replicates standard 2 2 2 Temperature Flow Gas Signal
Replicates sample 2 2 2 Step (°C) Time (s) (L/min) type Read storage
Expansion factor 1 1 1
1 85 30 0.3 Normal No No
Minimum reading Disabled Disabled Disabled 2 110 10 0.3 Normal No No
Smoothing 7 point 7 point 7 point 3 400 5 0.3 Normal No No
Concentration 1 1 1 4 400 5 0.3 Normal No No
decimal places 5 400 2.5 0 Normal No Yes
Wavelength 228.8 nm 283.3 nm 357.9 nm 6 1800 0.8 0 Normal Yes Yes
Slit width 0.5R nm 0.5 nm 0.2 nm 7 1800 2 0 Normal Yes Yes
Gain 45% 36% 42% 8 1800 2 0.3 Normal No Yes
Lamp current 4.0 mA 10.0 mA 7.0 mA
UltrAA Lamp No Yes No Lead furnace conditions
Lamp position 1 3 2 Temperature Flow Gas Signal
Step (°C) Time (s) (L/min) type Read storage
Background On On On
correction 1 85 30 0.3 Normal No No
Standard 1 1.0 µg/L 10.0 µg/L 5.0 µg/L 2 110 10 0.3 Normal No No
Standard 2 3.0 µg/L 25.0 µg/L 10.0 µg/L 3 600 5 0.3 Normal No No
4 600 5 0.3 Normal No No
Standard 3 5.0 µg/L 50.0 µg/L 20.0 µg/L 5 600 2.1 0 Normal No Yes
Reslope rate 0 0 0 6 2100 0.9 0 Normal Yes Yes
Reslope lower limit 75.00% 75.00% 75.00% 7 2100 2 0 Normal Yes Yes
Reslope upper limit 125.00% 125.00% 125.00% 8 2100 2 0.3 Normal No Yes
Recalibration rate 0 0 0
Calibration Quadratic origin Quadratic origin Quadratic origin Chromium furnace conditions
algorithm Temperature Flow Gas Signal
Calibration lower 20.00% 20.00% 20.00% Step (°C) Time (s) (L/min) type Read storage
limit 1 85 30 0.3 Normal No No
Calibration upper 150.00% 150.00% 150.00% 2 110 10 0.3 Normal No No
limit 3 1000 5 0.3 Normal No No
Total volume 27 µL 27 µL 22 µL 4 1000 1 0.3 Normal No No
5 1000 2 0 Normal No Yes
6 2700 0.8 0 Normal Yes Yes
7 2700 2 0 Normal Yes Yes
8 2700 2 0.3 Normal No Yes

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Table 3. Mercury Instrument Operating Conditions Calibration Solutions Preparation
Element matrix Hg – RoHS
All standards and blank were matrix-matched for the
Instrument type Vapor chemicals and reagents used in the sample preparation.
Concentration units µg/L
Sampling mode AutoMix
Calibration mode Concentration Certified Reference Materials
Measurement mode Integrate
Validation of the methods was carried out by using the
Replicates standard 3
Replicates sample 3 following certified reference materials:
Expansion factor 1
Minimum reading Disabled • Institute for Reference materials and Measurements
Smoothing 7 point (IRMM)—European Reference Materials ERM-EC 681
Concentration decimal places 2 Polyethylene 19 [10].
Wavelength 253.7 nm
Slit width 0.5R nm • National Metrology Institute of Japan (NMIJ) [11]—
Gain 35% Certified Reference Material CRM 8102a ABS resin10.
Lamp current 4.0 mA
UltrAA Lamp No
Lamp position 4 Sample Preparation
Background correction Off Method BS EN 1122:2001 [12] is the only reference method
Standard 1 20.00 µg/L
Standard 2 40.00 µg/L
for metal in plastics and provides details for the determination
Standard 3 60.00 µg/L of Cd in plastic. There is no standard published sample
Reslope rate 0 preparation method for the determination of other heavy
Reslope lower limit 75% metals in plastic.
Reslope upper limit 125%
Recalibration rate 0 The use of sulfuric acid in Method EN1122 prevents the
Calibration algorithm Quadratic origin detection of Pb because of the potential precipitation of
Calibration lower limit 20%
Measurement time 5.0 s PbSO4. On the other hand, EPA Method 3050 [13] Acid
Pre-read delay 60 s Digestion of Sediments, Sludges and Soils recommends the
Vapor type Cold vapor use of 1–2 g of sample in 10 mL HNO3 and heating at 95 °C,
Burner height 4.4 mm and is not suitable for the analysis of plastics. Experiments
show the 10 mL volume of HNO3 is too small, and the heating
Table 4. Characteristic Concentrations and Correlation Coefficients
temperature of 95 °C is not high enough to decompose the
Lead Chromium Cadmium Mercury plastic material.
Characteristic 1.8 µg/L 0.2 µg/L 0.10 µg/L 0.28 µg/L
concentration EPA Method 3053 [14] Microwave Assisted Acid Digestion
Correlation 0.9999 1.0000 1.0000 1.0000
coefficient of Siliceous and Organically Based Matrices, recommends
microwave digestion with the use of HNO3 and HF. Since
HF is only required for samples of siliceous matrices, EPA
Materials and Reagents Method 3051A [15] Microwave Assisted Acid Digestion of
Reagents Sediments, Sludges, Soils, and oils (a microwave digestion
method that uses only HNO3) is adequate. This avoids the
All chemicals and reagents used were of analytical grade.
hazards associated with the use of HF.
• Nitric acid. 60%, Analar, BDH
A summary of various sample preparation methods used in
• Hydrochloric acid. 32%, Univar, Ajax Finechem this work is listed in Table 5.
Table 5. Digestion Methods
• Sulfuric acid. SP Gr. 1.84, Merck
Digestion methods Analyte(s)
• Hydrogen peroxide. 35%, Merck EN 1122 (H2SO4-H2O2) Cd
HNO3-H2O2 Cd, Pb, Cr
• Water, distilled deionized, Milli-Q purification system
EPA 3051A Cd, Pb, Cr, Hg
(Millipore) (Microwave digestion with HNO3)

3
Method EN 1122 (H2SO4-H2O2 Digestion) Table 6. MARS 5 Microwave Conditions
Power Pressure Temperature
Accurately weigh 1 g of sample into a 250-mL beaker, add Step (w) Percent Ramp (PSI) (°C) Hold
10 mL of H2SO4, cover with a watch glass, heat on a hot
1 300 100 10 350 170 10
plate at high temperature to decompose and carbonize the
2 300 100 0.1 350 170 5
organic substances. When white fumes are evolved, continue
to heat for about 15 minutes. Remove the beaker from the
hot plate and allow to cool for about 10 minutes. Add slowly Results and Discussion
four 5 mL portions of H2O2 solution. Allow the reaction to
subside after each addition. Heat again for about 10 minutes Analytical Results
and allow to cool for 5 minutes. Add a further 5 mL portion
Table 7. Analytical Results
of H2O2 solution and heat again. Stop the addition of H2O2
Chromium Lead Cadmium Mercury
when no more organic matter remains. Allow to cool to room Method (mg/kg) (mg/kg) (mg/kg) (mg/kg)
temperature and transfer the mixture quantitatively to a 100- EN 1122 (H2SO4-H2O2 digestion)
mL volumetric flask. Make up the mark with Milli-Q water. EC681 17.7 – 21.3 –
NMIJ 28.1 – 10.6 –
HNO3-H2O2 Digestion
Accurately weigh 1 g of sample into a 250-mL beaker, add HNO3-H2O2 digestion
25 mL of HNO3, cover with a watch glass, heat on a hot plate EC681 17.4 13.6 21.8 4.59
until all dissolved. Cool for 5 minutes, and then add slowly in 1 NMIJ 27.7 110.0 10.9 –
mL aliquots 10 mL of H2O2. Care must be taken to ensure that
losses do not occur due to excessive vigorous effervescence. EPA Method 3051A (Microwave digestion with HNO3)
Continue heating the mixture until the volume is reduced to EC681 17.7 13.7 21.9 4.63
approximately 5 mL. After cooling, transfer the mixture to a NMIJ 27.8 110.5 10.7 –
100-mL volumetric flask, and make up to the mark with Milli-Q
water. Filter to remove any organic plastic precipitate. Certified concentrations
EC681 17.6 ± 0.7 13.7 ± 0.8 21.7 ± 0.7 4.50 ± 0.15
EPA Method 3051A (Microwave digestion with HNO3) NMIJ 27.87 ± 0.35 109.9 ± 0.89 10.77 ± 0.2 –
Accurately weigh 0.5 g of sample into a fluorocarbon microwave
vessel equipped with a controlled pressure relief mechanism. Detection Limits
Add 10 mL concentrated HNO3 to the vessel. Seal the vessel
The instrument detection limit is expressed as the
according to the manufacturer’s instructions. Properly place
concentration equal to three times the standard deviation of
the vessel in the microwave system. Digest at 175 °C for 10
the blank concentration.
minutes. After cooling, carefully uncap and vent each vessel in
a fume cupboard. Quantitatively transfer the mixture to a 50-mL
volumetric flask, and make up to the mark with Milli-Q water. Table 8. Detection Limits
Filter to remove any organic plastic precipitate. WEEE/RoHS maximum Instrument detection limit
Element (µg/kg) (µg/kg)
MARS 5 Microwave Conditions Cadmium 100 0.015

• Vessel: HP500 Chromium 1000 0.089

Lead 1000 0.33
• Mode: Ramp to Temperature Mercury 1000 0.030

4
Conclusions Waste. Washington D.C. Viewed 8 Nov 2006; <http://
www.epa.gov/SW-846/pdfs/8082.pdf>.
It should be noted that in the current regulations, the
6. US Environmental Protection Agency. EPA Method
maximum level allowed for these metals in plastics are
8270C. Semivolatile organic compounds by Gas
too high for normal graphite furnace measurement. The
Chromatography/Mass Spectrometry (GC/MS).
digested samples would require significant dilution before
December 1996. US EPA Office of Solid Waste.
measurement leading to possible significant errors. This
Washington D.C. Viewed 8 Nov 2006; <http://www.
indicates that if a simple pass/fail test is required, the
epa.gov/sw-846/pdfs/8270c.pdf>
measurement of the lead, chromium and cadmium could be
performed using flame atomization. Vapor generation would 7. R. Brittain. Varian GC/MS Application Note Number
still be required for the determination of mercury. 75: Fast, sensitive and selective determination of
Polybrominated Diphenylethers by Tandem Mass
However, the levels of metals present in the available Spectrometry. September 2004; Varian, Inc.
reference materials are too low for flame atomization to yield
accurate and precise measurements. This requires the use of 8. J. Wolska. Elemental analysis in the plastic industry.
graphite furnace measurements discussed in this application Plastic Additives & Compounding. May/June 2003;50–
note. The limitation is the skill required to conduct the sample 55.
digestion. The measurement of lead, chromium, cadmium 9. T. Nham Tran. Varian ICP-OES Application Note
and mercury in polymers is shown to be very simple as the Number 40: Monitoring Heavy Metals by ICP-OES for
levels present in the analytical solutions are well above the Compliance with RoHS and WEEE Directives. April
instrument detection. 2006; Varian, Inc.
10. European Reference Materials. 2004–2007. European
References Reference Materials. Belgium. Viewed 8 Nov 2006;
<http://www.erm-crm.org>.
1. T. Ernst, R. Popp, R. van Eldik. Quantification of heavy
metals for the recycling of waste plastics from the 11. National Metrology Institute of Japan. 2003. National
electrotechnical applications. Talanta 2000;53:347– Metrology Institute of Japan. Viewed 8 Nov 2006;
357. <http://www.nmij.jp>.

2. A. Ritter, E. Michel, M. Schmid, S. Affolter. 12. European Standard EN 1122. Plastic—Determination

Interlaboratory test on polymers: determination of of Cd—Wet decomposition method, March 2001.
heavy metals in polymer metrices. Polymer Testing, 13. US Environmental Protection Agency. EPA Method
2004;23:467–474. 3050B. Acid digestion of sediments, sludge, and
3. US Environmental Protection Agency. EPA Method oils. December 1996. US EPA Office of Solid Waste.
3060A. Alkaline Digestion for Hexavalent Chromium. Washington D.C. Viewed 8 Nov 2006; <http://www.
December 1996. US EPA Office of Solid Waste. epa.gov/SW-846/pdfs/3050b.pdf>.
Washington D.C. Viewed 8 Nov 2006; <http://www. 14. US Environmental Protection Agency. EPA Method
epa.gov/sw-846/pdfs/3060a.pdf>. 3052. Microwave assisted acid digestion of siliceous
4. US Environmental Protection Agency. EPA Method and organically based matrices. December 1996. US
7196A. Chromium, Hexavalent (Colorimetric). July EPA Office of Solid Waste. Washington D.C. Viewed 8
1992. US EPA Office of Solid Waste. Washington D.C. Nov 2006; <http://www.epa.gov/epaoswer/hazwaste/
Viewed 8 Nov 2006; <http://www.epa.gov/sw-846/ test/pdfs/3052.pdf>.
pdfs/7196a.pdf>. 15. US Environmental Protection Agency. EPA Method
5. US Environmental Protection Agency. EPA Method 3051A. Microwave assisted acid digestion of sediments,
8082. Polychlorinated Biphenyls (PCBs) by Gas sludge, soils and oils. January 1998. US EPA Office
Chromatography. December 1996. US EPA Office of Solid of Solid Waste. Washington D.C. Viewed 8 Nov 2006;
<http://www.epq.gov/sw-846/pdfs/3051a.pdf

5
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February 1, 2012
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