Transcript 08_SOC-testing

Meeting the requirements
of the ELV Directive:
Measurement of Substances of
Concern (SOCs)
Maré Linsky and Retha Rossouw
National Metrology Laboratory
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2005
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Overview
 European Union Directives
 Analytical Techniques
 Developing an In-house Analyses Method
 Outsourcing Analyses
 National Metrology Laboratory
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European Union Directives
 End-of-Life Vehicles (ELV) Directive 2000/53EC
Goal: Reduce waste generated by vehicles at the end of their lives,
though the collection, re-use and recycling of vehicle components.
- Production and Design should facilitate dismantling, re-use, recovery and
recycling
- Increase the use of recycled material
- Reduce the use of hazardous substances
- Maximum allowable levels of heavy metals e.g. Cd, Cr(VI), Hg and Pb
 Waste Electrical and Electronic Equipment Directive (WEEE)
2002/96/EC
 Restrictions on Hazardous Substances Directive (RoHS) 2002/95/EC
- Also similar directives being proposed in China, Australia & California
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Typical applications of SOCs
(functional vs contaminant)
• Cadmium [Cd]:
• Mercury [Hg]:
- Pigments and stabilizers in plastics
- Batteries
- NiCd Batteries (exempt until Dec ‘08)
- Relay-contacts, micro-switches
- Fluorescent lamps (to be labeled)
• Hexavalent Chromium [Cr(VI)]:
- Anti-corrosive coatings (exempt until
July ‘07)
- Anti-corrosive coatings – Nut and
Bolt assemblies (exempt until July ‘08)
- Plasticizers
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• Lead [Pb]:
- Pigments in paint
- Minor element in steels, aluminium
- Stabilizers and pigments in PVC
- Batteries (to be labeled)
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European Union End-of-Life Vehicles (ELV)
Directive 2000/53EC
Maximum limits (%) *
EU Directive
Cd
Cr(VI)
Hg
Pb
ELV Directive **
0,01
0,10
0,10
0,10
WEEE and RoHS
Directives
0,01
0,10
0,10
0,10
* 0,1 % = 1000 ppm = 1000 mg/kg = 1000 µg/g
** Annex II: List of Material Exemptions
- Pb as alloying element
- Cr(VI) in corrosion preventative coatings
- Hg in discharge lamps and instrument panel displays
- Cd in batteries for electrical vehicles
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Recommended SOC testing scheme
Representative, homogeneous
sample
ED-XRF Screening
ELV
Non-Compliant
> 125 ppm Cd
< 75 ppm Cd
> 1250 ppm Hg, Pb
< 750 ppm Cr, Hg, Pb
Cd: 75 – 125 ppm
Hg, Pb: 750 – 1250 ppm
Cr > 750 ppm
Accurate Verification Test
Cd, Pb:
Hg:
Cr(VI):
• ED-XRF
• CVAAS
• UV-Vis
• WD-XRF
• CVAF
• IC
• AAS
• ICP-OES
• ICP-OES
• HG-ICP-OES
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ELV Compliant
WDXRF
(Solid with sample preparation)
 (Non)-destructive
 High accuracy
 Excellent precision & long term stability
 Good resolution & sensitivity
 Multi-element analysis
 Well-established technique
 Some sample preparation
 Qualified, experience staff
 Expensive
 Calibration Standards and Certified
Reference Materials (CRM)
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EDXRF
(Solid with sample preparation)
 Fast
 Generally not portable
 (Non)-destructive
 Some sample preparation required
 Sample Area
 Experienced staff
 Good precision, accuracy
 Moderately expensive
 Fair sensitivity
 Calibration Standards and Certified
Reference Materials (CRM)
 Multi-element analysis
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EDXRF
(Solid – Minimal preparation)
 Simple, fast
 Generally not portable
 Non-destructive
 Fair sensitivity (poor excitation due
to low tube voltage)
 No sample preparation
 Sample Area (some control)
 Good precision, accuracy
 Multi-element analyses
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 Moderately expensive
 Calibration Standards and Certified
Reference Materials (CRM)
Handheld EDXRF – Instruments
(Solid – No preparation)
 Portable, flexible
 Sample Area (large, difficult to control)
 Simple, fast
 Poor reproducibility, accuracy
 Non-destructive
 Poor sensitivity (poor excitation due to
low tube voltage)
 No sample preparation
 Multi-element analysis
 Inexpensive
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 Instrument Calibration
 Safety
GDOES
(Solid with minimal preparation)
 Only conducting samples
 Small sample area
 Analysis of sample layers
 Good precision and long term stability
 Good sensitivity and accuracy
 Multi-element analysis
 Flat surface areas
 Some sample preparation
 Qualified, experienced staff
 Calibration Standards and Certified
Reference Materials (CRM)
 Expensive
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AAS
(Solution based analysis)
 Simple, well established technique
 Not expensive
 Sample Preparation required
(destructive)
 Dedicated laboratory
 Matrix tolerant
 Traceable, certified solution standards
available
 Qualified, experienced staff
 Sequential technique (mostly)
 Narrow working range
 LODs
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ICP-OES
(Solution based analysis)
 Excellent Accuracy, Precision
 Excellent Sensitivity (low LOD)
 Dedicated laboratory
 Matrix tolerant
 Traceable, certified standard
solutions available
 Multi-element analysis
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 Sample Preparation required
(destructive and time consuming)
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 Qualified, experienced staff
 Expensive
UV Vis – Spectroscopy
Cr(VI) analysis - Solution based analysis
 Simple, well established technique
 Not expensive
 Traceable, certified solution standards available
 IEC recommended technique (RoHS Directive)
 Sample Preparation required (destructive and
time consuming)
 Unstable analyte
 Matrix tolerance
 Dedicated laboratory
 Qualified, experienced staff
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Ion Chromatography
Cr(VI) analysis - Solution based analysis
 Established technique
 Traceable, certified solution standards
available
 Sample Preparation required (destructive
and time consuming)
 Unstable analyte
 Matrix tolerant
 Dedicated laboratory
 Very low LODs
 Qualified, experienced staff
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Hg analysis
(Solution based analysis)
• Cold Vapor Atomic Absorption (CVAAS)
• Cold Vapor Atomic Fluorescence (CVAF)
• Hydride Generation ICP-OES
• Direct Mercury Analyzer (DMA)
 Excellent sensitivity
 Traceable, certified solution standards
available
 Established techniques
 Sample preparation generally required
(destructive and time consuming)
 Dedicated laboratory
 Specialized technique
 Qualified, experienced staff
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Typical Equipment employed
for SOC Testing
Solid sample analysis:
- Minimal sample preparation required:
ED-XRF
Energy Dispersive X-Ray Fluorescence Spectroscopy
- Some sample preparation required:
WD-XRF
Wavelength Dispersive X-Ray Fluorescence Spectroscopy
GD-OES
Glow Discharge Optical Emission Spectroscopy
Solution based analysis:
AAS
Atomic Absorption Spectroscopy
ICP-OES
Inductively Coupled Plasma Optical Emission Spectroscopy
UV-Vis
Ultra-Violet Visible Spectroscopy
IC
Ion Chromatography
CV-AAS
Cold Vapor Atomic Absorption Spectroscopy
HG-ICPOES
Hydride Generation ICP-OES
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Calibration Standards and
Certified Reference Materials
Requirements:
- Accredited or reputable manufacturer
- SI traceable (mole, gram)
- Uncertainty of measurement
- Matrix (e.g. plastic, metal)
- Concentration levels
Examples of Reference Materials’ Suppliers:
- Industrial Analytical (local)
- Merck (local)
- JFJ Industries (local)
- COMAR (European Database)
- NIST (USA)
- Equipment Suppliers (traceablity)
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Summary: SOC testing
Representative, homogeneous
sample
ED-XRF Screening
ELV
Non-Compliant
> 125 ppm Cd
< 75 ppm Cd
> 1250 ppm Hg, Pb
< 750 ppm Cr, Hg, Pb
Cd: 75 – 125 ppm
Hg and Pb: 750 – 1250 ppm
Cr > 750 ppm
Accurate Verification Test
Cd, Pb:
Hg:
Cr(VI):
• ED-XRF
• CVAAS
• UV-Vis
• WD-XRF
• CVAF
• IC
• AAS
• ICP-OES
• ICP-OES
• HG-ICP-OES
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ELV Compliant
Developing an In-house Analytical Method
 Instrument selection:
• Screening vs Accurate analysis
• Detection limit of system vs. legislative limits (LOD vs. LOQ)
 Sample preparation:
• Special facilities
• Additional equipment
 Instrument calibration:
• Fundamental Principals / Calibration standards
• Working Range vs. Sample Concentration
• Certified Reference Materials (calibration / verification)
 Experienced Staff
 ISO 17025 Accreditation
 Cost
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Outsourcing Analyses
 Laboratory accredited to ISO 17025 (www.sanas.co.za)
Accreditation Scope:
• Cd, Cr(VI), Hg and Pb
• Matrix (plastics, metals, etc.)
• Concentration levels
• Analytical techniques
 Quality assurance when laboratory is not accredited:
• Submit Reference Standard (i.e. known concentration)
• Submit sample in duplicate
• Analysis by different techniques / laboratories
NOTE: Homogeneity of sample is critical
 Turn-around times
 Cost
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Interpretation of Results
 Certificate of Analysis:
Concentration ± Uncertainty (Unit); k = 2 at a level of
confidence of 95%
 ELV Compliance:
Concentration + Uncertainty < ELV limit
Concentration (mg/kg)
1400
1200
1000
800
600
Verify
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Fail
Pass
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Verify
Pass
Verify
Fail
NML Project : Meeting the SOC demands of
the ELV Directive
 NLA-Database: South African laboratories
• Contact persons
• Accreditation / Experience
- Matrix (plastics, metals, etc.)
- Techniques available (XRF, ICP, etc.)
- Concentration levels (major, minor, trace)
 Certified Reference Materials (CRMs)
• Identify which materials are available
• Calibration materials supplied by instrument manufacturers: SI traceability
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NML Project : Meeting the SOC-demands of
the ELV-Directive (2)
 Consultation:
• Assess current situation
• Assisting with development of in-house analytical capabilities
• Assisting with ISO 17025 accreditation
 Evaluation of analytical techniques available at the NML:
 GD-OES
 UV-Vis
 FT-IR
 WD-XRF
 ICP-OES
 TGA-MS
 LA-ICP-MS
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To Conclude



Analytical Techniques
•
Screening vs. Quantitative Approach (e.g. EDXRF vs. ICP-OES)
•
Sample preparation
Calibration standards
•
SI traceable
•
Matrix matched
•
Reputable manufacturer
Laboratories
•
Experienced vs ISO 17025-accreditation
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NML Contacts
Maré Linsky
Tel:
(012) 841-3974
e-mail:
[email protected]
Retha Rossouw
Tel:
(012) 841-2607
e-mail:
[email protected]
Copyright © CSIR
2005
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Summary: Analytical Techniques
Sample
Prep
Required?
Screening
Quantitative
LOD
(ppm)
Skill of
Operator
Cost
ED-XRF
~


ppm
Medium
$$
WD-XRF
~
~

ppm
Med-High
$$$
AAS



ppm
Med-High
$$
ICP-OES



ppb
High
$$$
GF-AAS



ppb
High
$$
CV-AAS



ppb
Med-High
$$
HG-ICPOES



ppb
High
$$$
GD-OES
~
~
~
ppm
Med-High
$$$
UV-Vis



ppm
Medium
$$
IC



ppm
High
$$
Technique
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Instrument Manufacturers
•
Bruker AXS
•
CETAC
•
Horiba Jobin Yvon (Wirsam Scientific)
•
Milestone (Apollo Scientific)
•
Oxford Instruments (SMM Instruments)
•
PANalytical
•
Spectro Analytical Instruments
•
Shimadzu (LabWorld)
•
Thermo Electron Corporation
•
Varian (SMM Instruments)
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