1. Copyright © CSIR 2005 www.csir.co.za Meeting the requirements of the ELV Directive: Measurement of Substances of Concern (SOCs) Maré Linsky and Retha Rossouw National Metrology Laboratory

2. Copyright © CSIR 2005 www.csir.co.za Overview  European Union Directives  Analytical Techniques  Developing an In-house Analyses Method  Outsourcing Analyses  National Metrology Laboratory

3. Copyright © CSIR 2005 www.csir.co.za 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

4. Copyright © CSIR 2005 www.csir.co.za Typical applications of SOCs (functional vs contaminant) Cadmium [Cd]: - Pigments and stabilizers in plastics - NiCd Batteries (exempt until Dec ‘08) Mercury [Hg]: - Batteries - 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 Lead [Pb]: - Pigments in paint - Minor element in steels, aluminium - Stabilizers and pigments in PVC - Batteries (to be labeled)

5. Copyright © CSIR 2005 www.csir.co.za European Union End-of-Life Vehicles (ELV) Directive 2000/53EC EU Directive Maximum limits (%) * CdCr(VI)HgPb ELV Directive ** 0,010,10 WEEE and RoHS Directives 0,010,10 * 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

6. Copyright © CSIR 2005 www.csir.co.za Recommended SOC testing scheme Representative, homogeneous sample ED-XRF Screening > 125 ppm Cd > 1250 ppm Hg, Pb < 75 ppm Cd < 750 ppm Cr, Hg, Pb Accurate Verification Test Cd, Pb: ED-XRF WD-XRF AAS ICP-OES ELV Non-Compliant ELV Compliant Cd: 75 – 125 ppm Hg, Pb: 750 – 1250 ppm Cr > 750 ppm Hg: CVAAS CVAF ICP-OES HG-ICP-OES Cr(VI): UV-Vis IC

7. Copyright © CSIR 2005 www.csir.co.za 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)

8. Copyright © CSIR 2005 www.csir.co.za EDXRF (Solid with sample preparation) Fast (Non)-destructive Sample Area Good precision, accuracy Fair sensitivity Multi-element analysis  Generally not portable  Some sample preparation required  Experienced staff  Moderately expensive  Calibration Standards and Certified Reference Materials (CRM)

9. Copyright © CSIR 2005 www.csir.co.za EDXRF (Solid – Minimal preparation) Simple, fast Non-destructive No sample preparation Sample Area (some control) Good precision, accuracy Multi-element analyses  Generally not portable  Fair sensitivity (poor excitation due to low tube voltage)  Moderately expensive  Calibration Standards and Certified Reference Materials (CRM)

10. Copyright © CSIR 2005 www.csir.co.za Handheld EDXRF – Instruments (Solid – No preparation) Portable, flexible Simple, fast Non-destructive No sample preparation Multi-element analysis Inexpensive  Sample Area (large, difficult to control)  Poor reproducibility, accuracy  Poor sensitivity (poor excitation due to low tube voltage)  Instrument Calibration  Safety

11. Copyright © CSIR 2005 www.csir.co.za GDOES (Solid with minimal preparation) Small sample area Analysis of sample layers Good precision and long term stability Good sensitivity and accuracy Multi-element analysis  Only conducting samples  Flat surface areas  Some sample preparation  Qualified, experienced staff  Calibration Standards and Certified Reference Materials (CRM)  Expensive

12. Copyright © CSIR 2005 www.csir.co.za AAS (Solution based analysis) Simple, well established technique Not expensive Matrix tolerant Traceable, certified solution standards available  Sample Preparation required (destructive)  Dedicated laboratory  Qualified, experienced staff  Sequential technique (mostly)  Narrow working range  LODs

13. Copyright © CSIR 2005 www.csir.co.za ICP-OES (Solution based analysis) Excellent Accuracy, Precision Excellent Sensitivity (low LOD) Matrix tolerant Traceable, certified standard solutions available Multi-element analysis  Sample Preparation required (destructive and time consuming)  Dedicated laboratory  Qualified, experienced staff  Expensive

14. Copyright © CSIR 2005 www.csir.co.za 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

15. Copyright © CSIR 2005 www.csir.co.za Ion Chromatography Cr(VI) analysis - Solution based analysis Established technique Traceable, certified solution standards available Matrix tolerant Very low LODs  Sample Preparation required (destructive and time consuming)  Unstable analyte  Dedicated laboratory  Qualified, experienced staff

16. Copyright © CSIR 2005 www.csir.co.za 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

17. Copyright © CSIR 2005 www.csir.co.za 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: AASAtomic 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

18. Copyright © CSIR 2005 www.csir.co.za 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)

19. Copyright © CSIR 2005 www.csir.co.za Summary: SOC testing Representative, homogeneous sample ED-XRF Screening > 125 ppm Cd > 1250 ppm Hg, Pb < 75 ppm Cd < 750 ppm Cr, Hg, Pb Accurate Verification Test Cd, Pb: ED-XRF WD-XRF AAS ICP-OES Hg: CVAAS CVAF ICP-OES HG-ICP-OES Cr(VI): UV-Vis IC ELV Non-Compliant ELV Compliant Cd: 75 – 125 ppm Hg and Pb: 750 – 1250 ppm Cr > 750 ppm

20. Copyright © CSIR 2005 www.csir.co.za 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

21. Copyright © CSIR 2005 www.csir.co.za 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

22. Copyright © CSIR 2005 www.csir.co.za Interpretation of Results  Certificate of Analysis: Concentration ± Uncertainty (Unit); k = 2 at a level of confidence of 95%  ELV Compliance: Concentration + Uncertainty < ELV limit

23. Copyright © CSIR 2005 www.csir.co.za 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

24. Copyright © CSIR 2005 www.csir.co.za 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

25. Copyright © CSIR 2005 www.csir.co.za 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

26. Copyright © CSIR 2005 www.csir.co.za NML Contacts Maré Linsky Tel:(012) 841-3974 e-mail:mlinsky@csir.co.za Retha Rossouw Tel:(012) 841-2607 e-mail:rrossouw@csir.co.za

27. Copyright © CSIR 2005 www.csir.co.za Summary: Analytical Techniques Technique Sample Prep Required? ScreeningQuantitative LOD (ppm) Skill of Operator Cost ED-XRF ~  ppmMedium$$ WD-XRF ~~  ppmMed-High$$$ AAS  ppmMed-High$$ ICP-OES  ppbHigh$$$ GF-AAS  ppbHigh$$ CV-AAS  ppbMed-High$$ HG-ICP- OES  ppbHigh$$$ GD-OES ~~~ ppmMed-High$$$ UV-Vis  ppmMedium$$ IC  ppmHigh$$

28. Copyright © CSIR 2005 www.csir.co.za 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)