Copyright © CSIR Meeting the requirements of the ELV Directive: Measurement of Substances of Concern (SOCs) Maré Linsky and Retha Rossouw National Metrology Laboratory

Copyright © CSIR Overview  European Union Directives  Analytical Techniques  Developing an In-house Analyses Method  Outsourcing Analyses  National Metrology Laboratory

Copyright © CSIR 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

Copyright © CSIR 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)

Copyright © CSIR 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

Copyright © CSIR 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

Copyright © CSIR 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)

Copyright © CSIR 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)

Copyright © CSIR 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)

Copyright © CSIR 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

Copyright © CSIR 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

Copyright © CSIR 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

Copyright © CSIR 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

Copyright © CSIR 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

Copyright © CSIR 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

Copyright © CSIR 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

Copyright © CSIR 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

Copyright © CSIR 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)

Copyright © CSIR 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

Copyright © CSIR 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 Accreditation  Cost

Copyright © CSIR Outsourcing Analyses  Laboratory accredited to ISO ( 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

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

Copyright © CSIR 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

Copyright © CSIR 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 accreditation  Evaluation of analytical techniques available at the NML:  GD-OES  UV-Vis  FT-IR  WD-XRF  ICP-OES  TGA-MS  LA-ICP-MS

Copyright © CSIR 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 accreditation

Copyright © CSIR NML Contacts Maré Linsky Tel:(012) Retha Rossouw Tel:(012)

Copyright © CSIR 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$$ IC  ppmHigh$$

Copyright © CSIR 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)