Meeting the requirements of the ELV Directive: Measurement of Substances of Concern (SOCs)

1
Meeting the requirements of the ELV Directive
Measurement of Substances of Concern (SOCs)

• Maré Linsky and Retha Rossouw

National Metrology Laboratory
2
Overview

• European Union Directives
• Analytical Techniques
• Developing an In-house Analyses Method
• Outsourcing Analyses
• National Metrology Laboratory

3
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
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
European Union End-of-Life Vehicles (ELV)
Directive 2000/53EC
EU Directive Maximum limits () Maximum limits () Maximum limits () 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

6
Recommended SOC testing scheme
Representative, homogeneous sample
ED-XRF Screening
gt 125 ppm Cd gt 1250 ppm Hg, Pb
lt 75 ppm Cd lt 750 ppm Cr, Hg, Pb
ELV Non-Compliant
ELV Compliant
Cd 75 125 ppm Hg, Pb 750 1250 ppm Cr gt
750 ppm
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

7
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
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
EDXRF (Solid Minimal preparation)

• Generally not portable
• Fair sensitivity (poor excitation due to low
  tube voltage)
• Moderately expensive
• Calibration Standards and Certified Reference
  Materials (CRM)

• Simple, fast
• Non-destructive
• No sample preparation
• Sample Area (some control)
• Good precision, accuracy
• Multi-element analyses

10
Handheld EDXRF Instruments (Solid No
preparation)

• Sample Area (large, difficult to control)
• Poor reproducibility, accuracy
• Poor sensitivity (poor excitation due to low
  tube voltage)
• Instrument Calibration
• Safety

• Portable, flexible
• Simple, fast
• Non-destructive
• No sample preparation
• Multi-element analysis
• Inexpensive

11
GDOES (Solid with minimal preparation)

• Only conducting samples
• Flat surface areas
• Some sample preparation
• Qualified, experienced staff
• Calibration Standards and Certified Reference
  Materials (CRM)
• Expensive

• Small sample area
• Analysis of sample layers
• Good precision and long term stability
• Good sensitivity and accuracy
• Multi-element analysis

12
AAS(Solution based analysis)

• Sample Preparation required (destructive)
• Dedicated laboratory
• Qualified, experienced staff
• Sequential technique (mostly)
• Narrow working range
• LODs

• Simple, well established technique
• Not expensive
• Matrix tolerant
• Traceable, certified solution standards available

13
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
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
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
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
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

18
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
Summary SOC testing
Representative, homogeneous sample
ED-XRF Screening
gt 125 ppm Cd gt 1250 ppm Hg, Pb
lt 75 ppm Cd lt 750 ppm Cr, Hg, Pb
ELV Non-Compliant
ELV Compliant
Cd 75 125 ppm Hg and Pb 750 1250 ppm Cr gt
750 ppm
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

20
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
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
Interpretation of Results

• Certificate of Analysis
• Concentration Uncertainty (Unit) k 2 at a
  level of confidence of 95
• ELV Compliance
• Concentration Uncertainty lt ELV limit

23
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
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
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
NML Contacts
Maré Linsky Tel [phone] e-mail mlinsky
_at_csir.co.za Retha Rossouw Tel (012)
841-2607 e-mail rrossouw_at_csir.co.za
27
Summary Analytical Techniques
Technique 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-ICP-OES ? ? ? ppb High
GD-OES ppm Med-High
UV-Vis ? ? ? ppm Medium
IC ? ? ? ppm High
28
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)