copyright © csir 2005 meeting the requirements of the elv directive: measurement of substances of...

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


Overview

European Union Directives

Analytical Techniques

Developing an In-house Analyses Method

Outsourcing Analyses

National Metrology Laboratory


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


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)


European Union End-of-Life Vehicles (ELV) Directive 2000/53EC

EU Directive Maximum limits (%) *

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


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 ppmHg, Pb: 750 – 1250 ppmCr > 750 ppm

Hg:

• CVAAS

• CVAF

• ICP-OES

• HG-ICP-OES

Cr(VI):

• UV-Vis

• IC


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)


EDXRF (Solid with sample preparation)

Fast

(Non)-destructive

Sample Area

Good precision, accuracy

Fair sensitivity


Generally not portable

Some sample preparation required

Experienced staff

Moderately expensive



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



Handheld EDXRF – Instruments (Solid – No preparation)

Portable, flexible

Simple, fast

Non-destructive

No sample preparation


Inexpensive

Sample Area (large, difficult to control)

Poor reproducibility, accuracy

Poor sensitivity (poor excitation due to low tube voltage)

Instrument Calibration

Safety


GDOES (Solid with minimal preparation)

Small sample area

Analysis of sample layers

Good precision and long term stability

Good sensitivity and accuracy


Only conducting samples

Flat surface areas

Some sample preparation

Qualified, experienced staff


Expensive


AAS(Solution based analysis)

Simple, well established technique

Not expensive

Matrix tolerant

Traceable, certified solution standards available

Sample Preparation required (destructive)

Dedicated laboratory


Sequential technique (mostly)

Narrow working range

LODs


ICP-OES (Solution based analysis)

Excellent Accuracy, Precision

Excellent Sensitivity (low LOD)

Matrix tolerant

Traceable, certified standard solutions available


Sample Preparation required (destructive and time consuming)



Expensive


UV Vis – Spectroscopy Cr(VI) analysis - Solution based analysis

Simple, well established technique

Not expensive


IEC recommended technique (RoHS Directive)


Unstable analyte

Matrix tolerance




Ion Chromatography Cr(VI) analysis - Solution based analysis

Established technique


Matrix tolerant

Very low LODs


Unstable analyte




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


Established techniques

Sample preparation generally required (destructive and time consuming)


Specialized technique



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


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)


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 ppmHg and Pb: 750 – 1250 ppmCr > 750 ppm


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


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


Interpretation of Results

Certificate of Analysis:

Concentration ± Uncertainty (Unit); k = 2 at a level of confidence of 95%

ELV Compliance:

Concentration + Uncertainty < ELV limit

600

800

1000

1200

1400

Verify Fail Pass Verify Pass Verify Fail

Co

nce

ntr

atio

n (

mg

/kg

)


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


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


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


NML Contacts

Maré Linsky

Tel: (012) 841-3974

e-mail: [email protected]

Retha Rossouw

Tel: (012) 841-2607

e-mail: [email protected]


Summary: Analytical Techniques

TechniqueSample

Prep Required?

Screening QuantitativeLOD

(ppm)Skill of

OperatorCost

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 $$


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)

copyright © csir 2005 meeting the requirements of the elv directive: measurement of substances of...

Documents