DISCUSSION OF IEC TC111 IEC STANDARD 62321 AND John Sieber Research Chemist Inorganic Chemical Metrology Group john.sieber@nist.gov 301-975-3920 January 13, 2009

IEC TC111 – Standards for Sampling and Analysis IEC 62321 Ed.1 (WG3) - Procedures for the Determination of Levels of Regulated Substances in Electrotechnical Products, Published 2008-12-11. IEC 62596 Ed.1/PAS (HWG3) - Electrotechnical products – Guideline for the sampling procedure for the determination of restricted substances, Publication imminent.

The TC111 Approach TC111 generally follows a “Top Down” Supply Chain Approach WG1 - Materials Declaration WG2 - Environmentally Conscious Design WG3 - Determination of Regulated Substances in Electrotechnical Products Ad Hoc Working Groups and Project Teams HWG 3 - Sample Disjointment PT 62476 - Guidance for Assessing Products’ Conformity PT 62542 - Standardization of Environmental Aspects – Glossary of Terms HWG4 - Recycling, Reuse and Recovery

Are There Requirements? IEC 62321 is an independent standard. It does not require use of other IEC standards. Choose the appropriate standards for your needs. In theory, IEC TC111 standards are voluntary. Companies may choose to use standard test methods and standard guides from other SDOs. Laboratories must document that their implementation of the standard test method has been validated and is under statistical control. Choices and actions are subject to requirements of contractual agreements. Participation in the process.

IEC 62321 Normative Chapters 1 Scope Normative references ISO/IEC Guide 98:1995, ISO Guide to the expression of uncertainty in measurement (GUM) ISO 3696, Water for analytical laboratory use – Specification and test methods ISO 5961, Water quality – Determination of cadmium by atomic absorption spectrometry ISO 17025, General requirements for the competence of testing and calibration laboratories Terms, definitions and abbreviations Notes: Results must be expressed in SI units with uncertainty estimates. Laboratories must comply with ISO 17025 by validating their implementation of each test method.

IEC 62321 Normative Chapters Test methods – Overview 4.1 Field of application 4.2 Sample 4.3 Test methods flow chart 4.4 Adjustment to the matrix 4.5 Limits of detection and quantification 4.6 Test report 4.7 Alternative test methods Alternative test methods, digestion methods or analytical techniques may be used once the performance effectiveness has been validated according to the performance-based measurement system (PBMS) criteria referenced in the quality control clauses of the test methods. Any deviation from the described test methods shall be evaluated and documented in the test report.

4.3 Flow Chart for Planning Testing of a Sample - This is an “entity-based” decision process. - Each organization must decide how to sample a product and how to test each sample. - Both IEC TC111 and ASTM F40 recognize that guidance is needed. - Some enforcement bodies recognize that guidance and cooperation are essential.

IEC 62321 Normative Chapters Mechanical sample preparation This clause describes common techniques for mechanical size reduction of electrotechnical products, their sub-units or portions thereof, prior to analysis for regulated substances. The test method clauses in this standard have requirements for sample handling and preparation in specific situations. This clause provides general guidance on processing selected portions of an item. The user may elect to apply one or more of the approaches described in this clause to create samples to be submitted for testing. Selection of the appropriate technique(s) depends on the required particle size for the test method to be used. Alternative methods of mechanical sample preparation can be used provided that the required particle size of the sample is achieved without contaminating or compromising the sample with regulated substances. This chapter does not appear to be normative. Notice underlined statements. 62596/PAS has been developed to address the need for guidance on sampling and sample preparation. JRS

IEC 62321 Normative Chapters Screening by X-ray fluorescence spectrometry (XRF) Supported by Informative Annex D Practical application of screening by X-ray fluorescence spectrometry (XRF) Annex D provides detailed discussions of matrix and interference effects, guidance for interpretation of results, and a close look at validation results. These substances in similar media outside of the specified concentration ranges may be analysed according to this test method; however, the performance has not been established for this standard. The XRF technique covers handheld, benchtop, and research grade instruments of both EDXRF and WDXRF designs.

IEC 62321 Normative Chapters Determination of mercury in polymers, metals and electronics by CV-AAS, CVAFS, ICP-OES and ICP-MS Supported by Informative Annex E Practical application of determination of mercury in polymers, metals and electronics by CV-AAS, CV-AFS, ICP-OES and ICP-MS Options are given for sample digestion (hot plate or microwave). Calibration procedures and calculations are specified. Annex E is a brief look at a piece of equipment and examples for instrument conditions. Volunteer laboratories...participated in an international interlaboratory study to determine whether the procedures yield replicable (and reliable) results. Four certified reference materials were given to different laboratories to determine Hg. The ratio between the assigned value and the determined value was between 90 % and 97 %. Detailed results are listed in Table 8. Remarks on limits of detection and limits of quantification are given in Clause 4. ALL VALIDATION CRMS WERE PLASTIC. THE METHOD HAS NOT BEEN VALIDATED BY TC111 FOR ADDITIONAL MATERIALS.

IEC 62321 Normative Chapters Determination of lead and cadmium in polymers by ICP-OES, ICP-MS and AAS Determination of lead and cadmium in metals by ICP-OES, ICP-MS and AAS Determination of lead and cadmium in electronics by ICP-OES, ICP-MS and AAS Supported by Informative annexes Annex F Practical application of determination of lead and cadmium in polymers by ICP-OES, ICP-MS & AAS Annex G Practical application of determination of lead and cadmium in metals by Annex H Practical application of determination of lead and cadmium in electronics by Each chapter has options for sample digestion and measurement with specified calibration and calculation procedures. Validation results showed quantitative performance for each matrix.

IEC 62321 Informative Annexes Annex A Determination of PBB and PBDE in polymers by GC-MS This annex specifies a gas chromatography-mass spectrometry (GC-MS) test method for the determination of monobrominated to decabrominated biphenyls (PBB) and monobrominated to decabrominated diphenyl ethers (PBDE) in polymers of electrotechnical products having PBB and PBDE contents in the range of 100 mg/kg to 2 000 mg/kg and as high as 100 000 mg/kg for decaBDE. PBB and PBDE compounds are determined using Soxhlet extraction of the polymer with separation by gas chromatography-mass spectrometry (GC-MS) using single ion monitoring (SIM). NOTE For informative purposes, the test method has also been developed in order to allow the detection and quantification of decaBDE (BDE-209). It is, however, important to remember that decaBDE is not regulated. This method was made informative in part because it was somewhat controversial (negative votes and decaBDE) and in part because it could not be validated by enough labs (recovery issues). Development efforts continue. JRS

IEC 62321 Informative Annexes Annex B Test for the presence of hexavalent chromium (Cr(VI)) in colourless and coloured corrosion-protected coatings on metals Annex C Determination of hexavalent chromium (Cr(VI)) in polymers and electronics by the colorimetric method Annex B is qualitative determination of the presence of Cr(VI) in colourless and coloured corrosion-protection coatings on metallic samples. Annex C is quantitative determination of Cr(VI) in polymers and electronic components. The method uses alkaline digestion procedures to extract Cr(VI). Both methods use colorimetric measurements after reaction of Cr(VI) in solution with 1,5-diphenylcarbazide. These methods were made informative in part because they were somewhat controversial (negative votes) and in part because there was debate about the validation studies. Development efforts continue. JRS

Future Activities and Objectives Tasks for 2009-2010: 1. Split 62321 into a family of “parts” 2. Incorporate PAS 62596 3. Improve BFR and Cr+6 methods Chapters 1 - 4 and References, S. MacLeod (UL) & J. Zietlow (Sony) Merge Chapter 5 Mechanical sample preparation with IEC 62596 Ed.1/PAS Guidelines for sampling procedures, M. Ten Houten Chapter 6 Screening S. Piorek (ThermoFisher) Chapter 7 Mercury M. Takenaka (Toshiba) Chapters 8 - 10 Lead & Cadmium, K. Budde (Siemens) & J. Zietlow Annex A PBB & PBDE S. MacLeod Annexes B & C Hexavalent Chromium, S. Lau (IBM) Interlaboratory Studies, H. Hinrichs (Bureau Veritas)