QUALITY OF AIR PROTECTION 2008 Workshop –for West Balkan contries Importance of National References Laboratories for Air Quality role on the AQ/AC chain Jiri Novak Head of Central Laboratories for Ambient Air, Czech Republic

Contents Introduction - Legislation QA - Quality Assurance QC - Quality Control ISO IEC 17025:2005 Traceabilty chain National Reference Laboratory/Competent Authority/ associated laboratory of National Metrology Institute AQUILA Recomendations to NRL´s

Introduction On the tasks specified for the Competent Authority(CA)/National Reference Laboratory in the proposed Directive on the AAQ and CA for Europe: Article 3 point(c.): MS shall designate at the appropriate levels the CA and bodies(NRL) for the following: Ensuring the accuracy of measurements-in the context of DQO where relevant,the CA/NRL and bodies shall comply with Section C of Annex I. Annex 1 Section C. - CA/NRL shall ensure following: all measurement undertaken in relation to the assesment of AAQ pursuant to Art. 6 and 9 are traceable in accordance with

Introduction – cont. with the requirements set out in section of the ISO/IEC 17025:2005 Institutions operating networks and individual stations have an established QA/QC system CA/NRL – taking part in Community-wide intrecomparisions covering pollutants regulated in this Directive, are accredited according to EN/ISO by 2010 for the reference methods referred in AnnexVI. CA can be designated at the political level, but national laboratories or NRL are designated at the technical level (this distinction is not clear in the proposed Directive)

Quality Assurance(QA) General Principle of QA ISO defines QA as follows Quality Assurance – all planned and systematic actions necessary to provide confidence that a product, process or service will satisfy given requirements for quality - QA refers to the overall managment of the process involved in obtaining the data–i.e QA relates to measuring process, therefore QA activities for AQ monitoring networks might include: - Network design - Station siting - Instrument selection - Instrument service and repair

QA – cont. - Operationl manual - Instrument calibration (Calibration Laboratory/NRL) - Site, analyser and calibration audit (CA/NRL) In theory, if all of the QA activities are undertaken correctly and in compliance with relevant CEN standard and detailed local operating procedures at all times, then there is an expection that the measurements will fulfil the requirements of the EU Directives without other checking. Ongoing QA: - Calibration of analyser (at least every 6 months) - Certification of test gases ( at least every 6 months)

QA – cont. - Zero/Span check (at least every two weeks – better 23 hours) - Lack of fit (linearity) check (every year + after repair) - Convertor efficiency for NOx analysers (at least every year) - Test sample manifold (at least every 3-years) - Change particulate filter (at least every 3-months – maybe 2 weeks for very polluted stations!!) - Test sample lines (at least every 6-months) - Regular analyser maintenance (as required) The CA/NRL needs to ensure that procedures are in place for the these on-going QA check and that results are documented and any necessary remedial action taken.

Quality Control(QC) General Principle of QC ISO defines QC as follow Quality Control – operational techniques and activities that are used to fulfil given requirements for quality QC activities could include: - Data checking (Data ratification – Plausibility check) - Quality review and feedback - Uncertainty requirements ( QC refers to the activities undertaken to check and optimise data accuracy and precision after collectioon – is concerned primarily with outputs)

Appendix – CEN Standard Method SO2 EN 14212:2005 NOx,NO EN 14211:2005 PM10 EN 12341:1999 PM2.5 EN 14907:2005 Benzene EN 12622:2005 CO EN 14626:2005, Ozone EN 14625:2005 The CEN standard methods for gaseous pollutants provide details of the reference method of measurement for each pollutant, specific analyser tests to be performed and requirements for on-going QA/QC of analyser. These standards provide a methodology for uncertainty evalution to enable measurement uncertainty to be directly compared with specified DQO.

ISO IEC 17025:2005 Chapter Specific requirements Calibration ….that calibrations and measurements made by the laboratory are traceable to System of Units (SI) for gases – mass (mol) AND A Calibration laboratory established traceability of its own measurement standards and measuring instruments to the SI by means of an unbroken chain of calibrations or comparisons linking them to relevant primary standard (for gases Primary Reference Material – PRM) of the SI units of measurement. To link to SI units may be achieved by reference to national measurements standards. (ozone is exception – reference to Standard Reference Photometer)

Scheme of traceability chain Example of traceabilty chain Calibration Laboratory/National Reference Laboratory/associated laboratory of National Metrology Institute - Czech Republic Primary Reference Material (PRM) – NMi,NPL gases – SO2, NO, CO,BTX - VOC) (Certificated Reference Material – CRM for HM, PAH) Standard Reference Photometer (SRP) for ozone measurement

Scheme of traceability chain

Pracovní etalon – analyzátor (PE-A) KLI Working etalon - analyzer Provozní měřidlo – analyzátor AMS Operational analyzer Pracovní etalon - analyzátor (PE-A) Pob lab. Working etalon – analyzer Regional laboratory Pobočková laboratoř, AMS Regional laboratory Kalibrační laboratoř imisí - KLI Calibration laboratory Pracovní etalon – analyzátor (PE-A) KLI Working etalon - analyzer Standardní referenční fotometr ozónu (SRP) KLI Standard Reference Photometer for ozone measurement kalibrační kontrola Calibration check A), B) Multipoint calibration (4-5 point) vícebodová kalibrace (4-5 bodů) A)-nastavení měřícího rozpětí dle ČSN EN – 9.5. Zero/span check B) –ověření linearity dle ČSN EN – Linearity check Scheme for Ozone

Calibration Laboratory/National Reference Laboratory - Summary Traceability to SI unit PRM Dilution units - Static or Dynamic units Working etalon - analysers - gas cylinders Standard Reference Photometer for ozone measurement

Working etalon + dynamic dilution unit

Working etalon, analysers + gas cylinders

Dilution unit – Static manometric injection

Dilution unit – Static manometric injection- PRM

Standard Reference Photometer –SRP No.17, NIST

AQUILA There is association of National Reference Laboratories - AQUILA Air Quality National Reference Laboraqtories Meetings cca 2 times per year – JRC Ispra Italy min.50% of time – discussion for QA/QC system-program in EU including Directive, Daugter Directive, tests etc.

Recomendation to NRL´s 1. Ensure that number, distribution and siting of monitoring stations in monitoring network conforms to the Directive requirements 2. Any new analysers purchased to networks used for demonstrating Directive compliance should by type tested to the appropriate CEN procedure – all analysers used in monitoring networks need to be replaced with type tested analysers within 5 years of the implementation of the Directive 3. CEN QA/QC procedures need to be introduced into the monitoring networks 4. Data uncertainties need to be calculated by the CEN methodology for every analyser, every year 5. Obtain the appropriate ISO accreditation 6. Participate in the appropriate EU Commmunity-wide QA programmes 7 Examine and review procedures and quality issues on a regular basis to adapt and improve

Recomendations to NRL´s – cont. 8. Ensure that documented QA procedures (SOP) are in place for all insitutions operating networks and individual stations within the MS 9. Where equivalent analysers are used, ensure that correct procedures have been followed for the demonstration of equivalence and that a report has been supplied to the Commission for approval 10. Ensure that all data reported to the Commission comply with the Directive requirements and the recomendations of the Data Exchange Group.