Inter laboratory comparisons for sulphur dioxide in nitrogen for ambient air and stack gas emission monitoring.

Transcription

1 Inter laboratory comparisons for sulphur dioxide in nitrogen for ambient air and stack gas emission monitoring. James Tshilongo 20 September 2011, T & M Workshop

2 Overview Gas Metrology. Regulatory. Gas Metrology of South Africa. Preparation strategy. International measurement equivalence. Why Regional Comparison is important Comparison with local industry (Gas Suppliers) Background of SO 2 Comparison Proposed Schedule for Two Comparison. Price for participation Coordinating Laboratory

3 Gas Metrology Stable CO, CO 2, O 2, propane Natural gas (CH 4 ) Partially stable SO 2, NO, NO 2, H 2 S, VOCs and H 2 O Unstable HCl, NH 3, Ozone, Formaldehyde

4 Gases Stable CO, CO 2, O 2, propane Natural gas (CH 4 ) Stable in Cylinders Partially stable SO 2, NO, NO 2, H 2 S, VOCs and H 2 O Stable in Cylinders at High Concentrations Unstable HCl, NH 3, Ozone, Formaldehyde Dynamic Methods

5 Industry sector Green House Gases (GHG s) Air pollution

6 Performance environment (Regulatory) The Kyoto Protocol for reducing greenhouse gas (GHG) emissions; South Africa acceded to the Kyoto protocol in mid 2002 The National Air Quality Act No. 39 of 2004 The Stockholm convention (a global treaty to protect human health and the environment); SA signed this treaty in 2001 Countries and trade regions impose regulations and directives to trade goods, protect the health of their people and the environment; Stricter legislation and the initiation of environmental programs are being applied globally

7 Gas Metrology Laboratory of the NMISA The NMISA is mandated to provide measurement traceability for air pollution monitoring in South Africa. NMISA has been identified by the Department of Environmental Affairs to host the National Reference Laboratory (NRL) for Air Quality Management.

8 Gas Metrology Laboratory Preparation and certification of Primary Reference Gas Mixtures (stack gas emissions, automotive exhaust emissions, ambient air monitoring) Calibration of breathalysers, & air pollution analysers Purity Analysis Multi-component & Condensable gas mixtures

9 PREPARATION STRATEGY OF GAS STANDARDS Pure Gases/Liquids (Purity Analysis) Gravimetric Preparation (ISO 6142:2001) Verification of Primary Standard Gas Materials (PSMs) vs Other NMIs Mixtures (ISO 6143) Verification of Primary References Gas Materials (PRGMs) vs PSMs NMISA Certificates (PRGMs)

10 Gas Metrology Laboratory of the NMISA The NMISA is mandated to provide measurement traceability for air pollution monitoring in South Africa. NMISA has been identified by the Department of Environmental Affairs in South Africa to host the National Reference Laboratory (NRL) for Air Quality Management. NMISA (Gas metrology Lab) has participated in various International Key Comparisons.

11 WHAT IS THE NEXT STEP!!!!! Key Comparison with Other NMI s around the WORLD

12 Establishing international measurement equivalence for gas metrology in SA In the beginning CCQM-K3. EUROMET.QM-K3, APMP.QM-K3 CCQM-K4, APMP.QM- K4, EUROMET. QM-K4 Today EURO.QM-K4.1 EURO.QM-S4 CCQM-K52 CCQM-K53 CCQM-K51

13 CCQM-K3: Automotive emission gases

14 CCQM-K3: Automotive emission gases

15 CCQM-K4: Ethanol in air

16 EURO.QM-K4.1: 120 µmol/mol Ethanol in air Euramet.QM-K4.1 Ethanol in Nitrogen Equivalence Degrees of CEM INMETRO NMISA NPL VNIIM VSL Laboratory

17 EURO.QM-S4: Preparative study for automotive exhaust emissions ivalence (mmol mol -1 ) Degree of equi IPQ INMETRO VSL L a b o r a to r y NMISA SMU CO results 2 % mol/mol

18 EURO.QM-S4: Preparative study for automotive exhaust emissions Degree of equ uivalence (mmol mol -1 ) INMETRO VSL NMISA L a b o r a to r y IPQ SMU CO 2 results 12 % mol/mol

19 EURO.QM-S4: Preparative study for automotive exhaust emissions 1 5 Degree of equ uivalence (µmol mol -1 ) IPQ VSL INMETRO L a b o r a to r y NMISA SMU Propane results 1000 µmol/mol

20 CCQM-K52: 360 µmol/mol CO 2 in air

21 CCQM-K51: 5 µmol/mol CO in nitrogen CCQM-K51 Carbon monoxide in nitrogen Degrees of equivalence (%) -2-3 NMIJ NMISA UBA (D) VNIIM SMU NPL CERI BAM CEM CENAM GUM INMETRO IPQ JRC KRISS LNE METAS NIM NIMT NIST VSL NPLI FMI NMIA Laboratory

22 Some challenging key comparison. Challenges CCQM-P73 CCQM-K71 CCQM-K74, CCQM-P110 CCQM-K76 APMP.QM-K41 CCQM-P28, BIPM.QM-K1

23 CCQM-P73: 30 to 70 µmol/mol NO in nitrogen (Gravimetry) CCQM-P73 (LIMAS 11UV analysis) CCQM-K1.c EUROMET-K1.c D/ mol/mol KRISS (M1) KRISS (M15) CSIR-NML (M2) CSIR-NML (M16) CERI (M3) CERI (M14) VALCRM1 (M4) VALCRM2 (M11) VALCRM3 (M17) LNE (M5) LNE (M19) SMU (M6) SMU (M18) CENAM (M7) CENAM (M20) VNIIM (M8) VNIIM (M22) NIST (M9) NIST (M24) NMIA (M10) NMIA (M23) IPQ (M12) IPQ (M25) NMi-VSL (M13) NMi-VSL (M21) NPL NIST NMi-VSL BNM-LNE KRISS NRLM* NRCCRM VNIIM OMH BNM-LNE NPL VNIIM NMi-VSL GUM CEM METAS CHMI FMI IPQ Laboratory (cylinder)

24 CCQM-K71: Stack gas mixtures CO results 40 ppm

25 CCQM-K71: Stack gas mixtures CO 2 results 12 % mol/mol

26 CCQM-K71: Stack gas mixtures Propane results 6 ppm

27 CCQM-K71: Stack gas mixtures NO results 80 ppm

28 CCQM-K74: 10 µmol/mol NO 2 in nitrogen D (µmol/mol) NMISA Laboratory

29 CCQM-P28: Ambient level ozone (420 nmol/mol)

30 WHY THIS REGIONAL COMPARISON IS IMPORTANT NMISA Gas metrology as part of Gas Analysis Working Group (GAWG) has a mandate to provide measurement traceability to the air pollution monitoring industry. Environmental assets and natural resources that are well protected and continually enhanced (Monitoring Gases) Designed to test the capabilities of the participants to measure the sulphur dioxide concentration levels at ambient and stack emission level. This will give evidence of the calibration and measurement capability of the participant laboratory for SO 2. Strive to create a cleaner environment for all South Africans and contribute to a better and safer Africa and world

31 Comparison between NMISA and Company A. (70 µmol.mol -1 Nitric Oxide in Nitrogen)

32 Background For Regional Comparison Sulphur dioxide (SO 2 ) is a naturally occurring compound emitted from volcanoes and various industrial processes. This compound is regulated in many countries for emissions from point sources due to the link to acid rain. Reference gases of SO 2 in air or nitrogen are used for the calibration of analysers used to measure sulphur dioxide levels in ambient air and fixed sources (stacks) from industry. Sulphur dioxide is one of the most important substances in view of environmental and human health problems. SO 2 has been the subject of two prior CCQM key comparisons, CCQM-K1d (at 100 µmol/mol and 1000 µmol/mol) completed in 1997, and CCQM-K26b (at 200 nmol/mol) completed in In 2009 the NMISA started to participate in international key comparisons for sulphur dioxide such as CCQM-K71 for stack gas mixtures, where sulphur dioxide was also included in the range of 20 to 200µmol.mol -1. In 2010, the National Institute of Standards and Technology (NIST) in the USA coordinated the international key comparison, CCQM-K76, for 100 µmol/mol SO 2 in nitrogen, where the NMISA also participated.

33 CCQM-K71: Stack gas mixtures SO 2 results 80 ppm

34 CCQM-K76- Draft A results (2010/2011) - Coordinating Lab: NIST

35 Proposed PT SCHEME/COMPARISON SCHEDULE FOR (50 to 70 µmol.mol -1 of SO 2 in nitrogen) July 2011 August to September 2011 Draft protocol to participating laboratory Registration of participant October 2011 Preparation of gravimetric mixture + first verification measurement (evaluation of shortterm stability) October / November 2011 November /December Shipment of cylinder to participating laboratory Start of comparison 20 th January 2012 Report due to coordinating laboratory 20 th January 2012 Cylinders due to coordinating laboratory February 2012 March 2012 Second verification measurement Final report

36 Proposed PT SCHEME/COMPARISON SCHEDULE FOR (800 to 850 µmol.mol -1 of SO 2 in nitrogen) December 2011 January/February 2012 Draft protocol to participating laboratory Registration of participant March / April 2012 Preparation of gravimetric mixture + first verification measurement (evaluation of shortterm stability) May / June 2012 June /July 2012 End August 2012 End August 2012 September 2012 October 2012 Shipment of cylinder to participating laboratory Start of comparison Report due to coordinating laboratory Cylinders due to coordinating laboratory Second verification measurement Final report

37 PRICE FOR COMPARISON Gas TAF delegates wanted us to prepare one sample, Cylinder move from one participant to another. Challenge: Contaminations. It was agree that the comparison must be R7500 per cylinder. Some company ask if its possible to get the cylinder back to them as a Primary Reference Gas Mixture (Cost:R8500) Price include shipping to and from participants and renting for those who want cylinder back as PRGM. Time frame includes: (preparation + First & Second Verification / Analysis, Stability)

38 Coordinating Laboratory Coordinating Laboratory: Gas Metrology of National Metrology institute of South Africa (NMISA) Field: Amount of Substance Subject: Sulphur Dioxide (SO 2 ) in Nitrogen at 50 to 70 µmol/mol for the ambient air monitoring and 800 to 850 µmol.mol -1 for stack gas emissions monitoring. Study co-ordinator: James Tshilongo ( jtshilongo@nmisa.org)

39 Thank you