Final report, Ongoing Key Comparison BIPM.QM-K1, Ozone at ambient level, comparison with NMISA, (July 2012)

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1 Final report, Ongoing Key Comparison BIPM.QM-K1, Ozone at ambient level, comparison with NMISA, (July 01) Joële Viallon 1*, Philippe Moussay 1, Faraz Idrees 1, Robert Wielgosz 1, Angelique Botha 1 BIPM (Bureau International des Poids et Mesures), Pavillon de Breteuil, F-931 Sèvres, France NMISA (National Metrology Institute of South Africa ), Private Bag X34 Lynnwood Ridge 0040 South Africa Abstract As part of the ongoing key comparison BIPM.QM-K1, a comparison has been performed between the ozone standard of the World Meteorological Organisation maintained by the National Metrology Institute of South Africa (NMISA ) and the common reference standard of the key comparison, maintained by the Bureau International des Poids et Mesures (BIPM). The instruments have been compared over a nominal ozone amount-of-substance fraction range of 0 nmol/mol to 500 nmol/mol. Contents: 1. FIELD.... SUBJECT PARTICIPANTS ORGANIZING BODY RATIONALE TERMS AND DEFINITIONS MEASUREMENT SCHEDULE MEASUREMENT PROTOCOL REPORTING MEASUREMENT RESULTS POST COMPARISON CALCULATION DEVIATIONS FROM THE COMPARISON PROTOCOL MEASUREMENT STANDARDS MEASUREMENT RESULTS AND UNCERTAINTIES ANALYSIS OF THE MEASUREMENT RESULTS BY GENERALISED LEAST-SQUARE REGRESSION DEGREES OF EQUIVALENCE HISTORY OF COMPARISONS BETWEEN BIPM SRP7, SRP8 AND API SUMMARY OF PREVIOUS COMPARISONS INCLUDED IN BIPM.QM-K CONCLUSION REFERENCES APPENDIX 1 - FORM BIPM.QM-K1-R1-NMISA * Author for correspondence. jviallon@bipm.org, Tel: , Fa: BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 1 of 1

2 1. Field Amount of substance.. Subject Comparison of reference measurement standards for ozone at ambient level. 3. Participants BIPM.QM-K1 is an ongoing key comparison, which is structured as an ongoing series of bilateral comparisons. The results of the comparison with the National Metrology Institute of South Africa (NMISA ) are reported here. 4. Organizing body BIPM. 5. Rationale The ongoing key comparison BIPM.QM-K1 has been running since January 007. It follows the pilot study CCQM-P8 that included 3 participants and that was performed between July 003 and February 005 [1]. It is aimed at evaluating the degree of equivalence of ozone photometers that are maintained as national standards, or as primary standards within international networks for ambient ozone measurements. The reference value is determined using the NIST Standard Reference Photometer (BIPM-SRP7) maintained by the BIPM as a common reference. 6. Terms and definitions - nom : nominal ozone amount-of-substance fraction in dry air furnished by the ozone generator - A,i : ith measurement of the nominal value nom by the photometer A. - A : the mean of N measurements of the nominal value nom measured by the photometer A : A 1 N N i 1 A, i - s A : standard deviation of N measurements of the nominal value nom measured by the N 1 photometer A : sa ( A, i A ) N 1 i 1 - The result of the linear regression fit performed between two sets of data measured by the photometers A and B during a comparison is written: A aa,b B ba, B. With this notation, the photometer A is compared against the photometer B. a A,B is dimensionless and b A,B is epressed in units of nmol/mol. 7. Measurement schedule The key comparison BIPM.QM-K1 was initially organised as year cycles. The 007 to 008 round, the results of which are published in the Key Comparison Database of the BIPM, included 16 participants. The second round of BIPM.QM-K1 started in March 009 for a period of 4 years, following the decision of the CCQM/GAWG to reduce the repeat frequency BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page of 1

3 of bilateral comparisons. Measurements reported in this report were performed on 6 June 01 at the BIPM. 8. Measurement protocol The comparison protocol is summarized in this section. The complete version can be downloaded from the BIPM website ( K1_protocol.pdf). This comparison was performed following protocol A, corresponding to a direct comparison between the NMISA standard API and the common reference standard BIPM-SRP7 maintained at the BIPM. A comparison between two (or more) ozone photometers consists of producing ozone-air mitures at different amount-of-substance fractions over the required range, and measuring these with the photometers Ozone generation The same source of purified air is used for all the ozone photometers being compared. This air is used to provide reference air as well as the ozone air miture to each ozone photometer. Ambient air is used as the source for reference air. The air is compressed with an oil-free compressor, dried and scrubbed with a commercial purification system so that the mole fraction of ozone and nitrogen oides remaining in the air is below detectable limits. The relative humidity of the reference air is monitored and the mole fraction of water in air typically is less than 3 μmol/mol. The mole fraction of volatile organic hydrocarbons in the reference air was measured (November 00), with no mole fraction of any detected component eceeding 1 nmol/mol. The NMISA ozone generator API 401, serial number 106, was used to produce ozone in dry air. A common dual eternal manifold in Pyre is used to furnish the necessary flows of reference air and ozone air mitures to the ozone photometers. The two columns of this manifold are vented to atmospheric pressure. 8.. Comparison procedure Prior to the comparison, all the instruments were switched on and allowed to stabilise for at least 8 hours. The pressure and temperature measurement systems of the instruments were checked at this time. If any adjustments were required, these were noted. For this comparison, no adjustments were necessary. One comparison run includes 10 different amount-of-substance fractions distributed to cover the range, together with the measurement of zero reference air at the beginning and end of each run. The nominal amount-of-substance fractions were measured in a sequence imposed by the protocol (0, 0, 80, 40, 10, 30, 30, 370, 170, 500, 70, and 0) nmol/mol. Each of these points is an average of 10 single measurements. For each nominal value of the ozone amount-of-substance fraction nom furnished by the ozone generator, the standard deviation s SRP7 on the set of 10 consecutive measurements SRP7,i recorded by BIPM-SRP7 was calculated. The measurement results were considered as valid if s SRP7 was less than 1 nmol/mol, which ensures that the photometers were measuring a stable ozone concentration. If not, another series of 10 consecutive measurements was performed. BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 3 of 1

4 8.3. Comparison repeatability The comparison procedure was repeated continuously during two cycles of hours each to evaluate its repeatability. The participant and the BIPM commonly decided when both instruments were stable enough to start recording a set of measurement results to be considered as the official comparison results SRP7 stability check Normally, a second ozone reference standard, BIPM-SRP8, is included in the comparison to verify its agreement with BIPM-SRP7 and thus follow its stability over the period of the ongoing key comparison. This was not feasible during this comparison, as the NMISA ozone generator delivers insufficient flow of ozone in air. BIPM-SRP8 and BIPM-SRP7 were compared in the week before the measurements reported here. 9. Reporting measurement results The participant and the BIPM staff reported the measurement results in the result form BIPM.QM-K1-R1 provided by the BIPM and available on the BIPM website. It includes details on the comparison conditions, measurement results and associated uncertainties, as well as the standard deviation for each series of 10 ozone amount-of-substance fractions measured by the participant s standard and the common reference standard. The completed form BIPM.QM-K1-R1-NMISA-1 is given in Appendi Post comparison calculation All calculations were performed by the BIPM using the form BIPM.QM-K1-R1. It includes the two degrees of equivalence that are reported as comparison results in the Appendi B of the BIPM KCDB (key comparison database). Additionally, the degrees of equivalence at all nominal ozone amount-of-substance fractions are reported in the same form, as well as the linear relationship between the participant standard and the common reference standard. 11. Deviations from the comparison protocol The standard deviation s RS on 10 successive measurements recorded with the BIPM-SRP7 was not always less than 1 nmol/mol, as required in the protocol of the comparison. This demonstrates that NMISA s ozone generator was not operating in a stable regime. These instabilities have less effect on the standard deviations s NS on measurements recorded with the NMISA standard because this instrument performs an automatic moving average on 3 successive measurements. This feature could not be turned off. As no stable regime could be reached when performing further measurements, it was decided to continue the comparison and to include the value s RS in the uncertainty associated with NMISA measurement results, as this was a characteristic of the ozone generator normally used with NMISA instrument. 1. Measurement standards The instruments maintained by the BIPM are Standard Reference Photometers (SRP) built by the NIST. More details on the NIST SRP principle and its capabilities can be found in []. The following section describes briefly the instruments measurement principle and their uncertainty budgets. BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 4 of 1

5 1.1. Measurement equation of a NIST SRP The measurement of the ozone amount-of-substance fraction by an SRP is based on the absorption of radiation at 53.7 nm by ozonized air in the gas cells of the instrument. One particularity of the instrument design is the use of two gas cells to overcome the instability of the light source. The measurement equation is derived from the Beer-Lambert and ideal gas laws. The number concentration (C) of ozone is calculated from: C 1 T P L T P opt std std ln( D) where is the absorption cross-section of ozone at 53.7 nm under standard conditions of temperature and pressure, cm /molecule [3]. L opt is the mean optical path length of the two cells; T is the measured temperature of the cells; T std is the standard temperature (73.15 K); P is the measured pressure of the cells; P std is the standard pressure ( kpa); D is the product of transmittances of two cells, with the transmittance (T r ) of one cell defined as T r I I ozone air where I ozone is the UV radiation intensity measured from the cell when containing ozonized air, and I air is the UV radiation intensity measured from the cell when containing pure air (also called reference or zero air). Using the ideal gas law equation (1) can be recast in order to epress the measurement results as a amount-of-substance fraction () of ozone in air: (1) () 1 T Lopt P N A R ln( D) where N A is the Avogadro constant, mol 1, and R is the gas constant, J mol 1 K 1 (3) The formulation implemented in the SRP software is: where 1 T Pstd ln( D) L T P opt std is the linear absorption coefficient at standard conditions, epressed in cm 1, linked to the absorption cross-section with the relation: (4) NA P R T std std (5) BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 5 of 1

6 1.. Absorption cross-section for ozone The linear absorption coefficient under standard conditions used within the SRP software algorithm is cm 1. This corresponds to a value for the absorption cross section of cm /molecule, rather than the more often quoted cm /molecule. In the comparison of two SRP instruments, the absorption cross-section can be considered to have a conventional value and its uncertainty can be set to zero. However, in the comparison of different methods or when considering the complete uncertainty budget of the method the uncertainty of the absorption cross-section should be taken into account. A consensus value of.1 % at a 95 % level of confidence for the uncertainty of the absorption cross-section has been proposed by the BIPM and the NIST in a recent publication [4] Condition of the BIPM SRPs Compared to the original design described in [], SRP7 and SRP8 have been modified to deal with two biases revealed by the study conducted by the BIPM and the NIST [4]. In 009, an SRP upgrade kit was installed in the instruments, as described in the report [5] Uncertainty budget of the common reference BIPM-SRP7 The uncertainty budget for the ozone amount-of-substance fraction in dry air () measured by the instruments BIPM-SRP7 and BIPM-SRP8 in the nominal range 0 nmol/mol to 500 nmol/mol is given in Table 1. Component (y) Optical Path L opt Pressure P Temperature T Ratio of intensities D Absorption Cross section Table 1: Uncertainty budget for the SRPs maintained by the BIPM Source Uncertainty u(y) Distribution Standard Uncertainty Combined standard uncertainty u(y) Sensitivity coefficient c i y contribution to u() c i u( y) nmol/mol Measurement Rectangular cm scale Repeatability Normal 0.01 cm 0.5 cm Correction Lopt Rectangular 0.5 cm factor Pressure gauge Rectangular 0.09 kpa Difference kpa Rectangular kpa between cells P Temperature Rectangular 0.03 K probe 0.07 K Temperature T Rectangular K gradient Scaler Rectangular 8 10 resolution Repeatability Triangular Dln( D) 0.8 Hearn value cm²/molecule cm²/molecule As eplained in the protocol of the comparison, following this budget the standard uncertainty associated with the ozone amount-of-substance fraction measurement with the BIPM SRPs can be epressed as a numerical equation (numerical values epressed as nmol/mol): 3 u( ) (0.8) (.9 10 ) (6) BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 6 of 1

7 1.5. Covariance terms for the common reference BIPM-SRP7 As eplained in section 14, correlations between the results of two measurements performed at two different ozone amount-of-substance fractions with BIPM-SRP7 were taken into account using the software OzonE. Details about the analysis of the covariance can be found in the protocol. The following epression was applied: where: u( i, j) i j u b (7) u ( ) u ( T) u ( P) u Lopt b T P Lopt (8) The value of u b is given by the epression of the measurement uncertainty: u b = Condition of the NMISA standard API The NMISA API is a UV photometric analyser, which is used as a transfer standard for the calibration of customers ozone generators. It was calibrated at the BIPM against BIPM-SRP7 two weeks before this comparison Uncertainty budget of the NMISA API The ozone amount-of-substance fraction measured measured by the NMISA API during the comparison was corrected with the regression data from the calibration of the instrument, to give the value corrected that was used in the comparison form: corrected a0 a1 measured measured (9) In the same manner the value u( measured ) was corrected using the data from the regression analysis performed during the same calibration: corrected 0 1 ( measured ) measured 1 measured 0, 1 u u a a u u a u a a (10) Where the standard uncertainties on the parameters of the regression are u(a1) = for the slope and u(a0) = 0.41 nmol mol -1 for the intercept. The covariance between the two parameters is cov(a0, a1) = nmol mol -1. The u( measured ) values were obtained by linearly combining (with root sum squares), the standard deviation of SRP7 s RS with the standard deviation of the API s NS, measured during the comparison. These values were then further combined linearly (with root sum squares) with the zero drift uncertainty for measurements at 0 nmol/mol nominal value: measured uzero_drif t ( measured ) (11) Or with the span drift uncertainty for all other measurements: 3 measured uspan_drif t ( measured ) (1) So that the uncertainty associated with measured (not corrected) values with the API is the combination of three terms: BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 7 of 1

8 (13) 13. Measurement results and uncertainties Details of the measurement results, the measurement uncertainties and the standard deviations at each nominal ozone amount-of-substance fraction are provided in appendi (form BIPM.QM-K1-R1-NMISA-1). 14. Analysis of the measurement results by generalised least-square regression The relationship between both standards was first evaluated with a generalised least-square regression fit, using the software OzonE. This software, which is documented in a publication [7], is an etension of the previously used software B_Least recommended by the ISO standard 6143:001 [8]. It includes the possibility to take into account correlations between measurements performed with the same instrument at different ozone amount-of-substance fractions. It also facilitates the use of a transfer standard, by handling of unavoidable correlations, which arise since this instrument needs to be calibrated by the reference standard. In a direct comparison, a linear relationship between the ozone amount-of-substance fractions measured by the instrument i and SRP7 is obtained: a a (14) i 0 1 SRP7 The associated uncertainties on the slope u(a 1 ) and the intercept u(a 0 ) are given by OzonE, as well as the covariance between them and the usual statistical parameters to validate the fitting function. Because the NMISA API was calibrated by the BIPM-SRP7 instrument prior to this comparison, the values of the two instruments are correlated. Covariance terms between the values associated with each instrument at the same nominal amount-of-substance fraction should be calculated and taken into account. Unfortunately, this feature is not implemented in the software OzonE. As the least-square results are given in this report for information only, parameters were calculated without these covariances Least-squares regression results The relationship between standard API and SRP7 is: (15) SRP15 SRP7 The standard uncertainties on the parameters of the regression are u(a 1 ) = for the slope and u(a 0 ) = 0.46 nmol/mol for the intercept. The covariance between the two parameters is cov(a 0, a 1 ) = nmol mol -1. The least-squares regression results confirm that a linear fit is appropriate, with a sum of the squared deviations (SSD) of 0.64 and a goodness of fit (GoF) equals to To assess the agreement of the standards using equations 11 and 1, the difference between the calculated slope value and unity, and the intercept value and zero, together with their measurement uncertainties need to be considered. In this comparison, the value of the BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 8 of 1

9 intercept is not consistent with an intercept of zero, considering the uncertainty in the value of this parameter; i.e a 0 < u(a 0 ), and the value of the slope is consistent with a slope of 1; i.e. 1 a 1 < u(a 1 ). 15. Degrees of equivalence Degrees of equivalence are calculated at two nominal ozone amount-of-substance fractions among the twelve measured in each comparison, in the nominal range 0 nmol/mol to 500 nmol/mol: 80 nmol/mol and 40 nmol/mol. These values correspond to points number 3 and 4 recorded in each comparison. As an ozone generator has limited reproducibility, the ozone amount-of-substance fractions measured by the ozone standards can differ from the nominal values. However, as stated in the protocol, the value measured by the common reference SRP7 was epected to be within 15 nmol/mol of the nominal value. Hence, it is meaningful to compare the degree of equivalence calculated for all the participants at the same nominal value Definition of the degrees of equivalence The degree of equivalence of the participant i, at a nominal value nom is defined as: D (16) i i SRP7 where i and SRP7 are the measurement result of the participant i and of SRP7 at the nominal value nom. Its associated standard uncertainty is: u( D ) u u (17) i i SRP7 where u i and u SRP7 are the measurement uncertainties of the participant i and of SRP7 respectively. For this particular comparison, because the NMISA API was calibrated by the BIPM-SRP7 instrument prior to the comparison, the values of the two instruments are fully correlated. This is taken into account in the calculation of the uncertainty of the degrees of equivalence using the following formula: u( D ) u( ) (1 a ) u( ) (18) i i 1 SRP7 Where a 1 is the slope of the linear relationship between NMISA API and SRP7 (equation 9). Here, because a 1 is very close to 1, equation 15 can be written: u( D ) u( ) u( ) (19) i i SRP Values of the degrees of equivalence The degrees of equivalence and their uncertainties calculated in the form BIPM.QM-K1-R1- NMISA-1 are reported in the table below. Corresponding graphs of equivalence are displayed in Figure 1. The epanded uncertainties are calculated with a coverage factor k =. Table : degrees of equivalence of the NMISA at the ozone nominal amount-ofsubstance fractions 80 nmol/mol and 40 nmol/mol BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 9 of 1

10 NMISA Nominal value / (nmol/mol) i / u i / SRP7 / u SRP7 / D i / u(d i ) / U(D i ) / NMISA (nmol/mol) (nmol/mol) (nmol/mol) (nmol/mol) (nmol/mol) (nmol/mol) (nmol/mol) (k = ) Nominal value 80 nmol/mol 15 (k = ) Nominal value 40 nmol/mol 10 5 Di / (nmol/mol) 0 Di / (nmol/mol) Figure 1: degrees of equivalence of the NMISA at the two nominal ozone amount-ofsubstance fractions 80 nmol/mol and 40 nmol/mol The degrees of equivalence between the NMISA standard and the common reference standard BIPM SRP7 indicate good agreement between the standards. A discussion on the relation between degrees of equivalence and CMC statements can be found in [1]. 16. History of comparisons between BIPM SRP7, SRP8 and API Results of previous comparisons performed since the first one in 004 during the pilot study CCQM-P8 are displayed in Figure together with the results of this comparison. To show the stability of the reference standard BIPM-SRP7, results of comparisons between BIPM- SRP7 and BIPM-SRP8 are also displayed. The slopes a 1 of the linear relation SRPn = a 0 + a 1 SRP7 are represented together with their associated uncertainties calculated at the time of each comparison. Results of comparisons before 010 have been corrected to take into account the changes in the reference BIPM-SRP7 described in [5] which eplains the larger uncertainties associated with the corresponding slopes. Figure shows that all standards included in these comparisons stayed in close agreement. BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 10 of 1

11 Slope BIPM-SRP8 Série5 NMISA SRP8 (P8) (k =) Sep. 04 Jul 08 Aug10 Jul Figure : Results of previous comparisons between SRP7, SRP8 and NMISA standards realised at the BIPM. Uncertainties are calculated at k =, with the uncertainty budget in use at the time of each comparison. 17. Summary of previous comparisons included in BIPM.QM-K1 The comparison with NMISA is the siteenth in the round of BIPM.QM-K1. An updated summary of BIPM.QM-K1 results can be found in the BIPM key comparison database: Conclusion For the third time since the launch of the ongoing key comparison BIPM.QM-K1, a comparison has been performed between South Africa s ozone national standard held by the NMISA and the common reference standard of the key comparison, maintained by the BIPM. The instruments have been compared over a nominal ozone amount-of-substance fraction range of 0 nmol/mol to 500 nmol/mol. Degrees of equivalence of this comparison indicated good agreement between the two standards. 19. References [1] Viallon J, Moussay P, Esler M, Wielgosz R, Bremser W, Novák J, Vokoun M, Botha A, Janse Van Rensburg M, Zellweger C, Goldthorp S, Borowiak A, Lagler F, Walden J, Malgeri E, Sassi M P, Morillo Gomez P, Fernandez Patier R, Galan Madruga D, Woo J-C, Doo Kim Y, Macé T, Sutour C, Surget A, Niederhauser B, Schwaller D, Frigy B, Györgyné Váraljai I, Hashimoto S, Mukai H, Tanimoto H, Ahleson H P, Egeløv A, Ladegard N, Marsteen L, Tørnkvist K, Guenther F R, Norris J E, Hafkenscheid T L, Van Rijn M M, Quincey P, Sweeney B, Langer S, Magnusson B, Bastian J, Stummer V, Fröhlich M, Wolf A, Konopelko L A, Kustikov Y A and Rumyanstev D V, PILOT STUDY: International Comparison CCQM-P8: Ozone at ambient level, Metrologia, 006, 43, Tech. Suppl., BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 11 of 1

12 [] Paur R J, Bass A M, Norris J E and Buckley T J 003 Standard reference photometer for the assay of ozone in calibration atmospheres Env. Sci. Technol. NISTIR 6369, 5 pp [3] ISO : 1996 Ambient air - Determination of ozone - Ultraviolet photometric method (International Organization for Standardization) [4] Viallon J, Moussay P, Norris J E, Guenther F R and Wielgosz R I, A study of systematic biases and measurement uncertainties in ozone mole fraction measurements with the NIST Standard Reference Photometer, Metrologia, 006, 43, [5] Viallon J, Moussay P, Idrees F and Wielgosz R I 010 Upgrade of the BIPM Standard Reference Photometers for Ozone and the effect on the on-going key comparison BIPM.QM-K1 Rapport BIPM-010/07, 16 pp [6] Viallon J, Moussay P, Wielgosz R I, Novák J and Vokoun M, Final report of the ongoing key comparison BIPM.QM-K1: Ozone at ambient level, comparison with CHMI, 007, Metrologia, 008, 45, Tech. Supl., [7] Bremser W, Viallon J and Wielgosz R I, Influence of correlation on the assessment of measurement result compatibility over a dynamic range, Metrologia, 007, 44, [8] ISO 6143:001 Gas analysis - Comparison methods for the determining and checking the composition of calibration gas mitures - (International Organization for Standardization) Appendi 1 - Form BIPM.QM-K1-R1-NMISA-1 See the following pages. BIPM QM-K1 NMISA 107 Final report doc 9 Jul. 13 Page 1 of 1

13 Ozone comparison form BIPM.QM-K1-R1 Version.0 Modified on 14/09/007 OZONE COMPARISON RESULT - PROTOCOL A - DIRECT COMPARISON Participating institute information Institute Address Contact Telephone NMISA Private Bag X34 Lynnwood Ridge 0040 South Africa Angelique Botha abotha@nmisa.org Manufacturer Type Serial number Instruments information Reference Standard NIST SRP SRP7 National Standard API page 1 page page 3 page 4 page 5 general informations comparison results measurements results comparison description uncertainty budgets Content of the report BIPM.QM-K1-R1-NMISA-1.ls Page 1 08/01/013

14 Ozone comparison form BIPM.QM-K1-R1 Version.0 Modified on 14/09/007 comparison reference standard (RS) - national standard (NS) Operator F.Idrees Location BIPM/Room CHEM09 Comparison begin date / time 7/07/01 18:00 Comparison end date / time 8/07/01 08:30 Comparison results Equation NS a NS, RS RS b NS, RS Least-square regression parameters a TS,RS u (a TS,RS ) b TS,RS u (b TS,RS ) u(a,b) (nmol/mol) (nmol/mol) (nmol/mol) E-04 (Least-square regression parameters will be computed by the BIPM using the sofwtare OzonE v.0) Degrees of equivalence at 80 nmol/mol and 40 nmol/mol: Nom value D i u (D i ) U (D i ) (nmol/mol) (nmol/mol) (nmol/mol) (nmol/mol) All degrees of equivalence (k=) Di /nmol/mol nominal value /nmol/mol BIPM.QM-K1-R1-NMISA-1.ls Page 08/01/013

15 Ozone comparison form BIPM.QM-K1-R1 Version.0 Modified on 14/09/007 Nominal value Measurement results Reference Standard (RS) National standard (NS) RS nmol/mol s RS nmol/mol u ( RS ) nmol/mol NS nmol/mol s NS nmol/mol u ( NS ) nmol/mol measured Point Number Degrees of Equivalence Nom value D i u (D i ) U (D i ) (nmol/mol) (nmol/mol) (nmol/mol) (nmol/mol) Covariance terms in between two measurement results of each standard Equation u(, ) i j i j Value of for the reference standard Value of for the national standard 8.50E E+00 Note 1 :values measured by the NMISA national standard API400 have been corrected according to the calibration performed at the BIPM on 0 July 01 as eplained with the uncertainty budget Note : due to the calibration, the NMISA values are fully correlated with SRP7 values This is taken into account in the calculation of the degrees of equivalence uncertainty: ud ( ) u ( ) u ( ) i i ref BIPM.QM-K1-R1-NMISA-1.ls Page 3 08/01/013

16 Ozone comparison form BIPM.QM-K1-R1 Version.0 Modified on 14/09/007 Comparison conditions Ozone generator manufacturer API Ozone generator type 401 Ozone generator serial number 106 Room temperature(min-ma) / C Room pressure (min-ma) / hpa Zero air source compressor + BekoKAT + dryer+ aadco 737-R Reference air flow rate (L/min) 10 L/min to SRP7 Sample flow rate (L/min) 4.6 L/min for SRP7 and API400 Instruments stabilisation time more than 4 hours both Instruments acquisition time /s (one measurement) SRP7 5 s / API s Instruments averaging time /s SRP7 none / API s Total time for ozone conditioning more than 4 hours both Ozone mole fraction during conditioning (nmol/mol) 1000 nmol/mol Comparison repeated continously (Yes/No) Yes If no, ozone mole fraction in between the comparison repeats *** Total number of comparison repeats realised 15 Data files names and location D:\Data\01\c ls As written in the procedure BIPM/CHEM-T-05 Instruments checks and adjustments Reference Standard National Standard Page 4 BIPM.QM-K1-R1-NMISA-1.ls 08/01/013

17 Ozone comparison form BIPM.QM-K1-R1 Version.0 Modified on 14/09/007 Uncertainty budgets (description or reference ) Reference Standard BIPM-SRP7 uncertainty budget is described in the protocol of this comparison: document BIPM.QM-K1 protocol, date 10 Januray 007, available on BIPM website. It can be summarised by the formula: 3 u ( ) (0.8) (.9 10 ) Uncertainty budget: BIPM.QM K1 National Standard where, u u a a u u a u a a corrected 0 1 measured measured 1 measured 0 1 u a 0 a 1 u a 1 u a, a nmol/mol nmol/mol corrected a0 a1 measured where a 0 a nmol/mol To epress the uncertainty as an equation u u measured measured measured Thus 5 u u measured measured measured BIPM.QM-K1-R1-NMISA-1.ls Page 5 08/01/013