ASTM_DS55-1974.pdf

FINAL REPORT on INTERLABORATORY COOPERATIVE STUDY OF THE PRECISION AND ACCURACY OF THE MEASUREMENT OF NITROGEN DIOXIDE CONTENT IN THE ATMOSPHERE USING ASTM METHOD D1607 J.F.Foster and G.H.Beatty Battelle Memorial Institute ASTM DATA SERIES PUBLICATION DS 55 List price$5.00 05-055000-17#AMERICAN SOCIETY FOR TESTING AND MATERIALS 1916 Race Street,Philadelphia,Pa.19103 BY AMERICAN SOCIETY FOR TESTING AND MATERIAL 1974 Library of Congress Catalog Card Number:73-94362 NOTE The Society is not responsible,as a body,for the statements and opinions advanced in this publication.Battelle is not engaged in research for advertising,sales promotion,or publicity purposes,and this report may not be reproduced in full or in part for such purposes./Printed in West Point,Pa.March 1974 TABLE OF CONTENTS Page INTRODUCTION 1 SUMMARY OF RESULTS AND CONCLUSIONS 1 EXPERIMENTAL PROGRAM.,3 ASTM Test Method D1607 3 Apparatus 4 Sampling Generating System 5 Spiking Procedure 11 Sampling Procedure.11 Test Sites 13 Site No.1,Los Angeles,California 13 Site No.2,Bloomington,Indiana 14 Site No.3,Manhattan,New York City 14 Participating Laboratories 16 STATISTICAL DESIGN OF EXPERIMENTAL PROGRAM 17 STATISTICAL ANALYSIS OF NITROGEN DIOXIDE MEASUREMENTS 21 Statistical Measures 21 Reproducibility 21 Repeatability 21 Accuracy 23 Comparability 23 Analysis of Reproducibility.23 Experimental Data 23 Evaluation of Reproducibility 24 Analysis of Repeatability 40 Experimental Data 40 Evaluation of Repeatability 40 Analysis of Accuracy .48 Analysis of Comparability 51 Analysis of Laboratory,Block,and Outlet Effects Using Latin Squares and Randomized Blocks 53 DISCUSSION AND CONCLUSIONS 64 RECOMMENDATIONS 65 ACKNOWLEDGEMENTS 67 REFERENCES 69 APPENDIX STANDARD METHOD OF TEST FOR NITROGEN DIOXIDE CONTENT OF THE ATMOSPHERE(GREISS-SALTZMAN REACTION).73 LIST OF TABLES Page Table 1.Sampling Pattern of Nitrogen Dioxide Experiments at Los Angeles Site 19 Table 2.Sampling Pattern of Nitrogen Dioxide Experiments at Bloomington Site 20 Table 3.Sampling Pattern of Nitrogen Dioxide Experiments at Manhattan Site 22 Table 4.Data From Nitrogen Dioxide Experiments(Blocks 1-24)at Los Angeles Site Arranged by Block and Outlet Position 25 Table 5.Data From Nitrogen Dioxide Experiments(Blocks 1-24)at Bloomington Site Arranged by Block and Outlet Position 28 Table 6.Data From Nitrogen Dioxide Experiments(Blocks 1-24)at Manhattan Site Arranged by Block and Outlet Position .31 Table 7.Block Statistics(Blocks 1-24)for Unspiked Samples of Nitrogen Dioxide From Los Angeles 34 Table 8.Block Statistics(Blocks 1-24)for Unspiked Samples of Nitrogen Dioxide From Bloomington 35 Table 9.Block Statistics(Blocks 1-24)for Unspiked Samples of Nitrogen Dioxide From Manhattan 35 Table 10.Block Statistics(Blocks 1-24)for Spiked Samples of Nitrogen Dioxide From Los Angeles 36 Table 11.Block Statistics(Blocks 1-24)for Spiked Samples of Nitrogen Dioxide From Bloomington 37 Table 12.Block Statistics(Blocks 1-24)for Spiked Samples of Nitrogen Dioxide From Manhattan 37 Table 13.Complete List of Statistical Outliers and Corresponding Revised Block Statistics 41 Table 14.Data From Blocks 25-32 of Nitrogen Dioxide Experiments at Los Angeles Site Arranged by Block 42 Table 15.Data From Blocks 25-32 of Nitrogen Dioxide Experiments at Bloomington Site Arranged by Block.43 Table 16.Data From Blocks 25-32 of Nitrogen Dioxide Experiments at Manhattan 44 Table 17.Block Statistics(Blocks 25-32)for Samples of Nitrogen Dioxide 45 ii LIST OF TABLES(Continued)Pae Table 18.Correlation Matrix for Unspiked Samples from Los Angeles.54 Table 19.Correlation Matrix for Spiked Samples from Los Angeles 54 Table 20.Correlation Matrix for Unspiked Samples from Bloomington.55 Table 21.Correlation Matrix for Spiked Samples from Bloomington 55 Table 22.Correlation Matrix for Unspiked Samples from Manhattan 56 Table 23.Correlation Matrix for Spiked Samples from Manhattan 56 Table 24.F-Fractiles Obtained From Latin Square Analysis of Nitrogen Dioxide Measurements of Los Angeles Samples 58 Table 25.F-Fractiles Obtained From Latin Square Analysis of Nitrogen Dioxide Measurements of Bloomington Samples 59 Table 26.F-Fractiles Obtained From Latin Square Analysis of Nitrogen Dioxide Measurements of Manhattan Samples 60 Table 27.Variance Analysis of Unspiked Samples From Bloomington.62 Table 28.Variance Analysis of Spiked Samples From Bloomington.62 Table 29.Variance Analysis of Unspiked Samples From Manhattan 62 Table 30.Variance Analysis of Spiked Samples From Manhattan 62 LIST OF FIGURES Figure 1.Schematic Arrangement of Sampling Apparatus for ASTM Method D1607 6 Figure 2.Sampling Apparatus for ASTM D1607 7 Figure 3.Absorption Train for ASTM D1607 8 Figure 4.Parallel Absorption Trains for Concurrent Sampling by ASTM D1607 8 Figure 5.Sampling System Used for Evaluation of ASTM Method D1607 for Determining Nitrogen Dioxide in the Atmosphere 9 xxx LIST OF FIGURES(Continued)Page Figure 6.Sixteen-Position Sampling Manifold Used in Unspike