ASTM_DS55S1-1974.pdf

FINAL REPORT on INTERLABORATORY COOPERATIVE STUDY OF THE PRECISION AND ACCURACY OF THE MEASUREMENT OF SULFUR DIOXIDE CONTENT IN THE ATMOSPHERE USING ASTM METHOD D2914 J.F.Foster and G.H.Beatty Battelle Memorial Institute ASTM DATA SERIES PUBLICATION DS 55-S1 List price$5.00 05-055010-17 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:73-94363 NOTE The Society is not responsible,as a body,for the statements and opinions advanced in this publication.S.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 D 2914 3 Preparation 3 Collection 4 Analysis 4 Apparatus 5 Sample Generating System 8 Spiking Procedure 12 Sampling Procedure 12 Test Sites 14 Site No.1,Los Angeles,California 14 Site No.2,Bloomington,Indiana 15 Site No.3,Manhattan,New York City 15 Participating Laboratories.15 STATISTICAL DESIGN OF EXPERIMENTAL PROGRAM 17 STATISTICAL ANALYSIS OF SULFUR DIOXIDE MEASUREMENTS 22 Statistical Measures 22 Reproducibility 22 Repeatability 22 Accuracy 22 Comparability 23 Analysis of Reproducibility 23 Experimental Data 23 Evaluation of Reproducibility 33 Analysis of Repeatability 39 Experimental Data 39 Evaluation of Repeatability 44 Analysis of Accuracy 47 Analysis of Comparability 50 Analysis of Laboratory,Block,and Outlet Effects Using Latin Squares and Randomized Blocks 52 DISCUSSION AND CONCLUSIONS 63 RECOMMENDATIONS 64 ACKNOWLEDGEMENTS 66 REFERENCES 68 APPENDIX TENTATIVE METHOD OF TEST FOR SULFUR DIOXIDE CONTENT OF THE ATMOSPHERE(WEST-GAEKE METHOD)71 LIST OF TABLES Page Table 1.Sampling Pattern of Sulfur Dioxide Experiments at Los Angeles Site.19 Table 2.Sampling Pattern of Sulfur Dioxide Experiments at Bloomington Site.20 Table 3.Sampling Pattern of Sulfur Dioxide Experiments at Manhattan Site.21 Table 4.Data From Sulfur Dioxide Experiments(Blocks 1-24)at Los Angeles Site Arranged by Block and Outlet Position 24 Table 5.Data From Sulfur Dioxide Experiments(Blocks 1-24)at Bloomington Site Arranged by Block and Outlet Position.27 Table 6.Data From Sulfur Dioxide Experiments(Blocks 1-24)at Manhattan Site Arranged by Block and Outlet Position 30 Table 7.Block Statistics(Blocks 1-24)for Unspiked Samples of Sulfur Dioxide From Los Angeles 34 Table 8.Block Statistics(Blocks 1-24)for Unspiked Samples of Sulfur Dioxide From Bloomington 35 Table 9.Block Statistics(Blocks 1-24)for Unspiked Samples of Sulfur Dioxide From Manhattan 35 Table 10.Block Statistics(Blocks 1-24)for Spiked Samples of Sulfur Dioxide From Los Angeles 36 Table 11.Block Statistics(Blocks 1-24)for Spiked Samples of Sulfur Dioxide From Bloomington 37 Table 12.Block Statistics(Blocks 1-24)for Spiked Samples of Sulfur Dioxide From Manhattan 37 Table 13.Complete List of Statistical Outliers and Corresponding Revised Block Statistics 40 Table 14.Data From Blocks 25-32 of Sulfur Dioxide Experiments at Los Angeles Site Arranged by Block and Outlet Position.41 ii LIST OF TABLES(Continued)Page Table 15.Data From Blocks 25-32 of Sulfur Dioxide Experiments at Bloomington Site Arranged by Block and Outlet Position 42 Table 16.Data From Blocks 25-32 of Sulfur Dioxide Experiments at Manhattan Site Arranged by Block and Outlet Position 43 Table 17.Block Statistics(Blocks 25-32)for Samples of Sulfur Dioxide.45 Table 18.Correlation Matrix for Unspiked Samples From Los Angeles 53 Table 19.Correlation Matrix for Spiked Samples From Los Angeles 53 Table 20.Correlation Matrix for Unspiked Samples From Bloomington 54 Table 21.Correlation Matrix for Spiked Samples From Bloomington 54 Table 22.Correlation Matrix for Unspiked Samples From Manhattan 55 Table 23.Correlation Matrix for Spiked Samples From Manhattan 55 Table 24.F-Fractiles Obtained From Latin Square Analysis of Sulfur Dioxide Measurements of Los Angeles Samples 57 Table 25.F-Fractiles Obtained From Latin Square Analysis of Sulfur Dioxide Measurements of Bloomington Samples 58 Table 26.F-Fractiles Obtained From Latin Square Analysis of Sulfur Dioxide Measurements of Manhattan Samples 59 Table 27.Variance Analysis of Unspiked Samples From Bloomington 61 Table 28.Variance Analysis of Spiked Samples From Bloomington 61 Table 29.Variance Analysis of Unspiked Samples From Manhattan 61 Table 30.Variance Analysis of Spiked Samples From Manhattan 62 in LIST OF FIGURES Page Figure 1.Schematic Arrangement of Sampling Apparatus for ASTM Method D 2914.6 Figure 2.Sampling Apparatus for ASTM Method D 2914 8 Figure 3.Sampling Apparatus for ASTM Method D 2914 9 Figure 4.Parallel-Sampling Trains for Concurrent Measurements by ASTM Method D 2914 9 Figure 5.Sample Generating System Used for Evaluation of ASTM Method D 2914 for Determining Sulfur Dioxi