SAMPLING AND CALIBRATION FOR ATMOSPHERIC MEASUREMENTS A symposium sponsored by ASTM Committee D-22 on Sampling and Analysis of Atmospheres Boulder, CO, 12-16 Aug 1985 ASTM SPECIAL TECHNICAL PUBLICATION 957 John K Taylor, National Bureau of Standards, editor ASTM Publication Code Number (PCN) 04-957000-17 1916 Race Street, Philadelphia, PA 19103 # Copyright by ASTM Int'l (all rights reserved); Sun Dec 27 14:15:08 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authorized Library of Congress Cataloging-in-Publication Data Sampling and calibration for atmospheric measurements (ASTM special technical publication; 957) "ASTM publication code number (PCN) 04-957000-17." Papers presented at the Conference on Sampling and Calibration for Atomspheric Measurements Includes bibliographies and index Air quality—Measurement—Congresses Air—Pollution, Indoor—Measurement—Congresses I Taylor, John K (John Keenan), 1912 II ASTM Committee D22 on Sampling and Analysis of Atmospheres III Symposium on Sampling and Calibration for Atmospheric Measurements (1985: Boulder, Colo.) IV Series TD890.S26 1987 628.5'3 87-12439 ISBN 0-8031-0955-5 Copyright © by AMERICAN SOCIETY FOR TESTING AND MATERIALS 1987 Library of Congress Catalog Card Number: 87-12439 NOTE The Society is not responsible, as a body, for the statements and opinions advanced in this publication Printed in Baltimore MD August 1987 Copyright by ASTM Int'l (all rights reserved); Sun Dec 27 14:15:08 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authoriz Foreword The symposium on Sampling and Calibration for Atmospheric Measurements was held in Boulder, Colorado, 12-16 August 1985 The symposium was sponsored by ASTM Committee D-22 on SampUng and Analysis of Atmospheres John K Taylor, National Bureau of Standards, Richard G Melcher, Dow Chemical Company, and Harry L Rook, National Bureau of Standards, presided as symposium chairmen John K Taylor is editor of this publication Copyright by ASTM Int'l (all rights reserved); Sun Dec 27 14:15:08 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authorize Related ASTM Publications Quality Assurance for Environmental Measurements, STP 867 (1985), 04-867000-16 Toxic Materials in the Atmosphere: Sampling and Analysis, STP 786 (1982) 04-786000-17 Sampling and Analysis of Toxic Organics in the Atmosphere, STP 721 (1981), 04-721000-19 Air Quality Meteorology and Atmospheric Ozone, STP 653 (1978), 04653000-17 Calibration in Air Monitoring, STP 598 (1976), 04-598000-17 Copyright by ASTM Int'l (all rights reserved); Sun Dec 27 14:15:08 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authorize A Note of Appreciation to Reviewers The quality of the papers that appear in this pubUcation reflects not only the obvious efforts of the authors but also the unheralded, though essential, work of the reviewers On behalf of ASTM we acknowledge with appreciation their dedication to high professional standards and their sacrifice of time and effort ASTM Committee on Publications Copyright by ASTM Int'l (all rights reserved); Sun Dec 27 14:15:08 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further repr ASTM Editorial Staff Helen M Hoersch Janet R Schroeder Kathleen A Greene Bill Benzing Copyright by ASTM Int'l (all rights reserved); Sun Dec 27 14:15:08 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authorize Contents Introduction GENERAL TOPICS General Principles of Sampling—BYRON KRATOCHVIL Principles of Calibration—JOHN K TAYLOR 14 INDOOR AIR—GENERAL Overview of Indoor Air Quality Sampling and Analysis— HAL LEVIN 21 Indoor Air Quality Measurements—ROY C FORTMANN, N I R E N L N A G D A , A N D MICHAEL D KOONTZ 35 Field Measurements for Air Quality in Office Buildings: A ThreePhased Approach to Diagnosing Building Performance Problems—ELIA M STERLING, EDWARD D MCINTYRE, CHRISTOPHER W COLLETT, JACK MEREDITH, AND T H E O D O R D STERLING 46 Sampling of Microbiological Contaminants in Indoor Air— AHARON FRADKIN 66 AMBIENT AIR Precision and Accuracy Assessment Derived from Calibration Data—HARRY L ROOK 81 The EPA's Role in the Quality Assurance of Ambient Air Pollutant Measurements—JOHN C PUZAK AND FRANK F MCELROY 87 Parts-Per-Billion Gaseous Mixtures: A New Challenge— ROBERT B DENYSZYN AND TOM SASSAMAN 101 Trace Gas Calibration Systems Using Permeation Devices— GERALD D MITCHELL Copyright Downloaded/printed University 110 by by of Tunable Diode Laser Absorption Spectrometry for Ultra-Trace Measurement and Calibration of Atmospheric Constituents—ALAN FRIED AND ROBERT SAMS 121 Special Calibration Systems for Reactive Gases and Other Difficult Measurements—w D DORKO AND E E HUGHES 132 WORKPLACE ATMOSPHERES Strategy for Industrial Hygiene Monitoring in the Chemical Industry—SAM K NORWOOD 141 Laboratory and Field Validation of Solid Sorbent Samplers— RICHARD G MELCHER 149 The U S Army's New Industrial Hygiene Sampling Guide— FREDERIC B E L K I N AND RICHARD W BISHOP 166 Detector 'Dibes—ELMER S MCKEE AND PAUL W MCCONNAUGHEY 176 Recent Developments in the Sampling and Analysis of Isocyanates in Afr—VENKATRAM DHARMARAJAN, ROBERT D LINGG, KARROL S BOOTH, AND DAVID R HACKATHORN 190 Collection and Analysis of Airborne Hexamethylene Diisocyanate by a Modified OSHA Method—GEORGE E PODOLAK, RICHARD A CASSIDY, GEORGE G ESPOSITO, AND DONALD J KIPPENBERGER 203 SUMMARY Summary 215 Author Index 219 Subject Index 221 Copyright Downloaded/printed University by by of STP957-EB/Aug 1987 Introduction This publication contains the texts of a series of papers presented at the Conference on Sampling and Calibration for Atmospheric Measurements sponsored by ASTM Committee D-22 on SampUng and Analysis of Atmospheres This conference was held at the University of Colorado, Boulder, Colorado, during 12-16 August 1985 It was the seventh in a series of biannual conferences to advance the state of the art of atmospheric measurements Previous conferences were devoted to the following subjects Conference Date Title (Pubhcation Date) 1973 Instrumentation for Monitoring Air Quality ASTM ST? 555 (1974) Calibration in Air Monitoring ASTM STP 598 (1976) Air QuaUty Meteorology and Atmospheric Ozone ASTM STP 653 (1978) Sampling and Analysis of Toxic Organics in the Atmosphere ASTM STP 721 (1981) Toxic Materials in the Atmosphere, Sampling and Analysis ASTM STP 786 (1982) Quality Assurance for Environmental Measurement ASTM STP 867 (1985) 1975 1977 1979 1981 1983 The 1983 Conference on Quality Assurance for Environmental Measurements focused on the general topic of data quality Throughout that conference, the question of the reliability calibration and the relevance of samples frequently was called to attention Accordingly, it was decided to devote the 1985 conference to a comprehensive discussion of these topics The papers discuss them from four points of view: General Aspects, Indoor Air, Ambient Air, and Workplace Atmospheres The Committee D-22 sponsored conferences have provided a forum for the presentation of state-of-the-art papers in selected areas and the opportunity for both formal and informal discussions by the attendees The publication of the papers serves to extend the benefits of the conference to a wider audience John K Taylor Coordinator for Chemical Measurement Assurance and Voluntary Standardization, Center for Analytical Chemistry, National Bureau of Standards, Gaithersburg, MD; editor Copyright by ASTM Int'l (all Copyright 1987 b y AS FM International www.astm.org Downloaded/printed by University of Washington (University rights of reserved); Washington) PODOLAK ET AL ON AIRBORNE HEXAMETHYLENE DIISOGYANATE 209 TABLE 2—HDI recoveries from laboratory prepared samples (averages of six "spikes" at seven concentration levels) Theoretical Value, ppb" Found Value, ppb" 25 20 10 Average 21.67 20.33 9.73 5.12 2.88 1.86 1.12 % Recovery, Relative Standard Deviation, X % 86.68 101.65 97.30 102.47 95.89 93.00 112.00 98.43 2.88 13.94 1.61 15.86 5.58 2.85 8.79 7.36 " ppb = values calculated on basis of 60 L (volume air) per sample with theoretical values for HDI in the range of to 25 ppb (calculated on basis of a 60-L air sample) Field Phase The primary objective of the first field study was to obtain a comparison of impinger and nonimpinger HDI sampling methods Furthermore, tests were conducted to provide insight regarding the stability of the urea derivatives during transit and storage A total of 160 samples were collected at a CARC spray facility using the three different modes of collection: impingers, filters, and tubes Some samples were analyzed at the test site while others were sent under varying conditions to the laboratory No discernable differences were noted between results of the samples analyzed immediately at the site and those that were shipped to the laboratory for analysis Consequently, average results for each collection mode setup were calculated regardless of post-test treatment of the samples Data comparing the sampling methods are presented in Table No data for impinger samples collected in pyridyl piperazine/toluene sorbent are included Data rehability from this procedure was poor because of acute evaporation losses and breakage and spillage of samples that occurred in transit As shown in Table 3, the GC impinger method produced consistently higher results when compared with HPLC methods These high results may be attributed to the presence of an interfering compound, such as hexamethylene diamine Conversely, competitive reactions with HDI may take place between the reagent and other paint components that would suppress the results from reagent-impregnated filters [75] The tubes gave the lowest results Furthermore, open-face filters provided higher results than closed-face filters The low results for the tubes and closed-face cassettes can be explained by the fact that in each case all of the sample impinged on a small area of collection medium thereby consuming all of the reagent available at a specific site, thus producing low results Subsequently, impregnated tubes and closed-face filter samplers were deleted from the sampling scheme The second field study was conducted using filters impregnated with a ten times greater amount of l-(2-P)P than called for in the OSHA procedure This reagent increase was decided upon to ensure the total in situ derivatization of large amounts of HDI when encountered in sampled atmospheres Relatively high HDI concentrations are generally found in CARC spraying operations of large items (for example, trucks) At the same time an assessment was made of the recoveries of HDI collection in relation to the increased air velocities through the l-(2-P)P impregnated filters Thefiltersfor this purpose were prepared Copyright ASTM Int'l (all rights reserved); Sun l-(2-P)P Dec 27 14:15:08 EST 2015 in three by different configurations and their content adjusted accordingly (see Ex- Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authoriz 210 SAMPLING AND CALIBRATION FOR ATMOSPHERIC MEASUREMENTS TABLE 3—Results from first field survey (airborne HDI concentrations measured at a CARC application site by different sampling and instrumental procedures—each entry average of three samples).' HPLC Test No GC" Impinger, •ppb Filters, ppb Tubes, ppb 10 11 12 13 14 15 16 6.53 6.57 8.38 10.52 11.97 7.28 21.41 17.34 21.58 18.67 32.00 28.10 11.76 12.20 13.20 18.20 6.04 4.93 7.09 3.62 4.74 2.47 7.46 6.37 5.74 5.73 3.50 12.87 4.97 4.60 1.30 2.42 2.11 1.97 4.13 3.99 2.90 3.17 0.86 2.80 2.38 5.05 5.78 5.57 3.12 2.30 4.30 4.13 " Samples to were collected in open-face cassettes, the rest were collected in the closed-face mode '' Marcali solution (10 mL) ' l-(2-P)P-based samplers TABLE 4—Results from second field test (airborne HDI in ppm—samples collected using three sizes of filters with adjusted l-(2-P)P loadings), i Filter Surface Area Test Set No Sample No 1/2 1/4 1 1" 2' 3° 4" 5" 6" 7" 8° 9" 4.3 nd' 9.0 nd 5.5 nd 191.4 nd 179.2 nd 222.8 nd 2.1 nd 2.6 nd 4.2 nd 1.9 nd 3.5 nd 2.4 nd 59.4 nd 85.0 nd 44.2 nd 1.3 nd 1.7 nd 1.4 nd 2.3 nd 0.3 nd 0.6 nd 15.6 1.8 33.2 1.2 88.4 0.7 1.1 nd 1.2 nd 0.5 nd ' Back-up filters ' nd = by none detected Copyright ASTM Int'l (all rights reserved); Sun Dec 27 14:15:08 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authoriz PODOLAK ET AL ON AIRBORNE HEXAMETHYLENE DIISOCYANATE 211 perimental section) To determine a potential HDI breakthrough at increased air velocities, all samplers were backed up with secondary filters irrespective of the configuration of the employed filter The cassettes holding back-up filters were placed downstream of each test filter The results from the test are entered in Table Note, the results from this test are given in ppm They are grouped in test sets and aligned according to the size of filters Filters within each set were assigned positions at random The sample results from Set exhibit relatively high HDI concentrations They were obtained by purposely positioning the nozzle of the paint spray gun very close to the samplers The smallest filters (one-fourth of surface area) with the greatest velocities (7.31 cm/s) applied in this test allowed breakthrough of HDI Results obtained from filter samples allowing lesser velocities and with the flow rates measuring L/min, registered no HDI breakthrough Furthermore, the results of this test proved that high airborne HDI concentrations are likely to occur in this type of CARC-spraying operation In the final stage of the field phase, 96 filter samples and nine impinger test samples were collected in a CARC paint spray booth and analyzed The results from this test are presented in Table The samples, denoted as A series, were analyzed according to the OSHA procedure, and all others (B and C series) by employing the newly developed technique for the removal of excess derivatizing reagent The transport modes of Series B and C were also different The comparison between the results from the A and C series showed equivalent performance of both the OSHA method and the new technique In addition, there were no discernable differences when comparing B and C series results, thus indicating no HDI-urea losses occurred due to the shipping of samples in the filter cassettes The B and C series filters were impregnated each with a tenfold increased amount of 1(2-F)P as opposed to the A series that contained only 0.1 mg of reagent per filter No positive conclusions were drawn as to whether OSHA's original amount was sufficient to quantitatively collect all of the HDI present in the sampled air Since the GC-impinger monitoring procedure was not part of the comparison study of the OSHA and OSHAmodified methods, the data from this perfunctory part of the test are not included in Table As in the first field study, the GC-impinger results were consistently higher than those obtained from corresponding l-(2-P)P filter samples (See Field Test and Table 3) In the analyses of B and C samples using the new HPLC procedure, the HDI-urea peak eluted at approximately 13 Since the normally late-emerging oligomer and l-(2-P)P peaks were disposed of by flushing to waste, samples could be injected in approximately TABLE 5—Results from third field study" (comparative sampling and analysis by OSHA's and modified methods) Test No A' OSHA Method, ppb B' Modified Method, ppb C Modified Method, ppb 1.31 8.56 2.72 3.73 1.77 0.52 0.43