1、 STD.API/PETRO PUBL 344-ENGL 1998 O732290 Ob30343 459 = Critical Review of Source Sampling and Analysis Methodologies for Characterizing Organic Aerosol and Fine Particulate Source Emission Profiles Health and Environmental Affairs Department API PUBLICATION NUMBER 344 PREPARED UNDER CONTRACT BY: GL
2、EN ENGLAND AND BENJAMIN TOBY 18 MASON IRVINE, CALIFORNIA 9261 8 ENERGY AND ENVIRONMENTAL RESEARCH CORPORATION BARBARA ZIELINSKA DESERT RESEARCH INSTITUTE PO Box 60220 RENO, NEVADA 89506-0220 ENERGY AND ENVIRONMENTAL ENGINEERING CENTER JUNE 1998 American Petroleum Ins titute FOREWORD API PUBLICATIONS
3、 NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED. API IS NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS, MANWAC- TURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMPLOYEES, A
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5、HOD, APPARATUS, OR PRODUCT COV- ERED BY LETTERS PATENT. NEITHER SHOULD ANYTHING CONTAINED IN ITY FOR INFRINGEMENT OF LEITERS PATENT. THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- i All rights reserved. No part of this work may be reproduced, stored in a retrieval system, or transmi
6、tted by any means, electronic, mechanical, photocopying, recording, or otherwise, without prior written permission from the publisher Contact the publisher, API Publishing Services, 1220 L Street, N. W, Washington, D.C. 20005. Copyright O 1998 American Petroleum Institute . 111 Previous page is blan
7、k STD.API/PETRO PUBL 344-ENGL 1998 I 0732290 Ob10345 221 W ACKNOWLEDGMENTS THE FOLLOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT: API STAFF CONTACT Karin Ritter, Health and Environmental Affairs Department MEMBERS OF
8、 THE PM SOURCE CHARACTERIZATION WORKGROUP Karl Loos, Shell, Chairperson Dan Baker, Shell Irv Crane, Exxon Lee Gilmer, Texaco Miriam Lev-On, ARCO Al Verstuyft, Chevron Dan Van Der Zanden, Chevron Stephen Ziman, Chevron iv Section Page ACRONYMS EXECUTIVE SUMMARY . ES- 1 1 . INTRODUCTION 1-1 REPORT ORG
9、ANIZATION . . 1-2 2 . BACKGROUND 2-1 NATIONAL AMBIENT PM2.5 STANDARDS 2-1 PARTICULATE MATTER IN THE ATMOSPHERE . 2-1 Particle Size 2-2 Factors Affecting Ambient Particle Size and Composition 2-2 Chemical Composition . 2-6 AEROSOL FORMATION . 2-9 Primary Particles 2-9 Secondary Particles: Chemical an
10、d Physical Transformation in the Atmosphere 2-11 Secondary Sulfate Pathways . 2-12 Secondary Nitrate Pathways . 2-13 Secondary Organic Aerosols 2-15 PETROLEUM INDUSTRY COMBUSTION SOURCES 2-23 AMBIENT AIR SAMPLING AND ANALYSIS METHODS 3-1 AMBIENT PARTICULATE SAMPLING METHODS . 3-1 Size-Selective Inle
11、ts 3-1 Filter Media and Filter Holders . 3-3 3 . Flow Measurement, Control, and Movement . 3-4 FILTER ANALYSIS METHODS 3-4 Mass 3-4 Elements 3-5 Ions 3-5 STD=API/PETRO PUBL 344-ENGL 1998 0732290 Ob10347 OT4 m 3 . AMBIENT AIR SAMPLING AND ANALYSIS METHODS continued . Carbon Measurements 3-6 Speciated
12、 Organic Compounds 3-6 ORGANIC GAS SAMPLING AND ANALYSIS METHODS 3-7 Whole-Air Sampling 3-7 Preconcentration Methods 3-9 Selective Methods of Compound Preconcentration 3-10 Semi-Volatile Compounds . 3-11 4 . TRADITIONAL STATIONARY SOURCE EMISSION MEASUREMENTS . 4-1 PARTICULATE EMISSIONS . 4-3 PARTIC
13、LE SIZE DISTRIBUTION AND PMiO . 4-5 PM2.5 PRECURSORS 4-7 Semivolatile Organic Compounds 4-7 Ammonia . -4-9 NO, and SO, 4-12 4-12 so, Elemental Analysis . 4-13 5 . AEROSOL SOURCE EMISSIONS MEASUREMENTS 5-1 DILUTION SAMPLING VERSUS TRADITIONAL APPROACHES . 5-1 EVOLUTION OF DILUTION SAMPLER DESIGNS . 5
14、-4 CURRENT DILUTION SAMPLER DESIGNS 5-8 Caltech System . 5-10 Desert Research Institute (SRI) System . 5-13 Nuclear Environmental Analysis, Inc . (NEA) System 5-15 URG System 5-19 Southern Research Institute System . 5-21 California Air Resources Board System . 5-23 CONSIDERATIONS FOR PETROLEUM INDU
15、STRY SOURCE TESTS . 5-25 Portability 5-25 Sample Collection . 5-25 Sampling Media Selection 5-26 6 . RECOMMENDATIONS 6-1 TEST OBJECTIVES 6. 1 TEST METHODOLOGY . 6. 1 Dilution Ratio 6-5 Residence Time 6-5 Particle Losses 6-6 Sample Contamination . 6-7 Flow Control and Measurement . 6-7 Field Use 6-8
16、7 . REFERENCES 7-1 2.1 . 2.2 . 2.3 . 2.4 . 2.5 . 2.6 . 2.7 . 4.1 . 4.2 . 4.3 . 4.4 . I 4.5 . 5.1 . i 5.2 . 5.3 . 5.4 . 5.5 . 5.6 . 5.7 . 5.8 . 5.9 . STD.API/PETRO PUBL 344-ENGL 1998 = 0732290 ObL0349 977 = LIST OF FIGURES Figure Fine Particulate Formation Pathways . 2-3 Idealized Size Distribution o
17、f Particles in Ambient Air 2-3 Aging Time for Homogeneously Distributed Particles of Different Aerodynamic Diameters in a 100 m Deep Mixer Layer . Gravitational Settling is Assumed for Both Still and Stirred Chamber Models 2-5 Mass Balance on the Chemical Composition of Annual Mean Fine Particle Con
18、centration, 1982, for (a) West Los Angeles and (b) Rubidoux (Riverside) California 2-8 Surface Area Distribution of Particles from the Combustion of Several Organics and from Automobiles and a Candle . 2-10 Mass Chromatograms of the Molecular Ion of the Nitrofluorantheses (NF) and Nitropyrenes (NP)
19、Formed from the Gas-Phase Reaction of Fluoranthene and Pyrene with the OH Radicals and Present in Ambient Particulate Sample Collected at Torrance, California 2-22 Emissions of POM from Selected Petroleum Industry Combustion Devices . 2-29 EPA Method 5 Particulate Matter Sampling Train . 4-4 Illustr
20、ation of Draft EPA Method 206 Sampling Train Assembly . 4-11 Continuous Emissions Monitoring System . 4-14 Collection in H,O, Impingers) 4-15 Distilled Oil-Fired Industrial Boiler 5-3 Early Dilution Sampling Methods 5-6 EPA Method O010 Sampling Train for SVOCs 4-8 Controlled Condensation Sampling Tr
21、ain for SO, (with Modification for SO, Organic Carbon Collected by Filtration vs . Dilution Sampling Procedure for Caltech Dilution Sampling System Design 5-11 Schematic Diagram of the DRI Dilution System . 5-14 Dilution Tunnel Sampler on Top of Test Shed . 5-16 NEA (Keystone) Dilution Sampling Syst
22、em Design . 5-18 URG Dilution Sampling System Design . 5-20 SRI Dilution Sampling System Design 5-22 California ARB Dilution Sampling System . 5-24 Fi eure 5- 1 O. 6-1. Table 2-1. 2-2. 2-3. 2-4. 2-5. 2-6. 2-7. 2-8. 2-9. 4-1. 4-2. 5-1. 5-2. 5-3. STD-APIIPETRO PUBL 344-ENGL 3998 0732290 Ob30350 699 LI
23、ST OF FIGURES continued . Pag.e Typical Sampling Protocol . 5-27 Overview of Recommended Measurements for Characterizing Emissions of Fine Particulate, Especially Organic Aerosols, and Its Precursors from Combustion Devices 6-3 LIST OF TABLES Chemicals in Primary Particles Emitted from Different Emi
24、ssion Sources . 2-7 Calculated Atmospheric Lifetimes for Gas-Phase Reactions of Selected Gas-Phase Compounds with Atmospherically Important Reactive Species 2-15 The Maximum Concentrations of Nitrofluoranthene (NF) and Nitropyrene (NP) Isomers Observed at Three South Coast Air Basin Sampling Sites .
25、 2-20 Apportionment of Carbonaceous Aerosols in South Coast Air Basin 2-24 Petroleum Industry Stationary Combustion Devices . . ._. . . . _. 2-25 Summary of Particulate Emissions from Oil-Fired Boilers . . . . . 2-26 Particulate Emissions and Particle Size Data for Selected Non-Fired Refinery Air Em
26、ission Sources 2-27 Total Filterable Particulate and PMi Emissions from FCCUs in Southern EPA Method 201N202 Results for Oil- and Gas-Burning Boilers and Turbines . 2-28 Flue Gas Source Sampling and Analytical Methods . . 4-2 Method 301 Validation Results for Source Vost Train . 4-10 Comparison of T
27、otal Particulate Concentration Using Dilution Sampling Versus Comparison of PAH Emissions from a Diesel Engine Using CAM Method 429 and Dilution Sampling . 5-4 Features of Published Dilution Sampler Designs . . . . . 5- 10 California . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
28、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-27 EPA Method 5 5-2 CLm 2-NF AAS AC API ASME C Caco, Caltech CARE3 ccu Cl2 CO2 D, cm CO DHS DNPH DRI dscm EASA EC ECD EER EPA ESP F FCCU FID ft RIR g-rn- GUMS GC H2SO4 HEPA HEST Hg hivol “O2 HNO, H
29、O2 HPLC HRSG IC IC engine ICP STD*API/PETRO PUBL 3q4-ENGL 1998 W 0732290 ObL035L 525 ACRONYMS micrometer (micron) 2-Nitrofluoranthene atomic adsorption spectrometry automated chromatography American Petroleum Institute American Society of Mechanical Engineers boiigpoint benzo alpyrene centigrade n-p
30、entadecane propane California calcium carbonate California Institute of Technology California Air Resources Board caytic cracking unit chlorine (molecular) centimeter carbon monoxide carbon dioxide 50 percent cutoff diameter Department of Health Services 2,4 dinitrophenyIhydrazine Desert Research In
31、stitute dry standard cubic meter electrical aerosol size analyzer elemental carbon electron capture detector Energy and Environmental Research Corporation Environmental Protection Agency electrostatic precipitator Fahrenheit fluidized catalytic cracking unit flame ionization detector feet fourier tr
32、ansform infrared spectroscopy grams per cubic centimeter mass spectrometric detector gas chromatography sulfuric acid high efficiency particulate air high efficiency sampling train mercury high volume nitrous acid nitric acid hydroperoxyl radical high performance liquid chromatography heat recovery
33、steam generator ion chromatography internal combustion engine inductively coupled plasma INA4 K2C03 Lc MS NAAQS NaCl NaNO, NaOH Ncm NDIR NEA NF ng “3 (“,)*SO, NH,HSO, “,NO3 NMHC NO NGO3 NO2 NO3 NO, NP o;: OH PAH PAK PAN PAQ PCB PEE PM PMio PM2.5 POM PPbV PSDS PSVOC PUF PVC RADS Re ROG SCAQMD SCAQS S
34、CR sec instrumental neutron activation analysis potassium carbonate liquid chromatography liters per minute milligram magnesium carbonate microorifce uniform deposit impactor mass spectrometry sodim carbonate national ambient air quality standards sodium chloride sodiumnitrate sodium hydroxide norma
35、l cubic meter (OOC) non-dispersive infrared Nuclear Environmental Analysis, Inc. nitrofluoranthene nanogram ammonia ammonium sulfate ammonium bisulfate ammonium nitrate non-methane hydrocarbons nitric oxide nitrogen dioxide nitrate (ion) oxides of nitrogen nirop yrene ozone organic carbon hydroxyl (
36、radical) polycyclic aromatic hydrocarbons polycyclic aromatic ketones peroxyacetyi niirate polycyclic aromatic quinones polychlorinated biphenyls proton induced X-ray emission particulate matter particulate matter equal to or smaller than 10 microns in diameter particulate matter equal to or smaller
37、 than 2.5 microns in diameter polycyclic organic matter parts per billion (volume) plume simulation dilution sampler particulatdsemi-volatile organic compound sampler polyurethane foam poly vinyl chloride reduced artifact dilution sampler Reynolds number reactive organic gases South Coast Air Quaiit
38、y Management District southern California Air Quality Study selective catalytic NOx reduction second STD-API/PETRO PUBL 344-ENGL 1998 0732290 Ob30353 3T8 SFS so2 so3 SOCAB sox SRI T TA TCE TEA TMO TOR TOT TSP URG UV VOC VIV WSPA XRF sequential filter samplers sulfur dioxide sulfur trioxide South Coa
39、st Air Basin oxides of sulfur Southern Research Institute thermal thennai absorption trichloroethylene triethanolamine thermal manganese oxidation thenrdoptical reflectance thedoptical transmission total suspended particulate University Research Glassware ultraviolet volatile organic compounds volum
40、e per volume Western States Petroleum Association X-ray fluorescence EXECUTIVE SUMMARY This report presents a critical review of sampling and analysis techniques for characterizing stationary source emissions of organic aerosols, fine particulate matter, and their precursors. This information is int
41、ended for use in designing future measurement programs for characterizing emissions from stationary sources which contribute to fine particle concentrations in the atmosphere. The review is based on relevant literature and discussions with technicalkcientific experts in academia, industry and the re
42、gulatory community. The benefits and drawbacks of various measurement approaches are discussed, and a recommended approach for combustion sources is presented. BACKGROUND The recent change in the National Ambient Air Quality Standards (NAAQS) for particulate matter (PM) includes new annual and 24-ho
43、ur standards for particles 2.5 pm or less in diameter, referred to collectively as PM2.5. The geologic component of PM2.5 is typically 10 percent or less; the balance is typically sulfates, nitrates and carbon (e.g., sulfuric acid, ammonium bisulfate, ammonium sulfate, ammonium nitrate, and organic
44、and elemental carbon). Organic compounds are important components of particulate matter and most of the particulate organic carbon is believed to reside in the fine particle fraction. For example, in an early study of the Los Angeles area, organic compounds constituted approximately 30 percent of th
45、e fine particle mass. Particulate matter may be either directly emitted into the atmosphere (primary particulate) or formed there by chemical reactions and physical transformations (secondary particulate). The majority of primary particulate emissions from combustion are found in the PM2.5 or smalle
46、r size range, especially with clean burning fuels such as gas. Sulfates and nitrates are the most common secondary particles, although organic carbon also can result from reaction of volatile organic compounds. The gaseous precursors of most particulate sulfates and nitrates are sulfur dioxide, sulf
47、ur trioxide, and oxides of nitrogen. Secondary organic aerosol formation mechanisms are not well understood due to the multitude of precursors involved and the rates of formation which are heavily dependent on meteorological variables and the concentrations of other pollutants. It is believed, howev
48、er, that atmospheric transformations leading to the formation of secondary aerosol from gas-phase primary organic emissions may be significant in some areas, particularly during the summertime. The chemical composition of PM2.5 strongly suggests combustion devices as the principal source in urban ar
49、eas. ES-1 STD-APIIPETRO PUBL 3YY-ENGL 1998 m 0732290 Ob10355 170 m PETROLEUM INDUSTRY COMBUSTION SOURCES Petroleum industry combustion devices likely are minor sources of carbonaceous aerosols in ambient fine particulate matter. An estimate of fine carbonaceous aerosol emissions from major sources in the Los Angeles area based on 1982 data showed that emissions from natural and refinery gas combustion (0.5 percent), petroleum industrial processes (0.7 percent), and coke calciners (0.6 percent) comprised a minor but significant fraction (1.8 percen
