Draft 3 Guideline on Speciated Particulate Monitoring PREPARED BY Judith C. Chow John G. Watson Desert Research Institute P.O. Box 60220 Reno, NV 89506 PREPARED FOR Neil Frank Jim Homolya Office of Air Quality Planning and Standards (MD-14) U.S. Environmental Protection Agency Research Triangle Park, NC 27711 August 1998 TABLE OF CONTENTS Page List of Tables .................................................... iii List of Figures .................................................... v 1.0 INTRODUCTION ................................................. 1-1 1.1 Background ................................................ 1-1 1.2 Objectives .................................................. 1-2 1.3 Related Documents ........................................... 1-2 1.4 Guide to Document .......................................... 1-3 2.0 PHYSICS AND CHEMISTRY OF ATMOSPHERIC PARTICLES ............ 2-1 2.1 Particle Size Distributions ...................................... 2-1 2.2 Major Chemical Components ................................... 2-2 2.3 Properties that Quantify Source Contributions ...................... 2-5 2.4 Particle Properties that Affect Human Exposure and Health ........... 2-11 3.0 PARTICLE SAMPLERS ............................................ 3-1 3.1 Sampler Components ......................................... 3-1 3.1.1 Size-Selective Inlets ................................... 3-1 3.1.2 Filter Media and Filter Holders ........................... 3-3 3.1.3 Flow Measurement, Control, and Movement ................. 3-6 3.2 Federal Reference and Equivalent Methods ......................... 3-7 3.2.1 PM2.5 Federal Reference Method .......................... 3-7 3.2.2 Class I PM2.5 Federal Equivalent Method ................... 3-8 3.2.3 Class II PM2.5 Federal Equivalent Method ................... 3-9 3.2.4 Class III PM2.5 Federal Equivalent Method .................. 3-9 3.3 IMPROVE Samplers ......................................... 3-9 3.4 Research Samplers .......................................... 3-10 4.0 LABORATORY ANALYSIS METHODS ............................... 4-1 4.1 Filter Analysis Protocols ....................................... 4-1 4.2 Filter Handling and Storage .................................... 4-2 4.3 Mass Measurement Methods .................................... 4-5 4.4 Elemental Analysis Methods .................................... 4-6 4.5 Water-Soluble Ion Analysis Methods ............................ 4-12 4.6 Carbon Analysis Methods ..................................... 4-17 4.6.1 Thermal Manganese Oxidation Method for Carbon ........... 4-18 4.6.2 Thermal Optical Reflectance/Transmission Method for Carbon .. 4-19 4.6.3 Filter Transmission for Light Absorbing Carbon ............. 4-20 4.7 Organic Speciation .......................................... 4-21 4.8 Individual Particle Analysis .................................... 4-23 4.8.1 CCSEM Analysis .................................... 4-24 i TABLE OF CONTENTS (continued) Page 4.8.2 Electron Microprobes ................................. 4-27 4.8.3 Transmission Electron Microscopy ....................... 4-27 5.0 MEASUREMENT ARTIFACTS AND INTERFERENCES ................. 5-1 5.1 Particle and Gas Removal in Inlets ............................... 5-1 5.2 Ammonium Nitrate Volatilization ................................ 5-2 5.3 Sulfur Dioxide and Oxides of Nitrogen Adsorption ................... 5-3 5.4 Organic Carbon Adsorption and Volatilization ...................... 5-3 5.5 Liquid Water Content ......................................... 5-4 5.6 Electrostatic Charge .......................................... 5-5 5.7 Passive Deposition and Recirculation ............................. 5-5 6.0 QUALITY ASSURANCE ........................................... 6-1 6.1 Standard Operating Procedures .................................. 6-1 6.2 Quality Audit Objectives ....................................... 6-2 6.3 Laboratory Performance Audit .................................. 6-2 7.0 DATA BASE MANAGEMENT AND DATA VALIDATION ................ 7-1 7.1 Data Base Requirements ....................................... 7-2 7.2 Data Validation .............................................. 7-3 7.3 Substrate Data Processing ...................................... 7-4 8.0 MONITORING STRATEGIES ....................................... 8-1 8.1 General Approach ............................................ 8-1 8.2 Analysis of Archived PM2.5 FRM Filters ........................... 8-3 8.3 Variations to FRM or FEM Sampling ............................. 8-4 8.4 Saturation Sampling .......................................... 8-5 8.5 Precursor Gaseous Sampling .................................... 8-6 9.0 SUMMARY ................................................... 9-1 10.0 BIBLIOGRAPHY ................................................ 10-1 ii LIST OF TABLES Page Table 2-1 Examples of Organic Compounds Found in Different Emission Sources and in Ambient Air .................................. 2-15 3 Table 2-2 Average PM10 Composition (µg/m ) in Selected Urban and Non-Urban U.S. Areas ...................................... 2-16 3 Table 2-3 Average PM2.5 Composition (µg/m ) in Selected Urban and Non-Urban U.S. Areas ...................................... 2-22 Table 2-4 Receptor Model Source Contributions to PM10 .................... 2-27 Table 3-1 Size-Selective Inlets for Aerosol Sampling ....................... 3-12 Table 3-2 Commonly Used Filter Media for Particulate Sampling and Analysis .... 3-16 Table 3-3 Filter Holders and their Characteristics .......................... 3-24 Table 3-4 Flow Measurement, Flow Control, and Flow Movers ............... 3-27 Table 3-5 U.S. EPA Designated Reference and Equivalent Methods for PM10 .... 3-32 Table 3-6 Filter-Based Particle Sampling Systems ......................... 3-34 Table 3-7 Test Specifications for PM2.5 Equivalence to FRM ................. 3-40 Table 3-8 Continuous Aerosol Sampling and Analysis Systems ................ 3-41 Table 4-1 Detection Limits of Air Filter Samples for Different Analytical Methods . 4-28 Table 4-2 Examples of Minimum Detection Limits for Low-Volume and Medium-Volume Gas and Particle Measurements .................. 4-31 Table 4-3 Summary of Filter Acceptance Test Results Performed at DRI's Environmental Analysis Facility between 1992 and 1997 ............. 4-33 Table 4-4 Federal Filter Specifications for PM2.5 Sample Collection ............ 4-38 Table 4-5 Examples of Filter Impregnation and Extraction Solutions Applied in Ion Chromatographic Analysis .............................. 4-39 iii LIST OF TABLES (continued) Page Table 4-6 Summary of Ion Chromatographic Compliance Testing Methods ...... 4-40 Table 4-7 Examples of Commercial Quality Control Standards for Anion and Cation Analysis ............................................ 4-43 Table 4-8 Carbon Analysis Method Characteristics ......................... 4-45 Table 4-9 Sampling and Analysis Methods for Common Ambient VOC Classes ... 4-49 Table 6-1 Examples of Standard Operating Procedures to be Applied in the PM2.5 Chemical Speciation Monitoring Network .................... 6-4 Table 6-2 Examples of Laboratory Performance Audit Observables ............. 6-7 Table 7-1 Examples of Ambient Field Sampling Data Validation Flags ........... 7-6 Table 7-2 Examples of Chemical Analysis Data Validation Flags ............... 7-9 Table 8-1 Example of Program Plan Outline for PM2.5 Measurement and Modeling . 8-7 iv LIST OF FIGURES Page Figure 2-1 Idealized size distribution of particles in ambient air. ............... 2-30 Figure 2-2 Size distributions of several particulate source emissions. ........... 2-31 Figure 2-3 Comparison between calculated and measured ammonium at the ten SJVAQS/AUSPEX sites for PM2.5 and PM10 size fractions. .......... 2-32 Figure 2-4 Geological material source profiles derived for northwestern Colorado. 2-33 Figure 2-5 Motor vehicle source profiles derived for northwestern Colorado. .... 2-34 Figure 2-6 Emissions from burning source profiles derived for northwestern Colorado. ............................................... 2-35 Figure 2-7 Coal-fired boiler source profiles derived for northwestern Colorado. ... 2-36 Figure 2-8 Deposition of particles inhaled into the human body. ............... 2-37 Figure 3-1 Characteristics of sampling effectiveness curves for WINS and other PM2.5 inlets. ............................................. 3-49 Figure 3-2 Changes in particle size distribution after passing through PM2.5 and PM10 inlets. .......................................... 3-50 Figure 3-3 Schematic of a modified SA-246 PM10 inlet. ..................... 3-51 Figure 3-4 Schematic of a WINS PM2.5 inlet. ............................. 3-52 Figure 3-5 Comparison of PM2.5 measurements from two WINS samplers with simultaneous measurements from dichotomous and IMPROVE samplers at the Bakersfield site between 01/21/97 and 03/19/97. ...... 3-53 Figure 3-6 National parks and monuments, national wildlife refuges, national forests, Indian reservations, and IMPROVE background monitoring sites. ................................................... 3-54 v LIST OF FIGURES (continued) Page Figure 4-1 Flow diagram of the sequential filter samplers for PM2.5 mass, light absorption, elements, ions, and carbon measurements at the Welby site during winter and summer 96 and the Brighton and Welby sites during winter 97. ......................................... 4-51 Figure 4-2 Flow diagram of filter processing and chemical analysis activities for the aerosol and gaseous