£EPA
Environmental Protection EPA-600/R-03/100a
Agency November 2003
Source Sampling Fine
Particulate Matter: A
Kraft Process Hogged
Fuel Boiler at a Pulp and
Paper Facility: Volume 1,
Report
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EPA-600/R-03/100a
November 2003
Source Sampling Fine Particulate
Matter: A Kraft Process Hogged Fuel
Boiler at a Pulp and Paper Facility:
Volume 1, Report
by
Joan T. Bursey and Dave-Paul Dayton
Eastern Research Group, Inc.
1600 Perimeter Park Drive
Morrisville, NC 27560
Contract No. 68-D7-0001
EPA Project Officer: N. Dean Smith
Air Pollution Prevention and Control Division
National Risk Management and Research Laboratory
Research Triangle Park, NC 27711
Prepared for:
U.S. Environmental Protection Agency
Office of Research and Development
Washington, DC 20460
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Abstract
Fine particulate matter of aerodynamic diameter 2.5 |im or less (PM25) has been
implicated in adverse health effects, and a National Ambient Air Quality Standard for PM2 5
was promulgated in July 1977 by the U.S. Environmental Protection Agency. A national
network of ambient monitoring stations has been established to assist states in determining
areas which do not meet the ambient standard for PM2 5. For such areas, it is important to
determine the major sources of the PM2 5 so states can devise and institute a control strategy
to attain the ambient concentrations set by the standard.
One of the tools often used by states in apportioning ambient PM2 5 to the sources is a
source-receptor model. Such a model requires a knowledge of the PM2 5 chemical
composition emitted from each of the major sources contributing to the ambient PM2 5 as
well as the chemical composition of the PM2 5 collected at the receptor (ambient monitoring)
sites. This report provides a chemical composition profile for the PM2 5 emitted from an
auxiliary boiler fired with a mixture of wood bark (hogged wood waste) and bituminous coal
at a pulp and paper mill utilizing the Kraft process. The boiler was rated to generate a
maximum of 889 Mbtu/hour and was equipped with a control system which included a
multicyclone-electroscrubber system installed on the flue gas duct and bag filters installed
on the vents of the coal bins, scrubber ash silo, and boiler ash silo. Along with the PM2 5
emission profile, data are also provided for gas-phase emissions of several organic
compounds. Gaseous reduced sulfur compound emissions, however, were not included in
this study. Data are presented both as mass emission factors (mass of emitted species per
unit mass of fuel consumed) and as mass fraction compositions (e.g., mass fraction of
individual components comprising the PM2 5). Data are provided in a format suitable for
inclusion in the EPA source profile database, SPECIATE.
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting
the Nation's land, air, and water resources. Under a mandate of national environmental laws,
the Agency strives to formulate and implement actions leading to a compatible balance
between human activities and the ability of natural systems to support and nurture life. To meet
this mandate, EPA's research program is providing data and technical support for solving
environmental problems today and building a science knowledge base necessary to manage
our ecological resources wisely, understand how pollutants affect our health, and prevent or
reduce environmental risks in the future.
The National Risk Management Research Laboratory (NRMRL) is the Agency's center for
investigation of technological and management approaches for preventing and reducing risks
from pollution that threaten human health and the environment. The focus of the Laboratory's
research program is on methods and their cost-effectiveness for prevention and control of
pollution to air, land, water, and subsurface resources; protection of water quality in public
water systems; remediation of contaminated sites, sediments and ground water; prevention
and control of indoor air pollution; and restoration of ecosystems. NRMRL collaborates with
both public and private sector partners to foster technologies that reduce the cost of
compliance and to anticipate emerging problems. NRMRL's research provides solutions to
environmental problems by: developing and promoting technologies that protect and improve
the environment; advancing scientific and engineering information to support regulatory and
policy decisions; and providing the technical support and information transfer to ensure
implementation of environmental regulations and strategies at the national, state, and
community levels.
This publication has been produced as part of the Laboratory's strategic long-term research
plan. It is published and made available by EPA's Office of Research and Development to
assist the user community and to link researchers with their clients.
Lawrence W. Reiter, Acting Director.
National Risk Management Research Laboratory
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EPA Review Notice
This report has been peer and administratively reviewed by the U.S. Environmental
Protection Agency and approved for publication. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Information
Service, Springfield, Virginia 22161.
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Table of Contents
Volume 1, Report
Section Page
Abstract ii
List of Tables viii
List of Figures x
Nomenclature xi
Acknowledgments xii
Introduction 1
Characterization of a Hogged Fuel Boiler at a Pulp and Paper Facility 2
Report Organization 4
Conclusions 5
Methods and Materials 7
Description of Test Equipment 8
Dilution Sampling System 9
Dilution Sampling System Control Instrumentation 12
Sample Collection Arrays 14
Process Description/Site Operation 14
Pre-Test Survey 18
Experimental Procedures 19
Preparation for Test Setup 19
Traverse Point Determination Using EPA Method 1 19
Volumetric Flow Rate Determination Using EPA Method 2 21
Pitot Tube Calibration 21
Calculation of Average Flue Gas Velocity 21
Nozzle Size Determination 23
Measurement of 02, C02, and CO Concentrations for Calculating Stack
Parameters 23
Stationary Gas Distribution (as Percent Volume) 23
Dry Molecular Weight of Flue Gas 23
Wet Molecular Weight of Flue Gas 24
Determination of Average Moisture Using EPA Method 4 24
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Table of Contents (continued)
Section Page
Volume of Dry Flue Gas Sampled at Standard Conditions (dscf) 24
Volume of Water Vapor at Standard Conditions (dscf) 25
Calculation of Moisture/Water Content (as percent volume) 25
Calculation of Dry Mole Fraction of Flue Gas 26
Setup of the Dilution Sampling System 26
Pre-Test Leak Check 29
Orifice Flow Check 31
Determination of Test Duration 31
Canister/Veriflow Blanks 31
Determination of Flow Rates 32
Sample Collection Arrays 32
Dilution Chamber Sample Collection Arrays 32
Residence Chamber Sample Collection Arrays 34
Denuder Sampling 35
Use of the ELPI Particle Size Distribution Analyzer 35
Measurement of 02 and C02 Process Concentrations 37
Operation of the Dilution Sampling System with Sample Collection Arrays 37
Dilution System Sample Collection Arrays: Train Recovery 47
Laboratory Experimental Methodology 49
PM2 5 Mass 49
Elemental Analysis 49
Water-Soluble Inorganic Ions 49
Elemental Carbon/Organic Carbon 50
Organic Compounds 50
Carbonyl Compounds 51
Canister Analyses: Air Toxics and Speciated Nonmethane Organic
Compounds 53
Particle Size Distribution Data 54
Results and Discussion 59
Calculated Emission Factors for PM Mass, Carbonyls, and Nonmethane Organic
Compounds 59
Gas-Phase Carbonyl Compounds Profile 60
Gas-Phase Air Toxic Compounds—Whole Air Samples 63
Gas-Phase Speciated Nonmethane Organic Compounds Profile 64
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Table of Contents (continued)
Section Page
PM2 5 Elemental/Organic Carbon, Major Inorganic Ion, and Major Element Profile 64
Particle Size Distribution Data 64
PM2 5 Semivolatile Organic Compounds 74
Measurement of 02 and C02 75
Quality Assurance/Quality Control 79
Field Sampling 79
Carbonyl Compound Analysis 81
Concurrent Air Toxics/Speciated Nonmethane Organic Compound (SNMOC)
Analysis 83
PM Mass Measurements, Elemental Analysis, Water-Soluble Ion Analysis,
Organic/Elemental Carbon, and GC/MS Analysis 85
References 91
Volume 2, Appendices
A Table of Unit Conversions A-l
B Hogged Fuel Boiler No. 2 Sample Log with Sample IDs and Chain of Custody
Documentation B-l
C Example Calculations: NMOC, Carbonyl, and PM2 5 Mass Emission
Factors C-l
D Data Tables for Individual PM25 Mass Measurements D-l
E Data Tables for Individual Carbonyl Samples E-l
F Data Tables for Individual NMOC Samples F-l
G Data Tables for Individual Air Toxics Samples G-l
H Data Tables for Individual PM2 5 Elemental Samples H-l
I Data Tables for Individual PM2 5 EC/OC Samples 1-1
J Data Tables for Individual PM2 5 Inorganic Ion Samples J-l
K Supporting Calibration and Data Tables for Individual Semivolatile
Organic Compounds K-l
L List of ERG SOPs and EPA MOPs by title I.-l
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List of Tables
Table Page
1 Sampling Medium Used for Collection of Samples, Analysis Performed,
Analytical Method, and Responsible Laboratory 7
2 Analysis of Coal and Wood Chip Hogged Fuel 17
3 Hogged Fuel Boiler No. 2 Fuel Use During the Test Period 18
4 EPA Method 1 Traverse Point Locations for the Circular Hogged Fuel Boiler No. 2
Exhaust Duct 20
5 Average Flue Gas Velocity for Each Traverse Point 22
6 Moisture Recovery for Method 4 24
7 Blank Values for Veriflows and Canisters 31
8 Denuder Sampling Scheme 36
9 Run Time Summary Information, Test Run 1 (11/27/01) 38
10 Run Time Summary Information, Test Run 2 (11/28/01) 40
11 Run Time Summary Information, Test Run 3 (11/29/01) 41
12 Carbonyl Compounds Analyzed by High Performance Liquid Chromatography:
Method Detection Limits 52
13 Method Detection Limits for Air Toxics Compounds (Analytical Method TO-15) . 54
14 Method Detection Limits for Speciated Nonmethane Organic Compounds 56
15 Fine Particle, Carbonyl, and Nonmethane Organic Compound Emission
Factors from a Hogged Fuel Boiler at a Pulp and Paper Facility 60
16 Gas-Phase Carbonyl Compounds Profile, Hogged Fuel Boiler (Carbonyl
Compounds Collected in Diluted Stack Gas Corrected for Carbonyl
Compounds in Dilution Air) 61
17 Summarized Analytical Results for Air Toxics Compounds Observed on Each
of the Three Test Days (11/27/01 through 11/29/01) 63
18 Speciated and (Speciated + Unspeciated) NMOC Data for All Three Test
Days, with Mass Fraction, Mean, and Uncertainty 65
19 Fine Particle Chemical Composition of Emissions from a Hogged Fuel Boiler
at a Pulp and Paper Facility 69
20 Particle Size Distribution Data 70
21 Organic Compounds Positively Identified in the PM2 5 Emissions from the
Hogged Fuel Boiler 74
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List of Tables (continued)
Table Page
22 Field Sampling Equipment Quality Control Measures 80
23 Carbonyl Analysis: Quality Control Criteria 81
24 Quality Control Procedures for the Concurrent Analysis for Air Toxics
and SNMOCs 84
25 PM Mass Measurements: Quality Control Criteria 86
26 Elemental Analysis: Quality Control Criteria 86
27 Water-Soluble Ion Analysis: Quality Control Criteria 87
28 Quality Control Procedures for Organic/Elemental Carbon Analysis of PM2 5 88
29 Quality Control Procedures for Gas Chromatography-Mass Spectrometry
Analysis of Semivolatile Organic Compounds 89
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List of Figures
Figure Page
1 Diagram of the Dilution Sampler and Dilution Air Conditioning System 10
2 Instrumentation for Control and Analysis of the Dilution Sampler 13
3 Hogged Fuel Boiler No. 2 Sampling Port Location 15
4 Hogged Fuel Boiler Sampling Location Layout—Top View 16
5 Hogged Fuel Outdoor Coal Storage Area 16
6 Hogged Fuel Outdoor Wood Storage Area 17
7 Dilution System Sampling Module Positioned at the Sampling Location 27
8 Dilution System Sampling Probe Installed in 6 in. id Flanged Port 27
9 Dilution System Control Module Positioned at the Sampling Location 28
10 ELPI Positioned at the Sampling Location 28
11 Dilution System with All Sample Collection Arrays and Instruments Attached ... 29
12 Recovery and Recharge Area for Denuders Used in the Dilution Sampling System 30
13 Sample Collection Arrays Used for Testing at the Hogged Fuel Boiler 33
14 Blower Flow, Day 1 (11/27/01) 43
15 Dilution Flow. Day 1 (11/27/01) 43
16 Venturi Flow, Day 1 (11/27/01) 44
17 Blower Flow, Day 2 (11/28/01) 44
18 Dilution Flow, Day 2 (11/28/01) 45
19 Venturi Flow, Day 2 (11/28/01) 45
20 Blower Flow, Day 3 (11/29/01) 46
21 Dilution Flow. Day 3 (11/29/01) 46
22 Venturi Flow, Day 3 (11/29/01) 47
23 Plots of Particle Counts vs. Size, Particle Mass vs. Size, and Particle Mass
per Stage for Test Day 1 (11/27/01) 71
24 Plots of Particle Counts vs. Size, Particle Mass vs. Size, and Particle Mass
per Stage for Test Day 2 (11/28/01) 72
25 Plots of Particle Counts vs. Size, Particle Mass vs. Size, and Particle Mass
per Stage for Test Day 3 (11/28/01) 73
26 02 and C02 Concentrations for Hogged Fuel Boiler No. 2 on Test Day 1 (11/27/01) 76
27 02 and C02 Concentrations for Hogged Fuel Boiler No. 2 on Test Day 2 (11/28/01) 77
28 02 and C02 Concentrations for Hogged Fuel Boiler No. 2 on Test Day 3 (11/29/01) 78
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Nomenclature
Term Definition
CMB chemical mass balance
DNPH 2,4-dinitrophenylhydrazine
EC/OC elemental carbon and organic carbon
ELPI electrical low pressure impactor
EPA U.S. Environmental Protection Agency
ERG Eastern Research Group
FID flame ionization detector
GC gas chromatography analytical technique
GRAV gravimetric analytical technique
HEPA high efficiency particulate arresting
HPLC high performance liquid chromatography analytical technique
HVLC high volume, low concentration
IC ion chromatography analytical technique
MDLs method detection limits
MOPs method operating procedures
MS mass spectrometry analytical technique
MSD mass selective detector
NH3 ammonia
NMOCs nonmethane organic compounds
NOx nitrogen oxides
PM particulate matter
PM2 5 particulate matter of aerodynamic diameter 2.5 |im or less
PM10 particulate matter of aerodynamic diameter 10 |im or less
PUF polyurethane foam
QAPPs quality assurance project plans
SIPs State Implementation Plans
SNMOCs speciated nonmethane organic compounds
SOPs standard operating procedures
SOx sulfur oxides
TMS trimethylsilyl
TOE thermal-optical evolution
VOCs volatile organic compounds
XRF X-ray fluorescence analytical technique
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Acknowledgments
Dave-Paul Dayton, Mark Owens, and Robert Martz of Eastern Research Group, Inc.
(ERG) were responsible for conducting sampling at the test site and for preparing collected
samples for transport to the analytical laboratories. Amy Frame, Donna Tedder, and Laura
VanEnwyck of ERG were responsible for the volatile organic compound and carbonyl
analyses. Joan Bursey and Raymond Merrill of ERG provided calculations, data analysis,
and sections of the report pertaining to the ERG work on this project. Wendy Morgan of
ERG prepared the typewritten manuscript.
Michael Hays, Kara Linna, and Jimmy Pau of the EPA, NRMRL-RTP, were responsible
for the analysis of organic compounds, elements, and ionic species. Yuanji Dong, John Lee,
David Proffitt, and Tomasz Balicki of ARCADIS, Geraghty & Miller, Inc., provided
technical support in preparing the dilution sampling system and sampling substrates, in
performing the elemental/organic carbon analyses, and in extracting organic compounds
from the various sampling substrates. N. Dean Smith was the EPA Project Officer
responsible for overall project performance.
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Introduction
In July 1997, the U.S. Environmental Protection Agency (EPA) promulgated new
National Ambient Air Quality Standards for ambient particulate matter (PM) of
aerodynamic diameter 2.5 |im or less (PM2 5) and revised the existing standard for ambient
particles of aerodynamic diameter 10 |im or less (PM10). In 1999, a national network of
ambient monitoring stations was started under the overall guidance of the EPA's Office of
Air Quality Planning and Standards to assist the States in determining regulatory non-
attainment areas and to develop State Implementation Plans (SIPs) to bring those areas into
compliance with the law for PM2 5 and revised PM10 regulations. One component of the
monitoring network is a number of regional airsheds in which intensive coordinated PM-
related research will be carried out to better understand the linkages between source
emissions and actual human dosages of fine PM.
The mission of the Emissions Characterization and Prevention Branch of the Air
Pollution Prevention and Control Division is to characterize source emissions and to
develop and evaluate ways to prevent those emissions. Source characterization as defined
here includes the measurement of PM mass emission factors, source PM profiles (PM
chemical composition and associated chemical mass emission factors), and emission factors
for ambient aerosol precursors such as sulfur oxides (SOx), nitrogen oxides (NOx), and
ammonia (NH3).
PM mass emission factors are used in emission inventories and as inputs to atmospheric
dispersion models that yield estimates of ambient PM concentrations from considerations of
atmospheric transport and transformation of emitted particles. Emissions composition data
are used in receptor models to enable apportionment of ambient concentrations of PM to the
various sources that emitted the particles. EPA has interest and investments in source
apportionment, ambient monitoring, and regulatory matters related to fine PM. For example,
states rely on source-receptor and dispersion models to target major sources of PM25 and to
devise cost-effective strategies for achieving compliance with the standard. EPA has a
longstanding effort to produce the models for use by the States and EPA. An example of a
source-receptor model is the Chemical Mass Balance (CMB) model, which requires as input
chemical composition data from both ambient and source samples. The field test reported
here focused on the collection of fine particles emitted by a hogged fuel boiler at a pulp and
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paper facility. Data were collected to evaluate new measurement techniques and to update
and improve source emission profiles and emission factors for PM2 5. For this particular
model, more and better source data are needed to allow:
The characterization of secondary organic aerosols formed by condensation of
semivolatile organic compounds and/or reaction of volatile organic compounds to
form higher molecular weight aerosols;
Increased differentiation of specific sources within source types; and
The major sources of ammonia emissions, which result in ammonium sulfate and
ammonium nitrate fine PM.
These data needs exist because:
Relatively few data exist on the organic composition of PM, particularly of
carbonaceous PM2 5, and the data that do exist represent only 5 wt% or less of the
total organic fraction of the PM;
Current PM2 5 organic speciation profiles are derived from tests of only a few sources
within a relatively few air sheds across the United States;
Certain organic components of PM2 5 may be responsible for observed adverse
human health effects associated with ambient fine PM;
Organic aerosols typically represent approximately 30% to 40% of the mass of
ambient PM2 5 in urban areas; and
Unlike SOx and NOx, ammonia emissions are poorly characterized since ammonia is
not considered a "criteria pollutant." However ammonia, in combination with
atmospheric sulfate and nitrate, forms secondary PM, which represents a substantial
portion of the total fine PM in ambient air.
Characterization of a Hogged Fuel Boiler at a Pulp and
Paper Facility
A sampling campaign was conducted during the last quarter of 2001 at a large pulp and
paper mill using the Kraft process to measure emissions from three of the mill's major
sources of atmospheric emissions; i.e., a recovery boiler fired with concentrated liquid
wastes (black liquor) from the wood digestion and pulp washing processes, an auxiliary
boiler combusting a mixture of wood bark (hogged wood waste) and bituminous coal, and a
vent from the smelt dissolving tank. This test report presents results from the emissions
testing of the auxiliary (hogged fuel) boiler. The primary aim of these tests was to determine
the amount and nature of the fine PM (PM2 5) emitted.
Previous work to determine PM emissions for this type of source focused on the
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filterable and condensible fractions of total PM emitted as measured by EPA Method 51 or
Method 202.2 A number of potential biases have been identified with the use of these EPA
methods including a negative mass bias when filterable PM is collected in a hot exhaust
stream without first cooling and diluting the exhaust, and a positive mass artifact of
condensible PM when the hot exhaust is quenched by passing it through a series of cold
impinger solutions without first diluting the exhaust stream. To minimize these sampling
artifacts, the present test campaign employed a state-of-the-art dilution sampling system
designed to dilute and cool the hot exhaust gas to near ambient conditions prior to collecting
the PM. Also, sufficient time was provided prior to collection of the PM to enable any
semivolatile organic compounds to distribute between the gas and particle phases as they
would do in the ambient air downstream from the stack. Sampling in this way should yield
more accurate, artifact-free, PM mass emission factors and particles whose composition is
the same as that in the ambient air downstream of the source.
In pulp and paper mills, process steam is largely supplied by combustion of concentrated
black liquor in the recovery boiler. Organic compounds present in the concentrated black
liquor constitute the combustible fuel for the recovery boiler. However, in most cases, the
recovery boiler alone cannot supply all of the heat to generate the process steam needed.
Conventional boilers burning coal, oil, natural gas, wood bark, or some combination of these
fuels are used to make up the deficiency. The boiler tested in this research was used to
provide auxiliary process steam and utilized as fuel a mixture of 72.6 wt% wood bark
(hogged wood waste), 27.4 wt% low-sulfur bituminous coal, and an insignificant amount of
high volume, low concentration (HVLC) gases from the black liquor evaporation process.
The HVLC gases typically make up less than 1% of the total fuel consumed during normal
operation.
The hogged fuel boiler tested was rated to generate a maximum of 889 MBtu/hour and
was equipped with a multistage control system, composed of the following components:
One multicyclone/electroscrubber system (one electrified granular filter bed);
Three bag filters installed on the de-entrainment vessel for the granular media used
in the electroscrubber;
Two filters installed on vents on the two coal bins;
Two bag filters installed on the vents of the boiler ash silo;
Two bag filters installed on vents on the scrubber ash silo; and
One bag filter installed on the storage vessel which holds the gravel media used in
the electroscrubber.
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Although fine PM was the focus of this particular test campaign, gas-phase organic
emissions were also collected concurrently and analyzed. Reduced sulfur gas emissions,
such as hydrogen sulfide, methyl mercaptan, and dimethyl sulfide, were not tested. This
report presents the results of these tests which were conducted over a 3-day period in late
October to early November of 2001. Prior to the sampling runs, EPA Methods l3, 24, and 45
were performed to establish the stack gas velocity, temperature, pressure, and exhaust gas
moisture content.
This report describes the nature of the source, the method of sampling, analysis methods
used to determine the composition of the PM and gas phase emissions, and the analysis
results—both in the form of mass emission factors (mass of emitted species per mass of fuel
consumed) and as mass fraction compositions. Results presented as mass emission factors
are expected to be useful in emission inventories. The composition of PM and gas-phase
emissions expressed as mass fractions can be used as source profiles for input to source-
receptor models used to apportion ambient atmospheric pollutants to the various sources
contributing to the ambient air pollution.
Report Organization
This report is organized into five additional sections plus references and appendices,
which are in a separate volume. Section 2 provides a summary of results and conclusions
derived from the study results, and Section 3 describes the process operation and the test
site. Section 4 outlines the experimental procedures used in the research, and Section 5
presents and discusses the study results. Section 6 presents the quality control/quality
assurance procedures used in the project to ensure generation of high quality data.
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Conclusions
During three replicate test runs conducted during three consecutive days (11/27-29/01),
the fine PM (PM2 5) emission factor averaged 50.0 mg/kg of fuel and was fairly consistent
(48.2-52.0 mg/kg fuel). This value is roughly twice the PM25 mass emission factor found
for the recovery boiler at the same facility. The size distribution of fine PM emitted from the
hogged fuel boiler was bimodal with a minor peak at 0.13 |im and a major peak at 1.7 |im
particle aerodynamic diameter. The overall mean diameter of the PM2 5 particles was 1.16
|im.
Approximately 68.5% of the PM composition by mass was identified and quantified.
Sulfate and chloride ions constituted 10% of the PM mass. Aluminum and silicon were the
dominant elements and together comprised 32.8%. Silicon, aluminum, and iron are the three
elements typically found in coal in the largest amounts. This fact, along with the possibility
of minor amounts of crustal material (alumino-silicate minerals) admixed with the wood and
coal fuels probably accounts for the predominance of these elements in the fine PM emitted.
Potassium was found to constitute 6.8% of the PM mass on average. Potassium is frequently
considered a marker for combustion of biomass (hogged wood waste in this case).
Elemental and organic carbon together averaged 7.9% of the fine PM mass. Organic
carbon alone (a measure of the organic compound content of the PM) was determined to be
6.2 wt% of the PM mass emitted. Although a number of organic compounds, principally
alkanes, were positively identified in the organic carbon fraction, the amounts of these
individual organic species were generally below the analytical limits for accurate
quantitation. Consequently, mass emission factors and composition mass fractions for the
individual organic compounds in the fine PM could not be accurately determined.
Significant concentrations of //-hexane, methylene chloride, and acetone were also
observed in the gas samples collected from the dilution sampler during all three test days
with unusually high concentrations of these compounds observed on the second test day.
However, the presence of these compounds may be artifactual. Different sets of the XAD-
coated annular denuders were extracted near the sampling location using these same three
solvents, and the denuders were placed into service on an alternating schedule to avoid
exceeding the capacity of a single set of denuders during a test run. Therefore, the presence
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of these three compounds in the stack gas samples collected by the dilution sampler and in
the ambient air sample collected on the stack are considered suspect and are likely due to
contamination arising from on-site extraction of the organic denuders. Values for
nonmethane organic compounds (both speciated and total), carbonyl compounds (both
speciated and total), and air toxics compounds have been recalculated deleting these
compounds on the second test day (11/28/01).
Gas-phase nonmethane organic compound emissions on the first and third test days were
about twice the level found in the recovery boiler emissions at the facility (11.30 mg/kg of
fuel for the hogged fuel boiler versus 5.92 mg/kg of fuel for the recovery boiler). On only
the second test day (11/28/01), the gas-phase nonmethane organic compound (NMOC)
emissions were much higher (246.96 mg/kg fuel) largely due to the presence of a single
compound, //-hexane. The //-hexane is a contaminant arising from the solvents used to
extract the denuders on-site. When the values are recalculated for 11/28/01 deleting n-
hexane, a value of 34.07 mg/kg fuel is obtained, much more consistent with the other test
days. When values for Test Day 2 were recalculated with the omission of acetone, a value of
2.74 mg/kg fuel was obtained.
Gas-phase carbonyl compound emissions on the first and third test days were about three
times the emission levels found in the Recovery Boiler emissions at the same facility (3.46
mg/kg fuel vs. 1.12 mg/kg fuel, respectively). Similarly to the NMOCs, the total gas-phase
carbonyl emissions were much higher on Test Day 2 (79.12 mg/kg fuel) largely due to the
presence of high levels of acetone observed in the emissions on that day.
Ambient air at the plant site was sampled on Test Day 1 (11/27/01) and was found to
contain 1147.86 |ig/m3 of gas-phase NMOCs with «-hexane, 3-methyl-pentane,
methylcyclopentane, and a-pinene being the dominant species. //-Hexane alone accounted
for approximately 35% of the NMOCs in the ambient air on that day. Methylene chloride
was the only air toxic compound found in the ambient air in significant quantities. Sampling
of the ambient air was done to ensure the dilution air cleanup system associated with the
dilution sampler was removing any pollutants present in the ambient air prior to being mixed
with the stack gas. Samples of the cleaned dilution air confirmed that ambient background
gases resulting from the on-site handling of the denuders and PM were indeed removed.
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Methods and Materials
A field test was conducted (November 27 to 29, 2001) on hogged fuel boiler No. 2 at a
pulp and paper facility to obtain source emissions measurements of high and known quality.
The objectives of the testing activities were to evaluate the sampling equipment and to
characterize the fine particulate and volatile organic emissions from a Kraft Process hogged
fuel boiler. To simulate the behavior of fine particles as they enter the ambient atmosphere
from an emissions source, dilution sampling was performed to cool, dilute, and collect
gaseous and fine particulate emissions from the hogged fuel boiler exhaust. Gaseous and
fine particulate samples collected were chemically characterized. Eastern Research Group
(ERG) coordinated all field test activities; laboratory testing activities were divided between
EPA and ERG according to the breakdown shown in Table 1.
Table 1. Sampling Medium Used for Collection of Samples, Analysis Performed,
Analytical Method, and Responsible Laboratory
Sampling Medium Analysis Method Laboratory
Teflon Filter
PM2 5 Mass
Gravimetric (GRAV)
EPA
Teflon Filter
Elemental Analysis
X-Ray Fluorescence (XRF)
EPA
Teflon Filter
Inorganic Ions
Ion Chromatography (IC)
EPA
Quartz Filter
Elemental Carbon/ Organic
Carbon
Thermal-Optical Evolution
(TOE)
EPA
Quartz Filter, XAD-4
Denuder, and PUF
Semivolatile Organic Species
Gas Chromatography/ Mass
Spectrometry (GC/MS)
EPA
DNPH-Impregnated
Silica Gel Tubes
Carbonyl Compounds
High Performance Liquid
Chromatography (HPLC)
ERG
SUMMA Canisters
Air Toxics
Speciated Nonmethane
Organic Compounds
Method TO-15 (GC/MS)
ERG Concurrent Analysis
ERG
Particle Size Analyzer
Particle sizes
Electrical Low Pressure
Impactor (ELPI)
ERG
ERG performed source sampling to collect artifact-free, size-resolved particulate matter
in a quantity and form sufficient to identify and quantify trace elements and organic
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compounds and to distinguish gas-phase and particle-phase organic compounds. Total
particulate matter mass in the diluted and cooled emissions gas was size resolved at the
PM10 and PM25 cut points with the PM2 5 fraction further continuously resolved down to 30
nm diameter using an electrical low pressure impactor (ELPI). Fine particle emission
profiles can be used in molecular marker-based source apportionment models, which have
been shown to be powerful tools to study the source contributions to atmospheric fine PM.
To assist in the characterization of the hogged fuel boiler stationary source emissions
and to obtain chemical composition data representative of particle emissions after cooling
and mixing with the atmosphere, ERG performed the following activities at the test site:
Performed preliminary measurements using EPA Methods l3, 24, and 45 to evaluate
source operating conditions and parameters;
Installed the precleaned dilution sampling system, sample collection trains, and
ancillary equipment at the field site without introduction of contaminants;
Calibrated flow meters before and after sampling, monitoring, and adjusting gas
flows (as necessary) throughout the tests;
Acquired process data for the test periods, including temperatures, pressures, flows,
and such;
Determined the type of combustion fuel and the rate of consumption during the
source testing;
Collected three sets of stationary source samples as prescribed in the Site-Specific
Test Plan, including one set of field blanks; and
Recovered the dilution sampling unit and sample collection arrays for analysis for
specific parameters and returned the dilution sampling unit to EPA.
ERG transported the dilution sampling system to the test site to collect integrated
samples, performed whole air analysis of volatile organic compounds collected in SUMMA-
polished stainless steel canisters and gas-phase carbonyl compounds collected on silica gel
cartridges impregnated with 2,4-dinitrophenylhydrazine (DNPH), and evaluated particle size
distribution data. EPA was responsible for pretest cleaning of the dilution sampling system,
for analysis of semivolatile organic compounds from XAD-4 denuders and polyurethane
foam (PUF) sampling modules resulting from the test efforts, and for characterization of the
particle phase emissions and mass loading on quartz and Teflon filters.
Description of Test Equipment
The test equipment consisted of a dilution sampling system and its instrumentation.
8
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Dilution Sampling System
The dilution sampling system used in the source test was based on an original design by
L. M. Hildemann6 which was modified to incorporate more secure closure fittings and
electronic controls. Automatic flow control and data acquisition capabilities were added to
the dilution sampler to improve the ease of operation of the unit. A touch screen interface
connected to the main controller was used to monitor current conditions and allow set points
to be entered into the system readily. A laptop computer was used for continuous monitoring
of operating parameters and logging of the sampler operation.
The dilution sampling system dilutes hot exhaust emissions with clean air to simulate
atmospheric mixing and particle formation. Control of residence time, temperature, and
pressure allows condensible organic compounds to adsorb onto fine particles as they might
in ambient air. The sampler is also designed and fabricated to minimize any contamination
of samples, especially organic compound contamination, and to minimize particle losses to
the sampler walls. A preliminary investigation into particle losses within the sampler was
conducted as part of another source sampling campaign at a different site. Results of that
study indicate that particle losses in the sampler (including wall losses in the probe, dilution
tunnel, and residence chamber) amounted to approximately 21.2% of the total PM that
entered the sampler from the stack. However, those losses include all of the nominally PM10
material that passed through the in-stack PM10 cyclone, not just PM2 5 material alone.
Therefore, losses of PM2 5 particles would be expected to be less than 21.2%. Hildemann
reported losses of approximately 7% in a dilution sampler of the same design and
dimensions, but his value did not include probe losses.
Figure 1 shows a schematic diagram of the dilution sampling system and dilution air
cleaning and conditioning system. As shown, the dilution air cleaning system provides high
efficiency particulate arresting (HEPA) and activated carbon-filtered air. Acid gases (if
present) will not be removed completely by the dilution air cleaning system, but the
presence of acid gases can be monitored in the dilution tunnel immediately downstream of
the dilution air inlet. The dilution air cleaning system can be modified to add a heater,
cooler, and dehumidifier as needed. Cleaned dilution air enters the main body of the
sampling system prior to the dilution sample arrays.
The key zones of the dilution sampling system and their function are described below.
9
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Turbulent Mixing Chamber
Re = 10,000
RESIDENCE
TIME
CHAMBER
ACCESS
PORTS \
STACK
EMISSIONS
10 jim
CYCLONE
2.1 jim
CYCLONES
(HIGH-VOL*
FILTER
1=!VENTURI
HEATED INLET LINE
STACK
EMISSIONS INLET
SAMPLE
ARRAYS
D1—C]
D2—[]
D3—C]
Blower
SAMPLE
ARRAYS
R.3
R5
R2
R6
R4
ACTIVATED
CARBON
BED
HE PA
FILTER
COOLING
UNIT
BLOWER
LUTION
AIR
DILUTION AIR
INLET
VACUUM
PUMPS
Figure 1. Diagram of the Dilution Sampler and Dilution Air Conditioning System.
-------
Sample Inlet Zone—
Stack Emissions Inlet: designed to allow stationary source exhaust gas to be sampled
through an inlet cyclone separator to remove particles with nominal aerodynamic
diameters greater than 10 |im, The PM10 cyclone prevents large particles from
entering the sampler to plug or damage the equipment. Three ports are dedicated to
sampling the dilution air before it mixes with the source gas.
Heated Inlet line: 3/4 in. heated stainless steel sampling probe draws source gas
through a venturi meter into the main body of the sampler. Sample flow rate can be
adjusted from 15 to 50 L/min (typically 30 L/min).
Venturi Meter—
Constructed of low carbon, very highly corrosion-resistant stainless steel; equipped
for temperature and pressure measurement. Wrapped with heating coils and insulated
to maintain the same isothermal temperature as the inlet cyclone and inlet line.
Turbulent Mixing Chamber—
The mixing chamber incorporates an entrance zone, U-bend, and exit zone. The
inside diameter is 6 in., which yields a Reynolds number of approximately 10,000 at
a flow rate of 1000 L/min. Dilution air enters the mixing chamber in a direction
parallel to the flow of source gas. Hot source emission gas enters the chamber
perpendicular to the dilution air flow, 4.5 in. downstream of the dilution air inlet.
The combined gas flow travels 38 in. before entering the U-bend. After the residence
chamber transfer line, the mixing chamber continues for 18 in. then expands to an in-
line, high-volume sampler filter holder. Collected particulate material has not
experienced time to equilibrate with the gas phase in the diluted condition. Sampling
and instrumentation ports are installed on the turbulent mixing chamber at various
locations, as shown in Figure 1.
Residence Time Chamber—
The inlet line to the residence time chamber expands from a 2-in. line (sized to
provide a quasi-isokinetic transfer of sample gas from the turbulent mixing chamber
to the residence time chamber at a flow rate of approximately 100 L/min) within the
mixing chamber to a 7-in. line at the wall of the residence chamber. The flow rate is
controlled by the total sample withdrawal from the bottom of the residence time
chamber and provides a 60-sec residence time in the chamber. Twelve ports are
installed at the base of the residence time chamber, nine ports for sample withdrawal
and three ports for instrumentation.
11
-------
Sample Collection Zone—
Samples collected from the sampling ports at the base of the residence time chamber
have experienced adequate residence time for the semivolatile organic compounds to
repartition between the gas phase and the particle phase.
Because it is very difficult to maintain both isokinetic sampling and a fixed cyclone size
cut during most stack sampling operations, the inlet cyclone may be operated to provide a
rough PM10 cut while maintaining near-isokinetic sampling. The rough inlet size cut has
minimal impact on sampling operations since the dilution sampling system is used mainly to
collect fine particulate matter from combustion sources, and the critical fine particle size cut
is made at the end of the residence time chamber. Typically, the calculated total time the
sample spends in the dilution sampling system ranges from 58 to 75 sec with 2 to 3 sec for
the turbulent mixing chamber and 56 to 72 sec for the residence chamber.
Dilution Sampling System Control Instrumentation
Instrumentation for control and analysis of the dilution sampling system is shown in
Figure 2. Differential pressure measurements made across the venturi and orifice meters are
used to determine the dilution air flow rate, the sample gas flow rate, and the exhaust gas
flow rate. Since flow equations used for determination of the flow across venturi and orifice
meters correct for flowing temperature and pressure, the flowing temperature and pressure
of the venturi and orifice meters must be recorded during sampling operations.
Thermocouples for monitoring temperature are placed at each flow meter as well as at the
inlet PM10 cyclone, at various points on the sample inlet line, at the inlet to the mixing
chamber U-bend, and at the outlet of the residence time chamber. An electronic relative
humidity probe is used to determine the relative humidity of the sample gas. The dilution
sampling system is equipped with automated data logging capabilities to better monitor
source gas testing operations and to minimize manpower requirements during sampling
operations. Dilution sampling system flows and temperatures are monitored and controlled
automatically at set points established by the operator using a QSI Corporation QTERM-
K56 electronic touch screen interface. The dilution sampling system was operated by three
testing staff members during the test at the Kraft Process hogged fuel boiler.
In operation, the source sample flow, the dilution air flow, and the total air flow (not
including the sample collection arrays) were each measured by separate flow meters and
pressure transducers. A venturi meter measured the source sample flow and orifices were
used for the dilution and total flows. A ring compressor was used to push the dilution air
through a HEPA filter, a carbon adsorber, and a final filter into the turbulent mixing
12
-------
Key:
TE = Temperature Indicator
PT = Pressure Indicator
RH = Relative Humidity Indicator
PM 10
Cyclone
HEPA Filter
Carbon Bed
Dilution Air
Blower
TE-104
TE-108
PT-101
TE-101
TE-102
TE-105
TE-103
Figure 2. Instrumentation for Control and Analysis of the Dilution Sampler.
TE-109
Residence
Time
Chamber
RH-1
Am bient
PT-103
TE-106
PT-104
TE-107
Exhaust
Blower
-------
chamber. The compressor motor was modulated by a variable frequency drive to match the
desired dilution flow based on a set point entry. A separate blower (connected to a speed
controller adjusted to achieve the desired sample flow based on a set point entry) at the end
of the dilution sampling system pulled the source sample flow through the venturi. Flow
through this blower consisted of the dilution airflow plus the source sample flow, not
including the flow exiting through the sample collection arrays.
The main controller modulated the power used to heat the sample probe (32 in. long, one
heated zone). The controller switched solid-state relays on and off as needed to maintain the
probe temperature, which had been entered by the operator.
Sample Collection Arrays
Virtually any ambient sampling equipment—including filters of various types (quartz,
Teflon, Nylon), denuders, polyurethane foam (PUF) modules, DNPH-impregnated silica gel
sampling cartridges, SUMMA polished canisters, cyclones, particle size distribution
measurement instrumentation—can be employed with the dilution sampling system. The
exact number and type of sample collection array is uniquely configured for each test.
Process Description/Site Operation
The hogged fuel boiler can fire hogged fuel, No. 6 fuel oil, coal, waste oil, sludge, and
HVLC gases, singly or in combination, generating up to 889 MBtu/hour maximum heat
input from the combined fuels; only hogged wood and coal were used as fuel during the
testing. The hogged fuel boiler is equipped with a multistage control system composed of
the following components:
One multicyclone/electroscrubber system (one electrified granular filter bed);
Three bag filters installed on the de-entrainment vessel for the granular media used
in the electroscrubber;
Two filters installed on vents of the north and south coal bins;
Two bag filters installed on the vents of the boiler ash silo;
Two bag filters installed on vents on the scrubber ash silo; and
One bag filter installed on the storage vessel which holds the gravel media used in
the electroscrubbers.
The hogged fuel boiler No. 2 sampling location was in the vertical exit stack down-
stream of the multistage control system, with the sampling port installed at a point that
meets EPA Method 1 requirements for length of straight run and for orientation of the port
with respect to the plane of bends in the ductwork. The sampling port, elevated
14
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approximately 90 feet above ground level, is shown in Figure 3; a schematic diagram of the
layout of the sampling site is shown in Figure 4. The area around the sampling port is an
enclosed space (called the dough-nut) approximately eight feet wide from the stack wall to
the outside wall of the doughnut.
Flanged Sampling Port
Located Here
Figure 3. Hogged Fuel Boiler No. 2 Sampling Port Location.
Access to this location required use of elevator and stairs to a catwalk-type platform.
The sampling equipment was lifted by crane to the location shown in Figure 3, and the
dilution unit was then rolled into position in the doughnut. The control unit was located just
inside the door of the enclosed space and was connected to the dilution unit using electrical
wiring and approximately 10 feet of flexible hose.
Supplemental equipment was brought to the sampling location by elevator and stairs.
There was no space in the vicinity of the sampling port to place an enclosure for preparation
of sampling components or for recovery of the sample collection arrays. Therefore, an
appropriate area at ground level was identified for sampling component preparation and for
sample collection array recovery and preparation for transport to the laboratories.
The hogged fuel (coal and wood chips) was stored outdoors in large piles near the
hogged fuel boiler (Figures 5 and 6, respectively). Samples of the coal and wood chips were
collected during Test Day 2; analytical results for these fuel samples are shown in Table 2.
Fuel use for Flogged Fuel Boiler No. 2 during the testing period is summarized in Table 3.
15
-------
Top View
Hogged Fuel Boiler Sampling Location Layout
Catwalk
and
Platform
Flexible
'fHose/
Stack
Interior
Probe
Dilution^
Unit
Exterior
Enclosure
Wall
Arrays ELf
Stack Wall
and
Insulation
Sampling Location
Elevation is
- 90 feet above
Grade
Enclosed
Doughnut Housing
Figure 4. Hogged Fuel Boiler Sampling Location Layout—Top View.
Figure 5. Hogged Fuel Outdoor Coal Storage Area.
16
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Figure 6. Hogged Fuel Outdoor Wood Storage Area
Table 2. Analysis of Coal and Wood Chip Hogged Fuel
Coal Content Wood Chip Content
Constituent
As Received
Dry
As Received
Dry
Moisture
4.10%
46.60%
Volatile Matter
35.29%
36.80%
42.41%
79.41%
Fixed Carbon
53.21%
55.49%
8.95%
16.77%
Ash
7.40%
7.71%
2.04%
3.82%
Sulfur
0.68%
0.71%
0.04%
0.07%
Carbon
74.55%
77.74%
26.54%
49.70%
Hydrogen
4.51%
4.70%
3.07%
5.76%
Nitrogen
1.53%
1.60%
0.07%
0.13%
Oxygen
7.23%
7.54%
21.64%
40.52%
Chlorine
0.11%
—
0.12%
0.23%
Btu per pound
13335
13906
4392
8224
17
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Table 3. Hogged Fuel Boiler No. 2 Fuel Use During the Test Period
Total
Combined
Combined
Test
Weight
Overall Total
Overall Total
Test
Fuel
Feed Rate
Duration
Used
Weight Used
Weight Used
No.
Type
(lbs/min)
(min)
(lbs)
(lbs)
(kg)
1
Coal
506.7
479
242,709.3
1
Wood
1,236.7
479
592,379.3
1
835,088.6
378,789.8
2
Coal
504.7
480
242,240.0
2
Wood
1,357.7
480
651,360.0
2
893,600.0
405,330.1
3
Coal
470.0
481
226,070.0
3
Wood
1,333.3
481
641,317.3
3
867.387.3
393.440.2
Pre-Test Survey
A thorough survey of the test site was conducted to determine that the test equipment
could gain access to the test location and that the dilution sampling system and the control
module would fit in the test location, to identify and gain access to the utilities needed to
operate the dilution sampling system and its ancillary equipment, to arrange for the instal-
lation of a sample collection port (Figure 3) in the boiler exhaust stack, and to determine and
evaluate the means of positioning the dilution sampling system at the desired location. The
pre-test survey considered access to utilities and personnel, legal, and safety requirements.
Limited source data—such as exhaust gas flow rate and velocity, exhaust gas temperature
and water vapor content, and approximate particulate matter concentration—were obtained
for estimating appropriate dilution ratios and duration of sample collection. Arrangements
were made to position the dilution sampling system inside the enclosed housing attached to
the boiler exhaust stack (Figure 3) approximately 90 ft above ground level. A second pre-
test survey was made to verify that the sampling port had been installed correctly, that all
necessary utilities had been installed, and that arrangements for lifting the dilution sampling
system to the sampling platform were complete. The dilution sampling system, the control
module, and all ancillary equipment were then transported to the test site, and the dilution
air supply/control module and the sampler module were positioned at the sampling location
using a crane supplied and operated by the facility. Electrical power (250V, single phase, 40
A) was provided and installed by the facility.
18
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Experimental Procedures
The EPA/ECPB dilution sampling system (schematic diagram in Figure 1), sample
collection arrays, sample substrates, and dilution air cleaning system were used for sampling
undiluted hot exhaust gas streams. To minimize introduction of contaminants, EPA
precleaned and preassembled the dilution sampling system and sample collection arrays in a
clean environment prior to transport to the test site. The dilution sampling system and
dilution air cleaning system were assembled on separate portable aluminum frames
equipped with wheels and tie-down and hoisting lugs for transport to and from the test site.
A crane provided by the facility was used to position the dilution sampling system at the test
site. ERG maintained the dilution sampling system and sample collection arrays in a
contaminant-free condition prior to collection of recovery boiler samples and field blanks.
A sampling system blank test was performed prior to transporting the dilution sampling
system to the test site to ensure that the system had been cleaned properly and was leak free.
The blank test was performed in the laboratory by completely assembling the dilution
sampling system, including the sample collection arrays connected to the residence time
chamber, and all instrumentation. The blank test was conducted for a time period consistent
with the expected duration of the source tests (approximately eight hours). Following the
blank test, the dilution sampling system was shut down in reverse order from start-up, and
all substrates were unloaded, preserved as appropriate, and analyzed to verify the absence of
contamination in the dilution sampling system.
Preparation for Test Setup
Prior to the deployment of the dilution sampling system at the test site and initiation of
sampling with the dilution sampling system and associated sample collection arrays, EPA
Methods l3, 24, and 45 were conducted to establish key experimental parameters for test
conditions.
Traverse Point Determination Using EPA Method 1
EPA Method l2 was used to establish the number and location of sampling traverse
points necessary for isokinetic and flow sampling. These parameters are based on how much
duct distance separates the sampling ports from the closest downstream and upstream flow
19
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disturbances. The hogged fuel boiler No. 2 sampling site is located on the vertical wall of a
boiler duct, with the sampling port at a location that meets EPA Method 1 requirements for
length of straight run and for orientation of the port with respect to the plane of bends in the
duct work. Sampling at the test site was performed at the point determined by Method 1 to
represent the average velocity of the exhaust duct used on hogged fuel boiler No. 2 (Figure
3). Although the overall duct diameter was 12 ft, only 6 ft (or approximately one-half of the
diameter) were traversed to determine stack velocity because the longest probe available for
the dilution system was 6 ft long.
The following duct dimensions were measured:
Center of stack to outside of nipple (Distance A): 89 in.
Inside of near wall to outside of nipple (Distance B): 17 in.
Inside stack dimension from center of stack to inside of near wall: 72 in.
Traverse point locations for a the circular hogged fuel boiler duct are listed in Table 4. A
table of metric unit conversions is provided in Appendix A.
Table 4. EPA Method 1 Traverse Point Locations for the Circular Hogged Fuel Boiler
No. 2 Exhaust Duct
Traverse
Fraction of Inside Stack
Traverse Point
Point
Dimension3
Distance from Stack Wall
Location
Number
(%)
(in.)
(in.)
1
2.6
1 %
18%
2
8.2
5%
22%
3
14.6
10 »/2
27 »/2
4
22.6
16 %
33 %
5
34.2
24 %
41 %
6
65.8
47%
64 %
7
77.4
55 %
12 V,
8
85.4
61 »/2
78 »/2
9
91.8
66 Vs
83 1/s
10
97.4
70 1/s
87 1/s
a Inside stack depth from center of stack to inside of near wall: 72 in. Distance from lip of flange to inside stack wall: 17 in.
The absolute pressure of the flue gas (in inches of mercury) was calculated according to the
equation
PS-P"'W6 (4"»
20
-------
where:
PS = absolute gas pressure, inches of mercury
Pbar = barometric pressure, inches of mercury (29.91 in.)
Pg = gauge pressure, inches of water (static pressure) (-0.95 in.).
The value 13.6 represents the specific gravity of mercury (1 in. of mercury = 13.6 in. of
water). For the stack tested, the absolute gas pressure under the test conditions was 29.84
in. of mercury.
Volumetric Flow Rate Determination Using EPA Method 2
Volumetric flow rate was measured according to EPA Method 23. A K-type thermo-
couple and S-type pitot tube were used to measure flue gas temperature and velocity,
respectively. All of the isokinetically sampled methods that were used incorporated EPA
Method 2.
Pitot Tube Calibration
The EPA has specified guidelines concerning the construction and geometry of an
acceptable S-type pitot tube. If the specified design and construction guidelines are met, a
pitot tube coefficient of 0.84 is used. Information pertaining to the design and construction
of the S-type pitot tube is presented in detail in Section 3.1.1 of report EPA 600/4-77-027b.
Only S-type pitot tubes meeting the required EPA specifications were used. Pitot tubes were
inspected and documented as meeting EPA specifications prior to field testing.
Calculation of Average Flue Gas Velocity
The average flue gas velocity for each traverse point is calculated using the equation
Vs = average flue gas velocity, ft/sec
Kp = pitot constant (85.49)
Cp = pitot coefficient (dimensionless), typically 0.84 for S-type
APmg = average flue gas velocity head, inches of water
460 = 0 °F, expressed as degrees Rankin
Ts = flue gas temperature, °F (320 °F)
Ps = absolute stack pressure (barometric pressure at measurement site plus stack static
pressure), inches of mercury (29.84 in.)
K = KpxCpX
(4-2)
V Ps x Ms
where:
21
-------
Ms = wet molecular weight, pounds per pound-mole (28.26 lb/lb-mole).
The flue gas velocity calculated for each traverse point and the average velocity are
shown in Table 5. The velocity at traverse points 9 and 10 are closest to the average
velocity. However, sampling at traverse point 9 or 10 was not possible because neither of
the two probes available with the Dilution Sampling System were long enough to reach
traverse point 9 or 10. Only traverse points 1 to 6 could be reached using the available
dilution system probes. Consequently, Traverse Point No. 3 was selected for sampling
because it represented the accessible point closest to the calculated average velocity.
Table 5. Average Flue Gas Velocity for Each Traverse Point
Traverse Point
Velocity
(Calculated in Table 4)
(ft/min)
1
1797.2
2
2007.1
3
2173.5
4
2329.6
5
2260.0
6
2309.2
7
2232.2
8
2114.8
9
2155.1
10
2155.1
Average Velocity
2153.4
The average flue gas velocity of 2153.4 ft/min was assumed constant for all three test
days. However, there was a range of approximately 7% in the fuel feed rate among the three
test days, and the coal content ranged from 27% to 35% of the fuel. The exact nature of the
effect of the variation in these parameters on the emission factors is uncertain. Since the
term "kg of fuel" appears in the denominator of the emission factor, an increase or decrease
in the fuel feed will have a direct effect on the value of the emission factor. The change in
composition of the fuel will also have an effect on the amount and size of the particulate
matter as well as the amount and composition of the gas phase emissions, but the exact
nature and value of this effect and the interaction with an increase or decrease in the fuel
feed rate are unknown.
22
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Nozzle Size Determination
It is desirable to sample at or near isokinetic velocities at the probe inlet nozzle. The
nozzle size is based on the required sample flow rate. Prior to using an Excel macro to
perform nozzle size calculations according to the procedures of EPA Method 51, the velocity
in the stack (feet per minute) must be determined from the pitot traverses prior to the start of
the test run. The additional input required by the macro is sampling rate (liters/minute). The
nozzle selected for use at hogged fuel boiler No. 2 was 0.299 in. inside diameter (id).
Measurement of ()2, C02, and CO Concentrations for Calculating Stack Parameters
The 02 and C02 concentrations were determined using a Fyrite bulb during the traverse.
The CO concentration was determined using the facility's installed CO continuous
emissions monitor (certified).
Stationary Gas Distribution (as Percent Volume)
The following concentrations were measured:
02 = 13.0%V
C02 = 8.0%V
CO = 0.03%V
The percentage of nitrogen (N2) was calculated by
N2%V = 100 - (02%V + C02%¥ + CO%V) = 78.97%V (4.3)
Dry Molecular Weight of Flue Gas
The dry molecular weight of the flue gas (Md) was calculated by
Md = (0.44 x C02%¥) + (0.32 x 02%V) + [0.28 x (CO%V + N2%V)]
- 29.80 lb/lb* mole
where:
Md = molecular weight of flue gas, dry basis (lb/lb-mole)
C02%V = percent C02 by volume, dry basis (8.0)
02%V = percent 02 by volume, dry basis (13.0)
CO%V = percent CO by volume, dry basis (0.03)
N2%V = percent N2 by volume, dry basis (78.97)
0.44 = molecular weight of C02, divided by 100
0.32 = molecular weight of 02, divided by 100
0.28 = molecular weight of N2 or CO, divided by 100.
23
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Wet Molecular Weight of Flue Gas
The wet molecular weight of the flue gas (Ms) was calculated by
Ms = (Md x Mfd) + (0,18 x H20%V)
= 28.26 wet lb/lb* mole
where:
Ms = wet molecular weight of flue gas, wet lb/lb-mole
Md = molecular weight of flue gas, dry basis (29.80 lb/lb • mole)
Mfd = dry mole fraction of effluent gas, calculated as [1 - H2O%V/100] (0.869)
0.18 = molecular weight of H20, divided by 100
H20%V = percent H20, by volume (13.11).
Determination of Average Moisture Using EPA Method 4
EPA Method 45 was used to determine the average moisture content of the duct gas. A
gas sample was extracted from the boiler, moisture was removed from the sample stream,
and the moisture content was determined gravimetrically. The initial weight of the
impingers was recorded before sampling. When sampling was completed, the final weights
of the impingers were recorded, and the weight gain was calculated. The weight gain and the
volume of gas sampled were used to calculate the average moisture content (percent) of the
duct gas. Method 4 was incorporated into the techniques used for all of the manual sampling
methods that were used during the test. The measurements shown in Table 6 were made
prior to the actual test dates, using Method 4 to determine moisture recovery.
Table 6. Moisture Recovery for Method 4
Weight of
Impinger Weight
Impinger
Impinger
Weight
Impinger
Impinger
Contents
Tip
Final
Initial
Gain
Number
Solution
(g)
Configuration
(g)
(g)
(g)
1
Water
100
Standard
672.4
608.6
63.8
2
Water
100
Standard
621.0
573.6
47.4
3
Empty
"
Standard
496.9
483.6
13.3
4
Silica Gel
300
Standard
776.9
759.2
17.7
Total Weight Gain (g)
142.2
Volume of Dry Flue Gas Sampled at Standard Conditions (dscf)
The volume of dry flue gas sampled under standard conditions was calculated by
24
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V ft,, = 17.64x yxV x
m(std) J m
where:
A H
P +
bar 13.6
460+ T
47.632 dscf
(4-6)
V,
m(std)
= volume of dry gas sampled at standard conditions, dry standard cubic feet (dscf)
Vm = volume of gas metered, cubic feet, dry (44.607 ft3)
y = dry gas meter calibration factor (0.980)
Pbar = barometric pressure at measurement site, inches of mercury (29.91 in.)
AH = sampling rate, measured as differential pressure at the meter orifice, inches of
water (1.72 in.)
Tm = dry gas meter temperature, °F (62.3 °F).
The constant 17.64 was used to convert to standard conditions (84.7 °F, 30.24 in.
mercury); 460 is 0 °F in degrees Rankin. Using measured values from the field data sheet,
the volume of dry flue gas sampled at standard conditions is calculated to be 44.35 dscf.
Volume of Water Vapor at Standard Conditions (dscf)
The volume of water vapor under standard conditions was calculated by
K,(std) = 0.04707 x Vic = 6.693 dscf (4-7)
where:
VW(Std) = volume of water vapor at standard conditions, dry standard cubic feet (dscf)
Vlc = volume of liquid catch (142.2 mL).
The constant 0.04707 is the standard cubic feet per gram (or milliliter) of water at
standard conditions. Using the total weight gain for water determined using Method 4
(Table 7, above), the volume of water vapor at standard conditions is calculated to be 13.231
dscf.
Calculation of Moisture/Water Content (as percent volume)
The moisture content of the gaseous stack emissions is calculated by
f */// t
11 0%V = 100 X r; =13.11 %V
''ulstji ' m(shi) V )
Using values measured using EPA Method 4 and values calculated previously, the
moisture content was calculated to be 13.11 %V.
25
-------
Calculation of Dry Mole Fraction of Flue Gas
The dry mole fraction of flue gas is calculated by
H,0%V
Mjii = 1 - "j oq = 0.869 (4-9)
where:
Mfd = dry mole fraction of flue gas.
Using the percent moisture determined above, the dry mole fraction of flue gas is
calculated as 0.869.
Setup of the Dilution Sampling System
The hogged fuel boiler No. 2 sampling location was the vertical wall of a boiler duct,
with the sampling port 95 feet above ground level (schematic diagram of test site in Figure
4). The area surrounding the sampling port was an enclosed circular housing with an
average width of 48 in. Access to this location was by a catwalk-type platform. The large
pieces of the dilution sampling system (i.e., the dilution sampling system itself, the control
unit) were lifted up to the sampling location using a crane provided and operated by the
facility, then rolled into position at the sampling port (Figure 3).
The enclosed housing shown in Figure 4 allowed minimal space around the dilution
sampling unit and the control unit. The control unit for the dilution sampling system was
located just inside the enclosed housing doorway and was connected to the dilution
sampling unit by 10 feet of flexible stainless steel tubing. The dilution sampling system
positioned at the sampling location is shown during operation in Figure 7.
Figure 8 shows the sampling probe installed in the 6 in. flanged port used for sampling.
The control module (Figure 9) was located just inside the enclosed housing doorway, and
was connected to the dilution sampling unit. An Electric Low Pressure Impactor (ELPI),
manufactured by Dekati (Figure 10), with associated laptop computer was also connected to
the sampling module together with other sample collection arrays; sample collection arrays
are visible in the background. The dilution system sampling module with all sample
collection arrays and instruments attached is shown in Figure 11: note the ELPI in the
foreground and the various sample collection arrays (the white filter holders are readily
26
-------
Figure 7. Dilution System Sampling Module Positioned at the Sampling
Location.
Figure 8. Dilution System Sampling Probe Installed in 6 in. id Flanged Port.
27
-------
Figure 9. Dilution System Control Module Positioned at the Sampling
Location.
Figure 10. ELPI Positioned at the Sampling Location
28
-------
Figure 11. Dilution System with All Sample Collection Arrays and
Instruments Attached.
visible) attached to the various ports of the dilution system sampling module. Because of the
lack of available space in the immediate vicinity of the sampling location, sample recovery
(with the exception of the denuders) was conducted inside the ERG mobile laboratory
located on the host facility property. Figure 12 shows the denuders being recovered at the
sample collection location. The denuders had to be recovered and recharged every 30
minutes. Consequently, the denuders sample collection arrays were transported intact to the
recovery area in the ERG mobile laboratory and disassembled. Samples were then labeled,
packaged for transport, and placed in a chest-style freezer. Sample logs with sample
identification are shown in Appendix B; copies of the chain of custody documentation are
also included in Appendix B.
Pre-Test Leak Check
To perform a pre-test leak check on the assembled dilution sampling system in the field,
the end of the probe was plugged with a Swagelok fitting. Solvent-cleaned blank-off plates
were inserted in place of the orifice plates at the orifice meter run flanges using gaskets on
each side. A new, tared, 8x10 in. quartz filter was inserted into the filter holder, and the
fittings were carefully sealed. A vacuum pump was attached to the residence chamber, and a
29
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Figure 12. Recovery and Recharge Area for Denuders Used in the Dilution
Sampling System.
Magnehelic gauge was attached to an available port. The valve between the pump and the
chamber was opened, and the vacuum was read as the pump was turned on. A stopwatch
was started as the reading passed 27 in., and the valve between the pump and the chamber
was closed. The leak rate was timed between 25 to 20 in. and again from 20 to 15 in., and
the two times were averaged. Using the recorded data, the leakage rate in cubic feet/minute
was calculated according to Equation 4-10.
leakage rate = x Fx CF < 0.1 ft / min (4-10)
where:
leakage rate = rate of leakage (ft3/min)
AP = change in pressure (12 in. water)
AT = time increment (240 sec)
V = volume of the evacuated dilution sampler (15.3 ft3)
CF = unit conversion factors (60 sec/min; 1 atm/406.8 in. water)
The criteria for an acceptable leak are less than or equal to 0.1 ft3/ min, or more than 1
min 53 sec for a pressure change of 5 in. water. For this test, an average time of 2 min was
30
-------
required for a 5-in. pressure change to occur. The resulting leak rate was 0.094 ft3/min,
satisfying the criteria for acceptability.
Orifice Flow Check
Critical orifice flows on the sampling pumps were checked without sample collection
arrays in place by using a rotameter to verify that the channels on sampling array pumps
were the specified flow rate of 16.7 L/min. Rotameters were calibrated with a National
Institute of Standards and Technology (NIST) traceable electronic bubble flow meter, and
the readings were converted to flow (liters per min) using a spreadsheet.
Determination of Test Duration
To ensure the best possible collection of PM, the sampling tests were conducted for the
maximum amount of time permitted by the facility (eight hours).
Canister/Verifiow Blanks
Prior to deployment in the field, SUMMA-polished canisters and Veriflow canister
filling units were cleaned, and blank analysis was performed in the laboratory. All units met
the cleanliness criterion of less than 10 ppbC (parts per billion carbon, Table 7).
Table 7. Blank Values for Veriflows and Canisters
Blank Value
Unit
(ppbC)
Veriflows
EPA Unit #418 (Source Veriflow)
ERG-1 Ambient Veriflow
EPA Unit #315 (Dilution Veriflow)
5.0
1.0
0.0
Canisters
4005
4004
1482
1484
1478
4037
4044
3552
0.0
2.0
0.0
0.0
0.0
4.0
0.0
0.0
31
-------
Determination of Flow Rates
A Visual Basic macro was written to process raw data files of flow rate information and
convert this information to actual flow based on temperature, pressure, and calibration data.
For venturi flows, the macro converted differential pressure into a reported flow rate. The
square root of the differential pressure was then multiplied by a previously determined
calibration factor based on the flowing temperature, and the resulting value was converted to
standard liters per minute (sL/min) using Ideal Gas Law relationships (1 atm, 70 °F).
Calibration data for the venturi were generated by placing a dry gas meter at the inlet to
the sample probe. The flows reported by the data acquisition system were corrected to actual
liters per minute (aL/min) and compared to those produced by the dry gas meter corrected to
the venturi conditions. An Excel macro automatically selected a correct calibration value to
be applied based on the flowing temperature.
Since the actual venturi flow depended on the operating conditions, the set point value
displayed and entered on the viewing screens needed to be adjusted to achieve the desired
flow. Information to be entered included the desired flow, flow temperature, flow pressure,
and barometric pressure; the Excel macro automatically selected the correct value to be
applied based on the flow temperature.
Sample Collection Arrays
Prior to actual testing (Test Run 1, 11/27/01; Test Run 2, 11/28/01; Test Run 3,
11/29/01), sample collection arrays were attached to various ports on the dilution sampling
system, as shown in Figure 13. Ten sampling ports were available and were attached to
either the dilution chamber or the residence chamber (available sampling ports are shown in
Figure 1.). The following sample collection arrays were used for Tests 1, 2, and 3.
Dilution Chamber Sample Collection Arrays
Samples of the dilution air were collected to evaluate the analyte background in the
dilution air.
• Dilution Chamber Collection Array Dl, Port #D1
Sample Collection Array Dl collected gas-phase semivolatile organic compounds,
particle-bound organic materials, and metals. The array consisted of a cyclone
separator to remove particulate matter with an aerodynamic diameter greater than 2.5
|im. One leg contained a quartz filter followed by two PUF sampling modules in
series. The other leg of Array Dl consisted of a Teflon filter.
32
-------
Dilution chamber
Port #D1
Port #D2 Port #D3
B QF B TF
Cyclone
Residence chamber
Port #R2 Port #R3
TF B TF
Port #R5 Port #R6
B TF B TF
Port #R4
B QF Bqf
Cyclone
Port #R8
g QF g QF
Cyclone
Field Blanks
1
1
QF
TF
PUF 1 Pair
SUMMA 1
DNPH 1
Total
Substrates
QF
8
TF
6
PUF
9 Pair
Denuder
2
SUMMA
4
DNPH
7
Port #R10
PUF
BQF E=3<:
Leaend
QF
= Quartz Filter
KOH QF
KOH Quartz Filter
TF-0.5
= Teflon® Filter - 0.5
TF
= Teflon® Filter
PUF
= Polyurethane Foam Sampling Module
Denuder
= Denuder
SUMMA
= SUMMA® Canister
DNPH
= 2,4-Din it rophenyl hydrazine
-impregnated silica gel cartridge
Figure 13. Sample Collection Arrays Used for Testing at the Hogged Fuel Boiler.
33
-------
• Dilution Chamber Collection Array D2, Port #D2
Sample Collection Array D2 collected fine particulate matter and gas-phase organic
compounds. This array consisted of a single filter unit followed by a SUMMA
polished stainless steel canister.
• Dilution Chamber Collection Array D3, Port #D3
Sample Collection Array D3 collected carbonyl compounds using three DNPH
impregnated silica gel sampling cartridges in series and a pump.
Residence Chamber Sample Collection Arrays
Samples of the air were collected from the residence chamber to evaluate the analyte
presence in diluted stationary source air.
• Residence Chamber Sample Collection Array R2, Port #R2
Sample Collection Array R2 collected fine particulate matter. The array consisted of
a 2.5 |im cyclone followed by two identical legs containing Teflon filters.
• Residence Chamber Sample Collection Array R3, Port #R3
Sample Collection Array R3 collected fine particulate matter and carbonyl
compounds. This array consisted of a pair of carbonyl collection cartridges in series,
with a pump.
• Residence Chamber Sample Collection Array R4, Port #R4
Sample Collection Array R4 collected fine particulate matter on paired quartz filters
for total carbon and elemental analysis, as well as semivolatile organic compounds
using two PUF sampling modules in series. This sampling array consisted of a 2.5
|im cyclone with two quartz filters in parallel; one of these quartz filters was
followed by two PUF sampling modules in series.
• Residence Chamber Sample Collection Array R5, Port #R5
Sample Collection Array R5 collected fine particulate matter and gas-phase organic
compounds. This array consisted of a single sintered stainless steel filter unit
followed by a SUMMA polished stainless steel canister.
• Residence Chamber Sample Collection Array R6, Port #R6
Sample Collection Array R6 collected fine particulate matter. This array consisted of
a 2.5 |im cyclone followed by two identical legs containing Teflon filters.
• Residence Chamber Sample Collection Array R8, Port #R8
Sample Collection Array R8 collected fine particulate matter on paired quartz filters
for total carbon and elemental carbon analysis and collected semivolatile organic
compounds using two PUF sampling modules in series. This sample collection array
consisted of a 2.5 |im cyclone with two quartz filters in parallel; one of these quartz
filters was followed by two PUF sampling modules in series.
34
-------
• Residence Chamber Sample Collection Array RIO, Port #R10
Sample Collection Array RIO collected fine particulate matter on two quartz filters
in parallel and collected semivolatile organic compounds on two XAD-4-coated
denuders in series and on two PUF sampling modules in series. This sample collec-
tion array consisted of a 2.5 |im cyclone immediately prior to two XAD-4-coated
annular denuders in series, followed by two identical legs each containing a quartz
filter; one of these quartz filters is followed by two PUF sampling modules in series.
Denuder Sampling
In the field, denuders were used in series as pairs on Residence Chamber Port #10. On
Test Day 1, the paired denuders were changed and extracted every half hour across the
duration of testing, as shown in Table 8. The paired denuders were removed from the
sample collection array and separated. Each denuder was rinsed with a mixture of methylene
chloride:acetone:hexane in a volume ratio of 2:3:5. The solvent mixture was added to the
denuder and the denuder tube was capped and shaken (four times); an internal standard was
added to the first extraction. The rinses were combined in a precleaned glass jar for paired
denuders, the jar was labeled and sealed with Teflon tape. Chain of custody documentation
was initiated for the extract, and the jar was stored over ice. Denuder extracts for each half-
hour sampling episode were combined, but each half-hour sampling episode generated a
separate sample (i.e., 13 denuder extract samples generated). After extraction, the denuders
and caps were dried using high purity nitrogen and capped until ready for re-use. A different
sampling scheme was used for the paired denuders on Test Days 2 and 3. The first pair of
denuders collected sample for a half hour, the second set of paired denuders collected
sample for 1 hour, the third pair for 2 hours, and the fourth pair for 4 hours, as shown in
Table 8. A denuder sampling log is included in Appendix B.
Use of the ELPI Particle Size Distribution Analyzer
In addition to the sample collection arrays, an ELPI continuous particle size analyzer
was used on the residence chamber to collect data on particle size distribution in the diluted
source sample. The ELPI measures airborne particle size distribution in the size range 30 to
1000 nm (0.03 to 10 |im) with 12 channels. The principle of operation is based on charging,
inertial classification, and electrical detection of the aerosol particles. The instrument
consists primarily of a corona charger, low pressure cascade impactor, and multichannel
electrometer.
35
-------
Table 8. Denuder Sampling Scheme
Test
Pair Number
Duration
Number
(min)
1
1
35
2
30
3
30
4
30
5
30
6
30
7
30
8
30
9
27
10
30
11
30
12
30
13
30
Total
13 samples
392 min
2
1
30
2
60
3
120
4
240
Total
4 samples
450 min
3
1
30
2
60
3
120
4
240
Total
4 samples
450 min
In operation, the sample first passed through a unipolar positive polarity charger in
which particles in the sample were electrically charged by small ions produced in a corona
discharge. After the charger, the charged particles were size classified on a low pressure
impactor. The impactor is an inertial device classifying the particles according to their
aerodynamic diameter, not their charge. The stages of the impactor are insulated electrically,
and each stage is connected individually to an electrometer current amplifier. The charged
particles collected in a specific impactor stage produce an electrical current, which is
recorded by the respective electrometer channel. A larger charge correlates to a higher
particle population. The current value of each channel is proportional to the number of
particles collected and thus to the particle concentration in the particular size range. The
36
-------
current values are converted to an aerodynamic size distribution using particle size-
dependent relationships describing the properties of the charger and the impactor stages.
The precalibrated instrument was transported to the field and placed in the vicinity of the
sample collection arrays on a sturdy table. Twenty minutes prior to the start of the test run,
the ELPI was turned on to warm up and equilibrate. The computer was turned on, and the
sample acquisition program was initiated in the flush mode. On the ELPI, the sample flow
was manually adjusted to the manufacturer's specifications (vacuum setting to 100 ± 1
mbar). The ELPI was set to monitor the range of 0.03 to 10 |im (30 to 1000 nm) midpoint
particle diameter to provide an indication of particle size distribution in the range below 10
|im, as well as the concentration distribution of the particles within this size range. The data
system was initially set up to collect data for particles ranging from 0.03 to 10 |im; the
particles were collected over the duration of each test.
Shortly before the initiation of the test run, the data system was programmed to collect
particulate data that encompassed the expected duration of the test run. The ELPI was the
last piece of equipment connected to the residence chamber. When the test run was started,
the inlet line was attached to the port, and flushing of the inlet line was terminated by the
data system. Data were continually saved on the computer hard drive, and a real-time
display on the computer screen showed the particle distribution. Graphical presentations of
the data were prepared off-line.
For each run, impactor stages were covered with tared aluminum foils. After test runs,
the foils were recovered and individually weighed for additional mass data.
Measurement of 02 and C02 Process Concentrations
Measurements taken using Fyrite bulbs every 30 minutes across the duration of the test
each day (17 points) were used to determine 02 and C02 concentrations during test
conditions.
Operation of the Dilution Sampling System with Sample
Collection Arrays
After completion of the pre-test run to establish experimental parameters for the test, the
dilution sampling system was prepared for a full test run. Sampling probe temperature set
points were set equal to or slightly above the measured stack temperature. The system was
equilibrated at temperature. Sample collection arrays were loaded with appropriate
collection media, and flow/leak checks were performed with each array to ensure that the
37
-------
entire system would be leak free in operation. Sampler flows were set just before initiation
of the test to prevent heat loss from the heated probe. The blower and the ring compressor
were started to achieve a slightly positive pressure; then the blower flow was adjusted to
cause the stack gas to flow into the dilution sampling system after the probe was inserted
into the duct. Sample collection array pumps were started, and valves for the SUMMA
canisters were opened to initiate canister air sample collection. The sampling process was
carefully monitored by the sampling team based on the pressure change in the canister to
ensure that the filters were not overloaded in the course of sampling. Start time and other
pertinent data were recorded.
At the end of the eight-hour sampling interval, the sampling process was stopped by
stopping the pumps for the sample collection arrays and closing the valves on the SUMMA
canisters. The probe was withdrawn from the stack, the blower and ring compressor were
turned off, and heaters were turned off and allowed to cool. Each sample collection array
was leak checked at the end of the sampling period and ending flow rates were documented.
Experimental parameters for Tests 1, 2, and 3 are shown in Tables 9 to 11; blower flow,
dilution flow, and venturi flow for Tests 1, 2, and 3 are shown graphically in Figures 14
through 22. The dilution ratio is defined as the sum of the dilution airflow rate plus the
sample gas flow rate divided by the sample gas flow rate. The dilution ratio averaged 45.5
for the three tests conducted on the hogged fuel boiler.
Table 9. Run Time Summary Information, Test Run 1 (11/27/01)
Run Parameter Value
Start Time 8:37:06 A.M.
End Time 4:35:46 P.M.
Run Time 478.67 min
Barometric Pressure 29.53 in. Hg
Nozzle Size #9, 0.299 in. id (160 °C, 2153.4 fit/min)
Canister Flow dilution canister, 8.125 cm3/min
residence chamber canister 8.125 cm3/min
ambient canister, 9.375 cm3/min
continued
38
-------
Table 9. (concluded)
Measurement Parameter Value
Venturi Flow
PT-101C
TE-104e
Dilution Flow
PT-102
TE-108
Blower Flow
PT-103
TE-105
Dilution Ratio
TE-101
TE-102
TE-103
30.52 aL/min3 (18.75 sL/minb)
-1.35 in. WCd
198.31 °C
880.96 aL/min (843.92 sL/min)
-1.75 in. WC
27.11 °C
742.52 aL/min (682.13 sL/min)
-16.67 in. WC
29.93 °C
46.12
187.85 °C
200.28 °C
not used
Sample Flow Rates
Sample
Location
Port
Start/
End
Flow
Average Flow
(sL/min) (aL/min) (sL/min)
pm25
pm25
Dilution Air
Dilution Air
—
start
end
17.19
17.19
17.30
17.30
17.19
pm25
pm25
Residence Chamber
Residence Chamber
10
10
start
end
16.89
16.29
16.99
16.39
16.59
pm25
pm25
Residence Chamber
Residence Chamber
8
8
start
end
17.19
17.19
17.30
17.30
17.19
pm25
pm25
Residence Chamber
Residence Chamber
6
6
start
end
17.19
17.19
17.30
17.30
17.19
pm25
pm25
Residence Chamber
Residence Chamber
4
4
start
end
17.04
17.04
17.14
17.14
17.04
pm25
pm25
Residence Chamber
Residence Chamber
2
2
start
end
17.04
17.04
17.14
17.14
17.04
DNPH
Residence Chamber
3
start
0.80
0.81
0.80
DNPH
Residence Chamber
3
end
0.80
0.81
DNPH
Dilution Chamber
3
start
0.83
0.83
0.83
DNPH
Dilution Chamber
3
end
0.83
0.83
a aL/min = actual liters per minute
b sL/min = standard liters per minute
c PT = pressure transducer
d WC = water column
e TE = thermocouple
39
-------
Table 10. Run Time Summary Information, Test Run 2 (11/28/01)
Run Parameter Value
Start Time 8:18:04 A.M.
End Time 4:18:14 P.M.
Run Time 480.03 min
Barometric Pressure 29.62 in. Hg
Nozzle Size #9, 0.299 in. id (160 °C, 2153.4 ft/min)
Canister Flow dilution canister, 8.125 cm3/min
residence chamber canister 8.125 cm3/min
Measurement Parameter Value
Venturi Flow
PT-101C
TE-104e
Dilution Flow
PT-102
TE-108
Blower Flow
PT-103
TE-105
Dilution Ratio
TE-101
TE-102
TE-103
30.54 aL/mina (18.72 sL/minb)
-1.44 in. WCd
20.52 °C
881.27 aL/min (843.82 sL/min)
-1.78 in. WC
28.15 °C
742.46 aL/min (681.84 sL/min)
-16.55 in. WC
31.10 °C
46.13
190.55 °C
200.01 °C
not used
Sample Flow Rates
Sample
Location
Port
Start/
End
Flow
Average Flow
(sL/min) (aL/min) (sL/min)
pm25
Dilution Air
—
start
17.21
17.27
pm25
Dilution Air
—
end
17.06
17.12
pm25
Residence Chamber
10
start
16.01
16.07
pm25
Residence Chamber
10
end
16.16
16.22
pm25
Residence Chamber
8
start
17.06
17.12
pm25
Residence Chamber
8
end
17.21
17.27
pm25
Residence Chamber
6
start
17.06
17.12
pm25
Residence Chamber
6
end
17.06
17.12
pm25
Residence Chamber
4
start
17.21
17.27
pm25
Residence Chamber
4
end
17.06
17.12
17.14
16.09
17.14
17.06
17.14
continued
40
-------
Table 10. (concluded)
Sample Flow Rates
Start/ Flow Average Flow
Sample
Location
Port
End
(sL/min)
(aL/min)
(sL/min)
pm25
pm25
Residence Chamber
Residence Chamber
2
2
start
end
17.36
17.21
17.42
17.27
17.29
DNPH
Residence Chamber
3
start
0.83
0.83
0.82
DNPH
Residence Chamber
3
end
0.80
0.81
DNPH
Dilution Chamber
3
start
0.85
0.85
0.85
DNPH
Dilution Chamber
3
end
0.85
0.85
a aL/min = actual liters per minute
b sL/min = standard liters per minute
c PT = pressure transducer
d WC = water column
e TE = thermocouple
Table 11. Run Time Summary Information, Test Run 3 (11/29/01)
Run Parameter Value
Start Time 8:00:00 A.M.
End Time 4:00:30 P.M.
Run Time 480.50 min
Barometric Pressure 29.68 in. Hg
Nozzle Size #9 0.299 in. id (160 °C, 2153.4 ft/min)
Canister Flow dilution canister, 8.125 cm3/min
residence chamber canister 8.125 cm3/min
Measurement Parameter Value
Venturi Flow
PT-101C
TE-104e
Dilution Flow
PT-102
TE-108
Blower Flow
PT-103
TE-105
Dilution Ratio
TE-101
TE-102
TE-103
30.54 aL/min3 (18.77 sL/minb)
-1.48 in. WCd
200.10 °C
878.49 aL/min (845.52 sL/min)
-1.79 in. WC
27.23 °C
742.39 aL/min (684.68 sL/min)
-16.86 in. WC
30.18 °C
46.10
190.64 °C
199.89 °C
not used
continued
41
-------
Table 11. (concluded)
Sample Flow Rates
Sample
Location
Port
Start/
End
Flow
Average Flow
(sL/min) (aL/min) (sL/min)
pm25
pm25
Dilution Air
Dilution Air
—
start
end
17.24
17.24
17.24
17.24
17.24
pm25
pm25
Residence Chamber
Residence Chamber
10
10
start
end
16.04
16.04
16.04
16.04
16.04
pm25
pm25
Residence Chamber
Residence Chamber
8
8
start
end
17.09
17.09
17.09
17.09
17.09
pm25
pm25
Residence Chamber
Residence Chamber
6
6
start
end
17.24
17.09
17.24
17.09
17.17
pm25
pm25
Residence Chamber
Residence Chamber
4
4
start
end
17.24
17.09
17.24
17.09
17.17
pm25
pm25
Residence Chamber
Residence Chamber
2
2
start
end
17.24
17.24
17.24
17.24
17.24
DNPH
Residence Chamber
3
start
0.87
0.87
0.84
DNPH
Residence Chamber
3
end
0.80
0.80
DNPH
Dilution Chamber
3
start
0.99
0.99
0.97
DNPH
Dilution Chamber
3
end
0.94
0.94
a aL/min = actual liters per minute
b sL/min = standard liters per minute
c PT = pressure transducer
d WC = water column
e TE = thermocouple
42
-------
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Figure 14. Blower Flow, Day 1 (11/27/01).
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1—sianflard *-
¥
S 01 :0
-------
Actual
Standard
8:00:00 9:00:00 10:00:00 11:00:00 12:00:00 13:00:00 14:00:00 15:00:00 16:00:00 17:00:00 18 00:00
Time
Figure 16. Venturi Flow, Day 1 (11/27/01).
600
200
0 •
7:0l>;CK) 8:00:00 8:00:00 10:00:00 11:00:00 12:00:00 13:00:00 14:00:00 15:00:00 16:00.00 17:00:00 18:00:00
Time
Figure 17. Blower Flow, Day 2 (11/28/01).
44
-------
1200
1000
Actual
800
Standard
600
400
200
7:0 ) 00 WWUD 9 00 00 10:00:00 11:00:00 12 00:00 13:00 00 14:00:00 15 00:00 16:00 00*17:00 00 18 00 00
-200
Time
Figure 18. Dilution Flow, Day 2 (11/28/01).
j Actual
f i
I f Standard
*
[ " i '
t
i :
>•£»
V
7:00:00 8:00:00 9:00:00 10:00:00 11:00:00 12:00:00 13:00:00 14:00:00 15:00:00 16:00:00 17:00:00 18:00:00
Time
Figure 19. Venturi Flow, Day 2 (11/28/01).
45
-------
1000
800
c
"E
600
400
200
-200
Standard
0 ¦
7:0100 8:00.00 9 00.00 10 00:00 11:00:00 12:00:00 13:00:00 14 00:00 15:00:00 16:00:00 17:0)0:00
Time
Figure 20. Blower Flow, Day 3 (11/29/01).
1200
800
c 600
1
400
-200
Actual
Standard
P
7:00:00—STJOiOO 9:00:00 10:00:00 11:00:00 12:00:00 13:00:00 14:00:00 15:00:00 16:000b 17:00:00
Time
Figure 21. Dilution Flow, Day 3 (11/29/01).
46
-------
60 t
50
40
Actual
Standard
20
7:00:00 8:00:00 9:00:00 10:00.00 11:00:00 12 00:00 13:00:00 14 00:00 15:00:00 16:00:00 17:00:00
Time
Figure 22. Venturi Flow, Day 3 (11/29/01).
Dilution System Sample Collection Arrays: Train Recovery
At the end of the sampling period, the pumps on the dilution system were turned off, and
recovery of the dilution sampling system consisted of removing the sample collection arrays
and turning off the particle size analyzer. Sample collection arrays were then carried to the
recovery area and disassembled, the parts were carefully labeled, and the components of the
sample collection arrays were carefully packaged for transport back to the laboratories.
The sample collection arrays were removed sequentially at the cyclone connection. Each
individual collection array was removed, and the ends of the assembly were covered with
aluminum foil. As each sample collection array was removed from the dilution sampling
system, the sampling aperture was covered to avoid introduction of any contaminants into
the dilution sampling system. The ends of the sample collection array were capped and the
array placed in a secure container for transport to the sample recovery area.
In the sample recovery area, the sample collection arrays were disassembled into the
following components:
47
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PUF modules were disassembled from the sample collection array as a module. Both
ends of the PUF sampling module were capped, the module placed in a sealable
plastic bag, the bag appropriately labeled, and chain of custody documentation
initiated.
Filters were positioned in specific filter holder assemblies as part of several of the
sample collection arrays. In the sample recovery area, the filter holder assemblies
were disassembled, and the filter was removed with Teflon-tipped tweezers and
placed in a prenumbered custom filter container with a locking lid. The appropriate
label was affixed to the filter container, and chain of custody documentation was
initiated. The filter holder assembly was reassembled without the filter, placed in a
sealable plastic bag, and labeled.
Denuders were disassembled, the ends of the sorbent tube closed with Teflon caps
and sealed with Teflon tape, the sealed denuder tubes placed in a sealable plastic
bag, labeled, and chain of custody documentation initiated.
Carbonyl sampling tube assemblies (two carbonyl sampling tubes in series) were
disassembled. The ends of the individual tubes were sealed with plastic caps and the
sealed tubes placed in an aluminum foil packet, labeled to preserve the front/back
order from the sample collection array, placed in a plastic bag, labeled, and chain of
custody documentation initiated.
Canister sampling was terminated by closing the valve on the canister at the end of
the sampling period. The canister with closed valve was disconnected from the
dilution sampling system and capped; chain of custody documentation was initiated.
At a later time, extraction was performed on-site for the denuders. The denuders were
rinsed with a mixture of methylene chloride:acetone:hexane in a volume ratio of 2:3:5. The
solvent mixture was added to the denuder, and the denuder tube was capped and shaken four
times. An internal standard was added to the first extraction. The rinses were combined in a
precleaned glass jar for paired denuders; the jar was labeled and sealed with Teflon tape;
chain of custody documentation was initiated for the extract, and the jar was stored over ice.
After extraction, the denuders and caps were dried using high purity nitrogen and capped
until ready for reuse.
Denuders, PUF modules, and filters were all bagged and stored over ice. Canisters and
carbonyl tubes were transported to the ERG laboratory for analysis; and the filters, PUF
modules, and denuder extracts were transported to the EPA laboratory for analysis. Chain of
custody documentation and field sample log with sample identification are supplied in
Appendix B.
48
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Laboratory Experimental Methodology
Components of the sample collection arrays, filters, DNPH-impregnated silica gel tubes
used to sample carbonyl compounds, and canisters used to sample volatile organic
compounds were returned for analysis to EPA and ERG laboratories (see Table 1 for
responsible laboratory). The analyses described in the following sections were performed
with the analytical methodology used by the respective laboratories summarized in Table 1;
standard operating procedures (SOPs) (ERG) and method operating procedures (MOPs)
(EPA) supporting the analyses are listed in Appendix L.
PM2 5 Mass
Teflon membrane (Gelman Teflon) filters of 2 |im pore diameter were used to collect
fine PM samples for mass determinations. Filters before and after sample collection were
maintained at 20-23 °C and a relative humidity of 30%-40% for a minimum of 24 hours
prior to weighing on a microbalance. Sample mass was determined by gravimetric analysis
before and after sample collection.
Elemental Analysis
Individual elements above atomic number 9 (fluorine) were measured using a Philips
Model 2404, wavelength-dispersive, X-ray fluorescence (XRF) spectrometer running the
UniQuant program. This program gives qualitative and quantitative information on the
elements present on a Teflon membrane filter. The filter to be analyzed was covered with a
0,4-|im thick Prolene film, which was attached using glue. The glue was only on the outer
rim of the filter and did not interfere with the analysis. Only elements that gave amounts
greater than one standard error above the detection limit were reported.
Water-Soluble Inorganic Ions
Teflon filter samples were analyzed for major inorganic anions and cations using a
Dionex DX-120 ion chromatograph equipped with a 25-|iL sample loop and a conductivity
detector. Major ions determined were chloride, nitrate, sulfate, calcium, magnesium,
potassium, and ammonium. Prior to extraction, the filters were wetted with 350 to 500 |iL of
ethanol. Two sequential extractions with HPLC-grade water were performed using mild
sonication of the filters followed by filtration of the extracts. The two extracts were
combined for analysis.
49
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Anions were separated using an Ion Pac AS 14 (4 x 250 mm) column with an alkyl
quaternary ammonium stationary phase and a carbonate-bicarbonate mobile phase. Cations
were separated using an Ion Pac CS12 (4 x 250 mm) column with an 8-|im
poly(ethylvinylbenzene-divinylbenzene) macroporous substrate resin functionalized with a
relatively weak carboxylic acid stationary phase and a sulfuric acid mobile phase. Ion
concentrations were determined from four-point calibration curves using an external
standard method. All samples were extracted and analyzed in duplicate or triplicate.
Elemental Carbon/Organic Carbon
Elemental carbon and organic carbon (EC/OC) content of PM samples collected on pre-
fired quartz filters was determined by National Institute for Occupational Safety and Health
(NIOSH) Method 5040 (NIOSH, 1994)7 using a Sunset Laboratory thermal evolution
instrument. In this method, a 1.0 x 1.5 cm punch of the quartz filter sample is placed in the
instrument, and organic and carbonate carbon are evolved in a helium atmosphere as the
temperature is raised to 850 °C. Evolved carbon is catalytically oxidized to C02 in a bed of
granular Mn02 then reduced to methane in a methanator. Methane is subsequently
quantified by a flame ionization detector (FID). In a second stage, the sample oven
temperature is reduced, an oxygen-helium mixture is introduced, and the temperature is
increased to 940 °C. With the introduction of oxygen, pyrolytically generated carbon is
oxidized, and the transmittance of a laser light beam through the filter increases. The point
at which the filter transmittance reaches its initial value is defined as the split between OC
and EC. Carbon evolved prior to the split is considered OC (including carbonate), and
carbon volatilized after the split is considered EC. Elemental carbon evolved is similarly
oxidized to C02 and subsequently reduced to methane to be measured by the FID.
Organic Compounds
Individual organic compounds present in the fine PM collected on pre-fired quartz filters
were determined by extracting the filters with hexane (two extractions) followed by a 2:1
mixture by volume of benzene and isopropanol (three extractions). Prior to extraction, the
filters were composited as necessary to achieve a total of approximately 0.5 mg of OC and
spiked with a mixture of 16 deuterated internal recovery standards. These standards were
selected to represent the range of expected solubilities, stabilities, chromatographic retention
times, and volatilities of organic compounds present in the samples. All extracts from the
five extraction steps were combined and concentrated using an automated nitrogen blow-
down apparatus.
50
-------
An aliquot of the combined extract was derivatized with diazomethane to yield methyl
esters of any fatty acids which might be present. After the methylation reaction was
complete, the methylated extract aliquot was reconcentrated by nitrogen blow-down. A
separate portion of the methylated extract was derivatized a second time using
bis(trimethylsilyl)- trifluoroacetamide-N,0-bis(trimethylsilyl) acetamide (Sylon BFT)
reagent to convert compounds such as levoglucosan and cholesterol to their trimethylsilyl
(TMS) derivatives. Both derivatization reactions were performed in order to allow the
compounds to be separated and eluted from a gas chromatograph column. Since the TMS
derivatives are somewhat unstable over time, the silylation was carried out just prior to
analysis.
Gas chromatography coupled with a mass spectrometer detector (GC/MS) was used to
identify and quantify the individual organic compounds present in the extracts. A Hewlett-
Packard 6890 GC equipped with an HP 5973 mass spectrometer detector was used. A 5-MS
column (30 m, 0.25 mm diameter, 0.25 |im film thickness) was employed along with an
injector temperature of 65 °C and a GC/MS interface temperature of 300 °C. The initial GC
oven temperature was set at 65 °C with an initial hold time of 10 minutes. The oven
temperature was then ramped upward at 10 °C/min to 300 °C and held at the upper
temperature for an additional 41.5 minutes. Helium was used as the carrier gas (1 mL/min),
and the GC was operated in the split/splitless mode.
Positive identification of target compounds was obtained by comparing mass spectra of
the analytes with those obtained from 132 authentic compound standards. Iso- and anteiso-
alkanes were identified using secondary standards derived from paraffin candle wax.
Additional compounds were identified as "probable" based on a comparison of the GC
retention times and mass spectra with commercially available spectral libraries.
Quantification of the individual compounds involved referencing each compound against
one or more of the deuterated internal standards spiked into the sample to correct for losses
of the analytes that may have occurred in the compositing, extracting, concentrating, and
derivatizing steps. An extensive set of standards of target compounds at known
concentrations, which also included the deuterated internal standard compounds, was used
to establish three-point or five-point calibration curves from which the concentrations of the
analytes were determined.
Carbonyl Compounds
Sep-Pak chromatographic-grade silica gel cartridges impregnated with DNPH were used
in series for carbonyl sample collection. The tubes were used in series to check for
51
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compound breakthrough. Following sample collection in the field, the cartridges and
accompanying chain of custody documentation were transported to the ERG laboratory,
where they were logged into the laboratory sample tracking system. The cartridges were
extracted and analyzed for the carbonyl compounds listed in Table 12 using an adaptation of
EPA Compendium Method TO-11 A, "Determination of Formaldehyde in Ambient Air
Using Adsorbent Cartridge Followed by High Performance Liquid Chromatography
(HPLC)".8 The analytical instrument was a Varian 5000 HPLC with a multiwavelength
detector operated at 360 nm. The HPLC was configured with a 25-cm, 4.6-mm id, C18 silica
analytical column with a 5-|im particle size. An automatic sample injector was used to inject
25-|iL aliquots into the HPLC. MDLs9 for the carbonyl analysis are shown in Table 12.
Table 12. Carbonyl Compounds Analyzed by High Performance Liquid
Chromatography: Method Detection Limits
Method Detection Limits8
Compound
CAS No.
(^g)
formaldehyde
50-00-0
0.0838
acetaldehyde
75-07-0
0.0916
acetone
67-64-1
0.0428
propionaldehyde
123-38-6
0.0934
crotonaldehyde
4170-30-3
0.1283
butyraldehyde
123-72-8
0.0956
benzaldehyde
100-52-7
0.0959
isovaleraldehyde
590-86-3
0.1076
valeraldehyde
110-62-3
0.1758
o-tolualdehyde
529-20-4
0.1439
m-tolualdchydc
620-23-5
0.1439
/Molualdchydc
104-87-0
0.1439
hexaldehyde
66-25-1
0.1377
2,5 -dimethylbenzaldehyde
5779-94-2
0.13373
diacetyl
432-03-8
0.01543
methacrolein
78-85-3
0.01253
2-butanone
78-93-3
0.01253
glyoxal
107-22-2
0.04123
acetophenone
98-86-2
0.02503
methylglyoxal
78-98-8
0.02443
octanal
124-13-0
0.01003
nonanal
124-19-6
0.01823
a Estimated value.
52
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The chromatography data acquisition system was used to retrieve data from the HPLC.
The data were processed and peak identifications were made using retention times and
relative retention times determined by analysis of analytical standards. After peak
identifications were made, the concentration of each target analyte was determined using
individual response factors for the carbonyl compounds.
Per Table 23, daily calibration checks were performed to ensure that the analytical
procedures were in control. Daily quality control checks were performed after every 10
samples on the days that samples were analyzed, with compound responses within ±15% of
the current calibration curve. Compound retention time drifts were also measured from the
analysis of the quality control check sample and tracked to ensure that the HPLC was
operating within acceptable parameters.
As part of the daily quality control check, if the analysis of the daily quality control
sample was not acceptable, a second quality control standard was injected. If the second
quality control check also did not meet acceptance criteria or if more than one daily quality
control check did not meet acceptance criteria, a new calibration curve (at five concentration
levels) was established. All samples analyzed with the unacceptable quality control checks
would be reanalyzed.
An acetonitrile system blank was analyzed after the daily calibration check and before
sample analysis. The system was considered in control if target analyte concentrations were
less than the current method detection limits.
Canister Analyses: Air Toxics and Speciated Nonmethane Organic
Compounds
The combined analysis for gas-phase air toxics and speciated NMOCs (SNMOCs) was
performed on a GC/FID/mass selective detector (MSD). A Hewlett-Packard 5971 MSD and
a Hewlett-Packard 5890 Series II GC with a 60-m by 0.32-mm id and a 1 -|im film thickness
J&W DB-1 capillary column followed by a 2:1 splitter was used to send the larger portion of
the column effluent to the MSD and the smaller fraction to the FID. The chromatograph
oven containing the DB-1 capillary column was cooled to -50 °C with liquid nitrogen at the
beginning of the sample injection. This temperature was held for five minutes and then
increased at the rate of 15 °C per minute to 0 °C. The oven temperature was then ramped at
6 °C/minute to 150 °C, then ramped at 20 °C/minute to 225 °C and held for eight minutes.
The gas eluting from the DB-1 capillary column passed through the 2:1 fixed splitter to
divide the flow between the MSD and the FID.
53
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The air toxics analysis was performed according to the procedures of EPA Compendium
Method TO-15, "Determination of Volatile Organic Compounds (VOCs) in Air Collected in
Specially Prepared Canister and Analyzed by Gas Chromatography/Mass Spectrometry
(GC/MS)".10 The analysis of SNMOCs was performed according to the procedures of
"Technical Assistance Document for Sampling and Analysis of Ozone Precursors".8
Detection limits9 for air toxics are shown in Table 13 and for the SNMOCs in Table 14.
Particle Size Distribution Data
The ELPI was operated and collected data during all three test days. Data were reduced
using the Dekati software package.
Table 13. Method Detection Limits for Air Toxics Compounds (Analytical Method TO-
15)10
Compound
CAS No.
Method Detection Limit1
(lig/m3)
Acetylene
74-86-2
0.24
Propylene
115-07-1
0.17
Dichlorodifluoromethane
75-71-8
0.40
Chloromethane
74-87-3
0.24
Dichlorotetrafluoroethane
1320-37-2
0.70
Vinyl chloride
75-01-4
0.31
1,3-Butadiene
106-99-0
0.31
Bromomethane
74-83-9
0.70
Chloroethane
75-00-3
0.42
Acetonitrile
75-05-8
0.84
Acetone
67-64-1
1.23
T richlorofluoromethane
75-69-4
0.45
Acrylonitrile
107-13-1
0.91
1,1 -Dichloroethene
75-35-4
0.79
Methylene chloride
75-09-2
0.42
T richlorotrifluoroethane
26523-64-8
1.07
trans- 1,2-Dichloroethylene
56-60-5
0.47
1,1 -Dichloroethane
75-34-3
0.65
Methyl tert-butyl ether
1634-04-1
1.29
Methyl ethyl ketone
78-93-3
0.88
Chloroprene
126-99-8
0.73
cis-1,3 -Dichloroethylene
156-59-2
0.79
Bromochloromethane
74-97-5
1.26
continued
54
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Table 13. (concluded)
Method Detection Limit9'a
Compound
CAS No.
(Rg/m3)
Chloroform
67-66-3
0.49
Ethyl tert-butyl ether
637-92-3
1.25
1,2-Dichloroethane
107-06-2
0.48
1,1,1 -Trichloroethane
71-55-6
0.65
Benzene
71-43-2
0.25
Carbon tetrachloride
56-23-5
1.01
tert-Amyl methyl ether
994-05-8
1.00
1,2-Dichloropropane
78-87-5
0.65
Ethyl acrylate
140-88-5
1.31
Bromodichloromethane
75-27-4
0.80
Trichloroethylene
79-01-6
0.75
Methyl methacrylate
80-62-6
1.47
cis-1,2-Dichloropropene
10061-01-5
0.82
Methyl isobutyl ketone
108-10-1
1.36
trans-1,2-Dichloropropene
10061-02-6
1.00
1,1,2-Trichloroethane
79-00-5
0.65
Toluene
108-88-3
0.45
Dibromochloromethane
124-48-1
1.36
1,2-Dibromoethane
106-93-4
1.23
«-Octanc
111-65-9
0.56
T etrachloroethylene
127-18-4
0.81
Chlorobenzene
108-90-7
0.55
Ethylbenzene
100-41-4
0.35
m-, /^-Xy lene
108-38-3/106-42-3
0.87
Bromoform
75-25-2
1.65
Styrene
100-42-5
0.59
1,1,2,2-Tetrachloroethane
79-34-5
0.82
o-Xylene
95-47-6
0.43
1,3,5 -T rimethylbenzene
108-67-8
0.69
1,2,4-Trimethylbenzene
95-63-6
0.69
m-Dichlorobcnzcnc
541-73-1
0.60
Chloromethylbenzene
100-44-7
0.72
/;-Dichlorobenzene
106-46-7
1.08
o-Dichlorobenzene
95-50-1
0.72
1,2,4-Trichlorobenzene
120-82-1
0.89
Hexachloro-1.3 -butadiene
87-68-3
1.28
a MDLs reported here are based on nominal injection volume of 200 mL of gas.
55
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Table 14. Method Detection Limits for Speciated Nonmethane Organic Compounds
Method Detection Limits8
Compound
CAS No.
(|J-g/m
Ethylene
74-85-1
0.50
Acetylene
74-86-2
0.47
Ethane
74-84-0
0.54
Propylene
115-07-1
0.44
Propane
74-98-6
0.46
Propyne
74-99-7
0.42
Isobutane
75-28-5
0.43
Isobutene/1 -butene
115-11-7/106-98-0
0.21
1,3-Butadiene
106-99-0
0.40
«-Butane
106-97-8
0.43
fra«s-2-Butene
624-64-6
0.42
C7.V-2-Butene
590-18-1
0.42
3 -Methyl-1 -butene
563-45-1
0.32
Isopentane
78-78-4
0.33
1-Pentene
109-67-1
0.32
2-Methyl-1 -butene
563-46-2
0.45
/7-Pentane
109-66-0
0.33
Isoprene
78-79-4
0.31
fra«s-2-Pentene
646-04-8
0.33
c7.v-2-Pcntene
627-20-3
0.33
2-Methyl-2-butene
513-35-9
0.32
2,2-Dimethylbutane
75-83-2
0.46
Cyclopentene
142-29-0
0.31
4-Methyl-1 -pentene
691-37-2
0.45
Cyclopentane
287-92-3
0.32
2,3-Dimethylbutane
79-29-8
0.46
2-Methylpentane
107-83-5
0.46
3-Methylpentane
96-14-0
0.46
2-Methyl-1 -pentene
763-29-1
0.46
1-Hexene
592-41-6
0.46
2-Ethyl-l-butene
760-21-4
0.45
/7-Hexane
110-54-3
0.46
fra«s-2-Hexene
4050-45-7
0.46
c7.v-2-Hcxcne
7688-21-3
0.46
Methylcyclopentane
96-37-7
0.45
2,4-Dimethylpentane
108-08-7
0.35
Benzene
71-43-2
0.42
Cyclohexane
110-82-7
0.45
2-Methylhexane
591-76-4
0.40
continued
56
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Table 14. (concluded)
Method Detection Limits8
Compound
CAS No.
(lie/m
2,3 -Dimethylpentane
565-59-3
0.40
3-Methylhexane
589-34-4
0.40
1-Heptene
592-76-7
0.39
2,2,4-Trimethylpentane
540-84-1
0.51
«-Hcptanc
142-82-5
0.40
Methylcyclohexane
108-87-2
0.39
2,2,3-Trimethylpentane
564-02-3
0.51
2,3,4-Trimethylpentane
565-75-3
0.51
Toluene
108-88-3
0.37
2-Methylheptane
592-27-8
0.51
3-Methylheptane
589-81-1
0.51
1-Octene
111-66-0
0.50
/7-Octanc
111-65-9
0.51
Ethylbenzene
100-41-4
0.52
m-, /;-Xylcnc
108-38-3/106-42-3
0.47
Styrene
100-42-5
0.46
o-Xylene
95-47-6
0.47
1-Nonene
124-11-8
0.40
/7-Nonanc
111-84-2
0.41
Isopropylbenzene
98-82-8
0.38
a-Pincnc
80-56-8
0.39
/7-Propylbcnzcnc
103-65-1
0.38
m-Ethyltolucnc
620-14-4
0.38
/;-Ethyltolucnc
622-96-8
0.38
1,3,5 -T rimethylbenzene
108-67-8
0.38
o-Ethyltoluene
611-14-3
0.38
P-Pinene
127-91-3
0.39
1,2,4-Trimethylbenzene
95-63-6
0.38
1-Decene
872-05-9
0.33
«-Decane
124-18-5
0.33
1,2,3 -Trimethylbenzene
526-73-8
0.38
m-Dicthylbcnzcnc
141-93-5
0.32
/;-Dicthylbcnzcnc
105-05-5
0.32
1-Undecene
821-95-4
0.49
/7-Undccanc
1120-21-4
0.50
1-Dodecene
112-41-4
0.49
/7-Dodccanc
112-40-3
0.50
1-Tridecene
2437-56-1
0.49
/7-Tridccanc
629-50-5
0.50
57
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58
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Results and Discussion
Analyses were performed in either EPA or ERG laboratories according to the
responsibilities delineated in Table 1 and with the analytical procedures described in the
previous section. Results of these analyses are discussed in this section.
Emission Factors for PM2 5 Mass and Gas-Phase
Carbonyls and Nonmethane Organic Compounds
Emission factors (mass of species emitted per unit mass of fuel consumed) for PM2 5
mass, gas-phase carbonyl compounds, and gas-phase NMOCs are shown in Table 15.
Examples of the emission factor calculations are provided in Appendix C. Supporting
analytical data for the PM2 5, carbonyl, and NMOC results are provided in Appendices D, E,
and F, respectively. Concentrations of PM25, carbonyl compounds, and NMOCs in the
diluted stack gas were corrected for the concentrations of these species in the cleaned
dilution air. Significant concentrations of //-hexane, methylene chloride, and acetone were
also observed in the gas samples collected from the dilution sampler during all three test
days with unusually high concentrations of these compounds observed on the second test
day. However, the presence of these compounds may be artifactual. Different sets of the
XAD-coated annular denuders were extracted near the sampling location using these same
three solvents, and the denuders were placed into service on an alternating schedule to avoid
exceeding the capacity of a single set of denuders during a test run. Therefore, the presence
of these three compounds in the stack gas samples collected by the dilution sampler and in
the ambient air sample collected on the stack are considered suspect and are likely due to
contamination arising from on-site extraction of the organic denuders. Values for NMOC
(both speciated and total), carbonyl compounds (both speciated and total), and air toxics
compounds have been recalculated deleting these compounds on the second test day
(11/28/01). DNPH-coated silica gel cartridge and SUMMA canister field blank samples for
carbonyl compounds and NMOC, respectively, were obtained only during the first test day
but did not show significant levels of either acetone or //-hexane. Methylene chloride was
also observed in much higher amounts in the stack gas on Test Day 2. Values for the PM2 5
mass emission factors were very consistent for the three test days and averaged 49.99 mg/kg
fuel.
59
-------
Table 15. Fine Particle, Carbonyl, and Nonmethane Organic Compound Emission
Factors from a Hogged Fuel Boiler at a Pulp and Paper Facility
Standard
Emission Factor 11/27/01 11/28/01 11/29/01 Mean Deviation
PM2 5 Mass Emission Factor (mg/kg fuel
51.95
49.82
48.19
49.99
1.89
burned)
Speciated Carbonyl Compounds Mass
3.46
0.90a
1.12
1.83
1.42
Emission Factor (mg/kg fuel burned)
Total (speciated + unspeciated) Carbonyl
3.46b
2.74a
1.99
2.73
0.74
Compounds Mass Emission Factor (mg/kg
fuel burned)
Speciated NMOC Mass Emission Factor
12.24
25.32a
22.97
20.18
6.89
(mg/kg fuel burned)
Total (speciated + unspeciated) NMOC
11.30
34.07a
13.28
19.55
12.61
Mass Emission Factor (mg/kg fuel burned)
a Suspected artifactual compounds (acetone and w-hexane) were deleted in the calculation of emission factors.
b On Test Day 1, the difference between residence chamber air and dilution air was slightly negative for unspeciated
carbonyl compounds, indicating more carbonyl compounds in the dilution air. The value of zero is used to determine
total carbonyl compounds.
Gas-Phase Carbonyl Compounds Profile
Analytical results in terms of the mass fractions of individual gas-phase carbonyl
emissions for each of the three test days are shown in Table 16. Mass fractions were
calculated by dividing the mass of an individual compound by the total mass of speciated
plus unspeciated carbonyl compounds. The suspected artifactual value for acetone on Test
Day 2 was omitted from the calculations. The "RC-DA" notation in the tabular column
headings indicates that amounts of individual carbonyl compounds found in the diluted stack
gas samples were background corrected by subtracting the amounts of the same carbonyl
compounds found in the dilution air. Tabulated "Total Unspeciated" carbonyl compounds
represent the total mass of compounds characterized as carbonyl compounds but not
specifically identified because no analytical standards were available. Amounts of the
unspeciated compounds are based on the analytical calibration factor for formaldehyde. The
unspeciated carbonyl compounds account for a significant portion of the reported total
carbonyl compound mass in each case. Uncertainties in the reported averages are the
standard deviation of the three replicate test results. Supporting data for carbonyls can be
found in Appendix E.
60
-------
Table 16. Gas-Phase Carbonyl Compounds Profile, Hogged Fuel Boiler (Carbonyl Compounds Collected in Diluted Stack
Gas Corrected for Carbonyl Compounds in Dilution Air)
Carbonyls
Carbonyls
Carbonyls
Field
RC-DA
Mass
RC-DA
Mass
RC-DA
Mass
Mean
Blank
11/27/01
Fraction
11/28/01
Fraction
11/29/01
Fraction
Mass
Compound
CAS No.
(US)
(US)
11/27/01
(US)
11/28/01
(UB)
11/29/01
Fraction
Uncertainty
formaldehyde
50-00-0
0.0360
0.2770
0.0567
0.4400
0.0924
0.2400
0.0848
0.0484
0.0412
acetaldehyde
75-07-0
0.0650
NDa
ND
0.9220
0.1937
0.4520
0.1597
0.0558
0.0901
acetone
67-64-1
0.1810
3.9360
0.8057
NDb
ND
0.6700
0.2367
0.6682
0.3818
propionaldehyde
123-38-6
ND
0.1260
0.0258
0.0690
0.0145
0.0510
0.0180
0.0148
0.0129
crotonaldehyde
4170-30-0
ND
ND
ND
ND
ND
ND
ND
ND
ND
butyr/isobutyraldehyde
123-72-8
0.0520
0.0830
0.0170
0.0680
0.0143
0.0710
0.0251
0.0142
0.0125
benzaldehyde
100-52-7
ND
0.0680
0.0139
0.0430
0.0090
0.0360
0.0127
0.0090
0.0075
isovaleraldehyde
590-86-3
ND
ND
ND
ND
ND
ND
ND
ND
ND
valeraldehyde
110-62-3
ND
0.0690
0.0141
0.0470
0.0099
0.0320
0.0113
0.0086
0.0073
o-tolualdehyde
529-20-4
ND
ND
ND
ND
ND
ND
ND
ND
ND
/M-toliialdchydc
620-23-5
ND
ND
ND
ND
ND
ND
ND
ND
ND
/Molualdchydc
104-87-0
ND
ND
ND
0.0330
0.0069
ND
ND
0.0001
0.0002
hexaldehyde
66-25-1
0.0180
0.1080
0.0221
0.0540
0.0113
0.0210
0.0074
0.0100
0.0111
2,5-dimethylbenzaldehyde
5779-94-2
ND
ND
ND
ND
ND
ND
ND
ND
ND
diacetyl
431-03-8
ND
0.0040
0.0008
ND
ND
ND
ND
0.0003
0.0005
methacrolein
78-85-3
ND
0.0020
0.0004
ND
ND
ND
ND
0.0001
0.0002
2-butanone
78-93-3
0.0160
0.0360
0.0074
0.0660
0.0139
0.0380
0.0134
0.0071
0.0064
glyoxal
107-22-2
0.0830
0.0060
0.0012
ND
ND
ND
ND
0.0004
0.0007
acetophenone
98-86-2
ND
0.0390
0.0080
0.0280
0.0059
0.0300
0.0106
0.0063
0.0054
methylglyoxal
78-98-8
0.0480
0.0500
0.0102
0.0620
0.0130
0.0030
0.0011
0.0039
0.0055
octanal
124-13-0
ND
0.0810
0.0166
0.0310
0.0065
ND
ND
0.0056
0.0095
nonanal
124-19-6
0.1250
ND
ND
0.1100
0.0231
0.0030
0.0011
0.0007
0.0006
continued
-------
Table 16. (Concluded)
Compound
CAS No.
Field
Blank
(U2)
Carbonyls
RC-DA
11/27/01
(U2)
Mass
Fraction
11/27/01
Carbonyls
RC-DA
11/28/01
(U2)
Mass
Fraction
11/28/01
Carbonyls
RC-DA
11/29/01
(U2)
Mass
Fraction
11/29/01
Mean
Mass
Fraction
Uncertainty
Sum, Speciated
0.6240
4.8850
1.0000
1.9730
0.4145
1.6970
0.5497
0.8421
0.2535
Sum, Unspeciated
0.8730
C
2.7865
0.5855
1.2745
0.4503
0.2368
0.3019
Total (speciated + unspeciated)
1.4970
4.8850
4.7595
2.9215
Standard
Mean
Deviation
Emission Factor, mg/kg fuel
(Speciated)
3.4555
0.8991
1.1230
1.83
1.42
Emission Factor, mg/kg fuel
(Total)
3.4555
2.7411
1.9920
2.73
0.74
a ND = not detected.
b Carbonyl values are skewed by an artifactual, high value for acetone on Day 2 of testing (November 28, 2001). This value has been deleted.
c The difference between RC and DA for unspeciated carbonyl compounds was slightly negative on the first test day.
On
to
-------
Gas-Phase Air Toxic Compounds—Whole Air Samples
The ERG concurrent analysis produces analytical results for both air toxics and
speciated/unspeciated NMOCs; these results are presented separately. Method detection
limits for the air toxics compounds are shown in Table 13, with values typically 1.65 |ig/m3
or less. Most of the values for the small number of air toxic compounds actually observed at
the hogged fuel boiler are at the lower end of the calibration curve for this analysis;
analytical results are shown in Table 17. Analytical results for an ambient canister taken at
the test location are included for reference. The concentrations observed in the ambient air
on Test Day 1 (the only day an ambient sample was taken) are higher than the
concentrations observed in the stack for nearly all of the air toxic compound emissions on
any test day. Methylene chloride was found at fairly high concentrations in the ambient air
sample taken on Test Day 1 and in the stack emissions on Test Day 2. Test Day 2 was also
the day the high concentrations of //-hexane and acetone, considered to be artifactual, were
detected in the stack gas samples. Supporting data for the air toxics are presented in
Appendix G.
Each of the Three Test Days (11/27/01 through 11/29/01)
RC-DA
RC-DA
RC-DA
Ambient
11/27/01
11/28/01
11/29/01
Compounds Detected
CAS No.
(Hg/m3)
(Hg/m3)
(Hg/m3)
(Hg/m3)
acetylene
74-86-2
0.39
0.31
0.30
0.48
propylene
115-07-1
NDa
0.30
0.08
ND
dichlorodifluoromethane
75-71-8
2.58
ND
ND
ND
chloromethane
74-87-3
1.80
ND
ND
ND
trichlorofluoromethane
75-69-4
1.40
ND
ND
ND
methylene chloride
75-09-2
485.21
61.59
NDb
8.67
trichlorotrifluoroethane
26253-64-8
0.60
ND
ND
ND
1,1,1 -trichloroethane
71-55-6
0.13
ND
ND
ND
benzene
71-43-2
2.24
9.35
10.94
9.59
carbon tetrachloride
56-23-5
0.61
ND
ND
ND
toluene
108-88-3
0.74
0.52
0.38
0.33
ethylbenzene
100-41-4
0.14
0.20
0.30
0.22
m-, /^-xylene
108-38-3/106-42-3
0.67
ND
ND
ND
o-xylene
95-47-6
0.16
ND
ND
ND
1,2,4-trimethylbenzene
95-63-6
0.20
0.23
ND
ND
a ND = not detected.
b Consistent with other gas-phase compounds, artifactual methylene chloride is deleted on Test Day 2.
63
-------
Gas-Phase Speciated Nonmethane Organic Compounds Profile
Analysis of whole air samples of dilution air and residence chamber air using ERG's
concurrent analysis generated analytical data for SNMOCs, as well as unspeciated NMOCs.
Analytical results are presented as mass fractions of total NMOC (speciated plus
unspeciated). Mass emission rates of total SNMOCs and total (speciated plus unspeciated)
NMOCs are also provided. Reported results include a correction for any amounts of NMOC
found in the air used to dilute the sampled stack gas. The "RC-DA" notation in the table
column headings indicates this correction, which was obtained by subtracting the amounts
found in the dilution air (DA) from the amounts found in the samples collected from the
sampler residence chamber (RC). Uncertainties associated with the averages in the tables are
standard deviations of the three test day results. Analytical results are reported in Table 18.
Supporting data for the NMOC analysis are shown in Appendix F.
PM2 5 Elemental/Organic Carbon, Major Inorganic Ion, and
Major Element Profile
Emissions of EC/OC, major inorganic ions, and major elements are reported in Table 19
as mass fraction of measured PM2 5 mass. Uncertainties in the reported mass fraction
averages are expressed as the standard deviation of the replicate results.
Particle Size Distribution Data
The ELPI system was operated in a "charged" mode on all three test days (11/27/01,
11/28/01, and 11/29/01) and collected data on particle size distribution in the range from
approximately 30 to 10,000 nm. The ELPI was run in continuous mode throughout all three
of the analytical runs. When the dilution sampling system was started and flow was initiated,
the ELPI operational mode was changed from "flush" mode to "sampling" mode. Stack
emissions were collected for the entire run of slightly more than eight hours.
The accumulated results of the individual runs are summarized in the following tables,
diagrams, and figures. Table 20 lists the collected mass in each of twelve stages for each test
day. The mean particle diameter of each stage is listed in increasing size order from 42.78 to
8328.12 nm. Figures 23, 24, and 25 show the particle counts versus size expressed as log
plots dN/dlog(Dp) and particle mass versus size expressed as log plots dM/dlog(Dp). A bar
graph of particle mass by channel is also shown in these figures.
64
-------
Table 18. Speciated and (Speciated + Unspeciated) NMOC Data for All Three Test Days, with Mass Fraction, Mean, and
Uncertainty
SNMOC
SNMOC
SNMOC
RC-DA
Mass
RC-DA
Mass
RC-DA
Mass
Mean
11/27/01
Fraction
11/28/01
Fraction
11/29/01
Fraction
Mass
Compound
CAS No.
(U2)
11/27/01
(US)
11/28/01
(US)
11/29/01
Fraction
Uncertainty
ethylene
74-85-1
0.0024
0.0137
0.0030
0.0057
0.0028
0.0139
0.0111
0.0047
acetylene
74-86-2
0.0016
0.0090
0.0016
0.0029
0.0023
0.0114
0.0078
0.0044
ethane
74-84-0
0.0016
0.0093
0.0023
0.0044
0.0023
0.0111
0.0082
0.0035
propylene
115-07-1
0.0026
0.0148
0.0025
0.0047
0.0020
0.0097
0.0097
0.0050
propane
74-98-6
0.0020
0.0115
0.0019
0.0035
0.0024
0.0118
0.0089
0.0047
propyne
74-99-7
NDa
ND
ND
ND
ND
ND
ND
ND
isobutane
75-28-5
0.0011
0.0060
0.0007
0.0013
0.0011
0.0053
0.0042
0.0025
isobutene/1 -butene
115-11-7/106-98-0
0.0037
0.0212
0.0024
0.0045
0.0025
0.0124
0.0127
0.0083
1,3-butadiene
106-99-0
ND
ND
ND
ND
ND
ND
ND
ND
//-butane
106-97-8
0.0020
0.0113
0.0021
0.0039
0.0026
0.0126
0.0093
0.0047
trans-2-butene
624-64-6
0.0012
0.0066
0.0009
0.0016
0.0011
0.0051
0.0045
0.0026
c/s-2-butene
590-18-1
0.0019
0.0106
0.0017
0.0031
0.0015
0.0074
0.0071
0.0037
3 -methyl-1 -butene
563-45-1
ND
ND
ND
ND
ND
ND
ND
ND
isopentane
78-78-4
0.0022
0.0124
ND
ND
0.0025
0.0122
0.0082
0.0071
1-pentene
109-67-1
0.0011
0.0060
0.0019
0.0035
0.0015
0.0074
0.0056
0.0020
2-methyl-1 -butene
563-46-2
ND
ND
ND
ND
ND
ND
ND
ND
//-pcntanc
109-66-0
0.0020
0.0110
0.0022
0.0041
0.0013
0.0065
0.0072
0.0035
isoprene
78-79-4
0.0008
0.0044
ND
ND
ND
ND
0.0015
0.0025
;ra/?.v-2-pcntcnc
646-04-8
0.0015
0.0084
0.0012
0.0023
0.0014
0.0069
0.0058
0.0032
c/.v-2-pcntcnc
627-20-3
0.0015
0.0084
0.0013
0.0025
0.0018
0.0088
0.0065
0.0035
2 -me thy 1-2 -butene
513-35-9
ND
ND
ND
ND
ND
ND
ND
ND
2,2-dimethylbutane
75-83-2
0.0035
0.0201
0.0036
0.0068
0.0076
0.0374
0.0214
0.0153
cyclopentene
142-29-0
ND
ND
ND
ND
ND
ND
ND
ND
4-methyl-1 -pentene
691-37-2
ND
ND
ND
ND
ND
ND
ND
ND
cyclopentane
287-92-3
0.0013
0.0073
0.0013
0.0025
0.0014
0.0067
0.0055
0.0026
continued
-------
Table 18. (continued)
Compound
CAS No.
SNMOC
RC-DA
11/27/01
(U2)
Mass
Fraction
11/27/01
2,3 -dimethylbutane
79-29-8
0.0026
0.0146
2-methylpentane
107-83-5
0.0414
0.2343
3-methylpentane
96-14-0
0.0020
0.0110
2-methyl-1 -pentene
763-29-1
ND
ND
1-hexene
592-41-6
0.0029
0.0165
2-ethyl-l-butene
760-21-4
ND
ND
«-hexane
110-54-3
0.0086
0.0488
;ra«.v-2-hc\cnc
4050-45-7
ND
ND
c/.v-2-hc.\cnc
7688-21-3
ND
ND
methylcyclopentane
96-37-7
0.0018
0.0104
2,4-dimethylpentane
108-08-7
0.0014
0.0079
benzene
71-43-2
0.0326
0.1844
cyclohexane
110-82-7
0.0021
0.0117
2-methylhexane
591-76-4
0.0033
0.0188
2,3 -dimethylpentane
565-59-3
0.0027
0.0152
3-methylhexane
589-34-4
0.0014
0.0079
1-heptene
592-76-7
0.0095
0.0538
2,2,4-trimethylpentane
540-84-1
0.0013
0.0073
rt-hcptanc
142-82-5
0.0014
0.0077
methylcyclohexane
108-87-2
0.0014
0.0079
2,2,3 -trimethylpentane
564-02-3
ND
ND
2,3,4-trimethylpentane
565-75-3
0.0015
0.0086
toluene
108-88-3
0.0025
0.0139
2-methylheptane
592-27-8
0.0010
0.0055
3-methylheptane
589-81-1
0.0011
0.0064
1-octene
111-66-0
ND
ND
SNMOC
SNMOC
RC-DA
Mass
RC-DA
Mass
Mean
11/28/01
Fraction
11/29/01
Fraction
Mass
(US)
11/28/01
(US)
11/29/01
Fraction
Uncertainty
0.0028
0.0052
0.0027
0.0132
0.0110
0.0051
0.0392
0.0731
0.0282
0.1380
0.1485
0.0811
0.0348
0.0650
0.0027
0.0132
0.0297
0.0306
ND
ND
ND
ND
ND
ND
0.0036
0.0067
0.0023
0.0114
0.0116
0.0049
ND
ND
ND
ND
ND
ND
1.4510b
ND
0.0191
0.0932
0.0473
0.0466
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.2064
0.3851
0.0038
0.0185
0.1380
0.2141
0.0020
0.0037
0.0023
0.0114
0.0077
0.0039
0.0416
0.0776
0.0356
0.1740
0.1453
0.0589
0.0019
0.0035
0.0024
0.0116
0.0089
0.0047
0.0008
0.0015
0.0032
0.0156
0.0120
0.0092
0.0033
0.0061
0.0035
0.0173
0.0129
0.0060
0.0012
0.0023
0.0016
0.0078
0.0060
0.0032
ND
ND
ND
ND
0.0179
0.0311
ND
ND
0.0232
0.1134
0.0402
0.0635
0.0020
0.0036
0.0010
0.0050
0.0054
0.0021
0.0018
0.0033
0.0014
0.0067
0.0060
0.0024
ND
ND
ND
ND
ND
ND
0.0012
0.0023
0.0012
0.0057
0.0055
0.0032
0.0018
0.0033
0.0018
0.0086
0.0086
0.0053
0.0012
0.0023
0.0010
0.0050
0.0042
0.0017
0.0016
0.0030
0.0013
0.0063
0.0052
0.0019
ND
ND
ND
ND
ND
ND
continued
-------
Table 18. (continued)
Compound
CAS No.
SNMOC
RC-DA
11/27/01
(U2)
Mass
Fraction
11/27/01
//-octane
111-65-9
0.0025
0.0139
ethylbenzene
100-41-4
0.0011
0.0062
///-xylene//?-xylene
108-38-3/106-42-3
0.0021
0.0117
styrene
100-42-5
ND
ND
o-xylene
95-47-6
0.0055
0.0309
1-nonene
124-11-8
ND
ND
n-nonane
111-84-2
0.0016
0.0090
isopropylbenzene
98-82-8
0.0009
0.0053
alpha-pinene
80-56-8
ND
ND
//-propylbcnzcnc
103-65-1
ND
ND
///-cthyltolucnc
620-14-4
0.0007
0.0038
/?-cthyltolucnc
622-96-8
0.0011
0.0064
1,3,5-trimethylbenzene
108-67-8
ND
ND
o-ethyltoluene
611-14-3
0.0015
0.0086
beta-pinene
127-91-3
ND
ND
1,2,4-trimethylbenzene
95-63-6
0.0009
0.0051
1-decene
872-05-9
ND
ND
n-decane
124-18-5
0.0016
0.0093
1,2,3 -trimethylbenzene
526-73-8
ND
ND
///-dicthylbcnzcnc
141-93-5
ND
ND
/j-dicthylbcnzcnc
105-05-5
ND
ND
1-undecene
821-95-4
ND
ND
//-undccanc
1120-21-4
0.0001
0.0007
1-dodecene
112-41-4
ND
ND
//-dodccanc
112-40-3
0.0009
0.0051
1-tridecene
2437-56-1
ND
ND
SNMOC
SNMOC
RC-DA
Mass
RC-DA
Mass
Mean
11/28/01
Fraction
11/29/01
Fraction
Mass
(US)
11/28/01
(US)
11/29/01
Fraction
Uncertainty
0.0025
0.0047
0.0024
0.0116
0.0101
0.0048
0.0011
0.0021
ND
ND
0.0028
0.0031
0.0029
0.0054
0.0012
0.0061
0.0077
0.0035
ND
ND
ND
ND
ND
ND
0.0060
0.0112
0.0059
0.0288
0.0236
0.0108
ND
ND
ND
ND
ND
ND
0.0027
0.0050
0.0021
0.0103
0.0081
0.0028
0.0018
0.0033
0.0013
0.0063
0.0050
0.0015
ND
ND
ND
ND
ND
ND
0.0009
0.0017
0.0014
0.0067
0.0028
0.0035
0.0009
0.0016
0.0009
0.0044
0.0032
0.0015
0.0009
0.0017
0.0010
0.0050
0.0044
0.0024
ND
ND
0.0009
0.0044
0.0015
0.0025
ND
ND
ND
ND
0.0029
0.0050
ND
ND
ND
ND
ND
ND
0.0010
0.0019
0.0008
0.0040
0.0037
0.0016
ND
ND
ND
ND
ND
ND
0.0016
0.0030
0.0011
0.0055
0.0059
0.0032
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.0013
0.0025
ND
ND
0.0010
0.0013
ND
ND
ND
ND
ND
ND
0.0001
0.0001
ND
ND
0.0017
0.0029
ND
ND
ND
ND
ND
ND
continued
-------
Table 18. (concluded)
Compound CAS No.
SNMOC
RC-DA
11/27/01
(U2)
Mass
Fraction
11/27/01
SNMOC
RC-DA
11/28/01
(US)
Mass
Fraction
11/28/01
SNMOC
RC-DA
11/29/01
(US)
Mass
Fraction
11/29/01
Mean
Mass
Fraction
Uncertainty
«-tridecane 629-50-5
ND
ND
ND
ND
ND
ND
ND
ND
Total Speciated
0.1768
1.0001
0.4015
0.7491
0.1955
0.9556
0.9016
0.1339
Total Unspeciated
0.0000
0.0000
0.1344
0.2508
0.0091
0.0445
0.0984
0.1338
Total (speciated + unspeciated)0
0.1768
0.5359
0.2046
Standard
Mean
Deviation
Speciated Emission Factor (mg/kg fuel burned)
12.2357
25.3226"
22.9732
20.18
6.98
Total (speciated + unspeciated) Emission Factor
11.3011
34.0711"
13.2803
19.55
12.61
(mg/kg fuel burned)
a ND = not detected.
b The high artifactual level of w-hexane has been deleted for this test day.
c Total NMOC with unknowns in |ig/m3 is an estimate based on propane only.
-------
Table 19. Fine Particle Chemical Composition of Emissions from a Hogged Fuel
Boiler at a Pulp and Paper Facility
11/27/01 11/28/01 11/29/01 Mean Uncertainty
PMj ; Composition (mass fraction)
Organic Carbon
0.0588
0.0628
0.0638
0.0618
0.0026
Elemental Carbon
0.0140
0.0172
0.0212
0.0175
0.0036
Elements (mass fraction)
Silicon
0.1778
0.1674
0.1710
0.1721
0.0053
Aluminum
0.1641
0.1513
0.1538
0.1564
0.0068
Potassium
0.0690
0.0612
0.0738
0.0680
0.0064
Iron
0.0450
0.0474
0.0448
0.0457
0.0014
Sulfur
0.0308
0.0250
0.0301
0.0286
0.0032
Calcium
0.0242
0.0224
0.0244
0.0237
0.0011
Titanium
0.0163
0.0158
0.0162
0.0161
0.0003
Chlorine
0.0091
0.0086
0.0106
0.0094
0.0010
Sodium
0.0085
0.0091
0.0100
0.0092
0.0008
Phosphorus
0.0055
0.0054
0.0062
0.0057
0.0004
Magnesium
0.0052
0.0049
0.0054
0.0052
0.0003
Zinc
0.0027
0.0032
0.0022
0.0027
0.0005
Vanadium
0.0011
0.0012
0.0010
0.0011
0.0001
Major Water-Soluble Ions (mass fraction)
Sulfate 0.0868 0.0833 0.0858 0.0853 0.0018
Potassium 0.0226 0.0201 0.0280 0.0236 0.0040
Chloride 0.0142 0.0158 0.0143 0.0148 0.0009
a ND = Not Detected
Foils from each impactor stage were recovered in the field for individual gravimetric
mass determinations. Foils were tared before shipment to the field, used for collection with
each sampling run, and individually recovered for determination of mass using a sensitive
electronic balance. After mass determination, the foils were also available for organic mass
determinations. Plots of particle counts versus size, particle mass versus size, and particle
mass versus stage are shown for each test day in Figures 23, 24, and 25. The mass of
particles collected appears to be a maximum at Stage 8 (1276.71 nm) for the first two test
days and at Stage 9 (2010.57 nm) on the third test day.
69
-------
Table 20. Particle
Size Distribution
Data
November 27, 2001
Stage3
1
2
3
4
5
6
7
8
9
10
11
12
Di,b nm
42.78
80.03
132.82
208.19
320.04
506.03
803.12
1276.71
2010.57
3157.47
5212.98
8328.12
dN/dlog(Dp),c 1/cm3
2.90xl04
7.38xl04
6.77xl04
2.05xl04
2.34xl03
6.91xl02
5.23 xlO2
0.000
1.25xl02
12.8
1.17
5.60x10"'
M,d mg/m3
0.0004
0.0047
0.0169
0.0181
0.0075
0.0099
0.0270
NDe
0.0967
0.0443
0.0196
0.0307
dM/dlog(Dp), mg/m3
VO
X
©
1.98xl0"2
8.30xl0"2
9.70 xlO"2
4.02 xlO"2
4.68 xlO"2
1.42 xlO"1
0.000
5.30x10"'
2.11x10"'
8.68 xlO"2
1.69x10"'
November 28, 2001
Stage
i
2
3
4
5
6
7
8
9
10
11
12
Di, nm
42.78
80.03
132.82
208.19
320.04
506.03
803.12
1276.71
2010.57
3157.47
5212.98
8328.12
dN/dlog(Dp), 1/cm3
1.98xl04
6.23 xlO4
6.78xl04
2.55xl04
4.75 xlO3
8.12xl02
5.14xl02
3.74xl02
1.48xl02
10.6
6.45x10"'
1.21
M, mg/m3
0.0002
0.0039
0.0170
0.0224
00153
0.0116
0.0265
0.0864
0.1149
0.0367
0.0108
0.0665
dM/dlog(Dp), mg/m3
8.10X10"4
1.67xl0"2
8.32xl0"2
1.20 xlO"1
8.16 xlO"2
5.51 xlO"2
1.39x10"'
4.07x10"'
6.30x10"'
1.75x10"'
4.79 xlO"2
3.67x10"'
November 29, 2001
Stage
1
2
3
4
5
6
7
8
9
10
11
12
Di, nm
42.78
80.03
132.82
208.19
320.04
506.03
803.12
1276.71
2010.57
3157.47
5212.98
8328.12
dN/dlog(Dp), 1/cm3
1.99xl04
5.48xl04
6.62xl04
2.74xl04
6.53 xlO3
1.09xl03
5.37xl02
3.65xl02
1.30xl02
8.75
1.04
1.60
M, mg/m3
0.0003
0.0035
0.0166
0.0241
0.0210
0.0155
0.0277
0.0843
0.1008
0.0302
0.0174
0.0879
dM/dlog(Dp), mg/m3
8.14X10"4
1.47xl0"2
8.12xl0"2
1.30x10"'
1.12 xlO"1
7.37 xlO-2
1.46 xlO"1
3.97x10"'
5.53x10"'
1.44x10"'
7.69 xlO"2
4.85x10"'
a Stage shows the individual stages of the 12-stage ELPI.
b Di is the midpoint value used in the distribution calculations; Di is the geometric mean of the boundaries of each stage.
c Particle counts are expressed as log dN/dlogDp, 1/cm3, or as log dM/dlogDp, mg/cm3, and plotted vs. particle diameter (Dp).
d M is the mass distribution, which gives the total mass of all particles in each size range. Mass distribution is calculated by multiplying the current distribution by the
conversion vector and by a vector formed from the masses of spheres having diameter equal to midpoint values (Di) of each stage.
e ND = not detected.
-------
Particle Counts vs Size
°E 80,000
_o
^ 60,000
Q.
Q 40,000
O)
.2 20,000
"O
10 100 1000 10000
Dp, nm
Particle Mass vs Size
co
E 0.6
10000
Dp, nm
Particle Mass
CO
E
0.12
0.10
0.08
« 0.06
re 0.04
0.02
0
10 11
Figure 23. Plots of Particle Counts vs. Size, Particle Mass vs.
Size, and Particle Mass per Stage for Test Day 1 (11/27/01).
71
-------
Particle Counts vs Size
°E 80,000
0
^ 60,000
Q.
0, 40,000
O)
.2 20,000
"O
1 «
10
I—p—I II III
Dp, nm
1111
10000
Particle Mass vs Size
CO
E 0.8 -
B)
£ 0.6 --
Q 0.4
O)
O 0.2
T3
T3
10
100
1000
10000
Dp, nm
Particle Mass
co
E
O)
E
to
V)
<0
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0
10 11 12
Stage
Figure 24. Plots of Particle Counts vs. Size, Particle Mass vs.
Size, arid Particle Mass per Stage for Test Day 2 (11/28/01).
72
-------
Particle Counts vs Size
CO
E 80,000
o
T-„ 60,000
Q.
Q, 40,000
o
£ 20,000
T3
10 100 1000 10000
Dp, nm
Particle Mass vs Size
co
E 0.6
O)
E
0.4
Q.
Q
§ 02
T3
i o
T3
10 100 1000 10000
Dp, nm
Particle Mass
CO
E
0.12
0.10
^ 0.08
« 0.06
(A
W 0.04
S
0.02
0
10 11 12
Figure 25. Plots of Particle Counts vs. Size, Particle Mass vs.
Size, and Particle Mass per Stage for Test Day 3 (11/28/01).
73
-------
PM2 5 Semivolatile Organic Compounds
Thermal evolution analysis by NIOSH Method 5040 of fine PM samples collected on
quartz filters revealed the presence of organic carbon averaging about 6 wt.% of the PM2 5
over the three test days. This result implies the presence of some organic compounds in the
particle-phase material. Fine PM samples collected on quartz filters and gas-phase
semivolatile organic compounds collected on PUF plugs and organic denuders were
extracted from the collection media with a solvent system consisting of
benzene:hexane:isopropanol (for filter samples) or methylene chloride:hexane:acetone (for
PUFs and denuders) followed by GC/MS analysis of the extracts. This analysis approach
revealed the presence of only trace quantities of a few organic species, none of which were
above the quantitation limits for the analysis method employed. Quantitation limits for the
semivolatile species were taken to be the lowest concentrations of standards used to
establish the GC/MS analysis calibration curves. The concentration ranges of these
standards are shown in Appendix K.
Table 21 lists those organic compounds that were positively identified above detection
limits and above the amounts found in the cleaned dilution air in the fine PM, all of which
are relatively high molecular weight hydrocarbons. These results were obtained by GC/MS
analysis of the solvent extract of composited quartz filters from Sampling Ports #R4 and
#R8 on the dilution sampler residence chamber for all three test days. These filters were not
fronted by XAD-coated annular denuders. No quantifiable gas-phase organic compounds
were found on the denuders on Port #R10 or on the PUF plugs following the quartz filters
on any of the test days. Compositing the quartz filters for all three test days was necessary in
order to achieve even the semi-quantitative results reported. Although exact quantitation of
the individual trace compounds was not possible, on a relative scale, the straight-chain n-
alkanes marked with an asterisk (*) in Table 21 were present in the largest amounts,
generally 30 to 50 times higher than the rest.
Table 21. Organic Compounds Positively Identified in the PM25 Emissions from the
Hogged Fuel Boiler
«-Docosane
«-Tricosane*
«-Triacontane
/7-Tctracosanc
/'so-Tetracosane
/7-Pcntacosanc*
/.vo-Pcntacosanc
an le iso -Pen taco san c
/7-Hcxacosanc*
/w-Hcxacosanc
an le iso - He xaco san c
/7-Hcptacosanc*
zso-Heptacosane
an te iso - He ptaco san c
/7-Octacosanc*
z'so-Octacosane
anteiso-Octacosane
/7-Nonacosanc*
«-Hentriacontane
74
-------
Measurement of 02 and C02
Observed values for each test day are shown in Figures 24 through 26. Average
concentrations of 02 and C02 for each test day are shown below:
• 11/27/01: 02 = 7.4%V; C02 = 11,3%V;
• 11/28/01: 02 = 6.8%V; C02 = 11,9%V; and
• 11/29/01: 02 = 5.9%V; C02 = 13.6%V.
75
-------
14 0
Op Avg - 7.4%V
C02 Avg = 11,3%V
LT>
m
m
Ln
Ln
Ln
Ln
m
Ln
Ln
Ln
Ln
Ln
Ln
Ln
Ln
Ln
CO
o
CO
o
CO
o
CO
o
CO
o
CO
o
CO
o
CO
o
CO
oci
d
d
o
d
c\i
-------
02 Avg - 6 8%V
C02 Avg = 11 9%V
00
00
CO
00
CO
CO
oo
CO
00
00
CO
CO
00
CO
CO
00
CO
1—
¦*—
¦*-
•*—
•*-
T-
GO
00
Oj
Oj
o
o
T—
T—
c\i
cvi
CO
CO
"St
LO
LO
co
T—
-1—
-1—
-1—
-i—
-i—
T—
-I—
1—
T—
1—
"1—
T—
Time
Figure 27. 02 and COz Concentrations for Hogged Fuel Boiler No. 2 on Test Day 2 (11/28/01).
-------
14.0
12.0
10.0
>
8.0
O
6.0
4.0
Op Avg = 5.9%V
COs Avg = 13.6%V
2.0
0.0
o
o
o
O
o
o
o
o
o
o
o
o
o
o
o
o
o
o
s?
o
CO
o
CO
o
CO
o
CO
o
CO
o
CO
o
CO
o
CO
CD
C7)
ay
o
o
^
c\j
C\j
CO
CO
LO
LO
(6
Time
Figure 28. Oz and C02 Concentrations for Hogged Fuel Boiler No. 2 on Test Day 3 (11/29/01).
-------
Quality Assurance/Quality Control
The sampling and analysis procedures performed for this study adhered to approved
EPA Quality Assurance Project Plans (QAPPs) QTRAK No. 9905110 and QTRAK No.
9900211, respectively. MOPs (EPA) and SOPs (ERG), which describe the quality control
(QC) checks performed for each procedure, are listed in Appendix L. QAPPs, MOPs, SOPs,
and files of raw data and QC supporting data for the project were archived for future
reference. Summaries of the QC measures implemented for the field sampling activities and
for the various analytical methods are presented in Tables 22 through 29.
Field Sampling
In field sampling with the dilution sampling system, the following QC procedures were
implemented:
A leak check of the dilution sampling system with all sample collection arrays was
performed before field testing was initiated;
Pitot tubes and meter boxes were calibrated;
Analytical balance(s) were calibrated;
Flow control collection devices for the canisters were calibrated using a primary
flow standard;
Multipart forms recording field conditions and observations were used for canisters
and carbonyl samples; and
Strict chain of custody documentation for all field samples was maintained.
Field sampling equipment QC requirements that were met in the course of preparing for
the field test and execution of testing activities are summarized in Table 22.
79
-------
Table 22. Field Sampling Equipment Quality Control Measures10
Acceptance
Criteria
Equipment
Effect
Criteria
Achieved?
Orifice meters (volumetric gas
Ensures the accuracy of flow
±1%
Yes
flow calibration)
measurements for sample
collection
Venturi meters (volumetric gas
Ensures the accuracy of flow
±l%of
Yes
flow calibration)
measurements for sample
reading
collection
Flow transmitter (Heise gauge
Ensures the accuracy of flow
±0.5% of
Yes
with differential pressure)
measurements for sample
range
collection
Analytical balances
Ensures control of bias for all
Calibrated
Yes
project weighing
with Class S
weights
Thermocouples
Ensures sampler temperature
±1.5 °C
Yes
control
Relative humidity probes
Ensures the accuracy of moisture
±2% relative
Yes
measurements in the residence
humidity
chamber
Sampling equipment leak
Ensures accurate measurement of
1%
Yes
check and calibration (before
sample volume
each sampling run)
Sampling equipment field
Ensures absence of
<5.0% of
Yes
blanks
contamination in sampling
sample
svstem
values
Strict chain of custody procedures were followed in collecting and transporting samples
and in sampling media to and from the field sampling location. Sample substrates (filters,
denuders, PUF modules, DNPH cartridges) were prepared in advance in accordance with the
numbers and types of samples designated in the sampling matrix of the approved field test
plan. Clean SUMMA polished collection canisters and the DNPH-coated sampling
cartridges used to collect carbonyl compounds were prepared and supplied by ERG. The
PUF, XAD-4-coated denuders and PM2 5 sampling substrates were prepared and supplied by
EPA. Chain of custody forms were initiated when the sampling media were prepared. Each
sample substrate was assigned a unique identification number by the laboratory supplying
the substrates. Copies of the chain of custody forms are included in Appendix B.
Sample identification numbers include a code to track:
Source type;
80
-------
Test date(s);
Sampler type;
Substrate type;
Sampler chamber (i.e., dilution chamber or residence chamber);
Sampler port;
Lane/leg;
Position; and
• Holder number.
For samples to be analyzed in the EPA laboratories, whole sample collection arrays were
assembled by EPA, assigned a unique tracking number, and used for sample collection.
Sample collection arrays were recovered in the field as a complete unit and transferred to the
EPA laboratory for disassembly and analysis.
After collection, samples were transported to the analysis laboratories by ERG with
careful documentation of sample collection and chain of custody records for the samples
being transported. Samples were stored in a secure area until they were transported to the
laboratories performing the analysis.
Carbonyl Compound Analysis
QC criteria for the carbonyl analysis performed by ERG are shown in Table 23.
Supporting calibration and QC data are a part of the project file at ERG.
Table 23. Carbonyl Analysis: Quality Control Criteria
Quality Acceptance Corrective Criteria
Parameter Control Check Frequency Criteria Action Achieved?
HPLC Column
Analyze second
At setup and 1
Resolution between
Eliminate
Efficiency
source QC
per sample
acetone and
dead volume,
sample (SSQC)
batch
propionaldehyde
backflush, or
>1.0
replace
Column efficiency
column;
>500 plates
repeat
analysis
Linearity
Analyze
At setup or
Correlation
Check
Check
5-point
when
coefficient >0.999,
integration,
calibration
calibration
relative error for
reintegrate or
curve and
check does not
each level against
recalibrate
SSQC in
meet
calibration curve
triplicate
acceptance
±20% or less
criteria
Relative Error
(continued)
81
-------
Table 23. (continued)
Parameter
Quality
Control Check
Frequency
Acceptance
Criteria
Corrective Criteria
Action Achieved?
Linearity
Check
(continued)
Retention
Time
Multipoint
Calibration:
0.01 |ig/mL
0.02 |ig/mL
0.05 |ig/mL
0.10 |ig/mL
0.30 |ig/mL
0.50 |ig/mL
per compo-
nent
Calibration
Check
Calibration
Accuracy
Analyze
calibration
midpoint
Analyze each
point of trace-
able standards
SSQC
Once per 10
samples
Analyze
standard at 0.15
|lg/mL from a
second source
Minimum of
every 6
months or
when the
analytical
column is
replaced or
when detector
lamp is
replaced
Once per 12
hours
Once after
calibration in
triplicate
Intercept acceptance
should be < 10,000
area counts/
compound;
correlates to 0.06
mg/mL
Acetaldehyde,
benzaldehyde,
hexaldehyde within
retention time
window established
by determining 3 c
or ±2% of the mean
calibration and
midpoint standards,
whichever is greater
r <0.9999
85-115% recovery
85-115% recovery
Check
integration,
reintegrate or
recalibrate
Check system
for plug,
regulate
column
temperature,
check
gradient and
solvents
Check instru-
ment for
malfunction;
reinspect
standards. If
calibration
still fails,
reprepare
standards and
recalibrate.
Check
integration,
recalibrate or
reprepare
standard,
reanalyze
samples not
bracketed by
acceptable
standard
Check
integration;
recalibrate or
reprepare
standard,
reanalyze
samples not
bracketed by
acceptable
standard
Yes
Yes
Yes
Yes
Yes
(continued)
82
-------
Table 23. (concluded)
Quality
Acceptance
Corrective
Criteria
Parameter
Control Check
Frequency
Criteria
Action
Achieved?
System Blank
Analyze
Bracket
Measured
Locate
Yes
acetonitrile
sample batch,
1 at beginning
and 1 at end
concentration
<5 x MDL
contamina-
tion and
document
levels of
contamina-
tion in file
Duplicate
Duplicate
As collected
±20% difference
Check
Yes
Analyses
samples
integration;
check
instrument
function; re-
analyze
duplicate
samples
Replicate
Replicate
Duplicate
< 10% relative
Check
Yes
Analyses
injections
samples only
percent difference
for concentrations
greater than 1.0
|lg/mL
integration,
check
instrument
function, re-
analyze
duplicate
samples
Method
Analyze
One MS/MSD
80-120% recovery
Check
Yes
Spike/Method
MS/MSD
per 20 samples
for all compounds
calibration,
Spike
check
Duplicate
extraction
(MS/MSD)
procedures
Concurrent Air Toxics/Speciated Nonmethane
Organic Compound (SNMOC) Analysis
The analytical system performing the concurrent analysis is calibrated monthly and
blanked daily prior to sample analysis. A QC standard is analyzed daily prior to sample
analysis to ensure the validity of the current monthly response factor. Following the daily
QC standard analysis and prior to the sample analysis, cleaned, dried air from the canister
cleaning system is humidified and then analyzed to determine the level of organic
compounds present in the analytical system. Upon achieving acceptable system blank
results—less than or equal to 20 ppbC—sample analysis begins. Ten percent of the total
number of samples received are analyzed in replicate to determine the precision of analysis
for the program. After the chromatography has been reviewed, the sample canister is
returned to the canister-cleaning laboratory to be prepared for subsequent sample collection
83
-------
episodes or sent to another laboratory for further analysis. QC procedures for the Air Toxics
and SNMOC analyses are summarized in Table 24.
Table 24. Quality Control Procedures for the Concurrent Analysis for Air Toxics and
SNMOCs
Criteria
Quality Control
Acceptance
Corrective
Achieved
Check
Frequency
Criteria
Action
?
Air Toxics Analysis
Bromofluorobenzene
Daily prior to
Evaluation criteria
Retune mass
Yes
Instrument Tune
calibration check
in data system
spectrometer;
Check
software;
clean ion
consistent with
source and
Method TO-15
quadrupoles
Five-point Calibration
Following any
RSD of response
Repeat
Yes
Bracketing the
major change,
factors <30%
individual
Expected Sample
repair, or
relative retention
sample
Concentration
maintenance if
times (RRTs) for
analysis; repeat
(0.25-15 ppbv)
daily QC check is
target peaks ±0.06
linearity check;
not acceptable.
units from mean
prepare new
Calibration is valid
RRT
calibration
for six weeks if
standards and
calibration check
repeat analysis
criteria are met.
Calibration Check
Daily
Response factor
Repeat
Yes
Using Midpoint of
<30% bias from
calibration
Calibration Range
calibration curve
check; repeat
average response
calibration
factor
curve
System Blank
Daily following
0.2 ppbv/analyte or
Repeat analysis
Yes
tune check and
MDL, whichever is
with new
calibration check
greater
blank; check
Internal Standard
system for
(IS) area response
leaks,
±40% and retention
contamination;
time ±0.33 min of
reanalyze
most recent
blank.
calibration check
Laboratory Control
Daily
Recovery limits
Repeat
Yes
Standard (LCS)
70-130%
analysis; repeat
Internal Standard
calibration
Retention Time
curve.
±0.33 min of most
recent calibration
continued
84
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Table 24. (concluded)
Quality Control
Check
Frequency
Criteria
Acceptance Corrective Achieved
Criteria Action ?
Replicate Analysis
Samples
SNMOC Analysis
System Blank
Analysis
Multiple Point
Calibration
(Minimum 5);
Propane Bracketing
the Expected Sample
Concentration Range
(4-100 ppbC)
Calibration Check:
Midpoint of
Calibration Curve
Spanning the Carbon
Range (C2-C10)
Replicate analysis
All duplicate field
samples
All samples
Daily, following
calibration check
Prior to analysis
and monthly
Daily
All duplicate field
samples
<30% RPD for
compounds
>5 x MDL
IS RT ±0.33 min of
most recent
calibration
20 ppbC total
Correlation
coefficient
(r2) >0.995
Response for
selected
hydrocarbons
spanning the
carbon range
within ±30%
difference of
calibration curve
slope
Total NMOC
within ±30% RSD
Repeat sample
analysis
Repeat
analysis; check
system for
leaks; clean
system with
wet air
Repeat
individual
sample
analysis; repeat
linearity check;
prepare new
calibration
standards and
repeat
Repeat
calibration
check; repeat
calibration
curve.
Repeat sample
analysis
Yes
Repeat analysis Yes
Yes
Yes
Yes
Yes
PM Mass Measurements, Elemental Analysis, Water-Soluble Ion
Analysis, Organic/Elemental Carbon, and GC/MS Analysis
QC criteria for analyses of PM25 mass and PM2 5 elements, ions, and speciated organics
are summarized in Tables 25 through 29; supporting data are included in the project file in
the EPA laboratory.
85
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Table 25. PM Mass Measurements: Quality Control Criteria
Parameter
Quality Control
Check
Frequency
Acceptance
Criteria
Corrective
Action
Criteria
Acheived
?
Deposition on
Analyze
Bracket sample
Mass within
Adjust mass
Yes
Filter during
laboratory filter
batch, 1 at
±15 mg of
for deposition
Conditioning
blank
beginning and
previous weight
1 at end
Laboratory
Analyze
Bracket sample
Mass within
Adjust mass
Yes
Stability
laboratory control
batch, 1 at
±15 mg of
to account for
filter
beginning and
previous weight
laboratory
1 at end
difference
Balance
Analyze standard
Bracket sample
Mass within
Perform
Yes
Stability
weights
batch, 1 at
±3 mg of
internal
beginning and
previous weight
calibration of
1 at end
balance;
perform
external
calibration of
balance
Table 26. Elemental Analysis: Quality Control Criteria
Quality Control Acceptance Corrective Criteria
Parameter Check Frequency Criteria Action Achieved?
Performance Analyze monitor Once per <2% change in Recalibrate Yes
Evaluation sample month each element
Check from previous
measurement
86
-------
Table 27. Water-Soluble Ion Analysis: Quality Control Criteria
Parameter
Quality Control
Check
Frequency
Acceptance
Criteria
Corrective
Action
Criteria
Achieved
?
Linearity
Check
Analyze 4-point
calibration curve
At setup or
when
calibration
check does
not meet
acceptance
criteria
Correlation
coefficient
r2 >0.999
Recalibrate
Yes
System Dead
Volume
Analyze water
Bracket
sample batch,
1 at beginning
and 1 at end
Within 5% of
previous analysis
Check
system
temperature,
eluent, and
columns
Yes
Retention
Time
Analyze standard
At setup
Each ion within
±5% of standard
retention time
Check
system
temperature
and eluent
Yes
Calibration
Check
Analyze 1 standard
Once every
4-10 samples
85-115%
recovery
Recalibrate
or reprepare
standard, re-
analyze
sample not
bracketed
by
acceptable
standard
Yes
System Blank
Analyze HPLC
grade water
Bracket
sample batch,
1 at beginning
and 1 at end
No quantifiable
ions
Reanalyze
Yes
Replicate
Analyses
Replicate
injections
Each sample
< 10% RPD for
concentrations
greater than
1.0 mg/L
Check
instrument
function, re-
analyze
samples
Yes
87
-------
Table 28. Quality Control Procedures for Organic/Elemental Carbon Analysis of PM25
Quality Control
Check
Frequency
Acceptance
Criteria
Corrective
Action
Criteria
Achieved?
Instrument Gas
Flows
Amount of
Internal Standard
(CH4/He) in
Calibration Gas
Loop
Instrument Blank
3-Point
Calibration with
Standard Sucrose
Solutions
Bracketing
Concentration
Range
1-Point
Calibration with
Standard Sucrose
Solution
Once at start of
each new batch of
source samples
every six months
Whenever
methane tank is
changed
Obtain best
polynomial fit to 6
data points for each
gas
Determine volume
of calibration gas
loop
Start of each run <0.2 |ig C/cm2
Start of new set of
samples
Within 5% of
previous calibration
Start of each
analysis
Within 5% of
previous calibration
Re-enter data into
instrument
operation software
Re-enter new
calibration gas
loop volume in
instrument
operation software
Repeat oven bake-
out
Repeat calibration
Repeat calibration
Yes
Yes
Yes
Yes
Yes
88
-------
Table 29. Quality Control Procedures for Gas Chromatography-Mass Spectrometry
Analysis of Semivolatile Organic Compounds
Quality Control
Check
Frequency
Acceptance
Criteria
Corrective
Action
Criteria
Achieved
?
Mass Spectrometer
Daily prior to
Mass assignments
Retune mass
Yes
Instrument Tune
calibration check
m/z = 69, 219, 502
spectrometer;
Check
(± 0.2)
clean ion
Peak widths =
source
0.59-0.65
Relative mass
abundances = 100%
(69); >30% (219);
> 1% (502).
Five-Point Calibration
Following
Correlation
Check
Yes
Bracketing the
maintenance or
coefficient of either
integration,
Expected
repair of either gas
quadratic or linear
reintegrate or
Concentration Range
chromatograph or
regression >0.999
recalibrate
mass spectrometer
or when daily
quality control
check is not
acceptable
Calibration Check
Daily
Compounds in a
Repeat
Yes
Using Midpoint of
representative
analysis;
Calibration Range
organic compound
repeat
suite >80% are
calibration
±15% of
curve
individually
certified values.
Values >20% are
not accepted.
System Blank
As needed after
Potential analytes
Repeat
Yes
system maintenance
less than or equal to
analysis;
or repair
detection limit
check system
values
integrity.
Reanalyze
blank
Retention Time Check
Daily
Verify that select
Check inlet
Yes
compounds are
and column
within ±2% of
flows and the
established retention
various
time window
GC/MS
temperature
zones
89
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90
-------
References
1. U. S. Government Printing Office, EPA Method 5, Determination of Particulate Matter
Emissions from Stationary Sources, in Code of Federal Regulations, Title 40, Part 60,
Appendix A, pp. 371-443, Washington, DC, 1989.
2. U.S. EPA Technology Transfer Network, Emissions Measurement Center,
Determination of Condensible Particulate Emissions from Stationary Sources,
http://www.epa.gov/ttn/emc/promgate/m-202.pdf (Accessed February 2005)
3. U.S. Government Printing Office, EPA Method 1, Sample and Velocity Traverses for
Stationary Sources, in Code of Federal Regulations, Title 40, Part 60, Appendix A, pp.
181-206, Washington, DC, 1989.
4. U.S. Government Printing Office, EPA Method 2, Velocity -S-Type Pitot, in Code of
Federal Regulations, Title 40, Part 60, Appendix A, pp. 214-253, Washington, DC,
1989.
5. U.S. Government Printing Office, EPA Method 4, Moisture Content, in Code of Federal
Regulations, Title 40, Part 60, Appendix A, pp. 347-371, Washington, DC, 1989.
6. Hildemann, L.M., G.R. Cass, and G. R. Markowski. A Dilution Stack Sampler for
Collection of Organic Aerosol Emissions: Design, Characterization and Field Test.
Aerosol Science and Technology 10:193-204, 1989.
7. NIOSH Method 5040, Elemental Carbon (Diesel Particulate). NIOSH Manual of
Analytical Methods (NMAM), 4th Edition, Department of Health and Human Services
(NIOSH) Publication 94-113, August, 1994.
8. U. S. EPA. Technical Assistance Document for Sampling and Analysis of Ozone
Precursors, U.S. Environmental Protection Agency, National Exposure Research
Laboratory, Office of Research and Development, Research Triangle Park, NC, EPA-
600/R-98-161, September 1998. NoNTIS number available. Document is available
from Ambient Monitoring Technology Information Center (AMTIC) Bulletin Board.
(http://www.epa.gov/ttnamtil/files/ambient/pams/newtad.pdO
9. Federal Register. Volume 49, Number 209, Appendix B to Part 136—Definition and
Procedure for the Determination of the Method Detection Limit—Revision 1.11, pp.
198-199, October 26, 1984.
10. U.S. EPA. Compendium of Methods for the Determination of Toxic Organic Compounds
in Ambient Air. EPA/625/R-96/010b (NTIS PB99-172355). Center for Environmental
Research Information, National Risk Management Research Laboratory, Office of
91
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Research and Development, U.S. Environmental Protection Agency, Cincinnati, OH,
January 1999.
11. U.S. EPA. Quality Assurance Project Plan. Source Sampling of Fine Particulate Matter.
N. Dean Smith. QTRAK No. 99051. National Risk Management Research Laboratory,
Air Pollution Prevention and Control Division, U.S. Environmental Protection Agency,
Research Triangle Park, NC.
12. U.S. EPA. Quality Assurance Project Plan. Chemical Analysis of Fine Particulate
Matter. N. Dean Smith. QTRAK No. 99002/III, Revision 4, August 2001. National Risk
Management Research Laboratory, Air Pollution Prevention and Control Division, U.S.
Environmental Protection Agency, Research Triangle Park, NC.
92
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
EPA-600/R-03/100a
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Source Sampling Fine Particulate Matter: A Kraft Process
Recovery Boiler at a Pulp and Paper Facility: Volume 1,
Rpnnrt
5. REPORT DATE
November 2003
6. PERFORMING ORGANIZATION CODE
7. AUTHORS
Joan T. Bursey and Dave-Paul Dayton
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Eastern Research Group, Inc.
1600 Perimeter Park Drive
Morrisville, NC 27560
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
Contract No. 68-D7-001
12. SPONSORING AGENCY NAME AND ADDRESS
U. S. EPA, Office of Research and Development
Air Pollution Prevention and Control Division
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final: 02/05/01 - 05/30/03
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES
The EPA Project Officer is N. Dean Smith, mail drop E343-02, phone (919) 541-2708
16. ABSTRACT
The report provides a profile of the chemical composition of particulate matter (PM) with aerodynamic
diameter 2.5 |_im or less (PM25) emitted from an auxiliary boiler at a pulp and paper facility using the Kraft
pulping process. The auxiliary boiler was fired with a mixture of wood bark (hogged wood waste) and
bituminous coal and was rated to generate a maximum of 889 Mbtu/hour. It was equipped with a control
system that included a multicyclone-electroscrubber system installed on the flue gas duct and bag filters
installed on the vents of the coal bins, scrubber ash silo, and boiler ash silo. The data obtained during this
research will assist States in determining the major sources of PM2 5 so they can devise and institute a
control strategy to attain the ambient concentrations set by the National Ambient Air Quality Standard for
PM2 5 that was promulgated in July 1977 by the U.S. EPA. Along with the PM2 5 emission profile, data are
also provided for gas-phase emissions of several organic compounds. Data are provided in a format
suitable to be included in the EPA source profile database, SPECIATE.
17. KEYWORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Paper Industry
Wood Pulp
Fine Particulate Matter
Chemical Composition
Organic Compounds
Volatility
Pollution Control
Stationary Sources
13B
11L
14G
07D
07C
20M
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
104
20. SECURITY CLASS (This Page)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION IS OBSOLETE
forms/admin/techrpt.frm 7/8/99 pad
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