£EPA
United States EPA-600/R-03/099a
Environmental Protection
Agency November 2003
Source Sampling Fine
Particulate Matter: A
Kraft Process Recovery
Boiler at a Pulp and
Paper Facility: Volume 1,
Report
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EPA-600/R-03/099a
November 2003
Source Sampling Fine Particulate
Matter: A Kraft Process Recovery
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 such a profile for a Recovery Boiler at a pulp and paper facility.
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 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 Recovery Boiler at a Pulp and Paper Facility 2
Report Organization 3
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 22
Measurement of 02, C02, and CO Concentrations for Calculating Stack
Parameters 22
Stationary Gas Distribution (as Percent Volume) 23
Dry Molecular Weight of Flue Gas 23
Wet Molecular Weight of Flue Gas 23
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 25
Setup of the Dilution Sampling System 26
Pre-Test Leak Check 29
Orifice Flow Check 30
Determination of Test Duration 31
Canister/Veriflow Blanks 31
Determination of Flow Rates 31
Sample Collection Arrays 32
Dilution Chamber Sample Collection Arrays 32
Residence Chamber Sample Collection Arrays 34
Use of the ELPI Particle Size Distribution Analyzer 35
Measurement of 02 and C02 Process Concentrations 36
Operation of the Dilution Sampling System with Sample Collection Arrays 36
Dilution System Sample Collection Arrays: Sample Recovery 46
Laboratory Experimental Methodology 47
PM2 5 Mass 47
Elemental Analysis 48
Water-Soluble Inorganic Ions 48
Elemental Carbon/Organic Carbon 48
Organic Compounds 49
Carbonyl Compounds 50
Canister Analyses: Air Toxics and Speciated Nonmethane Organic
Compounds 51
Particle Size Distribution Data 52
Results and Discussion 53
Calculated Emission Factors for PM Mass, Carbonyls, and Nonmethane Organic
Compounds 53
Gas-Phase Carbonyl Compounds 54
Gas-Phase Air Toxic Compounds 54
Gas-Phase Speciated Nonmethane Organic Compounds 57
EC/OC, Major Inorganic Ions, and Major Elements 62
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Table of Contents (continued)
Section Page
Particle Size Distribution Data 63
Semivolatile Organic Compounds 63
Process 02 and C02 Concentrations 68
Quality Assurance/Quality Control 73
Field Sampling 73
Carbonyl Compound Analysis 75
Concurrent Air Toxics/Speciated Nonmethane Organic Compound (SNMOC)
Analysis 77
PM Mass Measurements, Elemental Analysis, Water-Soluble Ion Analysis,
Organic/Elemental Carbon, and GC/MS Analysis 79
References 85
Volume 2, Appendices
A Table of Unit Conversions A-l
B Recovery Boiler No. 5, Test 1, Chain of Custody Documentation B-l
C Sample Log with Sample IDs C-l
D List of ERG SOPs and EPA MOPs by Title D-l
E Method Detection Limits for Carbonyl Compounds, Air Toxics,
and Speciated NMOCs E-l
F Example Calculations F-l
G PM Emission Factor Calculations G-l
H Data Tables for Individual PM25 Mass Measurements H-l
I Supporting Data for Carbonyl Analysis 1-1
J Supporting Data for Air Toxics Analysis J-l
K Supporting Data for Speciated and Unspeciated Nonmethane Organic
Compounds K-l
L Data Tables for Individual PM25 EC/OC Samples L-l
M Data Tables for Individual PM2 5 Elemental Samples M-l
N Data Tables for Individual PM2 5 Inorganic Ion Samples N-l
O Supporting Calibration and Data Tables for Individual Semivolatile
Organic Compounds 0-1
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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 Black Liquor 16
3 Recovery Boiler No. 5 Fuel Use During the Test Period 17
4 Process Data for Testing Days: Black Liquor, Black Liquor Solids, and #2 Oil ... 18
5 EPA Method 1 Traverse Point Locations for Recovery Boiler No. 5 Exhaust
(a Rectangular Duct) 20
6 Average Flue Gas Velocity for Each Traverse Point (Average Flue Gas Velocity) . 22
7 Moisture Recovery for Method 4 (Measured on 10/29/01) 24
8 Blank Values for Veriflows and Canisters 31
9 Run Time Summary Information, Test Run #1 (10/30/01) 37
10 Run Time Summary Information, Test Run #2 (10/31/01) 38
11 Run Time Summary Information, Test Run #3 (11/01/01) 40
12 Fine Particle, Carbonyl, and Nonmethane Organic Compound Emission Factors
from a Recovery Boiler at a Pulp and Paper Facility 53
13 Carbonyl Compounds, Recovery Boiler: Carbonyl Compounds Collected in
Dilution Air Subtracted from Carbonyl Compounds Collected in Residence
Chamber, with Mass Fraction of Each Analyte, Mean, and Uncertainty 55
14 Summarized Analytical Results for Air Toxics Compounds Observed on Each
of the Three Test Days (10/30/01 through 11/1/01) 57
15 Speciated and (Speciated + Unspeciated) NMOC Data for All Three Test Days,
with Mass Fraction, Mean, and Uncertainty 58
16 Fine Particle Chemical Composition of Emissions from a Recovery Boiler
at a Pulp and Paper Facility 62
17 Particle Size Distribution Data 64
18 Field Sampling Equipment Quality Control Measures 74
19 Carbonyl Analysis: Quality Control Criteria 75
20 Quality Control Procedures for the Concurrent Analysis for Air Toxics
and SNMOCs 78
21 PM Mass Measurements: Quality Control Criteria 80
22 Elemental Analysis: Quality Control Criteria 80
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List of Tables (continued)
Table
23 Water-Soluble Ion Analysis: Quality Control Criteria
24 Quality Control Procedures for Organic/Elemental Carbon Analysis of PM25
25 Quality Control Procedures for Gas Chromatography-Mass Spectrometry
Analysis of Semivolatile Organic Compounds
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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 Schematic Diagram of Layout of Recovery Boiler No. 5 Sampling Site 15
4 Recovery Boiler Sampling Port Location 15
5 Dilution Sampling System Positioned at the Sampling Location During Operation. 27
6 Dilution Sampling Probe Installed in 6-in. ID Flanged Port 27
7 Dilution System Control Module Positioned at the Sampling Location 28
8 Dilution System with Sample Collection Arrays and Instruments Attached 28
9 Dilution System Sampling Module with All Sample Collection Arrays and
Instruments Attached. White Filter Holders Are Readily Visible 29
10 Recovery Area for Dilution Sampling System Sample Collection Arrays 30
11 Sample Collection Arrays Used with Recovery Boiler No. 5 33
12 Blower Flow, Day 1 (10/30/01) 41
13 Dilution Flow. Day 1 (10/30/01) 42
14 Venturi Flow, Day 1 (10/30/01) 42
15 Blower Flow, Day 2 (10/31/01) 43
16 Dilution Flow, Day 2 (10/31/01) 43
17 Venturi Flow, Day 2 (10/31/01) 44
18 Blower Flow. Day 3 (11/01/01) 44
19 Dilution Flow. Day 3 (11/01/01) 45
20 Venturi Flow, Day 3 (11/01/01) 45
21 Plots of Particle Counts vs. Size, Particle Mass vs. Size, and Particle Mass
per Stage for Test Day 1 (10/30/01) 65
22 Plots of Particle Counts vs. Size, Particle Mass vs. Size, and Particle Mass
per Stage for Test Day 2 (10/31/01) 66
23 Plots of Particle Counts vs. Size, Particle Mass vs. Size, and Particle Mass
per Stage for Test Day 3 (11/01/01) 67
24 02 and C02 Concentrations for Recovery Boiler No. 5 on Test Day 1 (10/30/01) . . 69
25 02 and C02 Concentrations for Recovery Boiler No. 5 on Test Day 2 (10/31/01) . . 70
26 02 and C02 Concentrations for Recovery Boiler No. 5 on Test Day 3 (11/01/01) . . 71
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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
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 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 recovery 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.
Characterization of a Recovery Boiler at a Pulp and Paper
Facility
During the last quarter of 2001, a sampling campaign was conducted at a large pulp and
paper mill to measure emissions from three of the mill's sources of emissions to the
atmosphere; i.e., a recovery boiler fired with concentrated liquid wastes from the wood
digestion and pulp washing processes, an auxiliary boiler combusting a mixture of wood
bark (hogged wood waste) and coal, and a vent from the smelt tank. The primary aim of
these tests was to measure the mass emission factors and chemical compositions of the fine
particulate matter emitted. This test report presents results from the emissions testing of the
recovery boiler.
Previous work to determine PM emissions for this type of source focused on the
filterable and condensible fractions of total PM emitted as measured by EPA Method 5 or
Method 202.1 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.
Recovery boilers, common to nearly all pulp and paper mills, are usually one of the
major contributors to atmospheric emissions from the mill. Processing wood chips in a pulp
mill utilizing the Kraft process involves digesting the wood in a solution of sodium sulfide
and sodium hydroxide. The spent digestion liquor combined with water used to wash the
resulting pulp is called "black liquor." After undergoing concentration by evaporation to
about 65% solids, the black liquor is fed to the recovery boiler as fuel. Dissolved organics in
the concentrated black liquor are combusted in the recovery boiler to yield heat to generate
process steam and to convert sodium sulfate formed in the process back to sodium sulfide
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which can be recycled to the digestion step as a reactant. The recovery boiler tested here was
equipped with two parallel electrostatic precipitators with 169,194 linear feet of plate area
per precipitator, installed in the flue gas exhaust ducting.
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 1, 2, and 42'3'4
were performed to establish the stack gas velocity, temperature, pressure, and exhaust gas
moisture content. The exhaust gas flow rate was calculated from these measurements and
was assumed to remain constant throughout the following three-day test series.
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 such as the CMB model employed by environmental regulatory agencies
for apportioning ambient PM to the various sources contributing to the ambient PM.
Report Organization
This report is organized into five additional sections plus references and appendices.
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
Combustion of organic components in the black liquor fuel was essentially complete in
the recovery boiler as evidenced by the non-detectable amount of organic carbon in the fine
PM emissions and by the very low quantities of volatile organic compounds in the gas-phase
emissions from the boiler. Total measured non-methane organic compounds in the gas-phase
emissions amounted to 43.6 |ig/m3 on average, which was lower than the concentration of
these compounds found in the ambient air at the facility (74.0 |ig/m3). The lower
concentration of organic compounds in the boiler emissions may be attributed to the fact that
the ambient air used to dilute the stack gas prior to sample collection was purged of
contaminants before mixing with the stack gas.
On the first test day (10/30/01) of the three-day test series, the boiler was fired with a
mixture of black liquor and #2 distillate oil (8.8 wt% oil, 91.2 wt% black liquor). Firing on
this day was occasioned by repair of one of the two fuel inlet nozzles, which normally inject
black liquor into the boiler. On the second and third days of testing, only black liquor was
used as the fuel. On the single test day when distillate oil was used together with black
liquor as the boiler fuel, the PM mass emissions, the elemental carbon content of the fine
PM, and the mass emissions of gaseous nonmethane organic compounds were significantly
higher than on the other two test days. For this reason, uncertainties associated with the
reported emission factors are higher when results of all three test days are considered than
when only the results of the second and third test days are considered. The higher emission
factors for Day 1 should be viewed as anomalous and reflective of an upset condition in the
boiler operation.
Even when the relatively higher emissions measured on Test Day 1 are included, the
measured emission factors for fine PM are lower than estimated in the EPA's emission
inventory (AP-42) for pulp and paper recovery boilers equipped with electrostatic
precipitators. EPA's current estimates for this source category are 1000 mg of total PM/kg
of fuel and 600 mg of PM2 5 per kg of fuel. These estimates are based on previous
measurements of the filterable portion of PM emitted as defined by EPA Method 5,
"Determination of Particulate Matter Emissions from Stationary Sources." Mass emission
factors of PM2 5 determined by this study range from 45.4 to 10.6 mg per kg of fuel with an
average over all three tests of 23.3 mg per kg of fuel. In this connection, it should also be
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noted that this particular recovery boiler had just completed two months of line-out
operation (i.e., checkout and optimization) following a major reconditioning and overhaul of
the system, including replacement of the burners.
Results of the three replicate test runs conducted during three consecutive days may be
summarized as follows. Essentially no organic compounds were detected in either the fine
PM or the gas-phase emissions from the recovery boiler stack, indicating that the organic
components of the black liquor fuel were essentially completely combusted in the boiler.
Organic carbon in the collected fine PM (a measure of the organic composition of the PM)
was non-detectable, and the total volatile organic compounds (total VOCs) in the collected
gas-phase emissions amounted to only 33.6 mg/m3 on average. In fact, the total VOC
concentration in the boiler emissions averaged slightly less than that found in the ambient
air at the plant site (40.4 mg/m3). This observation may be attributed to the fact that the
ambient air used to cool and dilute the sampled exhaust gas had been rigorously purged of
organics prior to mixing with the exhaust gas.
PM25 mass emissions ranged from 10.6 to 45.4 mg per kg of fuel with an average of 23.3
mg per kg fuel over the three test days. The highest emission factor (45.4 mg per kg fuel)
was found on the one day #2 distillate oil was added to the black liquor fuel (8.8 wt% oil,
91.2 wt% black liquor). Reasons for a higher mass emission factor for fine PM when co-
firing the boiler with oil are not clear.
Approximately 83% of the PM2 5 mass was identified and quantified and was found to
consist largely of sodium and/or potassium sulfate with a smaller amount of sodium and/or
potassium chloride. The mean aerodynamic particle diameter of the PM2 5 was found to be
1.31 |im.
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Methods and Materials
A field test was conducted (October 30-November 1, 2001) on a recovery boiler 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
recovery 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 recovery 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
particulate matter.
To assist in the characterization of the recovery 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 1, 2, and 42"4 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,
fuel consumption, 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.
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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. Hildemann5 and 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.
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.
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.
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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.
-------
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.
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
11
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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. For the test conducted on October
30-November 1, 2001, the calculated total time the sample spent in the dilution sampling
system was 73 sec with 2.4 sec for the turbulent mixing chamber and 70.6 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 recovery boiler.
In operation, the source sample flow, the dilution airflow, 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
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.
12
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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
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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, 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 testing episode.
Process Description/Site Operation
The recovery boiler tested (referred to as "Recovery Boiler No. 5") burns as much as 130
tons per hour of black liquor solids. Recovery Boiler No. 5 is equipped with two electrostatic
precipitators (169,194 feet of plate area per precipitator) installed on the flue gas exit system
from the boiler. The Recovery Boiler No. 5 sampling site is located on the vertical wall of a
boiler duct, with a sampling port 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 location is elevated approximately 50 feet above ground level. A
schematic diagram of the layout of the sampling site is shown in Figure 3. The area around
the sampling port is 16 to 17 feet long and approximately 36 in. wide.
Access to this location required use of a catwalk-type platform. The whole site is in a
"welled" area, enclosed on three sides, with limited access from above because of pipes and
duct work. Large pieces of sampling equipment (i.e., the dilution sampling system and the
control unit) were lifted up to the sampling location using a crane available at the site. The
dilution sampling system was lifted to the location shown in Figure 3 then rolled into position
at the sampling port (Figure 4) on an elevated secondary platform constructed to facilitate
rolling the dilution sampling system along a corridor with railings on one side. With the
agreement of the facility staff, some of these railings were removed to allow passage of the
dilution sampling unit along the corridor.
The elevated walkway shown in Figure 3 allowed minimal space around the dilution
sampling system. The control unit for the dilution sampling system was therefore located on
the opposite side of the elevated walkway (Figure 3) and connected to the dilution sampling
unit by approximately 10 feet of flexible tubing.
14
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Flow
Test Duct
Sample—~jTrr™
Port !_~
Dilution Air
Hose 1
-~-Probe
Sample Rumps
Control
System
Raised
Catwalk
Sample Platform
Elevation = 45 above grade
Figure 3. Schematic Diagram of Layout of Recovery Boiler No. 5
Sampling Site.
Existing
Port
Recovery Boiler No. 5
Stack Duct Work
Location of
Recovery Boiler
Sampling Port
Existing
Port
Figure 4. Recovery Boiler Sampling Port Location.
15
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Supplemental equipment such as the ELPI was transported up stairs to reach the sampling
site. There was no space in the vicinity of the sampling port for location of an appropriate
enclosed area for preparation of sampling components or for recovery of the sample
collection arrays. An appropriate area at ground level was therefore identified for preparation
of sampling components and for recovery of the sample collection arrays and preparation for
transport to the laboratories.
Recovery Boiler No. 5 burns the high concentration of heavy black liquor solids generated
in the concentrator. The combustion process in the boiler oxidizes the organic compounds to
produce heat and allows the inorganic solids (smelt) to be recovered at the base of the boiler.
Recovery Boiler No. 5 (one of several recovery boilers that function independently) is a
noncontact, low-odor boiler with a rated capacity of 520 gal/min of black liquor (density 11.4
lb/gal) or a mass flow rate of 121 tons per hour black liquor solids (BLS). In addition,
Recovery Boiler No. 5 is equipped to fire fuel oil during startup, shutdown, and malfunction.
The heat recovered is used to produce 35% of the steam and electricity required by the
facility. Smelt recovered at the base of the boiler is dropped into both of the two smelt
dissolving tanks. At the request of ERG, a sample of the black liquor was collected for
analysis by facility environmental staff. The black liquor sample was collected at the inlet to
the fuel injector during the first test day; analytical results are shown in Table 2.
Table 2. Analysis of Black Liquor
Parameter Value
Sulfur 2.73%
Btu per pound 4208
Ash 23.18%
Carbon 23.86%
Hydrogen 6.93%
Nitrogen 0.07%
Oxygen 43.23%
Chlorine 870.6 ppm
Exhaust gases from Recovery Boiler No. 5 are routed through two parallel electrostatic
precipitators (ESPs) for particulate control prior to release to the atmosphere through the
No. 1 Hogged Fuel Boiler stack. The ash generated in the ESPs contains large amounts of
sodium in the form of sodium sulfate (Na2S04) and is known as the "salt cake." This salt cake
is recovered by pumping heavy liquor from a tank called "the precipitator mix tank" to a
ribbon mixer in the base of the ESPs. This heavy liquor/salt cake combination is then
16
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discharged to a salt cake mix tank where it is heated and mixed with direct steam injection
prior to being fed to the recovery boiler. However, the volume of recovered salt cake injected
is negligible compared to the volume of black liquor injected. A significant amount of vapor
is generated in the salt cake mix tank, which is captured and controlled by the
Noncondensible Gases System. The precipitator mix tank vents to the atmosphere.
One of the purposes of the recovery boiler is to chemically convert the inorganics in the
black liquor into a form that can later be recovered and converted to white liquor, mostly
sodium hydroxide (NaOH), to recycle to the digesters. This conversion is accomplished by
control of the combustion process to the extent that the Na2S04 present in the black liquor or
generated in the oxidizing section of the furnace is predominantly converted into sodium
sulfide (Na2S) and sodium carbonate (Na2C03), which comprise the smelt. This is the
principal reason for recycling the ash (salt cake, Na2S04) from the ESPs. The sulfates are
produced in the oxidizing section of the boiler, where odor-producing sulfides and mercaptans
are minimized by conversion to sulfur dioxide (S02).
The fuel use for Recovery Boiler No. 5 during the testing period is summarized in
Table 3. A more detailed description of the fuel fired for each specific test is provided in
Table 4.
Table 3. Recovery Boiler No. 5 Fuel Use During the Test Period (Average Stack Gas
Velocity Based on Traverse = 2745.8 ft/min)
Total Volume Combined Overall
Test Fuel Feed Rate Test Duration Used Total Volume
# Type (gal/min) (min) (gal) Used (gal)
1
Black Liquor3
265.43
482
127937.3
1
#2 Oil
41.31
482
19911.4
1
147848.7
2
Black Liquor
471.43
480
226483.2
2
#2 Oil
None
480
0
2
226483.2
3
Black Liquor
506.33
479
242532.1
3
#2 Oil
None
479
0
3
242532.1
a Black Liquor Nominal Density = 11.4 lb/gal
17
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Table 4. Process Data for Testing Days: Black Liquor, Black Liquor Solids, and #2 Oil
Test
#
Test
Date
2001
Start
Time
End
Time
Black
Liquor"
Firing Rate
(gpm)
Black
Liquor
Solids
(%)
Tons
Black Liquor
Solids/Hour
Total Tons
Black
Liquor
Solids
Fired
#2 Oil
Firing
Rate
(gal/min)
1
10/30
0850
1650
265.43
67.72
61.47
491.79
41.31
2
10/31
0800
1600
471.84
67.74
109.31
874.49
0
3
11/1
0730
1530
506.33
67.75
117.32
938.55
0
"Black Liquor nominal density, 11.4 lb/gal
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
installation of a sample collection port (Figure 4) at the outlet of the electrostatic
precipitators, 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 on a
catwalk platform at the test location (Figure 3). 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 1, 2, and 4 were conducted to establish key experimental parameters for test
conditions.
Traverse Point Determination Using EPA Method 1
EPA Method 1, "Sample and Velocity Traverses for Stationary Sources" (40 CFR Part 60,
Appendix A, pp. 181-206),2 was used to establish the number and location of sampling
traverse points necessary for isokinetic and flow sampling. These parameters are based on
19
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how much duct distance separates the sampling ports from the closest downstream and
upstream flow disturbances. The Recovery Boiler No. 5 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 from the two electrostatic
precipitators used on Recovery Boiler No. 5 (Figure 3).
The following duct dimensions were measured:
Inside of far wall to outside of nipple (Distance A): 150 in.
Inside of near wall to outside of nipple (Distance B): 4 in.
Inside stack dimensions: 146 in.
Traverse point locations for a the rectangular recovery boiler duct are listed in Table 5. A
table of metric unit conversions is shown in Appendix A.
Table 5. EPA Method 1 Traverse Point Locations for Recovery Boiler No. 5 Exhaust
(a Rectangular Duct)
Traverse Fraction of Inside Stack Traverse Point
Point Dimension3 Distance from Stack Wall Location
Number (%) (in.) (in.)
1
5.0
7 %
11 %
2
15.0
21 %
25%
3
25.0
36 »/2
40 »/2
4
35.0
51 1/8
55 1/s
5
45.0
65 %
69 %
6
55.0
80%
84%
7
65.0
94 %
98%
8
75.0
109 »/2
113 »/2
9
85.0
124 1/s
128 1/s
10
95.0
138 3/4
142 3/4
a Inside stack depth: 146 in. Distance from lip of flange to inside stack wall: 4 in.
The absolute pressure of the flue gas (in inches of mercury) was calculated according to the
equation
PS= Pb +— (4_1)
bar 13/)
20
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where:
PS = absolute gas pressure, inches of mercury
Pbar = barometric pressure, inches of mercury (30.24 in.)
Pg = gauge pressure, inches of water (static pressure) (0.11 in.).
The value 13.6 represents the specific gravity of mercury (1 inch of mercury =13.6 inches
of water). For the stack tested, the absolute gas pressure under the test conditions was 30.248
inches of mercury.
Volumetric Flow Rate Determination Using EPA Method 2
Volumetric flow rate was measured according to EPA Method 2, "Velocity-S-Type Pitot"
(40 CFR Part 60, Appendix A, pp. 214-153).3 A K-type thermocouple 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
K = Kr x C„ x
ap„x(460+t;) (4_2)
P. X M.
where:
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 (0.28 in.)
460 = 0 °F, expressed as degrees Rankin
Ts = flue gas temperature, °F (367.7 °F)
Ps = absolute stack pressure (barometric pressure at measurement site plus stack static
pressure), inches of mercury (30.248 in.)
21
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Ms = wet molecular weight, pounds per pound-mole (27.67 pounds/pound-mole).
The flue gas velocity calculated for each traverse point and the average velocity are
shown in Table 6.
Table 6. Average Flue Gas Velocity for Each Traverse Point (Average Flue Gas
Velocity)
Traverse Point
Velocity
(Calculated in Table 5)
(ft/min)
1
2276.5
2
2641.2
3
2743.7
4
2809.6
5
2776.7
6
2461.4
7
2874.4
8
2937.4
9
2968.5
10
2968.5
Average Velocity
2745.8
The point of average velocity has the closest relationship to Traverse Point #3.
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 5 (40 CFR part
60, Appendix A, pp. 371-443), 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 Recovery Boiler No. 5
was 0.267 in. 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).
22
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Stationary Gas Distribution (as Percent Volume)
The following concentrations were measured:
02 = 6.5%V
C02 = 13.0%V
CO = 0.03%V
The percentage of nitrogen (N2) was calculated by
N2%V = 100 - (02%V + C02%V + CO%V) = 80.47%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)]
= 30.36 lb/lb*niole
(4-4)
where:
Md = molecular weight of flue gas, dry basis (lb/lb-mole)
C02%V = percent C02 by volume, dry basis (13.0)
02%V = percent 02 by volume, dry basis (6.5)
CO%V = percent CO by volume, dry basis (0.03)
N2%V = percent N2 by volume, dry basis (80.47)
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.
Wet Molecular Weight of Flue Gas
The wet molecular weight of the flue gas (Ms) was calculated by
Ms — (Md x M^ ) + (0.18 x H?0%V)
= 27.67 wet lb/lb* mole
where:
Ms = wet molecular weight of flue gas, wet lb/lb-mole
Md = molecular weight of flue gas, dry basis (30.36 lb/lb-mole)
Mfd = dry mole fraction of effluent gas, calculated as [1 - H2O%V/100] (0.7826)
0.18 = molecular weight of H20, divided by 100
H20%V = percent H20, by volume (21.739).
23
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Determination of Average Moisture Using EPA Method 4
EPA Method 4, "Moisture Content," (40 CFR Part 60, Appendix A, pp. 347-371),4 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. Before sampling, the initial weight of the impingers was
recorded. 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 by computer. 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 7 were made on October 29, 2001.
Table 7. Moisture Recovery for Method 4 (Measured on 10/29/01)
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
792.8
569.3
223.8
2
Water
100
Standard
626.6
584.8
41.8
3
Empty
"
Standard
513.6
507.8
5.8
4
Silica Gel
300
Standard
771.0
761.3
9.7
Total Weight Gain (g)
281.1
Volume of Dry Flue Gas Sampled at Standard Conditions (dscf)
The volume of dry flue gas sampled under standard conditions was calculated by
K(std) = ^^xyxVmx
Pbar +
A H
13.6
460+ T
= 47.632 dscf
(4-6)
where:
V,
m(std)
= volume of dry gas sampled at standard conditions, dry standard cubic feet (dscf)
Vm = volume of gas metered, cubic feet, dry (49.418 ft3)
y = dry gas meter calibration factor (0.980)
Pbar = barometric pressure at measurement site, inches of mercury (30.24 in.)
AH = sampling rate, measured as differential pressure at the meter orifice, inches of
water (1.82 in.)
24
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Tm = dry gas meter temperature, °F (84.7 °F).
The constant 17.64 was used for conversion to standard conditions; 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 47.632 dscf.
Volume of Water Vapor at Standard Conditions (dscf)
The volume of water vapor under standard conditions was calculated by
Vw(std) = volume of water vapor at standard conditions, dry standard cubic feet (dscf)
Vlc = volume of liquid catch (281.1 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
J"/"
H, 0%V = 100 x —— =21.7 %V (a o
^ ¦ hmud)
Using values measured using EPA Method 4 and values calculated previously, the
moisture content was calculated to be 21.7%V.
Calculation of Dry Mole Fraction of Flue Gas
The dry mole fraction of flue gas is calculated by
where:
Mfd = dry mole fraction of flue gas.
Using the percent moisture determined above, the dry mole fraction of flue gas is
calculated as 0.783.
K&d) = 0,04707 x Vlc =13,231 dscf
(4-7)
where:
(4-9)
25
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Setup of the Dilution Sampling System
The Recovery Boiler No. 5 sampling location was the vertical wall of a boiler duct, with
the sampling port elevated approximately 50 feet above ground level (schematic diagram of
test site in Figure 3). The area around the sampling port was 16 to 17 feet long and
approximately 36 inches wide. Access to this location was by a catwalk-type platform. The
whole site was in a "welled" area and enclosed on three sides with limited access from above
because of pipes and duct work. The large pieces of the dilution sampling system (i.e., the
dilution sampling system itself and 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 4) on an elevated secondary platform constructed to facilitate rolling the
sampling unit along a corridor, which had railings on one side.
Since the elevated walkway shown in Figure 3 allowed minimal space around the dilution
sampling unit, the control unit for the dilution sampling system was located on the opposite
side of the elevated walkway and connected to the dilution sampling unit by approximately 10
feet of flexible tubing. The dilution sampling system positioned at the sampling location is
shown during operation in Figure 5.
Figure 6 shows the sampling probe installed in the 6 in. flanged port used for sampling.
The control module (Figure 7) was located on the opposite side of the elevated walkway,
connected to the dilution sampling unit using the flexible tubing visible at the left side of the
control unit.
An ELPI, manufactured by Dekati (Figure 8), with associated laptop computer, was also
connected to the sampling module together with other sample collection arrays; one sample
collection array is visible in the background.
The dilution system sampling module with all sample collection arrays and instruments
attached is shown in Figure 9. Note the ELPI in the foreground and the various sample
collection arrays (the white filter holders are readily visible) attached to the various ports of
the dilution system sampling module.
26
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Figure 5. Dilution Sampling System Positioned at the Sampling Location
During Operation.
Figure 6. Dilution Sampling Probe Installed in 6-in. id Flanged Port.
27
-------
Figure 7. Dilution System Control Module Positioned at the Sampling
Location.
Figure 8. Dilution System with Sample Collection Arrays and Instruments
Attached.
28
-------
Figure 9. Dilution System Sampling Module with All Sample Collection
Arrays and Instruments Attached. White Filter Holders Are Readily Visible.
Sample collection arrays were transported intact to the recovery area in the mobile laboratory
(note two assembled collection arrays on the table in front of the analyst) and disassembled.
Samples were then labeled, packaged for transport, and placed in a chest-style freezer. Chain
of custody forms for the samples are shown 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, 8- x 10-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
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. As the reading
passed 27 in., a stopwatch was started 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.
29
-------
Figure 10. Recovery Area for Dilution Sampling System Sample Collection
Arrays.
leakage rate = x F x ( '/•' < 0.1 ft/min (4-10)
where:
leakage rate = rate of leakage (ft3/min)
AP = change in pressure (in. water)
AT = time increment (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 1 min 51 sec was
required for a 5-in. pressure change to occur. The resulting leak rate was 0.1 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
30
-------
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/Veriflow 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 8).
Table 8. Blank Values for Veriflows and Canisters
Blank Value
Unit (ppbC)
Veriflows
EPA Unit #418 (Source Veriflow)
0.3
ERG-1 Ambient Veriflow
1.2
EPA Unit #315 (Dilution Veriflow)
6.3
Canisters
4030
2.4
1439
1.4
1435
3.7
4010
1.1
1480
1.4
3970
0.0
1892
0.1
4039
0.2
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
31
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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 was dependent upon 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, 10/30/01; Test Run #2, 10/31/01; Test Run #3,
11/01/01), sample collection arrays were attached to various ports on the dilution sampling
system, as shown in Figure 11. 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.
• 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.
32
-------
Dilution chamber
Port#D1
Port #D2 Port#D3
B QF B TF
Residence chamber
Port #R2 Port #R3
B TF B TF
Port #R5 Port#R6
tf gTF
Port#R4
B qf g qf
Cyclone
Port#R8
B qf g qf
Cyclone
Field Blanks
QF 1
TF 1
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
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-Dinitrophenylhydrazine
-impregnated silica gel cartridge
Figure 11. Sample Collection Arrays Used with Recovery Boiler No. 5.
33
-------
• 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 Teflon 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.
• 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
34
-------
denuders in series and on two PUF sampling modules in series. This sample collection
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.
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.
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 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.
35
-------
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 on 10/29/0 lto 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 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
36
-------
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 12
through 20. 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. For the three replicate test runs
conducted on the recovery boiler, the dilution ratio averaged 45.5.
Table 9. Run Time Summary Information, Test Run #1 (10/30/01)
Run Parameter Value
Start Time 8:46:55 A.M.
End Time 4:49:20 P.M.
Run Time 482.42 min
Barometric Pressure 29.93 in. Hg
Nozzle Size #8 (186.5 °C, 2745.8 fit/min)
Canister Flow dilution canister, 8.125 cm3/min
residence chamber canister 8.125 cm3/min
ambient 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
29.31 aL/min3 (20.25 sL/minb)
-1.21 in. WCd
151.71 °C
863.23 aL/min (861.48 sL/min)
-1.52 in. WC
19.32 °C
861.19 aL/min (819.92 sL/min)
-16.74 in. WC
22.15 °C
43.61
101.28 °C
149.88 °C
149.89 °C
continued
37
-------
Table 9. (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
17.08
17.08
17.10
17.10
17.08
pm25
pm25
Residence Chamber
Residence Chamber
10
10
start
end
15.59
14.43
15.61
14.45
15.01
pm25
pm25
Residence Chamber
Residence Chamber
8
8
start
end
17.38
17.38
17.40
17.40
17.38
pm25
pm25
Residence Chamber
Residence Chamber
6
6
start
end
17.69
17.69
17.71
17.71
17.69
pm25
pm25
Residence Chamber
Residence Chamber
4
4
start
end
17.53
17.38
17.55
17.40
17.46
pm25
pm25
Residence Chamber
Residence Chamber
2
2
start
end
17.69
17.69
17.71
17.71
17.69
DNPH
Residence Chamber
3
start
1.51
1.51
1.49
DNPH
Residence Chamber
3
end
1.46
1.46
DNPH
Dilution Chamber
3
start
1.26
1.27
1.25
DNPH
Dilution Chamber
3
end
1.24
1.24
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 10. Run Time Summary Information, Test Run #2 (10/31/01)
Run Parameter Value
Start Time 7:59:03 A.M.
End Time 3:59:05 P.M.
Run Time 480.03 min
Barometric Pressure 29.91 in. Hg
Nozzle Size #8 (186.5 °C, 2745.8 fit/min)
Canister Flow dilution canister, 8.958 cm3/min
residence chamber canister 8.125 cm3/min
continued
38
-------
Table 10. (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
30.57 aL/min3 (18.88 sL/minb)
-1.13 in. WCd
201.95 °C
865.21 aL/min (859.33 sL/min)
-1.27 in. WC
20.77 °C
858.83 aL/min (813.40 sL/min)
-15.82 in. WC
24.23 °C
46.59
182.43 °C
196.83 °C
197.05 °C
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
17.65
17.65
17.44
17.44
17.65
pm25
pm25
Residence Chamber
Residence Chamber
10
10
start
end
17.65
17.65
17.44
17.44
17.65
pm25
pm25
Residence Chamber
Residence Chamber
8
8
start
end
17.80
17.50
17.59
17.29
17.65
pm25
pm25
Residence Chamber
Residence Chamber
6
6
start
end
17.65
17.65
17.44
17.44
17.65
pm25
pm25
Residence Chamber
Residence Chamber
4
4
start
end
17.80
17.65
17.59
17.44
17.73
pm25
pm25
Residence Chamber
Residence Chamber
2
2
start
end
17.80
17.80
17.59
17.59
17.80
DNPH
Residence Chamber
3
start
1.23
1.21
1.18
DNPH
Residence Chamber
3
end
1.14
1.12
DNPH
Dilution Chamber
3
start
1.18
1.17
1.16
DNPH
Dilution Chamber
3
end
1.14
1.12
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
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Table 11. Run Time Summary Information, Test Run #3 (11/01/01)
Run Parameter
Value
Start Time
End Time
Run Time
Barometric Pressure
Nozzle Size
Canister Flow
7:30:05 A.M.
3:29:07 P.M.
479.03 min
29.85 in. Hg
#8 (186.5 °C, 2745.8 ft/min)
dilution canister, 8.958 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
30.57 aL/miir1 (18.87 sL/minb)
-1.01 in. WCd
201.32 °C
870.16 aL/min (854.46 sL/min)
-1.20 in. WC
23.54 °C
865.45 aL/min (810.83 sL/min)
-15.93 in. WC
26.80 °C
46.34
186.96 °C
196.85 °C
196.85 °C
Sample Flow Rates
Start/
Flow
Sample
Location
Port
End
(sL/min)
(aL/min)
pm25
Dilution Air
—
start
17.63
17.46
pm25
Dilution Air
—
end
17.63
17.46
pm25
Residence Chamber
10
start
17.32
17.16
pm25
Residence Chamber
10
end
17.17
17.01
pm25
Residence Chamber
8
start
17.78
17.61
pm25
Residence Chamber
8
end
17.63
17.46
pm25
Residence Chamber
6
start
17.63
17.46
pm25
Residence Chamber
6
end
17.78
17.61
pm25
Residence Chamber
4
start
17.78
17.61
pm25
Residence Chamber
4
end
17.78
17.61
Average Flow
(sL/min)
17.63
17.24
17.71
17.71
17.78
continued
40
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Table 11
. (concluded)
Sample Flow Rates
Start/
Flow
Average Flow
(sL/min)
Sample
Location
Port
End
(sL/inin)
(aL/min)
I'M <
pm25
Residence Chamber
Residence Chamber
2
2
start
end
17.78
17.78
17.61
17.61
17.78
DNPH
Residence Chamber
3
start
1.32
1.31
1.31
DNPH
Residence Chamber
3
end
1.29
1.28
DNPH
Dilution Chamber
3
start
1.13
1.12
1.13
DNPH
Dilution Chamber
3
end
1.13
1.12
a aL/min = actual liters per minute
b sL/min = standard liters per minute
c PT = pressure transducer
a WC = water column
e TE = thennocouple
c
E
-200
Actual
Standard
:
):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 12. Blower Flow, Day 1 (10/30/01).
41
-------
c
E
> Standard
k
i:0(^ 9:00:00 10:00:00 11:00:00 12:00:00 13:00:00 14:00:00 15:00:00 16:00:00 1
:00 18:0
Time
Figure 13. Dilution Flow, Day 1 (10/30/01).
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 14. Venturi Flow, Day 1 (10/30/01).
42
-------
1200
1000
Actual
Standard
600
400
200
):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
7:0
-200
Time
Figure 15. Blower Flow, Day 2 (10/31/01).
c
E
600
400
200
0
7:0
Actual
Standard
-1 r~
J:W 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:C?0fl0 17:03:00
Time
Figure 16. Dilution Flow, Day 2 (10/31/01).
43
-------
60
50
Actual
Standard
o 1 1 1 1 1 1 1 1 ! 1
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 17. Venturi Flow, Day 2 (10/31/01).
¦
| Actual
Standard
*
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 18. Blower Flow, Day 3 (11/01/01).
44
-------
1200
1000
Actual
800
Standard
c 600
E
23
400
200
7:0
!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
-200
Time
Figure 19. Dilution Flow, Day 3 (11/01/01).
Actual
C
E
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 20. Venturi Flow, Day 3 (11/01/01).
45
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Dilution System Sample Collection Arrays: Sample
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:
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.
46
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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 is supplied in Appendix B. The field sample log with sample
identification is provided in Appendix C.
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 D.
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.
47
-------
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.
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)6 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.
48
-------
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.
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.
49
-------
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 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 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)".7 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. MDLs8 for
the carbonyl analysis are shown in Appendix E.
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 19, 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
50
-------
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 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 l-|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.
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)".9 The analysis of speciated nonmethane organic compounds was performed
according to the procedures of "Technical Assistance Document for Sampling and Analysis of
Ozone Precursors".7 Detection limits8 for air toxics and for the speciated nonmethane organic
compounds are shown in Appendix E.
51
-------
Particle Size Distribution Data
The ELPI was operated and collected data during all three test days. Data were reduced
using the Dekati software package.
52
-------
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.
Calculated Emission Factors for PM Mass, Carbonyls, and
Nonmethane Organic Compounds
Emission factors reported in Table 12 show the following:
Uncertainties are the standard deviations of the values for each of the three tests;
Uncertainties in reported emission factors reflect the fact that the recovery boiler was
operated differently on Day 1 than on Days 2 and 3. Reported uncertainties are smaller
if the results of only Days 2 and 3 are considered;
Values for the Tests 2 and 3 PM2 5 mass emissions decrease by a factor of
approximately three compared to the value for Test 1. Test 1 (10/30/01) was
conducted on the only day #2 oil was burned in addition to black liquor;
The highest value for the NMOC emission factor (both speciated and total) is
observed on 10/30/01, the day #2 oil was burned; and
Carbonyl compounds show their lowest value on the day #2 oil was burned.
Table 12. Fine Particle, Carbonyl, and Nonmethane Organic Compound Emission
Factors from a Recovery Boiler at a Pulp and Paper Facility
Emission Factor 10/30/01" 10/31/01 11/01/01 Mean Standard
Deviation
PM2 5 Mass Emission Factor (mg/kg fuel
45.41
10.57
13.92
23.30
19.22
burned)
Speciated Carbonyl Compounds Mass
0.0741
1.1209
0.4788
0.5579
0.7402
Emission Factor (mg/kg fuel burned)
Total (speciated + unspeciated) Carbonyl
0.5548
1.7382
1.0783
1.1238
0.5930
Compounds Mass Emission Factor (mg/kg
fuel burned)
Speciated NMOC Mass Emission Factor
4.4157
2.0432
1.9267
2.7952
1.4046
(mg/kg fuel burned)
Total (speciated + unspeciated) NMOC
9.0266
4.3971
4.3294
5.9177
2.6926
Mass Emission Factor (mg/kg fuel burned)
a Fuel on this day was a mixture of black liquor and #2 distillate oil.
53
-------
Supporting data for emission factor calculations are shown in Appendices F and G.
Supporting data for individual PM2 5 mass measurements are presented in Appendix H.
Gas-Phase Carbonyl Compounds
Analytical results for the carbonyl field samples for each of the three test days are shown
in Table 13. Results of the analysis are reported for the difference between the summed paired
DNPH-impregnated silica gel tubes for the residence chamber (RC) and the summed paired
DNPH-impregnated silica gel tubes for the dilution air (DA). At the bottom of the table, the
entry reported as "Total Unspeciated" is the total mass (front plus back tube) of the
compounds characterized as carbonyl compounds but not identified as a specific compound
because no analytical standard was available. The entry reported as "Total Speciated plus
Unspeciated" includes the total mass (front and back tube) of both specifically identified
carbonyl compounds and unspeciated carbonyl compounds.
A significant portion of the reported results for carbonyl compounds are the unspeciated
compounds. Masses for these unspeciated carbonyl compounds are based on the calibration
factor for formaldehyde. Mass fractions shown in Table 13 were calculated by dividing the
mass of each species by the total (speciated plus unspeciated) mass of the carbonyl
compounds found. Reported uncertainties for each species are the standard deviations of
results from the three source sampling tests. For Test Days 1 and 3, more unspeciated
carbonyl compounds are reported than speciated compounds. The field blank is included in
Table 13 as a reference. On Test Day 1, when both #2 oil and black liquor were burned, only
unspeciated carbonyl compounds show an analytical value above the field blank. On Test
Days 2 and 3, when only black liquor was burned, the overall level of carbonyl compounds
(both speciated and unspeciated) was significantly higher than on Day 1. Supporting data
showing results for each individual carbonyl sampling tube (front and back) are included in
Appendix I. Additional quality control checks for the carbonyl analysis are presented in Table
19.
Gas-Phase Air Toxic Compounds
Analytical results for the air toxics canister samples are shown in Table 14. The ERG
concurrent analysis produces analytical results for both air toxics and speciated/nonspeciated
nonmethane organic compounds; these results are presented separately.
Method detection limits (MDLs) for air toxic compounds are shown in Appendix E, with
values typically 1.65 |lg/m3 or less. The values for the small number of air toxic compounds
54
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Table 13. Carbonyl Compounds, Recovery Boiler: Carbonyl Compounds Collected in Dilution Air Subtracted from Carbonyl
Compounds Collected in Residence Chamber, with Mass Fraction of Each Analyte, Mean, and Uncertainty
Carbonyls
Carbonyls
Carbonyls
Field
RC-DA
Mass
RC-DA
Mass
RC-DA
Mass
Mean
Blank
10/30/01
Fraction
10/31/01
Fraction
11/01/01
Fraction
Mass
Compound
CAS No.
(US)
(US)
10/30/01
(US)
10/31/01
(UB)
11/01/01
Fraction
Uncertainty
formaldehyde
50-00-0
0.0235
0.8200
0.2447
1.2550
0.1476
1.7495
0.2953
0.2292
0.0751
acetaldehyde
75-07-0
0.0760
0.4590
0.1370
3.4015
0.4001
0.3250
0.0549
0.1973
0.1803
acetone
67-64-1
0.1965
NDa
ND
0.4060
0.0478
0.3090
0.0522
0.0333
0.0289
propionaldehyde
123-38-6
ND
ND
ND
0.0195
0.0023
0.0255
0.0043
0.0022
0.0022
crotonaldehyde
4170-30-0
ND
ND
ND
ND
ND
ND
ND
ND
ND
butyr/isobutyraldehyde
123-72-8
0.0460
0.0290
0.0087
0.0195
0.0023
0.0360
0.0061
0.0057
0.0032
benzaldehyde
100-52-7
ND
0.0140
0.0042
0.0100
0.0012
0.0145
0.0024
0.0026
0.0015
isovaleraldehyde
590-86-3
ND
ND
ND
ND
ND
ND
ND
ND
ND
valeraldehyde
110-62-3
0.0065
ND
ND
0.1095
0.0129
ND
ND
0.0043
0.0074
o-tolualdehyde
529-20-4
ND
0.0155
0.0046
ND
ND
ND
ND
0.0015
0.0027
/M-toliialdchydc
620-23-5
ND
ND
ND
ND
ND
ND
ND
ND
ND
/Molualdchydc
104-87-0
0.0365
0.0235
0.0070
ND
ND
ND
ND
0.0023
0.0040
hexaldehyde
66-25-1
0.0170
0.0085
0.0025
0.0205
0.0024
0.0070
0.0012
0.0020
0.0007
2,5-dimethylbenzaldehyde
5779-94-2
ND
ND
ND
ND
ND
ND
ND
ND
ND
diacetyl
431-03-8
ND
ND
ND
ND
ND
ND
ND
ND
ND
methacrolein
78-85-3
ND
ND
ND
0.0210
0.0025
ND
ND
0.0008
0.0014
2-butanone
78-93-3
0.0230
ND
ND
0.1620
0.0191
0.1850
0.0312
0.0168
0.0157
glyoxal
107-22-2
0.0900
0.0830
0.0248
0.0720
0.0085
0.0870
0.0147
0.0160
0.0082
acetophenone
98-86-2
ND
ND
ND
0.0040
0.0005
ND
ND
0.0002
0.0003
methylglyoxal
78-98-8
0.0420
0.0470
0.0140
0.0320
0.0038
ND
ND
0.0059
0.0073
octanal
124-13-0
ND
0.0270
0.0081
0.0320
0.0038
ND
ND
0.0039
0.0040
nonanal
124-19-6
0.0990
ND
ND
0.0220
0.0026
ND
ND
0.0009
0.0015
continued
-------
Table 13. (Concluded)
Field
Carbonyls
RC-DA
Mass
Blank
10/30/01
Fraction
Compound CAS No.
(U2)
(us)
10/30/01
Sum, Speciated
0.6560
1.5265
0.4555
Sum, Unspeciated
0.7885
1.8245
0.5445
Total (speciated + unspeciated)
1.4445
3.3510
Emission Factor, mg/kg fuel (Speciated) 0.0741
Emission Factor, mg/kg fuel (Total) 0.5548
a ND = not detected.
On
Carbonyls Carbonyls
RC-DA Mass RC-DA Mass Mean
10/31/01 Fraction 11/01/01 Fraction Mass
(USi) 10/31/01 (ut;) 11/01/01 Fraction Uncertainty
5.5865 0.6570 2.7385 0.4622
3.0195 0.3551 3.2935 0.5559
8.5025 5.9245
1.1209
1.7382
0.4788
1.0783
0.5579 0.7402
1.1238 0.5930
-------
Table 14. Summarized Analytical Results for Air Toxics Compounds Observed on
Each of the Three Test Days (10/30/01 through 11/1/01)
RC-DA
RC-DA
RC-DA
Ambient
10/30/01
10/31/01
11/1/01
Compounds Detected
CAS No.
(Hg/m3)
(Hg/m3)
(Hg/m3)
(Hg/m3)
acetylene
74-86-2
0.71
1.95
0.37
0.30
propylene
115-07-1
0.26
0.38
0.29
0.27
dichlorodifluoromethane
75-71-8
2.85
0.09
NDa
ND
chloromethane
74-87-3
1.11
0.02
ND
ND
trichlorofluoromethane
75-69-4
1.41
ND
ND
ND
methylene chloride
75-09-2
0.15
ND
ND
ND
trichlorotrifluoroethane
26253-64-8
0.65
ND
ND
ND
1,1,1 -trichloroethane
71-55-6
0.16
ND
ND
ND
benzene
71-43-2
0.74
0.60
0.76
1.08
carbon tetrachloride
56-23-5
0.65
ND
ND
ND
toluene
108-88-3
1.11
0.71
0.69
0.69
ethylbenzene
100-41-4
0.30
0.28
0.25
0.22
m-, /^-xylene
108-38-3/106-42-3
1.40
0.69
1.00
1.11
o-xylene
95-47-6
0.35
0.37
0.25
0.23
1,3,5-trimethylbenzene
108-67-8
0.08
ND
ND
ND
1,2,4-trimethvlbenzene
95-63-6
0.31
0.29
0.25
0.30
a ND = not detected.
actually observed occur at the lower end of the calibration curve for this analysis; analytical
results are shown in Table 14. Analytical results for an ambient canister taken at the test
location are included for reference. For nearly all of the air toxic compounds, the values
observed in the ambient air are higher than the values observed in the stack emissions.
Supporting data for the air toxics are shown in Appendix J, with analytical results for each
individual canister.
Gas-Phase Speciated Nonmethane Organic Compounds
Analysis of whole air samples of dilution air and residence chamber air generated
analytical data for speciated nonmethane organic compounds (SNMOC), as well as
unspeciated NMOC. Analytical results are presented as mass fractions of total NMOC
(speciated plus unspeciated). Mass emission factors of total SNMOC and total (speciated
plus unspeciated) NMOC are also provided. Mass fractions in Table 15 represent the mass
of each species divided by the total mass (speciated plus unspeciated) of the NMOCs found.
Uncertainties are the standard deviations of results from the three replicate sampling runs.
Results (Table 15) are reported as the difference between residence chamber samples and
dilution air. The dilution air is used to dilute the stationary source matrix; samples of the
57
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Table 15. Speciated and (Speciated + Unspeciated) NMOC Data for All Three Test Days, with Mass Fraction, Mean, and
Uncertainty
Compound
CAS No.
RC-DA
10/30/01
(U2)
Mass
Fraction
10/30/01
RC-DA
10/31/01
(US)
Mass
Fraction
10/31/01
RC-DA
11/01/01
(US)
Mass
Fraction
11/01/01
(U2)
Mean
Mass
Fraction
Uncertainty
ethylene
74-85-1
375.04
0.0162
359.87
0.0184
347.4519
0.0170
0.0172
0.0011
acetylene
74-86-2
852.09
0.0369
82.50
0.0042
30.22804
0.0015
0.0142
0.0197
ethane
74-84-0
273.60
0.0118
143.04
0.0073
181.7271
0.0089
0.0093
0.0023
propylene
115-07-1
192.04
0.0083
137.03
0.0070
106.5256
0.0052
0.0068
0.0016
propane
74-98-6
287.07
0.0124
254.38
0.0130
306.2917
0.0150
0.0135
0.0013
propyne
74-99-7
NDa
ND
ND
ND
ND
ND
ND
ND
isobutane
75-28-5
133.72
0.0058
115.91
0.0059
89.84241
0.0044
0.0054
0.0009
isobutene/1 -butene
115-11-7/106-98-0
112.94
0.0049
204.62
0.0105
161.4141
0.0079
0.0077
0.0028
1,3-butadiene
106-99-0
ND
ND
ND
ND
ND
ND
ND
ND
rt-butane
106-97-8
266.85
0.0116
235.12
0.0120
204.4243
0.0100
0.0112
0.0011
trans-2-butene
624-64-6
149.95
0.0065
144.51
0.0074
160.1486
0.0078
0.0072
0.0007
c/.v-2-butcnc
590-18-1
205.74
0.0089
178.78
0.0091
172.9703
0.0085
0.0088
0.0004
3 -methyl-1 -butene
563-45-1
ND
ND
ND
ND
ND
ND
ND
ND
isopentane
78-78-4
253.50
0.0110
246.68
0.0126
220.0737
0.0108
0.0115
0.0010
1-pentene
109-67-1
154.40
0.0067
127.65
0.0065
130.5928
0.0064
0.0065
0.0002
2-methyl-1 -butene
563-46-2
ND
ND
ND
ND
ND
ND
ND
ND
rt-pentane
109-66-0
175.96
0.0076
128.01
0.0065
168.8772
0.0083
0.0075
0.0009
isoprene
78-79-4
137.19
0.0059
98.05
0.0050
109.856
0.0054
0.0054
0.0005
trans-2-pentene
646-04-8
ND
ND
ND
ND
ND
ND
ND
ND
c/.v-2-pcntcnc
627-20-3
184.67
0.0080
174.29
0.0089
223.1725
0.0109
0.0093
0.0015
2 -me thy 1-2 -butene
513-35-9
ND
ND
ND
ND
ND
ND
ND
ND
2,2-dimethylbutane
75-83-2
245.10
0.0106
343.28
0.0176
311.659
0.0152
0.0145
0.0035
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
172.10
0.0075
165.41
0.0085
201.9837
0.0099
0.0086
0.0012
continued
-------
Table 15. (continued)
Compound
CAS No.
RC-DA
10/30/01
(U2)
Mass
Fraction
10/30/01
2,3 -dimethylbutane
79-29-8
304.65
0.0132
2-methylpentane
107-83-5
521.00
0.0226
3-methylpentane
96-14-0
253.21
0.0110
2-methyl-1 -pentene
763-29-1
ND
ND
1-hexene
592-41-6
334.32
0.0145
2-ethyl-l-butene
760-21-4
ND
ND
«-hexane
110-54-3
231.55
0.0100
;ra«.v-2-hc.\cnc
4050-45-7
ND
ND
67.v-2-hc.xcnc
7688-21-3
ND
ND
methylcyclopentane
96-37-7
201.48
0.0087
2,4-dimethylpentane
108-08-7
218.50
0.0095
benzene
71-43-2
222.75
0.0096
cyclohexane
110-82-7
172.29
0.0075
2-methylhexane
591-76-4
128.88
0.0056
2,3 -dimethylpentane
565-59-3
385.66
0.0167
3-methylhexane
589-34-4
285.78
0.0124
1-heptene
592-76-7
ND
ND
2,2,4-trimethylpentane
540-84-1
278.05
0.0120
//-heptane
142-82-5
167.06
0.0072
methylcyclohexane
108-87-2
239.77
0.0104
2,2,3 -trimethylpentane
564-02-3
ND
ND
2,3,4-trimethylpentane
565-75-3
162.91
0.0071
toluene
108-88-3
253.41
0.0110
2-methylheptane
592-27-8
132.94
0.0058
3-methylheptane
589-81-1
150.05
0.0065
1-octene
111-66-0
ND
ND
Mass
RC-DA
Mass
RC-DA
Fraction
Mean
10/31/01
Fraction
11/01/01
11/01/01
Mass
(US)
10/31/01
(US)
(U2)
Fraction
Uncertainty
284.72
0.0146
282.4648
0.0138
0.0139
0.0007
506.97
0.0259
40.00183
0.0020
0.0168
0.0130
237.98
0.0122
298.9277
0.0146
0.0126
0.0019
ND
ND
ND
ND
ND
ND
305.61
0.0156
307.5659
0.0150
0.0150
0.0006
ND
ND
ND
ND
ND
ND
182.81
0.0094
150.0387
0.0073
0.0089
0.0014
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
165.59
0.0085
181.6989
0.0089
0.0087
0.0002
187.03
0.0096
214.8958
0.0105
0.0098
0.0006
389.29
0.0199
448.9918
0.0219
0.0172
0.0066
229.37
0.0117
235.723
0.0115
0.0102
0.0024
123.25
0.0063
134.9571
0.0066
0.0062
0.0005
331.00
0.0169
354.2172
0.0173
0.0170
0.0003
120.21
0.0062
206.5288
0.0101
0.0095
0.0031
172.84
0.0088
255.1943
0.0125
0.0071
0.0064
229.19
0.0117
156.1459
0.0076
0.0105
0.0025
152.85
0.0078
164.2417
0.0080
0.0077
0.0004
165.77
0.0085
185.5208
0.0091
0.0093
0.0010
ND
ND
ND
ND
ND
ND
152.76
0.0078
131.4064
0.0064
0.0071
0.0007
241.11
0.0123
256.731
0.0125
0.0120
0.0009
131.50
0.0067
138.8695
0.0068
0.0064
0.0006
148.36
0.0076
143.2338
0.0070
0.0070
0.0005
ND
ND
ND
ND
ND
ND
continued
-------
Table 15. (continued)
Compound
CAS No.
RC-DA
10/30/01
(U2)
Mass
Fraction
10/30/01
«-octane
111-65-9
192.49
0.0083
ethylbenzene
100-41-4
128.49
0.0056
m-xx l c nc/p-xx l c nc
108-38-3/106-42-3
175.96
0.0076
styrene
100-42-5
ND
ND
o-xylene
95-47-6
128.78
0.0056
1-nonene
124-11-8
ND
ND
n-nonane
111-84-2
103.16
0.0045
isopropylbenzene
98-82-8
188.23
0.0082
alpha-pinene
80-56-8
ND
ND
«-propyl benzene
103-65-1
107.22
0.0046
/H-cthvltolucnc
620-14-4
94.56
0.0041
p-cthvltolucnc
622-96-8
188.43
0.0082
1,3,5-trimethylbenzene
108-67-8
111.28
0.0048
o-ethyltoluene
611-14-3
137.00
0.0059
beta-pinene
127-91-3
129.17
0.0056
1,2,4-trimethylbenzene
95-63-6
129.07
0.0056
1-decene
872-05-9
ND
ND
n-decane
124-18-5
120.67
0.0052
1,2,3 -trimethylbenzene
526-73-8
ND
ND
/w-diethylbenzene
141-93-5
124.04
0.0054
/j-dicthylbcnzcnc
105-05-5
ND
ND
1-undecene
821-95-4
ND
ND
//-undccanc
1120-21-4
130.44
0.0056
1-dodecene
112-41-4
ND
ND
//-dodccanc
112-40-3
ND
ND
1-tridecene
2437-56-1
ND
ND
RC-DA
10/31/01
(US)
Mass
Fraction
10/31/01
RC-DA
11/01/01
(US)
Mass
Fraction
11/01/01
(U2)
Mean
Mass
Fraction
Uncertainty
123.52
0.0063
160.239
0.0078
0.0075
0.0010
114.55
0.0059
117.9519
0.0058
0.0057
0.0002
ND
ND
205.9864
0.0101
0.0059
0.0052
ND
ND
ND
ND
ND
ND
156.70
0.0080
210.0796
0.0103
0.0080
0.0023
ND
ND
ND
ND
ND
ND
127.38
0.0065
113.8588
0.0056
0.0055
0.0010
165.77
0.0085
197.4386
0.0096
0.0088
0.0008
ND
ND
ND
ND
ND
ND
122.98
0.0063
146.4229
0.0072
0.0060
0.0013
101.81
0.0052
88.57691
0.0043
0.0045
0.0006
215.91
0.0110
139.0502
0.0068
0.0087
0.0022
80.91
0.0041
76.20716
0.0037
0.0042
0.0006
139.93
0.0072
134.5052
0.0066
0.0066
0.0006
0.00
ND
ND
ND
0.0019
0.0032
102.26
0.0052
143.3241
0.0070
0.0059
0.0009
ND
ND
ND
ND
ND
ND
106.66
0.0055
89.66163
0.0044
0.0050
0.0006
ND
ND
ND
ND
ND
ND
ND
ND
130.5928
0.0064
0.0039
0.0034
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
81.64
0.0042
ND
ND
0.0033
0.0029
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
continued
-------
Table 15. (concluded)
RC-DA Mass
10/30/01 Fraction
Compound CAS No. (n<;) 10/30/01
«-tridecane 629-50-5 ND ND
Total Speciated
Total Unspeciated
Total (speciated + unspeciated)b
11005.22 0.476618
12085.01 0.523382
23090.23
Speciated NMOC Mass Emission Factor (mg/kg 4.4157
fuel burned)
Total (speciated + unspeciated) NMOC Mass 9.0266
Emission Factor (mg/kg fuel burned)
a ND = not detected.
b Total NMOC with unknowns is an estimate based on propane only.
Mass
RC-DA Mass RC-DA Fraction Mean
10/31/01 Fraction 11/01/01 11/01/01 Mass
(llg) 10/31/01 pig) (u.g) Fraction Uncertainty
ND ND ND ND ND ND
9237.38 0.4726
10308.06 0.52739
19545.44
2.0432
4.3971
9368.49 0.457679
11101.07 0.542321
20469.56
1.9267
4.3294
5922.41 5450.64
6699.04 6147.19
21035.08 1838.81
2.7952 1.4046
5.9177 2.6926
-------
dilution air have not been exposed to the stationary source matrix. The residence chamber
air represents the sample of the diluted stationary source matrix collected at the end of the
residence chamber. Supporting data for the NMOC/SNMOC analyses are shown in
Appendix K; mass emission factor calculations are shown in Appendix F.
EC/OC, Major Inorganic Ions, and Major Elements
Emissions of EC/OC, major inorganic ions, and major elements are reported in Table 16
as mass fraction of measured PM2 5 mass. Results reported in Table 16 show the following:
Organic carbon (as defined by NIOSH Method 5040) in the PM2 5 was below
detectable limits;
Potassium is found in significant amounts in the recovery boiler emissions and is
indicative of the biomass fuel contribution;
• Nearly all of the potassium in the particulate matter from the recovery boiler is
water-soluble; and
By far, the major components of the particulate matter from the recovery boiler were
elemental sodium and potassium and the ions sulfate and chloride. Organics
constituted a small, nonquantifiable fraction of the particulate matter recovered from
the recovery boiler emissions.
Supporting data are presented in Appendices L, M, and N.
Table 16. Fine Particle Chemical Composition of Emissions from a Recovery Boiler
at a Pulp and Paper Facility
10/30/01 10/31/01 11/01/01 Mean Uncertainty
PM-2.5 Composition (mass fraction)
Organic Carbon
NDa
ND
ND
ND
—
Elemental Carbon
0.0043
0.0003
0.0010
0.0019
0.0021
Elements (mass fraction)
Sodium
0.2952
0.2934
0.2964
0.2950
0.0088
Sulfur
0.1556
0.1742
0.1758
0.1685
0.0112
Potassium
0.0279
0.0262
0.0282
0.0274
0.0011
Chlorine
0.0207
0.0202
0.0216
0.0208
0.0007
Magnesium
0.0005
0.0029
0.0022
0.0003
0.0002
Major Water-Soluble Ions (mass fraction)
Sulfate
0.4528
0.5056
0.5062
0.4882
0.0307
Potassium
0.0239
0.0269
0.0256
0.0255
0.0015
Chloride
0.0196
0.0201
0.0193
0.0197
0.0004
a ND = Not Detected
62
-------
Particle Size Distribution Data
The ELPI system was operated in a "charged" mode on all three test days 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.
Results of the individual runs are summarized in the following tables, diagrams, and
figures. Table 17 lists the collected mass in each of twelve stages for each test day. The
mean particle diameter (Di) of each stage is listed in increasing size order from 42.78 to
8328.12 nm. Also shown are 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 plot
of particle mass by channel is also shown.
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. Plots of particle counts versus size, particle mass versus size, and particle
mass versus stage are shown for each test day (Figures 21, 22, and 23). 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.
Semivolatile Organic Compounds
Thermal evolution analysis of fine PM samples collected on quartz filters indicated there
were no detectable quantities of organic carbon in the PM emitted from the recovery boiler.
Nevertheless, the presence or absence of particle-phase or gas-phase semivolatile organic
compounds in the recovery boiler emissions was checked by GC/MS analysis of solvent
extracts from the quartz filters and PUF plug samples collected during the tests. Results of
these analyses confirmed the absence of quantifiable organic species as shown in Appendix
G in which standard deviations reported for the mass emission factors of individual organic
compounds equal or exceed the average values in every case.
63
-------
Table 17. Particle Size Distribution Data
October 30, 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
1.02xl04
0.00
0.00
0.00
6.02xl02
2.28xl03
2.85 xlO3
1.17xl03
1.74xl02
6.94
8.04x10"'
1.76 xlO"1
M,d mg/m3
0.0001
NDe
ND
ND
0.0019
0.0327
0.1473
0.2703
0.1352
0.0240
0.0135
0.0096
dM/dlog(Dp), mg/m3
4.16X10"4
0.00
0.00
0.00
1.03 xlO"2
1.55X10"1
7.73 xlO"1
1.27
7.42x10"'
1.14X10"1
5.96xl0"2
5.32xl0"2
October 31, 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
0.00
0.00
105.
0.00
26.3
756.
1.09xl03
480.
64.1
1.72
4.63 xlO"1
0.00
M, mg/m3
ND
ND
ND
ND
0.0001
0.0108
0.0563
0.1109
0.0497
0.0060
0.0078
ND
dM/dlog(Dp), mg/m3
0.00
0.00
1.29X10"4
0.00
4.52X10"4
5.13xl0"2
2.95 xlO"1
5.23 xlO"1
2.73 xlO"1
2.84 xlO"2
3.43 xlO"2
0.00
November 1, 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
0.00
0.00
0.00
0.00
0.00
723.
1.15xl03
698.
256.
26.8
8.75
0.00
M, mg/m3
ND
ND
ND
ND
ND
0.0103
0.0596
0.1614
0.1988
0.0927
0.1466
ND
dM/dlog(Dp), mg/m3
0.00
0.00
0.00
0.00
0.00
4.91xl0"2
3.13X10"1
7.61X10"1
1.09
4.42 xlO"1
6.49x10"'
0.00
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
CO
E
1000
o
800
Q.
600
Q
o>
400
o
200
z
o
T3
10
-I 1—I—I I 11 I
100 1000
Dp, nm
10000
CO
£ 1.5
D)
E
^ 10
Q.
Q
O)
0
TJ
1
~o
0.5
Particle Mass vs Size
10
-I—I I 1 I 111
100 1000
Dp, nm
10000
CO
E
o>
E
CO
V)
CO
0.30
0.25
0.20
0.15
0.10
0.05
0
Particle Mass
—i 1 1 r-
2 3 4 5 6 7 8 9 10 11 12
Stage
Figure 21. Plots of Particle Counts vs. Size, Particle Mass vs.
Size, and Particle Mass per Stage for Test Day 1 (10/30/01).
65
-------
Particle Counts vs. Size
E 1500
1000
100 1000
Dp, nm
10000
Particle Mass vs Size
100 1000
Dp, nm
10000
Particle Mass
CO
E
o>
E
0.12
0.10
0.08
0.06
(0
« 0.04
(O
S 0.02
0.00
I I I I I
^~l
1 2 3 4 5
6 7 8 9 10 11 12
Stage
Figure 22. Plots of Particle Counts vs. Size, Particle Mass vs.
Size, and Particle Mass per Stage for Test Day 2 (10/31/01).
66
-------
Particle Counts vs. Size
E 1500
o
1000
Q-
Q
O)
o
"O
500
z
"U
10
100
1000
10000
Dp, nm
Particle Mass vs. Size
CO
E 1.5
O)
£
-C 1.0
Q.
Q
O) 0.5
0
TJ
1 o
T3
10 100 1000 10000
Dp, nm
0.25 i
0.20 -
£ 0.15 -
% 0.10 -
CO
S 0.5 -
Particle Mass
-
_
1 1 1 T i "I
1 2 3 4 5 6 7 8
Stage
9
10
11
12
Figure 23. Plots of Particle Counts vs. Size, Particle Mass vs.
Size, and Particle Mass per Stage for Test Day 3 (11/01/01).
67
-------
Process 02 and C02 Concentrations
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:
• 10/30/01: 02 = 7.4%V; C02 = 11.3%V;
• 10/31/01: 02 = 6.8%V; C02 = 11,9%V; and
• 11/01/01: 02 = 5.9%V; C02 = 13.6%V.
68
-------
14.0
12.0
> 10.0
8.0
6.0
4.0
02 Avg = 7.4%V
m— C02 Avg = 11,3%V
2.0
0.0
o
o
o
o
o
o
o
o
O
O
o
o
o
o
o
O
O
LO
C\J
LO
CvJ
LO
C\J
LO
C\|
LO
OJ
LO
OJ
LO
CvJ
LO
CVJ
LO
CO
a>
6}
O
o
-1-
1—
cSJ
CO
CO
LO
LO
CO
CO
1—
T—
T—
T
T
T
T
1—
T
T
T
T
T
T—
Time
Figure 24. 02 and COz Concentrations for Recovery Boiler No. 5 on Test Day 1 (10/30/01).
-------
16.0
14.0
12.0
>
as
¦V
C
10.0
o
+J
c
a>
u
6.0
c
o
o
4.0
+— Os Avg = 6.8%V
«-C02 Avg= 11,9%V
2.0
0.0
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
CO
o
CO
o
CO
o
CO
o
CO
o
CO
o
CO
o
CO
o
co
cd
o
o
-------
16.0
>
5?
O
o
14.0
12.0
. 10.0
c
0
1
F 8.0
d)
O 6.0
4.0
2.0
0.0
02 Avg = 5.9%V
C02 Avg = 13.6%V
o
CO
o
o
CO
o
CO
CO
o
o
O)
o
CO
aj
o
o
o
CO
o
o
o
CO
o
o
c\i
o
CO
6J
o
o
CO
o
CO
CO
o
o
o
CO
o
o
LO
o
CO
Time
Figure 26. 02 and COz Concentrations for Recovery Boiler No. 5 on Test Day 3 (11/01/01).
-------
72
-------
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, which describe the quality control (QC) checks performed for
each procedure, are listed in Appendix D. QAPPs, MOPs, 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 18 through 25.
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 18.
73
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Table 18. 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;
74
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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 19.
Supporting calibration and QC data are a part of the project file at ERG.
Table 19. 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)
75
-------
Table 19. (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)
76
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Table 19. (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
77
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episodes or sent to another laboratory for further analysis. QC procedures for the Air Toxics
and SNMOC analyses are summarized in Table 20.
Table 20. 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
78
-------
Table 20. (concluded)
Criteria
Quality Control
Acceptance
Corrective
Achieved
Check
Frequency
Criteria
Action
?
Replicate Analysis
All duplicate field
<30% RPD for
Repeat sample
Yes
samples
compounds
analysis
>5 x MDL
Samples
All samples
IS RT ±0.33 min of
Repeat analysis
Yes
most recent
calibration
SNMOC Analysis
System Blank
Daily, following
20 ppbC total
Repeat
Yes
Analysis
calibration check
analysis; check
system for
leaks; clean
system with
wet air
Multiple Point
Prior to analysis
Correlation
Repeat
Yes
Calibration
and monthly
coefficient
individual
(Minimum 5);
(r2) >0.995
sample
Propane Bracketing
analysis; repeat
the Expected Sample
linearity check;
Concentration Range
prepare new
(4-100 ppbC)
calibration
standards and
repeat
Calibration Check:
Daily
Response for
Repeat
Yes
Midpoint of
selected
calibration
Calibration Curve
hydrocarbons
check; repeat
Spanning the Carbon
spanning the
calibration
Range (C2-C10)
carbon range
curve.
within ±30%
difference of
calibration curve
slope
Replicate analysis
All duplicate field
Total NMOC
Repeat sample
Yes
samples
within ±30% RSD
analysis
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 21 through 25.
79
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Table 21. 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 22. 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
80
-------
Table 23. 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
85-15%
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
81
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Table 24. 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
82
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Table 25. 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
83
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84
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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. 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.
3. 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.
4. 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.
5. 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.
6. 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.
7. 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
8. 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.
9. 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
Research and Development, U.S. Environmental Protection Agency, Cincinnati, OH,
January 1999.
85
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10. 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.
11. 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.
86
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
EPA-600/R-03/099a
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 a recovery boiler at a pulp and paper facility using the Kraft
pulping process. Recovery boilers, common to nearly all pulp and paper mills, are usually one of the major
contributors to atmospheric emissions from the mill. Processing wood chips in a pulp mill utilizing the Kraft
process involves digesting the wood in a solution of sodium sulfide and sodium hydroxide. The spent
digestion liquor combined with water used to wash the resulting pulp is called "black liquor." After
undergoing concentration by evaporation to about 65% solids, the black liquor is fed to the recovery boiler
as fuel. Dissolved organics in the concentrated black liquor are combusted in the recovery boiler to yield
heat to generate process steam and to convert sodium sulfate formed in the process back to sodium sulfide
which can be recycled to the digestion step as a reactant. The recovery boiler tested here was equipped
with two parallel electrostatic precipitators with 169,194 linear feet of plate area per precipitator, installed in
the flue gas exhaust ducting. 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 PM25 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
98
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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