&ER&
United States Industrial Environmental Research EPA-600/7-80-040
Environmental Protection Laboratory March 1980
Agency Research Triangle Park NC 27711
Preliminary
Characterization of
Emissions from
Wood-fired Residential
Combustion Equipment
Interagency
Energy/Environment
R&D Program Report
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RESEARCH REPORTING SERIE
Research reports of the Office of Research and Oevelopmer
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3. Ecological Research
4. Environmental Monitoring
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RESEARCH AND DEVELOPMENT series. Reports in this series result from the
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EPA-600/7-80-040
March 1980
Preliminary Characterization of Emissions
from Wood-fired Residential
Combustion Equipment
by
D.G. DeAngelis, D.S. Ruffin,
and R.B. Reznik
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45418
Contract No. 68-02-1874
Task No. 23
Program Element No. 1AB015; ROAP 21AXM071
EPA Project Officer: John O. Milliken
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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PREFACE
The Industrial Environmental Research Laboratory (IERL) of the
U.S. Environmental Protection Agency (EPA) has the responsibility
for insuring that pollution control technology is available for
stationary sources to meet the requirements of the Clean Air Act,
the Federal Water Pollution Control Act, and solid waste legisla-
tion. If control technology is unavailable, inadequate, or un-
economical, then financial support is provided for the develop-
ment of the needed control techniques for industrial and extrac-
tive process industries. Approaches considered include: process
modifications, feedstock modifications, add-on control devices,
and complete process substitution. The scale of the control
technology programs ranges from bench- to full-scale demonstra-
tion plants.
Monsanto Research Corporation (MRC) has contracted with the EPA to
investigate the environmental impact of various industries which
represent sources of pollution in accordance with the EPA's re-
sponsibility as outlined above. Dr. Robert C. Binning serves as
MRC Program Manager in this overall program entitled "Source
Assessment," which includes the investigation of sources in each
of four categories: combustion, organic materials, inorganic
materials, and open sources. Dr. Dale A. Denny of the Industrial
Processes Division at Research Triangle Park serves as EPA Pro-
ject Officer. Reports prepared in this program are of three
types: Source Assessment Documents, State-of-the-Art Reports,
and Special Project Reports.
Source Assessment Documents contain data on emissions from spe-
cific industries. Such data are gathered from literature,
government agencies, and cooperating companies. Sampling and
analysis are also performed by the contractor when the available
information does not adequately characterize the source emissions.
These documents contain information that is used by IERL to decide
whether emissions reduction is necessary.
State-of-the-Art Reports include data on emissions from specific
industries which are also gathered from the literature, govern-
ment agencies and cooperating companies. However, no extensive
sampling is conducted by the contractor for such industries.
Results from such studies are published as State-of-the-Art
Reports for potential utility by the government, industry, and
others having specific needs and interests.
111
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Special project reports provide specific information which is
applicable to a number of source types or has special utility
to EPA as part of a particular source assessment study. This
special project report, "Preliminary Characterization of Emissions
from Wood-Fired Residential Combustion Equipment," was prepared
to provide a general characterization of air emissions from the
residential combustion of wood. In this study, Dr. Ronald A.
Venezia of the Chemical Processes Branch, Mr. Warren Peters of
the Process Technology Branch, and Dr. John 0. Milliken of the
Special Studies Branch served as EPA Task Officers.
IV
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ABSTRACT
This report describes a study conducted to quantify criteria pol-
lutants and characterize other atmospheric emissions from wood-
fired residential combustion equipment. Flue gases were sampled
from a zero clearance fireplace and two air-tight cast iron
stoves (baffled and nonbaffled design). Four wood types were
tested, oak-seasoned and green- and pine-seasoned and green.
Samples were analyzed for particulates, condensable organics,
nitrogen oxides, carbon monoxide, sulfur oxides, organic species,
and individual elements.
Considerable variability was observed in results under different
test conditions. Average emission rates, expressed as grams of
pollutant emitted per kilogram of wood burned, compared favorably
with other studies on residential wood combustion. In most cases,
variations in emission rates could not be correlated with either
combustion equipment or wood type, and were ascribed to systematic
errors or the effect of other variables such as excess air level
or arrangement of wood. Combustion equipment did influence
emissions of CO, NOx and POM's. Emissions of CO and POM's were
higher from wood-burning stoves, while NOX emissions were higher
from fireplaces. The only significant effect of wood type was
the production of larger amounts of organic materials during the
combustion of green pine.
Particulate emissions were determined to be organic in nature
(50% to 80% carbon) and of resinous quality. Condensable organic
emissions were greater in magnitude than the filterable particu-
late emissions.
The report was submitted in partial fullfillment of Contract No.
68-02-1874 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency. The study described
in this report covers the period January 1979 to October 1979.
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CONTENTS
Preface iii
Abstract v
Figures viii
Tables ix
Abbreviations xi
Acknowledgements xii
1. Introduction 1
2. Summary 3
3. Test Program and Procedures 7
Design of test program 7
Test wood 15
Test conditions 16
Sampling methods and equipment 17
Laboratory separation and analysis procedures. . 35
4. Results 44
Emissions summary 44
Energy efficiency testing 66
5. Discussion of Results and Conclusions 68
Effect of combustion equipment 68
Effect of wood type 69
Effect of woodburning cycle 70
Effect of creosote deposition on representative
sampling 71
General remarks and conclusions 71
References 73
Appendices
A. Thermal efficiency test data for the baffled and
nonbaffled woodburning stoves 77
B. Statistical analyses of particulate, condensable
organics, nitrogen oxides, and carbon
monoxide emissions 112
C. POM audit sample results 117
Glossary 143
Conversion Factors and Metric Prefixes 145
vn
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FIGURES
Number Page
1 Sampling point elevations for testing of fireplace
and wood stoves 12
2 Baffled air-tight stove showing primary and secondary
combustion air flow pattern 13
3 Nonbaffled airtight stove showing generalized
combustion-air flow pattern 14
4 EPA Method 5 train proportionality factor (K) versus
stack temperature for several flue gas moisture
contents 19
5 Schematic of EPA Method 5 sampling train with back-up
filter for particulate and condensable organic
material collection . 19
6 Diagram of sampling train for aldehydes 23
7 Diagram of sampling train for POM screening 23
8 Arrangement of sample spots and blank on filter paper
for POM screening 24
9 Schematic of POM train components and sample recovery. 26
10 Schematic of source assessment sampling system .... 28
11 Sample handling and transfer-nozzle, probe, cyclones,
and filter 30
12 Sample handling and transfer - XAD-2 module 32
13 Sample handling and transfer of impinger contents for
those SASS runs made for chemical analysis 33
14 POM train sample analysis scheme for organic species
and POM compounds 39
15 Carbon monoxide concentration in the flue gas from a
wood-burning stove as a function of time 53
16 Flue gas temperature versus time for the nonbaffled
stove burning seasoned oak 70
17 Particulate emission during the combustion of 2.27 kg
of oak 71
Vlll
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TABLES
Number Pac
1 Summary of Emissions for Criteria Pollutants and
POM's from Wood-Fired Residential Combustion
Equipment 5
2 Summary of Overall Test Program . . 8
3 Test Matrix Code Employed for Sample Control .... 10
4 Proximate and Ultimate Analysis of Wood Used in the
Test Program 16
5 Calibration of POM Spot Test 25
6 SASS Train Impinger System for Trace Elements. ... 27
7 Retention Times for Aldehydes 37
8 Combustion Residue Sample Test Conditions and Bio-
assays Performed 43
9 Summary of Emissions for Criteria Pollutants and POM's
From Wood-Fired Residential Combustion Equipment . 45
10 Summary of Test Conditions During Testing of Wood-
fired Residential Combustion Equipment 46
11 Particulate Emissions From Wood-Burning Fireplaces
and Stoves 47
12 Particulate Loading of SASS Train Composition Ex-
pressed as Percent of Total Particulate Catch. . . 48
13 Carbon, Hydrogen, and Nitrogen Content of Particulate
Emissions From Wood-Burning Fireplaces and Stoves. 48
14 Elemental Emissions Obtained From the Nonbaffled
Woodburning Stove 50
15 Condensable Organic Materials Emissions 51
16 Nitrogen Oxide Emissions 51
17 Carbon Monoxide Emissions 52
18 S02 Emissions From the Nonbaffled Wood-Burning Stove 54
19 Low-Molecular-Weight Hydrocarbon Emissions From
Wood-Burning Fireplaces and Stoves 55
20 Mass of Organic Material Recovered for GC/MS Analysis 56
IX
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TABLES (continued)
Number
21 Major Organic Species Emissions 57
22 Organic Loading of POM Train and SASS Train 59
23 POM Emissions 60
24 Aldehyde Emissions 61
25 Flue Gas POM Concentrations by UV Fluorescence Screen-
ing of Grab Samples Versus Conventional Sampling and
Analysis 62
26 Results of Bioassays Performed on SASS and Combustion
Residue Samples 64
27 Definition of Range of EC5o Values 65
28 Summary of Efficiency Test Data Obtained on the
Baffled and Nonbaffled Wood-Burning Stoves .... 67
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ABBREVIATIONS
acf — actual cubic feet
acfh — actual cubic feet per hour
cfm — cubic feet per minute
dscf — dry standard cubic feet
GC-MS — gas chromatograph-mass spectrometer
ICAP — inductively coupled argon plasma
KD — Kuderna-Danish
Nm3 — volume in cubic meters at standard conditions
(i.e., 20°C and 1 atm)
POM — polycyclic organic matter
ppm — parts per million
SASS — Source Assessment Sampling System
SIM — selected ion mode
XI
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ACKNOWLEDGEMENTS
The authors wish to acknowledge the assistance of Dr. Ronald A.
Venezia, Warren Peters, and John O. Milliken, who served as EPA
Task Officers at various stages of this program. Their unified
effort and dedication to program objectives provided the working
environment necessary for expeditious completion of this test
program.
In addition, the authors wish to thank Dr. Edward Bobalek of the
EPA, Lawrence Garrett of the U.S. Forest Service, Dr. Larry John-
son, Bill Kuykendal, and Ray Merrill of the EPA, Dennis Murphy of
Vail, Colorado, William Reefe of the Colorado State Health Depart-
ment, Cedric Samborn of the State of Vermont, Sara Simon of EPA
Region I, and Pierre Pinault of the Canadian Air Pollution Control
Directorate for their helpful input in planning and executing this
test program.
Special acknowledgement is due Dr. Glen Maples, Dr. David Dyer,
Dr. Timothy Maxwell and especially Tom Pruit of the Mechanical
Engineering Department at Auburn University for their hospitality
and assistance during the field sampling effort. Their coopera-
tion and support directly affected the success of this program.
Xll
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SECTION 1
INTRODUCTION
Residential combustion of wood for space heating has found re-
newed interest in this country due to the rising cost of oil and
natural gas and the uncertainty of their availability in the
future. The popularity of burning wood in open fireplaces for
aesthetic reasons has also increased greatly in recent years.
Current estimates indicate that as many as 1.5 million new fire-
places and wood burning stoves are being installed annually.
Existing knowledge of the emissions from the woodburning equip-
ment indicates that this trend poses a potential environmental
problem. This potential problem has been already realized in
communities, where a high concentration of wood-burning units has
caused local ambient air quality problems.
Only a limited amount of emissions data exists on residential
wood combustion; however, these data indicate a high variability
in emissions and suggest the possibility of potential hazardous
levels of certain pollutant species. Various organic species
including POM (polycyclic organic material) compounds are prob-
ably the most environmentally significant pollutants from resi-
dential wood combustion; although previous emission measurements
have done little to identify or quantify them.
Because of the rapid growth of wood-burning for primary home
heating and aesthetic purposes, both regional and national EPA
officials have become concerned over the potential environmental
impact of large-scale residential combustion of wood. Large-
scale residential combustion of wood could produce a dramatic
adverse effect on local air quality, and the EPA is responsible
for averting or minimizing such effects. The major problem con-
fronting the EPA has been the absence of an adequate data base
upon which to make policy decisions.
The objective of this special project was to determine the physi-
cal and chemical characteristics of airborne emissions from wood-
fired residential combustion equipment. These characterization
data are necessary to supplement existing data on wood combustion
so that more objective estimates of the impact of this source on
ambient air quality can be made. The sampling program included
the collection of sufficient field data to identify and quantify
pollutants not previously measured and to supplement the data on
known pollutants.
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One fireplace and two woodburning stoves were tested while burn-
ing four types of wood. Exit gases were measured for particu-
lates, condensable organics, sulfur dioxide (SO2), nitrogen
oxides (NOX), carbon monoxide (CO), organic species including
polycyclic organic materials (POM's), and individual elements.
Bioassay tests were also conducted on the stack emissions and
bottom ash. Testing was performed at Auburn University, Auburn,
Alabama, during March and April 1979, and samples were analyzed
later in the year.
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SECTION 2
SUMMARY
This report presents the results of a test program conducted by
the U.S. Environmental Protection Agency, Monsanto Research
Corporation, and Auburn University to characterize emissions from
wood-fired residential combustion equipment. The program was
undertaken because of the increased usage of wood for home heat-
ing and aesthetic purposes and because of the potential environ-
mental impact from increased emission levels. Although a limited
amount of testing has been done by others on this source type,
those tests have not thoroughly characterized emissions of
organic species, which have the greatest potential for adverse
effects.
In this program emission testing was conducted on a zero-clearance
fireplace and two air-tight cast iron stoves. The air-tight
stoves were of common design; one was baffled to increase flue
gas retention. The units were larger varieties capable of accept-
ing about 15 kg of wood per charge. Combustion conditions were
maintained in the air-tight stoves by manipulation of the air
inlet vents until combustion was not excessive (flames reaching
into the exhaust pipe) but also not starved for air (no visible
flame present). Stack temperature was also used to aid in this
control. The wood burning rate ranged from 6.0 kg/hr to 8.4 kg/
hr. The fireplace was operated with glass doors open and damper
fully open. The wood burning rate in the fireplace ranged from
9.6 kg/hr to 11 kg/hr.
Thermal efficiencies for air-tight stoves have been reported to
be as high as 80%; however, in this program the two units tested
were operated in the range of 40% to 60% thermal efficiency
(useful heat recovered, divided by the heat content of the wood).
The fireplace employed was tested and found to have a maximum
thermal efficiency of about 23%. This study was conducted under
conditions which approximated optimum thermal efficiency for the
fireplace. Tests were conducted on each unit burning four vari-
eties of wood. Both yellow pine and red oak were obtained (green
and seasoned) locally in Auburn, Alabama, where testing was
conducted.
Quantitative emissions testing employed EPA methods from the
Federal Register to measure sulfur oxides (SOX), nitrogen oxides
-------
oxides (NOX), and carbon monoxide (CO). EPA Method 5 was used to
measure both filterable particulate matter and condensable organ-
ics. Semiquantitative testing was performed using modified EPA
methods and a Source Assessment Sampling System (SASS train) to
measure POM's, organic species, and trace elements. Volatile
hydrocarbons were measured by GC/FID, and aldehydes were collected
by midget impingers containing sodium bisulfite and analyzed by
GC. Samples for bioassay were collected with the SASS train. A
technique to screen for POM compounds was also tested in this
program.
Average emission rates, expressed as grams of pollutant emitted
per kilogram of wood burned, for the three combustion devices and
four test woods, as measured in this program, are presented in
Table 1 for criteria pollutants and total POM's. Results indicate
that the air-tight stoves have significantly higher emission rates
for CO and POM's, while NOX emissions were greater from the fire-
place. Wood type did not appear to be a major variable, although
combustion of green pine produced higher levels of organic pollu-
tants. There are many significant variables in the residential
wood combustion process, and the results of this program only
represent one set of conditions. However, they do represent a
significant portion of the source population. Indications are
that wood-burning rate is a variable worthy of future study.
Other conclusions and observations were made during this test pro-
gram. Filterable particulate emissions were determined to be
organic in nature (50% to 80% carbon) and had resinous qualities.
Condensable organic emissions were greater in magnitude than the
filterable particulates, often by a factor of two. These two
emission species are sometimes reported collectively as total
particulate emissions. Sulfur oxide emissions were found to be
quite low (approximately O.2 g/kg) because of the low fuel sul-
fur content.
Elemental emission rates, expressed as grams of pollutant emitted
per kilogram of wood burned, as determined from one SASS train
run, were generally on the order of 1 mg/kg or less. These values
are two or three orders of magnitude lower than typical elemental
concentrations in wood, indication that most of the wood elemen-
tal content is not released to the atmosphere upon combustion.
Flue gas temperature measurements indicated that the combustion
process was cyclic in nature and that certain emissions may be
affected by this. Carbon monoxide emissions were found to vary
by more than an order of magnitude during burning of one charge
of wood. Nitrogen oxides, on the other hand, were fairly stable
and unaffected by changing combustion conditions. It is expected
that organic emissions, or those directly related to organic
emissions (such as particulates), will follow a pattern similar
to that of the CO emissions; however, this was not quantified in
this program.
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TABLE 1.
SUMMARY OF EMISSION RESULTS FOR CRITERIA POLLUTANTS AND
POM's FROM WOOD-FIRED RESIDENTIAL COMBUSTION EQUIPMENT
Wood burning
device
Fireplace
Fireplace
Fireplace
Fireplace
Baffled stove
Baffled stove
Baffled stove
Baffled stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Wood type
Seasoned oak
Green oak
Seasoned pine
Green pine
Seasoned oak
Green oak
Seasoned pine
Green pine
Seasoned oak
Green oak
Seasoned pine
Green pine
matter
2.3
2.5
1.8
2.9
3.0
2.5
3.9
7.0
2.5
1.8
2.0
6.3
(0.13)
(0.19)
(0.10)
(0.21)
(0.17)
(0.19)
(0.21)
(0.51)
(0.14)
(0.13)
(0.11)
(0.46)
Condensable
organics
6.3 (0.35)
5.4 (0.40)
5.9 (0.32)
9.1 (0.67)
4.0 (0.22)
3.8 (0.28)
4.1 (0.23)
12 (0.88)
6.0 (0.34)
3.3 (0.25)
5.6 (0.31)
10 (0.74)
Emission rate, g/kqa (iiq/j)&
Volatile
hydrocarbons NOx SO*
19 (1.1) 2.4
1.9
1.4
1.7
0.4
0.7
2.8 (0.15) 0.5
0.8
0.4
0.3 (0.02) 0.5
0.2
3.0 (0.22) 0.4
(0.13)
(0.14)
(0.08)
(0.13)
(0.02)
(0.05)
(0.03)
(0.06)
(0.02) 0.16 (0.009)
(0.04)
(0.01) 0.24 (0.013)
(0.03)
co
30
22
21
15
110
120
270
220
370
91
150
97
(1.7)
(1.6)
(1.2)
(1.1)
(6.2)
(9.0)
(15)
(16)
(21)
(6.8)
(8.2)
(7.1)
POM
0.025 (0.0014)
0.036 (0.0026)
0.21 (0.012)
0.37 (0.020)
0.19 (0.011)
0.32 (0.024)
p
Blanks indicate no data were obtained.
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In most cases over 50% of the organic material collected during
sampling was nonchromatographable by GC/MS. This nonchromato-
graphable material was indicated to be largely high molecular
weight organic acids and high molecular weight fused ring aro-
matics (e.g., POM's). Over 75 organic compounds were identified
upon characterization of the chromatographable organic material
present in the flue gas; 22 of these were POM's, while the re-
maining organic materials identified were dominated by aldehydes,
furans, phenols, and naphthalenes.
The POM screening test conducted in the field was found to com-
pare fairly well with more quantitative measurements. Because
the field technique is rapid and somewhat subjective, results are
determined as a range of POM concentrations. These ranges
varied from encompassing the quantitative value to differing by
a factor of 15 from the more quantitative results.
Twelve SASS runs were made to provide samples for bioassay: one
for each test condition. Each SASS run resulted in two samples
for bioassay: The first consisted of the methylene chloride
extract of all front-half material (cyclone and filter catches
and wash residues). The second sample submitted consisted of the
methylene chloride extract of the XAD-2 resin and the methylene
chloride rinse of the XAD-2 module. Twelve samples of each were
submitted for Salmonella/microsome mutagenesis assay (Ames Test)
and clonal toxicity (CHO) assay. Combustion residue samples
(ash) were also collected from each test condition, and eight out
of twelve were submitted for bioassay. All of the SASS train
samples showed mutagenic activity (with the Ames test) and also
exhibited high to moderate toxicity by the CHO assay. Ash sam-
ples showed no mutagenic response and exhibited either no toxi-
city or low toxicity.
Because the significant pollutants from wood-burning are related
to inefficient combustion, their emission levels may be sensitive]
to variables in mode of operation such as fuel charge, physical
arrangment of fuel and air-to-fuel ratio. Further studies on
residential wood burning would be useful to quantify the effects
of these variables and other design variables. Design modifica-
tions and standards for operation should be studied as a means
of improving combustion and reducing emissions.
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SECTION 3
TEST PROGRAM AND PROCEDURES
DESIGN OF TEST PROGRAM
The objectives of this program were to 1) identify emissions
from residential wood-fired combustion equipment not previously
characterized, 2) measure emission rates of all major emissions
from these wood-fired units, and 3) conduct bioassay analyses on
the emissions. Table 2 presents a summary of the test program,
including the major test variable and the types of samples that
were collected and analyzed.
Prior to this study five other testing programs had been com-
pleted to measure emissions from residential wood-fired combus-
tion (1-5). Most of those programs concentrated on emissions of
particulate matter; although some data were obtained on carbon
monoxide (CO) and hydrocarbon emissions. In one program, three
measurements of POM compounds were made; in another program, the
presence of carbonyls, phenols, organic acids, and nitrogen ox-
ides (NOX) was established. Only two of these studies employed
(1) Snowden, W. D., D. A. Alguard, G. A. Swanson, and W. E.
Stolberg. Source Sampling Residential Fireplaces for Emis-
sion Factor Development. EPA-450/3-76-010, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina,
November 1975. 173 pp.
(2) Source Testing for Fireplaces, Stoves, and Restaurant Grills
in Vail, Colorado (Draft). Contract 68-01-1999, U.S. Environ-
mental Protection Agency, Denver, Colorado, December 1977.
26 pp.
(3) Butcher, S. S., and D. I. Buckley. A Preliminary Study of
Particulate Emissions from Small Wood Stoves. Journal of
the Air Pollution Control Association, 27(4):346-347, 1977.
(4) Clayton, L., G. Karels, C. Ong, and T. Ping. Emissions from
Residential Type Fireplaces. Source Tests 25C67, 26C67, 29C67,
40C67, 41C67, 65C67, and 66C67, Bay Area Air Pollution Control
District, San Francisco, California, 31 January 1968. 68 pp.
(5) Butcher, S. S., and E. M. Sorenson. A Study of Wood Stove
Particulate Emissions. Journal of the Air Pollution Control
Association, 29 (7):724-728, 1979.
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TABLE 2. SUMMARY OF OVERALL TEST PROGRAM
oo
Combustion
equipment
Test Airtight
Condi- Fire- stove Typ*
tion olace No. 1 No. 2 Oak Pine
A-l x x
A-l x x
A-2 x x
A-2 x x
A-3 x x
A-3 x x
A-4 x x
A-4 x x
B-l x x
B-l x x
B-2 x x
B-2 X x
B-3 x x
B-3 * x
B-4 x x
B-4 x x
C-l x x
C-l x x
C-2 x x
C-2 x x
C-3 x x
C-3 x x
C-4 x x
C-4 x x
Mood
Moisture
Low
(seasoned)
x
X
X
X
X
X
X
X
X
X
X
X
level
High
(green)
x
x
X
X
X
X
X
X
X
X
X
X
Front-
half
partic-
ulates
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Samples collected and analyzed
EPA Method 5 SASSb
High train
molecular- samples c
Conden- weight for Volatile
sable organic chemical hydro- Alde-j
or^anics POM speciation assay carbon hydes
x x
x x x x
X
X
X X
X
X X
X
X
X
X X
X XX
X
X
X X
X
X XX
X
X X
X XXX
(continued)
POM train employing EPA Method S equipment supplemented with XAD-2 resin trap.
Particulates by size (<1 pm. 1 pm to 3 ym, 3 pm to 10 pm, >10 um), organic species, POM, trace elements.
CGC/FID.
Midget impinger train; formaldehyde by Schiff's test colorimetric method; other aldehydes by GC/FID.
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TABLE 2 (continued)
Combustion
equipment
Test Airtight
condi- Fire- stove Type
tion place No. 1 No. 2 Oak Pine
A-l x x
A-l x x
A-2 x x
A-2 x x
A- 3 x x
A- 3 x x
A-4 x x
A-4 x x
B-l x x
B-l x x
B-2 x x
B-2 x x
B-3 x x
B-3 x x
B-4 x x
B-4 x x
C-l x x
C-l x x
C-2 x x
C-2 x x
C-3 x x
C-3 x x
C-4 x x
C-4 x x
Samples collected and
Wood
Moisture
Low
(seasoned)
x
X
X
X
X
X
X
X
X
X
X
X
level
High
(green)
x
x
X
X
X
X
X
X
X
X
X
X
NOx6
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
rof
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
°a'g
C02S
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
SASS
train
C, H, and samples^
N of par- for
ticulate" bioassay
x
x
X
X X
X
X
X
X X
X
X
X X
X
X
X
X
analyzed
POM .
screening
x
x
X
X
X
X
X
X
X
X
X
X
Ash
samples
for
bioassay SOa
x
x
X
X
X
X
X
X
X x
X
X X
X
6EPA Method 7.
Orsat for CO at >1,000 ppm; Drager tube for CO at <1,000 ppm.
q
3Orsat.
Perkin Elmer elemental analyzer.
Particulates by size (<1 ym, 1 pm to 3 Mm, 3 pm to 10 Mm, >10 pm). Samples collected for bioassay testing of emission
species by EPA.
j
POM screening performed on two types of samples: POM samoles collected via the use of the POM train and POM samples
collected via a midqet impinger train containing methvlene chloride.
-------
standard sampling and analytical methods approved by the EPA.
Results of these studies indicated that emissions from the resi-
dential combustion of wood are highly variable and additional
data are necessary to adequately perform an environmental impact
assessment. The available data on POM emissions, although limi-
ted, indicate that this pollutant may be emitted at a rate sig-
nificantly higher (on a per Joule basis) than from residential
oil or gas combustion.
Two air-tight wood burning stoves and one zero-clearance fire-
place were selected for testing in this program. Although many
varieties of residential wood-burning equipment exist, the de-
signs chosen for testing represent a significant portion of the
equipment population. Because wood is such a highly variable
fuel, an in-depth assessment of representative fuel woods and
the resulting combustion emissions was beyond the scope of this
program. The wood types chosen for testing - red oak (green and
seasoned) and yellow pine (green and seasoned) - although not
available in all regions of the country, are representative of
the range of wood types burned in this source category.
Table 3 presents the test matrix code employed in this program.
The code uses a letter to designate the combustion equipment
tested and a number to designate the wood type. This code had
its greatest utility in identifying and tracking test runs,
field samples, data sheets, sample logs, analysis requests and
analytical results.
TABLE 3. TEST MATRIX CODE EMPLOYED FOR SAMPLE CONTROL
Combustion
equipment
Fireplace
Baffled stove
Nonbaffled stove
Seasoned
oak
A-l
B-l
C-l
Wood
Green
oak
A- 2
B-2
C-2
type
Seasoned
pine
A- 3
B-3
C-3
Green
pine
A- 4
B-4
C-4
Test Site and Facilities
Investigations into the emissions from wood-burning stoves and
fireplaces were conducted at the wood-burning laboratory of
Auburn University. This test site is operated by the Department
of Mechanical Engineering at Auburn with funds supplied by the
Department of Energy, the Fireplace Institute, and private
manufacturers.
This facility has over 15 different wood combustion devices avail-
able for testing. Thermal efficiency testing can be performed
either by the flue gas analysis technique or by calorimeter room.
10
-------
The calorimeter room was not available for this study. Two elec-
tronic balances were, however, available which can support com-
bustion equipment for wood burning rate determination. A com-
puter terminal was installed at the test site to be used for data
logging, storage and manipulation, and thermal efficiency determi-
nation. Typical computer outputs are shown in Appendix A.
Emission testing was facilitated by the large work area available
and support facilities such as tables, scaffolding, ample elec-
trical circuits, power tools, hardware, chilled running water for
impinger trains, lab benches, a refrigerator for sample preserva-
tion, and sinks.
The staff at Auburn provided technical assistance in setting up
and carrying out this program, provided combustion units and
supporting material, and conducted thermal efficiency tests paral-
lel to emission testing.
Combustion Equipment
The testing program was designed to measure the emissions from
typical wood-fired combustion equipment burning wood types repre-
sentative of the varieties available in the United States. The
selection of combustion equipment was determined by the repre-
sentativeness of the equipment based on current trends. Accord-
ing to the U.S. Bureau of the Census, 452,000 new homes were
built in 1975 with fireplaces, and about 550,000 wood-burning
stoves were shipped by manufacturers (6, 7). A large variety of
stoves encompassing several basic combustion-chamber designs are
available on the market. Because the emphasis is now on energy
efficiency, air-tight metal stoves, which are claimed to be 50%
to 70% energy efficient, are becoming very popular. As the
figures indicate, fireplaces remain popular either for aesthetic
reasons or out of ignorance of their inefficient heat recovery.
The fireplace chosen for study was a sheet metal zero-clearance
type equipped with glass doors and a forced-air circulation sys-
tem to distribute heat away from the firebox. All tests on the
fireplace were performed with the glass doors open and forced air
fans on. The firebox was lined with 0.025 m firebrick and the
flue damper was nonpositioning, i.e., it was either wide open or
fully closed. The fuel bed was supported by a cast iron grate
elevating the fire about 0.1 m from the bottom of the firebox.
Flue gases from the fireplace exited from the top of the firebox
(6) Construction Report; Bureau of the Census Series C26; Charac-
teristics of New Housing: 1976. U.S. Department of Commerce,
Washington, D.C., July 1977. 77 pp.
(7) Current Industrial Reports, Selected Heating Equipment.
Bureau of the Census MA-34N(75)-1, U.S. Department of Com-
merce, Washington, D.C., July 1976. 6 pp.
11
-------
through an 0.2 m (8-in.) metal duct. This duct was made from the
inner wall of a triple-wall stove pipe which had the middle and
outer wall removed to facilitate sampling. The flue pipe dis-
charged into a roof vent approximately 4 meters above the top of
the firebox. This method of discharge reduced the effect of wind
on the combustion air draft. Figure 1 shows the location of the
various sampling points relative to the top of the firebox.
These points were essentially the same for sampling of the wood-
burning stoves.
DISCHARGE (ELEV. 4.0m)
VELOCITY IELEV. 3.2m)
• EPA-5 AND POM TRAINS (ELEV. 12 m)
• COy 0? CO. GC/FID BAG SAMPLE (ELEV. 2.1 m)
•SASS TRAIN 11.8m)
• POM SCREENING. N0x>ALDEHYDES. S02 (ELEV. 1.7 m)
-(ELEV. 1.0m)
NOTE: aOOR ELEVATION 0 m
Figure 1.
Sampling point elevations for testing
of fireplace and wood stoves.
The two wood burning stoves tested were of the popular air-tight
variety. One was baffled and the other was nonbaffled. Both
were cast iron combustion units with a flat upper surface avail-
able for cooking but not often employed for that purpose. Com-
bustion air is provided in these units by a passive draft system
in which room air enters the firebox through adjustable vents in
the door located at the front of the unit.
The baffled stove, shown in Figure 2 (8), was an air tight, two-
level, boilerplate radiant heater. The firebox, which is made of
steel plate, was 0.69 m long, 0.46 m high, and 0.44 m wide, and
(8) Dyer, D. F., T. T. Maxwell, and G. Maples. Improving the
Efficiency, Safety and Utility of Woodburning Units, Volume 3
Quarterly Report No. W.B.-4. Contract ERDA EC77SO5552,
Department of Energy, Washington, D.C., September 15, 1978.
12
-------
aUEPIPE
U)
0.0
1
n
^j
0.15m
L~I]
^-
i
\
E
^
c
\
-o
m -i.-
n
IT
o*
i
1 -
1
J
lVv XBAFFLE
1 ^^--^^: SECONDARY Al R ABOVE Fl RE
\
s^
fr-
xPR|f
ll II II
WRY AIR BELOW FIRE
i n n
n M m
1
\
\
I
®N o=
AIR REGULATORS
t r^
y J
=» ©
© ©f
« 0. 44 m »
SIDE VIEW
FRONT VIEW
Figure 2. Baffled air-tight stove showing primary and
secondary combustion air flow pattern (8).
-------
was lined with firebrick. The lower level of the top extended
into the interior of the stove to form a baffle that required the
smoke and exhaust gases to flow around to exit the unit. In
addition, the flue pipe extended into the upper chamber created
by the baffle. Thus, the exhaust from the combustion zone had to
travel around two baffles in an "S" shaped flow pattern. Both
primary and secondary combustion air entered through registers in
the cast iron door. The baffled stove is somewhat unique in that
it has three air regulators in the door rather than two as is
common among other stoves of this type. The lower two air regu-
lators are intended to supply primary combustion air while the
upper inlet is intended to supply secondary air. This stove
weighs approximately 200 kg (450 Ib).
The nonbaffled stove is an air-tight, boiler plate radiant heater
The combustion zone dimensions are approximately 0.61 m high,
0.4 m wide and 0.71 m long. Two air inlets are located on the
door of the stove. This unit, shown in Figure 3, weighs approxi-
mately 160 kg (350 Ib) . This unit was also lined with firebrick.
o.«m
FRONT VIEW
-
ADJUSTABLE^.
AIR INLETS
!
o
^^
i
-0 0
i
i
\
~K4rt^4Hl
(• 0.33m — »j i
* 0.42m -*]
T
0.36m
1
T
II
62m
*• 0.09m
EXHAUST-*-
SIDE VIEW
015ml
• 0.33m —
\
l^
\
t\
\
v
j
rr
\
\,
\
Ss.
— . —
-a 38m »\
t
0.16m
v.
-X,
^—
U
'"'^FURNACEAIR
Figure 3. Nonbaffled airtight stove showing generalized
combustion-air flow pattern (8).
14
-------
Each unit employed a 0.15 m (6-in.) flue pipe which discharged
emissions into a roof vent as did the fireplace. The stoves
were mounted on an electronic balance during testing to monitor
wood combustion rates and to facilitate heat efficiency testing
by Auburn University. The effect of sampling equipment on the
balance readings was negligible because the sampling equipment
was suspended by cables from piping and structural beams.
Each wood-burning stove was capable of accepting up to about
14 kg of split firewood. Heat release rates during testing
ranged from 63,300 KJ/hr to 150,000 KJ/hr, while measured heat
efficiency3 ranged from 22% to 52%. The resultant rates for
delivery of useful space heat are probably more representative
for houses using wood as the primary heat source vis-a-vis
secondary or auxiliary space heating. Under different conditions
of operation these values could have had even greater variance.
TEST WOOD
The selection of wood to be burned in the test equipment was
based on availability and range of resin content. Oak and pine
were chosen at the high and low moisture conditions represented
by green wood and seasoned wood. Moisture content and heat
release rate have been suggested as the two most important vari-
ables of the fuel wood that affect burning rate and, in turn,
emission rates. Although the heating value (J/kg) of pine is not
much different from that of oak, the heat release rate of pine is
much greater because of its lower density and higher resin
content.
Auburn University obtained the test wood from local sources. The
green wood was cut several weeks prior to testing, and the sea-
soned wood was cut about 4 to 6 months prior to testing. The
wood was obtained about 1 week before testing began and was
stored indoors at the wood-burning laboratory.
The test wood was cut to lengths of about 0.5m which occupied
most of the length of the wood stove combustion chamber. Pieces
larger than about 0.08 m in diameter were split to approximately
that size. Samples of the unsplit wood were submitted to Indus-
trial Testing Laboratory in St. Louis, Missouri, for proximate
and ultimate analysis. The results of these tests are presented
in Table 4. Moisture content is based on the wood as received
and not on oven-dried wood as is often the case for data pre-
sented in the literature on wood. Moisture content was the only
parameter that drastically changed from one sample to another,
with green wood having 27% to 30% moisture and seasoned wood only
4% to 5% moisture. Relative to values reported in the literature
Useful heat recovered divided by the heat content of the wood
burned.
15
-------
(9, 10), the moisture content of the seasoned wood falls at the
low extreme. Other parameters varied only slightly on a dry
basis. Sulfur was found in the wood at a level of about 0.01%,
which is approximately the detection limit of the sulfur determi-
nation technique.
TABLE 4. PROXIMATE AND ULTIMATE ANALYSIS
OF WOOD USED IN THE TEST PROGRAM
Wood com-
position
Moisture,9 \
Volatile
matter, \
Fixed
carbon, %
Ash, %
Sulfur, %
Carbon , %
Hydrogen, %
Nitrogen, %
Oxygen, %
Heating0
value ,
MJAg
Btu/lb
Seasoned
As
received
4.25
82.72
12.28
0.75
0.01
45.89
6.29°
-------
Thus 6 kg to 14 kg of wood was charged to each stove, and 4.5 kg
to 10 kg was charged to the fireplace. Several charges of wood
were allowed to burn before testing began to allow the equipment
to reach thermal equilibrium and to establish a bed of coals in
the combustion device. Initial startup, although possibly gener-
ating significant emissions, was not studied because of the
difficulty in quantifying its contribution to the total burn
covering at least several wood charges.
Combustion conditions were maintained in the air-tight stoves by
manipulation of the air inlet vents until combustion was not
excessive (flames reaching into the exhaust pipe) but also not
starved for air (no visible flame present). Stack temperature
was also used to aid in this control. The wood burning rate
ranged from 6.0 kg/hr to 8.4 kg/hr. The fireplace was operated
with glass doors open and damper fully open. The wood burning
rate in the fireplace ranged from 9.6 kg/hr to 11 kg/hr. These
burning rates are believed to be representative for wood stoves
used for primary heating in the northern United States and for
fireplaces. Wood stoves used for auxilary heating or for primary
heating outside the north will have lower burning rates.
Emission sampling was conducted after at least four charges of
wood had burned. Grab samples, as in the case of NOx and CO,
were taken at various stages of the burn cycle and from different
wood charges. Integrated sampling, such as EPA-5, POM train, and
SASS train sampling, was conducted during the combustion of a
minimum of one charge of wood and often during combustion of two
or more wood charges. Sampling equipment operation was therefore
maintained during the charging of a load of wood to the combus-
tion equipment. No other disturbances to the fuel bed took place
except for an occasional manipulation of the fuel bed to prevent
smothering the fire, and this was kept to a minimum. Ash or
combustion residue was not removed during testing but remained
in the combustion equipment overnight to allow combustion to
approach completion and to permit handling of the ash for sample
collection.
SAMPLING METHODS AND EQUIPMENT
Sampling methods and equipment were selected on the basis of the
type and quality of data required, the physical arrangement of
the test site, and the nature of the combustion process. The
specific techniques employed for collecting each pollutant in
this program are described below.
Particulate and Condensable Organics
The procedure and equipment used for the quantitative particulate
collection meet specifications outlined in Method 5 of the Federal
17
-------
Register (11). Previous studies on coal-fired residential heating
devices have indicated a flat velocity profile across the stack
(12). Because of the small stack diameters (0.15 m and 0.20 m) ,
single-point sampling was used to determine the mass emission
rates with the probe tip placed in the center of the exhaust stacl
Mass emissions were collected over a period of 45 min to 120 min,
corresponding to sampling volumes of approximately 0.6 Nm3
(normal cubic meters) to 1.7 Urn3 of stack gas. Emissions from
the airtight stoves produced high mass loadings and resulted in
the shorter sampling times and collection of less than the recom-
mended sample volume of 1.7 Mm3. Sampling was initiated after
several charges of wood had burned and continued through at least
one additional charge of wood.
Probe tip selection was based on the desire to have extended
sampling times and the need for isokinetic sampling. Because of
the cyclic nature of the combustion process, the temperature at
the point of sampling varied by as much as 280°C. Rather than
use average stack temperatures to determine sampling parameters
such as the K factor3 (see reference 13 for the function of the
K factor), the temperature at each reading (5-min intervals) was
used to determine a new < factor. Figure 4 is a reproduction of
a graph employed in the field for K factor determination.
Particulate emissions were also measured with the POM train and
the SASS train discussed later in this section.
Condensable organic material was determined from the back-half
portion of the Method 5 sampling train (Figure 5) . The back hall
of the train consists of water-filled impingers that collect most
materials passing through the front-half filter. This material
ic factor is a proportionality factor relating stack velocity
measurement pressure differential and gas meter orifice pressure
differential to obtain isokinetic sampling.
(11) Environmental Protection Agency - Part II - Standards of
Performance for New Stationary Sources - Revision to Refer-
ence Method 1-8. Method 5 - Determination of Particulate
Emissions from Stationary Sources. Federal Register,
42(160):41776-41782, August 1977.
(12) DeAngelis, D. G., and R. B. Reznik. Source Assessment:
Coal-Fired Residential Combustion Equipment Field Tests.
EPA-600/2-78-004c, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, June 1977. 81 pp.
(13) Yergovich, T. W. Development of a Practical Source Samplini
Slide Rule. Journal of the Air Pollution Control Associa-
tion, 26(6):590-592, 1976.
18
-------
350
300
250
200
ce
o
I 150
100
50
PROBE TIP DIAMETER • O.OZ03m
PITOT TUBE COEFFICIENT • 0.79
ORIFICE METER COEFFICIENT • 1.851
FlUE GAS MOISTURE • 10%
X
FLUE GAS MOISTURE -15%
100 200 300 400 500
STACK TEMPERATURE. °C
600
Figure 4. EPA Method 5 train proportionality factor
(K) versus stack temperature for several
flue gas moisture contents.
THERMOMETER
IMPINCER TRAIN
OR BACKHALf HlItR THERMOMHER
TEMPERATURE
PROBE
—i*}—L
MAIN VALVE
CHECK VALVE
VACUUM LINE
Figure 5. Schematic of EPA Method 5 sampling train with
back-up filter for particulate and condensable
organic material collection.
19
-------
is sometimes considered a part of the total sample. In addition,
a back-up filter was inserted between the third and fourth
impinger. A previous study on fireplase emissions employing a
back-up filter found that a significant mass collected on this
filter (1). This same study showed that the back half of the
Method 5 train and back-up filter contained from 50% to 80% of
the total material collected when sampling fireplace emissions.
This material has been observed to be an organic-type residue.
In this study the material collected in the back half of the EPA
Method 5 train accounted for 54% to 76% of the total mass col-
lected; 12% to 39% of the back-half mass was collected on the
back-up filter.
The impinger solutions were observed to range from yellow to
light brown in color, while the back-up filter catches were con-
sistently yellow. No phase separation was observed. Connecting
glassware was dotted with brown resinous material which proved
difficult to recover. Final cleaning of glassware was accom-
plished by soaking in acetone.
Sulfur Oxides
Although sulfur oxide emissions were expected to be low from
residential wood burning devices, two measurements employing EPA
Method 6 were made (14). Analysis of the test wood indicated
little or no variation in sulfur by wood type. Emission tests
for SO2 were run on combustion of seasoned oak and seasoned pine
in an airtight stove. Fireplace emissions of S02 would be less
concentrated and more difficult to detect.
Nitrogen Oxides
EPA Method 7 was employed, as specified in the Federal Register
(15), to determine emissions of nitrogen oxides. Because this is
a grab sample method, six samples were taken at each test condi-
tion. These were collected over a period of time long enough to
obtain samples during the burn of several wood charges and repre-
senting various stages of the burning cycle. Each sample con-
sisted of about 2 L of flue gas collected over 30 s.
(14) Environmental Protection Agency - Part II - Standards of
Performance for New Stationary Sources - Revision to Refer-
ence Method 1-8. Method 6 - Determination of Sulfur Dioxide
Emissions from Stationary Sources. Federal Register,
41(111):23083-23085, August 1977.
(15) Environmental Protection Agency - Part II - Standards of
Performance for New Stationary Sources - Revision to Refer-
ence Method 1-8. Method 7 - Determination of Nitrogen
Oxide Emissions from Stationary Sources. Federal Register,
42(160):41784-41796, August 1977.
20
-------
Carbon Monoxide, Oxygen, and Carbon Dioxide
Concentrations of carbon monoxide (CO), oxygen (O2), and carbon
dioxide (C02) in the flue gas were determined as directed under
EPA Method 3 employing the Orsat technique (16). These measure-
ments were performed as part of the heat efficiency testing con-
ducted by Auburn University. Ten grab samples were collected for
analysis during the burning of one charge of wood. These values
provide a profile of the change in flue gas composition during a
burning cycle, and their average provides the average CO composi-
tion for determination of emission rates, expressed as grams of
pollutant emitted per kilogram of wood burned.
Because the fireplace employs excessive dilution air, the flue
gas concentrations of CO were be-low the detection limit of the
Orsat technique. Therefore, Tedlar bag samples were collected
over 15-min to 30-min intervals and analyzed with Drager tubes
(17). Drager tubes are normally used in workplace environments
where it is necessary to determine very small concentrations of
CO in ambient air with maximum reliability in a short time.
Tubes are packed with a reagent that reacts when contacted with
CO to produce a color change. The volume of reagent changing
color indicates the volume of CO present in a fixed volume of
sample.
The Drager tube employed (carbon monoxide 10/b) contains a pre-
cleanse layer that retains interfering gases (e.g., petroleum
distillates, benzene, hydrogen sulfide). Acetylene and hydrogen
in concentrations greater than 50% are indicated as CO but were
not a problem in this program. The detection range of the tube
was from 100 parts per million (ppm) to 3,000 ppm with a relative
standard deviation of 10% to 15% (17).
Low Molecular Weight Hydrocarbons
The Ci-Ce hydrocarbon emissions were sampled and analyzed on site,
Flue gas samples were collected in Tedlar bags for analysis by
gas chromatography. The samples were analyzed by the Varian 1400
gas chromatography-flame ionization detector with temperature
programming capabilities. Breathing air and high purity hydrogen
(16) Environmental Protection Agency - Part II - Standards of
Performance for New Stationary Sources - Revision to Refer-
ence Method 1-8. Method 3 - Gas Analyses for Carbon
Dioxide, Excess Air, and Dry Molecular Weight. Federal
Register, 42(160):41768-41771, August 1977.
(17) Detector Tube Handbook, Air Investigations, and Technical
Gas Analysis with Drager Tubes, 2nd Edition, compiled by
Kurt Liechnitz. Dragerwerk AG, Lubeck, Federal Republic
of Germany, October 1973. 164 pp.
21
-------
were used to sustain the flame, and prepurified nitrogen was used
as the carrier gas.
The column employed was the Chromosorb 102 (1.8 m long x 3.2 x
10~3 m I.D.). The column oven was programmed to run from 50°C to
150°C at 20°C/minute. This was a sufficient temperature range to
chromatograph all the hydrocarbon components.
Samples df stack gas were injected into a 1-mL sample loop and
directed from the loop to the column by the carrier gas. The
gas separates in the column and is sent to the flame ionization
detector where an electrical signal proportional to the concentra-
tion of hydrocarbons present actuates a strip chart recorder for
permanent record keeping.
A stopwatch was used to determine the exact time each hydrocarbon
component was separated. Standard gas peaks were also timed to
match these against the unknown hydrocarbons for species identi-
fication. Peak heights were measured on the hydrocarbon unknowns
and compared against the peak heights of the standards to deter-
mine the relative concentration of the unknowns.
This method is sensitive to hydrocarbons in the C-i-C5 range from
10 ppm to 10,000 ppm.
Formaldehyde and Other Aldehydes
No standard methods have been developed for sampling aldehydes
in stack gas emissions. The method employed in this program
is designed for ambient air sampling as reported in Reference 18.
The method was modified for stack gas sampling by drawing flue
gas through a 10% aqueous sodium bisulfite solution (NaHSO3).
The sampling apparatus included a glass probe with a plug of
glass wool to filter out particulates, two midget impingers con-
taining 10 mL of 10% aqueous sodium bisulfite solution (NaHS03),
an empty impinger, a pump, a flowmeter, and a dry test meter.
Sampling was conducted at a rate of 2 L/min for a period of
15 min to 30 min. A diagram of the sampling system is shown in
Figure 6.
After sample collection, the impinger contents were transferred
to a 100-mL sample bottle. The glass wool plug was removed and
discarded. All glassware from the probe to the dry impinger was
rinsed with three portions of 10% NaHSO3, and the rinses were
added to the sample bottle.
(18) Methods of Air Sampling and Analysis. American Public
Health Association, Washington, D.C., 1972. pp. 190-198
22
-------
GLASS
GLASS WOOL PROBE
I
^
10% NaHSO
-
t
E
_
MPTY
3 _
SOLUTION
?i (7=1
DRY TESl
METER
\
FLOWMETER
ICE BATH
Figure 6. Diagram of sampling train for aldehydes.
POM Screening
An ultraviolet (UV) fluorescence technique for detection of POM
compounds has been reported by Smith & Levins (19). This tech-
nique was employed in this program for field screening. Samples
for screening were collected in a midget impinger train contain-
ing methylene chloride. Figure 7 illustrates the setup of this
train.
BASS PROBE
-TERONLINE
ROWMETER
"ICE BATH
Figure 7. Diagram of sampling train for POM screening.
Approximately 0.014 m3 of flue gas were collected over a period
of about 45 minutes in this train. Loss of methylene chloride
during sampling due to evaporation amounted to about 15 mL (20%)
It was observed at the completion of a run that the first im-
pinger contents were a light yellow color while the contents of
(19) Smith, E. M., and P. L. Levins. Sensitized Fluorescence for
the Detection of Polycyclic Aromatic Hydrocarbons. F.PA-600/
7-78-182, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, September 1978. 31 pp.
23
-------
the third impinger were nearly clear. To prevent dilution of the
overall sample, the contents of the third impinger were used to
make three successive rinses of the probe assembly. All impinger
contents and rinses were combined in a Level I cleaned (20) glass
bottle.
Screening for POM's was performed by employing the basic tech-
nique reported by Smith & Lewis (19). One microliter of the
combined train sample was spotted twice onto a clean Whatman
filter using a microcapillary tube. One spot was treated with
1 yL of a naphthalene solution (60 mg/L) to increase the sensi-
tivity of that spot to UV fluorescence. Naphthalene was also
spotted alone as a blank and its intensity, when fluorescent,
was subjectively subtracted from the sample intensity. It was
determined in the laboratory that reagent-grade naphthalene
often contains contaminants that fluoresce under UV light.
Figure 8 illustrates the spotting arrangement of the samples
and naphthalene blank.
o o o
IpL NAPHTHALENE
OF BLANK OF
SAMPLE SAMPLE
PLUS
NAPHTHALENE
Figure 8. Arrangement of sample spots and blank
on filter paper for POM screening.
The spotted filter paper was inserted into a box containing the
UV light source where the fluorescence was observed visually and
recorded. Subjective visual adjustment was made when the naphtha-
lene blank also fluoresced.
Table 5 presents the calibration of the technique as determined
via benzo(a)pyrene standard.
(20) Hamersma, J. W., S. L. Reynolds, and R. F. Maddalone. IERL-
RTP Procedure Manual: Level I Environmental Assessement.
EPA-600/l-76-160a, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, June 1976. 147 pp.
24
-------
TABLE 5. CALIBRATION OF POM SPOT TEST
Approximate
Visual observation mass of POM's
Spot without sensitizer Spot with sensitizer in spot,, pg
Fluorescent Strong fluorescence >1,000
None Strong fluorescence 100 - 1,000
None Weak fluorescence 10 - 100
None None
POM and Other Organic Species by POM Train
A modified Method 5 procedure was used to obtain samples of
particulate, POM, and other organic emissions. The modification
added an XAD-2 resin trap between the filter and impinger system
of the standard Method 5 train to collect organic species. A
cooler trap was inserted between the filter and the resin trap
to reduce the gas temperature to 21°C before its entry into the
resin trap. The remaining impingers were made up according to
the EPA Method 5 procedure (11).
At the completion of a sampling run, the resin trap was removed
and capped. The entire train, from probe tip to filter holder,
was cleaned with methylene chloride and the sample was bottled
in amber glass. Cooler trap contents were measured, and the
liquid was poured into an amber bottle. Contents of the water
impingers were also measured in order to determine the quantity
of condensed water, and the contents were stored in a separate
amber bottle. The silica gel impinger contents were weighed,
and the material discarded. All samples were stored in a
refrigerator on site and delivered to MRC's Dayton Laboratory
on ice.
This system also determined particulate emissions in accordance
with the standard Method 5 procedure since the front-half of
the train remained unchanged.
The basic Method 5 schematic was shown earlier in Figure 5. Fig-
ure 9 shows the components and sample recovery procedure for the
modification.
Operation of this train parallels that discussed earlier for the
EPA Method 5 train in terms of sample volume, sampling time and
other operating procedures.
SASS Train Samples
The SASS train employed in the environmental assessment portion
of this study was used to sample for particulate loading,
25
-------
ro
RINSE,
METHYLENE
CHLORIDE
rt
CONTENTS
(MEASURE
VOLUME)
•51
V
t
J
i \
^-\
1
X-N
fly
/ /
2
1
1
§
(V)
CONTENTS
(MEASURE
V(
4
)LU
MD
k 4
. }
LJ
c\
1
/-\ r>
1
r\
yjj )vi R1NSE
( t / C METHYLENE
3
-C
e
§
U
4 / CHLORIDE:
d J|
o ~r
9>S
§S
U
rt
4
\
WEIGH!
CONTENTS 1 °ISC|ARD
(MEASURE
VC
—7—
ILUME)
h
rt
3
Figure 9. Schematic of POM train components and sample recovery
-------
particle size data, organic compounds including POM's, individual
elements, and bioassay samples. The SASS train system, depicted
in Figure 10 (20), employs a set of three cyclones and a filter
for particle size fractionation, a solid sorbent (XAD-2) trap,
for organic species, a trace inorganic impinger trap, and a sys-
tem for flow measurement and gas pumping. The SASS train is a
high volume sampler which collects sufficient sample for inorgan-
ic and organic analysis of emissions species that are undetected
in conventional systems.
The SASS train sampled inorganic and organic emissions simulta-
neously. Inorganic species were primarily collected by the
cyclones and filters. Volatile inorganics were also collected in
the solid sorbent trap and the impinger solutions. Organic spe-
cies were primarily collected in the solid sorbent trap, although
other portions of the train (particulate samples, impinger solu-
tions, and rinse solutions) are solvent extracted to recover any
other organic material. It is believed that organic species
greater than Ce in molecular weight will be retained in the
adsorber trap, and compounds in the Ci-Ce molecular weight range
will pass through the system without being trapped.
The impinger portion of the train consists of four impingers.
The impinger order, impinger contents, and purpose of each im-
pinger are shown in Table 6. In the collection of samples for
bioassay, the impingers were charged only with water and dis-
carded at the conclusion of each test after volume change had
been recorded.
TABLE 6. SASS TRAIN IMPINGER SYSTEM FOR TRACE ELEMENTS (20)
Impinger
Reagent
Quantity
Purpose
30% H202 750 mL
2 0.2 M (NH4)2S208 750 mL
+ 0.02 M AgN03
3 0.2 M (NH4)2S208 750 mL
-I- 0.02 M AgN03
4 3-8 Mesh silica gel 750 g
(color indicating)
Trap reducing gases such as S02
to prevent depletion of oxida-
tive capability of trace-element-
collecting impingers 2 and 3.
Collection of volatile trace ele-
ments by oxidative dissolution.
Collection of volatile trace ele-
ments by oxidative dissolution.
Prevent moisture from reaching
pumps.
27
-------
STACK
THERMOCOUPLE
HEATER
CON-
TROLLER
00
CONVECTION
ZUWUVLUI IVI!
OVEN
FILTER
STAINLESS STEEL PROBE
GAS COOLER
CAS
TEMPERATURE
THERMOCOUPLE
DRY GAS METER/ORIFICE METER
CENTRAL!ZED TEMPERATURE
AND PRESSURE READOUT
CONTROL MODULE
OVEN
THERMOCOUPLE
XAO-2
CARTRIDGE
CONDENSATE
COLLECTOR
IMPINGER/COOLER
TRACE ELEMENT
COLLECTOR
IMPING ER
THERMOCOUPLE
10-CFM VACUUM PUMP (2)
Figure 10. Schematic of source assessment sampling system (20)
-------
Before sampling, the SASS train components were passivated with
1:1 (on a volume basis) aqueous nitric acid. All surfaces asso-
ciated with organic collection were cleaned with distilled water,
isopropyl alcohol, and methylene chloride in succession. These
components were dried with a stream of clean air or nitrogen.
Impingers were cleaned first with distilled water and then with
isopropyl alcohol.
At the site, the train was assembled, and the oven was heated to
205°C before each run. The resin trap was maintained at 20°C
during a run. A leak check was made before and after each run;
a leak rate less than 0.0014 m3 per minute at 508 mm Hg was con-
sidered acceptable.
The suggested sample volume of 30 m3 became unrealistic in this
program for several reasons. The first attempt at a SASS train
run took approximately 7 hours excluding startup and leak checks,
and required three filter changes due to high loading. The
accumulation of condensed organic material on inner surfaces of
the train was so severe that clean-up time doubled and required
soaking components in methylene chloride overnight to recover
the sample. Approximately 2 to 3 times the expected volume of
methylene chloride was used to recover the sample and clean the
train. This/ coupled with the potential risk involved in han-
dling highly concentrated pollutants, resulted in the decision to
sample only 15 m3 of flue gas. Although organic buildup remained
greater than desired, the situation was manageable. The large
sample volumes did require more time to process, especially in
laboratory extraction and separation. The basic SASS train
sample recovery and clean-up procedures are specified in the
Level I Procedures Manual3 and shown in Figures 11 to 13 (20).
Figure 12 differs from the recommended procedure for cleanup
of the XAD-2 module in that the condensate is usually extracted
with methylene chloride in the field. The decision to omit this
step was made after the first SASS run when, upon extraction of
the condensate, it was observed that the extraction step was not
removing a significant fraction of the organic material based on
color. After discussion with the EPA, it was decided that a more
complex laboratory extraction was needed, and that the condensate
should be collected in an amber bottle, properly preserved and
transported to MRC with the remaining samples.
The field study conducted in this program took place prior to
publication of the revised Level I Procedures Manual (20); how-
ever, some procedural changes were transmitted from EPA to MRC
by phone during the field study.
29
-------
PROBE AND
NOZZLE
METHYLENE CHLORIDE
RINSE INTO AMBER GLASS CONTAINER
ADD TO 10 urn
CYCLONE RINSE
U)
O
3«/m CYCLONE
10 pm CYCLONE
STEP 1: TAP AND BRUSH
CONTENTS FROM WALLS
AND VANE INTO LOWER
CUP RECEPTACLE
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL ON WALLS AND VANE
INTO CUP (METHYLENE CHLORIDE)
REMOVE LOWER CU P RECEPTACLE
AND TRANSFER CONTENTS INTO
A TARED NALGENE CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER (METHYLiNE LHLUKluti
INTO PROBE RINSE CONTAINER
fcOMI
v_
1
STEP 1: TAP AND BRUSH CONTENTS
FROM WALLS INTO LOWER CUP RECEPTACLE
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL WITH METHYLENE CHLORIDE
INTO CUP
STEP 3: RINSE WITH METHYLENE CHLORIDE
INTERCONNECT TUBING JOINING
lOiim TO 3 »m CYCLONES INTO AMBER
GLASS CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
A TARED NALGENE CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
AN AMBER GLASS CONTAINER
COMBINE
ALL RINSES
FOR SHIPPING
•*\AND ANALYSIS,
Figure 11.
Sample
probe,
handling and transfer-nozzle,
cyclones, and filter (20).
(continued)
-------
STEP 1: TAP AND BRUSH
CONTENTS FROM WALLS
INTO LOWER CUP RECEPTACLE
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL WITH METHYLENE CHLORIDE
INTO CUP
STEP 3: RINSE WITH METHYLENE CHLORIDE
INTERCONNECT TUBING JOINING
3 Mm TO 1 Mm CYCLONES INTO AMBER GLASS
CONTAINER
STEP 1: REMOVE FILTER AND
SEAL IN TARED PETRI DISH
STEP 2: BRUSH PARTICULATE FROM
BOTH HOUSING HALVES INTO A
TARED NALGENE CONTAINER
STEP 3: WITH METHYLENE CHLORIDE
RINSE ADHERED PARTICULATE
INTO AMBER GLASS CONTAINER
STEP 4: WITH METHYLENE CHLORIDE
RINSE INTERCONNECT TUBE
JOINING 1 nm CYCLONE TO HOUSING
INTO AMBER GLASS CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
A TARED NALGENE CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
AN AMBER GLASS CONTAINER
NOTE - ALL BRUSHES MUST HAVE NYLON BRISTLES.
ALL NALGENE CONTAINERS MUST BE HIGH
DENSITY POLYETHYLENE.
Figure 11 (continued)
-------
STEP NO. 1
COMPLETE XAD-2 MODULE
AFTER SAMPLING RUN
R&EASE CLAMP JOINING XAD-2
CARTRIDGE SECTION TO THE UPPER
GAS CONDITIONING SECTION
REMOVE XAD-2 CARTRIDGE FROM
CARTRIDGE HOLDER. REMOVE FINE
MESH SCREEN FROM TOP OF CART-
RIDGE. EMPTY RESIN INTO WIDE
MOUTH GLASS AMBER JAR.
REPLACE SCREEN ON CARTRIDGE.
REINSERT CARTRIDGE INTO MODULE.
JOIN MODULE BACK TOGETHER.
REPLACE CLAMP.
OPEN CONDENSATE RESERVOIR
VALVE AND DRAIN AQUEOUS
CONDENSATE INTO AMBER BOTTLE
STEP NO. 2 CLOSE CONDENSATE RESERVOIR VALVE
RELEASE UPPER CLAMP AND
LI FT OUT INNER WELL
WITH GOTH UNITIZED WASH BOTTLE
(METHYLENE CHLORIDE)
RINSE INNER WELL SURFACE INTO AND
ALONG CONDENSER WALL SO THAT RINSE
RUNS DOWN THROUGH THE MODULE AND
INTO CONDENSATE COLLECTOR
WHEN INNER WELL IS CLEAN.
PLACE TO ONE SIDE
RINSE ENTRANCE TUBE INTO MODULE
INTERIOR. RINSE DOWN THE CONDENSER
WALL AND ALLOW SOLVENT TO
FLOW DOWN THROUGH THE SYSTEM
AND COLLECT IN CONDENSATE CUP
RELEASE CENTRAL a AMP AND
SEPARATE THE LOWER SECTION
(XAD-2 AND CONDENSATE CUP)
FROM THE UPPER SECTION (CONDENSER)
THE ENTIRE UPPER SECTION IS NOW
_CLEAN._
RINSE THE NOW EMPTY XAD-2 SEC ~
TION INTO THE CONDENSATE CUP
RELEASE LOWER CLAMP AND
REMOVE CARTRIDGE SECTION
FROM CONDENSATE CUP
THE CONDENSATE RESERVOI R NOW
CONTAINS All RINSES FROM THE
ENTIRE SYSTEM.DRAIN INTO AN
AMBER BOTTLE VIA DRAIN VALVE.
Figure 12. Sample handling and transfer - XAD-2 module (20)
32
-------
ADD RINSE FROM
CONNECTING LINE
LEADING FROM
XAD-2 MODULE
TO FIRST IMPINGER
IMPINGER 1
I
TRANSFER TO
NALGENE CONTAINER
RINSE WITH 1:1
ISOPROPYL ALCOHOL (IPA)/-
DlSTILLED WATER AND ADD
IMPINGER 2
TRANSFER TO
NALGENE CONTAINER
RINSE WITH 1:1
-ISOPROPYL ALCOHOL (IPA)/
DISTILLED WATER AND ADD
o
IMPINGER 3
TRANSFER TO
NALGENE CONTAINER
COMBINE AND
MEASURE TOTAL
VOLUME FOR
SINGLE ANALYSIS
RINSE WITH 1:1
1— ISOPROPYL ALCOHOL (I PA)/
DISTILLED WATER AND ADD
J
IMPINGER 4
SILICAGa
DISCARD
Figure 13.
Sample handling and transfer of impinger contents for
those SASS runs made for chemical analysis (20).
33
-------
Wood and Combustion Residue
Samples of the test wood were obtained by Auburn University prior
to testing. MRC submitted these samples to Industrial Testing
Laboratories, St. Louis, Missouri, for proximate and ultimate
analysis. Combustion residues ("ash") were quantitatively
removed from the combustion unit after being allowed to burn out
and cool overnight. The mass was weighed and saved in polyeth-
ylene jars for bioassay analysis.
Flue Gas Velocity Measurement
Because flue gas velocities were generally below 200 m/min and
often below 100 m/min, it was necessary to employ a velocity meas-
uring system more sensitive to low velocities than the "S" type
pitot tube and conventional micromanometer.
The flue-gas velocity measurement device chosen for this study
was a Model 308R fluidic flowmeter (FluiDynamic Devices Limited,
Canada). The working element of the unit is a free, unbounded
jet. The jet, composed of a supply fluid compatible with the
gas to be measured, issues from a nozzle and is directed toward
two total head receiver ports. At zero cross flow, the pressure
cone produced by the jet covers both receiver ports equally,
establishing a zero pressure differential. When the product to
be measured flows across and entrains with the jet, the jet
deflects. This places unequal pressures on the receiver ports,
establishing a pressure differential between them. The differ-
ential varies directly with the gas flow and is measured with a
suitable manometer. This device was coupled to a strip chart
recorder for permanent recording of low rate changes. Velocity
measurement and recording was excellent initially; however, after
about an hour of operation, the readings became erratic. The
problem appeared to be a buildup of creosote or soot on the edges
of the nozzles which resulted in a change of calibration. Re-
calibration of the unit proved to be only a temporary solution
since either more buildup occurred or previous buildup broke off.
Cleaning the probe also provided only a temporary solution, and
the device was finally taken out of service.
Velocities for this program were finally determined by employing
an "S" type pitot tube and a Meriam micromanometer (Model 34FB2,
serial No. U43843) with a range of 0-37.36 mm Hg. This manometer
uses a scale of much greater expansion than the typical field
micromanometer and employs a vernier adjustment to obtain a
velocity reading in inches of water. The manometer was extremely
sensitive to velocity changes at low flow rates and could be ac-
curately read down to 1.87 x lO"4 mm Hg.
34
-------
Fuel Burning Rate Determination
The wood burning stoves tested and the associated flue pipe were
mounted on an electronic scale which provided digital readout of
mass. Readings were taken prior to and immediately after charg-
ing wood to determine the weight of a wood charge. Readings
were also taken at the start-up and shut-down of various sampling
trains to facilitate emission factor determination. Auburn
University also took weight readings at 5-min intervals during
efficiency testing.
As a precaution against sampling probes affecting weight readings
during thermal expansion and contraction of the stack, the sam-
pling trains were suspended by cables and balanced. In this way,
any upward or downward movement of the stack caused the train to
pivot rather than exert a force against the stack and influence
weight readings. Weight readings taken with and without the
trains in place showed no more than 0.05 kg influence on the
weight determination.
Because of the size and mass of the fireplace, the electronic
scales could not be utilized. However, the 5-min weight readings
during testing of the wood burning stoves showed that the wood
mass decrease during combustion was nearly linear. Therefore,
by weighing all wood charges to the fireplace and observing the
length of burn of several wood charges, the mass burned during
testing could be determined from the length of the test.
LABORATORY SEPARATION AND ANALYSIS PROCEDURES
At the completion of each two-week interval of field sampling,
individual bottles containing the contents and clean-up solutions
of the various sampling trains were delivered to MRC's Dayton
Laboratory. The laboratory effort included separation schemes
and analytical procedures in order to characterize the source
emissions. The following section presents the details of these
procedures.
Particulates and Condensable Organics
Samples for particulate analysis from the Method 5 train (front
half washings and filter) were analyzed according to the Method 5
procedure as specified in the Federal Register (11). The back-
half portion of the train (impinger contents and back-up filter)
was used to determine the mass of condensable organic material.
The back-up filter was desiccated overnight to a constant weight.
The impinger solutions were evaporated to dryness at about 95°C
and weighed to determine the residue mass. The combination of
residue mass and filter weight gain is reported as condensable
organic material.
35
-------
Particulate emissions were also determined from the front-half
mass of the POM train. This portion of the POM train is identi-
cal to the Method 5 train and the particulates were determined
accordingly. After mass determination the particulate samples
were submitted for POM and organic analysis.
In addition to the above analyses, particulate samples were sub-
mitted to industrial Testing Laboratories (St. Louis, Missouri)
for analysis of carbon, hydrogen, and nitrogen using a Perkin
Elmer Model 240 elemental analyzer.
Samples recovered from the front half of the SASS train were also
used to semiquantitatively measure particulate emissions. All
front-half washes were evaporated to dryness. These samples,
along with the cyclone catches and filters, were desiccated over-
night to a constant weight. The resulting mass collected was
used to determine particulate emissions by size fraction.
Sulfur Oxides and Nitrogen Oxides
Method 6 samples for SOa determination were analyzed using the
Federal Register procedure (14). Samples collected by Method 7
for NOX determination were partially worked up at the test site
by recording ambient temperature, barometric pressure, and in-
ternal flask pressure and adjusting the solution pH for NOX fixa-
tion. Final analysis for NOX was conducted at MRC's Dayton
Laboratory. All procedures followed those given in the Federal
Register (15).
Formaldehyde
Aldehydes were collected in an impinger containing a 10% sodium
bisulfite solution. Concentrations of formaldehyde greater than
or equal to 0.02 ppm were determined using Tentative Method 110
as proposed by the Interscience Committee (17). In this proced-
ure, a mixture of chromotropic acid and sulfuric acid is used as
the reagent. The transmittance is read at 580 nm. Saturated
aldehydes gives less than 0.01% positive interference, and the
unsaturated aldehyde acrolein results in a few percent positive
interference. Ethanol and higher molecular weight alcohols and
olefins in mixtures with formaldehydes are negative interferen-
ces. However, concentrations of alcohols in air are usually much
lower than formaldehyde concentrations and, therefore, are not a
serious interference.
This was not the original method attempted but was resorted to
after three other methods were tried and failed to show color
development for 90 ppm formaldehyde (ECHO) in 10% NaHS03. The
methods attempted were 1) modified Sniffs with para-rosaniline
36
-------
and HC1 (21), 2) modified Shiffs with para-rosaniline and H2SO«*
(21), and 3) MBTH (22). One reviewer of this report noted that
the analysis method chosen was not generally considered reliable,
and that the presence of polar organics would tend to reduce the
reliability even more.
Other Aldehydes
C2 to C5 aldehydes were collected in impingers containing a 10%
NaHSOi» solution. The analysis method is patterned after Tenta-
tive Method 110 as proposed by the Interscience Committee and
can be found in Reference 18.
The aldehydes were measured using GC/FID. The GC column was
stainless steel (1.7 m x 3 mm) packed with uncondenonylphthalate
on firebrick followed by a 4 m x 3 mm stainless steel column
packed with 15% by weight Carbowax 20M on Chromasorb, 60 to 80
mesh. Retention times for the various species, under the condi-
tions given in Reference 18 are presented in Table 7.
TABLE 7. RETENTION TIMES FOR ALDEHYDES
Retention time,
Compound min
Acetaldehyde 3.92
Propionaldehyde 5.11
Isobutylaldehyde 5.91
n-Butyraldehyde 7.77
Crotonaldehyde unknown
POM Train Sample Pretreatment
Samples collected from the Modified EPA Method 5 sample train
were received from the field in the following forms:
Particulate samples from the probe washes
Glass fiber filter
XAD-cartridge
Contents of water impingers and cooler trap
Methylene chloride rinses
(21) Lyles, G. R., F. B. Dowling, and V. J. Blanchard. Quanti-
tative Determination of Formaldehyde in Parts Per Hundred
Million Concentration Level. Journal of the Air Pollution
Control Association, 15 (3):106-108, 1965.
(22) Tentative Method of Analysis for Formaldehyde Content of the
Atmosphere (MBTH-Colorimetric Method - Applications to Other
Aldehydes). Health Laboratory Science, 7 (3):173-178, 1970.
37
-------
The XAD-2 trap, probe washings, and the filter were subjected to
Soxhlet extraction with methylene chloride (CHaCla) for 24 hr.
The CH2C12 was then reduced to a volume of approximately 5 mL by
means of rotary evaporation at a pressure greater than 10 mm Hg
and a water bath temperature of less than 45°C. Following volume
reduction, the sample underwent a solvent exchange with hexane
and was reduced to 10 mL by Rotovap. It was observed that a
significant portion of the material that was soluble in methylene
chloride would not go into hexane. This material was recovered
and resolubilized in methylene chloride. A solid precipitate
also formed during solvent exchange but was not analyzed. The
hexane-soluble fraction was separated into eight fractions on a
silica gel column. An aliquot of each fraction was then reduced
in volume using a Kuderna-Danish evaporator and transferred to a
tare-weighed micro-weighing pan, and the remaining solvent evapo-
rated in air. Each dried fraction was weighed and then redis-
solved in a minimum quanity of methylene chloride. The eight
fractions are shown in Figure 14. All eight fractions of one run
were analyzed on GC/MS. It was found that the most cost effec-
tive approach for analysis was to analyze fraction 1 separately
and combine fractions 2, 3, and 4 as well as fractions 5, 6, and
7. Fraction 8 was observed to contain little or no detectable
organic compounds and was therefore dropped from the scheme.
The water impinger contents of one run underwent an acid, base,
ether extraction. It was determined by TOC analysis of the re-
maining aqueous phase that only 30% of the organic carbon was
extracted and the remainder was contained in the aqueous phase.
The water impinger contents of the remaining runs were evaporated
to dryness under vacuum, and the residue was recovered in metha-
nol. Ultimately, the following samples were submitted for GC/MS
analysis:
• Hexane-soluble fraction 1
• Hexane-soluble fractions 2, 3, 4
• Hexane-insoluble fraction in methylene chloride
• Impinger water residue in methanol
Figure 14 presents the analysis flow diagram for the POM train
samples.
The hexane-soluble fractions were analyzed for organic species
on a Hewlett-Packard GC/MS system (Model 5982-A or HP5983-A)
using the following general conditions: 6.4 m x 1.8 m glass
column packed with 3% Dexsil 400 on Chromosorb W-HP, 60°C,
2 min/16°C per minute/280°C (on HP5982-A) or 300°C (on HP5983-A),
helium flow: 30 mL/min. In addition, POM's were specifically
sought for using SIM (Selected Ion Monitoring) programming.
The hexane-insoluble samples were found to be largely nonchro-
matographable; however, the chromatographable portion contained
a significant mass of organic compounds. This material was
38
-------
SaVtNT EXCHANGE
IHEXAK)
1
. . 1
SOLID PRECIPITATE
HEXANE SOLUUES
LIQUID
OWOMATOGRAPHIC
SEPARATIONS
1 FRACTIONS
ALIPHATIC
HYDROCARBONS
GC/MSFOR
ORGANIC SPECIES
Figure 3,4,
POM train sample analysis scheme for
organic species and POM compounds.
39
-------
examined by GC/MS under the same conditions as the hexane-soluble
fractions. A variety of species, including POM's, were detected
and quantitated. A DIP (Direct Injection Probe) run was also
made on one of these samples and revealed, in addition to the
species already identified by GC/MS, a continuous stream of ions,
many above 301 (the molecular ion of dibenzopyrene). This sug-
gests a variety of high molecular weight fused-ring aromatics
(e.g., POM's, M.W. greater than 302). As an example, a POM of
molecular weight 326 could be isolated. Here, the "bake-off
temperature of the DIP is the limiting factor in the amount of
material generating this pattern.
Likewise, a GC run of a methanol solution of the aqueous residue
revealed no detectable species (with some programming). A DIP
run on this sample, yielded only ions associated with organic
(aliphatic) acids. No molecular ions were generated to provide a
molecular weight range; however, the broadness of the thermogram
suggests a rather high molecular weight range (probably greater
than 284 - stearic acid).
Direct injection of the water from the impingers into the GC/MS
provided no information; no organic species were detectable in
the sample at the level provided (approximately 5 to 50 pg/mL
for general response range).
The method used for POM analysis employed a peak-area quantita-
tion technique with computer-reconstructed chromatograms from the
GC/MS. All data were collected in the electron impact (El) mode
because of the abundance of available El-mass spectra.
Gas chromatographic separation was achieved using a 6-ft Dexsil
400 glass column with temperature programming from 160°C for 2
rain, rising to 280°C at 8°C/min, and becoming isothermal at
280°C. The carrier gas was helium at a flow rate of 30 mL/min.
The mass spectrometer, operating in the El mode, was programmed
to scan the 35-350 atomic mass unit (amu) range as the POM compo-
nents eluted from the gas chromatograph. The data system recon-
structed the chromatogram using the total ion mode. POM's were
located by their molecular mass ions which were displayed using
the selected ion mode (SIM). Their identity was confirmed by
examination of their mass spectra and retention times. Samples
and standards were run in SIM for quantitation.
Standard responses were determined for each POM of interest
using varying concentrations of standards in methylene chloride,
and calculating average mass ion peak area per unit concentra-
tion. Sample peaks were compared with standard response factors
that were obtained under the same conditions of attenuation,
injection volume (2 yL), and tuning condition.
40
-------
SASS Train Work-Up and Analysis
The Source Assessment Sampling System (SASS) employed in this
program allowed the collection of many components of an emission
source in a single test. However, the separation and analysis
schemes were complex because of the many components. Once
separation was accomplished, the analytical method for any par-
ticular component class or compound (e.g., trace metals or POM)
was identical regardless of the source of the sample. As a
result, a major portion of the analytical effort concerned the
separation of components prior to analysis.
At the completion of a sample run, the samples collected by this
system included the contents of the three cyclones, the filter,
the combined probe and cyclone washes, the XAD-2 resin trap, the
XAD-2 trap condensate, the XAD-2 washes, and the combined im-
pinger collection and washes.
In order to determine a mass loading, the materials collected
from the cyclones and filter were individually weighed. The
probe and cyclone wash was evaporated to dryness and weighed, and
this plus the cyclone-collected material and the filter catch
provided a "front half" mass for the calculation of the particu-
late emission rate. All of the solid materials were then com-
bined and extracted with methylene chloride for 24 hr in a
Soxhlet extractor in order to extract organic materials.
At this point, five samples existed:
extracted solids (filter, cyclones, XAD-2 resin)
solid extract containing organics
resin trap washes
resin trap condensate
impinger contents
Chemical Analysis—
Two SASS train runs were made for chemical analysis: one for
organic analysis only and one for organic and trace element anal-
ysis. The trains differed only in impinger solutions where the
train for organic analysis employed only distilled, deionized
water and that for trace element analysis employed the reagents
shown earlier in Table 6. The separation and analysis scheme for
organic compounds closely paralled that used for the POM train
shown in Figure 14. In this case, the resin module condensate
was combined with the impinger solutions, prior to evaporation.
Prior to extraction, a 5-g portion of XAD-2 resin was saved for
trace element analysis. The remaining solids were also submitted
for trace element analyses as were the resin trap condensate and
reagent impinger solutions. Atomic absorption was used to
41
-------
determine arsenic, mercury, and selenium (23). Inductively
coupled argon plasma emission spectroscopy was used to quantify
aluminum antimony, barium, boron, cadmium, calcium, chromium,
cobalt, copper, iron, lead, magnesium, manganese, molybdenum,
nickel, phosphorus, silicon, silver, sodium, strontium, tin,
titanium, vanadium, and zinc. The AtomComp with I CAP forms an
analytical system for simultaneous multielement determinations of
trace metals at the sub-ppm level in solutions. The basis of the
method is atomic emission promoted by coupling the sample, neb-
ulized to form an aerosol, with high temperature argon plasma
produced by passage of argon through a powerful radio-frequency
field (24).
All of the solid samples were digested before analysis using the
acid digestion Parr bomb technique originally developed by Bernas
and modified by Hartstein for trace metal analyses of coal dust
by atomic absorption (25, 26). This method employs the Parr 4145
Teflon-lined bomb and involves digestion of powdered samples in
ULTRAR brand (69% to 71%) redistilled nitric acid at 150°C. The
accuracy of this method for coal dust analysis, reported for 10
metals, ranged from 94% for beryllium to 106% for nickel using
10-mg samples. Sample solutions produced by acid digestion were
diluted with distilled deionized water to reduce acid concentra-
tions to approximately 2% and submitted for analysis.
Aqueous impinger solutions from the SASS train were analyzed for
the volatile elements which could not be 100% collected by the
filter, i.e., mercury, arsenic, selenium, and antimony.
Bioassay—
Twelve SASS runs were made to provide samples for bioassay: one
for each test condition. Bioassay was conducted by Litton
Bionetics for the EPA under separate contract. Each SASS run
resulted in two samples for bioassay. The first consisted of the
(23) Metals by Atomic Absorption Spectrophotometry. in:
Standards Methods for the Examination of Water and Waste-
water, 14th Edition. American Public Health Association,
Washington, D.C., 1976. pp. 143-270.
(24) Jarrell-Ash Plasma AtomComp for the Simultaneous Determina-
tion of Trace Metals in Solutions (manufacturer's brochure).
Catalog 90-975, Jarrell-Ash Company, Waltham, Massachusetts.
5 pp.
(25) Bernas, B. A New Method for Decomposition and Comprehensive
Analysis of Silicates by Atomic Absorption Spectrometry
Analytical Chemistry, 40(11):1682-1686, 1968.
(26) Hartstein, A. M., R. W. Freedman, and D. W. Platter. Novel
Wet-Digestion Procedure for Trace-Metal Analysis of Coal by
Atomic Absorption. Analytical Chemistry, 45(3):611-614,
42
-------
methylene chloride extract of all front-half material (cyclone
and filter catches and wash residues). It was determined that
bioassay of the individual components would be meaningless
because most of the front-half catch was recovered in the
washings, indicating the train did not effectively size the
particles. Because of the organic nature of the material col-
lected, it was desired to only test the methylene chloride
soluble fraction.
The second sample submitted consisted of the methylene chloride
extract of the XAD-2 resin and the methylene chloride rinse of
the XAD-2 module. The methylene chloride solvent was exchanged
for dimethyl sulfoxide (DMSO) prior to submitting the samples to
Litton. Twelve samples of each were submitted for Salmonella/
microsome mutagenesis assay (Ames Test) and clonal toxicity (CHO)
assay.
Combustion Residue^
Combustion residue samples (ash) were collected from each test
condition, and 8 were submitted to Litton for bioassay. Table 8
presents the bioassays performed on each of these samples.
TABLE 8. COMBUSTION RESIDUE SAMPLE TEST
CONDITIONS AND BIOASSAYS PERFORMED
Sample
code
A-l
A- 2
A- 3
B-2
B-3
C-2
C-3
C-4
Test condition
Fireplace - seasoned oak
Fireplace - green oak
Fireplace - seasoned pine
Baffled stove - green oak
Baffled stove - seasoned pine
Nonbaffled stove - green oak
Nonbaffled stove - seasoned pine
Nonbaffled stove - green pine
Bioassay
performed
Ames and RAM
Aquatic^
Whole animal
Ames and RAM
Ames and RAM
Whole animal
Aquatic b
Ames and RAM
Cytotoxicity.
3Aquatic ecological effects (acute static bioassay -
Daphnia).
'Acute in-vivo in rodents.
43
-------
SECTION 4
RESULTS
Test results for the sampling and analysis of emissions from
residential wood-burning stoves and fireplaces are discussed in
this section. Each emission species measured is addressed
separately and correlated to test parameters where possible.
Overall conclusions and potential implications of the test
results are then considered. Because a wide range of combustor
designs, operating conditions, and fuel types could not be
studied in detail in this program, caution should be exercised
in extrapolating these results to other combustion equipment,
wood types, or test conditions.
EMISSIONS SUMMARY
Emission ratesa, expressed as grams of pollutant emitted per kilo-
gram of wood burned, for the test conditions used in this program
are summarized in Table 9 for criteria pollutants and POM emis-
sions. These data were obtained by employing standard EPA
methods except in the case of POM's which were measured with a
modified EPA method. Other less quantitative or more specific
emission data are presented later in this section. Additional
test parameters which were measured to characterize combustion
conditions are presented in Table 10.
Particulate Emissions
Particulate emissions were determined by measuring the mass of
material collected by the front half of the SASS train, the POM
train and the EPA Method 5 train. The results, reported in
Table 11, shows that there is no significant variation between
the emissions from the fireplace and the wood stoves. A statis-
tical analysis supports this conclusion (see Appendix B) . The
particulate emission rates, expressed as grams of pollutant
emitted per kilogram of wood burned, vary from 0.6 g/kg to 6.0
g/kg wood burned. This variation can be attributed to the vari-
able nature of the combustion process.
Emission rates are expressed as grams of pollutant emitted per
kilogram of wood burned (g/k) throughout this report.
44
-------
U1
TABLE 9. SUMMARY OF EMISSION RESULTS FOR CRITERIA POLLUTANTS AND
POM'S FROM WOOD-FIRED RESIDENTIAL COMBUSTION EQUIPMENT
Hood burning
device
Fireplace
Fireplace
Fireplace
Fireplace
Baffled stove
Baffled stove
Baffled stove
Baffled stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Wood type
Seasoned oak
Green oak
Seasoned pine
Green pine
Seasoned oak
Green oak
Seasoned pine
Green pine
Seasoned oak
Green oak
Seasoned pine
Green pine
Particulate
matter3
2.3
2.5
1.8
2.9
3.0
2.5
3.9
7.0
2.5
1.8
2.0
6.3
(0.13)
(0.19)
(0.10)
(0.21)
(0.17)
(0.19)
(0.21)
(0.51)
(0.14)
(0.13)
(0.11)
(0.46)
Condensable
organics"
6.3
5.4
5.9
9.1
4.0
3.8
4.1
12
6.0
3.3
5.6
10
(0.35)
(0.40)
(0.32)
(0.67)
(0.22)
(0.28)
(0.23)
(0.88)
(0.34)
(0.25)
(0.31)
(0.74)
Emission rate, ykg" (tig/J)" .
Volatile .
hydrocarbons0 N0xd S0xe COT
19 (1.1) 2.4
1.9
1.4
1.7
0.4
0.7
2.8 (0.15) 0.5
0.8
0.4
0.3 (0.02) 0.5
0.2
3.0 (0.22) 0.4
(0.13)
(0.14)
(0.08)
(0.13)
(0.02)
(0.05)
(0.03)
(0.06)
(0.02)
(0.04)
(0.01)
(0.03)
30
22
21
15
110
120
270
220
0.16 (0.009) 370
91
0.24 (0.013) 150
97
(1.7)
(1.6)
(1.2)
(1.1)
(6.2)
(9.0)
(15)
(16)
(21)
(6.8)
(8.2)
(7.1)
POM9
0.025
0.036
0.21
0.37
0.19
0.32
(0.0014)
(0.0026)
(0.012)
(0.020)
(0.011)
(0.024)
"Front half of EPA Method 5 and POM train. Averaged when two values are available.
bBack half of EPA Method 5. Averaged when two values available.
CGC/FID.
EPA Method 7. Average of 6 grab samples.
6EPA Method 6.
fEPA Method 3 (Orsat) for stoves, average of 10 samples. Drager tube for fireplace, 15-30 minute composite.
train (EPA Method 5 modified with XAD resin trap) .
-------
TABLE 10. SUMMARY OF TEST CONDITIONS DURING TESTING OF
WOOD-FIRED RESIDENTIAL COMBUSTION EQUIPMENT
Wood burning
device
Fireplace
Fireplace
Fireplace
Fireplace
Baffled stove
Baffled stove
Baffled stove
Baffled stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Wood type
Seasoned oak
Green oak
Seasoned pine
Green pine
Seasoned oak
Green oak
Seasoned pine
Green pine
Seasoned oak
Green oak
Seasoned pine
Green pine
Wood
burning
rate,3
kg/min
0.18
0.17
0.19
0.16
0.14
0.11
0.12
0.10
0.13
0.11
0.12
0.13
Temperr
ature ,
°C
152
207
236
207
307
300
378
247
384
240
304
305
Average
Velocity,
m/min
308
347
367
332
184
117
146
213
128
89
109
111
stack gas conditions
Flowb
rate,
Nm3/min
6.5
6.4
6.5
6.5
1.5
0.9
1.0
2.0
0.9
0.9
0.9
0.8
H20,b
%
3.8
4.2
3.8
0.5
13
11
15
11
11
4
11
15
co2,c
%
0.5
0.5
0.5
0.5
7.7
9.2
14
9.4
14
11
11
9.9
o2,c
%
21
21
21
21
13
11
4.4
11
5.5
9.3
8.4
10
co,c
%
0.07
0.05
0.04
0.04
0.7
1.1
2.8
0.9
2.8
1.0
1.6
1.5
Average burning rate during EPA Method 5, POM, and SASS train operation.
Determined from average EPA Method 5 data.
>*
"Determined by Orsat and DrSger tube.
-------
TABLE 11. PARTICULATE EMISSIONS FROM WOOD
BURNING FIREPLACES AND STOVES
-------
TABLE 12. PARTICULATE LOADING OF SASS TRAIN COMPOSITION EXPRESSED
AS PERCENT OF TOTAL PARTICULATE CATCH3
Particulate loading, %
Combustion
equipment
Fireplace
Baffled stove
Nonbaffled stove
Front
Wood type half wash
Seasoned oak
Green oak
Seasoned pine
Green pine
Seasoned oak
Green oak
Seasoned pine
Green pine
Seasoned oak
Green oak
Seasoned pine
Green pine
64
23
69
76
7
53
61
11
51
64
67
66
Large
cyclone
2
1
2
2
2
1
2
1
3
1
1
1
Middle
cyclone
1
0
3
0
3
2
2
2
4
0
0
1
of total
Small
cyclone
2
1
2
0
1
0
1
2
4
1
1
1
Filter
32
75
24
22
88
44
35
84
38
34
31
32
Some values do not add up to 100% because of round-off error.
An analysis of the filter catch was performed to determine the
composition of the particulate emissions. Table 13 presents the
carbon, hydrogen, and nitrogen content of particulates collected
on EPA Method 5 filters and POM train filters after methylene
chloride extraction.
TABLE 13. CARBON, HYDROGEN, AND NITROGEN CONTENT OF PARTICULATE
EMISSIONS FROM WOOD BURNING FIREPLACES AND STOVES
Test
condition
code Sample identification
A- 4
A-4
B-l
B-l
B-3
B-3
EPA- 5 front half filter catch
PCM train filter catch after extraction
EPA-5 front half filter catch
POM train filter catch after extraction
EPA-5 front half filter catch
POM train filter catch after extraction
Composition of
particulate , %
Carbon
50.7
64.6
50.8
38.6
79.0
76.5
Hydrogen
1.9
2.1
1.7
2.4
2.1
2.1
Nitrogen
0.3
0.2
0.6
0.4
0.3
0.3
The composition of the particulates remained essentially unchanged
after methylene chloride extraction indicating 1) that no organic
material was extractable from the particulates or 2) that what was
extracted had a carbon content identical to that of the nonextract-
able fraction.
48
-------
About 40% of the particulate matter was unaccounted for by
carbon, hydrogen, and nitrogen analysis. Inorganic components
should be negligible because of the low fuel ash content (less
than 1%). Therefore, based on the fuel analysis (Table 13), it
would be reasonable to conclude that the remaining portion is
oxygen. The analysis of the particulates then compares closely
with the fuel analysis on a dry basis with about 60% carbon in
the particulates and about 50% carbon in the wood. The slight
difference can be attributed to some loss of hydrogen and oxygen
during combustion. The actual chemical structure of the particu-
lates, however, in no way resembles that of the wood. The par-
ticulates were a dark brown or black sooty, carbon-black-like
material which exhibited some resinous qualities.
Trace Elements
This is the first study undertaken to characterize the magnitude
of trace element emissions from wood-fired residential heating
equipment. Table 14 presents emission rates, expressed as grams
of pollutant emitted per kilogram of wood burned, for 29 elements
identified in the analysis of samples taken while burning green
pine in the nonbaffled stove. The emission rates determined
during this study range from 1.4 x 10~7 g/kg to 4.2 x 10~2 g/kg.
The highest values measured (1.8 x 10~2 g/kg for silver and
4.2 x 10~2 g/kg for zinc) are believed to be in error. Silver
analysis with the ICAP technique tends to give high readings at
low concentrations, and many of the elements (including silver)
were near their detection limits in this analysis. The high
reading for zinc may result from volatilization of zinc from the
galvanized stack.
The ash composition of wood can range from 0.2% to 2.2%, with
calcium, potassium, phosphorus, sodium, and magnesium being the
predominant elements (10, 27-30). These same elements have
relatively high emission rates in Table 14 (on the order of 10~3
g/kg), but the absolute value of the emission rates is two or
three orders of magnitude lower than their typical concentration
(27) Schorger, A. W. Chemistry of Cellulose and Wood. McGraw-
Hill Book Company, New York, New York, 1926. p. 51.
(28) Young, H. E. Preliminary Estimates of Bark Percentages and
Chemical Elements in Complete Trees of Eight Species in
Maine. Forest Products Journal, 21(5):56-59, 1971.
(29) Mingle, J. G., and R. W. Boubel. Proximate Fuel Analysis
of Some Western Wood and Bark. Wood Science, l(l):29-36,
1968.
(30) Fernandez, J. H. Why Not Burn Wood? Chemical Engineering,
84(11):159-164, 1977.
49
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TABLE 14. ELEMENTAL EMISSIONS OBTAINED FROM
THE NONBAFFLED WOODBURNING STOVE
Emission
species
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Emission
rate,
q/kq
1.5 x 10-3
2.3 x 10-°
1.3 x 10-*
2.0 x 10-*
1.4 x 10~7
7.3 x 10-*
3.6 x 10~s
4.7 x 10-3
9.0 x 10-*
6.0 x 10-B
1.7 x 10-*
3.1 x lO-3
4.8 x 10-*
2.9 x 10-*
1.9 x 10-*
Emission
species
Mercury
Molybdenum
Nickel
Phosphorus
Selenium
Silicon
Silver
Sodium
Strontium
Tin
Titanium
Vanadium
Yttrium
Zinc
Emission
rate,
q/kg
1.3 x 10-*
2.3 x 10-*
1.7 x 10-3
7.0 x 10-*
1.3 x 10-*
2.7 x 10~3
1.8 x 10-a
3.0 x 10-3
1.1 x 10-5
3.8 x 10-*
1.0 x lO-5
1.5 x 10-*
9.3 x 10-s
4.2 x 10-2
in wood. Thus only a small fraction of the trace element con-
tent of wood is emitted to the atmosphere.
Condensable Organics
Condensable organic emissions were determined by measuring the
mass of material collected in the back of the EPA Method 5 par-
ticulate train. The back half of this train consisted of impin-
gers containing distilled water and a back-up filter which col-
lected most of the materials passing through the front-half fil-
ter. The impinger solutions ranged from yellow to light brown
in color, while the back-up filter catches were consistently
yellow. Connecting glassware was dotted with brown resinous
material which proved difficult to recover. This material, if
emitted, would condense in the atmosphere and could be considered
as part of the particulate emissions; however, for this study, it
is reported separately.
Emission rates for condensable organic material, expressed as
grams of pollutant emitted per kilogram of wood burned, are pre-
sented in Table 15 and range from an average of 2.2 g/kg to 14
g/kg. A statistical analysis indicates that condensable organic
emissions are over two times higher when burning green pine than
when burning the other three wood types tested (see Appendix B).
The combustion equipment type had no significant effect on con-
densable, organic emission rates. The condensable organics
accounted for 54% to 76% of the total mass collected by the EPA
Method 5 train (see Table 11); 12% to 39% of the back-half mass
was collected on the back-up filter.
50
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TABLE 15. CONDENSABLE ORGANIC MATERIAL EMISSIONS
(gAg)
Type of wood
Combustion
equipment
Fireplace
Baffled stove
Nonbaffled stove
Seasoned
oak
6.3
4.0
6.0
Green
oak
5.4
5.4
2.2
3.3
Seasoned
pine
5.9
4.1
5.6
Green
pine
9.1
14.3
9.4
10.1
3As determined from back half of EPA Method 5 train.
Nitrogen Oxides
A total of 72 samples were collected for the analysis of NOX
emissions from wood-burning stoves and fireplaces. Six samples
were taken randomly throughout several burning cycles of each
test condition so that the resulting emission rates, expressed
as grams of pollutant emitted per kilogram of wood burned, would
be representative of the wood burning process. The resulting
NOx emission rates are presented in Table 16.
TABLE 16. NITROGEN OXIDE EMISSIONS
(g/kg)
Type of wood
Combustion
equipment
Fireplace
Baffled stove
Nonbaffled stove
Seasoned
oak
2.3
2.5
2.7
2.6
2.0
2.1
2.4a
0.7
0.3
0.3
0.6
0.3
0.2
0.4a
0.6
0.2
0.4
0.2
0.7
0.5
0.4*
Green
oak
3.5
3.3
0.2
2.1
2.0
0.2
1.9a
0.9
0.3
0.8
1.2
0.7
0.3
0.7«
0.5
0.7
0.4
0.8
0.4
0.4
0.58
Seasoned
pine
0.8
1.0
2.2
1.3
1.6
1.6
1.48
0.4
0.3
0.8
0.1
0.7
0.6
0.5*
0.2
0.1
0.2
0.2
0.2
0.3
0.2*
Green
pine
1.9
1.7
1.8
1.8
1.7
1.3
1.7a
0.3
0.8
0.6
1.1
0.9
0.9
0.98
0.5
0.2
0.5
0.7
0.3
0.2
0.48
Average.
The consistency of the replicate samples indicates that the stage
of the burning cycle had negligible effect on NOX emissions.
This is verified statistically in Appendix B.
51
-------
A statistical analysis was performed to determine the effect of
combustion equipment and wood type on NOx emission rates
(Appendix B). The results support the observed difference in
NOX emissions between the fireplace and stoves. No significant
difference exists between NOx emissions from the wood types
tested. However, the statistical analysis revealed a large
error term, indicating an unknown variable was influencing the
NOx emission rates.
Based on average emission rates, expressed as grams of pollutant
emitted per kilogram of wood burned, the fireplace emits about
four times as much NOx as the stoves per unit of wood burned. In-
creased NOx emissions are generally associated with higher com-
bustion temperatures. This is consistent with the lower CO and
POM emissions (products of incomplete combustion) associated with
the fireplace since higher combustion temperatures are indicative
of greater combustion efficiency. A possible explanation for
this may be the higher combustion air velocities associated with
the fireplace which cause more rapid burning and thus higher tem-
peratures. The burning rate of the fireplace was about 40%
greater than that of the stoves.
Carbon Monoxide
Carbon monoxide (CO) is a product of incomplete combustion and is
a major pollutant emitted from wood-burning fireplaces and stoves
Table 17 presents the CO emission rates, expressed as grams of
pollutant emitted per kilogram of wood burned, determined in this
program; they range from 11 g/kg to 40 g/kg for the fireplace and
from 83 g/kg to 370 g/kg for the stoves.
TABLE 17. CARBON MONOXIDE EMISSIONS
(g/kg)
Type of wood
Combustion
equipment
Fireplace
h
Baffled stove
K
Nonbaffled stove
Seasoned
oak
40
19
110
370
Green
oak
26
18
110
130
87
77
109
Seasoned
pine
11
38
15
270
270
150
Green
pine
15
180
260
110
99
83
83
110
aAs determined by Drager tube analysis of a bag sample.
As determined by Or sat analysis; average of 10 grab
samples.
52
-------
Although it appears that the emission rates for the wood burning
stoves are higher, a statistical analysis does not support this
conclusion (see Appendix B). According to this analysis an un-
accounted for variable exerted significant influence on the CO
emission rates. Formulation of CO is apparently very sensitive
to changing fuel bed conditions, and this may account for the
variability between replicate test results. Figure 15 presents
CO concentrations in the flue gas from a wood-burning stove
versus time over one combustion cycle.
10 15 20 25 30 35 40 « 50 55
TIME INTO BURNING CYCLE, min
60 65 70 75
Figure 15.
Carbon monoxide concentration in the flue gas from
a wood-burning stove as a function of time.
This graph shows greater than an order of magnitude change in CO
concentration in 20 minutes. With this high variability in one
burning cycle, consistent results between series of tests should
not be expected. The average CO emission rates, expressed as
grams of pollutant emitted per kilograms of wood burned, in Table
17 represent the average of 10 grab samples taken in one burning
cycle for the wood-burning stoves and a 15-min to 30-min inte-
grated sample for the fireplaces. The results for the individual
grab samples follow the general trend shown in Figure 15 and can
be found in Appendix A.
Sulfur Oxides
Sulfur oxide emissions were anticipated to be very low because of
the low fuel sulfur content (0.01%). Therefore, only two samples
were collected for S02 analysis. Both samples were taken from
the nonbaffled stove. The results are presented in Table 18 as
S02 emission rates, expressed as grams of pollutant emitted per
kilograms of wood burned.
Based on the fuel sulfur content the maximum possible SO2 emis-
sion rates would be approximately 0.2 g/kg. The average meas-
ured SO2 emission rate of 0.2 g/kg is in obvious agreement,
53
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TABLE 18. SO2 EMISSIONS FROM THE NON-
BAFFLED WOODBURNING STOVE
Emission
Wood type rate, g/kg
Seasoned oak 0.16
Seasoned pine 0.24
but each individual measurement differed by 20%. High variability
would be expected because the fuel sulfur analysis and SOa analy-
sis were both near the detection limit.
Low-Molecular-Weight Volatile Hydrocarbons
Low-molecular-weight volatile hydrocarbon emissions were deter-
mined by GC/FID from bag samples of flue gas collected over a
15-min to 20-min interval at four test conditions. The emission
rates/ expressed as grams of pollutant emitted per kilogram of
wood burned, for individual species are reported in Table 19. No
additional effort was made to quantify these emissions because
of the added labor requirements and the relatively lower environ-
mental impact anticipated when compared to the higher-molecular-
weight organics. Significant effort was expended in quantifying
high-molecular-weight organic emissions as discussed later in
this section.
The emission rates indicate high variability, in agreement with
previous studies where total volatile hydrocarbon emission
rates from fireplaces ranged from 2 g/kg to 400 g/kg (1, 2).
Major Organic Species
Emissions of organic material greater than Ce were collected for
analysis by the POM train and the SASS train, both of which em-
ployed an XAD-2 resin trap. The collected organic material was
extracted from the XAD-2 resin and the remainder of the sampling
train and submitted for analysis by GC/MS. The details of this
procedure are presented in Section 3. The organic material could
only be partially characterized because a major part was nonchro-
matographable by GC/MS.
As explained in Section 3, the organic loading of each sampling
system during testing was quite high in spite of the reduced
volume of sample collected. As a result large quantities of
organic materials had to be recovered from various components of
the sampling system. In all cases a significant quantity of
organic matter was trapped in the aqueous impingers after passing
through the filter and XAD-2 resin trap. That which was recovered
from the resin and the particulate fractions would only partially
dissolve in hexane during the sample workup. A portion of this
insoluble material was soluble in methylene chloride, but there
54
-------
TABLE 19. LOW-MOLECULAR-WEIGHT HYDROCARBON EMISSIONS*
(g/kg)
Emission species
Fireplace Baffled stove
seasoned oak seasoned pine
Nonbaffled stove
Green oak Green pine
Methane,
C-i to C2 hydrocarbons
Ethylene, C2Ht»
Ethane , CzHe
C2 to Ca hydrocarbons
Propylene,
Propane ,
Ca to C*» hydrocarbons
Butylene ,
Butane,
Cn to Cs hydrocarbons
Pentene,
Pentane,
CB to Ce hydrocarbons
Hexene,
Hexane,
>Ce hydrocarbons
Total
0.5
15
<0.08
2.6
0.5
19
0.5
0.2
0.3
0.1
0.08
0.08
0.5
0.5
0.5
2.8
0.02
2.4
0.04
0.6
0.3
0.3
3.0
Note: Blanks indicate emissions not detected.
Determined by GC/FID at test site.
remained an insoluble solid white residue. Table 20 presents the
mass of organic material recovered for GC/MS analysis. It was
found that the hexane-soluble fraction was totally chromatograph-
able while the methylene chloride fraction of hexane-insoluble
material was largely nonchromatographable. The chromatographable
portion, however, did contain approximately 50% of the POM com-
pounds recovered from the total system. The nonchromatographable
portion was indicated to be largely high molecular weight fused-
ring aromatics (e.g., POM's, MW greater than 302).
The organic material recovered from the aqueous portion of the
sampling train was for the most part nonchromatographable. Ions
associated with organic acids were found and determined to be of
molecular weight greater than 284, e.g., stearic acid. The de-
tection limit of GC/MS for organic acids is quite high and their
presence may go undectected.
Emission rates, expressed as grams of pollutant emitted per kilo-
gram of wood, burned, for the major organic species, except POM's
(see Table 23), identified by GC/MS are presented in Tables 21
and 22. Because of limitations in the recovery, separation and
55
-------
TABLE 20. MASS OF ORGANIC MATERIAL RECOVERED FOR GC/MS ANALYSIS
(g)
Sample fraction
Hexane- inso lubl e
Test run conditions
Combustion
equipment
Fireplace
Fireplace
Fireplace
Baffled stove
Baffled stove
Nonbaff led stove
Nonbaffled stove
Nonbaffled stove
Wood type
Seasoned oak
Seasoned oak
Green pine
Seasoned oak
Seasoned pine
Seasoned oak
Green pine
Green pine
Sampling
system
train
PCM
SASS
POM
POM
POM
POM
POM
SASS
Hexane-
soluble
0.135
0.301
0.183
0.190
0.341
0.272
1.04
6.95
Methyl ene
chloride-
soluble
a
1.07
0.088
0.566
0.241
0.326
0.142
4.29
Solid
residue
a
~a
"a
0.105
0.096
-
Aqueous
extract
0.016
16.8
0.042
1.86
0.090
0.239
0.205
_b
No material recovered in this fraction.
The SASS train impinger contents and condensate were used for trace element
analysis.
identification of organic compounds, the nature of the fuels and
the combustion process, other species may have been emitted and
escaped detection. However, many compounds of environmental
interest (i.e., POM's) have been identified and quantified.
Table.21 presents the emission rates, expressed as grams of pol-
luttant emitted per kilogram of wood burned, for major organic
species emitted, other than POM's, for four test conditions.
The POM train and SASS train were both employed for collection
of these species and the results are reported separately in the
table. Over 50 organic species were identified, in addition to
POM compounds, in the flue gas from wood-burning stoves and fire-
places. Specific organic acids (i.e., actetic acid, formic acid,
etc.) were not identified because of the very high detection
limit, but their presence was expected and has been substantiated
as mentioned earlier. Generally speaking, the organic species
identified were dominated by the naphthalenes, furans, phenols,
cresols, and aldehydes. Total organic emission rates based on
individual speciation for each condition ranged from 0.2 g/kg to
2.9 g/kg including POM's. A comparison of these values to the
emission rates for condensable organic material (2.2 g/kg to
14 g/kg) presented earlier reveals that approximately 85% of the
condensable material was not identified by GC/MS. This is in
general agreement with the earlier discussion (see Table 20)
regarding the large amount of nonchromatographable organic
material.
56
-------
TABLE 21.
MAJOR ORGANIC
(gAg)
SPECIES EMISSIONS
tuftled stove
Major organic species identified
Ethyl benzene/xylenes
Indan*
Indent
Methyl indanes
Methyl indents
Napthalene
Methyl-naphthalenes
Cj-alkyl-naphthalenes
Biphenyl
Acenaphthylene
Acenaph thane
Benzo furan
Dibenzo furan
Fluorene
Anthracene/phenanthrene
Fhwiol
Cresols
Ca-alkyl phenols
Ca-alkyl phenols
C»-alkyl phenols
Benzaldehyde
d-alkyl benxaldehyda
Ca-alkyl benr aldehyde
Ca-alkyl benzaldehyde
Methyl furans
Ca-alkyl-furans/furfural
Cj-alkyl-furans/methylfurfural
C»-alkyl-furans/Ca-a.lkylfurfural
/ntthoxy phenols
Catechol
Naphthol
Methoxy phenols
Methyl methoxy phenols
Ca-alkyl nethoxy phenol*
Ca-alkyl nethoxy phenols
C«-alkyl methoxy phenols
Cs-alkyl methoxy phenols
Fluorenone
Fluorenone isomei
An throne
Benzan throne
Dimethoxy phenol
Hydroxy methoxy benzaldehyde
Hydroxy nethoxy acetophenone
Hydroxy methoxy benzoic acid
Hydroxy dimethoxy benzaldehyde
Hydroxy dimethoxy acetophenone
Hydroxy dimethoxy cinnamaldehyde
Ca-alkyl biphenyls (or isomers)
Cs-alkyl biphenyls (or isomers)
C»-alkyl biphenyls (or isomers)
Di-Cs alkyl-phthalate
Aliphatics
Total
Seasoned
POM train
0.0059
0.0029
0.0189
0.0315
0.0151
0.0623
0.0082
0.0069
0.0027
0.0110
0.0014
0.0041
0.0096
0.0110
0.0219
0.0123
0,2251
Fireplace
oak
SASS train
0.0076
0.0046
0.0038
0.0012
0.0063
0.0007
0.0032
0.0032
0.0120
0.0185
0.0601
0.0387
0.0179
0.0131
0.0004
0.0003
0.001S
0.0040
0.0014
0.0010
0.0047
0.0076
0.0073
0.0059
0.0147
0.0152
0.0022
0.0134
0.0412
0.0496
0.0011
0.0011
0.0011
0.0987
0.0228
0.0125
0.0607
0.0402
O.0135
0.0125
0.0231
0.0116
0.0328
0.0011
0.6941
Green pine
POM train
0.0123
0.0070
0.0166
0.0319
0.0094
0.0526
0.0084
0.0052
0.0029
0.0127
0.0016
0.0062
0.0068
0.0146
0.0348
0.0845
0.0470
O.0280
0.0157
0.0029
0.0035
0.0249
0.0105
0.0211
0.0034
0.0055
0.0094
0.0099
0.0066
0.0679
0.0004
0.0005
0.0008
0.0018
0.0144
0.0097
0.0435
0.6349
Seasoned
oak
POM train
0.0129
0.0123
0.0394
0.0317
0.0324
0.2729
0.0700
0.0290
0.0228
0.0754
0.0069
0.0150
0.0365
0.0224
0.0729
0.126S
0.1477
0.0949
0.0343
0.0122
0.0233
0.0131
0.0075
0.0041
0.0060
0.0053
0.0004
0.0034
0.0049
0,0023
0.0021
0.0002
1.2407
Seasoned
pine
POM train
0.0043
0.0136
0.0571
0.0815
0.0229
0.2356
0.0513
0.0214
0.0193
0.0792
0.0076
0.0083
0.0355
0.0243
0.0754
0.0926
0.1379
0.0594
0.0134
0.0167
0.0203
0.0206
0.0068
0.0120
0.0146
0.0130
0.0099
0.0086
0.0019
0.0038
0.0034
0.0017
0.0056
0.0011
1.1178
Nonbaffled stove
Seasoned oak
POM train
0.0342
0.0623
0.0643
0.0248
0.0264
0.3078
0.0311
0.0209
0.0220
0.0561
0.0097
0.0460
0.0238
0.0842
0.0442
0.2107
0.0720
0.0198
0.0093
0.0174
0.0106
0.0137
0.0398
0.0129
0.0159
0.0047
0.0042
0.0025
0.0136
0.0041
0.0061
0.0050
0.0023
0.0063
0.0103
0.0051
0.0007
1.3448
Green
POH train
0.1148
0.0421
0.1369
0.0230
0.0329
0.4393
0.0816
O.OS64
0.0139
0.0463
0.0132
0.0008
0.0011
0.0939
0.3616
0.4170
0.1512
0.0620
0.0092
0.0413
0.0918
0.0413
0.0689
0.1148
0.0734
0.0067
0.0038
0.0022
0.0037
0.0038
0.0023
0.014S
0.0004
0.0008
0.0011
0.0057
0.0053
0.0002
0.0038
2.583
pine
SASS train
0.00085
0.0012
0.0070
0.0029
0.0033
0.0007
0.0055
0.0006
0.0026
0.0026
0.0058
0.011
0.0363
0.0282
0.0148
0.0012
0.0002
0.0015
0.0033
0.0027
O.OOS7
0.0044
0.0121
0.0212
0.0227
0.012S
0.0541
0.0006
0.0008
0.0010
0.0023
0.0129
0.0079
0.0006
0.0038
0.295
Notes Blanks indicate emission factor not identified.
-------
By use of a direct injection probe (DIP) , it was determined that
a large fraction of the material that collected in the water im-
pingers was organic (aliphatic) acids of a rather high molecular
weight range, probably greater than 284 molecular weight (i.e.,
stearic acid). The remaining fraction of nonchromatographable
material was also examined by DIP probe technique and showed a
continuous stream of ions, many above 302 atomic mass units
(dibenzopyrene). This suggests emissions of a variety of high
molecular weight fused ring aromatics (i.e., POM's, MW greater
than 302).
The emission rates, expressed as grams of pollutant emitted per
kilogram of wood burned, presented in Table 21 suggest that for
species other than POM's the combustion equipment and wood type
had little effect on the individual emission rates. The results
of the two SASS train runs deserve some comment. Tests conducted
on the fireplace using the SASS train and POM train compare rea-
sonably well for compounds identified in both trains. It is not
expected that a close correspondence would exist because of the
difference in sampling times and sample volumes between the two
trains. Many more compounds were identified in the SASS train
sample, which is understandable because its larger sample volume
provides more material for analysis. This is most obvious in the
fireplace samples where the flue gas is much more dilute than the
flue gas from the stoves. Because of the additional species
identified, the total emission rate for chromatographable species
calculated from the SASS train is about 3 times greater than that
calculated from the POM train.
The remaining SASS run was conducted on the nonbaffled stove burn-
ing green pine. Compared to the corresponding POM train run the
SASS train results are about an order of magnitude lower instead
of higher as expected. The apparent explanation for this dis-
crepancy is that XAD-2 resin in the SASS train was overloaded
during sampling. The data in Table 20 were used to prepare
Table 22 showing the organic loading of the XAD-2 resin for all
of the POM train and SASS train runs.
Although the organic loading of the SASS run in question does not
appear higher than in the run performed on the fireplace, it does
not reflect the fact that the organic material collected in the
impinger and the condensate was not recovered. In the SASS run
on the fireplace in Table 20, presented earlier, the organic
material passing through the resin and trapped in the aqueous
components is 92% of the total organic loading. If this same
ratio is applied to the SASS run on the nonbaffled stove, the
mass of organics passing through the resin and trapped in the
impingers and condensate would be about 140 grams. This corres-
ponds to an organic loading of 121 percent of the virgin XAD-2
resin weight. An organic loading of much less than this would
overload the XAD-2 resin, indicating that overloading may have
occurred in some of the runs. This would explain the observed
low emission rates.
58
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TABLE 22. ORGANIC LOADING OF POM TRAIN AND SASS TRAIN
Combustion
equipment
Fireplace
Fireplace
Fireplace
Baffled stove
Baffled stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Wood type
Seasoned oak
Seasoned oak
Green pine
Seasoned oak
Seasoned pine
Seasoned oak
Green pine
Green pine
Sampling Organic loading,
system % of virgin
train XAD-2 resin
POM
SASS
POM
POM
POM
POM
POM
SASS
1
15
2
1.5
4
4
7a
>9a
The impinger contents and condensate from this run were used
for trace element analysis and the organic contents are there-
fore unknown.
Because XAD-2 resin selectively adsorbs organic species at vary-
ing rates, different organics break through at different tiroes
as the resin becomes overloaded. A highly sensitive technique
for screening POM's was used on one SASS run used to collect
samples for bioassay (baffled stove burning seasoned oak). Test
samples were taken from the sampling train before and after the
XAD-2 resin (specifically the rinse of the XAD-2 module and the
aqueous condensate). The results showed no POM's present after
the XAD-2 resin, and indicated that POM breakthrough did not
occur. The consistency of POM results from all runs on wood-
burning stoves, except the SASS run previously discussed, indicate
that POM breakthrough probably did not occur. Because the fire-
place flue gas was much more dilute, there is greater certainty
that POM breakthrough did not occur on the fireplace runs.
Emission rates, expressed as grams of pollutant emitted per kilo-
gram of wood burned, for individual POM compounds and total POM's
are presented in Table 23. Wood type does not appear to signif-
icantly influence POM emissions, but the total POM emission rate
was an order of magnitude lower for the fireplace than for the
woodburning stove. This is consistent with the CO and NOX
results, which indicate more efficient combustion and/or higher
combustion temperature in the fireplace. Comparison of the SASS
train results with those from the POM train for POM emissions
follows the same pattern as was discussed earlier for major
organic species and need not be reported.
In a previous study on the emissions from coal-fired residential
combustion system high concentrations of the POM compound 7,12-
dimethylbenzanthracene (DMBA) or its isomers (i.e., C2-alkly-
benzanthracenes/benzphenanthrenes/-chrysenes) were found in the
flue gas (12). This compound is known to be a strong animal car-
cinogen, and its potential presence in combustion flue gases is
of concern to the EPA. The EPA, therefore, requested Arthur D.
Little, Inc., to verify the test results; the EPA also submitted
an audit sample to MRC containing DMBA. Preliminary results from
Arthur D. Little have confirmed the presence of DMBA. The audit
sample results are presented in Appendix C.
59
-------
Cv
o
TABLE 23.' POM EMISSIONS
(9/kg)
Fireplace
POM compounds
Anthracene/phenanthrene
M*thyl-anthracenea/-ph*nan thrones
Ca-alkyl-«nthracenes/-pnenanthrene*
Cyclopenta-anthracenas/~phenanthrenas
Fluoranthene
Pyrene
Methyl-fluoranthenes/-pyrenes
Beaso (ghi) f luoranthene
Cyolopenta [edjpyrene
Beaco (c)phenanthrena
Bens (a) aBthracene/ohrysene
Methyl-bensanthracenes
— benspheiuuithfefies/— chKyssAssi
Ca-alkyl-bensanthraoenes/
-beasophenanthrenea/
-chrysenes
Benzofluoranthenes
Benxopyrenea/perylene
Methyl eholanthrene
Zndeno < 1 , 2 , 3-ed ) py rene
Banco (ghi)perylene
Anthanthrene
Diben*anthracenes/-phenanthreiMS
Dibenzocarbaaoles
Dibenzopyrene*
h
Total
Seasoned
oak
POM train SAS8 train
0.0082
0.0027
^0.0014
-------
Isomers of DMBA have also been found in this program on wood-fired
combustion systems, although, they represent less than 5% of the
total POM mass emitted. The lower-molecular-weight POM compounds
were found to exist in the highest concentration.
Because formaldehyde and certain other aldehydes were not expected
to be identified by GC/MS but were anticipated to be present in
the flue gas, a separate sampling train was employed specifically
for these compounds.
Table 24 presents the results of the aldehyde analysis as emis-
sion rates, expressed as grams of pollutant emitted per kilogram
of wood burned. Three trains were employed at each test condi-
tion, and flue gas samples were collected for approximately 20
min to 30 min in each case. The average of the 3 sets of results
for each test condition are more representative than the individ-
ual tests because of the short sampling times. As was the case
TABLE 24. ALDEHYDE EMISSIONS
(g/kg)
Aldehyde type
Formaldehyde
Average
Propionaldehyde
•Average
h
n-Butyraldehyde
Average
Xsobutyraldehyde
Average
Acetaldehyde
Average
Pentanol
Average
Fireplace
Seasoned oak
0.4
0.2
0.5
0.4
_C
.
_c
0.2
.
0.1
1.4
0.5
-^***
Baffled «tov«
Seasoned pine
0.02
0.02
0.4
0.1
~~
0.1
0.9
o.a
0.6
0.2
0.1
0.1
0.03
0.2
0.1
0.1
Nonbaffled stove
Green oak
0.5
0.3
0.1
0.3
0.1
0.1
0.1
1.7
0.6
0.1
O.S
0.2
0.2
0.1
0.1
0.03
Green pine
0.2
0.3
0.4
0.3
0.4
0.3
0.2
0.2
O.S
0.2
2.1
10.7
4.3
0.04
0.6
0.1
0.2
Note: Blanks indicate emission species not detected.
Analysed by colorlaetrlc technique employing ehmatropic acid.
Analyzed by GC/FID.
The calculated emission rate was 550 gAgi this is obviously erroneous
but could not be readily attributed to any traceable error in calculation.
analysis, or sampling.
61
-------
for the organic species presented in Table 21, the aldehyde
emission rates were not influenced by the combustion equipment
or wood type. The apparently high or low emission rates for any
one species are within the variability of the test results.
POM Screening Results
A method to screen for POM compounds present in flue gas emis-
sions was employed in this program in an attempt to determine its
utility for field application. The analytical method has been
reported in the literature (19) and was discussed earlier in
Section 3 along with the sampling technique. The results of the
field screening are presented in Table 25 along with laboratory
screening the field samples and the GC/MS results of the 6 POM
train samples. Because of the semiquantitative nature of the
screening technique, the results are presented as a range of
possible values.
TABLE 25. FLUE GAS FROM POM CONCENTRATIONS BY UV FLUO-
RESCENCE SCREENING9 OF GRAB SAMPLES VERSUS
CONVENTIONAL SAMPLING AND ANALYSIS
ODBbustion
equipment
Fireplace
Fireplace
Fireplace
Fireplace
Baffled stove
Baffled stove
Baffled stove
Baffled stove
Nonbaff led stove
Honbaff led stove
Nonbaf fled stove
Nonbaffled stove
Hood Lype
Seasoned oak
Green oak
Seasoned pine
Green pine
Seasoned oak
Green oak
Seasoned pine
Green pine
Seasoned oak
Green oak
Seasoned pine
Green pine
Field
430
200
40
410
110
5,000
44.000
210
60
430
20
430
PON
results
- 4.300
- 2.000
- 430
- 4,100
- 1.100
- 50,000
- 440,000 •
- 2,100
- 600
- 4.300
- 220
- 4,300
screening results
Laboratory
test t
220 -
200 -
40 -
410 -
110 -
2.500 -
14,000 -
110 -
20 -
40 -
20 -
20 -
2,200
2.000
430
4,100
1.100
25.000
440,000
1,100
200
430
220
220
GC/MS results
Laboratory of POH
test II train saBples
220 -
400 -
20 -
210 -
110 -
5,000 -
44,000 -
110 -
40 -
40 -
20 -
40 -
2,200
4.000
220
2,100
1.100
SO.OOO
440,000
1.100
390
430
220
430
450
5)0
12.000
21.000
9,800
16,000
Mote: Blanks indicate no data vere obtained.
Test procedure «as based on visual observation and MS at best seBiquantitative) as a result POM
concentrations are expressed as a range, ftozeescnt bttveen laboratory and field BeasuresKnts
indicates reproducibility in observation of fluorescent intensity.
MicrograB* of PON per actual cubic Mter of floe 9«s.
In all but two cases the laboratory observation of UV fluorescence
on the screening samples was consistent with the field results.
The quantitative flue gas concentrations as determined by GC/MS
indicate that the screening technique produced reasonable results.
In two cases the range of POM concentration determined by screen-
ing actually included the quantitative value, while in two other
cases, the range missed the quantitative value by factors of 2
and 4. The remaining two cases differed by factors of 11 and 15.
Of the four ranges that varied from the quantitative value, two
were low and two were high. In the sampling method employed for
screening flue gas was collected for only 30 to 60 minutes.
Therefore, it was expected that some variability would exist be-
tween results obtained by this method and those obtained by the
62
-------
POM train since flue gas samples were collected over 60 min to
120 min in the latter. Therefore, the cyclic nature of the wood-
burning process makes the screening sample the least representa-
tive. However, considering that the sampling and analysis for
the screening method was completed in the field in about 2 hours,
the level of uncertainty may be an acceptable trade-off.
Bioassay Results
Bioassay results for the twelve SASS train runs and for the com-
bustion residue samples (ash) are reported in Table 26 (31).
Discussions of the results observed for each bioassay test are
given in the following subsections. Specific test procedures can
be found in a report prepared by Litton Bionetics, Inc., (LBI)
for the EPA under a separate contract (31).
Ames Mutagenicity Assay—
The Ames Mutagenicity Assay test evaluates samples for genetic
activity in the Salmonella/microsome plate assays with and with-
out the addition of mammalian metabolic activation preparations.
The genetic activity of a sample is measured in these assays by
its ability to revert the Salmonella indicator strains from his-
tidine dependence to histidine independence. The degree of ge-
netic activity of a sample is reflected in the number of revert-
ants that are observed on the histidine free medium.
The results shown in Table 26 show that all of the emission sam-
ples (twenty-four) tested exhibited mutegenic activity. None of
the four samples of combustion residue showed mutegenic activity
(31).
CHO Clonal Toxicity Assays—
This test determined the cytotoxicities of twenty-four residen-
tial wood combustion emission samples to cultured Chinese hamster
cells (CHO-Kl cell line). The measure of cytotoxicity was the
reduction in colony-forming ability after a 24-hour exposure to
the test material. After a period of recovery and growth, the
number of colonies that developed in treated cultures was com-
pared to the colony number in unexposed vehicle control cultures.
The concentration of test material that reduced the colony number
by 50% was estimated graphically and referred to as the ECso
value (effective concentration for 50% survival). The toxicity
of the test materials is evaluated as high, moderate, low, or
nondetectable according to the range of EC5o values (Table 27).
(31) Level I Bioassays on Thirty-Two Residential Wood Combustion
Residue Samples. Contract 68-02-2681, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina.
(Final report submitted to the EPA by Litton Bionetics,
Inc., November 1979). 211 pp.
63
-------
TABLE 26. RESULTS OF BIOASSAYS PERFORMED ON SASS AND COMBUSTION RESIDUE SAMPLES (31)
Sample
code*
A-l
A-l
A-l
A-2
A-2
A-2
A- 3
A- 3
A-3
A-4
A- 4
B-l
B-l
B-2
B-2
B-2
B-3
B-3
B-3
B-4
B-4
C-l
C-l
C-2
C-2
C-2
C-3
C-3
C-3
C-4
C-4
C-4
(1)
(2)
(3)
(1)
(2)
(3)
(1)
(2)
(3)
(1)
(2)
(1)
(2)
(1)
(2)
(3)
(1)
(2)
(1)
(2)
(1)
(2)
-------
The cytotoxicity results indicated that the combined organic
module rinse plus XAD-2 resin extracts were, as a group, more
toxic than the particulate catch extracts. Within each group,
the fireplace samples were either the least toxic or in the least
toxic half of the test samples, and the nonbaffled stove extracts
were generally the most toxic. No generalizations regarding the
fuel source were apparent. Twenty-one of the twenty-four samples
tested were considered highly toxic, the others were described as
moderately toxic, or at the moderate-to-high toxicity borderline.
These results are given in Table 26 (31).
TABLE 27. DEFINITION OF RANGE OF EC5o VALUES
ECso values,
Toxicity yg/L
High <10
Moderate 10 to 100
Low 100 to 1,000
Nondetectable >1,000
Formulated by Litton Bio-
netics, Inc., under EPA
Contract 68-02-2581, Tech-
nical Directive No. 301.
Rabbit Alveolar Macrophage (RAM) Cytotoxicity Assays—
This assay determined the cytotoxicities of four bottom ash
samples to rabbit alveolar macrophages in short term culture.
The cells were exposed to the test material for 20 hours and the
following five cellular variables were measured: percent via-
bility index, total protein, total ATP, and ATP content per 106
cells. Each parameter was compared to the corresponding value
obtained for untreated control cell cultures. Then the concen-
trations of test material that reduced each parameter by 50%
were estimated graphically and referred to as the EC5o values.
This assay was limited to applied concentrations in the 3 yg/L to
1,000 yg/L range.
All four test materials (bottom ashes) were evaluated as having
low toxicity to RAM cells because the most sensitive assay pa-
rameter (usually ATP content) yielded ECso values in the 100 to
1,000 yg/L concentration range (31).
Level I Rodent Toxicity—
The Level I rodent toxicity test evaluates the acute toxicity of
the test materials when administered orally to male and female
rats. Attempts were made to test two combustion residue (ash)
samples. This test was abandonded when it proved impossible to
prepare a liquefied form of the combustion residue (31).
65
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Freshwater Toxicity Assays—
Freshwater toxicity assay determines the toxicity of the combus-
tion residue samples during 48-hour static exposure. The acute
toxicities of two of the combustion residue samples were deter-
mined for the freshwater invertebrate Daphnia magna.
The toxicity of the test materials is evaluated as high, moderate,
low, or nondetectable according to the range of ECso values
(Table 27). Both samples tested had nondetectable toxicity (31).
ENERGY EFFICIENCY TESTING
The energy efficiency of the combustion equipment tested in this
program was measured by Auburn University. The efficiency of the
wood-burning stoves was determined using a stack gas analysis
technique (32). The useful heat lost in the flue gas plus the
potential heat lost in combustible components of the flue gas
were determined and subtracted from the heat released by the wood
to arrive at a value for heat recovered and thus efficiency. The
procedure was repeated at 2-1/2-min intervals throughout the burn
of one charge of wood to observe the changes occurring during the
combustion cycle and to arrive at an average efficiency. Actual
calculations and various data correlations were performed by com-
puter. Appendix A presents the computer printouts of the raw
data and of calculated results from efficiency testing. The re-
sults are summarized in Table 28.
Fireplace efficiencies cannot be determined by this method be-
cause of the large volume of ambient air drawn into the fireplace
flue which dilutes the combustion gases. Previous tests conducted
in a calorimeter room on the fireplace resulted in a maximum
efficiency of 23%. Since there were no combustion air controls
on the fireplace and since it was operated in this study with the
heat recovery system turned on, it is reasonable to assume that
the efficiency of this fireplace remained fairly stable and near
its peak during testing.
Wood-burning stove efficiencies ranged from 22% to 52%, averaging
about 45%. Essentially no difference was seen between the baffled
and nonbaffled stove efficiencies. Higher efficiencies might be
achievable under different modes of operation such as a starved
air condition.
(32) Maxwell, T. T., D. F. Dyer, and G. Maples. Efficiency and
Heat Output Measurements for Residential rood Heating Appli-
ances. -In: Wood Heating Seminar 6, Wood Energy Institute,
Chicago, Illinois, February 1980. pp. 119-228.
66
-------
TABLE 28. SUMMARY OF EFFICIENCY TEST DATA OBTAINED ON
THE BAFFLED AND NONBAFFLED WOOD-BURNING STOVES
Combustion
device
Baffled stove
Baffled stove
Baffled stove
Baffled stove
Baffled stove
Baffled stove
Baffled stove
Nonbaffled stove
Nonbafflcd stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Nonbaffled stove
Nonbafflcd stove
Nonbaffled stove
Efficiency, %
Wood type
Seasoned oak
Seasoned oak
Green oak
Seasoned pine
Seasoned pine
Green pine
Green pine
Seasoned oak
Green oak
Green oak
Green oak
Seasoned pine
Green pine
Green pine
Green pine
Green pine
Green pine
Average Range
34
37
45
52
48
49
44
43
37
22
48
47
39
48
51
33
49
16
30
37
46
38
39
35
28
23
18
40
46
31
42
34
11
40
- 43
- 43
- 56
- 61
- 62
- 59
- 54
- 52
- 50
- 39
- 65
- 64
- 55
- 55
- 64
- 49
- 57
Average
excess
air, %
160
92
99
17
21
96
91
25
200
211
73
58
86
42
68
135
51
Combustion air vent settling
Top vent"
Full open
Open 2 turns
Open 1 turn
Open 1 turn
Open 1 turn
Open 1 turn
Open 1 turn
Bottom ventsc
Full open
Open 2 turns
Open 2 turns
Full open
Open 2 turns
Full open
Full open
Open 1.5 turns
Open 2.5 turns
Open 2 turns
Open 2 turns
Open 1 turn
Open 2.5 turns
Open 3 turns
Open 1.5 turns
Open 2 turns
Open 2.5 turns
Flue gas
temperature, °C Total wood
Average
310
328
272
372
321
324
326
413
297
390
324
282
320
437
326
315
410
Range charge, kg
170
266
204
275
225
144
241
166
177
208
227
186
169
206
180
182
223
- 391
- 385
- 354
- 401
- 359
- 428
- 461
- 426
- 443
- 599
- 372
- 485
- 569
- 581
- 428
- 443
- 566
13.5
13.5
11.2
9.1
9.4
6.0
8.6
11.7
13.1
13.4
9.2
10.8
9.1
6.4
11.1
11.0
9.2
Average
burning
rate, kg/hr
7.3
7.3
6.8
10.9
9.9
9.7
8.1
9.9
8.6
7.3
8.4
7.1
8.4
10.2
8.4
6.9
8.2
Note: Blanks indicate data not applicable.
Average and range of one test burning one wood charge.
Provides secondary combustion air.
Provides primary combustion air.
-------
SECTION 5
DISCUSSION OF RESULTS AND CONCLUSIONS
The preceding section presented test results from the sampling of
emissions from three wood-fired residential combustion systems.
The effect of certain test variables on individual emission
species was also observed and discussed. This section examines
more general correlations among the test parameters and draws
certain tentative conclusions from the data.
EFFECT OF COMBUSTION EQUIPMENT
Three combustion units were tested during this study: a residen-
tial fireplace, a baffled wood-burning stove, and a nonbaffled
wood-burning stove. A number of differences were noted in the
emissions from the stoves versus the fireplace. Both stoves,
however, behaved similarly. Carbon monoxide and POM emission
rates, expressed as grams of pollutant per kilogram of wood
burned, were an order of magnitude higher from the stoves than
from the fireplace, while NOX emission rates averaged four times
higher from the fireplace. Because of the scatter in the data
and the limited number of tests, only the NOX emission rates
were statistically different. No trends were noted in emissions
of particulate matter and hydrocarbons, although a high varia-
bility was evident in the test results.
These results suggest that conditions were more favorable for com-
plete combustion in the residential fireplace. Indeed, an exami-
nation of the wood-burning rate reveals that wood was consumed in
the fireplace at a rate 40% greater than in the stoves, evidence
of a hotter fire and better combustion. Both carbon monoxide and
POM's are products of incomplete combustion, and they would be
expected to be emitted in greater amounts under poorer combustion
conditions. It is unclear, though, why particulates and hydro-
carbons do not also exhibit higher emission rates from the stoves,
since they too form as a result of incomplete combustion. It is
possible that the high variability in the data has obscured the
true situation. Additional sampling would be needed to verify
this supposition.
Emissions of NOX depend primarily on combustion temperatures so
long as sufficient excess air is present for complete combustion.
Thus it is not surprising that higher NO» emission rates.
68
-------
expressed as grams of pollutant emitted per kilogram of wood
burned, occurred in the fireplace tests where hotter temperature
prevailed.
No significant differences were noted in emissions between the
two air-tight stoves tested during this program. The baffled
stove was designed to improve combustion efficiency by providing
longer retention time, a secondary combustion zone, and secondary
combustion air. These features are designed to allow combustion
of organic material escaping from the primary combustion zone.
Under the test conditions in this program the baffled stove pro-
vided no improvements in combustion as evidenced by the emission
rates and energy efficiencies.
Wood-burning stoves can be operated under starved air conditions
by closing the air vents in the stove doors, a practice followed
by some people to extend the burning cycle. However, in this pro-
gram, tests were conducted on stoves operated with an adequate
supply of combustion air. Under starved air conditions the wood-
burning unit acts more like a wood gasifier or pyrolysis device,
and causes creosote3 formation and build-up in the flue pipes.
Creosote formation is a fire hazard because of the potential for
ignition of the accumulated build-up. For this reason those
organizations promoting wood heating are educating the public in
this area, and are discouraging operation at the starved air
condition. More important to emission testing is the difficulty
in obtaining and characterizing representative samples during
starved air burning. Higher organic emissions can cause sampling
trains to become overloaded and fouled unless they are operated
for very short time intervals. Because of low air flow, flue gas
velocity becomes almost impossible to measure. Finally, complex
sample matrices become monumental analysis tasks. The end result
can easily be a long and costly test program yielding question-
able data. With this in mind, no testing was done in the current
program under starved air conditions, even though some stoves are
operated in this manner and are expected to produce higher levels
of organic emissions.
EFFECT OF WOOD TYPE
Of the four woods burned in this program, only yellow pine in the
green state had any noticeable effect on emissions. Particulate,
condensable organic, and POM emission rates, expressed as grams
of pollutant emitted per kilogram of wood burned, were all higher
when burning green pine, but usually by less than a factor of 3.
Examination of the fuel analysis (see Table 4) does not reveal
any significant difference in the basic chemical components of
aThe term creosote, although not technically correct, is commonly
used to describe the condensed resinous material collected on
chimney and flue pipe walls.
69
-------
the green pine. In all cases the composition is either close to
all of the other woods, or close to at least one other wood. A
difference would probably be found upon a more detailed chemical
analysis of the volatile portion of the wood. It has been
reported that softwoods contain from 0.8% to 25% resinous material
while hardwoods contain only 0.7% to 3% (10). The combination of
the high resin content and high moisture of the green pine appar-
ently influences the emissions generated when burning this wood
type. It has been suggested that particulate emission rates,
expressed, as grams of pollutant emitted per kilograms of wood
burned, (including the condensable organics) are directly affected
by initial fuel charge and inversely affected by the combustion
rate corrected for moisture (5).
EFFECT OF WOODBURNING CYCLE
Residential wood burning in fireplaces and stoves is cyclic in
nature, not only because it is a batch process but also because
wood burns in stages. Briefly the burning stages are drying,
distillation of volatile matter, and burning of carbonaceous
residue. All three stages occur simultaneously, however, drying
and distillation dominate early in the burn of a single charge
of wood. Figure 16 illustrates the variation in flue gas temper-
ature during the performance of one SASS train run on a wood-
burning stove measured 0.8 m from the flue gas exit. The wide
variation in temperatures and cyclic nature are indicative of
the nature of the combustion process.
n
• mm
OK MM SWR OF IMS
Figure 16. Flue gas temperature versus time for the
nonbaffled stove burning seasoned oak.
Basic combustion products (CO, C02, and H2O) have been shown to
cycle through the burn of one wood charge earlier in this section
More complete data are given in Appendix A. Others have shown
that particulate emissions also cycle during the wood burinq proc
ess as demonstrated in Figure 17 (5) . It would therefore be
70
-------
reasonable to assume that organic species such as POM's would also
cycle, being emitted at a higher rate during the early part of a
burn. A more extensive sampling program would be required to
measure this phenomenon.
1.0
•? 0.8
I
S
c 0.41
o
a
£ 0.21
\
£3C
10
20 30 40
Time (minutei)
50
60
Figure 17.
Particulate emissions during the
combustion of 2.27 kg of oak (5).
EFFECT OF CREOSOTE DEPOSITION ON REPRESENTATIVE SAMPLING
Because sampling probes were not located directly at the flue gas
discharge point, there was a question whether some of the emis-
sions sampled would normally condense onto the flue pipe wall in-
stead of being released to the atmosphere. Unpublished tests
conducted at the Auburn Woodburning Laboratory using an air-tight
stove show that the flue gas must be cooled to 125°C to 155°C
before significant amounts of creosote condense within the stack.
Because flue gas temperatures rarely dropped below this limit
during emission testing, it is believed that the samples collected
represent the actual emissions. This was verified by examination
of the flue pipe which revealed a minimum deposit of soot. As
mentioned earlier, however, creosote formation can be expected
when stoves are operated under starved air conditions.
GENERAL REMARKS AND CONCLUSIONS
This investigation is the most comprehensive program undertaken
to characterize emissions from residential wood-burning devices.
Nevertheless, test results apply only to the equipment and fuels
tested and only under the operating conditions employed in this
program. Caution should be exercised in extrapolating these
results to other test conditions. Because data obtained in this
study are in general agreement with other studies of this source
type, a certain degree of extrapolation may be justified. Fur-
ther studies to examine the effect of variables such as wood
geometry, firing rate, air-fuel ratio, combustion temperature,
design, ambient conditions, and secondary air is recommended to
provide more information on emission variables.
71
-------
The results of previous studies on fireplace for the most part
are supported by this program; however, the scope of those
studies was not as comprehensive. One study performed in Vail,
Colorado, on fireplace emissions reported significantly higher
emission rates, expressed as grams of pollutant emitted per kilo-
gram of wood burned (2). High altitude has been suggested as a
possible cause of this difference. Experts in the combustion
area consider this explanation highly unlikely, and it is probab-
ly due to some other variable. No studies to date have quantified
emissions from air-tight stoves under starved air conditions.
Because of the many variables associated with air-tight stoves, a
more extensive study would be necessary to examine this type of
operation. It is reasonable to assume that reducing the rate of
combustion will produce higher emission levels unless there is
some provision in the stove design which favors complete combus-
tion of evolved organics. The baffled stove design apparently is
not achieving this goal as intended.
Because of the nature of the residential wood combustion process
(large pieces of fuel, highly resinous fuel, uneven fuel distri-
bution, and hand-feeding in batches), the actual instantaneous
combustion efficiency is lower than in most other conventional
combustion systems. Thus, organic emissions are relatively high.
Because the organic emissions include a number of potentially
hazardous compounds (aldehydes, POM's, etc.), the trend toward
greater residential wood usage may have a significant impact on
local air quality. The emphasis on wood combustion in air-tight
stoves as an alternate energy source may greatly increase the
magnitude of the problem. The environmental impact of this
problem needs to be evaluated and emphasis needs to be placed on
sound engineering design of wood-burning equipment so that the
desired energy efficiency can be obtained in an environmentally
acceptable manner.
72
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REFERENCES
1. Snowden, W. D. , D. A. Alguard, G. A. Swanson, and W. E.
Stolberg. Source Sampling Residential Fireplaces for Emis-
sion Factor Development. EPA-450/3-76-010, U.S. Environmen-
tal Protection Agency, Research Triangle Park, North
Carolina, November 1975. 173 pp.
2. Source Testing for Fireplaces, Stoves, and Restaurant Grills
in Vail, Colorado (draft). Contract 68-01-1999, U.S. En-
vironmental Protection Agency, Denver, Colorado, December
1977. 26 pp.
3. Butcher, S. S., and D. I. Buckley. A Preliminary Study of
Particulate Emissions from Small Wood Stoves. Journal of
the Air Pollution Control Association, 27 (4) :346-347, 1977.
4. Clayton, L. , G. Karels, C. Ong, and T. Ping. Emissions from
Residential Type Fireplaces. Source Tests 25C67, 26C67,
29C67, 40C67, 41C67, 65C67, and 66C67, Bay Area Air Pollu-
tion Control District, San Francisco, California, 31 January
1968. 68 pp.
5. Butcher, S. S., and E. M. Sorenson. A Study of Wood Stove
Particulate Emissions. Journal of the Air Pollution Control
Association, 29(7):724-728, 1979.
6. Construction Report; Bureau of the Census Series C26; Charac-
teristics of New Housing: 1976. U.S. Department of Com-
merce, Washington, D.C., July 1977. 77 pp.
7. Current Industrial Reports, Selected Heating Equipment.
Bureau of the Census MA-34N(75)-1, U.S. Department of Com-
merce, Washington, D.C., July 1976. 6 pp.
8. Dyer, D. F., T. T. Maxwell, and G. Maples. Improving the
Efficiency, Safety and Utility of Woodburning Units, Volume
3, Quarterly Report No. W.B.-4. Contract ERDA EC77S05552,
Department of Energy, Washington, D.C., September 15, 1978.
9. Soderstrom, N. Heating Your Home with Wood. Popular Science
Skill Book, Times Mirror Magazines, Inc., New York, New York,
1978. 199 pp.
73
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10. Wood Chemistry, Second Edition, Volume 2, Wise, L.E., and
E. C. Jahn, eds. Reinhold Publishing Co., New York, New
York, 1974. pp. 475-479.
11. Environmental Protection Agency - Part II - Standards of
Performance for New Stationary Sources - Revision to Refer-
ence Method 1-8. Method 5 - Determination of Particulate
Emissions from Stationary Sources. Federal Register,
42(160):41776-41782, August 1977.
12. OeAngelis, D. G. and R. B. Reznik. Source Assessment:
Coal-fired Residential Combustion Equipment Field Tests.
EPA-600/2-78-004c, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, June 1977. 81 pp.
13. Yergovich, T. W. Development of a Practical Source Sampling
Slide Rule. Journal of the Air Pollution Control Associa-
tion, 26(6):590-592, 1976.
14. Environmental Protection Agency - Part II - Standards of
Performance for New Stationary Sources - Revision to Refer-
ence Method 1-8. Method 6 - Determination of Sulfur Dioxide
Emissions from Stationary Sources. Federal Register,
41(111):23083-23085, August 1977.
15. Environmental Protection Agency - Part II - Standards of
Performance for New Stationary Sources - Revision to Refer-
ence Method 1-8. Method 7 - Determination of Nitrogen Oxide
Emissions from Stationary Sources. Federal Register,
42(160):41784-41786, August 1977.
16. Environmental Protection Agency - Part II - Standards of
Performance for New Stationary Sources - Revision to Refer-
ence Method 1-8. Method 3 - Gas Analyses for Carbon Dioxide,
Excess Air, and Dry Molecular Weight. Federal Register,
42(160):41768-41771, August 1977.
17. Detector Tube Handbook, Air Investigations, and Technical
Gas Analysis with Drager Tubes, 2nd Edition, compiled by
Kurt Leichnitz. Dragerwerk AG., Lubeck, Federal Republic
of Germany, October 1973. 164 pp.
18. Methods of Air Sampling and Analysis. American Public
Health Association, Washington, D.C., 1972. pp. 190-198.
19. Smith, E. M., and P. L. Levins. Sensitized Fluorescence for
the Detection of Polycyclic Aromatic Hydrocarbons. EPA-600/
7-78-182, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, September 1978. 31 pp.
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20. Hamersma, J. W., S. L. Reynolds, and R. F. Maddalone. IERL-
RTP Procedures Manual: Level I Environmental Assessment.
EPA-600/2-76-160a, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, June 1976. 147 pp.
21. Lyles, G. R. , F. B. Dowling, and V. J. Blanchard. Quanti-
tative Determination of Formaldehyde in Parts Per Hundred
Million Concentration Level. Journal of the Air Pollution
Control Association, 15 (3):106-108, 1965.
22. Tentative Method of Analysis for Formaldehyde Content of the
Atmosphere (MBTH-Colorimetric Method - Applications to Other
Aldehydes). Health Laboratory Science, 7 (3):173-178, 1970.
23. Metals by Atomic Absorption Spectrophotometry. In: Stan-
dard Methods for the Examination of Water and Wastewater,
14th Edition. American Public Health Association, Washing-
ton, D.C., 1976. pp. 143-270.
24. Jarrell-Ash Plasma AtomComp for the Simultaneous Determina-
tion of Trace Metals in Solutions (manufacturer's brochure).
Catalog 90-975, Jarrell-Ash Company, Waltham, Massachusetts.
5 pp.
25. Bernas, B. A New Method for Decomposition and Comprehensive
Analysis of Silicates by Atomic Absorption Spectrometry.
Analytical Chemistry, 40(11):1682-1686, 1968.
26. Hartstein, A. M. , R. W. Freedman, and D. W. Platter. Novel
Wet-Digestion Procedure for Trace-Metal Analysis of Coal by
Atomic Absorption. Analytical Chemistry, 45 (3) :611-614,
1973.
27. Schorger, A. W. Chemistry of Cellulose and Wood. McGraw-
Hill Book Company, New York, New York, 1926. p. 51.
28. Young, H. E. Preliminary Estimates of Bark Percentages and
Chemical Elements in Complete Trees of Eight Species in
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29. Mingle, J. G. , and R. W. Boubel. Proximate Fuel Analysis
of Some Western Wood and Bark. Wood Science, l(l):29-36,
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31. Level I Bioassays on Thirty-two Residential Wood Combustion
Residue Samples. Contract 68-02-2681, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina.
(FinaL report submitted to the EPA by Litton Bionetics, Inc.,
November 1979). 211 pp.
32. Maxwell, T. T., D. F. Dyer, and G. Maples. Efficiency and
Heat Output Measurements for Residential Wood Heating Appli-
ances. In: Wood Heating Seminar 6, Wood Energy Institute,
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37 pp.
76
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APPENDIX A
THERMAL EFFICIENCY TEST DATA FOR THE BAFFLED
AND NONBAFFLED WOODBURNING STOVES
Thermal efficiency tests were conducted by Auburn University
during the emission testing program. Timing of individual effi-
ciency tests was not always synchronized with emission testing
because of the length of the emission testing and the need for
an undisturbed system during efficiency testing. Efficiency test
data were analyzed by computer to determine the thermal efficien-
cy and other combustion parameters. The computer also calculated
various other correlations.
The computer output for the thermal efficiency determination con-
tains the following information at specific times of the wood
burning cycle: mass of unburned wood, flue gas temperature, per-
cent C02, percent Oa, percent CO, percent combustibles, percent
efficiency, air-fuel ratio, theoretical air and heat release
rate. The following correlations are also provided by the com-
puter output and are presented in this Appendix:
(1) Percent efficiency versus heat release
(2) Flue temperature versus time
(3) Percent COa, O2, CO and combustibles versus time
(4) Air-fuel ratio versus time
(5) Heat release versus time
(6) Weight wood unburned versus time
(7) Percent efficiency versus time
In many instances the curves are off scale. Auburn University's
computer program is equipped to handle small charges of wood and
the scales employed could not accomodate the larger charges used
during this test program.
77
-------
kMUOD BURNING TEST RESULTS fl-l
fOM
TEST NUMBER t 1-3/14/79
UATE OF TEST : MARCH 14, 1979
AN81ENT TEMPERATURE :
75 OEti F
DAMPER SETTING :
FULL OPEN /ALL THREE
FUEL l SPLIT RtO UAK * PIECES g-f
<*01 STORE CONTENT 30.0 * NHV- -61/4.7
f ME
LBS rfOUD FLOt iAS XCO2
I6NP IF)
2
65
67
13
72
7>
T7
83
82
•5
•7
9J
92
95
95
0
34.0
556.J
55o.O
552.0 6.5 14.2
118525.
0.9 0.9 42.8 i.81 4.40 88430.
83*30.
74046.
0*894.
88430.
O.8 1.4 33.5 9.29 4..0 88394.
59299.
74096.
/4096.
592»3.
59299.
59263.
0.* l.l 38.4 10.14 4.40 46355.
R MARKS
AVtIAbE rttAT RELEASEDt
AVERACt HtAT OUTPUT :
AVERAGE eFMLIENCY :
97841.4 ITU/HR
33164.2 BTU/HR
33.9 t
TEST BV TIN. GLENN. PHIL, t TON
78
-------
I
.
TES1 NUMBER B-l
1-3/U/79
TEST NUMBER i-|
1-3/H1/79
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-------
MOUO BURNIi4G TEST RESULTS
TEST NUMBER : 2-3/IW79
DATE OF TEST : HARCH 1«*. 1979
AN4IENI
0*1 PER SETTING :
77 DEC F
ALL THREE 1.4LETS JPEM TMO TURNS
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80
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ca
TEST NUMBER
2-3/14/79 B
TEST NUMBER 8-1
2-3/1M/79
• CO?. » OZ.» C0,» COHB
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-------
BURNING TEST RESULTS 8*3
WOOD
TEST NUMBER : 1-3/19/79
OATE OF TEST : HARC-t 19.1979
AMBIENT TEMPERATURE : 76 DEG f
DA1PER SETTING :
BOTTOM FULL OPEN . TOP UPEN ONE TURN
FUEL : SEASONED PINE
MOISTURt CONTENT 25.0 * HHV» -6450.0
TINt LaS riJUO FLUE GAS *C02 (02
TEMP (Fl
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-------
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TEST NUMBER B-3
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TEST NUMBER 8-3
1-3/19/79
C82. « 02.« C0.> COM6
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- £ is
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-------
W30D BURNING TEST RESULTS
TEST NUMBER : 2-3/19/79
OATE OF TEST : HAACH 19,1979
4H3IENT TEMPERATURE : 81 OEG F
DAMPCR SETTINU :
BOTTOM UPEN TWO TURNS, TOP OPEN ONE TJRN
FUtL : ^EASONtO PINE
MJISTURfc CONTENT 25.0 I HHV- -6450.0
TMt L3S WOJO FLUE GAS «C32
I£MP (F)
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RATIO
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17
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27
30
32
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15.7 3.5 3.2 2.9 44.2 3.92
15.6 3.6 3.5 3.3 41.6 3.78
14.4 4.8 3.6 3.3 39.4 3.98
15.6 3.7 3.3 3.2 41.9 3.84
15.1 4.0 2.8 2.1 47.5 4.35
13.4 6.3 1.0 0.6 57.3 5.9tt
4.69
4.69
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108352.
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92857.
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REMARKS
AVERAGE HEAT RELEASEUi 141041.2 BTJ/HR
AVERAGE HI AT OUTPUT : 66942.2 BTU/HR
AVEgAUc EFflCIEriCY I 47.5 S
TEST BY TON* PHIL* AND
86
-------
|
I
TEST NUMBER 8-3
2i3/19/79
n
75
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TEST NUMBER l-»
2-3/19/79
• COZ. » 02.« C0.« COMB
0 10 M 30 tO SO BO
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-------
WOOD BURNING TEST RESULTS
NO*
TEST NUMBER : 1-3/15/79
DATE OF TEST t MARCH 15»1979
AMBIENT TEMPERATURE
71 DEO F
DAMPER SETTING :
TOP-1 TURNt BOTTOM-FULL OPEN
FUEL : SPLIT 'GREEN' PINE
MOISTURE CONTENT 30.0 Z HHV= -6174.7
TIME LBS WOOD FLUE GAS XC02
TEMP (F)
X02
0
2
5
7
10
12
15
17
20
22
25
27
30
32
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573.0
632.0 10.9 9.9
728.0
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783.0
801.0 14.1 5.8
802.0
790.0 11.9 8.3
732.0
702.0 9.4 10.0
XCO XCOM ZEFF A/F
RATIO
1.1 0.4 45.6 12.75
0.6 0.0 55.4 22.71
1.3 1.6 39.4 7.83
1.3 2.9 35.4 5.35
1.6 0.6 54.2 5.58
0.4 0.3 59.3 5.74
0.3 O.5 54.8 6.68
0.5 0.0 57.7 8.37
THEO HEAT RLSE
AIR BTU/HR
4.4O
4.40
4.40
4.40
4.4O
4.40
4.40
4.40
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118561.
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163027.
133359.
148193.
59263.
74096.
44465.
REMARKS
AVERAGE HEAT RELEASED: 130409.0 BTU/HR
AVERAGE HEAT OUTPUT : 63249.0 BTU/HR
AVERAGE EFFICIENCY : 48.5 Z
TEST CONDUCTED BY TOM PRUITT AND PHIL MAULDIN
88
-------
••
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TEST NUMBER »-1
1-3/15/79
75
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TEST NUMBER •-•/
1-3/15/79
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TIM HIN
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£
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0 10 20 30 40 SO 60
I I Ml HIN
-------
TEST NUMBER
UATfc OF TEST
BURNING TEST RESULTS $-.U
0.4 1.8 45.1 3.44
0.3 2.2 42.1 5.41
0.8 0.7 5J.8 t>.46 4.40
0.3 0.3 49.0 10.37 4.4U
AE4ARKS
AVtKAGL HtrAT HfcLtAStU: 1099UV.8 BTU/HR
AVfcftAGt HEAT OUTPUT : 479^6.5 BTU/HR
fcFFC.IENCY : 43.0 X
90
-------
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1-3/16/79
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TEST NUMBER B-t
1-3/16/79
« C02. x OJ,« CO." COHB
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TINE HIM
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10 20 30 10 50 60
TIME HIM
-------
UOOO BURNING TEST RESULTS
TFST NUMBER : 1-4/04/79-
UATE dF TEST : APRIL 4.. 1979
AMBIENT TEMPERATURE : 81 OEG F
HAMPER SETTING :
1.5 TURNS OPEN
FUEL : SEASON* O RED OAK
10ISTURF CONTENT 30.0 X
-6174.7
TIME L8S WJiJO FLUE GAS tCU2
TEHP (Fl
«U2 *CJ XCOM
«/F
KATIO
THcO HcAI KLifc
AVERAGE HFAT RELEASED: 133943.3 BTU/HR
3 BTU/HR
43.1 X
HtAT OUTPUT I
4VERAGE EFFICIENCY :
0
?
5
7
10
1?
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17
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77
75
27
10
\f
35
37
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42
45
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547.0
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549.0
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569.0
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567.0
597.0
607.0
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594.0
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2.8
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2.2
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1.8
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2.7
3.4
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TEST tONUUCTEJ BY OtbdlE (, JAW.R
92
-------
TEST DUMBER C'l TEST NUHBER C-l
l-H/OM/79 l-H/OH/79
« C02. » 02.» C0.« COMB
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'
\
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^
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-------
HOOD BURNING TEST RESULTS C -JL
/** I*, 14,
TFST NUMBER J 1-3/29/79 ' fOM
DATF Of TEST : MARCH 29.1979 IA/.M ft*
AMAIPNT TEMPERATURE S 82 OCvi F
OA4PFR SKTTMli :
TuO ANO ONE-HALF TURNS QPIU
FUEL : GREE.4 UAKISPLIT)
CONTENT' 39.0 < MHV- -5910.1
TIME
I »S WOOU FLUE GAS XCU2
TEMP ift
XJ2
7
70
72
74
77
HO
H7
15
• 7
1
30
0
)J
0
30
0
iO
10
O
30
O
iO
0
V)
O
3.1
0
30
J
Id
O
to
0
iO
J
10
J
30
0
30
1}
30
J
ill
J
in
2d.S
27.9
27.1
26.4
25.5
24.5
23.2
27.0
21.6
20. a
19.
18.
17.
15.
It.
13.
12.
11.
10.
9.9
9.1
S.i
7.8
/.3
6.7
b.l
5.6
5.0
4.6
4. 1
1.7
3.2
2.8
2.4
1.9
1.5
1.2
453.0
400*0
350.11
398.0
408.0
492. 0
492.0
528.0
537.0
S34.0
542.0
562.0
540.0
557.0
58J.O
575.0
S86.0
589.0
586.0
621.0
628.0
612.0
588.0
563.0
599.0
610.0
622.0
635.0
612.0
582.0
775.0
660.0
645.0
830.0
582.0
567.0
535. 0
3.d 17.2 0.7 1.5 <3.1 13.29 4.22
3.1 17.4 0.5 0.1 33.7 21.94 4.22
7.8 12.4 1.1 1.0 4*. 7 8.19 *.22
8.0 12.1 1.3 1.1 42.9 7.7J 4.22
7.6 12.2 l.J 0.4 09.6 d.6o 4.2c
'
A. 5 13.0 1.1 1.5 J».2 7.82 t.22
7.i 13.0 0.4 0.6 to. 4 9.>2 t.22
.
7.« 13.8 0.3 2.9 2t.7 6.9d 4.22
6.0 14.7 0.6 1.0 34.0 10.47 4.22
COL
4.7 16.2 d. 5 1.1 2t.O 12. oj 4.22
0.
l£ 7of b.
11J04C.
S9J1 7.
12 f£*4.
l<*ia*2.
1 d<«4i)l«
1 702U3.
I41d0 /.
164134.
1B44.J1.
17J2J3.
1 )4«U1.
Id44ul.
I?u0u».
l36iJ4u.
12/64t.
1 1 1 o 11 3.
70921.
5o/3 7.
7U421.
56723.
5 u 7S / .
70«1.
•jo!2*.
•*292V.
RFHAkKS
AVFMACE HEAT RELF.ASEOI 111852.5 BTU/Hft
AtflfKAGE HEAT OUTPUT I 4U823.0 BTU/HR
thflCIENCY t 3o.S X
TEST CuMOOCffct 8r uLi-NN I HUE
94
-------
TEST NUMBER C-JL
M
11
10
'
,:;
r
g
*
1 •
1 0
1
—
_
-3/89/7
1600
1500
1200
ik
„. "°°
•
UJ
*-600
3
^300
0
h
- •
»**-*"
- . .
- -
^«**
TEST NUMBER C-2.
1-3/29/79
• C02. « 02.« CO.* COMB
70 1110 210 280 3SO
HERT RISE BTU/MH X103
0 10 V 20 30 40 SO 60
TIN&HIN
0 10 20 30 HO SO 60
II* HIM
0 10 20 30 40 50 .60
TINE HIN
0 10 20 30 fO SO 60
TIME M1H
10 20 30 110 50 60
TIHE HIN
0 10 20 30 40 50 60
TINE HIN
-------
HOOD BURNING TtST RESULTS "*
TFST MMBEft : 2-3/29/79
DATE OF TEST J MARCH 29* 1979
AMRIENT TEMPERATURE I
82 UEG F
DMPtR SETTING J
TWO TURNS EACH
FUEL J GRFErt HAM SPLIT!
•40I&TJRE CONTENT 33.0 t HHV«
-5910.1
T1NF L8S -UOO FLUE GAS SCO2 «02 «CO «CON XfcFf- A/F THEO HEAI RL-.L
TEMP IFI HAT1U A1K
0
2
5
7
IJ
I?
IS
IT
?«J
7?
«
PT
«
\r
15
17
4O
«,/
«.•>
»7
SO
V
55
57
AO
A?
t.5
67
70
1?
n
?i
HO
A?
irt
«r
90
92
95
«*7
100
10?
IOS
0
30
0
JJ
0
JO
0
M
O
30
3
«O
O
W
0
30
O
»0
4
10
J
Id
0
u
O
3d
0
Id
a
id
j
J3
0
»J
d
)d
J
Ml
0
30
0
3d
0
29.6
29.2
2fl.fr
28.d
77.3
26.S
2%. 7
29.0
M.I
21.3
4?.*
?1.4
2J.6
1«.A
ia.a
17.9
IA.9
15.9
It. 8
13.*
I?. 9
12.0
II. 1
1J.2
«.3
d.5
r.a
7.2
t>.6
a.l
>.&
S.t
*.7
4.2
).«
i.i
3.1
2.9
2.6
?.+
2.1
l.fl
1.7
407.3
416.0
453.0
459.0
467.0
525.0
50*. 0
951.0
567. 0
657.0
636.0
635.0
6*4. 0
697.0
708.0
139.0
•29.0
•58. J
862.0
•54.0
549.0
570.0
1027.0
1110.0
1053.0
997.J
1020.0
942.0
•82.0
869.0
•75.0
887.0
882.0
d39.0
125.0
655.0
633.0
649.0
661.0
644.0
628.0
573.0
981. 0
0.
bo/iJ.
BSIIV.
7.1 13.5 1.0 l.» 38.1 8.22 «.22 9V31I.
11J446.
U3*dJ.
«.0 12.* 1.2 l.» 38.5 7.3* 4.22 VV282.
12/o/d.
113-.OJ.
7.0 13.4 1.0 1.1 35.4 8.74 4.22 U7t*4.
12764*.
I27t.ro.
6.4 19.O 0.8 10.6-20.1 3.65 4.22 t*ie>2.
113*0J.
6.4 13.5 J.7 0.5 J2.1 10.11 <».22
6.9 13.o 0.9 1.2 20.1 d.ttv +.22
7.0 13.6 J.4 0.7 17.I *.*3 *.22
6.9 13.9 '0.2 0.4 20.3 IJ.li 4.22
6.2 14.4 0.2 0.3 29.7 12.0*
e-a,
11J446.
dillv.
20J61.
3.0 16.7 J.3 O.d 26.2 23.63 4.22 liloJ.
AtfE«*»C »*AT
AtfcRlGI- tCAT OUTPtIT *
AtfER*Gc EFFICIENCY s
94222.9 BTU/MR
20581.8 8TU/HR
21.8 I
TEST CONDUCTED ay LES c Nut
96
-------
•
'
TEST NUMBER C-i
n
7S
|
£ 80
u
4"
£ 90
8
e is
0 _
—
- - o
•
•
•1
—
--
—
2-3/29/79
ISOO
1200
•" 800
s
^300
.
- —
5
r*~
\
I*
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f~/
1 \
>
!
TEST NUMBER
2-3/29/79
HER! «LSE BlU/Hfl xio'
0 10 20 SO «« SO 10
TIDE WIN
?0 30 40 SO 60
TINE MIN
0 10 20 JO 110 SO 60
TINE HIM
0 10 ?0 30 HO 50 80
Tint MIN
-------
MOOD BURNING TEST RESULTS C-JL
TfcST HU4BER : 1-4/03/79
DATE OF TEST : APRIL 3, 1979 lt«
A4HIENT TtMPkRATURE : 75 OEG F
OA4PER SE fTING :
TrfU TURNS EACH
FUEL : GREEN RED OAK
401 STlJRt CU.^TENT 33.0 *
HHV» -&910.1
TME LiJS rfJUU
0 0 20.2
7 30 19.7
5 0 l«.d
7
10
1?
15
17
70
?2
25
77
10
37
31
37
40
47
45
-»7
50
52
55
62
3i)
o
40
0
30
0
30
3
30
0
30
0
30
0
30
0
30
0
30
0
30
17.7
lo.S
14.2
13.7
12.2
11.2
10.3
9.t
«.•> .
7.6
6.8
6.0
i. 3
4.7
4. I
3.7
3.2
2.7
2.3
1.0
FLUE GAS
TEMP (F)
489.0
441.3
525.0
558.0
581.0
597.0
587.0
597.0
.624.0
644.0
645.0
645.0
646.0
663.0
680.0
690.0
701.0
635.0
586.0
618.0
634.0
695.0
674.0
607.0
XC02
11.3
12.3
11.9
11. 1
12.0
11.5.
12.0
11.4
8.5
7.5
«U2
8.9
7.5
8.1
9.1
b.l
8.3
.
8.2
d.9
12.2
13.5
zcu
2.0
1.0
1.4
1.2
1.0
1.2
0.9
0.3
0.1
SCO*
0.3
2.0
1.8
l.b
1.5
O.o
1.7
1.4
1.3
1.2
*tFF
64.6
44.9
45.3
43.7
4/.5
5b.3
44.8
45.6
44.6
39.7
A/F
RATIO
6.94
4.81
5.14
5.50
5.41
6.19
5.31
5.81
8.20
9.12
THcJ
AIK
4.22
4.22
4.22
4.22
4..
1276^4.
127 o4t.
11348U.
1134du.
V92d2.
tibll'J.
l>!> JJ4.
it»7b 7.
7J921.
70**^. 1 .
5f> It 3.
Ol4b7.
REMARKS
AVERAGE HEAT RELEASED: 10U934.0 BTU/HR
*
AVERAGE HEAT OUTPUT : 52639.5 BTU/HR
AVERAr.t EFFICIENCY : 48.3 X
98
-------
'. •
'1 1
n
N
ft
10
IS
i
...
x
•
...
i
•
-*•-
— I
....
- -
—
._
-
—
—
0 70 mo 210 260 SSO «
EST NUMf
-4/03/7
1800
1500
1200
b.
900
IU
" BOO
s
^300
0
IER C-2.
!
-
. ...
^
!'«>
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.*»••
.
-
r^
HCM W.SE BIU/HB XIO3
0 10 20 30 10 SO M
TIME H1N
«M
0 10 20 30 110 50 60
TIME M1N
10 20 30 110 SO 80
II Ml M1N
TEST NUMBER C-Z.
1-11/03/79
* C02. x 02.» C8.« COHB
0 10 20 SO 110 SO 60
TIHC HIM
0 10 to 30 ID SO M
TIRE N1N
0 10 20 30 <40 SO 60
TIBE MIN
-------
MOOD BURNING TEST RESULTS C-3
TFSI NUMBER : 2-3/28/79 H/4
**«
OATF OF TFST ! MARCH 28. 1»T9
AfMlFNT TEMPERATURE I 7? DEC f ••»•*««
DANPFR SETTING t
ONE TURN EACH
FUEL : itASONEU PINE
CONTENT 30.0 * HHV- -6 If*. 7
TI1E L»S -QUO FLUE GAS «C02 402 «CO «O* «FF A/F Trttu .I-4T RLSt
TEIW j ^ ..2 Q **.
> 0 22!9 47«Io £?!*•
» 13 27.6 492.0 10.0 10.U 1.4 1.3 >0.1 6.S4 4.40 ^32°.*
r id 22.0 904.0 l II it /
"a '» *»•<» 5M.O !""'*
1' 0 20.2 534.0 13.J 6.4 4.4 1.9 44.3 4.74 4.4J
If W 14.4 540.0
t"» 0 Id.9 563.0
If 30 17.a 569.0 13.0 6.4 2.6 2.1 4o.J 4.54 4.,0
'J O 16.7 575.0
>i tO 15.8 594.0 4JJ«v
?> " islo 61010 4J** *"° 2"2 »•'«••* *•« *.40 U1K.3'.
>» iO 14.2 673^0 !fis!!T*
»0 O 13.2 685.0 i,Jl£j
w fo ill*5 ifi-2 "•* 7^ 2-2 Ul **-6 >-*5 *•*" «"«•'
«? 30 12.2 675.0 , OiUx
^» 3 11.4 674.0 llaifcl
»? 0 10.7 691.0 13.2 3.6 2.8 1.2 *•»_•, k-«n ^.^ ,.«_^:
10 1J.6 697.0
M16V.
- 0 9.7 705.0 13**i9
^ *° 9.? 1*6.0 ,fr*?'
«5 3 rt.7 905.0
*t J '*** «76.0 12.0 7.0 1.2 O.i 4V.V 6.15 4.^
••7 >0 7.a 86?.0
»J O 7.2 866.0 «,„-,,
W *0 6.3 799.0 i.-lit'
5S 0 6.2 791.0 Ue34
•*7 30 b.O 798.J 11.2 d.d J.4 O.I t.6.6 1.27 ,.40 2ie3ll
"° " ».2 152.0
€^ »J 4.4 705.0
«5 O 4.3 656.0
?T J"i ^'? *!t*° *'* lj*fc %)'6 *•* **•' *•** *•*"
A7 3d 3.4 613.J
?j > »-* *i».o T;:::-
W »0 i.3 664.0 !*,**'
« .» 3.j *42.o ,cijr
77 *J 2.4 592.0 d««6*
*J a i.v 5O4^> /4-jft
** *° l-? *89.0 2J«Jl"
*•» '* ••* *«5.0 7.2 12.8 J.2 0.0 63.* 11.32 4.40
t«AT RELEASED! V1197.1 BTU/hh
t*AT OUTPUT : 4b981.1 BTU/Hk
Ef-l-lCIENCY 2 47.3 «
TEST CLNUUcTcJ
-------
TEST NUMBER C-3
2-3/28/79
Z to
•H
*
ut
PEHCEIIT
— u
m o
t-
0 70 IUO 210 280 350 «0
HCRT RLSf BIU/MB «10S
I DUU
1500
1200
ta.
900
" 600
S
^300
.
1
-
-
j
1
• -
- -
^ «f;
x*f i
...
—
>••*•
-
A
w
...
_
10 20 30 VO SO 60
HIM
TEST NUMBER C-S
2-3/28/79
* CO?. « OJ.» C0.« C8M8
\
. i
_ i
0 10 20 30 40 . 50 60
TIKE KIN
10 20 30 HO 50 60
TIME MIN
0 10 20 30 40 50 60
TIME MIN
-------
TFSI NUMBER
DATE OF TEST
HOOO BURNING TEST RESULTS C'*/
1-3/22/79 '
MARCH 22 t 1979
, /4, 'c.
AMBIENT TEMPERATURE :
7B DEC F
DAHPfcR SETTING :
BOTH DAMPERS TWO AND ONE HALF TURNS OPEN
FIIFL : WET flHE
NUISTURF Cl IN TEN I 30.0 X HHV- -6020.0
TIME LrtS WOOD FLUE GAS XCU2
TEMP IFI
0
•f
s
5
r
10
i?
i?
15
17
70
72
?$
77
79
13
12
15
17
••0
45
46
47
50
SI
•>2
•>-,
i7
J-*
AO
A2
0
10
S")
0
30
0
i)
30
0
3O
0
10
0
30
IS
0
30
0
10
J
0
%
to
0
0
10
0
10
0
o
10
7J.O
lv.2
19.0
Id. 4
lri.0
1 7.4
16.9
to.d
16.0
15. 1
14.6
li.9
!
-------
TEST NUMBtR
1-3/22/79
m
>
i;
B
--
T
1
J . ...
• t
' 1
_
"
i
_
.. .
__
- -
0
HERT BLSE BTU/HH XIOS
10 20 30 40 50 60
TINE MIN
280
210
140
l
c 70
10 20 30 10 SO 60
TIKE MIN
10 20 30 HO 50 60
TIME "IN
TEST NUMBER
1-3/22/79
• CO?. * 0?.« C0.« COHB
0 10 20 30 MO SO 60
IIHE HIM
0 10 JO 30 10 50 60
TIME BIN
j L
10 20 30 40 50 80
TINE KIN
-------
tfOOO BURNING TEST RESULTS C-*/
TEST iWHrtER : 1-3/23/79
UATE OF TEST : MARCH 23. 1979
AMBIENT TEMHFRATURE : 72 OEG F
DA^PtR SETTING :
dUTH DAMPERS OPEN THREE IUKNS
FUEL : MET PINt
CU.MTfcNT 30.0 £ HHV= -6020.0
TIME i as
0 0 !<•
MUQO
? JO I J . 3
4
5
7
10
10
12
14
15
15
17
19
70
72
77
75
75
77
30
37
35
17
RF-4A*
30 12
0 17
iO 1 1
.) la
*5 10
30 V
30 9
0 a
4J T
30 7
O o
0 :>
0 -»
iO t.
0 3.
«»5 • H.
30 3.
a 2.
30 1.
.7
. 3
.7
.6
.J
.5
.3
.2
. 9
.0
.4
. •)
.9
..3
.9
.6
. 1
.2
.5
0 0.3
iO .).
KS
AVEKAtic
Atft-ftAGr
2
HEAT
HEAT
FLJE GAS 4CU2
TEMP IF)
402.0
436.0
533.0
510.0
558.0
643.0
647.0
705.0
772.0
889.0
884.0
969.0
1078.0
1075.0
1013.0
1007.0
1019.0
1023.0
980.0
978.0
550. J
920.0
851.0
d.4
9.9
10.7
12.9
14.3
16.6
14.1
It. 6
13.8
12.9
ia.6
4EU2
11.6
10. 0
9.1
6.5
4.9
2.6
5.7
3.1
o.3
6.5
4.f
RELEASED! 133886.1
OUTPUT
i 63o91.2
1.3
1.0
1.8
2.1
2.3
1.3
1.0
0.5
0.1
0.0
1.2.
0.9
1.3
1.5
l.t
1.5
0.3
d.-t
*"
0.1
0.3
0*0
XtFF A/F
RATIO
45. o 7.»5
44.4 6.44
41. V 5.83
43. / 5.02
42.7 4.56
49.4 *.oO
44.4 5.23
52.2 5.00
51. S 6.J1
55.3 6.43
«*7.Jl /".7C.
1
Thlfu HcAf KLiE
AIR bTU/HR
0.
i 1 !>5V1.
'+.^J lut)37b.
2dodd V.
4.40 8o702.
15d907.
4.*0 289007.
1032OO.
4.-*0 lUJoOO.
192o5^.
4. 40 2l6oo 7.
15/024.
•*. »0 144504.
IdObOb).
•*.40 IBJouO.
7213*.
130 J?3.
't.tO 1443Uu.
1O32JO.
^••»0 liOJjJ.
101129.
4.40 101124.
B6702.
ff ^J-f
t.
I fit ft 4>R.
BTU/HR
BTU/Hk
AVERAut EFFICIENCY : 47.6
104
-------
•'I
7S
5 60
5 30
u
a
u
»- IS
a
- --
a
«*
C
r-
_..
0
i
0 70 HO 210 2BO 350 420
HEHT RISE BTU/HR KIO3
. „
ST NUMB
-3/23/7
I BOO
1SOO
1200
900
a.
X
w
"~ 600
3
^ 300
ER C-4
-
-
/
^
-
^V
_..-
10 20 30 10 SO BO
TIME HIM
TEST NUMBER C-1
1-3/23/79
* C02. « 02.» C0.« COBB
0 10 10 30 40 SO 60
TINC NIN
0 10 20 30 40 50 60
TINE NIN
10 ?0 30 40 50 60
TIME KIN
10 ?0 30 40 50 60
TINE M1N
H
75
u 60
t IS
Ul
>
5 30
u
a
LU
»- 15
(i
-••*
^*/-
/-
! f
3 1-
i i :
1
I i
0 10 20 30 40 SO 60
T1HE MIN
-------
MOOD BURNING ItST RESULTS C'l
TFST NUMAtK : 2-3/2i/79
DATE UF TEST : MARCH 23. 1979
AHfUtUr TEMPERATURE » 77 OEG F
DA4PFR SETTING I
iuTH OAHPERS OPEN 1.5 TURNS
FUFL : «ET PINF
Mm STORE CONTENT 30.3 X Hrt»- -6020.J
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FFflCIfcNT.Y S >0.7 X
TEST lONOtxTEO df HUt t BUi>T
106
-------
:
TEST NUMBER C-f
2-3/23/79
TEST NUMBER C-1
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TIME MIN
-------
NQOi) BURNING TEST RESULTS
TEST MUN9ER t 1-3/26/79
OAft Of TEST : MARCH 26. 1979
«««M*Mi
AtHIEMT TtHPERATURE :
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-------
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TEST NUMBER C-1
l-3/^6/7^
TEST NUMBER C-
1-3/26/79
1
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TIME M1N
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TIME M1N
-------
WOOD BURNING TEST RESULTS
TF%T NUMBER : 1-3/27/79
DATfc OF TEST : MARCH 27. 1979
:M<* *•'*•«
AMHIENT TEMPERATURE
70 OEG F
UA4PFR SETTING :
BOTH DAMPERS UPEN 2 1/2 TUKNS
FUEL : wFT PINE
iTUAF CONTENT 30.0 X HHV= -6020.J
TIM* L«S MOOO FLUE GAS XCU2
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Hi-AT OUTPUT : 93J/7.V BTU/Hfv
EFf-ICIENCV : 49.0 X
l-UNOUCTtJ BY ^LENN Afcu oukT
110
-------
TEST NUMBER
1-3/27/79
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600
300
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10 10 3D 40 50 6C.
TIKE KIN
TEST NUMBLR C-
1-3/27/79
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-------
APPENDIX B
STATISTICAL ANALYSES FOR PARTICULATE, CONDENSABLE ORGANICS,
NITROGEN OXIDES AND CARBON MONOXIDE EMISSIONS DATA
METHOD
The three controlled variable factors during this sampling pro-
gram were 1) combustion equipment type, 2) wood type, and, in some
instances, 3) sampling method. A statistical analysis was per-
formed to determine if the type of wood burned and/or type of
combustion equipment employed had a significant effect on pollu-
tion emission rates, expressed as grams of pollutant emitted per
kilogram of wood burned.
The Analysis of Variance (ANOVA) technique was used to determine
which factors in an experiment or test account for the greatest
variation in a measured parameter. In this case the ANOVA tech-
nique was used to determine if the type of combustion equipment,
the type of wood, or both, cause a significant change in pollu-
tion emission rates during controlled burning experiments. This
technique determines which of these two factors is significant.
However, if a large error term in the ANOVA matrix indicates that
1) a large systematic error is present, or 2) a factor not
accounted for in the experiment (such as, for example, amount of
oxygen available) is causing the significant change in the meas-
ured parameters.
The students' "t" test was employed to determine if the mean
emission rates for the two sources could have come from the same
population. For example: Given a mean emission rate for fire-
p_laces_ (X-i) and a mean emission rate for wood stoves (Xa) , does
X, = Xa?
Assuming unequal population variances (0i2 * Oa2), the t statistic
is computed as follows:
t = |Xi - X2|
f n-i na
and
112
-------
/S,2
\ ni
/si*\2
Vm )
•f Sa2V
(S2*\
, Ua )
V =
n-, - 1 n2 - 1
where X-i,X2 = the means of the emission rates, expressed as
grams of pollutant emitted per kilogram of wood
burned, for stoves and fireplaces, respectively
s12,s22 = the associated variances
n-i,n2 = the number of data points
v = the number of degrees of freedom for t
Once the t statistic is obtained, it is compared with the standard
tabulated statistical value for the same number of degrees of
freedom. A "t" value greater than that given in the tables indi-
cates a statistically significant difference in the means, i.e.,
the means are not from the same population. A "t" value less than
or equal to the table value indicates that there is no statistical
difference in the means.
The following discussions describe the statistical analysis for
carbon monoxide (CO), nitrogen oxides (NOX), condensable organics,
and particulate emission rates. It was assumed that 1) combus-
tion equipment, 2) type of wood, and 3) sampling method were the
major contributors to variation in emission rate levels. Table
B-l shows the maximum number of levels for each factor used in
the ANOVA matrix.
TABLE B-l. ANOVA MATRIX FACTOR LEVELS
Wood type Combustion equipment Sampling method
Seasoned oak Fireplace EPA Methods
Green oak Baffled stove SASS Train
Seasoned pine Non-baffled stove
Green pine
No. of levels =4 No. of levels =3 No. of levels = 2
113
-------
CARBON MONOXIDE (CO) ANALYSIS
The student's "t" test showed that there was no difference in the
mean emission rates, expressed as grains of pollutant emitted per
kilogram of wood burned, for the baffled and non-baffled stoves.
These data were combined and a (4x2) matrix of 4 wood types and
2 combustion types were run through ANOVA. Differences in samp-
ling equipment were not included due to lack of data.
TABLE B-2. ANOVA MATRIX FOR CO EMISSIONS
Factor
Wood type
Combustion equipment
Error
Total
DF
3
1
3
7
SS
8779
25536
7127
41441
MS
2926
25536
2376
0
calc.
1.23
3.54
-
^
Ftable (90%)
9.28
10.13
-
™"
Variance, %
21
62
17
"
Although a large portion of the variance (62%) is due to the com-
bustion equipment factor, this variation is not significant at the
90% level. This factor has only two levels (fireplace and stove),
so its effect cannot be adequately measured. Furthermore, this
experiment was not replicated; therefore, random and systematic
error is confounded. In order to determine if, indeed, these
factors are significant, more data are needed. Otherwise, another
factor as yet unaccounted for may have had more significance than
those chosen.
NITROGEN OXIDES (NOX) ANALYSIS
An analysis of variance (ANOVA) was also performed to determine
whether the type of wood burned and/or the type of combustion
equipment had a significant effect on the NOx emissions. The
resulting ANOVA matrix is shown in Table B-3.
TABLE B-3. ANOVA MATRIX FOR NOx EMISSIONS
Factor
Mood type
Combustion equipment
Interaction
Replicates
Error
Total
DF
3
2
6
5
55
71
SS
0.876
23.6
1.39
1.70
19.0
47.0
MS
0.292
11.8
0.231
0.340
0.345
-
Fcalc.
0.0046
1.24
-
-
-
"table (90%)
2.20
2.42
-
.
_
Variance , %
1.9
50
3
3.6
40
114
-------
A large portion of the variance (50%) in this experiment was
caused by the type of combustion equipment. However, the error
term is also large (40%); therefore, the F value is low (1.24).
It can not be concluded that the combustion equipment type causes
a statistically significant effect at the 90% confidence level
because the error term obscures this effect. The large error
term indicates that an "unknown" factor was not accounted for
in the experiment or that the systematic error was very large.
To determine if the mean NOX emission rates, expressed as grams
of pollutant emitted per kilogram of wood burned, differed signif-
icantly among the three combustion equipment types, a student "t"
test for equality of means was performed. This test indicates
that the two means are from different populations, i.e., it can
be concluded that the NOX emissions from the fireplaces were
higher than the emissions from the stoves. For this test, the
data from the two stove types were combined and treated as one
factor since there was no statistical difference between them.
PARTICULATE EMISSIONS ANALYSIS
The combustion equipment - sampling method interaction caused
the most variation but neither of these factors caused a statis-
tically significant variation. Without replication of sampling
runs, the error term is confounded (see Table B-4).
TABLE B-4. ANOVA MATRIX FOR PARTICULATE EMISSIONS
Factor
DF
SS
MS
calc.
F
table Variance, %
Combustion equipment
Sampling method
Wood type
Interaction
Error
Total
3
1
2
3
6
23
10.598
4.717
5.46
15.03
8.137
55.24
3.533
4.717
2.73
5.01
1.356
1.3
0.58
0.67
1.85
-
4.76
5.99
5.14
4.76
—
19
9
10
27
15
CONDENSABLE ORGANIC EMISSION ANALYSIS
An anlysis of variance indicates that the type of wood burned
causes a significant variation in the condensable organic emis-
sion rates, expressed as grams of pollutant emitted per kilogram
of wood burned. The type of equipment employed is not significant
(see Table B-5).
115
-------
TABLE B-5. ANOVA MATRIX FOR CONDENSABLE
ORGANIC EMISSIONS
Factor DF SS MS Fcalc. Ftable (95%) Variance, %
Wood 3 68.74 22.91 6.76 4.76 86
Combustion equipment 2 1.096 0.5481 0.11 5.14 1.4
Error 6 10.17 1.695 13
Total 11 80.011 -
116
-------
APPENDIX C
POM AUDIT SAMPLE RESULTS
This Appendix provides the results of an audit sample containing
POM's submitted to MRC by Research Triangle Institute, Inc. at
the request of the EPA Process Measurements Branch and Special
Studies group. Although the intention of this audit was to veri-
fy results of a recently completed study on residential coal-
fluid systems, it was also viewed as having utility in the
quality assurance area of this program on wood-fired combustion.
The audit sample containing a prepared mixture of POM's was coded
and submitted for GC/MS analysis along with the POM train and
SASS train samples in this study. A summary of the audit sample
results appears below in Table C-l.
TABLE C-l. SUMMARY OF POM AUDIT SAMPLE ANALYSIS
RTI mixture
1,2-Benzanthracene, MW 228
Chrysene, MW 228
Triphenylene, MW 228
7,12 DMBA, MW 256
Benz(a)pyrene, MW 252
—
RTI
Gravimetric
MRC identification mixture
Benzanthracene/chrysene , MW 228
7,12 DMBA (or isomers), MW 256
BenzCa or e) pyrene/perylene ,
MW 252
Napthobenzothiophene , MW 234
205
159
103
90
49
b
MRC
RTI GC/MS
analysis analysis
171
'194 4673
80 121
41 61
b 12
Isomers not resolved by MRC GC/MS system.
Possible contaminant, not added to RTI mixture.
Background information and details of the analysis are provided
in the following texts taken from RTI and MRC reports and
correspondence.
117
-------
GC/MS ANALYSIS FOR POM'S IN RTI PAH-1
Two vials were submitted for quantitative/qualitative GC/MS
analysis of POM content (given in terms of micrograms per milli-
liter) . The two vials were the same, both designated as RTI
PAH-i , so only one analysis was made. The solvent was determined
to be benzene. The analysis was performed on the HP5983-A GC/MS
system under the following GC conditions:
1/4" x 6" (0.006 m x 0.15 m) glass column packed with 3%
Dexsil 400 on Chromasorb W-MP
160°C - 2 min/8°C per min/300°C - 15 min
Helium Flow: 30 mL/min
Initial runs were made to identify POM species present. Four
peaks were observed: Major peak - molecular ion 228 at ^11.5
min, 2nd largest peak - molecular ion 256 at ^14.5 min, 3rd
largest peak - molecular ion 252 at %15.6 min, and the 4th weak
peak - molecular ion 234 at ^11.2 min. Because of the wide range
in concentration levels, a special standard mix was prepared to
approximate the concentrations of the sample. The identification
of the POM's based on spectra and retention time are as follow:
(1) Mol. Wt. 234
(2) Mol. Wt. 228
(3) Mol. Wt. 256
Napthoben zothiophene
Benz(a)anthracene or chrysene (or other
4-fused ring isomers
C2-alkyl-benzanthracene/-benzphenanthrene/
-chrysene, e.g., 7,12-dimethyl
benz(a)anthracene
(4) Mol. Wt. 252 — Benz (a or ejpyrene/perylene (retention
time too late for benzofluoranthenes)
Standards used for quantitation were napthobenzothiophene (1,2-
benzodiphenylene sulfide), benz(a)anthracene, 7,12-dimethly-
benz(a)anthracene, and benz(a)pyrene. Calculations and quantita-
tion are shown below.
Calculations: Standard Response - Peak Area T Concentration
Area
yg/mL
Sample Concentration — Peak Area T Standard Response
yg/mL
2 standard runs made and averaged; 2 sample runs made and averaged
Napthobenzothiophene
Standard Response: 9793 - 55 yg/mL •* 178 yg/mL ,_,
0967 55 yg/mL - 163 yg/mL x/1 per
Sample Concentration: 1878 - 171 yg/mL •* 11 yg/mL
2171 171 yg/mL - 13 yg/mL
12 yg/mL
118
-------
Benz(a)anthracene/chrysene (or isomer)
Standard Response: 75567 - 365 yg/mL - 207/yg/mL
70071 - 365 yg/mL - 192 yg/mL
Sample Concentration: 88134 - 200/yg/mL - 441 yg/mL
98718 - 200/yg/mL * 494 yg/mL
200 yg/mL
467 yg/mL
Ca-alkylbenzanthracenes (e.g., 7,12-Dimethylbenz(a)anthracene)
Standard Response:
4778 - 75 yg/mL * 64/yg/L
3980 - 75 yg/mL - 53/yg/L
Sample Concentration: 6029 - 59 yg/mL -* 102 yg/L
8203 - 59 yg/mL - 139
Benz(a or e)pyrene/Perylene
59 yg/mL
Standard Response:
Sample Concentration:
10573
9085
9717
10229
60 yg/mL - 176/yg/mL
60 yg/mL - 151/yg/mL
164/yg/mL - 59 yg/mL
164/yg/mL -» 62 yg/mL
164 yg/mL
61 yg/mL
Results Summary:
Napthobenzothiophene -* 12 yg/mL
Benz(a)anthracene/chrysene (or isomer) - 467 yg/ml
C2-alkylbenzanthracene (or isomer) — 121 yg/ml
Benz(a or e)pyrene/perylene - 61 yg/mL
Attached are the chromatograms/ion traces (234 ion trace not
shown) for both sample runs as well as the mass spectra of the
compounds and the area tables. The same is attached for one of
the standard runs. Some "splitting" occurred for mass above 250
AMU but it is felt that since there should be an equal chance of
occurrence for both sample and standard mix, the average of two
runs for each should produce acceptable results.
119
-------
** SPECTRUM
t'Prt>'RTI PON STD MIX, 40— 400PPM, 3UL
fc-I-GC 160-2/8x300 6'DEXSIL 400 GN6x7L
**
FRH 11301
1ST SC/PG:
X- .35 V"
253.0
256.0
228.
TI
9085.
A- 70071.
1 I i i i l
I I
I I
IS
-------
for
FILE NUMBER 113O1
ENTRY TIME
MASS
AREA
1 10.7
2 13.9
r — 3 15.0
4 10.0
(J5 10.6
6 11.4
7 14.6
8 15.8
9 10.7
10 11.3
228.0
256.0
252.0
234.0
234.0
223.0
256.0
252.0
234.0
234.0
75567.
4778.
10573.
10307.
514.
70071 .
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Monsanto
MONSANTO MSCAftCN CORFOKATON
Oiyton Lcboritory
ISIS Nickol» Road
Dirt on. Okie 45407
Phom: (513) 288-3411
TWX 810-459-1681
23 August 1979
Dr. W. F. Gutknecht
Research Triangle Institute
P.O. Box 12194
Research Triangle Park
North Carolina 27709
Dear Dr. Gutknecht:
Enclosed is a summary report of our GC/MS analysis of your sample
RTZ PAH- 1. We are also enclosing for your information the chrom-
atograms/ion traces for the sample and standard runs as well as
the mass spectra of the compounds and the area tables.
I would very much appreciate it if you could forward to me as
soon as possible the compound identities and concentrations in
the audit sample. Besides being of great utility in evaluating
our analytical methods, we plan to present a comparison of our
results with the RTI values in our forthcoming sampling report on
residential wood combustion emissions.
If you have any questions, please call me or Dr. Joseph Brooks,
Research Group Leader, GC/MS technology group.
Sincerely,
Daryl DeAngelis
DD/tak
Enclosure
cc Dr. Larry Johnson
EPA-RTP
Mr. John Milliken
EPA-RTP MD-63
• Mktitfiiry of Mon»MO Cemptlrf
138
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Preparation of 7,12 Dimethylbenzanthracene Audit Sample
for Monsanto Research Corporation
Introduction
In a report dated June 1978 and titled "Source Assessment: Coal-Fired
Residential Combustion Equipment Field Tests, June 1977" (EPA-600/2-78-004o),
Monsanto Research Corporation reported finding a level of 7,12, dimethylbenz-
anthracene (7,12 DMBA) which was about ten times as high as any other POM
identified. This fact has caused some alarm as 7,12 DMBA is a potent carcinogen.
In order to test the accuracy of both the qualitative and quantitative aspects
of the analysis, RTI prepared and sent MRC an appropriate audit sample. MRC
sent Arthur D. Little, Inc. an aliquot of the original sample upon which the
high 7,12 DMBA results were based; ADL was to perform a verification analysis
of this sample. Thus RTI sent an aliquot of its audit sample to ADL to be
analyzed along with the original sample. The audit samples were sent to MRC
and ADL on May 7, 1979.
Sample Design
The value for 7,12 DMBA reported by MRC in the June 1978 document may
well be correct. If it is not correct, two sources of error could be 1)
inaccurate identification of the compound, i.e., a compound of mass equal
to 7,12 DMBA being incorrectly designated 7,12 DflBA, or 2) poor separation of
compounds similar to 7,12 DMBA leading to inaccurate quantification. Most
other sources of error, such as miscalculation, have been eliminated. To test
these two error sources, it was decided to prepare a mixture of POM's similar
to and including 7,12 DMBA which would elute from a Dexsil column (the type
used by MRC) as a group. The compounds selected were: 1,2 benzanthracene,
chrysene, triphenylene, 7,12 DMBA and benz(a)pyrene.
A "realistic" audit sample wouTd have consisted of a deposit of these
compounds on an aliquot of XAD-2 resin, the material used to collect the orginal
sample. However, this complex sample would have introduced extraction as
a possible error source, which would have the potential of complicating an
analysis of the audit results. Thus EPA and RTI decided that the audit sample
should be simple, and accordingly, the audit sample consisted of the five
compounds dissolved in benzene at concentrations suitably high to prevent
interpretation problems due to being near detection limits. The possibility
of a second audit sample prepared with XAD-2 resin is still being considered.
139 :
-------
Sample Preparation and Verification
The compounds were purchased from commercial sources or obtained from
other groups In the Research Triangle Park. All were used without further
purification. The compounds (all solids) were weighed out In the RTI Toxic
Substances Laboratory and dissolved In Burdick and Jackson benzene. The
resultant concentrations are shown in the table below. This solution was
analyzed by Dr. Santosh Gangwal of RTI using a Varian 3700 GC and a 25 meter,
WCOT, capillary column containing OV101. His results, which have an estimated
uncertainty of +30%, are also shown 1n this table.
POM Audit Sample,
ug/mL in benzene
Compound RTI Expected Value* GC Value
1,2 benzanthracene 205 171
chrysene 159
(194)**
triphenylene 103
7.12 DMBA 90 80
benz(a)pyrene 49 41
*Based on gravimetric method of preparation
**A value for chrysene plus triphenylene is reported as these substances
are not resolved on the GC system used.
Sample Packaging
Aliquots of several ml each were placed in 7.4mL vials which had been
cleaned using the Level 1 procedure for cleaning glassware. The caps used
on the vials were Teflon-lined. Also, each cap was secured to the vial with
a tube of heat-shrink Teflon overlapping both the vial and the cap.
140
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RESEARCH TRIANGLE INSTITUTE
,0,T OF,,C. .OX ,,,.4
R (<« < A R C H T R I A N 0 I. K PARK. NORTH CAROLINA > 7 T a t
SYSTEMS AND MEASUREMENTS DIVISION
August 29, 1979
Mr. Daryl DeAngelis
Monsanto Research Corporation
Dayton Laboratory
1515 Nicholas Road
Dayton, Ohio 45407
Dear Mr. DeAngelis:
The results of your GC/MS analysis of the RTI audit sample have been
received and compared to expected results. These results are as follows:
RTI AUDIT MIXTURE MRC ANALYSIS RESULT
1,2 benzanthracene, benz(a)anthracene/chrysene
MW 228, 205 pg/mL (or isomer), MW 228,
467 ug/mL
chrysene, MW 228, *
159
triphenylene, MM 228,
103
7,12 DMBA, MW 256, 7,12 DMBA (or isomer)
90 ug/mL MU 256, 121 ug/mL
benz(a)pyrene, benz(a)pyrene/perylene,
MW 252, 49 wg/mL MU 252, 61 ug/mL
naphthobenzothiophene
MM 234, 12 ug/mL
From the ion current trace, it appears that the 1,2 benzanthracene,
chrysene and triphenylene were not resolved on your column. The total,
expected concentration for these three substances, I.e., 467 yg/mL, matches
your value for MW 228 exactly. There is good agreement between expected
and reported values for 7,12 DMBA and benz(a)pyrene. The naphthobenzothio-
phene was not purposely included 1n the audit mixture; it could be there as
(»!•) ««l-(0a« FROM RALEIGH. DURHAM
141
-------
an impurity though we have no evidence for Its presence.
If you should have any questions regarding these values or the prepara-
tion of the audit mixture, please do not hesitate to call.
Sincerely,
\fjU>
H. F. Gutknecht, Ph.D
WFG/nzh
cc: Or. L. D. Johnson (EPA)
Mr. John Milliken (EPA)
142
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GLOSSARY
ash: The incombustible matter remaining after the incinceration
of wood.
baffled stove: A stove structured with a piece of horizontal
sheet metal above the fire so that the combustion gases must
circulate around the sheet before they leave the stove.
creosote: A colorless or yellowish oily liquid containing a mix-
ture of phenolic compounds. Creosote is usually contained
in the tar of woods.
criteria pollutants: Those for which air quality standards have
been established.
damper: Valve or plate used to regulate the flow of air to a com-
bustion process.
draft: Pressure difference causing flow of a fluid, usually
applied to convection flow as in chimneys.
emission rate: As used in this report: grams of pollutant
emitted per kilogram of wood burned.
flue: Enclosed passage for conveying combustion gases to the
atmosphere.
green wood: Freshly cut wood containing most of its original
moisture content.
nonbaffled stove: A stove which lacks a metal divider between the
fire and flue resulting in direct exit of combustion gases.
proximate analysis: Fuel analysis on the basis of percent fixed
carbon, volatile matter, moisture, and ash.
seasoned wood: Wood which has been cured by drying to ensure a
uniform moisture content.
soot: Impure black carbon with oily compounds obtained from the
incomplete combustion of resinous materials, oils, wood, or
coal.
143
-------
ultimate analysis: Fuel analysis on the basis of elemental con-
tent; namely, carbon, hydrogen, oxygen, nitrogen, sulfur,
and ash.
zero clearance fireplace: A fireplace with enough air space
around its heated surfaces that allows it to be placed next
to a combustible wall.
144
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CONVERSION FACTORS AND METRIC PREFIXES (33)
CONVERSION FACTORS
To convert from
Degree Fahrenheit
Degree Celsius
Pound-mass
Pounds/hour
British thermal unit
(Btu)
Pound mass
(avoirdupois)
Ton (short, 2,000
Ib mass)
Pound mass/foot3
Mile2
Foot
Inch
Foot3
Pound-mass
Pound-force/in2
(psi)
To
Multiply by
Prefix Symbol
Giga G
Mega M
Kilo k
Milli m
Micro y
Degree Celsius (°C)
Kelvin (°K)
Gram (g)
Gram/second (g/s)
Joule (J)
Kilogram (kg)
Kilogram (kg)
Kilogram/meter3 (kg/m3)
Kilometer2 (km2)
Meter (m)
Meter (m)
Meter3 (m3)
Metric ton
Pascal (Pa)
METRIC PREFIXES
Multiplication
factor
toC = (toF - 32)/1.8
toK = toC + 273.15
4.535 x 102
1.260 x 10~1
1.055 x 103
4.535 x 10-1
9.074 x 102
1.602 x 101
2.591
3.048 x 10-1
2.540 x 10~2
2.832 x 10~2
4.535 x 10-*
6.897 x 103
Example
109
106
103
10~3
ID-6
1 Gg = 1 x 109 grams
1 MJ = 1 x 106 joules
1 kPa = 1 x 103 pascals
1 mg = 1 x 10~3 gram
1 ym = 1 x 10~c meter
(33) Standard for Metric Practice. ANSI/ASTM Designation
E 380-76 Std 268-1976, American Society for Testing and
Materials, Philadelphia, Pennsylvania, February 1976.
37 pp.
145
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TECHNICAL REPORT DATA
(Please read Inuructioni on the reverse before completing)
REPORT NO.
EPA-600/7-80-040
2.
3. RECIPIENT'S ACCESSION NO.
. TITLE AND SUBTITLE
Preliminary Characterization of Emissions from
Wood-fired Residential Combustion Equipment
5. REPORT DATE
March 1980
6. PERFORMING ORGANIZATION CODE
AOTHOR(S)
D. G. DeAngelis, D. S. Ruff in, and R. B. Reznik
8. PERFORMING ORGANIZATION REPORT NO.
MRC-DA-963
. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45418
1O. PROGRAM ELEMENT NO.
1AB015; ROAP 21AXM071
11. CONTRACT/GRANT NO.
68-02-1874, Task 23
2. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final: 1/79-1/80
14. SPONSORING AGENCY CODE
EPA/600/13
s. SUPPLEMENTARY NOTES iERL.RTp project officer is John O. Milliken, Mail Drop 63,
919/541-2745.
16. ABSTRACT
The report describes a study to quantify criteria pollutants and character-
ize other atmospheric emissions from wood-fired residential combustion equipment.
Flue gases were sampled from a zero clearance fireplace and from two airtight cast
iron stoves (baffled and nonbaffled). Four woods were tested: seasoned and green
oak and seasoned and green pine. Samples were analyzed for particulates, conden-
sable organics, NOx, CO, SOx, organic species, and individual elements. Consider-
able variability was observed in results under different test conditions. Average
emission factors compared favorably with other studies on residential wood combus-
tion. In most cases, variations in emission factors could not be correlated with
either combustion equipment or wood type, and were ascribed to systematic errors
or the effect of such variables as excess air level and wood arrangement. Combus-
tion equipment influenced emissions of CO, NOx, and POMs. Emissions of CO and
POMs were greater from wood-burning stoves, while NOx emissions were greater
from fireplaces. The only significant effect from wood type was the production of
more organic materials during combustion of green pine. Particulate emissions
were organic (50% to 80% carbon) and of resinous quality. More condensable orga-
nics were emitted than filterable particulate.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Field/Group
Pollution
Wood
Combustion
Fireplaces
Stoves
Chemical Properties
Residential Buildings
Pollution Control
Stationary Sources
Wood Stoves
13B
11L
21B
13A
07D
11M
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
158
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 O-71)
146
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