states EPA-600/7-82-038a
Environmental Protection
Agency May 1982
oEPA Research and
Development
ENVIRONMENTAL ASSESSMENT OF
A LOW-EMESDN OIL-FIRED
RESIDENTIAL HOT WATER
CONDENSING HEATING SYSTEM
Volume L Technical Results
Prepared for
Office of Air Quality Planning and Standards
Prepared by
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8 "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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Acurex Technical Report TR-81-78/EE
ENVIRONMENTAL ASSESSMENT OF A LOW-EMISSION OIL-FIRED
RESIDENTIAL HOT WATER CONDENSING HEATING SYSTEM
Volume I: TECHNICAL RESULTS
April 1982
Acurex Project 7600
Contract 68-02-3188
for
EPA Project Officer - R. E. Hall
Combustion Research Branch
Energy Assessment and Control Division
Industrial Environmental Research Laboratory
Research Traingle Park, North Carolina 27711
by
C. Castaldini
Acurex Corporation
Energy & Environmental Division
485 Clyde Avenue
Mountain View, California 94042
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CONTENTS
Figures iv
Tables v
Acknowledgements vi
1. Executive Summary 1
1.1 Residential Heater 1
1.2 Furnace Operation and Test Arrangement 4
1.3 Emission Measurements and Results 5
References for Section 1 15
2. Introduction 16
References for Section 2 24
3. Source Description 25
References for Section 3 31
4. Emissions Results 32
4.1 Furnace Operation and Test Arrangement 32
4.2 Flue Gas and Water Emissions 34
References for Section 4 58
5. Environmental Assessment 59
5.1 Source Analysis Model Evaluations 59
5.2 Bioassay Analysis 64
References for Section 5 65
Appendices
A. Test Equipment and Procedures 66
B. Trace Element Concentrations 82
C. Conversion Factors 92
m
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FIGURES
Number
1-1 Residential Hot Water Heater Equipped with Low-Emission
Distillate Oil -Fired Burner ................. 2
1-2 Schematic of the M.A.N. Residual Oil-Fired Burner ....... 3
1-3 Hot Water Residential Heating System Cycle Temperature
Profiles ........................... 7
1-4 Gas Sampling Location ..................... 8
3-1 Residential Hot Water Heater Equipped With Low-Emission
Distillate Oil -Fired Burner ................. 26
3-2 Schematic of the M.A.N. Residential Oil-Fired Burner ..... 27
3-3 Schematic of the Hot Water Tank ................ 29
3-4 Heat Exchanger Assembly .................... 30
4-1 Hot Water Residential Heater Temperature Profiles ....... 36
4-2 Gas Sampling Locations .................... 38
4-3 Strip Chart Recordings of Emissions During a Typical 40
Burner Cycle ........................
TABLES
1-1 Hot Water Residential Heating System Test Operating
Conditions ........................ 6
1-2 Summary of Flue Gas and Water Emissions ............ TO
1-3 Organic Extract Summary -- XAD-2 Sorbent Extract ....... 12
1-4 Bioassay Analysis Results .................. 14
2-1 Completed Tests During the Current Program .......... 20
4-1 Hot Water Residential Heating Systems Test Operating
Conditions ......................... 35
4-2 Flue Gas Emissions
4-3 Ultimate Fuel Analysis of Distillate Oil
iv
-------
TABLES (CONCLUDED)
Number Page
4-4 Trace Element Emissions 44
4-5 C-| to Cg Flue Gas Hydrocarbon Analysis 48
4-6 Results of TCO and Gravimetric Analyses of Total Extract
Samples 50
4-7 Summary of Infrared Spectrometry Analysis of Total
Extract Samples 51
4-8 Gravimetric and TCO Results of Column Chromatography
of the XAD-2 Samples 52
4-9 Infrared Analysis of Column Chromatography Fractions 53
4-10 Organic Extract Summary -- XAD-2 Sorbent Extract 54
4-11 Compounds Sought in GC/MS Analysis and Their Detection
4-12 Results of Quantification of POM Compounds 57
5-1 Flue Gas and Water Discharge Severities (Health-Based)
Greater than 0.1 for the Hadwick Furnace Equipped with
Low-N0x M.A.N. Burner 61
5-2 Bioassay Analysis Results 63
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ACKNOWLEDGEMENTS
Recognition for the success of the test program described herein
is due to the cooperation and technical support of Karl H. Klatt,
president of Karlsons Blueburner Systems Ltd. of Canada who arranged for
the procurement of the test furnace and Niels Rudi Pedersen of Danish
Aircraft Systems A/S who provided technical expertise on the operation of
the burner and furnace. Appreciation is also extended to the Acurex
source test team composed of Bob Markoja, Paul Jarman, and Gregg Nicoll
for their dedication and enthusiasm.
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SECTION 1
EXECUTIVE SUMMARY
This report describes emission results obtained from laboratory
testing of flue gas and liquid streams from a residential hot water heater
burning distillate oil. This work was performed for the Industrial
Environmental Research Laboratory (IERL) of the Environmental Protection
Agency (EPA) under the Combustion Modification Environmental Assessment
(CMEA) program, EPA contract No. 68-02-3188. The primary objective of the
tests was to measure flue gas and liquid emissions and to evaluate the
operating efficiency of the heater under simulated domestic operation in
the laboratory.
1.1 RESIDENTIAL HEATER
The residential heater tested in this program represents an
innovative European design utilizing a condensing flue gas system and a
high efficiency low-NO burner. The heater, illustrated in figure 1-1, is
A
targeted for the commercial and residential North American market through
Karlsons Blueburner Systems Ltd. of Canada. The burner, illustrated in
figure 1-2, is manufactured by Maschinenfabrik Augsburg-Nurnberg (M.A.N.)
of West Germany. The burner utilizes a finely atomized oil and recirculated
hot combustion gases mixed with fresh air to complete combustion of the
fuel in the burner pipe. The combustion of the fuel in the mixing tube
produces a stable "blue flame" which has become the trademark of this
-------
Figure 1-1. Residential Hot Water Heater Equipped With Low-Emission
Distillate Oil-Fired Burner (reference 1-1)
-------
Seal
Damper Mixing
Pipe
Burner
Pipe
Figure 1-2. Schematic of the M.A.N. Residual Oil-Fired
Burner
-------
burner design. The recirculation of the combustion gases also causes
NOX emissions to be 40 to 50 percent lower than those from a
conventional high-pressure atomizing burner widely used for residential
oil-fired furnaces.
The firebox is completely immersed in water. Combustion products
pass over the tank water surface and through a series of baffles and heat
exchanger tubes before they exit the furnace exhaust duct. The cooling
water, which serves to absorb the heat from the furnace and carry it to
the residence, enters through a heat exchanger tube located near the top
of the furnace and then goes through the immersed copper coils before it
exits. Condensation of the flue gas moisture begins when cool water meets
combustion products on their way out of the tank, condensing practically
all the water produced by combustion of the fuel.
1.2 FURNACE OPERATION AND TEST ARRANGEMENT
The test program called for the analysis of discharged water as
well as flue gas samples. Therefore, prior to the start of the test, the
interior surfaces of the water tank and cooling coils were subjected to
rigorous cleaning to remove all traces of solid organic and inorganic
material which might contaminate the initial water charge and lead to
erroneous conclusions. Following the cleaning, the tank was filled with
municipal tap water. A tap water sample from the tank was then collected
and used as a blank for all analyses of water discharge samples.
The tank water was then subjected to approximately one week of
conditioning to simulate as-found heater operation. Conditioning took
place by operating the heater in a cyclic mode (approximately 10 min
burner on, 20 min burner off), similar to the cycle that was implemented
during the test. After a week of cyclic firing, the pH of the tank
-------
reached a constant value of about 3.0. At that point, a tank water sample
was collected to be analyzed for anions, trace elements, and organic
concentrations.
An electronic data logger (Autodata 8) was used to record minute-by-
minute temperature readings of ambient air, stack flue gas, inlet water,
outlet water, and tank water during both burner-on and burner-off periods.
Table 1-1 summarizes heater settings and operating conditions during the
test. Figure 1-3 illustrates temperature profiles recorded during a typical
burner-on/burner-off cycle. The entire test period included 19 such cycles
for a total test time of 242 min.
The thermal efficiency of the heater calculated from the heat output
(the area in figure 1-3 between water-out and water-in temperatures), water
flowrate, and heat input (total fuel used during the test) measured 101 per-
cent. Because measurements of water flowrate and total fuel used are not
considered accurate to three significant figures, the efficiency of the unit
may have been slightly overestimated, as the greater than 100 percent would
indicate. However, it is safe to say that the thermal efficiency of this
condensing system is essentially 100 percent as indicated by measurements
of flue gas temperatures which were often lower than combustion air tempera-
tures.
1.3 EMISSION MEASUREMENTS AND RESULTS
Flue gas measurements were made at the exit of the furnace at
approximately 1m (3 ft) from the base of the uninsulated exhaust pipe as
shown in figure 1-4. Flue gas measurements included:
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Table 1-1. Hot Water Residential Heating System
Test Operating Conditions
• M.A.N. burner operating conditions:
-- Burner oil pressure 1.03 MPa (150 psig)
— Oil temperature ambient
-- Burner on-time 11 to 14 min
-- Burner off-time 22 to 25 min
-- Distillate oil flow 0.45 ml/sec (0.49 gal/hr)
• Hot water heating system initial settings and operating conditions:
— Tank water capacity 56.8 1 (15 gal)
-- Tank water at start of test 53.0 1 (14 gal)
-- Cooling water flow 107 ml/s (1.7 gal/min)
-- Tank water thermostat setting 54 to 55°C (129 to 131°F)
-- Average inlet water temperature 13°C (56°F)
-- Average rise of outlet water temperature 19°C (35°F)
-- Average rise of tank water temperature 32°C (58°F)
— pH of tank water 2.7
-- Approximate tank water discharge rate 0.47 ml/s (0.43 gal/hr)
-- Flue gas temperature 16.7 to 27.8°C (62 to 82°F)
-------
Cycle No. 7
Q Tank water temperature
Q Water out temperature
Q Water in temperature
£ Stack temperature
S
J
Cycle No. 8
< bOCXDOOCXDOCXDOOCKDOOO^^
i i i i i i i i i i i i i i i i i i i i
6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
Time after start of cycle (nhnutes)
Figure 1-3. Hot Water Residential Heating System Cycle
Temperature Profiles
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I I
I I
I Exhaust duct extending approx. 3m (9 ft)
above the furnace
co
High Volume Stack
Sampler (HVSS) for
particulates and
modified HVSS for
S02-S03 emissions
Exit flue
gas temperature
thermocouple
Source Assessment Sampling System (SASS) train
Gas flow anemometer
Bacharach smoke spot and sample
probe for gas chromatography
analysis
approx. 1m
(approx. 3 ft)
Furnace
Burner
Figure 1-4. Gas Sampling Location
-------
• Continuous monitoring for NOX, NO, CO, C02, 0,,, and TUHC
t Source Assessment Sampling System (SASS) for trace elements and
organic emissions
• EPA Method 5 for solid and condensable particulate mass emissions
• EPA Method 8 for sulfur species (S02> S03)
• Grab sample for onsite analyses of C-, - Cg hydrocarbons by
gas chromatography
t Bacharach smoke spot
Water samples at the end of the test were collected for laboratory
analysis of trace elements, organics, and anions. Bioassay tests were
also performed on the extract of the organic sorbent in the SASS and for
the water sample at the end of the test to estimate the potential toxicity
and mutagenicity to mammalian organisms.
Table 1-2 summarizes both flue gas and water emissions measured in
the test program. Emissions are presented in nanograms per Joule heat
input (ng/J) and in terms of their respective potential health hazard. The
potential health hazard is given by the Discharge Severity (DS) which is
defined as the ratio of the concentration of a pollutant to an appropriate
Discharge Multimedia Environmental Goal (DMEG). DMEG values were developed
by EPA for use in Environmental Assessment programs. They correspond to
maximum pollutant concentrations considered safe for short term exposure
(reference 1-2, 1-3). A DS greater than 1.0 suggests a potential hazard,
and more refined chemical analysis may be required to quantify specific
compounds present. Table 1-2 lists criteria emissions measured in the gas
stream and trace elements in both gas and liquid streams for which the
health-based DS exceeded 0.1.
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Table 1-2. Summary of Flue Gas and Water Emissions
Compound
Criteria Pollutant and
Other Vapor Phase
Emissions
CO
NO (as N02)
N02
TURC (as C3H8)
S02
SOj (vapor)
Solid particulate
Condensable particulate
Smoke
Organic Categories
Aldehydes
Carboxylic acid
Trace Elements & Anions
Copper, Cu
S0{ (condensed)
NOf (condensed)
Chloride, Cl"
Chromium, Cr
Iron, Fe
Lead, Pb
Manganese, Mn
Nickel , Ni
Selenium, Se
Sodium, Na
Sulfur, S
Zinc, Zn
Total Discharge
Severity (TDS)
Weighted Discharge
Severity (WDS), g/s
Flue Gas
Average
Concentration
(ng/J)
11.9
37.1
0
1.5
106.3
0
1.3
1.4
0
3.8 x 10";?
7.6 x 10"b
2.2 x 10"3
--
--
~ ~ n
1.3 x 10",
5.9 x 10",
1.1 x 10";?
5.2 x 10"*
3.3 x 10"J
9.6 x 10'5
>8.0 x 10'2
1.8 x 10'].
2.9 x 10"J
--
__
DS
(ND)
7.7 x 10"1
1.1 x 101
1.2 x 1073
1.0 x 101
"A
NAd
NA
--
0.40
0.20
3.0 x 10"2
--
—
--
3.4 2
2.1 x 10",
1.9 x 10 a
2.8 x 10"!;
5.7 x 10"'
1.3 x 10'3
>1.1 x 10' '
4.8 x 10-1
1.9 x 10"J
27.0
2,600
Waste Water
Average
Concentration
(ng/J)
--C
--
-.
--
--
--
--
--
--
--
1.1 x 10]
2.2 x 10'
1.5 x 10",
2.2 x 10 '%
1.1 x 10":
1.6 x 10"'
1.3 x 10"3
2.2 x 10*J
1.6 x 10'2
2.2 x 10'3
>2.2 x ID"1
_ _
..
DS
(ND)
_
--
—
--
--
--
--
--
--
100
67 ,
9.3 x 10"^
1.7 x 10-1
2.8
6.7
2.8 x 10" i
7.6 x 10"'
4.4
2.0
>4.0 x 10'1
185
8.7
Flue gas 02 and C02 concentrations are 1.9 and 12.9 percent respectively, dry basis
ND nondimensional
cDashes indicate that pollutant was not sought in the analysis or was below
detectable limit
d not applicable
10
-------
For the flue gas stream, NO and SCL emissions were responsible
for the highest DS values, both exceeding unity by nearly a factor of 10.
CO and total hydrocarbons were present at concentrations posing less concern
(DS less than 1.0). Four elements with DS greater than 0.1 were found in
the flue gas. These were chromium, nickel, sodium, and sulfur, with only
chromium having a DS exceeding unity. Both chromium and nickel can be
introduced as contaminants in sample preparation procedures prior to Spark
Source Mass Spectrometry (SSMS) analysis.
Total organic emissions in the flue gas measured 3.5 mg/dscm. Infrared
spectrometry (IR) and Low Resolution Mass Spectrometry (LRMS) indicated that
the organic matter consisted primarily of aliphatic hydrocarbons (about
90 percent), alcohols (about 4 percent), and carboxylic acids, esters, ketones,
or amines (about 5 percent). Table 1-3 summarizes these organic emission
results for the flue gas. The DS values shown in table 1-2 were calculated
assuming the levels shown in table 1-3 consisted entirely of the compound
with the lowest DMEG potentially present in the respective MEG category. In
this respect, the organic category DS values in table 1-3 represent conserva-
tive upper bounds.
Organic matter in the waste water was found to be at concentrations
less than detectable. Gas Chromatography/Mass Spectrometry (G'C/MS) analysis
of the organic sorbent extract showed the presence of anthracene/phenanthrene
and naphthalene in nonhazardous concentrations ranging from 2 to 36 yg/dscm.
Trace elements in the tank water for which DS exceeded unity were
copper, chromium, iron, nickel, and selenium. Copper levels significantly
exceeded those of any other trace element. This was probably caused by
11
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Table 1-3. Organic Extract Summary -- XAD-2 Sorbent Extract
Total Organics,
mg
TCO, mg
GRAV, mg
LCI
75
52
23
LC2
2
0.2
2
LC3
<3
<0.85
<2
LC4
<2
<0.1
<2
LC5
<2
<0.02
<2
LC6
2
<0.02
2
LC7
4
<0.02
4
2
85
54
31
Category
Aliphatic HCs
Aldehydes
Carboxylic Acids
Assigned Intensity -- mg/dscm
LCI
100--2.6
LC2
LC3
100-<0.11
LC4
LC5
LC6
LC7
100--0.14
2.6
0.11
0.14
-------
leaching of copper coils immersed in the warm acidic water. Concentrations
of copper in the 480 to 505 mg/1 range were detected using the more accurate
rate AA analysis versus greater than 10 mg/1 reported using the SSMS analysis.
Concentrations of 1,000 mg/1 of SO^ and 7 mg/1 of NO^ caused by
dissolution of SO? and NOo in condensed water in the flue gas, resulted in
acidic tank water with a pH of about 3.0. The DS for SO^ (as H2S04) is 67,
the second highest after copper. Nitrate concentrations, however, are not
sufficiently high to pose an environmental concern.
Total Discharge Severity (TDS), defined as the sum of all DS, for the
liquid stream exceeded that of the gas stream due primarily to the copper
and sulfate concentrations in the water. However, based on the total flow-
rate of each stream, the exhaust gas still poses a higher environmental risk
relative to the waste water as indicated by the Weighted Discharge Severity
(WDS) which is defined as the TDS times the mass flowrate of the stream.
Bioassay tests were performed on the organic sorbent (XAD-2) extract
and the tank water discharge -- bioassay results reported here are for health
effects tests only. These tests are (1) the Ames assay, based on the property
of Salmonella typhimurium mutants to revert due to exposure to various
classes of mutagens; (2) the cytotoxicity assay (CHO) of mammalian cells in
culture to measure cellular metabolic impairment and death resulting from
exposure to soluble and particulate toxicants; and (3) acute toxicity tests
in live rodents (RAT) to identify in vivo toxic effects of unknown compounds.
The results of these assays are summarized in table 1-4 for both the flue gas
sample (organic sorbent extract) and a liquid sample (tank water discharge
recovered at the end of the test). The responses recorded in the biological
tests varied from nondetectable to moderate toxicity and mutagenicity.
13
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Table 1-4. Bioassay Analysis Results
Sample
Organic sorbent XAD-2
Tank water discharge
Evaluation3
CHOb
L/ND
M
Amesc
Mc
ND
RATb
--
ND
ND = nondetectable toxicity/mutagenicity
L = low toxicity
M = moderate toxicity/mutagenicity
Toxicity test
cMutagenicity test
14
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REFERENCES FOR SECTION 1
1-1. "Hadwick 105," sales brochures provided by the Danish Aircraft
Systems A/S, Hobrovej 180 DK 9560 Hadsund.
1-2. Cleland, J. G., and G. L. Kingsbury, "Multimedia Environmental Goals
for Environmental Assessment: Volumes I and II," EPA-600/7-77-136 a,
b, U.S. Environmental Protection Agency, November 1977.
1-3. Kingsbury, G. L., et al., "Multimedia Environmental Goals for
Environmental Assessment: Volumes III and IV," EPA-600/7-79-176a,b,
August 1979.
15
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SECTION 2
INTRODUCTION
This report presents results of and describes environmental tests
performed for the Industrial Environmental Research Laboratory (IERL) of
EPA under the Combustion Modification Environmental Assessment (CMEA)
program, EPA contract No. 68-02-3188. The CMEA started in 1976 as a three-
year study, NO EA, EPA contract No. 68-02-2160, having the following five
X
objectives:
• Determine multimedia environmental stresses from stationary
combustion sources and combustion modification technology
• Develop and document control application guidelines to minimize
these stresses
• Identify stationary source and combustion modification R&D
prioriti es
• Support environmental assessment methodology development
• Disseminate program results to intended users
During the first year of the N0x EA, data and methodologies for
the environmental assessment were compiled. Furthermore, priorities for
the schedule and level of effort for the various source/fuel/control
combinations were identified. This effort revealed major data qaos
particularly for noncriteria pollutants (organic emissions and trace
16
-------
elements) for virtually all combinations of stationary combustion sources
and combustion modification techniques. Consequently, a series of seven
environmental field test programs was undertaken to fill these data gaps.
The results of these tests are documented in seven individual reports
(references 2-1 through 2-7) and in the final NO EA report summarizing
/\
the entire three-year effort (reference 2-8).
The current CMEA program has, as major objectives, the continuation
of multimedia environmental field tests initiated in the original NO EA
/\
program. These new tests, using standardized Level 1 sampling and
analytical procedures (reference 2-9) are aimed at filling the remaining
data gaps and addressing the following priority needs:
• Advanced NO controls
A
— Evaluation of controls with regard to the impending New
Source Performance Standard (NSPS)
-- Evaluation of controls designated Best Available Control
Technology (BACT)
t Alternate fuels
• Secondary sources
• EPA program data needs
— Residential oil combustion
-- Wood firing in residential, commercial, and industrial
sources
-- High interest emissions determination (dioxins,
radionuclides, etc.)
• Nonsteady-state operations
Residential distillate oil-fired heating systems have in recent
years been the subject of intensive investigation to assess the thermal
17
-------
efficiencies as well as their emissions. Results of these studies,
sunmarized in a NOX EA report (reference 2-10), have shown that
conventional residential warm air and hot water heating systems in the
field often have relatively low thermal efficiencies and that their
emissions, although small on a unit-by-unit basis, can often contribute
significantly to ambient air quality deterioration in urban areas during
the winter season. Furthermore, laboratory analyses of flue gas samples
have shown that total organic emissions measured on a heat input basis
from distillate oil-fired residential heaters operating in cyclic mode can
be significantly above organic emissions from other major stationary
combustion source categories (reference 2-11).
A number of low-emission, high-efficiency residential heating
systems/burners have been developed in recent years. In the NOX EA
program, flue gas emissions from one such low-emission, high-efficiency
residential warm air furnace were evaluated (reference 2-4). During the
current CMEA, two other residential heating systems have been investi-
gated. This report presents results of a hot water domestic furnace
in which the exhaust gas temperature is well below the water dew point
and thus the latent heat of water in the flue gas is recovered. This
condensing hot water furnace is equipped with a low emission distillate
oil-fired burner developed by Maschinenfabrik Augsburg-Nurnberg (M.A.N.)
and a subject of recent investigations by the IERL of the EPA. The
objectives of this test program were to assess multimedia emissions in gas
and liquid streams from the heater and to evaluate the operating
efficiency of the unit under simulated domestic operation in the
laboratory. Since this innovative domestic furnace design has not been
18
-------
installed in the United States, field tests under actual field operation
could not be pursued.
As mentioned earlier, concurrently with this test program, a second
residential low emission and improved efficiency furnace was also tested.
This furnace, developed by the Rocketdyne Division of Rockwell
International under EPA sponsorship, uses a conventional design
incorporating a state-of-the-art warm air furnace with modified low
emission burner and firebox designs. Results of the tests on the
Rocketdyne/EPA furnace are presented in a separate report (reference
2-12). Table 2-1 lists all the tests performed to date in the CMEA effort,
outlining the source tested, fuel used, combustion modification controls
implemented and the level of sampling and analysis performed in each case.
Results of these test programs are presented in separate reports available
through EPA.
-------
Table 2-1. Completed Tests During the Current Program
Source
Spark ignited natural
gas-fired reciprocating
internal combustion
engine
Compression ignition
diesel-f ired
reciprocating internal
combustion engine
Low-N0x residential
condensing heating
system furnished by
Karlsons Slueburner
Systems Ltd. of Canada
1
Rocketdyne/EPA
low-NOx residential
forced warm air furnace
Description
Large bore, 6 cylinder,
opposed piston, 186 kW
(250 Bhp)/cyl, 900 rpm
Model 38TDS8-1/8
Large bore, 6 cylinder
opposed piston, 261 kW
(350 Bhp)/cyl, 900 rpm
Model 38TDD8-1/8
Residential hot water
heater equipped with
M.A.N. low-NOx burner,
0.55 mJ/s (0.5 gal/hr)
firing capacity, con-
densing flue gas
Residential warm air
furnace with modified
high pressure burner and
firebox, 0.83 ml/s
(0.75 gal/hr) firing
capacity
Test Points
Unit Operation
-- Baseline (pre-NSPS)
-- Increased air-fuel
ratio aimed at
meeting proposed
NSPS of 700 ppm
corrected to 15
percent 02 and
standard atmospheric
conditions
-- Baseline (pre-NSPS)
-- Fuel injection retard
aimed at meeting pro-
posed NSPS of 600 ppm
corrected to 15 per-
cent 03 and standard
atmospheric conditions
Low-N0x burner design
by M.A.N.
Low-N0x burner design
and integrated furnace
system
Sampling Protocol
Engine exhaust:
-- SASS
-- Method 5
-- Gas sample (Cj - C6 HC)
-- Continuous NO, NOX, CO,
C02, 02, CH4, TUHC
Fuel
Lube oi 1
Engine exhaust:
- SASS
-- Method 8
— Method 5
-- Gas sample (Ci - C$ HC)
-- Continuous NO, NOX, CO,
C02, 02, CH4, TUHC
Fuel
Lube oil
Furnace exhaust:
-- SASS
-- Method 8
— Method 5
-- Gas sample (Ci - C^ HC)
-- Continuous NO, NOX, CO,
C02, 02, CH4, TUHC
Fuel
Waste water
Furnace exhaust:
- SASS
-- Method 8
-- Controlled condensation
-- Method 5
-- Gas sample (Cj - Cf, HC)
-- Continuous NO, NOX, CO,
C02, 02, CH4, TUHC
Fuel
Test Collaborator
Fairbanks Morse
Division of Colt
Industries
Fairbanks Morse
Division of Colt
Industries
PO
o
-------
Table 2-1. Continued
Source
Pulverized coal-fired
uti lity boiler,
Conesville station
Industrial boiler
Industrial boiler
Industrial boiler
Description
400 MW tangenti ally
fired - new NSPS
design aimed at
meeting 301 ng/J
NOX limit
1.14 kg/s steam
(9,000 Ib/hr)
fired with a mixture
of coal-oil-water (COW)
1.89 kg/s steam
1.89 kg/s steam
(15,000 Ib/hr)
hot water
firetube fired with a
mixture of coal-oil-
water (COW)
3.03 kg/s steam
(24,000 Ib/hr) watertube
fired with a mixture of
coal-oil (COM)
Test Points
Unit Operation
ESP inlet and outlet -
one test
-- Baseline (COW)
-- Controlled S02
emissions with
limestone injection
— Baseline (COW)
-- Controlled SO?
emissions with
N32C03 injection
-- Baseline test only
with COM
Sampling Protocol
ESP inlet and outlet
- SASS
-- Method 5
— Controlled condensation
-- Gas sample (Cj - C$ HC)
-- Continuous NO, NOX, CO,
C02, 02
Coal
Bottom ash
ESP ash
Boiler outlet
- SASS
— Method 5
— Method 8
-- Controlled Condensation
-- Gas sample (Ci-Cc HC)
-- Continuous 02, C0;>,
CO, NOX
Fuel
Boiler outlet
-- SASS
-- Method 5
— Method 8
-- Controlled Condensation
-- Gas sample (Cj - C^ HC)
-- Continuous 02, C02 NOX
Fuel
Boiler outlet
-- SASS
— Method 5
-- Controlled Condensation
-- Continuous 02, C02, NOX,
TUHC, CO
-- N20 grab sample
Fuel
Test Collaborator
Exxon Research and
Engineering (ERtE)
Envirocon
Adelphi University
PETC and General
Electric (GE)
PO
-------
Table 2-1. Continued
Source
Description
Test Points
Unit Operation
Sampling Protocol
Test Collaborator
Oil refinery vertical
crude oil heater
2.54 Ml/day
(16,000 bbl/day) natural
draft process heater
burning oil/refinery gas
Baseline
Staged combustion
using air injection
lances
Heater outlet
-- SASS
— Method 5
-- Controlled condensation
-- Gas sample (Ci - 05 HC)
-- Continuous 02, NOX, CO,
CO?, HC
NjO grab sample
Fuel oil
Refinery gas
KVB
Industrial boiler
8.21 kg/s steam
(65,000 Ib/hr)
watertube burning
mixture of refinery gas
and residual oi1
Baseline
Ammonia injection
using the noncatalytic
Thermal DeNOx
process
Economizer outlet
-- SASS
-- Method 5, 17
-- Controlled condensation
-- Gas sample (C\ - Cf, HC)
-- Ammonia emissions
-- N20 grab sample
-- Continuous 02, NOX,
CO, C02
Fuels (refinery gas and
residual oil)
Industrial boiler
2.52 kg/s steam
(20,000 Ib/hr) watertube
burning wood waste
Baseline (dry wood)
Wet (green) wood
Boiler outlet
-- SASS
-- Method 5
-- Controlled condensation
-- Gas sample (Cj - Cf, HC)
-- Continuous 02, NOX, CO
Fuel
Flyash
North Carolina
Department of
Natural Resources,
EPA IERL-RTP
Industrial boiler
3.16 kg/s steam
(29,000 Ib/hr)
firetube with refractory
firebox burning wood waste
-- Baseline (dry wood)
Outlet of cyclone particulate
col lector
-- SASS
— Method 5
-- Controlled condensation
-- Gas sample (Cj - Cf, HC)
-- Continuous 02, NOX, CO
Fuel
Bottom ash
North Carolina
Department of
Natural Resources,
EPA IERL-RTP
-------
Table 2-1. Concluded
Source
Description
Test Points
Unit Operation
Sampling Protocol
Test Collaborator
Enhanced oil recovery
steam generator
6.31 kg/s steam
(50,000 Ib/hr)
equipped with MHI low-NOx
burner firing crude oil
Emissions performance
mapping
Extended tests at
"optimum" emissions
performance
Exhaust duct
— SASS
— Method 5
-- Method 8
-- Gas sample (C-i - Ce HC)
-- NgO grab sample
-- Continuous 02, NOX, CO
C02, TUHC
Fuel
no
CO
-------
REFERENCES FOR SECTION 2
2-1. Larkin, R. and E. B. Higginbotham, "Combustion Modification
Controls for Stationary Gas Turbines: Volume II -- Utility Unit
Field Test," EPA-600/7-81-122b, July 1981.
2-2. Higginbotham, E. B., "Combustion Modification Controls for
Residential and Commercial Heating Systems: Volume II -- Oil-fired
Residential Furnace Field Test," EPA-600/7-81-123b, July 1981.
2-3. Higginbotham, E. B. and P. M. Goldberg, "Combustion Modification
NOX Controls for Utility Boilers: Volume I -- Tangential
Coal-fired Unit Field Test," EPA-600/7-81-124a, July 1981.
2-4. Sawyer, J. W. and E. B. Higginbotham, "Combustion Modification
NOX Controls for Utility Boilers: Volume II -- Pulverized-coal
Wall-fired Unit Field Test," EPA-600/7-81-124b, July 1981.
2-5. Sawyer, J. W. and E. B. Higginbotham, "Combustion Modification
NOX Controls for Utility boilers: Volume III -- Residual-oil
wall-fired Unit Field Test," EPA-600/7-81-124c, July 1981.
2-6. Goldberg, P. M. and E. B. Higginbotham, "Industrial Boiler
Combustion Modification NOX Controls: Volume II -- Stoker
Coal-fired Boiler Field Test -- Site A," EPA-600/7-81-126b,
July 1981.
2-7. Lips, H. I. and E. B. Higginbotham, "Industrial Boiler Combustion
Modification NOX Controls: Volume III -- Stoker Coal-fired
Boiler Field Test -- Site B," EPA-600/7-81-126c, July 1981.
2-8. Waterland, L. R. et al., "Environmental Assessment of Stationary
Source NOX Control Technologies -- Final Report," Acurex Report
FR-80-57/EE, April 1980.
2-9. Lentzen, D. E. et al., "IERL-RTP Procedure Manual: Level 1
Environmental Assessment (Second Edition)," EPA-600/7-78-201
October 1978.
2-10. Castaldini, C. et al., "Combustion Modification Controls for Resi-
dential and Commercial Heating Systems -- Volume 1- Environmental
Assessment," EPA-600/7-81-123a, July 1981.
2-11. Castaldini, C., "Organic Emissions in Stationary Combustion Sources
Under Baseline and Low-N0x Operation," ASME paper presented at
the Winter Annual Meeting, Chicago, Illinois, November 1980
2-12. DeRosier, R., "Environmental Assessment of Low Emission Oil-Fired
Residential Warm Air Furnace," Acurex Draft Report No TR 31
July 1981. '
24
-------
SECTION 3
SOURCE DESCRIPTION
The residential hot water heater, illustrated in figure 3-1,
combines a low-emission, high-efficiency distillate oil-fired burner with
a condensing heat exchanger. The burner, manufactured by M.A.N., utilizes
blue flame combustion technology developed by Professor Buschulte of the
German Research and Testing Laboratory for Air and Space Travel (DFVLR).
Its design produces NO emission levels which are normally 40 to 50
J\
percent below those from conventional residential oil-fired high-pressure
atomizing burners.
The burner, illustrated in figure 3-2, utilizes finely atomized oil
and recirculated hot combustion gases mixed with fresh air to complete the
combustion of the fuel in the burner pipe. The fuel oil can be
pressurized to 2.1 MPa (approximately 300 psi) and is atomized by a 60
hollow cone nozzle delivering about 0.53 ml/s (0.5 gal/hr). The
combustion of the fuel in the mixing tube produces a stable blue flame
which has become the trademark of this burner design. Because the M.A.N.
burner recirculates the combustion gases internally within the burner pipe
where combustion is completed, retrofit installation on existing
residential heating systems is possible. Although other blue flame burner
designs have been developed and implemented in the United States
(reference 3-2), the retrofit capability of the M.A.N. design has made it
25
-------
Figure 3-1. Residential Hot Water Heater Equipped With
Low-Emission Distillate Oil-Fired Burner
(reference 3-1)
26
-------
Seal
Oil [
Damper
Mixing
Pipe
Burner
Pipe
Figure 3-2. Schematic of the M.A.N. Residential Oil-Fired Burner
27
-------
attractive as a potential technique for reducing NO emissions from
A
existing residential units.
Figures 3-3 and 3-4 illustrate the hot water tank and heat
exchanger assembly, respectively. The firebox, shown in figure 3-3 is
completely immersed in water. The water level reaches approximately 2 cm
(less than one inch) below the top of the three exhaust pipes. This water
level is controlled by positioning the condensed water drain spout.
Before the combustion products exit the furnace exhaust duct, they pass
over the water surface and through a series of baffles and heat exchanger
tubes. The baffle and heat exchanger tubes configuration is illustrated
in figure 3-4.
The cooling water, which serves to absorb the heat from the furnace
and carry it to the residence, enters through a heat exchanger tube
located near the top of the furnace and then goes through the immersed
copper coils before it exits. Condensation of the water in the flue gas
begins when cool water meets combustion products on their way out of the
tank, condensing practically all the water produced by combustion of the
fuel.
Condensing heating systems for domestic hot water or warm air have
been proposed as a means of reducing residential fuel consumption
(reference 3-4). The Hadwick 105 furnace tested during this program
represents one such condensing heating design where combustion
efficiencies exceeding 95 percent under normal cyclic operation can be
achieved. This high thermal recovery represents a significant improvement
over cyclic efficiencies of existing residential heating systems which are
normally at about 75 to 80 percent (references 3-4, 3-5).
28
-------
Furnace exhaust duct
Firebox exhaust
pipes
Hot
water
thermo-
couple
location
Burner
axis
Waste
tank
drain
Condensed water
drain spout
Figure 3-3. Schematic of the Hot Water Tank (reference 3-3)
29
-------
Cool ing water
outlet
Cool ing
water
inlet
Copper
coils
immersed
in water
Figure 3-4. Heat Exchanger Assembly (reference 3-
3-3)
30
-------
REFERENCES FOR SECTION 3
3-1. "Hadwick 105," sales brochures provided by the Danish Aircraft
Systems A/S, Hobrovej 180 DK 9560 Hadsund.
3-2. "The Blueray System," Fuel Oil & Oil Heat, Vol. 36, No. 5,
pp. 42-44, May 1977.
3-3. Jydsk Teknologisk Institut - Danish Aircraft Systems A/S, 42-47097-8.
3-4. Putman, A. A. et al., "Survey of Available Technology for the
Improvement of Gas-Fired Residential Heating Equipment," Battelle
Columbus Laboratories and AGA report for DOE Brookhaven Labs,
BCL 51067, August 1979.
3-5. Castaldini, C. et al., "Combustion Modification Controls for
Residential and Commercial Heating Systems -- Volume 1: Environ-
mental Assessment," EPA-600/7-81-123a, July 1981
31
-------
SECTION 4
EMISSIONS RESULTS
The objectives of this test program were to measure exhaust
emissions during normal cyclic operation and to quantify the pollutant
concentrations in the water stream leaving the furnace. This section
describes the test arrangement and presents emissions results measured in
the exhaust flow gas duct and condensed water leaving the tank.
4.1 FURNACE OPERATION AND TEST ARRANGEMENT
The condensing hot water residential furnace tested in this program
has just recently been introduced to the North American market. Although
in widespread use in some countries in Western Europe, there are no known
domestic installations in the United States or Canada. Therefore, a new
unit was obtained by the Danish Aircraft Systems A/S in cooperation with
the Karlsons Blueburner Systems Ltd. of Canada. This unit was set up in
the Acurex combustion laboratory where access to emissions monitoring
equipment was relatively straightforward.
Since the test program called for analysis of water samples
collected during and at the conclusion of the test, the interior surfaces
of the water tank, exhaust duct, and cooling coils were subjected to
rigorous cleaning prior to the test. The objective of the cleaning
procedure, which included water with soap wash followed by distilled water
rinse, methyl alcohol, and methylene chloride in that order, was to remove
32
-------
all traces of solid organic and inorganic material which might contaminate
the initial water charge and lead to erroneous test conclusions.
Following the cleaning procedure, the tank and coils were rinsed
with an initial charge of tap water poured into the tank through the
exhaust flue gas duct. The tank and heat exchanger coils were rinsed by
first filling the tank to its capacity, approximately 56.8 1 (15 gal),
then draining the water through the drain plug. After the tap water
rinse, approximately 41.61 (11 gal) were poured into the tank. This
water served as the initial charge used for the test program. A tap water
sample and a sample obtained from the water in the tank were collected to
establish the initial contaminants in the water by laboratory analysis at
the start of the test.
In order to obtain water samples representative of "as-found"
furnace conditions, it was necessary to condition the initial charge of
tap water in the tank by operating the furnace over a period of a few days
under normal domestic operating practices. Thus the furnace was left
operating in a cyclic mode (approximately 10 min on, 20 min off) for about
one week. The condensed flue gas water raised the level of the tank water
to the overflow setting. Any water collected from the overflow drain was
then monitored intermittently for its pH level. After the week of
preconditioning the water, the pH level reached a constant value of about
3.0. At that point, another water sample was taken from the tank drain
valve to be analyzed for anions, trace elements, and condensed organic
concentrations. This sample, together with the water sample collected at
the end of the test, served to establish the steady state reached through
the conditioning period of the tank water. An electronic data logger
33
-------
(Autodata 8) was used to record temperatures of ambient air, stack flue
gas, inlet water, outlet water, and tank water on a 1-min interval during
both burner-on and burner-off periods.
Table 4-1 summarizes burner and furnace operating settings
throughout the test program. Cycle frequency of the burner was controlled
by adjusting the setting of the tank water thermostat and the cooling
water flow rate. A thermostat setting of approximately 54°C (129°F)
and a cooling water flow rate of 107 ml/s (1.7 gal/min) resulted in
burner cycle frequencies of 11 to 14 min on, 22 to 25 min off. These
settings were maintained nearly constant throughout the test period.
Figure 4-1 illustrates the temperature profiles measured with the data
logger during a typical on-off burner cycle.
The following section presents emissions measured in both gaseous
and liquid streams leaving the furnace.
4.2 FLUE GAS AND WATER EMISSIONS
The sampling and analysis procedures used in this test program
conform to the EPA Level 1 protocol (reference 4-1) for gas and liquid
streams. Flue gas measurements were made at the exit of the furnace at
approximately 1m (3 ft) from the base of the uninsulated exhaust pipe,
as shown in figure 4-2. Flue gas measurements included:
• Continuous monitors for NO, N0x, CO, C02, 02, TUHC
• Source Assessment Sampling System (SASS) for trace elements and
organic emissions
• EPA Method 5 for solid and condensable particulate mass
emissions
• EPA Method 8 for sulfur species (S0?, SO^)
L- *J
34
-------
Table 4-1. Hot Water Residential Heating System
Test Operating Conditions
M.A.N. burner operating condition:
— Burner oil pressure 1.03 MPa (150 psig)
— Oil temperature ambient
— Burner on-time 11 to 14 min
-- Burner off-time 22 to 25 min
— Distillate oil flow 0.45 ml/s (0.49 gal/hr)
Hot water heating system initial settings and operating conditions:
— Tank water capacity ~56.8 1 (15 gal)
-- Tank water at start of test -53.0 1 (14 gal)
-- Cooling water flow 107 ml/s (1.7 gal/min)
— Tank water thermostat setting 54 to 55°C (129 to 131°F)
-- Average inlet water temperature 13°C (56 F)
-- Average rise of outlet water temperature 19°C (35°F)
-- Average rise of tank water temperature 32°C (58°F)
~ pH of tank water 2.7
-- Approximate tank water discharge rate ~0.47 ml/s (0.43 gal/hr)
— Flue gas temperature 16.7 to 27.8°C (62 to 82°F)
35
-------
Tarn water temperature
Water out temperature
Water in temperature
Stack temperature-
50
40
Time after start of cycle (minutes)
Figure 4-1. Hot Water Residential Heater Temperature Profiles
36
-------
t Grab sample for onsite analysis of C-, - Cfi hydrocarbons by
gas chromatography
• Bacharach smoke spot
Appendix A describes this equipment, and the sampling and analytical
procedure used.
4.2.1 Criteria Pollutant and Other Vapor Phase Emission Results
Table 4-2 lists emissions of CO, C02, NO, N02, TUHC, particulate,
sulfur oxide, and smoke in the flue gas during the period of firing.
During the test there were peaks of CO and hydrocarbon emissions at the
start and end of burner-on times. The peak emissions at the start of each
cycle are included in the reported levels; however, the effects of burner
shut-off were not evaluated. Since the blower and the fuel pump were
shut off at the same time, there was no forced air when the burner was
shut off. Thus, the combustion air flowrate is unknown, and the CO and
hydrocarbon emission rates at the end of the firing cycle cannot be
evaluated.
Burner startup peak emissions averaged 150 ppm for CO and 15 ppm
for hydrocarbons. The NO started at zero and reached approximately 70 ppm
on the average, at 1.9 percent average 0,,. Smoke emissions measured with
the Bacharach hand pump kit were zero during the entire burner-on period.
Figure 4-3 is a copy of a portion of the strip chart recorder depicting
emission traces for CO, C02, NO, and 02 during one typical burner on-off
cycle operation of the furnace.
NO emissions averaged 37.1 ng/J, as N02, over the duration of the
test. This level, although significantly higher than NO emissions measured
for a Blueray warm air furnace (reference 4-2), represents a 40 percent
37
-------
I I
I I
Exhaust duct extending approx. 3m (9 ft)
above the furnace
CO
CO
High volume stack
sampler (HVSS) for
particulates and
modified HVSS for
emissions
Exit flue
gas temperature
thermocouple
Source Assessment Sampling System (SASS) train
Gas flow anemometer
Bacharach smoke spot and sample
probe for gas chromatography
analysis
approx. 1m
(approx. 3 ft)
Furnace
V
^
Burner
Figure 4-2. Gas Sampling Locations
-------
Table 4-2. Flue Gas Emissions'
Spec i es
02 (percent dry)
C02 (percent dry)
HzO (percent)
C0a (ppm @ 0 percent 02)
(ng/J)
NO (ppm @ 0 percent 02)
(ng/J as N02)
N02
TUHC (ppm @ 0 percent 02)
(ng/J as C3H8)
S02 (ppm @ 0 percent 02)
(ng/J)
S03
Solid participate (ng/J)
Method 5
Condensable parti cul ate (ng/J)
Method 5
Solid parti cul ate (ng/J)
SASS
Smoke (Bacharach)
Range
1.4 - 2.4
12.6 - 14.0
2.7 - 3.0
15 - 51
4.5 - 15.2
68 - 79
33.2 - 38.6
Ob
0.5 - 9
0.2 - 4.1
—
—
Ob
—
—
—
0
Average
1.9
12.9
2.9
40
11.9
76
37.1
0
3.3
1.5
156
106.3
0
1.3
1.4
1.2
0
Includes peak emissions at the start of burner-on cycle
""l^ and S03 were absorbed in the condensing water
39
-------
JAN
M.A.M. residential burner test
typical cycle emissions
CO reads 40 ppm during steady state
160 ppm light-off peak
145 ppm shut-off peak
C02 reads 13.2 percent average
TPK
I ! I
CO and CO,
12*
Burner off \
M.A.N. residential burner test
— typical cycle emissions
02 reads 1.9-2.05 percent
NOX reads -60 ppm at cycle start to
-70 ppm at burner shut-off
0? and NO,
Figure 4-3. Strip Chart Recordings of Emissions
During a Typical Burner Cycle
40
-------
emissions reduction from conventional residential heating systems burning
distillate oil (reference 4-3). The effect of condensation of flue gas
moisture on NCU emissions was obvious in that apparently any NOp present
in the flue gas was absorbed by the condensed moisture and eventually ended
up in the tank water. Analysis of anions in the tank water and condensate
drain collected during the test shows, in fact, that nitrates were present
in the water. Results of water analysis are presented in section 4.2.2.
It should be noted that the level of NO measured during this test
program may not be fully representative because of the relationship between
fuel nitrogen and NO emissions. Table 4-3 summarizes the ultimate analysis
of the distillate oil used in the program. As indicated, the nitrogen
content of the oil averaged 0.04 percent making it a relatively high nitro-
gen distillate. Assuming 100 percent conversion of fuel nitrogen to NO,
its contribution to total NO emissions could account for nearly 80 percent.
Thus, for lower nitrogen distillate oils, NO emissions from this furnace
may be lower than the 37.1 ng/J (as NOp) measured during the current tests.
Sulfur species (S02 and SO,) in the exhaust gas were analyzed by
EPA Method 8, and sulfate on particulate by turbimetric methods. As
expected, S02 was the only sulfur species found in the exhaust gas. Both
gaseous S03 and sulfate were apparently absorbed in the condensing water;
sulfur leaving the furnace as S0? accounted for 118 percent of the total
fuel sulfur input based on a fuel oil analysis of 0.2 percent sulfur and
44.6 MJ/kg (19,190 Btu/lb) heating value.
Particul ate emissions were measured by both EPA Method 5 and SASS
techniques. Solid particulate matter collected on the filter and inside
-------
Table 4-3. Ultimate Fuel Analysis of Distillate Oil (Percent by Weight)
Carbon (C)
Hydrogen (H)
Sulfur (S)
Nitrogen (N)
Oxygen (0)
(by difference)
Heating value
Gravity °API @ 60°F
86.94
13.23
0.20
0.04
--
44.6 MJ/kg (19,190 Btu/lb)
33.75
42
-------
the probe were very consistent between the two sampling techniques: 1.3
versus 1.4 ng/J. Particulate matter condensed in the impinger section of
the Method 5 train accounted for about 50 percent of the total particulate
matter emissions.
Bacharach smoke emissions were measured throughout the test program
at various time intervals after fuel light-off. Smoke numbers were
consistently zero throughout each firing period. The absence of smoke and
relatively low CO emission peaks during burner light-off are attributable
to the fuel oil delay valve of the M.A.N. burner which prevented ignition
for approximately 15 sec after the burner blower went on.
4.2.2 Trace Element Analyses
The fuel sample from the inlet to the furnace, the SASS train
samples from the furnace gas outlet, and water discharge samples were
analyzed for 73 trace elements using Spark Source Mass Spectrometry (SSMS)
and Atomic Absorption (AA) techniques. Once the trace element concentra-
tions were determined by laboratory analysis, trace element flowrates
for fuel inlet, flue gas vapor and condensed phases, and water discharges
could be computed. Trace element concentrations and flowrates are presented
in appendix B.
Distillate fuel oil is relatively free of mineral matter, thus
inorganic emissions from combustion of this fuel are generally very
small. Table 4-4 summarizes trace element levels above the detection
limit of the analysis in the fuel oil, exhaust gas and water discharge
samples. As shown, the concentration of most of the elements in all input
and output streams is well below the ng/J level. Of all trace elements
in the fuel oil, chlorine, aluminum, calcium, potassium, titanium, silicon,
and iron were found at the highest concentrations (0.112 to >2.24 ng/J).
43
-------
Table 4-4. Trace Element Emissions (pg/J)
Element
Aluminum
Antimony
Arsenic
Barium
Boron
Bromine
Cadmium
Calcium
Cereium
Cesium
Chlorine
Chromium
Cobalt
Copper
Fluorine
Gallium
Iron
Lanthanum
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Neodymi urn
Nickel
Phosphorus
Potassium
Fuel Oil
>2200
__b
0.45
6.7
0.90
67
0.45
>2200
--
--
1600
9.0
0.90
11
22
0.45
220
--
4.5
0.45
45
4.5
<2.2
<2.2
--
22
22
160
Flue Gas
>27
0.019
0.065
1.5
>21
0.66
--
>21
0.058
0.016
--
1.3
0.42
2.2
5.3
0.034
5.9
0.42
1.1
0.090
14
0.52
0.18
1.1
0.0021
3.3
0.85
16
Water
11
0.44
0.20
--
0.66
--
0.13
--
--
--
--
11
1.5
noooa
2.2
--
150
--
1.3
--
33
2.2
--
2.2
--
15
8.8
22
Closure
Out/In
>0.017
--
<0.59
0.22
>24
0.0098
0.29
>0.0092 !
i
--
!
--
1.4
1.8
1000
0.33
0.076
0.71
--
0.53
0.20
1.1
0.61
<0.082
1.5
--
0.83
0.43
0.24
- Continued -
44
-------
Table 4-4. Concluded
Element
Rubidium
Scandium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Tantalum
Tellurium
Tin
Titanium
Vanadium
Yttrium
Zinc
Zirconium
Fuel Oil
0.22
<0.22
--
560
--
90
—
4.5
—
4.5
0.67
110
0.45
0.45
16
0.90
Flue Gas
0.016
--
0.096
>30
0.0021
>85
0.085
18
0.19
0.16
0.042
5.0
0.42
0.11
2.9
--
Water
__
0.2
2.2
88
--
--
--
>220
0.88
0.13
<0.13
2.2
--
<4.4
>220
0.22
Closure
Out/In
<0.071
<0.99
--
>0.21
--
>0.94
--
>53
--
0.065
<0.26
0.064
0.94
<10
>14
0.25
aSSMS analysis resulted in a less accurate value of about
>0.22 ng/J instead of value obtained with AA analysis
shown here; leaching of copper coils is suspected.
Dashes indicate levels below the detection limit.
45
-------
No traces of chlorine were found in the flue gas suggesting that it also
was absorbed into the tank water. For the other elements only a fraction of
the fuel oil concentration was accounted for by the flue gas and the tank
water discharge.
Copper, molybdenum, zinc, cobalt, chromium, and boron show outlet
concentrations higher than accounted for by the fuel oil. With the excep-
tion of boron, the contribution of these elements in the tank water was
significantly higher than that from the flue gas. This is true especially
for copper which had the highest concentration of any element in the waste
water. This copper concentration suggests that leaching of heat transfer
copper coils may have occurred. Leaching of other metal surfaces may have
contributed to high concentration of other metallic elements. Nickel,
however, also an element found in the stainless steel tank, did not show an
outlet concentration higher than that in the fuel oil. Cobalt and boron
results are questionable.
The sulfur content of the fuel oil by SSMS is significantly lower
than sulfur content measured by the ultimate fuel analysis. This is due
to oxidation of the sulfur to SOo during pretreatment of the fuel oil sample
prior to SSMS analysis.
Measurement of the anions in the tank water discharge shows the
presence of chloride, nitrate, and sulfate. Chloride is most likely due
to conversion of chlorine in the fuel to hydrochloric acid (HC1) and sub-
sequent HC1 absorption in the condensing water. Nitrate and sulfate anions
are due to the absorption of NOo and SCU, respectively, by condensed flue
gas water vapor, which drops into the tank water and is then discharged by
the furnace.
46
-------
4.2.3 Organic Analyses
Organic analyses were performed on selected flue gas samples accord-
ing to the EPA Level 1 protocol outlined in appendix B (reference 4-1).
Gaseous C-j to Cg hydrocarbon compounds in the flue gas having boiling points
nominally less than 100°C (212°F) were analyzed onsite by gas chromatography.
Samples collected in the SASS train were extracted with methylene chloride
in a Soxhlet apparatus. The extracts were then subjected to Total Chroma-
tographable Organic (TCO) and gravimetric (GRAV) analyses which determine
species with boiling points nominally in the ranges of 100 to 300°C (212 to
572°F) and greater than 300°C (572°F). Infrared (IR) spectra of the total
sample extracts were also performed. Liquid column chromatography (LC)
separations of the organic sorbent extract was performed followed by IR
analyses of organics eluted in each LC fraction and Low Resolution Mass
Spectrometry (LRMS) of those fractions containing organic matter in excess
of 0.5 mg/dscm. In addition, Gas Chromatography/Mass Spectrometry (GC/MS)
analysis of total sample extracts was performed to identify specific poly-
nuclear aromatic and other organic compounds. A discussion of the analytical
results follows.
4.2.3.1 GI to C6 Flue Gas Hydrocarbon Analysis
Onsite analysis of C-, to Cg flue gas hydrocarbons was conducted
during the test. The grab samples were taken at different times during
the duration of a cycle: at startup of the burner, 5 min into the cycle,
and at the end of the cycle. The results of these analyses are presented
in table 4-5. As shown, the concentrations of C-| to Cg hydrocarbon
emissions were less than the ppm level.
47
-------
Table 4-5. C-| to Cg Flue Gas Hydrocarbon Analysis (ppm, dry)
Test Time
GI (methane)
C2 (ethane)
03 (propane)
04 (butane)
GS (pentane)
GS (hexane)
Beginning
of Burn Cycle
0.4
<0.2
<0.5
<0.5
<1.0
<1.0
5 Min into
Burn Cycle
<0.2
<0.2
<0.5
<0.5
<1.0
<1.0
End of
Burn Cycle
<0.2
<0.2
<0.5
<0.5
<1.0
<1.0
43
-------
These results contrast with the total hydrocarbon emission data measured
with continuous Flame lonization Detector (FID) data. The FID data reported
in section 4.2.1 indicated levels ranging from 0 to 9 ppm and an average of
3.3 ppm. In light of the Gas Chromatography (GC) analyses reported here, the
continuous FID analyzers are not sensitive to hydrocarbon levels in the range
of 1 to 5 ppm.
4.2.3.2 Total Chromatographable Organic (TCP) and Gravimetric
Analyses of Organic Extracts
TCO and gravimetric analyses were performed on the filter, XAD-2 sorbent,
and organic module condensate extracts. The results of the analyses for both
flue gas and waste water samples are presented in table 4-6. The flue gas re-
sults indicate that 74 percent of all the organic emissions were of compounds
in the TCO range and collected in the XAD-2. The total concentration of
organic matter in the flue gas measured only 3.5 mg/dscm. This organic emis-
sion concentration compares to an average of 5.0 mg/dscm measured from five
conventional residential warm air furnaces (reference 4-4) and 26.3 mg/dscm
for one low-NO furnace design (reference 4-2), all burning distillate oil
J\
and operating in a cyclic mode. The water analysis results indicate that
some organic matter condensed in the water; however, the total concentration
measured less than 0.1 mg/1 of waste water discharge, corresponding to an
emission rate significantly lower than that of the flue gas stream.
4.2.3.3 Infrared (IR) Spectra of Total Extracts
The results of the IR spectra determinations for the total extract
samples are summarized in table 4-7. IR spectrometry is used to identify
the organic functional groups present in the sample. The spectra suggested
the potential presence of aliphatic hydrocarbons and alcohols in all samples.
The XAD-2 extract and the tank discharge contain many more organic categories.
49
-------
Table 4-6. Results of TCO and Gravimetric Analyses
of Total Extract Samples
en
O
Stream
Flue
gas
Water
Sample
Filter
XAD-2 extract
Organic module
condensate
extract
Total flue
gas sample
Tap water
Tank water
blank
Tank water
discharge
TCO Results
(mg)
_.
74
<0.02
74
<0.02
<0.02
0.5
Gravimetric
Results
(mg)
3
18
5
26
<2
<2
<2
Total Organic
in the Sample
(mg)
3
92
5
100
<2
<2
0.5
Concentration
in the Sample
(mg/dscm)
0.1
3.2
0.2
3.5
(mg/1)
<0.1
<0.1
<0.1
-------
Table 4-7. Summary of Infrared Spectrometry Analysis
of Total Extract Samples
Stream
Sample Type
Compound Categories Potentially Present
Flue gas
Water
XAD-2 extract
Organic module
condensate
extract
Filter
Tap water
Tank water
blank
Tank water
discharge
Aliphatic hydrocarbons, carboxylic acids,esters,
alcohols, ketones, aldehydes, amines
No peaks
No peaks
No peaks
No peaks
Aliphatic hydrocarbons, sulfonamide
51
-------
4.2.3.4 Liquid Chromatography Fractionation
The XAD-2 sample extract was separated via liquid chromatography to
fractionate the organic matter into seven polarity fractions. Results of
TCO and GRAV analyses of each fraction are summarized in table 4-8.
Table 4-8. Gravimetric and TCO Results of Column
Chromatography of the XAD-2 Samples
Fraction
LCI
LC2
LC3
LC4
LC5
LC6
LC7
Total
TCO
(mg)
52
0.2
0.85
0.1
<0.01
<0.01
<0.01
53
Gravimetric
(mg)
23
2
<2
<2
<2
2
4
31
Total
(mg)
75
2
<3
<2
<2
2
4
84
(mg/dscm)
2.6
0.07
0.1
<0.07
<0.07
0.07
0.14
3.0
Results are based on total organics recovered
in each fraction corrected to total organics
in the original sample.
Results indicate that 90 percent of the organic matter eluted in the first
fraction, which typically contains aliphatic hydrocarbons. Lesser amounts
eluted in fractions 2, 3, 6, and 7, which generally contain aromatics (LC2
and LC3) and oxygenates (carboxylic acids, alcohols, esters, ketones, etc. --
LC6 and LC7).
4.2.3.5 Infrared and Low Resolution Mass Spectral (IR and LRMS)
Analyses of Fractions from Column Chromatography
Samples from column chromatography fractionation of the organic sorbent
extract were analyzed using Level 1 infrared and Low Resolution Mass Spectral
52
-------
(LRMS) techniques. Table 4-9 summarizes the IR results. Only LCI and LC3
(which contained most of the organic matter) show interpretable spectra.
Table 4-9. Infrared Analysis of Column
Chromatography Fractions
Fraction
LCI
LC2
LC3
LC4
LC5
LC6
LC7
Frequency,
cm" '
2920--2840
--
3500—2940
2920—2840
--
--
--
Intensity3
S
--
S
S
--
--
--
Possible
Assignment
CH aliphatic
No peaks
OH alcohols
CH aliphatic
No peaks
No peaks
No peaks
S = strong intensity
LRMS analysis was performed only on LCI because this fraction alone exceeded
the 0.5 mg/dscm threshold established in the Level 1 protocol. Results
of this analysis confirmed the presence of aliphatic hydrocarbons as the
major organic category present.
Table 4-10 summarizes organic analysis results for the exhaust gas
stream from the residential heater. The top portion of the table summarizes
the Total Chromatographable Organic (TCO) and Gravimetric (GRAV) analyses of
the organic sorbent XAD-2 extract eluted in the seven liquid chromatography
fractions (LC). The bottom portion of the table summarizes the organic
categories found in each sample using infrared spectrometry (IR) and Low
Resolution Mass Spectrometry (LRMS) and their estimated concentrations
based on the total organic level in the sample. In summary, aliphatic
53
-------
Table 4-10. Organic Extract Summary -- XAD-2 Sorbent Extract
Total Orgam'cs,
mg
TCO, mg
GRAV, mg
LCI
75
52
23
LC2
2
0.2
2
LC3
<3
<0.85
<2
LC4
<2
<0.1
<2
LC5
<2
<0.02
<2
LC6
2
<0.02
2
LC7
4
<0.02
4
I
85
54
31
Category
Aliphatic HCs
Aldehydes
Carboxylic Acids
Assigned Intensity -- mg/dscm
LCI
100--2.6
LC2
LC3
100-<0.11
LC4
LC5
LC6
LC7
100—0.14
2.6
0.11
0.14
-------
hydrocarbons account for nearly 90 percent of all the organic matter while
alcohols and carboxylic acids, esters, ketones, or amines account for the
remaining 10 percent.
4.2.3.6 Gas Chromatography/Mass Spectrometry Analysis of POM Compounds
Gas Chromatography/Mass Spectrometry (GC/MS) analyses of gas sample
extracts were performed to detect and quantify specific polycyclic organic
matter and other organic compounds. The compounds sought in the analysis
and their respective detection limits are listed in table 4-11. The results
of the GC/MS analyses are summarized in table 4-12. As shown, naphthalene
and phenanthrene were the only ROM's found to be in concentrations above the
detection limit of the analysis. The concentrations of these compounds in
the exhaust gas are two orders of magnitude lower than the total organic
concentration of 3.5 mg/dscm.
4.2.3.7 Summary of Organic Emissions
Most of the organic compounds detected in the exhaust gas of the
Hadwick/Karlsons furnace are aliphatic hydrocarbons (about 90 percent).
These hydrocarbons are probably directly attributable to unburned fuel oil
in the flue gas which is often the result of frequent burner startups. Small
amounts of oxygenated compounds (carboxylic acids, alcohols, ketones, esters,
etc.) were also apparently present. They can be attributed to partially
burned fuel. Some POM compounds in low concentrations were found, but these
make up a small portion of the total hydrocarbon emissions; their concentra-
tions are significantly below hazardous guideline levels used by EPA to
establish the need for further testing. A discussion of these hazardous
guideline levels in given in section 5.
55
-------
Table 4-11. Compounds Sought in GC/MS Analysis and
Their Detection Limits (ng)
8 4-bromophenyl phenyl ether
la bis(2-chloroisopropyl)ether
2a bis(2-chloroethoxy)methane
8a hexachlorobutadiene
40a hexachlorocyclopentadiene
la isophorone
la naphthalene
8a nitrobenzene
4a N-nitrosodiphenylamine
40a N-nitrosodi-n-propylamine
3a bis(2-ethylhexyl)phthalate
3a butyl benzyl phthalate
la di-n-butyl phthalate
2a di-n-octyl phthalate
2a diethyl phthalate
2a dimethyl phthalate
5a benzo(a)anthracene
7a benzo(a)pyrene
8a 3,4-benzofluoranthene
8a benzo(k)fluoranthene
5a chrysene
la acenaphthylene
la anthracene
40a benzo(ghi)perylene
2a fluorene
la phenanthrene
40a dibenzo(a,h)anthracene
40a indeno(l,2,3-cd)pyrene
2a pyrene
20 2,3,7,8-tetrachlorodibenzo-p-dioxin
2a acenaphthene
100a benzidine
8a 1,2,4-trichlorobenzene
8a hexachlorobenzene
8a hexachloroethane
3a bis(2-chloroethyl)ether
2a 2-chloronaphthalene
4a 1,2-dichlorobenzene
8a 1,3-dichlorobenzene
4a 1,4-dichlorobenzene
20a 3,3-dichlorobenzidine
10a 2,4-dinitrotoluene
10a 2,6-dinitrotoluene
la 1,2-diphenylhydrazine (as azobenzene)
2a fluoranthene
4a 4-chlorophenyl phenyl ether
40 anthanthrene
40 benzo(e)pyrene
-- dibenzo(a,H)pyrene
dibenzo(a,i)pyrene
40 dibenzo(c,g)carbozole
40 7,12 dimethyl benz(a)anthracene
40 3-methyl cholanthrene
40 perylene
40 benzo(c)phenanthrene
Authentic standard run
bMolecular weight too high for direct analysis by base/neutral run
56
-------
Table 4-12. Results of Quantification of POM Compounds
on
Compound
Naphthalene
Phenanthrene/
anthracene
Molecular
Weight
128
178
Quantity (ng)
Filter
<1
<1
XAD-2
94
4
OMC
<1
<1
Tank
Water
9
2
Total Emissions
Flue gas
(pg/dscm)
36
2
Water
(V9/1)
0.4
0.08
-------
REFERENCES FOR SECTION 4
4-1. Lentzen, 0. E. et al., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment," EPA-600-2-76-160a, NTIS PB 275 850/AS,
June 1976.
4-2. Higginbotham, E. B-, "Combustion Modification Controls for Resi-
dential and Commercial Heating Systems: Volume II, Oil-Fired
Residential Furnace Test," EPA-600/7-81-123b, July 1981
4-3. Castaldini, C., "Combustion Modification Controls for Residential
and Commercial Heating Systems: Volume I Environmental Assessment,'
EPA-600/7-81-123a, July 1981.
4-4. Surprenant, N. F. et al., "Emission Assessment of Conventional
Stationary Combustion Systems, Volume 1: Gas- and Oil-Fired
Residential Heating Sources," EPA-600/7-79-029b, May 1979.
58
-------
SECTION 5
ENVIRONMENTAL ASSESSMENT
This section presents the potential environmental impact for the
source tested and discusses the bioassay testing of flue gas and water
discharge samples collected from the furnace. The environmental impact is
quantified using a Source Analysis Model (SAM) developed for general use
within all IERL EA programs. Bioassay analyses are conducted for testing
the toxicity and mutagenicity of waste streams. Both the SAM and bioassay
analyses are aimed at identifying problem areas and providing the basis
for ranking streams for further consideration in the environmental
assessment.
5.1 SOURCE ANALYSIS MODEL EVALUATIONS
The model used to evaluate the Level 1 data obtained from the M.A.N./
Hadwick residential furnace system is the rapid screening model, SAM IA
(reference 5-1). SAM IA includes no treatment of pollutant transport or
transformation, so evaluations employ effluent stream concentration goals,
termed Discharge Multimedia Environmental Goals (DMEG's, reference 5-2, 5-3)
A compound's DMEG corresponds to a concentration considered safe for acute
exposure.
The SAM IA model defines two indices of potential hazard. The
first, termed Discharge Severity (DS), is defined as the ratio of the
concentration of a pollutant to its DMEG. In Level 1 evaluations, the
59
-------
discharge concentration used is that determined for each MEG category of
components analyzed in the effluent sample, while the DMEG used is that for
the most toxic species potentially present for the MEG category. A stream
Total Discharge Severity (IDS) is also defined as the sum of the OS's cal-
culated for the discharge stream. When a DS exceeds unity, more refined
chemical analysis may be required to quantify specific compounds present.
The second SAM IA hazard index, termed Weighted Discharge Severity
(WDS), is defined as the product of DS with the discharge stream mass flow-
rate. The WDS is an indicator of the magnitude of a potential hazard and
can be used to rank the needs for controls for waste streams.
SAM IA evaluations were performed on each set of test data reported
in section 4 using health-based DMEG's. Results are summarized in table 5-1.
Only discharge severities for those species with a DS greater than 0.1 are
listed.
In the flue gas stream, NO and S0? emissions were responsible for
the highest DS values, both exceeding unity by nearly a factor of 10. The
DS for CO and total hydrocarbons (primarily aliphatic) suggest that these
were present in nonhazardous concentrations (DS <1.0). Four elements with
DS greater than 0.1 were found in the flue gas. These were chromium, nickel,
sodium, and sulfur, with only chromium having a DS exceeding unity. Both
chromium and nickel emissions, however, are suspected contaminants in sample
preparation prior to the Spark Source Mass Spectrometry (SSMS) analysis.
The only organic categories of potential concern in the flue gas
emissions are aldehydes, with DS of 0.4 and carboxylic acids, with DS of 0.2.
These DS values were calculated assuming that the organic matter eluting in
LC3 (for aldehydes) and in LC6 and LC7 (for carboxylic acids) of the XAD-2
60
-------
Table 5-1.
Flue Gas and Water Discharge Severities (Health-Based)
Greater than 0.1 for the Hadwick Furnace Equipped with
Low-N0x M.A.N. Burner
Pollutant
Copper, Cu
Sulfate, S0~
NO
so2
Iron, Fe
Nickel, Ni
Chromium, Cr
Selenium, Se
CO
Manganese, Mn
Sulfur, S
Zinc, Zn
Aldehydes
Lead, Pb
Carboxylic acids
Sodium, Na
Total Discharge Severity
(TDS)a
Weighted Discharge
Severity (WDS)b, g/s
MEG Category
78
53
47
53
72
76
68
54
42
71
53
81
7A
46
8A,B
28
--
Flue Gas
3.0 x 10"2
11.0
10.0
1.5 x 10"2
0.57
3.4
1.3 x 10"3
0.77
2.8 x 10"4
0.48
1.9 x 10"3
0.40
1.9 x 10"2
0.20
>0.11
27.0
2,600
Tank Water
Discharge
100
67
6.7
4.4
2.8
2.0
0.76
>0.4
0.28
--
™ ™
185
8.7
TDS =
DWDS = M x E.J OS., where M is the mass flowrate of the stream in
grams per second.
61
-------
extract consisted entirely of the compound with the lowest DMEG in the
respective organic categories potentially present. Table 4-10 noted that
aldehydes were possibly present in LC3. The DS for this category was cal-
culated assuming the LC3 organic content consisted entirely of acrolein,
the aldehyde with the lowest DMEG. Correspondingly, table 4-10 noted that
carboxylic acids, alcohols, esters, ketones, or amines were potentially
present in LC6 and LC7 fractions. In addition, IR data suggest that none
of these are aromatic. Thus the compound with the lowest DMEG consistent
with the above is a carboxylic acid (saturated long chain acids of molecular
weight between 228 and 285). The DS noted in table 5-1 assumes the entire
amount of LC6 and LC7 organics in the XAD-2 extract consisted of this compound.
Thus, these DS values represent conservative estimates of the potential
hazard posed by organic emissions from the furnace.
Trace elements in the tank water for which DS exceeded unity were
found to be copper, chromium, iron, nickel, and selenium. Copper levels
significantly exceeded those of any other trace element in the waste water.
The high concentration of copper in the waste water is attributed to leach-
ing of heat transfer copper coils immersed in the warm acidic water. In fact,
concentrations of most other metallic trace elements including iron, chro-
mium, lead, nickel and zinc can also be attributed to leaching of metal
surfaces in contact with the water. Sulfates, nitrates and chloride
concentrations of about 1,000, 7 and 3 mg/1 resulted in DS values of 67,
0.093, and 0.17, respectively. Sulfuric acid in the waste water represents
the greatest potential environmental concern, second only to copper.
Total discharge severity for the liquid stream exceeded that of the
gas stream due primarily to the high concentrations of copper and sulfates.
62
-------
Table 5-2. Bioassay Analysis Results
Sample
Organic sorbent XAD-2
Tank water discharge
Evaluation3
CHOb
L/ND
M
Amesc
Mc
ND
RATb
—
ND
ND = nondetectable toxicity/mutagenicity
L = low toxicity
M = moderate toxicity/mutagenicity
Toxicity test
cMutagenicity test
63
-------
However, based on the total flowrate of each stream, the exhaust gas still
poses a higher environmental risk relative to the waste water as indicated
by the Weighted Discharge Severity (WDS).
5.2 BIOASSAY ANALYSIS
The Level 1 bioassay protocol includes testing for both health and
ecological effects (reference 5-4). Bioassay results presented here are
limited to health effects tests. These tests consist of (1) the Ames assay,
based on the property of Salmonella typhimurium mutants to revert due to
exposure to various classes of mutagens; (2) the cytotoxicity assay (CHO)
of mammalian cells in culture to measure cellular metabolic impairment and
death resulting from exposure to soluble toxicants; and (3) acute toxicity
tests in live rodents (RAT) to identify in vivo toxic effects.
The results of these assays are summarized in table 5-2 for both
the organic sorbent extract from the train and a tank water discharge
sample. The responses varied from nondetectable to moderate toxicity and
mutagenicity.
64
-------
REFERENCES FOR SECTION 5
5-1. Herther, M. A. and L. R. Waterland, "SAM IA: A Rapid Screening Model
for Environmental Assessment of Fossil Energy Process Effluents,"
Acurex Report TR-77-50D, March 1982.
5-2. Cleland, J. G. and G. L. Kingsbury, "Multimedia Environmental Goals
for Environmental Assessment: Volumes I and II," EPA-600/7-77-
136a,b, November 1977.
5-3. Kingsbury, G. L. et al., "Multimedia Environmental Goals for Environ-
mental Assessment: Volumes III and IV," EPA-600/7-79-176a,b, August
1979.
5-4. Duke, K. M. et al., "IERL-RTP Procedures Manual: Level 1 Environmental
Assessment Biological Tests for Pilot Studies," EPA-600/7-77-043,
April 1977.
65
-------
APPENDIX A
TEST EQUIPMENT AND PROCEDURES
A.I CONTINUOUS MONITORING SYSTEM AND CALIBRATION GASES
The residential heating system was set up in the Acurex combustion
laboratory where hookup to the continuous air emissions monitoring system
could easily be accomplished. A schematic of the gaseous emission
monitoring system used for the test program is shown in figure A-l. In
most applications, a sample from the flue gas is pulled through a heated
filter where the particulates are removed. From the heated filter, the
sample flows through a heated Teflon line to an oven. Additional filtra-
tion is performed in the oven and the sample is split into three streams.
Calibration or zero gas is added at this point. From the heated oven, the
three sample lines pass through a refrigerant dryer where the sample is
condensed to a dew point of 2°C (35°F) and condensed water is
removed. From the dryer, each sample gas passes through a pump and
another filter prior to entering the continuous gas analyzers. Table A-l
lists the analyzers and the principle of operation for each of the gaseous
emissions measured.
Because the exhaust gas of the furnace tested is already below its
dew point, 24 to 32°C (75 to 90°F), a heated sample line and filter were
not necessary. However, no modification to the sample conditioning system
was made since the impact of heating the sample gas to approximately 121°C
66
-------
CTl
Sample
probe
Furnace
exhaust
pipe
Heated
line
Heated
Filter
Cal gases
Chemiluminescent
Pumps
Figure A-l. Emission Monitoring System
-------
Table A-l. Gaseous Emissions Monitoring Equipment
Instrument
NO
CO
CO
CO 2
02
UHC
Sample gas
conditioner
Principle of
Operation
Chemi luminescence
Nondispersive
Infrared (NDIR)
Nondispersive
Infrared (NDIR)
Paramagnetic
Flame lonization
Detection (FID)
Ref ri gerant
dryer-condenser
Manufacturer
Air Modeling
ANARAD
ANARAD
Ethyl Intertech
Ethyl Intertech
Hankison
Models
32C
500R
AR600R
Magnos 5T
FID
E-46-SS
Instrument
Range
0-5 ppm
0-10 ppm
0-100 ppm
0-250 ppm
0-1000 ppm
0-5000 ppm
0-1000 ppm
0-15 percent
0-20 percent
0-5 percent
0-21 percent
0-100 ppm
0-300 ppm
0-1000 ppm
0-3000 ppm
0-10000 ppm
0-30000 ppm
10 scfm
68
-------
(250°F) on the concentration of water insoluble pollutants, such as CO
and NO, was considered negligible.
A.2 PARTICULATE TESTS
Particulate mass emission tests were conducted in accordance with
EPA Methods 1 through 5 of the Federal Register. The following sampling
equipment was used:
• A 316 stainless steel sampling nozzle properly sized for
isokinetic sampling
• A 0.9m (3 ft) heated stainless-steel-lined probe was used to
isokinetically extract samples from the stack. The probe was
kept at 121°C (250°F) as required by the EPA Method 5 and
was equipped with a thermocouple to measure stack temperature
and a calibrated S-type pitot tube to measure velocity
pressure. However, because the gas velocity was extremely low
for this source, a gas flow anemometer was used instead.
t A Teflon-coated stainless steel 142 rrrn (5.6 in.) filter holder
• An impinger train containing four glass bottles to collect
moisture and condensable material escaping the filter
• A 4.7 1/s (10 cfm) carbon vane pump modified for very low
leakage around the shaft
t A control module to monitor temperature, pressure, and flowrate
throughout the sampling train. For this test, the orifice AH
is indicated on a 0 to 1.5 kPa (0 to 6 in. W.G.) magnehelic
gauge where the smallest division is 25 Pa (0.1 in. W.G.). The
control module contains a Rockwell Model 415 dry gas meter to
69
-------
measure the total volume of gas sampled to the nearest 0.14 1
(0.005 ft ). An orifice meter (after the dry gas meter) is used
to measure the instantaneous flowrate through the sampling train
to ensure sampling is done isokinetically.
Figure A-2 illustrates all these components of the High Volume Stack
Sampler (HVSS) used for conducting the test program. The cyclone shown in
the figure was not used in this test program.
A.2.1 Sample Collection
Sample collection took place on the 10 cm (4 in.) diameter uninsulated
stack at approximately 1m (3 ft) from the furnace exit. Once the sample
train was assembled, leak checks were performed before and after the test.
Upon completion of the test, the probe and nozzle were cleaned and the
impinger solutions were measured and recorded. The filter holder was
sealed and brought to the cleanup laboratory for reclaiming. The particu-
late test was performed at a fixed location along the diameter of the
stack because of its small size.
A.2.2 Sample Recovery
Figure A-3 illustrates the Method 5 sample recovery utilized to
measure total particulate mass collected with the HVSS train. Solid
particulate matter is defined as all particulate mass collected ahead of
the filter impinger section: the filter, the probe, and the nozzle.
Condensable particulate matter is obtained from gravimetric analysis of
impinger liquids and impinger rinses. The impinger solutions are treated
with ethyl ether to separate the organic matter from the liquid and solid
samples.
70
-------
Stack temperature T.C.
Impinoers
Fine adjustment
by pass valve
Orifice AP
magnehelic gage
Dry test meter
Vacuum
gage
Coarse
adjustment
valve
Air tight
vacuum
pump
.Vacuum
line
Figure A-2. Acurex High Volume Stack Sampler
-------
FILTER
DESICCATE AND
WEIGH TO
CONSTANT WEIGHT
PROBE. NOZZLE
AND FILTER WASH
EVAPORATE AT
ROOM TEMPERATURE
AND PRESSURE
EVAPORATE AT
ROOM TEMPERATURE
AND PRESSURE
MEASURE VOLUME
TO -1 ml
DESICCATE AND
WEIGH TO
CONSTANT WEIGHT
EXTRACT WITH
3 x 25 ml
ETHYL ETHER
EXTRACT WITH
3 x 25 ml
ETHYL ETHER
EXTRACT WITH
3 x 25 ml
CHLOROFORM
FILTER THROUGH
47 mm TYPE A
GLASS FILTER
EVAPORATE AT
ROOM TEMPERATURE
AND PRESSURE
DESICCATE AND
WEIGH TO
CONSTANT WEIGHT
FILTER THROUGH
CONSTANT WEIGHT
ROOM TEMPERATURE
CONSTANT WEIGHT
NOTES
II ALL WEIGHTS ARE TO NEAREST 001g
/I DESICCATE ALL SAMPLES FOR 24 HOURS PRIOR TO WEIGHING
Figure A-3. Sample Analysis Scheme for Participate Sampling Train
72
-------
A.3 SULFUR EMISSIONS
S02 and SCL emissions were measured using a modified HVSS sampler
in accordance with EPA Method 8 procedures. In this procedure, a gas
sample is extracted from a single point in the stack. In the impinger
train for this method the first bottle contains isopropanol and the second
contains hydrogen peroxide. A filter is placed between the two impinger
bottles. Sulfuric acid mist and any vapor phase SCL is trapped in the
isopropanol impinger. The backup filter traps any carryover mist. SOp
is absorbed in the HpCU impinger. After completion of a test the filter
is rinsed with isopropanol; the rinse solution is added to the isopropanol
impinger solution. Absorbed SCL and ^SO. in the isopropanol and SCL in
the H?CL are determined separately by barium-thorin titration.
A.4 TRACE ELEMENTS AND ORGANIC EMISSIONS
Emissions of inorganic trace elements and organic compounds were
sampled with the Source Assessment Sampling System (SASS). Designed and
built for ERA'S Industrial Environmental Research Laboratory for Level 1
environmental assessment, the SASS collects large quantities of gas and
particulate samples required for subsequent analyses of inorganic and
organic emissions as well as particle size measurement.
The SASS system, illustrated in figure A-4, is similar to the High
Volume Stack Sampler (HVSS) system utilized for total particulate mass
emission tests described in the previous section with the exception of:
• Particulate cyclones heated in the oven with the filter to
232°C (450°F)
t The addition of a gas cooler and organic sampling module
t The addition of necessary vacuum pumps
The cyclones were not employed in these tests.
73
-------
Convection oven.
Filter
SUInless
steel
staple
nozzel
Stack T.C.
Stack
velocity
magnehel1C|
gauges
11/2" Tefloi?
line
Isolation
lall valve
Stainless steel
probe assembly
Gas temperature T.C.
/2" Teflon line
Oven T.C
Sorbent cartridge
Heater controller
Imp/cooler trace
element collector
Orifice AH
magneheHc
gauge
Implnger
T.C.
Ice bath
600 grams
\_s1l1ca gel
desleant
500 ml
0.2 M Ag NO,
0.2 H (NH.)J S.O
500 ml 4 2 2
30*
Heavy will•
vacuum line
Figure A-4. Source Assessment Sampling Train Schematic
-------
—I
en
i
MMTICUtATf
i
It
PWOH AHO , , f ,
'l^T* WIWMT Wt
MffMVC
1 OMOAfMC* I
1 J— ' ,
ONCANICf
f
»>•
KSMt
nut
,
JM H
WtICK
louwct 1 »l WACITV
i
OACM
1
11 I I
• >Mv X*0.» M »^*NO
t NtlCHT MOOUli M^IMOt« __ ._
MVlMGcn
1 J
1 »i« ' 4 ^ j
•OMHtoiT I»MWO*I»K
NINM
IUHMCAMICI 1 . "*•** J [ [COMB.IW
1 ^ 1 ' i '*'
Figure A-5. Exhaust Gas Analysis Protocol
-------
SAMPLE
IU C'CLONt — — —
r ILTtR
SORBENT CARTRIDGE
AQUEOUS CONDENSATE
FIRST IMPINGER
SECOND AND THIRD
IMPIUKFRC mMBIWCn
I/I
V> Z Z
u u 2 2
_" (r0- U 5
U u* o < u*
T^ T V K °
S S* z 2 o «, 1
t- irtU- K- I" 5>
u criz j 5< ' 5 50? ' i "fl
v uccoc o KUU <• • • «
>— — < SPLIT
•^ ^- • • •
^•1 ^ * * *
. . . ^- - — - ^^^ SPLIT
*
> A A A A
SPLIT \
SCRAMS ^ ^ ^
COMBINE
^ AQUEOUS PORTION
\v ORGANIC EXTRACT N.
/ * *
. ._.« — •
TOTALS
* K "»oui'«d. tampK should b« nt n>d« for biologic*! inalytn *t thn point.
Thu ,itp n ttqu>r*d to d('m« ih« total mra of p*rticul«t* citch If th« »mpl« »cMd> 10% of th« total cyden* »nd
Mitt umplt M*ight (xoccM to in.lym. If th* am pit n I«Q than 10% of the catch, hold in rrxr««
Figure A-6. Flue Gas Analysis Requirements of SASS Samples
76
-------
Schematics outlining the sampling and analytical procedures using
the SASS equipment are presented in figures A-5 and A-6.
Inorganic analyses of solid and liquid samples from the SASS train
and fuels were performed by Spark Source Mass Spectroscopy (SSMS) for most
of the trace elements. Atomic Absorption Spectrometry (AAS) was used for
analyses of mercury (Hg), antimony (Sb), arsenic (As), and additional
elements (nickel and copper) for which results by SSMS were deemed question-
able. Anions were determined by ion chromatography. Quantitative infor-
mation on total organic emissions was obtained by Total Chromatographable
Organics (TCO) and by Gravimetry (GRAV) analyses. Gas Chromatography/Mass
Spectroscopy (GS/MS) was used by Polycyclic Organic Matter (POM) and other
organic species analysis of sample extracts. Figure A-7 illustrates the
organic analysis methodology followed during the current program.
Passivation of the SASS train with 15 percent by volume HN03
solution was performed prior to equipment preparation and sampling to
produce biologically inert surfaces. Detailed description of equipment
preparation, sampling procedures, and sample recovery are discussed in
reference A-l and will not be repeated here. These procedures were
followed in the course of the current test program.
A.5 Cj_ - C6 HYDROCARBON SAMPLING AND ANALYSIS
Acurex used a grab sampling procedure in order to obtain a sample
of flue gas for Ci - Cfi hydrocarbon analysis. Samples of the flue gas
were extracted using a heated glass probe (figure A-8). The probe was
attached to a heated 250-ml gas sampling bulb. The probe was maintained
at 150°C (302°F) and the gas sampling bulb at 130°C (266°F). A
diaphragm pump was used to pull samples through the probe and sampling
77
-------
Organic Extract
or
Neat Orqanic Liquid
1
Ov
*
J1 itU Hiidiybib ^
Concentrate
Extract
* *
GC/MS Analysis,
POM, and other Infrared Analysis
organic species
X
t t
Repeat TCO
Gravimetric Analysis
if necessary
Aliquot containino
95-100 mg
1
Solvent
Exchange
I
Liouid
Chroma tographic
Separation
f t t '
I
I t t *
Seven Fractions
t
Infrared Analysis
I
\ t
Mass Spectra
Analysis
TCO
Gravimetric
Analysis
Figure A-7. Organic Analysis Methodology
78
-------
Duct
^
>*v
^
^
y1^
0
T/C
N
O
1. Heated glass probe
2. Teflon stopcock
3. 250-ml heated glass gas sampling bulb
4. Tubing connection
5. Sample pump (1 cfm)
Figure A-8. C, - Cfi Hydrocarbon Sampling System
-------
bulb. This purge was continued until all visual signs of condensation had
disappeared. At that time, the back stopcock of the sampling bulb was
closed and the pump was disconnected. Once the sampling bulb pressure had
come to equilibrium with the stack pressure, the sample was sealed and
transported to the onsite laboratory for analysis.
The gas sampling bulbs were equipped with a septum port. A
gas-tight syringe was used to extract a measured amount of sample. Samples
were analyzed on a Gas Chromatograph (GC) with a Flame lonization Detector
(FID). Both methane and nonmethane hydrocarbons were measured with each
injection using a Varian Model 3700 GC with FID, automatic injection loop,
and an automatic linear temperature programming capability, located at the
Acurex laboratory in Mountain View, California. Table A-2 details the
instrument specifications.
The GC was calibrated before and after each test in order to determine
instrument drift. Blank samples were also run in order to quantify any
sampling equipment interferences.
Sample data were recorded continuously on a strip chart recorder.
After the detection of the methane peak, the column was back-flushed to
the detector for analysis of the remaining nonmethane hydrocarbons. Each
gas sampling bulb was analyzed several times to ensure a representative
sample analysis.
REFERENCES FOR APPENDIX A
A-l. Lentzen, D. E. et al., "IERL-RTP Procedures Manual: Level 1 Environ-
mental Assessment (Second Edition)," EPA-600/7-78-201, October 1978.
80
-------
Table A-2. Gas Chromatograph Specifications
Van'an Model 3700 Gas Chromatograph:
Sensitivity ! x 10'12 A/mV at attenuation 1 and
nap 10-12 fl/mV
Zero range
Noise (inputs capped)
Time constant
Gas required
range 10-12 A/mV
-10-11 to ID'9 A (reversible with
internal switch)
5 x 10~15 A; 0.5 yV peak to peak
220 ms on all ranges (approximate 1 sec
response to 99 percent of peak)
Carrier gas (helium), combustion air,
fuel gas (hydrogen)
81
-------
APPENDIX B
TRACE ELEMENT CONCENTRATIONS
Symbols appearing in the tables:
DSCM Dry standard cubic meter at 1 atm and 15 C
MCG Microgram
PPM Part per million by weight
SEC Second
< Less than
> Greater than
Trace elements having concentrations less than the detectable limit
or having a blank value greater than the sample value were given an arbitrary
concentration of zero.
Detectability limits for the various SASS samples were the following:
• 10 + 3 ym cyclones -- <0.1 yg/g
• Filter -- <0.1 yg/g
• XAD-2 -- <0.1 yg/g
0 Impinger and organic -- <0.001 yg/ml
module concentrate
• Tank water -- <0.001 yg/ml
82
-------
SECTION B.I
TRACE ELEMENT CONCENTRATIONS
(ppm)
83
-------
oo
PPM
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BAR IUM
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
CCrtALT
COPPER
FLUCRINE
GALL IUM
GERMANIUM
IRON
LANTHANUM
LEAD
LITHIUM
MAGANESF
MAGNESIUM
MERCURY
MOLYBOFNUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
RUBIDIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
CHLORIDE
NITRATE
M.A.N. RESIDENTIAL
LOW NOX
PPM
FUEL OH TAP HATER BLANK
>.100E+03
.0 E + 30
.200E-01
.300E+00
.400E-01
.300E»00
.200E-01
>.100E»33
.0 E+OO
.0 E + OO
.700E+02
.400E+00
,<.OOE-01
.SOOE+00
.100E+01
.2COF-01
.0 E+OO
.1OOE+02
.0 E + 00
.200E+00
.200E-01
.200F+00
.200E+01
<.100f+03
.LOOE+00
.0 E+00
.100E+01
.0 f + 00
.IOOE+01
.700E+01
<.1COE-01
<.100E-01
.0 E+OO
.250E+02
.0 F+00
.<.OOE+01
.0 E+OO
.200E+00
.0 e+oo
.200E+00
.0 E+OO
.300E-01
.SOOF+01
.0 F»00
.200E-01
.200E-01
.700E+00
.<>COE-Ot
.0 E»00
.0 E»00
.0 E»00
..100F*02
.700E-01
<.200E-02
.200E-02
.*OOE-02
.900E-02
.0 E+00
.200E»00
.0 E*00
.IOOE-01
.0 E»00
.600E-02
>.100E»02
.0 E+00
.IOOE+00
.0 E+00
.300E-02
.100E-02
.900E+00
.500E-01
<.200E-02
.0 E+00
.0 £+00
.200F + 00
.0 e+oo
.200E+00
.200F-01
.«OOE+00
.0 e+oo
.0 E+00
.200E-01
.0 F+00
.1 OOF+00
.0 E+00
<. IOOE-02
.0 E+00
.400E-OI
.200E-01
.0 F+00
.0 E+00
WATER TANK SAMPLF
.0 F»00
.0 F»00
.0 F»00
.0 F»00
.0 E+00
. lOOE + 00
.0 E+00
>.100F+02
.800F-02
.0 F+00
.0 F+00
.700E+00
.200E-01
.505F+01
.IOOE+00
.0 E+00
.200E-02
>.'.OOF+02
.100F-01
.TOOE-01
.0 E+00
.190E+00
. XOOF+00
.0 E+00
.300F+00
.0 E+00
.100E+01
.0 F+00
.0 E+00
.0 E+00
.0 E+00
,*OOE-02
.lOOF+00
.0 E+00
.300F-01
.0 F+00
.200F-01
>.IOOE+02
.0 F+00
.200F-01
.0 E+00
.0 E+00
. 'OOF»00
0.200F-01
.AOOF-02
.5noc-oi
>. 1 OOE+02
.300F-01
.1OOF+Ol
.700F + 01
FURNACE H20 fXJUFT
.500E + 00
.200F-01
<.900E-02
.0 E+00
.300E-OI
.0 E+00
.600E-02
.0 E+00
.0 E+00
.0 E+00
.3 E+00
.500E+00
.700E-01
.t OOE + 00
.0 F+00
.0 F+00
.700E + 01
.0 E+00
.f.OOE-01
.0 e+oo
.1 OOE + 00
.1 50F + 01
.0 E+OO
. I OOE + 00
.3 F+00
.700F+00
.0 E+00
.40JE + 00
.100E+01
.3 E+OO
.100F-01
.1 OOE + 00
.400E + 01
.0 E+OO
.0 E+OO
.0 F+00
>.t OOE + 02
<.<>OOF-01
.600F-0?
.0 E+OO
<.bOOF-02
.1 OOE + 00
.0 E+OO
.3 F+00
<.200F + 00
>.! OOF + 0?
.IOOE-01
.100E + 01
.700E+OI
SULFATC
.0 E+OO
.0 E+OO
,9<50F+03
.IOOE + 0<>
-------
00
01
PPM
_ ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BAR IUM
BORON
BROMINE
CAOMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
IRON
LANTHANUM
LEAO
LITHIUM
MAGANESE
MAGNESIUM
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
RUBIDIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
STRCNTIUM
SULFUR
TANTALUM
TELLURIUM
M.A.N. RESIDENTIAL
LOW NCX
PPM
FILTER + MASHFS XAD-2
>.110E+06
.0 E+00
.0 E+00
.786E+CK
>.110F+06
.112E+03
.0 E+00
>.HOE»06
.225E»03
.0 E+00
.0 E+00
.900E+03
.225E+03
.337E+04
.110E+05
.110E+02
<.670E+02
.560E+04
.225E+03
.225E+04
.225E+03
.225E+09
.340E+05
.0 E + 00
,560E*03
.UOE+02
.337E+03
.0 E+00
.0 E + 00
.0 E+00
.0 E»30
.0 £+00
>.IIOE+06
.1106*02
>.UOE+06
.450E+03
.780E+05
.0 E+00
.0 E+00
.0 E«-00
.0 F»00
.0 E*00
.0 E»00
.0 F*00
.400E»00
.0 E»00
.0 E*00
.0 E»00
.0 E + 30
.0 E»00
.0 E*00
.0 E»00
.0 E*00
.0 e»oo
.0 e*oo
.0 E»OO
.0 E»00
.0 E+00
.0 E+00
.0 E*00
.0 E+00
.0 E»00
<.IOOE+00
.600E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 6+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.500E+01
.100E+00
.0 E+00
1ST 1MPINGER
>.430E+00
.0 F*00
.0 E+00
.0 E+00
.200F-02
.0 E+00
.0 E+00
.0 E + 00
<.IOOP-02
<.IOOE-02
.0 E+00
.700E-01
.0 E+00
.100E+00
. 200E+00
.200E-02
.0 E+00
.300E+00
.0 E+00
.400F-01
.300E-02
,?OOE-Ol
.500E+00
<. IOOE-02
.0 E+00
.0 E+00
.200F+00
.0 E+00
.0 F+00
.IOOF.+01
<. IOOE-02
.0 E+00
.600E-02
.feOOE+00
.0 E+00
2ND t 3RD 1MP1NGER
.0 F+00
<.300F-0?
<.l OOE-Ol
.0 E+00
.0 E+00
.0 E+00
.0 F+00
.0 E+00
.0 F+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 F+00
<.100E-02
.9 E+00
.0
.0
.0
E+00
E+00
F+00
.0 E+00
.0 E+00
.0 E+00
.0 E + 00
.3 E+00
.0 E+00
.0 E+00
.0 E+00
>.IOOF+02
<.200F-02
.100E-01
.0
.0
.0
.0
.0
E+00
E + 00
E+00
E+00
E + 00
THULIUM
TIN
TITANIUM
TUNGSTEN
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
CHLORIDE
NITRATE
.0 E+00
.225E+03
.112E+0*
.0 E+00
.225E+04
.560E»02
.0 E»00
.0 E»00
.0 F_»00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 F + 00
.0 E + 00
.300E+00
.0 E+00
.0 E+00
.0 E+00
0. 130F+00
.0 E+00
.0 F+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
SULFATE
.0 E+00
.0 E+00
.0 E+00
.0 E+00
-------
GAS CONCENTRATION
00
CD
M.A.N. RESIDENTIAL
LOW NOX
MCG/OSCM
ELEMENT FILTER * WASHFS XAD-2
ALUMINUM
ANTIMONY
ARSENIC
BAPIUM
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CES IUM
CHLORINE
CHROMIUM
COBALT
COHPER
FLUCRINE
GALLIUM
GERMANIUM
IRCN
LANTHANUM
LEAD
LITHIUM
MAGANESF.
MAGNESIUM
MERCURY
MOLYBDENUM
NEOOYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
RUBIDIUM
SCANDIUM
SELENIUM
SILICCN
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THULIUM
T IN
TITAN IUM
TUNGSTEN
VANADIUM
.YTTR IUM
ZINC
ZIRCONIUM
CHLORIUE
NITRATE
SULFATE
.0 E+00
.0 E+00
> .544E+02
.554E-01
.0 E+00
.!11F+00
.0 E+00
.0 E+00
.1 IIF+OO
.167F+01
< .332E-01
.277E+01
.1 11E+00
.lllE + Ol
.111E+00
.LllE+06
.168E+02
.0 E»00
,277E*00
.0 E»00
.223E*ni
.0 E+00
.0 F+00
.0 E+00
.0 F»00
.223E*00
. 3B6F»02
.0 F+QO
.0 E^00
.n F»on
.1 HE + yo
.^Si,F»00
.0 E»00
.1 I lEfOl
• 277F-OI
.33'.? *0l
.0 F*00
.0 E*00
.0 E+00
.0 E*00
.0
.0
.0
.0
.0
E+00
F+00
£+00
F+00
F + 00
.168F+01
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 F+00
.0 E+00
.0 F+00
.0 F+00
.0 F+00
.0 E+00
.0 £+00
.0 F+00
.0 E+00
.0 E+00
.253E + 01
.0
.0
.0
.0
.0
E»00
FOO
E*00
EtOO
.0 E+00
.0 E+00
.0 F+00
.0 F+00
.0 E»00
.0 FtOO
.0 F»00
.2UF + 02
.0 E+00
.0 F+00
.0 F+00
.0 F+00
.0 E+00
.0 E+00
.0 F+00
.0 F+00
.0 F+00
. 0 E+00
.0 F+00
.0 E+00
1ST IMPINGFP
) .16RF+02
.0 E+00
.0 F+00
.0 F+00
.839F.-0!
.0 F+00
.0 F+00
.0 F+00
< , .168E+03
.0 E+00
.*! 9E+00
.0 E+00
.0 F+nn
,12bF+02
.0 F + 00
F+00
F » i > 0
.0
.0
.0
.3
F+00
F+00
F+00
t 3RD IMPINGFP
.0 E+00
< . 170E-03
.0 £+00
.0 F+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0
.0
.0
.0
.0
E+00
e+oo
E+00
E+00
F+00
.0 F+00
.0 E+00
.0 E+00
.0 F+00
.0 F+00
.0 E+00
.0 E+00
.0 E+00
< .170E-0*
.0 E+00
.0 E+00
.0 F+00
.0 E+00
.0 E+00
.0 E+00
.0 F+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 F+00
.0 F+00
.0 F+0-)
.0 E+ao
.0 F+00
.0 E+00
.0 F+PO
.0 F+00
.0 E+00
.0 F+00
.0 F+00
.0 E+00
.0 F+00
FUPN4CF
n I
> ,71?F + 0->
< .51 IF 04
< .! 70F-0?
.1 74F+0'
.0 F+00
.13RF+01
.111 F+00
.R9?E-0'
.111 E+00
.279F + OT
..'37P+00
.1 11F+06
.37RF+02
.14AF-02
.0 F+00
.223E+01
.4IPF+0?
< .4I9F-01
.0 E+00
.757F+00
5 .479F + 03
,<>21F +00
-------
CO
MASS/HEAT INPUT
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
80RON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
IRON
LANTHANUM
LEAD
LITHIUM
MAGANESE
MAGNESIUM
MERCURY
MOLYBDENUM
NEtlDYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
RUBIDIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THUL IUM
TIN
TITANIUM
TUNGSTEN
VANADIUM
YTTRIUM
UNC
ZIRCONIUM
CHLORIDE
NITRATE
H.A.M. RESIDENTIAL
LOW NDX
NG/J
KIEL OIL FURNACE H20 OUTLET
.0 F+00
.449E-03
.673E-02
.897F-03
.673F-02
.449E-03
) .224F+OI
.0 E+00
.0 F + 00
.157E + 01
.897F-02
.897E-03
.112E-01
.224E-01
.449E-03
.0 £ + 00
.224E+00
.0 F + 00
.449F-02
.449E-03
.449E-02
.449E-01
< .224E-02
.224E-02
.0 E + 00
.224E-01
.0 E+00
.224E-01
.157E*00
.0 E+00
.56IE tOO
.0 E*00
.897E-01
.0 F+00
.0 E*00
.0 F*00
.673E-03
.112E»00
.0 F+00
.449E-03
.110E-01
.157E-01
.B97F-03
.0 F*00
.0 E»00
< .198E-03
.0 E+00
.661E-03
.0 E+00
.132E-03
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.llOE-Ol
.154E-02
.106 F+00
.220E-02
.0 E+00
.154F+00
.0 F+00
.132F-02
.0 F+00
.220E-02
.331E-01
.0 £+00
.220E-02
.0 F+00
.154E-01
.0 E+00
.882E-02
.220E-01
.0 E+00
.220E-03
.220E-02
.882E-OI
.0 E+00
.0 E+00
.0 E+00
> .220E+00
< .882E-03
.132E-03
.0 E+00
< .132E-03
.220F-02
.0 E+00
.0 E+00
> .220E+00
.220E-03
.220E-01
.154E+30
FURNACF OUTLFT
> .271E-01
< .194E-07
< .64SF-07
.148C-02
> .207E-01
.662E-03
.0 E+00
> .207E-01
,42«E-04 .303E-01
.207E-05
> .846E-01
.B48E-04
) .1R2F+00
. I60E-03
-------
oo
CO
MASS/HEAT INPUT
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BOSON
BROMINE
CADMIUM
CALC IUM
CEP IUM
CESIUM
CHLOPINE
CHKOMIUM
COBALT
COPPER
FLUCRINE
G4LLIUM
GERMANIUM
IRON
LANTHANUM
LEAD
L ITHIUM
MAGANESE
MAGNESIUM
MERCURY
MOLYBDENUM
NEOOYMIUM
NICKEL
NIOBIUM
PHCSPHORUS
POTASSIUM
RUBIDIUM
SCANDIUM
SELENIUM
SILICCN
SILVER
SODIUM
STRONTIUM
SUIEUR
TANTALUM
TELLURIUM
THULIUM
TIM
7 ITANIUM
TUNGSTEN
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
CHLORIDE
NITRATF
M.A.N. RESIDENTIAL
LOW NOX
NG/J
FILTER » WASHES XAD-2
> .207F-01
.0 FOG
.0 E+00
.148F-0?
> .207E-OI
.2tlE-0<.
.0 E + 00
> .207E-01
.0 E+00
.0 E+00
. 170F-03
.635E-03
.207£-02
.207E-05
< .126E-0'.
.105E-02
.42*6-03
.640E-02
.0 E+00
.L05E-03
.207E-05
.635F.-04
.0 E+00
.8-.BE-03
.0 E+00
.0 F + OO
.0 E+00
.0 E+00
> .207E-01
.207E-05
) .207E-01
.8*8E-04
. U7E-01
.0 E+00
.0 E+00
.0 E+00
21 1E-03
0 F+00
42-VE-03
1 OSF-Od
127E-02
0 E+00
0 E+00
0 E»00
.0
.0
.0
.0
.0
F + 00
E + 00
E + 00
E + 00
E+00
.641F-03
.0 E+00
.0 F+00
.0 E+00
.0 E+00
E + 00
E+00
F+00
.0 E+00
.0 E+00
.0 F+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.0 E+00
< .160E-03
.962E-03
.0
.0
.0
.0
E+00
E + 00
F + 00
E+00
.0 E+00
.0
.0
.0
.0
.0
E + 00
E + 00
F + 00
E + 00
F+00
.0 F+00
.0 E+00
.801E-02
.160F-03
.0 F+00
F+00
F+00
F+00
F+00
F + 00
F + 00
E + 00
E + 00
E+00
E+00
1ST IMPINGFR
5 .631F-02
.0 F+00
.0 F+00
.0 c+00
.3! 9E-04
.0 F + 00
.0 E+00
.0 E+00
< . 160F-OV
< ,160F-0<,
.0 F*or»
.I12F-02
.0 F+00
.160E-02
.3I9E-02
.319E-079F-03
.798E-02
< .160E-04
.0 E+00
.0 E+00
.319F-02
.0 F+00
.0 E+00
. KSOE-01
< .I60F-04
.0 Ft 00
.958F-04
.958F-Q?
.0 F+00
> .fr38E-)l
.0 F+00
> .IfrOF + OO
< .319E-04
.1 iSOF-0^
.0 E+00
.0 E+00
. * 79F-D2
.0 F+00
.0 c»nn
.0 r»00
0 .?ORF-0?
.0 c+00
.0 F+00
.0 FtOO
2NH t 3RD 1MPIN<",FP
.0
< .19
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
E+00
.= -07
oc _ n "7
F+OO
E+OP
E+00
F + OO
F+OO
E+00
F+OO
E + 00
E+on
F + OO
E + 00
E + 00
F + OO
E+00
E+00
F+OO
F + OO
E + 00
F + OO
E + 00
< . 648F-08
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
. 0
.0
.0
.0
.0
.0
.0
E+00
E+00
E+00
F+OO
E+00
F+oo
E+oo
F+OO
F + OO
E+OO
F+OO
E+00
E+00
F + OO
F+OO
E + 00
E+00
F + OO
F+OO
F + OO
C+UO
r+oo
F+OO
F + OO
E + 00
E + 00
FL)ONACf f'MTl
> .?T r-0'
.0 F+00
> .707F-01
< . I f-CI' 04
.0 c+m
. "576P-0?
< .1 76^-03
.I07C-02
0?
.0 F+00
.' f-OF-0'
.0 F+00
.95RE-0'.
.0 F+01
. r. r»oo
.0 e+oo
.0 F+00
SULFATE
E»00
E+00
.0 E+00
+00
.0 F+OO
-------
oo
MASS/TIME
ELEMENT
ALUHINUM
ANTIMONY
ARSENIC
BARIUM
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLCRINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
IRON
LANTHANUM
LEAD
LITHIUM
HAGANESE
MAGNESIUM
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
RUBIDIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THULIUM
TIN
TI TANIUM
TUNGSTEN
VANADIUM
'YTTRIUM
ZINC
ZIRCONIUM
CHLORIDE
NITRATE
SULFATE
M.A.N. RESIDENTIAL
LOW NOX
MCG/SEC
FUEL OIL FURNACE H20 OUTLET
.227F+00
.907E-02
.«0«E-02
.0 E+00
.136E-01
.0 E+00
.272F-02
.0 E+00
.0 E+00
.0 E+00
.0 E+00
.227E+00
.318E-01
.2I8E+OI
.0 E+00
.923E-02
.138E+00
.185E-01
.138E+00
.923E-02
> .461E+02
.0 E+00
.0 E+00
.323E+02
.185E+00
.185E-01
.231E+00
.461E+00
.923E-02
.0 E+00
.461E+01
.0 E+QO
.923E-01
.923E-02
.923E-01
.923E+00
< .461E-01
.461E-01
.0 E+00
.461E+00
.0 E+00
.461E+00
.323E+01
< .<»61E-02
< .461E-02
.0 E+00
.115E+02
.0 E+00
.185E+01
.0 E+00
.923E-01
.0 E+00
.923E-01
.0 E+00
.138E-01
.231H+01
.0 E+00
.923E-02
.9?3E-02
.323E+QO
.185E-01
.0 E+00
.0 F+00
.0 E+00
.0 E+00
.0 E+00
.318E+OI
.0 E+00
.272E-01
.0 E+00
.681 E+00
.0 E+00
.45AE-01
.0 E+00
.318E+00
.0 E+00
.181E+00
.0 E+00
.454E-02
.4S4E-01
.181E+01
.0 E+00
.0 E+00
.0 E+00
< .181E-01
.272E-02
.0 E+00
< .272E-02
.454E-01
.0 E+00
.0 F+00
< .907F-01
FURN4CF OUTIFT
> .5S8E+00
< .'.OOE-06
< .M3E-05
.305E-01
.136F-01
.0 F+00
> .476E+00
.872E-03 .623E+00
5 .375E+01
.330F-02
-------
MASS/TIME
ELEMENT
"ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BORCN
BROMINE
CAOMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
IRON
LANTHANUM
LEAD
LITHIUM
MAGANESE
MAGNESIUM
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
RUBIDIUM
SCANDIUM
SELENIUM
SILICCN
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLUP IUM
THULIUM
TIN
TI TANIUM
TUNGSTEN
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
CHLORIDE
NITRATE
SULFATE
M.4.N. RESIDENTIAL
LCW NOX
MCG/SEC
FILTER t WASHES XAD-2
.0 FtOO
.0 EtOO
.305E-01
. .l3lEtoi
.0 FtOO
> .32SEt01
< .6S7E-03
.328F-02
.0 FtOO
.0 EtOO
.985E-01
.0 FtOO
E-t-00
EtOO
.0
.0
.0
.0
.0
EtOO
EtOO
Etf>0
2ND £ 3RD IMPINGER
.0 EtOO
< .133F-05
.0
.0
.0
. 0
.0
.0
.0
.0
.0
.0
.0
.0
.3
.3
.0
.0
.0
.0
.0
.0
FtOO
EtOO
FtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
EtOO
FtOO
EtOO
EtOO
EtOO
FtOO
EtOO
EtOO
EtOO
< .133E-06
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
. 0
.0
.0
.0
EtOO
EtOO
EtOO
EtOO
E+00
EtOO
EtOO
EtOO
FtOO
EtOO
EtOO
FtOO
EtQ3
EtOO
EtOO
EtOO
EtOO
EtOO
FtOO
FtOO
EtOO
EtOO
EtOO
EtOO
Etno
FtOO
FUPNACF PIPTLFT
< .400F-06
< .' ??E-OS
.Tnsp-O'
•) .'.27EtOO
. 1 ^F-Ol
.0 FtOO
> ,426FtOO
.872F-03
-------
IN » FUEL OIL
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
FLUORINE
GALLIUM
GERMANIUM
IRON
LANTHANUM
LEAD
LITHIUM
MAGANESE
MAGNESIUM
MERCURY
MOLYBDENUM
NECDYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
RUBIDIUM
SCANDIUM
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
VANADIUM
YTTRIUM
ZINC
ZIRCONIUM
CHLORIDE
NITRATE
SULFATE
M.A.N. RESIDENTIAL
I OH Nnx
FURNACE MASS BALANCE
HUT - FXHAUST CAS » FURNACE WATER
TOTAL IN TOTAL OUT
.461E»0?
-------
APPENDIX C
CONVERSION FACTORS
MULTIPLIERS TO CONVERT EMISSION FACTORS FROM
g/kg TO OTHER UNITS FOR NO. 2 OIL3
To obtain emission factor Multiply emission factor in
in these units g/kg fuel by
Gaseous pollutants and parti cul ate:
kg/1000 1 fuel 0.862
g/106 cal input 0.092
^ lb/1000 gal 7.194
lb/106 Btu input 0.051
Gaseous pollutants;!3
ppm at 3 percent 02, dry 1770
~~
ppm at 0 percent 02, dry 2065
"RTF
ppm at 12 percent C02 1597
~~
Parti culates:
lb/106 scf flue gas at 3 percent 02 4.58
lb/106 scf flue gas at 0 percent 02 5.27
lb/106 scf flue gas at 12 percent C02 4.13
a Typical no. 2 fuel oil having 33 API gravity
" MW = molecular weight of pollutant
92
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
. REPORT NO
EPA-600/7-82-038a
3. RECIPIENT'S ACCESSION NO.
. TITLE AND SUBTITLE
Environmental Assessment of a Low-emission oil-
fired Residential Hot Water Condensing Heating
System; Volume L Technical Results
5. REPORT DATE
Mav 1982
6. PERFORMING ORGANIZATION CODE
AUTHOFUS)
8. PERFORMING ORGANIZATION REPORT NO.
C. Castaldini
;. PERFORMING ORGANIZATION NAME AND ADDRESS
Acurex Corporation
485 Clyde Avenue
Mountain View, California 94042
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-3188
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
Final; 7/80-2/81
14. SPONSORING AGENCY CODE
EPA/600/13
is.SUPPLEMENTARY NOTES jERL-RTP project officer is Robert E. Hall, Mail Drop 65, 919/
541-2477. Volume II is a data supplement.
is. ABSTRACT rpne repOrt gjves results of a test program measuring air and water emis-
sions from a high-efficiency hot-water residential heating system of European
design, utilizing a condensing flue gas system and a low emission burner. Criteria
and noncriteria emissions, including trace elements and organic species in both flue
gas and condensate waste water streams, were measured. NO (as NO2), CO, total
UHC (as propane), and total particulate emissions measured about 37, 12, 1. 5, and
2.7 ng/J heat input, respectively. Absorption of sulfates and nitrates in the waste
water resulted in a constant pH of 3.0. Total organic emissions in the flue gas mea-
sured 3. 5 mg/dscm; they were below the detectable limit in the waste water. Several
inorganic trace elements, including chromium, copper, iron, and nickel, in the
waste water were attributed to leaching of heat transfer metal surfaces by the warm
acidic water. Bioassays were also performed to evaluate the potential health hazard
of the streams. Results indicate nondetectable to moderate toxicity and mutagenicity.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
Pollution Waste Water
Assessments Condensates
Hot Water Heating Measurement
Residential Buildings
Fuel Oil
Flue Gases
Pollution Control
Stationary Sources
Environmental Assess-
ment
13 B
14 B
13A
13M
21D
21B
07D
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
99
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
93
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