SEPA
United States Industrial Environmental Research EPA-600 7-80-087
Environmental Protection Laboratory April 1980
Agency Research Triangle Park NC 2771 1
Environmental
Assessment of an Oil-fired
Controlled Utility Boiler
Interagency
Energy/Environment
R&D Program Report
-
-------
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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EPA-600/7-80-087
April 1980
Environmental Assessment of an
Oil-fired Controlled
Utility Boiler
by
C. Leavitt, K, Arledge, C. Shih,
R. Orsini, A. Saur, W. Hamersma,
R. Maddalone, R. Beimer, G. Richard,
S. Unges, and M. Yamada
TRW, Inc.
One Space Park
Redondo Beach, California 90278
Contract No. 68-02-2613
Task No. 8
Program Element No. EHE624A
EPA Project Officer: Michael C. Osborne
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
ABSTRACT
A comprehensive emissions assessment was performed on the Haynes No. 5
boiler during oil firing. Level 1 and Level 2 procedures were utilized to
characterize pollutant emissions. Results of the comprehensive assessment,
in conjunction with assumed typical and worst case meteorological conditions,
were utilized to estimate the environmental impact of emissions from this
type of unit. Principal conclusions indicated are as follows: 1) The risk
of violating National Ambient Air Quality Standards (NAAQS) due to criteria
pollutant emissions is low. 2) Little adverse health effect is anticipated
as a result of SO^, S0.~, and particulate emissions projected from wide-
spread use of oil-fired units of the type tested. 3) The impact of trace
element burdens in drinking water, plant tissue, soil and the atmosphere is
negligible. 4) The risk of plant damage due to criteria pollutant emissions
is remote. 5) The likelihood of plant damage due to trace element emissions
is remote.
n
-------
Environmental
Protection Agency
Region 9
CONTENTS JUN 1 1 1980
Abstract ii
Metric Conversion Factors and Prefixes . iv
1. Introduction 1
2. Summary and Conclusions 3
3. Test Setting 7
4. Assessment of an Oil-fired Utility Boiler 16
5. Environmental Impact Assessment 33
Appendices
A. Simplified Air Quality Model 58
B. Organic Analysis Methods 64
lii
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TABLES
Number Page
2-1 Summary of Pollutant Emissions From an Oil-fired Utility
Boiler 4
3-1 Boiler Number 5 Design Data 11
3-2 Typical Fuel Oil Analysis 13
4-1 Summary of Test Conditions 17
4-2 Summary of Ultimate Fuel Analysis 18
4-3 Concentration of Major Trace Elements in Oil 19
4-4 Existing and Proposed Federal Emission Standards for
Oil-fired Utilities 21
4-5 Comparison of Average Criteria Pollutant Emissions with
EPA AP-42 Emission Factors for Oil-fired Utility Boilers . 21
4-6 Summary of Criteria Pollutant Emissions 22
4-7 SOpj S03, and SO," Emissions 25
4-8 Summary of Sulfate Emissions 25
4-9 Emission Concentrations of Trace Elements. . . 27
4-10 Emission Factors for Trace Elements 29
4-11 POM Emissions from Oil Firing 31
5-1 Emission Rates from a Controlled 353 MW (Gross) Oil-fired
Utility Boiler 34
5-2 Annual Emissions 35
5-3 Comparison of Federal Air Quality Standards With Air
Quality Predicted to Result From Oil Combustion in a 353
MW (Gross) Utility Boiler 37
5-4 Health Impacts of Sulfate Aerosol 41
5-5 Expected Trace Element Concentrations in Vicinity of a
353 MW (Gross) Oil-fired Utility Boiler 43
5-6 Annual Deposition of Trace Elements in Vicinity of
Controlled Oil-fired Power Plants 45
5-7 Long Term Effect of Controlled Oil-fired Utility Boiler
Emissions on Soil Concentrations of Trace Elements .... 45
5-8 Long Term Effect of Controlled Oil-fired Boiler Emissions
on Concentrations of Elements in Plants 46
5-9 Trace Element Concentration in Runoff Water in Vicinity
of Controlled Oil-fired Utility Boiler 48
iv
-------
TABLES (Continued)
Number Page
5-10 Projected Ozone Concentrations Which Will Produce, for
Short Term Exposures, 20 Percent Injury to Economically
Important Vegetation Grown Under Sensitive Conditions. . . 50
5-11 Sensitivity of Common Plants to SO^ Injury 53
A-l Stack Parameters and Plume Rise 61
A-2 Predicted Maximum Ambient Concentrations of Criteria
Pollutants 62
B-l Sample Code for Organic Samples Analyzed 67
B-2 Results of TCO Analysis of Unconcentrated and Concentrated
Samples 69
B-3 Results of Field GC Analysis 70
B-4 Gravimetry of Sample Concentrates 71
B-5 Interpretation of Infrared Spectra of Sample Concentrates. 73
B-6 Summary of GC/MS Samples and Analyses From the Oil-fired
Site 76
B-7 GC/MS Analysis of 141-XMB-SE-KD (Blank) Combined Extracts. 76
B-8 GC/MS Analysis of 142 SASS Composite 77
B-9 GC/MS Analysis of 143 SASS Composite 78
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FIGURES
Number Page
3-1 Plot Plan Haynes Power Plant 8
3-2 Schematic of the Oil Boiler 9
3-3 System Schematic 12
5-1 Health Effects from Sulfate Levels Resulting From Oil
Combustion in Utility Boilers 40
5-2 Increase in Mortality Rates in Vicinity of Oil-fired
Utility Boilers as a Result of SOo and Total Particulate
Emissions 42
5-3 N02 Threshold Concentrations for Various Degrees of Plant
Injury 51
5-4 S02 Dose-Injury Curves for Sensitive Plant Species .... 53
B-l Flow Chart of Sample Handling and Analysis Procedures. . . 66
vi
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METRIC CONVERSION FACTORS AND PREFIXES
CONVERSION FACTORS
To convert from
Degrees Celsius (°C)
Joule (0)
Kilogram (kg)
Kilojoule/kilogram (kJ/kg)
Megagram (Mg)
Megawatt (MW)
Moter (m)
Meter3 (rn3)
Moter3 (m3)
Meter3 (m3)
To
Degrees Fahrenheit (°F)
Btu
Pound-mass (avoirdupois)
Btu/lbm
Ton (2000 lbm)
Horsepower (HP)
Foot (ft)
Barrel (bbl)
Foot3 (ft3)
Gallon (gal)
Multiply by
t(°F) = 1.8 t(°C) + 32
9.478 x 10"4
2.205
4.299 x 10"1
1.102
1.341 x 103
3.281
6.290
3.531 x 101
2.642 x 102
Nanogram/joule (ng/J)
Picogram/joule (pg/J)
Ib /million Btu
Ib /million Btu
2.326 x 10
2.326 x 10
-3
-6
PREFIXES
Multiplication
Prefix
Peta
Tera
Giga
Mega
Kilo
Milli
Micro
Nano
Pico
Symbol
P
T
G
M
k
m
V
n
P
Factor
10
1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
0
15
1?
J £
9
6
3
-3
-6
-9
-12
1
1
1
1
1
1
1
1
1
Pm =
Tm =
Gm =
Mm =
km -
mm =
ym =
nm =
pm =
Examp_l_
1
1
1
1
1
1
1
1
1
x
x
X
X
X
X
X
X
X
10
10
10
10
10
10
10
10
10
e
meters
12
meters
g
meters
meters
3
meters
rneter
meter
-9
meter •
-12
meter
VI1
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SECTION 1
INTRODUCTION
Conventional methods for conversion of fuels into usable forms of
energy historically have impacted all segments of the environment. Most
conventional combustion processes emit sulfur oxides, nitrogen oxides,
carbon oxides, particulate matter and other potentially harmful pollutants
to the air. Conventional fuel combustion processes are playing an in-
creasing role in the movement toward national energy independence. As a
result, the potential for adverse environmental impact is also increasing.
In recognition of these facts, IERL-RTP established the Conventional
Combustion Environmental Assessment program (CCEA) to conduct comprehensive
assessments of the effects of combustion pollutants on human health,
ecology, and the general environment. The assessments will result in re-
commendations for control technology and standards development to control
adverse effects within acceptable limits.
This report details results of a comprehensive emissions assessment
performed on the Haynes No. 5 utility boiler in Long Beach, California.
The No. 5 unit is a once-through, supercritical boiler with a net electric
generating capacity of 346 MW. Although either oil or gas may be burned
in this unit, tests described herein were performed exclusively during oil
firing. The unit has a horizontally-opposed wall fired furnace and is
equipped with off-stoichiometric firing and flue gas recirculation for NOY
/\
control. No particulate or SO controls are utilized.
A
Based on 1978 data, non-tangential units comprise 59% of all generating
capacity for residual oil-fired utility boilers. The average size for
non-tangential units is 100 MW which is a factor of three smaller than the
tested unit. Only 18% of all non-tangential oil-fired generating capacity
is associated with NO controls although 54% of the capacity provided by
A
controlled horizontally-opposed firing is associated with some form of off-
stoichiometric firing in conjunction with flue gas recirculation. Oil-fired
utility boilers typically do not utilize particulate or SO controls. Since
/\
-------
the Haynes No. 5 unit is somewhat larger than the average non-tangential
utility boiler, it may be considered typical of large horizontally-opposed
units with N0¥ controls.
A
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SECTION 2
SUMMARY AND CONCLUSIONS
A comprehensive emissions assessment was performed on the number 5
boiler at Haynes Power Plant in Long Beach, California. The plant is owned
and operated by the Department of Water and Power of the City of Los Angeles.
The number 5 boiler is a Babcock and Wilcox supercritical Universal-Pressure
boiler with a net electrical generating capacity of 346 MW. Either low
sulfur oil or natural gas may be fired in the horizontally-opposed wall
fired furnace of the number 5 unit. MO emissions are controlled with off-
A
stoichiometric firing and flue gas recirculation.
Emissions testing was performed during oil-fired operation. Level 1
and Level 2 (1) analyses were performed on the fuel oil and the flue gas.
Level 1 analyses were performed to determine NO and hydrocarbon concentra-
A w *
tions in the flue gas. Concentrations of CO, S02, S03, SO.', Cl", F", and
total particulates in the flue gas were determined by Level 2 analyses.
Trace element concentrations in the flue gas were estimated from Level 1
analysis of the fuel oil assuming all trace elements were emitted from the
stack. No significant liquid or solid waste streams are produced by the
boiler unit.
Results of the emissions assessment are presented in Table 2-1. Measured
emissions of the criteria pollutants and SO^ correspond well with published
AP-42 (2) emission data from oil-fired utility boilers although measured
NO and total organic emissions were somewhat lower. Reduced NOV emissions
A X
are the result of NO control systems on the number 5 unit.
A
Of the 39 trace elements studied during this effort, only the estimated
flue gas concentrations of Cr and Ni were found to exceed their respective
Discharge Multimedia Environmental Goal (DMEG) values. Hence, emission
factors for these elements have been included in the emissions summary table.
Speciation of organic compounds present in the flue gas indicated the
presence of aliphatic hydrocarbons, benzaldehyde, trimethyl cyclohexane-one,
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TABLE 2-1. SUMMARY OF POLLUTANT EMISSIONS
FROM AN OIL-FIRED UTILITY BOILER
Pollutant Emission Factor, ng/J
NO * (as N09 near full load) 116 ± 2.12ftt
" £
C0f 6.6 ± 3.1m
S02* 98 ± 7.0ttt
S03** 1.14
S04=** 1.27
Total Organicsft 0.42-0.58
Total Parti oil ates** 7.5 ± 1.2ttf
_**
Cl 1.34
_**
F 0.061
***
Cr . 0.002
***
Ni 0.2
NO was determined by continuous chemiluminescent analysis (Level 1).
j. x
CO was determined by continuous non-dispersive infrared analysis
(Level 2).
SOg v/as determined by continuous pulsed fluorescence analysis and by
the CCS (Level 2).
SO,, SO/, Cl" and F" were determined by analysis of the CCS (Level 2).
tt
C-|- C-J6 fractions were determined by gas chromatograph while the >C-jg
fraction was determined gravimetrically (Level 1).
Total particulates were determined by a modified Method 5 procedure
(Level 2).
***
Trace element emission factors were estimated from the SSMS fuel
analysis under the assumption that all trace elements in fuel would
be emitted from the stack. Only the estimated flue gas concentrations
of Cr and Ni were found to exceed their respective DMEG values.
The indicated uncertainty represents one standard deviation.
-------
t^ substituted acetophenone, methyl esters of benzole acid and substituted
benzoic acid, diethylphthalate, and ethylbenzaldehyde at concentrations
3 3
between 0.02 ug/m and 2 yg/m . POM emissions consisted primarily of
naphthalene. With the exception of the possible presence of benzo(a)-pyrene
(benzopyrenes were detected but benzo(a)pyrene was not specifically identi-
fied), comparison of measured concentrations of organics with their
respective DMEG values indicates that all POM compounds were present at
levels too low to be of environmental concern.
An environmental impact assessment was performed based upon emission
rates measured at the Haynes No. 5 boiler and assumed typical and worst case
type meteorological parameters. Principal conclusions indicated by this
assessment are as follows:
• The environmental acceptability of emissions from oil-fired
boilers is largely dependent on site-specific factors such
as background pollution levels and meteorology. However,
the risk of violating NAAQS due to criteria pollutant emis-
sions from an oil-fired boiler (353 MW gross output scale)
like Haynes No. 5 appears low.
• Based on the Lundy-Grahn Model for health effects associated
with suspended sulfate levels, limited adverse health
effects would result from these emissions. Similar results
were obtained with this model considering the effects of
S02 and total particulate emissions on people older than 40
years of age.
t The impact of trace element burdens in drinking water, plant
tissue, soil and the atmosphere as a result of measured
emissions from this oil-fired utility boiler is generally
orders of magnitude less than allowable exposure levels.
t The risk of plant damage due to criteria pollutant emissions
from this oil-fired boiler appears to be remote. However,
the effect of secondary pollutants formed by reactions
between NOX and hydrocarbons, and the synergistic effects of
$02 in the presence of ozone are uncertain.
• The likelihood of damage occurring in plants due to trace
elements from oil firing at Haynes appears remote.
-------
REFERENCES FOR SECTION 2
Hamersma, J.W., D.G. Ackennan, M.M. Yamada, C.A. Zee, C.Y. Ung, K.T.
McGregor, J.F. Clausen, M.L. Kraft, J.S. Shapiro, and E.L. Moon.
Emissions Assessment of Conventional Stationary Combustion Systems,
Methods and Procedures Manual for Sampling and Analysis. Report
prepared by TRW Systems Group for the U.S. Environmental Protection
Agency. EPA-600/7-79-029a. January 1979.
Compilation of Air Pollution Emission Factors, AP-42, Part A.
Edition. U.S. Environmental Protection Agency. August 1977.
Third
-------
SECTION 3
TEST SETTING
PLANT DESCRIPTION
The oil-fired utility boiler tested was Boiler Number 5 at Haynes
Power Plant, Long Beach, California. The boiler is owned and operated by
the Department of Water & Power of the City of Los Angeles. Boiler Number
5 is one of six boiler units at the facility. It burns either natural gas
or low sulfur oil, and utilizes off-stoichiometric firing and flue gas
recirculation to control NO emissions.
7\
The Haynes Power Plant is located in the urban Los Angeles Basin
approximately 32 kilometers south of downtown Los Angeles. Figure 3-1
shows a general plot plan of the entire facility, and Figure 3-2 shows the
general material flow diagram for the unit tested.
As shown in Figure 3-1 the facility has six boiler units. This number
is made up of three identical pairs of boilers, that is units 1 and 2 are
identical, units 3 and 4 are identical, and units 5 and 6 are identical.
Fuel for the facility is supplied by ARCO, Coastal States Marketing,
and Asiatic Petroleum. It is usually transported to the facility by pipe-
line. There is approximately 1,000,000 barrels of oil storage capacity at
the facility.
Water for boiler feed water makeup, fire fighting, and general usage
is supplied by the City of Long Beach Water System. Waste water from general
wash-down, and contaminated condensate is treated on site in settling ponds
and ultimately discharged into the San Gabriel River. Metal cleaning waste
solutions are removed via vacuum trucks and hauled to designated waste
disposal areas.
Boiler
Boiler Number 5 was built to the Department of Water and Power's
specifications by Babcock and Wilcox. It is a double reheat, supercritical
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UNIT
6
GT 6
OCUJ
GAS TURBINE
GT 5
UNIT
4
UNIT
3
I GT3 I
UNIT
2
UNIT
1
GT2
GT1
ADMIN
BLDG
PARKING
Figure 3-1. Plot Plant Haynes Power Plant
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AIR
HEATER
sx\\\\v
\\N UN IT NO. 5
AIR
HEATER
RECIRCULATION
FAN
FEEDWATER
HEATERS
T
RECIRCULATION
FAN
CONDENSATE
FROM
L.P. TURBINE
FORCED
DRAFT
FAN
FORCED
DRAFT
FAN
Figure 3-2. Schematic of the Oil Boiler
FLUE
GAS TO
STACK
OUTSIDE
AIR
OUTSIDE
AIR
STEAM
TO
H.P. TURBINE
-------
pressure, horizontally-opposed wall fired, Universal-Pressure boiler. The
boiler can burn either natural gas or oil. Boiler number 5 was put into
commercial operation in August 1966. Table 3-1 contains the boiler specifi-
cation data. A schematic diagram of the boiler and ancillary equipment is
given in Figure 3-2.
Combustion air is supplied to the unit by two forced draft fans.
Prior to entering the combustion zone the temperature of the air is in-
creased to approximately 550 K in the preheater section. The air preheaters
recover heat from the flue gas and transfer it to the combustion air via
heat exchangers.
Fuel is usually brought to the facility via natural gas and oil pipe-
lines. The oil is continuously circulated through the system to avoid
gumming and waxing due to settling of heavy hydrocarbons. The oil is pumped
about the facility at a rate of 0.024 m /s.
Combustion air is supplied to the unit by two variable speed fluid
drive, air foil blade fans. Each fan supplies 10,100 m3 of air at 300 K
at a pressure of 113 kPa.
Recirculation of the flue gas to the boiler combustion zone is accom-
plished by two constant speed, damper controlled fans. Each flue gas
3
recirculation fan delivers 5500 m at 648 K at a pressure rise of 4.16 kPa.
Figure 3-3 is a simplified schematic of the system showing the
generalized flow through the system. Super heated steam leaves the boiler,
passes through the high pressure turbine and is then routed back to the
boiler where it passes through the 1st reheater. From the 1st reheater the
steam is sent to the intermediate pressure turbine and is then routed back
to the boiler where it passes through the 2nd reheater. From the 2nd re-
heater the steam is sent to the low pressure turbine. From the low pressure
turbine the steam is sent to a condenser. From the condenser the liquid
passes through a system of eleven heaters arranged in series where it is
heated and returned to the boiler. The heaters are supplied with steam
from various points in the system.
The boiler powers two generators. One is driven by the high and inter-
mediate pressure turbines, the other by the low pressure turbines. The
10
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TABLE 3-1. BOILER NUMBER 5 DESIGN DATA
Type
Manufacturer
Number of Burners
Burner Arrangement
Air Preheater
Combustion Air Temperature
Combustion Air Volume
Recirculation Gas
Volume
Temperature
Reheat
Design Steam Rate
Super Heat
First Reheat
Second Reheat
Design Generating Capacity
Oil/gas
Babcock & Wilcox
24
Front and Rear Firina
Yes
572 K
6.02 m3/s (300 K)
Yes
3.26 m3/s
647 K
Two Stage
16,200 Kg/s, 25 MPa, 811 K
13,700 Kg/s, 7.3 MPa, 835 K
12,100 Kg/s, 2.6 MPa, 849 K
353 MW (gross)
combined generators have a capacity of 353 MW (i.e., maximum gross output
is 353 MW as opposed to the salable or net output of 346 MW).
The fuel oil specifications are critical because burning of "clean"
fuel constitutes the only S02 and particulate control mechanism. A typical
fuel oil analysis is presented in Table 3-2. Because the boiler can burn
gas, the oil tests were scheduled such that they occurred after the boiler
had been burning only oil for at least a week.
Air Quality Control
Emissions of sulfur dioxide and particulates are controlled by burning
low sulfur fuel oil, by the furnace design, and by rigorous maintenance and
operational procedures.
Off-stoichiometric firing and flue gas recirculation are used to
minimize NOV emissions. Off-stoichiometric firing consists of running each
A
11
-------
I
mi
AT
,.'!
:R
-1 1
si
I ^T
CONDENSER
Figure 3-3. System Schematic
-------
TABLE 3-2. TYPICAL FUEL OIL ANALYSIS
Heating Value 44,000 KJ/Kg
Viscosity, SUS at 333 K 112.9
Sulfur, % by Weight 0.18
Ash, Weight % of Oil 0.030
Specific Gravity of 289 K 0.9100
Water Content, % 0.21
Metal (ppn)
Iron 9.3
Vanadium 3.9
Nickel 5.1
Sodi urn 30
Calcium 0.13
Magnesium 5.6
Copper 0.40
Potassium 1.85
Lead 2.3
Zinc 0.51
Aluminum 1.0
Data were provided by Haynes personnel. No information is available
regarding the number of samples analyzed or standard deviations of
analyses.
burner fuel rich (i.e., less than stoichiometric oxygen). The remainder of
the oxygen necessary for complete combustion is added to the furnace either
through burners to which the fuel feed has been terminated or through
special air injection points called "NO ports". Running the burners fuel
/\
rich stretches out each flame and causes it to burn cooler. NO is formed
A
two ways, by thermal fixation of atmospheric nitrogen and from the fuel
nitrogen. Lowering the combustion temperature reduces the rate at which
atmospheric nitrogen is converted to NO . Also, fuel rich flames are
/\
oxygen deficient. Reduced availability of oxygen minimizes NO formation
J\
from both of the mechanisms outlined above.
13
-------
Flue gas recirculation consists of recirculating some part of flue
gas through the burners. This procedure results in combustion air with a
reduced oxygen concentration which in turn reduces the NO formation rates.
A
Liquid Effluents
No significant liquid streams are produced by the boiler.
Solid Waste
No significant solid wastes are produced by the boiler.
OIL-FIRED UTILITY TEST
The only major emission source at the oil-fired utility site is the
stack. There are no emission controls other than rigid fuel specifications,
except for NO. Control of NOV is by off-stoichiometric firing and flue
A X
gas recirculatiori. Therefore, only two streams were sampled, the fuel oil
feed and the stack emissions. No solid or liquid streams were sampled.
The stack emissions of criteria pollutants are very low. As a result,
analysis of the particulates and organics was difficult because of small
sample sizes.
Emissions were characterized using EPA's phased approach to sampling
and analysis. This approach utilizes two separate levels of sampling and
analytical effort (Level 1 and Level 2). Level 1 is a sampling and analysis
procedure accurate within a factor of about 3. This level provides pre-
liminary assessment data and identified problem areas and information gaps
which are then utilized in the formulation of the Level 2 sampling and
analysis effort. Level 2 provides more accurate detailed information that
confirms and expands the information gathered in Level 1. The methods and
procedures used are, in some instances, modified for Level 1 sampling and/or
analysis procedures and are documented in the manual, "Combustion Source
Assessment Methods and Procedures Manual for Sampling and Analysis",
September 1977. The Level 2 methods and procedures included "state-of-the-
art" techniques as adapted to the needs of this site. Normally all Level
1 samples are analyzed and evaluated before moving to Level 2. However,
because of program time constraints, the Level 1 and Level 2 samples were
obtained during the same test period.
14
-------
The Source Assessment Sampling System (SASS) was used to collect both
gaseous and particulate emission samples at the scrubber inlet and outlet
for Level 1 organic and inorganic analysis. The train v/as run for 6 to 8
hours until a minimum of 30 cubic meters of gas had been collected.
Previous sampling and analysis efforts had indicated possible inter-
ference of SASS train materials on certain organic and inorganic analysis
when at the lower detection limits of Level 2 methods. To avoid this
possibility, all glass sampling trains were used to collect Level 2 samples.
Two Method 5 sampling trains were modified for Level 2 organic and inorganic
sample acquisition. Both trains sample approximately 10 cubic meters of
flue gas during a 6- to 8-hour run time.
A controlled condensate train (Goksoyr-Ross) was used at each location
to obtain samples for S0o> SOg (as FLSO^), particulate sulfate, HC1 and HF.
15
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SECTION 4
EMISSION ASSESSMENT OF AN OIL-FIRED UTILITY BOILER
TEST CONDITIONS
Four tests were performed firing residual fuel oil. Electrical output
at this site ranged from 218 to 330 gross MW, corresponding to 62 to 94%
of full-load capacity. These test conditions are tabulated in Table 4-1.
Efficiencies and emission factors for oil firing are computed using the heat
input from oil feed rates. The accuracy of tabulated steam production rates
has been estimated to be about 1325, based on oil feed rates and gross
electrical output. Oxygen concentrations presented are the averages
obtained from continuous monitoring at the stack. Typical furnace oxygen
levels for normal operation are 3 to 4%. Using fuel oil analyses, this
oxygen range corresponds to an excess air input of approximately 16 to 22%.
Flue gas flow rates were computed from the oxygen concentration at the
stack, fuel analyses, and fuel feed rates (estimated from steam production
rate data) using the following expression:
4.762 (nc + n$ + .45 n^) + .9405 nH - 3.762 nQ
1 - 4.762 (02/100)
where:
nFG
nPQ = 9ram moles of dry effluent per gram of fuel
n. = gram moles of element j per gram of fuel
J
02 = volumetric Og concentration in percent
Flue gas flow rates are expressed as dry standard cubic meters per second;
standard temperature and pressure are defined as 293 K and 101.3 kPa,
respectively.
Ultimate analyses of the fuel oil are presented in Table 4-2, along
with averages and standard deviations. Analysis results indicate that the
main fuel components and heat contents were essentially constant during the
test period. Variation in oxygen contents is attributed to the low fuel
oxygen content and the fact that oxygen is determined by difference.
16
-------
TABLE 4-1. SUMMARY OF TEST CONDITIONS
Test
No.
141
142
143
144
Electrical
Output
(Gross)
MW
330
218
325
310
% of
Maximum
Load
94
62
92
88
Nominal
Fuel Feed
Rate,
kg/hr
69,000
54,900
66,300
61,700
Steam
Production
Rate, ,.
kg/hr x 10°
0.781
0.536
0.860
0.717
Overall
Efficiency
39
32
40
40
Average 02
in Flue Gas
6.35
5.76
5.66
5.98
Excess Air
At Furnace
16-22
16-22
16-22
16-22
Flue Gas
Flow Rate
dscm/s
300
230
280
270
-------
TABLE 4-2. SUMMARY OF ULTIMATE FUEL ANALYSIS
Component
Carbon
Hydrogen
Ni trogen
Sulfur
Ash
Oxygen
Heating Value (kJ/kg)
141
86.94
12.41
0.37
0.21
0.01
0.06
43,994
142
86.41
12.40
0.16
0.17
0.00
0.86
44,224
Test
143
86.60
12.33
0.17
0.16
0.01
0.73
44,131
144
86.21
12.43
0.87
0.19
0.01
0.98
44,035
Average
86.54
12.39
0.39
0.18
0.01
0.66
44,096
a*
0.31
0.04
0.33
0.02
0.01
0.41
103
a = one standard deviation.
f Oxygen concentration by difference.
Additional analyses were performed on a composite oil sample (tests
141-144) to determine concentrations of trace and minor elements. The oil
analysis was performed by spark source mass spectrometry (SSMS), except for
mercury, which was performed by elemental sparging. These data are presented
in Table 4-3. Typical ranges of some trace and minor elements in U.S. and
foreign crude oils and in fuel oils are also presented for comparison.
Analyses of most trace and minor elements for which typical oil values are
available appear to be consistent with the literature values. However,
several elements, notably Br, Cl, Cu, F, Fe, Ge, K, Pb, Rb, and V are some-
what lower than the cited literature values. The significance of these
concentration differences is not apparent due to the limited quantity of
published data. Comparison of SSMS data with typical oil analyses from the
Haynes plant (Table 3-8) indicates excellent agreement for Cu, Fe, K, Ni,
V, and Zn. However, Al, Ca, Na, and Mg were indicated to be major components
by SSMS although they are normally present at the ppm level. Pb was detected
at somewhat lower levels than normal for oil burned at this plant.
18
-------
TABLE 4-3. CONCENTRATION OF MAJOR TRACE ELEMENTS IN OIL
Element
Al
As
B
Ba
Be
Br
Ca
Ce
Cl
Co
Cr
Cs
Cu
F
Fe
Ga
Ge
Hg
K
La
ppm in
Fuel Oil
MC+
<0.01
0.5
0.5
<0.01
<0.01
MC+
<0.01
0.1
0.5
0.09
0.07
0.1
<0.01
2
0.08
<0.01
0.07**
3
0.01
Typical
Concentration,
ppmt
4
0.0006-1.1
0.4
1
0.08
0.1
14
0.006
12
2
0.002-0.02
0.09
3
0.1
0.003-14
0.4
0.2
0.02-30
34
No Data
Reference
2
1
2
2
2
2
2
2
2
2
1
2
2
2
1. 3
2
2
1
2
Element
Li
Mg
Mn
Mo
Ma
Ml
P
Pb
Pr
Rb
Sc
Se
Si
Sr
Th
Ti
U
V
Zn
ppm in
Fuel Oil
0.02
MC+
0.04
0.1
MC+
8
1
0.04
<0.01
<0.01
<0.01
0.02
4
0.09
<0.2
0.3
<0.2
1
0.2
Typical
Concentration,
ppmt
0.06
13
0.001-6
0.9
31
14-68
1
3
No Data
2
0.02
0.03-1
17
0.1
No Data
2
0.7
15-590
1
Reference
2
2
1
2
2
2, 4
2
2
2
2
1
2
2
2
2
2, 4
2
Composite sample analyzed by SSMS (Level 1).
References 1 and 3 provided ranges for U.S. and foreign crude oils. References 2 and 4 provided either
average values or ranges for residual oil.
MC indicates a major component for which SSMS did not provide a numerical value.
*
Mercury was analyzed by elemental sparging (Level 1).
-------
FLUE GAS EMISSIONS
Criteria Pollutants
Federal New Source Performance Standards (NSPS) currently in effect
define allowable emission rates of NOY (as N09), S00 and total particulates
A £ L.
from fossil fuel fired utility boilers having 25 MW or greater output.
More stringent limitations have been proposed by EPA for NOX, S02 and total
particulate emissions. Federal NSPS currently address neither CO nor total
hydrocarbon emissions. Existing NSPS and corresponding proposed emission
standards for oil-fired utility boilers are summarized in Table 4-4. It
should be noted that this plant is not required to meet NSPS; they are
provided for comparison only.
A total of 4 tests v/ere performed. Criteria pollutant emissions data
for these tests are summarized in Table 4-5 and compared with the EPA AP-42
emission factors for uncontrolled sources (5). In Table 4-6, average
emissions data are presented. The emissions data are discussed by specific
pollutant in the ensuing subsections.
Nitrogen Oxides—
NO emissions were monitored continuously by chemiluminescent instru-
A
mentation. The NO emission factor near full load condition was 116 ng/J,
A
which is 62£ lower than the average NO emission factor of 309 ng/J
A
tabulated in AP-42 (5). The lower NO emission factor was due to the use
A
of flue gas recirculation and off-stoichiometric firing for NO control.
A
Measured NO emissions are slightly below the NSPS limit of 130 ng/J for
A
oil-fired utility boilers.
Carbon Monoxide-
Average CO emissions were 6.6 ng/J. This is in reasonable agreement
with the AP-42 emission factor of 14.7 ng/J for oil-fired utility boilers,
considering the normal scatter in reported CO data.
Sulfur Dioxide—
S02 emissions were monitored continuously by pulsed fluorescent
analyzer for all tests. Additionally, S02 was determined in conjunction
with the Goksoyr-Ross Controlled Condensation System (CCS) for Test 143.
20
-------
TABLE 4-4. EXISTING AND PROPOSED FEDERAL EMISSION STANDARDS
FOR OIL-FIRED UTILITIES
Pollutant
NSPS
Proposed Standard
NOX (as N02)
SOo
Total
Participates
130 ng/J
(0.30 Ib/MM Btu)
344 ng/J
(0.80 Ib/MM Btu)
43 ng/J
(0.10 Ib/MM Btu)
130 ng/J (0.30 Ib/MM Btu)
520 ng/J (1.20 Ib/MM Btu)
max. with 85% reduction to
85 ng/J (0.20 Ib/MM Btu)
13 ng/J (0.03 Ib/MM Btu)
TABLE 4-5. COMPARISON OF AVERAGE CRITERIA POLLUTANT EMISSIONS WITH
EPA AP-42 EMISSION FACTORS FOR OIL-FIRED UTILITY BOILERS
Pollutant
*
NOX (as N02 near full load)
C0f
SO *
2
**
Total Organics
Total Parti culatestf
Emission
Test Data
116
6.6
98
0.42-0.58
7.5
Factor (nq/J)
AP-42
Emission Factor
309
14.7
84
2.94
14.2
NO was determined by continuous chemiluminescent analysis (Level 1).
t
CO was determined by continuous non-dispersive infrared analysis (Level 2),
S09 was determined by continuous pulsed fluorescence analysis (Level 2).
tt
Cl-Cie fractions were determined by gas chromatograph while the >C,g
fraction was determined gravimetrically (Level 1).
Total particulates v/ere determined by a modified Method 5 procedure
(Level 2).
21
-------
TABLE 4-6. SUMMARY OF CRITERIA POLLUTANT EMISSIONS
IV)
ro
Test No.
141
142
143
144
Average
Emission Factor (ng/J)
NO
(as N02)
114
91
117
98
105
CO
11.3
5.2
5.6
4.5
6.6
•MI^BH^HH^MMBMBHM
so2
105
95
90*
103
98
CTC6
Organlcs*
0.35-0.56
0.29-0.43
0.11-0.22
NDf
0.25-0.40
C7"C16
Organlcs
NDf
0.02
0.02
NDt
0.02
>C16
Organlcs
NDf
0.16
0.14
NDf
0.15
Total
Organlcs
NDf
0.47-0.61
0.27-0.38
NDt
0.37-0.50
Total
Parti culates
NDf
8.3
6.6
NDf
7.5
Upper limit values Include detection limits.
f ND - data not available.
* Average of continuous monitoring (105 ng/J) and CCS (75.6 ng/J) data for Test 143.
-------
Average S02 emissions were 98 ng/J for oil firing. This uncontrolled
emission factor is higher than the AP-42 emission factor of 84 ng/J for oil
firing but is well below the NSPS limit of 344 ng/J for oil-fired utility
boilers.
Total Organics—
In the determination of organic emissions, gas chromatographic analyses
were performed on grab bag samples of flue gas and catches from the Level 1
sampling (SASS train). Additionally, gravimetric analyses were performed
on Level 1 samples to quantify high molecular weight organics. Each bag
sample was collected over an interval of 30 to 45 minutes, with a single
sample being collected per test. These samples were utilized to measure
C, to Cg hydrocarbons. The SASS train collects approximately 30 cubic
meters of flue gas which are drawn isokinetically during the test. Samples
from the SASS train were analyzed to determine organics higher than Cg.
The C7 to C16 fraction was determined by gas chromatograph while organics
higher than C,g were determined gravimetrically.
Measured organics consisted primarily of the C-j-Cg fraction. Average
emissions of the C-,-Cg fraction were 0.25 to 0.40 ng/J while those for the
Cy-C-ic and higher molecular weight fractions were 0.02 ng/J and 0.15 ng/J,
respectively.
Average organic emissions were 0.4-0.5 ng/J, which is only 15% of the
reported AP-42 value of 2.94 ng/J for oil-fired utility boilers. The higher
"measured" organic value includes the detection limit concentrations for
fractions which were not detected and, as such, represents an upper limit.
Total Particulates--
Average emissions of total particulates were 7.5 ng/J. The measured
particulate emission factor is only about half the reported AP-42 value of
14.2 ng/J, probably due to the extremely low ash content (0.01%) of the
fuel oil burned. Measured emissions are well below the NSPS limit of 43
ng/J.
23
-------
Particulate Size Distribution
Due to the extremely light particulate loading, particulate size
distribution data are not available. However, data available from the
literature have indicated that generally 90 wt. % of emitted particulates
are less than 7 ym for oil-fired boilers (7).
In a recent draft document issued by the Health Effects Research
Laboratory (HERL) of EPA (8), it is stated that larger particulates (from
3 to 15 ym) deposited in the upper respiratory system (in the nasopharynx
and conducting airways) can also be associated with health problems. This
is in contrast to the past belief that particulates of health consequence
were those less than 3 ym size and deep-lung penetrable. The area of
concern now is particulates which are 15 ym and less, which have been
designated as "inhaled particulates" (IP). For oil firing, it can be
reasonably assumed that almost all the particulates emitted are 15 ym or
less.
Sulfur Compounds; SOo. SO^, and S0^~
Sulfur species were determined using several methods. SOp at the stack
was continuously monitored during all tests using a pulsed fluorescent
analyzer. During test 143, the CCS was also used to collect SC^ (from the
impinger), SO, (condensed as HgSO^), and S0^~ (by anion analysis of the
particulate catch). Sulfur speciation data are listed in Table 4-7. An
average of 97.7% of the output sulfur is emitted as SCL.
Parti cul ate sulfate represented 1.1% of sulfur emissions. Sulfate
emissions broken down into water- and acid-soluble fractions are presented
in Table 4-8. The bulk (>872») of the parti cul ate sul fates was present in
the water-soluble fraction.
Approximately 1.2% of the sulfur emitted was in the form of SOg. The
S03 emissions were lower than typical values reported in the literature (9),
probably because of the lower vanadium and nickel content of the fuel oil
burned, and because of the use of flue gas recirculation which reduces the
oxygen concentration and, therefore, reduces SO formation rate.
24
-------
TABLE 4-7. S02, S03, AND S04 EMISSIONS
Sulfur
Compound
S09
L.
S03
SV
Test No.
141
142
143
144
143
Average
143
143
Sarupl i ng
Method
Continuous
"
11
11
CCS
CCS
CCS
Stack
Gas
ng/J
105
95
105
103
75.6
98
1.14
1.27
Mole % of Total
Sulfur Species
in Flue Gas
97.7
1.2
1.1
Level 2 procedures v/ere utilized.
TABLE 4-8. SUMMARY OF SULFATE EMISSIONS
Test
No.
143
Sampling
Point
Stack
Water Soluble
Sul fates
ng/J % of Total
1.27 >87.0
Acid Soluble
Sul fates
ng/J % of Total
<0.19 <13
Total
ng/J
1.27-1.46
Level 2 procedures were utilized.
25
-------
Inorganics
Trace element concentrations in the flue gas were computed by assuming
that all trace elements present in the fuel oil are emitted in the stack.
Trace elements in the fuel oil were determined using spark source mass
spectrometry (SSMS).
Concentrations of 39 major trace elements present in the flue gas are
presented in Table 4-9. To assess the hazard potential of these emissions,
the emission concentrations are compared with the DMEG values. The DMEG
values are emission level goals developed under direction of EPA, and can
be considered as concentrations of pollutants in undiluted emission streams
that will not adversely affect those persons or ecological systems exposed
for short periods of time (10). The DMEG values tabulated represent air
concentrations which were derived from human health considerations based on
the most hazardous compound formed by the element in question. Only
chromium and nickel exceeded their DMEG values at the stack. Chromium and
nickel have low DMEG values due to considerations of potential human
carcinogenicity. Emission factors for the trace elements analyzed are
presented in Table 4-10.
Chloride and Fluoride Emissions
Specific anion analysis was performed on extracts from particulate
catches and iropinger solutions from the Goksoyr-Ross sampling train (Test
143). Emissions of Cl" and F" were 1.34 ng/J and 0.061 ng/J, respectively.
However, anticipated emissions based on SSMS analysis of a composite fuel
sample from Tests 141-144 are 0.002 ng C1~/J and 0.0002 ng F"/J. Whether
this discrepancy is the result of analytical problems or due to significant
variation in Cl~ and F" contents of the different fuel samples cannot be
conclusively determined from available data. Yet, ultimate fuel analyses
indicate little variation among the fuel samples. Also, it is known that
halogens are not determined well by SSMS. Fluorine is particularly difficult
to analyze by SSMS. On the other hand, specific ion electrode analyses are
generally accurate to within approximately 15%. Hence, it appears reason-
able to conclude that the observed discrepancy is primarily the result of
analytical problems associated with SSMS analyses of Cl" and F" in the fuel
oil.
26
-------
TABLE 4-9. EMISSION CONCENTRATIONS OF TRACE ELEMENTS
Element
AH
As
B
Ba
Be
Br
Ca*
Ce
Cl
Co
Cr
Cs
Cu
F
Fe
Ga
Ge
Hq**
K
La
Li
Mg+
Mn
Mo
Ha*
Ni
P
Pb
Pr
Rb
Sc
Se
Si
Sr
Th
Ti
U
V
Zn
Flue Gas
Concentration*
mg/m3
0.066
<0.0007
0.03
0.03
<0.0007
<0.0007
0.0086
<0.0007
0.007-H-
0.03
0.006
0.005
0.007
<0.0007tt
0.1
0.005
<0.0007
0.005
0.2
0.0007
0.001
0.37
0.003
0.007
2.0
0.5
0.07
0.003
<0.0007
<0.0007
<0.0007
0.001
0.3
0.006
0.01
0.02
<0.01
0.07
0.01
DMEG for Air
(Health Basis)
mg/m3
5.2
0.0020
3.1
0.50
0.0020
10
16
37
No Data
0.050
0.0010
82
0.20
2.5
1.0
5.0
0.56
0.050
2.0
no
0.022
6.0
5.0
5.0
53
0.015
0.10
0.15
No Data
120
53
0.20
10
3.0
No Data
6.0
0.009
0.50
4.0
Discharge
Seven' tyf
0.013
<0.3
0.01
0.06
<0.3
<0. 00007
0.0005
<0. 00002
— — _
0.6
6
0.00006
0.03
<0.0003
0.1
0.001
<0.2
0.1
0.1
0.000006
0.05
0.062
0.0006
0.001
0.038
30
0.7
0.02
___
<0. 000006
sO. 00001
0.005
0.03
0.002
— — «.
0.003
si
0.1
0.002
- Continued -
27
-------
TABLE 4-9. (Continued)
*
Estimates based on average trace element content of the fuel oil, as
analyzed by SSMS.
Discharge severity is defined as the ratio of the discharge concentration
to the DMEG value.
Estimates based on typical trace element content of the fuel oil reported
for this site. SSMS analyses performed on the fuel oil samples indicated
Al, Ca, Mg, and Na as major components without specific numerical values
being given.
Mercury was determined by elemental sparging (Level 1).
Specific ion analysis performed on the Goksoyr-Ross catch (test 143)
indicate that the chloride and fluoride concentrations may be as high as
4.7 and 0.2 ng/m3, respectively. This discrepancy is considered to result
primarily from analytical problems associated with SSMS analysis of these
halides.
28
-------
TABLE 4-10. EMISSION FACTORS FOR TRACE ELEMENTS
Element
Alt
As
B
Ba
Be
Br
Cat
Ce
Cl
Co
Cr
Cs
Cu
F
Fe
Ga
Ge
Ha
K
La
Emission Factor,
ng/J
0.023
<0.0002
0.01
0.01
<0.0002
<0.0002
0.0030
<0.0002 .
0.002 (1.34)*
0.01
0.002
0.002
0.002 .
<0.0002 (0.061)*
0.03
0.002
<0.0002
0.002
0.7
0.0002
Element
Li
Mqt
Mn
Mo
Hat
Ni
P
Pb
Pr
Rb
Sc
Se
Si
Sr
Th
Ti
U
V
Zn
Emission Factor,
ng/J
0.0003
0.13
0.001
0.002
0.70
0.2
0.02
0.02
<0.0002
<0.0002
sO.0002
0.0003
0.1
0.002
0.003
0.007
iO.003
0.02
0.003
Computed assuming that all trace elements in the fuel were emitted
through the stack. Fuel trace elements were determined by SSMS with
the exception of Hg which was determined by elemental sparging.
Emission factors for Al, Ca, Mg, and Na are based on typical fuel
concentrations of these elements for this site. SSMS analyses
indicated these elements as major components without specific
numerical values being given.
* Values in parentheses were obtained from specific ion analysis of the
Goksoyr-Ross catch from Test 143.
29
-------
Specific Organic Compounds
Selected samples were analyzed by combined gas chromatography/mass
spectrometry (GC/MS) for the identification of organic compounds present.
The organic compounds identified include aliphatic hydrocarbons, benzal-
dehyde, trimethyl cyclohexane-one, ^ substituted acetophenone, the methyl
esters of benzoic acid and substituted benzoic acid, diethylphthalate, and
3
ethylbenzaldehyde, at concentration levels between 0.02 and 2 yg/m .
Emissions of polycyclic organic matter (POM) determined by GC/MS are
summarized in Table 4-11. Naphthalene is the principal component of the
POM emissions. Benzopyrenes were detected at low levels but specific
isomers cannot be differentiated. Hence, it is not known whether benzo(a)-
pyrene was present. With the exception of the possible presence of
benzo(a)pyrene, all POM compounds from oil firing are at levels too low to
be of environmental concern.
LIQUID WASTE
There are no significant wastewater streams associated with the oil-
fired boiler tested.
SOLID WASTE
There are no significant solid wastes generated from the oil-fired
boiler tested.
30
-------
TABLE 4-11. POM EMISSIONS FROM OIL FIRING
Compound
Naphthalene
Phenanthridine
Dibenzothiophene*
Anthracene/
phenanthrene
Fluoranthene
Pyrene
Chrysene/
benz(a)anthracene
**
Benzopyrene and
perylenes
Tetramethyl - . .
phenanthrene
Total
Emission 3
Concentration, yg/m
Test 142 Test 143
7 3
0.3
0.6
1 0.2
1
1
0.1
0.04
0.6
11.0 3.8
DMEG
Value
vg/m^
50,000
No data
23,000
1,600
90,000
230,000
45
0.02
1,600
Discharge
Severity
Test 142 Test 143
0.0001 <0.
ND
<0.0001
0.0006 0.
<0.0001
<0.0001
0.0022
2
0.
0001
0001
--
--
--
0004
Level 2 procedures were utilized.
f Due to the low compound concentration, phenanthridene has not been
positively identified.
Due to the low compound concentration, dibenzothiophene has not been
positively identified. Also, the DMEG value for dibenzothiophene is
assumed to be the same as that for benzothiophene.
The DMEG value for benzo(a)pyrene is used in the computation of the
discharge severity.
DMEG value for tetramethyl phenanthrene is assumed to be the
same as that for phenanthrene.
31
-------
REFERENCES FOR SECTION 4
1. Magee, E.H., H.J. Hall, and G.M. Varga, Jr. Potential pollutants in
Fossil Fuels. Report prepared by ESSO Research and Engineering Co.
for EPA under contract No. 68-02-0629. June 1973.
2. Tyndall, M.F., F.D. Kodras, J.K. Pickett, R.A. Symonds, and W.C. Tu.
Environmental Assessment for Residual Oil Utilization - Second Annual
Report. Report prepared by Catalytic Inc. for EPA under contract No.
68-02-2155. EPA-600/7-78-175. September 1978.
3. Woodle, R.A. and W.B. Chandler, Jr. Mechanism of Occurrence of Metals
in Petroleum Distillates. Industrial and Engineering Chemistry 44:
2591, November 1952.
4. Bennett, R.L. and K.J. Knapp. Particulate Sulfur and Trace Metal
Emissions from Oil-fired Power Plants. Presented at AIChE meeting.
June 1977.
5. Compilation of Air Pollution Emission Factors, AP-42, Part A. Third
Edition. U.S. Environmental Protection Agency. August 1977.
6. Ctvrtnicek, T.E. and S.J. Rusek. Applicability of NOX Combustion
Modifications to Cyclone Boilers (Furnaces). Report prepared by
Monsanto Research Corp. for the U.S. Environmental Protection Agency.
EPA-600/7-17-006. January 1977. NTIS PB 263 960.
7. Fine Particulate Emission Inventory and Control Survey. Prepared by
Midwest Research Institute for the U.S. Environmental Protection Agency,
EPA-450/3-74-040. January 1974. NTIS PB 234 156.
8. Miller, S.S. Inhaled Particulates. Environmental Science and Tech-
nology 12 (13): 1353-1355. December 1978.
9. Homolya, J.B. and J.L. Cheney. An Assessment of Sulfuric Acid and
Sulfate Emissions from the Combustion of Fossil Fuels. In Workshop
Proceedings on Primary Sulfate Emissions from Corabustion~S~ources.
Volume 2 - Characterization. EPA-600/9-78-020b. August 1978.
10. Cleland, J.6. and G.L. Kingsbury. Multimedia Environmental Goals for
Environmental Assessment. Volumes 1 and 2. EPA-600/7-77-136a.
November 1977.
32
-------
SECTION 5
ENVIRONMENTAL IMPACT ASSESSMENT
This section presents an evaluation of impacts resulting from emissions
from oil combustion in utility boilers similar to the emissions observed at
the Haynes station. The evaluation is conducted in five parts. The first
part introduces background information pertinent to the development of the
environmental assessment, including a review of relevant studies, plant
emissions, and air quality forecasts. In the succeeding parts, the major
health, ecological, and economic impacts resulting from oil firing in con-
trolled utility boilers of the type tested are estimated. The final section
assesses the implications of the impacts for energy development by consi-
dering: 1) the additional controls which may be needed to mitigate the
expected damage levels, and 2) the potential effect of such control needs
on energy cost and energy resource development.
INTRODUCTION
Economic and environmental concerns over the nation's energy develop-
ment policies have precipitated several research efforts to evaluate the
consequences of all phases of energy development, from fuel production to
fuel end use. To organize the various efforts into a systematic, coordinated,
environmental assessment structure, the Environmental Protection Agency is
implementing a Conventional Combustion Environmental Assessment (CCEA)
Program. This program has been established for the purpose of integrating
together separate data generated by past and current studies into a complete
environmental assessment of conventional combustion processes. The integra-
tion procedure involves coordination and information exchange between EPA
related studies to: 1) determine the extent to which the total environmental,
economic, and energy impacts of conventional combustion process can be
assessed, 2) identify additional information needed for complete assessment,
3) define the requirements for modifications or additional developments of
control technology, and 4) define the requirements for modified or new
standards to regulate pollutant emissions. The CCEA Program coordinates
33
-------
and integrates current and future studies encompassing a wide spectrum of
environmental assessment areas and conventional combustion processes.
Integration of these studies, including the present effort, will provide
the basis for energy policies which result in the expanded use of conven-
tional combustion processes at reasonable environmental, economic, and
energy costs.
AIR QUALITY
Model Plant Emissions
Air quality impacts of oil firing in utility boilers were estimated
based on a hypothetical model plant. The model plant was characterized
using emission factors derived from the Haynes plant test data and assumed
meteorological parameters. The model plant was assumed to have the same
fuel and boiler characteristics as the Haynes station. The criteria pollu-
tant emission rates utilized are shown in Table 5-1. Comparison of the
measured trace element emission concentrations with DMEG values revealed
that the flue gas contained only 2 elements which exceed their DMEG values
at the stack, Cr and Ni. Hence, only these trace elements were considered
in the analysis.
TABLE 5-1. EMISSION RATES FROM A CONTROLLED 353 MW
(GROSS) OIL-FIRED UTILITY BOILER
Pollutant Emissions, gm/sec
NO 95.2
CO 5.4
S02 80
Total Organics 0.34 - 0.4
Total Particulates 6.2
Cr* 0.002
Ni* 0.2
Trace element concentration in the flue gas (based upon fuel analyses)
exceeds DMEG value.
34
-------
Annual Emissions
Estimated annual emissions for oil-fired plants generating 353 MW
(gross) are presented in Table 5-2. These estimates are based on the
emission factors determined for the Haynes No. 5 boiler during oil firing.
For annual emission computations, the plant was assumed to operate at 93%
of its maximum load with 40% overall efficiency, for 7008 hours/year (80%
of the year). These assumptions are based upon measurements made during
the test period and operability data provided by Haynes personnel.
Impact on Air Quality
The duration of exposure is important in determining effects of changing
air quality. The highest concentrations occur for short periods (usually
less than one hour) under meteorological conditions causing plume trapping.
The stack emissions are trapped under an inversion layer, with the plume
spreading downward. The frequency of occurrence and the severity of plume
trapping conditions varies depending on the site. As a conservative worst
case estimate in this study, plume trapping conditions were assumed to
persist for periods as long as three hours.
TABLE 5-2. ANNUAL EMISSIONS*
Pollutant
NOV
x
so2
SO,
3
so4"
CO
Total Organics
f r
1 6
C7"C16
>C16
Total Parti culates
kg/yr
2.40 x 106
2.0 x 106
2.36 x 104
2.63 x 104
c
1.4 x 10s
7.7 x 103 - 10 x 103
5.2 x 103 - 8.3 x 103
y
4 x NT
3.1 x 103
5
1.5 x 10°
-fired plants generating 353 MW operating 7008 hours/year.
35
-------
Typical 24 hour maximum concentrations were estimated assuming Gaussian
steady state plume dispersion under conditions of low wind speed and stable
atmosphere. Typical 24 hour levels were translated to annual expected con-
centrations by applying ratios for the one day maximum and annual mean as
empirically derived from the Continuous Air Monitoring Project (1, 2, 3, 4).
The effective stack height was estimated based on assumed meteorological
conditions, and the actual stack height of the Haynes unit.
Maximum predicted levels for criteria pollutants in the vicinity of
the model plant are presented in Table 5-3. Ambient concentrations resulting
from oil firing are in conformance with all tabulated air quality standards.
The short term maximum concentrations present the most significant air
pollution problem. For any of the pollutants, it should be noted that the
short term maximum concentrations generally occur infrequently, depending
on site meteorology, and are usually of very brief duration (about 1 hour or
less). The maximum concentration levels are localized within a distance of
about one-half to four miles from the boiler stack. These concentrations
diminish to about one-half the peak level another one to eight miles further
downwind. Concentrations of CO and total organics are seen to be in-
significant with respect to short term NAAQS. Hence, these compounds will
not be considered further.
Federal standards limiting deterioration of air quality are generally
more restrictive than the NAAQS. Included in Table 5-3 is a list of the
allowable increments of deterioration for the three classes of growth and
development areas. Allowable emissions may depend primarily on the existing
air quality and the allowable deterioration increment. Consequently, siting
of the plants would be a major consideration in their environmental accept-
ability, since areas which already experience marginally acceptable air
quality may not tolerate the increases projected to occur.
HEALTH IMPACT
The health effects of exposure to high concentrations of the various
pollutants are well known and have been tabulated throughout the literature
(5). However, the specific extent to which health is affected by ambient
pollutant exposure levels (dose-response relationships) is unclear. Moreover,
36
-------
TABLE 5-3. COMPARISON OF FEDERAL AIR QUALITY STANDARDS
WITH AIR QUALITY PREDICTED TO RESULT FROM OIL
COMBUSTION IN A 353 MW (GROSS) UTILITY BOILER
3
Concentration, yg/m
Pollutant Model
Plant NAAQS
PSD
Class
I
**
Increments
Class Class
II III
Annual Mean
HOX
CO
SOo
2
Total Organlcs
Total Particulates
24 Hour1"
NOX
CO
so2
Total Organics
Total Particulates
1-3 Hour*
0.1
2
0.01
0.1
8
0.4
6
0.04
0.5
100
80
75
20
19
40
37
tt
365
260
91 182
10
37
75
NOV
x
CO
so2
Total Organics
Total Particulates
260
15
230
1
18
___
40,000tf
1,300
160
« _ _
___ ___ ___
— — —
25 512 700
— — —
__ _ ___ ___
The expected annual average levels were estimated based on the conser-
vative end of the range of typical ratios for 24 hour maximum to annual
as reported in the Air Quality Criteria Documents (1, 2, 3, 4).
Based on typical meteorological conditions for 24 hour period.
Based on worst case meteorological conditions (plume trapping).
**
Prevention of significant deterioration standards (PSD).
ft The NAAQS for CO are 40,000 yg/m3 for a 1 hour period and 10,000 yg/m
for an 8 hour period.
37
-------
it is unclear how pollutant specific dose-response curves may be related
to the overall health effects of the gas-aerosol complex associated with
fossil fuel combustion products.
Most attempts to establish dose-response functions for ambient pollu-
tion levels involve the formulation of some indicator which is then assumed
to represent the entire spectrum of primary and secondary pollutants present.
The indicator (usually sulfur dioxide, total particulates, or sulfates) is
then related to mortality or morbidity data for various areas by various
statistical approaches designed to factor out effects of other variables
(e.g., population age, climatology, etc.). Dose-response curves derived
from these studies are then employed to estimate health effects of air
quality changes resulting from proposed projects.
Recently, the health effects model by Lundy and Grahn (6) has been
developed for application in the National Coal Utilization Assessment Studies
being conducted at Argonne National Laboratories. The model combines
mortality functions for suspended sulfates as developed by Finch and Morris
(7) and age-dependent and established response curves for cigarette smoke.
The mortality dose-response functions for suspended sulfates are based on
statistical studies of various populations experiencing different sulfate
exposures. Unlike the dose-response air pollution studies, investigations
of smokers have been relatively well controlled with respect to age, degree
of exposure, and effect. Thus, to expand the predictability of the sulfate
dose-response curves to populations of different age distribution (e.g.,
future populations), the cigarette response curves are adjusted to fit the
observed mortality/sulfate data, resulting in a model which predicts age-
specific death rates. This elaboration is important because death rates
vary exponentially with age, and shifts in the age distribution of a
population will result in substantial shifts in total mortality. According-
ly, the Lundy-Grahn Model utilizes projections of the population age
distribution to estimate the age-specific and total death rates due to air
pollution at any specific time in the future. The basic relationship of
the model is:
bX
B(X' XO) =
38
-------
where B is the number of excess deaths per year for the population of age
•5
X which was exposed to the sulfate concentration S (in yg/m) since age Xo.
The constants a,b,c and d are coefficients to fit the model to cigarette
smoking mortality data and response data for a specific population subgroup
exposed to air pollution.
The Lundy-Grahn Model is being used in the ongoing National Coal Utili-
zation Assessment Program to estimate excess mortality resulting from
increased coal utilization. Air diffusion modeling was conducted first to
predict a population-weighted exposure increase for suspended sulfates. The
Lagrangian Statistical Trajectory Model of Argonne National Laboratory (8),
which assumes a constant transformation of S02 to sulfate, is employed in
the estimation procedure. This technique has been applied to oil firing;
based on the predicted exposure increase and projections of the population
age distribution, excess death rates are calculated for each age and summed
to yield the expected mortality associated with oil combustion. Figure 5-1
presents the adjusted projections for an oil firing scenario through the
year 2020. The figure indicates that the expected health effects caused by
air pollution (as indexed by suspended sulfates) from oil-firing of con-
trolled utility boilers are minimal. The maximum impact is expected to
occur in the year 2000, when the proportion of population in the highest
risk age groups will be greatest. For each million persons, the expected
increase in death rate when oil firing of utility boilers is prevalent is
49 persons per million.
Health effects caused by sulfate levels may also be expressed in terms
of morbidity. Table 5-4 presents data for increases in incidents of health
disorders due to ambient sulfate exposures. In those areas which already
experience high sulfate levels, respiratory disease may increase signifi-
cantly with increases of suspended sulfates due to increased fuel consumption,
3
For example, in areas where the threshold level 10 yg/m is exceeded regu-
larly, the contribution of 2.4 yg/m of sulfate concentration associated
with controlled oil-fired boilers would be estimated to produce a 32%
increase in the incidence of chronic respiratory disease caused at the
threshold level.
39
-------
oo;
<
• LU
O >-
fc"*
f-o
3S
«=C LU
ii
LU
CO
-------
TABLE 5-4. HEALTH IMPACTS OF SULFATE AEROSOL
Pollute nt and
Health Effect
Si'1 fates
TortfTity
Aggravation of
Heart and Lung
Disease in Elderly
Aggravation of
Asthnia
Lower Respiratory
DiS2P.se in Children
Chronic Respiratory
Disease
Nonsisokers
Smokers
Population at Risk -
Total Population •
Same as above for
oxidants function
Sane as cbove for
oxidants function
Sane as above for
nitrogen dioxide
function
62 percent of
population ags 21
or older
38 percent of
population age 21
or o]dsr
Assumed Baseline
Frequency of
Disorder within
Population at Risk
Dally death rate of
2.58 per 100, DOO
Same
Same
Sams
Two percent
prevalence
Ten percent
prevalence
PolTutcnt
Concentration
Threshold
For Effect
25 iig/n3 for
one day or
more
9 yg/rc3 fcr
ons day or
rare
6 yjAn3 for*
one" day or
mere
13 ug/m3 for
several years
10 va/m3 for
several years
15 gg/m3 for
several years
>
Effect Increase a> ;
of Bsseline Pcr
Pc'Ui^art 'JrcU Abnv.-.
Tt-irc^^o^c1
2.5S por 10 ug/r.3
74. 1 2 par 70 pg/n3
33.5- per 10 vg/n3
75.95 psr 10 vg/^3
13« per 10 pc/ns
73. Si pr>r 10 vg/n3
Reference 9.
-------
In addition to potential health effects created by long range sulfate
levels from utility boilers, high concentrations of pollutants in the pro-
ximity of the power plant pose a potentially serious health problem. The
Lundy-Grahn model may also be applied to estimate mortality effects caused
by ambient levels of SCL and total suspended particulates. The model gives
the following relationships when fitted to Lave and Seskin dose-response
data (6) for S02 and total suspended particulate (TSP):
.823e-'064X
per 10 males:
100e
"'2(X ' Xo)
(.835 TSP + .715 S02)
(• nccQ-088X
per 10b females: '-^^ (.835 TSP + .715 S02)
1 + 100e"'2(X " Xo)
If the model is applied for average concentrations expected to occur in the
vicinity of a power plant (Table 5-3), the expected increase in mortality
is appreciable. Figure 5-2 illustrates the estimated impact on mortality.
When boilers are fired with oil, the increased death rate is about 19 male
and 9 female deaths per million persons per year, at age 50.
o
a:
• «C
O Lul
i_- >-
a**^*
UJ ~j
=50
£X CO
a:
50-1-
40-
30-
ui z
oo
»—I
5J 20- •
i
LU:
CO '
CO
cc
ID-
Male response
Female response
10
20
30 40 50 60
POPULATION AGE
Figure 5-2. Increase in Mortality Rates in Vicinity
of Oil-fired Utility Boilers as a Result
of S00 and Total Particulate Emissions.
42
-------
Effect of Trace Elements--
Trace elements from combustion emissions enter the atmosphere and are
then dispersed to the upper atmosphere or deposited in the environment
around the sources. The principal routes of entry to man are by inhalation,
drinking water, and food.
Table 5-5 summarizes estimates of the annual average atmospheric con-
centrations of Cr and Ni expected in the vicinity of a single oil-fired
utility boiler of 353 MW gross capacity. These elements were examined
because their stack concentrations exceeded their respective DMEG values.
Also included in Table 5-5 is a listing of concentrations considered accept-
able for continuous ambient exposure. The allowable concentrations are
based on proposed regulations for control of air pollution from hazardous
waste management facilities, as required by Section 3004 of the Resource
Conservation and Recovery Act. It is clear that the air concentrations of
trace elements resulting from operation of the utility boiler are several
orders of magnitude below either the allowable exposure level or typical
urban air concentrations.
TABLE 5-5. EXPECTED TRACE ELEMENT CONCENTRATIONS IN VICINITY
OF A 353 MW (GROSS) OIL-FIRED UTILITY BOILER
Annual Ambient
Element Concentration
vg/m3
Cr 0.00003
Ni 0.004
Typical
Urban Air
Concentration
vg/m3
.010
1.40
Allowable
Exposure
Levelt
yg/m^
50
100
Based on data reported in References 10, 11, and 12.
Based on ambient air objectives proposed for hazardous waste
management facilities (13).
43
-------
A primary concern in emissions of trace elements is the contribution
of these elements to body burden due to exposure to water and food. To
estimate this contribution, pollutant deposition rates are approximated by
the product of the ambient concentrations and the deposition velocity of
the pollutant. The deposition rate is dependent on particle size. As dis-
cussed previously particles emitted from an oil-fired boiler are predomi-
nantly less than 7 ym in diameter. Available data indicate that the median
particle size is in the 1 ym to 3 ym range. The deposition velocity of
particles this size over grass surfaces is approximately 0.1 to 0.2 cm/sec
(14). Accordingly, the deposition rates of the various trace elements were
approximated and are shown in Table 5-6.
The significance of the deposition rates is evaluated by considering
the associated effect on drinking water and diet. The pathway to drinking
water is by run-off of soil particles containing deposits of trace elements,
and the pathway to the diet is by plant uptake from trace elements in the
soil. In either pathway, the incremental concentration of elements in the
soil determines the extent of the potential impact. Table 5-7 summarizes
the maximum predicted soil concentration in the .vicinity of the oil-fired
model plant. The concentrations are estimated by assuming mixing of the
deposited elements to a depth of 10 cm, and over a period of 40 years. For
these trace elements, only minor increases over the background soil levels
would be expected. The significance of elevated soil concentrations is
evaluated by considering the associated increase in trace element concentra-
tion in plant tissues and drinking water.
The concentration of elements in plant tissues is related to the bio-
logically available fraction of the elements in the soil. This is often
expressed as the soluble concentration in the soil, and is some fraction of
the total concentration reported in Table 5-7. Plants possess the ability
to concentrate elements from dilute soil solutions. This ability is depen-
dent on the concentration of elements in the soil, and usually increases with
decreasing soil concentrations. The ratio of concentration of elements in
plants to the concentration in the soil is known as the concentration ratio.
Table 5-8 lists average plant concentration ratios for various elements.
The data are based on various published data as compiled in a study by
44
-------
TABLE 5-6. ANNUAL DEPOSITION OF TRACE ELEMENTS IN VICINITY
OF CONTROLLED OIL-FIRED POWER PLANTS
Element
Annual Deposition Rate ,
g/m2-yr.
Cr
Ni
1.9 x 10
2.5 x 10
-6
-4
Calculated by assuming a particulate deposition velocity
of 0.2 cm/sec. The deposition velocity is multiplied by
the annual average concentration to estimate the total
deposition rate. The deposition rate is calculated for the
location where the maximum average annual concentration
occurs.
TABLE 5-7. LONG TERM EFFECT OF CONTROLLED OIL-FIRED UTILITY BOILER
EMISSIONS ON SOIL CONCENTRATIONS OF TRACE ELEMENTS
Increased Soil
Element Concentration
After 40 Years*,
mg/kg
Typical
Soil
Concentration'5'
mg/kg
Increase Over
Average Soil
Concentrations,
Cr
Ni
0.001
0.07
40
40
0.003
0.2
Based on deposition rate (Table 5-6), an assumed mixing depth of
10 cm and soil density of 1.5 gm/cm3.
Based on data compiled in Reference 15.
45
-------
TABLE 5-8. LONG TERM EFFECT OF CONTROLLED OIL-FIRED BOILER
EMISSIONS ON CONCENTRATIONS OF ELEMENTS IN PLANTS
Concentration Solubility* Typical Increase in
Element Ratios* of Elements Concentration Concentration
01 in Plants,* of Plants,t
rig/kg rng/kg
10
Cr
N1
250
331
0.004
0.1
.23 0.00001
3 0.02
Extracted from Reference 15.
f Calculated by multiplying concentration ratio by the incremental increase
in soil concentration (Table 5-7) by the fraction of the element which is
soluble.
Battelle (15). The effect of increased trace element soil loadings (caused
by 40 years of boiler emissions) on concentration of the elements in plants
is then estimated by assuming that the soluble portion of the loadings is
available for plant takeup. The estimates reveal that oil firing produces
less than a 1% increase in concentrations of chromium and nickel in plants.
The actual impact of trace element emissions on plant burden depends greatly
on many site-specific variables, such as temperature, precipitation, soil
type, water chemistry, and plant species at a given site.
Trace elements also enter the plant via foliar absorption. Intake
from the leaf surface to the interior occurs through stomatal openings,
walls of epidemal cells, and leaf hairs. Although relatively little is
known regarding the efficiency of foliar intake, it would appear that the
plant burden produced by soils containing long term deposits is several
orders of magnitude greater than that which could be transferred from foliar
interception of trace elements in the atmosphere. Soil concentrations are
the result of accumulation of elements over the long-term, and crops raised
in these soils tend to concentrate the trace elements in the plant tissue.
46
-------
By contrast, the foliar intake rate can be no greater than the deposition
rate on the plant surface, and there is much uncertainty regarding the
efficiency of the plant in absorbing the deposited particles. Thus, it is
clear that the soil uptake scenario (Table 5-8) represents the more adverse
case for plant uptake of trace elements. This scenario assumes no inter-
ference (e.g., animal or crop uptake) with trace element buildup in soils
over a 40 year period, and a fixed concentration of elements in the soil
despite crop uptake.
Trace elements emissions could also affect the quality of drinking
water. The impact of trace element particle deposition on runoff water
concentration will be related to the relative increase in soil concentration
due to long term atmospheric deposition of elements. The actual runoff con-
centrations may be estimated by applying average sediment burden rates for
representative runoff per unit of watershed area. The sediment is assumed
to carry the cumulative deposits of metals originating from the boiler
emissions. Table 5-9 summarizes estimates of increased soluble metals con-
centrations for runoff waters in the vicinity of the model plant. Runoff
water in this vicinity contains trace elements at levels from six to nine
orders of magnitude less than the potable water standard.
IMPACT ON ECOLOGY
The ecological environment will be affected by air emissions and by
solid waste residuals generated by air pollution control equipment.
Effect of Air Emissions
A major ecological impact category most likely to be affected by
utility boiler emissions is plant life. Of the major gaseous pollutants
emitted by fossil fuel combustion, plant life is most affected by SOg and
NO in the concentration ranges expected. Concentrations of CO and hydro-
A
carbons produced by oil firing of utility boilers would be expected to cause
negligible impact on vegetation (4, 16). The maximum levels of NOX and SOg
expected to occur in the vicinity of utility boilers may exceed the
threshold injury values for these pollutants. Sensitive plants in the
vicinity of the utility boiler could suffer injury, although such injury
would be limited to a downwind sector a few miles from the plant.
47
-------
00
TABLE 5-9. TRACE ELEMENT CONCENTRATION IN RUNOFF WATER IN VICINITY
OF CONTROLLED OIL-FIRED UTILITY BOILER
Element
Cr
Ni
Typical
Background
Concentration
of Soluble
Metals In
Runoff Water*
mg/1
1 x 10"5
1 x 10"4
Increase in
Soluble Metals
Concentration
in Soil After
40 Yearst
mg/kg
4 x 10"8
7 x 10"5
Increase in
Soluble Metals
Concentration
In Runoff Water*
After 40 Years
mg/1
4 x 10"11
7 x 10"8
EPA Proposed
Maximum
Acceptable
Concentration
for Livestock
mg/1
1
—
Standard
As Critical
Concentration
in Potable
Water
mg/1
2 x 10"2
5 x 10"2
Based on average soil parti culate runoff rate of 1000 mg/1 of runoff water, and soluble endogenous
concentration of metals in soils (15).
f Based on increase in trace element concentration (Table 5-7) and solubility of elements (Table 5-8)
* Based on average soil particle runoff rate of 1000 mg/1 of runoff water, and increased soluble
metals concentration in soil after 40 years.
-------
The secondary pollutants (ozone and peroxyacytylnitrates) formed by
reaction of hydrocarbons and nitrogen oxides are considerably more toxic
than either of the precursors alone. The formation of secondary compounds
in boiler stack plumes and the impact of the boiler nitrogen oxides emis-
sions on urban photochemical smog depend on complex relationships which
are not yet totally understood. Therefore, it is not possible to reliably
estimate the effect of NOV emissions levels on levels of photochemical com-
A
pounds. However, based on typical regional emissions figures, it appears
that emissions from power plant fuel combustion provide a significant source
of the regional emissions of NO necessary for photochemical smog. Approxi-
A
mately 28% of the nation's NOX emissions are produced by combustion in power
plants (17).
If NOV emissions from utility boilers are a significant contributor to
A
photochemical smog, then there is valid concern that boiler emissions may
contribute to plant injury. The effects of photochemical air pollution on
plant life have been observed frequently at various different severities
throughout the United States. In addition, the effect of the major consti-
tuents of photochemical smog (products of nitrogen oxides and organic com-
pounds) on plants has been investigated separately. The pigmentation of
small areas of palisade cells is characteristic of ozone injury, and a
bronzing of the undersurface of leaves is typical for peroxyacytylnitrate
injury. Table 5-10 illustrates the relatively low levels of ozone which
will produce significant plant injury to crops. The concentrations shown
are typical of many areas experiencing photochemical air pollution, and
suggest the necessity for concern over sources emitting high levels of NOX>
Nitrogen oxides may also cause injury to vegetation by direct contact.
The significant oxides of nitrogen are NO and NO . The major oxide in com-
A
bustion emissions is NO. However, after residence in the atmosphere, NO is
converted to NO,, by photolysis and by photochemical interaction with hydro-
carbons. The effect of NOp on plant life has been studied under controlled
laboratory conditions. Acute injury is characterized by collapse of cells
and subsequent development of necrotic patterns. Chronic injury, caused by
exposure to low concentrations over long periods, is characterized by
chlorotic or other pigmented patterns in leaf tissue. Such injury results
49
-------
TABLE 5-10. PROJECTED OZONE CONCENTRATIONS WHICH WILL PRODUCE, FOR
SHORT TERM EXPOSURES, 20 PERCENT INJURY TO ECONOMICALLY
IMPORTANT VEGETATION GROWN UNDER SENSITIVE CONDITIONS*
Concentrations
Time, Hr
0.2
0.5
1.0
2.0
4.0
8.0
producing injury
Sensitive
0.40-0.90
0.20-0.40
0.15-0.30
0.10-0.25
0.07-0.20
0.05-0.15
in three types
Intermediate
0.80-1.10
0.35-0.70
0.25-0.55
0.20-0.45
0.15-0.40
0.10-0.35
of plants, ppm
Resistant
1.00 and up
0.60 and up
0.50 and up
0.40 and up
0.35 and up
0.30 and up
*
Reference 18.
in reduction of growth and reproduction. Only limited data are available
to characterize the effect of NO on plants. Generally, it appears that NO
leads to effects somewhat similar to those observed for N02, but at slightly
higher threshold concentrations. Therefore, for worst case evaluations of
the impact of ambient NO levels, it is assumed that NOV exists as NO,, and
A X t
that the NOX levels are not depleted by the photochemical reactions which
typically occur in urban areas.
Figure 5-3 illustrates the threshold concentrations at which various
degrees of damage result from exposure to NOg. As the long term concentra-
tion of NOX in the vicinity of the model plant is estimated at 2 yg/m3,
injury to plants from oil firing is not likely to occur. Even the maximum
short term ambient concentration of NOV near the oil-fired boiler, which is
3
estimated to be 260 yg/m , is below the threshold levels which induce plant
injury.
50
-------
0.01
0.1
„ !
DAYS
1.0
10
f
100
1030-j.
CL.
CL
CV
o
U-
c
o
I—•<
H-
8
100
10-
o.i
•: -1000
IH:ATH
1
100
THRESHOLD FOR FOLIAR LESIONS
METABOLIC AND GHOWTl-i PFFECTS
ro
cv;
O
•10 1'
•1.0
10,000
0.1 i!c 10 100 1000
DURATION OF EXPOSURE (HOURS)
Figure 5-3. NOg Threshold Concentrations for Various
Degrees of Plant Injury (19).
Acute short term injury to vegetation by SOg exposure is characterized
by damaged leaf areas which first appear as water soaked spots, and later
appear as bleached white areas or darkened reddish areas. Chronic S02
injury is usually characterized by chlorosis (yellowing) which develops from
lower concentrations over extended periods of time. Either acute or chronic
SOg injury may result in death or reduced yield of the plant if the extent
of the damaged tissue exceeds 5 to 30 percent of the total amount of foliage.
51
-------
The impact of the expected SOg concentrations varies with the plant
species. Threshold injury in sensitive plants may be caused by short-term
o
S00 levels as low as 30 ug/m (20). Table 5-11 summarizes the broad cate-
gories of sensitivity for different plants. Grain, vegetable, pasture, and
forage crops are susceptible to SOg damage for most of the growing season.
These crops may suffer yield reductions in areas where power plants such as
that of the present study are located, although the damage v/ould be relati-
vely localized. Data presented in Figure 5-4 indicate that the peak short
3
term S02 concentration of 230 yg/m near the oil-fired boiler may exceed the
injury threshold of sensitive plants, although the damage would be slight.
It should be noted that the plant damage thresholds illustrated by
Figure 5-4 apply to conditions of temperature, humidity, soil moisture,
light intensity, nutrient supply, and plant age which cause maximum sus-
ceptibility to injury. The occurrence of such conditions are rare. In
fact, in the unlikely event that all such conditions are met, the dose-
response curves indicate that plant injury could occur without a violation
of the federal air quality standard for the 3 hour or 24 hour concentration
of SOp. Additional susceptibility may also result from synergistic effects
of sulfur dioxide and other pollutants. Particularly relevant to the urban
environment are combinations of sulfur dioxide and ozone. Moderate to
severe injury of tobacco plants have been observed for four hour exposures
q
to concentrations of 0.1 ppm (262 ug/m ) SOg in combination with 0.03 ppm
ozone. Because high ozone levels are a frequent problem in the vicinity of
urban areas, susceptibility to plant injury by S02 pollution is greater
when utility boilers are also sited in urban areas. One of the major con-
cerns associated with fossil fuel utilization is acid precipitation resulting
from wet deposition of suspended sulfur and nitrate compounds. Data show
that there has been an intensification of acidity in the northeastern region
of the U.S. since the mid 1950's. Precipitation in a large portion of the
eastern U.S. averages between pH 4.0 and 4.2 annually. Values between pH
2.1 and 3.6 have been measured for individual storms at distances several
hundred miles downwind of urban centers. The areas experiencing highest
acidity are typically downwind of the areas where sulfur emissions are
highest (19, 22).
52
-------
TABLE 5-11. SENSITIVITY OF COMMON PLANTS TO S02 INJURY
Vegetation
Sensitive intoiT*cliatt Resistant
'.:-jiic pin--1 Kaple ' Sufjar ;njjjle
r.oldfci'irod Virginia irccpor Phlox
f.nttOri.o.';fi V.'hito 03r Gok
Viiv.ir.ia 'cri-oper F.lm Mdplc
,'••;«. or Short loaf pine Shrub!:/ willow
n.jssrlitrry '.stcr
I}::- Linden
v;ild §rcpfi
A:-sric«'i eln
Wnito Ash
Virijinij pine -•
Tulip tree
Cro;>s
Str.si'.ive Inten-Pi!iatc
Alfalfa Irish Potato
Borloy Clover
Oils Sweet clover
Rye
Wi.c?.t
Siveei; potato
Soybcaii
Sweet clover
Cotton Tobacco
Clover
1
Resistant
Corn
.Sor.;l.j7!
Reference 21.
SO, DOSE-INJURY CURVES
FOR SENSITIVE PLANT SPECIES
DAMAGE LIKELY
INJURY OR DAMAGE
POS?!c'.LE
(THKESIIOL!) RANGE)
DURATION OF EXPOSURE, hi
Figure 5-4. SOg Dose-Injury Curves for Sensitive
Plant Species (20).
53
-------
Acid rain affects plant life in varying degrees depending on the pH
and the type of plant species. Experiments show that the effects on plants
may include reduction in growth or yield, leaf damage, death, and chlorosis.
Acid rain also has been shown to affect aquatic organisms, and it is be-
lieved that thousands of lakes are now experiencing reductions in fish
population due to acidification between pH 5.0 and 6.0 (19). The level of
3
sulfates estimated to result from oil firing is about 2.4 yg/m , a level
not expected to result in significant acid precipitation. Based on tests
of the utility boiler of this study, it appears that emissions from oil
firing are not apt to cause adverse plant burdens of either chromium or
nickel.
ECONOMIC IMPACT
The direct economic impacts associated with residuals of fuel combus-
tion involve the costs of damages (or benefits) sustained when the residuals
enter the environment. Second order economic impacts associated with the
residuals involve the alterations that occur in employment, the tax base,
energy prices, income, and land values due to the damages (or benefits)
resulting from combustion residuals. The quantification of direct economic
impacts involves the difficult task of ascribing economic values to environ-
mental changes. Quantification of second order economic effects are yet
more difficult because of gaps in knowledge which make it impossible to
determine the complex relationships between cost and the numerous socio-
economic factors involved.
A number of ongoing energy related studies are attempting to develop
sophisticated economic models which will predict the cost of environmental
damages (6, 21, 23). The models address the cost of visibility reduction,
health effects (morbidity and mortality), and certain second order effects.
Utilization of the models requires substantial input data involving regional
demography and emission source distributions. The models require further
refinement and are currently under continuing development. The data base
or scope of the present program did not permit the adaption and utilization
of such models.
54
-------
The extent of the economic impacts resulting from residuals of 353 MW
oil-fired utility boilers is proportional to the extent of the environmental
damages which occur. The analyses have shown that while some impact of
emissions from the oil-fired boiler tested in this study may occur, federal
ambient air quality standards for sulfur oxides and nitrogen oxides will
probably not be violated in the vicinity of the model plant. However, in
spite of conformance with air quality standards, the economic cost of plant
emissions in the affected areas may be significant. These costs include
medical expenses, loss of productivity, cost of cleanup and maintenance for
soiling damages, and reduced crop revenues.
Whatever the extent to which additional controls may be required for
oil-fired boilers, the cost of such controls will probably be relatively
minor compared to the overall operating cost of a boiler and other factors
affecting the overall costs. Even when predicted pollutant loadings meet
environmental standards, it is not entirely clear whether the increasing use
of fossil fuels may be continued at the forecasted levels of control tech-
nology without potential long term environmental damages. If it is found
that long term effects of pollution (e.g., trace metals accumulation, lake
acidity, land use) are unacceptable, then more stringent environmental
regulations can be expected, and it is clear that energy cost will increase
with increasing control requirements.
55
-------
REFERENCES FOR SECTION 5
1. U.S. Department of Health, Education, and Welfare. Air Quality Criteria
for Sulfur Oxides. AP-50. March 1967.
2. U.S. Department of Health, Education, and Welfare. Air Quality Criteria
for Nitrogen Oxides. January 1971.
3. U.S. Department of Health, Education, and Welfare. Air Quality Criteria
for Particulate Matter. January 1969.
4. U.S. Department of Health, Education, and Welfare. Air Quality Criteria
for Carbon Monoxide. March 1970.
5. Waldbott, G. Health Effects of Environmental Pollutants. 1973.
6. Lundy, R.T. and D. Grahn, Argonne National Laboratory. Predictions of
the Effects of Energy Production on Human Health. Paper presented at
the Joint Statistical Meetings of the American Statistical Association
Biometric Society, Chicago, Illinois. August 1977.
7. Finch, S. and S. Morris, Brookhaven National Laboratory. Consistency
of Reported Health Effects of Air Pollution. BNL-21808.
8. Sheih, C. Application of a Langrangian Statistical Trajectory Model to
the Simulation of Sulfur Pollution over North Eastern United States.
Preprints of Third Symposium on Atmospheric Turbulence, Diffusion, and
Air Quality. 1976.
9. Nelson, W., J. Knelson, V. Hasselblab, Health Effects Research Labora-
tory of Environmental Protection Agency. Air Pollutant Health Effects
Estimation Model. EPA Conference on Environmental Modeling and Simula-
tion, Cincinnati. April 1976.
10. Effects of Trace Contaminants from Coal Combustion. Proceedings of a
Workshop Sponsored by Division of Biomedical and Environmental Research
and Development Administration, August 1976, Knoxville, Tennessee.
11. Sullivan, R.J. Litton Systems, Inc. Air Pollution Aspects of Iron and
its Compounds. U.S. Department of Commerce/National Bureau of Standards,
September 1969.
12. Y.C., Athanassiadis, Litton Systems, Inc. Air Pollution Aspects of
Zinc and its Compounds. U.S. Department of Commerce/National Bureau
of Standards, September 1969.
56
-------
13. Draft of proposed rules for "Standards Applicable to Owners and
Operators of Hazardous Waste Treatment, Storage, and Disposal Facili-
ties". Obtained from Office of Solid Waste, Environmental Protection
Agency. March 1978.
14. Sehmel, G., Battelle Pacific Northwest Laboratories. Pacific Northwest
Laboratory Annual Report for 1972. BNUL-1751, Volume II, 1973.
15. Vaughan, B., et al, Battelle Pacific Northwest Laboratories. Review of
Potential Impact on Health and Environmental Quality from Metals
Entering the Environment as a Result of Coal Utilization. August 1975.
16. Department of Health, Education, and Welfare. Air Quality Criteria
for Hydrocarbons. March 1970.
17. U.S. Environmental Protection Agency. 1975 National Emissions Report.
May 1978.
18. Department of Health, Education, and Welfare. Air Quality Criteria
for Photochemical Oxidants. March 1970.
19. Glass, N., Office of Health and Ecological Effects. Ecological Effects
of Gaseous Emissions from Coal Combustion. November 1977.
20. Argonne National Laboratory. The Environmental Effects of Using Coal
for Generating Electricity. Prepared for Nuclear Regulatory Commission.
Washington, D.C. May 1977.
21. Argonne National Laboratory. A Preliminary Assessment of the Health
and Environmental Effects of Coal Utilization in the Midwest. January
1977.
22. Argonne National Laboratory. Assessment of the Health and Environmental
Effects of Power Generation in the Midwest, Vol. II, Ecological Effects.
April 1977.
23. Ford, A. and H.W. Lorber, Los Alamos Scientific Laboratory. Methodolo-
gy for the Analysis of the Impacts of Electric Power Production in the
West. January 1977.
57
-------
APPENDIX A
SIMPLIFIED AIR QUALITY MODEL
Simple ambient air quality models were used to estimate the maximum
expected ground level concentrations of criteria pollutants. It is
important to recognize that these air quality values are estimates only.
based upon several simplified assumptions, as discussed below. Two sets
of meteorological conditions were considered: worst case and typical.
Conditions were selected that are representative of what could reasonably
be expected to occur almost anywhere in the country but are not specific
to the area of the plant from which the pollutant emission rates were
obtained. It was assumed that all species were inert. No photochemical
reactions were considered.
There are several meteorological conditions which can produce high
ground level pollutant concentrations. These conditions can result in
plume coning, looping, fumigation, and trapping, all of which can cause
high ambient concentrations. In the case of coning, high levels occur
along the plume centerline. Looping causes high ground level concentrations
at points where the plume impacts the ground. Fumigation causes high ground
level concentrations which are generally lower than those from plume
trapping. For this study it was assumed that plume trapping constituted
the worst case in terms of ground level concentrations.
Trapping conditions occur when an inversion layer or stable air aloft
inhibits upward dispersion of the plume. Although the plume is trapped by
the capping stable layer at height L, the plume distribution is still
Gaussian in the horizontal and uniform in the vertical directions. Ambient
concentrations can be estimated by the following equation (1):
r
*-
exp . 1/2 + exp .
(1)
N-l L °z
58
-------
+ exp - 1/2 (zrH±2Nk)2 + exp _ (z±H±2NL)2] j
az °z J >
Where: X (x,y,z;H) = Concentration at point (x,y,z) assuming an
effective stack height of H, yg/m^
H = Effective stack height, m
Q = Pollutant emission rate, kg/hr
H = Mean wind speed, m/s
a = Concentration distribution within the plume
in the horizontal (^y) and vertical (^z)
directions, m
z = Height above the ground, m
J = Maximum wind speed class index, unitless
N = Wind speed class index, unitless
L = Height of the stable layer, m
At ground level (z=0) and at the plume center line (y=0)
Equation (1) reduces to:
2
+2NL
(2)
For typical conditions, ground level concentrations were calculated
using a Gaussian solution to the convective diffusion equation (2):
2 2
X (x,y,o) = yq Q . exp - {(H2/2az ) + ( y2/2ay ) } (3)
y z s
Where: X = Concentration, g/m
Q = Pollutant release rate, g/s
•
a a, = Crosswind and vertical plume standard deviations, m
y» z
q = Mean wind speed, m/s
H = Effective stack height, m
x,y = Downwind and crosswind distances, m.
59
-------
At the plume center-line, Equation (3) reduces to:
X (x.o.o) = m 9 - exp - -L (4))
TOy V 2a£2
The maximum value of this equation occurs at the distance where
a = H /
In Equations (3) and (4), H is defined by:
H = H? + AH (5)
Where Hg = physical height of the stack and H » plume rise, both, expressed
in meters. There are more than 30 plume-rise formulas in the literature,
all of which require empirical determination of one or more constants, for
the purpose of this study, the Briggs plume rjs.e formula was chosen to
calculate the final plume rise in stable conditions,
AH * 2.6 ( rfr) C6)
Where: AH - Plume rise, ro
v = Wind speed, m/s
s * Stability parameter, unitless
F = Buoyancy flux.
The stability parameter, s, is defined as:
S - 1 H (7)
e 3 z
2
Where: g = Gravitational constant, m/s ;
e = Potential air temperature, K
3G/3Z = (3T^z) + 0,0098 K/m, the potential temperature
gradient. Based on the normal lapse rate, 3T/3Z, of
temperature in the atmosphere of -0.0065 K/m, a value
of .0033 K/m was employed for Jia in this study,
3Z
60
-------
The buoyancy flux, F, is defined as:
F = f1 gwr2 (8)
Where AT = Stack temperature minus the ambient air temperature, K
T = Stack temperature, K
2
g = Gravitational constant, m/s
w = Stack exit velocity, m/s
r = Inside radius of the stack, m.
The plume rise was calculated using Equation (6). The data used for
the calculations are shown in Table A-l. The values selected for wind speed
are discussed below.
TABLE A-l. STACK PARAMETERS AND PLUME RISE
Stack temperature, K 394
Ambient temperature, K 293
Stack exit velocity, m/s 24
2
Stack area, m 26
Stack height, m 73
Equation (2) was used to estimate maximum ambient concentrations
resulting from short term meteorological conditions causing plume trapping.
As a worst case estimate for this study, plume trapping conditions were
assumed to persist for periods as long as three hours. Equation (4) was
used to estimate maximum ambient concentrations for condtions which could
typically persist over a 24 hour period. For the 24 hour concentration
forecasts, typical conditions of wind speed (4 m/sec) and atmosphere sta-
bility (Class D stability) were assumed to persist. For the short-term
plume trapping, conditions of low wind speed (1 m/sec) and a moderately
unstable atmosphere (Class B stability) were assumed to persist throughout
the applicable averaging period. These conditions were selected because
61
-------
they produce high ground level concentrations. The inversion inducing
plume trapping was assumed to be at an elevation equivalent to the
effective stack height (504 m). Results of these calculations are
presented in Table A-2.
TABLE A-2. PREDICTED MAXIMUM AMBIENT CONCENTRATIONS
OF CRITERIA POLLUTANTS
Pollutant
Pollutant Concentration,
ug/n\3
24 hour period:
N0x
CO*
S02
Particulates
Total organics
Plume trapping:
NOX
CO
S02
Particulates
Total Organics
8
0.4
6
0.5
0.04
260
15
230
18
1
62
-------
REFERENCES FOR APPENDIX A
1. Bierly, E. W., and E. W. Hewson. Some Restrictive Meteorological
Conditions to be Considered in the Design of Stacks, Journal Applied
Meteorology, 1,3, 383-390, 1962.
2. Slade, D. H. Meteorology and Atomic Energy, U. S. Atomic Energy
Commission, 1968.
63
-------
APPENDIX B
ORGANIC ANALYSES - OIL FIRING
Sample Preparation
Emissions from the stack at the oil-fired utility boiler were sampled
both while the unit was operating at 62 and 92% of full load. The test run
at 62% of full load conditions will be referred to as test 142; the run at
92% of full load will be called test 143.
Two additional test runs were made, using the SASS train, which were
not analyzed. All samples from the four tests were prepared for analysis
using procedures detailed in Reference B-2, with modifications whenever
necessary to ensure Level 2 quality data would be produced. The steps
involved for each sample type are summarized below.
XAD-2 resins: Each sample was extracted in a Soxhlet apparatus
for 24 hours with methylene chloride.
Filters: Each sample was extracted In a Soxhlet apparatus for
24 hours with methylene chloride.
XAD-2 module condensates: Each sample was extracted three
times with methylene chloride at adjusted pH condition
to first 11, and then 2. The volume of methylene chloride
used for each extraction was ten percent of the condensate
volume.
Organic rinses: No preparation required.
One milliliter aliquots were taken of all these samples for subsequent
TCO analysis. Then the solutions were concentrated to 10 ml in Kuderna-
Danish evaporators. Aliquots taken for analyses Included 1 ml for TCO,
1 ml for GRAV/IR and a composite for GC/MS prepared as follows:
CD-LEA-KD 1 ml CDB-LEA-KD 1 ml
CD-LEB-KD 1 ml CDB-LEB-KD 1 ml
XR-SE-KD 2 ml XRB-SE-KD 2 ml
PF-SE-KD 2 ml PFB-SE-KD 2 ml
PR-O-KD 2 ml MAB-O-KD 4 ml
MR-O-KD 2 ml
64
-------
The flow diagram in Figure B-l shows the sample handling and analysis
scheme used. The sample code is explained in Table B-l.
Summary
Level 1 —
The total amounts of organics found in the stack emissions during these
two tests are shown below:
Test C1"C6 C7"C16 * C16 ^ota1 Or9anics
142 850-1241 yg/m3 61 .1 yg/m3 478 yg/m3 1389-1780 yg/m3
143 327-652 54.6 397 779-1104
The field GC analysis showed measurable amounts of only C-j , i.e.,
methane. The laboratory GC analysis indicated about fifty percent of the
3
less volatile materials were in the Cg boiling range. The other 20 yg/m
were reasonably well distributed throughout the entire 200°C boiling point
range being examined.
A peak-by-peak evaluation of the chromatograms of the Cy-C-ic compounds
shows no signs of the acetone condensation products mesityl oxide (a Cg) or
diacetone alcohol (a CQ).
The amount of material less volatile than n-heptane in individual
samples was too low to trigger the Level 1 liquid chroma tographic separation
procedure. Also, the infrared spectra of XAD-2 resin samples were in-
distinguishable from the resin blank.
Level 2--
Results of the analysis of the combined SASS train extracts and the
controls are summarized as follows:
1) The compounds found in the combined SASS train extracts
and which are believed to have been present in the gas
sample are present at 2 yg/m3 or less. Many of the
compounds identified in the total sample are sorbent
resin artifacts.
2) Some compounds could not be identified by computerized
data reduction techniques. These are believed to be
si li cone artifacts, for the most part.
65
-------
1 ml allqu
N »
JH]
t * i 1 ml all
JTCOJ
F
ot
quot
yes
LC
RACTIONATION
frcol
}GRAV/IR|
I—*T
IGC/MSI
H^
IS THE SAMPLE
ADEQUATELY
CHARACTERIZED
.no
SPECIAL
ANALYSIS
I solution
.XfsN.
^r CONTENT. ^S..,, no
"V^ bOO yg/m" ^^
bulk
. » r .L
IKUOERNA-DANISH
CONCENTRATION
* 1 mi aliquot
JGRAV |
1 ^
B
COMPOSITE
SASS TRAIN
SAMPLES
10 ml
^•Jl '
1^^^^™^^™^
Cr/uc 1
uu/ro-i
IS THE
ADEQUJ
CHARAC
SAMPLE yes / N
in Y , . . . f 5TOP I
TERIZED v-^ '
no
SPECIAL
ANALYSES
Figure B-l. Flow Chart of Sample Handling and Analysis Procedures
66
-------
TABLE B-l. SAMPLE CODE FOR ORGANIC SAMPLES ANALYZED
SAMPLE CODE
•XXX-XX-XX-XX-XX-
cr>
Site
Identification
Sample
Type
Sample
Preparation
First Level
Analysis
Second Level
Analysis
141
142
143
144
CD-condensate
from XAD-2
module
PR-solvent probe
rinse
MR-solvent XAD-2
module rinse
XR-XAD-2 resin
PF-filters
XM-composite of
SASS train
component
samples
0-no preparation
LEA-liquid-liquid
extraction,
acidified
sample
LEB-liquid-liquid
extraction,
basic sample
SE-Soxhlet solvent
extraction
KD-K-D
concen-
tration
GC-C7-C16
GI-GRAV/IR
MS-GC/MS
LC-LC separation
-------
3) Some POM were found in the samples at levels ranging
from less than 0.05 to 10 vg/m3 of sampled gas.
Level 1 Data
Total Chromatographable Organics Analysis (TCO)--
TCOs were performed as described earlier. All samples were analyzed
both prior to and after the Kuderna-Danish concentration step. The results
of the C7-C,g analyses on the K-D concentrates are given in Table B-2.
The unconcentrated samples did not contain any detectable quantity of
hydrocarbons, and are, therefore, not listed.
Field Gas Chromatographic Analyses—•
The chromatographic analyses performed in the field make use of a
Shimadzu GC-Min 1 gas chromatograph with dual flame ionization detectors.
Separations are made on a 183 cm x 0.32 cm stainless steel Poropak Q
packed column.
Calibration and quantitation is accomplished using the same techniques
as in the laboratory. The n-alkanes and the data reporting ranges are
listed below.
C1 -160 to -100°C C4 0 to 30°C
C2 -100 to - 50°C C5 30 to 60°C
C3 - 50 to 0°C Cg 60 to 90°C
The detection limits for the field GC analyses, properly calibrated
3
with C,-C, standards, are 0.1 ppm or 65 yg/m hydrocarbon as methane.
Results of the field analysis are summarized in Table B-3.
Gravimetry for C13 and Higher Hydrocarbons-
Gravimetric determinations were performed on the concentrates of
solvent rinses and extracts in accordance with the procedure in Reference
B-2: a one milliliter aliquot was taken from each sample and evaporated to
dryness in an aluminum pan. The residues were then weighed on a micro-
balance. The results are presented in Table B-4.
68
-------
TABLE B-2. RESULTS OF TCO ANALYSIS OF UNCONCENTRATED AND CONCENTRATED SAMPLES
10
0
Hydrocarbon Content, pg/m
Sample
142-CD-LEA-KD-GC
142-CD-LEB-KD-GC
143-CD-LEA-KD-GC
143-CD-LEB-KD-KC
142-XR-SE-KD-GC
143-XR-SE-KD-GC
142-PF-SE-KD-GC
143-PF-SE-KD-GC
142-PR-O-KD-GC
143-PR-O-KD-GC
142-MR-O-KD-GC
143-MR-O-KD-GC
C7
LB
LB
LB
< 0.1
0.4
0.4
0
0
0
0
0
0
C8
0
0
0
0
26.5
28.1
LB
0
0
0.2
0
0
C9
0
0
0
0
1.0
2.2
0
0.9
2.9
3,6
4.6
3.6
-------
TABLE B-3. RESULTS OF FIELD GC ANALYSIS
3
Hydrocarbon Content, vg/m
Sample GI Cg C3 C^ Cg Cg
141 981 <65 <262 <131 < 65 < 65
142 850 < 65 <131 < 65 < 65 < 65
143 327 < 65 < 65 < 65 < 65 < 65
144 (no data)
Total
981 - 1569
850 - 1241
327 - 652
-------
TABLE B-4. GRAVIMETRY OF SAMPLE CONCENTRATES
Sampl e
142-CD-LEA-KD-GI
142-CD-LEB-KD-GI
143-CD-LEA-KD-GI
143-CD-LEB-KD-GI
142-XR-SE-KD-GI
143-XR-SE-KD-GI
142-PF-SE-KD-GI
143-PF-SE-KD-GI
142-PR-O-KD-GI
143-PR-O-KD-GI
142-MR-O-KD-GI
143-MR-O-KD-GI
141-COB-LEA-KD-GI
141-COB-LEB-KD-GI
141-XRB-SE-KD-GI
141-PFB-SE-KD-GI
141-MCB-O-KD-GI
141-MAB-O-KD-GI
Weight
mg/ml
0.078
0.051
0.103
0.050
1.470
1.582
0.135
0.093
0.159
0
0.142
0.138
0.075
0.036
0.582
0.121
0.075
0.109
Correction for
Blank, mg/ml
LB
LB
0.028
0.013
0.954
1.104
0.014
LB
0.110
0
0.077
0.070
Aliquot
Factor
XI 0
XI 0
xio
X10
XIO
XIO
XIO
XIO
XIO
XIO
XIO
XIO
Sample 3
Volume, m
24.4
24.4
30.6
30.6
24.4
30.6
24.4
30.6
24.4
30.6
24.4
30.6
Net Gcav,
yg/nr
0
0
9.2
4.2
396
361
5.7
0
45.1
0
31.5
22.9
-------
Infrared Analyses (IR) on Samples Concentrated in Kuderna-Danish Evaporators--
Each of the concentrates weighing more than 0,5 mg was also scanned by
infrared (IR) spectroscopy. After the final weighing, the residue in each
weighing pan was redissolved in methylene chloride and smeared onto a NaCl
window. The resulting spectra and the compound classes whose presence was
identified are summarized in Table B-5. The spectra of the samples were
indistinguishable from those of the blanks.
Other Analyses—
3
No sample contained more than 0.5 mg/m of organic material. Applying
stated Level 1 decision criteria, the organic analysis was halted. A com-
posite sample of all the SASS train components was prepared for Level 2
organic work.
Level 2 Data
Two different GC/MS analyses were performed. GC/MS was performed using
parameters as similar as possible to those used in the Total Chromatographable
Organics (TCO) analysis. The objective of this approach was to identify
peaks seen in the TCO chromatograms. In addition, several of the samples
in this study were also subjected to a specific POM analysis using a Dexsil
300 column. Both of these techniques are described in Reference B-2. A
total of three samples was submitted for this effort. A description of the
samples analyzed is presented in Table B-6.
Tables B-7 through B-9 present the results of the GC/MS analyses as
source concentrations. DMEG values are also given. Compounds marked with
an asterisk were not found in the blank, as described in the next paragraph.
Except for the possible benzopyrene in the 142 SASS composite, DMEG values
for compounds in Tables B-8 and B-9 were at least 1600 times larger than the
concentrations found. Benzopyrene was not positively identified, but if the
compound was benzopyrene, it is present at a level 32% above its DMEG value.
The results for the blank sample (Table B-7) are included in this
document because chemical compound contribution from the blank is substan-
tial v/hen compared to the samples. Furthermore subtraction of the blank
levels from the sample levels could lead to misinterpretation of the data.
72
-------
TABLE B-5. INTERPRETATION OF INFRARED
SPECTRA OF SAMPLE CONCENTRATES
Samp! e
Identifica-
tion
141-XRB-SE-KD-
GI
Band
Location,
cm"1
3400
3060
2920, 2860
1720
1690, 1670, 1640,
1630
1600
1550
1530
1510, 1480
1460"
1450
1410
1370
1345
1270
mo
930
700
Band
Intensity
W
W
S
M
W
U
W
W
W
M
M
W
M
M
M
S
W
N
Compound
Classification
OH, NH or C « 0 overtone
CH stretch-aromatic
CH stretch-aliphatic
C = 0
C = C
Jenzene ring
<02 antisym stretch
tenzene ring
tenzene ring
sf\n
«Hn
Carboxylic acid
CH3
NO, sym stretch
C-6-C
C-O-H
Carboxylic acid
Ben.zene ring substitution
Indicates esters, poly-
ethylene oxide with
alcohol possible, i.e.,
resin
N.B. Samples 142-XR-SE-KD-
61 and 143-XR-SE-KD-GI
indistinguishable from
blank
- Continued -
73
-------
TABLE B-5 (Continued)
Sampl e
Identifica-
tion
142-XR-SE-KD-GI
Band
Location,
cm"1
3560-3140
3060
2920, 2860
1720
1710
1640, 1630
1600
1550
1500, 1495, 1480
1470
1460, 1450
1410
1370
1345
1270
1175
1105
1025, 1015
940
855
835
800
755
710
Band
Intensity
W
W
S
S
S
W
U
W
W
N
W
W
W
M
W
S
W
W
W
K
W
W
W-
Compound
Classification
OH, NH or C » 0 overtone
CH stretch-aromatic
'CH stretchraliphatic
C = 0
C « 0
C = C
Benzene ring
N02 antisym stretch
Benzene ring
CH2
Carboxylic acid
CH3
N02 sym stretch
C-O-C
Unassigned
C-O-H
Unassigned
Carboxylic acid
Benzene ring substitution
- Continued -
74
-------
TABLE B-5 (Continued)
Sampl e
Identifica-
tion
Band
Location,
cm'l
Band
Intensity
Compound
Classification
143-XR-SE-KD-GI
3600-3150
3060
2960, 2920/2870
1720
1710
1640, 1630, 1600,
1530, 1510, 1500
1490, 1470
1.550
1460
1450
1410
1370
1275
1250
1175
1100
1030
940
850, 800, 760, 710
W
W
M
M
N
W
W
W
W
W
W
N
M
U
M
W
W
OH, NH or C = 0 overtone
CH stretch-aromatic
CH stretch-aliphatic
C = 0
C = 0
Unsaturation; 1600 in
benzene ring
N02 antisym stretch
CH2
Carboxy!ic acid
CH3
C-O-C
c-o-c
Unassigned
C-O-H
Unassigned
Carboxylic acid
Benzene ring substitution
75
-------
TABLE B-6. SUMMARY OF 6C/MS SAMPLES AND ANALYSES
FROM THE OIL-FIRED SITE
Sample No.
Description
142-XM-SE-KD
143-XM-SE-KD
141-XMB-SE-KD
Composite of SASS Train Extract and Rinse
Concentrates
Composite of SASS Train Extract and Rinse
Concentrates
Composite of Blank Samples Related to SASS Train
Sampling; Also Concentrated
TABLE B-7. GC/MS ANALYSIS OF 141-XMB-SE-KD
(BLANK) COMBINED EXTRACTS
Compound
Level 2 Analysis
Dlethyl benzene
Ethyl styrene
Netliyllndene
Naphthalene
Chloronaphthalene
(Internal Standard)
Ethyl talphenyl or Mphenylethane
Unknown
TMO Components believed to be
Trine thy 1 propenyl naphtha 1 ene
and DlhydrtMethylphenylbenzofuran
Unknown Sillcone Compound
C18H22
Mixture believed to contain
Hexadecyloxypentadecyl - 1.
3-D1oxane and an alcohol >C]4.
Butyl 1 sobutyl phthal ate
Unknown S 111 cone
Unknown Sillcone
Unknown Sillcone
01 octyl phthal ate
POM Analysis
Naphthalene
Possible
Trl Methyl propenyl naphtha 1 ene
Concentration
In Extract
ug/«l
26
60
3
44
20
1*
1
29
13
9
73
17
2
5
4
34
24
11
Simulated
Concentration
In Sampled Gas
wg/m3*
3
7
0.4
5
2
2
0.1
3
2
1
9
2
0.2
0.6
0.5
4
3
1.3
1
Theoretical Sample Volume of 30 m used.
76
-------
TABLE B-8. GC/MS ANALYSIS OF 142 SASS COMPOSITE
Compound
level 2 Analysis
Ethyl styrene
Nethyllndene
Naphthalene
*B«nza1dehyde
*Tr1methylcyclohexene-one
*C. Substituted Acetophenone
•Substituted Benzole Acid. Methyl
Ester
Chloro naphthalene
(Internal Standard)
Ethyl biphenyl or 01 phenyl ethane
Unknown SlUcone
*D1ethylphthalate
Unknown
Two compounds believed to be
Trimethylpropenylnaphthalene and
Di hyd romethyl phenyl benzof uran
Unknown SI 11 cone
Unknown SlUcone
Unknown
Hexadecyloxypentadecyl - 1,
3-D1oxane
Butyl 1 sobuty 1 phtha 1 ate
*Fluoranthene
*Pyrene
Unknown Si li cone
Dioctylphthalate
POM Analysis
Naphthalene
'Possible Phenanthridene NU179
Possible Trimethylpropenylnaphthalene
'Probable POM KW184
•Phenanthrene
*Fluoranthene
*Pyrene
•Chrysene or other MU228 PON
•Benzopyrene or other MW252 POM
Concentration
In Sampled Gas
wg/m3
4
0.3
4
2
0.4
0.3
0.4
3
0.7
0.7
0.7
0.3
2
0.6
3
0.4
2
1
2
0.6
0.7
25
10
0.3
2
0.6
1
1
1
0.1
0.0)
DMEG Value
ng/m3
5.9E4
No Data
4.1E4+
6.1E4
___
—
5E3
...
• V —
• »
• .—
...
...
9E4
2.3E5
—
—
...
No Data
—
Unknown
1.6E3
9E4
2.3E5
2.2E3
2E-2
Detected compounds not found in blank sample: 141-XHB-SE-KO.
These are presuned to be 1n the gas sample.
Value is for acetophenone.
77
-------
TABLE B-9. GC/MS ANALYSIS OF 143 SASS COMPOSITE
Compound
Level 2 Analysis
Possible trans Chlorocyclohexanol
Methylbenzene
Ethyl styrene
•Benzole Acid, Methyl ester
Possible Methyllndene
Nethyl Indent (Isomer)
•Ethylbenzaldehyde
Naphthalene
•Trine thylcyclohexene-one
*C2 Substituted Acetophenone
•Possible C3 Substituted Phenol
Chi oronaphtnalene
(Internal Standard)
Ethylblphenyl or. Dlphenyl ethane
•Unknown (apparent nle wt 180)
•Dlethylphthalate
Unknown SlUcone
Two Compounds believed to be
Trlnethylpropenylnaphthalene and
DlhydroMthylphenylbenzofuran
Unknown SlUcone
Unknown S1 11 cone
Unknown S1 11 cone
Unknown 51 11 cone
Unknown SlUcone
Unknown; Apparent wle wt 343
Butyl 1 sobutyl phthalate
Unknown SlUcone
•TetraKthyl phenanthrene-
Unknown SlUcone
Oloctylphthalate
POM Analysis
Naphthalene
Possible
Trine thy 1 propenyl naphtha 1 ene
•Anthracene or Phenanthrene or
Other MW178 POM.
Concentration
In Sanoled Gas
w9/"«3
o.s
2
2
0.02
0.07
0.1
0.4
2
O.S
0.2
O.S
2
0.1
0.4
0.2
0.4
2
O.S
0.4
3
0.4
0.4
1
0.8
1
0.6
0.4
2
6
0.5
0.2
OMEG Value
ug/m3
—
—
—
6.1E4
—
—
5.9E4+
—
NO Data
4.1E4+
1 .5E4*
—
—
5E3
...
«•
—
—
-T-
...
...
_—
1.6E3
• ••
...
•••
—
1.6E3
Detected compounds not found 1n blank sanple: 141-XMB>SE-KO.
Presumed to exist 1n sample gas.
* Value given 1s for parent compound.
* Value Is for ethyl phenol.
78
-------
The compounds which have been found in the two samples (Tables B-8 and
B-9) and which are absent in the mixture of blank resin artifacts have been
designated by an asterisk preceding their name. One will notice that only
7 to 8 compounds have been so designated. None of these compounds have been
3
determined to be in the sample gas at levels exceeding 2 yg/m .
The lower portions of Tables B-7, B-8, and B-9 present the results of
the specific POM analysis performed. Several POM compounds were found in
the 142-XM-SE-KD sample when the computerized search techniques for POM were
used. Three of the compounds were also found by the nonspecific Level 2
technique. In sample 143-XM-SE-KD, only one compound was found by specific
POM analysis which was not found in the blank.
79
-------
REFERENCES FOR APPENDIX B
B-l. Leavitt, C., et al. Environmental Assessment of Coal and Oil Firing
in a Controlled Industrial Boiler. Appendix B. Report prepared by
TRW for the U.S. Environmental Protection Agency. EPA-600/7-78-164a.
August 1978.
B-2. Hamersma, J.W., D.G. Ackerman, M.M. Yamada, C.A. Zee, C.Y. Ung, K.J.
McGregor, J.F. Clausen, M.L. Kraft, J.S. Shapiro, and E.L. Moon.
Emissions Assessment of Conventional Stationary Combustion Systems -
Method and Procedures Manual for Sampling and Analysis. Report
prepared by TRW for the U.S. Environmental Protection Agency.
EPA-600/7-79-029a. January 1979.
80
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-600/7-80-087
2.
3. RECIPIENT'S ACCESSION-NO.
, TITLE AND SUBTITLE
Environmental Assessment of an Oil-fired
Controlled Utility Boiler
5. REPORT DATE
April 1980
6. PERFORMING ORGANIZATION CODE
c Leavitt,K. Arledge, C. Shih,R. Orsini,
A. Saur ,W. Hamersma,R. Maddalone ,R. Beimer,
j. Richard, S. Unges and M. Yamada
. PERFORMING ORGANIZATION NAME AND ADDRESS
TRW, Inc.
One Space Park
Redondo Beach, California 90278
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
EHE624A
11. CONTRACT/GRANT NO.
68-02-2613, TaskS
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 6/78-12/79
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES IERL_RTP project officer is Michael C. Osborne, Mail Drop 62,
919/541-3996.
is. ABSTRACT
repO1^. gjves results of a comprehensive emissions assessment of the
Haynes No. 5 boiler during oil-firing. Levels 1 and 2 procedures were used to char-
acterize pollutant emissions. Assessment results , in conjunction with assumed ty-
pical and worst case meteorological conditions , were used to estimate the environ-
mental impact of emissions from this type of unit. Principal conclusions were: (1)
The risk of violating NAAQS due to criteria pollutant emissions is low. (2) Little
adverse health effect is anticipated as a result of SO2, SO4 (--), and particulate
emissions projected from widespread use of oil-fired units of the type tested. (3) The
impact of trace element burdens in drinking water, plant tissue, soil, and the atmos-
phere is negligible. (4) The risk of plant damage due to criteria pollutant emissions
is remote. (5) The likelihood of plant damage due to trace element emissions is
remote.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Assessments
Boilers
Fuel Oil
Combustion
Sulfur Oxides
Dust
Pollution Control
Stationary Sources
Environmental Asses-
sment
Utility Boilers
Particulate
13B
14B
13A
2 ID
21B
07B
11G
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
81
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