United States
Environmental Protection
Agency
Atmospheric Sciences Research
Laboratory
Research Triangle Park NC 27711
Research and Development
EPA/600/S3-85/030 June 1985
Project Summary
Measurement of Sulfur and
Carbon Species Emissions from
Oil-Fired Commercial and
Institutional Boilers
S. E. Miller
This project was conducted to provide
improved emission data that are used to
support urban particulate models. The
objectives of the study were twofold: to
determine emission factors for primary
sulfate and carbon from a variety of
commercial and industrial heating units
burning fuel-oil, and to evaluate and
compare the performance of the mini-
• atureacid condensation system (MACS)
and the acid condensation system (ACS)
methods for determining free sulfuric
• acid (HaSO4).
The emission data summarized in the
report are the result of two field studies
in Philadelphia, PA, the first during
March-April 1982 and the second dur-
ing the Philadelphia Aerosol Study in
August 1982. Five boilers were moni-
tored in the studies. Two were utility
boilers, and the remainder were small
process steam or heating boilers ranging
in size from 23.600 to 50,000 Ib/h.
Emission data for sulfur species, carbon
species, and trace elements are pre-
sented in the report.
This Project Summary was developed
by SPA's Atmospheric Sciences Re-
search Laboratory, Research Triangle
Park, NC, to announce key findings of
the research project that is fully docu-
mented in a separate report of the same
title (see Project Report ordering infor-
mation at back).
Introduction
During the past decade, receptor-
oriented models have evolved rapidly and
are now recognized as distinct disciplines.
The models have been widely accepted
and are currently one of the primary tools
employed by control agencies to estimate
the impact of sources at receptor sites. As
is often the case, the rapid evolvement of
models for particulate matter has resulted
in certain inadequacies. Although large
volumes of data have been accumulated
' on the chemical and physical characteris-
tics of particulate matter, little is known
about its sources and subsequent contri-
bution to levels at specific receptor sites.
The source impact on ambient loadings at
these sites is recognized as an approxi-
mation at best. This approximation is due
largely to many variables (primarily
meteorological) that are random in nature,
change with space and time, and may
combine with other variables in a non-
linear manner. If modeling of particulate
emissions is to acquire its anticipated
prominence in air particulate control
programs, additional research is needed
to more adequately define the boundaries
of the models and to rectify some of the
inherent weaknesses, such as those
described above. Additional work is also
needed to improve the sampling and
analytical techniques used in assessing
the effect of individual sources.
This research program was initiated in
support of a program to provide improved
source emission data for urban particulate
models. The objectives of the study were
twofold: to determine emission factors for
primary sulfate and carbon from a variety
of commercial and industrial heating units
burning fuel-oil, and to evaluate and
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compare the performance of the minia-
ture acid condensation system (MACS)
and the acid condensation system (ACS)
methods for determining free sulfuric
acid (HzS04).
The data summarized in this report are
the results of two individual work assign-
ments (WA-6 and WA-12) emanating
from EPA Contract No. 68-02-3487. The
field portion of WA-6 was conducted in
Philadelphia, PA, from March 22 to April
6,1982 (winter study). Work assignment
12 was conducted in Philadelphia from
August 4 to August 14, 1982 (summer
study). Five boilers were monitored in the
study. Two of the units tested were utility
boilers. The remaining three units were
small process steam or heating boilers
ranging in size from 23,500 to 50,000
Ib/h.
Procedure and Results
Paniculate Matter
Particulate matter was collected by
using EPA Method 5 for the determination
of mass loading, sulfate and carbon
content, and trace element analysis. Mass
loading was determined from the front
half rinse of the Method 5 train (i.e., probe
nozzle, probe, and front half of the filter
holder, and the filter catch). Following
mass loading determinations, the filters
were divided into three sections. One half
of each filter was used for elemental
composition analysis via a Siemens Model
MRS wavelength dispersive X-ray spec-
trometer. One quarter of each filter was
used to determine carbon forms (organic
carbon, elemental carbon, total carbon,
and CO3") by using an automated thermal-
optical method. The final quarter of each
filter was analyzed for paniculate sulfate
by ion chromatography.
The average particulate emission rate
for the three heating boilers was 0.67
kg/h, with a range of 0.18 to 1.73 kg/h.
The average emission rate for the two
utility boilers was 11.53 kg/h, with a
range of 4.78 to 20.40 kg/h.
The average particulate sulfate emis-
sion rate for the three heating boilers was
0.24 kg/h, with a range of 0.06 to 0.39
kg/h. The two utility boilers averaged
2.63 kg/h, with a range of 0.56 to 5.63
kg/h.
Total carbon emissions for the three
heating boilers averaged 18.44 g/h, with
a spread of 3.42 to 48.56 g/h. The average
total carbon emissions from the two utility
boilers was 1471.21. g/h, with a spread of
74.86 to 4171.33 g/h.
Trace elemental emission data and the
full complement of analytical results,
including blanks and duplicate runs, are
appended in the report.
Primary Su/fates
Sulfur dioxide (S02) and H2SO4 emis-
sion data were obtained at each boiler by
two methods: the Acid Condensation
System (ACS) and the Miniature Acid
Condensation System (MACS). The two
systems are very similar except for the
H2S04 collector. The ACS train condenses
the H2S04 in a temperature-controlled
(60°C, 140°F) condensation coil, and the
MACS train uses a temperature-control-
led (60°C, 140°F) glass wool plug. For
comparison purposes, both trains were
run concurrently from the same sampling
port. The tests were conducted as single
point samples, with average AP values
determined from Method 5 particulate
runs.
During the initial study, flow problems
were encountered in the MACS system.
With repeated use, the glass wool was
redistributed and collected at one end of
the holder, restricting the gas flow and
resulting in a high pressure drop across
the system. The change in pressure made
it extremely difficult to maintain a con-
sistent and repeatable sampling rate. This
problem was alleviated during the second
half of the study by enlarging the bore size
of the glass wool holder and packing the
wool in a more serviceable manner.
During the initial study (winter study),
when flow problems were encountered,
plotted data for the MACS method versus
the ACS method showed a substantial
variability between the two systems, with
the MACS system producing much lower
readings. When the flow problem was
alleviated (summer study), good agree-
ment between the two methods was
achieved, with little constant or propor-
tional bias in the MACS method relative
to the ACS method.
The H2S04 data collected by the MACS
and ACS systems during the summer
study are summarized in Table 1. The full
complement of S02 and H2S04 analytical
results is presented in the report. .
Conclusions
The results of this study provide evi-
dence that the MACS can serve as a
primary sulfate characterization method
for combustion-source measurements.
Within experimental error, the glass wool
plug will collect H2S04 as well as the
Goksoyr-Ross-type condenser. The study
also shows, as was evident in the winter
study (initial study), that both metho
(MACS and ACS) must be used w
caution. Both methods of evaluation a
subject to certain critical sampling parai
eters(filtration temperature and sampli
flow rate) which, if varied for any reasc
will result in incomparable and erroneo
data.
Total carbon and trace element emi
sion data are presented in the report, b
conclusions are left to the reader.
Table 1. Summary of H^SO4 Data, A(
Versus MACS, Summer Study
Test
Number
PES-1
PES-2
PES-3
PES-4
PES-B
SBS-1
SBS-2
SBS-3
SBS-4
SBS-S
SBS-6
SBS-7
SBS-8
ACS
(ppm)
4.35
2.29
2.45
2.20
4.49
0.83
0.74
0.77
0.79
0.84
0.74
0.81
0.77
MACS
(ppm)
5.35
1.86
1.60
2.00
1.00
0.23"
0.76
0.81
0.77
0.74
0.74
0.78
0.80
*Data not included in statistical analysis due
anomalous value for MACS technique.
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S. f. Miller is withBattelle Columbus Laboratories, Columbus, OH 4^201.
Roy L. Bennett is the EPA Project Officer (see below).
The complete report, entitled "Measurement of Sulfur and Carbon Species
Emissions from Oil-Fired Commercial and Institutional Boilers, "(0>
85-207 520/AS; Cost: $10.00, subject to change) will be available
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Atmospheric Sciences Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC27711
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