United States      Office of Air Quality
Environmental Protection  Planning and Standards
Agency        Research Triangle Park NC 27711
A,r
                       EPA-450/3-84-16
                       September 1984
Development and
Evaluation of
Method 5B—
Background
Information for
Proposed
Reference Method



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                                 EPA-450/3-84{16
      Development and Evaluation of
Method 5B—Background  Information for
       Proposed Reference Method
             Emission Standards and Engineering Division
             U.S. ENVIRONMENTAL PROTECTION AGENCY
                  Office of Air and Radiation
             Office of Air Quality Planning and Standards
                Research Triangle Park, NC 27711

                    September 1984

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This report has been reviewed by the Emission Standards and Engineering Division of the Office
of Air Quality Planning and Standards, EPA, and approved for publication. Mention of trade
names or commercial products is not intended to constitute endorsement or recommendation
for  use. Copies of this report are avialable through the Library Services Office (MD-35), U.S.
Environmental  Protection Agency, Research Triangle Park,  N.C. 27711, or from National
Technical  Information Services, 5285 Port Royal Road, Springfield, Virginia 22161.

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Introduction
     On June 11,  1979,  the Environmental Protection Agency (EPA)
promulgated standards  of  performance  for new electric utility steam
generating units.   In  the preamble  to the  regulation (44 FR 33580), EPA
acknowledged that using Method  5  to sample for particulate matter in gas
streams containing large  amounts  of sulfuric acid mist could lead to
collection of condensed sulfuric  acid mist as part of the particulate
sample.  Because particulate control  devices, that were identified as best
emission reduction systems, do  not  remove  sulfuric acid mist, EPA concluded
that the particulate matter sample  should  not include the condensed acid
mist and agreed to develop a test procedure that would allow the
measurement of nonsulfuric acid particulate matter (NSAPM).
     Two approaches can be used to  measure NSAPM.  One is to use a sampling
procedure that collects particulate but does not collect sulfuric acid, and
the other is to use the existing  sampling  procedure  (Method 5) and then
remove any condensed sulfuric acid  from the sample.
     Conceptually, the first approach seems easier,  but it presents some
difficult problems in  execution.  The physical state of sulfuric acid in
the stack depends on three variables, the  temperature of the gas, the
concentration of water vapor, and the concentration  of sulfur trioxide
($03).  As an example, at 155°C and 10 percent water vapor, a gas stream
can contain about 82 ppm  of uncondensed $03, but at  150°C and 10 percent
water vapor, a gas stream can contain only about 52  ppm.  This makes it
obvious that one needs to control the temperature  of the sampling system
very precisely and evenly to prevent  the collection  of condensed sulfuric
acid, but the sampling equipment  used with Method  5  does not lend itself

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readily to this kind of precise  temperature control.  Higher sampling
temperatures could  be used,  but  construction materials become a problem.
Removing condensed  sulfuric  acid after  sampling has two major advantages:
(1) It allows the tester greater flexibility in the choice of sampling
equipment and conditions,  and  (2)  it  confines operations requiring very
precise control to  the laboratory.  For these reasons, the second approach,
that of removing any condensed sulfuric acid after the sample is collected,
was chosen as the more promising one.
     Of the possible procedures  for removing condensed sulfuric acid, the
two most commonly used are:  (1)  heating the samples in an oven to evaporate
the sulfuric acid before weighing, and  (2) weighing the samples to constant
weight, then chemically measuring the condensed sulfuric acid and
subtracting its weight.  These two techniques were compared using
particulate samples collected  at a coal-fired power plant burning a very
high sulfur coal and equipped  with a  wet  scrubber.  For this set of
samples, the two techniques  gave comparable results for NSAPM.
     Each technique has its  own  advantages and  disadvantages.  The heating
technique is relatively quick  and simple, but it  is not specific for
condensed sulfuric acid since any substance that  has  a  similar boiling
point would also be evaporated.   The  analysis/subtraction technique  is  more
specific since there are very few interferences with  the chemical
measurement, but it is more time consuming and  requires a very accurate
weighing of the sample while it still contains  sulfuric acid.  This  can be
difficult because  sulfuric acid is very hygroscopic,  and  the  samples may

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not reach constant weight.   Because the heating  technique  seemed  to have
fewer problems, it was the  technique chosen  for  initial development.

Method Development
     A working method tentatively entitled Method  5B  was drafted.  The
method allowed the tester the option of collecting samples at any
temperature up to 260°C, but specified that  the  samples be returned to the
laboratory and heated in a  laboratory oven at  160°C for 3  hours before
desiccating and weighing.
     To determine the effect of sample collection  temperature, a  series of
comparative tests were conducted at three different sites.  Two of the test
sites were coal-fired boilers, and the other was an oil-fired boiler.  The
sulfur content of the fuel  varied according  to site.   A series of paired
samples were collected at each site using a  dual train system.  The filter
and sample probe of one train was maintained at  121°  +_ 25°C as specified in
Method 5, while the filter  and probe of the  other  train was maintained at
160° _+ 25°C.   The samples from all  sites were  first desiccated at room
temperature and then weighed.  Following this  initial  weighing, samples
from some sites were extracted with isopropyl  alcohol  (IPA) to remove the
sulfuric acid.  The IPA extract was then analyzed  for sulfuric acid by
barium-thorin titration and the resultant weight of sulfuric acid was
subtracted from the initial sample weights.  Samples  from  other sites were
heated to 160°C for 3 hours, desiccated, and weighed.  All samples from a
particular site were treated in the same manner.

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     The results from these tests  are summarized in Tables 1-3.  As
expected, the initial  sample weights of the samples filtered at 121°C were
consistently higher than  those  filtered at 160°C.  This can easily be seen
from the tables.  However,  after both pairs of samples were treated to
remove the condensed sulfuric acid, this  relationship did not really
change.  Although the differences  between Method 5 and 5B samples became
smaller, the samples collected  by  Method  5 were still consistently higher
than those collected by Method  5B.  This  can  also be seen clearly from the
tables.  Although the reason for  this difference could not be determined, it
was apparently related to the relative  amounts of condensed sulfuric acid
collected with the sample.
     The Environmental Monitoring and Systems Laboratory  of EPA  conducted
similar  tests concurrent with the testing described  above.  Their report
also concluded  that "sampling below the acid  dew  point and failure  to keep
the particulate material  dry during sampling  cause  a positive bias  in the
sample results  - a bias that is not removed by washing with IPA  or  by
heating  to  316°C."  While  the source of this  positive bias is unknown,  it
is  clear that samples  should not be collected at temperatures below the
acid dew point.  Therefore, the working draft of Method  5B was  revised  to
require that samples  be collected at temperatures of 160° + 25°C.   However,
 some questions  remained as to the most suitable temperature  for conditioning
 the filters in  the laboratory prior to weighing.

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     Table 1.   COAL-FIRED BOILER  NUMBER  1
RATIO OF CONCENTRATION TO REFERENCE  CONDITION
    (Method 5B - Following I PA Extraction)
Sample method
Analysis condition
Ambient
I PA extraction
5
1.54
1.15
r~ SB
1.03
1.00
     Table 2.  COAL-FIRED BOILER NUMBER 2
RATIO OF CONCENTRATION TO REFERENCE CONDITION
        (Method 5B - Heated to 160°C)
Sampl e method
Analysis condition
Ambient
Oven heat - 160°C
5
2.58
1.60
5B
1.07
1.00
          Table 3.  OIL-FIRED BOILER
RATIO OF CONCENTRATION TO REFERENCE CONDITION
        (Method 5B - Heated to 160°C)
Sampl e method
Analysis condition
Ambient
Oven heat - 160°C
b
6.73
2.00
5B
3.80
1.00

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     Using the revised draft of Method 5B, EPA began a second test program
to evaluate the consistency  of the method and to determine the effects of
different conditioning temperatures  on the measured NSAPM.  Tests were
conducted at two different sources.  The first was a coal-fired boiler
equipped with an electrostatic precipitator and a flue gas desulfurization
unit, and the second was  an  oil-fired unit equipped with a mechanical dust
collector.  Both units were  burning  fuels with relatively high sulfur
contents, ranging from 2.4 to 3.5 percent sulfur.
     Samples were collected  with a sampling system, called a quad train,
which allows the tester to collect four simultaneous samples divided into
two pairs, each pair of which is collected under the same conditions.  The
advantage of this system is  that a large number of paired samples can be
collected in a relatively brief period of time.  This minimizes the  effect
of temporal variations in source emissions making comparison between
sampling methods easier.   A  more complete explanation of this sampling
system and it's operation can be found in the emission test reports.
     The detailed sampling and  analytical matrices for the coal-fired
boiler are shown in Tables 4 and 5,  and for the oil-fired boiler in  Tables
6 and 7.  All the samples were  collected with the filter and probe operated
at 160°F except for those samples where the probe was heated to 204°F.
There were two basic patterns of analysis.  Most samples were desiccated at
ambient temperature and weighed, and then conditioned in a laboratory oven
at temperatures varying from 160°C to 316°C for periods of 6 to 24 hours
before being desiccated and reweighed.  The remaining samples were

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            Table 4.  SAMPLE MATRIX FOR COAL-FIRED  BOILER

Run
no.
1
2
3
4
5
6
7
8
9
10

Sampl e
train no.
1A
IB
1C
ID
2A
2B
2C
2D
3A
3B
3C
3D
' 4A
4B
4C
4D
5A
5B
5C
5D
6A
6B
6C
6D
7A
7B
7C
7D
8A
8B
8C
8D
9A
9B
9C
9D
10A
10B
IOC
10D

MSB
160°C (320°F)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Sampl e method3
M5B-P400
160°-204°C (320°-400°F)

X
X

X
X


X
X

X
X


M5W
160°C (320°F)
X
X

X
X


X
X

X
X


a M5B - Probe and filter  heated  to 160°C  (320°F).
  M5B-P400 - Probe heated to 204°C; filter heated to 160°C.
  M5W - Probe and filter  heated  to 160°C; water rinse of nozzle, probe,
   and front filter holder glassware.

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          Table 5.  ANALYTICAL MATRIX FOR COAL-FIRED BOILER
Run
no.
1
2
3
4
5
6
7
8
9
10
Samp! e
train no.
1A
IB
1C
ID
2A
2B
2C
2D
3A
3B
3C
3D
4A
4B
4C
4D
5A
5B
5C
50
6A
6B
6C
6D
Sampl e
method
Thermogravi metric
conditionings
Ambient
160° 232°
316°C
MSB X
MSB X
M5BW
M5BW
M5B-P400J
M5B-P400J
MSB
MSB
M5BW
M5BW
MSB
MSB
MSB
MSB
M5B-P400
M5B-P400
MSB
MSB
MSB
M5B
M5B
MSB
M5BW
M5BW
7A IM5B-P400
7B IM5B-P400
7C M5B
7D M5B
8A M5BW
8B M5BW
8C MSB
8D MSB
9A MSB
9B MSB
9C MSB -P 400
9D M5B-P400
10A MSB
108 MSB
IOC MSB
10D M5B
X (24)
X
X (24)
X


X
X (24)
X
X
X
X (24)
X
X (24)
X (24)
X (24)

X (24)
X
Ambient
232°
316°C



X
X
X
X (24)



X (24)
X (24)
X (24)
X
Ambient
316°C


X
X (24)
X
X




X (24)
X (24)
1
Water
soluble sulfate
determination*5
X
X

X
X


X
X

X
X


a Thermogravimetric conditioning  of  probe  rinse  and filter fractions at
   indicated temperatures after initial  desiccation and ambient weights
   were obtained.   The designation  (24)  for  selected  samples indicates a
   heat period of 24 hours.   All  other samples were heat-conditioned for
   6 hours.

b In this procedure, the mass of total  water soluble  sulfates  in the
   sample was determined and subtracted from the total sample  mass.

NOTE:,  All  back halves represent  a modified  Method 8, with analysis for
       sulfates as sulfuric  acid  and sulfur  dioxide.
                                      8

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              Table 6.   SAMPLE MATRIX  FOR OIL-FIRED BOILER

Run
no.
1
2
3
4
5
6
7
8
9
10

Sampl e
train no.
1A
IB
1C
ID
2A
2B
2C
2D
3A
3B
3C
3D
4A
4B
4C
4D
5A
5B
5C
5D
6A
6B
6C
6D
7A
7B
7C
7D
8A
8B
8C
8D
9A
9B
9C
90
IDA
10B
IOC
10D

MSB
160°C (320°F)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Sample method3
M5B-P400
160°-204°C (320°-400°F)


X
X
X
X



X
X

X
X

M5W
160°C (320°F)
X
X
X
X




X
X



a MSB - Probe and filter heated to  160°C.
M5B-P400 - Probe heated to 204°C;  filter heated  to 160°C.
M5W - Probe and filter heated  to 160°C;  water  rinse of nozzle, probe,
 and front filter holder glassware.

                                     9

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           Table 7.  ANALYTICAL MATRIX FOR OIL-FIRED BOILER
Run
no.
1
2
3
4
b
6
V
8
9
10
1
Sample I Sample
train no. I method
1A
IB
1C
ID
2A
2B
2C
2D
3A
3B
3C
4D
4A
4B
4C
4D
5A
5B
5C
5D
6A
68
6C
6D
7A
7B
7C
7D
8A
8B
8C
8D
9A
98
9C
9D
10A
10B
IOC
10D
Thermogra vi metric
conditioning3
Ambient
160° 232°
316°C
M5BW |
M5BW
MSB X
MSB 1 X
MSB
MSB
M5BW
M5BW
MSB
MSB
M5B-P400
M5B-P400
M5B-P400
M5B-P400
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
M5BW
MSB
M5BW
MSB
M5B
M5B-P400
MSB
M5B-P400
MSB
MSB
MSB
MSB
MSB
M5B-P400
MSB
M5B-P400
X (24)
X (24)
X
X
X
X
X
X
X
X
X
X
X (24)
X (24)


X (24)
X
X (24)
X


Ambient
232°
316°C





X (24)
X (24)
X
X
X
X


X
X
X
X
Ambi ent
316°C
Water
soluble sulfate
determination^
X
X
X
X






X (24)
X (24)
X
X





X
X



  Thermogravimetric conditioning of probe rinse and filter fractions at
   indicated  temperatures after initial desiccation and ambient weights
   were  obtained.  The  designation (24) for selected samples indicates a
   heat  period  of 24  hours.  All other samples were heat-conditioned for
   6  hours.

  in  this procedure,  the mass of total water-soluble sulfates in the
   sample was determined and subtracted from the total sample mass.
NOTE:
All  back halves represent a  modified  Method 8, with analysis for
 sulfates as sulfuric  acid and  sulfur dioxide.
                                    10

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treated with ammonium hydroxide  to  convert any sulfuric acid to ammonium
sulfate before the total  particulate matter was weighed.  The water soluble
sulfate content was then  measured by a  separate method and subtracted from
the total  particulate matter weight.  This procedure, identified as Method
5W here, is a modification of a  procedure used by the Texas Air Control
Board.   The full text of  the procedure  can be found  in the emission test
reports.

Discussion
     The results from the coal-fired boiler  test are summarized in Table 8,
and the results from the  oil-fired  boiler test are summarized in Table 9.
The average and 95 percent confidence  interval for the average of these
data are shown graphically in Figures  1 and  2.
     There are some noticeable differences  in the results from the two
separate tests.  Perhaps, the most  striking  is that  the samples from the
coal-fired boiler experienced the largest weight change going from ambient
conditioning to conditioning at 160°C,  while the samples from the oil-fired
boiler  showed the greatest change between conditioning at 225°C and 316°C.
     As expected, the particulate weight measured by Method 5W was, in
general, lower than that measured after heating, though those samples
heated  to 316°C showed relatively good  agreement.  This was expected since
Method  5W measures all water soluble sulfates and not just sulfuric acid.
It also indicated that ammonium sulfate which decomposes at 279°C was
probably present in the samples.
                                       11

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Table 8. COMPARISON OF FILTERABLE PARTICULATE CONCENTRATION FROM A
COAL-FIRED BOILER AFTER HEAT CONDITIONING AT INDICATED TEMPERATURES^
Run no.
1A
IB
2C&
2D
3C
3D
4A
48
5A
5Bb
5C
5D
6A
6B
7C
7D
8Cb
8D
9A&
9B
lOAb
10B
lOCb
10D
Sample
type
M5B
MSB
M5B
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
MSB
Average
Ambi ent
Total
weight,
*r9
25.9
79.7
56.6
34.3
. 58.8
69.6
26.7
26.7
47.6
46.2
54.0
48.2
33.6
33.8
80.0
86.3
92.3
88.8
57.1
58.2
45.0
38.5
85.4
77.3
Concen-
tration,
mg/dNm^
12.0
37.6
28.5
17.5
18.9
22.0
7.8
7.9
14.2
13.9
16.6
14.8
10.6
10.7
25.5
26.5
29.5
27.3
17.3
17.8
13.5
11.7
26.3
23.1
„ 18-8
ac = 7.8
N = 24
160°C
Total
weight,
mg
13.9
16.0
18.2
11.8
—
— .
21.1
16.3
24.4
19.5
28.6
31.3
19.0
19.7
_
25.5
27.7
Concen-
tration,
mg/dNm3
6.4
7.5
9.2
6.0
_
^
6.3
4.9
7.7
6.1
9.1
9.6
6.1
6.1
_
7.7
8.4
c 7'2
ac = 1.4
N = 14
232°C
Total
weight,
mg
8.8
10.3
19.4
9.1
_
12.1
17.1
17.9
17.1
16.4
20.9
15.5
22.4
30.4
19.7
18.5
25.4
24.8
22.3
30.1
29.4
Concen-
tration,
mg/dNm3
4.1
4.9
9.8
4.6

3.5
5.1
5.4
5.3
5.0
6.6
4.9
7.2
9.3
6.3
5.7
7.8
7.5
6.8
9.3
8.8
6.4
0C = 1.9
N = 20 |
316°C
Total
weight,
mg
6.9
8.9
14.6
5.4
13.1
26.6
11.0
11.2
14.7
13.9
13.2
13.2
17.8
11.6
13.6
26.5
15.5
12.3
18.5
20.5
21.2
19.2
25.9
22.6
Concen-
tration,
mg/dNm
3.2
4.2
7.4
2.8
4.2
8.4
3.2
3.3
4.4
4.2
4.1
4.1
5.6
3.7
4.3
8.1
5.0
3.8
5.6
6.3
6.4
5.8
8.0
6.7
5.1
a~ = 1.7
N = 25

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                       Table 8.  COMPARISON OF FILTERABLE PARTICIPATE CONCENTRATION  FROM A
                      COAL-FIRED BOILER AFTER HEAT CONDITIONING AT INDICATED  TEMPERATURES*
                      ._   	                  (Continued)
1
1 Samp! e
Run no. | type
2A*5 IM5B-P400
2B IM5B-P400
4~C JM5B-P400 |
4D IM5B-P400
7A JM5B-P400 |
7B IM5B-P400
9~CE JM5B-P400 |
9D JM5B-P400
Average
I AmTT
Total
weight,
mg
1 29.1
26.2
1 40.8
27.2
[ 4b.4
38.0
I 3176
39.0
a(
K
'ent
Concen-
tration,
mg/dNm3
14.2
13.0
12.0
7.9
14.1
11.6
10.0
12.0
11.8
: = 2.1
= 8
16(
Total
weight,
mg
17.2
12.6
w»
26.5
20.5

c
)"C
Concen-
tration,
mg/dNm3
8.4
6.3

8.0
6.3
:
7.2
>c = 1.1
N = 4
23;
Total
weight
mg
17.3
8.7
18.6
22.0
19.3
20.1
oc
F
,oc
Concen-
tration,
mg/dNm3
8.4
4.3
5.5
6.7
5.9
6.2
, 6.2
' = 1.4
1 = 6
31f
Total |
weight, I
mg 1
14.1
7.0
15.8
12.4
15.7
17.1
15.4
17.9
ac
r
56C
Concen-
tration,
mg/dNm3
6.9
3.5
4.7
3.6
4.8
5.2
4.9
5.5
, 4.9
' = 1.1
J = 8
a  Includes both filter and probe rinse fractions.
b  Heat conditioning intervals for these samples  were 24 hours; all  others were 6 hours.
c  Standard deviation with N-l weighting for  sample data.
d  Number of data points.

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Table 9.  COMPARISON  OF  FILTERABLE  PARTICIPATE  CONCENTRATION  FROM AN



 OIL-FIRED BOILER AFTER  HEAT  CONDITIONING  AT  INDICATED TEMPERATURESa
Run no.
1C
ID
2A&
2Bb
3A
3B
	 1
4C
4D
5A
5B
5Ch
5Db
Samp! e
type
M5B
M5B
M5B
M5B
M5B
M5B
M5B
M5B
M5B
M5B
M5B
M5B
Ambient
Total
weight,
mg
336.7
309.3
389.7
378.0
356.9
376.6
348.6
346.0
235.5
230.9
219.2
217.9
Concen-
tration,
mg/dNm3
185.0
168.9
196.5
190.5
186.8
199.2
201.8
196.5
165.0
163.5
167.2
163.7
reiTT 1
Total
weight,
mg
283.6
265.6
337.9
327.7
311.1
332.4
319.8
317.5
201.2
196.0
186.1
183.5
Concen-
tration,
mg/dNm3
155.8
145.1
170.4
165.2
162.8
175.8
185.2
180.3
141.0
138.8
142.0
137.9
2~3T°C
Total
weight,
mg
266.1
251.0
1
326.6
304.2
298.2
317.1
310.6
306.2
185.4
182.8
178.5
173.7
Concen-
tration,
mg/dNm3
1 1
146.2
137.0
1 1
164.7
153.3
1 1
156.0
167.7
179.8
173.9
129.9
129.5
136.2
130.5
	 316 (
otal I
weight,
mg
194.8
226.1
1 1
222.2
175.9
251.1
241.7
r— "•"• 1
1 1
241.1
234.6
152.6
120.0
103.7
113.3
C
Concen-
tration,
mg/dNm3
107.0
123.5
I
112.0
88.7
131.4
127.8
139.6
133.2
106.9
85.0
79.1
85.1

-------
Table 9.   COMPARISON  OF FILTERABLE  PARTICIPATE  CONCENTRATION  FROM  AN

 OIL-FIRED BOILER AFTER HEAT  CONDITIONING  AT  INDICATED TEMPERATURES^
                                 (Continued)
Run no.
6Ab
6Bb
6C
6D
7B
7D
8Ab
8C
9A&
9Bb
9C
9D
10A
IOC
Sampl e
type
M5B
M5B
M5B
MSB
M5B
M5B
M5B
M5B
M5B
MSB
MSB
MSB
MSB
MSB
Average
Ambient
Total
weight,
mg
229.3
216.8
169.6
186.1
221.9
215.5
156.8
112.6
252.9
261.2
204.7
224.6
260.6
210.0
Concen-
tration,
mg/dNm3
161.1
155.3
140.0
150.3
159.0
157.3
181.1
131.5
171.7
180.9
151.8
162.3
171.8
159.6
169.9
a = 18.3
N = 26
160°C
Total
weight,
mg
-
-
105.6
89.8
-

Concen-
tration,
mg/dNm3


121.9
104.9


r 151.9
a = 23.0
N = 14
232°C
Total
weight,
mg
182.8
168.3
135.1
145.1
152.1
153.0
100.2
84.9
-
203.1
176.8
Concen-
tration,
mg/dNm3
128.5
120.6
111.6
117,2
109.0
111.7
115.7
99.2

133.9
134.4
135.7
a = 22.3
N = 22
316°C
Total
weight,
mg
127.5
101.2
104.8
113.0
101.6
93.5
51.5
51.2
117.5
116.7
122.1
119.3
157.8
123.5
Concen-
tration,
mg/dNm3
89.6
72.5
86.5
91.3
72.8
68.2
59.5
59.8
79.8
80.8
90.6
86.2
104.0
93.8
r 94.4
a = 22.5
N = 26

-------
                      Table 9.   COMPARISON OF FILTERABLE PARTICULATE CONCENTRATION FROM AN

                       OIL-FIRED BOILER AFTER HEAT CONDITIONING AT INDICATED TEMPERATURESa
                                                  (Continued)
Run no.
3C
3D
4A
4B
8B
8D
10B
10D
Sampl e
type
M5B-P400
M5B-P400
M5B-P400
M5B-P400
1
M5B-P400
M5B-P400
M5B-P400
M5B-P400
Average
Ambient 160"C 232UC 316UC
Total
weight,
mg
335.2
351.4
398.9
398.0
111.5
105.5
226.1
213.8
Concen-
tration,
rng/dNm-^
211.1
193.8
202.2
194.0
134.5
133.2
151.6
158.8
172.4
a = 31.4
N = 8
Total
weight,
mg
296.8
314.3
369.1
365.6
87.9
85.3
-
Concen-
tration,
mg/dNm3
186.9
173.4
187.1
178.2
106.0
107.7

r 156.5
a = 38.8
N = 6
Total
weight,
mg
284.2
300.3
357.7
349.9
79.3
74.2
179.9
181.6
Concen-
tration,
mg/dNm3
179.0
165.6
181.3
170.5
95.7
93.7
120.7
134.9
c 142-7
a = 36.4
N = 8
Total
weight,
mg
230.8
245.7
291.5
276.8
59.1
55.7
136.0
124.7
Concen-
tration,
mg/dNm3
145.3
135.5
147.7
134.9
71.3
70.3
91.2
92.6
r 111.1
° = 33.1
N = 8
a  Includes both filter and probe rinse  fractions.
b  Heat conditioning intervals for these samples were 24 hours, all others were 6 hours.
c  Standard deviation with N-l weighing  for  sample data.
d  Number of data points.

-------
   30
          AMBIENT
   20
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o
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160
100
                         160-232 °C
                     ._.   IUU-£..4<
                                           AMBIENT
                160232-
                316 °C
I
                                                    160°C
                                   1
             160 232 °C
                                                              \
                                                                      160-
                      232-316 °C
                         f
i
           MSB-—>-OVEN    OVEN
                   HEAT    HEAT
                 OVEN     MSB	»OV£N    OVEN    OVEN    M5W
                 HEAT     P400     HEAT    HEAT    HEAT

                 SAMPLE/ANALYSIS CONDITIONS
                              Figure 1.   Coal-fired boiler.

-------
  210
— AMB
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AMBIENT
ENT 16C
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  160
  150 —
  140 —
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  100 —
   90 —
   80 —
   70
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                          160-232 °C
                                                             160-232 °C
                                    160-232-
                                    316 °C
                                                                                       -1
                                                   160-232-
                                                    31S"°C
                                                              I
            MSB-
• QVF.W
 HEAT
OVEN
HEAT
OVEN
HEAT
MSB-
P400
                                                     •OVEN
                                                      HEAT
OVEN
HEAT
OVEN
HEAT
M5W
                                   SAMPLE/ANALYSIS CONDITIONS
                              Figure 2.
                        Oil-fired boiler.
                            18

-------
     One of the principal  purposes  of  the  testing program was to estimate
the repeatability of Method 58.   As shown  in Figures 1 and 2, the precision
(which also includes temporal  variations)  of the method varies somewhat
with the method of analysis.   The poorest  precision was usually produced by
ambient conditioning followed  by  weighing  while Method 5W usually showed
the best precision.   Some care must be exercised when analyzing the
precision of the samples taken at the  oil-fired boiler, because there were
a number of process  upsets during these tests which caused substantial
variations in the emission rate from test  to test.  These variations
between runs tend to obscure the  variation between samples within a run.
To eliminate this between-run  variation, the standard deviation for the
samples within a run were averaged  over all runs for the different
analytical techniques and plotted along with the 95 percent confidence
interval of the average in Figures  3 and 4.  These figures show that the
samples from the oil-fired boiler follow a similar pattern to that of the
coal-fired boiler.
     When the results from the samples collected with the probe at 204°C
are compared with those collected with the probe at 160°C, one can see that
the samples collected with the higher  temperature probe weigh less after
ambient conditioning.  This indicates  that the higher probe temperature is
successful in reducing the amount of condensed sulfuric acid collected.
This is not unreasonable since it is more  difficult to maintain an even
temperature throughout the length of the probe, and the higher overall
temperature is more likely to  ensure that  the gas stream does not contact
any sections of the probe that are  cooler  than 160°C.  However, after
                                      19

-------
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160 °C 1
i :
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IENT
i
i

160 232 °C 	
OC
i
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160-232-
316 °C
1 <
1 1

i
M5B — frOVEN OVEN OVEN M5B 	 »• OVEN OVEN OVEN M5W
HEAT HEAT HEAT P400 HEAT HEAT HEAT
                                                   SAMPLE/ANALYSIS CONDITIONS
                                               Figure 3.   Coal-fired boiler.

-------
                   20
ro
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a
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i

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-r 160-232-







4


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y
t i

MSB — *OVEN OVEN OVEN M5B- — * OVEN OVEN OVEN M5W
HEAT HEAT HEAT P400 HEAT HEAT HEAT
                                              SAMPLE/ANALYSIS CONDITION
                                           Figure 4.   Oil-fired boiler.

-------
conditioning the samples  at  temperatures of 160°C or higher, this
difference in weight disappears.  This is shown clearly in Tables 10 and
11.  These tables are summaries  of the data which have been normalized
using Method 58 samples conditioned at 160°C as the reference.

Conclusions
     Samples collected at 160°C  will  contain minimal amounts of sulfuric
acid compared to samples  collected at 120°C (250°F).  While heating the
probe to 204°C during sampling  is  even more effective in preventing
condensed sulfuric acid  from collecting on the sample, the extra effort
required to maintain this temperature in the probe is not justified since
any condensed sulfuric acid  can  be satisfactorily removed by heating the
sample in an oven after collection.
     The repeatability of the measurement  is improved by heating the
samples to 160°C after collection  as  compared to ambient conditioning, but
there is little or no gain in precision upon heating to higher
temperatures.  Although,  of  all  the methods tested, Method 5W showed the
best repeatability, it cannot distinguish  between sulfuric acid and other
water soluble sulfates and is not  a suitable technique for measuring NSAPM
from electric utility boilers.
     Collecting samples for NSAPM  at  a  probe and filter temperature of
160°C and conditioning these samples  at 160°C prior to weighing is the
best technique for measuring NSAPM from electric utility boilers.  The
conditioning temperature of 160°C  provides the  best compromise between
                                      22

-------
           Table 10.   COAL-FIRED  BOILER



RATIO OF CONCENTRATION TO REFERENCE  CONDITION



            (MSB heated to 160°C)        	
Condition
Samp! e
Analysis
1. Ambient desiccation
2. Oven heat:
Sequenced 160°C
232°C
315°C
3. Water extraction
M5B
2.61

1.00
0.89
0.71
--
M5B-P400
1.64

1.00
0.86
0.68

M5W




--
0.71
                          23

-------
         Table 11.   OIL-FIRED BOILER



RATIO OF CONCENTRATION TO REFERENCE  CONDITION



          (MSB heated to 160°C)
Condition
Analysis
Sampl e
1. Ambient desiccation
2. Oven heat:
Sequenced



160°C
232°C
315°C
3. Water extraction
M5B
1.12

1.00
0.89
0.62
__
M5B-P400
1.13

1.03
0.94
0.73
--
M5W
--

--
--
—
0.55
                        24

-------
a temperature high enough  to  evaporate  any condensed sulfuric acid but not
so high as to decompose or evaporate  other materials which are intended to
be counted as particulate  matter.

Bibliography
     1.  Pierce,  R.R.   Estimating Acid  Dew Points  in Stack Gases.  Chemical
Engineering.  Vol. No.: 125-128.   April  1977.
     2.  PEDCo Environmental.  Summary  Report:  Compound Evaluation of
Methods 5 and 17.  Prepared for U.S.  Environmental  Protection Agency.
Research Triangle Park, N.C.   February  1983.   56 p.
     3.  Cornett, C.L. and W.H. McDonald (Monsanto Research Corporation).
Emission Test Report.   Caterpillar Tractor Company, East Peoria,  Illinois.
Prepared for U.S. Environmental Protection Agency.  Research Triangle Park,
N.C.  EMB Report 81-IBR-14.  June 1982.
     4.  Cornett, C.L. and R.G. Beer.  (Monsanto Research  Corporation).
Emission Test Report.   DuPont Corporation, Parkersburg, West Virginia.
Prepared for U.S. Environmental Protection Agency.  Research Triangle Park,
N.C.  February 1982.  Emission Measurement Branch  Report 80-IBR-12.
     5.  Day, D.R.  (Monsanto Research  Corporation).   Emission Test Report.
Boston Edison Company, Everett, Massachusetts.  Prepared for U.S.
Environmental Protection Agency.  Research Triangle Park,  N.C.   July 1980.
Emission Measurement Branch Report 81-IBR-15.
                                      25

-------
     6.  Prohaska,  J.   (PEDCo  Environmental).  Evaluation of Method 5B
at a Coal-Fired Boiler.   Prepared  for  U.S. Environmental Protection
Agency.  Research Triangle Park, N.C.   September 1983.  Emission
Measurement Branch  Report	.
     7.  Prohaska,  J.   (PEDCo  Environmental).  Evaluation of
Method 5B at an Oil-Fired Boiler.  Prepared for U.S. Environmental
Protection Agency.   Research Triangle  Park, N.C.  September 1983.
Emission Measurement Branch Report  	.
                                      26

-------
                                       TECHNICAL REPORT DATA
                               (Please read Instructions on the reverse before completing)
                                 2.
                                                                 3. RECIPIENT'S ACCESSION NO.
 4. TITLE AND SUBTITLE
  Development and  Evaluation  of Method  5B -  Background
   Information for Proposed Reference Method
               5. REPORT DATE
                 September 1984
               6. PERFORMING ORGANIZATION CODE
  Gary  McAlister
                                                                 8. PERFORMING ORGANIZATION REPORT NO.
                                ND ADORES
  Emission Measurement Branch
  Emission Standards  and Engineering Division
  U.S.E.P.A.
  Research Triangle Park, North Carolina  27711
                                                                 10. PROGRAM ELEMENT NO.
               11. CONTRACT/GRANT NO.
            G AGENCY NAME AND ADDRESS
                                                                 13. TYPE OF REPORT ANO PERIOD COVERED
  Same  as  above
                                                                 14. SPONSORING AGENCY CODE

                                                                    EPA 200/04
  6. ABSTRACT
       This  report discusses the development of Method 5B.  Results from  tests at

  fossil-fuel-fired  boilers are  summarized  and compared.
                                  KEY WORDS AND DOCUMENT ANALYSIS
                   DESCRIPTORS
18. DISTRIBUTION STATEMENT

  Release unlimited
                                                 b.lDENTIFIERS/OPEN ENDED TERMS
19. SECURITY CLASS (ThisReport)
  Unclassified
                                                  !0. SECURITY CLASS (Thispage)
                                                    Unclassified
EPA Form 2220-1 (Rev. 4-77)    PREVIOUS EDITION is OBSOLETE
                                                                              c.  cos AT I Field/Group
21. NO. OF PAGES
     21
                             22. PRICE

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...w—

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