United States
Environmental Protection
Agencv
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 84-GLS-9
October 1984
Air
NESHAP - Glass
Manufacturing
Arsenic
Emission Test Report
Indiana Glass Company
Dunkirk, Indiana
-------
SUMMARY TEST REPORT
STANDARDIZATION AND VALIDATION OF
METHODOLOGY TO MEASURE INORGANIC
ARSENIC EMISSIONS FROM
STATIONARY SOURCES
Indiana Glass Company
Dunkirk, Indiana
by
PEI Associates, Inc.
(formerly PEDCo Environmental, Inc.)
11499 Chester Road
P.O. Box 46100
Cincinnati, Ohio 45246-0100
Contract No. 68-02-3767
Work Assignment No. 66
Change No. 1
PN 3583-6
and
Contract No. 68-02-3849
Work Assignment No. 11
PN 3615-11
Task Manager
Mr. Daniel Bivins
Emission Standards and Engineering Division
Emission Measurement Branch
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
October 1984
-------
DISCLAIMER
This report was furnished to the U.S. Environmental Protec-
tion Agency, Emission Measurement Branch, by PEI Associates,
Inc., Cincinnati, Ohio, in fulfillment of Contract No. 68-02-
3767, Work Assignment No. 66, Change No. 1. Its contents are
reproduced herein as received from PEI. The opinions, findings,
and conclusions are those of the authors and not necessarily
those of the EPA. Mention of company or product names does not
constitute endorsement or recommendation for use.
11
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CONTENTS
Paqe
Figures iv
Tables vi
Acknowledgment vii
1. Introduction 1-1
2. Summary and Discussion of Test Results 2-1
2.1 Sampling and analytical protocol 2-1
2.2 Test results—elevated temperature runs 2-2
2.3 Method 108 traverse test results 2-15
2.4 Process samples 2-18
3. Project Quality Assurance 3-1
4. Sampling Location and Test Methods 4-1
4.1 Sampling and analytical procedures 4-7
5. Process Operation 5-1
Appendices
A Computer Printouts and Example Calculations A-l
B Field Data B-l
C Laboratory Data C-l
D Sampling and Analytical Procedures D-l
E Equipment Calibration Procedures and Results E-l
F Process Description and Operation During Testing F-l
111
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FIGURES
Number Page
2-1 Quad Train System for Elevated Temperature Tests 2-3
3-1 Pre-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-1, Train A) 3-6
3-2 Pre-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-5, Train B) 3-7
3-3 Pre-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-8, Train D) 3-8
3-4 Pre-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-10, Train C) 3-9
3-5 Pre-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-9, Single Point-Traverse
Tests) 3-10
3-6 Pre-Test Thermocouple Digital Indicator Audit
Data Sheet (Indicator No. 220) 3-11
3-7 Pre-Test Thermocouple Digital Indicator Audit
Data Sheet (Indicator No. 221) 3-12
3-8 Pre-Test Onsite Audit Data Sheet 3-13
3-9 Pre-Test Onsite Audit Data Sheet 3-14
3-10 Mid-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-1) 3-15
3-11 Mid-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-5) 3-16
3-12 Mid-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-8) 3-17
3-13 Mid-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-10) 3-18
IV
-------
FIGURES (continued)
Number Page
3-14 Mid-Test Thermocouple Digital Indicator Audit Data
Sheet (Indicator No. 220) 3-19
3-15 Mid-Test Thermocouple Digital Indicator Audit Data
Sheet (Indicator No. 221) 3-20
3-16 Mid-Test Onsite Audit Data Sheet 3-21
3-17 Mid-Test Onsite Audit Data Sheet 3-22
3-18 Post-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-1) 3-23
3-19 Post-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-5) 3-24
3-20 Post-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-8) 3-25
3-21 Post-Test Audit Report: Dry Gas Meter by Critical
Orifice (Meter Box FB-11) 3-26
3-22 Post-Test Thermocouple Digital Indicator Audit Data
Sheet (Indicator No. 220) 3-27
3-23 Post-Test Thermocouple Digital Indicator Audit Data
Sheet (Indicator No. 221) 3-28
3-24 Example of Unacceptable Dry Gas Meter Audit 3-29
3-25 Example of Onsite Calibration Data Sheet 3-31
4-1 Quad Train System for Elevated Temperature Tests 4-2
4-2 Four-Train Sampling System Showing Nozzle, Pitot
Tube, and Thermocouple Position 4-3
4-3 Furnace Exit Stack Elevation 4-5
4-4 Furnace Exit Stack Sampling Port Location 4-6
v
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TABLES
Number Page
2-1 Summary of Sample Conditions 2-4
2-2 Summary of Arsenic Analytical Results - Quad
and Reference Train Runs 2-5
2-3 Statistical Data for Grouped Runs 2-7
2-4 Statistical Data for Grouped Runs - EMSL Quad
Train Tests 2-10
2-5 Summary of Sample and Flue Gas Conditions
Arsenic Traverse Tests 2-16
2-6 Summary of Arsenic Analytical Results - Traverse
Train 2-17
2-7 Process Sample Analytical Results 2-19
3-1 Field Equipment Calibration 3-3
3-2 Arsenic Blank Data 3-32
3-3 Arsenic Laboratory Reagent Blank Data 3-34
3-4 Linear Regression Data (Flame) 3-36
3-5 Arsenic Audit Results 3-37
3-6 Arsenic Standard Addition Results 3-39
3-7 Linear Regression Data (Furnace) 3-41
3-8 Duplicate Analysis Data 3-43
vi
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AC KNOWLEDGMENT
This test program was conducted for the Emission Standards
and Engineering Division of the EPA Office of Air Quality Plan-
ning and Standards. The program was part of a larger study
directed by EPA's Source Branch of the Environmental Monitoring
Systems Laboratory, Quality Assurance Division, to evaluate
proposed EPA Method 108. Mr. Thomas E. Ward was the EMSL Task
Manager.
Mr. Daniel Bivins, EPA-EMB Task Manager, provided overall
project coordination and guidance and observed the test program.
Mr. Ronald Myers, EPA lead engineer, Industrial Studies Branch,
provided project coordination relative to process operation and
overall project scope. Mr. Larry Keller, representing Radian
Corporation (an EPA contractor) monitored process operation
throughout the test period. Mr. Charles Bruffey was the PEI
Project Manager. Principal authors were Messrs. Charles Bruffey
and Thomas Wagner.
VII
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SECTION 1
INTRODUCTION
Arsenic is listed as a hazardous air pollutant under Section
112 of the Clean Air Act (National Emission Standards for Hazard-
ous Air Pollutants). To protect public health from unreasonable
risks associated with exposure to airborne arsenic, the U.S.
Environmental Protection Agency (EPA) has developed standards to
decrease inorganic arsenic emissions from the following source
categories: high-arsenic primary copper smelters, low-arsenic
primary copper smelters, and glass manufacturing plants.
To support the standards review process and provide addi-
tional arsenic emissions data from glass manufacturing facili-
ties, PEI Associates, Inc., under contract to Research Triangle
Institute and directed by the Source Branch of the EMSL Quality
Assurance Division and the Emission Standards and Engineering
Division - Emission Measurement Branch, performed a series of
atmospheric emission tests on a glass melting furnace at Indiana
Glass Company in Dunkirk, Indiana. These tests were conducted
from May 17 through 19, 1984, as part of a larger study designed
to evaluate the sampling and analytical procedures for measuring
inorganic arsenic from stationary sources. Proposed Method 108*
provides total arsenic results (particulate plus gaseous frac-
tion) .
40 CFR 61, Appendix B, Method 108, July 1983.
1-1
-------
The primary objective of this test program was to determine
the precision of proposed Method 108. Relative standard devia-
tions (the standard deviation expressed as a percent of the mean
value) of four-train (quad) sample runs were used to estimate
method precision. A total of nine quad train runs representing
36 individual samples were conducted using Method 108 sampling
and analytical procedures as described in the Quality Assurance
Project Plan developed and submitted in January 1984 to the EPA
Environmental Monitoring Systems Laboratory. These data are
summarized in a report issued to EMSL-QAD.
In this specific portion of the test program, four quad-
train tests were conducted using Method 108 procedures except
that probe and filter temperatures were elevated to approximately
204°C and 288°C in order to evaluate the effects of increased
sampling train temperature on arsenic distribution in the sam-
pling train. During these runs, a single Method 108 sampling
train (121°C) was run for reference purposes. Three Method 108
traverse tests were also conducted to provide additional data in
support of the arsenic standards developed to date.
Section 2 summarizes and discusses the test results; Section
3 addresses quality assurance considerations specific to this
project; Section 4 describes the sampling locations and test
procedures; and Section 5 describes source operation. Appendix A
presents sample calculations and computer printouts; Appendices B
and C contain the field data sheets and laboratory analytical
1-2
-------
results, respectively; Appendix D details the sampling and ana-
lytical procedures; Appendix E summarizes equipment calibration
procedures and results; and Appendix F contains a process descrip-
tion and the furnace operating data for the test period.
1-3
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SECTION 2
SUMMARY AND DISCUSSION OF TEST RESULTS
2.1 SAMPLING AND ANALYTICAL PROTOCOL
A four-train (quad) sampling system was used to collect
samples at the furnace exit stack. This system allows four
trains to sample simultaneously at essentially a single point in
the stack (see Section 4).
Because this sampling approach allows simultaneous sampling
at essentially a single point, it reduces the effect of varia-
tions in the velocity and particulate profiles on the sampling
results. It also permits a statistically significant number of
samples to be taken in a short amount of time. Further, since
two of the four trains are identical for every run, the within-
train precision can be determined at the same time as the rela-
tionship of the different trains is being compared.
The Quad runs conducted were designed to evaluate the effect
of arsenic collection at elevated sampling temperatures. Two of
the trains were heated to approximately 204°C (400°F) and two
trains were heated to approximately 288°C (550°F) for comparative
purposes. Additionally, in three of the four quad tests con-
ducted, backup filters were maintained at approximately 121°C
(250°F) prior to the impinger section.
2-1
-------
Figure 2-1 depicts the quad train configuration used for
these tests. Individual train components were recovered and
analyzed for arsenic separately to evaluate the distribution of
arsenic in the sampling train. In each train, the contents of
the first and second impingers were recovered, combined, and
analyzed for arsenic and the third and fourth impingers were
recovered, combined, and analyzed for arsenic. The probe rinse
and front filter were recovered and analyzed according to pro-
cedures defined in Method 108. In Trains A and D, the back-half
glassware of the front filter, the glass connector, and the
front-half glassware of the backup filter were rinsed with 0.1 N
NaOH and this rinse was analyzed for arsenic. The backup filter
was analyzed separately in each case.
During these runs, a single Method 108 sampling system
(designated RT) (121°C) was run for reference purposes. Three
multipoint traverse tests utilizing a single Method 108 train
were also conducted at the completion of the quad-train tests.
In each train, the probe and filter temperatures were set at
a predetermined temperature and monitored using multiterminal
digital indicators with thermocouple leads located in each probe
and immediately behind the Method 5 filter frits.
2.2 TEST RESULTS—ELEVATED TEMPERATURE RUNS
Table 2-1 summarizes sampling conditions for the quad train,
reference train, and traverse train (designated CD) test runs.
Table 2-2 summarizes the arsenic analytical results by sample
2-2
-------
BACKUP
METHOD 5
FILTER
IMPINGER
TRAINS
(204°C) (288°C)
HEAT BOXES
BACKUP
'METHOD 5
FILTER
(12TC)
Az
B-
FRONT VIEW
B A D C
CO CO CD CO
oo oo
er oc a; of.
D. Q- CL O.
OD OA
oC OB
BACK VIEW
Figure 2-1. Quad train system for elevated temperature tests,
2-3
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TABLE 2-1. SUMMARY OF SAMPLE CONDITIONS
Run
No.
IDA
10B
IOC
10D
10-RT
11A
11B
11C
11D
11 -PT
1ZA
12B
12C
120
12-RT
13A
13B
13C
13D
13-RT
CD-I
CO-2
CD-3
Sampling
type
Modified
Method 108
Method 108
Modified
Method 108
Method 108
Modified
Method 108
Method 108
Modified
Method 108
Method 108
Method 108
Method 108
Method 108
Date (1984)
and
time (24-h)
5/17
11:45-12:55
5/17
11:45-12:55
5/17
17:11-18:21
5/17
17:11-18:21
5/18
10:59-12:09
5/18
10:59-12:09
5/18
15:36-16:46
5/18
15:36-16:46
5/19
10:32-11:45
5/19
13:05-14:18
5/19
15:12-16:22
Metered
volume,
dsm3
1.07
1.12
1.18
1.09
1.41
1.02
1.12
1.14
1.00
1.33
1.23
1.33
1.34
0.29
1.53
1.14
1.28
1.30
1.13
1.37
1.03
1.06
1.07
Isoki-
netic, %
101.0
97.5
101.2
100.4
96.0
101.2
97.8
100.2
99.3
98.7
107.1
103.0
101.2
101.2
99.8
94.5
98.2
101.4
100.0
100.6
105.6
102.1
100.3
Mois-
ture, *
8.4
8.9
8.4
8.6
8.1
8.5
6.9
8.3
8.8
8.4
8.6
8.4
8.6
9.1
8.5
8.9
8.7
8.6
9.7
9.0
8.0
8.3
7.7
Sampling conditions
Gas
temper-
ature, °C
298
298
298
298
301
301
301
301
301
311
286
286
286
286
292
274
274
274
274
301
260
255
248
Probe
temper-
ature, °C
208
206
248
178
121
193
200
295
286
121
205
210
279
174
121
208
209
281
279
121
147
188
180
Filter
temper-
ature, °C
204
206
284
286
121
201
210
262
285
124
208
210
261
284
122
206
209
239
263
122
143
124
123
Backup fil-
ter temper-
ature, "C
91
NA
NA
120
NA
NA
NA
NA
NA
NA
118
NA
NA
104
NA
122
NA
NA
121
NA
NA
NA
NA
2-4
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TABLE 2-2. SUMMARY OF ARSENIC ANALYTICAL RESULTS
QUAD AND REFERENCE TRAIN RUNS
ro
i
en
Run
No.
10A
10B
IOC
10D
10-RT
11A
11B
11C
11DC
11-RT
12A
12B
12C
12Dd
12-RT
13A
13B
13C
13D
13-RT
Sample
volume,
dNm3
1.07
1.12
1.18
1.09
1.41
1.02
1.12
1.14
1.00
1.33
1.23
1.33
1.34
0.292
1.53
1.14
1.28
1.30
1.13
1.37
Arsenic sample weights, mg
Probe
rinse
0.323
0.686
0.483
0.775
1.09
0.792
0.666
0.618
0.468
1.21
0.280
0.786
0.490
0.627
1.11
0.926
0.866
0.845
0.786
1.31
Front3
filter
8.50
9.26
9.81
9.81
11.17
7.57
9.19
8.98
1.75
11.17
10.48
10.86
10.96
2.05
10.79
9.26
10.55
10.35
9.55
11.50
Total
front
half
8.82
9.95
10.29
10.59
12.26
8.36
9.86
9.60
2.22
12.38
10.76
11.65
11.45
2.68
11.90
10.19
11.42
11.20
10.34
12.81
Back-half5
Glass
connector
0.05
NA
NA
0.05
NA
NA
NA
NA
NA
NA
0.05
NA
NA
0.05
NA
0.05
NA
NA
0.05
NA
Backup
filter
0.05
NA
NA
0.05
NA
NA
NA
NA
NA
NA
0.05
NA
NA
0.05
NA
0.05
NA
NA
0.05
NA
Impingers
1 & 2
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
2.38
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.10
Impingers
3 & 4
0.05
0.05
0.05
0.05
NA
0.05
0.05
0.05
0.21
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
NA
Total
back half
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
2.59
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.10
Concentration,
ng/dsm3
Front
half
8.24
8.88
8.72
9.72
8.70
8.20
8.80
8.42
2.72
9.31
8.75
8.76
8.54
9.18
7.78
8.94
8.92
8.62
9.15
9.35
Back
half
-
-
-
-
-
-
-
-
2.59
-
-
-
-
-
-
-
-
-
-
0.07
Total
train
8.24
8.88
8.72
9.72
8.70
8.20
8.80
8.42
4.81
9.31
8.75
8.76
8.54
9.18
7.78
8.94
8.92
8.62
9.15
9.42
The front filter data include the Parr bomb results, which constituted approxmately 1 percent of the total arsenic on
the filter.
NaOH rinse and impinger solution blank values ranged from 0.0 to 0.05 mg, therefore, back half values less than 0.05
mg are not reported.
cRun 11D is considered void due to a ruptured filter frit and subsequent loss of sample (see Pages 2-8 and 2-12).
Run 120 was terminated approximately 14 minutes into the test due to a ruptured filter frit support (see Page 2-12).
-------
fraction, and Table 2-3 presents statistical data for the grouped
quad runs.
Sample volumes were consistent and ranged between 1.00 and
1.34 dsm3 for the quad runs conducted during the full test
period. Quad Run 12D was terminated approximately 14 minutes
into the test due to a broken filter frit; the sample volume for
this run was 0.292 dsm3. Sample volumes for the reference train
tests ranged between 1.33 and 1.53 dsm3. Isokinetic sampling
rates ranged from 96.0 to 107.1 percent, which is within the
acceptable range of 90 to 100 percent. The probe and filter
temperatures represent average values determined from data
recorded on the field data sheets. The desired temperature for
paired Trains A and B was 204°C and for paired Trains C and D,
288°C. As shown, filter temperatures for Trains A and B ranged
from 201°C to 210°C and the probe temperatures ranged between
193° and 210°C. In Trains C and D, the filter temperatures were
more variable ranging between 239° and 286°C, and the probe
temperatures ranging from 174° to 295°C. The backup filter
temperatures in Runs 10A and 10D, 12A and 12D, and 13A and 13D
ranged from 91° to 122°C. No backup filters were utilized for
Quad Run 11. In each quad test, the reference train probe and
filter temperature was maintained at approximately 121°C.
The moisture content of the stack gas was generally con-
sistent in each run, and the average gas temperatures ranged from
274° to 310°C.
As shown in Table 2-2, arsenic sample weights are reported
in milligrams (mg) for each sample fraction analyzed. The front
2-6
-------
TABLE 2-3. STATISTICAL DATA FOR GROUPED RUNS
Quad Run
No.a
10A
10B
IOC
10D
11A
11B
11C
11D
12A
12B
12C
12D
13A
13B
13C
13D
Overall
means
Individual
run value
8.24
8.88
8.72
9.72
8.2
8.80
8.42
4.81
8.75
8.76
8.54
9.18
8.94
8.92
8.62
9.15
Group, mean
fcb
8.89
8.47
8.68
8.91
8.74e
°' ,
mg/dsm
0.617
0.304
0.124
0.218
0.367f
RSD,d
%
6.9
3.6
1.4
2.4
4.209
Sample Nos. 11D and 12D are considered invalid and are not included
in the group data.
Mean concentration.
cWithin-run standard deviation with N-l weighting for sample data.
Within-run relative standard deviation is the standard deviation
expressed as a percent of the mean concentration.
p
Simple averages of tabulated data.
Pooled standard deviation;\J £o .
~
2-7
-------
filter weight includes results for both the NaOH extract and the
Parr bomb (HF/HNO-) extract. The extract results constituted
approximately 1 percent of the total arsenic on the filter.
Arsenic was found mainly in the front half (probe and fil-
ter) of each of the 16 individual trains with the exception of
Run 11D. During this run, the filter frit support ruptured but
sampling continued until completion of the run. Obviously, some
arsenic was carried to the back half of the sampling train as
evidenced by the reported weight (2.59 mg) in the back half. Run
11D is considered an invalid sample and is not included in any of
the grouped averages or statistical calculations.
The total amount of arsenic found in the front half was 99
percent in each case, and at least 90 percent of this amount was
found in the filter fraction. No significant amount of arsenic
was present in any of the back-half components. The 0.05 mg
limit reported in Table 2-2 was established after careful anal-
ysis of the sample "blank" data. These data are summarized in
Section 3 of this report. In summary, 60 percent of the blank
values for the NaOH rinse and H-O impinger solutions were at or
below the analytical detection limit (0.002 to 0.005 mg); the
remaining blank values ranged up to a maximum value of 0.05 mg.
Values below 0.05 mg were considered insignificant because the
back-half arsenic content constituted less than 0.5 percent of
the total arsenic collected, the liquid fraction blank data were
variable, and 8.4 mg was the minimum amount of arsenic collected
in any one train run for at least 60 minutes. Note that in Run
2-8
-------
12D, the total arsenic collected was 2.7 mg. The filter frit
support ruptured approximately 14 minutes into the test and
sampling was immediately terminated. The train was disassembled
and recovered according to routine procedures. No significant
amount of arsenic was present in the back half of the train in
this run, and since the concentration is comparable with the
within-run data, the sample run is considered representative.
Because only 0.292 dsm3 was metered, however, the sample volume
does not conform to Method 108 specifications; therefore, the
concentration value is not included in the group statistical data
presented in Table 2-4.
The statistical data presented in Table 2-3 are comparable
with data obtained during the EMSL-QAD portion of this test pro-
ject. Statistical data for nine Method 108 quad train runs (36
individual samples; 121°C sample temperature) showed an overall
mean of 9.59 mg/dsm3 with mean arsenic concentrations of indi-
vidual quad runs ranging from 8.48 to 10.55 mg/dsm3. The stan-
dard deviations of the EMSL tests ranged from 0.10 to 1.45
mg/dsm3 with a pooled mean value of 0.59 mg/dsm3. The mean
relative standard deviation (RSD) for the nine runs was 6.14
percent. Table 2-4 summarizes the EMSL quad train results.
The standard deviations of the elevated temperature quad
runs ranged from 0.124 to 0.617 mg/dsm3 with a pooled mean value
of 0.367 mg/dsm3. The RSD values ranged from 1.4 to 6.9 percent
with a mean RSD of 4.2 percent. The mean arsenic concentration
of the individual quad runs ranged from 8.20 to 9.72 mg/dsm3 with
2-9
-------
TABLE 2-4. STATISTICAL DATA FOR GROUPED RUNS - EMSL QUAD TRAIN TESTS
Quad
run
No.
1A
IB
1C
ID
2A
2B
2C
2D
3A
3B
3C
3D
4A
4B
4C
4D
5A
SB
5C
5D
6A
6B
6C
6D
7A
7B
7C
7D
Concentration, mg/dsm3
Individual
run value
9.11
8.87
6.35
9.58
8.82
10.05
9.22
9.28
9.26
10.24
10.13
10.04
9.53
9.28
8.73
9.17
10.62
10.53
10.62
10.42
9.93
9.96
9.92
10.48
9.57
9.13
9.95
9.82
Groupamean
8.48
9.34
9.92
9.18
10.55
10.07
9.62
°-b,
mg/dsm3
1.45
0.514
0.446
0.334
0.10
0.272
0.361
RSD,C
%
17.1
5.5
4.5
3.6
0.95
2.7
3.8
(continued)
2-10
-------
TABLE 2-4 (continued)
Quad
run
No.
8A
8B
8C
80
9A
9B
9C
9D
Overal means
Concentration, mg/dsm3
Individual
run value
10.24
9.95
9.44
9.57
9.06
9.21
9.24
9.76
-
Group.mean
9.80
9.32
9.59d
a,
mg/dsm3
0.365
0.305
0.5896
RSD,C
%
3.7
3.3
6.14f
Mean concentration.
Within-run standard deviation with N-l weighting for sample data.
cWithin-run relative standard deviation is the standard deviation expressed
as a percent of the mean concentration.
Simple averages of tabulated data.
ePooled standard deviation;
RSD
10 -/X.
n
n
2-11
-------
an overall mean of 8.74 mg/dsm3. The overall mean of the ele-
vated temperature runs compares to within 10 percent of the
overall mean of the EMSL quad runs.
As shown in Table 2-2, the Method 108 reference train tests
that ran concurrently with the quad train tests are comparable
relative to total arsenic concentration and distribution. Over-
all, there is less than a 10 percent difference between the quad
run means and the reference train arsenic concentrations. In Run
10, the quad group mean was 8.89 mg/dsm3 compared with the refer-
ence train value of 8.70 mg/dsm3. In Run 11, the quad group mean
excluding 11D was 8.47 mg/dsm3 and the reference train value was
9.31 mg/dsm3. The group mean in Run 12 excluding 12D was 8.68
mg/dsm3 and the reference train value was 7.78 mg/dsm3. In Run
13, the quad group mean was 8.91 mg/dsm3 compared with 9.42
mg/dsm3 for the reference train.
These data in conjunction with the EMSL quad run data sug-
gest no significant difference between arsenic concentrations
measured by Method 108 (121°C) and modified Method 108 (elevated
sample temperature) at this source. The data also indicate no
significant difference between samples collected at 204°C and
those collected at 288°C.
Several factors observed during this test series that could
have affected sample results are addressed as follows. The
filter frit supports for Quad Runs 11D and 12C and 12D ruptured
during testing. The ruptures were attributed to the deteriora-
tion of the silica rubber gasket due to the sample temperature
2-12
-------
(288°C) and subsequent failure under vacuum. As mentioned in
Subsection 2.2, Run 11D was not terminated when the gasket
failed; consequently, a significant amount of arsenic was found
in the back half of the sampling train. The arsenic measured by
Train 11D, however, did not compare with the within-run samples
on a total weight basis. Because particulate was noticeable on
the frit, it was rinsed with 0.1 N NaOH into the container hold-
ing the contents of the first two impingers. Sample fractions
from this run were reanalyzed and rechecked; no discrepancies
were found in the reported analytical data.
Runs 12C and 12D were terminated immediately upon rupture of
the frit. In Train 12C, the rupture occurred with less than one
minute to go in the 70-minute test; in Train 12D, the rupture
occurred approximately 14 minutes after the start of the test.
In each case, no significant amount of arsenic was found in the
back half of the train. Also, the arsenic concentrations deter-
mined in these two runs are comparable with the within-run data.
New filter frits were used in each quad run, thereby minimizing
this problem.
Several back-half samples (connector glassware and backup
filters) from Quad Runs 10, 11, and 12 were contaminated by a
brown, oily substance believed to be volatilized probe heat tape
glue. This phenomenon is attributed to the high temperatures to
which the probes were heated and the use of an asbestos string
gasket material at the nozzle end of the probe. When heated to
288°C, the heat tape used in the construction of the probe heat-
ing system burned resulting in the volatilization of the tape
2-13
-------
glue. A visual inspection of the affected probes showed a heavy
deposit of contaminant on the asbestos gaskets as well as
distinct trails of the contaminant on the nozzle end of the glass
liner.
A heavier disposition of the contaminate was observed on the
trains heated to 288°C than those heated to 204°C. The material
was recovered by using the 0.1 N NaOH rinse and a nylon brush for
each affected sample fraction. Since the material was recovered
and digested according to Method 108 in a Parr bomb, any arsenic
from the gas stream that might become bound to the material would
be analyzed thus precluding a low bias on sample results. As the
back-half results indicate (Table 2-2), no arsenic was found in
these "contaminated" sample fraction; thus any bias in arsenic
measurements is believed to be minimal.
Another phenomenon associated with the filter frit support
occurred during the 288°C runs. Experiments conducted in our
laboratory showed that the standard glass frit filter support
with a silicon rubber gasket could withstand temperatures up to
260°C.
Above 260°C, deterioration of the gasket was noticeable as
evidenced by a light film of material on the filter holder glass-
ware. The material was believed to be a form of silicon oxide.
This same white material was present on all of the 288°C filter
glassware. A recovered sample from the laboratory experiment was
analyzed for arsenic. A detection limit of 0.003 milligrams per
liter was established for this sample and no detectable arsenic
was found. The data indicate that this material would not cause
2-14
-------
a high bias in arsenic results from these runs. Since the mate-
rial is recoverable and would be digested in a Parr bomb, any
arsenic from the gas stream which might become bound to the
material would be analyzed thus precluding a low bias on sample
results.
2.3 METHOD 108 TRAVERSE TEST RESULTS
Table 2-5 summarizes the sample and flue gas conditions and
Table 2-6 presents the arsenic emissions data for the Method 108
traverse tests.
Triplicate tests were conducted at the completion of the
quad train runs following procedures described in Method 108.
Twenty-four traverse points (12 per port) were used to traverse
the cross-sectional area of the stack. Each point was sampled
for 2.5 minutes yielding a total test time of 60 minutes.
Sample volumes for the three tests were consistent and
ranged from 1.03 to 1.07 dsm3. Isokinetic samples rates ranged
from 100.3 to 105.6 percent. The flue gas volumetric flow in
actual cubic meters per minute (m3/min) averaged 886 m3/min (440
dsm3/min at 20°C and 760 mmHg). The gas temperature and moisture
content averaged 254°C and 8.0 percent, respectively. Flue gas
composition was determined by analyzing integrated bag samples
collected during each test with an Orsat gas analyzer. Oxygen
(Op), carbon dioxide (CO-), and carbon monoxide (CO) contents
averaged 13.9, 3.8, and 0.0 percent, respectively.
As presented in Table 2-6, the total arsenic catch in milli-
grams ranged from 8.67 mg for Test CD-3 to 9.65 mg for Test CD-2.
2-15
-------
TABLE 2-5. SUMMARY OF SAMPLE AND FLUE GAS CONDITIONS
ARSENIC TRAVERSE TESTS
Run No.
CD-I
CD-2
CD-3
Date
(1984)
5/19
5/19
5/19
Average
Mete red
volume,
dsm3
1.03
1.06
1.07
1.05
Moisture
content,
%
8.0
8.3
7.7
8.0
Stack gas
tempera-
ture, °C
260
255
248
254
Gas composition,3 %
02
14.8
12.1
14.8
13.9
C02
3.2
4.7
3.5
3.8
CO
0.0
0.0
0.0
0.0
Volumetric.
flow rate
m3/min
851
903
903
886
dsm3/min
418
446
455
440
Isoki-
netic, %
105.6
102.1
100.3
-
Gas composition determined using an Orsat gas analyzer.
'Volumetric flow rate in actual cubic meters per minute (m3/min) and dry standard cubic meters
per minute (dsmVmin).
-------
TABLE 2-6. SUMMARY OF ARSENIC ANALYTICAL RESULTS
TRAVERSE TRAIN
Run No.
CD-I
CD-2
CD-3
Metered
volume,
dsm3
1.03
1.06
1.07
Average
Sample
weight, mg
Total arsenic
9.60
9.65
8.67
9.31
Concentra-
tion, mg/dsm3
9.32
9.10
8.10
8.84
Mass emission
rate, kg/h
0.23
0.24
0.22
0.23
2-17
-------
Total arsenic concentration averaged 8.84 mg/dsm3 with a corre-
sponding average mass emission rate of 0.23 kilograms per hour
(kg/h). These average results obtained by multipoint, isokinetic
traverse techniques are comparable to results obtained during the
quad train runs.
2.4 PROCESS SAMPLES
Several finished glass samples were obtained during the test
program to determine the arsenic content on a weight basis.
Table 2-7 summarizes the process sample results. Results were
consistent and the arsenic content by weight was approximately
0.05 percent. The samples analyzed were drinking mugs and three
portions of each mug (top, handle, and bottom) were analyzed.
Initially, glass chunks from the three sample fractions were
placed in Teflon bombs and digested using the Parr bomb procedure
from EPA Method 108. After extended heating, the glass chunks
did not dissolve. Additional glass fragments were ground in an
agate mortar and pestle and the resulting powder was placed in
Teflon bombs and digested per the Method 108 Parr bomb procedure.
After extended heating, a white precipitate remained in the bomb.
The sample was filtered through a Teflon filter and the filtrate
was analyzed for arsenic per Method 108. The remaining precipi-
tate was gelatinous in nature rather than a dense powder of the
original sample. The precipitate was redigested using a Parr
bomb and the resulting solution was analyzed for arsenic per
2-18
-------
TABLE 2-7. PROCESS SAMPLE ANALYTICAL RESULTS
Sample type
Drinking mug
Drinking mug
Lab No.
DM924
DM924
DM924
DM929
DM929
DM929
DM929R
Description
5/14; #2535 (handle)
5/14; #2535 (top)
5/14; #2535 (bottom)
5/19; #2540 (handle)
5/19; #2540 (top)
5/19; #2540 (bottom)
5/19; $2540 (bottom)
Total arsenic,
% by weight
0.052
0.055
0.059
0.055
0.059
0.055
0.058
2-19
-------
Method 108. This fraction consistently contained approximately 1
percent of the amount of arsenic found in the original filtrate.
These numbers were combined and reported.
2-20
-------
SECTION 3
PROJECT QUALITY ASSURANCE
Because the desired end product of testing is to achieve
representative emission results, quality assurance is one of the
main facets of stack sampling. Quality assurance guidelines
provide the detailed procedures and actions necessary for defin-
ing and producing acceptable data. Five such documents were used
in this test program to ensure the collection of acceptable data
and to provide a definition of unacceptable data. The following
documents comprise the Quality Assurance Project Plan prepared by
PEI and reviewed and approved by the Environmental Monitoring
Support Laboratory of the EPA (see Volume II - Appendix F); the
detailed site test plan prepared by PEI and reviewed by the
Emission Measurement Branch; the EPA Quality Assurance Handbook
Volume III, EPA-600/4-77-027; the PEI Emission Test Quality
Assurance Plan; and the PEI Laboratory Quality Assurance Plan.
The last two, which are PEI's general guideline manuals, define
the company's standard operating procedures and are followed by
the emission testing and laboratory groups.
In this specific test program, the following steps were
taken to ensure that the testing and analytical procedures
produced quality data.
3-1
-------
0 Calibration of all field sampling equipment.
0 Checks on train configuration and calculations.
0 Onsite quality assurance checks (i.e., leak checks of
the sampling train, pitot tube, and Orsat line) and
quality assurance checks of all test equipment prior to
use.
0 Use of designated analytical equipment and sampling
reagents.
0 Internal and external audits to ensure accuracy in
sampling and analysis.
Table 3-1 lists the sampling equipment used to perform the
arsenic tests and the calibration guidelines and limits. In
addition to the pre- and post-test calibrations, a field audit
was performed on the metering systems and thermocouple digital
indicators used in the sample runs. PEI-constructed critical
orifices were used in the dry gas meter audits. The onsite
audits were made at the beginning, middle, and end of the test
program. Figures 3-1 through 3-23 present the results of the
pre-test, mid-test, and post-test onsite audits. These data were
used to assess the operational status of the sampling equipment
relative to guidelines established by the U.S. EPA. The results
of the three field audits indicate that the sample equipment was
functioning properly throughout this test series.
Figure 3-24 is an example of an unacceptable meter box
audit. The audit value for the meter coefficient deviation was
greater than ±5 percent, which was considered unacceptable by the
PEI Project Manager; therefore, the meter box was not used for
this test program.
3-2
-------
TABLE 3-1. FIELD EQUIPMENT CALIBRATION
Equipment
Meter box
Pitot tube
Digital
indicator
Thermocouple
ID No.
FB-1 Train A
FB-5 Train B
FB-8 Train D
FB-10 Train C
FB-9 (Traverse
tests)
FB-9 (Reference
train tests)
513
514
508
220
221
411 - (stack)
412 - (stack)
601 - Probe
605 - Filter
Calibrated
against
Wet test meter
Standard pitot
tube
Millivolt
signals
ASTM-3F
Allowable error
Y ±0.02 Y
AH (3 ±0.15
(Y ±0.05 Y post-test)
Cp ±0.01
0.5%
1.5%
(±2% saturated)
Actual
error
0.004
0.09
+1.35
0.002
0.05
+0.10
0.006
0.07
-0.20
0.012
0.07
-0.52
0.013
0.08
+1.30
-
-
0.2%
0.4%
0.4%
0.2%
0.8%
1.0%
Within
allowable
limits
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
OK
OK
X
X
X
X
X
X
Comments
Visually
inspected
on site
OJ
I
U)
(continued)
-------
TABLE 3-1 (continued)
Equipment
Thermocouple
(cont'd)
Orsat analyzer
Impinger
thermometer
Mettler
balance
Barometer
Dry gas
thermometer
ID No.
614 - Probe
615 - Probe
616 - Probe
618 - Probe
619 - Probe
620 - Filter
141
433
434
435
446
385
M-l
407
FB-1
FB-5
FB-8
Calibrated
against
Standard gas
ASTM-3F
Type S weights
NBS traceable
barometer
ASTM-3F
Allowable error
±0.5%
±2°F
±0.5 g
+0.10 in.Hg.
(0.20 post-test)
±5°F
Actual
error
0.4%
0.6%
0.5%
0.6%
0.6%
1.2%
0.0%
0.2%
0.0%
1.2°F
0.5°F
1.0°F
1.0°F
1.0°F
+0.1 g
0.01
in.Hg.
4°F
5°F
4°F
2°F
2°F
3°F
Within
allowable
limits
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Comments
co2
CO
Inlet
Outlet
Inlet
Outlet
Inlet
Outlet
(continued)
-------
TABLE 3-1 (continued)
Equipment
Dry gas
thermometer
(cont'd)
Probe nozzle
ID No.
FB-10
FB-9
1A
IB
1C
ID
2A
2B
2C
2D
5-106 (RT
tests)
2-117
(Traverse
tests)
Calibrated
against
Caliper
Allowable error
Dn ±0.004 in.
Actual
error
2°F
2°F
2°F
2°F
0.001 in.
0.002 in.
0.000 in.
0.001 in.
0.002 in.
0.002 in.
0.000 in.
0.002 in.
0.001 in.
0.003 in.
Within
allowable
1 imits
X
X
X
X
: X
X
X
X
X
X
X
X
X
X
Comments
Inlet
Outlet
Inlet
Outlet
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
-5-
CLIENT;
BAROMETRIC PRESSURE (P):
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
CLIENT:
BAROMETRIC PRESSURE (Pbar);^go 1n.Hg METER BOX NO.
ORIFICE NO.
ORIFICE K FACTOR:
X/£>
PRETEST
AUDITOR:
1n.H0
Orifice
manometer
reading
AH,
1n.H20
P05
Dry gas
meter
reading
ft3
^tf.fcc
;2.6>3,60c
Temperatures
Ambient
Tai/Taf
°F
•^o
?o
Average
V
°F
10
Dr
Inlet
°F
•^
&o
/gas meter
Outlet
°F
1^
^
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
CLIENT:
BAROMETRIC PRESSURE (Pbar):Pi££ 1n.Hg METER BOX NO
ORIFICE NO. 3 PRETEST
'' "^ AUDITOR*
ORIFICE K FACTOR:
/f/ 1n.H20
Orifice
manometer
reading
AH,
1n.H,0
Dry gas
meter
reading
w
ft3
Temperatures
Ambient
Ta1/Taf
°F
Average
Dr
Inlet
T11/Tif
°F
/ gas meter
Outlet
Average
Duration
of
run
0
m1n.
7/.S
Dry gas
meter
V ft3
/3.200
V|nstd'
ft3
/P.?*/
Vmact»
ft3
/P 5? ?
Audit,
Y
O3*&-
Y
devia-
tion, %
dP^I
Audit
AH(a,
1n.H20
/7V
AH@ Devia-
tion, 1n.H20
<9.07
m
std
17.647(Vm)(Pbar + AH/13.6)
m
act
1203( 0 )( K )(Pbflr)
(Ta + 460)
Audit Y "
m
std
x 100
Audit AH(? = (0.0317)(AH)(Pbar)(Tm + 460)
0
1n.H0
Audit Y must be in the range, pre-test Y ±0.05 Y.
Audit AHP must be in the range pre-test AH@ ±0.15 inches
Figure 3-3. Pre-test audit report: dry gas meter by
critical orifice (Meter Box FB-8, Tram D).
3-8
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
CLIENT:
BAROMETRIC PRESSURE (Pbar): "Z?'*° in.Hg METER BOX NO.
ORIFICE NO. /2- _ PRETEST
ORIFICE K FACTOR: ^."R^S^O'^ AUDITOR;/Su'
SO ~
AHf /. #/ ,1n.H,0
Orifice
manometer
reading
AH,
1n.H20
/ft?
Dry gas
meter
reading
VV
ft3
O^o. too
031. <1*o
Temperatures
Ambient
Ta1/Taf
°F
•}o
?l
Average
T,-
•F
10.6
Dr
Inlet
°F
^(s>
^
/gas meter
Outlet
VV'
7z-
^
Average
°F
H&
Duration
of
run
0
min.
*2 I •*"*"
Dry gas
meter
V ft3
/1,00V
v
std'
ft3
/6>'?>q3
v
act*
ft3
K,414
Audit,
Y
oj1*
AH@ Devia-
tion, 1n.H20
0.0(0
m
std
17.647(Vm)(Pbar * AH/13.6)
(Tm + 460)
m
act
1203( 0 )( K )(Pbflr)
(Ta + 460)
1/2
Audit Y
m
'act
m
'std
Y deviation
Audit Y - Pre-test Y
Audit Y
x 100 «= -
Audit AH(? = (0.0317)(AH)(Pbar)(Tm + 460)
AH/13.6)
Audit Y must be 1n the range, pre-test Y ±0.05 Y.
Audit AH@ must be In the range pre-test AH@ ±0.15 Inches H20.
Figure 3-4. Pre-test audit report: dry gas meter by
critical orifice (Meter Box FB-10, Train C).
3-9
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
CLIENT:
BAROMETRIC PRESSURE (PhaJ: P^£2_in.Hg METER BOX NO.
ORIFICE NO.
bar
ORIFICE K FACTOR:
PRETEST Y:.
AUDITO
Orifice
manometer
reading
AH,
in.H20
->,zs
Dry gas
meter
reading
vv
ft3
OT*.Ooo
0^/3,3-00
Temperatures
Ambient
Tai/Taf»
°F
Tz_
^3^
Average
V
&•
Dry gas meter
Inlet
VTif
°F
^Z-
^ ^
Outlet
w-
°F
^Z-
^
Average
°F
^.5
Duration
of
run
0
min.
ZL'S <&&
Dry gas
meter
v ft3
70.-2.
v
std'
ft3
PO./«
v
act*
ft3
19.117,
Audit,
Y
0*50
Y
devia-
tion, %
-3.15
Audit
AH@,
in.H20
,2.06
AH@ Devia-
tion, in.H20
0.02, .
m
std
17.647(Vm)(Pbar + AH/13.6)
m
act
1203( 0 )( K )(Pbar)
(Ta + 460)
1/2
Audit Y =
m
'act
m
Y deviation =
Audit Y - Pre-test Y
Audit Y
x 100 = -3.
std
Audit AH@ = (0.0317)(AH)(Pbar)(Tm + 460)
Y TVJ(Pbar + AH/13.6)
in.H20
Audit Y must be in the range, pre-test Y ±0.05 Y.
Audit AH@ must be in the range pre-test AH@ ±0.15 inches H^
Figure 3-5. Pre-test audit report: dry gas meter by critical
orifice (Meter Box FB-9, Single Point-Traverse Tests).
3-10
-------
THERMOCOUPLE DIGITAL INDICATOR
AUDIT DATA SHEET
Date 6~~ //'
Indicator No.
Operator
Test Point
No.
1
2
3
4
Millivolt
signal*
Equivalent
temperature,
°F*
32-
2-OO
5^0
/1 44
Digital Indicator
temperature reading,
°F
3,2-.
203~
*S^o
/Mb
Is
Difference,
I
G*O
- o.s<^
o.o
-o.(Z_
Percent difference must be less than or equal to 0.5%.
Percent difference:
(Equivalent temperature °R* Digital Indicator temperature reading °R)(100%)
(Equivalent temperature R)
Where °R « °F * 460°F
These values are to be obtained from the calibration data sheet for the
calibration device.
Figure 3-6. Pre-test thermocouple digital indicator
audit data sheet (Indicator No. 220).
3-11
-------
THERMOCOUPLE DIGITAL INDICATOR
AUDIT DATA SHEET
Date ^ - //• *?T Indicator No. P«2-/ Operator
zz
Test Point
No.
1
2
3
4
Millivolt
signal*
Equivalent
temperature,
°F*
33-
3-&O
-^o
//fy
Digital Indicator
temperature reading,
•F
So
c2-0 1
54o
/Ifa
Difference,
X
0,41
-0./5
O.o o
— 0. 1^
Percent difference must be less than or equal to 0.52.
Percent difference:
(Equivalent temperature °R- Digital Indicator temperature reading °R)(100'%)
(Equivalent temperature^R)
Where °R • °F + 460°F
These values are to be obtained from the calibration data sheet for the
calibration device.
Figure 3-7. Pre-test thermocouple digital indicator
audit data sheet (Indicator No. 221).
3-12
-------
Audit Name
ON-SITE AUDIT DATA SHEET
Date:
Auditor:
"— ' 7^
Equipment
*%?, Meter box
£?' Inlet thermo.
poO „
F6Z- Meter box
& ' outlet thermo.
£AS
/ *-*^
<*
?Z
^/
62
^
1>V
(01:
&a
£&
6?
(ol-
#A
Deviation
3
Z
*
2
*/
2~
Ji
1
z
z
?
3
X4
Max. fcflowable
Deviation
5°F
5°F
2°F
7°F
See table
0.7%
0.5 grams
0.20 in. Hg
Reference temp. °F
Max. deviation °F
32-140
7
141-273
9
274-406
11
407-540
13
541-673
15
674-760
17
* Correction factor:
NWS value (1n. Hg) - [Altitude (ft)/1000(ft/in. Hg)] + 0.74 1n. Hg**
** 0.74 1n. Hg Is the nominal correction factor for the reference barometer
against which the field barometer was calibrated.
If 1t is not feasible to perform the audit on any piece of equipment, record
"N/A" in the space provided for the data.
Figure 3-8. Pre-test onsite audit data sheet.
3-13
-------
ON-SITE AUDIT DATA SHEET
Audit
Equipment
^'?Meter box
F&1> Inlet thermo.
£'° Meter box
pd t outlet thermo.
r*35 Impinger
ua< thermometer
i-?-*
Stack
thermometer
or
Thermocouple
Orsat
analyzer
Trip
balance
Barometer
Reference
ASTM-3F at
ambient temp.
ASTM-3F at
ambient temp.
ASTM-3F at
ambient temp.
ASTM-3F at
ambient temp.
ASTM-3F at
stack temp.
% 02 in
ambient air
IOLM std.
weight
Corrected*
NWS value
Reference
Value
%
Gf ^m
+ ^7
t<*
20.8%
Value
Determined
^
<*><<>
r?
Deviation
3
2-
O
Max. Allowable
Deviation
5°F
5°F
2°F
7°F
See table
0.7%
0.5 grams
0.20 in. Hg
Reference temp. °F
Max. deviation °F
32-140
7
141-273
9
274-406
11
407-540
13
541-673
15
674-760
17
* Correction factor:
NWS value (in. Hg) - [Altitude (ft)/1000(ft/in. Hg)] + 0.74 in. Hg**
** 0.74 in. Hg is the nominal correction factor for the reference barometer
against which the field barometer was calibrated.
If 1t is not feasible to perform the audit on any piece of equipment, record
"N/A" in the space provided for the data.
Figure 3-9. Pre-test onsite audit data sheet.
3-14
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
CLIENT:
BAROMETRIC PRESSURE (Pbar):P?y^2-1n.Hg METER BOX NO
ORIFICE NO. -T#3 PRETEST Y:
ORIFICE K FACTOR; -
f 2 1n.H0
Orifice
manometer
reading
AH,
1n.H20
^o
Dry gas
meter
reading
vv
ft3
3bl3oo
&6.200
Temperatures
Ambient
°F
&q
^
Average
V
"F
*7
Dry gas meter
Inlet
VTif
°F
^3
^0
Outlet
w
°F
^
^^
Average
V
"F
n*
Duration
of
run
0
min.
^
Dry gas
meter
V ft3
/^/3^o
Vm
mstd'
ft3
&W
Vm
macf
ft3
/3.ZOO
Audit,
Y
OKI
Y
devia-
tion, %
-, 1 iL'2-
Audit
AHP,
in.H20
/•W
AH@ Devia-
tion, 1n.H20
o.o*.
m
std
17.647(Vm)(Pbar. AH/13.6)
ft>
m
act
1203( 0 )( K )(Pbar)
(Ta + 460)
Audit
m
m
std
it Y
Audit Y
x 100 - -
Audit AH@ = (0.0317)(AH)(Pbar)(Tm + 460)
Audit Y must be 1n the range, pre-test Y ±0.05 Y.
Audit AH@ must be in the range pre-test AH@ ±0.15 inches
Figure 3-10. Mid-test audit report: dry gas meter
by critical orifice (Meter Box FB-1).
3-15
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
CLIENT:
- Q A vN
BAROMETRIC PRESSURE (Pbar):^7££ln.Hg METER BOX NO.
ORIFICE NO. • ? PRETEST
AUDITOR*
ORIFICE K FACTOR:
"•- i. — ~ -f
Orifice
manometer
reading
AH,
1n.H20
J?,/O
Dry gas
meter
reading
vv
ft3
6 33.500
66?,6tfo
Temperatures
Ambient
Ta1/Taf
°F
3O
^O
Average
V
•F
T°
Dr
Inlet
T11/T1f
°F
tf/%6
Y
devia-
tion, %
-/.%
Audit
AH@,
in.H20
/•fz-
AH@ Devia-
tion, 1n.H20
O .0-2-
m
std
17.647(Vm)(Pbar + AH/13.6)
m
act
1203( 0 )( K )(Pbflr)
(Ta * 460)
172
ft'
Audit Y
deviation
Aud1t Y
"std
S^^51 Y x 100 - -/.
Audit AH0 = (0.0317)(AH)(Pbar)(Tm + 460)
Audit Y must be 1n the range, pre-test Y ±0.05 Y.
Audit AHP must be in the range pre-test AHP ±0.15 inches H,0.
1n.H0
Figure 3-11. Mid-test audit report: dry gas meter
hv rritical orifice (Meter Box FB-5).
3-16
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
CLIENT:
BAROMETRIC PRESSURE (Pbar): P£~>Z-1n.Hg METER BOX NO.
ORIFICE NO. ^6 PRETESTJfc-
1n.H,0
ORIFICE K
Orifice
manometer
reading
AH,
1n.H20
P.*S
FACTOR: 5-P^X/O" * AUDITtfc^^W^f^^eW^-^
Dry gas
meter
reading
vv
ft3
1W.OOC
-tfO.tov
Temperatures
Ambient
Ta1/Taf
°F
6>3
^
Average
Ta-
"F
^
Dr
Inlet
W
°F
^^
•fc^
/ gas meter
Outlet
Toi/Tof»
°F
«^4
-S^r-
Average
V
•F
^.Z5
Duration
of
run
min.
/**
Dry gas
meter
V fts
/35oo
Vm
mstd«
ft3
/PdM.
y
act*
ft3
/P.?V9-
Audit.
Y
^.-w&
Y
devia-
tion, %
aVo
Audit
AHP,
1n.H20
/.-Z-2-
AH@ Devia-
tion, 1n.H20
o.of .
m
'std
17.647(V )(P. + AH/13.6)
m
"act
1203( 0 )( K )(Pbar)
(Ta + 460)
1/2
Audit Y
m
'act
m
Y deviation -
std
Y
10° --
Audit AHP = (°-0317)(AH)(pbar)(Tm + 460)
Audit Y must be 1n the range, pre-test Y ±0.05 Y.
Audit AHC must be in the range pre-test AHP ±0.15 inches
Figure 3-12. Mid-test audit report: dry gas meter
by critical orifice (Meter Box FB-8).
3-17
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
CLIENT:
BAROMETRIC PRESSURE (P.._):^5z.In.Hg METER BOX NO.
ORIFICE
ORIFICE K FACTOR:
/Z~
bar
PRETEST
AUDITOR:
in.H,0
Orifice
manometer
reading
AH.
1n.H20
tf°
Dry gas
meter
reading
Vvf.
ft3
4t&.*oo
^,£00
Temperatures
Ambient
Tai/Taf
°F
?o
TO
Average
Ta-
"F
yo
Dry gas meter
Inlet
°F
*??-
4t
Outlet
°F
?Z-
*?(
Average
Tm-
'F
f/-5
Duration
of
run
min.
^~
Dry gas
meter
V ft3
l?3a°
Xtd'
ft3
/3.o^?>
Xcf
ft3
//. vv^
Audit,
Y
O.fVf
Y
devia-
tion, %
-/.fo
Audit
AHP,
1n.H20
/?f
AH@ Devia-
tion, 1n.H20
0°1 .
m
'std
17.647(Vm)(Pbar * AH/13.6)
• p.053 ft3
m
act
1203( 0 )( K )(Pbflr)
(Ta + 460)
1/2
Audit Y
Y deviation
Audit Y
"std
Audit AH@ = (0.0317)(AH)(Pbar)(Tm + 460)
x 100 - -
AH/13.6)
Audit Y must be 1n the range, pre-test Y ±0.05 Y.
Audit AHP must be in the range pre-test AHP ±0.15 inches H~0.
Figure 3-13. Mid-test audit report: dry gas meter
by critical orifice (Meter Box FB-10).
1n.H0
3-18
-------
THERMOCOUPLE DIGITAL INDICATOR
AUDIT DATA SHEET
Date
Indicator No. PP-O
Test Point
No.
1
2
3
4
Millivolt
signal*
Equivalent
temperature,
•F*
3^
^00
-5VO
//f^
Digital Indicator
temperature reading,
•F
33
*2^
t52>?
J144
Difference,
X
*.*
*.*<
.1
0
Percent difference must be less than or equal to 0.51.
Percent difference:
(Equivalent temperature °R- Digital Indicator temperature reading CR)(100£)
(Equivalent temperature °R)
Where °R • °F * 460°F
These values are to be obtained from the calibration data sheet for the
calibration device.
Figure 3-14. Mid-test thermocouple digital indicator
audit data sheet (Indicator No. 220).
3-19
-------
THERMOCOUPLE DIGITAL INDICATOR
AUDIT DATA SHEET
Date
Indicator No.
/
Operator
Test Point
No.
1
2
3
4
Millivolt
signal*
Equivalent
temperature,
•F*
32-
poo
-5^0
//fV
Digital Indicator
temperature reading,
•F
P
-------
Audit Name:-z-
Deviation
/
2-
^
J>
o
2_
Max. Allowable
Deviation
5°F
5°F
2°F
7°F
See table
0.7%
0.5 grams
0.20 in. Hg
Reference temp. °F
Max. deviation °F
32-140
7
141-273
9
274-406
11
407-540
13
541-673
15
674-760
17
* Correction factor:
NWS value (in. Hg) - [Altitude (ft)/1000(ft/in. Hg)] + 0.74 in. Hg**
** 0.74 in. Hg is the nominal correction factor for the reference barometer
against which the field barometer was calibrated.
If 1t is not feasible to perform the audit on any piece of equipment, record
"N/A" in the space provided for the data.
Figure 3-16. Mid-test onsite audit data sheet.
3-21
-------
Audit Name:
ON-SITE AUDIT DATA SHEET
Date:
%c/
Equipment
^ / Meter box
T5>5 inlet thermo.
£o , Meter box
^fy outlet thermo.
^^ Impinger
436 thermometer
Stack
thermometer
or
Thermocouple
Orsat
analyzer
Trip
balance
Barometer
Reference
ASTM-3F at
ambient temp.
ASTM-3F at
ambient temp.
ASTM-3F at
ambient temp.
ASTM-3F at
ambient temp.
ASTM-3F at
stack temp.
% O^ 1n
ambient air
IOLM std.
weight
Corrected*
NWS value
Reference
Value
•57
1?
JJ
20.8%
fa
M
Value
Determined
li
S3
53
S-%
rr
Deviation
*~ 1
^>
o
1
Max. Allowable
Deviation
5°F
5°F
2°F
7°F
See table
0.7%
0.5 grams
0.20 in. Hg
Reference temp. °F
Max. deviation °F
32-140
7
141-273
9
274-406
11
407-540
13
541-673
15
674-760
17
* Correction factor:
NWS value (in. Hg) - [Altitude (ft)/1000(ft/in. Hg)] + 0.74 in. Hg**
** 0.74 1n. Hg 1*the nominal correction factor for the reference barometer
against which the field barometer was"calibrated.
If 1t is not feasible to perform the audit on any piece of equipment, record
"N/A" 1n the space provided for the data.
Figure 3-17. Mid-test onsite audit data sheet.
3-22
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
CLIENT: U5£PA
DATE: ^
BAROMETRIC PRESSURE (Pbar)= '¥Ll£ In.Hg METER BOX NO. F£ - I
ORIFICE NO. i3 ^_ PRETEST Y: Q.^k^ AHP 1,72, 1n.HtO
ORIFICE K FACTOR: 6.377*1&"^ AUDITOR:
Orifice
manometer
reading
AH,
1n.H20
2.I5
Dry gas
meter
reading
YV
ft3
V9o,ozr
£83.330
Temperatures
Ambient
T.1/Taf
°f
78
-78
Average
V
°F
78
Dry gas meter
Inlet
W
°F
11
S^
Outlet
T0l/T0f
°F
11
13
Average
V
°F
%zr
Duration
of
run
0
min.
X5.O
Dry gas
meter
V ft3
m*
'3.J0T
mstd»
ft3
/if/0
Xcf
ft3
/2,m
Audit,
Y
tiro
Y
devia-
tion, X
-/.JT
Audit
AHP,
1n.H20
/,7T
AH(? Devia-
tion, 1n.H20
-i-o, 05-
"std
460)
ft3
m
act
1203( 0 )( K )(Pbar)
(T * 460)
1/2
Audit Y =
m
'act
Y deviation
Audit Y - Pre-test Y
Audit Y
x 100 * -
"std
Audit AH(? = (0.0317)(AH)(Pbar)(Tm + 460)
Audit Y must be 1n the range, pre-test Y ±0.05 Y.
Audit AHP must be In the range pre-test AHP ±0.15 Inches
Figure 3-18. Post-test audit report: dry gas meter by
critical orifice (Meter Box FB-1).
3-23
-------
FIELD AUDIT REPORT: DRY GAS HETER
BY CRITICAL ORIFICE
DATE:
CLIENT: (J5£Pf>
BAROMETRIC PRESSURE (P): ffiA?1n.Hg METER BOX NO.
ORIFICE NO.
ORIFICE K FACTOR:
PRETEST Y: p.983 AHP L
AUDITOR:
1n.H20
no&
Orifice
manometer
reading
AH,
1n.H20
/3o
Dry gas
meter
reading
W
ft3
gg^.730
S
Average
V
"F
-78
Dry gas meter
Inlet
VTif
°F
&(*
&8
Outlet
T0l/T0f
°F
go
^2^
Average
Tm-
°F
H
Duration
of
run
0
min.
is-.o
Dry gas
meter
V ft'
II Mo
mstd»
ft3
n\n
Xcf
ff
IOXST
Audit,
Y
All
Y
devia-
tion, %
-ivf
Audit
AH0,
in.H20
/.
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
CLIENT:
BAROMETRIC PRESSURE (Pbar);^/O 1n.Hg METER BOX NO. FB-ff
ORIFICE NO. 1 PRETEST Y: Q.99O AH& 1.91 1n.H20
ORIFICE K FACTOR:
Orifice
manometer
reading
AH,
1n.H20
yt\o
Dry gas
meter
reading
vv
ft3
oiinoo
£X/f.Zeo
Temperatures
Ambient
Ta1/Taf
°F
^
*3-2~
Average
Ta-
"F
PO
Dr
Inlet
°F
^^f
^^
/gas meter
Outlet
VTof
°F
^0
^3>
Average
°F
P5.r
Duration
of
run
0
min.
3f-J'
Dry gas
meter
V fts
M tioo
Vm
mstd'
ft3
Zf.ftK
Vm
"act'
ft3
Zy,2T7
Audit,
Y
,?rf
Y
devia-
tion, %
-,n
Audit
AHP,
in.H20
l.lf-
AH(? Devia-
tion, 1n.H20
-t-.o? .
17.647(Vm)(P .AH/13.6)
m
460)
'act
1203( 0 )( K )(Pbflr)
(Ta + 460)
1/2
ft3
Audit Y •
m
'act
m
Y deviation
std
Audit Y - Pre-test Y
Audit Y
x 100 = -
Audit AH? = (0.0317)(AH)(Pbar)(Tm + 460)
Audit Y must be 1r, the range, pre-test Y ±0.05 Y.
Audit AHP must be in the range pre-test AHP ±0.15 Inches H^O.
Figure 3-20. Post-test audit report: dry gas meter by
critical orifice (Meter Box FB-8).
1n.H20
3-25
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE:
CLIENT:
BAROMETRIC PRESSURE (Pbar):<2§/£ In.Hg METER BOX NO. £B~ (O
ORIFICE NO. to PRETEST YQ.96T7 AHP \.l\ 1n.H,0
ORIFICE K FACTOR: 5.£*M * IcT^ AUDITOR:
1
Orifice
manometer
reading
AH,
1n.H20
2,3-0
Dry gas
meter
reading
W
?Z2 .Too
W7*°
Temperatures
Ambient
Tai/Taf
°F
"W
??
Average
Of
Dr
Inlet
T11/T1f
°F
*?*f
^
y gas meter
Outlet
°F
^0
^/
Average
Tm-
"F
ttr
Duration
of
run
0
min.
/f^
Dry gas
meter
V ft3
a/^
Vm
mstd*
ft3
Iti*?
Vm
macf
ft3
/^JT7
Audit,
Y
,1U
Y
devia-
tion, %
-,lo
Audit
AHP,
1n.H20
/,fr
AH(? Devia-
tion, 1n.H20
^,^/ .
"std
17.647(Vm)(Pbar + AH/13.6)
460)
ft3
m
act
1203( 0 )( K )(Pbflr)
(T * 460)
172
t3
Audit Y =
m
'act
m
Y deviation
Audit Y - Pre-test Y
Audit Y
x 100 « ^
'std
Audit AHC< = (0.0317)(AH)(Pbar)(Tm + 460)
Audit Y must be 1n the range, pre-test Y ±0.05 Y.
Audit AH3 must be 1n the range pre-test AHP ±0.15 Inches H20.
Figure 3-21. Post-test audit report: dry gas meter by
critical orifice (Meter Box FB-10).
i.HoO
3-26
-------
THERMOCOUPLE DIGITAL INDICATOR
AUDIT DATA SHEET
Date
Indicator No. IIP
Operator
Test Point
No.
1
2
3
4
Millivolt
signal*
Equivalent
temperature,
•F*
•*>?•
^oo
-s*t°
//
2°?^
-5*5 f
//W
Difference,
1
,w
.v>
.or
.00
Percent difference must be less than or equal to 0.5%.
Percent difference:
(Equivalent temperature °R- Digital Indicator temperature reading eR)(100t)
(Equivalent temperature °R)
Where °R « °F * 460°F
These values are to be obtained from the calibration data sheet for the
calibration device.
Figure 3-22. Post-test thermocouple digital indicator
audit data sheet (Indicator No. 220).
3-27
-------
THERMOCOUPLE DIGITAL INDICATOR
AUDIT DATA SHEET
Date
- /f "
Indicator No. 2,21
Operator
Test Point
No.
1
2
3
4
Millivolt
signal*
Equivalent
temperature.
•F*
32.
0
-SfO
/PW
Digital Indicator
temperature reading,
•F
*
-------
FIELD AUDIT REPORT: DRY GAS METER
BY CRITICAL ORIFICE
DATE: ---
CLIENT:
BAROMETRIC PRESSURE (P):P#£? 1n.Hg METER BOX NO. f&
ORIFICE NO.
ORIFICE K FACTOR ;
bar
PRETEST
AUDITOR
/,?31n.H.O
|"V^57^SE*X*^^^
Orifice
manometer
reading
AH,
1n.H20
/.io
Dry gas
meter
reading
w
ft3
(0?4.*>*. 300
Temperatures
Ambient
Ta1/Taf
°F
£,*
6K
Average
°F
^
Dry gas meter
Inlet
°F
To
?-o
Outlet
VTof
°F
^>?
(o^
Average
°F
&.*
Duration
'Of
irun
- 0
min.
IU> 6O
Dry gas
meter
V fts
"'std'
ft3
m
'act'
ft3
offz
AH@ Devia-
tion, 1n.H20
m
'std
'act
Audit Y
17.647(Vm)(Pbar * AH/13.6)
**"
1203( 0 )( K )(Pbflr)
(Tfl + 460)
1/2
m
'act
Y deviation
m
'std
Audit Y - Pre-test Y
Audit Y
100
Audit AH(3 = (0.0317)(AH)(Pbar)(Tm + 460)
Audit Y must be 1n the range, pre-test Y ±0.05 Y.
Audit AHP must be in the range pre-test AH@ ±0.15 inches H^O.
Figure 3-24. Example of unacceptable dry gas meter audit.
3-29
-------
PEI personnel calculated the sampling rates on site. The
data were rechecked and validated at the end of the test program
by computer programming. Some minor discrepancies between the
hand calculations and computer printouts resulted primarily
because of round-off error. Overall, the data compared favor-
ably. Figure 3-25 presents an example calculation form PEI using
during this test program. Computerized example calculations are
presented in Appendix A.
As an additional check of the reliability of the method used
to analyze the samples/ two blank trains were assembled in the
recovery area, capped off, and set aside for about 2 hours. The
first blank train was assembled at the beginning of the test
series using clean glassware. On the same day as Quad Runs 1, 8,
and 9 (EMSL work), the second blank train was assembled with
glassware used during previous sampling runs. The blank trains
were recovered in the same manner as the test samples. These
samples were shipped to the laboratory and analyzed by the same
procedures as those used for the actual emission samples. In
addition to the blank sampling train, aliquots of the field
reagents used in the collection and recovery of the samples were
obtained daily and analyzed by the same procedures as those used
for the actual samples. Table 3-2 presents the results of the
blank sample trains and field blank analyses. The results are
considered reasonable and indicate that background arsenic
contamination was not a problem in the sample recovery area. The
results of the blanks are relatively small.
3-30
-------
ISOKINETIC CALCULATION
41.
SITE
. TEST NO.
1. »ol*» Of dry fit M^lod COrrvcUd to
tUnd«r« condition!. toU: V Milt ta
corrtcttd for iMkigt 1f in/ llikigt
nUt tacttd L ).
r, „, i
t_ • 11. «s » v • T tar • TTT
•ltd • I !• J
1$^ ^
V.<«
2. »elu«» of Mtf Mpor it tUnferd COn-
•itlont, ft'.
V • 0.04707»j •
"ltd IC
3. Neiltvrt content 1n tuck 911.
1 • "ltd •
•ltd "ltd
4. Or; acltculir «»1JM of lUCk fit.
Mfl • 0.440 (t COj) • O.UO (t Oj)
• 0.7(0 (» «j • » CO) •
I. ltol»cul«r Might of tuck tu-
ft. Stick vtlocU/ It tUCt condition*.
*pt
T. iMttMtlC Mrt«t««n
». T.
S 1 • "tU 1*1 1T.V
t. * B. • • I ». • (!••_.)
• • 9 VI
V ft*
t
%.r. 1".Hg
AH. 1n.H20
T«-'R
V . dscf
"std
V1c. 9
vw .ft3
*$td
Bws
J-Bws
* C02
%JXf^).
1 N2 * X CO
Md, Ib/lb-nole
H$. Ib/lbHBlt
P 1fl t4
r»tit1c* in'H2
P,. 1n.H9
T^. "R
ysr
Cp
V,. fps
On. 1n.
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Figure 3-25. Example of onsite calibration data sheet.
3-31
-------
TABLE 3-2. ARSENIC BLANK DATA
Blank sample train arsenic values'
Train No.
1
2
Filter, yg
32.8
30.8
NaOH probe
rinse, yg
8.0
7.8
Impinger
section, yg
22.2
11.6
Total train
blank, yg
63.0
50.2
Field blank arsenic values
Date
samples
taken
5/17/84
5/18/84
5/19/84
Corresponding
Run No.
10 + 11
12 + 13
CD1 - CDS
Average blank values
Filter
total , yg
26.7
29.3
28.8
28.3
NaOHb ,
mg/liter
0.0168
0.0137
0.0153
0.0153
H20C,
mg/liter
0.0085
0.0101
0.0111
0.0099
Sample train was fully assembled in recovery area and then recovered and
analyzed as a sample.
5Between 235 and 238 ml 'of NaOH was used to rinse the probe. Between 179
and 456 ml of the NaOH was used to rinse Impingers 1 and 2. Between 128
and 184 ml of the NaOH was used to rinse Impingers 3 and 4. Between 119
and 180 ml of the NaOH was used to rinse the connector. The maximum blank
for the NaOH corresponds to 6 yg for the probe rinse, 8 yg for the impinger
samples, and 3 yg for the connector samples.
"On both days, 300 ml of water was added to arsenic Impingers 1 and 2 and
150 ml to Impingers 3 and 4. The maximum blank for the water corresponds
to 3 yg for Impingers 1 and 2 and 2 vg for Impingers 3 and 4.
3-32
-------
Laboratory reagent blank analyses were performed during the
analysis of the field samples. The results of these analyses are
presented in Table 3-3. The average value for five filter blanks
was 29.7 yg out of a range of 26.7 to 32.8; a blank correction of
30 yg was used to correct all the reported data. All of the
blank values for the rinse and impinger samples were near the
analytical detection limit of 2 to 8 yg. Because of the vari-
ability and relatively small value of the blank, no average value
was determined and no blank corrections applied.
Values below 50 yg were considered insignificant and not
reported because 8360 yg (7570 on the filter) was the minimum
amount of arsenic determined in any train and the blanks for the
liquid sample fractions varied considerably.
Each sample was first analyzed by the flame technique.
Samples whose concentrations were below 30 mg/liter were also
analyzed using the graphite furnace. Actual sample concentra-
tions were either gre.ater than 100 or less than 10 ppm. The
30-mg/liter limit was based on previous experience with Method
108, which indicated good agreement above this level. As the
analyses were completed and the data were reduced by the labora-
tory, the results were reviewed by the Quality Assurance Officer
(QAO). The QAO reviewed instrument calibration, the analysis of
the standard reference solution (SRS), agreement between flame
and furnace results, and general consistency of the data. He
then prepared a list of samples for reanalysis.
3-33
-------
TABLE 3-3. ARSENIC LABORATORY REAGENT BLANK DATA
Date
(1984)
6/8
Filter
total , yg
2.4
Rinse,3
mg/ liter
0.0079
Impingers,
mg/liter
0.0079
Connector,0
mg/ liter
0.0079
Between 235 and 328 ml of sample were received as the rinse fraction.
The maximum laboratory reagent blank corresponds to 3 yg for this
fraction.
Between 532 and 817 ml of sample were received as the Impingers 1 and
2 fractions and between 280 and 340 ml as the Impingers 3 and 4 frac-
tion. These correspond to maximum laboratory reagent blanks of 6 yg
and 3 ug, respectively.
cBetween 119 and 180 ml of sample were received as the connector
fraction. The maximum laboratory reagent blank corresponds to 1 yg for
this fraction.
3-34
-------
The analysis was performed in five batches by flame atomic
absorption. Eighteen sets of standards (0, 10, 30, 50, 80, 100
ppm) were analyzed with the samples. The linear regression data
for all the standards analyzed with a given batch of samples are
presented in Table 3-4. The average correlation coefficient is
0.9989, out of a range of 0.9994 to 0.9985. The average detec-
tion limit is 2.3 ppm. A value of twice the range of the 0-ppm
standard above the Y-intercept was used to calculate the detec-
tion limit. A standard reference solution independently prepared
from AS-O., with a nominal value of 150 ppm was analyzed (1-2
dilution) with each set of standards. (Standards were prepared
from a commercially available 1000-ppm standard solution.) The
average value obtained in the 18 analyses of this standard
reference solution (SRS) was 157.4 ppm, with a standard deviation
(SD) of 3.81 ppm [2.4 percent relative standard deviation (RSD)].
Only 1 of the 18 determinations made fell outside the range of
the mean ±2 SD (one was 166 ppm).
These data indicate that the precision and accuracy of the
flame atomic absorption analyses are well within acceptable
limits. The percent difference of the average measured value of
the SRS and its predicted value is 4.9 percent; the RSD of the
measured value is 2.4 percent.
The results of the audit samples supplied by EPA and deter-
mined by flame atomic absorption (listed in Table 3-5) are
consistent with the data just presented. The relatively large
difference at 10 ppm is predictable in that it is only 5 times
the average detection limit.
3-35
-------
TABLE 3-4. LINEAR REGRESSION DATA (FLAME)
Date
(1984)
6/4
6/5
6/5
6/11
6/13
No. of
standard
curves
4
2
2
5
5
Y-intercept
0.0031
0.0048
0.0056
-0.0011
0.0041
Slope
0.00489
0.00500
0.00496
0.00490
0.00450
Correlation
coefficient
0.9990
0.9994
0.9985
0.9990
0.9987
Detection
limit, ppm
2.1
1.2
1.6
1.6
4.9
3-36
-------
TABLE 3-5. ARSENIC AUDIT RESULTS
EPA No.
B-3-I
B-4-I
G-l-I
G-3-I
H-l-I
H-2-I
B-3-I*
B-4-I3
WP-4753
Cone 6
Lab No.
DC329
DC330
DC331
DC332
DC333
DC334
DC329
DC330
DM562
Volume, ml
500
500
500
500
500
500
500
500
1000
Arsenic
concentration
EPA values,
mg As/liter
10
10
100
100
40
40
10
10
0.207-0.393
Measured,
mg/ liter
10.2
11.7
111
107
43.9
43.9
11.1
10.7
0.356
Total
As, mg
5.12
5.83
55.6
53.3
22.0
22.0
5.54
5.34
0.356
Graphite furnace analysis.
3-37
-------
Table 3-6 presents the results of 10 samples checked by the
method of standard addition. The slopes of all the standard
addition analyses are between 0.9 and 1.1 except for those of
DM697, DM688, and DM660, which is probably due to an error in the
spiking or the fact that no given point was in the regression
analysis because a less-than value is unusable. An analysis of
the results of the unspiked samples and the X-intercepts (stan-
dard addition values) revealed that only Sample DM697 showed a
significant difference. The results for DM697 were expected,
based on the slope; the results of standard addition show no
\
consistent bias attributable to the sample matrices.
The samples were analyzed by atomic absorption in which
graphite furnace techniques were used. All samples below 30 ppm
were analyzed by furnace techniques. Sample concentrations were
either greater than 100 ppm or less than 10 ppm. Values obtained
from flame and furnace techniques cannot be accurately compared
below 10 ppm because this value is too close to the flame detec-
tion limit. Twelve sets of standards (0, 0.01, 0.05, 0.10, and
0.15 mg/liter) were analyzed with the samples. All the data sets
were reduced by linear regression analysis (see Table 3-7). The
average correlation coefficient for the linear regression anal-
ysis was 0.9970, out of a range of 0.9980 to 0.9954. The average
detection limit for the graphite furnace was 0.0033 ppm. A value
of twice the range of the 0-ppm standard above the Y-intercept
was used to calculate the detection limit.
3-38
-------
TABLE 3-6. ARSENIC STANDARD ADDITION RESULTS
Lab Number
DM643 Filter
DM670 Filter
DM697 Filter
DM736 Filter
DM637 Bomb
DM688 Bomb
DM650 Rinse
Spike,
ppm
0
20
30
40
0
20
30
40
0
20
30
40
0
20
30
40
0
20
30
40
0
20
30
40
0
20
30
40
Previously
determined
flame, ppm
26.16
30.07
31.45
28.24
<2.6
<3.5
<2.9
Measured,
ppm
22.45
45.58
52.03
62.70
29.12
47.80
56.92
69.60
35.35
48.47
57.37
66.26
26.90
47.36
60.48
66.93
<4.9
10.88
18.67
29.79
<4.9
11.55
20.22
28.45
<4.9
8.44
18.89
27.79
Linear
regression analysis
Slope = 0.992
Y intercept = 23.36
Corr. = 0.9955
X intercept = -23.54
Slope = 0.995
Y intercept = 28.48
Corr. = 0.9974
X intercept = -28.64
Slope = 0.769
Y intercept = 34.55
Corr. = 0.9964
X intercept = -44.90
Slope = 1.030
Y intercept = 27.24
Corr. = 0.9957
X intercept = -26.45
Slope = 0.946
Y intercept = 0.87
Corr. = 0.9949
X intercept = -0.92
Slope = 0.845
Y intercept = 3.2
Corr. = 0.9999
X intercept = -3.76
Slope = 0.968
Y intercept =0.98
Corr. = 0.9989
X intercept = -1.01
(continued)
3-39
-------
TABLE 3-6 (continued)
Lab Number
DM740 Rinse
DM660 Impinger
DM717 Impinger
Spike,
ppm
0
20
30
40
0
20
30
40
0
20
30
40
Previously
determined
flame, ppm
5.5
<2.1
<1.3
Measured,
ppm
<4.9
10.66
19.11
30.45
<4.9
11.55
17.11
26.45
<4.90
7.55
16.00
25.56
Linear
regression analysis
Slope = 0.990
Y intercept =0.28
Corr. = 0.9965
X intercept = -0.28
Slope = 0.745
Y intercept = 3.47
Corr. = 0.9894
X intercept = -4.66
Slope = 0.900
Y intercept =1.64
Corr. = 0.9994
X intercept = -1.82
3-40
-------
TABLE 3-7. LINEAR REGRESSION DATA (FURNACE)
Date
(1984)
6/8
6/11
6/15
No. of
standard
curves
2
4
4
Y-intercept
-0.0011
0.0019
-0.0014
Slope
4.081
4.316
3.853
Correlation
coefficient
0.9980
0.9975
0.9954
Detection
limit, ppm
0.0039
0.0028
0.0031
3-41
-------
A standard reference solution independently prepared from
As203 with a nominal value of 0.0750 ppm was analyzed with each
set of standards. (Standards were prepared from a commercially
available 1000-ppm standard solution.) The average value ob-
tained for the 21 analyses of this SRS was 0.0751 ppm with a
standard deviation of 0.0027 (3.6 percent relative standard
deviation). Historically, the mean value for this SRS is 0.0762,
with a standard deviation of 0.0027. The values obtained for the
SRS solution during this project are in good agreement with our
historical data. These data indicate that the precision and
accuracy of the furnace atomic absorption analyses are well
within acceptable limits. The difference in the average measured
value of the SRS and its predicted value is 0.2 percent; the RSD
of the measured value is 3.6 percent.
The results of audit samples analyzed using the graphite
furnace were listed in Table 3-5. These values are consistent
with the previous value and the accepted values. The results of
duplicate analysis are presented in Table 3-8. The absolute
value of the percent difference was calculated according to the
following equation.
X, _ X2
% Difference =
where X, and x~ are the individual values
X is the average of X., and X-
3-42
-------
TABLE 3-8. DUPLICATE ANALYSIS DATA
Sample fraction
Filter
Bomb
Rinse
Impinger
Filter3
Bomb3
Rinse6
Impinger
Arsenic, g
8,310, 8,470
8,770, 9,130
9,690, 9,590
10,900, 11,100
10,900, 11,300
10,400, 10,300
10,800, 10,700
10,900, 10,400
99, 93
351, 294
498, 467
290, 269
610, 648
768, 657
50, 48
4, 5
36, 35
39, 32
61, 56
40, 28
66, 51
678, 693
623, 629
35, 30
32, 29
4, 49
227, 191
33, 30
5, 45
43, 39
153, 55
% Difference
1.4
3.0
1.0
1.8
3.6
1.0
0.9
4.7
6.2
17.7
6.4
7.5
6.0
15.6
4.1
22.2
2.8
19.7
8.5
35.3
25.6
2.2
1.0
15.4
9.8
170
17.2
9.5
160
9.8
94
Same aliquot analyzed on different days.
3Sample aliquot prepared and analyzed on different days.
3-43
-------
Filter samples were analyzed using flame atomic absorption,
and all other sample fractions were analyzed using the graphite
furnace technique.
The first 16 values reported are based on duplicate analysis
of the same sample aliquot on the same day using the same cali-
bration curves. The agreement on the front filters is very good.
These filters contained better than 90 percent of the total
arsenic collected. The average percent difference for the
primary filter is 2.4 percent. The agreement for the other
sample fractions is acceptable and will not have a significant
influence on the overall method precision because they represent
less than 10 percent of the total arsenic collected.
The next five values reported are based on repeat analysis
of the same sample aliquot on different days using different
calibration curves. The agreement is good considering the
relatively small amount of arsenic contained in these fractions.
The last 10 values reported are based on repeat analysis of
different sample aliquots prepared and analyzed on different days
using different calibration curves. The agreement for the two
rinse samples (the only two containing a significant amount of
arsenic) is very good.
3-44
-------
SECTION 4
SAMPLING LOCATION AND TEST METHODS
This section describes the sampling sites and test methods
used to characterize arsenic emissions from each source evalu-
ated.
A four-train (quad) sampling system was used to collect
samples at the exit stack of the glass melting furnace. This
system allows four trains to sample simultaneously at essentially
a single point in the stack (see Figures 4-1 and 4-2).
Because this sampling approach allows four trains to sample
simultaneously at essentially a single point, it reduces the
effect of variations in the velocity and particulate profiles on
the sampling results. It also permits a statistically signifi-
cant number of samples to be taken in a short amount of time.
Further, since all four trains are identical for every run, the
within-train precision can be determined at the same time as the
relationship of the different trains is being compared. This
methodology for determining method precision was developed and
validated in a previous EPA study.* A total of four quad-train
runs representing 16 individual samples were collected. During
*
Mitchell, W. J., and M. R. Midgett. A Means to Evaluate the
Performance of Stationary Source Test Methods. ES and T,
10:85-88, 1976.
4-1
-------
BACKUP
METHOD 5
FILTER
IMPINGER
TRAINS
(204°C) (288°C)
HEAT BOXES
BACKUP
•METHOD 5
FILTER
(izrc)
B A D C
CO CD CD CO
oo oo
oc cc oc o;
0.0. 0. O-
oD oA
OC oB
BACK VIEW
Figure 4-1. Quad train system for elevated temperature tests
4-2
-------
3 1n.
THERMOCOUPLE
2 1n.
1 in/
1 1n.
„,*] '
1n. H
3/4 1n
S" TYPE PITOT TUBEft
2:
[* 2 In. -—+\
Figure 4-2. Four-train sampling system showing nozzle, pitot
tube, and thermocouple position.
4-3
-------
these runs, a single Method 108 train was run with the nozzle
positioned as close to the quad nozzle arrangement as possible
without causing interference.
All samples were collected at the furnace exit stack as
depicted in Figures 4-3 and 4-4. Ambient ejector air is con-
trolled automatically to maintain furnace pressure and is intro-
duced angularly as depicted in Figure 4-3 at a volume ratio of
about 1:1 to the furnace gases. According to plant personnel,
the furnace gas temperature is about 760°C (1400°F), and exit gas
temperatures ranged between 260° and 316°C (500° and 600°F),
which indicated that the gases were relatively well mixed at the
sample cross section. Single-point, isokinetic sampling tech-
niques were used in each quad run and reference train tests.
Prior to sampling, a complete velocity and temperature profile
was established using procedures described in EPA Methods 1 and
2.* The velocity and temperature data were used to select sample
nozzle sizes so as to maintain isokinetic sample rates and ensure
adequate sample volume [0.85 dscm (30 dscf)] in each train. The
quad nozzle assembly was positioned approximately 52 cm (20.5
in.) from the inside wall of the stack in each run. Sampling
rates generally ranged between 0.014 dsm3/m (0.50 dscf/m) and
0.017 dsm3 (0.60 dscf/m), and sampling times were typically 60
and 70 minutes.
In the Method 108 traverse tests, 24 sampling points were
used to traverse the cross-sectional area of the stack. Each
*
40 CFR 60, Appendix A, Reference Methods 1 and 2, July 1983,
4-4
-------
142 on
, .
(3 ft 0 In
BUTTERFLY
VALVE
CHAIN
ADJUSTMENT
7.6 m
. .
(25 ft 0 1n.)
1.5 in
(5 ft 0 1n.)
(36 1n.)
V i.d. '
VENTURI
MIXING
7.9 m
(26 ft 0 1n.)
1 '
0.76 m
(2 ft 6 1n
1.4 m
(4 ft 7 1n.]
...I I
._,
.) / EJECTOR \
l'"°\
CHAMBER
TRANSITION
f
EJECTOR
(AMBIENT
AIR)
r r
i \
SASES \
1 | FURNACE |
( *1 ft 6 1nJ
1 1
1
GROU
Figure 4-3. Furnace exit stack elevation (no scale)
4-5
-------
3-1/2 1n. 1.d.
SAMPLE PORT
BUTTERFLY
VALVE
AXIS
6 in. i.d.
SAMPLE PORT
(QUAD TRAIN)
STACK I.D. (3 SAMPLE
PORT: 104 cm (41 in.)
CROSS SECTION
Figure 4-4. Furnace exit stack sampling port location
(no scale).
4-6
-------
point was sampled for 2.5 minutes, yielding a total test time of
60 minutes.
4.1 SAMPLING AND ANALYTICAL PROCEDURES
The sampling and analytical procedures used in this test
program followed those described in EPA Reference Methods 1
through 4* and proposed Method 108 as detailed in the site test
plan prepared by PEI and reviewed by EMB. The procedures, which
are described briefly here, are detailed in Appendices D and F.
4.1.1 Velocity and Gas Temperature
A Type-S pitot tube and an inclined draft gauge manometer
were used to measure gas velocity pressures at the test sites.
Temperature was measured with a thermocouple and digital readout.
During each sample run, velocity and temperature measurements
were taken at a single sampling point in the duct. Prior to each
test series, separate velocity measurements were taken by tra-
versing the entire sample cross-sectional area to determine an
average value. Measurements were taken in accordance with proce-
dures outlined in Reference Method 2 of the Federal Register.*
4.1.2 Molecular Weight
Flue gas composition was determined in accordance with the
basic procedures described in Reference Method 3.* Grab samples
were collected before any sampling began to establish baseline
contents of oxygen, carbon dioxide, and carbon monoxide. Bag
*
40 CFR 60, Appendix A, Reference Methods 1 through 4, July 1983.
4-7
-------
samples were collected at least twice daily during sampling at
each source and analyzed with an Orsat gas analyzer. An inte-
grated bag sample was also collected during each Method 108
traverse test and analyzed using an Orsat gas analyzer.
Method 108* was used to measure arsenic concentration except
that the impingers containing hydrogen peroxide (H-O.) for SO-
determination were eliminated due to low (less than 30 ppm)
concentrations of S0_. All tests were conducted isokinetically
by regulating the sample flow rate relative to the gas velocity
in the stack as measured by the pitot tube and thermocouple
attached to the quad probe arrangement (see Figure 4-2). Each
individual sampling train consisted of a heated glass-lined
probe, a heated 7.6-cm (3-in.) diameter glass fiber filter (What-
man Reeve Angel 934AH), and a series of four Greenburg-Smith
impingers followed by a vacuum line, vacuum gauge, leak-free
vacuum pump, dry gas meter, thermometers, and a calibrated ori-
fice. In each train, probe and filter temperatures were moni-
tored using digital indicators and thermocouple leads located in
each probe and immediately behind the Method 108 filter frit. In
Quad Runs 10, 12, and 13, a 53-cm (21-in.) glass connector was
used to attach the front filter to a backup filter maintained at
approximately 121°C. The impingers followed the backup filter in
these runs.
The amount of water collected in the impinger section of the
sampling train was measured gravimetrically at the end of each
Method 108 is proposed. 40 CFR 61, Appendix B, Method 108,
July 1983.
4-8
-------
sample run to determine the moisture content of the flue gas.
The contents of the first two impingers, each of which had been
charged initially with 150 ml of distilled water, were trans-
ferred to a polyethylene container. These impingers and all
connecting glassware (including the back half of the filter
holder) as well as a third (empty) impinger were rinsed with 0.1
N NaOH; the rinse was then added to the container. The contents
of the first two impingers and 0.1 N NaOH rinse were analyzed for
arsenic by atomic absorption. In the elevated temperature runs,
the third and fourth impingers were recovered and analyzed simi-
lar to Impingers 1 and 2.
4-9
-------
SECTION 5
PROCESS OPERATION
Tests were performed on the uncontrolled emissions from a
regenerative natural-gas-fired glass melting furnace. The fur-
nace evaluated has a pull-rate capacity of 90 to 100 tons/day and
produces primarily crystal glass utilizing arsenic as a condition-
ing and refining agent. Furnace pressure is maintained by use of
an induced-draft ejector system as described in Section 4. Data
collected during this study indicate that the furnace gases and
the ejector air were adequately mixed at the sampling location.
Personnel from Radian Corporation (an EPA contractor) moni-
tored the furnace operation during each test. Appendix F of this
report contains a detailed process description and a summary of
furnace operating data.
5-1
------- |