EPA/600/R-94/038c
September 1994
Quality Assurance Handbook
for
Air Pollution
Measurement Systems:
Volume III
Stationary Source-Specific
Methods
Work Assignment II-228
EPA Contract No. 68-D1-0009
Prepared For:
Ms. Ellen Streib
Quality Assurance Support Branch
Quality Assurance and Technical Support Division
AREAL, Environmental Protection Agency
Research Triangle Park, NC 27711
Through:
Research Triangle Institute
Center for Environmental Measurements and Quality Assurance
P.O. Box 12194
Research Triangle Park, NC 27709
Prepared By
Entropy, Incorporated
Roger T. Shigehara, Lisa M. Grosshandler
and Theresa A. Russell
P.O. Box 12291
Research Triangle Park, NC 27709
September 30, 1994
^§9 Printed on Recycled Paper
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DISCLAIMER
This document was prepared by Entropy, Inc. under Contract No. 68-D1-0009, Work Assignment
No. II-228. This document has been reviewed by the Quality Assurance Support Branch, Quality
Assurance and Support Division, Atmospheric Research and Exposure Assessment Laboratory, U.S.
Environmental Protection Agency. However, the contents do not necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use by EPA or by Entropy.
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PART I
1.0 INTRODUCTION
The Quality Assurance Handbook for Air Pollution Measurement
Systems is comprised of five volumes: Volume I (Principles),
Volume II (Ambient Air Specific Methods), Volume III (Stationary
Source Specific Methods), Volume IV (Meteorological
Measurements), and Volume V (Acid Deposition Measurements).
The earlier edition of Volume III contained descriptions of 20
Environmental Protection Agency (EPA) test methods and 2550
pages. This revised edition covers 78 EPA test methods and 450
pages. The fourfold increase in the number of test methods and
fivefold reduction in the number of pages was accomplished: (1)
by removing duplication between methods; (2) by removing the copy
of the original Federal Register which contained the test method;
and (3) by providing only the information on the features which
make the test method unique.
The copy of the test method as published in the Federal Register
was removed to encourage the user of Volume III to obtain the
most current edition of Title 40 of the Code of Federal
Regulations (40 CFR) before conducting an emissions test for
regulatory purposes. EPA stationary source test methods covered
in this edition of Volume III are found in Parts 60 and 61 of
Title 40 of the CFR. The CFR is an authoritative, legally
binding document which is amended and updated frequently. It is
the law. In contrast, Volume III is a guidance document only and
has no legal standing unless the CFR specifically requires the
tester to follow Volume III.
This edition of Volume III provides data sheets which identify
the essential information which must be collected when using the
EPA test method for regulatory purposes. These data sheets are
in the public domain and may be copied without seeking approval
from the EPA.
The data sheets conform to the latest version of the EPA test
method as published in the CFR; they are structured to serve as
quality assurance/quality control (QA/QC) checklists for
assessing the completeness, accuracy, precision,
representativeness, reasonableness and legibility of the test
data collected. The EPA is aware that the technology specified
in the CFR for some of the test methods (e.g.. Methods 15, 16, 18
and 25) is obsolete. In such cases the users should modify the
forms to conform to the test methodology they are using.
We plan to revise Volume III again in 1997 following the format
of this edition. We welcome comments from users concerning:
errors they found in. this edition, the usability of the new
-------
format, points where clarification is needed, and suggestions to
improve further the usability of Volume III. Comments should be
sent to
Coordinator for QA Handbook
EPA MD-77B
Research Triangle Park, NC 27711
1.1 QA OBJECTIVES
The objectives of a QA program are to produce data that are
complete, representative, and of known precision and accuracy.
These terms are defined in detail in Volume I of the QA Handbook
(Principles, EPA 600/R94-038a). Readers desiring complete
definitions of these terms should consult Volume I, which is
available at no cost from the EPA's Center for Environmental
Research Information, 26 W. Martin Luther King Dr., Cincinnati,
OH 45268.
1.1.1 Completeness
Completeness is the percentage of the required field and laboratory
measurements and all necessary documentation that was achieved.
For short term tests, completeness should be 100%.
1.1.2 Precision and Accuracy
Precision and accuracy are measures of data quality. These
measures are included in the reference test methods and procedures
in the form of equipment, reagent, ,and performance specifications,
e.g., calibration accuracy, precision of triplicate analyses,
percent recoveries, and traceabilities to primary standards. All
equipment, reagent, and performance specifications should be met.
1.1.3 Representativeness
Representativeness is defined by the "when, " "how, " and "how many"
measurements taken. These conditions are usually specified within
the regulation, e.g., source operating at maximum capacity using
high sulfur content fuel, Method 6C for S02 at a single point at
the centroid of the stack, three 20-minute runs, etc. If not
specified in the regulations, all interested parties must agree
upon the desired "representative" conditions before any
measurements are taken.
1.2 EQUIPMENT, REAGENT and PERFORMANCE SPECIFICATIONS
The EPA test methods use equipment, reagent, and performance
specifications to define "acceptable" errors in measurements. The
accuracy of each measurement or set of measurements is determined
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through calibration against reference standards defined within the
test methods. These specifications are listed under the apparatus,
reagent, procedure, and calibration sections of the test method.
Emission measurements, e.g., average pollutant emission rate for
the test period, involve many individual measurements. Each
measurement has an uncertainty; therefore, the overall data quality
(precision and accuracy) of the emission measurement is a
combination of the individual uncertainties. Because process
conditions also affect the measurement variations, the data quality
is usually not mentioned within the test method.
1.3 DOCUMENTATION
In litigation, the test results may be subjected to the
requirements of legal rules of evidence. Therefore, complete and
accurate records should be kept to document that the testing
conformed to the prescribed test procedures. Two important items
of documentation are discussed below.
1.3.1 Data Sheets and Other Field Notes
Data sheets document that all pertinent data were collected and
recorded. Data sheet forms should clearly identify the process
tested, the date and time, the test' location, and the sampling
personnel. Examples of such data sheets are included in this
edition of Volume.III.
Records should be in indelible ink. Mistakes should never be
erased; they should be lined out, initialed, and the correct data
written above. The test supervisor should assemble all original
data sheets for inclusion in the test report.
1.3.2 Chain-of-Custody
The purpose of the chain-of-custody is to prevent losses, mixups,
accidental contamination, and tampering, and to document the
integrity of the data.
• Identification. Reagents, filters, and
recovered samples must be positively identified.
Containers or filters must have a unique
identification number. Figure 1 shows an example of
a standardized identification sticker for each of
the four containers needed to collect a sample for
EPA Method 5.
• Contamination and Tampering. All samples should be
secured to prevent contamination and tampering.
Sample containers should be placed in a locked
sample box or sealed with a self-adhesive sticker
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that has been signed and numbered by the sample
custodian. This sticker must break when the
container is opened.
Chain-of-Custody Record. The chain-of-custody
record is necessary to show that the sample
analyzed was the same sample taken. Figure 2 shows
a form for particulate samples which establishes
the chain-of-custody from the test site to the
laboratory. Each recipient of the sample should
sign the form. A general rule to follow in sample
handling is "the fewer hands the better."
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Figure 1.
Typical labels used for samples collected for a source test of
paniculate manor using EPA Test Method 5.
PLANT:
JOB* DATE: / /
RUN#:
MATRIX: 200mLOIH2O
LOT#:
FINAL WT.
TARE WT.
FV, mLs. «B
RINSE ADDED IN FIELD? YES NO
PLANT:
JOB *: DATE: / /
RUN*:
MARK LIQUID LEVEL ON LABEL
IF APPLICABLE
'
Reagent Container
Rinse Container
PLANT:
JOB#:
RUN#:
FILTER ID #:
DATE: / /
RUN*
FINAL WT.
TAREWT.
Filter Container
Silica Gel Container
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2.0 QUALITY ASSURANCE
The QA Project Plan (QAPP), also known as the Site Specific Test
Plan (SSTP), is the main vehicle for obtaining quality data on a
test-by-test basis. A QAPP (SSTP) for an emission test should
contain the following information, as appropriate.
2.1 TITLE PAGE (WITH APPROVAL SIGNATURES)
2.2 TABLE OF CONTENTS
• List of contents and page numbers
• List of figures and page numbers
• List of tables and page numbers
• Appendix with test methods.
2.3 INTRODUCTION
2.3.1 Summary of Test Program
Identify or state,'as applicable, the following:
• Responsible groups or organizations
• Overall purpose of the emission test (e.g., determine
compliance with an emission limit, measure process stream
losses, obtain engineering data for designing control
. equipment)
. • Regulation(s), if applicable
• Plant description: industry; name of plant; plant
location; processes of interest; emission points arid
sampling locations, etc.
• Pollutants to be measured
• Expected dates of test.
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2.3.2 Test Program Organization
Include the following:
• Organizational chart with lines of communication.
• Names and phone numbers of responsible individuals
• If necessary, a discussion of the specific, organizational
responsibilities.
2.4 SOURCE DESCRIPTION ; , ,
2.4.1 Process Description .
Include the following:
• A flow diagram which provides a general description of
the basic process and indicates the, emission and process
stream test points
• Discussion of unit or equipment operations that might
affect testing or test results, e.g., batch .operation,
high moisture or high temperature effluent, presence of
interfering compounds, plant schedule
• List of key operating parameters and standard operating
ranges, production rates, or feed rates, if available.
2.4.2 Control Equipment Description
Include the following:
• Description of all air pollution control systems
• Discussion of typical control equipment operation and, if
necessary, a schematic
• Normal operating ranges of key parametersr if available.
2.5 TEST PROGRAM
2.5.1 Objectives
Restate the overall purpose of the test program and list (in order
of priority) the specific objectives for both emissions and process
operation data.
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2.5.2 Test Matrix
Include a table showing the following (include schematics, if
helpful):
• Sampling locations
• Number of runs
• ' ' Sample type/pollutant sampled
• Sampling method
• Sample run time
• Analytical method
• Analytical laboratory.
2.6 SAMPLING LOCATIONS
2.6.1 Sampling Locations
Provide a schematic of each location, including the duct diameter,
direction of flow, dimensions to nearest upstream and downstream
disturbances (including number, of duct diameters), location and
configuration of the sampling ports, nipple length and port
diameters, number and configuration of traverse points.
Confirm that the sampling location meets EPA criteria ,(if not,, give
reasons and discuss effect on results) and discuss any nonstandard
traversing or measurement schemes employed.
2.6.2 Process Sampling Locations
If process stream samples will be taken, include the following:
• Schematic of sampling locations
• Discussion of each measurement location and discussion on
the representativeness of each of these locations.
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2.7 SAMPLING AND ANALYTICAL PROCEDURES
2.7.1 Test Methods
Include the following:
• Schematic of each sampling train
• Flow diagram of the sample recovery
• Flow diagram of sample analysis
• Description of any modifications and reasons for them
• Discussion of any problems in sampling or analysis.
NOTE: If a non-EPA method is used in place of an EPA-approved
method, explain the reason. EPA methods published in the CFR and
other readily available standard methods, such as, ASTM and ASME
methods can be incorporated by reference. Any other test method
used should be placed in the test report. Be sure that non-EPA
methods are written in detail equivalent to that of the EPA
methods.
2.7.2 Process Data
Include a description of analytical, sampling, or other procedures
for obtaining process stream and control equipment data.
2.8 QA/QC ACTIVITIES '
2.8.1 QC Procedures
Provide the following for each test method:
• Data sheets
• QC check lists (could be part of the data sheets),
• QC control limits
• Discussion of any special QC procedures. ,
Examples of QC checks are calibrations of instruments, matrix
spikes, duplicate analyses, internal standards, blanks, linearity
checks, drift checks, response time checks, and system bias checks.
10
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2.8.2 QA Audits
For each of the- test methods for which an audit is to be conducted,
• list (if applicable) the following:
• Type of audits to be conducted
• Limits of acceptability
• Supplier of audit material
• Audit procedure
• Audit data sheet/QC check list.
2.8.3 QA/QC Checks of Data Reduction
Describe the following:
• Procedure for assuring accurate transfer of raw data and
accuracy of calculations
• Data quality indicators, such as: using F0 factors to
validate Orsat, GEM, CO2/O2 data, comparing process Q>
monitor and CEM O2 data, comparing flow rates measured at
different locations or by different sampling methods,
comparing data with previous field test results (if
applicable), and running mass balances.
2.8.4 Sample Identification and Custody
Include the following:
• Names of those responsible for these activities
• Sample identification and chain-of-custody procedure to
be used
• Sample identification label
• Chain-of-custody form
• Sample log sheet.
2.9 PLANT ENTRY AND SAFETY
2.9.1 Safety Responsibilities
Identify the person responsible for ensuring compliance with plant
entry,_ health, and safety requirements and the person who has the
authority to impose or waive facility restrictions. Also identify
11
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TABLE OF PROCEDURES AND i)ATA SHEETS
Method
1
1A
2
2A
2B
2C
2D
3
3A
3B
4
5
5A
5B
Description
Sample and Velocity Traverses
Flow Verification/Attemative Site
Sample and Velocity Traverses - Small Ducts
Velocity/Volumetric Flow Rate
Type S Pitot Tube Inspection
Leak-check of Fltot Tube System
Type S Fltot Tube
Barometric Pressure
Barometer
Temperature Sensors
Pressure Sensors
Direct Volume Flow Rate - Small Ducts
Metering System
Volume Flow Rate - Gasoline Vapor Incinerators
Volume Flow Rate - Small Ducts (Std Pitot)
Volume Flow Rate - Small Pipes and Ducts
Dry Molecular Weight
eak-Check of Orsat Analyzer
eak-check of Flexible Bags
eak-check of Non-isokinetic Sampling Trains
Oxygen and Carbon Dioxide
Emission Rate Correction Factor or Excess Air
Moisture (Reference)
Moisture (Approximation)
articulate Matter
eak-check of Isokinetic Sampling Train
eak-check of Metering System (After Pump)
Metering System/Orifice Check
Metering System
Metering System - Critical Orifices
'robe Nozzle
ry Gas Meter as Calibration Standard
ritical Orifices as Calibration Standards
articulate Matter - Roofing Operations
onsulfuric Acid Paniculate Matter
SS
2
2A
2B
2C
2D
3A
5
5A
5
FP
1
la
1A
2
2a
2b
2A
2B
2C
2D
3
3a
3b
3c
3A
3B
4
4a
5
5a
5b
QC5
5A
5B
FDS
1
la, 1b
1A
2
2A
2B
2D
3
6C
3B
4
4a
5
5
5
LP
5
5A
5B
LDS
.
5
5A
5
CP
2
2a
2d
2e
2f
2A
5
5a
5b
5c
5d
CDS
2
2a,b,c
2d
2d
2d
2A
2D
6C,6Ca
5
5b
5c
5d
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Method
5D
BE
SF
5F{alt)
6
6(alt)
6A
6B
6C
7
7A
7B
7C
7D
7E
8
10
IDA
10B
11
12
13A
13B
14
15
15A
16
16A
Description
'bsrtive Pressure Fabric Filters
Wool Fiberglass Insulation Manufacturing
Jonsulfate Paniculate Matter
vlonsulfate Particulate Matter
Sulfur Dioxide
Metering System
Sulfur Dioxide
Critical Orifice
Sulfur Dioxide, Carbon Dioxide, and Moisture
Sulfur Dioxide, Carbon Dioxide - Daily Emissions
Sulfur Dioxide
Interference Check
Nitrogen Oxides
Evacuated Flasks
Spectrophotometer
\Jitroflen Oxides - Ion Chromatograph ,
Nitrogen Oxides - Ultraviolet
Nitrogen Oxides - Alkaline Permanganate
Nitrogen Oxides - Alkaline Permanganate
Nitrogen Oxides
Sulfuric Acid and Sulfur Dioxide
Carbon Monoxide
Carbon Monoxide
Reaction Bulb
Carbon Monoxide
Hydrogen Sulfide
Inorganic Lead
Total Fluoride - Colorimetric
Total Fluoride - Specific Ion
Roof Monitors - Primary Aluminum
Manifold/Anemometer System
Propeller Anemometer
Reduced Sulfur
Reduced Sulfur
Reduced Sulfur
Reduced Sulfur
Hydrogen Sulfide in Cylinders
SS
5
5E
5F
5Fa
6
6a
' 6A
6A
6C
7
7A
7B
7C
7D
6C
8
10
10A
10B
11
12
ISA
13A
14
15
15A
16
16A
FP
5D
5E
SF
5F
6
6a
6A
6B
6C
6Ca
7
7
7
7C
6/7C
7E
8
10
10A
10A
11
12
13A
ISA
14
14a
15
ISA
16
16A
16Aa
FDS
5
5
5
5
6
6a
6A
6B
6C
7
7
7
7C
6/7C
6C
5
10
10A
10A
11
5
5
5
14
14a
15
ISA
15
16A
LP
5
5E
5F •
5Fa
6
6
6
6
7
7A
. 7B
7C
7D
8
10A
10B
11
12
13A
13B
13A/B
6
6
16Aa
LDS
5
5E
5F
5Fa
6
6
6
6
7
7A
7B
7C
7D
6
10A
10B
11
12
13A
13B
13A/B
6
6
CP
6
6a
-
\7
7a
10A
14
CDS
6
7
6C,6Ca
7
7a
6C.6Ca
10A
14
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Method
16B
17
18
20
21
22
23
24
24A
25
25A
25B
26
26A
27
101
101A
102
103
104
105
106
1O7
107 A
108
108 A
108B
108C
QA1
Description
Reduced Sulfur
Particulate Matter
Gaseous Organic Compounds - GC
Integrated Bag Sampling
Direct Interface Sampling and Analysis
Dilution Interface Sampling and Analysis
Adsorption Tube Sampling and Analysis
Nitrogen Oxides - Gas Turbines
Volatile Organic Compound Leaks
Visible Fugitive Emissions
PCDD and PCDF
Pre-test Procedures
Surface Coating
Printing Inks
TGNMO as Carbon
Gaseous Organics - FIA
Gaseous Organics - NDIR
Hydrogen Halides and Halogens
Hydrogen Halides and Halogens - Isokinetic
Vapor Tightness - Gasoline Delivery Tanks
Mercury - Chloro-alkali
Mercury - Sewage Sludge
Mercury - Chloro-alkali (Hydrogen Stream)
Beryllium Screening
Beryllium
Mercury - Sewage Sludge
Vinyl Chloride
Vinyl Chloride - Process
Vinyl Chloride - Process
Arsenic
Arsenic in Ore
Arsenic in Ore
Arsenic in Ore
Quality Assurance Audit Samples
SS
16B
5
20
23
25
25A
25A
26
26A
101
101
101
104
105
106
107
107 A
108
108 A
108 A
108C
FP
16B
17
18
18a
18b
18c
18d
20
20a
21
22
23
25
25A
25A
26
26
27
101
101A
102
103
104
105
106
107
107A
108
FDS
16B
5
18
18a
18b
18c
6a,18a,d
20
20a,b,c
21
22,22a
23
25
25A
25A
26
5
27
5
5
5
103
5
105
106
107
107
5
LP
5
18.
18a
23
23a
25,25a
26
26A
101
101A
101
103
104
105
106
107
107A
108
108A
108B
108C
QA1
LDS
5
18
18a
20
23
26
26
101
101
101
•
104
105
106.
107
107 A
108
108
108/C
108C
CP
18
21
.. 24
24A
CDS
18a,b,c
20
21
23,23a
24
24A
*
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Method
PS1
PS2
PS3
PS4
PS4A
PS5
PS6
PS7
Description
- tv -X- ^ *«y^^. •>*-••:
'„ „"* vV«&.Vi' - V" ;% "••
Opacity
Sulfur Dioxide and Nitrogen Oxides •
Alternative
Oxygen and Carbon Dioxide
Carbon Monoxide
Carbon Monoxide
Total Reduced Sulfur
Pollutant Mass Rates
Hydrogen Sulfide
SS
•• f :'' f
FP
, PSP,
1,a,b,c
2,a,b,c
2d
2,a,b,c
2,a,b,c
2,a,b,c
2,a,b,c
2,a,b,c
2,a,b,c
FDS
PSDS
1a,b,c
2
2
2
2
2
2
2
LP
PS
2
3
4
4A
5
6
7
LDS
.• .-
CP
*"*,*'
CDS
'; ,"^
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9/30/94-: F1-1
FIELD PROCEDURE 1
Sample and Velocity Traverses
Note: The data sheet (FDS) serves as a summary sheet; hence, there is no Summary Sheet.
A. Measurement Site
1. Select a site located a 2 equivalent
diameters (De's) downstream and 2:0.5 De
upstream from any flow disturbance such as
a bend, expansion, or contraction in the
stack, or from a visible flame.
2. If criteria above cannot be met, consider the
alternative procedure for determining the
acceptability of a measurement location in
FP 1a.
B. Number of Traverse Points
1. Refer to Figure F1 -1 (see FDS1 -2. right side
for paniculate traverses and left side for
velocity, non-particulate traverses) and
select the number of traverse points that
corresponds to the number of De's upstream
and downstream.
2. Select the higher of the two numbers of
traverse points, or a greater value, such that
the number is:
a. For circular stacks, a multiple of 4.
b. Rectangular stacks, one of those shown
in Table F1-1.
C. Cross-sectional Layout and Location of
Traverse Points for Circular Stacks
1. Locate the traverse points on two
perpendicular diameters according to
Table F1 -2 and Figure F1 -2.
2. For particulate traverses, locate one diameter
in a plane containing the greatest expected
concentration variation, e.g., after bends, in
the plane of the bend.
3. Stacks with D0 >24 Inches
a. If any traverse points fall within 1.00 in.
of the stack wall, relocate them away
from the wall by either 1.00 in. or a
distance equal to the nozzle ID,
whichever is larger. These relocated
traverse points (on each end of a
diameter) are the "adjusted" traverse
points.
b. Whenever two successive traverse
points are combined to form a single
adjusted traverse point, treat the
adjusted point as two separate traverse
points, both in the sampling (or velocity
measurement) procedure, and in
recording the data.
4. Stacks with D0's <24 Innhss
Follow the procedure in step C3, except use
0.50 in. instead of 1.00 in.
D. Cross-sectional Layout and Location of
Traverse Points for Rectangular Stacks
1. Determine the grid configuration from
Table F1 -1, and locate the traverse point at
the centroid of each elemental area (see
example in Figure F1-3).
2. If more than the minimum number of
traverse points is used, expand the
"minimum number of traverse points" matrix
(see Table F1 -1) by adding the extra traverse
points along one or the other or both legs of
the matrix; the final matrix need not be
balanced. For example, if a 4 x 3 "minimum
number of points" matrix were expanded to
36 points, the final matrix could be 9 x 4 or
12x3, and would not necessarily have to
be 6 x 6.
Traverse Distance
%o( diameter
4.4
14.7
29.5
70S
85.3
95.6
o
o
o
0
o
.
o
I
I
I
I
I
I
I
I
I
I
I
o
o
_J
o
o
o
o
Rgure F1-2. Circular stack cross-section layout.
Figure F1-3. Rectangular stack cross-section layout.
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9/30/94: FD1-1
Client/Plant Name
City/State
FIELD DATA SHEET 1
Sampling and Velocity Traverse Points
Job#
Date/Time
Test Location
Personnel
Portl.D.
Distance from Far Wall to Outside of Port
Nipple Length and/or Wall
Stack/Duct (/} Blue
Thickness
Print ( ) Measured ( )
Depth/Diameter (> 12 In. ?)
Width (if rectangular)
Equiv. Diameter (if rect.)
D0 - 2 D W/(D + W)
KeaW(>113/n.2?J
A = n D2/4 or D W
Upstream fe2 D,?)
Downstream feO.SD,?)
Distance
Rectangular
DO
Matrix
No. Pts*
* Cffcto larger of two.
Pt.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
% Duct
Depth
Dist. from
Inside Wall*
''•
Dist. from
Outside of
Port
Do not place closer to stack walls than:
1.0 in. for stack dia. >24 in.
0.5 in. for stack dia. 12 to -s24 in.
Sketch of Location: In the space above, sketch a flow diagram of the test location; show the distance from the ports to
flow disturbances before and after. Sketch the cross-sectional area; show sampling port locations. In horizontal ducts,
check for dust buildups and measure or estimate the depth.
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: FD1-2
CONSIDERATIONS
1. If test location is after a cyclone or inertial demister following venturi scrubbers or if the stack has tangential
I™ Pr° configurations that tend to induce swirling, verify that cyclonic flow does not exist. See FP la
(Check here // verification is made a,.J attach FDS 1a. If cyclonic flow exists, modify source by
2. IfD
3.
and attach FDS 1b.
4. For rectangular stacks, a balanced matrix layout must be used, i.e., one of the matrices shown in Table F1-1
unce the minimum sample .point matrix requirement is met, an unbalanced matrix may be used. For example if
you need a 3 x 3 matrix, but have ten ports, you may use a 3 x 10 or a 4 x 10 matrix. A 2 x 5 or 2 x lO.matrix
IS DOT 3CCGpi3DIG«
5. For paniculate traverses, one of the diameters must be in the plane containing the greatest expected
concentration variation, e.g., after bends, in the plane of the bend.
6' if~ny+°ith? sp^cifica*ions are n°t met, check with enforcement agency to determine whether the agency will
accept the location. Attach a statement of the agency's decision to this data sheet and obtain signature
if A <113 ^for rectan9Ular-do not use
d™nstfea™' °r <°'5 D« W»m torn* flow disturbance, e.g., bend, expansion, or
2T 3 "S \ T*' d° "Ot USB tMs meth°d' *«*'»**'**' ^nduct the procedure in
determme whether the location is acceptable. Check here _ if this option is used
No.
Pts
9
12
16
20
25
TABLE F1-1
Matrix
3x3
4x3
4x4
5x4
5x5
No.
Pts
30
36
42
49
Matrix
6x5
6x6
7x6
7x7
Figure F1-1
Us» higher of two numbers.
It >3 or >2 diameters and 1 duct .diameter
Is <24 Inches, use 8 or 9 points.
Valnelly Parltailato
DIAMETERS
UP DOWN
12 7
6
16 ~\
2.U
12
16
1 1.5
20
I_
-------
9/30/94: F1a-1
FIELD PROCEDURE 1a
Flow Verification or Alternative Measurement Site
Note: Use section A after such devices as cyclones and inertia! demisters following venturi scrubbers, or
in stacks having tangential inlets or other duct configurations that tend to induce swirling to check, for the
presence or absence of cyclonic flow.
A. Flow Verification B. Alternative Measurement-Site
1. Set up the apparatus (see FP 2). Level and
zero the manometer. Position the Type S
pitot tube at each traverse point, in
succession. The "0° reference" is when the
planes of the face openings of the pitot tube
are perpendicular to the stack cross-
sectional plane.
2. Rotate the pitot tube (up to ±90° yaw
angle) until a null reading is obtained.
Carefully determine and record the value of
the rotation angle (a) to the nearest degree
(see FDS 1a).
This alternative applies to sources < 2 De
downstream or <0.5 D. upstream, apd is limited
to ducts > 24 in.
1. Use 40 traverse points for circular ducts
and 42 points for rectangular ducts.
2. Prepare the directional probe and differential
pressure gauges as recommended by the
manufacturer.
3. Optional: Leak-check the system (see
FP 2a).
4. Level and zero the manometers.
Periodically check the level and zero during
the traverse. • •'•
5. Obtain the readings shown in FDS 1 b at
each traverse point, and determine the yaw
and pitch angles.
6. Mandatory: Leak-check the system (see
FP 2a). Failing the leak-check invalidates
the test run.
-------
9/30/94: FD1a-1
FIELD DATA SHEET 1 a
Flow Verification
Test
Point
No. of Pts:
Yaw Angle
(deg)
Sum:
Avg:
Test Location
Job# Date/Time
Pitot ID # Personnel
Note: To combine this information with the preliminary traverse for Method 5
sampling, use the data sheet under Method 5.
CONSIDERATIONS
Are the face openings of the Type S pitot tube parallel to each other and
perpendicular to the axis passing through both?
When the face of the pitot tube is parallel to the axis of thp tt-irif nr HI n-+
does the yaw angle indicator read zero?
Average yaw angle < 20°? If not, do not use this location. Alternatively,
modify the source by using straightening vanes or use another location that
satisfies Method 1 criteria.
No. of Pts = includes points with 0° yaw.
Sum = sum of absolute values
Avg = Sum/(No. of Pts)
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: FD1b-1
FIELD DATA SHEET 1b
Alternative Measurement Site
Test Loca
Date/Tirm
Duct Size
Note: Th
minimal;
Test
Pt
tion JOD ff
5 No. of TestPts (/):
>24//7.
fs alternative proce
the procedure gene
Yaw
*
n
n _ M
p,-fb
(?) 3-D
dure is Urn
rally applit
p,-p,
Pitot
Personnel
42 (Rectangular) 40 (Circular,
ited to ducts >24 inches in diameter where blockage and wall effects are
>s to sites <2Dg downstream and <0.5 De upstream from flow disturbances.
Pitch
•
n
M aV9
HI
Test
Pt
Avg (abs)
Post-test
Yaw
P4-Ps
PI - P2
Pitch
Ri
Leak Check (Stable for > 15 seconds at 3 in. H2O?)
(n-D
RI :S20° and SD =310°? If so, use at >24or 25 traverse points for particulate sampling and 5:16 for velocity
measurements.
QA/QC Chock
Completeness
Legibility
, Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/3O/94: FTA-1
FIELD PROCEDURE 1A
Sample and Velocity Traverses in Small Stacks or Ducts
Note: '''his procedure is the same as that in FP 1, except for the special provisions that apply to small
stacks or ducts, i.e., 4 in. £ D < 12 in. or 12.57in.2 £A<113 in.2.
A. Selection of Measurement Site
1. Paniculate Measurements - Steady or
Unsteady Flow
Select a site as shown in Figure F1A-1 (see
FDS 1A).
2. Paniculate (Steady Flow> or Velocity (Steady
or Unsteady Flow) Measurements
If the average total volumetric flow rate
in a duct is constant with respect to time
or if only velocity measurements are -
required, select one location and use the
same criterion as in FP 1.
Conduct velocity traverses before and
after paniculate sampling to demonstrate
steady state conditions, i.e.,
vf/v, £1.10.
a.
b.
B. Number of Traverse Points
Particulate Measurements (Steady or
Unsteady Flow)
1. Use FP 1 except consider the distance
between the velocity and sampling sites in
addition to the upstream and downstream
distances.
2. Choose the highest of the three numbers of
traverse points as in FP 1.
-------
9/30/94: FD1A-1
FIELD DATA SHEET 1A
Sampling and Velocity Traverse Point Determination
(Small Stacks or Ducts)
Test Location.
Date/Time
Job*
Personnel,
So7?A?pp!ies only when 4 in. * D <12 in. (circular) and 12.57 in.2 , A <113 in.2 (rectangular). A standard type pitot tube
must be used for the velocity measurements and must WOT be attached to the sampling probe.
Use FDS 1 and attach this sheet to it. The following are pertinent to FP 1 A:
Distance from Ports to Flow Disturbances (see figure below)
Std Pitot Tip Plane
Distance De No. Pts
Sampling Port
Distance De No. Pts
Upstream B.
Downstream A.
C.
B
Use the upstream/downstream distances as in FP 1 to determine the minimum number of traverse points; use the highest of
the four numbers of traverse points.
If the source operates under steady flow conditions and one test location is used for both velocity and particulate matter
measurements, the average velocity after the particulate sampling run must agree within ±10% of that before the test run.
Attach appropriate FDSs.
Figure F1A-1.
Re
<
A and B = Velocity port distuibanees distances
BandC= Sampling port disturbances distance
>
NOTE : This is dimension to
/pilot tip, not to port.
*2 Do i2 Do
\\P*T b " w VJ
\ 1 ' T
I i -•••••«-^&a»£?, ( ^^
^0
1 .
'•Vi'
<
V H • ? '
Velocity \ Asampling Flow distuibance
port pot
NOTE: Velocity port must be downstream from sampling port.
AH three distances (A, B. and C) must be shown on
sampling location schematic.
QA/QC Check
Completeness _
Legibility.
Accuracy.
Specifications.
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
SUMMARY SHEET 2
9/30/94: S2-1
Client/Plant Name
Job No.
Sampling Location
Run ID#
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Abs Stack Pressure (Pb + Pg/13.6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temp (460 + ts), R
Moisture Content, fraction
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Stack Area, ft2
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(tsi +460) Ap]1/2
Average Velocity, ft/sec
Volumetric Flow Rate, dscfh
Volumetric Flow Rate, wscfh
Post-test Calibration Checks
Temperature and Barometer
Differential Pressure Sensor
Run #1
Run #2
Run #3
%CO2
%02
%{CO + N2) FDS 3
FDS 2
FDS 2
FDS 2
FDS 2
FDS 2
FDS 2
FDS 2
FDS 1
FDS 1
FDS 2
FDS 2
FDS 2
SS2
FDS 2
SS2
FDS 4
FDS 3
FDS 3
Avg
M
Ap
[TsiAP]
V
1/2
Q
Q
sd
FDS 3
FDS 1
CDS2a
FDS 2
FDS 2
SS2
SS2
SS2
CDS2d
CDS2d
v - 85.49 C
17.64 (3600)
CL_ =
-------
9/30/94: F2-1
FIELD PROCEDURE 2
Stack Gas Velocity and Volumetric Flow Rate
(Type S Pitot Tube)
A, Pretest Preparations
1. Inspect or calibrate Type S pitot tube
(see CP 2 or CP 2a).
2. Calibrate barometer (see CP 2d).
B. Procedure
1. ' Set up the apparatus as shown in
Figure F2-1. Use FDS 2.
2, Optional: Leak-check the setup (see FP 2a).
3. Level and zero the manometer.
4. Record all necessary data as shown in
FDS 2.
5. Measure the velocity head and temperature
at each traverse point.
6. Measure the static pressure in the stack.
7. Determine the atmospheric pressure.
8. Determine the stack gas dry molecular
weight (see FP 3).
9. Obtain the moisture content from FP 4 (or
equivalent) or from FP 5.
10. Determine the cross-sectional area of the
stack or duct at the sampling location.
Whenever possible, physically measure the
stack dimensions rather than using
blueprints.
11. Mandatory: Leak-check the pitot tube setup
(see FP 2a).
12. Check pitot tube for damage.
13. If any Ap ^0.05 in. H2O, check the
necessity of using a more sensitive
differential pressure gauge (T <1.05).
See FDS 2.
C. Post-test Calibrations
After each test series (use CDS 2d):
1. Calibrate temperature gauges (see CP 2e).
2. Calibrate differential pressure gauges other
than inclined manometers, e.g., magriehelic
gauges (see CP 2f).
1.80-2S4cm-
(0.75-1.0 In.)
_Lcc
7.62 on (3 h.)'
LMk-FrM Connsctions
'Suggested (Interference Free)
Pilot lube/Thermocouple Spacing
Figure F2-1. Type S Pitot Tube Manometer Assembly.
-------
9/30/94: FD2-1
FIELD DATA SHEET 2
Velocity Head, Temperature, and Stack Pressure Measurements
Client/Plant Name
City/State
Job*
Date
Test Location/Run #
Personnel
Note: Ensure thatpitot tube is aligned parallel to the stack or duct axis.
PitotTubelD#
Pitot Tube Coefficient (Cb)
Ap Gauge Sensitivity
Barometric Pressure (Pb) (in. Hg)
Test Location Elevation Difference
from Bar,, (positive if higher) (B) (ft)
Corr Pb = Ph - 0.001 B (in. Hg)
(vO Piezometer Type S
Static Pressure (Pa) (in. H2O)
Post-test Leak Check: Side
Pressure Tap Ap (in. H2O)
Stable for 15 seconds? (yes no)
A B
Pitot Tube Condition:
Damaged?
Post-test Intercomponent Spacing:
Level/Zero Checks: Mark Pt. #'s with an asterisk (*)
Velocity Traverses
Start Time: Finish Time:
Pt.
#
Ap
in. H2O
Temp.
°F
Pt.
#
Average:
Ap
in. H20
Temp.
°F
QA/QC Check
Completeness
Legibility,
Checked by:
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: FD2-2
CHECKLIST
Velocity Differential Pressure Gauge
Pressure gauge sensitivity
in. H2O.
Calculate T and ensure that T ^ 1 .05.
T =
PJ *
where:
£pj = individual velocity head reading at traverse point i, in.
H20.
n= total number of traverse points.
Temperature Gauge
Ensure that the temperature gauge (thermocouple) attached to the pilot tube is in an interference-free
arrangement, i.e., at least 3/4 inch clearance'.
Ensure that the sensor tip is not touching any metal.
Pressure Probe Manometer
Ensure readability of the manometer ^0.1 in. Hg.
Barometric Pressure, FP 2a, Procedure 2 (if used)
Weather Station Value, A
Weather Station Elevation, B
Test Location Elevation, C
Barometric Pressure, Pb = A + 0.001 (B - C)
in. Hg
ft
ft
in. Hg
-------
FIELD PROCEDURE 2a
Leak-Check of Pitot Tube System
9/30/94: F2a-1
feas? 3n H, ' eSSUre mus
least 3 in. H20 velocity pressure registers on stable for at least 15 seconds)
the manometer, and close off the impact
opening. 3. Do the same for the static pressure side,
except use suction to obtain -3 in. H20.
-------
9/30/94: F2b-1
FIELD PROCEDURE 2b
Barometric Pressure
A. Procedure 1 B. Procedure 2
1. Read and record the field barometer at the 1. Obtain the station pressure or absolute
sampling location. barometric pressure Pr from a nearby
2. If the field barometer is read at ground level N,ational Weather Service station and its
or at an elevation different from the ' elevat.on (A) ,n feet above sea level.
sampling location, adjust the reading at a 2. Determine the elevation (B) of sampling
rate of 0.1 in. Hg per 100 ft (see step B3, location in feet above sea level.
except Pr would be the field barometer ,„ „ . . . . .
reading). Calculate the site barometric pressure (Pb)
as follows:
Pb = Pr + 0.001 (A-B)
-------
9/3O/94: C2-1
CALIBRATION PROCEDURE 2
Type S Pitot Tube Inspection
Note: Method 2 provides the criteria for an acceptably constructed Type S pitot tube. However, the
procedure for making the necessary measurements is not specified. One approach is given below.
1. Use a vise with faces that are parallel and 5.
perpendicular. Use a carpenter's level
(or similar) to make this check.
Measure the external tube diameter (Dt) with a
micrometer, machinist's rule, or internal
caliper.
2. Place the pitot tube in the vise, and level the
pitot tube horizontally using the degree
indicating level or the carpenter's level.
3. Place a degree indicating level as shown on
CDS 2.
4. Measure distance A, which is PA plus PB.
Method 2 specifies that PA = PB, but does not
give any tolerance for this measurement.
Experience has shown that this measurement is
very difficult; therefore, it is suggested that
PA = PB = A/2.
6. Record all data as shown on CDS 2.
7. Calculate dimensions w and z as shown on
CDS 2.
-------
9/30/94: CD2-1
CALIBRATION DATA SHEET 2
Type S Pitot Tube Inspection
D*Qr*o Indicating lev*I position for
dtttrmlnlng cti tnd 02.
Digr«* Indicating l«v«l position for
determining PI and PI.
I ^
Dcgra* Indicating Uvel position for
determining®.
Degree indicating level position for
deteminingYthen calculate Z.
Level and Perpendicular?
Obstruction?
Damaged?
a, (-10° £ o, ^ +10°)
a2 (-10° £ a2£i +10°)
6, (-5° i S, S +5°)
B2 (-5° £ &2 £ +5°)
Y
0
z - AtanK (^ 0.125")
w = AtanG (<; 0.03125")
Dt (3/16" £ Dt s; 3/8")
A
A/2Dt (1.05 s PA/Dt £1.5)
CW/QC CA0C*
Completeness _
Legibility
Accuracy
Specifications
Reasonableness
Certification
\ certify that the Type S pitot tube/probe ID# meets or exceeds all specifications,
criteria and/or applicable design features and is hereby assigned a pitot tube calibration factor Cp of 0.84.
Certified by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: C2a-7
CALIBRATION PROCEDURE 2a
Type S P:tot Tube
A. Preliminaries
1. Check the Type S pitot tube construction
specifications (see CP 2 and attach CDS 2).
Do not use pitot tubes that do not meet the
alignment specifications for the face
openings.
2. Permanently mark ID# and mark one leg of
the tube A and the other, B.
3. Check the standard type pitot tube
specifications (see CP 2b)
4. Check the calibration flow system
specifications (see CP 2c).
5. Consider the items in section C.
B. Procedure
1. Fill the manometer with oil that is clean and
of the proper density. Inspect and leak-check
all pitot lines. A manometer setup using
three-way valves as shown in Figure C2a-1
will facilitate the operation.
2. Turn on the fan, and allow the flow to
stabilize.
3. Level and zero the manometer. Position and :
align the standard pitot tube at the calibration
point. Seal the entry port surrounding the
tube. Read and record Apstd (see CDS 2a).
4. Remove the standard pitot tube from the
duct, and disconnect it from the manometer.
Seal the standard entry port.
5. Connect the Type S pitot tube to the
manometer. Open the Type S entry port.
Check the manometer level and zero, insert
and align the A side of the Type S pitot tube
at the same measurement point as that of the
standard pitot tube. Seal the entry port
surrounding the tube. Read and record Aps.
6. If the B side is also being calibrated, align the
B side. Read and record Aps.
7. Remove the Type S pitot tube from the duct,
and disconnect it from the manometer.
8. Repeat steps B3 through B7 until three pairs
of Ap readings have been obtained for A side
and, if applicable, B side).
9. Calculate Cp as shown on the data sheet.
C. Spec/a/ Cons/derations
1 • Isolated Type S Pitot Tube. Must be used
alone or, if used with other components
(nozzle, thermocouple, sample probe), in an
arrangement that is free from aerodynamic
interference effects (see Figures C2a-2
through C2a-4)
2. Type S Pitot Tube-Thermocouple
Combinations (without sample probe). Must
be used in same configuration of pitot tube-
thermocouple combination or with other
components in an interference-free
arrangement (Figures C2a-2and C2a-4).
3. Assemblies with Sample Probes. Check for
blockage effect before calibrating as shown
in Figures 2a-5a and 2a-5b. If necessary,
the calibration point may be a few inches
off-center. If blockage is significant, adjust
calibration coefficient as shown in CDS 2a-1.
4. Probe Assemblies in Non-interference Free
Arrangements. Perform separate calibrations
with each of the commonly used nozzle sizes
in place.
5. Probe Assemblies Always Used in Same
Orientation. Calibration of only the side used
is acceptable.
6- Unacceptable Assemblies. Impact pressure
opening plane of the pitot tube below the
entry plane of the nozzle (see Figure C2a-2).
7. Single Velocity Calibration at 3,OOOfpm.
Type S pitot tube coefficients are ±3% for
the measurement of velocities above 1,000
fpm and to ±5% to ±6% for the
measurement of velocities between 60O and
1 ,OOO fpm.
-------
Fbwstratghteners
(if required)
Type S pilot
tube port
Pitot tube calibration set-up.
Figure C2a-1.
TypeS Pitot Tube
I xa1.90cm(*iln.)(orD
Sampling Nozzle
.1.3cm('/4ln.)
A. Bottom View; showing minimum pilot tube-nozzle separation.
Sampling
Nozztev.
Static Pressure
Opening Plane
B. Side View; to prevent pilot tube from Interfering with gas •
flow streamlines approaching the nozzle, the Impact pressure
opening plane of the pHot tube shall be even with or above the
nozzle entry plane.
Figure C2a-2. Proper Pitot Tube-Sampling Nozzle Configuration.
-------
W »7.62 cm
(3H.)
Temperature Sensor
:»1.80 cm
(3/4 In)
Temperature Sensor
)p, Type SFHol Tube
Typ«S Pilot Tuba
Samp
iiil
inn
Figure C2a-3. Proper Thermocouple Placement to Prevent Interference;
t\ between 0.48 and 0.95 cm (3/16 and 3/8 in.).
Typ»SRtc«Tub«
Hin
Probe I
ml
Y * 7.62 cm (3 In.) |
Figure C2a-4. Minimum Pilot-Sample Probe Separation Needed to Prevent
Interference; D, between 0.48 and O.S5 cm (3/16 and 3/8 In.).
Estimated Tl y w~l
Sheath = I ' " " I x 10o
Blockage IpuctAisal
(a) (b)
Figure C2a-S. Projected-Area Models for Typical Pltot Tube Assemblies.
-------
9/30/94: CD2a-1
CALIBRATION DATA SHEET 2a
Type S Pitot Tube
"A" Side Calibration
Run No.
1
2
3
APstd
in. H2O
APS
in. H2O
Cp(Side A)
Cp(s)
Deviation
Deviation = Cp(s) - Cp (A or B)
Avg Dev » o(A or B) = -
!Cp(s)-Cp(AorB)i
"B" Side Calibration
Run No.
1
2
3
Ap8td
in. H2O
Ap8
in. H20
Cp(Side B)
CD(S)
Deviation
o(A or B) must be £0.01 |Cp(Side A) -Cp{Side B) £ 0.01
Average = [Cp{Side A) + Cp{Side B)]/2 = _ •_
If the intent is to always use either Side A or Side B orientation, that side only need be calibrated. Otherwise use the
average of Side A and Side B of the p'rtot tube that meets the specifications above for Cp.
QA/aC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Certification
I certify that the Type S p'rtot tube/probe ID#
, the standard type pitot tube, and the calibration
setup meet or exceed all specifications, criteria and/or applicable design features and hereby assign a pitot tube
calibration fa
Certified by:
calibration factor Cp of
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
CALIBRATION DATA SHEET 2b
Verification of Standard Pitot Tube Design Specifications
9/30/94- CD2M
Shape of tip = (/) Hemispherical _ Ellipsoidal _ Conical
Size of static pressure holes = about 0. 1
Static pressure holes equally spaced in a piezometer ring configuration?
Tube diameter (Dt) = __i_ _ inch
Junction = _
Distance A (DA) = . _
Distance B (DB) = _
90°?
inch DA/Dt =
inch DB/Dt =
: 6?
8?
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
Section x-x
£
Curved or
frittered junction
90 bend
Static holes
in outside
tube only
Hemispherical tip
impact opening -
inner tube only"
QA/QC Check
Completeness
Certification
Certified by:
Legibility
Accuracy
Specifications
Reasonableness
assigned a pttot tube coefficient Cp of 0.99.
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: CD2c-1
Duct Dimensions
Depth/Diameter a: 12 in. (?)
Width (if rect.) ^10 in. (?)
Equiv. Dia. (if rect), De
Distances to disturbances
Upstream ^8D,(?)*
Downstream 2:2 Du (?)*
* If not, demonstrate acceptability
Yaw angle £2 degrees (?)
Pitch angle ^2 degrees (?)
Flow Steadiness
Ap
3000 fpm
CALIBRATION DATA SHEET 2c
Type S Calibration Setup
A©
A© Is the lapse time before Ap changes
by ±2% in minutes (time it
takes to read Ap for standard
p'rtot and Type-S p'rtot tubes).
Flow straighteners
(if required)
\
Blower
8D (minimum)
2D
(minimum).
Flow
9
.Type S pilot
lube port
fO>30.5 cm (12in)
Pilot tube calibration syslem.
Standard pilot
tube port
Sel
screws
Standard
pitot tube
TypeS
pitot tube
Pitot tube calibration set-up.
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Certification . .
I certify that the calibration setup for the Type S pitot tube meets or exceeds all specifications, criteria and/or
applicable design features.
Certified by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: 026-1
A.
1.
2.
B.
1.
CALIBRATION PROCEDURE 2d
Barometer
Procedure 1
Compare the field barometer reading against
that of a mercury-in-glass barometer.
Adjust the field barometer reading to within
±0.1 in. Hg.
Procedure 2
Obtain the station value or absolute
barometric pressure Pr from a nearby
National Weather Service station and its
elevation (A) in feet above sea level.
2. Determine the elevation (B) in feet above
sea level of the site of the field barometer.
3. Calculate the site barometric pressure (Pb)
as follows:
Pb = Pr + 0.001 (A-B)
4. Compare the field barometer reading
against Pb obtained in step 3.
5. Adjust the field barometer reading to within
±0.1 in. Hg.
-------
9/30/94: CD2d-1
CALIBRATION DATA SHEET 2d
Post-test Calibrations
Barometer
Mercury (M)
Field (F)
F-M
^±0.1 in. Hg?
Temperature
Abs Average Stack Temperature. S
Reference Temperature R
Temperature Reading T
S/R =
T/R =
(0.90 to 1. 10?)
(Meet criterion?)
Denote source of temperature: Oil bath _ Other (Explain)
Method 2: T/R
Method 2 A T/R
0.985 to 1.015
0.98 to 1.02
Pressure Sensor (if other than inclined or mecury-in-glass)
Check (/) Differential U-Tube Other
Low to high values span range of Ap's?
Level
Pressure Side
Low
Mid
High
Vacuum Side
Low
Mid
High
Gauge (A)
Low to high values span range of pressures
Reference (B)
A/B (0.95 to 1.05?)
Reference: Inclined gauge-oil or mercury-in-glass.
QA/QC Check
Completeness _
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: C2e-1
CALIBRATION PROCEDURE 2e
Temperature Sensors
A. References
Use as appropriate the following:
1. For s 761 °F, ASTM mercury-in-glass
reference thermometers.
2. Reference thermocouple/potentiometer, MIST
calibrated. Suitable for > 761 °F.
3. Thermometric fixed points, e.g., ice bath and
boiling water (corrected for barometric
pressure).
B. Measurement
1. Select the calibration temperature to within
±10% of the absolute average stack
temperature. (Use CDS 2d).
2. Select the appropriate references from
section A.
3. Compare the field temperature sensors
against the appropriate references (must be
within ±1.5% of the absolute reference
temperature,-unless otherwise specified).
C. Notes
Although not stated in the Code of Federal Regulations, EPA has found the following to be acceptable as
an alternative to calibrating thermocouples at ±10% of absolute stack temperature (see EMTIC GD-28
Alternate Method for Thermocouple Calibration"):
1. Check the thermocouples against a reference thermometer at ambient conditions and at either an ice
point or some elevated temperature other than ambient.
2. The temperatures of both sensors at both temperatures must agree within ±2°F for the
thermocouple to be considered accurate.
-------
9/30/94: C2f-1
CALIBRATION PROCEDURE 2f
Pressure Sensors
A. Differential Pressure Sensors
Calibrate or check the calibration of differential
pressure sensors other than inclined manometers
as follows:
1. Connect the differential pressure sensor
to a gauge-oil manometer as shown in
Figure C2f-1.
2. Vent the vacuum side to the atmosphere, and
place a pressure on each system.
3. Compare Ap readings of both devices at
three or greater levels that span the range.
4. Repeat steps A1 through A3 for the vacuum
side; vent the pressure side and for the
vacuum side and place a vacuum on the
system.
5. The readings at the three levels must agree
within ±5% of the reference sensor.
B. U-Tube Manometers
Calibrate or check the calibration of U-tube
manometers or other pressure gauges other than
mercury-in-glass manometers as follows: Use the
same procedure as that in section A, except use a
mercury-in-glass manometer as the reference.
To pressure source or
verted to atmosphere
Manometer
To vacuum system or
vented to atmosphere
Rgure C2M. Differential pressure sensor check.
-------
: S2A-1
SUMMARY SHEET 2A
Client/Plant Name FDS 2A
Job No. FDS 2A
Sampling Location FDS 2A
RunlD# FDS2A
Test Date FDS 2A
Run Start Time FDS 2A
Run Finish Time FDS 2A
Net Run Time, min 0 FDS 2A
Barometric Pressure, mm Hg Pb FDS 2A
Average Meter Gauge Pressure, mm Hg Pg FDS 2A
Average Meter Temperature, K T FDS 2A
Initial Meter Calibration Factor Yj CDS 2A
Final Meter Calibration Factor Yf CDS 2A
Average Meter Calibration Factor Ym CDS 2A
Initial Meter Reading, m3 Vmi FDS 2A
Final Meter Reading, m3 Vmf FDS 2A
Metered Volume, m3 vms $S 2A
Volumetric Flow Rate, wscfh Qs SS 2A
Post-test Calibration Checks
Temperature and Barometer CDS 2d
Metering Device CDS 2A
= 0.3853
Run #1 Run #2 Run #3 Avg
-------
9/30/94: F2A-1
FIELD PROCEDURE 2A
Direct Measurement of Gas Volume Through Pipes
and Small Ducts
Note: This procedure applies to determining gas flow rates in pipes and small ducts, either in-line or at
exhaust positions in range ofO to 50°C.
Preliminaries 2. For sources with continuous, steady emission
flow rates (see FDS 2A).
a. Record the initial meter volume reading,
meter temperature(s), meter pressure, and
barometric pressure, and start the
A.
1,
Select an appropriate volume meter. Consider
the manufacturer's recommended capacity
(minimum and maximum) of the meter,
temperature, pressure, corrosive characteristics,
the type of pipe or duct, severe vibrations, and
other factors that may affect the meter
calibration.
2. Calibrate the volume meter to within ±2%.
Sea CP 2.
3. Install the gas meter. Use flange fittings,
wherever possible, and gaskets or other seal
materials to ensure leak-tight connections.
B. Measurement
1. Leak-check the volume meter as follows:
a. For a meter under positive pressure, apply
a small amount of liquid leak detector
solution containing a surfactant to the
connections.
b. For a meter under negative pressure, block
the flow at the inlet of the line, if possible,
and watch for meter movement. If this
procedure is not possible, visually check all
connections, and ensure leak-tight seals.
stopwatch.
b. Throughout the test period, record the
meter temperatures and pressure so that
average values can be determined.
c. At the end of the test, stop the timer, and
record the elapsed time, the final volume
reading, meter temperatures, pressure, and
barometric pressure.
3. For sources with noncontinuous, non-steady
emission flow rates, use step B2 with the
addition of the following: Record all the meter
parameters and the start and stop times
corresponding to each process cyclical or
noncontinuous event.
C. Post-test Calibrations
1. Calibrate the volume meter (must be •& ±5%
from the initial). If >5%, either void the test
series or use whichever meter coefficient value
fl.e., before or after) that gives the greater
value of pollutant emission rate. (See CP 2A).
2. Check the temperature gauge calibration at
ambient temperature (must be < ±2% of
absolute temperature). (See CP 2e).
-------
9/30(34',
FIELD DATA SHEET 2A
Volume Flow Rate - Direct
Client/Plant Name.
City/State
Job#
Date/Time
Test Location/Run #
Personnel
Meter Type
Meter ID#
Date Meter Last Calibrated
Barometer ID#
Time
Run/Clock
Start Time Finish Time
Bar Pressure, mm Hg: Start
Vol Rdg (VJ
(m3)
Average
Finish Ava. P.
Meter
Pressure, Pg
(mm Hg)
Temperature
tnf'C)
Tm(K)
Post-test Calibrations
Attach CDS 2d and CDS 2A temperature, barometer, meter calibrations.
Stopwatch accurate to ±1 sec?
For meter, Y/V, = (0.95 to 1.05?)
QA/QC Check
Completeness _
Checked by:
Legibility.
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: CP2A-1
CALIBRATION PROCEDURE 2A
Metering System
A, Preliminaries
1. Select a standard reference meter such as a
spirometer or wet test meter that has a
capacity consistent with that of the
metering system.
2. Set up the metering system in a
configuration similar to that used in the field
installation, i.e., in relation to the flow
moving device.
3. Connect the temperature and pressure •
gauges as they are to be used in the field.
4. Connect the reference meter to the inlet of
the flow line, if appropriate for the meter.
5. Begin gas flow through the system, and
check the system for leaks.
2. Run triplicates at each flow rate.
3. Obtain the necessary data (see CDS 2A).
C. Alternative
A standard pitot tube may be used for the
reference measurement provided that:
1. A duct with <:8 diameters upstream and
-------
CALIBRATION DATA SHEET 2A
Metering System
Metering System ID#
Date
Barometric Pressure, Pb
Initial Calibration Recalibration
mm Hg Personnel
Capacity of Ref Meter
>Max Cap of Metering Syst?
Flow
Rate of
Max Cap
0.3
0.6
0.9
Run
No.
1
2
3
1
2
3
1
2
3
Reading
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Initial
Final
Reference
(m6)
A
(mm Hg)
Metering System
(m™)
om
(mm Hg)
Time
9
(min)
vm
'
Avg Y
Note: If reference measurements are made with a standard pitot tube, attach FDS 2.
For each run, difference of maximum and minimum Ym «s 0.030?
1m/v'm/ °-95 to 1-05? (For recalibration only; conduct the calibration at one flow rate (intermediate) and with
the meter pressure set at the average value of previous field test.
Ym =
QA/QC Check
Completeness
Legibility
(Vmf-Vm,)(tm(avg)+273) (Pb+Pg(avg))
Accuracy _ Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: S2B-1
Client/Plant Name
Job No.
Sampling Location
Run ID#
SUMMARY SHEET 2B
FDS2B
FDS2B
FDS2B
FDS2B
Run#1
Run #2
Run #3
Avg
Test Date
Run Start Time
Run Finish Time
Net Run Time, min
Barometric Pressure, mm Hg
Average Meter Gauge Pressure, mm Hg
Average Meter Temperature, K
Initial Meter Calibration Factor
Final Meter Calibration Factor
Average Meter Calibration Factor
Initial Meter Reading, m3
Final Meter Reading, m3
Metered Volume, m3
Calibration Gas Factor
Mean Inlet Organic Concentration, ppm
Mean Outlet Organic Concentration, ppm
Mean Outlet CO Concentration, ppm
Mean Outlet CO2 Concentration, ppm
Exhaust Gas Volume, m3
Exhaust Gas Volume flow Rate, m3/min
Post-test Calibration Checks
Temperature and Barometer
Metering Device
V
,8
K
coe
CO
'2e
V.
FDS2B
FDS2B
FDS2B
FDS2B
FDS 2B
FDS2B
FDS2B
CDS2A
CDS2A
CDS2A
FDS2B
FDS2B
SS2B
FDS 25A
FDS 25A
FDS 25A
FDS 10
FDS 6C/SS 3A
SS 2B
SS2B
CDS2d
CDS2A
0.3853
K (HO)
61 B K (HCe) + C02e + C0e - 300
where K is the calibration gas factor as follows:
ethane = 2; propane = 3, butane = 4;
other = appropriate response factor.
"es
0
-------
9/3O/94: F2B-7
... _ „ FIELD PROCEDURE 2B
Exhaust Gas Vqlume Flow Rate From Gasoline Vapor Incinerators
Note: This procedure applies to the measurement of exhaust volume flow rate from incinerators that
process gasoline vapors consisting primarily of alkanes, alkenes, and/or arenes (aromatic
M^^T'oxf aS^Td thdt the am°Um °f aUxWarY fuel is Eligible. This procedure combines
Methods 2A, 25A or 25B, and 10 (for CO and CO2). Refer to respective FP's and attach respective
t-Ui> s to the test report.
A. Preliminaries
1.
2.
3.
Select and calibrate the volume meter as in
Method 2A. (See CP 2A).
Install the volume meter in the vapor line to
incinerator inlet according to the procedure
in Method 2A.
At the volume meter inlet, install a sample
probe (see Method 25A). Connect to the
probe a leak-tight sample line (stainless steel
or equivalent) and an organic analyzer
system (see Method 25A or 25B).
At the incinerator exhaust, install a sample
probe (see Method 25A) and connect the
CO2, CO, and organic analyzers. A sample
manifold may be used.
Heat samples lines* if necessary, to prevent
condensation.
Connect data output recorders, and prepare
and calibrate all equipment and analyzers.
For the C02 analyzer, follow the procedures
in Method 10, but substitute CO2 calibration
gas where the method calls for CO
calibration gas. Use span value of 15 % for
the CO2 analyzer.
B. Sampling
1. Inject all calibration gases at the connection
between the probe and the sample line. If a
manifold system is used for the exhaust
analyzers, operate all the analyzers and
sample pumps during the calibrations. Do
not use methane as a calibration gas.
4.
5.
6.
4.
5.
2. At the beginning of test run, record the
initial parameters for the inlet volume meter
(see Method 2A), mark all of the recorder
strip charts to indicate the start of the test.
3. Record the inlet organic and exhaust CO2,
CO, and organic concentrations throughout
the test run.
During periods of process interruption and
halting of gas flow, stop the timer and mark
the recorder strip charts so that data from
this interruption are not included in the
calculations.
At the end of the test period, record the
final parameters for the inlet volume meter
and mark the end on all of the recorder strip
charts.
6. At the conclusion of the sampling period,
introduce the calibration gases for each
analyzer.
7. If an analyzer output does not meet the
specifications of the method, invalidate the
test data for the period. Alternatively,
calculate the volume results using initial
calibration data and using final calibration,
data and report both resulting volumes.
Then, for emissions calculations, use the
volume measurement resulting in the
greatest emission rate or concentration.
8. Attach FDS's from Method 2A, Method
25A or 25B, Method 10, and CO2 analyzer.
-------
9/30/94: FD2B-1
FIELD DATA SHEET 2B
Volume Flow Rate - Indirect
Client/Plant Name.
City/State
Test Location/Run #
, Personnel
Job#
Date/Time
Date Last Calibrated.
Pqrnm^rintt Bar Press, Pb Start Finish mm Hg Date Last Calibrated
Time
Run/Clock
Volume
Meter Rdg
(m3)
Average
Pressure, Pg
(mm Hg)
Temperature
(°C)
T.(K)
, ;
Post-test Calibrations
Attach FDS 2d and CDS 2A temperature, barometer, meter calibrations.
For meter, Y,/Y| =.
. (0.95 to 1.05?)
QA/QC Check
Completeness
Legibility.
Accuracy.
Checked by:
Personnel (Signature/Date)
Specifications.
Reasonableness
Team Leader (Signature/Date)
-------
9/3O/94: S2C-1
Client/Plant Name
Job No.
Sampling Location
RunID#
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Absolute Stack Pressure, in. Hg
Average Stack Temperature, °F
Avg Absolute Stack Temperature, R
Moisture Content, fraction
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Stack Area, ft2
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(tsj +460) Ap]1/2
Average Velocity, ft/sec
Volumetric Flow Rate, dscfh
Volumetric Flow Rate, wscfh
Post-test Calibration Checks
Temperature and Barometer
Differential Pressure Sensor
SUMMARY SHEET 2C
FDS2
FDS2
FDS2
FDS2
FDS2
FDS2
FDS2
FDS1A
FDS1
FDS2
FDS2
FDS2
SS2
FDS2
SS2
B.,
%CO2
%02
%(CO+N2)
6d
FDS4
FDS3
FDS3
FDS3
FDS3
FDS1
CDS2a
FDS2
FDS2
SS2
SS2
SS2
CDS2d
CDS2d
Run#1
Run #2
Run #3
Avg
-------
9/30/94: F2C-1
FIELD PROCEDURE 2C
Velocity and Volumetric Flow Rate from Small Stacks or Ducts
(Standard Pitot Tube)
Note: This procedure is used in conjunction with Method 1A. ?ne procedure is the same as that in
Method 2, except that a standard type pitot tube or the alternative pitot tube (see Figure F2C-1) is used
instead of a Type S. Use FDS 2. Other variations are as follows:
1. Conduct the measurements at the traverse
points specified in Method 1 A.
2. Take the velocity head (Ap) reading at the
final traverse point. If the Ap at the final
traverse point is unsuitably low, select
another point.
3. Clean out the impact and static holes of the
standard p'rtot tube by "back-purging" with
pressurized air.
4. Take another Ap reading (after the back-
purge).
5. The ratio of the Ap readings (after divided by
before) must be between 0.95 and 1.05 for
the traverse to be acceptable.
6. If "back purging" at regular intervals is part
of the procedure, then take comparative
Ap readings, as above, for the last two back
purges at which suitably high Ap readings
are observed.
4 Static
Holes.
3/8 D
Impact Opening
16 D
Rgure F2C-1. Modified Hemispherical-Nosed Pitot Tube.
-------
Qs = 17.64 Ym Qm
9/3O/94- S2D-1
SUMMARY SHEET 2D
Run #1 Run #2 Run #3 Avg
Client/Plant Name FDS 2D
Job No. FDS 2D
Sampling Location FDS 2D
Run 1D# FDS 2D
Test Date FDS 2D
Run Start Time FDS 2D
Run Finish Time FDS 2D
Net Run Time, min 0 FDS 2D
Barometric Pressure, in. Hg Pb FDS 2D
Average Meter Gauge Pressure, in. Hg P FDS 2D
Average Meter Temperature, R T FDS 2D
Initial Meter Calibration Factor Yj CDS 2D
Final Meter Calibration Factor Yf CDS 2D
Average Meter Calibration Factor Ym CDS 2D
Initial Meter Reading, cfm Q^ FDS 2D
Final Meter Reading, cfm Q FDS 2D
Volumetric Flow Rate, scfm Q8 SS 2D
Post-test Calibration Checks
Temperature and Barometer CDS 2d
Metering Device CDS 2D
-------
9/30/94: F2D-1
FIELD PROCEDURE 2D
Gas Volume Flow Rates in Small Pipes and Ducts
Note: In applying this procedure, use particular caution for intermittent or variable gas flows. The
apparatus, installation, and leak-check procedures are the same as that for Method 2A, except for the
following:
A. Preliminaries
1. Select a gas metering rate or flow element
device, e.g., rotarneter, orifice plate, or other
volume rate or pressure drop measuring
device, capable of measuring the stack flow
rate to within ±5%. In selecting this
metering device, consider the following:
a. Capacity of the metering device (must be
sufficient to handle the expected
maximum and minimum flow rates at the
stack gas conditions).
b. Magnitude and variability of stack gas
flow rate, molecular weight,
temperature, pressure, dewpoint, and
corrosive characteristics, and pipe or
duct size.
2. Calibrate the metering system according to
CP 2A; however, use CDS 2D.
B. Volume Rate Measurement
1. Continuous, Steady Flow
a. Record the barometric pressure at the
beginning of the test run.
b. At least once an hour or at & 12 equally
spaced readings, measure the metering
device flow rate or pressure drop
reading, the metering device
temperature and pressure, and other
parameters during the test run.
(See FDS 2D).
c. Measure the barometric pressure at the
end of the test run.
2. Noncontinuous and Nonsteadv Flow
a. Use volume rate devices with particular
caution. Calibration will be affected by
variation in stack gas temperature,
pressure and molecular weight.
b. Use the procedure in step B1 with the
addition of the following: Measure all
the metering device parameters on a
time interval frequency sufficient to
adequately profile each process cyclical
or noncontinuous event. A multichannel
continuous recorder may be used.
-------
9/30/94: FD2D-1
FIELD DATA SHEET 2D
Flow Rate Measurement
Client/Plant Name job #
City/State
Date/Time
Test Location/Run # Personnel
Meter ID#
Meter Cal. Coef , Ymi Date 1 ast Calibrated
Barometer ID# Bar Press, Ph Start Finish in. Ho n^t* i «t rain,™*-*
Time
Run/Clock
Average
Flow Rate
Rdg
(cfm)
Pressure
(in. Hg)
•
Temperature
°F
R
t
Post-test Calibrations
Attach CDS 2d and CDS 2D temperature, barometer, meter calibrations.
For meter recalibration, Yf/Ymi =
(0.95 to 1.05?)
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: CD2D-1
CALIBRATION DATA SHEET 2D
Metering System
Metering System \D#
Date
Barometric Pressure, Pb
Initial Calibration Recalibration
in. Hg
Personnel
Capacity of Ref Meter
>Max Cap of Metering Syst?
Flow
Rate of
Max Cap,
0.3
0.6
0.9
Run
No.
1
2
3
1
2
3
1
2
3
Reading
Initial
Rnal
Initial
Final
Initial
Rnal
Initial
Rnal
Initial
Rnal
Initial
Rnal
Initial
Final
Initial
Final
Initial
Final
Reference
vr
(cf)
*r
(°F)
Pr
(in. Hg)
Metering System
Qm
(cfm)
*m
(°F)
Pm
(in. Hg)
Time
0
(min)
*
Ym
Avg Y
Note: If reference measurements are made with a standard pitot tube, attach FDS 2.
For each run, difference of maximum and minimum Ym £ 0.030?
Ym/Yml 0.95 to 1.05? (For recalibration only; conduct the calibration at one flow rate (intermediate) and with
the meter pressure set at the average value of previous field test.
QA/QC Check
Completeness
Legibility
Accuracy
(Pb+Pg(avg))
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: F3-1
FIELD PROCEDURE 3
Dry Molecular Weight
Note: This procedure includes three different types of sampling techniques. Select the appropriate
procedure for the test. Use FDS 3.
A. Single-point, Grab Sampling and Analysis
1. Set up the equipment as shown in
Figure F3-1. Ensure all connections ahead of
the analyzer are tight.
2. Optional: If an Orsat analyzer is used, leak-
check the analyzer (see FP 3a).
3. Place tip of probe at the centroid of the stack
cross section or at a point no closer to the
walls than 3.3 ft.
4. Purge the sampling line long enough to allow
at least five exchanges.
5. Draw a sample into the analyzer, and
immediately analyze ft for %C02 and %62.
6. Calculate the dry molecular weight.
7. Repeat the sampling, analysis, and
calculation procedures until the dry molecular
weights of any three grab samples differ from
their mean by no more than 0.3 Ib/lb-mole.
8. Report average of these three molecular
weights to the nearest 0.1 Ib/lb-mole.
B. Single-point, Integrated Sampling and
Analysis
1. Optional: Leak-check the flexible bag. (see
FP3b).
2. Set up the equipment as shown in
Figure F3-2.
3. Optional: Leak-check the train (see FP 3c).
4. Evacuate the flexible bag, and connect the
probe.
5. Place tip of probe at the centroid of the stack
cross section or at a point no closer to the
walls than 3.3 ft. Purge the sampling line,
connect the bag, and ensure that all
connections are tight.
6. Sample at a constant rate, simultaneously
with, and for the same total length of time
as, the pollutant emission rate determination
until 30 L of sample gas or desired volume
has been collected.
7. Obtain one integrated flue gas sample during
each pollutant emission rate determination.
8. Optional: If an Orsat analyzer is used, leak-
check the Orsat analyzer (see FP 3a) before
the determination.
9. Within 8 hr after the sample is taken,
analyze ft for %C02 and %02.
10. Calculate the dry molecular weight.
11. Repeat the analysis and calculation
procedures until the individual dry molecular
weights for any three analyses differ from
their mean by no more than 0.3 Ib/lb-mole.
. 12. Report the average these three molecular
weights to the nearest 0.1 Ib/lb-mole.
C. Multi-point, Integrated Sampling and
Analysis
1. For equivalent stack diameter (De) <24 in.,
use &8 traverse points for circular stacks
and 2:9 for rectangular stacks, and
& 12 traverse points for all other cases.
2. Locate the traverse points according to
Method 1.
3. Follow the procedures outlined in Section B,
except for the following: Traverse all
sampling points, and sample at each point
for an equal length of time. Record
sampling data as shown in FDS 3. See also
FDS 5 if sampling is conducted with
particulate sampling.
D. Alternatives and Modifications
1. Rather than using an integrated sample, an
Orsat may be used to analyze individual grab
samples obtained at each point.
2. If either C02 or 02 is measured,
stoichiometric calculations may be used to
determine Md.
3. An Md = 30.0 for processes burning natural
gas, coal, or oil may be used.
-------
ToAmlynr
Figure F3-1. Grab-Sampling Train.
Rigid Conlilntr
Figure F3-2. Integrated Gas-Sampling Train.
-------
9/30/94: FD3-1
FIELD DATA SHEET 3
Dry Molecular Weight
Client/Plant Name
Job #
City/State
Date
Test Location/Run #
Personnel
Orsat/Fyrite (Single-point, Grab or Integrated, Sampling and Analysis)
Orsat ID:
Time of Sample
Collection
Time of
Analysis
Fyrite ID:
%CO2 Rdg
(A)
%02 Rdg
(B)
Analyzer Leak-Check OK?:
%O2
(B-A)
Md = 0.440 %CO2 + 0.320 %O2 + 0.280 %(CO + N2)
Bag ID:
Bag Leak-Check OK?
%{CO + N2)
(100-B)
Average
Each Md ^0.3 Ib/lb-mole from average?
Md
Ib/lb-mole
Train Leak-Check OK?
Note: The equation for Md does not consider argon in air (about 0.9% M = 39.9) and introduces a negative error of
about 0.4%.
Multi-point, Integrated Sampling
Time
Traverse Pt.
Average
Flow Rate, Q
% Deviation
<±10%?
% Dev. = (Q-Q )/Q x 100, <±10%
-tavg'"-'avg
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: F3a-1
FIELD PROCEDURE 3a
Leak-Check of Orsat Analyzer
1. Bring the liquid level in each pipette up to the 3. Record the meniscus position. Wait 5:4 min.
reference mark on the capillary tubing, and a Each pjpette |jqujd level must not fall
then close the pipette stopcock. below the bottom of the capillary
2. Raise the leveling bulb sufficiently to bring tubing.
the confining liquid meniscus onto the b Burette meniscus must not change
graduated portion of the burette, and then >b.2 mL.
close the manifold stopcock.
-------
9/30/94: F3b-1
FIELD PROCEDURE 3b
Leak-Check of Flexible Bags
Note: There are several variations of this leak-check procedure. Select the appropriate procedure.
A. Procedure A B_ Procedures
1. Connect bag to a water manometer. This Procedure is a variation of Procedure A.
2. Pressurize the bag to 2 to 4 in. H2O. 1. Follow steps A1 and A2.
3. Allow the bag to stand for 10min. 2. Allow the bag to stand overnight.
4. Any displacement in the water manometer 3. A deflated bag indicates a leak
indicates a leak.
-------
9/30/94: F3c-1
FIELD PROCEDURE 3c
Leak-Check of Non-isokinetic Sampling Trains
Note: There are several variations of this leak-check procedure. Select the one specified.
A, Procedure A
1. Place a vacuum gauge at the condenser inlet
(or other specified point), pull a vacuum
2:10 in. Hg, plug the outlet at the quick
disconnect, and then turn off the pump.
2. The vacuum must remain stable for &30
sec.
B. Procedure B
1. Temporarily insert a vacuum gauge at or
near the probe inlet.
2. Plug the probe inlet (or other specified
point), and pull a vacuum &10 in. Hg.
3. Note the time rate of change of the dry gas
meter dial (must be ^2% of average
sampling rate).
4. Carefully release the probe inlet plug before
turning off the pump.
C. Procedure C
1. Temporarily insert a vacuum gauge at or
near the probe inlet, and temporarily attach
a rotameter (0 to 40 cc/min) or a 50-cc soap
bubble meter to the dry gas meter outlet.
2. Plug the probe inlet (or other specified
point), and pull a vacuum a 10 in. Hg.
3. Note the reading (must be £2% of average
sampling rate).
4. Carefully release the probe inlet plug before
turning off the pump.
D. Procedure D (Pump Leak-check)
It is suggested (not mandatory) that the pump
be leak-checked separately, either before or after
the sampling run. If done before, do it before the
train leak-check; if done after, do it after the train
leak-check. To leak-check the pump, proceed as
follows:
1. Disconnect the drying tube from the probe-
impinger assembly.
2. Place a vacuum gauge at the inlet to the
pump.
3. Pull a vacuum of a10 in. Hg, plug or pinch
off the outlet of the flow meter, and then
turn off the pump (must remain stable for
a: 30 sec).
£. Procedure £
1. For components after the pump, apply a
slight positive pressure.
2. Apply a liquid (e.g., detergent in water) at
each joint, and check for gas bubbles.
-------
9/30/94: S3A-1
SUMMARY SHEET 3A
Oxygen and Carbon Dioxide
Run #1 Run #2 Run #3 Avg
Client/Plant Name FDS 6C
Job No. FDS 6C
Sampling Location . FDS 6C
Run ID # FDS 6C
Test Date FDS 6C
Run Start Time FDS 6C
Run Finish Time FDS 6C
Oxygen
Average Gas Concentration, dry basis, ppm C" FDS 6C
Avg System Cal Bias Check Responses for
Zero Gas, ppm C0 FDS 6C
Avg System Cal Bias Check Responses for
Upscale Cal Gas, ppm Cm FDS 6C
Actual Cone of Upscale Cal Gas, ppm C FDS 6C
ma
Effluent gas concentration, dry basis, ppm Cgas SS 3A
Carbon Dioxide
Average Gas Concentration, dry basis, ppm C FDS 6C
Avg System Cal Bias Check Responses for
Zero Gas, ppm C0 FDS 6C
Avg System Cal Bias Check Responses for
Upscale Cal Gas, ppm Cm FDS 6C
Actual Cone of Upscale Cal Gas, ppm Cma FDS 6C
Effluent gas concentration, dry basis, ppm Cgas SS 3A
C =(C-C0)
cm-c0
-------
9/30/94: F3A-1
FIELD PROCEDURE 3A
Oxygen and Carbon Dioxide
(Instrumental Analyzer Procedure)
Note: The procedure for FP 3A is essentially the same as that for FP 6C, except for the obvious changes
due to the gases being analyzed. Follow FP 6C (use FDS 6CJ, except for the following:
A. Variations from FP 6C
1. Obtain calibration gases (CO2 in N2 or CO2 in
air or gas mixtures of CO2/SO2, O2/SO2, or
O2/CO2/SO2 In N2).
2. For O2 monitors that cannot analyze zero
gas, use a calibration gas concentration
equivalent to <10% of span for the zero gas.
3. For non-Protocol 1 calibration gases,
Method 3 is the reference method and the
acceptance criteria is ±5% or 0.2% O2 or
C02, whichever is greater (see CDS 6Ca).
4. Initially and whenever changes are made in
the instrumentation that could alter the
interference response (e.g., changes in the
type of gas detector), conduct an
interference response test according to
FP 20, step B3.
5. Select a measurement site and sampling
points using the same criteria that are
applicable to tests performed using
Method 3B.
6. Run for the same sampling time per run as
that used for Method 3B plus twice the
stable response time for the instrument.
B. Quality Control Procedures
The following quality control procedures are
recommended when the results of this
method are used for an emission rate
correction factor, or excess air
determination. The tester should select one
of the following options for validating
measurement results (see FDS 3B):
1. If both 02 and C02 are measured, use the
procedures in Method 3B.
2. If only O2 is measured, use an Orsat or
Fyrtte analyzer to measure the CO2
concentration at the sample by-pass vent
discharge. Run duplicates concurrent with
at least one run, and average the results for
each run. Then use the procedures in
Method 3B.
3. If only CO2 is measured, follow the
procedure in step B2, except measure O2.
Investigate differences between FP 3A and
the duplicate Fyrite analyses of >O.5%.
-------
9/30/94-
FIELD PROCEDURE 3B
Emission Rate Correction Factor or Excess Air
Note: This procedure is the same as that in Method 3 except for what follows here and below: Do not
use a Fyrite-type gas analyzer without prior approval from the Administrator. Use an Orsat analyzer only
in this method. For 4.0% CO2 or > 15% O^ the measuring burette of the Orsat must have at least
0.1% subdivisions. It is suggested that both CO2 and O2 be measured to validate results.
A. Single-point, Grab Sampling and Analysis
1. Mandatory: Leak-check the Orsat analyzer
(see FP 3a). Do not proceed without passing
this leak-check.
2. In analyzing the sample, make repeated
passes through each absorbing solution until
two consecutive readings are the same, with
three to four passes between readings. (If
constant readings cannot be obtained after
three consecutive readings, replace the
absorbing solution.)
3. Mandatory: After the analysis is completed,
leak-check the Orsat analyzer.
B. Single-point, Integrated Sampling and
Analysis
1. Mandatory: The optional leak-checks in
FP 3, steps B1 (flexible bag) and B3
(sampling train) are mandatory.
2. Mandatory: Leak-check the Orsat analyzer
(see FP 3a).
3. Analyze the sample within 4- hr after the
sample is taken.
4. Analyze the sample as in step A2 of the
procedure.
5. Repeat the analysis until any three analyses
meet the criteria in FDS 3B.
6. Average three acceptable values and report
to the nearest 0.1 % for CO2, O2> or CO.
7. Mandatory: After the analysis is completed,
leak-check the Orsat analyzer.
C. Multi-point, Integrated Sampling and
Analysis
Follow section C of FP 3 and section B of
this procedure.
D. Quality Control Procedures
When both CO2 and 02 are measured,
calculate F0 and compare values against those in
FDS3B-1.
E Notes
1. Section D does not apply to processes that:
a. Remove CO2 or 02.
b. Add 02 (e.g., oxygen enrichment) and
N2 in proportions different from that of
air.
c. Add CO2 (e.g., cement or lime kilns).
.d. Have no fuel factor, F0, values
obtainable (e.g., extremely variable
waste mixtures).
2. Section D does not detect sample dilution
resulting from leaks during or after sample
collection.
3. Section D applies to samples collected
downstream of most lime or limestone flue-
gas desulfurization units as the CO2 added
or removed from the gas stream is not
significant in relation to the total %CO2.
The %CO2 from other types of scrubbers
using only water or basic slurry can be
significantly affected and would render the
F0 check minimally useful.
-------
9/30/94: FD3B-1
FIELD DATA SHEET 3B
Emission Rate Correction and Excess Air
Client/Plant Name
City/State
Job #
Date
Test Location/Run #
Personnel
Orsat (Single Point, Grab or Integrated, Sampling and Analysis)
Orsat ID:
Time of Sample
Collection
Time of
Analysis
Average (report to ±0.1 % abs):
Bag ID:
Leak-Check £
%CO2 Rdg
(A)
before OK? Leak-C
%02 Rde
(B)
Triplicates differ by: £0.2%
•s.0.3% lor >4.
Bag Leak-Check OK? Before After
%02
(B-A)
heck After Ol
%CO Rdg
(C)
-------
9/30J94* FD3B-2
DATA VALIDATION
Fuel Type
Coal:
Anthracite and lignite
Bituminous
Oil:
Distillate
Residual
Gas:
Natural
Propane
Butane
Wood
Wood bark
F0 Range
1.016-1.130
1.083-1.230
1.260-1.413
1.210-1.370
1.600-1.836
1.434-1.586
1.405-1.553
1.000-1.120
1.003-1.130
If calculated F0 values are beyond the acceptable ranges shown in
this table, investigate the following before accepting the test
results:
• Strength of the solutions in Orsat.
• Analyzing technique against air or other known
concentration.
• Fuel factor.
Level of the emission rate relative to the compliance level,
i.e.; if the measured emissions are much lower or much
greater than the compliance limit, repetition of the test would
not significantly change the compliance status of the source
and would be unnecessarily time consuming and costly.
An acceptability range of ±12% is appropriate for the F0 factor of
mixed fuels with variable fuel ratios.
F -
%CO,
%CO2, %O2, and %CO are on a dry basis. If CO is
present in measurable quantities by this method,
adjust the O2 and CO2 values before calculating F0
as follows:
- %CO2 + %CO
i) = %O2 -0.5 %CO
-------
-------
9/30/94: F4-1
FIELD PRpCEDURE 4
Moisture
Note- Use this procedure for accurate determinations of moisture content (such as are needed to
calculate emission data).
A. Preliminaries
1. Use at least the following number of traverse
points and locate them according to
Method 1.
a. 8 for circular <24 in. diameter.
b. 9 for rectangular <24 in. equivalent
diameter.
c. 12 for all other cases.
2. Place known volumes of water in the first
two impingers.
3. Weigh the silica gel to ±0.5 g, and transfer
the silica gel to the fourth impinger;
alternatively, weigh the silica gel plus
impinger.
4. Determine the sampling rate to collect
&21 scf at £0.75 cfm simultaneously with,
and for the same total length of time as, the
pollutant emission rate run, if appropriate.
5. If gas stream is saturated or laden with
moisture droplets, attach a temperature
sensor (±2°F) to the probe. See section E.
B. Sampling
1. Set up the sampling train as shown in
Figure F4-1.
2. Optional: Check the volume metering
system (see QCP 5).
3. Turn on the probe heater and (if applicable)
the filter heating system to temperatures of
about 248°F; allow time for the
temperatures to stabilize. Place crushed ice
in the ice bath container.
4. Optional: Leak-check the sampling train
from the inlet of the first impinger inlet or, if
applicable, the filter holder (see FP 5a,
section F).
5. Position the probe tip at the first traverse
point. Sample at a constant (±10%) flow
rate. Record data as shown in FDS 4.
6. Traverse the cross section, sampling at each
traverse point for an equal length of time.
7. Add more ice and, if necessary, salt to
maintain 2=68°F at the silica gel outlet.
8. At completion of sampling, disconnect the
probe from the filter holder (or from the first
impinger).
9. Mandatory: Leak-check the sampling train
as in step B4.
C. Sample Recovery
1. Measure the volume of the moisture
condensed to the nearest mL.
2. Determine the increase in weight of the silica
gel (or silica gel plus impinger) to ±0.5 g.
Record data on FDS 4.
3. Calculate the moisture percentage.
4. Verify constant sampling rate.
D. Post-test Calibrations
Calibrate metering system, temperature
gauges, and barometer (see calibration
section). Attach applicable CDS's
E. Saturated or Moisture Droplet-Laden Gases
1. Measure the stack gas temperature at each
traverse point. Calculate the average stack
gas temperature.
2. Determine the saturation moisture content
by (a) using a psychrometric chart and
making appropriate corrections if stack
pressure is different from that of the chart,
or (b) using saturation vapor pressure tables.
3. Use the lower of this value or the value from
section C.
DIHf
Figure F4-1. Moisture sampling train.
-------
9/30/94: FD4-1
FIELD DATA SHEET 4
Moisture Content (Reference)
Client/Plant Name
City/State
Job #
Date
Test Location/Run #
Personnel
Dry Gas Meter Cal Factor, Y =
Trav.
Pt.
Samplg
Time
(min)
Stk
Temp
(°F)
AH
(in. H2O)
Vol.
Rda, vm
(cf)
Avg:
AV
(cf)
% Dev
f£ 10%?)
DGM Temp., tm
In, °F
Out, °F
Imp.
Temp.
°F
- '
Analytical Data
Final
Initial
Difference
Impinger Volume
(mL)
vf
Vj
Silica gel weight
Xg)
Wf,
W,
= 0.04707 (V( - V,)
V P
Vwsg(std) = 0.04715 (W, - W,)
17 fid. Y
17.64 Y
R =
ws
V
wsg(std)
,, v
vwo(std) vwsg(std) vm(std)
QA/QC Check
Completeness
Checked by: _
Legibility
Accuracy
Personnel (Signature/Date)
Team Leader (Signature/Date)
Specifications
Reasonableness
-------
9/30/94: F4a-1
FIELD PROCEDURE 4a
Moisture Conte.it (Approximation)
Note: Use this procedure to approximate moisture
to a pollutant emission measurement run.
A. Preliminaries
1. Calibrate metering system according to
CP6.
2. Calibrate the barometer according to CP 2d.
B. Sampling
1. Refer to Figure F4a-1. Place exactly 5 mL
water in each impinger.
2. Leak-check the sampling train according to
FP 3c, procedure B or C.
3. Connect the probe, insert it into the stack,
and sample at a constant rate of 2 L/min
until the dry gas meter registers about 1.1
ft3 or until visible liquid droplets are carried
over from the first impinger to the second.
4. Record temperature, pressure, and dry gas
meter readings as shown in FDS 4a.
content to aid in setting isokinetic sampling rates prior
C. Sample Recovery
1. After sampling, combine the contents of the
two impingers, and measure the volume to
the nearest 0.5 ml.
2. Calculate the moisture content {see FDS 4a).'
D. Alternatives
Use drying tubes, wet bulb-dry bulb
techniques, condensation techniques,
stoichiometric calculations, previous
experience, etc.
Heated
Probe
Fitter
(Glass Wool)
Silica
Gel Tube
Rate
Meter
Figure F4a-1. Moisture Sampling Train - Approximate Method.
-------
Post-test Calibration Checks
Temperature and Barometer
Differential Pressure Sensor
Metering System
Run #1 Run #2
9/30/94: S5-2
Run #3 Avg
CDS2d
CDS2d
CDS 5
Vm(sw) - 17.64 VmY-
°-04707
-•
13.6]
Q,, = 17.64 (3600) (1-BJv. A
1 s(avg)
0.09450 TsVmfsld)
P.v.A,,e(1-BJ
Vs - 85.49 C
'avg
c. = 0.001
V,
m(sld)
-------
: FS-1
FIELD PROCEDURE 5
Isokinetic Sampling Trains
A. Pretest Preparation
1. Weigh several 200- to 300-g portions of
silica gel in air-tight containers to ±0.5 g.
Record the total weight of the silica gel plus
container on each container.
2. Check filters visually against light for
irregularities and flaws or pinhole leaks.
Label the filters on the back side near the
edge using numbering machine ink.
3. Desiccate the filters at 20 ± 5.6°C and
ambient pressure for &24 hr, and weigh at
intervals of ==6 hr to a constant weight, i.e.,
SO.5 mg change from previous weighing;
record results to ±0.1 mg. During each
weighing, do not expose the filter to the
laboratory atmosphere for >2 min and a
relative humidity >50%.
B. Preliminary Determinations
1. Select the sampling site and the number of
sampling points (see FP 1).
2. Determine the stack pressure, temperature,
and the range of velocity heads (see FP 2).
3. Optional: Leak-check the pitot lines
(see FP 2a).
4. Determine the moisture content (see FP 4a).
5. Determine or estimate the dry molecular
weight (see FP 3).
6. Select a nozzle size. Do NOT change nozzle
size during the sampling run.
7. Select the proper differential pressure gauge
(see FP 2).
8. Select a suitable probe liner and probe length
such that all traverse points can be sampled.
9. Select the total sampling time and standard
sample volume specified in the test
procedures for the specific industry. Select
equal sampling times of ^2 min per point.
C. Preparation of Collection Train
1. During preparation and assembly of the
sampling train, keep all openings covered to
avoid contamination. Use either ground-glass
stoppers, plastic caps, or serum caps to close
the openings.
2. See Figure F5-1. Prepare impingers as
follows:
a. Impingers 1 and 2: 100 mL water in
each.
b. Impinger 3: Empty.
3.
4.
5.
6.
c. Impinger 4: 200 to 300 g of
preweighed silica gel.
Place the silica gel container in a clean place.
Using a tweezer or clean disposable surgical
gloves, place filter in the filter holder. Check
the filter for tears after assembly.
Mark the probe with heat resistant tape {or
other) to denote the proper distance into the
stack or duct for each sampling point.
Set up the train. Turn on and set probe and
filter box heaters. Place crushed ice around
the impingers.
7. Optional: Leak-check the sampling train (see
FP5aand FP 5b).
D. Sampling
1. Record data shown in FDS 5. Record the
initial dry gas meter (DGM) reading.
2. Level and zero the manometer.
3. Clean the portholes.
4. Remove the nozzle cap, verify that the filter
and probe heating systems are up to
temperature, and check pitot tube,
temperature gauge, and probe alignments
and clearances.
5. Close the coarse adjust valve. If necessary
to overcome high negative stack pressure,
turn on the pump. Position the nozzle at the
first traverse point. Immediately start the
pump, and adjust the flow to isokinetic
conditions.
6. When the probe is in position, block off the
openings around the probe and porthole.
7. Traverse the stack cross-section. Conduct
leak-checks, as required (see FP 5a). Do not
bump the probe nozzle into the stack walls.
a. Keep the temperature around the filter
holder (probe outlet or filter outlet, if
applicable) at the proper level.
b. Add more ice and, if necessary, salt to
maintain a temperature of <68°Fat the
condenser/silica gel outlet.
c. Periodically check the level and zero of
the manometer.
d.
Record DGM readings at the beginning
and end of each sampling time
increment, before and after each leak-
check, and when sampling is halted.
-------
Temperature
Temperature staok
Sensor .Wall Jj>
Nozzle I //f Heat Traced
Impinger Train Optional, May Be Replaced
By An Equivalent Condenser
Temperature
Sensor
Figure F5-1. Particulate Sampling Train.
-------
9/30/94: F5-2
e. Take other readings shown in FDS 5 at
least once at each sample point during
each time increment and additional
readings when significant changes
(20% variation in Ap readings)
necessitate additional adjustments in
flow rate.
8. At the end of the sample run, turn off the
coarse adjust valve, remove the probe and
nozzle from the stack, turn off the pump,
record the final DGM meter reading.
9. Mandatory: Leak-check the sampling train
(see FP 5a). Optional: See FP 5b.
10. Mandatory: Leak-check the pitot lines
(see FP 2a).
11. Allow the probe to cool. Then, wipe off all
external PM near the tip of the probe nozzle,
and place a cap over it.
12. Before moving the sampling train to the
cleanup site, remove the probe from the
sampling train, wipe off the silicone grease,
and cap the open outlet of the probe. Do not
lose any condensate that might be present.
Wipe off the silicone grease from the filter
inlet, and cap it.
13. Remove the umbilical cord from the last
impinger, and cap the impinger. After wiping
off the silicone grease, cap off the filter
holder outlet and impinger inlet.
14. Transfer the probe and filter-impinger
assembly to the cleanup area that is clean
and protected from the wind.
E. Sample Recovery
1. Place 200 mL acetone from the wash bottle
being used for cleanup in a glass sample
container labeled "acetone blank."
2. Inspect the train prior to and during
disassembly, and note any abnormal
conditions.
3. Container No. 1 (Filter)
a. Using a pair of tweezers and/or clean
disposable surgical, gloves, carefully
remove the filter from the filter holder,
and place it in its identified petri dish
container. If necessary, fold the filter
such that the PM cake is inside the fold.
b. Using a dry Nylon bristle brush and/or a
sharp-edged blade, carefully transfer to
the petri dish any PM and/or filter fibers
that adhere to the filter holder gasket.
Seal the container.
4. Container No. 2 (Acetone Rinses)
Recover particulate matter from the probe
nozzle, Swagelok fitting, probe liner (use a funnel
to aid in transferring liquid washes to the
container), front half of the filter holder, and (if
applicable) the cyclone, and recover all rinses in a
glass container as follows;
a. Before cleaning the front half of filter
holder, wipe clean all joints of silicone
grease.
b. Rinse with acetone, brush with a Nylon
bristle brush, and rinse with acetone
until there are no visible particles. Make
a final acetone rinse.
c. For probe liner, repeat rinse, brush, rinse
sequence at least three times for glass
liners, and six times for metal liners.
d. Make a final rinse of the brush with
acetone.
e. After completing the rinse, tighten the
lid on the sample container. Mark the
height of the fluid level. Label the
container.
5. Container No. 3 (Silica Gel)
a. Determine whether silica gel has been
completely spent, and note on FDS its
condition.
b. Using a funnel, transfer the silica gel
from impinger 4 to its original container,
and seal. Use a rubber policeman (do
not use any liquid), if necessary, to
remove the silica gel from the impinger.
c. If a balance is available, weigh the spent
silica gel to the nearest 0.5 g.
6. Impinger Water
a. Note on FDS any color or film in the
liquid catch.
b. Measure the liquid volume in impingers
1, 2, and 3 to within ± 1 mL (with a
graduated cylinder) or weigh liquid to
within ±0.5 g.
c. Discard the liquid, unless analysis of the
impinger catch is required. Store as is
appropriate.
7. Whenever possible, ship sample containers
in an upright position.
-------
9/30/94: F5-3
f. Variations
1. If high pressure drop across the filter causes
difficulty in maintaining isokinetic sampling,
replace the filter. Suggestion: Use another
complete filter assembly rather than changing
the filter itself. Before installing a new filter
assembly, conduct a leak-check (see FP 5a).
Add the filter assembly catches for the total
PM weight.
2. Use a single train for the entire sample run,
except when simultaneous sampling is
required in two or more separate ducts or at
two or more different locations within the
same duct, or, in cases where equipment
failure necessitates a change of trains. In all
other situations, obtain approval from the
Administrator before using two or more
trains.
3. When two or more trains are used, analyze
separately the front-half and (if applicable)
Impinger catches from each train unless
Identical nozzle sizes were used on all trains.
In this case, the front-half catches from the
Individual trains may be combined (as may
the implnger catches) and one analysis of
front-half catch and one analysis of impinger
catch may be performed. Consult with the
Administrator for details concerning the
calculation of results when two or more
trains are used.
4. Use more silica gel in impinger 4, if
necessary, but ensure that there is no
entrainment or loss during sampling.
5. If a different type of condenser (other than
Impingers) is used, measure the amount of
moisture condensed either volumetrically or
gravimetrically.
6. If the total paniculate catch is expected to
exceed 100 mg or when water droplets are
present in the stack gas, use a glass cyclone
between the probe and filter holder.
7. If a flexible line is used between the first
Impinger or condenser and the filter holder,
disconnect the line at the filter holder, and let
any condensed water or liquid drain into the
Impingers or condenser.
6. Alternatives
1. Sampling trains using metering systems
designed for higher flow rates than 1 cfm
may be used.
2. For moisture content, weigh the silica gel
and its impinger or sampling holder before
and after sampling to the nearest 0.5 g.
3. Rathei than labeling filters, label the shipping
containers (glass or plastic petri dishes), and
keep the filters in these containers at all
times except during sampling and weighing.
4. Rather than successive desiccations, oven
dry the filters at 105°C for 2 to 3 hr,
desiccate for 2 hr, and weigh.
5. Deionized distilled water may be used
instead of acetone when approved by the
Administrator and shall be used when
specified by the Administrator; in these
cases, save a water blank, and follow the
Administrator's directions on analysis.
6. Acceptable alternatives to glass liners are
metal liners (e.g., 316 stainless steel,
Incoloy 825 or other corrosion resistant
metals) made of seamless tubing.
H. Suggestions
1. Use either borosilicate or quartz glass probe
liners for stack temperatures up to about
900°F. Use quartz liners for temperatures
between 900 and 1,650 °F. The softening
temperature for borosilicate is 1,508°F,and
for quartz it is 2,732°F.
2. Whenever practical, make every effort to use
borosilicate or quartz glass probe liners.
Metal liners may bias results high.
3. Nomographs to aid in the rapid adjustment of
the isokinetic sampling rate without
excessive computations are available (see
APTD-0576 for details). Limitations: Type S
pitot tube C- = 0.85 ± 0.02 and
Md = 29 ± 4.
4. For large stacks, consider sampling from
• opposite sides of the stack to reduce the
length of probes.
5. Center and place the gasket properly to
prevent the sample gas stream from
circumventing the filter.
6. Do not cap off the probe tip tightly while the
sampling train is cooling down as this would
create a vacuum in the filter holder, which
may draw water from the impingers into the
filter holder.
-------
9/30/94'.
Method
FIELD DATA SHEET 5
Isokinetic Sampling Trains
Client/Plant Name
City/State
Personnel
Date
Job #
Test Location
Run #
Equipment Checks
Pitot Leak-Chk:
Pre Post
Nozzle:
Pre Post
TC:
Pre Post
Orsat system
Rlter*
Tare Wt.
Equipment IPO's
Rgnt Box Sampl'a Box tt
Meter Box Y Umbilical
Pitot Cr Tedlar Bag
Noz'l Dn Orsat Pump
TC Readout TC Probe
Isokinetic Set-Up Data
AH
-------
9/30/94: FD5-2
Method
Client/Plant Name
Test Location
FIELD DATA SHEET 5 (continued)
Isokinetic Sampling Trains
Job #.
Run*
L
N
E
28
27
2*
2*
30
31
32
33
34
3C
31
37
J*
3»
40
41
42
43
44
46
4*
47
4*
40
CO
*0
•1
•2
•3
•4
es
Sample
Point
FINAL
Clock
Time
DGM
Reading (cf)
tj(°F)
t0(°F)
Pttot
AP
(In. H20)
Stack
Temp.
(°F)
Orifice (In. Hg)
Actual
Ideal
Gauge
Vacuum
(In. Hg)
*
Filter
"-.
Impinger
Exit
QA/QC Check
Completeness _
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: FD5-3
FIELD DATA SHEET 5 (Continued)
Moisture Analytical Results
Client/Plant Name
City/State ^___
Job #.
Test Location
Barometric Pressure
Personnel
Date ,
Run Number
Impinger 1 : ( )
Final, mL
Initial, mL
Water Catch, mL
Impinger 2: ( )
Final, mL
Initial, mL
Water Catch, mL
Impinger 3: ( )
Final, mL
Initial, mL
Water Catch, mL
Condensed Water, mL
i
I
Impinger volumes may be measured collectively.
Silica Gel:
Final Weight, g.
Tared Weight, g.
Absorbed Water, g.
1 g = 1 mL
Total Water Collected,
Vlo mL
|
Balance No.
Balance Type (•/} Triple Beam
Electronic
Reagent Box #
Volume measured to within ± 1.0 mL?
Weights measured to ±0.5 g?
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: L5-1
LABORATORY PROCEDURE 5
Participate Matter
A. Analysis
1. Container No. 1 (Filter)
a. Leave the contents in the shipping
container or transfer the filter and any
loose PM from the sample container to a
tared glass weighing dish.
b. Desiccate for 24 hr in a desiccator
(anhydrous calcium sulfate).
c. Weigh to a constant weight, and report
the results to the nearest 0.1 mg.
"Constant weight" means a difference of
no more than 0.5 mg or 1% of total
weight less tare weight, whichever is
greater, between two consecutive
weighings, with no less than 6 hr of
desiccation time between weighings.
2. Container No. 2 (Acetone Rinses)
a. Note the level of liquid in the container,
determine loss (if any), and note loss on
LDS5.
b.
c.
d.
Measure the liquid either to ± 1 mL or
weigh the liquid to ±0.5 g.
Transfer the contents to a tared 250-mL
beaker, and evaporate to dryness at
ambient temperature and pressure.
Desiccate for 24 hr, and weigh to a
constant weight.
e. Report the results to the nearest 0.1 mg.
3. Container No. 3 (Silica Gel)
a. If not done in the field, weigh the spent
silica gel (or silica gel plus impinger) to
the nearest 0.5 g.
4. "Acetone Blank" Container
a. Measure the acetone in this container
either volumetrically or gravimetrically.
b. Transfer the acetone to a tared 250-mL
beaker, and evaporate to dryness at
ambient temperature and pressure.
c. Desiccate for 24 hr, and weigh to a
constant weight.
d. Report the results to the nearest
0.1 mg.
B. Alternative
1. Container No. 1
a. Oven dry the sample at 105°C for 2 to
3 hr, and cool in a desiccator.
b. Weigh the sample and use this weight
as a final weight.
2. Container No. 2 and Acetone Blank'
a. Evaporate at temperatures higher than
ambient, but below the boiling point of
the solvent.
b. To prevent "bumping," closely supervise
the evaporation process; swirl
occasionally the contents of the beaker
to maintain an even temperature.
c. Use extreme care, as acetone is highly
flammable and has a low flash point.
-------
9/30/94: LD5-1
LABORATORY DATA SHEET 5
Paniculate Matter
Client/Plant Name • Job #
City/State Analyst
Barometric Pressure " Ha Lab Ambient Temp. °F Relative Humidity in Lah (
-------
9/30/94: F5a-1
FIELD PROCEDURE 5a
Leak-Check of Isokinetic Sampling Train
A. From Probe Nozzle
1. After assembling the sampling train, turn on
and set the filter and probe heating systems
to the desired operating temperatures. Allow
time for the temperatures to stabilize.
2. Plug the nozzle. Fully open the bypass valve
and close the coarse adjust valve. Then start
the pump.
3. Slowly close the bypass valve until the
desired vacuum Is reached. Do not reverse
direction of bypass valve; this will cause
, water to back up into the filter holder. If the
desired vacuum is exceeded, either leak-
check at this higher vacuum or end the leak-
check as shown in step A5, and start over.
4. Allow the flow rate to stabilize, then
determine the leakage rate using DGM
readings and a watch. Record the leakage
rate.
5. End the leak-check as follows: first slowly
remove the plug from the inlet to the probe,
and Immediately turn off the vacuum pump.
This prevents the water in the impingers from
being forced backward into the filter holder
and silica gel from being entrained backward
into the third impinger.
B. Specifications
1. Vacuum: &15 in. Hg or S: maximum
vacuum reached during test run.
2. Leakage Rate: :s0.02 cfm or :S4% of
average sampling rate, whichever is less.
C. Alternative Procedure for Asbestos String
Connection
Leak-check as in section A at 15 in. Hg, or as
follows:
1. Do not connect the probe to the train during
the leak-check.
2. First, leak-check the train from the inlet to
the filter holder (cyclone, if applicable) at
15 in. Hg vacuum.
3. Then, connect the probe to the train, and
leak-check from the probe nozzle at about
1 in. Hg vacuum.
D. Leak-Checks During Sample Run
1. If, during the sampling run, a component
(e.g., filter assembly or impinger) change
becomes necessary, leak-check the train
immediately before the change is made at
S: maximum vacuum recorded up to that
point in the test run.
2. Immediately after component changes, leak-
checks are optional.
£ Metering System with Diaphragm Pump
1. Make a 10-min calibration run at 0.'Q2 cfm
(seeCPS).
2. At the end of the run, determine the
difference of the measured wet'test meter
and DGM volumes, and divide by 10 to
obtain the leak rate.
F. From Other Train Components
Follow section A, except leak-check from the
inlet of the specified component, e.g., inlet to the
filter holder or inlet to the first impinger.
-------
: F5b-1
FIELD PROCEDURE 5b
Leak-Check of Metering System (After Pump)
1. Close the main valve on the meter box
(see Figure F5b-1).
2. Insert a one-hole rubber stopper with rubber
tubing attached into the orifice exhaust pipe.
3. Disconnect and vent the low side of the
orifice manometer.
6.
Close off the low side orifice tap. Blow into
the rubber tubing and pressurize the system
to 5 to 7 in. H2O.
Pinch off the tubing, and observe the
manometer for one minute.
If there is a loss of pressure on the
manometer, correct leak in the metering
system.
Blow Into Uting
until manometer
reads 5 to 7
inches water
column
Pump
Figure F5b-1. Leak check of meter box.
-------
9/30/94: Q5-1
QUALITY CONTROL PROCEDURE 5
Metering System/Orifice Check
A. Procedure 1 - Y0 Check 4. Divide Yc by Y. If the ratio is not within
°' tO1 •O3'check he meteri"9
1. Operate the metering system (i.e., pump, . , . . .. .. „ ^
volume meter, and orifice) at AH@ (from before be9™9 the test-
CDS 5) for 10 min.
B. Procedure 2 - Critical Orifice
2. Record the volume collected, the DGM
temperature, and the barometric pressure. 1 • lnsert the critical orifice, calibrated against a
wet test meter or spirometer, into the inlet of
3. Calculate a DGM calibration check value, Yc, the sampling meter box.
as follows:
2. Follow the procedure described in CP 5d.
0.0319 (V460) 1/2 •
where:
Y0 = DGM calibration check value,
dimensionless.
10= Run time, min.
Vm = Volume of gas sample as measured by
DGM, dcf.
Td = Average DGM temperature, °F.
Pb = Barometric pressure, in. Hg.
0.0319 = (0.0567 in. Hg/°R)(0.75 cfm)2
-------
9/30/94: CB-1
CALIBRATION PROCEDURE 5
Metering System
A. Initial
1. Optional: Leak-check the metering system
(see FP 5a). Any leaks are calibrated into the
DGM calibration factor (Y); the post-test
calibration checks for any changes.
2. Connect the metering system inlet to the
outlet of a wet test meter (WTM). See
Figure C5-1.
3. Run the metering system pump for about
15 min at the AI-U value.
-------
9/30/94: CD5-1
CALIBRATION DATA SHEET 5
Metering System
Metering System ID#.
Date
Barometric Pressure, Pb
Initial Calibration Recalibration
in. Hg Personnel
Capacity: WTM =
cf/rev?) Spirometer:
If a splfomoter Is used, modify data sheet accordingly.
Flow
Rate of
Max Cap
0.5
1.0
1.5
2.0
3.0
4.0
WTM
vw
(cf)
5
5
10
10
10
10
tw
(°F)
Metering System
vd
(cf)
tj
(°F)
t0
(°F)
Avg td
(°F)
Ap
(in. H2O)
Time
e
(min)
Avg
Y,
',.
AH@i
AH
(in. H20)
0.5
1.0
1.5
2.0
3.0
4.0
y VwPb(td + 460)
V/O , Arl \ /+ _,_ xcn\
d b 136 ^*
00319AHfp,,+ AH ) / . x«r>
u.ujijnn^b 13_6J (tw + 46o)eP
-------
9/30/94: CBa-1
CALIBRATION PROCEDURE 5a
Metering System Using Critical Orifices
A. Initial
1. Record the barometric pressure.
2. Calibrate the metering system using CP 5d
and record the information listed in CDS 5d.
3. Calculate DGM volume tVm(std)], critical
orifice volume [Vcr{std)], and DGM calibration
factor (Y).
4. Average the DGM Yj values for each of the
flow rates. Ys £ ±2% from average.
B. Recalibration
1. Compare the DGM Y factors obtained from
two adjacent orifices each time a DGM is
calibrated; e.g., when checking orifice
13/2.5, use orifices 12/10.2and 13/5.1.
2. If any critical orifice yields a DGM Y factor
differing > ±2% from the others, recalibrate
the critical orifice (see CP 5d).
-------
9/30/94: C5b-1
CALIBRATION PROCEDURE 5b
Probe Nozzle Diameter
A. Initial Calibration
1. Using a micrometer, measure the inside
diameter of the nozzle to the nearest
0.001 in.
2. Make three separate measurements using
different diameters each time.
3. Average the measurements.
4. Permanently and uniquely identify each
nozzle.
B. Recalibration
1. When nozzles become nicked, dented, or
corroded, reshape and sharpen.
2. Recalibrate as in section A.
-------
9/30/94: CDSb-1
CALIBRATION DATA SHEET 5b
Probe Nozzle Diameter
Date
Nozzle ID#
Nozzle Diameter, Dn (inches)
0)
(2)
(3)
Hi-Lo
Avg
Intls
»Dn
OK
QA/QC Check
Initial each diameter measurement (last column) only if the following are met.
Each diameter measured to within ±0.001 inches?
High - Low ^0.004 inches?
Complete, legible, accurate, and reasonable?
-------
9/30/94: CP 5c-1
CALIBRATION PROCEDURE 5c
Dry Gas Meter as a Calibration Standard
Note: A dry gas meter (DGM) may be used as a calibration standard for volume measurements in place of
the wettest meter (WTM) specified in section 5.3 of Method 5. Do not use the standard DGM in the field,
and if transported, care for it as any other laboratory instrument.
A. Initial
1. Set up the components as shown in
Figure C5c-1. A spirometer instead of the
WTM may be used.
2. Run the system at 1 cfm. The Ap at the
inlet side of the DGM must be <4 in. H2O.
If not, use larger diameter tubing
connections and straight pipe fittings to
lower the Ap.
3. Run the pump for ^5 min at about 0.35 cfm.
4.
5.
Collect the data as shown in the CDS 5c.
Use at least five different flow rates over the
range of 0.35 to 1.2 cfm or over the
operating range. Make triplicate runs at each
of the flow rates.
Calculate flow rate, Q, and the DGM
coefficient, Ydl, for each run.
6. Average the three Yd. values at each flow
rate.
7. Plot Yd, versus Q for the DGM. Use this
curve as a reference to calibrate other
DGM's and to determine whether its
recalibration is required.
B. Recalibration
Recalibrate the standard DGM against a WTM
or spirometer annually or after every 200 hr of
operation, whichever comes first.
C. Alternative
As an alternative to full recalibration
(section A), a two-point calibration check may be
made as follows:,
1. Follow the same procedure and equipment
arrangement as for a full recalibration, but
run the meter at only two flow rates, e.g.,
0.5 and 1.0 cfm).
2. Calculate Ydo for these two points.
3. Compare each Yde values with Yd9 values
from the meter calibration curve. If the two
coefficients are within 1.5% of the
calibration curve values at the same flow
rate, the meter need not be recalibrated until
the next date for a recalibration check.
D. Method 6 Applicability
A DGM may be used as a calibration standard
for volume measurements in place of the WTM
specified in section 5.1 of Method 6. Follow the
same steps as that in section A, except for the
following:
1. Calibrate the DGM at 1 L/min against a
WTM (± 1 %) having a capacity of 1 L/rev or
3 L/rev.
2. Calibrate the Method 6 meter box at
1 L/min.
Temperature
Sensors
Thermometer
Orifice
manometer
Vacuum
Gauge
Air inlet
Pump
Figure C5c-1. Sample meter system calibration setup.
-------
9/30/94: CD5c-1
CALIBRATION DATA SHEET 5c
Dry Gas Meter as a Calibration Standard
Dry Gas Meter ID#
Date
Barometric Pressure, Pb
Initial Calibration Recalibration
in. Hg Personnel
Capacity: WTM =
1 cf/rev?) Spirometer:
(^ 14 cf?)
Nom.
Q
(cfm)
0.40
0.60
0.80
1.00
1.20
WTM
vw
(cf)
tw
(°R
DGM
Vd8
(cf)
ti
(°F)
to
(°F)
Av9 tds
(°F)
Ap
(in. H2O)
Time
(min)
FR
Q
(cfm)
Meter Coeff.
Yd3
••
Avg
Yds
'
-
-
- "
™ '""
'*''' /
S.. f
M P
Q = 17.64 -^ b
V
0 (tw + 460)
460)
13.6
For each flow rate, Yd3 (maximum - minumum) ^0.030 for 3 successive runs?
At 1 cfm, Ap ^4.0 in. H2O?
Each Ya, = 1.00 ± 0.05?
If alternative recalibration, recalibration T^ within ± 1.5% of initial calibration "Yds at each flow rate?
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: CP 5d-1
CALIBRATION PROCEDURE 5d
Critical Orifices as Calibration Standards
A. Selection of Critical Orifices
1. Select five critical orifices to cover the range
between 0.35 and 1.20 cfm or the expected
operating range. Two of the critical orifices
must bracket the expected operating range.
2. Use three of these five critical orifices to
calibrate the DGM. Save the other two as
spares and to better bracket the range of
operating flow rates. Hypodermic needle
sizes and tubing lengths shown below give
the following approximate flow rates:
Approximate Sizes/Flow Rates
for Critical Orifices
Gauge/in.
12/3.0
12/4.0
13/1.0
13/2.0
13/3.0
13/4.0
cfm
1.15
1.06
0.91
0.83
0.79
0.73
Gauge/in.
14/1.0
14/2.0
14/3.0
15/1.25
15/3.0
15/4.0
cfm
0.69
O.61
0.57
0.50
0.41
0.37
3. To adapt these needles to a Method 5 type
sampling train, do the following:
a. Insert a serum bottle stopper, 13- by
20-mm sleeve type, into a 1/2-in.
Swagelok quick connect.
b. Insert the needle into the stopper as
shown in Figure C5d-1.
4. Determine suitability and the appropriate
operating vacuum of the critical orifices as
follows:
a. Turn on the pump, fully open the coarse
adjust valve, and adjust the by-pass
valve to give a vacuum reading
corresponding to about half of
atmospheric pressure.
b. Observe the meter box orifice
manometer reading, AH. Slowly
increase the vacuum reading until a
stable reading is obtained on the meter
box orifice manometer.
c. Record the critical vacuum for each
orifice. Do not use orifices that do not
reach a critical value.
B. Critical Orifice Calibration
1. Leak-check the Method 5 metering system
(see FP 5a) from its inlet. The leakage rate
must be zero, i.e., no detectable movement
of the DGM dial for 1 min.
2. Leak-check that portion of the sampling train
between the pump and the orifice meter
(see FP 5b).
3. Calibrate the metering system (see CP 5),
and record the DGM calibration factor, Y.
4. Insert the critical orifice into the inlet of the
metering system. Do not use any
connections at the inlet of the orifice.
5. Warm up the system for 15 min.
6. Leak-check the system (see FP 5a) from the
inlet of the critical orifice.
7. Record the information listed in CDS 5d.
8. Conduct duplicate runs at a vacuum of 1 to
2 in. Hg above the critical vacuum. Run for
at least 5 min each, using complete
revolutions of the DGM. (As a guideline,
duplicate runs should not differ by more
than 3.0 sec to achieve ±0.5% in K'.)
I
Critical
Ortta)
s==s
'?==:
||
\ ^
Serum
Stopper
—
Qul
Con
Figure C5d-1. Critical Orifice Adaptation to Method 5 metering system.
-------
9/30/94: CD5d-1
CALIBRATION DATA SHEET 5d
Critical Orifice/Metering System
Check (/) Initial Calibration
Check (/) Critical Orifices
Recalibration
Date
Metering System
Personnel
Grit. Orifice/Meter Box ID#
Run No.
Meter Box Inlet: Leak = 0?
Cr. Orifice Inlet: Leak = 0?
Cr. Orifice Inlet: Leak
DGM Final Rdg (cf)
DGM Initial Rdg (cf)
Difference, Vm (cf )
DGM Inlet/Outlet Temp
Initial (°F)
Final (°F)
Average, tm (°F)
Time (Diff ss3 sec?) (min/sec)
Time, Q . (mm)
Orifice AH (in. H2O)
Bar Pressure, Pb (in. Hg)
Amb Temp., tamb (°F)
Pump Vacuum (in. Hg)
K' Factor
Average K' Factor
Diff s ±0.5% from avg?
Vm(std) (Cf)
Vcr(std) (Cf)
DGM Calib. Factor, Y,
Yj :< ± 0.02 from avg?
AH@
AH@ =s 0.02 from avg?
/
/
/
/
/
/
/
/
/
/
/
/
/
/ .
/
f
1
1
Pb(tm +460)6
Vm(std) = 17.64V,,
13.6
_ *cr(std)
cr(std(
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: S5A-1
Client/Plant Name
Job No.
Sampling Location
Run ID #
SUMMARY SHEET 5A
Paniculate Matter
FDS5
FDS5
FDS 5
FDS5
Run#1
Run #2
Run #3 Avg
Test Date
Run Start Time
Run Finish Time
FDS5
FDS5
FDS5
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, mln
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Abs Stack Pressure (Pb + Pg/13.6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temperature (ts + 460), R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(t,, +460) Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Volumetric Flow Rate, dscfh
Volumetric Flow Rate, wscfh
Isoklnetic Sampling Rate, % %l
Acetone Blank, mg Wt
Total Paniculate Mass (Blank Corr.), mg mn
Paniculate Concentration, g/dscf cs
FDS1
FDS 1
G FDS 5
Dn FDS 5
Y CDS 5
AH FDS 5
Pb FDS 5
Pg FDS 5
PS SS5
ts FDS 5
Ts SS5
%CO2 FDS 3
%O2 FDS 3
%(CO + N2) FDS 3
Mrf FDS 3
m
m(std)
V,
Ic
V,
w(std)
CP
Ap
|Ap]
1/2
fDS5
FDS 5
SS5
FDS 5
SS5
SS5
CDS 2a
FDS 5
FDS 5
SS5
FDS 1
SS5
SS5
SS5
LDS5A
LDS5A
SS5
-------
9/30/94: S5A-2
Run #1 Run #2 Run #3 Avg
Post-test Calibration Checks
Temperature and Barometer CDS 2d
Differential Pressure Sensor CDS 2d
Metering system CDS 5
-------
9/30/94: F5A-1
FIELD PROCEDURE 5A
Particulars Matter from Asphalt Roofing Operations
Note: The sampling procedure is the same as that in FP 5, except for the items noted below:
A. Pretest Preparation
1. Thoroughly clean each component with
soap and water followed by at least three
1,1,1-trichloroethane (TCE) rinses. Use the
probe and nozzle brushes during at least
one of the TCE rinses (refer to step E4 of
FP 5 for rinsing technique). Cap or seal the
open ends of the probe liners and nozzles to
prevent contamination during shipping.
2. When the stack gas moisture is > 10%, use
a precollector cyclone. Do not use the
cyclone under other, less severe conditions.
B. Preparation of Collection Train
1. Set up the sampling train as shown in
Figure F5-1 and, if used, place the
precollector cyclone between the probe and
filter holder. If stack gas temperatures are
>480°F, water-cooled probes may be
required to control the probe exit
temperature to 108 ± 18°F.
2. Do not use stopcock grease on ground glass
joints unless grease is insoluble in TCE.
3. Install a temperature gauge to measure to
within ±5.4°F the sample gas at the exit
end of the filter holder.
C. Sampling and Sample Recovery
1. Maintain the gas temperature exiting the
filter at 108 ± 18°F. Maintain the
temperature of the precollector cyclone, if
used, at 108 ± 18°F.
2. The sample recovery is the same as that in
FP 5, except for the following additions and
deviations:
a. Use TCE (in glass wash bottles) instead
of acetone to recover the sample into
Container No. 2. Measure the total
amount of TCE used in the rinses.
b. Include the rinses of the cyclone and
cyclone collection flask (if used) in this
container.
c. Save a portion of the TCE used for
cleanup as a blank. Take 200 mL of this
TCE directly from the wash bottle being
used, and place it in a glass sample
container labeled TCE Blank."
d. Use as sample storage containers,
chemically resistant, borosilicate glass
bottles, with rubber-backed Teflon
screw cap liners or caps that are
constructed so as to be leak-free, and
resistant to chemical attack by TCE,
500-mL or 1,000-mL.
-------
9/30/94: L5A-1
LABORATORY PROCEDURE 5A
Participate Matter from Asphalt Roofing Operations
A. Analysis
1. Container No. 1 (Filter)
a.
b.
c.
d.
Transfer the fitter from the sample
container to a tared glass weighing dish,
and desiccate for 24 hr in a desiccator
(anhydrous calcium sulfate).
Rinse Container No. 1 with a measured
amount of TCE, and analyze this rinse
with the contents of Container No. 2.
Weigh the filter to a constant weight,
i.e., a difference of no more than 10% or
2 mg {whichever is greater) between two
consecutive weighings made 24 hr apart.
Report the "final weight" to the nearest
0.1 mg as the average of these two
values.
2. Container No. 2 (Probe to Filter Holder)
a.
b.
d.
Before adding the rinse from Container
No. 1 to Container No. 2, determine loss
(if any), and note loss on LDS 5A.
Measure the liquid in this container either
volumetrically to ± 1 mL or
gravimetrically to ±0.5 g.
If the volume of condensed water
present in the TCE rinse (look for a
boundary layer or phase separation)
appears >5 mL, separate the oil-TCE
fraction from the water fraction using a
separator/ funnel. Measure the volume
of the water phase to the nearest mL;
add this amount to step E6 of FP 5.
Extract the water phase with several
25 mL portions of TCE until, by visual
observation, the TCE does not remove
any additional organic material.
Evaporate the remaining water fraction
to dryness at 200 °F, desiccate for 24 hr,
and weigh to the nearest 0.1 mg.
e. Combine the TCE from step 1 with the
TCE from step 2c, which includes the
TCE from the water phase extractions.
f. Transfer the TCE and oil to a tared
beaker, and evaporate the TCE at
ambient temperature and pressure (may
take several days).
g. Do not desiccate the sample until the
solution reaches an apparent constant
volume or until the odor of TCE is not
detected.
h. When it appears that the TCE has
evaporated, desiccate the sample, and
weigh it at 24-hr intervals to obtain a
"constant weight." Report the results
to the nearest 0.1 mg.
3. Container No. 3 (Silica Gel)
If not done in the field, weigh the spent silica
gel (or silica gel plus impinger) to the nearest
0.5 g using a balance.
4. "TCE Blank" Container
a. Measure the TCE in this container either
volumetrically or gravimetrically.
b. Transfer the TCE to a tared 250-mL
beaker, and evaporate to dryness at
ambient temperature and pressure.
c. Desiccate for 24 hr, and weigh to a
constant weight. Report the results to
the nearest 0.1 mg.
B. Alternative
TCE liquid samples may be dried in a controlled
temperature oven at temperatures up to 100°F
until the TCE is evaporated.
-------
9/30/94: L5B-1
LABORATORY PROCEDURE SB
Nonsulfuric Add Participate Matter
Note: This laboratory procedure is the same as that in LP 5, except for the following fuse LDS 5):
1. Dry the probe sample at ambient 3. Cool in a desiccator for 2 hr, and weigh to
temperature. constant weight.
2. Then oven dry the probe and filter samples at
a temperature of 320 ± 10°F for 6 hr.
-------
FIELD PROCEDURE 5D
^articulate Matter from Positive Pressure Fabric Filters
fh
the
A.
1.
9/30/94: F5D-1
''6XCept for idemifYin9 ^ropriate alternative locations and procedures for
from positive pressure fabric filters (use FDS 5).
a.
b.
Determination of Measurement Site 3.
Stacks Meeting Method 1 Criteria. See
FP1.
Short Stacks Not Meeting FP 1 Criteria. Use
either of the following:
Stack extensions and FP 1.
Flow straightening vanes of the "egg-
crate" type (see Figure F5D-1). Locate
the measurement site downstream of
the straightening vanes £t2 De of the
largest vane opening and >0.5 D of
the stack diameter upstream of the
stack outlet.
Roof Monitor or Monovent (e.g., peaked roof
monitor and ridge vent). See Figure F5D-2.
Use a measurement site at the base of the
monovent and upstream of any exhaust
point (e.g., louvered vent).
Compartment Housing. Sample immediately
downstream of the filter bags directly above
the tops of the bags as shown in the
examples in Figure F5D-2. Depending on
the housing design, use sampling ports in
the housing walls or locate the sampling
equipment within the compartment housing.
B. Determination of Number and Location of
Traverse Points
Because a performance test consists of 5:3
test runs and because of the varied configurations
of positive pressure fabric filters, there are several
schemes for combining the number of traverse
points and the three test runs. Q
1. Single Stacks Meeting Method 1 Criteria. 1.
a. Use FP 1.
4.
2.
b.
a.
Sample all traverse points for each test
run.
Other Single Measurement Sites.
Use 5:24 traverse points (this includes
roof monitor or monovent and single
compartment housing. For example, for
a rectangular measurement site, such as
a monovent, use a balanced 5x5
traverse point matrix.
Sample all traverse points for each test
run.
b.
Multiple Measurement Sites. Sampling from
two or more stacks or measurement sites
may be combined fora test run, provided the
following guidelines are met:
a. For <. 12 measurement sites, sample all
sites. For > 12 measurement sites,
sample 12 or 50% of the sites,
whichever is greater. Evenly, or nearly
evenly, distribute the measurement sites
sampled among the available sites; if
this cannot be done, sample all sites.
b. Sample the same number of
measurement sites for each test run.
c. Use 5:24 traverse points (sum of
traverse points from tested
measurement sites) per test run, except
when a test run is combining two stacks
that FP 1 specifies fewer than -12 points.
d. If the 24 traverse points per test run
criterion is met, the number of traverse
points per measurement site may be
reduced to eight.
e. Alternative: Conduct a test run for each
measurement site individually using the
criteria in step B1 or B2 for number of
traverse points (5:3 runs are required for
a performance test). If more than three
measurement sites are sampled, the
number of traverse points per
measurement site may be reduced to
eight as long as 5:72 traverse points are
sampled for all the tests.
Examples
Example 1: Nine circular measurement sites
of equal areas.
a. Each of three test runs - traverse three
measurement sites using four points per
diameter (eight points per measurement
site).
b. Run #1 - sample sites 1, 2, and 3;
run #2 - sample sites 4, 5, and 6; and
run #3 - sample sites 7, 8, and 9.
c. Alternative: For each run, test
separately all nine measurement sites
using eight points per site.
-------
. 0.20 x D
(Call Size)
0.45 x D
NOTE: Position Straighteners So That Cell Sides Are Located
Approximately 45° From Traverse Diameters,
Figure F5D-1. Example of Flow Straightening Vanes.
Ventilator Throat
Sampling Sites
Entry Ports for
Sampling Above
Rlter Bags
Ventilator Throat
Sampling Sites
Entry Ports for
Sampling Above
Filter Bags
Figure F5D-2. Acceptable Sampling Site Locations for (a) Peaked Roof; and
(b) Ridge Vent Type Fabric Filters.
-------
2. Example 2: Thirty rectangular measurement
sites of equal areas. At least 50% or
15 sites must be sampled.
a. Each of three test runs - traverse five
measurement sites using a 3 x 3
traverse point matrix for each site.
b. Number the sites consecutively from
1 to 30 and sample all the even
numbered (or odd numbered) sites.
c. Alternative: Sample separately each of
15 measurement sites using step B1 or
B2 to determine the number and
location of traverse points.
3. Example 3: Two measurement sites of
equal areas.
a. Each of three test runs - traverse both
measurement sites using step B3 to
determine number of traverse points.
b. Alternative: Conduct two full emission
test runs of each measurement site
using step B1 or B2 to determine the
number of traverse points.
9/30/94: F5D-2.
4. Note: For other test schemes, such as
random determination of tuverse points for
a large number of measurement sites,
consult with the Administrator.
D. Velocity Determination
1. If velocities at the measurement site is too
low to measure accurately (i.e., velocity
head <0.05 in. H2O), measure the gas flow
rate at the fabric filter inlet following the
procedures in FP 2.
2. Calculate the average gas velocity at the
measurement site using the information from
step D1, and use this velocity to determine
and maintain isokinetic sampling rates.
3. Note: Block and make leak-tight all sources
of gas leakage, into or out of the fabric filter
housing between the inlet measurement site
and the outlet measurement site.
-------
9/30/94: S5E-1
SUMMARY SHEET 5E
Particulate Matter
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Abs Stack Pressure (Pb + Pg/13.6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temperature (ts + 460), R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(ts) +460) Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Volumetric Flow Rate, dscfh
Volumetric Flow Rate, wscfh
Isokinetlc Sampling Rate, %
Acetone Blank, mg
Water Blank, mg
M5 Particulate Mass (Blank Corr.), mg
TOC Particulate Mass, mg
Water Rinse Particulate Mass, mg
M5E Particulate Mass, (Blnk Corr.), mg
M5E Particulate Concentration, g/dscf
6
Dn
Y
AH
Pb
pg
PS
TSS
%C02
%02
%{CO + N2)
Md ,
tm
v
Vm(std)
v
Vw(std)
ws
c
Ap
rrsiAp]1/2
vs
A
Qsd
QSW
Wa
waw
mn
mc
mww
mn
cc
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 1
FDS 1
FDS 5
FDS 5
CDS 5
FDS 5
FDS 5
FDS 5
SS5
FDS 5
SS5
FDS 3
FDS 3
FDS 3
FDS 3
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS2a
FDS 5
FDS 5
SS5
FDS 1
SS5
SS5
SS5
LDS5
LDS 5E
LDS5
LDS5E
LDS5E
SS5E
SS5E
Run #1
Run #2
Run #3
Avg
-------
Post-test Calibration Checks
Temperature and Barometer
Differential Pressure Sensor
Metering System
Run #1
9/30/94: S5E-2
Run #2 Run #3 Avg
CDS2d
CDS2d
CDS 5
mn (M5E) m mn (MS) + mww - Ww + m,
0.001 —2-
Vm(std)
-------
9/30/94: F5E-1
FIELD PROCEDURE 5E
Particulrte Emissions from Wool
Fiberglass Insulation Manufacturing
Note: This procedure /s the same as that in FP 5, except for the following (use FDS 5):
A, Sampling
1. Insert a temperature gauge in the rear half
of the filter holder to measure the sample
gas exit temperature.
2. Substitute O.1 N NaOH for water in the
impingers.
3. Use only borosilicate or quartz glass liners.
4. Use only glass storage bottles and funnels.
B. Sample Recovery
1. Use water to rinse and clean the probe parts
prior to the acetone rinse. Save portions of
the water, acetone, 0.1 N NaOH used for
cleanup as blanks.
2. Container No. 1 (Filter). Use FP 5, step E3.
3. Container No. 2 (Water Rinses). Use FP 5,
step E4, except rinse with water and do not
brush. Put all the water wash in one
container, seal, and label.
4. Container No. 3 (Acetone Rinses). Use FP 5,
step E4, for the acetone rinse.
5. Container No. 4 (Silica Gel). Use FP 5,
step E5.
6. Container No. 5 (Impinger Liquid)
a. Measure the liquid in the first three
impingers and record the volume or
weight. See FP 5, step EG.
b. Do not discard this liquid, but transfer it
into a sample container using a funnel
(glass or polyethylene).
c. Rinse each impinger thoroughly with
0.1 N NaOH three times, as well as the
graduated cylinder (if used), and the
funnel and put these rinsings in the
same sample container.
d. Seal the container and label to clearly
identify its contents.
-------
9/3O/94: L5E-1
LABORATORY PROCEDURE 5E
Farticulate Emissions from Wool
Fiberglass Insulation Manufacturing
A. Reagent Preparation
Reagent preparation is the same as that in
LP 5, except for the following:
1. CO2-Free Water. Boil for 15 min distilled or
deionized water and cool to room
temperature in closed container with a cover
vented with an Ascarrte tube. Prepare fresh
as needed.
2. Sodium Hydroxide, 0.1 N. Dissolve 40 g
NaOH in water, and dilute to 1 L.
3. Organic Carbon Stock Solution. Dissolve
2.1254 g dried potassium biphthalate in
CO2-f ree water, and dilute to 1 L in a
volumetric flask. This solution contains
1000mg/L organic carbon.
4. Inorganic Carbon Stock Solution. Dissolve
4.404 g anhydrous sodium carbonate in
about 500 mL CO2-free water in a 1-L
volumetric flask. Add 3.497 g anhydrous
sodium bicarbonate to the flask, and dilute to
1 L with CO2-f ree water. This solution
contains lOOOmg/L inorganic carbon.
B. Analysis
The procedures for analysis are the same as
that in LP 5 with exceptions noted as follows
(Use LDS 5 and LDS 5E):
1. Container No. 1 (Filter!. Use LP 5, step A1,
except dry the filters at 20 ± 6°C and
ambient pressure.
2. Containers No. 2 and 3 (Water and Acetone
Rinses). Use LP 5, step A2, except
evaporate the samples at 20 ± 6°C and
ambient pressure.
3. Container No. 4 (Silica Gel). Use LP 5,
step A3.
4. "Water and Acetone Blank" Containers. Use
LP 5, step A4, except evaporate the samples
at 20 ± 6°C and ambient pressure.
C. TOO Analysis Preparation
1. Follow the manufacturer's instructions for
assembly, testing, calibration, and operation
of the analyzer.
2. Dilute with CO2-free water 10, 20, 30, 40,
and 50 mL of the two stock solutions to
1000 mL and 30, 40, and 50 mL of the two
stock solutions to 500 mL. Include blanks.
3. Inject samples of these solutions into the
analyzer, and record the peak heights. Plot
the peak height vs concentration (mg/L).
4. Container No. 5 (Irnpinger Liquid). Prepare
the sample for analysis as follows:
a. Measure and record the liquid volume of
each sample.
b. If the sample contains solids or
immiscible liquid matter, homogenize the
sample with a blender or ultrasonics
(may be key to ±10% repeatability).
c. To remove inorganic carbon that inhibits
repeatable TOC determinations, transfer
a representative portion of 10 to 15 mL
to a 30-mL beaker, and acidify with
about 2 drops of cone. HCI to a pH of 2
or less.
d. Warm the acidified sample at 50°C in a
water bath for 15 min.
D. TOC Analysis
1. While stirring the sample with a magnetic
stirrer, withdraw a 2O- to 50-//L sample
from the beaker, and inject it into the total
carbon port of the analyzer.
2. Inject an identical sample into the inorganic
carbon port of the analyzer.
3. Measure the peak heights.
4. Repeat the injections until three consecutive
peaks for both total carbon and inorganic
carbon are obtained within ±10% of the
average.
5. Analyze the 0.1 N NaOH blank in a similar
manner.
6. Correct the peak heights by subtracting the
blank peak height, and determine the sample
concentration.
-------
9/30/94: LD5E-1
LABORATORY DATA SHEET 5E
Paniculate Matter
Client/Plant Name
City/State
Job #
Analyst
Analytical balance I.D. #
Density of Water
g/mL
Date
Note: This Is a supplement to LDS 5 for the analysis of PM in the water rinse. In using LDS 5 for Method 5E, relabel
Container No. 2 as Container No. 3. Calculate the total PM weight as shown below.
Run Identification
Container No. 2 (Water Rinse) ID#
Volume/wgt, Vww ( Any Loss ?){mL/g)
Tare wgt (If applicable) (g)
Difference {if applicable), Www (g)
Wot #1: Date/time (mg)
Wat #2: Date/time (mg)
Wat #3: Date/time (mg)
Container tare wgt (mg)
Difference, mww (mg)
Water Blank ID#
Volume/weight, Vw (mL/g)
Tare weight (if applicable) (g)
Difference (if applicable), Ww (g)
Wat #1: Date/time , (mg)
Wot #2: Date/time (mg)
Container tare wgt {mg)
Difference, mw (mg)
Cw « mw/I(Vw pw) or Ww] (mg/g)
H2O blnk, Ww » Cw IVWW pw or Www] (mg)
Total wgt ofPM, mn* (mg)
Sample Appearance
•
Calculate the total weight of PM from Method 5E as follows:
m,, (Method 5E) = mn (Method 5) + mww - Ww + mc (LDS 5Ea)
QA/QC Chock
Completeness.
Checked by: _
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
Client/Plant Name
TOC Analyzer ID#
Temp, of total carbon column
LABORATORY DATA SHEET 5E (Continued)
Participate Matter - Wool Fiberglass Industry
Job #
Calibration Date Analyst
__ °F Temp, of inorganic carbon column
9/30/94: LD5E-2
Date
°F
Time
Total
Carbon Port
Inorganic
Carbon Port
Working Stds, ( mg/L)
Injection 1
Injection 2
Average
Injection 1
Injection 2
Average
10
20
30
40
50
60
80
100
Note: The acidification and warming steps are not necessary for preparation of the standard curve. Correct peak
heights for blank. \
Plot of calibration curve attached?
Run
No.
NaOH Blank
Sample
Vol., mL
Injection
Vol., fjL
(V,)
Total Carbon Peak
Height, mm (Tc)
1 2 3 Avg
Inorganic Carbon Peak
Height, mm (lc)
1 2 3 Avg
Total Organic
Carbon, mg/L
nvg (Ctoo)
•
Condensed
PM, mg
(mc)
Notes:
a. Repeat the injections until three consecutive peaks are obtained within ± 10% of the average.
b. Correct peak heights for blank before determining concentrations.
Calculate the mass of condensed PM as follows:
mc - 0.001 CtoeVs
Sample concentrations blank corrected?
Appropriate dilution factor applied to samples that were diluted?
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: S5F-1
SUMMARY SHEET 5F
Paniculate Matter
Run #1
Fiun #2 Run #3 Avg
Client/Plant Name
Job No.
Sampling Location
Run ID »
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H20
Abs Stack Pressure (Pb + Pg/13.6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temperature (t. + 460), R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(tsj +460) Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Volumetric Flow Rate, dscfh
Volumetric Flow Rate, wscfh
Isokinetic Sampling Rate, %
Water Blank, mg
Mass Ammonium Sulfate, mg
Mass Particulate in Residue, mg
Mass Particulate (Blnk Corr.), mg
M5E Particulate Concentration, g/dscf
e
D
Y
AH
pb
pg
PS
T6
%CO2
%02
%(CO+N2)
Md
tm
vm
Vm(std)
V.c
Vw(std)
BW8
CP
Ap
V8
A
Q8d
Q«w
mwb
m8
mr
mn
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS1
FDS 1
FDS 5
FDS 5
CDS 5
FDS 5
FDS 5
FDS 5
SS5
FDS 5
SS5
FDS 3
FDS 3
FDS 3
FDS 3
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS2a
FDS 5
FDS 5
SS5
FDS1
SS5
SS5
SS5
LDS5F
LDS5F
LDS5F
SS5F
SS5F
-------
Run#1
Post-test Calibration Checks
Temperature and Barometer
Differential Pressure Sensor
Metering System
CDS2d
CDS2d
CDS 5
9/30/94: S5F-2
Run #2 Run #3 Avg
mn = mr - mwb
cc = 0.001
*m(std)
-------
9/30/94: F5F-1
FIELD PROCEDURE 5F
Nonsulfate Participate Matter
Note: The procedure is the same as that in FP 5, except for the following:
1. Maintain the probe outlet and fitter
temperatures 320° ± 25 °F.
2. Recover the sample using water instead of
acetone.
-------
9/30/94: LBF-1
LABORATORY PROCEDURE 5F
Nonsulfate Particulate Matter
A. Reagent Preparation
The reagents are the same as that for LP 5
with the following exceptions:
1. Stock Standard Solution, 1 mg
(NH4)2SO4/mL. Dry enough primary standard
grade (NH4)2SO4 at 105 to 110°C for ^2 hr.
Then dissolve exactly 1.000 g dried
(NH4)2SO4 in water in a 1 L volumetric flask,
and dilute to 1 L. Mix well.
2. Working Standard Solution, 25 /.tg
(NH4)2SO4/mL. Pipet 5 mL stock standard
solution into a 200-mL volumetric flask.
Dilute to 200 mL with water.
3. Standards. Prepare a blank and five
standards by adding 0.0, 1.0, 2.0, 4.0, 6.0,
and 10.0 mL of working standard solution
(25 jt/g/mL) to a series of six 50-mL
volumetric flasks (masses equal 0, 25, 50,
100, 150, and 250 /jg, respectively). Dilute
each flask to volume with water, and mix
well.
4. Eluent Solution, O.OO24 M Na2CO3/O.OO3
M NaHC03. Weigh 1.018 g Na2CO3 and
1.008 g NaHCO3, and dissolve in 4 L water.
5. Phenolphthalein Indicator. Dissolve 0.05 g
3,3-Bis(4-hydroxyphenyl)1-(3H)-isobenzo-
furanone in 50 mL ethanol and 50 mL water.
B. Sample Preparation
1. Cut the filter into small pieces, and place it in
a 125-mL Erlenmeyer flask with a ground
glass joint equipped with an air condenser.
(Run a blank with an unused filter from the
same lot as that of the sample through the
same procedure, except for the obviously
inapplicable parts.)
2. Rinse the shipping container with water, and
pour the rinse into the flask. Add water to
the flask until it contains about 75 mL.
3. Place the flask on a hot plate. Gently reflux
the contents for 6 to 8 hr. Then cool.
4. Transfer solution to a 500-mL volumetric
flask. Rinse the Erlenmeyer flask with water,
and transfer the rinsings to the volumetric
flask including the pieces of filter.
5. Transfer the probe rinse to the same 500-mL
volumetric flask with the filter sample. Rinse
the sample bottle with water, and add the
rinsings to the volumetric flask. Dilute the
sample to exactly 500 mL with water.
6. Allow the sample to settle until all solid
material is at the bottom of the volumetric
flask. If necessary, centrifuge a portion of
the sample.
7. Pipet 5-mL of the sample into a 50-mL
volumetric flask, and dilute to 50-mL with
water.
C. Sulfates Analysis
1. Analyze the blank and standards; subtract
the blank from each value. Measure peak
heights, if symmetrical; otherwise, calculate
peak areas. See LDS 5F.
2. Prepare or calculate a linear regression plot
of fjg versus peak heights/areas, and
determine the slope and its reciprocal.
Resultant concentrations must <~1% from
each known standard mass (i.e., 25, 50,
100, 150, and 250 fjg).
3. Analyze a set of duplicate samples, and then
a second set of standards as previously.
Use the same injection volume for both
standards and samples. Average the sample
results (must agree within ±5% of their
mean). Perform this duplicate analysis
, sequence on the same day.
4. Dilute any sample and the blank with equal
volumes of water if the concentration
exceeds that of the highest standard.
5. Document each sample chromatogram by
listing the following: injection point, injection
volume, sulfate retention time, flow rate,
detector sensitivity setting, and recorder
chart speed.
D. Sample Residue Analysis
1. Quantitatively transfer the remaining
contents of the volumetric flask to a tared
250-mL beaker. Add the water rinsings to
the tared beaker. Use LDS 5Fa.
2. Run a water blank in parallel (volume equal
to that of the sample).
3. Evaporate the water in an oven at 105°C
until about 100 mL of water remains.
Remove the beakers from the oven, and
allow them to cool.
4. Add five drops of phenolphthalein indicator,
and add cone. NH4OH until solution turns
pink.
5. Return the samples to the oven at 105°C,
and evaporate the samples to dryness. Cool
the samples in a desiccator, and weigh the
samples to constant weight.
-------
9/30/94: LD5F-1
LABORATORY DATA SHEET 5F
Nonsulfate Paniculate Matter (Sulfate Determination)
Client/Plant Name
Job #
ion Chromatograph 1D#
Ambient Temp.
_Column Type
Calibration Date/Time
°C
Analyst
Note: Attach plot of calibration curve. Determine slope of curve and its reciprocal IS). Multiply S by peak height or
area and determine deviation of each point from the fine. The deviation must be £ 7% of the concentration at each
point.
Chfomatographic Conditions: Eluent:
Detector Sensitivity
Flow rate:
Injection Points (marked?) Injection Volume
Chart Speed Retention Times: Sulfate _
. Sample ID#
O.O^g/mL(Blnk)
25//o/mLStd
SO^a/mLStd
100//g/mLStd
150//g/mLStd
250//g/mLStd
Volume
Loss, V,
1*^'^y^s vX
=*> «s*,i«"n«JBw».
: f f.f^^' ~.f^vt^.
•.* "*,lS«»«,^!lV,
>*.- «*^xi?*>IS4M
"^5^t^ £* f^ff ^"f ^"%
~^^&j$
\ ' x\ (-J4,'
Sample
Volume, V6
(mL)
""•"•5 yM-y?ffj$^ "i-vAw ^
3§ftK ^«,>/j^?& '"s ^ *
SSS«;C?t
''V^Sw^'S ^o CSX ^v-i
.E,.^t"K4^
fb^S? ^ s"° ^i>^iA^'s':' % < •*
^^^*
,. %*A* ^ ^ ^-.^X •• «^
Peak Height/Area, H (Hj/Avg ^0.05?)
#1
•
#2*
Avg
Blnk Corr, Hc
>,•"• <»;?'<<.'' ..,-;''
:-,x£ ^ fj»jf •'-);,
•
AS in
SampI, ms
l^g)
ff " * *• f * , ^
...r.'r.^.^
.
Hc ** 0.099 (Havo - Bavgj ms = Hc S F F = Dilution factor, only if sample is diluted to bring into
calibration range. 0.099 = 99/1000
* Perform inject #2 for standards after a set of field samples.
QA/OC Chock
Completeness
Deviation from least square line to measured point £7% of the concentration at each point?
Legibility Accuracy Specifications . Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/3O/94: LD5F-2
LABORATORY DATA SHEET 5F (Continued)
Nonsulf ate Paniculate Matter (Sample Residue Determination)
Client/Plant Name
City /State
Job#
Analyst
Barometric Pressure
Hg Lab Amb Temp.
Analytical balance I.D. #
°F Relative Humidity in Lab
Date
50%?)
Run Identification
Sample ID#
Volume, Vw ( Any Loss ?) (mL)
Filter tare wgt, mf (mgj
Wgt #1 : Date/time (mg)
Wgt #2: Date/time (mg)
Wgt #3: Date/time , mt (mg)
Beaker tare wgt, mbk (mg)
Mass in residue (mt - mf - mbk), mr (mg)
Blank ID
Volume, Vb (mL)
Filter tare wgt (g)
Wgt #1 : Date/time (mg)
Wgt #2: Date/time (mg)
Wgt #3: Date/time - (mg)
Beaker tare wgt (mg)
Difference, mw (mg)
Cw = mw/Vb (mg/mL)
* Mass in Blank (Cw Vs), mwb (mg)
Sample Appearance
* V is the volume of sample evaporated = 495 mL.
1wb
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: S5Fa-1
SUMMARY SHEET 5Fa
Participate Matter
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Abs Stack Pressure (Pb + Pg/13.6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temperature (ts + 460), R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide -*• Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(t8, +460) Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Volumetric Flow Rate, dscfh
Volumetric Flow Rate, wscfh
Isokinetic Sampling Rate, %
Water Blank, mg
Mass Ammonium Sulfate, mg
Mass Particulate in Residue, mg
Mass Particulate (Blnk Corr.), mg
M5E Particulate Concentration, g/dscf
e
Dn
Y
AH
Pb
pg
PS
TS
%C02
%02
%(CO + N2)
Md
tm
vm
Vm(std)
V.c
Vw(std)
Bws
c
Ap
[Tsi Ap]1/2
vs
A
Qsd
QSW
mwb
ms
mr
mn
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 1
FDS1
FDS 5
FDS 5
CDS 5
FDS 5
FDS 5
FDS 5
SS5
FDS 5
SS5
FDS 3
FDS 3
FDS 3
FDS 3
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS2a
FDS 5
FDS 5
SS5
FDS 1
SS5
SS5
SS5
LDS5F
LDS 5Fa
LDS5F
SS5F
SS5F
Run #1
Run #2
Run #3
Avg
-------
9/30/94: S5Fa-2
Run #1 Run #2 Run #3 Avg
Post-test Calibration Checks
Temperature and Barometer
Differential Pressure Sensor
Metering System
CDS2d
CDS2d
CDS 5
mn = mr - mwb - ms
c. - 0.001
"m(std)
-------
9/30/94: L5Fa-1
LABORATORY PROCEDURE 5Fa
Nonsulfate Participate Matter (Alternative)
Note: This procedure is an alternative to that in LP 5F.
A. Reagent Preparation
The reagents are the same as that for LP 6,
except for the addition of 1 M HCI.
HCI, 1 M. Add 8.3 mL cone. HCI {12 M) to
50 mL water in a 100-mL volumetric flask.
Dilute to 100 mL with water.
B. Ion Exchange Column Preparation
1. Slurry the resin with 1 M HCI in a 250-mL
beaker, and allow to stand overnight.
2. Place glass wool, 1-in. deep, in the bottom of
the glass column. Rinse the slurried resin
twice with water. Resuspend the resin in
water, and pour sufficient resin into the
column to make a bed 2 inches deep.
Eliminate air bubbles in the resin or glass
wool. If necessary, stir the resin with a glass
rod to remove air bubbles.
3. Place a 1 in. plug of glass wool on top of the
resin. Do not let the liquid level fall below
the top of the upper glass wool plug.
4. Rinse the column with water until the eluate
gives a pH 2:5 (use pH paper).
5. Regenerate or replace resin after 20 sample
aliquots or if end point of the titration
becomes unclear.
C. Sample Extraction and Residue
1. Extract the sample using LP 5F, step B,
except do not dilute the sample to 500 mL.
2. Treat and tare filters as follows:
a. Place at least one clean glass fiber filter
for each sample in a Buchner funnel, and
rinse the filters with water.
b. Remove the filters from the funnel, dry
them in an oven at 105 ± 5°C, and cool
in a desiccator.
c. Weigh each filter to a constant weight,
and record weight to nearest 0.1 mg.
3. Filter the extracted sample as follows:
a. Assemble the vacuum filter apparatus,
and place one of the clean, tared glass
fiber filters in the Buchner funnel.
b. Decant the liquid portion of the extracted
sample through the tared filter into a
clean, dry, 500-mL filter flask.
c. Rinse all the particulate matter
remaining in the volumetric flask onto
the filter with water. Rinse the
particulate matter with more water.
d. Transfer the filtrate to a 500-mL
volumetric flask, and dilute to 500 mL
with water.
e. Dry the filter and filtered material
overnight at 105 ± 5°C, cool in a
desiccator, and weigh to the nearest
0.1 mg.
4. Determine solids in filtrate as follows:
a. Dry a 250-mL beaker at 75 ± 5°C, and
cool in a desiccator; then weigh to
constant weight to nearest 0.1 mg.
b. Pipette 200 mL of the filtrate that was
saved into the tared 250-mL beaker;
add five drops of phenolphthalein
indicator and sufficient concentrated
ammonium hydroxide to turn the
solution pink.
c. Carefully evaporate the contents of the
beaker to dryness at 75 ± 5°C. Check
for dryness every 30 min. Do not
continue to bake the sample once it has
dried.
d. Cool the sample in a desiccator, and
weigh to constant weight to nearest
0.1 mg.
D. Analysis
1. Adjust the flow rate through the ion
exchange column to 3 mL/rhin.
2. Pipette a 20 mL aliquot of the filtrate onto
the top of the ion exchange column, and
collect the eluate in a 50-mL volumetric
flask. Rinse the column with two 15-mL
portions of water. Stop collection of the
eluate when the volume in the flask reaches
50-mL.
3. Run duplicates. Pipette a 20-mL aliquot of
the eluate into a 250-mL Erlenmeyer flask,
add 80 mL 100% isopropano) and two to
four drops of thorin indicator, and titrate to a
pink end point using 0.0100 N barium
perchlorate.
4. Run a water blank with each series of
samples. Blank values must be <5 mg.
5. Duplicate analyses must agree within ± 1 %
or ±0.2 mL, whichever is larger. Duplicates
through resin must agree within ±5%.
-------
9/30/94: LDSFa-1
LABORATORY DATA SHEET 5Fa
Nonsulf ate Paniculate Matter - Alternative
Client/Plant Name
City/State
Job No.
Sampling Location
Analyst
Run
No.
Blank
Date Anal'
/zed Time
j Analyzed
Volume (mL)
Extract,
Filtrate,
v,
Eluate,
Aliquot,
va
Titrat'n,
Titrat'n
Avg,
vt
AS
(mg)
ms
Titrant Standardization Against Sulfuric Acid 0.01 DON Mass of Ammonium Sulfate:
1
2
3
Volumes (mL)
H2SO4
vs
Ba +
vt
Average, N
Normality
(Nt)
N, =
NSVS
V,
Titrations repeated and volumes averaged?
Blank run with every sample series?
Replicate blank titration values agree within ± 1 %
or ±0.2 mL?
_ 66.07 (Vt- Vc) N Ve V(
'-
Ve = Volume of titrant used for titration blank, ml
Ion exchange and titrations performed on
duplicate portions of filtrate?
Results agree within ±5% ?
Ion exchange column regenerated or replaced
after 20 samples?
QA/aC Check
Completeness
Checked by:
Legibility
Accuracy_
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
-------
9/30/94: S6-1
Client/Plant Name
Job No.
Sampling Location
Run ID#
Test Date
Run Start Time
Run Finish Time
Traverse Points (if applicable)
Net Run Time, min
Dry Gas Meter Calibration Factor
Barometric Pressure, in. Hg
Average DGM Temperature, °F
Avg Abs DGM Temperature {460 + tm), R
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Normality, Ba Perchlorate Titrant, meq/mL
Volume of Sample Solution, mL
Volume of Sample Aliquot Titrated, mL
Average Volume Titrant for Sample, mL
Volume Titrant for Blank, mL
SO2 Concentration, Ib/dscf
Audit Relative Error, %
Post-test Calibration Checks
Temperature and Barometer
Metering System
SUMMARY SHEET 6
Sulfur Dioxide
FDS6
FDS6
FDS6
FDS6
FDS6
FDS6
FDS6
e
Y
V,
m
m(std)
N
Vu
-S02
RE
FDS 1
FDS6
CDS 6
FDS 6
FDS 6
SS6
FDS 6
SS6
LDS6
LDS6
LDS6
LDS6
LDS6
SS6
QA 1
CDS2d
CDS 6
Run#1
Run #2
Run #3
Avg
Vm(std) = 17.64 VmY-
1
(V,-Vtb)N U
= 7.061 x 10-5
m(std)
-------
Surg* Tank
Figure F6-1. SQj Sampling Train.
-------
9/30/94: F6-1
FIELD PROCEDURE 6
Sulfur Dioxide
A. Pre-test Preparations
1. Calibrate the metering system (see CP 6).
2. Determine the number and location of
sampling points and sampling time.
3. Prepare the sampling train as follows:
a. Add 15 mL 80% isopropanol into the
midget bubbler.
b. Add 15 mL 3% H2O2 into each.of the
first two midget impingers.
c.
d.
e.
f.
Leave the final midget impinger dry.
Assemble the train as shown in
Figure F6-1.
Adjust probe heater to a temperature
sufficient to prevent water condensation.
Place crushed ice and water around the
impingers.
B. Samp/ing
1. Optional: Leak-check the sampling train
(see FP 3c, sections C and D).
2. Record the initial DGM reading and
barometric pressure.
3. Position the tip of the probe at the first
sampling point, connect the probe to the
bubbler, and start the pump.
4. Adjust the sample flow (rotameter) to a
constant rate of about 1.0 L/min. Maintain
this constant rate (±10%) during the entire
sampling run.
5. Traverse, if applicable. Take readings (DGM,
temperatures at DGM and at impinger outlet,
and rate meter) at least every 5 min.
6. Add more ice during the run to keep the
temperature of the gases leaving the last
impinger at <68°F.
7. At the conclusion of the run, turn off the
pump, remove probe from the stack, and
record the final readings.
8. Mandatory: Leak-check the sampling train
(see FP 3c, section C).
C. Sample Recovery
1. Drain the ice bath, and purge the remaining
part of the train by drawing clean ambient air
through the system for 15 min at the
sampling rate. Pass air through a charcoal
filter or through an extra midget impinger
with 15 mL 3% H202 or use ambient air
without purification.
2. Disconnect the impingers after purging.
Discard the contents of the midget bubbler.
(Saving this portion until after analysis may
be helpful to explain anomalies.)
3. Pour the contents of the midget impingers
into a leak-free polyethylene bottle for
shipment.
4. Rinse the three midget impingers and the
connecting tubes with water, and add the
washings to the same storage container.
5. Seal and identify the sample container. Mark
the fluid level.
D. Post-test Calibrations
Conduct post-test calibration checks of
metering system and temperature gauges
according to CP 2d and CP 2e (use CDS 2d and
CDS 6).
E. Elimination of Ammonia Interference
Use FP 6 above, with the following
modifications:
1. Use a high efficiency in-stack filter (glass
fiber) that is unreactive to SO2, e.g.,
Whatman 934 AH.
2. Maintain the probe at 525 °F during
sampling.
3. Do not discard the isopropanol solution in
the midget bubbler (step C2), but
quantitatively recover the solution into
container containing the solutions from the
midget impingers (step C3).
4. Alternatives:
If SOg is expected to be insignificant,
the midget bubbler may be deleted from
the sampling train.
If an approximate SO3 concentration is
desired, the midget bubbler contents
may be recovered in a separate
polyethylene bottle.
a.
b.
-------
9/30/94: FD6-1
FIELD DATA SHEET 6
Gaseous Pollutant Sampling
Method (CffCfe) 6 6A 6B 7C 7D
Client/Plant Name
City/State
Job*
Date/Time
Test Location/Run #
Personnel
Train ID#/SampIe Box #
Start Time , End Time.
DGM Cal Coef., Y
Ambient Temp., °F_
Bar. Pressure, Pb _
in. Hg
Trav.
Pt.
Sampig
time
(min)
Total Time,
».
DGM Rdg
(cf)
Volume, Vm
Rotameter
Rdg
(cc/min)
Avg
Temperature (°F)
DGM
*
Avg, tm
Imp. Exit
Max
*z68°F?
Flow Rate Deviation
AVm
(
Avg
AVm/AVm
0.90-1.10?
Proper probe heat (no condensation)?
Purge Rate (at avg rotameter rdg)?
Purge Time min (a 15 min)?
Sample Recovery
Fluid level marked?
Sample container sealed?
Sample container identified?
Post-Test Calibrations:
Attach CDS 2d and CDS 6. Temperature specification for the DGM thermometer is £±5.4 °F.
Leak-Checks £0.02 Avg Flow Rate at a 10 in. Hg vac.
Run*
Pre (optional) (cc/min)
Post (mandatory) (cc/min)
Vacuum (a 10 in. Hg ?)
.
QA/aC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94'. L6-1
LABORATORY PROCEDURE 6
Sulfur Oxides
A. Reagent Preparation
1. Isopropanol. Check each lot of isopropanbl
for peroxide impurities as follows:
a. Shake 10 mL isopropanol with 10 mL
freshly-prepared 10% potassium iodide
solution.
b. Prepare a blank by similarly treating
10mL water.
c. After 1 minute, read the absorbance at
352 nanometers on a spectrophoto-
meter, using a 1-cm path length.
d. If absorbance >0.1, do not use the
alcohol.
2. Thorin Indicator, 1 -(o-arsonophenylazo)-2-
naphthol-3,6-disulfonic acid, disodium salt, or
equivalent. Dissolve 0.20 g in 100mL
water.
3. Sulfuric Acid Standard, 0.0100 N. Purchase
or standardize to ±0.0002 N against
0.0100 N NaOH which has previously been
standardized against potassium acid
phthalate (primary standard grade).
4. Barium Standard Solution, 0.0100 N.
Dissolve 1.95 g Ba{CI04)2»3H20 in 200 mL
water, and dilute to 1 L with isopropanol.
Alternatively, 1.22 g BaCI2»2H20 may be
used instead of the perchlorate. Standardize
this solution as follows:
a. Add 100 mL 100% isopropanol to 25 mL
standard sulfuric acid solution.
b. Titrate with the barium perchlorate or
barium chloride solution.
c. Run duplicate analyses until titrations
agree within ± 1 % or ±O.2 mL,
whichever is larger, and average these
titrations.
d. Calculate the normality using the
average titration volume.
5. QA Audit Samples. Obtain from EPA
(seeQAD.
B. Analysis
1. Note level of liquid in the sample container,
and determine loss; note this loss, if any, on
the LDS.
2. Transfer the contents of the storage
container to a 100-mL volumetric flask, and
dilute to exactly 100 mL with water.
3. Pipette a 20-mL aliquot of this solution into
a 250-mL Erlenmeyer flask.
4. Add 80 mL 100% isopropanol and' two to
four drops thorin indicator.
5. Titrate to a pink endpoint using 0.0100 N
barium standard solution.
6. Repeat steps 3 through 5 until duplicates
agree within ±1 % or ±0.2 mL, whichever
is larger, and average the titration volumes.
7. Run a blank with each series of samples.
8. Concurrently analyze the two audit samples
and a set of compliance samples.
-------
9/30/94: LD6-1
LABORATORY DATA SHEET 6
Sulfur Oxides
Client/Plant Name
Analyst
Job #
Date/Time
Std Sulfurtc Acid Normality, NSA.
(±0.0002?)
Isopropanol Check OK ?
Sample ID #
Standard Barium
Audit Sample #1
Audit Sample #2
Blank
Volume
Loss, V|
(mU
Sample
Volume, Vs
(mL) ,
Aliquot
Volume, Va
(mL)
Volume titrant, Vt (mL)
Run 1
Run 2
'-
*
Average
•
AH duplicates agree within ±1% (i.e., Vt1/Vt2 from 0.99 to 1.01) or ±0.2 mL, whichever is larger?
Normality of Barium Solution, N = NSA [VSA/Vt(bar)]
QA/ac Chock
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: C6-1
CALIBRATION PROCEDURE 6
Metering System
A. Initial Calibration
1. Leak-check the metering system (drying
tube, needle valve, pump, rotameter, and
DGM) from the inlet to the drying tube
according to FP 3c, section A.
2. Remove the drying tube..
3. Connect a 1 L/rev wet test meter to the
inlet of the metering system.
4. Make three independent calibrations runs,
using at least five revolutions of the DGM
per run.
5. Calculate the calibration factor Y for each
run, and average the results (must be
£ ± 2 % from the average).
A Post-test Calibration Cheek
1. Do not conduct a leak-check.
2. Remove the drying tube. Connect a 1 L/rev
wet test meter to the inlet of the metering
system.
3. Make two or more independent runs, using
at least three or more revolutions of the
DGM per run.
4. Calculate the calibration factor Y for each.
run, and average the results (must be
s; ±5% of Y,. If not, recalibrate the
metering system and for the calculations,
use the calibration factor (initial or
recalibration) that yields the lower gas
volume for each test run.
C. Alternative
A dry gas meter calibrated for a standard may
be used in place of the wet test meter in step A3.
See CP 5c.
-------
9/30/94: CD6-1
CALIBRATION DATA SHEET 6
Metering System
Meter B
WetTes
Initial C;
Run
No.
ox# Date
t Meter # " Barometric Pressure. Ph in. H.q
alteration Recalibration • Personnel
Rotam.
Rdg
(cc/min)
WTM
vw
(L)
<•%
Am
(in. H2O)
DGM
Vol(L)
vd
V*
Temp. (°F)
td
tdo
Time
9
(min)
Avg, Yd
Meter
Coeff.
Y,
V
Y. =
13.6
DGM Volume/Rev. Vr =
Run
No.
Initial Calibration
(Vtf - Vd)A/r
zS.O
Y/Yd
0.98 to 1.02 ?
Re-Calibration
(V0, - Vd|)/Vr
23.0?
Yd(rc)/Ydi
0.95 to 1 .05 ?
QA/QC Check
Completeness.
Checked by.
Legibility.
Accuracy.
Personnel (Signature/Date)
Specifications _
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: S6a-1
SUMMARY SHEET 6a
Sulfur Dioxid a (Alternative)
Run #1 Run #2 Run #3 Avg
Client/Plant Name FDS 6
Job No. FDS 6
Sampling Location FDS 6 I
Run ID# FDS 6
Test Date FDS 6a
Run Start Time FDS 6a
Run Finish Time ' FDS 6a
Traverse Points (if applicable) FDS 1
Net Run Time, min Q FDS 6a
Avg Cal Flow Rate, cfm Q8td FDS 6a
Barometric Pressure, in. Hg Pb FDS 6a
Critical Orifice Inlet Vac during Cal, in. Hg Pc FDS 6a
Critical Orifice Inlet Vac during Sampling, in. Hg P8r FDS 6a
Ambient Air Moisture Content, fraction B...a FDS 6a
Vyfl
Impinger Outlet Moisture Content, fraction Bwo FDS 6a
Volume of Metered Gas Sample, dscf vm(etd) ss 6a
Normality, Ba Perchlorate Titrant, meq/mL N LDS 6
Volume of Sample Solution, mL V8 LDS 6
Volume of Sample Aliquot Titrated, mL Va LDS 6
Average Volume Titrant for Sample, mL Vt LDS 6
Volume Titrant for Blank, mL vb LD*» 6
SO2 Concentration, Ib/dscf CSO2 SS 6a
Post-test Calibration Checks
Temperature and Barometer • CDS 2d
Metering System FDS 6a
v -Q en B > s
1BM"Ql" ""^
= 7.061 x ID'6
-------
Surgt Tank
Silk* O«l Ctfllc*!
DiylngTub* Orffc*
Figure F6S-1. SO Sampling Train using a Critical Orfftce.
-------
9/30/94-. F6a-1
FIELD PROCEDURE 6a
Critical Orifice Sampling Train
Note: This procedure describes the technique for sampling trains using critical orifices. The midget
impinger trains are as specified, e.g.. Method 6.
1. Prepare the sampling train as shown in
Figure F6a-1.
2. Optional: Leak-check the sampling train
(see FP 3c, sections C and D); add surge
tank before rotameter).
3. Determine the %moisture of the ambient air
using the wet and dry bulb temperatures or,
if appropriate, a relative-humidity meter.
4. Calibrate the entire sampling train as follows:
a. Attach a 500-cc soap bubble meter to
the inlet of the probe.
b. Set the outlet vacuum 1 to 2 in. Hg
above the critical vacuum.
c. Determine the volumetric flow rate
(see FDS 6a).
d. Calculate the standard volume of air
measured by the soap bubble meter and
standard volumetric flow rate.
5. Use the same vacuum used during the
calibration run. Start the watch and pump
simultaneously.
6. Take readings as shown in FDS 6a at least
every 5 min.
7. At the end of the sampling run, stop the
watch and pump simultaneously.
8. Conduct a post-test calibration run as in
step 4 (see FDS 6a).
9. Average Qstd from both calibration runs.
10. Calculate the sample gas volume Vm(std).
11. Determine the ratio of the molecular weights
of air to stack gas, Ma/Ms. If this ratio is
0.97 to 1.03, the term (Ma/Ms)1/2 may be
dropped from the equation (see SS 6a).
12. Drain the ice bath, and purge the sampling
train by drawing clean ambient air through
the system for 15 min. Pass air through a
charcoal fitter or through an extra midget
impinger with 15 mL 3% H2O2 or use
ambient air without purification.
-------
9/30/94: FD6a-1
FIELD DATA SHEET 6a
Critical Orifice Sampling Train
Client/Plant Name
City/State
Train IDff
Job#
Date/Time
Dry Molecular Weight of Stack Gas, Md
Moisture Content of Amb. Air, Bwa
Personnel
Crit. Orifice ID#
Run No.
Bubble Meter Vol, Veb cc
Time, 0 sec
Bar. Press., Pb in. Hg
Amb Temp., tamb °F
Inlet Vac, P0 in. Hg
S: Cr/t, Vac.??
Outlet Vac., in. Hg
Flow Rate, Q8td cc/min
Average Q,td cc/min
Post 5etd/Pre Q8td
Average Pro/Post Q6td, cfm
Crit. Vac. in. Hg
1
2
3
4
(0.95 to 1.05?)
Elapsed
Time
(min)
Outlet
Temp
(°F)
Vacuum (in. Hg)
Inlet
•
Outlet
Rotam
Rdg
[cc/min)
Moisture Content of Impinger Outlet, B,
wo.
Ib/lb-mole
(fraction)
(fraction)
Avg Pre/Post Q,td = 3.531 x 10'5 Q8td
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: C6a-1
CALIBRATION PROCEDURE 6a
Critical Orifice
Note: Critical orifices used in midget type impinger trains are calibrated in the field. This CP covers the
selection and check for suitability.
1. Select a critical orifice for the desired flow
rate. The needle sizes and tubing lengths
shown below give the following approximate
flow rates.
Approximate Sizes/Flow Rates
for Critical Orifices
Gauge/cm
21/7.6
22/2.9
22/3.8
cc/min
1100
1000
900
Gauge/cm
23/3.8
23/5.1
2473.2
cc/min
500
450
400
2. To adapt these needles to a Method 6 type
sampling train, do the following.
a. Insert sleeve type, serum bottle
stoppers into two reducing unions.
b. Insert the needle into the stoppers as
shown in Figure F6a-1.
3. Determine suitability and the appropriate
operating vacuum of the critical orifices as
follows:
a. Temporarily attach a rotameter and
surge tank to the outlet of the sampling
train.
b. Turn on the pump, and adjust the valve
to give an outlet vacuum reading
corresponding to about half of the
atmospheric pressure.
c. Observe the rotameter reading. Slowly
increase the vacuum until a stable
reading (critical vacuum) is obtained on
the rotameter and record this value.
d. Do not use orifices that do not reach a
critical value.
4. Identify the critical orifice.
-------
SUMMARY SHEET 6A
Sulfur Dioxide, Carbon Dioxide, and Moisture
Method (circle) 6A 6B
Client/Plant Name
Job No.
Sampling Location
Run ID#
Test Date
Run Start Time
Run Finish Time
Traverse Points (if applicable)
Net Run Time, min 0
Dry Gas Meter Calibration Factor Y
Barometric Pressure, in. Hg Pb
Average DGM Temperature, °F tm
Absolute Average DGM Temperature, R Tm
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
C02 Absorber, Initial Weight, g
C02 Absorber, Final Weight, g
Volume CO2, scf
CO2 Concentration, % dry
vm(std)
mai
maf
VCO2(std)
CCQ2
Moisture, Initial Weight, g mwi
Moisture, Final Weight, g m^
Volume Moisture, scf vw{std)
Moisture Concentration, % Cw
FDS6
FDS6
FDS6
FDS6
FDS6
FDS6
FDS6
FDS1
FDS6
CDS 6
FDS6
FDS6
SS6
FDS6
SS6
FDS6A
FDS6A
SS6A
SS6A
FDS6A
FDS6A
SS6A
SS6A
Normality, Ba Perchlorate Titrant, meq/mL N LDS 6
Volume of Sample Solution, mL V8 LDS 6
Volume of Sample Aliquot Titrated, mL Va LDS 6
Average Volume Titrant for Sample, mL Vt LDS 6
Volume Titrant for Blank, mL Vb LDS 6
S02 Concentration, Ib/dscf CSO2 SS 6
Carbon F-factor, scf/mrnBtu Fc M-19
SO2 Emission Rate, Ib/mmBtu ESO2 SS 6A
Post-test Calibration Checks
Temperature and Barometer CDS 2d
Metering System CDS 6
Run#1
Run #2
9/30/94: S6A-1
Run #3 Avg
5.467 x 10-
- mal)
"w(std)
X 100
"m(sld) + *
V,
x 100
= 32.03
mso
3 = Fc (1.829 x 109) ^~-
32 c (ma,-mai)
-------
9/3O/94: F6A-1
FIELD PROCEDURE 6A
Sulfur Dioxide, Moisture, and Carbon Dioxide
A. Pre-test Preparation
1. Prepare the sampling train as shown in
Figure F6A-1.
a. Add 15 mL 80% isopropanol into the
first midget bubbler. Insert glass wool
into the top of the isopropanol bubbler.
b. Add 15 mL 3% H2O2 into each of the
first two midget impingers.
c. Add about 25 g Drierite to fourth vessel.
2. Clean the outsides of the bubblers and
impingers, and weigh simultaneously all four
vessels at room temperature (20 °C) to
±O.1 g.
3. Prepare the CO2 absorber as shown in
Figure F6A-2. Check the absorber by
rotating the cylinder in a horizontal position.
The CO2 absorbing material should not shift
or have open spaces or channels.
4. Clean and dry the outside of the cylinder, and
weigh at room temperature to ±O.1 g.
Assemble the train as shown in Figure F6A-1.
5. Adjust the probe heater to a temperature
sufficient to prevent condensation.
a. Downstream of wet scrubbers, use a
heated out-of-stack filter (either
borosilicate glass wool or glass fiber
mat). The filter may be within the
heated section of the sampling probe,
but not within 15 cm of the probe inlet
or any unheated section of the probe.
b. Heat the probe and filter to s20°C
above the source temperature, but not
>120°C.
6. Place crushed ice and water around the
impingers and bubblers to cover at least
two-thirds of their length.
7. Mount the CO2 absorber outside the water
bath in a vertical flow position with the
sample gas inlet at the bottom.
B. Sample Concentration Sampling
1. Collect the sample following FP 6, section B.
Remove the CO2 absorber after the leak-
check and before purging of the sampling
train.
2. After purging, disconnect the isopropanol
bubbler and the impingers.
a. Allow about 10 min for them to reach
room temperature.
b. Clean and dry the outsides, and weigh
them simultaneously.
C. Sample Recovery
1. Discard (or save, if desired) the contents of
the isopropanol bubbler. Transfer the
contents of the midget impingers into a leak-
free polyethylene bottle for shipping.
a. Rinse the two midget impingers and
connecting tubes with water, and add to
the same storage container.
b. Mark the fluid level. Seal and identify
the sample container.
2. Allow about 10 min for the CO2 absorber to
warm to room temperature, clean and dry
the outside, and weigh to ±O.1 g. Discard
used Ascarite II material.
D. Post-test Calibrations
Conduct post-test calibration checks of
metering system and temperature gauges.
(See CP 2d, CP 2e, and CP6).
£. Emission Rate Sampling for FP 6A and 6B
When only the emission rate of S02 (ng/J) is
needed, use the same procedure as that in FP 6a,
except for the following;
1.
A dry gas meter is not needed (see
Figure F6A-1).
2. The weighing steps of the isopropanol
bubbler, the SO2 absorbing impingers or the
moisture absorber (steps A2 and B2 of
FP 6A) may be omitted.
3. During sampling, dry gas meter readings,
barometric pressure, and dry gas meter
temperatures need not be recorded.
F. Alternatives/Suggestions
1. Other types of impingers and bubblers, such
as Mae West for SO2 collection and rigid
cylinders for moisture absorbers containing
Drierite, may be used with proper attention
to reagent volumes and levels.
2. Flexible tubing, e.g., Tygon, may be used to
connect the last SO2 absorbing bubbler to
the Drierite absorber and to connect the
Drierite absorber to the CO2 absorber.
3. A second, smaller CO2 absorber containing
Ascarite II may be added in line downstream
of the primary CO2 absorber as a
breakthrough indicator. Ascarite II turns
white when CO2 is absorbed.
4. A heated Teflon connector may be used to
connect the filter holder or probe to the first
impinger.
-------
if T" """ •"!
U I -/o*j" >
T«mp«r*tur*
Ctnstr
Figure F6A-1. Sampling Train.
-------
9/30/94: FD6A-1
FIELD DATA SHEET 6A
Moisture and Carbon Dioxide
Client/Plant Name
Job #
Test Location/Run #
Personnel
Note: Use FDS 6 or 6B for SO2 data and attach this data sheet.
Moisture Determination:
Bubblers/lmpingers
Initial wgt, mw, (g)
Final wgt, mwf (g)
CO2 Determination: CO2 Absorber
Initial wgt, mai (g)
Final wgt, maf (g)
'.
QA/QC Chock
Completeness
Checked by:
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: S6C-1
SUMMARY SHEET 6C
Sulfur Dioxide
Run #1 Run #2 Run #3 Avg
Client/Plant Name FDS 6C
Job No. FDS 6C
Sampling Location FDS 6C
Run ID # FDS 6C
Tost Date FDS 6C
Run Start Time FDS 6C
Run Finish Time FDS 6C
Average Gas Concentration, dry basis, ppm C FDS 6C
Avg System Cal Bias Check Responses for
Zero Gas, ppm C0 FDS 6C
Avg System Ca! Bias Check Responses for
Upscale Cal Gas, ppm Cm FDS 6C
Actual Cone of Upscale Cal Gas, ppm Cm. FDS 6C r
Effluent Gas Concentration, dry basis, ppm COM SS 6C
Interference Check Value from FP 6Ca CIC » SS 6
Post-test Calibration Check
System calibration bias check FDS 6C
-------
9/30/94: F6C-1
4.
6.
FIELD PROCEDURE 6C
Sulfur Dioxide
(Instrumental Analyzer Procedure)
A. Preparations
1. Obtain SO2 calibration gases (SO2 in N2 or
SO2 in air or gas mixtures of SO2/CO2,
SO2/O2 or SO2/CO2/O2 in N2).
2. For fluorescence-based analyzers, use
calibration gases that contain
concentrations of O2 and CO2 within
± 1 % O2 and ± 1 % CO2 of that of the
effluent samples introduced to the analyzer
or, alternatively, use SO2 in air and
correction factors for O2/CO2 quenching.
3.. Use three calibration gases as specified
below:
a. High-Range. 80 to 100% of span.
b. Mid-Range. 40 to 60% of span.
c. Zero. SO2 concentration ±5%, conduct at least three
additional analyses until the results of six
consecutive runs agree within ±5% or
±5 ppm, whichever is greater, of the
average. Then use this average for the
cylinder value.
Prepare and calibrate the gas analyzer and
data recorder. Adjust system components
as necessary.
B. Analyzer Calibration Error
Conduct this test initially and each time the
system exceeds the system bias and drift
specifications.
1. Introduce the zero, mid-range, and high-
range gases to the measurement system at
any point upstream of the gas analyzer. Do
not make any adjustments to the system
except those necessary to adjust the
calibration gas flow rate at the analyzer.
2. Record the analyzer responses to each
calibration gas on CDS 6C.
C. Sampling System Bias Check
Conduct this bias check initially and after each
sampling run.
1. Introduce the calibration gases at the
calibration valve installed at the outlet of the
sampling probe. Operate the system at the
normal sampling rate, and make no
adjustments to the measurement system
other than those necessary to adjust the
calibration gas flow rates at the analyzer.
Wait until a stable response is achieved
before taking readings.
2. Introduce either the mid-range or high-range
gas, whichever is closest to the effluent
concentrations, and record the analyzer
response and the time ft took to reach a
stable response on FDS 6C.
3. Introduce zero gas, and record the analyzer
response and the time it took to reach a
stable response.
D. Emission Test Procedure
1. Select the sampling site and sampling points
as in Method 6. Set up the sampling system
as shown in Figure F6C-1.
2. Sample at each measurement point using the
same sampling rate as that used during the
sampling system bias check. Maintain
constant sampling rate (i.e., ±10%) during
the entire run.
3. Use the same sampling time per run as that
used for Method 6 plus twice the stable
response time for the instrument. Then
determine the average effluent
concentration.
4. Use the following options to determine the
average gas concentration.
By integration of the area under the
curve for chart recorders.
By averaging measurements recorded at
equally spaced intervals over the entire
run: Runs i1 hr must have recorded
measurements at 1 -minute intervals or a
minimum of 30 measurements,
whichever is less restrictive and runs
> 1 hr must have measurements at
2 min intervals or a minimum of
96 measurements, whichever is less
restrictive.
a.
-------
9/30/94: F6C-2
E. Post-Run Tests
1. Following each run, or before adjustments
are made to the measurement system
during the run, determine the sampling
system bias. Do not make any adjustments
to the measurement system untH after the
drift checks are completed. Record the
system responses on FDS 6C.
2. If the sampling system does not pass the
bias test at either the zero or upscale
calibration values, void the run. Repeat the
calibration error and bias tests before the
next run.
3. If the sampling system passes the bias
check, calculate the zero and upscale
calibration drift to determine whether the
calibration error and system bias tests must
be conducted before the next run.
F. Alternatives
1. Step A3c. For zero gas,'ambient air may be
used by purifying the air through a charcoal
filter or through one or more irrtpingers
containing a solution of 3% H262.
2. A calibration curve established prior to the
analyzer calibration error check may be used
to convert the analyzer response to the
equivalent gas concentration introduced to
the analyzer. However, the same correction
procedure shall be used for all effluent and
calibration measurements obtained during
the test.
leafed Filter
By-Pass Row
Control Valve v
Sample Transport Une
Sample By-Pass
Vent
L/^U£N
c^=^
Pump
Figure F6C-1. Measurement System Schematic.
-------
9/30/94: FD6C-1
Method
FIELD DATA SHEET 6C
Analyzer Calibration Bias and Drift
Client/Plant Name
City/State
_Job #
Date
Test Location
Note: Indicate units. Analyzer ID#
Personnel
Span
Upscale Value, C.
Note: Conduct this test initially and after each sampling run. Introduce gas at probe outlet.
If interference test is required, attach appropriate data sheets from Method 6. Avg Syst Peso = (Pre + Post)/2
(M 6C results x 7% of M 6 results?) -
Run
No.
1
2
3
4
5
6
7
8
9
10
11
12
Level
Upscale
Zero
Upscale
Zero
Upscale
Zero
Upscale
Zero
Upscale
Zero
Upscale
Zero
Upscale
Zero
Upscale
Zero
Upscale
Zero
Upscale
Zero
Upscale
Zero
Upscale
Zero
Time
Analyzer
Resp
•
Pre
• System
Resp
System
%Bias
Post
System
Resp
System
%Bias
% Drift
Stable
Resp
Time
*..
••
Avg
Syst
Resp
. Normal operation and no adjustments to system except to adjust calibration gas flow rates at analyzer?
_• %Syst Bias = 1OO (Syst Resp - Anal Resp)/Span (£ ±5% of span?J %Drift = Post - Pre (s ±3% of span?I
. Failure of bias test (or exceeding cal drift spec) requires repeat of cal error (CDS 6C> and bias tests before next run.
— Legibility Accuracy Specifications Reasonableness
QA/QC Check
Completeness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: FD6C-2
FIELD DATA SHEET 6C (Continued)
Sample Concentration
CIlent/F
City/St
TestLo
Noto: i
Run
No.
'lant Name
ate
Job #
Date
cation Personnel
'ndicate units. Void sample runs that faff the bias test (see FDS 6C, pg 1).
Meas
Pt
Time
Sampl
Rate
Syst
Resp
ft
Cone
Run
No.
Meas
Pt
Time
' : •
Sampl
Rate
Syst
Resp
•
Cone
___ Sampling rate same (within ±10%) as that used during the sampling system bias check at each measurement
point?
QA/QC Check
Completeness
Sampling time includes twice the average stable system response time before average concentration determined?
Legibility Accuracy Specifications Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
Method
CALIBRATION DATA SHEET 6C
Analyzer Calibration Error
9/30/94: CD6C-1
Client/Plant Name
City/State
Job #
Test Location
Date/Time
Personnel
Type of Calibration Gas: Protocol 1 (attach manufacturer's certification) Analysis (attach CDS 6Ca)
fluorescence-based Analyzers: Cal gas SO2/CO2/O2 in N2 with O2 and CO2 within ± 1 % O2 or ± 1 % CO, of
effluent concentration; or. Correction factors for O2/CO2 attached.
Conduct this test mft/al/y and each time system fails system bias/drift specs. Introduce gas at any point upstream of
analyzer.
Note: Indicate units.
Analyzer ID#
Span
Run
No.
1
2
3
4
5
6
Level
Zero
Mid-range
High-range
Zero
Mid-range
High-range
Zero
Mid-range
High-range
Zero
Mid-range
High-range
Zero
Mid-range
High-range
Zero
Mid-range
High-range
Cylinder
Value
•
Analyzer
Response
Absolute
Difference
%Cal Error
(of span) (^2%?)
QA/QC Check
Completeness
%Cal Error - Absolute Difference x 1QO
Span
No adjustments made to system except for adjusting flow rate of calibration gases at the analyzer?
— Legibility Accuracy Specifications Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: F6Ca-1
FIELD PROCEDURE 6Ca
Interference Check
Note: For each individual analyzer, conduct this interference check for at least three runs during the
initial field test on a particular source category. Retain the results, and report them with each test
performed on that source category. Use SS 6, FDS 6, and LDS 6.
1. Assemble the modified Method 6 train as
shown in Figure 6Ca-1, and install the
sampling train to obtain a sample at the by-
pass discharge vent of measurement system.
2. Record the initial dry gas meter reading.
3. Open the flow control valve concurrent with
the initiation of the sampling period, and
adjust the flow to 1 L/min (±10%).
(Note; Avoid over-pressurizing the impingers
and causing leakage.)
4. Record appropriate data as shown in FDS 6.
5. At the end of the test run, record the final
dry gas meter reading.
6. Recover and analyze the contents of the
midget impingers, and determine the SO2
gas concentration using the procedures of
Method 6 (see LDS 6). Determine the
average gas concentration exhibited by the
analyzer for the run (see SS 6).
Excess
Sample Vent
Sample
By-pass Vent
(15 ml each)
Figure F6Ca-1. Interference Check Sampling Train.
-------
Date
Cylinder ID#:
Methods
Zero:
CALIBRATION DATA SHEET 6Ca
Analysis of Calibration Cylinder Gases
(Must be ^6 months before test)
Mid:
9/30/94: F6Ca-1
Span
High:
Personnel
Attach appropriate field, laboratory, calibration data sheets (List}:
Run No.
1
2
3
4
5
6
Average
Max % Dev
Tag Value, ppm
Zero
«0.25% of span?)
Mid-Range
(40%-60% of span?)
High-Range
(80%-100%ofspan?)
Runs in triplicate or sextuplet sets are consecutive?
Specification
Max % Dev from Average*
Average Diff from Tag Value*
Method 6
£±5% or ±5 ppm
=£±5% or ±5 ppm
Method 7
£±10% or ±10 ppm
£±10% or ±10 ppm
Method 3
£±5% or ±0.2% abs
£±5% or ±0.2% abs
* Whichever is greater.
If avg diff from tag value > specification, use the avg of the 6 runs as the cylinder value.
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
-------
9/30/94: S7-1
SUMMARY SHEET 7
Nitrogen Oxides
Client/Plant Name FDS 7 Run #1 Run #2 Run #3 Avn
Job No.
Sampling Location
Run.D# .
Test Date FDS -,
Run Start Time FDS 7
Run Finish Time CP.O -i
-r- ~ . rUo /
Traverse Points (if applicable) FDS 7
Initial Temperature, °F t. Fpg -,
Initial Absolute Temperature, R TI ' SS 7
Final Temperature, °F *. FDS 7
Final Absolute Temperature, R T SS 7
Initial Barometric Pressure, in. Hg p.. pDS 7
Initial Vacuum, in. Hg p . cne 7
Initial Absolute Pressure, in. Hg p.9' SS 7
Final Barometric Pressure, in. Hg P FDS 7
Final Vacuum, in. Hg p FDg 7
Final Absolute Pressure, in. Hg p°f ss 7
Flask Volume, ml y QQO -,
Volume Absorbing Reagent, mL Vf FDS 7
Gas Sample Volume, mL V° SS 7
Spectrophotometer Calibration Factor K LDS 7
Sample Solution Volume, mL ° LDS 7
Average N02 Per Sample, //g m. LDS 7
Sample Concentration, Ib/dscf C^8 SS 7
Audit Relative Error, % RE
Post-test Calibration Checks
Temperature, Barometer, and Vacuum Gauges CDS 2d
Note: Consider Pgi and Pf to be positive.
CVjgj)
QA1
(460+ t,) (460-
C = 6.242 X 10'5 "
-------
!ueeze
3ulb
Probs
FBtar
\
Air-Tight
Pump
Thermometer
Figure F7-1. Sampling Train, Flask Valve, and Flask.
-------
9/30/94: F7-1
FIELD PROCEDURE 7
Nitrogen Oxides (Evacuated Flask)
Note: Except for some minor variations, this procedure is also used for Method 7A or 7B.
A. Pre-test Preparation
1. Pipette 25 mL of absorbing solution into a
sample flask.
2. Retain enough absorbing solution to prepare
the calibration standards.
B. Sampling
1. Assemble the sampling train as shown in
Figure F7-1, and place the probe at the
sampling point.
2. Ensure that all fittings are tight and leak-free,
and that all ground glass joints have been
greased properly with a high-vacuum, high-
temperature chlorofluorocarfaon-based
stopcock grease.
3. Evacuate the flask to --3 in. Hg absolute
pressure, preferably to the vapor pressure of
water at existing temperature.
4. Check for leakage by observing the
manometer for any pressure fluctuation (must
not vary >0.4 in. Hg in 1 min).
5. Record the data as shown in FDS 7.
6. Purge the probe and the vacuum tube using
the squeeze bulb. If condensation occurs in
the probe and the flask valve area, heat the
probe, and purge until the condensation
disappears.
7. Take flask pressure readings.
8. Extract sample slowly until pressures in the
flask and sample line (i.e., duct, stack) are
equal (usually 15 sec); a longer period
indicates a "plug" in the probe.
9. After collecting the sample, close the flask
valve, and disconnect the flask from the
sampling train.
10. Shake the flask for at least 5 min and let the
flask set for ^ 16 hr.
C. Sample Recovery
1. Shake the contents for 2 min.
2. Connect the flask to a mercury filled U—tube
manometer.
3. Open the valve from the flask to the
manometer, and record the flask temperature,
the barometric pressure, and the flask
vacuum.
4. Transfer the contents of the flask to a leak-
free polyethylene bottle. Rinse the flask twice
with 5-mL portions of deionized distilled
water, and add the rinse water to the bottle.
5. Adjust the pH to between 9 and 12 by
adding 1 N NaOH, dropwise (about 25 to
35 drops). Check the pH by dipping a
stirring rod into the solution and then
touching the rod to the pH test paper.
Remove as little material as possible during
this step.
6. Seal and label the container. Mark the
height of the liquid level.
D. Post-test Calibrations
Calibrate thermometers, barometer, and vacuum
gauges (if other than mercury manometer). See CP
2d, 2e, and 2f.
E Method 7A
1. FP 7A is the same as that for FP 7, except
omit step C5 (adjusting the pH). Use FDS 7.
2. FP 7A may be subject to a low bias when
S02 >2000 ppm.
F. Method 7B
1. . Apply this procedure to emissions from nitric
acid plants only.
2. Follow the procedure in FP 7 up and
including step C2. Use FDS 7. Do not
increase H202 concentration.
3. Transfer the contents of the flask to a
100-mL volumetric flask.
4. Rinse the flask three times with 10-mL
portions of deionized distilled water, and add
to the volumetric flask.
5. Dilute to 100 mL with deionized distilled
water. Mix thoroughly. Analyze the sample
(see LP 7B).
G. Sampling Gas Stream with Insufficient
Oxygen
Introduce oxygen into flask by one of the
following three methods:
1.
2.
3.
Before evacuating the sampling flask, flush
with pure cylinder oxygen, then evacuate
flask to i3 in. Hg absolute pressure.
Inject oxygen into the flask after sampling.
Terminate sampling with a minimum of 2 in.
Hg vacuum remaining in the flask, record
this final pressure, and then vent the flask to
the atmosphere until the flask pressure is
almost equal to atmospheric pressure.
-------
9/30/94: FD7-1
FIELD DATA SHEET 7
Evacuated Flask Sample
Method (Circle) 7 7A 7B
Client/Plant Name
City/State .
Job #
Date/Time
Test Location/Run #
Personnel
Clock
Time
.titan,,.-.* •'•-i-'':;, ;J!'V
t ' •"
,,i"', -: i ••'•
A" ' ,, ;
n
Jf '•
^
p I
••' i. .. ::-•'''!: '
V ^ . 1.' , , .. • ^y
,,» ,
Steps
Initial Vacuum (£3 in. abs ?) (in. Hg)
Leak Check (£0.4 in. Hg/min ?) (in. Hg}
Flask ID/Valve #
Flask/Valve Volume (cc)
•Initial Temperature, tj (°F)
Initial Barometric Pressure, Pb, (in. Hg)
Purge (no condensation?) (•)
Initial Vacuum (Leg A + Leg B), Pg, (in. Hg)
Initial Pressure, P, (in. Hg)
Shake for 5 minutes ? (•)
Flask stand f or £s 1 6 hr ? (•)
Shake for 2 minutes ? • (•)
Final Flask Temperature, tj (°F)
Rnal Barometric Pressure, Pbf (in. Hg)
Final Vacuum (Leg A + Leg B), Pgf (in. Hg)
Final Pressure, Pf (in. Hg)
Adjust pH (9-1 2), M7 only? (•)
Seal and mark liquid level? (•)
Label container ? (•)
Sample Volume, Vsc (mL)
Sample #
Sample #
Sample #
i •
<
Sample #
(P P1
•=• - -=-\ Add 460 to tf and t, to obtain Tf and Ts, respectively.
'i 'ij
Post-test Calibrations
Attach FDS 2d for pressure, barometric pressure, and temperature post-test checks (temperature < ±2°F).
QA/aC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: L7-1
5.
6.
2.
3.
4.
5.
LABORATORY PROCEDURE 7
Nitrogen Oxides
4.
A. Reagent Preparation
1. Hydrogen Peroxide, 3%. Dilute 30% H202
1:9 with deionized distilled water. Prepare
fresh daily.
2. Absorbing Solution. Cautiously add 2.8 mL
cone. H2S04 to 1 L of deionized distilled
water. Mix well, and add 6 mL 3% H2O2.
Use within 1 week of preparation. Do not
expose to extreme heat or direct sunlight.
3. Sodium Hydroxide, 1 N. Dissolve 40 g NaOH
in deionized distilled water, and dilute to 1 L.
Potassium Nitrate Standard. Dry KN03 at 105
to 110°C for at least 2 hr just before
preparation. Dissolve exactly 2.198 g dried
KN03 in deionized distilled water, and dilute to
1 L with deionized distilled water in a
1000-mL volumetric flask.
Working Standard KN03 Solution, 100//g
N02/mL. Dilute 10 mL standard solution to
100 mL with deionized distilled water. ,
Phenoldisulfonic Acid Solution. Dissolve 25 g
pure white phenol solid in 150 mL cone.
H2S04 on a steam bath. Cool, add 25 mL
fuming H2S04 (15 to 18% by weight free
sulfur trioxide - HANDLE WITH CAUTION),
and heat at 100°C for 2 hr. Store in a dark,
stoppered bottle.
7. QA Audit Samples. Obtain from EPA
(see QA 1).
B. Spectrophotometer Calibration Factor Kc
1. Calibrate the wavelength scale of the
Spectrophotometer, if not done within the
past six months. (See CP 7a).
7.
8.
Add 0.0 mL, 2.0 mL, 4.0 mL, 6.0 mL, and
8.0 mL of the KN03 working standard solution
Loml7 = ,100 ^9 N°2>to a series of five
50-mL volumetric flasks.
To each flask, add 25 mL of absorbing
solution, 10 mL deionized distilled water, and
I N Na-,9,H, d,r°Pwise until the pH is between
9 and 12 (about 25 to 35 drops each).
Dilute to the mark with deionized distilled
water, and mix thoroughly.
Pipette a 25-mL aliquot of each solution into
a separate porcelain evaporating dish.
6. Follow steps D6 through D13.
Measure the absorbance of each solution, at
410 nm or the wavelength determined in
CP7a.
Repeat this calibration procedure on each day
that samples are analyzed.
9.
C.
2.
Calculate the Spectrophotometer calibration
factor K0.
Spectrophotometer Calibration Quality Control
Multiply the absorbance value obtained for
each standard by the Kc factor (least squares
slope) to determine the distance each
calibration point lies from the theoretical
calibration line.
These calculated concentration values should
not differ from the actual concentrations (i.e.,
100, 200, 300, and 400 //g N02) >7% for
three of the four standards.
D. Analysis
1. Note the level of the liquid in the sample
containers, and determine loss; note this loss,
if any, on the analytical data sheet.
2. Immediately prior to analysis, transfer the
contents of the shipping container to a 50-mL
volumetric flask, and rinse the container twice
with 5-mL portions of deionized distilled
water. .:
3. Add the rinse water to the flask, and dilute to
mark with deionized distilled water; mix
thoroughly.
4. Pipette a 25-mL aliquot into the porcelain
evaporating dish.
Return any unused portion of the sample to
the polyethylene storage bottle.
Evaporate the 25-mL aliquot to dryness on a
steam bath, and allow to cool.
7. Add 2 mL phenoldisulfonic acid solution to the
dried residue, and triturate thoroughly with a
polyethylene policeman. Ensure the solution
contacts all the residue.
8. Add 1 mL deionized distilled water and 4
drops of cone, sulfuric acid. Heat the solution
on a steam bath for 3 min with occasional
stirring. Allow the solution to cool.
9. Add 20 mL deionized distilled water, mix well
by stirring. Add cone, ammonium hydroxide,
dropwise, with constant stirring, until the pH
is 10 (as determined by pH paper).
10. If the sample contains solids, filter as follows
(centrifuging may also be used):
5.
6.
a.
b.
Filter through Whatman No. 41 filter
paper into a 100-mL volumetric flask.
Rinse the evaporating dish with three
5-mL portions of deionized distilled
water.
c. Filter these three rinses.
-------
d. Wash the fitter with at least three 15-mL
portions of deionized distilled water.
e. Add the filter washings to the contents of
the volumetric flask, and dilute to the
mark with deionized distilled water.
f. If solids are absent, transfer the solution
directly to the 100-mL volumetric flask
and dilute to the mark with deionized
distilled water.
11. Mix the contents of the flask thoroughly, and
measure the absorbance at the wavelength
used for the standards, using the blank
solution as a zero reference.
9/30/94: L7-2
12. Dilute the sample and the blank with equal
volumes of deionized distilled water if the
absorbance exceeds A4/ the absorbance of
the 400-fjg N02 standard.
13. Concurrently analyze the two audit samples
and a set of compliance samples, if
applicable, in the same manner as the
samples.
-------
Client/Plant Name
Analyst
Spectrophotometer ID#
Date of Last Calibration
LABORATORY DATA SHEET 7
Nitrogen Oxides
(£6 months?)
Job#
Date/Time
, Wavelength
K.
9/30/94: LD7-1
nm
Volume of
Working
Std
(mL) .
0.0
* 2.0
4.0
6.0
8.0
(A)
Mass NO2 in
Std
(TO N02)
0
100
200
300
400
(B)
Absorbance
(OD)
AO
A,
A2
A3
A4
(C)
KcAj
(fjg NO2)
(C) - (A)
(fJQ N02)
QCChk
fc/g N02)
£±7?
£±14?
£±21?
£±28?
Sample ID#
Audit Sample #1
Audit Sample #2
Volume
Loss, V|
(mL)
Sample
Volume, V8
(mL)
Aliquot
Volume, Va
(mL)
Absorbance
A
(OD)
Mass/
Samp, m
U/g N02)
.
Average
™ava
(fJQ N02)
= 2K0AF 2 = 50/25
F = Dilution factor, if sample was diluted to bring absorbance into
calibration range.
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: C7-1
CALIBRATION PROCEDURE 7
Evacuated Flask
1. Assemble the flask and flask valve, and fill
with deionized distilled water to the
stopcock. A hypodermic syringe may be
helpful.
2. Measure the volume of water to ± 10 mL,
using a 500-mL glass (Class A) graduated
cylinder.
3. Make duplicate runs and average the
volumes.
4. Record this average volume on the flask.
5. If flask valves are not switched, this
calibration is required once.
-------
9/30/94: CD7-1
CALIBRATION DATA SHEET 7
Evacuated Flasks
5OO-ml glass (Class A) graduated cylinder?
Date
Flask
ID#
Flsk Valve
ID#
Run#1
(cc)
QA/QC Check
Completeness Legibility Accuracy
Checked by:
Run #2
(cc)
Specifical
Average
(cc)
Personnel
(Signature)
ions Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: C7a-1
CALIBRATION PROCEDURE 7a
Spectrophotometer Calibration
Note: Recalibrate the wavelength scale of the Spectrophotometer every 6 months as follows:
A. Calibration Check B. Alternative Calioration Check
1. Use an energy source with an intense line 1.
emission such as a mercury lamp, or use a
series of glass filters spanning the measuring
range of the Spectrophotometer, to check the
calibration of the Spectrophotometer. Follow
the manufacturer's recommended
procedures.
2. The wavelength scale of the
Spectrophotometer must agree to within
±5 nm at all calibration points; otherwise,
repair and recalibrate the Spectrophotometer.
Use 410 nm for all measurements of the 2.
standards and samples.
If the instrument is a double-beam
Spectrophotometer, scan the spectrum
between 400 and 415 nm using a 200 //g
N02 standard solution in the sample cell and
a blank solution in the reference cell. If no
peak occurs, the Spectrophotometer is
probably malfunctioning; repair it. When a
peak is within the 400 to 415 nm range, use
the wavelength at which this peak occurs for
the measurement of absorbance of both the
standards and the samples.
For a single-beam Spectrophotometer, follow
the scanning procedure described above,
except scan separately the blank and
standard solutions. For the measurements of
samples, use the wavelength at which the
maximum difference in absorbance between
the standard and the blank occurs.
-------
9/30/94: CD7b-1
CALIBRATION DATA SHEET 7b
Spectrophotometer
(Alternative Procedure)
Spectrophotometer ID#
Personnel
Date
, Date of Prev. Cal.
(^ 6 months between calibrations?)
This data sheet is designed for a single-beam Spectrophotometer. For a double-beam Spectrophotometer, fill in the
second column only.
Spectrophotometer
setting
(nm)
399
400
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
Absorbance of
200 UQ NO2 Standard
(OD)
Absorbance of
blank
(OD)
Actual Absorbance
of Standard
(OD)
Circle the wavelength at which the maximum peak absorbance (last column for single-beam and second
column for double-beam) occurs.
If there is no peak absorbance, repair or recalibrate the Spectrophotometer.
QA/QC Check
Completeness
Legibility
Accuracy
Checked by:
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: S7A-1
SUMMARY SHEET 7A
Nitrogen Oxides
Run #1 Run #2 Run #3 Avg
Client/Plant Name = FDS 7
Job No. FDS 7
Sampling Location FDS 7
RunID* FDS7
Test Date FDS 7
Run Start Time FDS 7
Run Finish Time FDS 7
Traverse Points {if applicable) FDS 7
Initial Temperature, °F t-t FDS 7
Initial Absolute Temperature, R Tj SS 7
Final Temperature, °F % FDS 7
Final Absolute Temperature, R Tf SS 7
Initial Barometric Pressure, in. Hg Pbi FDS 7
Initial Vacuum, in. Hg Pgi FDS 7
Initial Absolute Pressure, in. Hg P( SS 7
Final Barometric Pressure, in. Hg Pbf FDS 7
Final Vacuum, In. Hg P^ FDS 7
Final Absolute Pressure, in. Hg Pf SS 7
Flask Volume, mL Vf CDS 7
Volume Absorbing Reagent, mL Va FDS 7
Gas Sample Volume, mL Vso SS 7
Chromatographic Calibration Factor S LDS 7A
Sample Solution Volume, mL LDS 7A
Average N02 Per Sample, //g m LDS 7A
Sample Concentration, Ib/dscf C SS 7A
Audit Relative Error, % RE QA1
Post-test Calibration Checks
Temperature, Barometer, Vacuum Gauge CDS 2d
C = 6.242 X 10-5 Jp-
"sc
-------
9/30/94: L7A-1
LABORATORY PROCEDURE 7A
Nitrogen Oxides (Ion Chromatographic Method)
A. Reagent Preparation
1. Stock Standard Solution, 1 mg N02/mL.
Dry NaNO3 at 105 to 110°C for i2 hr just
before preparing the standard solution.
Dissolve exactly 1.847 g dried NaN03 in
deionized distilled water, and dilute to 1 L
in a volumetric flask. Mix well. Date this
solution. Do not use after 1 month.
2. Working Standard Solution, 25 jt/g/mL.
Dilute 5 ml of the standard solution to
200 mL with deionized distilled water in a
volumetric flask, and mix well.
3. Eluent Solution, 0.0024 M Na2C03/0.003 M
NaHCO3. Weigh 1.018 g Na2C03 and
1.008 g NaHC03, and dissolve in 4 L
deionized distilled water. Other eluents
appropriate to the column type may be
used.
4. Quality Assurance Audit Samples. Obtain
from EPA {see QA 1).
B. Sample, Standards, and Chromatograph
Preparations (-
1. Analyze samples within 4 days after
collection.
2. Note the level of the liquid in the container,
and determine loss; note this loss, if any, on
the laboratory data sheet.
3. Immediately before analysis, transfer the
contents of the shipping container to a
50-mL volumetric flask, and rinse the
container twice with 5-mL portions of
deionized distilled water. Add the rinse
water to the flask, and dilute to the mark
with deionized distilled water. Mix
thoroughly.
4. Pipet a 5-mL aliquot of the sample into a
50-mL volumetric flask, and dilute to the
mark with deionized distilled water. Mix
thoroughly. For each set of determinations,
prepare a reagent blank by diluting 5 mL of
absorbing solution to 50 mL with deionized
distilled water. (Alternatively, eluent
solution may be used in all sample,
standard, and blank dilutions.)
5.
6.
Prepare a series of five standards by
adding 1.0, 2.0, 4.O, 6.O, and 10.O mL of
working standard solution (25 yug/mL) to a
series of five 50-mL volumetric flasks.
(Masses are 25, 50, 100, 150, and 250
/jg.) Dilute each flask to volume with
deionized distilled water, and mix well.
Calibrate the conductivity detector
according to manufacturer's specifications
prior to initial use.
C. Analysis
1. Inject the calibration standards.
2. Inject samples and a blank, using same
injection volumes as that of the standards.
3. Inject another set of calibration standards.
4. Repeat step C2 with a duplicate set of
samples and blank.
5. Inject a final set of calibration standards.
6. Analyze the audit samples, if applicable.
7. Determine peak heights (if symmetrical) or,
, in all other cases, peak areas. Determine
the averages.
8. Prepare or calculate a linear regression plot
of the standards in //g (x-axis) versus their
peak heights or areas. Determine the slope,
and its reciprocal. If any point deviates
from the line by more than 7% of the
concentration, remake and reanalyze.
(See LDS 7A).
9. Perform all analyses on the same day.
Dilute any sample and the blank with equal
volumes of deionized distilled water if the
concentration exceeds that of the highest
standard.
10. Document each sample chromatogram by
listing the following analytical parameters:
injection point, injection volume, nitrate and
sulfate retention times, flow rate, detector
sensitivity setting, and recorder chart
speed. (See LDS 7A).
-------
9/30/94: LD7A-1
LABORATORY DATA SHEET 7A
Nitrogen Oxides
Client/Plant Name
Analyst
Job #
Date/Time
Note: Attach plot of calibration curve. Determine slope of curve and its reciprocal (S). Multiply S by by peak height
or area and determine deviation of each point from the line. The deviation must be <.?% of the concentration at
each point.
Chromatographi
Detector Sensith
Flow rate:
c Conditions:
/ity
Eluent: (O.OOSMNal
Injection Point Inje
Chart Speed
Cal. Stds
(mL)
1.0
2.0
4.0
6.0
10.0
(fig N02)
25
50
100
150
250
Initial
Hgt/Area
Retention Times: Nitrate
VCOyO. 0024 M Na2CO^?
ction Volume
5 Sulfate
Final
Hgt/Area
Avg
' Hgt/Area
Sample 1D#
•
Blank, B
Audit Sample #1
Audit Sample #2
Volume
• Loss, Vj
(mL)
.
Sample
Volume, Vs
ImL)
•
Peak Height/Area, H (Hj/Avg
-------
9/30/94: S7B-1
SUMMARY SHEET 7B
Nitrogen Oxides
rr t/DI . .. Run#1 Run #2 Run #3 Avg
Client/Plant Name PDS 7
Job No. FDS 7
Sampling Location PDS 7
RunID* . . FDS7
Test Date FDS 7
Run Start Time FDS 7
Run Finish Time PDS 7
Traverse Points {if applicable) FDS 7
Initial Temperature, °F tf FDS 7
Initial Absolute Temperature, R • Tj SS 7
Final Temperature, °F tJ FDS 7
Final Absolute Temperature, R Tf SS 7
Initial Barometric Pressure, in. Hg p.. FDS 7
Initial Vacuum, in. Hg p ! pos 7
Initial Absolute Pressure, in. Hg p?' SS 7
Final Barometric Pressure, in. Hg Pbf FDS 7
Final Vacuum, in. Hg p pos 7
Final Absolute Pressure, in. Hg Pf SS 7
Flask Volume, mL Vf CDS 7
Volume Absorbing Reagent, mL Va FDS 7
Gas Sample Volume, mL V° SS 7
Spectrophotometer Calibration Factor Kc LDS 7B
Sample Solution Volume, mL * LDS 7B
Average NO2 Per Sample, fig m LDS 7B
Sample Concentration, Ib/dscf C SS 7B
Audit Relative Error,% RE QAI
Post-test Calibration Checks
Temperature, Barometer, Vacuum Gauge CDS 2d
C = 6.242 x 1Q-5 —
-------
9/30/94: L7B-1
LABORATORY PROCEDURE 7B
Nitrogen Oxides
(Ultraviolet Spectrophotometry)
Note: This procedure is similar to that of Method 7, except for the following:
A. Reagent Preparation
1. Working Standard KNO3 Solution, 10
pg NOa/mL. Dilute 10 mL of the standard
solution to 1000 mL with deionized distilled
water.
2. Quality Assurance Audit Samples. Obtain
fromEPA(seeQAI).
B. Determination of Spectrophotometer
Standard Curve
1. Add 0.0 mL, 5 mL, 10 mL, 15 ml, and
20 mL KNO3 working standard solution to a
series of five 100-mL volumetric flasks.
2. To each flask, add 5 mL absorbing solution.
Dilute to the mark with deionized distilled
water. The resulting solutions contain 0.0,
50, 100, 150, and 200 fjg NO2,
respectively.
3. Measure the absorbance by ultraviolet
Spectrophotometry at 210 nm, using the
blank as a zero reference.
4. Plot absorbance vs. //g NO2. Calculate the
spectrophotometer calibration factor.
(See LDS 7B).
C. Analysis
1. Pipette a 20-mL aliquot of sample into a
100-mL volumetric flask. If other than
20-mL is used, adjust standards and blank
solutions accordingly.
2. Dilute to 100 mL with deionized distilled
water.
3. Analyze the sample on the ultraviolet
Spectrophotometry at 210 nm, using the
blank as zero reference.
4. With each set of compliance samples or
once per analysis day, or once per week
when averaging continuous samples,
analyze each performance audit in the same
manner as the sample to evaluate the
analyst's technique and standard
preparation. (Set QA 1).
-------
LABORATORY DATA SHEET 7B
Nitrogen Oxides
Client/Plant Name
Analyst
Spectrophotometer ID#
Date of Last Calibration
J ^6 months?)
Job*
Date/Time
Wavelength
K0 = 50
9/30/94: LD7B-1
_nm (210nm?J
Volume of
Working Std
(ml)
0.0
5.0
10.0
15.0
20.0
(A)
Mass NO2 in Std
fc/9 N02)
0
50
100
150
200
(B)
Absorbance
(OD)
AO
AI
A2
A3
A4
(C)
KcA,
(UQ N02)
,-
Sample ID#
Audit Sample #1
Audit Sample #2
Volume
Loss, V,
(mL) '
Sample
Volume, Vs
(mL)
Aliquot
Volume, Va
(mL)
Absorbance
A
(OD)
Mass/
Samp, m
(V9 N02)
Average
mavg
(/>g N02)
m-5K0AF 5- 100/20 F = Dilution factor, if sample was diluted to bring absorbance into
calibration range.
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: S7C-1
Client/Plant Name
Job No.
Sampling Location
Run ID*
Test Date
Run Start Time
Run Finish Time
Traverse Points (if applicable)
Net Run Time, min
Dry Gas Meter Calibration Factor
Barometric Pressure, in. Hg
Average DGM Temperature, °F
Absolute Average DGM Temperature, R
Average C02, %
Correction Factor for C02
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Spectrophotometer Calibration Factor
Average NO2 Per Sample, jjg
Sample Concentration, Ib/dscf
Audit Relative Error, %
Post-test Calibration Checks
Temperature and Barometer
Metering System
SUMMARY SHEET 7C
Nitrogen Oxides
FDS 6/7C
FDS 6/7C
FDS 6/7C
FDS 6/7C
FDS6/7C
FDS 6/7C
FDS1
0
Y
'm
Tm
%CO2
X
vm
Vm(std)
m
C
RE
FDS 6/7C
FDS 6/7C
FDS 6/7C
FDS 6/7C
FDS6/7C
FDS7C
SS7C
FDS 6/7C
SS6 .
LDS7C
LDS7C
SS7C
QA1
CDS2d
CDS 6
Run#1
Run #2
Run #3 Avg
100
(100-%CO2)
17.64 VmXY-t
'm
C = 6.242 x 10'5 ——
V.
m(std)
-------
9/30/94: F7C-1
FIELD PROCEDURE 7C
Nitrogen Oxides (Alkaline-Permanganate)
A. Pre-test Preparation
1. Prepare the collection train as follows:
a. Add 200 mL KMn04/NaOH solution to
each of three impingers.
b. Assemble the train as shown in
Figure F7C-1.
c. Adjust probe heater to a temperature
sufficient to prevent water
condensation.
2. Determine the sampling point or points.
3. Optional: Leak-check the sampling train
(see FP 3c, sections C and D).
4. Optional: Check of rotameter calibration
accuracy as follows:
a. Disconnect the probe from the first
impinger, and connect the filter.
b. Start the pump, and adjust the
rotameter to read between 400 and
500 cc/min.
c. After the flow rate has stabilized,
measure the volume sampled from the
DGM and the sampling time. Collect
enough volume to measure accurately
the flow rate, and calculate the flow
rate (must be < BOO cc/min for the
sample to be valid).
B. Sampling
1. Record the initial DGM reading and
barometric pressure. Use FDS 6 and attach
FDS 7C.
2. Position the tip of the probe at the sampling
point, connect the probe to the first
impinger, and start the pump. Adjust the
sample flow to between 400 and
500 cc/min.
3. Once adjusted, maintain a constant flow
rate during the entire sampling run. Sample
for 60 min.
4. Record the DGM temperature, and check
the flow rate at least every 5 min.
5. At the conclusion of each run, turn off the
pump, remove probe from the stack, and
record the final readings.
6. Divide the sample volume by the sampling
time to determine the average flow rate
(must be <500 cc/min.
7. Mandatory: Leak-check the sampling train
(see FP 3c, sections C and D).
8. During sampling, use Method 3 (Orsat or
Fyrite) to measure C02 of the stack gas near
the sampling point. If single-point grab
sampling procedure is used, conduct
measurements at least three times (near the
start, midway, and before the end of a run),
and the average C02 concentration. •
C. Sample Recovery
1 . Disconnect the impingers. Pour the
contents of the impingers into a 1 L
polyethylene bottle using a funnel and a
stirring rod (or other means) to prevent
spillage.
2. Rinse the impingers and connecting tubes
' with deionized distilled water until the
rinsings are clear to light pink, and add the
rinsings to the bottle.
3. Mix the sample, and mark the solution level.
Seal and identify the sample container.
D. Post-test Calibrations
Conduct post-test calibrations of metering
system and temperature gauges. (See FP 2d and
CP 6).
E. Special Considerations
1 . For relative accuracy (RA) testing of
continuous emission monitors, the minimum
sampling time is 1 hr, sampling 20 min at
each traverse point.
2. For RA tests with S02 ^ 1 200 ppm, sample
for 30 min (10 min at each point).
-------
Prci« (End P»dc«d
with Quwtz or
Surj.Tink
Figure F7C-1. NOj, Sampling Train.
-------
9/30/94: FD7C-1
FIELD DATA SHEET 7C
Nitrogen Oxides (Alkaline Permanganate)
Client/Plant Name _
Test Location/Run #
Job#
Personnel
Use FDS 6 and attach this data sheet. For CO2 (integrated sample), use FDS 3 and attach to FDS 6.
Continuation sheet of FDS 6 for FDS 7C
Trav.
Pt.
Samplg
time
(min)
Total Time,
*s
DGM Rdg
(cf)
Volume, Vm
Rotamefer
Rdg
(cc/min)
Avg
Temperature (°F)
DGM
Avg, tm
Imp. Exit
Max
=3 68 °F?
Flow Rate Deviation
AVm
Avg
AVm/AVm
0.90- 1.10?
For Fyrite, single point analysis, fill in information in table.
Fyrite, Single Point Grab Sampling
Run#
1
2
3
Clock Time
Beginning
Midway
Ending
Average:
%CO2
Flow Rate £500 cc/min?
If Relative Accuracy test of OEMS:
Sampling time of 1 hr, 20 min/point?
SO2 £t 1200 ppm? Run for 30 min, 10 min/point.
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: L7C-1
LABORATORY PROCEDURE 7C
Nitrogen Oxides
A. Reagent Preparation
1. Potassium Permanganate, 4.0%, Sodium
Hydroxide, 2.0%. Dissolve 40.0 g KMn04
and 20.0 g NaOH in 940 mL water.
2. Oxalic Acid Solution. Dissolve 48 g
(COOH)2-2H20 in water, and dilute to
500 mL. Do not heat.
3. Sodium Hydroxide, 0.5 N. Dissolve 20 g
NaOH in water, and dilute to 1 L.
4. Sodium Hydroxide, 10 N. Dissolve 40 g
NaOH in water, and dilute to 100 mL.
5. Ethylenediamine Tetraacetic Acid (EOTA)
Solution, 6.5%. Dissolve (using a magnetic
stirrer) 6.5 g EDTA (disodium salt) in water,
and dilute to 100 mL.
6. Column Rinse Solution. Add 20 mL 6.5%
EDTA solution to 960 mL water, and adjust
the pH to 11.7 to 12.0 with 0.5 N NaOH.
7. Hydrochloric Acid (HCI), 2 N. Add 86 mL
cone. HCI to a 500-mL volumetric flask
containing water, dilute to volume, and mix
well. Store in a glass-stoppered bottle.
8. Sulfanilamide Solution. Add 20 g
sulfanilamide (melting point 165 to 167°C)to
700 mL water. Add, with mixing, 50 mL
cone, phosphoric acid (85%), and dilute to
1 L. Refrigerate. Do not use after 1 month.
9. N-(1-Naphthyl)-EthyIenediamine
Dihydrochloride (NEDA) Solution. Dissolve
0.5 g NEDA in 500 mL water. Use only if
this aqueous solution has an absorption peak
at 320 nm over the range of 260 to 400 nm.
Protect from sunlight and refrigerate. Do not
use after 1 month.
10. Cadmium. See Matheson Coleman and Bell,
2909 Highland Avenue, Norwood, Ohio
45212, as EM Laboratories Catalogue
No. 2001. Prepare (in an exhaust hood away
from flame as H2 is liberated) by rinsing in
2 N HCI for 5 min until the color is silver-
grey. Then rinse the cadmium with water
until the rinsings are neutral when tested
with pH paper.
11. NaN02 Standard Solution, Nominal
Concentration, 1000jt/g NO27mL. Desiccate
NaN02 overnight. Accurately weigh 1.4 to
1.6 g NaN02 (assay of 97% NaN02 or
greater), dissolve in water, and dilute to 1 L.
Calculate the exact NO2" concentration. Do
not use after 6 months.
12. KN03 Standard Solution. Dry KN03 at
110°C for 2 hr, and cool in a desiccator.
Accurately weigh 9 to 10 g KN03 to within
0.1 mg, dissolve in water, and dilute to 1 L.
Calculate the exact NO3" concentration. Do
not use after 2 months.
13. Spiking Solution. Pipette 7 mL KN03
standard into a 100-mL volumetric flask, and
dilute to volume.
14. Blank Solution. Dissolve 2.4 g KMn04 and
1.2 g NaOH in 96 mL water. Alternatively,
dilute 60 mL KMn04/NaOH solution to
100mL.
15. Quality Assurance Audit Samples. Obtain
from EPA (see QA 1).
B. Calibration Curve lor Spectrophotometer
1. Dilute 5.0 mL NaN02 standard solution to
200 mL with water to obtain nominally 25 //g
NO2"/mL. Using pipettes, prepare at least
three calibration standards each for the linear
and slightly nonlinear curve to cover the
range of 0.25 to 3.00//g NO2"/mL. '
2. Analyze the standards and a water blank.
3. Plot the net absorbance vs. //g NO2"/mL.
Draw a smooth curve through the points and
the origin. The curve should be linear from
zero up to an absorbance of about 1.2 with a
slope of about 0.53 absorbance units///g
NO2"/mL. The curve is slightly nonlinear from
an absorbance of 1.2 to 1.6.
C. Sample Preparation
1. Prepare a cadmium reduction column as
follows:
a. Fill the burette with water. Add freshly
prepared cadmium slowly with tapping
until no further settling occurs. Final
height of the cadmium column should be
39 cm. Do not use cadmium (e.g.,
regenerated) that causes a band of
cadmium fines.
b. When not in use, store the column under
rinse solution (A6).
2. Note the level of liquid in the sample
container, and determine loss; note this loss,
if any, on the laboratory data sheet.
3. Quantitatively transfer the contents to a 1 L
volumetric flask, and dilute to volume.
4. Take a 100-mL aliquot of the sample and
blank (unexposed KMn04/NaOH) solutions,
and transfer to 400-mL beakers containing
magnetic stirring bars.
5. Using a pH meter, add cone. H2S04 with
stirring until a pH of 0.7 is obtained.
-------
6. Allow the solutions to stand for 15 min.
7. Cover the beakers with watch glasses, and
bring the temperature of the solutions to
5O°C. Keep <60°C.
8. Dissolve 4.8 g oxalic acid in a minimum
(about 50 ml_) volume of water at room
temperature. Do not heat the solution.
9. Slowly add oxalic acid solution to the KMn04
until it becomes colorless. If the color is not
completely removed, prepare more of the
oxalic acid solution, and add until a colorless
.solution is obtained.
10. Add an excess of oxalic acid by dissolving
1.6 g oxalic acid in 50 mL water, and add
6 mL to the colorless solution.
11. If suspended matter is present, add cone.
H2S04 until a clear solution is obtained.
12. Allow samples to cool to room temperature,
and ensure samples remain clear.
13. Adjust the pH to 11.7 to 12.0 with
10 N NaOH.
14. Quantitatively transfer the mixture to a
Buchner funnel containing GF/C filter paper,
and filter the precipitate. Filter the mixture
into a 500-mL filtering flask. Wash the solid
material four times with water.
15. When filtration is complete, wash the Teflon
tubing, transfer the filtrate to a 500-mL
volumetric flask, and dilute to volume. The
samples are now ready for cadmium
reduction.
16. Pipette a 50-mL aliquot of the sample into a
150-mL beaker, and add a magnetic stirring
bar.
17. Pipette in 1 .OmL 6.5% EDTA solution, and
mix.
18. Set stopcock to establish a flow rate of 7 to
9 mL/min of column rinse solution through
the cadmium reduction column. Use a 50-mL
graduated cylinder to collect and measure the
solution volume.
19. After the last of the rinse solution has passed
from the funnel into the burette, but before
air entrapment can occur, add sample, and
collect it in a 250-mL graduated cylinder.
9/30/94: L7C-2
20. Complete the quantitative transfer of the
sample to the column as the sample passes
through the column. After the last of the
sample has passed from the funnel into the
burette, start adding 60 mL column rinse
solution, and collect the rinse solution until
the solution just disappears from the funnel.
21. Quantitatively transfer the sample to a
200-mL volumetric flask (250-mL may be
required), and dilute to volume. The samples
and blank are now ready for NO2" analysis.
22. Run two spiked samples with every group of
samples passed through the column.
a. Prepare spiked samples by taking 50-mL
aliquots of the sample suspected to have
the highest NO2" concentration, and
adding 1 mL spiking solution.
b. Calculate spike recovery and column
efficiency. If either is < 95%, prepare a
new column, and repeat the cadmium
reduction.
D. Analysis
1. Pipette 10 mL sample into a culture tube. Do
not use test tubes, unless it has a low blank
NO2~ value.
2. Pipette in 10 mL sulfanilamide solution and
1.4 mL NEDA solution.
3. Cover the culture tube with parafilm, and mix
the solution.
4. Prepare a blank in the same manner using the
sample from treatment of the unexposed
KMn04/NaOH solution (A1).
5. Prepare a calibration standard to check the
slope of the calibration curve.
6. After a 10-min color development interval,
measure the absorbance at 540 nYn against
water.
7. Read //g N02VmL from the calibration curve.
If the absorbance is greater than that of the
highest calibration standard, pipette less than
10 mL, and repeat the analysis.
8. Determine the NO2' concentration using the
calibration curve obtained in B3.
9. Analyze the audit samples, if applicable.
-------
9/30/94: LD7C-1
LABORATORY DATA SHEET 7C
Nitrogen Oxides
Client/Plant Name
Analyst
Job#
Spectrophotometer ID#
Date of Last Calibration
Date/Time
Wavelength
nm
(£.6 months?)
Volume of
Working
Std
(mL)
(A)
Mass N02 in
Std
(f/fl N02)
(B)
Absorbance
(OD)
AI
A2
A3
(C)
(A/g°Nc!2)
(C) - (A)
(A/9 NO2)
QCChk
(A/9 N02)
Sample ID#
Blank
Spiked Sample #1
Spiked Sample #2
Audit Sample #1
Audit Sample #2
Volume
Loss, V|
(mL)
Sample
Volume, V8
(mL)
Aliquot
Volume, Va
(mL)
Absorbance
A
(OD)
NO2
Analyzed, S
(A/9>
NO2 in
Samp, m
(A/9)
.=
F m (Spiked - Unspiked)
Spike Cone
QA/QC Check
Completeness
(S-B)
E
S = Sample
B = Blank
E = Column Efficiency (must be
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
Client/Plant Name
Job No.
Sampling Location
Run ID#
Test Date
Run Start Time .......
Run Finish Time
Traverse Points (if applicable)
Net Run Time, min
Dry Gas Meter Calibration Factor
Barometric Pressure, in. Hg
Average DGM Temperature, °F
Absolute Average DGM Temperature, R
Average CO2/ %
Correction Factor for CO2
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Average N02 Per Sample, /jg
Sample Concentration, Ib/dscf
Audit Relative Error, %
Post-test Calibration Checks
Temperature and Barometer
Metering System
SUMMARY SHEET 7D
Nitrogen Oxides
FDS 6/7C
FDS 6/7C
FDS 6/7C
FDS 6/7C
FDS 6/7C
FDS6/7C
FDS 1
e
Y
Pb
tin
%CO2
X
m
m(std)
m
C
RE
FDS 6/7C
FDS 6/7C
FDS 6/7C
FDS 6/7C
FDS 6/7C
FDS 7C
SS7C
FDS 6/7C
SS7C
LDS7D
SS7D
QA1
CDS2d
CDS 6
Run#1
Run #2
9/30/94: S7D-1
Run #3 Avg
C = 6.242 x 1(rs
m
'm(std)
-------
9/30/94: L7D-1
LABORATORY PROCEDURE 7D
Nitrogen Oxide
A. Reagent Preparation
1. The following are the same as that in LP 7C:
a. Potassium Permanganate, 4.0%, Sodium
Hydroxide, 2.0% (A1).
b. Standard Potassium Nitrate (A12).
c. Blank Solution (A14).
2. Hydrogen Peroxide, 5%. Dilute 30% H202
1:5 (v/v) with water.
3. Eluent, 0.003 M NaHC03/0.0024 M Na2C03.
Dissolve 1.008 g NaHC03 and 1.018 g
Na2C03 in water, and dilute to 4 L. Other
eluents capable of resolving nitrate ion from
sulfate and other species present may be
used.
4. Quality Assurance Audit Samples. Obtain
fromEPA(seeQAI).
B. Calibration Curve for Ion Chromatograph.
1. Dilute a given volume (1.0 mL or greater) of
the KN03 standard solution to a known
volume with water.
2. With the KN03 solution prepare at least four
standards to cover the range of the samples
being analyzed. Use pipettes for all
additions.
3. Prepare the Chromatograph and set the
conditions to operate properly.
4. Analyze standards according to section D.
5. Determine peak height or area, and plot the
individual values versus concentration in
/jg NOg'/mL. Do not force the curve through
zero. Draw a smooth curve through the
points. Use linear regression to determine
the calibration equation.
C. Sampfe Preparation
1. Note the level of liquid in the sample
container, and determine loss; note this loss,
if any, on the laboratory data sheet.
2. Quantitatively transfer the contents to a 1 L
volumetric flask, and dilute to volume.
3. Prepare samples 36 hr after collection to
ensure that all N02' is converted to N03~.
4. Take a 50-mL aliquot of the sample and
blank, and transfer to 250-mL Erlenmeyer
flasks. Add a magnetic stirring bar. Stir as
fast as possible without loss of solution.
5. Using a 5-mL pipette, add 5% H202.
6. When the KMn04 color appears to have been
removed, allow the precipitate to settle, and
examine the supernatant liquid. If the KMn04
color persists, add more H202, with stirring,
until the supernatant liquid is clear. The
faster the stirring rate, the less volume of
H202 required to remove the KMn04.
7. Quantitatively transfer the mixture to a
Buchner funnel containing GF/C filter paper,
and filter. Filter the mixture into a 500 mL
filtering flask. Wash the solid material four
times with water.
8. When filtration is complete, wash the Teflon
tubing, quantitatively transfer the filtrate to a
250-mL volumetric flask, and dilute to
volume. Analyze the samples and blank.
D. Analysis
1. Establish a stable baseline.
2. Inject a sample of water, and determine
whether any N03~ appears in the
chromatogram.
3. If N03' is present, repeat the water
load/injection procedure approximately five
times; then re-inject a water sample, and
observe the chromatogram.
4. When no N03" is present, the instrument is
ready for use.
5. Inject calibration standards.
6. Inject samples and a blank.
7. Repeat the calibration standards injection (to
compensate for any drift in response of the
instrument).
8. Measure the N03~ peak height or peak area,
and determine the sample concentration from
the calibration curve.
9. Analyze the audit samples, if applicable.
-------
9/30/94'. LD7D-1
LABORATORY DATA SHEET 7D
Nitrogen Oxides
Client/Plant Name
Analyst
Job#
Date/Time
Water/NOg- Check (OK?)
Chromatographic Conditions:
Eluent:
Full scale range: (3 uMHO)?
Flow rate:
Cat. Stds
fc/g/NOg-)
(2.5m
Initial
L/min)? Retentior
(0.003M NaHCO ^0.0024 M Na2CO3)?
Sample loop: (0.5 mL)?
i time:
fappn
tx. 15minJ?
Final
Sample ID#
Blank, B
Audit Sample #1
Audit Sample #2
Volume
Loss, V|
(mL)
Sample
Volume, Vs
(mL)
Aliquot
Volume, Va
(mL)
Peak
Height/Area
N02
Analyzed, S
-------
9/30/94: F7E-1
FIELD PROCEDURE 7E
Nitrogen Oxides
(Instrumental Analyzer Procedure)
Nota: The procedure for FP 7E is essentially the same as that for FP 6C, except for the ob vious differences
due to the gases being analyzed and the detection device. The analyzer must be based on the principles of
chomilumlnescence. Follow FP 6C, except for the following:
1. Obtain calibration gases (NO in N2). Ambient
air may be used for the zero gas.
2. For non-Protocol 1 calibration gases.
Method 7 is the reference method and the
acceptance criterion is ±10% or 10 ppm,
whichever is greater. See CDS 6Ca.
3. Initially and whenever changes are made in
the instrumentation that could alter the
Interference response (e.g., changes in the
gas detector), conduct the interference
response test according to FP 20, step B3.
4. If the NO2 concentration within the sample
stream is >5% of the NOX concentration,
conduct an NO2 to NO conversion efficiency
test according to FP 20, step B5.
5. Select a measurement site and sampling
points using the same criteria that are
applicable to tests performed using
Method?.
6. Run for the same sampling duration per run
as that used for Method 7 plus twice the
stable response time for the instrument.
-------
Date
Analyzer Type
9/30/94: LD7E-1
LABQRATQRY DATA SHEET 7E
Interference Response
Personnel
Analyzer ID#
Test Gas
Nominal Concentration
Actual Concentration
Method 20
CO
S02
CO2
°2
500 ± 50 ppm
200 ± 20 ppm
.,.,10 ± 1 %
20.9 ±1%
Analyzer Response
% of Span
Span Value:
Method: Span Value:
«/0 of Span = Analyzer Response x 10Q
* Instrument Span
•v
Sum of the interference responses to the test gas for either the NOX or diluent analyzer <2% of span value?
NO2-NO Converter Efficiency
Peak response recorded during test
Response recorded at end of 3O minutes
% Decrease from peak response
(Attach strip chart or recorder readout)
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
-------
9/30/94: S8-1
SUMMARY SHEET 8
Sulfuric Acid Mist anJ Sulfur Dioxide
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Absolute Stack Pressure, in. Hg
Average Stack Temperature, °F
Average Absolute Stack Temperature, R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
DGM Sample Volume, dcf
DGM Sample Volume, dscf
Volume Water Condensed, mL
Volume Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(tsi +460)Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Volumetric Flow Rate, dscfh
Volumetric Flow Rate, wscfh
Isokinetic Sampling Rate, %
Normality, Ba Perchlorate Tftrant, meq/mL
Y
AH
%CO
%{CO + N2
Md
••m
m
V.
m(std)
Ic
w(std)
Ap
IT8i Ap]1/2
A
Qs
Qs
%l
N
Run #1
Run #2
Run #3
Avg
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 1
FDS 1
FDS 5
FDS 5
CDS 5
FDS 5
FDS 5
FDS 5
SS5
FDS 5
FDS 5
FDS 3
FDS 3
FDS 3
FDS 3 •
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS2a
FDS 5
FDS 5
SS5
FDS 1
SS5
SS5
SS5
LDS6
-------
9/30/94: S8-2
Run #1 Run #2 Run #3 Avg
Sulfuric Acid Mist
Volume of Sample Solution, mL Vs LDS 6
Volume of Sample Aliquot Titrated, mL Va LDS 6
Average Volume Titrant for Sample, mL Vt LDS 6
Volume Trtrant for Blank, mL Vb LDS 6
Acid Mist Concentration, Ib/dscf CH2SO4 ss 8
Sulfur Dioxide
Volume of Sample Solution, mL V6 LDS 6
Volume of Sample Aliquot Titrated, mL Va LDS 6
Average Volume Trtrant for Sample, mL Vt LDS 6
Volume Titrant for Blank, mL Vb LDS 6
Sulfur Dioxide Concentration, Ib/dscf Cso2 ss 6
Audit Relative Error, % RE QA1
Post-test Calibration Checks
Temperature and Barometer CDS 2d
Metering System CDS 5
Vm(std)
-------
9/30/94: F8-1
FIELD PROCEDURE 8
Sulfuric Acid Mist and Sulfur Dioxide
Note: This procedure is the same as that in Method 5 with some variations. Follow the procedure in
FP 5, except for .the obviously inapplicable parts. Some specifics are given below:
A. Pre-test Preparation
1. Inspect the filters, but do not desiccate,
weigh, or identify.
2. If the effluent gas can be considered dry,
i.e., moisture free, do not weigh the silica
gel.
3. Prepare the collection train (Figure F8-1.) as
follows:
a. Place 100 mL 80% isopropanol in the
first impinger.
b. Place 100 mL 3% hydrogen peroxide in
both the second and third impingers.
c. Retain a portion of each reagent for use
as a blank solution.
d. Place about 200 g silica gel in the
fourth impinger.
e. For moisture content, weigh each of the
first three impingers (plus absorbing
solution) to the nearest 0.5 g, and
record these weights. Weigh also the
silica gel (or silica gel plus container) to
the nearest 0.5 g, and record.
4. Optional: Leak-check the sampling train
(see FP 5a) from the inlet to the first
impinger. Adjust the probe heater to the
minimum temperature required to prevent
condensation.
B. Sampling
1. Do not exceed 1.0 cfm during the run.
2. Periodically check the connecting line
between the probe and first impinger for
signs of condensation. Adjust probe heater
as necessary to minimum temperature
required to prevent condensation.
3. If component changes are made during a
run, leak-check immediately before each
change, and record all leak rates.
Immediately after component changes, leak-
checks are optional.
4. At conclusion of run, drain the ice bath and,
with the probe disconnected, purge the
remaining part of the train with clean
ambient air for 15 min at the average flow
rate used for sampling. Either pass the air
through a charcoal filter or use ambient air
(without cleaning).
C. Sample Recovery
1. Container No. 1 (Sulfurir: Ahiri Mist)
. a. Transfer the contents of the first
impinger to a 250-mL graduated
cylinder.
b. Rinse the probe, first impinger, all
connecting glassware before the filter,
and the front half of the filter holder
with 80% isopropanol. Add the rinse
solution to the cylinder. Dilute to 250
mL with 80% isopropanol.
c. Add the filter to the solution, mix, and
transfer to the storage container.
Protect the solution against
evaporation.
d. Mark the level of liquid on the
container, and identify the sample
container.
2. Container No. 2 (SO2)
a; Transfer the solutions from the second
and third impingers to a 1 L graduated
cylinder.
b. Rinse all connecting glassware
(including back half of filter holder)
between the filter and silica gel
impinger with water, and add this rinse
water to the cylinder.
c. Dilute to 1 L with water.
d. Transfer the solution to a storage
container.
e. Mark the level of liquid on the
container. Seal and identify the sample
container.
,3. Container No. 3 (Silica Gell
If moisture is to be determined, see FP 5,
step E5.
-------
Figure F&-1. Sulfuric Acid Mist Sampling Train.
-------
9/30/94: L8-1
LABORATORY PROCEDURE 8
Sulfuric Acid Mist and Sulfur Dioxide
Note: LP 8 is the same as LP 6, except for the following variations to handle the larger samples. Use
LDS 6 for the analysis.
1. Container No. 1
a. Shake the container. If the filter breaks
up, allow the fragments to settle for a
few minutes before removing a sample.
b. Pipette a 100-mL aliquot of this solution
into a 250-mL Erlenmeyer flask and
titrate for sulfates.
2. Container No. 2.
a. Thoroughly mix the solution in the
container.
b. Pipette a 10-mL aliquot of sample into a
250-mL Erlenmeyer flask and add 40 mL
100% isopropanol.
G. Titrate for sulfates (see LP 6).
-------
-------
9/30/94: S10-1
SUMMARY SHEET 10
Carbon Monoxide
Run #1 Run #2 Run #3 Avg
Client/Plant Name FDS 10
Job No. FDS 10
Sampling Location FDS 10
Run ID # FDS 10
Test Date FDS 10
Run Start Time FDS 10
Run Finish Time FDS 10
Concentration of CO measured, dry, ppm Cco NDtR FDS 10
Vol. fraction of CO2 in sample, (%CO2/100) FCO2 FDS 3/3B
Cone, of CO in stack, dry, ppm Cco ^3^ SS 10
CO slack ~ GO NOIR
0
-------
Filter
(Glass Wool)
Probe
Condenser
Ice Water
Bath
To Analyzer
Figure F10-1. Continuous Sampling Train.
Filter
(Glow Wool)
\
Rata Mater
Condansar •
Ico Water
Bath
Quick
Disconnect
Rigid Container
Rgure F10-2. Integrated Gas-Sampling Train.
Sample
Needle 17=
Vah/e rJL,
Figure F10-3. Analytical Equipment.
Rate Meter
-------
9/30/94: F10-1
FIELD PROCEDURE 10
Carbon Monoxide
A. Pro-Test Preparation
Obtain a CO analyzer using nondispersive
infrared spectrometry, or equivalent. Obtain
from the manufacturer a certification that the
analyzer meets the specifications below:
Parameter
Range (min)
Output (min)
Min detectable sensitivity
Rise time, 90% (max)
Fall time, 90% (max)
Zero drift (min)
Span drift (max)
Precision
Noise (max)
Linearity (max dev)
Interference rejection ratio
Specification
0-1000ppm
0-1 OmV
20 ppm
30 sec
30 sec
10%in8hr
10% in 8 hr
±2% of full scale
±1% of full scale
2% of full scale
CO2: 1000 to 1
H2O: 500 to 1
2. Obtain CO calibration gases (CO in N2),
certified by the manufacturer to be within
±2% of the specified concentration, as
follows:
a. Span. £ 1.5 times the applicable
performance standard.
b. High-Range. About 60% of span.
c. Mid-Range. About 30% of span.
d. Zero. Prepurified grade of N2.
B. Continuous Sampling
1. Set up the equipment as shown in
Figures F10-1 and F10-2. Ensure that
all connections are leak free.
2. Prepare the CO analyzer according the
manufacturer's instructions. Allow at least
1 hr for warm-up. Calibrate the CO analyzer
according to the manufacturer's procedures
using N2 and the calibration gases. Record
the data on FDS 10.
3. Place the probe in the stack at a sampling
point, and purge the sampling line with stack
gas.
4. Connect the analyzer, and draw sample into
the analyzer. Allow 5 min for the system to
stabilize, then record the analyzer reading.
5. Before introducing each sample, purge
analyzer with N2.
6. After the test, check the zero and the span
again.
7. Determine the CO2 content of the gas
according to Method 3 or 36 integrated
sampling procedure (attach appropriate data
sheets).
C. Integrated Sampling
1. Leak-test the flexible bag. Evacuate the bag
with a pump followed by a dry gas meter.
After evacuation, the meter should indicate
zero flow.
2. Set up the equipment as shown in •-
Figure F10-3 with the bag disconnected.
Evacuate the flexible bag again, if necessary.
3. Place the probe in the stack at a sampling
point, and purge the sampling line with stack
gas.
4. Connect the bag. Ensure -fjiatall
connections are leak free.
5. Sample at a rate proportional to the stack
velocity. Use a pitot tube, if velocity is
varying with time.
6. Analyze the bag sample using appropriate
procedures in section B.
7. Determine the CO2 content as in step B7.
D. Alternatives
1. The sample conditioning system described in
Method 10A, sections 2.1.2 and 4.2, may
be used instead of the silica gel and ascarite
traps.
2. CO2 may be determined by weighing the
ascarite CO2 removal tube and computing
CO2 concentration from the gas volume
sampled and the weight gain of the tube.
-------
9/30/94: FD10-1
FIELD DATA SHEET 10
Analyzer Calibration
Client/Plant Name
City/State
Job #
Date/Time
Test Location,
Analyzer ID* _
Personnel
(Attach manufacturer's certification) Span
Note: Indicate units.
Analysis
Ctock
Time
Flow
Rate
Vel (Ap)
(if nee.)
Analyzer
Resp
Avg, Cco ND)R
CO Cone
(ppm)
Notts Attach FDS 3or3B for CO2 Analysis.
.5 Emission Limit)
Calibration Data
Level
Zero
Mid-range
(-30% span)
High-range
(-60% span)
Cylinder
Value
Analyzer
Response
». •
Attach plot of Cylinder Value vs. Analyzer Response.
,.-. . ,
Post-test Zero and Span Check
Level
Zero
Upscale
Cylinder
Value
Analyzer
Response
Drift
-
Analyzer Specifications
Parameter
Range (min)
Output (min)
Min detectable sensitivity
Rise time, 90% (max)
Fall time. 90% (max)
Zero drift (min)
Span drift (max)
Precision
Noise (max)
Linearity (max dev)
Interference rejection ratio
Specification
0-1 000 ppm
0-10.mV
20 ppm
30 sec
30 sec
10% in 8 hr
10%in8hr
±2% of full scale
±1% of full scale
2% of full scale
CO,: 1000 to 1
H2O: 500 to 1
QA/QC Check
Completeness
Legibility
Accuracy
Checked by:
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: S10A-1
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse points
Traverse Matrix (if rectangular)
Net Run Time, min
Sampling Rate, mL/min
C02 Concentration, fraction
Field Temperature, °C
Field Barometric Pressure, mm Hg
Average Absorbance
Absorbance, Reagent Blank
Room Temperature, °C
Lab Barometric Pressure, mm Hg
Bag Moisture Content
Cal Curve CO Concentration, ppm
Bag CO Concentration, ppm dry
Stack CO Concentration, ppm dry
SUMMARY SHEET 10A
Carbon Monoxide
FDS 10A
FDS 10A
FDS 10A
FDS 10A
FDS 10A
FDS 10A
FDS 10A
FDS 1
FDS1
6
a*
A
Ar
FDS 10A
FDS 10A
FDS 10A
FDS 10A
FDS 10A
LDS 10A
LDS 10A
LDS 10A
LDS 10A
LDS 10A
LDS 1OA
SS10A
SS10A
Run #1
Run #2
Run #3 Avg
-------
9/30/94: F10A-1
FIELD PROCEDURE 10A
Carbon Monoxide
A. Protest Preparation
1. Optional: Leak-check the bags before
sampling according to FP 3.
2. Loosely pack glass wool in the tip of the
probe.
3. Place 400 mL alkaline permanganate solution
in the first two irnpingers and 250 mL in the
third.
4. Evacuate the Tedlar bag completely using a
vacuum pump.
5. Assemble the sampling train as shown in
F10A-1. Do not connect the Tedlar bag to
the system at this time.
6. Leak-check the sampling system as follows:
plug the probe inlet, open the 3-way valve,
and pull a vacuum of ~250 mm Hg on the
system. No flow on the rate meter indicates
the system is leak free.
B. Sampling
1. Insert the probe into the stack and draw
sample through the system at 300 mL/min
± 10% and purge the system for 5 min.
2. Connect the evacuated Tedlar bag to the
system, and sample at a rate of 300 mL/min
for 30 min, or until the Tedlar bag is nearly
full.
3. Replace the scrubber solution after every
fifth sample or every 50 L of stack gas
when the concentration of SO2 or NOX is
< 1000 ppm and CO2 is < 15%, and more
often if greater.
4. Measure the CO2 content.to the nearest
0.5% each time a CO sample is collected. A
simultaneous grab sample with a Fyrite
analyzer is acceptable.
suck
xv
Prob*
Flur
(QlMiWccQ
V f
400 mL 250 mL
KMnQ4/NaOH
Rgure F10A-1. Sampling Train.
-------
9/30/94: FD10A-1
FIELD DATA SHEET 10A
Carbon Monoxide
: Name job #
Bar Press, Ph
on Personnel
mm Hg Date
-
City/State
Test Location
Optional pre-test leak check acceptable?
Bag evacuated until rotameter reads zero?
Sample line purged at 300 mL/min ± 10% for a5 min
before each sample?
Note start and end times:
Run#1
Run #2
Run #3
Time
Run #1
Rot Rdg
(mL/min)
Temp
Run #2
Time
Rot Rdg
(mL/min)
Temp
Run #3
Time
Rot Rdg
(mL/min)
Temp
Run#1
Run #2
. Run #3
Sampling rate 300 ± 30 mL/min?
Sampling time &30 min or bag almost full?
Fyrite CO2 (If Method 3 is used, attach FDS)
Rotameter Calibration Data Sheet attached?
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: L10A-1
LABORATORYPROCEDURE 10A
Carbon Monoxide
A. Reagents
1. Alkaline Permanganate, 0.25 M
KMnO4/1.5 M NaOH. Dissolve 40 g KMnO4
and 60 g NaOH in water, and dilute to 1 L.
2. Sodium Hydroxide, 1 M. Dissolve 40 g
NaOH in -900 mL of water, cool, and dilute
to1 L.
3. Silver Nitrate, 0.1 M. Dissolve 8.5 g AgNO3
in water, and dilute to 500 mL.
4. Para-Sulfaminobenzoic Acid (p-SABA), 0.1 M.
Dissolve 10.0 g p-SABA in 0.1 M NaOH, and
dilute to 500 mL with 0.1 M NaOH.
5. Colorimetric Solution. AddlOOmLof
p-SABA solution and 100 mL of AgNO3
solution into a flask. Mix, and add 50 mL of
1 M NaOH with shaking (should be clear and
colorless). Do not use after 2 days.
6. Standard Gas Mixtures. Use at least two
CO concentrations (in N2) between 50 and
1000 ppm (NIST-traceable) to span each
calibration range.
B, Equipment Preparation and Analysis
1. Calibrate the reaction bulbs as follows
(UseCDSlOA).
a. Weigh the empty bulb to ±0.1 g.
b. Fill the bulb to the stopcock with water,
and weigh to ±0.1 g.
c. Measure room temperature of water.
Calculate the volume to ±0.001 L using
the density of water at the measurement
' temperature.
2. Collect the standards according to FP 10A
to span 0-400 ppm or 40O-1000 ppm, or
both if samples occur in these ranges.
3. Assemble the system shown in L10A-1.
Pipet 10.O mL of the colorimetric reagent
into each gas reaction bulb, and attach the
bulbs to the system.
4. Evacuate the reaction bulbs and leak-check
the system as follows:
a. Open the stopcocks to the reaction
bulbs, but leave the valve to the Tedlar
bag closed.
b. Turn on the pump, fully open the coarse-
adjust flow valve, and slowly open the
fine adjust valve until the pressure is
reduced to at least 40 mm Hg.
c. Close the coarse adjust valve, and
observe the manometer after >2 min.
5.
6.
7.
8.
9.
A pressure increase of s1 mm Hg
indicates a leak.
d. Measure the vacuum pressure to
± 1 mm Hg, and close the reaction bulb
stopcocks.
Flush the manifold completely at least twice
as follows:
a. Open the Tedlar bag valve, and allow
the system to come to atmospheric
pressure.
b. Close the bag valve, open the pump
coarse adjust valve, and evacuate the
system again.
Transfer the standards and field samples
from each bag into the reaction bulbs as
follows (Analysis of each standard and
sample requires a set of three bulbs):
a. Close the pump coarse adjust.valve,
open the Tedlar bag valve, and let the
system fill to atmospheric pressure.
b. Open the stopcocks to the reaction
bulbs, and let the entire system come to
atmospheric pressure.
c. Close the bulb stopcocks, remove the
bulbs, record the room temperature and
barometric pressure to nearest mm Hg.
d. Place the bulbs on the shaker table with
their main axis either parallel to or
perpendicular to the plane of the table
top.
e. Purge the bulb-filling system with
ambient air for several minutes between
samples.
Prepare a set of three bulbs containing
colorimetric reagent but no CO as a reagent
blank.
Shake the samples for exactly 2 hr.
Immediately after shaking or as quickly as
possible, measure the absorbance of each
bulb sample at 425 nm if CO is <4OO ppm
or at 600 nm if CO is >400 ppm.
a. Use a small portion of the sample to
rinse a spectrophotometer cell several
times before taking an aliquot for
analysis.
b. If one cell is used to analyze multiple
samples, rinse the cell several times
between samples with water.
c. Use water as the reference. Reject the
analysis if the blank absorbance is
-------
10. Calculate the average absorbance for each
set of standards {two sets of three required
for each range). Plot a calibration curve
absorbance vs concentration. Draw a
smooth curve through the points. The curve
should be linear over the two concentration
ranges.
11. Reject the standard set if any of the
individual bulb absorbances differ from the
set mean by more than 10%.
9/30/94: L10A-2
12. Determine the CO concentration of each bag
sample using the calibration curve for the
appropriate concentration range.
C. Post- Test Leak-Check
Mandatory: Leak-check the bag according to
FP 3b.
Kudlon Bulbs
Flgura L10A-1. S.mplt Bulb Fining System.
-------
9/30/94: S10B-1
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse points
Traverse Matrix (if rectangular)
Net Run Time, min
Sampling Rate, mL/mln
C02 Concentration, fraction
Field Temperature, °C
Field Barometric Pressure, mm Hg
Average Injection Area
Average Response Factor
Room Temperature, °C
Lab Barometric Pressure, mm Hg
Bag Moisture Content
Cal Curve CO Concentration, ppm
Bag CO Concentration, ppm dry
Stack CO Concentration, ppm dry
SUMMARY SHEET 10B
Carbon Monoxide
FDS 10A
FDS 10A
FDS 10A
FDS 10A
FDS 10A
FDS 10A
FDS 10A
FDS1
FDS1
FDS 10A
0-8
F
tf
Pb
A
R
tf
Pb
Bw
%
c
FDS 10A
FDS 10A
FDS10A
FDS 10A
LDS 10B
LDS 1 0B
LDS 10B
LDS 10B
LDS 10B
LDS 1 0B
LDS 10B
SS 10B
Run*!
Run #2
Run ;"3 Avg
C=Cb(1-F)
-------
9/30/94: L10B-1
LABORATORYPROCEDURE 10B
Carbon Monoxide
A. Equipment Preparation and Checks
1. Obtain three standard gases with nominal
CO of 20-, 200-, and 1,000-ppm CO in N2
and standard CH4 gas of 1,000 ppm in air.
2. Establish an appropriate carrier flow rate and
detector temperature for the specific
instrument used.
3. Calibrate the analyzer as follows:
a. Inject in triplicate each of the standard
CO gases in step A1.
b. Calculate the average response factor
(area/ppm) for each gas and the overall
mean of the response factor values.
4. Analyze each new tank of carrier gas with
the GC analyzer in triplicate to check for
contamination.
5.
B.
1.
2.
a.
b.
Chec* the reduction catalyst efficiency as
follows:
Bypass the heated reduction catalyst,
and analyze in triplicate the 1,000 ppm
CH4 gas to calibrate the analyzer.
Repeat the procedure using 1,000-ppm
CO with the catalyst in operation.
c. Calculate the reduction catalyst
efficiency.
Analysis
Purge the sample loop with sample, and then
inject the sample.
Analyze each sample in triplicate, and
calculate the average sample area (A).
3. Determine the bag CO concentration.
-------
9/30/94: LD10B-1
LABORATORY DATA SHEET 10B
Carbon Monoxide
Client/Plant Name
City/State
Job #
Date
Gas Chromatograph ID #_
Room Temperature, °C _
Analyst
Barometric Pressure, Pb
Chromatograph Operation
mm Hg
' Parameter
N2 cylinder pressure
N2 flow rate setting
N2 backflush flow rate
Burner air supply
Burner air flow rate
H? cylinder pressure
Setting
psig
cc/min
cc/min
psig
cc/min
psig
(/)
Parameter
H2 flow rate
Oven temperature
Injection port
Detector
FID stabilized?
Setting
cc/min .
°C
°C
°C
(/)
Calibration
Sample
(Off
Injection 1
Area
Injection 2
Area
Injection 3
Area
Average
Area, A ,
Response
Factor, Rj
Carrier Gas Blank Check
Cylinder ID#
, ,' \ ••
>"* ':?$' '.-:•
CO concentration in the cylinder <5 ppm?
Reduction Catalyst Efficiency Check
1,000ppm CH4
Certified value
1 ,000 ppm CO
Certified value
/^
• ~,-.V"-.'
-.«• f '
S*~ >'<,**,
CO response within ±5% of the certified gas value?
Unoarity Chock
20 ppm CO
Certified value
200 ppm CO
Certified value
1,000 ppm CO
Certified value
Average Response Factor (R) =
Average response factor of each cal gas within ±2.5% of average response factor (R)7
Relative standard deviation for each set of triplicate injection < ±2%?
-------
9/30/94: LD10B-2
Sample Analysis
Samp
No.
Sample ID#
Injection 1
Area
Injection 2
Area
Injection 3
Area
Avg. Area
(A)
Conden-
sation?
(/)
Moisture
in Bag
-------
-------
9/30/94: S11-1
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (if rectangular)
Net Run Time, min
Barometric Pressure, mm Hg
DGM Calibration Factor
DGM Temperature, °C
DGM Sample Volume, L
DGM Sample Volume, L
Sample
Normality, Standard Iodine
Volume Titrated, 50 mL
Normality, Standard Thiosulfate
Volume Titrant, mL
Blank
Normality, Standard Iodine
Volume Titrated, 50 mL
Normality, Standard Thiosulfate
Volume Titrant, mL
H2S Concentration, mg/dscm
Post-test Calibration Checks
Temperature
Barometer
Metering System
SUMMARY SHEET 11
Hydrogen Sulfide
FDS 11
FDS 11
FDS 11
FDS 11
FDS 11
FDS 11
FDS 11
FDS1
FDS1
.0
Y6
'm(std)
N
.T
NT
,T
NT
TT
"H2S
FDS 11
FDS 11
CDS 6
FDS 11
FDS 11
SS11
LDS11
LDS11
LDS11
LDS 11
LDS 11
LDS 11
LDS 11
LDS 11
SS11
CDS2d
CDS2d
CDS 6
Run #1
Run #2 Run #3 Avg
Vm(std) . 0.3858 Y ^
CH,, = 17.04 X 103
. - [V^N, -
'm(std)
-------
9/30/94: F11-1
FIELD PROCEDURE 11
Hydrogen Sulfide of Fuel Gas Streams in Petroleum Refineries
A Sampling Preparation
1. Assemble the sampling train as shown in •
Figure F11-1.
a. Place 15 ml_ of 3% H202 solution in the
first impinger.
b. Leave the second impinger empty.
c. Place 15 mL of the CdS04 solution in
the third, fourth, and fifth impingers.
d. Place the impinger assembly in an ice
bath container, and place crushed ice
around the impingers. Add more ice
during the run, if needed.
2. Optional: Leak-check the sampling train as
follows:
a. Connect the rubber bulb and
manometer to the first impinger, as
shown in Figure F11-1. Close the
petcock on the DGM outlet.
b. Pressurize the train to 10 in. H2O with
the bulb, and close off the tubing
connected to the rubber bulb.
c. Time pressure drop (must be ^0.4-in.
drop in pressure in 1 min).
B. Sampling
1. Purge the connecting line between the
sampling valve and the first impinger as
follows:
a. Disconnect the line from the first
impinger, and open the sampling valve.
b. Allow process gas to flow through the
line for 1 to 2 min. Close the sampling
valve, and reconnect the line to the
impinger train.
2. Open the petcock on the dry gas meter
(DGM) outlet. Record the initial DGM
reading and the barometric pressure.
3. Open the sampling valve, and then adjust
the valve to obtain about 1 L/min. Maintain
a constant (±10%) flow rate during the
test.
4. Sample for at least 10 min. Take DGM and
temperature readings at least every 5 min.
5. At the end of the sampling time, close the
sampling valve, and record the final DGM
volume and temperature readings.
6. Mandatory: Leak-check the train (see A2).
7. Disconnect the impinger train from the
sampling line, and connect the charcoal tube
and the pump, as shown in Figure F11 -1.
8. Purge the train at 1 L/min with clean
ambient air for 15 min.
9. After purging, cap the open ends, and
remove the impinger train to a clean, well-
lighted area that is away from sources of
heat or direct sunlight.
C. Sample Recovery
Because analysis must immediately follow
sample recovery, see LP 11 for sample recovery.
Figure F11-1. H,S Sampling train.
-------
9/30/94: FD11-1
FIELD DATA SHEET 11
Hydrogen Sulf'de
Client/Plant Name
City/State
Job #
Date/Time
Test Location/Run #
Personnel
Train ID#/Sample Box #
Start Time End Time
DGM Cal Coef., Y
Ambient Temp., °C_
Bar. Pressure, Pb
mm Hg
Trav.
Pt.
Sarhplg
time
(min)
Total Time,
G*
DGM Rdg
(L)
„
Volume, Vm
Rotameter
Rdg
(cc/min)
Avg
Temperature (°C)
DGM
Av9, tm
Imp. Exit
Max
=£20°C?
Flow Rate Deviation
AVm
Avg
AVm/AVm
6.90- 1.10?
Leak-checks £0.4 in. H20/min
Run*
Pre (optional) (in./min)
Post (mandatory)(in./min)
Pressure (in. H2O)
Purge Rate
Purge Time
mm
Post-Test Calibrations:
Attach CDS 2d and CDS 6 for temperature (:£ ±5.4°F), barometer, and metering system calibration checks.
QA/QC Check
Completeness
Checked by: _
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: L11-1
LABORATORY PROCEDURE 11
Hydrogen Sulfide
A. Sample Recovery
1. Discard the contents of the H202 impinger.
2. Carefully transfer the contents of the third,
fourth, and fifth impingers into a 500-mL
Iodine flask. Rinse with water the
impingers and connecting glassware and
quantitatively transfer the rinse into the
iodine flask.
3. For a blank, add 45 mL CdS04 absorbing
solution to an iodine flask.
4. Pipette exactly 50 mL 0.01 N I2 solution
into a 125-mL Erlenmeyer flask. Add 10
mL 3 M HCI to the solution.
Note: If Antifoam B was not used or if
significant quantities of yellow CdS remain in the
impingers, go to step B6 (alternative).
5.
6.
Quantitatively transfer the acidified I2 into
each iodine flask. Stopper the flask
immediately, and shake briefly.
Alternative; Use the acidified I2 solution
(step B4) to extract any remaining CdS from
the third, fourth, and fifth impingers and
connecting glassware as follows:
a. Immediately after pouring the acidified I2
into an impinger, stopper it and shake for
a few moments, then transfer the liquid
directly to the iodine flask. Do not
transfer any rinse portion from one
impinger to another. Once the acidified
I2 solution has been poured into any
glassware containing CdS, stopper the
container at all times except when
adding more solution, and do this as
quickly and carefully as possible.
b. After adding any acidified I2 solution to
the iodine flask, allow a few minutes for
absorption of the H2S before adding any
further rinses.
c. Repeat the I2 extraction until any visible
CdS is removed from the impingers.
d. Quantitatively rinse all the I2 from the
impingers, connectors, and the beaker
into the iodine flask using water.
Stopper the flask and shake briefly.
7.
Allow the iodine flask to stand about
30 min in the dark for absorption of the H2S
into the I2.
8. Analyze the samples and blank immediately.
9. Recalibrate the metering system and
temperature gauges (see FP 2d and CP 6).
B. Reagent Preparation
1. CdS04 Absorbing Solution. Dissolve 41 g
3CdS04-8H2Oand 15 mL 0.1 M H2SO4 in a
1-L volumetric flask containing about 0.75 L
water. Dilute to volume with water. Mix
thoroughly. The pH should be 3 ± 0.1.
(Optional: Add 10 drops Dow-Corning
Antifoam B.) Shake well before use. Do not
use after 1 month.
. 2. H202, 3%. Dilute 30% H202 1:9 by volume,
as needed. Prepare fresh daily.
3. Hydrochloric Acid Solution, 3 M. Add
240 mL cone. HCI (s.g. 1.19}to500mL
water in a 1-L volumetric flask. Dilute to 1 L
with water. Mix thoroughly.
4. Iodine Solution, 0.1 N. Dissolve 24 g Kl in
30 mL water. Add 12.7 g resublimed I2 to
the Kl solution. Shake the mixture until the
I2 is completely dissolved. If possible, let
the solution stand overnight in the dark.
Slowly dilute the solution to 1 L with water,
with swirling. Filter the solution if it is
cloudy. Store solution in a brdwn-glass
reagent bottle.
5. .Standard I2 Solution, O.01 N. Pipette
100.0 mL 0.1 N iodine solution into a 1 L
volumetric flask, and dilute to volume with
water. Standardize daily. Protect this
solution from light. Keep reagent bottles and
flasks tightly stoppered.
6. Standard Sodium Thiosulfate Solution,
0.1 N. Dissolve 24.8 g sodium thiosulfate
pentahydrate (Na2S203-5H20) or 15.8 g
anhydrous sodium thiosulfate (Na2S203) in
1 L water, and add 0.01 g anhydrous sodium
carbonate (Na2C03) and 0.4 mL chloroform
(CHCI3) to stabilize. Mix thoroughly by
shaking or by aerating with nitrogen for
about 15 min, and store in a glass-
stoppered, reagent bottle.
7. Standard Sodium Thiosulfate Solution,
0.01 N. Pipette 50.0 mL the standard 0.1 N
Na2S2O3 solution into a volumetric flask, and
dilute to 500 mL with water.
8. Alternative to A7: Standard Phenylarsine
Oxide Solution, 0.01 N. Dissolve 1.80 g
C6H5AsO in 150 mL 0.3 N sodium
hydroxide. After settling, decant 140 mL of
this solution into 800 mL water. Bring the
solution to pH 6-7 with 6 N HCI, and dilute
to 1 L with water.
-------
c.
1.
2.
9. Starch Indicator Solution. Suspend 10 g
soluble starch in 100 mL water, and add
15 g KOH pellets. Stir until dissolved,
dilute with 900 mL water, and let stand for
1 hr. Neutralize the alkali with cone. HCI,
using an indicator paper similar to Alkacid
test ribbon, then add 2 mL glacial acetic
acid as a preservative.
0.1 NNa2S2O3 Reagent Standardizations
Weigh and transfer 2 g dried potassium
dichromate (K2Cr207) to a 500-mL
volumetric flask. Dissolve in water and
dilute to exactly 500 mL.
In a 500-mL iodine flask, dissolve about 3 g
Kl in 45 mL water, then add 10 mL 3 M HCI
solution. Pipette 50 mL dichromate solution
into this mixture. Gently swirl the solution
once, and allow it to stand in the dark for
5 min. Dilute the solution with 100 to
200 mL water, washing down the sides of
the flask with part of the water. Titrate
with 0.1 N Na2S2O3 until the solution is
light yellow.
Add 4 mL starch indicator and continue
titrating slowly to a green end point.
Repeat titrations until replicate analyses
agree within 0.05 mL, and average these
values.
Calculate the normality. Repeat each week,
or after each test series, .whichever time is
shorter.
O.O1 N CgHgAsO Standardization (if
applicable)
Weigh and transfer 2 g K2Cr207 to a 500-
mL volumetric flask. Dissolve in water, and
dilute to exactly 500 mL.
2. In a 500 mL iodine flask, dissolve
approximately 0.3 g Kl in 45 mL water; add
10mL3MHCI. Pipette 5 mL dichromate
solution into the iodine flask. Gently swirl
the contents of the flask once allow to
stand in the dark for 5 min. Dilute the
solution with 100 to 200 mL water,
washing down the sides of the flask with
part of the water. Titrate with
0.01 N C6HsAsO until the solution is light
yellow.
3. Add 4 mL starch indicator, and continue
titrating slowly to a green end point.
4.
5.
D.
1.
5.
E.
1.
L11-2
4. Repeat titrations until replicate analyses
agree within 0.05 mL, and average these
values.
Calculate the normality. Repeat each week
or after each test series, whichever time is
shorter.
0.01 NI2 Reagent Standardization
Pipette 25 mL standard I2 solution into a
125-mL Erlenmeyer flask. Add 2 mL
3 M HCI. Titrate rapidly with standard
0.01 N Na2S2O3 solution or with 0.01 N
C6H5AsO until the solution is light yellow,
using gentle mixing.
2. Add four drops starch indicator solution, and
continue titrating slowly until the blue color
just disappears.
3. Repeat titrations until replicate values agree
within 0.05 mL, then average these values.
4. Calculate normality of the I2 solution.
Repeat daily.
F. Analysis
1. Test starch indicator solution for
decomposition by titrating with 0.01 N I2
solution, 4 mL starch solution in 200 mL
water that contains 1 g Kl. If more than
4 drops of 0.01 N I2 standard solution are
required to obtain the blue color, prepare a
fresh solution.
2. Conduct titration analyses immediately after
recovery to prevent loss of I2 from the
sample. Avoid direct sunlight. (See
LDS11).
3. Rapidly titrate each sample with 0.01 N
Na2S2O3 solution (or 0.01 N CeH5AsO, if
applicable), in an iodine flask, to a light
yellow color.
4. Add 4 mL starch indicator solution, and
continue titrating slowly until the blue color
just disappears.
5. Titrate the blanks in the same manner as the
samples.
6. Run blanks each day until replicate values
agree within O.05 mL, and average them.
-------
9/30/94: LD11-1
LABORATORY DATA SHEET 11
Hydrogen Sulfide
Client/Plant Name
City/State
Analyst
Job #
Date Analyzed
Sampling Location
Time Analyzed
Run
No.
Blank # 1
Blank # 2
Sample
Total, V
(mL)
Aliquot, A
(mL)
Factor,
F = V/A
Sample Titration
TI
(mL)
T2
(mL)
\
( •
Avg, VT-T
(mL)
No.
1
2
Avg
K2Cr207, W
(g)
Thiosulfate Standard Titration
Volume, Vs
(mL)
Normality,
MS
Iodine Standard Titration
Aliquot, V(
(25 mL)
Volume, VT
(mL)
Normality,
N,
•
Analyses started within 1 hr of sampling?
Titrations done 30 min after adding acidified
Iodine solution?
All replicate titrations agree within 0.05 mL?
Starch indicator tested for decomposition?
Ns = 2.039 —
NT = 0.10 Ns
N. =
NTVT
V,
Note: This data sheet is designed to be used with standard thiosulfate solution; if standard phenylarsine is used,
make the necessary changes according to Method 11.
QA/ac Check
Completeness
Checked by: _
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: SS12-1
SUMMARY SHEET 12
Inorganic Lead
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Absolute Stack Pressure, in. Hg
Average Stack Temperature, °F
Average Absolute Stack Temperature, R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pilot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [{tsi +460) Ap]W2
Velocity, ft/sec
Stack Area, ft2
Volumetric Flow Rate, dscfh
Volumetric Flow Rate, wscfh
Isokinetic Sampling Rate, %
Pb Concentration from Cal Curve, /jg
Sample Volume, mL
Aliquot Volume, mL
Dilution Factor, if applicable
Total Pb in Sample, //g
Pb Concentration, Ib/dscf
Post-test Calibration Checks
Temperature and Barometer
Metering System
e
Dn
Y"
AH
Pb
Pg
PS
ts
Ts
%CO2
%02
%(CO + N2)
Md
tm
vm
Vm(std)
V|c
Vw(std)
Bws
CP
Ap
[TsiAp]1'2
vs
A
Qsd
Qsw
%l
cc
V°
F8
r°
^ Pb
Cph
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 1
FDS 1
FDS 5
FDS 5
CDS 5
FDS 5
FDS 5
FDS 5
SS5
FDS 5
FDS 5
FDS 3
FDS 3
FDS 3
FDS 3
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS2a
FDS 5
FDS 5
SS5
FDS 1
SS5
SS5
SS5
LDS 12
LDS 12
LDS 12
SS 12
SS12
o° -
°Pb -
^F
CDS2d
CDS 5
Run#1
Run #2
Run #3 Avg
= 2.205 x 10-9
Pb
m(std)
-------
9/30/94: F12-1
FIELD PROCEDURE 12
Inorganic Lead
Note: The sampling procedure is the same as that in FP 5, except for the following (use FDS 5 for the
sampling data}.
A. Sampling
1. Use a filter with a lot assay for lead; the
filter need not be weighed.
2. Assemble the train as shown in Figure F12-
1. Use impingers rather than an alternative
condenser system.
3. In each of the first two impingers, place
100 mL 0.1 N HN03 (rather than water).
4. Use as sample storage containers 1 L
borosilicate glass bottles with screw-cap
liners that are either rubber-backed Teflon or
leak-free and resistant to chemical attack by
0.1 N HN03.
B. Sample Recovery
1. The sample recovery procedure for
Containers 1, 2, and 3 is the same as that
in FP 5, except for the following:
a. Use 0.1 N HNO3 as the rinse rather than
water; save a blank of the acid.
b. Use glass rather than a polyethylene
funnel.
2. Container No. 4 (Impingers}. Several
sample containers may be used. Clean each
of the first three impingers and connecting
glassware in the following manner:
a. Wipe the impinger ball joints free of
silicone grease, and cap the joints.
b. Rotate and agitate each impinger, so that
the impinger contents might serve as a
rinse solution.
c. Remove the outlet ball joint cap, and
drain the contents through this opening
into a 500-mL graduated cylinder; do not
separate the impinger parts (inner and
outer tubes) during this operation.
Measure the liquid volume to within
2 mL. Alternatively, weigh the liquid to
within 0.5 g. Note any color or film
observed in the impinger catch.
d. Transfer the contents to Container No. 4.
e. Measure and record the total amount of
0.1 N HN03 used for rinsing in this step
and in step f below. Pour about 30 mL
0.1 N HN03 into each of the first three
Impingers and agitate the impingers.
Drain the 0.1 N HN03 through the outlet
arm of each impinger into Container
No. 4. Repeat this operation a second
time; inspect the impingers for any
abnormal conditions.
f. Wipe the socket joints of the glassware
connecting the impingers free of silicone
grease and rinse each piece of
glassware twice with 0.1 N HN03;
transfer this rinse into Container No. 4.
(Do not rinse or brush the glass- fritted
filter support.)
g. Mark the height of the fluid level and
label and identify the container.
C. Alternatives
1. Simultaneous Determination of Particulate
and Lead Emissions. Method 5 (FR 5) may
be used to simultaneously determine Pb
provided that:
a. Acetone is used to remove particulate
from the probe and inside of the filter
holder as specified by Method 5.
b. 0.1 N HN03"is used in the impingers.
c. A glass fiber filter with a low Pb
background is used.
d. The entire train contents, including the
impingers, are treated and analyzed for
Pb.
2. Filter Location. A filter may be used
between the third and fourth impingers
provided that the filter is included for
analysis for Pb.
3. In-Stack Filter. An in-stack filter may be
used provided that:
a. A glass-lined probe and at least two
impingers, each containing 100 mL
0.1 N HN03/ are used after the in-stack
filter.
b. The probe and impinger contents are
recovered and analyzed for Pb.
(Recover sample from the nozzle with
acetone if a particulate analysis is to be
made.)
-------
Temperature
Temperature8^ Sensor
Heat —L
Temperature
Sensor
Type S Pilot
Tube
Manometer Temperature
Figure F12-1. Inorganic Lead Sampling Train.
-------
9/30/94: L12-1
LABORATORYPROCEDURE 12
Inorganic Lead
A. Reagent Preparation
1. Nitric Acid, 0.1 N. Dilute 6.5 mL cone. HN03
to 1 L with water.
2. HN03/ 6 N. Dilute 390 mL cone. HN03 to 1 L
with water.
3. HNO3, 50% (v/v). Dilute 500 mL cone. HN03
to 1 L with water.
4. Stock Lead Standard Solution, 1000//g
Pb/mL. Dissolve 0.1598 g Pb(N03)2 in about
60 mL water, add 2 mL cone. HN03, and
dilute to 100 mL with water.
5. Working Lead Standards. Pipet 0.0, 1.0,
2.0, 3.0,4.0, and 5.0 mL stock lead
standard solution into 250-mL volumetric
flasks. Add 5 mL cone. HN03 to each flask,
and dilute to volume with water. These
working standards contain 0.0, 4.0,8.0,
12.0,16.0, and 20.0//g Pb/mL, respectively.
Prepare, as needed, additional standards at
other concentrations in a similar manner.
6. Hydrogen Peroxide, 3%. Dilute 10 mL 30%
H202 to 100 mL with water.
B. Sample Preparation
1. Container No. 1 (Filter)
a. Cut the filter into strips and transfer the
strips and all loose particulate matter into
a 125-mL Erlenmeyer flask. If the
estimated particulate catch is greater
than 800 mg, use a 250-mL flask (see
step B3).
b., Rinse the petri dish with 10 mL
50% HN03 to insure a quantitative
transfer, and add to the flask.
2. Containers No. 2 and No. 4 (Probe and
Impingers)
a. Check the liquid level in Containers No. 2
and No. 4, and determine and record
loss (if any) on LDS 12.
b. Combine the contents of Containers
No. 2 and No. 4, and take to dryness on
a hot plate.
3. Sample Extraction for Lead
a. Based on the approximate stack gas
particulate concentration and the total
volume of stack gas sampled, estimate
the total weight of particulate sample
collected.
b. Then transfer the residue from
Containers No. 2 and No. 4 to the
125-mL Erlenmeyer flask that contains
the filter using rubber policeman and
10 mL 50% HN03 for every 100 mg of
sample collected in the train or a
minimum of 30 mL 50% HN03,
whichever is larger.
c. Place the Erlenmeyer flask on a hot
plate, and heat with periodic stirring for
30 min at just below the boiling point. •
If the sample volume falls below 15 mL,
add more, 50% HN03. Add 10 mL 3%
H202, and continue heating for 10 min.
Add 50 mL hot (80° C) water, and heat
for 20 min. Remove the flask from the
hot plate, and allow to cool.
d. Filter the sample through a Millipore
membrane filter, or equivalent, and
transfer the filtrate to a 250-mL
volumetric flask. Dilute to volume with
water.
4. Filter Blank
a. Take two filters from each lot of filters
' used in the sampling train.
b. Cut each filter into strips, and place
each filter in a separate 125-mL
Erlenmeyer flask.
c. Add 15 mL 50% HN03, and treat as
described in step B using 10 mL
3% H202 and 50 mL hot water. Filter
and dilute to a total volume of 100 mL
with water.
5. HN03 Blank
a. Take the entire 200 mL 0.1.N HN03 to
dryness on a steam bath.
b. Add 15 mL 50% HN03, and treat as
described in section B3 using 10 mL
3% H202 and 50 mL hot water. Dilute
to a total volume of 100 mL with water.
C. Analysis
1. Calibrate the spectrophotometer as follows:
a. Measure the absorbance of the standard
solutions using the instrument settings
recommended by the spectrophotometer
manufacturer. Repeat until good
agreement (< ±3%) is obtained
between two consecutive readings.
-------
9/30/94: L12-2
b. Plot the absorbance (y-axis) versus
concentration in //g Pb/mL (x-axis).
Draw or compute a straight line through
the linear portion of the curve. Do not
force the calibration curve through zero,
but if the curve does not pass through
the origin or < ±0.003 absorbance
units, check for incorrectly prepared
standards and for curvature in the
calibration curve.
c. To determine stability of the calibration
curve, run a blank and a standard after
every five samples, and recalibrate, as
necessary.
2. Lead Determination
a. Determine the absorbance for each
source sample, the filter blank, and
0.1 N HN03 blank. Analyze each sample
three times in this manner. Make
appropriate dilutions, as required, to
bring all sample Pb concentrations into
the linear absorbance range of the
spectrophotometer.
b. If the Pb concentration of a sample is at
the low end of the calibration curve and
high accuracy is required, take the
sample to dryness on a hot plate and
dissolve the residue in the appropriate
volume of water to bring it into the
optimum range of the calibration curve.
c. If high concentrations of copper are
present, analyze the samples at
283.3 nm.
3. Container No. 3 (Silica Gel). If not done in
the field, weigh the spent silica gel (or silica
gel plus impinger) to the nearest 0.5 g.
D. Check for Matrix Effects
Check at least one sample from each source
using the Method of Additions as follows:
1. Add or spike an equal volume of standard
solution to an aliquot of the sample solution,
then measure the absorbance of the resulting
solution and the absorbance of an aliquot of
unspiked sample.
2. Calculate the Pb concentration C« in //g/mL
of the sample solution. Volume corrections
are not required if the solutions as analyzed
are made to the same final volume.
Therefore, C, and C. represent Pb
concentrations before dilutions.
3. Method of Additions procedures described
on pages 9-4 and 9-5 of the section entitled
"General Information" of the Perkin Elmer
Corporation Atomic Absorption
Spectrophotometry Manual, No. 303-0152
may also be used.
4. If the results of the Method of Additions
procedure used on the single source sample
is > ±5% of the value obtained by'the
routine atomic absorption analysis, then
reanalyze all samples from thersource using
the Method of Additions procedure.
-------
9/30/94: LD12-1
LABORATORY DATA SHEET 12
Inorganic Lead
Client/Plant Name
Job #
Daterrime
Spcctrophotometer ID#
Wavelength
_nm Analyst
Working Standards (UQ Pb/mU
Absorbance 1 , A1
Absorbance 2, A2
Q/C chk (AT - Ajjl/A, (£ ±3%) (/)
0.0
4.0
8.0
12.0
16.0
20.0
Plot of calibration curve attached?
Curve £ ±0.003 absorbance units of the origin?.
Note: If copper is present in high concentrations, use 283.3 nm to analyze the samples.
Sample ID#
Filter Blank
0.1 N HNO3 Blank
Spiked Sample
Unspiked Sample
Cal Blank*
Cal Standard*
Volume (mL)
Loss, V,
Smpl, Vs
A|iqt, Va
Absorbance, A (OD)
AI
A2
A3
Avg
(•'•
Corr**
\
''
Pb
Cone, Cc
U/g/mL)
* Run these calibration checks (blank and standard) every 5 samples.
** Subtract filter and 0.1 N HN03 blanks from average absorbance.
Matrix Check Spike:
/•» r* •
Cs = Pb concentration
Dilutions?
Ca = Pb standard concentration, //g/mL =
A, - A. AS = Absorbance, unspiked sample
Aj = Absorbance, spiked sample
Cf £i ±0.05unspiked concentration?
Note: If the 5% specification is not met, run all samples using Method of Addition.
QA/CLC Chock
Completeness
Checked by: _
Legibility
Accuracy
Specification^
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: LO12a-1
LABORATORY DATA SHEET 12a
Matrix Analysis
Client/Plant Name
Job #
Date/Time
Analyst
Note: This is a generic form for the Methods of Addition. Add the proper units. Make any adjustments as
appropriate.
\ ' " ^ ^ <^rrr ^ v?
Sample ID
Spiked Sample, S
Unspiked Sample, U
Difference, D
Standard, R
%R = (D - R)/R
Measurement Units
i
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
-------
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Abs Stack Pressure (Pb + Pg/13.6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temperature (ts + 460), R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(tsi +460) Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Isokinetic Sampling Rate, %
Total Fluoride in Sample, mg
In-stack Concentration of F, mg/ft3
Post-test Calibration Checks
Temperature and Barometric Pressure
Differential Pressure Gauges
Metering System
SUMMARY SHEET 13A
Total Fluoride
FDS5
FDS5
FDS5
FDS5
FDS5
FDS5
FDS5
FDS 1
FDS 1
FDS 5
Y
AH
%CO2
%02
%(CO + N2)
"•m
m(std)
'Ic
/w(stdj
rrsi AP]
%i
1/2
FDS 5
CDS 5
FDS 5
FDS 5
FDS 5
SS5
FDS 5
SS5
FDS 3
FDS 3
FDS 3
FDS 3
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS2a
FDS 5
FDS 5
SS5
FDS 1
SS5
LDS 13A
SS13A
CDS2d
CDS2d
CDS 5
Run#1
9/30/94: S13A-1
Run #2 Run #3 Avg
C, =
' m(std)
-------
9/30/94: F13A-1
FIELD PROCEDURE 13A
Total Fluoride
(SPADNS Zirconium Lake Method)
This field procedure applies also to Method 13B, except references to chloride and sulfate interferences
are not applicable. The sampling procedure is the same as that in FP 5, except for the following:
A. Sampling
1. The filter position is interchangeable (see
Figure F13A-1).
a. If placed between the probe and first
irnpinger, use a Whatman No. 1 filter and
borosilicate glass or stainless steel with a
20-mesh stainless steel screen filter
support and a silicone rubber gasket; do
not use a glass frit or a sintered metal
filter support in this position.
b. If placed between the probe and first
irnpinger, use any suitable medium (e.g.,
paper, organic membrane) with the
following specifications: (1) Able to
withstand prolonged exposure to
temperatures up to 275 °F. (2) Has
efficiency &95% for 0.3pm dioctyl
phthalate smoke particles. (3) Has a
blank value of <0.015 mg F/cm2 of filter
area. (In general, glass fiber filters have
high and/or variable F blank values, and
will not be acceptable for use.)
2. When moisture condensation is a problem, a
filter heating system set at =s248 ± 25°F
may be used.
3. Use impingers rather than an alternative
condenser system.
4. For the sample storage containers for
irnpinger water, use high-density
polyethylene bottles.
5. The filter need not be weighed. Before the
test series, determine the average F blank
value of at least three filters from the lot to
be used for sampling (see LP 13A).
6. Select the nozzle size to maintain isokinetic
sampling rates below 1.0 cfm.
7. Grease on sample-exposed surfaces may
cause low F results due to adsorption.
B. Sample Recovery
The quantitative sample recovery technique is
the same as that in FP 5. Water is used as the
wash rather than acetone. Recover the samples
in the following containers:
1. Container No. 1 (Probe, Filter, and Irnpinger
Catches).
a. Using a graduated cylinder, measure to
the nearest mL the volume of the water
• in the first three impingers; include any
condensate in the probe in this
determination.
b. Transfer the irnpinger water from the
graduated cylinder into this polyethylene
container.
c. Add the filter to this container. (The
filter may be handled separately using
procedures subject to the
Administrator's approval.)
d. .Add the water washings from all
sample-exposed surfaces (including the
probe nozzle, probe fitting, probe liner,
first three impingers, irnpinger
connectors, and filter holder). Use
<500 mL for the entire wash.
2. Container No. 2 (Sample Blank)
a. Prepare a blank by placing an unused
filter in a polyethylene container and
adding a volume of water equal to the
total volume in Container No. 1.
b. Process the blank in the same manner
as that for Container No. 1.
3. Container No. 3 (Silica Gel). Use FP 5,
step E5.
-------
Type S Pilot
Tube
Stick
Will
A He"
S \ Traced
I I Glait-lined
U / Probe
I Optional Filler I
•Holder Location)
Filler
Holder Temperature
\Sensor
A 9
Figure F13A-1. Fluoride Sampling Train.
Connecting Tube
12 mm ID
1-Liter
Flask"
500-ml _
Ertenmeyer
Flask
Condenser
Figure L13A-1. Fluoride Distillation Apparatus.
-------
9/30/94: L13A-1
LABORATORY PROCEDURE13A
Total Fluoride
(SPADNS Zirconium Lake Method)
A. Reagent Preparation
1. Phenolphthalein Indicator. Dissolve 0.1 g
phenolphthalein in a mixture of 50 mL
90% ethanol and 50 mL water.
2. Sulfuric Acid, 25%. Mix 1 part of cone.
H2SO4 with 3 parts of water.
3. Fluoride Standard Solution, 0.01 mg F/mL.
Oven dry at 110°C for &2 hr. Dissolve
0.2210 g of NaF in 1 L water. Dilute 100 mL
of this solution to 1 L with water.
4. SPADNS Solution [4,5
Dihydroxy-3-(p-SuIfophenylazo)-2,7-
Naphthalene-Disulfonic Acid Trisodium Salt].
Dissolve 0.960 ± 0.010 g SPADNS reagent
in 500 mL water. Solution stored in a
well-sealed bottle protected from the sunlight
is stable for at least 1 month.
5. Spectrophotometer Zero Reference Solution.
Prepare daily. Add 1O mL SPADNS solution
to 100 mL water, and acidify with a solution
prepared by diluting 7 mL cone. HCI to 10 mL
with water.
6. SPADNS Mixed Reagent. Dissolve
0.135 ± 0.005 g of ZrOCI2-8H2O in 25 mL .
water. Add 350 mL cone. HCI, and dilute to
500 mL with water. Mix equal volumes of
this solution and SPADNS solution to form a
single reagent. This reagent is stable for at
least 2 months.
B. Sample Preparation and Distillation
1. Check the liquid levels in Containers No. 1
and No. 2, and determine and record loss (if
any) on LDS 13A.
2. Container No. 1 (Probe, Filter, and Impinger
Catches)
a. Filter contents, including the sampling
filter, through Whatman No. 541 filter
paper into a 1500-mL beaker.
b. If the filtrate volume >900 mL, make
the filtrate basic (red to phenolphthalein)
with NaOH, and evaporate to <900 mL.
c. Place the filtered material (including
sampling filter) in a nickel crucible, add a
few mL of water, and macerate the
filters with a glass rod.
d. Add 100 mg CaO (certified grade
^0.005% F) to the crucible, and mix the
contents thoroughly to form a slurry.
Add two drops of phenolphthalein
indicator. Place the crucible in a hood
under infrared lamps or on a hot plate at
low heat. Evaporate the water
completely. During the evaporation of
the water, keep the slurry basic (red to
phenolphthalein) to avoid loss of F. If
the indicator turns colorless (acidic)
during the evaporation, add CaO until
the color turns red again.
e. After evaporating the water, place the
crucible on a hot plate under a hood,
and slowly increase the temperature
until the Whatman No. 541 and
sampling filters char completely (may
take several hours).
f. Place the crucible in a cold muffle
furnace. Gradually (to prevent smoking)
increase the temperature to 600 °C, and
maintain until the contents are reduced
to an ash. Remove the crucible from
the furnace, and allow to cool.
g. Add about 4 g crushed NaOH to the
crucible, and mix. Return the crucible
to the muffle furnace, and fuse the
sample for 10 min at 600dC.
h. Remove the sample from the furnace,
and cool to ambient temperature. Using
several rinsings of warm water, transfer
the contents of the crucible to the
beaker containing the filtrate. To assure
complete sample removal, rinse finally
with two 20-mL portions of 25%
H2SO4, and carefully add to the beaker.
Mix well, and transfer to a 1-L
volumetric flask. Dilute to volume with
water, and mix thoroughly. Allow any
undissolved solids to settle.
3. Container No. 2 (Sample Blank). -Treat in the
same manner as described in step B2.
C. Distillation
1. Adjust the acid/water ratio of the distillation
flask as follows:
a. Using a protective shield, place 400 mL
water in the distillation flask, and add
200 mL cone. H2S04. (Caution:
Observe standard precautions when
mixing H2SO4 with water. Slowly add
the acid to the flask with constant
swirling.)
b. Add some soft glass beads and several
small pieces of broken glass tubing, and
assemble the apparatus as shown in
Figure L13A-1. Heat the flask until it
reaches 175°C. Discard the distillate.
-------
9/30/94: L13A-2
2. Cool the contents of the distillation flask to
<8O°C. Pipet an aliquot of sample
containing less than 10.0 mg F directly into
the distillation flask, and add water to make a
total volume of 220 mL added to the
distillation flask. (To estimate the appropriate
aliquot size, select an aliquot of the solution,
and treat as described in step D2.)
3. If the sample contains chloride, add 5 mg
Ag2SO4 to the flask for every mg of chloride.
Note: It may be easier to use the Specific
Ion Electrode Method (Method 13B).
4. Place a 250-mL volumetric flask at the
condenser exit. Heat the flask as rapidly as
possible with a Bunsen burner, and collect all
the distillate up to 1.75°C. During heatup,
play the burner flame up and down the side
. of the flask to prevent bumping. Conduct the
distillation as rapidly as possible (15 min or
less). Slow distillations produce low F
recoveries. Caution: Be careful not to exceed
175 °C to avoid causing H2SO4to distill over.
5. If F distillation in the fractional mg range is to
follow distillation in the mg range, add
220 mL of water, and distill it over as in the
acid adjustment step to remove residual F
from the distillation system.
6. After every tenth distillation, check the
distillation flask for carry-over of
interferences or poor F recovery by using a
water blank and a standard solution. Change
the acid whenever the F recovery is less than
90% or the blank value exceeds O.1 //g/mL.
D. Analysis
1. Spectrophotometer Calibration
a. Add 10 mL SPADNS mixed reagent to
50 mL water for the blank standard.
b. Dilute 0, 2, 4, 6, 8, 10, 12, and 14 mL
of the 0.01 mg F/mL standard fluoride
solution to 100 mL with water.
c. Pipet 50 mL from each solution, and
transfer each to a separate 100-mL
beaker. Then add 10 mL SPADNS mixed
reagent to each to make 0, 10, 20, 30,
40, 50, 60, and 70 //g F (0 to
1.4 fjg/mL), respectively.
d. After mixing, place the reference
standards and reference solution in a
consta.nt temperature (± 1 °C) bath for
30 min. Then read the absorbance with
the spectrophotometer within 2 hr.
e. With the spectrophotometer at 570 nm,
use the reference solution (step D1a) to
set the absorbance to zero.
f. Determine the absorbance of the
standards. Prepare a calibration curve
by plotting /JQ F/50 mL versus
absorbance on linear graph paper.
Prepare the standard curve initially and
thereafter whenever the SPADNS mixed
reagent is newly made. Also, run a
calibration standard with each set of
samples and, if it differs from the
calibration curve by ±2%, prepare a
new standard curve.
2. Containers No. 1 and No. 2
a. Dilute the distillate in the volumetric
flasks to exactly 250 mL with water,
and mix thoroughly. Pipet a suitable
aliquot of each sample distillate
(containing 10 to 40 fjg F/mL) into a
beaker, and dilute to 50 mL with water.
Use the same aliquot size for the blank.
Add 10 mL SPADNS mixed reagent and
mix thoroughly.
b. Place the sample in the same constant-
temperature bath as that c6ntaining the
standard solutions for 30 min. A 3°C
difference between the sample and
' standard solutions produces an error of
about 0.005 mg F/L.
c. Set the spectrophotometer to zero
absorbance at 570 nm with the
reference solution, and check the
spectrophotometer calibration with the
standard solution.
d. Determine the absorbance of the
samples, and determine the
concentration from the calibration
curve.
e. If the concentration does not fall within
the range of the calibration curve,
repeat the procedure using a different
size aliquot.
3. Container No. 3 (Silica Gel). If not done in
the field, weigh the spent silica gel (or silica
gel plus impinger) to the nearest 0.5 g.
-------
9/30/94: LD13A-1
LABORATORY DATA SHEET 13A
Total Fluoride - SPADNS Zirconium Lake
Client/Plant Name
Job #
Date/Time
Spectrophotometer ID#
Wavelength 750 nm { /
Ambient Temp.
Analyst
°F Bath Temp.
°F Calibration Date
Working Standards
U/g F/mL)
Absorbance 1
Absorbance 2
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
SPADNS reagent prepared within the last two months?
Plot of calibration curve attached?
Zero reference solution prepared daily?
Note: Run a calibration standard with every set of samples and if it differs from the curve by 5: ±2%, run a new
calibration curve.
Sample ID ft
Cal Std
Sample
Vol.,
vt
(ml)
Aliquot
Vol.,
At
(ml)
Chloride in
Sample,
(mg)
Ag2S04
Added,
(mg)
Vol. of
Distillate,
vd
(ml)
Aliquot of
Distillate,
Ad
(mL)
Absorption
at 570 nm,
(O.D.)
//g F in •
sample
Total weight
of F,
Ft
(mg)
_ Standards and samples placed in same constant temperature bath?
Total Fluoride in Sample, mg:
F • 10"
QA/aC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: S13B-1
SUMMARY SHEET 13B
Total Fluoride
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Abs Stack Pressure (Pb + Pg/13;6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temperature (ts + 460), R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume- of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(tsi +460) Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Isokinetic Sampling Rate, %
Total Fluoride in Sample, mg
In-stack Concentration of F, mg/ft3
Post-test Calibration Checks
Temperature and Barometric Pressure
Differential Pressure Gauges
Metering System
r. - F<
e
Y"
AH
pb
*.
%CO2
%02
%(CO + N2)
Md
m
m
Vm(std)
Vw
-------
9/30/94: L13B-1
LABORATORYPROCEDURE13B
Total Fluoride
(Specific Ion Electrode Method)
A. Reagent Preparation
1. Phenolphthalein Indicator. Dissolve 0.1 g
phenolphthalein in a mixture of 50 mL 90%
ethanol and 50 mL water.
2. Sodium Hydroxide, 5 M. Dissolve 20 g
NaOH in 100 mL water.
3. H2SO4, 25% (v/v). Mix 1 part cone. H2SO4
with 3 parts of water.
4. Total Ionic Strength Adjustment Buffer
(TISAB). Use commercially-prepared TISAB
or prepare as follows: Place about 500 mL
water in a 1-L beaker. Add 57 mL glacial
acetic acid, 58 g NaCI, and 4 g
cyclohexylene dinitrilo tetraacetic acid. Stir
to dissolve. Place the beaker in a water bath
to cool it. Slowly add 5 M NaOH to the
solution, measuring the pH continuously with
a calibrated pH/reference electrode pair, until
the pH is 5.3. Cool to room temperature.
Pour into a 1-L volumetric flask, and dilute to
volume with water.
5. Fluoride Standard Solution, 0.1 M. Oven dry
some NaF for &2 hr at 110°C, and store in a
desiccator. Then add 4.2 g NaF to a 1-L
volumetric flask, and add enough water to
dissolve. Dilute to volume with water.
B. Specific Ion Electrode Calibration
1. Pipet 10 mL 0.1 M fluoride standard solution
into a 100-mL volumetric flask, and make up
to the mark with water for a 10"2 M standard
solution. Use 10 mL 10~2 M solution to make
a 10"3 M solution in the same manner.
Repeat the dilution procedure, and make 10"4
and 10'5 solutions.
2. Pipet 50 mL of each standard into a separate
beaker. Add 50 mL TISAB to each beaker.
3. Place the electrode in the most dilute
standard solution. Stir the solution with a
magnetic stirrer during measurement to
minimize electrode response time. If the
stirrer generates enough heat to change
solution temperature, place a piece of
temperature insulating material, such as cork,
between the stirrer and the beaker. When a
steady mv reading is obtained, record that
value. This may take several minutes.
4. Between measurements, soak the fluoride
sensing electrode in water for 30 sec, and
then remove and blot dry.
5. Analyze the standards going from dilute to
concentrated standards.
6. Plot the millivolt reading on the linear axis of
semilog graph paper versus concentration
(nominal value) on the log axis. When
50 mL 10~2 M standard is diluted with 50 mL
TISAB, the nominal concentration is still
"10~2 M." The calibration curve should be a
straight line; however/ some electrodes may
be slightly nonlinear between 10~5 and
10"* M. If this occurs, use additional
standards between these two
concentrations.
7. Calibrate the fluoride electrode daily, and
check it hourly. Prepare fresh fluoride
standardizing solutions daily (10~2 M or less).
Store fluoride standardizing solutions in
polyethylene or polypropylene containers.
8. Note: Certain specific ion meters have been
designed specifically for fluoride electrode
use and give a direct readout of fluoride ion
concentration. These meters may be'used in
lieu of calibration curves for fluoride
measurements over a narrow concentration
ranges. Calibrate the meter according to the
manufacturer's instructions.
C. Analysis
1. Containers No. 1 and No. 2
a. Distill suitable aliquots from each
container.
b. Dilute the distillate in the volumetric
flasks to exactly 250 mL with water,
and mix thoroughly.
c. Pipet a 25-mL aliquot from each of the
distillate and separate beakers. Add an
equal volume of TISAB, and mix.
d. Analyze the samples in the same
manner and at the same temperature as
that of the calibration standards
(±2°C). Hold dilute samples (below
10"4 M fluoride ion content) in
'_ polyethylene beakers during
measurement.
e. Determine concentration from the
calibration curve.
2. Container No. 3 (Silica Gel). If not done in
the field, weigh the spent silica gel (or silica
gel plus impinger) to the nearest 0.5 g.
-------
9730/94: LD13B-1
LABORATORY DATA SHEET 13B
Total Fluoride - Specific Ion Electrode
Client/Plant Name
Meter ID#
Job #
Electrode ID#
Date/Time
Calibration Date
Ambient Temp. °F
Calibration standard mix date
Bath Temp.
Analyst
Working Standards:
Molarity (M)
Electrode Potential (mV) 1
Electrode Potential (mV) 2
10'1
10-.2
10'3
10"4
10'5
Control
Sample
Note: Concentration of the control sample determined from the curve must be between O.OO2Mand 0.01 M.
Plot of calibration curve attached?
Sample
No.
Sample
ID#
Sample
Vol., Vt
(mL)
Aliquot
Vol., A,
(mL)
Diluted
Distillate Vol.,
Vd (mL)
Electrode Potential mV
mV1 mV2 mVavg -
Mof F
in
sample
Total Wgt
of F, Ft
(mg)
Total Weight of Fluoride in Sample , mg:
V,
A,
, = 19 -^ Vd M
Fluoride electrode calibrated daily?
Electrode calibration checked hourly?
Fluoride standardizing solution prepared fresh
daily?
Fluoride standardizing solutions stored in
polyethylene or polypropylene containers?
QA/QC Check
Completeness
Legibility
Accuracy
Checked by:
Personnel (Signature/Date)
Ambient temperatures fluctuate > ±2°C from
the temperature that the standards were
measured?
Sample and standards conditioned in a constant
temperature bath before measuring?
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
-------
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
SUMMARY SHEET 14
Total Fluoride
FDS5/14
FDS5/14
FDS5
FDS 5/14
FDS 5/1 4
FDS 5
FDS 5
Run#1
9/3O/94: S14-1
Run #2 Run #3 Avg
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
FDS1
FDS1
FDS 5
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Abs Stack Pressure (Pb + Pg/13.6), in. Hg
Average Duct Temperature, °F
Avg Abs Duct Temperature, (ts + 460)
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average t(tsi +460) Ap]1/2
Average Duct Velocity, ft/sec
Isokinetic Sampling Rate, %
Manifold Duct Diameter at Sampling Pt, in.
Manifold D (D x 0.3048), m
Manifold Barometric Pressure, mm Hg
Manifold Nozzle Diameter, m
Average Roof Monitor Temperature, °C
Avg Abs Roof Monitor Temp, (273 + tr), K
Y
AH
%CO2
%O2
%(CO + N2
Md
vm(std)
V,c
Vw(std)
B
CP
Ap
[Tsi Ap]
1/2
bm
Ddn
FDS 5
CDS 5
FDS 5
FDS 5
FDS 5
SS5
FDS 5
SS5
FDS 3
FDS 3
FDS 3
FDS 3
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS2a
FDS 5
FDS 5
SS5
SS5
FDS 5
SS14
FDS 14
FDS 14a
FDS 14
SS14
-------
Avg Manifold Anemometer Velocity, m/min v
Desired Duct Velocity, m/sec vd
Manifold Isokinetic Ratio, %
Isokinetic Correction Factor
Overall Roof Monitor Velocity, m/min
Roof Monitor Open Area, m2
Roof Monitor Volumetric Flow, scmm
Total Fluoride in Sample, mg
Concentration of Fluoride, mg/ft3
Post-test Calibration Checks
Temperature and Barometer
Differential Pressure Gauge
Metering System
%lm
F
vmt
A
Qsd
FDS 14
SS 1 4
SS 14
SS 14
FDS 14
FDS 1 4
SS 14
LDS 13A/B
LDS 13A/B
CDS 2d
CDS 2d
CDS 5
Run #1
Run #2
9/30/94: S14-2
Run #3 Avg
60
F = 1 +
-120
200
Multiply emission rate by F, only if %lm >120%.
0.3855
-------
9/30/94:
FIELD PROCEDURE 14
Fluoride Emissions from Potroom Roof Monitors for
Primary Aluminum Plants
Note: FP 14 describes the measurements of flow rates and fluoride concentrations from potroom roof
monitors in primary aluminum plants.
A. Roof Monitor Velocity
1. A day (24 hr) before the test run, turn on the
exhaust fan and adjust flow rate to an
estimated isokinetic condition (i.e., average
velocity at the manifold nozzles equal to the
average velocity at the roof monitor) to
condition the ductwork.
2. Estimate the average velocity at the roof
monitor before each run using the
anemometer (the one in the section
containing the sampling manifold) readings
from 24 hr before or from any other
information. If velocities are anticipated to
be significantly different because of different
potroom operations, the test run may be
divided into two or more "sub-runs," and an
average velocity for each sub-run may be
estimated.
3. Adjust the fan to isokinetic conditions (see
Equation F14-1). Perform a pitot tube
traverse of the sample duct (using either a
standard or Type S pitot tube) according to
FP 2 to verify isokinetic conditions. Once a
run or sub-run has begun, do not make any
isokinetic rate adjustments.
V —
H
8 Pn Vm
60 Drt2
Eq. F14-1
where:
vd = Desired velocity in duct at
measurement location, m/sec.
Dn = Diameter of a manifold nozzle, m.
Dd = Diameter of duct at measurement
location, m.
vm = Average velocity in the roof monitor,
m/min.
B. Fluoride Sampling/Velocity Determination
1. Each test run shall be S:8 hr (times for all
runs shall be about within ±10% of the
average); during each run, the operation of
all pots shall be representative of normal
operating conditions underneath the
sampling manifold. For more recently-
constructed plants, 24 hr or more may be
required to be representative of all potroom
operations.
2. Sample the duct and recover and analyze the
sample using Method 13A or 13B. Use a
single train for the entire sampling run or for
each sub-run. If a separate train is used for
each sub-run, sampling nozzles must have
areas within ±2% of the average.'. For each
sub-run, perform a complete traverse of the
duct.
3. During the test run, record the'velocity or
volumetric flowrate readings of each
propeller anemometer at least every 15 min
at equal time intervals (or continuously).
4. Record the temperature of the roof monitor
every 2 hr during the test run.
-------
9/30/94: FD14-1
FIELD DATA SHEET 14
Potroom Roof Monitors of Primary Aluminum Plants
Client/Plant Name
City/State
Run #
Date
Job
Start Time
Personnel
m2 Bar. Press., Pb.
mm Hg
Roof Monitor Open Area, A
End Time Note: Mark with asterisk (*) the manifold anemometer.
Clock
time
(hr/min)
0:15
0:30
0:45
1:00
1:15
1:30
1:45
2:00
2:15
2:30
2:45
3:00
3:15
3:30
3:45
4:00
4:15
4:30
4:45
5:00
5:15
5:30
5:45
6:00
Anemometers (m/min)
1
2
3
4
Temp.
tr
(°C)
Clock
time
(hr/min)
6:15
6:30
6:45
7:00
7:15
7:30
7:45
8:00
8:15
8:30
8:45
9:00
9:15
9:30
9:45
10:00
10:15
10:30
10:45
11:00
11:15
11:30
11:45
12:00
Average, vm
Overall Average, vmt
Anemometers (m/min)
1
2
3
I1 '
•
4
Temp,
*r
(°C)
•
QA/aC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications_
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: FUa-1
FIELD PROCEDURE 14a
Manifold/Anemometer System
A. Manifold System Construction
Construct the manifold system using the
general configuration and dimensions shown in
Figures F14a-1 and F14a-2; dimensions may be
slightly altered to fit a particular roof monitor.
Details are:
Eight nozzles, 0.4O to 0.50 m ID, each leg
with a flow regulator, e.g., blast gate or
valve.
1,
2. Length of the manifold system from the first
nozzle to the eighth: 35 rri or 8% of the
length of the potroom (or potrobm segment)
roof monitor, whichever is greater.
3. Round ductwork from the roof monitor
manifold, 0.30 to O.40 m ID.
4. Stainless steel, aluminum, or other
construction material for all sample-exposed
surfaces. Note: Aluminum construction
requires 6 weeks of conditioning with
fluoride-laden roof monitor air before initial
test. Other materials of construction require
comparative testing to demonstrate no loss
of fluorides in the system.
5. Leak-free connections in the ductwork.
6. Two sample ports in a vertical section of the
duct between the roof monitor and exhaust
fan, &10 D. downstream and ^3 D.
upstream from flow disturbances, 90° apart,
and one traverse line in the plane of the
nearest upstream duct bend.
B. Roof Monitor Air Sampling System
Installation
1. Balance the flow rates in the eight individual
nozzles to approximate the average effluent
velocity in the roof monitor. Measure the
velocity at the center of each manifold leg
duct; use a standard pilot tube (not a Type S)
into a <2.5 cm diameter hole (see
Figure F14a-2) in the manifold. Ensure that
there is no leakage around the pitot tube.
Use the blast gate (or valve) to adjust the
flow. Fasten each blast gate (or valve) so
that it will remain in position, and close the
pitot port holes. Perform this calibration
when the manifold system is installed or, if
preassembled on the ground, before being
installed.
2. Install anemometers as follows:
a. Single, Isolated Potroom. Divide roof
monitor length by 85 m, round off to
nearest whole number. For a roof
monitor 130 m long, round off to two.
Divide the monitor cross-section into as
many equal areas as this number.
b. Two or More (Potrooms). Follow the
procedure in step B2a for each potroom
(or segment) that contains a sampling
manifold.
c. Install an anemometer at the centroid of
each equal area, except for those within
the manifold section. Install these at
the midpoint of the width of the roof
monitor or at a point of average velocity
(based on a velocity traverse made
during normal operations) and install at
least one anemometer within 10 m of
the center of the manifold.
3. Install at least one manifold system fpr each
potroom group (as defined in Subpart S,
Section 60.191) near the midsection of the
potroom (or potroom segment), or above
pots that are representative of normal
operating conditions, and close to one of the
propeller anemometers. Avoid the ends.
Center the sample nozzles in the throat of
the roof monitor (see Figure F14a-1).
4. Install a thermocouple in the roof monitor
near the sample duct.
C. Notes
1. The roof monitor shown in Figure F14a-1 is a
general type. If the general guidelines
cannot be met, consult with the
Administrator.
2. Sufficient velocities should be maintained in
the system to prevent F deposition.
-------
Roof Monitor
Sample Extraction
Duct
SScml.D.
<-"*s
S^x"
2
10 Duct Dia.
Exhaust Min
Stack
^
ft •—
mum •
3 Duct Dia.
fMinimun
£-•;
I
« . ^m— • ••,
Is— ^
Sample Ports in
Vertical Duct
Section as Shown
/ 7.5 cm Dia.
Pot Room
BchaustBlovrar
Figure F14a-1. Roof Monitor Sampling System.
Figure F14a-2. Sampling Manifold and Nozzles.
-------
9/30/94: FD14a-1
FIELD DATA SHEET 14a
Manifold/Anemometer System
Client/Plant Name
City/State
Date
Job #
Personnel
Check (/): Single, Isolated Potroom Two or More Potrooms
Potroom Length, Lp = m 0.08 Lp = m
Manifold Length, Lm = m (fe higher of 35 m or 0.08 Lp)
No. of Anemometers, Lp/85 = (round off to nearest whole number)
Sample Extraction Location: Diameter, D. = m (0.30 to 0.40 m ?)
Upstream, U m U/D. = (&10?)
Downstream, D _m DID, = (fe3 ?)
Manifold Nozzle Diameter, Dn = m (0.40 to 0.50 m ?)
Construction Material (/): Stainless Steel Aluminum Other
Sample extraction two ports 90° apart?
General configuration and dimensions similar to Figures F14a-1 and
F14a-2?
Connection leak-free? (By visual inspection)
Thermocouple installed near sample duct in roof monitor?
Anemometer at centroid of
each equal area?
Manifold anemometer within
10 m of manifold center?
Manifold anemometer at
midpoint of width? If not,
show velocity traverse:
Velocity Traverse of Width
Ft
Ap
Sketch location of manifold in relation
to roof monitor (give dimensions):
Pitot Tube ID#
Coefficient
Run No.
Nozzle No.
1
2
3
4
5
6
7
8
Average
1
Ap
in. H2O
2
Ap
in. H2O
3
Ap
in. H2O
4
Ap
in. H2O
•
5
Ap
in. H2O
QA/QC Check
Completeness Legibility Accuracy Specifications Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
Power
Regulator
Tachometer - D.C. Motor
Combination
(Accurat
Anemometer
Digital
Voltmeter
(Accurate to ± *A mv)
I I I I I I
Figure C14-1. Typical RPM Generator.
Side
(A)
Front
Side
(B)
Front
Figure C14-2. Check of Anemometer Starting Torque. A "y"
Gram Weight Placed "x" Centimeters from Center of
Propeller Shaft Procedures a Torque of "xy" g-cm. The
Minimum Torque Which Produces a 90° (approximately)
Rotation of the Propeller is the "Starting Torque."
-------
FPM
(m/min)
20
(6)
40 60 80 100 120 140
(12) (18) (24) (30) (36) (42)
THRESHOLD VELOCITY FOR HORIZONTAL MOUNTING
Figure C14-3. Typical Curve of Starting Torque vs. Horizontal
Threshold Velocity for Propeller Anemometers. Based on
Data Obtained by R.M. Young, Company, May, 1977.
-------
9/30/94: C14-1
CALIBRATION PROCEDURE 14
Propeller Anemometers
A. Calibration
1. Obtain a "reference" performance curve
relating anemometer signal output to air
velocity (covering the velocity range of
interest) from the manufacturer. A
"reference" performance curve is one that
has been derived from primary standard
calibration data, with the anemometer
mounted vertically. "Primary standard" data
are obtainable by:
a. Direct calibration of one or more of the
anemometers by the National Institute of
Standards and Technology (MIST).
b. NIST-traceable calibration.
c. Calibration by direct measurement of
fundamental parameters such as length
and time (e.g., by moving the
anemometers through still air at
measured rates of speed, and recording
the output signals).
2. Check the signal output of the anemometer
by using an accurate rpm generator (see
Figure C14-1) or synchronous motors to spin
the propeller shaft at a minimum of three
evenly spaced rpm settings, e.g., 60 ± 15,
900 ± 100, and 1800 ± 100 rpm and
measuring the output signal at each setting.
Output signal readings must be £ ±5% of
manufacturer's value at each setting.
3. Inspect the propeller for any significant
damage or warpage and replace damaged or
deformed propellers.
4. Check the anemometer threshold velocity as
follows:
a. Mount the anemometer as shown in
Figure C14-21A).
b. Fasten a known weight (a straight-pin
will suffice) to the anemometer propeller
at a fixed distance from the center of the
propeller shaft to generate a known
torque; e.g., a 0.1-g weight, placed
10 cm from the center of the shaft, will
generate a torque of 1.0 g-cm. Try
different combinations of weight and
distance to estimate the starting torque,
and determine the threshold velocity of
the anemometer (for horizontal
mounting) using a graph such as
Figure C14-3 (obtained from the
manufacturer). Horizontal threshold
velocity must be ^50 fpm.
5. Compare temperature readings from the
thermocouple-potentiometer system against
reference thermometers at 0, 100, and
15Q°C. Measured temperatures must be
within ±5°C at each of the reference
temperatures.
6. Check the calibration of each recorder and
counter at a minimum of three points,
approximately spanning the expected range
of velocities. Use the calibration procedures
recommended by the manufacturer, or other
suitable procedures. Difference for the three
calibration points must be ^ ±5%.
B. Periodic Performance Checks
1. Check the calibration of the propeller
anemometers, thermocouple-potentiometer
system and the recorders and counters
within 60 days before the first performance
test and, thereafter, at 12-month intervals.
2. If any of the above systems fail the ,
performance checks or if any repairs or
replacements are made during the
12 months, conduct the periodic
performance checks at 3-month intervals,
until sufficient information (consult with the
Administrator) is obtained to establish a
modified performance check schedule and
calculation procedure. Note: Failure of the
first annual performance checks does not
require recalculating the data for the past
year.
-------
9/30/94: CD14-1
CALIBRATION DATA SHEET 14
Propeller Anemometers
Client/Plant Name
City/State,
Date
Job #
Personnel
Attach "reference" performance curve of anemometer output to velocity; starting torque vs. velocity; recorder/counter
calibration curve.
Anemometer ID#
RPM
60 ± 15
900 ± 100
1800 ± 100
Threshold Velocity
Weight (g)
Distance (cm)
Velocity
Recorder/Counter
Pt 1
Pt2
Pt3
Thermocouple
0°C
100°C
150°C
Damaged/Warped ?
Rdg
Ref
Rdg/Ref
s±5% ?
s 50 f pm ?
Rdg
Rdg
Ref
Ref
Rdg/Ref
£±5% 7
Diff
s±5°C ?
Rdg
Ref
Rdg/Ref
£±5% 7
^50 fpm 7
Rdg
Rdg
Ref
Ref
Rdg/Ref
£±5% 7
- •
Diff
<±5°C7
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
-------
Client/Plant Name
Job No.
Sampling Location
Run ID #
9/30/94: S15-1
SUMMARY SHEET 15
Reduced Sulfur Compounds
FDS 15
FDS 15
FDS 15
FDS 15
Run#1
Run #2
Run #3
Avg
Test Date
Run Start Time
Run Finish Time
Concentration H2S, ppm
Concentration COS, ppm
Concentration CS2, ppm
Avg SO2 Equivalent, ppm
Sample Line Loss Ratio
Corr Avg SO2 Equivalent, ppm
Post-test Calibration Checks
Flow Meter Calibration
Dilution Factor
H2S
COS
CS,
SO
LR
SO
2e
2ec
FDS 15
FDS 15
FDS 15
FDS 15
FDS 15
FDS 15
FDS 15
FDS 15
SS 15
FDS 15
FDS 15
SO -
2ec
-------
To GC/FPD Analyzers
10:1 1(?:1
SlatsWbon/vSSr o^.hh.r
i Fitter A\ oCiUDDcr
i 1 1 1
t.pf<>ba^ -(Hvi — h '
\ FiLr
i
t
Positive
.Jj-N
Permeationl
Tube | /^
Calibration. pr~
Gas 1 x
4 I
LL
i-4-j-^
t-
_
_ _... «
p
)
• IV—
JC
r
v.
^
)
3-VVay
Valve
^&! ^
Diluent Air
1 1
13SO(jc/min
H
E
EJ
Flowmetor
2Spsl
Clean
Dry Air
I
r->»^t-1 Dilution Box
Diaphragm
Pump Vent
Figure F15-1. Sampling and Dilution Apparatus.
To Instruments And
Dilution System
Row Meter
Diluent Air Or
Nitrogen
Figure C15-1. Apparatus for Reid Calibration.
-------
9/30/94: F15-1
FIELD PROCEDURE 15
Reduced Sulfur Compounds
Note: Methods 15 and 16 are identical except for the reduced sulfur compounds being analyzed.
Method 15 is used to determine hydrogen sulfide (H2S), carbonyl sulfide (COS), and carbon disulfide
(CS2) from tail gas control units of sulfur recovery plants. Method 16 is used to determine H2S, methyl
mercaptan (MeSH), dimethyl sulfide fDMSJ, and dimethyl disulfide (DMDS).
The forms in this section contain the information required by the test method; we are aware that
some of the technology specified in the test method is obsolete. In these cases, the user should modify
the forms to make them consistent with the technology used.
A. Optional Pretest Procedures
1. Leak-check all components, sample lines,
and connections.
a. For components upstream of the sample
pump, use FP 3c, section A, except
conduct the leak-check at >2 in. Hg
vacuum and 1 min.
b. For components after the pump, use
FP 3c, section E.
2. Observe the response of flowmeters or of
the GC output to changes in flow rates or
calibration gas concentrations and ascertain
the response to be within predicted limits.
B. Calibration
1. Equilibrate the permeation tubes (H2S, COS,
and CS2) for 24 hr at the calibration
temperature (± 0.1 ° C). (For Method 16,
use permeation tubes for H2S, MeSH, DMS,
and DMDS.)
2. Generate a series of three or more known
concentrations spanning the linear range of
the FPD (approximately 0.5 to 10 ppm for a
1 -mL sample) for each of the sulfur
compounds.
3. Bypassing the dilution system, inject the
standards into the GC/FPD analyzers until
the response of any one of three injects at
each concentration varies no more than
±13% from their average (hereafter called
precision). For Method 16, the precision
requirement is ±5%.
4. Generate a least squares equation of the
concentrations vs. the appropriate GC/FPD
response units (log-log relationship).
5. Calibrate each stage of the dilution system
using a known concentration of H2S from
the permeation tube system. (See Figure
C15-1.) Determine from the GC/FPD the
concentration of the diluted calibration in
ppm to within ±13% (or ±5% for Method
16) precision. Then calculate the dilution
factor.
C. Sampling and Analysis Procedure
1. Assemble the apparatus as shown in Figure
F15-1. Calibrate the system before the first
run as in section B.
2. Insert the sampling probe into the test port;
plug off open areas to prevent dilution air
from entering the stack. Begin sampling,
and dilute the sample approximately 9:1.
Condition the entire system with sample for
at least 15 min before analyzing.
3. For each sample run, analyze 16 individual
injects of the diluted sample on the GC/FPD
analyzer over 3 to 6 hr.
4. If sample concentrations decreases during a
sample run and the decrease is not due to
process conditions, check for clogging in the
sample probe. If the probe is clogged,
invalidate the test run, and restart the run.
5. After each run, inspect the sample probe.
D. Post-test Procedures
1. Determine the sample line loss as follows:
a. Introduce into the sampling system at
the probe inlet H2S of known
concentration (using permeation tubes
or H2S/air mixture in a gas cylinder,
traceable to permeation tubes) within
±20% of the applicable standard.
b. Compare the resulting measured
concentration with the known value
(must be <:20% loss).
2. After each run, or after a series of runs
made within a 24-hr period, recalibrate the
GC/FPD analysis and dilution system using
only H2S (or other permeaht). Compare
against the calibration curve obtained before
the test runs. If the means of the triplicates
differ ^5%, either void the intervening runs
or use the calibration data set that gives the
highest sample values.
-------
3. After a complete test series, calibrate each
flowmeter in the permeation tube flow
system with a wet test meter or soap
bubble meter (must agree within ±5% of
the initial calibration).
£. Alternatives
1. Step B1. Inject samples of calibration gas
at 1 -hr intervals until three consecutive
hourly samples agree within ± 13% of their
average.
2. Step B4. Plot the GC/FPD response in
current (amperes) vs. their causative
concentrations in ppm on log-log coordinate
graph paper for each sulfur compound.
9/30/94: F15-2
Section B. Calibrate the GC/FPD system by
generating a series of three or more
concentrations of each sulfur compound and
diluting these samples before injecting them
into the GC/FPD system. A separate
determination of the dilution factor is not
necessary, however, precision of ±13% still
applies.
-------
9/30/94: FD15-1
Method (SJ 15 16
Client/Plant Name .
City/State ___
FIELD DATA SHEET 15
Reduced Sulfur Compounds
Date
Job #
Personnel
Calibration (/) Initial
Post-Test (Post-test requires calibration with only H2S; must be <5% of initial)
Cone.
Level
1
2
3
1
2
3
1
2
3
1
2
3
Cone.,
C
(ppm)
H2S
GC/FPD Response: %Dev = s* ± 13% for FP 15; :£ ±5% for FP 16
Inject #1
•
Inject #2
Inject #3
Average
'-.
*'
High % Dev
Note: Plot response vs. concentration; attach graph.
Use only if dilution is necessary.
Stage
1
2
H2S
Cone.
(ppm)
GC/FPD Resp: % Dev = £ ± 13% forFP 15; £±5% for FP 16
Inject #1
Inject #2
Inject #3
Average
% Dev
Meas.
Cone.
(ppm)
Dilution
Factor
Sample Line Loss:
Ref Gas
Ref Cone, Cr
Meas. Cone, C_
ppm
LR = Cm/Cr =
Post-test Flow Meter Calibration (permeation tube flow system):
Initial Cal Factor, Yj Post-Test Cal Factor, Yf
ppm
(0.80 to 1.20 ?)
Yf/Y= =
'f'i
(0.95 to 1.05?)
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: FD15-2
FIELD DATA SHEET 15 (Continued)
Source Measurements
Sampling Location
Analyst
Run #
Inject.
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
H2S{16/16)
Resp
Cone
(ppm)
COS (15)/ MeSH (16)
Resp
Cone
(ppm)
CS2 (15)/DMS (16)
Resp
Cone
(ppm)
DMDS (16)
Resp
Cone
(ppm)
D.F.
.
f
.
Avg, S02e
SO2
Equiv.
(ppm)
- '
Method 15: SO2 Equiv. = ppm H2S + ppm COS + (2 x ppm CS2)
Method 16: S02 Equiv. = ppm H2S + ppm MeSH + ppm DMS + (2 x ppm DMDS)
QA/O.C Check
Completeness _
Checked by:
Legibility
Accuracy
Specifications_
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: S15A-1
SUMMARY SHEET 15A
Reduced Sulfur Compounds
Client/Plant Name ;
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
. Run Finish Time
Barometric Pressure, mm Hg
Average Sample DGM Temp., °C
Average Combustion DGM Temp., °C
Sample DGM Calibration Factor
Combustion DGM Calibration Factor
Vol. of Metered Sample Gas, dL
Vol. of Metered Combustion Gas, dL
Vol. of Metered Sample Gas, dsL
Vol. of Metered Combustion Gas, dsL
Sample
Normality of, Titrant, meq/mL
Volume of Aliquot, mL
Volume of Solution, mL
Volume of Titrant, mL
Volume of Titrant for Blank, mL
System Performance (COS)
DGM Calibration Factor
Avg DGM Temperature, °C
Vol. of Metered Gas, dL
Vol. of Metered Gas, dsL
Normality of Titrant, meq/mL
Volume of Aliquot, mL
Volume of Solution, mL
Volume of Titrant, mL
Volume of Titrant for Blank, mL
Sample Concentration of TRS as SO2, ppm
Recovery Gas Ref Concentration, ppm
Recovery Gas Measured Concentration, ppm
Recovery Efficiency, %
Audit Relative Error, %
Post-test Calibration Checks •
Temperature and Barometer
Metering System
Vms(std) = 0.3858 VmsYs
273)
Pb
tms
TT1C
Ys
vL
me
Vms(std)
"rnc(std)
N
va
vs
vt
vtb
Yp
mp
Mnp(std)
N
V
vs
vt
CTRS
CRG
CRGm
R
RE
FDS 1 5 A
FDS 1 5 A
FDS 1 5A
FDS 15A
FDS 15A
FDS 15A
FDS15A
FDS 1 5A
FDS 15A
FDS 15A
FDS 15A
FDS 1 5A
FDS 15A
FDS 15A
SS15A
SS15A
LDS 6
LDS 6
LDS 6
LDS 6
LDS 6
LDS 15A
LDS 15A
LDS 15A
SS15A
LDS 6
LDS 6
LDS 6
LDS 6
LDS 6
SS15A
FDS 1 5A
SS 15A
SS 15A
QA1
CDS2d
CDS 6
Run#1
Run #2
Run #3
Avg
CTRS = 12025
(VVlb)N -1
\ i
["ms(std) ~ "
Use the above equation to calculate Vmp(std); using the Use the above equation to calculate CRGrn; using the
appropriate data. appropriate data.
V,
mc(std)
0.3858
RGm
RG
x100
-------
Tvmpcratura
Figure F15A-1. Sampling Train.
ToMbdno
ChifflbM-
Mircury
Minomttir
Rgure F15A-2. Combustion Air Delivery System.
Minlfold
Nttrogen
Figure F15A-3. COS Recovery Gas Generator System.
-------
9/30/94: F15A-1
FIELD PROCEDURE 15A
, • Reduced Sulfur Compounds
Note: FP 15* is a procedure in which Method 6 is used after a dilution and oxidation system to convert
reduced sulfur compounds to SO2- •
A. Sampling Train Preparation
1. Set up the sampling train as shown in
Figure F15A-1. Prepare the Method 6 part of
the train as in FP 6, except use 20 mL H2O2.
2. Set the oxidation furnace at 1100 ± 50 °C
and the probe and filter temperature high
enough to prevent visible condensation of
moisture. : . ,
3. Optional: Leak-check the sampling train as in
FP 3c, sections C and D, including the
combustion air delivery system from the
needle valve forward.
4. Optional: Conduct two 30-min system
performance checks in the field according to
section C.
B. Sample Collection
1.
2.
3.
4.
Adjust the pressure on the second stage of
the regulator on the combustion air cylinder
to 10 psig and the combustion air flow rate
to 0.50 L/min (±10%). See Figure F15A-2.
Inject combustion air into the sampling train,
start the sample pump, and open the stack
sample gas valve (do all these operations
within 30 sec to avoid pressurizing the
sampling train).
Sample as in Method 6 at 2.0 L/min (±10%)
for 1 hr (three 1-hr samples are required for
each run) or for 3 hr.
Monitor and record the combustion air
manometer reading at regular intervals during
sampling.
5. At the end of sampling, turn off the sample
pump and combustion air simultaneously
(within 30 sec of each other).
6. Mandatory: Leak-check the sampling train
(see FP 3c, section C).
7. Recover the sample as in FP 6, except do
not purge the sample.
8. Mandatory: Conduct a performance system
check after each 3-hr run or after three 1-hr
samples. See section C.
9. Optional: Rinse and brush the probe and
replace the filter before the next run.
C. System Performance Check
1. Adjust the flow rates to generate COS
concentration in the range of the stack gas
or within ±20% of the applicable standard
at a total flow rate of at least 2.5 L/min.
See Figure F15A-3, if dilution is.required.
2. Calibrate the flow rate from both sources
with a soap bubble flow tube.
3. Collect 30-min samples, and analyze in the
normal manner. Collect the samples through
the probe of the sampling train using a
manifold or some other suitable device. Do
not replace the particulate filter and do not
clean the probe before this check.
4. Analyze the samples as in LP 6. Analyze
field audit samples, if applicable.
-------
9/30/94: FD15A-1
FIELD DATA SHEET 15A
Reduced Sulfur Compound?
Client/Plant Name
City/State
Job#
Date/Time
Test Location/Run #
Personnel
Sample Train IDtf/Sample Box #
DGM Cal Coef., Ys
Amb Temp., °C_
Combustion Train ID#/Sampie Box # ^___ DGM Cal Coef., Yc
Start Time End Time ; Bar. Pressure, Pb
mm Hg
Trav
Pt.
Samplg
time
(min)
0
DGM Sample Volume
DGM Rdg
(L)
vms
Temp,
Avg, tms
Rot Rdg
(L/min)
±10%
of Avg?
Imp. Exit
Temp
Max
«s20°C?
DGM Comb. Volume
DGM Rdg
(L)
me
Temp,
Avg, tmo
Press
(mm Hg)
•
Avg, Pm_
*•** me
Rot Rdg
(L/min)
'..
0.50 ±
0.05?
Furnace
Temp
1100±
50?
Proper probe heat (no condensation)?
Sampfo Recovery
Fluid level marked?
Sample container sealed?
Sample container identified?
Leak-Checks rsO.02 Avg Flow Rate at Ss10 in. Hg vac.
Run*
Pre (optional) (cc/min)
Post (mandatory) (cc/min)
Vacuum (a 10 in. Hg ?)
Post-Test Calibrations
Attach CDS 2d and CDS 6. Temperature specification for the DGM thermometer is :£ ±5.4°F.
QA/dC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: FD15A-2
FIELD DATA SHEET 15A (Continued)
System Performance Check
Client/Plant Name
City/State
Train ID#
Job #
Date/Time
Personnel
DGM Calibration Factor, Yc
Rotameter Calibration
Train ID#
Rotameter Rdg L/min
Bubble Meter Vol, Vsb L
Time, 0 sec
Bar. Press., Pb mm Hg
Amb Temp., tamb °C
Flow Rate, Qstd L/min
Average Qstd L/min
COS
N2
Samplg
time
(min)
0
5
10
15
20
25
30
Total
Time, 0S
COS
Rotam Rdg
(L/rnin)
Avg
N2
Rotam Rdg
(L/min)
Avg
DGM
Rdg
(U
Volume, Vmp
Temperature (°C)
DGM
Av9'tmp
Imp. Exit
Max
i*200C?
Flow Rate Deviation
AVm
Avg
AVm/AVm
0.90-1.10?
Reference COS Cylinder Concentration, C,
cos
ppm
QA/QC Check
Completeness
= 23.13
Legibility
Qn
!•> o -"COS
°RG - °COS 7^ ~
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
-------
Client/Plant Name
Job No.
Sampling Location
Run ID #
9/30/94: S16-1
SUMMARY SHEET 16
Reduced Sulfur Compounds
FDS 15
FDS15
FDS 15
FDS 15
Run#1
Run #2
Run #3
Avg
Test Date
Run Start Time
Run Finish Time
FDS 15
FDS 15
FDS 15
Concentration H2S, ppm
Concentration MeSH, ppm
Concentration DMS, ppm
Concentration DMDS, ppm
Average SO2 Equivalent, ppm
Sample Line Loss Ratio
Corr Avg SO2 Equivalent, ppm
Post-test Calibration Checks
Flow Meter Calibration
Dilution Factor
H2S
MeSH
DMS
DMDS
LR
so2ec
FDS 15
FDS 15
FDS 15
FDS 15
FDS 15
FDS 15
SS16
FDS 15
FDS 15
so,
SO.
2«
LR
-------
After a complete test series, calibrate each
flowmeter in the permeation tube flow
system with a wet test meter .or soap
bubble meter (must agree within ±5% of
the initial calibration).
9/30/94: F16-2
Section B. Calibrate the GC/FPD system by
generating a series of three or more
concentrations of each sulfur compound and
diluting these samples before injecting them
into the GC/FPD system. A separate
determination of the dilution factor is hot
necessary, however, precision of ± 1.3 % still
applies.
£. Alternatives
1. Step B1. Inject samples of calibration gas
at 1 -hr intervals until three consecutive
hourly samples agree within ±13% of their
average.
2. Step B4. Plot the GC/FPD response in
current (amperes) vs. their causative
concentrations in ppm on log-log coordinate
graph paper for each sulfur compound.
-------
FIELD PROCEDURE 16A
Reduced Sulfur Compounds
Note: F,
oxidizing system to convert reduced sulfur compounds to
A. Sampling Train Preparation 4
2/S/95'. F16A-1
SO,
1. Set up the sampling train as shown in
Figure F16A-1. Prepare the Method 6 part of
the train as in FP 6, except use 20 mL H2O2.
Add 100 mL citrate buffer into the first and
second impingers of the SO2 scrubber; leave
the third empty. Keep the Teflon line
between the heated filter and citrate scrubber
as short as possible.
2. -Set the oxidation furnace at 800 ± 100°C
and the probe and filter temperature high
enough to prevent visible condensation of
moisture.
3. Bypassing all sample collection components,
draw stack gas into the citrate scrubber for
10 min at 2 L/min. Then assemble the train.
4. Optional: Leak-check the sampling train as in.
FP 3c, sections C and D.
5. Optional: Conduct two 30-min system
performance checks in the field according to
section C.
B. Sample Collection
1.
2.
3.
Sample as in Method 6 at 2.0 L/min (±10%)
for 1 hr (three 1-hr samples are required for
each run) or for 3 hr.
Mandatory: At the end of sampling, leak-
check the sampling train as in FP 3c,
section C.
Recover the sample as in Method 6, except
do not purge the sample.
C.
1.
S02.
Mandatory: Conduct a performance system
check after each 3-hr run or after three 1-hr
samples. See section C and FDS 16A.
Optional: Rinse and brush the probe with
water, replace the filter, and change the
citrate solution.
System Performance Check
Adjust the flow rates to generate H2S
concentration in the range of the stack gas
or within ±20% of the applicable standard
and an O2 concentration > 1 % at a total
flow rate of at least 2.5 L/min. See
Figure F16A-2.
Calibrate the flow rate from both sources
with a soap bubble flow tube.
Collect 30-min samples, and analyze in the
normal manner. Collect the samples through
the probe of the sampling train using a
manifold or some other suitable device. Do
not replace the paniculate filter nor the
citrate solution and do not clean the probe
before this check.
Analyze the samples as in LP 6, except for
1-hr samples, use a 40-mL aliquot, add
160 mL of 100% isopropanol, and four
drops of thorin.
5. Analyze field audit samples, if applicable.
Note: Sample recovery must be 100±20% for
data to be valid. Do not use recovery data to
correct the test results. However, if the
performance check results do not affect the
compliance or noncompliance status of the
affected facility, the Administrator may accept the
results.
2.
3.
4.
-------
Air
Figure F18A-1. Sampling Train.
'o 16A Simplng Pro&t
Figure F16A-2. Recovery Gas Dilution System.
_
-------
FIELD DATA SHEET 16A
Reduced Sulfur Compounds
2/8/95: FD16A-1
Client/Plant Name
City/State
Job#
Date/Time
Test Location/Run #
Personnel
Train ID#/Sample Box#.
Start Time
DGM Cal Coef., Y
Ambient Temp., °C_
End Time
(Sampling Time: Three 1-hr samples or One 3-hr sample?)
Bar. Pressure, Pb
.mm Hg
Trav
Pt.
Samplg
time
(min)
Total
Time, 95
DGM Rdg
(L)
•
Volume, Vm
Rotam
Rdg
(L/min)
•
Avg
Temperature (°C)
DGM
Avg.V.
Imp. Exit
Max
i20°C?
Flow Rate Deviation
AVm
Avg
AVm/AVm
,
2.0 ± 0.2?
Furnace
Temp
(°C)
800±
100?
. Proper probe heat (no condensation)?
Sample Recovery
No purge?
Fluid level marked?
Sample container sealed?
Sample container identified?
Leak-Checks -_0.02 Avg Flow Rate at _>10 in. Hg vac.
Run#
Pre (optional) (cc/min)
Post (mandatory) (cc/min)
Vacuum (^10in. Hg ?)
Post-Test Calibrations
Attach CDS 2d and CDS 6; temperature specification for DGM is i±5.4°F.
QA/QC Check (Include second page)
Completeness Legibility
Accuracy.
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
2/8/95: FD16A-2
FIELD DATA SHEET 16A (Continued)
System Performance Check
Client/Plant Name
City/State
Train ID#
Job*
Date/Time
Personnel
DGM Calibration Factor, Yp
Note: Check req'd after each 3-hr run or after three 1-hr runs.
Rotameter Calibration
Train ID#
Rotameter Rdg, L/min
Bubble Meter Vol. Vsb L
Time, 6 sec
Bar. Press., Pb mm Hg
Amb Temp., t,mb °C
Flow Rate, QM L/min
Average QM L/min
H2S
Air
Samplg
time
(min)
0
5
10
15
20
25
30
Total
Time, 6,
H2S
Rotam Rdg
(L/min)
Avg
Air
Rotam Rdg
(L/min)
Avg
DGM
Rdg
W
Volume, Vmp
Temperature (°C)
DGM
Avg, t^p
Imp. Exit
Max s20°C?
Flow Rate Deviation
AVm
Avg
AVm/AVm
0.90-1.10?
Reference H2S Cylinder Concentration, CH2S
Flow rate: Total = H2S + Air =
ppm (about stack concentration or ±20% standard?)
L/min (:>2 L/min?) Air = L/min (* 0.048 Total?)
= 21.13
QH2s
LDS 6 Check:.
QA/QC Check
Completeness _
K 2 QH s + QAir
For 1-hr samples, 40 mL aliquot, 160mL 100%IPA, and 4 drops of thorin used?
Legibility.
Accuracy.
Specifications _
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: F16Aa-1
FIELD PROCEDURE 16Aa
H2S Content in Cylinder Gases
A.
1.
2.
3.
4.
B.
1.
C.
1.
Pre-test Preparations
Calculate gas sample volumes in liters.
Divide the cylinder gas value by the ppm-
liters factor provided below:
H2S cylinder gas
concentration (ppm)
5 to < 30 ppm
30 to < 500 ppm
500 to < 1500 ppm
Factor
ppm-L
650 ppm-L
800 ppm-L
1000 ppm-L
Select a critical orifice within the following
flow rate range :
H2S cylinder gas
cone, (ppm)
5 to < 50 ppm
50 to <250 ppm
250 to < 1000 ppm
> 1000 ppm
Critical orifice
flow rate, (mL/min)
1500 ±500 ppm
500 ±250 ppm
200 ±50 ppm
75 ±25 ppm
Calibrate the critical orifice with the
sampling train according to FP 6a.
Determine the approximate sampling time
for a cylinder of known concentration.
Divide the gas sample volume times 1000
by the critical orifice flow rate.
Sampling Train Preparation
Connect the Teflon tubing. Teflon tee, and
rotameter to the flow control needle valve
as shown in Figure F16Aa-1. Vent the
rotameter to an exhaust hood. Plug the
open end of the tee.
Approximate the critical orifice flow rate
by connecting the critical orifice to the
sampling system as shown in
Figure F16Aa-1 without the H2S cylinder.
Connect a rotameter to the inlet of the first
impinger. Turn on the pump, and increase
vacuum to about half atmosphere. Slowly
increase the vacuum until a constant flow
rate is reached. Record the vacuum reading
as the critical vacuum. Ensure that this
flow rate is in the range shown in step A2
before proceeding.
Sample Collection
Five to 10 min prior to sampling, open the
cylinder valve while keeping the flow
control needle valve closed. Adjust the
delivery pressure to 20 psi. Open the
needle valve slowly until the rotameter
shows a flow rate ~50 to 10O mL above the
flow rate of the critical orifice being used in
the system.
2. Place 50 mL zinc acetate solution in the first
two impingers, leave the third impinger
empty and assemble as shown in
Figure F16Aa-1. Make sure the ground-glass
fittings are tight. Connect the Teflon sample
line to the first impinger. Protect the
absorbing solution from light during sampling
by covering the impingers with a dark cloth
or piece of plastic.
3. Record the information on the data sheet.
Open the closed end of the tee. Connect the
sampling tube to the tee, ensure a tight
connection. Start the sample pump and
stopwatch simultaneously. Sample for the
period determined in step A4.
4, Turn off the pump and stopwatch.
Disconnect the sampling line from the tee
and plug it. Close the needle valve-followed
by the cylinder valve. Record the sampling
time. •
5. Conduct a post-test critical orifice calibration
run using the calibration procedures outlined
in step A3. The Q^,, obtained before and
after the test cannot differ by >5%.
D. Sample Recovery
1. Do not detach the stems from the bottoms
of the impingers. Add 20.0 mL 0.01 N
iodine solution through the stems of the first
two impingers, dividing it between the two
(add ~ 15 mL to the first impinger and the
rest to the second).
2. Add 2 mL HCI solution through the stems,
dividing it between the two impingers.
3. Disconnect the sampling line and store the
impingers.
£. Post-test Calibration Checks
Calibrate barometer according to FP 2d.
-------
Temperature
Sensor
Silica Gol Critical
Drying Tubo Orifice
SurfittTank
Figure F16Aa-1. Recovery Check Gas Sampling Train.
-------
9/30/94: FD16Aa-1
FIELD DATA SHEET 16Aa
Hydrogen Content in Cylinder Gases
Client/Plant Name
City /State
Run#
Bar Press, Ph jn. I
Cylinder tag value
Calculated sample time
Start time
Personnel
"19 Amb Temperature
ppm Calculated sample volume
min. Sample Tim* -
Job #
Test Location
°F Date
L Critical orifice flow rate mL/min
Sample Vol. x 1000
Critical Orifice Flow Rate
End time
Use FDS 6a to collect the necessary data (attach to this data sheet). In addition, note the following:
Vent Rotameter Reading:
Before pump is on After pump is on Difference = critical orifice meter flow rate?
Using the information from FDS 6a, calculate Vm(std) using the equation below:
» \/ 7C *««..' n . M_
Ma - molecular weight of ambient air saturated at impinger temperature. At 25°C, use Ma = 28.5 g/g-mole.
gas (nitrogen) saturated at impinger temperature. At 25°C, use
Ms =
QA/QC Check
Completeness
Checked by: _
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: L16Aa-1
LABORATORYPROCEDURE16Aa
H2S Content in Cylinder Gases
A. Reagents:
1. Zinc Acetate Absorbing Solution. Dissolve
20 g zinc acetate in water and dilute to 1 L.
2. Standard Potassium Bi-iodate [KH(IO3)2,
0.100 N. Dissolve 3.249 g anhydrous
KH(IO3)2 in water and dilute to 1 L.
3, Standard Sodium Thiosulfate {Na2S203),
, 0.1 N. Dissolve 24.8 g sodium thiosulfate
pentahydrate (Na2S203-5H20) or 15.8 g
anhydrous sodium thiosulfate (Na2S203) in
1 L water, and add 0.01 g anhydrous
sodium carbonate (Na2C03) and 0.4 mL
chloroform (CHCI3) to stabilize. Shake
thoroughly or aerate with nitrogen for about
15 min, and store in a glass-stoppered,
reagent bottle. Standardize according to
step B1.
4. Standard Na2S2O3, 0.01 N. Pipette
100.0 mL 0.1 N Na2S203 solution into a 1-L
volumetric flask, and dilute to the mark with
water.
5. Iodine, 0.1 N. Dissolve 24 g Kl in 30 mL
water. Add 12.7 g resublimed I2 to the Kl
solution. Shake the mixture until the I2 is
completely dissolved. If possible, let the
solution stand overnight in the dark. Slowly
dilute the solution to 1 L with water, with
swirling. Filter the solution if it is cloudy.
Store solution in a brown-glass reagent
bottle.
6. Standard I2, 0.01 N. Pipette 100.0 mL
0.1 N I2 into a 1 L volumetric flask, and
dilute to volume with water. Standardize
following step B2 daily. Protect this
solution from light. Keep reagent bottles
and flasks tightly stoppered.
7. HCI, 10%. Add 230 mL cone. HCI to
770 mL water.
8. Starch Indicator. To 5 g starch (potato,
arrowroot, or soluble), add a little cold
water, and grind in a mortar to a thin paste.
Pour into 1 L of boiling water, stir, and let
settle overnight. Use the clear supernatant.
Preserve with 1.25 g salicylic acid, 4 g zinc
chloride, or a combination of 4 g sodium
propionate and 2 g sodium azide per liter of
starch solution. Some commercial starch
substitutes are satisfactory.
B. Standardizations
1. Na2S2O3, 0.1 N. Standardize the 0.1 N
Na2S203 as follows: To 80 mL water,
stirring constantly, add 1 mL cone. H2S04,
10.0 mL 0.100 N KH(IO3)2 and 1 g Kl.
Titrate immediately with 0.1 N NaS203,
until the solution is light yellow. Add 3 mL
starch solution and titrate until the blue color
just disappears. Repeat the titration until
replicate analyses agree within 0.05 mL.
Take the average volume of Na2S2O3
consumed, and calculate the normality to
three decimal figures (see LDS).
2. Iodine, 0.01 N. Standardize the '0.01 N I2
as follows:
a. Pipet 20.0 mL 0.01 N I2 into a 125-mL
Erlenmeyer flask. Titrate with standard
0.01 N Na2S2O3 until the solution is light
yellow. Add 3 mL starch solution, and
continue titrating until the blue color just
disappears.
b. If the normality of the iodine tested is
not 0.010, add a few mL 0.1 N I2 if it is
low, or a few mL water if it is high, and
standardize again. Repeat the titration
until replicate values agree to ±0.05 mL.
Calculate the normality to three decimal
places.
C. Blank Analysis
During sample collection, run a blank as
follows:
1. Add 100 mL zinc acetate solution, 20.0 mL
0.01 N I2/ and 2 mL 10% HCI to a 250-mL
Erlenmeyer flask. Titrate, while stirring, with
0.01 N Na2S203 until the solution is light
yellow. Add starch, and continue titrating
until the blue color disappears.
2. Some difficulties in the titration include:
a. The solution will turn slightly white in
color near the end point, and the
disappearance of the blue color is hard to
recognize.
b. A blue color may reappear in the solution
about 30 to 45 sec after the titration
end point is reached.
D. Sample Analysis
1. After the sample has been stored in the
impingers for 30 min rinse the impinger
stems into the impinger bottoms.
2. Titrate the impinger contents with 0.01 N
Na2S203. Do not transfer the contents of
the impinger to a flask because this may
result in a loss of iodine and cause a positive
bias.
3. Analyze a blank with each sample, as the
blank titer has been observed to change over
the course of a day.
-------
9/30/94: LD16Aa-1
LABORATORY DATA SHEET 16Aa
Hydrogen Sulfide Content in Cylinder Gases
Client/Plant Name
City/State _____
Analyst
Date Analyzed
Job #
Sampling Location
Time Analyzed
Standardizations:
No.
1
2
Avg
Thiosulfate Standard Titration
Volume, Vs
(mL)
Normality,
NT
Iodine Standard Titration
Aliquot, V|
(20 mL)
Volume, VT
(mL)
Normality,
N,
~
V
N, =
Sample Analysis:
V,
Run
No.
Blank # 1
Blank # 2
Blank # 3
Total Sample
Vol. (mL)
100
100
10O
100
100
100
100
100
100
First Impinger, V^
(mL)
Second Impinger, V2
(mL)
Total Standard used*VT
(mL)
-------
9/30/94: S16B-1
SUMMARY SHEET 16B
Reduced Sulfur Compounds
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Avg TRS Concentration, ppm
Sample Line Loss Ratio
Corr Avg TRS Concentration, ppm
CTRS
LR
CTRSc
FDS 16B
FDS 16B
FDS16B
FDS16B
FDS16B
FDS 16B
FDS 16B
FDS 16B
FDS 16B
SS16B
Run#1
Run #2
Run #3
Avg
CTRS
LR
-------
9/30/94: F16B-1
FIELD PROCEDURE 16B
Reduced Sulfur Compounds
Note: FP 16Bis a combination of Methods 16 (same as Method 15) and 16A. The oxidized sulfur
compounds are measured using gas chromatography/flame photometric detection. The O2 content in the
flue gas must be fe / %. Use FDS 16B.
A. Sampling Train Preparation
1. Set up the sampling train as shown in
Figure F16B-1. Prepare the sampling train
according to section A of FP 16A.
2. Set up the GC/FPD system according to
FP 15, section B (Methods 15 and 16 are
identical).
C. System Performance Check
Conduct this check according to FP 16A,
section C, except use measurements of the
GC/FPD to determine the precision.
B. Sample Collection
1. Sample according to FP 15, section C.
2. If the sample is diluted determine the precise
dilution factor.
Probe
Heater Box
with Filter
SO2
Scrubbing
Impinger
Gas Chromatographic-
Flame Photometric
Analyzer
Dilution
Vacuum
Pump
Tube
Furnace
Figure F16B-1. Sampling Train.
-------
9/30/94: FD16B-1
FIELD DATA SHEET 16B
Reduced Sulfur Compounds
Client/Plant Name
City/State
Date
Job #
Personnel
Calibration (/) Initial
Post-Test
(^ ±5% DH1?) Sampling Location
Cone.
Level
1
2
3
S02 Cone.,
C
(ppm)
GC/FPD Response: %Dev = «; ±5%
Inject #1
Inject #2
Inject #3
Average
High % Dev
Note: Plot response vs. concentration; attach graph.
Use only If dilution Is necessary.
Fyrite O2
(1 % ?)
Stage
1
2
SO2
Cone.
(ppm)
GC/FPD Resp: % Dev =
-------
9/30/94: F17-1
FIELD PROCEDURE 17
Paniculate Matter
Note: The sampling and analytical procedures are the same as Method 5, except for the following (Use
Method 5 data sheets, except do not use the column for Filter Holder Temperature in FDS 5):
A. Sampling Train
1. Do not use this method in stacks that
contain liquid droplets or are saturated with
water vapor.
2. Thimble glass fiber filters may also be used.
3. An interference free arrangement of in-stack
filter assembly and Type S pitot tube (see
Figure F17-1) must be used, or the pitot
tube must be calibrated as assembled.
4. Flexible tubing may be used between the
probe extension and condenser. Long
tubing lengths may affect the moisture
determination.
B. Preliminary Determinations
1.. Make a projected-area model of the probe
extension-filter holder assembly, with the
pitot tube face openings positioned along
the centerline of the stack, as shown in
Figure F17-2.
2. Calculate the estimated cross-section
blockage, as shown in Figure F17-2. If the
blockage exceeds 5% of the duct cross
sectional area, the tester has the following
options: (1) use a suitable out-of-stack
filtration method or (2) use separate
sampling and velocity measurement sites.
C. Sampling
For the leak-check procedure, use FP 5a with
the following modifications:
1. Plug the inlet to the probe nozzle with a
material that will be able to withstand the
stack temperature.
2. Insert the filter holder into the stack and wait
about 5 min (or longer, if necessary) before
turning on the pump to allow the.system to
come to equilibrium with the temperature of
the stack gas stream.
T«itp«ntura
Imphgir Train Oplfcml. Miy B> R.plac.d
«y An Equkitonl Cmtmtn
T«mp«ralur*
Smtor
Tomponlur* In-SUck
Senior FM«r
^"-'^'^sa^a i ii
/ VKS C>
117.0 cm (J In.)' Tuo« *••«». I
• SUJJ.H.S (MI«r«r
-------
In-Sltck
Pfatit Extension
A»*mbly
Figure 17-2. ProJected-Area Mod«lof Crosc-Stdlon Blockage (Approximale Average for
a Simple Traversa) Caused by an In-Stack Fitter Hotder*Probe Extension Assembly.
-------
9/30/94: F18-1
FIELD PROCEDURE 18
Gaseous Organic Compounds
(Gas Chromatography)
Note: This procedure attempts to analyze about 90% of the total gaseous organics emitted from an
industrial source and does not identify and measure trace amounts of organic compounds, such as those
found in building air and fugitive emission sources. This procedure will not determine compounds that (1) are
polymeric (high molecular weight), (2) can polymerize before analysis, or (3) have very low vapor pressures
at stack or instrument conditions.
The forms in this section contain the information required by the test method; we are aware that some
of the technology specified in the test method is obsolete. In these cases, the user should modify the forms
to make them consistent with the technology used.
A. Pretest Survey and Pretest Survey Sampling
1. Obtain (from pretest surveys, literature
surveys, experience, discussions with plant
personnel, etc.) all information necessary to
design the emission test, e.g., see FDS 18.
2. Obtain pretest survey samples of the gas and
analyze to confirm the identity and
approximate concentrations of the specific
compounds. The following sections include
suggested sampling procedures.
B. Glass Sampling Flasks
1. Cleaning Procedure. Clean a 250-mL double-
ended glass sampling flask with Teflon
stopcocks, without grease, as follows:
a. Remove the stopcocks from both ends
of the flasks, and wipe the parts to
remove any grease. Clean the
stopcocks, barrels, and receivers with
methylene dichloride. Clean all glass
ports with a soap solution, then rinse
with tap and deionized distilled water.
b. Place the flask in a cool glass annealing
furnace, and heat up to 500°C and
maintain at 500°C for 1 hr. Then shut
off and open the furnace to allow the
flask to cool.
c. Reassemble the flask. Purge the
assembly with high-purity N2 for 2 to
5 min. Close off the stopcocks after
purging to maintain a slight positive N2
pressure. Secure the stopcocks with
tape.
2. Evacuated Flask Procedure. Use this
procedure or the purged flask procedure
(section B3) to collect the samples. At this
time, the EPA does not approve using
SUMMA" canisters for collecting Method 18
samples.
a. Evacuate the flask to the capacity of a
high-vacuum pump; then close off the
stopcock leading to the pump.
b. Attach a 6-mm OD glass tee to the flask
inlet with a short piece of Teflon tubing.
c. Select a 6-mm OD borosilicate sampling
probe of sufficient length. Enlarge one
end to 12-mm OD and insert a glass
wool plug. Attach the other end of the
probe to the tee with a short piece of
Teflon tubing. Connect a rubber suction
bulb to the third leg of the tee.
d. Place the filter end of the probe at the
centroid of the duct or at a point * 1 m
from the stack wall and, using the
rubber suction bulb, purge the probe
completely with stack gases.
e. Open the stopcock to the grab flask
until the pressure in the flask reaches
duct pressure. Close off the stopcock,
and remove the probe from the duct.
f. Remove the tee from the flask and tape
the stopcocks to prevent leaks during
shipment.
g. Measure the duct temperature and
pressure.
3. Purged Flask Procedure. Use this procedure
or the evacuated flask procedure
(section B2) to collect the samples.
a. Attach one end of the sampling flask to
a rubber suction bulb. Attach the other
end to a 6-mm OD glass probe as ,
described in step B2c.
b. Place the filter end of the probe as in
step B2d, and use the suction bulb to
completely purge the probe and flask.
c. Close off the stopcock near the suction
bulb, and then close off the stopcock
near the probe.
d. Remove the probe from the duct, and
disconnect both the probe and suction
bulb. Tape the stopcocks to prevent
leakage during shipment.
e. Measure the duct temperature and
pressure.
-------
9/30/94: F18-2
C. Flexible Bags
1. Prepare new bags made of Tedlar or
aluminized Mylar. Leak-check them before
field use (see FP 3b).
2. Fill the bag with N2 or air, allow to stand for
24 hr, and analyze the gas by GC at high
sensitivity for organics.
Note: The volume of the evacuated bag must
be known when doing an in-the-bag dilution
of the sample.
3. Collect the samples according to FP 18a.
D. Other Measurements
1. Obtain the moisture content from plant
personnel or measure directly, using either
psychrometry (<59°C) or Method 4.
2. Obtain the static pressure from the plant
personnel or measure it.
E. Final Sampling and Analysis Procedure
Considering safety (flame hazards), source
conditions, and pretest survey results, select an
appropriate sampling and analysis procedure. The
following are some considerations:
1. In situations where a H2 flame is a hazard and
no intrinsically safe GC is suitable, use the
flexible bag collection technique or an
adsorption technique.
4.
5.
Use the direct interface method if the source
effluent is <100 C, the moisture content of
the gas does not interfere with the analysis
procedure, the physical requirements of the
equipment can be met at the site, and the
source gas concentration is low enough that
detector saturation is not a problem. Adhere
to all safety requirements with this method.
If the source gases require dilution, use a
dilution interface and either the bag sample
or adsorption tubes. The choice between
these two techniques will depend on the
physical layout of the site, the source
temperature, and the storage stability of the
compounds if collected in the bag.
Sample polar compounds by direct
interfacing or dilution interfacing to prevent
sample loss by adsorption on the bag.
Use stainless steel, Pyrex glass, or Teflon
materials of construction for sample-exposed
surfaces.
6. See subsequent procedures.
-------
I. Client/Plant Name
Address
Corporate Contact
Plant Contact
Test Location(s)
9/30/94: FD18-1
FIELD DATA SHEET 18
Gaseous Organic Compounds
Preliminary Site-Survey
Job #
Date
Phone #
Phone #
II. Process Description
Raw Material
Products
Operating Cycle:
III. Sampling Site
A. Site Description
Check: Batch
Continuous
Cyclic
Timing of batch or cycle:
Best time to test:
Duct/stack shape and dimensions
Material
Upstream distance to flow disturbance
Downstream distance to flow disturbance
No. of ports available Port inside diameter
Size of access area
Hazards
Wall thickness
inches
inches
inches
inches
diameters
diameters
Port nipple length
inches
Ambient temperature at test location
B. Properties of the gas stream
Temperature Range °F
Velocity
Static pressure
Moisture Content
Paniculate Content
ft/sec
in. H2O
Data source
Data source
Data source
Data source
Data source
Gaseous components:
N
2_
CO
CO,
Hydrocarbons
Ppm
Hydrocarbon components:
ppm
ppm
ppm
ppm
-------
9/30/94: FD18-2
FIELD DATA SHEET 18 (Continued)
C. Sampling consideration
Location to set up GC
Special hazards to be considered_
Power availability at sample location
Power availability for GC
Plant safety requirements
Vehicle traffic rules
Plant entry requirements_
Security agreements
Potential Problems
D. Site Diagrams. (Attach additional sheets if required).
-------
9/30/94: L18-1
LABORATORY PROCEDURE 18
GC Analysis Development
A. Selection of GC Parameters
1. Using the pretest survey information, select
a column that provides good resolution and
rapid analysis time. Consulting column
manufacturers is recommended.
2. Using the standards (see CP 18) and
selected column, perform initial tests to
determine appropriate GC conditions for the
compounds of interest.
3. Analyze the audit described in 40 CFR
Part 61, Appendix C, Procedure 2,
"Procedure for Field Auditing GC Analysis."
SeeLDS18.
4. Prepare pretest survey samples as follows:
a. If the samples were collected on an
adsorbent, extract the sample as
recommended by the manufacturer for
removal of the compounds with a
solvent suitable to the type of GC
analysis.
b. Prepare other samples in an appropriate
manner.
c. Heat the pretest survey sample to the
duct temperature to vaporize any
condensed material.
5. Inject the samples into analyzer using the
GC conditions determined in step A2.
Identify all peaks by comparing the known
retention times of calibration standards.
Identify any remaining unidentified peaks
that have areas >5% of the total using
GC/mass spectroscopy (GC/MS),"
GC/infrared techniques, or estimation of
possible compounds by their retention times
compared to known compounds, with
confirmation by further GC analysis.
a. To inject a sample, draw sample
through the loop at a constant rate
(100 mL/min for 30 sec). Be careful not
to pressurize the gas in the loop.
b. Turn off the pump and allow the gas in
the sample loop to come to ambient
pressure. Activate the sample valve.
c. Determine the GC parameters
(seeLDS18).
6. Vary the GC parameters during subsequent
injections to determine the optimum
settings. After determining the optimum
settings, perform repeat injections of the
sample to determine the retention time of
each compound (must be repeatable to
within ±6.5 sec).
7. If the concentrations are too high for
appropriate detector response, use a
smaller sample loop or dilutions gas
samples and, for liquid samples, dilute with
solvent.
B. Preparation of Calibration Curves
1. Establish proper GC conditions.
2. Inject each standard (three per attenuator
range) until two consecutive injections give
area counts within ±5% of their average.
See CP 18 for the preparation of calibration
'• standards.
3. Plot concentrations along the abscissa and
the calibration area values along the
ordinate. Perform a regression analysis,
and draw the least squares line.
C. Relative Response Factor
1. Relate the calibration curve from the
cylinder standards for a single organic to
the GC response curves of all the
compounds in the source by response
factors developed in the laboratory.
2. Use this single organic compound to
"calibrate" the GC in the field for all
compounds measured.
-------
9/30/94: LD18-1
LABORATORY DATA SHEET 18
GC Chromatographlc Conditions
Client/Plant Name
City /State
Job #
Date
Test Locations)
Components to be analyzed
Expected concentration
Suggested chromatographic column
Column flow rate
mL/min Head pressure
mm Hg
Column temperature: Isothermal
Injection port/sample loop temperature
Detector flow rates: Hydrogen
Chart speed
Air/Oxygen
inches/minute
Compound data:
Compound
°C Programmed from
°C to
°C at
°C Detector temperature
mL/min head pressure • mm Hg
_ mL/min head pressure mm Hg
' Retention times Attenuation
Inject #1 Inject #2
°C/min
Retention times repeatable to £ ±0.5 seconds?
-------
9/30/94: C18-1
CALIBRATION PROCEDURE 18
Calibration Gas Preparation
A. Cafiucation Standards
Using the information from FP 18, prepare or
obtain enough calibration standards so that there
are at least three different concentrations of each
organic compound expected to be measured.
Select the concentrations to bracket the stack
levels. Mixtures may be used. Use one of the
following procedures in the following sections for
preparing standards or the respective NIOSH
procedures: -
B. Dilution of High Concentration Cylinder
Standard
1. Refer to Figures C18-1 «1:20 dilution) and
C18-2 (> 1:2Q dilution) or use commercially
available dilution systems. Calibrate with
diluent gas the rotameters or other flow
meters using a bubble meter, spirometer, or
wet test meter (see CDS 18a).
2. Leak-check the Tedlar bag according to
FP 3b. Set up the system as shown in
Figure C18-1 or Figure C18-2.
3. Adjust the gas flow to provide the desired
dilution {< 1:20 dilution). Fill the bag with
sufficient gas for GC calibration. Do not
overfill and cause the bag to pressurize.
See CDS 18b.
4. Calculate the diluted concentration.
C. Preparation of Standards from Volatile
Materials - Gas Injection Technique
Use this procedure for organic compounds that
exist entirely as a gas at ambient conditions.
SeeCDSISc.
1. Leak-check the 10-L Tedlar bag according to
FP 3b.
2. Evacuate the bag, and meter in 5.0 L of air or
N2 through an appropriate dry gas meter.
3. While the bag is filling, inject with a O.5-ml
syringe a known quantity of the "pure" gas
of the organic compound through the wall of
the bag or through a septum-capped tee at
the bag inlet. Withdraw the syringe needle,
and immediately cover the resulting hole with
a piece of masking tape.
4. Place each bag on a smooth surface, and
alternately depress opposite sides of the bag
50 times to mix the gases.
5. Calculate each organic standard
concentration.
D. Preparation of Standards from Volatile
Materials - Liquid Injection Technique •
1. Use the equipment shown in Figure C18-3
and CDS 18c. Calibrate the dry gas meter
with a wet test meter or a spirometer. Use a
water manometer for the pressure gauge and
glass, Teflon, brass, or stainless steel for all
connections. Connect a valve to the inlet of
the 50-liter Tedlar bag.
2. Assemble the equipment as shown in
Figure C18-3, and leak-check the system.
Completely evacuate the bag. Fill the bag
with hydrocarbon-free air, and evacuate the
bag again. Close the inlet valve.
3. Turn on the hot plate, and allow the water to
reach boiling. Connect the bag to the
impinger outlet. Record the initial meter
reading, open the bag inlet valve, and open
the cylinder. Adjust the rate so that the bag
will be completely filled in about 15 min.
Record meter readings.
4. • Allow the liquid organic to equilibrate to
room temperature. Using a 1.0- or 10-uL
syringe, inject the desired liquid volume into
the flowing air stream through the impinger
inlet septum. Use a needle of sufficient
length to permit injection of the liquid below
the air inlet branch of the tee. Remove the
syringe.
5. When bag is filled, stop the pump, and close
the bag inlet. Record the meter readings.
6. Disconnect the bag from the impinger outlet,
and either set it aside for at least 1 hr or
massage the bag to ensure complete mixing.
7. 'Determine the solvent liquid density at room
temperature; accurately weigh a known
volume (use a ground-glass stoppered 25-mL
volumetric flask or a glass-stoppered specific
gravity bottle) of the material to ± 1.0 mg.
Alternatively, use literature values at 20 °C.
8. Calculate each organic standard
concentration.
-------
Valve
Component
Gat
Cylinder
M
Hxi 1
1 1 1
Compone
WithF
Va
Valve
-co .ffii r—
DHuent
Gas
Cylinder
ri
nt Rotameters
ow Control
Ives
""]
T" Connector
/
1
4
TedU
1 i i
NOTE: Use 6-mm Teflon Tubing for C
Figure C18-1. Single-Stage Calibration Gas Dilution System.
Rota mete
High
Concentration
Waste
i—Needle Valves
Low
Pure Substance or
Pun) Substance/Nitrogen Mixture
Pressure pressure
Regulator Regulator
Diluent Air Diluent Air
NOTE Use 6-mm Teflon tubing for connections.
Figure C18-2. Two-Stage Dilution Apparatus.
Nitrogen
Cylinder
NOTE: Use 6-mm Teflon tubing for connections.
Figure C18-3. Apparatus for Preparation of Liquid Materials.
-------
9/3O/94: CDT8a-T
CALIBRATION DATA SHEET 18a
Flowmeter Calibration
Flowmeter ID •• Flowmeter type
Calibration device (/): Bubble meter Spirometer
Wet test meter
Date
Lab Temp, Tlab
Lab Barometric Pressure, P|ab
mm Hg
Analyst
Note: If a spirometer or bubble meter is used, revise the data sheet. For an example of a bubble meter used as a
calibration device, see FP 6a.
Flowmeter
Reading
(as marked)
Temp.
(K)
Abs Press.
(mm Hg)
Calibration Device (WTM)
Time, Q
(min)
Vol, Vw
(L)
Temp., Tw
(K)
Am
(cm H2O)
Vstd
(L)
Flow rate, qc
(mL/min)
Vm(std) = 0.3858 Vw -*.
w
qc =
v..
Plot: Flowmeter readings vs flow rate (qc) at standard conditions. Attach plot.
Note: If the flowmeter is viscosity dependent, generate calibration curves that cover the operating pressure and
temperature ranges of the flowmeter.
.Note: The following may be used to calculate flow rate readings for rotameters at standard conditions (0,^), but
should be verified before application.
Flow rate:
f~T
CL- = 1.611 C U*
Laboratory conditions (Q|at,)
Standard conditions (Qstd)
QA/QC Check
Completeness
Checked by: _
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: CD18b-1
CALIBRATION DATA SHEET 18b
Gas Standard Preparation by Dilution of Cylinder Standard
Client/Plant Name
City/State
GC!D#
Job #
Date
Date Last Calibration
Analyst
Cylinder Standard: Organic
Certified concentration, C_
. ppm
Standards Preparation:
Stags 1
Stngo 2
(if used)
GC Operating Conditions:
Organic peak identification
and calculated
concentrations:
Standard Mixture #
Std gas flowmeter reading
Diluent gas flowmeter reading
Lab temperature (K)
Barometric pressure, * (mm Hg)
Std gas flow rate, std cond., qr1 (mL/min)
Diluent gas flow rate, std cond., qrf1 (mL/min)
Calculated concentration, Cs (ppm)
Std gas flowmeter reading
Diluent gas flowmeter.reading
Stage 1 gas flow rate, std cond., qr7 (mL/min)
Diluent gas flow rate, std cond., qd;) (mL/min)
Calculated concentration, CK (ppm)
Sample loop vol., (ml)
Sample loop temp. (°C)
Carrier gas flow rate, (mL/min)
Column temp. Initial, (°C)
Rate Change (°C/min)
Final, (°C)
Injection time (24-hour clock)
Distance to peak, , (cm)
Chart speed (cm/min)
Organic retention time, (min)
Attenuation factor
Peak area, (mm2)
Peak Area x attenuation factor, (mm2)
1
2
'.
(•'•" ' " '
•
3
••
Plot: Peak area x attenuation factor vs calculated concentration.
QA/aC Check
Completeness
Checked by:
One-stage: C8 = Cc —^— Two-stage: Cs = Cc f—^—) f—^—}
\ **i *"/ \ ^^ ^* /
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: CD18c-7
CALIBRATION DATA SHEET 18c
Gas Standards by Gas/Liquid Injection into Bags
Client/Plant Name
City/State
GC ID #
Job #
Date
Date Last Calibration
Analyst
Standards Preparation:
GC Operating Conditions:
Organic peak identification
and calculated
concentrations:
Standard Mixture #
Organic:
Bag I.D.
DGM Y
Final DGM reading (L)
Initial DGM reading (L)
Metered volume, Vm (L)
Avg DGM temp, Tm (K)
Avg DGM Press, Pn (mm Hg)
Avg Bar pressure, Ph (mm Hg}
Abs DGM press, Ph + P0 (mm Hg)
Abs syringe temp, Ts (K)
Abs syringe press, PB (mm Hg)
Vol. gas in syringe, Gu (mL)
Density of liquid organic, p (g/mL)
Vol. liquid in syringe, L,, . dA.)
Sample loop vol. (mL)
Sample loop temp. (°Q
Carrier gas flow rate (mL/min)
Column temp. Initial, (°C)
Rate Change (°C/min)
Final, (°C)
Injection time (24-hour clock)
Distance to peak (cm)
Chart speed (cm/min)
Organic retention time (min)
Attenuation factor
Peak height (mm)
Peak area (mm2)
Peak area x attenuation factor (mm2)
Calculated cone., C, (ppm)
1
2
•.
— , —
'..
,.•,,
3
„_ .
. .
Plot: Peak area x attenuation factor vs calculated concentration.
Gas-injection: C' = 103 GvF>sTm
Liquid-injection: Cs = 6.24x10'
,4 LvPT
QA/aC Check
Completeness
VmYPmTs
Legibility _. Accuracy Specifications Reasonableness
.Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
Vent
Filter
(Glats.WooO
Figure F18a-1. Integrated Bag Sampling Train.
STeflolfTublng
PVC Tubing
Probe
Pinch Clamp
Grommet
Alright Steal Dtum
Flowmetor •
A
\ Sample Bag
Evacuated Steel
Drum
Figure F18a-2. Explosion Risk Gas Sampling Method.
-------
9/30/94: F18a-1
FIELD PROCEDURE 18a
Integrated Bag Sampling
A. Evacuated Container Procedure
Refer to the sample train shown in
Figure F18a-1 and FDS 18a. Collect triplicate
samples from each sample location.
1. Leak-check both the bags and the container
as follows:
a. Connect a water manometer using a tee
connector between the bag or rigid
container and a pressure source.
b. Pressurize the bag or container to 2 to
4 in. H2O, and allow it to stand
: overnight. A deflated bag indicates a
leak.
2. Purge the probe as follows: Connect the
vacuum line from the needle valve to the
Teflon sample line from the probe. Place the
probe inlet at the centroid of the stack, or at
a point & 1 m from the stack wall, and purge
at 0.5 L/min for sufficient time to purge the
line several times.
3. Evacuate the bag as follows: Connect the
vacuum line to the bag, and evacuate until
the rotameter indicates no flow.
4. Reconfigure the sample and vacuum lines for
sampling, and sample proportional to the
stack velocity. As a precaution, direct the
gas exiting the rotameter away from
sampling personnel.
5. At the end of the sample period, shut off the
pump, disconnect the sample line from the
bag, and disconnect the vacuum line from
the bag container. Record the information
shown in FDS 18a.
6. Protect the Tedlar bag and its container from
sunlight. When possible, perform the
analysis within 2 hr of sample collection.
SeeLP 18a.
7. After analysis, leak-check both the bags and
the container as in step 1.
B. Direct Pump Procedure
Follow section A, except for the following
variations:
1. Place the pump and needle valve between
the probe and the bag.
2. Leak-check the system, and then purge with
stack gas before connecting to the
previously,evacuated bag.
C. Explosion Risk Area Bag Sampling Procedure
Use this method whenever there is a possibility
of an explosion due to pumps, heated probes, or
other flame producing equipment. Follow step A,
except replace the pump with another evacuated
container (see Figure F18a-2).
D. Other Modified Bag Sampling Procedures
If condensation occurs in the bag during
sample collection and a direct interface'system
cannot be used, use either of the following
modifications:
1. Heating. Heat (conforming to safety
restrictions) the box containing the sample
bag to the source temperature (assuming
system can withstand this temperature).
Maintain the temperature until analysis.
2. Dilution. Leak-check the system (leaky
systems may create a potentially explosive
atmosphere). Using the setup shown in
Figure C18-3 (without midget impinger
section), meter an inert gas into the Tedlar
bag. Take the partly filled bag to the source,
and meter the source gas into the bag
through heated sampling lines and a heated
flowmeter, or Teflon positive displacement
pump. As a quality control check, dilute and
analyze a gas of known concentration and
validate technique by checking the dilution
factor.
-------
9/30/94: FD18a-1
Client/Plant Name
City/State
Test Location/Run #
FIELD DATA SHEET 18a
Integrated Bag Sampling
Job #
Date
Personnel
Sample No.
Source temperature (°C)
Probe temperature ; (°C)
Source pressure, Pg (mm Hg)
Barometric pressure, Pb (mm Hg)
Abs source pressure (Pb + Pg), Ps (mm Hg)
Ambient temperature (°C)
Sample flow rate (approx) . , (L/min)
Bag No.
Start time
Finish time
1
2 , ,
,. ,,
3
QA/aC Check
Completeness
Checked by: _
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: U8a-1
LABORATORYPROCEDURE 18a
Integrated Bag Sample Analysis
A. Analysis
1. Connect the needle valve, pump, charcoal
tube, and flowmeter to draw gas samples
through the gas sampling valve.
2. Flush the sample loop with gas from one of
the three Tedlar bags containing a calibration
mixture, and analyze the sample.
3. Obtain at least two chromatograms for the
sample or until the peak areas from two
consecutive injections agree to within ±5%
of their average.
4. After obtaining acceptable results, analyze
the other two calibration gas mixtures in the
same manner.
5. Prepare the calibration curve by using the
least squares method.
6. Analyze the two field audit samples by
connecting each Tedlar bag containing an
audit gas mixture to the sampling valve.
Calculate the results; report the data to the
audit supervisor. If the results are
acceptable, proceed with the analysis of the
source samples.
7. Analyze the source gas samples by
connecting each of the three bag samples to
the sampling valve with a piece of Teflon
tubing identified with that bag. Follow the
restrictions on replicate samples specified for
the calibration gases (step A3).
8. After all three bag samples have been
analyzed, repeat the analysis of the
calibration gas mixtures. Use the average of
the two calibration curves to determine the
respective sample concentrations. If the two
calibration curves differ by >5% from their
mean value, then report the final results by
both calibration curves.
B. Recovery Study
1. Prepare (if not already available) calibration
gas mixtures of all target compounds within
40 to 60% of the average concentration of
the three bag samples. If not detected, use a
concentration 5 times the detection limit of
that compound.
2. Select one of the three bag samples and
analyze in duplicate as in step A3. Then
spike the bag sample with calibration gas
mixtures of all the target pollutants.
3. Analyze the bag sample three times after
spiking and average the results.
4. Calculate the recovery, R, for each target
compound (must be 0.70sR:s 1.30).
5. Adjust field sample concentrations using R
for each compound.
C. Determination of Bag Water Vapor Content
1. Measure the ambient temperature and
barometric pressure near the bag.
2. From a water saturation vapor pressure
table, determine and record the water vapor
content of the bag as a decimal figure.
Assume the relative humidity to be 100%
unless a lesser value is known.
D. Notes
1. Eliminate resolution interferences by
selecting appropriate GC column and
detector or by shifting the retention times
through changes in the column flow rate and
the use of temperature programming.
2. Periodically analyze blanks that consist of
hydrocarbon-free air or N2 to demonstrate
that analytical system is essentially free from
contaminants.
3. To eliminate sample cross-contamination that
occurs when high-level and low-level
samples or standards are analyzed
alternately, thoroughly purge the GC sample
loop between samples.
4. To assure consistent detector response,
prepare calibration gases in dry air.
-------
9/30/94: LD18a-1
LABORATORY DATA SHEET 18a
GC Analysis of Field Samples
Client/Plant Name
City/State
Job #
Date
Sample Moisture Content, Bv
Personnel
Note: Conduct a pre- and post-test calibration using three gas mixtures from CDS 18b or c, plot calibration curve,
and attach. Record the average barometric pressure and temperature of the pre- and post-test conditions here:
mm Hg
K
Note: Use more data sheets as needed.
Chromatograph Operation
Parameter
Sample loop volume (mL)
Sample loop temp, T? (K)
Column temp initial (°C)
Column temp, program rate {°C/mL)
Column temp final (°C)
Carrier gas flow rate (mL/min)
Setting
Parameter
Detector temp (°C)
Chart speed (cm/mfn)
Sample flow rate (mL/min)
Dilution gas flow rate (mL/min)
Dilution Gas used (symbol)
Dilution ratio, Df
Setting
'..
Bar. pressure during sample analysis, P-.
mm Hg
Samples to be analyzed in addition to field samples: Two Audits, Blanks, Spiked and Unspiked Field Sample
Sample
ID
Inject'n
Time
(Clock)
Organic
Compnt
Dist to
Peak
(cm)
Retent.
Time
(sec)
Atten.
Factor
AC
Peak Area,
V
(mm2)
AcxAm
(mm2)
Cone.
Cs
(ppm)
Calc Cor
Cc
(ppm)
The pre- and post- calibration curves are
within 5% of their mean value? If not,
report final results by comparison to both
calibration curves.
Audit analyses agree ±10% of the audit
concentrations?
CsPrT,Fr
Peak areas from 2 consecutive injections
agree ±5% of their average?
QA/aC Check
Completeness
Checked by: _
Legibility
C P,Tr(1-Bws)
Fr = Response factor, if needed.
Accuracy Specifications Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: LD18a-2
LABORATORY DATA SHEET 18a (Continued)
Bar. pressure during sample analysis, Pj mm Hg
Sample
IP
Inject' n
Time
(Clock)
Organic
Compnt
Dist to
Peak
(cm)
Retent.
Time
(sec)
Atten.
Factor
AC
Peak Area,
v
(mm2)
AoxAm
(mm2)
Cone.
cs
(ppm)
.
Calc Cone
cc
(ppm)
, .
Peak areas from 2 consecutive injections
agree ±5% of their average?
C
P.Trd-BJ
Fr = Response factor, if needed.
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: LD18a-3
LABORATORY DATA SHEET 18a (Continued)
Recovery Study Bag ID
Target
Compound
Unspiked Bag (ppm)
Inj. 1
Inj. 2
Avg, u
Spiked Bag (ppm)
Amt, s*
Inj. 1
Inj. 2
Inj. 3
Avg, t
;.-. , '
' '
Recover- •
R
* Theoretical concentration of spiked target compound.
Concentrations In spiked bag sample must be 40 to 60%
that of unspiked. If target compound is not detected in
unspiked bag sample, spiked bag sample must be at least
5 times the detection limit.
s
0.70 £R :£ 1.30 for tests to be valid.
Data Summary
Average of duplicate injects that met the ±5% criterion.
Target
Compound
QA/QC Chock
Completeness
Checked by:
Run #1 (ppm)
CC1*
Legibility
CC1/R
Run #2 (ppm)
CC2
Cc2/R
Run #3 (ppm)
CC3
co3/R
Corr
Avg"
(ppm)
Accuracy Specifications Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
2/13/95; Fm-1
FIELD PROCEDURE 18b
Direct Interface Sampling and Analysis
1. Assemble the sampling system as shown in
Figure F18b-1. Prepare the GC accordingly.
Ensure all connections are tight.
2. Turn on the probe and sample line heaters to
achieve a 0 to 3°C above the source
temperature.
3. While the probe and sample line are being
heated, disconnect the sample line from the
gas sampling valve, and attach the line from
the calibration gas mixture. Flush the sample
loop with calibration gas and analyze a
portion of that gas. Calibrate the system
with other concentration levels.
4. After successfully calibrating the system,
turn the gas sampling valve to flush position,
then reconnect the probe sample line to the
valve. Attach the mid-level calibration gas
for at least one target compound to the inlet
of the probe or as close as possible to the
inlet of the probe, but before the filter.
5.
6.
7.
8.
9.
Analyze the mid-level cal; Jration gas until
two consecutive samples are within ±5% of
their mean value (this value must be within
±10% of the value obtained in step 3).
Analyze two field audit samples, if
applicable, through the gas sampling valve at
the same instrument conditions as that for
the source samples.
Reconfigure the train for sampling. Move
the probe to the sampling position, and draw
source gas into the probe, heated line, and
sample loop.
After thorough flushing, analyze the sample
in duplicate using the same conditions
(especially the same pressure) as that for the
calibration gas mixture until the duplicates
agree within ±5% of their mean value.
Remove the probe from the source and
analyze a second calibration gas mixture.
10. Record all data on FDS 18b.
Figure F18b-1 Direct Interface Sampling Syitem.
-------
2/13/95: FD18b-1
FIELD DATA SHEET 18b
GC Direct Interface Analysis
Client/Plant Name
City/State
Job #
Date
Personnel
Sample Moisture Content, BW8 ___^_
Note: Conduct a pre- and post-test calibration using three gas mixtures from CDS 18b or c, plot calibration curve,
and attach. Record the average barometric pressure and temperature of the pre- and post-test conditions here:
mm Hg
Note: Use more data sheets as needed.
Chromatograph Operation
Parameter
Sample loop volume (mL)
Sample loop temp, T( (K)
Column temp initial (°C)
Column temp, program rate {°C/mLJ
Column temp final (°C)
Carrier gas flow rate (mL/min)
Setting
• Parameter
Detector temp <°C)
Chart speed (cm/min)
Sample flow rate (mL/min)
Setting
Bar. pressure during sample analysis, Ps.
mm Hg Probe/sampling line set at 0-3°C above stack
temperature?
Samples to be analyzed in addition to field samples: Two Audits, Mid-Cal Mixture from the inlet to the probe or as
close as possible, but before the filter. (Concentration from probe and from analyzer must be within 10%.)
Sample
ID
Inject'n
Time
(Clock)
Organic
Compnt
Distto
Peak
(cm)
Retent.
Time
(sec)
Atten.
Factor
AC
Peak Area,
V
(mm2)
AcxAm
(mm2)
Cone.
C,
(ppm)
Calc Cone
cc
(ppm)
The pre- and post- calibration curves are within
5% of their mean value? If not, report final
results by comparison to both calibration curves.
Peak areas from 2 consecutive injections agree
±5% of their average?
Audit analyses agree ±10% of the audit
concentrations?
Concentration from probe and from analyzer
within ±10%?
P,Tr(1-BJ
QA/aC Check
Completeness
Legibility
Accuracy
Response factor, if needed.
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
FIELD DATA SHEET 18b (Continued)
Bar. pressure during sample analysis, Pj mm Hg
9/30/94: FD18b-2
Sample
ID
Inject'n
Time
(Clock)
Organic
Compnt
Dist to
Peak
(cm)
Retent.
Time
(sec)
Atten.
Factor
AC
Peak Area
(rnrrv2)
Ac* Am
(mm2)
-
Cone.
cs
(ppm)
-
-
Calc Cone
Co
(ppm)
Peak areas from 2 consecutive injections agree
±5% of their average?
QA/dC Chock
Completeness
° P,T,<1-B,J
Response factor, if needed.
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
2/13/95: FD18b-3
FIELD DATA SHEET ~,8ti (Continued)
Recovery Study Average of duplicate injects that met the ±5% criterion.
Target
Compound
(Mid-level)
At Analyzer (ppm)
Inj. 1
Inj. 2
Avg*, A
From Probe (ppm)
Inj. 1
Inj. 2
Avg, P
Recovery
R
Data Summary
R =
A-P
R = 0.90 to, 1.10 for tests to be valid.
Averages of duplicate injects that met the ±5% criterion.
Target
Compound
Run #1 '
(ppm)
Run #2
(ppm)
Run #3
(ppm)
Avg
(ppm)
QA/QC Check
Completeness
Checked by: _
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
2/13/95: F18c-1
FIELD PROCEDURE 18c
Dilution Interface Sampling and Analysis
Note: The apparatus required for this direct interface procedure is basically the same as that described in
FP 18b, except a dilution system is added between the heated sample line and the gas sampling valve.
The apparatus is arranged so that either a 1O:1 or 100:1 dilution of the source gas can be directed to the
chromatograph. A pump of larger capacity is also required, and this pump must be heated and placed in
the system between the sample line and the dilution apparatus. Use FDS JSc.
1. Assemble the apparatus by connecting the
heated box, shown in Figure F18c-1,
between the heated sample line from the
probe and the gas sampling valve on the
chromatograph. Leak-check the system prior
to the dilutions so as not to create a
potentially explosive atmosphere.
2. Vent the source gas from the gas sampling
valve directly to the charcoal filter (eliminate
the pump and rotameter). Heat the sample
probe, sample line, and heated box. Insert
the probe and source thermocouple at the
, centroid of the duct.
3. Measure the source temperature, and adjust
all heating units to 0 to 3°C above this
temperature. If this temperature is above the
safe operating temperature of the Teflon
components, adjust the heating to maintain a
temperature high enough to prevent
condensation of water and organic
compounds.
4. Analyze a high concentration calibration gas
(one of the target compounds) of known
composition through the probe inlet (or as
close as possible to the inlet) at either the
10:1 or 1OO:1 dilution stages, as appropriate
(if necessary, vary the flow of the diluent
gas to obtain other dilution ratios) to verify
the operation of the dilution system and
integrity of sampling system.
5. Analyze the calibration gas until two
consecutive samples are within ±5% of
their mean value. Determine the
concentration of the diluted calibration gas
using the dilution factor and the calibration
curves prepared in the laboratory (must be
within ± 1O% of the expected values).
6. Verify the GC operation using a low
concentration standard by diverting the gas
into the sample loop and bypassing the
dilution system.
7. Analyze two field audit samples'using either
the dilution system, or directly connect to
the gas sampling valve as required.
8. After the dilution system and GC operations
are satisfactory, analyze the source gas in
duplicate until two consecutive values are
within ±5% of their mean.
9. Analyze again the calibration gas mixtures.
VMM M CMm« Aiwra
HIMM ••» It 130-C or Satire* T«m*«rafu
o«
1330 ccMM
Figure F18C-1. Schematic Diagram of me Heated Box Required
-------
2/13/95: FDISc-1
FIELD DATA SHEET 18c
GC Dilution Interface Analysis
Client/Plant Name
City/State
Job #
Date
Personnel
Sample Moisture Content, Bw,
flfoto: Conduct a pre- and post-test calibration using three gas mixtures from CDS 18b or c, plot calibration curve,
and attach. Record the average barometric pressure and temperature of the pre- and post-test conditions here:
Pr.
mm Hg
Note: Use more data sheets as needed.
Chrornatograph Operation
Parameter
Sample loop volume (mL)
Sample loop temp, T; (K)
Column temp initial (°C)
Column temp, program rate (°C/mU
Column temp final (°CJ
Carrier gas flow rate (mL/min)
Setting
Parameter
Detector temp (°C)
Chart speed (cm/min)
Sample flow rate (mL/min)
Dilution gas flow rate (mL/min)
Dilution Gas used (symbol)
Dilution ratio, Df
Setting
i
Bar. pressure during sample analysis,
mm Hg _ Probe/sample line set at 0-3° C above stack
temperature?
Samples to be analyzed in addition to field samples: Two Audits, High-Cal Mixture from the inlet to the probe or as
dose as possible, but before the filter, and through the appropriate dilution system (Concentration determined must
ba within ± 1 0% of expected value.)
Sample
ID
Inject'n
Time
(Clock)
Organic
Compnt
Distto
Peak
(cm)
Retent.
. Time
(sec)
Atten.
Factor
AC
Peak Area,
V
(mm2)
AcxAm
(mm2)
Cone.
Ca
(ppm)
•
Calc Cone
Cc
(ppm)
The pre- and post- calibration curves are within
5% of their mean value? If not, report final
results by comparison to both calibration curves.
Peak areas from 2 consecutive injections agree
±5% of their average?
Audit analyses agree ± 10% of the audit
concentrations?
QA/aC Check
Completeness Legibility Accuracy
Concentration of High-Cal gas within ±10% of
expected value?
C
c"
Fr = Response factor, if needed.
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30J94*. TOIBc-2
FIELD DATA SHEET 18c (Continued)
Bar. pressure during sample analysis, Pf mm Hfl
Sample
ID
Inject'n
Time
(Clock)
_
Organic
Compnt
Dist to
Peak
(cm)
Retent.
Time
(sec)
Atten.
Factor
AC
•
Peak Area,
(mm2)
Ac* Am
(mm2)
•
Cone.
cs
(ppm)
V
Calc Cone
cc
(ppm)
•
Peak areas from 2 consecutive injections agree
±5% of their average?
C
P,Tf(1-B,J
QA/QC Check
Completeness
Legibility
Accuracy
Response factor, if needed.
_ Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
2/13/95: FD18c-3
FIELD DATA SHEET 18c (Continued)
Recovery Study Average of duplicate injects that met the ±5% criterion.
Target
Compound
(High-level)
At Analyzer (using lower C9nc) (ppm)
In}. 1
Inj. 2
Avg*
From Probe (ppm)
Inj. 1
Inj. 2
Avg, P
Recovery
R
Dttt Summary
jnd Level. C — ppm
Q_ C-P
11 ' c
R = 0.90 to 1 .1 0 for tests to be valid
* Averages of duplicate injects that met the ±5% criterion.
Target
Compound
Run #1 *
(ppm).
Run #2
(ppm)
Run #3
(ppm)
Avg
(ppm)
\
•
QA/aC Check
Completeness
Checked by:
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: F18d-1
FIELD PROCEDURE 18d
Adsorption Tube Sampling and Analysis
A. Sampling
1,
2.
Note: Refer to the National Institute for Occupational Safety and Health (N'OSH) method for the
cno'^f organ!cs to be saf"Ple5% but ^20%
of initial, use the average of the two to
calculate sample volume.
1
2.
3.
-------
Probe
Adsorption
Tube
Supplemental
Adsorption
Tube
(as required)
Vacuum Guage .
J-H— r— | JLoi
/ Soip
/ F&
1 (fore*
X
Vint
c
Flowmit«r 1
Needle , H1
Valve *-
IH3 ^1 /T\__i?J
Critical Orifice Silica Gel
Drying Tube
Surge Tank
Pump
Figure F18d-1. Adsorption Tube Sampling System.
-------
9J30J94: FD18d-1
FIELD DAT A SHEET 18d( Attachment)
Recovery Study
Note: Three sets of spiked and unspiked runs are needed. Attac.'. this FDS to LDS 18a.
Target
Compound
Spiked Train
Mass Meas
ms
Ot/9)
Sampl Vol.
vs
(U
Unspiked Train
Mass Meas,
mu
U/9)
Sampl Vol.
VU
(L)
Spiked
Amt, S
U/g)
Meas
Amt, mv
U/g/U
Recovery
R
Note: Average the R's from the three runs. This average R
must be £0.70 Ravg £1.30 for each target compound for
the results to be valid.
Data Summary * Average of duplicate injects that met the ±5% criterion.
Target
Compound
-:
Run #1 (ppm)
C*
01
CC1/R
.
Run #2. (ppm)
CC2
CC2/R
Run #3 (ppm)
CC3
cc3/R
Corr
Avg
(ppm)
„ -
QA/QC Check
Completeness
Checked by: _
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
-------
9/30/94: S20-1
SUMMARY SHEET 20
Nitrogen Oxides
Run #1 Run #2 Run #3 Avg
Client/Plant Name FDS 20c
Job No. FDS 20c
Sampling Location FDS 20c
Run ID # FDS 20c
Test Date FDS 20c
Run Start Time FDS 20c
Run Finish Time FDS 20c
Moisture Content, fraction Bws FDS 4
Low-load
Avg NOX Concentration, ppm at 15% O2 Cadj FDS 20c
Mid-load
Avg NOX Concentration, ppm at 15% O2 Cadj FDS 20c
Peak-load
Avg NOX Concentration, ppm at 1.5% O2 Cadj FDS 20c
Avg O2 Concentration, % %O2 FDS 20c
Avg SO2 Concentration, ppm CSO2 FD^ ®
Avg SO2 Concentration, ppm at 15% O2 C^ SS 20
_ 5.9
20.9-%O2
/Vote.- /A CO2 is the diluent gas measured, see FDS 20c for determining Cadj for SO2.
-------
Figure F20-1. Measurement System Design.
-------
9/30/94: F20-1
FIELD PROCEDURE 20
Nitrogen Oxides and Oxygen
(Gas Turbines)
Note: This procedure is preliminary to the measurement of the stack gases. For measurement of the
stack gases, see FP 20a.
A. Calibration Gases
1. Obtain NOX calibration gases (NO in N2) as
follows:
a. High-level. 80% to 90% of span value.
b. Mid-level. 45% to 55% of span value.
c. Low-level. 20% to 30% of span value.
d. Zero. <0.25% of span value. Ambient
air may be used for the NOX zero gas.
2. Obtain diluent calibration gases as follows:
a. High-level. Purified air at 20.9% O2 or
8% - 12% CO2 in air.
b. Mid-level. 11 % to 15% O2 in N2 or
2% - 5% CO2 in air.
c. Zero. Purified N2 or purified air
«100 ppm CO2)
3. Use Protocol 1 gases or analyze the cylinder
gases within one month of the emission test
(see FP 6C, steps A4 and A5 and CDS 20),
using Methods 7 and 3 as the reference
methods for NOX and O2 or CO2 respectively.
Acceptance criteria for each triplicate result
must be (from the average) ±10% or
±10 ppm, whichever is greater, for NOX and
±0.5% O2 for O2. For the use of
manufacturer's tag values, the triplicate
average of the reference methods must be
±5% for NOX and 0.5% O2 for O2. If these
criteria are not met, conduct an additional set
of three reference test runs until all six runs
agree (from the average) within ±10% or
±10 ppm, whichever is greater, for NOX and
±0.5% O2 for O2. Use the average of these
six runs as the cylinder gas value.
B. Preliminary Procedures
1. Prepare the system and set up the
measurement system. An example of an
acceptable system is shown in Figure F20-1.
2. Calibration Error Check. Before each test
program, conduct the calibration checks for
both the NOX and the diluent analyzers as
follows:
a. First, introduce zero gases and the mid-
level calibration gases, and set the
analyzer output responses to the
appropriate levels.
b. Then, introduce each of the remainder of
the calibration gases, one at a time, to
the measurement system. Record the
responses on FDS 20.
c. NOX monitor only: For a valid calibration
check the linear curve determined by
the zero and mid-level gases must
predict the low-level and high-level gas
values ±2% of the span value.
3. Interference Response Test. Conduct an
interference response test on each analyzer
once before its initial use in the field and
after changes are made in the
instrumentation that could alter the
interference response, e.g., changes in the
type of gas detector. Data from interference
response tests conducted by the instrument
vendor are acceptable.
a. Introduce the following gases into the
measurement system separately, or as
gas mixtures.
• CO: 500 ± 50 ppm
• SO2: 200 ± 20 ppm
• C02: 10 ± 1%
• O2: 20.9 ± 1 %
-. b. Record the response of the system to
these components in concentration
units; record the values on LDS 20.
4. Response Time Test. Conduct the response
time test before each test program and
whenever changes are made to the
measurement system. Perform three runs,
and record the data as shown in FDS 20. A
stable value is equivalent to a change of
<1 % of span value for 3O sec or <5% of
the measured average concentration for 2
miri.
a. Introduce zero gas into the system at
the calibration valve until all readings
are stable; then, switch to monitor the
stack effluent until a stable reading is
obtained. Record the upscale response
time.
b. Introduce high-level calibration gas into
the system. Once the system has
stabilized at the high-level calibration
concentration, switch to monitor the
stack effluent and wait until a stable
value is reached. Record the downscale
response time.
5. Conversion Efficiency. Determine the NO2
to NO conversion efficiency (if applicable,
e.g., NO2 &5% of total NOX) before each
test program. A converter is not necessary if
the NO2 portion of the exhaust gas is less
than 5% of the total NOX concentration or if
-------
the gas turbine is operated at 90% or more
of peak load capacity.. (The NO2 to NO
converter check described in title 40,
Part 86: Certification and Test Procedures for
Heavy-duty Engines for 1979 and Later
Model Years, may be used. Attach
appropriate FDS.)
a. Add gas from the mid-level NO in N2
calibration gas cylinder to a clean,
evacuated, leak-tight Tedlar bag. Dilute
this gas approximately 1:1 with 20.9%
O2, purified air.
9/30/94: F20-2
b. Immediately attach the bag outlet to the
calibration valve assembly and begin
operation of the sampling system.
Operate the sampling system, recording
the NOX response for at least 30 min.
See FDS 20.
-------
9/30/94: FD20-1
FIELD DATA SHEET 20
Analyzer Zero, Calibration, Response Time, Conversion Efficiency
Client/Plant Name -
City/State
Test Location
NOX Analyzer ID#
Diluent Analyzer ID#
Personnel
Span value
Soan value
Job #
Date
ppm
% (O, or CO?)
Determine Calibration Error prior to the first test run:
NOX
Analyzer
Diluent
Analyzer
Zero
Low-level
Mid-level
High-level
Zero
Mid-level
High-level
Calibration Gas
Cylinder ID #
Gas Value (ppm or %)
Analyzer
Response (ppm or %)
Cal Error Result
{% of span)
** f, V. ''f
: f
\ •* s
f *.
^ , c
'" * — ^.V-
NOX £2% of span?
Diluent £2% of span?
% Cal Error = Analyzer Response -Gas Value x 10Q
Span Value
Determine Response Time:
Run No.
1
2
3
Average
Slower Time
NOX Analyzer
Upscale (sec.)
Downscale (sec.)
Diluent Analyzer (O2 or CO2)
Upscale (sec.)
Downscale (sec.)
The slower time is the system response time.
Stable Response = <1% span value for 30 sec or <5% of 2-min average? '
NO2-NO Convener Efficiency
Peak response recorded during test
Response recorded at end of 30 minutes
% Decrease from peak response
(Attach strip chart or recorder readout)
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
FIELD DATA SHEET 20 (Continued)
Zero and Calibration Drift
Client/Plant Name
City/State
Test Location
Personnel
9/30/94: FD20-2
Job #
bate
Dotormtno %Drfft after every test run:
Run*
Condition
Cylinder Value
Analyzer Response
Initial
Final
Difference
(Initial - Final)
% Drift
HOX Anafyzer
Zero
Mid-level
Diluent Analyzer
Zero
Mid-level
NOK Analyzer
Zero
Mid-level
Diluent Analyzer
Zero
Mid-level
NOX Anatyzet
Zero
Mid-level
Diluent Analyzer
Zero
Mid-level
% Drift = lDifferf"cel x 100
Span Value
QA/aC Chock
Completeness
Checked by: _
, Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
Date
Analyzer Type
9J30J94: LD20-1
LABORATORY DATA SHEET 20
Interference Response
Personnel
Analyzer ID#
Test Gas
Nominal Concentration
Actual Concentration
Analyzer Response
% of Span
Method 20 Span Value:
CO
SO2
CO2
02
500 ± 50 ppm
200 ± 20 ppm
10 ± 1 %
20.9 ± 1 %
Method: Span Value:
% of Span = Analyzer Response x
Instrument Span
Sum of the interference responses to the test gas for either the NOX or diluent analyzer <2% of span value?
QA/QC Check
Completeness
Checked by: _
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: CD20-1
Date
Cylinder ID#: Zero:
CALIBRATION DATA SHEET 20
Analysis of Calibration Gases
(Must be within 1 month before the test)
Low: Mid:
NOX Span
High:
Reference Method for NOX
(Attach appropriate data sheets) Personnel
NOX
Run No.
1
2
3
4
5
6
Average
Max % Dev
Tag Value, ppm
Low-Level
(2O%-3O% of span value?)
Mid-Level
(45%-55% of span value?)
High-Level
•'
(80%-90% of span value?)
Max %Dev s±10%or ±10 ppm from average?
Average ppm ^ ±5% of tag value? If not, use the average of the six runs as the cylinder value.
Cylinder ID#: Zero: Mid: High: ,
Reference Method used
(Attach appropriate data sheets) Personnel
Diluent (O2 or CO2)
Run No.
1
2
3
4
5
6
Average
Max % Dev
Tag Value, ppm
Mid-Level
'
(11%-15% O2?) or
(2%-5% CO 2?)
High-Level
(20.9% O2?) or
(8%-12% CO2)
Max % Dev £ ±0.5% O2 or CO2 from average?
Average %O2 £ ± 0.5 % O2 or CO2 from tag value? If not, use the average of the six runs as the cylinder
value.
QA/aC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: F20a-1
FIELD PROCEDURE 20a
Gas Turbines
Note: Before conducting this procedure, see FP 20.
A. Sampling Site and Traverse Points
1. Select a sampling site as close as practical
to, but not within 5 ft or 2 De (whichever is
less) of, the turbine exhaust to the
atmosphere.
. a. Whenever possible, locate the sampling
site upstream of the point of introduction
of dilution air into the duct.
b. Locate sample ports before or after the
upturn elbow to accommodate the
configuration of the turning vanes and
baffles and to permit a complete,
unobstructed traverse of the stack.
c. For supplementary-fired, combined-cycle
plants, locate the sampling site between
the gas turbine and the boiler.
2. Select a minimum number of preliminary
diluent traverse points as follows:
a. For the following cross-sectional areas,
• <16.1 ft2, use 8 points.
• 16.1 to 107.6 ft2, use 8 plus one
additional sample point for each
2.2 ft2 above 16.1 ft2.
• > 107.6 ft2, use 49 (48 for circular
stacks).
b. For circular ducts, use a multiple of 4
points, and for rectangular ducts, use a
balanced matrix, i.e., 3x3, 4x3, 4x4,
5x4, 5x5, 6x5, 6x6, 7x6, or 7x7.
Round off the number of points
(upward), when appropriate.
3. Use Method 1 to locate the preliminary
diluent traverse points.
B. Preliminary Diluent Measurements
1. While the gas turbine is operating at the
lowest percent of peak load, measure the
O2 or CO2 concentration at each traverse
point for at least 1 min plus the average
system response time. Record the average
steady-state concentration of O2 or CO2 at
each point on FDS 20a.
2. Select 8 sampling points at which the lowest
O2 concentrations or highest CO2
concentrations were obtained. Use these
same points for all the test runs at the
different turbine load conditions.
C.
NOX and Diluent Measurements
Conduct three test runs at each of the
specified load conditions as follows:
1. At the beginning of each NOX test run and,
as applicable, during the run, record turbine
data as indicated in FDS 20b. Also, record
the location and number of the traverse
points on a diagram (see FDS 20a)
2. Determine the average steady-state
concentration of diluent and NOx at each of
the selected traverse points and record the
data on FDS 20c. Sample at each point for
at least 1 min plus the average system
response time.
3. After sampling the last point, record the final
turbine operating parameters.
4. Immediately after each test run at each load
condition or if adjustments are necessary for
the measurement system during the tests,
determine the calibration drifts at zero and
the mid-level values. Make no adjustments
to the measurement system until after the
drift checks are made. Record the data on
FDS 20. Exceedance of the specified limits
invalidates the test run preceding the check.
Alternatively, recalibrate the measurement
system and recalculate the measurement
data. Report the test results based on both
the initial calibration and the recalibratipn
data.
D. SO2 Measurement
Determine the SO2 concentration at only the
100% peak load condition using Method 6, or
equivalent, during the test. If fuel sampling and
analysis is used to demonstrate compliance and
the fuel sulfur content meets the limits of the
regulation, this test is not required.
1. Select at least 6 points from those required
for the NOX measurements; use two points
for each sample run.
2. Sample at each point for at least 1O min.
3. Use the average of the diluent readings
obtained during the NOX test runs at the
traverse points corresponding to the SO2
traverse point, to correct the integrated SO2
concentrations to 15% O2.
-------
FIELD DATA SHEET 20a
Preliminary Diluent Traverse
Client/Plant Name
City/State
Job #
9/30/94: FD20a-1
Date
Personnel
Turbine ID: Manufacturer/Type
Serial #
Sampling Site Dist from Exhaust
No. of Traverse Pts
Load
ft2
(^5 ft or 2 D0, whichever is less?) Cross-Section Area, A
16.1 ft2 = >8; 16.1 to 107.6ft2 = 8 + A/2.2; >107.6ft2 = 49 (48 for circ. ducts)
(Turbine operating at the lowest percent of peak load?)
Traverse
Pt
Diluent
Cone.
(%)
Traverse
Pt
Diluent
Cone.
(%)
Traverse
Pt
Diluent
Cone.
(%)
Traverse
Pt
Diluent
Cone.
(%)
Circle traverse points selected for NOX measurements. Sketch a diagram of sampling site and cross-section below.
QA/QC Chuck
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
Client/Plant Name
City/State
FIELD DATA SHEET 20b
Gas Turbine Operation Record
Job #
9/30/94: FD20b-1
Date
Personnel
Turbine ID: Manufacturer/Type
Serial #
Fuel Ultimate Analysis
C
H
O
N
S
Ash
H2O
Trace metals fused in smoke suppression}
Na
Va
K
etc.
Indicate units where applicable.
Load/Run #
Time
Fuel
Flow Rate
Steam/Water
Flow Rate
Amb Temp
Amb,
Humidity
Amb Pressure
Describe fuel flow and water or steam flow rate measurement methods.
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
Client/Plant Name
City/State
Turbine ID: Manufacturer/Type
NOx Analyzer Type/ID #
9/30/94: FD20c-1
FIELD DATA SHEET 20c
Gas Turbine Emissions
Job #
Date
Personnel
Serial #
Diluent Analyzer Type/ID #
Indicate units where applicable. Use the average steady-state value (concentrations) from recorder or instrument
readout.
Load/Run #:
Sample
Pt
Clock Time
(min)
Load/Run #:
Sample
Pt
Clock Time
(min)
Load/Run #:
Sample
Pt
Clock Time
(min)
Amb temp: Amb pressure:
Diluent
(%)
NOX
(ppm)
Sample
Pt
Clock Time
(min)
Diluent
(%)
•(
NOX
(ppm)
Amb temp: Amb pressure:
• Diluent
(%)
NOX
(ppm)
Sample
Pt
Clock Time
(min)
Diluent
(%)
NOX
(ppm)
Amb temp: Amb pressure:
Diluent
(%)
NOX
(ppm)
Sample
Pt
Clock time
(min)
Diluent
(%)
NOX
(ppm)
QA/aC Chock
Completeness
Checked by: _
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
. Reasonableness
Team Leader (Signature/Date)
-------
9/3O/94; F21-1
FIELD PROCEDURE 21
Volatile Organic Compound Leaks
Note: A leak definition concentration based on a reference compound is specified in each applicable
regulation. This procedure is intended to locate and classify leaks only, and is not to be used as a direct
measure of mass emission rates from individual sources. The data sheets (FDS and CDS) serve as a
summary; hence, there is no Summary Sheet.
A. Pretest Preparations
Calibrate and check the instrumentation
according to CP 21.
1.
2.
3.
Type I - Leak Definition Based on
Concentration
Place the probe inlet at the surface of the
component interface where leakage could
occur. Move the probe along the interface
periphery.
If the meter reading increases, slowly sample
the interface until the maximum reading is
obtained. Hold this position for about two
times the instrument response time.
Record and report all maximum observed
meter reading >LDC as specified in the
regulation reporting requirements.
4. Examples of the application of this general
technique to specific equipment types are:
a. Valves - Circumference of stem exiting
the packing and flange periphery.
Survey valves of multipart assemblies
where a leak could occur.
b.
c.
d.
e.
f.
Flanges and Other Connections - Outer
edge of the flange-gasket interface and
circumference of the flange.
Pump or Compressor Seals - If
applicable, determine the type of shaft
seal. Survey local area ambient'VOC
concentration and determine if
detectable emissions exist.
Pressure Relief Devices - For those
devices equipped with an enclosed
extension, or horn, the center of the
exhaust area to the atmosphere.
Process Drains - For open drains, as near
as possible to the center of the area
open to the atmosphere. For covered
drains, surface, periphery of the cover.
Open-ended Lines or Valves - Center of
the opening to the atmosphere.
h.
Seal System Degassing Vents,
Accumulator Vessel Vents, Pressure
Relief Devices - If applicable, emission
points in ducting or piping before the
control device.
Access Door Seals - Door seal interface
and periphery.
C. Type II - "No Detectable Emission"
1. Determine the ambient concentration around
the source by moving the probe randomly
upwind and downwind 1 to 2 meters from
the source or, if interferences exist, closer to
the source down to 25 cm. Then move the
probe to the surface of the source and
measure as in section B. Determine the
difference. When the regulation also
requires that no detectable emissions exist,
visual observations and sampling surveys are
required.
2.. Examples of this technique are:
a. Pump or Compressor Seals.
b. Seal System Degassing Vents,
Accumulator Vessel Vents, Pressure
Relief Devices - Any vents upstream of
the device.
D. Alternative Screening Procedure
1. A soap solution may be used under the
following conditions:
a. No continuously moving parts.
b. Surface temperatures >freezing point of
the soap solution or < boiling point.
c. No open areas that the soap solution
cannot bridge.
d. No evidence of liquid leakage.
2. Spray a soap solution over all potential leak
sources: No bubbles indicate no detectable
emissions or leaks.
3. If any bubbles are observed, use the
instrument techniques (section B or C).
-------
9/30/94: FD21-1
FIELD DATA SHEET 21
Volatile Organic Compounds Leaks
ClientfPlant Name Date Job #
Citv/State Personnel
Attach CDS 21 to thfs data sheet. Resoonse Time:
Equipment Type
Type I
LDC
QA/aC Check
Completeness Legibility
Checked by:
Cm >LDC
sec
Type II
Upwind
Downwind
Avg
-
Diff = Cm - Avg
,
Accuracy Specifications Reasonableness
Personnel (Signature/Date) Team Leader (Signature/Date)
-------
9/30/94: C21-1
CALIBRATION PROCEDURE 21
Volatile Organic Compound Leaks
A. Procedure
1. From the regulations, determine the leak
definition concentration (LDC) and reference
compound, e.g., 10,000 ppm as methane.
2. For the calibration gases, obtain a
manufacturer-certified reference compound at
about the LDC and zero gas (air, < 10 ppm
VOC).
3. Determine the species of organic compounds
to be measured and obtain gases of known
concentrations (in air) at about 80% LDC or,
if limited by volatility or explosivity, 90% of
the standard saturation concentration or 70%
of the lower explosive limit, respectively.
4. Assemble the equipment in the configuration
to be used and start up the instrument
according to the manufacturer's instructions.
5. Calibrate the instrument with the reference
compound. If the meter readout cannot be
adjusted to the proper value, take corrective
actions before proceeding.
6. Determine the response factor for each of the
organic species in step A3 as follows (this
step need not be repeated at subsequent
intervals):
a. Run triplicates, alternating between the
known mixture and zero gas.
b. Calculate response factors for the
individual compounds (must be <10).
7. Determine the calibration precision initially
and at subsequent 3-month intervals or at the
next use, whichever is later, as follows:
a. Run triplicates, alternating between zero
and the calibration gas without any
adjustments to zero and span.
b. Calculate the precision (see CDS 21)
from the three values (must be := 10%).
8. Determine the response time, initiallv and
whenever the sample pumping system or
flow configuration is modified such that it
would change the response time, as follows:
a. Run triplicates. Introduce zero gas into
the instrument sample probe. When the
meter reading has stabilized, switch
quickly to the calibration gas.
b. Measure the time from switching to
when 90% of the final stable reading is
attained.
c. Calculate the average response time
(must be £30 sec),
B. Alternatives
1. Rather than certified calibration gases, the
user may prepare the calibration gases using
any accepted gaseous preparation procedure
that will yield a mixture accurate to ±2%.
Replace these prepared standards .daily
unless it can be demonstrated that
degradation does not occur during storage.
2. Rather than the reference compound,
another compound may be used as the
. calibration gas provided that a conversion
factor is determined.
3. Published response factors for the
compounds of interest for the instrument or
detector type may be used instead of actual
measurements. See the references in
Method 22.
-------
9/30/94: CD21-1
CALIBRATION DATA SHEET 21
Volatile Organic Compounds Leaks
Client/Plant Name
City/State
Date
Job #
Personnel
Applicable Regulation _
Leak Definition Ref Compound and Concentration
Actual Certified Cal Gas Cone Cat Gas (if other than reference compound)
Response Factor
If published response factors are used, fill in first and last columns only.
Organic
Compounds
Cone.
(ppm)
Response
#1
Response
#2
•
Response
#3
Average
(ppm)
•
"
RF
« 10 ?)
Cal Gas Cone.: Calibration Precision
Run No.
Meas. Cone. (ppm)
1
2
3
Avg,
Diff
% (* 10 ?)
Response Time
Run No.
Time (sec)
1
2
3
Avg f^30 sec ?)
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specif ications_
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: F22-1
FIELD PROCEDURE 22
Visible Fugitive Emissions from Material
Sources and Smoke Emissions from Flares
Note: Read initially the written materials found in Citations 1 and 2 in the Bibliography of Method 22 or
attend the lecture portion of the Method 9 certification course to be trained and knowledgeable about the
effects on the visibi/ity of emissions caused by background contrast, ambient lighting, observer position
relative to lighting, wind, and the presence ofuncombined water (condensing water vapor). The data
sheet serves as a summary; hence, there is no Summary Sheet.
A. Preliminary Determinations
1. Determine the applicable subpart and the
process to be observed, i.e., affected
facility, building, or housing structure and
the requirements for observations.
2. Determine ah observation location of .
potential emissions, i.e., outside observation
of emissions escaping the building/structure
or inside observation of emissions directly
emitted from the affected facility process
unit.
3. Select a position that enables a clear view of
the potential emission point(s) and where
the sun is not directly in the observer's
eyes. This position should be > 15 feet, but
<0.25 miles, from the emission point.
4. Record the information on FDS 22 (outdoor
locations) or on FDS 22a (indoor locations).
5. For indoor locations, measure the level of
illumination as close to the emission
sources(s) as is feasible. The illumination
must be > 100 lux (10 foot candles).
6. Choose an observation period that meets the
requirements for determining compliance. If
the process operation is intermittent or
cyclic, it may be convenient for the
observation period to coincide with the
length of the process cycle.
B. Observations
1. Determine the observation period as follows:
a. Start the accumulative stopwatch when
observation period begins, and record
the clock time.
b. Stop and start (without resetting) the
stopwatch during breaks (process
shutdowns, observer rest breaks) in the
observation period. Record the
corresponding clock times.
c. Stop the stopwatch at the end of the
observation period, and record the clock
time. The accumulated time on the
stopwatch is the observation period.
2. Determine the total time that visible
emissions were observed as follows:
a. During the observation period,
continuously watch the emission source.
b. Upon observing an emission (condensed
water vapor is not considered an
emission), start the second accumulative
stopwatch; stop the watch when the
emission stops.
c. Continue this procedure for the entire
observation period. The accumulated
elapsed time on this stopwatch is the
emission time.
3. If the observation period is terminated
because fugitive emissions from other
sources (e.g., road dust) obscure a clear
view of the affected facility to such a degree
that the observer questions the validity of
continuing observations, note this fact on
the FDS.
C. Observer Rest Breaks
1 . Take a rest break every 1 5 to 20 min for
5 to 10 min.
2. For extended observation periods, alternate
two observers between observations and
breaks.
D. Alternative
The observation period (optional) may be
ended if the emission time indicates
noncompliance. For example:
1 .
2.
If the standard is £6 min in any hour, then
observations may be stopped after emission
time is >6 min.
If the standard £"\Q% of the time in any
hour, then observations may be terminated
after emission time is >6 min (10% of an
hour).
-------
-------
9/30/94*. SS23-1
SUMMARY SHEET 23
Client/Plant Name
Job No.
Sampling Location
Sample ID#
Test Date
Run Start Time
Run Finish Time
Traverse Points (if applicable)
Net Run Time, min
Dry Gas Meter Calibration Factor
Avg Pressure Differential Across Orifice, in. H2O
Barometric Pressure, in. Hg
Absolute Average Temperature, R
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Gas Sample {Vm(std) x 0.02832), dscm
Concentration of PCDD/PCDF, pg/m3
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,4,5,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDD
OCDD
OCDF
Total Concentration of PCDD's/PCDF's, pg/m3 CTr SS 23
Run#1
Run #2 Run #3
e
V
AH
Pb
Tm
vm
Vm(std)
Vm(std)
c,
Cj
Cj
c.
Cj
c,
Cj
Cj
c,
Cj
Cj
Cj
c.
Cj
Cj
Cj
FDS23
FDS23
FDS23
FDS23
FDS23
FDS23
FDS23
FDS1
FDS23
FDS23
FDS23
FDS05
FDS05
FDS05
SS05
SS05
LDS23
IDS 23
LDS23
LDS23
IDS 23
LDS23
LDS23
LDS23
LDS23
LDS23
LDS23
LDS23
LDS23
IDS 23
LDS23
LDS23
Avg
CT, = £0,
M
-------
Temperature
Sensor
Inclined RerirculatronlS
Manometer pump IS
Bl-lJ
X b
IliJ IbJ Ib! I™
f
Ice
'atei
Bath
Empty 1Q0 mL Empty
HPLC Water
Inclined .
Manometer
Vacuum
Line
Figure F23-1. Sampling Train.
-------
9/30/94: F23-1
FIELD PROCEDURE 23
Polychlorinated Dibenzo-p-dioxins (PCDD) and Polychlorinated Dibenzofurans (PCDF)
Note: This sampling procedure is basically the same as that of Method 5. Precfean components
according to LP 23a.
A. Major Exceptions
1. Do not use sealing greases in assembling the
train.
2. Use nozzle material made of nickel, nickel-
plated stainless steel, quartz, or borosilicate
glass.
3. Use pesticide quality for acetone, methylene
chloride, and toluene.
4. As sample storage containers of washes, use
amber glass bottles with leak-free Teflon-
lined caps.
B. Pretest Preparation
1. See LP 23a for pre-test procedures.
2. Soak for several hours in chromic acid
cleaning solution all glass components of the
train upstream of and including the adsorbent
module. Then clean the components as
described in section 3A of the "Manual of
Analytical Methods for the Analysis of
Pesticides in Human and Environmental
Samples." Especially ensure the removal of
residual silicone grease sealants on ground
glass connections of used glassware.
3. Load the adsorbent trap in a clean area
(never in the field) to avoid contamination.
Fill the trap with 20 to 40 g XAD-2. Follow
with glass wool and tightly cap both ends of
the trap.
4. Add 100 pL of each of the five surrogate
standards (see Table 23-1) to each trap.
4. Prepare the sampling train as follows:
a. Place ~ 100 mL water in the second and
third impingers.
b. Leave the first and fourth impingers
empty.
c. Transfer ~ 200 to 300 g preweighed
silica gel from its container to the fifth
impinger.
C. Sampling
1. Assemble the train as shown in Figure F23-1.
Turn on the adsorbent module and condenser
coil recirculating pump and begin monitoring
the adsorbent module gas entry temperature.
2. Ensure proper sorbent temperature gas entry
temperature before proceeding and before
initiating sampling. Never exceed 50°C
because thermal decomposition of the
XAD-2 adsorbent resin will occur. During
testing, do not exceed 20 °C for the XAD-2
(necessary for efficient capture of PCDD and
PCDF).
D. Sample Recovery
Follow the general procedure in Method 5.
Use aluminum foil or Teflon tape to close off both
ends of the probe. Close off the inlet to the train
with Teflon tape, a ground glass cap, or aluminum
foil. Do not smoke (possible contaminating
source) in the cleanup area. Treat the samples as
follows:
1. Container No. 1. Either seal the filter holder
or carefully remove the filter from the filter
holder and place it in its identified container.
2. Adsorbent Module. Remove th'e module
from the train, tightly cap both ends, label it,
. cover with aluminum foil, and store on ice
for transport to the laboratory.
3. Container No. 2. Quantitatively recover
material deposited in the nozzle, probe
transfer lines, the front half of the filter
holder, and the cyclone, if used, as follows:
a. Brush the probe while rinsing three
times each with acetone and then rinse
three times with methylene chloride.
b. Rinse the back half of the filter holder
and connecting line between the filter
and condenser three times with
acetone.
c. Soak the connecting line with three
separate portions of methyiene chloride
for 5 min each.
d. If used, rinse the condenser in the same
manner as the connecting line.
e. Mark the level of the liquid on the
container and label.
4. Container No. 3. Follow step D3 using
toluene as the rinse solvent. Mark the liquid
level on the container and label.
5. Impinoer Water. Treat as in Method 5.
6. Silica Gel. Treat as in Method 5.
-------
Method
Client/Plant Name
City/State
Test Location/Run
FIELD DATA SHEET 23
Date
BarPb ;
Personnel
Job #
in. Hg Stk P_
9/30/94: FD23-1
in. H2O
Eouloment Checks
Phot Loak-Cbk:
ft* Pott
Nozzle:
Pro Pott
F8tif »
Prob*
Uner
XAD I.D. *
Htr cett'o
Amblcmo
TSroa:
Start
End
E«Md
Equipment IDtf's
Rant Box Sampl'a Box #
Mater Box Y • Umbilical
Rtot Cp Tedlar Baa
Noz'l Dn Orsat Pump
TC Readout TC Probe
Isokinetic Set-Up Data
AH/a
Metr temp
Est %HjO
Stk temp
Ref AD
C factor
K factor
Leak-Checks
Vac., in. Ha
DGM init. cf
DGM finl, cf
Leak Rate, cfm
Silica Gel.
SG + (check) Container Impinfler
' Initial wgt fl
Final wgt , fl
L
1
N
E
1
2
3
4
C
a
7
•
•
10
It
12
13
14
IB
IB
17
1*
1S
30
21
22
23
24
26
SimpI
PC*
Clock
Tbna
QA/aC Check
Completeness
DGM
Rdg
(cf)
("b
<°£)
Pitot Ap
On. H20)
Stk temp
(°F)
Orifice (in. H2O)
Acfl
',
Ideal
Vac.
(in. Hg)
Gas Temperatures (°F)
Fitter
'Imping
exit
Cond.
<68°F
-
Legibility Accuracy Specifications Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: L23-1
LABORATORY PROCEDURE 23
Polychlormated Dibenzo-p-dioxins and Polychlorinated Dibenzofurans
Note: Extract all samples within 3O days of collection and analyze within 45 days of extraction.
Preclean components according to LP 23a.
A. Reagent Preparation
1. Chromic Acid Cleaning Solution. Dissolve
20 g sodium dichromate in 15 nr>L of water,
and then carefully add 400 mL of cone.
sulfuric acid.
2. Potassium Hydroxide, 2%. Prepare in the
ratio of 2 g KOH/100 mL water.
3. Sodium Hydroxide, 1.0 N. Dissolve 40 g
NaOH in water, and dilute to 1 L with water.
4. Basic Alumina. Before use, activate the
alumina by heating for 16 hr at 130°C.
Store in a desiccator. Pre-activated alumina,
purchased from a supplier, may be used as
, i received.
5. Silica Gel Impregnated with H2SO4. Combine
100 g silica gel with 44 g cone. H2SO4 in a
screw capped glass bottle and agitate
thoroughly. Disperse the solids with a
stirring rod until a uniform mixture is
obtained. Store the mixture in a glass
container with a Teflon lined screw cap.
6. Silica Gel Impregnated with NaOH. Combine
39 g 1 N NaOH with 100 g silica gel in a
screw capped glass bottle and agitate
thoroughly. Disperse solids with a stirring
rod until a uniform mixture is obtained. Store
the mixture in glass container with a Teflon-
lined screw cap.
7. Carbon/Celite. Combine 10.7 g AX-21
carbon with 124 g Celite 545 in a 250-mL
glass bottle with a Teflon-lined screw cap.
Agitate the mixture thoroughly until a uniform
mixture is obtained. Store in the glass
container. •
8. Unlabelled and Internal Standards. Prepare
100 pgl/jL in 10-mL nonane containing the
unlabelled analytes and isotopically labelled
PCDD and PCDF as shown in Table L23-1.
9. Surrogate Standards. Prepare 100 pg///L in
10-mL nonane containing the isotopically
labelled PCDD and PCDF as shown in
Table L23-.1.
10. Recovery Standards. Prepare 500 pg///L in
10-mL nonane containing the isotopically
labelled PCDD and PCDF as shown in
Table L23-1.
B. Sample Extraction System Preparation
1. Place an extraction thimble, 1 -g silica gel,
and a plug of glass wool into the Soxhlet
apparatus, charge the apparatus with
toluene, and reflux for 2:3 hr. Remove the
toluene and discard it, but retain the silica
gel.
2. Remove the extraction thimble from the
extraction system and place it in a glass
beaker to catch the solvent rinses.
C. Sample Preparation and Extraction
. The items in steps C1, C2, C3, and C4 are
extracted simultaneously.
1. Container No. 1 (Filter). Transfer contents
directly to the glass thimble of the extraction
system.
2. Adsorbent Cartridge. With the glass frit in
the up position, suspend the adsorbent
module directly over the extraction thimble in
the beaker. Using a Teflon squeeze bottle,
flush the XAD-2 with toluene into,the
thimble onto the bed of cleaned silica gel.
Thoroughly rinse the glass module, and
catch the rinsings in the beaker containing
the thimble. If the resin is wet, loosely pack
the resin in the thimble to increase extraction
. efficiency. Add the XAD-2 glass wool plug
' into the thimble.
3. Container No. 2 (Acetone and Methylene
Chloride). Concentrate the sample to about
1-5 mL using the rotary evaporator
apparatus at <37°C. Rinse the sample
container three times with small portions of
methylene chloride (MeCI2) and add these to
the concentrated solution and evaporate to
near dryness. Add this concentrate to the
extraction apparatus.
4. Internal Standards. Add 100pLofthe
internal standards (see Table L23-1) to the
extraction thimble.
5. Extraction. Extract as follows:
a.
b.
c.
Cover the contents of the extraction
thimble with the cleaned glass wool
plug to prevent the XAD-2 resin from
floating into the solvent reservoir of the
extractor. Place the thimble in the
extractor.
Add the toluene from the beaker to the
solvent reservoir. Pour additional
toluene to fill the reservoir -2/3 full.
Add Teflon boiling chips and assemble
the apparatus. Adjust the heat source
to cause the extractor to cycle three
times per hour. Extract the sample for
16 hr.
-------
Table L23-1. Minimum Requirements for Initial and Daily Calibration Response Factors.
Compound
Unlsbetad Analvtes:
2.3.7.8-TCDD
2,3.7.8-TCDF
1,2,3,7.8-PoCDD
1,2,3.7,8-PeCDF
2,3,4,7,8-PeCDF
1.2,4,5.7.8-HxCDD
1.2,3,6.7,8-HxCDD
1,2,3.7,8,9-HxCDD
1,2.3.4.7,8-HxCDF
1,2,3,6,7.8-HxCDF
1.2.3,7,8.9-HxCDF
2,3,4.6,7,8-HxCDF
1,2,3.4.6.7,8-HpCDD
1,2.3,4,6,7,8-HpCDF
OCDD
OCDF
Internal Standards:
13C12-2,3,7,8-TCDD
13C12-1,2.3,7.8-PeCDD
13C12-1,2,3.6,7.8-HxCDD
13C12-1 ,2.3.4.6,7,8-HpCDD
13C12-OCDD
13C, 2-2.3.7 ,8-TCDF
l3C12-1,2,3,7.8-PeCDF
1 3C, 2-1 ,2,3,6,7,8-HxCDF
13C12-1 ,2.3,4,6,7,8-HpCDF
Surrogate Standards:
37CI4-2,3,7.8-TCDD
13C12-2,3,4,7,8-PeCDF
l3C12-1,2,3.4.7,8-HxCDD
l3Cl2-1.2,3,4,7,8-HxCDF
13C12-1,2,3,4,7,8.9-HpCDF
Alternate Standard:
13C12-1.2,3,7,8.9-HxCDF
Recovery Standards:
13C12-1,2,3,4-TCDD
13C12-1,2,3.7.8,9-HxDD
Relative response factors
Initial Calibration
RSD
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
30
25
30
25
30
30
30
30
30
30
25
25
25
25
25
25
NA
NA
Daily Calibration
% difference
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
30
25
30
25
30
30
30
30
30
30
25
25
25
25
25
25
NA
NA
-------
Table L23-2. Elemental Compositions and E*act Masses of the Ions Monitored
by High Resolution Mass Spectrometry for PCDD's and PCDF's.
Descriptor No.
2
f
3 :
4
Accurate Mass
292.9825
303.9016
305.8987
315.9419
317.9389
319.8965
321.8936
327.8847
330.9792
331.9368
333.9339
339.8597
341.8567
351.9000
353.8970
355.8546
357.8516
367.8949
369.8919
375.8364
409.7974
373.8208
375.8178
383.8639
385.8610
389.8157
391.8127
392.9760
401.8559
403.8529
445.7555
430.9729
407.7818
409.7789
417.8253
419.8220
423.7766
425.7737
435.8169
437.8140
479.7165
430.9729
441 .7428
443.7399
457.7377
459.7348
469.7779
471.7750
513.6775
442.9728
Ion Type
LOCK
M
M + 2
M
M + 2
M
M + 2
M
QC
M
M + 2
M + 2
M + 4
M + 2
M + 4
M + 2
M+4
M + 2
M + 4
M + 2
M + 2
M + 2
M + 4
M
M + 2
M + 2
M + 4
LOCK
M + 2
M + 4
M + 4
QC
M + 2
M + 4
M
M + 2
M + 2
M + 4
M + 2
M + 4
M + 4
LOCK
M + 2
M + 4
M + 2
M + 4
M + 2
M + 4
M + 4
QC
Elemental Composition
C7F1t
C12H435CI40
C12H435CI370
13C12H435CI40
13C,2H435CI337ciO
C,2H435CI02
C12H43!5CI337CI02
C12H437CI402
C7F13
13C12H435CI402
13C,2H435CI37CIO2
C12H335CI437ciO
C12H335CI337CI20
13C12H335CI437CIO
13C12H335CI37CI20
C12H335CI337CI02
C,2H335CI337CI2O2
13C,2H335CI437C|02
13C12H335CI337CI2O2
c12H435ci537qo
c12H335ci637eio
C12H235CI537CIO
C12H235ci437ci20
13C12H235CI60
13C12H235ci537dO
C,2H235ci537C|02
C12H535CI437CI2O2
CgF15
'3C12H235CI537CI02
13C12H235CI437CI20
GLj 35oi 37/**i o
1 9**9 ^**R wlnv
CgF,7
C12H35CI637ciO
C12H35CI537ci20
13C12H35CI70
13Cl2H35CI637ciO
C,2H35CI637a02
C12H35CI537CI202
13C,2H35CI637CI02
13C12H35CI537a202
C12H35CI737CI20
C9F17 ;
C123SCI737CIO
C,235CI637CI2O
C1235C1737CI02
C1235CI637CI202
13C1235CI737CI02
13C1235CI637CI2O2
C1235a837a2°2
C1"F1-
Analyte
PFK
TCDF
TCDF
TCDF
-------
9/30/94: L23a-1
LABORATORY PROCEDURE 23a
Polychlorinated Dibenzo-p-dioxins and Polychlorinated Dibenzofurans (PCDF)
Pre-Test Procedures
Note: Clean all glassware as described in section A of the "Manual of Analytical Methods for the
Analysis of Pesticides in Human and Environmental Samples."
A. Fitter Precleanlng
Clean all filters before using as follows:
1. Prepare the extraction system (see LP 23,
stepBD.
2. Place £50 filters in the thimble onto the
silica gel bed and top with the cleaned glass
wool.
3. Charge the Soxhlet with toluene and reflux
for 16 hr.
4. After extraction, allow the Soxhlet to cool,
remove the filters, and dry them under a
clean N2 stream.
5. Store the filters in a glass petri dish sealed
with Teflon tape.
B. Adsorbent Precleanfag
Clean thoroughly the adsorbent resin •
(Amberlite XAD 2) before using as follows:
1. Use a giant Soxhlet extractor with an all- •
glass filter thimble containing an extra-course
frit. Recess the frit 10-15 mm above the
crenelated ring at the bottom of the thimble
to facilitate drainage.
2. Carefully retain the resin in the extractor cup
with a glass wool plug and a stainless steel
ring (resin floats on methylene chloride).
3. Sequentially extract the resin as shown in the
following Table:
Solvent
Water
Water
Methanol
Methylene
Chloride
Toluene
Procedure
Place resin in a beaker, rinse once
with water, and discard water. Fill
with water a second time, let
overnight, and discard water.
stand
Extract for 8 hr.
Extract for 22 hr.
Extract for 22 hr.
Extract for 22 hr.
4. Dry the adsorbent resin as follows:
a. Connect a standard commercial liquid N2
cylinder to the drying column with a
length of cleaned copper tubing, 0.95-
cm ID, coiled to pass through a heat
source (e.g., water-bath heated from a
steam line).
b. Purge the resin with warmed N2 (warm
to the touch but not over 40°C) until all
the residual solvent is removed. Adjust
the flow rate to gently agitate the
particles but not so excessive as to
cause the particles to fracture.
5. Check the resin for residual toluene as
follows:
a. Weigh 1.0 g dried resin into a small vial,
add 3 mL toluene, cap the vial, and
shake it well.
b. Inject 2-fjL sample of the extract into a
gas chromatograph operated under the
following conditions:
Column
Carrier Gas
Detector
Injection Port
Temp.
Detector Temp.
Oven Temp.
6 ft x 1/8 in. stainless steel
containing 10% OV-101 on
1 00/1 20 Supelcopprt.\
Helium at a rate of 30 mL/min.
Flame ionization detector
operated at a sensitivity of
4 x E-1 1 A/mV.
250°C
305°C
30°C for 4 min; programmed
to rise at 40°C/min until it
reaches, 250 °C; return to
30 °C after 17 min
c. Inject 2.5 fjL methylene chloride into
100 mL toluene to obtain 100//g/g, and
analyze as in step B5b.
d. Compare the chromatograms from steps
B5b and B5c (methylene chloride must
be £lOOO/yg/g of adsorbent).
6. Store the adsorbent in a wide mouth amber
glass container with a Teflon-lined cap or in
one of the glass adsorbent modules (tightly
seal with glass stoppers).
7. Use resin within 4 weeks of cleaning or, if
precleaned adsorbent is purchased in sealed
containers, use within 4 weeks after the seal
is broken.
C. Glass Wool Precleaning
1. Immerse sequentially in three aliquots of
methylene chloride
2. Dry in a 110°Coven.
-------
9/30794: L23a-2
3. Store in a methylene chloride-washed glass
jar with a Teflon-lined screw cap.
D. Water Storage Container
Rinse glass container with methylene chloride
before storing water.
£. Sod/urn Su/fate
1. Rinse granulated, reagent grade sodium
sulfate with MeC12 .
2. Oven dry. Store the cleaned material in a
glass container with a Teflon-lined screw
cap.
F. Silica Gel (Bio-Sil A)
1.
Activate the silica gel by heating for
SsSOmin at 180°C.
2. After cooling, rinse the silica gel sequentially
with methanol and MeCI2.
3. Heat the rinsed silica gel at 50 °C for 10 min,
then increase the temperature gradually to
180°Cover 25 min and maintain at 180°C
for 90 min.
4. Cool at room temperature and store in a
glass container with a Teflon-lined screw
cap.
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-------
9/30/94: L24-1
LABORATORY PROCEDURE 24
Volatile Matter Content, Water Content, Density,
Volume Solids, and Weight Solids of Surface Coatings
Note: The laboratory data sheet (LDS 24) serves as
A. Applicable Standard Methods
Follow procedures specified in the standard
methods below:
1. ASTM D 1475-60 (Reapproved 1980),
Standard Test Method for Density of Paint,
Varnish, Lacquer, and Related Products.
2. ASTM D 2369-81, Standard Test Method for
Volatile Content of Coatings.
3. ASTM D 3792-79, Standard Test Method for
Water Content of Water Reducible Paints by
Direct Injection into a Gas Chromatograph.
4. ASTM D 4017-81, Standard Test Method for
Water in Paints and Paint Materials by the
Karl Fischer Titration Method.
5. ASTM D 4457-85, Standard Test Method for
Determination of Dichloromethane and
1,1,1-Trichloroethane in Paints and Coatings
by Direct Injection into a Gas Chromatograph.
B. Volatile Matter Content
1. Using ASTM D 2369-81, determine the
volatile matter content (may include water) of
the coating.
2. Run duplicate sets of analyses for each
coating until the criterion in LDS 24 is met.
a summary; hence, there is no Summary Sheet.
C. Water Content
1. For waterborne (water reducible) coatings
only, determine the weight fraction of water
using either ASTM D 3792-79 or ASTM
D 4017-81.
2. Run duplicate sets of determinations until
the criterion in LDS 24 is met.
D. Coating Density
1. Determine the density of the surface-
coating using ASTM D 1475-60.
2. Run duplicate sets of determinations for
each coating until the criterion in LDS 24
is met.
£. So/ids Content
Calculate the volume fraction solids of the
coating using the manufacturer's formulation.
F. Exempt Solvent Content
Determine the weight fraction of Exempt
Solvents using ASTM D 4457-85.
-------
9/30/94: LD24-1
LABORATORY DATA SHEET 24
VOC in Surface Coatings
Client/Plant Name
Analyst
Job*
Attach appropriate ASTM analytical data and summarize the information below:
Sample ID#
Date
Difference zzWithin-Lab Values?
Run No.
Volatile Matter Content, Wv
Water Content, Ww
Density, Dc
Solids, V,
Wgt Fract'n Nonaq. Vol. Matter
Solvent-Borne, W0 «= Wv
Waterbome, W0 = Wv - Ww
Wat Fract'n Solids, W. - 1 - Wv
1
-
2
Diff
•
Avg
Within-Lab
0.015 Wv =
0.029 Ww =
0.00 1 kg/liter
t
OK?
-•
Confidence Limit Calculations for Waterbome Coatings
LCLWV « 0.953 Wv
UCLWW « 1.075WW
LCL D0 - D0 + 0.002
QA/dC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: L24A-1
LABORATORY PROCEDURE 24A
Volatile Matter Content and Density of
Printing Inks and Related Coatings
Note: The laboratory data sheet (LDS 24A) serves as a summary; hence, there is no Summary Sheet.
A. Weight Fraction VOC
1. Run triplicate analyses. Shake or mix the
sample thoroughly to suspend completely all
the solids. Label and weigh to the nearest
0.1 mg a weighing dish.
2. Use a 5-mL syringe without a needle to
remove a sample of the coating. Weigh the
syringe and sample to the nearest 0.1 mg.
3. Transfer 1 to 3 g of the sample to the tared
weighing dish. Reweigh the syringe and
sample to the nearest 0.1 mg.
4. Heat the weighing dish and sample in a
vacuum oven at 510 ± 51 mm Hg absolute
and at 120 ± 2°C for 4 hr.
5. Allow the weighing dish to cool, and reweigh
it to the nearest 0.1 mg.
B. Coating Density
Determine the density of the ink or
related coating using ASTM D 1475-60
(Reapproved 1980).
C. Solvent Density
Run triplicate analyses. Determine the
density of the solvent using ASTM D 1475-60
(reapproved 1980).
D. Alternative
Rather than using a vacuum oven, heat the
weighing dish and sample in a forced draft oven
at 120 ± 2°Cfor24hr.
-------
9/30/94: LD24A-1
LABORATORY DATA SHEET 24A
Printing Inks
Client/Plant Name
Analyst
Job #
Date
Attach appropriate ASTM analytical data and record the information below:
Sample ID#
Run No.
Weighing Dish, Mx, (g)
Syringe/Sample, Mcy, (g)
Syringe/Sample, Mcy2 (g)
Weighing Dish/Sample, M^ (g)
Solvent Density, D0 (kg/L)
Coating Density, De (kg/L)
Wgt Fract'n VOC, W0
Vol Fract'n VOC, V0
1
2
3
Avg
/,
Sample
Run No.
Weighing Dish, Mxt (g)
Syringe/Sample, M,.yl, (g)
Syringe/Sample, Mey2 (g)
Weighing Dish/Sample, M^ (g)
Solvent Density, D0 (kg/liter)
Coating Density, Dc (kg/liter)
Wgt Fract'n VOC, W0
Vol Fract'n VOC, V0
1
2
3
Avg
Mcy1 ~
V -
• n
QA/QC Check
Completeness.
Checked by: _
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/3O/94: S25-1
SUMMARY SHEET 25
Total Gaseous Nonmethane Organic Emissions as Carbon
Client/Plant Name
Job No.
Sampling Location
Run ID #
FDS25
FDS25
FDS25
FDS25
Run#1
Run #2
Run #3
Avg
Test Date
Run Start Time
Run Finish Time
FDS25
FDS25
FDS25
Sample Tank Volume, L
Pre-test Barometric Pressure, mm Hg
Pre-test Tank Pressure, mm Hg
Post-test Tank Pressure, mm Hg
Pre-test Tank Temperature, °C
Abs. Pre-test Tank Temperature (tti + 273), K
Post-test Tank Temperature, °C
Abs. Post-test Tank Temperature, K
Daily Response Factor for CO2
Daily Response Factor for NMO
ICV Volume, m3
ICV Final Pressure, mm Hg
ICV Final Temperature, K
Final Tank Pressure, mm Hg
Final Tank Temperature, K
Volume of Metered Gas Sample, dscm
Concentration of Noncondensible
Organics in Tank, ppm C
Organics in Stack, ppm C
Concentration of Condensible
Organics in ICV, ppm C
Organics in Stack, ppm C
TGNMO Concentration in Stack
TGNMO Concentration, ppm C
TGNMO Concentration, mg C/dscm
Audit Relative Error, %
V
Pti
FDS25
FDS25
FDS25
FDS25
FDS25
SS25
FDS25
SS25
DRFC02 LDS 25a
DRFNMO LDS25a
Vv LDS 25a
Pf LDS 25a
Tf LDS 25a
tf
"tm
ITU
RE
LDS25a
LDS 25a
SS25
LDS 25a
SS25
LDS 25a
SS25
SS25
SS25
QA 1
= 0.3857 V
t
c,=
PI
-"tm
mc = 0.4993 C
-------
Samp!*
Tank
Figure F25-1. Sampling Train.
-------
9/30/94; F25-1
FIELD PROCEDURE 25
Total Gaseous Nonmethane Organic Emissions as Carbon
Note: The forms in this section contain the information required by the test method; we are aware that some
of the technology specified in the test method is obsolete. In these cases, the user should modify the forms
to make them consistent with the technology used.
A. Sampling
1. Determine the sample tank volume by
weighing it empty and then filling with
deionized distilled water; weigh to ± 5 g,
and record. Alternatively, measure the
volume of water used to ±5 mL.
2. Select a total sample time ^minimum
sampling time specified in the applicable
.subpart of the regulation, and calculate
sampling rate based on sample tank volume.
3. Leak-check the sample tank as follows:
Evacuate the sample tank to 10 mm Hg
absolute pressure or less. Then close the
sample tank valve, and allow the tank to sit
for 30 min. The tank vacuum must not
change > ±2 mm Hg. This step may be
conducted either in the laboratory or the
field.
4. Just before assembly, measure the tank
vacuum with a mercury U-tube manometer.
Record this vacuum, the ambient
temperature, and the barometric pressure at
this time. Close the sample tank valve and
assemble the sampling system as shown in
Figure F25-1. Immerse the condensate trap
body in dry ice. Keep the point where the
inlet tube joins the trap body 2.5 to 5 cm
above the top of the dry ice.
5. Mandatory: Calculate or measure the
approximate volume of the sampling train
from the probe tip to the sample tank valve.
After assembling the sampling train, plug
the probe tip, and make certain that the
sample tank valve is closed. Turn on the
vacuum pump, and evacuate the sampling
system from the probe tip to the sample
tank valve to ^ 10 mm Hg absolute pressure.
Close the purge valve, turn off the pump,
wait <5 min, and recheck the indicated
vacuum (this constitutes the leak-check).
Calculate the maximum Ap in cm Hg (i 1 %
of sampling rate); see FDS 25.
6. Unplug the probe tip, and place the probe
into the stack perpendicular to the duct or
stack axis; locate the probe tip at a single
preselected point of average velocity facing
nozzle away from the direction of gas flow.
Seal the sample port sufficiently to prevent
air in-leakage around the probe.
7. Set the probe temperature controller to
129 °C and the filter temperature controller
to 121 °C. Allow the probe and filter to heat
for about 30 min before purging the sample
train.
8. Close the sample valve, open the purge
valve, and start the vacuum pump. Set the
purge rate between 60 and 100 cc/min, and
purge the train with stack gas for ^ 10 min.
9. Check the dry ice level around the
condensate trap, and add dry ice if
necessary. Record the clock time. Wait
until the temperatures at the exit ends of the
probe and filter are within their specified
range, then close the purge valve and stop
the pump. Open the sample valve and the
sample tank valve.
10. Set the flow control valve to the selected
sampling rate, and maintain a cpnstant rate
(±10%) during sampling.
11. Record the sample tank vacuum and
, flowmeter setting at 5-min intervals. (See
FDS 25). End the sampling when required
sampling time is reached or when a constant
flow rate cannot be maintained because of
reduced sample tank vacuum.
12. Note: If sampling is stopped because of the
latter condition in step A11, proceed as
follows: After closing the sample tank valve,
remove the used sample tank from the
sampling train (without disconnecting other
portions of the sampling train). Take
another evacuated and leak-checked sample
tank, measure and record the tank vacuum,
and attach the new tank to the sampling
train. Proceed with the sampling until the
required minimum sampling time has been
exceeded.
13. After sampling is completed, close the flow
control valve, and record the final tank
vacuum; then record the tank temperature
and barometric pressure.
B. Sample Recovery
1. Close the sample tank valve, and disconnect
the sample tank from the sample system.
2. Disconnect the condensate trap at the flow
metering system, and tightly seal both ends
of the condensate trap. Do not include the
probe from the stack to the filter as part of
the condensate sample.
-------
3. Keep the trap packed in dry ice until the
samples are returned to the laboratory for
analysis.
4. Identify and label the condensate trap and
the sample tank(s).
Notes
1. Organic participate matter interferes, but is
eliminated by particulate filter.
2. Absorbed CO2 in condensed water produce
a positive bias. Determine CW =
(%CO2){%H2O). As a guideline, if CW is
£100, the bias can be considered
insignificant. Thus, a source having 10%
CO2 and 10% water vapor would not have a
significant bias, but a source having 10%
COj and 20% water vapor might have a
significant bias.
4.
9/30/94: F25-2
This method tends to give high biases for
low concentrations (t'100 ppm C) and low
bias for high concentrations. For low
concentrations, consider Method 25A.
For low molecular weight organics, consider
a totally automated semicontinuous
nonmethane organics (NMO) analyzer ,
interfaced directly to the source.
-------
2/9/35: FD25-1
FIELD DATA SHEET 25
Total Gaseous Nonmethane Organic Emissions as Carbon
Client/Plant Name
City/State
Job*
Date •
Test Location/Run #
Thermocouple I.D.
Trap 1.6.
Train Vol. from probe tip to sample tank valve. -V,
Personnel
Sample Train I.D.
. cc
Tank I.D.
Start time
Tank Vol. V
Stop time
L
Sample tank pre-test leak-check J i ±Apcate after 5 min)?
Time
(5-min interv)
Tank Vacuum Pressure
(mm Hg)
Flowmeter Setting
(cc/min)
Probe exit Temp.
(0C)k>129?)
Filter Inlet Temp.
(QC)(a121)
Pb Tank Temp Tank Press.
(mm Hg) . t, (°G) P, (mm Hg)
Post-test
Sampling rate between 60 and 100 cc/min?
A second sample tank necessary? If so Tank I.D..
Constant rate (±10 cc/min) maintained?
Tank Vol.
QA/QC Check
Completeness.
(Attach another FDS 25 data sheet with pertinent data filled out; write NA for not applicable parts)
Legibility Accuracy Specifications Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
I r 1 n..
-------
9/30/94; L25-1
LABORATORY PROCEDURE 25
Total Gaseous Nonmethane Organic Emissions as Carbon
A. Calibration Standards
Each calibration gas must have a manufacturer
recommended maximum shelf life (i.e., no change
> ±5% from its certified value), date of gas
cylinder preparation, and certified organic
concentration affixed to the cylinder before
shipment to the buyer. Obtain the following
standard gas mixtures:
1. Propane: nominal 20 ppm, 200 ppm, and
3000 ppm, in air.
2. Methane: nominal 1 %, in air.
3. C02: nominal 50 ppm, 500 ppm, and 1 %, in
air. The 1 % mixture must have < 1 ppm
nonmethane organics (NMO).
4. Propane Mixture: nominal 50 ppm CO,
50 ppm CH4, 2% CO;,, and 20 ppm C3H8, in
air.
5. Hexane: nominal 50 ppm, in air.
6. Toluene: nominal 20 ppm, in air.
7. Methanol: nominal 100 ppm, in air.
B. Equipment Preparation
1. Perform all the necessary functions to bring
the analyzer into proper working order.
2. Set the carrier gas flow to 29.5 cc/min He
and 2.2 cc/min O2. Set the column oven to
85°C.
C. NMO Analyzer Performance Test
Perform these tests before the system is
first placed in operation, after any shutdown
> 6 months, and after any major modification of
the system.
1- Oxidation Catalyst Efficiency Check. Turn
off or bypass the NMO analyzer reduction
catalyst. Make triplicate injections of 1 %
methane standard, and average the FID
response for unoxidized CH4 (must be < 1 %
of the methane concentration).
2. Reduction Catalyst Efficiency Check. With
the oxidation catalyst unheated or bypassed
and the heated reduction catalyst bypassed,
make triplicate injections of 1 % methane
standard, and average the FID response.
Repeat this procedure with both catalysts
operative (must be ±5% of each other).
3. Analyzer Linearity Check and NMO
Calibration. While operating both the
oxidation and reduction catalysts,
a. Make triplicate injections of each
propane standard (A1), and calculate
the average response factor
(area/ppm C) for each concentration,
relative standard deviation or RSD
(±2%) and the overall mean or RFNMO
(± ±2.5% of average).
b. Make triplicate injections of each CO2
standard (A3), and calculate the average
response factor (area/ppm C) for each
concentration, RSD (i±2%), and the
overall mean response factor (RFC02)
U-±2.5%). In addition, RFC02 =;10% of
R|rNMO-
4. System Performance Check. Make triplicate
injections of the calibration gases listed in •
A4 through A7, and average (measured
NMO value for each gas must be ^ ±5% of
the expected value).
D. Performance Check of Condensate Recovery
Apparatus
Perform these tests before the system is first
placed in operation, after any shutdown of
*6 months, and after any major modification of
the system, or at the specified frequency.
1 • Carrier Gas and Auxiliary O. Blank Check.
Analyze each new tank of carrier gas or
auxiliary O2 with the NMO analyzer to check
for contamination.
a. Purge the sample loop with the cylinder
gases, and then inject the sample into
.the NMO analyzer. After the CO2 (if
any) elutes (about 100 sec under the
specified operating conditions) and as
soon as the detector response returns
to baseline following the CO2 peak,
switch the carrier gas flow to backflush,
and raise the column oven temperature
to 195°'C as rapidly as possible (e.g.,
30°C/min).
b. Record any measured CH4, CO, C02, or
NMO, and sum. Return the column
oven temperature to 85°C before the
next analysis. Analyze each cylinder
gas in triplicate, and average (the sum
of the averages must be <5 ppm).
2. System Performance Check. Construct and
insert a liquid sample injection unit (see
Figure L25-1) into the condensate recovery
and conditioning system in place of a
condensate trap, ^nd set the carrier gas and
auxiliary O2 flow ,-y;es to normal operating
levels. Proceed as follows:
-------
1—I I H*MHVMn> I d
J,./\.A »r»«««
GW '"® >»•!«
Sample
Tank
Figure L2S-2. Condmcat* Rccxwwy SyrUm. Cq purg*.
-------
a. Attach an evacuated intermediate
collection vessel (ICV) to the system,
and switch from system vent to collect.
With the carrier gas routed through the
injection unit and the oxidation catalyst,
make separate injections {in triplicate) of
50 ill hexane, 10 pL hexane, SO f/L
decane, and 10 f/L decane into the
injection port.
b. Follow the procedure in step G to
recover the sample. Measure the final
ICV pressure, and then analyze the
vessel to determine the CO2
concentration.
c. For each injection, calculate the
% recovery and average (must be
100 ± 10% with a relative standard
deviation < 5 % for each set of triplicate
injections).
E. NMO Analyzer Daily Calibration
Conduct these steps before and immediately
after the analysis of each set of samples or on a
daily basis (whichever occurs first).
1. CO2 Response Factor. Conduct step C3b
with 1% CO2 calibration gas (must be --±5%
of the initial RFC02 (step C3b). Use this daily
response factor (DRFC02) for analyzer
calibration and the calculation of measured
CO2 concentrations in the ICV samples.
2. NMO Response Factors. Conduct step C4
with only the propane mixture standard (A4)
(must be -- ±5% of the initial RFNMO
(step C4). Use this daily response factor
. (DRFNMO) for analyzer calibration and
calculation of NMO concentrations in the
sample tanks.
F. Condensate Recovery System Check
See Figure L25-2. Each day before analyzing
any samples, perform the following tests:
1. Leak-Check. With the carrier gas inlets and
the sample recovery valve closed, install a
clean condensate trap in the system, and
evacuate the system to ± 10 mm Hg absolute
pressure. Pressure change must be <2 mm
Hg after 10 min.
2. System Background Test- Adjust the carrier
gas and auxiliary O2 flow rate to their normal
values of 100 cc/min and 150 cc/min,
respectively, with the sample recovery valve
in vent position. Using a 10-mL syringe
withdraw a sample from the system effluent
through the syringe port. Inject this sample
into the NMO analyzer, and measure the CO2
content (must be <10 ppm).
9/30/94: L25-2
3. Catalyst Efficiency Check. Conduct this
check as follows:
a. Replace the carrier gas cylinder with the
1 % methane standard. Set the four-
port valve to the recovery position, and
attach an ICV to the recovery system.
With the sample recovery valve in vent
position and the flow-control and ICV
valves fully open, evacuate the
manometer or gauge, the connecting
tubing, and the ICV to i 10 mm Hg
absolute pressure. Close the flow-
control and vacuum pump valves.
b.
c.
G.
After the NDIR response has stabilized,
switch the sample recovery valve from
vent to collect. When the manometer or
pressure gauge begins to register a
slight positive pressure, open the flow-
control valve. Adjust the flow to
maintain atmospheric pressure ±10% in
the system. Continue collecting the
sample in a normal manner until the ICV
is filled to a nominal gauge pressure of
300 mm Hg.
Close the ICV valve, and remove the
ICV from the system. Place the sample
recovery valve in the vent position, and
return the recovery system to its normal
carrier gas and normal operating
conditions. Analyze the ICV for CO2
using the NMO analyzer (must be
<±2% of the methane standard
concentration.
Condensate Trap CO2 Purge and Sample
Tank Pressurization and Analysis
Before analysis, the NMO and recovery
systems must have met the performance
specifications in steps C through F. The
condenser trap may contain significant amounts
of CO2, which must be removed before analyzing.
To avoid loss of any condensed organics and
residual sample gases, the trap is purged with
zero air and the purged gases are collected in the
original sample tank.
1. Set the four-port valve of the condensate
recovery system in the CO2 purge position as
shown in Figure L25-2. With the sample
tank valve closed, attach the sample tank to
the sample recovery system. With the
sample recovery valve in the vent position
and the flow control valve fully open,
evacuate the manometer or pressure gauge
to the vacuum of the sample tank. Next,
close the vacuum pump valve, open the
sample tank valve, and record the tank
pressure.
-------
lyrtnf.
Hit
Figure L2S-3. Condantato Recovery System, collection of trap organic*.
-------
2.
4.
5.
H.
Attach the dry-ice-cooled condensate trap to
the recovery system, and initiate the purge
by switching the sample recovery valve from
vent to collect position. Adjust the flow
control valve to maintain atmospheric
pressure in the recovery system. Continue
the purge until C02 in the trap effluent is
<5 ppm.
After the NDIR response has reached a
minimum level, extract with a 10-mL syringe
a sample from the syringe port before the
NDIR, and analyze CO2 in the trap effluent
with the NMO analyzer.
After the completion of the CO2 purge, use
the carrier gas bypass valve to pressurize the
sample tank to approximately 1,060 mm Hg
absolute pressure with zero air.
Analyze the sample for NMO in the sample
tank as in step D, except purge the loop with
sample.
Recovery of the Condensate Trap Sample
and Analysis
. See Figure L25-3. Attach the ICV to the
sample recovery system. With the sample
recovery valve in a closed position, between
vent and collect, and the flow control and
ICV valves fully open, evacuate the
manometer or gauge, the connecting tubing,
and the ICV to 10 mm Hg absolute pressure
Close the flow-control and vacuum pump
valves.
Begin auxiliary oxygen flow to the oxidation
catalyst at a rate of 150 cc/min, then switch
the four-way valve to the trap recovery
position and the sample recovery valve to
collect position (see Figure L25-3). After the
manometer or pressure gauge begins to
register a slight positive pressure, open the
flow control valve. Adjust the flow-control
valve to maintain atmospheric pressure in the
system within ±10%.
Now, remove the condensate trap from the
dry ice, and allow it to warm to ambient
temperature while monitoring the NDIR
response. If after 5 min, CO2 in the catalyst
effluent is below 10,000 ppm, stop the
auxiliary oxygen flow to the oxidation
catalyst. Begin heating the trap by placing it
in a furnace preheated to 200°C. Once
heating has begun, carefully monitor the
NDIR response to ensure that the catalyst
effluent concentration does not exceed
50,000 ppm. Whenever CO2 exceeds
50,000 ppm, supply auxiliary oxygen to the
catalyst at the rate of 15O cc/min.
9/30W'. L25-3
4. Begin heating the tubing that connected the
heated sample box to the condensate trap
only after CO2 falls below 10,000 ppm. This
.tubing may be heated in the same oven as
the condensate trap or with an auxiliary heat
source such as a heat gun. Heating
temperature must not exceed 200°C. If a
heat gun is used, heat the tubing slowly
along its entire length from the upstream end
to the downstream end, and repeat the
pattern for a total of three times. Continue
the recovery until CO2 drops to < 10 ppm as
determined by syringe injection as described
under the condensate trap CO2 purge
procedure, step G3.
5. After the sample recovery is completed, use
the carrier gas bypass valve to pressurize the
ICV to approximately 1060 mm Hg absolute
pressure with zero air.
6. Analyze the recovered condensate sample as
in step D1a, except purge loop with sample
and record the value obtained for the
condensible organic material (Ccm) measured
as CO2 and any measured NMO.
I. Audit Samples
If appropriate, analyze the audit samples.
-------
9/30/94: LD25-1
LABORATORY DATA SHEET 25
Total Gaseous IMonMethane Organic Emissions as Carbon
Client/Plant Name
City/State
Analyzer ID #
Job*
Date
Trapl.D.
Analyst
Performance Test
Sample ID
or Condition
FID
Area 1
FID
Area 2
FID
Area3
Avg
A
AvaRF
(ppmC/Area)
RSD
Diff.
from Avg
Oxidation Catalyst Efficiency Test: 1 % CH., Certified Concentration
Red. cat. off/bypassed
"' "', '1 /"
' ^
, - ,
RF {from cal) x A » ppm (<±1% of certified concentration?)
Reduction Catalyst Efficiency Check: 1 % CH4 Certified Concentration ,
Both catalysts off/bypassed
Both catalysts operative
•V {'f ' / ^
'" i'
•M- /
' ,• * ff f
A(on)/A(off) - (20.95?)
Linearity Chock Note: Differences are calculated from overall average.
20 ppm C,H8
Certified Cone.
200 ppm CjH,
Certified Cone.
§,000 ppm CaH,
ertifiedcone.
RSD < ±2%? Avg RF of each cal gas < ±2.5% of RFNMO? RFNMO = Avg
50 ppm CO,
Certified Cone.
500 ppm CO2
Certified Cone.
1%CO,
Certified Cone.
RSD < ±2%? Avg RF of each cal gas <; ±2.5% of RF002? RFC02 = Avg
System Performance Check
Propane Mixture
Certified Cone.
50 ppm Hexane
Certified Cone.
20 ppm Toluene
Certified Cone.
100 ppm Methanol
Certified Cone.
Cone, ppm
RFC02<10%RFNMO?
- , ''
'<< , ' ,,
" ''
t -' ' ,
' ;•
*'!.
; ":
, 7- '
Each gas value < ±5% of the certified cone.?
-------
LABORATORY DATA SHEET 25 (Continued)
Condensate Recovery Apparatus
9/30/94: LD25-2
Sample
ID#
=============
Carrier Gas or Auxiliar
CH4
CO
CO2
NMO
Sum of CHV CC
System Performance C
50. lA. Hexane
10ywL Hexane
50 [A- Decane
1 0 /A. Decane
Injection 1
Area
=========
/ O2 Blank Che
Injection 2
Area
=========
ck: Cyl
•
Injection 3
Area
========
nder ID #
Average
Area
=========
Sum
Cone,
(ppm)
'
, CO2, or NMO concentration in the cylinder c5 ppm?
heck: Concentrations are for ppm C02/ C^,
Average % recovery 100 ±10% and RSD <5% for each set of triplicate injections?
RSD
(%)
=====
•••••••••• "• %%,% -^>^
; f '
\ f
=======
%
Recovery
=1======
x""" >
t~* -- ::
':• ,
^/*
'
=====
Molecular Weight of Injection Liquid, m
Liquid Volume Injected, L
Density of Liquid Injected, p
Number of Carbon in Liquid, N
Intermediate Tank Volume, Vv
Hexane =
10 or 50 {A.
Hexane =
Hexane =• 6
m V P C
% Recovery = 1.604 — — — -^
I P T, N
Decane
Decane =
Decane =10
g/g-mole
g/cc
%Recovery = 1.604 — -^ _L -^2.
L p Tf N
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Analyst (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
2/9/95: LD25a-1
LABORATORY DATA SHEET 25a
Total Gaseous Organic Emissions as Carbon
Client/Plant Name
City/State
Job #
Date
Analyzer ID #
Analyst
NMO Operating Conditions
He carrier gas flow [29.5 cc/min]
Column Oven Temp. 185°F]
cc/min O2 carrier gas flow [2.2 cc/min]
cc/min
Note: Use the daily response factors (DRFCO2 or DRFNMO ) for analyzer calibration and calculation of CO2 in ICV and
NMO In sample tank.
Daily Calibration
Sample ID#
Area 1
Area 2
Area 3
Avg. Area
DRF
NMO Analyzer CO2 Response Factor: •
1% CO2 Certified
Concentration
\
DRFC02 s;± 5% of the initial RFC02 (from LDS 25)7 <
NMO Response Factors: Analyze for propane only.
Propane Mixture
Certified Cone.
DRFNMO a: ±5% of the initial RFNMO (from LDS 25)7
Condensata Recovery System Background Test
System Effluent, C02
C02 content <10 ppm?
Condonsate Recovery System Catalyst Efficiency Check
1%CH4
Certified Cone.
-
ppm CO2 ,
ppm CO2
ICV C02 concentration ss ±2% of CH4 certified cone.?
Condensate recovery system leak-checked at £10 mm Hg absolute for 10 min (<2 mm Hg change?)
LDS 25 attached and data indicate acceptable performance?
Analyst certification attached? Certification should state that no shutdown of the NMO analytical apparatus
of greater than 6 months occurred or no major modifications of the system were made after the performance
test date for the NMO analyzer and condensate recovery system.
-------
LABORATORY DATA SHEET 25a (Continued)
Condensate Trap Recovery
ICV initial pressure :£ 10 mm Hg absolute?
Auxiliary O2 flow rate at 150 cc/min?
If warm up at ambient for 5 min yields CO2
< 10,000 ppm, aux. O2 stopped?
If heating trap to 200°C yields CO2 > 50,000
ppm, aux O2 supplied at 150 cc/min?
2/9/95: LD25a-2
Sample recovered from tubing that connected
the heated sample box to condensate trap?
Recovery continued 10 mL syringe samples by
NMO analyzer are < 10 ppm CO2?
ICV tank pressurized to 1060mm Hg?
Sample Analysis
ICV Analysis
Sample
ID#
Blank
Area 1
CO2 NMO
•
. i—— Sum' C"m " ppm CO" + DDm NMO
Area 2
CO2 NMO
AreaS
CO2 NMO
Avg.*
C02
Area
CO2
Cone.,
( ppm C )
Avg.«
NMO
Area
NMO
Cone.,
(ppm C)
'-
. *
Sum,
Ccm
(ppm C)
Run #
ICV ID
ICV Vol., Vv
(m3)
ICV Final Press., Pf
(mm Hg)
ICV Final Temp, Tf
(K)
3
Blank
Condensate Trap CO2 Purge and Sample Tank Pressurization
Sample collected until 10-mL syringe samples analyzed by NMO analyzer are <5 ppm CO2?
Sample tank pressurized with zero air to a final pressure of about 1060 mm Hg?
Sample Tank Analysis
Sample ID*
Blank
Tank Final Press.,
Ptf (mm Hg)
Tank Final
Temp.. Ttf (K)
Area 1
Area 2
Area 3
Avg"
Area
Cone., C
(ppm C)
If more than three injects are used, average all injects.
_ Legibility Accuracy
QA/QC Check
Completeness
Checked by:
Analyst (Signature/Date)
Sample loop purged with sample before analysis?
Specifications Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: F25A-2
2. Determine the amount of drift (must be <3%
of span value) for zero and mid-level gases.
3. If drift is <:3%, invalidate the test results
preceding the check and repeat the test
following corrections to the measurement
system. Alternatively, recalibrate the test
measurement system as in step B, and report
the results using both sets (before and after
the test period) of calibration data.
G. Notes
A 40% H2/60% He or 40% H2/60% N2 fuel
gas mixture is recommended to avoid an O2
synergism effect that reportedly occurs
when O2 varies significantly from a mean
value.
F. Alternatives
1. Calibration Gases. Non-propane standards
may be used, provided that appropriate
corrections are made for response factors.
2. FIA Modifications. For high concentrations
of organics (>1.0% as propane)
modifications to most commonly available
FIA's are necessary/ such as using a smaller
diameter sample capillary to decrease the size
of the sample to the FIA.
3-W«y
Valve
CXJ
Stack
Figure F25A-1. Organic Concentration Measurement System.
-------
9/30/94; FD25A-1
FIELD DATA SHEET 25A
Total Gaseous Organics
Client/Plant Name
City/State
Job#
Date
Test Location
Analyzer ID#_
Personnel _
Span value
ppm
Determine Calibration Error before (within 2 hr) the first test run:
Organic
Analyzer
Zero
Low-level
Mid-level
High-level
Calibration Gas
Cylinder ID #
Gas Value (ppm or %)
Analyzer
Response (ppm or %)
Cal Error Result
(% of span)
' V*
% Cal Err s±5% of cal gas?
multiplication factor.
Determine Response Time:
Run No.
1
Average
Organic Analyzer
Upscale (sec.)
% Cal Error = Analyzer Response - Gas Value .
Gas Value
check each additional range with a mid-level calibration gas to verify the
Sampling
Upscale time is 95% of the step change.
Sample Pt
Start
Time
Stop
Time
Response
Organic Cone, (ppm)
Average Cone., C
avg
Run*
1
2
3
Condition
Zero
Mid-level
Zero
Mid-level
Zero
Mid-level
Cylinder Value
Analyzer Response
Initial
Final
Difference
(Initial - Final)
% Drift
% Drift = I Difference | inn
Span Value % Drift ^±3% of span value
QA/QC Check
Completeness _
Legibility.
Accuracy,
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
-------
9/3O/94: S26-1
SUMMARY SHEET 26
Hydrogen Halides and Halogens
Run #1 Run #2 Run #3 Avg
Client/Plant Name FDS 26
Job No. FDS 26
Sampling Location FDS 26
Run ID # FDS 26
Test Date FDS 26
Dry Gas Meter Calibration Factor Y FDS 26
Barometric Pressure, mm Hg Pb FDS 26
Average DGM Temperature, °C tm FDS 26
Volume of Metered Gas Sample, L Vm FDS 26
Volume of Metered Gas Sample, dsL vm(std) ss 26
Sample Concentration, fjg/mL S LDS 26
Blank Concentration, fjg/mL B LDS 26
Sample Mass of Halide, jt/g mHX SS 26
Sample Mass of Halogen, //g mX2 SS 26 •
Stack Concentration, mg/dscm C SS 26
Audit Relative Error, % RE QA1
Post test Calibration Checks
Temperature and Barometer CDS 2d
Metering System CDS 6
= k(S-B)
K = 1.028 for HCI
K = 1.013forHBr
K = 1.053 for KF
200(S-B)
C = 10-3-
m
Vm(ald)
, 0.3858
-------
Mae West
Impinger or
Drying Tube
Gas Flow
Empty S^/ \/
Temperature 15 mL 0.1 N 15 mL 0.1 N
H2S04 NaOH
Silica Gel
Sensor
I
Surge Tank
Air-Tight
Pump
Figure F26-1. Sampling Train.
-------
9/30/94: F26-1
FIELD PROCEDURE 26
Hydrogen Halide and Halogen - Midget Impingers
A. Preparation of Sampling Train
1. Prepare the sampling train shown in
Figure F26-1 as follows:
_, a. Pour 15 mL acidic absorbing solution
into each of the first two impingers, and
15 mL alkaline absorbing solution into
each of the second pair of impingers.
b. Place fresh silica gel, or equivalent, in
the drying tube or impinger at the end of
the train.
c. For high moisture sources or > 1 re-
sampling times, use the empty impinger
as shown in Figure F26-1 before the
first impinger.
2. Adjust and maintain the probe temperature
and the temperature of the filter and the
stopcock to 2:20°C above the source
temperature, but :£ 120° C.
3. Optional: Leak-check the sampling train and
pump separately according to FP 3c,
sections C and D.
4. Connect the purge line to the stopcock, and
turn the stopcock to purge the probe (see
Figure F26-1 A), and purge at a rate of
2 L/min for &5 min before sampling.
B. Sampling
1. Turn on the sampling pump, pull a slight
vacuum of ~1 in. Hg on the impinger train,
then turn the stopcock to sample stack gas
through the impinger train (Figure F26-1C).
2. Adjust the sampling rate to 2 L/min, as
indicated by the rate meter, and maintain
within ±10% during the entire sampling run.
3. Record the data as required on FDS 26.
Take appropriate readings at 5-min intervals.
4. Sample &1 hr. Shorter sampling times may
introduce a significant negative bias in the
HCI concentration.
5. Mandatory: Leak-check the sampling train
after the sampling run (see FP 3c, section C).
C. Sample Recovery
1. Acidic Absorbing Impingers
a. Disconnect the impingers after sampling
and quantitatively transfer the contents
of the knockout impinger (if used) and
acid impingers to a leak-free storage
bottle.
b. Add the water rinses of each of these
impingers and connecting glassware to
the storage bottle.
2. Alkaline Absorbing Impinoers
a. Quantitatively transfer the contents of
the alkaline impingers to a leak-free
storage bottle.
b. Add the water rinses of each of these
impingers and connecting glassware to
the storage bottle.
c. Multiply 25 mg sodium thiosujfate per
"ppm" of halogen anticipated in the
stack gas by the "dscm" stack gas
sampled, and add this ampunt to
storage container. [Note: This amount
of sodium thiosulfate includes a safety
factor of ~ 5 to assume complete
reaction with the hypohalous acid to
form a second Cl~ ion in the alkaline
solution]
3. Blanks
b.
c.
Save portions of both absorbing
reagents equivalent to the amount used
in the sampling train. Dilute to the
approximate volume of the
corresponding samples using rinse water
directly from the wash bottle being
used.
Add the same amount of sodium
thiosulfate to the alkaline absorbing
solution blank.
Save a portion of the rinse water
directly from the wash bottle.
4.
Seal all sample and blank bottles, shake to
mix, and label. Mark the fluid level.
-------
9/30/94: LD26-1
LABORATORY DATA SHEET 26
Hydrogen Halides and Halogens
Client/Plant Name _
City/State
Job No.
Sampling Location
Ion Chromatograph ID #
Analyst
Date
QC Sample Cone, /yg/mL: CI"
Br'
Abs Soln: Acidic Alkaline
Sample
No.
Sample
ID#
Cal. Standard 1
Cal. Standard 2
Cal. Standard 3
Cal. Standard 4
Blank
QC Sample
Audit #1
Audit #2
Peak Height (H) or Area (A)
cr
Br~
F-
Concentration, //g/mL
cr
Br"
F-
Plot of peak height or area vs. halide
concentration (/ug/mL) attached?
Injections done in duplicate and agree within
±5% of average?
QA/QC Chock
Completeness _
Checked by: _
Average response from duplicate injections used
to determine concentration?
Audit samples within ±10% of actual
concentration? Note: Samples that are
analyzed to demonstrate compliance must
include a set of two audit samples.
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: S26A-1
SUMMARY SHEET 26A
Hydrogen Halides and Halogens
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Abs Stack Pressure (Pb + Pg/13.6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temperature (ts + 460), R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(tsi+460) Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Isokinetic Sampling Rate, %
Sample Concentration, /jg/mL
Blank Concentration, //g/mL
Volume of Diluted Sample, mL
Sample Mass of Halide, //g
Sample Mass of Halogen, /jg
Stack Concentration, mg/dscf
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 1
FDS 1
G FDS 5
Dn FDS5
Y CDS 5
AH FDS 5
Pb FDS 5
Pg FDS5
Ps SS5
ts FDS 5
Ts FDS 5
%CO2 FDS 3
%O2 FDS 3
%(CO + N2) FDS 3
Md FDS 3
V
m(std)
B
'w(std)
ws
CP
Ap
[Tsi Ap]1'2
S
B
mHX
mX2
C
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS 2a
FDS 5
FDS 5
SS5
FDS 1
SS5
LDS26
LDS26
LDS26
SS26A
SS26A
SS26A
Run#1
Run #2
Run #3
Avg
Audit Relative Error, %
RE
QA 1
-------
9/30/94: S26A-2
Run #1 Run #2 Ruri #3 Avg
Post-test Calibration Checks
Teniperatureand Barometer
Differential Pressure Gauges
Metering Systems
CDS2d
CDS2d
CDS 5
k~ 1.028forHCI
k» 1.013 for HBr
k- 1.053 for HF
10-3m
-------
9/30/94: F26A-1
FIELD PROCEDURE 26A
Hydrogen Halides and Halogens
(Isokinetic Procedure)
Note: This procedure is the same as that for Method 5, except for the variations noted below (see also
Figure F26A-1 for variations in the sampling train). The hydrogen halides (HX) include hydrogen chloride
(HCI), hydrogen bromide (HBr), and hydrogen fluoride (HF)] and the halogens (X2) include chlorine (CI2)
and bromine (Br2). Ground glass stoppers, plastic caps, serum caps,- Teflon tape, Parafilm, or aluminum
foil may be used to close openings of train component after preparation, before sampling, during
transport to and from the sampling site, and prior to sample recovery. Use FDS 5.
A. Sampling
1. Particulate matter may also be determined
concurrently with this method. If so, do not
use the alternative Teflon probe liner, cyclone
and filter holder, but use the Teflon filter
support. If a participate is not to be
determined, do not desiccate or weigh
the filter.
2. When the stack temperature >410°F, use a
one-piece glass nozzle/liner assembly.
3. Add the following reagents (see
Figure F26A-1).
a. 50mL0.1 N H2S04 to the condensate
impinger, if used.
b. 100 mL 0.1 N H2SO4 in each of the next
two impingers.
c. 100 mL 0.1 N NaOH in each of the
following two impingers.
d. 2OO-300 g of preweighed silica gel from
its container to the last impinger.
4. Maintain a temperature >248°F around the
filter and (cyclone, if used).
5. If the condensate impinger becomes too full,
recover condensate for moisture and HX
analysis. Recharge impinger with 50 mL
0.1 N H2SO4, and replace impinger into
sampling train. Conduct required leak-
checks. Subtract leak-check volume from
total volume.
6. Before disassembling the train, visually
inspect the probe liner and filter for signs of
moisture. If any moisture is visible, or
whenever the optional cyclone is used (even
if moisture is not visible), perform the
following procedure. Upon completing the
test run, connect the ambient air conditioning
tube at the probe inlet and purge the train
with the filter heating system at 248°F at a
low flow rate (e.g., AH = 1 in. H20) for
30 min. Remove the conditioning tube, and
examine the cyclone and filter for any visible
moisture. If moisture is still visible, repeat
this step for 15 min, and observe again.
Keep repeating until the cyclone is completely
dry (critical step).
B. Sample Recovery
After recovery, seal the lids of all storage
containers around the circumference with Teflon
tape. Recover the samples as follows:
1.
4.
Container No. 1 (Optional: Filter Catch).
Same as FP 5, step E3.
Container No. 2 (Optional: Front Half Rinse.
Same as FP 5, step E4.
Container No. 3 (Knockout and Acid
Impinger Catch for Moisture and Hydrogen
Halide Determination). Same as FP 5,
step E6, except:
a. Quantitatively transfer this liquid to a
leak-free sample storage container.
Rinse these impingers and connecting
glassware including the back portion of
the filter holder (and flexible tubing, if
used) with water and add these rinses
to the storage container.
b. Seal the container, shake to mix, and
label. Mark the fluid level.
Container No. 4 (Alkaline Impinger Catch for
Halogen and Moisture Determination). Same
as FP 5. step E6, except:
a. Quantitatively transfer this liquid to a
leak-free sample storage container.
Rinse these two impingers and
connecting glassware with water and
add these rinses to the container.
b. Add 25 mg sodium thiosulfate per ppm
halogen-dscm of stack gas sampled.
Seal the container shake to mix, and
label: mark the fluid level. Retain
alkaline absorbing solution blank and
analyze with the samples.
5. Container No. 5 (Silica Gel for Moisture
Determination). Same as FP 5, step E5.
-------
9/30/94: F26A-2
6. Container Nos. 6 through 9 (Reagent Blanks).
Save portions of the absorbing reagent (0.1
N H2SO4 and 0.1 N NaOH) equivalent to the
amount used in the sampling train; dilute to
the approximate volume of the corresponding
samples using rinse water directly from the
wash bottle being used. Add the same ratio
of sodium thiosulfate solution used in
container No. 4 to the 0.1 N NaOH absorbing
reagent blank. Also, save a portion of the
rinse water alone and a portion of the
acetone equivalent to the amount used to
rinse the front half of the sampling train.
Place each in a separate, labeled sample
container.
7. Shipment. Prior to shipment, recheck all
sample containers to ensure that the caps are
well-secured. Ship all liquid samples upright
and all paniculate filters with the particulate
catch facing upward.
C. Alternatives
1. Do not use metal liners. Water-cooling of the
stainless steel sheath is recommended at
temperatures exceeding 500°C. Teflon may
be used in limited applications for stack
temperatures between 250°F and 410°F
(point where Teflon is estimated to become
unstable).
2. The first impinger shown in Figure F26A-1
(knockout or condensate impinger) is optional
and is recommended as a water knockout
trap for high moisture conditions.
3. Teflon impingers are an acceptable
alternative.
4. When the stack gas temperature is 410°F, a
quartz fiber filter may be used instead of the
Teflon mat (e.g., Pallflex TX40H145) filter.
D. Notes
1. The acidic absorbing solution is for the HX,
and the alkaline for the X2. Halogens have a
very low solubility in the acidic solution and
pass through to the alkaline solution where
they are hydrolyzed to form a proton (H"1"),
the halide ion, and the hypohalous acid (HCIO
or HBrO).
2. The post-test purge with conditioned air is to
vaporize any halides/halogens dissolved in
condensed moisture or liquid droplets in the
cyclone and on the filter and transfer the
gases to the absorbing solutions.
3. Sodium thiosulfate is added to the alkaline
solution to assure reaction with the
hypohalous acid to form a second halide ion
such that 2 halide ions are formed for each
molecule of halogen gas.
4. Interferences
a. Chlorine dioxide (CI02) and ammonium
, chloride (NH4CI), which produce halide
ions upon dissolution, are potential
interferences.
b. The halogen gases that disproportionate
to HX and an hypohalous acid upon
dissolution in water interfere with the
halides measurement, but the acidic
absorbing solution greatly reduces the
dissolution of any halogens.
c. Simultaneous presence of both HBr and
CI2 may cause a positive bias in HCI and
a negative bias in CI2 and affect the
HBr/Br2 split between the acid and
caustic impingers.
d. High concentrations of nitrogen oxides
(NOX may produce sufficient nitrate
(NO3~) to interfere with measurements of
very low Br' levels.
e. When HX <20 ppm, a negative bias
may result, perhaps due to reaction with
small amounts of moisture in the probe
and filter.
5. The in-stack detection limit for HCI is
approximately 0.02 fjg/L of stack gas; the
analytical detection limit for HCI is
0.1 /jg/mL. Detection limits for the other
analyses should be similar.
6. The 25 mg sodium thiosulfate/ppm halogen
includes a safety factor of approximately 5
to assure complete reaction with the
hypohalous acid to form a second CI" ion in
the alkaline solution.
-------
9/30/94: L26A-1
LABORATORY PROCEDURE 26A
Hydrogen Halides and Halogens
Note: This procedures for analyzing Containers Nos. 1 and 2 and Acetone Blank (Optional particulate
matter determination) and Container No. 5 (silica gel) are the same as that in Method 5 and the rest of
the samples are the same as that in Method 26, with the following variations (attach appropriate data
sheets, i.e. LDS 5 and LDS 26).
A. Reagent Preparation
Prepare separate reagent blanks of each absorbing
reagent for analysis with the field samples as
follows:
1. Dilute 200 mL of each absorbing solution
(250 mL of the acidic absorbing solution, if a
condensate impinger is used) to the same
final volume as the field samples using the
blank sample of rinse water.
2. If a particulate is determined, collect a blank
sample of acetone.
B. Analysis
1. Analyze the Cl samples within 4 weeks after
collection for HCI and CI2.
2. Container Nos. 3 and 4 and Absorbing
Solution and Water Blanks. Quantitatively
transfer each sample to a volumetric flask or
graduated cylinder and dilute with water to a
final volume within ± 50 mL of the largest
sample.
3. If the values from duplicate injections are not
within ±5% of their mean, repeat the
duplicate injections and use all four values to
determine the average response.
-------
-------
9/30/94: F27-1
FIELD PROCEDURE 27
Vapor Tightness of Gasoline Delivery Tank
A. Pretest Preparations
1. Empty the delivery tank of all liquid.
2.
8.
Purge as much as possible the delivery tank
of all volatile vapors by any safe, acceptable
method. Two methods are as follows; the
first is more effective than the second.
a. Carry a load of non-volatile liquid fuel,
such as diesel or heating oil, immediately
prior to the test.
b. Blow ambient air into each tank
compartment for at least 20 min.
3.
As much as possible, maintain isothermal
conditions. Allow the tank temperature to
equilibrate in the test environment. During
the test, protect the tank from extreme
environmental and temperature variability,
such as direct sunlight.
4. Open and close each dome cover.
5. Connect static electrical ground connections
to tank. Attach the liquid delivery and vapor
return hoses (optional), remove the liquid
delivery elbows, and plug the liquid delivery
fittings. (Note: If liquid delivery hose is not
attached, inspect it for tears or holes, or fill
with water to detect any liquid leakage.)
6. Attach the test cap to the end of the vapor
recovery hose.
7. Connect the pressure-vacuum supply hose
and the pressure-vacuum relief valve to the
shut-off valve. Attach a manometer to the
pressure tap.
Connect compartments of the tank internally
to each other if possible. If not possible, test
each compartment separately, as if it were an
individual delivery tank.
B. Pressure Test
1. Connect the pressure source to the pressure-
vacuum supply hose.
2. Open the shut-off valve in the vapor recovery
hose cap. Apply air pressure slowly,
pressurize the tank to P,, the initial pressure
specified in the regulation.
3. Close the shut-off and allow the pressure in
the tank to stabilize, adjusting the pressure if
necessary to maintain pressure of P,. When
the pressure stabilizes, record the time and
initial pressure.
4. At the end of "t" minutes, record the time
and final pressure.
Repeat steps B2 through B4 until the change
in pressure for two consecutive runs agrees
within ± 12.5 mm H2O. Calculate the
arithmetic average of the two results.
Disconnect the pressure source from the
pressure-vacuum supply hose, and slowly
open the shut-off valve to bring the tank to
atmospheric pressure.
C. Vacuum Test
5.
6.
1.
2.
3.
4.
5.
6.
Connect the vacuum source to the pressure-
vacuum supply hose.
Open the shut-off valve in the vapor
recovery hose cap. Slowly evacuate the
tank to Vjf the initial vacuum specified in the
regulation.
Close the shut-off valve and allow the
pressure in the tank to stabilize, adjusting
the pressure if necessary to maintain a
vacuum of V,. When the pressure stabilizes,
record the time and initial vacuum.
At the end of "t" minutes, record the'time
and final vacuum.
Repeat steps C2 through C4 until the change
in vacuum for two consecutive runs agrees
within ±12.5 mm H2O. Calculate the
arithmetic average of the two results.
Disconnect the vacuum source from the
pressure-vacuum supply hose, and slowly
open the shut-off valve to bring the tank to
atmospheric pressure.
D. Post-Test Clean-up
Disconnect all test equipment and return the
delivery tank to its pretest condition.
£. Alternative Procedures
1. To obtain either pressure or vacuum, pump
water into the bottom of a delivery tank or
drain water out of the bottom. Slight
alterations of any of the specific step-by-step
procedures to accommodate these
mechanisms are permissible.
2. For techniques other than specified above
for purging and pressurizing a delivery tank,
obtain prior approval from the Administrator.
Provide a demonstrated equivalency with the
above method.
-------
Tank Owner
Address
Test Location/Run #
Tank ID#
9/30/94: FD27-1
FIELD DATA SHEET 27
Gasoline Delivery Tank Pressure Test
Job #
Date/Time
Personnel
Bar. Pressure, Pb
in. Hg Ambient Temp., °F_
Pressure Test
Applicable Reg
Initial Pressure
Run*
1
2
ulation Time, t = minutes
P( - mm H,O Allowable Pressure Change, Ap =
Initial
Pressure, P(
(mm H2O)
Time
Final
Pressure, Pf
(mm H2O)
Time
Average
mm H,O
Diff , Ap
(mm H2O)
n..
r"-~ .
Vacuum Test
Applicable Reg
Initial Vacuum,
Run#
1
2
ntatinn Time, t = minutes
V, - mm H,O Allowable Vacuum Change, Av = mm H20
Initial
Vacuum, Vs
(mm H2O)
Time
Final
Vacuum, Vf
(mm H2O)
Time
Average
Diff,Av
(mm H2O)
Difference between Runs 1 and 2 ^ ± 12.5mm H2O?
QA/ac Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
Witnessing Inspector
Name
(Signature/Date)
Affiliation
-------
9/30/94: S1O1-1
Method (circle) 101.101A 102
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H20
Abs Stack Pressure (Pb + Pg/13.6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temperature (460 + ts), R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mple
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(tsi +460) Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Isokinetic Sampling Rate, %
Mercury in original solution, //g
Mercury Emission Rate, g/day
Audit Relative Error, %
Matrix Check
SUMMARY SHEET 101
Mercury
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS 5
FDS1
FDS1
6 FDS 5
Dn FDS 5
Y CDS 5
AH FDS 5
Pb FDS 5
Pg FDS 5
P8 SS5
ts FDS 5
Ts SS5
%CO2 FDS 3
%O2 FDS 3
%(CO + N2) FDS 3
Md FDS 3
V,
m
'mlstd)
Ic
w(std)
ws
CP
Ap
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS2a
FDS 5
%l
[TsiAp]1/2 FDS 5
SS5
FDS1
SS5
LDS 101
SS101
QA 1
LDS 12a
'Hg
ml
R
RE
Run#1
Run #2
Run #3
Avg
-------
9/30/94: S101-2
Method (circle) 101 101A 102
Post-test Calibration Checks
Temperature and Barometer
Differential Pressure Gauges
Metering System
R - 17.64
v. A (86.400 V10"6)
P.
Run#1
Run #2 Run #3 Avg
CDS2d
CDS2d
CDS 5
-------
9/30/94: F101-1
FIELD PROCEDURE 101
Participate an<* Gaseous Mercury Emissions
from Chlor-Alkali Plants
Note: This field procedure is the same as that in Method 5. Follow the general procedure given in FP 5,
except for the items noted below. Use FDS 5.
A. Pretest Preparation
1. Omit the directions for the filter.
2. Clean all glassware (probe, impingers, and
connectors, including sample recovery
glassware) by rinsing with 50% HNO3, tap
water, 0.1 M ICI, tap water, and finally
deionized distilled water.
B. Preliminary Determinations
1. Select a nozzle size to maintain isokinetic
sampling rates below 1.0 cfm.
2. Select the sampling time ( at least 2 hr) that
accurately determines the maximum
emissions that occur in a 24-hr period. For
cyclic operations, run sufficient runs to
accurately represent the emissions over the
cycle.
3. When Hg or SO2 concentrations are high,
indicated by reddening (liberation of free
iodine) in the first impinger, the sample run
may be divided into two or more subruns to
avoid depletion of absorbing solution.
C. Preparation of Sampling Train
1. Assemble the train as shown in
Figure F101-1.
a. Place 100 mL 0.1 M ICI in each of the
first three impingers.
b. Place about 200 g preweighed silica gel
in the fourth impinger.
c. An empty impinger may be inserted
between the third impinger and the silica
gel to remove excess moisture.
2. Use a Viton A O-ring for the nozzle when
stack temperatures are < 500° For a
fiberglass string gasket when >500°F.
D. Sample Recovery
1. The cleanup area must be free of Hg
contamination.
2. Container No. 1 (Impinger/Probe)
a. Measure the liquid in the first three
impingers to within 1 mL. Place the
contents into a 1000-mL glass sample
bottle.
b. Add any condensate and all washings to
the 1000-mL glass sample bottle.
c. Rinse probe nozzle, fitting, and
liner with two 50-mL portions-of 0.1 M
ICI.
d. Rinse the probe nozzle, fitting, and liner,
and each piece of connecting glassware
between the probe liner and the back
half of the third impinger with £400 mL
water.
e. Tighten the lid on the container; mark
the liquid level. Label the container.
3. Container No. 2 (Silica Gel)
See FP 5, step E5.
4. Container No. 3 (Absorbing Solution Blank)
Place 50 mL 0.1 M ICI absorbing solution in
a 100-mL sample bottle. Seal and label the
container.
-------
Temperature .
'" . s..»r S***
Will H««tTr«ctd
T«mpor«tur«
Stnsor
Minomtlir
RgureF101-1. Mercury Sampling Train.
-------
9/30/94: L101-1
LABORATORY PROCEDURE 101
Paniculate and Gaseous Mercury Emissions
from Chlor-Alkali Plants
A. Reagent Preparation
1. Nitric Acid, 50%. Slowly adding the acid to
the water, mix equal volumes of cone.
HNO3 and water.
2. Potassium Iodide, 25%. Dissolve 250 g Kl
in water, and dilute to 1 L.
3.
4.
5.
6.
7.
Iodine Monochloride (ICI) Stock Solution,
1.0 M. Add 800 mL cone. HCI to 800 mL
25% Kl. Cool. While stirring vigorously,
slowly add 135 g potassium iodate (KIO3),
until a clear orange-red solution occurs.
Cool, and dilute to 1800 mL with water.
Keep the solution in amber glass bottles.
ICI Absorbing Solution, 0.1 M. Dilute
100 mL 1.0 M ICI stock solution to 1 L with
water. Keep the solution in amber glass
bottles and in darkness. Do not use after
two months.
Tin (II) Solution. Prepare fresh daily, and
keep sealed. Dissolve 20 g tin (II) chloride
[or 25 g tin (II) sulfate] crystals in 25 mL
cone. HCI. Dilute to 250 mL with water.
Do not use other acids for HCI.
Hg Stock Solution, 1 mg/mL. Prepare and
store all Hg standard solutions in glass
containers. Dissolve 0.1354 g Hg (II)
chloride in 75 mL water in a 100-mL glass
volumetric flask. Add 10 mL cone. HN03/
and adjust the volume to 100 mL with
water. Mix thoroughly. Do not use after
one month.
Sulfuric Acid, 5%. Dilute 25 mL cone.
H2SO4 to 500 mL with water.
8. Intermediate Hg Standard Solution,
10//g/mL. Prepare fresh weekly. Pipet
5.0 mL Hg stock solution into a 500-mL
glass volumetric flask, and add 20 mL
5% H2SO4 solution. Dilute to 500 mL with
water. Thoroughly mix the solution.
9. Working Hg Standard Solution, 200 ng/mL.
Prepare fresh daily. Pipet 5.0 mL
"Intermediate Hg Standard Solution" into a
250-mL volumetric glass flask. Add 10mL
5% H2SO4 and 2 mL 0.1 M ICI absorbing
solution that was taken as a blank and
dilute to 250 mL with water. Mix
thoroughly.
B. Sample Preparation
1. Note the level of liquid in the sample
containers, and determine loss; note this
loss, if any, on LDS 101.
C.
1.
2. Container No. 1 (Impinger/Probe)
a. Transfer contents into a 1000-mL
volumetric flask, and adjust volume to
1000 mL with water.
b. Pipet 2 mL of diluted sample into a
250-mL volumetric flask. AddlOmL
5% H2SO4, and adjust the volume to
250 mL with water. This solution is
stable for 72 hr. (Note: The dilution
factor will be 250/2 for this solution.)
Equipment Preparation
Clean all glassware, both new and used, as
follows: Brush with soap and water, liberally
rinse with tap water, soak for 1 hr in
50% HNO3, and then rinse with deionized
distilled water.
2. Set the flow rate through the aeration cell to
1.5 ± 0.1 L/min.
a. Assemble the aeration system (see
Figure L101-1).
b. Set the outlet pressure on the aeration
gas cylinder regulator to S: 10 psi.
c. Use a flowmetering valve and bubble
flowmeter to set the flow rate.
3. Calibrate the optical cell heating system as
follows:
a. Add 50 mL of water to the bottle
section of the aeration cell, and attach
to the bubbler section of the cell.
b. Attach the aeration cell to the optical
cell, aerate at 1.5 L/min,,and determine
the minimum variable transformer
setting (not to exceed 20 volts) to
prevent condensation in optical cell and
connecting tubing.
4. Calibrate \hespectrophotometerand
recorder as follows:
Set the spectrophotometer wavelength
to 253.7 nm. Set the heating system
on the optical cell at the minimum
temperature to prevent condensation.
first add 50 mL water to the aeration
cell bottle, and then pipet 5.0 mL of the
working Hg standard solution (or any
Hg-containing solution) into the aeration
cell. Never switch the order.
a.
b.
-------
Nitrogen
Cylinder
Exit Arm
Stopcock
To Hood
1 To Variable
II Transformer
Figure L101-1. Schematic of Aeration System.
-------
c. Place a Teflon-coated stirring bar in the
bottle. First close the aeration cell exit
arm stopcock and ensure that there is no
flow through the bubbler. Then, attach
the bottle section to the bubbler section
of the aeration cell.
d. Pipet 5 mL stannous chloride solution
into the aeration cell through the side
arm, and immediately stopper the side
arm. Stir for 15 sec, turn on the
recorder, open the aeration cell exit arm
stopcock, and immediately initiate
aeration with continued stirring.
e. Determine maximum absorbance of the
standard, and set this value to read 90%
of the recorder full scale.
D. Calibration Curve
1. After setting the recorder scale, repeat
steps C4a through C4d using 0.0-, 1.0-,
2.0-, 3.0-, 4.0-, and 5.0-mL aliquots of the
working standard solution (final amount of
Hg in the aeration cell is 0, 200,400, 600,
800, and 1000ng, respectively).
2. Repeat until two consecutive peaks agree
within 3% of their average value. [Note:
Bring all solutions to room temperature to
obtain reproducible results. Temperature
affects the release rate of elemental Hg
from a solution, the shape of the absorption
curve, and the point of maximum
absorbance.]
3. To prevent Hg carryover from one sample to
another, do not close the aeration gas tank
valve and do not disconnect the aeration
cell from the optical cell until the recorder
pen has returned to the baseline.
4. Between samples,
a. It is unnecessary to disconnect the
aeration gas inlet line from the aeration
cell.
b. After separating the bottle and bubbler
sections of the aeration cell, place the
bubbler section into a 6OO-mL beaker
containing - 400 mL water.
c. Rinse the bottle section of the aeration
cell with water to remove all traces of
the tin (II) reducing agent.
d. Wash the aeration cell parts with cone.
HCI if any of the following conditions
occur:
• A white film appears on any inside
surface of the aeration cell
• The calibration curve changes
suddenly.
9/30/94: L101-2
• Replicate samples do not yield
reproducible results.
5. Subtract the average peak height (or peak
area) of the 0.0-mL aliquot blank from the
averaged peak heights of the other aliquot
standards. The blank absorbance should be
=£2% of full-scale; if greater, check for Hg
contamination of a reagent or carry-over of
Hg from a previous sample.
6. Plot the corrected peak height of each
standard solution versus the corresponding
final total Hg weight in the aeration cell
(in ng), and draw the best-fit straight line.
This line should either pass through the
origin or pass through a point no further
from the origin than ±2% of the recorder
full scale. If not, check for nonlinearity of
the curve and for incorrectly prepared
standards.
E. Analysis
1. Container No. 1 (Impinger/Probe)
a. Analyze an appropriately sized'aliquot
(1 to 5 mL) of the diluted sample until
two consecutive peak heights agree
within ±3% of their average. The peak
maximum of an aliquot (except the 5 mL
aliquot) must be > 10% of the recorder
full scale. If the 1.0 mL aliquot is off
scale on the recorder, dilute the source
sample.
b.
c.
Run a blank and standard after every
five samples; recalibrate as necessary.
Check at least one sample from each
test by the method of standard
additions to confirm that matrix effects
have not interfered in the analysis (see
LP 12, section D).
2. Container No. 2 (Silica Gel)
Weigh and record the spent silica gel to the
nearest O.5 g using a balance.
F. Alternative Analytical Apparatus
Alternative systems are allowable as long as
they meet the following criteria:
1. A linear calibration curve is generated and
two consecutive samples of the same aliquot
size and concentration agree within ±3% of
their average.
2. Spike recovery of Hg (II) is ^95%.
3. Reducing agent is added after the aeration
cell is closed.
4. The aeration bottle bubbler does not contain
a frit.
-------
9/30/94: L101-3
5. Any Tygon tubing is as short as possible and
conditioned until blanks and standards yield
linear and reproducible results.
6. If manual stirring is done before aeration, it
is done with the aeration cell closed.
7. A drying tube is conditioned as the Tygon
tubing above.
-------
9/60J94-. UMOV1
LABORATORY DATA SHEET 101
Mercury
Client/Plant Name
Job #
Date
Spectrophotometer ID#
Wavelength (253.7nm?)
Date of Last Calibration
Temp, of optical cell °F Analyst ___
(:s6 months?)
Working Stds
(mL)
0.0
1.0
2.0
3.0
4.0
5.0
Peak Height (H)
1 2 Avg.
H
(Blk corr)
- ,X$«™V'
CH
(ng Hg)
0.0
200
400
600
800
1000
Note: Repeat each standard until two consecutive peaks agree within 3% of their average value.
Plot calibration curve [Havg {corr) vs. CHg. Best fit straight line must pass through origin ±2% of F.S.
Sample ID#
Blank
Standard
Vol.
Loss,
(mL)
Sample
Vol., Vf
(mL)
Dilution
Factor,
D.F.
Aliquot
Vol., S
(mL)
Peak Height, H
1 2 Avg.
I1'-'
H
Blk corr
CHg
blk corr
(ng)
mHg
U*T
mHg = fig in the original solution:
All solutions at room temperature before analysis?
Peak maximum of an aliquot greater than 10% of the recorder full scale?
A blank and standard run after every 5 samples?
One sample checked by the method of standard additions? (Attach LDS).
rriu
CHg(D.F.)V(1CT
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: F101A-1
FIELD PROCEDURE 101A
Participate and Gaseous Mercury Emissions
from Sewage Sludge Incinerators
Nate: This method is similar to Method 101, except acidic
sample collection and for the following variations: Use FDS
A. Preliminaries
potassium permanganate solution is used for
5. ' ' '
1. Use fiberglass filters whenever participate
matter concentration is high. When the
filter is ahead of the impingers, use the
probe heating system to minimize the
condensation of gaseous Hg.
2. Use a filter holder made of borosilicate glass
with a rigid stainless steel wire-screen filter
support (do not use glass frit supports), a
silicone rubber or Teflon gasket, and a filter
heating system.
3. If high oxidizable organic content
completely bleaches the purple color of the
KMn04 solution, divide the sample run into
two or more subruns.
4. If there is excess water condensation,
collect two runs to make one sample.
& Preparation of Sampling Train and Sampling
1. Clean all glass sampling and sample
recovery components by rinsing with 50%
HN03, tap water, 8 N HCI, tap water, and
finally Dl water.
2. Place 50 mL of 4% KMnO4 in the first
impinger and 100 mL in each of the second
and third impingers.
3. If a filter is used, see FP 5, step C4.
4. Maintain a temperature around the filter (if
applicable) at 248 ± 25°F during sampling.
C. Sample Recovery
1. Container No. 1 (Impinger/Probe/Filter
Holder)
a. Measure the liquid volume in the first
three impingers to within ± 1 mL. Place
in 1000-mL glass sample bottle.
b. Rinse these components with a total of
250 to 400 mL of fresh 4% KMnO4
solution; add all washings to the
1000-mL sample bottle.
c. Remove any residual brown deposits on
the glassware using the minimum
amount of 8 N HCI required; add to the
sample bottle.
2. Container No. 2 (Silica Gel)
See FP 5, step E5.
3. Container No. 3 (Filter)
a. Carefully remove the filter from the filter
holder, place it in a 100-mL glass
sample bottle, and add 20 to 40 mL 4%
KMn04. If necessary, fold the filter
such that the particulate cake is inside
the fold.
b. Transfer any particulate matter arid filter
fibers that adhere to the filter holder
gasket to the sample bottle by using a
dry Nylon bristle brush and a
sharp-edged blade. Seal and label the
container.
3. Container No. 4 (Filter Blank)
If a filter was used, treat an unused
filter from the same filter lot used for
sampling in the same manner as
Container No. 3.
4. Container No. 5 (Absorbing Solution Blank)
Place 500 mL 4% KMnO4 absorbing
solution in a 1000-mL sample bottle.
Seal and label the container.
-------
9/30/94: L101A-1
LABORATORY PROCEDURE 1O1A
Particulate and Gaseous Mercury
Emissions from Sewage Sludge Incinerators
Note: This laboratory procedure is similar to LP 101, except for the permanganate absorbing solution
(used instead of iodine monochloride) and for the variations below. Use LDS 101.
A. Reagent Preparation
1. Sulfuric Acid, 10%, Mix 100 ml cone.
H2SO4 with 900 mL water.
2. KMnO4 Absorbing Solution, 4%. Dissolve
40 g KMn04 in 10% H2S04 to make 1 L.
Prepare fresh daily and store in glass
bottles.
3. Sodium Chloride-Hydroxylamine Solution.
Dissolve 12 g NaCI and 12 g hydroxylamine
sulfate (or 12 g hydroxylamine
hydrochloride) in water; dilute to 100 mL.
4. Hydrochloric Acid, 8 N. Dilute 67 mL cone.
HCI to 100 mL with water.
5. Nitric Acid, 15%. Dilute 15 mL cone. HNO3
to 100 mL with water.
6. Potassium Permanganate, 5%. Dissolve 5 g
KMn04 in water; dilute to 100 mL.
B. Sample Preparation
1 • Container Nos. 3 and A (Filter and Filter
Blank)
a. Place contents, including the filter, in
separate 250-mL beakers, and heat the
beakers on a steam bath until most of
the liquid has evaporated. Do not take
to dryness.
b. Add 20 mL cone. HNO3 to the beakers,
cover them with a watch glass, and heat
on a hot plate at 70°C for 2 hr.
c. Remove from the hot plate, and filter the
solution through Whatman No. 40 filter
paper. Save the filtrate for Hg analysis.
Discard the filter.
2. Container Mo. 1 (Impinger/Probe/Filter
Holder)
a. Filter contents through Whatman 40
filter paper to remove the brown MnO2
precipitate.
b. Wash the filter with 50 mL 4% KMnO4
absorbing solution, and add this wash to
the filtrate. Discard the filter.
c. Combine the filtrates from Container
Nos. 1 and 3, dilute to a known volume
with water. Mix thoroughly.
3. Container Mo. 5 (Absorbing Solution Blank).
a. Treat this container as described in
step B3.
C.
1.
a.
b.
c.
b. Combine this filtrate with the filtrate
from Container No. 4, and dilute to a
known volume with water. Mix
thoroughly.
Equipment Preparation
Calibrate the optical cell heating system as in
LP 101, step C3, except add 25 mL water to
the bottle section of the aeration cell.
Calibrate the spectrophotometer and
recorder as follows:
Set the spectrophotometer wavelength
at 253.7 nm. Set the optical cell
heating system (see step C1).
First add 25 mL water to the aeration
cell bottle, and then pipet 5.0 mL
working Hg standard solution (or any
Hg-containing solution) into the aeration
cell. Never switch the order.
Place a Teflon-coated stirring bar in the
bottle. Close the stopcock on the
aeration cell exit arm, and ensure that
there is no flow through the bubbler.
d. Add 5 mL 4% KMnO4, 5 mL 15% HNO3,
and 5 mL 5% KMn04 to the aeration
bottle, and mix well. Now, attach the
bottle section to the bubbler section of
the aeration cell.
e. Add 5 mL sodium chloride
hydroxylamine in 1 -mL increments until
the solution is colorless.
f. Add 5 mL tin (II) solution to the aeration
bottle through the side arm, and
immediately stopper the side arm. Stir
the solution for 15 sec, turn on the
recorder, open the aeration cell exit arm
stopcock, and immediately initiate
aeration with continued stirring.
g. Determine the maximum absorbance of
the standard, and set this value to read
90% of the recorder full scale.
D. Analysis
1. Follow the procedure to establish the
calibration curve (see LP 101, section D)
with appropriately sized aliquots (1 to 10
mL) of the samples until two consecutive
peak heights agree within ±3% of their
average value. See LP 101, section E for
additional steps.
-------
9/30/94: L101A-2
2. If the 10-mL sample is below the detectable
limit, use a larger aliquot (up to 20 mL), but
decrease the volume of water added to the
aeration cell.
3. If the Hg content of the absorbing solution
and filter blank is below the working range
of the analytical method, use zero for the
blank.
-------
9/30/94: F102-1
FIELD PROCEDURE 102
Paniculate and Gaseous Mercury Emissions
Chlor-Alkali Plants (Hydrogen Streams)
Note: Although similar to Method 10i, Method 102 requires changes to accommodate the sample being
extracted from a hydrogen stream. Conduct the test according to Method 101, except as shown below:
1. Do not use the probe heating system, unless
otherwise specified.
2. Do not use the glass fiber filter, unless •
otherwise specified.
3. Conduct the test in a safe manner.
= 0.00154AHaCp2Tm-
a. Remove the meter box cover to avoid
possible explosive mixtures.
b. Operate only the vacuum pump during
the test. Avoid use of other electrical
equipment, e.g., heaters, fans, and
timers.
c. Seal the sample port to minimize
leakage of H2 from the stack.
d. Connect &0.50-inch ID Tygon tubing to
the exhaust from the orifice meter and
vent exhaust at least 10 ft away. A
smaller ID tubing may affect the orifice
meter calibration. Ensure that the
exhaust fine is not bent or pinched.
4. Optional: Calibrate the meter box (see CP 5)
at flow conditions that simulate the
conditions at the source using either
hydrogen or some other gas having similar
Reynolds Number. (A smaller orifice
diameter will help.)
5. If a nomograph is used,
a. Calculate the C factor to account for the
differences in molecular weights
(29 vs. 2) as follows:
where:
AHfl, =
'm
"d =
Meter box calibration factor,
in. H2O.
Pitot tube calibration coefficient,
dimensionless.
Absolute temperature of gas at the
orifice, °R.
Absolute pressure of stack gas, in.
Hg.
Absolute pressure of gas at the
meter, in. Hg.
Fraction by volume of water vapor
in the stack gas.
Dry molecular weight of stack gas,
Ib/lb-mole.
b. If the C factor exceeds the values
specified on the existing operating
nomograph, expand the C scale
logarithmically.
6. If a calculator is used to set isokinetic rates,
use the isokinetic equation.
-------
-------
9/30/94: F103-1
4.
B.
FIELD PROCEDURE 103
Beryllium Screening
3.
A. Pretest Preparation
1. Clean all glassware by soaking in acid wash
for 2 hr.
2. Select a sample site (see FP 1; attach data
sheet) that is as close as practicable to the
point of atmospheric emission. If possible,
avoid sampling stacks < 1 ft in diameter.
Select three points that proportionately divide
the diameter, or are located at 25, 50, and
75% of the diameter from the inside wall. If
the 8/2 criterion in FP 1 is not met, sample
four points or more that proportionately
divide the diameter.
For horizontal ducts, sample on a
vertical line through the centroid.
For rectangular ducts, sample on a line
through the centroid and parallel to a
side.
Select a sampling period or periods necessary
to determine the maximum emissions that
would occur in a 24-hr period.
a. In cyclic operations, perform sufficient
sample runs to determine the emissions
that represent the cycle.
a.
b.
b. Use
hr sampling time.
Sampling
1. Beryllium is hazardous; take care to minimize
exposure.
2. Conduct one run at each sampling point. At
least 3 runs comprise a test.
3.
4.
5.
Assemble the sampling train as shown in
Figure F103-1.
Leak check the sampling train on-site
(see FP 5a).
For each run, sample isokinetically at a rate
&0.5 cfm. Measure and record the
information as shown in FDS 103.
C. Sample Recovery
1. Remove the filter (and backup filter, if used)
and any loose particulate matter from filter
holder, and place in sample container.
2. Clean the probe with acetone and a brush or
long rod and cotton balls. Wash into the
sample container with the filter.
3. Wash out the filter holder with acetone, and
add to the same sample container.
4. Prepare a blank from the acetone used in the
sample recovery. Record the total.amount of
acetone used in sample recovery. Blanks
may be deleted if prior analysis shows
negligible amounts.
D. Quality Control
1. Attach a dry gas meter, spirometer, rotameter
(calibrated for prevailing atmospheric
conditions) to the inlet of the complete
sampling train.
2. Check calculated isokinetic rate against
measured rate.
Meter-Pump System
Figure F103-1. Beryllium Screening Method; SampteTrain Schematic.
-------
9/30/94: FD103-1
FIELD DATA SHEET 103
Beryllium Screening
Client/Plant Name
City/State
Personnel
Start Time
End Time
Date
Job #
Test Location
Run #/Sampling Ft
Sampling Pt #
Nozzle Diameter, Dn (in.)
Initial Velocity
Ap (in. H20)
Stack Temp erature, t^ ( ° F)
Bar Pressure, Pbl (in. Hg)
Wet-bulb Temperature, twb ( ° F)
Moisture Content, Bws (fraction)
Isokinetic Sampling Rate feO-Scfm?) (cfm)
Final Velocity
Ap (in. .H20)
Stack temperature, tgj (°F)
Bar pressure, Pbf (in. Hg)
Isokinetic Sampling Rate (^0.5 cfm?) (cfm)
Initial/Final Isokinetic Rates (±20%)
Leak Rate (^1% of sampling rate?)
Stack Area, Ag (ft2)
Sampling Time, 6 (mini
/.
r'"
Quality Control Check of Isokinetic Calculation and Regulation
DGM/Spirometer Volume, Vd (cf)
Time, G (min)
Rate, Vd/fl (cfm)
Calculated Isokinetic Rate (cfm)
QA/dC Check
Completeness _
Legibility
Checked by:
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: L103-1
LABORATORYPROCEDURE 103
Beryllium Screening
Note: Because this is a screening method, the analytical procedure does not contain detailed steps or
specifications. Judgment is left to the reviewer as to the adequacy of the procedure based on the test
report.
A. Reagent Preparation
Prepare acid wash (50% HCI) solution by
adding equal parts cone. HCI slowly and carefully
to the water.
B. Analysis
1. Prepare the samples suitable for the
analytical instrument. Any currently
acceptable method such as atomic
absorption, spectrographic, fluorometric,
chromatographic, or equivalent may be used.
2. Prepare and calibrate the analytical
equipment according the procedures
suggested by the manufacturer, or the
procedures for the selected analytical
method.
3. Analyze the samples for Be.
-------
-------
9/3O/94: S1O4-1
Client/Plant Name
Job No.
Sampling Location
Run ID #
SUMMARY SHEET 104
Beryllium
FDS5
FDS5
FOS5
FDS5
Run#1
Run #2
Run #3
Avg
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Abs Stack Pressure (Pb +. Pg/13.6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temperature (460 + ts), R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(tsj +460) Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Isokinetic Sampling Rate, %
Total Beryllium, /t/g
Beryllium Emission Rate, g/day
FDS5
FDS5
FDS5
FDS 1
FDS1
6 FDS 5
Dn FDS 5
Y CDS 5
AH FDS 5
Pb FDS 5
Pg FDS 5
Ps SS 5
ts FDS 5
Ts SS 5
%CO2 FDS 3
%02 FDS 3
%(CO + N2) FDS 3
Md FDS 3
'm
'mtstd)
V
w(std)
*ws
CP
Ap
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS2a
FDS 5
[TsiAp]1/2 FDS 5
mB«
R
SS5
FDS 1
SS5
LDS 104
SS104
-------
Run#1
Post-test Calibration Checks •
Temperature and Barometer
Pressure Differential Gauges
Metering System
9/30/94: S104-2
Run #2 Run #3 Avg
CDS2d
CDS2d
CDS 5
R - 17.64
me.vsA(86.400u10-6)
*W(Std>J
-------
9/30/94: F1O4-1
FIELD PROCEDURE 104
Beryllium
Note: The field procedure is the same as that in Method 5 except as noted below. Follow the general
procedure given in FP 5, except for the items noted below. Be is a hazardous substance; therefore,
precautions must be taken to minimize exposure. Use FDS 5.
A. Preliminaries
1. Soak all glassware (probe, impingers,
connections, sample recovery apparatus) in
wash acid for 2 hr and rinse with water.
2. Omit the directions for filters, except check
them visually against light for irregularities
and flaws.
3. Select a nozzle size to maintain isokinetic
sampling rates below 1.0 cfm.
4. Select the sampling time (at least 2 hr)
accurately determines the maximum
emissions that occur in a 24-hr period. For
cyclic operations, run sufficient sample runs
to accurately represent the emissions over
the cycle.
B. Preparation of Sampling Train
1. Assemble the train as shown in FP 5.
a. Place 100 mL of water in each of the
first two impingers, and leave the third
impinger empty. Save a portion of the
water for a blank analysis.
b. Place -200 g of preweighed silica gel in
the fourth impinger.
c. An empty impinger may be inserted
between the third impinger and the silica
gel to remove excess moisture.
2. Use a Viton A O-ring for the nozzle when
stack temperatures are <500°F or a
fiberglass string gasket when >500°F.
Other connecting systems using either
316 stainless steel or Teflon ferrules may be
used.
3. If condensation occurs, use probe and filter
heaters set at or above stack temperature
to prevent condensation.
4. If temperature affects filter (e.g., Millipore
AA is limited to - 225 °F), move the filter
holder downstream of first impinger if the
stack gas is > -200°F.
5. Glassware can be reused for subsequent
tests after rinsing twice with water. If not
used within 2 days, repeat the initial acid
wash procedure.
C. Sample Recovery
1. The cleanup area must be free of Be
contamination.
2. Container No. 1 Place the filter and any
loose participate matter from the filter holder
in this container.
3- Container No. 2 (Impinger/Washingg) In this
container, place the following:
a. Contents in the first three impingers.
Measure and record volume (to the
nearest 1 mL).
b. Water and acetone (measure amounts
of each) rinsings of the probe and all
glassware between it and the back half
of the third impinger. In cleaning the
probe, use acetone and a brush or a
long slender rod and cotton balls
(include in container).
4. Container No. 3 (Silica Gel)
See FP 5, step E5.
5. Blanks
Save a portion of the water and acetone used
in recovery for blank determinations.
-------
9/30/94: L104-1
LABORATORYPROCEDURE 104
Beryllium
A. Reagent Preparation
1. Hydrochloric Acid, 50%. Add one part HCI
to one part water (used as acid wash).
2. Sulfuric Acid, 12N. Dilute 33 mL cone.
H2SO4 to 1 L with water.
3. HCI, 25%. Add one part HCI to three parts
water.
4. Standard Beryllium Solution, (1 fjg Be/mL).
Dissolve 10 mg Be in 80 mL 12 N H2SO4,
and dilute to 1 L with water. Dilute a 10-mL
aliquot to 100 mL with 25% HCI. Prepare
fresh daily. Equivalent strength Be stock •
solutions may be prepared from Be salts such
as BeCI2 and Be(NO3)2 (98% minimum
purity).
B. Apparatus and Sample Preparation
1. Soak all glassware in wash acid for 2 hr and
rinse with water.
2. Container No. 1 (Filter)
a.
c.
Transfer the filter and any loose
particulate matter from the sample
container to a 150-mL beaker.
Add 35 mL cone. HNO3. Heat on a
hotplate until light brown fumes are
evident (very important; otherwise, •
dangerous perchlorates may result from
the subsequent HCIO4 digestion.
Cool to room temperature, add 5 mL
cone. H2SO4 and 5 mL cone. HCIO4
(only use HCIO4 under a hood).
3. Container No. 2 (Impinger/Washes) .
a. Place a portion of the contents into a
150-mL beaker, and put on a hotplate.
Add portions of the remainder as
evaporation proceeds and evaporate to
dryness.
b. Cool the residue, and add 35 mL cone.
HNO3. Heat on a hotplate until light
brown fumes are evident.
c. Cool to room temperature, add 5 mL
cone. H2SO4 and 5 mL cone. HCIO4
(under a hood).
4. Container No. 3 (Silica Gel)
Weigh the spent silica gel, and report to the
nearest gram.
5. Combine the samples from Container Nos. 1
and 2 for ease of analysis.
a. Place on a hotplate, and evaporate to
dryness in a HCIO4 hood.
b. Cool and dissolve the residue in
10.0mL25%HCI.
c. If necessary, perform further dilution of
sample with 25% HCI to bring within
calibration range.
C. Analysis
1. Prepare the atomic absorption
spectrophotometer according to the
manufacturer's instruction.
2. Analyze the prepared samples at 234.8 nm
using a nitrous oxide/acetylene flame.
US8LDS104.
D. Notes
1. Aluminum, silicon and other elements can
interfere with this method if present in large
quantities. To eliminate these interferences,
see B. Fleet, et al., "A Study of Some Matrix
Effects in the Determination of Beryllium by
Atomic Absorption Spectroscopy in the
Nitrous Oxide-Acetylene Flame,"
Talanta 17:203,1970.
2. Method 104 has no directions for blanks.
Treat a clean filter and the water and
acetone blanks according to steps B2 and
B3, respectively.
-------
9/60/94: LD104-1
LABORATORY DATA SHEET 104
Beryllium
Client/Plant Name
Job #
Date
Spectrophotometer ID#
Date of Last Calibration
(^6 months?)
Wavelength (23'
1.8 nm?) Temp, of optical cell °F Analyst
Working Stds
(//g/mL)
0.0
Peak Height (H)
1 2 Avg.
H
(Blk corr)
<.
( 6Be)
0.0
Note: Repeat each standard until two consecutive peaks agree within 3% of their average value.
Plot calibration curve [Havg (corr) vs. CBe. Best fit straight line must pass through origin ±2% of F.S.
Sample ID#
Blank
Standard
Vol.
Loss,
(mL)
Sample
Vol., Vf
{mLj
Dilution
Factor,
D.F.
«
Aliquot
Vol., S
(mL)
Peak Height, H
1 2 Avg.
H '
Blk corr
eBe
blk corr
( )
mBe
( )
mBe = fjQ in the original solution:
All solutions at room temperature before analysis?
Peak maximum of an aliquot greater than 10% of the recorder full scale?
A blank and standard run after every 5 samples?
One sample checked by the method of standard additions? (Attach LDS).
m,
'Be
CB.(D.F.)Vf10-
I-3
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
-------
9/3O/94: S1O5O
SUMMARY SHEET 105
Mercury
Run #1 Run #2 Run #3 Avg
Client/Plant Name FDS 105
Job No. FDS 105
Sample ID # FDS 105
Test Date FDS 105
Run Start Time FDS 105
Run Finish Time . FDS 105
Sample Time Increment hr FDS 105
Sample Volume per Grab Sample L FDS 105
Solids Content of Blended Sludge Fsb LDS 105
Solids Content of Sludge Before Blending Fsm LDS 105
Weight Wet Blended Sample, g Swb LDS 105
Digested Sample Volume, mL Vs LDS 105
Digested Aliquot Volume, mL Va LDS 105
Mass of Hg in Aliquot, //g m LDS 101
Cone, of Hg in Digested Sample, fjg/g Cm SS 105
Avg of Three 8-Hr Samples, fjg/g Cmfavg) SJ> 105
Concentration of Hg, dry, fjg/g M SS 105
mV.
o_
m
M
-------
9/30/94: F105-1
FIELD PROCEDURE 105
Mercury in Wastewater Treatment Plant Sewage Sludge
Sampling
Withdraw equal volume increments of sludge, for a total of at least 15 L, at intervals of 30 minutes,
over an 8-hr period. Place samples in a rigid plastic container.
-------
Client/Plant Name
City/State
Start Time
9)30)94:
FIELD DATA SHEET 105
Mercury
Job #
Stop Time
Personnel
Date
Sample ID
Time
(hr)
0:00
0:30
1:00
1:30
2:00
2:30
3:00
3:30
4:00
4:30
5:00
5:30
6:00
6:30
7:00
7:30
8:00
Total Vol
Sample Vol
(U
Sample ID
Time
(hr)
0:00
0:30
1:00
1:30
2:00
2:30
3:00
3:30
4:00
4:30
5:00
5:30
6:00
6:30
7:00
7:30
8:00
Total Vol
Sample Vol
(L)
Sample ID
Time
(hr)
0:00
0:30
1:00
1:30
2:00
2:30
3:00
3:30
4:00
4:30
5:OO
5:30
6:00
6:30
7:00
7:30
8:00
Total Vol
Sample Vol
(U
*''"
Volume of sludge equal increments?
Total volume sample > 15 L?
Sample containers sealed and labeled?
Comments:
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: L105-1
LABORATORY PROCEDURE 105
Mercury in Wastewater Treatment Plant Sewage Sludge
Note: This laboratory procedure is similar to LP 1O1A, except for the variations below. Use LDS 105.
A. Reagents
1. Aqua Regia. Carefully add one volume cone.
HNO3 to three volumes cone. HCI. Prepare
immediately before use.
2. Mercury (II) Stock Solution, 1 mg Hg/rhL.
Stable for at least one month. Dissolve
135.4 mg ACS reagent-grade HgCI2 in 75 mL
water, add 10 mL cone. HNO3, and adjust
the volume to 100.0 mL with water. Mix
thoroughly.
3. Nitric Acid, 15%. Dilute 15 mL cone. HNO3
to 100 mL with water.
4. Intermediate Mercury Standard Solution,
10//g Hg/mL. Prepare fresh weekly. Pipet
5.0 mL Hg stock solution.into a 500-mL
volumetric flask, and add 20 mL 15% HNO3
solution. Adjust the volume to 500 mL with
water. Mix thoroughly.
5. Working Mercury Standard Solution, 200 ng
Hg/mL. Pipet 5.0 mL "Intermediate Mercury
Standard Solution" into a 250-mL volumetric
flask. Add 20 mL 15% HNO3, and adjust the
volume to 250 mL with water. Mix
thoroughly. Prepare fresh daily.
6. Tin (II) Solution. Dissolve 20 g tin (II)
chloride [or 25 g tin (II) sulfate] crystals in
25 mL cone. HCI (do not use other acids for
HCI). Dilute to 250 mL with water. Prepare
fresh daily, and keep sealed.
7. Sodium Chloride-Hydroxylamine Solution.
Dissolve 12 g NaCI and 12 hydroxylamine
sulfate (or 12 g hydroxylamine hydrqchloride)
In water; dilute to 100 mL.
8. Potassium Permanganate, 5%. Dissolve 5 g
KMn04 in water; dilute to 100 mL.
B. Sampte Preparation
1. Sludge Mixing
a. Transfer the entire 15-L sample to a 57-L
capacity mortar mixer. Mix the sample
for S:30 min at 30 rpm.
b. Using a 200-mL beaker, take six 100-mL
portions of sludge, and combine in a 2-L
blender. Blend the sludge for 5 min; add
water as necessary to give a fluid
consistency.
c. Immediately after stopping the blender,
use a 50-mL beaker to withdraw four
20-mL portions of blended sludge and
place them in separate, tared 125-mL
Erlenmeyer flasks.
c. Reweigh each flask to determine the
exact amount of sludge added.
2. Solids Content of Blended Sludge
a.
b.
Dry one of the 20-mL blended samples
from step B1c in an oven at 105°Cto
constant weight.
Cool in a desiccator between weighings;
weigh the dry sample.
3. Aqua Reoia Digestion of Blended Sludge
a. To each of the three remaining 20-mL
samples from step B1c, add 25 mL aqua
regia, and digest the samples on a hot
plate at low heat (do not boil) for
30 min, or until samples are a pale
yellow-brown color and are void of the
dark brown color characteristic of
organic matter. Remove from the hot
plate, and allow to cool.
b. Filter each digested sample separately
through an S and S No. 588 filter, or
equivalent, and rinse the filter contents
with 50 rnL water.
c. Transfer the filtrate and filter washing to
a 100-mL volumetric flask, and carefully
dilute to volume with water.
4. Solids Content of Sludge Before Blending
a. Using a 200-mL beaker, remove two
100-mL portions of mixed sludge from
the mortar mixer, and place in separate,
tared 400-mL beakers.
b. Reweigh each beaker to determine the
exact amount of sludge added. Dry in
an oven at 105°C, and cool in a
desiccator to constant weight.
C. Equipment Preparation
This is the same as that in Method 101 A,
section C, except calibrate the spectrophotometer
and recorder as follows:
1. Set the spectrophotometer wavelength to
253.7 nm.
2. Make certain the optical cell is at the
minimum temperature that will prevent water
condensation from occurring.
3. First add 25 mL water and 3 drops
Antifoam B to the aeration-cell bottle. Then
pipet 5.0 mL working Hg standard solution
(or any Hg-containing solution) into the
aeration cell. Never switch the order.
-------
4. Place a Teflon-coated stirring bar in the
bottle. Add 5 mL 15% HNO3 and 5 mL
5% KMnO4 to the aeration bottle, and mix
well.
5. Attach the bottle section to the bubbler
section of the aeration cell, close stopcock
on the aeration cell exit arm, and ensure
there is no flow through the bubbler.
6. Add 5 mL sodium chloride-hydroxylamine
solution to the aeration bottle and mix. If the
solution does not become colorless, add
sodium chloride-hydroxylamine solution in
1 -mL increments until the solution is
colorless.
9/30/94-. U05-2
7. Add 5 mL tin (II) solution to the aeration
bottle through the side-arm, and immediately
stopper the side arm. Stir the solution for
15 sec, turn on the recorder, open the
aeration cell exit arm stopcock, and
immediately initiate aeration with continued
stirring.
8. Determine the maximum absorbance of the
standard, and set this value to read 90% of
the recorder full scale.
-------
9/30/94: LD105-
LABORATORY DATA SHEET 105
Mercury
Client/Plant Name
Job #
Date
Spectrophotometer ID#
Date of Last Calibration
Analyst
months?)
Note: Use LDS 101 for the analysis of the digested blended sludge and this data sheet for solids content of the
sewage sludge samples.
Solids Content of Blended Sludge
Sample 1D#
Wgt Flask, Wf (gl
Wgt Flask +Smpl,W(s (g)
Wot Flask + Smpl Dried, Wfd {g)
Water, Wwb - Wfs - WM (g)
Wet Smpl, Swb « Wfs - Wf (g)
Solids Content, F«.h - 1-WW/SW
'-.
Note: The digested blended sludge sample volume (V^J is 100 mL (denoted as Vfin LDS 101). The aliquot volume
(VJls denoted as S In LDS 101. Therefore, forLP 105, make changes accordingly.
Solids Content of Sludge Before Blending
Sample ID
Wgt Beaker, Wb (g)
Wgt Beaker + Smpl, Wbs (g)
Wgt Dried Beaker + Smpl, Wbd {g)
Water, Ww - Wbg - Wbd (g)
Wet Sampl, Sw = Wbs - Wb (g)
Solids Content, F,m = 1-WW/SW
QA/O.C Check
Completeness _
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: S106-1
SUMMARY SHEET 106
Vinyl Chloride
Run #1 Run #2 Run #3 Avg
Client/Plant Name FDS 106
Job No. FDS 106
Sampling Location FDS 106
Run ID # FDS 106
Test Date FDS 106
Run Start Time FDS 106
Run Finish Time FDS 106
Barometric Pressure, in. Hg Pb FDS 106
Ambient Temperature, °F t FDS 106
Velocity Pressure, in. H2O Ap FDS 106
% Proportional %P FDS 106
Vinyl Chloride Analyzed, ppm Cc LDS 106
Bar. Pressure During Cal., mm Hg Pf LDS 106
Bar. Pressure During Analysis, mm Hg P{ LDS 106
Loop Temp. During Analysis, K T; LDS 106
Loop Temp. During Cal., K Tr LDS 106
Lab Ambient Temperature, °C tamb LDS 106
Moisture Content in Bag, fraction Bwb LDS 106
Vinyl Chloride in Bag, ppm Cb SS 106
-------
9/30/94: F106-1
FIELD PROCEDURES 106
Vinyl Chlorida
A. Pretest Preparatioi.
1. Mandatory: Leak check the bags according
to FP 3b. Check the rigid container for leaks
in the same manner.
2. For each sample bag in its rigid container,
place a rotameter in line between the bag and
the pump inlet. Evacuate the bag. A
rotameter reading going to zero when the bag
appears empty indicates no leaks.
3. Establish the sampling rate at half the bag
volume divided by the sampling time.
B. Preparation of Sampling Train
1. Assemble the sample train as shown in
Figure 106-1.
2. Join the quick connects as illustrated, and
ensure all connections are tight.
3. Place the end of the probe at the centroid of
the stack and start the pump with the needle
valve adjusted to the desired rate.
4. Allow enough time to purge the line several
times, change the vacuum line from the
container to the bag and evacuate the bag
until the rotameter indicates no flow.
C. Sampling
1. Protect the bag container from sunlight.
2. Reposition the sample and vacuum lines and
sample at a rate proportional to the stack
velocity. Direct the gas exiting the
rotameter away from sampling personnel at
all times. Record the information shown on
FDS 106.
3. At the end of sampling, shut off the pump,
disconnect the sample line from the bag, and
disconnect the vacuum line from the bag
container.
4. Keep the sample bags out of direct sunlight
until analysis.
Teflon'
Sample Line
Heated Probe
Vacuum Line
I
Filter
(Glass Wool)
Pump
Figure F106-1. Integrated-Bag Sampling Train.
-------
Client/Plant Name
City/State
Run*
Bar Press, Pb
in. Hg
9/30/94: FD106-1
FIELD DATA SHEET 106
Vinyl Chloride
Job #
Test Location
Personnel
Amb Temperature
, °F
Date
Pre-test leak check acceptable?
Sample line purged several times before
sampling?
Bag evacuated until rotameter reads zero?
Container protected from sunlight during
sampling?
Time
Rotameter
reading
(in.H20)
.Avg
%Dev
%Dev
"^Proportional' = Highest%Dev
Sample rate kept proportional to the stack velocity?
Bag sample at least half full?
Bag sample stored out of the sunlight?
QA/QC Check
Completeness
Legibility
Accuracy
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: L106-1
LABORATORY PROCEDURE 106
Vinyl Chloride
A. Equipment Preparation
1. Set column to 100°C and detector to
150°C.
2. Determine and maintain optimum H2 and 02
flow rates during all chromatography
operations.
3. Using zero helium or N2 as the carrier gas,
establish a flow rate in the range consistent
with the manufacturer's requirements for
satisfactory detector operation. A flow rate
of -40 mL/min should produce adequate
separations.
4. Observe the base line periodically and
determine that the noise level has stabilized
and that base line drift has ceased.
5. Purge the sample loop for 30 sec at
100 mL/min, shut off flow, allow the sample
loop pressure to reach atmospheric pressure
as indicated by the water manometer, then
activate sample valve to analyze the sample.
B. Calibration
1. Obtain three manufacturer-certified cylinder
gas standards of vinyl chloride (VC) having
concentrations (Cc) of 5, 10, and 50 ppm.
2. Analyze the zero gas and each gas
standard. Record the information indicated
in LDS 106.
3. Measure VC peak area Am by a disc
integrator, electronic integrator, or a
planimeter.
4. Calculate A0 = Am A, (attenuator setting).
Repeat until two consecutive injection areas
are within 5%, then plot the average of
those two values versus Cc. Draw a
straight line through the points derived by
the least squares method.
5. Determine the retention time (the distance
on the chart from the time of injection time
to the time at which the peak maximum
occurs divided by the chart speed).
6. Perform calibration daily, or before and after
the analysis of each emission test set of bag
samples, whichever is more frequent. For
each group of sample analyses, use the
average of the two calibration curves which
bracket that group to determine the
respective sample concentrations.
7. If the two calibration curves differ by more
than 5 % from their mean value, then report
the final results by both calibration curves.
8. Immediately after preparing the calibration
curve and before analyzing the samples,
Analyze the audit samples described in
Appendix C, Procedure 2: "Procedure for
Field Auditing GC Analysis."
C. Sample Preparation
1. With a new piece of Teflon tubing identified
for that bag, connect a bag inlet valve to the
GC sample valve. Switch the valve to
receive gas from the bag through the sample
loop.
2. Arrange the equipment so the sample gas
passes from the sample valve to a
100-mL/min rotameter with flow control
valve followed by a charcoal tube and a
1-in. H2O pressure gauge.
3. Maintain sample flow by a vacuum pump or
container pressurization if the collection bag
remains in the rigid container.
4. After purging the sample loop, allow the
pressure gauge to return to zero before
activating the gas sampling valve.
D. Sample Analysis
1. Record the data indicated in LDS 106. Mark
the position of the pen on the chart at the
time of sample injection.
2. From the chart, note the peak having the
retention time corresponding to vinyl chloride
as determined in step B5.
3. Measure and record the peak heights, Hm.
4. Record Am and retention time.
5. Repeat the injections until two consecutive
values for the total area of the VC peak do
not vary more than ±5%.
6. Use the average value for these two total
areas to compute the bag concentration.
7. Compare the ratio of Hm to Am for the VC
sample with the same ratio for the standard
peak that is closest in height. If these ratios
differ by more than 10%, the VC peak may
not be pure (possibly acetaldehyde is.
present) and the secondary column should
be employed.
-------
E. Moisture Determination
1. Measure the ambient temperature and
barometric pressure near the bag.
2. From a water saturation vapor pressure
table, determine and record the water vapor
content of the bag as a decimal figure,
assuming a relative humidity of 100%.
F. Preparation of Standard Mixtures
(Alternative)
1. Leak-check the 16-inch square Tedlar bag
according to FP 3b.
2. Evacuate the bag, and meter in 5.0 L of N2.
3. For a 50-ppm vinyl chloride concentration,
a. While the bag is filling, use the 0.5 mi-
syringe to inject 250 //L of 99.9 + %
vinyl chloride gas through the wall of
the bag.
b. After withdrawing the syringe,
immediately cover the resulting hole
with a piece of adhesive tape.
4. For 10- and 5-ppm concentrations, repeat
step E3, except use the 50-//L syringe to
inject in 50 jt/L and 25 //L, respectively.
5. Place each bag on a smooth surface and
alternately depress opposite sides of the
bag 50 times to further mix the gases. Do
not use the gas mixture standards after
10 days.
9/30/94: L106-2
6. Do not reuse a bag if the new gas mixture
standard is a lower concentration than that
of the previous gas mixture standard.
G. Alternatives
1. Other column and operating parameters may
be used, provided" that adequacy is
confirmed through an adequate supplemental
analytical technique, such as analysis with a
different column or GC/mass spectroscopy,
and the data are available for review by the
Administrator.
2. Other chromatographic columns may be
used provided that the precision and
accuracy specifications are met in the
analysis of vinyl chloride standards and
resolution of the vinyl chloride peak is
adequate, i.e., the area overlap of the vinyl
chloride peak and an interferant peak is not
more than 10% (see 40 CFR Part 61,
Appendix C, Procedure 1: "Determination of
Adequate Chromatographic Peak
Resolution").
3. GC system must be capable of producing a
response to 0.1-ppm vinyl chloride that is at
least as great as the average noise level.
(Response is measured from the average
value of the base line to the maximum of the
wave form, while standard operating
conditions are in use.)
-------
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9/30/94: S107-1
Client/Plant Name
Job No.
Sampling Location
Sample ID #
Test Date
Sample Time
Abs Amb Temperature (tt + 273), K
Barometric Pressure, kPa
Response Factor, area counts/ppm
Sample Weight, g
Total Solids, fraction
Equilibrium Temperature, 90 °C
Abs Equilibrium Temp (t2 + 273), K
Vial Volume, cm3
Vinyl Chloride Concentration (As/Rf), ppm
Volume of Vapor Phase, cm3
Vinyl Chloride Monomer, ppm
v _ v m(TS) m(1-TS)
9 v 1.36 0.9653
SUMMARY SHEET 107
Vinyl Chloride
FDS 107
FDS 107
FDS 107
FDS 107'
FDS 107
FDS 107
LDS 107
LDS 107
LDS 107
m
TS
rvc
LDS 107
LDS 107
LDS 107
SS107
LDS 107
LDS 107
SS107
-SS 107
Run#1
Run #2
Run #3
Avg
62.5 V
62360 m
5- + 6.52x10-*(TS)T,
D-7(1 - TS)T.
-------
9/30/94: F107-1
FIELD PROCEDURE 107
Vinyl Chloride Content of Inprocess Wastewater Samples,
Polyvinyl Chloride Resin, Slurry, Wet Cake,
and Latex Samples
A. PVC Sampling
1. Purge tap line on the tank or silo with the
resin or slurry.
2. Fill a 60-mL sample bottle under the tap, and
immediately cap the bottle. To prevent the
cap from loosening, wrap adhesive tape
around the cap and bottle.
3. Label each bottle, and record the date, time,
and sample location both on the bottles and
in a log book.
4. Keep samples refrigerated until analysis.
B. Water Sampling
1. Fill the vials bubble-free to overflowing so
that a c6nvex meniscus forms at the top.
2. Carefully place the sealing disc, with the
Teflon side down, on the opening of the
vial.
3. Place the aluminum seal over the disc and
the neck of the vial, and crimp into place.
4. Label the vial. Record the date, time, and
sample location both on the vials and in a
log book.
5. Keep samples refrigerated until analysis.
-------
9/3O/94: FD1O7-1
FIELD DATA SHEET 107
Vinyl Chloride
Client/Plant Name
City/State Personnel
Tap line
purged?
Sample ID
Sample Type
Date
Time
,.-,. • ",
Comments:
QA/QC Check
Completeness Legibility Accuracy Specifications Reasonableness
Checked by:
Team Leader (Signature/Date)
-------
9/30/94: L107-1
LABORATORY PROCEDURE 107
Vinyl Chloride
A. Sample Preparation
1. Tare sample vials including the septum and
aluminum cap to ±0.7%. Obtain all weights
to within ±0.7%.
2.
Resin Samples
For suspension resins, prepare a
a.
volumetric cup to hold 0.1 to 4.5 g.
Open the sample bottle, and add the cup
volume of resin to the tared sample vial.
Weigh, then add 100/A. or ~2 equal
drops of water, and immediately seal the
vial.
b. For dispersion resins, weigh the sample
in an aluminum dish, transfer the sample
to the tared vial, and weigh.
c. Prepressurize the samples. This is not
required if the sample weight is <0.2 g
or If the absolute prepressurization value
Is within 30% of the atmospheric
pressure.
3. Suspension Resin Slurry and Wet Cake
Samples
a. Decant the water from a wet cake
sample, and turn the sample bottle
upside down onto a paper towel.
b. Wait for the water to drain, place
-0.2 to 4.0 g of the wet cake sample in
a tared vial, seal immediately, and
weigh.
4. Dispersion Resin Slurry and Geon Latex
Samples
a. Do not filter the samples. Thoroughly
mix the sample, and immediately add to
a tared vial ~8 drops (0.25 to O.35 g) of
slurry or latex with 'a medicine dropper.
b. Seal the vial as soon as possible and
weigh.
5. Inprocess Wastewater Samples
a. Quickly add ~ 1 cc of water sample
using a medicine dropper.
b. Seal the vial as soon as possible, and
weigh.
& Equipment Preparation.
1. Install the chromatographic column and
condition overnight at 160 °C. In the first
operation, purge the Porapak columns for
1 hr at 230°C. (Do not connect the exit end
of the column to the detector while
conditioning. Ensure that the H2 and air to
the detector are turned off while the column
is disconnected.)
2. Adjust N2 carrier flow rates, calculate the
prepressurization pressure (P), adjust the
burner air supply flow rate, H2 supply flow
rate, set the temperatures for the oven,
dosing line, injection block, sample chamber,
and water temperature, ignite the flame
ionization detector, balance the amplifier,
and program the chromatograph. See
LDS 107.
3. With a soap film flowmeter and stopwatch,
measure the flow rate at the exit end of the
column, check the burner air supply flow
rate, and the H2 supply flow rate.
4. After setting the N2, calculate "P."
Note: Because of gauge errors, the
apparatus may over-pressurize the vial
(indicated by an audible double injection).
Too low vial pressures cause inadequate
time for head-space gas equilibrium.
Therefore, run several standard gas'samples
at various pressures around the calculated
pressure, and then select the highest
pressure that does not produce a double
. injection.
C. Calibration
1. Prepare two vials each of 50-, 500-, 2,000-,
and 4,000-ppm calibration standards as
follows:
a. Use a 1/8-in. stainless steel line from
the cylinder to the vial (Do not use
rubber or Tygon tubing). Purge the
sample line from the cylinder into a
properly vented hood for several
minutes before filling the vials.
b. Place 100 /A. or about two equal drops
of distilled water in the sample vial, then
fill the vial with the VCM/N2 standard,
rapidly seat the septum, and seal with
the aluminum cap.
c. After purging, reduce the flow rate to
500 to 1000cc/min. Place end of
tubing into vial (near bottom). Position
a septum on top of the vial, pressing it
against the 1 /8-in. filling tube to
minimize the size of the vent opening
and prevent mixing air with the standard
in the vial.
-------
: U07-2
d. Wearing rubber gloves, purge each vial
with standard for 90 sec, during which
time gradually slide the filling tube to the
top of the vial. After the 90 sec, remove
the tube with the septum, and
simultaneously seal the vial.
e. Pressurize (if required for samples) the
sealed vial for 60 sec using the vial
prepressurizer. Test the vial for leakage
by placing a drop of water on the
septum at the needle hole.
D. Vinyl Chloride Analysis
1. Analyze samples within 24 hr after
collection.
2. Prepressurize samples (if required) for 1 hr
(not to exceed 5 hr).
3. Condition all samples and standards at 90°C
for 1 hr.
4. If the aluminum sample vial caps have a
center section, remove it before placing into
sample turntable to avoid damaging the
injection needle.
5. Place the numbered sample vials in the
corresponding numbered positions in the
turntable. Insert samples in the following
order:
a. Positions 1 and 2: If the analyzer has not
been used for 2:24 hr, old 2000-ppm
standards (for conditioning).
b. Position 3: 50-ppm standard, freshly
prepared.
c. Position 4: 500-ppm standard, freshly
prepared.
d. Position 5: 2000-ppm standard, freshly
prepared.
e. Position 6: 400O-ppm standard, freshly
prepared.
f. Position 7: Sample No. 7 (This is the first
sample of the day, but is given as 7 to
be consistent with the turntable and the
integrator printout.)
g. Position rest of samples, then insert the
second set of 50-, 500-, 2000-, and
4000-ppm standards.
6. Start the analysis program according to the
manufacturer's instructions.
7. After the instrument program advances to
the "B" (backflush) mode, adjust the
nitrogen pressure regulator to balance the
nitrogen flow rate at the detector as was
obtained in the "A" mode.
8. Plot A., the integrator area counts for each
standard sample, versus Cc, the
concentration of vinyl chloride in each
standard sample.
9. Draw a straight line through the points
derived by the least squares method.
10. Perform a calibration for each 8 hrs the
chromatograph is used.
E. Total Solids
For wet cake, slurry, resin solution, and PVC
latex samples, determine total solids (TS) for each
sample as follows:
1. Weigh the aluminum pan, add ~3r4 g
sample, and weigh before and after placing
in a draft oven (105-110°C).
2. Dry samples to constant weight. After first
weighing, return the pan to the oven for a
short period of time, and then reweigh to
• verify complete dryness.
F. Alternatives
An alternative to step D10 is as follows:
1. Calibrate with duplicate 50-, 500-, 2,000-C
and 4,000-ppm standards (a four-point
calibration) on a monthly basis.
2. Analyze in duplicate the 500-ppm standard
[2,000-ppm standard for dispersion resin
(excluding latex resin) samples] once per
shift, or once per chromatograph carrousel
operation (if less frequent than once per
shift).
3. If both analyses are within ±5% of the most
recent four-point calibration curve, step F1
may be continued. If not, perform a
complete four-point calibration.
-------
9/30/94: LD107-1
LABORATORY DATA SHEET 107
Vinyl Chloride
Client/Plant Name
City/State
Job No.
Date
Gas Chromatograph ID #
Amb. Temp, T1 °C
Vial Volume cc
Analyst
Bar. pressure. Pb
mm Hg/7.5
kPa
Sample Preparation
Sample
ID#
Tare
(g)
Samp + Tare
(g)
Sample, m
(g)
<0.2 g?
(/»
CalcP
(kPa)
±30%Pb
(/)
T,
P * -rrr (P,-67.47)-10 All unchecked samples prepressurized?
where: PJ « GC abs. dosing pressure "A" mode, kPa
Selected P-j » kPa (Highest that does not produce a double injection).
Chromatograph Operation
Parameter
N2 Cylinder Pressure
N2 Cylinder Flow
Burner Air Cyl Pressure
Burner Air Flow
H2 Cylinder Pressure
H2 Flow
Oven Temp
Dosing Temp
Setting
50 psig
30.0 cc/min
50 psig
275 ± 25 cc/min
30 psig
35 ± 5 cc/min
140°C
, 150°C
{/)
Parameter
Injection Block Temp
Water Bath Temp, t2
Dosing Time
Analysis Time
Backflushing Time
Stabilization Time
Analysis/Sample
Setting
170°C
90 ± 1°C
2 sec
70% of VCM
Retention Time
2x Analysis Time
0.5 to 1 .0 min
1
(/)
Bubble Flow Meter Checks:
Volume, cc
Time, min
Flow Rate, cc/min
N,
Burner Air
H,
-------
9/30/94: LD107-2
Samp
No.
Sample
ID#
50 ppm
500 ppm
2000 ppm
4000 ppm
Sample Concentration
Peak
Hgt, Hs
Area,
As
VC Cone,
C (ppm)
Samp
No.
Sample
ID#
50 ppm
500 ppm
2000 ppm
4000 ppm
Peak
Hgt, Hs
Area.
As
VC Cone,
C (ppm)
Calculate Rs = AS/CS for each of the standards. Then average Rs to obtain Rf if calibration curve
passes through zero; otherwise, use the calibration curve to determine each sample concentration.
C = AJR,
Sample ID#
Tare (g)
Tare/Sample (g)
Wgt Wet Smpl (g)
Dry Wgt 1 (g)
Dry Wgt 2 (g)
Dry Wgt 3 (g)
Wgt Solids (g)
Total Solids
Total Solids Determination
- -
Wgt Solids = Dry Wgt - Tare
Total Solids, fraction = Wgt Solids/Wgt Wet Sample
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: S107A-1
Client/Plant Name
Job No.
Sampling Location
Sample ID #
Test Date
Sample Time
Response Factor, ppm/mm
Peak Height of Sample, mm
Total Solids
Vinyl Chloride In Resin, ppm
Vinyl Chloride in Volatile Material, ppm
Vinyl Chloride In Solvents, ppm
SUMMARY SHEET 107A
Vinyl Chloride
FDS 107
FDS 107
FDS 107
FDS 107
-FDS 107
FDS 107
TS
'•'rvcCrosin)
Crvc(vol.)
Crvc(solv.)
IDS 107 A
LDS101A
LDS 107 A
SS 107 A
SS 107A
SS 107 A
Run#1
Run #2
Run #3
Avg
H.R,(1000)
-------
9/30/94: F107A-1
FIELD PROCEDURE 107A
Vinyl Chloride in Solvents, Resin Solvents Solutions,
Polyvinyl Chloride Resin, Resin Slurry,
Wet Resin, and Latex Samples
Note: Use FDS 107.
1. Purge the tap on the tank, silo, or pipeline 3. Label each bottle, and record the date, time,
with its contents. sample location, and material.
2. Fill a wide-mouth pint sample bottle, and
immediately cap the bottle.
-------
Interfering Peak
o:
1
2 3 1
Time, minutes
Figure L107A-1.
-------
9/30/94: L107A-1
LABORATORY PROCEDURE 107A
Vinyl Chloride in Solvents, Resin Solvents Solutions, Polyvinyl Chloride Resin,
Resin Slurry, Wet Resin, and Latex Samples.
A.
1.
Sample Preparation
Tetrahydrofuran (THF). Inject 10^L THF
into the gas chromatograph (GC). For the
reagent to be acceptable, the chromatogram
must look like Figure L107A-KB). If the
chromatogram looks like Figure L107A-KA),
sparge the THF with pure N2 for about 2 hr
using the fritted glass sparger to remove the
interfering peak, and analyze again.
2. Resin Samples
a. Weigh 9.00 ±0 .01 g THF or N,N-
Dimethylaceamide (DMAC) in a tared
20-mL vial.
b. Add 1.00 ± 0.01 g resin, and close the
vial tightly with the screw cap, and
shake until the resin dissolves
completely (may require several minutes
to several hours, depending on the
nature of the resin).
3. Suspension Resin Slurry and Wet Resin
Sample
a. Filter the slurry using a small Buchner
funnel with vacuum; continue only as
long as a steady stream of water is
exiting from the funnel. Excessive
filtration could cause some loss of vinyl
chloride monomer (VCM).
b. Perform step A2.
4. Latex and Resin Solvent Solutions
a. Thoroughly mix the samples.
b. Perform step A2.
5. Solvents and Non-viscous Liquid Samples
Inject the neat samples directly into the GC.
B. Equipment Preparation
1. Install the GC column, and condition
overnight at 70°C. Do not connect the exit
end of the column to the detector while
conditioning.
2. Adjust the N2 carrier, burner air supply flow
rate, H2, and N2 flow rates, optimize the H2
flow to yield the most sensitive detector
response without extinguishing the flame,
set the GC oven, injection port, and detector
temperatures, ignite the FID (allow 1 hr
warmup), set recorder pen at zero and start
chart drive, and set attenuation to yield
desired peak height (function of VCM
content). SeeLDS107A.
3. With a soap film flowmeter and stopwatch,
measure the N2, burner air supply, and H2
flow rates.
C. Standards Preparation
1. Prepare an -1 % by weight solution as
follows:
a. Tare a 125-mL glass-stoppered flask,
add THF or DMAC, and weigh. Multiply
the THF or DMAC weight by 0.01.
b. In a hood, bubble vinyl chloride gas into
the THF or DMAC. Adjust the vinyl
chloride flow from the cylinder so that
the vinyl chloride dissolves essentially
completely in the THF or DMAC and is
not blown to the atmosphere. Take
care not to volatilize any of the solution.
c. Stopper the flask and swirl the solution
to effect complete mixing.
d. Weigh the stoppered flask to nearest
0.1 mg.
2. Pipet 10 mL of the ~ 1 % solution into a
100-mL glass-stoppered volumetric flask,
and fill to mark with THF or DMAC to obtain
~ 1,000 ppm by weight. Cap the flask and
invert 10 to 2O times.
3. Pipet 50-, 10-, 5-, 1-, 0.5-, and 0.1-mL
aliquots of the -1,000 ppm solution into
10-mL glass stoppered volumetric flasks.
Dilute to the mark with THF or DMAC, cap
the flasks and invert each 10 to 20 times.
These solutions contain -500,100, 50, 10,
5, and 1 ppm vinyl chloride. Calculate the
exact concentration of each one. Keep
refrigerated in stoppered bottles, and renew
every 3 months.
D. Standards and Sample Analyses
1. Remove needle from 50-/vL syringe. Open
standard or sample vial and draw 50-/JL
solution into the syringe. Recap the vial.
Reattach the needle. While holding the
syringe vertically (needle point up), eject
40 //L into an absorbent tissue. Wipe needle
with tissue. Then inject 10//L into the GC.
2. Repeat until two consecutive values for the
height of the vinyl chloride peak do not vary
more than 5%. Then average the values.
3. Four minutes after sample injection, actuate
the back flush valve to purge the first 4 feet
of the chromatographic column of solvent
and other high boilers.
-------
4. Record on the chromatograph strip chart the
sample identification.
5. Vinyl chloride elutes at 2.8 min.
Acetaldehyde elutes at 3.7 min. Analysis is
complete when chart pen becomes stable.
After 5 min, reset back flush valve and
inject next sample.
6. For the standards, prepare a chart plotting
peak height, Hc, obtained from the
chromatogram of each solution versus the
known concentration, Cc. Draw a straight
line through the points derived by the least
squares method.
E, TotalSoKds
For wet resin, resin solution, and PVC latex
samples, determine the total solids (TS) for each
sample as follows:
1. Tare the weighing dish (aluminum) to the
nearest mg. Make all weighings to the
nearest mg.
9/30/94: L107A-2
2. If water is the major volatile component, add
3- to 5-g sample to the tared dish and
weigh.
3. If volatile solvent is the major volatile
component, transfer a portion of the sample
to a 20-mL screw cap vial, cap immediately,
and weigh. Uncap the vial and transfer a
3- to 5-g sample to a fared dish. Recap the
vial and reweigh.
4. Place sample in a 130°C oven for 1 hr.
Remove, allow to cool to room temperature
in a desiccator, and weigh.
F. Quality Control
1. Replace the septum after five sample
injections.
2. Replace the sample port liner with a clean
spare after five sample injections.
3. If the GC has been shut down overnight,
rerun one or more samples from the
preceding day to test stability and precision
' prior to starting on the current day's work
-------
LABORATORY DATA SHEET 107A
Vinyl Chloride
9)30/94: LD107A-1
Client/Plant Name Job #
City/State parp
Gas Chromatograph ID
# Analyst
Standard Preparation
DMAC may be used instead of THF
A
Tare
(g)
===
B
Tare + THF*
(g)
=======
C = B- A
THF
(g)
===========:
D
VC + B
. (g)
======
E = D - B
Sample
(g)
=========
(100EJ/C
VC Cone.
(%)
===
Parameter
N2 cylinder pressure
N2 flow rate setting
N2 backflush flow rate
Burner air supply
Burner air flow rate
H, cylinder pressure
Chromatograph Operation
Settina
60 psig
40.0 cc/min
40.0 cc/min
40 psig
250-300 cc/min
60 psig
(/)
Parameter
asaasaaassaaaa
H2 flow rate
Oven temperature
Injection port
Detector
FID stabilized?
Setting
30-40 cc/min
70°C
100°C
300 °C
*•' '"
(/I
Bubble flow Meter Checks:
Volume, cc
Time, min
Flow rate, cc/min
N,
Burner Air
Total Solids Determination
Sample ID#
Tare (g)
Tare/Sample (g)
Volatile
Syr + Samp (g)
Syr + Samp (g)
Wet Sample (g)
Dry Wgt 1 (g)
Dry Wgt 2 (g)
Dry Wgt 3 (g)
Total Solids (TS)
— | •^-^•^-^»,
Total Solids =
Wel9ht
Wet Sample
-------
9/30/94: LD107A-2
Sample Concentration
Use the calibration curve to determine each sample concentration and calculate response factor Rf = CC/HC for each
Samp
No.
Sample
Cone, Cc
1 ppm
5 ppm
10 ppm
50 ppm
1 00 ppm
500 ppm
Peak Hgt (mm)
Hoi
Hc2
Hc1/Hc2<5%?
Avg, Hc
Response
Factor
Rf =
-------
9/3O/94: S1O8-J
Client/Plant Name
Job No.
Sampling Location
Run ID #
Test Date
Run Start Time
Run Finish Time
Net Traverse Points
Traverse Matrix (Rectangular)
Net Run Time, min
Nozzle Diameter, in.
Dry Gas Meter Calibration Factor
Average AH (orifice meter), in. H2O
Barometric Pressure, in. Hg
Stack Static Pressure, in. H2O
Abs Stack Pressure (Pb + Pg/13.6), in. Hg
Average Stack Temperature, °F
Avg Abs Stack Temperature (ts + 460), R
Carbon Dioxide, % dry
Oxygen, % dry
Carbon Monoxide + Nitrogen, % dry
Dry Molecular Weight, Ib/lb-mole
Average DGM Temperature, °F
Volume of Metered Gas Sample, dcf
Volume of Metered Gas Sample, dscf
Volume Water Condensed, mL
Volume of Water Vapor, scf
Moisture Content, fraction
Pitot Tube Coefficient
Average Velocity Pressure, in. H2O
Average [(tsi +460) Ap]1/2
Velocity, ft/sec
Stack Area, ft2
Volumetric Flow Rate, dscfh
Volumetric Flow Rate, wscfh
Isokinetic Sampling Rate, %
Total Arsenic Mass, (IQ
Stack Cone, of Arsenic, g/dscm
Arsenic Mass Emission Rate, g/hr
Audit Relative Error, %
SUMMARY SHEET 108
Arsenic
FDS5
FDS5
FDS5
FDS5
FDS5
FDS5
FDS5
FDS 1
FDS1
0 FDS 5
Dn FDS 5
Y CDS 5
AH FDS 5
Pb FDS 5
Pg FDS 5
Ps SS5
ts FDS 5
Ts SS5
%C02 FDS 3
%O2 FDS 3
%(CO + N2) FDS 3
Md FDS3
V.
m(std)
V,
Ic
Vw(std)
Bws
CP
Ap
ITsi Ap]1/2
A
Qsd
Qsw
%l
Ea
RE
FDS 5
FDS 5
SS5
FDS 5
SS5
SS5
CDS2a
FDS 5
FDS 5
SS5
FDS 1
SS5
SS5
SS5
SS 108
SS108
SS108
QA 1
Run#1
Run #2
Run #3
Avg
-------
Post-test Calibration Checks
Temperature and Barometer
Differential Pressure Gauges
Metering System
Run#1
Run #2
9/30/94: S108-2
Run #3 Avg
CDS2d
CDS2d
CDS 5
C. = 10"
m,
V,
m(8td)
-------
9/30/94: F108-1
FIELD PROCEDURE 108
Participate and Gaseous Arsenic Emissions
Note: The sampling procedure is similar to that of Method 5.
given in FP 5, except for the items noted below (Use FDS 5):
A. Preliminaries _
l».
1 . The filter does not need to be weighed or be
unreactive to SO2 or SO3.
2. Select a nozzle size to maintain isokinetic d<
sampling rates below 1 .0 cfm.
3. Assemble the train as shown in FP5.
B. Sampling e-
1 . Maintain 225 to 275 °F around the filter.
2. Maintain isokinetic sampling below 1 .0 cfm.
C. Sample Recovery
Recover the samples as in FP 5, Containers
Nos. 1 through 3, except use 0.1 N NaOH for the
cleanup solvent instead of acetone. Treat the
impinger water as follows:
1. Label the impinger water sample container as
Container No. 4 {Impinger Water).
2. Clean each of the first two impingers and
connecting glassware in the following
manner:
Wipe the impinger ball joints free of
silicone grease, and cap the joints.
Weigh the impinger and liquid to ±O.5 g
(for moisture determination). Note any
color or film observed in the impinger
catch.
a.
b.
3.
4.
Therefore, follow the general procedure
Rotate and agitate each impinger, using
the impinger contents as a rinse
solution.
Transfer the liquid to Container No. 4.
Remove the outlet ball-joint cap, and
drain the contents through this opening
without separating the impinger parts.
[Note: In step C2e and in step C2f
below, measure and record the total
amount 0.1 N NaOH used for rinsing.]
Pour about 30 mL of 0.1 NaOH into
each of the first two impingers, and
agitate. Drain through the outlet of
each impinger into Container No. 4.
Repeat the operation. Inspect the
impingers for any abnormal conditions.
Rinse each piece of connecting
glassware and the back half of the filter
holder twice with 0.1 N NaOH; transfer
to Container No. 4. [Do not rinse or
brush the glass-fritted fitter support.]
g. Mark the hiejght of the fluid level. Label
the container.
For a blank> take 200 mL 0.1 N NaOH
solution directly from the wash bottle being
used and place it in a plastic sample
container labeled "NaOH blank."
Save a sample of the water, and place it in a
container labeled "H2O blank."
f
-------
9/30/94: L108-1
LABORATORYPROCEDURE 108
Particulate and Gaseous Arsenic Emissions
A. Reagent Preparation
1. Sodium Hydroxide, 0.1 N. Dissolve 4.00 g
NaOH in —500 mL water in a 1 L volumetric
flask. Dilute to 1.0 L with water.
2. Sodium Borohydride, 5%. Dissolve 5.00 g
NaBH4 in -500 mL 0.1 N NaOH in a 1-L
volumetric flask. Dilute to 1.0 L with 0.1 N
NaOH.
3. Potassium Iodide, 30%. Dissolve 300 g Kl in
500 mL water in a 1 -L volumetric flask.
Dilute to 1.0 L with water.
4. Nitric Acid, 0.8 N. Dilute 52 mL cone. HN03
to 1.0 L with water.
5. Nitric Acid, 50%. Add 50 mL cone. HNO3 to
50 mL water.
6. Stock Arsenic Standard, 1 mg/mL. Dissolve
1.3203 g primary standard grade As2O3 in
20 mL 0.1 N NaOH in a 150-mL beaker.
Slowly add 30 mL cone. HN03. Heat the
resulting solution and evaporate just to
dryness. Transfer the residue quantitatively
to a 1 L volumetric flask. Dilute to 1.0 L with
water.
7. Working Arsenic Solution, 1.0 //g As/mL.
Pipet 1.0 mL stock arsenic standard into an
acid-cleaned, 1 L volumetric flask containing
—500 mL water and 5 mL cone. HNO3.
Dilute to 1.0 L with water.
8. Nickel Nitrate, 5%. Dissolve 24.780 g nickel
nitrate hexahydrate in water in a 10O-mL
volumetric flask. Dilute to 100 mL with
water.
9. Nickel Nitrate, 1 %. Pipet 20 mL 5% nickel
nitrate solution into a 100-mL volumetric
flask. Dilute to 100 mL with water.
10. Hydrogen Peroxide, 3%. Pipet 50 mL 30%
H2O2 into a 500 mL volumetric flask. Dilute
to 500 mL with water.
11. QA Audit Samples. Obtain from EPA
(seeQA 1).
B. Sample Preparation
1. Note the level of liquid in Sample Container
Nos. 2 and 4, and determine loss; note this
loss, if any, on the laboratory data sheet.
2. Container No, 2
a. Using a glass fiber filter, filter the
contents into a 200-mL volumetric flask.
Combine the filtered material with the
contents of Container No. 1.
b. Dilute the filtrate to 200 mL with water.
Pipet 50 mL into a 150-mL beaker. Add
10 mL.conc. HNO3, bring to a boil, and
evaporate to dryness.
c. Allow to cool, add 5 mL 50% HN03, and
then warm and stir.
d. Allow to cool, transfer to a 50-mL
volumetric flask, dilute to volume with
water, and mix well.
3. Container No. 1
a. Place the filter and loose particulate
matter in a 150-mL beaker. Add the
filtered material from Container No. 2.
b. Add 50 mL 0.1 N NaOH. Stir and warm
on a hot plate at low heat (do not boil) for
-15 minutes.
c. Add 1O mL cone. HNO3, bring to a boil,
then simmer for -15 min.
d. Filter the solution through a glass fiber
filter. Wash with hot water, and catch
the filtrate in a clean 150-mL beak'er.
e. Boil the filtrate, and evaporate to dryness.
f. Cool, add 5 mL 50% HNO3, then warm
and stir.
g. Allow to cool. Transfer to a 50-mL
volumetric flask, dilute to volume with
water, and mix well.
4. Container No. 4
a. Transfer the contents to a 500-mL
volumetric flask. Dilute to 500 mL with
water.
b. Pipet 50 mL of the solution into a 150-mL
beaker.
c. Add 10 mL cone. HN03, bring to a boil,
and evaporate to dryness.
d. Allow to cool, add 5 mL 50% HNO3/ and
then warm and stir.
e. Allow the solution to cool, transfer to a
50-mL volumetric flask, dilute to volume
with water, and mix well.
5. Blanks
a. Take two filters from each lot of filters
used in the sampling. Cut each filter into
strips, and treat each filter individually as
directed in section B3, beginning with
step B3b.
b. Treat separately 50 mL 0.1 N NaOH and
50 mL water, as directed in section B4,
beginning with step b.
-------
9/30/94: U08-2
C. Calibration
1. Prepare and operate the spectrophotometer
according to the manufacturers' instruction
manual. The lower limit of flame atomic
absorption spectrophotometry is 10/yg
As/mL. If the arsenic concentration of any
sample is <10//g/mL, use the graphite
furnace or vapor generator (either may also
be used for sample concentrations up to
30 fjglmL.
2. Prepare the standards as follows:
a. High Level Procedure. Pipet 1, 3, 5, 8,
and 10 mL of the 1,0-mg As/mL stock
solution into separate 100-mL volumetric
flasks, each containing 5 mL cone. HNO3.
b. Low Level Vapor Generator Procedure.
Pipet 1,2,3, and 5 mL of 1.0 fjg As/mL
standard solution into the separate
100-mL reaction tubes.
c. Low Level Graphite Furnace Procedure.
Pipet 1, 5, 10, and 15 mL of 1.0//g
As/mL standard solution into the separate
100-mL flasks along with 2 mL 5% nickel
nitrate solution and 10 mL 3% H2O2
solution.
3. Dilute to the mark with water. Then treat the
standards in the same manner as the samples
as in section D.
4. Prepare a standard curve of absorbance
versus concentration. [Note: For instruments
equipped with direct concentration readout
devices, preparation of a standard curve will
not be necessary.]
D. Analysis
1. Measure absorbance of standards, blanks,
and samples against 0.8 N HNO3. If the
sample concentration falls outside the range
of the calibration curve, make an appropriate
dilution with 0.8 N HNO3.
2. Using the appropriate standard curve,
determine the arsenic concentration in each
sample fraction and blank. For the arsenic
concentration in the filter blank, use the
average of the two blank values from each
lot.
3. Vapor Generator Procedure
a. If necessary, screen the samples by
conventional atomic absorption to
determine the approximate concentration.
b. Place a sample containing between 0 and
5 fjg arsenic in the reaction tube, dilute to
15 mL with water.
c. Pipet 15 mL cone. HCI into each tube.
Add 1 mL 30% Kl solution. Place the
reaction tube into a 50 °C water bath for
5 min.
d. Cool to room temperature. Connect the
reaction tube to the vapor generator
assembly. When the instrument response
has returned to baseline, inject 5.0 mL
5% NaBH4, and integrate the resulting
spectrophotometer signal over a 30-sec
time period.
4. Graphite Furnace Procedure
a. Dilute the digested sample so that a 5-mL
aliquot contains <1.5//g of arsenic.
b. Pipet 5 mL of this digested solution into a
10-mL volumetric flask. Add 1 mL 1%
nickel nitrate solution, 0.5 mL
50% HNO3, and 1 mL 3% H2O2, and
dilute to 10 mL with water.
c. Inject the sample in the furnace for
analysis.
5. Check absorbance of standards frequently
against 0.8 N HNO3 {reagent blank) during
the analysis to ensure that base-line drift has
not occurred.
6. Mandatory: Check for matrix effects on the
arsenic results (see LP 12, section D).
7. Weigh the silica gel contents of Container No.
3 (see FP 5, step E5).
8. Analyze the audit samples, if applicable.
-------
9/30/94: LD108-1
LABORATORY DATA SHEET 108
Arsenic
Method (circle) 108,108A, 108B
Client/Plant Name
City/State
Job*
Spectrophotometer ID #
Date
Date Last Calibration
Analyst
Std Vol
(mL)
Std Cone
Absorbance
108: High Level Std Vol = 0.0, 1.0, 3.0, 5.0, 8.0, 10.0 mL
Std Cone = 0, 10, 30, 50, 80, 100//g/mL
108: Vapor Generator = 0.0, 1.0, 2.0, 3.0, 5.0 mL
Std Cone = 0, 1.0, 2.0, 3.0, 5.0//g
108: Graphite Furnace = 0.0, 1.0, 5.0, 10.0, 15.0 mL
Std Cone = 0, 10, 50, 100, 150 ng/mL
108A: Std Vol = 0.0, 1.0. 5.0, 10.0. 25.0 mL
Std Cone = 0, 10, 50, 100, 250fjglmL
108B: Std Vol = 0.0, 1.0, 5.0, 10.0, 25.0 mL
Std Cone = 0, 10, 50. 100. 250j/g/mL
Rot Absorbance vs. Concentration and attach graph (not necessary for direct readout instruments).
Sample
Number
Sample ID #
0.8N HN03
Filter blank
Filter blank
Reagent blank
**•
•
Audit #1
Audit #2
Ore Sample Wgt, W (mg)
Sample Volume,
Vn (mL)
Dilution
Factor, Fd
Absorbance
•
Concentration,
Ca U/g/mL)
Mass, m
'. UQ
mn » C. Fd Vn m, * mn(filters) + mn(probe) + mn(impingers) -mn(filter blank) - mn(NaOH) - mn(H2O)
Matrix effects checked? (Attach LDS.) Baseline drift checked?
QA/aC Check
Completeness _
Checked by:
Legibility
Accuracy
Specifications
Reasonableness
Analyst (Signature/Date)
Team Leader (Signature/Date)
-------
Method (circle) 108A 108B
Client/Plant Name
Job No.
Run ID #
Test Date
Weight of Ore Sample, mg
Dilution Factor
Sample Cone, of Arsenic, fjg/mL
Arsenic in Ore, %
Audit Relative Error, %
SUMMARY SHEET 108A
Arsenic
w
Fd
Ca
%As
LDS 108
LDS 108
LDS 108
LDS 108
LDS 108
LDS 108
LDS 108
SS 108 A
9/30/94: S108A-1
Run#1
Run #2
Run #3
Avg
RE
QA 1
-------
9/30/94: L108A-1
LABORATORY PROCEDURE 108A
Inorganic Arsenic
Note: Use LDS 108.
A, Reagent Preparation
The reagents, 0.1 N NaOH (prepare half the
amount), 5% sodium borohydride, 5% nickel
nitrate, 1 mg As/mL stock arsenic standard
(except rather than evaporating just to dryness,
heat in an oven at 105°C for 2 hr), and QA audit
samples, are the same as that in Method 108. In
addition, prepare the following:
1. Nitric Acid, 0.5 N. Add 32 mL cone. HNO3
to a 1-L volumetric flask with water, dilute
to volume with water.
2. Potassium Chloride Solution, 10%. Dissolve
10 g KCl in water, add 3 mL cone. HNO3,
and dilute to 100 mL.
3. Standard Arsenic Solutions. Pipet 1,5, 10,
and 25 mL stock As solution into separate
100-mL volumetric flasks. Add 10mLKCI
solution and dilute to the mark with 0.5 N
HNO3 to obtain 10, 50,100, and 250 ^g
As/mL.
B. Sample Preparation
1. Obtain a sample that is representative of the
ore lot (representative samples routinely
collected for metals analysis may be used).
Grind the sample to a finely pulverized state.
2. Weigh 50 to 500 mg of finely pulverized
sample to the nearest 0.1 mg.
3. Transfer the sample into the Teflon cup of
the digestion bomb. Add 2 mL each of
cone. HNO3 and HF. Seal the bomb
immediately to prevent the loss of any
volatile arsenic compounds that may form.
3. Heat in an oven 105°C for 2 hr. Remove
from the oven and cool.
4. Using a Teflon filter, quantitatively filter the
digested sample into a 50-mL polypropylene
volumetric flask.
5. Rinse the bomb three times with small
portions of 0.5 N HNO3, filter the rinses into
the flask, add 5 mL 10% KCl solution to the
flask, and dilute to 50 mL with 0.5 N HN03.
C. Analysis
1. Dilute 10 mL 10% KCl solution to 100 mL
with 0.5 N HNO3 and use this as a reagent
blank. *"""
2. Analyze the samples as in FP 108, except
use the reagent in step C1 of this procedure
as the reagent blank and make appropriate
dilutions with 0.5 N HNO3.
-------
9/30/94: L108B-1
LABpRATORYPROCEDURE 1088
Arsenic Content in Ore Samples from Nonferrous Smelters
A. Reagents and Spectrophotometer
Preparation
1. Prepare the spectrophotometer as in LP 108,
section C.
2. Prepare stock arsenic standard (1.0 mg
As/mL) as follows:
a. Dry some primary grade As203 at
105°C.
b. Dissolve 1.3203 g in a 400-mL beaker
with 10 mL HNO3 and 5 mL HCI. Cover
with a watch glass and heat gently until
dissolution is complete.
c. Add 10 mL HNO3 and 25 mL HCI04,
evaporate to strong fumes of HCI04 and
reduce to about 20 mL.
d. Cool, add 100 mL of water and 100 mL
HCI, and transfer quantitatively to a 1 L
volumetric flask. Dilute to volume with
water and mix.
3. Prepare standard solutions as follows:
a. Pipet 1,5, 10, and 25 mL stock As
solution into separate 100-mL flasks.
b. Add 2 mL HCI04, 10 mL HCI, and dilute
to the mark with water to obtain 10, 50,
100, and 25O//g As/mL. For lower level
arsenic samples, use Method 1O8C.
4. Measure the standard absorbances against
the reagent blank. Check these absorbances
frequently against the blank during the
analysis to ensure that baseline drift has not
occurred.
5. Prepare a standard curve of absorbance
versus concentration. (Note: For instruments
equipped with direct concentration readout
devices, preparation of a standard curve will
not be necessary.) In all cases, follow
calibration and operational procedures in the
manufacturer's instruction manual. Maintain
a laboratory log of all calibrations.
6. Obtain QA Audit Samples. See QA 1.
B. Sample Preparation
1. Weigh 100 to 1000 mg of finely pulverized
sample to the nearest 0.1 mg. Transfer the
sample to a 150-mL Teflon beaker.
2. Dissolve the sample by adding (in this order)
15 mL HNO3, 10 mL HCI, 10 mL HF, and
10 mL HCI04, and let stand for 10 min.
3. In a HCIO4 fume hood, heat on a hot plate
until 2-3 mL HCI04 remain, then cool. Add
20 mL water and 10 mL HCI. Cover and
warm until the soluble salts are in solution.
Cool, and transfer quantitatively to a 100-mL
volumetric flask. Dilute to the mark with
water.
C. Analysis
1. Determine the absorbance of each sample
using the blank as a reference.
2. If the sample concentration falls outside the
range of the calibration curve, appropriately
dilute with 2% HCI04/10% HCI (prepared by
diluting 2 mL cone. HCI04 and 10 mL cone.
HCI to 100 mL with water).
3. • Determine the As concentration in each
sample from the calibration curve.
4. Mandatory: Check for matrix effects
according to LP 12, section D.
5. If applicable, analyze the audit samples.
-------
9/30/94: L108C-1
LABORATORY PROCEDURE 108C
Arsenic Content in Ore Samples from Nonferrous Smelters
Note: This method is applicable to samples having an analytical concentration less than 10 fjg As/mL.
A. Reagent Preparation
1. Dilute Hydrochloric Acid. Add one part cone.
HCI to nine parts water.
2, Ammonium Molybdate Solution, 5 g/L.
Dissolve 0.5 g {NH4)6Mo7024.4H20 in water
in a 100-mL volumetric flask, and dilute to
the mark. Use freshly-prepared.
3. Standard Arsenic Solution, 10 //g As/mL.
Dissolve 0.1320 g of As203 in 100 mL HCI in
a 1-L volumetric flask. Add 200 mL water,
cool, dilute to the mark with water, and mix.
Transfer 100 mL of this solution to a 1-L
volumetric flask, add 40 mL HCI, cool, dilute
to the mark, and mix.
4. Hydrazine Sulfate Solution, 1 g/L. Dissolve
0.1 g (NH2)2-H2SO4 in water, and dilute to
100 mL in a volumetric flask. Use freshly-
prepared.
5. Potassium Bromate (KBrO3) Solution, 0.03%.
Dissolve 0.3 g KBrO3 in water, and dilute to
1 L with water.
6. 1:1 HCI:Water. Slowly add one part cone.
HCI to one part water.
7. Obtain QA audit samples, if applicable
(seeQAD.
B. Sample Preparation
1. Weigh 1.0 g of finely pulverized sample to
the nearest 0.1 mg.
2. Transfer the sample to a 300-mL Erlenmeyer
flask and add (in this order) 15 mL HNO3,
4 mL HCI, 2 mL HF, 3 mL HCIO4, and 15 mL
H2S04.
3. In a HCIO4 fume hood, heat on a hot plate to
decompose the sample. Then heat while
swirling over an open flame until dense,
white fumes evolve.
4. Cool, add 15 mL water, swirl to hydrate the
H2S04 completely, and add several boiling
granules. Cool to room temperature.
5. Add 1 g KBr, 1 g hydrazine sulfate, and
50 mL HCI. Immediately attach the
distillation head with thermometer and dip
the side arm into a 50-mL graduated cylinder
containing 25 mL water and 2 mL bromine
water. Keep the graduated cylinder
Immersed in a beaker of cold water during
distillation.
6. Distill until the vapor in the flask reaches
107°C. When distillation is complete,
remove the flask from the hot plate, and
simultaneously wash down the side arm
with water as it is removed from the
cylinder.
7. If the expected arsenic content is from
0.0020 to 0.10%,
a. Dilute the distillate to the 50-mL mark of
the cylinder with water, stopper, and
mix.
b. Transfer a 5.0-mL aliquot to a 50-mL
volumetric flask. Add 10 mL water and
a boiling granule. Place the flask on a
hot plate, and heat gently until the
bromine is expelled and the color of
methyl orange indicator persists upon
the addition of 1-2 drops. Cool the
flask to room temperature.
c. Neutralize just to the yellow color of the
indicator with dropwise additions'; of
NH4OH. Bring back to the red color by
dropwise addition of dilute HCI, and add
10mL excess.
8. If the expected arsenic content is from
0.0002 to 0.0010%, ;
a. Transfer either the entire initial distillate
or the measured remaining distillate
from above to a 250-mL beaker. Wash
the cylinder with two successive
portions of cone. HNO3, adding each
portion to the distillate in the beaker.
b. Add 4 mL cone. HCIO4, a boiling
granule, and cover with a flat watch
glass placed slightly to one side. Boil
gently on a hot plate until the volume is
reduced to about 10 mL.
c. Add 3 mL HNO3, and continue the
evaporation until HCIO4 is refluxing on
the beaker cover. Cool briefly, rinse the
underside of the watch glass and the
inside of the beaker with about 3-5 mL
water, cover, and continue the
evaporation to expel all but 2 mL of the
HCIO4.
-------
9/30/94: L108C-2
d.
e.
f.
Note: If the solution appears cloudy ,
due to a small amount of antimony
distilling over, add 4 mL 1:1 HCI:water
and 5 mL water, cover, and warm
gently until clear. If cloudiness persists,
add 5 mL HNO3 and 2 mL H2SO4.
Continue the evaporation of volatile
acids to solubilize the antimony until
dense white fumes of H2SO4 appear.
Retain at least 1 mL of the H2SO4.
To the 2 mL HCIO4 solution or 1 mL
H2SO4 solution, add 15 mL water, boil
gently for 2 min, and then cool.
Proceed with the molybdenum blue
color development by neutralizing the
solution directly in the beaker just to the
yellow indicator color by dropwise
addition of NH4OH. Just bring back the
red color by dropwise addition of dilute
HCI.
Transfer the solution to a 50-mL
volumetric flask, and rinse the beaker
successively with 10 mL dilute HCI,
followed by several small portions of
, water. At this point the volume of
solution in the flask should ^40 mL.
C Calibration
1. Transfer 1.0, 2.0, 4.0, 8.0, 12.0, 16.0, and
20.0 mL of standard arsenic solution
(10 fig/mL) to each of seven 50-mL
volumetric flasks. Dilute to 20 mL with dilute
HCI.
2. Add one drop of methyl orange solution and
neutralize to the yellow color with dropwise
addition of NH4OH. Just bring back to the
red color by dropwise addition of dilute HCI,
and add 10 mL in excess.
3. Proceed with the color development as
described in section D.. Plot the
photometric readings of the calibration
solutions against yug As per 50 mL of
solution. From the curve, determine the As
concentration in each sample.
D. Analysis
1. Add 1 mL KBrO3 solution to the flask and
heat on a low-temperature hot plate to about
50°Cto oxidize the arsenic and methyl
orange.
2. Add 5.0 mL ammonium molybdate solution
to the warm solution and mix. Add 2.0 mL
of hydrazine sulfate solution, dilute until the
solution comes within the neck of the flask,
and mix.
3. Place in a 400-mL beaker, 80% full of
boiling water, for 10 min. Supply enough '
heat to prevent the water bath from cooling
much below the boiling point upon inserting
the volumetric flask. Remove the flask, cool
to room temperature, dilute to the-mark, and
mix.
4. Transfer a suitable portion of the reference
solution to an absorption cell, and adjust the
photometer to the initial setting, using a light
band centered at 660 nm. While
maintaining this photometer adjustment,
take the photometric readings of the
calibration solutions followed by the
samples.
5. If applicable, analyze the audit samples.
-------
Client/Plant Name_
City/State
Photometer ID #
9/30/94: LD108C-1
LABORATORY DATA SHEET 108C
Arsenic
Job #
Date Last Calibration
Date
Analyst
Sample
No.
e
Sample
ID#
0.2 //g/mL Std
0.4//0/mLStd
0.8 //g/mL Std
1.6 //g/mL Std
2.4 //g/mL Std
3. 2 //g/mL Std
4.0 //g/mL Std
Audit
Sample Wgt,
W(g)
Aliquot Vol.,
(mL)
Dilution
Factor
--
Absorbance
\
',
(•'••
•
As Cone.,
Ca (//g/mL)
•
Plot Calibration Curve: Absorbance vs Concentration (//g As/50 mL)
QA/QC Chock
Completeness
Checked by: _
Legibility
Accuracy
Specifications
Reasonableness
Analyst (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: Ql-1
QUALITY ASSURANCE 1
Quality Assurance Audit Samples
A. Procedure
Quality Assurance Audit Samples are prepared
by EPA's Atmospheric Research and Exposure
Assessment Laboratory, Quality Assurance and
Technical Support Division, Mail Drop 77A,
Research Triangle Park, North Carolina 27711.
1. Only when making compliance
determinations, obtain a quality assurance
audit sample set from the Quality Assurance
Management Office at each EPA regional
office or the responsible enforcement
agency. Make this request at least 30 days
prior to the test date to allow sufficient time
for sample delivery.
2. The same analysts, analytical reagents, and
analytical system must be used for both
compliance samples and the EPA audit
samples; if this condition is met, auditing of
subsequent compliance analyses for the
same enforcement agency within 30 days is
not required.
3. An audit sample set may not be used to
validate different sets of compliance
samples under the jurisdiction of different
enforcement agencies, unless prior
arrangements are made with both
enforcement agencies.
4. Concurrently analyze the audit samples and
a set of compliance samples.
5.. Calculate the concentrations as specified in
the audit instructions.
6. The concentrations of the audit samples
obtained by the analyst must agree within
the prescribed specifications. If the
specification is not met, reanalyze the
compliance samples and audit samples, and
include initial and reanalysis values in the
test report.
7. Failure to meet the specification may require
retests until the audit problems are resolved.
However, if the audit results do not affect
the compliance or noncompliance status of
the affected facility, the Administrator may
waive the reanalysis requirement, further
audits, or retests and accept the results of
the compliance test. While steps are being
taken to resolve audit analysis problems, the
Administrator may also choose to use the
data to determine the compliance or
noncompliance status of the affected
facility.
8. Indication of acceptable results may be
obtained immediately by reporting the audit
results in the units specified by the QA
instructions and compliance results by
telephone to the responsible enforcement
agency.
9. Include the results of all audit samples, their
identification numbers, and the analyst's
name with the results of the compliance
determination samples in appropriate
reports to the EPA regional office or the
appropriate enforcement agency. Include
this information with subsequent
compliance analyses for the same
enforcement agency during the 30-day
period.
B. Methods 6/6A/6B/8 Audit Samples
1. Each set will consist of two vials having
sulfate solutions of unknown
concentrations.
2. Specification: ±5% of actual
concentrations.
3. For Method 6B only:
a. Analyze the audit samples at, least once
for every 30 days of sample collection.
b. If more than one analyst performed the
sample analyses during the 30-day
sampling period, each analyst must
perform the audit analyses and all audit
results must be reported.
C. Methods 7/7A/7B/7C/7D Audit Samples
1. Each set will consist of two vials having
nitrate solutions of unknown
concentrations.
2. Specification: ±10% of the actual audit
concentrations.
3. For Method 7B only: Analyze the audit
samples with each set of compliance
samples or once per analysis day, or once
per week when averaging continuous
samples.
4. For Method 7C only: When requesting
audit samples, specify appropriate
concentration range.
D. Method ISA Audit Samples
1. Each set will consist of two vials having
sulfate solutions of unknown
concentrations.
2. Specification: ±5% of actual
concentrations.
-------
9/30/94: Q1-2
E Method ISA Audit Samples
1. Each set will consist of two vials having
sulfate solutions of unknown
concentrations.
2. Specification: ±5% of actual
concentrations.
F. Method 18 Audit Samples
1. Each set will consist of two audit cylinders
or vials.
2. Specification: ±10% of the actual audit
concentrations.
3. Analyze the audit samples prior to the
sample analyses.
4. Perform the analysis audit described in
40CFR, Part 61, Appendix C, Procedure 2:
"Procedure for Field Auditing GC Analysis."
5. Audit cylinders obtained from commercial
gas manufacturers may be used provided:
a. the manufacturer certifies the audit
cylinder, and
b. an independent analysis of the audit
cylinder is performed yielding a
concentration within ± 5% of the
reported concentration.
6. Method 23 Audit Samples
1. Each audit sample contains unknown
quantities of tetra through octa isomers of
PCDD and PCDF.
2. Analyze one audit sample with each set of
compliance samples.
H. Method 25 Audit Samples
1. Each set will consist of two vials having
organlcs of unknown concentrations.
2. Specification: ±20% of the actual audit
concentrations.
3. Calculate the concentration of the audit
samples in ppm.
/. Method 26/26A Audit Samples
1. Each set will consist of two vials having
chloride solutions of unknown
concentrations.
2. Specification: ±10% of the actual audit
concentrations.
3. Calculate the concentration of the audit
samples in mg/dscm.
J. Method 1O6 Audit Samples
1 . Each set will consist of two cylinders
containing vinyl chloride in nitrogen.
2. Analyze the audit samples prior to the
sample analyses.
3. Perform the analysis audit described in
4OCFR, Part 61, Appendix C, Procedure 2:
"Procedure for Field Auditing GC Analysis."
4. The concentrations of the audit cylinders
should be:
a. 5 to 20 ppm vinyl chloride, and
b. 20 to 50 ppm vinyl chloride.
5. Audit cylinders obtained from commercial
gas manufacturers may be used provided:
a. the manufacturer certifies the audit
cylinder, and
b. an independent analysis of the audit
cylinder is performed yielding a
concentration within ±5% of the
reported concentration.
K. Method 108/1 08A/108B/108C Audit
Samples
1 . Each set will consist of two vials having
arsenic solutions of unknown
concentrations. •
2. Calculate the concentration in g/dscm.
CALCULATIONS
Calculate the relative error (RE) for the QA
audit samples in percent as follows:
RE =
x 100
where:
Cd = Determined audit sample
concentration.
Ca = Actual audit sample concentration.
Note: Determine the concentrations In the units
specified in the audit instructions, i.e., ensure that
both Cd and Caare in the same units.
-------
9/30/94: P1-1
PERFORMANCE SPECIFICATION PROCEDURE 1
Performance Specification Verification
Note: Test each COM3 that conforms to the design specifications (PSP 1b) with the data recording
system to be employed during monitoring. If different data recording systems are used during the
performance test and monitoring, obtain prior approval from, the Administrator.
A. Equipment Preparation
1. Measure the mounting distance between the
transmitter and receiver/reflector unit at the.
source (do not use distances from
engineering drawings). Then, set up and
calibrate the COM3 using the measured path
length according to the manufacturer's
written instructions.
2. If the COMS has automatic path length
adjustment, follow the manufacturer's
instructions to adjust the signal output from
the analyzer in order to yield results based on
the emission outlet path length.
3. Set the instrument and data recording system
ranges so that maximum instrument output is
within the span range specified in the
applicable subpart.
4. Align the instrument so that maximum
system response is obtained during a zero (or
upscale) check performed across the
simulated monitor path length. As part of
this alignment, include rotating the reflector
unit (detector unit for single pass
instruments) on its axis until the point of
maximum instrument response is obtained.
5. Zero and span the instrument according to
the manufacturer's instructions. Perform the
zero alignment adjustment by balancing the
response of the COMS so that the simulated
zero check coincides with the actual zero
check performed across the simulated
monitor path length. At this time, measure
the indicated upscale calibration value (must
be 5: applicable opacity standard, but
sO.5 applicable span value).
B. Calibration Error Test
1. Insert the calibration attenuators (low, mid,
and high range) in the transmissometer path
at or as near the midpoint of the
measurement path as feasible. If a particular
instrument requires placement in the
instrument housing, attach data from the
manufacturer showing this procedure is
acceptable. Ensure that the entire beam
received by the detector passes through the
attenuator and that interference from
reflected light is minimized.
2. Make a total of five nonconsecutive readings
for each filter.
3. Calculate the calibration error for each of the
three test attenuators. If the path length is
adjusted by the measurement system,
subtract the "path adjusted" calibration
attenuator values from the values indicated
by the measurement system recorder.
C. System Response Test
1. Insert the high-range calibration attenuator in
the transmissometer path five times, and
determine the upscale and downscale
response times.
2. Calculate the system response time.
D. Optical and Zero Alignment
Install the COMS on the affected facility
according to the manufacturer's writteni\
instructions and PSP 2a. Perform either of the
following optical and zero alignment procedures.
1. Preferred Procedure
a. When the facility is not in operation,
optically align the light beam of the
transmissometer upon the optical
surface located across the duct or stack
(i.e., the retroreflector or photodetector,
as applicable) according to the
manufacturer's instructions; verify the
alignment with the optical alignment
sight.
b. Under clear stack conditions, verify the
zero alignment (step A5) by assuring
that the monitoring system response for
the simulated zero check coincides with
the actual zero measured by the
transmissometer across the clear stack.
Adjust the zero alignment, if necessary.
(Note: The stack should be monitored
and the data output (instantaneous real-
time basis) examined to determine
whether fluctuations from zero opacity
are occurring before a clear stack
condition is assumed to exist.)
c. After the affected facility has been
started up and the effluent stream
reaches normal operating temperature,
recheck the optical alignment. If the
optical alignment has shifted, realign the
optics.
-------
9/30/94: P1-2
2. Alternative Procedure
a. If the facility is operating and a zero
stack condition cannot practicably be
obtained, use the zero alignment
obtained during step A4 before installing
the transmissometer on the stack.
b. Install the system at the source and align
the optics according to the
manufacturer's instruction. Verify the
alignment with the optical alignment
sight.
c. Verify the zero alignment and adjust, if
necessary, the first time a clear stack
condition is obtained after completion of
the operational test period.
£. Conditioning Period
1. After completing the preliminary field
adjustments, operate the COM3 according to
the manufacturer's instructions for an initial
conditioning period of & 168 hr while the
source is operating. A successful
conditioning period is as follows:
a. Except during times of instrument zero ,
and upscale calibration checks, the
COMS measures the effluent gas opacity
and produces a permanent record of the
COMS output.
b. No unscheduled maintenance, repair, or
adjustment is made.
c. Except for periods of source breakdown
(record the dates and times of process
shutdown), the 168-hr period is
continuous. If the interruption is due to
monitor failure, restart the 168-hr period
when the monitor becomes operational.
2. Conduct daily zero calibration and upscale
calibration checks; and, when accumulated
drift exceeds the daily operating limits, make
adjustments and clean the exposed optical
surfaces. The data recorder must reflect
these checks and adjustments.
3. At the end of the operational test period,
verify that the instrument optical alignment is
correct.
F. Operational Test Period
1. After completing the conditioning period,
operate the system for an additional 168hr
(need not follow immediately after the 168-hr
conditioning period). A successful
operational test is the same as that for the
conditioning period.
2. The following are permissible during the
operational test period.
a. Zero and calibration adjustments, optical
surface cleaning, and optical
realignment (optional) only at 24-hr
intervals or at such shorter intervals if
specified by the manufacturer's written
instructions. (Make a record of these
operations.)
b. Automatic zero and calibration
adjustments without operator
intervention or initiation at any time.
6. Zero and Upscale Drift Tests
1. At the outset of the 168-hr operational test
period, measure the initial simulated zero (or
^10% opacity) and upscale opacity
readings.
2. After each 24-hr interval, check the zero
reading before any optional or required
cleaning and adjustment (adjustments and
cleaning must be performed when the
accumulated zero calibration or upscale
calibration drift exceeds the 24-hr .drift
specification of ±2% opacity).
a. If no adjustments are made after the
zero check, record the final zero reading
as the initial zero reading for the next
24-hr period.
b. If adjustments are made, record the zero
value after adjustment as the initial zero
value for the next 24-hr period.
c. If the instrument has automatic zero
compensation and the zero value cannot
be measured before compensation is
entered, then record the amount of
. automatic zero compensation (as
opacity) for the final zero reading of
each 24 hour period.
3. After the zero calibration value has been
checked and any optional or required
adjustments have been made, check the
simulated upscale calibration value. Follow
the same general rule as in step G2.
4. Determine the 24-hr zero and calibration
drifts.
H. Retest
1. If the COMS fails one of the preliminary
tests, repeat the performance testing for the
failed specification prior to conducting the
operational test period.
2. If the COMS fails to meet the specifications .
for the operational test period, repeat the
operational test period; depending on the
cause of failure, it may be necessary to
repeat the design and preliminary
performance tests.
-------
9/30/94: P1a-1
PERFORMANCE SPECIFICATION PROCEDURE 1 a
Installation and Measurement Location
Note: The intent is to install the COMS at a location where the ^parity measurements are representative
of the total emissions, generally one where the stack gases are well-mixed.
A. Measurement Location
Install the continuous opacity monitoring
system (COMS) at a location that is:
1. Downstream from all participate control
equipment.
2. Where condensed water vapor is not present.
3. Free of interference from ambient light
(applicable only if transmissometer is
responsive to ambient light).
4. Accessible to permit routine maintenance.
B. Measurement Path
Select a measurement path that passes
through a centroidal area equal to 25% of the
cross section. For additional requirements or
modifications, see Figures P1a-1 through P1a-5.
C. Alternative Locations and Measurement
Paths
Demonstrate acceptability of alternative
locations and measurement paths as follows:
1. Select a measurement location and path that
meet the criteria in steps A and B. Select
the alternative location and path.
'2. Measure the opacities at the two locations or
paths for S2 hr and determine the average
opacity. Measurement may be measured at
different times, if the process operating
conditions are same.
3. Acceptability Criteria: Alternative/Reference
£ ±0.10 or Alternative minus Reference £
±2%.
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Figure P1 a-1. Transmissometer location downstream of a bend in
a vertical stack.
Figure P1a-2. Transmissometer location upstream of a bend in
a vertical stack.
-------
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Figure P1»-4. Tnntmisconwler location greater than (our diameters downstream
of a vertical bend In a horizontal stack.
Figure P1a-5. Transmnsometer location less than four diameters dow
of a vertical bend in a horizontal stack.
-------
PERFORMANCE SPECIFICATION DATA SHEET 1a
Calibration Error Determination
Client/Plant Name
Job #
9/30/94: PD1a-1
Date
Analyzer Manufacturer/Model/Serial No.
COMS Location
Pathlength, L-,
Personnel
Outlet Pathlength, L2
COMS Output Pathlength Corrected? Yes No
OD, = OD2
Range
Low
Mid
High
Calibrated Neutral Density Filter Values
Actual (1)
Optical Density, OD
Opacity, Op
Path-Adjusted (2)
Optical Density, OD
Opacity, Op
Run
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Level
Low
Mid
High
Low
Mid
High
Low
Mid
High
Low
Mid
High
Low
Mid
High
Cal Filter
Path-Adjusted
(% Op)
*
Instrument
Reading
(%0p)
Arithmetic Mean, ~x
Confidence Coefficient, CC
Calibration Error, |)<| + |CC|
Arithmetic Difference (% Op)
Low
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QA/QC Check
Completeness
Leaibility
n-1
Accuracy
cc = Ws -=
v/n
Specifications
Reasonableness
Checked by:
Personnel (Signature/Date)
ream Leader (Signature/Date)
-------
9/30/94: P1b-1
PERFORMANCE SPECIFICATION PROCEDURE 1 b
Design Specifications Verification
Note: This procedure will not apply to all instrument designs and will require modification in some cases;
all procedural modifications are subject to the approval of the Administrator.
A. Spectral Response
1. Obtain detector response, lamp emissivity,
and filter transmittance data from their
respective manufacturers, and develop the
effective spectral response curve of the
transrnissorneter.
2. Then determine the peak and mean spectral
response wavelengths, and the maximum
response at any wavelength below 400 nm
and above 700 nm expressed as a
percentage of the peak response.
B. Angle of View
1. Set up the receiver as specified by the
manufacturer's written instructions.
2. Draw an arc with radius of 3 m in the
horizontal direction. Using a small (<3 cm)
nondirectional light source, measure the
receiver response at 5-cm intervals on the arc
for 30 cm on either side of the detector
centerline.
3. Repeat step B2 in the vertical direction.
4. For both horizontal and vertical directions,
calculate the response of the receiver as a
function of viewing angle (26 cm of arc, 3-m
radius, equals 5°). Determine angle of view.
C. Angle of Projection
1. Set up the projector as specified by the
manufacturer's written instructions.
2. Conduct steps B2 and B3.
3. For both the horizontal and vertical
directions, calculate the response of the
photoelectric detector as a function of the
projection angle, and determine the angle of
projection.
D. Optical Alignment Sight
Instruments that provide an absolute zero
check while in operation and while maintaining
the same optical alignment during measurement
and calibration may omit this step (e.g., some
"zero pipe" units).
1. Set up the instrument in the laboratory
according to manufacturer's written
instructions for a monitor path length of
8 m..
2. Align, zero, and span the instrument. Insert
an attenuator of 10% (nominal opacity) into
the instrument path length.
4.
5.
Slowly misalign the projector unit by rotating
it vertically until a positive or negative shift
of 2% opacity is obtained by the data
recorder. Then, following the
manufacturer's written instructions, check
the alignment. The alignment procedure
must indicate that the instrument is
misaligned.
Repeat this test for lateral misalignment of
the projector.
Repeat steps D2 and D4 with the receiver or
retroreflector unit (i.e., lateral misalignment
only).
E. Other Design Features
1. Access to External Optics. Access the
optical surfaces exposed to the effluent
stream and clean the surfaces without
removing the unit from the source mounting
or without disturbing the optiqal alignment.
2. Slotted Tube. Measure the length of the
slotted portion (s). Check if slotted tube is of
sufficient size and orientation so as not to
interfere with the free flow of effluent
through the entire optical volume of the
transrnissorneter photodetector.
a. Obtain data from the manufacturer that
the transrnissorneter minimizes light
reflections (at least data from laboratory
operation of the transrnissorneter both
with and without the slotted tube in
position).
b. If the slot length is <90% of the
effluent path length, provide
comparative data between slotted tube
and another instrument that meets the
requirement according to PSP 1a,
step C.
F. Alternatives
1. Design Specification Verification. Obtain a
Manufacturer's Certificate of Conformance in
lieu of doing the above.
a. The certificate must state that the first
analyzer randomly sampled from each
month's production was tested
according to the above procedures and
satisfactorily met all requirements of
section 5 of Performance Specification 1
(PS1).
-------
b. If any of the requirements were not met,
the certificate must state that the entire
month's analyzer production was
resampled according to the military
standard 105D sampling procedure (MIL-
STD-105D) inspection level II; was
retested for each of the applicable
requirements under section 5 of PS 1;
and was determined to be acceptable
under MIL-STD-105D procedures,
acceptable quality level 1.0.
9/30/94: P1b-2
c. The certificate must include the results
of each test performed for the
analyzer(s) sampled during the month
the analyzer being installed was
produced.
2. Soectral Response (Step A). Laboratory
measurements of the instrument's spectral
response curve may be conducted. These
procedures are subject to approval of the
Administrator.
-------
9/30/94: PD1b-1
PERFORMANCE SPECIFICATION DATA SHEET 1b
Response Time
Client/Plant Name
Job #
Date
Analyzer Manufacturer/Model/Serial No.
COM3 Location
Personnel
High Range Calibration Filter Value:
«
Actual Optical Density (Opacity)
Path-Adjusted Optical Density (Opacity)
Upscale Response Value (0.95 x Filter Value),
Downscale Response Value (0.95 x Filter Value),
%Op -
%Op =
Upscale
Downscale
Run No.
1
2
3
4
5
1
2
3
4
5
Average
Response Time
(sec)
QA/ac Check
Completeness
Legibility
Checked by:
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
9/30/94: P1c-1
A. Selection
1. Based on the span value specified in the
applicable subpart, select a minimum of three
calibration attenuators (low, mid, and high
range) using table CP1.
PERFORMANCE SPECIFICATION PROCEDURE 1c
Calibration Attenuator
Note: If this procedure is conducted by the filter or screen manufacturer or by an independent laboratory,
obtain a statement certifying the values and certifying that the specified procedure, or equivalent, was used.
B. Attenuator Calibration
1. Select a calibration spectrophotometer
meeting the following minimum design
specifications:
a. Wavelength range: 400-700 nm
b. Detector angle of view: < 10°
c. Accuracy: <0.5% transmittance, N1ST-
traceable calibration.
2. Make measurements on required filters or
screens at wavelength intervals of £20 nm.
(As an alternative procedure, use the
calibration spectrophotometer to measure
the C.I.E. Daylightc luminous transmittance
of the attenuators.
3. Check the attenuators several times, at
different locations on the attenuator.
C. Attenuator Stability Checks ,
1. Check attenuator values at intervals
£ stability period guaranteed by the
manufacturer or £3 months, whichever is
more frequent. Recheck at least every 3
months.
2. If desired, the stability checks with a high-
quality laboratory transmissometer
(secondary) other than the calibration
spectrophotometer may be used. The same
instrument must always be used for the
stability checks. Determine a base value on
the secondary instrument by measuring
attenuators immediately following initial
calibration.
3. Recalibrate the attenuator on the calibration
spectrophotometer or replace it with a new
attenuator if values change by a: ±2%
opacity:
Table CP1 . Required Calibration Attenuator Values
(Nominal)
Span Value
(% Opacity)
40
50
60
70
80
90
100
Calibrated Attenuator Optical Density
(Equivalent Opacity), D2
Low-Range
0.05(11)
0.1 (20)
0.1 (20)
0.1 (20)
0.1 (20)
0.1 (20)
0.1 (20)
Mid-Range
0.1 (20)
0.2 (37)
0.2 (37)
0.3 (50)
0.3 (50)
0.4 (60)
0.4 (60)
High-Range
0.2 (37)
0.3 (50)
0.3 (50)
0.4 (60)
0.6 (75)
0.7 (80)
0.9 (87.5)
2. For systems with automatic path length
compensation, calculate the attenuator
values required to obtain a system response
equivalent to the applicable values shown in
table CP1.
3. A series of filters with nominal optical density
(opacity) values of 0.1(20), 0.2(37), 0.3(5O),
0.4(60), 0.5(68), 0.6(75), 0.7(80), 0.8(84),
0.9(88), and 1.0(90) are commercially
available. Within this limitation of filter
availability, select the calibration attenuators
having the values given in table CP1 or
having values closest to those calculated in
step A2.
4. Obtain the selected attenuators along with
specified time over which the attenuator
values can be considered stable and any
special handling and storing procedures
required to enhance attenuator stability.
-------
9/30/94: PD1c-
Client/Plant Name
PERFORMANCE SPECIFICATION DATA SHEET 1c
Zero and Calibration Drift
Job*
Date
Analyzer Manufacturer/Model/Serial No.
COMS Location Personnel
Pathlength, L1 Emission Outlet Pathlength, L2
Upscale Calibration Value: Actual OD (Opacity) {
Output Pathlength Corrected? Yes No
J Path-Adjusted OD (Opacity) (
Date
Time
Begin
End
% Opacity
Zero
Reading8
Initial
A
Final
B
Arithmetic Mean, x"
Confidence Coefficient, CC
Zero Drift = |x"| +|CC|
Zero
Drift
C=B-A
Zero
Adj?
Upscale Cal
Reading
Initial
D
Final
E
Upscale
Drift
F=E-D
Arithmetic Mean, ~x
Confidence Coefficient, CC
Calibration Drift = |x"| + |CC|
Cal
Drift
G=F-Cb
Span
Adj?
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b If zero was adjusted manually or automatically prior to upscale check, then use C = 0.
QA/aC Check
Completeness
Checked by: _
Legibility
Accuracy
Specifications
Reasonableness
Personnel (Signature/Date)
Team Leader (Signature/Date)
-------
9/30/94: P2-1
PERFORMANCE SPECIFICATION PROCEDURE 2
Performance Specification Test
A. Pretest Preparation
1. Install the continuous emission monitoring
system (GEMS) and prepare the reference
method (RM) test site. See PSPs 2a, 2b,
and 2c.
2. Prepare the CEMS for operation.
B. Calibration Drift (CD) Test
1. Select a time period when the affected
facility will operate >50% of normal load, or
as specified in an applicable subpart, for
7 consecutive days.
2. Determine the magnitude of the CD once
each day (at 24-hr intervals) for
7 consecutive days at the low-level value
(LLV) and HLV. If periodic automatic or
manual adjustments are made to the CEMS
zero and calibration settings, conduct the CD
test immediately before these adjustments, or
conduct it in such a way that the CD can be
determined.
a. Introduce to the CEMS the reference
gases, gas cells, or optical filters (these
need not be certified).
b. Record the CEMS response and subtract
this value from the reference value (see
PDS 2).
;
C. Relative Accuracy Test
1. Select a time period when the affected
facility will operate >50% of normal load, or
as specified in an applicable subpart, for the
test period. The RA test may be conducted
during the CD test period.
2. For instruments that use common
components to measure more than one
effluent gas constituent, test all channels
simultaneously.
3. Conduct at least nine sets of all necessary
RM tests. Conduct each set (including
diluent, if applicable, and moisture, if needed)
within a period of 30 to 60 min. Note: If
more than nine sets are taken, up to three
sets of the test results may be rejected so
long as the total number is &9; report all
data, including the rejected data.
4. Use the following strategies for the RM tests.
Mark the beginning and end of each RM test
run (including the exact time of the day) on
the CEMS chart recordings or other
permanent record of output.
a. For integrated samples, e.g., Method 6
and Method 4, make a sample traverse
of at least 21 min, sampling for 7 min at
each traverse point.
b. For grab samples, e.g.. Method 7, take
one sample at each traverse point,
scheduling the grab samples so that
they are taken within a 3-min period or
are an equal interval of time apart over a
21-min (or less) period. A test run for
grab samples must be made up of at
least three separate measurements.
c. Note: If CEMS RA tests are conducted
during new source performance
standards performance tests, RM results
obtained during CEMS RA tests may be
used to determine compliance as long as
the source and test conditions are
consistent with the applicable
regulations.
5. Correlate the CEMS and the RM test data as
to the time and duration as follows:
a. Determine from the CEMS final output
(the one used for reporting) the
integrated average pollutant
concentration or emission rate for each
pollutant RM test period.
b. Consider system response time, if
important, and confirm that the pair of
results are on a consistent moisture,
temperature, and diluent concentration
basis.
c. Compare each integrated CEMS value
against the corresponding average RM
value. Use the following guidelines to
compare the CEMS integrated average
value against the RM values.
• If the RM has an integrated
sampling technique, use the RM
results.
• If the RM has a grab sampling
technique, use the average from all
grab samples taken during the test
run. If the pollutant concentration
is varying with time over the run,
the arithmetic average of the CEMS
value recorded at the time of each
grab sample may be used.
-------
9/30/94: PS2-1
PERFORMANCE SPECIFICATIONS 2
SO2 and NOX
A. Performance Specifications
1. Instrument Zero and Span: See PSP 2c.
2. Calibration Drift: =s2.5% of span value.
Determine CD for each pollutant or diluent
monitor In the system in terms of
concentrations.
3. Relative Accuracy: £20% of the mean value
of the RM test data in terms of the units of
the emission standard or 10% of the
applicable standard, whichever is greater.
a. For SO2 emission standards between
0.30 and 0.20 Ib/million Btu, 15% of
, emission standard.
b. For SO2 emission standards below
0.20 Ib/million Btu, 20% of emission
standard.
B. Test Procedure
1. Relative Accuracy Test. See PSP 2.
2. Reference Method. Unless otherwise
specified in an applicable subpart of the
regulations, the following or any approved
alternative:
a. Method 6 for SO2
b. Method 7 for NOX
c. Method 4 for moisture
d. Method 3B for diluent. •
-------
9/30/94: PD2-1
Client/Plant Name
City/State
Test Location
Analyzer Type/ID* _
Note: Indicate units.
PERFORMANCE SPECIFICATION DATA SHEET 2
Calibration Drift
Job#
Date/Time
Personnel
Span
Day
1
2
3
4
5
6
7
Level
Low-level
High-level
Low-level
High-level
Low-level
High-level
Low-level
High-level
Low-level
High-level
Low-level
High-level
Low-level
High-level
Date and
time
Calibration
value
Monitor
value
Difference
•••
%SV
(<:2.5%?)
,,
Facility at >50% of normal load?
Test conducted immediately before any zero and calibration adjustments?
QA/QC Check
Completeness
Checked by:
Legibility
Accuracy
Personnel (Signature/Date)
Specifications
Reasonableness
Team Leader (Signature/Date)
-------
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-------
9/30/94: P2a-1
PERFORMANCE SPECIFICATION PROCEDURE 2a
Installation and Measurement Location
P'~te: The acceptability of a Continuous Emission Monitoring System (OEMS) location is determined by
passing the relative accuracy (RAI test. Suggested measurement locations and points or paths that are
most likely to provide data that will meet the RA requirements are listed below.
A. Overall
Select a location that is
1. s 2 D. downstream from the nearest control
device, the point of pollutant generation, or
other point at which a change in the pollutant
concentration or emission rate may occur.
2. &0.5 D. upstream from the effluent exhaust
or control device.
B. Point OEMS
Select a measurement point that is either
1. & 1.0 meter from the stack or duct wall.
2. Within or centrally located over the centroidal
area of the stack or duct cross section.
C. Path OEMS
Select an effective measurement path that is
either
1. Totally within the inner area bounded by a
line 1.0 meter from the stack or duct wall.
2. Have at least 70% of the path within the
inner 50% of the stack or duct cross-
sectional area.
3. Centrally located over any part of the
centroidal area.
-------
9/30/94: P2b-1
PERFORMANCE SPECIFICATION PROCEDURE 2b
Reference Method Measuremei.t Location and Traverse Points
A. Procedure
1. Select a Reference Method (RM)
measurement point (the CEMS and RM
locations need not be the same) that is
a. 5:2 D. downstream from the nearest
control device, the point, of pollutant
generation, or other point at which a
change in the pollutant concentration or
emission rate may occur.
b. S:0.5 D. upstream from the effluent
exhaust or control device.
2. Establish a "measurement line" that passes
through the centroidal area and in the
direction of any expected stratification. If
this line interferes with the CEMS
measurements, displace the line up to 30 cm
(or 5% of D. of the cross section, whichever
is less) from the centroidal area.
3. Locate three traverse points at 16.7, 50.0,
and 83.3% of the measurement line.
4. Conduct all necessary RM tests within 3 cm
(but no less than 3 cm from the stack or duct
wall) of the traverse points.
B. Alternatives
1. StepAla. When pollutant concentration
changes are due solely to diluent leakage
(e.g., air heater leakages) and pollutants and
diluents are simultaneously measured at the
same location, 0.5 D. may be used in lieu of
2D..
2. Step A3. If the measurement line is longer
than 2.4 meters and pollutant stratification is
not expected, the three traverse points may
be on the line at 0.4, 1.2, and 2.0 meters
from the stack or duct wall. This option
must not be used after wet scrubbers or at
points where two streams with different
pollutant concentrations are combined.
3. Step A3. Other traverse points may be
selected, provided that they can be shown
to the satisfaction of the Administrator to
provide a representative sample over the
stack or duct cross section.
-------
9/30/94: P2c-1
PERFORMANCE SPECIFICATIONS PROCEDURE 2c
Instrument Zero and Span
A.
1.
2.
Equipment and Design Specifications
Data Recorder Scale. The CEMS data
recorder response range must include zero
and a high-level value. Select the high-level
value (HLV) as follows:
a. For uncontrolled emission (e.g., at the
inlet of a flue gas desulfurization unit),
select HLV between 1.25 and 2 times
the average potential emission level,
unless otherwise specified in an
applicable subpart of the regulations.
b. For controlled emissions (including
emissions in compliance with an
applicable regulation), select the HLV
between 1.5 times the pollutant
concentration corresponding to the
emission standard level and the span
value.
c. Establish the data recorder output so
that the HLV is read between 90% and
100% of the data recorder full scale.
The calibration gas, optical filter, or cell
values used to establish the data
recorder scale should produce zero and
HLV readings.
Calibration Drift. Design must allow the
determination of calibration drift at zero and
HLV.
B. Alternatives
1.
4.
5.
StepAla. A lower HLV may be used;
however, emissions that exceed the full-
scale limit of the CEMS must be measured in
accordance with the requirements of
applicable regulations.
Step A1c. The scale requirement may not
be applicable to digital data recorders.
Step A1c. A calibration gas, optical filter, or
cell value between 50% and 100% of HLV
may be used in place of HLV, provided the
data recorder full-scale requirements are
met.
Step A2. The CEMS design may allow
calibration drift determinations to be
conducted at a low-level value {zero to 20%
of HLV) and at a value between 50 and
100% of HLV.
Step A2. The Administrator may.approve a
single-point calibration-drift determination.
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9/30/94: P2d-1
PERFORMANCE SPECIFICATION PROCEDURE 2d
Alternative Procedure
Note: This is an alternative to the RA procedure in section 7 of PS 2, if the criteria in paragraphs
60.13(c)(1) and (2) are met. Use of this procedure does not preclude the requirements to complete the
CD tests nor any other requirements specified in the applicable regulations) for reporting OEMS data and
performing CEMS drift checks or audits.
1. Conduct a complete CEMS status check
following the manufacturer's written
instructions. Include operation of the light
source, signal receiver, timing mechanism
•functions, data acquisition and data reduction
functions, data recorders, mechanically
operated functions {mirror movements, zero
pipe operation, calibration gas valve
operations, etc.), sample filters, sample line
heaters, moisture traps, and other related
functions of the CEMS, as applicable. Do not
proceed until all parts of the CEMS are
functioning properly.
2. Obtain reference cylinder gases or calibration
cells that produce known responses at two
measurement points within the following
ranges:
Measurement Range
Measure-
ment
Point
1
2
Pollutant
Monitor
20-30%
of span
value
50-60%
of span
value
Diluent
Monitor
for CO2
5-8% by
volume
10-14%
by
volume
Diluent
Monitor
for O2
4-6% by
volume
8-12%
by
volume
Use certified cylinder gases, i.e.,
traceable to National Institute of
Standards and Technology (NIST)
gaseous standard reference material
(SRM) or NIST/EPA approved gas
manufacturer's certified reference
material (CRM) following EPA traceability
protocol Number 1. CRM's may be used
directly as alternative RA cylinder gases.
A list of gas manufacturers that have
prepared approved CRM's is available
from EPA.
b. Use calibration cells certified by the
manufacturer to produce a known
response in the CEMS, traceable to SRM
or CRM gases or reference methods (the
calibration cell certification procedure is
subject to approval of the
Administrator).
3. Operate each monitor in its normal sampling
mode as nearly as possible.
a. When using cylinder gases, pass the
cylinder gas through all filters,
scrubbers, conditioners, and other
monitor components used during normal
sampling and as much of the sampling
probe as practical.
b. When using calibration cells, do not by-
pass the CEMS components used in the
normal sampling mode during the RA
determination. These include light
sources, lenses, detectors, and
reference cells.
4. Challenge each monitor (both pollutant and
diluent, if applicable) with the reference
cylinder gases or calibration cells three times
at each point. Do not dilute gas from a
cylinder when challenging the CEMS. Allow
for a sufficient period of time to assure
adsorption-desorption reactions on the CEMS
surfaces have stabilized before taking
readings.
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9/3O/94; PS3-1
PERFORMANCE SPECIFICATIONS 3
O2 and CO2
A. Performance Specifications
1. Instrument Zero and Span: See PSP 2c.
2. Calibration Drift: £0.5% O2 or CO2 from
the reference value of the gas, gas cell, or
optical filter.
3. Relative Accuracy: (UsePDS3-1.) ^20%
of the mean value of the RM test data or
1.0% O2 or CO2, whichever is greater.
B. Test Procedure
1. Relative Accuracy Test. See PSP 2.
2. Reference Method. Unless otherwise
specified in an applicable subpart of the
regulations. Method 3B or any approved
alternative.
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9/3O/94: PS4-1
2.
3.
PERFORMANCE SPECIFICATIONS 4
Carbon Monoxide
A. Performance Specifications
1 . Instrument Zero and Span: See PSP 2c.
Calibration Drift: s5% of established span
value from the reference value of the
calibration gas, gas cell, or optical filter for
6 out of 7 test days (e.g., the established
span value is 1000 ppm for subpart J
affected facilities).
Relative Accuracy: (Use PDS 3-1)
of the mean value of the RM test data in
terms of the units of the emission standard
or ^5% of the applicable standard,
whichever is greater.
B. Test Procedure
1. Relative Accuracy Test. See PSP 2.
2. Reference Methods. Unless otherwise
specified in an applicable subpart of the
regulation. Method 10. When evaluating
nondispersive infrared continuous emission
analyzers, use the alternative interference
trap specified in section 10.1 of Method 1O.
Method 10A or 10B is an acceptable
alternative to Method 10.
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9/30/94: PS6-1
FIELD PERFORMANCE SPECIFICATION PROCEDURE 6
Continuous Emission Rate
A. Performance Specifications
1. Data Recorder Scale: SeePSP2c.
2. Calibration Drift.
a.
b.
Flow rate parameters: s3% of the
respective high-level value (HLV).
Other analyzers: See respective
performance specifications.
Relative Accuracy: (UsePDS3-1) £20% of
the mean value of the RM's test data in
terms of the units of the emission standard,
or 10% of the applicable standard, whichever
is greater.
B. Test Procedure
1. Relative Accuracy Test. See PS 2. For CD
of parameters that are selectively measured
by the GERMS (e.g., velocity pressure, flow
rate), use two analogous values (e.g. Low:
0-20% of full scale; High: 50-100% of full
scale). Introduce to the emission rate
monitor the reference signals (these need not
be certified).
2. Reference Methods. Unless otherwise
specified in an applicable subpart of the
regulations,
a. Flow rate: Methods 2, 2A, 2B, 2C, or
2D, as applicable.
b. Others: See appropriate regulations.
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9/30/94: PS7-1
PERFORMANCE SPECIFICATIONS 7
Hydrogen Sulfida
A. Performance Specifications B. Test Procedure
1. Instrument Zero and Span: See PSP 2c. 1. Relative Accuracy Test. See PSP 2.
2. Calibration Drift: :s5% of the established 2. Reference Method. Method 11, unless
span value from the reference value of the otherwise specified in an applicable subpart
calibration gas or reference source for 6 out of the regulation.
of 7 test days (e.g., the established span
value is 300 ppm for subpart J fuel gas
combustion devices).
3. Relative Accuracy: (UsePDS3-1) s20%of
the mean value of the RM test data in terms
of the units of the emission standard or 10% - ,, • - :
of the applicable standard, whichever is
greater.
•D.S. GOVERNMENT PRINTING OFFICE: 1996-750-001/41024
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