EPA-650/4-74-005-k
GUIDELINES FOR DEVELOPMENT
OF A QUALITY ASSURANCE PROGRAM:
VOLUME XI • DETERMINATION
OF BERYLLIUM EMISSIONS
FROM STATIONARY SOURCES
by
P. S.Wohlschlegel
F. Smith
D. E. Wagoner
Research Triangle Institute
Research Triangle Park, North Carolina 27709
Contract No. 68-02-1234
ROAP No. 26BGC
Program Element No. 1HA327
EPA Project Officer: Steven M. Bromberg
Environmental Monitoring and Support Laboratory
Office of Monitoring and Technical Support
Research Triangle Park, North Carolina 27711
Prepared for
U.S. Environmental Protection Agency
Office of Research and Development
Washington, D.C. 20460
April 1976
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EPA REVIEW NOTICE
This report has been reviewed by the Environmental Monitoring and
Support Laboratory, Research Triangle Park, North Carolina, of the
U. S. Environmental Protection Agency and approved for publication.
Approval does not signify that the contents necessarily reflect
the views and policies of the Environmental Protection Agency, nor
does mention of trade names or commercial products constitute en-
dorsement or recommendation for use.
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TABLE OF CONTENTS
Section Page
LIST OF FIGURES v
LIST OF TABLES vi
ABSTRACT vii
I INTRODUCTION i
II OPERATIONS MANUAL 5
2.0 GENERAL 6
2.1 APPARATUS SELECTION 10
2.2 EQUIPMENT CALIBRATION 19
2.3 PRESAMPLING PREPARATION 27
2.4 ON-SITE MEASUREMENTS 41
2.5 POSTSAMPLING OPERATIONS (Base Laboratory) 55
III MANUAL FOR FIELD TEAM SUPERVISOR 69
3.0 GENERAL 70
3.1 ASSESSMENT OF DATA 71
3.2 SUGGESTED PERFORMANCE CRITERIA 74
3.3 COLLECTION AND ANALYSIS OF INFORMATION TO
IDENTIFY TROUBLE 74
IV MANUAL FOR MANAGER OF GROUPS OF FIELD TEAMS 89
4.0 GENERAL 90
4.1 FUNCTIONAL ANALYSIS OF TEST METHOD 93
4.2 ACTION OPTIONS 102
4.3 PROCEDURES FOR PERFORMING A QUALITY AUDIT 107
4.4 DATA QUALITY ASSESSMENT 115
LIST OF REFERENCES 128
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TABLE OF CONTENTS (Continued)
A-
Section Page
APPENDIXES
APPENDIX A REFERENCE METHOD 132
APPENDIX B ILLUSTRATED USE OF NOMOGRAPHS 138
APPENDIX C ILLUSTRATED AUDIT PROCEDURES 144
APPENDIX D GLOSSARY OF SYMBOLS 150
APPENDIX E GLOSSARY OF TERMS 153
APPENDIX F CONVERSION FACTORS 155
IV
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LIST OF FIGURES
Figure No. Title Page
1. Operational flow chart of the measurement process. 7-9
2. Sampling train. 11
3. Dry gas meter and orifice meter calibration and calcu-
lation form. 23
4. Beryllium measurement checklist. 30-32
5. Sample data form for beryllium emissions determinations. 42-44
6. Sample calculation and data analysis form. 62-63
7. Sample control for the range, RG, of R replicates. 84
8. Sample control chart for the range, RG, of percent iso-
kinetic, I, sampling for three test; runs per field test. 85
9. Sample control chart for the average percent of isokinetic
sampling per field test. 86
10. Sample control chart for the measurement of working stan-
dard solutions. 88
11. Summary of data quality assurance program. 94
12. Added cost vs precision for selected action options for
mercury emission rate determinations. 106
13. Average cost vs audit level (n). 109
14. Sample form for recording audit data. 113
15. Example illustrating p < 0.10 and satisfactory data qual-
ity. 121
16. Example illustrating p > 0.10 and unsatisfactory data
quality. 121
17. Flow chart of the audit level selection process. 124
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LIST OF TABLES
Table No. Title Page
1. Suggested Performance Criteria. 75
2. Factors for Control Charts for the Range, RG. 83
3. Means and Variabilities of Parameters Affecting V ..• 102
4. Beryllium Emission Determination Checklist to be Used
by Auditor. 110-111
5. Computation of the Mean Difference, d, and Standard
Deviation of the Differences, s,. 118
6. Sample Plan Constants, k for P{Not Detecting a Lot with
Proportion P outside Limits L and U) <_ 0.1. 122
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ABSTRACT
Guidelines for the quality assurance of the determination of beryllium
emission rates from stationary sources by the Federal reference method
are presented. These include:
1. Good operating practices
2. Directions on how to assess performance and qualify data
3. Directions on how to identify trouble and improve data quality
4. Directions to permit design of auditing activities
The document is not a research report. It is designed for use by oper-
ating personnel.
This work was submitted in partial fulfillment of Contract Durham
68-02-1234 by Research Triangle Institute under the sponsorship of
the Environmental Protection Agency. Work was completed as of Febru-
ary 1976.
VII
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SECTION I
INTRODUCTION
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1 INTRODUCTION
This document presents guidelines for developing a quality assurance
program for Method 104, Determination of Beryllium Emissions from Stationary
Sources. This method was published by the Environmental Protection Agency
in the Federal Register, April 6, 1973, and is reproduced as appendix A
of this report for convenience of reference.
This document is divided into four sections:
Section I, Introduction. The introduction lists the overall
objectives of a quality assurance program and delineates the program
components necessary to accomplish the given objectives.
Section II, Operations Manual. This manual sets forth recommended
operating procedures to insure the collection of data of high quality,
and instructions for performing quality control checks designed to give an
indication or warning that invalid data or data of poor quality are being
collected, allowing for corrective action to be taken before future
measurements are made.
Section III, Manual for Field Team Supervisor. This manual contains
directions for assessing data quality on an intralaboratory basis and for
collecting the information necessary to detect and/or identify trouble.
Section IV, Manual for Manager of Groups of Field Teams. This
manual presents information relative to the test method (a functional
analysis to identify the important operations variables and factors,
and statistical properties of and procedures for carrying out auditing
procedures for an independent assessment of data quality).
The objectives of this ouality assurance program for Method 104 are to:
1. Minimize systematic errors (biases) and control random variability
(precision) within acceptable limits in the measurement process,
2. Provide routine indications for operating purposes of satisfactory
performance of personnel and/or equipment,
3. Provide for prompt detection and correction of conditions that
contribute to the collection of poor quality data, and
4. Collect and supply information necessary to describe the quality
of the data.
To accomplish the above objectives, a quality assurance program must con-
tain the following components:
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1. Recommended operating procedures,
2. Routine training of personnel and evaluation of performance of
personnel and equipment,
3. Routine monitoring of the variables and parameters that may have
a significant effect on data quality,
4. Development of statements and evidence to qualify data and detect
defects, and
5. Action strategies to increase the level of precision/accuracy in
the reported data.
Component (2) above will be treated for all the methods in the final report
of this contract.
Implementation of a properly designed quality assurance program should
enable measurement teams to achieve and maintain an acceptable level of
precision and accuracy in their stack gas composition measurements. It will
also allow a team to report an estimate of the precision of its measurements
for each source emissions test.
Variability in emission data derived from multiple tests conducted at
different times includes components of variation from:
1. Process conditions,
2. Equipment and personnel variation in field procedures, and
3. Equipment and personnel variation in the laboratory.
In many instances time variations in source output may be the most signi-
ficant factor in the total variability. The error resulting from this
component of variation is minimized by knowing the time characteristics of
the source output and collecting the gas sample at a rate proportional to
the stack gas velocity. The sampling period should span at least one com-
plete output cycle when possible. If the cycle is too long, either the
sample collection should be made during a portion of the cycle represent-
tative of the cycle average, or multiple samples should be collected and
averaged.
Quality assurance guidelines for Method 104 as presented here are designed
to insure the collection of data of acceptable quality by prevention,
detection, and quantification of equipment and personnel variations in both
the field and the laboratory through:
1. Recommended operating procedures as a preventive measure,
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2. Quality control checks for rapid detection of undesirable
performance, and
3. A quality audit to independently verify the quality of the data.
The scope of this document has been purposely limited to that of a
field and laboratory document. Additional background information is con-
tained in the final report under this contract.
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SECTION II
OPERATIONS MANUAL
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SECTION II OPERATIONS MNUAL
2.0 GENERAL
This manual sets forth recommended procedures for the determination
of beryllium (Be) emissions from stationary sources according to Method 104
(Method 104 is reproduced from the Federal Register and is included as
appendix A of this document). Quality control procedures and checks
designed to give an indication or warning that invalid or poor quality
data are being collected are written as part of the operating procedures
and are to be performed by the operator on a routine basis. In addition,
the performance of special quality control procedures and/or checks as
prescribed by the supervisor for assurance of data quality may be required
of the operator on special occasions.
The sequence of operations to be performed for the measurement process
is given in figure 1. Each operation or step in the method is identified
by a block. Quality checkpoints in the measurement process, for which
appropriate quality control limits are assigned, are represented by blocks
enclosed by heavy lines. Other quality checkpoints involve go/no-go checks
and/or subjective judgments by the test team members with proper guidelines
for decisionmaking spelled out in the procedures.
The precision/accuracy of data obtained from this method depends upon
equipment performance and the proficiency with which the operator performs
his various tasks. From equipment calibration through on-site measure-
ment, calculations, and data presentation, this method is susceptible to
a variety of errors. Detailed instructions are given for minimizing or
controlling equipment error, and procedures designed to minimize personnel
errors are recommended. Before using this document, the operator should
study Method 104 as reproduced in appendix A in detail. In addition, the
quality assurance documents of this series for Methods 2, 3, and 4 should
be read and followed.
It is assumed that all apparatus satisfies the reference method speci-
fications and that the manufacturer's recommendations will be followed
when using a particular piece of equipment. it is also assumed that the
analyst performing the analyses is trained in the operation of an atomic
absorption spectrometer utilizing a ^O/acetylene burner.
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APPARATUS SELECTION
1. SELECT EQUIPMENT ACCORDING TO THE
GUIDELINES GIVEN IN SUBSCC'i ION 2.1
FOR THE SOURCE TO BE TESTED.
EQUIPMENT CALIBRATION
2. CALIBRATE EQUIPMENT ACCORDING TO
SUBSECTION 2.2.
PRESAMPLING PREPARATION
3. OBTAIN PROCESS DATA, SELtCT/PRtPAPE
SAMPLING SITE, DETERMINE LOGISTICS
FOR PLACING EQUIPMENT ON-SITE, and
DETERMINE STACK CONDITIONS T , V ,
Bwo'ANDMd' S "
4. CHECK OUT SAMPLING TRAIN AND RELATED
COMPONENTS.
5. PACKAGE AND SHIP EQUIPMENT.
ON-SITE MEASUREMENTS
6. MOVEMENT OF EQUIPMENT TO SAMPLING
SITE AND SAMPLE RECOVERY AREA.
EQUIPMENT
SELECTION
\
/
EQl!]P,'-;ti!T
CALIBRATION
>
f
PRELIMINARY
SITE VISIT
(OPTIONAL)
\
/
APPARA"! US
CHECK
\
f
PACKAGE
EQUIPMENT
FOR
SHIPMENT
\
i
TRANSPORT
EQUIPMENT
TO SITE
Figure 1. Operational flow chart of the measurement process.
7
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7.
9.
10.
13.
PRELIMINARY MEASUREMENTS AND SETUP
WILL INCLUDE DUCT MEASUREMENT,
PERCENT H90, MOLECULAR WEIGHT (M ),
AND SAMPLE BOX LOGISTICS. s
DETERMINATION OF MAXIMUM AND MINIMUM
AP AND STACK GAS TEMPERATURE.
11.
12.
SET NOMOGRAPH UTILIZING THE PRELIMINARY
STACK GAS PARAMETERS [app. B].
ASSEMBLE AND LEAK-CHECK THE SAMPLING
TRAIN.
10
COLLECT A MINIMUM SAMPLE VOLUME OF
1.7 m3 (60 FT3). MAINTAIN ISOKINETIC
CONDITIONS DURING SAMPLING,
PERFORM FINAL LEAK CHECK OF THE ENTIRE
SAMPLING TRAIN.
11
12
OBTAIN SAMPLE FROM FILTER HOLDER, PROBE
NOZZLE AND IMPINGERS. MEASURE TOTAL
CONDENSATE (IMPINGER VOLUME AND SILICA
GEL WEIGHT GAIN) ACETONE, WATER
WASHES.
13
Figure 1. Operational flow chart of the measurement process—continued,
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14.
VALIDATE THE DATA BY CHECKING ALL
DATA SHEETS FOR COMPLETENESS.
15.
DISASSEMBLE AND INSPECT EQUIPMENT FOP
DAMAGE SUSTAINED BUT NOT DETECTED
DURING SAMPLING.
16. PACKAGE EQUIPMENT FOR RETURN TRIP TO
BASE LABORATORY.
POSTSAMPLING OPERATIONS
17. PREPARE SAMPLES FOR ANALYSIS.
18.
19.
20.
PREPARE WORKING ANALYTICAL
CURVE AND ANALYZE SAMPLES.
PERFORM NECESSARY CALCULATIONS TO
OBTAIN RATE OF BERYLLIUM EMISSIONS
AND PERCENT ISOKINETIC VARIATION.
FORWARD THE DATA FOR FURTHER INTERNAL
REVIEW OR TO THE USER.
14
15
16
17
18
19
20
DATA
VALIDATION
DISASSEMBLE
AND CHECK
EQUIPMENT
PACKAGE
EQUIPMENT
FOR SHIPMENT
PREPARE
SAMPLE
ANALYZE
SAMPLE
PERFORM
CALCULATIONS
REPORT
DATA
Figure 1. Operational flow chart of the measurement process—continued,
9
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2.1 APPARATUS SELECTION
A schematic of an assembled beryllium sampling train with all com-
ponents identified is shown in figure 2. Additional specifications,
criteria and/or design features as applicable are given in this section
to aid in the selection of equipment to insure the collection of data
of consistent quality. Procedures and, where applicable, limits for
acceptance checks are given. The descriptive title, identification num-
ber, if applicable, and the results of the acceptance check are recorded
in the receiving record file, dated, and signed by the individual perform-
ing the check.
2.1.1 Nozzle
2.1.1.1 Design Characteristics. Design of the nozzle, serving as an in-
terface between the sampling probe and the flue gas, should result in min-
imum disturbance of the flow pattern and sample gas characteristics. The
nozzle must be inert to the sample gases at the temperatures encountered in
the field. A new nozzle should be visually checked for identification, i.e.,
verify that it is the size, shape, and composition ordered. The nozzle
should also be checked for damage according to subsection 2.3.2.1(1), and
the nozzle tip diameter should be measured according to subsection 2.2.1.
A nozzle not satisfying any one of the above checks should be rejected.
The nozzle should be thin-walled with a beveled, sharp leading edge.
The bevel should be on the outside of the nozzle with a continuous, smooth
inside surface, i.e., a constant internal diameter must be preserved. A
button-hook-shaped nozzle (see figure 2) is required to allow for easy in-
sertion through small ports when sampling a thick-walled stack. For nozzles
greater than 1.90 cm (3/4 in) inside diameter, either an L-shaped or a
smooth, continuous 90-degree-bend nozzle is acceptable.
A set of three nozzles with 6.4 mm (1/4 in.), 9.5 mm (3/8 in.) and
13 mm (1/2 in.) inside diameters is recommended. Low stack velocities,
high moisture content, or high stack temperatures may require 5 mm (3/16
in.) or 15 mm (5/8 in.) diameter nozzles in order to achieve isokinetic
sampling. These larger sizes are not stock items but are available from
the manufacturer by special order.
10
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c:
ro
CD
C
Q.
(O
O)
S-
11
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The following specifications are recommended:
Material:
Temperatures below 871°C (1600°F)
Temperatures above 871°C (1600°F)
Temperatures up to 1371°C (2500°F)
Wall Thickness:
Angle of Taper:
Distance from Tip of Nozzle to
First Bend:
Inside Diameter:
Probe Nozzle Brush:
Seamless stainless steel (316)
tubing for 2- to 3-hour
exposures (ref. 1).
Quartz
Nickel-base alloys such as In-
conel (subject to severe cor-
rosion in the presence of
fluorine or chlorine)
1.65 mm (0.065 in.)
< 30°
At least two times the outside
nozzle diameter
Available in increments of 1.6
mm (1/16 in.)
See section 2.1.2.
2.1.2 Sampling Probe
The sampling probe should be made of borosilicate (Pyrex) glass
and encased in a steel sheath. The probe mu t be equipped with a heat-
ing system which will regulate the probe in 3t and exit temperatures to
avoid condensation and reevaporation of the moisture in the sample gas.
The probe material must be non-reactive with the gas constituents so as
not to introduce a bias into the analytical method. Because of this, a
knowledge of the stack gas composition and temperature is necessary to
select the correct probe. A new probe should be visually checked for identi-
fication, i.e., verify that it is the length and composition ordered. The
probe should be checked for cracks or breaks and leak-checked on a sampling
train as described in subsection 2.3.2.1(2). Also, the probe heating system
should be calibrated according to subsection 2.2.2. Any probe not satisfying
the acceptance check should be repaired, if possible or rejected.
A probe brush of an appropriate size and shape is necessary to clean
the probe liner and nozzle prior to and after sampling.
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The following specifications are suggested for the probe and probe
brush:
Probe Material:
Temperature < 480°C (900°F)
Thick-walled borosilicate glass or
quartz glass
Temperature < 900°C (1650°F) Quartz
Inside Diameter:
Heating System:
Temperature requirements
at the exit and within
.03 m (12 in) of the in-
let
1.3 cm (.5 in.) approximately
No greater than 93 + 14°C
(200 + 25°F) with a gas flow
of 0.021 m3/min (.75 ft3/min)
at room temperature
Note 1: The general requirement here is to prevent con-
densation prior to the filter during sampling.
In most cases a heating capacity to attain and
hold 93°C (200°F) at the exit end of the probe
under field conditions is sufficient. This gen-
eral requirement is tempered with the fact that
a membrane filter will collapse at - 107°C (225°F).
Probe Brush:
Bristles
Handles
Extensions
Nylon
Stainless steel wire
Inert material and at least as long
as the probe.
2.1.3 Filter Holder
The filter holder should be durable, easy to load, and leak-free in
normal applications. The design must be such that the filter material is
not torn as the holder is tightened. Also, the only flow through the hold-
er must be through the filter. New filter holders are checked visually for
cracks and sharp edges that could puncture or tear a filter. The filter
holder with a filter installed is placed in a sampling train and leak-
checked at about 380 mm Hg(15 in. Hg) vacuum as directed in subsection
2.4.3.5. Disassemble the holder and check the filter for punctures and
cuts. Reject the holder if any of the checks are negative and cannot be
13
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corrected.
The glass frit should always be cleaned before sampling according
to the manufacturer's recommendations. A standard cleaning procedure is
not applicable to all filter supports due to the variation in construct-
ion materials, but this construction material should allow the rinsing of
the interior surface of the filter holder and frit with 1:1 (V/V) hydro-
chloric acid and water. This wash should be followed with a final rinse
of distilled, deionized water.
Specifications for the filter holder are:
Material: Borosilicate (Pyrex) glass (other
materials may be used if approved
by the EPA administration)
Leak Sealant: Non-reactive to the stack gases
Filter Support Media: Glass frit
2.1.4 Filter Holder Box
The filter box must be equipped with a heating system and a temper-
ature monitoring device to regulate the temperature around the filter hold-
er during sampling if condensation is a problem. A dial-type thermometer
is recommended for monitoring the temperature.
Visually check the filter holder box for damage. Check the heating
system by calibrating it as directed in subsection 2.2.2. Reject the box
if it is damaged or if a temperature of 93 + 14°C (200 + 25°F) cannot
be maintained. The heating system and thermometer should meet the follow-
ing criteria:
Desired Temperature: At or above stack gas temperature but
not greater than 107°C (225°F)
Thermometer:
Accuracy + 3°C (+ 5.4°F)
Range 16° to 149°C (60° to 300°F)
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2.1.5 Impingers/Condenser/Container
The sample gas, having passed through the filter, must be cooled to
20°C (68°F) or less, and the moisture content of the stack gas measured.
To accomplish this task, four impingers are connected in series. The first,
third and fourth impingers (see figure 2) are of the modified Greenburg-
Smith design. The second impinger is of the Greenburg-Smith design with the
standard tip. Each impinger is checked visually for damage, such as breaks
or cracks, and manufacturing flaws, such as poorly shaped connections. The
container should be checked for damage and filled with water to see if it
leaks. Reject any item that is faulty.
The fourth impinger is required (charged with 200 g of preweighed sili-
ca gel) to remove moisture and to protect the vacuum pump and dry gas meter.
The reference method requires that the condensate trap be used to keep the
effluent gas temperature at 20 C (68 F) or less. Ice containers are avail-
able in commercial trains or can be fabricated from closed-pore expanded
polyethylene. The efficiency of the ice bath can be increased by the addi-
tion of salt.
Specifications are as follows:
Second Impinger: Tip must be large enough to allow
an impinger full of water to
drain in at least 6 to 8 seconds
(this avoids excessive pressure
drop in the sampling system)
Modified Impingers: Replace tip with a 13 mm (1/2 in,)
diameter glass tube extending
to within 13 mm from the bottom
of the flask
Joints: Inert, leak-free
2.1.6 Vacuum Pump
The vacuum pump must be capable of maintaining a constant flow rate
of the sample gas. Two types of vacuum pumps are commonly used: a modi-
fied sliding fiber vane pump and a diaphragm pump. The pump should be
leak-checked upon placing the pump in a sampling train such as in figure 2.
15
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With the pump running, adjust the system to 381 mm Hg (15 in. Hg) with the
inlet of the metering system closed. The dry gas meter dial should not
move after the adjustment has been made. The absence of valve float must
also be verified when a diaphragm pump and by-pass valve are used in the
sampling train.
Suggested specifications for the vacuum pump follow:
Desired Flow Rate: ,
At zero vacuum .11 m /min (4 ft /min)
At 508 mm Hg (20 in. Hg) .03 m3/min (1 ft3/min)
(with the pump outlet at or
near standard pressure, i.e.,
760 mm Hg)
Vacuum (Inlet Plugged): 380 mm Hg (15 in. Hg)
2.1.7 Dry Gas Meter
A new dry gas meter must be calibrated according to section 2.2.3.
It should meet the following requirement:
test meter) at«flow rates of
.008 to .034 m /min (0.3 to
Accuracy: +2 percent (compared to a wet
test meter)
.008 to .034
1.2 ft3/min)
2.1.8 Orifice Meter
Construction details of the orifice meter are given by Martin
(ref. 2). Significant design criteria are listed below. After visually in-
specting the orifice meter and the inclined manometer (or equivalent differ-
ential pressure gage) for damage, the instruments are assembled in a sam-
pling train as shown in figure 2 and calibrated as directed in subsection
2.2.3. If AH@ is outside the limits outlined below (and discussed in
subsection 2.2.3), the orifice meter should not be used with a commercially
available sampling nomograph. If AH@ is greater than 53 mm (2.1 in.) of
water, the orifice opening can be made larger (ref. 2) to lower AH@ to an
acceptable value. Low values of AH@ cannot be corrected. Values of AH@
16
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outside the above limits are acceptable when actual values are used to
calculate the relationship of AH to AP (i.e., a nomograph is not: used)
for each field test. The value of AH@ should be inscribed on or other-
wise affixed to the orifice meter box.
Specifications for this instrumentation include:
Orifice Diameter: 47 cm (3/16 in.)
AH@ at 21°C (70°F) and 46.7 + 6.4 mm H20 (1.84 + 0.25 in. H2
760 mm Hg (29.92 in. Hg):
Inclined Manometer Range: 0 to 203 or 250 mm HO (0 to 8 or
10 in. H20)
Inclined Portion of Scale:
Range 0 to 25 mm H20 (0 to 1 in. HO)
Divisions 0.25 mm HO (0.01 in. HO)
Vertical Portion of Scale:
Range 25 to 203 or 254 mm HO (1 to 8
or 10 in. H20)
Divisions 2.5 mm HO (0.1 in. HO)
2.1.9 The rmometers
Three dial-type thermometers are suitable for monitoring the inlet
and outlet temperatures of the dry gas meter and the sample gas as it
leaves the last impinger. All of the above temperatures can be monitored
by other means, such as a thermocouple or thermistor, but even then a
dial-type thermometer is recommended as a backup system.
Dial-type thermometers are easily damaged. Each new thermometer
should be visually checked for damage, such as a dented or bent stem. Each
thermometer is then calibrated as directed in subsection 2.2.4. A ther-
mometer should read within + 2,8°C (+ 5°F) of the true value when checked
in an ice water bath and/or + 3.9°C (+ 7°F) when checked In boiling water.
Damaged thermometers that cannot be calibrated should be rejected.
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Suggested thermometer data includes:
Range: 0 to 50°C (30° to 120°F)
Accuracy: +1% of absolute temperature
2.1.10 Vacuum Gage
The vacuum gage must be checked visually for damage and cali-
brated according to the directions in subsection 2.2.7. Any gage which
is damaged and/or too erratic to be calibrated is rejected.
A vacuum gage with the following specifications is adequate for
monitoring the sampling train vacuum:
Range: 0 to 76 cm Hg (0 to 30 in. Hg)
Divisions: 25 mm Hg (1 in. Hg)
2.1.11 Check Valve
A one-way check valve equipped with convenient-sized fittings is
required in the sampling train. Visually check for stripped thread and
blow alternately in each end to check for proper operation.
2.1.12 Valves
Two metering valves(1 ball and 1 needle) with convenient-sized
fittings are required in the sampling train. Locate the valves in the
sampling train and check for proper operation. Reject any valve that
cannot be adjusted over the desired operating range.
2.1.13 Stack Gas Velocity Measuring System
See the Quality Assurance Document of this series for Determination
of Stack Gas Velocity and Volumetric Flow Rate (type-S pitot tube) (ref. 3)
for a discussion of this system.
2.1.14 Stack Gas Temperature Measuring System
This system is treated as a subsystem of the velocity measuring
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system and is discussed in the document referenced in the preceding sub-
section (i.e., 2.1.13). A more recent discussion is also found in refer-
ence 4. The temperature measuring system must be installed so that the
sensor extends beyond the probe tip and does not touch metal. The posi-
tion should be about 1.9 to 2.5 cm (0.75 to 1 in.) from the pitot tube
and probe nozzle to avoid interference with the gas flow (fig. 2).
2.1.15 Stack Gas Pressure Measuring System
This system is treated as a subsystem of the velocity measuring
system and is discussed in the document referenced in subsection 2.1.13.
2.1.16 Filter Media
The filter media are not reusable and all new filters must be
visually checked for pinholes and tears. Any filter with a flaw is re-
jected. A Millipore AA, or equivalent, should be used. It is suggested
that a Whatman 41 filter be placed immediately against the downstream
side of the Millipore filter. In subsequent analysis, all filters must
be analyzed.
2.1.17 Atomic Absorption Spectrophotometer
An atomic absorption spectrophotometer equipped with a N-0/acety-
lene burner is required to measure the absorbance of beryllium at 234.8
nm (app. A). A Perkin-Elmer Model 303, or its equivalent, has been found
acceptable to accomplish the analysis. A standard containing 3 i^g/m& Be
should give an absorbance reading of approximately 0.4 absorbance units.
2.2 EQUIPMENT CALIBRATION
2.2.1 Nozzle Tip Diameter
The inside diameter of each new nozzle should be measured with a
micrometer to the nearest 0.025 mm (0.001 in.). Make three individual
measurements using different diameters (rotate about 45 each time) and
19
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calculate an average diameter. The range (i.e., difference in smallest
and largest values) of the 3 measurements should not exceed 0.1 mm
(0.004 in.). Number the nozzle and record the number and diameter of
the nozzle to the nearest 0.025 mm (0.001 in.) in the laboratory cali-
bration logbook. Etch or permanently fix the average diameter on the
nozzle. The nozzle should be checked visually for nicks, dents, corro-
sion, and out-of-roundness before each field test. Repair and recalibrate
prior to use if any damage is detected.
2.2.2 Probe Heater and Filter Box Calibration
Set up the sampling train with the probe connected to the sampling
3 3
box. With the nozzle detached and a flow rate of 0.021 m /min (0.75 ft /
min), profile the temperature in the probe as the heat is increased. De-
termine the inlet and outlet temperatures of the probe at a determined
minimum reference point corresponding to the stack gas temperature. If
the inlet and outlet temperatures are not greater than the stack gas
temperature, an adjustment must be made. If the probe is not equipped
to continuously monitor its temperature, the temperature should be plotted
as a function of percent of the power setting (ref. 5). It should be
noted that outside skin temperature is only a pseudo temperature and will
not be the actual temperature inside the probe.
A thermocouple with leads approximately 3 meters long can be used
with a potentiometer readout to profile the probe temperature (draw the
thermocouple along the inside length of the probe while maintaining a sam-
3
pie flow rate of 0.021 m /min. An alternate approach would be to use a
remote reading thermometer.
The filter box temperature can be monitored with a thermocouple,
thermistor, or dial-type thermometer. Adjust the voltage supply until
the box temperature is greater than the minimum stack gas temperature.
The temperature should not vary more than +14°c (+25°F) over a 2-hour
period. (Care should be taken as membrane filters deteriorate at tempera-
tures greater than 107°C).
20
-------
In all temperature calibrations, the reference points should be an
ice bath and boiling water (corrected for pressure).
The probe and filter box heating units should be calibrated when new,
after repairs, or any time the presampling check indicates that the system
is not functioning properly.
2.2.3 Dry Gas Meter and Orifice Meter
An initial check should be made of the sampling train to check for
"proper operation of the pump, dry gas meter, vacuum gage, and dry gas
meter thermometer(s). After the meter system components have been checked,
the vacuum system should be leak-checked. This is done by plugging the in-
let side of the metering system, pulling a vacuum of 635 mm Hg (25 in. of
3
Hg), and observing the dry test meter. If the leakage exceeds .00057 m /
3
min (0.02 ft /min), the leak(s) must be found and eliminated until the
above specification is satisfied.
A second qualitative leak check is required if a diaphragm pump is
used in the sampling train. One way to accomplish this check is to insert
a valve into the train between the pump and the dry gas meter. With
both the bypass valve and the inserted valve closed, pressurize the out-
let side of the pump to the capacity of the pump. After the initial surge
of bubbles in the impingers have subsided, all activity in the impingers
should cease. If this phenomenon does not occur then further testing should
be done to determine the source of the leak.
The dry gas meter should be calibrated when new, and a three-point
check performed prior to each field trip. (The postcalibration check for
one test serves as the precalibration check for the next test.) Calibra-
tion is performed by making simultaneous total volume measurements with a
calibrated wet test meter and the dry gas meter in the meter box. The
wet test meter must be of the proper capacity and accuracy. For commercial
o
sampling trains, the wet test meter capacity must be at least 0.028 m /rev
21
-------
3
(1 ft /rev) with an accuracy of + 1 percent. The wet test meter must be
{*_.
of the proper capacity; otherwise, at the higher flow rates the linkage
in the wet test meter will slip, producing an erratic correlation with the
volume recorded by the dry gas meter. The recommended calibration pro-
cedures are as follows:
1. If a diaphragm pump and bypass valve are used, check the sampling
system for valve float in the following manner (ref. 6). (The wet test
meter is not required while checking for valve float in this manner.)
a) Operate the sampling system at orifice readings between 1.3
mm and 130 mm H«0 (0.05 and 5 in. H?0). Initially, operate the system at
33
0.0212 m /min (0.75 ft /min) for 10 minutes before taking data.
b) Take data through the above range at flow rates of 0.002,
0.008, 0.014, 0.019, and 0.028 m3/min (0.1, 0.3, 0.5, 0.7, and 1.0 ft3/
min), once with the bypass closed and once with it completely open.
Time each setting for 1 minute. Record the AH setting (orifice reading)
and the initial and final volumes on the dry test meter.
c) Calculate AH@ from the two sets of data (see ref. 6).
AH@ * K AH (1)
v2
where K = 4.48 x 10 "" m in metric units, and K = 0.56 ft
in English units. Plot two curves (one with the bypass valve opened and
the other with it closed) of AH@ versus the volume_ (V) recorded by the
dry test meter. If the valves are floating, the two curves will not coin-
cide. Ideally, the curves should coincide and be horizontal over the
entire range; in practice, the curve will probably have a slight slope.
This initial check for valve float is performed once after building
or purchasing a sampling train aid must be repeated whenever a new pump
is installed in the system. Valve float, if present, must be corrected
(ref. 6).
22
-------
Date Calibration By
Barometric Pressure, Pu =
Dry Gas fleter No.
„ in.Hg
Wet Test Meter No.
Wet Test Meter Capacity
Date of Wet Test Keter
Calibration
Orifice
manometer
setting,
AH,
mm HoO
(in H?0)
2.5(0.1)
5.1(0.2)
7.6(0.3)
12.7(0.5)
25.4(1.0)
50.8(2.0)
101.6(3.0)
127,0(5.0)
203.2(8.0)
Gas vol .
v,ret test
meter
>~
m3(ft°)
0.071(2.5)
0.071(2.5)
0.071(2.5)
0.14 (5)
0.14 (5)
0.28 (10)
0.28 (10)
0.28 (10)
0.28 (10)
Gas vol .
dry gas
meter
vd>
m3(ft3)
Temperature
Wet test
Meter
V
°C(°F)
'
Dry gas meter
Inl et
tdi,
°C(°F)
Outlet
• tdo,
°C(°F)
Avg.
ld,
°C(°F)
Time
0,
min
Average
Y
AH (?
Calculations
AH
0.1
0.2
0.3
0.5
1.0
2.0
3.0
4.0
8.0
AH
13.6
0.00735
0.0147
0.0221
0.0368
0.0735
0.147
0.221
0.294
0.588
Y
Vw Pb ^d + 273>
/ £H I / \
Vd(Pb+ 13.6/ [\+ 273|
AH@
nmo AH R*w + 273) 012
.0012 AH W '
pb tW 273^ L vw J
Figure 3. Dry gas meter and orifice meter calibration and calculation form.
23
-------
2. Determination of AH@ and y is as follows:
a) The wet test meter is placed upstream of the sampling system
with its outlet connected to the inlet (sample umbilical connection) of
the meter box (ref. 5). These connections must be leak-free.
b) Operate the pump for 15 minutes to warm up the pump and wet
3
the surface of the wet test meter (~ 0.021 m /min).
c) Collect and record (as shown in figure 3) the calibration
data by setting AH on the orifice manometer and letting a given volume of
air pass through the wet test meter (the larger the volume, the greater
the accuracy). Repeat the above procedures until the data are collected.
Always have the bypass valve open. A stop watch or laboratory timer is
used to record the elapsed time (6) of the calibration.
The symbols in figure 3 are:
3 3
V = Gas volume passing through the wet test meter, m (ft )
w
3 3
V. = Gas volume passing through the dry test meter, m (ft )
d
t = Temperature of the gas in the wet test meter, C ( F)
w
t .= Temperature of the inlet gas of the dry test meter, C ( F)
d.
i
t = Temperature of the outlet gas of the dry test meter, C ( F)
o
t, = Average temperature of the gas in the dry test meter, obtained
by the average of t , and t , , C ( F)
i o
9 = Time of calibration run, minutes
AH = Orifice manometer setting, with a resultant orifice meter pressure
drop, mm H-O (in. H?0)
£ tL.
y = Ratio of volumetric measurement by wet test meter to dry test
meter. Tolerance = + 0.02
P, = Barometric pressure, mm Hg (in. Hg)
AH@ = Orifice meter pressure differential that gives a flow rate of
0.021 m3/min (0.75 ft /min), mm HO (in. HO). Tolerance = + 3.8
mm HO (0.15 in. HO)
24
-------
d) Calculate y and AH@ for each orifice manometer setting and
record on the calibration sheet as depicted in figure 3. The value of
Y should be 1.0 + 0.02; adjust the linkage of the dry test meter (if
needed) as directed by the manufacturer until this tolerance is obtained.
Plot curves of AH@ versus AH (orifice manometer setting in mm of water).
The value of AH@ should be 46.7 + 6.4 mm H20 (1.84 + 0.25 in. H20) with
a variability no greater than + 3.8 mm HO (0.15 in. HO) over the range
of 13 to 203 mm HO (0.5 to 8 in. HO) of water across the orifice. If
this is not obtained, adjust the orifice opening or replace the orifice
as directed in reference 2 and recalibrate.
3
The value of AH@ obtained at a flow rate of 0.021 m /min is etched
on the orifice meter. The completed form in figure 3 is filed in the
calibration log book.
2.2.4 Thermometers
Thermometers are calibrated against a mercury-in-glass thermome-
ter with at least 1 C divisions at two or three points as applicable.
The points are an ice bath, room temperature, and boiling water (cor-
rected for pressure). A thermometer should be calibrated when new and
checked at one point before each field test. A calibration curve should
be constructed if the test thermometer does not read within + 1 percent
of the mercury-in-glass thermometer (both readings in K).
Record all calibration data in the calibration logbook.
2.2.5 Stack Gas Velocity Measuring System
The procedure for calibrating a type-S pitot tube is given in the
Quality Assurance Document of this series applicable to Method 2, Deter-
mination of Stack Gas Velocity and Volumetric Flow Rate (type-S Pitot
Tube) (ref. 3), with one exception: the type-S pitot tube should be cal-
ibrated in the same configuration that it is to be used or the free space
between the nozzle and pitot tube must be at least 1.9 cm (0.75 in.). If
the sampling train is designed for sampling at higher than normal flow rates
25
-------
thereby requiring the use of larger size nozzles, the free space shall
be set on the largest sized nozzle to be used.
The coefficient should not vary more than + 5 percent of the average
over the operating range. If the average coefficient is outside the
range of 0.83 to 0.87 and a sampling nomograph is used in maintaining iso-
kinetic conditions, corrections must be made as directed in subsection
2.4.3.1.
2.2.6 Stack Gas Temperature Measuring System
A temperature-measuring device attachable to a pitot tube and capable
of measuring the stack gas temperature to within 1.5 percent of the minimum
absolute stack gas temperature is required. A high-quality mercury bulb
thermometer calibrated at ice water and boiling water (corrected for local
pressure) temperatures and readable to the nearest .3 C (IF) is an accept-
able laboratory standard for calibration of temperature-measuring devices.
The calibration procedure is contained in section 2.1.2.2 of the Quality
Assurance Document of this series for Method 2, Determination of Stack Gas
Velocity and Volumetric Flow Rate (type-S Pitot Tube) (ref. 3).
2.2.7 Barometer
The field barometer should be checked against a mercury barometer
before each field test. If the two differ by more than +5.1 mm Hg
(0.2 in. Hg) adjust, calibrate, or replace the field barometer as appli-
cable. Record the results in the calibration logbook. Date and sign
the entry.
2.2.8 Atomic Absorption Spectrophotometer
A Spectrophotometer is required which is capable of measuring the
absorption at 234.8 nm. A Perkin Elmer Model 303 or equivalent equipped
with a N_0 acetylene burner is recommended.
26
-------
2.2.9 Orsat Analyzer (optional)
A standard Orsat analyzer may be used at combustion sources for the
determination of stack gas molecular weight. See the document of this
series entitled "Gas Analysis for Carbon Dioxide, Excess Air and Dry Mo-
lecular Weight", based on Method 3 (ref. 7).
2.3 PRESAMPLING PREPARATION
2.3.1 Preliminary Site Visit (optional)
The main purpose of a preliminary site visit is to gather informa-
tion to design and implement an efficient source test. Prior preparation
will result in the prevention of unwarranted loss of time, expenses, and
injury to test and/or plant personnel. A test plan conceived from a
comprehensive set of parameters will result in more precise and accurate re-
sults. This preliminary investigation (on-site) is optional and not a
requirement. An experienced test group can, in most cases, obtain suf-
ficient information on the source through communications with the plant
engineer. The information should include pictures (diagrams) of the
facilities.
2.3.1.1 Process (Background data on process and controls). It is recom-
mended that the tester become familiar with the operation of the plant
before a preliminary site visit is made. Data from similar operations
that have been tested should be reviewed if they are available and appli-
cable.
2.3.1.2 Sampling Site Preparedness. The management of each facility
tested should provide an individual who understands the plant process and
has the authority to make decisions concerning plant operation to work
with the test team. This would include decisions concerning whether the
plant would be operated at normal conditions or at rated capacity. This
individual or individuals will supervise installation of ports, sampling
platform, and electrical power. If the above installations are already
27
-------
in existence, they should be examined for their suitability for obtaining
a valid test and for overall safety conditions (ref. 8). If the sampling
platform, port size, and locations are sufficient, the diameter, area of
the stack^ and wall thickness should be determined. If ports have to be
installed, specify at least 8 cm (3 in.) ports with plugs. Ten centimeter
(4 in.) ports are preferred. Port locations should be based upon Method 1
of the Federal Register (ref. 9). One electric drop should be available
at the test facility with 120-volt, 20-ampere service.
2.3.1.3 Stack Gas Conditions. The following can be determined on the
initial site survey, either by measurement or estimation:
1. T = Approximate stack gas temperature
avg
2. P = Static pressure (positive or negative)
s
3. AP and AP . - Maximum and minimum velocity pressure heads
4. B = Approximate moisture content
wo
5. M = Molecular weight calculated from approximate
S
gas constituent concentrations.
The above parameters can be roughly determined using an inclined
manometer with a range of 0-127 mm HO (0-5 in. HO), a type-S pitot tube,
and a manual thermometer or thermocouple attached to the pitot tube with a
potentiometric readout device. The moisture content (approximate) can be
determined by the wet bulb-dry bulb method, and the gaseous constituents
by hand-held indicator kits. Nomographs are useful in checking and esti-
mating the preliminary required data (ref. 10).
2.3.1.4 Methods and Equipment for Transporting Apparatus to Test Site.
Ropes, block and tackle, and other hoisting equipment should belong in the
repertoire of any stack sampler. The initial site visit should include
a preconceived plan between plant personnel and tester on how the equip-
ment can best be transported to the sampling site. Electric forklifts
should be utilized when at all possible. In addition to the above, it
is recommended, when permissible, that pictures be taken of the hoisting
28
-------
and sampling areas, so that any further correspondence (either by
letter or telephone) will be clarified.
2.3.2 Apparatus Check
Each item to be used should be visually checked for damage and/or
excessive wear before each field test. Items should be repaired or re-
placed if judged to be unsuitable for use by the visual inspection.
Figure 4 shows a checklist for the three phases of a field test. It
is meant to serve as an aid to the individuals concerned with procuring
and checking the required equipment, and as a means for readily determin-
ing the equipment status at any point: in time. The completed form should
be dated, signed by the field crew supervisor, and filed in the operational
logbook upon completion of a field test. This includes initiating the
replacement of worn or damaged items of equipment. Procedures for perform-
ing the checks are given in the appropriate subsections of this operations
manual; a check is placed in the proper row and column of the checklist
as the check/operation is completed.
In addition to a visual check, the following performance and/or cal-
ibration checks are performed before each field test.
2.3.2.1 Sampling Train. The design specifications of the particulate
sampling train used by EPA are described in APTD-0581 (ref. 2). Commer-
cial models of this train are available. Each individual train must: be
examined to see if it is in compliance with the specifications in APTD-
0581 (ref. 2) or its equivalent. In addition, the Office of Air Programs
Publication No. APTD-0576 is a valuable source (ref. 5).
1. Nozzle. The nozzle is visually checked for damage, especially
the sharp leading edge, and the tip opening is checked for out-of-round-
ness. If there is any sign of damage or out-of-roundness of the tip, the
nozzle diameter should be calibrated according to subsection 2.2.1. Clean
the nozzle by scrubbing with tap water, followed with a wash (2 hours) in
1:1 (V/V) hydrochloric acid-water wash and rinsed with distilled, deionized
water. An alternate cleaning procedure when rust and/or organic materials
29
-------
PRESAMPUNG CHECKLIST
TEST SITE
CREW SUPERVISOR
DATE
Date and Initial Appropriate Slock as Procedure is Completed
ITEM
SAMPLING PREPARATION AND
SAMPLING APPARATUS:
1. Nozzle
2. Probe
3. Filter Holder
4. Filter Holder Box
5. Filters
6. Thermometers
7. Impinqers
8. Vacuum Pump
9. Dry Gas Meter
10. Orifice Meter
11. Inclined Manometer
12. Vacuum Gage
13. Check Valve
14. Meterinq Val ves
15. By-Pass Valve
16. Type-S Pitot Tube
17. Connectinq Lines
18. Barometer
19. Inclined Manometer
?0. Stack Temperature Measuring
System
SAMPLE RECOVERY:
21 . Probe Brush
12. Storage Containers
23. Graduated Cylinders
24. Wash Bottles
REAGENTS :
25. Silica Gel
26. Distilled Water
27. Crushed Ice
28. Filters
DOCUMENTATION:
29. Data Sheets
CALCULATIONS & DATA VALIDATION:
30. Samplinq Nomograph
31. Combustion Nomographs
32. Pocket Calculator
TOOLS AND EQUIPMENT:
33. Transportation Equipment
34. Safety Equipment
35. Tools and Spare Parts
36. Miscellaneous Supplies
Visual Check
for- Damage
Leak Check
Sampl ing Train
?999999W999'
KX>OC>Q<
>oo
^x566<^XXy>6<3
SSSSSS888S
CKXXXXXXXXX^
xxxxxxxxxxx>
6^XXXXXXXXXX
VYvvvvvyyvsX
XXKXXXXXXXX?
OOCKXXXXXXXX
(XJXXXXXXXXXXf
r?yyyyvvyyy>X<
^SSSSSSSSSS
XwsXXXXXX?"*
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Performance/
Calib. Check
S888888888
OOO
>666660^XXX
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;xx*xw?gw
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Figure 4. Beryllium measurement checklist
30
-------
TEST
ON-SITE MEASUREMENT CHECKLIST
CREW SUPERVISOR
DATE _
Date and Initial Appropriate Block as Procedure is Completed
ITEM
SAMPLING PREPARATION AND
SAMPLING APPARATUS:
1. Nozzle
2. Probe .
3. Filter Holder
4. Filter Holder Box
5. Filters
6. Thermometers
7. Impingers
8. Vacuum Pump
9. Dry Gas Meter
10. Orifice Meter
11 . Inclined Manometer
12. Vacuum Gage
13. Check Valve
14. Metering Valves
15. By-Pass Valve
16. Type-S Pitot Tube
17. Connecting Lines
18. Barometer
19. Inclined Manometer
20. Stack Temperature Measuring
System
SAMPLE RECOVERY:
21. Probe Brush
22. Storage Containers
23. Graduated Cylinders
24. Wash Bottles
REAGENTS:
25. Silica Gel
26. Distilled Water
27. Crushed Ice
28. Filters
DOCUMENTATION:
29. Data Sheets
CALCULATIONS & DATA VALIDATION:
30. Sampling Nomograph
31. Combustion Nomographs
32. Pocket Calculator
TOOLS AND EQUIPMENT:
33. Transportation Eguipment
34. Safety Eguipment
35. Tools and Spare Parts
36. Miscellaneous Supplies
Unpacked or
Purchased On-Site
Assembled and
Performance Checked
1
<:
C£.
CD
^.
— !
<:
UO
^
c_;
LU
3C
00000<
X»6O6666
•wywwyyxxXXX
xxx^?W3«5sXXXXX
>99vXXxxxVxxyS6^
xX?vvvvvvvvvyys
KXXXXXX>00
C>OCXX>O6666666566665x5
Dissasembled and
Packaged for Shipment
^V9999<^999QOOOO<
Figure 4. Beryllium measurement checklist (continued)
31
-------
POST-SAMPLING CHECKLIST
TEST SITE
CREW SUPERVISOR
DATE
Date and Initial Appropriate Block as Procedure is Completed
ITEM
SAMPLING PREPARATION AND
SAMPLING APPARATUS:
1. Nozzle
2. Probe
3. Filter Holder
4. Filter Holder Box
5. Filters
6. Thermometers
7. Impinqers
8. Vacuum Pump
9, Dry Gas Meter
10. Orifice Meter
11. Inclined Manometer
12. Vacuum Gage
13. Check Valve
14. Meterinq Valves
15. By-Pass Valve
16. Type-S Pitot Tube
17. Connectinq Lines
18. Barometer
19. Inclined Manometer
20. Stack Temperature Measuring System
SAMPLE RECOVERY:
21 . Probe Brush
22- Storage Containers
23. Graduated Cylinders
24. Wash Bottles
REAGENTS:
25. Silica Gel
26. Distilled Water
27. Crushed Ice
28. Filters
DOCUMENTATION:
29. Data Sheets
CALCULATIONS AND DATA VALIDATION:
30. Sampling Nomograph
31. Combustion Nomographs
32. Pocket Calculator
TOOLS AND EQUIPMENT:
33. Transportation Equipment
34. Safety Equipment
35. Tools and Spare Parts
36. Miscellaneous Supplies
Inspect for Damage
and/or Excess Wear
9sXX^9ysS^XXX><
XXXXXXX?WQV?W
oood
Accepted for
Future Use
^^xxxxxxxxxx^
("v''v"V"V ^/ v y "y y x X X X ^
To Be
Replaced
o
-------
are present is to precede the tap water wash by soaking the nozzle in sul-
furic acid. At all times protect the knife edge from being damaged. A
damaged knife edge must be repaired or the nozzle discarded. Minor repairs
may be done by the tester with a file and assorted tools. An alternate
approach, especially with major damage, is to send the nozzle to a quali-
fied machine shop.
2. Probe. Check the probe in the following manner:
a) Disassemble probe and check for breakage of inner liner or
damage to other parts of probe.
b) Clean all metal parts with acetone.
c) Reassemble probe and clean inner liner with brush, using
tap water and acetone. In extreme cases, the glass liner can be cleaned
with a stronger cleansing agent. Following the initial wash, the glass
liner (interior surface) should be soaked for 2 hours in a 1:1 (V/V) hy-
drochloric acid-water wash. The final rinse should be with distilled,
deionized water and acetone (reagent grade) that has been analyzed for Be.
The acid wash is easily accomplished by placing a glass female socket
over the end of the male outlet of the probe. The acid is added to the
inlet side, and the probe is allowed to stand vertically for the duration
of the wash period.
d) Check to see if probe will heat to the desired temperature
to prevent condensation. The probe temperature can be profiled with
a remote reading thermometer or with a thermocouple with a readout
device.
e) The probe should be sealed on the nozzle side and checked
for leaks at a vacuum of 380 mm Hg (15 in. Hg).
f) Cover the open ends of the probe with serum caps or equiva-
lent.
At temperatures greater than 260 C (500 F) or if asbestos string has
been used as a gasket between the glass probe and the union holding the
nozzle to the probe and probe sheath, the probability of leakage exists.
Most stacks have a negative pressure; therefore, a leak would introduce
33
-------
diluent air into the system and result in a low bias. This problem can
be eliminated by:
a) Sealing the sheath from the outside air with a rubber stopper
or its equivalent (ref. 2), and
b) Drilling a 0.3 mm (1/8 in.) hole in the sheath on the opposite
side of the pitot tube just behind the nut.
This modification also prevents "out" gases resulting from deterioration
of the probe from contaminating the stack sample (ref. 11).
3. Sampling Train Leak-Check. Assemble the sampling train as shown
in figure 2. With all the impingers empty, leak-check the sampling train
by plugging the probe inlet and pulling a vacuum of 380 mm Hg (15 in. Hg).
Leaks greater than 2 percent of the sampling rate (i.e., about 0.0006 m /
3
min or 0.02 ft /min) as indicated by the dry gas meter should be found
and corrected before continuing.
Note 2: The leak-check cannot be made through the probe if
asbestos string is used in the gasket. In this case,
leak-check as described in 2.4.3.6. Following this
initial leak-check at 280 mm (15 in.) Hg vacuum,
connect the probe and leak-check at 25 mm (1.0 in.)
Hg vacuum. A leakage rate greater than 0.00057 m3/
min (0.02 ft^/min) is unacceptable.
Note 3; If using stopcock grease, use only the high temper-
ature type.
2.3.2.2 Dry Gas Meter Calibration Check. After the sampling train leak-
check has been satisfactorily completed in the system as directed, follow
the same procedure as used in calibrating the dry gas meter (see subsec.
2.2.3); make runs at AH settings equivalent to flow rates of about 0.01,
0.02, and 0.03 m /min (0.50, 0.75, and 1.0 ft3/min). Calculate Y for
each run (see equation in fig. 3). If Y at either one of the three points
falls outside the range of 1.0 + 0.02, the dry gas meter should be (1) ad-
justed and recalibrated, (2) recalibrated and a calibration curve con-
structed, or (3) replaced. Record the results in the calibration log-
book. Date and sign the entry.
2.3.2.3 Needle Valve(s) Check. The needle valve(s) should be disassem-
bled and cleaned or replaced at any sign of erratic flow-rate behavior
34
-------
attributable to the needle valve as observed during the above checks or
when unable to regulate the flow rate at desired levels. Document the
adequacy of the needle valve with a check mark in the performance check
column of the presampling checklist (figure 4).
2.3.2.4 Probe Heater Check. Connect the probe heating system. The probe
should become uniformly hot to the touch within a few minutes after being
turned on. If it does not heat properly, repair or replace as necessary.
Document as part of the sampling probe performance check for the presam-
pling phase (figure 4).
2.3.2.5 Filter Holder Box Heater. Check the heating system to verify
that a temperature sufficient to prevent condensation can be maintained
for at least 1 hour at laboratory conditions.
2.3.2.6 Barometer. The barometer is checked as a part of the stack gas
pressure measuring system in the Quality Assurance Document of this series
applicable to Method 2 (ref. 3).
2.3.2.7 Stack Gas Velocity Measuring System. Check the velocity measur-
ing system according to the directions given in the Quality Assurance
Document of this series for Method 2. Visual and performance checks are
documented in figure 4 under visual check for damage and performance and/
or calibration check for the presampling phase of the field test. If a
calibration check is made, it should be recorded, dated, and signed in
the calibration logbook.
2.3.2.8 Filter. The filter should be permanently numbered along its
outside edge, where particulates (Be) will not be collected, for identifi-
cation. Each lot of filters should be checked by the analytical technique
for background concentration of Be. Results of the check are recorded in
the laboratory logbook. The lot of filters should be rejected if the
background Be is above the minimum detectable of the analytical technique.
Filters are placed in inert containers and sealed with the filter number
written on the container.
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2.3.3 Package Equipment for Shipment
An important aspect of any source testing method in terms of logis-
tics, time of sampling, and quality of data is the packing of equipment
with regard to (1) accessibility in the field, (2) ease of movement on
site, and (3) optimum functioning of measurement devices in the field.
Equipment should be packed under the assumption that it will receive se-
vere treatment during shipping and field operation.
2.3.3.1 Type-S Pitot Tube and Probe. Pack the pitot tube and probe in
a case protected by expanded polyethylene or other suitable packing ma-
terial. An ideal container is a wooden case or equivalent lined with ex-
panded polyethylene in which separate compartments are cut to hold the
individual devices. It is also recommended that inserts for the individual
nozzles be provided. The case should have handles that can withstand
hoisting and should be rigid enough to prevent bending or twisting of the
devices during shipping and handling.
2.3.2.2 Differential Pressure Gage (Dual Inclined Manometer). Always
close all valves on the pressure gage. Pack it in a suitable case for
shipment. Spare parts, such as 0-rings and gage oil (dual inclined
manometer), should also be packed.
2.3.3.3 Stack Temperature Measuring Device. The temperature-measuring
device (thermocouple, thermistor, remote reading thermometer, etc.) should
be protected from breakage; i.e., placed in a tube or a suitable shipping
container. If the device is an integral part of the pitot tube, it can be
shipped in the type-S pitot tube shipping case.
2.3.3.4 Barometer. The barometer should be packed in a shock-mounted
(spring system) carrying case.
2.3.3.5 Pitot Tube Lines and Sample Line (Umbilical). All pitot tube lines
and sample lines should be coiled to utilize the smallest amount of space.
The ends should be connected together and sealed to prevent dust and dirt
from impairing their operation. For shipment all lines should be stored
in a case (foot locker) for protection and portability.
36
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2.3.3.6 Glassware (Impingers, U-Joints, etc.). A word of caution is needed
in the use of glassware. It is expensive and fragile, but with sensible
handling and packing its failure rate and resultant costs are minimal. Gen-
erally, breakage of glassware occurs during packing and movement to the
sampling facility. It is recommended that glass impingers be packed in a
suitable case with approximate dimensions of 50 x 50 x 50 cm (20 x 20 x 20
in.) with a three-tiered layer of expanded polyethylene in which holes are
cut to hold the glass impingers. At least 13 mm (1/2 in.) of cushioning
material should be placed in both top and bottom of the shipping case (ref.
12). A separate case lined with expanded polyethylene, with layers of 80 mm
(3 in.) polyethylene, can be used to carry the rest of the individual glass
joints, filter holders, and filters. One major point to consider in ship-
ping cases is the construction materials. Durable containers, although more
expensive to build, are the most cost effective in the long term. A poorly
constructed shipping case of inferior material will quickly deteriorate.
2.3.3.7 Metering System (Meter Box Assembly). A standard (commercial unit:
including pump, vacuum gage, dry test meter, inclined manometer, etc., are
contained in one meter box. This meter box should be placed in a shipping
container lined with a cushioning material such as polyurethane.
If the vacuum pump is not integral to the meter box, it should be
packed in a shipping container unless its housing is sufficient for travel.
Additional pump oil should be packed with the pump if oil is required for
its operation.
2.3.3.8 Sampling and Sample Recovery. Sampling and sample recovery
equipment include the following:
1. Probe brush (commercial unit) or fabricated tube as long as the
probe.
2. Glass wash bottles.
3. Leakless glass storage containers (500 m£) for collected samples
and retention of blanks.
4. Graduated cylinder (250 m£).
37
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5. Silica gel: indicating type, 6-16 mesh, dried at 175°C (350°F)
for 2 hours in preweighed lots of approximately 200 g (two/test).
6. Ice chest and water container.
7. Acetone: AA (atomic absorption) grade.
8. Distilled, deionized water.
9. Wash acid: 1:1 (V/V) hydrochloric acid-water solution.
All glass bottles or glass storage containers should be packed with
cushioning material at the top and bottom of the case with some form of
divider to separate the components. One shipping case can contain the
acetone, preweighed silica gel ( plastic, for ~ 300 m£), glass wash bot-
tles, graduated cylinders, and probe brush. A water container and ice
chest can be shipped as is. It is recommended in certain cases that these
two items be purchased on-site. A general rule of thumb in source test-
ing is "when possible, always carry a spare."
Prior to the field test all glass storage bottles and the graduated
cylinders must be cleaned in 1:1 (V/V) hydrochloric acid water and rinsed
with distilled, deionized water.
2.3.3.9 Source Sampling Tools and Equipment. The need for specific
tools and equipment will vary from test to test. A listing of the most
frequently used tools and equipment is given below:
1. Equipment Transportation
(a) A lightweight handtruck that can be used to transport cases
and that can be converted to a four-wheel cart for supporting the meter
box control unit.
(b) A 13 mm (1/2 in.) continuous filament nylon rope with large-
throat snap hook and snatch block for raising and lowering equipment on
stacks and roofs.
(c) Tarpaulin or plastic to protect equipment in case of rain.
Sash cord, 6 mm (1/4 in.) diameter for securing equipment and tarpaulin.
(d) One canvas bucket, useful for transporting small items up
and down the stack.
38
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2. Safety Equipment
a) Safety harness with nylon and steel lanyards, large-throat
snap hooks for use with lanyards for hooking over guard rails or safety
line on stack.
b) A fail-safe climbing hook for use with climbing harness
when climbing ladders having a safety cable.
c) Hard hats with chin straps and winter liners, gas masks,
safety glasses and/or safety goggles, and first aid kit.
d) Protective clothing, including the following: appropriate
suits for both heat and cold, gloves (both asbestos arid cloth) , arid
steel—toed shoes.
e) Steel cable, 5 mm (3/16 in.) diameter, with thimbles, cable
clips, and turn-buckles. These are required for installing a safety line
or for securing equipment to the stack structure.
3. Tools and Spare Parts
a) Electrical and Power Equipment
1) Circular saw
2) Variable voltage transformer
3) Variable speed electrical drill and bits
4) Ammeter-voltmeter-ohmeter (VOM)
5) Extension cords: Light (No. 14 AWG) ., 2 cords x 8 m
(25 ft) long
6) 2-3 wire electrical adapters
7) 3-wire electrical triple taps
8) Thermocouple extension wire
9) Thermocouple pluga
10) Fuses
11) Electrical wire
b) Tools
1) Tool boxes (one large, one small)
2) Screwdrivers
(a) One set flat blade
(b) One set Phillips
39
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3) C-clamps (2): 150 mm (6 in.), 80 mm (3 in.)
c) Wrenches
1) Open end set: 6 to 25 mm (1/4 to 1 in.)
2) Adjustables: 305 mm (12 in.), 150 mm (6 in.)
3) One chain wrench
4) One 305 mm (12 in.) pipe wrench
5) One Allen wrench set
d) Miscellaneous
1) Silicone sealer
2) Silicone vacuum grease (high temperature)
3) Pump oil
4) Manometers (gage oil)
5) Antiseize compound
6) Pipe fittings
7) Dry cell batteries
8) Flashlight
9) Valves
10) Dial thermometers, 150 mm (6 in.) and 915 mm (36 in.)
11) Vacuum gage
12) SS tubing: 6 mm (1/4 in.), 9 mm (3/8 in.), 13 mm (1/2 in.);
short lengths
13) Heavy-duty wire (telephone type)
14) Adjustable packing gland
2.3.3.10 Data Recording. Pack one large briefcase with at least the
following:
1. Nomograph for maintaining isokinetic conditions,
2. Data sheets or data notebook,
3. Carbon paper,
4. Slide rule or electronic calculator,
5. Psychrometric charts,
6. Combustion nomographs (ref. 10),
40
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7. Pencils, pens, and
8. Calibration data, AH@, y» and Cp,
2.4 ON-SITE MEASUREMENTS
The on-site measurement activities include transporting the equip-
ment to the test site, unpacking and assembling the equipment, confirm-
ing duct measurements and traverse points (such preliminary determinations
should be accomplished in a site visit), molecular weight determinations
of the stack gas, moisture content, setting of the nomograph, sampling,
sampling recovery, and data recording. A sample data form is shown in
figure 5. Every quantitative stack or measurement data should be recorded
on such a form.
2.4.1 Transport of Equipment to the Sampling Site
The most efficient means of transporting or moving the equipment
from floor level to the sampling site (as decided during the preliminary
site visit) should be used to place the equipment on-site. Care should
be exercised against damaging the test equipment during the moving phase.
Utilization of plant personnel or equipment (winches and forklifts) in
moving the sampling gear is highly recommended.
2.4.2 Preliminary Measurements and Setup
2.4.2.1 Duct Measurement. Measure the duct dimensions and determine the
number of traverse points according to Method 104 (appendix A) or accord-
ing to the latest revision of Method 1 which is contained in the Final
Report for this contract.
2.4.2.2 Sample Box Logistics. Once the sampling points are selected and
the probe has been marke^d with either a china marker or heat-bonding fiber-
glass tape (<370°C - 700°F) the most efficient setup for the sample box
must be determined. A poor choice will create a backbreaking and time-
consuming sampling experience. Two rail systems exist for sampling, (mono-
rails and duorails) in which the sampling box moves on a track(s). Each
41
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TEST IDENTIFICATION
PLANT NAME _ _"' TEAM SUPERVISOR
LOCATION ___ DATE OF TEST
SOURCE _____ TIME
OPERATOR(S) _ ___________ RUN NO.
SAMPLING SITE "IDENTIFICATION
STACK NUMBER
STACK DIMENSIONS:
d m, L m, W
STACK AREA m2
DISTANCE FROM UPSTREAM DISTURBANCE m
DISTANCE FROM OUTLET OR DOWNSTREAM DISTURBANCE
APPARATUS IDENTIFICATION
NOZZLE DIAMETER • mm DIFFERENTIAL PRESSURE GAGE:
DRY GAS METER NUMBER _________ RANGE mm H20
Y DIVISION mm H20
SAMPLING PROBE LENGTH BAROMETER NUMBER
ORIFICE METER AH? mm H20 C
PITOT TUBE NUMBER
RUN INFORMATION
SAMPLE BOX NUMBER PROBE HEATER SETTING °C
FILTER NUMBERS FILTER BOX HEATER SETTING °C
SILICA GEL NUMBERS
SAMPLING TRAIN LEAKAGE RATE m3/min at mm Hg Vacuum
PRELIMINARY DATA FOR ISOKINETIC SAMPLING
APavg mm H2r Bwo
Pbar nm H0 Ts °K
Pg _ mm Hg "C" FACTOR
P. = (pk,^ + PJ mm Hg AMBIENT TEMPERATURE
S Dai 5
Figure 5. Sample data form for beryllium emissions determinations.
42
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3
a
c
o
o
en
c
o
cfl
c
•H
03
d
o
•H
W
W
•H
0)
•H
O
14-1
e
»-i
o
I"
a
m
a)
oo
43
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VOLUME OF LIQUID COLLECTED (V
Final
Initial
*
Liquid Collected
Conversion to mJ
Impinger Volume
(mi)
mi
mi
mi
Silica Gel
Weight (g)
g
g
g
mi
Total Volume
Collected
V1 (mi)
c
mi
**
Liquid collected = Final - Initial
Convert weight of water to volume of water by dividing total weight
increase by density of water (Ig/ml).
Figure 5. Sample data form for beryllium
(continued).
emissions determinations
44
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individual sampling situation will dictate the system of the sample box
support. It is recommended that the sampling box be modified to allow at
least two alternate methods of support.
2.4.2.3 Stack Gas Moisture Content. Determine the approximate moisture
content of the stack gases by Method 4 or its equivalent (ref. 13). If
the particular source has been tested before or a good estimate of the
moisture is available, this should be sufficient. The reference method
uses the condensate collected during the sampling for the moisture content
used in final calculations.
2.4.2.4 Molecular Weight of Stack Gas. Determine the dry molecular weight
of the gas stream by Method 3 (ref. 7). It is recommended that the sample
be of the integrated type for two reasons: 1) the possibility of a more
representative sample and, 2) the convenience of taking the sample at the
stack and being able to transport the sampling bag to a more suitable area
for Orsat analysis.
2.4.2.5 Stack Temperature and Velocity Heads. Get up and level the dual
inclined manometer and determine the minimum and maximum velocity head
(AP) and the stack temperature (T ). This is done most efficiently with
a type-S pitot tube, with a temperature-sensing device attached. The AP's
are determined with an inclined manometer by drawing the pitot tube across
the stack diameter in two directions (circular stack with 90 ° traverses).
This must be done in order to pick the correct nozzle size and to set the
nomograph. Incorrect selection of nozzle size and/or setting of the
nomograph may result in not being able to reach the isokinetic rate, there-
by voiding the sample. Determine the static pressure as directed in the
Quality Assurance Document of this series for Method 2 (ref 3). If the
stack temperature is greater than 93°C (200°F), arrangements must be made
to prevent deterioration of the filter, e.g., move the filter to a posi-
tion between the third and fourth impingers.
45
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2.4.3 Sampling
The on-site sampling includes making a final selection of proper
nozzle size, setting the nomograph (if used), loading the filter into the
filter holder, preparing and assembling the sampling train, making an ini-
tial leak-check, inserting the probe into the stack, sealing the port,
sampling isokinetically while traversing, recording the data, and making
a final leak-check of the sampling system. Sampling is the foundation of
source testing. Critical problems in testing result from poor or incorrect
sampling more frequently than from any other part of the measurement pro-
cess. The analytical process (laboratory) can never correct for errors
made in the field resulting from poor judgment or instrumental failure.
If the initial site survey, apparatus check and calibration, and preliminary
measurement and setup on-site have been implemented properly, the testing
should go smoothly with a minimal amount of effort and crises.
2.4.3.1 Preliminary Setting of the Nomograph. The setup of the nomograph
using the parameters obtained in subsection 2.4.2 is given in detail in
appendix B of this document. A procedure is included in the appendix for
checking the nomograph for correct design (accuracy).
Note 4: If the coefficient, Cp, of the type-S pitot tube
being used is outside the range of 0.85 + 0.02,
compute the ratio (C /0.85)2 and multiply this
constant times the correction factor, C, obtained
from the nomograph. Use this new "C" factor in
setting the nomograph for isokinetic sampling
(see appendix B for further discussion).
2.4.3.2 Selection of Nozzle Size. After the nozzle size and appropriate
probe length have been selected, insert the nozzle in the probe sheath
union and tighten the union. Do not use wrenches; finger-tight is suf-
ficient in most cases. Using uncontrolled pressure in tightening the
union will result in a broken or cracked inner-liner. Keep the ball joint
and nozzle tip protected from dust and dirt with a serum cap or equivalent.
46
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2.4.3.3 Assembling of Sampling Train. Assemble the glass itnpinger train
as follows:
1. Measure 200 m£ of distilled water in the graduated cylinder
5-m£ divisions) and place approximately 100 m£ of the water
in each of the first two impingers
2. The third impinger is left empty.
3. Place approximately 200 g of preweighed indicating silica gel
into the fourth impinger.
The first, third, and fourth impingers are modified Greenburg-Smith
while the second impinger is of the standard Greenburg-Smith design.
Place the impingers into the sample box and assemble the sampling train
using the appropriate U-joints. A very light coat of silicone grease (ace-
tone insoluble) should be applied carefully to the joints, to avoid leaks
in the system. Depending upon the design of the impinger, apply the
lubricant in a manner that prevents contact with the sample.
The loading of the impingers into the sample box can be done in the
laboratory by sealing the inlet to the first impinger, the outlet of the
third impinger, and inlet and outlet of the silica gel impinger. This is
practical only when the sampling site is near and the logistics are suit-
able.
The impingers must be maintained in an ice bath during sampling to
remove the condensibles and to keep the exit gas at or below 20°C (68°F).
2.4.3.4 Loading of Filter. Load the filters as follows:
1. The filters are removed from their sealed container and placed in
the filter holder with the Millipore filter toward the probe. The filter
should have an identification number, and the filter holder should be
numbered with a semipermanent marker to preserve the integrity of the: sample
Make certain that the filters are centered correctly in the holder. The
filter should be tightened until the two halves are secure. Overtighten-
ing the two halves can break the filter holder or tear the filter.
2. Place the filter holder into the sample box and connect the exit
of the filter to the inlet of the first impinger. Plug the inlet of the
47
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filter with a glass ball to check for leaks. Connect the meter box (vacuum
port) to the sample box with the appropriate umbilical cord.
2.4.3.5 Leak-Check. Leak-check the sampling train by plugging the inlet
to the filter holder, turning on the vacuum pump, and opening the valve
system until the vacuum in the system reaches 381 mm Hg (15 in. Hg). A
3 3
leakage rate not in excess of 0.0006 m /min (0.02 ft /min) at 381 mm Hg
is acceptable. Release the pressure in the system but do not turn off
the pump until the following sequence has been completed:
1. Slowly release the pressure in the system by carefully opening
(twisting) the glass ball in the inlet of the filter holder.
2. Shut the coarse valve (main vacuum valve).
3. When the vacuum gage reads zero vacuum, remove the glass ball
and shut down the pump.
2.4.3.6 Installation of Probe. Mount the probe in the sampling box and
connect the probe to the inlet of the filter and leak-check in the follow-
ing manner:
1. Seal the inlet of the probe nozzle with a serum cap.
2. Turn on vacuum pump.
3. Open the valve system and adjust the vacuum to 381 ram Hg (15 in.
Hg).
4. Check the leakage rate on the dry gas meter. A leakage rate not
3 •}
in excess of 0.0006 m /min (0.02 ft /min) at 381 mm Hg (15 in. Hg)
is acceptable.
Note 5: If an asbestos string is used in the fabrication
of the probe nozzle to the probe liner connection,
leak-check at 25 mm Hg (1 in. Hg) vacuum only. If
a leak-free connection in the nozzle is employed,
the total train, filter and probe, can be initially
checked at 381 mm Hg (15 in. Hg) vacuum.
5. After completion of the leak check, release the pressure as fol-
lows :
a) Slowly release vacuum by carefully opening (squeezing) the
serum cap until the system pressure is back to ambient (monitor with
48
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built-in vacuum gage).
b) Turn valve system off (coarse valve).
c) Turn off the vacuum pump.
Operations in subsections 2.4.3.5 and 2.4.3.6 can be combined, there-
by requiring only one initial leak-check. Record leakage rate on the form
in figure 3.
2.4.3.7 Taking of Sample. Turn on the sample box and fill the impinger
train container with crushed ice. The meter box operator should now re-
check the setting of the nomograph while the sample box operator checks
the filter box temperature gage to confirm that it is coming up to operat-
ing temperature; likewise, he can touch the probe to see if it is heating.
It is recommended that a thermocouple be mounted next to the glass liner
so that the probe temperature can be monitored.
As soon as the filter box temperature (if applicable) and the probe
temperature have reached the minimum stack gas temperature, commence
sampling.
1. Remove the plug or cap from the sampling port and remove the
dust (participates) on the port walls by utilizing a wire brush
or its equivalent. Remove the serum cap from the nozzle tip.
Record the initial volume of the test meter on the data log
sheet of figure 5.
2. If the sample gas is hot, start at the traverse point farthest
from the port and draw the probe out as the test continues.
Asbestos gloves should be used in handling hot sampling probes
and pitot tubes.
Note 6: If the stack gas temperature is >_ 93°C (200°F) in
all probability the filter holder should be placed
between the third and fourth impingers.
3. Attach a proper electrical ground to the probe and sampling system.
4. Insert the probe to the farthest traverse point with the nozzle
pointing directly into the gas stream. Seal the port and imme-
diately start: the pump. Adjust the coarse and fine control valves
49
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until isokinetic conditions are obtained. Note the time and
record it on the data log sheet of figure 5.
5. Maintain isokinetic conditions during the entire sampling period.
Sample for an equal amount of time at each traverse point. The
time period at each traverse point should be long enough to set
the sample rate and record the required data. The time period
at each traverse point must be long enough to obtain a total
sampling period representative of the process being monitored.
While sampling, reset the nomograph if:
a) The temperature in the stack changes more than + 14°C (25°F)
for T < 793°C (1460°F) or + 28°C (50°F) for T > 793°C, or
b) T (average temperature of meter) varies more than + 6°C
(11°F).
Adjust the sampling rate for every point and maintain the isokinetic
rate by continuous observation. Record the meter volume when sampling
has been completed at each individual traverse point. Take readings at
each sampling point, at least every 5 minutes (or during sampling period
at each traverse point): all the readings and adjustments should not be
attempted for time intervals of less than 2 minutes. When significant
changes in stack conditions are observed, compensating adjustments in
flow rate should be made to maintain isokinetic conditions. Record on
the data log sheet of figure 5 the traverse point number, stack tempera-
ture (Tg) , velocity pressure head (AP, mm H~0 or in. H^O) , (orifice pres-
sure differential (AH, mm Hg or in. H?0) , gas temperature at dry gas meter
(Tm_ ) and Tm or T , °C or °F), sample box temperature, condenser
in out avg
temperature, and the probe temperature if the probe has a thermocouple
and appropriate readout.
6. When sampling at one traverse point has been completed, move
the sampler to the next point as quickly as possible. Close the
control valve only when transferring the sampler from one sample
port to the other. Exclude the time required to transfer the
sampler from one port to another from the total sampling time.
50
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Upon transfer of the sampler to another port, the following procedures
should be followed:
a) Monitor the vacuum through the system. An increase of vacuum
is an indication of particulate buildup on the filter, collapse of the
membrane filter, or plugging of the last impinger by wet silica gel.
Loss in vacuum is an indication of a broken impinger, connector, filter,
or a loose connection.
b) Keep the impingers iced down (i.e., monitor the condenser
temperature) to hold the temperature below 20°C (68°F). Add salt to the
ice bath if necessary.
c) Check the line voltage with a voltmeter if a digital temper-
ature system is utilized.
Note 7: Digital temperature systems may read erroneously
with a drop in line voltage and/or interference
from electromagnetic fields.
d) Make sure that the dual inclined manometer is level and that
the pitot tube and pitot tube lines are unobstructed. A signal of trou-
ble would be AP's that are not representative of the velocity heads
obtained in a velocity traverse made during a preliminary site visit.
e) All data should be recorded on a data log sheet as depicted
in figure 5.
7. At the completion of the test, close the coarse control valve
on the meter, remove the probe from the stack, and turn off the
pump. Remove the probe carefully from the stack, making certain
that the nozzle does not scrape dust from the inside of the port.
Keep the nozzle elevated to prevent sample loss. Place a serum
cap or equivalent over the nozzle tip and leak-check the system
at 51 mm Hg (2 in. Hg) vacuum above the operating vacuum during
the test. The vacuum during the leak check should be no greater
than 381 mm Hg (15 in. Hg). (Do not boil the water in the im-
pingers.) Follow the same leak-check procedures as outlined in
subsection 2.4.3.5. Seal the end of the nozzle. Disconnect the
51
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pitoL tube lines and umbilical. Protect the pitot tube and
umbilical connections with tape or an appropriate equivalent.
Record on the data log sheet of figure 5 the leakage rate in
3 T
m /min (ft /min) and the vacuum at which the leak check was
performed. Check all connectors such as umbilical connection,
pitot tube lines, glass connections, etc. for evidence of mal-
function. Record all abnormalities on the data log sheet. The
logging of abnormalities will not necessarily void the sample,
but it may help to improve the quality of sampling performance.
2.4.4 Sample Recovery
The reference method requires a quantitative transfer of the impinger
solutions and filters to suitable storage containers. These transfers
should be performed in a "laboratory-type" area to prevent contamination
of the test samples. Move the sampling train and probe to the sample
recovery area. Care should be taken to prevent loss or contamination
of the samples. If the probe must be removed before moving to the
recovery area, the probe should be sealed at both ends (serum caps), and
the inlet of the filter plugged with a glass ball.
2.4.4.1 Container No. 1. Wipe the exterior of the filter holder sur-
face to remove any excess dust or extraneous material. Remove the filter
from the holder, place the filters in a precleaned glass container, and
seal it. It is recommended that a piece of paper (smooth surface) be
placed under the filter holder as the filter is being removed to pre-
vent loss of sample. Removal of the filter is more efficient if tweezers
are utilized. Teflon-tipped tweezers and a Teflon or a clean stainless
steel scalpel should be used to handle filters. If a filter is torn,
all pieces must be saved. Any loose particulate matter (or filter
material clinging to the frit) should be placed in this container. Record
date, time of test, location of test, and the number of the run on this
container. This data should also be recorded on the data log sheet of
figure 5.
52
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2.4.4.2 Container No. 2. Wash all internal surfaces of the filter with
distilled,- deionized water and atomic absorption grade acetone. Determine
the volume of liquid (acetone and water) and place in the container.
Note 8: An alternate procedure for determining the amount
of liquid (acetone and water) is by weighing (+ .5g).
A balance accurate to + 1 g is sufficient.
It is recommended that the probe be washed by attaching a graduated
cyclone flask to the end of the probe and washing the probe contents into
the container. This wash may require emptying the flask into container
No. 2 several times. A brush (length >_ probe length) should be used to
loosen particulate matter. Record total volume of acetone wash, date,
time of test, location, and run number on the container and on the da,ta
sheet of figure 5. Measure the total volume in the first three impingers
by transferring their contents into a graduate with a measurement accuracy
of + .6 percent. This data should be recorded on container No. 2 and on the
data log sheet of figure 5, Rinse the first three impingers with water
and acetone and transfer to the graduate. Transfer the solution in the
graduate into container No. 2. All measurements are read to the nearest
m£ for correction for blanks in the final analysis. Place at least
300 m£ of acetone and 300 m£ of the water into separate properly identi-
fied sample containers for blanks. Record total volume of water, acetone
wash, date, time of test, location, and run number on the sample and blank
containers and on the data sheet of figure 5.
2.4.4.3 Container No. 3. Transfer the silica gel from the fourth impinger
into its original preweighed container. Label the container with, date,
time of test, location, and any other pertinent data. This information
should also be recorded on the data log sheet. All sample containers
should be glass with caps lined with Teflon.
2.4.5 Sample Logistics (Data) and Packing of Equipment
The above procedures are followed until the required number of tests
are completed. The following is recommended at the completion of test-
ing.
53
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1. Check all sample containers for proper labeling Ctime and date
of test, location of testing, number of test, and any other pertinent
documentation). This function should be performed at the end of each
individual test or prior to such test if the impingers are to be utilized
in further tests before returning to the laboratory.
2. All data recorded during field testing should be recorded in
duplicate (carbon paper). One set of data should be mailed to the base
laboratory, the other hand-carried. This precaution can prevent a very
costly mistake.
3. All sample containers should be properly packed in a sample box
for shipment to the base laboratory. All boxes should be properly labeled
to prevent loss of the samples.
2.4.6 Data Validation
Following the directions given in subsection 2.5.3, calculate and/or
determine the following:
1. Moisture content of the stack gas, B
wo
2. Stack gas molecular weight on a wet basis, M .
3. The average stack gas velocity, (v )
4. The percent of isokinetic sampling for the sample run, I.
Compare these measured values to theoretical values derived from com-
bustion nomographs (ref. 10) or to values obtained by other measurement
methods, e.g., measuring B by the wet bulb-dry bulb method.
wo
Any large inexplicable differences in measured and theoretical values
should be noted and special care taken to reduce the variability of that
specific parameter for the next run. If the percent of isokinetic samp-
ling is outside the range of 0.90 to 1.10, the run should be repeated.
If it is known that the particle size distribution is below about 5 ym,
the EPA Administrator may option to accept the data even if I is outside
the interval of 100 + 10 percent.
Values of B and M as measured by the first sample run should be
wo s
used in setting isokinetic conditions for subsequent runs unless there
54
-------
is reason to doubt their validity when compared with the values derived
from preliminary measurements or estimates.
2.5 POSTSAMPLING OPERATIONS (Base Laboratory)
2.5.1 Apparatus Check
2.5.1.1 Type-S Pitot Tube. The type-S pitot tube is checked according to
the Quality Assurance Document of this series for Method 2.
2.5.1.2 Dry Gas Meter and Orifice Meter (Sampling Train). A postcheck
(a postcheck for one test can serve as the presampling check for the
next test) should be made of the sampling train to check for proper opera-
tion of the pump, dry test meter, vacuum gage, and dry test meter ther-
mometers. Leak-check the vacuum system. Determine Y and AH@ at three
points in the operating range. This not only checks on the system for
future testing but also gives confidence in the data from the previous
field test. This is a recommended procedure to improve the data quality
and to prevent field sampling under assumed conditions.
2.5.2 Analysis (Laboratory)
The requirement for a precise and accurate analysis requires an
experienced analyst and familiarity with the analytical method; calibra-
tion is of the utmost importance, and neglect in this area is unaccept-
able. The analytical method is based upon an acid digestion (perchloric
acid, etc.), followed by the determination of Be at the 234.8-nm line
utilizing an atomic absorption spectrophotometer.
2.5.2.1 Apparatus
1. Atomic Absorption Spectrophotometer. An instrument as described
in subsection 2.1.17.
2. Hotplate. A general duty hotplate is required for evaporation
and digestion of samples.
3. Perchloric Acid Fume Hood. The laboratory hood or fume cupboards
should be noncombustible, constructed of metal or stoneware, and
left either unpainted or protected with an inorganic coating such
as porcelain. Glycerinelitharge should not be used as a sealant
55
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on hood end blower systems; tetrafluoroethylene plastic and
fluorocarbon greases are the best materials for this service.
Only a fluorocarbon grease should be used as blower lubricant.
Any other type of lubricant should be considered hazardous
(ref. 8).
4. Pipettes. An ample number of (1, 3, 5, 8, 10 m£) pipettes (volume-
tric, Class A) are required for preparing standards and samples
for analysis.
5. Volumetric Flasks. All volumetric glassware for preparing stan-
dards and samples should be volumetric, Class A.
6. Analytical Balance. An analytical balance that weighs to 0.1 mg
is required to prepare standards.
7. Aspirating Bulb. Bulbs should be utilized in pipetting all solu-
tions.
2.5.2.2 Reagents (Calibration and Analysis)
1. Water: deionized, distilled
2. Acetone: atomic absorption (AA) grade
3. Hydrocloric Acid: concentrated (ACS grade)
4. Nitric Acid: concentrated (ACS grade)
5. Perchloric Acid: concentrated, 70 percent (ACS grade)
6. Beryllium Powder: 98 percent minimum purity
Note 9: In lieu of beryllium powder, beryllium salt
(Be(N03)2'3H20) of 98 percent purity can be
utilized.
2.5.2.3 Standard Beryllium Solution (Stock Solution)
1. Prepare a 12 N sulfuric acid solution by adding 33.3 m£ of concen-
trated H2SO, to 66.6 m£ H?0 in a 100 m£ volumetric fiask.
2. Dissolve 100.0 mg of the beryllium metal, weighed on an analyti-
cal balance, in 80 m£ of the 12 N sulfuric acid solution and
dilute to a volume in a 1000-m£ volumetric flask (class A) with
distilled, deionized water to give a 100-yg/m£ Be standard.
3. Prepare a typical working analytical curve by pipetting 1, 2, 3,
and 4 m£ of the stock solution into four 100 m£ volumetric flasks
56
-------
and diluting to volume with 25 percent V/V hydrochloric acid, giv-
ing concentrations of "L, 2, 3, and 4 ug/tn£, respectively., These
dilute standards should be prepared fresh daily.
Note 10: If interferences such as aluminum ( 500 yg/m£) or
high concentrations of silicon and magnesium are
present, the standards prepared must contain the
same reagents and major matrix elements as pre-
sent in the sample solutions. Oxine (8-hydroxy
quinoline) has been added to samples and standards
to control interferences (ref. 14).
2.5.2.4 Working Analytical Curve. General guidelines for preparing a
working analytical curve are:
1. Prepare standard solutions from the 100-yg/m£ solution in suit-
able class A volumetric flasks.
2. Set up the atomic absorption instrument as directed by the manu-
facturer at the 234.8-nm line for determination of Be utilizing
a N 0-C2H2 flame.
3. Establish the working range of the instrument (linearity). A
typical linear calibration curve is obtained from 0 to 4 yg/m£.
A standard containing 3 yg/m£ Be will give an absorbance reading
of approximately 0.4 absorbance units.
Note 11: If the concentrations of the field samples are
below 1 pg/m&, a calibration curve shall be pre-
pared covering the range from 0 to 1 yg/m£. In
most cases this will require scale expansion.
2.5.2.5 Sample Preparation. The sample preparation is a wet digestion
in concentrated perchloric acid.
1. Container No. 1. Transfer the filters and any loose particulate
matter from the container into a 150-m£ beaker. Add 35 m£ con-
centrated nitric acid to the sample container, then transfer to
the 150-m£. beaker. Heat on a hotplate until light-brown, fumes
are no longer present to destroy all organic matter.
Note 12: The analyst must insure that the sample is heated
until light brown fumes are no longer given off
after the initial nitric acid addition; otherwise,
57
-------
dangerous organic perchlorates may result from
the subsequent perchloric acid digestion. All
organic matter must be destroyed before the addi-
tion of perchloric acid. In some cases the
nitric acid addition and heating until brown
fumes are no longer given off will have to be
repeated to remove organic residues.
Note 13; Perchloric acid should be used only under a
perchloric acid hood. The existing ductwork
must be washable to prevent the buildup of
dangerous perchlorates.
Note 14: The presence of a black residue in the beaker
indicates incomplete oxidation. If an organic
residue remains, add 50 m£ nitric acid and repeat
digestion.
Cool to room temperature and add 5 m£ concentrated sulfuric acid
and 5 m£ concentrated perchloric acid; then follow instructions
in subsection 2.5.2.6.
2. Container No. 2. Place a portion (50-75 m£) from Container No. 2
into a 150-m£ beaker and put on a hotplate. Add a couple of
glass boiling beads to minimize bumping. Add portions of the
remaining solution as evaporation proceeds and evaporate to
dryness. Do not leave the beaker on the hotplate after the
liquids have evaporated. Cool the residue and add 35 mH of con-
centrated nitric acid. Heat the acid solution on a hotplate as
directed in (1) above. Cool to room temperature and add 5 m£
concentrated sulfuric acid and 5 m£ perchloric acid. Then con-
tinue to subsection 2.5.2.6.
2.5.2.6 Sample Analysis. Samples from subsection 2.5.2.5 may be com-
bined here for ease of analysis. A complete transfer when combining sam-
ples should be done with a 1:1 (V/V) sulfuric acid-perchloric acid rinse
solution.
1. After transfer, place on a hotplate and evaporate to dryness in
a perchloric acid hood.
2. Cool the residue.
3. Dissolve the residue in 10 m£ of 25 percent V/V hydrochloric
58
-------
acid. The sample is now ready for analysis.
Note 15: If prior experience suggests a concentrated solu-
tion exceeding the linear range of the working
analytical curve, do not combine the two sample
solutions (2.5.2.5). An alternative to this
approach is a further dilution of the concen-
trated sample with 25 percent V/V hydrochloric
acid. When employing this latter procedure,
aspirate a minimum volume of the original sam-
ple solution before dilution. The dilution would
require an aliquot from the original sample diluted
to volume with 25 percent V/V hydrochloric acid.
The dilution ratio is dependent upon the sample
concentrations and must be determined by the
analyst.
Analyze the samples at 234.8 nm using a nitrous oxide-acetylene
flame. When utilizing a nitrous oxide-acetylene flame, allow
the burner to warm up without aspiration for several minutes.
This will help to reduce carbon formation. After continuous
operation of the nitrous oxide burner head, deposits will build
up near the slot causing a ragged flame. The burner slot should
be cleaned at frequent intervals or whenever the flame becomes
ragged. Report results in yg/mJi and record the total volume of
25 V/V hydrochloric acid to the nearest m£. In recording the
volume of solution, any dilution factors must be incorporated
for subsequent calculations to determine the total yg of Be in
the original sample volume.
Note 16: Aluminum, silicon, and other elements interfere
with this method if present in large quantities.
Standard methods are available to effectively
eliminate these interferences (refs. 14, 15).
Three ways are most commonly utilized:
(a) Standards matching the sample composition
may be prepared. Utilization of this method
suggests that the analyst has some independent
knowledge of the sample history. This method
should not be used unless the overall compo-
sition of the sample is known and its
composition does not vary from sample to sam-
ple.
59
-------
b) Addition of buffer solutions to both standards
and samples.
c) The use of additive methods.
In most analyses a combination of methods two and
three will yield the most precise and accurate
analysis. Several things must be taken into con-
sideration when an additional method (c) is uti-
lized:
(1) The absorbance must be linear over the con-
centration range being analyzed.
(2) Chemical interferences must be constant over
the range of metal concentrations.
(3) It is assumed that the entire absorption sig-
nal is due to the element being absorbed.
This assumption must be verified for a sam-
ple series by checking the absorption at a
nearby non-absorbing line (i.e., for the ele-
ment being analyzed for) or by utilizing a
background correction with a continuous
source.
5. Blank preparation and analysis. A 300-m£ water blank (distilled,
deionized water used in the field) and a 300-m£ acetone blank
(acetone used in field sampling) should be prepared and analyzed
as described in subsections 2.5.2.5(2) and 2.5.2.6(2,3). Report
results in )Jg/m£ Be for both water and acetone.
Standards should be interspersed with samples and blanks since the
calibration can change slightly with time. The standard working curves
should be run prior to and after sample analysis.
In considerations of the fact that the major source of beryllium is
the mineral beryl (3 BeO-Al^O,, • 6810,-,) which includes two of the major
interferences (i.e., Al and Si) in the atomic absorption method the fol-
lowing is recommended:
a) Field samples should be analyzed by the standard procedure as
outlined in this document.
b) In addition to the above, a concentrated standard solution of
Be should be added to the sample in microliter portions to check for
60
-------
interferences by method of standard additions (ref. 14).
If the analyzed values for Be by the standard procedures and the
method of standard additions differs by 25 percent (after background cor-
rection), it is suggested that 8 hydroxyquinoline be added to samples and
standards (ref. 13) to control interferences and the method of standard
additions be employed as discussed in note 12 above.
2.5.2.7 Moisture Content (Silica Gel). Weigh the original preweighed
container No. 3 containing silica gel utilized in the field. Record the
final weight in a table such as figure 5.
•»
2.5.3 Calculations
Calculation errors due to procedural or mathematical mistakes can be
a large component of total system error. Therefore, it is recommended
that each set of calculations be repeated or spot-checked (every third
calculation), preferably by a team member other than the one who performed
the original calculations. If a difference greater than a typical round-off
error is detected, the calculations should be checked step by step until
the source of error is found and corrected. A computer program is
advantageous in reducing calculation errors. A standardized computer program
could be developed to treat all raw field data. If a computer program
is used, the original data entry should be checked, and if differences
are observed, a new computer run made. Figure 6 shows a sample form which
can be used to log computations.
2.5.3.1 Volume of Water Vapor, ws_. The volume of water vapor in the gas
sample at stack conditions is calculated using the V-|_ value determined
from the table in figure 5 and the following equation:
V = K V1 (2)
w w 1 P '
s c s
where V = Volume of water vapor in the gas sample at stack conditions
Ws 3 3
mJ (ftJ)
61
-------
CALCULATIONS AND DATA ANALYSIS
(1) VOLUME OF WATIR VAPOR (Stack Conditions)
T ,
V = .00346 V —— = m
Ws c s
where V^ = m£ P = nun Hg
(2) DRY GAS VOLUME (Stack Conditions):
AH
/ H N
(p + avg-)
\ bar 13.6 /
T P - --- "
s m s
where V = _________ m P = _ mm Hg
IH - D3F — ~ --
AH
T = _ °K avg = __ mm H0
mm Hg
(3) DRY GAS VOLUME (Standard Conditions):
AH
I P. + -r?-
V = .3874 V
tn , m
std
where V = m P. " mm Hg
m — bar °
T = °K AH " nun H_0
m avg 2
(4) TOTAL GAS VOLUME (Stack Conditions):
s s
where V = m
m
3 3
V = m
(5) MOISTURE CONTENT OF STACK GAS:
V
0.0013 1c ... , . .
Bwo ° TV + 0.0013\ = (dimensionless)
( "std )
where V - mi
Figure 6. Sample calculation and data analysis form
62
-------
(6) MOLECULAR WEIGHT (Wet Basis):
M = Mj (1-B ) + 18 R = g/g-mole
s d wo wo "
where M = g/gm-mole
d
B = g/g-mole
(7) AVERAGE STACK GAS VELOCITY:
avg ' 3'"96 Cp
where C = _ ^_ (diraensionless) P = _ mm Hg
g • _ nm H201/2 Mg = __ g/g-mole
(T ) = _ °K
(8) BERYLLIUM COLLECTED:
Wt * V* Ci - Vw Cw - Va Ca
where Y = _ m£ G - __ _ _ yg/m!
mi C -= _ ug/mi
- ' — ' - ' —
(9) TOTAL BERYLLIUM EMISSIONS:
.0864 W (v ) A
t s'avg s
total
where wt " - US (vs)avg = - ./sec
(10) ISOKINETIC VARIATION:
100 V
.
total
—= percenc
Where Vtotal
n s avg
3
-------
K = 0.00346 """ "*0v '"
w m£ K
3
= ( 0.00267 in Hf ^ t— ) when these units are used
mJ6 R
V = Total volume of liquid collected in impingers and silica gel,
Q
T = Average stack gas temperature, °K (°R)
S
P = Stack pressure, mm Hg (in. Hg)
s
The stack pressure is determined by:
P = P, + Static pressure
s bar — K
2.5.3.2 Sample Dry Gas Volume, ^ms, Correct the sample volume measured
by the dry gas meter to stack conditions using this equation:
V
m
s
T
~\T-
m
/ AHav
[ Pbar + 13.6
V ps
(3)
where
V = Volume of gas sample through the dry gas meter at stack
m 01
S , . J , r- J\
conditions, m (ft )
V = Volume of gas sample through the dry gas meter at meter
m 33
conditions, m (ft )
T = Average temperature of stack gas, °K(°R)
T = Average dry gas meter temperature, °K(°R)
P = Barometric pressure at the orifice meter, mm Hg (in, Hg)
Dei IT
AH = Average pressure drop across the orifice meter, mm H_0
(in. H20)
13.6 = Specific gravity of mercury
P = Stack pressure, P, + static pressure, mm Hg (in. Hg)
s
Temperatures are converted to degrees Kelvin (Rankine) , and all pressures
are recorded to the nearest 2.5 mm Hg (0.1 in. Hg) . Average the dry gas meter
64
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temperatures of the [(T )°C] and [(T )°C] to obtain the average tempera-
ture of the gas flowing through the meter during the test. Average the pres-
sure of the stack (P ). Determine the average orifice pressure drop by
totaling the AH values at each traverse point and dividing by the total number
of traverse points. Orifice pressure readings and the calculated average in
millimeters of water should be rounded to two significant digits (e.g., 0.12
or 1.2). Record V to the nearest .003 m (0.1 ft ).
m
s
2.5.3.3 Total Gas Volume, total. Use equation 104-4 (from app. A) to cal-
culate the total gas volume where:
V ^ , = V 4- V (4)
total m w
s s
where
3 3
V = Total volume of gas sample at stack conditions, m (ft )
total 3 3
Vm = Volume of gas through dry gas meter at stack conditions, m (ft )
S 33
Vw = Volume of water vapor in gas sample at stack conditions, m (ft )
o
(See subsection 2.5.3.2)
2.5.3.4 Stack Gas Molecular Weight on a Wet Basis, M . Calculate the stack
gas molecular weight by
M = M, (1 - B ) + 18B (->)
s d wo wo
where M is given by
M, = 0.44(%C00) + 0.32(%(L) + 0.28(100 - %C00 - %0 ) (6)
d 2 2 22
and %CO and %0 are the averages of percent CO and 0 determinations,
respectively, according to the Quality Assurance Document of this series for
Method 3, (ref. 7).
Record M to three significant digits (i.e., —._) on the data sheet of
S
figure 6.
65
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2.5.3.5 Average Stack Gas Velocity (v ) . Use the following equation
s'avg
to calculate the average stack gas velocity (ref. 5):
where
(v ) = K C (/AP)
s avg P P av§ V T> M (7)
(v ) = Average stack gas velocity, m/s (ft/s)
S d.Vg
Kp = 34-98 m ( g-mm Hg \
sec y g-mole °K mm HO
- [85.53 ft /lb-in Hg \l/2
\ sec I Ib-mole °R in. H?(
when these units are used
C = Pitot tube coefficient, dimensionless
(T ) = Average stack gas temperature, °K (°R)
s avg
= Average square root of the velocity head of stack gas,
avg ; 1/2
/mm Hg (in. H~0) (see figure 5)
P = Stack pressure, P^OT. + static pressure, mm Hg (in. Hg)
S
M = Molecular weight of stack gas on a wet basis, the summation
o
of the products of the molecular weight of each component
multiplied by its volumetric proportion in the mixture,
g/g mole (Ib/lb-mole) [2.5.3.4].
2.5.3.6 Total Beryllium Collected, W . Determine the total weight of beryllium
collected using this equation:
W = V7 C7 - V C - V C (8)
t II w w a a
66
-------
where
W - Total collected weight of beryllium, yg
V- = Total volume of hydrochloric acid (from subsec. 2.5.2.6(2)), m&.
Q
t = Concentration of beryllium found in sample, yg/m£.
V = Total volume of water used in sampling (impinger contents plus all
w
wash amounts), m£.
C = Blank concentration of beryllium in water, yg/m£
w
V = Total volume of acetone used in sampling (all wash amounts), m£
a
C = Blank concentration of beryllium in acetone, yg/m£
a
2.5.3.7 Total Beryllium Emissions. Calculate the total beryllium emissions
from each stack per day by utilizing the following equation which applies to
a continuous operation. For operations that are cyclic in nature, use only
the time per day that each stack is in operation. The total emissions from
a source will be the summation of results from all stacks.
W (v )
R =
t
s avg s 86,400 s/d
Vtotal 106 yg/g (9)
where
R = Rate of emission, g/d
W, = Total weight of beryllium collected, yg (from subsec. 2.5.3.6)
33
V ., = Total volume of gas sample at stack conditions, m (ft ) (from
total
subsec. 2.5.3.3)
(v ) = Average stack gas velocity, m/s (ft/s) (from subsec. 2.5.3.5)
s avg 2 2
A = Stack area, m (ft )
s
86,400 = Number of seconds per day
2.5.3.8 Isokinetic Variation. The comparison of the velocity of gas in the
67
-------
probe tip versus the actual stack gas velocity is calculated using equation
104-8 (from app. A).
100 V
(10)
I
avg
where
I = Percent of isokinetic sampling
Total volume of
subsec. 2.5.3.3)
V 33
total = Total volume of gas sample at stack conditions, m (ft ) (from
2 2
A^ = Probe tip area, m (ft )
6 = Sampling time, s
(v ) = Average stack gas velocity, m/s (ft/s) (from subsec. 2.5.3.5)
s avg
68
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SECTION III
MANUAL FOR FIELD TEAM SUPERVISOR
69
-------
SECTION III MANUAL FOR FIELD TEAM SUPERVISOR
3.0 GENERAL
The term "supervisor" as used in this document applies to the
individual in charge of a field team. He is directly responsible for the
validity and the quality of the field data collected by his team. He may
be a member of an organization which performs source sampling under
contract to government or industry, a government agency performing source
sampling, or an industry performing its own source sampling activities.
It is the responsibility of the supervisor to identify sources of
uncertainty or error in the measurement process for specified situations
and, if possible, eliminate or minimize them by applying appropriate
quality control procedures to assure that the data collected are of accept-
able quality. Specific actions and operations required of the supervisor
for a viable quality assurance program are summarized in the following
listing.
1. Monitor/Control Data Quality
a. Direct the field team in performing field tests according to
the procedures given in the Operations Manual.
b. Perform or qualify results of the quality control checks
(i.e., assure that checks are valid).
c. Perform necessary calculations and compare quality control
checks to suggested performance criteria.
d. Make corrections or alter operations when suggested per-
formance criteria are exceeded.
e. Forward qualified data for additional internal review or to
user.
2. Evaluate Routine Operation
a. Obtain from team members immediate reports of suspicious
data or malfunctions. Initiate corrective action or, if necessary, specify
special checks to determine the trouble; then take corrective action.
Document the corrective action taken.
70
-------
b. Examine the team's log books periodically for completeness
and adherence to operating procedures.
c. Approve data sheets, calibration checks, etc., for filing.
3. Evaluate Overall System
a. Evaluate available alternative(s) for accomplishing a given
objective in light of experience and needs,
b. Evaluate operator training/instructional needs for specific
operations.
Consistent with the realization of the objectives of a quality
assurance program as given in section I, this section provides the super-
visor with brief guidelines and directions for:
1. Collection of information necessary for assessing data quality
on an intrateam basis;
2. The use of performance criteria to insure the collection of data
of acceptable precision/accuracy;
3. Isolation, evaluation, and monitoring of major components of
system variability.
In subsection 3.1, a method of assessing data quality on an
intrateam basis is given. This method involves calculating a sample
standard deviation using the three replicate runs required in a field
test and calculating 90 percent confidence limits for the average of the
three replicates.
Subsection 3.2 presents suggested criteria for judging equipment
performance, frequency of calibration, and isokinetic sampling.
Directions for the collection and analysis of information to identify
trouble, and subsequently, the control of data quality within acceptable
limits are given in the third subsection.
3.1 ASSESSMENT OF DATA
The beryllium emission rate, R, for a particular field test is the
average of at least three replicates. Intrateam assessment of data
quality as discussed herein provides for an estimate of the precision of
71
-------
r
-------
-------
the measurements. Precision in thts case refers to replicability, i.e.,
the variability among replicates and is expressed as a coefficient of
variation. This precision statement combines variability due to process
changes and to measurement errors. This technique does not provide the
information necessary for estimating measurement bias (see subsection
4.1.2 for a discussion of bias) that could occur, for example, from an
error in determining the pitot tube coefficient, nozzle cross-sectional
area, or the orifice meter calibration. However, if the operating pro-
cedures given in the Operations Manual are followed, the bias should be
small in most cases. An independent quality audit which would make
possible a bias estimate is suggested and discussed in section IV, the
Management Manual.
3.1.1 Calculating Precision of Field Data
Each field test is comprised of at least three sample runs. Using
the sample runs as replicates, a standard deviation can be calculated.
This calculated standard deviation is a combined measure of the measure-
ment and process variabilities. The standard deviation is calculated by
(11)
where s{R} = The calculated standard deviation for the
three sample runs, g/d,
R-i (Rn) (RQ) = Beryllium emission rate for sample run 1
(2)(3), g/d,
R = Average beryllium emission rate calculated
from the three sample runs, i.e., 1/3(R, + R-
R3), g/d, and
2 = The number of replicates minus one (degrees
of freedom).
— 2
(R - R) H
- (R2
-
9
R)2 +
(R3 - R)2 '
2
1/2
72
-------
3.1.2 Reporting Data Quality
It is recommended that the average measured beryllium emission rate,
R, be reported with 90 percent confidence limits. Assuming that R is
normally distributed (this is usually a valid assumption since sample
means tend to be normally distributed even for non-normal parent distribu-
tions) and using S{R} as calculated in 3.1.1 above to estimate the standard
deviation, exact confidence limits can be calculated for the true R value
using the Student t-distribution with r - 1 = 2 degrees of freedom. This
assumes no bias in the average values. The average measured value with
90 percent confidence limits is reported as
R + 2.92
where R = The average of three replicates, g/d.
S{R) = Estimated standard deviation of R based on three
replicates, g/d.
2.92 = 95^— percentile of the Student t-distribution with
2 degrees of freedom which yields a 90 percent
confidence interval.
n = The number of replicates, i.e., n = 3 for this case.
For example, if for a given field test R = 8.52 g/d and s{R} was cal-
culated to be .49 g/d the reported value with 90 percent confidence limits
would be
$.52 g/d + (2.92X.49 g/d) j 7T
or the true beryllium emission rate, R , would be assumed to be in the
interval
7.69 g/d <_ R f 9.35 g/d
The utility of the above statement follows from the fact that if this
procedure for computing confidence limits is followed for several field
73
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tests, then 90 percent of the time the true R value will be contained
within the given limits (assuming that R is not biased). It is recom-
mended that the 90 percent confidence limits be reported with the field
data form in the Operations Manual.
3.2 SUGGESTED PERFORMANCE CRITERIA
Data assessment as discussed in the previous subsection is based on
the premise that all variables are controlled within a given level, there-
by guarding against large undetected biases in the measurement process.
These levels of suggested performance criteria are the values given in the
Operations Manual for determining when equipment and/or personnel vari-
ability is out of control. Criteria for judging performance are summarized
in table 1.
3.3 COLLECTION AND ANALYSIS OF INFORMATION TO IDENTIFY TROUBLE
In a quality assurance program, one of the most effective means of
preventing trouble is to respond immediately to indications of suspicious
data or equipment malfunctions. There are certain visual and operational
checks that can be performed while the measurements are being made to
help insure the collection of data of good quality. These checks are
written as part of the routine operating procedures in section II. In
order to effectively apply preventive-type maintenance procedures to the
measurement process, the supervisor must know the important variables in
the process, know how to monitor the critical variables, and know how to
interpret the data obtained from monitoring operations. These subjects
are discussed in the following subsections.
3.3.1 Identification of Important Variables
Determination of the beryllium emission rate requires a sequence of
operations and measurements that yields as an end result a number that
serves to represent the average beryllium emission rate for that field
test. There is no way of knowing the accuracy, i.e., the agreement between
the measured and the true value, for a given field test. However, a
74
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Table 1. Suggested Performance Criteria
1. Suggested Criteria for Equipment Performance
(a) Dry Gas Meter: .98 £ y £ 1.02
(b) Barometer: + 5.08 mm Hg (+0.2 in. Hg)
(c) Thermometers: + 2.8°K (+ 5°R) at 273°K (492°R) or + 3.9°K
(+ 7°R) at 373°K (672°R)
(d) Stack Temperature + 2.8°K (+ 5°R) at 273°K (492°R) or + 3.9°K
Measuring System: (+ 7°R) at 373°K (672°R)
3 3
(e) Sampling Train Leakage: Less than .00057 m /min (0.02 ft /min) at
381 mm Hg (15 in. Hg) vacuum
(f) Meter Orifice: AH@ constant within 3.81 mm HO (+ 0.15 in.
H»0) over the operating range.
(g) Probe Nozzle Diameter: Range of three different diameter
measurements less than .010 cm (0.004 in.).
(h) Type-S Pitot Tube: C constant within + 5 percent over working
range and each calibration check is within
1.2 percent of the original C .
2. Suggested Criteria for Performing Equipment Calibration
(a) Above items (a) through (g) are calibrated when new and checked before
each field test and recalibrated any time the check results fall outside
the prescribed performance limits.
(b) Item (h) the type-S pitot tube is calibrated when new, before every
third field test, or at any sign of damage.
3. Suggested Criteria for Percent Isokinetic
0.90 < I < 1.10
75
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knowledge of the important variables and their characteristics allows
for the application of quality control procedures to control the effect
of each variable at a given level during the field test, thus providing
a certain degree of confidence in the validity of the final result.
A functional analysis of this method of measuring the beryllium
emission rate of a stationary source was made to try to identify important
components of system error. The method has been subjected to one col-
laborative test (ref 16). The results from this test were used, along
with results from an evaluation study of Method 5 and (ref. 17), to
estimate rtie overall system error. The use of the Method 5 evaluation is
valid because the identical field procedures are used for Method 104.
Individual error components were estimated using engineering judgment in
a manner such that their combined variability is consistent with overall
system error.
Variability in emissions data derived from multiple repetitions
include components of variation from:
1. Process conditions,
2. Equipment and personnel in field procedures, and
3. Equipment and personnel in the laboratory.
In many instances time variations in source output may be the most
significant factor in the total variability. In order to judge the
relative magnitudes of measurement variability and process output vari-
ability, process parameters should be monitored throughout the test.
The exact process data to be obtained are dependent upon the process being
tested. In general, all factors which have a bearing on the emissions
should be recorded on approximately a 15-minute interval (ref. 18). These
factors include process or fuel weight rate, production rate, temperature
and pressure in the reactor and/or boiler, control equipment, fan and/or
damper settings, pressure drop or other indicator of beryllium collection
efficiency. Sample forms for combustion, incineration, and process
sources are given in reference 18.
76
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It is most important to realie-e that the larger measurement errors
result from poor operator technique such as loss or gain of collected
beryllium during sample recovery, or poor orientation and positioning
of the probe during sample collection. Such deviations from recommended
procedures cannot be evaluated or corrected for. It is important to
observe and eliminate such occurrences while the test is in process.
Sources of variation due to equipment includes the type-S pitot
tube, sampling nozzle cross-sectional area, orifice meter, dry gas meter,
probe heater, and sample box heater. These are all controlled through
a calibration check before each field test. Also, the probe and sample
box heaters are checked periodically during the test. Important error
sources checked immediately before and/or during sample collection
includes sampling train leaks, the sample gas temperature leaving the
last impinger, and isokinetic sampling conditions. Assuming good operator
technique, these error sources are discussed below and each one's effect
on the determination of the beryllium emission rate is derived from a
functional analysis of the measurement process in subsection 4.1.
The analysis phase of this method is also subject to large vari-
ability if proper care is not exercised. All discussions of the analysis
phase assume that the analysis is made by atomic absorption. The precision
and accuracy of the data obtained from this method of analysis depend
upon equipment performance and the proficiency and conscientiousness of the
analyst performing the task.
A summary of the important parameters is given below. The parameters
are roughly given in ascending order of importance. Importance is quali-
tatively derived from the estimated error range of a parameter weighted by
its estimated frequency of occurrence.
3.3.1.1 Equipment Calibration. Equipment calibration is the backbone of
any quality assurance program. It is important that the calibration pro-
cedure be carried out correctly, that the calibration standards are pro-
perly calibrated and maintained, and that the frequency of calibration is
adequate.
77
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Important calibration constants and how they influence measurement
accuracy include the following:
1. Error in^the pitot tube calibration coefficient is directly
reflected in the stack gas velocity determination and is doubled in the
process of determining isokinetic sampling rates. This error could be very
large if the pitot tube is not calibrated under actual field test condi-
tions, i.e., strapped to the sampling probe with isokinetic sampling con-
ditions maintained at each calibration point.
2. Error in determining the nozzle diameter is quadrupled in the
process of determining isokinetic sampling rates and is doubled in the
percent of isokinetic sampling calculation. One source of error here is
the use of an out-of-round nozzle. The average nozzle diameter is used to
calculate the area of a circle which yields a larger than true cross-
sectional area if the nozzle tip is not round.
3. Dry gas meter inaccuracy appears directly in the concentration
and beryllium emission rate determinations.
4. The orifice meter calibration constant is used in determining
isokinetic sampling conditions and any error in the constant is doubled
in setting the sampling rate. Also, if AH@, the pressure drop across
3 o
the orifice that gives a flow rate of -021 m /min (0.75 ft /min) at 21°C
(70°F) and 760 mm Hg (29.92 in. Hg) varies from 46.7 mm H20 (1.84 in. H20),
and a nomograph is used to set isokinetic sampling conditions, an error
results. It is recommended that an orifice meter with a AH@ outside the
range of 40.4 to 53.1 mm HO (1.59 to 2.09 in. HO) not be used in con-
junction with a nomograph.
3.3.1.2 Anisokinetic Sampling. Anisokinetic sampling can occur from error
in the calibration constants of the pitot tube, orifice meter, and nozzle
diameter. It can also result to a lesser degree, usually, from measure-
ment error in the moisture content and molecular weight of the stack gas.
Errors from the above sources will not be directly reflected in the percent
78
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of isokinetic sampling calculation. Therefore, it is important to deter-
mine each parameter as accurately as possible, either through calibrations
or careful measurements.
Failure or, in some instances, the inability to make adjustments in
the sampling rate as the stack gas velocity varies or as the deposited
particulate matter plugs the filter can result in anisokinetic sampling.
Use of a nomograph can be a cause of anisokinetic sampling because of
(1) any inaccuracy in the nomograph, (2) use of preset values for C , AH@,
and M, (these errors can be eliminated by using actual values and adjust-
ing the correction factor on the nomograph), and (3) operator error in
setting the nomograph. The sum of these errors is quantified to a cer-
tain extent by the percent of isokinetic sampling calculation.
Deviation from isokinetic sampling cannot be related directly to error
in the measurement process (see subsection 4.1). However, failure to
maintain isokinetic sampling conditions under otherwise normal operations
reflects the lack of alertness and, perhaps even the level of competency,
of the field crew.
3.3.1.3 Sample Recovery. The technique used by, and the attitude of, the
crew members in sample recovery are of paramount importance to measurement
precision and accuracy. Use of an inadequate sample recovery area in terms
of space, lighting, or cleanliness will incr-ease the probability of error.
Results from a collaborative test (ref. 16) have shown that the recovery
of beryllium-containing particles with the washing of the probe, filter
holder, and impingers is a major source of error when compared to the filter-
only collection. An estimate (ref. 16) of 77 percent of the total beryllium
collected is from the wash solution in the second sample container (sec-
tion 2.4.4.2), hence contamination of the wash solution, failure to properly
clean all of the sampling equipment, or loss of wash solution could cause
considerable error in the final measurement value.
3.3.1.4 Analysis. The analysis phase is subject to error from any of the
following:
1. Sample handling. Exposure to the atmosphere at any time between
sample collection and analysis could result in contamination or
79
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loss of the sample. Also, insolubles that penetrate the filter
and are caught in the impingers may be lost in transfers to and
from container 2 due to the non-homogeneity of the sample.
2. Digestion. Failure to thoroughly dissolve any of the particles
from either of the two sample containers in the solution will
be a source of negative error in the final measurement value.
Stated simply, the large beryllium containing particles will not
absorb the 234.8 nm wavelength of energy.
3. Preparation of standards. Preparation of standards for a working
analytical curve can be a source of errors if proper techniques
are not followed and care taken in the process.
4. Setting and maintaining standard conditions throughout the analy-
sis period. Errors can arise from improper instrument tuning, a
ragged burner gas flame, and an incorrect aspiration rate. Mea-
surement of working standard solutions before and after field
sample analysis, blank samples measured before every field sample
and methods for eliminating interferences from other metals are
used to ensure data of acceptable quality from the analysis phase
of the measurement method.
3.3.1.5 Calculations. Calculations for this method are known to be a
major source of error. Some calculations involve several terms and should
only be attempted (for the final report) at a desk or work table and pre-
ferably with the aid of a calculator or at least a good slide rule. A
computer program using raw data as an input is highly recommended for mak-
ing the final calculations.
As a check, it is recommended that all calculations be independently
repeated from raw data.
3.3.2 How to Monitor Important Variables
In general, if the procedures outlined in the Operations Manual are
followed, the major sources of measurement variability will be in control.
It is felt, however, that the supervisor should visually check certain
parameters and operations periodically while measurements are being made
80
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to insure good operator technique and the proper use of equipment. The
parameters and operations to check are essentially those recommended for
the auditor as listed in subsection 4.3.
Results of the calibration checks for the dry gas meter, orifice
meter, nozzle diameter, and pitot tube should be checked before each field
test. Any item of equipment not satisfying the suggested performance
criteria of table 1 should be calibrated or replaced.
There appears to be a need for actual field data on several of the
parameters or variables involved in this measurement method in order to
better judge their influence on measurement variability. One of the most
effective means of identifying and quantifying important sources of vari-
ability is through the use of quality control charts. Quality control
charts will provide a basis for action with regard to the measurement pro-
cess; namely, whether the process is satisfactory and should be left alone,
or whether the process is out of control and action should be taken to
find and eliminate the causes of excess variability. In the case of this
method in which documented precision data are scarce, the quality control
charts can be evaluated after a period of time to determine the range of
variation that can be expected under normal operating conditions. Also,
even though results from individual field tests are within bounds, trends
can be identified and corrective action taken further improving data
quality through the proper use of control charts.
Discussions of control charts and instructions for constructing and
maintaining them are given in many textbooks in statistics and quality
control, such as in references 19 and 20.
It is good practice to note directly on control charts the reason for
out-of-control conditions, if determined, and the corrective actions taken.
It is also good practice to maintain control charts in large size, e.g.,
8-1/2 x 11 (inches) or larger and to keep them posted on a wall for view-
ing by all concerned, rather than have them filed in a notebook. Recom-
mended control charts are discussed below.
3.3.2.1 Pitot Tube Calibration Coefficient. A sample control chart for
pitot tube calibration checks is given in the quality assurance document
81
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of this series for Method 2—Determination of Stack Gas Velocity and
Volumetric Flow Rate (type-S pitot*tube)—(ref. 3), page 38.
3.3.2.2 Range Chart for Beryllium Emission Rate Replicates. In compliance
testing where it is desired to determine the source output at a fixed level
of operation, a large range in the three replicates would suggest process
variability and/or measurement variability. Expressing the range, RG, as
a percent of the average, i.e., the difference in the largest and smallest
of the three replicates divided by the average of the three replicates, all
multiplied by 100; a control chart with limits as given in figure 7 can be
used initially. These limits are based on the assumption of equal vari-
ability in the source output and the measurement process. (As field data
becomes available more appropriate estimates can be made.) Therefore, the
coefficient of variation used in constructing the control chart becomes
/2~ x CV{R} = /2~ x 37 = 52. The upper control limit (UCL) is calculated
using the following equation:
UCL = D2 CV = D2 x /2~~ CV{R} (13)
where D« is the factor for three-sigma control limits (3a) for range values
when standards are given (ref. 21). Table 2 lists several D^ values as
a function of the number of samples. Determining limits in this way serves
as a starting point in the analysis of the data. When a data point falls
out of bounds on this graph, the process data should be checked to see if
the process changed between runs and the percent of isokinetic calculations
checked to see if one run was significantly different from the others in
order to identify the cause of the excessive variability. Note then that
exceeding the upper control limit does not necessarily invalidate the test
data.
3.3.2.3 Mean and Range Charts for Percent of Isokinetic Sampling. Main-
taining isokinetic sampling conditions is important in beryllium sampling.
Control charts displaying the range and mean of percent isokinetic sampling
provide, at a glance, means for evaluating the performance of a team or
groups of teams over an extended period of time. If deviations from
* See section 4.1.4 for CV{R} = 27.
82
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Table 2. Factors for Control Charts for the Range, RG
Number of
Samples
n
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Factor for
Center Line
d2
1.128
1.693
2.059
2.326
2.534
2.704
2.847
2.970
3.078
3.173
3.258
3.336
3.407
3.472
Factor for Control Limits
Lower
Dl
0
0.3
0
0
0
0.205
0.387
0.546
0.687
0.812
0.924
1.026
1.121
1.207
Upper
D2
3.686
4.358
4.698
4.918
5.078
5.203
5.307
5.394
5.469
5.534
5.592
5.646
5.693
5.737
isokinetic greater than + 10 percent are not allowed, i.e., the run has
to be repeated, then in a rough way 10 percent can be taken as the 3(7
value giving a standard deviation of about 3.3 percent. Based on three
replicates and the above standard deviation, the range chart and mean
charts are given in figures 8 and 9, respectively.
The RG values are plotted sequentially as they are obtained and con-
nected to the previously plotted point with a straight line. Corrective
action, such as instruction in proper operating technique, should be taken
before the next field test any time one of the following criteria are
exceeded:
1. One point falls outside the UCL.
2. Seven consecutive points fall above the RG line.
Exceeding the first criteria will usually indicate poor technique or equip-
ment malfunction between sample runs of a particular field test. Exceed-
ing the second criteria indicates a systematic error due to equipment
83
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160
| 140
8. 120
'§ 100
o
o
- 80
x
g 60
40
FIELD TEST
NO.
DATE
FIELD TEAM
PROBLEM
AND
CORRECTIVE
ACTION
.
-
~
" /
~
1
>»»^
s
f
2
S
^~S
3
UCL'
/\
r \
\
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>
4
= 158
\
V
5
^
6
,
"f"
RG =
7
c
cu
t)
c
O ^
0 C
~o 'o
15 Q.
^ OJ
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T3 >
O to
u —
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QJ
E «
03 C
a ^
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u 5
o *-
t- 0)
CL -Cl
V
62
8
A
9
c c
D 3
*- ^
o E
H- O
--P ^
o^ QJ
8 ^
wo
g i-
. — . ~o
1— 1 c
' — ' ^S
CJ (^
^ -C ¥
0 "ro g-
~ "^ ^
c c 0
g 0 c
53 V £
CL EC 5
X
10
*UCL = D2CV = 4.358 x 37 x /2
TRG =d2CV = 1.693 x 25.7 x /2
158.4
43.5
Figure 7. Sample control for the range, RG of R replicates.
84
-------
c
o
CD
Q.
~C
'£
01
c
ro
CC
18
16
14
12
10
8
6
4
2
UCL = 14.4*
FIELD TEST
NO.
10
DATE
FIELD TEAM
PROBLEM
AND
CORRECTION
ACTION
*UCL = D2o = 4.358 X 3.3 = 14.4
tRG = d2a = 1.693 X 3.3 = 5.6
Figure 8. Sample control chart for the range, RG of percent
isokinetic, 1, sampling for three test runs per
field test.
85
-------
c
8
0)
D.
01
c
c
CD
U
U.
o>
Q.
CL>
>
<
106
104
102
100
96
94
UCL = 105.7*
Warning Limit = 103.6
Warning Limit = 96.2
LCL = 94.3
FIELD TEST NO.
10
DATE
FIELD TEAM
PROBLEM AND
CORRECTIVE
ACTION
*UCL = I + 3a{l}= 100 + 3 X 3.
105.7
Figure 9. Sample control chart for the average percent of
isokinetic sampling per field test.
86
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bias or poor technique. (Note that the UCL can be exceeded without violat-
**-t
ing the I = 100 + 10 interval for any one run.)
The I values, i.e., average percent of isokinetic sampling per three
sampling runs, are plotted sequentially as they are obtained from field
tests and connected to the previously plotted point with a straight line.
Corrective action, such as instruction in proper operating technique
and/or performing equipment calibration checks should be taken before
attempting the next field test any time one of the following criteria is
exceeded::
1. One point falls outside the UCL or LCL.
2. Two out of three consecutive points fall in the warning zone
(between 2a and 3a limits).
3. Seven consecutive points fall on the same side of the center line.
Exceeding the first criteria will usually indicate poor technique or
equipment malfunction. The second and third criterion when exceeded indi-
cate an assignable source of variability due either to faulty equipment or
a consistent error in performing the operation procedures.
3.3.2.4 Control Chart for the Measurement of Working Standard Solutions.
Frequent measurement of working standard solutions is the best means of
assuring stability of the spectrometer during sample analysis. It is
assumed herein that deviations greater than +_ 0.18 yg/m£ from the known
value are sufficient to require the development of a new calibration curve.
Assuming that the difference in the measured (C ) and known concentrations
m
(C ) is normally distributed about a zero mean with a standard deviation
of 0.6 yg/m£, a control chart such as shown in figure 10 can be used.
Corrective action such as generating a new calibration curve should
be taken any time one of the following criteria is exceeded:
1. One point falls outside the UCL or LCL.
2. Two out of three consecutive points fall in the warning zone
(between the 2<3 and 3(7 limits) .
3. Seven consecutive points fall on the same side of the center line.
87
-------
U
I
01
G
c
0)
>-l
01
14-1
14-1
FIELD TEST
NO.
Upper Control LimitL
. Warning Limit
Warning Limit
Lower Control Limit
10
DATE
FIELD TEAM
PROBLEM
AND
CORRECTIVE
ACTION
Figure 10. Sample control chart for the measurement of work-
ing standard solutions.
-------
SECTION IV
MANUAL FOR MANAGER OF GROUPS OF FIELD TEAMS
89
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SECTION IV MANUAL FOR MANAGER OF GROUPS OF FIELD TEAMS
4.0 GENERAL
The guidelines for managing quality assurance programs for use with
Test Method 104 - Reference Method for Determination of Beryllium Emis-
sions from Stationary Sources are given in this part of the field docu-
ment. This information is written for the manager of several teams for
measuring source emissions and for the appropriate EPA, State, or Federal
Administrators of these programs. It is emphasized that if the analyst
carefully adheres to the operational procedures and checks of Section II,
then the errors and/or variations in the measured values should be con-
sistent with the performance criteria as suggested. Consequently, the
auditing routines given in this section provide a means of determining
whether the stack sampling test teams of several organizations, agencies,
or companies are following the suggested procedures. The audit function
is primarily one of independently obtaining measurements and performing
calculations where this can be done. The purpose of these guidelines is
to:
1. Present information relative to the test method (a functional
analysis) to identify the important operations and factors.
2. Present a methodology for comparing action options for improving
the data quality and selecting the preferred action.
3. Present a data quality audit procedure for use in checking adher-
ence to test methods and validating that performance criteria are being
satisfied.
4. Present the statistical properties of the auditing procedure in
order that the appropriate plan of action may be selected to yield an
acceptable level of risk to be associated with the reported results.
These four purposes will be discussed in the order stated in the
sections which follow. The first section will contain a functional analy-
sis of the test method with the objectives of identifying the most impor-
tant factors which affect the quality of the reported data and estimating
90
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the expected variation and bias in the measurements resulting from equipment
and operator errors.
Section 4.2 contains several actions for improving the quality of the
data; for example, by improved analysis techniques, instrumentation, and/or
training programs. Each action is analyzed with respect to its potential
improvement in the data quality as measured by its precision. These
results are then compared on a cost basis to indicate how to select the
preferred action. The cost estimates are used to illustrate the metho-
dology. The manager or supervisor should supply his own cost data and
his own actions for consideration. If it is decided not to conduct a
data audit, sections 4.1 and 4.2 would still be appropriate as they contain
a functional analysis of the reference method and of alternative methods
or actions.
There are no absolute standards with which to compare the routinely
derived measurements. Furthermore, the taking of completely independent
measurements at the same time that the routine data are being collected
(e.g., by introducing two sampling probes into the stack and collecting
two samples simultaneously) is not considered practical due to the con-
strained environmental and space conditions under which the data are being
collected. Hence, a combination of an on-site system audit, including
visual observation of adherence to operating procedures, and quantitative
performance audits is recommended as a dual means of independently check-
ing on the source emissions data.
The third section contains a description of a data quality audit pro-
cedure. The most important variables identified in section 4.1 are con-
sidered in the audit. The procedure involves the random sampling of n
stacks from a lot size of N = 20 stacks (or from the stacks to be tested
during a three-month period, if less than 20) for which one firm is conduct-
ing the source emissions tests. For each of the stacks selected, indepen-
dent measurements will be made of the indicated variables. These measure-
ments will be used in conjunction with the routinely collected data to
91
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estimate the quality of the data being collected by the field teams,
The data quality audit procedure is an independent check of data col-
lection and analysis techniques with respect to the important variables.
It provides a means of assessing data collected by several teams and/or
firms with the potential of identifying biases/excessive variation in the
data collection procedures. A quality audit should not only provide an
independent quality check, but also identify the weak points in the mea-
surement process. Thus, the auditor, an individual chosen for his back-
ground knowledge of the measurement process, will be able to guide field
teams in using improved techniques. In addition, the auditor is in a
position to identify procedures employed by some field teams which are
improvements over the current suggested ones, either in terms of data
quality and/or time and cost of performance. The auditor's role will thus
be one of aiding the quality control function for all field teams for
which he is responsible, utilizing the cross-fertilization of good mea-
surement techniques to improve the quality of the collected and reported
data.
The statistical sampling and test procedure recommended is sampling
by variables. This procedure is described in section 4.4. It makes max-
imum use of the data collected, and it is particularly adaptable to the
small lot size and, consequently, the small sample size applications.
The same sampling plans can be employed in the quality checks performed
by a team or firm in its own operations. The objectives of the sampling
and test procedure are to characterize data quality for the user and to
identify potential sources of trouble in the data collection process for
the purpose of correcting the deficiencies in data quality.
Section 4.4.4 describes how the level of auditing, i.e., the sample
size n, may be determined on the basis of relative cost data and prior
information about the data quality. This methodology is described in
further detail in the Final Report on the Contract. The cost data and
prior information concerning data quality are supplied to illustrate the
procedure and these data must be supplied by the manager of groups of
92
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field teams depending upon the conditions particular to his responsibility.
Figure 11 provides an overall summary of the several aspects of the
data quality assurance program as described in these documents. The flow
diagram is subdivided into four areas by solid boundary lines. These
areas correspond to specific sections or subsections of the document as
indicated in the upper right hand corner of each area. The details are
considered in these respective sections of the document and will not be
described here.
4.1 FUNCTIONAL ANALYSIS OF TEST METHOD
Test Method 104 - Reference Method for Determination of Beryllium
Emissions from Stationary Sources—as described in appendix A of this docu-
ment is subjected to a functional analysis in this section. This method,
in addition to its use in determining beryllium emissions, is also used to
simultaneously determine the moisture content of the stack gas and to
perform a velocity traverse from which the volumetric flow rate can be
calculated. These results combined with the stack gas composition as
measured by Method 3 yield a beryllium emission rate for the source being
tested.
A functional analysis of the measurement process is performed for
the following purposes:
1. To identify variables, operations, and factors that can influence
the quality of the measurement data.
2. To determine how elements of uncertainty are propagated through
the system to the resulting data.
3. To estimate the mean values and ranges of the various error
sources existing under normal operating conditions and to determine the
probable uncertainty to be associated with the reported measurements.
The results of the functional analysis provide information for the
following:
1. Setting acceptable limits on data quality, i.e., precision and
accuracy.
93
-------
Pollutant
Measurement
Method
Subsection 4.1
Functional
Analysis
Estimate Ranges
and Distributions
of Variables
Identify and Rank
Sources
Bias/Variation
Perform Overall
Assessment
Section III
Subsections 4.3 and 4.4
Subsection 4.2
Develop Standards
for Audit Procedure
Develop Standards
for Q. C.
Procedure
Data
are of
Satisfactory
Quality
Institute
QC Procedure
for Critical
Variables
Evaluate Action Options
for Improving Data
Quality
Assess Data
Continue to Use
Measurement Meth,
as Specified
Cost of
Implementing
Actions
Select Optimal
Action and
Implement
Modified
Measurement
Method
Quality Using
Audit Data
Data
Quality
Satisfactory
Yes
Continue to Use
Measurement Method
as Specified
Figure 11. Summary of data quality assurance program.
94
-------
2. Implementing quality controls to those factors that would other-
wise result in excessive uncertainty in the resulting data,
3. Application of appropriate quality assurance practices (audits)
at critical points in the measurement system with acceptable limits to
be considered and actions to be taken when limits are exceeded.
This method for determining beryllium emission rates has been sub-
jected to one collaborative test (ref. 16) hence some quantitative data is
available. Except for the analysis phase, this method is almost identical
in procedures and equipment to those required by Method 5 (ref. 16).
For this reason, test data from the sampling phases of Method 5 is
directly applicable to the same phases of Method 104 and has also been
used in this document to depict representative accuracy and precision data.
Estimates of the mean value and variability associated with the individual
variables in the measuring rpocess were made using data from published
documents. If data were not available, engineering judgments were used
•
to estimate variable limits.
The functional analysis is discussed in two stages. Variable evalua-
tion and range estimates are discussed first. For example, the mean value
and variability on which the beryllium emission rate, R, depends will be
given. Second, a variance analysis is performed to determine the sensitivity
of the emission rate measurement to each of the variables. The results
of this analysis are the basis for many of the limits used throughout this
document.
The beryllium emission rate is calculated from the relationship:
Qs
R = K x W x ^ (14)
total
where R = Rate of beryllium emissions, g/d
K = 8.6 x 10~2 £Z5T
yg-d
W = Total weight of beryllium collected, yg
t 3
Q = Volumetric flow rate of the stack gas, m /s
s 3
V = Total volume of gas sample at stack conditions, m .
t o taJ-
95
-------
The variability of the beryllium emission rate, R, will consist of com-
ponents of variability from the individual determinations of W , Q , and
L o
V . Each of these three terms will be discussed separately below
following a short definition of terms.
The variance analysis conducted in this section provides a statis-
tical means of identifying important variables in the measurement pro-
cess based on estimated variances and coefficients of variations. The
mathematical basis for the procedures are described in the Final Report
on Contract 68-02-0598 (ref. 22).
Many different measures of variability are conceivable depending
upon the circumstances under which the measurements are performed. Only
two extreme situations will be discussed here. They are:
1. Repeatability, is a measure of the variability in determinations
made on the same sample (i.e., the same source with source parameters
held as constant as possible) by the same field team using the same
equipment over a short period of time. The repeatability standard devia-
tion and the coefficient of variation are symbolized by a and CV respectively,
2. Reproducibility is the variability associated with measurements
made of the same sample (i.e., same source with source parameters held as
constant as possible) by different field teams using different equipment
over extended periods of time. The reproducibility standard deviation and
the coefficient of variation are symbolized by <3 and CV respectively.
R R
The above definitions are based on a statistical model where each
determination of the rate of beryllium emissions is the sum of three com-
ponents as follows:
R = R + b + e (15)
where R = the measured rate of beryllium emissions, g/d
R = the general average, rate of beryllium emissions, g/d
b = an error term representing the difference between laboratories,
g/d
e = a random error occurring in each measurement, g/d.
96
-------
In general, b can be considered as the sum:
b = b + b (16)
r s
where:
b = random component
b = systematic component
S
The term b is considered to be constant during any series of measurements
performed under repeatable conditions, but to behave as a random variate
in a series of measurements performed under reproducible conditions. Its
variance is denoted by
2
var b = O (17)
l_j
2
where a is the variance between laboratories or field teams, including
L
the variance between analysts and between equipment.
The term e represents a random error occurring in each measurement.
Its variance is denoted by
2
var e = a , (18)
7
where a is called the repeatability variance.
The reproducibility standard deviation is related to the between
laboratories variance and the repeatability variance by
: L •
Repeatability and reproducibility of beryllium emission rate deter-
minations will be discussed in the following subsections.
4.1.1 Weight of Beryllium Collected, W . The total collected beryllium,
W , is given by
W = W + e (20)
where W represents the true beryllium mass per unit volume of stack gas
97
-------
at stack conditions and e is the error associated with the collection and
analysis of the beryllium sample. Important sources of error in the deter-
mination of W include:
1. Deviation from isokinetic sampling, (I);
2. Loss or gain of sample during sample recovery, (SR);
3. Volumetric measurement of collected sample, blank, and
impinger contents plus wash amounts, (V); and
4. Variability in the spectrophotometric analysis phase of
the measurement process, (A).
These four sources of error are independent; hence, the coefficient of
variation of W , CV{W }, can be estimated by:
™2/TT , _ a2{i) +a2{SR} +q2{v} + a2{A>
CV |W } - --—
wt
2
Using the ratios discussed in the following paragraphs, CV {W } can be
estimated to be .10. Therefore CV{W } = 31 percent.
4.1.1.1 Nonisokinetic sampling (I). Deviation from isokinetic sampling con-
ditions can result in measurement error which is directly related to
the degree of departure from isokinetic conditions and the particle size
•distribution in the sample gas. Departure from isokinetic ^^mling ran
occur, for instance, as a result of failure to adjust the nozzle velocity
as the stack gas velocity varies. This type of departure will be detected
when the percent of isokinetic sampling is calculated. Deviations from
isokinetic sampling can also occur when errors are made in the pitot tube
coefficient or in the nozzle diameter determinations. Unlike the example
given above, these deviations from isokinetic sampling are not detectable
from any checks that can be performed in the field.
Sample gases containing particle size distributions extending into
the 25 ym and above sizes are sensitive to ncnsokinetic sampling error and
each particle size distribution should be evaluated separately. In beryl-
lium sampling the particle size is usually small; therefore, slight devia-
tions from isokinesis (on the order of + 10 percent from the acceptable
-------
range) will contribute negligibly to the overall system error. Based
on this statement, then an estimated error in the beryllium emission
rate determination due to nonisokinesis (a{l}/W.) is .08.
4.1.1.2 Sample recovery (SR). A loss or gain of sample during sample
recovery is mostly a function of technique and of the work area used for
sample recovery. Sample recovery involves transferring the filter from the
filter holder to a sample container and removing particulate matter lodged
in the nozzle, probe, filter holder, and connecting glassware. No quanti-
tative data are available for estimating this source of error. For this
analysis, a coefficient of variation for repeatability of 2 percent is
assumed. This, of course, indicates the best that can be achieved and
does not include large deviations due to mistakes, accidents, or poor
technique. A a(SR}/W of .25 is assumed.
4.1.1.3 Volumetric measurement of collected sample, blank, and impinger
contents,(V). The volumetric measurement error is a combination of three
measurements as required by equation 7, section 2,5.3.6. Assuming that
each volume is measured to the nearest m£, a a{V}/W of .07 is reas.onahle
as a result of the three independent measurements.
4.1.1.4 Analysis (A). Primary sources of variability in the analysis
phase of the beryllium emission rate determination are discussed in
subsection 3.3.1.4. They include:
1. Sample handling,
2. Preparation of standards, and
3. Setting and maintaining standard conditions throughout the
analysis period.
Based on the analysis information acquired from reference 16, an estimated
ratio of a{A}/W of .15 is used in this document for illustrative purposes.
This assumes that well-trained analysts make the determination in accor-
dance with the recommendations in section 2 of this document in well-
equipped laboratories.
99
-------
4.1.2 Volumetric Flow Rate, Q , A functional analysis of the method
" i -- - — - T g -
used to measure volumetric flow rate was made in the quality assurance
guidelines document for Method 2 (ref. 3). The results of that analysis
will be used here without repeating the analysis itself, A repeatability
coefficient of variation of 2.33 percent was derived for the volumetric flow
rate. This value is used here as an estimate of how well a field team
can repeat its measurement using the same equipment, assuming the velocity
profile remains constant, and with only short periods of time between
measurements. A higher value of 3 percent is used to represent the
reproducibility coefficient of variation.
4.1.3 Total Volume of Gas Sample at Stack Conditions, total. The total
gas sample volume is given by
V_ _ , = V + V (22)
total m w
s s
where 3
V , = Total gas sample volume at stack conditions,m
t O tclX
V = Volume measured by the dry gas meter at stack
s 3
conditions, m
3
V = Volume of water vapor at stack conditions, m
w
s
In terms of measured parameters the total gas sample volume is given by
AH
„ V s \ bar 13.6 / , K Vn s
Vtotal = m T P + W lc P- (23)
s
where: V = Volume of gas sample through the dry gas meter (meter
m 3
conditions), m
T = Average temperature of stack gas, °K
S
T = Average dry gas meter temperature, °K
P = Barometric pressure at the orifice meter, mm Hg
AHa = Average pressure drop across the orifice meter, mm H-O
13.6 = Specific gravity of mercury
P = Stack pressure, (Barometric + static pressure), mm Hg
S
100
-------
V = Total volume of liquid collected in impingers and silica
£
gel, m£.
= .00346 mm Hg - m
w
°K
Variability in V is a combination of variability of the dry gas meter,
m
inaccuracy of the calibration standard, and sampling train leaks, including
those leaks undetected because of pump valve float. Assuming coefficients
of variation of 1 percent, 0.4 percent, and 0.5 percent for the dry gas
meter, calibration standard, and sampling train leaks, respectively, results
in a CVJV \ = 1.2 percent.
( '
m
CV.JP
(
I
) = 0.
bar) = 0.3 percent and CVJT I = 0.5 percent are assumed from pre-
vious documents of this series (ref . 3) .
Variability in AH is believed to be primarily due to reading error
(inclined manometer) and calibration error in determining AH@ (AH@ is the
3 3
pressure drop across the orifice meter resulting in a .021 m /min (0.75 ft /min)
flow rate at standard temperature and pressure) . The pressure drop across
the orifice, i.e., AH is relatively constant with no fluctuations and hence,
easily read on an inclined monometer. Also, random reading error is
averaged out because AH as used in equation (2) is an average of at Least
12 readings. Therefore, the variability of the average pressure drop should
be adequately characterized by a coefficient of variation of 1 percent,
i.e.,{CV AH } = 1 percent. These assumptions are summarized in table 3.
The estimated variance of V , , as given by equation 3, section
2.5.3.3 can be derived from the following equation:
(.007)2a2{Ts}
(-.009)2 a2
(.003)2 a2
+ (.0002)2 a2
JAHavg}
+ (-.005)
(.002)2 a2
= .0039
101
-------
Table 3. Means and Variabilities of Parameters Affecting V
total
Parameter
Vl
T °
s
P
s
V
m
T
m
bar
^H
avg
Mean Value
252 m£
405°K(730°R)
707 mm(27.9 in. Hg)
1.7 m3(60 ft3)
294°K(530°R)
760 mm Hg(29.9 in. Hg)
102 mm H~0(4 in. H00)
2 2
Estimated CV
for Repeatability
CV{V7 }= 1.0%
J-c
CV{T }= 1.5%
s
CV{P }= 0.9%
s
CV{V }= 1.2%
m
CV{T }= 0.5%
m
CV{P, }= 0.3%
bar
CV{AH}= 1.0%
Since CV2(Vtotal} = ^Xotal^ Vta/' then CV{Vtotal} is 2.9 percent. The
most important variables in the determination of V , are clearly T and V .
total s m
4.1.4 Beryllium Emission Rate, R.
The beryllium emission rate is calculated with equation 14 section
2.5.3.7. The variance of this determination can be calculated as follows
(derived by using the Taylor series for the variance of a ratio) :
(24)
cv {R} = cv2 |wt| + cv2 |QS| + cv2 {v
Using the coefficients of variation discussed in previous paragraphs
2
CV {R} = .14 and CV {R} = 37 percent. This coefficient of variation
is used here for illustrative purposes and is reasonable for sampling by
experienced crews with adequate equipment.
4.2 ACTION OPTIONS
Suppose it has been determined as a result of the functional analysis
and/or the reported data from the checking and auditing schemes, that
102
-------
the data quality is not consistent with suggested standards or with the
user requirements. Poor data quality may result from (1) a lack of ad-
herence to the control procedures given in section II—Operations Manual,
or (2) the need for an improved method or instrumentation for taking
the measurements. It is assumed in this section that (2) applies; that
is, the data quality needs to be improved beyond that attainable by fol-
lowing the operational procedures given for the reference method.
The selection of possible actions for improving the data quality can
best be made by those familiar with the measurement process and by the
judicious use of the functional analysis as described in section 4.1. For
each action, the variance analysis can be performed to estimate the vari-
ance, standard deviation, and coefficient of variation of the pertinent
measurement(s). In some cases it is difficult to estimate the reduction
in specific variances, which are required to estimate the precisions of the
pertinent measurements. In such cases, an experimental study should be
made of the more promising actions based on preliminary estimates of pre-
cision/bias and costs of implementation of each action. This preliminary
analysis would follow the methods suggested below;
AO: Reference Method
Al: Crew Training (cost of $1000 per 20 stacks)
A2: Use of NBS Standard Reference Materials (cost of $750 per
laboratory per year)
A3: Use of Programmable Minicalculator in lieu of Nomographs
(cost of $350 per 20 stacks)
The costs given for each action are additional costs above that of the
reference method. Assumptions concerning the reduction in variances
(or improved precisions), are given for each action in the following
paragraphs.
(1) Crew Training, Al. It is assumed that the coefficient of variation
of R is reduced by 25 percent, or,
CVJR Al} = 0.75 CVJR
103
-------
The notation CVJRJAl} denotes the "estimated CV of R given that Al is
implemented"; the vertical line is to be interpreted as "given that;"
and the letters following the vertical line designate the implemented
action as defined above. This results in a straightforward computation
of CV{R|AI} = 0.75 x 25.7 = 19.3 percent.
In estimating the cost for implementing this action it was assumed
that one crew member be sent to a reputable source sampling school one
week out of a year. The cost of the school plus subsistence is estimated
to be $1000 in excess of salary and benefits. This cost is prorated
over 20 source tests which is a reasonable number of tests per team per
year.
(2) Standard Reference Materials, A2. The purchase and use of Standard
Reference Materials (SRM's) acquired from the National Bureau of Standards
is recommended for the analysis phase of the beryllium determination. From
the SRM's, which are available in a set of three millipore filters in
plastic cylinders certified at three different amounts of beryllium, a
set of standard reference samples can be made for calibration of the
spectrophotometer. Stated simply, the filters would be dissolved in an
appropriate acid such as sulfuric acid or nitric acid and hydrogen peroxide
and the resulting concentrated solutions stored in polyethelene containers.
The working beryllium standard solutions are then diluted to the range of
the NBS standard samples and the values compared and calibrated. These
working standards are used throughout the measurement process to con-
tinually check the calibration of the spectrophotometer.
It is assumed that the coefficient of variation of R is reduced by
40 percent, or
CV{R|A2l = 0.60CV{RJAO}.
This results in a CV{R|Al} = 15.4 percent. An estimate of the cost based
on the cost of a set of NBS filters, the additional manhours required to
dilute and compare the standard working solutions, is $7^0 per laboratory
per year. Assuming an average of 20 stacks sampled per year the figure
is $750 per 20 source tests.
104
-------
(3) Minicalculator in Lieu of Nomographs, A3. It is assumed that the
coefficient of v;
lowing equation:
coefficient of variation of V /V is reduced in accordance with the fol-
n s ..
CV{R|A3} = 0.90 CV {R|AO}.
Therefore CV{R|A3} = 23.1 percent. An increase in precision and accuracy
should be realized since exact values of C , AH@, and M, would be used
P a
to determine isokinetic conditions rather than the mean values of their
expected range as are now built into the nomograph. Also, routine cal-
culation errors (i.e., error in setting and reading the nomograph) should
be greatly reduced. A programmable mini-calculator can be purchased for
about $350. Cost of programming should be more than recovered in samp-
ling time saved as a result of using the calculator. The increased cost
is taken as #350 per 20 source tests.
4.2.1 Actions Applied in Combination
In addition to treating each action separately, some of the actions
can be combined to yield a further reduction in the variance of R or
an increase in the precision. The assumptions stated above for the
individual actions are applied in combination where appropriate to obtain
an overall estimate. For example, applying actions Al and A2 in combina-
tion results in a CV{R} = 11.58 percent. The costs are assumed to be
additive, i.e. costs for applying Al and A2 separately are added to
obtain the cost of applying both Al and A2. Similarly the costs are
added for other combinations.
4.2.2 Comparison of Actions
The added cost per 20 stacks is plotted as a function of the pre-
cision of the estimated R's as measured by its coefficient of variation,
CVfR}, in figure 12. Examination of the plotted results enables one to
quickly identify the action or combination of actions which will yield
results of some desired precision. In practice it may not be reasonable
to insist that the data be of a specified precision, but that the cost
105
-------
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106
-------
of reporting poor quality data is a rapidly increasing function of the
data quality for data of variability exceeding a specified value. The
selection of the best action option then becomes a trade-off between the
overall cost and the expected precision to be achieved by its implemen-
tation. The cost of implementing an action plus the cost of reporting
poor quality data are added to obtain an overall cost for the action.
(An assumed function of the cost of reporting poor quality data is shown
as the solid curve in figure 12 as an illustration only. Its exact
shape and location on the graph would have to be determined from actual
cost data) .
4.3 PROCEDURES FOR PERFORMING A QUALITY AUDIT
"Quality audit" as used here implies a comprehensive system of planned
and periodic audits to verify compliance with all aspects of the quality
assurance program. Results from the quality audit provide an independent
assessment of data quality. "Independent" means that the individuals
performing, and as much as possible of the equipment used in the audit,
are different from the regular field crew and equipment. From these
data both bias and precision estimates can be made for the measurement
process.
The auditor, i.e., the individual performing the audit, should have
extensive background experience in source sampling, specifically with
the characterization technique that he is auditing. He should be able
to establish and maintain good rapport with field crews.
The functions of the auditor are summarized in the following list:
1. Observe procedures and techniques of the field team during
on-site measurements.
2. Perform certain independent checks, and from previous
training and experience, estimate the validity of the
field crew's measurements.
3. Check/verify applicable records of equipment calibration
checks and quality control charts in the field team's home
laboratory.
107
-------
4. Perform calculations using data obtained from the audit.
5. Compare the audit value with the field team's test value.
6. Inform the field team of the comparison results specifying
any area(s) that need special attention or improvement.
7. File the records and forward the comparison results with
appropriate comments to the manager.
4.3.1 Frequency of Audit
The optimum frequency of audit is a function of certain costs and
desired level of confidence in the data quality assessment. A methodology
for determining the optimum frequency using relevant costs is presented
in subsection 4.4.4. For the costs assumed in this document, an optimum
level of n = 5 for a lot size of N = 20 results as shown in figure 13.
However, costs will vary among field teams and types of field tests.
Therefore, the most cost effective auditing level will have to be derived
using local cost data according to the procedure given in subsection
4.4.4 and in the final report on this contract.
4.3.2 Collecting Audit Information
While at the sampling site, the auditor should observe the field
team's overall performance of the field test. Table 4 is a sample check-
list of the operations to observe. Each item on the list should be
checked yes or no according to whether it was performed as recommended
in the operations manual and, if applicable, the result was within speci-
fied limits. Those items checked no should be explained under comments.
No checklist can cover all situations; the auditor must utilize his good
judgment and include other checks as deemed desirable for a specific
situation.
A completed checklist with all yes checks implies that in the opinion
of the auditor the measurement was made in such a manner that large biases
resulting from poor technique are not likely to be present.
In addition to the above observations, the auditor should independently
108
-------
$8000
w
i
O
u
0>
60
n)
1-1
$6000 .
$4000
$2000
P
4567
Audit Level (n)
p = Proportion defective E-^.asurements in the "lot"
P{Acc. lot with p) < 0.1
10
Figure 13. Average cost vs audit level (n)
109
-------
Table 4. Beryllium Emission Determination Checklist to be Used by Auditor
YES
NO
OPERATION
EQUIPMENT PREPARATION AMD CHECK
1. Sampling train assembled and leak checked.
2. Probe and filter box heaters checked and set for proper
temperatures.
3. Stack gas temperature measuring system assembled and
checked for proper operation by comparing to a mercury
in glass thermometer.
4. Stack gas velocity measuring system assembled and checked
for proper operation.
5. Orsat analyzer assembled and checked (if used).
PRELIMINARY MEASUREMENTS
6. Selection of traverse points according to Method 1.
7. Moisture content by Method 4, or equivalent.
8. Molecular weight by Method 3, or equivalent.
9. Measurement of stack dimensions.
10. Mark probe for sampling at traverse points.
SAMPLE COLLECTION
11. Equal sampling time at each traverse point.
12. Probe temperature satisfactory throughout the test.
13. Filter box temperature at appropriate temperature to pre-
vent condensation throughout the test.
14. Sample gas temperature at last impinger -x, 20°C (68°F)
throughout the test.
15. Isokinetic sampling checked and adjusted if necessary
at least every 5 minutes.
16. Leak check of sampling train before and after each run.
SAMPLE RECOVERY
17. Satisfactory handling and movement of probe and filter
to sample recovery area.
18. Recovery area satisfactory (i.e., space, cleanliness, etc.)
110
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Table 4. Beryllium Emission Determination Checklist to be Used by Auditor
(continued)
YES
NO
OPERATION
19. Sample recovery procedure adequate.
20. Proper labeling of sample containers.
21. Determination of moisture content procedure adequate.
ANALYSIS
22. Proper calibration of the spectrophotometer.
23. Careful dilution techniques used in diluting field samples
and standard samples.
DOCUMENTATION
24. All information recorded on data sheet as obtained.
25. All unusual conditions recorded.
COMMENTS
111
-------
as
da*
0
:V-
tot
And S
tot
Ot
dS"
^d ^- ^ese
ret -d
. ^t-\ *-
- 0'
,ed °u ,.. a-
„ ot
ot
as
^ot<
i1*^
1SV
,0-cd "^a •-« a
•55.
•t^
A rot
.te
-------
determine the stack dimensions. This should be carried out with the reali-
zation that the meajurement is to be used as an estimate of the average
dimension of the stack. Therefore, for example, a stack which could be
out of round should have its diameter measured from as many sampling ports
as possible and the average diameter used as the stack diameter in sub-
sequent calculations. Record the cross-sectional area, A , on the form
sa
of figure 14.
The auditor should obtain from the field team a complete set of test
data, i.e., the data form of figure 5 filled in through the section on
recorded test data, for all sample runs.
In the field team's home laboratory the auditor should verify, by
checking calibration records and field data sheets from previous field
tests, that the performance criteria as given in table 1 of section III
have been satisfied over the period since the last audit. Also, using
his own calibrated standards, perform the following calibration checks.
1. Using his own calibrated wet test meter, or equivalent,
calibrate the dry gas meter and the orifice meter as directed in sub-
section 2.2.3 of section II. Record these audit values as Y and AH@
a
in the form in figure 14.
2. Determine the sampling nozzle diameter, D , according to
na
the procedure of subsection 2.2.1. Calculate the cross-sectional area,
A , in square meters by
2
A = 0.25 x ~ x (D )2 x -— = ^~ (25)
na 7 na n n6 2
10 mm
A = 7.85 x 10 7 x (D )2 = m2.
na na —•—
Record D and A on the audit data sheet of figure 14.
na na
3. Using a calibrated pitot tube, calibrate the field pitot
tube according to the procedure given in subsection 2.1.2, of the quality
assurance document of this series for Method 2. The field pitot tube
112
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AUDIT MEASUREMENTS
STACK CROSS-SECTIONAL ARFA, A
DRY GAS METER CALIBRATION, yg *
ORIFICE METER CALIBRATION, /'HP
a
SAMPLING NOZZIE DIAMETER, 0
SAMPLING NOZZLE CROSS-SECTIONAL AREA,
PITOT TUBE CALIBRATION COEFFICIENT, Cn
Dimensionless
mm H20
Dimensionless
1. v = V * Y =
ma ni
CALCULATIONS
3
AH
T V P, 4-
2 v = V — --^l—
raa m T P
s m s
m at stack conditions
3. V .00346 V, —-
wa IP
s c s
4. V . - V + V
total m w
ass
5. V - .3874 V
"
AH
0.0013 V,
6. B
wo V + 0.0013
"std
ditr^n^ionless
7. M M,(1-B ) + 18B
sa d wo wo
g/g-mole
3.(v ) - 34.96 C (/AP) •»/ —-?-—
sa avg p avg •' D "
n/sec
9. W V0Cn - V C - V C
ta £ £ w w j a
10.
•OE6/1 Wave As
total
100 V
T (oral
T ""^
g/day
percent
n » avg
12. d = -—- x 100
K
percent
Figure 1A. Sample form for recording audit data
113
-------
is calibrated in the sampling configuration, i.e., the pitot tube
is strapped to the sampling probe and isokinetic sampling conditions
are maintained when reading the velocity pressure head with the field pitot
tube. The average coefficient, C , applicable to the AP range measured
in the field test is determined from this calibration data. Record C
Pa
on the form in figure 14.
4.3.3 Treatment of Audit Data
Using the above audit data where applicable and the raw field data,
perform the calculations indicated in figure 14. All variables are in the
same units as used in subsection 2.5.3 of the operations manual. In
figure 14, audit measurements and/or parameters computed using audit mea-
surements are subscripted with an a. Parameters such as (i/S?) , (T ) ,
K avg s avg
M , and B should be calculated by the auditor from the original field
s wo
data. All calculations are recorded on the audit data sheet of figure 14.
The auditor's report of a specific field test to the manager should
include copies of (1) a completed data sheet from the field team (fig. 5,
pp. 41-3), (2) a completed checklist with comments (table 4, p.11C), (3)
a completed audit data sheet with calculations (fig. 14, p. 109), and (4)
a summary of the field team's strong/weak points with an overall numerical
rating and recommended actions as discussed in the following subsection.
4.3.4 Overall Evaluation of Field Team Performance
In a summary-type statement, the field team should be evaluated on
its overall performance. Using the checklist filled out in the field
(table 4) in conjunction with the results of the comparison of audit and
field team values of R and the circumstances under which the test was
performed, field team perforamnce could be rated on a scale of 1 to 5 as
follows:
5 - Excellent
4 - Above average
3 - Average
114
-------
2 - Acceptable, but below average
1 - Unacceptable
Justification for the rating in the form of a list of the team's
strong/weak points with recommendations for improving weak points should
be included in the auditor's report.
4.4 DATA QUALITY ASSESSMENT
Two aspects of data quality assessment are considered in this section.
The first considers a means of estimating the precision and accuracy of
the reported data, e.g., reporting the bias, if any, and the standard
deviation associated with the measurements. The second consideration is
that of testing the data quality against: given standards using sampling
by variables. For example, lower and upper limits, L and U, may be selected
to include a large percentage of the measurements and outside of which it
is desired to control the percentage of measurements to, say, less than
10 percent. If the data quality is not consistent with these limits, L
and U, then action is taken to correct the possible deficiency before
future field tests are performed and to correct the previous data when
possible.
The determination of the audit level is indicated by using estimated
costs associated with falsely inferring that good (poor) quality data are
of poor (good) quality and with auditing n stacks. In addition, prior
information concerning data quality is assumed in order to determines an
expected or average cost resulting from the statistical sampling plan.
The cost estimates provided herein are assumed for the purpose of illus-
trating the methodology. It is emphasised that managers need to supply
their own costs in making such analyses.
4.4.1 Estimating the Precision/Accuracy of the Reported Data
Methods for estimating the precision (standard deviation) and bias
of the mercury emission rate (R) measurements were given in section 4.1.
This section will indicate how the audit data collected in accordance
with the procedure described in section 4.3 will be utilized to estimate
115
-------
the precision and accuracy of the measure of interest. Similar techniques
can also be used by a specific firm or team to assess their own measure-
ments. However, in this case no bias data among firms can be obtained.
The audit data collected as a result of following the procedures in the
previous section are the measured and audited values of R and the difference.
R. - R .
d. = —J 23- x 100 (26)
J R .
where R. = Field measured value of the beryllium emission rate,
average of three replicates, and
R . = Audited value of the beryllium emission rate, average
aj
of three replicates.
Let the mean and standard deviation of the differences d., j = 1, ...n
field tests be denoted by d and s ,, respectively. Thus,
11
d" = y) d./n, (27)
r
=
L
-,1/2
n - ? 1
C (d. - d) /(n - 1) . (28)
4.4.2 Statistical Tests
The mean d is an estimate of the relative bias in the measurements
(i.e., relative to the audited value). Assuming the audited data to be
unbiased, the existence of a bias in the field data can be checked by
the appropriate t-test, i.e.,
116
-------
- o . (29)
See reference 23 for a discussion of the t-test. If t is significantly
large in absolute values, i.e., greater than the tabulated value of t with
n - 1 degrees of freedom, which is exceeded by chance only 5 percent of
the time, then the bias is considered to be real and some check should be
made for a possible cause of the bias. If t is not significantly large,
then the bias should be considered zero or negligible.
The standard deviation, s,, is a function of both the standard devia-
d
tion of the field measurements and of the audit measurements. Assuming
the audited measurements are obtained with much greater precision than the
field measurements, then the calculated s , is an estimate of the standard
d
deviation of the field measurement. Furthermore, since s, is in percent,
it is an estimate of the coefficient of variation, CV{R}. Table 5, con-
tains an example calculation of d and s,, starting with the differences
d
for a sample size of n = 5. See the final report on the contract for
further information concerning this result.
The calculated standard deviation can then be utilized to check the
reasonableness of the assumption made in section 4.1 concerning CV{R} = 25.7
percent for R = 2.0 g/d, for example. (Remember that CV{R } is equal
to a{d}.) The calculated standard deviation, s,, may be directly checked
against the assumed value, a{d}, by using the statistical test procedure
»
f a2{d}
2
where X /f is the value of a random variable having the chi-square dis-
2
tribution with f = n - 1 degrees of freedom. If X /f is larger than the
tabulated value exceeded only 5 percent of the time, then it would be
concluded that the test procedure is yielding results with more variability
than is acceptable due to some assignable cause of large variation .
117
-------
Table 5. Computation of the Mean Difference, d, and
Standard Deviation of the Differences, s .
General formulas
R. - R .
1 J 2 aJ ~ 1 AA
-L . Q . — A J_(JU
J R .
o
d, d /
1 1
o
d,
d3 d/
d d 2
4 4
, 2
d5 d5
£ d £ d 2
2 d=£^-
n
o _2 _ £ dj2 -(Edj)2/n
j. s. —
m rir
d sd
Specific example
Data
L/U L«U
32.0 1024.0
19.5 380.3
10.3 106.1
12.1 146.4
14.6 213.2
88.5 1870.0
d = 17.7%
3 <; - 75 9
J. sd o.y
4. s, = 8.7%
d
118
-------
The measured values should be reported along with the estimated bias,
d, standard deviation, s ,, the number of audits, n, and the total number
of field tests, N, sample (n _< N) . Estimates, i.e., s and d, which are
significantly different from the assumed population parameters should be
identified on the data sheet. For example, based on the data of table 5,
if the field team reported a value of R = 2.0 g/d for one of the
N field tests not audited, then that measurement would be reported
as
1. Measured value, R = 2.0 g/d
2. 'Calculated bias, f{R> = d x R = .35 g/d
3. Calculated standard deviation, cHR} = s x R = 0.174 g/d
4. Auditing level, n = 5, N = 20
From the above data, users of the data can calculate confidence limits
appropriate to what the data are to be used for.
2
The t-test and X -test described above, and in further detail in the
final report on this contract, are used to check on the biases and stan-
dard deviations separately. In order to check on the overall data quality
as measured by the percent of measurement deviations outside prescribed
limits, it is necessary to use the approach described in subsection 4.4.3
below.
4.4.3 Sampling by Variables
Because the lot size (i.e., the number of field tests performed by
a team or laboratory during a particular period, normally a calendar quar-
ter) is small, N = 20, and consequently, the sample size is small on the
order of n = 3 to 7, it is important to consider a sampling by variables
approach to assess the data quality with respect to prescribed limits.
That is, it is desired to make as much use of the data as possible. In
the variables approach, the means and standard deviations, of the sample
of n audits are used in making a decision concerning the data quality.
Some background concerning the assumptions and the methodology is
repeated below for convenience. However, one is referred to one of a
119
-------
number of publications having information on sampling by variables;
e.g., see references 24-27. The discussion below will be given in regard
to the specific problem herein which has some unique features as com-
pared with the usual variable sampling plans.
In the following discussion, it is assumed that only R is audited
as directed in sections 4.3.2.1 and 4.3.2.2.
The difference between the team-measured and audited value of R
is designated as d., and the mean difference over n audits by d, that is,
n r\r\ HI K . "~ R
d = 100 £ f_j__ai_|. (31)
n ^ R .
Theoretically, R. and R . should be measures of the same beryllium
J aJ
emission rate, and their difference should have a mean of zero on the
average. In addition, their differences should have a standard devia-
tion approximately equal to that associated with measurements of R. sep-
arately.
Assuming three standard deviation limits (using the assumed CV = 25.7
percent as derived in the variance analysis of subsection 4.1), the values
-3(25.7%) = -77.1 percent and 3(25.7%) = 77.1 percent define lower and
upper limits, L and U, respectively, outside of which it is desired to
control the proportion of differences, d.. Following the method given in
reference 24, a procedure for applying the variables sampling plan is
described below. Figures 15 and 16 illustrate examples of satisfactory
and unsatisfactory data quality with respect to the prescribed limits L
and U.
The variables sampling plan requires the sample mean difference, d;
the standard deviation of these differences, s,; and a constant, k, which
d
is determined by the value of p, the proportion of the differences out-
side the limits of L and U. For example, if it is desired to control
at 0.10 the probability of not detecting lots with data quality p equal
120
-------
p = Pn + Po < 0.10
Figure 15. Example illustrating p < 0.10 and satisfactory data quality.
p (percent of measured
differences outside
limits L and U) > 0.10
Figure 16. Example illustrating p > 0.10 and unsatisfactory data quality.
12.1
-------
to 0.10 (or 10% of the individual differences outside L and U) and if
the sample size n = 5, then the value of k can be obtained from a table
such as table 6. The values of d and s, are computed in the usual manner;
d
see table 5 for formulas and a specific example. Given the above infor-
mation, the test procedure is applied and subsequent action is taken in
accordance with the following criteria:
1. If both of the following conditions are satisfied:
d - k s , > L = -77.1 percent,
d —
d + k s < U = +77.1 percent
d —
the individual differences are considered to be consistent with the
prescribed data quality limits and no corrective action is required.
2. If one or both of these inequalities is violated, possible
deficiencies exist in the measurement process as carried out for that
particular lot (group) of field tests. These deficiencies should be
identified and corrected before future field tests are performed. Data
corrections should be made when possible, i.e., if a quantitative basis
is determined for correction.
Table 6. Sample Plan Constants, k for P{Not Detecting a Lot
with Proportion P Outside Limits L and U} <_ 0.1
Sample size n
3
5
7
10
12
k(p
3
1
1
1
1
= 0.2)
.039
.976
.721
.595
.550
k(P
4
2
2
2
2
= 0.1)
.258
.742
.334
.112
.045
122
-------
Using the values of d and s in table 6, k = 2.742 for a sample size
n = 5, and p = 0.10, the test criteria can be checked; i.e.,
d - k sd = 17.7 - 2.742(8.7) = -6.2 > L = -77.1 percent
and
d + k sd = 17.7 + 2.742(8.7) = 41.6 < U = 77.1 percent.
Therefore, both conditions are satisfied and the lot of N = 20 measurements
is consistent with the prescribed quality limits. The plan is designed
to protect* against not detecting lots with 10 percent or more defects
(deviations falling outside the designated limits L and U) with a risk
of 0.10; that is, on the average, 90 percent of the lots with 10 percent
or more defects will be detected by this sampling plan.
4.4.4 Cost Versus Audit Level
The determination of the audit level (sample size n) to be used in
assessing the data quality with reference to prescribed limits L and U
can be made on a statistical basis by defining acceptable risks for type
I and type II errors, knowing or estimating the quality of the incoming
data, and specifying the described level of confidence in the reported
data, or on a cost basis as described herein. In this section, cost data
associated with the audit procedure are estimated or assumed for the pur-
pose of illustrating a method of approach and identifying which costs
should be considered.
A model of the audit process, associated costs, and assumptions made
in the determination of the audit level is provided in figure 17. It is
assumed that a collection of source emissions tests for N stacks is to be
made by a particular firm, and that n measurements (n _< N) are to be
audited at a cost, C = b + en, where b is a constant independent for n,
A
and c is the cost per stack measurement audited. In order to make a specific
determination of n, it is also necessary to make some assumptions about the
123
-------
Collection of Source Emission
Tosts (Lots of Size N)
£
50% of Lots
< 10% Defective
Acceptable
Quality
Not Acceptable
Quality
Audit n
Measurements
t
h
A
_ 50% of Lots
> 10% Defective
Audit n
Measurements
Select Audit
Parameter n, k
Data Declared
to be of
Acceptable
Quality
Data Declared
not to be of
Acceptable
Quality
Report
Data
Data Declared
to be of
Acceptable
Quality
Institute Action to
Improve Data Quality
(Correct Data if
Possible)
_£
Expected Cost of
Treating Poor
Quality Data as
Good Quality Data
CG|p = $15,000
Expected Cost of
Falsely Inferring
Data are of Poor
Quality Cp)G =
$10,000
Expected Cost
Saving of Taking
Correct Action with
Respect to Poor
Quality Data
C*IB = $7,500
Figure 17. Flow chart of the audit level selection process.
124
-------
quality of the source emissions data from several firms. For example,
it is assumed in this analysis that 50 percent of the data lots are of
good quality, i.e., one half of the firms are adhering to good data
quality assurance practice, and that 50 percent of the data lots are of
poor quality. Based on the analysis in section 4.1, good quality data
is defined as that which is consistent with the estimated precision/bias
using the reference method. Thus, if the data quality limits L and U
are taken to be the lower and upper 3a limits corresponding to limits
used in a control chart, the quality of data provided by a firm adhering
to the recommended quality assurance procedures should at most contain
about 0.3 percent defective measurements (i.e., outside the limits defined
by L and U). Herein, good quality data are defined as that containing at
most 10 percent defective measurements. The definition of poor quality
data is somewhat arbitrary, for this illustration it is taken as 25 per-
cent outside L and U.
In this audit procedure the data are declared to be of acceptable
quality if both of the following inequalities are satisfied
d + ks < U (32)
d
d - ks, > L, (33)
d
where d and s, are the mean and standard deviation of the data quality
d
characteristic (i.e., the difference; of the field and audited measure-
ments) being checked, and not of desired quality if one or both inequali-
ties is violated, as described in section 4.3. The cost associated with
these actions are assumed to be as follows:
C = Audit cost = b + en. b is assumed to be zero for this example
/I
and c is taken as $600/measurement.
C | = Cost of falsely inferring that the data are of poor quality, P,
r | G
given that the data are of good quality, G. This cost is
assumed to be one-half the cost of collecting emissions data for
N = 20 stacks (i.e., 0.5 x $1000 x 20 = $10,000). This cost
125
-------
would include that of searching for an assignable cause of the
inferred data deficiency when none exists, partial repetition
of data collection, decision resulting in the purchase of equip-
ment to reduce emission levels of specific pollutants, etc.
C = Cost savings resulting from correct identification of poor
quality data. This cost is taken to be $7,500, i.e., equal to
one-half of C i or equal to 0.375 x $1,000 x 20, the total cost
I
of data collection.
These costs are given in figure 17. These cost data are then used in
conjunction with the a priori information concerning the data quality to
select an audit level n. Actually, the audit procedure requires the
selection of the limits L and U, n, and k. L and U are determined on the
basis of the analysis of section 4.1. The value of k is taken to be the
value associated with n in table 6 of section 4.4.3, i.e., the value
selected on a statistical basis to control the percentage of data outside
the limits L and U. Thus, it is only necessary to vary n and determine
the corresponding expected total cost E(TC) using the following cost model.
E(TC) = -CA - 0.5 Pp|G Cp|G + 0.5 Pp p Cp|p - 0.5 PG|P CG p (34)
where the costs are as previously defined. The probabilities are defined
in a similar way to the corresponding costs.
P. = Probability that a lot of good quality data is falsely
r G
inferred to be of poor quality due to the random variations
in the sample mean
samples of size n.
in the sample mean d and standard deviation, s , in small
P = Probability that a lot of poor quality data is correctly
identified as being of poor quality.
P I = Probability that a lot of poor quality data is incorrectly
b | P
judged to be of good quality due to sampling variations of
d and s.
126
-------
These three probabilities are conditional on the presumed lot quality
and are preceded by a factor of 0.5 in the total cost model to correspond
to the assumed percentage of good (poor) quality data lots.
In order to complete the determination of n, it is necessary to
calculate each of the conditional probabilities using the assumptions stated
for a series of values of n (and associated k which is given in table 11),
The computational procedure is given in the Final Report of this contract.
These calculations were made for the cases n = 3, 5, 7, and 10 and for two
degrees of control on the quality of the data that can be tolerated, i,e.,
p = 0.2 and p = 0.1, the portion outside the limits L and U for which it
is desired to accept the data as of good quality with probability less than
or equal to 0.10. These computed probabilities are then used in conjunc-
tion with the costs associated with each condition, applying equation (34)
to obtain the average cost versus sample size n for the two cases p = 0.1
and 0.2. The curves obtained from these results are given in figure 13.
It can be seen from these curves that the minimum cost is obtained by
using n ~ 5 independent of p. However, it must be recognized that the
costs used in the example are for illustrative purposes and may vary from
one region to another, thus within the reasonable uncertainty of the
estimated costs, values of n between 3 and 7 would seem to be reasonable.
The assumed costs suggest that p = 0.2 is more cost effective, which tends
to permit data of poorer quality to be accepted.
127
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LIST OF REFERENCES
128
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LIST OF REFERENCES
1. E. S. Kopecki. "Stainless Steels." Machfhe Design, 1970 Metals Ref-
erence Issue 4, Vol. 42, Cleveland Ohio: Penton Publishing Company,
February 12, 1970.
2. R. M. Martin, Construction Details of Isokinetic Source Sampling
Equipment, Publ. No. APTD-0581, Air Pollution Control Office,
Environmental Protection Agency, Research Triangle Park, North Caro-
lina; 1971.
3. Franklin Smith and Denny E. Wagoner, Guidelines for Development of a
Quality Assurance Program, "Determination of Stack Gas Velocity and
Volumetric Flow Rate (Type-S Pitot Tube)," EPA-68-02-1234, Environ-
mental Protection Agency, Research Triangle Park, North Carolina; 1974.
4. Franklin Smith, Denny E. Wagoner, and Pamela Wohlschlegel, Guidelines
for Development of a Quality Assurance Program,"Determination of Par-
ticulate Emissions from Stationary Sources," EPA Contract Number 68-02-
1234, Program Element Numbers 1HA327, Quality Assurance and Environ-
mental Monitoring Laboratory, National Environmental Research Center,
Research Triangle Park, North Carolina; 1975.
5. J. J. Rom, Maintenance, Calibration, and Operation of Isokinetic
Source Sampling Equipment, Publ. No. APTD-0576. Office of Air Pro-
grams, Environmental Protection Agency, Research Triangle Park, North
Carolina; 1972.
6. W. S. Smith. Stack Sampling News 1, No. 7; 1974.
7. Franklin Smith and Denny E. Wagoner, Guidelines for Development of a
Quality Assurance Program, "Gas Analysis for Carbon Dioxide, Excess
Air, and Dry Molecular Weight," EPA-68-02-1234, Environmental Protect-
ion Agency, Research Triangle Park, North Carolina; June 1974.
8. "Occupational Safety and Health Standards: National Consensus Stan-
dards and Established Federal Standards." Federal Register 35, No.105;
May 29, 1971.
9. "Standards of Performance for New Sources." Federal Register 36, No.
247; December 23, 1971.
10. W. S. Smith and D. J. Grose, Stack Sampling Nomographs for Field Esti-
mations, Entropy Environmentalists, Inc., Research Triangle Park, North
Carolina; 1973.
11. W. S. Smith, Stack Sampling News 1, No. 1; 1973.
129
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LIST OF REFERENCES (continued)
12. R. F. Yarnor, Industrial Source Sampling, Ann Arbor Science Pub-
lishers, Inc.; 1971.
13. Franklin Smith and Denny E. Wagoner, Guide for Development of a
Quality Assuiiance Program; "Determination of Moisture Content," EPA-
68-02-1234, Environmental Protection Agency, Research Triangle Park,
North Carolina; 1974.
14. B. Fleet, K. V. Liberty, and T. S. West, "A Study of Some Matrix
Effects in the Determination of Beryllium by Atomic Absorption Spec-
troscopy in the Nitrous Oxide - Acetylene Flame," Talana, 17:203; 1970.
15. I. M. Kolthoff, E. B. Sandell, E. J. Meechan, and Stanley Bruckenstein,
Quantitative Chemical Analysis, p. 418, McMillan Company, New York;
1969.
16. Paul C. Constant, Jr., and Michael C. Sharp , "Collaborative Study of
Method 104 — Reference Method for Determination of Beryllium Emission
from Stationary Sources," EPA-68-02-1098, Environmental Protection
Agency, Research Triangle Park, North Carolina; 1974.
17. W. J. Mitchell, Evaluation Report: Additional Studies on Obtaining
Replicate Particulate Samples from Stationary Sources, Environmental
Protection Agency, Research Triangle Park, North Carolina; 1973.
18. Administrative and Technical Aspects of Source Sampling for Particu-
late s , Publ. No. APTD-1289, Environmental Protection Agency, Research
Triangle Park, North Carolina; May 1971.
19. E. L. Grant and R. S. Leavenworth, Statistical Quality Control, 4th
ed., St. Louis: McGraw-Hill; 1972.
20. D. A. Simons, Practical Quality Control, Reading, Massachusetts:
Addison-Wesley Publishing Company; 1970. •
21. Glossary and Tables for Statistical Quality Control, Statistics Tech-
nical Committee, American Society for Quality Control, Milwaukee,
Wisconsin; 1973.
22. Franklin Smith and A. Carl Nelson, Jr., Guidelines for Development of
a Quality Assurance Program, "Measuring Pollutants for Which National
Ambient Air Quality Standards Have Been Promulgated," Final Report
Contract No. 68-02-0598, Quality Assurance and Environmental Monitor-
ing Laboratory, National Environmental Research Center, Research Tri-
angle Park, North Carolina; August 1973.
130
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LIST OF REFERENCES (continued)
23. A. Hald, Statistical Theory with Engineering Applications, New York:
John Wiley and Sons; 1952.
24. D. B. Owen, "Variables Sampling Plans Based on the Normal Distribu-
tion," Technometrics, 9, No.3; August 1967.
25. D. B. Owen, "Summary of Recent Work on Variables Acceptance Sampling
with Emphasis on Non-normality," Techn ome t ri c s 11, 1969.
26. Kinji Takogi, "On Designing Unknown Sigma Sampling Plans Based on a
Wide Class on Non-normal Distributions," Technometrics 14, 1972.
27. C. Eisenhart, M. Hastay, and W. A. Wallis, eds, Techniques of Statis-
tical Analysis, Statistical Research Group, Columbia University, New
York: McGraw-Hill; 1947.
131
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APPENDIX A
132
-------
8846
RULES AND REGULATIONS
PROBE
TYPES
PI TOT TUBE
£
sample is digested in an acki solution and
analyzed by atomic absorption spectropho-
tometry.
1.2 Applicability.—This method Is appli-
cable for the determination of beryllium
emissions in ducts or stacks at stationary
sources. Unless otherwise specified, this
method is not intended to apply to gaa
streams other than those emitted directly
to the atmosphere without further
processing.
2. Apparatus—2.1 Sampling train.—A
schematic of the sampling train used by
EPA is shown in figure 104-1. Commercial
models of this train are available, although
construction details are described in APTD-
0581,1 and operating and maintenance pro-
cedures are described in APTD-0576. The
components essential to this sampling train
are the following:
2.1.1 Nozzle.—Stainless steel or glass with
sharp, tapered leading edge.
2.1.2 Probe.—Sheathed Pyrex2 glass. A
heating system capable of maintaining a
minimum gas temperature in the range of
the stack temperature at the probe outlet
during sampling may be used to prevent
condensation from occurring.
HEATED AREA FILTER HOLDER THERMOMETER CHECK
WAIVE
VACUUM
LINE
IMPINGERS ICE BATH
BY-PASS. VALVE
VACUUM
GAUGE
!ALVE
THERMOMETERS
DRY TEST METER
AIR-TIGHT
'PUMP
Figure 104-1. Beryllium sampling train
2.1.3 Pilot tube.—Type S (figure 104-2),
or equivalent, with a coefficient within 5 per-
cent over the working range, attached to
probe to monitor stack gas velocity.
2.1.4 Filter holder.—Pyrex glass. The filter
holder must provide a positive seal against
leakage from outside or around the filter.
A heating system capable of maintaining the
filter at a minimum temperature in the range
of the stack temperature may be used to
prevent condensation from occurring.
2 1.5 Impingers.—Pour Greenburg-Smith
impingers connected in series with glass ball
joint fittings. The first, third, and fourth
impingers may be modified by replacing the
tip with a '/a-inch l.d glass tube extending
to one-half inch from the bottom of the
flask,
2.1 6 Metering system.—Vacuum gauge,
leakless pump, thermometers capable of
measuring temperature to within 5° F, dry
gas meter with 2 percent accuracy, and re-
lated equipment, described in APTI>~0581,
to maintain an isokinetic sampling rate and
to determine sample volume.
2.1.7 Barometer.—To measure atmos-
pheric pressure to ± 0.1 in Hg.
2.2 Measurement of stack conditions
(stack pressure, temperature, moisture and
velocity)—2.2.1 Pilot tube.—Type S, or
equivalent, with a coefficient within 5 percent
over the working range.
2.2.2 Differential pressure gauge.—In-
clined manometer, or equivalent, to measure
velocity head to within 10 percent of the
minimum value.
1 These documents are available for a nom-
inal cost from the National Technical In-
formation Service, U.S. Department of Com-
merce, 5285 Port Royal Bead, Springfield,
Va. 22151.
2 Mention of trade names on specific prod-
ucts does not constitute endorsement by the
Environmental Protection Agency.
RtOiltR, VOL. 38, NO. 66—FRIDAY, APRlt 6, 1973
i :< 3
-------
RULES AND REGULATIONS
8847
TUBING ADAPTED
however, most sample sites differ to some
degree and temporary alterations such as
stack extensions or expansions often are re-
quired to insure the best possible sample
site. Further, since beryllium is hazardous,
care should be taken to minimize exposure.
Finally, since the total quantity of beryllium
to be collected is quite small, the test must
be carefully conducted to prevent contami-
nation or loss of sample.
4.2 Selection of a sampling site and mini-
mum number of traverse points.
4.2.1 Select a suitable sampling site that
is as close as practicable to the point of at-
mospheric emission. If possible, stacks
•Figure 104-2. Pilot tube - manometer assembly,
2.2.3 Temperature gage.—Any tempera-
ture measuring device to measure stack tem-
perature to within 5° F.
2.3,4 Pressure gage.—Pilot tube and in-
clined manometer, or equivalent, to measure
stack pressure to within 0.1 in Hg.
2.2.5 Moisture determination.—Wet and
dry bulb thermometers, drying tubes, con-
densers, or equivalent, to determine stack
gas moisture content to within 1 percent.
2.3 Sample recovery—2.3.1 Probe clean-
ing rod.—At least as long as probe.
2.3.2 Leakless glass sample bottles.—500
ml.
2.3.3 Graduated cylinder.—250 ml.
2.3.4 Plastic jar.—Approximately 300 ml.
2.4 Analysis—2.4.1 Atomic absorption
spectrophotometer.—To measure absorbance
at 234.8 nm. Perkin Elmer Model 303, or
equivalent, with N2O/acetylene burner.
2.4.2 Hot plate.
2.4.3 Perchloric acid fume hood.
3. Reagents—3.1 Stock reagents.—3.1.1
Hydrochloric acid.—Concentrated.
3.1.2 Perchloric acid.—Concentrated, 70
percent.
3.1.3 Nitric acid.—Concentrated.
3.1.4 Sulfuric acid.—Concentrated.
3.1.5 Distilled and deionized water.
3.1.6 Beryllium powder.—98 percent mini-
mum purity.
3.2 Sampling—3.2.1 Filter. — Millipore
AA, or equivalent. It is suggested that a
Whatman 41 filter be placed immediately
against the back side of the Millipore filter
as a guard against breaking the Millipore
filter. In the analysis of the filter, the What-
man 41 filter should be included with the
Millipore filter.
3.2.2 Silica gel.—Indicating type, 6 to 16
mesh, dried at 350° F for 2 hours.
3.2.3 Distilled and deionised water.
3.3 Sample recovery—3.3.1 Distilled and
deionised water.
3.3.2 Acetone.—Reagent grade.
3.3.3 Wash acid.—1.1 V/V hydrochloric
acid-water.
3.4 Analysis.—3.4.1 Sulfuric acid solu-
tion, 12 N.—Dilute 333 ml of concentrated
sulfuric acid to 1 1 with distilled water.
3.4.2 25 percent V/V hydrochloric acid-
water.
3.5 Standard beryllium solution—3.5.1
stock solution.—l fig/ml beryllium. Dis-
solve 10 mg of beryllium in 80 ml of 12 N
sulfuric acid solution and dilute to a volume
of 1000 ml with distilled water. Dilute a 10 ml
aliquot to 100 ml with 25 percent V/V hydro-
chloric acid, giving a concentration of 1
/ig/ml. This dilute stock solution should be
prepared fresh daily. Equivalent strength (in
beryllium) stock solutions may be prepared
from beryllium salts as Bed,, and Be (NO.,).,
(98 percent minimum purity).
4. Procedure. 4.1 Guidelines for source
testing are detailed In the following sections.
These guidelines are generally applicable;
smaller than 1 foot in. diameter should not
be sampled.
4.2.2 The sampling site should be at least
8 stack or duct diameters downstream and
2 diameters upstream from any flow disturb-
ance such as a bend, expansion or contrac-
tion. For a rectangular cross-section, deter-
mine an equivalent diameter from the
following equation:
D,=2LW
L+W
where:
Df—equivalent diameter
L — length
W=width
eq. 104-1
NUMBER OF DUCT DIAMETERS UPSTREAM'
(DISTANCE A)
3
z
5
20
10
FROM POINT Or ANY TYPE Or
DISTURBANCE (BF.ND, EXPANSION CONTRACTION. ETC.*
10
NUMBER OF DUCT DIAMETERS DOWNSTREAM'
(DISTANCE Bl
Figure 101-3. Minimum num&er of traverse points.
Figure 104-4. Cross section of circular stack showlng/Iocatlon of
traverse points on perpendicular diameters.
Figure 104-5. cross section or rectangular stack divided Into 12 equal
areas, with traverse points at centroid of each area.
4.2.3 When the above sampling site cri-
teria can be met, the minimum number of
traverse points is four (4) for stacks 1 foot
in diameter or less, eight (8) for stacks larger
than 1 foot but 2 feet in diameter or less, and
twelve (12) for stacks larger than 2 feet.
4.2.4 Some sampling situations may ren-
der the above sampling site criteria Imprac-
tical. When this is the case, choose a con-
venient sampling location and use figure
104-3 to determine the minimum number
of traverse points. However, use figure 104-3
only for stacks l foot, in diameter or larger.
4.2.5 To use figure 104-3, first measure
the distance from the chosen sampling lo-
cation to the nearest upstream and down-
stream disturbances. DLvide this distance by
the diameter or equivalent diameter to deter-
mine the distance in terms of pipe diameters.
Determine the corresponding number of
traverse points for each distance from fig-
ure 104-3. Select the higher of the two num-
bers of traverse points, or a greater value,
such that for circular stacks the number is
a multiple of four, and for rectangular stacks
the number follows the criteria of section
4.3.2.
4.2.6 If a selected sampling point is closer
than 1 inch from the stack wall, adjust the
location of that point to ensure that the
sample is taken at least 1 inch away from the
wall.
4.3 Cross-sectional layout and location of
traverse points.
FEDERAL REGISTER, VOL. 38, NO. 66—FRIDAY, APRIL 6, 1973
134
-------
8848
RULES AND REGULATIONS
*|i
«~ ">
A Sa
+j +J +j
•O 1o bD
a » a
§»>§
du
ore i
e of
° F. o
ngers. Add
he temperatu
mpinger at 70
llium tram operation. — 4.6.1 For
record the data required on the
eet shown in figure 104-6. Take
t each sampling point at least
minutes and when significant changes
conditions necessitate additional ad-
a
4. B
ch run,
ample s
adings
ery 5
stac
4J Q< -)J rt ft) Q)
a
x
re
ev
in
stments in flow rate.
4.6.2 Sample at a rate of 0.5 to 1.0 ft.Vmin.
mples shall be taken over such a period or
riods as are necessary to accurately deter-
ine the maximum emissions which would
iod. In the case of
s, ent tests shall be
llow rate determination
f th issions which will
duration of the cycle. A mini-
me of 2 hours is recommended.
perio
fficie
ur
m
pe
mi
occur in a 24-hou
cyclic operation
made so as to al
or calculation o
occur over the
mum sample ti
hird impinger empty, and place
200 g of preweighted silica gel
pinger. Save a portion of the
as a blank in the sample
the train and the probe as
** 4) TS -3
u
1.
.
check the sampling train at the
The leakage rate should not be
ercent of the desired sampling
sation in the probe or filter is
s will be
rovide a
empera
h as th
-
k
e.
.
p
en
ers, leave the
approximatel
in the fourt
distilled wat
analysis. Set
in figure 104
4.5 2 Lea
sampling sit
in excess of 1
rate. If cond
a problem, probe and filter
required. Adjust the heaters
temperature at or above the
ture. However, membrane filt
Millipore AA are limited to a
the stack gas is in excess of about 200° P.,
consideration should be given to an alternate
procedure such as moving the fUter holder
downstream of the first impinger to insure
that the filter does not exceed its tempera-
II
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-------
RULES AND REGULATIONS
8849
from the stack and handle in accordance with
the sample recovery process described in § 4.7.
4.7 Sample recovery.—4.7.1 (All glass
storage bottles and the graduated cylinder
must be precleaned as In § 4.5.1.) This opera-
tion should be performed in an area free of
possible beryllium contamination. When the
sampling train is moved, care must be exer-
cised to prevent breakage and contamination.
4.7.2 Disconnect the probe from the im-
pinger train. Remove the filter and any loose
particulate matter from the filter holder and
place In a sample bottle. Place the contents
(measured to ±1 ml) of the first three im-
pingers into another sample bottle. Rinse the
probe and all glassware between it and the
back half of the third impinger with water
and acetone, and add this to the latter sam-
ple bottle. Clean the probe with a brush or a
long slender rod and cotton balls. Use acetone
while cleaning. Add these to the sample bot-
tle. Retain a sample of the water and acetone
as a blank. The total amount of wash water
and acetone used should be measured for ac-
curate blank correction. Place the silica gel
in the plastic jar. Seal and secure all sample
containers for shipment. Tf an additional test
Is desired, the glassware can be carefully dou-
ble rinsed with distilled water and reassem-
bled. However, if the glassware is to be out of
use more than 2 days, the initial acid
wash procedure must be followed.
4 8 Analysis.
4.8.1 Apparatus preparation.—Clean all
glassware according to the procedure of sec-
tion 4.5.1. Adjust the instrument settings
according to the instrument manual, using
an absorption wavelength of 234.8 nm.
4.8.2 Sample preparation.—The digestion
of beryllium samples is accomplished in part
In concentrated perchloric acid. Caution:
The analyst must insure that the sample is
beated to light brown fumes after the Initial
nitric acid addition; otherwise, dangerous
perchlorates may result from the subsequent
perchloric acid digestion. Perchloric acid also
should be used only under a perchloric acid
hood.
4.8 2.1 Transfer the filter and any loose
particulate matter from the sample container
to a 150 ml beaker. Add 35 ml concentrated
nitric acid. Heat on a hotplate until light
brown fumes are evident to destroy all or-
ganic matter. Cool to room temperature and
add 5 ml concentrated sulfuric acid and 5
ml concentrated perchloric acid. Then pro-
ceed with step 4.8.2.4.
4,8.2.2 Place a portion of the water and
acetone sample into a 150 ml beaker and put
on a hotplate. Add portions of the remainder
as evaporation proceeds and evaporate to dry-
ness. Cool the residue and add 35 ml concen-
trated nitric acid. Heat on a hotplate until
light brown fumes are evident to destroy any
organic matter. Cool to room temperature
and add 5 ml concentrated sulfuric acid, and
5 ml concentrated perchloric acid. Then pro-
ceed with step 4.8.2.4.
4.8 2 3 Weigh the spent silica gel and re-
port to the nearest gram.
4.824 Samples from 4.8.2.1 and 48.2.2-
may be combined here for ease of analysis.
Replace on a hotplate and evaporate to dry-
ness in a perchloric acid hood. Cool and dis-
solve the residue in 10.0 ml of 25 percent
V/V hydrochloric acid. Samples are now
ready for the atomic absorption unit. The
beryllium concentration of the sample must
be within the calibration range of the unit.
If necessary, further dilution of sample with
25 percent V/V hydrochloric acid must be
performed to bring the sample within the
calibration range.
4.8.3 Beryllium determination.—Analyze
the samples prepared in 4.8.2 at 234.8 nm
using a nitrous oxide/acetylene flame. Alumi-
num, silicon and other elements can inter-
fere with this method if present in large
quantities. Standard methods are available,
however, to effectively eliminate these inter-
ferences (see Reference 5).
5. Calibration—5.1 Sampling train.—
5 1.1 Use standard methods and equipment
as detailed in APTD-0576 to calibrate the rate
meter, pitot tube, dry gas meter and probe
heater (if used). Recalibrate prior to each
test series
5.2 Analysis.—5.2.1 Standardization is
made with the procedure as suggested by the
manufacturer with standard beryllium solu-
tion. Standard solutions will be prepared
from the stock solution by dilution with 25
percent V/V hydrochloric acid. The linearity
of working range should be established with
a series of standard solutions. If collected
samples are out of the linear range, the
samples should be diluted. Standards should
be interspersed with the samples since the
calibration can change slightly with time.
6. Calculations—6.1 Average dry gas meter
temperature, stack temperature, stack pres-
sure and average orifice pressure drop.—See
data sheet (figure 104-6).
6.2 Dry gas volume.—Correct the sample
volume measured by the dry gas meter to
stack conditions by using equation 104-2.
6.3 Volume of water vapor.
T
eq. 104-2
where1
Vm,=Volume of gas sample through the dry gas meter
(stack conditions), ft1
Vm =Volume of gas sample through the dry gas meter
(meter conditions), ft'.
T,=Average temperature of stack gas, °R.
Tm=Average dry gas meter temperature, °R.
Pb.t = Barometric pressure at the orifice meter, in Hg.
A//= Average pressure drop across the orifice meter,
in HiO.
13 6 = Specific gravity of mercury.
P, = Stack pressure, Pb»r ± static pressure, in Hg.
where:
K^
T/ic
P.
6.4
where'
"-.—""«p. eq. 104-3
=Volume of water vapor in the gas sample (stack
conditions), ft3.
=0.00267 f , when these units are used.
ml .kt
= Total volume of liquid collected in impkigers
and silica gel (see figure 104-7), ml.
= Average stack gas toreperature, °R.
= Stack pressure, Pb,r±static pressure, in Hg.
Total gas volume.
eq. 104-4
tal volume of gas sample (stack conditions),
ft3.
Fm<=Volume of gas through dry gas meter (stack
conditions), ft3.
FK.=Volume of water vapor in gas sample (stack
conditions), ft3.
6.5 Stack gas velocity.
Use equation 104-5 to calculate the stack
gas velocity.
eq. 104-5
where:
(»•)•»«.=Average stack gas velocity, feet per
second.
Ib-lnHg
, when
sec V Ib mole-°R-inH)O /
these units are used.
C,=Pitot tube coefficient, dimensionless.
(T.) ,T.,=Average stack gas temperature, °R.
(VAp).v«.=Average square root of the velocity head
of stack gas (inHsO)1/1 (see figure 104-8).
P,=Stack pressure, Pb»r±static pressure, in
Hg.
M,=Molecular weight of stack gas (wet basis).
the summation of the products of the
molecular weight of each component
multiplied by its volumetric proportion
in the mixture, Ib/lb-mole.
FINAL
INITIAL
LIQUID COLLECTED
TOTAL VOLUME COLLECTED
VOLUME Of LIQUID
WATER COLLECTED
IMPINGED
VOLUME.
ml
SILICA GEL
WEIGHT.
0
f ml
INCREASE BY DENSITY OF WATER. (1 «/nnlJ:
INCREASE, t
total
VOLUME WATER, ml
Figure 104-7. Analytical date.
FEDERAL REGISTER, VOl. 38, NO, 66-nfWDAY, APRIL 6, 1973
136
-------
8850
RULES AND REGULATIONS
PLANT.
DATE
RUN NO.
STACK DIAMETER, in.
BAROMETRIC PRESSURE, in.
STATIC PRESSURE IN STACK (Pg), in. Hg._
OPE RATORS
SCHEMATIC OF STACK
CROSS SECTION
Traverse point
number
Velocity head,
in. H2O
AVERAGE:
Stack Temperature
Figure 104-8. Velocity traverse data.
Figure 104-8 shows a sample recording
sheet for velocity traverse data. Use the aver-
ages in the last two columns of figure 104-8
to determine the average stack gas velocity
from equation 104^5.
6.6 Beryllium collected.—Calculate the
total weight of beryllium collected by using
equation 104-6.
Wi = V
-------
APPENDIX B
138
-------
APPENDIX B ILLUSTRATED USE OF
The material in this appendix is, in the most part v, reproduced from
APTD-0576 (ref. 5).
NOMOGRAPHS
The correction factor nomograph (fig. Bl) and the operating nomograph
(fig. B2) have been designed for use with the sampling train as aids for
rapid isokinetic sampling rate adjustments and for selection of proper
nozzle size. To determine the correction factor, C, on the nomograph, the
following information is first required:
(1) Percent moisture, %H20. This may be determined from a previous
test or presurvey, or before the sample run.
(2) Orifice calibration factor, AH@. This is determined from the
laboratory calibration (see section on Calibration).
(3) Meter temperature, T . Temperature at the meter rises above
m
ambient temperature because of the pump and can easily be estimated with
experience. An estimate within 10°F (approximately + 1 percent error) is
all that is necessary (an initial estimate of about 25°F above ambient
temperature has been used). This approximation above ambient temperature
is not required if the pump is located outside the meter box console.
, H-O
• Tbo-
-i 0
-I 5
Figure
Nomograph for correction factor, C.
139
-------
(4) Stack pressure, P . This is measured before the sample run; or
s
if the sampling site is near the exit of the stack, atmospheric pressure
is used.
(5) Meter pressure, P . Same as atmospheric pressure.
To obtain correction-factor, C (fig. Bl) :
(1) Draw line from AH@ to T to obtain point "A" on reference line 1
m
(ref. 1-).
(2) Draw line from point "A" to %H~0 to obtain point "B" on reference
line 2 (ref. 2).
(3) Draw line from point "B" to the calculated value P /P to obtain
s in
correction factor, C.
To select the nozzle size and to set the K-factor on the operating
nomograph, the following information is first required:
(1) C factor. This is obtained from the correction-factor noEiograph
(fig. Bl).
Note; If the coefficient, C , of the type-S pitot tube Is not
~~ P
equal to .85 jf .02, the following is required: (a) Mul-
/C \
tiply C times I ~oTJ = CT for the correct C factor in
obtaining the K-factor, or (b) if C1 is less than 0.5, then
/C \2
use C and multiply each AP reading by I -y,.- I for each adjust-
ment.
(2) Stack temperature, T . This is determined in °F by a rough
temperature traverse to within +_ 25°F before the sample run.
(3) Average velocity pressure, AP. This is determined by a rough
preliminary pitot traverse, using the average of minimum and maximum AP's
in inches of water.
(4) Exact available nozzle sizes, D. This is obtained from the cali-
bration of available nozzles.
To select the nozzle size and to set the K-factor pivot point, use the
following procedure (fig. B2):
(1) Set correction factor, C, on sliding scale to the reference mark,
"A."
(2) Align T with average AP, note probe tip diameter on D-scale, and
select exact nozzle size closest to it.
140
-------
CORRECTION
FACTOR.
c PITOT READING,
ORIFICE READING,
A H
1 0— I
3
3 —
7 —
5— -
=
"S
5-^=
==
4-^
_^
3-^
~
"E
2
H
—
-
—
,
—
0 3— •
0 3 1
^ --
' ,
o 5-^g
0 5-=
0 4-E:
0 3-r=
0 2— —
0 1
REF A —
•^REF 3
-••»
' •«-»
2 0
— 1 5
"" STEP 1
— 1 0
— 09
— 03
— 07
06
— 0 5
• _^
-
— 2500
— 2000
^
— \ 500
H
: —
-—I 000
300
— TOO.
^L- 500
•^— 400
___
•**• r°-l-
_00
-
_ IOC
0
STAC*
TEVfP^RATuRE,
5
SLIDING
SCA^E
CUT ALONG -INE3
A.P
K FACTOR 0 00,
^?rf^
^ •
'-•.I
r-l 0 Z
— —
=-0 9 -=
E_o a o 02-|
_ =
=-07 033-=
~ 0 04-=
=~'J ° 0 35-=
~" T " h "
=-05 — =
— o j3 ~T:
E~ ° 2~z
^-04 -
— ^ ~
— 33 —^
— -I
1 — •* " ~^
— ^ " : = -
17' ' ^^ 5 — ^
- - -0 .7^|
II_ D , 0 8-3
~ 1 D-=
r
I ~E
2 0-5
3 0-=
4 C— ^
o , 5 ;_g
50—^
3 :— T
.= C^
EXAMPLE C 0
K .- dimension le ^i Tc - 300 °P
Figure B2. Use of the nomograph in selecting nozzle size
and setting K factor.
141
-------
(3) Align T with exact nozzle size selected and obtain a value on
s
the AP scale.
(4) Align the AP value with reference mark, "B", on AH scale, and set
the K-factor pivot point.
To obtain the orifice meter settings, AH, for isokinetic conditions
after the K-factor pivot point has been set, use the following procedure
(fig. B3):
(1) Position the pitobe nozzle at the sampling point.
(2) Read the pitot tube AP.
(3) Align the AP through the K-factor pivot point
(4) Obtain AH and adjust metering valves.
The nomograph assumes the following, once the K-factor pivot point is
set:
(1) T does not change more than 25° for T < 1000°F or 50° for
S S
T > 1000°F.
s
(2) D is not changed during the test.
(3) T was estimated correctly and does not vary more than 10° .
(4) Percent H_0 remains constant, within +_ 1.0 percent.
(5) P and P remain constant, within +1.0 percent.
s in.
142
-------
CORRECTION
FACTOR,
C . PITOT READING,
ORIFICE READING.
AH
10—
a —
a—
__
7— •
S-m
•f
•1
_^ ""
^
.=:
3 =
—
—
~
""
2
z
—
~"
1__
0 9—"
0 8 —
0.7 —
0.6-=
0 5-=
-=
0.4-r=
-=
0 3^
5
5
0 2—
—
~
—
0.1 —
REF A .—
~REF 8
£XA
*~^^v1P[^ p
'-~*^2
*A(\tfpl r- ' "
"" ••--L.
— 2 0
~
— 1 5
-
"~
"™
1.0
— 0 9
Z-0 8
^0.7
«. 0 6
"™
— 05
"""
— 2500
-
— JOOO
*~
1 500
-
— -\ 000
~
^- 800
Z—
-^600
•,-7^0--^
— 400 "••
t— 300
— ZOO
— 100
— 0
STACK
TEMPERATURE,
Ts
SLIDING
SCALE
CUT ALONG LINES
AP
K FACTOR o.ooi —
'»»PIVOT POINT
^ •• '^5i* ^\.
'^^^^
—
0 002-=
-3
0 003-jj
0 004-=
PROBE o oo5-=
TIP DIAMETER, -3
pj 0.006—^
001—=
'«<:
"^
•— 1.0 ~
2 —
-— 09 —
E_o a o 02-|
; _§
^07 0 03 -J
— ;
" 0 04— =
=-0 6 ;
= 0 05-5
=" o at,-f
r-o 5 ~5
Z 0 08— -
5" 0 2-f
E ° -— ~
0 3-=
E -|
S^- l*-=
— * ^^*^*
~ 07—2
— 02 ° '-=
"~ 1 0-=
— -
~ ~
_ 2 0-=
| 3 0-£
k— 4 0^^
=:
— 01 5 °-^
6 0-=
8 n ~
1 0 0-^
AH : in. HjO
C : dimensions
TC -.OF
K
D
AP
dimension less
i n.
in. H-,0
EX AMP L E 1 AP : 0 5
AH -. I 2
EX AMP L E 2 AP : 0 6
AH : 1 S3
Figure B3. Nomograph operation to obtain desired orifice meter settings
143
-------
APPENDIX C
144
-------
ILLUSTRATED AUDIT PROCEDURES
A flow chart of the operations involved in an auditing program from
first setting desired limits on the data quality to filing the results is
given below. Assumed numbers are used and a sample calculation of an audit
is performed in the flow chart. Each operation is referred to the section
in the text of the report where it is discussed.
145
-------
MANAGER
5.
6.
7.
LIMITS FOR DATA QUALITY CAN BE SET BY WHAT
IS DESIRED OR FROM THE NATURAL VARIABILITY
OF THE METHOD WHEN USED BY TRAINED AMD
COMPETENT PERSONNEL. FOR THIS EXAMPLE, IT
IS ASSUMED THAT CVOO = 25.7 PERCENT
(subsec.4.1), AND USING + 3 CV{R}, THE
LIMITS ARE L = -77.1 PERCENT AND U = 77.1
PERCENT.
FROM PRIOR KNOWLEDGE OF DATA QUALITY, ESTIMATE
THE PERCENTAGE OF FIELD MEASUREMENTS FALLING
OUTSIDE THE ABOVE LIMITS. IF NO INFORMATION
IS AVAILABLE, MAKE AN EDUCATED GUESS. IT IS
ASSUMED IN THIS EXAMPLE THAT 50 PERCENT OF THE
FIELD DATA ARE OUTSIDE THE LIMITS L AND U
(subsec. 4.4.4).
DETERMINE: (1) COST OF CONDUCTING AN AUDIT,
(2) COST OF FALSELY INFERRING THAT GOOD DATA
ARE BAD, (3) COST OF FALSELY INFERRING THAT
BAD DATA ARE GOOD, AND (4) COST SAVINGS FOR
CORRECTLY IDENTIFYING BAD DATA (subsec. 4.4.4).
DETERMINE THE AUDIT LEVEL EITHER BY (1) MINI-
MIZING AVERAGE COST USING EQUATION (17) OF
SUBSECTION 4.4.4, OR (2) ASSURING A DESIRED
LEVEL OF CONFIDENCE IN THE REPORTED DATA
THROUGH STATISTICS. FOR THIS EXAMPLE, THE
AUDIT LEVEL IS TAKEN AS n = 5 (fig. U).
BY TEAMS, TYPES OF SOURCES, OR GEOGRAPHY,
GROUP FIELD TESTS INTO LOTS (GROUPS) OF ABOUT
20 THAT WILL BE PERFORMED IN A PERIOD OF ONE
CALENDAR QUARTER.
SELECT n OF THE N TESTS FOR AUDITING. COMPLETE
RANDOMIZATION MAY NOT BE POSSIBLE DUE TO AUDI-
TOR'S SCHEDULE. THE PRIMARY POINT IS THAT THE
FIELD TEAM SHOULD NOT KNOW IN ADVANCE THAT
THEIR TEST IS TO BE AUDITED.
ASSIGN OR SCHEDULE AN AUDITOR FOR EACH FIELD
TEST.
SET DESIRED
LOWER AND UPPER
LIMITS FOR DATA
QUALITY, L AND U
ESTIMATE AVERAGE
QUALITY OF FIELD
DATA IN TERMS OF
L AND U
DETERMINE OR
ASSUME RELEVANT
COSTS
DETERMINE AUDIT
LEVEL FROM
STATISTICS, OR
AVERAGE COST
GROUP FIELD TESTS
INTO LOT SIZES OF
ABOUT N - 20
RANDOMLY SELECT
n OF THE N TESTS
FOR AUDITING
ASSIGN/SCHEDULE
AUDITOR(S) FOR
FOR THE n AUDITS
T
146
-------
AUDITOR
8.
10.
11
12.
13.
THE AUDITOR OBTAINS APPROPRIATE CALIBRATED
EQUIPMENT AND SUPPLIES FOR THE AUDIT
(subsec. 4.3).
OBSERVE THE FIELD TEAM'S PERFORMANCE OF THE
FIELD TEST. FILL IN THE AUDITOR'S CHECKLIST
(table 4) AND NOTE ANY UNUSUAL CONDITIONS
THAT OCCURRED DURING THE TEST.
PREPARE EQUIPMENT
AND FORMS
REQUIRED IN AUDIT
IN THE FIELD TEAM'S HOME LABORATORY, MAKE
INDEPENDENT DETERMINATIONS OF Cp, Dn, y, AND
AH@ (subsec. 4.3) ACCORDING TO THE CALIBRATION
PROCEDURES GIVEN IN SUBSECTION 2.2.
10
OBSERVE ON-SITE
PERFORMANCE
OF TEST
.
t
VERIFY CALIBRATION
RECORDS AND PERFORM
CALIBRATION CHECKS
IN TEAM'S HOME
LABORATORY
STARTING WITH THE RAW DATA FROM THE FIELD
AND USING AUDIT VALUES, PERFORM ALL THE
CALCULATIONS NECESSARY TO ARRIVE AT A VALUE
FOR d (subsec. 4.3, fig. 13).
THE AUDITOR'S REPORT SHOULD INCLUDE (1) DATA
SHEET FILLED OUT BY THE FIELD TEAM (fig. 5),
(2) AUDITOR'S CHECKLIST WITH COMMENTS
(table 4), (3) AUDIT DATA SHEET WITH CALCULA-
TIONS (fig. 13), and (4) A SUMMARY OF THE
TEAM'S PERFORMANCE WITH A NUMERICAL RATING
(subsec. 4.3).
THE AUDITOR'S REPORT IS FORWARDED TO THE
MANAGER.
n
PERFORM CALCULA-
TIONS TO DETERMINE
R - R
d - —
R
x 100
12
PREPARE
AUDIT
REPORT
13
FORWARD
REPORT TO
MANAGER
14. COLLECT THE AUDITOR'S REPORTS FROM THE n
AUDITS OF THE LOT OF N STACKS. IN THIS
CASE n = 5 AND ASSUMED VALUES FOR THE
AUDITS ARE d] =32.0, d2 - 19.5, da = 10.3,
d = 12.1, and d5 = 14.6 (table 5 ).
14
COMBINE
RESULTS OF
n AUDITS
T
147
-------
15. CALCULATE d AND Sd ACCORDING TO THE SAMPLE IN 15
TABLE 10. RESULTS OF THIS SAMPLE CALCULATION
SHOW d - 17.7%, AND sd - 8.7% (table 55 subsec.
4.4.3).
16. USE A t-TEST TO CHECK d. FOR SIGNIFICANCE, FOR 16
THIS EXAMPLE t = 17.7/5/6.7 - 4.5. THE
TABULATED t-VALUE FOR 4 DEGREES OF FREEDOM AT
THE 0.05 LEVEL IS 2.132; HENCE, d IS NOT
SIGNIFICANTLY DIFFERENT FROM 0 AT THIS LEVEL.
ALSO, sd IS CHECKED AGAINST THE ASSUMED VALUE
OF 25.7 PERCENT BY A CHI-SQUARE TEST.
X2/f = s?/a2{d} = (8.7)2/(25.7)2 = C.ll,
THE TABULATED VALUE OF x2/4 AT THE 95 PER-
CENT LEVEL IS 0.711; HENCE, SH IS MOT SIGNIF-
ICANTLY DIFFERENT FROM 25.7 PERCENT.
17. OBTAIN THE VALUE OF k FROM TABLE 11, FOR n = 5 17
AND p = 0.1. THIS VALUE TS 2.742, THEN
3 + k sd = J7.7 + (1.976)(8.7) - 34.9 AND
d _ |< Sd = M.I + (1.976)(8.7) = .51
(subsec. 4.4.3).
18. COMPARE THE ABOVE CALCULATIONS WITH LIMITS 18
L AND U (subsec. 4.4.3). FOR THIS EXAMPLE
3 + k s. = 41.6 < U =!77.1
d - k sd = -6.2 > L = -77.1
BOTH CONDITIONS ARE SATISFIED, GO TO 20.
(IF EITHER OF THE LIMITS HAD BEEN EXCEEDED,
CONTINUE TO 19.)
19. STUDY THE AUDIT AND FIELD DATA FOR SPECIFIC 19
AREAS OF VARIABILITY, SELECT THE MOST COST-
EFFECTIVE ACTION OPTION(S) THAT WILL RESULT
IN GOOD QUALITY DATA (subsec. 4.2). NOTIFY
THE FIELD TEAMS TO IMPLEMENT THE SELECTED
ACTION OPTION(S).
20. A COPY OF THE AUDITOR'S REPORT SHOULD BE SENT 20.
TO THE RESPECTIVE FIELD TEAM. ALSO, THE DATA
ASSESSMENT RESULTS, i.e., CALCULATED VALUES OF
3, SH, AND COMPARISON WITH THE LIMITS L AND U
SHOULD BE FORWARDED TO EACH TEAM INVOLVED IN
THE N FIELD TESTS.
CALCULATE THE
MEAN, d, AND
STANDARD
DEVIATION, sd
I
TEST
d AND s
CALCULATE
3 + k s
AND
d - k s.
'd
IsL
COMPARE
(16) WITH
L AND U
MODIFY
MEASUREMENT
METHOD
INFORM
FIELD TEAMS
OF AUDIT
RESULTS
T
148
-------
21. THE FIELD DATA WITH AUDIT RESULTS ATTACHED ARE
FILED. THE AUDIT DATA SHOULD REMAIN WITH THE
FIELD DATA FOR ANY FUTURE USES.
FILE AMD
CIRCULATE OR
PUBLISH FIELD
DATA
149
-------
APPENDIX D
150
-------
APPENDIX D GLOSSARY OF SYMBOLS
This is glossary of symbols as used in this document. Symbols used and
defined in the reference method (appendix A) are not repeated here.
SYMBOL DEFINITION
N Lot size, i.e., the number of field tests to be treated as
a group.
n Sample size for the quality audit (section IV).
CV{X} Assumed or known coefficient of variation (100 av/uv)
A A
CV{X} Computed coefficient of variation (100 sv/X) from a finite
A
sample of measurements.
a{X} Assumed standard deviation of the parameter X (population
standard deviation).
s{X} Computed standard deviation of a finite sample of measure-
ments (sample standard deviation)
t{X} Computed bias of the parameter X for a finite sample
(sample basis).
Rg Range, i.e., the difference in the largest and smallest
values in r replicate analyses.
e{M } Random error associated with the measurement of particulate
n
mass, M .
d. The percent difference in the audit value and the value of
R arrived at by the field crew for the jth audit.
d Mean difference between R. and R . for n audits expressed
3 aj
as a percent.
s. Computed standard deviation of differences between R. and
R . expressed as a percent.
aJ
p Percent of measurement outside specified limits L and U.
k Constant used in sampling by variables (section IV).
P{Y} Probability of event Y occurring
t, _ -i \ Statistic used to determine if the sample bias, d. is
significantly different f"om zero (t-test).
2 2
X /(n - 1) Statistic used to determine if the sample variance, s , is
2
significantly different from the assumed variance, a , of
the parent distribution (chi-square test)
151
-------
APPENDIX D
GLOSSARY OF SYMBOLS (CONTINUED)
SYMBOL
L
U
CL
LCL
UCL
R
R
_a
R
DEFINITION
Lower quality limit used in sampling by variables.
Upper quality limit used in sampling by variables.
Center line of a quality control chart.
Lower control limit of a quality control chart.
Upper control limit of a quality control chart.
Beryllium emission rate reported by the field team for
a sample run.
Beryllium emission rate calculated by the auditor.
Average beryllium emission rate for a field test, L.e.,
the average of three sample runs, g/d.
152
-------
APPENDIX E
153
-------
APPENDIX E GLOSSARY OF TERi^S
The following glossary ]is^.s and defines the statistical terras as used
in this document.
Accuracy A measure of the error of a process expressed as a
comparison between the average of the measured values
and the true or accepted value. It is a function of
precision and bias.
Bias The systematic or nonrandom component of measurement
error.
Lot A specified number of objects D be treated as a
group, e.g., the number of field tests to be conducted
by an organization during a specified period of time,
Measurement method. . A set of procedures for making a measurement.
Measurement process . The process of making a measurement including method,
personnel, equipment, and environmental conditions.
Population The totality of the set of items, units, er measure-
ments, real or conceptual, that is under consideration.
Precision The degree of variation among successive, independent
measurements (e.g., on a homogeneous material) under
controlled conditions, and usually expressed as a
standard deviation or, as is done here, as a
coefficient of variation.
Quality audit .... A management tool for independently assessing data
quality.
Quality control
check Checks made by the field crew on certain items of
equipment and procedures to assure data of good
quality.
Sample Objects drawn, usually at random, from the lot for
checking or auditing purposes.
154
-------
APPENDIX F
-------
APPENDIX F
CONVERSION FACTORS
Conversion factors for converting the U.S. customary units to the
International System of Units (SI)* are given below.
To Convert from
foot
inch
inch of mercury (in. of Hg) (32°F)
inch of mercury (in. of Hg) (60°F)
millimeter mercury (mmHg) (32°F)
inch of water (in. of H20) (29.2°F)
inch of water (in. of HO) (60°F)
To_
Length
meter (m)
meter (m)
Pressure
Newton/meter^
Newton/meter'
Newton/meter (N/m )
Newton/meter (N/m )
(N/mp
pound-force (Ibf avoirdupois)
pound-mass (Ibm avoirdupois)
degree Celsius
degree fahrenheit
degree rankine
degree fahrenheit
kelvin
foot/second
foot/minute
cubic foot (ft )
2
foot /minute
foot /second
Newton/meter (N/m )
Force
Newton (N)
Mass
kilogram (kg)
Temperature
kelvin (K)
kelvin (K)
kelvin (K)
degree Celsius
degree Celsius
Velocity
meter/second (m/s)
meter/second (m/s)
Volume
r~ 3 1 3^
meter (m )
Volume /Ti
Multiply by
0.3048
0.0254
3386.389
3376.85
133.3224
249.082
248.84
3 3
meter /second (m /s)
3 3
meter /second (m /s)
4.448222
0.4535924
iR = tc + 273.15
~v = (t,,+459.67)/l.
K. r
t = t /I.8
rs. A.
t« "
L ,-» ~"
"K
- 32)/1.8
- 273.15
0.3048
0.00508
0.02832
0.0004719
0.02832
Metric Practice Guide (A Guide to the Use of SI, the International Systems
of Units), American National Standard Z210.1-1971, American Society for
Testing and Materials, ASTM Designation:E380-70, Philadelphia, Pa., 1971.
156
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 REPORT NO.
EPA-650/4-74-005k
2.
3. RECIPIENT'S ACCESSIOWNO.
4. TITLE AND SUBTITLE
GUIDELINES FOR DEVELOPMENT OF A QUALITY ASSURANCE
PROGRAM: DETERMINATION OF BERYLLIUM EMISSION FROM
STATIONARY SOURCES
5. REPORT DATE
April 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
P. S. Wohlschlegel, F. Smith, D. E. Wagoner
8. PERFORMING ORGANIZATION REPORT NO.
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
Research Triangle Park, NC 27709
10. PROGRAM ELEMENT NO.
1HA327
11. CONTRACT/GRANT NO.
68-02-1234
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Monitoring and Support Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Washington, D. C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Guidelines for the quality assurance of the determination of beryllium emission
rates from stationary sources by the Federal reference method are presented. These
include:
1. Good operating practices
2. Directions on how to assess performance and qualify data
3. Directions on how to identify trouble and improve data quality
4. Directions to permit design of auditing activities
The document is not a research report. It is designed for use by operating
personnel.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Quality Assurance
Quality Control
Air Pollution
Gas Analysis
b IDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
13H
14D
13B
07D
14B
13. DISTRIBUTION STATEMENT
Release to Public
19 SECURITY CLASS (This Report)
-Unclassified
21 NO OF PAGES
156
20 SECURITY CLASS (This page)
Unclassified
22 PRICE
EPA Form 2220-1 (9-73)
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