p ro Atmospheric Research and Exposure Assessment Laboratory
§ $ CHEMISTRY. METEOROLOGY. METHODS DEVELOPMENT. MODELING. MONITORING. PHYSICS. QUALITY ASSURANCE
EPA/600/R-92/234
December 1992
GUIDELINES FOR MERCURY MEASUREMENTS
PROM STATIONARY SOURCES: QUALITY ASSURANCE HANDBOOK
SECTION 3.19
Office of Modeling, Monitoring Systems and Quality Assurance
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 2771 1
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TECHNICAL RFPQRT DATA
1. REPORT HO.
EPA/600/R-92/234
3.
PB93-131209
4. TITLE AND SUBTITLE
Guidelines for Mercury Measurements from Stationary
Sources: Quality Assurance Handbook, Section 3.19
5.REPORT DATE
December 1992
6.PERFORMING ORGANIZATION CODE
7. AUTBOR(S)
Frank Wilshire, EPA; Peter Grohse, RT1; Bill DeWees,
DeeCo
8.PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
PO Box 12194
Research Triangle Park, NC 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-D1-0009 (QA VII)
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
ORD/AREAL/MRDD/SMRB
Research Triangle Park, North Carolina 27711
13.TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
To beVincluded as Section 3.19 of the Quality Assurance Handbook, Volume III
-V. i •
16. ABSTRACT ~
e
Method 101A (M101A)Vis similar to Method 101 for the determination of mercury (Hg)
from stationary sources. In M101A, however, acidic potassium permanganate solution
is used for sample collection instead of acidic iodine monochloride solution. This
method applies to the determination of particulate and gaseous mercury emissions
from sewage sludge incinerators and other sources (as specified in the
regulations). Particulate and gaseous Hg emissions are withdrawn isokinetically
from the source and collected in acidic potassium permanganate solution. The
collected Hg (in mercuric form) is reduced to elemental Hg, which is then aerated
from the solution into an optical cell and measured by atomic absorption
spectrophotometry. After initial dilution, the range of this method is 20 to 800
ng Hg/mli.The upper limit can be extended by further dilution of the sample. The
sensitivity of the method depends on the recorder/spectrophotometer combination
selected.^" The collection efficiency of the sampling method can be affected by
excessive oxidizable matter in the stack gas that prematurely depletes the
potassium permanganate solution. The method descriptions given are based upon the
method promulgated October 15, 1980, and on corrections and additions published in
the Federal Register on September 12, 1984, and September 23, 1988. Also, current
updates in M101A analytical procedures are included in Section 3.19.10, for the
recovery of Hg from the filter catch in the analytical step 7.3.2 of the method.
17.
KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/ OPEN ENDED TERMS
c.COSATI
16. DISTRIBUTION STATEMENT
19. SECURITY CLASS (This Report)
21.NO. OF PAGES
143
20. SECURITY CLASS (This Pa*e)
.4
22. PRICE
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GUIDELINES FOR MERCURY MEASUREMENTS
PROM STATIONARY SOURCES: QUALITY ASSURANCE HANDBOOK
SECTION 3.19
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NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
ii
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Section No 3.19
Dace September 3, 1992
Page 1
Section 3.19
METHOD 101A—DETERMINATION OF PARTICULATE AND GASEOUS
MERCURY EMISSIONS FROM STATIONARY SOURCES
OUTLINE
Number
Section Documentation of Pages
SUMMARY 3.19 1
METHOD HIGHLIGHTS 3.19 2
METHOD DESCRIPTION
1. PROCUREMENT OF APPARATUS
AND SUPPLIES 3.19.1 18
2. CALIBRATION OF APPARATUS 3.19.2 25
3. PRESAMPLING OPERATIONS 3.19.3 7
4. ON-SITE MEASUREMENTS 3.19.4 19
5. POSTSAMPLING OPERATIONS 3.19.5 29
6. CALCULATIONS 3.19.6 10
7. MAINTENANCE 3.19.7 4 _
8. AUDITING PROCEDURE 3.19.8 * 4
9. RECOMMENDED STANDARDS FOR
ESTABLISHING TRACEABILITY 3.19.9 1
10. REFERENCE METHODS 3.19.10 18
11. REFERENCES 3.19.11 2
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Section No 3.19
Date September 3, 1992
Page 1
SUMMARY
Method 101A, for determining particulate and gaseous mercury (Hg) emissions
from stationary sources, is similar to Method 101. In 101A, however, acidic potassium
permanganate (KMnOJ solution is used for sample collection instead of acidic iodine
monochloride. This method applies to determining particulate and gaseous mercury (Hg)
emissions from sewage sludge incinerators and other sources as specified in the
regulations. Particulate and gaseous Hg emissions are withdrawn isokinetically from
the source and collected in an acidic KMnO, solution. The collected Hg (in mercuric
form) is reduced to elemental Hg, which is then aerated from the solution into an
optical cell and measured by atomic absorption spectrophotometry (AAS).
After initial dilution, the range of this method is 20 to 800 ng Hg/mL. The
upper limit can be extended by further dilution of the sample. The sensitivity of the
method depends on the recorder/ spectrophotometer combination selected. The collection
efficiency of the sampling method can be affected by excessive oxidizable matter in the
stack-gas that prematurely depletes the KMnO, solution.
The method descriptions given are based on the method1'2'1 promulgated October
15, 1980, and on corrections and additions published on September 12, 1984, and
September 23, 1988 (Section 3.19.10).
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Section No 3.19
Date September 3, 1992
Page 1
METHOD HIGHLIGHTS
Section 3.19 describes the procedures and specifications for determining
particulate and gaseous mercury emissions from sewage sludge incinerators and other
stationary sources as specified in the regulations. New procedures were added to
Method 101A1 on the basis of EPA-conducted development and evaluation of mercury
sampling and analysis. The major changes for Method 101A are:
1. The impinger KMnO« absorbing solution and the 8 N hydrochloric acid
(HCl) rinse are no longer combined in the field during sample recovery.
2. The impinger KMnO, absorbing solution must be filtered.
3. The filtrate must be analyzed within 24 h of filtration.
4. The residue on the filter from the filtration step must be digested with
8 N HCl.
5. The HCl digestate and the final field sample recovery rinse of HCl are
combined and analyzed separately from the KMn04 filtrate.
1. Procurement of Apparatus and Supplies
Section 3.19.1 (Procurement of Apparatus and Supplies) gives specifications,
criteria, and design features for the equipment and materials required for Method 101A.
This section can be used as a guide for procuring and initially checking equipment and
supplies. The activity matrix (Table 1.1) at the end of the section is a summary of
the details given in the text and can be used as a quick reference.
2. Pretest Preparations
Section 3.19.2 (Calibration of Apparatus) describes the required calibration
procedures and considerations for the Method 101A sampling equipment. Required
accuracies for each component also are included. A pretest checklist (Figure 3.1 in
Subsection 3.19.3) or a similar form should be used to summarize the calibration and
other pertinent pretest data. The calibration section may be removed along with the
corresponding sections for the other methods and made into a separate quality assurance
reference manual for personnel involved in calibration activities.
Section 3.19.3 (Presampling Operations) provides testers with a guide for
preparing equipment and supplies for field tests. A pretest preparation form can-be
used as an equipment checkout and packing list. Because of the potential for high
blank levels, special attention must be paid to preparing the sampling equipment.
Also, testers must ensure that any required audit samples are obtained for the test by
the responsible regulatory agency.
Activity matrices for calibrating the equipment and the presampling operations
(Tables 2.1 and 3.1) summarize the activities.
3. On-Site Measurements
Section 3.19.4 (On-Site Measurements) contains step-by-step procedures for
sample collection, sample recovery, and sample preparation for transport. The on-site
checklist (Figure 4.3, Section 3.19.4) provides testers with a quick method for
checking the on-site requirements. Table 4.1 provides an activity matrix for all
on-site activities.
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Section No 3.19
Date September 3, 1992
Page 2
4. Posttest Operations
Section 3.19.5 (Posttest Operations) presents the posttest equipment
procedures and a step-by-step analytical procedure for determination of mercury.
Posttest calibrations are required for the sampling equipment. The posttest operations
form (Figure 5.9, Section 3.19.5) provides some key parameters that testers and
laboratory personnel must check. The step-by-step sample preparation and analytical
procedure descriptions can be removed and made into a separate quality assurance
analytical reference manual for laboratory personnel.
Section 3.19.6 (Calculations) provides testers with the required equations,
nomenclature, and significant digits. A calculator or computer should be used, if
available, to reduce the chances of error.
Section 3.19.7 (Maintenance) provides testers with a guide for a maintenance
program. This program is not required, but it should reduce equipment malfunctions.
Activity matrices (Tables 5.1, 6.1, and 7.1) summarize all postsampling, calculation,
and maintenance activities.
5. Auditing Procedures
Section 3.19.8 (Auditing Procedure) provides a description of necessary
activities for conducting performance and system audits. The data-processing
procedures and a checklist for a systems audit also are included in this section.
Table 8.1 is an activity matrix for conducting the performance and system audits.
Section 3.19.9 (Recommended Standards for Establishing Traceabi-lity) provides
the primary standard to which the analytical data should be traceable.
6. References
Section 3.19.10 contains the promulgated Method 101A; Section 3.19.11 contains
the references cited throughout the text.
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Section No. 3.19.1
Date September 3, 1992
Page 1
1.0 PROCUREMENT OP APPARATUS AMD SUPPLIES
Before Method 101A can yield results, it must be employed accurately.
Consequently, all users are advised to read this document and to adopt its procedures.
Alternative procedures should be employed only if they are outlined herein.
This section describes equipment specifications, criteria, and design features
for the sampling train used for Method 101A. It is intended to help users with
equipment selection. A schematic of the sampling train is shown in Figure 1.1 as an
aid in the discussion that follows.
This section also describes procedures and limits, where applicable, for
acceptance checks. Calibration data generated by the acceptance checks should be
recorded in the calibration log book.
When procuring equipment and supplies, users should record the descriptive
title of the equipment, identification number (if applicable), and the results of
acceptance checks in a procurement log.
The following procedures and descriptions are provided only as guidance and
may not be required for the initial ordering and check-out of the equipment and
supplies. Testers should note, however, that many of these procedures are required at
a later step in the sampling and analytical procedures. Instituting these or similar
procedures as routine practices for checking new equipment and supplies, therefore,
will prevent later problems and/or delays in test programs. At the end of this
section, Table 1.1 provides a summary of quality assurance activities for procurement
and acceptance of apparatus and supplies.
1.1 Sams!inq
The sampling train shown in Figure 1.1 is similar to the Method 5 train
(Method 5 refers to 40 CFR Part 60). The Method 101A sampling train consists of the
following components:
1.1.1 Nozzle—The no2zle shall be made of nickel, nickel-plated stainless-steel,
quartz, or borosilicate glass. The tapered angle should be <30°, with taper on the
outside to preserve a constant inside diameter (ID).
A range of nozzle ID'S—for example, 0.32 to 1.27 cm (0.125 to 0.5 in.)—in
increments of 0.16 cm (0.0625 in.) should be available for isokinetic sampling. Larger
nozzle sizes may be required if very low flows are encountered.
Upon receipt of the nozzle(s) from the manufacturer, users should inspect it
for roundness, for the proper material, and for damage to the tapered edge (nicks,
dents, and burrs). Check the diameter with a micrometer; calibration procedures are
described in Section 3.18.2. A slight variation from exact sizes is normal. Engrave
each nczzle with an identification number for inventory and calibration purposes. See
Section 3.18.3 for proper cleaning procedures.
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HEATED AREA
TEMPERATURE
SENSOR
\_
PROBER (pf
^"1
[41
r
STACK
^ALL
THERMOMETER
\ FILTER HOLDER
T (OPTIONAL)
CHECK
VALVE
THERMOMETER |
I
TYPE S /
PITOT TUBE
\
1
PITOT MANOMETER
IMPINGERS^
THERMOMETERS
ICE BATH
TEMPERATURE SENSOR
\
Cl
PROBE
?
a
7T
f
PITOT TUBE
ORIFICE
o
BY-PASS VALVE
5
MAIN
VALVE
/
VACUUM
DRY GAS
METER
GAUGE
AIR TIGHT
PUMP
•flow
B> f (D
IQ rt o
It i» rt
to (n o
VACUUM
§ °
A OJ
•i .
M
u>
LINE
Figure'1.1. Schematic of Method 101A sampling train.
vo
to
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Section No. 3.19.1
Date September 3, 1992
Page 3
1.1.2 Pi tot Tube-The pitot tube, preferably of Type S design, should meet the
requirements of Method 2, Section 3.1.2 of this Handbook. The pitot tube is attached
to the probe as shown in Figure 1.1. The proper pitot-tube/sampling-nozzle
configuration to prevent aerodynamic interference is shown in figures 2.6 and 2.7 of
Method 2, Section 3.1.2 of this Handbook.
The pitot tube should be inspected visually for both vertical and horizontal
tip alignments. If the tube is purchased as an integral part of a probe assembly,
check the dimensional clearances using figures 2.6 and 2.7 (of Method 2, Section
3.1.2). Repair or return any pitot tube that does not meet specifications. The
calibration procedure for a pitot tube is covered in Section 3.4.2 of this Handbook.
1.1.3 Differential Pressure AP-The differential pressure gauge should be an inclined
manometer or the equivalent, as specified in Method 2, Section 3.1.2 of this Handbook.
Two gauges are required. One is used to monitor the stack velocity pressure, whereas
the other is used to measure the orifice pressure differential.
Initially, check the gauge against a gauge-oil manometer at a minimum of three
points: 0.64 mm (0.025 in.); 12.7 mm (0.5 in.); and 25.4 mm (1.0 in.) H:0. The gauge
should read within 5% of the gauge-oil manometer at each test point. Repair or return
to the supplier any gauge that does not meet these requirements.
1.1.4 Probe Liner-The probe liner is made of borosilicate or quartz glass tubing.
(Note: Do not use metal probe liners.) If a filter is used ahead of the impingers,
testers must use the probe heating system to minimize the condensation of gaseous Hg.
A heating system is required that will maintain an exit gas temperature of 120 ± 14 °C
(248 ± 25 °F) during sampling. Other temperatures may be specified by a subpart of the
regulations and must be approved by the Administrator for a particular application.
Because the actual probe outlet temperature is not usually monitored during sampling,
probes constructed in accordance to APTD-0581 and calibrated according to procedures
in APTD-0576 will be acceptable.
Either borosilicate or quartz glass liners may be used for stack temperatures
up to about 480 °C (900 °F), but quartz glass liners must be used from 480 to 900 °C
(900 to 1650 °F). Either type of liner may be used at higher temperatures for short
periods, with Administrator approval. However, the absolute upper limits-the softening
temperatures of 820 °C (1508 °F) and 1500 °C (2732 °F)-for borosilicate and quartz,
respectively, must be observed.
Upon receiving a new probe, users should check it visually to see whether it
is the length and composition ordered. The probe also should be checked visually for
breaks or cracks, and it should be checked for leaks on a sampling train (Figure 1.1).
Leak checks should include a proper nozzle-to-probe connection with a Viton O-ring,
Teflon® ferrules, or asbestos string.
The probe heating system should be checked as follows:
1. With a nozzle attached, connect the probe outlet to the inlet of the
metering system.
2. Connect the probe heater to an outlet and turn it on for 2 or 3 min.
The probe should become warm to the touch.
3. Start the pump and adjust the needle valve until it indicates a flow
rate of about 0.02 m3/min (0.75 ft5/min) .
4. Be sure the probe remains warm to the touch; the heater should be
capable of maintaining an exit air temperature of 100 °C (212 °F)
minimum. Failure indicates that the probe should be repaired, returned
to the supplier, or rejected.
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Section No. 3 .19.1
Date September 3, 1992
Page 4
1.1.5 Filter Holder (OptionalJ-The filter holders should be made of borosilicate
glass with a rigid, stainless-steel wire-screen filter support. Do not use glass frit
supports. A silicone rubber or Teflon gasket is essential to provide a positive seal
against leakage from outside or around the filter. Upon receipt, assemble the filter
holder with a filter and conduct a leak check. There should be no leak at a vacuum of
15 in. of Hg.
1.1.6 Impingers—Four Greenburg-Smith impingers must be connected in series with
leak-free, ground glass fittings or any similar leak-free, noncontaminating fittings.
For the first, third, and fourth impingers, testers may use impingers that are modified
by replacing the tip with a 13-mm ID (0.5 in.) glass tube extending to 13 mm (0.5 in.)
from the bottom of the flask. The connecting fittings should form leak-free,
vacuum-tight seals. See Section 3.19.3 for proper cleaning procedures.
Upon receipt of a standard Greenburg-Smith impinger, users should fill the
inner tube with water. If the water does not drain through the orifice in 6 to 8 s or
less, the impinger tip should be replaced or enlarged to prevent an excessive pressure
drop in the sampling system. Each impinger should be checked visually for damage:
breaks, cracks, or manufacturing flaws, such as poorly shaped connections.
1.1.7 Acid Trap-The acid trap should be a Mine Safety Appliances™ airline filter,
catalog number 81857, with acid absorbing cartridge and suitable connections, or the
equivalent. Upon receipt, check the part number to ensure the part is correct.
1.1.8 Filter Heating Systero-Any heating system may be used that is capable of
maintaining the filter holder at 120 ± 14 °C (248 ± 25 °F) during sampling. Other
temperatures may be specified by a subpart of the regulations or approved by the
Administrator for a particular application. A gauge capable of measuring temperatures
to within 3 °C (5.4 °F) should be provided to monitor the temperature around the filter
during sampling.
Before sampling, the heating system and the temperature monitoring device
should be checked. For convenience, the heating element should be easily replaceable
should a malfunction occur during sampling.
1.1.9 Metering Systero-The metering system should consist of a vacuum gauge, a vacuum
pump, thermometers capable of measuring ± 3 °C (5.4 °F) of true value in the range-of
0 to 90 °C (32 to 194 °F), a dry-gas meter with 2% accuracy at the required sampling
rate, and related equipment as shown in Figure 1.1. Other systems capable of
maintaining metering rates within 10% of the isokinetic sampling rate and of
determining sample volumes to within 2% of the isokinetic rate may be used if approved
by the Administrator. Sampling trains with metering systems designed for sampling
rates higher than those described in APTD-0581 and APTD-0576 may be used if the above
specifications can be met. When the metering system is used with a pitot tube, it
should permit verification of an isokinetic sampling rate through the use of a
nomograph or by calculation.
Upon receipt or after construction of the system, users should perform both
positive and negative pressure leak checks before beginning the system calibration
procedure described in Subsection 2.1 of Section 3.19.2. Any leakage requires repair
or replacement of the malfunctioning item.
1.1.10 Barometer-h mercury, aneroid, or other barometer capable of measuring
atmospheric pressure to within ± 2.5 mm (0.1 in.) Hg is required.
A preliminary check of a new barometer should be made against a
mercury-in-glass barometer or the equivalent. In lieu of a barometer check, the
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Section No. 3.19.1
Date September 3, 1992
Page 5
absolute barometric pressure may be obtained from a nearby weather service station and
adjusted for elevation difference between the station and the sampling point. Either
subtract 2.5 mm Hg/30 m (0.1 in. Hg/100 ft) from the station value for an elevation
increase, or add the same for an elevation decrease. If the barometer cannot be
adjusted to within 2.5 mm (0.1 in.) Hg of the reference barometric pressure, it should
be returned to the manufacturer or rejected.
1.1.11 Gas Density Determination Equipment—h temperature sensor and a pressure gauge
are required as described in Method 2 (Section 3.1.2 of this Handbook). Additionally,
a gas analyzer as described by Method 3 may be required. The temperature sensor should
be permanently attached to either the probe or the pitot tube. In either case, it is
recommended that a fixed configuration (Figure 1.1) be maintained. The sensor also may
be attached just prior to field use, as described in Section 3.19.2.
1.2 Sample Recovery
1.2.1 Glass Sample Bottles Sample bottles should be 1000- and 100-mL without leaks
and with Teflon-lined caps. Upon receipt, check visually for cracks in the glass.
Ensure that the cap liners are Teflon, because other material can result in sample
contamination and reaction with the KMn04. Because of the potential reaction of the
KMnO« with the acid, there may be pressure buildup in the sample storage bottles.
Venting is highly recommended. A No. 70-72 hole drilled in the container cap and
Teflon liner has been found to allow adequate venting without loss of sample.
1.2.2 Graduated Cylinder—A 250-mL cylinder is required.
1.2.3 Funnel and Rubber Policeman-These items are used to aid in transferring silica
gel to containers; they are not necessary if silica gel is weighed in the field.
1.2.4 Funnel—A glass funnel is needed to aid in sample recovery.
1.3 Sample Preparation and Ha Analysis
1.3.1 Volumetric Pipets—Class A 1-, 2-, 3-, 4-, 5-, 10-, and 20-mL pipets are
required.
1.3.2 Graduated Cyhnder-A 25-mL cylinder is required.
1.3.3 Steajn Bath-Refers to 40 CFR, Part 60, Appendix B, Method 101A.
1.3.4 Atomic Absorption Spectrophotometer-kny atomic absorption unit is suitable,
provided it has an open sample presentation area in which to mount the optical cell.
Follow the instrument settings recommended by the manufacturer. Instruments designed
specifically for measuring mercury using the cold-vapor technique are commercially
available and may be substituted for the atomic absorption spectrophotometer.
1.3.5 Optical CelJ-The optical cell should be of cylindrical shape, with quartz end
windows and having the dimensions shown in Figure 1.2. Wind the cell with
approximately 2 m of 24-gauge nichrome heating wire, and wrap with fiberglass
insulation tape or the equivalent; do not let the wires touch each other. A heat lamp
mounted above the cell or a moisture trap installed upstream, of the cell may be used
as alternatives. Upon receipt, check the dimensions and the capability of the heating
system.
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Section No. 3.19.1
Date September 3, 1992
Page 6
1.3.6 Aeration Cel2-The aeration cell should be constructed according to the
specifications in Figure 1.3. Do not use a glass frit as a substitute for the blown
glass bubbler tip shown in Figure 1.3.
1.3.7 Recorder—The recorder must be matched to the output of the spectrophotometer
described above. As an alternative, an integrator may be used to determine peak area
or peak height.
1.3.8 Variable Transformer*-This item is needed to vary the voltage on the optical
cell from 0 to 40 volts.
1.3.9 Hood-A hood is required for venting the optical cell exhaust.
1.3.10 FJow Metering Valve— Refers to 40 CFR, Part 60, Appendix B, Method 101A.
1.3.11 Flow Meter-k rotameter, or equivalent, is required that is capable of
measuring a gas flow of 1.5 L/min. Upon receipt, calibrate the flow meter at a flow
rate of 1.5 L/min with a bubble meter or wet-test meter.
1.3.12 Aeration Gas Cylinder-The cylinder must contain nitrogen or dry, Hg-free air
and must be equipped with a single-stage regulator.
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Section No. 3.19.1
Date September 3, 1992
Page 7
11/9 female ball socket
LENGTH NECESSARY TO FIT SOLUTION CELL
TO SPECTROPHOTOMETER
(END VIEW)
TO VARIABLE TRANSFORMER
VENT TO HOOD
OD
2.5 etn
*-mm OD
3 *1 em DIAMETER
QUARTZ WINDOWS
AT EACH END
(FRONT VIEWI
NOTES
CELL WOUND WITH 24-GAUGE NICHROME WIRE
TOLERANCESiS PERCENT
Figure 1.2.
Optical cell.
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Section No. 3.19.1
Date September 3, 1992
Page 8
FROM TANK
1IA MALE BALL JOINT
4-mm BORE TEFLON STOPCOCK
BUBBLER ,
PORTION '
-—» 1
TO
IOPTICAL CELL
11/22 GROUND CLASS JOINT
IB/9 MALE BALL JOINT
IB/22 OROUND
GLAU JOINT
WITH STOPPER
ALL DIMENSIONS IN an
UNLESS OTHERWISE NOTED
BLOWN GUUS BUBBU*
•omi PORTION
AffROX-OB^r 4A«n OD toy XB^n ID
Figure 1.3. Aeration cell.
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Section No. 3.19.1
Date September 3, 1992
Page 9
1.3.13 TuJbing-The tubing is required for connections. Use glass tubing (ungreased
ball and socket connections are recommended) for all connections between the solution
cell and the optical cell; do not use Tygon tubing, other types of flexible tubing, or
metal tubing as substitutes. Testers may use Teflon, steel, or copper tubing between
the nitrogen tank and the flow meter valve (Section 5.3.7), and Tygon, gum, or rubber
tubing between the flow meter valve and the aeration cell.
1.3.14 Flow Kate Calibration Equipment-This equipment consists of a bubble flow meter
or a wet-test meter for measuring a gas flow rate of 1.5 ± 0.1 L/min.
1.3.15 Volumetric Fiasfcs-These flasks must be Class A, with pennyhead standard taper
stoppers; the required sizes are 100-, 250-, 500-, and 1000-mL.
1.3.16 Volumetric Pipets-These pipets must be Class A; the required sizes are 1-, 2-,
3-, 4-, and 5-mL.
1.3.17 Graduated Cylinder— A 50-mL cylinder is required.
1.3.18 Magnetic Stirrer- A general purpose laboratory-type stirrer is required.
1.3.19 Magnetic Stirring Bar- A Teflon-coated stirring bar is required.
1.3.20 Trip Balance— A trip balance capable of weighing to ± 0.5 g is required. Upon
receipt, check balance with standard weights.
1.3.21 Analytical Balance-An analytical balance capable of weighing up to ± 0.5 mg
is required. Upon receipt, check balance with standard weights.
1.4 Alternative Analytical Apparatus
If any alternative analytical apparatus is to be used, it must pass the
performance criteria described in Section 3.19.5.5. Alternative Hg cold-vapor
analytical systems are available commercially from most atomic absorption manufacturers
and employ automated flow-injection techniques. Such systems automatically inject
sample solutions into continuous reagent streams containing the reducing reagent.
Mercury is usually measured as a solution concentration (e.g., mg Hg/L). An example
of a typical cold-vapor AA instrument using flow injection is shown in Figure 1.4.
Such systems are allowable as long as they meet the following criteria:
1.4.1 Calibration Curve Linearity-The system must generate a linear calibration
curve, and two consecutive samples of the same aliquot size and concentration must
agree within 3% of their average.
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Multichannel Pump
Inert Gas
Dilute HC1
Mixing Colls
Sample
Reducing Reagent
Spectrophotometer w/ Optical Cell
Gas/Liquid Separator
Autosampler
To Vent
oooo
oooo
oooo
oooo
To Waste
Figure 1.4. Typical' Cold Vapor* AA instrumentation using flow injection.
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Section No. 3.19.1
Date September 3, 1992
Page 11
1.4.2 Spike Recovery—The system must allow for recovery of a minimum of 95% of the
spike when an aliquot of a source sample is spiked with a known concentration of Hg
(II) compound.
1.5 Reagents
1.5.1 Sampling and Sample Recovery—Use ACS reagent-grade chemicals or the
equivalent, unless otherwise specified. The following reagents are used in sampling
and recovery:
Water-Deionized distilled, meeting ASTO specifications for Type I Reagent
Water-ASTM Test Method D 1193-77. If high concentrations of organic matter are not
expected to be present, users may eliminate the KMn04 test for oxidizable organic
matter. Use this water in all dilutions and solution preparations.
Nitric Acid (HNO}), 50* (v/vJ-Mix equal volumes of concentrated HN03 and water,
being careful to add the acid to the water slowly.
Silica Gei-Indicating type, 6- to 16-mesh. If previously used, dry at 175 °C
(350 °F) for 2 h. Testers may use new silica gel as received.
Filter (Optional)—Glass fiber filter, without organic binder, exhibiting at
least 99.95% efficiency on 0.3-nm dioctyl phthalate smoke particles. Testers may use
the filter in cases where the gas stream contains large quantities of particulate
matter, but they should analyze blank filters for Hg content.
Sulfuric Acid IH:SOt), 10% (v/v)— Slowly add 100 mL of concentrated H2S04 to 900
mL of water and mix cautiously.
Absorbing Solution, 4$ KMn04 (w/v)—Prepare fresh daily. Dissolve CO g of KMn04
in sufficient 10% H2S04 to make 1 L. Prepare and store in glass bottles to prevent
degradation.
Caution: To prevent autocatalytic decomposition of the permanganate solution, filter
it through Whatman1" 541 filter paper. In addition, owing to the reaction of the KMnO,
with the acid, there may be pressure buildup in the sample storage bottle. These
bottles should not be filled to capacity and should be vented, both to relieve excess
pressure and to prevent explosion of the container: A No. 70-72 hole drilled in the
container cap and Teflon liner is recommended.
Hydrochloric Acid-Trace metals grade HC1 is recommended. If other grades are
used, the Hg level must be less than 3 ng/mL Hg. Upon receipt, check manufacturer's
guarantee or analyze the acid for background contamination.
Hydrochloric Acid, 8 N-Dilute 67 mL of concentrated HC1 to 100 mL with water
(slowly add the HC1 to the water).
-------
Section No. 3.19.1
Date September 3, 1992
Page 12
1.5.2 Analysis—'The reagents needed for analysis are listed below:
Tin (II) Solution-Prepare fresh daily and keep sealed when not being used.
Completely dissolve 20 g of tin (II) chloride [or 25 g of tin (II) sulfate] crystals
(Baker7* Analyzed reagent grade or any other brand that will give a clear solution) in
25 mL of concentrated HCl. Dilute to 250 mL with water. Do not substitute HNOJr H2S04,
or other strong acids for the HCl.
Sodium Chloride-Hydroxylamine Solution-Dissolve 12 g of sodium chloride and
12 g of hydroxylamine sulfate (or 12 g of hydroxylamine hydrochloride) in water and
dilute to 100 mL.
Hydrochloric Acid, 8 N-Dilute 67 mL of concentrated HCl to 100 mL with water
(slowly add the HCl to the water).
Nitric Acid, 15% (v/v)— Dilute 15 mL of concentrated HN03 to 100 mL with water.
Mercury Stock Solution, 1 mg Hg/mL-Prepare and store all Hg standard solutions
in borosilicate glass containers. Completely dissolve 0.1354 g of Hg (II) chloride in
75 mL of water. Add 10 mL of concentrated HN03 and adjust the volume to exactly 100
mL with water. Mix thoroughly. This solution is stable for at least 1 month.
Intermediate Hg Standard Solution, 10 \xg/n>Lr-Prepare fresh weekly. Pipet 5.0
mL of the Hg stock solution (Section 6.2.5) into a 500-mL volumetric flask, and add 20
mL of 15% HNO, solution. Adjust the volume to exactly 500 mL with water. Thoroughly
mix the solution.
Working Hg Standard Solution, 200 ng Hg/irlr- Prepare fresh daily. Pipet 5.0 mL
from the Intermediate Hg Standard Solution (Section 6.2.6) into a 250-mL volumetric
flask. Add 5 mL of 4% KMnO, absorbing solution and 5 mL of 15% HN03. Adjust the volume
to exactly 250 mL with water. Mix thoroughly.
Potassium Permanganate, 5% (w/v)— Dissolve 5 g of KMnO, in water and dilute to
100 mL.
Fiiter-Use a Whatman 40, or equivalent.
-------
Section No. 3.19.1
Date September 3, 1992
Page 13
TABLE 1.1 ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS AND SUPPLIES
Apparatus
1
1
(Acceptance limits
1
1
(Frequency & method
(of measurement
1
(Action if
|requirements
|are not met
1
Samplina
I
1
1
1
1
1
Probe liner
1
|Specified material
|of construction;
I equipped with
|heating system
|capable of
Imaintaining 120 °C
|s 14°C (248 °C S
125 °F) at the exit
1
1
|Visually check and
I run the heating
|system
1
1
1
1
1
1
1
|Repair,
I return to
I supplier, or
I reject
1
1
1
1
1
Probe
nozzle
|Nickel, nickel-
Iplated stainless-
|steel, quartz, or
Iborosilicate
Iglass, tapered <
13 0°; difference in
Imeasured diameter
I< 0.1 mm (0.004
I in . ) ; no nicks,
I dents, or
I corrosion
j (Subsec. 1.1.2)
1
Ivisually check
|before each test;
|use a micrometer to
I measure ID before
|field use; after
(each repair
1
1
1
1
1
1
1
|Reshape and
|sharpen,
I return to
I the supplier,
|or reject
1
1
(
1
1
1
1
Pitot tube
I Type S (Sec.
|3.1.2); attached
|to probe with im-
Ipact (high press-
lure) opening plane
leven with or above
I nozzle entry plane
1
Ivisually check for
Iboth vertical and
I horizontal tip
I alignments;
I calibrated according
I to Sec. 3.4.2
1
1
|Repair or
I return to
|supplier
1
1
1
1
Differ-
ential
pressure
gauge
|Meets criteria
I (Sec. 3.1.2) ;
lagree, within 5%
|of gauge-oil
I manometer
1
1
I Check against a
I gauge-oil manometer
|at a minimum of 3
|points; 0.64
I (0.025) ; 12.7 (0.5) ;
I 2 5.4 (1.0) mm. (in)
|h2o
1
I Repair or
I return to
I supplier
1
1
1
1
1
Vacuum
gauge
I 0-760 mm (0-30
I in.) Hg, ± 25 mm
I (1 in. ) at 380 mm
I in.) Hg
|Check against
|mercury U-tube
|manometer upon
|receipt
|Adjust or
|return to
|supplier
1
(Continued)
-------
Section No. 3.19.1
Date September 3, 1992
Page 14
TABLE 1.1 (Continued)
Apparatus
1
1
(Acceptance limits
1
1
I Frequency & method
|of measurement
1
(Action if
|requirements
I are not met
1
Vacuum pump
|Leak free; capable
|of maintaining a
|flow rate of
j 0.02 - 0.03 mJ/min
|(0.66 to 1.1
|ft3/min) for pump
I inlet vacuum of
I 380 mm (15 in.) Hg
1
(Check upon receipt
I for leaks and
I capacity
1
1
1
1
1
1
I Repair or
I return to
I supplier
1
1
1
1
Orifice
meter
|AH@ of 46.74 t
I 6.35 mm (1.84 ±
I 0.25 in.) HjO at
{ 68 °F (not
Imandatory)
1
|Upon receipt,
I visually check for
I damage and calibrate
(against wet-test
I meter
1
I Repair, if
I possible,
I otherwise
I return to
(supplier
1
Impingers
|Four Greenburg-
|Smith connected in
|a series, leak-
Ifree, noncontamin-
lating fittings
1
|Visually check upon
|receipt; check
|pressure drop
|(Subsec. 1.1.6)
1
1
I Return to
|supplier
1
1
1
1
Filter
holder
(opt ional)
I Leak-free;
Iborosilicate glass
1
1
(Visually check
|before use; conduct
|leak check
1
(As above
1
1
Filter
support
|Rigid stainless-
|steel wire screen
1
1
Ivisually check upon
|receipt, conduct
I leak check
1
|Repair or
I return to
(manufacturer
Filter
heating
system
I Capable of
(maintaining filter
|holder at
|temperature of
1120 °C ± 14 °C
I(248 °F ± 25°F)
1
|Visually check upon
I receipt and run
|heating system
|checkout
1
1
1
(Repair or
|return to
(manufacturer
1
1
1
1
Dry-gas
meter
|Capable of
(measuring volume
Iwithin 2% at a
|flow rate of
I 0 . 02 ir.'/min
|(0.75 ft'/min)
1
|Check for damage
lupon receipt and
(calibrate (Sec.
I 3 .4 .2 ) against
Iwet-test meter
1
1
|Reject if
|damaged,
(behaves
(erratically,
| or cannot be
|properly
|adjusted
(Continued)
-------
Section No. 3.19.1
Date September 3, 1992
Page 15
TABLE 1.1 (Continued)
Apparatus
1
1
(Acceptance limits
1
1
I Frequency & method
|of measurement
1
lAction if
I requirements
I ere not met
1
Acid Trap
|Mine Safety Appli-
lances air line
|filter acid ab-
sorbing cartridge
1
|Visually check upon
|receipt
1
1
I Return to
|supplier
1
1
1
Thermo-
meters
|± 1 °C (2 °F) of
|true value in the
|range of 0 to
|25 °C (32 to
|77 °F) for impin-
|ger thermometer
land ± 3 °C
|(5.4 °F) of true
lvalue in the range
|of 0 to 90 °C
|(32 to 194 °F) for
|dry-gas meter
|thermometers
1
I Check upon receipt
|for dents or bent
|stem, and calibrate
| (Sec. 3.4.2) against
|mercury-in-glass
|thermometer
1
1
1
1
1
1
1
1
iReject if
tunable to
I calibrate
1
1
1
1
1
1
1
1
1
1
1
Barometer
I Capable of
|measuring
I atmospheric
|pressure within
j 2.5 mm (0.1 in.)
1 Hg
1
1
1
I Check against a
|mercury-in-glass
|barometer or
I equivalent;
I calibrate
| (Sec. 3.1.2)
1
1
1
|Determine
I correction
|factor, or
Ireject if
I difference
|more than
|± 2.5 mm
1(0.1 in.) Hg
1
Gas density
determi-
nation
equipment
|Meet the
(requirements in
|Sec. 3.2.1
1
1
|Conduct checks shown
|in Sec. 3.2.1,
lupon receipt
1
1
I Repair,
|replace, or
I return to
I supplier
1
Sample
Recovery
1
1
l
1
1
1
1
Glass
sample
bottles
1
|Leak-free, Tef-
|Ion lined caps,
11000 and 100 mL
1
1
I Visually check upon
|receipt for cracks,
|ensure that caps are
|Teflon
1
I Replace or
I return to
I supplier
(Continued)
-------
Section No. 3 .19.1
Date September 3, 1992
Page 16
TABLE 1.1 (Continued)
Apparatus
1
1
|Acceptance limits
1
1
I Frequency & method
I of measurement
1
I Action if
I requirements
|are not met
1
Sample
Preparat ion
and
Analysis
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Glassware
1
|Class A
1
1
1
l
IVisually check upon
|receipt
1
1
1
I Replace or
I return to
|supplier
1
AA spec-
trometer
|Suitable optical
|resolution system
land detector
1
1
I Perform appropriate
I calibrations
|according to Sec. 5
1
1
|Return to
Imanufacturer
|or repair and
I re-check
1
Recorder or
electronic
integrator
|See owner's manual
1
1
1
|Upon receipt, check
1
1
1
|Repair or
I return to
(manufacturer
1
Optical
cell
|See Figure 1.2
1
1
1
|Upon receipt, check
I to ensure correct
I dimensions, check
I heating system
1
|Return to
[manufacturer,
I clean as
|needed
Aeration
cell
|See Figure 1.3
1
1
1
(visually check
1
1
1
i J
|Repair or
|return to
(manufacturer
1
Moisture
removal
system
I Heated cell or
Imoisture trap
|to remove
|condensation
Ifrom optical cell
1
I Calibrate whenever
|system is turned on
1
1
1
1
(Calibrate
|heated cell
|or change
Idesiccant
1
1
Regulator
|Proper fittings
land pressure
I control
1
1
1
1
|Upon receipt,
|attach to cylinder
land check
1
1
1
1
(Return to
(manufacturer,
|repair,
|or replace
|fitting and
|re-check
1
Flowmeter
|Capable of
|measuring flow
|of 1.5 L/min
1
|Calibrate with
|bubble meter or
|wet-test meter
|upon receipt
|Return to
(manufacturer
|or repair and
I recalibrate
(Continued)
-------
Section No. 3.19.1
Date September 3, 1992
Page 17
TABLE 1.1 (Continued)
Apparatus
1
1
I Acceptance limits
1
1
I Frequency & method
|of measurement
1
lAction if
I requirements
|are not met
1
Variable
transformer
|Capable of varying
|voltage from 0 to
|40 volts
1
Ivisually check
lupon receipt
1
1
I Return to
(manufacturer
|or repair
1
Aeration
gas
cylinder
I Nitrogen or dry,
|Hg-free air equip-
Iped with regulator
1
Ivisually check
lupon receipt
1
1
I Return to
|supplier
1
1
Tubing
I See Sec. 1.3.13
|for specifications
|of tubing for the
I connections
1
Ivisually check to
I ensure proper type
I tubing
1
1
I Replace
1
1
1
1
Trip
balance
I Capable of
Imeasuring within
1 0.5 g
1
I Check with standard
I weights upon receipt
land before each use
1
I Replace or
I return to
Imanufacturer
1
Analytical
balance
I Capable of weigh-
|ing to ± 0.5 mg
1
I As above
1
1
I As above
1
1
Alternative
analytical
apparatus
I Capable of gene-
rating a linear
I calibration curve;
|two consecutive
I samples of equal
Isize and concen-
tration agree ± 3%
|of average; and £
I 95% recovery of
I known concentra-
tion of spiked
I sample
1
I See owner's manual
1
1
1
1
1
1
1
1
1
1
1
1
I Return to
I supplier
1
1
1
1
1
1
1
1
1
Sair.pl ina
and
Sample
Recovery
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Reagents
1
|ACS reagent grade
|or Hg blank level
I specif led
1
Ivisually check upon
I receipt or conduct
|Hg analysis
i
|Return to
|supplier or
|replace
(Continued)
-------
Section No. 3.19.1
Date September 3, 1992
Page 18
TABLE 1.1 (Continued)
Apparatus
1
1
I Acceptance limits
1
1
I Frequency & method
|of measurement
1
I Action if
I requirements
|are not met
1
Water
|Deionized, dis-
|tilled meeting
|ASTM D1193-77
|specifications
1
I Check each lot or
|specify type when
I ordering
1
I
I Replace or
|return to
|supplier
1
1
Silica gel
|Indicating type,
I 6- to 16-mesh
1
I
|Upon receipt, check
I label for grade
|or certification
1
I Return to
I supplier
1
Filter
(optional)
|Glass fiber with-
|out organic bin-
jder; 99.95% col-
lection efficiency
I for 0.3 |im dioctyl
Iphthalate smoke
I particles
1
(Manufacturer's gua-
rantee that filters
|were tested accord-
|ing to ASTM D 2986-
|71; observe under
I light for defects
1
1
I Return to
|supplier
1
1
1
1
1
1
Analysis
1
1
1
1
1
1
Reagents
I
|ACS reagent grade
|or equivalent;
|prepared as
I described in
I Sec. 1.5.3
1
1
1
1
|Upon receipt, check
|label for grade or
|certification; Check
|stability of
|prepared solution
I and prepare when
•|necessary
1
i
|Replace or
|return to
I supplier
1
1
1
1
Filter
|Whatman 4 0
|or equivalent
1
1
|Upon receipt, check
|label for grade
1
1
|Replace or
|return to
|supplier
1
-------
Section No. 3.19.2
Date September 3, 1992
Page 1
2.0 CALIBRATION OF APPARATUS
Calibrating the apparatus is one of the more important functions in
maintaining data quality. The detailed calibration procedures for the sampling
apparatus included in this section were designed for the sampling equipment specified
in Method 5 and described in the previous section. Calibrating the analytical
equipment is described in Section 3.19.5, which details the analytical procedures.
Table 2.1, at the end of this section, summarizes the quality assurance (QA) functions
for the calibrations. All calibrations, including those performed on the analytical
equipment, should be recorded on standardized forms and retained in a calibration log
book.
2.1 Metering System
The dry-gas meter (DGM) in the sampling system's meter console must be
calibrated against a primary standard meter (wet-test meter or spirometer). An
alternate procedure is to calibrate against a second reference meter (dry-gas meter or
critical orifice) that has been calibrated against a primary standard meter.
2.1.1 Wet-Test Meter-Wet-test meters are calibrated by the manufacturer to an
accuracy of ± 0.5%. The calibration must be checked initially upon receipt and yearly
thereafter. A wet-test meter with a capacity of 3.4 m3/h (120 ft3/h) or 30 L/revolution
(1 ftVrev) will be needed to calibrate the dry-gas meter. For large wet-test meters
(>30 L/rev), there is no convenient method for checking the calibration; consequently,
several methods are suggested, and other methods may be approved by the Administrator.
The initial calibration may be checked by any of the following methods:
1. Certification from the manufacturer that the wet-test meter is within
1% of true value at the wet-test meter discharge, so that only a leak
check of the system is then required.
2. Calibration by any primary-air or liquid-displacement method tHat
displaces at least one complete revolution of the wet-test meter.
3. Comparison against a smaller wet-test meter that has previously been
calibrated against a primary-air or liquid-displacement method, as
described in Section 3.5.2 of this Handbook.
4. Comparison against a dry-gas meter that has previously been calibrated
against a primary-air or liquid-displacement method.
The test-meter calibration should be checked annually. The calibration check
can be made by the same method as that of the original calibration; however, the
comparison method need not be recalibrated if the calibration check is within 1% of the
true value. When this agreement is not obtained, the comparison method or wet-test
meter must be recalibrated against a primary-air or liquid-displacement method.
2.1.2 Dry-Gas Meter as a Calibration Standard-A DGM may be used as a calibration
standard for volume measurements in place of the wet-test meter specified in Section
5.3 of Method 5, provided that it is calibrated initially and recalibrated periodically
as follows:
Standard Dry-Gas Meter Calibration-The DGM to be calibrated and used as a
secondary reference meter should be of high quality and should have appropriate
capacity (e.g., 3 L/rev [0.1 ftJ/rev] ) . A spirometer (400 L or more capacity), or
equivalent, may be used for this calibration, although a wet-test meter is usually more
practical. The wet-test meter should have a capacity of 30 L/rev (1 ft3/rev) and
should be capable of measuring volume to within 1.0%. Wet-test meters should be
-------
Section No. 3 .19.2
Date September 3, 1992
Page 2
checked against a spirometer or a liquid displacement meter to ensure accuracy.
Spirometers or wet-test meters of other sizes may be used, provided that the specified
accuracies of the procedure are maintained. The initial calibration may be checked by
any of the following methods:
1. Set up the components as shown in Figure 2.1. A spirometer, or
equivalent, may be used in place of the wet-test meter in the system.
2. Run the pump for at least 5 min at a flow rate of about 10 L/min (0.35
cfm) to condition the interior surface of the wet-test meter. The
pressure drop indicated by the manometer at the inlet side of the DGM
should be minimized (no greater than 100 mm H20 [4 in. H20] at a flow
rate of 30 L/min [1 cfm]). Using large diameter tubing connections and
straight pipe fittings will accomplish this minimization.
3. Collect the data as shown in the example data sheet (see Figure 2.2).
Make triplicate runs at each of the flow rates and at no less than five
different flow rates. The range of flow rates should be between 10 and
34 L/min (0.35 and 1.2 cfm) or over the expected operating range.
4. Calculate flow rate, Q, for each run using the wet-test meter volume
(Equation 2-1), Vw, and the run time, 0. Calculate the DGM coefficient
(Equation 2-2), Ydi, for each run. These calculations are as follows:
vw
Q = K, Equation 2-1
(tw + t.td) 6
where:
V„ (td. + t,td) Ph.,
Yds = Equation 2-2
Vdf (t. «• t.ld) (PUr ~ Ap/13.6)
K; = 0.3858 for international system of units (SI); 17.64 for English
units.
Vw = Wet-test meter volume, liter (ft3) .
Vdr = Dry-gas meter volume, liter (ft3) .
tdJ = Average dry-gas meter temperature, °C (°F).
t,td = 273 °C for SI units; 460 °F for English units.
tw = Average wet-test meter temperature, °C (°F).
Pba. = Barometric pressure, mm Hg (in. Hg) .
Ap = Dry-gas meter inlet differential pressure, mm H20 (in. H20) .
0 = Run time, min.
-------
VACUUM
GAUGE
¦T PUS
»Al»E
REEDU TAIW
PWIN »AlfE
closed
OUT TtST HEIt*
MIR OVT1ET
AIR-TIGHT mm
AIR INICT
cmirict
MMOHCTER
UVU VbMt
MNTtR
IE¥EI
GAUGE
WATER OUT
•*) t> w
0 0 »
B ft n
ID (6 rt
H*
uiino
A 3
U
rt Z
ffi 0
Figure 2.1. Sample meter system calibration getup.
It u>
H •
10
io
KJ
-------
Da t e :
Diy-gns Metpf Identification:
Barometric Pressure (P, ) : in. Hg
Spi ro-
meter
(wet
me t e r)
gas
volume
op
Dry-
gas
meter
pres-
sure
(Ap)
in. H,0
Time
(0)
min
Flow
rate
(0)
cfm
Meter
coef-
f icient
(Yd,)
1 . 20
Q ~ 17-64 U (t. + 460)
Eguat ion 1 t» O v>
0> B> (6
v _ u_ (t, +460) P,
vh (i. +4bU) ( + Ap J y*
[ ' ITT ^
Equation 2
FigurJe 2-2 Dry-^as meter calibration data form.
to m
vo
vo
K>
-------
Section No. 3.19.2
Date September 3, 1992
Page 5
5. Compare the three Y^, values at each of the flow rates and determine the
maximum and minimum values. The difference between the maximum and
minimum values at each flow rate should be no greater than 0.030. Extra
sets of triplicate runs may be made to complete this requirement. In
addition, the meter coefficients should be between 0.95 and 1.05. If
these specifications cannot be met in three sets of successive
triplicate runs, the meter is not suitable as a calibration standard and
should not be used as such. If these specifications are met, average
the three Yd, values at each flow rate resulting in five average meter
coefficients, Y„,.
6. Prepare a curve of meter coefficient, Yd,, versus flow rate, Q, for the
DGM. This curve shall be used as a reference when the meter is used to
calibrate other DGM's and to determine whether recalibration is
required.
Standard Dry-Gas Meter Recalibration-Recalibrate the standard DGM against a
wet-test meter or spirometer annually or after every 200 hours of operation, whichever
comes first. This requirement is valid provided the standard DGM is kept in a
laboratory and, if transported, cared for as any other laboratory instrument. Abuse
to the standard meter may cause a change in the calibration and will require more
frequent recalibrations.
As an alternative to full recalibration, a two-point calibration check may be
made. Follow the same procedure and equipment arrangement as for a full recalibration,
but run the meter at only two flow rates (suggested rates are 14 and 28 L/min [0.5 and
1.0 cfm]). Calculate the meter coefficients for these two points and compare the
values with the meter calibration curve. If the two coefficients are within 1.5% of
the calibration curve values at the same flow rates, the meter need not be recalibrated
until the next date for a recalibration check.
2.1.3 Critical Orifices as Calibration Standards-Critical orifices may be used as
calibration standards in place of the wet-test meter specified in Section 5.3 of Method
5, provided that they are selected, calibrated, and used as follows:
Selection of Critical Orifices-The procedure that follows describes the use
of hypodermic needles or stainless-steel needle tubing that have been found suitable
for use as critical orifices. Other materials and critical orifice designs may be
used, provided the orifices act as true critical orifices (i.e., a critical vacuum can
be obtained, as described in Section 7.2.2.2.3 of Method 5). Select five critical
orifices of appropriate size to cover the range of flow rates between 10 and 34 L/min
or the expected operating range. Two of the critical orifices should bracket the
expected operating range.
A minimum of three critical orifices will be needed to calibrate a Method 5
DGM; the other two critical orifices can serve as spares, providing better selection
for bracketing the range of operating flow
• ,.Ti
«. 1 /' '
-------
Section No. 3.19.2
Date September 3, 1992
Page 6
rates. The needle sizes and tubing lengths shown below give the following approximate
flow rates:
Flow rate,
Gauge/cm L/min
12/7.6 32.56
12/10.2 30.02
13/2.5 25.77
13/5.1 23.50
13/7.6 22.37
13/10.2 20.67
Flow rate,
Gauge/cm L/min
14/2.5 19.54
14/5.1 17.27
14/7.6 16.14
15/3.2 14.16
15/7.6 11.61
15/10.2 10.48
These needles can be adapted to a Method 5-type sampling train as follows:
Insert a serum bottle stopper, 13- by 20-mm (0.5-in. by 75-in.) sleeve type, into a
13-mm (0.5-in.) Swagelok1* quick-connect fitting. Insert the needle into the stopper,
as shown in Figure 2.3.
Initial Critical Orifice CaliJbration-The procedure described in this section
uses the Method 5 meter box configuration with a DGM, as described in Section 2.1.8 of
Method 5, to calibrate the critical orifices. Other schemes may be used, subject to
the approval of the Administrator. The critical orifices must be calibrated in the
same configuration as they will be used (i.e., there should be no connections to the
inlet of the orifice).
Prior to calibrating the critical orifices, the dry-gas meter in the meter box
must be calibrated. Before calibrating the meter box, leak check the system as
follows:
1. Fully open the coarse adjust valve and completely close the bypass
valve.
2. Plug the inlet.
3. Turn on the pump and determine whether there is any leakage. The
leakage rate must be zero (i.e., no detectable movement of the DGM dial
must be seen for 1 min) .
4. Check also for leakages in the portion of the sampling train between the
pump and the orifice meter. See Section 5.6 for the procedure; make any
corrections, if necessary. If leakage is detected, check for cracked
gaskets, loose fittings, worn 0-rings, etc., and make the necessary
repairs.
-------
Section No. 3.19.2
Date September 3, 1992
Page 7
QUICK
CONNECT
SERUM
STOPPER
CRITICAL
' ORIFICE
Critical orifice adaptation to Method 5-type metering system.
METER BOX
O
©.
CRITICAL ORIFICE
Apparatus setup.
Figure 2.3 Critical orifice and apparatus setup.
-------
Section No. 3.19.2
Date September 3, 1992
Page 8
After determining that the meter box is leak-free, calibrate it according to
the procedure given in Section 5.3. Make sure that the wet-test meter meets the
requirements stated in Subsection 2.1.1. Check the water level in the wet-test meter.
Record the DGM calibration factor, Y. The critical orifice is then calibrated as
follows:
1. Set up the apparatus as shown in Figure 2.3.
2. Allow a warm-up time of 15 min. This step is important to equilibrate
the temperature conditions through the DGM.
3. Leak check the system as described above. The leakage rate must be
zero.
4. Before calibrating the critical orifice, determine its suitability and
the appropriate operating vacuum as follows: Turn on the pump, fully
open the coarse adjust valve, and adjust ,the bypass valve to give a
vacuum reading corresponding to about half an atmospheric pressure.
Observe the meter box orifice manometer reading, AH. Slowly increase
the vacuum reading until the meter box orifice manometer shows a stable
reading. Record the critical vacuum for each orifice. Orifices that
do not reach a critical value must not be used.
5. Obtain the barometric pressure using a barometer as described in Section
2.1.9 of Method 5. Record the barometric pressure, P^,., in mm Hg (in.
Hg) .
6. Conduct duplicate runs at a vacuum of 25 to 50 mm Hg (1 to 2 in. Hg)
above the critical vacuum. The runs must be at least 5 minutes each.
The DGM volume readings must be in increments of complete revolutions
of the DGM. As a guideline, the times should not differ by more than
3.0 s (this includes allowance for changes in the DGM temperatures) to
achieve ± 0.5% in K'. Record the information listed in Figure 2.4.
7. Calculate K' using Equation 2-3.
K'
K, Vr Y (P^, + AH/13.6) Ta
Pt»r T. 6
Equation 2-3
where:
K'
= Critical orifice coefficient, [ (m3) (°K)1/J] / [ (mm Hg)
(min) ] { [ (ft3) (°R)1/J) ] / [ (in. Hg) (min) ] } .
= Absolute ambient temperature, °K (°R).
Average the K' values. The individual K' values should not differ by more than ± 0.5%
from the average.
-------
Section No. 3.19.2
Date September 3, 1992
Page 9
Date
Train ID
Critical orifice K' factor
Dry-Gas Meter
Final reading
Initial reading
Difference, V,„
Inlet/outlet temperatures
Initial
Final
Avg. temperature, tff
Time, 0
Orifice man. rdg., A H
Bar. pressure, P,,,.
Ambient temperature, t„t
Pump vacuum
Vrlildl m; (ft3)
Critical orifice ID
V,
cr (stdi
m3 (ft3)
m! (ft5)
m3 (ft3)
°C (°F)
°C (°F)
°C (°F)
min/s
min
mm ( in.) H20
mm (in.) Hg
°C (°F)
mm (in.) Hg
m3 (ft3)
Run number
1 2
DGM cal. factor, Y
Figure 2.4. Data sheet for determining DGM Y factor.
-------
Section No. 3.19.2
Date September 3, 1992
Page 10
Using the Critical Orifices as Calibration Standards—The dry-gas meter is
calibrated using the critical orifices as the secondary standard as follows:
1. Record the barometric pressure.
2. Calibrate the metering system according to the procedure outlined in
Sections 7.2.2.2.1 to 7.2.2.2.5. Record the information listed in
Figure 2.5.
3. Calculate the standard volumes of air passed through the DGM and the
critical orifices and calculate the DGM calibration factor, Y, using the
equations below:
where:
= K, Vr [P„.r + (AH/13.6) ] /T. Equation 2-4
vcn.t.di = K' !PMi 6) /T^b1'2 Equation 2-5
Y = Vcn.idi/V,lltj| Equation 2-6
Veil.ldl = Volume of gas sample passed through the critical orifice,
corrected to standard conditions, dsem (dscf).
K' = 0.3858 °K/mm Hg for metric units
= 17.64 °R/in. Hg for English units.
4. Average the DGM calibration values for each of the flow rates. The
calibration factor, Y, at each of the flow rates should not differ by
more than ± 2% from the average.
Recalibration of critical orifices-To determine the need for recalibrating the
critical orifices, compare the DGM Y factors obtained from two adjacent orifices each
time a DGM is calibrated. For example, when checking orifice 13/2.5, use orifices
12/10.2 and 13/5.1. If any critical orifice yields a DGM Y factor differing by more
than 2% from the others, recalibrate the critical orifice according to the initial
calibration procedures above.
2.1.4 Sample Meter System-The sample meter system—consisting of the pump, vacuum
gauge, valves, orifice meter, and dry-gas meter—should be calibrated by stringent
laboratory methods before it is used in the field. The calibration should be
re-checked after each field test series. This re-check is designed to provide testers
with a method that can be used more often and with less effort, to ensure that the
calibration has not changed. When the quick check indicates that the calibration
factor has changed, testers must again use the complete laboratory procedure to obtain
the new calibration factor. After recalibration, the metered sample volume must be
multiplied by either the initial or the recalibrated calibration factor—that is, the
one that yields the lower gas volume for each test run.
-------
Section No. 3.19.2
Date September 3, 1992
Page 11
Date
Train ID
Critical orifice ID
Drv-Gas Meter
Final reading
Initial reading
Difference, Vr
Inlet/outlet temperatures
Initial
Final
Avg. temperature, tr
Time, 0
Orifice man. rdg., A H
Bar. pressure, Pu.,
Ambient temperature, tW!.
Pump vacuum
K' factor
DGM cal. factor
m3 (ft3)
m3 (ft3)
m3 (ft3)
°C (°F)
°C (°F)
°C (°F)
min/s
min
mm (in.) H20
mm (in.) Hg
°C (°F)
mm (in.) Hg
Run number
1 2
Average
Figure 2.5. Data sheet for determining K' factor.
-------
Section No. 3.19.2
Date September 3, 1992
Page 12
Before calibrating the metering system for the first time, conduct a leak
check. The meter system should be leak-free. Both positive (pressure) and negative
(vacuum) leak checks should be performed. The following pressure leak check procedure
will check the metering system from the quick-connect inlet to the orifice outlet and
will check the orifice-inclined manometer:
1. Disconnect the orifice meter line from the downstream orifice pressure
tap (the one closest to the exhaust of the orifice) ; plug this tap
(Figure 2.1).
2. Vent to the atmosphere the negative side of the inclined manometer. If
the inclined manometer is equipped with a three-way valve, this step can
be performed by turning the valve on the negative side of the ori-
fice-inclined manometer to the vent position.
3. Place a one-hole rubber stopper with a tube through its hole into the
exit of the orifice; connect a piece of rubber or plastic tubing, as
shown in Figure 2.1.
4. Open the positive side of the orifice-inclined manometer to the
•reading* position; if the inclined manometer is equipped with a
three-way valve, this will be the line position.
5. Plug the inlet to the vacuum pump. If a quick-connect with a leak-free
check valve is used on the control module, the inlet will not have to
be plugged.
6. Open the main valve and the bypass valve.
7. Blow into the tubing connected to the end of the orifice until a
pressure of 127 to 178 mm (5 to 7 in.) H20 has built up in the system.
8. Plug or crimp the tubing to maintain this pressure.
9. Observe the pressure reading for a 1-min period. No noticeable movement
in the manometer fluid level should occur. If the meter box has a leak,
a bubbling-type leak check solution may aid in locating it.
After the metering system is determined to be leak-free by the positive leak
check procedure, the vacuum system to and including the pump should be checked by
plugging the air inlet to the meter box. If a quick-connect with a leak-free stopper
system is presently on the meter box, the inlet will not have to be plugged. Turn the
pump on, pull a vacuum within 7.5 cm (3 in.) Hg of absolute zero, and observe the
dry-gas meter. If the leakage exceeds 0.00015 nvVmin (0.005 ft3/min), the leak(s) must
be found and minimized until the above specifications are satisfied.
Checking the meter system for leaks before initial calibration is not
mandatory, but it is recommended.
Note: For metering systems with diaphragm pumps, the normal leak check
procedure described above will not detect leakages within the pump. For these cases,
the following leak check procedure is suggested: Make a 10-min calibration run at
0.00057 nr/min (0.02 ft!/min); at the end of the run, take the difference between the
measured wet-test meter and the dry-gas meter volumes; divide the difference by 10 to
get the leak rate. The leak rate should not exceed 0.00057 m5/min (0.02 ft3/min) .
Initial calibration-The dry-gas meter and the orifice meter can be calibrated
simultaneously and should be calibrated when first purchased and any time the posttest
check yields a Y outside the range of the calibration factor Y +0.05 Y. A calibrated
wet-test meter (of proper size, with +1% accuracy) should be used to calibrate the
dry-gas meter and the orifice meter. The dry-gas meter and the orifice meter should
be calibrated in the following manner:
-------
Section No. 3.19.2
Date September 3, 1992
Page 13
Before its initial use in the field, leak check the metering system.
Leaks, if present, must be eliminated before proceeding.
Assemble the apparatus, as shown in Figure 2.6, with the wet-test meter
replacing the probe and impingers-that is, with the -outlet of the
wet-test meter connected to a needle valve that is connected to the
inlet side of the meter box.
Run the pump for 15 min with the orifice meter differential (AH) set at
12.7 mm (0.5 in.) H20 to allow the pump to warm up and to permit the
interior surface of the wet-test meter to be wetted.
Adjust the needle valve so that the vacuum gauge on the meter box is
between 50 and 100 mm (2 to 4 in.) Hg during calibration.
Collect the information required on the forms provided (Figure 2.7).
Sample volumes, as shown, should be used.
Calculate Y, for each of the six runs, using the equation in Figure 2.7
under the Y, column, and record the results on the form in the space
provided.
Calculate the average Y (calibration factor) for the six runs using the
following equation:
Y1 + Y2 «• Y3 * Y4 + Y5 + Y6
= Equation 2-7
-------
Section No. 3.19.2
Date September 3, 1992
Page 14
THERMOMETERS
CONTROL
1 VALVES
UTUBE
MANOMETER
THERMOMETER
J U-TUBE
MANOMETER
WET TEST METER
PUMP
DRY CAS METER
Figure 2.6. Equipment arrangement for dry-gas meter calibration.
-------
Section No. 3.19.2
Date September 3, 1992
Page 15
Date
Meter box number
Barometric pressure, Pb =
in. Hg Calibrated by
Ori-
fice
mano-
meter
set-
ting
(AH) ,
in. HjO
Gas volume
Temperatures
Time
(0),
min
AH .
°F
Outlet
(tde),
°F
Avg3
(td)
°F
0.5
5
1.0
10
1.5
10
1
1
2.0 110
1
1 1 1
1 1 1
3.0 110
1
1 1 1
1 1 I
**
O
»-»
o
1 1 1 1
1 1 1 1
1 1
AK, | |
in. |AH |Y, =
H,0 113.6 |
1 1
1 1
0.5 10.0368 |
1 1
I.0 |0.07 37 |
1 1
1.5 | 0.110 |
! 1
2.0 |0.147 |
1 1
3.0 (0.221 I
' 1
4.0 |0.294 |
I 1
1 Avg | |
1 1 1
1
V„PB(td + 460) | 0.0317 AH (tw + 460)0 :
lAHQ. =
VdjPb ~ AH *(tv + 46) | Pb (t„ + 460) Vw
1 13.6/ |
1
1
1
1
1
1
1
1
1
1
1
1
1
* If there is only one thermometer on the dry-gas meter, record the temperature under td.
Figure 2.7. Dry-gas meter calibration data (English units, front side).
-------
Section No. 3.19.2
Date September 3, 1992
Page 16
Nomenclature:
V„ = Gas volume passing through the wet-test meter, ft3.
Vd = Gas volume passing through the dry-gas meter, ft3.
t„ = Temperature of the gas in the wet-test meter, °F.
tdl = Temperature of the inlet gas of the dry-gas meter, °F.
td0 = Temperature of the outlet gas of the dry-gas meter, °F.
td = Average temperature of the gas in the dry-gas meter, obtained by the
average tdl and td0 , °F.
AH = Pressure differential across orifice, in. H20.
Y, = Ratio of accuracy of wet-test meter to dry-gas meter for each run.
Tolerance Y, = Y ± 0.02 Y.
Y = Average ratio of accuracy of wet-test meter to dry-gas meter for all
six runs. Tolerance Y = Y ± 0.01 Y.
AH@, = Orifice pressure differential at each flow rate that gives 0.75
ft!/min of air at standard conditions for each calibration run, in.
of H:0. Tolerance = AH@ ± 0.15 (recommended).
AH@ = Average orifice pressure differential that gives 0.75 ft3/min of air
at standard conditions for all six runs, in. H20. Tolerance = 1.84
± 0.25 (recommended).
0 = Time for each calibration run, min.
Pt = Barometric pressure, in. Hg.
Figure 2.7. Dry-gas meter calibration data (English units, backside)
-------
Section No. 3.19.2
Date September 3, 1992
Page 17
Record the average on Figure 2.7 in the space provided.
Clean, adjust, and recalibrate, or reject the dry-gas meter if one or
more values of Y fall outside the interval Y ± 0.02 Y. Otherwise, the
average Y is acceptable and should be used for future checks and
subsequent test runs.
Calculate AH@, for each of the six runs using the equation in Figure
2.7A or 2.7B under the AH0, column, and record on the form in the space
provided.
Calculate the average AH0 for the six runs using the following equation:
AH@1 + AH@2 -f AHS3 + AH®4 + AHGS AH06
= Equation 2-8
6
Record the average on Figure 2.7 in the space provided.
Adjust the orifice meter or reject it if AH®, varies by more than ±3.9
mm (0.15 in.) H20 over the range of 10 to 100 mm (0.4 to 4.0 in.) H20.
Otherwise, the average AH0 is acceptable and should be used for sub-
sequent test runs.
Posttest calibration check—After each field test series, conduct a
metering-system calibration check, as specified in Subsection 2.1.4, except for the
following variations:
1. Three calibration runs at a single intermediate orifice meter setting
may be used with the vacuum set at a maximum value reached during the
test series. The single intermediate orifice meter setting should be
based on the previous field test. A valve must be inserted between the
wet-test meter and the inlet of the metering system to adjust the
vacuum.
2. If a temperature-compensating dry-gas meter was used, the calibratlton
temperature meter must be within t 6 °C (10.8 °F) of the average meter
temperature during the test series.
3. Use Figure 2.8 to record the required information.
If the calibration factor Y deviates by <5% from the initial calibration
factor Y, then the dry-gas meter volumes obtained during the test series ^re
acceptable. If Y deviates by >5%, recalibrate the metering system and use whichever
meter coefficient (initial or recalibrated) yields the lowest gas volume for each test
run.
Alternate procedures (e.g., using the orifice meter coefficients or critical
orifices) may be used.
8.
9.
10.
AH@
11.
-------
Section No. 3.19.2
Date September 3, 1992
Page 18
Date
Metering System ID No.
Barometric pressure, Pb =
Ori-
I
|Spiro-
fice
|meter
mano-
| (wet
meter
j test)
set-
Igas
ting
|volume
AH
1 (VJ
in. Hg
1 ft3
Dry-gas
meter
volume
(VJ
ft3
Temperatures
Spiro-
meter
(wet
meter)
(tj
°F
Dry-gas meter
Inlet
(tj
°F
Outlet
(tc)
°F
Avg
(tj
°F
Time
(0)
min
Calculations
Yi
AH
in H20
IP* +
S7T
"TT!T
460
1
460)
AH@,
0.0317 AH
"TOT
XTt
(t„ + 460
VI 1
]2
Average
Ratio of reading of wet-test meter to dry-gas meter; tolerance for
individual values ± 0.02 from average.
Orifice pressure differential that equates to 0.75 cfm of air @ 68 °F
and 29.92 in. of Hg, in. H20; tolerance for individual values ± 0.20
for average.
Figure 2.8. Example data sheet for calibration of metering system
(English units).
Y
AH @ =
-------
Section No. 3.19.2
Date September 3, 1992
Page 19
2.2 Temperature Gauges
2.2.1 Impinger Thermometer—The thermometer used to measure the temperature of the
gas leaving the impinger train should initially be compared with a mercury-in-glass
thermometer that meets ASTM E-l No. 63C or 63F specifications. This procedure is as
follows:
1. Place both the reference thermometer and the test thermometer in an ice
bath. Compare readings after they stabilize.
2. Remove the thermometers from the bath and allow both to come to room
temperature. Again, compare readings after they stabilize.
3. Accept the test thermometer if its reading agrees to within 1 °C (2 °F)
of the reference thermometer reading at both temperatures. If the
difference is greater than 1 °C (2 °F) , the thermometer should be
adjusted and recalibrated until the criteria are met, or it should be
rejected. Record the results on Figure 3.1 of Section 3.19.3.
2.2.2 Dry-gas Thermometers-The thermometers used to measure the metered gas sample
temperature should be compared initially with a mercury-inglass thermometer as above,
using a similar procedure.
1. Place the dial type (or equivalent) thermometer and the mercury-in-glass
thermometer in a hot water bath, 40 to 50 °C (104 to 122 °F). Compare
the readings after they stabilize.
2. Allow both thermometers to come to room temperature. Compare readings
after thermometers stabilize.
3. Users should accept the dial type (or equivalent) thermometer under the
following conditions: The values must agree to within 3 °C (5.4 °F) at
both points; the temperature differentials at both points are within 3
°C (5.4 °F), and the temperature differential is taped to the thermome-
ter and recorded on the pretest sampling check form (Figure 3.1).
4. Prior to each field trip, compare the temperature reading of the
mercury-in-glass thermometer at room temperature with that of the meter
system thermometer. The values or corrected values should be within 6
°C (10.8 °F) of one another, or the meter thermometer should be replaced
or recalibrated. Record any temperature correction factors on Figure
3.1 of Section 3.19.3 or on a similar form.
2.2.3 Stack Temperature Sensor-The stack temperature sensor should be calibrated
upon receipt or checked before field use. Each sensor should be uniquely marked for
identification. The calibration should be performed at three points and then extra-
polated over the range of temperatures anticipated during actual sampling. For the
three-point calibration, a reference ASTM mercury-in-glass thermometer should be used.
The following procedure is recommended for calibrating stack temperature
sensors (thermocouples and thermometers) for field use.
1. For the ice-point calibration, form a slush from crushed ice and liquid
water (preferably deionized, distilled) in an insulated vessel such as
a Dewar flask. Taking care that they do not touch the sides of the
flask, insert the stack temperature sensors into the slush to a depth
of at least 2 in. Wait 1 min to achieve thermal equilibrium and record
the readout on the potentiometer. Obtain three readings taken at 1-min
intervals.
Note: Longer times may be required to attain thermal equilibrium
with thick-sheathed thermocouples.
-------
Section No. 3.19.2
Date September 3, 1992
Page 20
2. Fill a large Pyrex beaker with water to a depth >4 in. Place several
boiling chips in the water and bring the water to a full boil using a
hot plate as the heat source.
Insert the stack temperature sensor(s) in the boiling water to a
depth of at least 2 in., taking care not to touch the sides or bottom
of the beaker.
Place an ASTM reference thermometer alongside the sensor(s). If
the entire length of the mercury shaft in the thermometer cannot be
immersed, a temperature correction will be required to give the correct
reference temperature.
After 3 min, both instruments will attain thermal equilibrium.
Simultaneously record temperatures from the AS*IW reference thermometer
and the stack temperature sensor three times at 1-min intervals.
3. For thermocouple, repeat Step 2 with a liquid (such as cooking oil) that
has a boiling point in the 150 to 250 °C (300 to 500 °F) range. Record
all data on Figure 2.9. For thermometers other than thermocouples,
repeat Step 2 with a liquid that boils at the maximum temperature at
which the thermometer is to be used, or place the stack thermometer and
reference thermometer in a furnace or other device to reach the required
temperature.
Note: If the thermometer is to be used at temperatures higher than the
reference thermometers can record, the stack thermometer may be
calibrated with a thermocouple previously calibrated with the above
procedure.
4. If the absolute values of the reference thermometer and thermocouple(s)
agree to within 1.5% at each of the three calibration points, plot the
data on linear graph paper and draw the best-fit line to the three
points or calculate the constants of the linear equation using the
least-square method. The data may be extrapolated above and below the
calibration points to cover the entire manufacturer's suggested range
for the thermocouple. For the portion of the plot or equation that
agrees within 1.5% of the absolute reference temperature, no correction
need be made. For all portions that do not agree within 1.5%, use the
plot or equation to correct the data.
If the absolute values of the reference thermometer and stack
temperature sensor (other than the thermocouple) agree to within 1.5%
at each of the three points, the thermometer may be used over the range
of calibration points for testing without applying any correction
factor. The data cannot be extrapolated outside the calibration points.
-------
Section No. 3.19.2
Date September 3, 1992
Page 21
Date _____ Thermocouple No.
Ambient temperature °F Barometric pressure in. Hg
Calibration person Reference: mercury-in-glass °F
other °F
Reference
point
number
Source"
(specify)
Reference
thermometer
temperature,
°F
Thermocouple
potentiometer
temperature,
°F
Temperature6
difference,
%
Type of calibration system used.
(ref temp, °F * 460) - (test thermom temp, °F + 460) v inn _ ^
ref temp, UF * 460
Figure 2.9. Stack temperature sensor calibration data form.
-------
Section No. 3.19.2
Date September 3, 1992
Page 22
2.3 Probe Heater
The probe heating system should be calibrated prior to field use according to
the procedure outlined in APTD-0576. Probes constructed according to APTD-0581 need
not be calibrated if the curves of APTD-0576 are used.
2.4 Barometer
The field barometer should be adjusted initially and before each test series
to agree to within 2.5 mm (0.1 in.) Hg of the mercury-inglass barometer or with the
station pressure value reported by a nearby National Weather Service station, corrected
for elevation. The correction for elevation difference between the station and the
sampling point should be applied at a rate of -2.4 mm Hg/30 m (-0.1 in. Hg/100 ft).
Record the results on the pretest sampling check form (Figure 3.1 of Section 3.19.3).
2 . 5 Probe Nozzle
Probe nozzles should be calibrated before initial use in the field. Using a
micrometer, measure the ID of the nozzle to the nearest 0.025 mm (0.001 in.). Make
three measurements using different diameters each time, and obtain the average. The
difference between the high and the low numbers should not exceed 0.1 mm (0.004 in.).
When nozzles become nicked, dented, or corroded, they should be reshaped, sharpened,
and recalibrated before use. Each nozzle should be permanently and uniquely
identified. Figure 2.10 is an example of a nozzle calibration data form.
2 . 6 Pitot Tube
The Type S pitot tube assembly should be calibrated using the procedure
outlined in Section 3.1.2 of this Handbook for Method 2.
2 .7 Trip Balance
The trip balance should be calibrated initially by using Class S standard
weights and should be within 0.5 g of the standard weight. Adjust or return the
balance to the manufacturer if limits are not met.
-------
Section No. 3.19.2
Date September 3, 1992
Page 23
Date _______Calibrated by
Nozzle
ID No.
Nozzle Diameter"
AD"
mm (in.)
mm (in.)
mm (in.)
D.'
mm (in.)
d3
mm (in.)
Three different nozzle diameters, mm (in.) ; each diameter must be measured
within (0.025 mm) 0.001 in.
Maximum difference between any two diameters, mm (in.), AD <(0.10 mm) 0.004
in.
Average of D,, D. , and Dj.
where:
" =
b AD =
c D.vs
Figure 2.10. Nozzle calibration data form.
-------
Section No. 3 .19.2
Date September 3, 1992
Page 24
TABLE 2.1. ACTIVITY MATRIX FOR EQUIPMENT CALIBRATION
Apparatus
1
1
|Acceptance limits
1
I Frequency & method
|of measurement
1
|Action if
I requirements
I are not met
1
Wet-test
meter
|Capacity 23.4
jnvVh (120 ft3/h) ;
| accuracy within
|± 1.0*
1
1
|Calibrate initially,
land then yearly by
|liquid displacement
1
1
1
|Adjust until
I specifications
|are met, or
|turn to
(manufacturer
1
Dry-gas
meter
|Y, = Y ± 0.02 Y
1
1
1
1
1
|Calibrate vs.
|wet-test meter
I initially, and when
Iposttest check
|exceeds Y ± 0.05 Y
1
I Repair, or
|replace and then
I recalibrate
1
1
1
Critical
|K' = K ± 0.03 K'
1
1
1
1
|Calibrate vs. wet,
|dry, or bubble meter
|upon receipt and
|after each test
I Repair and then
|recalibrate,
|or replace
1
1
Thermo-
meter
IImpinger thermo-
jmeter ± 1 °C (2
|°F); dry-gas meter
|thermometer l 3 °C
1(5.4 °F) over
|range; stack
|temperature sensor
|± 1.5% of absolute
|temperature
1
1
|Calibrate each ini-
tially as a separate
|component against a
|mercury-in-glass
|thermometer; then
|before each trip
|compare each as part
|of the train with
|the mercury-in-glass
|thermometer
1
|Adjust;
I determine
|a constant
|correction
|factor;
|or reject
1
1
1
1
1
Probe
heating
system
|Capable of
Imaintaining 120 °C
|± 14 °C (248° ± 25
|°F) at a flow rate
|of 2 0 L/min
|(0.71 ft'/min
1
I Calibrate component
|initially by APTD-
| 0576; if constructed
jby APTD-0581, or use
|published calibra-
tion curves
1
I Repair, or
|replace and
|then reverify
|the calibrat ion
1
1
1
Barometer
| ± 2.5 mm (0.1 in. )
|Hg of mercury-in-
|glass barometer
1
1
Icalibrate initially
|vs. mercury-in-glass
|barometer; check
|before and after
leach field test
|Adjust to agree
|with a certified
|barometer
1
1
(Continued)
-------
Section No. 3.19.2
Date September 3, 1992
Page 25
TABLE 2.1.
(Continued)
Apparatus
1
1
|Acceptance limits
I
1
I Frequency & method
|of measurement
1
I Action if
I requirements
I are not met
1
Probe
nozzle
(Average of three
I ID measurements of
Inozzle; difference
1 between high and
| low SO . 1 mm
|(0.004 in.)
I
(Use a micrometer to
I measure to nearest
I 0.02 5 mm (0.001 in.)
1
1
1
1
I Recalibrate,
I reshape, and
I sharpen when
Inozzle becomes
I nicked, dented
I corroded
1
Trip
balance
|500 —g capacity;
(capable of measur-
|ing within ± 0.5 g
|Check with standard
iClass S weights upon
|receipt
(Adjust, replace
|or return to
(manufacturer
-------
-------
Section No. 3.19.3
Date September 3, 1992
Page 1
3.0 PRESAMPLING OPERATIONS
This section addresses preparing and packing sampling supplies-and equipment.
The pretest preparations form (Figure 3.2 of Method 5, Section 3.4.3) can be used as
an equipment checklist, a status form, and a packing list for Methods 1-4 and Method
101A. The (QA) activities for the presampling operations are summarized in Table 3.1
at the end of this section.
A pretest check will have to be made on most of the sampling apparatus.
Figure 3.1 should be used to record the pretest calibration checks. A schematic of the
EPA Method 101A sampling train is shown in Figure 1.1. Commercial models of this
system are available. Each train must be in compliance with the specifications of the
reference method, Section 3.19.10.
3.1 Apparatus Check and Calibration
3.1.1 Nozzles and Probe Liners-The probe's heating system should be checked to see
that it is operating properly. The probe should be sealed at the inlet or tip and
checked for leaks at a vacuum of 380-mm (15 in.) Hg, and the probe must be leak-free
under these conditions. The nozzles should be calibrated using the procedures in
Subsection 2.5 of Section 3.19.2. Clean the probe and the nozzle's internal surfaces
using the procedures described above in Section 3.2. The ends of the probe and the
ends of the nozzle should be sealed with a Teflon film.
3.1.2 Filter Holder, Impingers, and Other Glassware-Ensure that all glass meets the
specifications described in Subsection 1 of Section 3.19.1, has been cleaned according
the procedures described below, and is sealed with a Teflon film or glass stoppers.
Clean all sample-exposed glassware with the following procedures:
1. Soak glassware in 50% HN03 for a minimum of 1 h.
2. Rinse with tap water.
3. Rinse with 8 N HC1.
4. Rinse with tap water.
5. Rinse with DI water.
3.1.3 Dry-Gas Meter—A dry-gas meter calibration check should be made using fe-he
procedure in Section 3.19.2.
3.1.4 Fi1ters—Check for flaws and store.
3.1.5 Silica Gei-Either dry the used silica gel at 175 °C (350 °F) or use fresh
silica gel and weigh several 200- to 300-g portions in airtight containers to the
nearest 0.5 g. Record the total weight (silica gel plus container) for each container.
The silica gel does not have to be weighed if the moisture content is not to be
determined.
3.1.6 Thermometers-The thermometers should be compared to the mercury-in-glass
reference thermometer at ambient temperature.
-------
Section No. 3.19.3
Date September 3, 1992
Page 2
Date Calibrated by
Method box number AH@
Dry-Gas Meter*
Pretest calibration factor Y _________ (within 2% of the average factor for each
calibration run).
Impinqer Thermometer
Was a pretest temperature correction used? ves no
If yes, temperature correction ______ (within 3 °C (5.4 °F) over range)
Stack Temperature Sensor*
Was a stack temperature sensor calibrated against a reference thermometer?
yes no
If yes, give temperature range with which the readings agreed within 1.5% of
reference value ______ to ______ °K (°R) .
Barometer
Was the pretest field barometer reading correct? ves no (within 2.5-mm
(0.1 in.) Hg of the mercury-in-glass barometer).
Nozzle'
Was the nozzle calibrated to the nearest 0.025-mm (0.001 in.)?
yes no.
'Most significant items/parameters to be checked.
Figure 3.1. Pretest sampling checks.
-------
Section No. 3.19.3
Date September 3, 1992
Page 3
3.1.7 Barometer-The field barometer should be compared with the mercury-in-glass
barometer or the weather station reading, after making an elevation correction, prior
to each field trip.
3.2 Sample Recovery Equipment and Reagents
Clean all sample exposed-glassware using the following procedures:
1. Soak glassware in 50% HNOj for a minimum of 1 h.
2. Rinse with tap water.
3 . Rinse with 8 N HC1.
4. Rinse with tap water.
5. Rinse with D1 water.
3.2.1 Glass Sample Bottles-The sample bottles must be leak-free, must gave
Teflon-lined caps, and must be 1000 and 100 mL in size.
3.2.2 Graduated Cylinder-k 250-mL graduated cylinder is required.
3.2.3 Funnei and Rubber Policeman-These items aid in transferring the silica gel to
the container; they are not necessary if the silica gel is weighed in the field.
3.2.4 Funnel—A glass funnel is required to aid in sample recovery.
3.3 Equipment Packing
The accessibility, condition, and functioning of measurement devices in the
field depend on packing them carefully and on moving them carefully at the site.
Equipment should be packed to withstand severe treatment during shipping and field
operations. The material used to construct shipping cases is therefore important. The
following containers are suggested, but they are not mandatory.
3.3.1 Probe-Seal the inlet and outlet of the probe to protect it from breakage and
pack it in the container. An ideal container is a wooden case (or the equivalent)
lined with foam material and having separate compartments to hold the individual
probes. The case should have handles or eye-hooks that can withstand hoisting and that
are rigid enough to prevent bending or twisting during shipping and handling.
3.3.2 Impingers, Connectors, and Assorted Glassware-All impingers and glassware
should be packed in rigid containers and protected by polyethylene or other suitable
material. Individual compartments for glassware will help to organize and protect each
piece.
3.3.3 Volumetric Glassware-A sturdy case lined with foam material can contain drying
tubes and assorted volumetric glassware.
3.3.4 Meter Box-The meter box, which contains the manometers, orifice meter, vacuum
gauge, pump, dry-gas meter, and thermometers, should be packed in a shipping container
unless its housing is sufficient to protect components during travel. Additional pump
oil should be packed if oil is required. A spare meter box should be included in case
of failure.
3.3.5 Wash Bottles and Storage Containers—Storage containers and miscellaneous
glassware should be packed in a rigid, foam-lined container.
-------
Section No. 3.19.3
Date September 3, 1992
Page 4
3.3.6 Chemicals-Chemicals should be packed in a rigid, foam-lined container.
As mentioned in Subsection 1.5.1.6 (Absorbing Solution, 4% KMnO<), caution
must be exercised for the storage and transport of KMn04. To prevent autocatalytic
decomposition of the permanganate solution, filter it through Whatman 54J filter paper.
The reaction of the KMn04 with the acid may cause pressure buildup in the sample
storage bottle. These bottles should not be filled to capacity and should be vented
to relieve excess pressure and to prevent explosion of the sample. A No. 70-72 hole
drilled in the container cap and Teflon liner is recommended.
Also, caution should be exercised with the HC1 reagent because it is highly
corrosive.
3.3.7 Safety Equipment for Sampling Train Preparation and Sample Recovery-Safety
glasses and protective laboratory gloves should be packed for the personnel assigned
to prepare the sampling train and recover the sample. Serious injury can result from
contact with HC1 and KMnO«.
-------
Section No. 3.19.3
Date September 3, 1992
Page 5
TABLE 3.1 ACTIVITY MATRIX FOR PRESAMPLING OPERATIONS
Apparatus
1
1
(Acceptance limits
1
1
I Frequency & method
I of measurement
1
I Action if
I requirements
1 are not met
1
Apparatus
Check and
Calibration
1
1
1
1
1
1
|
1
1
1
1
Nozzles
and
probe
liners
1
|l. Probe heating
I system capable of
|heating to 120 °C
|± 14 °C at a flow
Irate of 20 L/min
1
1
|1. Check heating
|system initially and
|when moisture cannot
|be prevented during
|testing
1
1
|l. Repair or
I replace
1
1
1
|
1
|2. Probe leak free
I at 380-mm (15 in.)
1 Hg
1
I
|2. Visually check
(before test
1
1
|2. Replace
1
1
|
1
|3. Nozzles
I calibrated
I(Sec. 3.19.2
jSubsec. 2.4)
1
l
13 . Before test to
I nearest 0.025-mm
|with micrometer
1
|
1
|3. Recalibrate,
|reshape, or
I replace
1
1
1
| 4. Probe and
Inozzle free of
|contaminants
I(Sec. 3.2)
1
1
1
1
I 4. Clean internally
|by brushing with tap
|water, deionized
|distilled water, and
|acetone; air dry
Ibefore test
1
1
|4. Repeat
I cleaning and
|assembly
(procedures
1
1
1
Impingers,
filter
holders,
and other
glassware
|Meets specifica-
tions in Subsec. 1
j of Sec. 3.19.1;
I cleaned according
j to Sec. 3.19.3
|Subsec. 3.1.2; and
|sealed with
|Teflon or glass
I stoppers
1
I Before each test
1
1
1
1
1
1
1
1
1
|Repair or
|discard and
|replace
1
1
1
1
1
1
1
Dry-gas
meter
|Clean and readings
Iwithin 2% of
|average
|calibration factor
1
I Calibrate according
j to Sec. 3.19.2
1
1
1
|Repair or
|replace and then
|recalibrate
1
Filters
I Free of
|irregularities
Ivisually check prior
|to testing
|Replace
1
(Continued)
-------
Section No. 3.19.3
Date September 3, 1992
Page 6
TABLE 3.1 (Continued)
Apparatus
1
1
|Acceptance limits
1
1
|Frequency & method
|of measurement
1
lAction if
I requirements
|are not met
1
Silica gel
|Indicating, 6-16
|mesh, use fresh-
|or dry-used silica
jgel at 175 °C
| (350 °F)
1
1
1
1
1
I
|lf moisture content
lis to be determined,
I weigh several 200-
|to 300-g portions of
I silica gel
I (± 0.5 g); use
I airtight containers;
|record weight of
|container plus
|silica gel
1
I Replace or
Ireweigh
1
1
1
1
1
1
1
1
Thermo-
meters
I Calibrated, within
|l °c (2 °F) for
limpinger thermo-
|meter, ± 3 °C
1(5.4 °F) for
I dry-gas meter
I thermometer
1
I Calibrate against
I mercury-in-glass
|thermometer
|(Sec. 3.4.2) before
| each
1
1
I Replace
1
1
1
1
1
1
1
Barometer
I Calibrated, within
I 2.5-mm (0.1 in.)
1 Hg
1
1
1
|Calibrate against
I mercury-in-glass
I barometer (Sec.
|3.7.2) before each
j test
1
|Replace
1
1
1
1
Sample
Recovery
Eauioment
and
Reaaents
1
1
1
1
1
I
1
1
1
1
1
|
1
1
1
1
1
Glass
sample
bottles
1
Iciean, leakless,
|Teflon-lined caps
1
I
1
I Before each field
j test
1
1
1
|Replace
I
i
i
Graduated
cylinder
1
I Clean, glass and
I class A; 250 mL
|with <2 mL
|subdivisions
1
l
I Before each field
Itrip check for
I cracks, breaks, and
Imanufacturer flaws
1
1
|Replace
i
i
i
Funnel
Iciean, glass,
Iciass A
|Same as above
1
|Same as above
1
(Continued)
-------
Section No. 3.19.3
Date September 3, 1992
Page 7
TABLE 3.1 (Continued)
Apparatus
1
1
|Acceptance limits
1
1
I Frequency & method
I of measurement
1
|Act ion if
I requirements
|are not met
1
EouiDment
Dackina
1
1
1
1
1
1
1
1
1
Probe
1
|Rigid container
|protected by
|polyethylene foam
1
1
I Prior to each
I shipment
1
1
|Repack
1
1
I
Impingers,
connectors,
and
assorted
glassware
|Rigid container
I protected by
|polyethylene foam
1
1
1
|Prior to each
|shipment
1
1
1
1
|Repack
1
1
1
1
1
Volumetric
glassware
|Packed in original
I containers, if
(available, or a
|rigid container
|lined with foam
land marked
I"Fragile*
1
|Prior to each
|shipment
1
1
1
1
1
1
|Repack
1
1
1
1
1
1
1
Meter box
I Meter box case
land/or additional
Imaterial to
Iprotect train
|components; pack
I spare-meter box
1
|Prior to each
I shipment
1
1
1
1
1
|Repack
1
1
1
1
Wash
bottles
and
storage
containers
|Rigid foam-lined
I container
1
1
1
1
I Prior to each
I shipment
1
1
1
1
|Repack
1
1
1
1
Chemicals
|Rigid foam-lined
I container
1
I Prior to each
|shipment
1
|Repack
1
1
-------
Section No. 3.19.4
Date September 3, 1992
Page 1
4.0 ON-SITE MEASUREMENTS
On-site activities include transporting the equipment to the test site, unpacking
and assembling the equipment, sampling for particulate and gaseous, mercury, and
recording the data. The associated QA activities are summarized in Table 4.1 at the
end of this section.
4.1 Transport of Equipment to the Sampling Site
The most efficient means of transporting the equipment from ground level to the
sampling site (often above ground level) should be decided during the preliminary site
visit or by prior correspondence. Care should be taken to prevent damage to the
equipment or injury to test personnel during the moving. A clean "laboratory type*
area free of excessive dust and mercury compounds should be located and designated for
preparing the nozzle, probe, filter holder, and impingers and for sample recovery.
4.2 Preliminary Measurements and Setup
A preliminary survey should be conducted prior to sampling and analysis, unless
adequate prior knowledge of the source is available. Testing must be conducted at the
proper sampling locations and during the proper process and control equipment operating
cycles or periods. Testers should refer to Subsection 3.19.3.1 for information
typically needed to establish the proper sampling and analysis protocol.
Testers should have calculated the minimum sampling run time required, unless it
is known that the minimum time stated by the applicable regulations will be sufficient
to provide proof of compliance.
In this method, highly oxidizable matter may make it impossible to sample for the
desired minimum time. This problem is indicated by the complete bleaching of the
purple color of the KMn04 solution. In these cases, testers may divide the sample run
into two or more subruns to ensure that the absorbing solution will not be depleted.
In cases where excess water condensation is encountered, collect two runs to make one
sample.
4.2.1 Preliminary Measurements and Setup-The sampling site should be selected in
accordance with Method 1. If the duct configuration or some other factor makes this
impossible, the site should be approved by the Administrator prior to conducting the
test. A 115-V, 30-A electrical supply is necessary to operate the standard sampling
train. Either measure the stack and determine the minimum number of traverse points
by Method 1, or check the traverse points determined during the preliminary site visit
(Section 3.0) . Record all data on the traverse point location form shown in Method 1.
These measurements will be used to locate the pitot tube and the sampling probe during
preliminary measurements and actual sampling.
-------
Section No. 3 .19 .4
Date September 3, 1992
Page 2
4.3 Preparations for Sampling
The most common situations and problems are addressed in this section. Both
required and recommended QA/control checks and procedures are provided to assist in
collecting data of acceptable quality and to assess the accuracy of the sampling and
analysis.
On-site sampling includes the following steps:
1. Conducting preliminary measurements and setting up the recovery area.
2. Preparing and setting up the sampling system for leaks.
3. Connecting electrical service and checking the sampling system for leaks.
4. Heating the probe and filter to the proper temperature.
5. Inserting the probe into the duct and sealing the duct.
6. Isokinetic sampling.
7. Recording data.
8. Posttest leak check of the sampling system.
9. Recovering the sample and transporting it to the laboratory.
4.3.1 Stack Parameters-Check the sampling site for cyclonic or nonparallel flow as
described in Method 1 (Section 3.0). The sampling site must be acceptable before a
valid sample can be taken. Determine the stack pressure, temperature, and the range
of velocity heads encountered (Method 2). Determine the moisture content using the
approximation Method 4, or its alternatives, for the purpose of setting the isokinetic
sampling rate. If the identical source has been tested before or if a good estimate
of the moisture content is available, this should be sufficient. The reference method
(Section 3.4.10) uses the condensate collected during sampling to determine the
moisture content used in final calculations. If the stack is saturated with moisture
or has water droplets, the moisture content must also be determined by partial pressure
with the use of a more accurate stack gas temperature sensor (Method 4).
Determine the dry molecular weight of the stack gas, as required in Method 2.
If an integrated gas sample is required, follow Method 3 procedures and take the gas
sample simultaneously with, and for the same total length of time, as the particulate
run. The sampling and the analytical data forms for molecular weight determinations
are in Method 3.
Using the stack parameters obtained by these preliminary measurements, the tester
can set up the nomograph as outlined in APTD-0576 or use a calculator. An example-of
a nomograph data form is shown in Figure 4.1 of the Method 5, Section 3.4.4.
Select a nozzle size based on the range of velocity heads, so that it is not
necessary to change the size to maintain isokinetic sampling rates during the run.
Install the selected nozzle using a Viton A O-ring when glass liners are used. Other
connecting systems such as Teflon ferrules may be used. Mark the probe with heat
resistant tape or by some other acceptable method to denote the proper distance into
the stack or duct for each sampling point. Select a total sampling time greater than
or equal to the minimum total sampling time specified in the test procedures for the
specific industry so that:
1. The sampling time per point is >2 min (a greater time interval may be
specified by the Administrator).
2. The sample volume corrected to standard conditions exceeds the required
minimum total gas sample volume.
The latter can be based on an approximate average sampling rate. It is
recommended that the number of minutes sampled at each point be either an integer or
an integer plus one-half minute to avoid timekeeping errors. In some circumstances
(e.g., batch cycles), it may be necessary to sample for shorter times at the traverse
-------
Section No. 3.19.4
Date September 3, 1992
Page 3
points and to obtain smaller gas sample volumes. In these cases, the Administrator's
approval must be obtained first.
4.3.2 Sampling Train Preparation-During preparation of the sampling train, keep all
openings where contamination can occur covered until just prior to assembly or until
sampling commences. The glassware should have been cleaned as described in Section
3.19.3 by soaking in 50% HNOj and then rinsing with tap water, 8 N HCl, tap water, and
finally deionized distilled water. Prepare the individual sampling train components
as follows:
Impingers
1. Place 50 ml of fresh 4% KMnO, in the first cleaned impinger using a graduated
cylinder that has been properly cleaned,
2. Place 100 ml of fresh 4% KMn04 in the second and third impingers using a
graduated cylinder, and
3. Place 200 to 300 g of preweighed silica gel in the fourth impinger.
Precaution: It is extremely important that all sample recovery personnel wear
safety glasses and gloves due to the dangers associated with impinger solutions and
recovery solutions.
Record the weight of the silica gel and the container on the sample recovery data
form, Figure 4.1, or other similar data form. Place the empty container in a safe
place for use later in the sample recovery. If moisture content is to be determined
by impinger analysis, weigh each of the first three impingers to the nearest 0.5 g, and
record these weights. Place the silica gel container in a clean place for later use
in the sample recovery. Alternatively, the weight of the silica gel plus impinger may
be determined to the nearest 0.5 g and recorded.
-------
Section No. 3.19.4
Date September 3, 1992
Page 4
Plant Sample Data
Sample Location . Run No.
Sample Recovery Person Recovery Date
Filter(s) No.
MOISTURE
Impinaers
Final volume (wt)
Initial volume (wt)
Net volume (wt)
Total moisture
RECOVERED SAMPLE BLANK
Blank filter Container No. KMn0« added, sealed and level marked?
Blank KMn04 solution (650 mL) Container No. Sealed and level marked?
Blank HC1 solution (25 mL added to 200 mL H20) Container No.
Sealed and level marked?
ml (g) Final wt g g
ml (g) Initial wt g g
ml (g) Net wt g g
RECOVERED SAMPLE
KMn04 impinger contents and rinse (400 mL) Container No.
Sealed and level marked?
Filter Container No. KMnO, added, sealed and level marked?
HC1 solution (25 mL added to 200 mL H20) Container No.
Sealed and level marked?
Samples stored and locked?
Remarks:
Date of laboratory custody
Laboratory person taking custody
Remarks:
Figure 4.1. Sample recovery and integrity data form.
-------
Section No. 3.19.4
Date September 3, 1992
Page 5
The use of a filter is optional in Method 101A. However, because of the
digestion techniques used for sample preparation, it is highly recommended that a
filter be used. Assemble the filter holder as follows:
Filter (optional)
1. Using a tweezer or clean disposable surgical gloves, place a filter in the
filter holder. Be sure that the filter is properly centered and that the
gasket is properly placed to prevent the sample gas stream from circumventing
the filter.
2. Visually check the filter for damage after the assembly is completed.
3. The filter or filter sample container should be marked.
Record the filter number on the sample recovery data form and then place the
filter sample container in a clean place for later use in the sample recovery.
Assemble the probe and nozzle as follows:
Probe/nozzle assembly
1. The probe liner should be glass and cleaned using the procedures described
above.
2. Place the properly sized, calibrated, and cleaned nozzle on the inlet of the
probe using a Teflon ferrule or Viton O-ring connection.
The nozzle should be uniquely identified. Record the nozzle number and diameter
on the sampling data form.
4.3.3 Sampling Train Assembiy-Assemble the train as shown in Figure 1.1, using (if
necessary) a very light coat of silicone grease only on the outside of all ground-glass
joints to avoid contamination. The tester may find that it is beneficial to conduct
a leak check of the sampling train in the assembly area prior to taking the system to
the stack.
The sampling train is then transported to the stack. At the stack, place crushed
ice and water around the impingers. If not already an integral part of the probe
assembly, a temperature sensor should be attached to the metal sheath of the sampling
probe so that the sensor extends beyond the probe tip and does not touch any metSl.
The sensor's position should be about 1.9 to 2.54 cm (0.75 to 1 in) from the pitot tube
and the nozzle to avoid interference with the gas flow. Alternative arrangements are
shown in Method 2.
4.3.4 Sampling Train Leak Checks-Leak checks are necessary to assure that the sample
has not been biased low by dilution air. The reference method (Section 3.19.10)
specifies that leak checks be performed at certain times as discussed below.
Precest-A pretest leak check is recommended, but not required. If the tester
opts to conduct the pretest leak check, follow the procedure described below:
After the sampling train has been assembled, set the filter heating system at the
desired operating temperature. Allow time for the temperature to stabilize. If a
Viton A O-ring or other leak free gasket is used in connecting the probe nozzle to the
probe liner, leak check the tram at the sampling site by plugging the nozzle and
pulling a 380- mm (15 in) Hg vacuum. Note: A lower vacuum may be used if it is not
exceeded during the test.
If an asbestos string is used for the probe gasket, do not connect the probe to
the train during the leak check. Instead, leak check the train by first plugging the
inlet to the filter holder and pulling a 380-mm (15 in) Hg vacuum (see note in the
previous paragraph) . Then connect the probe to the train and leak check at about 25-mm
(1 in.) Hg vacuum.; alternatively, the probe may be leak checked with the rest of the
sampling train in one step at a 380-mm (15 in.) Hg vacuum. Leakage rates >4% of the
average sampling rate or 0.00057 m3/min (0.02 ftVmin) , whichever is less, are
unacceptable.
-------
Section No. 3.19.4
Date September 3, 1992
Page 6
The following leak check instructions for the sampling train are taken from APTD-
05813 and APTD-0576. Start the pump with the bypass valve fully open and the coarse
adjust valve closed. Open the coarse adjust valve and then slowly close the bypass
valve until the desired vacuum is reached. Do not reverse the direction of the bypass
valve; this will cause KMn04 solution to back up from the impingers into the filter
holder. If the desired vacuum is exceeded, either leak check at this higher vacuum or
end the leak check as described below and start over.
When the leak check is complete, first slowly remove the plug from the inlet to
the probe or the filter holder and then close the coarse adjust valve and immediately
turn off the vacuum pump. (This prevents the KMn04 in the impingers from being forced
back into the filter holder and prevents the silica gel from being forced back into the
third impinger.) Visually check to be sure KMn04 did not contact the filter and that
the filter has no tears before beginning the sampling.
During the Samplings-It a component (e.g., filter assembly or impinger) change is
necessary during the sampling run, a leak-check should be conducted before the change.
The leak-check should be done according to the procedure outlined above, except that
it should be at a vacuum equal to or greater than the maximum value recorded up to that
point in the test. If the leakage rate is <0.00057 m'/rnin (0.02 ft'/min) or 4% of the
average sampling rate (whichever is less), the results are acceptable, and no
correction need be applied to the total volume of dry gas metered. If, however, a
higher leakage rate is obtained, the tester either should record the leakage rate and
plan to correct the sample volume as shown in Section 6.3(b) of the Reference Method
(Section 3.19.10), or should void the sampling run. Note: Be sure to record the dry
gas meter reading before and after each leak-check performed during and after each test
run so that the sample volume can be corrected.
Posttest-A leak-check is mandatory at the conclusion of each sampling run. The
leak-check should be in accordance with the procedures in this section and at a vacuum
equal to or greater than the maximum value reached during the sampling run. If the
leakage rate is <0.00057 m'/min (0.02 ft'/min) or 4% of the average sampling rate
(whichever is less), the results are acceptable, and no correction need be applied~to
the total volume of dry gas metered. If, however, a higher leakage rate is obtained,
the tester either should record the leakage rate and correct the sample volume as shown
in Section 6.3(a) or 6.3(b) of the Reference Method (Section 3.19.10), or should void
the sample run. Note: Be sure to record the dry gas meter reading before and after
performing the leak check so that the sample volume can be corrected.
4.3.5 Sampling Train OperaCion-Just prior to sampling, clean the portholes to minimize
the chance of sampling deposited material. Verify that the probe and the filter
heating systems are up to the desired temperatures and that the pitot tube and the
nozzle are located properly. Follow the procedures below for sampling.
1. Record the initial dry gas meter readings, barometric pressure, and other
data as indicated in Figure 4.2.
2. Position the tip of the probe at the first sampling point with the nozzle tip
pointing directly into the gas stream. When in position, block off the open
area around the probe and the porthole to prevent flow disturbances and
unrepresentative dilution of the gas stream.
3. Turn on the pump and immediately adjust the sample flow to attain isokinetic
conditions. Nomographs, calculator programs, and routines are available to
aid in the rapid determination of the orifice pressure drop corresponding to
the isokinetic sampling rate. If the nomograph is designed as shown in APTD-
0576 it can be used only with an Type S pitot tube which has a Cp coefficient
of 0.85 t 0.02 and when the stack gas dry molecular weight (Ms) is 29 i 4.
If Cp and Ms are outside these ranges, do not use the nomograph without
-------
Section No. 3.19.4
Date September 3, 1992
Page 7
compensating for the differences. Recalibrate isokinetic rate or reset
nomograph if the absolute stack temperature (Ts) changes more than 10%.
4. Take other readings required by Figure 4.2 at least once at each sampling
point during each time increment.
5. Record the dry gas meter readings at the end of each time increment.
6. Repeat steps 3 through 5 for each sampling point.
7. Turn off the pump, remove the probe from the stack, and record the final
readings after each traverse.
8. Conduct the mandatory posttest leak check (Subsection 4.2.5) at the
conclusion of the last traverse (after allowing the nozzle to cool). Record
any leakage rate. Also, leak check the pitot lines (Method 2, Section 2.1);
the lines must pass this leak-check to validate the velocity pressure data.
9. Disconnect the probe, and then cap the nozzle and the end of the probe with
polyethylene or equivalent caps.
-------
Plant
City
Locat ion
Operator
Date
Meter calibration
Pitot tube
Probe length
(Y)
Run No.
Stack dia. mm (in).
Sample box No.
Meter box No.
Meter AH@
Probe liner material
Probe heater setting
Ambient temperature _
Barometric press (Pb)
Assumed moisture
Static press. (P„)
C Factor
Reference AH@
Sheet
Nozzle ID No.
of
ft Nozzle diameter
_ Thermometer No.
_ Final leak rate
mm (in)
°F
Hg
mm (in)
%H20
(in) Hg
mm
Vacuum during leak-check
Filter No(s).
Remarks:
m3/min (cfm)
mm (in) Hg
~r
Traverse
point
number
Sampling
time,
(0), min
Clock
time,
(24 h)
Vacuum,
mm
(in) Hg
Stack
temp
(Ts)
°C (°F)
Velocity
head
(APs)
mm
(in) Hg
Press
across
or if ice
meter
(AH), mm
(in) Hg
Gas sample
volume (Vm),
m3 (f 13)
Dry gas meter
temperature
Inlet |Outlet
°C(°F) j0C(°F)
Gas temp
leaving
impinger
°C(°F)
Filter
temp
°C(°F)
tj O W
pom
o
•a a
H- LJ
U> to
t*
H
to
KJ
Total
Max
Avg
Total
Avg
Avg
Max
_L
Figure 4.2. Method 101A field seimple data form.
-------
Section 3.19.4
Date April 3, 1992
Page 9
During the test run, a sampling rate of 10% of the isokinetic rate must be
maintained unless otherwise specified by the Administrator. The sampling rate must be
adjusted at any sampling point if a 20% variation in velocity pressure occurs.
Periodically during the test, observe the connecting glassware--fxom the probe,
through the filter, to the first impinger--for water condensation. If any is evident,
adjust the probe and/or filter heater setting upward until the condensation is
eliminated; add ice around the impingers to maintain the silica gel exit temperature
at 20 °C (68 °F).
The manometer level and zero should also be checked periodically during each
traverse. Vibrations and temperature fluctuations can cause the manometer zero to
shift.
4.4 Sample Recovery
The reference method (Section 3.19.10) requires that the sample be recovered from
the probe, from all glassware preceding the filter, from the front half of the filter
holder, from the filter, and from the impingers and connecting glassware in an area
sheltered from wind and dust to prevent contamination of the sample. Begin proper
cleanup procedure as soon as the probe is removed from the stack at the end of the
sampling period. Allow the probe to cool. When it can be safely handled, wipe off any
external particulate matter near the tip of the probe nozzle, and place a cap over it.
Do not cap off the probe tip tightly while the sampling train is cooling because the
resultant vacuum could draw liquid out from the impingers. Before moving the sample
train to the cleanup site, remove the probe from the train, wipe off the silicone
grease, and cap the open outlet of the probe and the inlet of the sample train.
Be careful not to lose any condensate that might be present. Wipe off the
silicone grease from the impinger. Use either ground-glass stoppers, plastic caps, or
serum caps to close these openings. The cappea-off impinger box and the capped
sampling probe can be transported to the cleanup area without risk of losing or
contaminating the sample. Transfer the probe, impinger assembly, and (if applicable)
filter assembly to a cleanup area that is clean, protected from the wind, and free of
Hg contamination. The ambient air in laboratories located in the immediate vicinity
of Hg-using facilities is not normally free of Hg contamination. Inspect the train
before and during disassembly, and note any abnormal conditions.
Precaution: It is extremely important that all sample recovery personnel w%ar
safety glasses and gloves due to the dangers associated with impinger solutions and
recovery solutions.
The following sample recovery sequence includes (1) recovery of the sample from
the impingers using KMnO,, Container 1; (2) recovery of any residual brown deposits
from the impingers using water, Container 1; (3) recovery of the sample from the probe
and connecting glassware using KMnO«, Container No.l; (4) recovery of any residual
brown deposits from the probe and connecting glassware using water, Container No.l; (5)
recovery of any residual brown deposits from sample train components not removed by
water with HC1, Container 1A; recovery of silica gel. Container 2; (6) recovery of the
filter, Container No. 3; (7) collecting a filter blank. Container No. 4; (8) collecting
an KMnO, reagent blank, Container No. 5; (9) collecting a water reagent blank, and (10)
collecting a HC1 reagent blank.
4.4.1 Impinger Contents (Container Nos. 1 and 1A>-Recover the samples follows:
1. Note the color of the reagent in each of the impingers and record the color
on the Sample Recovery Data Form. If the color of the KMnO, in the last
impinger has changed from the purple color, the sample run will be considered
invalid and must- be repeated. If all the impinger solution has been
-------
Section 3.19.4
Date April 3, 1992
Page 10
oxidized, the tester should (1) reduce the sample time or volume if the
reduced time or volume will comply with the applicable regulations, (2) add
another impinger containing KMnO«, or (3) use two sample trains per sample
run.
2. Using a properly cleaned graduated cylinder, measure the liquid in the first
three impingers to within 1 ml. Record the volume of liquid on the Sample
Recovery and Integrity Data Form. This information is needed to calculate
the moisture content of the effluent gas. (Use only graduated cylinders and
glass storage bottles that have been precleaned as in Section 3.19.3.)
3. Place the contents of the first three impingers in a properly cleaned,
1000-ml glass sample bottle (Container No. 1). Record the data on the sample
recovery data form.
4. Prior to recovering the sample, place 400-ml of fresh KMnO, in a graduated
cylinder for sample recovery. This solution is used to recover sample from
the probe nozzle, probe fitting, probe liner, and front half of the filter
holder (if applicable) and impingers (sample-exposed surfaces). Rinse the
impingers with a portion (about 100 ml) of the COO ml of fresh 4% KMnO,
solution to assure removal of all loose particulate matter from the
impingers; add all washings to the 1000-ml glass sample bottle (Container No.
1) .
5. To remove any residual brown deposits on the glassware following the
permanganate rinse, carefully rinse all the sample-exposed glassware with
approximately 100 ml of water. Add this rinse to Container No. 1. The
impingers should only require about 50 ml of the 100 ml of water.
6. If no visible deposits remain after this water rinse, do not rinse with 8 N
HCl. However, if deposits remain on the glassware after the water rinse,
place 25 ml of 8 N HCl in a graduated cylinder. Wash impinger walls and
stems with this 25 ml of 8 N HCl as follows: Place 150 ml of water in a
sample container labeled Container No. 1A. Use only a total of 25 ml of £ N
HCl to rinse all impingers. Wash the impinger walls and stem with the HCl by
turning and shaking the impinger so that the HCl contacts all inside
surfaces. Pour the HCl wash carefully while stirring into Container No. 1A.
Rinse all glassware that was exposed to HCl with 50 ml water, and add water
rinse to Container No. 1A. Label the sample bottle and record the sample
number on the Sample Recovery Data Form. The separate container is used for
safety reasons.
4.4.2 Probe and Connecting Glassware (Container No. lJ-The same sample bottle
(Container No. 1) as used above for the impinger contents and sample rinse is usually
adequate for the collection of all the rinses. Recover the sample from the probe liner
and connecting glassware as follows:
1. Clean the outside of the probe, the pitot tube, and the nozzle to prevent
particulates from being brushed into the sample bottle. Take care that dust
on the outside of the probe or other exterior surfaces does not get into the
sample during the quantitative recovery of the Hg (and any condensate) from
the probe nozzle, probe fitting, probe liner, and front half of the filter
holder (if applicable).
2. Carefully remove the probe nozzle and rinse the inside surface (using a nylon
bristle brush and several KMnO, rinses) into the sample bottle (Container No.
1) .
3. Clean the compression fitting by the same procedure. Rinse all sampleexposed
glassware components with the total of 400 ml of fresh 4% KMnO, solution as
-------
Section 3.19.4
Date April 3, 1992
Page 11
measured above. Add these washings to the 1000-ml glass sample bottle
(Container No. 1).
4. After the KMnO« rinse, use a small portion of the remaining 100 ml of water
to rinse the nozzle and connecting glass after the KMn04 rinse. Add the
rinses to Container 1.
The following probe rinsing procedure should be performed by two people to
preclude sample loss. The rinsing procedures for the probe liner and connecting
glassware is as follows:
1. Rinse the probe liner by tilting and rotating the probe while squirting fresh
4% KMn04 solution into the upper (or nozzle) end to assure complete wetting
of the inside surface.
2. Allow the KMnO, solution to drain into the 6ample bottle (Container 1) using
a funnel to prevent spillage.
3. Hold the probe in an inclined position and squirt KMnO« solution into the
upper end while pushing the probe brush through the liner with a twisting
motion, and catch the drainage in the sample bottle. Repeat the brushing
procedure three or more times until a visual inspection of the liner reveals
no particulate remaining inside.
4. Rinse the liner once more with KMnO« solution.
5. Rinse the brush with KMnO, solution into Container 1 to remove all sample that
is retained by the bristles.
6. Rinse the probe liner with the remaining 100 ml of water into Container 1.
7. Wipe all the connecting joints clean of silicone grease, and clean the inside
of the front half of the filter holder by rubbing the surface with a nylon
bristle brush and rinsing it with KMn04. Repeat the procedure at least three
times or until no particles are evident in the rinse.
8. Make a final rinse of the filter holder and brush.
9. Clean any connecting glassware which precedes the filter holder, using Steps
5 and 6.
After all washings have been collected in Container No. 1, tighten the lid on the
container to prevent leakage during shipment to the laboratory. It is recommended that
the lid have a No. 70-72 hole drilled in the container cap and Teflon liners for
pressure relief. Mark the height of the fluid level to determine whether leakage
occurs during transport. Label the container to identify its contents clearly, and
note it on the Sample Recovery Data Form.
4.4.3 Silica Gel (Container No. 2)—Note the color of the indicating silica gel to
determine whether it has been completely spent, and make a notation of its condition
on the sample recovery data form, Figure 4.3.
1. Transfer the silica gel from the fourth impinger to its original container
using a funnel and a rubber policeman, and seal the container. It is not
necessary to remove the small amount of dust particles that may adhere to
the impinger wall; since the weight gain is used for moisture calcula-
tions, do not use water or other liquids to transfer the silica gel.
2. Determine the final weight gain to the nearest 0.5 g, if a balance is
available.
4.4.4 Filter (Container No. 31-Carefully remove the filter (if used) from the filter
holder, place it in a 150-ml glass sample bottle, and add 20 to 40 ml of 4% KMn04 to
submerge the filter. If it is necessary to fold the filter, be sure that the
particulate cake is inside the fold. Carefully transfer, to the 150-ml sample bottle,
any particulate matter and filter fibers that adhere to the filter holder gasket by
using a dry Nylon.bristle brush and a sharp-edged blade. Seal the container. Clearly
-------
Section 3.19.4
Date April 3, 1992
Page 12
label the container to identify its contents. Mark the height of the fluid level to
determine whether leakage occurs during transport.
4.4.5 Filter Blank (Container No. 4)-If a filter is used for testing, initially take
an unused filter for each field test series and label as a filter blank. Treat the
filter blank in the same manner as described in Subsection 4.3.4 above.
4.4.6 Absorbing Solution Blank (Container No. 5)—Tor a blank, place 650 ml of 4% KMnO«
absorbing solution in a 1000-ml sample bottle. If the 100 ml water rinse was used
during recovery, carefully add a second 100 ml portion of water to Container No. 5.
It is recommended that the lid have a No. 70-72 hole drilled in the container cap and
Teflon liners for pressure relief. Mark the height of the fluid level to determine
whether leakage occurs during transport. Label the container as the KMn04 blank, and
seal the container.
4.4.7 8 N HC1 Blank (Container No. 6)-It 8 N HC1 was used (Container 1A) to remove any
residual brown deposits remaining after rinsing sample-exposed glassware with fresh 4%
KMnO, solution and water, place 25 ml of 8 N HCl used for removing the deposits in a
separate sample container (Container No. 6) containing 200 ml of water. Mark container
as the HCl blank, and seal the container.
4.5 Sample Logistics and Packino Equipment
Follow the sampling and sample recovery procedures until the required number of
runs are completed and blank samples are labeled. Log all data on the Sample Recovery
and Integrity Data Form, Figure 4.1. At the conclusion of the test:
1. Check all rinses and filters for proper labeling (time, date, location, test
run number, and any other pertinent documentation) . Be sure that blanks have
been set aside and labeled.
2. If possible, make a copy of the field data form(s) in case the originals arte
lost.
3. Examine all sample containers for damage and ensure that they are properly
sealed for transport to the base laboratory. Ensure that the containers are
labeled properly for shipping to prevent loss of samples or equipment.
4. Review the field sampling data form and any other completed data forms to
ensure that all data have been recorded and that all forms are present.
4 . 6 Systems Audit
A Method 101A sampling ana sample recovery checklist is presented in Figure 4.3.
-------
Section 3.19.4
Date April 3,
Page 13
Date Time • Operator Observer
Method 101A Sampling Procedures
Probe Nozzle: stainless steel glass
Button-hook elbow size
Cleaned according to sampling protocol?
Sealed with Teflon tape or other cover?
Probe liner: borosilicate quartz other _
Cleaned according to sampling protocol?
Openings sealed with Teflon tape?
Probe heating system:
Checked? Temperature Stable?
Pltot tube: Type S Other
Properly attached to probe (no interference to nozzle)?
Modifications:
Pitot tube coefficient
Differential Pressure Gauge: Inclined manometers
Magnahelics Ranges
Other Ranges
Cyclone (inlet only): borosilicate glass other
Cleaned according to sampling protocol?
Filter Bolder: borosilicate glass other
Frit material: glass Teflon other
Gasket material: silicone other
Cleaned according to sampling protocol?
Sealed with Teflon tape or glass caps?
Filter type(s):
Cleaned according to sampling protocol?
Impinger Train: number of impingers
Cleaned according to sampling protocol?
Contents: 1st 2nd 3rd
4th 5th 6th
Impinger weights recorded?
Proper connections?
Modifications
Silica gel: type new? used?
Figure 4.3. Field observation of Method 101A sampling and recovery.
-------
Section 3.19.4
Date April 3, 1992
Page 14
Date Time Operator Observer
Mathod 101A Sampling Procedures
Procedure
Barometer: mercury aneroid other
Gas Density Determination: temperature sensor
pressure gauge
Temperature sensor properly attached to probe?
Recent Calibrations: pitot tubes
meter box thermocouples/thermometers
Filters checked visually for irregularities?
Filters properly centered? labeled?
Sampling site properly selected?
Nozzle size properly selected?
Proper sampling time selected or calculated?
All openings of sampling train sealed (pretest
and posttest)?
Impingers, filter holder, probe, and nozzle assembled?
Cyclone attached (inlet only)?
Pitot lines checked for leaks and plugging?
Meter box leveled? Manometers zeroed?
AH@ from most recent calibration
Nomograph setup correctly? K factor
Pretest leak-check conducted? Leakage rate?
Care taken to avoid scraping nipple or stack wall?
Effective seal around probe when in-stack?
Probe moved to traverse points at proper time?
Figure 4.3. (Contined)
-------
Section 3.19.4
Date April 3, 1992
Page 15
Date Time Operator Observer
Method 101A Sampling Procedure®
Nozzle and pitot tubes kept parallel to stack at all times?
Filter(s) changed during run?
Any particulate lost during filter change?
Data forms completed and data recorded properly?
Nomograph setting changed with significant change in the stack temperature?
Velocity pressure and orifice pressure recorded accurately?
Posttest leak-check conducted? Leakage rate
at inches of mercury
Orsat analysis? Stack Integrated
Approximate stack temperature Gas sample volume
Percent isokinetic calculated
Comments
Figure 4.3. (Continued)
-------
Section 3.19.4
Date April 3, 1992
Page 16
Date Time Operator Observer .
Method 101A Sample Recovery
Reagent*:
Brushes: Teflon bristle other
Cleaned according to sampling protocol?
Wash bottles: glass other
Cleaned according to sampling protocol?
Storage container*: glass? other?
Cleaned according to sampling protocol?
Teflon cap liner? Leak free?
Small hole in cap to relieve pressure?
Filter container*: borosilicate glass other
Cleaned according to sampling protocol?
Graduated cylinder: borosilicate glass other
Subdivisions of graduated cylinder <2 ml?
Cleaned according to sampling protocol?
Balance type: Calibrated?
Probe allowed to cool sufficiently?
Probe and sample train openings covered?
Clean-up area(s) used
FMn04 Volume: Was 400 mL of KMnO, measured for recovery?
Filter handling: tweezers used? surgical gloves?
Any particulate lost?
KMnO, added to filter?
Probe handling: KKn04 rinses Brushed?
H,0 rinses Brushed?
Recovery of probe: probe nozzle probe fitting
probe liner front half of filter holder _
Figure 4.3. (Continued)
-------
Section 3.19.4
Date April 3, 1992
Page 17
Date Time Operator Observer
Method 101A Sample Recovery (eont)
HCl Volume: Was 25 mL of HCl measured for recovery?
Impinger handling: weighed? volumed?
KMnO, rinses H20 rinse __
HCl rinses
Blanks collected: filter
KMnO« (650 mL)
HCl (25 mL in 200 mL of H20)
Container No. 1: Sample No. 400 mL KMnO« rinse
Impinger contents Impinger Rinse
Probe rinse Nozzle rinse
Container No. 1A: Sample No. 25 mL HCl
Impinger rinse
Container No. 2 Silica gel: color? condition? weighed?
Samples labeled and stored properly?
- Liquid levels marked?
Remarks:
Figure 4.3. (Continued)
-------
Section 3.19.4
Date April 3, 1992
Page 18
TABLE 4.1. ACTIVITY MATRIX FOR ON-SITE MEASUREMENT CHECKS
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Preliminary
determinations and
measurements
Determine the
moisture content of
stack gas
Determine flow rate
of stack gas
Determine stack
temperature
Determine stack
dimensions
Determine dry
molecular weight of
stack gas
Select sampling time
£ minimum total sam-
pling time in
applicable emission
standard; number of
minutes between read-
ings should be an
integer
Once each field test;
use wet bulb/dry bulb
thermometer, Method 4,
or sling psychrometer
Once each field test,
using Method 1
Prior to and during
sampling
I
Prior to sampling,
using tape measure
Once each field test,
Method 2; if inte-
grated gas sample is
required, Method 3
Prior to sampling
Complete
Complete
Complete
Complete
Complete
Complete
Preparation of
collection train
Assemble train
according to
specifications in
Figure 1.1 and Sec.
3.18.4 Subsec. 4.3.3
Leak-check; Leak
rate < 4% or 0.00057
mVmin (0.02 ft3/
min), whichever is
less
Before each sampling
run
Complete
Leak-check before sam-
pling by plugging the
nozzle or inlet to
first impinger and by
pulling a vacuum of
380 mm (15 in) Hg
Correct the leak
(Continued)
-------
Section 3.19.4
Date April 3, 1992
Page 19
TABLE 4.1 (Continued)
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Sampling
(isokinetically)
Within 10* of
isokinetic condition
Standard check for
minimum sampling
time and volume;
sampling time/point
£ 2 min
Minimum number of
points specified by
Method 1
Leak-check; leakage
rate < 0.00057 m3/
min (0.02 ft3/min)
or 4% of the average
sampling volume,
whichever is less
Calculate for each
sample run
Make a quick calcu-
lation before each
test, and exact cal-
ulation after
Check before the first
test run by measuring
duct and using Method
1
Leak-check after each
test run or before
equipment replacement
during test at the
maximum vacuum during
the test (mandatory)
Repeat the test
run
Repeat the test
run
Repeat the pro-
cedure to comply
with specifica-
tions of Method 1
Correct the
sample volume,
or repeat the
sampling
Sample recovery
Sample free of
contamination
Transfer sample as
outlined in Sec 3.19.
4, subsec 4.5 after
each test run; label
containers and mark
level of solution in
container
Repeat the
sampling
Sample logistics
and packing of
equipment
All data recorded
correctly
All equipment
examined for damage
and labelled for
shipment
All sample contain-
ers and blanks
properly labelled
and packaged
After completion of
each test and before
packing; if possible,
make copies of forms
After completion of
each test and before
packing
Visually check upon
completion of each
sampling
Complete data
Repeat sampling
if damage occurred
during the test
Correct when
possible
-------
Section No. 3.19.5
Date September 3, 1992
Page 1
5.0 POSTSAMPLING OPERATIONS
The postsampling operations include postsampling calibration checks of
sampling equipment and analysis by atomic absorption spectrophotometry techniques. The
sample analysis includes calibrations and performance checks. Checklists for
monitoring the postsampling operations are provided at the end of this section. Table
5.1 at the end of this section summarizes the QA activities associated with the
postsampling operations.
5.1 Calibration Checks of Samplina Equipment
Posttest checks will have to be made on most of the sampling apparatus. These
checks will include three calibration runs at a single orifice meter setting, cleaning,
and/or routine maintenance. Cleaning and maintenance are discussed in Section 3.19.7
and in APTD 057 6. Figure 5.1 can be used to record the posttest checks.
5.1.1 Metering System-The metering system has two components that must be
checked—the dry-gas meter and the dry-gas meter thermometer(s).
The dry-gas meter thermometer(s) should be compared with the ASTM mer-
cury-in-glass thermometer at room temperature. If the two readings agree within 6 °C
(10.8 °F) , they are acceptable; if not, the thermometer must be recalibrated according
to Subsection 2.2 of Section 3.19.2 after the posttest check of the dry-gas meter. For
calculations, use the dry-gas meter thermometer readings (field or recalibration
values) that would give the higher temperatures. That is, if the field readings are
higher, no correction is necessary, but if the recalibration value is higher, add the
difference in the two readings to the average dry-gas meter temperature reading.
The posttest check of the dry-gas meter is described in Section 3.19.2. The
metering system should not have any leaks that were corrected prior to the posttest
check. If the dry-gas meter calibration factor (Y) deviates by <5% from the initial
calibration factor, the dry-gas meter volumes obtained during the test series are
acceptable. If Y deviates by >5%, recalibrate the metering system (Section 3.19.2).
For the calculations, use the calibration factor (initial or recalibration) that yields
the lower gas volume for each test run.
5.1.2 Stack Temperature Sensors-The stack temperature sensor readings should be
compared with the reference thermometer readings.
For thermocouple (s) , compare the thermocouple and reference thermometer values
at ambient temperature. If the values agree within 1.5% of the absolute temperature,
the calibration is considered valid. If the values do not agree within 1.5%, recali-
brate the thermocouple as described in Section 3.19.2 to determine the difference (AT.)
at the average stack temperature (T,) . NOTE: This comparison may be done in the field
immediately following the tests.
For thermometers, compare the reference thermometer:
1. At ambient temperatures for average stack temperature below 100 °C (212
°F) .
-------
Section No. 3.19.5
Date September 3, 1992
Page 2
Plant Calibrated by
Meter box number ___________ Date
Drv-Gas Meter
Pretest calibration factor, Y (within 2%)
Posttest check, Y* (within 5% of pretest value)
Recalibration required? yes no
If yes, calibration factor, Y (within 2%)
Lower calibration factor, Y for calculations (pretest or posttest)
Drv-Gas Meter Thermometers
Was a pretest temperature correction used? ves no
If yes, temperature correction _______ (within 5.4 °F over range)
Posttest comparison with mercury-in-glass thermometer? * (within 10.8 °F at ambient
temperature) °F
Recalibration required? ves no
Recalibration temperature correction? _____ (within 5.4 °F over range)
If yes, no correction necessary for calibration if meter thermometer temperature
is higher, if calibration temperature is higher, add correction to average meter
temperature for calculations.
Stack Temperature Sensor
Was a pretest temperature correction used? ves no
If yes, temperature correction °F (within 1.5% in. °R over range)
Average stack temperature of compliance test, T. _____________
Temperature of reference thermometer or solution __ °R (within 10% of T,)
Temperature of stack temperature for recalibration ___________
Difference between reference and stack thermometers, AT, _________ °R
Do values agree within 1.5%?* ves no
If yes, no correction necessary for calculations.
If no, calculation must be done twice-once with the recorded values and once with
the average stack temperature corrected to correspond to the reference
temperature differential (AT,). Both final results must be/reported.
Barometer
Was the pretest field barometer correct? ves no
Posttest comparison?* in. Hg (within 0.1 in. Hg)
Was recalibration required? ves no
If yes, no correction necessary for calculations when the field barometer has a
lower readings; if the mercury-in-glass reading is lower, subtract the difference
from the field data readings for the calculations.
Figure 5.1. Posttest calibration checks.
-------
Section No. 3.19.5
Date September 3, 1992
Page 3
2. In boiling water for stack temperatures from 100 °C to 200 °C.
3. In a boiling liquid with the boiling point above 200 °C for stack
temperatures between 200 to 405 °C. For stack temperatures above 405
°C, compare the stack thermometer with a thermocouple at a temperature
within 10% of the average stack temperature. If the absolute values
agree within 1.5%, the calibration is considered valid. If not,
determine the error (AT.) to correct the average stack temperature.
5.1.3 Barometer^The field barometer should be compared to a Hg-in-glass barometer.
If the readings agree within 5 mm (0.2 in.) Hg, the field readings are acceptable; if
not, use the lesser calibration value for the calculations. If the field barometer
reads lower than the Hg-inglass barometer, the field data are acceptable. If the
Hg-in-glass barometer gives the lower reading, use the difference in the two readings
(the adjusted barometric value) in the calculations.
5.2 Sample Preparation
Field samples and reagent blanks should be prepared concurrently, if possible.
Check the liquid level in each container to see whether liquid was lost during
transport. If a noticeable amount of leakage occurred, either void the sample or use
methods subject to the approval of the Administrator to account for the losses. Record
the findings of the liquid level check on the sample preparation data form, Figure 5.2,
or another suitable form. Then follow the procedures below.
5.2.1 Containers No. 3 end No. 4 (Filter and Filter Blank)—It a filter is used, the
following procedures apply:
1. Place the contents, including the filter, of Container No. 3 in a
separate, properly cleaned, and uniquely identified 250-mL beaker.
Using three rinses of approximately 10 mL of water, complete the sample
transfer from the container. Record the beaker number with the run
number on the sample preparation data form.
2. Place the contents of Container No. 4 in a properly cleaned 250-mL
beaker. Label it as the sample filter blank or as another suitable
name. Use three rinses of approximately 10 mL of water for the sample
transfer. Record the name on the sample preparation data form. -
3. Heat the beakers in a laboratory hood on a steam bath until most of the
liquid has evaporated. Do not take to dryness. Do not use direct
heating on a hot plate. Record the completion of the step on the sample
preparation data form.
4. Add 20 mL of concentrated HN03 to each beaker, cover each beaker with a
watch glass, and heat on a hot plate at 7 0 °C for 2 h in a laboratory
hood. Record completion of this step on the sample preparation data
form.
-------
Section No. 3.19.5
Date September 3, 1992
Page 4
Sample Preparation Data Form
Date Plant Name Sampling Location
Sample Preparation Checks
Sample Integrity Check: Have containers leaked?
Container 1 4
1A 5
2 6
3
Run Run Run Blank
12 3
Place a check to indicate completion
of step or record data as indicated.
Preparation of Filter Digest: Container No. 3
Sample No. for each 250-mL beaker _____
Contents added to a glass 250-mL beaker? ____
Heated carefully to near dryness
(not dryness) using a steam bath? _____
Volume of HNOj added to beaker 25 mL?
Covered with watch glass? ___
Heated at 70 °C on hot plate for 2 h? _____
How was temperature monitored? ____
Filtered through Whatman 40 paper ?
Date _____
Time
Rinsed beaker residue carefully through
the filter? _____
Saved filtrate?
Preparation of Sample No. A.l:
Are Container No. 1 contents <1000 mL?
If so, volume, mL
Are Container No. 1 contents filtered through
Whatman 4 0 paper?
Filter saved?
Filtrate added to mL glass volumetric flask?
Filter digest (above) added to flask with
Container No. 1 filtrate?
Completion of Sample No. A.l?
Date
Time
Figure 5.2. Sample preparation data form.
-------
Section No. 3.19.5
Date September 3, 1992
Page 5
Run Run Run Blank
12 3
Preparation of Sample No. HC1 A.2:
25 mL of 8N HC1 added to filter saved from
preparation of Sample No. A.l?
How was HC1 added?
Digestion started, Time
Date
Digestion completed, Time
Date
HCl digest dilution volume, mL
Preparation of Filter Blank:
Container 4 contents added to 250-mL beaker
Heated carefully to near dryness
(not dryness) using a steam bath?
Volume of HNOj added to beaker 25 mL?
Covered with watch glass?
Heated at 70 °C on hot plate for 2 h?
How was temperature monitored?
Preparation of Sample A.l Blank:
Are Container No. 5 contents diluted to same
volume as Container No. 1 contents?
Filtered through Whatman 4 0 paper?
Filter saved?
Filtrate added to 1000-mL glass
volumetric flask?
Filter blank (Container No. 4) digest (above)
added to same volumetric flask?
Time of completion of Sample No. A.l
Preparation of Sample No. HCl A.2 Blank:
25 mL of 8N HCl added to filter saved from
preparation of Sample No. A.l blank?
How was HCl added?
Time 24-h digestion started?
Date
Time
Time 24-h digestion completed?
Date
Time
HCl digest was diluted to 500 mL using glass
volumetric flask?
Figure 5.2. (Continued)
-------
Section No. 3.19.5
Date September 3, 1992
Page 6
Note: The analysts should use gloves and safety glasses and should avoid skin
contact and breathing the fumes from the HN03.
5. Remove the beaker from the hot plate and filter the solution from the
digestion of the contents of Container No. 3 through a separate Whatman
40 filter paper into a properly cleaned and identified (the same sample
identification number can be used) sample container using a vacuum
filtering system. Use three rinses of approximately 10 mL of water for
the sample transfer. The filtration should be conducted in a laboratory
• hood. Record the completion of this step on the sample recovery data
form.
6. Save the filtrate for addition to the Container No. 1 filtrate, as de-
scribed in Subsection 5.2.2. Discard the filter.
7. Filter the solution from the digestion of the contents of Container No.
4 (sample filter blank) through Whatman 40 filter paper, as described
above in Step 5, and save the filtrate for addition to the Container No.
5 filtrate, as described in Section 5.2.2. Discard the filter.
5.2.2 Container No. 1 (Impingers, Probe, and Filter Holder) and. If Applicable, 1A
(HCl Rinse)—The KMnO« impinger solution and rinse and HC1 rinse (if applicable) are
prepared as follows:
Note: Because of the hazardous nature of the HN03 and HCl solutions, analysts
must wear gloves and safety glasses and should avoid skin contact and breathing the
fumes from HN03 and HCl. The HN03 and KMn04 solutions should not come in contact with
oxidizable matter.
KMnO, Impinoer Solution and Sample Recovery Rinse
1. To remove the brown Mn02 precipitate, filter the contents of Container
No. 1 through a Whatman 40 filter into a properly cleaned and identified
1-L volumetric flask. Use three rinses of approximately 10 mL of water
for the sample transfer. "*
2. Save the filter for digestion of the brown Mn02 precipitate, as
described in steps 6 through 9 below, and record the date and time the
filtration step was completed on the sample preparation data form.
3. Add the sample filtrate from Container No. 3 produced in Subsection
5.2.1 above to the appropriate 1-L volumetric flask from Step 1, and
dilute to volume with water. If the combined filtrates are greater than
1000 mL, determine the volume to the nearest mL and record the volume
on the sample preparation data form. This volume will be used to make
the appropriate corrections for blank subtractions and emissions
calculations.
4. Mix thoroughly. The filtrate will be referred to as Analysis Sample No.
A.l.
5. The Analysis Sample No. A.l must be analyzed for Hg within 48 h after
completion of the filtration step. If the sample is not analyzed within
this period, steps 1 through 4 must be repeated, the additional Whatman
40 filter paper will be digested as described below in steps 6 through
9, and the digestion will be added to the sample.
Whatman 40 Filter and MnO- Precipitate
6. Place the saved filter, which was used to remove the brown MnO;
precipitate, into a container of appropriate size. Submerge the filter
with 25 mL of 8 N HCl and allow it and the brown residue to digest for
a minimum of 24 h at room temperature. Record the date and time for the
beginning of the digestion, on the sample preparation data form.
-------
Section No. 3.19.5
Date September 3, 1992
Page 7
Whatman 40 Filter, MnO, Precipitate, and HC1 Rinse
7. Filter the contents of Container No. 1A, HCl rinse (if applicable)
through a Whatman 40 filter into a properly cleaned and identified
500-mL volumetric flask. Use three rinses of approximately 10 mL of
water for the sample transfer. Record completion on the sample
preparation data form.
8. Filter the digestion of the brown Mn02 precipitate and Whatman filter
from Step 6 into the 500-mL volumetric flask from Step 7. Use three
rinses of approximately 10 mL of water for the sample transfer. Record
the date and time of the filtration on the sample preparation data form.
9. Dilute to volume with water. This solution will be referred to as
Analysis Sample No. HCl A.2. Save the solution for Hg analysis as
described in Subsection 5.3.4 below. Discard the filters.
5.2.3 Containers No. 5 (Absorbing Solution Blank) and No. € (HCl rinse blank)-The
procedures for preparing the blank solutions are described below:
Note: The same precautions should be taken with the blank solutions as were taken with
the sample solutions. The sample blanks have been designed to allow easy blank
subtraction from the sample. The volume of all solutions and the number of filters are
identical to the field samples. Therefore, the blank sample must be prepared at the
same time and in the same manner as the field samples.
KMn04 Reagent Blank Solution and Sample Recovery Blank Rinse
1. Treat Container No. 5 (650 mL of blank absorbing solution) the same as
Container No. 1 (described in steps 1 through 5 in Subsection 5.2.2).
Filter Blank
2. Add the filter blank filtrate from Container No. 4 (completed in steps
1 through 7 of Subsection 5.2.1 above) to the 1-L volumetric flask
(containing Container No. 5 filtrate), and dilute to volume. Mix
thoroughly.
3. This solution will be referred to as Analysis Sample No. A.l blank.
4. Analysis Sample No. A.l blank must be analyzed for Hg within 48 h after
the completion of the filtration step.
Whatman 40 Filter and KMnOt Reagent Blank Precipitate
5. Digest any brown precipitate remaining on the filter from the filtration
of Container No. 5 by the same procedure described in step 6 in
Subsection 5.2.2 above.
Whatman 40 Filter, KMnO, Blank Precipitate, and Blank HCl Rinse
6. Filter the contents of Container No. 6 by the same procedure described
in steps 7, 8, and 9 in Subsection 5.2.2 and combine into the 500-mL
volumetric flask with the filtrate from the digested KMnO, blank
precipitate. The resulting 500-mL combined dilute solution will be
referred to as Analysis Sample No. HCl A.2 blank. NOTE: As discussed in
Subsection 5.3.4 below, when analyzing samples A.l blank and HCl A.2
blank, always begin with 10-mL aliquots; this note applies specifically
to blank samples.
5.3 Analys is
Precise and accurate analysis requires that the Hg analysis system be
calibrated properly, which includes preparing calibration standards and field samples.
-------
Section No. 3.19.5
Date September 3, 1992
Page 8
For Method 101A, spectrophotometer calibration is conducted in conjunction with
analyzing the field samples (and QA samples). This section presents the steps for
analyzing the field samples and includes preparing sample and field blanks, as well as
describing how to quality control (QC) samples. It discusses the relationship between
analyzing the field samples and preparing the calibration curve.
5.3.1 Instrument Setup-Before use, clean all glassware, both new and used, as
follows: brush with soap and tap water, liberally rinse with tap water, soak for 1 h
in 50% HNOj, and then rinse with deionized distilled water.
Flow Calibration-Assemble the aeration system as shown in
Figure 5.3. Set the outlet pressure on the aeration gas cylinder regulator to a
minimum pressure of 500 mm Hg (10 parts per square inch [psi]); use the flow metering
valve and a bubble flow meter or wet-test meter to obtain a flow rate of 1.5 t 0.1
L/min through the aeration cell. After the flow calibration is completed, remove the
bubble flow meter from the system.
Optical Cell Heating System Calibration-Using a 25-mL graduated cylinder, add
25 mL of water to the bottle section of the aeration cell. Attach the bottle section
to the bubbler section of the cell. Connect the aeration cell to the optical cell and,
while aerating at 1.5 L/min, determine the minimum variable transformer setting
necessary to prevent condensation in the optical cell and in the connecting tubing.
(This setting should not exceed 20 volts.)
Wavelength Adjustment-Set the spectrophotometer wavelength at 253.7 nm and
make certain that the optical cell is at the minimum temperature needed to prevent
water condensation.
Recorder Adjustment-The Hg response may be measured by either peak height or
peak area. Peak height determinations may be performed manually by counting the
recorder paper divisions for a given peak from a best-drawn baseline. The peak height
from the baseline also may be measured conveniently using a millimeter ruler. Peak
area measurements are most conveniently accomplished electronically using an integrator
or similar device. For peak height determinations, set the recorder scale as follows:
Note: The temperature of the solution affects the rate at which elemental Hg is
released froir. a solution and, consequently, it affects the shape of the generated peak
as well as the peak height. Therefore, to obtain reproducible results using peak
height, bring all solutions to room temperature before use.
-------
Section No. 3.19.5
Date September 3, 1992
Page 9
NEEDLE VALVE FOR
FLOW CONTROL EXIT ARM TO HOOD
5TUTCOCK
©G
TO VARIABLE TRANSFORMER
AERATION
CELL
OPTICAL CELL
MAGNETIC STIRRING BAR
FLOW
METER
N, CYLINDER
MAGNETIC STIRRER
Figure 5.3. Schematic of aeration system.
-------
Section No. 3.19.5
Date September 3, 1992
Page 10
1. Place a Teflon-coated stirring bar in the bottle. Using a 25-mL
graduated cylinder, add 25 mL of laboratory pure water to the aeration
cell bottle. Pipet 5.0 mL of the working Hg standard solution to the
aeration cell.
2. Add 5 mL of the 4% KMnO, absorbing solution followed by 5 mL of 15% HNOj
and 5 mL of 5% KMn04 to the aeration cell and mix well using a swirling
motion.
3. Attach the bottle to the aerator making sure that: (1) the exit arm
stopcock is closed, and (2) there is no aeration gas flowing through the
bubbler.
4. Through the side arm, add 5 mL of sodium chloride hydroxylamine solution
in 1-mL increments until the solution is colorless.
5. Through the side arm, add 5 mL of the Tin (II) reducing agent to the
aeration cell bottle and immediately stopper the side arm.
6. Stir the solution for 15 s and turn on the recorder or integrator.
7. Open the aeration cell exit arm stopcock and initiate the gas flow.
8. Determine the maximum height (absorbance) of the standard and set this
value to read 90% of the recorder full scale.
5.3.2 Analytical Calibration Curve-After setting the recorder scale (Section 5.3.1),
the calibration is performed. To separate aeration cell bottles, add 25 mL of
laboratory pure water. Then add 0.0-, 1.0-, 2.0-, 3.0-, 4.0-, and 5.0-mL aliquots of
the working standard solution using Class A volumetric pipets. This corresponds to 0,
200, 400, 600, 800, and 1,000 ng of Hg, respectively. Proceed with the calibration,
following steps 2 through 7 of Section 5.3.1, Recorder Adjustment. Analyze the
calibration standards by measuring the lowest to the highest standard. Be sure to
allow the recorder pen to return fully to the baseline before the next standard is
analyzed. This step is particularly critical with peak area measurements. Repeat this
procedure on each aliquot size until two consecutive peaks agree within 3% of the
average.
Between sample analyses, place the aerator section into a 600-mL beaker
containing approximately 400 mL of water. Rinse the bottle section of the aeration
cell with a stream of water to remove all traces'of the reagents from the previous
sample. These steps are necessary to remove all traces of the reducing agent between
samples to prevent the loss of Hg before aeration. It will be necessary, however,-to
wash the aeration cell parts with concentrated HC1 if any of the following conditions
occur: (1) a white film appears on any inside surface of the aeration cell; (2) the
calibration curve changes suddenly; or (3) the replicate samples do not yield
reproducible results.
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Section No. 3 .19 .5
Date September 3, 1992
Page 11
Recorder or integrator responses should be documented on the analytical data
form for Calibraxon Standards (Figure 5.4). Subtract the average peak height (or peak
area) of the measurement blank (0.0-mL aliquot)-which should be less than 2% of
recorder full scale-from the averaged peak heights of the 1.0-, 2.0-, 3.0-, 4.0-, and
5.0-mL aliquot standards. If the blank absorbance is greater than 2% of full-scale,
the probable cause is Hg contamination of a reagent or carry-over of Hg from a
previous sample. Plot the corrected peak height of each standard solution versus the
corresponding total Hg mass in the aeration cell (in ng).
Calculating the measured standard Hg mass (P) may be performed in two ways:
a linear regression program provided by a hand calculator (or other computing device)
or the manual least squares method described below:
P = (S)(Y) Equation 5-1
where:
Y = Peak height or integrator response, mm or counts.
S = Response factor, ng/mm or ng/counts (from Equation 5-2).
and
x1y,+x2y:+xJy3t-x4y4+x5y5+x6ys
S = Equation 5-2
where:
x = Standard mass value, ng.
Complete the analytical data form for analyzing calibration standards (Figure
5.4) for each standard. Calculate the deviation of each standard measurement average
from the expected value (standard mass value), x. If the percent deviation from the
expected value is greater than 5% for any standard measurement, the calibration must
be repeated. -
5.3.3 QC Operations—The quality of the analytical results can be assessed by
analyzing a variety of standard reference solutions (SRMs) of known high accuracy, such
as those available from the National Institute Standards and Technology (NIST) and
other government agencies. Standard solutions prepared by commercial suppliers that
meet NIST traceability criteria are also useful. If these solutions are not available,
the analysis of laboratory-prepared standard solutions may be used from a source
(supplier) other than the source of the calibration standards. These solutions will
be known as QC solutions. For example, if the calibration standards were prepared by
dilutions of a 100 mg Hg/mL solution from supplier A (or from an in-house prepared
solution from the pure mercury salt), then a QC solution might be prepared from
dilutions of one of the following:
1. An NIST Hg solution or other SRM.
-------
Section No. 3.19.5
Date September 3, 1992
Page 12
Plant
Date
Location
Analyst
Standard
Identifier
Standard
mass
(x)
(ng Hg)
Integrator Response,
Peak Height or Area
(y), (mm)
Measured
Standard
mass
(P)
(ng Hg)
Deviation
(%)
1
2
Avg
Std 1
0
Std 2
200
Std 3
400
Std 4
600
Std 5
800
1
1
Std 6
1000
1
1
Equation for Linear Calibration Curve, Average Response as a function of standard
concentration.
y = mx + b = (
I x + (
)
where:
y = Instrument curve slope mm or area count
ng Hg
x = Standard concentration (ng Hg) =
b = I = Intercept term (mm or area count) =
Measured Standard Concentration (P)
Equation 1
Equation 2
Equation 3
Equation 4
P(ng Hg) = Average Instrument Response (v) - Intercept (I!
Calibration Curve Slope
- (
J. =
ng Hg
Equation 5
Deviation
Deviation (%) = P (no Hg) - x (no Hg) x 100%
x (ng Hg)
Deviation
(
> - <
x 100% =
Equation 6
Figure 5.4. Analytical data form for analysis of calibration standards.
-------
Section No. 3.19.5
Date September 3, 1992
Page 13
2. A commercial QC solution that has been tested against an N1ST solution
(or equivalent) by manufacturer A.
3. A 1,000-mg Hg/mL solution from manufacturer B.
Record analytical data for QC samples on Figure 5.5. QC solutipns may be used
for a variety of analytical accuracy assessments. These include three check samples
(Check Sample A, B, and C):
A. Checks of the accuracy of the calibration operations, Check Sample
A-When analyzed immediately following the calibration, the measured QC
sample value must be within 5% of the expected value described in this
section, or the calibration must be repeated. These QC samples are
known as Initial Calibration Verification (ICVs) Check samples.
B. Checks of the drift of the calibration, Check Sample B-For any of a wide
variety of conditions that may be related to instrument warmup or
instrument component deterioration, the repeated analysis of a given
sample or standard will vary over time. To ensure that the analysis is
*in control," a QC solution is measured at least every five samples.
If the average measured value of the QC solution has changed by more
than 10% from the expected value, the causes must be identified and
corrected. The calibration is then repeated, and all samples analyzed
since the last successful 'drift* QC sample analysis must be repeated.
This "drift" QC sample is known as a CCV sample. It is worth noting
that the CCV need not be a "standard" type solution; any Hg-containing
solution may be used for the CCV, provided the Hg level in the aeration
cell is between 200 and 1,000 ng. Again, the measured value of this
solution must not vary more than 10% from the expected value.
C. Measuring spike recovery check sample, Check Sample C-Spiking a digested
sample (a prepared sample) with a standard solution provides a means of
assessing Hg recovery associated with the measurement process (sample
matrix effect). The steps below must be followed to determine spike
recovery: "*
a. After completing all sample preparation steps in Subsections 5.2.1
and 5.2.2, spike a 10-mL aliquot of Analysis Sample No. A.l with 10
mL of spiking solution containing a similar concentration of Hg, or
with 10 mL of a spike at least 10 times greater than the detection
limit, whichever is greater.
b. Spike a 10-mL aliquot of Analysis Sample No. HCl A.2 with 10 mL of
spiking solution containing a similar concentration of Hg as the
field sample, or a spike at least 10 times greater than the
detection limit, whichever is greater.
c. After all samples are analyzed, subtract the results of the spiked
and unspiked samples. If this spike is not within 15% of the expe-
cted value, then the Hg response may be owing to matrix effects. If
so, all sample digests must be analyzed by the method of standard
additions (MSA).
-------
Date samples received Date samples analyzed
Plant Run number(s)
Location Analyst
Calibration factor (S) Intercept (I), if applicable
1
1
1
QC |
Sample
Number
1
1
1
Analys is
Number
Instrument
Response
(mm)
Mean
Instrument
Response
(mm)
Percent
Deviat ion
(ng Hg)
Mean
Instrument
Response
Blank
Corrected
(y)
Dilution
Factor
(F)
Mass
QC
Sample
(ng Hg)
Deviation of replicate measurements, (%)
(A, - A2)
A i 4- A?
2
x 100
(
) - (
) ~ (
± 100 =
? Mass of QC sample
without intercept
(ng Hg)
Mass of QC sample
with intercept
(ng Hg)
= S x y x F
= S (y - I) F
DOB
ft P> (®
3
•O
rt z
® O
ID U)
M .
M
W U)
| (
Figure 5.5. Analytical data form for analysis of QC samples.
\o
K)
-------
Section No. 3.19.5
Date September 3, 1992
Page 15
Operations involving the use of QC samples are described in more detail below.
Note that spikes always must be measured using the linear portion of the calibration
curve (as with actual samples). QC samples with Hg values exceeding the linear portion
of the calibration curve must be diluted and reanalyzed according .to the sample
analysis procedure (Subsection 5.4.3).
Preparing the JCV Solutions-lf the source of the ICV is a commercial
1,000-mg/mL stock solution, it must be diluted according to the procedure described in
Subsection 1.5.3 for intermediate and working standard solutions.
Measuring the ICV Solution-Analyze a 2- to 5-mL aliquot (i.e., 200-500 ng Hg)
of the ICV working standard solution (some mid-point aliquot). Duplicate measurements
should agree within 3% of the average. If not, determine the cause for error (consult
the laboratory supervisor if necessary), correct the problem, and recalibrate the
analysis system. Repeat as necessary. If the QC solution source is not a 1,000-mg
Hg/mL stock solution, prepare the intermediate QC solution (QC working solution) as
follows:
1. Pour about 15 mL of the solution into a clean beaker. NOTE: To avoid
contamination, do not pipet directly from the bottle.
2. Pipet (using a glass pipet of at least 5-mL volume) an appropriate
aliquot into a suitable clean glass volumetric flask, according to Table
5.2. Pipet 2 mL of the QC working solution for measurement. Use Table
5.2 to determine the expected values for the QC sample (ICV).
Preparing and Measuring the Initial Blank Verification (IBV) and Continuing
Blank Verification (CBV)—With the conventional measurement system, these verifications
may be performed merely by adding 50 mL of water, hydroxylamine sulfate solution, and
stannous chloride as described in Subsection 5.3.2.
Preparing and Measuring Spiked Sample, Check Sample C— To determine whetfTer
there are sample matrix effects during the measurement, one sample digest must be
analyzed in the presence of added Hg. The added (spiked) Hg recovery must be within
85-115%, or the MSA must be employed for each sample and blank digest.
-------
TABLE 5.2 PREPARATION OF QC SOLUTIONS
QC working
Volume of
Certitied value of
Aliquot of QC
solution
working solution
Expected Hg
QC source solution
source solution
Dilut ion
concentrat ion
taken for
value, (ng)
(ng Hg/mL)
for dilution,(mL)
Volume, mL
using Eq. 1
analysis, (mL)
using Eq. 2
C.,.,
A
vd
(ng Hg/mL)
Cw.
v„
M
<1
-
2
1-5
5
100
2
5-20
5
250
2
20-100
5
1000
2
C.M x A Equation 1
Vd
where:
Cut = Concentration oE QC "working" solution (WSQC), ng Hg/mL.
C„td = Concentration in ng Hg/mL of QC source solution (QC) .
Vd = Dilution volume in mL.
A = Aliquot of QC source solution added to volumetric flask in mL.
Miig = Cu„ x Vp. Equation 2
do w
where: <§ £ o
(t)
-------
Section 3.19.5
Date April 3, 1992
Page 17
below:
The procedure used to determine the existence of matrix effects is described
1. Analyze an aliquot of the sample and record the sample aliquot size used
(see Subsection 5.4.3).
2. Calculate the Hg content in ng of the sample aliquot.
3. Determine a working standard aliquot size that equals or exceeds the
sample response from Step 2.
4. Add the value determined from Step 3 to an additional sample aliquot
identical to that used in Step 1.
5. Analyze this spiked sample and record the response.
6. The spike recovery is calculated as follows:
% Recovery = C spiked sample - C sample x 100
C spike
Equation 5-3
where:
C spiked sample
= Measured Hg in spiked sample, mg.
C sample
= Measured Hg in unspiked sample, mg.
C spike
= Hg added to sample, mg.
Note: To ensure the validity of the spike measurement, it is imperative that
the measurement result fall within the range of the calibration.
Method of Standard Addition Analysis-If the recovery result obtained from the
section above on the measurement of spiked samples falls outside the 85-115% range,
then the MSA must be employed for all sample digest measurements. This procedure is
described below:
1. Repeat steps 1 and 2 of spiked sample measurement above to determine the
level of Hg in the sample (designated S0) .
2. To a second, identical sample aliquot, add a working standard volume
that contains a Hg level that is approximately 50% of the sample Hg
level. Refer to this spiked sample as S1( and record the exact aliquot
volume of sample and working standard used.
3. Analyze spiked sample (Sj) .
4. To another, identical sample aliquot, add a working standard aliquot
that contains an Hg level that is approximately equal to that of the
sample. Refer to this spiked sample as S2, and record the exact aliquot
volume of sample and working standard used.
5. Analyze the spiked sample (S2) .
6. To another, identical sample aliquot, add a working standard aliquot
that contains an Hg level that is approximately 1.5 times that at the
sample. Refer to this spiked sample as S3, and record the exact aliquot
volume of sample and working standard used.
7. Analyze the spiked sample (S3) .
8. The peak intensity of each solution is determined and plotted on the
vertical axis of a graph. The concentrations of the known standards are
plotted on the horizontal axis. When the resulting line is extrapolated
back to zero absorbance, the point of interception of the abscissa is
the concentration of the unknown. The abscissa on the left of the
-------
Section 3.19.5
Date April 3, 1992
Page 18
ordinate is scaled the same as on the right side, but in the opposite
direction from the ordinate. An example is shown in Figure 5.6.
Zero
Absorbance
Mass (ng)
Addition 0 Addn 1
Ko addition of
Expected
Addn 2
10OX of
Expected
Addn 3
150* of
Expected
Concentration
of Sample
Amount Amount Amount
STANDARD ADDITION PLOT
Figure 5.6. Method of standard additions for field samples.
To perform a valid MSA analysis, three criteria must be met:
1. The MSA standard curve must be linear using the criteria in Subsection
5.3.2.
2. The spiking level of Hg must be at least 50% of Hg in the sample.
3. The spiking level must be at least 10 times the detection limit
(approximately 20 ng).
-------
Section 3.19.5
Date April 3, 1992
Page 19
5.3.4 Field Sample Analysis—Repeat the procedure used to establish the calibration
curve with an appropriately sized aliquot (1 to 5 mL) of the diluted sample until'two
consecutive peak heights agree as follows:
Ng mass, ng Limits (% deviation from average)
<5 50
5-15 15
15-100 5
>100 3
An aliquot peak maximum (except the 5-mL aliquot) must be greater than 10% of
the recorder full scale. If the peak maximum of a 1-mL aliquot is off scale on the
recorder, further dilute the original source sample to bring the Hg concentration into
the calibration range of the spectrophotometer.
Run a CBV and a CCV at least after every five samples to check the
spectrophotometer calibration drift; recalibrate as necessary (see Subsection 5.3.3).
It is recommended that at least one sample from each stack test be checked by the
method of standard additions to confirm that matrix effects have not interfered with
the analysis (see Subsection 5.3.3). Record all data for field sample analysis on the
Method 101A field analysis data form. Figure 5.7, or similar form.
Analysis Samples No. A.l and NCI A.2—After sample preparation of each sample
run, two sample fractions must be analyzed for Hg to determine the total ng of Hg.
Analysis Sample No. A.l is the filtrate of the KMnO, absorbing solution and rinse and
the digestate of the glass fiber filter, if applicable. Analysis Sample No. A.l will
be 1,000 mL or more, measured to within 1 mL. Analysis Sample No. HC1 A.2 is the
digestate of residue and Whatman 40 filter paper and HCl rinse, if applicable.
Analysis Sample No. HCl A.2 will be 500 mL. A recommended sequence of analysis is
presented in Table 5.3. "*
Analysis Samples No. A.l Blank and HCl A.2 Blank-Each test series requires
that a sample blank be taken. The sample blank is prepared in the same manner as the
field samples. The analysis of the sample blank will have the same two fractions as
each field sample. The blank will be analyzed at the same time and in the same manner
as the field samples, with the exception that a 10-mL aliquot shall be used for
analysis. A recommended sequence of analysis is presented in Table 5.3.
Container No. 2 (Silica Gel)4-Weigh the spent silica gel (or silica gel plus
impinger) to the nearest 0.5 g using a balance. (This step may be conducted in the
field. )
-------
Date samples received Date samples analyzed
Plant Run number(s)
Location Analyst
Calibration factor (S) Intercept (I), if applicable
1
1
Field
Sample
Number
Analysis
Number
Instrument
Response
(mm)
Mean
Instrument
Response
(mm)
Percent
Deviation
(ng Hg)
Mean
Instrument
Response
Blank
Corrected
(y)
Dilution
Factor
(F)
Mass
Field
Sample
(ng Hg)
(A, - Aj)
Deviation of replicate measurements, (%) = x 100
A, 4- A-)
2
= J ) - ( L ioo =
J ) ~ ( L
2
Mass of QC sample 2? p? Jd
io ft n
(t> > o
o*d n
H
H- U>
without intercept = S x y x F
Mass of QC sample
with intercept = S (y - I) F
(ng Hg) " L
u> \o
Kfl
M
IO
VO
(O
I I
Figure 5.7. Analytical data form for analysis of field samples.
-------
Section 3.19.5
Date April 3, 1992
Page 21
TABLE 5.3 RECOMMENDED ANALYTICAL SEQUENCE'
Sequence No. Sair.ple ID Sequence No. Sample ID
1 IBV 21 HCl A.2, Run 1 spike
2 repeat 22 repeat
3 ICV 23 A. 1, Run 2
4 repeat 24 repeat
5 CCV6 25 HCl A.2, Run 2
6 repeat 26 repeat
7 A.1 blank 27 A.l, Run 3
8 repeat 28 repeat
9 HCl, A.2 blank 29 HCl A.2, Run 3
10 repeat 30 repeat
11 A.l, Run 1 31 CCV
12 repeat 32 repeat
13 A.l Spike, Run lc 33 CBV
14 repeat 34 repeat
15 HCl A.2 Run lc 35 Repeat Calibration
16 repeatd
17 CCV
18 repeat
19 CBV
2 0 repeat
"Assuming a valid calibration has been performed.
"If different than ICV.
cAny A.l spike from runs 1, 2, or 3.
dAt this point, if the recovery is 85 to 115%, proceed to Step 26; if
not, all samples must be run using MSA (Subsection 5.3.3).
-------
Section 3.19.5
Date April 3, 1992
Page 22
5.4 Alternate Analytical Apparatus
Alternative systems are allowable as long as they meet the following criteria:
5.4.1 Measurement Technigue-The system is based on cold vapor atomic absorption
techniques.
5.4.2 Analyte Recovery—Eighty-five-115% of the spike is recovered when an aliquot
of a source sample is spiked with a known concentration of Hg (II) compound.
5.4.3 Calibration Curve-A linear calibration curve is generated and two consecutive
standards of the same aliquot size and concentration agree within the following limits.
Hg mass, ng/mL Limits (i deviation from average)
<0.5 50
0.5-1.5 15
1.5-10 5
>10 3
5.4.4 Sensitivity-The system is capable of detecting 0.2 ng Hg/mL for flow-injection
systems or 20 ng Hg for batch systems.
An example of a flow-injection analytical system is depicted in Figure 1.3.
Note that these systems inject samples in a semicontinuous manner; consequently, the
solution concentration is monitored, not the total Hg in the entire sample. Therefore,
the total Hg in a given sample digest is calculated as follows:
M„. = CHg x V Equation 5-4
where:
MH5 = Total mg Hg in each sample digest from Section 5.2.
CHg = Measured concentration in mg Hg/mL.
V = Total volume in milliliters of the sample digest.
These calculations are shown in Section 3.19.6.
5.4.5 Data Quality Assessment for Alternate Analytical Systems-QC solutions used to
determine the accuracy of the calibration may be measured directly without performing
the calculations described in Subsection 5.3.3. This procedure, of course, is based
on the assumption that the sample concentration value does not exceed that of the
highest calibration standard, thereby requiring a dilution.
-------
Section 3.19.5
Date April 3, 1992
Page 23
Determining matrix effects on the measurement recovery is performed as
follows:
1. Determine the Hg concentration in the sample digest.
2. Remove two 10-mL aliquots of the digest and place in clean 20-mL
beakers.
3. To one aliquot, add 1 xnL of distilled deionized water and mix by
swirling the beaker (Sc) .
4. To the other aliquot, add 1 mL of a standard that is 10 to 20 times the
solution concentration of the sample; mix the beaker contents (SJ .
5. Measure both solutions for Hg content.
6. The recovery of the added spike is as follows:
M« - Ms0
% Recovery = X 100 Equation 5-5
where:
Ms; = mg Hg in spiked sample.
= mg Hg/mL in Sj x 11 mL.
Ms( = mg Hg in sample spiked with water.
= mg Hg/mL (of spiking solution) x 1 mL.
The recovery should be between 85-115%. Otherwise, the method of additions
must be employed for each sample of the sample run. _
Method of Additions-ln this method, equal volumes of sample are added to a DI
water blank and to three standards containing different known amounts of the test
element. The volume of the blank and the standards must be the same. The absorbance
(peak height, counts, etc.) of each solution is determined and then plotted on the
vertical axis of a graph. The concentration of the known standards are plotted on trhe
horizontal axis. When the resulting line is extracted back to 2ero absorbance, the
point of interception of the abscissa is the concentration of the unknown. The
abscissa on the left of the ordinate is scaled the same as on the right side, but in
the opposite direction from the ordinate. An example is shown in figure 5.6.
5.5 Posttest Checklist
Posttest checklists for QC sample analysis and field sample analysis are
presented in figures 5.8 and 5.9.
-------
Section 3.19.5
Date April 3, 1992
Page 24
QC Sample Analysis Checklist
Date ______ Plant Name Sampling Location
Calibration Standards and Matrix Checks
Mercury Stock Solution, 1 mg Hg/mL:
Prepared in-house? (Y/N)
Source of mercury (II) chloride
Commercial stock solution? (Y/N)
Source
Intermediate Mercury Standard Solution, 10 mg/mL:
Date prepared
Used glass pipet? (Y/N)
Source and grade of HNOj
Working Mercury Standard Solution, 200 ng Hg/mL:
Prepared today? (Y/N) _________________
Used glass pipet? (Y/N) ________________
Calibration Standards:
mL of working standards volume of volumetric flask, mL
#1
#2
#3
*4
*5
* 6
#7
Instrumentation:
Spectrophotometer type ________________
Moisture Removal System:
Optical cell heating system? ________ Calibrated?
Moisture trap used? ______________ What type?
Data Recording System:
Recorder Integrator _______ Other
Describe
Peak height ______________ Peak area
Figure 5.8. QC sample analysis.
-------
Section 3.19.5
Date April 3, 1992
Page 25
Cold Vapor Generation System:
Standard batch system? ___
Alternate system?
Describe alternate system?
Aeration gas Aeration gas flow
Gas cylinder? Peristaltic pump?
Standardization:
Glass pipets used?
mL of Standard value*
working standard (ng) Reading 1 Reading 2 %Difference
"If using an alternate system that uses flow injection this value may be expressed as
concentration, e.g., |ig/L, ng/L, etc.
Calibration coefficient
Offset at origin (measured response of calibration blank) no or % of scafe.
Initial Calibration Verification (ICV);
QC check sample source
Certified or expected concentration
Measured concentration r
% Difference
Initial Calibration Blank Verification (IBV):
Measured value
Below detection limit?
Matrix Interference Check:
Method cf additions performed for one test site sample?
Spike added
Spike recovered
% recovery = Spiked sar.ple value - unspiked sample value =
spike value
Figure 5.8. (Continued)
-------
Section 3.19.5
Date April 3, 1992
Page 26
If the recovery was outside of 85-115%, were samples run using the method of standard
additions?
Describe
Continuing Calibration Verification (CCV) - Check sample of standard to be reanalyzed
after every five samples:
Standard used (source) ^__
Expected value/unit
Was measured value/unit always within 10% of expected value?
Final Standardization:
Glass pipets used?
mL of Standard value*
working standard (ng) Reading 1 Reading 2 %Difference
"Alternate analytical systems may express Hg value as a concentration (e.g., mg/L Hg) .
Calibration coefficient
Offset at origin ng or % of scale.
Figure 5.8. (Continued)
-------
Section 3.19.5
Date April 3, 1992
Page 27
Sample Analysis Checklist
Date ________ Time _____ Operator Observer ¦
Sample Analysis
Were all sample digests analyzed within 48 h of preparation? (Y/N)
Were 10 mL of samples A.l blank and HC1 A.2 blank used as a minimum?
(Y/N)
Were duplicate measurements performed as a minimum for all blank and sample digests?
(Y/N)
Did duplicate measurements meet the "percent difference" criteria outlined in Table 5.2
(Y/N)
Was the largest possible aliquot (20 mL) used when a measurement was below the
detection limit? (Y/N)
If a sample measurement exceeded the highest calibration standard, were appropriately
smaller aliquots always taken to ensure that results fell within the calibration range?
(Y/N)
If 1-mL aliquots taken for measurement still were off scale, were sample digests
diluted so that results were within the linear range of the standards? (Y/N)
What volumetric glassware (pipets) was used to add sample digests to the aeration
flasks? (mL)
What volumetric glassware (pipets/flasks) was used to dilute sample digests?
_ (if necessary)
If the calibration check samples differed by greater than 10% of the expected values,
was the system recalibrated? (Y/N) -
Were CBV and CCV samples analyzed after ever five samples? (Y/N)
Were all samples run after the previously CBV and CCV sample analyses?
(Y/N)
Was the full standardization performed at the end of the sample analysis? (Y/N)
Figure 5.9. Method 101A sample analysis checklist.
-------
Section 3.19.5
Date April 3, 1992
Page 28
TABLE 5.1 ACTIVITY MATRIX FOR SAMPLE ANALYSIS
Characteristic
1
1
|Acceptance limits
1
1
(Frequency & method
|of measurement
1
|Action if
(requirements
|are not met
1
Sample
preparation
|Samples and
|blanks prepared
I under same
|conditions
1
1
|
1
1
1
1
1
I Adjust
(dilutions, if
I possible;
(otherwise report
|to Administrator
All
calibrations
|(1) Reagents and
|volumes used
I during
|measurement of
|samples and
I standards are
|identical
1
|Dilute samples so
Ithat matrix
(concentrations are
|are identical to
I original sample
I digest
1
(Reanalyze
I samples
1
1
1
1
1
I
l
1(2) Perform
I6-point
[calibration curve
I including
I calibration blank
|
1
I Prepare fresh
I daily
1
1
|
1
I Prepare fresh
I daily
1
1
1
l
1
1(3) Calibration
I coefficient
I better than 0.999
1
1
1
1
|Each calibration
I point is the
leverage of
|duplicate
(measurements
1
1
|Repeat
|calibration
1
1
1
Calibration
Verification
Check Samples
(ICV)
lAnalysis within
15% of expected or
(certified value
1
1
|Analyze after
(every calibration
1
1
1
I Ensure quality
|of check sample
(or repeat
I calibration
1
Calibration
Blanks
Verif icat ion
(IBV)
|Must be below
I detection limit
1
1
1
1
|Analyze after
|every
|calibration
1
1
1
|Check for
|potential
|contamination
(and repeat
I calibration
1
Continuing
Calibration
Verif ication
Sample (CCV)
|Must be within
110% of expected
I value
1
1
|Analyze after
(every 5th sample
1
1
1
|Repeat
|calibration
land repeat all
|samples since
|last successful
ICCV analysis
(Continued)
-------
Section 3 .19 .5
Date April 3, 1992
Page 29
TABLE 5.1 (Continued)
Characteristic
1
1
|Acceptance limits
1
1
|Frequency & method
|of measurement
1
lAction if
I requirements
I are not met
I
Continuing
Blank
Verification
(CBV)
|Must be below
(detection limit
1
1
1
1
|Analyze after
|every 5th sample
1
1
1
1
t
|Repeat
I calibration
(and repeat all
I samples since
I last successful
ICBV analysis
1
Matrix check
sample
|Recovery of
|sample digest
jspike 85-115%
1
1
1
1
1
|One sample digest
|from every stack
|test is spiked at
|a level at least
|equal to sample
|digest
|concentration
1
lAnalyze all
I samples using
I the method of
I standard
I additions
1
1
1
Duplicate
measurements
|See Subsec.
|5.3.2
1
|All standard and
|sample analyses
1
|Repeat until
|agreement is
|achieved
1
Data recording
|All pertinent
Idata recorded
I on figs . 5.1, 5.2
1
|Visually check
1
1
1
I Supply missing
j data
1
1
-------
Section No. 3.19.6
Date September 3, 1992
Page 1
6.0 CALCULATIONS
Calculation errors resulting from procedural or mathematical mistakes can be
a part of total system error. Therefore, it is recommended that each set of calcula-
tions be repeated or spotchecked, preferably by a team member other than the one who
performed the original calculations. If a difference greater than typical round-off
error is detected, the calculations should be checked step-by-step until the source of
error is found and corrected.
Calculations should be carried out to at least one extra decimal figure beyond
that of the acquired data and should be rounded off after final calculation to two
significant digits for each run or sample. All rounding of numbers should be performed
in accordance with the ASTO 380-76 procedures.
A computer program is advantageous in reducing calculation errors. If a
program is used, the original data entered 6hould be included in the printout for
review. If differences are observed, a new computer run should be made. A computer
program also is useful in maintaining a standardized format for reporting results. The
data shown will allow auditing the calculations.
Table 6.1 at the end of this section summarizes the QA activities for
calculations.
In the next section, nomenclature and equations have been divided into two
groups. The first group (Section 3.19.6.1 to 3.19.6.4) deals with sampling calcula-
tions. The second group (Section 3.19.6.5 to 3.19.6.13) deals with analytical and
emissions calculations.
6.1 Sampling Nomenclature from Method 5
A„ = Cross-sectional area of nozzle, mJ (ft2) .
Bwt = Water vapor in the gas stream, proportion by volume.
I = Percent of isokinetic sampling.
L, = Maximum acceptable leakage rate for either a pretest leak check or
for a leak check following a component change, equal to 0.0 0057
mVmin (0.02 cfm) or 4% of the average sampling rate, whichever is
less.
L, = Individual leakage rate observed during the leak check conducted
prior to the ¦ith• component change (i = 1, 2, 3...n), nvVmin (cfm).
Lj = Leakage rate observed during the posttest leak check, m3/min (cfm).
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lbmole).
PMr = Barometric pressure at the sampling site, mm Hg (in. Hg).
P, = Absolute stack gas pressure, mm Hg (in. Hg).
P,[d = Standard absolute pressure, 760 mm Hg (29.92 in. Hg) .
R = Ideal gas constant, 0.06236 [(mm Hg)(m3) ]/[(°K)(g-mole)] {21.85 [(-
in. Hg)(ft3)]/[(°R)(lb-mole)]).
-------
Section No. 3.19.6
Date September 3, 1992
Page 2
Absolute average DGM temperature, °K (°R).
Absolute average stack gas temperature, °K (°R).
Standard absolute temperature, 293 °K (528R).
Total volume liquid collected in impingers and silica gel, mL.
Volume of gas sample as measured by dry-gas meter, dcm (dcf).
Volume of gas sample measured by the dry-gas meter, corrected to
standard conditions, dscm (dscf).
Volume of water vapor in the gas sample, corrected to standard
conditions, scm (scf).
Stack-gas velocity, calculated by Method 2, Equation 2-9, using
data obtained from Method 5, m/s (ft/s) .
Dry-gas meter calibration factor.
Average pressure differential across the orifice meter, mm H20 (in.
H;0) .
Density of water, 0.9982 g/mL (0.002201 lb/mL).
Total sampling time, min.
Sampling time interval, from the beginning of a run until the first
component change, min.
Sampling time interval, between two successive component changes,
beginning with the interval between the first and second changes,
min.
Sampling time interval, from the final (nth) component change until
the end of the sampling run, min.
Specific gravity of mercury.
S/min.
Conversion to %.
-------
6.2
Conversion Factors
Section No. 3.19.6
Date September 3, 1992
Page 3
6.3
6.4
From
To
Multiply bv
scf
m3
0.02832
-g/ft3
gr/ft3
15.43
g/ft3
lb/ft3
2.205 x 10°
g/ft3
g/m3
35.31
Average Drv-Gas Meter Temperature and Average Orifice Pressure Drop
See data sheet (Figure 4.1).
Drv-Gas Volume
Correct the sample volume measured by the dry-gas meter to standard conditions
(20 °C, 760 mm Hg or 68 °F, 29.92 in. Hg) by using Equation 6-1.
. AH
Tscd (^bar
v = v y
ffl
TTTT
)
Tm P.td
V = K,VmY
* (-^)
AH
13.6' Equation 6-1
T.
where:
K, = 0.3858 °K/mm Hg for metric units.
= 17.64 °R/in Hg for English units.
Note: Equation 6-1 can be used as written unless the leakage rate observed
during any of the mandatory leak checks (i.e., the posttest leak check or leak checks
conducted prior to component changes) exceeds Lt. If L,, or L, exceeds L,, Equation 6-1
must be modified as follows:
(a) Case I. No component changes made during sampling run. In this case, replace Vr
in Equation 6-1 with the expression:
K - - i.) 9)
-------
Section No. 3.19.6
Date September 3, 1992
Page 4
(b) Case II. One or more component changes made during the sampling run. In this
case, replace V„ in Equation 6-1 by the expression:
[Vm - (Lj - LJ e, - £ (L, ~La) 6, - (Lp - La) ep]
i'2
and substitute only for those leakage rates (L, or Lp) that exceed L..
6.5 Volume of Water Vapor
* Vlc y.T"J - K, VJC Equation 6-2
1 V Bid
where:
K2 = 0.001333 m'/mL for metric units.
= 0.04707 ft'/mL for English units.
6 . 6 Moisture Content
B„s = Vb,(s:dl Equation 6-3
irtstd) w(std)
Note: In saturated or water droplet-laden gas streams, calculate the moisture
content of the stack gas in two ways: from the impinger analysis (Equation 6-3) a*id
from the assumption of saturated conditions. The lower for B„, shall be considered
correct.. The procedure for determining the moisture content based upon assumption of
saturated conditions is given in the Note of Section 1.2, Method 4. For the purposes
of this method, the average stack-gas temperature from Figure 4.2 may be used to make
this determination, provided that the accuracy of the in-stack temperature sensor is
i 1 °C [2 °F).
6 .7 Nomenclature frorr Method 2
A = Cross-sectional area of stack, mJ (ft5) .
= Water vapor in the gas stream (from Method 5 or Reference Method
4), proportion by volume.
C( = Pitot tube coefficient, dimensionless.
= Pitot tube constant - 34.97 for the metric system and 85.49 for
the English system.
Ma = Molecular weight of stack gas, dry basis (see Section 3.6),
g/g-mole (lb/lb-mole).
Mf = Molecular weight of stack gas, wet basis, g/g-mole (lb/lb-mole).
-------
Section No. 3.19.6
Date September 3, 1992
Page 5
= Ma (1 - B,,,) + 18.0 B„.
P,,., = Barometric pressure at measurement site, mm Hg (in. Hg) .
Pg = Stack static pressure, mm Hg (in. Hg).
P. = Absolute stack pressure, mm Hg (in. Hg),
= PMr + Ps
P,td = Standard absolute pressure, 760 mm Hg (29.92 in. Hg) .
Q,d = Dry volumetric stack gas flow rate corrected to standard condi-
tions, dsm3/h (dscf/h).
t, = Stack temperature, °C (°F).
Tt = Absolute stack temperature, °K (°R).
= 273 + t, for metric.
= 460 -f t, for English.
T„ld = Standard absolute temperature, 293 °K (528 °R) .
vt = Average stack gas velocity, m/sec (ft/s).
Ap = Velocity head of stack gas, mm H20 (in. H20) .
3,600 = Conversion factor, s/h.
18.0 = Molecular weight of water, g/g-mole (lb/lb-mole).
6.8 Average Stack Gas Velocity
v. = Kp Cp (v£F)
Tsiavg) Equation 6-4
-------
Section No. 3 .19.6
Date September 3, 1992
Page 6
6.9
Average Stack Gas, Dry Volumetric Flow Rate
Q = 3600 (1 -Bus) vs A T
^Btd Pc
p
s(avg) •* std
6.10 Isokinetic Variation
6.10.1 Calculation from Raw Data-
Equation 6-5
I =
100 T, [K, Vle
-------
6.12
Section No. 3.19.6
Date September 3, 1992
Page 7
Method 101A Calculations
6.12.1 Determining Compliance-Each performance test consists of three repetitions of
the applicable test method. For the purpose of determining compliance with an
applicable national emission standard, use the average of the results of all
repetitions.
6.12.2 Total Hg-Tor each source sample, correct the average maximum absorbance of the
two consecutive samples whose peak heights agreed within 3% of their average for the
contribution of the blank. Then calculate the total Hg content in |ig in each sample.
Correct for any dilutions made to bring the sample into the working range of the
spectrophotometer.
where:
f C
-------
Section No. 3.19.6
Date September 3, 1992
Page 8
S = Aliquot volume of sample added to aeration cell, mL.
SMk = Aliquot volume of blank added to aeration cell, mL.
Note: The maximum allowable blank subtraction for the HC1 is the lesser of the
two following values: (1) the actual blank measured value (Analysis Sample No. HC1 A.2
blank); or (2) 5% of the Hg content in the combined HC1 rinse and digested sample
(Analysis Sample No. HCl A.2).
m
( f ]ID Hj
l /Jcrl Hg
DF
T-
V,
filler)
*blk
where:
lcns JDFblk 10"3 Equation 6-10
•Si.
m,n,MHg = Total blank corrected jig of Hg in KMn04 filtrate and HN03 di-
gestion of filter sample.
C(,llIIHB = Total ng of Hg in aliquot of KMn04 filtrate and HNOj digestion
of filter analyzed (aliquot of Analysis Sample A.l).
ci!itr buiHsi = Total ng of Hg in aliquot of KMnO« blank and HN03 digestion of
blank filter analyzed (aliquot of Analysis Sample No. A.l
blank).
V(l(Ur, = Solution volume of original sample, normally 1000 mL for
samples diluted as described in Section 7.3.2 of Method 101A.
V, lt,u 1 = Solution volume of blank sample, 1000 mL for samples diluted as
described in Section 7.3.2 of Method 101A.
Note: The maximum allowable blank subtraction for the HCl is the lesser of the two
following values: (1) the actual blank measured value (Analysis Sample No. A.l blank);
or (2) 5% of the Hg content in the filtrate (Analysis Sample No. A.l).
-------
Section No. 3.19.6
Date September 3, 1992
Page 9
™Kg ~ * ™illir)Hg Equation 6~11
where:
= Total blank corrected Hg content in each sample, Jig.
ttiihci ,M9 = Total blank corrected Jig of Hg in HC1 rinse and HC1 digestate of
filter sample.
mimriMs = Total blank corrected |ig of Hg in KMn04 filtrate and HNOj di-
gestion of filter sample.
6.12.3 Mercury Emission J?ate-Calculate the Hg emission rate R in g/day for continuous
operations using Equation 101A-6 in Method 101A. For cyclic operations, use only the
time per day each stack is in operation. The total Hg emission rate from a source will
be the summation of results from all stacks.
mna vsA.(86,400xl0"6) r
R = K _J2 I i . Equation 6-12
lVmlstdl + Vw{.td)l ITJ Ps)
where:
nvf = Total blank corrected Hg content in each sample, jig.
v5 = Average stack gas velocity, m/s (fps).
As = Stack cross-sectional area, mJ (ftJ) .
86,400 = Conversion factor, s/day.
10'* = Conversion factor, g/Jig.
v».stdi = Dry-gas sample volume at standard conditions, corrected for
leakage (if any), m3 (ft3).
V.„.d = Volume of water vapor at standard conditions, m3 (ft3).
T„ = Absolute stack-gas temperature, CK (°R).
Ps = Absolute stack-gas pressure, mm Hg (in. Hg).
K = 0.3858 °K/mm Hg for metric units.
K = 17.64 °R/in. Hg for English units.
-------
Section No. 3 .19.6
Date September 3, 1992
Page 10
6.13 Determining Compliance
Each performance test consists of three repetitions of the applicable test
method. For the purpose of determining compliance with an applicable national emission
standard, use the average of the results of all repetitions.
6.14 Hq Calculation for Alternate Analytical Systems
For alternate analytical systems, in which Hg is measured as a concentration
(mg Hg/L of sample) the Hg in mg (m«g) in the original solution is calculated as
follows:
m„9 = CM0 x
-------
Section No. 3.19.7
Date September 3, 1992
Page 1
7.0 MAINTENANCE
The normal use of emission testing equipment subjects it to corrosive gases,
extremes in temperature, vibration, and shock. Keeping the equipment in good operating
order requires knowledge of the equipment and a program of routine maintenance
performed quarterly or after 1000 ft3 of operation, whichever is greater. In addition
to the quarterly maintenance, cleaning pumps and metering systems annually is
recommended. Maintenance procedures for the various components are summarized in Table
7.1 at the end of this section. The following procedures are not required, but they
are recommended to increase the reliability of the equipment.
7.1 Sampling Equipment
7.1.1 Pump-Several types of pumps may be used to perform Method 101A; the two most
common are the fiber vane pump with in-line oiler and the diaphragm pump. The fiber
vane pump requires a periodic check of the oiler jar. Its contents should be translu-
cent; the oil should be changed if not translucent. Use the oil specified by the
manufacturer. If none is specified, use SAE-10 nondetergent oil. Whenever a fiber
vane pump starts to run erratically, or during the yearly disassembly, the head should
be removed and the fiber vanes changed.
The diaphragm pump requires little maintenance. If the diaphragm pump leaks
or runs erratically, it is normally due to a bad diaphragm or malfunctions in the
valves; these parts are easily replaced and should be cleaned annually by complete
disassembly of the train.
7.1.2 Dry-Gas Weters-The dry-gas meter should be checked for excess oil and
component corrosion by removing the top plate every 3 months. The meter should be
disassembled, and all components should be cleaned and checked more often if the dials
show erratic rotation or if the meter will not calibrate properly. "
7.1.3 Inclined Manometer-The fluid should be changed when it is discolored or
contains visible matter and when it is disassembled yearly. No other routine
maintenance is required because the inclined manometer is evaluated during the leak
checks of both the pitot tube and the entire meter box. _
7.1.4 Sampling Train-All remaining sample train components should be visually
checked every 3 months, and they should be completely disassembled and cleaned or
replaced yearly. Many of the items, such as quick disconnects, should be replaced only
when damaged.
7.2 Analytical Instruments
7.2.1 Spectrophotometer-Consu.It the manufacturer's operation manual for specific
maintenance activities.
7.2.2 Peristaltic Pump Tubing-Inspect pump tubing daily. The tubing should not have
flat spots where it has contacted the pump rollers and should feel flexible. Replace
tubing if this is not the case.
7.2.3 Desiccant-If a moisture trap is used instead of a heated optical cell, the
desiccant should be replaced daily. Both tube ends should be filled with glass wool;
the dessicant must not be packed too tightly.
-------
Section No. 3.19.7
Date September 3, 1992
Page 2
7.2.4 Optical Celi—'The windows of the optical cell should be inspected daily for any
dust, dirt, or grease that will degrade light throughput and overall analytical
performance. Wash gently with detergent and rinse well. Dry by blotting with a towel
and wipe, if necessary, with lens paper only.
7.2.5 Spectrophotometer Windows—The windows of the spectrophotometer must also be
inspected (at least weekly) and cleaned as described in section above.
7.2.6 Tygon Connecting Tubing-Connection tubing must be inspected on a daily basis
(or more frequently) for condensation or dirt. Replace if
necessary. The existence of moisture after the dessicant trap (if used)
indicates that the dessicant needs replacing. Refer to Section 7.2.3.
-------
Section No. 3.19.7
Date September 3, 1992
Page 3
TABLE 7.1 ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS
Apparatus
1
I Acceptance
I limits
1
1
I Frequency and method
|of measurement
1
lAction if
|requirements
|are not met
1
Samclina
Eauioment
Routine
maintenance
1
1
|No erratic
|behavior
1
1
1
1
1
1
I Routine maintenance
|quarterly, or after
jlOOO ft3 of use;
(disassemble and
I clean yearly
1
1
1
I Replace parts
1
1
1
1
Fiber vane
pump
I Leak-free;
|required flow
1
1
1
1
|Periodic check of
|oil jar; oil changed
|if not translucent;
|change fiber vanes
|yearly or when
I running erratically
1
I Replace as
I needed
1
1
1
1
1
Diaphragm
pump
|Leak-free valves
I functioning
|properly;
1 required flow
1
|Clean valves during
lyearly disassembly
1
1
1
|Replace when
I leaking or when
I running
I erratically
1
Dry-gas
meter
|No excess oil,
|corrosion, or
lerratic dial
|rotat ion
1
1
1
1
1
1
1
|Check every three
|months for excess
|oil or corrosion by
|removing the top
|plate; check valves
|and diaphragm when
Imeter dial runs
I erratically or when
Imeter will not
I calibrate
1
|Replace parts as
|needed, or meter
1
1
1
1
1
1
1
Inclined
manometer
I No discoloration
|o£ or visible
I matter in the
I fluid
1
|Check periodically;
I change fluid during
lyearly disassembly
1
1
|Replace parts as
I needed
1
1
1
Sample
train
|No damage or
I leaks
1
1
1
1
1
Ivisually check every
|3 months; completely
|disassemble and
| clean or replace
| yearly
1
1
|lf failure
|noted, use
|another entire
|control console,
I sample box, or
|or umbilical
I cord
(Continued)
-------
Section No. 3.19.7
Date September 3, 1992
Page 4
TABLE 7.1 Checks (Continued)
Apparatus
1
|Acceptance
I limits
1
1
I Frequency and method
|of measurement
1
|Action if
|requirements
I are not met
1
Analytical
Instruments
1
1
I
1
1
1
1
1
I
Spectro-
photometer
1
|See owner's
I manual
I
1
|See owner's manual
|manual
1
1
|See owners
1
1
Peristaltic
pump tubing
I Flexible; no
I flat spots
1
I Visually inspect
I tubing daily
1
|Replace
1
Desiccant
I Fresh or dry
|used silica gel;
|no moisture
1
I Inspect daily
1
1
1
|Replace
1
1
1
Optical
cell
I Clean of dust,
Idirt, grease,
I etc.
1
1
|Inspect daily
1
1
1
|Clean gently
|with detergent;
|rinse; blot with
|towel
1
Spectro-
photometer
windows
I Same as above
1
1
1
I Inspect weekly
1
1
1
|Same as above
1
1
1
Tygon
connecting
tubing
|No condensation
|or dirt
1
1
I Inspect daily
1
1
1
|Replace
¦ ^
1
1
-------
Section No. 3.19.8
Date September 3, 1992
Page 1
8.0 AUDITING PROCEDURES
An audit is an independent assessment of data quality. Independence is
achieved when the persons performing the audit apply standards and equipment different
from the standards and equipment of the regular field team. Routine QA checks by a
field team are necessary to generate quality data, but they are not part of the
auditing procedure. Table 8.1 at the end of this section summarizes the QA functions
for auditing.
One performance audit is recommended when testing for compliance with National
Emission Standards for Hazardous Air Pollutants (NESHAPs), with New Source Performance
Standards (NSPS), and as required by other government agencies. A performance audit
is recommended when testing for other purposes; and two other performance audits are
recommended. The three performance audits are:
1. An audit of the analysis of Method 101A is recommended for NESHAPs. The
use of an NIST-traceable control sample is recommended for NSPS testing
and for other purposes.
2. An audit of the sampling is suggested by Method 101A and is recommended
by the QA Handbook.
3. An audit of the data processing is also recommended.
It is suggested that a systems audit be conducted as specified by the QA
coordinator in addition to these performance audits. The two performance audits and
the systems audit are described in detail in Subsections 8.1 and 8.2, respectively.
8.1 Performance Audits
Performance audits are conducted to evaluate quantitatively the quality of
data produced by the sampling, analysis, or the total measurement system (sample
collection, sample recovery, sample analysis, and data processing).
8.1.1 Performance Audit of Method 101A Analysis—A performance audit for Method 101A
analysis is recommended for NESHAPs and NSPS testing using a control sample that is
NIST-traceable. Although the control sample values are known to the analyst, the
successful analysis of a control sample, as described in Subsection 5.3.3, makes the
results traceable to an NIST standard. -
8.1.2 Performance Audit of the Field Test-The dry-gas meter calibration should be
checked by one of the two techniques shown below (meter orifice check or critical
orifice check).
Meter Orifice Check-Using the data obtained during the calibration procedure
described in Section 5.3, determine the AH, for the metering system orifice. The AHS
is the orifice pressure differential in units of in. H20 that correlates to 0.75 cfrn
of air at 528 °R and 2S.92 in. Hg. The AHe is calculated as follows:
&
Pbar Y2 K
AHf = T Equation 8-1
where:
AH = Average pressure differential across the orifice meter, in. H2C.
-------
Section No. 3.19.8
Date September 3, 1992
Page 2
T„ = Absolute average DGM temperature, °R.
Pb.r = Barometric pressure, in. Hg.
© = Total sampling time, min.
Y = DGM calibration factor, dimensionless.
V. = Volume of gas sample as measured by DGM, dcf.
Before beginning the field test (a set of three runs usually constitutes a
field test), operate the metering system (i.e., pump, volume meter, and orifice) at the
pressure differential for 10 min. Record the volume collected, the DGM tempera-
ture, and the barometric pressure. Calculate a DGM calibration check value, Yc, as
follows:
y - 10
c v.N
0.0319 ?. _
Equation 8-2
where:
Yc = DGM calibration check value, dimensionless.
10 r Run time, min.
0.0319.= (0.0567 in Hg/°R)(0.75 cfm)2.
Compare the Yc value with the dry-gas meter calibration factor, Y, to
determine that: 0.97Y
-------
Section No. 3 .19.8
Date September 3, 1992
Page 3
where:
vcn.td> = K' (Pt,., 0)/T„b1/J Equation 8-4
Y — VcrntdiEquation 8-5
vcn.idi = Volume of gas sample passed through the critical orifice, correct-
ed to standard conditions, dscm (dscf).
K' = 0.3858 °K/mm Hg for metric units
= 17.64 °R/in Hg for English units.
7. Average the DGM calibration values for each of the flow rates. The
calibration factor, Y, at each of the flow rates should not differ by
more than ± 2* from the average.
8.1.3 Performance Audit of Data Processing-Calculation errors are prevalent when
processing data. Data processing errors can be determined by auditing the recorded
data on the field and laboratory forms. The original and audit (check) calculations
should agree within round-off error; if not, all of the remaining data should be
checked. Data processing also may be audited by requiring that the testing laboratory
provide an example calculation for one sample run. This example calculation will
include all the calculations used to determine the emissions based on the raw field and
laboratory data.
8.2 System Audit
A system audit is an on-site, qualitative inspection and review of the total
measurement system. Initially, a system audit is recommended for each enforcement
source test, defined here as a series of three runs at a source.
The auditor should have extensive background experience with source sampling
or source test observation, specifically with Method 101A or Method 5. The auditor's
functions are summarized below:
1. Observe procedures and techniques of the field team during sample
collection and sample recovery.
2. Check/verify records of apparatus calibration checks and QC used in the
laboratory analysis.
While on-site, the auditor observes the source test team's overall
performance, including the following specific operations:
1. Setting up the sampling system and checking the sample train ana pitot
tube for leaks.
2. Collecting the isokinetic sampling.
3. Conducting the final leak checks.
4. Sample documentation procedures, sample recovery, and preparation of the
samples for shipment.
Figure 4.3 in Section 3.19.4 is a suggested field observation checklist for 101A
sampling and sample recovery, and Figure 5.9 in Section 3.19.5 is a suggested checklist
for 101A sample analysis.
-------
Section No. 3.19.B
Date September 3, 1992
Page 4
TABLE 8.1 ACTIVITY MATRIX FOR AUDITING PROCEDURES
Apparatus
1
|Acceptance
I limits
1
1
|Frequency and method
|of measurement
1
|Action if
I requirements
I are not met
1
Performance
audit of
analytical
phase
I Measured
I relative error of
I audit samples
jless than 15%
|(or other stated
lvalue) for both
|samples
1
1
iFreauencv: Once
|during every
I enforcement source
I test*
1 Method: Measure
I audit samples and
|compare results to
|true values
I
|Review
|operating
I technique and
I repeat audit
1
1
1
1
1
Volumetric
sampling
|Measured pretest
|volume within
|± 10% of the
I audit volume
1
1
1
1
1
IFreauencv: Once
I during every
I enforcement source
I test*
1 Method: Measure
I reference volume and
I compare with true
I volume
1
|Review
I operating
I techniques
1
1
1
1
1
1
Data
processing
errors
lOriginal and
I checked
I calculations
|agree within
|round-off error
1
1
1
IFreauencv: Once
|during every
I enforcement test*
1 Method: Independent
I calculations
|starting with
|recorded data
1
I Check and
I correct all data
|for the audit
|period
I represented _
|by the
|sampled data
1
Systems
audit-
observance
of
technique
I Operational
I technique as
|described in
Ithis section of
|the Handbook
1
1
1
1
1
1
1
1Freouencv: Once
I during every
I enforcement source
|source test* until
I experience gained,
|then every third
I test
1 Method: Observation
|of techniques
|assisted by audit
Ichecklist (Fig. 4.2)
1
I Explain to team
|their deviations
|from recommended"
|techniques and
|note on Fig. 4.2
1
1
1
1
1
1
1
•As defined here, a source test lor en 1 orcement comprises a series of three runs ac one source. Source test
for purposes other than enforcement may be audited at the frequency determined by the applicable group.
-------
Section No. 3.19.9
Date September 3, 1992
Page 1
9.0 RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
To achieve data of desired quality, two essential considerations are
necessary: (1) the measurement process must be in a state of statistical.control at the
time of the measurement; and (2) the systematic errors, when combined with the random
variation (errors or measurement), must result in an acceptable uncertainty. Evidence
of quality data results from performing QC checks and independent audits of the
measurement process, documenting these data, and using materials, instruments, and
measurement procedures that can be traced to an appropriate standard of reference.
Data must be routinely obtained by repeatedly measuring standard reference
samples (primary, secondary, and/or working standards) and by establishing a condition
of process control. The working calibration standards must be traceable to standards
of higher accuracy by using a control sample or by purchasing working calibration
standards that are NIST-traceable.
Performance audit samples are not required for determining compliance;
however, an NIST control sample is recommended (as discussed in Section 3.19.8). A
control sample is also recommended as an independent check on the measurement process
when the method is performed for other purposes. This procedure makes all the
compliance determination samples traceable to an NIST standard.
-------
Section No. 3.19.10
Date September 21, 1992
Page 1
10.0 REFERENCE METHODS: METHOD 101A-DETERMINATION OP PARTICULATE AND GASEOUS
MERCURY EMISSIONS PROM STATIONARY SOURCES
This method is similar to Method 101, except acidic potassium permanganate
solution is used instead of acidic iodine monochloride for sample collection.
1.0 APPLICABILITY AND PRINCIPLE
1.1 Applicability
This method applies to determining particulate and gaseous Hg emissions from
sewage sludge incinerators and other sources, as specified in the regulations.
1 .2 Principle
Particulate and gaseous Hg emissions are withdrawn isokinetically from the
source and collected in acidic potassium permanganate (KMnOJ solution. The Hg
collected (in mercuric form) is reduced to elemental Hg, which is then aerated from the
solution into an optical cell and measured by atomic absorption spectrophotometry.
2.0 RANGE AND SENSITIVITY
2 .1 Ranae
After initial dilution, the range of this method is 20 to 800 ng Hg/mL. The
upper limit can be extended by further dilution of the sample.
2.2 Sensitivitv _
The sensitivity of the method depends on the recorder/spectrophotometer
combination selected.
3.0 INTERFERING AGENTS
3 .1 Samelino
Excessive cxidizable matter in the stack-gas prematurely depletes the KMnC.
solution and, thereby, prevents further collection of Hg.
This section represents Method 101A and referenced procedures from Method 10.. Text
from Method 101 is shown in bold italics.
-------
Section No. 3.19.10
Date September 21, 1992
Page 2
3 .2 Analysis
Condensation of water vapor on the optical cell windows causes positive
interference.
4.0 PRECISION
Based on eight paired-train tests, the within-laboratory standard deviation
was estimated to be 4.8 (ig/mL in the concentration range of 50 to 130 ng/m3.
5.0 APPARATUS
5 .1 Sampling Train and Sample Recovery
Same as in Method 101, Sections 5.1 and 5.2, respectively, except for the
following variations:
5.1.1 Probe Nozzle, Pitot Tube, Differencial Pressure Gauge, Metering System,
Barometer, and Gas Density Determination Equipment—Same as in Method 5, Sections 2.1.1,
2.1.3, 2.1.4, 2.1.8, 2.1.9, and 2.1.10, respectively.
5.1.1 Probe Liner-Borosilicate or quartz glass tubing. Testers may use a heating
system capable of maintaining a gas temperature of 120 * 14 °C (248 x 25 °F) at the
probe exit during sampling to prevent water condensation. (Note: Do not use metal
probe liners.)
If a filter is used ahead of the impingers, testers must use the probe
heating system to minimize the condensation of gaseous Hg. If a filter is used ahead
of the impingers, testers must use the probe heating system to minimize the
condensation of gaseous Hg.
5.1.2 Filter Holder (Optional)—The holder should be composed of borosilicate glass
with a rigid stainless-steel wire-screen filter support (do not use glass frit
supports) and a silicone rubber or Teflon gasket, designed to provide a positive seal
against leakage from outside or around the filter. The filter holder must be equipped
with a filter heating system capable of maintaining a temperature around the filter
holder of 120 ± 15 °C (248 ± 25 °F) during sampling to minimize both water and gaseous
Hg condensation. Testers may use a filter in cases where the stream contains large
quantities of particulate matter.
5.1.3 Impingers-Four Greenburg-Smith impingers are required. They should be
connected in series with leak-free ground glass fittings or any similar leak-free,
noncontaminatlng fittings. For the first, third, and fourth impingers, testers may use
Impingers that are modified by replacing the tip with a 13-mm ID (O.S-ln.) glass tube
extending to 13 mm (0.5 in.) from the bottom of the flask.
-------
Section No. 3.19.10
Dace September 21, 1992
Page 3
5.2 Sample .Recovery
The following items are needed for sample recovery:
5.2.1 Glass Sample Bottles-Tbe bottles should be leaklees, with Teflon-lined caps,
1000 and 100 mL.
5.2.2 Graduated Cylinder-A 2S0-mL graduated cylinder is required.
5.2.3 Funnel and Rubber Fcliceman— These items aid in transferring silica gel to the
container; they are not necessary if the silica gel is weighed in the field.
5.2.4 Funnel—The funnel should be glass/ it aids in sample recovery.
5 .2 Analysis
Same as in Method 101, Sections 5.3 and 5.4, respectively, except as follows:
5.2.1 Volumetric Pipets-Pipets must be Class A, 1, 2, 3, 4, 5, 10, and 20 mL.
5.2.2 Graduated Cylinder-A 25-mL graduated cylinder is required.
5.2.3 Steam Bach-Same as Method 101.
5 . 3 Sample Preparation and Analysis
The following equipment is needed for sample preparation and analysis:
5.2.1 Ato.r.ic Absorption Spectrophotometer—Any atomic absorption unit is suitable,
provided it has an open sample presentation area in which to mount the optical cell.
Testers should follow the instrument settings recommended by the manufacturer. Instru-
ments designed specifically for measuring Hg using the cold-vapor technique are commer-
cially available and may be substituted for the atomic absorption spectrophotometer.
5.3.2 Optical Celi-The optical cell should be cylindrical, with quartz end windows
and the dimensions shown in Figure 101A-2. Wind the cell with approximately 2 m of
24-gauge nichrome heating wire and wrap with fiberglass insulation tape, or equivalent;
do not let the wires touch one another. As an alternative to the heating wire, testers
may use a heat lamp mounted above the cell or a moisture trap installed upstream of the
cell.
5.3.3 Aeration Cell-The cell must be constructed according to the specifications
in Figure 101A-3. Do not use a glass frit as a substitute for the blown glass bubbler
tip shown in Figure 101A-3. Aeration cells, available with commercial colc-vapor
instrumentation, may be used as an alternate apparatus.
5.3.4 Recoraer-The recorder must be matched to output of the spectrophotometer
described in Section 5.3.1.
5.3.5 'variable Transformer-The transformer is necessary for varying the voltage on
the optical cell from 0 to 40 volts.
5.3.6 Hood—A hood is reouired for ventino the optical, cell exhaust.
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Section No. 3.19.10
Date September 21, 1992
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5.3.7 Flow Metering Valve— Same as Method 101.
5.3.8 Flow Meter-A rotometer, or equivalent. Is required tiaat la capable of
measuring a gas flow of 1.5 L/min.
5.3.9 Aeration Gas Cylinder—The cylinder must contain nitrogen or dry, Hg-free air
and must be equipped with a single-stage regulator. As an alternative, aeration may
be provided by a peristaltic metering pump. If a commercial cold-vapor instrument is
used, follow the manufacturer's recommendations.
5.3.10 Tubing-The tubing Is require for making connections. Dse glass tubing
(ungreased ball- and socket-connections are recommended) for all connections between
the solution cell and the optical cell; do not use Tygon tubing, other types of
flexible tubing, or metal tubing as substitutes. Testers may use Teflon, steel, or
copper tubing between the nitrogen tank and t.be flow meter valve (Section 5.3.7), and
Tygon, gum, or rubber tubing between tJa« flow meter valve and the aeration cell.
5.3.11 Flow Rate Calibration Eguipment-This equipment consists of a bubble flow
meter or a wet-test meter for measuring a gas flow rate of 1.5 * 0.1 L/min.
5.3.12 Volumetric Flasks—These flasks must be Class A, with pennyhead standard taper
stoppers; tiie required sizes are 100, 250, 500, and 1000 mL.
5.3.13 Volumetric Fipets-These plpets must be Class A; the required sizes are 1, 2,
3, 4, 5, 10, and 20 mL.
5.3.14 Graduated Cylinder-A 25-mL cylinder is required.
5.3.15 Magnetic Stirrer-A general-purpose laboratory-type stirring bar is required.
5.3.16 Magnetic Stirring Bar-A Teflon-coated stirring bar is required.
5.3.17 Bslance-A balance capable of weighing to ± 0.5 g is required.
5.3.18
Steam Bath
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Section No. 3.19.10
Date September 21, 1992
Page 5
5.4 Alternative Analytical Apparatus
Alternative systems are allowable as long as they .meet the following
criteria:
5.4.1 The system must generate a linear calibration curve and two consecutive
samples of the same aliquot size and concentration must agree within Jt of their
average.
5.4.2 The system must allow for recovery of a minimum of 95% of the spike when an
aliquot of a source sample is spiked with a known concentration of Hg (II) compound.
5.4.3 The reducing agent should be added after the aeration cell is closed.
5.4.4 The aeration bottle bubbler should not contain a frit.
5.4.5 Any Tygon tubing used should be as short as possible and should be
conditioned prior to use until blanks and standards yield linear and reproducible
results.
5.4.6 If manual stirring is performed before aeration, the aeration cell should be
closed during the process.
5.4.7 A drying tube should not be used unless it is conditioned following the
procedure for the Tygon tubing, above.
6.0 REAGENTS
Use ACS reagent-grade chemicals or equivalent, unless otherwise specified.
6.1 Sampling and Recovery
The following reagents are used in sampling and recovery:
6.1.1 Water—Deior.ized distilled, meeting ASTM specifications for Type I Reagent
Water—ASTK Test Method D 1153-77. If high concentrations of organic matter are not
expected to be present, users may eliminate the KMnO; test for oxidizable organic
matter. Use this water in all dilutions and solution preparations.
6.1.2 Nitric Acid (HNOJ, 50% fv/vJ-Mix equal volumes of concentrated HN0:. and
water, being careful to add the acid to the water slowly.
6.1.3 Silica Gei-Indicating type, 6- to 16-mesh. If previously used, dry at 175
°C (350 °Fi for 2 h. Testers may use new silica gel as received.
6.1.4 Filter (Optional)—Glass fiber filter, without organic binder, exhibiting at
least 99.95% efficiency on 0.3-nm dioctyl phthalate smoke particles. Testers may use
the filter in cases where the gas stream contains large quantities of particulate
matter, but they should analyze blank filters for Hg content.
6.1.5 Sulfuric Acid (H:S04), 10% fv/v)— Add and mix 100 mL of concentrated H;.S0- to
9 00 mL of water.
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Page 6
6.1.6 Absorbing Solution, 4% KMnOt (w/v)-Prepare fresh daily. Dissolve 40 g of
KMnO, in sufficient 10% H;SOs to make 1 L. Prepare and store in glass bottles to
prevent degradation.
6.1.7 Hydrochloric Acid-Trace metals grade HCl is recommended. If other grades are
used, the Hg level must be less than 3 ng/mL Hg.
6.1.8 Hydrochloric Acid, 8 N-Dilute 67 mL of concentrated HCl to 100 mL with water
(slowly add the HCl to the water).
6.2 Analysis
The reagents needed for analysis are listed below:
6.2.1 Tin III) Solution-Prepare fresh daily and keep sealed when not being used.
Completely dissolve 20 g of tin (II) chloride [or 25 g of tin (II) sulfate] crystals
(Baker Analyzed reagent grade or any other brand that will give a clear solution) in
25 mL of concentrated HCl. Dilute to 250 mL with water. Do not substitute HNOJ( H;S04,
or other strong acids for the HCl.
6.2.2 Sodium Chloride-Hydroxylamine Solution—Dissolve 12 g of sodium chloride and
12 c of hydroxylamine sulfate (or 12 g of hydroxylamine hydrochloride) in water and
dilute to 100 mL.
6.2.3 Hydrochloric Acid, 8 Af-Dilute 67 mL of concentrated HCl to 100 mL with water
(slowly add the HCl to the water).
6.2.4 Nitric Acid, 15% (v/v)— Slowly add 15 mL of concentrated HNO, to 100 mL of
water. „
6.2.5 Mercury Stock Solution, 1 mg Hg/mL-Prepare and store all Hg standard
solutions in bcrosilicate glass containers. Completely dissolve 0.1354 g of Hg (II)
chloride in 75 mL cf water. Add 10 mL of concentrated HN0: and adjust the volume to
exactly 100 mL with water. Mix thoroughly. This solution is stable for at least 1
month. ~
6.2.6 Intermediaze Hg Standard Solution, 10 jig/mL-Prepare fresh weekly. Pipet 5.0
mL of the Hg stock solution (Section 6.2.5) into a 500-mL volumetric flask, and add 20
mL of 15% HNO. solution. Adjust the volume to exactly 500 mL with water. Thoroughly
mix the solution.
6.2.7 Working Hg Standard Solution, 200 ng Hg/irlr-Prepare fresh daily. Pipet 5.0
mL from the Intermediate Hg Standard Solution (Section 6.2.6) into a 250-mL volumetric
flask. Add 5 mL cf 4% KMnO,; absorbing solution and 5 mL cf 15% HNO;.. Adjust the volume
to exactly 250 mL with water. Mix thoroughly.
6.2.8 Pozassi uir. Permanganate, 5% fw/vj-Dissolve 5 g of KMn04 in water and dilute
to 100 mL.
6.2.5 Filter—Use a Whatman 40, or equivalent.
7.0
PROCEDURE
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Date September 21, 1992
Page 7
7.1. Samplina
The sampling procedure is the same as in Method 101, except for changes
associated with using KMnO< instead of IC1 absorbing solution and the possible use of
a filter. Because of the complexity of this method, testers should be trained and
experienced with all procedures to ensure reliable results. Because the amount of Hg
collected generally is small, Che method must be applied carefully to prevent sample
contamination or loss.
7.1.1 Pretest Preparation—Follow the general procedure given in Method 5, Section
4.1.1, but omit the directions on the filter.
7.1.2 Preliminary Determinations-The preliminary determinations are the same as
those given in Method 101, Section 7.1.2, except for the absorbing solution depletion
sign. In this method, high-oxidizable organic matter content may make it impossible
to sample for the desired minimum time. This problem is indicated by the complete
bleaching of the purple color of the KMnO< solution. In these cases, testers may
divide the sample run into two or more subruns to ensure that the absorbing solution
will not be depleted. In cases where excess water condensation is encountered, collect
two runs to make one sample.
7.1.2 Train Preparation
7.1.2.1 Sampling train preparation is the same as that given in Method 101, Section
7.1.3, except for the cleaning of the glassware (probe, filter holder, if used,
impingers, and connectors) and for the charging of the first three impingers. In this
method, clean all the glass components by rinsing with 50% HN0J( tap water, S N HC1,
tap water, and finally deionized distilled water. Then place 50 mL of 4% KMnO, in the
first impinger and 100 mL in each of the second and third impingers.
7.1.2.2 If a filter is used, place it with the filter holder with a pair of tweezers.
Be sure to center the filter, and place the gasket in the proper position to prevent
the sample gas stream from by-passing the filter. Visually check the filter for damage
after assembly is completed. Be sure to set the filter heating system at the desired
operating temperature after the sampling train has been assembled. ~
7.1.2.1 Follow the general procedure given in Method 5, Section 4.1.2, except as
follows: Select a nozzle size based on the range of velocity heads to ensure that it
is not necessary to change the nozzle size to maintain isokinetic sampling rates below
28 L/min (1.0 cfm).
7.1.2.2 Highly oxidizable organic content may make it impossible to sample for the
desired minimum time. This problem is indicated by the complete bleaching of the
purple color of the KHnO{ solution. If the purple color is expended in the last
(third) KMn04 impinger, the sample run is unacceptable and another run shall be
conducted. In these cases, testers may divide the sample run into two or more subruns
to ensure that the absorbing solution will not be depleted or a fourth impinger
containing 100 mL of KMn04 may be used. In cases where excess water condensation is
encountered, collect two runs to make one sample or add extra empty impinger before the
first impinger containing XXnOt solution.
7.1.3 All the glass components should been cleaned in the laboratory (a hood is
recommended) by soaking with SO% HNO} for 1 h and then by rinsing with tap water, 8 N
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Section No. 3.19.10
Date September 21, 1992
Page 8
HC1, tap water, and finally deionized distilled water. After cleaning, openings should
be covered Co prevent contamination.
7.1.3.1 Place 50 mL of 4% KMnO, in the first impinger and 100 mL in each of the
second ana third impingers. Take care to prevent the absorbing solution from
contacting any greased surfaces. Place approximately 200 g of preweighed silica gel
in the fourth impinger. Testers may use more silica gel, but they should be careful
to ensure that it is not entrained and carried out from the impinger during sampling.
Place the silica gel container in a clean place for later use in the sample recovery.
Alternatively, determine and record the weight of the silica gel plus impinger to the
nearest 0.5 g. (Note: Contact with KMn04 should be avoided.)
7.1.3.2 If a filter is used, place it in the filter holder with a pair of tweezers.
Be sure to center the filter, and place the gasket in the proper position to prevent
the sample gas stream from by-passing the filter. Check the filter for tears after
assembly is completed. Be sure to set the filter heating system at the desired
operating temperature after the sampling train has been assembled.
7.1.3.3 Install the selected nozzle using a Viton A O-ring when stack temperatures
are less than 260 °C (500 °F). Vse a fiberglass string gasket if temperatures are
higher. Other connecting systems using either 316 stainless-steel or Teflon ferrules
may be used. Mark the probe with heat-resistant tape or by some other method to denote
the proper distance Into the stack or duct for each sampling point. Assemble the train
as shown In Figure 101A-1, using (if necessary) a very light coat of silicone grease
on all ground glass joints. Grease only the outer portion to avoid contamination by
the silicone grease.
Note: An empty impinger may be inserted .between the filter and first impinger
containing KMnO. to remove excess moisture from the sample stream.
7.1.3.4 After the sampling train has been assembled, turn on and set the probe, if
applicable, at the desired operating Coxqperature. Allow time for the temperatures to
stabilize. Place crushed ice around the lmplngers.
7.1.4 Leak Check Procedures-Follow the leak check procedures outlined In Method 5,
Sections 4.1.4.1, 4.1.4.2, and 4.1.4.3.
7.1.3 Sampling Train Operation-In addition to the procedure given In Method 101,
Section 7.1.5, maintain a temperature around the filter (if applicable) of 120 * 14 °C
(24 8 t 25 °F).
7.1.5 Mercury Train Operation-Follow the general procedure given In Method 5,
Section 4.1.5, maintain a temperature around the filter (if applicable) of 120 s 14 °C
(248 t 25 °F). For each run, record the data required on a data sheet, such as the one
shown In Figure 101A-4.
7.1.6 Calculating Percent of Isokinetic Sampling—Same as In Method 5, Section
4.1.6.
7 . 2 Sample Recovery
Begin proper cleanup procedure as soon as the probe is removed from the stack
at the end of the sampling period. Allow the probe to cool. When it can be handled
safely, wipe off any external particulate matter near the nozzle tip ana place a cap
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Section No. 3.19.10
Date September 21, 1992
Page 9
over it. Do not cap the probe tip tightly while the sampling train is cooling because
the resultant vacuum would draw liquid from the impingers. Before moving the sample
train to the cleanup site, remove the probe from the train, wipe off the silicone
grease, and cap the open outlet of the probe. Be careful not to lose any condensate
that might be present. Wipe the silicone grease from the impinger. Use either
ground-glass stoppers, plastic caps, or serum caps to close these openings. Transfer
the probe, impinger assembly, and (if applicable) filter assembly to an area that is
clean, protected from the wind, and free of Hg contamination.
The ambient air in laboratories located in the immediate vicinity of Hg-using
facilities is not normally free of Hg contamination. Inspect the train before and
during assembly and note any abnormal conditions. Treat the sample as follows:
7.2.1 Container No. 1 (Impinger, Probe, ana Filter Holder) and, if Applicable, No.
1A (HCl Rinse)
7.2.1.1 Using a graduated cylinder, measure the liquid in the first three impingers
to within 1 mL. Record the volume of liquid present (see Figure 5-3 of Method 5 in 40
CFR Part 60). This information is needed to calculate the moisture content of the
effluent gas. (Use only graduated cylinder and glass storage bottles that have been
precleaned as described in Section 7.1.2) Place the contents of the first three
impingers into a 1000-mL glass sample bottle. Note: If a filter is used, remove the
filter from its holder, as outlined under Container No. 3 below.
7.2.1.2 Taking care that dust on the outside of the probe or other exterior surfaces
does not get into the sample, quantitatively recover the Hg (and any condensate) from
the probe nozzle, probe fitting, probe liner, and front half of the filter holder (if
applicable) and impingers as follows: Rinse these components with a total of 400 ml
of fresh 4% KMnO; solution, carefully ensuring removal of all loose particulate matter
from the impingers. Add all washings to the 1000-mL glass sample bottie. Remove any
residual brown deposits on the glassware following the permanganate rinse with
approximately 100 mL of water, carefully assuring removal of all loose particulate
matter from the impingers, and add this rinse to Container No. 1. If no visible
deposits remain after this water rinse, do not rinse with 8 N HCl. However, if
deposits do remain on the glassware after the water rinse, wash impinger walls and
stems with the same 25 mL of 8 N HCl and place the wash in a separate container labeled
Container No. 1A. Use the following procedure: Place 200 mL of water ir. a sample
container labeled Ccntainer No. 1A. Use only a total of 25 mL of 8 N HCl to rinse all
impingers. Wash the impinger walls and stem with the HCl by turning and shaking the
impinger so that the HCl contacts all inside surfaces. While stirring, pour the HCl
wash carefully into Container No. 1A. The separate container is used for safety
reasons.
7.2.1.3 After all washings have been collected in the sample container, tighten the
lid to prevent leakage during shipment to the laboratory. Mark the height of the fluid
level to help determine whether leakage occurs during transport. Label the container
to identify its contents cleariy.
7.2.2 Container No. 2 (Silica GeJj-Note the color of the indicating silica gel to
determine whether it has been completely spent and make a notation of its condition.
Transfer the silica gel from its impinger to its original container and seal the
container. A funnel may be used to pour the silica gel, and a rubber policeman may be
used to remove the silica gel from the impinger. It is not necessary to remove the
small amount of particles that may adhere to the impinger wall and are difficult .tc
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Section No. 3.19.10
Date September 21, 1992
Page 10
remove. Because the weight gain is to be used for moisture calculations, do not use
any water or other liquids to transfer the silica gel. If a balance is available in
the field, weigh the spent silica gel (or silica gel plus impinger) to the nearest 0.5
g and record this weight.
7.2.3 Container No. 3 (Filter)—It a filter was used, carefully remove it from the
filter holder, place it in a 100-mL glass sample bottle, and add 20 to 40 ml of 4%
KMnO,. If it is necessary to fold the filter, be sure that the particulate cake is
inside the fold. Carefully transfer to the 150-mL sample bottle any particulate matter
and filter fibers that adhere to the filter holder gasket by using a dry Nylon bristle
brush and a sharp-edged blade. Seal the container. Label the container to identify
its contents clearly. Mark the height of the fluid level to help determine whether
leakage occurs during transport.
7.2.4 Container No. 4 (Filter Blank)-It a filter was used, treat an unused filter
from the same filter lot used for sampling in the same manner as Container No. 3.
7.2.5 Container No. 5 (Absorbing Solution Blank)—For a blank, place 650 mL of 4 %
KMnO^ absorbing solution in a 1000-mL sample bottle. Seal the container.
7.2.6 Container No. € (HC1 Rinse Elankt-Fox a blank, place 200 mL of water in a
1000-mL sample bottle. While stirring, add 25 mL of 8 N HC1. Seal the container.
Only one blank sample per 3 runs is required.
7.3 Sample Preparation
Check the liquid level in each container to see if liquid was lost during
transport. If a noticeable amount of leakage occurred, either void the sample or use
methods subject tc the approval of the Administrator to account for the losses. Thgn
follow the procedures below:
7.3.1 Containers Nc. 3 and No. 4 (Filter and Filter Blank)—It a filter was used,
place the contents, including the filter, of Containers No. 3 and No. 4 in separate
250-mL beakers. Heat the beakers on a steam bath until most of the liquid has
evaporated. Do not take to dryness. Add 20 mL of concentrated HNO, to the beaker?,
cover them with a watch glass, and heat on a hot plate at 70 °C for 2 h. Remove from
the hot plate. Filter the solution from the digestion of the contents of Container Nc.
3 through Whatman 40 filter paper and save the filtrate for addition to the Container
No. 1 filtrate, as described below. Discard the filter. Filter the solution from the
digestion of the contents of Container No. 4 through Whatman 40 filter paper anc save
the filtrate for addition to the Container No. 5 filtrate, as described in Section
7.3.2 below. Discard the filter.
7.3.2 Container No. 1 (lir.pingers, Probe, and Filter Holder) and, if Applicable, No.
1A (HC1 Rinse!—Filter the contents of Container No. 1 through Whatman 40 filter paper
into a 1-L volumetric flask to remove the brown MnO_ precipitate. Save the filter.
Add the sample filtrate from Container No. 3 to the 1-L volumetric flask and dilute to
volume with water. If the combined filtrates are greater than 1000 mi, determine the
volume to the nearest mL and make the appropriate corrections for blank subtractions.
Mix thoroughly.
Mark the filtrate as Analysis Sample No. A.l and analyze for Hg within 48 h
after completing the filtration step. Place the saved filter, which was used to remove
'the brown KnO: precipitate, into a container of appropriate, size. Add 25 mL of 8 N KCl
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Section No. 3.19.10
Date September 21, 1992
Page 11
to the filter and allow the filter, with its brown residue, to digest for a minimum of
24 h at room temperature. Filter the contents of Container No. 1A through a Whatman
40 filter paper into a 500-mL volumetric flask. Then filter the digestion of the brown
MnO; precipitate from Container No. 1 and the Whatman paper filter into the 500-mL
volumetric flask. Dilute to volume with water. Mark this 500-mL dilute solution as
Analysis Sample No. HCl A.2 and analyze for Hg. Discard the filters.
7.3.3 Containers No. 5 (Absorbing Solution Blank) and No. 6 (HCl Rinse Blankj-Treat
Container No. 5 the same as Container No. 1. described in the previous section. Add
the filter blank filtrate from Container No. 4 to the 1-L volumetric flask and dilute
to volume. Mix thoroughly. Mark this as Sample No. A.l blank and analyze for Hg
within 48 h after completing the filtration step. Digest any brown precipitate
remaining on the filter from the filtration of Container No. 5, using the procedure
described in Section 7.3.2. Filter the contents of Container No. 6 using the procedure
described in Section 7.3.2 and combine into the 500-mL volumetric flask with the
filtrate from the digested blank MNO- precipitate. Mark this resultant 500-mL combined
dilute solution as Analysis Sample No. HCl A.2 blank. Note: When analyzing blank
samples A.l blank and HCl A.2 blank, always begin with 10-mL aliquots. This note
applies specifically to blank samples.
7.4 Analysis
7.4.1 Calibrate the spectrophotometer and recorder and prepare the calibration
curve as described in sections 8.1 and 8.2. Then repeat the procedure used to
establish the calibration curve with aliquots of appropriate size (1 to 10 mL) of the
samples (from sections 7.3.2 and 7.3.3) until two consecutive peak heights agree within
3% of their average value. If the 10-mL sample is below the detectable lirr.it, use a
larger aliquot (up to 20 mL), but decrease the volume of water added to the aeration
cell accordingly to prevent the solution volume from exceeding the capacity of the
. aeration bottle. If the peak maximum of a 1-mL aliquot is off scale, further dilute
the original sample to bring the Hg concentration into the calibration range of the
spectrophotometer. If the Hg content of the absorbing solution and filter blank is
below the working range of the analytical method, use 2ero for the blank.
7.4.2 Run a blank and standard at least after every five samples to check the
spectrophotometer calibration; recalibrate as necessary. It also is recommended that
at least one sample from each stack test be checked by the Method of Standard Additions
to confirm that matrix effects have not interfered with the analysis.
8.0 Calibration and Standarde
The calibration and standards are the same as in Method 101, Section 8,
except for the following variations:
6.1 Optical Cell Keatina System Calibration
Same as in Method 101, Section 8.2, but use a 25-mL graduated cylinder tc add
25 mL of water to the bottle section of the aeration cell.
8.2 Spectrophotometer and Recorder Calibration
8.2.1 The Hg response may be measured by either peak height or peak area. Note:
The temperature of the solution affects the rate at which elemental Hg is released;
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Section No. 3.19.10
Date September 21, 1992
Page 12
consequently, it affects the shape of the absorption curve (area) and the point of
maximum absorbance (peak height). To obtain reproducible results, all solutions must
be brought to room temperature before use.
8.2.2 Set the spectrophotometer wave length at 253.7 nm and make certain the
optical cell is at the minimum temperature that will prevent water condensation. Then
set the recorder scale as follows: Using a 25-mL graduated cylinder, add 25 mL of
water to the aeration cell bottle, and pipet 5 mL of the working Hg standard solution
into the aeration cell. Note: Always add the Hg-containing solution to the aeration
cell after the 25 mL of water.
8.2.3 Place a Teflon-coated stirring bar in the bottle. Add 5 mL of the 4% KMnOs
to the aeration bottle and mix well. Attach the bottle section to the bubbler section
of the aeration cell. Make certain that: (1) the aeration cell exit arm stopcock
(Figure 101-3 of Method 101) is closed (so that Hg will not prematurely enter the
optical cell when the reducing agent is being added); and (2) there is no flow through
the bubbler. Add 5 mL of sodium chloride hydroxylamine in 1-mL increments until the
solution is colorless. Now add 5 mL of tin (II) solution to the aeration bottle
through the side arm and immediately stopper the side arm. Stir the solution for 15
s, turn on the recorder, open the aeration cell exit arm stopcock, and immediately
initiate aeration with continued stirring. Determine the maximum absorbance of the
standard, and set this value to read 90% of the recorder full scale.
Before uam, clean all glassware, both new and used, as follows: Brush with
aoap and tap water, liberally rinse with tap water, soak for 1 b in 50% KNO}. Rinse
with delonlzed distilled water.
8.1 Flow Calibration
Assemble the aeration system as shown in Figure 101-5. Set the outlet
pressure on the aeration gas cylinder regulator to a minimum pressure of 500 mm Hg (10
pel), and use the flow metering valve and a bubble flow meter or wet-test meter to
obtain a flow rate of 1.5 * 0.1 L/mln through the aeration cell. After the flow
calibration is completed, remove the bubble flow meter from the system.
8.2 Optical Cell Heating System Calibration ~
Using a 25-mL graduated cylinder, add 25 mL of water to the bottle section
of the aeration cell and attach the bottle section to the bubbler section of the cell.
Attach Che aeration cell to the optical cell; while aerating at 1.5 L/mln, determine
the minimum variable transformer setting necessary to prevent condensation of moisture
in the optical cell and In the connecting tubing. (This setting should not exceed 20
volts.)
8.3 Spectrophotometer ar.d Recorder Calibration
8.3.1 The Hg response may be measured by either peak height or peak area. (Note:
The temperature of the solution affects the rate at which elemental Hg is released;
consequently, It affects the shape of the absorption curve [area] and the point of
maximum absorbance [peak height]. Therefore, to obtain reproducible results, bring all
solutions to room temperature before use.)
8.3.2 Set the spectrophotometer wavelength at 253.7 nm and make certain that the
optical cell Is at the minimum temperature that will prevent water condensation. Then
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Section No. 3.19.10
Date September 21, 1992
Page 13
set the recorder scale as follows: Using a 25-mL graduated cylinder, add 25 mL of
water to the aeration cell bottle and pipet 5 mL of tbe working Hg standard solution
into the aeration cell. (Note: Always add tbe Hg-contalnlng solution to the aeration
cell after Che 25 mL of water.)
8.3.3 Place a Teflon-coated stirring bar in the bottle. Using a 25-mL graduated
cylinder, add 25 mL of laboratory pure water to the aeration cell bottle. Pipet 5.0
mL of the working Hg standard solution to the aeration cell. Add 5 mL of the 4% KMn04
absorbing solution, followed by 5 mL of 15% HNO:. and 5 mL of 5% KMn04 to the aeration
cell, and mix well using a swirling motion. Attach the bottle to the aerator, making
sure that: (1) the exit arm stopcock is closed, and (21 there is no aeration gas
flowing through the bubbler. Through the side arm, add 5 mL of sodium chloride
hydroxylamine solution in 1 mL-increments until the solution is colorless. Through the
side arm, add 5 mL of the Tin (II) reducing agent to the aeration cell bottle, and
immediately stopper the side arm. Stir the solution for 15 s and turn on the recorder
or integrator. Open the aeration cell exit arm stopcock and initiate the gas flow.
Determine the maximum height (absorbance) of the standard, and set this value to read
90% of the recorder full scale.
8.4 Calibration Curve
8.4.1 After setting the recorder scale, repeat the procedure In Section 8.3 using
0-, 1-, 2-, 3-, 4-, and S-mL aliquots of the working standard solution (final amount
of Kg in the aeration cell Is 0, 200, 400, 600, 800, and 1000 ng, respectively).
Repeat this procedure on each aliquot size until two consecutive peaks agree within 3%
of their average value. (Note: To prevent Hg carryover from one sample to another, do
not close the aeration cell from the optical cell until the recorder pen has returned
to the baseline.)
8.4.2 It should not be necessary to disconnect the aeration gas inlet line from the
aeration cell when changing samples. After separating the bottle and bubbler sections
of the aeration cell, place the bubbler section into a 600-mL beaker containing
approximately 400 mL of water. Rinse the bottle section of the aeration cell with a
stream of water to remove all traces of the tin (II) reducing agent. Also, to prevent
the loss of Hg before aeration, remove all traces of the reducing agent between samples
by washing with water. It will be necessary, however, to wash the aeration cell parts
with concentrated HC1 if any of the following conditions occur: (1) a white film
appears on any Inside surface of the aeration cell; (2) the calibration curve changes
suddenly,- or (3) the replicate samples do not yield reproducible results.
8.4.3 Subtract the average peak height (or peak area) of the blank (0-mL
aliquot)-which should be less than 2k of recorder full scale-from the averaged peak
heights of the 1-, 2-, 3-, 4-, and 5-mL aliquot standards. If the blank absorbance Is
greater than 2% of full-scale, the probable cause is Hg contamination of a reagent or
carry-over of Hg from a previous sample. Plot the corrected peak height of each
standard solution versus the corresponding final total Hg weight In the aeration cell
(in ng), and draw the best-fit straight line. This line should either pass through the
origin or pass through a point no further from the origin than * 2 % of the recorder
full scale. If the line does not pass through or very near to the origin, check for
nonllnearity of the curve and for incorrectly prepared standards.
9.0 Calculations
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Section No. 3.19.10
Date September 21, 1992
Page 14
9.1 Drv-Gas Volume, Volume of Water Vapcr and Moisture Content. Stack-Gas
Velocity, Isokinetic Variation and Acceptable Results, and Determination of Compliance
Same as in Method 101, Sections 9.1, 9.2, 9.3, 9.6, and 9.7, • respectively,
but use data obtained from this test.
9.1 Drv-Gas Volume
Using the data from this teat, calculate V„„tdJ, the dry-gas maniple volume at
standard conditions (corrected for leakage, if necessary) as outlined In Section 6.3
of Method 5.
9.2 Volume of Water Vavor and Moisture Content
Using the data obtained from this test, calculate the volume of water vapor
Vurttdl and the moisture content Bw, of the stack-gas. Use equations 5-2 and 5-3 of
Method 5.
9. 3 Stack-Gas Velocity
Using the data from this test and Equation 2-9 of Method 2, calculate the
average stack-gas velocity v..
9.4 Isokmet ic Variation and Acceptable Results
Same as in Method 5, Sections 6.11 and 6.12, respectively.
9. 5 Determir.ir.c Cc.tidI ia.nce
Each performance test consists of three repetitions of the applicable test
method. For the purpose of determining compliance with an applicable national emission
standard, use the average of the results of all repetitions.
9.2 Total Mercurv
For each source sample, correct the average maximum absorbance of the two
consecutive samples whose peak heights agreed within 3% of their average for the
contribution of the blank. Ther. calculate the total Hg content in ^ig ir. each sample.
Correct for any dilutions made to bring the sample into the working range cf the
spectrophotometer.
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Section No. 3.19.10
Date September 21, 1992
Page 15
m(HCl) h:. =
[C(HC1)„: DF]
[C(HCl blk) k. DF,-,.] 1
•• I 10"' Equation 101A-1
^7
where:
m (HCl) H.
C(HC1:
h;
C1HC1 blk)
DF
DF.
Total blank corrected |ig of Hg in HCl rinse and HC1
digestate of filter sample.
Total ng of Hg analyzed in the aliquot from the 500-mL
Analysis Sample No. HCl A.2.
Total ng of Hg analyzed in aliquot of the 500-mL Anal-
ysis Sample No. HCl A.2 blank.
Dilution factor for the HCl digested Hg-containing
solution, Analysis Sample No. HCl A.2. This dilution
factor (DF) applies only to the intermediate dilution
steps because the original sample volume (V,)H._ of HCl
A.2 has been factored out in the equation, along with
the sample aliquot, (S). In Equation 6.9, the sample
aliquot, S, is introduced directly into the aeration
cell for analysis according to the procedure outlined in
Section 3.19.5.3.4. A dilution factor is required onty
if it is necessary to bring the sample into the analyti-
cal instrument's calibration range. If no dilution is
necessary, then DF equals 1.0.
Dilution factor for the Analysis Sample No. HCl A.2
blank. (Note: Normal dilution factor calculations apply
here. )
Solution volume of original sample, 500 mL for samples
diluted as described in Section 7.3.1.
1C" = Conversion factor, yig/ng.
£ = Aliquot volume of sample added to aeration cell, ml.
S,:. = Aliquot volume of blank added to aeration cell, mL.
Note: The maximum allowable blank subtraction for the HCl is the lesser of
the two following values: (1) the actual blank measured value (Analysis Sample No. HCl
A.2 blank); or (2) 5% of the Hg content in the combined HCl rinse and digested sample
(Analysis Sample No. HCl A.2).
where:
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Section No. 3.19.10
Date September 21, 1992
Page 16
[Cffltr blk) „ DFblk V,It!t.]l
^bik
10": Equation 1C1A-2
m(fltr)H. = Total blank corrected Jig of Hg in KMNOg filtrate and HNO.
digestion of filter sample.
C(fltr)H; = Total ng of Hg in aliquot of KMNO, filtrate and HNOj
digestion of filter analyzed (aliquot of Analysis Sample
No. A.1) .
Cffltr blk)H; = Total ng of Hg in aliquot of KMNO, blank and HN03 diges-
tion of blank filter analyzed (aliquot of Analysis
Sample No. A.l blank).
V....... = Solution volume of original sample, normally 1000 mL for
samples diluted as described in Section 7.3.2.
V.(lll = Solution volume of blank sample, 1000 mL for sarr.ples
diluted as described in Section 7.3.2
Note: The maximum allowable blank subtraction for the HC1 is the lesser of
the two following values: (1) the actual blank measured value (Analysis Sample No. A.l
blank); or (2) 5% of the Hg content in the filtrate (Analysis Sample No. A.l).
mh. = m(HCl) H. «• Equation 101A-3
where:
mH; = Total blank corrected Hg content in each sample, Hg.
ir.(HCl)M, = Total blank corrected ng of Hg in HC1 rinse and HC1 digestate
of filter sample.
m(fltr)u, = Total blank corrected ng of Hg in KKNO. filtrate and HNO;.
digestion of filter sample.
9.3 Mercurv Emission Rate
Calculate the Hg emission rate R in g/day for continuous operations using
Equation 1C1A-4. For cyclic operations, use only the time per day each stack is in
operation. The total Hg emission rate from a source will be the summation of results
from, all stacks.
where:
TTV
Tots! blank corrected Ha content in each samcle. uc.
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Section No. 3.19.10
Date September 21, 19
Page 17
mh vc A. (86,400 x 10" )
R = K - : , Equation 101A
\.Vp:,ld: * J (Tr/PJ
Average stack-gas velocity, m/sec (fps).
Stack cross-sectional area, m: (ft*).
Conversion factor, s/day.
Conversion factor, g/|ig.
Dry-gas sample volume at standard conditions, corrected
leakage (if any), m3 (ftJ).
Volume of water vapor at standard conditions, nr (ft3).
Absolute stack-gas temperature, °K (°R).
Absolute stack-gas pressure, mm Hg (in. Hg).
0.3858 °K/mm Hg for metric units.
17.64 °R/ir.. Hg for English units.
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Section No. 3.19.10
Date September 21, 1992
Page 18
10.1 Bibliography
1. Same as bibliography in Method 101.
2. Mitchell, W.J., M.R. Midgett, J.C. Suggs, and D. Albrinck. Test
Methods to Determine the Mercury Emissions from Sludge Incineration
Plants. EPA-600/4-79-058. September 1979. U.S. Environmental
Protection Agency (EPA). Research Triangle Park, NC.
3. Wilshire, Frank W. , J.E. Knoll, T.E. Ward, and M.R. Midgett.
Reliability Study of the U.S. EPA's Method 101A - Determination of
Particulate and Gaseous Mercury Emissions. Report No. 600/D-31/219
AREAL 367, NTIS Acc No. PB91-233361. U.S. Environmental Protection
Agency (EPA). Research Triangle Park, NC.
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Section No.3.19.11
Date September 3, 1992
Page 1
11.0 REFERENCES
1. Method 101A - Determination of Particulate and Gaseous Mercury Emissions from
Sewage Sludge Incinerators. Federal Register, Volume 47, July 8, 1982, p.
24703.
2. Corrections to Method 101A. Federal Register, Volume 49, September 12, 1984,
p. 35768.
3. Corrections to Method 101A. Federal Register, Volume 53, September 23, 1988,
p. 36972.
4. Method 101 - Determination of Particulate and Gaseous Mercury Emissions from
Chlor-Alkali Plants - Air Streams. Federal Register, Volume 38, May 6, 1973,
p. 08826.
5. Amendments to Method 101. Federal Register, Volume 47, July 8, 1982, p.
24703 .
6. Corrections to Method 101. Federal Register, Volume 49, September 12, 1984,
p. 35768.
7. Corrections to Method 101. Federal Register, Volume 53, September 23, 1988,
p. 36972.
8. Wilshire, Frank W., J.E. Knoll, T.E. Ward, and M.R. Midgett. Reliability
Study of the U.S. EPA's Method 101A - Determination of Particulate and
Gaseous Mercury Emissions. Report No. 600/D-31/219 AREAL 367, NTIS Acc No.
PB91-233361, U.S. Environmental Protection Agency, Research Triangle Park,
NC.
9. Addendum to Specifications for Incinerator Testing at Federal Facilities.
PHS, NCAPC. December 6, 1967.
10. Determining Dust Concentration in a Gas Stream. ASME Performance Test Code
No. 27. New York, NY. 1957.
11. DeVorkin, Howard, et al. Air Pollution Source Testing Manual. Air Pollution
Control District. Los Angeles, CA. November 1963.
12. Hatch, W.R., and W.I. Ott. Determination of Sub-Microgram Quantities of
Mercury by Atomic Absorption Spectrophotometry. Anal. Chem. 40:2085-87, 1968.
13. Mark, L.S. Mechanical Engineers' Handbook. McGraw-Hill Book Co., Inc. New
York, NY. 1951.
14. Martin, Robert M. Construction Details of Isokinetic Source Sampling
Equipment. EPA APTD-0581, U.S. Environmental Protection Agency. Research
Triangle Park, NC. April 1971.
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Section No.3.19.11
Date September 3, 1992
Page 2
15. Western Precipitation Division of Joy Manufacturing Co. Methods for
Determination of Velocity, Volume, Dust and Mist Content of Gases. Bulletin
WP-50. Los Angeles, CA. 1968.
16. Perry, J.H. Chemical Engineers' Handbook. McGraw-Hill Book Co., Inc. New
York, NY. 1960.
17. Rom, Jerome J. Maintenance, Calibration, and Operation of Isokinetic Source
Sampling Equipment. EPA APTD-0576, U.S. Environmental Protection Agency.
Research Triangle Park, NC. April 1972.
18. Shigehara, R.T., W.F. Todd, and W.S. Smith. Significance of Errors in Stack
Sampling Measurements. Stack Sampling News. 1(3):6-18, September 1973.
19. Smith, W.S., et al. Stack Gas Sampling Improved and Simplified with New
Equipment. APCA Paper No. 67-119. 1967.
20. Smith, W.S., R.T. Shigehara, and W.F. Todd. A Method of Interpreting Stack
Sampling Data. Stack Sampling News. 1(2):8-17, August 1973.
21. Specifications for Incinerator Testing at Federal Facilities. PHS, NCAPA.
1967 .
22. Standard Method for Sampling Stacks for Particulate Matter. In: 1971 Annual
Book of ASTO Standards, Part 23. ASTM Designation D 2928-71. Philadelphia, PA
1971.
23. Vennard, J.K. Elementary Fluid Mechanics. John Wiley and Sons, Inc. New York.
1947.
24. Mitchell, W.J., and M.R. Midgett. Improved Procedure for Determining Mercury
Emissions from Mercury Cell Chlor-Alkali Plants. J. APCA. 26:674-677, July
1976.
25. Shigehara, R.T. Adjustments in the EPA Nomograph for Different Pitot Tube
Coefficients and Dry Molecular Weights. Stack Sampling News. 2:4-11, October
1974 .
26. Vollaro, R.F. Recommended Procedure for Sample Traverses in Ducts Smaller
than 12 Inches in Diameter. U.S. Environmental Protection Agency, Emission
Measurement Branch. Research Triangle Park, NC. November 197 6.
27. Klein, R., and C. Hach. Standard Additions: Uses and Limitation in Spectro-
photometry Measurements. Amer. Lab. 9:21, 1977.
28. Water, Atmospheric Analysis. In: Annual Book of ASTM Standards, Part 31. ASTO
Designation D 1193-74. Philadelphia, PA. 1974.
29. Mitchell, W.J., M.R. Midgett, J.C. Suggs, and D. Albrinck. Test Methods to
Determine the Mercury Emissions from Sludge Incineration Plants. EPA-600-
/4-79-058, U.S. Environmental Protection Agency. Research Triangle Park, NC.
September 1979.
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