United States Environmental Monitoring Systems
Environmental Protection Laboratory
Agency Research Triangle Park NC 27711
Research and Development EPA-600/4-77-027b Dec. 1984
Quality Assurance
Handbook for
Air Pollution
Measurement
Systems:
Volume III. Stationary
Source Specific
Methods
Sections 3.8, 3.9,
3.10,and3.11
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Section No. 3.8
Revision No. 0
Date January 4, 1982
Page 1 of 2
Section 3.8
METHOD 10-DETERMINATION OF CARBON MONOXIDE EMISSIONS FROM
STATIONARY SOURCES
OUTLINE
Number of
Documentation pages
SUMMARY 3.8 1
METHOD HIGHLIGHTS 3.8 7
METHOD DESCRIPTION
1. PROCUREMENT OF APPARATUS
AND SUPPLIES 3.8.1 13
2. CALIBRATION OF APPARATUS 3.8.2 18
3. PRESAMPLING OPERATIONS 3.8.3 6
4. ON-SITE MEASUREMENTS 3.8.4 12
5. POSTSAMPLING OPERATIONS 3.8.5 5
6. CALCULATIONS 3.8.6 3
7. MAINTENANCE 3.8.7 2
8. AUDITING PROCEDURE 3.8.8 7
9. RECOMMENDED STANDARDS FOR
ESTABLISHING TRACEABILITY 3.8.9 7
10. REFERENCE METHOD 3.8.10 3
11. REFERENCES 3.8.11 2
12. DATA FORMS 3.8.12 11
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Section No. 3.8
Revision No. 0 *
Date January 4, 1982
Page 2 of 2 .*
SUMMARY
A gas sample is extracted from the stack either at a con-
stant rate using a continuous sampling train or at a rate propor-
tional to the stack velocity using an integrated sampling train.
The concentration of carbon monoxide (CO) from both sampling
methods is determined by a Luft-type nondispersive infrared
(NDIR) analyzer or equivalent analyzer. The method is applicable
to stationary sources when specified by a compliance procedure
and/or when the CO concentration is >_20 parts per million (ppm)
for a O-to-1000-ppm testing range. With this method, inter-
ferences can result from substances with strong infrared ab-
sorption energies. Interference ratios in the 1500-to-3000-ppm
testing range are 7 ppm CO per 3.5% for water (H2O) and 10 ppm CO
per 10% for carbon dioxide (C02). In the O-to-100-ppm range,-
they can be as high as 25 ppm CO per 3.5% H20 and 50 ppm CO per
10% C02. Major interferences can be avoided by using silica gel
and ascarite traps to remove H20 and C02, respectively; if traps
are used, the gas sample volumes must be adjusted. The method
description given herein is based on the Reference Method promul-
gated March 8, 1974 (Section 3.8.10) and on collaborative test-
ing.1 Blank forms for recording data are provided in the Method
Highlights and in Section 3.8.12 for the convenience of Handbook
users.
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Section No. 3.8
Revision No. 0
Date January 4, 1982
Page 1 of 7
METHOD HIGHLIGHTS
Section 3.8 describes specifications for determination of
carbon monoxide (CO) from stationary sources. A gas sample is
extracted from the stack using a continuous or integrated sam-
pling train and analyzed using a Luft-type nondispersive infrared
(NDIR) analyzer or the equivalent. Interferences include any
substance having a strong absorption of infrared energy. Major
interference problems caused by water (H20) and carbon dioxide
(C02) are removed using silica gel and ascarite traps, respec-
tively.
Continuous sampling is performed by connecting the NDIR to
the continuous sampling train and conducting the analysis. In-
tegrated sampling is performed by withdrawing a sample at a rate
proportional to stack gas velocity, into a Tedlar, or equivalent
evacuated bag. C02 content, for each sampling method can be
determined using the Method 3 integrated sampling procedure or by
weighing the ascarite C02 removal trap and computing CO2 con-
centration from the gas volume sampled and the weight gain of the
trap. Results of collaborative tests1'2 of Method 10 revealed
several problems which, if eliminated, may result in improved
precision and accuracy. Reference gases were cited as an area
where improved quality control is needed. A need for further
training of NDIR operators was also cited as another area that
needed improvement.
The blank data forms at the end of the highlights section
may be removed from the Handbook and used in the pretest, test,
and posttest operations. Each form has a subtitle (e.g., Method
10, Figure 5.1) to assist the user in finding a similar filled-in
form in the Method Description (e.g., in Section 3.8.5). On the
blank and filled-in forms, the item/parameters that can cause the
most significant errors are indicated with an asterisk.
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Section No. 3.8 "
Revision No. 0
Date January 4, 1982
Page 2 of 7
1. Procurement of Equipment
Section 3.8.1 (Procurement of Apparatus and Supplies) gives
the specifications, criteria, and design features for equipment
and materials required for performing Method 10 tests. This
section is designed to serve as a guide in the procurement and
initial check of equipment and supplies. The activity matrix
(Table 1.1) at the end of Section 3.8.1 can be used as a quick
reference; it follows the same order as the written description
in the main text.
2. Pretest Preparations
Section 3.8.2 (Calibration of Apparatus) provides a step-by-
step description of the required calibration procedures. De-
tailed methods and procedures are described for calibrating the
NDIR. The calibration section can be removed and compiled, along
with calibration sections from all other methods, into a separate
quality assurance reference manual for use by calibration person-
nel. A pretest checklist (Figure 3.1) or similar form should be
used to summarize the calibration data.
Section 3.8.3 (Presampling Operations) provides the tester
with a guide for supplies and equipment preparation for field
tests. The pretest preparation form (Figure 3.2) can be used as
an equipment checkout and packing list. The method for packing
and the recommended packing containers should help^ protect the
equipment, but are not required.
3. On-Site Measurements
Section 3.8.4 (On-Site Measurements) contains step-by-step
procedures for sampling using the continuous and integrated
methods. The procedure .for continuous sampling includes perform-
ing the analysis on-site at the time of sample collection; there-
fore, procedures for analyzing the continuous sample are included
in this section. The on-site measurement checklist (Figure 4.4)
is provided to assist the tester with a quick method of checking
requirements.
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Section No. 3.8
Revision No. 0
Date January 4, 1982
Page 3 of 7
4. Posttest Operations
Section 3.8.5 (Postsampling Operations) gives the posttest
equipment check procedures and a step-by-step analytical proce-
dure for integrated samples. Figure 5.1 or a similar form Should
be used to summarize the posttest calibration checks and should
be included in the emission test report.
Section 3.8.6 (Calculations) provides the tester with the
required equations, nomenclature, and suggested number of signif-
icant digits. It is suggested that, if available, a programmable
calculator be used to reduce chance of calculation error.
Section 3.8.7 (Maintenance) supplies the tester with a guide
for a routine maintenance program. The program is not a require-
ment, but is suggested for reducing equipment malfunctions.
5. Auditing Procedure
Section 3.8.8 (Auditing Procedure) provides a description of
necessary activities for conducting performance and system au-
dits. The performance audits include an audit of the analytical
phase and an audit of data processing. A system audit consists
of an on-site qualitative evaluation of the test team perform-
ance-. The performance and system audits provide an independent
assessment of data quality.
Section 3.8.9 (Recommended Standards for Establishing Trace-
ability) recommends the primary standards to which the sample
collection and analysis should be traceable.
6. References
Section 3.8.10 (Reference Method) contains a copy of the EPA
Reference Method.
Section 3.8.11 (References) provides the reader with a list
of all the references used in the compilation of this section of
the Handbook along with additional sources.
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Section No. 3.8 **
Revision No. 0
Date January 4, ,1982
Page 4 of 7
PRETEST SAMPLING CHECKS
(Method 10, Figure 3.1)
Date Completed by
Pitot Tube
Identification number Date
Dimensional specifications checked?* yes no
Calibration required? yes no
Date C
P
Rotameter
Identification number
Calibration required?* yes no
Barometer
Calibrated?* yes no
*Most significant items/parameters to be checked.
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Section No. 3.8
Revision No. 0
Date January 4, 1982
Page 5 of 7
PRETEST PREPARATIONS
(Method 10, Figure 3.2)
Apparatus check
Probe
Pyrex glass
Stainless steel
Filter
Pi tot tube
Type
Length
Calibrated*
Differential
pressure gauge
Air-cooled con-
denser
Clean
Leak checked*
Needle valve and
rotameter
Clean
Calibrated*
Barometer
Type
Calibrated*
Pump
Type
Leak checked
Flexible bag
Type
Leak checked*
Evacuated*
Acceptable
Yes
No
Quantity
required
Ready
Yes
No
Loaded
and packed
*Most significant items/parameters to be checked.
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Section No. 3.8"
Revision No. 0
Date January 4,^1982
Page 6 of 7
ON-SITE MEASUREMENTS CHECKLIST
(Method 10, Figure 4.4)
Continuous Sampling
Leak check prior to sampling (optional)
NDIR analyzer allowed to warm up (1 h minimum)*
Multipoint calibration curve constructed*
Sampling port plugged
Sampling flow rate properly set (manufacturer's recommended and
<_! Vrnin)*
Sampling system properly purged*
Posttest leak check (mandatory)*
All data properly recorded*
C02 concentration determined*
Integrated Sampling
Sampling rate selected for integrated sampling
Leak check prior to sampling (optional)
Sampling port plugged
Sampling train purged (5 times system volume or 10 min)*
Flexible bag properly sealed and labeled*
Posttest leak check (mandatory)*
All data properly recorded*
C02 concentration determined*
*Most significant item/parameters to be checked.
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Section No. 3.8
Revision No. 0
Date January 4, 1982
Page 1 of 1
POSTTEST SAMPLING CHECKS
(Method 10, Figure 5.1)
NDIR
Posttest zero check adjusted value
Posttest span check* within ±10% of pretest calibration
Recalibration required? yes no
If yes, void all data back to the last calibration check that
was within the ±10% limit
Rotameter
Pretest calibration factor, Y within ±5%
Posttest check,* Yr within ±10% of pretest
Recalibration recommended? yes no
If performed, recalibration factor, Y (Y not used for
emission calculations)
Rotameter cleaned? yes no
Analysis (Integrated Samples)
Calibration gases traceable to NBS standard gas*
NDIR allowed to warm up (1 h minimum)*
Multipoint calibration curve constructed*
Sampling lines .and analyzer properly purged (5 times system
volume or 10 min)*
Three successive readings made from each bag
Highest and lowest values differ by <_5%
*Most significant items/parameters to be checked.
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Section No. 3.8.1
Revision No. 0
Date January 4, 1982
Page 1 of 13
1.0 PROCUREMENT OF APPARATUS AND SUPPLIES
Carbon monoxide (CO) sampling trains used to obtain inte-
grated and continuous gas samples are shown in Figures 1.1 and
1.2, respectively. Table 1.1 at the end of this section summa-
rizes the quality assurance activities for procurement and ac-
ceptance of apparatus and supplies.
Specifications, criteria, and/or design features as applica-
ble are given in this section to aid in the selection of equip-
ment to ensure the collection of good quality data. Procedures
and limits for acceptance checks, where applicable, are given.
During the procurement of equipment and supplies, it is
suggested that a procurement log (Figure 1.3) be used to record
the descriptive title of the equipment; the identification num-
ber, if applicable; and the results of the acceptance checks.
Also, if calibration is required as part of the acceptance check,
the data are to be recorded in the calibration log book.
1.1 Sampling
1.1.1 Sampling Probe - The sampling probe should consist of a
316 seamless stainless steel tube or a sheathed borosilicate
(Pyrex) glass tube with an inside diameter (ID) of approximately
6 mm (0.24 in.); and equipped with an in-stack or out-stack
particulate filter. When an in-stack filter is used, the probe
should have an expanded ID of 38 to 40 mm (1.5 to 1.6 in.) for
the first 40 mm (1.6 in.) of the probe inlet. The expanded
section should be packed with glass wool prior to sampling. The
probe outlet must have a fitting suitable for attachment to an
air-cooled condenser inlet. A probe approximately 1.1 m (4 ft)
long is usually sufficient; the exact length can be determined
after a sampling site inspection. If the stack must be traversed
to obtain an integrated sample, the probe length should be chosen
accordingly.
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Section No. 3.8.1.
Revision No. 0
Date January 4, 1982
Page 2 of 13
RATE
METER
PROBE
\
r
FltTER
(GLASS WOOL)
PUMP
RIGID
AIRTIGHT
CONTAINER
Figure l.l. Sampling train for integrated analysis.
AIR-COOLED CONDENSER
TO ANALYZER
RIGID AIRTIGHT
CONTAINER
FILTER (GLASS WOOL)
7
VALVE
Figure...1.2. Sampling train for continuous analysis
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Item description
Ca/DMsst
Quantity
3
Purchase
order
number
Iff 6^ 0/4
Vendor
Aa Mom. Co.
Date
Ordered
/- s- -?«
Received
3-t-~ie>
Cost
jrzso
Dispo-
sition
KcAW ft* vsc
Comments
p> p)
iQ ft
(D ID
P>
o a
HI c:
M h
^
vo
Figure 1.3. Example of a procurement log. to
5« w
< O
H-rt
CO H-
H-0
O 3
1*
co
I •
oo
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Section No. 3.8..1
Revision No. 0
Date January 4, 1982
Page 4 of 13
The main criterion in selecting the probe material is that
it be nonreactive with the gas constituents so that it will not
introduce bias into the analysis.
Upon receiving a new probe, visually check it for adherence
to specifications (i.e., the length and composition ordered).
Check for breaks, cracks, and leaks. Leak check the probe;
connect it to a pump inlet, plug other end, and pull a 380 mm (15
in.) Hg vacuum. Leakage rates >0.00057 ms/min (0.02 ft3/min)
measured by the dry gas meter are unacceptable. Any probe not
satisfying the checks should be repaired if possible or returned
to the supplier.
1.1.2 Air-CooJ.ed Condenser - The condenser facilitates the
condensation of water from the gas being sampled. The coiled
tubes (Figures 1.1 and 1.2) allow the entering gas to cool to
near ambient temperature; lower temperatures can be obtained by
using a circulating water cooler or an ice bath.
The reservoir collects and holds the condensed water until
it is drained between sampling runs by a valve. The capacity of
the reservoir must be sufficient to collect all condensed mois-
ture from the gas during system purging and sampling, but it
should not be unnecessarily oversized because the added size
would increase the bulk of the sampling train and lengthen purg-
ing time. For example, a sampling train of l-£ volume (including
the condenser) should hold the condensate from about 100 £ of gas
(90-£ sample plus 5-£ displacements of the sampling train volume
plus 5-2 margin). With 20% water concentration in the stack
gases, the 100-£ sample would contain 20 £ of water vapor; when
condensed, the 20 £ of vapor would correspond to about 20 ml of
water; therefore, a condenser volume of 0.25 £ would allow an
adeguate operating margin. The amount of water that would be
collected can be estimated either from knowledge of the process
or by determining the moisture content (Method 3) and sample
volume.
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Section No. 3.8.1
Revision No. 0
Date January 4, 1982
Page 5 of 13
Check the condenser visually for damage, breaks, cracks, and
manufacturing flaws. The condenser should be leak free at a
draft gauge positive pressure of 25 mm (1 in. ELO) and at a
vacuum gauge reading of 380 mm (15 in.) Hg. If the condenser is
defective, repair it or return it to the supplier.
1.1.3 Needle Valve - A stainless steel needle valve with appro-
priate fittings to make it leak free is recommended to regulate
the flow in the sampling train. Install the valve and check for
proper operation. If the valve is defective or if it cannot
regulate the sample flow over the 0-to-l £/min (O-to-0.035
ft /min) range, repair it or return it to the supplier.
1.1.4 Vacuum Pump - The vacuum pump should be capable of main-
taining a flow rate of 1 £/min (0.035 ft /min) at 380 mm (15 in.)
Hg. A leak-free diaphragm pump (or the equivalent) must be used
because of inherently low contamination possibilities with this
type of pump.
A new pump should be visually checked for damage, leaks, and
capacity upon receipt. To. leak check the pump, install a vacuum
gauge in the pump inlet line; plug the inlet line, and run the
pump until the vacuum gauge reads 380 mm (15 in. ) Hg; then close
the pump outlet line, and turn the pump off. The vacuum gauge
should remain stable for 30 s. If defective, return it to the
supplier.
1.1.5 Rate Meter - The rate meter is a rotameter (or equivalent)
used to measure the sample gas flow rate in the range of 0 - 1
£/min (O-to-0.035 ft /min). Inspect the rotameter for cracks,
flaws, and erratic behavior, and check calibration as described
in Section 3.8.2. Return it to the supplier if it is damaged or
cannot be adjusted to within ±5% of the standard rate meter.
Clean and recalibrate if dust and/or liquid contamination is
suspected:
1.1.6 Flexible Bag - The flexible bag used to obtain the inte-
grated gas sample should be leak free and made of Tedlar (or an
equivalent material) with a capacity of 60-to-90 Si (2 to 3 ft3).
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Section No. 3 .8.. 1
Revision No. 0
Date January 4, 1982
Page 6 of 13
Upon receipt of a new bag, check for damage, correct fit-
tings, and capacity. Before using, leak check in the laboratory
by evacuating the bag with a leakless pump. When evacuation is
complete, there should be no flow through the dry gas meter. In
leak testing by evacuation, it is difficult to ascertain whether
the entire bag has been tested. If one wall of the bag presses
against another section and eventually cuts off the flow, the
absence of flow does not guarantee 'that all sections of the bag
are leak free. Therefore, an alternative and preferred test is
to pressurize the bag with air to approximately 51 mm (2 in.) H20
above atmospheric pressure and to monitor the pressure with a
draft gauge over a period of time. Loss of pressure over a 24-h
period should be considered an excessive leak, and the bag should
be repaired or replaced.
1.1.7 Pitot Tube - The pitot tube should be a Type S (or equiv-
alent) as described in Section 3.1 of this Handbook. The pitot
tube is to be used when the sampling rate is regulated propor-
tionally to the stack gas velocity (integrated sample), when the
velocity is varying over time, or when a velocity traverse (flow
rate determination) is conducted.
1.1.8 Wet Test Meter - The wet test meter is used to check the
calibration of the rotameter. The wet test meter should be
3
capable of measuring a volume of 2 i (0.070 ft ) with an accuracy
qf ±1% at a flow rate of 1 £/min (0.035 ft3/min).
Upon receiving a wet test meter, visually check it for
manufacturing defects and leaks, and calibrate it as described in
Section 3.8.2. If it is damaged, behaves erratically, or cannot
be properly adjusted, return it to the manufacturer.
1.1.9 Barometer - A mercury, aneroid, or other barometer capable
of measuring atmospheric pressure to within 2.5 mm (0.1 in.) Hg
may be used; however, in many cases the absolute barometric
pressure can be obtained from a nearby weather service station.
If the elevation of the sampling point is higher than that of the
weather station the reported barometric pressure is reduced at a
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Section No. 3.8.1
Revision No. 0
Date January 4, 1982
Page 7 of 13
rate of 2.5 mm Hg/30 m (0.1 in. Hg/100 ft) of elevation differ-
ence; if the sampling point is lower than the weather station,
the pressure is increased at the same rate. Note; Make sure the
weather service station gives the pressure without correction to
sea level.
Check the field barometer against a mercury-in-glass barom-
eter (or its equivalent). If the field barometer cannot be
adjusted to agree with the mercury-in-glass barometer, it is not
acceptable.
1.1.10 Vacuum Gauge - A vacuum gauge capable of measuring at
least 760 mm (30 in.) Hg is to be used to leak check the sampling
train. Check the vacuum gauge in a parallel leakless system with
a mercury U-tube manometer at a vacuum of 380 mm (15 in.) Hg. Be
sure the gauge agrees within ±25 mm (1.0 in.) Hg. If it does
not, adjust or reject.
1.2 Sample Analysis
1.2.1 Carbon Monoxide Analyzer - The CO analyzer should be a
Luft-type nondispersive infrared (NDIR) spectrometer (or equiva-
lent), which meets or exceeds the specifications in Appendices A
and B in Section 3.8.10. When purchasing a CO analyzer, have the
manufacturer demonstrate that it meets these specifications as
well as those advertised by the manufacturer. The best evidence
is a strip chart record of that analyzer's performance. Guide-
lines for instrument evaluation are given in "Procedures for
Testing Performance Characteristics of Automated Methods,"
Federal Register, Vol. 40, No. 33, February 18, 1975. If the
instrument is defective, return it to the manufacturer for re-
pair, adjustment, or replacement.
1.2.2 Drying Tube - A drying tube packed with 6 to 16 mesh
indicating-type silica gel (or equivalent) should be installed to
remove moisture from the sample. If not removed, the moisture
may interfere with the NDIR measurement of CO.
The tube can be made of stainless steel, glass, or plastic.
Each end of the tube should be packed with glass wool to prevent
the silica gel from entering the sampling train and the NDIR
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Section No. 3.8.1
Revision No. 0
Date January 4, 1982
Page 8 of 13
analyzer. The tube should be leak free at a vacuum of at least
380 mm (15 in.) Hg, and it should have a minimum capacity of
200 g of silica gel. If defective, repair or return to the
supplier.
1.2.3 Carbon Dioxide Removal Tube - Install a flexible plastic
tube packed with 500 g of ascarite to remove C02 from the sample.
If not removed, the C02 may interfere with the NDIR measurement
of CO. Keep tube in a vertical orientation to prevent channel-
ing.
A flexible plastic tube with a minimum ID of 2.5 cm (1.0
in.) and capped at the ends should be used (instead of a rigid
container). When CO, contacts the ascarite, it tends to form a
dense solid plug which can easily block the glass inlet tube of
an impinger. The inlet and outlet lines of the tube should be
configured to maximize exposure of sample gas to the ascarite and
to prevent plugging. Pack each end of the tube with glass wool
to protect the sampling train and the NDIR analyzer from ascarite
dust. Inspect the C02 removal tube for breaks, damage, and
correct fittings; it should be leak free at a vacuum of 380 mm
(15 in.) Hg. If defective, return to the supplier.
The drying tube and the CO. removal tube may be combined
into one unit containing layers of the two materials in the
quantities previously noted. The sample should pass first into
pure silica gel, then into a layer of silica gel and ascarite,
and finally through a layer of ascarite. Repack this tube with
silica gel and ascarite when the existing silica gel exhibits the
characteristic color change.
1.2.4 Filter - Place a filter in the sample in-take line of the
CO analyzer to remove particulates from the gas stream and to
prevent erroneous results and damage to the NDIR analyzer. If
the manufacturer of the CO analyzer specifies a filter type and
size, those should be followed; if not, a standard glass fiber
filter (e.g., MSA1106BH or the equivalent) can be used.
Upon receiving the filter, check for specifications (i.e.,
the type and size ordered). If incorrect, return to the manufac-
turer .
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Section No. 3.8.1
Revision No. 0
Date January 4, 1982
Page 9 of 13
1.2.5 Ice Water Bath - The drying tube and the C0_ removal tube
should be watertight and should be immersed in an ice water bath
of sufficient size to contain and ensure efficient operation of
the tubes. If .the size is incorrect, return the bath to the
supplier.
1.2.6 Carbon Dioxide Analyzer - Carbon dioxide in the gas stream
interferes with NDIR readings, thus use an ascarite trap to
remove all CO2. To correct the CO reading for the removed CO,,,
the percentage of C02 in the stream must be determined by using
an Orsat analyzer, as specified in Section 3.2 of the Handbook.
1.2.7 Recorder - A strip chart recorder is optional; however, it
provides a permanent record of NDIR readings. When ordering a
recorder, make sure that its operating voltage is compatible with
the NDIR voltage output.
Upon receiving a recorder, check for damage and proper
operation throughout its entire input voltage range. If defec-
tive, return it to the suppler.
1.3 Reagents
1.3.1 Calibration Gases - A multipoint calibration for the
selected measurement range of the CO analyzer requires three
known concentrations of calibration gases: one concentration of
CO in nitrogen (N2) for the upper value (span) of the selected
range and two CO concentrations at 30% and 60% of span. In
addition, a prepurified grade of N_ (containing <0.1 ppm CO) is
required for a zero gas.
The analyzer range cannot exceed the source performance
standard by >~L% times. For example, the standard for petroleum
refineries is 500 ppm, thus the maximum range for this industry
would be 750 ppm and the calibrating gases would be 30% and 60%
of 750 ppm—or approximately 225 ppm and 450 ppm. The range of
the analyzer selected should give the lowest possible high-end
reading without being lower than the span gas; for example, an
analyzer with ranges of 0 to 500 ppm, 0 to 1000 ppm, and 0 to
2000 ppm would be calibrated on the 0 to 1000 ppm range for 750
ppm CO.
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Section No. 3.8*1
Revision No. 0
Date January 4, 1982
Page 10 of 13 -
Because some calibration gases with certificate of analysis
have shown significant errors when compared with standard gases,
good quality control procedures require the gas manufacturer to
perform traceability analysis using NBS-Standard Reference
Materials (SRM) or gas manufacturer's Certified Reference
Materials (CRM). The EPA Traceability Protocol No. 1 should be
required of the gas manufacturer for traceability analysis. This
protocol is described in Section 3.0.4 of this Handbook. For
convenience, a summary of Protocol No. 1 as it applies to stan-
dards of CO in N2 is shown in Section 3.8.9. A list of gas manu-
facturer's that have prepared approved CRM's is available from
EPA at the following address:
U.S. Environmental Protection Agency
Quality Assurance Division (MD-77)
Research Triangle Park, North Carolina 27711
Attn: List of CRM Manufacturers
Calibration gases must be certified by the gas manufacturer
to within ± 2% of the specified concentration. Do not store gas
cylinders in areas subject to extreme temperature changes.
Before each calibration, check the cylinder pressure of each
2
calibration gas and replace any with < 1400 KN/m (200 psi)
pressure.
1.3.2 Silica Gel - Indicating-type 6 to 16 mesh should be dried
at 175°C (347°F) for at least 2 h. The color should be blue when
the water has been removed.
1.3.3 Ascarite - Ascarite (20 to 30 mesh) is commercially avail-
able. It consists of asbestos coated with sodium hydroxide which
forms sodium carbonate when exposed to C02. Eventually, the
ascarite is spent, and has to be replaced since it cannot be
regenerated.
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Section No. 3.8.1
Revision No. 0
Date January 4, 1982
Page 11 of 13
TABLE 1.1. ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS
AND SUPPLIES
Apparatus
and supplies
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Sampling
Sampling probe
Stainless steel (316)
or sheathed Pyrex glass
with filter to remove
particulate matter; no
damage, cracks or
breaks; leak free at
380 mm (15 in.) Hg
Visually check for
length and composi-
tion ordered; leak
check
Repair or re-
turn to sup-
plier
Air-cooled
condenser
Capacity sufficient to
collect all condensed
moisture from the sam-
ple gas; no damage,
cracks, or breaks,.
leak free at 25 mm
(1 in.) H20 positive
pressure and at 380 mm
(15 in.) Hg vacuum
Check for size and
damage; leak check
Repair or re-
turn to sup-
plier
Needle valve
Stainless steel; capable
of regulating the flow
rate over the range of
0 to 1 £/min (0 to
0.035 ftVmin); leak-
free fittings
Install in sampling
train; check for
proper operation;
leak check
Repair or re-
turn to sup-
plier
Vacuum pump
Leak-free diaphragm at
380 mm (15 in.) Hg or
equivalent; capable of
maintaining a flow rate
of 1 £/min (0 to 0.035
ftVmin) at 380 mm (15
in.) Hg for 30 S
Leak check; check for
for damage and
capability of main-
taining desired flow
rate
Return to
supplier
Rate meter
(continued)
Rotameter or equivalent;
no cracks, flaws, or
erratic behavior; mea-
sure gas flow in the
range of 0 - 1 £/min
(0 to 0.035 ftVmin);
agree within ±5% of
standard rate meter
Check for cracks and
flaws and calibrate
against a wet test
meter (Sec. 3.8.2)
Return to
supplier
-------
Section No. 3.8.1
Revision No. 0
Date January 4, 1982
Page 12 of 13 -
TABLE 1.1 (continued)
Apparatus
and supplies
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Flexible bag
Tedlar or equivalent;
capacity of 60 to 90 £
(2 to 3 ft3); leak
free at 51 mm (2 in.)
H20 for 24 h
Check for capacity,
damage, correct fit-
tings; leak check
Repair or
replace
Pi tot tube
Type S (Method 2,
Sec 3.1.1)
Calibrate according
to Sec 3.1.2
Repair or
return to
supplier
Wet test meter
Capable of measuring
total volume with
accuracy of ±1% at a
flow rate of 1 £/min
(0.035 ft3/min)
Upon assembly, leak
check all connections;
calibrate by liquid
displacement (Sec
3.8.2)
Reject if
damaged, be-
haves errati-
cally or can-
not be ad-
justed prop-
erly
Barometer
Capable of measuring
atmospheric pressure to
±2.5 mm (0.1 in.) Hg
Check against a mer-
cury- in-glass barom-
eter or equivalent
(Sec 3.8.2)
Determine
correction
factor, or
reject
Vacuum gauge
0 to 760 mm Hg range
±25 mm (1.0 in.) at
380 mm (15 in.) Hg
Check against a U-tube
mercury manometer upon
receipt
Adjust or
return to
supplier
Sample Analysis
CO analyzer
NDIR spectrometer or
equivalent; meets speci-
fications in Sec 3.8.10
Appendices A and B
Have supplier (1) de-
monstrate that it
meets or exceeds per-
formance specs, and
(2) provide a strip
chart record of runs
Return to
supplier for
repair, ad-
justment, or
replacement
Drying tube
Capacity of at least
200 g of silica gel;
leak free at 380 mm
(15 in.) Hg
Check upon receipt
for proper size;
leak check
Repair or re-
turn to sup-
plier
(continued)
-------
Section No. 3.8.1
Revision No. 0
Date January 4, 1982
Page 13 of 13
TABLE 1:1 (continued)
Apparatus
and supplies
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Filter
Type and size recom-
mended by NDIR manufac-
turer, or glass fiber
filter
Check upon receipt
for proper size and
type
Return to
supplier
C02 removal
tube
Contains 500 g of ascar-
ite; leak free at 380
mm Hg (15 in.); may
combine silica gel and
C02 removal tubes (Sec
3.8.1)
Check upon receipt
for proper size,
fittings, and leak
check
Return to
supplier
Ice water bath
Sufficient size to con-
tain drying and C02 re-
moval tubes
Check upon receipt
for proper size;
leak check
Return to
supplier
Recorder
(optional)
Strip chart recorder
with operating voltage
compatible with NDIR
or equivalent data
logger
Check for damage and
proper operation over
entire voltage range
Return to
supplier
Carbon dioxide
analyzers
Orsat analyzer (Method
3, Sec 3.2)
Check according to
Meth. 3, Sec 3.2
Return to
supplier
Reagents
Calibration
gases
Certified by manufac-
turer to ±2% of
specified concentra-
tion; traceability to
NBS-SRM or CRM (CO in
N2)
Traceability analysis
required of the gas
manufacturer using
EPA traceability
Protocol No. 1
Return to
supplier
Silica gel
Indicating-type 6 to 16
mesh; blue in color
Dry at 175°C (347°F)
for at least 2 h
prior to use
Discard or
return to
supplier
Ascarite
20 to 30 mesh
Check label for cor-
rect type
Return to
supplier
-------
Section No. 3.8.2
Revision No. 0
Date January 4, 1982
Page 1 of 18
2.0 CALIBRATION OF APPARATUS
Calibration of the apparatus is most important for maintain-
ing data quality. The calibration procedures are designed for
the equipment specified by Method 10 and described in the pre-
vious section. Table 2.1 summarizes the quality assurance activ-
ities for calibration. All calibrations should be recorded on
standardized forms and retained in a calibration log book.
2.1 Metering System
2.1.1 Wet Test Meter - The wet test meter must be calibrated and
must have the proper capacity. For Method 10, the wet test meter
should have a capacity of >2 £/min (0.070 ft3/min). No upper
limit is placed on the capacity; however, a wet test meter dial
should make at least one complete revolution at the specified
flow rate for each of the three independent calibrations.
Wet test meters are calibrated by manufacturers to an accu-
racy of ±0.5%. Calibration must be checked initially upon re-
ceipt and yearly thereafter. The following liquid positive
displacement technique can be used to verify and adjust, if
necessary, the accuracy of the wet test meter (Figure 2.1) to
1. Level the wet test meter by adjusting the legs until
the bubble in the level located on the top of the meter is cen-
tered.
2. Adjust the water volume in the meter so that the
pointer in the water level gauge just touches the meniscus
3. Adjust the manometer to zero by moving the scale or by
adding water to the manometer.
4. Set up the apparatus and calibration system. (Figure
2.1).
5. Fill the rigid-walled 5-gal jug with distilled water to
below the air inlet tube. Allow the system to equilibrate to
room temperature (about 24 h) before use.
-------
Section No. -3.8.2
Revision No. 0
Date January 4, 1982
Page 2 of 18
THERMOMETER
AIR INLET
AIR INLET
TUBE
5-•GAL RESERVOIR
SIPHON TUBE
VALVE
2000 ml LINE
TYPE A -
VOLUMETRIC
FLASK
WATER OUT /sTJ~_:
LEVEL ADJUST
Figure 2.1. Calibration check apparatus for wet test meter.
-------
Section No. 3.8.2
Revision No. 0
Date January 4, 1982
Page 3 of 18
6. Start water siphoning through the system, and collect
-the water in a 1-gal container, located in place of the class A
volumetric flask.
7. Check the operation of the wet test meter as follows:
If the manometer reading is <10 mm (0.4 in.) H2O, the meter is in
proper working condition. Continue to step 8. If the reading is
>10 mm (0.4 in.) H20, the meter is defective; return it to the
manufacturer for repair if the defect(s) (e.g., bad connections
or joints) cannot be corrected.
8. Continue the operation until the 1-gal container is
almost full and then plug the inlet to the saturator. If no leak
exists, the flow of liquid to the container should stop; if the
flow continues, correct for leaks. Turn the siphon system off by
closing the valve, and then unplugging the inlet to the wet test
meter.
9. Read the initial volume (V.) from the wet test meter
dial, and record it on the calibration log, Figure 2.2.
10. Place a clean, dry volumetric flask (Class A) under the
siphon tube, open the pinch clamp, and fill the flask to the
mark. Note; The flask must be large enough to allow at least
one complete revolution of the wet test meter dial with no more
than two fillings of the flask.
11. Start the flow of water, be sure the flow of liquid is
constant, and record the maximum wet test meter manometer reading
during the test.
12 Carefully fill the volumetric flask, shut off the
liquid flow at the 2-£ mark, and record the final volume (Vf)
from the wet test meter on Figure 2.2.
13. Perform steps 9 through 13 three times.
Since the water temperature in the wet test meter and the
reservoir has been equilibrated to ambient temperature and since
the pressure in the meter will equilibrate with that in the
reservoir after the water flow is shut off, the air volume can be
-------
Wet test meter serial number 43 -
Wet test meter flow range o-/zn
Volume of test flask, V
Date
80
Calibrated by
g,oo
Satisfactory leak check
Liquid in wet test meter and reservoir allowed to equilibrate with ambient temperature
Test
number
/
a
j
Manometer
reading,
mm H2O
S
S
S
Final
volume
(Vf), £
/.99
Z.oo
2.oO
Initial
volume
(Vi), SL
0
0
0
Total.
volume
> fu (ft (ft
ua rK O
(ft (ft H-ft
CO H-
^ Ci H-O
0)
u>
.o •
•CD
' K>
vo
CD
to
-------
Section No. 3.8.2
Revision No. 0
Date January 4, 1982
Page 5 of 18
compared directly to the liquid displacement volume. Any temper-
ature or pressure difference would be less than measurement error
and would not affect the final calculations.
The calibration error should not exceed ±1%; should this
error of magnitude be exceeded, check all connections within the
test apparatus for leaks, and gravimetrically check the volume of
the standard flask. Repeat the calibration procedure, and if the
tolerance level is not met, adjust the liquid level within the
meter (see manufacturer's manual) until the specifications are
met.
2.1.2 Rotameter - The Reference Method does not Require calibra-
tion of the rotameter; however, besides cleaning and maintaining
the rotameter according to manufacturer's instructions, its
calibration curve and/or marking should be checked upon receipt
and then after each test series. A procedure is as follows:
1. Prepare the apparatus (Figure 2.3) using short connec-
tions and tubing with the same ID used in the Method 10 sampling
train.
3
2. Start the air flowing at 0.5 £/min (0.02 ft /min) to
saturate the water in the wet test meter and to wet the interior
surfaces of the wet test meter.
3. Record the barometric pressure (Pn) on the rotameter
D
calibration form (Figure 2.4A or 2.4B).
4. Adjust the flow (Re) to 0.10 2/min (0.0035 ft3/min)
s
with the needle valve.
5. Use a stopwatch to measure the time (0) required to
make at least two revolutions of the wet test meter dial.
6. Repeat step 4 with the flow (R ) adjusted to 0.25,
S
0.50, 0.75, and 1.0 2/min (0.009, 0.018, 0.027, and 0.035
3
ft /mm) going from a flow of 1.0 to 0.10 2/mm. Record the
time, the rotameter reading (R_), the elapsed time of. the run
5
(6), the temperature of the liquid in the wet test meter (t ),
the manometer reading at the wet test meter (D ), and the total
volume displaced for each run (V).
Vr
-------
MANOMETER
ft THERMOMETER
NEEDLE
VALVE
AIR
OUTLET
PUMP
WET TEST METER
(V
AIR INLET
• \j t^j vO Crt
0> Pi (D fP
vQ ft < O
0) (D H-rt
tn H-
CT> Cj H- O
p) o a
O 3 3
Figure 2.3. Rotameter calibration assembly.
CO
.'
03
to
00
-------
Rotameter serial number
Location
Wet test meter number
Date 1-2.7-80
Barometric pressure, P
B
in. Hg Calibrated by
Rs'
ft3/min
0 027
e,
min
^
V
OF
(A
.V
in. H2O
-O.I
V
ft3
n.oAI
Vr'
ft3
O.O8I
QS'
ft3 /min
o.nsi
Rs =
e =
Dm =
V =
p_ =
rotameter setting, ft3/min (e. g., 0.009, 0.018, 0.027)
time of calibration run, min
temperature of the gas in wet test meter, °F
pressure drop on the wet test meter, in. H2O (a negative number if calibrated
as in Figure 2.3)
gas volume passing through wet test meter, ft3
gas volume passing through the rotameter corrected to STP, ft3
flow rate through rotameter, corrected to STP, ft3/min
standard temperature, 68°F
standard pressure, 29.92 in. Hg
+ 460>
Vw(PB
Dm/13-6)
17'65 VPB
(t
w
460)
(t
w
460)
= ft3 at STP.
V
~ = ft3 /min at STP.
o
Figure 2.4A. Rotameter calibration data form (English units).
*tJ O £0 W
(U (U (ft (ft
vQ ft< O
(ft (ft H-ft
W H-
•>J Q H-O
pop
PI as o
MHO'
C0k< .
00
vo
00
to
-------
Rotameter serial number
Location ^fapcF. Tesr
Wet test meter number 43
Date /-27-8Q
Barometric pressure, P_
mm Hg Calibrated by
go.
Rs'
£/min
O. 75"
6,
min
v3
V
°c
2.0
Dm'
mm H2O
-2.34
*
VW
£
£.25
V
£
-2.25"
V
£/min
0.7S-
Rs =
e =
Dm =
Vw =
V =
P_ =
V =
rotameter setting, £/min (e.g., 0, 0.50, 0.75)
time of calibration run, min
temperature of the gas in the test meter, °C
pressure drop on the wet test meter, mm H2O (a negative number if calibrated
as in Figure 2.3)
gas volume passing through wet test meter, £
gas volume passing through the rotameter corrected to STP, £
flow rate through rotameter, corrected to STP, £/min
standard temperature, 20°C
standard pressure, 760 mm Hg
Vw(PB + Dm/13-6) (ts + 273> °'386 Vw (PB + Dn/13'6>
m
(tw + 273)
(tw + 273)
= £ at STP.
V
6
-jj = £/min at STP.
Figure 2.4B. Rotameter calibration data form (Metric units).
to
jtf in
n n>
< o
n> (D H-rt
OT H-
00 QH-O
POP
030
H, c as
fu SS O
CD
10
*
00
*
to
vo
CD
to
-------
Section No. 3.8.2
Revision No. 0
Date January 4, 1982
Page 9 of 18
7. Calculate the volume (V ) at standard conditions (STP)
for each test point, and record on Figure 2.4A or B.
8. Calculate the standard flow rate (Q ) for each test
5
point, and record on Figure'2.4A or 2.4B.
9. Plot the rotameter setting (R ) versus the flow rate
s
(Q ) on linear graph paper by using a flexible rule to construct
5
a best-fit smooth curve through the data points. Note: A
typical relationship is shown in Figure 2.5. All data points
should be within ±2% of the best-fit curve.
10. Apply the following corrections to convert the flow
rate to STP if the rotameter is used in a field location where
the barometric pressure and/or temperature is different from
those recorded when the rotameter was calibrated.
/Pf 293 \1/2
Qs = Qf (?fo X t^J Equation 2-1
where
Q = flow rate corrected from field conditions to STP,
5
£/min;
Qf = flow rate at field conditions from calibration curve,
jfc/min;
Pf = barometric pressure at field conditions, mm Hg; and
tf = temperature at field conditions, average temperature of
sampling train, K.
2.1.3 Barometer - The field barometer should be adjusted upon
receipt and before each test series to ±2.5 mm (0.1 in.) Hg of a
mercury-in-glass barometer. If a field barometer is not availa-
ble, a nearby weather service barometric pressure can be used.
If the sampling point is higher in elevation than the
weather station, the reported barometric pressure is reduced at a
rate of 2.5 mm Hg/30 m (0.1 in. Hg/100 ft) of elevation differ-
ence; if the sampling point is lower than the weather- station,
the pressure should be increased at the same rate. Note; Make
sure that the pressure obtained from the weather station has not
been corrected to sea level conditions.
-------
300
250
~ 200
150
TOO
50
Section No. 3.-8.2
Revision No. 0
Date January 4, 1982
Page 10 of 18 •
\ \
1i r
I rT
FLOW METER SERIAL NO._2£ZJ_
LOCATION>
TEMPERATURE, °C £J
ATMOSPHERIC PRESSURE, mm H£
CALIBRATED BY IF' Jbfc
i I
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
FLOW RATE AT STP (Qs), liters/min
Figure 2.5. Typical rotameter calibration curve.
-------
Section No. 3.8.2
Revision No. 0
Date January 4, 1982
Page 11 of 18
2.2 Analysis System
2.2.1 Carbon Monoxide Analyzer - The NDIR and the associated
apparatus are shown in Figure 2.6; all components are the same as
those used in the sampling train. Prior to leak check and cali-
bration, add new or reconditioned indicating-type silica gel and
new ascarite. Then leak check the system by closing the gas
cylinder valves and excess flow valve; opening the control
needle valve; and turning on the pump. If the rate meter at the
NDIR inlet indicates flow, there is a leak. Check all connec-
tions and fittings for tightness. After the leak check, open the
excess flow valve, shut off the pump, turn on the power, and
allow the analyzer to warm up according to the manufacturer's
instructions. Because the NDIR analyzer is temperature sensi-
tive, allow it to warm up >2 h. When calibrating an analyzer,
follow the manufacturer's instructions for setting the zero and
the up-scale span point.
Calibration of NDIR analyzers may be multipoint checks; zero
and span checks; or a zero check. Multipoint calibration is used
to establish the calibration curve (or relationship) between the
analyzer output and the CO input; this type of calibration is
performed upon receipt of the analyzer, before any sampling
series, and immediately after maintenance or internal adjustments
of the analyzer. Zero and span checks establish whether the
predetermined calibration curve has changed during analysis; this
type calibration is performed at the. end of each test series or
at the start and end of each day for continuous sampling that
runs for more than a day. A zero check is used both to establish
whether the analyzer zero has drifted during a test and to adjust
the analyzer if it has drifted. The zero check is made before
each sample bag is analyzed for integrated samples.
Multipoint Calibration - The multipoint procedure can be
used for introducing calibration gases to the analyzer and for
plotting calibration curves.
-------
EXCESS FLOW
VALVE
RECORDER
EXCESS FLOW
RATE METER
RATE
CONTROL
NEEDLE
NDIR
SAMPLE
RATE METER
ZERO
GAS
SPAN
GAS
Figure 2.6. Calibration setup.
(u (u (D n>
vQ rt< O
n> n> H-rt
OT H-
MC-4 H-O
N>p> O 0
og0^
550
o •
00
to
00
VD
OO
-------
Section No. 3.8.2
Revision No. 0
Date January 4, 1982
Page 13 of 18
1. Open the excess flow valve and the control needle
valve, and then turn on the pump.
2. Open the zero gas cylinder valve, and adjust the sec-
ondary pressure regulator to deliver 10 pounds per square inch,
gauge (10 psig).
3. Adjust the zero gas control and the control needle
valves slowly and simultaneously until the excess flow meter
indicates a low rate (to ensure that air is not being pulled back
through the excess flow line by the pump) and until the derived
flow rate is reached at the sample rate meter. Note: Flow rates
of 0.5 to 1.0 £/min are normally recommended; most analyzers are
not sensitive to flow rate changes below 1.0 £/min, but the rate
established at calibration should be maintained throughout the
test series.
4. Set the analyzer zero by manufacturer's instructions
after a stable reading is established (a minimum of 5 min).
5. Adjust the recorder zero control knob until the trace
corresponds to the line representing 5% of the strip chart width
above the chart zero or baseline to allow for any negative zero
drift. If the strip chart already has an elevated baseline, use
it for the zero setting.
6. Mark the strip chart trace at adjusted zero, and record
the data on Figure 2.7.
7. Turn off the zero gas.
8. Open the span gas cylinder valve, and adjust the sec-
ondary pressure regulator to deliver 10 psig.
9. Open the span gas control valve until the excess flow
meter indicates a low flow (refer to step 3).
10. Check the sample rate meter to assure that the same
flow rate used to zero the analyzer is maintained; if not, adjust
the flow valves.
11. Set the analyzer span by manufacturer's instructions
after a stable trace is established (a minimum of 5 min). Note;
Some analyzers require two or more adjustments of the zero and
the span setting to get desired readings.
-------
Section No. 3.8*2
Revision No. 0
Date January 4, 1982
Page 14 of 18
Flow rate
Location SOURCE TSsr JAB Date 7-2.6-80
Analyzer number 2&7-L Range Q-/ooOa
Zero gas /\4 Cylinder pressure /soo
Span gas -740 Cylinder pressure
60% span gas 445 ppm Cylinder pressure
30% span gas 22.5 ppm Cylinder pressure 7530 PS/&
Operator
Cell pressure
Cylinder number /7-674N
Cylinder number
Cylinder number
Cylinder number
Zero control setting
Recorder type
Span control setting
Serial number
200
400 600
CO IN N2t
800
1000
Figure 2.7. Sample calibration curve.
-------
Section No. 3.8.2
Revision No. 0
Date January 4, 1982
Page 15 of 18
12. Mark the strip chart trace for the adjusted span, and
record the data on Figure 2.7.
13. Close the span gas cylinder valve and the control
valve, and remove the cylinder from the pressure regulator.
14. Replace the span gas cylinder with the reference gas
cylinder that contains the 60% of span concentration.
15. Open the reference gas cylinder valve, and adjust the
cylinder secondary pressure regulator to deliver 10 psig. Repeat
steps 9 and 10.
16. Allow a stable trace to be established on the recorder.
DO NOT ADJUST ANALYZER ZERO OR SPAN CONTROL. Mark the strip
chart trace, and record the data on the form.
17. Repeat steps 13 through 16 for the 30% span concen-
tration.
18. Plot concentration-versus-percentage relationship (Fig-
ure 2.7) after the multipoint calibration is complete.
19. Turn off all gas cylinders, and remove excess flow
valve and rate meter assembly.
The analyzer is now ready for sample analysis.
Zero and Span Checks - Follow this procedure in conducting
the zero and span checks:
1. Attach the excess flow rate meter and excess flow valve
assembly as shown in Figure 2.6.
2. Open the zero gas cylinder valve, and adjust the sec-
4
ondary pressure regulator to deliver 6.9 x lo Pa gauge (10
psig).
3. Adjust the zero gas control and the control needle
valves slowly and simultaneously until the excess flow meter
indicates a low flow and the sample rate meter reads the same as
it did during sampling.
4. Mark the strip chart trace as "unadjusted zero" and
record the data on Figure 2.8 after a stable zero trace is estab-
lished.
-------
Section No. 3.8.2.
Revision No. 0
Date January 4, 1982
Page 16 of 18
Location Sou ere.
Analyzer
LPtft
Operator ~T.
Date
Time
Test
number
Zero
unadjusted
adjusted
Span
unadjusted
adjusted
Percent
dif-
ference
If. 15
NR-1
-0.5-%
-O-
100%
Figure 2.8. Example calibration verification record chart.
-------
Section No. 3.8.2
Revision No. 0
Date January 4, 1982
Page 17 of 18
5. Adjust the analyzer zero to the zero reading estab-
lished in the multipoint calibration; mark the strip chart trace
as "adjusted zero"; and record the value on the form.
6. Turn off the zero gas.
7. Open the span gas cylinder valve, and adjust the sec-
ondary pressure regulator to deliver 10 psig.
8. Open the span gas control valve until the excess flow
meter indicates a flow.
9. Check the sample rate meter and be sure that the same
flow rate used to zero the analyzer is maintained. If not,
adjust the flow valves.
10. After a stable span trace is achieved, label as "un-
adjusted span" and record the value on Figure 2.8.
11. If the unadjusted span value (from the calibration
curve) differs from the span value determined during the multi-
point calibration by more than ±10%, reset the span setting. Use
Equation 2-2 to determine the percentage difference between the
two values.
C0c ~ c°s
% difference = —=7—5 x 100 Equation 2-2
COs
where
CO = concentration of span gas, and
CO - concentration of span gas as determined.
s
Zero Check - A zero check is needed at the beginning of each
integrated sample run and at the beginning and end of each con-
tinuous sampling test. Use the zero check and adjustment de-
scribed above. Record the zero check values on Figure 2.8.
-------
Section No. 3.8.?
Revision No. 0
Date January 4, 1982
Page 18 of 18
TABLE 2.1. ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Metering System
Wet test meter
Capacity >2 2/min;
accuracy ±1.0% for
small wet test meter
Calibrate initially
and quarterly by 1(i-
quid displacement
technique
Adjust until
specifications
are met, or
return to manu-
facturer
Rotameter
Clean and maintain by
manufacturer's instruc-
tions; calibrate to
±2%
Upon receipt and
after each field
trip
Adjust and re-
calibrate, or
reject
Barometer
±2.5 mm (0.1 in.) Hg
of mercury-in-glass
barometer
Calibrate initially
using a mercury-in-
glass barometer and
after each field
test
Adjust to
agree with
certified
barometer
Analysis System
Pi tot tube
Meth 2, Sec 3.1
Meth 2, Sec 3.1
Meth 2, Sec
3.1
CO analyzer
Multipoint calibration:
3-point (plus zero) to
to establish curve of
analyzer
Calibrate upon re-
ceipt, at the begin-
ning of any test se-
ries, and immediately
after maintenance or
internal adjustment,
calibrate by adjusting
span concentration to
agree with certified
gas concentration
Recalibrate
instrument
-------
Section No. 3.8.3
Revision No. 0
Date January 4, 1982
Page 1 of 6
3.0 PRESAMPLING OPERATIONS
The quality assurance activities for presampling operations
are summarized in Table 3.1 at the end of this section. (See
Section 3.0 of this Handbook for details on preliminary site
visits.) The Pretest Sampling Checks, Figure 3.1, and Pretest
Preparation Checklist, Figure 3.2, should be completed before
leaving for the field test.
3.1 Checking and Calibrating the Apparatus
3.1.1 • Sampling Train - The CO sampling trains, integrated and
continuous, are depicted in Figures 1.1 and 1.2, respectively.
Commercial models are available, or sampling trains can be manu-
factured in house if the apparatus complies with specifications
in the Reference Method (Section 3.8.10).
3.1.2 Probe - The probe should be cleaned internally by brushing
first with tap water, then with deionized distilled water, and
finally with acetone. Allow the probe to air dry. The objective
is to leave the probe contaminant free.
The probe should be sealed and then leak checked at a vacuum
of 380 mm (15 in.) Hg. See Section 3.8,1 for leak-check proce-
dures .
3.1.3 Air-Cooled Condenser - The air-cooled condenser should be
cleaned with tap water, then with deionized distilled water, and
finally rinsed with acetone and allowed to air dry. The objec-
tive is to leave the condenser contaminant free. Leak check the
condenser as described in Section 3.8.1.
3.1.4 Needle Valve and Rotameter - The metering valve and rota-
meter should be cleaned according to the manufacturer's recommen-
dations prior to each field trip or on any sign of erratic behav-
ior. After the rotameter is cleaned, it should be recalibrated
(Section 3.8.2).
3.1.5 Vacuum Pump - The vacuum pump should be inspected for
damage and leaks before each field trip. Leak test the pump as
described in Section 3.8.1.
-------
Section No. 3.8.3
Revision No. 0 *
Date January 4, 1982
Page 2 of 6
Date 7-/J- 8O Completed by J".
Pitot Tube
Identification number 76 3 Date
Dimensional specifications checked?* ^ yes _ no
Calibration required? _ _ yes _ t^" _ __ no
Date rr-//- ?6 _ C _ p. $4 _
Rotameter
Identification number
Calibration required?* _ ^ _ yes _ _ no
Barometer
Calibrated?* _ ^ _ yes _ _ __ no
*Most significant items/parameters to be checked.
Figure 3.1. Pretest sampling checks.
-------
Section No. 3.8.3
Revision No. 0
Date January 4, 1982
Page 3 of 6
Apparatus check
Probe
Pvrex glass ,/
Stainless steel
Filter ^^^ v\l06L
Pitot tube
Type '??
Length 5"
Calibrated* y£$
Differential
pressure gauge
/VCX^/27) fdtMOtftttfcL
Air-cooled con-
denser
Clean yg$
Leak checked* y^
Needle valve and
rotameter
Clean \fgS
Calibrated* y%$
Barometer
Type AtiZRO/D
Calibrated* ygS
Pump
Type D/APJ+RM^rf
Leak checked y/rs
Flexible bag
Type -fenLAR.
Leak checked* yg"5
Evacuated* y^
Acceptable
Yes
i/
\s
>/
V
\s
V
/
I/
iX
I/
No
Quantity
required
4
1 &X
A
4
4-
4
/
4
10
Ready
Yes
V
IX
I/
I/"
I/
/
^
iX
X
NO
Loaded
and packed
y£r
y^5
X^5
/£5
y^s
y£5
/^5
Kf5
vrs
*Most significant items/parameters to be checked.
Figure 3.2. Pretest preparation checklist.
-------
Section No. 3.8.3
Revision No. 0
Date January 4, 1982
Page 4 of 6
3.1.6 Flexible Bag - The flexible bag should be visually inspec-
ted for damage; leak checked; and evacuated before each field
trip. For leak-check procedures, see Section 3.8.1.
3.1.7 Pitot Tube - The presampling operations required prior to
using the pitot tube in the field are described in Method 2,
Section 3.1.
3.1.8 Barometer - The field barometer should be calibrated prior
to each field trip as described in Section 3.8.2.
3.2 Packing the Equipment for Shipment
3.2.1 Probe - Pack the probe in a case protected by polyethylene
foam or other suitable packing material. Seal and protect the
inlet and outlet of the probe from breakage. An ideal container
is a wooden case (or equivalent) with separate polyethylene-lined
compartments for individual pieces. The case should have handles
or eyehooks that can withstand hoisting and that are rigid enough
to prevent bending or twisting of the devices during shipping and
handling.
3.2.2 Air-Cooled Condenser, Needle Valve, Rotameter, and Vacuum
Pump - The air-cooled condenser, needle valve, rotameter,
and vacuum pump should be mounted securely in a permanent con-
tainer and cushioned (e.g., the pump bolted to the inside of a
wooden box with rubber bushings between the pump and the box
sides). Polyethylene foam can be used to cushion the components.
The container should have handles or eyehooks that can withstand
hoisting and that are rigid enough to prevent bending or twisting
of components during shipping and handling.
3.2.3 Miscellaneous Equipment - Flexible bags, barometer, pitot
tube, CO analyzer (if continuous sampling), and other miscella-
neous equipment needed in the field should be packed conveniently
and securely in containers and labeled (as to contents) for ease
of identification in the field.
-------
Section No. 3.8.3
Revision No. 0
Date January 4, 1982
Page 5 of 6
TABLE 3.1. ACTIVITY MATRIX FOR PRESAMPLING OPERATIONS
Operation
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Apparatus Check
and Calibration
Probe
Free of contaminants;
leak free
Clean internally by
brushing, using tap
water, deionized
distilled water, and
acetone, air dry;
seal and check for
leaks at 380 mm (15
in.) Hg prior to
field use
Repeat clean-
ing procedure;
repair or re-
place
Air-cooled
condenser
Free of contaminants;
leak free
As above
As above
Needle valve
and rotameter
Clean and without signs
of erratic behavior
Clean by manufactur-
er's recommendations
prior to each field
trip or at sign of
erratic behavior
Repair or re-
turn to manu-
facturer
Vacuum pump
No damage or leaks;
full oiler jar (if re-
quired)
Before field trip;
visually inspect for
damage; check oil
level; leak check as
described in Sec 3.8.1
Repair or
replace
Flexible bag
Leak free and evacu-
ated
Before field trip;
leak check according
to Sec 3.8.1, and
evacuate
Repair or
replace
Pi tot tube
Meth 2, Sec 3.1
Meth 2, Sec 3.1
Meth 2, Sec 3.1
Barometer
Agrees ±2.5 mm (0.1
in.) Hg with mercury-
iri-glass barometer
Before field trip,
calibrate against
barometer (Sec 3.8.1)
Adjust and
calibrate, or
replace
(continued)
-------
Section No. 3.8.3
Revision No. 0
Date January 4, 1982
Page 6 of 6
TABLE 3.1 (continued)
Operation
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Packing Equip-
ment for Ship-
ment
Probe
Rigid case; probe pro-
tected from breakage
Before field trip,
pack probe in
suitable container
Repack
Rotameter
Mounted in permanent
protective container
Before field trip,
mount permanently in
protective container
Permanently
mount in
protective
container
Flexible bag,
pi tot tube,
CO analyzer,
etc.
Packed in secure
container
Before field trip,
pack in shipping
container
Repack
-------
Section No. 3.8.4
Revision No. 0
Date January 4, 1982
Page 1 of 12
4.0 ON-SITE MEASUREMENTS
On-site measurement activities include transporting equip-
ment to the test site; making duct measurements; conducting a
velocity traverse; determining moisture content of stack gas;
sampling for CO; recording data on appropriate forms; and label-
ing samples and containers for shipping. A clean "laboratory"
type area free of excessive drafts should be designated for
equipment storage, sample recovery, train assembly, and documen-
tation.
Table 4.1 at the end of this section summarizes the quality
assurance activities for on-site measurements. Copies of all
field data forms mentioned in this section are in Section 3.8.12.
The on-site measurements checklist, Figure 4.4 at the end of this
section, provides the tester with a quick method for checking
requirements during sampling.
4.1 Equipment Transport
The most efficient means of transporting equipment from
ground level to the sampling site should be decided during the
preliminary site visit or through prior correspondence. Care
should be taken to prevent injury to test personnel or damage to
the test equipment during equipment transport.
4.2 Sampling
The on-site sampling includes the following steps:
1. Preliminary measurements and setup.
2. Preparation and setup of sampling train.
3. Preparation of the probe (placing filter in probe).
4. Connection to electric service.
5. Leak check of the entire sampling train.
6. Insertion of probe into the stack.
7. Sealing of the port.
8. Sampling (continuous or integrated).
9. Determination of stack gas C02 content.
10. Recording of the data.
-------
Section No. 3.8.4
Revision No. 0
Date January 4, 1982
Page 2 of 12
Upon completion of sampling, a leak check of the sampling
train is required.
4.2.1 Preliminary Measurements and Setup - The sampling site
should be selected in accordance with Method 1. If this is
impossible due to duct configuration or other reasons, the sam-
pling site location should be approved by the administrator. The
site must be acceptable before a valid sample can be taken.
Check for a 115-V, 20-A electrical service; this is adequate to
operate the standard sampling train. Measure the stack ID.
Either determine the minimum number of traverse points (Method 1)
or check the points already determined during .the preliminary
site visit. Record all data on the point location form (Section
3.0). These measurements may be needed to locate the pitot tube
and probe .during sampling.
4.2.2 Stack Parameters - Determine the stack pressure and tem-
perature; determine the range of velocity heads and the proper
differential pressure gauge for the range; and conduct a leak
check of the velocity pressure system (Method 2). Determine the
approximate moisture content (Method 4 or its alternatives) for
selecting the size of the condenser and the quantity of silica
gel required in the sampling train. If the source has been
tested before, an estimate of moisture based on previous test
data should be sufficient.
Determine the dry molecular weight of the stack gas. If an
integrated sample is required, follow the procedures for collect-
ing the sample simultaneously with (and for the same length of
time as) the CO sample, and use the sampling and analytical data
forms in Method 3.
If a traverse is required, select a probe length sufficient
for sampling all points. For large stacks, consider sampling
from opposite sides of the stack to reduce the length of the
probe. 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.
-------
Section No. 3.8.4
Revision No. 0
Date January 4, 1982
Page 3 of 12
Select a total sampling time greater than or equal to the
minimum total sampling time specified in the industry test proce-
dures. Selection should assure that the sampling time per point
(if traverse is required) is >2 min and that the sample volume
corrected to standard conditions exceeds the minimum total gas
sample volume required for that industry. The latter can be
based on an approximate average sampling rate. The number of
minutes sampled at each point (if a traverse is required) should
be an integer or an integer plus one-half minute to avoid time-
keeping errors. In some circumstances (e.g., batch cycles), it
may be necessary to sample for shorter times at the traverse
points and to obtain smaller gas volumes; if so, the adminis-
trator's approval must first be obtained.
4.2.3 Probe and Sampling Train Preparations - Prepare the probe
and the sampling train in the laboratory type area. First, place
a loosely packed filter of glass wool in the end of the probe.
(This filter should be changed after each test or after every 4 h
of sampling. ) Then if a continuous sample is required, fill the
drying tube with silica gel (minimum of 200 g is recommended),
and fill the CO2 removal tube with ascarite. During preparation
and assembly of the sampling train, keep all openings covered to
prevent contamination. Just before collecting the sample, con-
nect the probe and the flexible bag or NDIR analyzer to the
sampling train.
4.2.4 Continuous Sampling - Follow the procedure below to obtain
a continuous sample.
1. Leak check the train just before sampling by placing a
gauge at the probe inlet and pulling a vacuum of >_250 mm (10 in.)
Hg. Turn the pump off. Note: The vacuum should remain stable
for at least 30 s; if not, find and eliminate that leak before
slowly releasing the vacuum gauge. This leak check is optional.
2. Connect the NDIR analyzer to electrical service and
allow it to warm "up according to the manufacturer's recommenda-
tions (minimum of 1 h). Whenever possible a 2-h warmup is pre-
ferred.
-------
Section No. 3.8.4
Revision No. 0
Date January 4, 1982
Page 4 of 12
3. Perform a multipoint calibration (Section 3.8.2).
4. Connect the NDIR to the sampling train as illustrated
in Figure 4.1, and insert the probe into the stack at the prede-
termined sampling point.
5. Plug the sampling port to prevent dilution of the stack
gas by in-leakage of ambient air.
6. Immediately adjust the gas flow rate to that recom-
3
mended by the NDIR manufacturer [must be <_1 £/min (0.035 ft /
min)]. Purge the system by drawing at least 5 times the sampling
system volume through the train or by drawing until the analyzer
reading stabilizes.
7. Record the gas flow rate and the CO concentration on
the field data form for continuous sampling (Figure 4.2).
8. Check the strip chart recorder (if used) for proper
operation:
a. Chart speed control setting,
b. Gain control setting,
c. Ink trace readability,
d. Excess noise, and
e. Proper zero setting.
9. Determine the CO2 concentration (Method 3) simultan-
eously with the CO monitoring.
10. Remove the probe from the stack, place a vacuum gauge
at the probe inlet, perform*the leak check (step 1), and record
the leakage rate on the data form (Figure 4.2). This leak check
is mandatory.
11. Disconnect the NDIR, and cap off both ends of the
sampling train.
12. Perform the zero and span calibration (Section 3.8.2)
upon completion of the testing, or once a day if continuous
sampling lasts for more than one 24-h period.
13. Record the new zero and span settings in the comments
section of the data form (Figure 4.2), and record the values on
the strip chart recorder (if used).
-------
AIR-COOLED
CONDENSER
PROBE
*OE
FILTER
(GLASS WOOL)
HJ £j *x$ j/j
ID pj n> (D H-rt
to H-
tn d H-O
fU O »
oat)
1-4^ *-* *5?
rt\ c ^i
Figure 4.1. Continuous sampling apparatus.
00
•
4*
00
NJ
-------
Section No. 3.B.4
Revision No. 0
Date January 4., 1982
Page 6 of 12
Plant name
flmEe.\(Lft TNd.
Date
7- £3-80
. so
Sample location
Barometric pressure, jtatf(in.) Hg
Ambient temperature, >e^(°F) 76> Stack temperature, >C'(°F)
Intital leak check QK Final leak check
Operator 77 kJ/t.so*/
Clock
time,
24 h
12 :3o
,
,
Rotameter
setting,
Jtt/min
I f+- a /mfrrV-
o.^jt/mi*
CO cone,
ppm (dry basis)
^0
C02,
1-0
Comments
-
Figure 4.2. Field sampling data form for CO (continuous sample).
-------
Section No. 3.8.4
Revision No. 0
Date January 4, 1982
Page 7 of 12
4.2.5 Integrated Sampling - Integrated sampling is conducted at
a rate proportional to the stack gas velocity, which has a linear
relationship with the square root of the velocity head (AP).
Following is a recommended method for determining proportional
sampling rates:
1. Conduct a velocity traverse, and determine the maximum
velocity head (AP max) to be sampled.
2. Assign a sampling rate of 0.75 £/min (0.03 ft /min) to
AP max.
3. Determine the actual velocity head (AP).
4. Set the sampling flow rate using the following equa-
tion.
2S • 2m sT5s Equation 4-1
where
Q^ = maximum sampling rate, 0.75 2 /min (0.03 ft /min),
Q = sampling rate, £/min (ft /min),
s
AP = actual velocity head, mm (in.) H20, and
AP max = maximum velocity head, mm (in.) H20.
5. Determine the rotameter setting for the sampling rate
(Q ) from the rotameter calibration curve, and adjust the rota-
meter accordingly.
Using this procedure will ensure that the sampling rate will not
3
exceed 0.75 £/min (0.03 ft /min), and it will facilitate the
preparation of a table or graph for easy reference prior to
actual sampling.
Follow the procedure below to obtain an integrated sample.
1. Leak check the sampling train just prior to sampling by
placing a U tube or inclined manometer at the probe inlet and
pulling a vacuum of ^50 mm (2 in. ) H20. Turn the pump off.
Note; The vacuum should remain stable for at least 30 s. If a
leak is found, repair before proceeding; if not, slowly release
the vacuum gauge. This leak check is optional.
2. Disconnect the flexible bag from the sampling train,
and insert the probe into the stack at the sampling point; if a
-------
Section No. 3.8.4
Revision No. 0
Date January 4,. 1982
Page 8 of 12
traverse is to be conducted, place the probe at the first point
to be sampled.
3. Plug the sampling port to prevent dilution of the stack
gas by in-leakage of ambient air.
4. Purge the system by turning on the pump and drawing at
least 5 times the sampling system volume through the train, or
purge for 10 min, whichever is greater.
5. Adjust the sample gas flow rate—not to exceed 1 2/min
(0.035 ft3/min).
6. Connect the flexible bag to the sampling train (the
connections should ensure a leak-free system), and begin sampling
at a rate proportional to the stack gas velocity for the total
sampling time specified by the standard of performance for the
industry being sampled. The starting time for each test is when
the sample bag is connected.
7. Record all data on the field sampling data form (Figure
4.3).
8. . Determine the C02 concentration simultaneously with the
CO monitoring. If enough volume will be collected in the flexi-
ble bag, an Orsat analysis for C02 concentration may be performed
on the flexible bag used to collect the CO sample.
9. Disconnect and seal the flexible bag upon completion of
sampling. Take care not to dilute the contents with ambient air.
10. Turn off the vacuum pump, remove the probe from the
stack, and place a vacuum gauge at the probe inlet.
11. Repeat the leak check (step 1), and record the leakage
rate on the data form (Figure 4.2). This leak check is manda-
tory .
.12. Label each sample bag clearly and uniquely to identify
it with its corresponding data form.
4.3 Sample Recovery
Sample recovery should be performed in such a manner as to
prevent contamination of the test sample and maintain sample
integrity.
-------
Plant name TKATJS AMERICA
Date
Sample location
Barometric pressure, jam"(in.) Hg
Ambient temperature, /C' (°F) %°
Initial leak check
Operator
OA-
Stack temperature,
Final leak check
(°F)
Sampling
time,
min
5-
Clock
time,
24 h
/O:OO
Traverse
point
/
Velocity head
(APs), jn«r-(in.) H20
02-5
Rotameter
setting,
£/min (ft3 /min)
0- 56 -//W
CO
cone , ppm
(dry basis)
45"
*
C02,
%
9-5-
^J t^ 5^ Cfl
pj to n> n>
iQ rt< O
0> 0» H-rt
w H-
U3 GJ H- O
O
H,
Figure 4.3. Field sampling data form for CO (integrated sample).
0) !3 O
M O •
to
>u o •
00
vo
oo
to
-------
Section No. 3.8.4
Revision No. 0
Date January 4, 1982
Page 10 of 12
4.3.1 Continuous Sample Recovery - Continuous sampling for CO
requires no sample recovery other than an integrated bag sample
for C02. The integrated method for determination of C02 content
requires no sample recovery other than making sure the sample is
labeled. The label should clearly and uniquely identify the
sample with the test number, time of sampling and so forth.
(Analysis of this sample is discussed in Method 3, Section 3.2.)
4.3.2 Integrated Sample Recovery - Integrated sample recovery
for CO requires only that the gas bag be capped and properly
labeled. If an integrated sample was obtained to determine the
C02 content of the gas stream, it also should be capped and
labeled. The labels should clearly and uniquely identify the
test numbers, times of sampling, and so forth. The CQ2 sample
could be the same as that to be analyzed for CO content. Ana-
lysis of the C02 sample is discussed in Method 3, Section 3.2.
4.4 Sample Logistics (Data) and Equipment Packing ,
The sampling and the sample recovery procedures are followed
until the required number of runs are completed. At completion,
perform the following:
1. Return all samples to the base laboratory; check for
proper labeling (time, date, location, number of each test, and
other pertinent documentation).
2. Duplicate all data recorded during the field test by
using carbon paper or by using data forms and a laboratory note-
book. One set of data should be mailed to the base laboratory,
given to another team member, or given to the agency; the other
should be handcarried to prevent costly and embarrassing mis-
takes .
3. Examine all samples and sampling equipment for damage
and properly pack for shipment to the base laboratory. Properly
label all shipping containers to prevent loss of samples or
equipment.
The postsampling operations—apparatus checks, sample anal-
ysis, and calculations—are discussed in the next two sections.
-------
Section No. 3.8.4
Revision No. 0
Date January 4, 1982
Page 11 of 12
Continuous Sampling
Leak check prior to sampling (optional)
NDIR allowed to warm up (1 h minimum)*
0
Multipoint calibration curve constructed*
Sample port plugged _
Sample flow rate properly set (manufacturer recommended and
<.! Vmin)* fM»
Sample system properly purged* _
Posttest leak check (mandatory)*
All data properly recorded*
CO2 concentration determined* ^./i^J
Integrated Sampling
Sampling rate selected for integrated sampling
Leak check prior to sampling (optional)
Sample port plugged
Sample train purged (5 times system volume or 10 min)*
Flexible bag properly sealed and labeled*
Posttest leak check (mandatory)*
All data properly recorded*
C02 concentration determined*
*Most significant item/parameters to be checked.
Figure 4.4. On-site measurements checklist,
-------
Section No. 3.8".4
Revision No. 0
Date January 4,. 1982
Page 12 of 12
TABLE 4.1. ACTIVITY MATRIX FOR ON-SITE MEASUREMENTS
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Assembling
sampling
train
Meets specifications
in Fig 1.1 or Fig. 1.2
Before each sampling
Reassemble
Continuous
sampling
Leak checked, no de-
flection on a vacuum
gauge for a 30-s
C02 determination,
(Sec 3.8.1) leak check
after sampling, (same
as above)
Leak check the
system; calibrate the
NDIR before each
test, and after each
test run, or once a
day (Sec 3.8.2);
leak check after
sampling (mandatory)
Correct the
leak; repeat the
sampling; re-
calibrate; re-
peat the sam-
pling
Integrated
sampling
Leak checked, no de-
flection on a vacuum
gauge for a 30-s period;
C02 determination,
.sample volume, (Meth 3)
minimum time and volume
determined by applicable
standard of performance;
leak check after sam-
pling (no deflection on
a vacuum gauge for
30-s); sample propor-
tionally to stack gas
velocity for the spec-
ified length of time
Leak check the system;
leak check after
sampling (manda-
tory)
Correct the
leak; repeat the
sampling
Sample logis-
tics (data)
and packing
of equipment
All data recorded cor-
rectly; all equipment
checked for damage, and
labeled for shipment;
all sample containers
properly labeled and
packaged
After each sampling
and before packing
for shipment,
visually check
Complete the
data; repeat
sample if
damage occurred;
correct if
possible
-------
Section No. 3.8.5
Revision No. 0
Date January 4, 1982
Page 1 of 5
5.0 POSTSAMPLING OPERATIONS
Table 5.1 at the end of this section summarizes the quality
assurance activities for postsampling operations.
5.1 Apparatus Checks
Posttest checks must be made on most of the sampling appa-
ratus. Record the data from the zero and span checks of the NDIR
(continuous sampling only) and from the calibration, cleaning,
and/or routine maintenance (Section 3.8.7) of the rotameter on
Figure 5.1.
5.1.1 Rotameter - Calibration of the rotameter used during
sampling should be verified by a posttest check which is similar
to the initial calibration (Section 3.8.2) with the following
variations:
1. The metering system should not have had any leaks
corrected prior to the posttest check.
2. Only two flow rate checks need to be made. I f the
rotameter calibration factor (Y ) does not deviate >10% from the
initial calibration factor, the rotameter operation is accept-
able; if it does, the rotameter should be cleaned and recali-
brated (Section 3.8.2), but no calculations need be corrected.
Record all required data on Figure 5.1.
5.1.2 NDIR Calibration Check (Continuous Sampling Only) - Cali-
bration of the NDIR analyzer used during sampling must be checked
upon completion of the testing period. Use the zero and span
checks (Section 3.8.2). If the span check deviates more than
±10% of the pretest span value, void all data back to the last
acceptable calibration check.
5.2 Analysis Checks (Integrated Sampling Only)
The analyst should be familiar with the NDIR analyzer and
its calibration procedure in order to obtain a precise and accu-
rate analysis of samples and should use the analysis section of
Figure 5.1 for a quick check of requirements during analysis of
integrated samples.
-------
Section No. 3.8:5
Revision No. 0
Date January 4, 1982
Page 2 of 5
NDIR
Posttest zero check L^CL) _ adjusted value /Q
Posttest span check* fy^ within ±10% of pretest calibration
Recalibration required? _ yes
Multipoint calibration curve constructed* _
Sampling lines and analyzer properly purged (5 times system
volume or 10 min)* 6/A^>
Three successive readings made from each bag LL
Highest and lowest values differ by
-------
Section No. 3.8.5
Revision No. 0
Date January 4, 1982
Page 3 of 5
5.2.1 Calibration Gas Values - Concentrations of CQ in the zero
gas and in the calibration gases are determined as described in
Section 3.8.2. The concentrations reported by the manufacturer
should be traceable to an NBS-SRM or CRM standard gas.
5.2.2 NDIR Sample Values - After the analysis system is assem-
bled according to Figure 2.6, use the following procedure to
check the CO values:
1. Turn on the NDIR and allow it to warm up according to
the manufacturer's recommendations (minimum of 1 h).
2. Perform a multipoint calibration (Section 3.8.2, Sub-
section 2.2.1).
3. Connect the flexible bag to the NDIR (Figure 5.2), and
purge the sample lines and analyzer either by drawing at least 5
times the system volume through the system or by purging for 10
min whichever is greater.
4. Record at least three successive CO concentrations
determined by the NDIR and the calibration curve (step 2). Note:
The highest and lowest values should not differ by >5%.
5. Perform the zero and span checks (Section 3.8.2).
6. Repeat steps 3 through 5 for each bag sample.
Analyze the C02 integrated samples according to Method 3, Section
3.2.
-------
Section No. .3.8.5
Revision No. 0
Date January 4, 1982
Page 4 of 5 -
RECORDER
RATE
METER
A
CONTROL
NEEDLE
VALVE
NDIR
.in-
MPLE
RATE METER
Figure 5.2. Integrated sample analytical apparatus.
-------
Section No. 3.8.5
Revision No. 0
Date January 4, 1982
Page 5 of 5
TABLE 5.1. ACTIVITY MATRIX FOR POSTSAMPLING OPERATIONS
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Sampling
Rotameter
Within ±10% of de-
sired flow rate
Make.two independent
checks (Sec 3.8.2)
Clean and
recalibrate
NDIR (contin-
uous sampling
only)
Within ±10% of pretest
calibration
After testing, check
zero and span values
(Sec 3.8.2)
Recalibrate
and void all
data back to
last accept-
able check
Analysis (inte-
grated sample
only)
Calibration
gases
Traceability to NBS-
SRM or CRM performed
by manufacturer accord-
ing to Protocol No. 1
Sec 3.8.2
Return to
supplier
Sample values
Values within 5% of
each other
Make at least three
successive determina-
tions for each bag
sample for CO and
C02
Repeat the
analysis
-------
Section No. 3.8.6
Revision No. 0
Date January 4, 1982
Page 1 of 3
6.0 CALCULATIONS
Calculation errors due to mathematical mistakes can be a
large part of total system error. Therefore, each set of calcu-
lations should be repeated or spotchecked by a team member other
than the one who performed them originally. If a difference
greater than a typical round-off error is detected, the calcula-
tions should be checked step by step until the source of error is
found and corrected. Table 6.1 at the end of this section sum-
marizes the quality assurance functions for calculations.
A computer program can be advantageous in reducing calcula-
tion errors. If a standardized computer program is used, check
the original data entries; if differences are observed, make a
new computer run.
Carryout calculations, retaining at least one decimal figure
beyond that of the acquired data. Roundoff the final calcula-
tions to two significant digits for each run or sample in accord-
ance with the ASTM 380-76 procedures. Record the results on
Figure 6.1.
6.1 Nomenclature
The following nomenclature is used in the calculations.
C
CO. , = concentration of CO in stack, ppm by volume (dry
basis),
r
CONDIR = concentrati°n °f co measured by NDIR analyzer,
ppm by volume (dry basis),
p
C02 = volume fraction of C02 in sample (i.e., %C02 from
Orsat analysis divided by 100).
6.2, Calculations
The CO content (ppm) is measured by NDIR on a dry basis,
after the CO2 content of the sample gas has been removed. This
NDIR measurement must be corrected for the CO2 content (%) re-
moved .
-------
Section No. 3.8.6
Revision No. 0 •
Date January 4, 1982
Page 2 of 3
Plant
GJ\AJ'
, <*JsLiO .
Date
Operator
7-
location Qu££aL Si^^J^
.umber
1
mber / 01
or U. LU
-------
Section No. 3.8.6
Revision No. 0
Date January 4, 1982
Page 3 of 3
Use Equation 6-1 and the data from Figure 6.1 to correct the
NDIR reading.
Ccostaok = CCONDIR U " '^i*'
Equation 6-1
TABLE 6.1. ACTIVITY MATRIX FOR CALCULATION CHECKS
Characteristics
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Analysis data
form
All data and calcula-
tions shown on Fig 6.1
Visually check
Complete the
missing data
Calculations
Difference between
check and original
calculations less than
or equal to round-off
error
Repeat all calcula-
tions starting with
raw data for hand
calculations; check
all raw data input
for computer calcu-
lations, and hand
calculate using one
sample per test
Indicate any
errors on
Fig 6.1
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Section No. 3.8.7
Revision No. 0
Date January 4, 1982
Page 1 of 2
7.0 MAINTENANCE
Normal use of equipment subjects it to corrosive gases,
temperature extremes, vibrations, and shocks. Keeping the equip-
ment in good operating order over an extended period of time
requires not only knowledge of the equipment but also routine
maintenance. Maintenance of the entire sampling train should be
performed quarterly or after 2830 I (100 ft3) of operation,
whichever occurs first. Maintenance procedures for system com-
ponents are summarized in Table 7.1. The following procedures
are recommended, but not required, to increase the reliability of
equipment.
7.1 Pumps
Several types of pumps are used in commercial sampling
trains. Two of the 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 oil and
the oiler jar. The used oil (usually 10W nondetergent or machine
weight) should.be essentially the same translucent color as the
unused or spare oil, and the jar should be no less than half full
and leak free. When the fiber vane pump starts to run errati-
cally or when the head is removed each year, the fiber vanes
should be replaced.
The diaphragm pump requires little maintenance. If the pump
runs erratically, it is normally due to a bad diaphragm or mal-
functions in the valves; these parts are easily replaced and
should be cleaned annually by complete disassembly of the train.
7.2 Rotameter
A rotameter should be disassembled and cleaned according to
the manufacturer's instructions using the recommended cleaning
fluids annually or more often if erratic behavior occurs.
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Section No. 3.8.7
Revision No. 0
Date January 4, 1982
Page 2 of 2
7.3 NDIR Analyzer
The CO analyzer comes with a manual that specifies mainte-
nance procedures and how often each should be performed. Follow
the manufacturer's recommendations, and call an experienced field
service representative if internal adjustments are needed.
7.4 Other Sampling Train Components
All other sampling train components (probe, flexible bag,
etc.) should be visually checked quarterly and completely disas-
sembled and cleaned or replaced yearly. Many of the. items (e.g.,
quick disconnects) should be; replaced when damaged rather than
checked periodically. Normally the best procedure in the field
is to replace a component.
TABLE 7.1. ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Fiber vane pump
In-line oiler free of
leaks and at least half
full
Periodic check of oil
and oiler jar; remove
head and change fiber
vanes yearly
Replace or
refill oiler jar
as needed
Diaphragm pump
Leak-free valves;
diaphragm function-
ing properly
Clean valves during
yearly disassembly or
upon erratic behav-
ior
Replace if
cleaning will
not correct the
malfunction
Rotameter
Clean; no erratic
behavior
Clean by manufactur-
er's recommendations
yearly or upon errat-
ic behavior
Replace
NDIR analyzer
Clean; no erratic
behavior
Follow manufacturer's
recommendations
Call service
representative
for expert
repair
Sampling train
components
No damage; no erratic.
behavior
Visually check every
3 mo; completely dis-
assemble and clean or
replace yearly
Repair or
replace with
spare component
if in the field
-------
Section No. 3.8.8
Revision No. 0
Date January 4, 1982
Page 1 of 7
8.0 AUDITING PROCEDURE
An "audit" is an independent assessment of data quality.
Independence is achieved by using standards and equipment that
are different from those used by a regular field crew. Although
routine quality assurance checks conducted by a field team are
necessary in generation of good quality data, they are not con-
sidered as part of the auditing procedure. Table 8.1 at the end
of this section summarizes the quality assurance activities for
auditing.
Based on the results of collaborative tests of Method 10,l
two specific performance audits are recommended:
1. Audit of the analysis phase of Method 10.
2. Audit of data processing.
In addition to these performance audits, it is suggested
that a system audit be conducted as specified by the quality
assurance coordinator. The two performance audits and the system
audit are described below in Subsections 8.1 and 8.2.
, 8.1 Performance Audits
Performance audits are conducted by the auditor to quantita-
tively assess the quality of data produced by the total measure-
ment system (sample collection, sample analysis, and data pro-
cessing). Due to the limited sizes of most emission-testing
companies, it is recommended that these audits be performed by
the responsible control agency once during every enforcement
source test, regardless of whether the tests are conducted by
agency or private company personnel. A source test for enforce-
ment comprises a series of runs at one source.
8.1.1 Audit of Analysis Phase - An accuracy assessment should be
made on the analytical phase by means of a cylinder gas audit as
follows:
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Section No. 3.8.8
Revision No. 0
Date January 4, 1982
Page 2 of 7
1. Challenge the analyzer with an audit gas of known
concentration at two points. Audit Point 1 should be within 45
to 55% of analyzer full span and audit point 2 should be within
85 to 95% of analyzer full span.
Use a separate audit gas cylinder for audit points 1 and 2.
Do not dilute gas from the audit cylinder when challenging the
analyzer.
The analyzer should be challenged at each audit point for a
sufficient period of time to assure adsorption-desorption of the
system surfaces has stabilized.
2. Operate each analyzer in its normal sampling mode,
i.e., pass the audit gas through all filter, scrubbers, con-
ditioners, and other analyzer components used during normal
sampling and as much of the sampling probe as is practical.
3. Use audit gases that have been certified by comparison
to NBS-SRM or gas manufacturer's (CRM) following EPA Traceability
Protocol No. 1. As an alternative to Protocol No. I audit gases,
CRM may be used directly as audit gases. A list of gas manu-
facturers that have prepared approved CRM's is available from EPA
at the following address:
U.S. Environmental Protection Agency
Quality Assurance Division (MD-77)
Research Triangle Park, North Carolina 27711
Attn: List of CRM Manufacturers
The differences between the actual concentration of the
audit gas and the concentration indicated by the analyzer is used
to assess the percent accuracy (%A) of the test data as shown in
Figure 8.1. If the %A for an audit point is not within limits,
challenge the analyzer with the same concentration to verify the
response.
The calculated %A should be within ±15%. Results of the
calculated %A should be included in the enforcement source test
report as an assessment of accuracy of the analytical phase of
Method 10 during, the actual enforcement source test.
-------
Section No. 3.8.8
Revision No. 0
Date January 4, 1982
Page 3 of 7
Tester
Analyzer Ar.me. Model 41-1
Analyzer serial number M9~
Auditor (~f
Cylinder ID
Remarks
p j
Source
Range
- r.\o\
Date
«-)
Concentration
Audit cylinder
cone (CCQ)a, ppm
3 30
.>TS^
^0<
Analyzer response
4
v5-/^C
»fc5
*
Percent accuracy,
(%A), %*
v5".f>
^. ^
V. fc
%A =
- v
(LCO;a
x 100.
Figure 8.1. Example of an audit summary report.
-------
Section No. 3.8.8
Revision No. 0 '
Date January 4, 1982
Page 4 of 7
If the audit indicates that the analyzer is out of toler-
ance, corrective action must be taken.
If -the analysis is to be performed in the laboratory (inte-
grated sampling only), the above audit procedure can be used for
a pretest audit (optional).
8.1.2 Audit of Data Processing - The data reduction process in-
volves reading a strip chart record, calculating an average, and
transcribing or recording it.. :The data thus obtained can be com-
pared to the calibration curve as an independent check of the
entire data reduction process or, the audit may be accomplished
by providing the laboratory team with specific data (exactly as
would occur in the field) and requesting that copies of the data
reduction be returned to the evaluator.
When a difference between the originals and the audits on
data reduction and calculations exceeds round-off error, all data
from the source test should be checked, and the errors should be
clearly explained to the team to prevent or minimize reoccur-
rences .
8.2 System Audit
A system audit is an on-site qualitative inspection and
review of the quality assurance activities used by the test team
to evaluate the total measurement system (sample collection,
sample analysis, data processing, etc.). Initially, a system
audit specified by. a quality assurance coordinator should be
conducted for each enforcement source test, which by definition
comprises three runs at one source. After the team gains experi-
ence, the frequency of audit may be reduced—for example, to once
every four tests.
The auditor (i.e., the person performing the system audit)
should have extensive background experience in source sampling
and more specifically, with the measurement system that he is
auditing. The functions of the auditor are summarized in the
following:
1. Observe procedures and techniques of the field team
during sample collection.
-------
Section No. 3.8.8
Revision No. 0
Date January 4, 1982
Page 5 of 7
2. Check/verify the records of apparatus calibration and
the quality control charts used in the laboratory analysis.
3. Record the results of the audit and forward them with
comments on source team management to the quality assurance
coordinator so that any needed corrective actions may be imple-
mented.
The auditor should observe the field team's overall perform-
ance of the source test. Specific .operations to observe should
include, but not be limited to:
1. Setting up and leak testing the sampling train.
2. Use of proper zero and span gases.
3. Purging of sampling train.
4. Sampling rate (constant or proportional).
5. Sample recovery and preparations for shipment, if
applicable.
Figure 8.2 is a suggested checklist form for use by the
auditor in developing his/her own list of important techniques/
steps to observe.
-------
Section No. 3.8.8
Revision No. 0
Date January 4, 1982
Page 6 of 7 -
yes
V/
^Z
vX
_*/
w/
^
-^
.X
1^
no
—
comment
r>K
OPERATION
Presampling Preparations
1. Knowledge of process conditions
2. Traceability of calibration gas
established
3. Calibration of pertinent equipment,
J .in particular, the NDIR
On-Site Measurements
4. Leak test of sampling train
5. NDIR warmup per manufacturer's
recommendations
6. Purging the train prior to sampling
7. Proportional sampling
8. Frequency of zero and span checks
9. Drying agents checked and replaced
frequently
Posts ampling
10. Transfer and handling of sample
11. Data .reduction procedure/check
12. Calibration checks
GENERAL COMMENTS:
Figure 8.2. Method 10 checklist to be used by auditors.
-------
Section No. 3.8.8
Revision No. 0
Date January 4, 1982
Page 7 of 7
TABLE 8.1. .ACTIVITY MATRIX FOR AUDITING PROCEDURES
Audit
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Performance
Audit
Analysis phase
0.85
"Wn,
(Crn)
LU a
analyzer re-
sponse, ppm,
concentration
of audit cylin-
der, ppm
Once during every
source test,mea-
sure reference
sample and compare
to the true value
Review opera-
ting and cali-
bration tech-
niques/proce-
dures
Data processing
Original and check re-
sults agree within
roundoff error
Once during every
source test; perform
independent data
reduction and cal-
culations
Check and
correct all
data for the
test series
System Audit
Observance of
techniques
Operation technique as
described in this sec-
tion of the Handbook
Once during every
source test until
experience gained,
and then, every
fourth test, observe
techniques; use
audit checklist
(Fig 8.2)
Explain to
team any
deviations
from recom-
mended tech-
niques; record
data and com-
ments on Fig 8.2
-------
Section No. 3.8.9
Revision No. 0
Date January 4, 1982
Page 1 of 7
9.0 RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
To achieve data of desired quality, two considerations are
necessary:
1. The measurement process must be in a state of statisti-
cal control.
2. The systematic errors, when combined with the random
variations (errors of measurement), must result in a suitably
small uncertainty.
To ensure good data, it is necessary to perform quality control
checks and independent audits of the measurement process; to
document the data by quality control charts (as appropriate); and
to use materials, instruments, and procedures which can be traced
to a standard of reference.
The working calibration standards should be traceable to
primary or higher level standards such as the two listed below.
1. A wet test meter (2-£/min capacity) with a ±1% accuracy
verified by liquid displacement, as described in Section 3.8.2.
2. NBS-SRM and gas manufacturers CRM gases are considered
primary standards.
9.1 Traceability Protocol for Establishing True Concentration of
CO Gases used for Calibration and Audit
The traceability protocol described in this section is
intended to minimize systematic and random errors during the
analysis of calibration and audit gas standards and to establish
the true concentrations by means of National Bureau of Standards,
Standard Reference Materials (NBS-SRM's) or certified reference
materials or other NBS traceable gases.
Performance standards promulgated3'4'5 by the U.S. Environ-
mental Protection Agency (USEPA) for stationary sources require
continuous monitoring systems for specified pollutants. Extrac-
tive continuous monitoring systems for gaseous pollutants must be
calibrated and audited using gas standards that are accurate and
-------
Section No. 3.8.9
Revision No. 0
Date January 4, 1982
Page 2 of 7
stable. Traceability requires direct comparisons between the
calibration and audit gas standards and either an NBS-SRM or a
certified reference material or a gas manufacturer's primary
standard (GMPS) which is referenced to an NBS-SRM. All compari-
sons are made using an instrument calibrated with applicable
NBS-SRM1s. Traceability must be performed by the gas standard
manufacturer at the time of purchase; reanalysis to verify trace-
ability may be performed by, the gas standard manufacturer or by
the user.
9.2 Establishing Traceability of Commercial Cylinder Gases to
NBS-SRM Cylinder Gases
The following procedures for periodic multipoint calibra-
tions and daily instrument span checks are prescribed to minimize
systematic errors. Separate procedures for instrument span
checks are described for linear and nonlinear instruments. To be
linear, the difference between the concentrations indicated by
the calibration curve and the straight line drawn from the point
determined by the zero gas to the highest point determined by
calibration must not exceed 2% of full scale at any point on the
curve. A list of NBS-SRM CO cylinder gases recommended for
traceability of commercial cylinder gases is shown in Table 9.1.
TABLE 9.1. NBS-SRM CARBON MONOXIDE (CO) GASES AVAILABLE
FOR TRACEABILITY AND AUDIT OF CO GAS STANDARDS
NBS-SRM
number
1677b
1678b
1679b
1780a
1681a
Type
CO in N2
CO in N2
CO in N2
CO in N2
CO in N2
Size
£ at STP
870
870 ,
870
870
. 870
Nominal
concentrations
10 ppm
50 ppm
100 ppm
500 ppm
1000 ppm
-------
Section No. 3.8.9
Revision No. 0
Date January 4, i982
Page 3 of 7
9.2.1 Multipoint Calibration - A multipoint calibration curve
should be prepared monthly by using two SRM cylinder gases and
the zero gas. The zero gas must contain <_0.2% of the full-scale
concentration of the component being analyzed, and it must be
free of any impurity, that will cause a response on the analytical
instrument.
Multipoint calibration is accomplished by using a calibra-
tion flow system to dilute the SRM^of highest concentration with
the zero gas.
1. Read the responses for six points displaced from 0 to
100% of the instrument's full scale.
2. Plot the data, and draw the calibration curve.
3. Read the response for the SRM of lower concentration
without dilution.
4. Compare the apparent concentrations from the calibra-
tion curve to the true concentration of the lower SRM. Note; If
the difference between the apparent and the true is >3% of the
true concentration, repeat the multipoint calibration procedure.
5. Test the calibration curve for linearity. Proceed to
either Subsection 9.2.2 or 9.2.3.
9.2.2 Instrument Span Check for Linear Responses - The span
check should be performed at the start of each day that cylinder
gases are to be analyzed.
1. Read the instrument's response to the highest SRM (or
GMPS) in the range to be used and check the response to the zero
gas.
2. Adjust the response to the value obtained in the most
recent multipoint calibration, and proceed to Subsection 9.3.
Note; Cylinder gases analyzed with a linear instrument must not
have a concentration >15% above the highest available SRM concen-
tration.
9.2.3 Instrument Span Check for Nonlinear-Response - The span
check should be performed at the start of each day that cylinder
gases are to be analyzed.
-------
Section No. 3.8-.9
Revision No. 0
Date January 4, 1982
Page 4 of 7
1. Read the instrument's responses to two SRM's (or
GMPS's) in the range of calibration gases to be analyzed, and
check responses to zero gas.
2. Set the instrument's zero with the zero gas, and adjust
its response to the highest SRM (or GMPS) to the value obtained
in the most recent multipoint calibration.
3. Read the response to the lower SRM (or GMPS). Note;
If the response to the lower SRM (or GMPS) varies by >3% from the
response in the most recent multipoint calibration, a full multi-
point calibration must be performed (Subsection 9.2.1); other-
wise, proceed to Subsection 9.3. Calibration gases analyzed with
a nonlinear instrument must not have a concentration greater than
the highest available SRM concentration.
9.3 Determining True Concentrations of Cylinder Gases
Direct comparison of the cylinder gas to an SRM (or GMPS)
should compensate for variations in instrument responses between
the daily span check and the analyses; significant variations in
responses often result from changes in room temperature, line
voltage, and so forth. Analyses in this procedure should be per-
formed in triplicate (3 pairs) to expose erroneous data points
and excessive random variations in instrument responses.
After the gas cylinder has been filled, wait a minimum of 4
days before beginning the following procedure. If .necessary,
adjust the instrument span prior to the analyses, but do not
adjust it during the triplicate analyses.
1. Compare each cylinder gas directly with the nearest SRM
(or GMPS) by taking alternate readings of the SRM and calibration
gas responses in triplicate. Note; The response to zero gas
must be read frequently so that the change in successive zero
responses are not >1% of full scale.
2. For each of the six readings, determine the apparent
concentration of the SRM (or GMPS) or cylinder gas by referring
to the calibration curve.
-------
Section No. 3.8.9
Revision No. 0
Date January 4, 1982
Page 5 of 7
3. For each pair of readings—one SRM (or GMPS) and one
cylinder gas, calculate the true concentration of the cylinder
gas by using Equation 9-1:
True cone of cyl gas =
[appar cone of cyl ,as, x [£% g™ g| ™ {g ««{].
Equation 9-1
4. Determine the mean of the three values to get the true
concentration of the cylinder gas. Note; If any one of the
three values differs from the mean by >1.5%, discard the data,
reset the instrument span (if necessary), and repeat steps 1
through 4.
9.4 Using Gas Manufacturer's Primary Standards
Gas manufacturer's primary standards (GMPS) are gas mixtures
prepared in pressurized containers and analyzed against SRM
cylinder gases. Using GMPS's instead of SRM's will help to
conserve SRM's where large quantities of cylinder gases are
analyzed. A GMPS may be used for instrument span checks (Subsec-
tions 9.2.2 and 9.2.3) and for cylinder gas analyses (Subsection
9.3) if the following conditions are met.
1. A GMPS must have been analyzed against SRM cylinder
gases as described in Subsections 9.2 and 9.3 within 30 days of
their use for cylinder gas analysis, and should be compared on
the days that instrument multipoint calibrations are performed.
2. A GMPS must not have changed in concentration by >1%
per mo (average) for the 3-mo period prior to use for cylinder
gas analysis.
In no case may a GMPS be substituted for an SRM in multipoint
calibrations (Subsection 9.2.1).
9.5 Verifing Cylinder Gas Stability
The stability of each cylinder gas should be verified by a
second set of triplicate analyses (using the procedure in Subsec-
tion 9.3) a minimum of 7 days after the first set of triplicate
-------
Section No. 3.8.9
Revision No. 0
Date January 4, 1982
Page 6 of 7
analyses. The mean of the second triplicate analyses must not
differ from the mean of the first triplicate analysis by >1.5%.
9.6 Reanalyzing Cylinder Gases
Either the gas manufacturer or the user must reanalyze the
cylinder gas every 6 mo from the last analysis date by the pro-
cedure in Subsection 9.3. Cylinder gases used for audits may
need to be analyzed more often than every 6 mo. .
9.7 Minimum Cylinder Pressure
No cylinder gas with pressure <200 psi, as shown by the
cylinder gas regulator gauge, should be used.
9.8 Labeling the Cylinder and Preparing the Analysis Report
Each gas cylinder should have the following minimum trace-
ability information either on a gummed label affixed to the
cylinder wall and/or on a tag attached to the cylinder valve:
1. Cylinder number.
2. Mean concentration of cylinder gas, ppm or mol%.
3. Balance gas used.
4. Last analysis date.
5. Expiration date (6 mo after last analysis date for
reactive gases, and 12 mo after for diluent gases).
A written analysis report certifying that the cylinder gas
has been analyzed according to the protocol described in this
section should contain the following information:
1. Cylinder number.
2. Mean concentration of cylinder gas (ppm or mol%) on
vlast analysis date.
3. Replicate analysis data.
4. Balance gas used.
5. Numbers of NBS-SRM's used.
6. Analytical principle used.
7. Last analysis date.
-------
Section No. 3.8.9
Revision No. 0
Date January 4, 1982
Page 7 of 7
The user should maintain a file of all analysis reports for 3 yr.
9.9 Conducting Performance Audits
The USEPA will initiate a national performance audit program
of cylinder gases prepared by this protocol. Cylinder gases
prepared following the protocol will be obtained (directly or
indirectly) by the USEPA and analyzed in their laboratory for
accuracy compared to the gas manufacturer's reported concentra-
tion.
-------
Section No. 3.8.10
Revision No. 0
Date January 4, 1982
Page 1 of 3
10.0 REFERENCE METHOD
METHOD 10—DETERMINATION or CARSON MON-
OXIDE EMISSIONS rxox STATIONARY sotraczs
1. Principle and Applicability.
1.1 Principle. An Integrated or continuous
gas sample Is extracted from a sampling point
And analyzed for carbon monoxide (CO) con-
tent using a Luft-type nondljpersive infra-
red aualyzer (NDIR) or equivalent.
12 Applicability. This method Is appli-
cable for the determination of carbon mon-
oxide emissions from stationary sources only
when specified by the test procedures to?
determining compliance with new source
performance standards: The test procedure
will Indicate whether a continuous'• or an
Integrated sample is to be used.
3. Range and sensitlrity.
2.1 Range. 0 to 1.000 ppm.
2.2 Sensitivity. Minimum detectable con-
centration is 20 ppm for a 0 to 1,000 ppm
span.
3. Interference*. Any substance having a
strong absorption of Infrared energy "111
Interfere to some extent. For example, dis-
crimination ratios for water (R.O) »nd car-
bon dioxide (CO.) are 3.9 percent K..O per
7 ppm CO and 10 percent CO.. per 10 ppm
CO, respectively, for devices measuring ia lie
1.500 to 3.000 ppm range. For devices meas-
uring ia the 0 to 100 ppm range, Interference
ratios can be as high as 3.5 percent H.O per
36 ppm CO and 10 percent CO, per 60 ppm
CO. The use of silica gel and ascarite traps
will alleviate the major interference prob-
lems. The measured gas volume must be
corrected if these traps are used.
4. Precision and accuracy.
4.1 Precision. The precision of most NODS.
analyzer* U approximately ±3 percent of
•pan.
4J Accuracy. The accuracy of most NDIR
analyzers is approximately ±8 percent of
•pan after calibration.
6. Apparatus.
1 6.1 Continuous sample (Figure 10-1).
6.1.1 Probe. Stainless steel or sheathed
Pyrex' glass, equipped with a filter to remove
paniculate matter.
6.1.2 Air-cooled condenser or equivalent.
To remove any excess moisture.
62 Integrated sample (Figure 10-2).
6.2.1 Probe. Stainless steel or sheathed
Pyrex glass, equipped with a filter to remove
paniculate matter.
622 Air-cooled condenser or equivalent.
To remove any excess moisture.
{.3.3 Valve. Needle valve, or equivalent, to
to adjust flow rate.
6.2.4 Pump. Leak-free diaphragm type, or
equivalent, to transport gas.
6.2.5 Rate meter. Rotameter. or equivalent,
to measure a flow range from 0 to 1.0 liter
per nun. (0.035 dm).
5.2.6 flexible bop. Tedlar, or equivalent,
•with a capacity of 60 to 90 liters (2 to 3 11 •).
Leak-test the bag In the laboratory before
ndng by evacuating bag with a pump fol-
lowed by a dry gas meter. When evacuation
Is complete, there should be no flow through
the meter.
AM-COOUO ccNonui
nai
Ptfw« 1M. IMfnlM |t»IM«IU| Ml*.
6.2.7 PitoS tube. Type S, or equivalent, at-
tached to the probe so that the sampling
r*te can be regulated proportional to the
stack gas velocity when velocity if varying
with the time or a sample traverse U con-
ducted.
5.3 Analysis (Figure 10-3).
1 Mention of trade names or specific prod-
ucts does not constitute endorsement by the
Environmental Protection Agency.
*Taken from Federal Register, Protection of
Environment, Parts 50-69, page 790-792,
July 1, 1975.
-------
5.3.1 Carbon monoxide analyzer. Nondisper-
slve infrared ipectrometer. or equivalent.
Tills Instrument should be demonstrated,
preferably by the manufacturer, to meet or
exceed manufacturer's specification* and
those described in this method,
5.3.2 Drying tube. To contain approxi-
mately 300 g of sUlca gel.
6.3.3 Calibration gat. Refer to paragraph
6.1.
6.3.4 filter. Ac recommended by NDIB
manufacturer.
6.3.6 CO, removal tube. To contain approxi-
mately 600 g of aacaxlte.
6.3.6 Ice water both. For ascante and silica
gel tubes.
6.3.7 Value. Needle valve, or equivalent, to
adjust flow rate
63.8 Rate meter. Rotameter or equivalent
to measure gas flow rate of 0 to 1.0 liter per
mln. (0.036 cfm) through NDIR.
6.3.9 Recorder (optional)- To provide per-
manent record of NDTA readings.
6. Reagent*.
«M«IWI rrtrmit.
6.1 Calibration gases. Known concentration
of- CO in nitrogen (N,) for instrument span,.
prepurlfled grade- of Ni for zero, and two addi-
tional concentrations corresponding approxi-
mately to 60 percent and 30 percent span. The
span concentration shall not exceed 1.6 times
the applicable source performance standard.
The calibration gases shall be certified by
the manufacturer to be within ±1 percent
of the specified concentration.
6.2 Silica gel. Indicating type, 6 to 18 mesh.
dried at 176* C (M7* F) lor a hours.
84 Ajcorife. Commercially available..
7. Procedure.
7.1 Sampling.
Section No. 3.8.10
Revision No. 0.
Date January 4, 1982
Page 2 of 3
7.1.1 Continuous lampling. Set up the
equipment as shown In Figure 10-1 making
sure all connections are leak free. Place the
probe in the stack at a sampling point and
purge the sampling line: Connect the ana-
lyzer and begin drawing sample into the
analyzer. Allow 6 minutes for the system
to stabilize, then record the analyzer read-
ing as required by the test procedure. (See
T 7.3 and 8). CO, content of the gas may be
determined by using the Method 3 inte-
grated sample procedure (36 FR 24886). or
by weighing the ascartte CO, removal tube
and computing CO, concentration from the'
gas volume sampled and the weight gain
of the tube.
7.1.2 Integrates sampling. Evacuate the
flexible bag. Set up the equipment as shown
in Figure 10-2 with the bag disconnected.
Place the probe in the stack and purge the
sampling line. Connect the bag, making sure
that all connections are leak free. Sample at
a rate proportional to the stack velocity.
CO, content of the gas may be determined
by using the Method 3 integrated sample
procedures (36 FR 24886), or by weighing
the ascarlte CO, removal tube and comput-
ing CO, concentration from the gas volume
sampled and the weight gain of the tube.
7.2 CO Anoiysu. Assemble the apparatus aa
shown in Figure 10-3, calibrate the instru-
ment, and perform other required operations
as described in paragraph 8. Purge analyzer
with Nj prior to introduction of each sample-.
Direct the sample stream through the instru-
ment for the test period, recording the read-
ings. Check the zero and span again after the
test to assure that any drift or malfunction
is detected. Record the sample data on Table
10-1.
8. Calibration. Assemble the apparatus ac-
cording to Figure 10-3. Generally an instru-
ment requires a warm-up period before sta-
bility is obtained. Follow the manufacturer's^-
instructions for specific procedure. Allow a
minimum time of one hour for warm-up.
During this time check the sample condi-
tioning apparatus, i.e., filter, condenser, dry-
ing tube, and CO, removal tube, to ensure
that each component is in good operating
condition. Zero and calibrate the Instrument
according to the manufacturer'* procedure*
using, respectively, nitrogen and the callbra.
tion gases.
TABU 10-1.—Field data
Location.
Test —
Date __.„..
Operator ,
Comments:
Clock time
Rotameter netting, liter* per minute
(oubic feet per minute)
9, Calculation—Concentration of carbon monoxide. Calculate the concentration of carbon
monoxide in the stack using equation 10-1.
where:
cco....k "
.L.k"" concentration of CO in stack, ppm by volume (dry basis).
equation 10-1
CcoNIDR~conoentr&tlon °' CO measured by NDIR analy»er, ppm by Tolume (dry
basis).
™ volume fraction of COj In sample, Le., percent COi from Onat analyst
divided by 100.
-------
Section No. 3.8.10
Revision No. 0
Date January 4, 1982
Page 3 of 3
10. Bibliography- Analyzer Instruction Book, >-g«« Safety
10.1 McElroy, Prank. The Interteeh KDER-OO Appliances Co, Techntal Products Dt-
Analyzer. Presented at llth Methods nslon, Pittsburgh, Pa,
Conference on Air Pollution, University 10.4 Model! 215A. 3ISA, and 41&A Infrared
of California. Berkeley. Calif.. April 1. Analyzer*. Beckmaa Instruments, TT"»,
1870. Beckman Instructions 1635-8. Fuller-
10.2 Jacob*, M. B., et al.. Continuous Deter- ton, Calif, October 1907.
minatlon of Carbon Monoxide and Hy- 10.5 Continuous CO Monitoring System.
drocarbons In Air by a Modified Infra-, Model A5611, Intertech Corp, Princeton,
red Analyzer, J. Air Pollution Control K.J.
Association. 9(2): 110-114. August 19S9. 10.6 TOOK Infrared Gas Analyzers. Bendlx
10.3 MSA LIRA Infrared Gas and Liquid Corp., Ronceverte. West Virginia.
ADDENDA
A. Performance Specifications for NDIR Carbon Monoxide Analyzer*.
Range (minimum)..........—........... 0-lOOOppm.
Output (minimum) 0-10mV.
Minimum detectable sensitivity 20 ppm.
Rise time. 90 percent (maximum) 30 seconds.
Fall time, 90 percent (maximum). .— 30 seconds.
Zero drift (maximum)...... . ...... 10% In 8 hours.
Span drift (maximum). .—... 10% In 8 hours.
Precision (minimum).. ............ . ± 2% of full scale.
Noise (maximum)...... .........—...—. z 1% of full scale.
Linearity (maximum deviation).—. 2% of full scale.
Interference rejection ratio COr—1000 to l, H,O—900 to 1.
B. Definitions of Performance Specifica-
tions.
Range—The minimum and maximum
measurement limits.
Output—Electrical signal which is propor-
tional to the measurement; Intended for con-
nection to readout or data processing devices.
Usually expressed as millivolts or milllamps
full scale at a given Impedance.
Full scale—The maximum measuring limit
for a given range.
Minimum detectable sensitivity—Th6
smallest amount of input concentration that
can be detected as the concentration ap-
proaches zero.
Accuracy—The degree of agreement be-
tween a measured value and the true value:
usually expressed as •+ percent of full scale,
Time to 90 percent response—The time In-
terval from a step change In the input con-
centration at the instrument inlet to a read-
tag of 90 percent of the ultimate recorded
concentration.
Rise Time (90 percent)—The Interval be-
tween Initial response time and time to 90
percent response after a step increase in the
inlet concentration.
Fall Time (90 percent)—The interval be-
tween Initial response time and time to 90
percent response after a step decrease In the
Inlet concentration.
Zero Drift—The change In Instrument out-
put over a stated time period, usually 24
hours, of unadjusted continuous operation
when the input concentration Is zero; usually
expressed as percent full scale.
Span Drift—The change in instrument out-
put over a stated time period, usually 24
hours, of unadjusted continuous operation
when the input concentration Is a stated
upscale value; usually expressed as percent
full scale.
Precision—The .degree of agreement be-
tween repeated measurements of the same
concentration, expressed as the average de-
viation of the single results from the mean.
Notje—Spontaneous deviations from a
mean output not caused by input concen-
tration changes.
Linearity—The maximum deviation be-
tween an actual instrument reading and the
reading predicted by a straight line drawn
between upper and lower calibration points.
-------
Section No. 3.8.11
Revision No. 0
Date January 4, 1982
Page 1 of 2
11.0 REFERENCES
1. Collaborative Study of Method 10 - Reference Method for
Determination of Carbon Monoxide Emissions from Sta-
tionary Sources - Report of Testing. EPA-650/7-75-001.
Environmental Protection Agency, Research Triangle
Park, N.C. January 1975.
2. McKee, Herbert C., et al. Collaborative Study of
Reference Method for the Continuous Measurement of
Carbon Monoxide in the Atmosphere (Nondispersive Infra-
red Spectrometry). Project 01-2811, Contract No. CPA
70-40. Southwest Research Institute, San Antonio,
Texas. May 1972.
3. Requirements for Submittal of Implementation Plans and
Standards for New Stationary Sources - Emission Moni-
toring. Federal Register 40, Number 194, October 6,
1975.
4. Part 60 - Standards of Performance for New Stationary
Sources - Emission Monitoring Requirements and Revi-
sions to Performance Testing Methods, Federal Register
40, Number 246, December 22, 1975.
5. Part 60 - Standards of Performance for New Stationary
Sources - Primary Cooper, Zinc and Lead Smelters,
Federal Register 40, Number 10, January 15, 1976, p.
2332-2341.
ADDITIONAL REFERENCES
Cameron, J.M. Traceability? Journal of Quality Technology
7(4):193-195, October 1975.
Colucci, Joseph M. , and Charles R. Begeman. Carbon Monoxide in
Detroit, New York, and Los Angeles Air. Environmental Science
and Technology 3:41-47, January 1969.
Dechant, Richard F. , and Peter K. Mueller. Performance of a
Continuous NDIR Carbon Monoxide Analyzer. AIHL Report No. 57.
Air and Industrial Hygiene Laboratory, Department of Public
Health, Berkeley, California. June 1969.
McElroy, Frank. The Intech NDIR-CO Analyzer. Presented at the
llth Methods Conference in Air Pollution at the University of
California, Berkeley, California. April 1970.
-------
Section No. 3.8.11
Revision No. 0
Date January 4, 1982
Page 2 of 2
Moore, Hezekiah. A Critical Evaluation of the Analysis of Carbon
Monoxide with Nondispersive Infrared (NDIR). Presented at the
9th Conference on Methods in Air Pollution and Industrial Hygiene
Studies at Pasadena, California. February 7-9, 1968.
Smith, Franklin, D.E. Wagoner, and R.P. Donovan. Guidelines for
Development of a Quality Assurance Program: Volume VII - Deter-
mination of CO Emissions from Stationary Sources by NDIR Spec-
trometry. EPA-650/ 4-74-005-h. Research Triangle Institute,
Research Triangle Park, N.C. for U.S. Environmental Protection
Agency, Office of Research and Development, Research Triangle
Park, N.C. February 1975.
Smith, Walter S., and D. James Grove. Stack Sampling Nomographs
for Field Estimations. Entropy Environmentalists, Inc. Research
Triangle Park, N.C. 1973.
Tentative Method of Continuous Analysis for Carbon Monoxide
Content of the Atmosphere (Nondispersive Infrared Method). In:
Methods of Air Sampling and Analysis. American Public Health
Associations, Washington, D.C. 1972.
-------
Section No. 3.8.12
Revision No. 0
Date January 4, 1982
Page 1 of 11
12.0 DATA FORMS
Blank data forms with identifying titles are included here
for the convenience of the handbook user. No page-top documenta-
tion is given in the right-hand corners of these forms, as it is
on all other pages of this CO method description. Instead to
help the user find a corresponding form in the text, a number
(Form M10-1.3) is given in the lower right-hand corner to iden-
tify the section number (1) and the figure number (3) of the
Method 10 (M10) Handbook. Future revisions of this form, if
any, will be documented by 1.3A, 1.3B, and so forth. The four in
the Method Highlights subsection are shown by the MH following
the form numbers below.
Form Title
1.3 Procurement Log
2.2 Wet Test Meter Calibration Log
2.4A & 2.4B Rotameter Calibration Data Form
(English and Metric Units)
2.8 Calibration Verification Record Chart
3.1 (MH) Pretest Sampling Checks
3.2 (MH) Pretest Preparations
4.2 Field Sampling Data Form for CO
(Continuous Sample)
4.3 Field Sampling Data Form for CO
(Integrated Sample)
4.4 (MH) On-Site Measurements Checklist
5.1 (MH) Posttest Sampling Checks
6.1 Carbon Monoxide Calculation Form
8.1 Audit Summary Report
8.2 Method 10 Checklist To Be Used by
Auditors
-------
PROCUREMENT LOG
Item description
Quantity
Purchase
order
number
Vendor
Date
Ordered
Received
Cost
Dispo-
sition
Comments
Quality Assurance Handbook M10-1.3
-------
WET TEST METER CALIBRATION LOG
Wet test meter serial number
Wet test meter flow range
Volume of test flask, V
Date
Calibrated by
Satisfactory leak check
Liquid in wet test meter and reservoir allowed to equilibrate with ambient temperature
Test
number
Manometer
reading,
mm H2O
Final
volume
(Vf), £
Initial
volume
(V^, £
Totalb
volume
-------
ROTAMETER CALIBRATION DATA FORM (English Units)
Rotameter serial number
Location
Wet test meter number
Date
Barometric pressure, P_
D
in. Hg Calibrated by
Rs'
ft3/min
e,
min
V
°F
Dm'
in. H2O
Vw'
ft3
Vr'
ft3
ft3 /min
Rs =
0 =
Dm =
Vw =
V =
ts =
P_ =
rotameter setting, ft3/min (e. g., 0.009, 0.018, 0.027)
time of calibration run, min
temperature of the gas in wet test meter, °F
pressure drop on the wet test meter, in. H2O (a negative number if calibrated
as in Figure 2.3)
gas volume passing through wet test meter, ft3
gas volume passing through the rotameter corrected to STP, ft3
flow rate through rotameter, corrected to STP, ft3/min
standard temperature, 68°F
standard pressure, 29.92 in. Hg
460) 17.65V (P
V =
Vw(Pfi
Dm/13.6) (ts
-------
ROTAMETER CALIBRATION DATA FORM (Metric Units)
Rotameter serial number
Location
Barometric pressure, P^ mm Hg
Rs'
£/min
u -
e,
min
V
°C
Dm'
mm H2O
Wet test meter number
Date
• *
Calibrated by
V
£
V
£
OB'
£/min
R = rotameter setting, £/min (e.g., 0, 0.50, 0.75)
s
6 = time of calibration run, min
t = temperature of the gas in the test meter, °C
w
V =
P =
V =
pressure drop on the wet test meter, mm H2O (a negative number if calibrated
as in Figure 2.3)
gas volume passing through wet test meter, £
gas volume passing through the rotameter corrected to STP, £
flow rate through rotameter, corrected to STP, £/min
standard temperature, 20°C
standard pressure, 760 mm Hg
VPB + Dm/13-6> <% + 273) °'386 Vw ,(PB * Dm/13'6>
(t
w
273)
(tw + 273)
at STP.
= ~S = H/min at STP.
Quality Assurance Handbook M10-2.4B
-------
CALIBRATION VERIFICATION RECORD CHART
Locat
Analy
Time
ion
zer
Test
number
Zer<
unadjusted
3
adjusted
Operate.
Date
Spa:
unadjusted
r
n
adjusted
Percent
dif-
ference
Quality Assurance Handbook M10-2.8
-------
FIELD SAMPLING DATA FORM FOR CO
Plant name
Sample location
Barometric pressure, mm (in.) Eg
Ambient temperature, °C (°F)
Intital leak check
Date
Stack temperature, °C (°F)
Final leak check
Operator
Clock
time,
24 h
Rotameter
setting,
£/min
(ft3/min)
CO cone,
ppm (dry basis)
C02,
%
Comments
Quality Assurance Handbook M10-4.2
-------
Plant name
FIELD SAMPLING DATA FORM FOR CO
Date
Sample location
Barometric pressure, mm (in.) Hg
Ambient temperature, °C (°F)
Initial leak check
Operator
Stack temperature, °C (°F)
Final leak check
Sampling
time,
min
Clock
time,
24 h
Traverse
point
Velocity head
(AP ), mm (in. ) H2O
s
Rotameter
setting,
£/min (ft3/min)
CO
cone , ppm
(dry basis)
CO2,
%
Quality Assurance Handbook M10-4.3
-------
CARBON MONOXIDE CALCULATION FORM
Plant Date
Sample location
Test number
Bag number
Operator.
CO Concentration
CCONDIR = ppm (dry basis)
FC02 = . _ % -r 100 = 0.
Ccostack = CCONDIR
= (1 - CL ) =„ ppm (dry basis)
Errors:
Quality Assurance Handbook M10-6.1
-------
AUDIT SUMMARY REPORT
Tester
Analyzer
Source
Range
Analyzer serial number
Auditor
Cylinder ID
Remarks
Date
Concentration
Audit cylinder
cone (CCQ)a/ ppm
Analyzer response
m' Ppm
Percent accuracy,
(%A), %*
*
%A =
(cco)m - (c )
CQ C0a
Quality Assurance Handbook M10-8.1
-------
METHOD 10 CHECKLIST TO BE USED BY AUDITORS
yes
no
comment
OPERATION
Presampling Preparations
1. Knowledge of process conditions
2 . Traceability of calibration gas
established
3. Calibration of pertinent equipment,
in particular, the NDIR
On- Site Measurements
4. Leak test of sampling train
5. NDIR warmup per manufacturer's
recommendations
6. Purging the train prior to sampling
7. Proportional sampling
8. Frequency of zero and span checks
9. Drying agents checked and replaced
frequently
Posts ampling
10. Transfer and handling of sample
11. Data reduction procedure/check
12. Calibration checks
GENERAL COMMENTS:
Quality Assurance Handbook M10-8.2
-------
Section No. 3.9
Revision No. 0
Date January 4, 1982
Page 1.of 10
Section 3.9
METHOD 13B - DETERMINATION OF TOTAL FLUORIDE
EMISSIONS FROM STATIONARY SOURCES
(Specific-Ion Electrode Method)
OUTLINE
Number of
Section Documentation Pages
SUMMARY 3.9 1
METHOD HIGHLIGHTS 3.9 8
METHOD DESCRIPTION
1. PROCUREMENT OF APPARATUS
AND SUPPLIES 3.9.1 20
2. CALIBRATION OF APPARATUS 3.9.2 25
3. PRESAMPLING OPERATIONS 3.9.3 6
4. ON-SITE MEASUREMENTS 3.9.4 21
5. POSTSAMPLING OPERATIONS 3.9.5 19
6. CALCULATIONS 3.9.6 7
7. MAINTENANCE 3.9.7 3
8. AUDITING PROCEDURES 3.9.8 7
9. RECOMMENDED STANDARDS FOR
ESTABLISHING TRACEABILITY 3.9.9 1
10. REFERENCE METHOD 3.9.10 2
11. REFERENCES 3.9.11 1
12. DATA FORMS 3.9.12 22
-------
Section No. 3.9 ^
Revision No. 0
Date January 4, 1982
Page 2 of 10
SUMMARY
In Method 13B, total fluorides (gaseous and particulate) are
extracted isokinetically from the source by using a sampling
train similar to the one specified in Method 5 (Section 3.4 of
this Handbook); however, the filter does not have to be heated,
and it may be located either immediately after the probe or
between the third and fourth impingers.
, The specific-ion electrode method for quantitatively mea-
suring the fluorides collected in the train is applicable to
fluoride (F) emissions from stationary sources, but not to fluo-
rocarbons such as Freon. The concentration range of the method
is from 0.02 to 2,000 pg F/ml; <0-1 M9 F/ml requires extra care.
Sensitivity of the method has not been determined.
An interferent in the collection of fluorides is grease on
sample-exposed surfaces. The fluoride absorption into the grease
causes low results due to a lack of sample recovery. If it can
be shown to the satisfaction of the administrator that samples
contain only water soluble fluorides, fusion and distillation may
be omitted from the analysis.
-------
Section No. 3.9
Revision No. 0
Date January 4, 1982
Page 3 of 10
METHOD HIGHLIGHTS
Section 3.9 (Method 13B) describes specifications for the
sampling and analysis of total fluoride emissions from stationary
sources. A gas sample is isokinetically extracted from the
source stream, and the fluorides in the stream are collected in
the sampling train.
The sampling train is similar to that in EPA Method 5, with
a few exceptions—the filter does not have to be heated, and it
may be located either immediately after the probe or between the
third and fourth impingers. If it is between the probe and the
first impinger, a borosilicate glass or stainless steel filter
holder with a 20-mesh stainless steel screen filter support and a
silicone rubber gasket must be used. If it is between the third
and fourth impingers, a glass frit filter support may be used.
Sampling is generally the same as in Method 5, but a nozzle
size that will maintain an isokinetic sampling rate of <28 A/min
(<1.0 fts/min) must be used. Samples and standards must be the
same temperature during analysis by the specific-ion electrode
(SIE). A change of 1°C (2°F) will cause a 1.5% relative error in
the sample measurements. Lack of stability in the electrometer
can also cause significant error in the results, but the main
cause of error has been found to be distillation during sample
analyses.
The collected sample is recovered by transferring the mea-
sured condensate and impinger water to a sample container, adding
the filter and the rinsings of all sample-exposed surfaces to
this container, and fusing and distilling the sample. The dis-
tilled sample is then analyzed with a SIE. Fusion and distilla-
tion may be omitted if it can be shown to the satisfaction of the
administrator that the samples contain only water soluble fluo-
rides.
Collaborative tests have shown that fluoride concentrations
from 0.1 to 1..4 pg F/m3 could be determined with an intralabora-
tory precision of 0.037 pg F/m3 and an interlaboratory precision
-------
Section No. 3.9
Revision No. 0
Date January 4fc 1982
Page 4 of 10
of 0.056 M9 F/m3. For these tests six contractors, simultaneously
took duplicate samples from a stack. The collaborative test did
not find any bias in the analytical method.l ...
.The Method Description (Sections 3-.9.1 to 3.9.9) is based on
the detailed specifications in the Reference Method (Section
3.9.10) promulgated by EPA on June 20-, 1980.2
1. Procurement of Apparatus and Supplies
Section 3.9.1 gives specifications; criteria, and design
features for the required equipment and materials. The'sampling
apparatus for Method 13B has the same design features as that of
Method 5, except for the positioning of the filter in the"sam-
pling train. This section can be used as a guide for procurement
and initial checks of 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 3.9.2 describes the required calibration procedures
for the Method 13B sampling equipment (same as Method 5), except
for .the SIE. A pretest checklist (Figure 3.1 or a similar form)
should be used to summarize the calibration and other pertinent
pretest data.
Section 3.9.3 describes the preparation of supplies and
equipment needed for the sampling. The pretest preparation form
(Figure 3.2 of Section 3.4.3) can be. used as an equipment check-
list. Suggestions for packing the equipment and supplies for
shipping are given to help minimize breakage. •
Activity matrices for the calibration of equipment and the
presampling operations (Tables 2.1 and 3.1) summarize the activi-
ties detailed in the text.
3. On-site Measurements
Section 3.9.4 describes procedures for sampling and sample
recovery. A checklist (Figure 4.5) is an easy reference for
field personnel to use in all sampling activities.
-------
Section No. 3.9
Revision No. 0
Date January 4, 1982
Page 5 of 10
4. Posttest Operations
Section 3.9.5 describes the postsampling activities for
checking the equipment and the analytical procedures. A form is
given for recording data from the posttest equipment calibration
checks; a copy of the form should be included in the emission
test final report. A control sample of known (F) concentration
should be analyzed before analyzing the sample for a quality
control check on the analytical procedures. The detailed ana-
lytical procedures can be removed for use as easy references in
the laboratory. An activity matrix (Table .5.1) summarizes the
postsampling operations.
Section 3.9.6 describes calculations, nomenclature, and
significant digits for the data reduction. A programmed calcu-
lator is recommended to reduce calculation errors.
Section 3.9.7 recommends routine and preventive maintenance
programs. The programs are not required, but their use should
reduce equipment downtime;.
5. Auditing Procedures
Section 3.9.8 describes performance and system audits.
Performance audits for both the analytical phase and the data
processing are described. A checklist (Figure 8.2) outlines a
system audit.
Section 3.9.9 lists the primary standards to which the
working standards or calibration standards should be traceable.
6. References
Section 3.9.10 contains the promulgated Reference Method;
Section 3.9.11 contains the references used throughout this
text; and Section 3.9.12 contains copies of data forms recom-
mended for Method 13B.
-------
Section No. 3.9
Revision No. 0
Date January 4,, 1982
Page 6 of 10
PRETEST SAMPLING CHECKS
(Method 13B, Figure 3.1)
Date Calibrated by
Meter box number AH@
Dry Gas Meter*
Pretest calibration factor Y | (within ±2% of the
average factor for each calibration run).
Impinger Thermometer
Was a pretest temperature correction used? __^_ yes no
If yes, temperature correction _^___ (within ±1°C (2°F)
of reference values for calibration and within ±2°C (4°F) of
reference values for calibration check)
Dry Gas Meter Thermometers
Was a pretest temperature correction made? _i yes . no
If yes, temperature correction (within ±3°C (5.4°F) of
reference value for calibration and within 6°C (10.8°F) of
reference values for calibration check)
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 the reference values to K (°R)
Barometer
Was the pretest field barometer reading correct? yes 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.
-------
Section No. 3.9
Revision No. 0
Date January 4, 1982
Page 7 of 10
ON-SITE MEASUREMENTS
(Method 13B, Figure 4.5)
Apparatus
Probe nozzle: stainless steel glass
Button-hook elbow size
Clean? "
Probe liner: borosilicate quartz other
Clean?
Heating system*
Checked?
Pitot tube: Type S other
Properly attached to probe?*
Modifications
Pitot tube coefficient
Differential pressure gauge: two inclined manometers
gther sensitivity
Filter holder: borosilicate glass glass frit
filter support silicone gasket other
Clean?
Condenser: number of impingers
Clean?
Contents: 1st 2nd 3rd 4th
Cooling system
Proper connections?
Modifications
Barometer: mercury aneroid other
Gas density determination: temperature sensor type
pressure gauge
temperature sensor properly attached to probe?*
Procedure
Recent calibration: pitot tubes*
meter box* • thermometers/thermocouples'
Filters checked visually for irregularities?*
Filters properly labeled?*
Sampling site properly selected?
Nozzle size properly selected?*
Selection of sampling time?
All openings to sampling train plugged to prevent pretest con-
tamination?
Impingers properly assembled?
Filter properly centered?
Pitot tube lines checked for plugging or leaks?*
(continued)
-------
Section No. 3.9 '
Revision No. 0
Date January 4, 1982
Page 8 of 10
Figure 4.5 (continued)
Meter box leveled? Periodically?
Manometers zeroed?
AH@ from most recent calibration
Nomograph setup properly?
Care taken to avoid scraping nipple or stack wall?*
Effective seal around probe when in-stack?
Probe moved at proper time?
Nozzle and pitot tube parallel to stack wall at all times?*
Filter changed during run? '
Any particulate lost?
Data forms complete and data properly recorded?* . ' •
Nomograph setting changed when stack temp changed significantly?
Velocity pressure and orifice pressure readings recorded
accurately?*
Sampling performed at a rate less than 1.0 cfm
Posttest leak check performed?* (mandatory)
Leakage rate __i @ in. Hg
Orsat analysisfrom stack integrated
Fyrite combustion analysis sample location
Bag system leakchecked?*
If data forms cannot be copied, record:
approximate stack temp ' volume metered
% isokinetic calculated at end of each run
SAMPLE RECOVERY
Brushes: nylon bristle other
Clean?
Wash bottles: polyethylene or glass
Clean?
Storage containers: polyethylene other
Clean? Leakfree?
Graduated cylinder/or balance: subdivisions <2 ml?*
other
Balance: type
Probe allowed to cool sufficiently?
Cap placed over nozzle tip to prevent loss of particulate?*
During sampling train disassembly, are all openings capped?
Clean-up area description:
Clean? Protected from wind?
Filters: paper type
Silica gel: type (6 to 16 mesh)? new? used?
Color? Condition?
Filter handling: tweezers used?
surgical gloves? other
Any fluoride spilled?*
(continued)
-------
Section No. 3.9
Revision No. 0
Date January 4, 1982
Page 9 of 10
Figure 4.5 (continued)
Water distilled?
Stopcock grease: acetone-insoluble?
heat-stable silicone? other
Probe handling: distilled water rinse
Fluoride recovery from: probe nozzle
probe fitting probe liner
front half of filter holder
Blank: filter _^ ; distilled water _
Any visible particles on filter holder inside probe?:*
All jars adequately labeled? Sealed tightly?
Liquid level marked on jars?*
Locked up?
Filter blank
*M6st significant items/parameters to be checked.
-------
Section No. 3.9
Revision No. 0
Date January 4 ,% 1982
Page 10 of 10
METHOD 13B CHECKLIST FOR AUDITORS
(Method 13B, Figure 8.2)
Yes
No
Comment
OPERATION
Presampling Preparation
1. Knowledge of process conditions
2. Calibration of equipment, before each
field test
On-Site Measurements
3. Sample train assembly
4. Pretest leak check
5. Isokinetic sampling
6. Posttest leak check
7. Record process conditions during sample
collection
8. Sample recovery and data integrity
Postsampling
9. Accuracy and precision of control sample
analysis
10. Recovery of samples for distillation
11. Calibration checks
12. Calculation procedure/check
General Comments:
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 1 of 20
METHOD DESCRIPTION
I
1.0 PROCUREMENT OF APPARATUS AND SUPPLIES
A schematic of the sampling train used in Method 13B is
shown in Figure 1.1. The train and the sampling procedures are
similar to EPA Method 5; the procedures and equipment for Methods
13A and 13B are identical. Commercial models of the train are
available. For those who want to build their own, construction
details are in APTD-0581;3 allowable modifications are described
herein. The operating, maintenance, and calibration procedures
for the sampling train are in APTD-0576.4 Since correct usage is
important in obtaining valid results, all users are advised to
read this document and to adopt its procedures unless alterna-
tives are outlined herein.
Specifications, criteria, and/or design features are given
in this section to aid in the selection of equipment which as-
sures collection of good quality data. Procedures and limits
(where applicable) for acceptance checks are also given.
During procurement of equipment and supplies, a log (Figure
1.2) should be used to record the descriptive titles and identi-
fication numbers (if applicable) of the equipment and the results
of the acceptance checks; a blank copy of the procurement log is
in Section 3.9.12 for the convenience of the Handbook user. If
calibration is required for the acceptance check, a calibration
log should be used to record the data. Table 1.1 at the end of
this section summarizes the quality assurance activities for the
procurement and acceptance of apparatus and supplies.
1.1 Sampling Apparatus
1.1.1 Probe Liner - The sampling probe should be constructed of
borosilicate glass (Pyrex) or 316 stainless steel tubing with an
outside diameter (OD) of about 16 mm (0.625 in.); it should be
encased in a stainless steel sheath with an OD of 25.4 mm (1.0
in.).
-------
1.9-2.5 cm
(0.75-1 in.)
1.9 cm(0.75 1n.)
PITOT TUBE
TEMPERATURE
SENSOR
THERMOMETER
'•* CHECK
VALVE
TYPE S
PITOT TUBE
, OPTIONAL
FILTER HOLDER!
3
II i
IMPINGERS
THERMOMETERS
'VACUUM
LINE
ORIFICE
MANOMETER
DRY TEST
METER
AIR TIGHT
PUMP
'"tf \J £cj C/l
(U (V (1> (D
*9 d" < °
(D
-------
Item description
fleAe-r Corx5o\^.
Quantity
Purchase
order
number
Vendor
kksf Co
Date
Ordered
V/3/SO
Received
Cost
Dispo-
sition
Comments
{!) £U CD ft)
vQ ft < O
tt> (!) H-rt
W H-
OJ ^1 H- O
goo
^s ^ °
K) H O •
C3"** •
to
•t* o •
VD
•
Figure 1.2. Example of a procurement log.
00
KJ
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 4 of 20
A heating system may be required to maintain the exit gas at
120° ±14°C (248° ±256F) during sampling. Other temperatures may
be specified by a subpart of the regulations or approved by the
administrator. Since the probe outlet temperature is not usually
monitored during sampling, probes constructed in accordance to
APTD-05813 and calibrated with procedures in APTD-05764 will be
acceptable.
Upon receiving a new probe, visually check for specifica-
tions (i.e., the length and composition ordered) and for breaks
or cracks; leak check on a sampling train (Figure 1.1); and check
the nozzle-to-probe connection with a Viton-O-ring or with Teflon
ferrules for glass liners or stainless steel ferrules for stain-
less steel liners.
The probe heating system should be checked as follows:
1. Connect the probe by attaching the nozzle to the pump
inlet.
2. Connect the probe heater to the electrical source, and
turn it on for 2 or 3 min; it should become warm to the touch.
3. Start the pump, and adjust the needle valve until a
flow rate of about 0.02 m3/min (0.75 ft3/min) is achieved.
4. Be sure that the probe remains warm to the touch and
that the heater maintains the exit gas at a minimum of 100°C
(212°F); if not, repair, return to the supplier, or reject the
probe.
1.1.2 Probe Nozzle - The probe nozzle should be designed with a
sharp, tapered leading edge and should be constructed of either
seamless 316 stainless steel tubing or glass formed in a button-
hook or elbow configuration. The tapered angle should be £30°,
with the taper on the outside to preserve a constant inside
diameter (ID).
A range of nozzle ID's [e.g., 0.32 to 1.27 cm (0.125 to 0.5
in.) in increments of 1.6 mm (0.0625 in.)] should be available
for isokinetic sampling. Larger nozzle sizes may be required
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 5 of 20
for hi-vol sampling trains or for very low stack gas velocities.
Each nozzle should be engraved with an identification number for
inventory and for calibration purposes.
Upon receipt of the nozzle from the manufacturer and before
each test, inspect it for roundness and corrosion and for damage
(nicks, dents, and burrs) to the tapered edge, and check the ID
with a micrometer. (Calibration procedures are in Section
3.9.2.) Slight variations from exact ID'S should be expected due
to machining tolerances. Reshape, return to supplier or reject.
1.1.3 Pitot Tube - The pitot tube, preferably of Type S design,
shown in Figure 1.1 should meet the requirements of Method 2
(Section 3.1.2). Proper pitot-tube-sampling-nozzle configuration
for prevention of aerodynamic interference is shown in Figures
2.6 and 2.7 of Method 2 (Section 3.1.2).
Visually inspect the 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
Section 3.1.2. Repair or return any pitot tube that does not
meet specifications.
1.1.4 Differential Pressure Gauge - The differential pressure
gauge should be an inclined manometer or the equivalent, as
specified in Method 2, Section 3.1.2. Two gauges are required.
One is used to monitor the stack velocity pressure, and the other
to measure the orifice pressure differential.
Initially, check the gauges against a gauge-oil manometer at
a minimum of three points—0.64, 12.7, and 25.4 mm (0.025, 0.5,
and 1.0 in.) H20—to see if they read within 5% at each test
point. Repair or return to the supplier any gauge that does not
meet these requirements.
1.1.5 Filters - If the filter is between the third and fourth
impingers, use a Whatman No. 1 (or equivalent) filter, sized to
fit the filter holder. If it is between the probe and the first
impinger, use any suitable medium (e.g., paper or organic mem-
brane) as long as the filter can withstand prolonged exposure up
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 6 of 20
to 135°C (275°F) and has >_95% collection efficiency (£5% penetra-
tion) for 0.3-p dioctyl phthalate smoke particles.
Conduct the filter efficiency test before beginning the
sampling by using either the ASTM Standard Method D2986-71 or
test data from the supplier's quality control program. The
filter should have a low F blank value (£0.015 mg F/cm2 of filter
area);' determine the average values of at least three filters
from the lot to be used for sampling. Glass fiber filters gen-
erally have high and/or variable F blank values, and thus are not
acceptable.
1.1.6 Filter Holder - If the filter is located between the probe
and first impinger a borosilicate glass or stainless steel filter
holder with a 20 mesh stainless steel mesh frit filter support
and a silicone rubber gasket is required by the Reference Method.
If it is between the third and fourth impingers, the tester may
use borosilicate glass with a glass frit filter support and a
silicone rubber gasket. Other gasket materials (e.g., Teflon or
Viton) may be used if approved by the administrator.
The holder design must provide a positive seal against
leakage from the outside or around the filter. The holder should
be durable, easy to load, and leak free in normal applications.
Check visually before use. If immediately following the probe,
the filter should be positioned toward the flow.
1.1.7 Filter Heating System - Any heating system may be used
which is capable of maintaining the filter holder at 120° ±14°C
(248° ±25°F) during sampling. Other temperatures may be speci-
fied by a subpart of the regulations or approved by the admini-
strator. The heating element should be easily replaceable in
case of malfunction during sampling. A gauge capable of mea-
suring within 3°C (5.4°F) should be used to monitor the tempera-
ture around the filter during sampling.
Check the heating system and the temperature monitoring
device before sampling.
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 7 of 20
1.1.8 Condenser - Four impingers with leak-free, noncontaminated
ground-glass or similar fittings should be connected in series.
The first, third, and fourth impingers must be 3 modified
Greenburg-Smith design that has a glass tube (instead of inserts)
with an unconstricted 13-mm (0.5-in.) ID extending to within 13
mm (0.5 in.) of the flask bottom. The second impinger must be a
Greenburg-Smith with the standard.tip and plate. Modifications—
for example, using flexible connections between impingers, using
materials other than glass, or using a flexible vacuum hose to
connect the filter holder to the condenser—must be approved by
the administrator." The fourth impinger outlet connection must
allow insertion of a thermometer capable of measuring ±1°C (2°F)
of true value in the range of 0° to 25°C (32° to 77°F).
Alternatively, any system that cools the gas stream and
allows measurement of the condensed water and the water vapor
leaving the condenser, each to within 1 ml or 1 g, may be used
with approval from the administrator.
Upon receipt of a standard Greenburg-Smith impinger, fill
the inner tube with water; if the water does not drain through
the orifice in 6 to 8 s or less, replace or enlarge the impinger
tip to prevent an excessive pressure drop in the sampling system.
Check each impinger visually for damage—breaks, cracks, or
manufacturing flaws such as poorly shaped connections.
1.1.9 Metering System - 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 sam-
pling rate, and related equipment shown in Figure 1.1. Other
metering systems capable of maintaining rates within 10% of
isokinetic and determining sample volumes within 2% may be used
if approved by the administrator. Sampling trains with metering
systems designed for rates higher than those described in APTD-
0581s and APTD-05764 may be used if the above specifications can
be met.
-------
Section .No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 8 of 20
When the metering system, is used with a pitot tube, the
system should permit verification of an isokinetic sampling rate
with a nomograph or by calculation.
Upon receipt or after construction of the equipment, perform
both positive and negative pressure leak checks before beginning
the calibration procedure (Section 3.9.2). Adjust, repair, or
replace the malfunctioning item. Reject a dry gas meter if it
behaves erratically or if it cannot be adjusted. Reject the
thermometer if unable to calibrate.
1.1.10 Barometer - A mercury, aneroid, or other barometer capa-
ble of measuring atmospheric pressure to within ±2.5 mm (0.1 in.)
Hg is reguire'd.
Check a new barometer against a mercury-in-glass barometer
or the equivalent. In lieu of this, obtain the absolute barom-
etric pressure from a nearby weather service station and adjust
it for the elevation difference between the station and the sam-
pling point; accordingly, 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 agree within 2.5 mm (0.1 in.) Hg of the reference
barometric pressure, either return it to the manufacturer or
reject it.
1.1.11 Gas Density Determination Equipment - A temperature sen-
sor and a pressure gauge (Method 2, Section 3.1.2) are required.
A gas analyzer (Me'thod 3, Section 3.2.2) may be required.
The temperature sensor should be permanently attached to
either the probe or the pitot tube; in either case, a fixed
configuration (Figure 1.1) should be maintained. Alternatively,
the sensor may be attached just before field use (Section 3.9.2).
1.2 Sample Recovery Apparatus
1.2.1 Probe Liner and Nozzle Brushes - Nylon bristle brushes
with stainless steel wire handles are recommended. The probe
brush must be at least as long as the probe. A separate,
smaller, and very flexible brush should be used for the nozzle.
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 9 of 20
Visually check for damage upon receipt, and replace or
return to supplier if defective.
1.2.2 Wash Bottles - Two 500-ml wash bottles are recommended for
the probe and the glassware rinsings. Glass or polyethylene are
acceptable.
1.2.3 Sample Storage Containers - Recommended are 500 ml or 1000
ml chemically resistant, high-density polyethylene bottles for
storage of samples. The bottles must have leak proof screw caps
with leak proof, rubber-backed Teflon cap liners, or they must be
constructed to preclude leakage and to resist chemical attack;
wide-mouthed bottles are easiest to use.
Prior to field use, inspect the cap seals and the bottle cap
seating surfaces for chips, cuts, cracks, and manufacturing
deformities which would allow leakage.
1.2.4 Graduated Cylinder and/or Triple Beam Balance - Either a
250-ml glass (Class A) graduated cylinder or a triple beam
balance may be used to measure the water condensed in the imping-
ers during sampling. The graduated cylinder may also be used to
measure water initially placed in the first and second impingers.
In either case, the required accuracy is 1 ml or 1 g; therefore,
the cylinder^must have subdivisions <2 ml, and the balance should
be capable of weighing to the nearest 0.1 g.
1.2.5 Plastic Storage Containers - Several airtight plastic
containers are needed for storage of silica gel.
1.2.6 Funnel and Rubber Policeman - A funnel and .a rubber po-
liceman are needed to transfer the used silica gel from the
impinger to a storage container unless silica gel is weighed in
the field after the test. A Teflon policeman is helpful for
recovery of the filter. The funnel should be glass with a 100-mm
diameter and a 100-mm stem.
Visually check on receipt, and replace or return if damaged.
1.3 Distilling Apparatus
The fluoride distillation setup is shown in Figure 1.3.
1.3.1 Flasks - A long^necked, round bottom 1-liter flask with
24/40 joint grindings is needed for boiling the sample solution.
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 19 82,
Page 10 of "20
CONNECTING TUBE
12-rmnID
'24/40
THERMOMETER
TIP MUST
EXTEND BELOW
THE LIQUID LEVEL
WITH 10/30
24/40
1-liter
FLASK
BUNSEN
BURNER
24/40
CONDENSER
250 ml
VOLUMETRIC
FLASK
Figure 1.3. Fluoride distillation apparatus.
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 11 of 20
Also, a 250-ml volumetric (Class A) flask is needed to receive
the condensate.
1.3.2 Thermometer - A thermometer for checking the temperature
of the sample in the boiling flask should read within ±1°C (±2°F)
of the true value in the range of 100° to 200°C (212° to 392°F).
Check it against a mercury-in-glass thermometer.
1.3.3 Adapter - An adapter should have joint grindings (inner
and outer parts) that are 24/40 at the bottom and 10/30 at the
top that will hold a thermometer, and it should have a 24/40
joint grinding (inner part) at the end of the top sidearm that
joins the connector tube.
1.3.4 Connector Tube - A tube with a standard or a medium wall
and with a 13-mm (0.5 in.) ID is needed for connecting the
adapter to the condenser.
1.3.5- Condenser - A coiled integral Graham condenser (joint
grinding 24/40) with a jacket length of 300 mm (12 in.) is needed
for condensation of the distillate.
1.4 Miscellaneous Glassware
1.4.1 Beaker - A 1500-ml glass beaker (Class A) with 5-ml sub-
divisions is needed to receive the filtered sample from container
No. 1 or No. 2.
1.4.2 Pipettes - Several volumetric pipettes (Class A)—includ-
ing 5, 10, 20, 25, 50 mi's—should be available. Record the
stock numbers, and visually check for cracks, breaks, or manu-
facturer's flaws. If irregularities are found, either replace or
return to the supplier.
1.4.3 .Volumetric Flasks - The following volumetric flasks are
needed for performing the analysis: a 50-ml glass volumetric
flask (Class A) is needed to dilute the sample aliquot to 50 ml
with TISAB (total ionic strength adjustment buffer) in determina-
tion of fluoride concentration; a 1-J2. glass volumetric flask
(Class A) to dilute the fused sample to volume with distilled
water; and several 100-ml polyethylene volumetric flasks to
prepare the fluoride standardizing solution.
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 12 of 20
1.5 Reagents and other Supplies (Sampling)
Unless otherwise indicated, all reagents should meet the
specifications of the Committee on Analytical Reagents of the
American Chemical Society (ACS); otherwise, use the best avail-
able grade.
1.5.1 Silica Gel - Use indicating type 6-16 mesh. If previously
used, dry at 175°C (347°F) for at least 2 h before reusing. New
silica gel may be used as received.
1.5.2 Water - Deionized distilled water should conform to ASTM
specification D1193-74, Type 3. At the option of the analyst,
the KMn04 (potassium permanganate) test for oxidizable organic
matter may be omitted if high concentrations of organic matter
are not expected.
1.5.3 Crushed Ice - Enough crushed ice is • needed around the
impingers to maintain <20°C (68°F) at the impinger silica gel
outlet in order to avoid excessive moisture loss.
1.5.4 Stopcock Grease - Acetone insoluble, heat stable silicone
grease is required unless screw-on connectors with Teflon or
similar sleeves are used.
1.6 Reagents and Supplies (Sample Recovery and Analysis)
Unless otherwise indicated, all reagents should meet the
specifi.cations of the Committee on Analytical Reagents of the
American Chemical Society (ACS); otherwise, use the best avail-
able grade.
1.6.1 Calcium Oxide (CaO) - A reagent grade or a certified ACS
grade of CaO should contain £0.005% F.
1.6.2 Filters - Whatman No. 541 (or equivalent) filters are re-
quired for filtration of the impinger contents and preparation of
the sample for analysis.
1.6.3 Phenolphthalein Indicator - A reagent grade or a certified
ACS 0.1% phenolphthalein should be a 1:1 ethanol-water mixture.
1.6.4 Sodium Hydroxide - An ACS reagent grade (or the equiva-
lent) NaOH pellets and 5M NaOH reagent grade or ACS is needed.
1.6.5 Sulfuric Acid - An ACS reagent grade (or the equivalent)
concentrated H2S04 and 25% (v/v) reagent grade or ACS is needed.
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 13 of 20
1.6.6 Total Ionic Strength Adjustment Buffer (TISAB) - To ap-
proximately 500 ml of distilled water in a 1-2 beaker, add 57 ml
of glacial acetic acid, 58 g of sodium chloride, and 4 g of
cyclohexylene dinitrilotetra acetic acid (CDTA). Stir to dis-
solve. Place the beaker in a water bath until it cools. Then,
slowly add 5 M NaOH, while measuring the pH continuously with a
calibrated pH-reference electrode pair, until the pH is 5.3.
Cool to room temperature. Pour into a 1-2 flask, and dilute to
volume with distilled water. Commercially prepared TISAB buffer
may be substituted for the above.
1.6.7 Fluoride Standard Solution - To prepare a 0.1M fluoride
reference solution, add 4.20 grams of reagent grade sodium fluo-
ride (NaF) to a 1-2 volumetric flask, and add enough distilled
water to dissolve it. Dilute to volume with distilled water.
The NaF must be oven dried at 110°C for at least 2 h prior to
weighing.
1.7 Analytical Equipment
1.7.1 Bunsen Burner - A Bunsen burner capable of distilling 200
ml in <15 min is required for the boiling flasks.
1.7.2 Crucible - A nickel crucible with a capacity of 75 to
100 ml is needed to evaporate the water from the sample on a hot
plate.
Upon receipt, check for cracks or manufacturing flaws as
well as for capacity. If it does not meet specifications replace
or return it to the manufacturer.
1.7.3 Hot Plate - A hot plate capable of 500°C (932°F) is re-
quired for heating the sample in a nickel crucible.
Check upon receipt and before each use for damage. Check
the heating capacity against a mercury-in-glass thermometer. If
inadequate, repair or return the hot plate to the supplier.
1.7.4 Electric Muffle Furnace - An electric muffle furnace
— — - i
capable of heating to 600°C (1112°F) is needed to fuse the sam-
ple.
Check the heating capacity against a mercury-in-glass-ther-
mometer. Replace or return to the manufacturer any unit which
does not meet specifications.
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 14 of 20 • '
1.7.5 Balance - A balance with a capacity of 300 g ±0.5 g is
needed to determine moisture.
Check for damage against a series of standard weights upon
receipt and before each use. Replace or return to the manufac-
turer if damaged or if it does not meet specifications.
1.7.6 Analytical Balance - An analytical balance capable of
weighing to within 0.1 mg is needed for preparation of the stan-
dard fluoride solution and the analytical reagents. Check: the
balance frequently with Class S weights.
1.7.7 Constant Temperature Bath - A water bath is needed to
maintain a constant room temperature for optimum measurement-of
the sample concentration.
i.7.8 Fluoride Ion Activity-Sensing Electrodes - A fluoride ion
(F~) activity-sensing electrode is required in Method 13B for
determining of F~ ion activity in concentrations of from 1 to
10~ mol/£ (19,000 to 0.02 ppm). The electrode should be usable
from a pH of 1 to 8.5 at 10~6 mol/£, up to a pH of 11 at 10"2
mol/£ F~ concentration. Due to the complexing of F~ below pH of
4 and to the limited resistance of the electrode body to certain
concentrated acids, it is usually advisable to adjust the pH of
strongly acidic samples.
Check for damage and F~ sensing accuracy with a known con-
centration upon receipt and before each use. If not suitable,
replace or return to manufacturer. Either a single junction,
sleeve type reference electrode or a combination type fluoride
ion-sensing electrode built into one unit ma'y be used.
1.7.10 Electrometer - Either a pH meter with a millivolt scale
capable of ±0.1-mV resolution or a ion meter made especially for
specific-ion use is needed to read the ion activity or the F~
concentration.
1.7.11 Magnetic Stirrer - A magnetic stirrer and TFE* fluorocar-
bon-coated stirring bars are needed for uniform mixing of the
sample solution.
1.7'. 12 Stopwatch or Clock - A stopwatch or a clock is, needed to
check'minimum immersion time of electrode in sample.
*Mention ofany trade name or specific product does not consti-
tute endorcement by the Environmental Protection Agency.
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 15 of 20
TABLE 1.1 ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS
AND SUPPLIES
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sampling
Probe liner
Specified material of
construction; equipped
with heating system
capable of maintaining
120°±14°C (248° ±25°F)
at the exit
Visually check the
probe and run the
heating system
Repair, return
to supplier,
or reject
Probe nozzle
Stainless steel (316)
with sharp, tapered
angle <30°; differ-
ence in measured diam-
eters <0.1 mm (0.004
in.); ino nicks, dents,
or corrosion
Visually check upon
receipt and before
each test; use a mi-
crometer to measure
ID before field use
after each repair
Reshape and
sharpen, re-
turn to the
supplier, or
reject
Pi tot tube
Type S (Meth 2, Sec
3.1.2); attached to
probe with impact
(high pressure) opening
plane even with or
above nozzle entry
plane
Visually check for
vertical and hori-
zontal tip alignments;
check the configura-
tion and the clear-
ances; calibrate
(Sec 3.1.2, Meth 2)
Repair or re-
turn to sup-
plier
Differential
pressure
gauge (in-
clined ma-
nometer)
Meets criteria (Sec
3.1.2); agrees within
5% of gauge-oil
manometer
Check against a gauge-
oil manometer at a
minimum of three
points: 0.64(0.025);
12.7 (0.5); 25.4(1.0)
mm (in.) H20
As above
Filters
Capable of withstand-
ing temperatures to
135°C (275°F), 95%
collection efficiency
for 0.3 urn particles,
low F blank (<0.015
mg F/cm2)
Check each batch for
F blank values,
visibly inspect for
pin holes or flaws
Reject batch
(continued)
-------
Section No. 3.9.1
Revision No. 0 "
Date January 4, 1982
Page 16 of 20 -
TABLE 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Filter holder
Leak free; borosilicate
glass
Visually check before
use
Return to
supplier
Condenser
Four impingers, standard
stock glass; pressure
drop not excessive
Visually check upon
receipt; check pres-
sure drop
As above
Vacuum gauge
0-760 mm (0-30 in.) Hg,
±25 mm (1 in.) at
380 mm (15 in.) Hg
Check against mer-
cury U-tube manometer
upon receipt
Adjust or re-
turn to sup-
plier
Vacuum pump
Leak free; capable of
maintaining flow rate
of 0.02-0.03 mVmin
(0.7 to 1.1 ftVmin)
for pump inlet vacuum
of 380 mm (15 in.) Hg
Check upon receipt
for leaks and capaci-
ty
Repair or re-
turn to sup-
plier
Barometer
Capable of measuring
atmospheric pressure
±2.5 mm (0.1 in.) Hg
Check against a mer-
cury- in-glass barom-
eter or equivalent;
calibrate (Sec 3.1.2)
Determine cor-
rection fac-
tor, or reject
Orifice meter
AH@ of 46.74± 6.35 mm
(1.84 ± 0.25 in.) H20
at 20°C (68°F);
optional
Upon receipt, visual-
ly check for damage;
calibrate against wet
test meter
Repair or re-
turn to sup-
plier
Dry gas meter
Capable of measuring
volume within ±2% at a
flow rate of 0.02
nrVmin (0.7 ftVmin)
Check for damage upon
receipt and calibrate
(Sec 3.9.2) against
wet test meter
Reject if dam-
aged, behaves
erratically,
or cannot be
properly ad-
justed
(continued)
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 17 of
Table 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Thermometers
±1°C (2°F) of true
value in the range of
0° to 25°C (32° to 77°F)
for impinger thermometer
and ±3°C (5.4"°F) of true
value in the range of
0°C to 90°C (32° to
194°F) for dry gas
meter thermometers
Check upon receipt
for dents or bent
stem, and calibrate
(Sec 3.9.2) against
mercury-in-glass
thermometer
Reject if un-
able to cali-
brate
Sample Recovery
Probe liner and
probe nozzle
brushes
Nylon bristles with
stainless steel han-
dles; properly sized
and shaped
Visually check for
damage upon receipt
Replace or re-
turn to sup-
plier
Wash bottles
Polyethylene or glass,
500 ml
Visually check for
damage upon receipt
As above
Storage con-
tainer
.High-density polyeth-
ylene, 1000 ml
Visually check for
damage upon receipt;
be sure caps make
proper seals
As above
Graduated
cyli nder
Glass, Class A, 250 ml
Upon receipt, check
for stock number,
cracks, breaks, and
manufacturer flaws
As above
Funnel
Glass, Class A, diameter
100 mm; stem length
100 mm
Visually check for
damage upon receipt
As above
Rubber police-
man
Properly sized
Visually check for
damage upon receipt
As above
(continued)
-------
TABLE 1.1 (continued)
Section No. 3.9-. 1
Revision No. 0
Date January 4,_ 1982
Page 18 of 20
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Pipettes, volu-
metric flask
beaker, flask
adapter, con-
denser, con-
nection tube,
Erlenmeyer
flask
Glass, Class A
Upon receipt, check
for stock number,
cracks, breaks and
manufacturer flaws
Replace or re-
turn to sup-
plier
Distallation
Apparatus
Bunsen burner
Capable of distilling
220 ml in <15 min
Visually check upon
receipt; check heat-
ing capacity, check
for damage
Replace
Crucible
Nickel material; 75-
100 ml
Check upon receipt
for cracks or flaws
Replace or re-
turn to manu-
facturer
Analytical
Equipment
Hot plate
Heating capacity of
500°C (932°F)
Check upon receipt
and before each use
for damage; check
heating capacity
against mercury-in-
glass thermometer
Replace or re-
turn to manu-
facturer
Electric muffle
furnace
Heating capacity of
600°C
Check upon receipt
and before each use
for damage; check
heating capacity
upon receipt against
mercury-in-glass
thermometer
Replace or re-
turn to manu-
facturer
(continued)
-------
Section No. 3.9.1
Revision No. 0
Date January 4, 1982
Page 19 of 20
Table 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Balance
Capacity of 300 g ±0.5g
Check for damage and
against series of
standard weights upon
receipt and before
each use
Replace or re-
turn to manu-
facturer
Water bath
Capable of maintaining
constant room tempera-
ture
Check with mercury-
in-glass thermometer
Repair
Fluoride ion
activity-sen-
sing electrode
Capable of measuring
F concentration from
1 to 1C-6 mol/Jd
(19,000 to 0.02 ppm)
Check for damage and
F sensing accuracy
with a known con-
centration upon re-
ceipt and before
each use
Replace or re-
turn to manu-
facturer
Reference
electrode
Should provide stable
output
Check visually for
cracks or breaks
Replace or re-
turn to manu-
facturer
Electrometer
Capable of reading to
±0.1 mV resolution with
temperature compensa-
tion
Upon receipt and
before each use,
check for per-
formance accuracy
with a_known stan-
dard F solution
Replace or re-
turn to manu-
facturer '
Reagents
Filters
Whatman No.
equivalent
541 or
Visually check for
damage upon receipt'
Replace or re-
turn to sup-
plier
Silica gel
Indicating Type 6-16
mesh
Upon receipt check
label for grade or
certification
Replace or re-
turn to manu-
facturer
(continued)
-------
Section No. 3.9.. 1
Revision No. 0
Date January 4, 1982
Page 20 of 20 -
TABLE 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Reagents
Distilled water
Must conform to ASTM-
D1193-74, Type 3
Check each lot
Replace or re-
turn to manu-
facturer
Crushed ice
Check frozen condition
Stopcock grease
Acetone insoluble, and
heat stable silicon
grease
Upon receipt, check
label for grade or
certification
As above
Calcium oxide
powder
Reagent grade or cer-
tified ACS
As above
As above
Phenolphthalein
0.1% in 1:1 ethanol-
water mixture; reagent
grade or certified ACS
As above
As above
Sodium hy-
droxide
NaOH pellet 5M NaOH
reagent grade or cer-
tified ACS
As above
As above
Sulfuric acid
Concentrated, reagent
grade or certified ACS;
25% (v/v) reagent grade
or ACS
As above
As above
Fluoride stan-
dard solution
Reagent grade or ACS;
1 M concentration
As above
As above
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 1 of 25
2.0 CALIBRATION OF APPARATUS
Calibration of apparatus is one of the most important func-
tions in maintaining data quality. The detailed calibration
procedures in this section are designed for the equipment speci-
fied in Method 13B and described in the previous section. A
laboratory log book of all calibrations must be maintained.
Table 2.1 at the end of this section summarizes the quality
assurance activities for calibration.
2.1 Metering System
2.1.1 Wet Test Meter - A wet test meter with a capacity of 3.4
3 3
m /h (120 ft /h) will be needed to calibrate the dry gas me.ter.
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. For large wet test meters (>3£/rev),
there is no convenient procedure for checking the calibration;
for this reason, several methods are suggested, and others may be
approved by the administrator.
The initial calibration may be checked by any of the fol-
lowing methods:
1. Certification from the manufacturer that the wet test
meter is within +1% of true value at the wet test meter dis-
charge, so that only a leak check is needed.
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 by a primary air or liquid displace-
ment method (Section 3.5.2).
4. Comparison against a dry gas meter that has previously
been calibrated by a primary air or liquid displacement method.
The calibration of the test meter should be checked annual-
ly. This yearly calibration check can be made by the same method
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 2 of 25
as that of the original calibration; however, the comparison pro-
cedure need not be recalibrated if the check is within +1% of the
true value; if not within ±1%, either the comparison procedure or
the wet test meter must be recalibrated against a primary air or
liquid displacement method.
2.1.2 Sample Meter System - The sample meter system—consisting
of the pump, vacuum gauge, valves, orifice meter, and dry gas
meter—should be initially calibrated by stringent laboratory
procedures before it is used in the field. After initial accept-
ance, the calibration should be rechecked after each field test
series. The recheck procedure can be used by the tester often
and with little time and effort to ensure that calibration has
not changed. When the quick check indicates that the calibration
factor has changed, the tester must again use the complete labo-
ratory procedure to obtain a 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.
Before initial calibration, a leak check is recommended, but
it is not mandatory. Both positive (pressure) and negative
(vacuum) leak checks should be performed. Following is a pres-
sure leak-check procedure for checking the metering system from
the quick disconnect inlet to the orifice outlet and for checking
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), and plug this tap (Figure 2.1).
2. Vent the negative side of the inclined manometer to the
atmosphere. If the manometer is equipped with a three-way valve,
merely turn the valve that is on the negative side of the
orifice-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, and connect a piece of
rubber or plastic tubing to the tube, as shown in Figure 2.1.
-------
RUBBER
TUBING
RUBBER ORIFICE
STOPPER
BLOW INTO TUBING UNTIL
MANOMETER. READS 127 to
178 mm ( 5 TO 7 in.)
MAIN VALVE
CLOSED
ORIFICE/
MANOMETER
Figure 2.1. Positive leak check of metering system.
*d O £0 en
(U fo (D CD
iQ ft < O
(B fl> H-rt
_, to p.
tA>£ H-O
*" o "-i
LO
0«
vo
vo
00
K)
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 4 of 25 '
4. Open the positive side of the manometer to the "read-
ing" position; if the 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 discon-
nect 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 ori-
fice 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 1 min. No noticeable
movement in the manometer fluid level should occur. A bubbling-
type leak-check solution may aid in locating any leak in the
meter box.
After the metering system is determined to be leak free by
the positive leak-check procedure, check the vacuum system to and
including the pump.
1. Plug the air inlet to the metet box. If a quick dis-
connect with a leak-free stopper system is on the meter box, the
inlet will not have to be plugged.
2. Turn the pump on and pull a vacuum within 7.5 cm (3
in.) Hg of absolute zero.
3. Observe the dry gas meter. If leakage is > 0.00015
m3/min (0.005 ft3/min), find and minimize the leak(s) until the
above specifications are satisfied.
For metering systems with diaphragm pumps, the leak-check
procedures above will not detect leakages within the pump; the
following procedure is suggested:
1. Make a 10-min calibration run at 0.00057 m3/min (0.02
ft3/min).
2. At the end of the run, find the difference between the
measured wet test meter and the dry gas meter volumes, and divide
the difference by 10 to get the leak rate. The leak rate should
not exceed 0.00057 m3/min (0.02 ft3/min).
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 5 of 25
2.1.2.1 Initial calibration - The dry gas meter and the orifice
meter can be calibrated simultaneously, and both should be cali-
brated when first purchased and any time the posttest check
yields a Y outside the range of the calibration factor Y +0.05Y.
Use a calibrated wet test meter (properly sized, with +1%
accuracy) to calibrate both the dry gas meter and the orifice
meter (Figure 2.2) in the following manner:
1. Leak check the metering system (Subsection 2.1.2), and
eliminate any leaks before proceeding.
2 . Connect the air outlet of the wet test meter to the
needle valve at the inlet side of the meter box (Figure 2.2).
3. Run the pump for 15 min with the orifice meter differ-
ential (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.
4. 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 cali-
bration.
5. Record the required data on Figure 2.3A or 2.3B, using
sample volumes as shown.
6. Calculate Y. for each of the six runs, using the equa-
tion in Figure 2.3A or 2.3B, and' record the results on the form
in the space provided.
7. Calculate the average Y (calibration factor) for the
six runs, using the following equation:
Y + Y +Y + Y + Y +Y
* 2 3 4 5 *6 .
Record the average in the space provided on Figure 2.3A or
2.3B.
8. Clean, adjust, and recalibrate, or reject the dry
gas meter if one or more values are outside the interval Y
10.02Y; otherwise, the average Y is acceptable and should be
used for future . checks and test runs.
-------
AIR INLET
WET TEST METER
AIR OUTLET >v\_ ^-
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 7 of 25
Date
Meter box number f^-hi —
Barometric pressure, P, = p? 9. L^J- in- Hg Calibrated by
Orifice
manometer
setting
(AH),
in. H20
0.5
1.0
1:5
2.0
- 3.0
4.0
Gas volume
Wet test
meter
,
bF
7/, 5-
7/,S~
Dry gas meter
Inlet
ft,),
• 1
OF
91
1?
Outlet
(t, ),
o
°F
83
£S
Avg"
(t,),
°F
*1
Time
(6),
min
uy
fate
Avg
Y.
/r/7)V
AH@.,
in. HgO
/.7?
AH,
in.
Hf\
0.5
1.0
1.5
2.0
3.0
4.0
AH
13.6
0.0368
0.0737
0.110
0.147
0.221
0.294
„ Vw Pb(td + 460)
i AH
"d^b 13. 6"* Vl"w ~rwv/ J
is (39, L
•S". It (59 / 67 J £^3A 2r")
0.0317 AH [Ctw-A60)e]2
-"*•! P, (t + 460) 1 V J
D U L W J
/^>' 03/7^ do-sT>r7^.i?7. s>^/ o 7$>)7
&*), (<>*£)( fi^cT) 5 ~1
If there is only one thermometer on the dry gas meter, record the temperature
under t,.
d
Figure 2.3A. Dry gas meter calibration data (English units).
(front side)
-------
Nomenclature:
V = Gas volume passing through the wet test meter, ft3.
Tf
V, = Gas volume passing through the dry gas meter, ft?.
t ."= Temperature of the gas in the wet test meter, °F.
ifl
t, = Temperature of the inlet gas of the dry gas meter, °F.
t, = Temperature of the outlet gas of the dry gas meter, °F.
o
t, = Average temperature of gas in dry gas meter, obtained by average t, and
V °F- i
AH = Pressure differential across orifice, in. H2O.
Y. = Ratio of accuracy of wet test meter to dry gas meter for each run; tolerance Y. =
Y±0.02 Y. 1
Y = Average ratio of accuracy of wet test meter to dry gas meter for all six runs.
fiH@. = Orifice pressure differential at each flow rate that gives 0.75 ft3/min of air at
standard conditions for each calibration run, in. H2O; tolerance = AH@±0.15
(recommended).
AH@ = Average orifice pressure differential that gives 0.75 ft3/min of air at standard J" P» «> «>
conditions for all six runs, in. H20; tolerance = 1.84±0.25 (recommended). o> ron-lt
to H
00
>u o •
•» VD
•
Figure 2.3A. Dry gas meter calibration data (English units). (backside) £ ^>
00
KJ
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 9 of 25
Date
Barometric pressure, P. =
Meter box number
mm Hg Calibrated by
Orifice
manometer
setting
(AH),
.mm H£O
10
25
40
50
75
100
Gas volume
Wet test
meter
•+• — =£l— "1 ff 4- O7^
v^v*v not-' v1., A/Jj
a D Ij.O W
(O>«J3~) ( T36. ">^b9 / ")
Cr>,i5^ C 73 Y) ^2
-------
Nomenclature:
V = Gas volume passing through the wet test meter, m3 .
Vf
V, = Gas volume passing through the dry gas meter, m3 .
t = Temperature of the gas in the wet test meter, °C.
Vf
t, = Temperature of the inlet gas of the dry gas meter, °C.
t, = Temperature of the outlet gas of the dry gas meter, °C.
o
t, = Average temperature of gas in dry gas meter, obtained by average of t, and
t °c i
i_d , u. i
o
AH = Pressure differential across orifice, mm H2O.
Y. = Ratio of accuracy of wet test meter to dry gas meter for each run; tolerance Y. =
1 Y+0.02 Y.
Y = Average ratio of accuracy of wet test meter to dry gas meter for all six runs.
AH@. = Orifice pressure differential at each flow rate that gives 0.021 m3 of air at standard
conditions for each calibration run, mm H2O; tolerance AH@. = AH@±3.8 mm H2O
( recommended ) .
•n D Jd cr.
AH@ = Average orifice pressure differential that gives 0.021 m3 of air at standard con- »S £• < o
ditions for all six runs, mm H20; tolerance AH@ = 46.74 +6.3 mm H2O (recommended) n> o> p-r+
~ 01 H
M (-t H- O
6 = Time of each calibration run, mm. ° K 2 °
3 P
O C 2
P. = Barometric pressure, mm Hg. "^ ?j o
D ro^ •
Figure 2.3B Dry gas meter calibration data (metric units). (backside)
Ul • Ul
o •
oo •
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 11 of 25
9. Calculate AH@- for each of the six runs, using the
equation in Figure 2.3A or 2.3B, and record the results on the
form in the space provided.
10. Calculate the average AH@ for the six runs, using the
following equation:
AH@, + AH@, + AH@, + AH@A +
AH@ = - - - - - ^7 - — -
Record the average in the space provided on Figure 2.3A or 2.3B.
11. Adjust the orifice meter or reject it if AH(§L varies by
more than ±3.8 mm (0.15 in.) H2O over the range of 10 to 100 mm
(0.4 to 4.0 in.) H20; otherwise, the average AH@ is acceptable
and should be used for subsequent test runs.
2.1.2.2 Posttest .calibration check - After each field test
series, conduct a calibration check of the metering system (Sub-
section 2.1.2) except for the following variations:
1. Three calibration runs at a single intermediate orifice
meter setting may be used with the vacuum set at the maximum
value reached during the test series . The single intermediate
orifice meter setting should be based on the previous field test.
To adjust the vacuum, insert a valve between the wet test meter
and the inlet of the metering system.
2. If a temperature-compensating dry gas meter was used,
the calibration temperature for the dry gas meter must be within
+6°C (10.8°F) of the average meter temperature during the test
series.
3. Use Figure 2.4A or 2.4B to record the required data.
If the recalibration factor Y deviates by <5% from the
initial Y (determined in Subsection 2.1.2), the dry gas meter
volumes recorded during the test series are acceptable; if Y
deviates by >5%, recalibrate the metering system (Subsection
2.1.2), and use the coefficient (initial or recalibrated) that
yields the lower gas volume for each test run.
Alternate procedures — for example, using the orifice meter
coefficients — may be used, subject to the approval of the admini-
strator.
-------
Test numbers /)6 l~3 Date $-/3-8O Meter box number f
Barometric pressure, P. = £8. 7Si in. Hg Dry gas meter number
-7
Plant flcme.
Pretest Y
Q.
Orifice
manometer
setting,
(AH),
in. H20
•i.it
Gas volume
Wet test
meter
ft3
10
10
10
Dry gas
meter
(vd),
ft3
» 7& ^y
Temperature
Wet test
meter
(V,
°F
7*
Dry gas meter
Inlet
°F
£3
Outlet
(td>.
o
°F
7f
Average
°F
7^
Time
(e),
min
13.3*
Vacuum
setting,
in. Hg
3.o
Yi
o4*7
Yi
Vw Pb ^d + 460)
Vd(Pb + Ti:s)k + 460)
/o(as.7si)(s'y?}
/o.*A3(lS.7A+'~l)(S3A
Y =
If there is only one thermometer oh the dry gas meter, record the temperature under t ..
V = Gas volume passing through the wet test meter, ft3.
Tr
V . = Gas volume passing through the dry gas meter, ft3.
t = Temperature of the gas in the wet test meter, °F.
W
t . = Temperature of the inlet gas of the dry gas meter, °F.
t . = Temperature of the outlet gas of the dry gas meter, °F.
o
t . = Average temperature of the gas in the dry gas meter, obtained by the average of t.
AH = Pressure differential across orifice, in. H20. *
Y. = Ratio of accuracy of wet test meter to dry gas meter for each run.
Y = Average ratio of accuracy of wet test meter to dry gas meter for all three runs;
tolerance = pretest Y +0.05Y
P. = Barometric pressure, in. Hg.
9 = Time of calibration run, min.
Figure 2.4A. Posttest dry gas meter calibration data form (English units).
and t
*rj O 5d
to n» n>
«Q rt<
oc fl> (I> H-
m
C-i H-
»F.
o
rt
H-
0
o
H,OI s:
i-« o
U)
vo
ro
00
-------
lest numbers fl& l~3 Date S-/3-SO Meter box number _
Barometric pressure, P. = mm Hg Dry gas meter number
FW- 7
Plant ftc.me. fLoer
Pretest Y
Orifice
manometer
setting,
(AH),
mm H20
36
Gas volume
Wet test
meter
(vw),
m3
0.30
0.30
0.30
Dry gas
meter
(vd),
m3
34. / 7 44
iq.f73O
Temperature
Wet test
meter
(tw),
°C
A\
Dry gas meter
Inlet
"d.)'
°C
33.5"
Outlet
(td),
o
°C
Alf
Average
°C
Yi
Vw Pb (td + 273)
V. /Pb + AH Vt + 273\
d ( b 13. 6A /
0.30 (73oXa
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 14 of 25
2.2 Temperature Gauges
2.2.1 Impinger Thermometer - The thermometer used to measure
temperature of the gas leaving the impinger train should initial-
ly be compared with a mercury-in-glass thermometer which meets
ASTM E-l No. 3C or 3F specifications. The procedure is as
follows:
1. Place both the reference thermometer and the test
thermometer in an ice bath, and compare readings after they
stabilize.
2. Remove the thermometers from the bath, and allow both
to come to room temperature, compare readings after they stabi-
lize.
3. Accept the test thermometer if both of its readings
agree within 1°C (2°F) of the reference thermometer reading. If
the difference is greater than ±1°C (2°F), either adjust and
recalibrate it until agreement is obtained, or reject it.
2.2.2 Dry Gas Thermometers - The thermometers used to measure
the metered gas sample temperature should initially be compared
with a mercury-in-glass thermometer, using a similar procedure.
1. Place a dial type or an equivalent thermometer and a
mercury-in-glass thermometer in a hot water bath, 40° to .50°C
(105° to 122°F); compare the readings after the. bath stabilizes.
2. Allow both thermometers to come to room temperature and
compare readings after they stabilize.
3. Accept the dial type or equivalent thermometer if the
values agree within 3°C(5.4°F) at both points or if the temper-
ature differentials at both points are within ±3°C(5.4PF); tape
the temperature differential to the thermometer,' and record them
on the pretest sampling check form (Figure 3.1 of Section 3.9.3).
4. Before each field trip, compare the reading of the
mercury-in-glass thermometer at room temperature with that of the
meter system thermometer; the values or the corrected values
should agree within ±6°C (10.8°F) of one another, or the meter
thermometer should be replaced or recalibrated. Record . any
correction/factors on Figure 3.1 or on-a similar form.
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 15 of 25
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 temperature range anticipated during actual
sampling. For the three-point calibration, a reference mercury-
in-glass thermometer should be used. The following procedure is
recommended for calibrating stack temperature sensors (thermo-
couples and thermometers) for field use.
1. For the ice point calibration, form a slush from
crushed ice and water (preferably deionized distilled) in an
insulated vessel such as a Dewar flask; being sure that the
sensor does not touch the sides of the flask, insert the stack
temperature sensor 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 in 1-min
intervals. Note: . Longer times may be required to attain thermal
equilibrium with thick-sheathed thermocouples.
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.
Alongside the sensor(s), an. ASTM reference thermometer
should be placed. After 3 min, both instruments will attain
thermal equilibrium. Simultaneously record temperatures from the
ASTM reference thermometer and the stack temperature sensor three
times at 1-min intervals.
If the entire length of the mercury column in the thermom-
eter cannot be immersed, a temperature correction will be re-
quired to give the correct reference temperature.
3. For a thermocouple, repeat Step 2 with a liquid (e.g.,
cooking -oil) that has a boiling point 150° to 250°C (300° to
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 16 of 25
500°F), and record all data on Figure 2.5. For thermometers
other than thermocouples, either repeat Step 2 with a liquid that
boils at the maximum temperature that the thermometer is to be
used or place the stack thermometer and the reference thermometer
in a furnace or other device to attain the desired temperature.
Note; If the thermometer is to be used at temperatures higher
than the reference thermometer will record, calibrate the stack
thermometer with a thermocouple previously calibrated by the
above procedure.
4. If the absolute temperature of the reference thermom-
eter and the thermocouple (s) agree within ±1.5% at each of the
three calibration points, either plot the data on' linear graph
paper and draw the best-fit line between the points or calculate
the linear equation using the method of least-squares. For the
thermocouple, the data may be extrapolated above and below the
calibration points to cover the manufacturer's suggested range,"
for the portion of the plot (or equation) that agrees within
1.5% of the absolute reference temperature, no correction is
needed, but for all other portions that do not agree within
±1.5%, use the plot (or equation) to correct the data.
If the absolute temperatures of the reference thermometer
and stack temperature sensor (other than the thermocouple) agree
within ±1.5% at each of the three points, the thermometer may be
used for testing without applying any correction factor over the
range of calibration points, but the data cannot be extrapolated
outside the calibration points.
2.3 Probe Heater
The probe heating system should be calibrated before field
use according to the procedure in APTD-0576.4 Probes constructed
according to APTD-05813 need not be calibrated if the curves of
APTD-05764 are used.
2.4 Barometer
The field barometer should be adjusted initially and before
each test series to agree within ±2.5 mm (0.1 in.) Hg of the
mercury-in-glass barometer reading or with the value reported by
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 17 of 25
Date
Thermocouple number
Ambient temperature
Calibrator
C Barometric pressure
J. £ J
in. Hg
Reference: mercury-in-glass
other
Reference
point
number
0°
/oo" •
Source3
(specify)
IC£ t*Jf)T£4,
boi/if* uftTiA
Uoili'tfQ C*'£i''l/1
Reference
thermometer
temperature,
°C
/<
/
-------
Section No. 3.9.2.
Revision No. 0
Date January 4, 1982
Page 18 of 25 • '
a nearby National Weather Service station and corrected for
elevation. Correction for the elevation difference between the
station and the sampling point should be applied at a rate of
-2.5 mm Eg/30 m (0.1 in. Hg/100 ft). . Record the results on the
pretest sampling check form (Figure 3.1).
2.5 Probe Nozzle
Probe nozzles should be calibrated initially before use in
the field.
1. Use a micrometer to measure the ID of the nozzle to the
nearest 0.025 mm (0.001 in.).
2. Make three measurements using different diameters each
time.
3. Average the three measurements. The difference between
the high and the low numbers should not be £0.1 mm (0.004 in.).
4. Label each nozzle permanently and uniquely for identi-
fication.
5. Record the data on Figure 2.6, the nozzle calibration
form. If nozzles become nicked, dented, or corroded, reshape,
sharpen, and recalibrate before use.
2.6 Pitot Tube
The Type S pitot tube assembly should be calibrated using
the procedure in Section'3.1.2, Method 2.
2.7 Trip Balance
The trip balance should be calibrated initially by using
Class-S standard weights, and it should agree within ±0.5 g of
the standard weight. Adjust or return the balance to the manu-
facturer if limits are not met.
2.8 Fluoride Electrode
The fluoride (F~) electrode should be calibrated daily, and
checked hourly against serial dilutions of the 0.1M fluoride
standard solution. Use the following procedure to prepare and to
measure the concentration of the dilutions.
1. Pipette 10 ml of 0.1M NaF into a 100-ml volumetric
flask, and dilute to the mark with distilled water to get
0.01M NaF;,Cdllute 10 ml of the 0.01M solution to make a 0.001M
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 19 of 25
Date
Calibrated by
Nozzle
identi f ication
number
37
Nozzle Diameter3
jpar?ii.)
D2,
jam (in. )
D3,
pan (in. )
mm ( in . )
avg
where:
1,2,3,
three different nozzles diameters, mm (in.); each
diameter must be within (0.025 mm) 0.001 in.
AD = maximum difference between any two diameters, mm (in.),
AD £(0.10 mm) 0.004 in.
avg
= average of D,, D2, and
Figure 2.6 Nozzle calibration data form.
-------
Section No. 3.9%2
Revision No. j
Date January 4, 1982
Page 20 of 25
solution; continue in the same manner to get the 0.001M and the
0.00001M dilutions.
2. Pipette 50 ml of each NaF dilution into separate
beakers.
3. Add 50 ml of TISAB to each beaker.
4. Immerse the electrode into the most dilute standard
solution, and measure the developed potential while stirring the
solution with a magnetic stirrer. Note; Avoid stirring the
solution before immersing the electrode because entrapped air
around the crystal can cause erroneous readings or needle fluc-
tuations.
5. Keep the electrodes immersed in the solution 3 min in
order for it to stabilize before taking a final positive milli-
volt reading.
6. Record the reading on the laboratory form, Figure 2.7,
and remove the electrode from the sample.
7. Soak the electrode for 30 s in distilled water, and
then blot it dry.
8. Plot the millivolt value on the linear axis of semilog
graph paper and plot the known concentrations of fluoride stan-
dards on the log axis as shown in Figure 2.8. Note; Plot the
nominal value for concentrations of the standards on the log
axis; for example, when 50 ml of the 0.01M standard is diluted
with 50 ml TISAB, the concentration is plotted as 0.01M. Measure
the most dilute standard first and the most concentrated standard
last, as shown on Figure 2.8, to get a straight-line calibration
curve with nominal concentrations of 0.00001, 0.0001, 0.001,
0.01, and 0.1M NaF. To obtain the required precision, use 4 or 5
cycle semilog paper similar to that in Figure 2.8.
To check the accuracy of the calibration curve, prepare and
measure a control sample (Section 3.9.5). Prepare fresh stan-
dardizing solutions of <_0.01M NaF daily, and store the solutions
in polyethylene or polypropylene contains.
The fluoride electrode should be.checked periodically after
repeated use for responsiveness and sensitivity. Compare the
-------
section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 21 of 25
Date standards prepared
LABORATORY WORKSHEET
3-S-80
Temperature of standards t>(O .S* C.
Date
' SO
Electrode number
Standard number
/
£
3
4
s-
6
Control Sample
Concentration (M)
0.000001
0.00001
0.0001
0.001
0.01
0.1
o.ocr
Electrode potential (mV)
—
300
<2<^7
£01
/V?
10
IK
Note: The concentration of the control sample determined from the calibration
curve must be between 0.002M and 0.01M.
Signature of analyst
Signature of reviewer
Figure 2.7. Fluoride calibration data form. (Method 13B)
-------
Section No. 3,9.2
Revision No. 0
Date January 4, 1982
Page 22 of 25"
50
100
150
o
D-
§ 200
250
300
Date
y-
Sample temp
Analyst T
LOCQ n
Reviewer U) M
10
-4
-3
Results
Molarity
0.00001M
0.0001M
0.001M
0.01M
0.1M
Control
sample
10 10
FLUORIDE MOLARITY (M)
10
-2
10
-1
Figure 2.8. Fluoride calibration curve, Method 13B.
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 23 of 25
electrode responses or millivolt readings of samples or standards
of the same fluoride concentration. For equal concentrations of
fluoride, the electrode response should remain stable with each
analysis, if not, repair or replace the electrode.
Certain specific-ion meters designed specifically for fluoride
electrode use give direct readouts of F~ concentrations. These
meters may be used over narrow concentration ranges. Calibrate
the meter according to manufacturer's directions.
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 24 of 25
TABLE 2.1. ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Wet test meter
Capacity of >3.4 m3/h
(120 ft3/h);~accuracy
within ±1.0%
Calibrate initially
and yearly by liquid
displacement
Adjust to
meet specifi-
cations, or
return to
manufacturer
Dry gas meter
Y. = Y ± 0.02 Y at
flow rate of 0.02 -
0.03 nrVmin (0.7 -
1.1 ftVmin)
Calibrate with wet
test meter initially
to agree within Y ±
0.02 Y and when post-
test check is not
within Y ± 0.05 Y
Repair or re-
place, and
then recali-
brate
Thermometers
Impinger thermometer
+1°C (2°F); dry gas
meter thermometer
+3°C (5.4°F) over
applicable range
Calibrate each ini-
tially against a
mercury-in-glass
thermometer; before
field trip compare
each with mercury-
in-glass thermometer
Adjust, de-
termine a
constant cor-
rection fac-
tor, or re-
ject
Barometer
+2.5 mm (0.1 in.) Kg of
mercury-in-glass barom-
eter
Calibrate initially
vs mercury-in-glass
barometer; check
before and after
each field test
Adjust to
agree with
certified
barometer
Probe nozzle
Average three ID mea-
surements of nozzle;
difference between high
and low <0.1 mm
(0.004 in.)
Use a micrometer to
measure to near-
est 0.025 mm (0.001
in.)
Recalibrate,
reshape, and
sharpen when
nozzle be-
comes nicked,
dented, or
corroded
(continued)
-------
Section No. 3.9.2
Revision No. 0
Date January 4, 1982
Page 25 of 25
Table 2.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Stack tempera-
ture sensor
±1.5% of average stack
temperature, °R
Calibrate initially;
check after each
field test
Adjust or
reject
Trip balance
Standard Class-S
weights within ±0.5 g
of stated value
Verify calibration
when first purchased,
any time moved or
subject to .rough
handling, and during
routine operations
when not within
± 0.5 g
Have the
manufacturer
recalibrate
or adjust
Pi tot tube
Type S; initially
calibrated according to
Section 3.1, Meth 2;
tube ttps undamaged
Visually check
before each field
test
Repair or
replace
Fluoride
electrode
Calibration curve plot-
ted with F standard
solutions of 0.1M,
0.01M, 0.001M,
0.0001M, and 0.00001M
and corresponding mV
reading on semi log
graph paper; stable
electrode response
Calibrate with each
use and every hour
of continuous use;
check response
stability of elec-
trode after re-
peated use
Repair or
replace
-------
Section No. 3.9.3
Revision No. 0
Date January 4, 1982
Page 1 of 6
3.0 PRESAMPLING OPERATIONS
The quality assurance activities for presampling operations
are summarized in Table 3.1 at the end of this section. See
Sections 3.0.1 and 3.0.2, of this Handbook for general informa-
tion on preliminary site visits. See Section 3.4.3 (Method 5)
for more detailed and specific information of presampling opera-
tions for sampling equipment similar to the Method 13 equipment.
3.1 Apparatus Check and Calibration
Pretest checks must be made on most of the sampling apparat-
us. Figure 3.1 should be used to record data on the pretest
calibration checks. Figure 3.2 in Section 3.4 of this Handbook
is recommended to aid the tester in preparing an equipment check-
list, status form, and packing list.
3.1.1 Sampling Train - A schematic of the EPA Method 13 sampling
train (Figure 1.1) should be used for assembling the components
and for checking for compliance (specifications in the Reference
Method, Section 3.9.10).
3.1.2 Probe and Nozzle - Clean the probe and the nozzle inter-
nally by brushing first with tap water, then with deionized dis-
tilled water, and finally with acetone; allow both to dry in the
air. The probe should be sealed at the inlet or tip; should be
checked for leaks at a vacuum of 380 mm (15 in. ) Hg; and should
be leak free under these conditions. The probe liner, in extreme
cases, can be cleaned with stronger reagents; in either case, the
objective is to leave the liner free from contaminants. Check
the probe's heating system to see that it is operating properly
and that it prevents moisture condensation.
3.1.3 Impingers, Filter Holders, and Glass Connectors - All
glassware should be cleaned first with detergent and tap water
and then with deionized distilled water. All glassware should be
visually inspected for cracks or breakage and then repaired or
discarded if defective. If a filter is to be used between the
probe and the first impinger be sure that an acceptable stainless
steel mesh filter support is packed; glass frit supports are not
acceptable.
-------
Section No. 3.9.3
Revision No. 0
Date January 4, 1982
Page 2 of 6
Date S-//- &O Calibrated by
Meter box number F/3- / AH@ /, S
Dry Gas Meter*
Pretest calibration factor Y /. O/3 (within ±2% of the
average factor for each calibration run).
Impinger Thermometer
Was a pretest temperature correction used? _____ yes ^^ n°
If yes, temperature correction (within ±1°C (2°F)
of reference values for calibration and within ±2°C (4°F) of
reference value for calibration check)
Dry Gas Meter Thermometers
Was a pretest temperature correction made? . yes *^ no
If yes, temperature correction (within ±3°C (5.4°F) of
reference value for calibration and within 6°C (10.8°F) of
reference values for calibration check)
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 the reference values 3QO to 3&O K
Barometer
Was the pretest field barometer reading correct? ^yes 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. 3.9.3
Revision No. 0
Date January 4, 1982
Page 3 of 6
3.1.4 Pump - The vacuum pump should be serviced as recommended
by the manufacturer, or every 3 mo, or upon erratic behavior
(nonuniform or insufficient pumping action). Check the oiler
jars, if used, every 10 tests.
3.1.5 Dry Gas Meter - A dry gas meter calibration check should
be made using the procedure in Section 3.4.2.
3.1.6 Silica Gel - Either dry the used silica gel at 175°C
(347°F) for at least 2 h or use fresh silica gel. Weigh several
200- to 300-g portions in airtight containers to the nearest
0.5 g if the moisture content is to be determined. Record the
total weight (silica gel plus container) for each container.
3.1.7 Thermometers - The thermometers should be compared to a
mercury-in-glass reference thermometer at ambient temperature.
3.1.8 Barometer - The field barometer should be compared before
each field trip with a mercury -in -glass barometer or with a
weather station reading after making an elevation correction.
3.2 Reagents and Equipment
3.2.1 Filters - Check the filters visually against light for
irregularities, flaws, and pinhole leaks. Determine the F-blank
value by analyzing three filters chosen from each lot (Section
3.9.5); if the value is <_0.015 mg F/cm2 they are acceptable for
field use.
3.2.2 Water - 100 ml of deionized distilled water is needed for
each of the first two impingers and for sample recovery.
3.2.3 Ice - Crushed ice is needed to keep the gas that exits
into the last impinger below 21°C (70°F).
3.2.4 Stopcock grease - Silicone grease that is acetone insol-
uble and heat stable may be used sparingly at each connection
point of the sampling train to prevent gas leaks; but this is not
necessary if screw-on connectors with Teflon (or similar) sleeves
are used.
3.3 Equipment Packing
The accessibility, condition, and functioning of measurement
devices in the field depend on careful packing and on careful
-------
Section No. 3.9,3
Revision No. 0
Date January 4, 1982
Page 4 of 6
movement on site. Equipment should be packed to withstand severe
treatment during shipping and field handling operations. One
major consideration in shipping cases is the construction mate-
rials. The following containers are suggested, but are not
mandatory.
3.3.1 Probe - Seal the inlet and outlet of the probe to protect
the probe from breakage. Pack the probe inside a container that
is lined with polyethylene or other suitable material that is
rigid enough to prevent bending or twisting during shipping and
handling; an ideal container is a wooden case (or the equivalent)
with a separate compartment lined with foam material for each
probe, and should have handles or eye-hooks that can withstand
hoisting.
3.3.2 Impingers, Connectors, and Assorted Glassware - All im-
pingers and glassware should be packed in rigid containers and
protected by polyethylene or other suitable material. Individual
compartments will help to organize and protect each piece of
glassware.
3.3.3 Volumetric Glassware - A sturdy case lined with foam
material is suggested for 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 thermom-
eters—should be packed in a shipping container unless its hous-
ing is sufficiently protective for the components during travel.
Additional pump oil should be packed if oil is required. It is
advisable to carry a spare meter box 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. 3.9.3
Revision No. 0
Date January 4, 1982
Page 5 of 6
TABLE 3.1 ACTIVITY MATRIX FOR PRESAMPLING OPERATIONS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sampling train
probe and
nozzle
1. Probe, nozzle, and
liner free of contami-
nants; constructed of
borosilicate glass,
quartz, or equivalent;
metal liner must be
approved by admini-
strator
2. Probe leak free
at 380 mm (15 in.) Hg
3. Probe heating
system prevents mois-
ture condensation
1. Clean internally
by brushing with tap
water, deionized dis-
tilled water, and
acetone; air dry
before test
2. Check using pro-
cedures in Subsec 2.3
3. Check heating
system initially and
when moisture cannot
be prevented during
testing (Sec 3.4.1)
1. Repeat
cleaning and
assembly pro-
cedures
2. Replace
3. Repair or
replace
Impingers,
filter
holders, and
glass con-
nectors
Clean; free of breaks,
cracks, leaks, etc.
Clean with detergent,
tap water, and
deionized distilled
water
Repair or
discard
Pump
Sampling rate of 0.02-
0.03 mVmin (0.7 to
1.1 ftVmin) up to 380
mm (15 in.) Hg at pump
inlet
Service every 3 mo
or upon erratic be-
havior; check
oiler jars every 10
tests
Repair or re-
turn to manu-
facturer
Dry gas meter
Clean; readings ±2% of
of average calibration
factor
Calibrate according
to Sec 3.4.2; check
for excess oil
As above
(continued)
-------
Table 3.1 (continued)
Section No. 3.9.3
Revision No. 0
Date January 4,- 1982
Page 6 of 6
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Reagents and
Equipment
Filters
No irregularities,
flaws, pinhole leaks;
<0.015 mgF/cm2
Visually check before
testing; check each
lot of filters for F
content
Replace
Water
Deionized distilled
conforming to
ASTM-D1193-74, Type 3
Run blank evapora-
tions before field
use to eliminate high
solids (only required
if impinger contents
to be analyzed)
Redistill
replace
or
Stopcock grease
Acetone insoluble;
heat stable
Check label
receipt
upon
Replace
Packing Equip-
ment for
Shipment
Probe
Rigid container lined
with polyethylene foam
Prior to each ship-
ment
Repack
Impingers, con-
nectors, and
assorted
glassware
Rigid container lined
with polyethylene foam
As above
As above
Pump
Sturdy case lined with
polyethylene foam ma-
terial if not part of
meter box
As above
As above
Meter box
Meter box case and/or
additional material to
protect'train compon-
ents; pack spare meter
box
As above
As above
Wash bottles
and storage
containers
Rigid foam-lined con-
tainer
As above
As above
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page I of 21
4.0 ON-SITE MEASUREMENTS
The on-site activities include transporting equipment to the
test site, unpacking and assembling the equipment, making duct
measurements, performing the velocity traverse, determining
molecular weights and stack gas moisture contents, sampling for
fluorides, and recording the data. Table 4.1 at the end of this
section summarizes the quality assurance activities for on-site
activities. Blank forms to be used in recording data are in Sec-
tion 3.4.12 for the convenience of the Handbook user.
4.1 Handling of Equipment
The most efficient means of transporting or moving the
equipment from ground level to the sampling site should be de-
cided during the preliminary site visit (or prior correspon-
dence ). Care should be exercised to prevent damage to the test
equipment or injury to test personnel during the moving phase. A
"laboratory" area should be designated for assembling the sam-
pling train, placing the filter in the filter holder, charging
the impingers, recovering the sample, and documenting the re-
sults; this area should be clean and free of excessive drafts.
4.2 Sampling
The on-site sampling includes preliminary measurements and
setup, placing the filter in the filter holder, setting up the
sampling train, preparing the probe, checking for leaks along the
entire train, inserting the probe into the stack, sealing the
port, checking the temperature of the probe, sampling at desig-
nated points, and recording the data. A final leak check must
always be performed upon completion of the sampling.
4.2.1 Preliminary Site Measurements - These measurements are
needed for locating the pitot tube and the probe during the
sampling.
1. Be sure the site meets Method 1 specifications; if not,
due to duct configuration or other' reasons, have the site ap-
proved by the administrator.
-------
Section No. 3.9.4
Revision No. 0 "
Date January 4, 1982
Page 2 of 21 -
2. Be sure a 115-V, 30-A electrical supply is available
for operating the standard sampling train.
3. 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).
4. 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.
The site must be accepted before a valid sample can be taken.
4.2.2 Stack Parameters - By the following preliminary measure-
ments, the user can set up the nomograph as outlined in
APTD-0576.4 An example nomograph data form is Figure 4.1. Using
the stack parameters obtained, the isokinetic sampling rate can
be set.
1. Check the sampling site for cylonic or nonparallel flow
(Method 1, Section 3.0).
2. Determine the stack pressure, temperature, and the
range of velocity heads encountered (Method 2).
3. Calculate the moisture content by using Method 4 or
its alternatives. If the source has been tested before or if a
good estimate of the moisture is available, this value can be
used to avoid calculations. If the stack gas is saturated with
moisture or has water droplets, the moisture content must be
determined by using stack gas temperature sensor (Method 4).
4. Calculate the dry molecular weight (M,) of the stack
gas (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 fluoride sample.
5. Record the data on the sampling and the analytical data
forms for molecular weight determinations located in Section 3.2,
Method 3.
Note; The condensate collected during the sampling can be used
in the final calculations of moisture content (Section 3.9.6).
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 3 of 21
Plant
Date
3T-
Sampling location
Calibrated pressure differential across
orifice, in. H20
Average meter temperature (ambient + 20°F),
Percent moisture in gas stream by volume, %
Barometric pressure at meter, in. Hg
Static pressure in stack, in. Hg
(P ±0.073 x stack gauge pressure, in. H2
Ratio of static pressure to meter pressure
Average stack temperature, °F
Average velocity head, in. H20
Maximum velocity head, in. H20
C factor
Calculated nozzle diameter, in
Actual nozzle diameter, in.
Reference Ap, in. H2O
m
avg
wo
m
avg
A?/
- 0-01
0.3
/. a
G.3SS
O.Z1S
0-148
Figure 4.1. Nomograph data form (English units).
-------
Section No. 3.9..4
Revision No. 0
Date January 4, 1982
Page 4 of 21
4.2.3 Sampling Rate - Method 13 sampling is performed isokinet-
ically like Method 5, but the sampling rate must be <0.03 m /min
(1.0 ft /min) during the test; the maximum AH will limit the rate
to <0.03 m3/min (1.0 ft3/min).
1. Select a nozzle size based on the range of velocity
heads, so that the nozzle size will not have to be changed to
maintain an isokinetic sampling rate.
2. Select a nozzle that will maintain the maximum sampling
3 3
rate at <0.03 m /min (1.0 ft /min) during the run.
3. Check the maximum AH, using the following equation:
1.09 P M AH@
Maximum AH <_ = Equation 4-1
m
where
Maximum AH = pressure differential across the orifice that
produces a flow of 1.0 ft /min, in. H^O;
P = pressure of the dry gas meter, in. Hg;
M = molecular weight of the stack gas;
AH@ = pressure differential across the orifice that
produces a flow rate of 0.75 scfm, in. H20; and
T = temperature of the meter, °R.
4. Install the selected nozzle using a Viton A 0-ring if
glass or stainless steel liners are used; install the nozzle on a
stainless steel liner by using a leak-free mechanical connection
(APTD-05764) or Teflon ferrules.
5. Mark the probe with heat resistant tape or with another
acceptable means to denote the proper distance to which it should
be inserted into the stack or duct at each sampling point.
6. Select a total sampling time that is greater than or
equal to the minimum total sampling time specified in the test
procedures for the specific industry so that—
a. The sampling time per traverse point is >_2 min
(greater time interval may be specified by the administrator);
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 5 of 21
the number of minutes sampled at each point is either an integer
or an integer plus one-half minute to avoid timekeeping errors.
b. The sample volume corrected to standard conditions
exceeds the required minimum total gas sample volume (can be
based on an approximate average sampling rate). In some circum-
stances (e.g., batch cycles), it may be necessary to sample for
shorter times and to obtain smaller gas sample volumes; if so,
obtain the administrator's approval.
7. Record the data on the fluoride field data form (Figure
4.2).
4..2.4 Sampling Train Preparation - These steps are needed for
preparing the sampling train.
1. Keep all openings where contamination can occur covered
until just before assembly of the setup or before beginning the
sampling.
2. Place 100 ml of distilled water (a graduated cylinder
may be used) in each of the first two impingers.
3. Leave the third impinger empty.
4. Add 200-300 g of preweighed silica gel in the fourth
impinger and place the empty container in. a safe place for use
later in the sample recovery, and record the weight of the silica
gel and the container on the appropriate data form. 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.
5. Use tweezers or clean disposable surgical gloves to
place the filter in the filter holder.
6. 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.
4.2.5 Sampling Train Assemblage - The arrangement of .the sam-
pling train components is shown in Figure 1.1.
1. Apply if needed to avoid contamination a very light
coat of silicone grease, but only on the outside of all ground-
glass joints.
-------
Plant
City
Location
Operator
Date /r~,
M
uier
Meter calibration (Y) /./?/3
Pi tot tube (C ) /a #4
Sheet
/
of
J_
Probe length v/p j>j
Probe liner material
fiO
Run number
Stack diam. jmr\in.) 7/9,3
Probe heater setting /?.7
Ambient temperature
Nozzle identification number
Nozzle diameter /?;*,flftft nim
Thermometer number
Final leak rate
3/
(in.)
Sample box number
Meter box number •
Meter AH@
Barometric pressure (Pu) <3<3.23 -fflnr(1n.) Hg
Assumed moisture
Static pressure (
C Factor O.Qfo
Reference AP" /
) -O.6,
(in.) H20
(cfm)
Vacuum during leak check ^p
-mm-(in") Hg
Filter position
Maximum AH ^.^
Remarks
_4Bm-(in.) H20
Traverse
point
number
Sampling
time,
(0), min
Clock
time,
(24 h)
Vacuum,
mm
Stack
tempera-
ture
Velocity
head
(AP ),
-fflffl-
(in.) H20
Pressure
differ-
ential
across
orifice
meter (AH),
jnm-
(in.) H20
Gas sample
volume (V ),
(ft3)"1
Gas sample temp-
erature at dry
gas meter
Inlet, Outlet,
Temp
of gas
leaving
condenser
or last
impinger,
5e-(°F)
Filter
temp,
0
A/-/
/.n
n. 37
/o
/.o
.-73
-2.. a
7.0
60
5V.
Jd in
n> n>
< o
H-ft
01 H-
H-O
O V
O
CO
£,/
50
5Z>
JT/
UQ ft
(D 0)
CT,^
P>
3/3
5-7
3.5-
. 70
A*
SO
311
D.Z&
/, 7
62-
57
Total
Total
._
48.64-7
Avg
59
Max
Figure 4.2. Fluoride field data form.
V£>
CO
ro
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 7 of 21
2. Either place the filter immediately following the probe
or between the third and fourth impingers. Normally the filter
will be placed after the third impinger unless the filterable
particulate fluoride is to be measured. It is not necessary to
have filters in both positions. If in the front filter position,
use a 20-mesh stainless steel filter support with a silicone
outer seal.
3. Place crushed ice and water around the impingers.
4. Check the filter to be sure there are no tears.
5. Attach a temperature sensor to the metal sheath of the
sampling probe if it is not already an integral part of the
assembly, so that the sensor extends beyond the probe tip and
does not touch any metal; the sensor 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; other arrangements are
shown in Method 2.
4.2.6 Sampling Train Leak Checks - Leak checks are necessary to
ensure that the sample has not been biased low by dilution air.
The Reference Method (Section 3.9.10) specifies that leak checks
be performed .at certain times as discussed below. Leakage rates
<4% of the average sampling rate or 0.00057 m3/min (0.02
ft3/min), whichever is less, are acceptable.
4.2.6.1 Pretest - (optional) If the tester opts to conduct the
pretest leak check, the following procedure should be used after
the sampling train has been assembled.
1. Set the filter heating system at the desired operating
temperature.
2. Allow the temperature to stabilize.
3. If a Viton A 0-ring or other leak-free gasket is used
to connect the probe nozzle to the probe liner, leak check the
train at the sampling site by plugging the nozzle and pulling a
vacuum of 380 mm (15 in.) Hg. Note; A lower vacuum may be used
if it is not exceeded during the test.
4. If an asbestos string is used for the probe gasket, do
not connect the probe to the train; instead, first plug the inlet
-------
Section No. 3.9.4
Revision No. 0
Date January. 4., 1982
Page 8 of 21
to the filter holder and pull a vacuum of 380 mm (15 in.) Hg (see
previous note), and then connect the probe to the train to leak
check at a vacuum of about 25 mm (1 in.) Hg.
Alternatively, the probe may be leak checked with the rest
of the sampling train in one step at a vacuum of 380 mm (15 in.)
Hg (APTD-05813 and APTD-05764).
1. Start the pump with the bypass valve fully open and the
coarse adjust valve closed.
2. Open the coarse adjust valve, and slowly close the
bypass valve until the desired vacuum is reached. Note; Do not
reverse the direction of the bypass valve; this will cause dis-
tilled water to back up from the impingers into the filter
holder. If the desired vacuum is exceeded, either leak check at
the higher vacuum or end the leak check (step 3 below) and start
over.
3. When the leak check is complete, slowly remove the plug
from the inlet to the probe or the filter holder; close the
coarse adjust valve; and immediately turn off the vacuum pump to
prevent the impinger water from being forced back into the filter
holder and to prevent the silica gel from being forced back into
the third impinger.
4. Visually check to be sure that water did not contact
the filter and that the filter has no tears before beginning the
test.
4.2.6.2 During the Sampling - If. a component (e.g., filter
assembly or impinger) change is necessary during the test, con-
duct a leak check before the change, according to the step-by-
step procedure outlined above.
1. Record the initial dry gas meter reading on Figure 4.2.
2. Be sure the vacuum is equal to or greater than the
maximum value recorded up to that point in the test.
3. If the leakage rate is £0.00057 m3'min (0.02 ft3/min)
or 4% of the average sampling rate (whichever is less), the
results are acceptable, so no correction need be applied to the
total volume of dry gas metered.
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 9 of 21
4. If a higher leakage rate is obtained, either record the
leakage and correct the sample volume (Section 6.3(b) of the
Reference Method, Section 3.9.10), or void the sample run.
5. Record the final dry gas meter reading on Figure 4.2.
4.2.6.3 Posttest - (mandatory) At the conclusion of each sam-
pling run, conduct a leak check in accordance with the procedures
above.
1. Record the initial dry gas meter reading on Figure 4.2.
2. Be sure the vacuum is equal to or greater than the
maximum recorded during the sampling run.
3. If the leakage rate is £0.00057 m3/min (0.02 ft3/min)
or 4% of the average sampling rate (whichever is less), the
results are acceptable, so no correction need be applied to the
total volume of dry gas metered.
4. If a higher leakage rate is obtained, either record the
leakage rate and correct the sample volume (Section 6.3(a) or
6.3(b) of the Reference Method, Section 3.9.10), or void the
sample run.
5. Record the dry gas meter reading on Figure 4.2.
4.2.7 Sampling Train Operation - Just before beginning the
sampling, clean the portholes to minimize the chance of sampling
any deposited materials. Verify that the probe and the filter
heating systems (if required) are up to the desired temperatures
and verify that the pitot tube and the nozzle are positioned
properly. Follow the procedure below for sampling:
1. Record the initial dry gas meter readings, barometric
pressure, and other data on 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; maintain a sampling rate of
±10% of the isokinetic rate (unless otherwise specified by the
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 10 of 21 '
administrator), and adjust the rate at any sampling point if a
20% variation in velocity pressure occurs. Note; Do not exceed
the maximum AH. Use nomographs or programmed calculators to
rapidly determine the orifice pressure drop corresponding to the
isokinetic sampling rate. If the nomograph is designed as shown
in APTD-0576,4 use it only with a Type S pitot tube which has a
C coefficient of 0.85 ± 0.02 and only when the stack gas dry
molecular weight (Md) is 29 ± 4, if C and Mg are outside these
limits, do not use the nomograph without compensating for the
differences. Recalibrate the isokinetic rate or reset the nomo-
graph if the absolute stack temperature (T ) changes by >10%.
S
4. Take other required readings (Figure 4.2) at least once
at each sampling point during each time increment.
5. Record the final dry gas meter readings (Figure 4.2) 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;
record the final readings after each traverse.
8. Conduct the mandatory posttest leak check (Subsec-
tion 4.2.6.3) at the conclusion of the last traverse. Record any
leakage rate. Also, leak check the pitot lines (Method 2, Sec-
tion 3.1.2); 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.
Periodically during the test, observe the connecting glass-
ware—from 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 periodi-
cally during each traverse. Vibrations and temperature fluctua-
tions can cause the manometer zero to shift.
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 11 of 21
4.3 Sample Recovery
After the sampling is complete and the data are recorded for
all points, begin the cleanup procedure immediately.
1. Allow the probe to cool until it can be safely handled.
2. Wipe off all external particulate matter near the tip
of the probe nozzle.
3. Cap the tip loosely to keep from losing part of the
sample; capping it tightly while the sampling train is cooling
can cause a vacuum to form in the filter holder, and can cause
impinger water to.be drawn backward.
4. Remove the probe from the sample train before moving
the sample train to the cleanup site.
5. Wipe off the silicone grease, and cap the open outlet
of the probe; be careful not to lose any condensate that is
present.
6. Wipe off the silicone grease from the filter holder
inlet, and cap .this inlet.
7. Remove the umbilical cord from the last impinger and
cap the impinger.
8. Wipe off the silicone grease and then cap off the
filter holder outlet and any open impinger inlets or outlets with
ground-glass stoppers, plastic caps, or serum caps.
9. Transfer the probe and the filter-impinger assembly to
an area that is clean and protected from the wind to minimize the
chances of contaminating or losing any of the sample. Inspect
the train before and during disassembly, and note any abnormal
conditions.
4.3.1 Probe, Filter, and Impinger Catches - This step-by-step
procedure should be followed carefully to recover virtually all
of the sample collected in the probe, filter, and impinger.
1. Use a graduated cylinder to measure (to the nearest
1 ml) the volume of water in the first three impingers and any
condensate in the probe.
2. Record the values on the sample recovery and integrity
form Figure 4.3.
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 12 of 21 -
Plant QJlujry>.Lj>n 1-1 wo S/yvvji_CJlg-A^ Sample date
Sample location P/? nA^ln
&
~ >*
RECOVERED SAMPLE
Water rinse and
impinger contents Liquid level
container number SiSiDol marked? L^C^J
Water blank Liquid level
container number ot3r>/5C> marked? muz-
Samples stored and locked?
Remarks
Date of laboratory custody
Laboratory personnel taking custody ^) ovw^ d\ e-a/%
Remarks
Figure 4.3. Sample recovery and integrity data form.
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 13 of 21
3. Transfer the impinger water from the graduated cylinder
into a polyethylene container.
4. Add the filter to this container using procedures
subject to the Administrator's approval.
5. Be sure that dust on the outside of the probe or other
component (e.g., the probe nozzle, probe fitting, probe liner,
first three impingers, impinger connectors, and filter holder)
does not get into the sample while cleaning other sample-exposed
surfaces with deionized distilled water; use <500 ml for the
entire wash, and add these washings to the washings and the
filter in the polyethylene container. To this container add the
rinsings from the probe and nozzle, as described in the following
procedure.
Probe and Probe Nozzle - Having two people clean the probe
should minimize sample losses. Keep brushes clean and protected
from contamination at all times.
1. Carefully remove, the probe nozzle, use a Nylon bristle
brush to loosen particles from the inside surfaces; use a wash
bottle to rinse with deionized distilled water until no particles
i
are visible.
2. Brush and rinse the inside parts of the Swagelok. fit-
ting with deionized distilled water in a similar way.
3. Rinse the probe liner by squirting deionized distilled
water into the upper end of the probe and by tilting and rotating
the probe so that all inside surfaces are wetted, and let the
water drain from the lower end through a funnel (glass or poly-
ethylene) and into the container.
4. Follow the rinse with a cleaning with a probe brush.
Hold the probe in an inclined position, and squirt deionized
distilled water into the upper end while pushing the brush with a
twisting action through the probe and catching any water and
particulate matter that is brushed from the probe into the sample
container. Note; Brush three times, or at least six times for
stainless steel or other probes which have small crevices that
entrap particulate matter.
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 14 of 21
5. Rinse the brush with deionized distilled water, and
quantitatively collect these washings in the sample container.
6. After cleaning the brush, make a final rinse of the
probe by repeating steps 1-3.
Impinger and Filter Assembly - To recover fine particulates
from these components, brush, wash, and add the rinsings to the
container.
1. Rinse the inside surface of each of the first three
impingers and their connecting glassware three times using small
portions of deionized distilled water for each rinse, and brush
each sample-exposed surface with a Nylon bristle brush, to ensure
recovery of fine particulate matter. Make a final rinse of each
surface and the brush.
2. Be sure that all joints have been wiped clean of sili-
cone grease before brushing and rinsing with deionized distilled
water the inside of the filter holder (front-half only if after
the third impinger) three or more times as needed; make a final
rinse of the brush and filter holder.
Container - The following steps should be followed after all
water washings and particulate matter have been collected in the
sample container.
1. Tighten the lid so that water will not leak out when it
is shipped to the laboratory.
2. Mark the height of the fluid level so that the re-
ceivers can determine whether leakage has occurred during trans-
port.
3. Label the container clearly to identify its contents;
example sample label is shown in Figure 4.4.
4.3.2 Sample Blank - Prepare a blank by placing an unused filter
in a polyethylene container and by adding a volume of water equal
to the total volume in the average sample. Process the blank in
the same manner as the field samples.
4.3.3 Silica Gel - Note the color of the indicating silica gel
to determine whether it has been completely spent, and make a
notation of its condition on Figure 4.3.
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 15 of 21
Plant /)/tf/n/'/w>nn Jrfct.T'fA City CaflpsA L-I'T^, /£/vfl/-
rr //
Site J>7^r//€ Ourt-er Sample type p/ut&iJ? SArf>lc
Date ^-JX-9o Run number AS-^L
Front rinse D^ Front filter Q' Front solution D
Back rinse 0^ Back filter QT Back solution 0^
Solution Level marked
Volume: Initial Final J2
1C
Clean up by §
/ Qi
Figure 4.4. Example of a sample label.
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 16 of 21
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 calculations, 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 Sample Logistics (Data) and Packing of Equipment
Follow the sample recovery procedures for the required
number of test runs, and record all data on Figure 4.3. If the
probe and the glassware (impinger, filter holder, and connectors)
are to be used in the next test, rinse all with distilled deion-
ized water and then acetone. To document the data and to prepare
the sample for shipping the following steps are recommended after
the test.
1. Check all sample containers for proper labeling (time,
date, and location of tests, number of tests, and any other
pertinent data).. Be sure a blank has been taken and labeled.
2. Duplicate all data recorded during the field test, to
avoid costly mistakes, by using either carbon paper or data forms
and a field laboratory notebook. Avoid using water soluble pens.
3. Mail one set of data to the base laboratory or give it
to another team member or to personnel in the agency; handcarry
the other set.
4. Examine all sample and blank containers and sampling
equipment for damage and for proper packing for shipment to the
base laboratory, and label all shipping containers to prevent
loss of samples or equipment.
5. Make quick checks of sampling and sample recovery
procedures by using the on-site checklist, Figure 4.5.
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 17 of 21
Apparatus
Probe nozzle: stainless steel */__ glass
Button-hook \^ elbow size
Clean?
Probe liner: borosilicate quartz other
Clean?
Heating system*
Checked?
Pitot tube: Type S tx- . other
Properly attached to probe?*
Modifications :
Pitot tube coefficient
Differential pressure gauge: two inclined manometers
other | sensitivity o.OI - Q to /
Filter holder: borosilicate glass ^ glass frit
filter support silicone gasket other
Clean? S s I
Condenser: number of impingers
Clean?
Contents: 1st /oe>/^di #$0 2nd /oo^dL H^p 3rd -— 4th SJJJ^M^ OJL
Cooling system "
Proper connections?
Modifications
Barometer: mercury aneroid ^ other
Gas density determination: temperature sensor type
pressure gauge <£O
temperature sensor properly attached to probe?*
Procedure
Recent calibration: pitot tubes* tX" ^3^/v>ai/yL/a-iojM cAt.oJ<-,
meter box* fX" ; thermometers/thermocouples'
Filters checked visually for irregularities?*
Filters properly labeled?*
Sampling site properly selected? _
Nozzle size properly selected?*
Selection of sampling time?
UUJZ)
plug
All openings to sampling train plugged to prevent pretest con-
tamination?
Impingers properly "assembled?
Filter-properly centered?
Pitot tube lines checked for plugging or leaks?*
Figure 4.5. On-site measurements.
(continued)
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 18 of 21
-Figure 4.5 (continued)
Meter box leveled? /,JL&~> Periodically?
Manometers zeroed? V UULJCLJ
AH@ from most recent calibration
Nomograph setup properly?
Care taken to avoid scraping nipple or stack wall?*
Effective seal around probe when in-stack?
Probe moved at proper time?
Nozzle and pitot tube parallel tfo stack wall at all times?*
Filter changed during run?
Any particulate lost?
Data forms complete and data properly recorded?* LU^U
Nomograph setting changed when stack temp changed significantly?
LULCL)
Velocity pressure and orifice pressure readings recorded
accurately?*
Sampling performed at a rate <1.0 cfm?
Posttest leak check performed?* ^^^ (mandatory)
Leakage rate &. QI @ in. Hg /
Orsat analysis f^-J from stack _ integrated
f^^-J _
Fyrite combustion analysis _ sample location
Bag system leakchecked?*
If data forms cannot be copie'd, record:
approximate stack temp >3/ 7*f volume metered 81-J£ >.
% isokinetic calculated at end of each run 9 9 .%> &
SAMPLE RECOVERY
Brushes: nylon bristle other
Clean?
Wash bottles:0 polyethylene or glass L^L£^>
Clean? cjee-j:^'
Storage containers:polyethylene L^U^J other
Clean? iox^ Leakfree?
Graduated cylander/or balance:subdivisions <2 ml?*
other
Balance: type Ty^/n^o. ^J^^j ^
Probe allowed to cool sufficiently? t^^c^ C£S
Cap placed over nozzle tip to prevent loss of particulate?*
During sampling train disassembly, are all openings capped?
Clean-up area description: ^? A-^wt^/vt-^ /vo^J v5xwT-a-£fe^ Jla-Jr
Clean? LU^ Protected from wind?
_
Filters: paper cu^^ _ type
Silica gel: type0 (6 to 16 mesh)? new? ^^^ used?
Color? JULuLt ^ Condition?^
Filter handling: tweezers used? f^o^ _1_
surgical gloves? ^ other
Any fluoride spilled?* .^
(continued)
-------
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 19 of 21
Figure 4.5 (continued)
Water distilled?
Stopcock grease: acetone-insoluble?
heat-stable silicone? Bother
Probe handling: distilled water rinse ~
Fluoride recovery from: probe nozzle HJL^
probe fitting fo-^^ probe liner
front half of filter holder
Blank: filter j distilled water _
Any visible particles on filter holder inside probe?:*
All jars adequately labeled? t+ju^ , Sealed tightly?
Liquid level marked on jars?* o LJJL* >
Locked up?
-------
Section No. 3.9.4
Revision No. 0 *
Date January 4, 1982
Page 20 of 21 -
TABLE 4.1. ACTIVITY MATRIX FOR ON-SITE MEASUREMENT CHECKS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sampling
Filter
Centered in holder; no
breaks, damage, or con-
tamination during
loading
Use tweezers or surg-
ical gloves to load
Discard fil-
ter, and
reload
Condenser
(addition of
reagents)
100 ml of distilled
water in first two
impingers; 200-300 g
silica gel in fourth
impinger
of
Use graduated cylinder
to add water, or weigh
each impinger and its
contents to the near-
est 0.5 g
Reassemble
system
Assembling
sampling
train
1. Specifications
in Fig 1.1
2. Leak rate <4% of
sampling volume or
0.00057 mVmin (0.02
ftVmin), whichever is
less
1. Check specifica-
tions before each
sampling run
2. Leak check before
sampling by plugging
nozzle or inlet to
first impinger and
pulling a vacuum of
380 mm (15 in.) Hg
1. Reassert
ble
2. Correct
the leak
Sampling
(isokineti-
cally)
1. Within ±10% of
isokinetic condition
and at a rate of less
than 1.0 ftVmin
2. Standard checked
for minimum sampling
time and volume; sam-
pling time >2 min/pt
1. Calculate for
each sample run
2. Make a quick cal-
culation before test,
and exact calculation
after
1. Repeat
the test run
2. As above
(continued)
-------
TABLE 4.1 (continued)
Section No. 3.9.4
Revision No. 0
Date January 4, 1982
Page 21 of 21
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
3. Minimum number of
points specified by
Method 1
4. Leakage rate
<0.00057 mVmin (0.02
ftVmin) or 4% of the
average sampling vol-
ume, whichever is less
3. Check before the
first test run by mea-
suring duct and using
Method 1
4. Leak check after
each test run or be-
fore equipment re-
placement during test
at the maximum vacuum
during the test (man-
datory)
3. Repeat
the procedure
to comply
with specifi-
cations of
Method 1
4. Correct
the sample
volume or re-
peat the sam-
pling
Sample recovery
Noncontaminated sample
Transfer sample to
labeled polyethylene
container after each
test run; mark level
of solution in the
container
Repeat the
sampling
Sample
logistics,
data collec-
tion, and
packing of
equipment
1. All data recorded
correctly
1. After each test
and before packing
1. Complete
the data
2. All equipment exam-
ined for damage and
labeled for shipment
3. All sample contain-
ers and blanks properly
labeled and packaged
2. As above
3. Visually check
after each sampling
2. Repeat
the sampling
if damage
occurred ...dur-
ing the test
3. Correct
when possible
-------
Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 1 of 19
5.0 POSTSAMPLING OPERATIONS
The postsampling operations include checks on the apparatus
used in the field during sampling to measure volumes, tempera-
tures, and pressures, and analyses of the samples collected in
the field and forwarded to the base laboratory. Table 5.1 at the
end of this section summarizes the quality assurance activities
for the postsampling operations.
5.1 Apparatus Checks
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 mainte-
nance. Cleaning and maintenance are discussed in Section 3.4.7
and in APTD-0576.4 Figure 5.1 should be used to record data from
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 an
ASTM mercury-in-glass thermometer at room temperature. If the
two readings agree within ±6°C (10.8°F), the meter reading is
acceptable; if not, the meter thermometer must be recalibrated
(Subsection 2.2, Section 3.4.2) after the posttest check of the
dry gas meter. Use the higher meter thermometer reading (field
or recalibration value) in the calculations. If the field
readings are higher than the recalibration reading, no tempera-
ture correction is necessary; 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 Sec-
tion 3.4.2. Any leaks in the metering system should have been
corrected before the posttest check. If the dry gas meter cali-
bration factor (Y) deviates by <_5% from the initial calibration
factor, the meter volumes obtained during the test series are
-------
Section No. 3.9.5
Revision No. 0 •
Date January 4, 1982
Page 2 of 19
Plant nlurniNum •Smeller Calibrated by "77 J,oqO.n
Meter box number FB'I Date <*J> • 3 / - 8O
Dry Gas Meter
Pretest calibration factor, Y n. 92to (within ±2%)
Posttest check, Y* O.387 (within ±5% of pretest)
Recalibration required? yes ^ no
If yes, recalibration factor, Y (within ±2%)
Lower calibration factor, Y 0.3&6f for calculations (pretest or
posttest)
Dry Gas Meter Thermometers
Was a pretest temperature correction used? _j yes ^ no
If yes, temperature correction (within ±3°C (5.4°F) over
range)
Posttest comparison with mercury-in-glass thermometer?* (within
±6°C (10.8°F) at ambient temperature)
Recalibration required? | yes ^ no
Recalibration temperature correction?~ (within ±3°C
(5.4°F) over range)*
If yes, no correction necessary for calculations 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? yes */* no
If yes, temperature correction °C (°F) (within ±1.5% of
readings in K (°R) over range)
Average stack temperature of compliance test, T 7SO K
Temperature of reference thermometer or solution for recalib]
tion £-£8 K (@* (within ±10% of T ) ^-^
Temperature of stack thermometer for recalibration S~tS8 K (/RJ)
Difference between reference and stack thermometer temperaturesr
AT o K (°R)
Do values agree within ±1.5%?* tX* yes no
If yes, no correction necessary for calculations
If no, calculations 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 result values must be reported since there is no way
to determine which is correct
Figure 5;1 Posttest calibration checks.
(continued)
-------
Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 3 of 19
Figure 5.1 (continued)
Barometer
Was the pretest field barometer reading correct? )xx' yes no
Posttest comparison?* <3?9. S^" mm (in.) Hg (±2.5 mm (0.1 in.) Hg)
Was calibration required? yes ^ no
If yes, no correction necessary for calculations when the field
barometer has a lower reading; if the mercury-in-glass reading
is lower, subtract the difference from the field data readings
for the calculation
*Most significant items/parameters to be checked.
-------
Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 4 of 19
acceptable; if Y deviates by >5%, recalibrate the. metering system
(Section 3.9.2). In 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 sensors
(thermocouples and thermometers) should be compared with a refer-
ence thermometer or with a thermocouple if the temperature is
>405°C (761°F).
For thermocouple(s), compare the thermocouple and the ref-
erence thermometer readings at ambient temperature. If the
values agree within ±1.5% of the absolute temperature, the cali-
bration is valid; if not, recalibrate the thermocouple (Section
3.9.2) to determine the difference (AT ) in the absolute average
s
stack temperature 200°C (360°F) if T is between 200°C and 405°C (360° and
S
751°F). Compare the stack thermometer with a thermocouple at a
temperature that is within ±10% of Te if Te is >405°C (761°F).
S S
If the absolute temperatures agree within ±1.5% the calibration
is valid; if not, determine the error AT^ to correct the average
stack temperature.
5.1.3 Barometer - The field barometer should be compared to the
mercury-in-glass barometer. If the readings agree within ±5 mm
(0.2 in.) Hg, the field readings are acceptable; if not, use the
lower value for the calculations. If the field readings are
lower than the mercury-in-glass readings, the field data are
acceptable; if not, use the difference in the two readings (the
adjusted barometric value) in the calculations.
5.2 Base Laboratory Analysis
All fluoride samples should be checked by the analyst upon
receipt in the base laboratory for identification and sample
-------
Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 5 of 19
integrity. Any losses should be noted on the analytical data form
(Figure 5.2). Either void the sample or correct the data using a
technique approved by the administrator. If a noticeable amount
of sample has been lost by leakage, the following procedure may
be used to correct the volume.
1. Mark the new liquid level on the sample container.
2. Treat the sample as described in Subsection 5.2.3 and
nqte the final dilution volume (vsoin)-
3. Add water up to the initial mark on the container,
transfer the water to a graduated cylinder and record the initial
sample volume (vsoin;{) in milliliters.
4. Add water to the new mark on the container. Transfer
the water to a graduated cylinder, and record the final volume
(V , f) in millileters.
5. Correct the volume by using the following equation:
V = V Vsolni
soln' soln Vsolnf
where
V , , = sample volume to be used in the calculations, ml;
V , = total volume of solution in which fluoride is con-
tained, ml;
V , . = initial volume added to the container in the field,
soini
ml;
V olnf = final volume removed from the container in the base
1aboratory, ml.
6. Both the corrected and uncorrected values should be
submitted in the test report to the agency.
This analytical method is based on measurement of the activ-
ity or concentrations of fluoride ions (F~) in aqueous samples by
use of an appropriate calibration curve. Fluoride activity
depends, however, upon the total ionic strength of the sample and
the electrode does not respond to fluorides which are bound or
complexed. This difficulty is largely overcome by adding a
buffer of high total ionic strength and by requiring preliminary
distillation to eliminate interferent ions. The sample response
-------
Plant
Date
Sample location Su
er
Analyst
yes
Samples identifiable
Ambient temperature A £>. 5~°(L
Temperature of calibration standards
Temperature of samples <£&• 5~° C-
no All liquid levels at marks
Constant temperature bath used
Date calibration standards prepared
yes
yes
no
no
Sample
number
fiF-l
ftF-A
flF-3
fiF-4
Sample
identification
number
/?F - I/O
&F-JAO
AF-J30
flF-]4o
Total
volume of
sample,
(Vt), ml
1000
/OOO
] OO&
/ ODG
Aliquot
total sam-
ple added
to still
(At), ml
S&O
/ OO
/ O£>
/06
Diluted
volume of
distillate
collected
(Vd), ml
3S-&
3.5~O
A SO
AS-o
Electrode
potential ,
mV
373
A6>3
280
A17
Concentration
of fluoride
from cali-
bration curve,
(M), molarity
t>. oooo 7V
£> .0£>£> /A
^). Of>O&^-fff
o . ooo o / a.
Total
weight of
fluoride
in sample
(Ft), mg
3.S~/S~
5-.6 (D
\Q ft < O
0) fl> H- ft
Wl H-
(^ C^ H-O
PI O 3
P> S5 O
H O •
KJ •
O)
V£>
00
Total weight of fluoride in sample (F.)
F, = 19(Vd) (M)
Signature of analyst
Remarks:
Signature of reviewer or supervisor
t^a
Figure 5.2 Fluoride analytical data sheet.
-------
Section No.. 3.9.5
Revision No. 0
Date January 4, 1982
Page 7 of 19
to the ion-specific electrode is also monitored by a standard
reference electrode and a modern pH meter that has an expanded
millivolt scale.
Procedures are -detailed herein for preparing reagents,
blanks, control samples, distillation aliguots, reference and
working standards (including serial dilutions), and an expanded
calibration curve and procedure for treating, separating, and
measuring the fluoride in samples.
5.2.1 Reagents - The following reagents are needed for the
analyses of fluoride samples.
1. Calcium oxide (CaO) - ACS reagent grade powder or ACS
certified grade containing £0.005% fluoride.
2. Phenolphthalein indicator - 0.1% in 1:1 ethanol-water
mixture (v/v).
3. Sodium hydroxide (NaOH) - Pellets, ACS reagent grade or
the equivalent.
4. Sulfuric acid (H^SO^t) - Concentrated, ACS reagent grade
or the equivalent.
5. Filters - Whatman No. 541 or the equivalent.
6. Water - Deionized distilled to conform to ASTM specifi-
cation D1193-74, Type 3. The analyst may omit the Mn04 test for
oxidizable organic matter if high concentrations of organic
matter are not expected.
7. Total ionic strength adjustment buffer (TISAB) - Add
approximately 500 ml of distilled water to a l-£ beaker; to this
add 57 ml of concentrated glacial acetic acid, 58 g of sodium
chloride and 4 g of CDTA (cyclohexylenedinitrilotetraacetic
acid); and stir to dissolve. Place the beaker in a water bath
until it has cooled, and then slowly add about 150 ml of 5M NaOH,
while measuring the pH continuously with a calibrated pH elec-
trode and a reference electrode pair, until the pH is 5.3. Cool
to room temperature, pour into a 1-8, volumetric flask and dilute
to the l-£ mark with distilled water.
8. Hydrochloric acid (HC1) - Concentrated ACS reagent
grade or the equivalent.
-------
Section No. 3.9.5
Revision No. 0
Date January 4f< 1982
Page 8 of 19
9. Sodium fluoride (NaF) standard (0.1 M) - Dissolve 4.2 g
± 0.002 g ACS reagent grade NaF, which has been dried for a mini-
mum of 2 h at 110°C (230°F) and stored in a desiccator, in deion-
ized distilled water, and dilute to 1-2 with deionized distilled
water; this solution contains 0.1 M of Fluoride.
5.2.2 Blanks - The three blanks needed for the analysis are a
filter blank to ensure that the quality of the filter is accept-
able, a distillation blank to avoid cross contamination, and a
sample blank to analyze with the samples to verify the purity of
the reagents used in sampling and analyses.
1. Filter blanks - Determine the fluoride content of the
sampling filters upon receipt of each new lot and at least once
for each test series. Randomly select three filters from each
lot.
1. Add each filter to 500 ml of distilled water.
2. Treat the filters exactly like a sample (Subsec-
tion 5.2.3).
3. Use a 200 ml aliquot for distillation. Initially,
the filter blank must be <0.015 mg F/cm2; if not, reject this
batch and obtain a new supply of filters.
2. Distillation blank - Check the condition of the acid in
the distillation flask (Subsection 5.2.5) for cross-contamination
after every 10th sample by adding 220 ml of distilled water to
the still pot and then proceed with the analysis. If detectable
amounts of fluoride (>0.00001 M) are found in the blank, replace
the acid in the distillation flask.
3. Sample blank - Prepare the sample blanks in the field
at the same time and with the same reagents used for sample
recovery.
1. Add an unused filter from the same batch used in
sampling to a volume of distilled water equal to the average
amount used to recover the samples.
-------
Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 9 of 19
2. Treat the sample blank in the same manner as the
samples are treated (Subsection 5.2.3). Analyze the sample
blanks with the samples.
5.2.3 Sample Preparation - Use the following procedure to pre-
pare samples for distillation. Distillation is not required if
it can be shown to the satisfaction of the Administrator that
fluoride results are unaffected by the alternate analytical pro-
cedure (e.g., ash and fusion of particulate matter with subse-
quent ion selective electrode analysis, or direct electrode anal-
ysis of gases trapped in impingers).
1. Filter the contents of the sample container (including
the sample filter) through a Whatman No. 541 filter or the equiv-
alent into a 1500-ml beaker; if the filtrate volume is >_900 ml,
add NaOH to make the filtrate basic to phenolphthalein, and then
evaporate to <900 ml.
2. Place the Whatman No. 541 filter containing the insolu-
bles (including the sample filter) in a nickle crucible, add a
few milliliters of water; and macerate the filter with a glass
rod.
3. Add 100 mg or sufficient quantity of CaO to the nickel
crucible to make the slurry basic; mix thoroughly; and add a cou-
ple drops of phenolphthalein indicator, which turns pink in a ba-
sic medium. Note: If the slurry does not remain basic (pink)
during ^the evaporation of the water, fluoride will be lost; if
the slurry becomes colorless, it is acidic so add CaO until the
pink returns.
4. Place the crucible either in a hood area under infrared
lamps or on a hot plate at low heat (approximately 50-60°C)
(122-140°F), and evaporate the water completely; then place the
crucible on a hot plate under a hood and slowly increase the
temperature for several hours or until the filter is charred.
5. Place the crucible in a cold muffle furnace and gradu-
ally (to prevent smoking) increase the temperature to 600 °C
(1112°F); maintain the temperature until the crucible contents
are reduced to an ash containing no organic material; and remove
the crucible from the furnace to cool.
-------
Section No. 3.9.5
Revision No. 0.
Date January 4, 1982
Page 10 of 19
•
6. Add approximately 4 g of crushed NaOH pellets to the
crucible, and mix; return the crucible to the furnace, and fuse
the sample for 10 min at 600°C (1112°F); and then remove the
sample from the furnace, and cool it to ambient temperature.
7. Use several rinsings of warm distilled water to trans-
fer the contents of the crucible to the beaker containing the
filtrate (step 1) and finally, rinse the crucible with two 20-ml
portions of 25% (v/v) H2S04, and carefully add the rinses to the
beaker.
8. Mix well, and transfer the beaker contents to a 1-2
volumetric flask. Record this volume as Vt on the data form
(Figure 5.2). Dilute to volume with distilled water, and mix
thoroughly; and allow any undissolved solids to settle.
9. Weigh the spent silica gel and report the weight to the
nearest 0.5 g on the sample integrity and recovery form.
5.2.4 Acid-water Ratio - The acid-water ratio in the distilla-
tion flask should be adjusted by following this procedure. Use a
protective shield when carrying out the procedure.
1. Place 400 ml of distilled water in the 1-2 distillation
flask, and add 200 ml of concentrated H2S04. Slowly add the
H2SO4, while constantly swirling the flask.
2. Add soft glass beads and several small pieces of broken
glass tubing, and assemble the apparatus as shown in Figure 1.3.
3. Heat the flask until it reaches a temperature of 175°C
(347°F), and discard the distillate, and hold the flask for
fluoride separation by distillation.
5.2.5 Fluoride Separation (Distillation) - Fluoride in the
acid-water adjusted flask can be separated from other consti-
tuents in the aqueous sample by distilling fluosilicic (or hydro-
fluoric) acid from a solution of the sample in an acid with a
higher boiling point. Samples with low concentrations of fluo-
ride (e.g., samples from an inlet and outlet of a^ scrubber)
should be distilled first to eliminate contamination by carryover
of fluoride from the previous sample. If fluoride distillation
in the milligram range is to be followed by distillation in the
fractional milligram range, add 200 ml o.f deionized distilled
-------
Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 11 of 19
water and redistill similar to the acid adjustment procedure,
Subsection 5.2.4, to remove residual fluoride from the distilla-
tion system.
1. Cool the contents of the distillation flask (acid-water
adjusted) to <80°C (176°F).
2. Pipette an aliquot of sample containing <10.0 mg F into
the distilling flask, and add distilled water to make 220 ml.
The aliquot size (A.) should be entered on the data form (Figure
5.2). Note; For an estimate of the aliquot size that contains
£10 mg F, see Subsection 5.2.6.
3. Place a 250-ml volumetric flask at the condenser exit;
heat the distillation flask as rapidly as possible with a burner,
while moving the flame up and down the sides of the flask to
prevent bumping; conduct the distillation as rapidly as possible
(O.5 min). Slow distillations have been found to give low fluo-
ride recovery. Collect all distillate up to 175°C (347°F).
Caution; Heating >175°C (347°F) will cause H2SO4 to .distill
over. Note; The H2S04 in the distilling flask can be reused
until carryover of interferent or until poor fluoride recovery is
shown in the distillation blanks and the control samples.
4. Before distilling samples and after every 10th sample,
distill a control sample to check the analytical procedures and
interferences (Subsection 5.2.6).
5.2.6 Control Sample - A control sample should be used to verify
the calibration curve and the analytical procedures before and
during the analysis of the field samples. Use the following
procedures.
1. The 0.05M NaF control sample stock solution - Add 2.10
g of reagent grade anhydrous NaF to a l-£ volumetric flask; add
enough distilled water to dissolve; and dilute to 1-2 with dis-
tilled water.
2.. The 0.005M NaF working solution - Pipette 100 ml of the
0.05M NaF stock solution into a l-£ volumetric flask, and dilute
to the mark with distilled water to get the 0.005 M NaF working
solution. Note; The control should be within 0.004M and 0.006M
NaF; if not, take corrective action until these limits are met.
-------
Section No. 3.9.5
Revision No. 0 '
Date January 4, 1982
Page 12 of 19 .
3 . Analyze the working solution in the same manner as the
samples are analyzed (Subsections 5.2.5, 5.2.9, and 5.2.10).
5.2.7 Distillation Aliquot - The sample volume for distillation
should contain <10 mg F. Use the following procedure to estimate
the aliquot size.
1. Pipette a 25-ml aliquot of sample into a polyethylene
beaker.
2. Add an equal volume of TISAB buffer, and mix well.
3. Adjust the pH meter, and read the millivolts' for the
nondistilled sample and the calibration standard solutions (Sub-
section 5.2.8) .
4. Determine the molarity of the nondistilled sample from
the calibration curve, and determine the size of the aliquot for
distillation by substituting the molarity (M) of the nondistilled
sample in the following equation:
Uiquot for distillation <»!> -
(a)
The aliquot size is only an approximation since the interferring
ions have not been removed by distillation. If the estimate is
>220 ml, use 220 ml; if it is <220 ml, add distilled water to
make the total volume 220 ml; if required, dilute the sample to
get a minimum 1-ml aliquot.
.5.2.8 Calibration Standards - Use the 0.1M NaF reference stan-
dard (Subsection 5.2.1) "in the following procedure for preparing
serial dilutions.
1. Pipette 10 ml of 0.1M NaF into a 100-ml volumetric
flask, and dilute to volume with distilled water to get a 0.01M
standard.
2. Pipette 10 ml of the 0.01M standard solution to make a
0.001M solution in the same manner, and so on to make 0.0001M and
0.00001M solutions.
3 . Pipette 50 ml of each of the standard solutions into
separate polyethylene beakers, add 50 ml of TISAB buffer to each,
and mix well (50 ml of 0.01M diluted with 50 ml of TISAB is still
referred to as 0.01M). Prepare fresh 0.01M NaF standards daily.
-------
Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 13 of 19
A detailed explanation is in Section 3.9.2, Subsection 2.8 of
this method along with calibration curves (Figures 2.8 and 2.9 of
Section 3.9.2).
5.2.9 Sample Treatment - To treat the distilled fluoride in the
volumetric flask (from Subsection 5.2.5, step 3), follow this
procedure.
1. Dilute with distilled water to the 250-ml mark on the
volumetric flask at the condenser exit, and mix thoroughly.
2. Pipette 25-ml of the sample into a 50-ral volumetric
flask, dilute to the mark with TISAB buffer solution, and mix
well.
3. Bring the calibration standards and the samples to the
same temperature; if the ambient laboratory temperature fluctu-
ates more than ±2°C (4°F), condition the samples and standards in
a constant temperature bath.
5.2.10 Concentration Measurement - Some electrodes yield posi-
tive (direct F~ concentrations) and some yield negative (indi-
rect) values; if positive, recalibrate the electrode by using a
manufacturer-recommended standard, by adjusting the calibration
control (if needed) to the correct value, and by verifying the
calibration after measuring each standard and sample to prepare
the calibration curve.
Several precautions are needed before beginning the proce-
dure .
1. Keep the pH meter on standby, and rinse between mea-
surements .
2. Keep the electrodes in the storage solution to prevent
overdrying if long periods of time ^are expected between uses.
3. Do not allow the electrode to touch the side of the
beaker during or between measurements.
4. Use of a stirrer will minimize electrode response time,
but stirring a solution before immersing the electrode may entrap
air around the crystal and cause needle fluctuations and errone-
ous readings.
-------
Section No. 3.9..5
Revision No.. 0
Date January 4, 1982
Page 14 of 19 '
Use an ion-specific electrode in the following procedure for
measuring the F~ concentration.
1. Transfer each standard and each sample to a series of
150-ml polyethylene beakers, and arrange each series so that the
lowest concentration will be read first to avoid carryovers.
2. Rotate the switch of the pH meter to standby, and allow
a 30-min warm-up period.
3. Raise the electrode from the storage solution in the
beaker, and rinse either the electrode thoroughly with distilled
water or soak the fluoride-sensing electrodes in distilled water
for 30 s before removing and blotting dry. Note; This step
should be done between each measurement.
4. Turn the adjustment knob to calibrate; immerse the
electrode in the NaF standard of lowest concentration.
5. Rotate the switch to millivolts (mV), and turn the
adjustment knob to calibrate, read the millivolts of the known
buffer solution from the meter, and record the value on Figure
5.2. Rotate the selector knob .to standby.
6. Raise the electrodes carefully from the buffer solu-
tion, and rinse thoroughly (step 3).
7. Immerse the electrodes carefully into a beaker of
standard solution, and set the beaker on a magnetic stirrer.
Note: If stirrer generates enough heat to change solution tem-
perature, place insulating material (e.g., cork) between the
stirrer and the beaker.
8. Rotate the selector knob to mV, read the mV from the
meter, and record the value on Figure 5.2; allow the electrodes
to remain in the solution at least 3 min, and rotate the knob to
standby; take a final reading.
9. Repeat the above steps until all samples have been
read. Switch to standby, and then rinse and store the electrodes
in distilled water.
5.2.11 Expanded Calibration Curve - Use the following procedure
to construct an expanded calibration curve for analyzing samples
in the lower concentration range of <2 mg F/250 ml distillate and
-------
Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 15 of 19
for more accurate determinations of concentrations since samples
in the range are <0.001M NaF. Use this procedure to prepare
calibration standards, using the 0.1M NaF standard for serial
dilutions (Subsection 5.2.1).
1. Pipette 10 ml of the 0.1M NaF into a 1-2 volumetric
flask, and dilute to volume using distilled water to get a 0.001M
standard.
2. Pipette 10 ml of the 0.001M standard, and dilute it
to 100 ml to make a 0.0001M standard.
3. Pipette 10 ml of the 0.0001M standard, and dilute to
100 ml to make a 0.00001M standard solution.
4. Pipette 50 ml of the 0.001M standard into a 100-ml
volumetric flask, and dilute to volume with distilled water to
get a 0.0005M standard.
5. Pipette 10 ml of the 0.0005M standard into a 100-ml
volumetric flask, and dilute to volume to make a 0.00005M stan-
dard.
6. Calibrate the electrode, and construct a calibration
curve (Subsection 5.2.8). Note; As shown in Figure 5.3, the
nominal concentrations of 0.00001M, 0.00005M, 0.0001M, 0.0005M,
and 0.001M NaF should be plotted on the log axis and the elec-
trode potentials (mV) are plotted on a linear scale.
Control samples are needed to verify the expanded calibra-
tion curve and the analytical procedure before and during the
analysis of the field samples. Use the 0.005M control sample
(Subsection 5.2.1) for the serial dilutions.
1. Pipette 5 ml of the 0.005M control sample into a 100-ml
volumetric flask, and dilute to volume to get a 0.00025M control.
2. Pipette 50 ml of the 0.00025M control into a poly-
ethylene beaker, add 50 ml of TISAB buffer, mix well, and use to
validate the calibration curve and to provide hourly checks on
the daily calibration.
3. Analyze the control sample (Subsection 5.2.5), and
record the data on the laboratory worksheet (Figure 5.4).
-------
CJ
Q.
LU
Q
O
OH
140
160
180
200
240
260
280
300
Date
Sample temp
Analyst
Reviewer
Molaritv
0.00001
0.00005
0.0001
0.0005
0.001
Control
sample
0.00001
0.00005 0.0001 :
FLUORIDE MOLARITY, M .
Figure 5.3. .Expanded fluoride calibration curve.
MV
0.0005
0.001
t\$ Cx £0 to
0» (U (D fl>
ua rt < o
n> n> H-rt
w H-
M^ H-O
H,£ a: o
*5 ? '
vO ^ U)
*• o •
. ^ .vD
5 «
00
10
-------
Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 17 of 19
LABORATORY WORKSHEET
Date
Date standards prepared VX9a^ /
Temperature of standards
CL
Electrode number OOl
Standard number
1
2
3
4 .
5
Control sample
Concentration, M
0.001
0.0005
0.0001
0.00005
0.00001
O.OOOA^
Electrode potential, mV
£09
a&3
S6>7
£30
3oo
a^-^
Note: The control sample, from the calibration curve, must be between
0.0002M and 0.0003M.
Signature of analyst
s^x
Signature of reviewer
*/>9
Figure 5.4. Expanded calibration curve data form.
-------
Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 18 of 19 *
Table 5.1 ACTIVITY MATRIX FOR POSTSAMPLING OPERATIONS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
•Sampling
Apparatus
Dry gas meter
±5% of calibration
factor
Make three runs at a
single intermediate
orifice setting at
highest volume of
test (Sec 3.9.2)
Recalibrate;
use factor
that gives
lower gas
volume
Meter thermome-
ters
±6°C (10.8°F) ambient
temperature
Compare with ASTM
mercury-in-glass
thermometer after
each test
Recalibrate;
':se higher
temperature
for calcula-
tions
Barometer
±5 mm (0.2 in. ) at
ambient pressure
Compare with mercury-
in-glass barometer
after each test
Recalibrate;
use lower
barometric
value for
calculations
Stack tempera-
ture sensors
±1.5% of the reference
thermometer or thermo-
couple
Compare with ref-
erence temperature
after each run
Recalibrate;
calculate
with and
without tem-
perature cor-
rections
Base Laboratory
Analysis
Reagents
Prepare according to
Subsec 5.2
Prepare a calibration
curve when preparing
new reagent
Prepare new
solutions and
calibration
curves
(continued)
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Section No. 3.9.5
Revision No. 0
Date January 4, 1982
Page 19 of 19
Table 5.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Control sample
±2% when run with
fluoride standards and
±10% when distilled
and run with field
samples
Prepare new controls
before and during
analysis of field
samples
Prepare new
solution and
calibration
curve, and/or
change dis-
tillate
solution
-------
Section No. 3.9.6
Revision No. 0
Date January 4, 1982
Page 1 of 7
6.0 CALCULATIONS
Calculation errors due to procedural or mathematical mis-
takes can be a large part of total system error. Thus, each set
of calculations should be repeated or spotchecked, preferably by
a team member other than the one that performed the original
calculations. If a difference greater than a typical roundoff
error is detected, the calculations should be checked step-by-
step until the source of error is found and corrected.
A computer program is advantageous in reducing calculation
errors. If a standardized computer program is used, the original
data entry should be checked and if differences are observed, a
new computer run should be made.
Table 6.1 at the end of this section summarizes the quality
assurance activities for calculations. Retain at least one
significant digit beyond that of the acquired data. Roundoff
after the final calculations for each run or sample to two sig-
nificant digits, in accordance with ASTM 380-76. Record the
results on Figure 6.1A or 6.IB.
6.1 Nomenclature
Terms used in Equations 6-1 through 6-7 are defined here for
use in the Subsections that follow.
2 2
A = Area of nozzle, cross-sectional, m (ft )
A. = Aliquot of total sample added to still, ml
B • = Water vapor in the gas stream, proportion by
volume
C = Concentration of fluoride in stack gas corrected
to standard conditions of 20°C, 260 mm Hg (68°F,
29.92 in. Hg) on dry basis, mg/m (Ib/ft )
F. = Total weight of fluoride in sample, mg (Ib)
F., = Total weight of fluoride in sample blank, mg (Ib)
I = Percent of isokinetic sampling, %
-------
Section No. 3.9.6
Revision No. 0*
Date January 4, 1982
Page 2 of 7
SAMPLE VOLUME (ENGLISH UNITS)
Vm = ^8 . 6 if 7ft>, Tm = ,f J£ . £°R, Pbar = £2 - *3 in. Hg
Y = Q - 1 f £' AH = _/ . ^ I in. H20
Equation 6-1
P. + (AH/13.6)
'm(std) • 17'64 v mY -***-*• 22 •
FLUORIDE CONTENT IN SAMPLE
Vt = /£>oo. Oml, At = _/^>^>.£ml, Vd=*l j5~_p . o ml
M = O.Q O £ £>£"M
- V,. V-M ,
F«. = 4.19 x 10"° \ Q = ^/ . ]_ 9 O x 10 Ib Equation 6-4
CONCENTRATION OF FLUORIDE (ENGLIGH UNITS)
vm(std)
Ib
F * - F
C =35.31 -§ - — = 3 . / V X J_ Q Ib/dscf Equation 6-5
s vm(std)
All Other equations same as Methods 2 and 5.
Figure 6.1A. Fluoride calculation form (English units)..
-------
Section No. 3.9.6
Revision No. 0
Date January 4, 1982
Page 3 of 7
SAMPLE VOLUME (METRIC UNITS)
vm = L • J I £ m3 / Tm = 3 L 2 • £ °K' pbar = Z f ^ • £ mm Hg
Y = 0 . 994, AH = ,2 £ . 0 mm H20
Phar+ (AH/13.6)
Vm(std) = °-3858 Vm Y -fiSL'T - « > • * * 5 »3 Equation 6-1
in
FLUORIDE CONTENT IN SAMPLE
vt = - 2 & 9 ' £ m1' At = ^ - - ' ^ m1' Vd = - ^ - ' ^
M = £ - e Q Qo£w
V V
*V = 19 ta d M = <£ . 3 7 ,5"mg Equation 6-4
^ At
CONCENTRATION OF FLUORIDE (METRIC UNITS)
Vm(std) = - • ^ ^ ^ dscm' Ft = 2? • £Z& Ftb = 2 ' 2 $ & mg
F - F
C = -^ — = / . £ 7 ^ mg/dscm Equation 6-5
s vm(std)
All other equations same as Methods 2 and 5.
Figure 6.IB. Fluoride calculation form (metric units).
-------
Section No. 3.9.6
Revision No. 0
Date January 4, 1982
Page 4 of 7
M = Concentration of fluoride from calibration curve,
M
Mu = Molecular weight of water, 18.0 g/g-mole
(18.0 Ib/lb-mole)
Pw = Barometric pressure at sampling site, mm (in.) Hg
P = Absolute stack gas pressure at sampling site, mm
s (in.) Hg
Pstd = standard absolute pressure, 760 mm (29.92 in.) Hg
3
R = Ideal gas constant, 0.066236 mm Hg-m /K-g-mole
(21.83 in. Hg-ftV°R-lb-mole)
T = Absolute average dry gas meter temperature,
m viOn \
J\ \ K.)
T_ = Absolute average stack gas temperature, K (°R)
S
Tstd = standard absolute temperature, 293K (528°R)
V = Volume of distillate collected, ml
a
V. = Total volume of liquid collected in impingers and
silica gel, ml. (Volume of water in silica gel =
grams of silica gel weight increase x i ml/g;
volume of liquid collected in impinger = final
volume - initial volume)
V = Volume of gas sample measured by dry gas
meter, dcm (dcf)
V , . ,v = Volume of gas sample measured by dry gas meter
* ' corrected to standard conditions, dscm (dscf)
V = Stack gas velocity calculated by Method 2 (Equa-
tion 2-7) using data from Method 13, m/s (ft/s)
Vt = Total volume of sample, ml
V, td) = Volume of water vapor in gas sample corrected to
^ ' standard conditions, scm (scf)
Y = Dry gas meter calibration factor
AH = Average pressure differential across the orifice
meter, mm (in.) H2O
p = Density of water, 1 g/ml (0.00220 Ib/ml)
-------
Section No. 3.9.6
Revision No. 0
Date January 4, 1982
Page 5 of 7
0 = Total sampling time, rain
13.6 = Specific gravity of mercury
60 = s/min
100 = Factor for converting to percent, %
6.2 Dry Gas Volume, Corrected to Standard Conditions
Correct the sample volume measured by the dry gas meter
(V ) to standard conditions (20°C and 760 mm Hg or 68°F and 29.92
in. Hg) by using Equation 6-1. The absolute dry gas meter tem-
perature (T ) and orifice pressure drop (AH) are obtained by
averaging the field data.
TC<-H pna-r- * (AH/13.6)
\j - v v std bar
Vm(std) - VmY Tm Pgtd
Pbar + (AH/13.6)
= Kl V T Equation 6-1.
m
where
K, = 0.3858 K/mm Hg for metric units, and
= 17.64 °R/in. Hg for English units.
Note; If the leak rate observed during any mandatory leak check
exceeds the acceptable rate, the tester shall either correct the
value of Vm in Equation 6-1 (Subsection 3.2.6, Method 3), or in-
validate the test runs.
6.3 Volume of Water Vapor
Pw R T td
Vw(std) = Vic S£ ~P^f - K Vic Equation 6-2
•»»
where
K = 0.00133 m3/ml for metric units, and
= 0.04707 ft3/ml for English units.
-------
Section No. 3.9.6
Revision No. 0 -
Date January 4, 1982
Page 6 of 7
Bws = - - ^ Equation 6-3
6.4 Moisture Content of stack Gas
V
m(std) * Vw(std)
Note: If liquid droplets are in the gas stream, assume the
stream to be saturated; use a psychrometric chart to obtain
estimate of the moisture percentage.
6.5 Fluoride Content in Sample (Concentration)
F,_ = K ~ (V, x M) Equation 6-4
•C. At Q
where
K = 19 mg/mmole for metric units,
K = 4.19 x io5 Ibs for English units.
6.6 Concentration of Fluoride in Stack Gas
F- F
^ ^V\
C = K -r= Equation 6-5
5 vm(std)
K = 1.00 m3/m3 for metric units
K = 35.31 ft3/m3 for English units.
6.7 Isokinetic Variation (I)
The isokinetic variation (I) can be calculated from either
raw data or intermediate values using the following equations.
6.7.1 Calculation of I from Raw Data
100 x Ts [K Vi(. + (Y Vp/T,,) (Pbar + AH/13.6)]
Equation 6-6
where
K = 0.003454 mm Hg-m3ml-K for metric units, and
= 0.002669 in. Hg-ft3/ml-°R for English units.
6.7.2 Calculations of I from Intermediate Values
" T F
r std
= 60 f1-
-------
Section No. 3.9.6
Revision No. 0
Date January 4, 1982
Page 7 of 7
= K
T V
1s rn(std)
vsPsAn 6 (1-
where
6.7
K = 4.320 for metric units, and
= 0.09450 for English units.
Acceptable Results
If 90% £ I <. 110%, the results are acceptable.
If the
results are low in comparison to the standards and if I is beyond
the acceptable range, the administrator may opt to accept the
results; if not, reject the results and repeat the test.
Table 6.1 ACTIVITY MATRIX FOR CALCULATIONS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are mot met
Analysis data
form
All data and calcula-
tions given
Visual check
Complete the
missing data
values
Calculations
Difference between
check and original
calculations within
roundoff error; one
decimal figure re-
tained beyond that of
acquired data
Repeat all calcula-
tions starting with
raw data for hand
calculations; check
all raw data input
for computer cal-
culations and hand
calculate one sample
per test
Indicate
errors on
analysis data
form
Isokinetic
variation
90% < I < 110%; see
Eqs 6-6 and 6-7 for
calculation of I
Calculate I for
each traverse point
Repeat test;
adjust flow
rates to
maintain I
within ±10%
variation
-------
Section No. 3.9.7
Revision No. 0
Date January 4, 1982
Page 1 of 3
7.0 MAINTENANCE
Normal use of emission testing equipment subjects it to
corrosive gases, temperature extremes, vibrations, and shocks.
Keeping the equipment in good operating order over an extended
time requires routine maintenance and knowledge of the equipment.
Maintenance of the entire sampling train should be performed
either quarterly or after 1000 ft of operation, whichever occurs
sooner. Maintenance activities are summarized in Table 7.1 at
the end of this section; the following routine checks are recom-
mended, but not required, to increase reliabilty.
7.1 Pump
Several types of pumps are used in commercial sampling
trains; two of the most common are the fiber vane pump with
in-line oiler and the diaphragm pump. The fiber vane pump needs
a periodic check of the oil and the oiler jar. Used oil (usually
nondetergent or machine weight) should be about the same trans-
lucent color as unused or spare oil. When the pump starts to run
erratically or when the head is removed each year, the fiber
vanes should be changed.
The diaphragm pump requires little maintenance. If the
diaphragm pump leaks or runs erratically, it is normally due to a
bad diaphragm or to malfunctions in the valves; these parts are
easily replaced, and should be cleaned annually by complete dis-
assembly of the train.
7.2 Dry Gas Meter
The dry gas meter should be checked for excess oil and
component corrosion by removing the top plate every 3 mo. The
meter should be disassembled, and all components cleaned and
checked more often if the dials show erratic rotation or if the
meter will not calibrate properly.
-------
Section No. 3.9.7
Revision No. 0 •
Date January 4, 1982
Page 2 of 3
7.3 Inclined Manometer
The fluid should be changed when it is discolored, or when
it contains visible matter, and when it is disassembled yearly.
No other routine maintenance is required since the inclined
manometer is checked during the leak checks of both the pitot
tube and the entire meter box.
7.4 Sampling Train
All other sample train components should be visually checked
every 3 mo, and they should be completely disassembled and
cleaned or replaced yearly. Many of the parts, such as quick
disconnects, should be replaced when damaged rather than after
they are periodically checked. Normally, the best maintenance
procedure is to replace the entire unit—for example, a meter
box, sample box, or umbilical cord.
-------
Section No. 3.9.7
Revision No. 0
Date January 4, 1982
Page 3 of 3
Table 7.1 ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Fiber vane pump
Leak free; required
flow; no -erratic be-
havior
Periodic check of oil
and oiler jar; remove
head yearly and
change fiber vanes
Replace as
needed
Diaphragm pump
Leak-free valves func-
tioning properly; re-
quired flow
Clean valves during
yearly disassembly
Replace when
leaking or
when running
erratically
Dry gas meter
oil, corro-
No excess
sion, or erratic
rotation
dial
Check every 3 mo for
excess oil or corro-
sion; check valves
and diaphragm if
dial runs erratically
or if meter will not
calibrate
Replace parts
as needed, or
replace meter
Inclined manom-
eter
No discoloration of or
visible matter in the
fluid
Check periodically;
change fluid during
yearly disassembly
Replace parts
as needed
Other sampling
train com-
ponents
No damage or leaks; no
erratic behavior
Visually check every
3 mo; disassemble and
clean or replace
yearly
If failure
noted, re-
place meter
box, sample
box, or um-
bilical cord
Nozzle
No dents, corrosion,
or other damage
Visually check be-
fore and after each
test run
Replace noz-
zle or clean,
sharpen, and
recalibrate
-------
Section No. 3.9.8
Revision No. 0
Date January 4, 1982
Page 1 of 7
8.0 AUDITING PROCEDURES
An audit is an independent assessment of the quality of data
collected during all source tests, especially those required for
enforcement. "Independent" means that the individual(s) perform-
ing the audit and the standards and equipment used in the audit
are different from the regular field team and the standards and
equipment used in the source test. A source test for enforce-
ment comprises a series of runs at one source. Although quality
assurance checks by a field team are necessary for routinely
generating good quality data, they are not part of the auditing
procedure. Table 8.1 at the end of this section summarizes the
quality assurance activities for the auditors.
Based on a collaborative test1 of Method 13B, performance
audits are recommended for—
1. The sampling train volumetric flow measuring device,
2. The analytical phase, and
3. The data processing.
In addition to the three performance audits, a system audit
should be conducted as specified by the quality assurance coordi-
nator. The performance and the system audits are detailed in
Subsections 8.1 and 8.2.
8.1 Performance Audits
Performance audits—independent checks by an auditor to
assess data produced by the total measurement system (sample
collection and analysis, and data processing)—are quantitative
appraisals of data quality.
8.1.1 Audit of Sampling Train Volumetric Flow Metering Device -
The audit procedure described in this subsection can be used
to determine the accuracy of the flow metering device (dry gas
meter) in a sampling train. The dry gas meter is audited using a
calibrated critical flow orifice housed in a quick-connect cou-
pling and the following procedure:
-------
Section No. 3.9.8
Revision No. 0
Date January 4, 1982
Page 2 of 7
I. Remove the critical orifice from its case and insert it
into the gas inlet quick-connect coupling on the source sampling
meter box.
2. Turn the power to the meter box on and start the pump.-
3. Completely open the coarse flow rate control valve and
close the fine flow rate control valve to give a maximum vacuum
reading. Caution: A vacuum reading of <425 mm (17 in.) Hg will
result in flow rate errors.
4. Allow the orifice and source sampling meter box to
warmup for 45 min with flow controls adjusted as described in
step 3 before starting quality assurance runs. If the audit is
made at the conclusion of the sample run, the warmup period is
not necessary.
5. Make triplicate quality assurance runs. For each run,
record the initial and the final dry gas meter volumes, the dry
gas meter inlet and outlet temperatures, the internal orifice
pressure drop (AH), the ambient temperature, and the barometric
pressure. The duration of the run should be slightly >15 min.
The following procedure is recommended and should be performed
three times to provide the required triplicate quality assurance
runs: 15 min after a run is started, watch the dry gas meter
needle closely. As the needle reaches the zero (12 o'clock)
position, stop the pump and stopwatch simultaneously. Record the
dry gas meter volume and the time.
6. Calculate the corrected dry gas volume for each run
using Equation 8-1. For each replicate, record the corrected dry
gas volume in dry standard cubic meters, the sampling time in
decimal minutes, the barometric pressure in millimeters of Hg;
and the ambient temperature in degrees celcius.
= K vmY f!^
+ -£S-\
* 13.6 \
I
-------
Section No. 3.9.8
Revision No. 0
Date January 4, 1982
Page 3 of 7
Responsible control agencies can obtain a calibrated criti-
cal orifice (when available) prior to each enforcement source
test, conduct the audit, and return the orifice and data form to
EPA for evaluation. Orifices may be obtained from the Source
Test Audit coordinator, Quality Assurance Division, Environmental
Monitoring Systems Laboratory, USEPA, Research Triangle Park,
North Carolina 27711. It is also suggested that organizations
that conduct compliance tests participate in the .EPA semiannual
audit of volume meters.
8.1.2 Audits of the Analytical Phase - The two recommended
performance audits should be performed once during every enforce-
ment source test as two steps: (1) an optional pretest audit,
and (2) a mandatory audit during the analysis of the field sam-
ples.
8.1.2.1 Pretest Audit of Analytical Phase (Optional) - The pre-
test audit for determining the proficiency of the analyst, the
accuracy of the analytical procedure, and the accuracy of the
standards should be performed at the discretion of the agency
auditor, by using aqueous sodium fluoride (NaF) samples provided
to the laboratory before the enforcement source test. The NaF
samples may be prepared by the same procedures used for preparing
control samples (Section 3.9.5).
The pretest audit is especially recommended for a laboratory
with little or no experience with the Method 13B analytical
procedure (Section 3.9.5). The laboratory should notify the
agency/organization requesting the performance test of the intent
to test 30 days before the enforcement source test, and should
request that the following audit samples be provided: a 1-Jt
sample for a low concentration (0.2 to 1.0 mg F/dscm of gas
sampled or approximately 1 to 5 mg NaF/£ of sample) and a 1-2
sample for a high concentration (2.0 to 10.0 mg F/dscm of gas
sampled or approximately 10 to 50 mg NaF/£ of sample). At least
10 days before the enforcement source test, the agency/organiza-
tion should provide the audit samples. The laboratory could
analyze the low and high concentrations, and submit the results
to the agency/organization before the enforcement source test.
-------
Section No. 3.9.8
Revision No. 0 '
Date January 4, 1982
Page 4 of 7
Note: The analyst performing this optional audit must perform
the field sample analysis also (Subsection 8.1.3).
The agency/organization determines the percent accuracy, %A,
between the measured and the known concentrations of the audit
sample using Equation 8-2.
C (M)-CF(A)
% A = c (Aj 100 Equation 8-2
where
.Cp(M) = concentration of the audit sample measured by lab
analyst, mg/ml, and
Cp(A) = known concentration of the audit sample, mg/ml.
The %A is actually a measure of the inaccuracy of the analytical
phase.
The control limits for %A is expected to be within ±12% of
true value.
8.1.2.2 Audit of the Analysis (Mandatory) - The purpose of this
mandatory audit is to assess the data quality at the time of the
analysis; this audit is useful in checking computer programs and
manual methods of data processing. The agency should provide two
audit samples to be analyzed along with the field samples. The
percent accuracy (%A) of the audit samples (determined using
Equation 8-2) should be included in the enforcement source test
report as a measure of the inaccuracy (bias and imprecision) of
the analytical phase of Method 13B during the actual enforcement
source test.
8.1.3 Audit of Data Processing - Data processing errors may be
determined by independent (audit) calculations, starting with
data on the field and laboratory data forms. If a difference,
other than roundoff error is detected between the original and
the audit calculations, check all data calculations. Alterna-
tively, the data processing may be audited by providing the
testing laboratory with specific data sets (exactly as would
occur in the field) and by requesting that the results of the
data calculations be returned to the agency/organization.
-------
Section No. 3.9.8
Revision No. 0
Date January 4, 1982
Page 5 of 7
8.2 System Audit
A system audit—an on-site inspection and review of quality
assurance checks on the total measurement system (sample collec-
tion and analysis, data processing, etc.)—normally is a quali-
tative appraisal of data quality.
Initially, a system audit is recommended for each enforce-
ment source test. After the field team has acquired sufficient
experience with the method, the frequency of system audits may be
reduced—for example, to one of every four enforcement source
tests.
The auditor, i.e., the person performing the system audit,
should have extensive experience in source sampling, specifically
with the measurement system being audited. The auditor's respon-
sibilities are as follows:
1. Inform the field team of the results of pretest per-
formance audits, and specify any needed attention or improvement.
2. Observe the procedures and techniques used by the field
team during sample collection.
3. Check/verify the records of apparatus calibration
checks and the quality control charts used in the laboratory
analysis of control samples from previous source tests, if appli-
cable.
4. Forward the results of the system audit to field team
management so that appropriate corrective action may be ini-
tiated.
While on-site, the auditor should observe the field test team's
overall.performance, including the following:
1. Setting up and leakchecking the sampling train.
2. Preparing the absorbing solution, and adding it to the
impingers.
3. Checking the isokinetic sampling.
4. Conducting the posttest leak check.
5. Conducting the sample recovery, and checking the data
integrity.
Figure 8.2 is a checklist suggested for use by the auditor.
-------
Section No. 3.9.8
Revision No. 0 '
Date January 4, 1982
Page 6 of 7
iTes
No
Comment
OPERATION
JO
X
X
Presampling Preparation
1. Knowledge of process conditions
2. Calibration of equipment, before each
field test
On-Site Measurements
3. Sample train assembly
4. Pretest leak check
5. Isokinetic sampling
6. Posttest leak check
7. Record process conditions during sample
collection
8. Sample recovery and data integrity
Postsampling
9. Accuracy and precision of control sample
analysis
10. Recovery of samples for distillation
11. Calibration checks
12. Calculation procedure/check
General Comments
Figure 8.1. Method 13B checklist for auditors.
-------
Section No. 3.9.8
Revision No. 0
Date January 4, 1982
Page 7 of 7
TABLE 8.1. ACTIVITY MATRIX FOR AUDITING PROCEDURES
Audit
Acceptance limits
Frequency and method
of measurement
Action if
requi rements
are not met
Performance
Audit
Analytical
phase of
Method 13B
using aqueous
sodium fluo-
ride
Measured concentrations
of audit sample within
±12% of true value
Once during every
enforcement source
test; measure audit
samples and compare
their values with
known concentrations
Review
operating
technique
Data processing
errors
Difference between
original and audit
calculations within
roundoff error
Once during every
enforcement source
test, perform inde-
pendent calculations
starting with data
recorded on field
and laboratory forms
Check and
correct all
data; recal-
culate if
necessary
System audit
Operation technique as
described in Section
3.9
Once during every
enforcement test,
until experience
gained and then
every fourth test,
observe techniques;
use audit checklist
(Fig 8.2)
Explain to
team devia-
tions from
recommended
techniques;
note on
Fig 8.2
-------
Section No. 3.9.9
Revision No. 0
Date January 4, 1982
Page 1 of 1
9.0 RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
To acquire data of good quality, two considerations are
essential:
1. The measurement process must be in a state of statis-
tical control at the time of the measurement, and
2. The systematic errors, when combined with the random
variations (errors of measurement), must result in acceptable
uncertainty.
Other quality assurance activities include quality control checks
and independent audits of the total measurement system (Section
3.9.8); documentation of data by using quality control charts (as
appropriate); use of materials, instruments, and procedures that
can be traced to appropriate standards of reference; and use of
control standards and working standards for routine data collec-
tion and equipment calibration. Working standards should be
traceable to primary standards:
1. Dry gas meter calibrated against a wet test meter that
has been verified by liquid displacement (Section 3.9.2) or by a
spirometer.
2. Field samples analyzed by comparisons with standard
solutions (aqueous NaF) that have been validated with independent
control samples.
-------
10.0 REFERENCE METHOD*
Method J3B. Determination of Total Fluoride
Emissions From Stationary Sources: Specific
Ion Electrode Method
I. Applicability and Principle
1.1 Applicability. This method applies to
the determination of fluoride (FJ emissions
from stationary sources as specified In the
regulations. It does not measure
fluorocarbons. such as freons.
1.2 Principle. Gaseous and paniculate F
are withdrawn isokinetically from the source
and collected in water and on a filter. The
total F is then determined by the specific ion
electrode method.
2. Range and Sensitivity
The range of this method is 0.02 to 2.000 fig
F/ml: however, measurements of less than 0.1
>ig F/ml require extra care. Sensitivity has
not been determined.
3. Interferences
Crease on sample-exposed surfaces may
cause low F results because of adsorption.
Section No. 3.9.10
Revision No. 0
Date January 4, 1982
Page 1 of 2
4. Precision and Accuracy
4.1 Precision. 'The following estimates
are based on a collaborative test done at a
primary aluminum smelter. In the test, six'
laboratories each sampled the stack
simultaneously using two sampling trains for
a total of 12 samples per sampling run.
Fluoride concentrations encountered during
the test ranged from 0.1 to 1.4 mg F/ra*. The
within-laboratory and between-laboratory
standard deviations, which include sampling
and analysis errors, are 0X137 mg F/ra' with '
60 degrees of freedom and (1056 mg F/ra'
with five degrees of freedom, respectively.
4.2 Accuracy. The collaborative test did
not find any bias in the analytical method.
S. Apparatus
S.1 Sampling Train and Sample Recovery.
Same as Method 13A. Sections 5.1 and 5J.
respectively.
5.2 Analysis. The following items are
needed:
5.2.1 Distillation Apparatus. Bunsen
Burner, Electric Muffle Furnace. Crucibles.
Beakers,-Volumetric Flasks, Erlenmeyer
Flasks or Plastic Bottles, Constant
Temperature Bath, and Balance. Same as
Method ISA. Sections 5JJ to 5A9.
respectively, except include also 100-ml
polyethylene beakers.
5i2 Fluoride Ion Activity Sensing
Electrode.
5.2.3 Reference Electrode. Single
junction, sleeve type.
5.2.4 Electrometer." A pH meter with
millivolt-scale capable of iO.l-mv resolution.
or a specific ion meter made specifically for -
specific ion use..
5.2J Magnetic Stirrer and TFE *
Fluorocarbon-Coaied Stirring Bars.
& Reagents
6.1 Sampling and Sample Recovery.
Same as Method 13A. Sections 6.1 and 6A
respectively.
6£ Analysis. Use ACS reagent grade.
chemicals (or equivalent), unless otherwise
specified. The reagents needed for analysis
are as follows:
6£.l Calcium Oxide (CaO). Certified
grade containing 0.005 percent F or less.
6.2,2 Phenolphthalein Indicator.
Dissolve 0.1 g of phenolphthalein in a mixture
of 50 ml of 90 percent ethanol and 50 ml
deionized distilled water.
6.24 Sodium Hydroxide (NaOH).
Pellets.
6.2.4 Sulfuric Acid (H.SO.). Concentrated.
6.2£ Filters. Whatman No. 541. or
equivalent
6.2.6 Water. From same container as
6.1.2 of Method 13A.
6.2.7 Sodium Hydroxide. 5 Ml Dissolve
20 g of NaOH in 100 ml of deionized distilled
water.
6.2.8 Sulfuric Acid. 25 percent (V/V).
Mix! part of concentrated H,SO. with 3
parts of deionized distilled water.
*Taken from Federal Register, Vol
Friday, June 20, 19577
'Mention of any trad* name or specific product
do«t nw constitute endortemenl by th«
Environmental Protection Agency.
45, No... 121, pp. 41857-41858,
-------
Section No. 3.9.10
Revision No. -0
Date January 4, 1982
Page 2 of 2 .
&Z9 Total Ionic Strength Adjustment
Buffer (TISAB). .Place approximately 500 ml
of deionized distilled water in a 1-liter
beaker. Add 57 ml of glacial acetic acid. 58 g
of sodium chloride, and 4 g of cyclohexylene
dinitrilo tetraacetic acid. Stir to dissolve.
Place the beaker in a water bath to cool it
Slowly add 5 M NaOH to the solution.
measuring the pH continuously with a
calibrated pH/reference electrode pair, until
the pH is 5-3. Cool to room temperature. Pour
into a 1-liter volumetric flask, and dilute to
volume with deionized distilled water.
Commercially prepared TISAB may be
substituted for the above.'
B.Z10 Fluoride Standard Solution. 0.1 M.
Oven dry some sodium fluoride (NaF) for a
minimum of 2 hours at 110'C. and store in a
desiccator! Then add 42 g of NaF to a 1-liter
volumetric flask, and add enough deionized
distilled water to dissolve. Dilute to volume
with deionized distilled water.
7. Procedure
7.1 Sampling. Sample Recovery, and
Sample Preparation and Distillation. Same
as Method 13A. Sections 7.1,7.2. and 7.3,
respectively, except the notes concerning
chloride and sulfate interferences are not
applicable.
7.2 Analysis.
7.2.1- Containers No. 1 and No. 2. Distill
suitable aliquots from Containers No. 1 and
No. 2. Dilute the distillate in the volumetric
flasks to exactly 250 ml with deionized
distilled water and mix thoroughly. Pipet a
25-ml aliquot from each of the distillate and
separate beakers. Add an equal volume of
TISAB, and««»»- The sample should be at the
same temperature as the calibration
standards when measurements are made. If
ambient laboratory temperature fluctuates
• more than ±2*C from the temperature at
which the calibration standards were
"measured, condition samples and standards
in a constant-temperature bath before
measurement Stir the sample with a
magnetic stirrer during measurement to
minimize electrode response time. If the
•tirrer generates enough heat to change
solution temperature, place a piece of
temperature insulating material such as cork.
between the stirrer and the beaker. Hold
dilute samples (below 10~4M fluoride ion.
eeatent) in polyethylene beakers during
measurement
Insert the fluoride and reference electrodes
into the solution. When a steady millivolt
reading is obtained, record it This may take
several minutes. Determine concentration
from the calibration curve. Between electrode
measurements, rinse the electrode with
distilled water.
723 Container No. 3 (Silica Gel). Same
as Method 13A. Section 7.4.2.
8. Calibration
Maintain a laboratory log of all
calibrations.
8.1 Sampling Train. Same as Method
13A.
8J Fluoride Electrode. Prepare fluoride
standardizing solutions by serial dilution of
the 0.1 M fluoride standard solution. Pipet 10
ml of 0.1 M fluoride standard solution into a
100-ml volumetric flask, and make up to the
mark with deionized distilled water for a KT1
M standard solution. Use 10ml of 10"*M
solution to make a 10"'M solution in the
same manner. Repeat the dilution procedure
and make 10"* and 10'* solutions.
Pipet SO ml of each standard into a
separate beaker. Add 50 ml of TISAB to each
beaker. Place the electrode in the most dilute
standard solution. When a steady millivolt
reading is obtained, plot the value on the
linear axis of semilog graph paper versus
concentration on the log axis. Plot the
nominal value for concentration of the
standard on the log axis. e.g.. when 50 ml of
10~*M standard is diluted with SO ml of
TISAB. the concentration is still designated
"lO-'M."
Between measurements soak the fluoride
sensing electrode in deionized distilled water
for 30 seconds, and then remove and blot dry.
Analyze the standards- going from dilute to
concentrated standards. A straight-line
calibration curve will be obtained, with
nominal concentrations of 10"', 10~*. 10"*,
and 10*' fluoride molariry on the log axis
plotted versus electrode potential (in mv) on
the linear scale. Some electrodes may be
slightly nonlinear between 10" • and 10" «M. If
this occurs, use additional standards between
these two concentrations.
Calibrate the fluoride electrode daily, and
check it hourly. Prepare fresh fluoride
standardizing solutions daily (10~*M or less).
Store fluoride standardizing solutions in
polyethylene or polypropylene containers.
(Note: Certain specific ion meters have been
designed specifically for fluoride electrode
use and give a direct readout of fluoride ion
concentration. These meters may be used in
lien of calibration curves for fluoride
measurements over narrow concentration
ranges. Calibrate the meter according to the
manufacturer's instructions.)
ft Calculations
Carry out calculations, retaining at least
one extra, decimal figure beyond that of the
acquired data. Round off figure* after final
calculation.
9.1 Nomenclature. Same as Method 13A,_
Section 9.1. m addition:
M«F concentration from calibration cur
molariry.
9.2 Average Dry Gas Meter Temperature
and Average Orifice Pressure Drop. Dry Gas
Volume. Volume of Water Vapor and
Moisture Content Fluroide Concentration in
Stack Gas, and Isokinetic Variation and
Acceptable Results. Same as Method 13A.
Section 9.2 to 9.4,9.5.2, and 9.8, respectively.
94 Fluoride in Sample. Calculate the
amount of F in the sample using the
following:
JdlSA.
urvefl
(Vd) (M) Equation 13B-1
Where
K»19mg/ml.
10. References
\. Same as Method 13A. Citations 1 and 2
of Section 10.
2. MacLeod, Kathryn E. and Howard L.
Crist Comparison of the SPADNS—
Zirconium Lake and Specific Ion Electrode
Methods of Fluoride Determination in Stack
Emission Samples. Analytical Chemistry.
45:1272-1273.1973.
[FR Doe. SO-1SSM FiM 9-W-tft MS ••]
•IUJNO COOC M40-01-M
-------
Section No. 3.9.11
Revision No. 0
Date January 4, 1982
Page 1 of 1
11.0 REFERENCES
1. Standards of Performance Promulgated for Five Cate-
gories of Sources in the Phosphate Fertilizer Industry.
Federal Register, Vol. 42. August 6, 1975.
2. Determination of Total Fluoride Emissions from Station-
ary Sources; Specific Ion Electrode Method. Federal
Register, Vol. 45. June 20, 1980.
3. Martin, R. M. Construction Details of Isokinetic
Source Sampling Equipment. APTD-0581, USEPA, Air Pol-
lution Control Office, Research Triangle Park, North
Carolina. 1971.
4. Rom, J. J. Maintenance, Calibration, and Operation of
Isokinetic Source Sampling Equipment. AFTD-0576.
USEPA Office of Air Programs, Research Triangle Park,
North Carolina. 1972.
-------
Section No. 3.9.12
Revision No. 0
Date January 4, 1982
Page 1 of 22
12.0 DATA FORMS
Blank data forms are provided on the following pages for the
convenience of the Handbook user. Each blank form has the cus-
tomary descriptive title centered at the top of the page. How-
ever, the section-page documentation in the top right-hand corner
of each page of other sections has been replaced with a number in
the lower right-hand corner that will enable the user to identify
and refer to a similar filled-in form in the text section. For
example, Form M13B-1.2 indicates that the form is Figure 1.2 in
Section 3.9.1 of the Method 13B Handbook. Future revisions of
this form, if any, can be documented by 1.2A, 1.2B, etc. Fifteen
of the blank forms listed below are included in this section.
Three are in the Method Highlights Section as shown by the MH
following the form number and one is left blank in the text.
Form Title-
1.2 Procurement Log
2.3A & B Dry Gas Meter Calibration Data Form
(English and Metric units)
2.4A & B Posttest Meter Calibration Data Form
(English and Metric units)
2.5 Stack Temperature Sensor Calibration
Data Form
2.6 Nozzle Calibration Data Form
2.7 Fluoride Calibration Curve Data Form
3.1 (MH) Pretest Sampling Checks
4.1 Nomograph Data Form
4.2 Fluoride Field Data Form
4.3 Sample Recovery and Integrity Data Form
4.4 Sample Label
4.5 (MH) On-Site Measurement Checklist
5.1 Posttest Calibration Checks
-------
Section No. 3.9.12
Revision No. 0
Date January 4,.1982
Page 2 of 22
Form Title
5.2 Fluoride Analytical Data Form
5.3 Sample Analytical Data Form
5.4 Expanded Calibration Curve Data Form
6.1A & 6.IB Fluoride Calculation Data Form
(English, and Metric units)
8.2 (MH) Method 13B Checklist To Be Used by Auditors
-------
PROCUREMENT LOG
Item description
Quantity
Purchase
order
number
Vendor
Date
Ordered Received
Cost
Dispo-
sition
Comments
Quality Assurance Handbook M13A-1.2
-------
Date
DRY GAS METER CALIBRATION DATA (English units)
Meter box number
Barometric pressure, P, =
in. Hg Calibrated by
Orifice
manometer
setting
(AH),
in. H20
0.5
1.0
1.5
2.0
3.0
4.0
Gas volume
Wet test.
meter
^
^i - P, (td + 460) Vw
*If there is only one thermometer on the dry gas meter, record the temperature
under t,.
Quality Assurance Handbook M5-2.3A
-------
METER BOX CALIBRATION DATA AND CALCULATION FORM (English units)
Nomenclature:
V = Gas volume passing through the wet test meter, ft3.
VF
V, = Gas volume passing through the dry gas meter, ft3.
t = Temperature of the gas in the wet test meter, °F.
VF
t, = Temperature of the inlet gas of the dry gas meter, °F.
t, = Temperature of the outlet gas of the dry gas meter, °F.
o
t, = Average temperature of gas in dry gas meter, obtained by average t, and
t, , °F. i
o
AH = Pressure differential across orifice, in. H2O.
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;
AH@. = Orifice pressure differential at each flow rate that gives 0.75 ft3/min of air at
standard conditions for each calibration run, in. H2O; 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. H2O; tolerance = 1.84±0.25 (recommended).
0 = Time for each calibration run, min.
P^ = Barometric pressure, in. Hg.
Quality Assurance Handbook M5-2.3A (backside)
-------
Date
DRY GAS METER CALIBRATION DATA (metric units)
Meter box number
Barometric pressure, P. =
mm Hg Calibrated by
Orifice
manometer
setting
(AH),
mm HgO
10
25
40
50
75
100
Gas volume
Wet test
meter
(vw),
m3
0.15
0.15
0.30
0.30
0.30
0.30
Dry gas
meter
(vd),
m3
Temperatures
Wet test
meter
(v 273>
^ _ 0.00117 M K + 273> f
**! - p^ (t() + 273) VB
.,
alf there is only one thermometer on the dry gas meter, record the temperature
under t :
Quality Assurance Handbook M-5-2-.3B-
-------
METER BOX CALIBRATION DATA AND CALCULATION FORM (metric units)
Nomenclature:
V = Gas volume passing through the wet test meter, m3.
V, = Gas volume passing through the dry gas meter, m3.
t = Temperature of the gas in the wet test meter, °C.
Vf
t, = Temperature of the inlet gas of the dry gas meter, °C.
t, = Temperature of the outlet gas of the dry gas meter, °C.
o
t, = Average temperature of gas in dry gas meter, obtained by average of t, and
d td , °C. ai
o
AH = Pressure differential across orifice, mm H2O.
Y. = Ratio of accuracy of wet test meter to dry gas meter for each run; tolerance Y. =
1 Y+0.02 Y.
Y = Average ratio of accuracy of wet test meter to dry gas meter for all six runs;
AH@. = Orifice pressure differential at each flow rate that gives 0.021 m3 of air at standard
conditions for each calibration run, mm H2O; tolerance AH@. = AH@±3.8 nun H2O
(recommended).
AH@ = Average orifice pressure differential that gives 0.021 m3 of air at standard con-
ditions for all six runs, mm H2O; tolerance AH@ = 46.74 +6.3 mm H2O (recommended).
0 = Time of each calibration run, min.
P. = Barometric pressure, mm Hg.
Quality Assurance Handbook M5-2.3B (backside)
-------
Test numbers
POSTTEST DRY GAS METER CALIBRATION DATA FORM (English units)
Date Meter box number Plant
Barometric pressure, P. =
in. Hg Dry gas meter number
Pretest Y
Orifice
manometer
setting,
(AH),
in. H20
Gas volume
Wet test
meter
«
OF
Dry gas meter
Inlet
(td),
i
°F
Outlet
(td ),
o
°F
Average
(td),a
op-
Time
(9),
min
Vacuum
setting,
in. Hg
y.
i
Y.
i
V P, (t, + 460)
w b d
/ AH \/ , \
Vd lPb 13.6JVW *60/
Y =
If there is only one thermometer on the dry gas meter, record the temperature under t,.
V = Gas volume passing through the wet test meter, ft3.
V = Gas volume passing through the dry gas meter, ft3.
t = Temperature of the gas in the wet test meter, °F.
t, = Temperature of the inlet gas of the dry gas meter, °F.
i
t. = Temperature of the outlet gas of the dry gas meter, °F.
o
t. = Average temperature of the gas in the dry gas meter, obtained by the average of t. and td , °F.
All = Pressure differential across orifice, in. H20.
Y. - Ratio of accuracy of wet test meter to dry gas meter for each run.
Y = Average ratio of accuracy of wet test meter to dry gas meter for all three runs;
tolerance = pretest Y +0.05Y
P. = Barometric pressure, in. Hg.
6 = Time of calibration run, min.
Quality Assurance Handbook M5-2.4A
-------
POSTTEST METER CALIBRATION DATA FORM (Metric units)
Test numbers
Date
Meter box number
Plant
Barometric pressure, P. =
mm Hg Dry gas meter number
Pretest Y
Orifice
manometer
setting,
(AH),
mm H20
Gas volume
Wet test
meter
(vw),
m3
0.30
0.30
0.30
Dry gas
meter
(vd),
m3
Temperature
Wet test
meter
°C
Dry gas meter
Inlet
<%>•
°C
Outlet
(td),
0
°C
Average
-------
Date
STACK TEMPERATURE SENSOR CALIBRATION DATA FORM
Thermocouple number
Ambient temperature
Calibrator
*C Barometric pressure
in. Hg
Reference: mercury-in-glass
other
Reference
point
number
Source
(specify)
Reference
thermometer
temperature,
°C
Thermocouple
potentiometer
temperature,
°C
Temperature.
difference,
aType of calibration system used.
bf(ref temp, °C + 273) - (test thermom temp. °C + 273)1
Lref temp, °C + 273 J
Quality Assurance Handbook M5-2.5
-------
NOZZLE CALIBRATION DATA FORM
Date
Calibrated by
Nozzle
identification
number
Nozzle Diameter3
DI,
mm (in. )
D2,
mm (in.)
D3/
mm (in. )
AD,b
mm (in. )
avg
where:
•D
1,2,3,
AD =
three different; nozzles diameters, mm (in.); each
diameter must be within (0.025 mm) 0.001 in.
maximum difference between any two diameters, mm (in.),
AD £(0.10 mm) 0.004 in.
avg
= average of D,, D2/ and D-
Quality Assurance Handbook M5-2.6
-------
FLUORIDE CALIBRATION DATA FORM
LABORATORY WORKSHEET
Date standards prepared
Temperature of standards
Date
Electrode number
Standard number
Control Sample
Concentration (M)
0.000001
0.00001
0.0001
0.001
0.01
0.1
Electrode potential (mV)
Note: The concentration of the control sample determined from the calibration
curve must be between 0.002M and 0.01M.
Signature of analyst _
Signature of reviewer
Quality Assurance Handbook M5-2.7
-------
NOMOGRAPH DATA FORM (English units)
Plant
Date
Sampling location
Calibrated pressure differential across
orifice, in. H2O
Average meter temperature (ambient + 20°F), °F
Percent moisture in gas stream by volume, %
Barometric pressure at meter, in. Eg
Static pressure in stack, in. Eg
(P ±0.073 x stack gauge pressure, in. H20)
Ratio of static pressure to meter pressure
Average stack temperature, °F
Average velocity head, in. B20
Maximum velocity head, in. H20
C factor
Calculated nozzle diameter, in.
Actual nozzle diameter, in.
Reference Ap, in. H20
*H@
Tmavg
wo
p»
ps
*•/•.
Ts
avg
APavg
APmax
Quality Assurance Handbook M5-4.1
-------
PARTICULATE FIELD DATA FORM
Plant
City ^
Location
Operator
Date
Meter calibration (Y)
Pi tot tube (C )
Probe length "
Sheet
of
Run number ^__^__^
Stack diam, mm (in.)
Sample box number
Meter box number
Meter AH@
Probe liner material
Probe heater setting
Ambient temperature
Barometric pressure (P.)
Assumed moisture
Static pressure (P )
C Factor a
Reference AP
mm (in.) Hg
Nozzle identification number
Nozzle diameter mm (in.)
Thermometer number __^_^_^_^
Final leak rate ma/min (cfm)
Vacuum during leak check
mm (in.) Hg
mm (in.) H20
Filter position
Maximum AH
Remarks
mm (in.) H20
Traverse
point
number
Sampling
time,
(6), min
Total
Clock
time,
(24 h)
Vacuum,
mm
(in.) Hg
Max
Stack
tempera-
ture
(TJ,
°C(6F)
Avg
Velocity
head
(AP.),
mm
(in.) H20
Pressure
differ-
ential
across
orifice
meter (AH),
mm
(in.) H20
Gas sample
volume (V ),
•» (ft*)"1
-
Total
Gas sample temp-
erature at dry
gas meter
Inlet,
°C(°F)
Avg
Outlet,
°C(°F)
Avg
Temp
of gas
leaving
condenser
or last
impinger,
°C (8F)
Max
Filter
temp,
°C(°F)
Quality Assurance Handbook M5-4.2
-------
SAMPLE RECOVERY AND INTEGRITY DATA FORM
Plant Sample date
Sample location Run number
Sample recovery person Recovery date
MOISTURE
Impingers Silica gel
Final volume (wt) ml (g) Final wt g g
Initial volume (wt) ml (g) Initial wt g g
Net volume (wt) ml (g) Net wt g g
Total moisture g
Color of silica gel
Description of impinger water
RECOVERED SAMPLE
Water rinse and
impinger contents Liquid level
container number marked?
Water blank Liquid level
container number marked?
Samples stored and locked?
Remarks
Date of laboratory custody
Laboratory personnel taking custody
Remarks
Quality Assurance Handbook M5-4.3
-------
EXAMPLE OF A SAMPLE LABEL
Plant City
Site Sample type
Date Run number
Front rinse d Front filter D Front solution D
Back rinse D Back filter D Back solution D
Solution Level marked
• •
Volume: Initial Final _£
1 "" ' , t.
Clean up by fj
" " ce.
Quality Assurance Handbook M5-4.4
-------
POSTTEST CALIBRATION CHECKS
Plant Calibrated by
Meter box number Date
Dry Gas Meter
Pretest calibration factor, Y (within ±2%)
Posttest check, Y* ; (within ±5% of pretest)
Recalibration required? yes no
If yes, recalibration factor, Y (within ±2%)
Lower calibration factor, Y for calculations (pretest or
posttest)
Dry Gas Meter Thermometers
Was a pretest temperature correction used? _T yes no
If yes, temperature correction (within ±3°C (5.4°F) over
range)
Posttest comparison with mercury-in-glass thermometer?* (within
±6°C (10.8°F) at ambient temperature)
Recalibration required? yes _ no
Recalibration temperature correction?~ (within ±3°C
(5.4°F) over range)*
If yes, no correction necessary for calculations 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? yes no
If yes, temperature correction °C (°F) (within ±1.5% of
readings in K (°R) over range)
Average stack temperature of compliance test, T ^K (°R)
Temperature of reference thermometer or solution for recalib'ra-
tion K (°R)* (within ±10% of T )
Temperature of stack thermometer for recalibration K (°R)
Difference between reference and stack thermometer temperatures,
AT K (°R)
Do values agree within ±1.5%?* yes no
If yes, no correction necessary for calculations
If no, calculations 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 result values must be reported since there issno way
to determine which is correct
(continued)
Quality Assurance Handbook M5-5.1
-------
(continued)
Barometer
Was the pretest field barometer reading correct? yes no
Posttest comparison?* mm (in.) Hg (±2.5 mm (0.1 in.) Hg)
Was calibration required? yes no
If yes, no correction necessary for calculations when the field
barometer has a lower reading; if the mercury-in-glass reading
is lower, subtract the difference from the field data readings
for the calculation
*Most significant items/parameters to be checked.
-------
Plant
FLUORIDE ANALYTICAL DATA SHEET
Date
yes
Sample location
Samples identifiable
Ambient temperature
Temperature of calibration standards
Temperature of samples
Analyst
no All liquid levels at marks
Constant temperature bath used
Date calibration standards prepared
yes
yes
no
no
Sample
number
Sample
identification
number
Total
volume of
sample,
(Vt), ml
Aliquot
total sam-
ple added
to still
(At), ml
Diluted
volume of
distillate
collected
(Vd), ml
Electrode
potential ,
mV
Concentration
of fluoride
from cali-
bration curve,
(M), molarity
Total
weight of
fluoride
in sample
(Ft), mg
Total weight of fluoride in sample (F.)
V,
Ft =
t.
Signature of analyst
Remarks:
Signature of reviewer or supervisor
Quality Assurance Handbook M5-5.2
-------
EXPANDED CALIBRATION CURVE DATA FORM
LABORATORY WORKSHEET
Date
Date standards prepared _
Temperature of standards
Electrode number
Standard number
1
2
3
4
5
Control sample
Concentration, M
0.001
0.0005
0.0001
0.00005
0.00001
tote: The control sample, from the calibral
O002M and 0.0003M.
Electrode potential, mV
.ion curve, must be between
Signature of analyst
Signature of reviewer
Quality Assurance Handbook M5-5.4
-------
SAMPLE VOLUME (ENGLISH UNITS)
Vm = _ _ • ft3, Tm = . _ °R, Pbar =__.__ in. Hg
Y = _. , AH = _ . in. H20
Pbar+ (AH/13.6) 3
.^x = 17.64 V Y Dar T = . ftJ
m(std) m T
Equation 6-1
FLUORIDE CONTENT IN SAMPLE
V,_ = ml, A,. = ml, V. = .ml
U — —» — — — •£ — — — — Q __ — — _
M = _. M
c V, V ,M f.
F. = 4.19 x 10"3 ^. u = _ . x 10"° Ib Equation 6-4
r At
CONCENTRATION OF FLUORIDE (ENGLIGH UNITS)
Vstd) '--• ft». Ft • _ . x 10-6 Ib
Fyj = _ . x io"6 Ib
F — F
C =35.31 -| — = . Ib/dscf Equation 6-5
s vm(std) ~
All other equations same as Methods 2 and 5.
Quality Assurance Handbook M5-6.1A
-------
SAMPLE VOLUME (METRIC UNITS)
m _ . --- m>, Tm = ___ . _ "K, Pbar = ___ . _ mm Hg
V = >
Y = _ . ___ , AH = __ . _mmH20
Phar+ (AH/13.6) ,
Vm(std) = °-3858 Vm Y T - " - • ___ m Equation 6-1
ffi
FLUORIDE CONTENT IN SAMPLE
Vt = . _ml, A. = . _ml, V, = . _ml
M = _. M
Vt Vd
F. = 19 —T— M = mg Equation 6-4
-
CONCENTRATION OF FLUORIDE (METRIC UNITS)
Vm(std) = - ' dscm' Ft = - • ' Ftb = - '
Ft - F^
C = -s= = _ . mg/dscm Equation 6-5
5 vm(std)
All other equations same as Methods 2 and 5.
Quality Assurance Handbook M5-6.1B
-------
Section No. 3 .1-0
Revision No. 0
Date January 4, 1982
Page 1 of 7
Section 3.10
METHOD 13A - DETERMINATION OF TOTAL FLUORIDE
EMISSIONS FROM STATIONARY SOURCES
(SPADNS Zirconium Lake Method)
OUTLINE
Number of
Section. Documentation pages
SUMMARY 3.10 2
METHOD HIGHLIGHTS 3.10 4
METHOD DESCRIPTION
1. PROCUREMENT OF APPARATUS
AND SUPPLIES 3.10.1 13
2. CALIBRATION OF APPARATUS 3.10.2 5
3. PRESAMPLING OPERATIONS 3.10.3 3
4. ON-SITE MEASUREMENTS 3.10.4 3
5. POSTSAMPLING OPERATIONS 3.10.5 18
6. CALCULATIONS 3.10.6 7
7. MAINTENANCE 3.10.7 2
8. AUDITING PROCEDURES 3.10.8 1
9. RECOMMENDED STANDARDS FOR
ESTABLISHING TRACEABILITY 3.10.9 1
10. REFERENCE METHOD 3.10.10 5
11. REFERENCES 3.10.11 1
12. DATA FORMS 3.10.12 6
-------
Section No. 3.10
Revision No. 0
Date January 4, 1982
Page 2 of 7
SUMMARY
..:. ' ~-\ .
In Method 13A, total fluorides (gaseous and particulate)
are extracted isokinetically from the source by using a sampling
train similar to the one specified in Method 5 (Section 3.4 of
this Handbook). The filter is not required to be heated and may
be located immediately after the probe or between the third and
fourth impinger.
The SPADNS zirconium lake colorimetrie method for quantita-
tively measuring the fluorides collected in the train is appli-
cable to fluoride (F) emissions from stationary sources, but not
to fluorocarbons such as Freon. The concentration range of the
method is from 0.05 to 1.4 pg F/ml; the method is applicable to
much higher concentration by using sample dilutions. Sensitiv-
ity of the method has not been determined.
An interferent in the collection of fluorides is grease on
sample-exposed surfaces; due to adsorption the grease causes low
results. If it can be shown to the satisfaction of the admini-
strator that samples contain only water soluble fluorides,
fusion and distillation may be omitted from the analysis.
Interferences, such as >300 mg aluminium/2 and >0.3 mg
silicon dioxide/2, prevent complete recovery of fluoride during
laboratory analysis, however, sample distillation will eliminate
this problem. Chloride will distill over and interfere with the
SPADNS zirconium lake color reaction. This interference can be
prevented by adding silver sulfate (5 mg of silver sulfate/mg of
chloride) into the distillation flask. However, if chloride ion
is present, use of specific-ion electrode (Method 13B) is recom-
mended. Sulfuric acid carried over during distillation will
cause a positive interference; to avoid the carryover, stop the
distillation at 175°C (347°F). Residual chlorine will also
interfere with this colorimetric method, but should not be
present in the type of sample analyzed.
-------
Section No. 3.10
Revision No. 0
Date January 4, 1982
Page 3 of 7
The color obtained when colorimetric reagent is mixed with
the sample is stable for approximately 2 h. After formation of
the color, the absorbances of the sample and standard solutions
should be measured at the same temperature. A 3°C (5.4°F) dif-
ference between sample and standard solution temperatures will
produce an error of approximately 0.005 mg F/2.
The method description which follows is based on the Refer-
ence Method1 that was promulgated on June 20, 1980.
Section 3.10.10 contains a copy of the Reference Method and
blank data forms are provided in Section 3.10.12 for the conve-
nience of the Handbook user.
Note; Due to similarities between Method 13A and Method 13B
sampling and analytical equipment and procedures, only the
differences pertaining to Method 13A will be presented. How.-
e\ter, the activity matrices are all included whether or not
differences occur in the written descriptions. All other Method
13A descriptions will be referenced to the corresponding de-
scription in Section 3.9, Method 13B. This is done for both
time savings to the reader and cost savings to the Government.
-------
Section No. 3.10
Revision No. 0 '
Date January 4, 1982
Page 4 of 7
METHOD HIGHLIGHTS
Section 3.10 (Method 13A) describes specifications for the
sampling and analysis of total fluoride emissions from station-
ary sources. A gas sample is isokinetically extracted from the
source stream, and the fluorides in the stream are collected in
the sampling train.
The sampling train is similar to that in EPA Method 5, with
a few exceptions—the filter does not have to be heated and it
may be located either immediately after the probe or between the
third and fourth impingers. If it is between the probe and the
first impinger, a borosilicate glass or stainless steel filter
holder with a 20-mesh stainless steel screen filter support and
• *
a silicone rubber gasket must be used. If it is between the
third and fourth impingers, a glass frit filter support may be
used.
Sampling is generally the same as in Method 5, but a nozzle
size that will maintain an isokinetic sampling rate of <28 2/min
(<1.0 ft3/min) must be used. Samples and standards must be the
same temperature during analysis by the colorimetric method. A
change of 3°C (5.4°F) will cause an error of 0.005 mg F/£ in the
sample measurements. Distillation during sample analysis has
been found to be the main cause of error in this method.
The collected sample is recovered by transferring the mea-
sured condensate and impinger water to a sample container,
adding the filter and the rinsings of all sample-exposed sur-
faces to this container, and fusing and distilling the sample
for colorimetric analysis. Fusion and distillation may be
omitted if it can be shown to the satisfaction of the adminis-
trator that the samples contain only water soluble fluorides.
Results of collaborative tests2 show that fluoride concen-
trations from 0.1 to 1.4 mg F/m3 could be determined with an in-
tralaboratory precision of 0.044 mg F/m3 and an interlaboratory
-------
Section No. 3.10
Revision No. 0
Date January 4, 1982
Page 5 of 7
precision of 0.064 mg F/m3. Six contractors each simultaneously
took duplicate samples from the stack. The collaborative test
did not find any bias in the analytical method.2
The Method Description (Sections 3.10.1 to 3.10.9) is based
on the detailed specifications in the Reference Method (Section
3.10.10) promulgated by EPA on June 20, 1980.*
The appropriate blank data forms at the end of the Method
Highlights Section of Method '13B (Section 3.9) may be removed
from the Handbook and used in the pretest, test, and posttest
operations. Each form has a subtitle to assist the user in
finding a similar filled-in form in the method description. On
the blank and filled-in forms, the items/parameters that can
cause the most significant errors are designated with an as-
terisk.
1% Procurement of Apparatus and Supplies
Section 3.10.1 (Procurement of Apparatus and Supplies)
gives specifications, criteria, and design features for the
required equipment and materials. The sampling apparatus for
Method 13A has the same design features as that of Method 5,
except for the positioning of the filter in the sampling train.
This section can be used as a guide for procurement and initial
checks of 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 3.10.2 (Calibration of Apparatus) describes the
required calibration procedures for the Method 13A sampling
equipment (same* as Method 13B) for the colorimetric method. A
pretest checklist (Figure 3.1 in Section 3.9.3 or a similar
form) should be used to summarize the calibration and other
pertinent pretest data.
Section 3.10.3 (Presampling Operations) is the same as for
Method 13B.
-------
Section No. 3.10
Revision No. 0 •
Date January 4, 1982
Page 6 of 7
Activity matrices for the calibration of equipment and the
presampling operations (Tables 2.1 and 3.1) summarize the activ-
ities. . ,, . . . : . . . . .-'•...
3. On-site Measurements
Section 3.10.4 (On-Site Measurements) describes procedures
for sampling and sample recovery and is the same as for Method
13B.
4. Posttest Operations
Section 3.10.5 (Postsampling Operation) describes the
postsampling activities for checking the equipment and the
analytical procedures. A form is given for recording data from
the posttest equipment calibration checks; a copy of the form
should be included in the emission test final report. A control
sample of known (F) concentration should be analyzed before
analyzing the sample for a quality control check on the analyt-
ical procedures. The detailed analytical procedures can be
removed for use as easy references in the laboratory. An activ-
ity matrix (Table 5.1) summarizes the postsampling operations.
Section 3.10.6 (Calculations) describes calculations,
nomenclature, and significant digits for the data reduction. A
programmed calculator is recommended to reduce calculation
errors.
Section 3.10.7 (Maintenance) recommends routine and preven-
tive maintenance programs. The programs are not required, but
their use should reduce equipment downtime.
5. Auditing Procedures
Section 3.J.0.8 describes performance and system audits.
Performance audits for both the analytical phase and the data
processing are described. A checklist (Figure 8.2) outlines a
recommended system audit.
Section 3.10.9 lists the primary standards to which the
working standards or calibration standards should be traceable.
-------
Section No. 3.10
Revision No. 0
Date January 4, 1982
Page 7 of 7
6. References
Section 3.10.10 contains the promulgated Reference Method;
Section 3.10.11 contains the references cited throughout the
text; and Section 3.10.12 either contains copies of data forms
recommended for Method 13A or references the user to forms in
Method 13B.
-------
Section No. 3.10.1
Revision No. 0
Date January 4, 1982
Page 1 of 13
METHOD DESCRIPTION
1.0 PROCUREMENT OF APPARATUS AND SUPPLIES
A schematic of the sampling train used in Method 13 is
shown in Figure 1.1. The train and the sampling procedures are
similar to EPA Method 5; the procedures and equipment for
Methods 13A and 13B are identical. Commercial models of the
train are available. For those who want to build their own/
construction details are in APTD-0581;3 allowable modifications
are described therein. The operating, maintenance, and calibra-
tion procedures for the sampling train are in APTD-0576.4 Since
correct usage is important in obtaining valid results, all users
are advised to read that document and to adopt its procedures
unless alternatives are outlined therein.
Specifications, criteria, and/or design features are given
in this section to aid in the selection of equipment or any
components that are different from those in Section 3.9.1.
Procedures and limits (where applicable) for acceptance checks
are also given.
Table 1.1 at the end of this section summarizes the quality
assurance activities for the procurement and acceptance of
apparatus and supplies.
1.1 Miscellaneous Glassware
1.1.1 Pipettes - Several volumetric pipettes (Class A)—includ-
"i
ing 2, 4, 5, 6, 8, 10, 12, 14, 20, 25, 50 mi's—should be avail-
able. Record the stock numbers, and visually check for cracks,
breaks, or manufacturer's flaws. If irregularities are found,
either replace or return to the supplier.
1.1.2 Volumetric Flask - Several glass volumetric flasks, Class
A, (50-ml, 100-ml, 250-ml, 1000-ml) are needed to dilute the
sample and to prepare standards and agents.
-------
1.9-2.5 cm
(0.75-1.0 in.)
1.8 cm(0.75 In.)
PITOT TUBE
TEMPERATURE
7 SENSOR
THERMOMETER
CHECK
VALVE
TYPE S C
PITOT TUBE
, OPTIONAL .
FILTER HOLDER'
LOCATION
,iu o- ii
IMPINGERS
THERMOMETERS
ORIFICE
MANOMETER
AIR TIGHT
PUMP
DRY TEST
METER
Figure 1.1. Fluoride sampling train.
VACUUM
LINE
*x< O 5d to
P> P> C| H-O
Oi O 3
O 3 3
"»? «*
n» \is. o
M h O •
, •**• o •
' M
O
M .
VO M
00
-------
Section No. 3.10.1
Revision No. 0
Date January 4, 1982
Page 3 of 13
1.1.3 Erlenmeyer Flask or Plastic Bottle - A 500-ml Erlenmeyer
flask or plastic bottle is needed to store the SPADNS solution.
1.2 Reagents and Supplies (Sample Recovery and Analysis)
Unless otherwise indicated, all reagents should meet the
specifications of the Committee on Analytical Reagents of the
American Chemical Society (ACS); otherwise, use the best avail-
able grade.
1.2.1 Calcium Oxide (CaO) - A reagent grade 'or a certified ACS
grade of CaO containing <_0.005% F is needed.
1.2.2 Filters - Whatman No. 541 (or equivalent) filters are re-
quired for filtration of the impinger contents and recovery of
the sample.
1.2.3 Hydrochloric Acid (HC1) - An ACS reagent grade or the
equivalent concentrated HC1 is needed.
1.2.4 Phenolphthalein Indicator - A reagent grade or a certi-
fied ACS 0.1% phenolphthalein should be a 1:1 ethanol-water
mixture.
1.2.5 Silver Sulfate (Ag^SC^) - An ACS reagent grade or the
equivalent Ag2S04 should be used.
1.2.6 Sodium Hydroxide (NaOH) Pellets - An ACS reagent grade or
the equivalent is needed,
1.2.7 Sodium Fluoride (NaF) Standard - Dissolve 0.2210 g
±0.0005 g of reagent grade NaF in deionized distilled water and
dilute to 1000 ml. Dilute 100 ml of this solution to 1000 ml
with distilled water; 0.01 mg F/ml water. NaF should be oven
dried at 110°C for at least 2 h prior to weighing.
1.2.8 Sulfuric Acid (H^SO^) - An ACS reagent grade or the
equivalent concentrated H2S04 is needed.
1.2.9 Sulfuric Acid, 25 Percent (v/v) - Cautiously add 1 part
of concentrated H2S04 to 3 parts deionized distilled water.
-------
Section No. 3.10.1
Revision No. 0
Date January 4, 1982
Page 4 of 13
1.2.10 Water - Deionized distilled water needed as specified in
Table, 1.1 at the end of this section and in Section 3.9.1.
1.2.11 SPADNS Solution - Dissolve 0.960 ±0.010 g of SPADNS rea-
gent 4,5 dihydroxy-3-(parasulfophenylazo)-2,7-naphthalenedisul-
fonic acid trisodium salt (also called sodium-2-(parasulfo-
phenylazo)-l,8-dihydroxy-3,6-naphthalenedisulfonate) in dis-
tilled .water, and dilute to 500 ml. This diluted solution is
stable for about 1 mo if stored in a sealed bottle and protected
from direct sunlight. .
1.6.12 Reference Solution - Add 10 ml of the SPADNS solution'to
100 ml distilled water. Dilute 7 ml of concentrated HCl to 10
ml; then add the diluted HCl to the diluted SPADNS. This refer-
ence solution, which is needed to set the spectrophotometer zero
point, is stable for at least 2 mo. :
1.2.13 SPADNS Mixed Reagent (2rOClg • 8H?0 + HCl Mixed with
SPADNS Solution) - First prepare the zirconyl-acid reagent by
dissolving 0.135 ±0.005 g of zirconyl chloride octahydrate
(ZrOCl2'8H20) in 25 ml of distilled water. Then add 350 ml of
concentrated HCl, and dilute to 500 'ml with distilled water.
Next, prepare the SPADNS mixed reagent (.acid, zirconyl-SPADNS
solution) by combining egual volumes of the SPADNS solution and
the zirconyl-acid reagent. The mixed reagent will be stable for
at least 2 mo. ,
Check all reagents for grades, and ACS .certifications.
Replace or return to the manufacturer any reagent which does, not
meet the standards.
1.3 Analytical Equipment
• ;
1.3.1 Bunsen Burner - A Bunsen burner capable of distilling 200
ml in <15 min is required to heat the boiling flasks.
1.3.2 Crucible - A nickel crucible with a capacity of 75 to
100 ml is needed to evaporate the water from the sample on a hot
plate.
-------
Section No. 3.10.1
Revision No. 0
Date January 4, 1982
Page 5 of 13
Upon receipt, check for cracks or manufacturing flaws as
well as for capacity. If it does not meet specifications re-
place or return it to the manufacturer.
1.3.3 Hot Plate - A hot plate capable of 500°C (932°F) is re-
quired for heating the sample in a nickel crucible.
Check upon receipt and before each use for damage. Check
the heating capacity against a mercury-in-glass thermometer. If
inadequate, repair or return the hot plate to the supplier.
1.3.4 Electric Muffle Furnace - An electric muffle furnace
capable of heating to 600°C (1112°F) is needed to fuse the sam-
ple.
Check the heating capacity against a mercury-in-glass ther-
mometer. Replace or return to the manufacturer any unit which
does not meet specifications.
1.-3.5 Balance - A balance with a capacity of 300 g ±0.5 g is
needed to determine moisture.
Check for damage against a series of standard weights upon
receipt and before each use. Replace or return to the manufac-
turer if damaged or if it does not meet specifications.
1.3.6 Analytical Balance - An analytical balance capable of
weighing to within 0.1 mg is needed for preparation of the stan-
dard fluoride solution and the analytical reagents. Check the
balance frequently with Class S weights.
1.3.7 Constant Temperature Bath - For optimum measurement of
the sample concentration, a water bath is needed to maintain a
constant room temperature. This bath must maintain a constant
temperature of ±1°C (1.8°F) in the room temperature range.
Check upon* receipt and before each use for damage and tem-
perature constancy.
1.3.8 Spectrophotometer - A spectrophotometer is required for
determining the absorbance of the sample and the calibration
standards at a wavelength of 570 nanometers using a 1-cm path-
length.
-------
Section No. 3.10.1
Revision No. 0
Date January 4, 1982
Page 6 of 13 '
Check the spectrophotometer upon receipt and before each
use for proper operation according to the manufacturer's manual.
1.3.9 Spectrophotometer Cells - Glass cuvettes with 1-cm path-
length are required to contain sample and standards during the
absorbance measurements. Check upon receipt and before each use
for cracks or scratches on optical surfaces. Replace the cuvet-
tes necessary.
-------
Section No. 3.10.1
Revision No. 0
Date January 4, 1982
Page 7 of 13
TABLE 1.1. ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS
AND SUPPLIES
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sampling
Probe liner
Specified material of
construction; equipped
with heating system
capable of maintaining
120°±14°C (248° ±25°F)
at the exit
Visually check the
probe and run the
heating system
Repair, return
to supplier,
or reject
Probe nozzle
Stainless steel (316)
with sharp, tapered
angle <30°; differ-
ence iri measured diam-
eters <0.1 mm (0.004
in.); no nicks, dents,
or corrosion
Visually check upon
receipt and before
each test; use a mi-
crometer to measure
ID before field use
after each repair
Reshape and
sharpen, re-
turn to the
supplier, or
reject
Pi tot tube
Type S (Meth 2, Sec
3.1.2); attached to
probe with impact
(high pressure) opening
plane even with or
above nozzle entry
plane
Visually check for
vertical and hori-
zontal tip alignments;
check the configura-
tion and the clear-
ances; calibrate
(Sec 3.9.2)
Repair or re-
turn to sup-
plier
Differential
pressure
gauge (in-
clined ma-
nometer)
Meets criteria (Sec
3.1.2); agrees within
5% of gauge-oil
manometer
Check against a gauge-
oil manometer at a
minimum of three
points: 0.64(0.025);
12.7 (0.5); 25,4(1.0)
mm (in.) H20
As above
Filters
Capable of withstand-
ing temperatures to
135°C (275°F), 95%
collection efficiency
for 0.3 urn particles,
low F blank (<0.015
mg F/cm2)
Check each batch for
F blank values,
visibly inspect for
pin holes or flaws
Reject batch
(continued)
-------
Section No. 3.10.1
Revision So. 0
Date January 4, 1982
Page 8 of 13
TABLE 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Filter holder
Leak free; borosilicate
glass
Visually check before
use
Return to
supplier
Condenser
Four impingers, standard
stock glass; pressure
drop not excessive
Visually check upon
receipt; check pres-
sure drop
As above
Vacuum gauge
0-760 mm (0-30 in.) Hg,
±25 mm (1 in.) at
380 mm (15 in.) Hg
Check against mer-
cury U-tube manometer
upon receipt
Adjust or re-
turn to sup-
plier
Vacuum pump
Leak free; capable of
maintaining flow rate
of 0.02-0.03 mVmin
(0.7 to 1.1 ftVmin)
for pump inlet vacuum
of 380 mm (15 in.) Hg
Check upon receipt
for leaks and capaci-
ty
Repair or re-
turn to sup-
plier
Barometer
Capable of measuring
atmospheric pressure
±2.5 mm (0.1 in.) Hg
Check against a mer-
cury-in-glass barom-
eter or equivalent;
calibrate (Sec 3.1.2)
Determine cor-
rection fac-
tor, or reject
if difference
more than ±2.5
mm (0.1 in.)
Hg
Orifice meter
AH@ of 46.74± 6.35 mm
(1.84 ± 0.25 in.) H20
at 20°C (68°F);
optional
Upon receipt, visual-
ly check for damage;
calibrate against wet
test meter
Repair or re-
turn to sup-
plier
Dry gas meter
Capable of measuring
volume within ±2% at a
flow rate of 0.02
mVmin (0.7 ftVmin)
Check for damage upon
receipt and calibrate
(Sec 3.9.2) against
wet test meter
Reject if dam-
aged, behaves
erratically,
or cannot be
properly ad-
justed
(continued)
-------
Section No. 3.10.1
Revision No. 0
Date January 4, 1982
Page 9 of 13
TABLE 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Thermometers
±1°C (2°F) of true
value in the range of
0° to 25°C (32° to 77°F)
for impinger thermometer
and ±3°C (5.4°F) of true
value in the range of
0°C to 90°C (32° to
194°F) for dry gas
meter thermometers
Check upon receipt
for dents or bent
stem, and calibrate
(Sec 3.9.2) against
mercury-in-glass
thermometer
Reject if un-
able to cali-
brate
Sample Recovery
Probe liner and
probe nozzle
brushes
Nylon bristles with
stainless steel han-
dles; properly sized
and shaped
Visually check for
damage upon receipt
Replace or re-
turn to sup-
plier
Wash bottles
Polyethylene or glass,
500 ml
Visually check for
damage upon receipt
As above
Storage con-
tai ner
High-density polyeth-
ylene, 1000 ml
Visually check for
damage upon receipt;
be sure caps make
proper seals
As above
Graduated
cylinder
Glass, Class A, 250 ml
Upon receipt, check
for stock number,
cracks, breaks, and
manufacturer flaws
As above
Funnel
Glass, diameter 100 ram;
stem length 100 mm
Visually check for
damage upon receipt
As above
Rubber police-
Properly sized
man
Visually check for
damage upon receipt
As above
(continued)
-------
TABLE 1.1 (continued)
Section No. 3.10.1
Revision No. 0'
Date January 4, 1982
Page 10 of 13•
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Pipettes, volu-
metric flask,
beaker, flask
adapter, con-
denser, con-
nection tube,
Erlenmeyer
flask
Glass, Class A
Upon receipt, check
for stock number,
cracks, breaks and
manufacturer flaws
Replace or re-
turn to sup-
plier
Pi sti nation
Apparatus
Bunsen burner
Capable of distilling
220 ml in <15 min
Visually check upon
receipt; check heat-
ing capacity, check
for damage
Replace or re-
turn to manu-
facturer
Crucible
Nickel material; 75-
100 ml
Check upon receipt
for cracks or flaws
Replace or re-
turn to manu-
facturer
Analytical
Equipment"
Hot plate
Heating capacity of
500°C (932°F>
Check upon receipt
and before each use
for damage; check
heating capacity
against mercury-in-
glass thermometer
Replace or re-
turn to manu-
facturer
Electric muffle
furnace
Heating capacity of
600°C
Check upon receipt
and before each use
for damage; check
heating capacity
upon receipt against
mercury-in-glass
thermometer
Replace or re-
turn to manu-
facturer
(continued)
-------
Section No. 3.10.1
Revision No. 0
Date January 4, 1982
Page 11 of 13
TABLE 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Balance
Capacity of 300 g ±0.5g
Check for damage and
against series of
standard weights upon
receipt and before
each use
Replace or re-
turn to manu-
facturer
Water bath
Capable of maintaining
constant room tempera-
ture
Check with mercury-
in-glass thermometer
Repair
Spectropho-
tometer
Capable of measuring
absorbance at 570 nm
and providing >1 cm
light path
Check upon receipt
and before each use
for damage; see manu-
facturers' operating
manual
Replace or re-
turn to manu-
facturer
Reagents
Filters
Whatman No. 541 or
equivalent
Visually check for
damage upon receipt
Replace or re-
turn to sup-
plier
Silica gel
Indicating Type 6-16
mesh
Upon receipt check
label for grade or
certification"
Replace or re-
turn to manu-
facturer
Distilled water
Must conform to ASTM-
D1193-74, Type 3
Check each lot
Replace or re-
turn to manu-
facturer
Crushed ice
Check frozen condition
Stopcock grease
Acetone insoluble, and
heat stable silicon
grease
Upon receipt, check
label for grade or
certification
As above
(continued)
-------
Section No. 3.10.1
Revision No. 0-
Date January 4, 1982
Page 12 of 13 -
TABLE 1.1 (continued)
Apparatus
Reagents
Calcium oxide
powder
Phenolphthalein
Sodium hy-
droxide
Sulfuric acid
Silver sulfate
powder
Hydrochloric
acid
Sodium fluoride
solution
SPADNS solu-
tion
Acceptance limits
Reagent grade or cer-
tified ACS
0.1* in 1:1 ethanol-
water mixture; reagent
grade or certified ACS
NaOH pellet, 5M NaOH
reagent grade or cer-
tified ACS
Concentrated, reagent
grade or certified ACS;
25% (v/v) reagent grade
or ACS
Reagent grade or certi-
fied ACS
Concentrated, reagent
grade or certified ACS
0.01 mg F/ml , reagent
grade or certified ACS
Dissolve 0.960 + 0.010
g of SPADNS reagent,
4,5-dihydroxy-3-(p-
sulfophenylazo)-2,7-
naphthal enedi sul f oni c
acid tri sodium salt,
reagent grade or cer-
tified ACS
Frequency and method
of measurements
As above
As above
As above
As above
Upon receipt, check
label for grade or
certification
As above
As above
As above
Action if
requirements
are not met
As above
As above
As above
As above
Replace or re-
turn to manu-
facturer
As above
As above
As above
(continued)
-------
Section No. 3.10.1
Revision No. 0
Date January 4, 1982
Page 13 of 13
TABLE 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Reference
solution
Add 10 ml SPADNS solu-
tion to 100 ml dis-
tilled water; dilute
7 ml cone HC1 to 10
ml with distilled
water; add to diluted
SPADNS solution; rea-
gent grade or certi-
fied ACS
As above
As above
SPADNS mixed
reagent
Dissolve 0.135 + 0.005
g [ZrOCl2-8H20] in 25
ml distilled water; add
350 ml cone HC1; dilute
to 500 ml with distilled
water; mix equal volumes
of SPADNS solution and
the above zirconyl acid
reagent; reagent grade
or certified ACS
As above
As above
-------
Section No. 3.10.2
Revision No. 0
Date January 4, 1982
Page 1 of 5
2.0 CALIBRATION OF APPARATUS
Calibration of apparatus is one of the most important func-
tions in maintaining data quality. The detailed calibration
procedures included in this section are designed for the equip-
ment specified in Method 13A and described in the previous
section (Section 3.9.2). A laboratory log book of all cali-
brations must be maintained. Table 2.1 at the end of this
section summarizes the quality assurance activities for cali-
bration. This section is the same as Method 13B (Section 3.9.2)
with the exception of the calibration of the spectrophotometer
as detailed below.
2.1 Spectrophotometer
An initial calibration curve should be made to check the
operation of the spectrophotometer. Conduct the check as fol-
lows:
1. Prepare the blank standard by adding 10 ml of SPADNS
mixed reagent to 50 ml of distilled water.
2. Pipette 2.0, 4.0, 6.0, 8.0, 10.0, 12.0, and 14.0 ml of
the standard fluoride working solution into separate 100-ml
volumetric flasks. Dilute to the mark with distilled water.
3. Pipette 50 ml of each dilution into 100-ml beakers;
then pipette 10.0 ml of SPADNS mixed reagent into each and mix.
These standards will contain 0, 10, 20, 30, 40, 50, 60, and 70
pg F, respectively.
4. Place the reference standards and the reference solu-
tion in a constant temperature bath for 30 min before reading
the absorbances with the spectrophotometer. The bath must be
within ±3°C (5.4°F) of ambient temperature.
5. Set the spectrophotometer at 570 nm and use the refer-
ence solution to set at zero absorbance.
6. Determine the absorbance of the standards. Record
data on the standard data form as shown in Figure 2.1.
-------
Section No. 3.10.2
Revision No. 0
Date January 4, 1982
Page 2 of 5
Spectrophotometer number 3— /00
Calibration date ^f J/JJ#O
Analyst
SPADNS mix date
Ambient temperature
Spectrophotometer set at 570 nm
_°C Bath temperature
yes
J. /
Reference solution used to set zero absorbance
_ 10 ug <£>
Absorbance readings:
40 M9
50 ug
60 ug
10
Signature of Analyst
Signature of Reviewer
yes
°C
no
no
20 ug
70 ug
30 ug
blank
20 30 40 50
ug of fluoride per 50 ml
/L
60
70
iJ s
0-.
Figure 2.1. Fluoride calibration curve.
-------
Section No. 3.10.2
Revision No. 0
Date January 4, 1982
Page 3 of 5
7. The wavelength calibration should be checked initially
and yearly thereafter. This can be done using a didymium fil-
ter. See suppliers instructions for its use. The wavelength
should agree within ±10 nm. If not, contact the manufacturer's
representative for adjustment.
-------
Section No. 3.10.2
Revision No
Date January 4, 1982
Page 4 of 5
TABLE 2.1. ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Wet test meter
Capacity of >3.4 m3/h
(120 ft3/h);~accuracy
within ±1.0%
Calibrate initially
and yearly by liquid
displacement
Adjust to
meet specifi-
cations, or
return to
manufacturer
Dry gas meter
Y. = Y ± 0.02 Y at
flow rate of 0.02 •
0.03 mVmin (0.7 -
1.1 ftVmin)
Calibrate with wet
test meter initially
to agree within Y ±
0.02 Y and when post-
test check is not
within Y ± 0.05 Y
Repair or re-
place, and
then recali-
brate
Thermometers
Impinger thermometer
+1°C (2bF); dry gas
meter thermometer
+3°C (5.4°F) over
applicable range
Calibrate each ini-
tially against a
mercury-in-glass
thermometer; before
field trip compare
each with mercury-
in-glass thermometer
Adjust, de-
termine a
constant cor-
rection fac-
tor, or re-
ject
Barometer
+2.5 mm (0.1 in.) Hg of
mercury-in-glass barom-
eter
Calibrate initially
vs mercury-in-glass
barometer; check
before and after
each field test
Adjust to
agree with
certified
barometer
Probe nozzle
Average three ID mea-
surements of nozzle;
difference between high
and low <0.1 mm
(0.004 in.)
Use a micrometer to
measure to near-
est 0.025 mm (0.001
in.)
Recalibrate,
reshape, and
sharpen when
nozzle be-
comes nicked,
dented, or
corroded
(continued)
-------
Section No. 3.10.2
Revision No. 0
Date January 4, 1982
Page 5 of 5
TABLE 2.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Stack tempera-
ture sensor
±1.5% of average abso-
lute stack temperature,
°R
Calibrate initially;
check after each
field test
Adjust or
reject
Trip balance
Standard Class-S
weights within ±0.5 g
of stated value
Verify calibration
when first purchased,
any time moved or
subject to rough
handling, and during
routine operations
when not within
± 0.5 g
Have the
manufacturer
recalibrate
or adjust
Pi tot tube
Type S; initially
calibrated according to
Section 3.1, Meth 2;
tube tips undamaged
Visually check
before each field
test
Repair or
replace
Spectrophotom-
eter
Standard solutions
agree within ±2% of
calibration curve
Check standard solu-
tions for each test;
new calibration curve
made when standards
do not agree within
±2% of existing curve
or when SPADNS mixed
reagent is newly made
Make new rea-
gents and
calibration
curve
Wavelength
±10 nm
Yearly
Contact manu-
facturer 's
representa-
tive for
adjustment
-------
Section No. 3.10.3
Revision No. 0
Date January 4, 1982
Page 1 of 3
3.0 PRESAMPLING OPERATIONS
The quality assurance activities for presampling operations
are summarized in Table 3.1. See Section 3.0, of this Handbook
for details on preliminary site visits. This section is the
same as Method 13B (Section 3.9.3).
-------
Section No. 3.10.3
Revision No. 0••
Date January 4, 1982
Page 2 of 3
TABLE 3.1. ACTIVITY MATRIX FOR PRESAMPLING OPERATIONS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sampling train
probe and
nozzle
1. Probe, nozzle, and
liner free of contami-
nants; constructed of
borosilicate glass,
quartz, or equivalent;
metal liner must be
approved by admini-
strator
2. Probe leak free
at 380 mm (15 in.) Hg
3. Probe heating
system prevents mois-
ture condensation
1. Clean internally
by brushing with tap
water, deionized dis-
tilled water, and
acetone; air dry
before test
2. Visual-ly check
before test
3. Check heating
system initially and
when moisture cannot
be prevented during
testing (Sec 3.4.1)
1. Repeat
cleaning and
assembly pro-
cedures
2. Replace
3. Repair or
replace
Impingers,
filter
holders, and
glass con-
nectors
Clean; free of breaks
cracks, leaks, etc.
Clean with detergent,
tap water, and
deionized distilled
water
Repair or
discard
Pump
Sampling rate of 0.02-
0.03 m3/min (0.7 to
1.1 ftVmin) up to 380
mm (15 in.) Hg at pump
inlet
Service every 3 mo
or upon erratic be-
havior; check
oiler jars every 10
tests
Repair or re-
turn to manu-
facturer
Dry gas meter
Clean; readings ±2% of
of average calibration
factor
Calibrate according
to Sec 3.4.2; check
for excess oil
As above
(continued)
-------
Section No. 3.10.3
Revision No. 0
Date January 4, 1982
Page 3 of 3
TABLE 3.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Reagents and
Equipment
Filters
No irregularities,
flaws, pinhole leaks;
<0.015 mgF/cm2
Visually check before
testing; check each
lot of filters for F
content
Replace
Water
Deionized distilled
conforming to
ASTM-Oil93-74, Type 3
Run blank evapora-
tions before field
use to eliminate high
solids (only required
if impinger contents
to be analyzed)
Redistill or
replace
Stopcock grease
Acetone insoluble;
heat stable
Check label upon
receipt
Replace
Packing Equip-
ment for
Shipment
Probe
Rigid container lined
with polyethylene foam
Prior to each ship-
ment
Repack
Impingers, con-
nectors, and
assorted
glassware
Rigid container lined
with polyethylene foam
As above
As above
Pump
Sturdy case lined with
polyethylene foam ma-
terial if not part of
meter box
As above
As above
Meter box
Meter box case and/or
additional material to
protect train componr
ents; pack spare meter
box
As above
As above
Wash bottles
and storage
containers
Rigid foam-lined con-
tainer
As above
As above
-------
Section No. 3.10.4
Revision No. 0
Date January 4, 1982
Page 1 of 3
4.0 ON-SITE MEASUREMENTS
The on -site activities include transporting equipment to
the test site, unpacking and assembling the equipment, making
duct measurements, performing the velocity traverse, determining
molecular weights and stack gas moisture contents, sampling for
particulates, and recording the data. Table 4.1 summarizes the
quality assurance activities for on-site activities. Blank data
forms are in Sections 3.9.12 and 3.10.12 for the convenience of
the Handbook user. This section is the same as Method 13B
(Section 3.9.4).
-------
Section No. 3.10.4
Revision No. 0 .
Date January 4, 1982
Page 2 of 3
TABLE 4.1. ACTIVITY MATRIX FOR ON-SITE MEASUREMENT CHECKS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sampling
Filter
Centered in holder; no
breaks, damage, or con-
tamination during
loading
Use tweezers or surg-
ical gloves to load
Discard fil-
ter, and
reload
Condenser
(addition of
reagents)
100 ml of distilled
water in first two
impingers; 200-300 g
silica gel in fourth
impinger
of
Use graduated cylinder
to add water, or weigh
each impinger and its
contents to the near-
est 0.5 g
Reassemble
system
Assembling
samp!ing
train
1. Specifications
in Fig 1.1
2. Leak rate <4% of
sampling volume or
0.00057 mVmin (0.02
ft3/min), whichever is
less
1. Check specifica-
tions before each
sampling run
2. Leak check before
sampling by plugging
nozzle or inlet to
first impinger and
pulling a vacuum of
380 mm (15 in.j Hg
1. Reassem-
ble
2. Correct
the leak
Sampling
(isokineti-
cally)
1. Within ±10% of
isokinetic condition
and at a rate of less
than 1.0 ftVmin
2. Standard checked
for minimum sampling
time and volume; sam-
pling time >2 min
point
1. Calculate for
each sample run
2. Make a quick cal-
culation before test,
and exact calculation
after
1. Repeat
the test run
2. As above
(continued)
-------
TABLE 4.1 (continued)
Section No. 3.10.4
Revision No. 0
Date January 4, 1982
Page 3 of 3
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
3. Minimum number of
points specified by
Method 1
4. Leakage rate
<0.00057 mVmin (0.02
ftVmin) or 4% of the
average sampling vol-
ume, whichever is less
3. Check'before the
first test run by mea-
suring duct and using
Method 1
4. Leak check after
each test run or be-
fore equipment re-
placement during test
at the maximum vacuum
during the test (man-
datory)
3. Repeat
the procedure
to comply
with specifi-
cations of
Method 1
4. Correct
the sample
volume or re-
peat the sam-
pling
Sample recovery
Noncontaminated sample
Transfer sample to
labeled polyethylene
container after each
test run; mark level
of solution in the
container
Repeat the
sampling
Sample
logistics,
data collec-
tion, and
packing of
equipment
1. All data recorded
correctly
1. After each test
and before packing
1. Complete
the data
2. All equipment exam-
ined for damage and
labeled for shipment
3. All sample contain-
ers and blanks properly
labeled and packaged
2. As above
3. Visually check
after each sampling
2. Repeat
the sampling
if damage
occurred dur-
ing the test
3. Correct
when possible
-------
Section No. 3.10.5
Revision No. 0
Date January 4, 1982
Page 1 of 18
5.0 POSTSAMPLING OPERATIONS
The postsampling operations include checks on the apparatus
used in the field during sampling to measure volumes, tempera-
tures, and pressures, and analyses of the samples collected in
the field and forwarded to the base laboratory. Table 5.1 at
the end of this section summarizes the quality assurance activi-
ties for the postsampling operations.
The postsampling checks on the sample collection train are
the same as for Method 13B (Section 3.9.5). The analytical
method is different with exception of some of the sample prepa-
ration. The entire analytical procedure is detailed below.
5.1 Base Laboratory Analysis
All fluoride samples should be checked by the analyst upon
receipt in the base laboratory for identification and sample
integrity. Any losses should be noted on the analytical data
form (Figure 5.1). Either void the sample or correct the data
using a technique approved by the administrator. If a notice-
able amount of sample has been lost by leakage, the following
procedure may be used to correct the volume.
1. Mark the new level of the sample container.
2. Treat the sample as described in Subsection 5.2.3 and
note the final dilution volume (vsoin)-
3. Add water up to the initial mark on the container,
transfer the water to a graduated cylinder and record the ini-
tial sample volume (vsoin:; ) in milliliters.
4. Add water to the new mark on the container. Transfer
the water to a graduated cylinder, and record the final volume
(V , f) in milliliters.
5. Correct the volume by using the following equation:
V , = v Vsolni
soln soln V.,,, _
solnf
-------
Plant /i csn£ /-££".
Date 3/^o/8o
Samples identifiable " u^
Ambient temperature f23.°C
Sample was concentrated
TJ/t2£/4 Location /fA2/9#d
Analyst £e/5/n SPADNS mix date ^//s~/fO
yes no All liquid levels at mark *>-" yes
Temperature of samples ^?/'£ Temperature of standards J /
yes J/ no Solids fused and added to liquid L/* yes
no
•c
no
Sample
number
ftf=FA
flFc.
&FD&
AF-J
AFC.
Sample
identi-
fication
M/*?K *
•P-;lfsA
d'S /////
/OO
Absorb.
of sample
at 570 nm
OD
O. <5-<*S-
0. 480
O. 6,^0
o. aa$~
0. 4^75"
M9 F
in sample
S.I
/?. 7
<£/. 7
J a. O
Total
weight
of F
(Ft),
mg
O.ff-9
J. ^
tol
JTotal weight of fluoride in sample (F.)
F=10
-3
VtVd
ATA:P9F)
D 50 w
aControl samples results must be between 19.6 ug and 20.4 ug for «S & < o
(D n> H- rt
en H-
ts> C| p. o
a o a
undistilled sample on 18.0 an 22.0 ug for distilled sample
Remarks:
Lt d
033
HiC
£ *
»-• M O
Signature of analyst
a.
Signature of reviewer
Figure 5.1. Method 13A analytical data form.
vo.
OO •
N>
U)
I •
h-«
o
in
-------
Section No. 3.10.5
Revision No. 0
Date January 4, 1982
Page 3 of 18
where
Vsoln' = samP^e volume to be used in the calculations, ml;
V
soln = total volume of solution in which fluoride is con-
tained, ml;
Vsolni = initial volume added to the container in the
field, ml;
Vsolnf = final volume removed from the container in the
base laboratory, ml.
6. Both the corrected and uncorrected values should be
submitted in the test report to the agency.
If the spent silica was not weighed in the field, weigh the
silica gel and report the weight to the nearest 0.5 g on the
sample integrity and recovery form.
In the SPADNS colorimetric method, the volume measurements
of- the sample and the reagents are very important to the accura-
cy of the determination. The temperatures of the samples and
standards not only must be within 2°C (4°F), but also must be
constant throughout color development. Calibration curves may
be prepared for different temperatures. The analytical balance
must be checked with Class-S standard weights before each series
of weighings, and the data on the weighings must be recorded on
a calibration form (Figure 5.2).
The colorimetric method is based on the reaction between
flouride and a zirconium-dye; more specifically, fluoride reacts
with .the dye lake, and dissociates a portion of the dye into a
colorless complex anion (2rF7) and the dye. As the amount of
fluoride increases, the color either becomes progressively
lighter or changes in hue. The reaction rate between the
fluoride and zirconium ions is accelerated by the acidity of the
reagent; by increasing the proportion of acid, the reaction can
be practically instantaneous.
-------
Section No. 3.10.5
Revision No. 0
Date January 4, 1982
Page 4 of 18 •
Balance name
Classification of standard weights
Number
""
"S
-------
Section No. 3.10.5
Revision No. 0
Date January 4, 1982
Page 5 of 18
Colorimetric methods are subject to errors from interfering
ions; thus it will be necessary to distill the sample before
making the fluoride determination.
Procedures are detailed herein for preparing reagents,
blanks, control samples, distillation aliguots, reference and
working standards, and measuring the fluoride in samples.
5.2.1 Reagents - The following reagents are needed for the
analyses of fluoride samples.
1. Calcium oxide (CaO) - ACS reagent grade powder or ACS
certified grade containing £0.005% fluoride.
2. Phenolphthalein indicator - 0.1% in 1:1 ethanol-water
mixture (v/v).
3. Sodium hydroxide (NaOH) - Pellets, ACS reagent grade
or the equivalent.
4. Sulfuric acid (H9SOA) - Concentrated, ACS reagent
grade or the equivalent.
5. Filters - Whatman No'. 541 or the equivalent.
6. Water - Deionized distilled to conform to ASTM speci-
fication D1193-74, Type 3. The analyst may omit the KMn04 test
for oxidizable organic matter if high concentrations of organic
matter are not expected.
7. Silver sulfate (Ag^SCL)__ - ACS reagent grade or the
equivalent.
8. Hydrochloric acid (HC1) - Concentrated, ACS reagent
grade or the equivalent.
9. Sodium fluoride (NaF) standard - Dissolve 0.2210 g ±
0.0005 g ACS reagent grade NaF, which has been dried for a mini-
mum of 2 h at 110°C (230°F) and stored in a desiccator, in
*
deionized' distilled water, and dilute to 1-2 with deionized
distilled water; this solution contains 0.1 mgF/ml.
10. Sodium fluoride (NaF) working standard - Pipette 100
ml of the NaF standard into a 1-8. volumetric flask and dilute to
mark with deionized distilled water; this solution contains 0.01
mg F/ml.
-------
Section NO. 3.10.5
Revision No. 0
Date January 4, 1982
Page 6 of 18
11. SPADNS solution - Dissolve 0.960 ±0.010 g of SPADNS
reagent 4,5 dihydroxy-3-(parasulfophenylazo)-2,7-naphthalenedi-
sulfonic acid trisodium salt (also called sodium 2-(parasulfo-
phenylazo)-l,8-dihydroxy-3,6-naphthalenedisulfonate) in dis-
tilled water, and dilute to 500 ml; this solution is stable for
about 1 mo if stored in a well-sealed bottle and protected from
direct sunlight.
12. Reference solution - Add 10 ml of SPADNS solution to
100 ml of distilled water; dilute 7 ml of concentrated HC1 to 10
ml with distilled water and add it to the diluted SPADNS solu-
tion. Prepare the reference solution fresh daily and use it to
set the spectrophotometer zero point.
13. SPADNS mixed reagent - Dissolve 0.135 ±0.005 g of
zirconyl chloride octahydrate (ZrOCl, • 8H20) in 25 ml of dis-
tilled water; add 350 ml of concentrated HC1; and finally dilute
to' 500 ml with distilled water to get the zirconyl acid reagent.
Then, mix equal volumes of the SPADNS solution and zirconyl acid
reagent to produce the SPADNS mixed reagent, which is stable for
at least 2 mo.
5.2.2 Blanks - The three blanks needed for the analysis are a
filter blank to ensure that the quality of the filter is accept-
able, a distillation blank to protect against cross contamina-
tion, and a sample blank to analyze with the samples to verify
the purity of the reagents used in sampling and analysis.
1. - Filter blanks - Determine the fluoride content of the
sampling filters upon receipt of each new lot of and at least
once for each test series. Initially, select three filters
randomly from each lot.
*
a. Add each filter to 500 ml of distilled water.
b. Treat the filters exactly like a sample (Subsec-
tion 5.2.3).
c. Use a 200-ml aliquot for distillation. The
fluoride concentration of the filter blank must be <0.015 mg
F/cm2; if not, reject this batch and obtain a new supply of
filters.
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Section No. 3.10.5
Revision No. 0
Date January 4, 1982
Page 7 of 18
2. Distillation blank - Check the condition of the acid
in the distillation flask (Subsection 5.2.5) for cross-contami-
nation after every 10th sample by adding 220 ml of distilled
water to the still pot and then proceed with the analysis. If
detectable amounts of fluoride (>0.1 (jg F/ml) are found in the
blank, replace the acid in the distillation flask.
3. Sample blank - Prepare the sample blanks in the field
at the same time and with the same reagents used for sample
recovery.
a. Add an unused filter from the same batch used in
sampling to a volume of distilled water equal to the average
amount used to recover the samples.
b. Treat the sample blank in the same manner as the
samples are treated (Section 5.2.3). Analyze the sample blanks
with the samples.
5.2.3 Sample Preparation - Use the following procedure to pre-
pare samples for distillation. Distillation is not required if
it can be shown to the satisfaction of the Administrator that
fluoride results are unaffected by the alternate analytical pro-
cedure (e.g., ash and fusion of particulate matter with subse-
quent ion selective electrode analysis, or direct electrode
analysis of gases trapped in impingers).
1. Filter the contents of the sample container (including
the sample filter) through a Whatman No. 541 filter or the
equivalent into a 1500-ml beaker; if the filtrate volume is >_900
ml, add NaOH to make the filtrate basic to phenolphthalein, and
then evaporate to <900 ml.
2. Place the Whatman No. 541 filter containing the in-
solubles (including the sample filter) in a nickle crucible, add
a few milliliters of water; and macerate the filter with a glass
rod.
3. Add 100 mg or sufficient quantity of CaO to the nickel
crucible to make the slurry basic; mix thoroughly; and add a
couple drops of phenolphthalein indicator, which turns pink in a
basic medium. Note; If the slurry does not remain basic (pink)
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Section No. 3.10.5
Revision No. 0
Date January 4-, 1982
Page 8 of 18
•
during the evaporation of the water, fluoride will be lost; if
the slurry becomes colorless, it is acidic so add CaO until the
pink returns.
4. Place the crucible in a hood area either under in-
frared lamps or on a hot plate at low. heat (approximately 50-
60°C) (122-140°F), and evaporate the water completely; then
place the crucible on a hot plate under a hood and slowly in-
crease the temperature for several hours or until the filter is
charred.
5. Place the crucible in a cold muffle furnace and gradu-
ally (to prevent smoking) increase the temperature to 600°C
(1112°F); maintain the temperature until the crucible contents
are reduced to an ash containing no organic materials; and
remove the crucible from the furnace to cool.
6. Add approximately 4 g of crushed NaOH pellets to the
crucible, and mix; return the crucible to the furnace, and fuse
the sample for 10 min at 600°C (1112°F); and then remove the
sample from the furnace, and cool it to ambient temperature.
7. Use several rinsings of warm distilled water to trans-
fer the contents of the crucible to the beaker containing the
filtrate (step 1) and finally, rinse the crucible with two 20-ml
portions of 25% (v/v) H2S04, and carefully add the rinses to the
beaker.
8. Mix' well, and transfer the beaker contents to a 1-2
volumetric flask. Record the volume as Vfc on the data form
(Figure 5.1). Dilute to volume with distilled water, and mix
thoroughly; and allow any undissolved solids to settle.
5.2.4 Acid-water Ratio - The acid-water ratio in the distilla-
tion flask should be adjusted by following this procedure. Use
a protective shield when carrying out the procedure.
1. Place 400 ml of distilled water in the 1-2 distilling
flask, and add 200 ml of concentrated H2SO4. .Slowly add the
H2S04, while constantly swirling the flask.
2. .Add soft glass beads and several small pieces of
broken glass tubing, and assemble the apparatus.
-------
Section No. 3.10.5
Revision No. 0
Date January 4, 1982
Page 9 of 18
3. Heat the flask until it reaches a temperature of 175°C
(347°F), and discard the distillate, and hold the flask for
fluoride separation by distillation.
5.2.5 Fluoride Separation (Distillation) - Fluoride can be
separated from other constituents in the aqueous sample by dis-
tilling fluosilicic (or hydrofluoric) acid from a solution of
the sample in an acid with a higher boiling point. Samples with
low concentrations of fluoride (e.g., samples from an outlet of
a scrubber) should be distilled first to eliminate contamination
by carryover of fluoride from the previous sample. If fluoride
distillation in the milligram range is to be followed by distil-
lation in the fractional milligram range, add 200 ml of de-
ionized distilled water and redistill similar to the acid ad-
justment procedure, Subsection 5.2.4, to remove residual fluo-
ride from the distillation system.
1. Cool the contents of the distillation flask (acid-
water adjusted) to <80°C (176°F).
2. Pipette an, aliquot of sample containing <10.0 mg F
into the distillation'flask, and add distilled water to make 220
ml. The aliquot size (At) should be entered on the data form
(Figure 5.1). Note; For an estimate of the aliquot size that
contains 175°C (347°F) will cause H2S04 to
distill over. Note; The H2S04 in the distillation flask can be
-------
Section No. 3.10.5
Revision No. 0'
Date January 4, 1982
Page 10 of 18 "
reused until carryover of interferent or until poor fluoride
recovery is shown by the distillation blanks or the control
samples.
5. Before distilling the field samples and after every
tenth distillation of any sample, distill a control sample to
check the analytical procedures and interferences (Subsection
5.2.6).
5.2.6 Control Samples - A control sample should be used to
verify the calibration curve and the distillation recovery
before and during the analysis of the field samples. Use the
following procedures. Data should be recorded on the control
sample analytical data form (Figure 5.3).
1. 125 mg F/£ NaF control sample stock solution - Add
0.276 g of reagent grade anhydrous NaF to a l-£ volumetric
fl'ask; add enough distilled water to dissolve; and dilute to l-£
with distilled water.
2. 2.5 mg F/£ NaF distillation solution - Pipette 20 ml
of the 125 mg F/£ stock solution into a 1-jfc volumetric flask,
and dilute to the mark with distilled water to get the 2.5 mg
F/£ NaF distillation solution. Distill 200 ml of this solution
according to Subsection 5.2.5.
3. Pipette 4.0 ml of the control sample stock solution
into a 250-ml volumetric flask and dilute to the mark with dis-
tilled water. Analyze this solution colorimetrically in the
same manner as the samples are analyzed (Subsection 5.2.10).
5.2.7 Distillation Aliquot - The sample volume for distillation
should contain <10 mg F. Use the following procedure to esti-
mate the aliquot size.
1. Pipette a 1.0-ml aliquot of sample into a polyethylene
beaker.
2. Add 50 ml of distilled water.
3. Analyze by the procedure described in 5.2.10.
-------
Section No. 3.10.5
Revision No. 0
Date January 4, 1982
Page 11 of 18
Plant
Perli \\2-tf
Date of analysis
s//3/ro
Analyst LO . PO l'
1 1
Ambient temperature
*C
Date of calibration curve 5//3/?0 Temp, of calibration curve 3 / ° C
Concentration of control sample
Distilled
Undi stilled
Control sample temperature
Absorbance of control sample
Amount of F in control sample
from calibration curve
Percent error between measured
and calculated concentration
arc
o.
0.475
'. /
- 1.5 Jo
Were acceptable results obtained on control samples (less than 2% undis-
tilled and <10% distilled) tit
Signature of analyst
Signature of reviewer
>. 4
"7 .
Figure 5.3. Control sample analytical data form.
-------
Section No. 3.1p.5
Revision No. 0
Date January 4, 1982
Page 12 of 18
4. Determine the pg of F in the nondistilled sample from
the calibration curve, and determine the maximum size of the
aliquot for distillation by substituting the amount of F (fjg) in
the nondistilled sample in the following equation:
aliquot for distillation ,1) =
= Mg F1d4termined ?hen * 1-° ml nondistilled
xS IISGQ *
If the amount of F in the nondistilled. sample is >70 pg, de-
crease the aliquot taken for this estimation and change the
aliquot value input into the above equation. The aliquot size
is only an approximation since the interferring ions have not
been removed by distillation. If the estimate is >220 ml, use
220 ml; if it is <220 ml, add distilled water to make the total
volume added to the distillation flask 220 ml; if required,
dilute the sample so that a minimum 1-ml sample aliquot is added
to the distillation flask.
5.2.8 Determination of Chloride - A chloride determination is
necessary because of major interferences with Method 13A when a
relatively high concentration of chloride ions (Cl~) are present
in the collected sample. Chloride concentration depends on the
plant's material balance.
The mercuric nitrate procedure is introduced here for esti-
mating how much Ag2S04 is required for removal of chloride
interference. This procedure is easy to perform and has good
precision and accuracy. Reagents needed for this procedure
follow:
1. Standard sodium chloride solution (NaCl), 0.141 N
Dissolve 8.241 g NaCl (dried at 140°C (285°F) for 1-h) in chlo-
ride-free water, and dilute to l-£; contains 5 mg Cl/ml.
2. Nitric acid (HNOa), 0.1 N - Dilute 5 ml of concen-
trated HNO3 to 800 ml with distilled water.
-------
Section No. 3.10.5
Revision No. 0
Date January 4, 1982
Page 13 of 18
3. Mixed indicator reagent - Dissolve 5 g of diphenylcar-
bazone powder and 0.5 g of bromphenol blue powder in 750 ml of
95% ethyl or isopropyl alcohol, and dilute to 1 £ with the same
alcohol.
4. Standard mercuric nitrate (Hg(NOa)2) titrant, 0.141 N -
Dissolve 25 g of Hg(NO3)2«H20 in 900 ml of distilled water con-
taining 5 ml of concentrated HN03 (nitric acid). Dilute to 1 £.
The chloride equivalent of the titrant is 5.00 mg/ml.
The sample analysis for chloride determination is as fol-
lows:
1. Pipette 25 ml of a sample into a 150-ml beaker.
2. Add approximately 0.5 ml of indicator, and mix well;
the color should be purple.
3. Add 0.1N HNO3 drop-by-drop until the color just turns
ye.llow.
4. Titrate with 0.141N Hg(NO3)2 to the first appearance
of dark purple and record the number of milliliters used.
5 . Check the blank by titrating 100 ml of distilled water
containing 10 mg NaHC03 .
6. Calculate the concentration of chloride with the
following equation.
where
A = titrant used for sample, ml,
B = titrant used for blank, ml, and
N = normality of Hg (NO3)2, meg/ml.
Standardization of Hg (N03)2 for Chloride -
1. Titrate 15 ml of the standard NaCl with Hg (N03)2
reagent, using the method as previously described. Make at
least three replicates and obtain the average normality of Hg
(N03)2.
-------
Section No. 3.10.5
Revision No. 0'
Date January 4, 1982
Page 14 of 18 %
2. Calculate the normality of Hg (N03)2.
ml NaCl x N NaCl = ml Hg(N03)2 x N Hg (N03)2;
therefore,
- ml NaCL x N NaCl
-
M H,wwn ^ -
N Hg(N03)2
3. Calculate and add the required amount of silver sul-
fate for each sample:
__ ._ cn _ mg/A Cl" x ml aliquot (distilled) x 5
mg Ag2so4 -- 1000 ml
5.2.9 Calibration Standards - Use the sodium fluoride working
standard in Subsection 5.2.1 (0.01 mg/ml) in the following pro-
cedure. These standards cover the range of 0.2 - 1.4 pg F/mA.
1. Pipette 2.0, 4.0, 6.0, 8.0, 10.0, 12.0, and 14.0 ml
volumes of 0.01 mg F/ml NaF solution into seven separate 100-ml
volumetric flasks, and dilute to the mark with distilled water.
2. Pipette 50 ml of each of the each solutions into sepa-
rate 100-ml polyethylene beakers, add 10 ml of SPADM? mixed
reagent to each, and mix well.
3. Prepare the blank standard by pipetting 10 ml of
SPADNS mixed reagent to 50 ml of distilled water. These stan-
dards will contain 0, 10, 20, 30, 40, 50, 60, and 70 pg of
fluoride .
4. After mixing, place the calibration standards and
reference solution Subsection 5.2.1 in a constant temperature
bath for 30 minutes before reading the absorbance within ±3°C
(5.4°F) of the spectrophotometer . Note; Adjust all samples to
this same temperature before analysis. Since a 3°C difference
between samples^ and standards will produce an error of approxi-
mately 0.005 mg F/£, take care to see that samples and standards
are at nearly identical temperatures when absorbances are mea-
sured.
5.2.10 Determination of Fluoride Concentration - In Method 13A,
use the following steps to determine the amount of fluoride.
-------
Section No. 3.10.5
Revision No. 0
Date January 4, 1982
Page 15 of 18
1. Dilute the distillate to the mark in the 250-ml volu-
metric flask with distilled water, and mix thoroughly. Enter
this volume (V,) on the analytical data form (Figure 5.1).
2. Pipette a suitable aliquot (maximum of 50 ml) from the
distillate (containing 10 to 40 |jg F) (for the control samples,
a 10 ml aliquot is required); dilute to 50 ml with distilled
water; add 10 ml of SPADNS mixed reagent; and mix thoroughly.
Record the aliquot A, on the data form.
3. Place the sample in a bath that is constant at ±3°C
(5.4°F) of ambient temperature and which contains the standard
solutions for 30 min before reading absorbance with the spectro-
photometer.
4. Warm up the spectrophotometer for a suitable time (5
to 10 min) depending on the instrument; set the photometer to
zero absorbance with the reference solution at 570 nm; and
immediately obtain the absorbance readings of the standards,
control sample, and field samples.
5. Prepare a calibration curve by plotting the micrograms
(M9) F/50 m£ versus absorbance on linear graph paper, as de-
scribed in Section 3.10.2. Note; Prepare a new standard curve
whenever a fresh batch of any reagent is made up or when a dif-
ferent standard temperature is desired. Also, run an undis-
tilled control sample with each set of samples; if it differs
from the calibration curve by >±2%, prepare a new standard
curve.
6. Determine the \ig fluoride from the calibration curve
and record on the data form (Figure 5.1). The values of the
control samples should be 20 pg. For the undistilled sample, a
value between i9.6 and 20.4 \ig is acceptable; for the distilled
sample, a value between 18.0 and 22.0 |jg is the acceptable
range. If both values for the control samples fall within their
limits, the field sample results should also be acceptable.
However, if the undistilled sample is acceptable and the dis-
tilled is not, replace the contents of the distillation flask
and redistill all samples. If the distilled is acceptable and
-------
Section No. 3.10.5
Revision No. 0 ,
Date January 4, 1982
Page 16 of 18 -.
the undistilled sample is not, prepare fresh calibration stan-
dards and carefully check the temperature equilibrium. When
both samples are unacceptable, prepare a new calibration curve.
If this does not correct the problem, start over with all new
solutions and check with an analyst familiar with the procedure.
7. Repeat the procedure using a smaller size aliquot of
distillate if the fluoride concentration of the sample is not
within the range of the calibration curve.
8. Calculate the total weight as milligrams and the con-
centration of fluoride using the equations in Section 3.10.6 and
record on the data form (Figure 5.1).
The value of Ft obtained using Equation 6.4 of Section
3.10.6 for the distilled control sample should be 2.50 mg F;
acceptable values are between 2.25 and 2.75 mg F. The final
emission concentration in mg/dscm (Ib/dscf) should be reported
in the test report to the agency both corrected and uncorrected
for the sample blank.
-------
Section No. 3.10.5
Revision No. 0
Date January 4, 1982
Page 17 of 18
TABLE 5.1. ACTIVITY MATRIX FOR POSTSAMPLING OPERATIONS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sampling
Apparatus
Dry gas meter
±5% of calibration
factor
Make three runs at a
single intermediate
orifice setting at
highest volume of
test (Sec 3.10.2)
Recalibrate;
use factor
that gives
lower gas
volume
Meter thermome-
ters
±6°C (10.8°F) ambient
temperature
Compare with ASTM
mercury-in-glass
thermometer after
each test
Recalibrate;
use higher
temperature
for calcula-
tions
Barometer
±5 mm (0.2 in.) at
ambient pressure
Compare with mercury-
in-glass barometer
after each test
Recalibrate;
use lower
barometric
value for
calculations
Stack tempera-
ture sensors
±1.5% of the reference
thermometer or thermo-
couple
Compare with ref-
erence temperature
after each run
Recalibrate;
calculate
with and
without tem-
perature cor-
rections
Base Laboratory
Analysis
Reagents
Prepare according to
Subsec 5.2
Prepare a calibration
curve for each new
SPADNS reagent mix
Prepare new
solutions and
calibration
curves
(continued)
-------
Section No. 3.10.5
Revision No. 0 -
Date January 4, 1982
Page 18 of 18 •
TABLE 5.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Control sample
±2% when run with
fluoride standards and
±10% when distilled
and run with field
samples
Prepare new controls
before and during
analysis of field
samples
Prepare new
solution and
calibration
curve, and/or
change dis-
tillate
solution
-------
Section No. 3.10.6
Revision No. 0
Date January 4, 1982
Page 1 of 7
6.0 CALCULATIONS
Calculation errors due to procedural or mathematical mis-
takes can be a large part of total system error. Thus, each set
of calculations should be repeated or spotchecked, preferably by
a team member other than the one that performed the original
calculations. If a difference greater than a typical roundoff
error is detected, the calculations should be checked step-by-
step until the source of error is found and corrected.
A computer program is advantageous in reducing calculation
errors. If a standardized computer program is used, the origi-
nal data entry should be checked and if differences are ob-
served, a new computer run should be made.
Table 6.1 at the end of this section summarizes the quality
assurance activities for calculations. Retain at least one
significant digit beyond that of the acquired data. Roundoff
after the final calculations for each run or sample to two sig-
nificant digits, in accordance with ASTM 380-76. All calcula-
tions should be recorded on a calculation form such as the ones
in Figures 6.1A and 6.IB.
6.1 Nomenclature
Terms used in Equations 6-1 through 6-7 are defined here
for use in the sections that follow.
A, = Aliquot of distillate taken for color development,
a ml
= Area of nozzle, cross-sectional, m2 (ft2)
•
At = Aliquot of total sample added to still, ml
B = Water vapor in the gas stream, proportion by
volume
C = Concentration of fluoride in stack gas corrected
to standard conditions of 20°C, 760 mm Hg (68°F,
29.92 in. Hg) on dry basis, mg/m3 (lb/ft3)
F. = Total weight of fluoride in sample, mg (Ib)
-------
Section No. 3.10.6
Revision No. 0'
Date January 4, 1982
Page 2 of 7
SAMPLE VOLUME. (ENGLISH UNITS)
Vm = t
-------
Section No. 3.10.6
Revision No. 0
Date January 4, 1982
Page 3 of 7
SAMPLE VOLUME (METRIC UNITS)
Vm = L ' 3 2 I m3< Tm = £ L 0. °K, Pbar = 2
Y = Q. - 3. 2 te> AH = <3 fe- mm H2°
P + (AH/13.6)
Vm(std) = °-3858 Vm Y
= 1-22
Hg
Equation 6-1
m
vt .= L Q. Q. & • Q.
Ad =
•
Ft = 10
,
t d
FLUORIDE CONTENT IN SAMPLE
L' At = 3 Q. Q • Qmi, vd = ;
F) = ^ . V
ml
Equation 6-4
CONCENTRATION OF FLUORIDE (METRIC UNITS)
Vm(std) = L • 2 2 2 dscm Ft =
F. -
C = T
5
m(std)
= l_ - 2. 3 6 mg/dscm
0 ^ 0 mg
Equation 6-5
All other equations same as Methods 2 and 5.
Figure 6.IB. Fluoride calculation form (metric units).
-------
Section No. 3.10.6
Revision No. 0
Date January 4, 1982
Page 4 of 7
F^ = Total weight of fluoride in sample blank, mg (lb)
I = Percent of isokinetic sampling, %
MVJ = Molecular weight of water, 18.0 g/g-mole
(18.0 Ib/lb-mole)
Pbar = Barometric pressure at sampling site, mm (in.) Hg
P = Absolute stack gas pressure at sampling site, mm
(in.) Hg
= Standard absolute pressure, 760 mm (29.92 in.) Hg
R = Ideal gas constant, 0.066236 mm Hg-m3/K-g-mole
(21.83 in. Hg-ft3/°R-lb-mole)
T = Absolute average dry gas meter temperature,
I" VI On \
IS. ( t\)
T_ = Absolute average stack gas temperature, K (°R)
S
= Standard absolute temperature, 293K (528°R)
Vd = Total volume of distillate, ml
V. = Total volume of liquid collected in impingers and
silica gel, ml. (Volume of water in silica gel =
grams of silica gel weight increase x 1 ml/g;
volume of liquid collected in impinger = final
volume - initial volume)
V - Volume of gas sample measured by dry gas
m
meter, dcm (dcf)
V . .,, = Volume of gas sample measured by dry gas meter
* ' corrected to standard conditions, dscm (dscf)
V = Stack gas velocity calculated by Method 2 (Equa-
tion 2-7) using data from Method 13, m/s (ft/s)
Vt = Total volume of sample, ml
V = Volume of water vapor in gas sample corrected to
standard conditions, scm (scf)
Y = Dry gas meter calibration factor
AH = Average pressure differential across the orifice
meter, mm (in.) H2O
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Section No. 3.10.6
Revision No. 0
Date January 4, 1982
Page 5 of 7
Pw = Density of water, 1 g/ml (0.00220 Ib/ml)
0 = Total sampling time, min
pg F = Weight of fluoride/50 ml taken from the calibra-
tion curve, |jg
13.6 = Specific gravity of mercury
60 = s/min
100 = Factor for converting to percent, %
6.2 Dry Gas Volume, Corrected to Standard Conditions
Correct the sample volume measured by the dry gas meter
(Vm) to standard conditions (20°C and 760 mm Hg or 68°F and
29.92 in. Hg) by using Equation 6-1. The absolute dry gas meter
temperature (T ) and orifice pressure drop (poor) are obtained
by averaging the field data.
m(std) - m Tm
Pbar + (AH/13.6)
= Kl VmY T -- Equation 6-1.
m
where
K, = 0.3858 K/mm Hg for metric units, and
= 17.64 °R/in. Hg for English units.
Note: If the leak rate observed during any mandatory leak check
exceeds the acceptable rate, the tester shall either correct the
value of V in Equation 6-1 (Section 6.3, Method 3), or invali-
date the test runs.
*
6.3 Volume of Water Vapor
Vw(std) = Vic = K Vic Equation 6-2
where
K = 0.00133 m3/ml for metric units, and
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Section No. 3.10.6
Revision No. 0
Date January 4, 1982
Page 6 of 7
K = 0.0472 ft3 /ml for English units.
6.4 Moisture Content of Stack Gas
B = ^ - *l§tdj - . Equation 6-3
ws m(std) w(std)
Note; If liquid droplets are in the gas stream, assume the
stream to be saturated; use a psychrometric chart to obtain
estimate of the moisture percentage.
6.5 Fluoride Content in Sample (Concentration)
V Vd pg F
. F,. = K \ u. - Equation 6-4
r At Ad
where
K = 10" mg/|jg for metric units, and
K = 2.205 x 10 Ib/jjg for English units.
6/6 Concentration of Fluoride in Stack Gas
F - F
* *
C = K Equation 6-5
s m(std)
K = 1.00 m3/m3 for metric units, and
K = 35.31 ft3/m3 for English units.
6.7 Isokinetic Variation (I)
The isokinetic variation ( I ) can be calculated from either
raw data or intermediate values using the following equations.
6.7.1 Calculation of I from Raw Data
_ 100 x TS [K Vic + (Y Vm/Tm) (Pbar + AH/13.6)]
606v P A
s s n
Equation 6-6
where
K = 0.003454 mm Hg-m3ml-K for metric units, and
= 0.002669 in. Hg-ft3/ml-°R for English units.
6.7.2 Calculations of I from Intermediate Values
x Ts Vstd) Pstd
Equation 6.
-------
Section No. 3.10.6
Revision No. 0
Date January 4, 1982
Page 7 of 7
= K
T V
s vm(std)
VsAn 6 t1-8*
where
6.7
K = 4.320 for metric units, and
= 0.09450 for English units.
Acceptable Results
If 90% 1 I <. 110%, the results are acceptable. If the
results are low in comparison to the standards and if I is be-
yond the acceptable range, the administrator may opt to accept
the results; if not, reject the results and repeat the test.
TABLE 6.1. ACTIVITY MATRIX FOR CALCULATIONS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are mot met
Analysis data
form
All data and calcula-
tions given
Visual check
Complete the
missing data
values
Calculations
Difference between
check and original
calculations within
roundoff error; one
decimal figure re-
tained beyond that of
acquired data
Repeat all calcula-
tions starting with
raw data for hand
calculations; check
all raw data input
for computer cal-
culations and hand
calculate one sample
per test
Indicate
errors on
analysis data
form
Isokinetic
variation
90% < I < 110%; see
Eqs 6.6 and 6.7 for
calculation of I
Calculate I for
each traverse point
Repeat test;
adjust flow
rates to
maintain I
within ±10%
variation
-------
Section No. 3.10.7
Revision No. 0
Date January 4, 1982
Page 1 of 2
7.0 MAINTENANCE
Normal use of emission testing equipment subjects it to
corrosive gases, temperature extremes, vibrations, and shocks.
Keeping the equipment in good operating order over an extended
time requires routine maintenance and knowledge of the equip-
ment. Maintenance of the entire sampling train should be per-
formed either quarterly or after 1000 ft3 of operation, which-
ever occurs sooner. Maintenance activities are summarized in
Table 7.1. The following routine checks are recommended, but
not required, to increase reliabilty. This section is the same
as for Method 13B (Section 3.9.7).
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Section No. 3.10.7
Revision No. 0
Date January 4, 1982
Page 2 of 2
TABLE 7.1. ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Fiber vane pump
Leak free; required
flow; no erratic be-
havior-
Periodic check of oil
and oiler jar; remove
head yearly and
change fiber vanes
Replace as
needed
Diaphragm pump
Leak-free valves func-
tioning properly; re-
quired flow
Clean valves during
yearly disassembly
Replace when
leaking or
when running
erratically
Dry gas meter
No excess oil, corro-
sion, or erratic dial
rotation
Check every 3 mo for
excess oil or corro-
sion; check valves
and diaphragm if
dial runs erratically
or if meter will not
calibrate
Replace parts
as needed, or
replace meter
Inclined manom-
eter
No discoloration of or
visible matter in the
fluid
Check periodically;
change fluid during
yearly disassembly
Replace parts
as needed
Other sampling
train com-
ponents
No damage or leaks; no
erratic behavior
Visually check every
3 mo; disassemble and
clean or replace
yearly
If failure
noted, re-
place meter
box, sample
box, or um-
bilical cord
Nozzle
No dents, corrosion,
or'other damage
Visually check be-
fore and after each
test run
Replace noz-
zle or clean,
sharpen, and
recalibrate
-------
Section No. 3.10.8
Revision No. 0
Date January 4, 1982
Page 1 of 1
8.0 AUDITING PROCEDURES
An audit is an independent assessment of data quality.
Independence is achieved by using apparatus and standards that
are different from those used by the regular, field crew. Rou-
tine quality assurance checks by a field team are necessary for
obtaining good quality data, but they ate not part of the au-
diting procedure. Table 8.1 summarizes the quality assurance
activities for the auditing. This section is the same as Method
13B (Section 3.9.8).
TABLE 8.1. ACTIVITY MATRIX FOR AUDITING PROCEDURES
Audit
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Performance
Audit
Analytical
phase of
Method 13 A
using aqueous
sodium fluo-
ride
Measured concentrations
of audit sample within
acceptable limits of
true value, Section
3.9.8
Once during every
enforcement source
test; measure audit
samples and compare
their values with
known concentrations
Review
operating
technique
Data processing
errors
Difference between
original and audit
calculations within
roundoff error
Once during every
enforcement source
test, perform inde-
pendent calculations
starting with data
recorded on field
and laboratory forms
Check and
correct all
data; recaV
culate if
necessary
Systems audit
Operation technique as
described in Section
3.10.8
Once during every
enforcement test,
until experience
gained and then
every fourth test,
observe techniques;
use audit checklist
(Fig 8.2, Section
3.9.8)
Explain to
team devia-
tions from
recommended
techniques;
note on
Fig 8.2
-------
Section No. 3.10.9
Revision No. 0
Date January 4, 1982
Page 1 of 1
9.0 RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
To acquire data of good quality, two considerations are
essential:
1. The measurement process must be in a state of statis-
tical control at the time of the measurement, and
2. The systematic errors, when combined with the random
variations (errors of measurement), must result in acceptable
uncertainty.
Other quality assurance activities include quality control
checks and independent audits of the total measurement system
(Section 3.10.8); documentation of data by using quality control
charts (as appropriate); use of materials, instruments, and
•
procedures that can be traced to appropriate standards of refer-
ence; and use of control standards and working standards for
routine data collection and equipment calibration. Working
standards should be traceable to primary standards:
1. Dry gas meter calibrated against a wet test meter that
has been verified by liquid displacement (Section 3.9.2) or by
a spirometer.
2. Field samples, analyzed by comparisons with standard
solutions (aqueous NaF) that have been validated with indepen-
dent control samples.
-------
10.0 REFERENCE METHOD3
Section No. 3.10.10
Revision No. Or
Date January 4, 1982
Page 1 of 5
40 CFR Part 60 is amended by revising
Methods 13A and 13B of Appendix A to
read as follows:
Appendix A—Reference Test Methodo *
• * * * «
Method 13A. Determination of Total Fluoride
Emissions From Stationary Sources; SPADNS
Zirconium Lake Method
1. Applicability and Principle
U Applicability. This method applies to
the determination of fluoride (F) emissions
from sources as specified in the regulations. It
does not measure fluorocarbons, such as
fraons.
1.2 Principle. Gaseous and paniculate F~
ore withdrawn isokinetically from the source
and collected in water and on a filter. .The
total F is then determined by the SPADNS
Zirconium Lake colorimetric method.
2. Range and Sensitivity
The range of this method is 0 to 1.4 pg F/
ml Sensitivity has not been determined.
3. Interferences
Large quantities of chloride will interfere
with life analysis, but this interference can bf
prevented by adding silver sulfate into the
Distillation flask (see Section 7.3.4). If
chloride ion is present it may be easier to u»<-
the Specific Ion Electrode Method (Method
13B). Grease on sample-exposed surfaces
may. cause low F results due to adsorption.
4. Precision. Accuracy, and Stability
4.1 Precision. The following estimates
ore based on a collaborative test done at a
primary aluminum smelter. In the test, six
laboratories each sampled the stack.
simultaneously using two sampling trains for
a total of 12 samples per sampling run.
Fluoride concentrations encountered during
the test ranged from 0.1 to 1.4 mg F/m1.. The
within-laboratory and between-laboratory
standard deviations, which include sampling
and analysis errors, were 0.044 mg F/m* with
60 degrees of freedom and 0.064 mg F/mJ
with five degrees of freedom, respectively.
4.2 Accuracy. .The collaborative test did
not find any bias in the analytical method.
4.3 Stability. After the sample and
colorimetric reagent are mixed, the color
formed is stable for approximately 2 hours. A
3*C temperature difference between the
sample and standard solutions produces an
error of approximately 0.005 mg F/liter. To
avoid this error, the absorbances of the
sample and standard solutions must be*
measured at the same temperature.
5. Apparatus
5.1 Sampling Train. A schematic of the
sampling train is shown in Figure 13A-1; it is
similar to the Method 5 train except the filter
position is interchangeable. The sampling
train consists of the following components:
5.1.1 Probe Nozzle, Pitot Tube,
Differential Pressure Gauge. Filter Heating
System, Metering System, Barometer, and
Gas Density Determination Equipment
Same as Method 5. Sections 2.1.1. 2.1.3. 2.1.4.
2.1.6. 2.1.8. 2.1.9. and 2.1.10. When moisture
condensation is a problem, the filter heating
system is used.
5.1.2 Probe Liner. Borosilicate glass or
316 stainless steel. When the filter is located
immediately after the probe, the tester may
use a prob« heating system to prevent filter
plugging resulting from moisture
condensation, but the tester shall not allow
the temperature in the probe to exceed
120±14*C (24a±25'F).
5.14 Filter Holder. With positive seal
against leakage from the outside or around
the filter. If the filter is located between the
probe and first impinger. use borosilicate
glass or stainless steel with a 20-mesh
stainless steel screen filter support and a
silieone rubber gasket: do not use a glass frit
or a sintered metal filter support. If the filter
is located between the third and-fourth
impingers. the tester may use borosilicate
glass with a glass frit filter support and a
silieone rubber gasket. The tester may also
use other materials of construction with
approval from the Administrator.
5.1.4 Impingers. Four impingers
connected as shown in Figure 13A-1 with
ground-glass (or equivalent), vacuum-tight
fittings. For the first third, and fourth
impinger*, use the Greenburg-Smith design.
modified by replacing the tip with a 14-on-
inside-diameter (Vi in.) glass tube extending
to 14 on (V4 in.) from the bottom of the flask.
For the second impinger. use a Greenburg-
Smith impinger with the standard tip. The
tester may use modifications (e.g., flexible
connections between the impingers or
materials other than glass), subject to the
approval of the Administrator. Place a
thermome'ter, capable of measuring
temperature to within 1*C (2*F), at the outlet
of the fourth impinger for monitoring
purposes.
5.2 Sample Recovery. Th'fe following
items are needed:
5.2.1 Probe-Liner and Probe-Nozzle
Brushes. Wash Bottles, Graduated Cylinder
and/or Balance, Plastic Storage Containers,
Rubber Policeman. Funnel. Same as Method
5. Sections 2^.1 to ZZ2 and 2^5 to 12&.
respectively.*
5.24 Sample Storage Container. Wide-
mouth, high-density-polyethylene bottles for
impinger water samples, 1-liter.
5.3 Analysis. The following equipment in
needed:
54.1 Distillation Apparatus. Glass
distillation apparatus assembled as shown ia
Figure 13A-2.
544 Bunsen Burner.
5.3.3 Electric Muffle Furnace. Capable of
heating to 600'C.
54.4 Crucibles. Nickel. 75- to 100-mL
54.5 Beakers. 500-ml and 1500-mL
54.6 Volumetric Flasks. 50-ml.
54.7 Erlenmeyer Flasks or Plastic Bottloo.-
500-mL
544 Constant Temperature Bath.
Capable of maintaining a constant
temperature of ±1.0*C at room temperature
conditions.
54.9 Balance. 300-g capacity to measure
to ±0.5 g.
5.3.10 Spectrophotometer. Instrument
that measures absorbance at 570 run and
provides at least a l-cm light path.
5.3.11 Spectrophotometer Cells, l-cm
pathlength.
& Reagents
6.1 Sampling. Use ACS reagent-grade
chemicals or equivalent, unless otherwise
specified. The reagents used in sampling are
as follows:
6.1.1 Filters.
6.1.1.1 If the filter is located between tha
third and fourth impingers, use a Whatman'
No. 1 filter, or equivalent sized to fit the filter
holder.
OILUNC CODE ««SO-01-M
1 Mention of company or product name* doet net
constitute endorsement by the UJ5. Environmental
Prelection Agency.
*Taken from Federal Register. Vol. 45, No. 121, pp. 41852-41857,
Friday, June 20, 1980.
-------
Section No. 3.10.10
Revision No. 0
Date January 4, 19t2
Page 2 of 5
TSMKRATURE , , -,
SENSOR STACK WALL { OPTIONAL FILTER j
-• MOIE
(HOLDER LOCATION!
THERMOMETER
CHECK VALVE
VACUUM LINE
VACUUM QAU8I
ORIFICE
MANOMETER
AIR- TIGHT WMf
DRY TEST METER
Figure 13A-1. Fluoride sampling train.
CONNf CTINQ TIME
•HTHilVM
CONDENSER
ERLENMEVER
FLASK
Figure 13A-Z Fluoride di«ill«tion apparatus.
-------
•O.L2 If the filter is located between the
probe and fir*t impinger. use any suitable
medium (e.g., paper organic membrane) that
conforma to the following specification*: (1)
The filter can withstand prolonged exposure
to temperature* up to 135'C (27S'F). (2} The
filter bat at least 95 percent collection
efficiency (<5 percent penetration) for 0.3 jim
dioctyl phthalate smoke particles. Conduct
the filter efficiency test before the test series,
using ASTM Standard Method D 2986-71. or
use test data from the supplier's quality
control program. (3) The filter has a low F
blank value (<0.015 mg F/cm* of filter area).
Before the test series, determine the average
F blank value pf at least three filters.(from
the lot to be used for sampling) using the
applicable procedures described in Sections
7 J and 7.4 of this method. In general, glass
fiber filters have high and/or variable F
blank values, and will not be acceptable for
use.
8.1.2 Water. Deionized distilled, to
conform to ASTM Specification D1193-74.
Type 3. If high concentrations of organic
natter are not expected to be present, the
analyst may delete the potassium
permanganate te*t for oxidizable organic
matter.
8.1.3 Silica Gel. Crushed Ice, and
Stopcock Crease. Same as Method 5.
Section 3.1,2.3.1.4. and 3.15. respectively.
(L2 Sample Recovery. Water, from same
container as described in Section 6.1.2. is
needed for sample recovery.
8.3 Sample Preparation and Analysis.
The reagents needed for sample preparation
and analysis are as follows:
6.3.1 Calcium Oxide (CaO). Certified
grade containing 0.005 percent F or IBM.
6.3.2 Phenolphthalein Indicator.
Dissolve 0.1 g of pheaolphthalein in a mixture
of SO ml of 80 percent ethanol and 50 ml of
deiooixad distilled water.
6JJ Silver Soifate (Ag«SO.).
8.3.4 Sodium Hydroxide (NaOH).
Pellets.
6.3.5 Suifuric Add (H3O.). Concentrated.
6.3.6 Suifuric Acid. 25 percent (V/V).
Mix 1 part of concentrated H.SO. with 3
parts of deionized distilled water.
6-3.7 Filters. Whatman No. 541. or
equivalent
6JJ Hydrochloric Acid (HC1).
Concentrated.
6-33 Water. From same container as
described In Section 6.1-2.
6.3.10 Fluoride Standard Solution. 0.01 mg
F/mL Dry in an oven at 110'C for at least 2
hours. Dissolve 0-2210 g of NaF in 1 liter of
deionized distilled water. Dilute 100 ml of this
solution to 1 liter with deionized distilled
water.
6J.11 SPADNS Solution [4. 5 dihydroxy-3-
(p-sulfophenylazo)-2,7-naphlhalene-disulfonic
acid Irisodium sail). Dissolve 0560 ± 0.010
g of SPADNS reagent in 500 ml deionized
distilled water. If stored in a well-sealed
bottle protected from the sunlight, this
solution is stable for at least 1 month.
6.3.12 Spectrophotometer Zero Reference
Solution. Prepare daily. Add 10 ml of
SPADNS solution (6.3.11) to 100 ml deionized
distilled water*, and acidify with a solution
prepared by diluting 7 ml of concentrated HC1
to 10 ml with deionized distilled water.
6.3.13 SPADNS Mixed Reagent Dissolve
0.135 ± 0.005 g of zirconyl chloride
octahydrate (ZrOCl,. 4H.O) in 25 ml of
deionized distilled water. Add 350 ml of
concentrated HC1. and dilute to 500 ml with
deionized distilled water. Mix equal volumes
of this solution and SPADNS solution to form
a single reagent This reagent is stable for at
least 2 month*.
ft /TDC0ut/r9
7.1 Sampling. Because of the complexity
of this method, testers should be trained and
experienced with the text procedures to
assure reliable results.
7.1.1 Pretest Preparation. Follow the
general procedure given in Method 5. Section
4.1.1. except the filter need not be weighed.
T i 9 Preliminary Determination*.
Follow the general procedure given in
Method 5, Section 4.1-2-, except the nozzle
size selected must maintain isokiaetie
sampling rate* below 28 liters/min (1-0 cfm].
7.1 J Preparation of Collection Train.
Follow the general procedure given in
Method 5. Section 4.1.3. except for the
following variations:
Place 100 ml of deionized distilled water in
each of the first two impinger*. and leave the
third impinger empty. Transfer approximately
200 to 300 g of preweighed silica gel from it*
container to the fourth impinger.
^Assemble the train as shown in Figure
13A-1 with the filter between the third and
fourth impinger*. Alternatively, if a-20-mesh
stainless steel screen is used for the filter
support the tester may place the filter
between the probe and first impinger. The
tester may also use a filler heating system to
prevent moisture condensation, but shall not
allow the temperature around the filter bolder
to exceed 120 dt 14'C (248 ± 25'F). Record
the filter location on the data sheet
7.14 Leak-Check Procedures. Follow the
leak-check procedures given in Method 5,
Section* 4.1.4.1 (Pretest Leak-Check). 4.1.4.2
(Leak-Checks During the Sample Run), and
4.1.4J (Post-Test Leak-Check).
7JJ Fluoride Train Operation. Follow
the general procedure given in Method 5,
Section 4.1 -5. keeping the filter and probe
temperatures (if applicable) at 120 ± 14'C
(246 ± 25*F) and isokinetic sampling rates
below 28 liters/nun (1-0 cfm). For each run.
record the data required on a data sheet such
as the one shown in Method 5. Figure 5-2.
7.2 Sample Recovery. Begin proper
cleanup procedure a* 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 of! all external
paniculate matter near the tip of the probe
nozzle and place a cap over it to keep from
losing part of the sample. Do not cap off the
probe tip tightly while the sampling train is
cooling down, because a vacuum would form
in the filter holder, thus drawing impinger
water backward.
Before moving the sample train to the
cleanup site, remove the probe from the
sample train, wipe off the silicone grease, and
cap the open outlet of the probe. Be careful
not to lose any condensate. if present.
Remove the filter assembly, wipe off the
silicon* grease from-the filter bolder inlet.
Section No. 3.10.10
Revision No. 0
Date January 4, 1982
Page 3 of 5
and cap this inlet Remove the umbilical cord
from the .last impinger. and cap the impinger.
After wiping off the silicone grease, cap off*
the filter holder outlet and any open impingar
inlets and outlet*. The tester may use ground-
glass stoppers, plastic caps, or serum caps to
close these opening*.
Transfer the probe and filter-implnger
assembly to an area that i* clean and
protected from the-wind *o that the chances
of contaminating or losing the sample U
minimized.
Inspect the train before and during
disassembly, and note any abnormal
condition*. Treat the samples a* follows:
7.2.1 Container No. 1 (Probe. Filter, and
Impinger Catches). Using a graduated
cylinder, measure to the nearest ml. and
record the volume of the water in the first
three impinger* inrlade any condensate in
the probe in this determination. Transfer the
impinger water from the graduated cylinder
into this polyethylene container. Add the
filter to this container. (The filter may be
handled separately using procedure* subject
to the Administrator'* approval.) Taking can
that dust on the outside of the probe or other
exterior surfaces do** not get into the
•ample, dean all sample-exposed surface*
(including the probe nozzle, probe fitting,
probe liner, first three impingera, impinger
connector*; and filter holder) with deionized
distilled water. Use less Inrnn 500 ml for the
entire wash. Add the washings to the sampler
container. Perform the deionized distilled
water rinses as follows:
Carefully remove the probe nozzle and
rinse the inside surface with deionized
distilled water from a wash bottle. Brush with
a Nylon bristle brush, and rinse until the
rinse shows no visible particles, after which
make a final rinse of the inside surface. Brush
and rinse the inside parts of the Swagelok
fitting with deionized distilled water in •
similar way.
Rinse the probe Boer with deionized
distilled water. While squirting the water into
the upper end of the probe, tilt and rotate the
probe »o that all inside surface* will be
wetted with water. Let.the water drain from
the lower end into the sample container. The
tester may use a funnel (glass or
polyethylene) to aid in transferring the liquid
washes to the container. Follow the rinse
with a probe brush. Hold the probe in an
inclined position, and squirt deionizad
distilled water into the upper end as the
probe brush is being pushed with a.twisting
action through the probe. Hold the sample
container underneath the lower end of the'
probe, and catch any water and particulate
matter that is brushed from the probe..Run
the brush through the probe three times or
more. With stainless steel or other metal
probes, run the brush through in the above
prescribed manner at least six times since
metal probes have small crevices in which
particulate matter can be entrapped. Rinse
the brush with deionized distilled water, and
quantitatively collect these washings in the
sample container. After the brushing, make a
final rinse of the probe as described above.
It is recommended that two people clean
the probe to minimize sample losses.
Between sampling run*, keep brushes clean
and protected from contamination.
-------
Rinse the inside surface of each of the first
three impingers (and connecting glassware)
three separate times. Use a small portion of
deionized distilled water for each rinse, and
brush each sample-exposed surface with a
Nylon bristle brush, to ensure recovery of
fine paniculate matter. Make a final rinse of
tach surface and of the brush.
After ensuring that all Joints have been
wiped clean of the silicone grease, brush and
rinse with deionized distilled water the inside
of the filter holder (front-half only, if filter is
positioned between the third and fourth
impingers). Brush and rinse each surface
three times or more if needed. Make a final
rinse of the brush and filter holder.
After all water washings and participate
matter have been collected in the sample
container, tighten the lid so that water will
not leak out when it is shipped to the
laboratory. Mark the height of the fluid level
to determine whether leakage occurs during
transport Label the container clearly to
identify its contents.
123. Container No. 2 (Sample Blank).
Prepare a blank by placing an unused filter in
a polyethylene container and adding a
volume of water equal to the total volume in
Container No. 1. Process the blank in the
same manner as for Container No. 1.
7.2.3 ContainerNo^3 (Silica Gel). Note
the color of Jhe indicating silica gel to
' determine whether it has been completely
spent and make a notation of its condition.
Transfer the silica gel from the fourth
impinger to its original container and seal
The tester may use a runnel to pour the silica
gel and a rubber policeman to remove the
silica gel from the impinger. It is not
necessary to remove the small amount of dust
particles that may adhere to the impinger
wall and are difficult to remove. Since the
gain in weight 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, the tester may follow
the analytical procedure for Container No. 3'
in Section 7.4.2.
7.3 Sample Preparation and Distillation.
(Note the liquid levels in Containers No. 1
and No. 2 and confirm on the analysis sheet
whether or not leakage occurred during
transport. If noticeable leakage had occurred,
either void the sample or use methods.
subject to the approval of the Administrator,
to correct the final results.) Treat the contents
of each sample container as described below:
7.3.1 Container No. J (Probe. Filter, and
Impinger Catches). Filter this container's
contents, including the sampling filter,'
through Whatman No. 541 filter paper, or
equivalent, into a ISOO-ml beaker.
7.3.1.1 If the filtrate volume exceeds 900
ml. make the filtrate basic (red to
phenolphthalein) with NaOH, and evaporate
to less than 900 ml.
7.3.1.2 Place the filtered material
(including sampling filter) in a nickel crucible.
add a few nil of deionized distilled water,
and macerate the filters with a glass rod.
Add 100 mg CaO to the crucible, and mix
the contents thoroughly to form a slurry. Add
two drops of phenolphthalein indicator. Place
the crucible in a hood under infrared lamps
or on a hot plate at low heat. Evaporate the
water completely. During the evaporation of
the water, keep the slurry basic.(red to
phenolphthalein) to avoid loss of F. If the
indicator turns colorless (acidic) during the
evaporation, add CaO until the color turns
red again.
After evaporation of the water, place the
crucible on a hot plate under a hood and
slowly Increase the temperature until the
Whatman No. 541 and sampling filters char. It
may take several hours to completely char
the filters.
. Place the crucible in a cold muffle furnace.
Gradually (to prevent smoking] increase the
temperature to 600'C, and maintain until the
contents are reduced to-an ash. Remove the
crucible from the furnace and allow to cool
Add approximately 4 g of crushed NaOH to'
the crucible and «•«•»- Return the crucible to
the muffle furnace, and fuse the sample for 10
minutes at 600'C.
Remove the sample from the furnace, and
cool to ambient temperature. Using several
rinsings of warm deionized distilled water,
transfer the contents of the crucible to the
beaker containing the filtrate. To assure
complete sample removal, rinse finally with
two 20-ml portions of 25 percent HtSO* and
carefully add to the beaker. Mix well and
transfer to a 1-liter volumetric flask. Dilute to
volume with deionized distilled water, and
mix thoroughly. Allow any undissolved solids
to settle.
7.3.2 Container No. 2 (Sample Blank).
Treat in the same manner as described in
Section 7 J.I above.
7.3.3 Adjustment of Acid/Water Ratio in
Distillation Flask. (Use a protective shield
when carrying out this procedure.) Place 400
ml of deionized distilled water in the
distillation flask, and add 200 ml.of
concentrated tbSO* (Caution: Observe
standard precautions when mixing HiSO,
with water. Slowly add the add to the flask
with constant swirling.) Add some soft glass
beads and several Small pieces of broken
glass tubing, and assemble the apparatus as
shown in Figure 13A-2. Heat the flask until it
reaches a temperature of 175*C fo Adjust the
acid/water ratio for subsequent distillation*.
Discard the distillate.
7.3.4 Distillation. Cool the contents of
the distillation flask to below 80'C. Pipet an
aliquot of sample containing less than 10.0 mg
F directly into the distillation flask, and add
deionized distilled water to make a total
volume of 220 ml added to the distillation
flask. (To estimate the appropriate aliquot
size, select an aliquot of the solution and
treat as described in Section 7.4.1. This will
be an approximation of the F content because
of possible interfering ions.) Note: If the
sample contains chloride, add 5 mg of Ag>SO<
to the flask for every mg of chloride.
Place a 250-ml volumetric flask at the
condenser exit Heat the flask as rapidly as
possible with a Bunsen burner, and collect all
the distillate up to 175'C. During heatup, play
the burner flame up and down the side of the
flask to prevent bumping. Conduct the
distillation as rapidly as possible (15 minutes
or less). Slow distillations have been found to
produce low F recoveries. Caution: Be careful
not to exceed 175'C to avoid causing H,SO,
to distill over.
If F distillation in the mg range is to be
followed by a distillation in the fractional mg
Section No. 3.10.10
Revision No..0
Date January 4, 1982
Page 4 of 5 „
range, add 220 ml of deionized distilled water
and distill it over as in the add adjustment
step to remove residual F from the distillation
system.
The tester may use the add in the
distillation flask until there is carry-over of
interferences or poor F recovery. Check for
these every tenth distillation using •
deionized distilled water blank and •
' standard solution. Change the add whenever
the F recovery is less than 90 percent or the
blank value exceeds 0.1 fig/ml.
7.4 Analysis.
7.4.1, Containers No. 1 and No. 2. After
distilling suitable aliquots from Containers
No. 1 and No. 2 according to Section 7.3,4.
dilute the distillate in the volumetric flask* to
exactly 250 ml with deionized distilled water.
and mix thoroughly. Pipet a suitable aliquot
of each sample distillate (containing 10 to 40
>ig F/mlj into a beaker, and dilute to 50 ml
with deionized distilled water. Use the same
aliquot size for the blank. Add 10 ml of
SPADNS mixed reagent (&&13). and mix
thoroughly.
After mixing, place the sample in a
constant-temperature bath enntair.;^ the
standard solutions (tee Section &2) for SO
minutes before reading the abaorbance on the
spectrophotometer.
Set the spectrophotometer to zero
.absorbance at 570 nm with the reference
solution (&3.12). and check the
spectrophotometer calibration with the
standard solution. Determine the absorbance
of the sample*, and determine the
concentration from the calibration curve. If
the concentration does not fall within the
range of the calibration curve, repeat the
'procedure using a different size aliquot.
7.4.2 Container No. 3 (Silica Gel). Weigh
the spent silica gel (or silica gel plus
impinger) to the nearest OJ g using a balance.
The tester may conduct thi* step in the field.
& Calibration
Maintain a laboratory log of all
calibration*.
8.1 Sampling Train. Calibrate the
sampling train components according to the
indicated sections in Method 5: Probe Nozzle
(Section 5.1); Pilot Tube (Section 5.2);
Metering System (Section 5J): Probe heater
(Section 5.4); Temperature Gauges (Section
5.5); Leak Check of Metering System (Section
5.6); and Barometer (Section 5.7).
8-2 Spectrophotometer. Prepare the
blank standard by adding 10 ml of SPADNS
mixed reagent to 50 ml of deionized distilled
water. Accurately prepare a series of
standards from the 0.01 mg F/ml standard
fluoride solution (6.3.10) by diluting 0,2.4.6,
8.10,12, and 14 ml to 100 ml with deionized
distilled water. Pipet 50 ml from each solution
and transfer each to a separate 100-ml
beaker. Then add 10 ml of SPADNS mixed
reagent to each. These standards will contain
0.10,20, 30,40 50, 60. and 70 fig F (0 to 1.4 Mg/
ml), respectively.
After mixing, place the reference standards
and reference solution in a constant I
temperature bath for 30 minutes before
reading the absorbance with the
spectropholometer.'Adjust all sample* to thi*
same temperature before analyzing.
-------
Section No. 3.10.10
Revision No. 0
Date January 4, 1982
Page 5 of 5
• Ft « Total F in sample, mg.
fig F a Concentration from the calibration
curve. ;ig.
T» - Absolute average dry gas meter
temperature (see Figure 5-2 of Method 5).
•K CR).
T, m Absolute average stack gas temperature
(see Figure 5-2 of Method S). *K (*R).
V< m Volume of distillate collected, ml
Vn««4) - Volume of gas sample as measured
by dry gas meter, corrected to standard
conditions, dscm (dscf).
V, m Total volume of F sample, after final
dilution, ml.
™ Volume of water vapor in the gas
sample, corrected to standard conditions
scm(scf).
9.2 Average Dry Gas Meter Temperature
and Average Orifice Pressure Drop. See data
sheet (Figure 5-2 of Method 5).
9.3 Dry Gas Volume. Calculate V^^) and
adjust for leakage, if necessary, using the
equation in section 6-3 of Method 5.
9.4 Volume of Water Vapor and Moisture
Content Calculate the volume of water vapor.
V^tat) and moisture content Bw, from the data
obtained in this method (Figure 13A-1); use
Equations 5-2 and 5-3 of Method 5.
94 Concentration.
94.1 Total Fluoride in Sample. Calculate
the amount of F in the sample using the
following equation:
Eq. 13A-1
94 3. Fluoride Concentration in Stack Gas. Determine the F concentration in the stack
gas using the following equation:
With the ipectrophotometer at 570 am. use
the reference *olution (&3.12) to Mt the
absorbance to zero.
Determine the absorbance of the
standards. Prepare a calibration curve by
plotting pg F/50 ml versus absorbance on
linear graph paper. Prepare the standard
curve initially and thereafter whenever the
SPADNS mixed reagent is newly made. Also,
run a calibration standard with each set of
samples and if it differs from the calibration
curve by ±2 percent, prepare a new standard
curve.
& CalcuJationt
Carry out calculations, retaining at least
one extra decimal figure beyond that of the
acquired data. Round off figures after final
calculation. Other forms of the equations may
be used, provided that they yield equivalent
results.
9.1 Nomenclature.
A« - Aliquot of distillate taken for color
development nil.
A, » Aliquot of total sample added to still
ml
BM - Water vapor in the gas stream,
proportion by volume.
C, - Concentration of F in stack gas, mg/m'.
dry basis, corrected to standard
conditions of 780 mm rig (29.92 in. Hg)
and 293'K (528'R)
-3 Vt V
10 3 TT-
Xstd)
Eq. 13A-2
Where:
K = 35.31 ftVrn* if Va{at> is expressed in
English units.
= 1.00 m'/m' if VB.UUD is expressed in
metric units.
9.6 Isokinetic Variation and Acceptable
Results. Use Method 5, Sections 6.11 and
6.12.
10. Bibliography
1. Bellack. Ervin. Simplified Fluoride
Distillation Method. Journal of the American
Water Works Association. 503308.1958.
2. Mitchell. W. I.,}. C. Suggs, and F.).
Bergman. Collaborative Study of EPA method
13A and Method 13B. Publication No. EPA-
600/4-77-050. Environmental Protection
Agency. Research Triangle Park, North
Carolina. December 1977.
3. Mitchell. W. ]. and M. R. Midgett
Adequacv of Sampling Trains and Analytical
Procedures Used for Fluoride. Atro. Environ.
J0.-865-872.1976.
-------
Section No. 3.10.11
Revision No. 0
Date January 4, 1982
Page 1 of 1
11.0 REFERENCES
1. Determination of Total Fluoride Emissions from Sta-
tionary Sources; SPADNS Zirconium Lake Method.
Federal Register, Vol. 45. June 20, 1980.
2. Mitchell, W. J., J. C. Suggs, and F. J. Bergman. Col-
laborative Study of EPA Method 13A and Method 13B.
EPA-600/4-77-050.
3. Martin, R. M. Construction Details of Isokinetic
Source Sampling Equipment. APTD-0581, USEPA, Air Pol-
lution Control Office, Research Triangle Park, North
Carolina. 1971.
4. Rom, J. J. Maintenance, Calibration, and Operation of
Isokinetic Source Sampling Equipment. APTD-0576.
USEFA Office of Air Programs, Research Triangle Park,
North Carolina. 1972.
ADDITIONAL REFERENCES
Standard Methods for the Examination of Water and Wastewater,
Publishedjointly bythe American Public Health Association,
American Water Works Association and Water Pollution Control
Federation, 14th Edition (1975).
MacLeod, Kathryn E., and Howard L. Crist, "Comparison of the
SPADNS Zirconium Lake and Specific Ion Electrode Network of
Fluoride Determinations in Stack Emission Samples," Analytical
Chemistry 45:1272-1273. 1973.
-------
Section No. 3.10.12
Revision No. 0
Date January 4, 1982
Page 1 of 6
12.0 DATA FORMS
Blank data forms are provided on the following pages for
the convenience .of the Handbook user. Each blank form has the
customary descriptive title centered at the top of the page.
However, the section-page documentation in the top right-hand
corner of each page of other sections has been replaced with a
number in the lower right-hand corner that will enable the user
to identify and refer to a similar filled-in form in the text
section. For example, Form M13A-2.1 indicates that the form is
Figure 2.1 in Section 3.10.2 of the Method 13A Handbook. Future
revisions of this form, if any, can be documented by 2.1A, 2.IB,
etc. Four of the blank forms (the first listed below) are in-
cluded in this section. Eighteen are in Section 3.9.12 as shown
by the M13B following the form number.
Form
2.1
5.1
5.2
5.3
1.2 (M13B)
2.3A & B (M13B)
2.4A & B (M13B)
2.5 (M13B)
2.6 (M13B)
3.1 (M13B)
4.1 (M13B)
4.2 (M13B)
4.3 (M13B)
Title
Fluoride Calibration Curve Data Form
Method 13A Analytical Data Form
Analytical Balance Calibration Form
Control Sample Analytical Data Form
Procurement Log
Dry Gas Meter Calibration Data Form
(English and Metric units)
Posttest Meter Calibration Data Form
(English and Metric units)
Stack Temperature Sensor Calibration
Data Form
Nozzle Calibration Data Form
Pretest Sampling Checks
Nomograph Data Form
Fluoride Field Data Form
Sample Recovery and Integrity Data Form
-------
Section No. 3.10.12
Revision No. 0 '
Date January 4, 1982
Page 2 of 6
Form
Title
4.4 (M13B)
4.5 (M13B)
5.1 (M13B)
5.2 (M13B)
6.1A & 6.IB (M13B)
8.2 (M13B)
Sample Label
On-Site Measurement Checklist
Posttest Calibration Checks
Fluoride Analytical Data Form
Fluoride Calculation Data Form
(English and Metric units)
Method 13B Checklist To Be Used by Auditors
-------
Spectrophotometer number
Calibration dat
Ambient tempera
Spectrophotomet
Reference solut
Absorbance reac
40 ug
0.7
0.6
0.5
d
0 0.4
-------
Plant
Date
METHOD ISA ANALYTICAL DATA FORM
Location
Analyst SPADNS mix date
es identifiable
nt temperature
e was concentrated
yes no All liquid levels at mark yes
Temperature of samples Temperature of standards
yes no Solids fused and added to liquid yes
no
no
Sample
number
Sample
identi-
fication
Total .
volume
of sample
before
distill.
(Vt), ml
.
Aliquot
of
sample
for
distill.
(At), ml.
mg of
chloride
per liter
of sample
mg of
silver
chloride
added
Sample
volume
from still
(Vd), ml
Aliquot
of sample
for analysis
(Ad), ml
Absorb.
of sample
at 570 nm
OD
M9 F
in sample
Total
weight
of FD
(Ft),
mg
Total weight of fluoride in sample (F.)
F = 10
(;ug F)
Control samples results must be between 19.6 ug and 20.4 ug for
undistilled sample on 18.0 an 22.0 ug for distilled sample
Remarks:
Signature of analyst _
Signature of reviewer_
Quality Assurance Handbook M13A-5.1
-------
Balance name
Number
Classification of standard weights
Date
0.5000 g
1.0000 g
10.0000 g
50.0000 g
100.0000 g
Analyst
Quality Assurance Handbook M13A-5.2
-------
Plant
Date of analysis
Analyst
Date of calibration curve
Ambient temperature
Temp, of calibration curve
Concentration of control sample
Distilled
Undistilled
Control sample temperature
Absorbance of control sample
Amount of F in control sample
from calibration curve
Percent error between measured
and calculated concentration
Were acceptable results obtained on control samples (less than 2% undis-
tilled and <10% distilled)
Signature of analyst
Signature of reviewer
Quality Assurance Handbook M13A-5.3
-------
Section No. 3.11
Revision No. 0
Date January 4, 1982
Page 1 of 13
Section 3.11
METHOD 17—DETERMINATION OF PARTICULATE EMISSIONS FROM
STATIONARY SOURCES (IN-STACK FILTRATION METHOD)
OUTLINE
Number of
Section Documentati on pages
SUMMARY 3.11 2
METHOD HIGHLIGHTS 3.11 10
METHOD DESCRIPTION
1. PROCUREMENT OF APPARATUS
AND SUPPLIES 3.11.1 9
2. CALIBRATION OF APPARATUS 3.11.2 2
3. PRESAMPLING OPERATIONS 3.11.3 3
4. ON-SITE MEASUREMENTS 3.11.4 6
5. POSTSAMPLING OPERATIONS 3.11.5 1
6. CALCULATIONS 3.11.6 1
7. MAINTENANCE 3.11.7 2
8. AUDITING PROCEDURE 3.11.8 2
9. RECOMMENDED STANDARDS FOR
ESTABLISHING TRACEABILITY 3.11.9 1
10. REFERENCE METHOD 3.11.10 11
11. REFERENCES 3.11.11 1
12. DATA FORMS 3.11.12 1
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Section No. 3.11
Revision No. 0
Date January 4, 1982
Page 2 of 13"
SUMMARY
EPA Method 17 consists of procedures for the determination
of particulate emissions from stationary sources where particu-
late matter concentrations, over the normal range of temperature
associated with a source category, are known to be independent
of temperature.
This method, designed to be used in conjunction with EPA
Methods 1, 2, 3, and 4, describes an in-stack sampling system
along with proper sampling and analytical procedures.
A gas sample is extracted isokinetically from the source.
Particulate matter is collected on a glass fiber filter main-
tained at stack temperature. The mass of particulate matter is
determined gravimetrically after removal of uncombined water.
Particulate matter is not an absolute quantity; rather, it
is a function of temperature and pressure. Therefore, to pre-
vent variability in particulate matter emission regulations
and/or associated test methods, the temperature and pressure at
which particulate matter is to be measured must be carefully
defined. Of the two variables (i.e., temperature and pressure),
temperature has the greater effect upon the amount of particu-
late matter in an effluent gas stream; in most stationary source
categories, the effect of pressure appears to be negligible.
In Method 5 a temperature of 250° F is established as a
nominal reference temperature. Thus, where Method 5 is speci-
fied in an applicable subpart of the standards, particulate
matter is defined with respect to temperature. In order to
maintain a collection temperature of 250° F, Method 5 employs a
heated glass sample probe and a heated filter holder. This
equipment is somewhat cumbersome and requires care in its opera-
tion. Therefore, where particulate matter concentrations (over
the normal range of temperature associated with a specified
source category) are known to be independent of temperature, it
-------
Section No. 3.11
Revision No. 0
Date January 4, 1982
Page 3 of 13
is desirable to eliminate the glass probe and heating systems,
and sample at stack temperature.
This method describes an in-stack sampling system and
sampling procedures for use in such cases. It is intended to be
used only when specified by an applicable subpart of the stan-
dards, and only within the applicable temperature limits (if
specified), or when otherwise approved by the administrator.
This method is not applicable to stacks that contain liquid
droplets or are. saturated with water vapor. In addition, this
method shall not be used as written if the projected cross-sec-
tional area of the probe extension filter holder assembly covers
more than 5% of the stack cross-sectional area.
The Method Description which follows is based on the Refer-
ence Method that was promulgated on February 23, 1978.l
Note: Due to similarities between Method 5 and Method 17 sam-
pling and analytical equipment and procedures, only the differ-
ences pertaining to Method 17 will be presented. However, the
activity matrices are all included whether or not differences
occur in the written descriptions. All other Method 17 descrip-
tions will be referenced to the corresponding description in
Section 3.4, Method, 5. This is done for both time savings to
the reader and cost savings to the Government.
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Section No. 3.11
Revision No. 0 .
Date January 4, 1982
Page 4 of 13
METHOD HIGHLIGHTS
Specifications for Method 17 and Method 5 are very similar
with respect to calibration, sampling and analytical procedures.
The two most significant items of concern with Method 17 are the
filter holder design and the determination of method applicabil-
ity. The main reason for the problems with the filter holders
is that there are no design specifications stated for this ref-
erence method. As a result, several different commercial types
of filter holders exist on the market to date. Most of these
have some of the problems listed below and should be checked:
1. Filter holders do not remain leakless over the normal
range of temperature changes.
2. Filters do not seal properly with the filter holder
and allow particulate to circumvent the filter.
3. Filter holders tear the filter during assembly prior
to testing.
4. Particle penetration is suspected with some types of
filter holders due to a very high face velocity at the filter.
5. Filter cannot be easily removed from filter holder
during sample recovery.
6. Filter holder gasket material is unable to withstand
upper temperature limits of normal testing range.
7. Filter holder design makes assembly and disassembly
difficult.
8. Excess weight of filter holder causes probe sag in
the stack.
9. Large diameter of some filter holders prevents their
use in a 3 in. diameter port.
10. Some filter holders •• have a poor design for sample
recovery.
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Section No. 3.11
Revision No. 0
Date January 4, 1982
Page 5 of 13
Procedures for checking some of the problems have been pro-
vided in the method writeup. The remaining problems can only be
detected by using the filter holders in the field.
The second most significant concern is determining when
Method 17 is applicable. since the in-stack filtration method
was one of the first particulate methods used and is generally
easier to use, it has remained popular. Method 17 is currently
being substituted for Method 5 under certain conditions for
compliance determination with State and local air pollution
regulations. The New Source Performance Standards (NSPS) de-
fines when Method 17 can be used. However, a large number of
requests are being made to substitute Method 17 for Method 5 on
NSPS performance tests.
Depending on stack condition and pollutant composition,
Method 17 results can easily vary from as little as 10 percent
to as much as 200 percent in comparison to Method 5. Method 17
and Method 5 are not equivalent methods for many source catego-
ries, because the temperature at which the particulate is col-
lected can have a significant effect on the amount of particu-
late matter collected. Method 17 and Method 5 are equivalent
generally only when the particulate matter is independent of
temperature through the range of emission testing. As a rule of
thumb, the filter that is at a lower temperature (in-stack or
out-of-stack) will give equal or higher results than the filter
at the higher temperature.
The equivalency of Method 17 versus Method 5 may not even
be considered by the agency when allowing the use of Method 17.
The prime consideration may be the agency's legal definition of
particulate matter. As an example, if sulfuric acid is not
considered as particulate matter from power plants, the agency
may allow the use of Method 17 on power plants using even high
sulfur coal. The use of Method 17 in this case may yield a
lower measured emission rate value, but may be legally accept-
able.
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Section No. 3.11
Revision No. 0 .
Date January 4, 1982
Page 6 of 13
Method 17 does not have any special operational problems or
biases if all the prescribed procedures and specifications are
followed. As with Method 5, the most significant errors asso-
ciated with this method occur during sample collection and
recovery phase. Therefore, this method requires competent
personnel adhering to the procedures. Competence can be deter-
mined, most accurately, through observation and evaluation by a
qualified observer onsite.
The blank data forms at the end of this section may be
removed from the Handbook and used in the pretest, test, and
posttest operations. Each form has a subtitle (e.g., Method 17,
Figure 3.1) to assist the user in finding a similar filled-in
form in the method description (e.g., in Section 3.4.3 of Method
5). Only those forms that are different from those in Method 5
are included at the end of this section. On the blank and
filled-in forms, the items/parameters that can cause the most
significant errors are designated with an asterisk.
1. Procurement of Equipment
Section 3.11.1 (Procurement of Apparatus and Supplies)
gives the specifications, criteria and design features for
equipment and materials required for performing Method 17 tests.
Special design criteria have been established for the pitot
tube, nozzle, and temperature sensor assembly.
These criteria specify the necessary spacing requirements
for the various components of the assembly to prevent aerody-
namic interferences that could cause large errors in velocity
pressure measurement. Special attention has been paid to pro-
viding a detailed procedure for determining if the filter holder
design is sufficient to remain leak free through the normal
range of testing temperatures.
Section 3.11.1 is designed as a guide for the procurement
and initial check of equipment and supplies. The activity
matrix (Table 1.1) at the end of Section 3.11.1 can be used as a
quick reference; it follows the same order as the written de-
scription in the main text.
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Section No. 3.11
Revision No. 0
Date January 4, 1982
Page 7 of 13
2. Pretest Preparation
Section 3.11.2 (Calibration of Apparatus) is the same as
the calibration section for Method 5 (Section 3.4.2).
Section 3.11.3 (Presampling Operations) provides the tester
with a guide for supplies and equipment preparation for field
tests. The pretest preparation form can be used as an equipment
checkout and packing list. (Due to the length of this figure,
the blank data form is given only in Section 3.4.3, Figure 3.2).
This form was designed to provide the user with a single form
that can include any combination of Methods 1 through 8 and
Method 17 for the same field trip. The method for packing and
the description of packing containers should help protect the
equipment, but are not mandatory. Filter holders and impingers
may be loaded and charged in the base laboratory. If this is
done, seal the inlet and outlet of the filter holder, the im-
pingers containing water, and the impinger containing silica
gel.
3. On-site Measurements
Section 3.11.4 (On-site Measurements) contains a step-by-
step procedure for performing sampling and sample recovery.
Several on-site measurement requirements have been added which
will significantly improve the accuracy and precision of the
method. These added requirements include:
1. Do not use this method for saturated stacks with water
droplets,
2. Make a corresponding change in the sampling rate when
velocity pressure at each sampling point changes by >20%,
3. Leak check the sampling train at the conclusion of the
sampling run and prior to each component change during a sample
run,
4. Leak check the pitot tube at the conclusion of the
sampling run,
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Section No. 3.11
Revision No. 0
Date January 4, 1982
Page 8 of 13
5. Have one traverse diameter in a plane containing the
greatest expected concentration variation, and
6. Allow sufficient time for the filter holder to equili-
brate with the stack temperature.
The on-site measurement checklist (Figure 4.5) is provided to
assist the tester with a quick method of checking requirements.
4. Posttest Operations
Section 3.11.5 (Postsampling Operations) gives the posttest
equipment check procedures and a step-by-step analytical proce-
dure. Figure 5.1 of Section 3.4.5, or a similar form, should be
used to summarize the posttest calibration checks and should be
included in the emission test report.
The posttest operation forms (Figures 5.5 and 5.6 of Sec-
tion 3.4.5) will provide laboratory personnel with a summary of
analytical procedures used to determine the sample rinse and
filter weights. This analytical procedure is the same as for
Method 5 (Section 3.4.5).
Section 3.11.6 (Calculations) is the same as Method 5
(Section 3.4.6).
Section 3.11.7 (Maintenance) supplies the tester with a
guide for a routine maintenance program. The maintenance of the
in-stack filter holder is the only item different than Method 5
(Section 3.4.7).
5. Auditing Procedures
Section 3.11.8 (Auditing Procedures) contains a description
of necessary activities for conducting performance and system
audits. The performance audit is a check on calculation errors,
and therefore is not needed for the analytical phase since it
consists of only a gravimetric determination. Together, a per-
formance audit of data processing and a system audit of on-site
measurements should provide the independent assessment of data
quality needed to allow the collaborative test results to be
used in the final data evaluation.
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Section No. 3.11
Revision No. 0
Date January 4, 1982
Page 9 of 13
6. References
Section 3.11.9 (Recommended Standards for Establishing
Traceability) recommends the primary standards to which the
sample collection and analysis should be traceable.
Section 3.11.10 is the Reference Method and 3.11.11 (Refer-
ences) lists the references used in the compilation of this
section of the Handbook.
-------
PRETEST SAMPLING CHECKS
(Method 17, Figure 3.1)
Section No. 3.11
Revision No. 0 "'
Date January 4, 1982
Page 10 of 13
Date
Meter box number
Calibrated by
AH@
Dry Gas Meter*
Pretest calibration factor Y
tor for each calibration runj!
Impinger Thermometer
Was a pretest temperature correction used?
If yes, temperature correction
Dry Gas Meter Thermometers
(within ±2% of the average fac-
yes
no
(within ±3°C (5.4°F) over range)
yes
no
Was a pretest temperature correction made?
If yes, temperature correction (within ±3°C (5.4°F) over range)
Stack Temperature Sensor*
•
Was the stack temperature sensor calibrated against a reference thermometer?
yes ___________ no
If yes, give temperature range with which the readings agreed within ±1.5%
of the reference values to K (°R)
Barometer
Was the pretest field barometer reading correct? yes
(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
no
*Most significant items/parameters to be checked.
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Section No. 3.11
Revision No. 0
Date January 4, 1982
Page 11 of 13
ON-SITE MEASUREMENTS CHECKLIST
(Method 17, Figure 4.5)
Apparatus
Probe nozzle: stainless steel glass
Button-hook elbow size
Clean?
Pi tot tube: Type S other
Properly attached to probe?*"
Modifications
Pitot tube coefficient
Differential pressure gauge: two inclined manometers
other sensitivity
Filter holder: borosilicate glass stainless steel
Clean?
Condenser: number of impingers
Clean?
Contents: 1st 2nd 3rd 4th
Cooling system
Proper connections?
Modifications
Barometer: mercury aneroid other
Gas density determination: temperature sensor type
pressure gauge
temperature sensor properly attached to probe?*
Procedure
Recent calibration: pitot tubes* _______
meter box* thermometers/thermocoupl
Filters checked visually for irregularities?*
Filters properly labeled?*
Sampling site properly selected?
Nozzle size properly selected?*
Selection of sampling time?
All openings to sampling train plugged to prevent pretest contamination?
Impingers properly assembled? ZZII^ZIZZZZIZZZZZIIIIIZZIIIZZZZZIIIZI
Filter properly centered?
Pitot tube lines checked for plugging or leaks?*
Meter box leveled? Periodically?
Manometers zeroed?
AH@ from most recent calibration
Nomograph setup properly?
Care taken to avoid scraping nipple on stack wall?*
(continued)
-------
Section No. 3.11
Revision No. 0
Date January 4, 1982
Page 12 of 13
(continued)
Effective seal around probe when in-stack?
Filter holder allowed to equilibrate with stack temperature?
Probe moved at proper time?
Nozzle and pitot tube parallel to stack wall at all times?*
Filter changed during run?
Any particulate lost?
Data forms complete and data properly recorded?*
Nomograph setting changed when stack temp changed significantly?
Velocity pressure and orifice pressure readings recorded accurately?*
Posttest leak check performed?*(mandatory)
Leakage rate @ in. Hg
Orsat analysis from stack integrated
Fyrite combustion analysis ~sample location
Bag system leakchecked?*
If data forms cannot be copied, record:
approximate stack temp volume metered
% isokinetic calculated at end of each run
SAMPLE RECOVERY
Brushes: nylon bristle other
Clean?
Wash bottles: glass
Clean?
Storage containers: borosilicate glass other
Clean? Leakfree?
Petri dishes: glass polyethylene other
Clean?
Graduated cylinder/or balance:subdivisions <2 ml?'
other ~
Balance: type
Plastic storage containers: airtight?
Clean?
Probe allowed to cool sufficiently?
Cap placed over nozzle tip to prevent loss of particulate?*
During sampling train disassembly, are all openings capped?
Clean-up area description:
Clean? Protected from wind?
Filters: glass fiber type
Silica gel: type (6 to 16 mesh)? new? " used?
Color? Condition?
Filter handling: tweezers used?
surgical gloves? other
Any particulate spilled?* '
(continued)
-------
Section No. 3.11
Revision No. 0
Date January 4, 1982
Page 13 of 13
(continued)
Water distilled?
Stopcock grease: acetone-insoluble?
heat-stable silicone? other
Particulate recovery from: probe nozzle
probe fitting
front half of filter holder
Blank: acetone distilled water
Any visible particles on filter holder?:*
All jars adequately labeled? Sealed tightly?
Liquid level marked on jars?*
Locked up?
Acetone reagent:<0.001% residue?
glass bottles (required)
acetone blanks?
*Most significant items/parameters to be checked.
-------
Section No. 3.11.1
Revision No. 0
Date January 4, 1982
Page 1 of 9
1.0 PROCUREMENT OF APPARATUS AND SUPPLIES
A schematic of the sampling train used in Method 17 is
shown in Figure 1.1. Commercial models of this train are avail-
able. For those who want to build their own, construction
details for many, but not all of the train components are given
in APTD-0581.2 Allowable modifications are described in the
following sections.
The operating, maintenance, and calibrating procedures for
the sampling train are in APTD-0576.3 Since correct usage is
important in obtaining valid results, all users are advised to
read this document and adopt its procedures unless alternatives
are outlined herein.
In this section, applicable specifications, criteria, and/
or design features are given to aid in the selection of equip-
ment or any components that are different from those in Section
3.4.1. Procedures and limits (where applicable) for acceptance
checks are given.
Table 1.1 at the end of this section is a summary of the
quality assurance activities for the procurement and acceptance
of apparatus and supplies.
1.1 Sampling Apparatus
1.1.1 Filter Holder - An in-stack filter holder constructed of
borosilicate or quartz glass, or stainless steel is required by
the Reference Method. If a gasket is used, it should be made of
silicone rubber, Teflon, or stainless steel. Other filter
holders and gasket materials may be used subject to the approval
of the administrator. The holder should be durable, easy to
load, and leak free in normal applications. It is positioned
immediately following the nozzle, with the filter placed toward
the flow.
-------
x-y i 1.9 en 4
(0.7S tn.)
TEMPERATURE
criteria in-iiiw.il
SENSOR T£R
N
TYPE-S
PITOT TUBE
TEMPERATURE
SENSOR
\_
NOZZLE r^-flHI
IN-STACK"CO —
FILTER (
HOLDER J
TYPE-S
PITOT TUBE
1
>_^
STACK HALL
PROBE
1
PITOT \
MANOMETER!-
IMP1NGER TRAIN OPTIONAL, HAY BE REPLACED
BY AN EQUIVALENT CONDENSER
FLEXIBLE
.TUBING
THERMOMETER
ICE WATER BATH
THERMOMETER
ORIFICE
BY-PASS
VALVE
VACUUM GAUGE
-2__
VACUUM LINE
MAIN VALVE
VACUUM PUMP
SUGGESTED (INTERFERENCE -FREE) SPACINGS
Figure 1.1. Schematic of Method 17 sampling train.
(o o> n 9
uj rt < n
n n H-rt
VI !-••
K> CH H-O
oSg3
HI p fig
vo
Ul
u>
oo
K>
-------
Section No. 3.11.1
Revision No. 0
Date January 4, 1982
Page 3 of 9
One of the biggest problems with the Method 17 train is the
inability of some filter holders to remain leakless during the
wide range of temperatures for which they are used. To ensure
that each filter holder is properly designed, a leak check
should be performed as follows:
1. Assemble the sample probe, filter holder, and filter
as shown in Figure 1.1 with the exception that a steel plug or
blank should be used in place of the nozzle to provide a leak-
less seal. Note: The condenser section does not have to be
used. However, it is suggested that it be used to provide a
more normal leak check with regard to the amount of air volume
that is removed from the train and all of the standard connec-
tions will also be leak checked.
2. Perform the standard leak check at 380 mm Hg (15 in.
Hg) vacuum at ambient temperature. A leakage rate of 0.00057
m3/min (0.02 ft3/min) is allowed; however, under these labora-
tory conditions the entire train should be leakless.
3. Put the filter holder in an oven (a Method 5 filter
heater compartment can be used) at about 100°C (212°F) for about
30 min. Perform the leak check with the filter holder in the
oven. The filter holder should again remain leakless.
4. Remove the filter holder from the oven and let cool
for 30 min. Again run the leak check.
5. Place the filter holder in the oven at the maximum
temperature for which you plan to use the Method 17 filter
holder. Allow 30 min for the holder to reach this temperature
and then run the leak check. Note: This may require that the
gasket material be changed to a high temperature material.
6. Remove the filter holder and let cool for 30 min. Run
the final leak check.
If the filter holder passes these leak check procedures
then it is properly designed to remain leak free when properly
maintained. If the filter holder passes the leak checks at the
lower temperatures, but not the maximum temperature, the manu-
facturer may have to be contacted to either replace the filter
-------
Section No. 3.11.1
Revision No. 0 -
Date January 4, 1982
Page 4 of 9
holder or provide a gasket that is designed for higher tempera-
ture sampling. If the filter holder is unable to pass the leak
check procedure at 100°C return the holder to the manufacturer
unless sampling is to be performed only at ambient temperature.
1.1.2 Probe Extension - Any suitable rigid probe extension may
be used after the filter holder. After procuring a probe exten-
sion, the user should visually check it for specifications; that
is, is it the length and composition ordered? The probe exten-
sion should be visually checked for cracks or breaks, and it
should be checked for leaks on a sampling train (Figure 1.1).
This includes a proper, leak free filter holder to probe connec-
tion. It is suggested that when corrosive gases are present
during testing that the probe extension be made of stainless
steel. The use of a heated glass-lined probe should be con-
sidered by the tester when corrosive or condensible material are
present in the stack. The condensed or corroded materials in
the probe extension may drain or be back flushed into the filter
and contaminate the sample.
1.1.3 Condenser - It is recommended that an impinger system de-
scribed in Method 5 (Section 3.4) be used to determine moisture
content of the stack gas. Alternatively, a condenser that
allows the measurement of both the water condensed and the
moisture leaving the condenser, each to within 1 ml or 1 g, (as
described in Section 3.4.1) may be used.
-------
Section No. 3.11.1
Revision No. 0
Date January 4, 1982
Page 5 of 9
TABLE 1.1. ACTIVITY MATRIX FOR PROCUREMENT OF APPARATUS AND SUPPLIES
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sampling
Probe nozzle
Stainless steel (316)
or glass with sharp,
tapered angle <30°;
difference in measured
diameters <0.1 mm (0.004
in.); no nTcks, dents,
or corrosion (Sec 3.4.1)
Visually check before
each test; use a mi-
crometer to measure
ID before field use
after each repair
Reshape and
sharpen, re-
turn to the
supplier, or
reject
Filter holder
Leak free; borosilicate
or quartz glass or
stainless steel
Visually check before
use
Return to
supplier
Probe extension
Specified material of
construction; correct
length (Sec 3.4.1)
Visually check for
cracks and breaks,
leak check
Repair, re-
turn to sup-
plier, or re-
ject
Pi tot tube
Type S (Sec 3.1.2);
attached to probe with
impact (high pressure)
opening plane even with
or above nozzle entry
plane
Calibrated according
to Sec 3.1.2
Repair or re-
turn to sup-
plier
Differential
pressure
gauge
(manometer)
Meets criteria (Sec
3.1.2); agree within
5% of gauge-oil
manometer (Sec 3.4.1)
Check against a gauge-
oil manometer at a
minimum of 3 points:
0.64(0.025); 12.7
(0.5); 25.4(1.0) mm
(in.) H20
As above
Impingers
Standard stock glass;
pressure drop not ex-
cessive (Sec 3.4.1)
Visually check upon
receipt; check pres-
sure drop (Sec 3.4.1)
Return to
supplier
Filter holder
gasket
Provide a leak free
seal on filters within
the suggested manufac-
turers temperature
range
Upon receipt deter-
mine the acceptable
temperature range
for each gasket
material
Contact manu-
facturer to
determine
temperature
range
(continued)
-------
Section No. 3.11.1
Revision No. 0
Date January 4, 1982
Page 6 of 9
Table 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Vacuum gauge
0-760 mm (0-30 in.) Hg
range, ±25 mm (1 in.)
at 380 mm (15 in.)- Hg
Check against mer-
cury U-tube manometer
upon receipt
Adjust or re-
turn to sup-
plier
Vacuum pump
Leak free; capable of
maintaining a flow
rate of 0.02-0.03
mVmin (0.7 to 1.1
ftVmin) for pump
inlet vacuum of 380 mm
(15 in.) Hg
Check upon receipt
for leaks and capaci-
ty
Repair or re-
turn to sup-
plier
Orifice meter
AH@ of 46.74 ± 6.35 mm
(1.84 ± 0.25 in.) H20
at 68°F (not mandatory)
Upon receipt, visual-
ly check for damage
and calibrate against
wet test meter
Repair if
possible,
otherwise re-
turn to sup-
plier
Dry gas meter
Capable of measuring
volume within ±2% at <
flow rate of 0.02
mVmin (0.75 ftVmin)
Check for damage upon
receipt and calibrate
(Sec 3.4.2) against
wet test meter
Reject if
damaged, be-
haves errati-
cally, or
cannot be
properly ad-
justed
Thermometers
±1°C (2°F) of true
value in the range of
0° to 25°C (32° to 77°F)
for impinger thermometer
and ±3°C (5.4°F) of true
value in the range of
0°C to 90°C (32° to
194°F) for dry gas
meter thermometers
Check upon receipt
for dents or bent
stem, and calibrate
(Sec 3.4.2) against
mercury-in-glass
thermometer
Reject if un-
able to cali-
brate
Barometer
Capable of measuring
atmospheric pressure
within ±2.5 mm (0.1
in.) Hg
Check against a mer-
cury-in-glass barom-
eter or equivalent;
calibrate (Sec 3.1.2)
Determine
correction
factor, or
reject if
difference
more than
±2.5 mm (0.1
in.) Hg
(continued)
-------
Table 1.1 (continued)
Section No. 3.11.1
Revision No. 0
Date January 4, 1982
Page 7 of 9
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sample Recovery
Filter holder
and nozzle
brush
Nylon bristle with
stainless steel stem;
properly sized and
shaped
Visually check for
damage upon receipt
Replace or
return to
supplier
Wash bottles
Two; polyethylene or
glass; 500 ml
Visually check for
damage upon receipt
As above
Storage con-
tainer
Polyethylene or glass;
500 or 1000 ml
Visually check for
damage upon receipt
As above
Petri dishes
Glass or polyethylene;
sized to fit the glass
fiber filters
Visually check for
damage upon receipt
As above
Graduated
cyli nder
Glass and class A;
250 ml with subdivi-
sions <2 ml
Upon receipt, check
for stock number,
cracks, breaks, and
manufacturer flaws
As above
Balance
Capable of measuring
silica gel to ±0.5 g
Check with standard
weights upon receipt
and before each use
Replace or
return to
manufacturer
Funnel
Glass suitable for use
with sample bottles
Visually check for
damage upon receipt
Replace or
return to
supplier
Rubber police-
man
Properly sized
Visually check for
damage upon receipt
As above
Analytical
Equipment
Beakers and
weighing
dishes
Glass
Upon receipt, check
for stock number,
cracks, breaks, and
manufacturing flaws
Replace or
return to
manufacturer
(continued)
-------
Table 1.1 (continued)
Section No. 3.11.1
Revision No. 0.
Date January 4, 1982
Page 8 of 9
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Triple beam
balance
500-g capacity; cap-
able of measuring with-
in ±1 g
Check with standard
weights upon receipt
and before each use
Replace or
return to
manufacturer
Analytical
balance
Capable of measuring to
±0.1 mg
Check with standard
weights upon receipt
and before each use
As above
Filters
Glass fiber without
organic binder; 99.95%
collection efficiency
for 0.3 u dioctyl
phthalate smoke
particles
Manufacturer's guar-
antee that filters
were tested according
to ASTM D2986-71; ob-
serve under light
for defects
Return to
supplier
Temperature
gauge
Proper operating con-
dition
Visual inspection for
damage; compare with
a mercury-in-glass
at room temperature
As above
Hygrometer
Proper operating con-
dition
Visual inspection for
damage; compare with
another instrument
As above
Reagents
Silica gel
Indicating type 6-16
mesh
Upon receipt, check
label for grade or
certification
As above
Distilled water
Meets ASTM Dl193-74;
type 3 (only when
impinger particulate
catch included)
Check each lot, or
specify type when or-
deri ng
Replace or
return to
manufacturer
Stopcock grease
Acetone insoluble, heat
stable silicone grease
Upon receipt, check
label for grade or
certification
As above
(continued)
-------
Section No. 3.11.1
Revision No. 0
Date January 4, 1982
Page 9 of 9
Table 1.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Acetone
ACS grade; <0.001%
residue in glass
bottles
Upon receipt, verify
residue by evaporat-
ing a blank sample
Replace or
return to
plier
Desiccant
Indicating type anhy-
drous calcium sulfate
Upon receipt, check
for grade and certi-
fication
As above
-------
Section No. 3.11.2
Revision No. 0
Date January 4, 1982
Page 1 of 2
2.0 CALIBRATION OF APPARATUS
Calibration of apparatus is one of the most important func-
tions in maintaining data quality. The detailed calibration
procedures included in this section are designed for the equip-
ment specified by Method 17 as described in the previous sec-
tion. A laboratory log book of all calibrations must be main-
tained. Table 2.1 summarizes the quality assurance activities
for calibration. This section is the same as Method 5 (Section
3.4.2).
-------
Section No. 3.11.2
Revision No. 0-
Date January 4, 1982
Page 2 of 2
TABLE 2.1. ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Wet test meter
Capacity >3.4 mVh
(120 ftVh); accuracy
within ±1%
Calibrate initially,
and then yearly
by liquid dis-
placement (Sec
3.4.2)
Adjust until
specifica-
tions are
met, or re-
turn to
manufacturer
Dry gas meter
Y1 = Y +0.02 Y
Calibrate vs wet
test meter initially,
and when posttest
check exceeds
Y +0.05 Y
Repair, or
replace and
then recali-
brate
Thermometers
Impinger thermometer
+1°C (2°F); dry gas
meter thermometer
+3°C (5.4°F) over
range; stack tempera-
ture sensor ±1.5% of
absolute temperature
Calibrate each ini-
tially as a separate
component against a
mercury-in-glass
thermometer; then
before each field
trip compare each as
part of the train
with the mercury-in-
glass thermometer
Adjust; de-
termine a
constant
correction
factor; or
reject
Barometer
+2.5 mm (0.1 in.) Hg of
mercury-in-glass barom-
eter
Calibrate initially
vs mercury-in-glass
barometer; check
before and after
each field test
Adjust to
agree with a
certified
barometer
Probe nozzle
Average of three ID
measurements of nozzle;
difference between high
and low <0.1 mm
(0.004 in.)
Use a micrometer to
measure to near-
est 0.025 mm (0.001
in.)
Recalibrate,
reshape, and
sharpen when
nozzle be-
comes nick-
ed, dented,
or corroded
Analytical
balance
±1 mg of Class-S
weights
Check with Class-S
weights upon receipt
Adjust or
repair
-------
Section No. 3.11.3
Revision No. 0
Date January 4, 1982
Page 1 of 3
3.0 PRESAMPLING OPERATIONS
The quality assurance activities for presampling operations
are summarized in Table 3.1 at the end of this section. See
Section 3.0, of this Handbook for details on preliminary site
visits. This section is the same as Method 5 (Section 3.4.3)
with the exception of the filter holder as detailed below.
A pretest check will have to be made on most of the sam-
pling apparatus. Figure 3.2.shown in Section 3.4.3 (Method 5)
or a similar form is recommended to aid the tester in preparing
an equipment checklist, status form, and packing list for
Methods 1 through 8, Method 17, and particle sizing.
Filter holders should be washed with tap water, then with
deionized distilled water and rinsed with acetone. Allow the.
filter holder -to air dry. The filter holder should have been
checked for proper design to remain leakless at the temperature
for which sampling is to be performed. Inspect the filter
holder gasket and replace if necessary. The proper gasket
material must be used for the stack temperature expected (i.e.,
a Teflon gasket will not work at 500°F). It is usually best to
pack all types of gasket material normally used for that filter
holder in the event that the stack temperature is not the same
as reported in the pretest preparation. The manufacturer's sug-
gested temperature range should be known for each type of gasket
material used.
-------
Section No. 3.11.3
Revision No. 0
Date January 4, 1982
Page 2 of 3 •
TABLE 3.1 ACTIVITY MATRIX FOR PRESAMPLING OPERATIONS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Probe
1. Probe extension free
of contaminants
1. Clean probe in-
ternally by brushing
with tap water, de-
ionized distilled wa-
ter, and acetone; air
dry before test
1. Repeat
cleaning and
assembly pro-
cedures
2. Probe leak free
at 380 mm (15 in.) Hg
2. Visually check be-
fore test
2. Replace
Impingers,
filter
holders, and
glass con-
tainers
Clean and free of
breaks, cracks, leaks,
etc.
Clean with detergent,
tap water, and
deionized distilled
water
Repair or
discard
Pump
Sampling rate of 0.02-
0.03 m3/min (0.66 to
1.0 ftVmin) up to 380
mm (15 in.) Hg at pump
inlet
Service every 3 mo
or upon erratic be-
havior; check
oiler jars every 10
tests
Repair or re-
turn to manu-
facturer
Dry gas meter
Clean and readings
within ±2% of average
calibration factor
Calibrate according
to Sec 3.4.2; check
for excess oil
As above
Reagents and
Equipment
Sampling fil-
ters
Free of irregularities,
flaws, pinhole leaks;
desiccate 24 h at 20°
±5.6°C (68° ± 10°F),
or oven dry at 105°C
(220°F) 2 to 3 h;
constant weight ±0.1 mg
Visually check prior
to testing; weigh on
balance to 0.1 mg
prior to field use
Replace
(continued)
-------
Section Ho. 3.11.3
Revision No. 0
Date January 4, 1982
Page 3 of 3
Table 3.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Water
Deionized distilled
conforming to
ASTM-D1193-74, Type 3
Run blank evapora-
tions prior to field
use to eliminate high
solids (only required
if impinger contents
to be analyzed)
Redistill or
replace
Stopcock grease
Acetone insoluble,
heat stable silicone
grease
Check label data upon
receipt
Replace
Sample recovery
acetone
Reagent grade, £0.001%
residue in glas?
bottles
Run blank evapora-
tions upon receipt
Replace or
return to
supplier
Packing Equip-
ment for
Shipment
Impingers, con-
tainers, and
assorted
glassware
Rigid container pro-
tected by polyeth-
ylene foam
Prior to each ship-
ment
Repack
Pump
Sturdy case lined with
polyethylene foam ma-
terial if not part of
meter box
As above
As above
Meter box
Meter box case and/or
additional material to
protect train compon-
ents; pack spare meter
box
As above
As above
Wash bottles
and storage
containers
Rigid foam-lined con-
tainer
As above
As above
-------
Section No. 3.11.4
Revision No. 0
Date January 4, 1982
Page 1 of 6
4.0 ON-SITE MEASUREMENTS
The on -site activities include transporting equipment to
the test site, unpacking and assembling the equipment, making
duct measurements, performing the velocity traverse, determining
molecular weights and stack gas moisture contents, sampling for
particulates, and recording the data. Table 4.1 at the end of
this section summarizes the quality assurance activities for
on -site activities. Blank data forms are in Section 3.4.12
(Method 5) for the convenience of the Handbook user. This sec-
tion is the same as Method 5 (Section 3.4.4) with the exception
of the items detailed below.
4.1 SAMPLING
4.1.1 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 com-
mences .
Place 100 ml of distilled water (a graduated cylinder may
be used) in each of the first two impingers; leave the third im-
pinger empty; and place ^200-300 g of preweighed silica gel in
the fourth impinger. Record the weight of the silica gel and
the container on the appropriate 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.
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.
Note; Some filter holder designs require the use of a glass
fiber thimble. If this type of filter is used, ensure that a
good fit is made. Poor quality control in filter production by
-------
Section No. 3.11.4
Revision No. 0
Date January 4, '1982
Page 2 of 6
some manufacturers have resulted in a loose fit or the tearing
of the filter from too tight of a fit.4
4.1.2 Sampling Train Assemblage - Assemble the train as shown
in Figure 1.1, using (if necessary) a very light coat of sili-
cone grease only on the outside of all ground-glass joints to
avoid contamination. 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 metal. Its 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. Note; Because of the larger diameter of
the in-stack filter holders, it is critical that the 3 in.
minimum spacing be observed from the nozzle tip to the closest
portion of the filter holder.
4.1.3 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 3.11.10) specifies that leak
checks be performed at certain times as discussed below.
Pretest - A pretest leak check is recommended, but not re-
quired. If the tester opts to conduct the pretest leak check,
the following procedure should be used:
After the sampling train has been assembled, plug the
nozzle with a material that can withstand the stack temperature.
Place the filter holder in the stack and allow time for the fil-
ter temperature to stabilize with the stack temperature. Leak
check the train by pulling a 380 mm (15 in.) Hg vacuum. Note;
A lower vacuum may be used if it is not exceeded during the
test. Also after the filter holder has been heated to the stack
temperature, it may be necessary to remove it from the stack and
retighten before it will pass the leak check.
-------
Section No. 3.11.4
Revision No. 0
Date January 4, 1982
Page 3 of 6
Posttest - Same as for Method 5.
4.1.4 Sampling Train Operation - Just prior to placing probe
in-stack to heat filter holder, clean the portholes to minimize
the chance of sampling deposited material. Place the capped off
filter holder in the stack and allow sufficient time for the
filter holder to equilibrate with the stack temperature. This
may take as much as 30 min for some stacks.
4.2 SAMPLE RECOVERY
The Reference Method (Section 3.11.10) requires that the
sample be recovered from the nozzle and all sample exposed
portion of the filter holder and the filter in an area sheltered
from wind and dust to prevent contamination of the sample. The
capped-off impinger box or condenser system and the capped
sampling probe can be transported to the cleanup area without
risk of losing or contaminating the sample.
4.2.1 Filter - Initially take three unused filters for each
field test series and label them as filter blanks. (These three
should have been tared when the sample filters were tared, since
they are used as the control samples for the check on. the ana-
lytical balance.) The filter used for the sample run should be
recovered. Using a pair of tweezers and/or clean disposable
surgical type gloves, carefully remove the filter from the
filter holder, and place it in its designated petri dish. Any
filter fibers or particulates which adhere to the filter gasket
should be removed with a nylon bristle brush or a sharp blade
and placed in the container, which should then be closed,
sealed, and labeled. Note; When the filter holder is. opened
check the filter for tares in the collection area and check the
sealed area to determine if any particulate has bypassed the
seal or if the filter was improperly placed in the filter
holder.
4.2.2 Nozzle and Filter Holder - Initially, put a minimum of
200 ml of the acetone used for sample recovery in a sample
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Section No. 3.11.4
Revision No. 0
Date January 4, 1982
Page 4 of 6
bottle, mark the liquid level, seal, and label the bottle. Then
enter the bottle number on the sample recovery and integrity
form. A single sample bottle is usually adequate for the col-
lection of all the rinses; it should be labeled and recorded in
the same manner as the blank sample.
Clean the outside of the probe filter holder, pitot tube,
and nozzle to prevent particulates from being brushed into the
sample bottle. Carefully remove the probe nozzle, and rinse the
inside surface (using a nylon bristle brush and several acetone
rinses) into the sample bottle until no particles are visible in
the rinse. Then make one final rinse of the nozzle with the
acetone. Clean the swagelok fitting by the same procedure.
After rinsing each component, rinse the sample off the brush
into the sample container.
Distilled water may be used instead of acetone when ap-
proved by the administrator and should be used when specified by
the administrator. In these cases, save a water blank and
follow administrator's directions on analysis.
After ensuring that all joints are wiped clean of silicone
grease (if applicable), clean the inside of the front half
(sample exposed portion) of the filter holder by rubbing the
surface with the brush and rinsing with acetone. Rinse each
surface three times or more if needed to remove visible partic-
ulate. Make final rinse of the brush and filter holder.
After all the rinsings have been collected, tighten the lid
on the sample bottle securely. As a precaution in case of
leakage, mark the acetone level on the bottle, and note it on
the sample recovery form (Figure 4.4 of Method 5).
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Section No. 3.11.4
Revision No. 0
Date January 4, 1982
Page 5 of 6
TABLE 4.1. ACTIVITY MATRIX FOR ON-SITE MEASUREMENT CHECKS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sampling
Filter
Centered in holder; no
breaks, damage, or con-
tamination during load-
ing
Use tweezers or surg-
ical gloves to load
Discard fil-
ter, and re-
load
Condenser
(addition of
reagents)
100 ml of distilled
water in first two
impingers; 200-300 g
silica gel in fourth
impinger
of
Use graduated cylinder
to add water, or weigh
each impinger and its
contents to the near-
est 0.5 g
Reassemble
system
Assembling
sampling
train
1. Assembly specifica-
tions in Fig 1.1
1. Before each sam-
pling run
1. Reassem-
ble
2. Leak rate 2 min
2. Make a quick cal-
culation before test,
and exact calculation
after
As above
3. Minimum number of
points specified by
Method 1
3. Check before the
first test run by mea-
suring duct and using
Method 1
3. Repeat
the procedure
to comply
with specifi-
cations of
Method 1
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Section No. 3.11.4
Revision No. 0 .
Date January 4, 1982
Page 6 of 6
Table 4.1 (continued)
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
4. Leakage rate
<0.00057 m3/min (0.02
ftVmin) or 4% of the
average sampling vol-
ume, whichever is less
4. Leak check after
each test run or be-
fore equipment re-
placement during test
at the maximum vacuum
during the test (man-
datory)
4. Correct
the sample
volume, or
repeat the
sampling
Sample recovery
Noncontaminated sample
Transfer sample .to
labeled polyethylene
containers after
each test run; mark
level of solution in
the container
Repeat the
sampling
Sample
logistics,
data collec-
tion, and
packing of
equipment
1. All data recorded
correctly
1. After completion
of each test and be-
fore packing
1. Complete
data
2. All equipment exam-
ined for damage and
labeled for shipment
2. As -.above
2. Repeat
the sampling
if damage oc-
curred during
the test
3. All sample contain-
ers and blanks properly
labeled and packaged
3. Visually check
upon completion of
each sampling
3. Correct
when possible
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Section No. 3.11.5
Revision No. 0
Date January 4, 1982
Page 1 of 1
5.0 POSTSAMPLING OPERATIONS
Table 5.1 summarizes the quality assurance activities for
the postsampling operations. This section is the same as Method
5 (Section 3.4.5).
TABLE 5.1. ACTIVITY MATRIX FOR POSTSAMPLING OPERATIONS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Sampling
Dry gas meter
Within ±5% of calibra-
tion factor
Make three runs at a
single, intermediate
orifice setting and
at highest vacuum
occurring during test
(Sec 3.4.2)
Recalibrate
and use cali-
bration fac-
tor that
gives lesser
sample volume
Meter thermome-
ter
Within ±6°C (10.8°F)
at ambient pressure
Compare with ASTM
mercury-in-glass
thermometer after
each field test
Recalibrate
and use
higher tem-
perature for
calculations
Barometer
Within ±5 mm (0.2 in.)
Hg at ambient pressure
Compare with mercury
in-glass barometer
after each field
test
Recalibrate
and use lower
barometric
values for
calculations
Stack tempera-
ture
Within ±1.5% of the
reference check temp-
erature (°R)
After each run, com-
pare with reference
temperature
Recalibrate
and calculate
with and
without tem-
perature cor-
rection
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Section No. 3.11.6
Revision No. 0
Date January 4, 1982
Page 1 of 1
6.0 CALCULATIONS
Calculation errors due to mathematical mistakes can be a
large part of total system error. Therefore, each set of calcu-
lations should be repeated or spot checked by a team member
other than the one who performed them originally. If a differ-
ence greater than a typical roundoff error is detected, the
calculations should be checked step by step until the source of
error is found and corrected. A computer program can be advan-
tageous in reducing calculation errors. If a standardized
computer program is used, the original data entry should be
checked; if differences are observed, a new computer run should
be made. Table 6.1 summarizes the quality assurance activities
for calculations. This section is the same as Method 5 (Section
3.4.6).
TABLE 6.1. ACTIVITY MATRIX FOR CALCULATIONS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are mot met
Analysis data
form
All data and calcula-
tions given on the
form
Visual check
Complete the
missing data
values
Calculations
Difference between
checked and original
calculations not in
excess of roundoff
error; at least one
decimal figure beyond
that of acquired data
retai ned
Repeat all calcula-
tions starting with
raw data for hand
calculations and for
one sample per test
Indicate er-
rors in ana-
lysis; data
on Fig 6.1A
or B (Sec
3.4.6)
Isokinetic
variation
90% < I < 110%; see
Eqs 6.9 and 6.10 (Sec
3.4.6) calculation
of I
For each run, calcu-
late I
Repeat the
test, and ad-
just flow
rates to
maintain I
within ±10%
variation
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Section No. 3.11.7
Revision No. 0
Date January 4, 1982
Page 1 of 2
7.0 MAINTENANCE
Normal use of emission testing equipment subjects it to
corrosive gases, temperature extremes, vibrations, and shocks.
Keeping the equipment in good operating order over an extended
period of time requires routine maintenance and knowledge of the
equipment. Maintenance of the entire sampling train should be
performed either quarterly or after 1000 ft3 of operation,
whichever occurs sooner. Maintenance procedures are summarized
in Table 7.1. These procedures are recommended, but not re-
quired, to increase the reliabilty of the equipment. This
section is the same as Method 5 (Section 3.4.7) except for the
following addition.
Because of their design and use, many filter holders are
high maintenance items. The filter holder must be cleaned, the
bent and damaged parts replaced, the filter surfaces smoothed,
and the gaskets cleaned or replaced to ensure that the filter
holder remains leak tight, does not contaminate the sample and
does not tear the filter.
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Section No. 3.11.7
Revision No. 0 .
Date January 4, 1982
Page 2 of 2
TABLE 7.1 ACTIVITY MATRIX FOR EQUIPMENT MAINTENANCE CHECKS
Apparatus
Acceptance limits
Frequency and method
of measurements
Action if
requirements
are not met
Routine main-
tenance
No erratic behavior
Routine maintenance
quarterly; disassem-
ble and clean yearly
Replace parts
as needed
Fiber vane pump
Leak free; required
flow
Periodic check of oil
jar; remove head and
change fiber vanes
Replace as
needed
Diaphragm pump
Leak-free valves func-
tioning properly; re-
quired flow
Clean valves during
yearly disassembly
Replace when
leaking or
when running
erratically
Dry gas meter
No excess oil, corro-
sion, or erratic dial
rotation
Check every 3 mo for
excess oil or corro-
sion by removing the
top plate; check
valves and diaphragm
when meter dial runs
erratically or when
meter will not cali-
brate
Replace parts
as needed, or
replace meter
Inclined manom-
eter
No discoloration of or
visible matter in the
fluid
Check periodically;
change fluid during
yearly disassembly
Replace parts
as needed
Sample train
No damage or leaks
Visually check every
3 mo; completely
disassemble and clean
or replace yearly
If failure
noted, use
another en-
tire control
console, sam-
ple box, or
umbilical
cord
NozzTe
No dents, corrosion,
or other damage
Visually check be-
fore and after each
test run
Use another
nozzle or
clean,
sharpen, and
recalibrate
-------
Section No. 3.11.8
Revision No. 0
Date January 4, 1982
Page 1 of 2
8.0 AtJDITING PROCEDURE
An audit is an independent assessment of data quality.
Independence is achieved by using apparatus and standards that
are different from those used by the regular field crew. Rou-
tine quality assurance checks by a field team are necessary for
obtaining good quality data, but they are not part of the au-
diting procedure. Table 8.1 summarizes the quality assurance
activities for the auditing. This section is the same as Method
5 (Section 3.4.8) with the exception of the system audit de-
scription.
The major difference in the system audit of Method 17
versus Method 5 is that the in-stack filter holder is heated by
the stack. This temperature is critical 1) before test for the
pretest leak check, 2) during sample extraction, and 3) during
the posttest leak check. The observer should be satisfied that
the filter holder temperature is relatively close to the actual
stack temperature.
-------
Section No. 3.11.8
Revision No. 0>
Date January 4"; 1982
Page 2 of 2
TABLE 8.1. ACTIVITY MATRIX FOR AUDITING PROCEDURES
Audit
Acceptance limits
Frequency and method
of measurement
Action if
requirements
are not met
Volumetric
sampling
phase of
Method 17
Measured pretest volume
within ±10% of the
audit volume
Once during every en-
forcement source
test, measure ref-
erence volume, and
compare with true
volume
Review oper-
ating tech-
nique
Data processing
errors
Original and check caV
culations agree
Once during each
enforcement source
test, perform inde-
pendent calculations
starting with the
recorded data
Check and
correct all
data
Systems audit
Conducted method as
described in this sec-
tion of the Handbook
Once during each
enforcement test
until experience
gained, then every
fourth test, observe
techniques; use
audit checklist
Fig 8.1 (Sec 3.4.8)
Explain to
team the de-
viations
from recom-
mended tech-
niques; note
the devia-
tions on Fig
8.1 (Sec
3.4.8)
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Section No. 3.11.9
Revision No. 0
Date January 4, 1982
Page 1 of 1
9.0 RECOMMENDED STANDARDS FOR ESTABLISHING TRACEABILITY
To achieve data of desired quality, two considerations are
necessary: (1) the measurement process must be in a state of
statistical control, and (2) the systematic errors, when com-
bined with the random variations (errors of measurement), must
result in a suitably small uncertainty.
To ensure good data, it is necessary to perform quality
control checks and independent audits of the measurement pro-
cess; to document the data by quality control charts (as appro-
priate); and to use materials, instruments, and procedures which
can be traced to a standard of reference.
The working calibration standards should be traceable to
primary or higher level standards such as those listed below.
1. The dry gas meter should be calibrated against a wet
test meter which has been verified by liquid displace-
ment, as described in Section 3.4.2.
2. The analytical balance should be checked against
Class-S weights that are traceable to NBS standards.
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Section No. 3.11.10
Revision No. 0
Date January 4, 1982
Page 1 of 11
10.0 REFERENCE METHOD3
MTTHOD 17. DrrtMHNATIOH Of FAXTICULATZ
MISSIONS niOM STATIONARY SOURCES (IN-
STACK mTKATION MZTHOD)
Introduction
PartlQuiate nutter is not an absolute
quantUyr.rather. it is a function of tempera-
ture and1 pressure. Therefore, to prevent
variability In paniculate matter emission
regulations and/or associated test methods,
the temperature and pressure at which par-
ticulate matter is to be measured must be
carefully defined. Of the two variables (I.e..
temperature and pressure), temperature has
the greater effect upon the amount of par-
ticulate matter in an effluent gas stream; in
most stationary source categories, the effect
of pressure appears to be negligible.
In method 5. 250* P is established as a
nominal reference temperature. Thus.
where Method 5 is specified in an applicable
subpart of the standards, paniculate matter
Is defined with respect to temperature. In
order to maintain a collection temperature
of 290' F. Method 5 employs a heated glass
•ample probe and a heated filter holder.
This equipment is somewhat cumbersome
and requires care in its operation. There-
fore, where paniculate matter concentra-
tions (over the normal range of temperature
associated with a specified source category)
are known to be Independent of tempera-
ture, it is desirable to eliminate the glass
probe and heating systems, and sample at
stack temperature.
This method describes an la-stack sam-
pling system and sampling procedures for
use In such cases. It is intended to be used
only when specified by an applicable sub-
part of the standards, and only within the
applicable temperature Umltc (if specified).
or when otherwise approved by the Admin-
istrator.
1. Principle and Applicability.
I.I Principle. Paniculate matter Is with-
drawn Isokinetically from the source and
collected on a glass fiber filter maintained
at stack temperature. The paniculate mass
is determined gravimetricaUy after removal
of uncombined water.
1.2 Applicability. This method applies to
the determination of paniculate emissions
from stationary sources for determining
compliance with new source performance
standards, only when specifically provided
for in an applicable subpart of the stan-
dards. This method Is not applicable to
stacks that contain liquid droplets or are
saturated with water vapor. In addition, this
method shall not be used as written if the
projected cross-sectional area of the probe
extension-filter holder assembly covers
more than S percent of the stack cross-sec-
tional area (see Section 4.1.2).
2. Apparatus.
2.1 Sampling Train. A schematic of the
sampling train used in this method is shown
In Figure 17-1. Construction details for
many, but not all. of the train components
are given In APTD-0581 (Citation 21n Sec-
tion 7): for changes from the APTD-0581
document and for allowable modifications
to Figure 17-1. consult with the Administra-
tor.
Taken from Federal Register, Vol. 43, No. 37, Thursday,
February 23, 1978.
-------
TEMPERATURE IN STACK
SENSOR FILTER HOlOfR
f >1.
IMPINGER TRAIM OPTIONAL. MAY If REPLACED
•Y AN EOUIVAlf NT CONOEhSER
I > I.I cm (3 in.) *
THERMOMETER
CHICK
VAIVE
REVERSE-TYPE
PITOTTUIE
rt
-------
Section No. 3.11.10
Revision No. 0
Date January 4, 1982
Page 3 of 11
The operating and maintenance proce-
dures (or many of | the aampling train com-
ponent! are described In APTD-OS76 (Clta-
Uon 3 In Section T>. Since correct usage Is
Important in obtaining valid results, all
user* should read the APTD-0516 document
and adopt the operating and maintenance
procedures outlined In It, unless otherwise
specified herein. The sampling train con-
sists of the following components:
2.1.1 Probe Nozzle. Stainless steel (316)
or glass, with sharp, tapered leading edge.
The angle of taper shall be 030* and the
taper shall be on (the ouUlde to preserve a
constant Internal diameter. The probe
noBle shall be of | the button-hook or elbow
design, unless otherwise specified by the Ad-
ministrator. II made of stainless steel, the
nozzle shall be constructed from seamless
tubing. Other materials of construction may
be used subject to the approval of the Ad-
ministrator.
A range of sixes suitable for Uokinetlc
'"•T'lng should I be available. e.g.. 0.32 to
1.21 cm (H to H in>-*r larger If higher
volume sampling! trains are used—Inside di-
ameter (ID) nozzles in Increments of 0.16 cm
(Vi> In). Bach nozzle shall be calibrated ac-
cording to the procedures outlined In Sec-
tion S.I.
2.1.2 Filter Holder. The In-slack filter
holder shall be constructed of borosUleate
or quartz glass, or stainless steel; U a gasket
Is used. It shall be made of sillcone rubber.
Teflon, or stainless steel. Other holder and
gmsket matertalsj may be used subject to the
approval of the Administrator. The filter
bolder shall be
ttve seal against
designed to provide a posi-
leakage from the outside or
around the filter.
2.1.3 Probe Extension. Any suitable rigid
probe extension may be used after the filter
holder.
2.1.4 Pilot Tube. Type S. as described in
Section 2.1 of Method 2, or other device ap-
proved by the Administrator, the pilot tube
shall be attached to the probe extension to
allow constant monitoring of the stack gas
velocity (see Figure 11-1). The impact (high
pressure) opening plane of the pilot tube
shall be even with or above the nozzle entry
plane during sampling (see Method 2.
Figure 2-6b). It Is recommended: (1) that
the pilot tube have a known baseline coeffi-
cient, determined as outlined in Section 4 of
Method 2: and (2) that this known coeffi-
cient be preserved by placing the pilot tube
in an interference-free arrangement with re-
spect to the sampling nozzle, filter holder.
and temperature sensor (see Figure 11-1).
Note that the jl.9 cm (0.18 In) free-space be-
tween the nozzle and pilot tube shown in
Figure 11-1. ii| based on a 1.3 on (0.5 in) ID
nozzle. If the sampling train is designed for
sampling at higher flow rates than that de-
scribed In APTD-OSI1. thus necessitating
the use of larger sized nozzles, the free-
space shall be) 1.9 cm (0.16 In) with the larg-
est sized nozzle In place.
Source-sampling assemblies that do not
meet the minimum spacing requirements of
Figure 11-1 (or the equivalent of these re-
quirements, e.g.. Figure 2-1 of Method 2)
may be used: however, the pilot tube coeffi-
cients of such assemblies shall be deter-
mined by calibration, using methods subject
to the approval of the Administrator.
2.1.S Differential Pressure (Huge. In-
clined manometer or equivalent device
(two), as described in Section 2.2 of Method
2. One manometer shall be used for velocity
bead readings, and the other, for ori-
Hot differential pressure martinis
2.1.6 Condenser. It Is recommended that
the Implnger system described In Method S
be used to determine the moisture content
of the stack gas. Alternatively, any system
that allows measurement of both the water
condensed and the moisture leaving the con-
denser, each to within 1 ml or 1 g, may be
used. The moisture leaving the condenser
can be measured either by: (1) monitoring
the temperature and pressure at the exit of
the condenser and using Dalton's law of
partial pressures: or (2) passing the sample
gas stream through a silica gel trap with
exit gases kept below 20* C (68* F) and de-
termining the weight gain.
Flexible tubing may be used between the
probe extension and condenser. If means
other than silica gel are used to determine
the amount of moisture leaving the con-
denser, it Is recommended that silica gel still
be used between the condenser system and
pump to prevent moisture condensation In
the pump and metering devices and to avoid
the need to make corrections for moisture
m the metered volume.
2.1.1 Metering System. Vacuum gauge.
leak-free pump, thermometers capable of
measuring temperature to within 3* C (5.4*
F). dry gas meter capable of measuring
volume to within 2 percent, and related
equipment, as shown In Figure 11-1. Other
metering systems capable of «"^"«*'"'"g
sampling rates within 10 percent of Isokine-
tlc and of determining sample volumes to
within 2 percent may be used, subject to the
approval of the Administrator. When the
metering system is used in conjunction with
a pilot tube, the system shall enable checks
of Isoklnetlc rates.
Sampling trains utilizing metering sys-
tems designed for higher flow rates than
that described in APTD-OMl or APTD-0516
may be used provided that the specifica-
tions of this method are met.
2.1.8 Barometer. Mercury, aneroid, or
other barometer capable of measuring at-
mospheric pressure to within 2.5 mm Hg
(0.1 In. Hg). In many eases, the barometric
reading may be obtained from a nearby na-
tional weather service station, in which ease
the station value (which is the absolute
barometric pressure) shall be requested and
an adjustment for elevation differences be-
tween the weather station and sampling
point shall be applied at a rate of minus U
mm Hg (0.1 in. Hg) per 30 m (100 ft) eleva-
tion increase or vice versa for elevation de-
crease.
2.1.9 Gas Density Determination Equip-
ment. Temperature senior and pressure
gauge, as described in Sections 2.3 and 2.4 of
Method 2. and gas analyzer. U necessary, as
described in Method 3.
The temperature sensor shall be attached
to either the pilot tube or to the probe ex-
tension. In a fixed configuration. If the tem-
perature sensor is attached In the field: the
sensor shall be placed In an Interference-
free arrangement with respect to the Type
S pilot tube openings (as shown In Figure
11-1 or In Figure 2-1 of Method 2). Alterna-
tively, the temperature sensor need not be
attached to either the probe extension or
pilot tube during sampling, provided that a
difference of not more than 1 percent In the
average velocity measurement Is introduced.
This alternative Is subject to the approval
of the Administrator.
2.2 Sample Recovery.
2.2.1 Probe Nozzle Brush. Nylon bristle
brush with stainless steel wire handle. The
brush shall be properly sized and shaped to
brush out the probe nozzle.
2.2.2 Wash -Bottles—Two. Glass wash
bottles are recommended: polyethylene
wash bottles may be used at the option of
the tester. It is recommended that acetone
not be stored In polyethylene bottles for
longer than a month.
2.2.3 Glass Sample Storage Containers.
Chemically resistant, borosllicate glass bot-
tles, for acetone washes, 600 ml or 1000 ml.
Screw cap liners shall either be rubber-
backed Teflon or shall be constructed so as
to be leak-free and resistant to chemical
attack by acetone. (Narrow mouth glass bot-
tles have been found to be less prone to
leakage.) Alternatively, polyethylene bottles
may be used.
2.2.4 Petri Dishes. For filter samples:
glass or polyethylene, unless otherwise
specified by the Administrator.
2J.5 Graduated Cylinder and/or Bal-
ance. To measure condensed water to within
1 ml or 1 g. Graduated cylinders shall have
subdivisions no greater than 2 ml. Most lab-
oratory balances are capable of weighing to
the nearest 0.5 g or less. Any of these bal-
ances Is suitable for use here and in Section
2.3.4.
2.2.6 Plastic Storage Containers. Air
tight containers to store silica gel.
2.2.1 Funnel and Rubber Policeman. To
aid in transfer of silica gel to container: not
necessary If silica gel Is weighed In the field.
2.2.8 Funnel. Glass or polyethylene, to
aid In sample recover}'.
2.3 Analysis.
2.3.1 Glass Weighing Dishes.
2.3.2 Desiccator.
2.3.3 Analytical Balance. To measure to
within 0.1 mg.
2.3.4 Balance. To measure to within 0.9
mg.
2.3.6 Beakers. 250 ml.
2.3.6 Hygrometer. To measure the rela-
tive humidity of the laboratory environ-
ment.
2.3.1 Temperature Gauge. To measure
the temperature of the laboratory environ-
ment
3. Reagents.
3.1 Sampling.
3.1.1 Filters, The tn-stack filters shall be
glass mats or thimble fiber filters, without
organic binders, and shall exhibit at least
99.95 percent efficiency (00.05 percent pene-
tration) on 0.3 micron dioctyl phthalate
smoke particles. The filter efficiency tests
shall be conducted In accordance with
ASTM standard method D 2986-11. Test
data from the supplier's quality control pro-
gram are sufficient for this purpose.
3.1.2 Silica Gel. Indicating type. 6- u 16-
mech. If previously used, dry at 115* C (3SO*
F) for 2 hours. New silica gel may be used u
received. Alternatively, other types of desic-
canls (equivalent or better) may be used.
subject to the approval of the Administra-
tor.
3.1.3 Crushed Ice.
3.1.4 Stopcock Grease. Acetone-Insoluble.
heat-stable sillcone grease. This is not nec-
essary if screw-on connectors with Teflon
sleeves, or similar, are used. Alternatively.
other types of stopcock grease may be used.
subject to the approval of the Administra-
tor.
3.2 Sample Recovery. Acetone, reagent
grade. 00.001 percent residue. In glass bot-
tles. Acetone from metal containers general-
ly has a high residue blank and should not
be used. Sometimes, suppliers transfer ac-
etone to glass bottles from metal containers.
Thus, acetone blanks shall be run prior to
field use and only acetone with low blank
-------
values (00.001 percent) shall be used. la no
cue shall i blank value of greater than
0.001 percent of the weight of acetone used
be subtracted from the sample weight.
3.3 Analysts.
3.3.1 Acetone. Same as 3.2.
3.3.2 Deslccant. .Anhydrous calcium sul-
fate, Indicating type. Alternatively, other
types of desiccants may be used, subject to
the approval of the Administrator.
4. Procedure.
4.1 Sampling. The complexity of this
method is such that. In order to obtain reli-
able results, testers should be trained and
experienced with the test procedures.
4.1.1 Pretest Preparation. All compo-
nents shall be maintained and calibrated ac-
cording to the procedure described in
APTD-057S, unless otherwise specified
herein.
Weigh several 200 to 300 g portions of
silica gel in air-tight containers to the near-
est 0.5 g. Record the total weight of the
silica gel plus container, on each container.
As an alternative, the silica gel need not be
preweighed, but may be weighed directly in
Its impinger or sampling holder just prior to
train assembly.
Check filters visually against light for ir-
regularities and flaws or plnhole leaks.
Label filters of the proper slxe on the back
side near the edge using numbering ma-
chine ink. As an alternative, label the ship-
ping containers (glass or plastic petri dishes)
and keep the filters in these containers at
all times except during sampling and weigh-
ing.
Desiccate the filters at 20±S.«' C (68±10*
F) and ambient pressure for at least 24
hours and weigh at Intervals of at least 6
hours to a constant weight, i.e., 00.5 mg
change from previous weighing*, record re-
sults to the nearest 0.1 mg. During each
weighing the filter must not be exposed to
the laboratory atmosphere for a period
greater than 2 minutes and a relative hu-
midity above 50 percent. Alternatively
(unless otherwise specified by the Adminis-
trator), the filters may be oven dried at 105*
C (220* D for 2 to 3 hours, desiccated for 2
hours, and weighed. Procedures other than
those described, which account tor relative
humidity effects, may be used, subject to
the approval of the Administrator.
4.1.2 Preliminary Determinations. Select
the sampling site and the minimum number
of sampling points according to Method 1 or
as specified by the Administrator. Make a
project«d-area model of the probe exten-
sion-filler holder assembly, with the pltot
tube face openings positioned along the cen-
terline of the stack, as shown in Figure 11-2.
Calculate the estimated cross-section block-
age, as shown in Figure 17-2. If the blockage
exceeds 5 percent of the duct cross sectional
area, the tester has the following options:
(Da suitable out-of-stack filtration method
may be used Instead of In-slack filtration; or
(2) a special in-staek arrangement, in which
the sampling and velocity measurement
sites are separate, may be used; for details
concerning this approach, consult with the
Administrator (see also Citation 10 In Sec-
tion 7). Determine the stack pressure, tem-
perature, and the range of velocity heads
using Method 2: It is recommended that a
leak-check of the pltot lines (see Method 2.
Section 3.1) be performed. Determine the
moisture' content using Approximation
Method 4 or Its alternatives for the purpose
of making isokinetic sampling rate settings.
• Determine the stack gas dry molecular
weight, as described in Method 2. Section
3.6; if Integrated Method 3 sampling Is used
for molecular weight determination, the in-
tegrated bag sample shall be taken simulta-
neously with, and for the same total length
of time'as. the particular sample run.
Section No. 3.11.10
Revision No. 0 .
Date January 4, 1982
Page 4 of 11 *
STACK
WALL
IK-STACK FILTER.
PROIE EXTENSION
ASSEMUY
ESTIMATED
BLOCKAGE
fsMADED AREA]
* [_ DUCT AREA J
X 100.
Figure 17-2. Projected-area model of cross-section
blockage (approximate average for a sample traverse)
caused by an in-stack filter holder-probe extension
assembly.
-------
Section No. 3.11.10
Revision No. 0
Date January 4, 1982
Page 5 of 11
Select a nozzle atee based on the rmnre ot
velocity heads, such that It Is not necessary
te chante the nozzle size In order to main-
tain Isokinelic Bunpllnc ntes. Durtnc the
run. do not chance the noslr ilcr. Ensure
that the proper differential pressure taure
la chosen tor the range of velocity heads en-
countered (a«e Section 2.2 of Method 2).
Select a probe extension lenrth men thai
all trmvem potnU lean be ammpled. For lare*
•tackj. consider sampling from opposite
•Ide* of the tuck to reduce the length of
probes.
Select a total sampling time creater than
or equal to the minimum total sampling
time specified to the test procedures for the
specific Industry men that (1) Ov ssmnline
time per point Is not leu .than 3 minutes cor
tome greater time Interval if specified by
the Administrator). and (2) the sample
volume taker, (corrected to standard condi-
tions) will exceed the required minimum
total ns sample volume. The latter Is based
on an approximate averacr samplinc rale.
' It is recommended that the number of
minute* sampled at each point be an Interer
or an iniecer plus one-half minute, in order
to avoid timekeeping errors.
' In some circumstances, e.g.. batch cycles.
It may be necessary to sample for shorter
times at the traverse polnu and to obtain
•mailer cat sample volumes. In thesr cases.
the Administrator's approval must first be
•btatned.
4.1.S Preparation of Collection Train.
During preparation and auembly of the
sampling train, keep all opening* where con-
tamination cut occur covered until just
prior to assembly or until sampling is about
10 becln.
If Implncers are used to condense stack
fas moisture., prepare them as folio*?: place
100 ml of waier In earn of the first tvo Ira-
pincers, leave the third Implnger empty.
and transfer approximately 200 to JOO g of
preweighed silica eel from Its container to
the fourth implnger. More silica eel may be
used, but care should be taken to ensure
thai It Is noi entrained snd carried out from
the implncer during sampling. Place the
container in a clean place for later use In
the sample recovery. Alternatively, the
weigh: of the silica ce) plus Implnger may
be determined to the nearest O.S g and re-
cerdid.
If some means other than Implncers Is
' used to condense moisture, prepare the eon-
denser (and. if appropriate, silica eel for
condenser outlet) for .use.
Using a tweezer or clean disposable surgl-
c*J (loves, place a labeled (identified) and
weighed filter In the filter holder. Be sure
that the filter Is properly centered and the
fiuket properly placed so as not to allow the
sample gat stream to circumvent the filter.
Check filler for tears after auembly Is com-
pleted. Mark the probe extension with heat
resistant tape or by some other method to
denote the proper distance Into the slack or
duct for each samplinc point.
Assemble the train as In Figure 17-1. using
a very light coat ot sllieonr grease on all
ground glass joints and greasing only the
outer portion (see APTD-0516) to avoid pos-
sibility of contamination by the slllcone
grease. Place crushed ice around the im-
pingers.
4.1.4 Leak Cheek Procedures.
4.1.4.1 Pretest Leak-Check. A pretest
leak-check Is recommended, but not re-
quired. If the tester opu to conduct the pre-
test leak-cheek, the following procedure
shall be used.
After the samplinc train has been assem-
bled, plug the InlM to the probe nozzle with
a material thai will be able to withstand the
stack temperature. Insert the filter holder
into the stack and wait approximately 5
minutes (or longer, if necessary) to allow
the system to come to equilibrium with the
temperature of the stack gas.stream. Turn
on the pump and draw a vacuum ot al least
$80 mm Hg (IS In. Hg>; note thai a lower
vacuum may be used, provided thai It is not
exceeded during the test. Determine the
leakage rate. f. leakage rate In excess of 4
percent of the averace sampling rate or
0.00057 m'/mtn. (0.02 dm), whichever Is
less. Is unacceptable.
The following leak-cheek Instructions for
the samplinc train described in APTD-OJ70
and APTD-OSBl may be helpful. Start the
pump with by-pass valve fully open and
coarse adjust valve completely closed. Par-
tially open the coarse adjust valve and
slowly close the by-pass valve until the de-
sired vacuum Is reached. Do not reverse di-
rection of by-pass valve. If the desired
vacuum is exceeded, either leak-check al
thts'higher vacuum or end the leak-check u
shown below and start over.
When the leak-check Is completed, first
slowly remove the plug from the inlet to the
probe nozzle and immediately turn off the
vacuum pump. This prevents water from
being forced backward and keeps silica eel
from being entrained backward.
4.1.4.2 Leak-Check* Durtnc Sample Run.
If. during the sampling run, a component
(ex. filter assembly or impineer) chance be-
comes necessary, a leak
-------
PLANT
LOCATION.
orcnATon.
DATE
RUN NO.
SAMPLE BOX NO..
METER BOX N0._
METER A lip
C FACTOR
PITOT TUBE COEFFICIENT. Cp.
BAROMETRIC PRESSURE
ASSUMED MOISTURE. %
PROBE EXTENSION LENGTH. m(fU
NOZZLE IDENTIFICATION NO
AVERAGE CALIBRATED NOZZLE DIAMETER, em (In.).
FILTER NO
LEAK RATE.roVmiii,(cM
STATIC PRESSURE, mm H| (in. H|)
SCHEMATIC OF STACK CROSS SECTION
TRAVtASC POINT
NUMOtB
TOTAL
SAMTLINO
TIME
(01. min.
AVIRAGC
VACUUM
mm H|
(in. tl|)
STACK
TEMPERATURE
(T$).
•c (*FI
VELOCITY
HEAD
1APS».
nirnHjO
(In. MjD)
PRESSURE
DIFFERENTIAL
ACROSS
OniFICE
METER.
mm MjO
(in. HjO)
GAS SAMPLE
VOLUME.
mj (H]l
GAS SAMfTC TtMPtRATURE
AT OUT GAS ME TEH
WET.
•C («F»
Avn
OUTLET.
•C(«FI
Avil
Avg
TEMPERATURE
OF CAS
LEAVING
CONDENSER OR
LASTIMPINGER.
•C(°FI
hd O Jd to
(U pi (D ID
UJ rt
-------
Section No. 3.11.10
Revision No. 0
Date January 3, 1982
Page 7 of 11
Clean the portholes prior to the teat run
to minimize the chance at sampling the de-
posited material. To begin sampling, remove
the nozzle cap and verify that the pilot lube
and probe extension are properly posl-
Uoned. Position the nozzle it the (Inl tra-
verse point vlth the tip pointlnc directly
Into the gas stream. Immediately start the
pump and adjust the now to isoklnetic con-
ditions. Nomographs are available, which
•id In the r»pld adjustment to the Uoklnetlc
sampling rate without excessive computa-
tions. These nomorraphi art designed lor
UK when the Type 6 pilot tube coefficient
Is O.BirO.02. and the stack gas equivalent
density idry molecular weight) Is equal to
2J = 4. AJTD-0516 detain the procedure for
usmc the nomographs. If C, and M. are out-
fide the above suted ranres. do not use the
nomomphs unless appropriate steps (aee
Citation 1 In Section 7) are taken to com-
pensate for the deviations.
When the stack It under significant aega-
live pressur* (height of Implncer clem),
take care to clo»e the coarse adjust Talve
before Inserting the probe extension assem-
bly Into the stack to prevent water from
being forced backward. If necessary, the
pump may be turned oa with the coarse
adjust vilve closed.
When the probe is In position, block off
the openings around the probe and porthole
to prevent unrepresentative dilution of the
ras stream.
Tn verse the stack cross section, as re-
quired by Method 1 or as specified by the
Administrator, being careful not to bump
the probe nozzle into the stack rails Then
i*.-nplint near the walls or when removing
or inserting the probe extension through
the portholes, to minimize chance of ex-
tracting deposited material.
During the test run. take appropriate
neps (e.g.. adding crushed Ire to the 1m-
pinger ice bath) to maintain a temperature
of less than 20* C (68* F> at the condenser
outlet: this will prevent excessive moisture
losses. Also, periodically check the level and
tero of the manometer.
If the pressure drop across the filter be-
comes loo high, making isokinelic sampling
difficult la mainlaln. the filter may be re-
placed in the midst of a sample run. It Is
recommended that another complete (liter
holder assembly be used rather than at-
tempting lo change the filter Itself. Before a
new filler holder Is insialled. conduct a leak
check, as outlined in Section 4.1.4.2. The
lotsj paniculate weight stall Include the
sunur.aiion of all filler assembly niches.
A single train shall be used for the entire
sample run. except in cases where simulta-
neous sampling Is required in two or more
separate ducts or at two or more different
locations within the same duct, or, in cases
where equipment failure necessltales a
change of trains. In all other situations, the
use of two or more trains will be subject to
the approval of the Administrator. Note
that when two or more trains are used, a
separaie analysis of the collected panlcu-
lale from each Irain shall be performed.
unless identical nozzle sizes were used on all
iralns. In which case the particulate catches
from the individual trains may be combined
and a single analysis performed.
At the end of the sample run. turn off the
pump, remove the probe extension assembly
from the stack and record the final dry gas
meter reading. Perform a leak-check, as out-
lined in Section 4.1.4.3. Also, leak-check the
pilot lines as described in Section S.I of
Method 2: the lines must pass this leak-
cheek, la order to validate the velocity bead
data.
4.1.6 Calculation of Percent Isoktnellc.
Calculate percent Isoklnetic (see Section
6.1D LO determine whether another lest run
should be made. If there is difficulty in
maintaining Uoklnellc rates due to source
condllloni. consult with the Administrator
for possible variance on the isoklnellc rales.
4.2 Sample Recovery. Proper cleanup
procedure begins as soon as the probe ex-
tension assembly is removed from the stark
at the end of the sampling period. Allow the
assembly u> cool.
When Ihe assembly can be safely handled.
wipe off all extemaj paniculate mailer near
the tip of the probe nozzle and place a cap
over it Vo prevent losing or gaining panicu-
late mailer. Do not cap off the probe tip
Ughlly while the sampling train is cooling
down as this would create a' vacuum In the
tiller bolder, forcing condenser water back-
ward.
Bfloft moving th* sample train to the
cleanup tile, disconnect the filter bolder-
probe nozzle assembly from the probe ex-
tension: cap the open Inlel of the probe ex-
tension. Be careful not to loce any eonden-
sate. If present. Remove the umbilical cord
from the condenser outlet and cap the
outlet. If a flexible line is used between the
first impinger (or condenser) and the probe
extension, disconnect the line at the probe
extension and let any condensed water or
liquid drain into the Impingert or condens-
er. Disconnect the probe extension from the
condenser: cap the probe extension outlet.
Alter wiping off the sllicone grease, cap off
the condenser Inlet. Ground glass stoppers,
plastic caps, or serum caps (whichever are
appropriate) ma; be used to close these
openings.
Transfer both the filter holder-probe
nozzle assembly and the condenser to the
cleanup area. This ares, should be clean and
protected from the wind so that the chances
of contaminating or losing the sample will
be minimized.
S*ve a portion of the acetone used for
cleanup as a blank. Take 300 ml of this ac-
etone dtrecily from the wash bottle being
used and place It In a glaas sample container
labeled "acetone blank."
Inspect the train prior to and during dis-
assembly and note any abnormal conditions.
Treat the samples as follows:
Cor.£c
-------
Section Mo. 3.11.10
Revision Mo. 0
Date January 4, 1982
Page 8 of 11
IN* C (»»' P>. whichever to taw. tor I to »
hour*, eeeltd In the dMleuter. utd welche*
I* » eeniunt %eifht. un)eu etherwUe ipvrl
ftod by U>e A-»lnliu»tt-. The fester
ftteo 'opt u> oven dry the MJ»p»e £ «£•
Me »U£k umpenture or I0»' C (MO* r>.
whichever to lew. lor t to t houn, welf h the
"
*£ Oatt
ftun No..
Filur No.
Amount liquid lost durin| traniport
Aottoni blank volumt, ml _______
Acatoni wash volumi, ml _______
Aeatoni black concentration, mj/mj (aquation 174)
Aeatont wash blank, mj (aquation 17-5) ______
CONTAINER
NUMBER
1
2
TOTAL
WEIGHT OF 'ARTICULATE COLLECTED.
mg
FINAL WEIGHT
Ltss •ettoi
Wtight of pi
TARE WEIGHT
n0 blank
irticulatt miner
WEIGHT GAIN
FINAL
INITIAL
LIQUID COLLECTED
TOTAL VOLUME COLLECTED
VOLUME OF LIQUID
WATER COLLECTED
IMPINGER
VOLUME.
ml
SILICA GEL
WEIGHT.
8
g* ml
* CONVERT WEIGHT OF WATER TO VOLUME BY DIVIDING TOTAL Wt
INCREASE BY DENSITY OF WATER
>NCREASE" B . VOLUME WATER, ml
Vg/m!
Figure 17-4. Analytical data.
-------
Section No. 3.11.10
Revision No. 0
Date January 4, 1982
Page 9 of 11
Container No. 2. Note the level of liquid In
UM container and confirm on the analysis
•beet whether or .not leakage occurred
•taring transport. If a noticeable amount of
iMkace hat occurred, either void the sample
or uae method*, subject to the approval of
the Administrator, to correct the final re-
cult*. Measure the liquid In this container
either volumetrlcally to ±1 ml or gravtme-
trlcally to ±0.5 |. Transfer the content* to a
tared 230-ml beaker and evaporate to dry
Bttt at ambient temperature and pressure.
Desiccate (or 24 hours and weigh to a con-
ttant weight. Report the result* to the near-
est 0.1 ms.
Container No. t. This sup may be con-
ducted In the field. Weigh the spent silica
•el (or silica tel plus implncer) to the near-
est O.S • ustnc a balance.
Mcetone Blank" Container. Measure ac-
etone in this container either volumetrieally
or travimetrlcally. Transfer the acetone to a
tared JSO-ml beaker and evaporate to dry-
Dess at ambient temperature and pressure.
Desiccate for 94 hours and weigh to a eon-
•Unt weight. Report the results to .the near-
«*t 0.1 mg.
Nort.—At the option of the tester, the
•ontenu of Container No. 2 as well as the
acetone blank container may be evaporated
at temperatures higher than ambient. If
evaporation Is done at an elevated tempera-
ture, the temperature must be below the
toiling point of the solvent; also, to prevent
•bumping," the evaporation process must be
•Jowly supervised, and the contents of the
beaker must be swirled occasionally to
•maintain an even temperature. Use extreme
•re, as acetone is highly flammable and
has a low flash point.
8. Calibration. Maintain a laboratory log
•f all calibrations.
1.1 Probe Nozzle. Probe nozzles shall be
•Iterated before their Initial use In the
field. Using a micrometer, measure the
iHMe diameter of the nozzle to the nearest
0.025 mm (0.001 In.). Make three separate
measurements using different diameters
each time, and obtain the average of the
measurements. The difference between the
high and low numbers shall not exceed 0.1
mm «0.004 in.). When nozzles become
nicked, dented, or corroded, they shall be
reshaped, sharpened, and recalibrated
before use. Each nozzle shall be permanent-
ly and uniquely Identified.
8.2 Pltot Tube. If the pltot tube Is placed
In an interference-free arrangement with re-
spect to the other probe assembly compo-
nent*. It* baseline (tsolaUd tube) coefficient
shall be determined as outlined In Section 4
of Method 2. If the probe assembly is not in-
terference-free, the pilot tube assembly co-
efficient shall be determined by calibration.
using methods subject to the approval of
the Administrator.
5.3 Metering System. Before it* Initial
use In the field, the metering system shall
be calibrated according to the procedure
outlined in AJPTD-0576. Instead of physical-
ly adjusting the dry gas meter dial readings
to correspond to the wet test meter read-
Ings, calibration factors may be used to
mathematically correct the gas meter dial
readings to the proper values.
Before calibrating the metering system, it
Is suggested that a leak-check be conducted.
For metering systems having diaphragm
pumps, the normal leak-check procedure
will not detect leakages within the pump.
For these eases the following leak-check
procedure is suggested: make a 10-mlnute
calibration run at 0.00057 m'/min (0.02
cfm); at the end of the run, take the differ-
ence of the measured wet test meter and
dry gas meter volumes: divide the difference
by 10. to get the leak rate. The leak rate
should not exceed 0.00087 m'/min (0.02
cfm).
After each field use. the calibration of the
metering system shall.be checked by per-
forming three calibration runs at a single.
Intermediate orifice setting (based on the
previous field test), with the vacuum set at
the maximum value reached during the test
series. To adjust' the vacuum. Insert a valve
between the wet test meter and the Inlet of
the metering system. Calculate the average
value of the calibration factor. If the cali-
bration has changed by more than 5'per?
cent, recalibrate the meter over, the full
range of orifice settings, a* outlined In
AJTD-0576.
Alternative procedures, e.g., using the ori-
fice meter coefficient*, may be used, subject
to the approval of the Administrator.
Non.—If the dry gas meter coefficient
values obtained before and after a test
aeries differ by more than 5 percent, the
test series shall either be voided, or calcula-
tions for the test series shall be performed
using whichever meter coefficient value
(i.e.. before or after) gives the lower value of
total sample volume.
8.4 Temperature Oauges. Use the proce-
dure In Section 4.3 of Method 2 to calibrate
In-stack temperature gauges. Dial thermom-
eters, such as are used for the dry gas meter
and condenser outlet, shall be calibrated
against mercury-in-glass thermometers.
5.5 Leak Check of Metering System
Shown in Figure 17-1. That portion of the
sampling train from the pump to the orifice
meter should be leak checked prior to Initial
use and after each shipment. Leakage after
the pump will result in less volume being re-
corded than is actually sampled. The follow.
mg procedure Is suggested (see Figure 17-8).
Close the main valve on the meter box.
Insert a one-hole rubber stopper with
rubber tubing attached into the orifice ex-
haust pipe. Disconnect and vent the low fide
of the orifice manometer. Close off the low
side orifice tap. Pressurize the system to 19
to 18 cm (8 to 7 In.) water column by blow-
ing Into the rubber tubing. Pinch off the
tubing and observe the manometer for on*
minute. A loss of pressure on the mano-
meter Indicates a leak in the meter box;
teaks. If present, must be corrected.
-------
RUBBER
TUBING
RUBBER
STOPPER
ORIFICE
VACUUM
GAUGE
BLOW INTO TUBING
UNTIL MANOMETER
READS S TO 7 INCHES
WATER COLUMN
ORIFICE
MANOMETER
Figure 17-5. Leak check of meter box.
iifffitftf
£*f
fin
K\i
Ih
6?I
*?
t« "
a?s
§??
r- *- t>
C n r»
?l|
S!
I!f
|f
o - i^-SS o^
S * w » C crZ
I | i!'! II
M
9 35
r a&
^tf tj 2d en
o* PI ID n>
ifl ft < O
(D (0 H- rt
0» H-
•*» O
vo
UJ
-------
Section Mo. 3.11.10
Revision No. 0
Date January 4, 1982
Page 11 of 11
time Interval, from the final
component change, until tht tod of
tbt sampling run. mln.
|M. Specific gravity ot mercury.
••Bee/Bin.
W». Conversion to percent.
U Average *ry n* meter temperature
•jkd average ortfloe pressure drop. See d*u
•fjeet (Plgwe 17-a>.
U Drr Oas Volume. Correct tht cample
volume measured by tht dry gas meter to
•Undard conditions (to* C. 160 ma He or
•' F. MJ2 In. Eg) by using Equation 17-1.
•.< Aeelont Blank Concentration.
•(ltd)
*H
T7T
ritd
where:
Equation 17-1
K/mm Be (or metric unlu:
H.M* R/ln. He tor tntlUh unlu.
Hon.— Equation 17-1 an be UMd M writ-
ten unless tht leakage me observed during
•ay of tht mandatory leak ehecti (!.«.. the
•Mt-tect leak checfc or leak checks conduct-
•d prior to component cnuirei) tietedi U-
UU or L, tseted* U. Equation 11-1 muit be
••dlfltd w follow
U) CMt L No component ertuut* m»de
dwini wapllni run. In thU CMC. replace
V. In equation 17*1 wtth the expr*ulon:
(B) CM* n. One or more component
•ham n made during the aamplint run. In
tbto cue. replace V. In SqutUon 17-1 by the
txprtttlon:
IV. • (L, - L.) I, - J (L, - L,)
equation 11-4
•.7 Acetone Waih Blank.
W.-C.V^.
equation 11-6
•.I Total ^articulate Wtttht. Deurmlne
the total partleulate catch from tht «un of
the wtljhu obtained Iron conUinen 1 and
S leu tht acttent blank (Mt rifure 17-4).
Mon.— Refer to Section 4.14 to aatlst In
calculation of retulu Involving two or more
fliur MtcBbUa or two or more atmplinc
train*.
M rwtlculau ConeentraUon.
c,-(0.001
(.10 Conversion Factor*:
Equation 17-1
Muittvlr »y
g/n«.
I/ft-
•.eau:
U.41
S.KI > 10-'
U41
1.11 Uokinetle Variation.
(.11.1 Calculation from Raw Data.
MD T
y/T,)
Equation 17-7
where:
K.-O.OOJ4M mm Hg-nWml-'K for metric
units; 0.003669 in. Hg-ft'/ml-'R for Eng-
lish unlu.
(.11.3 Calculation from Intermediate
Values.
1. Addendum to Specification* for Inciner-
ator Twiini at r-denJ FMillUea. WU.
HCAPC. December 1. 1M1.
I. Uartin. Robert U.. ConitrucUon Detalli
of boklnetlc Bouree*vmpUn* Eaulpmcnt.
Envtronnienta] rrouction Atency. Re-
aearch Triantle farl, M.C. APTD-OM1.
April. 1171.
I. Rom. Jerome J. Hainunanee. Calibra-
tion. and Operation of I*okinetie Bounse-
•amplinr Equipment. Environmental Pro-
tectlon Ateney. Re*«arch Triaaclt Park.
K.C. AJTD-OS16. March. 1«72.
4. Smith. W. 8.. R. T. Shlithuv and W.
P. Todd. A Method of InterpreUac Buck
•ampltnr Data. Paper Pmenud at the Ord
Annual Meetint of tht Air Pollution Con-
trol Aaeodatlon. BL LeuU, Mo. June 14-11.
irto.
ft. Smith, W. B.. et aU Suck Omi BampUat
Improved and Simplified wtth New Equip-
•era. A1*CA Paper No. (7-Ut. 1M1.
(. BpecUleatient for Incinerator Tenint at
fMeral PtdliUct. PH8. NCAPC. lff<1.
1. Bhltehan, R. T, Adjuftmenu in the
EPA Nomograph for Different Pilot Tube
Coefficient! and Dry Molecular WeichU.
Buck Swnpllnc Newt 2:4-11. October. It14.
I. Vollaro. R. P. A Survey of Commercial-
ly Available ln*tnimenution for the Mea-
surement of bow-Rant e Oa* VeloelUej. U A.
Envlrorunenul Proieciloa Arency. Emission
Meaiurement Branch. Research Trlantle
Park. N.C. November. 1»7( (uapublUhtd
paper 1.
I. Annual Book of ASTM Standards. Part
M. Oueous PueU; Coal and Coke; Auno-
fpherte Analysis. American Society for Test-
tel and Maurlals. Philadelphia, Pa. 1174.
pe. (17422.
10. Vollaro. R. P. Recommended Proet-
durt tor Sample Traverses in Ducts Smaller
than 12 Inches in Dlaairt*-. 6 J. environ-
mental Prouctlon Armey. Enisilon Mea-
•urement Branch. Research Triantle Park,
N.C. November. >"(.
(See, 114.
a»M,
*§:1>
Alr Act U aat&ded «43
•ad substitute orUy for those leakage rates
(I* «r L,) which exceed U.
(.4 Volume of water vapor.
I •
Equation 17-3
where:
K.-0.001JJJ m'/ml for metric units; 0.04107
nvml for English unlu.
•J Moisture Content.
M
Vitd) * vw(itd)
Equation 17-J
Equation 17-1
where:
X..4.320 for metric unlu: O.OB4JO for Eng-
lish unlu.
(.12 Aecepublr ResulU. U M percent
010110 percent, the resulu are acceptable. If
the rerulu arc lo«' in eomparUon to the
stundird and 1 is beyond the accepuble
range, t-:. If I U lest than 90 percent, the Ad-
ministrator mty opt to accept the resulu.
CM Ciutlon 4 in Section 7 to make Judg-
ment*. Otherwise, reject tht resulu end
repeat the test.
7.
-------
Section No. 3.11.11
Revision No. 0
Date January 4, 1982
Page 1 of 1
11.0 REFERENCES
1. Standards of Performance for New Stationary Sources,
Federal Register, Vol. 43, No. 37, February 23, 1978.
2. Martin, R. M. Construction Details of Isokinetic
Source Sampling Equipment. Publication No. APTD-0581.
Air Pollution Control Office, EPA, Research Triangle
Park, N.C., 1971.
3. Rom, J. J. Maintenance, Calibration, and Operation of
Isokinetic Source Sampling Equipment. Pub. No. APTD-
0576. Office of Air Programs, EPA, Research Triangle
Park, N.C., 1972.
4. Mitchell, William J., M. Rodney Midgett, and C.
Bruffey. Comparative Testing of EPA Methods 5 and 17
at Nonmetallic Mineral Plants. EPA-600/4-80-022.
U.S. Environmental Protection Agency, Research Tri-
angle Park, N.C., April 1980.
-------
Section No. 3.11.12
Revision No. 0
Date January 4, 1982
Page 1 of 1
12.0 DATA FORMS
Blank data forms are in Method 5, Section 3.4.12, for the
convenience of the Handbook user. All forms are the same as for
Method 5 with the exception of Figures 3.1 and 4.5 which are in-
cluded in Method Highlights, Section 3.11.
ft U.S. GOVERNMENT PRINTING OFFICE: 1 9 9 1 - 5 - e • 1 e »» o 5 7 1
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