ASTM D6735-01(2009)
(Test Method)Standard Test Method for Measurement of Gaseous Chlorides and Fluorides from Mineral Calcining Exhaust Sources—Impinger Method (Withdrawn 2018)
Standard Test Method for Measurement of Gaseous Chlorides and Fluorides from Mineral Calcining Exhaust Sources—Impinger Method (Withdrawn 2018)
SIGNIFICANCE AND USE
This field-test method provides chloride and fluoride concentration results on a dry basis. Concentration data for gaseous chlorides and fluorides are assumed to be hydrochloric acid gas, and hydrofluoric acid gas when calculating mass emission rates.
Mass emission rates of HCl and HF can be calculated if the effluent volumetric flow rate is known. Volumetric flow rates can be calculated by conducting EPA Methods 1–4 or their equivalents.
This field test method provides data having bias and precision for HCl consistent with the values in Section 14. In addition, the test-specific bias can be assessed for each test by conducting the post-test quality assurance check. The procedure is identified as optional, and the performance of this procedure depends on the test specific data quality objectives, and end use of the data.
The test-specific precision may be determined by conducting paired-runs. Paired runs aid in identifying possible suspect data and provide backup in the event one train is invalidated. Performing paired runs depends on the test-specific data quality objectives.
The reaction of gaseous HCl with ammonia (NH3) to form solid ammonium chloride (NH4Cl) is well known. At stack temperatures common to the exits of baghouses and ESPs at mineral calcining facilities (that is, 250 to 450°F or 121 to 232°C), an equilibration between the gaseous HCl/NH3, the condensed NH4Cl(s), and the effluent particulate matter can exist. It is impossible to know the exact partition ratio between the gas and particulate phases of these compounds in the sampling system. Furthermore, it is very difficult to control the effects of these partitioning reactions within the various sampling system components.
Note 4—Use of this method is cautioned when trying to quantify HCl (g) in the presence of ammonium chloride and ammonia.
SCOPE
1.1 This method will measure the concentration of gaseous hydrochloric and hydrofluoric acids, and other gaseous chlorides and fluorides that pass through a particulate matter filter maintained at 177°C (350°F). This method is specific for sampling combustion effluent from mineral calcining industries and other stationary sources where the reactive/adsorptive nature of the particulate matter may affect measurements.
1.2 This method utilizes ion chromatography to quantify the aqueous samples, and thus measures only the C1- and F- ions.
1.3 Based on a one-hour sampling run, the method will provide results of known accuracy and precision for chloride and fluoride in-stack concentrations of 0.5 ppm (v) dry or greater. Extending the run duration and sampling a greater volume of effluent will extend the range to lower concentrations.
1.4 This method includes optional post-test quality assurance procedures to assess the bias of the test results, and optional paired sample train runs to assess the precision of test results.
WITHDRAWN RATIONALE
This method will measure the concentration of gaseous hydrochloric and hydrofluoric acids, and other gaseous chlorides and fluorides that pass through a particulate matter filter maintained at 177°C (350°F).
Formerly under the jurisdiction of Committee D22 on Air Quality, this test method was withdrawn in January 2018 in accordance with section 10.6.3 of the Regulations Governing ASTM Technical Committees, which requires that standards shall be updated by the end of the eighth year since the last approval date.
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D6735 − 01 (Reapproved 2009)
Standard Test Method for
Measurement of Gaseous Chlorides and Fluorides from
Mineral Calcining Exhaust Sources—Impinger Method
This standard is issued under the fixed designation D6735; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
INTRODUCTION
The bias and precision statements included in Section 14 of this test method are based on field test
measurements at limestone calcining sources. Procedures for assessing the test-specific bias and the
precision at each source are included in the body of the method.
Additional optional procedures are included in Appendix X1 that can be used to demonstrate the
biasandprecisionofthemethodforspecificsourcecategories.Theseprocedureswereusedtodevelop
the bias and precision statements included in Section 14 and may be applied when using the method
at sources where no previous test data have been acquired.
1. Scope mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
1.1 This method will measure the concentration of gaseous
hydrochloric and hydrofluoric acids, and other gaseous chlo-
2. Referenced Documents
rides and fluorides that pass through a particulate matter filter
2.1 ASTM Standards:
maintained at 177°C (350°F). This method is specific for
samplingcombustioneffluentfrommineralcalciningindustries D1356 Terminology Relating to Sampling and Analysis of
Atmospheres
and other stationary sources where the reactive/adsorptive
nature of the particulate matter may affect measurements. D2986 Practice for Evaluation of Air Assay Media by the
Monodisperse DOP (Dioctyl Phthalate) Smoke Test
1.2 Thismethodutilizesionchromatographytoquantifythe
- - (Withdrawn 2004)
aqueous samples, and thus measures only the C1 and F ions.
D3195 Practice for Rotameter Calibration
1.3 Based on a one-hour sampling run, the method will
D6348 Test Method for Determination of Gaseous Com-
provide results of known accuracy and precision for chloride
pounds by Extractive Direct Interface Fourier Transform
and fluoride in-stack concentrations of 0.5 ppm (v) dry or
Infrared (FTIR) Spectroscopy
greater. Extending the run duration and sampling a greater
2.2 EPA Standards:
volume of effluent will extend the range to lower concentra-
Method 1—Sample and Velocity Traverses for Stationary
tions.
Sources
1.4 This method includes optional post-test quality assur-
Method 2—Determination of Stack Gas Velocity and Volu-
ance procedures to assess the bias of the test results, and
metric Flow Rate (Type S Pitot Tube)
optional paired sample train runs to assess the precision of test
Method 3—Gas Analysis for Carbon Dioxide, Oxygen,
results.
Excess Air, and Dry Molecular Weight
Method 4—Determination of Moisture Content in Stack
1.5 This international standard was developed in accor-
Gases
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
This test method is under the jurisdiction of ASTM Committee D22 on Air the ASTM website.
Quality and is the direct responsibility of Subcommittee D22.03 on Ambient The last approved version of this historical standard is referenced on
Atmospheres and Source Emissions. www.astm.org.
Current edition approved Oct. 1, 2009. Published December 2009. Originally United States Environmental Protection Agency Code of Federal Regulations,
approved in 2001. Last previous edition approved in 2001 as D6735 – 01. DOI: 40 CFR Parts 60 and 63, available from the Government Printing Office,
10.1520/D6735-01R09. Washington, DC.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6735 − 01 (2009)
Method 301—Field Validation of Pollutant Measurement 3.2.16 spiked train, n—atraininwhichHCl(g)orHF(g)has
Methods from Various Waste Media been added after the test run to determine measurement system
bias.
3. Terminology
3.2.17 “u” tubes, n—connecting tubes constructed of either
glass or TFE-fluorocarbon to assemble the impinger train.
3.1 See Terminology D1356 for definition of terms used in
this test method.
3.2.18 volatile compounds, n—compounds that are gases at
the effluent temperature.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 analyte spike, n—the optional procedure contained in
4. Summary of Test Method
this method to assess bias attributed to the measurement
system. The analyte spike procedure consists of adding a
4.1 Sampling:
known amount of the certified compressed gas into the
4.1.1 This method involves collecting an integrated sample
impinger train upstream of the particulate filter after the end of
of stack gas in a series of five midget impingers. Two of the
a run.
five impingers contain 0.1 N H SO , two are empty and one
2 4
3.2.2 blanktrain,n—animpingertrainthatisassembledand contains silica gel.
recovered but does not collect effluent gas. The blank train 4.1.2 Sampling is conducted from a single point within the
provides an estimate of the amount of contamination that can stackorductataconstantsamplingrateof2L/min(65 %)for
occur during a field test. a period of at least one h per sample run.
4.1.3 The sampling system heated components must be
3.2.3 certified compressed gas, n—an HCl or HF gas stan-
maintained at a temperature of 350 6 15°F (177 6 8°C). The
dard that is certified by the manufacturer to a known degree of
sampling system is conditioned before conducting the first run
accuracy. For HCl and HF compressed gas standards the
by sampling 120 Lof stack gas at 2 L/min, and then discarding
accuracy is often certified to 5–10 % of the certified value.
the impinger solutions.
3.2.4 conditioning run, n—a sampling run conducted before
4.1.4 A test is comprised of three or more sample runs.
the first run of the test series. The impinger contents from the
conditioning run are not analyzed nor included in the test NOTE 1—The conditioning run is to minimize HCl and/or HF adsorp-
tion during the ensuing sampling runs by passivating active sites in the
results.
probe and filter box components.
3.2.5 cylinder gas analysis, n—a procedure to verify the
NOTE 2—The impingers from the conditioning run are rinsed thor-
concentration of the certified compressed gas and to provide
oughly with deionized water before recharging to start the first run.
Rinsing the probe and filter assembly must not be performed.
the direct cylinder value. See 11.2.7.4.
NOTE 3—The particulate matter from mineral calcining facilities
3.2.6 direct cylinder value, n—the value of the certified
adsorbs HCl and HF to varying degrees. The amount of adsorption
cylinder gas, or the value obtained from conducting the
dependsonprocessparametersandthephysical/chemicalpropertiesofthe
dust. Measures such as turning the probe nozzle opening away from the
cylinder gas analysis. See 11.2.7.4.
stack or duct flow minimize collection of particulate matter on the filter
3.2.7 hazardous air pollutants (HAPs), n—approximately
material and thus reduce the adsorption of HCl and HF. Other measures
188 compounds or groups of compounds identified in Title III
that reduce collection of particulate matter are acceptable. Such measures
include installing a shrouded large pore sintered filter (> 20 microns) on
of the Clean Air Act Amendments.
the end of the probe. This apparatus will reduce collecting particulate
3.2.8 impinger train, n—a series of midget impingers con-
matter while allowing gases and small particles to enter.
nected together by glass or TFE-fluorocarbon u-tubes.
4.2 Analysis:
3.2.9 midget impinger, n—cylindrical glass (or other appro-
4.2.1 Quantification of chloride and fluoride ions is accom-
priate material) containers that hold approximately 50 mL.
plished by analyzing an aliquot of the impinger solution using
3.2.10 mineral calcining industry, n—industries that use
ion chromatography.
thermal devices to remove CO and other compounds from
4.2.2 The total mass of chloride or fluoride ions collected in
non-ferrous mineral material.
the impinger solution sample is a product of the ion chromato-
graphic (IC) output in either mg or µg and the total volume of
3.2.11 paired runs, n—two impinger trains operated simul-
the sample. For example, if the IC analysis for chloride is 0.02
taneously at the same sampling location.
mg,andthetotalsamplevolumeis100mL,thenthetotalmass
3.2.12 partition ratio, n—the amount of a substance at
of chloride collected for the run is equivalent to 2 mg
equilibrium with its gas and particulate phases.
(assuming a 1-mL injection into the IC).
3.2.13 proportional controllers, n—a temperature control
4.2.3 Usethefollowingequationtodeterminethetotalmass
device that uses a sensor to make small adjustments to the
of chloride or fluoride ions in the sample.
power output. These types of controllers prevent wide fluctua-
~IC/IV!*~SV! 5 mg of ion in total sample (1)
tions in the temperature of the heated measurement system
components.
where:
3.2.14 reagent blank, n—a 20–30 mL sample of the 0.1 N IC = ion chromatographic results in mg,
IV = volume of sample injected into ion chromatograph in
H SO impinger solution that is diluted to 100 mL.
2 4
mL, and
3.2.15 samplingsystemleakcheck,n—aprocedurethattests
SV = sample volume in mL.
the sampling system for negative pressure leaks.
D6735 − 01 (2009)
4.2.4 The equivalent in-stack concentration of the sample is 6.2 Analytical Interferences—Ensuring that the chromato-
equivalent to the mg catch of anion in the impinger solution graphic conditions are optimized for separating chloride and
sample divided by the gas sample volume at standard condi- fluoride from other ions minimizes analytical interferences.
tions.
7. Apparatus
5. Significance and Use
7.1 Sampling—See Fig. 1.
5.1 This field-test method provides chloride and fluoride
7.1.1 Sample Probe Assembly, including a probe liner of
concentration results on a dry basis. Concentration data for
borosilicate glass, stainless steel, or TFE-fluorocarbon of (1)
gaseouschloridesandfluoridesareassumedtobehydrochloric
sufficientlengthtoreachthegassamplingpoint,(2)ofphysical
acid gas, and hydrofluoric acid gas when calculating mass
integrity to minimize adsorption of HCl and/or HF, and (3)
emission rates.
heated and controlled to sustain the sample temperature at 350
6 15°F (177 6 8°C). The internal diameter of the probe liner
5.2 Mass emission rates of HCl and HF can be calculated if
shouldbebetween0.25-0.5in.(0.1-2cm).Theprobeassembly
the effluent volumetric flow rate is known. Volumetric flow
shall minimize collection of particulate matter but allow gases
rates can be calculated by conducting EPA Methods 1–4 or
and small particles to pass.
their equivalents.
NOTE 5—The assembly could consist of an in-stack large pore sintered
5.3 This field test method provides data having bias and
filter (>20 microns) with a shroud, or a nozzle that is positioned away
precision for HCl consistent with the values in Section 14.In
from the flow stream.
addition, the test-specific bias can be assessed for each test by
NOTE 6—Aspecially designed probe that utilizes fore and aft indepen-
conducting the post-test quality assurance check. The proce-
dent heater and heater controllers has proven to be capable of maintaining
the 350°F temperature throughout the length of the probe. This is crucial
dure is identified as optional, and the performance of this
when a portion of the probe is inserted into a hot stack but the remainder
procedure depends on the test specific data quality objectives,
of the probe is out of the stack at a much cooler relative temperature. Use
and end use of the data.
ofthisprobedesignwillminimizeoreliminatemoisturecondensationand
thus adsorption of HCl and HF.
5.4 The test-specific precision may be determined by con-
ducting paired-runs. Paired runs aid in identifying possible
7.1.2 Particulate Filters, rated at 0.3 µm (or less), and
suspect data and provide backup in the event one train is
having an efficiency of 95 % or greater in accordance with
invalidated. Performing paired runs depends on the test-
Practice D2986. The filters are placed immediately after the
specific data quality objectives.
heated probe in a heated and temperature-controlled compart-
ment. A TFE-fluorocarbon-glass filter (75 % TFE-
5.5 The reaction of gaseous HCl with ammonia (NH)to
fluorocarbon, 25 % glass), or an ultra high purity quartz filter
form solid ammonium chloride (NH Cl) is well known. At
must be used to remove particulate matter.
stacktemperaturescommontotheexitsofbaghousesandESPs
7.1.3 Particulate Filter Holders, filter holders and supports
at mineral calcining facilities (that is, 250 to 450°F or 121 to
should be made out of TFE-fluorocarbon or TFE-fluorocarbon
232°C), an equilibration between the gaseous HCl/NH , the
coated stainless steel.
condensed NH Cl(s), and the effluent particulate matter can
exist. It is impossible to know the exact partition ratio between
NOTE 7—The TFE-fluorocarbon filter holder and filter support must be
the gas and particulate phases of these compounds in the
capable of withstanding the 350°F (177°C) filter temperature.
sampling system. Furthermore, it is very difficult to control the
7.1.4 Impingers, five midget impingers (about 50 mL vol-
effects of these partitioning reactions within the various sam-
ume) with straight stems and with leak-free glass connections.
pling system components.
Thefirstandfourthimpingersinthetrainareempty,thesecond
NOTE 4—Use of this method is cautioned when trying to quantify HCl two impingers each contain 15 mL of 0.1 N H SO absorbing
2 4
(g) in the presence of ammonium chloride and ammonia.
solution, and the fifth contains silica gel. Silicone grease may
be use to aid joining the impinger connections.
6. Interferences
7.1.5 Silica Gel (or equivalent), used to protect the dry gas
meter and pump. The silica gel is not part of the sample.
6.1 Sampling Interferences:
7.1.6 U-Tubes, glass or TFE-fluorocarbon connecting tubes
6.1.1 The particulate matter (dust) from mineral calcining
to assemble the impinger train.
industries adsorbs HCl and HF to a varying degree, which will
7.1.7 Leak Free Sample Connector, sample line to connect
reduce the amount of gaseous chloride and fluoride ions that
the silica gel i
...
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