ASTM D6735-01

Standard Test Method for Measurement of Gaseous Chlorides and Fluorides from Mineral Calcining Exhaust Sources—Impinger Method

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.

General Information

• Status: Historical
• Publication Date: 09-Dec-2001
• ICS: 71.040.50 - Physicochemical methods of analysis
• ICS: 71.060.10 - Chemical elements
• Technical Committee: D22 - Air Quality
• Drafting Committee: D22.03 - Ambient Atmospheres and Source Emissions

Relations

• Replaced By: ASTM D6735-01(2009) - Standard Test Method for Measurement of Gaseous Chlorides and Fluorides from Mineral Calcining Exhaust Sources—Impinger Method (Withdrawn 2018)
• Effective Date: 01-Oct-2009

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
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 D2986 Practice for Evaluation of Air Assay Media by the
Monodisperse DOP (Dioctyl Phthalate) Smoke Test
1.1 This method will measure the concentration of gaseous
D3195 Practice for Rotameter Calibration
hydrochloric and hydrofluoric acids, and other gaseous chlo-
D6348 Test Method for Determination of Gaseous Com-
rides and fluorides that pass through a particulate matter filter
pounds by Extractive Direct Interface Fourier Transform
maintained at 177°C (350°F). This method is specific for
Infrared (FTIR) Spectroscopy
samplingcombustioneffluentfrommineralcalciningindustries
2.2 EPA Standards:
and other stationary sources where the reactive/adsorptive
Method 1—Sample and Velocity Traverses for Stationary
nature of the particulate matter may affect measurements.
Sources
1.2 Thismethodutilizesionchromatographytoquantifythe
- -
Method 2—Determination of Stack Gas Velocity and Volu-
aqueous samples, and thus measures only the C1 and F ions.
metric Flow Rate (Type S Pitot Tube)
1.3 Based on a one-hour sampling run, the method will
Method 3—Gas Analysis for Carbon Dioxide, Oxygen,
provide results of known accuracy and precision for chloride
Excess Air, and Dry Molecular Weight
and fluoride in-stack concentrations of 0.5 ppm (v) dry or
Method 4—Determination of Moisture Content in Stack
greater. Extending the run duration and sampling a greater
Gases
volume of effluent will extend the range to lower concentra-
Method 301—Field Validation of Pollutant Measurement
tions.
Methods from Various Waste Media
1.4 This method includes optional post-test quality assur-
ance procedures to assess the bias of the test results, and
3. Terminology
optional paired sample train runs to assess the precision of test
3.1 See Terminology D1356 for definition of terms used in
results.
this test method.
2. Referenced Documents 3.2 Definitions of Terms Specific to This Standard:
3.2.1 analyte spike, n—the optional procedure contained in
2.1 ASTM Standards:
this method to assess bias attributed to the measurement
D1356 Terminology Relating to Sampling and Analysis of
system. The analyte spike procedure consists of adding a
Atmospheres
known amount of the certified compressed gas into the
impinger train upstream of the particulate filter after the end of
This test method is under the jurisdiction of ASTM Committee D22 on
a run.
Sampling and Analysis of Atmospheres and is the direct responsibility of Subcom-
mittee D22.03 on Ambient Atmospheres and Source Emissions.
Current edition approved December 10, 2001. Published February 2002. DOI:
10.1520/D6735-01. Withdrawn. The last approved version of this historical standard is referenced
For referenced ASTM standards, visit the ASTM website, www.astm.org, or on www.astm.org.
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM United States Environmental Protection Agency Code of Federal Regulations,
Standards volume information, refer to the standard’s Document Summary page on 40 CFR Parts 60 and 63, available from the Government Printing Office, Washing-
the ASTM website. ton, DC.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D6735 – 01
3.2.2 blank train, n—an impinger train that is assembled 4.1.3 The sampling system heated components must be
and recovered but does not collect effluent gas. The blank train maintained at a temperature of 350 6 15°F (177 6 8°C). The
provides an estimate of the amount of contamination that can sampling system is conditioned before conducting the first run
occur during a field test. by sampling 120 Lof stack gas at 2 L/min, and then discarding
the impinger solutions.
3.2.3 certified compressed gas, n—an HCl or HF gas
standardthatiscertifiedbythemanufacturertoaknowndegree 4.1.4 A test is comprised of three or more sample runs.
of accuracy. For HCl and HF compressed gas standards the
NOTE 1—The conditioning run is to minimize HCl and/or HF adsorp-
accuracy is often certified to 5–10 % of the certified value.
tion during the ensuing sampling runs by passivating active sites in the
3.2.4 conditioning run, n—a sampling run conducted before
probe and filter box components.
the first run of the test series. The impinger contents from the NOTE 2—The impingers from the conditioning run are rinsed thor-
oughly with deionized water before recharging to start the first run.
conditioning run are not analyzed nor included in the test
Rinsing the probe and filter assembly must not be performed.
results.
NOTE 3—The particulate matter from mineral calcining facilities ad-
3.2.5 cylinder gas analysis, n—a procedure to verify the
sorbs HCl and HF to varying degrees. The amount of adsorption depends
concentration of the certified compressed gas and to provide
on process parameters and the physical/chemical properties of the dust.
the direct cylinder value. See 11.2.7.4.
Measures such as turning the probe nozzle opening away from the stack
3.2.6 direct cylinder value, n—the value of the certified orductflowminimizecollectionofparticulatematteronthefiltermaterial
and thus reduce the adsorption of HCl and HF. Other measures that reduce
cylinder gas, or the value obtained from conducting the
collection of particulate matter are acceptable. Such measures include
cylinder gas analysis. See 11.2.7.4.
installing a shrouded large pore sintered filter (> 20 microns) on the end
3.2.7 hazardous air pollutants (HAPs), n—approximately
oftheprobe.Thisapparatuswillreducecollectingparticulatematterwhile
188 compounds or groups of compounds identified in Title III
allowing gases and small particles to enter.
of the Clean Air Act Amendments.
4.2 Analysis:
3.2.8 impinger train, n—a series of midget impingers con-
4.2.1 Quantification of chloride and fluoride ions is accom-
nected together by glass or TFE-fluorocarbon u-tubes.
plished by analyzing an aliquot of the impinger solution using
3.2.9 midget impinger, n—cylindrical glass (or other appro-
ion chromatography.
priate material) containers that hold approximately 50 mL.
4.2.2 The total mass of chloride or fluoride ions collected in
3.2.10 mineral calcining industry, n—industries that use
the impinger solution sample is a product of the ion chromato-
thermal devices to remove CO and other compounds from
graphic (IC) output in either mg or µg and the total volume of
non-ferrous mineral material.
the sample. For example, if the IC analysis for chloride is 0.02
3.2.11 paired runs, n—two impinger trains operated simul-
mg, and the total sample volume is 100 mL, then the total mass
taneously at the same sampling location.
of chloride collected for the run is equivalent to 2 mg
3.2.12 partition ratio, n—the amount of a substance at
(assuming a 1-mL injection into the IC).
equilibrium with its gas and particulate phases.
4.2.3 Usethefollowingequationtodeterminethetotalmass
3.2.13 proportional controllers, n—a temperature control
of chloride or fluoride ions in the sample.
device that uses a sensor to make small adjustments to the
~IC/IV!* ~SV! 5 mg of ion in total sample (1)
power output. These types of controllers prevent wide fluctua-
tions in the temperature of the heated measurement system
where:
components.
IC = ion chromatographic results in mg,
3.2.14 reagent blank, n—a 20–30 mL sample of the 0.1 N
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 sampling system leak check, n—a procedure that
SV = sample volume in mL.
tests the sampling system for negative pressure leaks.
4.2.4 The equivalent in-stack concentration of the sample is
3.2.16 spikedtrain,n—atraininwhichHCl(g)orHF(g)has
equivalent to the mg catch of anion in the impinger solution
been added after the test run to determine measurement system
sample divided by the gas sample volume at standard condi-
bias.
tions.
3.2.17 “u” tubes, n—connecting tubes constructed of either
glass or TFE-fluorocarbon to assemble the impinger train.
5. Significance and Use
3.2.18 volatile compounds, n—compounds that are gases at
5.1 This field-test method provides chloride and fluoride
the effluent temperature.
concentration results on a dry basis. Concentration data for
gaseous chlorides and fluorides are assumed to be hydrochloric
4. Summary of Test Method
acid gas, and hydrofluoric acid gas when calculating mass
4.1 Sampling:
emission rates.
4.1.1 This method involves collecting an integrated sample 5.2 Mass emission rates of HCl and HF can be calculated if
of stack gas in a series of five midget impingers. Two of the
the effluent volumetric flow rate is known. Volumetric flow
five impingers contain 0.1 N H SO , two are empty and one rates can be calculated by conducting EPA Methods 1–4 or
2 4
contains silica gel.
their equivalents.
4.1.2 Sampling is conducted from a single point within the 5.3 This field test method provides data having bias and
stack or duct at a constant sampling rate of 2 L/min (65 %) for precision for HCl consistent with the values in Section 14.In
a period of at least one h per sample run. addition, the test-specific bias can be assessed for each test by
D6735 – 01
(g) in the presence of ammonium chloride and ammonia.
conducting the post-test quality assurance check. The proce-
dure is identified as optional, and the performance of this
6. Interferences
procedure depends on the test specific data quality objectives,
6.1 Sampling Interferences:
and end use of the data.
6.1.1 The particulate matter (dust) from mineral calcining
5.4 The test-specific precision may be determined by con-
industries adsorbs HCl and HF to a varying degree, which will
ducting paired-runs. Paired runs aid in identifying possible
reduce the amount of gaseous chloride and fluoride ions that
suspect data and provide backup in the event one train is
reach the impinger solutions.
invalidated. Performing paired runs depends on the test-
6.1.2 Condensedwatervaporintheprobeandfilterareadue
specific data quality objectives.
to heater failure or poor heating will reduce the amount of
5.5 The reaction of gaseous HCl with ammonia (NH)to
gaseous chloride and fluoride ions reaching the impinger
form solid ammonium chloride (NH Cl) is well known. At
solutions.
stacktemperaturescommontotheexitsofbaghousesandESPs
6.1.3 Improper filter seating in the filter holder will allow
at mineral calcining facilities (that is, 250 to 450°F or 121 to
leakage of particulate matter into the impinger solutions. This
232°C), an equilibration between the gaseous HCl/NH , the
may result in more chloride and fluoride ions reaching the
condensed NH Cl(s), and the effluent particulate matter can
impinger solutions.
exist. It is impossible to know the exact partition ratio between
6.2 Analytical Interferences—Ensuring that the chromato-
the gas and particulate phases of these compounds in the
graphic conditions are optimized for separating chloride and
sampling system. Furthermore, it is very difficult to control the
fluoride from other ions minimizes analytical interferences.
effects of these partitioning reactions within the various sam-
pling system components.
7. Apparatus
NOTE 4—Use of this method is cautioned when trying to quantify HCl 7.1 Sampling—See Fig. 1.
FIG. 1 Sampling Train Configuration
D6735 – 01
and temperature controllers be used in the sampling probe. Determine the
7.1.1 Sample Probe Assembly, including a probe liner of
filter temperature by inserting a thermocouple into the filter holder behind
borosilicate glass, stainless steel, or TFE-fluorocarbon of (1)
the filter or attached directly to the exterior of the filter holder. The tester
sufficientlengthtoreachthegassamplingpoint,(2)ofphysical
must prevent the thermocouple sensor from the direct radiant heat from
integrity to minimize adsorption of HCl and/or HF, and (3)
the heater element, and allow sufficient time for the actual filter assembly
heated and controlled to sustain the sample temperature at 350
to reach thermal equilibrium before beginning sampling.
6 15°F (177 6 8°C). The internal diameter of the probe liner
7.1.12 Barometer, capable of measuring the atmospheric
shouldbebetween0.25-0.5in.(0.1-2cm).Theprobeassembly
pressure to within 2.5 torr (0.1 in. Hg, 10.1 Kpa).
shall minimize collection of particulate matter but allow gases
7.1.13 Ice, for impinger ice water bath.
and small particles to pass.
7.2 Sample Recovery:
NOTE 5—The assembly could consist of an in-stack large pore sintered
7.2.1 Polyethylene Wash Bottles, to contain the deionized
filter (>20 microns) with a shroud, or a nozzle that is positioned away
water or acid impinger solution.
from the flow stream.
7.2.2 Polyethylene Sample Storage Bottles, to store the
NOTE 6—Aspecially designed probe that utilizes fore and aft indepen-
samples.
dent heater and heater controllers has proven to be capable of maintaining
7.2.3 100 mL Graduated Cylinders, to measure the volume
the 350°F temperature throughout the length of the probe. This is crucial
of the impinger samples.
when a portion of the probe is inserted into a hot stack but the remainder
7.3 Reagent Preparation:
of the probe is out of the stack at a much cooler relative temperature. Use
7.3.1 Class A Volumetric Flasks, Graduated Cylinders and
ofthisprobedesignwillminimizeoreliminatemoisturecondensationand
thus adsorption of HCl and HF.
Pipets, to prepare the acid absorbing solution and to prepare
the diluted calibration standards for the ion chromatograph.
7.1.2 Particulate Filters, rated at 0.3 µm (or less), and
7.4 Instrumentation:
having an efficiency of 95 % or greater in ac
...