State of California

Air Resources Board

Method 13A

Determination of Total Fluoride Emissions from

Stationary Sources
(SPADNS Zirconium Lake Method)

Adopted: March 28, 1986

Amended: July 1, 1999
Method 13A - Determination of Total Fluoride Emissions from Stationary Sources
(SPADNS Zirconium Lake Method)

1. APPLICABILITY AND PRINCIPLE

1.1 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
Freons.

1.2 Principle. Gaseous and particulate F are withdrawn isokinetically from the source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.

Any modification of this method beyond those expressly permitted shall be considered a
major modification subject to the approval of the Executive Officer. The term Executive
Officer as used in this document shall mean the Executive Officer of the Air Resources
Board (ARB), or his or her authorized representative.

2. RANGE AND SENSITIVITY

The range of this method is 0 to 1.4 g F/ml. Sensitivity has not been determined.

3. INTERFERENCES

Large quantities of chloride will interfere with the analysis, but this interference can be
prevented by adding silver sulfate into the distillation flask (see Section 7.3.4). If chloride ion is
present, it may be easier to use 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 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/m 3. The
within-laboratory and between-laboratory standard deviations, which include sampling
and analysis errors, were 0.044 mg F/m3 with 60 degrees of freedom and 0.064 mg F/m3
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 3o C temperature difference between the sample and
standard solutions produces an error of approximately 0.005 mg F/liter. To avoid this
error, the absorbencies of the sample and standard solutions must be measured at the
same temperature.

July 1999 CARB Method 13A Page 1

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, respectively. 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 probe 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 oC (248  25 o F).

5.1.3 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 silicone 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 silicone rubber
gasket. The tester may also use other materials of construction with approval from
the Executive Officer.

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
impingers, use the Greenburg-Smith design, modified by replacing the tip with a
1.3-cm (1/2-in.) ID glass tube extending to 1.3 cm (1/2 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 Executive
Officer. Place a thermometer, capable of measuring temperature to within 1 oC (2oF),
at the outlet of the fourth impinger for monitoring purposes.

5.2 Sample Recovery. The following items are need:

5.2.1 Probe-liner and Probe-Nozzle Brushes, Wash Bottles, Graduated

Cylinder and/or Balance, Plastic Storage Containers, Rubber Policeman, and
Funnel. Same as Method 5, Sections 2.2.1, 2.2.2 and 2.2.5 to 2.2.8, respectively.

5.2.2 Sample Storage Container. Wide-mouth, high-density polyethylene bottles

for impinger water samples, 1 liter.

5.3 Analysis. The following equipment is needed:

5.3.1 Distillation Apparatus. Glass distillation apparatus assembled as shown in

Figure 13A-2.

July 1999 CARB Method 13A Page 2

 5.3.2 Bunsen Burner.

5.3.3 Electric Muffle Furnace. Capable of heating to 600 oC.

5.3.4 Crucibles. Nickel, 75- to 100-ml.

5.3.5 Beakers. 200-ml and 1500-ml.

5.3.6 Volumetric Flasks. 50-ml, 100 ml, 250 ml, 500 ml, and 1 liter.

5.3.7 Erlenmeyer Flasks or Plastic Bottles. 500-ml.

5.3.8 Constant Temperature Bath. Capable of maintaining a constant

temperature of 1.0oC at room temperature conditions.

5.3.9 Balance. 300-g capacity, to measure to 0.5 g.

5.3.10 Spectrophotometer. Instrument that measures absorbance at 570 nm and

provides at least a 1-cm light path.

5.3.11 Spectrophotometer Cells. 1-cm pathlength.

6. REAGENTS

Use ACS reagent-grade chemicals, or equivalent, unless otherwise specified.

NOTE: Mention of company or product names does not constitute endorsement by the Air
Resources Board.

6.1 Sampling. The reagents used in sampling are as follows:

6.1.1 Filters.

6.1.1.1 If the filter is located between the third and fourth impingers, use a
Whatman No. 1 filter, or equivalent, sized to fit the filter holder.

6.1.1.2 If the filter is located between the probe and first impinger, use any
suitable medium (e.g., paper, organic membrane) that conforms to the
following specifications: (1) The filter can withstand prolonged exposure to
temperatures up to 135 oC (275oF). (2) The filter has at least 95 percent
collection efficiency (<5 percent penetration) for 0.3 m 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/cm2 of
filter area). Before the test series, determine the average F blank value of at
least three filters (from the lot to be used for sampling) using the applicable
procedures described in Sections 7.3 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.

July 1999 CARB Method 13A Page 3

 6.1.2 Water. Deionized distilled, to conform to ASTM Specification D 1193-74,
Type 3. If high concentrations of organic matter are not expected to be present, the
analyst may delete the potassium permanganate test for oxidizable organic matter.

6.1.3 Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method 5,
Section 3.1.2, 3.1.4, and 3.1.5, respectively.

6.2 Sample Recovery. Water, from same container as described in Section 6.1.2, is
needed for sample recovery.

6.3 Sample Preparation and Analysis. The reagents needed for sample preparation
and analysis are as follows:

6.3.1 Calcium Oxide (Ca0). Certified grade containing 0.005 percent F or less.

6.3.2 Phenolphthalein Indicator. Dissolve 0.1 g of phenolphthalein in a mixture of

50 ml of 90 percent ethanol and 50 ml of water.

6.3.3 Silver Sulfate (Ag2SO4).

6.3.4 Sodium Hydroxide (Na0H), Pellets.

6.3.5 Sulfuric Acid (H2SO4), Concentrated.

6.3.6 Sulfuric Acid, 25 Percent (v/v). Mix 1 part of concentrated H2SO4 with 3
parts of water.

6.3.7 Filters. Whatman No. 541, or equivalent.

6.3.8 Hydrochloric Acid (HCl), Concentrated.

6.3.9 Water. Same as in Section 6.1.2.

6.3.10 Fluoride Standard Solution, 0.01 mg F/ml. Dry in an oven at 110oC for at
least 2 hours. Dissolve 0.2210 g of NaF in 1 liter of water. Dilute 100 ml of this
solution to 1 liter with water.

6.3.11 SPADNS Solution [4,5 dihydroxyy-3-(p-sulfophenylazo)-2,7-

naphthalene-disulfonic acid trisodium salt]. Dissolve 0.960  0.010 g of
SPADNS reagent in 500 ml 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 to 100 ml water, and acidify with a solution prepared by diluting
7 ml of concentrated HCl to 10 ml with water.

6.3.13 SPADNS Mixed Reagent. Dissolve 0.135  0.005 g of zirconyl chloride

octahydrate (Zr0Cl2.8H2O) in 25 ml of water. Add 350 ml of concentrated HCl, and
dilute to 500 ml with water. Mix equal volumes of this solution and SPADNS
solution to form a single reagent. This reagent is stable for at least 2 months.

July 1999 CARB Method 13A Page 4

7. PROCEDURE

7.1 Sampling. Because of the complexity of this method, testers should be trained and
experienced with the test 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.

7.1.2 Preliminary Determinations. Follow the general procedure given in Method

5, Section 4.1.2, except the nozzle size selected must maintain isokinetic sampling
rates below 28 liters/min (1.0 cfm).

7.1.3 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 water in each of the first two impingers, and leave the third
impinger empty. Transfer approximately 200 to 300 g of preweighed silica gel from
its container to the fourth impinger.

Assemble the train as shown in Figure 13A-1 with the filter between the third and
fourth impingers. 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 filter heating system to prevent moisture condensation,
but shall not allow the temperature to exceed 120  14oC (248  25oF). Record the
filter location on the data sheet.

7.1.4 Leak-Check Procedures. Follow the leak-check procedures given in

Method 5, Sections 4.1.4.1, 4.1.4.2, and 4.1.4.3.

7.1.5 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 
14oC (248  25oF) and isokinetic sampling rates below 28 liters/min (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 as soon as the probe is
removed from the stack at the end of the sampling period.

Allow the probe to cool. When it can be safely handled, wipe off all external particulate
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
backwards.

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 silicone grease
from the filter holder inlet, and cap this inlet. Remove the umbilical cord from the last

July 1999 CARB Method 13A Page 5

 impinger, and cap the impinger. After wiping off the silicone grease, cap off the filter
holder outlet and any open impinger inlets and outlets. The tester may use ground-glass
stoppers, plastic caps, or serum caps to close these openings.

Transfer the probe and filter-impinger assembly to an area that is clean and protected
from the wind so that the chance of contaminating or losing the sample is minimized.

Inspect the train before and during disassembly, and note any abnormal conditions.
Treat the samples as 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 impingers; include 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 procedures subject to the Executive Officer's approval.) Taking care that dust
on the outside of the probe or other exterior surfaces does not get into the sample,
clean all sample-expose surfaces (including the probe nozzle, probe fitting, probe
liner, first three impingers, impinger connectors, and filter holder) with water. Use
less than 500 ml for the entire wash. Add the washings to the sample container.
Perform the water rinses as follows:

Carefully remove the probe nozzle and rinse the inside surface with 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 water in a similar way.

Rinse the probe liner with water. While squirting the water into the upper end of the
probe, tilt and rotate the probe so that all inside surfaces 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 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 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 runs, 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 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 of the brush.

July 1999 CARB Method 13A Page 6

 After ensuring that all joints have been wiped clean of the silicone grease, brush
and rinse with 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 particulate 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.

7.2.2 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 Container No. 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. Transfer the silica gel from the fourth impinger to its original container,
and seal. The tester may use a funnel 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 leakage occurred during
transport. If noticeable leakage had occurred, either void the sample or use
methods, subject to the approval of the Executive Officer, to correct the final
results.) Treat the contents of each sample container as described below:

7.3.1 Container No. 1 (Probe, Filter, and Impinger Catches). Filter this
container's contents, including the sampling filter, through Whatman No. 541 filter
paper, or equivalent, into a 1500-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 ml of 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 Ca0 until the color turns red again.

After evaporation of the water, place the crucible on a hot plate under a hood,

July 1999 CARB Method 13A Page 7

 and slowly increase the temperature until the Whatman No. 541 and sampling
filters char. It may take several hours to char the filters completely.

Place the crucible in a cold muffle furnace. Gradually (to prevent smoking)
increase the temperature to 600 o 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 mix. Return the
crucible to the muffle furnace, and fuse the sample for 10 minutes at 600 o C.

Remove the sample from the furnace, and cool to ambient temperature.
Using several rinsings of warm 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 H2SO4, and carefully add to the
beaker. Mix well, and transfer to a 1-liter volumetric flask. Dilute to volume
with 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 7.3.1 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 water in the distillation
flask, and add 200 ml of concentrated H2SO4. (Caution: Observe standard
precautions when mixing H2SO4 with water. Slowly add the acid 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 oC to adjust the acid/water ratio for subsequent
distillations. Discard the distillate.

7.3.4 Distillation. Cool the contents of the distillation flask to below 80 oC. Pipet an
aliquot of sample containing less than 10.0 mg F directly into the distillation flask,
and add 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 Ag2SO4 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 oC. 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 oC to avoid causing H2SO4 to distill over.

If F distillation in the mg range is to be followed by a distillation in the fractional mg

range, add 220 ml of water, and distill it over as in the acid adjustment step to
remove residual F from the distillation system.

July 1999 CARB Method 13A Page 8

 The tester may use the acid in the distillation flask until there is carry-over of
interferences or poor F recovery. Check for these every tenth distillation using a
water blank and a standard solution. Change the acid whenever the F recovery is
less than 90 percent or the blank value exceeds 0.1 g/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
flasks to exactly 250 ml with water, and mix thoroughly. Pipet a suitable aliquot of
each sample distillate (containing 10 to 40 g F/ml) into a beaker, and dilute to 50
ml with water. Use the same aliquot size for the blank. Add 10 ml of SPADNS
mixed reagent (Section 6.3.13), and mix thoroughly.

After mixing, place the sample in a constant-temperature bath containing the

standard solutions (see Section 8.2) for 30 minutes before reading the absorbance
on the spectrophotometer.

Set the spectrophotometer to zero absorbance at 570 nm with the reference

solution (Section 6.3.12), and check the spectrophotometer calibration with the
standard solution. Determine the absorbance of the samples, 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 0.5 g using a balance. The tester may conduct this step in
the field.

8. CALIBRATION

Maintain a laboratory log of all calibrations.

8.1 Sampling Train. Calibrate the probe nozzle, pitot tube, metering system, probe
heater, temperature gauges, and barometer according to Method 5, Sections 5.1, 5.2,
5.3, 5.4, 5.5, and 5.7, respectively. Conduct the leak-check of the metering system
according to Method 5, Section 5.6.

8.2 Spectrophotometer. Prepare the blank standard by adding 10 ml of SPADNS

mixed reagent to 50 ml of water. Accurately prepare a series of standards from the 0.01
mg F/ml standard fluoride solution (Section 6.3.10) by diluting 0, 2, 4, 6, 8, 10, 12, and 14
ml to 100 ml with water. Pipet 50 ml from each solution, and transfer each to a separate
200-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 g F (0 to 1.4 g/ml), respectively.

After mixing, place the reference standards and reference solution in a constant
temperature bath for 30 minutes before reading the absorbance with the
spectrophotometer. Adjust all samples to this same temperature before analyzing.

With the spectrophotometer at 570 nm, use the reference solution (Section 6.3.12) to set
July 1999 CARB Method 13A Page 9
 the absorbance to zero.

Determine the absorbance of the standards. Prepare a calibration curve by plotting g

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.

9. CALCULATIONS

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.

Ad = Aliquot of distillate taken for color development, ml.

At = Aliquot of total sample added to still, ml.

Bws = Water vapor in the gas stream, proportion by volume.

Cs = Concentration of F in stack gas, dry basis, corrected to standard conditions of

760 mm Hg and 293 o K (29.92 in. Hg and 528 o R), mg/m3 (mg/ft3).

Ft = Total F in sample, mg.

g F = Concentration from the calibration curve, g.

Tm = Absolute average dry gas meter temperature (see Figure 5-2 of Method 5), oK
(oR).

Ts = Absolute average stack gas temperature (see Figure 5-2 of Method 5), oK (oR).

Vd = Volume of distillate as diluted, ml.

Vm(std) = Volume of gas sample as measured by DGM at standard conditions, dscm

(dscf).

Vt = Total volume of F sample, after final dilution, ml.

Vw(std)= Volume of water vapor in the gas sample at standard conditions, scm (scf)

9.2 Average DGM Temperature and Average Orifice Pressure Drop. See data sheet
(Figure 5-2 of Method 5).

9.3 Dry Gas Volume. Calculate Vm(std), and adjust for leakage, if necessary, using the
equation in Section 6.3 of Method 5.

July 1999 CARB Method 13A Page 10

9.4 Volume of Water Vapor and Moisture Content. Calculate Vw(std) and Bws from the data
obtained in this method (Figure 13A-l); use Equations 5-2 and 5-3 of Method 5.

9.5 Concentration.

9.5.1 Total Fluoride in Sample. Calculate the amount of F in the sample using the
following equation:

-3
10 V t V d
Ft = (μ g F) Eq. 13A-1
At Ad

9.5.2 Fluoride Concentration in Stack Gas. Determine the F concentration in the

stack gas using the following equation:

KFt
Cs = Eq. 13A-2
V m(std)

Where:
K = 1.00 m3/m3 if Vm(std) is expressed in metric units.

= 35.31 ft3/m3 if Vm(std) is expressed in English units.

9.6 Isokinetic Variation and Acceptable Results. Use Method 5, Sections 6.11.1 and 6.11.2.

10. BIBLIOGRAPHY

1. EPA Method 13A, Determination of Total Fluoride Emissions from Stationary Sources
(SPADNS Zirconium Lake Method), CFR40, Part 60, Appendix A

2. ARB Method 5, Determination of Particulate Matter Emissions from Stationary Sources

July 1999 CARB Method 13A Page 11

Temperature
Sensor Optional Filter
Holder Location

Probe
Stack Filter
Wall Holder
Temperature
Heat Traced Sensor
Type S Glass-lined
Pitot Tube Probe

Check
Valve

Type S Pitot Tube Ice

Water
Manometer Bath
Vacuum
Line

Temperature Impingers
Sensors
Vacuum
Gauge
Orifice

By-pass Main
Valve Valve

Dry Gas
Meter
Air-Tight
Pump

Figure 13A-1. Fluoride Sampling Train

 Connecting Tube
12 mm ID
T 24
S
40

Thermometer

T 24
S
40

With
T 24
S
40 S 24
T
40
Adapter
Adapter

T 24
S 40

Condenser

1-Liter
Flask

500-ml
Erlenmeyer
Flask

Figure 13A-2. Fluoride Distillation Apparatus.