ASTM D3269-96
(Test Method)Standard Test Methods for Analysis for Fluoride Content of the Atmosphere and Plant Tissues (Manual Procedures)
Standard Test Methods for Analysis for Fluoride Content of the Atmosphere and Plant Tissues (Manual Procedures)
SCOPE
1.1 These test methods describe manual procedures for the determination of fluoride in various types of samples. The procedures outlined, consequently, are appropriate to the analysis of ambient air samples taken by diverse sampling techniques when properly applied.
1.2 The values stated in SI units are to be regarded as the standard.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific precautionary statements are given in 10.7.1.3 and Ref (9).
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NOTICE: This standard has either been superseded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
Designation: D 3269 – 96 An American National Standard
Standard Test Methods for
Analysis for Fluoride Content of the Atmosphere and Plant
1,2
Tissues (Manual Procedures)
This standard is issued under the fixed designation D 3269; 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 (e) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.
1. Scope D 3268 Test Method for Separation and Collection of Par-
ticulate and Gaseous Fluorides in the Atmosphere (Sodium
1.1 These test methods describe manual procedures for the
Bicarbonate-Coated Glass Tube and Particulate Filter
determination of fluoride in various types of samples. The
Method)
procedures outlined, consequently, are appropriate to the analy-
D 3270 Test Methods of Analysis for Fluoride Content of
sis of ambient air samples taken by diverse sampling tech-
the Atmosphere and Plant Tissues (Semiautomated
niques when properly applied.
Method)
1.2 The values stated in SI units are to be regarded as the
E 1 Specification for ASTM Thermometers
standard.
1.3 This standard does not purport to address all of the
3. Terminology
safety concerns, if any, associated with its use. It is the
3.1 Definitions—For definitions of terms used in this test
responsibility of the user of this standard to establish appro-
method, see Terminology D 1356.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. Specific precau-
4. Summary of Test Methods
tionary statements are given in Note 4 and Ref (9).
4.1 Fundamentally, isolation of the fluoride followed by
analytis constitutes each of the methods. Because of the wide
2. Referenced Documents
range of types of samples and the care required in the analysis
2.1 ASTM Standards:
3 to provide a representative sample, reliable isolation of the
D 1193 Specification for Reagent Water
fluoride, and accurate measurement, the methods are prefaced
D 1356 Terminology Relating to Sampling and Analysis of
4 by discussion of general precautions and sample preparation as
Atmospheres
applied to specific cases.
D 1357 Practice for Planning the Sampling of the Ambient
Atmosphere
5. Significance and Use
D 3267 Test Method for Separation and Collection of Par-
5.1 These test methods may be used for the determination of
ticulate and Water-Soluble Fluorides in the Atmosphere
4 the fluoride content of particulate matter and gases collected in
(Filter and Impinger Method)
the atmosphere by passive and active monitors, including plant
material. The user is warned that the fluoride content of passive
collectors (including plant materials) gives a qualitative or
These test methods are under the jurisdiction of ASTM Committee D-22 on
Sampling and Anlysis of Atmospheresand are the direct responsibility of Subcom-
semiquantitative measure of atmospheric concentrations or
mittee D22.03on Ambient Atmospheres and Source Emissions.
deposition rates of fluorides.
Current edition approved April 10, 1996. Published June 1996. Originally
published as D3269 – 73 T. Last previous edition D3269 – 91e .
6. Apparatus
These test methods were originally written by the Intersociety Committee on
Methods for Ambient Air Sampling and Analysis and published as “Tentative
6.1 Crucible, nickel, inconel, or platinum.
Methods of Analysis for Fluoride Content of the Atmosphere and Plant Tissues
6.2 Beakers, nickel or platinum.
(Manual Methods)” 12204-01-68T pp. 246–265, Methods of Air Sampling and
6.3 Muffle Furnace.
Analysis, 1972, Parts A–F and 12202-01-72T, pp. 304–307, Health Laboratory
Science, Vol 9, No. 4, October 1972. This revision has been adapted from “Methods 6.4 Wiley Cutting Mill.
of Air Sampling and Analysis,” Intersociety Committee, edited by James P. Lodge,
Jr., 3rd Edition, Lewis Publishers, Inc., 1989, pp. 344–346 and 352–356. The
7. Reagents and Materials
methods are presented here essentially as published. The individuals participating in
7.1 Purity of Reagents—Reagents shall conform to the
the Intersociety Committee work and the sources of the methods are referenced in
the publications cites.
Annual Book of ASTM Standards, Vol 11.01
4 5
Annual Book of ASTM Standards, Vol 11.03. Annual Book of ASTM Standards, Vol 14.03.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
D 3269
specifications of the Committee on Analytical Reagents of the for 1 h. Glassware is washed with hot detergent solution
American Chemical Society, where such specifications are followed by a rinse in warm, dilute HCl or HNO (see 7.4 or
available. 7.6); it is finally rinsed with water and dried (see Note 1). All
7.2 Purity of Water—Water shall be Type II reagent water sampling devices, containers, volumetric glassware, reagent
conforming to Specification D 1193. Additionally, the water solutions, and so forth, are stored under suitable conditions of
used in the sampling and analytical procedure shall be dem- protection from airborne dusts and fumes and are reserved for
onstrated by testing with a specific ion electrode or by exclusive use in low-fluoride analysis. See Note 1.
concentration and photometric analysis to contain less than
NOTE 1—Caution: The distilling flasks should be cleaned using only a
0.005 μg/mL of F.
brush and water. Repeated use of alkaline cleaning solution produces an
7.3 Calcium Oxide, (CaO), with known low fluoride con-
etched surface that is difficult to clean and that tends to retain fluoride.
centration.
9.1.3 Before proceeding with analysis of samples, blank
7.4 Hydrochloric Acid, (2 %)—Dilute 5 mL of hydrochloric
determinations are repeated until satisfactorily low values (5
acid (HCl, sp gr 1.19) to 100 mL with water.
μg, or less, total fluoride per determination) are consistently
7.4.1 Hydrochloric Acid, (4 %)—Dilute 10 mL of hydro-
obtained. Calibration standards are analyzed whenever new
chloric acid (HCl, sp gr 1.19) to 100 mL with water.
batches of reagent solutions are prepared. In addition, one
7.5 Hydrogen Peroxide Solution, (30 %), (H O ).
2 2
blank and one standard determination are carried through the
7.6 Nitric Acid, (5 %)—Dilute 5 mL of nitric acid (HNO ,
entire analytic procedure with each set of ten or fewer samples.
sp gr 1.42) to 100 mL with water.
If samples are handled in larger sets, the ratio of one blank and
7.7 Phenolphthalein Indicator Solution (0.05 g/L)—
one standard per ten samples should be maintained.
Dissolve 0.5 g of phenolphthalein in 60 mL of ethyl alcohol
9.2 Sample Preparation:
and dilute to 1 L with water.
9.2.1 The techniques of sample recovery and preparation
7.8 Sodium Hydroxide (10 %)—Dissolve 10.0 g of sodium
will vary, as described below, with the sampling method and
hydroxide (NaOH) in water and dilute to 100 mL with water.
equipment, and will also depend upon the procedures selected
7.8.1 Sodium Hydroxide (20 %)—Dissolve 20.0 g of so-
for isolation and measurement of fluoride. Until proof to the
dium hydroxide (NaOH) in water and dilute to 100 mL with
contrary is established, samples are assumed to contain fluoride
water.
in refractory forms in addition to the commonly encountered
7.9 Sodium Hydroxide Alcoholic Solution,(1 N)—Dissolve
interfering materials. Many details involved in the determina-
4 g of NaOH in 5 mL of water and dilute to 100 mL with ethyl,
tion of gaseous and particulate fluorides in the atmosphere and
methyl, or Formula 30 denatured alcohol.
in vegetation are discussed by Pack, et al, (1) and automatic
apparatus for the determination of ambient atmospheric HF
8. Sampling
concentrations down to 0.1 ppb (v) has also been described (2).
8.1 See Practice D 1357 for general sampling procedures,
9.2.2 Particulate Fluorides:
and Test Methods D 3267 and D 3268 for procedures and
9.2.2.1 Particulate matter collected in air sampling generally
guidelines applicable to sampling atmospheric fluorides.
requires fusion with NaOH for conversion into soluble form
before separation of fluoride by Willard-Winter distillation (3).
9. General Precautions and Sample Preparation
This treatment is also necessary for materials containing
9.1 General Precautions:
fluoride associated with aluminum, for materials high in silica,
9.1.1 Fluorine is one of the more common elements and
and for many minerals.
occurs in at least trace amounts in virtually all natural and
9.2.2.2 Transfer the sample-bearing paper filter to a resistant
manufactured materials. Contamination by extraneous fluoride
crucible (see 6.1), for example, nickel, platinum, or Inconel,
may, therefore, come from such sources as sampling and
moisten with water, and make alkaline to phenolphthalein (see
laboratory apparatus, reagents, and from exposure to laboratory
7.7) using CaO (see 7.3). After evaporation to dryness, ignite
dust and fumes. Care must be exercised in the selection,
the paper in a muffle furnace at a temperature of 550 to 600°C
purification, and testing of reagents and apparatus, and only
until all carbonaceous material has been oxidized. Control
minimal exposures of samples should be permitted.
combustion of filters of the membrane (cellulose ester) type by
9.1.2 Vessels used for evaporation, ashing, or caustic fusion
drenching with alcoholic NaOH (see 7.9) solution and igniting
of samples are first rinsed with warm, dilute HCl or HNO (see
with a small gas flame.
7.4 or 7.6) solution, then with water and air dried under clean
9.2.2.3 Remove particulate matter, collected by electrostatic
toweling. Inconel crucibles used for fusion of ash may require
precipitation, from the surfaces of both electrodes with the aid
additional cleaning by boiling in 10 % NaOH (see 7.8) solution
of a rubber policeman and water. Make the resulting suspen-
sion alkaline to phenophthalein (see 7.7) with NaOH (see 7.9)
solution and evaporate to dryness.
Reagent Chemicals, American Chemical Society Specifications, American
9.2.2.4 Integrated samples, that is, those containing both
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
gaseous and particulate fluorides, that have been collected on
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, Alconox, available from Fisher Scientific Company, has been found suitable for
MD. this purpose.
7 9
Available on special order from G. Frederick Smith Chemical Co., P.O. Box The boldface numbers in parentheses refer to the references at the end of these
23344, Columbus, OH 43223. methods.
D 3269
glass fiber filters, are not amenable to fusion; filters are material from the dish; mix and determine the net mass. Store
transferred directly to the distillation flask. Integrated samples in a tightly stoppered bottle.
collected in impingers are transferred to beakers made of nickel 9.2.5.5 To effect quantitative release of fluoride combined
or other resistant materials, evaporated to dryness in the with silica in many varieties of vegetation, fusion of the
alkaline condition, and the residue ashed if organic matter is limed-ash with NaOH is required and is routinely performed on
present. all vegetation specimens (4-6). Transfer approximately1gof
9.2.2.5 Fuse the impinger sample, residue from ashing of a ash into a tared nickel, platinum, or Iconel crucible (see 6.1)
filter, or electrostatic precipitator catch, with2gof NaOH. and weigh accurately. Add about5gof NaOH pellets, cover
Dissolve the cold melt in a few millilitres (mL) of water, add the vessel, and fuse the contents for a few minutes over a gas
four or five drops of 30 % H O (see 7.5) to oxidize sulfites to burner. After cooling the melt, note its color; a blue-green color
2 2
sulfates, and boil the solution to destroy excess peroxide. The indicates the presence of manganese and treatment with
sample solution is then ready for isolation of fluoride. H O (see 7.5) is required as described in 11.7.2. Disintegrate
2 2
9.2.3 Ambient Gaseous Fluorides, Dry Collectors: the melt with hot water, washing down the lid and walls of the
9.2.3.1 Treat filter papers impregnated with calcium-based crucible. Reserve the resulting material for isolation of fluo-
fixative agents as described above for particulate fluorides, ride.
except that caustic fusion of the ashed residue is not required.
10. Isolation of Fluoride (Willard-Winter Distillation)
9.2.3.2 Filters impregnated with soluble alkalies are leached
10.1 Principle of Method—The prepared sample is distilled
with water, as are fixative-coated beads or tubes. Evaporate the
from a strong acid such as H SO or HClO in the presence of
washings in a suitable vessel and maintain in an alkaline
2 4 4
a source of silica. Fluoride is steam distilled as the fluosilicic
condition during reduction to a volume convenient for the
acid under conditions permitting a minimum of volatilization
subsequent fluoride separation procedure. Add four or five
and entrainment of the liberating acid (7).
drops of 30 % H O (see 7.5) and boil the solution to destroy
2 2
10.2 Range and Sensitivity—The Willard-Winter distillation
excess peroxide.
method, on the macroscale, can accommodate quantities of
9.2.3.3 Gaseous fluorides collected on glass fiber filters
fluoride ranging from 100 mg down to a few milligrams (mg).
cannot be quantitatively removed by leaching with water.
10.3 Interferences—Samples relatively free of interfering
Transfer such filters directly to the flasks in which Willard-
materials, and containing fluoride in forms from which it is
Winter distillations are to be conducted.
easily liberated, may be subjected to a single distillation from
9.2.4 Ambient Gaseous Fluorides, Wet Collectors:
HClO at 135°C. Samples containing appreciable amounts of
9.2.4.1 Transfer a sample collected in water or alkaline
aluminum, boron, or silica require a higher temperature and
solution to a suitably sized vessel, make alkaline to phenol-
larger volume of distillate for quantitative recovery. In this
phthalein (see 7.7) with NaOH (see 7.9), and evaporate to the
case, a preliminary distillation from H SO at 165°C is
desired volume. Treat the solution with 30 % H O (see 7.5)
2 4
2 2
commonly used (Note 2). Large amounts of chlorides are
and destroy the excess peroxide by boiling before proceeding
separated by precipitation with AgClO following the first
with the isolation and determination of fluoride.
distillation. Small amounts are held back in the second
...
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