ASTM D3269-96(2001)e1
(Test Method)Standard Test Methods for Analysis for Fluoride Content of the Atmosphere and Plant Tissues (Manual Procedures) (Withdrawn 2010)
Standard Test Methods for Analysis for Fluoride Content of the Atmosphere and Plant Tissues (Manual Procedures) (Withdrawn 2010)
SIGNIFICANCE AND USE
These test methods may be used for the determination of the fluoride content of particulate matter and gases collected in 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 semiquantitative measure of atmospheric concentrations or deposition rates of fluorides.
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).
WITHDRAWN RATIONALE
These test methods described manual procedures for the determination of fluoride in various types of samples. The procedures outlined, consequently, were appropriate to the analysis of ambient air samples taken by diverse sampling techniques when properly applied.
Formerly under the jurisdiction of Committee D22 on Air Quality, these test methods were withdrawn in February 2010 in accordance with subsection 10.5.3.1 of the Regulations Governing ASTM Technical Committees, which requires that standards shall be updated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.
General Information
Relations
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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.
´1
Designation:D3269–96 (Reapproved 2001)
Standard Test Methods for
Analysis for Fluoride Content of the Atmosphere and Plant
Tissues (Manual Procedures)
This standard is issued under the fixed designation D3269; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.
´ NOTE—Footnotes were deleted editorially throughout in March 2001.
1. Scope D3268 Test Method for Separation and Collection of Par-
ticulateandGaseousFluoridesintheAtmosphere(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)
proceduresoutlined,consequently,areappropriatetotheanaly-
D3270 Test Methods for 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
E1 Specification for ASTM Liquid-in-Glass 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 D1356.
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 10.7.1.3 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:
to provide a representative sample, reliable isolation of the
D1193 Specification for Reagent Water
fluoride, and accurate measurement, the methods are prefaced
D1356 Terminology Relating to Sampling and Analysis of
bydiscussionofgeneralprecautionsandsamplepreparationas
Atmospheres
applied to specific cases.
D1357 Practice for Planning the Sampling of the Ambient
Atmosphere
5. Significance and Use
D3267 Test Method for Separation and Collection of Par-
5.1 Thesetestmethodsmaybeusedforthedeterminationof
ticulate and Water-Soluble Gaseous Fluorides in the At-
thefluoridecontentofparticulatematterandgasescollectedin
mosphere (Filter and Impinger Method)
theatmospherebypassiveandactivemonitors,includingplant
material.Theuseriswarnedthatthefluoridecontentofpassive
These test methods are under the jurisdiction ofASTM Committee D22 onAir
collectors (including plant materials) gives a qualitative or
Quality and are the direct responsibility of Subcommittee D22.03 on Ambient
semiquantitative measure of atmospheric concentrations or
Atmospheres and Source Emissions.
deposition rates of fluorides.
Current edition approved April 10, 1996. Published June 1996. Originally
´1
published as D3269–73T. Last previous edition D3269–91 . DOI: 10.1520/
6. Apparatus
D3269-96R01E01.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
6.1 Crucible, nickel, inconel, or platinum.
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
6.2 Beakers, nickel or platinum.
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. 6.3 Muffle Furnace.
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959, United States.
´1
D3269–96 (2001)
6.4 Wiley Cutting Mill. 7.4 or 7.6) solution, then with water and air dried under clean
toweling. Inconel crucibles used for fusion of ash may require
7. Reagents and Materials
additionalcleaningbyboilingin10%NaOH(see7.8)solution
7.1 Purity of Reagents—Reagents shall conform to the
for 1 h. Glassware is washed with hot detergent solution
specifications of the Committee onAnalytical Reagents of the
followed by a rinse in warm, dilute HCl or HNO (see 7.4 or
American Chemical Society, where such specifications are
7.6);itisfinallyrinsedwithwateranddried(seeWarning).All
available.
sampling devices, containers, volumetric glassware, reagent
7.2 Purity of Water—Water shall be Type II reagent water
solutions, and so forth, are stored under suitable conditions of
conforming to Specification D1193. Additionally, the water
protection from airborne dusts and fumes and are reserved for
used in the sampling and analytical procedure shall be dem-
exclusive use in low-fluoride analysis. (Warning—The distill-
onstrated by testing with a specific ion electrode or by
ing flasks should be cleaned using only a brush and water.
concentration and photometric analysis to contain less than
Repeated use of alkaline cleaning solution produces an etched
0.005 µg/mL of F.
surface that is difficult to clean and that tends to retain
7.3 Calcium Oxide, (CaO), with known low fluoride con-
fluoride.)
centration.
9.1.3 Before proceeding with analysis of samples, blank
7.4 Hydrochloric Acid, (2 %)—Dilute5mLofhydrochloric
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-
chloric acid (HCl, sp gr 1.19) to 100 mL with water.
obtained. Calibration standards are analyzed whenever new
7.5 Hydrogen Peroxide Solution, (30%), (H O ).
batches of reagent solutions are prepared. In addition, one
2 2
7.6 Nitric Acid, (5 %)—Dilute 5 mL of nitric acid (HNO ,
blank and one standard determination are carried through the
sp gr 1.42) to 100 mL with water.
entireanalyticprocedurewitheachsetoftenorfewersamples.
7.7 Phenolphthalein Indicator Solution (0.05 g/L)—
Ifsamplesarehandledinlargersets,theratioofoneblankand
Dissolve 0.5 g of phenolphthalein in 60 mL of ethyl alcohol
one standard per ten samples should be maintained.
and dilute to 1 L with water.
9.2 Sample Preparation:
7.8 Sodium Hydroxide (10 %)—Dissolve 10.0 g of sodium
9.2.1 The techniques of sample recovery and preparation
hydroxide (NaOH) in water and dilute to 100 mL with water.
will vary, as described below, with the sampling method and
7.8.1 Sodium Hydroxide (20 %)—Dissolve 20.0 g of so-
equipment, and will also depend upon the procedures selected
dium hydroxide (NaOH) in water and dilute to 100 mL with
for isolation and measurement of fluoride. Until proof to the
water.
contraryisestablished,samplesareassumedtocontainfluoride
7.9 Sodium Hydroxide Alcoholic Solution,(1 N)—Dissolve
in refractory forms in addition to the commonly encountered
4gofNaOHin5mLofwateranddiluteto100mLwithethyl,
methyl, or Formula 30 denatured alcohol. interfering materials. Many details involved in the determina-
tion of gaseous and particulate fluorides in the atmosphere and
8. Sampling
in vegetation are discussed by Pack, et al, (1) and automatic
8.1 See Practice D1357 for general sampling procedures,
apparatus for the determination of ambient atmospheric HF
and Test Methods D3267 and D3268D3267D3268 for proce-
concentrationsdownto0.1ppb(v)hasalsobeendescribed(2).
dures and guidelines applicable to sampling atmospheric fluo-
9.2.2 Particulate Fluorides:
rides.
9.2.2.1 Particulatemattercollectedinairsamplinggenerally
requires fusion with NaOH for conversion into soluble form
9. General Precautions and Sample Preparation
before separation of fluoride byWillard-Winter distillation (3).
9.1 General Precautions:
This treatment is also necessary for materials containing
9.1.1 Fluorine is one of the more common elements and
fluoride associated with aluminum, for materials high in silica,
occurs in at least trace amounts in virtually all natural and
and for many minerals.
manufactured materials. Contamination by extraneous fluoride
may, therefore, come from such sources as sampling and 9.2.2.2 Transferthesample-bearingpaperfiltertoaresistant
laboratoryapparatus,reagents,andfromexposuretolaboratory crucible (see 6.1), for example, nickel, platinum, or Inconel,
dust and fumes. Care must be exercised in the selection,
moisten with water, and make alkaline to phenolphthalein (see
purification, and testing of reagents and apparatus, and only
7.7) using CaO (see 7.3). After evaporation to dryness, ignite
minimal exposures of samples should be permitted.
the paper in a muffle furnace at a temperature of 550 to 600°C
9.1.2 Vessels used for evaporation, ashing, or caustic fusion
until all carbonaceous material has been oxidized. Control
ofsamplesarefirstrinsedwithwarm,diluteHClorHNO (see
combustionoffiltersofthemembrane(celluloseester)typeby
drenching with alcoholic NaOH (see 7.9) solution and igniting
with a small gas flame.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
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, The boldface numbers in parentheses refer to the references at the end of these
MD. methods.
´1
D3269–96 (2001)
9.2.2.3 Removeparticulatematter,collectedbyelectrostatic electric furnace reserved for the ignition of low-fluoride
precipitation, from the surfaces of both electrodes with the aid materials. The ash should be white or gray, indicating removal
of a rubber policeman and water. Make the resulting suspen- of organic matter.
sion alkaline to phenophthalein (see 7.7) with NaOH (see 7.9) 9.2.5.4 When the ash has cooled, pulverize it and scrape all
solution and evaporate to dryness. material from the dish; mix and determine the net mass. Store
in a tightly stoppered bottle.
9.2.2.4 Integrated samples, that is, those containing both
9.2.5.5 To effect quantitative release of fluoride combined
gaseous and particulate fluorides, that have been collected on
glass fiber filters, are not amenable to fusion; filters are with silica in many varieties of vegetation, fusion of the
limed-ashwithNaOHisrequiredandisroutinelyperformedon
transferred directly to the distillation flask. Integrated samples
collectedinimpingersaretransferredtobeakersmadeofnickel all vegetation specimens (4-6). Transfer approximately1gof
ash into a tared nickel, platinum, or Iconel crucible (see 6.1)
or other resistant materials, evaporated to dryness in the
alkaline condition, and the residue ashed if organic matter is and weigh accurately. Add about5gof NaOH pellets, cover
the vessel, and fuse the contents for a few minutes over a gas
present.
burner.Aftercoolingthemelt,noteitscolor;ablue-greencolor
9.2.2.5 Fuse the impinger sample, residue from ashing of a
indicates the presence of manganese and treatment with
filter, or electrostatic precipitator catch, with2gof NaOH.
H O (see 7.5) is required as described in 11.7.2. Disintegrate
Dissolve the cold melt in a few millilitres (mL) of water, add
2 2
the melt with hot water, washing down the lid and walls of the
four or five drops of 30% H O (see 7.5) to oxidize sulfites to
2 2
crucible. Reserve the resulting material for isolation of fluo-
sulfates, and boil the solution to destroy excess peroxide. The
ride.
sample solution is then ready for isolation of fluoride.
9.2.3 Ambient Gaseous Fluorides, Dry Collectors:
10. Isolation of Fluoride (Willard-Winter Distillation)
9.2.3.1 Treat filter papers impregnated with calcium-based
10.1 Principle of Method—The prepared sample is distilled
fixative agents as described above for particulate fluorides,
from a strong acid such as H SO or HClO in the presence of
2 4 4
except that caustic fusion of the ashed residue is not required.
a source of silica. Fluoride is steam distilled as the fluosilicic
9.2.3.2 Filtersimpregnatedwithsolublealkaliesareleached
acid under conditions permitting a minimum of volatilization
withwater,asarefixative-coatedbeadsortubes.Evaporatethe
and entrainment of the liberating acid (7).
washings in a suitable vessel and maintain in an alkaline
10.2 Range and Sensitivity—TheWillard-Winterdistillation
condition during reduction to a volume convenient for the
method, on the macroscale, can accommodate quantities of
subsequent fluoride separation procedure. Add four or five
fluoride ranging from 100 mg down to a few milligrams (mg).
drops of 30% H O (see 7.5) and boil the solution to destroy
2 2
10.3 Interferences—Samples relatively free of interfering
excess peroxide.
materials, and containing fluoride in forms from which it is
9.2.3.3 Gaseous fluorides collected on glass fiber filters
easily liberated, may be subjected to a single distillation from
cannot be quantitatively removed by leaching with water.
HClO at 135°C. Samples containing appreciable amounts of
Transfer such filters directly to the flasks in which Willard-
aluminum, boron, or silica require a higher temperature and
Winter distillations are to be conducted.
larger volume of distillate for quantitative recovery. In this
9.2.4 Ambient Gaseous Fluorides, Wet Collectors:
case, a preliminary distillation from H SO at 165°C is
2 4
9.2.4.1 Transfer a sample collected in water or alkaline
commonly used (Note 1). Large amounts of chlorides are
solution to a suitably sized vessel, make alkaline to phenol-
separated by precipitation with AgClO following the first
phthalein (see 7.7) with NaOH (see 7.9), and evaporate to the
distillation. Small amounts are held back in the second distil-
desired volume. Treat the solution with 30% H O (see 7.5)
2 2
lation from HClO by addition of AgClO to the distillation
4 4
and destroy the excess peroxide by boiling before proceeding
flask. See Note 1.
with the isolation and determination of fluoride.
NOTE 1—Generally, samples from the atmosphere do not present a
9.2.5 Vegetation:
problem with aluminum and silicon inhibiting the distillation of fluoride.
9.2.5.1 Reduce the gross specimen to manageable size for
The presence of boron in amounts sufficient to interfere with subsequent
mixing by use of hand shears or, in the case of dried materials,
determinations of fluoride, is also unlikely. Where there is concern over
a Wiley cutting mill. Take a small portion (10 to 25 g) of the
these interferences, however, the distillation and analytical methods
should be selected to avoid the interferences or to establish the fact that
mixed specimen for determination of moisture by oven drying
they are not significant.
at 80°C for 24 to 48
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.