ASTM D2580-94(2001)
(Test Method)Standard Test Method for Phenols in Water by Gas-Liquid Chromatography
Standard Test Method for Phenols in Water by Gas-Liquid Chromatography
SCOPE
1.1 This test method covers a direct aqueous injection procedure for the gas-liquid chromatographic determination of phenols, cresols, and mono- and di-chlorophenols in water.
1.2 The precision and bias of the test method has been calculated from the results of interlaboratory analyses of three master solutions, each containing phenol, p-cresol, p-chlorophenol, 3,5-dichlorophenol.
1.3 The test method may be applied to waste water or concentrates that contain more than 1 mg/L of phenolic compounds. Therefore, for a comparison with Test Methods D1783, see Appendix X1.
1.4 The analyst should recognize that precision statements provided in and may not apply to waters of other matrices.
1.5 The values stated in SI units are to be regarded as the standard. The values given in parentheses are provided for information only.
1.6 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. For specific hazard statements, see Note 3.
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation:D 2580–94 (Reapproved 2001)
Standard Test Method for
Phenols in Water by Gas-Liquid Chromatography
This standard is issued under the fixed designation D 2580; 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 3856 Guide for Good Laboratory Practices in Laborato-
ries Engaged in Sampling and Analysis of Water
1.1 This test method covers a direct aqueous injection
D 4210 Practice for Intralaboratory Quality Control Proce-
procedure for the gas-liquid chromatographic determination of
2 dures and a Discussion Reporting Low-Level Data
phenols, cresols, and mono- and di-chlorophenols in water.
E 260 Practice for Packed Column Gas Chromatography
1.2 The precision and bias of the test method has been
E 355 Practice for Gas Chromatography Terms and Rela-
calculated from the results of interlaboratory analyses of three
tionships
master solutions, each containing phenol, p-cresol,
p-chlorophenol, 3,5-dichlorophenol.
3. Terminology
1.3 The test method may be applied to waste water or
3.1 Definitions—Definitions and terms are presented in
concentrates that contain more than 1 mg/L of phenolic
Practice E 355 and Terminology D 1129.
compounds. Therefore, for a comparison with Test Methods
3.1.1 The following terms used in this test method are
D 1783, see Appendix X1.
defined in Terminology D 1129 as follows:
1.4 The analyst should recognize that precision statements
3.1.2 ghosting— a gas-chromatographic interference, show-
provided in 16.1 and 16.2 may not apply to waters of other
ing as a peak, which appears at the same elution time as a
matrices.
component from previous injection.
1.5 The values stated in SI units are to be regarded as the
3.1.3 internal standard—a material present in or added to
standard. The values given in parentheses are provided for
samplesinknownamounttoserveasareferencemeasurement.
information only.
3.1.4 noise—an extraneous electronic signal that affects
1.6 This standard does not purport to address all of the
baseline stability.
safety concerns, if any, associated with its use. It is the
3.1.5 phenolic compounds—hydroxy derivatives of ben-
responsibility of the user of this standard to establish appro-
zene and its condensed nuclei.
priate safety and health practices and determine the applica-
3.1.6 retention time—the time that elapses from the intro-
bility of regulatory limitations prior to use. For specific hazard
duction of the sample until the component peak maximum is
statements, see Note 3.
reached.
2. Referenced Documents
4. Summary of Test Method
2.1 ASTM Standards:
3 4.1 This test method uses a single gas-liquid chromato-
D 1129 Terminology Relating to Water
3 graphic column for the separation of phenolic compounds and
D 1193 Specification for Reagent Water
4 a flame-ionization detector for their measurement. The peak
D 1783 Test Methods for Phenolic Compounds in Water
area of each component is measured and compared with that of
D 3370 Practices for Sampling Water from Closed Con-
a known standard to obtain quantitative results.Adiscussion of
duits
gas chromatography is presented in Practice E 260.
4.2 In this test method, elution of characteristic phenols
This test method is under the jurisdiction ofASTM Committee D-19 on Water
occurs in the following order: (1) o-chlorophenol, (2) phenol
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
and o-cresol, (3) m- and p-cresol, (4) 2,3-, 2,4-, 2,5- and
Organic Substances in Water.
2,6-dichlorophenols, (5) m- and p-chlorophenol, and (6) 3,4-
Current edition approved Sept. 15, 1994. Published November 1994. Originally
published as D 2580 – 67 T. Last previous edition D 2580 – 89.
dichlorophenol.
Baker, R. A., “Phenolic Analyses by Direct Aqueous Injection Gas Chroma-
4.2.1 For comparison purposes, see Appendix X1.
tography,” Journal American Water Works Association, Vol 58, No. 6, 1966, pp.
751–760.
Annual Book of ASTM Standards, Vol 11.01.
4 5
Annual Book of ASTM Standards, Vol 11.02. Annual Book of ASTM Standards, Vol 14.02.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 2580–94 (2001)
5. Significance and Use bore) open tubular, analytical capillary, etc., may be used if it
is shown to give precision and bias comparable to those
5.1 Phenolic compounds are sometimes found in surface
obtained in the interlaboratory study of this test method. The
waters from natural and industrial sources. Chlorination of
three columns cited in this procedure may be modified with the
such waters may produce odoriferous, objectionable tasting
understanding that the elution time and sensitivity may be
chlorophenols. These compounds may include o-chlorophenol,
altered.
p-chlorophenol, 2,6-dichlorophenol, and 2,4-dichlorophenol.
7.1.1 Carbowax 20-M —A 3-mm by 3-m ( ⁄8-in. by 10-ft)
6. Interferences stainless steel column packed with 60/80 mesh Chromosorb
W (acid washed and hexamethyldisilazane, (HMDS)-treated)
6.1 Particulate Matter—Particulate or suspended matter
coated with 20 weight % of Carbowax 20M-TPA (terephthalic
may, unless very finely subdivided, plug the needle used for
acid).
sample injection. Such matter may be removed by centrifuga-
7.1.2 Free Fatty Acid Phase, 1.5 m—A 3-mm by 1.5-m
tion or filtration, provided it is ascertained that compounds of
( ⁄8-in. by 5-ft) stainless steel column packed with 70/80 mesh
interest are not removed also. A colloid mill may be used, if
Chromosorb W (acid washed) coated with 5 weight % free
necessary,toprepareacolloidalsolutionorsuspensionsuitable
fatty acid phase.
for injection. Particulate matter may serve as condensation
7.1.3 Free Fatty Acid Phase, 3-m—A 3-mm by 3-m ( ⁄8-in.
nuclei for samples; acid treatment may often dissolve such
by 10-ft) stainless steel column packed with 60/80 mesh
interfering solids.
Chromosorb T coated with 10 % free fatty acid phase. Chro-
6.2 Nonphenolic Organics—Compounds which have the
mosorb T is a TFE-fluorocarbon 6 product which melts at
same retention value as the phenolic compounds will interfere
327°C and may begin to fuse above 250°C. It is available from
with the test. Such compounds may be eliminated by a suitable
suppliers of gas chromatographic materials.
preliminary separation technique.
7.2 Gas Chromatograph—A commercial or custom de-
NOTE 1—Refer to Test Methods D 1783.
signed gas chromatograph with a column oven capable of
6.3 Alkaline Compounds—Under strongly alkaline condi-
isothermal temperature control to at least 210 6 0.2°C. A unit
tions, some chlorophenols may form salts which reduce their
equipped for temperature programming will facilitate elution
volatility in the test. Also, some nonphenolic organics, for
of a mixture of phenolics of wide boiling-point range.This test
example, tar bases, may be more volatile in basic solution.
methoddescribesanisothermalanalysisusingasinglecolumn-
Simple pH adjustment to near neutral or slightly acid will
type gas chromatograph. Temperature programming is an
eliminate these interferences.
option of the analyst.
6.4 Ghosts—Elimination of ghosts or memory peaks is
7.3 Hydrogen Flame Ionization Detector.
requisite before chromatographic analyses are possible. In this
7.4 Recorder—To measure chromatographic output at a
test method, ghosts are minimized or eliminated by injecting 3
full-scale range of 1 mV with a response time of 1 s.
µL of water between all sample injections. This water wash
7.5 Syringe, 10-µL.
usually clears the injection port, column, and detector of
artifacts; however, repeated wash injections may be necessary
8. Reagents and Materials
toclearthesystem.Theelectrometershouldbesetatmaximum
8.1 Purity of Reagents—Reagent grade chemicals shall be
sensitivity during the wash injections to facilitate detection of
used in all tests. Unless otherwise indicated, it is intended that
ghosts.
all reagents shall conform to the specifications of the Commit-
NOTE 2—Glass injector inserts are recommended. Inserts are easy to
tee onAnalytical Reagents of theAmerican Chemical Society,
clean or replace and minimize clean-up difficulties. 11
where such specifications are available. Other grades may be
6.5 Other Interferences—It is beyond the scope of this test
used, provided it is first ascertained that the reagent is of
method to describe procedures for eliminating all possible
sufficiently high purity to permit its use without lessening the
interferences which might occur, particularly with highly
accuracy of the determinations.
contaminated industrial waste water. In addition, the chro-
8.2 Unless otherwise indicated, references to water shall be
matographic resolution of this test method is insufficient to
understood to mean Type II reagent water as specified in
differentiate among some isomeric alkyl phenols.
Specification D 1193.
8.3 Carrier Gases— Research grade nitrogen or helium of
7. Apparatus
highest purity are used as carrier gases.
7.1 Chromatographic Columns—Columns may be pur-
chased or prepared by the analyst. Variations of column
loading, length, diameter, support size, treatment, etc., are
Carbowax is a trademark of Union Carbide.
possible.Any column, for example, packed, wide bore (mega-
Chromosorb is a trademark of Johns, Mansville.
Available from Varian Aerograph, Walnut Creek, Calif.
Reagent Chemicals, American Chemical Society Specifications, American
Burttschell, R. H., et al., “Chlorine Derivatives of Phenol Causing Taste and Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Odor,” Journal American Water Works Association, Vol 51, No. 2, 1959. listed by the American Chemical Society, see Analar Standards for Laboratory
Baker, Robert A., “Trace Organic Analyses by Aqueous Gas-Liquid Chroma- Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
tography,” Air and Water Pollution Institute Journal, Pergamon Press,Vol 10, 1966, and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
pp. 591–602. MD.
D 2580–94 (2001)
8.4 Hydrogen (H)— For use with the flame ionization tight. Aqueous soap solutions may be used to locate minor
detector; may be obtained using a hydrogen generator, or from leaks but this should be done with caution. If soap solution
a high-purity tank supply. entersthesystem,itmayprovedifficulttoeliminateextraneous
8.5 Phenolic Compounds—Research grades of high purity peaks or stabilize the system. Do not use the soap method for
are required. Highest purity compounds may be prepared by leak testing near the ionization detector.
redistillation, recrystallization, or by using a preparatory gas
10.3 Column Conditioning:
chromatographic instrument.
10.3.1 Condition columns for at least 24 h at temperatures
30 to 50°C above the expected operating temperature before
NOTE 3—Warning—Phenolic compounds are skin irritants. Appropri-
use. Exercise caution to avoid exceeding the maximum allow-
ate safety measures should be taken to preclude contact with or inhalation
of phenolic compounds. able temperature for both the packing and substrate.
10.3.2 Disconnect the column at the end near the detector
The following phenolic compounds are suggested:
base to avoid deposition of volatiles on the detector during
8.5.1 o-Chlorophenol,
conditioning.
8.5.2 m-Chlorophenol,
10.3.3 Adjust carrier gas flow to about 20 to 40 mL/min for
8.5.3 p-Chlorophenol,
8.5.4 o-Cresol, a 3-mm ( ⁄8-in.) diameter column.
8.5.5 m-Cresol, 10.3.4 Occasional injection of 3 to 5 µL of water during
8.5.6 p-Cresol,
conditioning facilitates elution of impurities.
8.5.7 2,3-Dichlorophenol,
10.3.5 After conditioning, connect the column to the flame
8.5.8 2,4-Dichlorophenol,
ionization detector.
8.5.9 2,5-Dichlorophenol,
10.3.6 Adjust the hydrogen flow to the detector to about 25
8.5.10 2,6-Dichlorophenol, 1
mL/min for a 3-mm ( ⁄8-in.) diameter column. Adjust the air
8.5.11 3,4-Dichlorophenol, and
flow as specified in the instrument being used. Ignite the
8.5.12 Phenol.
detector.
10.3.7 Adjust the column temperature to the desired level.
9. Sampling
10.3.8 Adjust the carrier gas flow rate to 20 to 40 mL/min.
9.1 Collect the sample in accordance with Practices D 3370.
10.3.9 Observetherecorderbaseline.Whenabaselinedrift
9.2 Because of the possibility of oxidation or bacterial
is no longer apparent, the column is ready for use.
decomposition of phenols in the sample, the lapse of time
10.3.10 When the series of analyses are completed and the
beforeanalysesshouldbekepttoaminimum.Inaddition,keep
column is to be moved and stored, it is advisable to seal or cap
the sample cool and protected from atmospheric oxygen.
the ends.
10. Preparation of Chromatograph
11. Operating Conditions for Analysis
10.1 Install the packed column in the chromatograph using
suitable fittings. The use of antigalling thread lubricant is 11.1 Typical operating conditions are summarized in Table
advisable. 1.These operating parameters may be varied but analytical and
10.2 Conduct a leak test at approximately 103 kPa (15 psi) calibration test variations must be reconciled in calculating
above the operating pressure by shutting off the downstream results. For example, either nitrogen or helium may be used as
end of the system and pressurizing from the carrier gas supply. the carrier gas; recorder chart speeds of approximately 30 in./h
Shut off the cylinder valve and observe the pressure gage. If no are commonly employed; sample sizes of 3 to 5 µLare usually
drop is noted in 10 to 15 min, the system may be considered injected (see Figs. 1-5).
TABLE 1 Typical Operating Conditions for Chromatographic Columns
Column Number
1 2 3
(see 7.1.1) (see 7.1.2) (see 7.1.3)
Column and Packing
3-mby3-mm(10-ftby ⁄8-in.) 1.5-m by 3-mm 3-mby3-mm(10-ft
1 1
SS, 20 % Carbowax (5-ft by ⁄8-in.) by ⁄8-in.) SS, 10 %
20M-TPA, 60/80 Chromo- SS, 5 % FFAP, 70/80 Chromosorb W FFAP Chromosorb T
sorb W-HMDS
Carrier gas helium helium nitrogen
Carrier gas flow, mL/min 25 35 60
Temperature, °C:
Injection port 250 205 250
Column 210 147 188
Hydrogen for detector, mL/min 25 25 30
Chart speed, in. (mm)/h 12 (305) 12 12
Sensitivity, mV 1 1 1
Electrometer range 1 0.1 1
Attenuation 1 1 1
Sample vol,µ L 1 1 1
Figure reference Figs. 1 and 2 Fig. 5 Figs. 3 and 4
D 2580–94 (2001)
NOTE 1—Analyses were made with 3-m by 3-mm (10-ft by ⁄8-in.)
NOTE
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