1、Designation: D 2580 06Standard Test Method forPhenols in Water by Gas-Liquid Chromatography1This standard is issued under the fixed designation D 2580; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A nu
2、mber in parentheses indicates the year of last reapproval. Asuperscript 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. Scope1.1 This test method covers a direct aqueous injectionproce
3、dure for the gas-liquid chromatographic determination ofphenols, cresols, and mono- and di-chlorophenols in water.21.2 The precision and bias of the test method has beencalculated from the results of interlaboratory analyses of threemaster solutions, each containing phenol, p-cresol,p-chlorophenol,
4、3,5-dichlorophenol.1.3 The test method may be applied to waste water orconcentrates that contain more than 1 mg/L of phenoliccompounds. Therefore, for a comparison with Test MethodsD 1783, see Appendix X1.1.4 The analyst should recognize that precision statementsprovided in 16.1 and 16.2 may not app
5、ly to waters of othermatrices.1.5 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are provided forinformation only.1.6 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the
6、 user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. For specific hazardstatements, see Note 3.2. Referenced Documents2.1 ASTM Standards:3D 1129 Terminology Relating to WaterD 1193 Specification for Reag
7、ent WaterD 1783 Test Methods for Phenolic Compounds in WaterD 3370 Practices for Sampling Water from Closed ConduitsD 3856 Guide for Good Laboratory Practices in Laborato-ries Engaged in Sampling and Analysis of WaterD 4210 Practice for Intralaboratory Quality Control Proce-dures and a Discussion on
8、 Reporting Low-Level Data4E 260 Practice for Packed Column Gas ChromatographyE 355 Practice for Gas Chromatography Terms and Rela-tionships3. Terminology3.1 DefinitionsDefinitions and terms are presented inPractice E 355 and Terminology D 1129.3.1.1 The following terms used in this test method arede
9、fined in Terminology D 1129 as follows:3.1.2 ghosting a gas-chromatographic interference, show-ing as a peak, which appears at the same elution time as acomponent from previous injection.3.1.3 internal standarda material present in or added tosamples in known amount to serve as a reference measureme
10、nt.3.1.4 noisean extraneous electronic signal that affectsbaseline stability.3.1.5 phenolic compoundshydroxy derivatives of ben-zene and its condensed nuclei.3.1.6 retention timethe time that elapses from the intro-duction of the sample until the component peak maximum isreached.4. Summary of Test M
11、ethod4.1 This test method uses a single gas-liquid chromato-graphic column for the separation of phenolic compounds anda flame-ionization detector for their measurement. The peakarea of each component is measured and compared with that ofa known standard to obtain quantitative results.Adiscussion of
12、gas chromatography is presented in Practice E 260.4.2 In this test method, elution of characteristic phenolsoccurs in the following order: (1) o-chlorophenol, (2) phenoland o-cresol, (3) m- and p-cresol, (4) 2,3-, 2,4-, 2,5- and2,6-dichlorophenols, (5) m- and p-chlorophenol, and (6) 3,4-dichlorophen
13、ol.1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved Aug. 15, 2006. Published August 2006. Originallyapproved in 1967. Last previous edition
14、approved in 2001 as D 2580 94 (2001).2Baker, R. A., “Phenolic Analyses by Direct Aqueous Injection Gas Chroma-tography,” Journal American Water Works Association, Vol 58, No. 6, 1966, pp.751760.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at s
15、erviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4Withdrawn.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4.2.1 For comparison purposes, see Append
16、ix X1.5. Significance and Use5.1 Phenolic compounds are sometimes found in surfacewaters from natural and industrial sources. Chlorination ofsuch waters may produce odoriferous, objectionable tastingchlorophenols. These compounds may include o-chlorophenol,p-chlorophenol, 2,6-dichlorophenol, and 2,4
17、-dichlorophenol.56. Interferences6.1 Particulate MatterParticulate or suspended mattermay, unless very finely subdivided, plug the needle used forsample injection. Such matter may be removed by centrifuga-tion or filtration, provided it is ascertained that compounds ofinterest are not removed also.
18、A colloid mill may be used, ifnecessary, to prepare a colloidal solution or suspension suitablefor injection. Particulate matter may serve as condensationnuclei for samples; acid treatment may often dissolve suchinterfering solids.6.2 Nonphenolic OrganicsCompounds which have thesame retention value
19、as the phenolic compounds will interferewith the test. Such compounds may be eliminated by a suitablepreliminary separation technique.NOTE 1Refer to Test Methods D 1783.6.3 Alkaline CompoundsUnder strongly alkaline condi-tions, some chlorophenols may form salts which reduce theirvolatility in the te
20、st. Also, some nonphenolic organics, forexample, tar bases, may be more volatile in basic solution.Simple pH adjustment to near neutral or slightly acid willeliminate these interferences.6.4 GhostsElimination of ghosts or memory peaks isrequisite before chromatographic analyses are possible. In this
21、test method, ghosts are minimized or eliminated by injecting 3L of water between all sample injections. This water washusually clears the injection port, column, and detector ofartifacts; however, repeated wash injections may be necessaryto clear the system. The electrometer should be set at maximum
22、sensitivity during the wash injections to facilitate detection ofghosts.NOTE 2Glass injector inserts are recommended. Inserts are easy toclean or replace and minimize clean-up difficulties.6.5 Other InterferencesIt is beyond the scope of this testmethod to describe procedures for eliminating all pos
23、sibleinterferences which might occur, particularly with highlycontaminated industrial waste water.6In addition, the chro-matographic resolution of this test method is insufficient todifferentiate among some isomeric alkyl phenols.7. Apparatus7.1 Chromatographic ColumnsColumns may be pur-chased or pr
24、epared by the analyst. Variations of columnloading, length, diameter, support size, treatment, etc., arepossible. Any column, for example, packed, wide bore (mega-bore) open tubular, analytical capillary, etc., may be used if itis shown to give precision and bias comparable to thoseobtained in the i
25、nterlaboratory study of this test method. Thethree columns cited in this procedure may be modified with theunderstanding that the elution time and sensitivity may bealtered.7.1.1 Carbowax 20-M7A 3-mm by 3-m (18-in. by 10-ft)stainless steel column packed with 60/80 mesh ChromosorbW7,8(acid washed and
26、 hexamethyldisilazane, (HMDS)-treated) coated with 20 weight % of Carbowax 20M-TPA(terephthalic acid).7.1.2 Free Fatty Acid Phase, 1.5 mA 3-mm by 1.5-m(18-in. by 5-ft) stainless steel column packed with 70/80 meshChromosorb W (acid washed) coated with 5 weight % freefatty acid phase.7.1.3 Free Fatty
27、 Acid Phase, 3-mA 3-mm by 3-m (18-in.by 10-ft) stainless steel column packed with 60/80 meshChromosorb T coated with 10 % free fatty acid phase. Chro-mosorb T is a TFE-fluorocarbon 6 product which melts at327C and may begin to fuse above 250C. It is available fromsuppliers of gas chromatographic mat
28、erials.7.2 Gas ChromatographA commercial or custom de-signed gas chromatograph with a column oven capable ofisothermal temperature control to at least 210 6 0.2C. A unitequipped for temperature programming will facilitate elutionof a mixture of phenolics of wide boiling-point range. This testmethod
29、describes an isothermal analysis using a single column-type gas chromatograph. Temperature programming is anoption of the analyst.7.3 Hydrogen Flame Ionization Detector.7.4 RecorderTo measure chromatographic output at afull-scale range of 1 mV with a response time of 1 s.7.5 Syringe, 10-L.8. Reagent
30、s and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.9O
31、ther grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determinations.5Burttschell, R. H., et al., “Chlorine Derivatives of Phenol Causing Taste andOdor,” Journal American Water Works Association,
32、 Vol 51, No. 2, 1959.6Baker, Robert A., “Trace Organic Analyses by Aqueous Gas-Liquid Chroma-tography,” Air and Water Pollution Institute Journal, Pergamon Press, Vol 10, 1966,pp. 591602.7The sole source of Carbowax known to the committee at this time is UnionCarbide, P.O. Box 4393, Houston, TX 7721
33、0. If you are aware of alternativesuppliers, please provide this information to ASTM International Headquarters.Your comments will receive careful consideration at a meeting of the responsibletechnical committee,1which you may attend.8The sole source of supply of Chromosorb known to the committee at
34、 this timeis Johns Manville, P.O. Box 5108, Denver, CO 80217.9Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BD
35、H Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.D 2580 0628.2 Unless otherwise indicated, references to water shall beunderstood to mean reagent water that meets the purityspecifications of Type I or Typ
36、e II water presented in Specifi-cation D 1193.8.3 Carrier Gases Research grade nitrogen or helium ofhighest purity are used as carrier gases.8.4 Hydrogen (H) For use with the flame ionizationdetector; may be obtained using a hydrogen generator, or froma high-purity tank supply.8.5 Phenolic Compounds
37、Research grades of high purityare required. Highest purity compounds may be prepared byredistillation, recrystallization, or by using a preparatory gaschromatographic instrument.NOTE 3WarningPhenolic compounds are skin irritants. Appropri-ate safety measures should be taken to preclude contact with
38、or inhalationof phenolic compounds.The following phenolic compounds are suggested:8.5.1 o-Chlorophenol,8.5.2 m-Chlorophenol,8.5.3 p-Chlorophenol,8.5.4 o-Cresol,8.5.5 m-Cresol,8.5.6 p-Cresol,8.5.7 2,3-Dichlorophenol,8.5.8 2,4-Dichlorophenol,8.5.9 2,5-Dichlorophenol,8.5.10 2,6-Dichlorophenol,8.5.11 3,
39、4-Dichlorophenol, and8.5.12 Phenol.9. Sampling9.1 Collect the sample in accordance with Practices D 3370.9.2 Because of the possibility of oxidation or bacterialdecomposition of phenols in the sample, the lapse of timebefore analyses should be kept to a minimum. In addition, keepthe sample cool and
40、protected from atmospheric oxygen.10. Preparation of Chromatograph10.1 Install the packed column in the chromatograph usingsuitable fittings. The use of antigalling thread lubricant isadvisable.10.2 Conduct a leak test at approximately 103 kPa (15 psi)above the operating pressure by shutting off the
41、 downstreamend of the system and pressurizing from the carrier gas supply.Shut off the cylinder valve and observe the pressure gage. If nodrop is noted in 10 to 15 min, the system may be consideredtight. Aqueous soap solutions may be used to locate minorleaks but this should be done with caution. If
42、 soap solutionenters the system, it may prove difficult to eliminate extraneouspeaks or stabilize the system. Do not use the soap method forleak testing near the ionization detector.10.3 Column Conditioning:10.3.1 Condition columns for at least 24 h at temperatures30 to 50C above the expected operat
43、ing temperature beforeuse. Exercise caution to avoid exceeding the maximum allow-able temperature for both the packing and substrate.10.3.2 Disconnect the column at the end near the detectorbase to avoid deposition of volatiles on the detector duringconditioning.10.3.3 Adjust carrier gas flow to abo
44、ut 20 to 40 mL/min fora 3-mm (18-in.) diameter column.10.3.4 Occasional injection of 3 to 5 L of water duringconditioning facilitates elution of impurities.10.3.5 After conditioning, connect the column to the flameionization detector.10.3.6 Adjust the hydrogen flow to the detector to about 25mL/min
45、for a 3-mm (18-in.) diameter column. Adjust the airflow as specified in the instrument being used. Ignite thedetector.10.3.7 Adjust the column temperature to the desired level.10.3.8 Adjust the carrier gas flow rate to 20 to 40 mL/min.10.3.9 Observe the recorder base line. When a base line driftis n
46、o longer apparent, the column is ready for use.10.3.10 When the series of analyses are completed and thecolumn is to be moved and stored, it is advisable to seal or capthe ends.11. Operating Conditions for Analysis11.1 Typical operating conditions are summarized in Table1. These operating parameters
47、 may be varied but analytical andcalibration test variations must be reconciled in calculatingresults. For example, either nitrogen or helium may be used asTABLE 1 Typical Operating Conditions for Chromatographic ColumnsColumn and PackingColumn Number1(see 7.1.1)3-mby3-mm(10-ftby18-in.)SS, 20 % Carb
48、owax20M-TPA, 60/80 Chromo-sorb W-HMDS2(see 7.1.2)1.5-m by 3-mm(5-ft by18-in.)SS, 5 % FFAP, 70/80 Chromosorb W3(see 7.1.3)3-mby3-mm(10-ftby18-in.) SS, 10 %FFAP Chromosorb TCarrier gas helium helium nitrogenCarrier gas flow, mL/min 25 35 60Temperature, C:Injection port 250 205 250Column 210 147 188Hyd
49、rogen for detector, mL/min 25 25 30Chart speed, in. (mm)/h 12 (305) 12 12Sensitivity, mV 1 1 1Electrometer range 1 0.1 1Attenuation 1 1 1Sample vol, L 1 1 1Figure reference Figs. 1 and 2 Fig. 5 Figs. 3 and 4D 2580 063the carrier gas; recorder chart speeds of approximately 30 in./hare commonly employed; sample sizes of 3 to 5 L are usuallyinjected (see Figs. 1-5).12. Method of Compound Identification12.1 Compound identification is based upon the retentiontime. The retention times of the sample peaks are matched withthose of known standard
