1、Designation: D 1783 01Standard Test Methods forPhenolic Compounds in Water1This standard is issued under the fixed designation D 1783; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parenthes
2、es 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 These test methods cover the preparation of the sampleand the determinat
3、ion of the concentration of phenolic com-pounds in water. They are based on the color reaction of phenol(C6H5OH) with 4-aminoantipyrine and any color produced bythe reaction of other phenolic compounds is reported as phenol.The concentration of phenol measured represents the minimumconcentration of
4、phenolic compounds present in the sample.1.2 Phenolic compounds with a substituent in the paraposition may not quantitatively produce color with4-aminoantipyrine. However, para substituents of phenol suchas carboxyl, halogen, hydroxyl, methoxyl, or sulfonic acidgroups do produce color with 4-aminoan
5、tipyrine.1.3 These test methods address specific applications asfollows:Range SectionsTest Method AChloroform ExtractionTest Method BDirect Photometric0 to 100 g/L0.1 mg/L(100 g/L)11 to 1718 to 241.4 It is the users responsibility to assure the validity of thestandard test method for use in their pa
6、rticular matrix ofinterest.1.5 This standard does not purport to address all the safetyconcerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety andhealth practices and determine the applicability of regulatorylimitations prior to
7、 use. For specific hazard statements seeNote 1 and Note 3.2. Referenced Documents2.1 ASTM Standards:D 1129 Terminology Relating to Water2D 1192 Specification for Equipment for Sampling Waterand Steam in Closed Conduits2D 1193 Specification for Reagent Water2D 1293 Test Methods for pH of Water2D 2777
8、 Practice for Determination of Precision and Bias ofApplicable Methods of Committee D19 on Water2D 3370 Practices for Sampling Water from Closed Con-duits2D 5789 Writing Quality Control Specifications for StandardTest Methods for Organic Constituents2D 5810 Guide for Spiking Into Aqueous Samples2D 5
9、847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water Analysis23. Terminology3.1 DefinitionsFor definitions of terms used in these testmethods, refer to Terminology D 1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 phenolic compoundshydroxy derivati
10、ves of benzeneand its condensed nuclei.4. Summary of Test Methods4.1 Test MethodsAand B are photometric procedures basedon the reaction of steam-distillable phenolic compounds with4-aminoantipyrine.4.2 Test Method A differs from B mainly in that the sampleis extracted with chloroform, thereby provid
11、ing 20-fold greatersensitivity.4.3 Both procedures involve first separating the phenoliccompounds from the background matrix by distillation. Due tothe differing solubilities and boiling points of the variousphenolic compounds, each phenolic comes over in the distil-lation at a different rate. Some
12、phenolics will be substantiallytransferred near the beginning of the distillation and some willnot start to distill until near the end. For this reason somephenolics may not have been quantitatively transferred to thereceiving flask when the specified volume of distillate has beencollected.5. Signif
13、icance and Use5.1 Phenolic compounds are sometimes found in surfacewaters from natural and industrial sources. Their presence instreams and other waterways frequently will cause off flavor infish tissue and other aquatic food.1These test methods are under the jurisdiction of D19 on Water and are the
14、 directresponsibility of Subcommittee D19.06 on Methods for Analysis for OrganicSubstances in Water.Current edition approved Feb. 10, 2001. Published May 2001. Originallypublished as D 1783 60 T. Last previous edition D 1783 91 (1995).2Annual Book of ASTM Standards, Vol 11.01.1Copyright ASTM Interna
15、tional, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5.2 Chlorination of waters containing phenols may producechlorophenols that are odoriferous and objectionable tasting.6. Interferences6.1 Common interferences that may occur in waters arephenol-decomposing ba
16、cteria, reducing substances, andstrongly alkaline conditions of the sample. Provisions incorpo-rated in these test methods will minimize the effects of suchinterferences.6.2 Treatment procedures required prior to the analysis forremoval of interfering compounds may result in the unavoid-able elimina
17、tion or loss of certain types of phenolic com-pounds. It is beyond the scope of these test methods to describeprocedures for overcoming all of the possible interferences thatmay be encountered in the test methods, particularly withhighly contaminated water and industrial waste water. Theprocedures u
18、sed must be revised to meet the specific require-ments.6.3 A few methods for eliminating certain interferences aresuggested. (See Section 8 for descriptions of reagents re-quired.)6.3.1 Oxidizing AgentsIf the sample smells of chlorine, orif iodine is liberated from potassium iodide on acidification
19、ofthe sample, remove the oxidizing agents so indicated immedi-ately after sampling. The presence of oxidizing agents in thesample may oxidize some or all of the phenols in a short time.Ferrous sulfate or sodium arsenite solution may be added todestroy all of the oxidizing substances. Excess ferrous
20、sulfateor sodium arsenite do not interfere since they are removed inthe distillation procedure.6.3.2 Sulfur CompoundsCompounds that liberate hydro-gen sulfide (H2S) or sulfur dioxide (SO2) on acidification mayinterfere with the phenol determination. Treatment of theacidified sample with copper sulfa
21、te usually eliminates suchinterferences. Acidify the sample with sulfuric acid (H2SO4)orhydrochloric acid (HCl) until just acid to methyl orange. Thenadd a sufficient quantity of copper sulfate (CuSO4) solution togive a light blue color to the sample or until no more coppersulfide (CuS) precipitate
22、is formed. Excessive amounts of H2Sor SO2may be removed from the acidified sample by a briefaeration treatment or stirring before the addition of the CuSO4solution or both.NOTE 1Warning: Acidification of certain samples may produce vig-orous evolution of carbon dioxide (CO2), SO2,H2S, or other gases
23、.Therefore, perform the acidification cautiously and stir the samples duringthe process. Complete the evolution of gases before the sample isstoppered.6.3.3 Oils and TarsIf the sample contains oil or tar, somephenolic compounds may be dissolved in these materials. Analkaline extraction, in the absen
24、ce of CuSO4(Note 1), may beused to eliminate the tar and oil. Adjust the pH of the samplebetween 12 and 12.5 with sodium hydroxide (NaOH) pellets toavoid extraction of the phenols. Extract the mixture withcarbon tetrachloride (CCl4). Discard the oil- or tar-containinglayer. Remove any CCl4remaining
25、in the aqueous portion ofthe sample by gentle heating.NOTE 2The presence of CuSO4is detrimental since it is converted tocupric hydroxide (Cu(OH)2) by the NaOH. The Cu(OH)2acts as anoxidizing agent on phenols.7. Apparatus7.1 Buchner-Type Funnel with Coarse Fritted DiskAtleast three funnels are needed
26、 for determination of phenoliccompounds by Test Method A. Alternatively, standard glassfunnels and pre-fluted filter paper may be used. The funnelpaper must be large enough to hold5gofsodium sulfate.These funnels are not used in Test Method B.7.2 PhotometerA spectrophotometer or filter photometer,su
27、itable for use at 460 nm (Test Method A) or at 510 nm (TestMethod B), and accommodating a cell that gives a light path of1.0 to 10 cm shall be used. The size of the cell used will dependon the absorbance of the colored solutions being measured andthe characteristics of the photometer. In general, if
28、 the absor-bances are greater than 1.0 with a larger cell, the next smallersize cell should be used.7.3 Distillation ApparatusA 1-L, heat-resistant, distillingflask attached to a Graham condenser by means of a glass joint.7.4 pH MeterThis apparatus shall conform to the require-ments in Test Methods
29、D 1293.8. ReagentsNOTE 3Warning: Phenol, carbon tetrachloride, and chloroform arepotentially hazardous to human health. CautionAvoid inhalation anddirect contact. Use in a well-ventilated hood.8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is
30、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.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use
31、without lessening theaccuracy of the determination.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean water conforming toSpecification D 1193 Types I, II, III, or IV. Water used for thesetest methods shall be free of phenolic compounds, residualchlorine, an
32、d substances that interfere with the test. Watersufficiently free of phenolics can be generated by boiling thewater for 20 minutes.8.3 Aminoantipyrine Solution (20 g/L)Dissolve 2.0 g of4-aminoantipyrine in water and dilute to 100 mL. Prepare thisreagent fresh as used.NOTE 4The melting point of a sat
33、isfactory grade of4-aminoantipyrine ranges from 108.0 to 109.5C.8.4 Ammonium Chloride Solution (20 g/L)Dissolve 20 gof ammonium chloride (NH4Cl) in water and dilute to 1 L.8.5 Ammonium Hydroxide (NH4OH) (sp gr 0.90)Concentrated ammonium hydroxide (NH4OH).8.6 Carbon Tetrachloride (CCl4).3Reagent Chem
34、icals, 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, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand Nationa
35、l Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.D17830128.7 Chloroform (CHCl3).8.8 Hydrochloric Acid (HCl) (sp gr 1.19)Concentratedhydrochloric acid (HCl).8.9 Phenol Solution, Stock (1 mL = 10 mg phenol)Dissolve 1.00 g of phenol (C6H5OH) in freshly boiled andcooled water. Dilu
36、te to 1 000 mL with freshly boiled cooledwater. Prepare a fresh stock solution within 30 days of use.8.10 Phenol Solution, Intermediate(C6H5OH) (1 mL = 10g phenol)Dilute 10.0 mL of the stock solution to 1 000 mLwith freshly boiled and cooled water. Prepare this solutionfresh on the day it is used.8.
37、11 Phenol Solution, Standard (C6H5OH) (1 mL = 1.0g phenol)Dilute 50 mL of the intermediate solution to 500mL with freshly boiled and cooled water. Prepare this solutionfresh within2hofuse.8.12 Potassium Ferricyanide Solution (K3Fe(CN)6) (80g/L)Dissolve 8.0 g of (K3Fe(CN)6) in water and dilute to 100
38、mL. Filter if necessary. Prepare fresh weekly.8.13 Sodium Bisulfate (NaHSO4).8.14 Sodium Sulfate (Na2SO4), anhydrous and granular.8.15 Sulfuric Acid (H2SO4) (sp gr 1.84)Concentratedsulfuric acid (H2SO4).8.16 Sulfuric Acid Solution (H2SO4) (1+9)Cautiouslyadd one volume of concentrated H2SO4to nine vo
39、lumes ofwater with continuous cooling and mixing. Solution willbecome hot.9. Sampling9.1 Collect the sample in accordance with SpecificationD 1192 and Practices D 3370.9.2 When samples are composited, chill the samples or thecomposite sample immediately and keep at a temperature ofnot more than 4C d
40、uring the compositing period. The collec-tion time for a single composite sample shall not exceed 4 h. Iflonger sampling periods are necessary, collect a series ofcomposite samples. Then preserve such composite samples inaccordance with Section 10 until analyzed.10. Preservation of Samples10.1 Pheno
41、lic compounds in water are subject to bothchemical and biochemical oxidation. Preserve samples within4 h of collection. Acidify the samples to a pH between 0.5 and2.0 with H3PO4, HCl, H2SO4, or NaHSO4.10.2 To further minimize any changes in the phenoliccontent of the sample, keep it cold, preferably
42、 between 2C and4C until analysis. The preserved samples should be in glass,not plastic bottles, and preferably analyzed within 28 days aftercollection.TEST METHOD ACHLOROFORM EXTRACTION11. Scope11.1 This test method is generally applicable to water thatcontains less than 100 g/L (0.1 mg/L) of phenol
43、ic compounds.Lower levels may be achieved with different instruments andlarger cells. Higher levels can be achieved by dilution.11.2 The lowest levels of analyte detection or accuratequantitation are laboratory and sample matrix dependent and itis up to the users of the test method to determine thes
44、e levelsin their own situation.11.3 This test method was tested on municipal wastewatertreatment plant influent and effluent, lake water, river water,and industrial treatment plant effluent. It is the users respon-sibility to insure the validity of this test method for waters ofuntested matrices.12.
45、 Summary of Test Method12.1 This is a photometric test method, based on thereaction of steam-distillable phenolic compounds with4-aminoantipyrine at a pH of 10.0 6 0.2 in the presence ofK3Fe(CN)6. The antipyrine dye formed is extracted from theaqueous solution with chloroform and the absorbance isme
46、asured at 460 nm. The concentration of phenolic com-pounds in the sample is expressed in terms of micrograms perlitre of phenol C6H5OH.13. Calibration13.1 Prepare a series of 500-mL C6H5OH standards infreshly boiled and cooled water containing 0, 5, 10, 20, 30, 40,and 50 mL of standard C6H5OH soluti
47、on (1 mL = 1.0 gC6H5OH). Use all solutions at room temperature.13.2 Develop color in the series of standards and prepare thechloroform extracts in accordance with the procedures pre-scribed in Section 14 and 15.13.3 Measure the absorbance of each standard at 460 nmagainst the reagent blank as zero a
48、bsorbance. Plot the absor-bances against the corresponding weights in micrograms ofphenol.NOTE 5Make a separate calibration curve for each spectrophotometeror photoelectric colorimeter. Check each curve periodically to ensurereproducibility.14. Distillation Procedure14.1 Measure 500 mL of the sample
49、 into a beaker. Adjustthe pH of the sample to between pH 0.5 and 4 with H2SO4solution (1 + 9). Use methyl orange indicator solution or a pHmeter to aid in the pH adjustment. If the sample has beenpreviously preserved according to 10.1, this pH adjustmentstep may be omitted. Transfer the mixture to the distillationapparatus. Use a 500-mL graduated cylinder as a receiver.14.2 Distill 450 mL of the sample. Stop the distillation and,when boiling ceases, add 50 mL of water to the distillationflask. Continue the distillation until a total of 500
