1、Designation: D1783 01 (Reapproved 2012)Standard Test Methods forPhenolic Compounds in Water1This standard is issued under the fixed designation D1783; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A num
2、ber in parentheses indicates the year of last reapproval. Asuperscript 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.1. Scope1.1 These test methods cover the preparation of the sampleand
3、 the determination 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 minimumco
4、ncentration of 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
5、 with 4-aminoantipyrine.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
6、use in their particular 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 regulatorylimit
7、ations prior to use. For specific hazard statements see6.3.2 and 8.6.2. Referenced Documents2.1 ASTM Standards:2D1129 Terminology Relating to WaterD1192 Guide for Equipment for Sampling Water and Steamin Closed Conduits3D1193 Specification for Reagent WaterD1293 Test Methods for pH of WaterD2777 Pra
8、ctice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3370 Practices for Sampling Water from Closed ConduitsD5789 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Organic Constituents3D5810 Guide for Spiking into Aqueous Sam
9、plesD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water Analysis3. Terminology3.1 DefinitionsFor definitions of terms used in these testmethods, refer to Terminology D1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 phenolic compoundshydroxy deri
10、vatives of benzeneand its condensed nuclei.4. Summary of Test Methods4.1 Test Method A and Test Method B are photometricprocedures based on the reaction of steam-distillable phenoliccompounds with 4-aminoantipyrine.4.2 Test Method A differs from Test Method B mainly inthat the sample is extracted wi
11、th chloroform, thereby providing20-fold greater sensitivity.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-lati
12、on at a different rate. Some 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 distillat
13、e has beencollected.1These test methods are under the jurisdiction of D19 on Water and are the directresponsibility of Subcommittee D19.06 on Methods for Analysis for OrganicSubstances in Water.Current edition approved June 15, 2012. Published August 2012. Originallyapproved in 1960. Last previous e
14、dition approved in 2007 as D1783 01R07. DOI:10.1520/D1783-01R12.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM websi
15、te.3Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5. Significance and Use5.1 Phenolic compounds are sometimes found in surfacewaters from
16、 natural and industrial sources. Their presence instreams and other waterways frequently will cause off flavor infish tissue and other aquatic food.5.2 Chlorination of waters containing phenols may producechlorophenols that are odoriferous and objectionable tasting.6. Interferences6.1 Common interfe
17、rences that may occur in waters arephenol-decomposing bacteria, 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 inte
18、rfering compounds may result in the unavoid-able elimination 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 contam
19、inated water and industrial waste water. Theprocedures used 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 iod
20、ine is liberated from potassium iodide on acidification 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 to
21、destroy all of the oxidizing substances. Excess ferrous 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 determina
22、tion. Treatment of theacidified sample with copper sulfate 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
23、sample or until no more coppersulfide (CuS) precipitate 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. Warning: Acidification of certain samplesmay produce vigorous evolution
24、 of carbon dioxide (CO2), SO2,H2S, or other gases. Therefore, perform the acidificationcautiously and stir the samples during the process. Completethe evolution of gases before the sample is stoppered.6.3.3 Oils and TarsIf the sample contains oil or tar, somephenolic compounds may be dissolved in th
25、ese materials. Analkaline extraction, in the absence of CuSO4, may be used toeliminate the tar and oil. Adjust the pH of the sample between12 and 12.5 with sodium hydroxide (NaOH) pellets to avoidextraction of the phenols. Extract the mixture with carbontetrachloride (CCl4). Discard the oil- or tar-
26、containing layer.Remove any CCl4remaining in the aqueous portion of thesample by gentle heating.NOTE 1The 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 Fr
27、itted DiskAtleast three funnels are needed 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
28、 spectrophotometer or filter photometer,suitable 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 charact
29、eristics of the photometer. In general, if 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 con
30、form to the require-ments in Test Methods D1293.8. Reagents8.1 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 Societ
31、y,where such specifications are available.4Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understo
32、od to mean water conforming toSpecification D1193 Types I, II, III, or IV. Water used for thesetest methods shall be free of phenolic compounds, residualchlorine, and substances that interfere with the test. Watersufficiently free of phenolics can be generated by boiling thewater for 20 min.8.3 Amin
33、oantipyrine Solution (20 g/L)Dissolve 2.0 g of4-aminoantipyrine in water and dilute to 100 mL. Prepare thisreagent fresh as used.NOTE 2The melting point of a satisfactory grade of4-aminoantipyrine ranges from 108.0 to 109.5C.8.4 Ammonium Chloride Solution (20 g/L)Dissolve 20 gof ammonium chloride (N
34、H4Cl) in water and dilute to 1 L.8.5 Ammonium Hydroxide (NH4OH) (sp gr 0.90)Concentrated ammonium hydroxide (NH4OH).4Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical S
35、ociety, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.D1783 01 (2012)28.6 Carbon Tetrachloride (CCl4). Warning: Phenol, car-bon tetrachloride, and chloro
36、form are potentially hazardous tohuman health. Avoid inhalation and direct contact. Use in awell-ventilated hood.8.7 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 fr
37、eshly boiled andcooled water. Dilute 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 sol
38、utionfresh on the day it is used.8.11 Phenol Solution, Standard (C6H5OH) (1 mL = 1.0 gphenol)Dilute 50 mL of the intermediate solution to 500 mLwith freshly boiled and cooled water. Prepare this solutionfresh within2hofuse.8.12 Potassium Ferricyanide Solution (K3Fe(CN)6) (80g/L)Dissolve 8.0 g of (K3
39、Fe(CN)6) in water and dilute to 100mL. 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)Cautiously addone vol
40、ume of concentrated H2SO4to nine volumes of waterwith continuous cooling and mixing. Solution will become hot.9. Sampling9.1 Collect the sample in accordance with SpecificationD1192 and Practices D3370.9.2 When samples are composited, chill the samples or thecomposite sample immediately and keep at
41、a temperature ofnot more than 4C during 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.
42、 Preservation of Samples10.1 Phenolic 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 th
43、e sample, keep it cold, preferably 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
44、 than 100 g/L (0.1 mg/L) of phenolic 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
45、 the test method to determine these 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
46、for waters ofuntested matrices.12. 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
47、chloroform and the absorbance ismeasured 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,a
48、nd 50 mL of standard C6H5OH solution (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 nma
49、gainst the reagent method blank (blank) as zero absorbance.Plot the absorbances against the corresponding weights inmicrograms of phenol.NOTE 3Make 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 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 beenpreviousl
