1、Designation: D 1783 01 (Reapproved 2007)Standard 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 n
2、umber 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 These test methods cover the preparation of the sample
3、and 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 minimu
4、mconcentration 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 co
5、lor 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 f
6、or 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 regulatoryli
7、mitations prior to use. For specific hazard statements see6.3.2 and 8.6.2. Referenced Documents2.1 ASTM Standards:2D 1129 Terminology Relating to WaterD 1192 Guide for Equipment for Sampling Water andSteam in Closed Conduits3D 1193 Specification for Reagent WaterD 1293 Test Methods for pH of WaterD
8、2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD 3370 Practices for Sampling Water from Closed ConduitsD 5789 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Organic Constituents3D 5810 Guide for Spiking into
9、Aqueous SamplesD 5847 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 D 1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 phenolic compound
10、shydroxy derivatives 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
11、 extracted with 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 th
12、e distil-lation 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
13、 of distillate 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 Dec. 1, 2007. Published January 2008. Originallyapproved in 1960. La
14、st previous edition approved in 2001 as D 1783 01.2For 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 website.3Withdrawn.
15、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 natural and industrial sources. Their presence instreams and other waterways frequently will caus
16、e 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 interferences that may occur in waters arephenol-decomposing bacteria, reducing substances, andstrongly a
17、lkaline 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 elimination or loss of certain types of phenolic
18、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 used must be revised to meet the specific r
19、equire-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 ofthe sample, remove the oxidizing agents
20、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 sulfateor sodium arsenite do not interfere
21、 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 sulfate usually eliminates suchinterferences. A
22、cidify 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 is formed. Excessive amounts of H2Sor SO2m
23、ay 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 of carbon dioxide (CO2), SO2,H2S, or other gases. Therefore, perform the acidificationcautiously
24、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 these materials. Analkaline extraction, in the absence of CuSO4(Note ), may beused to eliminate the
25、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 in the aqueous portion ofthe sample by gentle hea
26、ting.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 Fritted DiskAtleast three funnels are needed for determination of phenoliccompounds by Test M
27、ethod 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,suitable for use at 460 nm (Test Method A) or at 51
28、0 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 the absor-bances are greater than 1.0 with a lar
29、ger 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 D 1293.8. Reagents8.1 Purity of ReagentsReagent g
30、rade 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.4Other grades may beused, provided it is first a
31、scertained 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 understood to mean water conforming toSpecification D 1193 Types I, II, III, or IV. Water used for
32、 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 Aminoantipyrine Solution (20 g/L)Dissolve 2.0 g of4-aminoantipyrine in water and dilute to 10
33、0 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 (NH4Cl) in water and dilute to 1 L.8.5 Ammonium Hydroxide (NH4OH) (sp gr 0.90)Concentrated
34、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 Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and
35、the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.D 1783 01 (2007)28.6 Carbon Tetrachloride (CCl4). Warning: Phenol, car-bon tetrachloride, and chloroform are potentially hazardous tohuman health. Avoid inhalation and direct contact. Use
36、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 freshly boiled andcooled water. Dilute to 1 000 mL with freshly boiled cooledwater. Prepar
37、e 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.8.11 Phenol Solution, Standard (C6H5OH) (1 mL = 1.0 gph
38、enol)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 (K3Fe(CN)6) in water and dilute to 100mL. Filter if necessary. Prepare fresh weekly.8.13 So
39、dium 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 volume of concentrated H2SO4to nine volumes of waterwith continuous cooling and mixing. Sol
40、ution will become 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 during the compositing period. The collec-tion time f
41、or 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 Phenolic compounds in water are subject to bothchemical a
42、nd 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 between 2C and4C until analysis. The preserved samp
43、les 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 phenolic compounds.Lower levels may be achieved with diffe
44、rent 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 these levelsin their own situation.11.3 This test method
45、 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. Summary of Test Method12.1 This is a photometric te
46、st 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 ismeasured at 460 nm. The concentration of phenolic com-
47、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 solution (1 mL = 1.0 gC6H5OH). Use all solutions at room t
48、emperature.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 method blank (blank) as zero absorbance.Plot the absorbances agains
49、t 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 beenpreviously preserved according to 10.1, this pH adjustmentstep may be omitted. Transfer the mixt
