1、Designation: D7065 17Standard Test Method forDetermination of Nonylphenol, Bisphenol A, p-tert-Octylphenol, Nonylphenol Monoethoxylate and NonylphenolDiethoxylate in Environmental Waters by GasChromatography Mass Spectrometry1This standard is issued under the fixed designation D7065; the number imme
2、diately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This
3、 test method covers determination of nonylphenol(NP), nonylphenol ethoxylate (NP1EO), nonylphenol di-ethoxylate (NP2EO), octylphenol (OP), and bisphenolA(BPA)that are partitioned into organic solvent, separated using gaschromatography and detected with mass selective detection.These compounds or iso
4、mer mixtures are qualitatively andquantitatively determined by this test method. This test methodadheres to selected ion monitoring mass spectrometry but fullscan mass spectrometry has also been shown to work wellunder these conditions. Either analysis may be used.1.2 The method detection limit (MDL
5、) and reporting limit(RL) for NP, NP1EO, NP2EO, OP, and BPA are listed in Table1.1.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address all of thesafety concerns, if any, associated wit
6、h its use. It is theresponsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.5 This international standard was developed in accor-dance with internationally recognized p
7、rinciples on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D1129 Terminology Relating t
8、o WaterD1193 Specification for Reagent WaterD3694 Practices for Preparation of Sample Containers andfor Preservation of Organic ConstituentsD3856 Guide for Management Systems in LaboratoriesEngaged in Analysis of WaterD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods
9、 for Water AnalysisD5905 Practice for the Preparation of Substitute WastewaterE691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method2.2 Other Publications:340 CFR Part 136, Appendix B Definition and Procedure forthe Determination of the Method Detection Limi
10、t3. Terminology3.1 Definitions:3.1.1 For definitions of terms used in this standard, refer toTerminology D1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 bisphenol A, BPA, nrepresents 4,4-dihydroxy-2,2-diphenylpropane.3.2.1.1 DiscussionCommercial bisphenol A is producedby the condensat
11、ion reaction of phenol and acetone to producepredominantly the 4,4-dihydroxy-2,2-diphenylpropane.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 app
12、roved Dec. 15, 2017. Published January 2018. Originallypublished in 2006. Last previous version approved in 2011 as D7065 11. DOI:10.1520/D7065-17.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandard
13、s volume information, refer to the standards Document Summary page onthe ASTM website.3Available from U.S. Government Printing Office, Superintendent ofDocuments, 732 N. Capitol St., NW, Washington, DC 20401-0001, http:/www.access.gpo.gov.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C
14、700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the
15、World Trade Organization Technical Barriers to Trade (TBT) Committee.13.2.2 environmental water, nshall refer to water testedusing this test method. See Section 5.3.2.3 nonylphenol, NP, nmixed isomers of branchedp-nonylphenol.3.2.3.1 DiscussionCommercial nonylphenol is producedby the reaction of phe
16、nol with commercial nonene. Commer-cial nonene is not simply a linear C9H18alpha olefin; it is acomplex mixture of predominantly nine-carbon olefins, calledpropylene trimer, containing no linear isomers. This synthesisresults in a mixture of various branched nonylphenol isomersrather than a discrete
17、 chemical structure. The branched nonylgroup is positioned predominantly in the para position on thephenol ring.3.2.4 octylphenol, OP, nrepresents 4-(1,1,3,3-tetramethylbutyl)phenol.3.2.4.1 DiscussionCommercial octylphenol is producedby the reaction of phenol and diisobutylene to produce pre-dominan
18、tly the 4-(1,1,3,3-tetramethylbutyl)phenol isomer.3.3 Abbreviations:3.3.1 n-NPnormal straight chain nonylphenol3.3.1.1 Discussionn-NP is used in this test method as asurrogate for NP, OP and BPA. n-NP is not produced commer-cially and is not expected to be found in environmental waters.3.3.2 n-NP1EO
19、normal straight chain nonylphenolethoxylate3.3.2.1 Discussionn-NP1EO is used in this test method asa surrogate for NP1EO and NP2EO. n-NP1EO is not producedcommercially and is not expected to be found in environmentalwaters.3.3.3 NP1EObranched nonylphenol monoethoxylate3.3.4 NP2EObranched nonylphenol
20、 diethoxylate4. Summary of Test Method4.1 This is a performance-based test method and modifica-tions are allowed to improve performance.4.2 For NP, NP1EO, NP2EO, BPA, and OP analysis, con-tinuous liquid-liquid extraction technique is used for watersamples.4.3 Continuous Liquid-Liquid Extraction Tech
21、niqueA1-Lvolume of sample adjusted to pH 2 is extracted with methylenechloride. The methylene chloride extract is dried using sodiumsulfate if needed, concentrated to a volume of 0.5 mL, and thenanalyzed by GC/MS operated in the selected ion monitoring(SIM) or full scan mode.4.4 The target compounds
22、 are identified by retention timeand confirmed by comparing the sample mass spectrum to thatof a known standard. The target compounds are quantitatedusing the quantitation ions of the target compounds utilizingthe internal standards acenaphthene-d10, and phenanthrene-d10.The final report issued for
23、each sample lists total concentrationof NP, NP1EO, NP2EO, BPA, and OP, if detected, or MDLs, ifnot detected, in g/L for water samples.5. Significance and Use5.1 Nonylphenol,4octylphenol, and bisphenol A have beenshown to have toxic effects in aquatic organisms. The source ofnonylphenol and octylphen
24、ol is prominently from the use ofcommon commercial surfactants. The most widely used sur-factant is NPEO which has an average ethoxylate chain of 9mol of ethoxylate. The ethoxylate chain is readily biodegradedto form NP1EO and NP2EO, nonylphenol carboxylate (NPEC)and, under anaerobic conditions, non
25、ylphenol. Nonylphenolwill also biodegrade, but may be released into environmentalwaters directly at trace levels. This test method has beeninvestigated for use with surface water and waste treatmenteffluent samples and is applicable to these matrices. It has notbeen investigated for use with salt wa
26、ter or solid samplematrices.5.2 The first reported synthesis of BPA was by the reactionof phenol with acetone by Zincke.5BPA has become animportant high volume industrial chemical used in the manu-facture of polycarbonate plastics and epoxy resins. Polycar-bonate plastic and resins are used in numer
27、ous productsincluding electrical and electronic equipment, automobiles,sports and safety equipment, reusable food and drinkcontainers, electrical laminates for printed circuit boards,composites, paints, adhesives, dental sealants, protectivecoatings, and many other products.6The environmental source
28、of BPA is predominantly from the decomposition of polycar-bonate plastics and resins. BPA is not classified as bio-accumulative by the U.S. Environmental Protection Agency(EPA) and will biodegrade. BPA may be released into theenvironment waters directly at trace levels through landfillleachate and s
29、ewage treatment plant effluents.6. Interferences6.1 Method interferences may be caused by contaminants insolvents, reagents, glassware and other apparatus that lead todiscrete artifacts or elevated baseline in the selected ion currentprofiles.All of these materials are routinely demonstrated to befr
30、ee from interferences by analyzing laboratory reagent blanksunder the same conditions as the samples.4U.S. EPA Office of Water, Aquatic Life Ambient Water Quality Criteria Nonylphenol Final, Document Number EPA-822-R-05-005, December 2005.Avail-able from United States Environmental ProtectionAgency
31、(EPA), William JeffersonClinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460, http:/www.epa.gov.5Zincke, T., 1905, “Mittheilungen aus dem chemischen Laboratorium derUniversitat Marburg,” Justus Leibigs Annals Chemie, Vol 343, pp. 7579.6Additional information about BPA is available at http
32、:/www.bisphenol-a.org.TABLE 1 Method Detection Limit (MDL) and Reporting LimitsAnalyteMDL,A(g/L)Reporting Range,B(g/L)NP 0.9 5.080.0NP1EO 1.2 10.0160.0NP2EO 1.8 20.0320.0OP 0.2 1.016.0BPA 0.3 1.016.0AMDL determined following the Code of Federal Regulations, 40 CFR Part 136,Appendix B.BLowest point o
33、f the reporting range is calculated from the LV1 concentrationcalibration standard in Table 4.D7065 1726.2 All glassware is scrupulously cleaned. All glassware iswashed in hot water with detergent such as powderedAlconox,Det-o-Jet, Luminox, or Citrajet,7rinsed in hot water and rinsedwith distilled w
34、ater. The glassware is then dried and heated inan oven at 250C for 15 to 30 min. All glassware is subse-quently cleaned with acetone and methylene chloride. Deter-gents containing alkylphenolic compounds must not be used.6.3 All reagents and solvents should be of pesticide residuepurity or higher to
35、 minimize interference problems.6.4 Matrix interferences may be caused by contaminantsthat are co-extracted from the sample. The extent of matrixinterferences will vary considerably from sample source tosample source, depending on variations of the sample matrix.7. Apparatus7.1 GC/MS System:7.1.1 Ga
36、s Chromatograph (GC) SystemAn analytical sys-tem complete with a temperature programmable gas chromato-graph and all required accessories including syringes, analyti-cal columns, autosamplers, and gases. The injection port mustbe designed for split/splitless when using the capillary col-umns.7.1.2 A
37、nalytical ColumnAn analytical column (DB-5MS30-m 0.25 mm ID; film thickness0.25 m or equivalent;(5 %-phenyl)-methylpolysiloxane) suitable for the analysis oftarget alkylphenols.87.1.3 Mass Spectrometer (MS) SystemAn MS systemcapable of scanning 45 to 500 amu every2sorless, using70 eV in the electron
38、 impact mode, and producing a massspectrum which meets all the criteria when 50 ng of decafluo-rotriphenylphosphine (DFTPP) is injected through the GCinlet.7.2 CLLE Apparatus.7.3 Organic Solvent Evaporation Device.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in
39、 all tests. Unless indicated otherwise, it is intended thatall reagents shall conform to the specifications of the Commit-tee onAnalytical Reagents of theAmerican Chemical Society.9Other reagent grades may be used provided it is first ascer-tained that they are of sufficiently high purity to permit
40、theiruse without affecting the accuracy of the measurement.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Type I of Specification D1193. It must be demonstrated thatthis water does not contain contaminants at concentrationssuf
41、ficient to interfere with the analysis.8.3 GasesResearch grade nitrogen or helium of highestpurity are used.8.4 Methylene Chloride, chromatography grade.8.5 Methanol, purge and trap grade.8.6 Branched Nonylphenol Monoethoxylate (NP1EO),available as a high purity custom standard.8.7 Branched Nonylphe
42、nol Diethoxylate (NP2EO), avail-able as a high purity custom standard.8.8 Branched Nonylphenol Ethoxylate Blend(NP1EONP3EO), where the composition is determined bygas chromatography.108.9 Nonylphenol (NP), 95 % para isomer (CAS # 84852-15-3).8.10 Octylphenol (OP), 99+ % 4-(1,1,3,3-tetramethylbutyl)p
43、henol (CAS # 140-66-9).8.11 Bisphenol A (BPA), 99+ % 4,4-ispropylidenediphenol(CAS # 80-05-7).8.12 Concentrated H2SO4(CAS # 7664-93-9)8.13 Internal Standard Mix, containing acenaphthene-d10and phenanthrene-d10.8.14 n-nonylphenol (CAS # 104-40-5).8.15 n-NP monoethoxylate (n-NP1EO, CAS # 104-35-8).8.1
44、6 Acetone, Reagent Grade (CAS # 67-64-1).8.17 Perfluorotributylamine, PFTBA (CAS # 311-89-7).9. Hazards9.1 Normal laboratory safety applies to this test method.Analysts should wear safety glasses, gloves and lab coats whenworking with acids. Methylene chloride is used as an extrac-tion solvent for t
45、his test method. Analysts should review theMSDS for all reagents used in this test method.10. Sample Collection, Preservation, and Storage10.1 Sampling:10.1.1 Grab samples must be collected in glass samplecontainers. Conventional sampling practices should be fol-lowed. Refer to Guide D3856 and Pract
46、ices D3694. Automaticsampling equipment should be as free as possible of Tygontubing and other potential sources of contamination. Samplesmust be iced or kept at 0 to 4C. Samples must be preventedfrom freezing.10.2 Preservation:10.2.1 Adjust to pH 2 with H2SO4. Store samples between0 and 4C from the
47、 time of collection until extraction. Extract7Alconox, Det-o-Jet, Luminox, and Citrajet are trademarks of Alconox, Inc.,White Plains, NY.8The sole source of supply of the columns known to the committee at this timeis J Eq 2) and Eq 6:Concentration g/L 5Ax!Is!Vt!Df!Ais!ARF!Vo!Vi!(6)where:Ax= area of
48、the characteristic ion for the compound to bemeasured,Ais= area of the characteristic ion for the internal standard,Is= amount of internal standard injected in nanograms(ng),Vo= volume of water extracted in milliliters (mL),Vi= volume of extract injected in microliters (L),Vt= volume of the concentr
49、ated extract in microlitres (L),andDf= dilution factor.15.1.1 The dilution factor for analysis of samples forsemi-volatiles by this test method is defined as follows:Df= L most concentrated extract used to make dilution + Lclean solvent/L most concentrated extract used to makedilution.15.1.2 If no dilution is performed, Df= 1.0.16. Single and Multi-Laboratory Precision and Bias16.1 Continuous Liquid/Liquid Extraction (CLLE) of Sub-stitute Wastewater Practice D5905 was determined by U.S.EPA Region 5 Chicago Regional Laboratory
