1、Designation: D 7065 06Standard 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 D 7065; the number im
2、mediately 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 T
3、his 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
4、isomer mixtures are qualitatively andquantitatively determined by this method. This method adheresto selected ion monitoring mass spectrometry but full scanmass spectrometry has also been shown to work well underthese conditions. Either analysis may be used.1.2 The method detection limit (MDL) repor
5、ting limit (RL)for NP, NP1EO, NP2EO, OP, and BPA are listed in Table 1.1.3 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 with its use.
6、 It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and to determine theapplicability of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 1193 Specification for Reagent WaterD 3694 Practices for Preparation of Sa
7、mple Containers andfor Preservation of Organic ConstituentsD 3856 Guide for Good Laboratory Practices in Laborato-ries Engaged in Sampling and Analysis of WaterD 5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water AnalysisD 5905 Practice for the Preparation of
8、 Substitute Wastewa-terE 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. Terminology3.1 NP represents nonylphenol which is mixed isomers ofbranched p-nonylphenol. Commercial nonylphenol (NP) isproduced by the reaction of phenol with commercial nonene
9、.Commercial nonene is not simply a linear C9H18alpha olefin;it is a complex mixture of predominantly nine-carbon olefins,called propylene trimer, containing no linear isomers. Thissynthesis results in a mixture of various branched nonylphenolisomers rather than a discrete chemical structure. The bra
10、nchednonyl group is positioned predominantly in the para positionon the phenol ring.3.2 OP represents octylphenol. Commercial octylphenol isproduced by the reaction of phenol and diisobutylene toproduce predominantly the 4-(1,1,3,3-tetramethylbutyl)phenolisomer.3.3 BPArepresents bisphenolA. Commerci
11、al bisphenolAisproduced by the condensation reaction of phenol and acetoneto produce predominantly the 4,48-isopropylidenediphenol iso-mer.3.4 NP1EO represents branched nonylphenol monoethoxy-late.3.5 NP2EO represents branched nonylphenol diethoxylate.3.6 n-NP and n-NP1EO represent normal straight c
12、hainnonylphenol and nonylphenol ethoxylate. n-NP and n-NP1EOare used in this method as surrogates. They are not producedcommercially and are not expected to be found in environmen-tal waters.1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of
13、 Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved Dec. 15, 2006. Published January 2007.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume
14、information, refer to the standards Document Summary page onthe ASTM website.TABLE 1 MDL and Reporting LimitsAnalyte MDL, (g/L) Reporting Range (g/L)NP 0.9 5.0-80.0NP1EO 1.2 10.0-160.0NP2EO 1.8 20.0-320.0OP 0.2 1.0-16.0BPA 0.3 1.0-16.01Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700
15、, West Conshohocken, PA 19428-2959, United States.3.7 Environmental water shall refer to water tested usingthis method. See Section 5.4. Summary of Test Method4.1 For NP, NP1EO, NP2EO, BPA, and OP analysis, con-tinuous liquid-liquid extraction technique is used for watersamples.4.2 Continuous Liquid
16、-Liquid Extraction TechniqueA1-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
17、.3 The target compounds 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 f
18、inal report issued for 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, octylphenol, and bisphenol A have beenshown to have toxic effects in aquatic organisms. The source ofno
19、nylphenol and octylphenol 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 an
20、aerobic conditions, nonylphenol. Nonylphenolwill also biodegrade, but may be released into environmentalwaters directly at trace levels. This method has been investi-gated for use with surface water and waste treatment effluentsamples and is applicable to these matrices. It has not beeninvestigated
21、for use with salt water or solid sample matrices.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 dem
22、onstrated to befree from interferences by analyzing laboratory reagent blanksunder the same conditions as the samples.6.2 All glassware is scrupulously cleaned. All glassware iswashed in hot water with detergent such as powderedAlconox,Deto-Jet, Luminox, or Citrojet, rinsed in hot water and rinsedwi
23、th distilled water. 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 residuepurit
24、y or higher to 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 S
25、ystem:7.1.1 Gas 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 co
26、l-umns.7.1.2 Analytical ColumnAn analytical column (DB-5MS30-m 3 0.25 mm i.d; film thickness0.25 m or equivalent;(5 %-phenyl)-methylpolysiloxane) suitable for the analysis oftarget alkylphenols.37.1.3 Mass Spectrometer (MS) SystemAn MS systemcapable of scanning 45 to 500 amu every2sorless, using70 e
27、V in the electron 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 chemical
28、s shall beused in 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.4Other reagent grades may be used provided it is first ascer-tained that they are of sufficiently high
29、purity to permit 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 D 1193. It must be demonstrated thatthis water does not contain contaminants at
30、 concentrationssufficient to interfere with the analysis.8.3 Carrier GasesResearch grade nitrogen or helium ofhighest purity are used as carrier gases.8.4 Methylene Chloride, chromatography grade.8.5 Methanol, purge and trap grade.8.6 Branched Nonylphenol Monoethoxylate (NP1EO),available as a high p
31、urity custom standard.3The 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:FIG. 4 Extracted Ion Chromatograms, Nonylphenol Monoethoxylate (NP1EO)FIG. 5 Extracted Ion Chromatograms, Nonylphenol Diethoxyl
32、ate (NP2EO)D7065069Ax= area of 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
33、 (L),Vt= volume of the concentrated extract in microliters(L), andDf= dilution factor.15.1.1 The dilution factor for analysis of samples forsemi-volatiles by this method is defined as follows:Df= L most concentrated extract used to make dilution + Lclean solvent/L most concentrated extract used to m
34、akedilution.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 D 5905 was determined by US EPARegion 5 Chicago Regional Laboratory. Substitute wastewaterwas prepared in acco
35、rdance with Practice D 5905. TritonX-100 was not used in the formulation because it containsalkylphenol ethoxylates. The liquid/liquid extraction techniquedescribed in Section 13 was used. Tables 7-10 contain thespiking levels and recoveries for all surrogates and targetcompounds. N-NP2EO is not a r
36、equired surrogate but includedfor added informational purposes.16.2 Separatory funnel extraction (SFE) using reagent waterby US EPA Region 5 Chicago Regional Laboratory. Theseparatory funnel extraction technique described in Section 13was used. Table 11 contains the spike level and percentrecoveries
37、 for all surrogates and target compounds.16.3 Multi-Laboratory ValidationThis test method hasbeen tested by eight laboratories using reagent water andPractice D 5905 substitute wastewater. The substitute waste-water did not contain Triton X-100 since it contains the analyteof interest. The substitut
38、e wastewaters were spiked with thetarget compounds at six concentration levels, as Youden pairs.The multi-laboratory data for the substitute wastewater is inTable 12 and Table 13.17. Keywords17.1 bisphenol A; continuous liquid-liquid extraction.; di-ethoxylate; ethoxylate; gas chromatography; mass s
39、pectrom-etry; monoethoxylate; Nonylphenol; octylphenol; waterTABLE 7 Single-laboratory CLLE Data5to20g/LSample NP Spike(PPB)NPRecovered(PPB)NP% Recoveryn-NP Spike(PPB)n-NPRecovered(PPB)n-NP% RecoveryMethod Blank 8 7.81 98Method Blank 8 7.36 92P or through the ASTM website(www.astm.org).TABLE X1.1 Am
40、ount of Compound (ng) in Each Isomer Group Based on Abundances in StandardsCompounds PercentAVG1 Std.Dev.ngGroupLevel 1ngGroupLevel 2ngGroupLevel 3ngGroupLevel 4NgGroupLevel 5NP 1 5.29 0.36 0.53 1.06 2.12 4.24 8.48NP 2 19.35 0.88 1.94 3.87 7.74 15.48 30.96NP 3 8.17 0.05 0.82 1.63 3.27 6.54 13.08NP 4
41、 4.79 0.17 0.48 0.96 1.92 3.84 7.68NP 5 14.29 0.20 1.43 2.86 5.72 11.44 22.88NP 6 4.88 0.15 0.49 0.98 1.95 3.90 7.80NP 7 5.39 0.05 0.54 1.08 2.16 4.32 8.64NP 8 5.02 0.14 0.50 1.00 2.01 4.02 8.04NP 9 2.24 0.09 0.22 0.45 0.90 1.80 3.60NP 10 19.02 0.50 1.90 3.80 7.61 15.22 30.44NP 11 7.74 0.28 0.77 1.5
42、5 3.10 6.20 12.40NP 12 3.82 0.08 0.38 0.76 1.53 3.06 6.12ng Total 10.00 20.00 40.00 80.00 160.00NP1EO 1 1.98 0.39 0.40 0.79 1.58 3.16 6.32NP1EO 2 15.01 1.54 3.00 6.00 12.01 24.02 48.04NP1EO 3 7.59 0.81 1.52 3.04 6.07 12.14 24.28NP1EO 4 6.86 0.31 1.37 2.74 5.49 10.98 21.96NP1EO 5 12.45 0.11 2.49 4.98
43、 9.96 19.92 39.84NP1EO 6 6.48 0.13 1.30 2.59 5.18 10.36 20.72NP1EO 7 8.25 0.35 1.65 3.30 6.60 13.20 26.40NP1EO 8 4.43 0.23 0.89 1.77 3.54 7.08 14.16NP1EO 9 25.34 0.84 5.07 10.14 20.27 40.54 81.08NP1EO 10 11.59 1.83 2.32 9.27 9.27 18.54 37.08ng Total 20.00 40.00 80.00 160.00 320.00NP2EO 1 2.53 0.65 1
44、.01 2.02 4.05 8.10 16.20NP2EO 2 15.86 2.26 6.34 12.69 25.38 76.0 152.0NP2EO 3 7.77 0.37 3.11 6.22 12.43 24.86 49.72NP2EO 4 13.56 0.17 5.42 10.85 21.70 43.40 86.80NP2EO 5 11.86 0.98 4.74 9.49 18.98 37.96 75.92NP2EO 6 6.07 0.52 2.43 4.86 9.71 19.42 38.84NP2EO 7 7.94 0.37 3.18 6.35 12.70 25.40 50.80NP2EO 8 5.10 0.19 2.04 4.08 8.16 16.32 32.64NP2EO 9 20.13 1.17 8.05 16.10 32.21 64.42 128.84NP2EO 10 9.19 0.58 3.68 7.35 14.70 29.40 58.80ng Total 40.00 80.00 160.00 320.00 640.00D70650613
