1、Designation: D7065 11Standard 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 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) reportin
5、g 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. It
6、 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:2D1193 Specification for Reagent WaterD3694 Practices for Preparation of Sample
7、Containers andfor Preservation of Organic ConstituentsD3856 Guide for Good Laboratory Practices in Laborato-ries Engaged in Sampling and Analysis of WaterD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water AnalysisD5905 Practice for the Preparation of Substit
8、ute Wastewa-terE691 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.Commerci
9、al 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 branchednony
10、l 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. Commercial bisphe
11、nolAisproduced 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 chainnonyl
12、phenol 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 Subcommi
13、ttee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved June 15, 2011. Published July 2011. Originallypublished 2006. Last previous version approved 2006 as D706506.DOI: 10.1520/D7065-11.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontac
14、t ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume 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 1.0-1
15、6.0BPA 0.3 1.0-16.01Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, 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-tinuo
16、us liquid-liquid extraction technique is used for watersamples.4.2 Continuous Liquid-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 th
17、enanalyzed by GC/MS operated in the selected ion monitoring(SIM) or full scan mode.4.3 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 co
18、mpounds utilizingthe internal standards acenaphthene-d10, and phenanthrene-d10.The final 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 bi
19、sphenol A have beenshown to have toxic effects in aquatic organisms. The source ofnonylphenol 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 rea
20、dily biodegradedto form NP1EO and NP2EO, nonylphenol carboxylate (NPEC)and, under anaerobic 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 treatme
21、nt effluentsamples and is applicable to these matrices. It has not beeninvestigated 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 b
22、aseline in the selected ion currentprofiles.All of these materials are routinely demonstrated 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
23、 as powderedAlconox,Deto-Jet, Luminox, or Citrojet, rinsed in hot water and rinsedwith 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 compound
24、s must not be used.6.3 All reagents and solvents should be of pesticide residuepurity 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 t
25、osample source, depending on variations of the sample matrix.7. Apparatus7.1 GC/MS System: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
26、. The injection port mustbe designed for split/splitless when using the capillary col-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 Spectromet
27、er (MS) SystemAn MS systemcapable of scanning 45 to 500 amu every2sorless, using70 eV 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 Evap
28、oration Device.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals 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 grad
29、es may be used provided it is first ascer-tained that they are of sufficiently high 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 specifica
30、tion D1193. It must be demonstrated thatthis water does not contain contaminants at 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 a
31、nd trap grade.8.6 Branched Nonylphenol Monoethoxylate (NP1EO),available as a high purity 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, Nonylphe
32、nol Monoethoxylate (NP1EO)FIG. 5 Extracted Ion Chromatograms, Nonylphenol Diethoxylate (NP2EO)D7065 119Ax= 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
33、of water extracted in milliliters (mL),Vi= volume of extract injected in microliters (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
34、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 US
35、 EPARegion 5 Chicago Regional Laboratory. Substitute wastewaterwas prepared in accordance with Practice D5905. Triton X-100was not used in the formulation because it contains alkylphenolethoxylates. The liquid/liquid extraction technique described inSection 13 was used. Tables 7-10 contain the spiki
36、ng levels andrecoveries for all surrogates and target compounds. N-NP2EOis not a required surrogate but included for added informationalpurposes.16.2 Separatory funnel extraction (SFE) using reagent waterby US EPA Region 5 Chicago Regional Laboratory. Theseparatory funnel extraction technique descri
37、bed in Section 13was used. Table 11 contains the spike level and percentrecoveries for all surrogates and target compounds.16.3 Multi-Laboratory ValidationThis test method hasbeen tested by eight laboratories using reagent water andPractice D5905 substitute wastewater. The substitute wastewa-ter did
38、 not contain Triton X-100 since it contains the analyte ofinterest. The substitute wastewaters were spiked with the targetcompounds at six concentration levels, as Youden pairs. Themulti-laboratory data for the substitute wastewater is in Table12 and Table 13.17. Keywords17.1 bisphenol A; continuous
39、 liquid-liquid extraction.; di-ethoxylate; ethoxylate; gas chromatography; mass spectrom-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
40、98Method Blank 8 7.36 92P or through the ASTM website(www.astm.org). Permission rights to photocopy the standard may also be secured from the ASTM website (www.astm.org/COPYRIGHT/).TABLE X1.1 Amount of Compound (ng) in Each Isomer Group Based on Abundances in StandardsCompounds PercentAVG1 Std.Dev.n
41、gGroupLevel 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 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
42、 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 1.55 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.
43、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 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 26.40N
44、P1EO 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 4.64 9.27 18.54 37.08ng Total 20.00 40.00 80.00 160.00 320.00NP2EO 1 2.53 0.65 1.01 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
45、.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 80.00 160.00 320.00 640.00D7065 1113
