1、Designation: D7742 17Standard Practice forDetermination of Nonylphenol Polyethoxylates (NPnEO, 3 #n # 18) and Octylphenol Polyethoxylates (OPnEO, 2 # n #12) in Water by Single Reaction Monitoring (SRM) LiquidChromatography/ Tandem Mass Spectrometry (LC/MS/MS)1This standard is issued under the fixed
2、designation D7742; the number immediately 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 revis
3、ion or reapproval.1. Scope1.1 This practice covers the determination of nonylphenolpolyethoxylates (NPnEO, 3 n 18) and octylphenol poly-ethoxylates (OPnEO, 2 n 12) in water by Single ReactionMonitoring (SRM) Liquid Chromatography/ Tandem MassSpectrometry (LC/MS/MS) using direct injection liquid chro
4、-matography (LC) and detected with tandem mass spectrometry(MS/MS) detection. This is a screening practice with qualifiedquantitative data to check for the presence of longer chainethoxylates in a water sample.1.1.1 All data are qualified because neat standards of eachalkylphenol ethoxylate (APEO) a
5、re not available and thesynthesis and characterization of these neat standards would bevery expensive. The Igepal2brand standards, which contain amixture of various chain lengths of the alkylphenol ethoxylates(APEOs), were used. The mixture was characterized in-houseassuming the instrument response
6、at an optimum electrosprayionization cone and collision voltage for each APEO was thesame. This assumption, which may not be accurate, is used todetermine qualified amounts of each ethoxylate in the stan-dards. The n-Nonylphenol diethoxylate (n-NP2EO) surrogatewas available as a neat characterized s
7、tandard, therefore, thisconcentration and recovery data was not estimated.APEOs arenot regulated by the EPA, but nonylphenol, a breakdownproduct of NPnEOs, is regulated for fresh and saltwaterdischargers. A request by a sewage treatment plant (STP) wasmade to make this practice available throughASTM
8、 in order toscreen for the influent or effluent from sources of APEOscoming into the STP. The interest lies in stopping the source ofthe longer chainAPEOs from entering the STPin order to meeteffluent guidelines. Based upon the above, this is a practicerather than a test method. A comparison between
9、 samples ispossible using this practice to determine which has a higherconcentration of APEOs.1.2 UnitsThe values stated in SI units are to be regardedas standard. No other units of measurement are included in thispractice.1.3 The estimated screening range shown in Table 1 wascalculated from the con
10、centration of the Level 1 and 7calibration standards shown in Table 4. These numbers arequalified, as explained in Section 1, and must be reported assuch. Figs. 1-5 show the SRM chromatograms of each analyteat the Level 1 concentration with the signal to noise (S/N) ratio.This is a screening practic
11、e and method detection limits are notgiven. The S/N ratio for each analyte at the Level 1 concen-tration must be at least 5:1 for adequate sensitivity. If theinstrument can not meet the criteria, the screening limit mustbe raised to an acceptable level.1.4 This standard does not purport to address a
12、ll of thesafety concerns, if any, associated with 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
13、in accor-dance with internationally recognized principles 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 Documents
14、2.1 ASTM Standards:3D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on Water1This practice is under the jurisdiction of ASTM Committee D19 on Water andis the direct responsibilit
15、y of Subcommittee D19.06 on Methods for Analysis forOrganic Substances in Water.Current edition approved Dec. 15, 2017. Published January 2018. Originallyapproved in 2011. Last previous edition approved in 2011 as D7742 11. DOI:10.1520/D7742-17.2Igepal is a trademark of Rhodia Operations, Aubervilli
16、ers, CA.3For 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.Copyright ASTM International, 100 Barr Harbor Drive,
17、PO Box C700, 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
18、 by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1D3856 Guide for Management Systems in LaboratoriesEngaged in Analysis of WaterD3694 Practices for Preparation of Sample Containers andfor Preservation of Organic ConstituentsD5847 Practice for Writing Quality Control Speci
19、ficationsfor Standard Test Methods for Water AnalysisE2554 Practice for Estimating and Monitoring the Uncer-tainty of Test Results of a Test Method Using ControlChart Techniques2.2 Other Standard:4EPA Publication SW-846 Test Methods for Evaluating SolidWaste, Physical/Chemical Methods3. Terminology3
20、.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 alkylphenol ethoxylates, nin this practice, nonylphe-nol polyethoxylates (NPnEO, 3 n 18) and octylphenolpolyethoxylates (OPnEO, 2 n 12) collectively
21、.3.2.2 screening limit, SL, nthe estimated concentration ofthe lowest-level calibration standard used for quantificationaccounting for the sample dilution.3.3 Abbreviations:3.3.1 mMmillimolar,1103moles/L3.3.2 NDnon-detect3.3.3 pptparts per trillion, ng/L4. Summary of Practice4.1 This is a performanc
22、e-based practice and modificationsare allowed to improve performance.4.2 For APEOs analysis, samples are shipped to the labbetween 0C and 6C containing 1 % formaldehyde andanalyzed within 7 days of collection. In the lab, an aliquot ofthe sample is filtered, spiked with surrogate, and analyzeddirect
23、ly by LC/MS/MS.4.2.1 Field samples from sewage systems propose a chal-lenging analysis. Since this is a screening technique to deter-mine if APEOs are present, a 1025 mL aliquot of the sampleis filtered through a PVDF syringe driven filter unit beforespiking with surrogate. It was demonstrated that
24、similar recov-eries of the APEOs are achieved filtered and unfiltered usingPVDF filters. Filtering using PTFE filters produced muchlower recoveries. This practice does not account for theAPEOsadhered to particulates or the sample bottle.4.3 Nonylphenol polyethoxylates (NPnEO, 3 n 18),octylphenol pol
25、yethoxylates (OPnEO, 2 n 12), andn-nonylphenol diethoxylate (n-NP2EO, surrogate) are identi-fied by retention time and one SRM transition. The targetanalytes and surrogates are quantitated using the SRM transi-tion by external calibration. The final report issued for eachsample lists their qualified
26、 concentration and the surrogaterecovery.5. Significance and Use5.1 This practice has been developed in support of the U.S.EPA Office of Water, Office of Science and Technology by theChicago Regional Laboratory (CRL).5.2 Nonylphenol (NP) and Octylphenol (OP) have beenshown to have toxic effects in a
27、quatic organisms. The promi-nent source of NP and OP is from common commercial4Available from National Technical Information Service (NTIS), 5301 ShawneeRd., Alexandria, VA 22312, http:/www.ntis.gov.TABLE 1 Estimated Screening RangeAnalyte Estimated ScreeningRange (g/L)Nonylphenoltriethoxylate (NP3E
28、O)0.7311.6Nonylphenoltetraethoxylate (NP4EO)1.118.3Nonylphenolpentaethoxylate (NP5EO)1.422.1Nonylphenolhexaethoxylate (NP6EO)1.828.2Nonylphenolheptaethoxylate (NP7EO)1.930.1Nonylphenoloctaethoxylate (NP8EO)1.829.2Nonylphenolnonaethoxylate (NP9EO)1.626.3Nonylphenoldecaethoxylate (NP10EO)1.524.1Nonylp
29、henolundecaethoxylate (NP11EO)1.321.3Nonylphenoldodecaethoxylate (NP12EO)1.015.7Nonylphenoltridecaethoxylate (NP13EO)0.6410.3Nonylphenoltetradecaethoxylate (NP14EO)0.416.5Nonylphenolpendecaethoxylate (NP15EO)0.213.4Nonylphenolhexadecaethoxylate (NP16EO)0.111.7Nonylphenolheptadecaethoxylate (NP17EO)0
30、.050.80Nonylphenoloctodecaethoxylate (NP18EO)0.0230.4Total NPnEO 16250Octylphenoldiethoxylate (OP2EO)0.142.3Octylphenoltriethoxylate (OP3EO)1.422.2Octylphenoltetraethoxylate (OP4EO)2.235.2Octylphenolpentaethoxylate (OP5EO)2.945.8Octylphenolhexaethoxylate (OP6EO)2.641.9Octylphenolheptaethoxylate (OP7
31、EO)2.540.4Octylphenoloctaethoxylate (OP8EO)1.828.8Octylphenolnonaethoxylate (OP9EO)1.117.6Octylphenoldecaethoxylate (OP10EO)0.629.9Octylphenolundecaethoxylate (OP11EO)0.264.2Octylphenoldodecaethoxylate (OP12EO)0.111.8Total OPnEO 16250n-Nonylphenoldiethoxylate (n-NP2EO)15.6250 (Not Estimated)D7742 17
32、2surfactants which are longer chain APEOs. The most widelyused surfactant is nonylphenol polyethoxylate (NPnEO) whichhas an average ethoxylate chain length of nine. TheAPEOs arereadily biodegraded to form NP1EO, NP2EO, nonylphenolcarboxylate (NPEC) and NP. NP will also biodegrade, but maybe released
33、 into environmental waters directly at trace levels.This practice screens for the longer chain APEOs which mayenter the STPat elevated levels and may cause a STPto violateits permitted discharge concentration of nonylphenol.6. Interferences6.1 Practice interferences may be caused by contaminants ins
34、olvents, reagents, glassware and other apparatus producingdiscrete artifacts or elevated baselines. All of these materialsare routinely demonstrated to be free from interferences byanalyzing laboratory reagent blanks under the same conditionsas the samples.6.2 All glassware is washed in hot water wi
35、th detergent suchas powdered Alconox, Det-o-Jet, Luminox, or Citrajet,5rinsedin hot water, and rinsed with distilled water. The glassware isthen dried and heated in an oven at 250C for 15 to 30 minutes.All glassware is subsequently cleaned with acetone and metha-nol. Detergents containing alkylpheno
36、lic compounds must notbe 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 can vary considerably from sampl
37、e source tosample source, depending on variations of the sample matrix.7. Apparatus7.1 LC/MS/MS System:7.1.1 Liquid Chromatography SystemA complete LC sys-tem is needed in order to analyze samples.6Any system that iscapable of performing at the flows, pressures, controlledtemperatures, sample volume
38、s, and requirements of the stan-dard may be used.7.1.2 Analytical ColumnWaters Atlantis dC18,72.1 150mm, 3 m particle size was used to develop this practice. Any5Alconox, Det-o-Jet, Luminox, and Citrajet are trademarks of Alconox, Inc.,White Plains, NY.6Waters ACQUITY H-Class Ultra Performance Liqui
39、d Chromatography(UPLC) System, a trademark of the Waters Corporation, Milford, MA, was used todevelop this practice. All parameters in this practice are based on this system andmay vary depending on your instrument.7Waters Atlantis dC18 is a trademark of the Waters Corporation, Milford, MA.FIG. 1 SR
40、M Chromatograms NP3EO-NP8EOD7742 173column that achieves adequate resolution may be used. Theretention times and order of elution may change depending onthe column used and need to be monitored.7.1.3 Tandem Mass Spectrometer SystemA MS/MS sys-tem capable of MRM analysis.8Any system that is capable o
41、fperforming at the requirements in this practice may be used.7.2 Filtration Device:7.2.1 Hypodermic syringeAlock-tip glass syringe capableof holding a Millex HV Syringe Driven Filter Unit PVDF 0.45m,9,10or similar, may be used.7.2.1.1 A25mLlock-tip glass syringe size is recommendedfor this practice.
42、7.2.2 FilterMillex HV Syringe Driven Filter Unit PVDF0.45 m was used to develop this practice, any similar filtermay be used.8. Reagents and Materials8.1 Purity of ReagentsHigh Performance Liquid Chroma-tography (HPLC) pesticide residue analysis and spectropho-tometry grade chemicals shall be used i
43、n all tests. Unlessindicated otherwise, it is intended that all reagents shallconform to the specifications of the Committee on AnalyticalReagents of the American Chemical Society.11Other reagentgrades may be used provided it is first ascertained that they areof sufficiently high purity to permit th
44、eir use without affectingthe accuracy of the measurement.8.2 Purity of WaterUnless indicated, references to watershall be understood to mean reagent water conforming to TypeI of Specification D1193. It must be demonstrated that thiswater does not contain contaminants at concentrations suffi-cient to
45、 interfere with the analysis.8.3 GasesUltrapure nitrogen and argon.8.4 Acetonitrile (CAS # 75-05-8).8.5 Methanol (CAS # 67-56-1).8AWaters Quattro Micro tandem quadrupole mass spectrometer, a trademark ofthe Waters Corporation, Milford, MA., was used to develop this practice. Allparameters in this pr
46、actice are based on this system and may vary depending on yourinstrument.9The sole source of supply of the Millex HV Syringe Driven Filter Unit PVDF0.45 m known to the committee at this time is Millipore Corporation, Catalog #SLHV033NS. If you are aware of alternative suppliers, please provide thisi
47、nformation to ASTM International Headquarters. Your comments will receivecareful consideration at a meeting of the responsible technical committee,1whichyou may attend.10Millex is a trademark of Merck KGAA, Darmstadt, Germany.11Reagent Chemicals, American Chemical Society Specifications, AmericanChe
48、mical 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 the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Roc
49、kville,MD.FIG. 2 SRM Chromatograms NP9EO-NP14EOD7742 1748.6 2-Propanol (CAS # 67-63-0).8.7 Acetone (CAS # 67-64-1).8.8 Nonylphenol pentaethoxylate mixture (several NPnEOisomer groups with an average of NP5EO, Igepal CO-520).8.9 Nonylphenol nonaethoxylate mixture (several NPnEOisomer groups with an average of NP9EO, Igepal CO-630).8.10 Octylphenol diethoxylate mixture (several OPnEO iso-mer groups with an average of OP2EO, Igepal CA-210).8.11 Octylphenol pentaethoxylate mixture (several OPnEOisomer
