ASTM D7742-17

Standard Practice for Determination of Nonylphenol Polyethoxylates (NPnEO, 3 ≤ n ≤ 18) and Octylphenol Polyethoxylates (OPnEO, 2 ≤ n ≤ 12) in Water by Single Reaction Monitoring (SRM) Liquid Chromatography/ Tandem Mass Spectrometry (LC/MS/MS)

SIGNIFICANCE AND USE
5.1 This practice has been developed in support of the U.S. EPA Office of Water, Office of Science and Technology by the Chicago Regional Laboratory (CRL).  
5.2 Nonylphenol (NP) and Octylphenol (OP) have been shown to have toxic effects in aquatic organisms. The prominent source of NP and OP is from common commercial surfactants which are longer chain APEOs. The most widely used surfactant is nonylphenol polyethoxylate (NPnEO) which has an average ethoxylate chain length of nine. The APEOs are readily biodegraded to form NP1EO, NP2EO, nonylphenol carboxylate (NPEC) and NP. NP will also biodegrade, but may be released into environmental waters directly at trace levels. This practice screens for the longer chain APEOs which may enter the STP at elevated levels and may cause a STP to violate its permitted discharge concentration of nonylphenol.
SCOPE
1.1 This practice covers the determination of nonylphenol polyethoxylates (NPnEO, 3 ≤ n ≤ 18) and octylphenol polyethoxylates (OPnEO, 2 ≤ n ≤ 12) in water by Single Reaction Monitoring (SRM) Liquid Chromatography/ Tandem Mass Spectrometry (LC/MS/MS) using direct injection liquid chromatography (LC) and detected with tandem mass spectrometry (MS/MS) detection. This is a screening practice with qualified quantitative data to check for the presence of longer chain ethoxylates in a water sample.  
1.1.1 All data are qualified because neat standards of each alkylphenol ethoxylate (APEO) are not available and the synthesis and characterization of these neat standards would be very expensive. The Igepal2 brand standards, which contain a mixture of various chain lengths of the alkylphenol ethoxylates (APEOs), were used. The mixture was characterized in-house assuming the instrument response at an optimum electrospray ionization cone and collision voltage for each APEO was the same. This assumption, which may not be accurate, is used to determine qualified amounts of each ethoxylate in the standards. The n-Nonylphenol diethoxylate (n-NP2EO) surrogate was available as a neat characterized standard, therefore, this concentration and recovery data was not estimated. APEOs are not regulated by the EPA, but nonylphenol, a breakdown product of NPnEOs, is regulated for fresh and saltwater dischargers. A request by a sewage treatment plant (STP) was made to make this practice available through ASTM in order to screen for the influent or effluent from sources of APEOs coming into the STP. The interest lies in stopping the source of the longer chain APEOs from entering the STP in order to meet effluent guidelines. Based upon the above, this is a practice rather than a test method. A comparison between samples is possible using this practice to determine which has a higher concentration of APEOs.  
1.2 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this practice.  
1.3 The estimated screening range shown in Table 1 was calculated from the concentration of the Level 1 and 7 calibration standards shown in Table 4. These numbers are qualified, as explained in Section 1, and must be reported as such. Figs. 1-5 show the SRM chromatograms of each analyte at the Level 1 concentration with the signal to noise (S/N) ratio. This is a screening practice and method detection limits are not given. The S/N ratio for each analyte at the Level 1 concentration must be at least 5:1 for adequate sensitivity. If the instrument can not meet the criteria, the screening limit must be raised to an acceptable level.  
FIG. 1 SRM Chromatograms NP3EO-NP8EO  
FIG. 2 SRM Chromatograms NP9EO-NP14EO  
FIG. 3 SRM Chromatograms NP15EO-NP18EO and n-NP2EO  
FIG. 4 SRM Chromatograms OP2EO-OP7EO  
FIG. 5 SRM Chromatograms OP8EO-OP12EO  
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety,...

General Information

• Status: Published
• Publication Date: 14-Dec-2017
• ICS: 71.100.40 - Surface active agents
• Technical Committee: D19 - Water
• Drafting Committee: D19.06 - Methods for Analysis for Organic Substances in Water

Relations

• Refers: ASTM E2554-18 - Standard Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques
• Effective Date: 01-Apr-2018
• Refers: ASTM E2554-18e1 - Standard Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques
• Effective Date: 01-Apr-2018

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D7742 − 17
Standard Practice for
Determination of Nonylphenol Polyethoxylates (NPnEO, 3#
n# 18) and Octylphenol Polyethoxylates (OPnEO, 2# n#
12) in Water by Single Reaction Monitoring (SRM) Liquid
1
Chromatography/ Tandem Mass Spectrometry (LC/MS/MS)
This standard is issued under the fixed designation D7742; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope possible using this practice to determine which has a higher
concentration of APEOs.
1.1 This practice covers the determination of nonylphenol
polyethoxylates (NPnEO, 3 ≤ n ≤ 18) and octylphenol poly- 1.2 Units—The values stated in SI units are to be regarded
ethoxylates (OPnEO, 2 ≤ n ≤ 12) in water by Single Reaction asstandard.Nootherunitsofmeasurementareincludedinthis
Monitoring (SRM) Liquid Chromatography/ Tandem Mass practice.
Spectrometry (LC/MS/MS) using direct injection liquid chro-
1.3 The estimated screening range shown in Table 1 was
matography(LC)anddetectedwithtandemmassspectrometry
calculated from the concentration of the Level 1 and 7
(MS/MS) detection. This is a screening practice with qualified
calibration standards shown in Table 4. These numbers are
quantitative data to check for the presence of longer chain
qualified, as explained in Section 1, and must be reported as
ethoxylates in a water sample.
such. Figs. 1-5 show the SRM chromatograms of each analyte
1.1.1 All data are qualified because neat standards of each
attheLevel1concentrationwiththesignaltonoise(S/N)ratio.
alkylphenol ethoxylate (APEO) are not available and the
Thisisascreeningpracticeandmethoddetectionlimitsarenot
synthesisandcharacterizationoftheseneatstandardswouldbe
given. The S/N ratio for each analyte at the Level 1 concen-
2
very expensive. The Igepal brand standards, which contain a
tration must be at least 5:1 for adequate sensitivity. If the
mixtureofvariouschainlengthsofthealkylphenolethoxylates
instrument can not meet the criteria, the screening limit must
(APEOs), were used. The mixture was characterized in-house
be raised to an acceptable level.
assuming the instrument response at an optimum electrospray
1.4 This standard does not purport to address all of the
ionization cone and collision voltage for each APEO was the
safety concerns, if any, associated with its use. It is the
same. This assumption, which may not be accurate, is used to
responsibility of the user of this standard to establish appro-
determine qualified amounts of each ethoxylate in the stan-
priate safety, health, and environmental practices and deter-
dards. The n-Nonylphenol diethoxylate (n-NP2EO) surrogate
mine the applicability of regulatory limitations prior to use.
was available as a neat characterized standard, therefore, this
1.5 This international standard was developed in accor-
concentration and recoverydatawasnotestimated.APEOsare
dance with internationally recognized principles on standard-
not regulated by the EPA, but nonylphenol, a breakdown
ization established in the Decision on Principles for the
product of NPnEOs, is regulated for fresh and saltwater
Development of International Standards, Guides and Recom-
dischargers.Arequest by a sewage treatment plant (STP) was
mendations issued by the World Trade Organization Technical
madetomakethispracticeavailablethroughASTMinorderto
Barriers to Trade (TBT) Committee.
screen for the influent or effluent from sources of APEOs
comingintotheSTP.Theinterestliesinstoppingthesourceof
2. Referenced Documents
thelongerchainAPEOsfromenteringtheSTPinordertomeet
3
2.1 ASTM Standards:
effluent guidelines. Based upon the above, this is a practice
D1129Terminology Relating to Water
rather than a test method. A comparison between samples is
D1193Specification for Reagent Water
D2777Practice for Determination of Precision and Bias of
Applicable Test Methods of Committee D19 on Water
1
This practice is under the jurisdiction ofASTM Committee D19 on Water and
is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
3
Current edition approved Dec. 15, 2017. Published January 2018. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 2011. Last previous edition approved in 2011 as D7742 – 11. DOI: contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
10.1520/D7742-17. Standards volume information, refer to the standard’s Document Summary page on
2
Igepal is a tr
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D7742 − 11 D7742 − 17
Standard Practice for
Determination of Nonylphenol Polyethoxylates (NPnEO, 3 #
n # 18) and Octylphenol Polyethoxylates (OPnEO, 2 # n #
12) in Water by Single Reaction Monitoring (SRM) Liquid
1
Chromatography/ Tandem Mass Spectrometry (LC/MS/MS)
This standard is issued under the fixed designation D7742; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1 This procedurepractice covers the determination of nonylphenol polyethoxylates (NPnEO, 3 ≤ n ≤ 18) and octylphenol
polyethoxylates (OPnEO, 2 ≤ n ≤ 12) in water by Single Reaction Monitoring (SRM) Liquid Chromatography/ Tandem Mass
Spectrometry (LC/MS/MS) using direct injection liquid chromatography (LC) and detected with tandem mass spectrometry
(MS/MS) detection. This is a screening practice with qualified quantitative data to check for the presence of longer chain
ethoxylates in a water sample.
1.1.1 All data are qualified because neat standards of each alkylphenol ethoxylate (APEO) are not available and the synthesis
2
and characterization of these neat standards would be very expensive. The Igepal®Igepal Brandbrand standards, which contain
a mixture of various chain lengths of the alkylphenol ethoxylates (APEOs), were used. The mixture was characterized in-house
assuming the instrument response at an optimum electrospray ionization cone and collision voltage for each APEO was the same.
This assumption, which may not be accurate, is used to determine qualified amounts of each ethoxylate in the standards. The
n-Nonylphenol diethoxylate (n- NP2EO) (n-NP2EO) surrogate was available as a neat characterized standard, therefore, this
concentration and recovery data was not estimated. APEOs are not regulated by the EPA, but nonylphenol, a breakdown product
of NPnEOs, is regulated for fresh and saltwater dischargers. A request by a sewage treatment plant (STP) was made to make this
practice available through ASTM in order to screen for the influent or effluent from sources of APEOs coming into the STP. The
interest lies in stopping the source of the longer chain APEOs from entering the STP in order to meet effluent guidelines. Based
upon the above, this is a practice rather than a Standard Method.test method. A comparison between samples is possible using this
practice to determine which has a higher concentration of APEOs.
1.2 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this
practice.
1.3 The estimated screening range shown in Table 1 was calculated from the concentration of the Level 1 and 7 calibration
standards shown in Table 4. These numbers are qualified, as explained in Section 11,, and must be reported as such. Figs. 1-5 show
the SRM chromatograms of each analyte at the Level 1 concentration with the signal to noise (S/N) ratio. This is a screening
practice and method detection limits are not given. The S/N ratio for each analyte at the Level 1 concentration must be at least
5:1 for adequate sensitivity. If the instrument can not meet the criteria, the screening limit must be raised to an acceptable level.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use.
1.5 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
1
This practice is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for Organic
Substances in Water.
Current edition approved June 15, 2011Dec. 15, 2017. Published July 2011January 2018. Originally approved in 2011. Last previous edition approved in 2011 as D7742
– 11. DOI: 10.1520/D7742-11.10.1520/D7742-17.
2
Igepal is a trademark of Rhodia Operations, Aubervilliers, CA.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocke
...