ASTM D7742-11

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Designation: D7742 − 11
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)
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 1.2 Units—The values stated in SI units are to be regarded
asstandard.Nootherunitsofmeasurementareincludedinthis
1.1 Thisprocedurecoversthedeterminationofnonylphenol
practice.
polyethoxylates (NPnEO, 3 ≤ n ≤ 18) and octylphenol poly-
ethoxylates (OPnEO, 2 ≤ n ≤ 12) in water by Single Reaction 1.3 The estimated screening range shown in Table 1 was
Monitoring (SRM) Liquid Chromatography/ Tandem Mass calculated from the concentration of the Level 1 and 7
Spectrometry (LC/MS/MS) using direct injection liquid chro- calibration standards shown in Table 4. These numbers are
matography(LC)anddetectedwithtandemmassspectrometry qualified, as explained in Section 1, and must be reported as
(MS/MS) detection. This is a screening practice with qualified such. Figs. 1-5 show the SRM chromatograms of each analyte
quantitative data to check for the presence of longer chain attheLevel1concentrationwiththesignaltonoise(S/N)ratio.
ethoxylates in a water sample. Thisisascreeningpracticeandmethoddetectionlimitsarenot
1.1.1 All data are qualified because neat standards of each given. The S/N ratio for each analyte at the Level 1 concen-
alkylphenol ethoxylate (APEO) are not available and the tration must be at least 5:1 for adequate sensitivity. If the
synthesisandcharacterizationoftheseneatstandardswouldbe instrument can not meet the criteria, the screening limit must
veryexpensive.TheIgepal®Brandstandards,whichcontaina be raised to an acceptable level.
mixtureofvariouschainlengthsofthealkylphenolethoxylates
1.4 This standard does not purport to address all of the
(APEOs), were used. The mixture was characterized in-house
safety concerns, if any, associated with its use. It is the
assuming the instrument response at an optimum electrospray
responsibility of the user of this standard to establish appro-
ionization cone and collision voltage for each APEO was the
priate safety and health practices and determine the applica-
same. This assumption, which may not be accurate, is used to
bility of regulatory limitations prior to use.
determine qualified amounts of each ethoxylate in the stan-
dards. The n-Nonylphenol diethoxylate (n- NP2EO) surrogate
2. Referenced Documents
was available as a neat characterized standard, therefore, this
2.1 ASTM Standards:
concentrationandrecoverydatawasnotestimated.APEOsare
D1193Specification for Reagent Water
not regulated by the EPA, but nonylphenol, a breakdown
D2777Practice for Determination of Precision and Bias of
product of NPnEOs, is regulated for fresh and saltwater
Applicable Test Methods of Committee D19 on Water
dischargers.Arequest by a sewage treatment plant (STP) was
D3856Guide for Management Systems in Laboratories
madetomakethispracticeavailablethroughASTMinorderto
Engaged in Analysis of Water
screen for the influent or effluent from sources of APEOs
D3694Practices for Preparation of Sample Containers and
comingintotheSTP.Theinterestliesinstoppingthesourceof
for Preservation of Organic Constituents
thelongerchainAPEOsfromenteringtheSTPinordertomeet
D5847Practice for Writing Quality Control Specifications
effluent guidelines. Based upon the above, this is a practice
for Standard Test Methods for Water Analysis
ratherthanaStandardMethod.Acomparisonbetweensamples
E2554Practice for Estimating and Monitoring the Uncer-
is possible using this practice to determine which has a higher
tainty of Test Results of a Test Method Using Control
concentration of APEOs.
Chart Techniques
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 For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Organic Substances in Water. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Current edition approved June 15, 2011. Published July 2011. DOI: 10.1520/ Standards volume information, refer to the standard’s Document Summary page on
D7742-11. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7742 − 11
TABLE 1 Estimated Screening Range
3. Terminology
Analyte Estimated Screening
3.1 Definitions:
Range (µg/L)
3.1.1 Screening Limit, SL, n—theestimatedconcentrationof
Nonylphenol 0.73–11.6
triethoxylate (NP3EO)
the lowest-level calibration standard used for quantification
Nonylphenol 1.1–18.3
accounting for the sample dilution.
tetraethoxylate (NP4EO)
Nonylphenol 1.4–22.1
3.1.2 Alkylphenol Ethoxylates, n—in this practice, nonyl-
pentaethoxylate (NP5EO)
phenol polyethoxylates (NPnEO, 3 ≤ n ≤ 18) and octylphenol
Nonylphenol 1.8–28.2
hexaethoxylate (NP6EO)
polyethoxylates (OPnEO, 2 ≤ n ≤ 12) collectively.
Nonylphenol 1.9–30.1
3.2 Abbreviations:
heptaethoxylate (NP7EO)
Nonylphenol 1.8–29.2
3.2.1 ppt—parts per trillion, ng/L
octaethoxylate (NP8EO)
–3
Nonylphenol 1.6–26.3 3.2.2 mM—millimolar,1×10 moles/L
nonaethoxylate (NP9EO)
3.2.3 ND—non-detect
Nonylphenol 1.5–24.1
decaethoxylate (NP10EO)
Nonylphenol 1.3–21.3
4. Summary of Practice
undecaethoxylate (NP11EO)
Nonylphenol 1.0–15.7
4.1 This is a performance-based practice and modifications
dodecaethoxylate (NP12EO)
are allowed to improve performance.
Nonylphenol 0.64–10.3
tridecaethoxylate (NP13EO)
4.2 For APEOs analysis, samples are shipped to the lab
Nonylphenol 0.41–6.5
tetradecaethoxylate (NP14EO) between 0°C and 6°C containing 1 % formaldehyde and
Nonylphenol 0.21–3.4
analyzed within 7 days of collection. In the lab, an aliquot of
pendecaethoxylate (NP15EO)
the sample is filtered, spiked with surrogate, and analyzed
Nonylphenol 0.11–1.7
hexadecaethoxylate (NP16EO) directly by LC/MS/MS.
Nonylphenol 0.05–0.80
4.2.1 Field samples from sewage systems propose a chal-
heptadecaethoxylate (NP17EO)
lenging analysis. Since this is a screening technique to deter-
Nonylphenol 0.023–0.4
octodecaethoxylate (NP18EO)
mine ifAPEOs are present, a 10–25 mL aliquot of the sample
Total NPnEO 16–250
is filtered through a PVDF syringe driven filter unit before
Octylphenol 0.14–2.3
spiking with surrogate. It was demonstrated that similar recov-
diethoxylate (OP2EO)
Octylphenol 1.4–22.2
eries of the APEOs are achieved filtered and unfiltered using
triethoxylate (OP3EO)
PVDF filters. Filtering using PTFE filters produced much
Octylphenol 2.2–35.2
lowerrecoveries.ThispracticedoesnotaccountfortheAPEOs
tetraethoxylate (OP4EO)
Octylphenol 2.9–45.8
adhered to particulates or the sample bottle.
pentaethoxylate (OP5EO)
Octylphenol 2.6–41.9
4.3 Nonylphenol polyethoxylates (NPnEO, 3 ≤ n ≤ 18),
hexaethoxylate (OP6EO)
octylphenol polyethoxylates (OPnEO, 2 ≤ n ≤ 12), and
Octylphenol 2.5–40.4
n-nonylphenol diethoxylate (n-NP2EO, surrogate) are identi-
heptaethoxylate (OP7EO)
Octylphenol 1.8–28.8
fied by retention time and one SRM transition. The target
octaethoxylate (OP8EO)
analytes and surrogates are quantitated using the SRM transi-
Octylphenol 1.1–17.6
tion by external calibration. The final report issued for each
nonaethoxylate (OP9EO)
Octylphenol 0.62–9.9
sample lists their qualified concentration and the surrogate
decaethoxylate (OP10EO)
recovery.
Octylphenol 0.26–4.2
undecaethoxylate (OP11EO)
Octylphenol 0.11–1.8
5. Significance and Use
dodecaethoxylate (OP12EO)
Total OPnEO 16–250
5.1 This practice has been developed in support of the US
n-Nonylphenol 15.6–250 (Not Estimated)
EPAOffice of Water, Office of Science and Technology by the
diethoxylate (n-NP2EO)
Chicago Regional Laboratory (CRL).
5.2 Nonylphenol (NP) and Octylphenol (OP) have been
2.2 Other Standard:
shown to have toxic effects in aquatic organisms. The promi-
EPA SW-846Test Methods for Evaluating Solid Waste,
nent source of NP and OP is from common commercial
Physical/Chemical Methods
surfactants which are longer chain APEOs. The most widely
used surfactant is nonylphenol polyethoxylate (NPnEO) which
hasanaverageethoxylatechainlengthofnine.TheAPEOsare
readily biodegraded to form NP1EO, NP2EO, nonylphenol
carboxylate(NPEC)andNP.NPwillalsobiodegrade,butmay
be released into environmental waters directly at trace levels.
This practice screens for the longer chain APEOs which may
Available from National Technical Information Service (NTIS), U.S. Depart-
entertheSTPatelevatedlevelsandmaycauseaSTPtoviolate
ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
www.epa.gov/epawaste/hazard/testmethods/index.htm its permitted discharge concentration of nonylphenol.
D7742 − 11
FIG. 1 SRM Chromatograms NP3EO-NP8EO
6. Interferences 7. Apparatus
6.1 Practiceinterferencesmaybecausedbycontaminantsin 7.1 LC/MS/MS System:
solvents, reagents, glassware and other apparatus producing 7.1.1 Liquid Chromatography System—Acomplete LC sys-
discrete artifacts or elevated baselines. All of these materials tem is needed in order to analyze samples. Any system that is
are routinely demonstrated to be free from interferences by capable of performing at the flows, pressures, controlled
analyzing laboratory reagent blanks under the same conditions temperatures, sample volumes, and requirements of the stan-
as the samples. dard may be used.
7.1.2 Analytical Column– Waters—Atlantis™ dC18, 2.1 ×
6.2 Allglasswareiswashedinhotwaterwithdetergentsuch
150 mm, 3 µm particle size was used to develop this practice.
aspowderedAlconox,Deto-Jet,Luminox,orCitrojet,rinsedin
Any column that achieves adequate resolution may be used.
hotwater,andrinsedwithdistilledwater.Theglasswareisthen
Theretentiontimesandorderofelutionmaychangedepending
dried and heated in an oven at 250ºC for 15 to 30 minutes.All
on the column used and need to be monitored.
glassware is subsequently cleaned with acetone and methanol.
7.1.3 Tandem Mass Spectrometer System—A MS/MS sys-
Detergents containing alkylphenolic compounds must not be
tem capable of MRM analysis. Any system that is capable of
used.
performing at the requirements in this practice may be used.
6.3 All reagents and solvents should be of pesticide residue
7.2 Filtration Device:
purity or higher to minimize interference problems.
7.2.1 Hypodermic syringe—A Lock Tip Glass Syringe ca-
6.4 Matrix interferences may be caused by contaminants
pable of holding a Millex® HV Syringe Driven Filter Unit
that are co-extracted from the sample. The extent of matrix
PVDF 0.45 µm or similar may be used.
interferences can vary considerably from sample source to
7.2.1.1 A 25 mL Lock Tip Glass Syringe size is recom-
sample source, depending on variations of the sample matrix.
mended for this practice.
Waters ACQUITY H-Class Ultra Performance Liquid Chromatography
(UPLC®) System was used to develop this test method.All parameters in this test
method are based on this system and may vary depending on your instrument.
AWaters Quattro Micro™ tandem quadrupole mass spectrometer was used to
developthistestmethod.Allparametersinthistestmethodarebasedonthissystem
and may vary depending on your instrument.
D7742 − 11
FIG. 2 SRM Chromatograms NP9EO-NP14EO
7.2.2 Filter—Millex®HVSyringeDrivenFilterUnitPVDF 8.4 Acetonitrile (CAS # 75-05-8)
0.45 µm (Millipore Corporation, Catalog # SLHV033NS) was
8.5 Methanol (CAS # 67-56-1)
used to develop this practice, any similar filter may be used.
8.6 2-Propanol (CAS # 67-63-0)
8. Reagents and Materials
8.7 Acetone (CAS # 67-64-1)
8.1 Purity of Reagents—High Performance Liquid Chroma-
8.8 Nonylphenol pentaethoxylate mixture (several NPnEO
tography (HPLC) pesticide residue analysis and spectropho-
isomer groups with an average of NP5EO, Igepal® CO-520)
tometry grade chemicals shall be used in all tests. Unless
indicated otherwise, it is intended that all reagents shall
8.9 Nonylphenol nonaethoxylate mixture (several NPnEO
conform to the specifications of the Committee on Analytical
isomer groups with an average of NP9EO, Igepal® CO-630)
Reagents of the American Chemical Society. Other reagent
8.10 Octylphenoldiethoxylatemixture(severalOPnEOiso-
gradesmaybeusedprovideditisfirstascertainedthattheyare
mer groups with an average of OP2EO, Igepal® CA-210)
of sufficiently high purity to permit their use without affecting
the accuracy of the measurement.
8.11 Octylphenol pentaethoxylate mixture (several OPnEO
8.2 Purity of Water—Unless indicated, references to water isomer groups with an average of OP5EO, Igepal® CA-520)
shall be understood to mean reagent water conforming toType
8.12 Formaldehyde (CAS # 50-00-0, 37 wt. % solution in
IofSpecification.Itmustbedemonstratedthatthiswaterdoes
water)
not contain contaminants at concentrations sufficient to inter-
fere with the analysis. 8.13 Ammonium Acetate (CAS # 631-61-8)
8.3 Gases—Ultrapure nitrogen and argon
8.14 n-Nonylphenol diethoxylate (n-NP2EO)
9. Hazards
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, D.C. For Suggestions on the testing of reagents not
9.1 Normal laboratory safety applies to this practice. Ana-
listed by the American Chemical Society, see Annual Standards for Laboratory
lysts should wear safety glasses, gloves, and lab coats when
Chemicals,BDHLtd.,Poole,Dorset,U.K.,andtheUnitedStatesPharmacopeiaand
working in the lab.Analysts should review the Material Safety
National Formulators, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. Data Sheets (MSDS) for all reagents used in this practice.
D7742 − 11
FIG. 3 SRM Chromatograms NP15EO-NP18EO and n-NP2EO
10. Sampling 11.2.4 Seal Wash—Solvent: 50 % CH CN /50 % Water;
Time: 5 minutes
10.1 Grab samples may be collected in 40 mL pre-cleaned
amber glass vials with Teflon® lined caps demonstrated to be 11.3 Mass Spectrometer Parameters:
free of interferences, larger sample sizes may be used since a 11.3.1 To acquire the maximum number of data points per
subsample aliquot is only required. All samples are preserved SRM channel while maintaining adequate sensitivity, the tune
with1%concentrationofformaldehyde,shippedbetween0°C parameters must be optimized according to the instrument.
and 6°C, and stored in the laboratory betwee
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