ASTM D7599-09

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D7599 – 09
Standard Test Method for
Determination of Diethanolamine, Triethanolamine,
N-Methyldiethanolamine and N-Ethyldiethanolamine in Water
by Single Reaction Monitoring Liquid Chromatography/
Tandem Mass Spectrometry (LC/MS/MS)
This standard is issued under the fixed designation D7599; 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 requirements in this test method, N-methyldiethanolamine may
have a 25 µg/L reporting limit.
1.1 This procedure covers the determination of dietha-
1.5 This standard does not purport to address all of the
nolamine, triethanolamine, N-methyldiethanolamine and
safety concerns, if any, associated with its use. It is the
N-ethyldiethanolamine (referred to collectively as ethano-
responsibility of the user of this standard to establish appro-
lamines in this test method) in surface water by direct injection
priate safety and health practices and determine the applica-
using liquid chromatography (LC) and detected with tandem
bility of regulatory limitations prior to use.
mass spectrometry (MS/MS). These analytes are qualitatively
and quantitatively determined by this method. This method
2. Referenced Documents
adheres to single reaction monitoring (SRM) mass spectrom-
2.1 ASTM Standards:
etry.
D1129 Terminology Relating to Water
1.2 This test method has been developed in support of the
D1193 Specification for Reagent Water
National Homeland Security Research Center, US EPA by
D2777 Practice for Determination of Precision and Bias of
Region 5 Chicago Regional Laboratory.
Applicable Test Methods of Committee D19 on Water
1.3 The values stated in SI units are to be regarded as
D3856 Guide for Good Laboratory Practices in Laborato-
standard. No other units of measurement are included in this
ries Engaged in Sampling and Analysis of Water
standard.
D3694 Practices for Preparation of Sample Containers and
1.4 The Detection Verification Level (DVL) and Reporting
for Preservation of Organic Constituents
Range for the ethanolamines are listed in Table 1.
D5847 Practice for Writing Quality Control Specifications
1.4.1 The DVL is required to be at a concentration at least
for Standard Test Methods for Water Analysis
3 times below the Reporting Limit (RL) and have a signal/
E2554 Practice for Estimating and Monitoring the Uncer-
noise ratio greater than 3:1. Fig. 1 displays the signal/noise
tainty of Test Results of a Test Method in a Single
ratios at the DVLs and at higher concentrations for
Laboratory Using a Control Sample Program
N-methyldiethanolamine.
2.2 Other Documents:
1.4.2 The reporting limit is the concentration of the Level 1
EPApublication SW-846 Test Methods for Evaluating Solid
calibration standard as shown in Table 2 for diethanolamine,
Waste, Physical/Chemical Methods
triethanolamine, and N-ethyldiethanolamine and Level 2 for
N-methyldiethanolamine. The reporting limit for
3. Terminology
N-methyldiethanolamine is set at 50 µg/L due to poor sensi-
3.1 Definitions:
tivity at a 5 µg/L concentration which did not meet the DVL
3.1.1 detection verification level (DVL), n—a concentration
criteria. The DVL for N-methyldiethanolamine is at 10 µg/L,
that has a signal/noise ratio greater than 3:1 and is at least 3
which forces a raised reporting limit (chromatograms are
times below the reporting limit (RL).
shown in Fig. 1). However, the multi-laboratory validation
3.1.2 reporting limit (RL), n—the concentration of the
required a spike of all target analytes at 25 µg/L. The mean
lowest-level calibration standard used for quantification.
recovery for N-methyldiethanolamine at this level was 88 % as
shown in Table 3. If your instrument’s sensitivity can meet the
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
This test method is under the jurisdiction of ASTM Committee D19 on Water Standards volume information, refer to the standard’s Document Summary page on
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor the ASTM website.
Organic Substances in Water. Available from National Technical Information Service (NTIS), U.S. Depart-
Current edition approved Dec. 1, 2009. Published January 2010. DOI: 10.1520/ ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
D7599-09. www.epa.gov/epawaste/hazard/testmethods/index.htm.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D7599 – 09
TABLE 1 Detection Verification Level and Reporting Range
5.2 This method has been investigated for use with reagent
Analyte DVL (µg/L) Reporting Range (µg/L) and surface water.
Diethanolamine 5 25-500
6. Interferences
Triethanolamine 5 25-500
N-Ethyldiethanolamine 5 25-500
6.1 Method interferences may be caused by contaminants in
N-Methyldiethanolamine 10 50-500
solvents, reagents, glassware and other apparatus producing
discrete artifacts or elevated baselines. All of these materials
are demonstrated to be free from interferences by analyzing
3.1.3 ethanolamines, n—in this test method, diethanola-
laboratory reagent blanks under the same conditions as
mine, triethanolamine, N-methyldiethanolamine and
samples.
N-ethyldiethanolamine collectively.
6.2 All glassware is washed in hot water with a detergent,
3.2 Abbreviations:
rinsed in hot water followed by distilled water. Detergents
3.2.1 ND—non-detect
containing ethanolamines must not be used to clean glassware.
The glassware is then dried and heated in an oven at 250°C for
4. Summary of Test Methods
15 to 30 minutes. All glassware is subsequently cleaned with
4.1 This is a performance-based method and modifications
acetone, then methanol.
are allowed to improve performance.
6.3 All reagents and solvents should be pesticide residue
4.2 For ethanolamines analysis, samples are shipped to the
purity or higher to minimize interference problems.
lab between 0°C and 6°C and analyzed within 7 days of
6.4 Matrix interferences may be caused by contaminants
collection. In the lab, the samples are spiked with surrogate,
that are co-extracted from the sample. The extent of matrix
filtered using a syringe-driven Millex HV PVDF filter unit and
interferences can vary considerably from sample source de-
analyzed directly by LC/MS/MS.
pending on variations of the sample matrix.
4.3 Diethanolamine, triethanolamine,
N-methyldiethanolamine and N-ethyldiethanolamine and
7. Apparatus
diethanolamine-D (surrogate) are identified by retention time
7.1 LC/MS/MS System
and one SRM transition. The target analytes and surrogate are
7.1.1 Liquid Chromatography (LC) System—A complete
quantitated using the SRM transitions utilizing an external
LC system is needed in order to analyze samples. A system
calibration. The final report issued for each sample lists the
that is capable of performing at the flows, pressures, controlled
concentration of diethanolamine, triethanolamine,
temperatures, sample volumes and requirements of the stan-
N-methyldiethanolamine and N-ethyldiethanolamine and the
dard may be used.
diethanolamine-D surrogate recovery.
7.1.2 Analytical Column-Waters—Atlantis HILIC Silica,
100 mm 3 2.1 mm, 3 µm particle size, or equivalent.
5. Significance and Use
7.1.3 Tandem Mass Spectrometer (MS/MS) System—A
5.1 N-Ethyldiethanolamine, N-methyldiethanolamine and
MS/MS system capable of MRM analysis. A system that is
triethanolamineareSchedule3compoundsundertheChemical
capable of performing at the requirements in this standard may
Weapons Convention (CWC). Schedule 3 chemicals include
be used.
those that have been produced, stockpiled or used as a
7.2 Filtration Device
chemical weapon, poses otherwise a risk to the object and
7.2.1 Hypodermic syringe—Alocktipglasssyringecapable
purpose of the CWC because they possess such lethal or
of holding a Millex HV Syringe Driven Filter Unit PVDF 0.45
incapacitating toxicity as well as other properties that might
µm (Millipore Corporation, Catalog # SLHV033NS) or similar
enable it to be used as a chemical weapon, poses otherwise a
may be used.
risk to the object and purpose of the CWC by virtue of it’s
7.2.1.1 A25-mLlock tip glass syringe size is recommended
importanceintheproductionofoneormorechemicalslistedin
since a 25-mL sample size is used in this test method.
Schedules 1 or 2, or it may be produced in large commercial
7.2.2 Filter—Millex HV Syringe Driven Filter Unit PVDF
quantities for purposes not prohibited under the CWC. Etha-
0.45 µm (Millipore Corporation, Catalog # SLHV033NS) or
nolamines have a broad spectrum of applications. They are
similar may be used.
usedtoproduceadhesives,agriculturalproducts,cementgrind-
ing aids, concrete additives, detergents, specialty cleaners,
8. Reagents and Materials
personal care products, gas treatments, metalwork, oil well
8.1 Purity of Reagents—High-performance liquid chroma-
chemicals, packaging and printing inks, photographic chemi-
tography (HPLC) pesticide residue analysis and spectropho-
cals, rubber, textile finishing, urethane coatings, textile lubri-
tometry grade chemicals shall be used in all tests. Unless
cants, polishes, pesticides, and pharmaceuticals. Ethanola-
indicated otherwise, it is intended that all reagents shall
mines are readily dissolved in water, biodegradable and the
bio-concentration potential is low.
AWatersAlliance High Performance Liquid Chromatography (HPLC) System
was used to develop this test method. The multi-laboratory study included Agilent
Additional information about CWC and ethanolamines are available on the and Waters LC systems.
Internet at http://www.opcw.org (2009). A Waters Quattro micro API mass spectrometer was used to develop this test
Additional information can be found on the Dow Chemical Company website method. The multi-laboratory study included Applied Biosystems, Varian and
at http://www.dow.com/amines/prod/index.htm (2009). Waters mass spectrometers.
D7599 – 09
FIG. 1 Example SRM Chromatograms Signal/Noise Ratios
TABLE 2 Concentrations of Calibration Standards (PPB)
8.6 Acetone (CAS # 67-64-1).
Analyte/Surrogate LV 1 LV 2 LV 3 LV 4 LV 5 LV 6 LV 7 8.7 Ammonium acetate (CAS # 631-61-8).
8.8 Diethanolamine (CAS # 111-42-2).
Diethanolamine 25 50 75 150 250 350 500
Triethanolamine 25 50 75 150 250 350 500
8.9 Triethanolamine (CAS # 102-71-6).
N-Ethyldiethanolamine 25 50 75 150 250 350 500
8.10 N-Ethyldiethanolamine (CAS # 139-87-7).
N-Methyldiethanolamine 25 50 75 150 250 350 500
8.11 N-Methyldiethanolamine (CAS # 105-59-9).
Diethanolamine-D (Surrogate) 25 50 75 150 250 350 500
8.12 Bis(2-hydroxyethyl)-D -amine; (Diethanolamine-D ),
8 8
where the ethylene moieties contain all H (CAS # 103691-51-
6).
conform to the Committee on Analytical Reagents of the
8.12.1 Diethanolamine-D is used as a surrogate in this
8 8
American Chemical Society. Other reagent grades may be
standard.
used provided they are first determined to be of sufficiently
highpuritytopermittheirusewithoutaffectingtheaccuracyof
9. Hazards
the measurements.
9.1 Normal laboratory safety applies to this method. Ana-
8.2 Purity of Water—Unless otherwise indicated, references
lysts should wear safety glasses, gloves, and lab coats when
towatershallbeunderstoodtomeanreagentwaterconforming
working in the lab.Analysts should review the Material Safety
toType 1 of Specification D1193. It must be demonstrated that
Data Sheets (MSDS) for all reagents used in this method.
this water does not contain contaminants at concentrations
sufficient to interfere with the analysis.
10. Sampling
8.3 Gases—Ultrapure nitrogen and argon.
10.1 Sampling—Grab samples must be collected in
8.4 Acetonitrile (CAS # 75-05-8).
$25-mL pre-cleaned amber glass bottles with Teflon-lined
8.5 Methanol (CAS # 67-56-1).
caps demonstrated to be free of interferences. This test method
requires a 25-mL sample size per analysis. Conventional
sampling practices should be followed. Refer to Guide D3856
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
and Practices D3694.
listed by the American Chemical Society, see Annual Standards for Laboratory
10.2 Preservation—Store samples between 0°C and 6°C
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
from the time of collection until analysis. Analyze the sample
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. within 7 days of collection.
D7599 – 09
TABLE 3 Multi-Laboratory Recovery Data in Reagent Water
Analyte Spike Conc. # Results # Labs Bias Precision
(ppb)
Mean Min Max Overall SD Pooled Overall Pooled
Recovery Recovery Recovery (%) within-lab RSD (%) within-lab
(%) (%) (%) SD (%) RSD (%)
Diethanolamine 25 24 6 96.34 51.00 156.96 31.31 10.96 32.50 9.49
Diethanolamine 50 24 6 101.41 54.00 154.80 29.54 7.97 29.13 7.91
Diethanolamine 200 24 6 101.57 61.00 138.00 20.98 10.50 20.66 10.85
Diethanolamine 425 24 6 102.06 70.00 138.82 17.98 5.90 17.61 5.70
Triethanolamine 25 24 6 87.70 35.96 157.20 27.00 25.18 30.79 27.48
Triethanolamine 50 24 6 94.95 67.00 121.66 16.39 9.57 17.26 9.66
Triethanolamine 200 22 6 105.00 79.50 132.00 14.06 11.81 13.39 11.52
Triethanolamine 425 24 6 96.94 40.00 144.94 27.56 4.41 28.43 5.76
N-Ethyldiethanolamine 25 24 6 90.61 31.00 132.00 39.42 7.47 43.51 10.42
N-Ethyldiethanolamine 50 23 6 111.88 49.00 146.00 28.71 7.19 25.66 7.56
N-Ethyldiethanolamine 200 24 6 106.20 60.00 134.00 23.09 11.96 21.74 12.23
N-Ethyldiethanolamine 425 24 6 99.67 51.00 130.00 23.07 4.68 23.15 6.01
N-Methyldiethanolamine 25 24 6 88.43 41.72 133.60 25.24 13.29 28.55 16.70
N-Methyldiethanolamine 50 24 6 102.28 56.00 153.80 25.85 8.73 25.27 8.22
N-Methyldiethanolamine 200 24 6 101.02 59.00 136.50 20.07 9.51 19.87 9.54
N-Methyldiethanolamine 425 24 6 94.75 63.00 115.76 15.02 3.34 15.85 3.72
Diethanolamine-D (Surrogate) 200 96 6 103.02 60.00 151.95 21.13 9.40 20.51 9.25
11. Preparation of LC/MS/MS multiple reaction monitoring (MRM) experiment window.
Variable parameters regarding retention times, SRM Transi-
11.1 LC Chromatograph Operating Conditions :
tions and cone and collision energies are shown in Table 5.
11.1.1 Injection volumes of all calibration standards and
The instrument is set in the Electrospray (+) positive setting.
samples are 25 µL. The first sample analyzed after the
Capillary Voltage: 0.5
...