ASTM D7598-16(2017)
(Test Method)Standard Test Method for Determination of Thiodiglycol in Water by Single Reaction Monitoring Liquid Chromatography/Tandem Mass Spectrometry
Standard Test Method for Determination of Thiodiglycol in Water by Single Reaction Monitoring Liquid Chromatography/Tandem Mass Spectrometry
SIGNIFICANCE AND USE
5.1 Thiodiglycol is a Schedule 2 compound under the Chemical Weapons Convention (CWC). Schedule 2 chemicals include those that are precursors to chemical weapons, chemical weapons agents or have a number of other commercial uses. They are used as ingredients to produce insecticides, herbicides, lubricants, and some pharmaceutical products. Schedule 2 chemicals can be found in applications unrelated to chemical weapons. Thiodiglycol is both a mustard gas precursor and degradant as well as an ingredient in water-based inks, ballpoint pen inks, dyes and some pesticides.4
5.2 This test method has been investigated for use with reagent and surface water.
SCOPE
1.1 This procedure covers the determination of thiodiglycol (TDG) in surface water by direct injection using liquid chromatography (LC) and detected with tandem mass spectrometry (MS/MS). TDG is qualitatively and quantitatively determined by this test method. This test method adheres to single reaction monitoring (SRM) mass spectrometry.
1.2 This test method has been developed by U.S. EPA Region 5 Chicago Regional Laboratory (CRL).
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 The detection verification level (DVL) and reporting range for TDG are listed in Table 1.
TABLE 1 Detection Verification Level and Reporting Range
Analyte
DVL (μg/L)
Reporting Range (μg/L)
Thiodiglycol
20
100–10 000
1.4.1 The DVL is required to be at a concentration at least 3 times below the reporting limit (RL) and have a signal/noise ratio greater than 3:1. Fig. 1 displays the signal/noise ratio at the DVL.
FIG. 1 Example SRM Chromatograms Signal/Noise at Detection Verification Level
1.4.2 The RL is the concentration of the Level 1 calibration standard as shown in Table 2. The reporting limit for this test method is 100 μg/L.
TABLE 2 Concentrations of Calibration Standards (PPB)
Analyte/Surrogate
LV 1
LV 2
LV 3
LV 4
LV 5
LV 6
LV 7
Thiodiglycol
100
250
500
1 000
2 500
5 000
10 000
3,3’-Thiodipropanol
100
250
500
1 000
2 500
5 000
10 000
1.5 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 and health practices and determine the applicability of regulatory limitations prior to use.
1.6 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.
General Information
Relations
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:D7598 −16 (Reapproved 2017)
Standard Test Method for
Determination of Thiodiglycol in Water by Single Reaction
Monitoring Liquid Chromatography/Tandem Mass
Spectrometry
This standard is issued under the fixed designation D7598; 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 2. Referenced Documents
1.1 This procedure covers the determination of thiodiglycol 2.1 ASTM Standards:
(TDG) in surface water by direct injection using liquid D1129Terminology Relating to Water
chromatography (LC) and detected with tandem mass spec- D1193Specification for Reagent Water
trometry (MS/MS). TDG is qualitatively and quantitatively D2777Practice for Determination of Precision and Bias of
determined by this test method. This test method adheres to Applicable Test Methods of Committee D19 on Water
single reaction monitoring (SRM) mass spectrometry. D3856Guide for Management Systems in Laboratories
Engaged in Analysis of Water
1.2 This test method has been developed by U.S. EPA
D3694Practices for Preparation of Sample Containers and
Region 5 Chicago Regional Laboratory (CRL).
for Preservation of Organic Constituents
1.3 The values stated in SI units are to be regarded as
D5847Practice for Writing Quality Control Specifications
standard. No other units of measurement are included in this
for Standard Test Methods for Water Analysis
standard.
E2554Practice for Estimating and Monitoring the Uncer-
tainty of Test Results of a Test Method Using Control
1.4 The detection verification level (DVL) and reporting
range for TDG are listed in Table 1. Chart Techniques
2.2 Other Documents:
1.4.1 The DVL is required to be at a concentration at least
3 times below the reporting limit (RL) and have a signal/noise U.S. EPA publication SW-846Test Methods for Evaluating
ratio greater than 3:1. Fig. 1 displays the signal/noise ratio at Solid Waste, Physical/Chemical Methods
the DVL.
3. Terminology
1.4.2 The RLis the concentration of the Level 1 calibration
standard as shown in Table 2. The reporting limit for this test 3.1 Definitions:
method is 100 µg/L.
3.1.1 For definitions of terms used in this standard, refer to
Terminology D1129.
1.5 This standard does not purport to address all of the
3.2 Definitions of Terms Specific to This Standard:
safety concerns, if any, associated with its use. It is the
3.2.1 detection verification level, DVL, n—a concentration
responsibility of the user of this standard to establish appro-
thathasasignal/noiseratiogreaterthan3:1andisatleastthree
priate safety and health practices and determine the applica-
times below the reporting limit (RL).
bility of regulatory limitations prior to use.
1.6 This international standard was developed in accor-
3.2.2 independent reference material, IRM, n—amaterialof
dance with internationally recognized principles on standard- known purity and concentration obtained either from the
ization established in the Decision on Principles for the
NationalInstituteofStandardsandTechnology(NIST)orother
Development of International Standards, Guides and Recom- reputable supplier. The IRM shall be obtained from a different
mendations issued by the World Trade Organization Technical
lot of material than is used for calibration.
Barriers to Trade (TBT) Committee.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
This test method is under the jurisdiction ofASTM Committee D19 on Water contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor Standards volume information, refer to the standard’s Document Summary page on
Organic Substances in Water. the ASTM website.
Current edition approved June 15, 2017. Published July 2017. Originally Available from National Technical Information Service (NTIS), U.S. Depart-
approved in 2009. Last previous edition approved in 2016 as D7598 – 16. DOI: ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
10.1520/D7598-16R17. 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
D7598−16 (2017)
TABLE 1 Detection Verification Level and Reporting Range
include those that are precursors to chemical weapons, chemi-
Analyte DVL (µg/L) Reporting Range (µg/L) cal weapons agents or have a number of other commercial
Thiodiglycol 20 100–10 000
uses. They are used as ingredients to produce insecticides,
herbicides, lubricants, and some pharmaceutical products.
Schedule2chemicalscanbefoundinapplicationsunrelatedto
chemical weapons. Thiodiglycol is both a mustard gas precur-
3.3 Acronyms:
sor and degradant as well as an ingredient in water-based inks,
3.3.1 CCC, n—Continuing Calibration Check
ballpoint pen inks, dyes and some pesticides.
3.3.2 IC, n—Initial Calibration
5.2 This test method has been investigated for use with
3.3.3 LC, n—Liquid Chromatography
reagent and surface water.
3.3.4 LCS/LCSD, n—Laboratory Control Sample/
Laboratory Control Sample Duplicate
6. Interferences
3.3.5 MDL, n—Method Detection Limit
6.1 Methodinterferencesmaybecausedbycontaminantsin
3.3.6 MeOH, n—Methanol
solvents, reagents, glassware and other apparatus producing
–3
3.3.7 mM, n—millimolar,1×10 moles/L
discrete artifacts or elevated baselines. All of these materials
3.3.8 MRM, n—Multiple Reaction Monitoring
are demonstrated to be free from interferences by analyzing
3.3.9 MS/MSD, n—Matrix Spike/Matrix Spike Duplicate
laboratory reagent blanks under the same conditions as
samples.
3.3.10 NA, adj—Not Available
3.3.11 ND, n—non-detect
6.2 All glassware is washed in hot water with a detergent,
rinsed in hot water followed by distilled water. The glassware
3.3.12 P&A, n—Precision and Accuracy
is then dried and heated in an oven at 250°C for 15 to 30
3.3.13 PPB, n—parts per billion
minutes. All glassware is subsequently cleaned with acetone,
3.3.14 PPT, n—parts per trillion
then methanol.
3.3.15 QA, adj—Quality Assurance
6.3 All reagents and solvents should be pesticide residue
3.3.16 QC, adj—Quality Control
purity or higher to minimize interference problems.
3.3.17 RL, n—Reporting Limit
6.4 Matrix interferences may be caused by contaminants
3.3.18 RSD, n—Relative Standard Deviation
that are co-extracted from the sample. The extent of matrix
3.3.19 RT, n—Retention Time
interferences can vary considerably from sample source de-
3.3.20 SDS, n—Safety Data Sheets
pending on variations of the sample matrix.
3.3.21 SRM, n—Single Reaction Monitoring
7. Apparatus
3.3.22 SS, n—Surrogate Standard
3.3.23 TC, n—Target Compound
7.1 LC/MS/MS System:
–6
3.3.24 µM, n—micromolar,1×10 moles/L
7.1.1 LiquidChromatography(LC)System—AcompleteLC
system is needed in order to analyze samples. This should
3.3.25 VOA, n—Volatile Organic Analysis
include a sample injection system, a solvent pumping system
4. Summary of Test Methods
capable of mixing solvents, a sample compartment capable of
maintaining required temperature and a temperature controlled
4.1 This is a performance based method and modifications
columncompartment.Asystemthatiscapableofperformingat
are allowed to improve performance.
the flows, pressures, controlled temperatures, sample volumes
4.2 Forthiodiglycolanalysis,samplesareshippedtothelab
and requirements of the standard may be used.
between0°Cand6°Candanalyzedwithin7daysofcollection.
7.1.2 Analytical Column —Any column that achieves ad-
Inthe lab, the samplesarespikedwithsurrogate,filteredusing
equateresolutionmaybeused.Theretentiontimesandorderof
a syringe-driven filter unit and analyzed directly by LC/MS/
elution may change depending on the column that is used and
MS.
need to be monitored.
4.3 Thiodiglycol and 3,3’-thiodipropanol (surrogate) are
identifiedbyretentiontimeandoneSRMtransition.Thetarget
analyteandsurrogatearequantitatedusingtheSRMtransitions
Additional information about CWC and thiodiglycol is available from the
utilizing an external calibration. The final report issued for
Organization for the Prohibition of Chemical Weapons (OPCW), http://
each sample lists the concentration of TDG and the 3,3’-
www.opcw.org.
thiodipropanol surrogate recovery.
AWatersAlliance High Performance Liquid Chromatography (HPLC) System
(a trademark of the Waters Corporation, Milford, MA), or equivalent, was found
5. Significance and Use suitable for use. The multi-laboratory study included Agilent and Waters LC
systems.
5.1 Thiodiglycol is a Schedule 2 compound under the
A SIELC—A Primesep SB 5 µm, 100 Å particle, 150 mm × 2.1 mm, or
Chemical Weapons Convention (CWC). Schedule 2 chemicals equivalent, was found suitable for use.
D7598−16 (2017)
FIG. 1Example SRM Chromatograms Signal/Noise at Detection Verification Level
TABLE 2 Concentrations of Calibration Standards (PPB)
Analyte/Surrogate LV 1 LV 2 LV 3 LV 4 LV 5 LV 6 LV 7
Thiodiglycol 100 250 500 1 000 2 500 5 000 10 000
3,3’-Thiodipropanol 100 250 500 1 000 2 500 5 000 10 000
7.1.3 Tandem Mass Spectrometer (MS/MS) System—A conform to the Committee on Analytical Reagents of the
7 9
MS/MS system capable of MRM analysis. A system that is American Chemical Society. Other reagent grades may be
capableofperformingattherequirementsinthisstandardmay used provided they are first determined they are of sufficiently
be used. highpuritytopermittheirusewithoutaffectingtheaccuracyof
the measurements.
7.2 Filtration Device:
7.2.1 Hypodermic Syringe—A luer-lock tip glass syringe 8.2 Purity of Water—Unless otherwise indicated, references
capable of holding a syringe-driven filter unit. towatershallbeunderstoodtomeanreagentwaterconforming
7.2.1.1 A25-mLlocktipglasssyringesizeisrecommended toType1ofSpecificationD1193.Itmustbedemonstratedthat
since a 25-mL sample size is used in this test method. this water does not contain contaminants at concentrations
7.2.2 Filter Unit —APVDFbefilterunitswereusedtofilter sufficient to interfere with the analysis.
the samples.
8.3 Gases—Ultrapure nitrogen and argon.
8. Reagents and Materials 8.4 Acetonitrile (CAS # 75-05-8).
8.5 Methanol (CAS # 67-56-1).
8.1 Purity of Reagents—High-performance liquid chroma-
tography (HPLC) pesticide residue analysis and spectropho-
8.6 Acetone (CAS # 67-64-1).
tometry grade chemicals shall be used in all tests. Unless
8.7 Ammonium formate (CAS # 540-69-2).
indicated otherwise, it is intended that all reagents shall
8.8 Formic acid (64-18-6).
A Waters Quattro micro API mass spectrometer (a trademark of the Waters
Corporation, Milford, MA), or equivalent, was found suitable for use. The
multi-laboratory study included Applied Biosystems and Waters mass spectrom- Reagent Chemicals, American Chemical Society Specifications, American
eters. Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
A Millex HV Syringe Driven Filter Unit PVDF 0.45 µm (Millipore listed by the American Chemical Society, see Annual Standards for Laboratory
Corporation, Catalog # SLHV033NS; Millex is a trademark of Merck KGAA, Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Darmstadt,Germany)hasbeenfoundsuitableforuseforthistestmethod,anyfilter and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
unit may be used that meets the performance of this test method may be used. MD.
D7598−16 (2017)
8.9 Thiodiglycol (CAS # 111-48-8). and sensitivity. Variable parameters regarding retention times,
SRMTransitions and cone and collision energies are shown in
8.10 3,3’-Thiodipropanol (CAS # 10595-09-2).
Table 4.
9. Hazards The instrument is set in the Electrospray (+) positive setting.
Capillary Voltage: 3.5 kV
9.1 Normal laboratory safety applies to this method. Ana-
Cone: Variable depending on analyte (Table 4)
Extractor: 2 Volts
lysts should wear safety glasses, gloves, and lab coats when
RF Lens: 0.2 Volts
working in the lab. Analysts should review the Safety Data
Source Temperature: 120°C
Sheets (SDS) for all reagents used in this test method.
Desolvation Temperature: 300°C
Desolvation Gas Flow: 500 L/hr
Cone Gas Flow: 25 L/hr
10. Sampling
Low Mass Resolution 1: 14.5
High Mass Resolution 1: 14.5
10.1 Sampling—Grabsamplesmustbecollectedin≥25-mL
Ion Energy 1: 0.5
pre-cleaned amber glass bottles withTeflon-lined caps demon-
Entrance Energy: –1
strated to be free of interferences. This test method requires a
Collision Energy: Variable depending on analyte (Table 4)
25-mL sample size per analysis. Conventional sampling prac- Exit Energy: 2
Low Mass Resolution 2: 15
tices should be followed. Refer to Guide D3856 and Practices
High Mass resolution 2: 15
D3694.
Ion Energy 2: 0.5
Multiplier: 650
10.2 Preservation—Store samples between 0°C and 6°C
–3
Gas Cell Pirani Gauge: 3.3 × 10 Torr
from the time of collection until analysis.Analyze the sample
Inter-Channel Delay: 0.02 seconds
Inter-Scan Delay: 0.1 seconds
within 1 day of collection.
Repeats: 1
Span: 0 Daltons
11. Preparation of LC/MS/MS
Dwell: 0.1 Seconds
11.1 LC Chromatograph Operating Conditions:
12. Calibration and Standardization
11.1.1 Injection volumes of all calibration standards and
samples are 50 µL. The first sample analyzed after the
12.1 The mass spectrometer must be calibrated per manu-
calibrationcurveisablanktoensurethereisnocarry-over.The
facturer specifications before analysis. In order that analytical
gradient conditions for the liquid chromatograph are shown in
values obtained using this test method are valid and accurate
Table 3.
within the confidence limits of the test method, the following
11.1.2 Temperatures—Column, 30°C; Sample
proceduresmustbefollowedwhenperformingthetestmethod.
compartment, 15°C.
12.2 Calibration and Standardization—To calibrate the
11.1.3 Seal Wash—Solvent: 50% Acetonitrile/50% Water;
instrument, analyze seven calibration standards containing the
Time: 5 minutes.
seven concentration levels of TDG and 3,3’-thiodipropanol
11.1.4 Needle Wash—Solvent: 50% Acetonitrile/50% Wa-
prior to analysis as shown in Table 2. A calibration stock
ter; Normal Wash, approximately 13 second wash time.
standard solution is prepared from standard materials or
11.1.5 Autosampler Purge—Three loop volumes.
purchased as certified solutions. Stock standard solution A
11.1.6 Specific instrument manufacturer wa
...
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