ASTM D7598-09
(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
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.
This 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 method. This method adheres to single reaction monitoring (SRM) mass spectrometry.
1.2 This test method has been developed in support of the National Homeland Security Research Center, US EPA by Region 5 Chicago Regional Laboratory.
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.
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.
1.4.2 The RL is the concentration of the level 1 calibration standard as shown in Table 2. The reporting limit for this method is 100 μg/L.
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.
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D7598 – 09
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. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
TABLE 1 Detection Verification Level and Reporting Range
1. Scope
Analyte DVL (µg/L) Reporting Range (µg/L)
1.1 This procedure covers the determination of thiodiglycol
Thiodiglycol 20 100–10 000
(TDG) in surface water by direct injection using liquid
chromatography (LC) and detected with tandem mass spec-
trometry (MS/MS). TDG is qualitatively and quantitatively
determined by this method. This method adheres to single
Applicable Test Methods of Committee D19 on Water
reaction monitoring (SRM) mass spectrometry.
D3856 Guide for Good Laboratory Practices in Laborato-
1.2 This test method has been developed in support of the
ries Engaged in Sampling and Analysis of Water
National Homeland Security Research Center, US EPA by
D3694 Practices for Preparation of Sample Containers and
Region 5 Chicago Regional Laboratory.
for Preservation of Organic Constituents
1.3 The values stated in SI units are to be regarded as
D5847 Practice for Writing Quality Control Specifications
standard. No other units of measurement are included in this
for Standard Test Methods for Water Analysis
standard.
E2554 Practice for Estimating and Monitoring the Uncer-
1.4 The Detection Verification Level (DVL) and Reporting
tainty of Test Results of a Test Method in a Single
Range for TDG are listed in Table 1.
Laboratory Using a Control Sample Program
1.4.1 The DVL is required to be at a concentration at least
2.2 Other Documents:
3 times below the reporting limit (RL) and have a signal/noise
EPApublication SW-846 Test Methods for Evaluating Solid
ratio greater than 3:1. Fig. 1 displays the signal/noise ratio at
Waste, Physical/Chemical Methods
the DVL.
1.4.2 The RL is the concentration of the level 1 calibration
3. Terminology
standard as shown in Table 2. The reporting limit for this
3.1 Definitions:
method is 100 µg/L.
3.1.1 detection verification level (DVL), n—a concentration
1.5 This standard does not purport to address all of the
that has a signal/noise ratio greater than 3:1 and is at least 3
safety concerns, if any, associated with its use. It is the
times below the reporting limit (RL).
responsibility of the user of this standard to establish appro-
3.1.2 reporting limit (RL), n—the concentration of the
priate safety and health practices and determine the applica-
lowest-level calibration standard used for quantification.
bility of regulatory limitations prior to use.
3.2 Abbreviations:
3.2.1 ND—non-detect
2. Referenced Documents
2.1 ASTM Standards:
4. Summary of Test Methods
D1129 Terminology Relating to Water
4.1 This is a performance based method and modifications
D1193 Specification for Reagent Water
are allowed to improve performance.
D2777 Practice for Determination of Precision and Bias of
4.2 For thiodiglycol analysis, samples are shipped to the lab
between0°Cand6°Candanalyzedwithin7daysofcollection.
In the lab, the samples are spiked with surrogate, filtered using
This test method is under the jurisdiction of ASTM Committee D19 on Water
a syringe driven Millex HV PVDF filter unit and analyzed
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
Organic Substances in Water. directly by LC/MS/MS.
Current edition approved Dec. 1, 2009. Published January 2010. DOI: 10.1520/
D7598-09.
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 Available from National Technical Information Service (NTIS), U.S. Depart-
Standards volume information, refer to the standard’s Document Summary page on ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
the ASTM website. 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 – 09
FIG. 1 Example 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 1000 2500 5000 10 000
3,3’-Thiodipropanol 100 250 500 1000 2500 5000 10 000
4.3 Thiodiglycol and 3,3’-thiodipropanol (surrogate) are 5.2 This method has been investigated for use with reagent
identified by retention time and one SRM transition.The target and surface water.
analyteandsurrogatearequantitatedusingtheSRMtransitions
6. Interferences
utilizing an external calibration. The final report issued for
each sample lists the concentration of TDG and the 3,3’-
6.1 Method interferences may be caused by contaminants in
thiodipropanol surrogate recovery.
solvents, reagents, glassware and other apparatus producing
discrete artifacts or elevated baselines. All of these materials
5. Significance and Use
are demonstrated to be free from interferences by analyzing
5.1 Thiodiglycol is a Schedule 2 compound under the
laboratory reagent blanks under the same conditions as
Chemical Weapons Convention (CWC). Schedule 2 chemicals
samples.
include those that are precursors to chemical weapons, chemi-
6.2 All glassware is washed in hot water with a detergent,
cal weapons agents or have a number of other commercial
rinsed in hot water followed by distilled water. The glassware
uses. They are used as ingredients to produce insecticides,
is then dried and heated in an oven at 250°C for 15 to 30
herbicides, lubricants, and some pharmaceutical products.
minutes. All glassware is subsequently cleaned with acetone,
Schedule 2 chemicals can be found in applications unrelated to
then methanol.
chemical weapons. Thiodiglycol is both a mustard gas precur-
6.3 All reagents and solvents should be pesticide residue
sor and degradant as well as an ingredient in water-based inks,
purity or higher to minimize interference problems.
ballpoint pen inks, dyes and some pesticides.
6.4 Matrix interferences may be caused by contaminants
that are co-extracted from the sample. The extent of matrix
4 interferences can vary considerably from sample source de-
AdditionalinformationaboutCWCandthiodiglycolisavailableontheInternet
at http://www.opcw.org (2009) pending on variations of the sample matrix.
D7598 – 09
7. Apparatus 9. Hazards
7.1 LC/MS/MS System 9.1 Normal laboratory safety applies to this method. Ana-
7.1.1 Liquid Chromatography (LC) System—A complete lysts should wear safety glasses, gloves, and lab coats when
LC system is needed in order to analyze samples. A system working in the lab.Analysts should review the Material Safety
that is capable of performing at the flows, pressures, controlled Data Sheets (MSDS) for all reagents used in this method.
temperatures, sample volumes and requirements of the stan-
dard may be used.
10. Sampling
7.1.2 Analytical Column-SIELC—Primesep SB 5 µm, 100
10.1 Sampling—Grab samples must be collected in
Å particle, 150 mm 3 2.1 mm or equivalent.
$25-mL pre-cleaned amber glass bottles with Teflon-lined
7.1.3 Tandem Mass Spectrometer (MS/MS) System—A
caps demonstrated to be free of interferences. This test method
MS/MS system capable of MRM analysis. A system that is
requires a 25-mL sample size per analysis. Conventional
capable of performing at the requirements in this standard may
sampling practices should be followed. Refer to Guide D3856
be used.
and Practices D3694.
7.2 Filtration Device
10.2 Preservation—Store samples between 0°C and 6°C
7.2.1 Hypodermic syringe—Alocktipglasssyringecapable
from the time of collection until analysis. Analyze the sample
of holding a Millex HV Syringe Driven Filter Unit PVDF 0.45
within 1 day of collection.
µm (Millipore Corporation, Catalog # SLHV033NS) or similar
may be used.
11. Preparation of LC/MS/MS
7.2.1.1 A25-mLlock tip glass syringe size is recommended
11.1 LC Chromatograph Operating Conditions :
since a 25-mL sample size is used in this test method.
11.1.1 Injection volumes of all calibration standards and
7.2.2 Filter—Millex HV Syringe Driven Filter Unit PVDF
samples are 50 µL. The first sample analyzed after the
0.45 µm (Millipore Corporation, Catalog # SLHV033NS) or
calibrationcurveisablanktoensurethereisnocarry-over.The
similar may be used.
gradient conditions for the liquid chromatograph are shown in
Table 3.
8. Reagents and Materials
11.1.2 Temperatures—Column, 30°C; Sample compart-
8.1 Purity of Reagents—High-performance liquid chroma-
ment, 15°C.
tography (HPLC) pesticide residue analysis and spectropho-
11.1.3 Seal Wash—Solvent: 50 % Acetonitrile/50 % Water;
tometry grade chemicals shall be used in all tests. Unless
Time: 5 minutes.
indicated otherwise, it is intended that all reagents shall
11.1.4 Needle Wash—Solvent: 50 % Acetonitrile/50 % Wa-
conform to the Committee on Analytical Reagents of the
7 ter; Normal Wash, approximately 13 second wash time.
American Chemical Society. Other reagent grades may be
11.1.5 Autosampler Purge—Three loop volumes.
used provided they are first determined they are of sufficiently
11.1.6 Specific instrument manufacturer wash/purge speci-
highpuritytopermittheirusewithoutaffectingtheaccuracyof
fications should be followed in order to eliminate sample
the measurements.
carry-over in the analysis of TDG.
8.2 Purity of Water—Unless otherwise indicated, references
11.2 Mass Spectrometer Parameters :
towatershallbeunderstoodtomeanreagentwaterconforming
11.2.1 In order to acquire the maximum number of data
toType 1 of Specification D1193. It must be demonstrated that
points per SRM channel while maintaining adequate sensitiv-
this water does not contain contaminants at concentrations
ity, the tune parameters may be optimized according to your
sufficient to interfere with the analysis.
instrument. Each peak requires at least 10 scans per peak for
8.3 Gases—Ultrapure nitrogen and argon.
adequate quantitation. This standard contains only one target
8.4 Acetonitrile (CAS # 75-05-8).
compound and one surrogate which are in different SRM
8.5 Methanol (CAS # 67-56-1).
experiment windows in order to optimize the number of scans
8.6 Acetone (CAS # 67-64-1).
and sensitivity. Variable parameters regarding retention times,
8.7 Ammonium formate (CAS # 540-69-2).
SRM Transitions and cone and collision energies are shown in
8.8 Formic acid (64-18-6).
Table 4.
8.9 Thiodiglycol (CAS # 111-48-8).
8.10 3,3’-Thiodipropanol (CAS # 10595-09-2).
TABLE 3 Gradient Conditions for Liquid Chromatography
AWatersAlliance High Performance Liquid Chromatography (HPLC) System
Time Flow Percent Percent Percent
was used to develop this test method. The multi-laboratory study included Agilent (min) (µL/min) CH CN Water 500 mmolar
and Waters LC systems. Ammonium
Formate/2%
A Waters Quattro micro API mass spectrometer was used to develop this test
Formic Acid
method. The multi-laboratory study included Agilent, Applied Biosystems, Varian
and Waters mass spectrometers.
0 300 0 95 5
Reagent Chemicals, American Chemical Society Specifications, American
2.5 300 0 95 5
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
6 300 90 5 5
listed by the American Chemical Society, see Annual Standards for Laboratory
10 300 90 5 5
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
12 300 0 95 5
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 16 300 0 95 5
MD.
D7598 – 09
TABLE 4 Retention Times, SRM Ions, and Analyte-Specific Mass Spectrometer Parameters
Analyte SRM Mass Transition Retention Time Cone Voltage Collision Energy
(Parent > Product) (min) (Volts) (eV)
Thiodiglycol 123.1 > 104.9 2.75 18 5
3,3’-Thiodipropanol 151.2 > 133.1 5.75 19 8
ensure optimum results. Stock calibration standards are rou-
The instrument is set in the Electrospray (+) positive setting.
Capillary Voltage: 3.5 kV
tinelyreplacedeverysixmonthsifnotpreviouslydiscardedfor
Cone: Variable depending on analyte (Table 4)
quality control failure. Calibration standards are not filtered.
Extractor: 2 Volts
RF Lens: 0.2 Volts
12.2.3 Inject each standard and obtain a chromatogram for
Source Temperature: 120°C
each one. An external calibration is used monitoring the SRM
Desolvation Temperature: 300°C
Desolvation Gas Flow: 500 L/hr transition of each analyte. Calibration software is utilized to
Cone Gas Flow: 25 L/hr
conduct the quantitation of the target analyte and surrogate.
Low Mass Resolution 1: 14.5
TheSRMtransitionofeachanalyteisusedforquantitationand
High Mass Resolution 1: 14.5
Ion Energy 1: 0.5
confirmation. This gives confirmation by isolating the parent
Entrance Energy: –1
ion, fragmenting it to the product ion, and also relating it to the
Collision Energy: Variable depending on analyte (Table 4)
retention time in the calibration standard.
Exit Energy: 2
Low Mass Resolution 2: 15
12.2.4 The calibration software manual should be consulted
High Mass resolution 2: 15
to use the software correctly. The quantitation method is set as
Ion Energy 2: 0.5
Multiplier: 650
anexternalcalibrationusingthepeakareasinppborppmunits
–3
Gas Cell Pirani Gauge: 3.3 3 10 Torr
as long as the analyst is consistent. Concentrations may be
Inter-Channel Delay: 0.02 seconds
calculated using the data system software to generate linear
Inter-Scan Delay: 0.1 seconds
Repeats: 1
regression or quadratic calibration curves. Forcing the calibra-
Span: 0 Daltons
tion through the origin is not recommended.
Dwell: 0.1 Seconds
12.2.5 Linear calibration may be used if the coefficient of
12. Calibration and Standardization 2
determination, r , is >0.98 for the analyte. The point of origin
12.1 The mass spectrometer must be calibrated per manu-
is excluded and a fit weighting of 1/X is used in order to give
facturer specifications before analysis. In order that analytical
more emphasis to the lower concentrations. If one of the
values obtained using this test method are valid and accurate
calibration standards other than the high or low point causes
within the confidence limits of the test method, the following
the r of the curve to be <0.98, this point must be re-injected or
proceduresmustbefollowedwhenperformingthetestmethod.
a new calibration curve must be regenerated. If the low or high
12.2 Calibration and Standardization—To calibrate the in-
(or both) poi
...
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