ASTM E2838-21

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: E2838 − 11 (Reapproved 2016) E2838 − 21
Standard Test Method for
Determination of Thiodiglycol on Wipes by Solvent
Extraction Followed by Liquid Chromatography/Tandem
Mass Spectrometry (LC/MS/MS)
This standard is issued under the fixed designation E2838; 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 procedure details the determination of thiodiglycol (TDG), also known as 2,2’-thiobis-ethanol, on wipes with
3,3’-thiodipropanol (TDP) as the surrogate. This method is based upon solvent extraction of wipes by either sonication or a
pressurized fluid extraction (PFE) technique as an alternative option. The extract is filtered, concentrated, and analyzed by liquid
chromatography/tandem mass spectrometry (LC/MS/MS). TDG is qualitatively and quantitatively determined.
1.2 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this
standard.
2 3
1.3 The Method Detection Limitmethod detection limit (MDL) and Reporting Rangereporting range for TDG are listed in Table
1.
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, health, and environmental 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.
2. Referenced Documents
2.1 ASTM Standards:
D653 Terminology Relating to Soil, Rock, and Contained Fluids
D1193 Specification for Reagent Water
D3694D2777 PracticesPractice for PreparationDetermination of Sample Containers and for Preservation of Organic Constitu-
entsPrecision and Bias of Applicable Test Methods of Committee D19 on Water
This test method is under the jurisdiction of ASTM Committee D34 on Waste Management and is the direct responsibility of Subcommittee D34.01.06 on Analytical
Methods.
Current edition approved June 1, 2016May 1, 2021. Published July 2016May 2021. Originally approved in 2011. Last previous edition approved in 20112016 as
E2838 – 11.E2838 – 11 (2016). DOI: 10.1520/E2838-11R16.10.1520/E2838-21.
The MDL is determined following the Code of Federal Regulations, 40 CFR Part 136, Appendix B utilizing solvent extraction of wipes by sonication.
Reporting range concentrations are calculated from Table 4 concentrations assuming a 10 μL injection of the lowest and highest level calibration standards with a 2 mL
final extract volume. Volume variations will change the reporting limit and ranges. The reporting limit (RL), lowest concentration of the reporting range, is calculated from
the concentration of the Level 1 calibration standard as shown in Table 4.
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 Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E2838 − 21
TABLE 1 Method Detection Limit and Reporting Range
A
MDL Reporting Range
CAS
Analyte
Number (μg/wipe) (μg/wipe)
Thiodiglycol 111-48-8 0.085 1-80
3,3’-Thiodipropanol 10595-09-2 Not done 1-80
(Surrogate) for surrogates
TABLE 1 Method Detection Limit and Reporting Range
A
MDL Reporting Range
CAS
Analyte
Number
(μg/wipe) (μg/wipe)
Thiodiglycol 111-48-8 0.085 1–80
3,3’-Thiodipropanol 10595-09-2 Not done 1–80
(Surrogate) for surrogates
A
Chemical Chemical Abstract Service (CAS), Aa division of the American Chemi-
cal Society, 2540 Olentangy River Road, Columbus, OH, 43202, USA.
D3740D5681 Practice for Minimum Requirements for Agencies Engaged in Testing and/or Inspection of Soil and Rock as Used
in Engineering Design and ConstructionTerminology for Waste and Waste Management
E2554 Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques
2.2 Other Documents:
EPA Publication SW-846 Test Methods for Evaluating Solid Waste, Physical/Chemical Methods
The Code of Federal Regulations, 40 CFR Part 136, Appendix B Appendix BThe Code of Federal Regulations
3. Terminology
3.1 Definitions—For definitions of terms used in this test method, refer to Terminology D5681.
3.2 Abbreviations:
–3
3.2.1 mM—millimolar, 1 × 10 moles/L
3.2.2 ND—non-detect
3.2.3 SRM—single reaction monitoring
3.2.4 MRM—multiple reaction monitoring
3.2.5 VOA—volatile organic analysis
4. Summary of Test Method
4.1 For TDG wipe analysis, samples are shipped to the lab between 0°C0 °C and 6°C.6 °C. The samples are to be extracted,
concentrated, and analyzed directly by LC/MS/MS within 7seven days of collection. The handling, storage, preservation, and
LC/MS/MS analysis are consistent between the two extraction procedures described in this test method. Only one extraction
procedure is required, documenting which was performed.
4.2 TDG and TDP are identified by retention time and one SRM transition. The target analyte and surrogate are quantitated using
the SRM transitions utilizing an external calibration. The final report issued for each sample lists the concentration of TDG and
the TDP recovery.
5. Significance and Use
5.1 This is a performance based performance-based method, and modifications are allowed to improve performance.
5.1.1 Due to the rapid development of newer instrumentation and column chemistries, changes to the analysis described in this
standard are allowed as long as better or equivalent performance data result. Any modifications shall be documented and
Available from National Technical Information Service (NTIS), U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://www.epa.gov/
epawaste/hazard/testmethods/index.htm
E2838 − 21
performance data generated. The user of the data generated by this Standardstandard shall be made aware of these changes and
given the performance data demonstrating better or equivalent performance.
5.2 TDG 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 non-military commercial uses. Schedule
2 chemicals can also be found in applications unrelated to chemical weapons. These chemicals are used as ingredients to produce
insecticides, herbicides, lubricants, and some pharmaceutical products. TDG is a mustard gas precursor and a degradant as well
as an ingredient in water-based inks, ballpoint pen inks, dyes, and some pesticides.
5.3 This method has been investigated for use on surface wipes. TDG is also a human metabolite resulting from sulfur mustard
exposure but this method has not been investigated for such determinations.
6. Interferences
6.1 Method interferences may be caused by contaminants in solvents, reagents, glassware, and other apparatus producing discrete
artifacts or elevated baselines. All of these materials shall be demonstrated to be free from interferences by analyzing laboratory
reagent blanks under the same conditions as samples.
6.2 All reagents and solvents shall be of pesticide residue purity or higher to minimize interference problems.
6.3 Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences
can vary considerably from sample source depending on variations of the sample matrix.
7. Apparatus
7.1 LC/MS/MS System:
7.1.1 Liquid Chromatography (LC) System —AAn LC system is required in order to analyze samples. AAn LC system that is
capable of performing at the flows, pressures, controlled temperatures, sample volumes, and requirements of the standard shall be
used.
7.1.2 Analytical Column —A column that achieves adequate resolution shall be used. The retention times and order of elution may
change depending on the column used and need to be monitored. A reverse-phase analytical column with strong embedded basic
ion-pairing groups was used to develop this test method.
7.1.3 Tandem Mass Spectrometer (MS/MS) System —AAn MS/MS system capable of multiple reaction monitoring (MRM)
analysis or a system that is capable of performing at the requirements in this standard shall be used.
7.2 Pressurized Fluid Extraction (PFE) Device (optional)—PFE devices with appropriately-sized appropriately sized extraction
cells are available that will accommodate the wipe sample sizes used in this test method. Cells shall be made of stainless steel or
Additional information about CWC and thiodiglycol is available on the Internet at http://www.opcw.org (2009).
A Waters Alliance®Alliance High Performance Liquid Chromatography (HPLC) System was used to develop this test method and generate the precision and bias data
presented in Section 17. The sole source of supply of the apparatus known to the committee at this time is Waters Corporation, Milford, MA 01757. If you are aware of
alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible
technical committee,Any HPLC system that produces results that meet or exceed the performance criteria of this test method which you may attend.may be used.
A SIELC- Primesep SB™SB 5 μm, 100 Å particle, 150 by 2.1 mm column was used to develop this test method and generate the precision and bias data presented in
Section 17. The sole source of supply of the apparatus known to the committee at this time is SIELC Technologies, Prospect Heights, IL 60070. If you are aware of alternative
suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical
committee,Any column that produces results that meet or exceed the performance criteria of this test method which you may attend.may be used.
A Waters Quattro micro™micro API mass spectrometer was used to develop this test method and generate the precision and bias data presented in Section 17. The sole
source of supply of the apparatus known to the committee at this time is Waters Corporation, Milford, MA 01757. If you are aware of alternative suppliers, please provide
this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee,Any mass
spectrometer that produces results that meet or exceed the performance criteria of this test method which you may attend.may be used.
A Dionex Accelerated Solvent Extraction (ASE®(ASE 200) system with appropriately-sized appropriately sized extraction cells was used to develop this test method
and generate the precision and bias data presented in Section 17. The sole source of supply of the apparatus known to the committee at this time is Dionex Corporation,
Sunnyvale, CA 94088. If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful
consideration at a meeting of the responsible technical committee,Any extraction system that produces results that meet or exceed the performance criteria of this test method
which you may attend.may be used.
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other material capable of withstanding the pressure requirements (≥2000 psi) necessary for this procedure. A pressurized fluid
extraction device shall be used that can meet the necessary requirements in this test method.
7.3 Glass Fiber Filters.
7.4 Solvent Blowdown Device, with 24- and 50-vial capacity trays and a water bath maintained at 50 to 60°C60 °C for analyte
concentration from solvent volumes up to 50 mL or similar device shall be used.
7.5 Sonication Device, capable of holding 40 mL vials.
7.6 Nitrogen Evaporation Device, equipped with a water bath that can be maintained at 50°C50 °C for final analyte concentration
(<10 mL volume) or similar shall be used.
7.7 Wipes.
7.8 Filter Paper.
7.9 Kuderna-Danish Vials (K-D),(K-D) Vials, 10 mL.
7.10 Amber VOA Vials, 40 mL for sonication, or 60 mL for PFE.
7.11 Filtration Device:
7.11.1 Hypodermic Syringe—A luer-lock tip glass syringe capable of holding a syringe driven syringe-driven filter unit.
7.11.1.1 A 25 or 50 mL luer-lock tip glass syringe size is recommended in this test method.
7.11.2 Filter Units —A filter unit of polytetrafluoroethylene (PTFE) 0.20 μm was used for the sonication extraction and a
polyvinylidene fluoride (PVDF) 0.22 μm was used for the PFE process. Either PTFE or PVDF filter units shall be used.
11 10
Whatman Glass Fiber Filters 19.8 mm, Part #No. 047017, specially designed for the PFE system were used to develop this test method and generate the precision
and bias data presented in Section 17. The sole source of supply of the apparatus known to the committee at this time is Dionex Corporation, Sunnyvale, CA 94088. If you
are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of
the responsible technical committee,Any filter that produces results that meet or exceed the performance criteria of this test method which you may attend.may be used.
The sole source of supply of the apparatus (a TurboVap LV) known to the committee at this time is A TurboVap LV by Caliper Life Sciences, Hopkinton, MA 01748.
If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting
of the responsible technical committee,01748 was used. Any evaporation system that produces results that meet or exceed the performance criteria of which you may
attend.this test method may be used.
The sole source of supply of the apparatus (a Bransonic® Model 5510 Sonicator) known to the committee at this time is A Bransonic Model 5510 Sonicator by Branson
Ultrasonics, Americas Headquarters, 41 Eagle Road, Danbury, CT 06810. If you are aware of alternative suppliers, please provide this information to ASTM International
Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee,06810 was used. Any sonicator that produces results that
meet or exceed the performance criteria of which you may attend.this test method may be used.
The sole source of supply of the apparatus (N-Evap An N-Evap 24-port nitrogen evaporation device) known to the committee at this time is device by Organomation
Associates Inc., West Berlin, MA 01503. If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will
receive careful consideration at a meeting of the responsible technical committee,01503 was used. Any evaporation system that produces results that meet or exceed the
performance criteria of which you may attend.this method may be used.
Certi-Gauze™Certi-Gauze pads, sterile, 3 by 3 in. (Part #No. 52639), were used to develop this test method and generate the precision and bias data presented in Section
17. The sole source of supply of the pads known to the committee at this time is Certified Safety Mfg, Kansas City, MO. If you are aware of alternative suppliers, please
provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee,Any
gauze pad that produces results that meet or exceed the performance criteria of this test method which you may attend.may be used.
Whatman 42 ashless, 125 mm filter paper (Catalog #No. 1442 125) werewas used to develop this test method and generate the precision and bias data presented in
Section 17. The sole source of supply of the filter paper known to the committee at this time is Whatman Inc., Building 1, 800 Centennial Avenue, Piscataway, NJ 08854.
If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting
of the responsible technical committee,Any filter paper that produces results that meet or exceed the performance criteria of this test method which you may attend.may
be used.
An IC Millex®-LG Syringe Driven Millex-LG Syringe-Driven Filter Unit PTFE 0.20 μm (Catalog #No. SLLGC25NS) and Millex®-GV Syringe Driven Millex-GV
Syringe-Driven Filter Unit PVDF 0.22 μm (Catalog #No. SLGV033NS) were used to develop this test method and generate the precision and bias data presented in Section
17. The sole source of supply of the filter units known to the committee at this time is Millipore Corporation, 290 Concord Road, Billerica, MA 01821. If you are aware of
alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible
technical committee,Any filter that produces results that meet or exceed the performance criteria of this test method which you may attend.may be used.
E2838 − 21
NOTE 1—Any filter unit brand may be used that meets the requirements of the test method.method may be used.
8. Reagents and Materials
8.1 Purity of Reagents—High Performance Liquid Chromatographyperformance liquid chromatography (HPLC) pesticide residue
analysis and spectrophotometry grade chemicals shall be used in all tests. Unless indicated otherwise, it is intended that all reagents
shall conform to the Committee on Analytical Reagents of the American Chemical Society. Other reagent grades may be used
provided they are first determined to be of sufficiently high purity to permit their use without affecting the accuracy of the
measurements.
8.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water conforming to
ASTM Type I of Specification D653D1193. It shall be demonstrated that this water does not contain contaminants at concentrations
sufficient to interfere with the analysis.
8.3 Gases—Nitrogen (purity ≥97%)≥97 %) and argon (purity ≥99.999%).≥99.999 %).
8.4 Acetic Acid (CH CO H, CAS# CAS No. 64-19-7).
3 2
8.5 Acetone (CH COCH , CAS #No. 67-64-1).
3 3
8.6 Acetonitrile (CH CN, CAS #No. 75-05-8).
8.7 Ammonium Formate (NH CO H, CAS #No. 540-69-2).
4 2
8.8 Formic Acid (HCO H, CAS# CAS No. 64-18-6).
8.9 Methanol (CH OH, CAS #No. 67-56-1).
8.10 Thiodiglycol (S(CH CH OH) , CAS #No. 111-48-8).
2 2 2
8.11 3,3’-Thiodipropanol (S(CH CH CH OH) , CAS #No. 10595-09-2).
2 2 2 2
8.12 Drying Agent.
8.13 Sand—Reagent Gradegrade sand, such as Ottawa Sand.sand.
9. Hazards
9.1 Normal laboratory safety applies to this method. Analysts shall wear safety glasses, gloves, and lab coats when working in
the lab. Analysts shall review the Material Safety Data Sheets (MSDS) for all reagents used in this method and shall be fully trained
to perform the tests.
10. Glassware Washing, Sampling, and Preservation
10.1 Glassware Washing—All glassware is washed in hot tap water with a detergent and rinsed in hot water conforming to ASTM
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, D.C. For suggestions on the testing of reagents not listed by
the American Chemical Society, see AnnualAnalar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulators,Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
Varian – Chem Tube – Hydromatrix®,Hydromatrix, 1 kg (Part #No. 198003) was used to develop this test method and generate the precision and bias data presented
in Section 17 by recommendation of the PFE manufacturer. The sole source of supply of the drying agent known to the committee at this time is Agilent Technologies, United
States, 5301 Stevens Creek Blvd, Santa Clara, CA 95051. If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your
comments will receive careful consideration at a meeting of the responsible technical committee,Any drying agent that produces results that meet or exceed the performance
criteria of this test method which you may attend. (Note: Some drying agents have been shown to clog PFE transfer lines.)may be used.
E2838 − 21
Type I of Specification D653D1193. The glassware is then dried and heated in an oven at 250°C250 °C for 15 to 30 minutes.min.
All glassware is subsequently cleaned with acetone and methanol, respectively.
10.2 Sampling—The wipe sample is folded and placed into a 40 mL pre-cleaned amber glass VOA vial with a PTFE-lined cap
in the field. The wipe is shipped to the laboratory between 0°C0 °C and 6°C.6 °C. The required surrogate and matrix spike solutions
are added to the wipe in the VOA vial at the laboratory. Field blanks are needed to follow conventional sampling practices.
10.3 Preservation—Store samples between 0°C0 °C and 6°C6 °C from the time of collection until analysis. Analyze the sample
within 7seven days of collection.
11. Preparation of LC/MS/MS
11.1 LC Chromatograph Operating Conditionschromatograph operating conditions for the LC used to develop this test method:
11.1.1 Injection volumes of all calibration standards and samples are 10 μL. The first sample analyzed after the calibration curve
is a blank to ensure there is no carry-over. The gradient conditions for the liquid chromatograph are shown in Table 2.
11.1.2 Temperatures—Column, 30°C;30 °C; Sample compartment, 15°C.15 °C.
11.1.3 Seal Wash—Solvent: 50% Acetonitrile/50%50 % Acetonitrile ⁄50 % Water; Time: 5 minutes.min.
11.1.4 Needle Wash—Solvent: 50% Acetonitrile/50%50 % Acetonitrile ⁄50 % Water; Normal Wash,normal wash, approximately a
13 second 13-s wash time.
11.1.5 Autosampler Purge—Three loop volumes.
11.1.6 Specific instrument manufacturer wash and purge specifications shall be followed in order to eliminate sample carry-over
in the analysis.
11.2 Mass Spectrometer Parameters:
11.2.1 To acquire the maximum number of data points per SRM channel while maintaining adequate sensitivity, the tune
parameters shall be optimized according to the instrument. Each peak requires at least 10ten scans per peak for adequate
quantitation. This standard contains one target compound and one surrogate which are in different SRM experiment windows in
order to optimize the number of scans and sensitivity. Variable parameters regarding retention times, SRM transitions, and cone
and collision energies are shown in Table 3 for the mass spectrometer used to develop this test method. Other mass spectrometer
parameters used in the development of this method are listed below:
The instrument is set in the Electrospray (+) positive source setting.
Capillary Voltage: 3.5 kV
Cone: Variable depending on analyte (Table 3)
Extractor: 2 V
RF Lens: 0.2 V
Source Temperature: 120°C
Source Temperature: 120 °C
Desolvation Temperature: 300°C
TABLE 2 Gradient Conditions for Liquid Chromatography
Percent
500 mM
Time Flow Percent Percent Ammonium
(min) (μL/min) CH CN Water Formate/
2%Formate/2 %
Formic Acid
0 300 0 95 5
2 300 0 95 5
3 300 50 45 5
6 300 90 5 5
10 300 90 5 5
12 300 0 95 5
16 300 0 95 5
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TABLE 3 Retention Times, SRM Transitions, and Analyte-Specific
Mass Spectrometer Parameters
SRM Mass Retention Cone Collision
Analyte Transition (m/z) Time Voltage 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
Desolvation Temperature: 300 °C
Desolvation Gas Flow: 500 L/hr
Desolvation Gas Flow: 500 L/h
Cone Gas Flow: 25 L/hr
Cone Gas Flow: 25 L/h
Low Mass Resolution 1: 14.5
High Mass Resolution 1: 14.5
Io
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