ASTM E2787-21

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: E2787 − 11 (Reapproved 2016) E2787 − 21
Standard Test Method for
Determination of Thiodiglycol in Soil Using Pressurized
Fluid Extraction Followed by Single Reaction Monitoring
Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/
MS)
This standard is issued under the fixed designation E2787; 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 covers the determination of thiodiglycol (TDG) in soil using pressurized fluid extraction (PFE). A
commercially available PFE system wasis used, followed by analysis 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 The Method Detection Limitmethod detection limit (MDL) and Reporting Rangereporting range for TDG are listed in Table
1.
1.2.1 The MDL is determined following the Code of Federal Regulations, 40 CFR Part 136, Appendix B.
1.2.2 The reporting limit (RL) is calculated from the concentration of the Level 1 calibration standard as shown in Table 4. The
RL for this method is 200 ppb. Reporting range concentrations are calculated from Table 4 concentrations assuming a 5 μL
injection of the lowest level calibration standard, 5 g sample, and a 2 mL final extract volume.
1.3 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this
standard.
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.
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 June 2016May 2021. Originally approved in 2011. Last previous edition approved in 20112016 as
E2787 – 11.E2787 – 11 (2016). DOI: 10.1520/E2787-11R16.10.1520/E2787-21.
The PFE system that was used to develop this test method was Accelerated Solvent Extraction (ASE®)(ASE) which is a patented technique by Dionex, Sunnyvale, CA
94088.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E2787 − 21
TABLE 1 Method Detection Limit and Reporting Range
Analyte MDL (ppb) Reporting Range (ppb)
Thiodiglycol 54 200–16 000
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
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,SW-846 Test Methods for Evaluating Solid Waste, Physical/Chemical Methods
40 CFR Part 136, Appendix B,B The 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
4. Summary of Test Method
4.1 This is a performance based performance-based method, and modifications are allowed to improve performance.
4.2 For TDG analysis, samples are shipped to the lab between 0 and 6°C.6 °C. In the lab, the soils are spiked with
3,3’-thiodipropanol (TDP, surrogate) and extracted by PFE. The extract is filtered using a syringe driven syringe-driven filter unit,
reduced in volume, reconstituted with water, and analyzed directly by LC/MS/MS within 7seven days.
4.3 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 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 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. TDG is both a mustard gas precursor and a degradant as well as an ingredient in
water-based inks, ballpoint pen inks, dyes, and some pesticides.
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.
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.htmhttp://www.epa.gov/epawaste/hazard/testmethods/index.htm.
Additional information about CWC and thiodiglycol is available on the Internet at http://www.opcw.org (2009).
E2787 − 21
5.2 This method has been investigated for use with soil.
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 are demonstrated to be free from interferences by analyzing laboratory reagent
blanks under the same conditions as samples.
6.2 All glassware is washed in hot water with a detergent and rinsed in hot water followed by distilled water. The glassware is
then dried and heated in an oven at 250°C250 °C for 15 to 30 min. All glassware is subsequently cleaned with acetone, then
methanol.
6.3 All reagents and solvents should be of pesticide residue purity or higher to minimize interference problems.
6.4 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 —A complete LC system is required in order to analyze samples. Any LC system that
is capable of performing at the flows, pressures, controlled temperatures, sample volumes, and requirements of the standard may
be used.
7.1.2 Analytical Column —A reverse-phase analytical column with strong embedded basic ion-pairing groups was used to
develop this test method. Any column that achieves adequate resolution may be used. The retention times and order of elution may
change depending on the column used and need to be monitored.
7.1.3 Tandem Mass Spectrometer (MS/MS) System —AAn MS/MS system capable of multiple reaction monitoring (MRM)
analysis or any system that is capable of performing at the requirements in this standard may be used.
7.2 Pressurized Fluid Extraction Device:
7.2.1 A PFE system was used for this test method with appropriately-sized appropriately sized extraction cells. Cells are available
that will accommodate the 5–10 5 to 10 g sample sizes used in this test method. Cells should be made of stainless steel or other
material capable of withstanding the pressure requirements (≥2000 psi) necessary for this procedure. Any pressurized fluid
extraction device may be used that can meet the necessary requirements in this test method.
7.2.2 Whatman Glass Fiber Filters—19.8 mm, Dionex Corporation, Part #No. 047017 were used because they are specially
designed for the PFE system used or equivalent.
7.3 A solvent blowdown device with 24- and 50-vial capacity trays and a water bath maintained at 60°C60 °C for analyte
concentration from solvent volumes up to 50 mL or similar device may be used.
7.4 A 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 may be used.
A Waters Alliance®Alliance High Performance Liquid Chromatography (HPLC) System was used to develop this test method. Waters Corporation, Milford, MA 01757.
SIELC–Primesep SB™SB 5 μm, 100 Å particle, 150 mm × 2.1 mm particle size was used to develop this test method, any column that achieves adequate resolution
may be used. SIELC Technologies, Prospect Heights, IL 60070.
A Waters Quattro micro™micro API mass spectrometer was used to develop this test method. Waters Corporation, Milford, MA 01757.
A Dionex Accelerated Solvent Extraction (ASE®(ASE 200) system was used for this test method with appropriately-sized appropriately sized extraction cells. Dionex
Corporation, Sunnyvale, CA 94088.
A TurboVap LV was used in this test method from Caliper Life Sciences, Hopkinton, MA 01748.
AAn N-Evap 24-port nitrogen evaporation device was used in this test method from Organomation Associates Inc., West Berlin, MA 01503.
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7.5 Filtration Device:
7.5.1 Hypodermic Syringe—A luer-lock tip glass syringe capable of holding a syringe driven syringe-driven filter unit of PTFE
0.20 μm or similar may be used.
7.5.1.1 A 25 or 50 mL luer-lock tip glass syringe size is recommended in this test method.
7.5.2 Filter—A filter unit of PTFE 0.20 μm or similar may be used.
7.5.2.1 Discussion—Any filter unit may be used that meets the requirements of the test method.
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
Type 1 of Specification D1193. It must be demonstrated that this water does not contain contaminants at concentrations sufficient
to interfere with the analysis.
8.3 Gases—Ultrapure nitrogen and argon.
8.4 Acetonitrile (CAS #No. 75-05-8).
8.5 2-Propanol (CAS #No. 67-63-0).
8.6 Methanol (CAS #No. 67-56-1).
8.7 Acetone (CAS #No. 67-64-1).
8.8 Ammonium Formate (CAS #No. 540-69-2).
8.9 Formic Acid (64-18-6).
8.10 Thiodiglycol (CAS #No. 111-48-8).
8.11 3,3’-Thiodipropanol (CAS #No. 10595-09-2).
8.11.1 Ottawa Sand Standard, (CAS #No. 14808-60-7) or equivalent.
8.11.2 Drying Agent, Varian–Chem Tube–Hydromatrix®, 1kg (Part #Tube–Hydromatrix, 1 kg (Part No. 198003) was used
because it was recommended by the PFE manufacturer or equivalent.
Millex®Millex HV Syringe Driven Filter Unit PTFE 0.20 mm (Millipore Corporation, Catalog #No. SLLGC25NS) was shown to perform in this test method,method;
any filter unit may be used if it can perform to the specifications in this test method.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, D.C. For Suggestionssuggestions 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.
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9. Hazards
9.1 Normal laboratory safety applies to this method. Analysts should wear safety glasses, gloves, and lab coats when working in
the lab. Analysts should review the Material Safety Data Sheets (MSDS) for all reagents used in this method.
10. Sampling
10.1 Sampling—Grab samples must be collected in pre-cleaned amber glass bottles with Teflon® lined PTFE-lined caps
demonstrated to be free of interferences. This test method requires at least a 5 g sample size per analysis. A 100 g sample amount
should be collected to allow for quality control samples and re-analysis. Conventional sampling practices should be followed.
10.2 Preservation—Store samples between 0 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 Conditions:
11.1.1 Injection volumes of all calibration standards and samples are 5 μL and are composed of primarily water. The first sample
analyzed after the calibration curve is a water 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 min.
11.1.4 Needle Wash—Solvent: 50% Acetonitrile/50%50 % Acetonitrile ⁄50 % Water; Normal Wash,normal wash, approximately a
13-s wash time.
11.1.5 Autosampler Purge—Three loop volumes.
11.1.6 Specific instrument manufacturer wash and purge specifications should 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 may be optimized according to your 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. Mass spectrometer parameters used in the development of this method are listed in
Table 3.
The instrument is set in the Electrospray (+) positive source setting.
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 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
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
Desolvation Temperature: 300 °C
Desolvation Gas Flow: 500 L/h
Cone Gas Flow: 25 L/h
Low Mass Resolution 1: 14.5
High Mass Resolution 1: 14.5
Ion Energy 1: 0.5
Entrance Energy: –1
Collision Energy: Variable depending on analyte (Table 3)
Exit Energy: 2
Low Mass Resolution 2: 15
High Mass resolution 2: 15
Ion Energy 2: 0.5
Multiplier: 650
-3
Gas Cell Pirani Gauge: 3.3 × 10 Torr
–3
Gas Cell Pirani Gauge: 3.3 × 10 Torr
Inter-Channel Delay: 0.02 s
Inter-Scan Delay: 0.1 s
Repeats: 1
Span: 0 Daltons
Dwell: 0.1 s
12. Calibration and Standardization
12.1 The mass spectrometer must be calibrated per manufacturer specifications before analysis. In order to obtain valid and
accurate analytical values within the confidence limits, the following procedures must be followed when performing the test
method.
12.2 Calibration and Standardization—To calibrate the instrument, analyze eight calibration standards containing the eight
concentration levels of TDG and TDP in water prior to analysis as shown in Table 4. A calibration stock standard solution is
prepared from standard materials or purchased as certified solutions. Aliquots of Level 8 are then diluted with water to prepare the
desired calibration levels in 2 mL amber glass LC vials. The calibration vials must be used within 24 h to ensure optimum results.
Stock calibration standards are routinely replaced every six months if not previously discarded for quality control failure. The
analyst is responsible for recording initial component weights carefully when working with pure materials and correctly carrying
the weights through the dilution calculations. Calibration standards are not filtered.
12.2.1 Inject each standard and obtain its chromatogram. An external calibration is used in monitoring the SRM transition of each
analyte. Calibration software is utilized to conduct the quantitation of the target analyte and surrogate. The SRM transition of each
analyte is used for quantitation and confirmation. This gives confirmation by isolating the parent ion, fragmenting it to the product
ion, and also relating it to the retention time in the calibration standard.
12.2.2 The calibration software manual should be consulted to use the software correctly. The quantitation method is set as an
external calibration using the peak areas in ppb or ppm units as long as the analyst is consistent. Concentrations may be calculated
using the data system software to generate linear regression or quadratic calibration curves. The calibration curves may be either
TABLE 4 Concentrations of Calibration Standards (PPB)
Analyte/Surrogate LV 1 LV 2 LV 3 LV 4 LV 5 LV 6 LV 7 LV 8
Thiodiglycol 500 1000 2000 4000 8000 16 000 32 000 40 000
3,3’-Thiodipropanol 500 1000 2000 4000 8000 16 000 32 000 40 000
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linear or quadratic depending on your instrument. Forcing the calibration curve through the origin is not recommended. Each
calibration point used to generate the curve must have a calculated percent deviation less than 30%30 % from the generated curve.
12.2.3 Linear calibration may be used if the coefficient of determination, r , is >0.98 for the analyte. The point of origin is
excluded, and a fit weighting of 1/X is used in order to give more emphasis to the lower concentrations. If one of the calibration
standards other than the high or low point causes the r of the curve to be <0.98, this point must be re-injected or a new calibration
curve must be regenerated. If the low or high (or both) point is excluded, minimally a five point five-point curve is acceptable,
but the reporting range must be modified to reflect this change.
12.2.4 Quadratic calibration may be used if the coefficient of determination, r , is >0.99 for the analyte. The point of origin is
excluded, and a fit weighting of 1/X is used in order to give more emphasis to the lower concentrations. If one of the calibration
standards, other than the high or low, causes the curve to be <0.99, this point must be re-injected or a new calibration curve must
be regenerated. If the low and/oror high (or both) point is excluded, a six point six-point curve is acceptable using a quadratic fit.
An initial eight point eight-point curve over the calibration range is suggested in the event that the low or high point must be
excluded to obtain a coefficient of determination >0.99. In this event, the reporting range must be modified to reflect this change.
12.2.5 The retention time window of the SRM transitions must be within 5%5 % of the retention time of the analyte in a midpoint
calibration standard. If this is not the case, re-analyze the calibration curve to determine if there was a shift in retention time during
the analysis, and the sample needs to be re-injected. If the retention time is still incorrect in the sample, refer to the analyte as an
unknown.
12.2.6 A midpoint calibration check standard must be analyzed at the end of each batch of 20 samples or within 24 h after the
initial calibration curve was generated. This end calibration check should be the same calibration standard that was used to generate
the initial curve. The results from the end calibration check standard must have a percent deviation less than 30%30 % from the
calculated concentration for the target analyte and surrogate. If the results are not within these criteria, the problem must be
corrected and either all samples in the batch must be re-analyzed against a new calibration curve or the affected results must be
qualified with an indication that they do not fall within the performance criteria of the test method. If the analyst inspects the vial
containing the end calibration check standard and notices that the sample evaporated affecting the concentration, a new end
calibration check standard may be mad
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