ASTM E2787-11(2016)

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)

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.5  
5.2 This method has been investigated for use with soil.
SCOPE
1.1 This procedure covers the determination of thiodiglycol (TDG) in soil using pressurized fluid extraction (PFE). A commercially available PFE system2 was 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 Limit (MDL) and Reporting 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 and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 31-May-2016
• ICS: 13.080.10 - Chemical characteristics of soils
• Technical Committee: D34 - Waste Management
• Drafting Committee: D34.01.06 - Analytical Methods

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: E2787 − 11 (Reapproved 2016)
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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
1.1 This procedure covers the determination of thiodiglycol
(TDG) in soil using pressurized fluid extraction (PFE). A
2. Referenced Documents
commercially available PFE system was used, followed by
2.1 ASTM Standards:
analysis using liquid chromatography (LC), and detected with
D653Terminology Relating to Soil, Rock, and Contained
tandemmassspectrometry(MS/MS).TDGisqualitativelyand
Fluids
quantitativelydeterminedbythismethod.Thismethodadheres
D1193Specification for Reagent Water
to single reaction monitoring (SRM) mass spectrometry.
D3694Practices for Preparation of Sample Containers and
1.2 The Method Detection Limit (MDL) and Reporting
for Preservation of Organic Constituents
Range for TDG are listed in Table 1.
D3740Practice for Minimum Requirements for Agencies
1.2.1 TheMDLisdeterminedfollowingtheCodeofFederal
Engaged inTesting and/or Inspection of Soil and Rock as
Regulations, 40 CFR Part 136, Appendix B.
Used in Engineering Design and Construction
1.2.2 The reporting limit (RL) is calculated from the con-
E2554Practice for Estimating and Monitoring the Uncer-
centrationoftheLevel1calibrationstandardasshowninTable
tainty of Test Results of a Test Method Using Control
4. The RL for this method is 200 ppb. Reporting range
Chart Techniques
concentrations are calculated from Table 4 concentrations
2.2 Other Documents:
assuminga5µL injection of the lowest level calibration
EPApublicationSW-846,TestMethodsforEvaluatingSolid
standard, 5 g sample, anda2mL final extract volume. 4
Waste, Physical/Chemical Methods
1.3 Units—The values stated in SI units are to be regarded
40 CFR Part 136, Appendix B,The Code of Federal Regu-
asstandard.Nootherunitsofmeasurementareincludedinthis
lations
standard.
3. Terminology
1.4 This standard does not purport to address all of the
3.1 Abbreviations:
safety concerns, if any, associated with its use. It is the
–3
3.1.1 mM—millimolar,1×10 moles/L
responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter-
3.1.2 ND—non-detect
mine the applicability of regulatory limitations prior to use.
3.1.3 SRM—single reaction monitoring
1.5 This international standard was developed in accor-
3.1.4 MRM—multiple reaction monitoring
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
4. Summary of Test Method
Development of International Standards, Guides and Recom-
4.1 This is a performance based method, and modifications
are allowed to improve performance.
This test method is under the jurisdiction ofASTM Committee D34 on Waste
Management and is the direct responsibility of Subcommittee D34.01.06 on
Analytical Methods. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved June 1, 2016. Published June 2016. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 2011. Last previous edition approved in 2011 as E2787–11. DOI: Standardsvolumeinformation,refertothestandard’sDocumentSummarypageon
10.1520/E2787-11R16. the ASTM website.
2 4
The PFE system that was used to develop this test method was Accelerated Available from National Technical Information Service (NTIS), U.S. Depart-
Solvent Extraction (ASE®) which is a patented technique by Dionex, Sunnyvale, ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
CA 94088. 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
E2787 − 11 (2016)
TABLE 1 Method Detection Limit and Reporting Range
7.1.1 Liquid Chromatography (LC) System —A complete
Analyte MDL (ppb) Reporting Range (ppb) LC system is required in order to analyze samples. Any LC
Thiodiglycol 54 200–16 000 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 col-
umn with strong embedded basic ion-pairing groups was used
4.2 For TDG analysis, samples are shipped to the lab
todevelopthistestmethod.Anycolumnthatachievesadequate
between 0 and 6°C. In the lab, the soils are spiked with
resolution may be used. The retention times and order of
3,3’-thiodipropanol (TDP, surrogate) and extracted by PFE.
elutionmaychangedependingonthecolumnusedandneedto
Theextractisfilteredusingasyringedrivenfilterunit,reduced
be monitored.
in volume, reconstituted with water, and analyzed directly by
7.1.3 Tandem Mass Spectrometer (MS/MS) System —A
LC/MS/MS within 7 days.
MS/MS system capable of multiple reaction monitoring
4.3 TDG and TDP are identified by retention time and one
(MRM)analysisoranysystemthatiscapableofperformingat
SRM transition. The target analyte and surrogate are quanti-
the requirements in this standard may be used.
tated using the SRM transitions utilizing an external calibra-
7.2 Pressurized Fluid Extraction Device:
tion. The final report issued for each sample lists the concen-
7.2.1 A PFE system was used for this test method with
tration of TDG and the TDP recovery.
appropriately-sized extraction cells. Cells are available that
will accommodate the 5–10 g sample sizes used in this test
5. Significance and Use
method. Cells should be made of stainless steel or other
5.1 TDG is a Schedule 2 compound under the Chemical
material capable of withstanding the pressure requirements
Weapons Convention (CWC). Schedule 2 chemicals include
(≥2000psi)necessaryforthisprocedure.Anypressurizedfluid
those that are precursors to chemical weapons, chemical
extraction device may be used that can meet the necessary
weapons agents or have a number of other commercial uses.
requirements in this test method.
They are used as ingredients to produce insecticides,
7.2.2 Whatman Glass Fiber Filters—19.8 mm, Dionex
herbicides, lubricants, and some pharmaceutical products.
Corporation, Part # 047017 were used because they are
Schedule2chemicalscanbefoundinapplicationsunrelatedto
specially designed for the PFE system used or equivalent.
chemical weapons.TDG is both a mustard gas precursor and a
7.3 A solvent blowdown device with 24- and 50-vial
degradant as well as an ingredient in water-based inks, ball-
capacity trays and a water bath maintained at 60°C for analyte
point pen inks, dyes, and some pesticides.
concentration from solvent volumes up to 50 mL or similar
5.2 This method has been investigated for use with soil.
device may be used.
7.4 A nitrogen evaporation device equipped with a water
6. Interferences
bath that can be maintained at 50°C for final analyte concen-
6.1 Methodinterferencesmaybecausedbycontaminantsin
tration (<10 mL volume) or similar may be used.
solvents, reagents, glassware, and other apparatus producing
7.5 Filtration Device:
discrete artifacts or elevated baselines. All of these materials
7.5.1 Hypodermic Syringe—A luer-lock tip glass syringe
are demonstrated to be free from interferences by analyzing
capableofholdingasyringedrivenfilterunitofPTFE0.20µm
laboratory reagent blanks under the same conditions as
or similar may be used.
samples.
7.5.1.1 A 25 or 50 mL luer-lock tip glass syringe size is
6.2 All glassware is washed in hot water with a detergent
recommended in this test method.
and rinsed in hot water followed by distilled water. The
7.5.2 Filter—A filter unit of PTFE 0.20 µm or similar may
glassware is then dried and heated in an oven at 250°C for 15
be used.
to 30 min.All glassware is subsequently cleaned with acetone,
then methanol.
A Waters Alliance® High Performance Liquid Chromatography (HPLC)
6.3 All reagents and solvents should be of pesticide residue System was used to develop this test method. Waters Corporation, Milford, MA
01757.
purity or higher to minimize interference problems.
SIELC–Primesep 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
6.4 Matrix interferences may be caused by contaminants
may be used. SIELC Technologies, Prospect Heights, IL 60070.
that are co-extracted from the sample. The extent of matrix
AWatersQuattromicro™APImassspectrometerwasusedtodevelopthistest
interferences can vary considerably from sample source de-
method. Waters Corporation, Milford, MA 01757.
pending on variations of the sample matrix.
ADionexAcceleratedSolventExtraction(ASE®200)systemwasusedforthis
test method with appropriately-sized extraction cells. Dionex Corporation,
Sunnyvale, CA 94088.
7. Apparatus
A TurboVap LV was used in this test method from Caliper Life Sciences,
Hopkinton, MA 01748.
7.1 LC/MS/MS System:
A N-Evap 24-port nitrogen evaporation device was used in this test method
from Organomation Associates Inc., West Berlin, MA 01503.
Millex® HV Syringe Driven Filter Unit PTFE 0.20 mm (Millipore
AdditionalinformationaboutCWCandthiodiglycolisavailableontheInternet Corporation,Catalog#SLLGC25NS)wasshowntoperforminthistestmethod,any
at http://www.opcw.org (2009). filter unit may be used if it can perform to the specifications in this test method.
E2787 − 11 (2016)
7.5.2.1 Discussion—Any filter unit may be used that meets strated to be free of interferences. This test method requires at
the requirements of the test method. leasta5g sample size per analysis. A 100 g sample amount
should be collected to allow for quality control samples and
8. Reagents and Materials
re-analysis. Conventional sampling practices should be fol-
8.1 Purity of Reagents—HighPerformanceLiquidChroma-
lowed.
tography (HPLC) pesticide residue analysis and spectropho-
10.2 Preservation—Store samples between 0 and 6°C from
tometry grade chemicals shall be used in all tests. Unless
thetimeofcollectionuntilanalysis.Analyzethesamplewithin
indicated otherwise, it is intended that all reagents shall
7 days of collection.
conform to the Committee on Analytical Reagents of the
American Chemical Society. Other reagent grades may be
11. Preparation of LC/MS/MS
used provided they are first determined to be of sufficiently
11.1 LC Chromatograph Operating Conditions:
highpuritytopermittheirusewithoutaffectingtheaccuracyof
11.1.1 Injection volumes of all calibration standards and
the measurements.
samples are 5 µL and are composed of primarily water. The
8.2 Purity of Water—Unless otherwise indicated, references
first sample analyzed after the calibration curve is a water
towatershallbeunderstoodtomeanreagentwaterconforming
blank to ensure there is no carry-over. The gradient conditions
toType1ofSpecificationD1193.Itmustbedemonstratedthat
for the liquid chromatograph are shown in Table 2.
this water does not contain contaminants at concentrations
11.1.2 Temperatures—Column, 30°C; Sample
sufficient to interfere with the analysis.
compartment, 15°C.
11.1.3 Seal Wash—Solvent: 50% Acetonitrile/50% Water;
8.3 Gases—Ultrapure nitrogen and argon.
Time: 5 min.
8.4 Acetonitrile (CAS # 75-05-8).
11.1.4 Needle Wash—Solvent: 50% Acetonitrile/50% Wa-
8.5 2-Propanol (CAS # 67-63-0).
ter; Normal Wash, approximately a 13-s wash time.
11.1.5 Autosampler Purge—Three loop volumes.
8.6 Methanol (CAS # 67-56-1).
11.1.6 Specific instrument manufacturer wash and purge
8.7 Acetone (CAS # 67-64-1).
specifications should be followed in order to eliminate sample
8.8 Ammonium Formate (CAS # 540-69-2).
carry-over in the analysis.
8.9 Formic Acid (64-18-6). 11.2 Mass Spectrometer Parameters:
11.2.1 To acquire the maximum number of data points per
8.10 Thiodiglycol (CAS # 111-48-8).
SRM channel while maintaining adequate sensitivity, the tune
8.11 3,3’-Thiodipropanol (CAS # 10595-09-2).
parameters may be optimized according to your instrument.
8.11.1 Ottawa Sand Standard, (CAS # 14808-60-7) or
Each peak requires at least 10 scans per peak for adequate
equivalent.
quantitation. This standard contains one target compound and
8.11.2 Drying Agent, Varian–Chem Tube–Hydromatrix®,
onesurrogatewhichareindifferentSRMexperimentwindows
1kg(Part#198003)wasusedbecauseitwasrecommendedby
in order to optimize the number of scans and sensitivity.
the PFE manufacturer or equivalent.
Variable parameters regarding retention times, SRM
transitions, and cone and collision energies are shown in Table
9. Hazards
3. Mass spectrometer parameters used in the development of
9.1 Normal laboratory safety applies to this method. Ana-
this method are listed in Table 3.
lysts should wear safety glasses, gloves, and lab coats when
workinginthelab.AnalystsshouldreviewtheMaterialSafety
TABLE 2 Gradient Conditions for Liquid Chromatography
Data Sheets (MSDS) for all reagents used in this method.
Percent
500 mM
10. Sampling
Time Flow Percent Percent
Ammonium
(min) (µL/min) CH CN Water
10.1 Sampling—Grab samples must be collected in pre- Formate/2%
Formic Acid
cleaned amber glass bottles with Teflon® lined caps demon-
0 300 0 95 5
2 300 0 95 5
Reagent Chemicals, American Chemical Society Specifications, American
3 300 50 45 5
Chemical Society, Washington, D.C. 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 Formulators, U.S. Pharmacopeial Convention, Inc. (USPC), 16 300 0 95 5
Rockville, MD.
E2787 − 11 (2016)
TABLE 3 Retention Times, SRM Transitions, and Analyte-Specific
transition of each analyte is used for quantitation and confir-
Mass Spectrometer Parameters
mation. This gives confirmation by isolating the parent ion,
SRM Mass Retention Cone Collision
fragmenting it to the product ion, and also relating it to the
Analyte Transition Time Voltage Energy
retention time in the calibration standard.
(Parent > Product) (min) (Volts) (eV)
12.2.2 Thecalibrationsoftwaremanualshouldbeconsulted
Thiodiglycol 123.1 > 104.9 2.75 18 5
3,3’-Thiodipropanol 151.2 > 1
...

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 E2787 − 11 (Reapproved 2016)
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 was 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 Limit (MDL) and Reporting 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 and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
D653 Terminology Relating to Soil, Rock, and Contained Fluids
D1193 Specification for Reagent Water
D3694 Practices for Preparation of Sample Containers and for Preservation of Organic Constituents
D3740 Practice for Minimum Requirements for Agencies Engaged in Testing and/or Inspection of Soil and Rock as Used in
Engineering Design and Construction
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
40 CFR Part 136, Appendix B, The Code of Federal Regulations
3. Terminology
3.1 Abbreviations:
-3
3.1.1 mM—millimolar, 1 × 10 moles/L
This test method is under the jurisdiction of ASTM Committee E54 on Homeland Security Applications and is the direct responsibility of Subcommittee E54.03 on
Decontamination.
Current edition approved Jan. 1, 2011June 1, 2016. Published March 2011June 2016. Originally approved in 2011. Last previous edition approved in 2011 as E2787 – 11.
DOI: 10.1520/E2787-11.10.1520/E2787-11R16.
The PFE system that was used to develop this test method was Accelerated Solvent Extraction (ASE®) which is a patented technique by Dionex, Sunnyvale, CA 94088.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. 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.htm
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E2787 − 11 (2016)
TABLE 1 Method Detection Limit and Reporting Range
Analyte MDL (ppb) Reporting Range (ppb)
Thiodiglycol 54 200–16 000
3.1.2 ND—non-detect
3.1.3 SRM—single reaction monitoring
3.1.4 MRM—multiple reaction monitoring
4. Summary of Test Method
4.1 This is a 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. 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 filter unit, reduced in volume, reconstituted
with water, and analyzed directly by LC/MS/MS within 7 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.
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°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 —A 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 :
Additional information about CWC and thiodiglycol is available on the Internet at http://www.opcw.org (2009).
A Waters Alliance® High Performance Liquid Chromatography (HPLC) System was used to develop this test method. Waters Corporation, Milford, MA 01757.
SIELC–Primesep 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™ API mass spectrometer was used to develop this test method. Waters Corporation, Milford, MA 01757.
A Dionex Accelerated Solvent Extraction (ASE® 200) system was used for this test method with appropriately-sized extraction cells. Dionex Corporation, Sunnyvale,
CA 94088.
E2787 − 11 (2016)
7.2.1 A PFE system was used for this test method with appropriately-sized extraction cells. Cells are available that will
accommodate the 5–10 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 # 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°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°C for final analyte concentration
(<10 mL volume) or similar may be used.
7.5 Filtration Device:
7.5.1 Hypodermic Syringe—A luer-lock tip glass syringe capable of holding a 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 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 # 75-05-8).
8.5 2-Propanol (CAS # 67-63-0).
8.6 Methanol (CAS # 67-56-1).
8.7 Acetone (CAS # 67-64-1).
8.8 Ammonium Formate (CAS # 540-69-2).
8.9 Formic Acid (64-18-6).
8.10 Thiodiglycol (CAS # 111-48-8).
8.11 3,3’-Thiodipropanol (CAS # 10595-09-2).
8.11.1 Ottawa Sand Standard, (CAS # 14808-60-7) or equivalent.
8.11.2 Drying Agent, Varian–Chem Tube–Hydromatrix®, 1kg (Part # 198003) was used because it was recommended by the
PFE manufacturer or equivalent.
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 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.
A TurboVap LV was used in this test method from Caliper Life Sciences, Hopkinton, MA 01748.
A N-Evap 24-port nitrogen evaporation device was used in this test method from Organomation Associates Inc., West Berlin, MA 01503.
Millex® HV Syringe Driven Filter Unit PTFE 0.20 mm (Millipore Corporation, Catalog # SLLGC25NS) was shown to perform in this test 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 Suggestions on the testing of reagents not listed by
the American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulators, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
E2787 − 11 (2016)
10.2 Preservation—Store samples between 0 and 6°C from the time of collection until analysis. Analyze the sample within 7
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; Sample compartment, 15°C.
11.1.3 Seal Wash—Solvent: 50% Acetonitrile/50% Water; Time: 5 min.
11.1.4 Needle Wash—Solvent: 50% Acetonitrile/50% Water; 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 10 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.
Capillary Voltage: 3.5 kV
Cone: Variable depending on analyte (Table 3)
Extractor: 2 V
RF Lens: 0.2 V
Source Temperature: 120°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 T
...