1、Designation: E2787 11 (Reapproved 2016)Standard Test Method forDetermination of Thiodiglycol in Soil Using PressurizedFluid Extraction Followed by Single Reaction MonitoringLiquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)1This standard is issued under the fixed designation E2787; the number
2、 immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1
3、 This procedure covers the determination of thiodiglycol(TDG) in soil using pressurized fluid extraction (PFE). Acommercially available PFE system2was used, followed byanalysis using liquid chromatography (LC), and detected withtandem mass spectrometry (MS/MS). TDG is qualitatively andquantitatively
4、 determined by this method. This method adheresto single reaction monitoring (SRM) mass spectrometry.1.2 The Method Detection Limit (MDL) and ReportingRange for TDG are listed in Table 1.1.2.1 The MDLis determined following the Code of FederalRegulations, 40 CFR Part 136, Appendix B.1.2.2 The report
5、ing limit (RL) is calculated from the con-centration of the Level 1 calibration standard as shown inTable4. The RL for this method is 200 ppb. Reporting rangeconcentrations are calculated from Table 4 concentrationsassuminga5Linjection of the lowest level calibrationstandard, 5 g sample, anda2mLfina
6、l extract volume.1.3 UnitsThe values stated in SI units are to be regardedas standard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this stan
7、dard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:3D653 Terminology Relating to Soil, Rock, and ContainedFluidsD1193 Specification for Reagent WaterD3694 Practices for Preparati
8、on of Sample Containers andfor Preservation of Organic ConstituentsD3740 Practice for Minimum Requirements for AgenciesEngaged in Testing and/or Inspection of Soil and Rock asUsed in Engineering Design and ConstructionE2554 Practice for Estimating and Monitoring the Uncer-tainty of Test Results of a
9、 Test Method Using ControlChart Techniques2.2 Other Documents:EPApublication SW-846, Test Methods for Evaluating SolidWaste, Physical/Chemical Methods440 CFR Part 136, Appendix B, The Code of Federal Regu-lations3. Terminology3.1 Abbreviations:3.1.1 mMmillimolar,110-3moles/L3.1.2 NDnon-detect3.1.3 S
10、RMsingle reaction monitoring3.1.4 MRMmultiple reaction monitoring4. Summary of Test Method4.1 This is a performance based method, and modificationsare allowed to improve performance.1This test method is under the jurisdiction of ASTM Committee E54 onHomeland Security Applications and is the direct r
11、esponsibility of SubcommitteeE54.03 on Decontamination.Current edition approved June 1, 2016. Published June 2016. Originallyapproved in 2011. Last previous edition approved in 2011 as E2787 11. DOI:10.1520/E2787-11R16.2The PFE system that was used to develop this test method was AcceleratedSolvent
12、Extraction (ASE) which is a patented technique by Dionex, Sunnyvale,CA 94088.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page ont
13、he ASTM website.4Available from National Technical Information Service (NTIS), U.S. Depart-ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http:/www.epa.gov/epawaste/hazard/testmethods/index.htmCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken,
14、PA 19428-2959. United States14.2 For TDG analysis, samples are shipped to the labbetween 0 and 6C. In the lab, the soils are spiked with3,3-thiodipropanol (TDP, surrogate) and extracted by PFE.The extract is filtered using a syringe driven filter unit, reducedin volume, reconstituted with water, and
15、 analyzed directly byLC/MS/MS within 7 days.4.3 TDG and TDP are identified by retention time and oneSRM transition. The target analyte and surrogate are quanti-tated using the SRM transitions utilizing an external calibra-tion. The final report issued for each sample lists the concen-tration of TDG
16、and the TDP recovery.5. Significance and Use5.1 TDG is a Schedule 2 compound under the ChemicalWeapons Convention (CWC). Schedule 2 chemicals includethose that are precursors to chemical weapons, chemicalweapons agents or have a number of other commercial uses.They are used as ingredients to produce
17、 insecticides,herbicides, lubricants, and some pharmaceutical products.Schedule 2 chemicals can be found in applications unrelated tochemical weapons. TDG is both a mustard gas precursor and adegradant as well as an ingredient in water-based inks, ball-point pen inks, dyes, and some pesticides.55.2
18、This method has been investigated for use with soil.6. Interferences6.1 Method interferences may be caused by contaminants insolvents, reagents, glassware, and other apparatus producingdiscrete artifacts or elevated baselines. All of these materialsare demonstrated to be free from interferences by a
19、nalyzinglaboratory reagent blanks under the same conditions assamples.6.2 All glassware is washed in hot water with a detergentand rinsed in hot water followed by distilled water. Theglassware is then dried and heated in an oven at 250C for 15to 30 min. All glassware is subsequently cleaned with ace
20、tone,then methanol.6.3 All reagents and solvents should be of pesticide residuepurity or higher to minimize interference problems.6.4 Matrix interferences may be caused by contaminantsthat are co-extracted from the sample. The extent of matrixinterferences can vary considerably from sample source de
21、-pending on variations of the sample matrix.7. Apparatus7.1 LC/MS/MS System:7.1.1 Liquid Chromatography (LC) System6A completeLC system is required in order to analyze samples. Any LCsystem that is capable of performing at the flows, pressures,controlled temperatures, sample volumes, and requirement
22、s ofthe standard may be used.7.1.2 Analytical Column7A reverse-phase analytical col-umn with strong embedded basic ion-pairing groups was usedto develop this test method.Any column that achieves adequateresolution may be used. The retention times and order ofelution may change depending on the colum
23、n used and need tobe monitored.7.1.3 Tandem Mass Spectrometer (MS/MS) System8AMS/MS system capable of multiple reaction monitoring(MRM) analysis or any system that is capable of performing atthe requirements in this standard may be used.7.2 Pressurized Fluid Extraction Device9:7.2.1 A PFE system was
24、 used for this test method withappropriately-sized extraction cells. Cells are available thatwill accommodate the 510 g sample sizes used in this testmethod. Cells should be made of stainless steel or othermaterial capable of withstanding the pressure requirements(2000 psi) necessary for this proced
25、ure.Any pressurized fluidextraction device may be used that can meet the necessaryrequirements in this test method.7.2.2 Whatman Glass Fiber Filters19.8 mm, DionexCorporation, Part # 047017 were used because they arespecially designed for the PFE system used or equivalent.7.3 A solvent blowdown devi
26、ce10with 24- and 50-vialcapacity trays and a water bath maintained at 60C for analyteconcentration from solvent volumes up to 50 mL or similardevice may be used.7.4 A nitrogen evaporation device11equipped with a waterbath that can be maintained at 50C for final analyte concen-tration (0.98 for the a
27、nalyte. The point of originis excluded, and a fit weighting of 1/X is used in order to givemore emphasis to the lower concentrations. If one of thecalibration standards other than the high or low point causesthe r2of the curve to be 0.99 for the analyte. The point oforigin is excluded, and a fit wei
28、ghting of 1/X is used in orderto give more emphasis to the lower concentrations. If one ofthe calibration standards, other than the high or low, causes thecurve to be 0.99. Inthis event, the reporting range must be modified to reflect thischange.12.2.5 The retention time window of the SRM transition
29、smust be within 5% of the retention time of the analyte in amidpoint calibration standard. If this is not the case, re-analyzethe calibration curve to determine if there was a shift inretention time during the analysis, and the sample needs to bere-injected. If the retention time is still incorrect
30、in the sample,refer to the analyte as an unknown.12.2.6 A midpoint calibration check standard must be ana-lyzed at the end of each batch of 20 samples or within 24 hafter the initial calibration curve was generated. This endcalibration check should be the same calibration standard thatwas used to ge
31、nerate the initial curve. The results from the endcalibration check standard must have a percent deviation lessthan 30% from the calculated concentration for the targetTABLE 3 Retention Times, SRM Transitions, and Analyte-SpecificMass Spectrometer ParametersAnalyteSRM MassTransition(Parent Product)R
32、etentionTime(min)ConeVoltage(Volts)CollisionEnergy(eV)Thiodiglycol 123.1 104.9 2.75 18 53,3-Thiodipropanol 151.2 133.1 5.75 19 8TABLE 4 Concentrations of Calibration Standards (PPB)Analyte/Surrogate LV 1 LV 2 LV 3 LV 4 LV 5 LV 6 LV 7 LV 8Thiodiglycol 500 1000 2000 4000 8000 16 000 32 000 40 0003,3-T
33、hiodipropanol 500 1000 2000 4000 8000 16 000 32 000 40 000E2787 11 (2016)4analyte and surrogate. If the results are not within these criteria,the problem must be corrected and either all samples in thebatch must be re-analyzed against a new calibration curve orthe affected results must be qualified
34、with an indication thatthey do not fall within the performance criteria of the testmethod. If the analyst inspects the vial containing the endcalibration check standard and notices that the sample evapo-rated affecting the concentration, a new end calibration checkstandard may be made and analyzed.
35、If this new end calibrationcheck standard has a percent deviation less than 30% from thecalculated concentration for the target analyte and surrogate,the results may be reported unqualified.12.3 If a laboratory has not performed the test before or ifthere has been a major change in the measurement s
36、ystem, forexample: new analyst or new instrument, perform a precisionand bias study to demonstrate laboratory capability.12.3.1 Analyze at least four replicates of a sample contain-ing TDG and TDP at a concentration between 4 and 10 ppm inOttawa sand. This test method was tested at 6.4 ppm. Eachrepl
37、icate must be taken through the complete analytical testmethod.12.3.2 Calculate the mean (average) percent recovery andrelative standard deviation (RSD) of the four values andcompare to the acceptable ranges of the quality control (QC)acceptance criteria for the Initial Demonstration of Perfor-mance
38、 in Table 5.12.3.3 This study should be repeated until the single opera-tor precision and mean recovery are within the limits in Table5.12.3.4 The QC acceptance criteria for the Initial Demon-stration of Performance in Table 5 were generated from asingle-laboratory. The analyst must be aware that th
39、e perfor-mance data generated from single-laboratory data tend to besignificantly tighter than those generated from multi-laboratorydata. It is recommended that the laboratory generate its ownin-house QC acceptance criteria which meet or exceed thecriteria in this standard. References on how to gene
40、rate QCacceptance criteria are Practice E2554 or Method 8000B inEPA publication SW-846 may be helpful.12.4 Surrogate Spiking Solution:12.4.1 A surrogate standard solution consisting of TDP isadded to each 5 g soil sample. The TDP is added to eachsample to achieve a concentration of 6.4 mg/kg (that i
41、s, 160 Lof a 200 ppm methanol solution containing TDP is added to a5 g soil sample). The result obtained for the surrogate recoverymust fall within the limits of Table 5. If the limits are not met,the affected results must be qualified with an indication thatthey do not fall within the performance c
42、riteria of the testmethod.12.5 Method Blank:12.5.1 Analyze a blank with each batch of 20 or fewersamples. The concentration of TDG found in the blank must bebelow the MDL. If the concentration of TDG is found abovethis level, analysis of samples is halted until the contaminationis eliminated, and a
43、blank shows no contamination at or abovethis level or the results must be qualified with an indication thatthey do not fall within the performance criteria of the testmethod.12.6 Laboratory Control Sample (LCS):12.6.1 To ensure that the test method is in control, analyzea LCS prepared with TDG at a
44、concentration in the reportingrange between 4 and 10 ppm. The LCS is prepared followingthe analytical method and analyzed with each batch of 20samples or less.An Ottawa sand sample is spiked with TDG toachieve a concentration of 6.4 mg/kg (that is, 160 L of a 200ppm methanol solution containing TDG
45、is added toa5gsoilsample). The result obtained for the LCS must fall within thelimits in Table 5.12.6.2 If the result is not within these limits, analysis ofsamples is halted until the problem is corrected, and either allsamples in the batch must be re-analyzed or the results must bequalified with a
46、n indication that they do not fall within theperformance criteria of the test method.12.7 Matrix Spike (MS):12.7.1 To check for interferences in the specific matrixbeing tested, perform a MS on at least one sample from eachbatch of 20 or fewer samples. This is accomplished by spikingthe sample with
47、a known concentration of TDG and followingthe analytical method. The matrix spike soil sample is spikedwith TDG to achieve a concentration of 6.4 mg/kg (that is, 160L of a 200 ppm methanol solution containing TDG is addedtoa5gsoil sample).12.7.2 If the spiked concentration plus the backgroundconcent
48、ration exceeds that of the Level 8 calibration standard,the sample must be diluted to a level near the midpoint of thecalibration curve.12.7.3 Calculate the percent recovery of the spike (P) usingEq 1:P 5 100?AVs1V! 2 BVs ?CV(1)where:A = concentration found in spiked sample,B = concentration found i
49、n unspiked sample,C = concentration of analyte in spiking solution,Vs= volume of sample used,V = volume of spiking solution added, andTABLE 5 Quality Control Acceptance CriteriaAnalyte/SurrogateTest Conc.(mg/kg)Initial Demonstration of Performance Lab Control SampleRecovery (%) Precision Recovery (%)LowerLimitUpperLimitMaximum% RSDLowerLimitUpperLimitThiodiglycol 6.4 30 130 46 30 1303,3-Thiodipropanol 6.4 30 130 39 30 130E2787 11 (2016)5P = percent recovery.12.7.4 The percent recovery of the spike shall fall within thelimits in Table 6. If the percent r
