1、Designation: E2787 11Standard 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 immediately follo
2、wing 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 This procedure co
3、vers 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 determined by thi
4、s 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 reporting limit (RL) is
5、calculated from the con-centration of the Level 1 calibration standard as shown in Table4. The RL for this method is 200 ppb. Reporting rangeconcentrations are calculated from Table 4 concentrationsassuminga5Linjection of the lowest level calibrationstandard, 5 g sample, anda2mLfinal extract volume.
6、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 standard to establish
7、 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 Preparation of Sample Cont
8、ainers 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 Test Method in a
9、 SingleLaboratory Using a Control Sample Program2.2 Other Documents:EPA publication SW-846, Test Methods for EvaluatingSolid Waste, Physical/Chemical Methods440 CFR Part 136, Appendix B, The Code of FederalRegulations3. Terminology3.1 Abbreviations:3.1.1 mMmillimolar, 1 3 10-3moles/L3.1.2 NDnon-dete
10、ct3.1.3 SRMsingle reaction monitoring3.1.4 MRMmultiple reaction monitoring4. Summary of Test Method4.1 This is a performance based method, and modificationsare allowed to improve performance.4.2 For TDG analysis, samples are shipped to the labbetween 0 and 6C. In the lab, the soils are spiked with3,
11、3-thiodipropanol (TDP, surrogate) and extracted by PFE.The extract is filtered using a syringe driven filter unit, reduced1This test method is under the jurisdiction of ASTM Committee E54 onHomeland Security Applications and is the direct responsibility of SubcommitteeE54.03 on Decontamination.Curre
12、nt edition approved Jan. 1, 2011. Published March 2011. DOI: 10.1520/E2787-11.2The PFE system that was used to develop this test method was AcceleratedSolvent Extraction (ASEt) which is a patented technique by Dionex, Sunnyvale,CA 94088.3For referenced ASTM standards, visit the ASTM website, www.ast
13、m.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4Available from National Technical Information Service (NTIS), U.S. Depart-ment of Commerce, 5285 Port Royal Road, Springfie
14、ld, VA, 22161 or at http:/www.epa.gov/epawaste/hazard/testmethods/index.htmTABLE 1 Method Detection Limit and Reporting RangeAnalyte MDL (ppb) Reporting Range (ppb)Thiodiglycol 54 20016 0001Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United Sta
15、tes.in volume, reconstituted with water, and 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
16、each sample lists the concen-tration of TDG 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
17、uses.They are used as ingredients to produce insecticides, herbi-cides, lubricants, and some pharmaceutical products. Schedule2 chemicals can be found in applications unrelated to chemicalweapons. TDG is both a mustard gas precursor and a degradantas well as an ingredient in water-based inks, ballpo
18、int pen inks,dyes, and some pesticides.55.2 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 dem
19、onstrated to be free from interferences by analyzinglaboratory 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. Al
20、l glassware is subsequently cleaned with acetone,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
21、 can vary considerably from sample source de-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 t
22、emperatures, sample volumes, and requirements 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
23、 ofelution may change depending on the column 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 Flu
24、id Extraction Device9:7.2.1 A PFE system was 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 requ
25、irements($2000 psi) necessary for this procedure. Any pressurizedfluid extraction 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
26、used or equivalent.7.3 A solvent blowdown device10with 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 fo
27、r final analyte concen-tration (0.98 for the analyte. 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.
28、 The point oforigin is excluded, and a fit weighting 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 T
29、he retention time window of the SRM transitionsmust 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-injec
30、ted. 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 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 th
31、e same calibration standard thatwas used to generate the initial curve. The results from the endcalibration check standard must have a percent deviation lessthan 30% from the calculated concentration for the targetanalyte and surrogate. If the results are not within these criteria,TABLE 3 Retention
32、Times, SRM Transitions, and Analyte-SpecificMass Spectrometer ParametersAnalyteSRM MassTransition(Parent Product)RetentionTime(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)Analy
33、te/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-Thiodipropanol 500 1000 2000 4000 8000 16 000 32 000 40 000E2787 114the problem must be corrected and either all samples in thebatch must be re-analyzed against a new calibration curve or
34、the affected results must be qualified 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 c
35、heckstandard may be made and analyzed. 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 b
36、een a major change in the measurement system, 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
37、 method was tested at 6.4 ppm. Eachreplicate 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 th
38、e Initial Demonstration of Perfor-mance 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-labora
39、tory. The analyst must be aware that the 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 t
40、his standard. References on how to generate 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 achie
41、ve a concentration of 6.4 mg/kg (that is, 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 thatth
42、ey do not fall within the performance criteria 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
43、 the contaminationis eliminated, and a 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 contro
44、l, analyzea LCS prepared with TDG at a 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
45、200ppm methanol solution containing TDG 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-analyze
46、d or the results must bequalified with an 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
47、 accomplished by spikingthe sample with 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
48、concentration plus the backgroundconcentration 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?AVs1 V! BVs?CV(1)where:A = concentration found in s
49、piked sample,B = concentration found in unspiked sample,C = concentration of analyte in spiking solution,Vs= volume of sample used,V = volume of spiking solution added, andP = percent recovery.TABLE 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 11512.7.4 The percent recovery of the spike shall fall within thelimits
