1、Designation: D8024 16Standard Test Method forDetermination of (Tri-n-butyl)-n-tetradecylphosphoniumchloride (TTPC) in Water by Multiple Reaction MonitoringLiquid Chromatography/Mass Spectrometry (LC/MS/MS)1This standard is issued under the fixed designation D8024; the number immediately following th
2、e 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 test method covers
3、the determination of (Tri-n-butyl)-n-tetradecylphosphonium chloride (TTPC) in water bydilution with acetone, filtration and analysis by liquidchromatography/tandem mass spectrometry. This test methodis not amenable for the analysis of isomeric mixtures ofTributyl-tetradecylphosphonium chloride. TTPC
4、 is a biocidethat strongly adsorbs to soils.2The water samples are preparedin a solution of 75 % acetone and 25 % water because TTPChas an affinity for surfaces and particles. The reporting rangefor this method is from 1004000 ng/L. This analyte isqualitatively and quantitatively determined by this
5、method.This test method adheres to multiple reaction monitoring(MRM) mass spectrometry.1.2 A full collaborative study to meet the requirements ofPractice D2777 has not been completed. This test methodcontains single-operator precision and bias based on single-operator data. Publication of standards
6、that have not been fullyvalidated is done to make the current technology accessible tousers of standards, and to solicit additional input from the usercommunity.1.3 The Method Detection Limit3(MDL) and ReportingRange4for the target analyte are listed in Table 1.1.3.1 The reporting limit in this test
7、 method is the minimumvalue below which data are documented as non-detects. Ana-lyte detections between the method detection limit and thereporting limit are estimated concentrations and are not re-ported following this test method. The reporting limit iscalculated from the concentration of the Leve
8、l 1 calibrationstandard as shown in Table 4 for TTPC after taking intoaccount a 2.5 mL water sample volume and a final dilutedsample volume of 10 mL (75 % acetone/25 % water). The finalsolution volume is 10 mL because a 7.5 mL volume of acetoneis added to each 2.5 mL water sample which is shaken and
9、filtered.1.4 UnitsThe values stated in SI units are to be regardedas standard. No other units of measurement are included in thisstandard.1.5 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
10、establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:5D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofAppli
11、cable Test Methods of Committee D19 on WaterD3856 Guide for Management Systems in LaboratoriesEngaged in Analysis of WaterD4841 Practice for Estimation of Holding Time for WaterSamples Containing Organic and Inorganic ConstituentsD5847 Practice for Writing Quality Control Specificationsfor Standard
12、Test Methods for Water AnalysisE2554 Practice for Estimating and Monitoring the Uncer-tainty of Test Results of a Test Method Using ControlChart Techniques1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forA
13、nalysis forOrganic Substances in Water.Current edition approved June 1, 2016. Published August 2016. DOI: 10.1520/D8024-16.2More information on TTPC can be found at http:/ and http:/iaspub.epa.gov/sor_internet/registry/substreg/searchandretrieve/advancedsearch/externalSearch.do?p_type=CASNO however,
14、 this test method is intended to be performancebased and alternative operating conditions can be used toperform this method provided data quality objectives areattained.4.2 ForTTPC analysis, samples are shipped to the lab on iceand analyzed within 14 days of collection. A sample (2.5 mL)is transferr
15、ed to a VOAvial, a TTPC spike solution is added toLaboratory Control and Matrix Spike samples before theaddition of acetone. An isotopically labeled TTPC surrogatewould be added at this point. An isotopically labeled TTPBr-D29 surrogate is now available and should be incorporated intothis method by
16、the user if requested by the customer.87.5 mLof acetone is them added and the solution is mixed by hand orvortex for 1 minute. The samples are then filtered through aNylon membrane syringe driven filter unit9and then analyzedby LC/MS/MS. All concentrations reported only to the report-ing limit.4.3 T
17、TPC is identified by comparing the single reactionmonitoring (SRM) transition and its confirmatory SRM tran-sitions if correlated to the known standard SRM transition(Table 3) and quantitated utilizing an external calibration. Thefinal report issued for each sample lists the concentration ofTTPC, if
18、 detected, or RL, if not detected, in ng/Land surrogaterecovery, if available.5. Significance and Use5.1 TTPC may be used in various industrial and commercialproducts for use as a biocide. Products containing TTPC havebeen approved for controlling algal, bacterial, and fungal6Available from U.S. Gov
19、ernment Printing Office, Superintendent ofDocuments, 732 N. Capitol St., NW, Washington, DC 20401-0001, http:/www.access.gpo.gov.7Available from United States Environmental ProtectionAgency (EPA),WilliamJefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460,http:/www.epa.gov.8A su
20、rrogate, TTPBr-D29, was custom synthesized by Cambridge IsotopeLaboratories Inc., Andover, MA 01810 and was found to be acceptable. Anycommercial source of TTPBr-D29 surrogate may be used, SRM transition 428.6 372.5 was used.9A Whatman Puradisc (a trademark of Whatman International Limited ofMaidsto
21、ne, Kent) 25 NYL Disposable Filter unit (Diameter 25 mm, 0.2 m Nylonmembrane syringe driven filter unit has been found suitable for use for this method,any filter unit may be used that meets the performance of this method may be used.TABLE 1 Method Detection Limit and Reporting RangeAnalyteMDL(ng/L)
22、Reporting Range(ng/L)TTPC 13 1004000D8024 162slimes in industrial water systems.2TTPC should not bepersistent in water but may be deposited in sediments atconcentrations of concern. Hence, there is a need for quick,easy and robust method to determine TTPC concentration attrace levels in water matric
23、es for understanding the sources andconcentration levels in affected areas.5.2 This method has been used to determine TTPC inreagent water and a river water (Table 8).NOTE 1This test method has been used to characterize TTPC in realworld water samples with success and similar recoveries as shown inT
24、able 8.6. Interferences6.1 All glassware is washed in hot water with detergent andrinsed in hot water followed by distilled water. The glasswareis then dried and heated in an oven at 250C for 15 to 30minutes. All glassware is subsequently rinsed and/or sonicatedwith acetone, n-propanol and/or aceton
25、itrile.6.2 TTPC should not be a common contaminant found in alaboratory, unless involved in the analysis or matrices thatcontain TTPC. TTPC has been found to continue to adhere toglassware and syringes after routine glassware washing. Rins-ing glassware with acetone, n-propanol and/or acetonitrile,
26、oreven sonication, may be required to remove TTPC. All of thematerials and supplies are routinely demonstrated to be freefrom interferences of TTPC by analyzing laboratory blanksunder the same conditions as the samples. If found, measuresshould be taken to remove the contamination or data should beq
27、ualified, background subtraction of blank contamination is notallowed.6.3 All reagents and solvents should be pesticide residuepurity or higher to minimize interference problems.6.4 Matrix interferences may be caused by contaminants inthe sample. The extent of matrix interferences can varyconsiderab
28、ly depending on variations in the sample matrices.6.5 Automatic pipettes with polypropylene tips were used toprepare the standards, spiking, and calibration solutions. Theuse of glass syringes for preparing standards, spiking, andcalibration solutions generated erratic results; glass syringesshould
29、be avoided for these critical tasks.Athoroughly cleaned10 or 20 mL hypodermic glass syringe with a nylon filter wasfound to perform well to filter the 10 mL prepared sample. 20mL Luer-Lock polypropylene syringes have also been shownto meet the performance of this test method; these aredisposable and
30、 do not require cleaning before use. It seemswhen preparing small volumes of solutions, concentrations areaffected by adhesion of TTPC to the syringe barrel or plunger.NOTE 2The use of PTFE, PVDF and polypropylene filter unitsresulted in poor performance and low recoveries.7. Apparatus7.1 LC/MS/MS S
31、ystem:TABLE 2 Gradient Conditions for Liquid ChromatographyTime(min)Flow(mL/min)Percent95 % Water: 5 % AcetonitrilePercentAcetonitrilePercent400 mM Ammonium Acetate(95 % Water: 5 % Acetonitrile)00.39 01040409511 0.4 0 95 512 0.4 95 0 515 0.4 95 0 5TABLE 3 Retention Time, SRM Ions, and Analyte-Specif
32、ic Mass Spectrometer ParametersChemicalPrimary/ConfirmatorySRMTransitionCone(V)Collision(eV)RetentionTime(minutes)Primary/ConfirmatorySRM Area RatioTTPCPrimary (Quantitation) 399.5229.3 40 458.1NAFirst Confirmatory 399.575.9 40 46 0.92Second Confirmatory 399.5343.5 40 10 3.02TABLE 4 Concentrations o
33、f Calibration Standards (ng/L)Concentrations(ng/L)LV1 LV2 LV3 LV4 LV5 LV6 LV7 LV8TTPC 25 50 100 200 400 600 800 1000TABLE 5 Preparation of Calibration StandardsSolution LV1 LV2 LV3 LV4 LV5 LV6 LV7 LV8AA25 L 50 L 100 L 200 L 400 L 600 L 800 L 1000 LBB975 L 950 L 900 L 800 L 600 L 400 L 200 L 0 LASolu
34、tion A: Level 8 stock solution prepared according to Section 12 and at Table 4 concentrations.BSolution B: 75 % Acetone, 25 % Water.D8024 1637.1.1 Liquid Chromatography System10A complete LCsystem is required in order to analyze samples, this shouldinclude a sample injection system, a solvent pumpin
35、g systemcapable of mixing solvents, a sample compartment capable ofmaintaining required temperature and a temperature controlledcolumn compartment. A LC system that is capable of perform-ing at the flows, pressures, controlled temperatures, samplevolumes, and requirements of this test method shall b
36、e used.7.1.2 Analytical Column11A reverse phase C18 particlecolumn was used to develop this test method.Any column thatachieves adequate resolution may be used. The retention timesand order of elution may change depending on the column usedand need to be monitored.7.2 Tandem Mass Spectrometer System
37、12A MS/MS sys-tem capable of multiple reaction monitoring (MRM) analysisor any system that is capable of meeting the requirements inthis test method shall be used.7.3 Adjustable Volume Pipettes10, 20, 100, and 1000 Land 5 and 10 mL.NOTE 3Any pipette may be used providing the data generated meetsthe
38、performance of this test method.7.3.1 Pipette TipsPolypropylene pipette tips free of re-lease agents or low retention coating of various sizes.7.4 Class A Volumetric Glassware.7.5 Filtration Device.7.5.1 Hypodermic SyringeA Luer-Lock tip glass or poly-propylene syringe capable of holding a syringe d
39、riven filterunit.7.5.2 A10 or 20 mL Lock Tip Syringe size is recommendedsince a 10 mL prepared sample size is used in this test method.If a smaller volume syringe is used, do not wash out the syringeor change filters while filtering the same sample if multiplerefills of the syringe is required in or
40、der to filter the 10 mLprepared sample.7.5.3 Filter Unit13Nylon filter units were used to filter thesamples.10A Waters Acquity UPLC H-Class System, or equivalent, has been foundsuitable for use.11A Waters Acquity UPLC BEH C18, 2.1 100 mm and 1.7 m particle sizecolumn, or equivalent, has been found s
41、uitable for use. It was used to develop thistest method and generate the precision and bias data presented in Section 16.12A Waters Xevo TQ-S triple quadrupole mass spectrometer, or equivalent, hasbeen found suitable for use.13AWhatman Puradisc 25 NYL Disposable Filter unit (diameter 25 mm, 0.2 mnyl
42、on membrane syringe driven filter unit) has been found suitable for use for thismethod. Any filter unit may be used that meets the performance of this method.TABLE 6 QC Acceptance CriteriaNOTE 1Table 6 data is preliminary until a multi-lab validation study is completed.AnalyteSpikeConc.ng/LInitial D
43、emonstration of Performance Laboratory Control SampleRecovery (%) Precision Recovery (%)Lower Limit Upper LimitMaximumLower Control Limit(LCL) %Upper Control Limit(UCL) % RSDTTPC 2000 70 130 30 70 130TABLE 7 MS/MSD QC Acceptance CriteriaNOTE 1Table 7 data is preliminary until a multi-lab validation
44、study is completed.AnalyteSpikeConc.ng/LMS/MSD PrecisionRecovery (%)RPD (%)Lower Limit Upper LimitTTPC 2000 70 130 30TABLE 8 Single-Laboratory Recovery Data in WaterSampleReagent Water P sample compartment,15C.11.2.3 Seal WashSolvent: 50 % methanol/5 0 % water;time: 5 minutes.11.3 Mass Spectrometer
45、Parameters:11.3.1 To acquire the maximum number of data points perSRM channel while maintaining adequate sensitivity, the tuneparameters may be optimized according to the instrument used.Each peak requires at least 10 scans per peak for adequatequantitation. Variable parameters regarding SRM transit
46、ions,and cone and collision energies are shown in Table 3. Thevalues for the following parameters are shown here forinformation only. These conditions should be checked andoptimized when required. Mass spectrometer parameters usedin the development of this method are listed below:The instrument is s
47、et in the Electrospray positive source setting:Capillary Voltage: 1 kVCone: Variable depending on analyteSource Temperature: 150CDesolvation Gas Temperature: 500CDesolvation Gas Flow: 900 L/hr14Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For
48、 suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.15Teflon is a trademark
49、of The Chemours Company, LLC, in Wilmington, DE.D8024 165Cone Gas Flow: 150 L/hrCollision Gas Flow: 0.15 mL/minLow Mass Resolution 1: 3High Mass Resolution 1: 14Ion Energy 1: 1Entrance Energy: 1Collision Energy: Variable depending on analyteExit Energy: 1Low Mass Resolution 2: 2.8High Mass Resolution 2: 14Ion Energy 2: 1Gain: 1.0Multiplier: 512.82Inter-Scan Delay: 0.003 seconds12. Calibration and Standardization12.1 The mass spectromete
