ASTM D8018-15(2020)
(Test Method)Standard Test Method for Determination of (Tri-n-butyl)-n-tetradecylphosphonium chloride (TTPC) in Soil by Multiple Reaction Monitoring Liquid Chromatography/Mass Spectrometry (LC/MS/MS)
Standard Test Method for Determination of (Tri-n-butyl)-n-tetradecylphosphonium chloride (TTPC) in Soil by Multiple Reaction Monitoring Liquid Chromatography/Mass Spectrometry (LC/MS/MS)
SIGNIFICANCE AND USE
5.1 This test method has been developed by the U.S. EPA Region 5 Chicago Regional Laboratory (CRL).
5.2 TTPC may be used in various industrial and commercial products for use as a biocide. Products containing TTPC have been approved for controlling algal, bacterial, and fungal slimes in industrial water systems.2 TTPC should not be persistent in water but may be deposited in sediments at concentrations of concern. Hence, there is a need for quick, easy, and robust method to determine TTPC concentration at trace levels in various soil matrices for understanding the sources and concentration levels in affected soils and sediments.
5.3 This method has been used to determine TTPC in sand, a commercial top soil, and four ASTM reference soils (Table 4).
SCOPE
1.1 This procedure covers the determination of (Tri-n-butyl)-n-tetradecylphosphonium chloride (TTPC) in a soil matrix by extraction with acetone, filtration, dilution with water, and analysis by liquid chromatography/tandem mass spectrometry. TTPC is a biocide that strongly adsorbs to soils.2 The sample extracts are prepared in a solution of 75 % acetone and 25 % water because TTPC has an affinity for surfaces and particles. The reporting range for this method is from 250 to 10 000 ng/kg. This analyte is qualitatively and quantitatively determined by this method. This method adheres to multiple reaction monitoring (MRM) mass spectrometry.
1.2 The method detection limit (Note 1) (MDL) and reporting range (Note 2) for the target analyte are listed in Table 1.
Note 1: The MDL is determined following the Code of Federal Regulations, 40 CFR Part 136, Appendix B, as a guide utilizing solvent extraction of soil. Two-gram sample of Ottawa sand was utilized. A detailed process determining the MDL is explained in the reference and is beyond the scope of this standard to be explained here.
Note 2: Reporting range concentration is calculated from Table 2 concentrations assuming a 50-μL injection of the Level 1 calibration standard for TTPC, and the highest level calibration standard with a 20-mL final extract volume of a 2-g soil sample. Volume variations will change the reporting limit and ranges.
1.2.1 The reporting limit in this test method is the minimum value below which data are documented as non-detects. Analyte detections between the method detection limit and the reporting limit are estimated concentrations and are not reported following this test method. The reporting limit is calculated from the concentration of the Level 1 calibration standard as shown in Table 2 for TTPC after taking into account a 2-g sample weight and a final extract volume of 20 mL in 75 % acetone/25 % water. The final extract volume is 20 mL because a 15-mL volume of acetone is added to each soil sample and only the liquid layer after extraction is filtered leaving the solid behind followed by the addition of 5 mL of water to the acetone extract.
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.
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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.
Designation: D8018 − 15 (Reapproved 2020)
Standard Test Method for
Determination of (Tri-n-butyl)-n-tetradecylphosphonium
chloride (TTPC) in Soil by Multiple Reaction Monitoring
Liquid Chromatography/Mass Spectrometry (LC/MS/MS)
This standard is issued under the fixed designation D8018; 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 20mLin75%acetone/25%water.Thefinalextractvolumeis
20mL because a 15-mL volume of acetone is added to each
1.1 This procedure covers the determination of (Tri-n-
soil sample and only the liquid layer after extraction is filtered
butyl)-n-tetradecylphosphonium chloride (TTPC) in a soil
leaving the solid behind followed by the addition of 5 mL of
matrix by extraction with acetone, filtration, dilution with
water to the acetone extract.
water, and analysis by liquid chromatography/tandem mass
spectrometry.TTPCisabiocidethatstronglyadsorbstosoils. 1.3 Units—The values stated in SI units are to be regarded
Thesampleextractsarepreparedinasolutionof75%acetone asstandard.Nootherunitsofmeasurementareincludedinthis
and 25% water because TTPC has an affinity for surfaces and standard.
particles. The reporting range for this method is from 250 to
1.4 This standard does not purport to address all of the
10000 ng/kg. This analyte is qualitatively and quantitatively
safety concerns, if any, associated with its use. It is the
determined by this method. This method adheres to multiple
responsibility of the user of this standard to establish appro-
reaction monitoring (MRM) mass spectrometry.
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
1.2 The method detection limit (Note 1) (MDL) and report-
1.5 This international standard was developed in accor-
ing range (Note 2) for the target analyte are listed in Table 1.
dance with internationally recognized principles on standard-
NOTE 1—The MDL is determined following the Code of Federal
ization established in the Decision on Principles for the
Regulations, 40 CFR Part 136, Appendix B, as a guide utilizing solvent
Development of International Standards, Guides and Recom-
extraction of soil. Two-gram sample of Ottawa sand was utilized. A
detailedprocessdeterminingtheMDLisexplainedinthereferenceandis mendations issued by the World Trade Organization Technical
beyond the scope of this standard to be explained here.
Barriers to Trade (TBT) Committee.
NOTE 2—Reporting range concentration is calculated from Table 2
concentrations assuming a 50-µL injection of the Level 1 calibration
2. Referenced Documents
standard for TTPC, and the highest level calibration standard with a
2.1 ASTM Standards:
20-mL final extract volume of a 2-g soil sample. Volume variations will
change the reporting limit and ranges. D1193Specification for Reagent Water
D2777Practice for Determination of Precision and Bias of
1.2.1 Thereportinglimitinthistestmethodistheminimum
Applicable Test Methods of Committee D19 on Water
value below which data are documented as non-detects. Ana-
D5681Terminology for Waste and Waste Management
lyte detections between the method detection limit and the
D5847Practice for Writing Quality Control Specifications
reporting limit are estimated concentrations and are not re-
for Standard Test Methods for Water Analysis
ported following this test method. The reporting limit is
E2554Practice for Estimating and Monitoring the Uncer-
calculated from the concentration of the Level 1 calibration
tainty of Test Results of a Test Method Using Control
standard as shown in Table 2 for TTPC after taking into
Chart Techniques
account a 2-g sample weight and a final extract volume of
2.2 Other Documents:
EPAPublication SW-846Test Methods for Evaluating Solid
This test method is under the jurisdiction ofASTM Committee D34 on Waste
Waste, Physical/Chemical Methods
Management and is the direct responsibility of Subcommittee D34.01.06 on
Analytical Methods.
Current edition approved Feb. 1, 2020. Published February 2020. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 2015. Last previous edition approved in 2015 as D8018–15. DOI: contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
10.1520/D8018-15R20. Standards volume information, refer to the standard’s Document Summarypageon
More information on TTPC can be found at http://www.buruenergy.com/wp- the ASTM website.
content/uploads/BE-Environmental-Properties-of-Proposed- Biocide-BE-91.pdf Available from NationalTechnical Information Service (NTIS), 5301 Shawnee
(2014) and http://iaspub.epa.gov/sor_internet/registry/substreg/searchandretrieve/ Rd.,Alexandria,VA22312,http://www.ntis.govorathttp://www.epa.gov/epawaste/
advancedsearch/externalSearch.do?p_type=CASNO&p=81741-28-8 (2014). hazard/testmethods/index.htm.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8018 − 15 (2020)
A
TABLE 1 Method Detection Limit and Reporting Range
based and alternative operating conditions can be used to
Analyte MDL (ng/kg) Reporting Range (ng/kg)
perform this method provided data quality objectives are
TTPC 32.7 250–10 000
attained. Mention of trade names or suppliers is not an
A
Acronyms are defined in 3.3.
endorsement of use; it is provided for informational purposes
only.Any apparatus, supply, standard, or reagent may be used
provided that it is shown to be acceptable to meet the
performance criteria of the method.
40 CFR Part 136,Appendix BDefinition and Procedure for
the Determination of the Method Detection Limit
4.2 ForTTPCanalysis,samplesareshippedtothelabonice
and analyzed within 14 days of collection.Asample (~2 g) is
3. Terminology
transferred to a VOA vial, a TTPC spike solution is added to
laboratorycontrolandmatrixspikesamplesbeforetheaddition
3.1 For determinations of terms used in this standard, refer
of acetone. An isotopically labeled TTPC surrogate could be
to Terminology D5681.
added at this point, presently requires a custom synthesis and
3.2 Definitions of Terms Specific to This Standard:
shouldbeincorporatedintothismethodbytheuserifrequested
3.2.1 batch QC, n—all the quality control samples and
by the customer. Then add 15 mL of acetone and hand shake
standards included in an analytical procedure.
or vortex for 1 min.The samples are allowed to settle, and are
3.2.2 reporting limit check sample, RLCS, n—this sample is
then filtered through a Nylon membrane syringe-driven filter
to verify that if the analyte was present at the reporting limit,
unit leavingthesolidsbehind,5mLofASTMType1wateris
it would be confidently identified.
added to the filtered extract and then analyzed by LC/MS/MS.
All concentrations reported, only to the reporting limit, using
3.3 Acronyms:
this method are based upon a dry weight basis.
3.3.1 CCC, n—continuing calibration check
3.3.2 IC, n—initial calibration 4.3 TTPC is identified by comparing the single reaction
monitoring (SRM) transition and its confirmatory SRM tran-
3.3.3 LC, n—liquid chromatography
sitions if correlated to the known standard SRM transition
3.3.4 LCS/LCSD, n—laboratory control sample/laboratory
(Table 3) and quantitated utilizing an external calibration. The
control sample duplicate
final report issued for each sample lists the concentration of
3.3.5 MDL, n—method detection limit
TTPC, if detected, or RL, if not detected, in ng/kg (dry weight
basis) and surrogate recovery, if available.
3.3.6 MeOH, n—methanol
–3
3.3.7 mM, n—millimolar,1×10 moles/L
5. Significance and Use
3.3.8 MRM, n—multiple reaction monitoring
5.1 This test method has been developed by the U.S. EPA
3.3.9 MS/MSD, n—matrix spike/matrix spike duplicate
Region 5 Chicago Regional Laboratory (CRL).
3.3.10 NA, adj—not available
5.2 TTPCmaybeusedinvariousindustrialandcommercial
3.3.11 ND, n—non-detect
products for use as a biocide. Products containing TTPC have
been approved for controlling algal, bacterial, and fungal
3.3.12 P&A—precision and accuracy
slimes in industrial water systems. TTPC should not be
3.3.13 PPT, n—parts per trillion
persistent in water but may be deposited in sediments at
3.3.14 QA, adj—quality assurance
concentrations of concern. Hence, there is a need for quick,
3.3.15 QC, adj—quality control
easy, and robust method to determine TTPC concentration at
trace levels in various soil matrices for understanding the
3.3.16 RL, n—reporting limit
sources and concentration levels in affected soils and sedi-
3.3.17 RLCS, n—reporting limit check sample
ments.
3.3.18 RSD, n—relative standard deviation
5.3 This method has been used to determine TTPC in sand,
3.3.19 RT, n—retention time
a commercial top soil, and four ASTM reference soils (Table
3.3.20 SDS, n—safety data sheets
4).
3.3.21 SRM, n—single reaction monitoring
6. Interferences
3.3.22 SS, n—surrogate standard
6.1 All glassware is washed in hot water with detergent and
3.3.23 TC, n—target compound
rinsed in hot water followed by distilled water. The glassware
3.3.24 TTPC—n-(tri-n-butyl)-n-tetradecylphosphonium
is then dried and heated in an oven at 250°C for 15 to 30 min.
chloride
3.3.25 VOA, n—volatile organic analysis
A custom synthesized surrogate, TTPC (D29), may be an inexpensive viable
surrogate.
4. Summary of Test Method
A Whatman Puradisc™ 25 NYL Disposable Filter Unit (diameter 25 mm,
0.2µm Nylon membrane syringe-driven filter unit) has been found suitable for use
4.1 The operating conditions presented in this test method
for this method; any filter unit may be used that meets the performance of this
have been successfully used in the determination of TTPC in
method may be used. The use of PTFE, PVDF, and polypropylene filter units
soil; however, this test method is intended to be performance resulted in poor performance.
D8018 − 15 (2020)
TABLE 2 Concentrations of Calibration Standards (ng/L)
Concentrations
LV1 LV2 LV3 LV4 LV5 LV6 LV7 LV8
(ng/L)
TTPC 25 50 100 200 400 600 800 1000
TABLE 3 Retention Times, SRM Ions, and Analyte-Specific Mass Spectrometer Parameters
Primary/
Retention Time
Chemical Primary/Confirmatory SRM Transition Cone (V) Collision (eV) Confirmatory SRM
(minutes)
Area Ratio
Primary (Quantitation) 399.5→ 229.3 40 45 NA
TTPC First Confirmatory 399.5→ 75.9 40 46 8.1 0.92
Second Confirmatory 399.5→ 343.5 40 40 3.02
TABLE 4 Single-Laboratory Recovery Data in Six Soil Types
Ottawa Sand ASTM Frederick Sand ASTM Silt
Sample
(2500 ng/kg spike) (2500 ng/kg spike) (2500 ng/kg spike)
MB 1
MB 2
P&A 1 2074.5 2121.4 1477.8
P&A 2 2244.6 2145.9 1482.3
P&A 3 2286.4 2171.3 1364.2
P&A 4 2077.8 2215.4 1543.9
P&A 5 2192.1 2038.5 1545.7
P&A 6 1953.1 2079.2 1462.1
Average Recovery (ng/kg) 2138.1 2128.6 1479.3
% Average Recovery 85.5 85.1 59.2
Standard Deviation 125.0 63.7 66.5
RSD (%) 5.8 3.0 4.5
ASTM Lean Clay ASTM Fat Clay Top Soil
Sample
(2500 ng/kg spike) (2500 ng/kg spike) (2500 ng/kg spike)
MB 1
MB 2
P&A 1 394.6 790.2 1764.4
P&A 2 986.4 783.2 1750.1
P&A 3 386.4 772.4 1758.9
P&A 4 392.4 774.9 1771.6
P&A 5 435.3 791.7 1659.6
P&A 6 375.5 751.7 1778.3
Average Recovery (ng/kg) 395.1 777.4 1747.2
% Average Recovery 15.8 31.1 69.9
Standard Deviation 20.8 14.8 44.0
RSD (%) 5.3 1.9 2.5
Allglasswareissubsequentlyrinsedorsonicated,orboth,with 6.4 Matrix interferences may be caused by contaminants in
acetone, n-propanol, or acetonitrile, or combinations thereof. the sample. The extent of matrix interferences can vary
considerably depending on variations in the sample matrices.
6.2 TTPC should not be a common contaminant found in a
laboratory, unless involved in the analysis or matrices that
6.5 Automatic pipettes with polypropylene tips are used
contain TTPC. TTPC has been found to continue to adhere to with this method. The use of glass syringes for standards
glassware and syringes after routine glassware washing. Rins-
preparation, spiking, and calibrations generated erratic results
ingglasswarewithacetone,n-propanol,oracetonitrile,orboth, and should be avoided.Athoroughly cleaned 20-mLhypoder-
or even sonication, may be required to remove TTPC. All of
micglasssyringewithaNylonfilterisusedtofilterthe20-mL
thematerialsandsuppliesareroutinelydemonstratedtobefree
sample extracts and has been shown to perform well when
from interferences and TTPC by analyzing laboratory blanks filtering these large volumes. Preparing small volumes of
under the same conditions as the samples. If found, measures
samplesandstandards,like1-mLcalibrationstandards,maybe
shouldbetakentoremovethecontaminationordatashouldbe affected by adhesion of TTPC to the syringe barrel or plunger.
qualified;backgroundsubtractionofblankcontaminationisnot
The use of PTFE, PVDF, and polypropylene filter units
allowed. resulted in poor performance and low recoveries.
6.3 All reagents and solvents should be pesticide residue
NOTE3—Theuseofpolypropylenedisposablesyringestofiltersamples
purity or higher to minimize interference problems. and polypropylene LC vials with polyethylene caps have been shown to
D8018 − 15 (2020)
perform in the performance criteria of the method and may be used.
American Chemical Society. Other reagent grades may be
used provided they are first determined to be of sufficiently
7. Apparatus
highpuritytopermittheirusewithoutaffectingtheaccuracyof
the measurements.
7.1 LC/MS/MS System:
7.1.1 Liquid Chromatography System —A complete LC
8.2 Purity of Water—Unless otherwise indicated, references
system is required in order to analyze samples; this should
towatershallbeunderstoodtomeanreagentwaterconforming
include a sample injection system, a solvent pumping system
toType1ofSpecificationD1193.Itshallbedemonstratedthat
capable of mixing solvents, a sample compartment capable of
this water does not contain contaminants at concentrations
maintaining required temperature, and a temperature-
sufficient to interfere with the analysis.
controlled column compartment.An LC system that is capable
8.3 Gases—Ultrapure nitrogen and argon.
of performing at the flows, pressures, controlled temperatures,
8.4 Acetone (CAS # 67-64-1).
sample volumes, and requirements of the standard shall be
used.
8.5 Acetonitrile (CAS # 75-05-8).
7.1.2 Analytical Column —A reverse-phase C18 particle
8.6 Methanol
...
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