ASTM D7644-10e2

Standard Test Method for Determination of Bromadiolone, Brodifacoum, Diphacinone and Warfarin in Water by Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)

SIGNIFICANCE AND USE
This test method has been developed by US EPA Region 5 Chicago Regional Laboratory (CRL).
Bromadiolone, brodifacoum, diphacinone and warfarin are rodenticides for controlling mice, rats, and other rodents that pose a threat to public health, critical habitats, native plants and animals, crops, food and water supplies. These rodenticides also present human and environmental safety concerns. Warfarin and diphacinone are first-generation anticoagulants, while bromadiolone and brodifacoum are second-generation. The anticoagulants interfere with blood clotting, and death can result from excessive bleeding. The second-generation anticoagulants are especially hazardous for several reasons. They are highly toxic and persist a long time in body tissues. The second-generation anticoagulants are designed to be toxic in a single feeding, but time-to-death occurs in several days. This allows rodents to feed multiple times before death, leading to carcasses containing residues that may be many times the lethal dose.  
This method has been investigated for use with reagent, surface, and drinking water for the selected rodenticides.
SCOPE
1.1 This procedure covers the determination of bromadiolone, brodifacoum, diphacinone and warfarin (referred to collectively as rodenticides in this test method) in water by direct injection using liquid chromatography (LC) and detected with tandem mass spectrometry (MS/MS). These analytes are qualitatively and quantitatively determined by this method. This method adheres to multiple reaction monitoring (MRM) mass spectrometry.
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.
TABLE 1 Detection Verification Level and Reporting Range  AnalyteDVL
(ng/L)Reporting Range
(ng/L) Bromadiolone20125-2500 Brodifacoum20125-2500 Diphacinone20125-2500 Warfarin20125-2500
FIG. 1 Example Primary SRM Chromatograms Signal/Noise Ratios
FIG. 2 Example Confirmatory SRM Chromatograms Signal/Noise Ratios

General Information

• Status: Historical
• Publication Date: 31-May-2010
• ICS: 13.060.50 - Examination of water for chemical substances
• Technical Committee: D19 - Water
• Drafting Committee: D19.06 - Methods for Analysis for Organic Substances in Water

Relations

• Replaces: ASTM D7644-10e1 - Standard Test Method for Determination of Bromadiolone, Brodifacoum, Diphacinone and Warfarin in Water by Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)
• Effective Date: 01-Jun-2010

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
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Designation:D7644 −10
StandardTest Method for
Determination of Bromadiolone, Brodifacoum, Diphacinone
and Warfarin in Water by Liquid Chromatography/Tandem
1
Mass Spectrometry (LC/MS/MS)
This standard is issued under the fixed designation D7644; 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
ε NOTE—This test method was corrected editorially in April 2011.
2
ε NOTE—This test method was corrected editorially in February 2012.
1. Scope 2. Referenced Documents
2
2.1 ASTM Standards:
1.1 This procedure covers the determination of
D1129Terminology Relating to Water
bromadiolone, brodifacoum, diphacinone and warfarin (re-
D1193Specification for Reagent Water
ferred to collectively as rodenticides in this test method) in
D2777Practice for Determination of Precision and Bias of
waterbydirectinjectionusingliquidchromatography(LC)and
Applicable Test Methods of Committee D19 on Water
detected with tandem mass spectrometry (MS/MS). These
D3694Practices for Preparation of Sample Containers and
analytesarequalitativelyandquantitativelydeterminedbythis
for Preservation of Organic Constituents
method. This method adheres to multiple reaction monitoring
D3856Guide for Management Systems in Laboratories
(MRM) mass spectrometry.
Engaged in Analysis of Water
1.2 The Detection Verification Level (DVL) and Reporting
D4841Practice for Estimation of Holding Time for Water
Range for the rodenticides are listed in Table 1.
Samples Containing Organic and Inorganic Constituents
1.2.1 The DVL is required to be at a concentration at least
D5847Practice for Writing Quality Control Specifications
3 times below the Reporting Limit (RL) and have a signal/ for Standard Test Methods for Water Analysis
noise ratio greater than 3:1. Fig. 1 displays the signal/noise
E2554Practice for Estimating and Monitoring the Uncer-
ratios of the primary single reaction monitoring (SRM) tainty of Test Results of a Test Method Using Control
transitions, and Fig. 2 displays the confirmatory SRM transi-
Chart Techniques
tions at the DVLs for the rodenticides.
2.2 Other Documents:
EPApublication SW-846Test Methods for Evaluating Solid
1.2.2 The reporting limit was calculated from the concen-
3
Waste, Physical/Chemical Methods
trationoftheLevel1calibrationstandard,asshowninTable4,
accounting for the dilution of a 40 mL water sample up to a
3. Terminology
final volume of 50 mL with methanol to ensure analyte
3.1 Definitions:
solubility.
3.1.1 detection verification level, DVL, n—a concentration
1.3 Units—The values stated in SI units are to be regarded
thathasasignal/noise(S/N)ratiogreaterthan3:1andisatleast
asstandard.Nootherunitsofmeasurementareincludedinthis
3 times below the Reporting Limit (RL).
standard.
3.1.2 reporting limit, RL, n—the concentration of the
1.4 This standard does not purport to address all of the
lowest-level calibration standard used for quantification ac-
safety concerns, if any, associated with its use. It is the
counting for the sample dilution.
responsibility of the user of this standard to establish appro-
3.1.2.1 Discussion—In this test method, a 40 mL sample
priate safety and health practices and determine the applica-
aliquot is diluted to a 50 mL final volume after thoroughly
bility of regulatory limitations prior to use.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
1
This test method is under the jurisdiction ofASTM Committee D19 on Water Standards volume information, refer to the standard’s Document Summarypageon
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor the ASTM website.
3
Organic Substances in Water. Available from National Technical Information Service (NTIS), U.S. Depart-
CurrenteditionapprovedJune1,2010.PublishedFebruary2011.DOI:10.1520/ ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
D7644-10E02. 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
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D7644−10
TABLE 1 Detection Verification Level and Reporting Range
allows rodents to feed multiple times before death, leading to
DVL Reporting Range carcassescontainingresiduesthatmaybemanytimesthelethal
Analyte
4
(ng/L) (ng/L)
dose.
Bromadiolone 20 125-2500
5.3 This method has been investigated for use with reagent,
Brodifacoum 20 125-2500
Diphacinone 20 125-2500
surface, and drinking water for the selected rodenticides.
Warfarin 20 125-2500
6. I
...