ASTM D7644-16

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
5.1 This test method has been developed by U.S. EPA Region 5 Chicago Regional Laboratory (CRL).  
5.2 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.4  
5.3 This test 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 test method. This test method adheres to multiple reaction monitoring (MRM) mass spectrometry.  
1.2 The Detection Verification Level (DVL) and Reporting Range for the rodenticides are listed in Table 1.  
1.2.1 The DVL is required to be at a concentration at least 3 times below the Reporting Limit (RL) and have a signal/noise ratio greater than 3:1. Fig. 1 displays the signal/noise ratios of the primary single reaction monitoring (SRM) transitions, and Fig. 2 displays the confirmatory SRM transitions at the DVLs for the rodenticides.  
1.2.2 The reporting limit was calculated from the concentration of the Level 1 calibration standard, as shown in Table 4, accounting for the dilution of a 40 mL water sample up to a final volume of 50 mL with methanol to ensure analyte solubility.  
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.

General Information

• Status: Historical
• Publication Date: 31-Jan-2016
• 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

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
Designation: D7644 − 16
Standard Test 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. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
1.1 This procedure covers the determination of
Barriers to Trade (TBT) Committee.
bromadiolone, brodifacoum, diphacinone and warfarin (re-
ferred to collectively as rodenticides in this test method) in
2. Referenced Documents
water by direct injection using liquid chromatography (LC) and
2
2.1 ASTM Standards:
detected with tandem mass spectrometry (MS/MS). These
D1129 Terminology Relating to Water
analytes are qualitatively and quantitatively determined by this
D1193 Specification for Reagent Water
test method. This test method adheres to multiple reaction
D2777 Practice for Determination of Precision and Bias of
monitoring (MRM) mass spectrometry.
Applicable Test Methods of Committee D19 on Water
1.2 The Detection Verification Level (DVL) and Reporting
D3694 Practices for Preparation of Sample Containers and
Range for the rodenticides are listed in Table 1.
for Preservation of Organic Constituents
1.2.1 The DVL is required to be at a concentration at least
D3856 Guide for Management Systems in Laboratories
3 times below the Reporting Limit (RL) and have a signal/
Engaged in Analysis of Water
noise ratio greater than 3:1. Fig. 1 displays the signal/noise
D4841 Practice for Estimation of Holding Time for Water
ratios of the primary single reaction monitoring (SRM)
Samples Containing Organic and Inorganic Constituents
transitions, and Fig. 2 displays the confirmatory SRM transi-
D5847 Practice for Writing Quality Control Specifications
tions at the DVLs for the rodenticides.
for Standard Test Methods for Water Analysis
1.2.2 The reporting limit was calculated from the concen-
E2554 Practice for Estimating and Monitoring the Uncer-
tration of the Level 1 calibration standard, as shown in Table 4,
tainty of Test Results of a Test Method Using Control
accounting for the dilution of a 40 mL water sample up to a
Chart Techniques
final volume of 50 mL with methanol to ensure analyte
3
2.2 Other Documents:
solubility.
U.S. EPA publication SW-846 Test Methods for Evaluating
1.3 Units—The values stated in SI units are to be regarded
Solid Waste, Physical/Chemical Methods
as standard. No other units of measurement are included in this
standard.
3. Terminology
1.4 This standard does not purport to address all of the
3.1 Definitions:
safety concerns, if any, associated with its use. It is the
3.1.1 For definitions of terms used in this standard, refer to
responsibility of the user of this standard to establish appro-
Terminology D1129.
priate safety, health, and environmental practices and deter-
3.2 Definitions of Terms Specific to This Standard:
mine the applicability of regulatory limitations prior to use.
3.2.1 detection verification level, DVL, n—a concentration
1.5 This international standard was developed in accor-
that has a signal/noise (S/N) ratio greater than 3:1 and is at least
dance with internationally recognized principles on standard-
3 times below the Reporting Limit (RL).
ization established in the Decision on Principles for the
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
1
This test method is under the jurisdiction of ASTM Committee D19 on Water contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for Standards volume information, refer to the standard’s Document Summary page on
Organic Substances in Water. the ASTM website.
3
Current edition approved Feb. 1, 2016. Published May 2016. Originally Available from National Technical Information Service (NTIS), U.S. Depart-
ɛ2
approved in 2010. Last previous edition approved in 2010 as D7644 – 10 . DOI: ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
10.1520/D7644-16. 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
1

---------------------- Page: 1 ----------------------
D7644 − 16
TABLE 1 Detection Verification Level and Reporting Range
4. Summary of Test Method
DVL Reporting Range
4.1 This is a performance based method, and modifications
Analyte
(ng/L)
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
´2
Designation: D7644 − 10 D7644 − 16
Standard Test 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. A number 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
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 test method. This test method
adheres to multiple reaction monitoring (MRM) mass spectrometry.
1.2 The Detection Verification Level (DVL) and Reporting Range for the rodenticides are listed in Table 1.
1.2.1 The DVL is required to be at a concentration at least 3 times below the Reporting Limit (RL) and have a signal/noise ratio
greater than 3:1. Fig. 1 displays the signal/noise ratios of the primary single reaction monitoring (SRM) transitions, and Fig. 2
displays the confirmatory SRM transitions at the DVLs for the rodenticides.
1.2.2 The reporting limit was calculated from the concentration of the Level 1 calibration standard, as shown in Table 4,
accounting for the dilution of a 40 mL water sample up to a final volume of 50 mL with methanol to ensure analyte solubility.
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.
2. Referenced Documents
2
2.1 ASTM Standards:
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
D2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
D3694 Practices for Preparation of Sample Containers and for Preservation of Organic Constituents
D3856 Guide for Management Systems in Laboratories Engaged in Analysis of Water
1
This test method is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved June 1, 2010Feb. 1, 2016. Published February 2011May 2016. Originally approved in 2010. Last previous edition approved in 2010 as D7644
ɛ2
– 10 . DOI: 10.1520/D7644-10E02.10.1520/D7644-16.
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 Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
TABLE 1 Detection Verification Level and Reporting Range
DVL Reporting Range
Analyte
(ng/L) (ng/L)
Bromadiolone 20 125-2500
Brodifacoum 20 125-2500
Diphacinone 20 125-2500
Warfarin 20 125-2500
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
D7644 − 16
FIG. 1 Example Primary SRM Chromatograms Signal/Noise Ratios
FIG. 2 Example Confirmatory SRM Chromatograms Signal/Noise Ratios
2

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D7644 − 16
D4841 Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
D5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis
E2554 Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques
3
2.2 Other Documents:
U.S. EPA publication SW-846 Test Methods for Evaluating Solid Waste, Physical/Chemical Methods
3. Terminology
3.1 Definitions:
3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.
3.2 Definitions:Definitions of Terms Specific to This Standard:
3.2.1 detection verification level, DVL, n
...