ASTM D8025-23

Standard Test Method for Determination of Select Pesticides in Water by Multiple Reaction Monitoring Liquid Chromatography Tandem Mass Spectrometry

SIGNIFICANCE AND USE
5.1 Pesticides may be used in various agricultural and household products. These products may enter waterways at low levels through run-off or misuse near water resources. Hence, there is a need for quick, easy and robust method to determine pesticide concentration in water matrices for understanding the sources and concentration levels in affected areas.  
5.2 This method has been single-laboratory validated in reagent water and surface waters (Tables 12-14).
SCOPE
1.1 This test method covers a method for analysis of selected pesticides in a water matrix by filtration followed with liquid chromatography/electrospray ionization tandem mass spectrometry analysis. The samples are prepared in 20 % methanol, filtered, and analyzed by liquid chromatography/tandem mass spectrometry. This method was developed for an agricultural run-off study, not for low level analysis of pesticides in drinking water. This method may be modified for lower level analysis. The analytes are qualitatively and quantitatively determined by this method. This method adheres to multiple reaction monitoring (MRM) mass spectrometry.  
1.2 A full collaborative study to meet the requirements of Practice D2777 has not been completed. This standard contains single-operator precision and bias based on single-operator data. Publication of standards that have not been fully validated is done to make the current technology accessible to users of standards, and to solicit additional input from the user community.  
1.3 A reporting limit check sample (RLCS) is analyzed during every batch to ensure that if an analyte was present in a sample at or near the reporting limit it would be positively identified and accurately quantitated within set quality control limits. A method detection limit (MDL) study was not done for this method, the method detection limits would be much lower than the reporting limits in this method and would be irrelevant. A RLCS was determined to be more applicable for this standard. If this method is adapted to report much lower or near the MDL then a MDL study would be warranted.  
1.4 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.5 The Reporting Range for the target analytes are listed in Table 1.  
1.5.1 The reporting limit in this test method is the minimum value below which data are documented as non-detects. The reporting limit is calculated from the concentration of the Level 1 calibration standard as shown in Table 6 after taking into account an 8 mL water sample volume and a final diluted sample volume of 10 mL (80 % water/20 % methanol).  
1.6 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.  
1.7 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.

General Information

• Status: Published
• Publication Date: 14-Apr-2023
• 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

• Refers: ASTM D1129-13(2020)e2 - Standard Terminology Relating to Water
• Effective Date: 01-May-2020
• Refers: ASTM E2554-18e1 - Standard Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques
• Effective Date: 01-Apr-2018
• Refers: ASTM E2554-18 - Standard Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques
• Effective Date: 01-Apr-2018
• Refers: ASTM E2554-13 - Standard Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques
• Effective Date: 01-Apr-2013
• Refers: ASTM D4841-88(2013)e1 - Standard Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
• Effective Date: 01-Jan-2013
• Refers: ASTM D4841-88(2013) - Standard Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
• Effective Date: 01-Jan-2013
• Refers: ASTM D2777-12 - Standard Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
• Effective Date: 15-Jun-2012
• Refers: ASTM D3856-11 - Standard Guide for Management Systems in Laboratories Engaged in Analysis of Water
• Effective Date: 15-Nov-2011
• Refers: ASTM D1129-10 - Standard Terminology Relating to Water
• Effective Date: 01-Mar-2010
• Refers: ASTM D4841-88(2008) - Standard Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
• Effective Date: 15-Jul-2008
• Refers: ASTM D2777-08 - Standard Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
• Effective Date: 15-Jan-2008
• Refers: ASTM E2554-07 - Standard Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method in a Single Laboratory Using a Control Sample Program
• Effective Date: 01-May-2007
• Refers: ASTM D1129-06ae1 - Standard Terminology Relating to Water
• Effective Date: 01-Sep-2006
• Refers: ASTM D1129-06a - Standard Terminology Relating to Water
• Effective Date: 01-Sep-2006
• Refers: ASTM D2777-06 - Standard Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
• Effective Date: 15-Aug-2006

Overview

ASTM D8025-23 is the internationally recognized standard test method for the determination of select pesticides in water using multiple reaction monitoring (MRM) liquid chromatography tandem mass spectrometry (LC-MS/MS). Developed by ASTM Committee D19 on Water, this method enables robust, quick, and accurate identification and quantification of a broad array of pesticide residues in a range of water matrices, such as surface waters impacted by agricultural runoff.

This standard is important for environmental monitoring, regulatory compliance, and research where precise and reliable quantification of pesticides is essential for protecting water quality and public health.

Key Topics

• Scope and Methodology

  • Covers analysis of multiple selected pesticides in water samples using filtration, followed by LC-MS/MS.
  • Samples are prepared in 20% methanol, filtered, and analyzed by LC-MS/MS utilizing MRM for both qualitative and quantitative determination.
  • Primarily developed for agricultural runoff studies, but can be adapted for other water types (not primarily for drinking water at very low detection levels).

• Target Analytes and Reporting Limits

  • Includes a wide range of pesticides such as 2,4-D, acetochlor, atrazine, dicamba, triclopyr, and more.
  • Reporting ranges are pesticide-specific, typically from low tens to hundreds of nanograms per liter (ng/L) up to several thousand ng/L.
  • Reporting limits are calculated from calibration standards and reflect the minimum quantifiable concentration.

• Quality Control Measures

  • Requires analysis of a reporting limit check sample (RLCS) for every batch to ensure that pesticides near the reporting limit are confidently identified and accurately quantified.
  • Use of isotopically labeled surrogate standards to track method performance and ensure data reliability.
  • Calibration and standardization steps emphasize external calibration using multilevel standards and regular quality checks.

• Laboratory Validation

  • Single-laboratory validation performed on reagent water and surface waters.
  • Precision and bias determined from single-operator data, making the method accessible while encouraging ongoing input from the user community.

• General Requirements

  • Strict adherence to SI units.
  • Emphasizes laboratory safety, including PPE, chemical handling, and environmental considerations.
  • Methods are performance-based, allowing alternative LC-MS/MS setups if performance goals are met.

Applications

• Environmental Monitoring

  • Used by environmental laboratories and agencies to detect and monitor pesticide contamination in rivers, lakes, streams, and other surface waters.
  • Essential for assessing non-point source pollution from agricultural activities and evaluating run-off controls.

• Regulatory Compliance

  • Supports compliance with environmental water quality standards by providing a validated method for pesticide analysis.
  • Useful for demonstrating adherence to national and international water protection regulations.

• Water Quality Assessment

  • Applied in watershed management and ecological risk assessment studies to determine the presence and concentration of pesticides.
  • Assists in tracing sources of contamination and evaluating the effectiveness of mitigation measures.

• Research

  • Utilized by researchers studying fate, transport, and degradation of pesticides in aquatic systems.
  • Valuable in developing new technologies for water treatment and remediation.

Related Standards

• ASTM D1129 - Terminology Relating to Water
• ASTM D1193 - Specification for Reagent Water
• ASTM D2777 - Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
• ASTM D3856 - Guide for Management Systems in Laboratories Engaged in Analysis of Water
• ASTM D4841 - Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
• ASTM D5847 - Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis
• EPA SW-846 - Test Methods for Evaluating Solid Waste, Physical/Chemical Methods

ASTM D8025-23 is a vital tool for any laboratory or regulatory body involved in monitoring water contaminants, supporting reliable pesticide testing and environmental stewardship.

Standards Content (Sample)

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: D8025 − 23
Standard Test Method for
Determination of Select Pesticides in Water by Multiple
Reaction Monitoring Liquid Chromatography Tandem Mass
Spectrometry
This standard is issued under the fixed designation D8025; 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 1.5 The Reporting Range for the target analytes are listed in
Table 1.
1.1 This test method covers a method for analysis of
1.5.1 The reporting limit in this test method is the minimum
selected pesticides in a water matrix by filtration followed with
value below which data are documented as non-detects. The
liquid chromatography/electrospray ionization tandem mass
reporting limit is calculated from the concentration of the Level
spectrometry analysis. The samples are prepared in 20 %
1 calibration standard as shown in Table 6 after taking into
methanol, filtered, and analyzed by liquid chromatography/
account an 8 mL water sample volume and a final diluted
tandem mass spectrometry. This method was developed for an
sample volume of 10 mL (80 % water/20 % methanol).
agricultural run-off study, not for low level analysis of pesti-
1.6 This standard does not purport to address all of the
cides in drinking water. This method may be modified for
safety concerns, if any, associated with its use. It is the
lower level analysis. The analytes are qualitatively and quan-
responsibility of the user of this standard to establish appro-
titatively determined by this method. This method adheres to
priate safety, health, and environmental practices and deter-
multiple reaction monitoring (MRM) mass spectrometry.
mine the applicability of regulatory limitations prior to use.
1.2 A full collaborative study to meet the requirements of
1.7 This international standard was developed in accor-
Practice D2777 has not been completed. This standard contains
dance with internationally recognized principles on standard-
single-operator precision and bias based on single-operator
ization established in the Decision on Principles for the
data. Publication of standards that have not been fully validated
Development of International Standards, Guides and Recom-
is done to make the current technology accessible to users of
mendations issued by the World Trade Organization Technical
standards, and to solicit additional input from the user com-
Barriers to Trade (TBT) Committee.
munity.
2. Referenced Documents
1.3 A reporting limit check sample (RLCS) is analyzed
during every batch to ensure that if an analyte was present in
2.1 ASTM Standards:
a sample at or near the reporting limit it would be positively
D1129 Terminology Relating to Water
identified and accurately quantitated within set quality control
D1193 Specification for Reagent Water
limits. A method detection limit (MDL) study was not done for
D2777 Practice for Determination of Precision and Bias of
this method, the method detection limits would be much lower
Applicable Test Methods of Committee D19 on Water
than the reporting limits in this method and would be irrel-
D3856 Guide for Management Systems in Laboratories
evant. A RLCS was determined to be more applicable for this
Engaged in Analysis of Water
standard. If this method is adapted to report much lower or near
D4841 Practice for Estimation of Holding Time for Water
the MDL then a MDL study would be warranted.
Samples Containing Organic and Inorganic Constituents
D5847 Practice for Writing Quality Control Specifications
1.4 Units—The values stated in SI units are to be regarded
for Standard Test Methods for Water Analysis
as standard. No other units of measurement are included in this
E2554 Practice for Estimating and Monitoring the Uncer-
standard.
tainty of Test Results of a Test Method Using Control
Chart Techniques
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. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved April 15, 2023. Published June 2023. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 2016. Last previous edition approved in 2016 as D8025 – 16. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D8025-23. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8025 − 23
TABLE 1 Reporting Range
3.3.5 LCS/LCSD, n—Laboratory Control Sample/
Analyte Reporting Ranges, (ng/L) Laboratory Control Sample Duplicate
2,4-D 250–10 000
3.3.6 MDL, n—Method Detection Limit
Acetochlor 250–10 000
Alachlor 250–10 000
3.3.7 MeOH, n—Methanol
Aldicarb 250–10 000
-3
3.3.8 mM, n—millimolar, 1 × 10 moles/L
Atrazine 62.5–2 500
Desethylatrazine 62.5–2 500
3.3.9 MRM, n—Multiple Reaction Monitoring
Desisopropylatrazine 125–5 000
Azoxystrobin 31.2–1 250
3.3.10 MS/MSD, n—Matrix Spike/Matrix Spike Duplicate
Bentazon 250–10 000
Carbaryl 250–10 000
3.3.11 NA, adj—Not Available
Chlorpyrifos 250–10 000
Clopyralid 25 000–1 000 000 3.3.12 ND, n—non-detect
Clothianidin 62.5–2 500
3.3.13 P&A, n—Precision and Accuracy
Diazinon 62.5–2 500
Dicamba 12 500–500 000
3.3.14 ppt, n—parts-per-trillion
Fipronil 250–10 000
Imidacloprid 62.5–2 500
3.3.15 QA, adj—Quality Assurance
Malathion 125–5 000
Methomyl 250–10 000
3.3.16 QC, adj—Quality Control
Metolachlor 62.5–2 500
3.3.17 RL, n—Reporting Limit
Metribuzin 125–5 000
Picloram 6 250–250 000
3.3.18 RLCS, n—Reporting Limit Check Sample
Propiconazole 62.5–2 500
Simazine 62.5–2 500
3.3.19 RSD, n—Relative Standard Deviation
Tebuconazole 62.5–2 500
Thiamethoxam 62.5–2 500
3.3.20 RT, n—Retention Time
Triclopyr 1 250–5 000
3.3.21 SDS, n—Safety Data Sheets
3.3.22 SRM, n—Single Reaction Monitoring
3.3.23 SS, n—Surrogate Standard
2.2 Other Document:
3.3.24 TC, n—Target Compound
EPA publication SW-846 Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods
3.3.25 VOA, n—Volatile Organic Analysis
3. Terminology
4. Summary of Test Method
3.1 Definitions:
4.1 The operating conditions presented in this standard have
3.1.1 For definitions of terms used in this standard, refer to
been successfully used in the determination of the select
Terminology D1129.
pesticides in water; however, this standard is intended to be
3.2 Definitions of Terms Specific to This Standard:
performance based and alternative operating conditions can be
3.2.1 batch QC, n—all the quality control samples and
used to perform this method provided data quality objectives
standards included in an analytical procedure.
are attained.
3.2.2 independent reference material, IRM, n—a material of
4.2 For pesticide analysis, samples are shipped to the lab on
known purity and concentration obtained either from the
ice and analyzed within 14 days of collection. A sample (8 mL)
National Institute of Standards and Technology (NIST) or other
is transferred to an amber VOA vial, an isotopically labeled
reputable supplier.
pesticide surrogate mix is added to all samples followed by a
3.2.2.1 Discussion—The IRM must be obtained from a
pesticide spike solution which is added only to the Reporting
different lot of material than is used for calibration.
Limit Check Samples, Laboratory Control and Matrix Spike
3.2.3 reporting limit, RL, n—the minimum concentration
samples before the addition of methanol. Then 2 mL of
below which data are documented as non-detects.
methanol is added to each sample and hand shaken or vortexed
3.2.4 reporting limit check sample, RLCS, n—a sample used
for 1 min. The samples are then filtered through a PTFE
to ensure that if the analyte was present at the reporting limit,
membrane syringe driven filter unit and then analyzed by
it would be confidently identified.
LC/MS/MS. All concentrations reported only to the reporting
limit.
3.3 Acronyms:
3.3.1 CCC, n—Continuing Calibration Check
4.3 The analysis of the sample requires two separate analy-
sis methods, one using the LC gradient conditions in Table 2
3.3.2 CRW, n—Chicago River Water
with the Methanol/Water/Ammonium Formate and the second
3.3.3 IC, n—Initial Calibration
using the LC gradient conditions in Table 3 with the Methanol/
3.3.4 LC, n—Liquid Chromatography
Water/Formic acid. Each analysis set is to be analyzed sepa-
rately in two different complete sample sequences which
includes the exact same samples and may even include the
Available from National Technical Information Service (NTIS), U.S. Depart-
same calibration level standards. The only analytes reported
ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
www.epa.gov/epawaste/hazard/testmethods/index.htm from the formic acid run conditions are 2,4-D, Clopyralid,
D8025 − 23
TABLE 2 Gradient Conditions for Neutral Liquid Chromatography
Percent
Percent
Time (min) Flow (mL/min) Percent Methanol 200 mM Ammonium Formate
95 % Water: 5 % Methanol
(95 % Water: 5 % Methanol)
0 0.3 95 0 5
1.5 0.3 95 0 5
9 0.3 0 95 5
12 0.3 0 95 5
13 0.3 95 0 5
16 0.3 95 0 5
TABLE 3 Gradient Conditions for Acidic Liquid Chromatography
Percent
Percent
Time (min) Flow (mL/min) Percent Methanol 4 % Formic Acid
95 % Water: 5 % Methanol
(95 % Water: 5 % Methanol)
0 0.3 95 0 5
1.5 0.3 95 0 5
6 0.3 0 95 5
9 0.3 0 95 5
10 0.3 95 0 5
13 0.3 95 0 5
Dicamba, Picloram, Triclopyr, 2,4-D (Ring-D3) and Dicamba- 7.1.1 Liquid Chromatography System—A complete LC sys-
D3, the rest of the analytes are reported from the ammonium tem is required in order to analyze samples, this should include
formate analysis run. a sample injection system, an autosampler, a solvent pumping
system capable of mixing solvents, a sample compartment
4.4 The pesticides are identified by comparing the single
capable of maintaining required temperature and a temperature
reaction monitoring (SRM) transition and its confirmatory
controlled column compartment. A LC system that is capable
SRM transitions if correlated to the known standard SRM
of performing at the flows, pressures, controlled temperatures,
transition (Tables 4 and 5) and quantitated utilizing an external
sample volumes, and requirements of the standard must be
calibration. The final report issued for each sample lists the
used.
concentration of pesticides, if detected, or RL, if not detected,
7.1.2 Analytical Column —A reverse phase C18 particle
in ng/L and surrogate recovery.
column was used to develop this test method. Any column that
achieves adequate resolution may be used. The retention times
5. Significance and Use
and order of elution may change depending on the column used
5.1 Pesticides may be used in various agricultural and
and need to be monitored.
household products. These products may enter waterways at
7.2 Tandem Mass Spectrometer System—A MS/MS system
low levels through run-off or misuse near water resources.
capable of multiple reaction monitoring (MRM) analysis or
Hence, there is a need for quick, easy and robust method to
any system that is capable of meeting the requirements in this
determine pesticide concentration in water matrices for under-
standard must be used. Electrospray ionization is utilized for
standing the sources and concentration levels in affected areas.
this standard.
5.2 This method has been single-laboratory validated in
7.3 Adjustable Volume Pipettes—10 μL, 20 μL, 100 μL,
reagent water and surface waters (Tables 12-14).
1000 μL, 5 mL, and 10 mL.
6. Interferences
7.3.1 Discussion—Any pipette may be used providing the
data generated meets the performance of the standard.
6.1 All glassware is washed in hot water with detergent and
7.3.2 Pipette Tips—Polypropylene pipette tips free of re-
rinsed in hot water followed by distilled water. The glassware
lease agents or low retention coating of various sizes.
is then dried and heated in an oven at 250 °C for 15 min to
30 min. All glassware is subsequently rinsed or sonicated, or
7.4 Class A Volumetric Glassware.
both, with acetone, n-propanol, acetonitrile, or a combination
7.5 Filtration Device:
thereof.
7.5.1 Hypodermic Syringe—A luer-lock tip glass syringe
6.2 All reagents and solvents should be pesticide residue
capable of holding a syringe driven filter unit.
purity or higher to minimize interference problems.
6.3 Matrix interferences may be caused by contaminants in
the sample. The extent of matrix interferences can vary 4
A Waters Acquity (a trademark of the Waters Corporation, Milford, MA) UPLC
considerably depending on variations in the sample matrices. BEH C18, 2.1 mm × 100 mm and 1.7 μm particle size column was used, if you are
aware of an alternative column that meets the performance of the standard, please
provide this information to ASTM International Headquarters. Your comments will
7. Apparatus
receive careful consideration at a meeting of the responsible technical committee,
7.1 LC/MS/MS System: which you may attend.
D8025 − 23
TABLE 4 SRM Ions and Analyte-Specific Mass Spectrometer Parameters
Primary/ ESI Mode Cone Collision
Chemical MRM Transition
Confirmatory Neg/Pos (V) (eV)
A
2,4-D Primary 218.9→160.9 Neg 20 14
Confirmatory 220.9→162.9 14
Acetochlor Primary 270.1→224.1 Pos 20 10
Confirmatory 270.1→148 18
Alachlor Primary 270.1→162 Pos 30 12
Confirmatory 270.1→238.1 18
Aldicarb Primary 213→88.9 Pos 20 16
Confirmatory 213→116 12
Atrazine Primary 216.1→174 Pos 20 18
Confirmatory 216.1→95.9 24
Desethylatrazine Primary 188→146 Pos 30 16
Confirmatory 188→78.8 22
Desisopropylatrazine Primary 174→96 Pos 30 16
Confirmatory 174→78.8 16
Azoxystrobin Primary 404.2→372.2 Pos 20 14
Confirmatory 404.2→344.2 24
Bentazon Primary 239→197 Pos 20 20
Confirmatory 239→175 20
Carbaryl Primary 202.1→145 Pos 10 10
Confirmatory 202.1→127 25
Chlorpyrifos Primary 350→197.9 Pos 30 20
Confirmatory 350→322 11
A
Clopyralid Primary 189.9→145.9 Neg 5 10
Confirmatory 191.9→147.9 10
Clothianidin Primary 250→169 Pos 20 15
Confirmatory 250→131.9 11
Diazinon Primary 305.1→169 Pos 30 20
Confirmatory 305.1→153 20
A
Dicamba Primary 218.9→174.9 Neg 10 8
Confirmatory 220.9→176.9 8
Fipronil Primary 435→330 Pos 30 15
Confirmatory 435→318 23
Imidacloprid Primary 256.1→209.1 Pos 30 17
Confirmatory 256.1→175 23
Malathion Primary 331.1→127 Pos 20 12
Confirmatory 331.1→285 6
Methomyl Primary 163→87.9 Pos 10 10
Confirmatory 163→105.9 11
Metolachlor Primary 284.1→252.1 Pos 30 16
Confirmatory 284.1→176.1 25
Metribuzin Primary 215.1→187.1 Pos 30 16
A
Picloram Primary 240.9→196.9 Neg 10 11
Confirmatory 238.9→194.9 11
Propiconazole Primary 342.1→158.9 Pos 30 22
Confirmatory 342.1→205 17
Simazine Primary 202→132 Pos 40 17
Confirmatory 202→124 17
Tebuconazole Primary 308.2→70 Pos 40 20
Confirmatory 308.2→125 28
Thiamethoxam Primary 292.1→211.1 Pos 20 12
Confirmatory 292.1→131.9 20
A
Triclopyr Primary 253.9→195.9 Neg 10 12
Confirmatory 253.9→217.9 Neg 10 6
Surrogates
A
2,4-D (Ring-D3) Primary 221.9→163.8 Neg 20 14
Atrazine (ethyl-D5) Primary 221.1→179 Pos 20 17
Desethylatrazine (iso-propyl-D7) Primary 195→146.9 Pos 20 18
Desisopropylatrazine (ethyl-D5) Primary 179→100.9 Pos 30 18
Bentazon -D7 Primary 246.1→182 Pos 20 20
Carbofuran (Ring-13C6) Primary 228.1→171 Pos 20 12
Clothianidin -D3 Primary 253→131.9 Pos 20 15
Diazinon (Diethyl-D10) Primary 315.2→170 Pos 30 20
A
Dicamba -D3 Primary 223.9→179.9 Neg 10 8
Imidacloprid -D4 Primary 260.1→213.1 Pos 30 15
Methomyl (Acetohydroxamate-13C2 15N) Primary 166→90.8 Pos 10 8
Simazine (Diethyl-D10) Primary 212.1→134 Pos 40 18
Tebuconazole (tert-Butyl-D9) Primary 317.2→69.9 Pos 40 20
Thiamethoxam -D3 Primary 295→214.1 Pos 30 12
A
Indicates analyzed under acidic LC conditions.
D8025 − 23
TABLE 5 SRM Ions, Retention times and SRM Ion Ratios
Retention
Primary/ MRM Primary/Confirmatory
Chemical Time
Confirmatory Transition SRM Area Ratio
Minutes
A
2,4-D Primary 218.9→160.9 7.6 1.5
Confirmatory 220.9→162.9
Acetochlor Primary 270.1→224.1 10.3 2.5
Confirmatory 270.1→148
Alachlor Primary 270.1→162 10.3 0.4
Confirmatory 270.1→238.1
Aldicarb Primary 213→88.9 8 2.1
Confirmatory 213→116
Atrazine Primary 216.1→174 9.2 3.6
Confirmatory 216.1→95.9
Desethylatrazine Primary 188→146 7.6 5.4
Confirmatory 188→78.8
Desisopropylatrazine Primary 174→96 6.6 1.3
Confirmatory 174→78.8
Azoxystrobin Primary 404.2→372.2 9.6 3.7
Confirmatory 404.2→344.2
Bentazon Primary 239→197 6.4 1.1
Confirmatory 239→175
Carbaryl Primary 202.1→145 8.8 3.6
Confirmatory 202.1→127
Chlorpyrifos Primary 350→197.9 11.4 1.8
Confirmatory 350→322
A
Clopyralid Primary 189.9→145.9 5.2 1.5
Confirmatory 191.9→147.9
Clothianidin Primary 250→169 6.9 1.6
Confirmatory 250→131.9
Diazinon Primary 305.1→169 10.6 1.6
Confirmatory 305.1→153
A
Dicamba Primary 218.9→174.9 7.1 1.5
Confirmatory 220.9→176.9
Fipronil Primary 435→330 10.3 5.7
Confirmatory 435→318
Imidacloprid Primary 256.1→209.1 6.9 1.1
Confirmatory 256.1→175
Malathion Primary 331.1→127 9.9 1.2
Confirmatory 331.1→285
Methomyl Primary 163→87.9 6.1 1.8
Confirmatory 163→105.9
Metolachlor Primary 284.1→252.1 10.3 2.4
Confirmatory 284.1→176.1
Metribuzin Primary 215.1→187.1 8.5 NA
A
Picloram Primary 240.9→196.9 5.9 1
Confirmatory 238.9→194.9
Propiconazole Primary 342.1→158.9 10.6 7.2
Confirmatory 342.1→205
Simazine Primary 202→132 7.6 5.4
Confirmatory 202→124
Tebuconazole Primary 308.2→70 10.5 11.2
Confirmatory 308.2→125
Thiamethoxam Primary 292.1→211.1 6.3 4
Confirmatory 292.1→131.9
A
Triclopyr Primary 253.9→195.9 7.8 2.9
Confirmatory 253.9→217.9
Surrogates
A
2,4-D (Ring-D3) Primary 221.9→163.8 7.6 NA
Atrazine (ethyl-D5) Primary 221.1→179 9.2 NA
Desethylatrazine (iso-propyl-D7) Primary 195→146.9 7.6 NA
Desisopropylatrazine (ethyl-D5) Primary 179→100.9 6.6 NA
Bentazon -D7 Primary 246.1→182 6.4 NA
Carbofuran (Ring-13C6) Primary 228.1→171 8.6 NA
Clothianidin -D3 Primary 253→131.9 6.9 NA
Diazinon (Diethyl-D10) Primary 315.2→170 10.6 NA
A
Dicamba -D3 Primary 223.9→179.9 7.1 NA
Imidacloprid -D4 Primary 260.1→213.1 6.9 NA
Methomyl (Acetohydroxamate-13C2, 15N) Primary 166→90.8 6.1 NA
Simazine (Diethyl-D10) Primary 212.1→134 7.6 NA
Tebuconazole (tert-Butyl-D9) Primary 317.2→69.9 10.5 NA
Thiamethoxam -D3 Primary 295→214.1 6.3 NA
A
Indicates analyzed under acidic LC conditions.
D8025 − 23
7.5.2 A 10 mL Lock Tip Glass Syringe size is recommended 8.14 Atrazine (CAS # 1912-24-9).
since a 10 mL prepared sample size is used in this test method.
8.15 Desethylatrazine (CAS # 6190-65-4).
If a smaller volume syringe is used, do not wash out the syringe
8.16 Desisopropylatrazine (CAS # 1007-28-9).
or change filters while filtering the same sample if multiple
refills of the syringe are required in order to filter the 10 mL
8.17 Azoxystrobin (CAS # 131860-33-8).
prepared sample.
8.18 Bentazon (CAS # 25057-89-0).
7.5.3 Filter Unit —PTFE filter units were used to filter the
8.19 Carbaryl (CAS # 63-25-2).
samples.
8.20 Chlorpyrifos (CAS # 2921-88-2).
7.6 Vials—2-mL autosampler vials (LC vials) with pre-slit
PTFE/silicone septa or equivalent.
8.21 Clopyralid (CAS # 1702-17-6).
7.7 Sonicator.
8.22 Clothianidin (CAS # 210880-92-5).
7.8 Oven—Capable to achieve 250 °C.
8.23 Diazinon (CAS # 333-41-5).
7.9 VOA Vials—Amber, 40 mL.
8.24 Dicamba (CAS # 1918-00-9).
8.25 Fipronil (CAS # 120068-37-3).
8. Reagents and Materials
8.26 Imidacloprid (CAS # 138261-41-3).
8.1 Purity of Reagents—High Performance Liquid Chroma-
tography (HPLC) pesticide residue analysis and spectropho-
8.27 Malathion (CAS # 121-75-5).
tometry grade chemicals must be used in all tests. Unless
8.28 Methomyl (CAS # 16752-77-5).
indicated otherwise, it is intended that all reagents must
conform to the Committee on Analytical Reagents of the 8.29 Metolachlor (CAS # 51218-45-2).
American Chemical Society. Other reagent grades may be
8.30 Metribuzin (CAS # 21087-64-9).
used provided they are first determined to be of sufficiently
8.31 Picloram (CAS # 1918-02-1).
high purity to permit their use without affecting the accuracy of
the measurements.
8.32 Propiconazole (CAS # 60207-90-1).
8.2 Purity of Water—Unless otherwise indicated, references
8.33 Simazine (CAS # 122-34-9).
to water must be understood to mean reagent water conforming
8.34 Tebuconazole (CAS # 107534-96-3).
to Type 1 of Specification D1193. It must be demonstrated that
this water does not contain contaminants at concentrations 8.35 Thiamethoxam (CAS # 153719-23-4).
sufficient to interfere with the analysis.
8.36 Triclopyr (CAS # 55335-06-3).
8.3 All prepared solutions are routinely replaced every year
8.37 Isotopically Labeled Pesticide Standards
if not previously discarded for quality control failure.
(Surrogates)—There are not isotopically labeled surrogates for
8.4 Gases—Ultrapure nitrogen and argon. every target analyte. The labeled surrogate only mimics its
unlabeled target analyte. The isotopically labeled carbofuran
8.5 Formic Acid (CAS # 64-18-6).
was chosen to mimic carbaryl. (Note—P&A data show that the
8.6 Acetonitrile (CAS # 75-05-8).
labeled carbofuran is not a good surrogate for carbaryl even
though they are structurally similar.) Surrogates may be added
8.7 Methanol (CAS # 67-56-1).
or deleted from the below list if new ones become available or
8.8 Ammonium Formate (CAS # 540-69-2).
if the existing ones are not readily available. The surrogate list
8.9 2-Propanol (isopropyl alcohol, CAS # 67-63-0).
is long and expensive to maintain. If surrogates are not
available at the time of analysis it will be mentioned in the case
8.10 2,4-Dichlorophenoxyacetic acid (2,4-D, CAS # 94-75-
narrative that accompanies the data, if extra surrogates are
7).
added this will also be mentioned in the case narrative (CAS
8.11 Acetochlor (CAS # 34256-82-1).
#’s are for the unlabeled native analyte).
8.12 Alachlor (CAS # 15972-60-8).
8.37.1 2,4-Dichlorophenoxyacetic acid (2,4-D (Ring-D3),
CAS # 94-75-7).
8.13 Aldicarb (CAS # 116-06-3).
8.37.2 Atrazine (ethyl-D5, CAS # 1912-24-9).
8.37.3 Desethylatrazine (iso-propyl-D7, CAS # 6190-65-4).
A Millipore IC Millex-LG PTFE/0.2μm membrane syringe driven membrane
8.37.4 Desisopropylatrazine (ethyl-D5, CAS # 1007-28-9).
filter unit (Millex is a trademark of Merck KGAA, Darmstadt, Germany) was used,
8.37.5 Bentazon (D7, CAS # 25057-89-0).
if you are aware of an alternative filter that meets the performance of the standard,
please provide this information to ASTM International Headquarters. Your com-
8.37.6 Carbofuran (Ring-13C6, CAS # 1563-66-2).
ments will receive careful consideration at a meeting of the responsible technical
8.37.7 Clothianidin (D3, CAS # 210880-92-5).
committee, which you may attend.
8.37.8 Diazinon (diethyl-D10, CAS # 333-41-5).
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Standard-Grade Reference Materials, American Chemical Society, Washington,
8.37.9 Dicamba (D3, CAS # 1918-00-9).
DC. For suggestions on the testing of reagents not listed by the American Chemical
8.37.10 Imidacloprid (D4, CAS # 138261-41-3).
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
8.37.11 Methomyl (Acetohydroxamate-13C2, 15N, CAS #
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
copeial Convention, Inc. (USPC), Rockville, MD. 16752-77-5).
D8025 − 23
8.37.12 Simazine (diethyl-D10, CAS # 122-34-9). 11.2.3 Seal Wash—Solvent: 50 % methanol ⁄50 % water;
8.37.13 Tebuconazole (tert-Butyl-D9, CAS # 107534-96-3). Time: 5 min.
8.37.14 Thiamethoxam (D3, CAS # 153719-23-4).
11.3 Mass Spectrometer Parameters:
9. Hazards 11.3.1 To acquire the maximum number of data points per
SRM channel while maintaining adequate sensitivity, the tune
9.1 Normal laboratory safety applies to this method. Ana-
parameters may be optimized according to the instrument used.
lysts should wear safety glasses, gloves, and lab coats when
Each peak requires at least 10 scans per peak for adequate
working in the lab. Analysts should review the Safety Data
quantitation. Variable parameters regarding SRM transitions,
Sheets (SDS) for all reagents used in this method.
and cone and collision energies are shown in Table 4. Mass
10. Sampling and Preservation spectrometer parameters used in the development of this
method are listed below.
10.1 Grab samples are collected in amber glass containers
11.3.2 The instrument is set in the Electrospray source
with inert-lined caps, such as, 40 mL amber VOA vials. As part
setting. The values for the following parameters are shown here
of the overall quality assurance program for this test method,
for information only. These conditions should be checked and
field blanks exposed to the same field conditions as samples are
optimized when required.
collected and analyzed according to this standard to assess the
potential for field contamination, refer to Guide D3856 as a Methanol/Water/Ammonium Formate Analysis Run Conditions
guide for sampling. This test method is based upon an 8 mL
Capillary Voltage: 1 kV in both ESI modes
sample size per analysis. If different sample sizes are used,
Cone: Variable depending on analyte
spiking solution amounts may need to be modified. EPA Source Offset (V) 10
Source Temperature: 150 °C
publication SW-846 may be used as a sampling guide. Samples
Desolvation Gas Temperature: 500 °C
must be shipped with a trip blank and between freezing and
Desolvation Gas Flow: 900 L/h
6 °C. Cone Gas Flow: 150 L/h
Collision Gas Flow: 0.15 mL/min
10.2 Once received the sample temperature is taken and
Low Mass Resolution 1: 2.7
High Mass Resolution 1: 14.7
should be less than 6 °C. If the receiving temperature is greater
Ion Energy 1: 0.5
than 6 °C, the sample temperature is noted in the case narrative
Entrance Energy: 1
accompanying the data. Samples should be stored refrigerated
Collision Energy: Variable depending on analyte
Exit Energy: 1
between 0 °C and 6 °C from the time of collection until
Low Mass Resolution 2: 2.8
analysis.
High Mass resolution 2: 14.7
Ion Energy 2: 1.5
10.3 The samples should be analyzed within 14 days of
Gain: 1.0
collection. No holding time study has been done on water
Multiplier: 535
Inter-Scan Delay: 0.003 s
matrices tested in this test method. Holding time may vary
Polarity Switching Inter-scan Delay: 0.020 s
depending on the matrix and individual laboratories should
determine the holding time in their matrix, refer to Practice
Methanol/Water/Formic Acid Analysis Run Conditions
D4841.
Capillary Voltage: Positive mode 2 kV, Negative mode 0.75 kV
11. Preparation of LC/MS/MS
Cone: Variable depending on analyte
Source Offset (V) 10
11.1 LC Chromatograph Operating Conditions:
Source Temperature: 150 °C
11.1.1 Injections of all standards and samples are made at a
Desolvation Gas Temperature: 300 °C
Desolvation Gas Flow: 1000 L/h
25 μL or 50 μL volume. Other injection volumes may be used
Cone Gas Flow: 300 L/h
to optimize conditions. Standards and sample extracts must be
Collision Gas Flow: 0.15 mL/min
in a 80:20 water:methanol solution. In the case of extreme Low Mass Resolution 1: 2.7
High Mass Resolution 1: 14.7
concentration differences amongst samples, it is wise to ana-
Ion Energy 1: 0.5
lyze a blank after a concentrated sample and before a dilute
Entrance Energy: 1
sample to minimize carry-over of analytes from injection to Collision Energy: Variable depending on analyte
Exit Energy: 1
injection. However, there should not be carry-over between
Low Mass Resolution 2: 2.8
samples. The LC utilized to develop this test method has a flow
High Mass resolution 2: 14.7
through LC needle design. The gradient conditions for the two Ion Energy 2: 1.5
Gain: 1.0
liquid chromatography analysis runs are shown in Tables 2 and
Multiplier: 535
3. The primary SRM transition chromatograms at the lowest
Inter-Scan Delay: 0.003 s
calibration level are shown in the Appendix, Figs. X1.1-X1.5. Polarity Switching Inter-scan Delay: 0.020 s
11.2 LC Auto Sampler Conditions:
12. Calibration and Standardization
11.2.1 Needle Wash Solvent—60 % acetonitrile ⁄40 %
2-propanol. 8 s wash time before and after injection. Instru- 12.1 The mass spectrometer must be calibrated as per
ment manufacturer’s specifications should be followed in order manufacturer’s specifications before analysis. Analytical val-
to eliminate sample carry-over. ues satisfying test method criteria have been achieved using the
11.2.2 Temperatures—Column, 35 °C; Sample following procedures. Prepare all solutions in the lab using
compartment, 15 °C. Class A volumetric glassware.
D8025 − 23
12.2 Calibration and Standardization—To generate a cali- and confirmatory SRM transitions of the pesticides and surro-
bration curve, analyze seven calibration standards of the gates. Calibration software is utilized to conduct the quantita-
pesticide compounds prior to sample analysis as shown in tion of the analytes using the primary SRM transition. The
Table 6. Calibration stock standard solution is prepared from ratios of the primary/confirmatory SRM transitions area counts
the target and surrogate spike solutions directly to ensure are given in Table 5 and will vary depending on the individual
consistency. Stock standard Solution A containing the pesti- tuning conditions. The primary/confirmatory SRM transitions
cides is prepared at Level 7 concentration and aliquots of that area ratio must be within 35 % of the individual labs’ accepted
solution are diluted to prepare Levels 1 through 6. The primary/confirmatory SRM transitions area ratio. The primary
following steps will produce 1 mL calibration standards with SRM transition of the analytes are used for quantitation and the
the concentration values shown in Table 6. The analyst is confirmatory SRM transitions for confirmation. This gives
responsible for recording initial component weights carefully added confirmation by isolating the parent ion, forming prod-
when working with pure materials and correctly carrying the uct ions via fragmentation, and relating it to the retention time
weights through the dilution calculations. in the calibration standard. Metribuzin and the surrogates only
12.2.1 At a minimum, five calibration levels are required have a primary SRM transition.
when using a linear calibration curve and six calibration levels 12.2.5 Depending on sensitivity and matrix interference
are required when using a quadratic calibration curve. An issues dependent on sample type, a confirmatory SRM transi-
initial seven point curve may be used to allow for the dropping tion may be substituted as the primary SRM transition for
of the lower level calibration point if the individual laborato- quantitation during analysis. This must be explained in a
ry’s instrument can’t achieve low detection limits. This should narrative accompanying the data. New primary/confirmatory
allow for at least a five or six point calibration curve to be ion ratios will then be determined if switching the SRM
obtained. transitions used to quantitate and confirm. The new primary/
12.2.2 Calibration stock standard Solution A (Level 7, Table confirmatory SRM transitions area ratio is required to be within
6) is prepared from the target and surrogate spike solutions 35 % of the individual labs’ new primary/confirmatory SRM
directly to ensure consistency. 1.25 mL of the surrogate spike transitions area ratio.
and 1.25 mL of the pesticide Target Spike Solution is added to 12.2.6 The calibration software manual should be consulted
a 50 mL volumetric flask and brought up to 50 mL volume with to use the software correctly. The quantitation method is set as
80:20 water and methanol solution. This stock standard Solu- an external calibration using the peak areas in ng/L units.
tion A (Level 7, Table 6) is diluted to prepare Levels 1 through Concentrations may be calculated using the data system
6 as shown in Tables 6 and 7. The preparation of the Level 7 software to generate linear regression or quadratic calibration
standard can be accomplished using appropriate volumes and curves. Forcing the calibration curve through the origin (X=0,
concentrations of stock solutions as per a particular laborato- Y=0) is not recommended. Curves should be evaluated using
ry’s standard procedure. relative error or relative standard error.
12.2.3 Aliquots of Solution A are then diluted with 80:20 12.2.7 Linear calibration may be used if the point of origin
water:methanol to prepare the 1 mL desired calibration levels is excluded and a fit weighting of 1/X is used in order to give
in 2 mL amber glass LC vials, as described in Table 7. The more emphasis to the lower concentrations. Each calibration
calibration vials must be used within 24 h to ensure optimum
results. Calibration standards are not filtered.
Management and Technical Requirements for Laboratories Performing Envi-
12.2.4 Inject each standard and obtain its chromatogram. An
ronmental Analysis; Module 4: Quality Systems for Chemical Testing; The NELAC
external calibration technique is used to monitor the primary Institute, 2017.
TABLE 6 Concentrations of Calibration Standards (ng/L)
Pesticide and Surrogate
LV1 LV2 LV3 LV4 LV5 LV6 LV7
Concentrations (ng/L)
Azoxystrobin 25 50 100 200 400 800 1 000
Atrazine, Desethylatrazine, Clothianidin, 50 100 200 400 800 1 600 2 000
Diazinon, Imidacloprid, Metolachlor,
Propiconazole, Simazine, Tebuconazole,
Thiamethoxam, Atrazine (ethyl-D5),
Desethylatrazine (iso-propyl-D7), Clothianidin-
D3, Diazinon (diethyl-D10), Imidacloprid-D4,
Simazine (diethyl-D10), Tebuconazole (tert-
Butyl-D9), Thiamethoxam-D3
Desisopropylatrazine, Malathion, Metribuzin, 100 200 400 800 1 600 3 200 4 000
Desisopropylatrazine (ethyl-D5)
2,4-D, Acetochlor, Alachlor, Aldicarb, 200 400 800 1600 3 200 6 400 8 000
Bentazon, Carbaryl, Chlorpyrifos, Fipronil,
Methomyl, 2,4-D (Ring-D3), Bentazon-D7,
Carbofuran (Ring-13C6), Methomyl
(Acetohydroxamate-13C2, 15N)
Triclopyr 1 000 2 000 4 000 8 000 16 000 32 000 40 000
Picloram 5 000 10 000 20 000 40 000 80 000 160 000 200 000
Dicamba, Dicamba-D3 10 000 20 000 40 000 80 000 160 000 320 000 400 000
Clopyralid 20 000 40 000 80 000 160 000 320 000 640 000 800 000
D8025 − 23
TABLE 7 Preparation of Calibration Standards
Solution LV1 LV2 LV3 LV4 LV5 LV6 LV7
A
A 25 μL 50 μL 100 μL 200 μL 400 μL 800 μL 1000 μL
B
B 975 μL 950 μL 900 μL 800 μL 600 μL 200 μL 0 μL
A
Solution A: Level 7 stock solution prepared according to 12.2 and at Table 6 concentrations.
B
Solution B: 80 % Water : 20 % Methanol.
point used to generate the curve must have a calculated percent 12.3.2 Calculate the mean (average) percent recovery and
deviation less than 25 % from the generated curve. relative standard deviation (RSD) of the four values and
12.2.8 Quadratic calibration may be used if the point of compare to the acceptable ranges of the QC acceptance criteria
origin is excluded, and a fit weighting of 1/X is used in order for the Initial Demonstration of Performance in Table 8.
to give more emphasis to the lower concentrations. Each
12.3.3 This study should be repeated until the single opera-
calibration point used to generate the curve must have a
tor precision and mean recovery are within the limits in Table
calculated percent deviation less than 25 % from the generated
8. If a concentration other than the recommended concentration
curve.
is used, refer to Practice D5847 for information on applying the
12.2.9 The retention time window of the SRM transitions
F test and t test in evaluating the acceptability of the mean and
must be within 5 % of the retention time of the analyte in a
standard deviation.
midpoint calibration standard. If this is not the case, re-analyze
12.3.3.1 The QC acceptance criteria for the Initial Demon-
the calibration curve to determine if there was a shift in
stration of Performance in Table 8 were generated from the
retention time during the analysis and the sample needs to be
single-laboratory data shown in the Precision and Bias Section
re-injected. If the retention time is still incorrect in the sample,
16. Data from reagent water and surface water are shown in the
refer to the analyte as an unknown.
Precision and Bias Section 16. It is recommended that each
12.2.10 A midpoint calibration check standard must be
laboratory determine in-house QC acceptance criteria which
analyzed at the end of each batch of 30 samples or within 24 h
meet or exceed the criteria in this standard. References
after the initial calibration curve was generated, the criteria in
generating QC acceptance criteria are ASTM Practices D2777,
the individual labs’ quality system may be more restrictive
D5847, E2554 and Method 8000 in EPA publication SW-846.
pertaining to the number of samples. This end calibration
check should come from the same calibration standard solution 12.4 Surrogate Spiking Solution:
that was used to generate the initial curve. The results from the
12.4.1 A surrogate spiking solution containing fourteen
end calibration check standard must have a percent deviation
isotopically-labeled pesticides (listed in Section 8) are added to
less than 30 % from the calculated concentration for the target
all samples. 50 μL of a methanolic solution containing the
analyte. If the results are not within these criteria, corrective
surrogates and concentrations are listed in Table 9, Concentra-
action including re-occurrence minimization is performed and
tions in Surrogate Spike Solution, is added to all 8 mL samples
either all samples in the batch are re-analyzed against a new
to achieve the concentration in the sample listed in Table 9,
calibration curve or the affected results are qualified with an
Concentration in Water Sample.
indication that they do not fall within the performance criteria
12.4.2 The result obtained for the surrogates must fall
of the test method. If the analyst inspects the vial containing
within the limits in Table 8.
the end calibration check standard and notices that the sample
12.4.3 There are fourteen surrogates for this analysis. The
evaporated affecting the concentration or other anomaly, a new
isotopically-labeled surrogate represents the unlabeled native
end calibration check standard may be made and analyzed. If
analyte. Carbofuran (Ring-13C6) represents carbaryl in this
this new end calibration check standard has a percent deviation
standard. No qualifications based on surrogate recovery need to
less than 30 % from the calculated concentration for the target
be made for the analytes that do not have representative
analyte, the results may be reported unqualified.
surrogates. It is left to the analyst’s judgment to qualify data
12.3 If a laboratory has not performed the test before or if
based upon non-representative surrogates. The user of the data
there has been a major change in the measurement system, for
must also make decisions based on all QC available. If the
example, new analyst, new instrument, etc., an instrument
result is not within these limits, sample analysis is halted until
qualification study including reporting limit check sample
corrective action resolving the problem has been performed.
(RLCS), calibration range determination and precision and bias
Impacted samples in the batch are either re-analyzed, or the
determination must be performed to demonstrate laboratory
results are flagged with a qualifier stating that they do not fall
capability.
within the performance criteria of the test method.
12.3.1 Analyze at least four replicates of a spiked water
12.5 Method Blank:
sample containing the pesticides at a prepared sample concen-
tration in the calibration range of Levels 3–6. A Level 4 12.5.1 A method blank for every 30 samples is prepared in
prepared sample concentration was used to set the QC accep- 8 mL of reagent water, which is taken through the sample
tance criteria in this method. The matrix and chemistry should preparation Section 13, to investigate for contamination during
be similar to the matrix used in this test method. Each replicate sample preparation. The concentration of target analytes in the
must be taken through the complete analytical test method blank must be at less than 25 % of the reporting limit or the
including any sample manipulation and preparation steps. data must be qualified as having a blank issue and the reporting
D8025 − 23
TABLE 8 QC Acceptance Criteria
NOTE 1—Table 8 data is preliminary until a multi-lab validation study is completed.
Initial Demonstration of Performance Laboratory Control Sample
Spiked Sample Recovery (%) Precision Recovery (%)
Analyte
Conc. (ng/L)
Maximum
Lower Limit Upper Limit Lower Limit Upper Limit
% RSD
2,4-D 2 000 70 130 30 70 130
Acetochlor 2 000 70 130 30 70 130
Alachlor 2 000 70 130 30 70 130
Aldicarb 2 000 70 130 30 70 130
Atrazine 500 70 130 30 70 130
Desethylatrazine 500 70 130 30 70 130
Desisopropylatrazine 1 000 70 130 30 70 130
Azoxystrobin 250 70 130 30 70 130
Bentazon 2 000 70 130 30 70 130
Carbaryl 2 000 50 130 30 50 130
Chlorpyrifos 2 000 50 130 30 50 130
Clopyralid 200 000 70 130 30 70 130
Clothianidin 500 70 130 30 70 130
Diazinon 500 70 130 30 70 130
Dicamba 100 000 70 130 30 70 130
Fipronil 2 000 60 130 30 60 130
Imidacloprid 500 70 130 30 70 130
Malathion 1 000 40 130 30 40 130
Methomyl 2 000 70 130 30 70 130
Metolachlor 500 70 130 30 70 130
Metribuzin 1 000 70 130 30 70 130
Picloram 50 000 70 130 30 70 130
Propiconazole 500 50 130 30 50 130
Simazine 500 70 130 30 70 130
Tebuconazole 500 70 130 30 70 130
Thiamethoxam 500 70 130 30 70 130
Triclopyr 10 000 70 130 30 70 130
Surrogates NA NA NA NA NA NA
2,4-D (Ring-D3) 2 000 70 130 30 70 130
Atrazine (ethyl-D5) 500 70 130 30 70 130
Desethylatrazine (iso-propyl-D7) 500 70 130 30 70 130
Desisopropylatrazine (ethyl-D5) 1 000 70 130 30 70 130
Bentazon -D7 2 000 70 130 30 70 130
Carbofuran (Ring-13C6) 2 000 70 130 30 70 130
Clothianidin-D3 500 70 130 30 70 130
Diazinon-(diethyl-D10) 500 70 130 30 70 130
Dicamba-D3 100 000 70 130 30 70 130
Imidacloprid-D4 500 70 130 30 70 130
Methomyl (Acetohydroxamate-13C2, 15N) 2 000 70 130 30 70 130
Simazine (diethyl-D10) 500 70 130 30 70 130
Tebuconazole (tert-Butyl-D9) 500 70 130 30 70 130
Thiamethoxam-D3 500 70 130 30 70 130
TABLE 9 Surrogate Spike Concentrations
12.6.1 Each batch or within the 24 h analysis window a
Concentration in Concentration in
reporting limit check sample must be analyzed. The reporting
Surrogate Surrogate Spike Water Sample
limit check sample is processed like a Laboratory Control
Solution (μg/L) (ng/L)
Sample just spiked at or near (1 to 2 times) the reporting limit.
Atrazine (ethyl-D5), Desethylatrazine 80 500
The concentration of the RLCS may be reported below the
(iso-propyl-D7), Clothianidin-D3,
Diazinon (diethyl-D10), Imidacloprid-
reporting limit since the spike is at or near the reporting limit.
D4, Simazine (diethyl-D10),
This sample is to ensure if the analytes were present at the
Tebuconazole (tert-Butyl-D9),
Thiamethoxam-D3
reporting limit that they would be identified. The recovery
Desisopropylatrazine (ethyl-D5) 160 1000
limits for the RLCS are 35 % to 150 %, if any analytes are
2,4-D (Ring-D3), Bentazon-D7, 320 2000
outside of these limits the QC exceedance is explained in a
Carbofuran (Ring-13C6), Methomyl
(Acetohydroxamate-13C2, 15N)
narrative accompanying the data or the batch is re-prepared and
Dicamba-D3 16 000 100 000
analyzed. A continued failure must be explained, investigated
and should be corrected.
12.6.2 To prepare the RLCS, 8 mL of reagent water is added
to a 40 mL VOA vial. The sample is spiked with 6.25 μL of the
target spike solution (see 12.7). The sample is then prepared as
limit must be raised to at least 3 times above the blank
described in Section 13.
contamination concentration.
12.6 Reporting Limit Check Sample (RLCS): 12.7 Laboratory Control Sample (LCS):
D8025 − 23
12.7.1 Analyze at least one LCS with the pesticides at a A V 1 V 2 BV
~ !
? S S?
P 5 100 (1)
mid-level prepared sample concentration. The concentration of CV
pesticides at a prepared sample concentration in the calibration
where:
range of Levels 3–6 should be used. The LCS is prepared
A = concentration found in spiked sample,
following the analytical method and analyzed with each
...

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.
Designation: D8025 − 16 D8025 − 23
Standard Test Method for
Determination of Select Pesticides in Water by Multiple
Reaction Monitoring Liquid Chromatography Tandem Mass
Spectrometry
This standard is issued under the fixed designation D8025; 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
1.1 This procedure test method covers a method for analysis of selected pesticides in a water matrix by filtration followed with
liquid chromatography/electrospray ionization tandem mass spectrometry analysis. The samples are prepared in 20 % 20 %
methanol, filtered, and analyzed by liquid chromatography/tandem mass spectrometry. This method was developed for an
agricultural run-off study, not for low level analysis of pesticides in drinking water. This method may be modified for lower level
analysis. The analytes are qualitatively and quantitatively determined by this method. This method adheres to multiple reaction
monitoring (MRM) mass spectrometry.
1.2 A full collaborative study to meet the requirements of Practice D2777 has not been completed. This standard contains
single-operator precision and bias based on single-operator data. Publication of standards that have not been fully validated is done
to make the current technology accessible to users of standards, and to solicit additional input from the user community.
1.3 A reporting limit check sample (RLCS) is analyzed during every batch to ensure that if an analyte was present in a sample
at or near the reporting limit it would be positively identified and accurately quantitated within set quality control limits. A method
detection limit (MDL) study was not done for this method, the method detection limits would be much lower than the reporting
limits in this method and would be irrelevant. A RLCS was determined to be more applicable for this standard. If this method is
adapted to report much lower or near the MDL then a MDL study would be warranted.
1.4 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this
standard.
1.5 The Reporting Range for the target analytes are listed in Table 1.
1.5.1 The reporting limit in this test method is the minimum value below which data are documented as non-detects. The reporting
limit is calculated from the concentration of the Level 1 calibration standard as shown in Table 6 after taking into account an 8
mL water sample volume and a final diluted sample volume of 10 mL (80 % water/20 % methanol).
1.6 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.
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, 2016April 15, 2023. Published August 2016June 2023. Originally approved in 2016. Last previous edition approved in 2016 as
D8025 – 16. DOI: 10.1520/D8025-16.10.1520/D8025-23.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8025 − 23
TABLE 1 Reporting Range
Analyte Reporting Ranges, (ng/L)
2,4-D 250–10 000
Acetochlor 250–10 000
Alachlor 250–10 000
Aldicarb 250–10 000
Atrazine 62.5–2 500
Desethylatrazine 62.5–2 500
Desisopropylatrazine 125–5 000
Azoxystrobin 31.2–1 250
Bentazon 250–10 000
Carbaryl 250–10 000
Chlorpyrifos 250–10 000
Clopyralid 25 000–1 000 000
Clothianidin 62.5–2 500
Diazinon 62.5–2 500
Dicamba 12 500–500 000
Fipronil 250–10 000
Imidacloprid 62.5–2 500
Malathion 125–5 000
Methomyl 250–10 000
Metolachlor 62.5–2 500
Metribuzin 125–5 000
Picloram 6 250–250 000
Propiconazole 62.5–2 500
Simazine 62.5–2 500
Tebuconazole 62.5–2 500
Thiamethoxam 62.5–2 500
Triclopyr 1 250–5 000
1.7 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.
2. Referenced Documents
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
D3856 Guide for Management Systems in Laboratories Engaged in Analysis of Water
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
2.2 Other Document:
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 of Terms Specific to This Standard:
3.2.1 batch QC, n—all the quality control samples and standards included in an analytical procedure.
3.2.2 independent reference material, IRM, n—a material of known purity and concentration obtained either from the National
Institute of Standards and Technology (NIST) or other reputable supplier.
3.2.2.1 Discussion—
The IRM shallmust be obtained from a different lot of material than is used for calibration.
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.
Available from National Technical Information Service (NTIS), U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://www.epa.gov/
epawaste/hazard/testmethods/index.htm
D8025 − 23
3.2.3 reporting limit, RL, n—the minimum concentration below which data are documented as non-detects.
3.2.4 reporting limit check sample, RLCS, n—a sample used to ensure that if the analyte was present at the reporting limit, it would
be confidently identified.
3.3 Acronyms:
3.3.1 CCC, n—Continuing Calibration Check
3.3.2 CRW, n—Chicago River Water
3.3.3 IC, n—Initial Calibration
3.3.4 LC, n—Liquid Chromatography
3.3.5 LCS/LCSD, n—Laboratory Control Sample/Laboratory Control Sample Duplicate
3.3.6 MDL, n—Method Detection Limit
3.3.7 MeOH, n—Methanol
-3
3.3.8 mM, n—millimolar, 1 × 10 moles/L
3.3.9 MRM, n—Multiple Reaction Monitoring
3.3.10 MS/MSD, n—Matrix Spike/Matrix Spike Duplicate
3.3.11 NA, adj—Not Available
3.3.12 ND, n—non-detect
3.3.13 P&A, n—Precision and Accuracy
3.3.14 ppt, n—parts-per-trillion
3.3.15 QA, adj—Quality Assurance
3.3.16 QC, adj—Quality Control
3.3.17 RL, n—Reporting Limit
3.3.18 RLCS, n—Reporting Limit Check Sample
3.3.19 RSD, n—Relative Standard Deviation
3.3.20 RT, n—Retention Time
3.3.21 SDS, n—Safety Data Sheets
3.3.22 SRM, n—Single Reaction Monitoring
3.3.23 SS, n—Surrogate Standard
D8025 − 23
3.3.24 TC, n—Target Compound
3.3.25 VOA, n—Volatile Organic Analysis
4. Summary of Test Method
4.1 The operating conditions presented in this standard have been successfully used in the determination of the select pesticides
in water; however, this standard is intended to be performance based and alternative operating conditions can be used to perform
this method provided data quality objectives are attained.
4.2 For pesticide analysis, samples are shipped to the lab on ice and analyzed within 14 days of collection. A sample (8 mL) is
transferred to an amber VOA vial, an isotopically labeled pesticide surrogate mix is added to all samples followed by a pesticide
spike solution which is added only to the Reporting Limit Check Samples, Laboratory Control and Matrix Spike samples before
the addition of methanol. Then 2 mL of methanol is added to each sample and hand shaken or vortexed for 1 minute. 1 min. The
samples are then filtered through a PTFE membrane syringe driven filter unit and then analyzed by LC/MS/MS. All concentrations
reported only to the reporting limit.
4.3 The analysis of the sample requires two separate analysis methods, one using the LC gradient conditions in Table 2 with the
Methanol/Water/Ammonium Formate and the second using the LC gradient conditions in Table 3 with the Methanol/Water/Formic
acid. Each analysis set is to be analyzed separately in two different complete sample sequences which includes the exact same
samples and may even include the same calibration level standards. The only analytes reported from the formic acid run conditions
are 2,4-D, Clopyralid, Dicamba, Picloram, Triclopyr, 2,4-D (Ring-D3) and Dicamba-D3, the rest of the analytes are reported from
the ammonium formate analysis run.
4.4 The pesticides are identified by comparing the single reaction monitoring (SRM) transition and its confirmatory SRM
transitions if correlated to the known standard SRM transition (Tables 4 and 5) and quantitated utilizing an external calibration.
The final report issued for each sample lists the concentration of pesticides, if detected, or RL, if not detected, in ng/L and surrogate
recovery.
5. Significance and Use
5.1 Pesticides may be used in various agricultural and household products. These products may enter waterways at low levels
through run-off or misuse near water resources. Hence, there is a need for quick, easy and robust method to determine pesticide
concentration in water matrices for understanding the sources and concentration levels in affected areas.
5.2 This method has been single-laboratory validated in reagent water and surface waters (Tables 12-14).
6. Interferences
6.1 All glassware is washed in hot water with detergent and rinsed in hot water followed by distilled water. The glassware is then
dried and heated in an oven at 250°C for 15 to 30 minutes. 250 °C for 15 min to 30 min. All glassware is subsequently rinsed or
sonicated, or both, with acetone, n-propanol, acetonitrile, or a combination thereof.
6.2 All reagents and solvents should be pesticide residue purity or higher to minimize interference problems.
TABLE 2 Gradient Conditions for Neutral Liquid Chromatography
Percent
Percent
Time (min) Flow (mL/min) Percent Methanol 200 mM Ammonium Formate
95 % Water: 5 % Methanol
(95 % Water: 5 % Methanol)
0 0.3 95 0 5
1.5 0.3 95 0 5
9 0.3 0 95 5
12 0.3 0 95 5
13 0.3 95 0 5
16 0.3 95 0 5
D8025 − 23
TABLE 3 Gradient Conditions for Acidic Liquid Chromatography
Percent
Percent
Time (min) Flow (mL/min) Percent Methanol 4 % Formic Acid
95 % Water: 5 % Methanol
(95 % Water: 5 % Methanol)
0 0.3 95 0 5
1.5 0.3 95 0 5
6 0.3 0 95 5
9 0.3 0 95 5
10 0.3 95 0 5
13 0.3 95 0 5
6.3 Matrix interferences may be caused by contaminants in the sample. The extent of matrix interferences can vary considerably
depending on variations in the sample matrices.
D8025 − 23
TABLE 4 SRM Ions and Analyte-Specific Mass Spectrometer Parameters
Primary/ ESI Mode Cone Collision
Chemical MRM Transition
Confirmatory Neg/Pos (V) (eV)
A
2,4-D Primary 218.9→160.9 Neg 20 14
Confirmatory 220.9→162.9 14
Acetochlor Primary 270.1→224.1 Pos 20 10
Confirmatory 270.1→148 18
Alachlor Primary 270.1→162 Pos 30 12
Confirmatory 270.1→238.1 18
Aldicarb Primary 213→88.9 Pos 20 16
Confirmatory 213→116 12
Atrazine Primary 216.1→174 Pos 20 18
Confirmatory 216.1→95.9 24
Desethylatrazine Primary 188→146 Pos 30 16
Confirmatory 188→78.8 22
Desisopropylatrazine Primary 174→96 Pos 30 16
Confirmatory 174→78.8 16
Azoxystrobin Primary 404.2→372.2 Pos 20 14
Confirmatory 404.2→344.2 24
Bentazon Primary 239→197 Pos 20 20
Confirmatory 239→175 20
Carbaryl Primary 202.1→145 Pos 10 10
Confirmatory 202.1→127 25
Chlorpyrifos Primary 350→197.9 Pos 30 20
Confirmatory 350→322 11
A
Clopyralid Primary 189.9→145.9 Neg 5 10
Confirmatory 191.9→147.9 10
Clothianidin Primary 250→169 Pos 20 15
Confirmatory 250→131.9 11
Diazinon Primary 305.1→169 Pos 30 20
Confirmatory 305.1→153 20
A
Dicamba Primary 218.9→174.9 Neg 10 8
Confirmatory 220.9→176.9 8
Fipronil Primary 435→330 Pos 30 15
Confirmatory 435→318 23
Imidacloprid Primary 256.1→209.1 Pos 30 17
Confirmatory 256.1→175 23
Malathion Primary 331.1→127 Pos 20 12
Confirmatory 331.1→285 6
Methomyl Primary 163→87.9 Pos 10 10
Confirmatory 163→105.9 11
Metolachlor Primary 284.1→252.1 Pos 30 16
Confirmatory 284.1→176.1 25
Metribuzin Primary 215.1→187.1 Pos 30 16
A
Picloram Primary 240.9→196.9 Neg 10 11
Confirmatory 238.9→194.9 11
Propiconazole Primary 342.1→158.9 Pos 30 22
Confirmatory 342.1→205 17
Simazine Primary 202→132 Pos 40 17
Confirmatory 202→124 17
Tebuconazole Primary 308.2→70 Pos 40 20
Confirmatory 308.2→125 28
Thiamethoxam Primary 292.1→211.1 Pos 20 12
Confirmatory 292.1→131.9 20
A
Triclopyr Primary 253.9→195.9 Neg 10 12
Confirmatory 253.9→217.9 Neg 10 6
Surrogates
A
2,4-D (Ring-D3) Primary 221.9→163.8 Neg 20 14
Atrazine (ethyl-D5) Primary 221.1→179 Pos 20 17
Desethylatrazine (iso-propyl-D7) Primary 195→146.9 Pos 20 18
Desisopropylatrazine (ethyl-D5) Primary 179→100.9 Pos 30 18
Bentazon -D7 Primary 246.1→182 Pos 20 20
Carbofuran (Ring-13C6) Primary 228.1→171 Pos 20 12
Clothianidin -D3 Primary 253→131.9 Pos 20 15
Diazinon (Diethyl-D10) Primary 315.2→170 Pos 30 20
A
Dicamba -D3 Primary 223.9→179.9 Neg 10 8
Imidacloprid -D4 Primary 260.1→213.1 Pos 30 15
Methomyl (Acetohydroxamate-13C2 15N) Primary 166→90.8 Pos 10 8
Simazine (Diethyl-D10) Primary 212.1→134 Pos 40 18
Tebuconazole (tert-Butyl-D9) Primary 317.2→69.9 Pos 40 20
Thiamethoxam -D3 Primary 295→214.1 Pos 30 12
A
Indicates analyzed under acidic LC conditions.
D8025 − 23
TABLE 5 SRM Ions, Retention times and SRM Ion Ratios
Retention
Primary/ MRM Primary/Confirmatory
Chemical Time
Confirmatory Transition SRM Area Ratio
Minutes
A
2,4-D Primary 218.9→160.9 7.6 1.5
Confirmatory 220.9→162.9
Acetochlor Primary 270.1→224.1 10.3 2.5
Confirmatory 270.1→148
Alachlor Primary 270.1→162 10.3 0.4
Confirmatory 270.1→238.1
Aldicarb Primary 213→88.9 8 2.1
Confirmatory 213→116
Atrazine Primary 216.1→174 9.2 3.6
Confirmatory 216.1→95.9
Desethylatrazine Primary 188→146 7.6 5.4
Confirmatory 188→78.8
Desisopropylatrazine Primary 174→96 6.6 1.3
Confirmatory 174→78.8
Azoxystrobin Primary 404.2→372.2 9.6 3.7
Confirmatory 404.2→344.2
Bentazon Primary 239→197 6.4 1.1
Confirmatory 239→175
Carbaryl Primary 202.1→145 8.8 3.6
Confirmatory 202.1→127
Chlorpyrifos Primary 350→197.9 11.4 1.8
Confirmatory 350→322
A
Clopyralid Primary 189.9→145.9 5.2 1.5
Confirmatory 191.9→147.9
Clothianidin Primary 250→169 6.9 1.6
Confirmatory 250→131.9
Diazinon Primary 305.1→169 10.6 1.6
Confirmatory 305.1→153
A
Dicamba Primary 218.9→174.9 7.1 1.5
Confirmatory 220.9→176.9
Fipronil Primary 435→330 10.3 5.7
Confirmatory 435→318
Imidacloprid Primary 256.1→209.1 6.9 1.1
Confirmatory 256.1→175
Malathion Primary 331.1→127 9.9 1.2
Confirmatory 331.1→285
Methomyl Primary 163→87.9 6.1 1.8
Confirmatory 163→105.9
Metolachlor Primary 284.1→252.1 10.3 2.4
Confirmatory 284.1→176.1
Metribuzin Primary 215.1→187.1 8.5 NA
A
Picloram Primary 240.9→196.9 5.9 1
Confirmatory 238.9→194.9
Propiconazole Primary 342.1→158.9 10.6 7.2
Confirmatory 342.1→205
Simazine Primary 202→132 7.6 5.4
Confirmatory 202→124
Tebuconazole Primary 308.2→70 10.5 11.2
Confirmatory 308.2→125
Thiamethoxam Primary 292.1→211.1 6.3 4
Confirmatory 292.1→131.9
A
Triclopyr Primary 253.9→195.9 7.8 2.9
Confirmatory 253.9→217.9
Surrogates
A
2,4-D (Ring-D3) Primary 221.9→163.8 7.6 NA
Atrazine (ethyl-D5) Primary 221.1→179 9.2 NA
Desethylatrazine (iso-propyl-D7) Primary 195→146.9 7.6 NA
Desisopropylatrazine (ethyl-D5) Primary 179→100.9 6.6 NA
Bentazon -D7 Primary 246.1→182 6.4 NA
Carbofuran (Ring-13C6) Primary 228.1→171 8.6 NA
Clothianidin -D3 Primary 253→131.9 6.9 NA
Diazinon (Diethyl-D10) Primary 315.2→170 10.6 NA
A
Dicamba -D3 Primary 223.9→179.9 7.1 NA
Imidacloprid -D4 Primary 260.1→213.1 6.9 NA
Methomyl (Acetohydroxamate-13C2, 15N) Primary 166→90.8 6.1 NA
Simazine (Diethyl-D10) Primary 212.1→134 7.6 NA
Tebuconazole (tert-Butyl-D9) Primary 317.2→69.9 10.5 NA
Thiamethoxam -D3 Primary 295→214.1 6.3 NA
A
Indicates analyzed under acidic LC conditions.
D8025 − 23
7. Apparatus
7.1 LC/MS/MS System:
7.1.1 Liquid Chromatography SystemSystem——A complete LC system is required in order to analyze samples, this should
include a sample injection system, an autosampler, a solvent pumping system capable of mixing solvents, a sample compartment
capable of maintaining required temperature and a temperature controlled column compartment. A LC system that is capable of
performing at the flows, pressures, controlled temperatures, sample volumes, and requirements of the standard shallmust be used.
7.1.2 Analytical Column —A reverse phase C18 particle column was used to develop this test method. Any column that achieves
adequate resolution may be used. The retention times and order of elution may change depending on the column used and need
to be monitored.
7.2 Tandem Mass Spectrometer SystemSystem——A MS/MS system capable of multiple reaction monitoring (MRM) analysis or
any system that is capable of meeting the requirements in this standard shallmust be used. Electrospray ionization is utilized for
this standard.
7.3 Adjustable Volume Pipettes—10, 20, 100 and 1000 μL and 5 and 10 mL.10 μL, 20 μL, 100 μL, 1000 μL, 5 mL, and 10 mL.
7.3.1 Discussion—Any pipette may be used providing the data generated meets the performance of the standard.
7.3.2 Pipette Tips—Polypropylene pipette tips free of release agents or low retention coating of various sizes.
7.4 Class A Volumetric Glassware.
A Waters Acquity (a trademark of the Waters Corporation, Milford, MA) UPLC H-Class System, or equivalent, has been found suitable for use.BEH C18, 2.1 mm × 100
mm and 1.7 μm particle size column was used, if you are aware of an alternative column that meets the performance of the standard, please provide this information to ASTM
International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, which you may attend.
A Waters Acquity (a trademark of the Waters Corporation, Milford, MA) UPLC BEH C18, 2.1×100 mm and 1.7 μm particle size column, or equivalent, has been found
suitable for use. It was used to develop this test method and generate the precision and bias data presented in Section 16.
A Waters Xevo (a trademark of the Waters Corporation, Milford, MA) TQ-S triple quadrupole mass spectrometer, or equivalent, has been found suitable for use.
D8025 − 23
7.5 Filtration Device:
7.5.1 Hypodermic Syringe—A luer-lock tip glass syringe capable of holding a syringe driven filter unit.
7.5.2 A 10 mL Lock Tip Glass Syringe size is recommended since a 10 mL prepared sample size is used in this test method. If
a smaller volume syringe is used, do not wash out the syringe or change filters while filtering the same sample if multiple refills
of the syringe are required in order to filter the 10 mL prepared sample.
7.5.3 Filter Unit —PTFE filter units were used to filter the samples.
7.6 Vials—2-mL autosampler vials (LC vials) with pre-slit PTFE/silicone septa or equivalent.
7.7 Sonicator.
7.8 Oven—Capable to achieve 250°C.250 °C.
7.9 VOA Vials—Amber, 40 mL.40 mL.
8. Reagents and Materials
8.1 Purity of Reagents—High Performance Liquid Chromatography (HPLC) pesticide residue analysis and spectrophotometry
grade chemicals shallmust be used in all tests. Unless indicated otherwise, it is intended that all reagents shallmust conform to the
Committee on Analytical Reagents of the American Chemical Society. Other reagent grades may be used provided they are first
determined to be of sufficiently high purity to permit their use without affecting the accuracy of the measurements.
8.2 Purity of Water—Unless otherwise indicated, references to water shallmust be understood to mean reagent water conforming
to Type 1 of Specification D1193. It shallmust be demonstrated that this water does not contain contaminants at concentrations
sufficient to interfere with the analysis.
8.3 All prepared solutions are routinely replaced every year if not previously discarded for quality control failure.
8.4 Gases—Ultrapure nitrogen and argon.
8.5 Formic Acid (CAS # 64-18-6)64-18-6).
8.6 Acetonitrile (CAS # 75-05-8)75-05-8).
8.7 Methanol (CAS # 67-56-1)67-56-1).
8.8 Ammonium Formate (CAS # 540-69-2)540-69-2).
8.9 2-Propanol (isopropyl alcohol, CAS # 67-63-0)67-63-0).
8.10 2,4-Dichlorophenoxyacetic acid (2,4-D, CAS # 94-75-7)94-75-7).
A Millipore IC Millex-LG PTFE/0.2μm membrane syringe driven membrane filter unit (Millex is a trademark of Merck KGAA, Darmstadt, Germany) has been found
suitable for use for this method, any filter unit may be used was used, if you are aware of an alternative filter that meets the performance of this method the standard, please
provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, may
be used. which you may attend.
Reagent Chemicals, American Chemical Society Specifications,ACS Reagent Chemicals, Specifications and Procedures for Reagents and Standard-Grade Reference
Materials, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for
Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC),
Rockville, MD.
D8025 − 23
8.11 Acetochlor (CAS # 34256-82-1)34256-82-1).
8.12 Alachlor (CAS # 15972-60-8)15972-60-8).
8.13 Aldicarb (CAS # 116-06-3)116-06-3).
8.14 Atrazine (CAS # 1912-24-9)1912-24-9).
8.15 Desethylatrazine (CAS # 6190-65-4)6190-65-4).
8.16 Desisopropylatrazine (CAS # 1007-28-9)1007-28-9).
8.17 Azoxystrobin (CAS # 131860-33-8)131860-33-8).
8.18 Bentazon (CAS # 25057-89-0)25057-89-0).
8.19 Carbaryl (CAS # 63-25-2)63-25-2).
8.20 Chlorpyrifos (CAS # 2921-88-2)2921-88-2).
8.21 Clopyralid (CAS # 1702-17-6)1702-17-6).
8.22 Clothianidin (CAS # 210880-92-5)210880-92-5).
8.23 Diazinon (CAS # 333-41-5)333-41-5).
8.24 Dicamba (CAS # 1918-00-9)1918-00-9).
8.25 Fipronil (CAS # 120068-37-3)120068-37-3).
8.26 Imidacloprid (CAS # 138261-41-3)138261-41-3).
8.27 Malathion (CAS # 121-75-5)121-75-5).
8.28 Methomyl (CAS # 16752-77-5)16752-77-5).
8.29 Metolachlor (CAS # 51218-45-2)51218-45-2).
8.30 Metribuzin (CAS # 21087-64-9)21087-64-9).
8.31 Picloram (CAS # 1918-02-1)1918-02-1).
8.32 Propiconazole (CAS # 60207-90-1)60207-90-1).
8.33 Simazine (CAS # 122-34-9)122-34-9).
8.34 Tebuconazole (CAS # 107534-96-3)107534-96-3).
8.35 Thiamethoxam (CAS # 153719-23-4)153719-23-4).
D8025 − 23
8.36 Triclopyr (CAS # 55335-06-3)55335-06-3).
8.37 Isotopically Labeled Pesticide Standards (Surrogates)—There are not isotopically labeled surrogates for every target analyte.
The labeled surrogate only mimics its unlabeled target analyte. The isotopically labeled carbofuran was chosen to mimic carbaryl.
(Note—P&A data show that the labeled carbofuran is not a good surrogate for carbaryl even though they are structurally similar.)
Surrogates may be added or deleted from the below list if new ones become available or if the existing ones are not readily
available. The surrogate list is long and expensive to maintain. If surrogates are not available at the time of analysis it will be
mentioned in the case narrative that accompanies the data, if extra surrogates are added this will also be mentioned in the case
narrative.narrative (CAS #’s are for the unlabeled native analyte).
8.37.1 2,4-Dichlorophenoxyacetic acid (2,4-D (Ring-D3), CAS # 94-75-7)94-75-7).
8.37.2 Atrazine (ethyl-D5, CAS # 1912-24-9)1912-24-9).
8.37.3 Desethylatrazine (iso-propyl-D7, CAS # 6190-65-4)6190-65-4).
8.37.4 Desisopropylatrazine (ethyl-D5, CAS # 1007-28-9)1007-28-9).
8.37.5 Bentazon (D7, CAS # 25057-89-0)25057-89-0).
8.37.6 Carbofuran (Ring-13C6, CAS # 1563-66-2)1563-66-2).
8.37.7 Clothianidin (D3, CAS # 210880-92-5)210880-92-5).
8.37.8 Diazinon (diethyl-D10, CAS # 333-41-5)333-41-5).
8.37.9 Dicamba (D3, CAS # 1918-00-9)1918-00-9).
8.37.10 Imidacloprid (D4, CAS # 138261-41-3)138261-41-3).
8.37.11 Methomyl (Acetohydroxamate-13C2, 15N, CAS # 16752-77-5)16752-77-5).
8.37.12 Simazine (diethyl-D10, CAS # 122-34-9)122-34-9).
8.37.13 Tebuconazole (tert-Butyl-D9, CAS # 107534-96-3)107534-96-3).
8.37.14 Thiamethoxam (D3, CAS # 153719-23-4)153719-23-4).
9. Hazards
9.1 Normal laboratory safety applies to this method. Analysts should wear safety glasses, gloves, and lab coats when working in
the lab. Analysts should review the Safety Data Sheets (SDS) for all reagents used in this method.
10. Sampling and Preservation
10.1 Grab samples are collected in amber glass containers with Teflon™ lined inert-lined caps, such as, 40 mL amber VOA vials.
As part of the overall quality assurance program for this test method, field blanks exposed to the same field conditions as samples
are collected and analyzed according to this standard to assess the potential for field contamination, refer to Guide D3856 as a guide
for sampling. This test method is based upon an 8 mL sample size per analysis. If different sample sizes are used, spiking solution
amounts may need to be modified. EPA publication SW-846 may be used as a sampling guide. Samples shallmust be shipped with
a trip blank and at less than 6ºC.between freezing and 6 °C.
10.2 Once received the sample temperature is taken and should be less than 6ºC.6 °C. If the receiving temperature is greater than
6ºC,6 °C, the sample temperature is noted in the case narrative accompanying the data. Samples should be stored refrigerated
between 0ºC and 6ºC0 °C and 6 °C from the time of collection until analysis.
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10.3 The samples should be analyzed within 14 days of collection. No holding time study has been done on water matrices tested
in this test method. Holding time may vary depending on the matrix and individual laboratories should determine the holding time
in their matrix, refer to Practice D4841.
11. Preparation of LC/MS/MS
11.1 LC Chromatograph Operating Conditions:
11.1.1 Injections of all standards and samples are made at a 25 or 50 μL 25 μL or 50 μL volume. Other injection volumes may
be used to optimize conditions. Standards and sample extracts shallmust be in a 80:20 water:methanol solution. In the case of
extreme concentration differences amongst samples, it is wise to analyze a blank after a concentrated sample and before a dilute
sample to minimize carry-over of analytes from injection to injection. However, there should not be carry-over between samples.
The LC utilized to develop this test method has a flow through LC needle design. The gradient conditions for the two liquid
chromatography analysis runs are shown in Tables 2 and 3. The primary SRM transition chromatograms at the lowest calibration
level are shown in the Appendix, Figs. X1.1-X1.5.
11.2 LC Auto Sampler Conditions:
11.2.1 Needle Wash Solvent—60 %60 % acetonitrile acetonitrile/40 % 2-propanol. 8 second ⁄40 % 2-propanol. 8 s wash time
before and after injection. Instrument manufacturer’s specifications should be followed in order to eliminate sample carry-over.
11.2.2 Temperatures—Column, 35°C;35 °C; Sample compartment, 15°C.15 °C.
11.2.3 Seal Wash—Solvent: 50 %50 % methanol methanol/50 % ⁄50 % water; Time: 5 minutes.5 min.
11.3 Mass Spectrometer Parameters:
11.3.1 To acquire the maximum number of data points per SRM channel while maintaining adequate sensitivity, the tune
parameters may be optimized according to the instrument used. Each peak requires at least 10 scans per peak for adequate
quantitation. Variable parameters regarding SRM transitions, and cone and collision energies are shown in Table 4. Mass
spectrometer parameters used in the development of this method are listed below.
11.3.2 The instrument is set in the Electrospray source setting. The values for the following parameters are shown here for
information only. These conditions should be checked and optimized when required.
Methanol/Water/Ammonium Formate Analysis Run Conditions
Capillary Voltage: 1 kV in both ESI modes
Cone: Variable depending on analyte
Source Offset (V) 10
Source Temperature: 150°C
Source Temperature: 150 °C
Desolvation Gas Temperature: 500°C
Desolvation Gas Temperature: 500 °C
Desolvation Gas Flow: 900 L/hr
Desolvation Gas Flow: 900 L/h
Cone Gas Flow: 150 L/hr
Cone Gas Flow: 150 L/h
Collision Gas Flow: 0.15 mL/min
Low Mass Resolution 1: 2.7
High Mass Resolution 1: 14.7
Ion Energy 1: 0.5
Entrance Energy: 1
Collision Energy: Variable depending on analyte
Exit Energy: 1
Low Mass Resolution 2: 2.8
High Mass resolution 2: 14.7
Ion Energy 2: 1.5
Gain: 1.0
Multiplier: 535
Inter-Scan Delay: 0.003 seconds
Inter-Scan Delay: 0.003 s
Polarity Switching Inter-scan Delay: 0.020 seconds
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Methanol/Water/Ammonium Formate Analysis Run Conditions
Polarity Switching Inter-scan Delay: 0.020 s
Methanol/Water/Formic Acid Analysis Run Conditions
Capillary Voltage: Positive mode 2 kV, Negative mode 0.75 kV
Cone: Variable depending on analyte
Source Offset (V) 10
Source Temperature: 150°C
Source Temperature: 150 °C
Desolvation Gas Temperature: 300°C
Desolvation Gas Temperature: 300 °C
Desolvation Gas Flow: 1000 L/hr
Desolvation Gas Flow: 1000 L/h
Cone Gas Flow: 300 L/hr
Cone Gas Flow: 300 L/h
Collision Gas Flow: 0.15 mL/min
Low Mass Resolution 1: 2.7
High Mass Resolution 1: 14.7
Ion Energy 1: 0.5
Entrance Energy: 1
Collision Energy: Variable depending on analyte
Exit Energy: 1
Low Mass Resolution 2: 2.8
High Mass resolution 2: 14.7
Ion Energy 2: 1.5
Gain: 1.0
Multiplier: 535
Inter-Scan Delay: 0.003 seconds
Inter-Scan Delay: 0.003 s
Polarity Switching Inter-scan Delay: 0.020 seconds
Polarity Switching Inter-scan Delay: 0.020 s
12. Calibration and Standardization
12.1 The mass spectrometer shallmust be calibrated as per manufacturer’s specifications before analysis. Analytical values
satisfying test method criteria have been achieved using the following procedures. Prepare all solutions in the lab using Class A
volumetric glassware.
12.2 Calibration and Standardization—To generate a calibration curve, analyze seven calibration standards of the pesticide
compounds prior to sample analysis as shown in Table 6. Calibration stock standard solution is prepared from the target and
surrogate spike solutions directly to ensure consistency. Stock standard Solution A containing the pesticides is prepared at Level
7 concentration and aliquots of that solution are diluted to prepare Levels 1 through 6. The following steps will produce 1 mL
TABLE 6 Concentrations of Calibration Standards (ng/L)
Pesticide and Surrogate
LV1 LV2 LV3 LV4 LV5 LV6 LV7
Concentrations (ng/L)
Azoxystrobin 25 50 100 200 400 800 1 000
Atrazine, Desethylatrazine, Clothianidin, 50 100 200 400 800 1 600 2 000
Diazinon, Imidacloprid, Metolachlor,
Propiconazole, Simazine, Tebuconazole,
Thiamethoxam, Atrazine (ethyl-D5),
Desethylatrazine (iso-propyl-D7), Clothianidin-
D3, Diazinon (diethyl-D10), Imidacloprid-D4,
Simazine (diethyl-D10), Tebuconazole (tert-
Butyl-D9), Thiamethoxam-D3
Desisopropylatrazine, Malathion, Metribuzin, 100 200 400 800 1 600 3 200 4 000
Desisopropylatrazine (ethyl-D5)
2,4-D, Acetochlor, Alachlor, Aldicarb, 200 400 800 1600 3 200 6 400 8 000
Bentazon, Carbaryl, Chlorpyrifos, Fipronil,
Methomyl, 2,4-D (Ring-D3), Bentazon-D7,
Carbofuran (Ring-13C6), Methomyl
(Acetohydroxamate-13C2, 15N)
Triclopyr 1 000 2 000 4 000 8 000 16 000 32 000 40 000
Picloram 5 000 10 000 20 000 40 000 80 000 160 000 200 000
Dicamba, Dicamba-D3 10 000 20 000 40 000 80 000 160 000 320 000 400 000
Clopyralid 20 000 40 000 80 000 160 000 320 000 640 000 800 000
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calibration standards with the concentration values shown in Table 6. The analyst is responsible for recording initial component
weights carefully when working with pure materials and correctly carrying the weights through the dilution calculations.
12.2.1 At a minimum, five calibration levels are required when using a linear calibration curve and six calibration levels are
required when using a quadratic calibration curve. An initial seven point curve may be used to allow for the dropping of the lower
level calibration point if the individual laboratory’s instrument can’t achieve low detection limits. This should allow for at least
a five or six point calibration curve to be obtained.
12.2.2 Calibration stock standard Solution A (Level 7, Table 6) is prepared from the target and surrogate spike solutions directly
to ensure consistency. 1.25 mL 1.25 mL of the surrogate spike and 1.25 mL 1.25 mL of the pesticide Target Spike Solution is added
to a 50 mL 50 mL volumetric flask and brought up to 50 mL 50 mL volume with 80:20 water and methanol solution. This stock
standard Solution A (Level 7, Table 6) is diluted to prepare Levels 1 through 6 as shown in Tables 6 and 7. The preparation of
the Level 7 standard can be accomplished using appropriate volumes and concentrations of stock solutions as per a particular
laboratory’s standard procedure.
12.2.3 Aliquots of Solution A are then diluted with 80:20 water:methanol to prepare the 1 mL desired calibration levels in 2 mL
amber glass LC vials, as described in Table 7. The calibration vials shallmust be used within 24 hours 24 h to ensure optimum
results. Calibration standards are not filtered.
12.2.4 Inject each standard and obtain its chromatogram. An external calibration technique is used to monitor the primary and
confirmatory SRM transitions of the pesticides and surrogates. Calibration software is utilized to conduct the quantitation of the
analytes using the primary SRM transition. The ratios of the primary/confirmatory SRM transitions area counts are given in Table
5 and will vary depending on the individual tuning conditions. The primary/confirmatory SRM transitions area ratio shallmust be
within 35 % 35 % of the individual labs’ accepted primary/confirmatory SRM transitions area ratio. The primary SRM transition
of the analytes are used for quantitation and the confirmatory SRM transitions for confirmation. This gives added confirmation by
isolating the parent ion, forming product ions via fragmentation, and relating it to the retention time in the calibration standard.
Metribuzin and the surrogates only have a primary SRM transition.
12.2.5 Depending on sensitivity and matrix interference issues dependent on sample type, a confirmatory SRM transition may be
substituted as the primary SRM transition for quantitation during analysis. This shallmust be explained in a narrative
accompanying the data. New primary/confirmatory ion ratios will then be determined if switching the SRM transitions used to
quantitate and confirm. The new primary/confirmatory SRM transitions area ratio is required to be within 35 % 35 % of the
individual labs’ new primary/confirmatory SRM transitions area ratio.
12.2.6 The calibration software manual should be consulted to use the software correctly. The quantitation method is set as an
external calibration using the peak areas in ng/L units. Concentrations may be calculated using the data system software to generate
linear regression or quadratic calibration curves. Forcing the calibration curve through the origin (X=0, Y=0) is not recommended.
Curves should be evaluated using relative error or relative standard error.
12.2.7 Linear calibration may be used if the coefficient of determination, r , is ≥ 0.98 for the analyte. The point of origin is
excluded and a fit weighting of 1/X is used in order to give more emphasis to the lower concentrations. If one of the calibration
standards other than the high or low point causes the r of the curve to be <0.98, this point shall be re-injected or a new calibration
curve shall be regenerated. Each calibration point used to generate the curve shallmust have a calculated percent deviation less than
30 % 25 % from the generated curve. If the low or high point(s), or both, are excluded, minimally a five point curve is acceptable
but the reporting range shall be modified to reflect this change.
12.2.8 Quadratic calibration may be used if the coefficient of determination, r , is ≥0.99 for the analyte. The point of origin is
excluded, and a fit weighting of 1/X is used in order to give more emphasis to the lower concentrations. If one of the calibration
TABLE 7 Preparation of Calibration Standards
Solution LV1 LV2 LV3 LV4 LV5 LV6 LV7
A
A 25 μL 50 μL 100 μL 200 μL 400 μL 800 μL 1000 μL
B
B 975 μL 950 μL 900 μL 800 μL 600 μL 200 μL 0 μL
A
Solution A: Level 7 stock solution prepared according to section 12.2 and at Table 6 concentrations.
B
Solution B: 80 % 80 % Water : 20 % 20 % Methanol.
Management and Technical Requirements for Laboratories Performing Environmental Analysis; Module 4: Quality Systems for Chemical Testing; The NELAC Institute,
2017.
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standards causes the curve to be <0.99, this point shall be re-injected or a new calibration curve shall be regenerated. If the low
or high point(s), or both, are excluded, minimally a six point curve is acceptable but the reporting range shall be modified to reflect
this change. Each calibration point used to generate the curve shallmust have a calculated percent deviation less than 30 % 25 %
from the generated curve.
12.2.9 The retention time window of the SRM transitions shallmust be within 5 % 5 % of the retention time of the analyte in a
midpoint calibration standard. If this is not the case, re-analyze the calibration curve to determine if there was a shift in retention
time during the analysis and the sample needs to be re-injected. If the retention time is still incorrect in the sample, refer to the
analyte as an unknown.
12.2.10 A midpoint calibration check standard shallmust be analyzed at the end of each batch of 30 samples or within 24 hours
24 h after the initial calibration curve was generated, the criteria in the individual labs’ quality system may be more restrictive
pertaining to the number of samples. This end calibration check should come from the same calibration standard solution that was
used to generate the initial curve. The results from the end calibration check standard shallmust have a percent deviation less than
30 % 30 % from the calculated concentration for the target analyte. If the results are not within these criteria, corrective action
including re-occurrence minimization is performed and either all samples in the batch are re-analyzed against a new calibration
curve or the affected results are qualified with an indication that they do not fall within the performance criteria of the test method.
If the analyst inspects the vial containing the end calibration check standard and notices that the sample evaporated affecting the
concentration or other anomaly, a new end calibration check standard may be made and analyzed. If this new end calibration check
standard has a percent deviation less than 30 % from the calculated concentration for the target analyte, the results may be reported
unqualified.
12.3 If a laboratory has not performed the test before or if there has been a major change in the measurement system, for example,
new analyst, new instrument, etc., an instrument qualification study including reporting limit check sample (RLCS), calibration
range determination and precision and bias determination shallmust be performed to demonstrate laboratory capability.
12.3.1 Analyze at least four replicates of a spiked water sample containing the pesticides at a prepared sample concentration in
the calibration range of Levels 3–6. A Level 4 prepared sample concentration was used to set the QC acceptance criteria in this
method. The matrix and chemistry should be similar to the matrix used in this test method. Each replicate shallmust be taken
through the complete analytical test method including any sample manipulation and preparation steps.
12.3.2 Calculate the mean (average) percent recovery and relative standard deviation (RSD) of the four values and compare to the
acceptable ranges of the QC acceptance criteria for the Initial Demonstration of Performance in Table 8.
12.3.3 This study should be repeated until the single operator precision and mean recovery are within the limits in Table 8. If a
concentration other than the recommended concentration is used, refer to Practice D5847 for information on applying the F test
and t test in evaluating the acceptability of the mean and standard deviation.
12.3.3.1 The QC acceptance criteria for the Initial Demonstration of Performance in Table 8 were generated from the
single-laboratory data shown in the Precision and Bias Section 16. Data from reagent water and surface water are shown in the
Precision and Bias Section 16. It is recommended that each laboratory determine in-house QC acceptance criteria which meet or
exceed the criteria in this standard. References generating QC acceptance criteria are ASTM Practices D2777, D5847, E2554 and
Method 8000 in EPA publication SW-846.
12.4 Surrogate Spiking Solution:
12.4.1 A surrogate spiking solution containing fourteen isotopically-labeled pesticides (listed in Section 8) are added to all
samples. 50 μL 50 μL of a methanolic solution containing the surrogates and concentrations are listed in Table 9, Concentrations
in Surrogate Spike Solution, is added to all 8 mL 8 mL samples to achieve the concentration in the sample listed in Table 9,
Concentration in Water Sample.
12.4.2 The result obtained for the surrogates shallmust fall within the limits in Table 8.
12.4.3 There are fourteen surrogates for this analysis. The isotopically-labeled surrogate represents the unlabeled native analyte.
Carbofuran (Ring-13C6) represents carbaryl in this standard. No qualifications based on surrogate recovery need to be made for
the analytes that do not have representative surrogates. It is left to the analyst’s judgment to qualify data based upon
non-representative surrogates. The user of the data must also make decisions based on all QC available. If the result is not within
D8025 − 23
TABLE 8 QC Acceptance Criteria
NOTE 1—Table 8 data is preliminary until a multi-lab validation study is completed.
Initial Demonstration of Performance Laboratory Control Sample
Spiked Sample Recovery (%) Precision Recovery (%)
Analyte
Conc. (ng/L)
Maximum
Lower Limit Upper Limit Lower Limit Upper Limit
% RSD
2,4-D 2 000 70 130 30 70 130
Acetochlor 2 000 70 130 30 70 130
Alachlor 2 000 70 130 30 70 130
Aldicarb 2 000 70 130 30 70 130
Atrazine 500 70 130 30 70 130
Desethylatrazine 500 70 130 30 70 130
Desisopropylatrazine 1 000 70 130 30 70 130
Azoxystrobin 250 70 130 30 70 130
Bentazon 2 000 70 130 30 70 130
Carbaryl 2 000 50 130 30 50 130
Chlorpyrifos 2 000 50 130 30 50 130
Clopyralid 200 000 70 130 30 70 130
Clothianidin 500 70 130 30 70 130
Diazinon 500 70 130 30 70 130
Dicamba 100 000 70 130 30 70 130
Fipronil 2 000 60 130 30 60 130
Imidacloprid 500 70 130 30 70 130
Malathion 1 000 40 130 30 40 130
Methomyl 2 000 70 130 30 70 130
Metolachlor 500 70 130 30 70 130
Metribuzin 1 000 70 130 30 70 130
Picloram 50 000 70 130 30 70 130
Propiconazole 500 50 130 30 50 130
Simazine 500 70 130 30 70 130
Tebuconazole 500 70 130 30 70 130
Thiamethoxam 500 70 130 30 70 130
Triclopyr 10 000 70 130 30 70 130
Surrogates N
...