ASTM D7600-16(2017)

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:D7600 −16 (Reapproved 2017)
Standard Test Method for
Determination of Aldicarb, Carbofuran, Oxamyl and
Methomyl by Liquid Chromatography/Tandem Mass
Spectrometry
This standard is issued under the fixed designation D7600; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
1.1 This procedure covers the determination of aldicarb,
carbofuran, oxamyl and methomyl (referred to collectively as
2. Referenced Documents
carbamates in this test method) in surface water by direct
2.1 ASTM Standards:
injection using liquid chromatography (LC) and detected with
D1129Terminology Relating to Water
tandemmassspectrometry(MS/MS).Theseanalytesarequali-
D1193Specification for Reagent Water
tativelyandquantitativelydeterminedbythistestmethod.This
D2777Practice for Determination of Precision and Bias of
test method adheres to multiple reaction monitoring (MRM)
Applicable Test Methods of Committee D19 on Water
mass spectrometry.
D3856Guide for Management Systems in Laboratories
1.2 This test method has been developed by U.S. EPA
Engaged in Analysis of Water
Region 5 Chicago Regional Laboratory (CRL).
D3694Practices for Preparation of Sample Containers and
1.3 The values stated in SI units are to be regarded as for Preservation of Organic Constituents
D5847Practice for Writing Quality Control Specifications
standard. No other units of measurement are included in this
standard. for Standard Test Methods for Water Analysis
E2554Practice for Estimating and Monitoring the Uncer-
1.4 The Detection Verification Level (DVL) and Reporting
tainty of Test Results of a Test Method Using Control
Range for the carbamates are listed in Table 1.
Chart Techniques
1.4.1 The DVL is required to be at a concentration at least
2.2 Other Documents:
3 times below the Reporting Limit (RL) and have a signal/
EPApublication SW-846Test Methods for Evaluating Solid
noise ratio greater than 3:1. Fig. 1 displays the signal/noise
Waste, Physical/Chemical Methods
ratios of the primary single reaction monitoring (SRM) transi-
tions and Fig. 2 displays the confirmatory SRM transitions at
3. Terminology
the DVLs for the carbamates.
3.1 Definitions:
1.4.2 The reporting limit is the concentration of the Level 1
3.1.1 For definitions of terms used in this standard, refer to
calibration standard as shown in Table 2 for the carbamates.
Terminology D1129.
1.5 This standard does not purport to address all of the
3.2 Definitions of Terms Specific to This Standard:
safety concerns, if any, associated with its use. It is the
3.2.1 carbamates, n—in this test method, aldicarb,
responsibility of the user of this standard to establish appro-
carbofuran, oxamyl and methomyl collectively.
priate safety and health practices and determine the applica-
3.2.2 detection verification level, DVL, n—a concentration
bility of regulatory limitations prior to use.
that has a signal/noise ratio greater than 3:1 and is at least 3
1.6 This international standard was developed in accor-
times below the reporting limit (RL).
dance with internationally recognized principles on standard-
3.2.3 independent reference material, IRM, n—amaterialof
ization established in the Decision on Principles for the
known purity and concentration obtained either from the
Development of International Standards, Guides and Recom-
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
This test method is under the jurisdiction ofASTM Committee D19 on Water contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor Standards volume information, refer to the standard’s Document Summary page on
Organic Substances in Water. the ASTM website.
Current edition approved June 15, 2017. Published July 2017. Originally Available from National Technical Information Service (NTIS), U.S. Depart-
approved in 2009. Last previous edition approved in 2016 as D7600 – 16. DOI: ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
10.1520/D7600-16R17. www.epa.gov/epawaste/hazard/testmethods/index.htm.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7600−16 (2017)
TABLE 1 Detection Verification Level and Reporting Range
report issued for each sample lists the concentration of
Analyte DVL (ng/L) Reporting Range (µg/L) aldicarb, carbofuran, oxamyl, methomyl and the BDMC sur-
Aldicarb 100 1–100 rogate recovery.
Carbofuran 100 1–100
Oxamyl 100 1–100
5. Significance and Use
Methomyl 100 1–100
5.1 The N-methyl carbamate (NMC) pesticides: aldicarb,
carbaryl, carbofuran, formetanate hydrochloride, methiocarb,
methomyl, oxamyl, pirimicarb, propoxur, and thiodicarb have
NationalInstituteofStandardsandTechnology(NIST)orother
been identified by EPAas working through a common mecha-
reputable supplier. The IRM shall be obtained from a different
nism.Theyaffectthenervoussystembyreducingtheabilityof
lot of material than is used for calibration
the enzyme cholinesterase. Cholinesterase inhibition was the
3.3 Acronyms:
primary toxicological effect of regulatory concern to EPA in
3.3.1 CCC, n—Continuing Calibration Check
assessingtheNMC’sfood,drinkingwaterandresidentialrisks.
3.3.2 IC, n—Initial Calibration
In most of the country, NMC residues in drinking water
sources are at levels that are not likely to contribute substan-
3.3.3 LC, n—Liquid Chromatography
tially to the multi-pathway cumulative exposure. Shallow
3.3.4 LCS/LCSD, n—Laboratory Control Sample/
private wells extending through highly permeable soils into
Laboratory Control Sample Duplicate
shallow, acidic ground water represent what the EPA believes
3.3.5 MDL, n—Method Detection Limit 4
to be the most vulnerable drinking water.
3.3.6 MeOH, n—Methanol
5.2 This test method has been investigated for use with
–3
3.3.7 mM, n—millimolar,1×10 moles/L
reagentandsurfacewaterfortheselectedcarbamates:aldicarb,
3.3.8 MRM, n—Multiple Reaction Monitoring carbofuran, oxamyl, and methomyl.
3.3.9 MS/MSD, n—Matrix Spike/Matrix Spike Duplicate
6. Interferences
3.3.10 NA, adj—Not Available
6.1 Methodinterferencesmaybecausedbycontaminantsin
3.3.11 ND, n—non-detect
solvents, reagents, glassware and other apparatus producing
3.3.12 P&A, n—Precision and Accuracy
discrete artifacts or elevated baselines. All of these materials
are demonstrated to be free from interferences by analyzing
3.3.13 PPB, n—parts per billion
laboratory reagent blanks under the same conditions as
3.3.14 PPT, n—parts per trillion
samples.
3.3.15 QA, adj—Quality Assurance
6.2 All glassware is washed in hot water with a detergent,
3.3.16 QC, adj—Quality Control
rinsed in hot water followed by distilled water. The glassware
3.3.17 RL, n—Reporting Limit
is then dried and heated in an oven at 250°C for 15 to 30
minutes. All glassware is subsequently cleaned with acetone,
3.3.18 RSD, n—Relative Standard Deviation
then methanol.
3.3.19 RT, n—Retention Time
6.3 All reagents and solvents should be pesticide residue
3.3.20 SDS, n—Safety Data Sheets
purity or higher to minimize interference problems.
3.3.21 SRM, n—Single Reaction Monitoring
6.4 Matrix interferences may be caused by contaminants
3.3.22 SS, n—Surrogate Standard
that are co-extracted from the sample. The extent of matrix
3.3.23 TC, n—Target Compound
interferences can vary considerably from sample source de-
–6
3.3.24 µM, n—micromolar,1×10 moles/L pending on variations of the sample matrix.
3.3.25 VOA, n—Volatile Organic Analysis
7. Apparatus
4. Summary of Test Methods
7.1 LC/MS/MS System:
7.1.1 LiquidChromatography(LC)System—AcompleteLC
4.1 This is a performance-based method and modifications
system is needed in order to analyze samples. This should
are allowed to improve performance.
include a sample injection system, a solvent pumping system
4.2 For carbamate analysis, samples are shipped to the lab
capable of mixing solvents, a sample compartment capable of
between0°Cand6°Candanalyzedwithin7daysofcollection.
maintaining required temperature and a temperature controlled
In the lab, the samples are spiked with surrogate, filtered using
columncompartment.Asystemthatiscapableofperformingat
a syringe-driven filter unit and analyzed directly by LC/MS/
MS.
4.3 Aldicarb, carbofuran, oxamyl, methomyl, and 4-bromo-
AdditionalinformationaboutcarbamatepesticidescanbefoundontheInternet
at http://www.epa.gov.
3,5-dimethylphenyl-N-methylcarbamate (BDMC, surrogate)
AWatersAlliance High Performance Liquid Chromatography (HPLC) System
are identified by retention time and two SRM transitions. The
(a trademark of the Waters Corporation, Milford, MA), or equivalent, was found
target analytes and surrogate are quantitated using the primary
suitable for use. The multi-laboratory study included Agilent and Waters LC
SRM transitions utilizing an external calibration. The final systems.
D7600−16 (2017)
FIG. 1Example Primary SRM Chromatograms Signal/Noise Ratios
FIG. 2Example Confirmatory SRM Chromatograms Signal/Noise Ratios
D7600−16 (2017)
TABLE 2 Concentrations of Calibration Standards (PPB)
8.3 Gases—Ultrapure nitrogen and argon.
Analyte/Surrogate LV 1 LV 2 LV 3 LV 4 LV 5 LV 6
8.4 Acetonitrile (CAS # 75-05-8).
Aldicarb 1 5 10 25 50 100
8.5 Methanol (CAS # 67-56-1).
Carbofuran 1 5 10 25 50 100
Oxamyl 1 5 10 25 50 100
8.6 Acetone (CAS # 67-64-1).
Methomyl 1 5 10 25 50 100
BDMC (Surrogate) 2 10 20 50 100 200
8.7 Ammonium acetate (CAS # 631-61-8).
8.8 Ammonium hydroxide (Concentrated, CAS # 1336-21-
6).
the flows, pressures, controlled temperatures, sample volumes
8.9 Aldicarb (CAS # 116-06-3).
and requirements of the standard may be used.
8.10 Carbofuran (CAS # 1563-66-2).
7.1.2 Analytical Column —A C18 column was used to
develop this test method. Any column that achieves adequate
8.11 Oxamyl (CAS # 23135-22-0).
resolution may be used. The retention times and order of
8.12 Methomyl (CAS # 16752-77-5).
elution may change depending on the column that is used and
8.13 4-Bromo-3,5-dimethylphenyl-N-methylcarbamate
need to be monitored.
(BDMC, CAS # 672-99-1).
7.1.3 Tandem Mass Spectrometer (MS/MS) System—A
8.13.1 BDMC is used as a surrogate in this standard.
MS/MS system capable of MRM analysis. A system that is
capableofperformingattherequirementsinthisstandardmay
9. Hazards
be used.
9.1 Normal laboratory safety applies to this method. Ana-
7.2 Filtration Device:
lysts should wear safety glasses, gloves, and lab coats when
7.2.1 Hypodermic syringe—A luer-lock tip glass syringe
working in the lab. Analysts should review the Safety Data
capable of holding a syringe-driven filter unit.
Sheets (SDS) for all reagents used in this test method.
7.2.1.1 A25-mLlocktipglasssyringesizeisrecommended
since a 25-mL sample size is used in this test method.
10. Sampling
7.2.2 Filter unit —PVDF filter units were used to filter the
10.1 Sampling—Grabsamplesmustbecollectedin≥25-mL
samples.
pre-cleaned amber glass bottles withTeflon-lined caps demon-
strated to be free of interferences. This test method requires a
8. Reagents and Materials
25-mL sample size per analysis. Conventional sampling prac-
8.1 Purity of Reagents—High-performance liquid chroma-
tices should be followed. Refer to Guide D3856 and Practices
tography (HPLC) pesticide residue analysis and spectropho-
D3694.
tometry grade chemicals shall be used in all tests. Unless
10.2 Preservation—Store samples between 0°C and 6°C
indicated otherwise, it is intended that all reagents shall
from the time of collection until analysis.Analyze the sample
conform to the Committee on Analytical Reagents of the
9 within 7 days of collection.
American Chemical Society. Other reagent grades may be
used provided they are first determined to be of sufficiently
11. Preparation of LC/MS/MS
highpuritytopermittheirusewithoutaffectingtheaccuracyof
11.1 LC Chromatograph Operating Conditions:
the measurements.
11.1.1 Injection volumes of all calibration standards and
8.2 Purity of Water—Unless otherwise indicated, references
samples are 100 µL. The first sample analyzed after the
towatershallbeunderstoodtomeanreagentwaterconforming
calibrationcurveisablanktoensurethereisnocarry-over.The
toType1ofSpecificationD1193.Itmustbedemonstratedthat
gradient conditions for the liquid chromatograph are shown in
this water does not contain contaminants at concentrations
Table 3.
sufficient to interfere with the analysis.
11.1.2 Temperatures—Column, 30°C; Sample
compartment, 15°C.
AWaters (a trademark of theWaters Corporation, Milford, MA) XBridge C18,
TABLE 3 Gradient Conditions for Liquid Chromatography
150 mm × 2.1 mm, 3.5 µm particle size, or equivalent, has been found suitable for
use.
Percent Percent 50 mmolar
Time Flow Percent
A Waters Quattro micro API mass spectrometer (a trademark of the Waters
95 % Water ⁄ NH OAc/NH OH in
4 4
(min) (µL/min) CH CN
Corporation, Milford, MA), or equivalent, was found suitable for use. The
5% CH CN 95 % Water/5 % CH CN
3 3
multi-laboratory study included Applied Biosystems and Waters mass spectrom-
0 300 0 95 5
eters.
2 300 0 95 5
A Millex HV Syringe Driven Filter Unit PVDF 0.45 µm (Millipore
4 300 30 65 5
Corporation, Catalog # SLHV033NS; a trademark of the Waters Corporation,
6 300 35 60 5
Milford, MA) has been found suitable for use for this test method, any filter unit
8 300 35 60 5
may be used that meets the performance of this test method may be used.
10 300 75 20 5
Reagent Chemicals, American Chemical Society Specifications, American
11.5 300 75 20 5
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
12 300 95 0 5
listed by the American Chemical Society, see Annual Standards for Laboratory
18 300 95 0 5
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
20 300 0 95 5
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 23 300 0 95 5
MD.
D7600−16 (2017)
11.1.3 Seal Wash—Solvent: 50% Acetonitrile/50% Water; 12. Calibration and Standardization
Time: 5 minutes.
12.1 The mass spectrometer must be calibrated per manu-
11.1.4 Needle Wash—Solvent: 50% Acetonitrile/50% Wa-
facturer specificatio
...