ASTM D5315-04(2017)e1
(Test Method)Standard Test Method for Determination of N-Methyl-Carbamoyloximes and N-Methylcarbamates in Water by Direct Aqueous Injection HPLC with Post-Column Derivatization
Standard Test Method for Determination of N-Methyl-Carbamoyloximes and N-Methylcarbamates in Water by Direct Aqueous Injection HPLC with Post-Column Derivatization
SIGNIFICANCE AND USE
5.1 N-methylcarbamates and n-methylcarbomoyloximes are used in agriculture as insecticides and herbicides. They are sometimes found in both surface and ground waters and can be toxic to animals and plants at moderate to high concentrations. The manufacturing precursors and degradation products may be equally as hazardous to the environment.
SCOPE
1.1 This is a high-performance liquid chromatographic (HPLC) test method applicable to the determination of certain n-methylcarbamoyloximes and n-methylcarbamates in ground water and finished drinking water (1).2 This test method is applicable to any carbamate analyte that can be hydrolyzed to a primary amine. The following compounds have been validated using this test method:
Analyte
Chemical Abstract Services
Registry Number A
Aldicarb
116-06-3
Aldicarb sulfone
1646-88-4
Aldicarb sulfoxide
1646-87-3
Baygon
114-26-1
Carbaryl
63-25-2
Carbofuran
1563-66-2
3-Hydroxycarbofuran
16655-82-6
Methiocarb
2032-65-7
Methomyl
16752-77-5
Oxamyl
23135-22-0 (A) Numbering system of Chemical Abstracts, Inc.
1.2 This test method has been validated in a collaborative round-robin study (2) and estimated detection limits (EDLs) have been determined for the analytes listed in 1.1 (Table 1). Observed detection limits may vary between ground waters, depending on the nature of interferences in the sample matrix and the specific instrumentation used. (A) Primary column—250 by 4.6 mm inside diameter Altex Ultrasphere ODS, 5 μm.(B) Confirmation column—250 by 4.6 mm inside diameter Supelco LC-1, 5 μm.(C) Estimated method detection limit in micrograms per litre.
1.3 This test method is restricted to use by, or under the supervision of, analysts experienced in both the use of liquid chromatography and the interpretation of liquid chromatograms. Each analyst should demonstrate an ability to generate acceptable results with this test method using the procedure described in 12.3.
1.4 When this test method is used to analyze unfamiliar samples for any or all of the analytes listed in 1.1, analyte identifications should be confirmed by at least one additional qualitative technique.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
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. Additional guidance on laboratory safety is available and suitable references for the information are provided (3-5).
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
Relations
Buy Standard
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.
´1
Designation:D5315 −04 (Reapproved 2017)
Standard Test Method for
Determination of N-Methyl-Carbamoyloximes and
N-Methylcarbamates in Water by Direct Aqueous Injection
HPLC with Post-Column Derivatization
This standard is issued under the fixed designation D5315; 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.
ε NOTE—Warning notes were editorially updated throughout in December 2017.
1. Scope 1.4 When this test method is used to analyze unfamiliar
samples for any or all of the analytes listed in 1.1, analyte
1.1 This is a high-performance liquid chromatographic
identifications should be confirmed by at least one additional
(HPLC) test method applicable to the determination of certain
qualitative technique.
n-methylcarbamoyloximes and n-methylcarbamates in ground
water and finished drinking water (1). This test method is 1.5 The values stated in SI units are to be regarded as
applicable to any carbamate analyte that can be hydrolyzed to standard. No other units of measurement are included in this
a primary amine. The following compounds have been vali- standard.
dated using this test method:
1.6 This standard does not purport to address all of the
Chemical Abstract Services
safety concerns, if any, associated with its use. It is the
A
Analyte Registry Number
responsibility of the user of this standard to establish appro-
Aldicarb 116-06-3
priate safety, health, and environmental practices and deter-
Aldicarb sulfone 1646-88-4
Aldicarb sulfoxide 1646-87-3
mine the applicability of regulatory limitations prior to use.
Baygon 114-26-1
Additional guidance on laboratory safety is available and
Carbaryl 63-25-2
suitable references for the information are provided (3-5).
Carbofuran 1563-66-2
3-Hydroxycarbofuran 16655-82-6
1.7 This international standard was developed in accor-
Methiocarb 2032-65-7
dance with internationally recognized principles on standard-
Methomyl 16752-77-5
ization established in the Decision on Principles for the
Oxamyl 23135-22-0
Development of International Standards, Guides and Recom-
A
Numbering system of Chemical Abstracts, Inc.
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
1.2 This test method has been validated in a collaborative
round-robin study (2) and estimated detection limits (EDLs)
2. Referenced Documents
have been determined for the analytes listed in 1.1 (Table 1).
Observed detection limits may vary between ground waters,
2.1 ASTM Standards:
depending on the nature of interferences in the sample matrix
D1129Terminology Relating to Water
and the specific instrumentation used.
D1192Guide for Equipment for Sampling Water and Steam
in Closed Conduits (Withdrawn 2003)
1.3 This test method is restricted to use by, or under the
D1193Specification for Reagent Water
supervision of, analysts experienced in both the use of liquid
D2777Practice for Determination of Precision and Bias of
chromatography and the interpretation of liquid chromato-
Applicable Test Methods of Committee D19 on Water
grams. Each analyst should demonstrate an ability to generate
D3370Practices for Sampling Water from Closed Conduits
acceptable results with this test method using the procedure
D3694Practices for Preparation of Sample Containers and
described in 12.3.
for Preservation of Organic Constituents
This test method is under the jurisdiction ofASTM Committee D19 on Water
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
Organic Substances in Water. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 15, 2017. Published January 2018. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1992. Last previous edition approved in 2011 as D5315–04 (2011). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D5315-04R17E01. the ASTM website.
2 4
The boldface numbers in parentheses refer to the references at the end of this The last approved version of this historical standard is referenced on
test method. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
´1
D5315−04 (2017)
TABLE 1 Relative Retention Times for the Primary and
3.2.4 internal standard, n—a pure analyte(s) added to a
Confirmation Columns and EDLs for the 10 Carbamate
solution in known amount(s) and used to measure the relative
Pesticides
responsesofotheranalytesandsurrogatesthatarecomponents
Retention Time (minutes)
of the same solution. The internal standard must be an analyte
Analyte
A B C
Primary Confirmation EDL
that is not a sample component.
Aldicarb 27.0 21.4 1.0
Aldicarb sulfone 15.2 12.2 2.0
3.2.5 laboratory duplicates (LD1 and LD2),n—two sample
Aldicarb sulfoxide 15.0 17.5 2.0
aliquots taken in the analytical laboratory and analyzed sepa-
Baygon (Propoxur) 29.6 23.4 1.0
rately with identical procedures. Analyses of LD1 and LD2
Carbaryl 30.8 25.4 2.0
Carbofuran 29.3 24.4 1.5 provide a measure of the precision associated with laboratory
3-Hydroxycarbofuran 23.3 19.0 2.0
procedures, but not with sample collection, preservation, or
Methiocarb 34.9 28.6 4.0
storage procedures.
Methomyl 18.4 14.8 0.50
Oxamyl 17.4 14.6 2.0
3.2.6 laboratory-fortified blank (LFB),n—an aliquot of
A
Primary column—250 by 4.6 mm inside diameterAltex Ultrasphere ODS, 5 µm.
reagent water to which known quantities of the test method
B
Confirmation column—250 by 4.6 mm inside diameter Supelco LC-1, 5 µm.
C
analytes are added in the laboratory. The LFB is analyzed
Estimated method detection limit in micrograms per litre.
exactly as a sample is; its purpose is to determine whether the
methodology is in control and whether the laboratory is
capableofmakingaccurateandprecisemethodsattherequired
test method detection limit.
E682Practice for Liquid Chromatography Terms and Rela-
3.2.7 laboratory-fortified sample matrix (LFM),n—an ali-
tionships
quot of an environmental sample to which known quantities of
2.2 U.S. Environmental Protection Agency Standard:
the test method analytes are added in the laboratory. The LFM
EPAMethod531.1Revision3.0,USEPA,EMSL-Cincinnati,
is analyzed exactly as a sample is; its purpose is to determine
whether the sample matrix contributes bias to the analytical
EPAMethod531.2Revision1.0,USEPA,EMSL-Cincinnati,
results. The background concentrations of the analytes in the
samplematrixmustbedeterminedinaseparatealiquotandthe
measuredvaluesintheLFMcorrectedforbackgroundconcen-
3. Terminology
trations.
3.1 Definitions:
3.2.8 laboratory performance check solution (LPC),n—a
3.1.1 For definitions of water terms used in this standard,
solutionofmethodanalytes,surrogatecompounds,andinternal
refer to Terminology D1129.
standards used to evaluate the performance of the instrument
3.1.2 For definitions of other terms used in this standard,
system with respect to a defined set of method criteria.
refer to Practice E682.
3.2.9 laboratory reagent blank (LRB),n—an aliquot of
3.2 Definitions of Terms Specific to This Standard:
reagent water treated exactly the same as a sample, including
3.2.1 calibration standard (CAL),n—a solution prepared
being exposed to all glassware, equipment, solvents, reagents,
from the primary dilution standard solution and stock standard
internal standards, and surrogates that are used with other
solutionsoftheinternalstandardsandsurrogateanalytes.CAL
samples. The LRB is used to determine whether method
solutions are used to calibrate the instrument response with
analytes or other interferences are present in the laboratory
respect to analyte concentration.
environment, the reagents, or the apparatus.
3.2.2 field duplicates (FD1 and FD2),n—two separate
3.2.10 primary dilution standard solution, n—a solution of
samples collected at the same time, placed under identical
severalanalytespreparedinthelaboratoryfromstockstandard
circumstances, and treated exactly the same throughout field
solutions and diluted as necessary to prepare calibration
and laboratory procedures.Analyses of FD1 and FD2 provide
solutions and other necessary analyte solutions.
a measure of the precision associated with sample collection,
preservation, and storage, as well as with laboratory proce-
3.2.11 quality control sample (QCS),n—a sample matrix
dures.
containing test method analytes or a solution of test method
analytesinawatermisciblesolventthatisusedtofortifywater
3.2.3 field reagent blank (FRB),n—reagent water placed in
or environmental samples. The QCS is obtained from a source
a sample container in the laboratory and treated in all respects
external to the laboratory and is used to check the laboratory
as a sample, including being exposed to sampling site
performance with externally prepared test materials.
conditions,storage,preservation,andallanalyticalprocedures.
The purpose of the FRB is to determine whether method
3.2.12 stock standard solution, n—a concentrated solution
analytes or other interferences are present in the field environ-
containing a single certified standard that is a method analyte,
ment.
or a concentrated solution of a single analyte prepared in the
laboratory with an assayed reference compound. Stock stan-
dard solutions are used to prepare primary dilution standards.
AvailablefromUnitedStatesEnvironmentalProtectionAgency(EPA),William
3.2.13 surrogate analyte, n—a pure analyte(s), which is
Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460,
http://www.epa.gov. extremely unlikely to be found in any sample, and which is
´1
D5315−04 (2017)
added to a sample aliquot in known amount(s) before extrac- 6.4 The quality of the reagent water used to prepare stan-
tion. It is measured with the same procedures used to measure dards and samples must conform to Specification D1193,
other sample components. The purpose of a surrogate analyte especially in TOC content. High reagent water TOC causes a
is to monitor the method performance with each sample. deterioration of column selectivity, baseline stability, and
analyte sensitivity.
4. Summary of Test Method
6.5 Eliminate all sources of airborne primary amines, espe-
4.1 Thewatersampleisfiltered,anda200to400-µLaliquot
ciallyammonia,whichareabsorbedintothemobilephasesand
is injected onto a reverse phase HPLC column. Separation of
effect sensitivity.
the analytes is achieved using gradient elution chromatogra-
phy. After elution from the HPLC column, the analytes are
7. Apparatus
hydrolyzed with sodium hydroxide (2.0 g/L NaOH) at 95°C.
7.1 Sampling Equipment:
The methylamine formed during hydrolysis is reacted with
6 7
7.1.1 Sample Bottle,60-mLscrewcapglassvials andcaps
o-phthalaldehyde (OPA) and 2-mercaptoethanol to form a
equipped with a PTFE-faced silicone septa. Prior to use, wash
highly fluorescent derivative that is detected by a fluorescence
the vials and septa as described in 6.1.1.
detector (5).
7.2 Filtration Apparatus:
4.2 This test method is applicable to any carbamte analyte
7.2.1 Macrofiltration Device, to filter derivatization solu-
that can be hydrolyzed to a primary amine, not necessarily
tionsandmobilephasesusedinHPLC.Itisrecommendedthat
methylamine.
47-mm, 0.45-µm pore size filters be used.
5. Significance and Use
7.2.2 Microfiltration Device,tofiltersamplespriortoHPLC
analysis. Use a 13-mm filter holder and 13-mm diameter,
5.1 N-methylcarbamatesandn-methylcarbomoyloximesare
0.2-µm polyester filters.
used in agriculture as insecticides and herbicides. They are
sometimesfoundinbothsurfaceandgroundwatersandcanbe
7.3 Syringes and Valves:
toxic to animals and plants at moderate to high concentrations.
7.3.1 Hypodermic Syringe, 10 mL, glass, with Luer-Lok
The manufacturing precursors and degradation products may
tip.
be equally as hazardous to the environment.
7.3.2 Syringe Valve, three-way.
7.3.3 Syringe Needle, 7 to 10 cm long, 17-gage, blunt tip.
6. Interferences
7.3.4 Micro Syringes, various sizes.
6.1 Test method interferences may be caused by contami-
7.4 Miscellaneous:
nants in solvents, reagents, glassware, and other sample pro-
7.4.1 Solution Storage Bottles, amber glass, 10 to 15-mL
cessing apparatuses that lead to discrete artifacts or elevated
capacity with TFE-fluorocarbon-lined screw cap.
baselines in liquid chromatograms. Specific sources of con-
taminationhavenotbeenidentified.Allreagentsandapparatus 7.5 High-Performance Liquid Chromatograph (HPLC):
must be routinely demonstrated to be free of interferences 7.5.1 HPLC System, capable of injecting 200 to 1000-µL
under the analysis conditions by running laboratory reagent aliquots and performing ternary linear gradients at a constant
blanks in accordance with 12.2. flow rate. A data system is recommended for measuring peak
6.1.1 Glassware must be cleaned scrupulously. Clean all areas.Table2liststheretentiontimesobservedfortestmethod
glassware as soon as possible after use by rinsing thoroughly analytesusingthecolumnsandanalyticalconditionsdescribed
with the last solvent used in it. below.
6.1.2 After drying, store glassware in a clean environment 7.5.2 Column 1 (Primary Column), 250-mm long by
to prevent any accumulation of dust or other contaminants. 4.6-mminsidediameter,stainlesssteel,packedwith5-µmC-18
Store the glassware inverted or capped with aluminum foil. material. Mobile phase is established at 1.0 mL/min as a
6.1.3 The use of high-purity reagents and solvents helps to
minimize interference problems.
6.2 Interfering contamination may occur when a sample Samplebottlevial,PierceNo.13075,availablefromPierceChemicalCo.,3747
N.MeridianRd.,Rockford,IL61101,orequivalent,hasbeenfoundsuitableforuse.
containing low concentrations of analytes is analyzed imme-
Samplebottlecap,PierceNo.12722,availablefromPierceChemicalCo.,3747
diatelyafterasamplecontainingrelativelyhighconcentrations
N.MeridianRd.,Rockford,IL61101,orequivalent,hasbeenfoundsuitableforuse.
of analytes.Apreventive technique is between-sample rinsing 8
Millipore Type HA, 0.45 µm for water, and Millipore Type FH, 0.5µ m for
organics, available from Millipore Corp., 80 Ashby Rd., Bedford, MA 01730, or
of the sample syringe and filter holder with two portions of
equivalent, has been found suitable for use.
water. Analyze one or more laboratory method blanks after
Millipore stainless s
...
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
´1
Designation: D5315 − 04 (Reapproved 2017)
Standard Test Method for
Determination of N-Methyl-Carbamoyloximes and
N-Methylcarbamates in Water by Direct Aqueous Injection
HPLC with Post-Column Derivatization
This standard is issued under the fixed designation D5315; 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.
ε NOTE—Warning notes were editorially updated throughout in December 2017.
1. Scope 1.4 When this test method is used to analyze unfamiliar
samples for any or all of the analytes listed in 1.1, analyte
1.1 This is a high-performance liquid chromatographic
identifications should be confirmed by at least one additional
(HPLC) test method applicable to the determination of certain
qualitative technique.
n-methylcarbamoyloximes and n-methylcarbamates in ground
water and finished drinking water (1). This test method is 1.5 The values stated in SI units are to be regarded as
applicable to any carbamate analyte that can be hydrolyzed to standard. No other units of measurement are included in this
a primary amine. The following compounds have been vali- standard.
dated using this test method:
1.6 This standard does not purport to address all of the
Chemical Abstract Services
safety concerns, if any, associated with its use. It is the
A
Analyte Registry Number
responsibility of the user of this standard to establish appro-
Aldicarb 116-06-3
priate safety, health, and environmental practices and deter-
Aldicarb sulfone 1646-88-4
Aldicarb sulfoxide 1646-87-3
mine the applicability of regulatory limitations prior to use.
Baygon 114-26-1
Additional guidance on laboratory safety is available and
Carbaryl 63-25-2
suitable references for the information are provided (3-5).
Carbofuran 1563-66-2
3-Hydroxycarbofuran 16655-82-6
1.7 This international standard was developed in accor-
Methiocarb 2032-65-7
dance with internationally recognized principles on standard-
Methomyl 16752-77-5
ization established in the Decision on Principles for the
Oxamyl 23135-22-0
Development of International Standards, Guides and Recom-
A
Numbering system of Chemical Abstracts, Inc.
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
1.2 This test method has been validated in a collaborative
round-robin study (2) and estimated detection limits (EDLs)
2. Referenced Documents
have been determined for the analytes listed in 1.1 (Table 1).
Observed detection limits may vary between ground waters,
2.1 ASTM Standards:
depending on the nature of interferences in the sample matrix
D1129 Terminology Relating to Water
and the specific instrumentation used.
D1192 Guide for Equipment for Sampling Water and Steam
in Closed Conduits (Withdrawn 2003)
1.3 This test method is restricted to use by, or under the
D1193 Specification for Reagent Water
supervision of, analysts experienced in both the use of liquid
D2777 Practice for Determination of Precision and Bias of
chromatography and the interpretation of liquid chromato-
Applicable Test Methods of Committee D19 on Water
grams. Each analyst should demonstrate an ability to generate
D3370 Practices for Sampling Water from Closed Conduits
acceptable results with this test method using the procedure
D3694 Practices for Preparation of Sample Containers and
described in 12.3.
for Preservation of Organic Constituents
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 Dec. 15, 2017. Published January 2018. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1992. Last previous edition approved in 2011 as D5315 – 04 (2011). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D5315-04R17E01. the ASTM website.
2 4
The boldface numbers in parentheses refer to the references at the end of this The last approved version of this historical standard is referenced on
test method. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
´1
D5315 − 04 (2017)
TABLE 1 Relative Retention Times for the Primary and
3.2.4 internal standard, n—a pure analyte(s) added to a
Confirmation Columns and EDLs for the 10 Carbamate
solution in known amount(s) and used to measure the relative
Pesticides
responses of other analytes and surrogates that are components
Retention Time (minutes)
of the same solution. The internal standard must be an analyte
Analyte
A B C
Primary Confirmation EDL
that is not a sample component.
Aldicarb 27.0 21.4 1.0
Aldicarb sulfone 15.2 12.2 2.0 3.2.5 laboratory duplicates (LD1 and LD2), n—two sample
Aldicarb sulfoxide 15.0 17.5 2.0
aliquots taken in the analytical laboratory and analyzed sepa-
Baygon (Propoxur) 29.6 23.4 1.0
rately with identical procedures. Analyses of LD1 and LD2
Carbaryl 30.8 25.4 2.0
Carbofuran 29.3 24.4 1.5
provide a measure of the precision associated with laboratory
3-Hydroxycarbofuran 23.3 19.0 2.0
procedures, but not with sample collection, preservation, or
Methiocarb 34.9 28.6 4.0
storage procedures.
Methomyl 18.4 14.8 0.50
Oxamyl 17.4 14.6 2.0
3.2.6 laboratory-fortified blank (LFB), n—an aliquot of
A
Primary column—250 by 4.6 mm inside diameter Altex Ultrasphere ODS, 5 µm.
reagent water to which known quantities of the test method
B
Confirmation column—250 by 4.6 mm inside diameter Supelco LC-1, 5 µm.
C
analytes are added in the laboratory. The LFB is analyzed
Estimated method detection limit in micrograms per litre.
exactly as a sample is; its purpose is to determine whether the
methodology is in control and whether the laboratory is
capable of making accurate and precise methods at the required
test method detection limit.
E682 Practice for Liquid Chromatography Terms and Rela-
3.2.7 laboratory-fortified sample matrix (LFM), n—an ali-
tionships
quot of an environmental sample to which known quantities of
2.2 U.S. Environmental Protection Agency Standard:
the test method analytes are added in the laboratory. The LFM
EPA Method 531.1 Revision 3.0, USEPA, EMSL-Cincinnati,
is analyzed exactly as a sample is; its purpose is to determine
whether the sample matrix contributes bias to the analytical
EPA Method 531.2 Revision 1.0, USEPA, EMSL-Cincinnati,
results. The background concentrations of the analytes in the
sample matrix must be determined in a separate aliquot and the
measured values in the LFM corrected for background concen-
3. Terminology
trations.
3.1 Definitions:
3.2.8 laboratory performance check solution (LPC), n—a
3.1.1 For definitions of water terms used in this standard,
solution of method analytes, surrogate compounds, and internal
refer to Terminology D1129.
standards used to evaluate the performance of the instrument
3.1.2 For definitions of other terms used in this standard,
system with respect to a defined set of method criteria.
refer to Practice E682.
3.2.9 laboratory reagent blank (LRB), n—an aliquot of
3.2 Definitions of Terms Specific to This Standard:
reagent water treated exactly the same as a sample, including
3.2.1 calibration standard (CAL), n—a solution prepared
being exposed to all glassware, equipment, solvents, reagents,
from the primary dilution standard solution and stock standard
internal standards, and surrogates that are used with other
solutions of the internal standards and surrogate analytes. CAL
samples. The LRB is used to determine whether method
solutions are used to calibrate the instrument response with
analytes or other interferences are present in the laboratory
respect to analyte concentration.
environment, the reagents, or the apparatus.
3.2.2 field duplicates (FD1 and FD2), n—two separate
3.2.10 primary dilution standard solution, n—a solution of
samples collected at the same time, placed under identical
several analytes prepared in the laboratory from stock standard
circumstances, and treated exactly the same throughout field
solutions and diluted as necessary to prepare calibration
and laboratory procedures. Analyses of FD1 and FD2 provide
solutions and other necessary analyte solutions.
a measure of the precision associated with sample collection,
preservation, and storage, as well as with laboratory proce-
3.2.11 quality control sample (QCS), n—a sample matrix
dures.
containing test method analytes or a solution of test method
analytes in a water miscible solvent that is used to fortify water
3.2.3 field reagent blank (FRB), n—reagent water placed in
or environmental samples. The QCS is obtained from a source
a sample container in the laboratory and treated in all respects
external to the laboratory and is used to check the laboratory
as a sample, including being exposed to sampling site
performance with externally prepared test materials.
conditions, storage, preservation, and all analytical procedures.
The purpose of the FRB is to determine whether method
3.2.12 stock standard solution, n—a concentrated solution
analytes or other interferences are present in the field environ-
containing a single certified standard that is a method analyte,
ment.
or a concentrated solution of a single analyte prepared in the
laboratory with an assayed reference compound. Stock stan-
dard solutions are used to prepare primary dilution standards.
Available from United States Environmental Protection Agency (EPA), William
3.2.13 surrogate analyte, n—a pure analyte(s), which is
Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460,
http://www.epa.gov. extremely unlikely to be found in any sample, and which is
´1
D5315 − 04 (2017)
added to a sample aliquot in known amount(s) before extrac- 6.4 The quality of the reagent water used to prepare stan-
tion. It is measured with the same procedures used to measure dards and samples must conform to Specification D1193,
other sample components. The purpose of a surrogate analyte especially in TOC content. High reagent water TOC causes a
is to monitor the method performance with each sample. deterioration of column selectivity, baseline stability, and
analyte sensitivity.
4. Summary of Test Method
6.5 Eliminate all sources of airborne primary amines, espe-
4.1 The water sample is filtered, and a 200 to 400-µL aliquot
cially ammonia, which are absorbed into the mobile phases and
is injected onto a reverse phase HPLC column. Separation of
effect sensitivity.
the analytes is achieved using gradient elution chromatogra-
phy. After elution from the HPLC column, the analytes are
7. Apparatus
hydrolyzed with sodium hydroxide (2.0 g/L NaOH) at 95°C.
7.1 Sampling Equipment:
The methylamine formed during hydrolysis is reacted with
6 7
7.1.1 Sample Bottle, 60-mL screw cap glass vials and caps
o-phthalaldehyde (OPA) and 2-mercaptoethanol to form a
equipped with a PTFE-faced silicone septa. Prior to use, wash
highly fluorescent derivative that is detected by a fluorescence
the vials and septa as described in 6.1.1.
detector (5).
7.2 Filtration Apparatus:
4.2 This test method is applicable to any carbamte analyte
7.2.1 Macrofiltration Device, to filter derivatization solu-
that can be hydrolyzed to a primary amine, not necessarily
tions and mobile phases used in HPLC. It is recommended that
methylamine.
47-mm, 0.45-µm pore size filters be used.
5. Significance and Use
7.2.2 Microfiltration Device, to filter samples prior to HPLC
analysis. Use a 13-mm filter holder and 13-mm diameter,
5.1 N-methylcarbamates and n-methylcarbomoyloximes are
0.2-µm polyester filters.
used in agriculture as insecticides and herbicides. They are
sometimes found in both surface and ground waters and can be
7.3 Syringes and Valves:
toxic to animals and plants at moderate to high concentrations.
7.3.1 Hypodermic Syringe, 10 mL, glass, with Luer-Lok
The manufacturing precursors and degradation products may
tip.
be equally as hazardous to the environment.
7.3.2 Syringe Valve, three-way.
7.3.3 Syringe Needle, 7 to 10 cm long, 17-gage, blunt tip.
6. Interferences
7.3.4 Micro Syringes, various sizes.
6.1 Test method interferences may be caused by contami-
7.4 Miscellaneous:
nants in solvents, reagents, glassware, and other sample pro-
7.4.1 Solution Storage Bottles, amber glass, 10 to 15-mL
cessing apparatuses that lead to discrete artifacts or elevated
capacity with TFE-fluorocarbon-lined screw cap.
baselines in liquid chromatograms. Specific sources of con-
tamination have not been identified. All reagents and apparatus 7.5 High-Performance Liquid Chromatograph (HPLC):
must be routinely demonstrated to be free of interferences 7.5.1 HPLC System, capable of injecting 200 to 1000-µL
under the analysis conditions by running laboratory reagent aliquots and performing ternary linear gradients at a constant
blanks in accordance with 12.2. flow rate. A data system is recommended for measuring peak
6.1.1 Glassware must be cleaned scrupulously. Clean all areas. Table 2 lists the retention times observed for test method
glassware as soon as possible after use by rinsing thoroughly analytes using the columns and analytical conditions described
with the last solvent used in it. below.
6.1.2 After drying, store glassware in a clean environment 7.5.2 Column 1 (Primary Column), 250-mm long by
to prevent any accumulation of dust or other contaminants. 4.6-mm inside diameter, stainless steel, packed with 5-µm C-18
Store the glassware inverted or capped with aluminum foil. material. Mobile phase is established at 1.0 mL/min as a
6.1.3 The use of high-purity reagents and solvents helps to
minimize interference problems.
6.2 Interfering contamination may occur when a sample Sample bottle vial, Pierce No. 13075, available from Pierce Chemical Co., 3747
N. Meridian Rd., Rockford, IL 61101, or equivalent, has been found suitable for use.
containing low concentrations of analytes is analyzed imme-
Sample bottle cap, Pierce No. 12722, available from Pierce Chemical Co., 3747
diately after a sample containing relatively high concentrations
N. Meridian Rd., Rockford, IL 61101, or equivalent, has been found suitable for use.
of analytes. A preventive technique is between-sample rinsing
Millipore Type HA, 0.45 µm for water, and Millipore Type FH, 0.5µ m for
of the sample syringe and filter holder with two portions of organics, available from Millipore Corp.,
...
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.
´1
Designation: D5315 − 04 (Reapproved 2011) D5315 − 04 (Reapproved 2017)
Standard Test Method for
Determination of N-Methyl-Carbamoyloximes and
N-Methylcarbamates in Water by Direct Aqueous Injection
HPLC with Post-Column Derivatization
This standard is issued under the fixed designation D5315; 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.
ε NOTE—Warning notes were editorially updated throughout in December 2017.
1. Scope
1.1 This is a high-performance liquid chromatographic (HPLC) test method applicable to the determination of certain
n-methylcarbamoyloximes and n-methylcarbamates in ground water and finished drinking water (1)). . This test method is
applicable to any carbamate analyte that can be hydrolyzed to a primary amine. The following compounds have been validated
using this test method:
Chemical Abstract Services
A
Analyte Registry Number
Aldicarb 116-06-3
Aldicarb sulfone 1646-88-4
Aldicarb sulfoxide 1646-87-3
Baygon 114-26-1
Carbaryl 63-25-2
Carbofuran 1563-66-2
3-Hydroxycarbofuran 16655-82-6
Methiocarb 2032-65-7
Methomyl 16752-77-5
Oxamyl 23135-22-0
________________
A
Numbering system of Chemical Abstracts, Inc.
1.2 This test method has been validated in a collaborative round-robin study (2) and estimated detection limits (EDLs) have
been determined for the analytes listed in 1.1 (Table 1). Observed detection limits may vary between ground waters, depending
on the nature of interferences in the sample matrix and the specific instrumentation used.
1.3 This test method is restricted to use by, or under the supervision of, analysts experienced in both the use of liquid
chromatography and the interpretation of liquid chromatograms. Each analyst should demonstrate an ability to generate acceptable
results with this test method using the procedure described in 12.3.
1.4 When this test method is used to analyze unfamiliar samples for any or all of the analytes listed in 1.1, analyte identifications
should be confirmed by at least one additional qualitative technique.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
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 safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. Additional guidance on laboratory safety is available and suitable references
for the information are provided (3-5).
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.
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 May 1, 2011Dec. 15, 2017. Published June 2011January 2018. Originally approved in 1992. Last previous edition approved in 20042011 as
D5315 – 04.D5315 – 04 (2011). DOI: 10.1520/D5315-04R11.10.1520/D5315-04R17E01.
The boldface numbers in parentheses refer to the references at the end of this test method.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
´1
D5315 − 04 (2017)
TABLE 1 Relative Retention Times for the Primary and
Confirmation Columns and EDLs for the 10 Carbamate
Pesticides
Retention Time (minutes)
Analyte
A B C
Primary Confirmation EDL
Aldicarb 27.0 21.4 1.0
Aldicarb sulfone 15.2 12.2 2.0
Aldicarb sulfoxide 15.0 17.5 2.0
Baygon (Propoxur) 29.6 23.4 1.0
Carbaryl 30.8 25.4 2.0
Carbofuran 29.3 24.4 1.5
3-Hydroxycarbofuran 23.3 19.0 2.0
Methiocarb 34.9 28.6 4.0
Methomyl 18.4 14.8 0.50
Oxamyl 17.4 14.6 2.0
A
Primary column—250 by 4.6 mm inside diameter Altex Ultrasphere ODS, 5 μm.
B
Confirmation column—250 by 4.6 mm inside diameter Supelco LC-1, 5 μm.
C
Estimated method detection limit in micrograms per litre.
2. Referenced Documents
2.1 ASTM Standards:
D1129 Terminology Relating to Water
D1192 Guide for Equipment for Sampling Water and Steam in Closed Conduits (Withdrawn 2003)
D1193 Specification for Reagent Water
D2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
D3370 Practices for Sampling Water from Closed Conduits
D3694 Practices for Preparation of Sample Containers and for Preservation of Organic Constituents
E682 Practice for Liquid Chromatography Terms and Relationships
2.2 U.S. Environmental Protection Agency Standard:
EPA Method 531.1,531.1 Revision 3.0, USEPA, EMSL-Cincinnati, 1989
EPA Method 531.2,531.2 Revision 1.0, USEPA, EMSL-Cincinnati, 2001
3. Terminology
3.1 Definitions—Definitions: For definitions of water terms used in this test method, refer to Terminology D1129. For definitions
of other terms used in this test method, refer to Practice E682.
3.1.1 For definitions of water terms used in this standard, refer to Terminology D1129.
3.1.2 For definitions of other terms used in this standard, refer to Practice E682.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 calibration standard (CAL)(CAL),—n—a solution prepared from the primary dilution standard solution and stock
standard solutions of the internal standards and surrogate analytes. CAL solutions are used to calibrate the instrument response with
respect to analyte concentration.
3.2.2 field duplicates (FD1 and FD2)FD2),—n—two separate samples collected at the same time, placed under identical
circumstances, and treated exactly the same throughout field and laboratory procedures. Analyses of FD1 and FD2 provide a
measure of the precision associated with sample collection, preservation, and storage, as well as with laboratory procedures.
3.2.3 field reagent blank (FRB)(FRB),—n—reagent water placed in a sample container in the laboratory and treated in all
respects as a sample, including being exposed to sampling site conditions, storage, preservation, and all analytical procedures. The
purpose of the FRB is to determine whether method analytes or other interferences are present in the field environment.
3.2.4 internal standard—standard, n—a pure analyte(s) added to a solution in known amount(s) and used to measure the relative
responses of other analytes and surrogates that are components of the same solution. The internal standard must be an analyte that
is not a sample component.
3.2.5 laboratory duplicates (LD1 and LD2)LD2),—n—two sample aliquots taken in the analytical laboratory and analyzed
separately with identical procedures. Analyses of LD1 and LD2 provide a measure of the precision associated with laboratory
procedures, but not with sample collection, preservation, or storage procedures.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
The last approved version of this historical standard is referenced on www.astm.org.
Published by the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, OH 45268, 1989.Available from United States
Environmental Protection Agency (EPA), William Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460, http://www.epa.gov.
´1
D5315 − 04 (2017)
3.2.6 laboratory-fortified blank (LFB)(LFB),—n—an aliquot of reagent water to which known quantities of the test method
analytes are added in the laboratory. The LFB is analyzed exactly as a sample is; its purpose is to determine whether the
methodology is in control and whether the laboratory is capable of making accurate and precise methods at the required test method
detection limit.
3.2.7 laboratory-fortified sample matrix (LFM)(LFM),—n—an aliquot of an environmental sample to which known quantities
of the test method analytes are added in the laboratory. The LFM is analyzed exactly as a sample is; its purpose is to determine
whether the sample matrix contributes bias to the analytical results. The background concentrations of the analytes in the sample
matrix must be determined in a separate aliquot and the measured values in the LFM corrected for background concentrations.
3.2.8 laboratory performance check solution (LPC)(LPC),—n—a solution of method analytes, surrogate compounds, and
internal standards used to evaluate the performance of the instrument system with respect to a defined set of method criteria.
3.2.9 laboratory reagent blank (LRB)(LRB),—n—an aliquot of reagent water treated exactly the same as a sample, including
being exposed to all glassware, equipment, solvents, reagents, internal standards, and surrogates that are used with other samples.
The LRB is used to determine whether method analytes or other interferences are present in the laboratory environment, the
reagents, or the apparatus.
3.2.10 primary dilution standard solution—solution, n—a solution of several analytes prepared in the laboratory from stock
standard solutions and diluted as necessary to prepare calibration solutions and other necessary analyte solutions.
3.2.11 quality control sample (QCS)(QCS),—n—a sample matrix containing test method analytes or a solution of test method
analytes in a water miscible solvent that is used to fortify water or environmental samples. The QCS is obtained from a source
external to the laboratory and is used to check the laboratory performance with externally prepared test materials.
3.2.12 stock standard solution—solution, n—a concentrated solution containing a single certified standard that is a method
analyte, or a concentrated solution of a single analyte prepared in the laboratory with an assayed reference compound. Stock
standard solutions are used to prepare primary dilution standards.
3.2.13 surrogate analyte—analyte, n—a pure analyte(s), which is extremely unlikely to be found in any sample, and which is
added to a sample aliquot in known amount(s) before extraction. It is measured with the same procedures used to measure other
sample components. The purpose of a surrogate analyte is to monitor the method performance with each sample.
4. Summary of Test Method
4.1 The water sample is filtered, and a 200 to 400-μL aliquot is injected onto a reverse phase HPLC column. Separation of the
analytes is achieved using gradient elution chromatography. After elution from the HPLC column, the analytes are hydrolyzed with
sodium hydroxide (2.0 g/L NaOH) at 95°C. The methylamine formed during hydrolysis is reacted with o-phthalaldehyde (OPA)
and 2-mercaptoethanol to form a highly fluorescent derivative that is detected by a fluorescence detector (5).
4.2 This test method is applicable to any carbamte analyte that can be hydrolyzed to a primary amine, not necessarily
methylamine.
5. Significance and Use
5.1 N-methylcarbamates and n-methylcarbomoyloximes are used in agriculture as insecticides and herbicides. They are
sometimes found in both surface and ground waters and can be toxic to animals and plants at moderate to high concentrations. The
manufacturing precursors and degradation products may be equally as hazardous to the environment.
6. Interferences
6.1 Test method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing
apparatuses that lead to discrete artifacts or elevated baselines in liquid chromatograms. Specific sources of contamination have
not been identified. All reagents and apparatus must be routinely demonstrated to be free of interferences under the analysis
conditions by running laboratory reagent blanks in accordance with 12.2.
6.1.1 Glassware must be cleaned scrupulously. Clean all glassware as soon as possible after use by rinsing thoroughly with the
last solvent used in it.
6.1.2 After drying, store glassware in a clean environment to prevent any accumulation of dust or other contaminants. Store the
glassware inverted or capped with aluminum foil.
6.1.3 The use of high-purity reagents and solvents helps to minimize interference problems.
6.2 Interfering contamination may occur when a sample containing low concentrations of analytes is analyzed immediately after
a sample containing relatively high concentrations of analytes. A preventive technique is between-sample rinsing of the sample
syringe and filter holder with two portions of water. Analyze one or more laboratory method blanks after analysis of a sample
containing high concentrations of analytes.
6.3 Matrix interference may be caused by contaminants present in the sample. The extent of matrix interference will vary
considerably from source to source, depending upon the water sampled. Positive analyte identifications must be confirmed using
the alternative conformational columns, or LC/MS.
´1
D5315 − 04 (2017)
A
TABLE 2 Retention Times for Method Analytes Retention Time
B C D
Analyte Primary Confirmation Confirmation
Minutes
Aldicarb sulfoxide 6.80 17.5
Aldicarb sulfone 7.77 12.2
Oxamyl 8.20 14.6
Methomyl 8.94 14.8
3-Hydroxycarbofuran 13.65 19
Aldicarb 16.35 21.4
Baygon (Propoxur) 18.86 24.4
Carbofuran 19.17 23.4
Carbaryl 20.29 25.4
Methiocarb 24.74 28.6
BDMC 25.28 .
A
Columns and analytical conditions are described in 7.5.2, 7.5.3.
B
Beckman Ultasphere ODS.
C
Supelco LC-1.
D
Waters Carbamate Analysis Column using ternary gradient conditions.
6.4 The quality of the reagent water used to prepare standards and samples must conform to D1193,Specification D1193,
especially in TOC content. High reagent water TOC causes a deterioration of column selectivity, baseline stability, and analyte
sensitivity.
6.5 Eliminate all sources of airborne primary amines, especially ammonia, which are absorbed into the mobile phases and effect
sensitivity.
7. Apparatus
7.1 Sampling Equipment:
6 7
7.1.1 Sample Bottle, 60-mL screw cap glass vials and caps equi
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.