ASTM D5315-04(2024)
(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
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, 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
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: D5315 − 04 (Reapproved 2024)
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.
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
1.5 The values stated in SI units are to be regarded as
water and finished drinking water (1). This test method is
standard. No other units of measurement are included in this
applicable to any carbamate analyte that can be hydrolyzed to
standard.
a primary amine. The following compounds have been vali-
dated using this test method: 1.6 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
Chemical Abstract Services
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
mine the applicability of regulatory limitations prior to use.
Aldicarb sulfoxide 1646-87-3
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
1.7 This international standard was developed in accor-
3-Hydroxycarbofuran 16655-82-6
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
mendations issued by the World Trade Organization Technical
Numbering system of Chemical Abstracts, Inc.
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). 3
2.1 ASTM Standards:
Observed detection limits may vary between ground waters,
D1129 Terminology Relating to Water
depending on the nature of interferences in the sample matrix
D1192 Guide for Equipment for Sampling Water and Steam
and the specific instrumentation used. 4
in Closed Conduits (Withdrawn 2003)
D1193 Specification for Reagent Water
1.3 This test method is restricted to use by, or under the
D2777 Practice for Determination of Precision and Bias of
supervision of, analysts experienced in both the use of liquid
Applicable Test Methods of Committee D19 on Water
chromatography and the interpretation of liquid chromato-
D3370 Practices for Sampling Water from Flowing Process
grams. Each analyst should demonstrate an ability to generate
Streams
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
E682 Practice for Liquid Chromatography Terms and Rela-
tionships
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 1, 2024. Published April 2024. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
ɛ1
approved in 1992. Last previous edition approved in 2017 as D5315 – 04 (2017) . Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D5315-04R24. the ASTM website.
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
D5315 − 04 (2024)
TABLE 1 Relative Retention Times for the Primary and
of the same solution; the internal standard must be an analyte
Confirmation Columns and EDLs for the 10 Carbamate
that is not a sample component.
Pesticides
3.2.5 laboratory duplicates (LD1 and LD2), n—two sample
Retention Time (minutes)
Analyte
aliquots taken in the analytical laboratory and analyzed sepa-
A B C
Primary Confirmation EDL
rately with identical procedures; analyses of LD1 and LD2
Aldicarb 27.0 21.4 1.0
provide a measure of the precision associated with laboratory
Aldicarb sulfone 15.2 12.2 2.0
Aldicarb sulfoxide 15.0 17.5 2.0
procedures, but not with sample collection, preservation, or
Baygon (Propoxur) 29.6 23.4 1.0
storage procedures.
Carbaryl 30.8 25.4 2.0
Carbofuran 29.3 24.4 1.5
3.2.6 laboratory-fortified blank (LFB), n—an aliquot of
3-Hydroxycarbofuran 23.3 19.0 2.0
reagent water to which known quantities of the test method
Methiocarb 34.9 28.6 4.0
Methomyl 18.4 14.8 0.50 analytes are added in the laboratory; the LFB is analyzed
Oxamyl 17.4 14.6 2.0
exactly as a sample is; its purpose is to determine whether the
A
Primary column—250 mm by 4.6 mm inside diameter Altex Ultrasphere ODS, 5
methodology is in control and whether the laboratory is
μm.
capable of making accurate and precise methods at the required
B
Confirmation column—250 mm by 4.6 mm inside diameter Supelco LC-1, 5 μm.
C
test method detection limit.
Estimated method detection limit in micrograms per litre.
3.2.7 laboratory-fortified sample matrix (LFM), n—an ali-
quot of an environmental sample to which known quantities of
5 the test method analytes are added in the laboratory; the LFM
2.2 U.S. Environmental Protection Agency Standard:
is analyzed exactly as a sample is; its purpose is to determine
EPA Method 531.1 Revision 3.0, USEPA, EMSL-Cincinnati,
whether the sample matrix contributes bias to the analytical
results; the background concentrations of the analytes in the
EPA Method 531.2 Revision 1.0, USEPA, EMSL-Cincinnati,
sample matrix must be determined in a separate aliquot and the
measured values in the LFM corrected for background concen-
trations.
3. Terminology
3.2.8 laboratory performance check solution (LPC), n—a
3.1 Definitions:
solution of method analytes, surrogate compounds, and internal
3.1.1 For definitions of water terms used in this standard,
standards used to evaluate the performance of the instrument
refer to Terminology D1129.
system with respect to a defined set of method criteria.
3.1.2 For definitions of other terms used in this standard,
refer to Practice E682.
3.2.9 laboratory reagent blank (LRB), n—an aliquot of
reagent water treated exactly the same as a sample, including
3.2 Definitions of Terms Specific to This Standard:
being exposed to all glassware, equipment, solvents, reagents,
3.2.1 calibration standard (CAL), n—a solution prepared
internal standards, and surrogates that are used with other
from the primary dilution standard solution and stock standard
samples; the LRB is used to determine whether method
solutions of the internal standards and surrogate analytes; CAL
analytes or other interferences are present in the laboratory
solutions are used to calibrate the instrument response with
environment, the reagents, or the apparatus.
respect to analyte concentration.
3.2.10 primary dilution standard solution, n—a solution of
3.2.2 field duplicates (FD1 and FD2), n—two separate
several analytes prepared in the laboratory from stock standard
samples collected at the same time, placed under identical
solutions and diluted as necessary to prepare calibration
circumstances, and treated exactly the same throughout field
solutions and other necessary analyte solutions.
and laboratory procedures; analyses of FD1 and FD2 provide a
measure of the precision associated with sample collection,
3.2.11 quality control sample (QCS), n—a sample matrix
preservation, and storage, as well as with laboratory proce-
containing test method analytes or a solution of test method
dures.
analytes in a water miscible solvent that is used to fortify water
or environmental samples; the QCS is obtained from a source
3.2.3 field reagent blank (FRB), n—reagent water placed in
external to the laboratory and is used to check the laboratory
a sample container in the laboratory and treated in all respects
performance with externally prepared test materials.
as a sample, including being exposed to sampling site
conditions, storage, preservation, and all analytical procedures;
3.2.12 stock standard solution, n—a concentrated solution
the purpose of the FRB is to determine whether method
containing a single certified standard that is a method analyte,
analytes or other interferences are present in the field environ-
or a concentrated solution of a single analyte prepared in the
ment.
laboratory with an assayed reference compound; stock standard
3.2.4 internal standard, n—a pure analyte(s) added to a solutions are used to prepare primary dilution standards.
solution in known amount(s) and used to measure the relative
3.2.13 surrogate analyte, n—a pure analyte(s), which is
responses of other analytes and surrogates that are components
extremely unlikely to be found in any sample, and which is
added to a sample aliquot in known amount(s) before extrac-
tion; it is measured with the same procedures used to measure
Available from United States Environmental Protection Agency (EPA), William
other sample components; the purpose of a surrogate analyte is
Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460,
http://www.epa.gov. to monitor the method performance with each sample.
D5315 − 04 (2024)
4. Summary of Test Method especially in TOC content. High reagent water TOC causes a
deterioration of column selectivity, baseline stability, and
4.1 The water sample is filtered, and a 200 μL to 400 μL
analyte sensitivity.
aliquot is injected onto a reverse phase HPLC column. Sepa-
6.5 Eliminate all sources of airborne primary amines, espe-
ration of the analytes is achieved using gradient elution
cially ammonia, which are absorbed into the mobile phases and
chromatography. After elution from the HPLC column, the
effect sensitivity.
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 7. Apparatus
to form a highly fluorescent derivative that is detected by a
7.1 Sampling Equipment:
fluorescence detector (5).
6 7
7.1.1 Sample Bottle, 60 mL screw cap glass vials and caps
4.2 This test method is applicable to any carbamate analyte equipped with a PTFE-faced silicone septa. Prior to use, wash
the vials and septa as described in 6.1.1.
that can be hydrolyzed to a primary amine, not necessarily
methylamine.
7.2 Filtration Apparatus:
7.2.1 Macrofiltration Device, to filter derivatization solu-
5. Significance and Use
tions and mobile phases used in HPLC. It is recommended that
47 mm, 0.45 μm pore size filters be used.
5.1 N-methylcarbamates and n-methylcarbomoyloximes are
used in agriculture as insecticides and herbicides. They are 7.2.2 Microfiltration Device, to filter samples prior to HPLC
sometimes found in both surface and ground waters and can be analysis. Use a 13 mm filter holder and 13 mm diameter,
0.2 μm polyester filters.
toxic to animals and plants at moderate to high concentrations.
The manufacturing precursors and degradation products may
7.3 Syringes and Valves:
be equally as hazardous to the environment.
7.3.1 Hypodermic Syringe, 10 mL, glass, with Luer-Lok
tip.
6. Interferences
7.3.2 Syringe Valve, three-way.
6.1 Test method interferences may be caused by contami-
7.3.3 Syringe Needle, 7 cm to 10 cm long, 17 gauge, blunt
nants in solvents, reagents, glassware, and other sample pro- tip.
cessing apparatuses that lead to discrete artifacts or elevated
7.3.4 Micro Syringes, various sizes.
baselines in liquid chromatograms. Specific sources of con-
7.4 Miscellaneous:
tamination have not been identified. All reagents and apparatus
7.4.1 Solution Storage Bottles, amber glass, 10 mL to
must be routinely demonstrated to be free of interferences
15 mL capacity with TFE-fluorocarbon-lined screw cap.
under the analysis conditions by running laboratory reagent
blanks in accordance with 12.2.
7.5 High-Performance Liquid Chromatograph (HPLC):
6.1.1 Glassware must be cleaned scrupulously. Clean all 7.5.1 HPLC System, capable of injecting 200 μL to
1000 μL aliquots and performing ternary linear gradients at a
glassware as soon as possible after use by rinsing thoroughly
with the last solvent used in it. constant flow rate. A data system is recommended for measur-
ing peak areas. Table 2 lists the retention times observed for
6.1.2 After drying, store glassware in a clean environment
test method analytes using the columns and analytical condi-
to prevent any accumulation of dust or other contaminants.
tions described below.
Store the glassware inverted or capped with aluminum foil.
7.5.2 Column 1 (Primary Column), 250 mm long by
6.1.3 The use of high-purity reagents and solvents helps to
4.6 mm inside diameter, stainless steel, packed with 5 μm C-18
minimize interference problems.
material. Mobile phase is established at 1.0 mL/min as a
6.2 Interfering contamination may occur when a sample
containing low concentrations of analytes is analyzed imme-
diately after a sample containing relatively high concentrations
Sample bottle vial, Pierce No. 13075, available from Pierce Chemical Co., 3747
of analytes. A preventive technique is between-sample rinsing
N. Meridian Rd., Rockford, IL 61101, or equivalent, has been found suitable for use.
of the sample syringe and filter holder with two portions of 7
Sample bottle cap, Pierce No. 12722, available from Pierce Chemical Co., 3747
water. Analyze one or more laboratory method blanks after N. Meridian Rd., Rockford, IL 61101, or equivalent, has been found suitable for use.
Millipore Type HA, 0.45 μm for water, and Millipore Type FH, 0.5 μm for
analysis of a sample containing hi
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