ASTM D5315-92(1998)

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An American National Standard
Designation: D 5315 – 92 (Reapproved 1998)
Standard Test Method for
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 D 5315; 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 (e) indicates an editorial change since the last revision or reapproval.
TABLE 1 Relative Retention Times for the Primary and
1. Scope
Confirmation Columns and EDLs for the 10 Carbamate
1.1 This is a high-performance liquid chromatographic
Pesticides
(HPLC) test method applicable to the determination of certain
Retention Time (minutes)
n-methylcarbamoyloximes and n-methylcarbamates in ground Analyte
A B C
Primary Confirmation EDL
water and finished drinking water (1) (also see EPA Method
Aldicarb 27.0 21.4 1.0
531.1, Revision 3.0). The following compounds can be deter-
Aldicarb sulfone 15.2 12.2 2.0
mined using this test method:
Aldicarb sulfoxide 15.0 17.5 2.0
Baygon 29.6 23.4 1.0
Chemical Abstract Services
A
Carbaryl 30.8 25.4 2.0
Analyte Registry Number
Carbofuran 29.3 24.4 1.5
Aldicarb 116-06-3
3-Hydroxycarbofuran 23.3 19.0 2.0
Aldicarb sulfone 1646-88-4
Methiocarb 34.9 28.6 4.0
Aldicarb sulfoxide 1646-87-3
Methomyl 18.4 14.8 0.50
Baygon 114-26-1
Oxamyl 17.4 14.6 2.0
Carbaryl 63-25-2
Carbofuran 1563-66-2 A
Primary column—250 by 4.6 mm inside diameter Altex Ultrasphere ODS, 5
3-Hydroxycarbofuran 16655-82-6
μm.
Methiocarb 2032-65-7 B
Confirmation column—250 by 4.6 mm inside diameter Supelco LC-1, 5 μm.
C
Methomyl 16752-77-5
Estimated method detection limit in micrograms per litre.
Oxamyl 23135-22-0
________________
1.5 The values stated in SI units are to be regarded as the
A
Numbering system of Chemical Abstracts, Inc.
standard.
1.2 This test method has been validated in a collaborative
1.6 This standard does not purport to address all of the
round-robin study (2) and estimated detection limits (EDLs)
safety concerns, if any, associated with its use. It is the
have been determined for the analytes listed in 1.1 (Table 1).
responsibility of the user of this standard to establish appro-
Observed detection limits may vary between ground waters,
priate safety and health practices and determine the applica-
depending on the nature of interferences in the sample matrix
bility of regulatory limitations prior to use. For specific hazard
and the specific instrumentation used.
statements, see Note 1 and Note 3. Additional guidance on
1.3 This test method is restricted to use by, or under the
laboratory safety is available and suitable references for the
supervision of, analysts experienced in both the use of liquid
information are provided (3-5).
chromatography and the interpretation of liquid chromato-
grams. Each analyst should demonstrate an ability to generate
2. Referenced Documents
acceptable results with this test method using the procedure
2.1 ASTM Standards:
described in 12.3.
D 1129 Terminology Relating to Water
1.4 When this test method is used to analyze unfamiliar
D 1192 Specification for Equipment for Sampling Water
samples for any or all of the analytes listed in 1.1, analyte
and Steam in Closed Conduits
identifications should be confirmed by at least one additional
D 1193 Specification for Reagent Water
qualitative technique.
D 2777 Practice for Determination of Precision and Bias of
Applicable Methods of Committee D-19 on Water
D 3370 Practices for Sampling Water from Closed Con-
This test method is under the jurisdiction of ASTM Committee D19 on Water
duits
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved Oct. 15, 1992. Published December 1992.
The boldface numbers in parentheses refer to the references at the end of this
test method. Annual Book of ASTM Standards, Vol 11.01.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 5315 – 92 (1998)
D 3694 Practices for Preparation of Sample Containers and whether the sample matrix contributes bias to the analytical
for Preservation of Organic Constituents results. The background concentrations of the analytes in the
E 682 Practice for Liquid Chromatography Terms and Re- sample matrix must be determined in a separate aliquot and the
lationships measured values in the LFM corrected for background concen-
2.2 U.S. Environmental Protection Agency Standard: trations.
EPA Method 531.1, Revision 3.0, USEPA, EMSL- 3.2.8 laboratory performance check solution (LPC)—a so-
Cincinnati, 1989 lution of method analytes, surrogate compounds, and internal
standards used to evaluate the performance of the instrument
3. Terminology
system with respect to a defined set of method criteria.
3.2.9 laboratory reagent blank (LRB)—an aliquot of re-
3.1 Definitions—For definitions of water terms used in this
agent water treated exactly the same as a sample, including
test method, refer to Terminology D 1129. For definitions of
being exposed to all glassware, equipment, solvents, reagents,
other terms used in this test method, refer to Practice E 682.
internal standards, and surrogates that are used with other
3.2 Definitions of Terms Specific to This Standard:
samples. The LRB is used to determine whether method
3.2.1 calibration standard (CAL)—a solution prepared
analytes or other interferences are present in the laboratory
from the primary dilution standard solution and stock standard
environment, the reagents, or the apparatus.
solutions of the internal standards and surrogate analytes. CAL
3.2.10 primary dilution standard solution—a solution of
solutions are used to calibrate the instrument response with
several analytes prepared in the laboratory from stock standard
respect to analyte concentration.
solutions and diluted as necessary to prepare calibration
3.2.2 field duplicates (FD1 and FD2)—two separate
solutions and other necessary analyte solutions.
samples collected at the same time, placed under identical
3.2.11 quality control sample (QCS)—a sample matrix
circumstances, and treated exactly the same throughout field
containing test method analytes or a solution of test method
and laboratory procedures. Analyses of FD1 and FD2 provide
analytes in a water miscible solvent that is used to fortify water
a measure of the precision associated with sample collection,
or environmental samples. The QCS is obtained from a source
preservation, and storage, as well as with laboratory proce-
external to the laboratory and is used to check the laboratory
dures.
performance with externally prepared test materials.
3.2.3 field reagent blank (FRB)—reagent water placed in a
3.2.12 stock standard solution—a concentrated solution
sample container in the laboratory and treated in all respects as
containing a single certified standard that is a method analyte,
a sample, including being exposed to sampling site conditions,
or a concentrated solution of a single analyte prepared in the
storage, preservation, and all analytical procedures. The pur-
laboratory with an assayed reference compound. Stock stan-
pose of the FRB is to determine whether method analytes or
dard solutions are used to prepare primary dilution standards.
other interferences are present in the field environment.
3.2.13 surrogate analyte—a pure analyte(s), which is ex-
3.2.4 internal standard—a pure analyte(s) added to a solu-
tremely unlikely to be found in any sample, and which is added
tion in known amount(s) and used to measure the relative
to a sample aliquot in known amount(s) before extraction. It is
responses of other analytes and surrogates that are components
measured with the same procedures used to measure other
of the same solution. The internal standard must be an analyte
sample components. The purpose of a surrogate analyte is to
that is not a sample component.
monitor the method performance with each sample.
3.2.5 laboratory duplicates (LD1 and LD2)—two sample
aliquots taken in the analytical laboratory and analyzed sepa-
4. Summary of Test Method
rately with identical procedures. Analyses of LD1 and LD2
4.1 The water sample is filtered, and a 200 to 400-μL aliquot
provide a measure of the precision associated with laboratory
is injected into a reverse phase HPLC column. Separation of
procedures, but not with sample collection, preservation, or
the analytes is achieved using gradient elution chromatogra-
storage procedures.
phy. After elution from the HPLC column, the analytes are
3.2.6 laboratory-fortified blank (LFB)—an aliquot of re-
hydrolyzed with sodium hydroxide (2.0 g/L NaOH) at 95°C.
agent water to which known quantities of the test method
The methylamine formed during hydrolysis is reacted with
analytes are added in the laboratory. The LFB is analyzed
o-phthalaldehyde (OPA) and 2-mercaptoethanol to form a
exactly as a sample is; its purpose is to determine whether the
highly fluorescent derivative that is detected by a fluorescence
methodology is in control and whether the laboratory is
detector (5).
capable of making accurate and precise methods at the required
test method detection limit.
5. Significance and Use
3.2.7 laboratory-fortified sample matrix (LFM)—an aliquot
5.1 N-methylcarbamates and n-methylcarbomoyloximes are
of an environmental sample to which known quantities of the
used in agriculture as insecticides and herbicides. They are
test method analytes are added in the laboratory. The LFM is
sometimes found in both surface and ground waters and can be
analyzed exactly as a sample is; its purpose is to determine
toxic to animals and plants at moderate to high concentrations.
6. Interferences
Annual Book of ASTM Standards, Vol 11.02.
6.1 Test method interferences may be caused by contami-
Annual Book of ASTM Standards, Vol 14.01.
nants in solvents, reagents, glassware, and other sample pro-
Published by the U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, OH 45268, 1989. cessing apparatuses that lead to discrete artifacts or elevated
D 5315 – 92 (1998)
A
TABLE 2 Retention Times for Method Analytes Retention Time
baselines in liquid chromatograms. Specific sources of con-
B C
tamination have not been identified. All reagents and apparatus Analyte Primary Confirmation
must be routinely demonstrated to be free of interferences
Minutes
Aldicarb sulfoxide 6.80 17.5
under the analysis conditions by running laboratory reagent
Aldicarb sulfone 7.77 12.2
blanks in accordance with 12.2.
Oxamyl 8.20 14.6
Methomyl 8.94 14.8
6.1.1 Glassware must be cleaned scrupulously. Clean all
3-Hydroxycarbofuran 13.65 19
glassware as soon as possible after use by rinsing thoroughly
Aldicarb 16.35 21.4
with the last solvent used in it. Follow by washing with hot Baygon 18.86 24.4
Carbofuran 19.17 23.4
water and detergent and rinsing thoroughly with tap and
Carbaryl 20.29 25.4
reagent water. Drain dry, and heat in an oven or muffle furnace
Methiocarb 24.74 28.6
BDMC 25.28 .
at 450°C for 1 h. Do not heat volumetric ware. Thermally
A
stable materials might not be eliminated by this treatment. Columns and analytical conditions are described in 7.5.2, 7.5.3.
B
Beckman Ultasphere ODS.
Rinsing thoroughly with acetone may be substituted for the
C
Supelco LC-1.
heating.
6.1.2 After drying and cooling, seal and store glassware in a
7.2.2 Microfiltration Device, to filter samples prior to HPLC
clean environment to prevent any accumulation of dust or other
analysis. Use a 13-mm filter holder and 13-mm diameter,
contaminants. Store the glassware inverted or capped with
0.2-μm polyester filters.
aluminum foil.
7.3 Syringes and Valves:
6.1.3 The use of high-purity reagents and solvents helps to
7.3.1 Hypodermic Syringe, 10 mL, glass, with Luer-Lok
minimize interference problems. Purification of solvents by
tip.
distillation in all-glass systems may be required.
7.3.2 Syringe Valve, three-way.
7.3.3 Syringe Needle, 7 to 10 cm long, 17-gage, blunt tip.
NOTE 1—Warning: When a solvent is purified, stabilizers added by the
7.3.4 Micro Syringes, various sizes.
manufacturer are removed, thus making the solvent potentially hazardous.
7.4 Miscellaneous:
NOTE 2—Caution: When a solvent is purified, preservatives added by
7.4.1 Solution Storage Bottles, amber glass, 10 to 15-mL
the manufacturer are removed, thus potentially reducing the shelf-life.
capacity with TFE-fluorocarbon-lined screw cap.
6.2 Interfering contamination may occur when a sample
7.5 High-Performance Liquid Chromatograph (HPLC):
containing low concentrations of analytes is analyzed imme-
7.5.1 HPLC System, capable of injecting 200 to 400-μL
diately after a sample containing relatively high concentrations
aliquots and performing binary linear gradients at a constant
of analytes. A preventive technique is between-sample rinsing
flow rate. A data system is recommended for measuring peak
of the sample syringe and filter holder with two portions of
areas. Table 2 lists the retention times observed for test method
water. Analyze one or more laboratory method blanks after
analytes using the columns and analytical conditions described
analysis of a sample containing high concentrations of ana-
below.
lytes.
7.5.2 Column 1 (Primary Column), 250 mm long by
4.6-mm inside diameter, stainless steel, packed with 5-μm C-18
6.3 Matrix interference may be caused by contaminants
material. Mobile phase is established at 1.0 mL/min as a
present in the sample. The extent of matrix interference will
linear gradient from 15:85 methanol: water to 100 % methanol
vary considerably from source to source, depending upon the
in 32 min. Data presented in this test method were obtained
water sampled. Positive identifications must be confirmed.
using this column.
7.5.3 Column 2 (Alternative Column), 250 mm long by
7. Apparatus
4.6-mm inside diameter, stainless steel, packed with 5-μm
7.1 Sampling Equipment: 17
silica beads coated with trimethylsilyl. Mobile phase is
7 8
7.1.1 Sample Bottle, 60-mL screw cap glass vials and caps
established at 1.0 mL/min as a linear gradient from 15:85
equipped with a PTFE-faced silicone septa. Prior to use, wash
methanol: water to 100 % methanol in 32 min.
the vials and septa as described in 6.1.1.
7.2 Filtration Apparatus:
Millipore stainless steel XX300/200, available from Millipore Corp., 80 Ashby
7.2.1 Macrofiltration Device, to filter derivatization solu-
Rd., Bedford, MA 01730, or equivalent.
tions and mobile phases used in HPLC. It is recommended that Nucleopore 180406, av
...