ASTM D5317-98(2011)
(Test Method)Standard Test Method for Determination of Chlorinated Organic Acid Compounds in Water by Gas Chromatography with an Electron Capture Detector
Standard Test Method for Determination of Chlorinated Organic Acid Compounds in Water by Gas Chromatography with an Electron Capture Detector
SIGNIFICANCE AND USE
Chlorinated phenoxyacid herbicides, and other organic acids are used extensively for weed control. Esters and salts of 2,4-D and silvex have been used as aquatic herbicides in lakes, streams, and irrigation canals. Phenoxy acid herbicides can be toxic even at low concentrations. For example, the 96 h, TLm for silvex is 2.4 mg/L for bluegills (1) . These reasons make apparent the need for a standard test method for such compounds in water.
SCOPE
1.1 This test method covers a gas chromatographic procedure for the quantitative determination of selected chlorinated acids and other acidic herbicides in water. Similar chemicals may also be determined by this test method, but it is the user's responsibility to verify the applicability of this test method to any compounds not listed in this scope. The acid form of the following compounds were interlaboratory tested using this test method, and the results were found acceptable:
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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
Designation: D5317 − 98 (Reapproved 2011)
Standard Test Method for
Determination of Chlorinated Organic Acid Compounds in
Water by Gas Chromatography with an Electron Capture
Detector
This standard is issued under the fixed designation D5317; 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 tography (GC) and in the interpretation of gas chromatograms.
Each analyst must demonstrate the ability to generate accept-
1.1 This test method covers a gas chromatographic proce-
ableresultswiththistestmethodusingtheproceduredescribed
dure for the quantitative determination of selected chlorinated
in 19.3. It is the user’s responsibility to ensure the validity of
acids and other acidic herbicides in water. Similar chemicals
this test method for waters of untested matrices.
may also be determined by this test method, but it is the user’s
responsibility to verify the applicability of this test method to 1.5 Analytes that are not separated chromatographically,
any compounds not listed in this scope. The acid form of the that is, which have very similar retention times, cannot be
following compounds were interlaboratory tested using this individually identified and measured in the same calibration
test method, and the results were found acceptable: mixture or water sample unless an alternate technique for
identification and quantitation exists (16.6, 16.7, and 16.8).
Analyte Chemical Abstract Services
Registry Number
1.6 When this test method is used to analyze unfamiliar
Bentazon 25057-89-0
samples for any or all of the analytes given in 1.1, analyte
2,4-D 94-75-7
2,4-DB 94-82-6
identifications must be confirmed by at least one additional
DCPA acid metabolites
qualitative technique.
Dicamba 1918-00-9
3,5-Dichlorobenzoic acid 51-36-5
1.7 The values stated in SI units are to be regarded as the
Dichlorprop 120-36-5
standard. The values given in parentheses are for information
5-Hydroxydicamba 7600-50-2
Pentachlorophenol (PCP) 87-86-5
only.
Picloram 1918-02-1
1.8 This standard does not purport to address all of the
2,4,5-T 93-76-5
2,4,5-TP (Silvex) 93-72-1
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
1.2 This test method may be applicable to the determination
priate safety and health practices and determine the applica-
ofsaltsandestersofanalytecompounds.Theformofeachacid
bility of regulatory limitations prior to use. For specific
is not distinguished by this test method. Results are calculated
warning statements, see Sections 6, 8, 9, and 10.
and reported for each listed analyte as the total free acid.
1.3 Thistestmethodhasbeenvalidatedinaninterlaboratory
2. Referenced Documents
testforreagentwaterandfinishedtapwater.Theanalystshould
2.1 ASTM Standards:
recognize that precision and bias reported in Section 18 may
D1129 Terminology Relating to Water
not be applicable to other waters.
D1193 Specification for Reagent Water
1.4 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 the use of gas chroma-
Applicable Test Methods of Committee D19 on Water
D3370 Practices for Sampling Water from Closed Conduits
D3856 Guide for Management Systems in Laboratories
This test method is under the jurisdiction of ASTM Committee D19 on Water
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor Engaged in Analysis of Water
Organic Substances in Water.
Current edition approved May 1, 2011. Published June 2011. Originally
ε1 3
approved in 1992. Last previous edition approved in 2003 as D5317 – 93 (2003) . For referenced ASTM standards, visit the ASTM website, www.astm.org, or
DOI: 10.1520/D5317-98R11. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
DCPA monoacid and diacid metabolites are included in the scope of this test Standards volume information, refer to the standard’s Document Summary page on
method; DCPA diacid metabolite is used for validation studies. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5317 − 98 (2011)
D4210 Practice for Intralaboratory Quality Control Proce- 5. Significance and Use
dures and a Discussion on Reporting Low-Level Data
5.1 Chlorinated phenoxyacid herbicides, and other organic
(Withdrawn 2002)
acids are used extensively for weed control. Esters and salts of
D5789 Practice for Writing Quality Control Specifications
2,4-D and silvex have been used as aquatic herbicides in lakes,
for Standard Test Methods for Organic Constituents
streams, and irrigation canals. Phenoxy acid herbicides can be
(Withdrawn 2002)
toxic even at low concentrations. For example, the 96 h, TL
m
2.2 EPA Standard:
for silvex is 2.4 mg/L for bluegills (1) . These reasons make
Method 515.1, Revision4.0,MethodsfortheDetermination
apparent the need for a standard test method for such com-
of Organic Compounds in Drinking Water
pounds in water.
2.3 OSHA Standard:
6. Interferences
29 CFR 1910 OSHA Safety and Health Standards, General
6.1 Method interferences may be caused by contaminants in
Industry
solvents, reagents, glassware and other sample processing
apparatus that lead to discrete artifacts or elevated baselines in
3. Terminology
gas chromatograms. All reagents and apparatus must be rou-
3.1 Definitions—For definitions of terms used in this test
tinely demonstrated to be free from interferences under the
method, refer to Terminology D1129.
conditions of the analysis by running laboratory reagent blanks
3.2 Definitions of Terms Specific to This Standard:
as described in 19.2.
3.2.1 internal standard—a pure analyte(s) added to a solu-
6.1.1 Glassware must be scrupulously cleaned (2). Clean all
tion in known amount(s) and used to measure the relative
glassware as soon as possible after use by thoroughly rinsing
responses of other method analytes and surrogates that are
with the last solvent used in it. Follow by washing with hot
components of the same solution.
water and detergent and thoroughly rinsing with dilute acid,
3.2.1.1 Discussion—The internal standard must be an ana-
tap, and reagent water. Drain dry, and heat in an oven or muffle
lyte that is not a sample component.
furnace at 400°C for 1 h. Do not heat volumetric ware.
3.2.2 surrogate analyte—a pure analyte(s), which is ex- Thorough rinsing with acetone may be substituted for the
heating. After drying and cooling, seal and store glassware in
tremelyunlikelytobefoundinanysample,andwhichisadded
to a sample aliquot in known amount(s) before extraction and a clean environment to prevent any accumulation of dust or
other contaminants. Store inverted or capped with aluminum
is measured with the same procedures used to measure other
sample components. foil. Thermally stable materials such as PCBs may not be
eliminated by this treatment.
3.2.2.1 Discussion—Thepurposeofasurrogateanalyteisto
monitor method performance with each sample. 6.1.2 The use of high purity reagents and solvents helps to
minimize interference problems. Purification of solvents by
4. Summary of Test Method distillation in all-glass systems may be required. ( Warning—
When a solvent is purified, stabilizers added by the manufac-
4.1 The compounds listed in 1.1, in water samples, are
turer are removed, thus potentially making the solvent hazard-
converted into sodium salts by adjusting the pH to 12 with
ous. Also, when a solvent is purified, preservatives added by
sodium hydroxide solution (240 g/L) and shaking for 1 h.
the manufacturer are removed, thus potentially reducing the
Extraneous neutral material is removed by extraction with
shelf-life.)
methylene chloride. The sample is acidified, the acids are
extracted with ethyl ether and converted to methyl esters using 6.2 The acid forms of the analytes are strong organic acids
diazomethane.After the excess reagent is removed, the methyl that react readily with alkaline substances and can be lost
estersaredeterminedbycapillarycolumnGCusinganelectron during sample preparation. Glassware and glass wool must be
capture (EC) detector. Other detection systems, such as micro- acid-rinsed with hydrochloric acid (1 + 9) and the sodium
coulometric and electrolytic conductivity, are not as sensitive sulfatemustbeacidifiedwithsulfuricacidpriortousetoavoid
as EC for measurement of chlorinated acid esters but are more analyte loses due to adsorption.
specific and less subject to interferences. A mass spectrometer
6.3 Organic acids and phenols, especially chlorinated
may also be used as a detector.
compounds, cause the most direct interference with the deter-
4.2 This test method provides a magnesium silicate mination.Alkaline hydrolysis and subsequent extraction of the
cleanupproceduretoaidintheeliminationofinterferencesthat basic sample removes many chlorinated hydrocarbons and
may be present. phthalateestersthatmightotherwiseinterferewiththeelectron
capture analysis.
6.4 Interferences by phthalate esters can pose a major
The last approved version of this historical standard is referenced on
problem in pesticide analysis when using the ECD. These
www.astm.org.
compounds generally appear in the chromatogram as large
EPA/600/4-88/039, 1989, available from Environmental Monitoring Systems
peaks. Common flexible plastics contain varying amounts of
Laboratory, U.S. Environmental Protection Agency, Cincinnati, OH 45268.
AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments,
732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401.
7 8
Florisil, a trademark of, and available from, Floridin Co., 2 Gateway Center, The boldface numbers in parentheses refer to the list of references at the end of
Pittsburgh, PA15222, or its equivalent, has been found satisfactory for this purpose. this test method.
D5317 − 98 (2011)
phthalates, which are easily extracted or leached during labo- 7.2.8 Vials, glass, 5 to 10-mL capacity with TFE-
ratory operations. Cross contamination of clean glassware fluorocarbon lined screw cap.
routinely occurs when plastics are handled during extraction
7.3 Boiling Stone, TFE-fluorocarbon.
steps, especially when solvent-wetted surfaces are handled.
7.4 Water Bath, heated, capable of temperature control
Interferences from phthalates can best be minimized by avoid-
(62°C). The bath should be used in a hood.
ingtheuseofplasticsinthelaboratory.Exhaustivepurification
of reagents and glassware may be required to eliminate
7.5 Diazomethane Generator—Assemble from two 20- by
background phthalate contamination (3). 155-mm test tubes, two neoprene rubber stoppers, and a source
of nitrogen as shown in Fig. 1.
6.5 Interfering contamination may occur when a sample
7.6 Glass Wool, acid washed and heated at 450°C.
containing low concentrations of analytes is analyzed imme-
diately following a sample containing relatively high concen-
7.7 Gas Chromatograph—Analytical system complete with
trations of analytes. Between-sample rinsing of the sample
temperature programmable GC suitable for use with capillary
syringe and associated equipment with methyl-t-butyl-ether
columns and all required accessories including syringes, ana-
(MTBE) can minimize sample cross contamination. After
lytical columns, gases, detector, and stripchart recorder.Adata
analysis of a sample containing high concentrations of
system is recommended for measuring peak areas. Table 1 lists
analytes, one or more injections of MTBE should be made to
retention times observed for test method analytes using the
ensure that accurate values are obtained for the next sample.
columns and analytical conditions described below.
7.7.1 Column 1 (Primary Column), 30-m long by 0.25-mm
6.6 Matrix interferences may be caused by contaminants
inside diameter (I.D.) DB-5 bonded fused silica column,
that are coextracted from the sample. Also, note that all
0.25-µm film thickness. Establish helium carrier gas flow at 30
analytes listed in Table 1 are not resolved from each other on
cm/s linear velocity and program oven temperature from 60°C
any one column, that is, one analyte of interest may be an
to 300°C at 4°C/m. Data presented in this test method were
interferent for another analyte of interest. The extent of matrix
obtained using this column (Table 1). The injection volume is
interferences will vary considerably from source to source,
2 µL splitless mode with 45 s delay. The injector temperature
depending upon the water sampled. The procedures in Section
is 250°C and the detector is 320°C. Alternative columns may
16 can be used to overcome many of these interferences.
be used in accordance with the provisions described in 19.3.
Positive identifications should be confirmed. See 16.6, 16.7,
7.7.2 Column 2 (Confirmation Column), 30-m long by
and 16.8.
0.25-mm I.D. DB-1701 bonded fused silica column, 0.25-µm
6.7 It is important that samples and working standards be
film thickness. Establish helium carrier gas flow at 30 cm/s
contained in the same solvent. The solvent for working
linear velocity and program oven temperature from 60°C to
standards must be the same as the final solvent used in sample
300°C at 4°C/m.
preparation. If this is not the case, chromatographic compara-
7.7.3 Detector, electron capture (ECD). This detector has
bility of standards to sample may be affected.
proveneffectiveintheanalysisoffortifiedreagentandartificial
ground waters. An ECD was used to generate the validation
7. Apparatus and Equipment
data presented in this test method. Alternative detectors,
7.1 Sample Bottle—Borosilicate amber, 1-L volume with
graduations, fitted with screw caps lined with TFE-
fluorocarbon. Protect samples from light. The container must
be washed and dried as described in 6.1.1 before use to
minimize contamination. Cap liners are cut to fit from sheets
and extracted with methanol overnight prior to use.
7.2 Glassware.
7.2.1 Separatory funnel, 2000-mL, with TFE-fluorocarbon
stopcocks, ground glass or TFE-fluorocarbon stoppers.
7.2.2 Tumbler bottle, 1.7-L with TFE-fluorocarbon lined
screw cap. Cap liners are cut to fit from sheets and extracted
with methanol overnight prior to use.
7.2.3 Concentrator tube, Kuderna-Danish (K-D), 10 or
25-mL, graduated. Calibration must be checked at the volumes
employed in the procedure. Ground-glass stoppers are used to
prevent evaporation of extracts.
7.2.4 Evaporative flask, K-D, 500-mL.Attach to concentra-
tor tube with springs.
7.2.5 Snyder column, K-D, three ba
...
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