5550 ' 905R80110
METHOD 645: ANALYSIS OF CERTAIN AMINE PESTICIDES AND
LETHANE IN WASTEWATER BY GAS CHROMATOGRAPHY
1. SCOPE AND APPLICATION
1.1 This method covers the determination of certain amine pesticides
and lethane in municipal and industrial wastewater. The following
parameters may be determined by this method.
Parameter CAS No.
Alachlor 15972-60-8
Butachlor 23184-66-9
Diphenamid 957-51-7
Fluridone 59756-60-4
Lethane 112-56-1
Norflurazon 27314-13-2
1.2 The estimated detection limit (EDL) for each parameter is listed in
Table 1. The EDL was calculated from the minimum detectable
response of the nitrogen/phosphorous detector equal to 5 times the
gas chromatographic (GC) background noise assuming a 10 mL final
extract volume of a 1 liter reagent water sample and a GC injection
of 5 pL. The EDL for a specific wastewater may be-different
depending on the nature of interferences in the sample matrix.
1.3 This is a gas chromatographic (GC) method applicable to the
determination of the compounds listed above in municipal and
industrial discharges. When this method is used to analyze
unfamiliar samples for any or all of the compounds listed above,
compound identifications should be supported by at least one
additional qualitative technique. Section 13 provides gas
chromatograph/mass spectrometer (GC/MS) conditions appropriate for
the qualitative confirmation of compound identifications.
1.4 This method is restricted to use by or under the supervision of
analysts experienced in the operation of gas chromatographs and in
the interpretation of chromatograms.
2. SUMMARY OF METHOD
2.1 The amine pesticides and lethane are removed from the sample matrix
by extraction with methylene chloride. The extract is dried,
exchanged into hexane, and analyzed by gas chromatography. Column
chromatography is used as necessary to eliminate interferences
which may be encountered. Measurement of the pesticides is
accomplished with a nitrogen/phosphorous specific'.detector.
U.S. Environmental Protection Agency
Region V, Library
230 South Dearborn Street
lllfnnk
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US. Environmental Protection Agency-
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2.2 Confirmatory analysis by gas chromatography/mass spectrometry is
recommended (Section 13) when a new or undefined sample type is
being analyzed if the concentration is adequate for such
determination.
3. INTERFERENCES
3.1 Solvent, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing
misinterpretation of gas chromatograms. All of these materials
must be demonstrated to be free from interferences under the
conditions of the analysis by running laboratory reagent blanks as
described in Section 9.1
3.1.1 The use of high-purity reagents and solvents helps to
minimize interference problems. Purification of solvents by
distillation in all-glass systems may be required.
3.1.2 Glassware must be scrupulously cleaned (1). Clean all
glassware as soon as possible after use by rinsing with the
last solvent used in it. This should be followed by
detergent washing with hot water and rinses with tap water
and reagent water. It should then be drained dry and heated
in a muffle furnace at 400°C for 15 to 30 minutes. Solvent
rinses with acetone and pesticide-quality hexane may be
substituted for the muffle furnace heating. Volumetric ware
should not be heated in a muffle furnace. After drying and
cooling, glassware should be sealed and stored in a clean
environment to prevent any accumulation of dust or other
contaminants. Store the glassware inverted or capped with
aluminum foil.
3.2 Interferences co-extracted from the samples will vary considerably
from source to source, depending on the diversity of the industrial
complex or municipality being sampled. While general cleanup
procedures are provided as part of this method, unique samples may
require additional cleanup approaches to achieve the detection
limits listed in Table 1.
4. SAFETY
4.1 The toxicity or careinogenicity of each reagent used in this method
has not been precisely defined; however, each chemical compound
should be treated as a potential health hazard. From this
viewpoint, exposure to these chemicals must be reduced to the
lowest possible level by whatever means available. The laboratory
is responsible for maintaining a current awareness file of OSHA
regulations regarding the safe handling of the chemicals specified
in this method. A reference file of material data handling sheets
should also be made available to all personnel involved in the
chemical analysis. Additional references to laboratory safety are
available and have been identified (2-4) for the information'of the
analyst.
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5. APPARATUS AND EQUIPMENT
5.1 SAMPLE CONTAINERS - Narrow-mouth glass bottles, 1-liter or 1-quart
volume, equipped with polytetrafluoroethylene (PTFE)-lined screw
caps. Wide-mouth glass bottles, 1-quart volume, equipped with
PTFE-lined screw caps may also be used. Prior to use, wash bottles
and cap liners with detergent and rinse with tap and distilled
water. Allow the bottles and cap liners to air dry, then muffle at
400°C for 1 hour. After cooling, rinse the cap liners with hexane,
seal the bottles, and store in a dust-free environment.
5.1.1 Automatic sampler (optional)—Must incorporate glass sample
containers for the collection of a minimum of 250 mL.
Sample containers must be kept refrigerated at 4°C and
protected from light during compositing. If the sampler
uses a peristaltic pump, a minimum length of compressible
silicone rubber tubing may be used. Before use, however,
the compressible tubing should be thoroughly rinsed with
methanol, followed by repeated rinsings with reagent water
to minimize the potential for contamination of the sample.
An integrating flow meter is required to collect
flow-proportional composites.
5.2 KUDERNA-DANISH (K-D) GLASSWARE
5.2.1 Synder column—Three-ball macro (Kontes K-503000-0121 or
equivalent).
5.2.2 Concentrator tube—10-mL, graduated (Kontes K-570050-1025 or
equivalent) with ground glass stopper.
5.2.3 Evaporative flask—500-mL (Kontes K-570001-0500 or
equivalent). Attach to concentrator tube with springs.
5.3 GAS CHROMATOGRAPHY SYSTEM
5.3.1 The gas chromatograph must be equipped with a glass-lined
injection port compatible with the detector to be used. A
data system is recommended for measuring peak areas.
5.3.1.1 Column 1—180 cm long by 2 mm ID, glass, packed with
10 percent OV-11 on Gas Chrom W-HP (100/120 mesh) or
equivalent.
5.3.1.2 Column 2—180 cm long by 2 mm ID, PyrexR glass,
packed with 3 percent Dexsil 300 on Chromasorb W-HP
(80/100 mesh) or equivalent.
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5.3.1.3 Column 3—180 cm long by 2mm ID Glass, packed with 3
percent SP-2100 on Supelcoport (100/120 mesh) or
equivalent.
5.3.1.4 Column 1 was used to develop the accuracy and
precision statements in Section 12. Guidelines for
the use of alternate column packings are provided in
Section 10.3.1.
5.3.1.5 Detector—Nitrogen/phosphorous. This detector has
proven effective in the analysis of wastewaters for
the parameters listed in the scope and was used to
develop the method performance statements in Section
12. Guidelines for the use of alternate detectors
are provided in Section 10.3.
5.4 CHROMATOGRAPHIC COLUMN—300 mm long x 10 mm ID Chromaflex, equipped
with coarse fritted bottom plate and PTFE stopcock. (Kontes
K-420540-0213 or equivalent).
5.5 DRYING COLUMN—Approximately 400 mm long x 20 mm ID borosilicate
glass, equipped with coarse fritted bottom plate.
5.6 MISCELLANEOUS
5.6.1 Balance—analytical, capable of accurately weighing to the
nearest 0.0001 g.
5.6.2 Separatory funnel—two-liter, equipped with PTFE stopcock.
5.6.3 Water bath—heated witheconcentric ring cover, capable of
temperature control (±2eC). The bath should be used in a
hood.
5.6.4 Standard solution storage containers—15-mL bottles with
PTFE-lined screw caps.
5.6.5 Boiling chips—Approximately 10/40 mesh. Heat to 400°C for
30 minutes or Soxhlet extract with methylene chloride.
REAGENTS AND CONSUMABLE MATERIALS
6.1 REAGENTS
6.1.1 Acetone, hexane, and methylene chloride—demonstrated to be
free of analytes.
6.1.2 Florisil—PR grade (60/100 mesh). Purchase activated at
1250°F and store in glass containers with glass stoppers or
foil-lined screw caps. Before use, activate each batch over-
night at 200°C in foil-covered glass containers. To prepare
for use, place the amount necessary for the number of
columns to be run in a 500-mL reagent bottle and add 2
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percent by weight of reagent water. Seal and mix thoroughly
by shaking or rolling for 10 minutes. Allow to stand for at
least 2 hours prior to use. The mixture must be
homogeneous. Keep the bottle tightly sealed to ensure
proper activity.
6.1.3 Reagent water—reagent water is defined as a water in which
an interferent is not observed at the method detection limit
of each parameter of interest.
6.1.4 Sodium hydroxide (NaOH) solution (ION)—dissolve 40 g NaOH
in reagent water and dilute to 100 ml.
6.1.5 Sodium sulfate—granular, anydrous. Condition by heating at
400°C for 4 hours in a shallow tray.
6.1.6 Sulfuric acid (HgSO/j) solution (1+1)—add measured
volume of concentrated H2$04 to equal volume of reagent
water.
6.1.7 Sodium thiosulfate—(ACS) Granular.
6.2 STANDARD STOCK SOLUTIONS (1.00 ug/uL)—These solutions may be
purchased as certified solutions or prepared from pure standard
materials using the following procedures.
6.2.1 Prepare standard stock solutions by accurately weighing
about 0.0100 grams of pure material. Dissolve the material
in hexane or other suitable solvent and dilute to volume in
a 10-mL volumetric flask. Larger volumes can be used at the
convenience of the analyst. If compound purity is certified
at 96% or greater, the weight can be used without correction
to calculate the concentration of the standard stock.
6,2.2 Store standard stock solutions at 4°C in 15-mL bottles
equipped with PTFE-lined screw-caps. Standard stock
solutions should be checked frequently for signs of
degradation or evaporation, especially just prior to
preparing calibration standards from them.
6.2.3 Standard stock solutions must be replaced after 6 months or
sooner, if comparison with check standards indicates a
problem.
7. SAMPLE COLLECTION, PRESERVATION, AND STORAGE
7.1 Collect all samples in duplicate. Grab samples must be collected
in glass containers. Conventional sampling practices (5) should be
followed, except that the bottle must not be prewashed with sample
before col lection.
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7.2 The samples must be iced or refrigerated at 4°C from the time of
collection until extraction.
7.3 Chemical preservatives should not be used in the field unless more
than 24 hours will elapse before delivery to the laboratory. If
the samples will not be extracted within 48 hours of collection,
the sample should be adjusted to a pH range of 6.0 to 8.0 with
sodium hydroxide or sulfuric acid.
7.4 All samples must be extracted within 7 days and completely analyzed
within 40 days of extraction (6).
8. CALIBRATION AND STANDARDIZATION
8.1 CALIBRATION
8.1.1 A set of at least three calibration solutions containing the
method analytes is needed. One calibration solution should
contain each analyte at a concentration approaching but
greater than the estimated detection limit (Table 1) for
that compound; the other two solutions should contain
analytes at concentrations that bracket the range expected
in samples. For example, if the detection limit for a
particular analyte is 0.2 ug/L, and a sample expected to
contain approximately 5 yg/l is analyzed, solutions of
standards should be prepared at concentrations representing
0.3 ug/L, 5pg/l, and 10 pg/L for the particular analyte.
8.1.2 To prepare a calibration solution, add an appropriate volume
of a standard stock solution to a volumetric flask and
dilute to volume with hexane.
8.1.3 Starting with the standard of lowest concentration, analyze
each calibration standard according to Section 10.3 and
tabulate peak height or area responses versus the mass of
analyte injected. The results can be used to prepare a
calibration curve for each compound. Alternatively, if the
ratio of response to concentration (calibration factor) is a
constant over the working range (<10% relative standard
deviation), linearity through the origin can be assumed and
the average ratio or calibration factor can be used in place
of a calibration curve.
8.1.4 The working calibration curve or calibration factor must be
verified on each working day by the measurement of one or
more calibration standards. If the response for any analyte
varies from the predicted response by more than ±10%, the
test must be repeated using a fresh calibration standard.
If the results still do not agree, generate a new
calibration curve.
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9. QUALITY CONTROL
9.1 MONITORING FOR INTERFERENCES
Analyze a laboratory reagent blank each time a set of samples is
extracted. A laboratory reagent blank is a one-liter aliquot of
reagent water. If the reagent blank contains a reportable level of
any analyte, immediately check the entire analytical system to
locate and correct for possible interferences and repeat the test.
9.2 ASSESSING ACCURACY
9.2.1 After every 10 samples, and preferably in the middle of each
day, analyze a laboratory control standard. Calibration
standards may not be used for accuracy assessments and the
laboratory control standard may not be used for calibration
of the analytical system.
9.2.1.1 Laboratory Control Standard Concentrate - from stock
standards prepared as described in Section 6.3,
prepare a laboratory control standard concentrate
that contains each analyte of interest at a
concentration of 2 ug/mL in acetone or other
suitable solvent.
9.2.1.2 Laboratory Control Standard - using a pipet, add
1.00 mL of the laboratory control standard
concentrate to a one-liter aliquot of reagent water.
9.2.1.3 Analyze the laboratory control standard as described
in Section 10. For each analyte in the laboratory
control standard, calculate the percent recovery
(P-j) with the equation:
loo si
where S-j = the analytical results from the
laboratory control standard, in pg/L; and
T-j = the known concentration of the spike,
in ug/L.
9.2.2 At least annually, the laboratory should participate in
formal performance evaluation studies, where solutions of
unknown concentrations are analyzed and the performance of
all participants is compared.
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9.3 ASSESSING PRECISION
9.3.1 Precision assessments for this method are based upon the
analysis of field duplicates (Sect. 7.1). Analyze both
sample bottles for at least 10% of all samples. To the
extent practical, the samples for duplication should contain
reportable levels of most of the analytes.
9.3.2 For each analyte in each duplicate pair, calculate the
relative range (7) (RRi) with the equation:
100 R,
RRi
where Rj = the absolute difference between the
duplicate measurements Xj and Xg, in
ug/L; and
X-j = the average concentration found ([Xj +
X2]/2), in wg/L.
9.3.3 Individual relative range measurements are pooled to
determine average relative range or to develop an expression
of relative range as a function of concentration.
10. PROCEDURE
10.1 SAMPLE EXTRACTION
10.1.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire
sample into a 2-liter separatory funnel. Check the pH of
the sample with wide-range pH paper and adjust to within the
range of 5 to 9 with sodium hydroxide or sulfuric acid.
10.1.2 Add 60 ml of methylene chloride to the sample bottle and
shake for 30 seconds to rinse the walls. Transfer the
solvent to the separatory funnel and extract the sample by
shaking the funnel for 2 minutes with periodic venting to
release vapor pressure. Allow the organic layer to separate
from the water phase for a minimum of 10 minutes. If the
emulsion interface between layers is more than one-third the
volume of the solvent layer, the analyst must employ
mechanical techniques to complete the phase separation. The
optimum technique depends on the sample, but may include
stirring, filtration of the emulsion through glass wool, or
centrifugation. Collect the extract in a 250-mL Erlenmeyer
flask.
10.1.3 Add an additional 60-mL volume of methylene chloride to the
sample bottle and complete the extraction procedure a second
time, combining the extracts in the Erlenmeyer flask.
10.1.4 Perform a third extraction in the same manner. Pour the
combined extract through a drying column containing about
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10 cm of anhydrous sodium sulfate, and collect it in a
500-mL K-D flask equipped with a 10 ml concentrator tube.
Rinse the Erlenmeyer flask and column with 20 to 30 ml of
methylene chloride to complete the quantitative transfer.
10.1.5 Add one or two clean boiling chips to the flask and attach a
three-ball Snyder column. Prewet the Snyder column by
adding about 1 ml of methylene chloride to the top. Place
the K-D apparatus on a hot water bath (80 to 85°C) so that
the concentrator tube is partially immersed in the hot water
and the entire lower rounded surface of the flask is bathed
in steam. Adjust the vertical position of the apparatus and
the water temperature as required to complete the
concentration in 15 to 20 minutes. At the proper rate of
distillation, the balls of the column will actively chatter
but the chambers will not flood. When the apparent volume
of liquid reaches 1 ml_, remove the K-D apparatus and allow
it to drain and cool for at least 10 minutes. Remove the
Snyder column and rinse the flask and its lower joint into
the concentrator tube with 1 to 2 ml of methylene chloride.
10.1.6 For FlorisilR column cleanup or gas chromatography, the
extract must be in hexane solution. To exchange the solvent
to hexane, add one or two fresh boiling chips to the flask
and ampul containing the extract, add 50 ml of hexane, and
reattach the Snyder column. Pour about 1 mL of hexane into
the top of the Snyder column, and concentrate the extract at
85 to 95°C in the hot-water bath as above. When the
apparent volume of liquid reaches 1 mL, remove the K-D
apparatus from the water bath and allow it to drain and cool
for at least 10 minutes.
10.1.7 Remove the Snyder column, rinse the flask and its lower
joint into the concentrator tube with 1 to 2 ml of hexane.
A 5-mL syringe is recommended for this operation. Dilute to
10 mL with hexane for analysis by gas chromatography
(Section 10.3) if cleanup is not required. If the extract
requires cleanup, proceed to Section 10.2. If the extracts
will be stored longer than 2 days, they should be
transferred to Teflon-sealed screw-cap bottles. Proceed
with gas chromatographic analysis.
10.1.8 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1,000 mL
graduated cylinder. Record the sample volume to the nearest
5 mL.
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10.2 CLEANUP AND SEPARATION
10.2.1 Cleanup procedures may not be necessary for a relatively
clean sample matrix. The cleanup procedures recommended in
this method have been used for the analysis of alachlor,
butachlor, diphenamid and lethane in various clean waters
and municipal effluents. The use of Florisil^ as the
cleanup material for fluridone and norflurazon has been
demonstrated to yield recoveries of less than 50 percent,
and is not recommended as a cleanup material for these
compounds. Use of specific detectors may obviate the
necessity for cleanup of relatively clean sample matrices.
If particular circumstances demand the use of an alternative
cleanup procedure, the analyst must determine the elution
profile and demonstrate that the recovery of each compound
of interest is no less than 85 percent.
10.2.2 Place the necessary amount of deactivated Florisil^ into a
20-mm-IO chromatographic column and tap the column to settle
the FlorisilR. Add 1 to 2 cm of anhydrous sodium sulfate
to the top of the Florisil^.
10.2.3 Pre-elute the column with 50 to 60 ml of hexane. Discard
the eluate and, just prior to exposure of the sodium sulfate
layer to the air, transfer the sample extract onto the
column by decantation. Complete the transfer by rinsing
with two additional 2-mL volumes of hexane. Alternatively,
a measured aliquot of the extract may be taken for cleanup.
10.2.4 Just prior to exposure of the sodium sulfate layer to the
air, elute the column with 100 ml hexane. Discard the
eluate and repeat the elution with 200 mL of 6-percent
acetone in hexane (volume/volume). Collect the eluate in a
500-mL K-D flask equipped with a 10-mL concentrator tube
(Fraction 1). All elutions should be carried out using a
flowrate of about 5 mL/minute.
10.2.5 Perform a second elution with 200 mL of 15-percent acetone
in hexane (Fraction 2). Collect each fraction in a separate
K-D apparatus. The elution pattern for these compounds is
shown in Table 3.
10.2.6 Determine, from Table 3, the fractions of interest and
concentrate by standard K-D technique, as indicated in
Paragraph 10.1.5, using hexane in place of methylene
chloride, to a volume of 10 mL.
10.2.7 Analyze the fractions by gas chromatography.
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10.3 GAS CHROMATOGRAPHY ANALYSIS
10.3.1 Recommended columns and detectors, and operating conditions
for the gas chromatography system are described in Section
5.3. Table 1 summarizes the recommended operating
conditions for the gas chromatograph. Included in this
table are estimated retention times and detection limits
that can be achieved by this method. Examples of the
separations achieved are shown in Figures 1-3. Other packed
columns, chromatographic conditions, or detectors may be
used if data quality comparable to Table 2 is achieved.
Capillary (open-tubular) columns may also be used if the
relative standard deviations of responses for replicate
injections are demonstrated to be less than 6 percent and
data quality comparable to Table 2 is achieved.
10.3.2 Inject 2 to 5 uL of the sample extract using the
solvent-flush technique (8). Record the volume injected to
the nearest 0.05 pL, the total extract volume, and the
resulting peak size in area or peak height units.
10.3.3 The width of the retention time window used to make
identifications should be based upon measurements of actual
retention time variations of standards over the course of
the day. Three times the standard deviation of a retention
time for a compound can be used to calculate a suggested
window size; however, the experience of the analyst should
weigh heavily in the interpretation of chromatograms.
10.3.4 If the response for the peak exceeds the working range of
the system, dilute the extract and reanalyze.
10.3.5 If the measurement of the peak response is prevented by the
presence of interferences, further cleanup is required.
11. CALCULATIONS
11.1 Determine the concentration (C) of individual compounds in
the sample in ug/L with the equation:
(A) (Vt)
~
where A = amount of material injected, in nanograms;
V-j = volume of extract injected, pL;
Vt = volume of total extract, uL; and
Vs = volume of water extracted, mL.
11.2 Report the results for the unknown samples in pg/L. Round
off the results to the nearest 0.1 ug/L or two significant
figures.
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12. METHOD PERFORMANCE
12.1 Estimated detection limits (EDL) and associated
chromatographic conditions are listed in Table l.(9) The
detection limits were calculated from the minimum detectable
response of the EC detector equal to 5 times the GC background
noise, assuming a 10-mL final extract volume of a 1-liter
sample and a GC injection of 5 pL.
12.2 Single laboratory accuracy and precision studies were
conducted by Environmental Science and Engineering (6), using
spiked samples. The results of these studies are presented in
Table 2.
13. GC/MS CONFIRMATION
13.1 It is recommended that GC/MS techniques be judiciously
employed to support qualitative identifications made with this
method. The mass spectrometer should be capable of scanning
the mass range from 35 AMU to a mass 50 AMU above the
molecular weight of the compounds of interest. The instrument
must be capable of scanning the mass range at a rate to
produce at least 5 scans per peak, but not to exceed 7 scans
per peak utilizing a 70-V (nominal) electron energy in the
electron impact ionization mode. A GC to MS interface
constructed of all-glass or glass-lined materials is
recommended. A computer system should be interfaced to the
mass spectrometer that allows the continuous acquisition and
storage on machine-readable media of all mass spectra obtained
throughout the duration of the chromatographic program.
13.2 Gas chromatographic columns and conditions should be selected
for optimum separation and performance. The conditions
selected must be compatible with standard GC/MS operating
practices. Chromatographic tailing factors of less than 5.0
must be achieved. The calculation of tailing factors is
illustrated in Method 625 (10).
13.3 At the beginning of each day that confirmatory analyses are to
be performed, the GC/MS system must be checked to see that all
DFTPP performance criteria are achieved (11).
13.4 To confirm an identification of a compound, the background
corrected mass spectrum of the compound must be obtained from
the sample extract and compared with a mass spectrum from a
stock or calibration standard analyzed under the same
chromatographic conditions. It is recommended that at least
25 nanograms of material be injected into the GC/MS. The
criteria below must be met for qualitative confirmation.
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13.4.1 The molecular ion and other ions that are present
above 10-percent relative abundance in the mass
spectrum of the standard must be present in the mass
spectrum of the sample with agreement to plus or
minus 10 percent. For example, if the relative
abundance of an ion is 30 percent in the mass
spectrum of the standard, the allowable limits for
the relative abundance of that ion in the mass
spectrum for the sample would be 20 to 40 percent.
13.4.2 The retention time of the compound in the sample
must be within 6 seconds of the same compound in the
standard solution.
13.4.3 Compounds that have similar mass spectra can be
explicitly identified by GC/MS only on the basis of
retention time data.
13.5 Where available, chemical ionization mass spectra may be
employed to aid in the qualitative identification process.
13.6 Should these MS procedures fail to provide satisfactory
results, additional steps may be taken before reanalysis.
These may include the use of alternate packed or capillary GC
columns or additional cleanup.
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REFERENCES
1. ASTM Annual Book of Standards, Part 31, D3694, "Standard Practice
for Preparation of Sample Containers and for Preservation,"
American Society for Testing and Materials, Philadelphia, PA, p.
679, 1980.
2. "Carcinogens - Working with Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, Aug. 1977.
3. "OSHA Safety and Health Standards, General Industry" (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206 (Revised,
January 1976).
4. "Safety in Academic Chemistry Laboratories," American Chemical
Society Publication, Committee on Chemical Safety, 3rd Edition,
1979.
5. ASTM Annual Book of Standards, Part 31, D3370, "Standard Practice
for Sampling Water," American Society for Testing and Materials,
Philadelphia, PA, p. 76, 1980.
6. Test procedures for Pesticides in Wastewaters, EPA Contract Report
#68-03-2897. Unpublished report available from U.S. Environmental
Protection Agncy, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio 45268.
7. "Handbook for Analytical Quality Control in Water and Wastewater
Laboratories," EPA-600/4-79-019, U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory -
Cincinnati, Ohio 45268, March 1979.
8. Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis;
Some Practical Aspects," Journal of the Association of Official
Analytical Chemists, 48, 103/ (1965).
9. "Evaluation of Ten Pesticide Methods," U.S. Environmental
Protection Agency, Contract No. 68-03-1760, Task No. 11, U.S.
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio
45268 (In Preparation).
10. "Methods for Organic Chemical Analysis of Municipal and Industrial
Wastewater" EPA-600/4-82-057, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory - Cincinnati, Ohio
45268.
11. Eichelberger, J.W., Harris, L.E., and Budde, W.L., Anal. Chem., 46,
1912 (1975).
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Table 1
Gas Chromatography and Detection Limits of Certain
Amines and Lethane
Parameter
Retention Time (minutes)
Column 1Column 2Column 3
Estimated
Detection Limit
(ug/L)
Alachlor
Butachlor
Diphenamide
Fluridone
Lethane
Norflurazon
6.9 —
10.5
10.8 —
2.2 2.45 2.1
2.0 —
18.4 —
0.2
0.3
0.2
0.5
0.1
0.02
Column 1:
180 cm long by 2 mm ID glass, packed with 10-percent OV-11 on Gas
Chrom W-HP, 100/120 mesh; nitrogen carrier gas at a flow rate of
30 mL/min. Column temperature is held at 225°C for 4 min. after
injection and then programmed to 275°C at 4°/min and held for 8
min.
Column 2:
Column 3:
180 cm long by 2 mm ID glass, packed with 3-percent Dexsil 300 on
Chromasorb W-HP, 80/100 mesh; nitrogen carrier gas at a flow rate
of 30 mL/min. Column temperature at 300°C isothermal.
180 cm long by 2 mm ID glass, packed wtih 3-percent SP-2100 on
Supelcoport, 100/120 mesh; nitrogen carrier gas at a flow rate of
40 mL/min. Column temperature at 275'C isothermal.
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Table 2
Single Laboratory Accuracy and Precision
Relative
Parameter
Alachlorn
Butachlor
Diphenamid
Fluridone**
Lethane
Norf lurazon**
* 1
2
3
Spike Average Standard
Matrix Range Number of Percent Deviation
Type* (ug/L) Replicates Recovery (%)
1
1
1
1
2
3
1
1
1
1
1
3
= Manufacturing
= Manufacturing
= Manufacturing
255
996
286
1,420
9.3
740
20.8
998
167
576
243
1,048
effluent wastewaters.
effluent wastewater +
effluent wastewater +
7
7
7
7
7
7
7
7
7
7
7
7
POTW
POTW
113
104
93
92
100
98
92
88
93
97
89
102
effluent at
effluent at
.1
.8
.8
.0
.4
.3
.6
.5
a
a
9.
13.
8.
4.
14.
7.
11.
11.
19.
29.
7.
- 6.
ratio of 1
ratio of 1
0
3
2
3
2
0
5
4
9
4
4
1
:200.
:1.
** Florisil cleanup not employed.
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Table 3
Florisil* Cleanup Recoveries
Solvent
Fraction**
1
2
Average Percent Recoveries
Alachlor Butachlor Diphenamid
103 95
ND ND 96
Lethane
106
ND
* Two-percent deactivated.
** 1 = 6-percent acetone/hexane.
2 = 15-percent acetone/hexane.
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u
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-------
r»VTF
U.S. Environmental Protection Agency
Region V, Library
230 South Dearborn Street
Chicago, Illinois 60604
-------
024
Retention Time (H1n.)
FIGURE 3. GAS CHROMATOGRAH OF FLURIOOME,' COLUMN 3.
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