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Ir.e Determination of Carbamate and Urea
Pesticides in Induatrial ar.d Municipal
Wastewater: Method 632
wSJ.S.) Environoental Monitoring and Support
Lai>.-Cincinnati, OH
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PB82-15608U
THE DETERMINATION
OF CARBAMATE AND UREA
PESTICIDES IN INDUSTRIAL
AND MUNICIPAL WASTEWATER
Hethod 632
Thoraas A. Pressley
and
James E. Longbottora
Physical and C^eaical Methods Brancri
Environmental Monitoring and Support Laboratory
Cincinnati, Ohio 45253
January 1982
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINHATI. OHIO 45263
«f»00*U f
NATIONAL TECHNICAL
information SERVICE
is :«'«-*«- a* cwmtct
71*^1.: 11 DID
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TECHNICAL REPORT DATA
rz&i /musuertont on iht tumt befcrr crymrictin?)
1. HfcPCHT NO. 2.
EPA-600/4-S2-Q14 REPORT
1. RECIPIENT'S ACJfcSStOVNO.
PBtt 1 5600 *
4. TITLE ANC SUUTITLt
The Determination of Carbamate and Urea Pesticides In
Industrial and Municipal Wastewater
Method 632
3. REPOR*" DATE
February 1932
6. PERFORMING
7. AUTHORS)
Thomas A. i.essley and James E, Longbottoir
B. PERFORMING ORGANISATION REPORT HO.
9. PERFORMING ORGANIZATION NAME AND AOOHESS
Environmental Monitoring and Sup^prt Lab - Cincinnati
Office of Research and Development
U. S. Environmental Protection Agenry
Cincinnati, Ohio 45268
10. PROGRAM ELEMENT NO.
ABEB1C
ii.£6NtRAcY;
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THE DETERMINATION OF CAP.2J.MATE AND UREA PESTICIDES
IN INDUSTRIAL AND MUNICIPAL WASTEWATER
METHOD 632
1. Scope and Application
1.1 This method covers the determination of certain carbamate and urea
pesticides. The following parameters can be determined by this
method:
Parameter
STORET No.
CAS No.
Amirocarfa
2032-59-9
Barban
—
101-27-9
Carbaryl
39750
53-25-2
Carbofuran
81405
1563-65-2
ChlorproohaCT
—
101-21-3
Diuron
3SS50
330-54-1
Fenuron
—
101-42-8
Fenuron-TCA
—
4432-55-7
Fluometaroo
—
2164-17-2
Linuron
—
330-55-2
Methiocarb
--
2032-65-7
Methonyl
33051
16752-77-5
Kexacarb3te
—
315-18-4
Monuron
—
150-68-5
Monuron-TCA
—
140-41-0
Neburon
555-37-3
Okamy1
—
23135-22-0
Prophaa
39052
122-42-9
Propoxur
—
114-26-1
Siduron
~
1982-49-6
Swep
—
1913-18-9
1.2 This meifccd cannot distinguish monuron from monuron-TCA and fenuron
from ferwon-TCA. Results for the paired parameters are reported
as nonuron and fenuron respectively.
1.3 This is a high performance liquid chromatographic (HPLC) method
applicable to the determination of the compounds listed above in
industrial and mur.-icipal discnarges as provided under 40 CFR
136.1. Any fsodification of this method beyond those expressly
1
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permitted, shall be considered a major modification subject to
application and approval of alternate test procedures under 40 CFR
136.4 and 136.5.
1.4 The method detection imit (MDlr defined in Section 15) for many of
the parameters are listed in Table 1. The MDL for a-specific
wastewater may differ from those listed, depending upon the nature
of interferences In the sample matrix.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of liquid chromatography and in the
interpretation of liquid chromatograms. Each analyst must demon-
strate the ability to generate acceptable results with this method
using the procedure described in Section 8.2.
1.6 Uhen this method is used to analyze unfamiliar sanples for any or
all of the compounds above, compound identifications should be
supported by at least one additional qualitative technique.
2. Sunr.ary of Method
2.1 A measured volume of sample, approximately 1-liter, ;s solvent
extracted with methylene chloride using a separatory funnel. The
methylene chloride extract is dried and concentrated to a volume of
10 ml or less. HPlC chromatographic conditions are described which
permit the separation and measurement of the compounds in the
extract by HPLC with a UV detector.''2
2.2 This method provides an optional Florisll column cleanup procedure
to aid in the elimination or reduction of interferences which may
be encountered.
3. Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware and other sanple processing apparatus that lead
to discrete artifacts or elevated baselines in liquid chromato-
grams. All reagents and apparatus must be routinely demonstrated
to be free from interferences under the conditions of the analysis
by running laboratory reagent blanks as describes in Section 8.5.
3,1.1 Glassware must be scrupulously cleaned.3 Clean all glass-
ware as soon as possible after use by thoroughly rinsing
with the last solvent used in it. Follow by washing with
hot water and detergent and thorough rinsing with tap and
reagent water. Drain dry, and heat in an oven or muffle
furnace at 400°C for 15 to 30 min. Do not heat volumetric
ware. Thermally stable materials such as PCSs, might not be
eliminated by this treatment. Thorough rinsing with acetone
and peiticioe quality hexane may be substituted for the
heating. After drying and cooling, seal and store glassware
2
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in a clean environment to prevent any accumulation of dust
or other contaminants. Store Inverted or capped with
aluminivi foil.
3.1.2 The use of high purity reagents and solvents helps to
minimize Interference problems. Turlfication of solvents by
distillation in all-glass systems may be required.
3.2 Matrix Interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences
will vary considerably from source to source, depending upon the
nature and diversity of the industrial complex or municipality
sampled. The cleanup procedure in Section 11 can be used to
overcome many of these interferences, but unique sasnples may
require additional cleanup approaches to achieve the MDL listed in
Table 1.
4. Safety
4.1 The toxicity or carcinogenicity of each reagent used in this method
has not been precisely defined; however, each chemical compound
must be treated as a potential health hazard. From this viewpoint,
exposure to thes^ 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 for the information of the analyst.
5. Apparatus and Materials
5.1 Sampling equipment, for discrete or composite sampling.
5.1.1 Grab sample bottle - Amber borosilicate or flint glass,
1-liter or 1-quart volume, fitted with screw caps lined with
TFE-fluorocarbon. Aluminum foil may-be substituted for TFE
if the sample is not corrosive. If amber bpttles are not
available, protect samples from light. Th£*container and cap
liner must be washed, rinsed with acetone or methylene
chloride, and dried before use to minimize contamination.
5.1.2 Automatic sampler (optional) - Must Incorporate glass sample
containers for the collection of a minimum of 250 ml.
Sample containers must be kept refrigerated it 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. 8efore use, however,
the compressible tubing must be thoroughly rinsed with
methanol, followed by repeated rinsings with reagent water
3
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to minimize thf» potential for contamination of the sample.
An integrating flow meter is required to collect flow
proportional composites.
5.2 Glassware (All specifications are suggested. Catalog numbers are
included for illustration only.)
5.2.1 Separator^ funnel - 2000-ml, with TFE-fluorocarbon stopcock,
ground glass or TFE stopper.
5.2.2 Drying column - Chromatographic column 400 ran long x 19 nrn
ID with coarse fritted disc.
5.2.3 Chromatographic column - 400 mm long x 19 mm ID with coarse
fritted disc at bottom and TFE-fluorocarbon stopcock (Kontes
K-420540-0224 or equivalent).
5.2.4 Flask, round bottom - 500-mlf with standard taper to fit
rotary evaporator.
5.2.5 Vials - Am^er glass, 10 to 15 mL capacity with
TFE-fluoiocarbon lined screw cap.
5.3 Rotary evaporator.
5.4 V'ncer bath - Heated, with concentric ring cover, capable of
temperature control (± 2°C). The bath should be used in a hcod,
5.5 Balance - Analytical, capable of accurately weighing to the nearest
0.0001 g.
5.5 Filtration apparatus - As needed to filter chrocatographic soivsrts
prior to HPLC.
5.7 Liquid chromatograph - High performance analytical system complete
with high pressure syringes or sample injection loop, analytical
columns, detector and strip chart recorder. A guard column is
recommended for all applications.
5.7.1 Gradient pumping system, constant flow.
5.7.2 Column - 30 cm long x 4 mm ID stainless steel packed with
p Bondapak Cjs (10 pm) or equivalent. This column was
used to develop the method performance statements in Section
14. Alternative columns may be used in accordance with the
provisions described 1n Section 12.1.
5.7.3 Detector - Ultraviolet, capable of monitoring at 254 nm and
280 nm. This detector has proven effective in the analysis
of wastewaters and was used to develop the method
performance statements in Section 14. Alternative
4
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detectors may be used in accordance with the provisions
described in Section 12.1.
6. Reagents
6.1 Reagent water - Reagent water Is defined as 9 water in which an
Interferent is not observed at the oeihod detection limit of each
parsneter of interest.
6.2 Acetone, acetonitrile, hexane, methylene chloride, methanol -
Pesticide quality or equivalent.
6.3 Ethyl ether - Nanograde. redistilled in glass if necessary. Must
be free of peroxides as indicated by EM Quant test strips.. (Avail-
able from Scientific Products Co., Cat. No. PI 126-8, and other
suppliers.) Procedures recommended for removal of peroxides are
provided with the test strips. After cleanup, 20 mL ethyl alcohol
preservative must be added *o each liter of ether.
6.4 Sodium sulfate - (ACS) Granular, anhydrous. Heat treat in a
shallow tray at 400°C for a minimu.ii of 4 h to remove phthalates
and other interfering organic substances. Alternatively, heat 16 h
at 450-500°C in a shallow tray or Soxhlet extract with methylene
chloride for 48 h.
6.5 Florisil - PR grade (60/100 mesh). Purchase activated at 1250°F
and store in dark in glass container with ground glass stopper or
foil-lined screw cap. Before use activate each batch at least 16 h
at 130°C in a foil covered glass container.
6.6 Acetic acid - Glacial.
6.7 Stock standard solutions (1.00 ug/pL) - Stock standard solutions
may be prepared from pure standard materials or purchased as
certified solutions.
C.7.1 Prepare stock standard solutions by accurately weighing
approximately 0.0100 g of pure material. Dissolve the
material in pesticide quality acetonitrile or methanol and
dilute to volume in a 10-mt volumetric flask. Larger
volumes may be used at the convenience of the analyst. If
compound purity is certified at 96% or greater, the weight
may be used without correction to calculate the concentra-
tion of the stock standard. Cocmercially prepared stock
standards may be used at any concentration if they are
certified by the manufacturer or by an independent source.
6.7.2 Transfer the stock standard solutions into TrE-fluorocarbon-
sealed screw cap vials. Store at 4°C and protect froo
light. Frequently check stock standard solutions for signs
of degradation or evaporation, especially just prior to
preparing calibration standards from then.
5
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6.7.3 Stock standard solutions must be replaced after six months
or sooner if comparison with check standards indicates a
problem.
7. Calibration
7.1 Establish HPLC operating parameters equivalent to those Indicated
1n Table 1. The HPLC system may be calibrated using either the
external standard technique (Section 7.2) or the internal standard
technique (Section 7.3).
7.2 External standard calibration procedure:
7.2.1 For each parameter of interest, prepare calibration
standards at a minimum of three concentration levels by
adding accurately measured volumes of one or more stock
standards to a volumetric flask and diluting to volume with
acetonitrile or methanol. One of fie external standards
should be representative of a concentration near, but above,
the method detection limit. The other concentrations should
correspond to the range of concentrations expected in the
sample concentrates or should define the working range of
the detector.
7.2.2 Using injections of 10 uL of each calibration standard,
tabulate peak height or area responses against the mass
injected. The results can be used to prepare a calibration
curve for each parameter. Alternatively, the ratio of the
response to the mass injected, defined as the calibration
factor (CF), may be calculated for each parameter at each
standard concentration. If the relative standard deviation
of the calibration facto*' is less than I0Z over the working
range, the average calibration factor can be used in place
of a calibration curve.
7.2.3 The working calibration curve or calibration factor must be
verified on each working shift by the measurement of one or
more calibration standards. If the response for any
parameter varies from the predicted response by more than
±10X, the test must be repeated using a fresh calibration
standard. Alternatively, a new calibration curve or
calibration factor must be prepared for that parameter.
7.3 Internal standard calibration procedure. To use this approach, the
analyst must select one or more internal standards similar in
analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the Internal standard
is not affected bv method or matrix interferences. Due to these
limitations, no internal standard applicable to all samples can be
suggested.
6
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7.3.1 Prepare calibration standards at a asfnimum of three concen-
tration levels for each parameter of interest by adding
volumes of one or acre stock standards to a volumetric
flask. To each calibration standard, add a known constant
amount of one or acre internal standards, and dilute to
volume with acet-jnttri'e or methanol. One of the standards
should be represeniati/e of a concentration near, but above,
the method detection litiit. The other concentrations should
correspond to the range tf concentrations expected in the
sample concentrates, or should define the working range of
the detector.
7.3.2 Using injections of 10 Ji of each calibration standard,
tabulate the peak height or area responses against the
concentration for each compound and internal standard.
Calculate response factors (RF) for each compound as follows:
RF ¦ (A5CjS)/(Ais Cs)
where:
As = Response for the parameter to be measured.
A-fs = Response for the internal standard.
C-js = Concentration of the internal standard in pg/L.
Cs ® Concentration of the parameter to be measured in
pg/L.
If the RF value over the working range is constant, less
than 1C1 relative stawiard deviation, the RF can be assumed
to be invariant and t*»e average RF nay be used fot calcula-
tions. Alternatively, the results may be used to plot a
calibration curve of resoonse ratios, As/Ajs against RF.
7.3.3 The working calibration curve or RF nust be verified on each
working shift by We measurement of one or more calibration
standards. If the response for any parameter varies from
the predicted response by more than ±1056, the test must be
repeated using a frash calibration standard. Alternatively,
a new calibration curve must be prepared for that compound.
7.4 The cleanup procedure in Secticn 11 utilizes Florisil chromato-
graphy. Florisil frtss different batches or sources may vary 1n
adsorptive capacity. To stantjsrdize the amount of Florisil which
is used, the use of lauric acid value is suggested. This
procedure^ determines the adsorption from hexane solution of
lauric acid, ¦'n mg, per g of Florisil. The amount of Florisil to
be used for f.-ach colusn is calculated by dividing this factor into
110 and multiplying by 20 g.
7.5 Before using any cleanup procedure, the analyst must process a
series of calibration starnJards through the procedure to validate
elutiort patterns ana the absence of interference from the reagents.
7
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8. Qua 111¦/ Control
8.1 Each laboratory using this method Is required to operate a formal
quality control program. The riinimum requirements of this program
consist of an initial demonstration r/r laboratory capability and
the analysis of spiked samples as a contiruing check on perfor-
mance. The laboratory 1s recuired to rcjintain performance records
to define the quality of data that is generated.
8.1.1 Before performing any analyses, the analyst must demonstrate
the ability to generate acceptable accuracy and precision
with this method. This ability is established as described
in Section 8.2.
8.1.2 In recognition of the rapid advances occurring in chromato-
graphy, the analyst is permitted certain options to improve
the separations or lower the cost of measurements. Each
time such modifications to the method are made, the analyst
1s required to repeat the procedure 1n Section 8.2.
8.1.3 The laboratory must spike and analyze a minimum of 10X of
all samples to monitor continuing laboratory performance.
This procedure is described 1n Section 8.4.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.2.1 Select a representative spike concentration for each
compound to be measured. Using stock standards, prepare a
quality control check sample concentrate in acetonitrile or
methanol 1000 times mor<3 concentrated than the selected
concentrations.
8.2.2 Using a pipet, add 1.00 mL of the check sample concentrate
to each of a minimjm of four lOOQ-rl aliquots of reagent
water. A representative wastewater may be used in place of
the reagent water, but one or more additional aliquots must
be analyzed to determine background levels, and the spike
level must exceed twice the background level for the test to
be valid. Analyze the aliquots according to the method
beginning in Section 10.
8.2.3 Calculate the average percent recovery (R), and the standard
deviation of the percent recovery (s), for the results.
Wastewater background corrections must be made before R and
s calculations are performed.
8.2.4 Table 2 provides single operator recovery and precision for
most of the carbamate and urea pesticides. Similar results
should be expected from reagent water for all compounds
listed in the method. Compare these results to the values
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calculated In Section 3.2.3. If the data are net compar-
able, review potential problem areas and repeat the test.
5.3 The analyst must calculate niethod performance criteria and define
the performance of the laboratory for each spike concentration and
paraiseter being measured.
8.3.1 Calculate upper and lower control lialts for method
performance as follows
Upper Control Limit fUCL) = R ~ 3 s
Lower Control Limit (LCL) * R - 3 s
where R and s are calculated as In Section 8.2.3.
The UCL and LCL can be used to construct control charts®
that are useful in observing trends in performance.
8.3.2 The laboratory must develop and maintain separate accuracy
statements of laboratory performance for wastewater
samples. An accuracy statement for the method is defined as
R i s. The accuracy statement should be developed by the
analysis of four aliquots of wastewater as described In
Section 8.2.2, followed by the calculation of R and s.
Alternatively, the analyst may use four wastewater data
points gathered through the requirac&eni. for continuing
quality control in Section P.4. The accuracy statements
should be updated regularly.®
8.4 The laboratory is required to collect in duplicate a portion of
their samples to monitor spike recoveries. The frequency cf spiked
sample analysis must be at least 102 of all samples cr one spiked
sanple per month, whichever is greater. One aliquot or the sample
musv be spi'
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analyzed to monitor the precision of the sampling technique. When
doubt exists ove*- the identification of a peak on the chromatogram,
confirmatory techniques such as chrortstography with a dissimilar
column, or ratio of absorbance at two or more wavelengths may be
used. Whenever possible, the laboratory should perform analysis of
quality control materials and participate in relevant performance
evaluation studies.
9. Sample Collection. Preservation, and Handling
9.1 Grab samples oust be collected in glass containers. Conventional
sampling practices5 should be followed; however, the bottle must
not be prerinsed with sample before collection. Composite samples
should be collected in refrigerated glass containers in accordance
with the requiresnents of the program. Automatic sampling equipment
must be as free as possible of plastic and other potential sources
of contamination.
9.2 The samples must be iced or refrigerated at A°C from the time of
collection until extraction.
9.3 All samples must be extracted within seven days and completely
analyzed within 40 days of extraction.
10. Sample Extraction
10.1 Mark the water irejnscus on the side of the sample bottle for later
determination of sarcple volume. Pour the entire sample into a
2-liter separatory funnel.
10.2 Add 60 mL methylene chloride to the sample bottle, seal, and shake
30 s to rinse t*e inner walls. Transfer the solvent to the separ-
atory funnel and extract the sample by shaking the funnel for 2 min
with periodic vesting to release excess pressure. Allow the organ-
ic layer to separate from the water phase for a minimum of 10 min.
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 upon the sample, but rcay include stirring, filtration of
the emulsion through glass wool, centrifugation, or other physical
methods. Collect the methylene chloride extract in a 250-mL
Erlenmeyer flask.
10.3 Add a second 60-tiL volume of methylene chloride to the sample
bottle and repeat the extraction procedure a second time, combining
the extracts *"n tHe Erlenmeyer flask. Perform a third extraction
in the same manner.
10.4 It is necessary to exchange the extract solvent to hexane 1f the
Florisil clean u? procedure is to be used. For direct HPLC
analysis the extract solvent must be exchanged to a solvent (either
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cethanol or acetonltrile) that Is compatible with the mobile
phrase. The analyst should only exchange a portion of the extract
to HPL.C solvent if there is a possibility that cleanup may be
necessary.
10.5 Pass a rneasured fraction or all of the combined extract through a
drying coluwt containing about 10 cm of anhydrous sodium sulfate
and collect the extract in a 500-mL round bottom flask. Rinse the
Erlemeyer flask and column with 20 to 30 mL of methylene chloride
to ccnplete the quantitative transfer.
10.6 Attach the 50G-
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11.2.1 Add a weight cf Florisil (nominally 20 g) predetermined by
calibration (Section 7.4 and 7.5), to a chromatographic
column. Settle the Florisil by tapping the column. Add
anhydrous sodium sulfate to the top of the Florisil to form
a layer 1 to 2 cm deep. Add 60 ml of hexane to wet and
rinse the sodium sulfate and Florisil. Just prior to
exposure of the sodium sulfate to air, stop the elutlon of
the hexare by closing the stopcock on the chromatography
column. Discard the eluate.
Tl.2.2 Adjust the sample extract volume to 10 rt with hexane and
transfer it from the volumetric flask to the Florisil
column. Rinse the flask twice with 1 to 2 nt hexane, adding
each rinse to the column.
11.2.3 Drain the colunn until the sodium sulfate layer is nearly
exposed. Elute the column with 200 mL of 20X ethyl ether in
hexane (V/V) (Fraction 1) using a drip rate of about 5
mL/min. Place a 500-mL round bottom flask under the chroma-
tography column. Elute the column again, using 200 mL of 6t
acetone in hexane (V/V) (Fraction 2), into a second flask.
Perform a third elution using 200 mL of 151 acetone in
hexane (V/V) (Fraction 3), and a final elution with 200 mL
of 50SC acetone in hexane (V/V) (Fraction 4), into separate
flasks. Hie elution patterns for five of the pesticides are
shown in Table 3.
11.2.4 Concentrate the eluates to 10 mL with a rotary evaporator as
described in Section 10.7, exchanging the solvent to
acetonitrile or methanol as required.
12. Liquid Chromatography
12.1 Table 1 summarizes the recommended operating conditions for the
liquid chromatograph. Included in this table are estimated
retention times and method detection limits that can be achieved by
this method. An example of the separations achieved by this column
is shown in Figure 1. Other HPLC columns, chromatographic condi-
tions, or detectors may be used if the requiresnents of Section 8.2
are met.
12.2 Calibrate the systers daily as described in Section 7. The
standards and extracts must be in the solvent (acetonitrile or
methanol) compatible with the mobile phase.
12.3 If the internal standard approach is being used, add the internal
standard to sanple extracts immediately before injection into the
instrument. Mix thoroughly.
12.4 Inject 10 uL of the sample extract. Record the volune Injected to
the nearest 0.05 vl, and the resulting peak size in area or peak
height units.
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12.5 The width of the retention time window used to make identifications
should be based upon measurements of actual retention time varia-
tions of standards over ^ne course of a day. Three times the
standard deviation of a retention time can be used to calculate a
suggested window size for a compound. However, the experience of
the analyst should weigh heavily in the interpretation of chromato-
grams.
12.6 If the response for the peak exceeds the working range of the
system, dilute the extract and reanalyze.
12.7 If the measurement of the peak response 1s prevented by the
presence of Interferences, further cleanup is required^
Calculations
13.1 Determine the concentration of individual compounds in the sample.
13.1.1 If the external standard calibration procedure is used,
. calculate the amount of naterial injected from the peak
response using the calibration curve or calibration factor
in Section 7.2.2. The concentration in the sample can be
calculated as follows:
(A)(Vt)
Concentration, yg/L « ——
where:
A = Amount of material Injected, in nanograms.
V-j = Volume of extract Injected in nL.
Vt = Volume of total extract in yl.
Vs = Volume of water extracted in ni.
13.1.2 If the Internal standard calibration procedure was used,
calculate the concentration in the sample using the response
factor (RF) determined in Section 7.3.2 as follows:
where:
As « Response for the parameter to be measured.
A*s * Response for the internal standard.
Is « Amount of internal standard added to each
extract in ug.
V0 = Volume of water extracted, in liters.
13.2 Calculate and report fenuron-TCA as fenuron and monuron-TCA as
monuron. Report results 1n micrograms per liter without correction
for recovery data. When duplicate and spiked sanples are analyzed,
report all data obtained with the sample results.
13
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13.3 For samples processed as part of a set where the laboratory spiked
sample recovery falls outside of the control limits in Section 8.3,
data for the affected parameters must be labeled as suspect.
14. Method Performance
14.'. The method detection limit (MIX.) is defined as the minimum
concentration of a substance that can be measured and reported with
9956 confidence that the value is above zero.'® The MDL
concentrations lifted in Table 1 were obtained using reagent water
or river water.'.'»
14.2 In a single laboratory, the average recoveries presented in Table 2
were obtained using this method.*''1 The standard deviations of
tha percent recoveries of these measurements are also included in
Table 2.
References
1. "Development of Analytical Test Procedures for Organic Pollutants in
Wastewater-Application to Pesticides," EPA Report 600/4-31-017, U.S.
Environmental Protection Agency, Cincinnati, Ohio 45268. PBI82 132507,
National Technical Information Service, Springfield, Va.
2. Farrington, D.S., Hopkins, R.G. and Ruzicka, J.H.A. "Determination of
Residues of Substituted Phenylurea Herbicides in Grain, Sell, and River
Water by Use of Liquid Chromatography," Analyst. 102, 377-331 (1977).
3. 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.
4. "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.
5. "0SHA Safety and Health Standards, Several Industry," (29 CFR 1910),
Occupational Safety and Health Administration, 0SHA 2206, (Revised,
January 1976).
6. "Safety in Academic Chemistry laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. ASTM Annual Book of Standards, Part 31, D3086, Appendix X3,
"Standardization of Florisil Column by Weight Adjustment Based on
Adsorption of Laurie Acid," American Society for Testing and Materials,
Philadelphia, PA, p 765, 1980.
14
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8. "Handbook for Analytical Quality Control in Water and Wastewater
Laboratories," EPA-600/4-79-019, U. S. Environmental Protection Agency,
Environmental Monitorind and Support Laboratory - Cincinnati, Ohio
45268, March 1979.
•9. ASTM Annual Book of Standards, Part 31, 03370, "Standard Practice for
Samplinn Water," American Society for Testing and Materials,
Philadelphia, PA, p. 76, 1980.
10. Glaser, O.A. et.al, "Trace Analysis for Wastewaters," Environnental
Science & Technology. 15, 1426 (1981).
11. "Pesticide Methods Evaluation," Letter Reports #12B, 18, 19, 20, 22 and
23 for EPA Contract No. 68-03-2697. Available from U.S. Environmental
Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati. Ohio 45268.
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TABLE 1
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
Parameter
Mobile Phase*
Retention
Time (Min)
UV
Wavelength
(nm)
Method
Detection
Limit
(wq/L)
Mexacarhate
A
8.7
254
0.52
Propoxur
A
14.3
230
0.11
Monuron
A
14.4
254
0.003
Carbaryl
A
17.0
280
0.02
Propham
A
17.2
254
0.07
Diuron
A
19.5
254
0.009
Linuron
A
21.0
254
0.009
Methiocarb
A
21.4
254
0.02
Chlorpropham
A
21.8
254
0.03
Barban
A
22.3
254
0.05
Neburon
A
24.3
254
0.012
Propoxur
3
2.0
280
0.11
Methomyl
B
6.5
254
8.9
Carbaryl
B
14.1
230
0.02
Diuron
B
15.5
254
0.009
Linuron
B
17.9
254
0.009
Propoxur
C
1.7
230
0.11
Carbofuran
C
3.5
2S0
3.2
Fluorometuron
C
3.6
254
11.1
Oxamy1
0
3.2
254
9.2
~Mobile Phase:
A Methanol /1% acetic acid, programmed linearly frca 5 to 95% methanol at
2.0 mL/min flow rate and at ambient tenperature.
B Acetonitrile/water, programmed linearly from 10% to 100% acetonitrile in
30 min at a flow rate of 2.0 nL/min.
C 50% acetonitrile In water at a flow rate of 2.0 cL/nin.
D 35% methanol in water at a flow rate of 2.0 mL/nrln.
Column: y Bondapak C-|q (10 pm) packed 1n a 20 cm long x 4 m ID stainless
steel column, with a Whatmann Co. PELL ODS ^30-38 iim) guard column, 7 cm
long x 4 mm ID.
16
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TABLE 2
SINGLE OPERATOR ACCURACY AND PRECISION
Average
Standard
Sample
Spike
No. of
Percent
Deviation
Parameter
Type*
(ug/L)
Analyses
Recovery
X
Fluorometuron
1
5C
7
93.9
7.0
2
50
7
80.0
7.2
4
1724
7
99
11.6
Propoxur
1
550
7
94.5
1.7
3
2200
105
3.0
4
550
7
87.2
7.3
5
0.5
93
6.0
Ox aroyl
1
100
7
87
8.4
2
53
7
84.9
5.5
2
1080
7
89.8
2.7
Methomyl
1
100
4
74.4
2.4
3
30660
4
48.2
2.8
2
100
91.8
2.8
2
1950
7
94.4
1.9
Diuron
1
10
89.8
1.0
3
500
4
56.1
5.0
2
10
7
90.0
2.5
2
400
7
95.7
3.2
5
0.05
98
4.7
L i naron
1
10
95.0
3.4
3
4000
4
72.2
5.1
2
10
7
93.0
1.5
2
210
7
103
4.6
5
0.05
99
4.7
Carbofuran
?
37
7
87.8
2.7
4
148
7
99.3
1.4
Barban
5
0.3
5
98
4.1
Carbaryl
5
0.1
5
101
4.1
Chlorpropham
5
0.2
5
95
3.9
Methiocarb
5
0.2
5
95
2.6
Mexacarbate
5
4.0
5
96
3.5
Monuron
5
0.05
5
97
1.7
Neburon
5
0.05
5
96
6.6
Propham
5
0.3
5
88
5.9
* = Sample Type
1 ¦ Reagent Water
2 * Municipal wastewater
3 = Industrial process water, pesticide manufacturing
4 » Industrial wastewater, pesticide manufacturing
5 ¦ River Water
17
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TABLE 3
FLORISIL FRACTIONATION PATTERNS
Percent Recovery by Fraction
Parameter
No. 1
No. 2
No. 3
No. 4
Diuron
0
0
24
58
Linuron
0
13
82
0
Methomyl
0
0
0
84
Oxamyl
0
0
92
0
Propachlor
0
94
0
0
Florisil eluate composition by fraction
Fraction 1 - 200 mL of 20% ethyl ether in hexane
Fraction 2 - 200 ml of b% acetone in hexane
Fraction 3 - 200 mL of 15% acetone in hexane
Fraction 4 - 200 mL of 50% acetone in hexane
18
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e
2
C
s
3
C
'
10
Minutes
15
20
Figure 1. Liquid chromatograra of diuron, linuron and
methonyi on Coluom 1. For conditions, see Table 1.
19
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