r Method 505! Analysis of Organohallde
Pesticides and Aroclors 1n Drinking Mater
by Mlcroextractlon and Gas Chroaatography
September 1986
Suppleaent to "Methods for the Determination
of Organic Compounds 1n Finished Drinking
Water and Raw Source Water*
Physical and Chemical Methods Branch
Environmental Monitoring and Support Laboratory
U. S. Environmental Protection Agency
Cincinnati, Ohio 45268
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KTHOO 505. ANALYSIS OF ORGANOHAUOE PESTICIDES AND AROCLORS IN
DRINKING WATER BY HICROEXTRACTION AND GAS CHROHATOGRAPHY
1. SCOPE AND APPLICATION
1.1 This method (1,2,3) 1s Applicable to the determination of the
following analytes 1n finished drinking water, drinking water
during Intermediate stages of treatment, and the raw source water:
Analyte CAS No.
Alachlor 15972-60-8
Aldrln 309-00-2
Chlordane 57-74-9
D1e1dr1n 60-57-1
EndHn 72-20-8
Heptachlor 76-44-8 '
Heptachlor Epoxlde 1024-57-3
Hexachlorobenzene 118-74-1
Llndane 58-89-9
Methoxychlor 72-43-5
Toxaphene 8001-35-2
Aroclor 1016 12674-11-2
Aroclor 1221 11104-28-2
Aroclor 1232 11141-16-5
Aroclor 1242 53469-21-9
Aroclor 1248 12672-29-6
Aroclor 1254 11097-69-1
Aroclor 1260 11096-82-5
1.2 PCBs are determined as Aroclors by this method.
1.3 For compounds other than the above mentioned analytes or for other
sample sources, the analyst must demonstrate the applicability of
the method by collecting precision and accuracy data on actual
samples (4) and provide qualitative confirmation of results by Gas
Chromatography/Mass Spectrometry (GC/MS) (5), or by GC analysis
using dissimilar columns.
1.4 The experimentally determined method detection limits (MDL) (6) for
the above organohalldes and Aroclors are shown 1n Table 1. Actual
detection limits are highly dependent upon the characteristics of
the gas chromatographlc system used (e.g. coluon type, age, and
proper conditioning; detector condition; and Injector mode and
condition).
2. SUMMARY OF METHOD
2.1 Thirty-five mL of sample are extracted wltfi 2 aL of hexane. Two uL
of the extract are then Injected Into a gas chromatograph equipped
with a linearized electron capture detector for separation and
-------
analysis. Aqueous calibration standards are extracted and analyzed
1n an Identical manner 1n order to compensate for possible
extraction losses.
2.2 The extraction and analysis time 1s 30 to 50 minutes per sample
depending upon the analytes and the analytical conditions chosen.
(See Tables 1-2 and Figures MO.)
2.3 Confirmatory evidence can be obtained using a dissimilar column.
When component concentrations 1n water samples are sufficiently
high, SC/MS may be employed.
3. INTERFERENCES
3.1 Impurities contained 1n the extracting solvent usually account for
the majority of the analytical problems. Solvent blanks should be
analyzed on each new bottle of solvent before use. Indirect dally
checks on the extracting solvent are obtained by monitoring the
laboratory reagent blanks (9.1.1). Whenever an Interference 1s
noted 1n the sample blank, the analyst should analyze another
solvent blank. Low level Interferences generally can be removed by
distillation or column chromatography (3); however, 1t 1s generally
more economical to obtain a new source solvent. An
Interference-free solvent 1s a solvent containing non-detectable
peaks at the retention times of the analytes of Interest.
3.2 Caution must be taken 1n the determination of endrln since 1t has
been reported that the splitless Injector may cause endrln
degradation (7). The analyst should be alerted to this possible
Interference resulting 1n an erratic response for endrln.
3.3 Variable amounts of pesticides and Aroclors from aqueous solutions
adhere to glass surfaces. It 1s recommended that sample transfers
and glass surface contacts be minimized.
3.4 Aldrin and methoxychlor are rapidly oxidized by chlorine.
Dechlor1nat1on with sodium thlosulfate at time of collection will
retard further oxidation of these compounds.
4. SAFETY
4.1 The toxldty and carc1nbgen1c1ty of chemicals used In this method
have not been precisely defined; each chemical should be treated as
a potential health hazard, and exposure to these chemicals should
be minimized. Each laboratory is responsible for maintaining
awareness of OSHA regulations regarding safe handling of chemicals
used in this method. Additional references to laboratory safety
are available (9-10) for the information of. the analyst.
4.2 The following organohalides have been tentatively classified as
known or suspected human or mammalian carcinogens: aldrin.
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Aroclors, chlordane, dleldrln, heptachlor, hexachlorobenzene, and
toxaphene. Pure standard materials and stock standard solutions of
these compounds should be handled 1n a hood or glovebox. A NIOSH/.
MESA approved toxic gas respirator should be worn when the analyst
handles high concentrations of these toxic compounds.
5. APPARATUS AND EQUIPMENT
5.1 SAMPLE CONTAINERS - 40-ot screw cap vials (Pierce #13075 or
equivalent) each equipped with a PTFE-faced slllcone septum (Pierce
#12722 or equivalent). Prior to use, wash vials and septa with
detergent and rinse with tap and distilled water. Allow the vials
and^septa to air dry at room temperature, place the vials 1n a
400*C oven for one hour, then remove and allow to cool 1n an area
known to be free of organlcs.
5.2 VIALS - auto sampler, screw cap with septa, 1.8 «L, Varlan
#96-000099-00 or equivalent or any other autosaapler vials not
requiring more than 1.8 oL sample volumes.
5.3 AUTO SAMPLER - Hewlett-Packard 7671A, or equivalent.
5.4 MICRO SYRINGES - 10 and 100 VL.
5.5 MICRO SYRINGE - 25 VL with a 2-1nch by 0.006-Inch needle - Hamilton
702N or equivalent.
5.6 PIPETTES - 2.0 and 5.0 mL transfer.
5.7 VOLUMETRIC FLASKS - 10 and 100 mL, glass stoppered.
5.8 STANDARD SOLUTION STORAGE CONTAINERS - 15-nL bottles with
PTFE-Uned screw caps.
5.9 GAS CHROMATOGRAPHY SYSTEM
5.9.1 The GC must be capable of temperature programming and should
be equipped with a linearized electron capture detector,
capillary column, and splUless Injector (0.5 m1n. spHtless
mode). Alternately, an on-co1umn Injector may be employed.
5.9.2 Three gas chromatographlc columns are recommended. Column A
should be used as the primary analytical column unless
routinely occurring analytes are not adequately resolved.
Columns B and C are recommended for use as confirmatory
columns when GC/MS confirmation 1s not available.
5.9.2.1 Column A - 0.32mm 10 x 30 M .long fused silica
capillary with chemically bonded methyl polysiloxane
phase (DB-1, l.Owm film, or-equivalent). The linear
velocity of the helium carrier gas is established at
25 on/sec. The column temperature is programmed
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from 180'C to 260*C at 4'C/m1n and held at 260*C
until all expected compounds have e luted. Injector
- temperature: 200'C. Detector temperature: 290*C.*
(See Table 1 for retention data.)
5.9.2.2 Column B (alternate confirmation column) - 0.32mm 10
x 30 M long fused silica capillary with a 1:1 nixed
phase of dimethyl s111cone and polyethylene glycol
(Durawax-OX3, 0.25vm film, or equivalent). The
column temperature 1s programmed from 100*C to 210*C
at 8'CMIn, and held at 210*C until all expected
compounds have e luted. Then the post temperature 1s
programed to 240*C at 8*C/m1n for 5 m1n. (See
Table 2 for retention data).
5.9.2.3 Column C (alternate confirmation column) - 0.32mm 10
x 25 M long fused silica capillary with chemically
bonded 50:50 Methyl-Phenyl $111 cone (OV-17, 1.5U
film thickness, or equivalent). The linear velocity
of the helium carrier gas 1s established at 39
cm/sec. The column temperature 1s programmed from
100'C to 260*C at 4*C/m1n and held at 260*C until
all expected compounds have e luted.
6. REAGENTS AND CONSUMABLE MATERIALS
6.1 REAGENTS
6.1.1 Hexane extraction solvent - UV Grade, Burdlck and Jackson
or equivalent.
6.1.2 Methyl alcohol - ACS Reagent Grade, demonstrated to be free
of analytes.
6.1.3 Sodium chloride, NaCl - ACS Reagent Grade - For pretreatment
before use, pulverize a batch of NaCl and place 1n a muffle
furnace at room temperature. Increase the temperature to
400* C and hold for 30 m1n. Place 1n a bottle and cap.
6.1.4 Sodium thlosulfate, NagS903 ACS Reagent Grade For
preparation of solution (0.04 g/mL), mix 1 g of
Na2^2^3 w
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6.3 STANDARD STOCK SOLUTIONS - These solutions wy be obtained as
certified solutions or prepared from pure standard materials using
the following procedures:
6.3.1 Prepare stock standard solutions (5000 ug/mL) by accurately
weighing about 0.0500 g of pure material. Dissolve the
material In nethanol and dilute to volume 1n a 10-mL
volumetric flask. Larger volumes can be used at the
convenience of the analyst. When compound purity 1s assayed
to be 961 or greater, the weight can be used without
correction to calculate the concentration of the stock
standard. Commercially prepared stock standards can be used
at any concentration 1f they are certified by the
manufacturer or by an Independent source.
6.3.2 Transfer the stock standard solutions Into Teflon-sealed
screw-cap bottles. Store at 4*C and protect from light.
Stock standard solutions should be checked frequently for
signs of degradation or evaporation, especially just prior
to preparing calibration standards from them.
6.3.3 Stock standard solutions must be replaced after six months,
or sooner 1f comparison with check standards Indicates a
problem.
6.4 SECONDARY DILUTION STANDARDS Use standard stock solutions to
prepare secondary dilution standard solutions that contain the
analytes 1n methane!. The secondary dilution standards should be
prepared at concentrations that can be easily diluted to prepare
aqueous calibration standards (Sect. 8.1.1) that will bracket the
working concentration range. Store the secondary dilution standard
solutions with minimal headspace and check frequently for signs of
deterioration or evaporation, especially just before preparing
calibration standards. The storage time described for stock
standard solutions 1n Sect. 6.4.3 also applies to secondary
dilution standard solutions.
7. SAMPLE COLLECTION. PRESERVATION. AND STORA6E
7.1 SAMPLE COLLECTION
7.1.1 Collect all samples 1n duplicate 40-mL bottles Into which 3
rag of sodium thlosulfate crystals have been added to the
empty bottles just prior to shipping to the sampling site.
Alternately, 75 wL of freshly prepared sodium thlosulfate
solution (0.04 g/nt) may be added to empty 40-mL bottles
just prior to sample collection. In collecting field
samples, 1t is recommended to add sodium thlosulfate
solution at the sampling site.
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7.1.2 When sampling from a water tap, open the tap and allow the
system to flush until the water temperature has stabilized
(usually about 10 min). Adjust the flow to about 500 mL/m1n
and collect duplicate samples from the flowing stream.
7.1.3 When sampling from a well, fill a w1de-aouth bottle or
beaker with sample, and carefully fill duplicate 40-ot
sample bottles.
7.2 SAMPLE PRESERVATION
7.2.1 The samples must be chilled to 4*C at the time of collection
and maintained at that temperature until the analyst 1s
prepared for the extraction process. Field samples that
will not be received at the laboratory on the day of
collection must be packaged for shipment with sufficient 1ce
to Insure that they will be maintained at 4*C until arrival
at the laboratory.
7.3 SAMPLE STORAGE
7.3.1 Store samples and extracts at 4*C until extraction and
analysis.
7.3.2 Extract all samples as soon as possible after collection.
Results of holding time studies suggest that all analytes
(aldrln, dleldrln, endrln, heptachlor epoxlde, hexachloro- .
benzene, Undane, and the aroclors) with the possible
exception of heptachlor may be extracted within 14 days
after collection. In general, heptachlor showed
Inconsistent results. If heptachlor 1s to be determined,
samples must be extracted within 7 days of collection.
Samples from which analytes have not been extracted within
these prescribed periods of time must be discarded and
replaced.
8. CALIBRATION AND STANDARDIZATION
8.1 CALIBRATION
8.1.1 At least three calibration standards are needed. One should
contain analytes at a concentration near but greater than
the method detection limit for each compound; the other two
should be at concentrations that bracket the range expected
1n samples. For example, If the MOL 1s 0.01 ug/L, and a
sample expected to contain approximately 0.10 ug/L 1s to be
analyzed, aqueous standards should be prepared at
concentrations of 0.02 ug/L, 0.10 ug/L, and 0.20 ug/L.
;^
8.-1.2 To prepare a calibration standard, add an appropriate volume
of a secondary dilution standard to a 35-
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water 1n a 40-mL bottle. Do not add less than 20 UL
of an alcoholic standard to the reagent water. Use a 25-uL
micro syringe and rapidly Inject the alcoholic standard Into
the middle point of the water volume. Remove the needle as
quickly as possible after Injection. Mix by Inverting and
shaking the capped bottle several times. Aqueous standards
must be prepared fresh dally.
8.1.3 Starting with the standard of lowest concentration, prepare,
extract, and analyze each calibration standard beginning
with Sect. 10.1.4 and tabulate peak height or area response
versus the concentration 1n the standard. The results are
to be used to prepare a calibration curve for each compound
by plotting the peak height or area response versus the
concentration. Alternatively, 1f the ratio of response to
concentration (calibration factor) 1s a constant over the
working range (<10X relative standard deviation), linearity
to the origin can be assumed and the average ratio or
calibration factor can be used 1n 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 an analyte
varies from the predicted response by more than *15X, the
test must be repeated using a fresh calibration standard.
If the results still do not agree, generate a new calibra-
tion curve or use a single point calibration standard as
described 1n Sect. 8.1.5.
8.1.5 Single point calibration 1s an acceptable alternative to a
calibration curve. Prepare single point standards from the
secondary dilution standard solutions. The single point
calibration standard should be prepared at a concentration
that produces a response close (*20X) to that of the
unknowns. Do not use less than 20 uL of the secondary
dilution standard solution to produce a single point
calibration standard 1n reagent water.
8.2 INSTRUMENT PERFORMANCE - Check the performance of the entire
analytical system dally using data gathered from analyses of reagent
blanks, standards, duplicate samples, and the laboratory control
standard (Sect. 9.2.2).
8.2.1 Significant peak tailing 1n excess of that shown for the
target compounds in the method chromatograms (Figures 1-10)
must be corrected. Tailing problems are generally traceable
to active sites on the GC column, improper column
Installation, or the detector operation.
8.2.2 Check the precision between replicate analyses. A properly
operating system should perform with an average relative
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standard deviation of less than 10*. Poor precision 1s
generally traceable to pneumatic leaks, especially at the
Injection port. If the 6C system 1s apparently performing -
acceptably but with decreased sensitivity, It may be
necessary to generate a new curve or set of calibration
factors to verify the decreased responses.
8.2.3 Observed relative area responses of endrin must meet the
following criteria: endrin £ 501 of total area.
9. QUALITY CONTROL
9.1 MONITORING FOR INTERFERENCES
9.1.1 Laboratory Reagent Blanks - A laboratory reagent blank 1s an
aliquot of reagent water analyzed as 1f 1t were a sample.
Add NgSjOa to laboratory reagent blanks. Analyze a
laboratory reagent blank each day and as necessary to
Identify sources of contamination. The laboratory reagent
blank should contain less than the HM. response of each
analyte.
9.2 ASSESSING ACCURACY
9.2.1 Each quarter, 1t 1s essential that the laboratory analyze
quality control check samples for each contaminant. If any
criteria established by USEPA are not met, corrective action
needs to be taken and documented.
9.2.2 After every 10 samples, and preferably 1n 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.
9.2.2.1 Laboratory Control Standard Concentrate - If
Internally prepared laboratory control standards
are used to provide the routine assessment of
accuracy, they should be prepared from a separate
set of stock standards. Fran stock standards
prepared as described 1n Sect. 6.4, add a suffi-
cient volume of each stock standard to methane1 1n
a 10-mL volumetric flask to yield a concentration
of 2.5 ug/mL and adjust to volume.
9.2.2.2 Laboratory Control Standard Add 20 uL of the
control concentrate to a 35-*. aliquot of reagent
water poured Into a 40-raL'bottle containing 75 ul
of 0.04 g/mL sodium thlosulfate.
9.2.2.3 Analyze the 35-mL aliquot as described In Sect.
10. For each analyte In the laboratory control
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standard, calculate the percent recovery (Pj)
the equation:
where S-f the analytical result from the
laboratory control standard, 1n ug/L;
and
TI the known concentration of the spike,
1n »g/L.
9.2.3 It 1s essential that the laboratory analyze an unknown
performance evaluation sample (when available) once per year
for all regulated contaminants measured. Results need to be
within acceptance limits established by USEPA for each
analyte.
10. PROCEDURE
10.1 SAMPLE PREPARATION
10.1.1 Remove samples from storage and allow them to equilibrate to
room temperature.
10.1.2 Remove the container caps. Withdraw and discard a 5-mL
volume using a transfer plpet. Replace the container caps
and weigh the containers with contents to the nearest 0.1 g
and record these weights for subsequent sample volume
determinations (Sect. 10.3).
10.1.3 Remove the container cap of each sample, and add 6 g NaCl
(Sect. 6.1.3) to the sample bottle. Recap and dissolve the
NaCl by Inverting and shaking the bottles several times
(approx. 20 sec).
10.2 EXTRACTION ANO ANALYSIS
10.2.1 Remove the cap, and using a transfer or automatic dispensing
plpet, add 2.0 mL of hexane. Recap and shake vigorously by
hand for l.mln. Invert the bottle and allow the water and
hexane phases to separate.
10.2.2 Remove the cap and carefully transfer approximately 0.5 mL
of hexane layer Into an autosampler vial using a disposable
glass plpet.
/^
10.2.3 Transfer the remaining hexane phase, being careful not to
Include any of the water phase, Into^a second autosampler
vial. Reserve this second vial at 4*C for an Immediate
reanalysls If necessary.
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10.2.4 Transfer the first sample vial to an autosampler set up to
Inject 1-2 ul portions Into the gas chroaatograph for
analysis (See Sect. 5.9 for SC conditions). Alternately,
1-2 ul portions of samples, blanks, and standards nay be
manually Injected, although an autosampler 1s strongly
recommended.
10.3 DETERMINATION OF SAMPLE VOLUME IN BOTTLES NOT CALIBRATED
10.3.1 Discard the remaining sanple/hexane Mixture from the sample
bottle. Shake off the remaining few drops using short,
brisk wrist movements.
10.3.2 Rewelgh the empty container with original cap and calculate
the net weight of sample by difference to the nearest 0.1 g
(Sect. 10.1.2 Blnus Section 10.3.2). This net weight (1n
grams) 1s equivalent to the volume of water (In mL)
extracted (Sect. 11.3).
11. CALCULATIONS
11.1 Identify the organohalldes In the sample chromatogram by comparing
the retention time of the suspect peak to retention times generated
by the calibration standards and the laboratory control standard.
Identify the multlcomponent compounds using all peaks that are
characteristic of the specific compound from chromatograms
generated with Individual standards. Select the most sensitive and
reproducible peaks for calculation purposes.
11.2 Use the calibration curve or calibration factor (Sect. 8.1.3) to
directly calculate the uncorrected concentration (C^) of each
analyte 1n the sample (e.g., calibration factor x response).
11.3 Calculate the sample volume (Vs) as equal to the net sample
weight:
Ys - gross weight (Sect. 10.1.2) - bottle tare (Sect. 10.3.2).
11.4 Calculate the corrected sample concentration as:
Concentration, »g/L C^ X y
11.5 Report the results for the unknown samples 1n Bg/L. Round off the
results to the nearest 0.1 ug/L or two significant figures.
12. ACCURACY AND PRECISION
12.1 Single laboratory (EMSl-C1nc1nnat1) accuracy and precision at
several concentrations in reagent, ground,'and tap water matrices
are presented In Table 3 (11). These results were obtained from
data generated with a DB-1 column.
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Table Z. Chromatographlc Conditions and Retention Data
of Organohallde Pesticides and Aroclors
Analyte
Alachlor
Aldrln
Butachlor
Chlorpyrlfos
Chlorpyrlf os-Methyl
01ch1oben1l
Olchlorvos
01eldr1n
Endrln
Heptachlor
Heptachlor Epoxlde
Hexachl orobenzene
Lindane
Hetolachlor
Methoxychlor
Propachlor
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Chlordane
Toxaphene
Column B
Retention T1mel. M1n
19.71
18.37
25.16
21.52
10.46,
11.20
8.91
45.08
33.30
17.53
24.61
13.35
18.35
21.42
14
15
20
10
15
20
15
20
16
22
20
35
26
42
16
26
27
.43
.11.
.64
.46,
.10,
.62,
.10.
.63,
.60,
.66,
.55,
.72,
.56,
.33,
.28,
.28
.68,
21
16
11
16
22
16
22
19
23
25
36
31
43
17
35
.02
.62.
.62,
.61,
.68,
.61,
.66.
.42,
.48,
.63,
.38,
.21,
.25,
.51.
.56,
19.45,
13.19
19.43,
25.61
19.44,
25.64
20.41,
24.20,
26.62,
44.80
33.72,
44.68
24.57,
40.67,
20
20
20
20
25
32
36
25
43
Column C
Retention T1mel. M1n
.43
.42
.42
.61
.62
.99
.29
.60
.29
21
21
26
24
22
8
1
27
29
19
24
15
18
23
36
14
10
22
8
10
16
22
16
22
20
25
25
30
10
12
19
25
28
32
.09
.39
.75
.36
.35
.09
.18,
.76
.17
.99
.63
.62
.67
.50
.44
.70
.27,
.63.
.36,
.73,
.23,
.61,
.24,
.59.
.69.
.09,
.84,
.42.
.92.
.98.
.03,
.67,
.80.
.16,
5.48
18.52,
23.84
8.54,
12.78
18.49,
23.83,
18.48,
23.80
22.59,
25.56,
28.73,
32.14
11.53,
14.55,
20.00,
25.96,
29.25,
34.40
20.75,
10.27,
20.71
25.63
20.66
23.79,
26.75
29.67
12.29,
15.48
22.84,
26.32
30.33
!More than one peak listed does not Implicate the total number of peaks
characteristic of the multi-component pesticide, listed peaks Indicate only the
ones chosen for quantification.
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13. REFERENCES
1. Glaze, W.W., L1n, C.C., Optimization of Liquid-liquid Extraction Methods
for Analysis of Organlcs 1n Water, EPA-600/S4-83-052, January 1984.
2. Henderson, J.E., Peyton, S.R. and Glaze, U.K. (1976). In "Identification
and Analysis of Organic Pollutants 1n Water* (L.H. Keith ed.),
pp. 105-111. Ann Arbor Sc1. Publ., Ann Arbor, Michigan.
3. Richard, J.J., Junk, G.A., 'Liquid Extraction for Rapid Determination of
Halomethanes 1n Water,' Journal AWWA. 69, 62, January 1977.
4. 'Handbook for Analytical Quality Control 1n Water and Wastewater
Laboratories,' EPA-600/4-79-019, U. S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio,
45268, March 1979.
5. Budde, W.L., Elchelberger, J.W., "Organic Analyses Using Gas
Chromatography-Mass Spectrometry,' Ann Arbor Science, Ann Arbor,
Michigan 1979.
6. Glaser, J.A. et al.. Trace Analyses for Wastewaters,' Environmental
Science and Technology. 15, 1426 (1981).
7. Bellar, T.A., Stemmer, P., Llchtenberg, J.J., "Evaluation of Capillary
Systems for the Analysis of Environmental Extracts," EPA-600/S4-84-004,
March 1984.
8. 'Carcinogens-Working with Carcinogens,' Department of Health, Education,
and Welfare, Public Health Service, Center for Disease Control, National
Institute of Occupational Safety and Health, Publication No, 77-206,
August, 1977.
9. 'OSHA Safety and Health Standards, General Industry," (29CFR1910),
Occupational Safety and Health Administration, OSHA 2206, (Revised,
January 1976).
10. "Safety In Academic Chemistry Laboratories," American Chenrlcal Society
Publication, Committee on Chemical Safety, 3rd Edition, 1979.
11. W1nf1eld, T., et al. "Analysis of Organohallde Pesticides 1n Drinking
Water by Mlcroextraction and Gas Chromatography." In preparation.
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Table 1, Chromatographlc Conditions and Method Detection Limits
of Organohallde Pesticides and Aroclors
Column A
Analyte Retention Time*. M1n MQL. Mq/L
Hexachlorobenzene 11.9 0.002
Llndane 12.3 0.003
Alachlor 1S.1 0.22S
Heptachlor 15.9 0.003
AldHn 17.6 0.007
Heptachlor Epoxlde 19.0 0.004
D1e1dr1n 22.1 0.012
EndHn 24.2 0.063
Methoxychlor 30.0 0.956
Aroclor 1016 13.6, 14.8, 15.2 0.08
16.2. 17.7
Aroclor 1221 7.7, 9.0, 15.9, 19.1, 15.0
24.7
Aroclor 1232 ll'.2, 14.7. 13.6. 15.2 0.48
17.7
Aroclor 1242 11.2. 13.6, 14.7, 15.2 0.31
17.7, 19.8
Aroclor 1248 14.8, 16.2, 17.1, 17.7 0.102
19.8, 22.0
Aroclor 1254 19.1. 21.9. 23.4. 24.9 0.102
26.7
Aroclor 1260 23.4, 24.9, 26.7, 28.2 0.189
29.9. 32.6
Chlordane 15.1, 15.9, 20.1, 20.9 0.14
21.3
Toxaphene 21.7, 22.5, 26.7, 27.2 1.0
iMore than one peak listed does not Implicate the total number of peaks
characteristic of the multi-component pesticide. Listed peaks Indicate
only the ones chosen for quantification.
Column A conditions: Column A - 0.32mm ID x 30 M long fused silica
capillary with methyl polyslloxane phase (OB-1, 0.25 ua film, or
equivalent). The linear velocity of the helium carrier gas Is established
at 25 cm/sec. The column temperature 1s programmed fro« 180*C to 260*C at
4"C/min and held at 260*C until all expected compounds have eluted.
Injector temperature: 200*C; detector temperture: 290*C.
-------
Table 2. Chromatographlc Conditions and Rententlon Data
of Organohallde Pesticides and Aroclor*
Column B Column C
Analyte Retention T1mel. M1n Retention Tlmgl. M1n
Alachlor
Aldrln
Butachlor
Chlorpyrlfos
Chlorpyrlf os-Methyl
D1chloben1l
Olchlorvos
D1eldr1n
Endrln
Heptachlor
Heptachlor Epoxlde
Hex ach 1 orobenzene
Llndane
Metolachlor
Methoxychlor
Propachlor
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Chlordane
Toxaphene
19.71
18.37
25.16
21.52
10.46, 21.02
11.20
8.91
45.08
33.30
17.53
24.61
13.35
18.35
21.42
14.43
15.11, 16.62, 19.45, 20.43
20.64
10.46. 11.62, 13.19
15.10. 16.61, 19.43, 20.42
20.62, 22.68, 25.61
15.10, 16.61, 19.44, 20.42
20.63, 22.66, 25.64
16.60, 19.42, 20.41, 20.61
22.66, 23.48, 24.20, 25.62
20.55, 25.63, 26.62, 32.99
35.72, 36.38, 44.80
26.56, 31.21, 33.72, 36.29
42.33, 43.25. 44.68
16.28, 17.51, 24.57, 25.60
26.28
27.68, 35.56, 40.67, 43.29
21.09
21.39
26.75
24.36
22.35
8.09
1.18, 5.48
27.76
29.17
19.99
24.63
15.62
18.67
23.50
36.44
14.70
10.27, 18.52, 20.75,
22.63, 23.84
8.36, 8.54, 10.27,
10.73, 12.78
16.23, 18.49, 20.71
22.61, 23.83, 25.63
16.24, 18.48, 20.66
22.59, 23.80
20.69, 22.59, 23.79,
25.09, 25.56, 26.75
25.84, 28.73, 29.67
30.42, 32.14
10.92, 11.53, 12.29,
12.98, 14.55, 15.48
19.03, 20.00, 22.84,
25.67, 25.96, 26.32
28.80, 29.25, 30.83
32.16, 34.40
than one peak listed does not Implicate the total number of peaks
characteristic of the multi-component pesticide. Listed peaks Indicate only the
ones chosen for quantification.
-------
Table 3. Matrix Effect on Single Laboratory Recovery
and Precision of Organohallde Pesticides and Aroclors
Compound
Alachlor
Aldrln
Chlordane
01eldr1n
Endrln
Heptachlor
Matrix1
RU
RU
6U
TU
RU
TU
RU
SW
TU
RU
6U
TU
RU
6U
TU
Number
of
Samples
6
7
3
7
3
3
8
7
8
8
7
7
7
6
8
6
6
6
6
6
7
6
. 6
6
7
6
8
8
Spike
Level
(uq/L)
0.50
0.05
1.8
0.05
1.2
1.2
0.17
3.4
0.17
3.4
0.10
3.6
0.10
3.6
0.10
3.6
0.10
3.6
0.10
3.6
0.10
3.6
0.032
1.2
0.032
1.2
0.032
1.2
Aver«9e
Accuracy
(% Recovery)
102
106
105
86
92
94
HA
NA
104
95
87
114
67
94
92
81
119
99
94
IX
106
85
77
80
37 .
r.
200
106
Relative
Standard
Dev1at1on(X)
13.1
18.9
4.9
18.9
15.7
5.6
8.0
3.6
11.8
10.1
19.6
8.0
15.0
9.1
17.1
17.3
25.0
6.6
21.5
11.3
13.2
14.6
13.3
9.3
18.3
13.8
11.3
15.8
-------
Table 3. (Continued)
Compound
Heptachlor Epoxlde
Hexachl orobenzene
Llndane
Methoxychlor
Toxaphene
Aroclor 1016
Aroclor 1221
Matrix1
RU
6U
TU
RW
6W
TU
RU
GW
TU
RU
RU
TU
RU
TU
RU
TU
Number Spike Average
of Level Accuracy
Samples (ng/t) « Recovery)
8
8
7
6
6
5
7
8
7
7
7
6
7
7
7
7
8
6
5
6
8
8
8
8
8
8
7
7
0.04
1.4
0.04
1.4
0.04
1.4
0.0025
0.09
0.002
0.09
0.0027
0.09
0.03
1.2
0.03
1.2
0.03
1.2
2.10
7.03
10
80
10
80
1.0
1.0
180
. *
180
100
115
90
103
112
81
104
103
91
101
in
88
91
111
88
109
103
93
100
98
HA
HA
110
114
HA
97
HA
92
Relative
Standard
.Dev1at1on(X)
15.6
5.7
15.8
6.7
6.7
7.3
13.0
6.4
12.0
4.4
15.6
15.2
7.1
4.5
8.8
3.1
7.9
19.8
21.0
11.1
12.6
15.3
8.6
11.8
6.6
7.7
8.3
10.4
-------
Table 3. (Continued)
Compound
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
Matrix1
RW
TW
RW
TU
RW
TW
RW
TW
RW
TW
Number
of
Samples
8
8
6
7
7
8
8
8
7
6
Spue
Level
(uq/l)
3.9
4.3
4.7
4.8
3.6
3.4
1.8
1.7
2.0
1.8
Average
Accuracy
(t Recovery)
NA
8$
NA
96
NA
84
NA
85
NA
88
Relative
Standard
Dev1at1on(X)
13.5
8.5
6.0
7.7
11.5
11.8
10.4
13.9
20.7
18.0
Matrix Identities
RW Reagent water
GW Ground water
TW - Tap Water
NA « Not applicable. A separate set of aqueous standards was not
analyzed, and the values shown for RW were used to calculate X
recovery for the TW matrix.
-------
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1 1 1 1 1 1 1 1 1 1
4 10 12 14 16 IB 20 22
(
« COLUMN: Fused silica capillary
> . LIQUID PHASE: DB-1
| FILM THICKNESS: 1.0wm
3 COLUMN DIMENSIONS: 0.32nw ID, 30 M Ion
1
3
5
|^
«
&
I °
fl|
ll
t
. A.
i ii i i ii ii I J
24 » 28 30 32 34 30 38 40 42 44
TIME (MIN)
Figure 1. Hexane spiked at 7.71 ug/L with heptachlor and llndane; 9.14 ug/L with heptachlor epoxlde;
11.4 ug/L with aldrln and hexachlorobenzene; 23 ug/L with butachlor, chlorpyrlfos, chlorpyrlfos-
methyl. dlclobenll, dleldrln, endrln, metolochlor, and propachlort and 44.9 ug/L with
mthoxychlor.
-------
A
COLUMN: Fused silica capillary
LIQUID PHASE; OB-1
FILM THICKNESS: 1.0Mn
COLUMN DIMENSIONS: 0.32tm ID, 30 M long
a 4 e 10 la 14 ie is ao aa 24 as as so sa 34 M as 40 42 44
TIME (MIN)
Figure 2. Hexane spiked it 11.4 ug/L with Arodor 1016.
-------
COLUMN: Fused silica capillary
LIQUID PHASE: OB-1
FILM THICKNESS: 1.0pm
COLUMN DIMENSIONS: 0.32nw ID. 30 M long
.A/V
a 4 10 la 14 10 10 20 22 94 2ft 88 30 39 94 30 38 40 42 44
TINE (MIN)
Figure 3. Hexane spiked at 171.4 ug/L with Aroclor 1221.
-------
COLUMN: Fused silica capillary
LIQUID PHASE: DB-1
FILM THICKNESS: 1.0p»
COLUMN DIMENSIONS: 0.32wn ID, 30 M long
/\ ^
10 12 14 18 18 20 22 24 20 28 90 32 34 38 38 40 42 44
TIME (MIN)
Figure 4. Hexane spiked at 57.1 ug/L with Aroclor 1232.
-------
Jl
COLUMN: Fused silica capillary
LIQUID PHASE: OB-1
FILM THICKNESS: 1.0pm
COLUMN DIMENSIONS) 0.32mm ID, 30 M long
I
a 4 6 8 10 la 14 16 16 20 22 24 » 28 30 32 34 M 38 40 42 44
TIME (MIN)
Figure 5. Hexane spiked at 57.1 ug/L with Aroclor 1242.
-------
COLUMN: Fused silica capillary
LIQUID PHASE: DB-1
FILM THICKNESS: 1.0pm
COLUMN DIMENSIONS: 0.32im ID, 30 M long
10 12 14 19
IS 20 22 24
TIME (HIM)
28 30 32 34 M 38 4O 42 44
Figure 6. Hexane spiked at 57.1 ug/L with Aroclor 12*8.
-------
COLUMN: Fused siHca capillary
LIQUID PHASE: OB-1
FILM THICKNESS: LOpm
COLUMN DIMENSIONS: 0.32m ID. 30 H long
a 4 8 10 la 14 16 18 20 22 24 2ft 28 30 32 34 36 38 40 42 44
TIME (MIN)
Figure 7. Hexane spiked at 42.9 ug/L with Aroclor 1254 .
-------
COLUMN: Fused silica capillary
LIQUID PHASE: OB-1
FILM THICKNESS: 1.0|im
COLUMN DIMENSIONS: 0.32mm ID, 30 M long
JU
r . .
A..
i i_
10 la 14
la 20 22
TINE (NIN)
24 29 28 30 32 34 36 38 40 42 44
Figure 8. Hexane spiked at 34.3 ug/L with Aroclor 1260.
-------
COLUMN: Fused silica capillary
LIQUID PHASE: DB-1
FILM THICKNESS: 1.0pm
COLUMN DIMENSIONS: 0.32nm ID, 30 M long
10 12 14 16 18 20 22 24 29 28 30 32 94 36 36 40 42 44
TIME (MIN)
Figure 9. Hexane spiked at 28.6 ug/L with chlordane.
------- |