United States
Environmental Protection
Agency
Environmental Monitoring & Support
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/4-81-045 Sept. 1982
vvEPA
Test Method
The Determination of
Polychlorinated Biphenyls in
Transformer Fluid and
Waste Oils
Thomas A. Bellar and James J. Lichtenberg
1. Scope
1.1 This is the EPA preferred method
for the determination of polychlorinated
biphenyls (PCBs) in waste oils according
to PCB regulations.1 This gas
chromatographic (GC) procedure is
applicable to the determination of
commercial mixtures of PCBs in
transformer fluids and certain other
hydrocarbon-based waste oils. The
method can be used to analyze waste oils
for individual PCB isomers or complex
mixtures of chlorinated biphenyls from
monochlorobiphenyl through
decachlorobiphenyl only if the isomers
have been previously identified by other
methods2 or by knowledge of the sample
history.
1.2 The detection limits are dependent
upon the complexity of the sample matrix
and the ability of the analyst to properly
maintain the analytical system. Using a
carefully optimized instrument, this
method has been shown to be useful for
the determination of commercial PCB
mixtures spiked into transformer fluid
over a range of 5.0 to 500 mg/kg. Based
upon a statistical calculation at 5 mg/kg
for a simple oil matrix, the method
detection limit for Aroclors 1221, 1 242,
1254, and 1260 is 1 mg/kg. The method
detection limit (MDL) is defined as the
minimum concentration of a substance
that can be measured and reported with
99% confidence that the value is above
zero.
1.3 This method is restricted to use by
or under the supervision of analysts
experienced in the use of gas
chromatography and in the interpretation
of gas chromatograms. Prior to sample
analysis, each analyst must demonstrate
the ability to generate acceptable results
with this method by following the proce-
dures described in Section 10.2.
2. Summary
2.1 The sample is diluted on a weight/
volume basis so that the concentration of
each PCB isomer is within capability of
the GC system (0.01 to 10 ng/^L).
2.2 The diluted sample is then injected
into a gas chromatograph for separation
of the PCB isomers. Measurement is
accomplished with a halogen-specific
detector which maximizes baseline
stability and minimizes interferences
normally encountered with other
detectors. The electron capture detector
(ECD) can normally be substituted for the
halogen-specific detector when samples
contain dichloro through
decachlorobiphenyl isomers (Aroclors
1016, 1232, 1242, 1248, 1254, 1260,
-------
1262 and 1268) or when the sample
matrix does not interfere with the PCBs.
Several cleanup techniques are provided
for samples containing interferences. A
mass spectrometer operating in the
selected ion monitoring mode of data
acquisition may also be used as the GC
detector when PCB levels are sufficiently
high and the PCB m/z ranges are free
from interference. Interferences may
occur in some waste oil samples even
after exhaustive cleanup.
2.3 The concentration of the PCBs are
calculated on a mg/kg basis, using
commercial mixtures of PCBs as
standards. The analysis time, not
including data reduction, is approximately
35 min/ sample.
3. Interferences
3.1 Qualitative misidentifications are
always a potential problem in GC
analysis. The use of a halogen-specific
detector and the analyst's skill in
recognizing chromatographic patterns of
commercial PCB mixtures minimizes this
possibility.
3.2 Whenever analyzed samples do not
provide chromatographic patterns nearly
identical to the standards prepared
from commerical PCBs, the
analyst must confirm the presence of
PCBs by one of three ways: by analysis
after column cleanup; by analysis on
dissimilar GC columns; or, by gas
chromatography/mass spectrometry
(GC/MS).
3.3 During the development and testing
of this method, certain analytical
parameters and equipment designs were
found to affect the validity of the
analytical results. Proper use of the
method requires that such parameters or
designs are to be used as specified. These
items are identified in the text by the
word "must." Anyone wishing to deviate
from the method in areas so identified
must demonstrate that the deviation does
not affect the validity of the data and
alternative test procedure approval must
be obtained through the USEPA,
Environmental Monitoring and Support
Laboratory, Equivalency Program, 26 W.
St. Clair Street, Cincinnati, Ohio 4526S.3
An experienced analyst may make
modifications to parameters or equipment
identified by the term "recommended."
Each time such modifications are made to
the method, the analyst must repeat the
procedure in Section 10.2. In this case,
formal approval is not required, but the
documented data from Section 10.2 must
be on file as part of the overall quality
assurance program.
3.4 Samplers which are diluted at a ratio
of 100:1 and are analyzed by electron
capture GC, consistently produce results
that are 10 to 20% lower than the true
value (See Section 12). This is due to
quenching of the detector response by
high boiling Hydrocarbons coeluting with
the PCBs. The degree of error is matrix
dependent and is not predictable for
samples of unknown origin. As the PCB
concentration approaches 20% of a
control level, [for example, 50 mg/kg, the
analyst mustiroutinely reanalyze a
duplicate spiked sample to determine the
actual recovery. The duplicate or diluted
sample is spiked at two times the electron
capture observed value and reanalyzed
according to Section 10.2. The results are
corrected accordingly.
4. Apparatus
4.1 Gas Chromatograph—The gas
chromatograph should be equipped with
on-column 1/i-inch injectors. The oven
must be large enough to accept a V4" OD
2-meter coiled glass column. If halogen-
specific detectors are used, then the
column ovenishould have programming
capabilities. '
4.2 Gas Chromatographic Detector
i
4.2.1 A hal'ogen-specific detector is
used to eliminate interferences causing
misidentifications or false-positive values
due to non-organohalides which
commonly coelute with the PCBs.
4.2.1.1 Electrolytic conductivity detector
— the Hall electrolytic conductivity
detector. Model 700-A (HED), available
from Tracor, Inc., has been found to
provide the sensitivity and stability
needed for the current PCB Regulations.1
4.2.1.2 Other halogen-specific
detectors, including older model
electrolytic conductivity detectors and
microcoulometric titration, may be used.
However, the stability, sensitivity, and
response time of these detectors may
raise the MDL and adversely affect peak
resolution. Each system must be shown
to be operating within requirements of
the PCB regulations by collecting single
laboratory accuracy and precision data
and MDL on simple spiked samples, as
described in Section 10.2.
4.2.2 Semi-specific detectors, such as
ECD, may be substituted when sample
chromatographic patterns closely match
those of the standards. Acid cleanup (See
Section 8.1) or Florisil slurry cleanup (See
Section 8.7) should be incorporated
routinely when the ECD is used. See
Section 3.4 for additional quality control
procedures for ECD.
4.2.3 Quantitative GC/MS techniques
can be used. The recommended approach
is selected ion monitoring, but the
GC/MS data system must have a
program that supports this method of
data acquisition. The program must be
capable of monitoring a minimum of eight
ions, and it is desirable for the system to
have the ability to change the ions
monitored as a function of time. For PCB
measurements, several sets of ions may
be used, depending on the objectives of
the study and the data system
capabilities. The alternatives are as
follows:
•4.2.3.1 Single ions for high sensitivity:
154, 188, 222, 256, 292, 326, 360, 394.
4.2.3.2 Short mass ranges which may
give enhanced sensitivity, depending on
the data system capabilities: 154-156,
188-192, 222-226, 256-260, 290-295,
322-328, 356-364, 390-398.
4.2.3.3 Single ions giving decreased
sensitivity but are selective for levels of
chlorination:2 190, 224, 260, 294, 330,
362, 394.
4.2.3.4 The data system must have the
capability of integrating an abundance of
the selected ions between specified limits
and relating integrated abundances to con-
centrations, using the calibration
procedures described in this method.
4.3 Gas Chromatographic Columns
4.3.1 The GC columns and conditions
listed below are recommended for the
analysis of PCB mixtures in oil. If these
columns and conditions are not adequate,
the analyst may vary the column
parameters to improve separations. The
columns and conditions selected must be
capable of adequately resolving the PCBs
in the various Aroclor mixtures so that
each Aroclor is identifiable through
isomer pattern recognition. (See Figures
1 through 6 to establish this.) To properly
use the calculation procedure described
in Section 11.5, the analyst must use the
methyl silicone liquid phase column,
-------
described in Section 4.3.2. Capillary
columns and their associated specialized
injection techniques are acceptable
alternatives; however, due to problems
associated with the use of capillary
columns the analyst must demonstrate
that the entire system will produce
acceptable results by performing the
operations described in Section 10.2.
4.3.2 Recommended primary analytical
column: Glass, ^-inch O.D. (2-mm I.D.),
6-ft. (180 cm) long, packed with Gas-
Chrom Q 100/120 mesh coated with 3%
OV-1.
Carrier gas: 40 to 60 mL/min (helium,
nitrogen or mixtures of methane in argon,
as recommended by the manufacturer of
the detector).
Temperature Program: 120°C isothermal
for 2 minutes, 6°/min to 220°C and hold
until all compounds elute. Figure 7 shows
a chromatogram of the PCB locator
mixture (See Section 5.8) analyzed under
these conditions. Each PCB peak has
been identified by assigning the same
relative retention times determined in the
isothermal runs (Figures 1 through 6).
Isothermal Operation: Aroclor 1221,
1232, or C\i through CI4 isomers —
recommended range 140 to 150°C
Aroclor 1016, 1242, 1248, 1254, 1260,
1262, 1 268, or CI3 through Cho isomers
— recommended range 170 to 200°C
4.3.3 Recommended confirmatory
column: Glass tubing, Vi-inch O.D. (2-mm
I.D.), 6-ft. (180 cm) long, packed with
Gas-Chrom Q 100/120 mesh coated with
1.5% OV-1 7 + 1.95% OV-210.
Carrier gas: 40 to 60 mL/min (helium,
nitrogen or mixtures of methane in argon,
as recommended by the manufacturer of
the detector).
Column temperatures: Aroclor 1221,
1232, or Cli through CI4 isomers
recommended range — 170 to 180°C.
Aroclor 1016, 1242, 1248, 1254, 1260,
1268, or CI3 through Clio isomers 200°C.
4.4 Volumetric flasks — 10, 100, 200,
and 250-mL. <
4.5 Pipets — 0.1 p, 1.0, and 5.0 mL
Mohr delivery (for viscous oils cut off tip
of pipet).
4.6 Micro syringes — 10.0/uL
4.7 Sample containers — 20 mL or
larger screw-cap bottles with Teflon-
faced cap liners. (Aluminum foil cap
liners can be used for non-corrosive
samples.)
4.8 Chromatographic column —
Chromaflex, 400-mm long x 19-mm I.D.
(Kontes K-420540-901 for equivalent).
4.9 Gel Permeation Chromatograph —
GPC Autoprep 1002 or equivalent,
available from Analytical Bio Chemistry
Laboratories, Inc.
4.10 Balance — Analytical, capable of
weighing 99 g with a sensitivity of ±
0.0001 g.
4.11 Kuderna-Danish (K-D) Evaporative
Concentrator Apparatus
4.11.1 Concentrator tube — 10 mL,
graduated (Kontes K-570050-1025 or
equivalent). Calibration must be checked.
Ground glass stopper (size 19/22 joint) is
used to prevent evaporation of solvent.
4.11.2 Evaporative flask — 500 mL
(Kontes K-57001-0500 or equivalent).
Attach "to concentrator tube with springs
(Kontes K-662750-001 2 or equivalent).
4.11.3 Snyder column—Three-ball
macro (Kontes K503000-0121 or
equivalent).
5. Reagents and Materials
5.1 Reagent safety precautions
5.1.1 The toxicity or carcinogenicity 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 Occupational
Safety and Health Administration
regulations regarding the safe handling of
the chemical 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.
5.1.2 PCBs have been tentatively
classified as known or suspected, human
or mammalian carcinogens. Primary
standards of these toxic compounds
should be prepared in a hood.
5.1.3 Diethyl ether should be monitored
regularly to determine the peroxide
content. Under no circumstances should
diethyl ether be used with a peroxide
content in excess of 50 ppm as an
explosion could result. Peroxide test
strips manufactured by EM Laboratories
(available from Scientific Products Co.,
Cat. No. P1126-8 and other suppliers) are
recommended for this test. Procedures
for removal of peroxides from diethyl
ether are included in the instructions
supplied with the peroxide test kit.
5.2 Hexane (mixed hexanes), isooctane,
acetonitrile, methylene chloride,
cyclohexane, and diethyl ether of
pesticide grade.
5.3 Recommended Column Packings
5.3.1 Gas Chromd 100/120 mesh
coated with 3% OV-1.
5.3.2 Gas Chrom Q 100/120 mesh
coated with 1.5% OV-17 + 1.95%
OV-210.
5.4 Standards
5.4.1 Aroclors 1016, 1221, 1232,
1242, 1248, 1254, 1260, 1262, 1268.
Primary dilutions of various Aroclors are
available from USEPA, Environmental
Monitoring and Support Laboratory,
Quality Assurance Branch, 26 W. St.
Clair Street, Cincinnati, Ohio 45268.
5.4.2 2-Chlorobiphenyl, 3-
chlorobiphenyl, and decachlorobiphenyl.
5.4.3 Pure, individual PCBs, as
identified in the sample by mass
spectrometry or indicated by retention
data.
5.4.4 Alumina (Fisher A540 or
equivalent).
5.4.5 Silica gel (Davison Grade 950 or
equivalent).
5.4.6 Florisil (PR grade or equivalent).
5.4.7 Sulfuric acid A.C.S.
5.4.8 Quality Control Check Sample —
Certified Samples of PCBs in oil matrices
are available from USEPA, Environmental
Monitoring and Support Laboratory,
Quality Assurance Branch, 26 W. St.
Clair Street, Cincinnati, Ohio 45268.
5.5 Standard Stock Solutions —Prepare
primary dilutions of each of the Aroclors
or individual PCBs by weighing
approximately 0-01 g of material within
± 0.0001 g. Dissolve and dilute to 10.0 mL
with isooctane or hexane. Calculate the
concentration in fjg/fjL. Store the primary
dilutions at 4°C in 10- to 15-mL narrow-
mouth, screw-cap bottles with Teflon cap
liners. Primary dilutions are stable
indefinitely if the seals are maintained.
The validity of inhouse-generated or
stored primary and secondary dilutions
must be verified on a quarterly basis by
analyzing Environmental Monitoring and
Support Laboratory-Cincinnati-Quality
-------
Control Check Samples or certified PCB
standards.
5.6 Working Standards — Prepare
working standards similar in PCB
composition and concentration to the
samples by mixing and diluting the
individual standard stock solutions. Dilute
the mixture to volume with pesticide
quality hexane. Calculate the
concentration in ng//A. as the individual
Aroclors (Section 11.4) or as the
individual PCBs (Section 11.5). Store
dilutions at 4°C in 10- to 15-mL narrow-
mouth, screw-cap bottles with Teflon cap
liners. If the seals are maintained, these
secondary dilutions can be stored
indefinitely. (See Section 5.5.)
5.7 Laboratory control standard (LCS) —
Prepare a LCS by spiking a PCB-free oil
typical of the matrix normally analyzed,
such as a transformer oil, at 50.0 mg/kg
with a PCB mixture typical of those
normally found in the samples, such as
Aroclor 1260 at 50.0 mg/kg.
5.8 PCB Locator Mixture — Prepare a
PCB locator mixture containing 0.1 ng/fiL
of 2-chlorobiphenyl, 0.1 ng/>L3-
chlorobiphenyl, 0.5 ng//uL Aroclor 1242,
0.5 ng/yuL Aroclor 1260, and 0.2 ng//uL
Aroclor 1268 in hexane (0.1 ng///Lof
decachlorobiphenyl can be substituted for
Aroclor 1268). Use the chromatogram
generated by the PCB locator mixture to
help identify the retention times of the
various PCB isomers commonly found in
commercial PCB mixtures.
6. Sample Collection and
Handling
6.1 Sample containers should have a
volume of 20 mL or more and have Teflon
or foil-lined screw caps.
6.2 Sample Bottle Preparation
6.2.1 Wash all sample bottles and seals
in detergent solution. Rinse first with tap
water and then with distilled water. Allow
the bottles and seals to drain dry in a
contaminant-free area. Then rinse seals
with pesticide-grade hexane and allow to
air dry.
6.2.2 Heat sample bottles to 400°C for
15 to 20 minutes or rinse with pesticide-
grade acetone or hexane and allow to air
dry.
6.2.3 Store the clean bottles inverted or
sealed until use.
6.2.4 Sample bottles can be reused.
Prior to reuse, rinse the bottles and seals
three times with hexane, allow to air dry,
and then proceed to Section 6.2.1.
6.3 Sample Preservation—The
samples should be stored in a cool, dry,
dark area until analysis. Storage times in
excess of four Weeks are not
recommended for unknown or undefined
sample matrices.
6.4 Sample Collection
6.4.1 Fill a large container, such as a
500-mL beaker, from a representative
area of the sample source. If practical,
mix the sample source prior to sampling.
6.4.2 Fill a minimum of two 20-mL
sample bottles; (Field Sample 1 (FS1) and
Field Sample 2 (FS2)) approximately 80%
full from the sampling container.
6.4.3 Repeajt Sections 6.4.1 and 6.4.2 if
there is a need to monitor sampling
precision, as described in Section 10.6.
7. Procedure
7.1 The approximate PCB concentration
of the sample may be determined by X-
ray fluorescence (total halogen
measurement), microcoulometry (total
halogen measurement), density
measurements, or by analyzing a very
dilute mixture,of the sample (10,000:1)
according to Section 7.4.
7.2 For samples in the 0- to 100-mg/kg
range, dilute at the rate of 100:1 in
hexane.
7.2.1 Pipet 1.0 mL of sample into a
100-mL volurnetric flask, using a 1.0-mL
Mohr pipet. For viscous samples, cut the
capillary tip of,f the pipet. Dilute to volume
with hexane. Stopper and mix.
7.2.2 Using|the same pipet as in
Section 7.2.1, deliver 1.0 mL of sample
into a tared 10-mL beaker weighed to
±.001 g. Rewpigh the beaker to ± .001 g
to determine the weight of sample used
in 7.2.1. !
7.2.3 As an alternative to Sections
7.2.1 and 7.2.2, weigh approximately 1 g
to ± .001 g of sample in a 100-mL
volumetric flask and dilute to volume with
hexane.
7.2.4 Analyze the diluted sample
according to Section 7.4 or store the
diluted sample in a narrow-mouth bottle
with a Teflon-lined screw cap.
7.3 For samples above 100 mg/kg in
concentration, dilute at a rate of 1000:1
in hexane.
7.3.1 Pipet 0.10 mL of sample into a
100-mL volumetric flask, using a 0.10
mL-Mohr pipet. Dilute to volume with
hexane, stopper and mix.
7.3.2 Using the same pipet as in
Section 7.3.1, deliver 0.10 mL of sample
into a tared 10-mL beaker to ± .0001 g.
Reweigh the beaker to determine the
weight of sample used in Section 7.3.1.
7.3.3 As an alternative to Sections
7.3.1 and 7.3.2, weigh approximately 0.1
g to ± .0001 g of sample and in a 100 mL
volumetric flask. Dilute to volume with
hexane.
7.3.4 Analyze the diluted sample
according to Section 7.4 or store in a
narrow-mouth bottle with a Teflon-lined
screw cap.
7.3.5 If the concentration of PCBs is
still too high for the chromatographic
system, prepare secondary dilutions from
Sections 7.3.1 or 7.3.3 until acceptable
levels are obtained.
7.4 Analyze the sample by injecting the
hexane mixture into the gas
chromatograph, using auto injectors or
the solvent flush technique.4
7.4.7 Recommended injection volumes:
Halogen-specific detector — 4 to 5//L,
ECD 2 to 3 //L Smaller volumes may be
injected when auto injectors are used if
the resulting MDL are acceptable.
Note: When semi-specific detectors are
used, cleanup techniques (See Section
4.2.2) should be routinely incorporated
into the analysis scheme prior to
injection.
7.5 If the resulting chromatogram
shows evidence of column flooding or
nonlinear detector responses, further
dilute the sample according to Section
7.3.5.
7.6 Determine whether or not PCBs are
present in the sample by comparing the
sample chromatogram to that of the PCB
locator mixture. Section 5.8.
7.6.1 If a series of peaks in the sample
match some of the retention times of
PCBs in the PCB locator mixture, attempt
to identify the source by comparing
chromatograms of each standard
prepared from commercial mixtures of
PCBs (See Section 5.6). Proceed to
Section 11.4 if the source of PCBs is
identified.
7.6.2 If the sample contains a complex
mixture of PCBs, proceed to Section 11.5.
7.6.3 If a dilution ratio of 1000:1
(Section 7.3) or higher was analyzed and
no measurable PCB peaks were detected,
analyze an aliquot of sample diluted to
100:1.
4
-------
7.6.4 If several PCB interference
problems are encountered or if PCB ratios
do not match standards, proceed to
Section 8. Use alternate columns or use
GC/MS2 to verify whether or not the
nonrepresentative patterns are due to
PCBs.
8. Cleanup
Several tested cleanup techniques are
described. Depending upon the
complexity of the sample, one or all of the
techniques may be required to resolve the
PCBs from interferences.
8.1 Acid Cleanup
8.1.1 Place 5.0 mL of concentrated
sulfuric acid into a 40-mL narrow-mouth
screw-cap bottle. Add 10.0 mL of the
diluted sample. Seal the bottle with a
Teflon-lined screw-cap and shake for one
minute.
8.1.2 Allow the phases to separate,
transfer the sample (upper phase) to a
clean narrow-mouth screw-cap bottle.
Seal with a Teflon-Hmed cap.
8.1.3 Analyze according to Section 7.4.
8.1.4 If the sample is highly
contaminated, a second or third acid
cleanup may be employed.
Note: This cleanup technique was tested
over a 6-month period, using both
electron capture and electrolytic
conductivity detectors. Care was taken to
exclude any samples that formed an
emulsion with the acid. The sample was
withdrawn well above the sample-acid
interface. Under these conditions, no
adverse effects associated with column
performance and detector sensitivity to
PCBs were noted. This cleanup technique
could adversely affect the
chromatographic column performance for
samples containing analytes other than
PCBs.
8.2 Florisil Column Cleanup
8.2.1 Variances between batches of
Florisil may affect the elution volume of
the various PCBs. For this reason, the
volume of solvent required to completely
elute all of the PCBs must be verified by
the analyst. The weight of Florisil can
then be adjusted accordingly.
8.2.2 Place a 20.0-g charge of Florisil,
activated at 130°C, into a Chromaflex
column. Settle the Florisil by tapping the
column. Add about 1 cm of anhydrous
sodium sulfate to the top of the Florisil.
Pre-elute the column with 70 to 80 mL of
hexane. Just before the exposure of the
sodium sulfate layer to air, stop the flow.
Discard the eluate.
8.2.3 Add 2.0 mL of the undiluted
sample to the column with a 2-mL Mohr
pipet. For viscous samples, cut the
capillary tip off the pipet. Add 225 mL of
hexane to the column. Carefully wash
down the inner wall of the column with a
small amount of the hexane prior to
adding the total volume. Collect and
discard the first 25.0 mL.
8.2.4 Collect exactly 200 mL of hexane
eluate in a 200-mL volumetric flask. All
the PCBs must be in this fraction.
8.2.5 Using the same pipet as in
Section 8.2.2, deliver 2.0 mL of sample
into a tared 10-mL beaker weighed to
± 0.001 g. Reweigh the beaker to
determine the weight of the sample
diluted to 200 mL.
8.2.6 Analyze the sample according to
Section 7.4.
8.3 Alumina Column Cleanup
8.3.1 Adjust the activity of the alumina
by heating to 200°C for 2 to 4 hours.
When cool, add 3% water (weightrweight)
and mix until uniform, Store in a tightly
sealed bottle. Allow the alumina to
equilibrate at least 30 minutes before
use. Adjust activity weekly.
5.3.2 Variances between batches of
alumina may affect the elution volume of
the various PCBs. For this reason, the
volume of solvent required to completely
elute all of the PCBs must be verified by
the analyst. The weight of alumina can
then be adjusted accordingly.
8.3.3 Place a 50.0-g charge of alumina
into a Chromaflex column. Settle the
alumina by tapping. Add about 1 cm of
anhydrous sodium sulfate to the top of
the alumina. Pre-elute the column with
70 to 80 mL of hexane. Just before
exposing the sodium sulfate layer to air,
stop the flow. Discard the eluate.
8.3.4 Add 2.5 mL of the undiluted
sample to the cojumn with a 5-mL Mohr
pipet. For viscous samples, cut the
capillary end off the pipet. Add 300 mL of
hexane to the column. Carefully wash
down the inner walls of the column with
a small volume of hexane prior to adding
the total volume. Collect and discard the
0- to 50-mL fraction.
8.3.5 Collect exactly 250 mL of the
hexane in a 250-mL volumetric flask. All
the PCBs must be in this fraction.
8.3.6 Using the same pipet as in
Section 8.3.4, deliver 2.5 mL of sample
into a tared 10-mL beaker (± 0.001 g).
Reweigh the beaker to determine weight
of sample diluted to 250 mL.
8.3.7 Analyze the sample according to
Section 7.4.
8.4 Silica Gel Column Cleanup.
8.4.1 Activate silica gel at 135°C
overnight.
8.4.2 Variances between batches of
silica gel may affect the elution volume of
the various PCBs. For this reason, the
volume of solvent required to completely
elute all of the PCBs must be verified by
the analyst. The weight of silica gel can
then be adjusted accordingly.
8.4.3 Place a 25-g charge of activated
silica gel into a Chromaflex column.
Settle the silica gel by tapping the
column. Add about 1 cm of anhydrous
sodium sulfate to the top of the silica gel.
8.4.4 Pre-elute the column with about
70 to 80 mL of hexane. Just before
exposing the sodium sulfate layer to air,
stop the flow. Discard the eluate.
8.4.5 Add 2.0 mL of the undiluted
sample to the column with a 2-mL Mohr
pipet. For viscous samples, cut the
capillary tip off the pipet.
8.4.6 Wash down the inner wall of the
column with 5 mL of hexane.
8.4.7 Elute the PCBs with 195 mL of
10% diethyl ether in hexane
(volume: volume).
8.4.8 Collect exactly 200-mL of the
eluate in a 200-mL volumetric flask. All
the PCBs must be in this fraction.
8.4.9 Using the same pipet as in
Section 8.4.5, deliver 2.0 mL of sample
into a tared 10-mL beaker (± 0.001 g).
Reweigh to determine the weight of
sample diluted to 200 mL.
8.4.10 Analyze the sample according to
Section 7.4.
8.5 Gel Permeation Cleanup
8.5.1 Set up and calibrate the gel
permeation chromatograph with an SX-3
column according to the instrument
manufacturer's instruction manual. Use
15% methylene chloride in cyclohexane
(volume:volume) as the mobile phase.
8.5.2 Place 1.0 mL of sample into a
100-mL volumetric flask, using a 1 -mL
Mohr pipet. For viscous samples, cut the
capillary tip off the pipet.
-------
8,5.3 Dilute the sample to volume,
using 15% methylene chloride in
cyclohexane (volume:volume).
8.5.4 Using the same pipet as in
Section 8.5.2, deliver 1.0 mL of sample
into a tared 10-mL beaker (± 0.001 g).
Reweigh the beaker (± 0.001 g) to
determine the weight of sample used in
Section 8.5.2.
8.5.5 As an alternative to Sections
8.5.2 and 8.5.3, weigh approximately 1 g
(± 0.001 g) of sample and dilute to 100.0
mL in 15% methylene chloride in
cyclohexane (volume:volume).
8.5.6 Inject 5.0 mL of the diluted
sample into the instrument. Collect the
fraction containing the Cd through Clio
PCBs (see instruction manual. Section
8.5.1) in a K-D flask equipped with a 10-
mL ampul.
8.5.7 Concentrate the Section 8.5.4
fraction down to less than 5 mL, using K-
D evaporative concentration techniques.
8.5.8 Dilute to 5.0 mL with hexane,
then analyze according to Section 7.4. Be
sure to use 100 mL as the dilution
volume for the final calculation.
8.6 Acetonitrile Partition
8.6.1 Place 10.0 mL of the previously
diluted sample into a 125-mL separatory
funnel. Add 5.0 mL of hexane. Extract the
sample four times by shaking vigorously
for one minute with 30-mL portions of
hexane-saturated acetonitrile.
8.6.2 Transfer and combine the
acetonitrile phases to a 1 -L separatory
funnel and add 650 mL of distilled water
and 40 mL of saturated sodium chloride
solution. Mix thoroughly for 30 to 35
seconds. Extract with two 100-mL
portions of hexane by vigorously shaking
about 15 seconds.
8.6.3 Combine the hexane extracts in a
I-L separatory funnel and wash with two
100-mL portions of distilled water.
Discard the water layer and-pour the
hexane layer through a column (Section
4.8) packed with 3 to 4 inches of
anhydrous sodium sulfate. Drain the
column into a 500-mL K-D flask equipped
with a 10-mL ampul. Rinse the
separatory funnel and column with three
10-mL portions of hexane.
8.6.4 Concentrate the extracts to 6 to
10 mL in the K-D evaporator in a hot
water bath, then adjust the volume to
10.0 mL. Be sure to use the correct
dilution volume (See Section 8.6.1) for
the final calculation.
8.6.5 Analyze according to Section 7.4.
8.7 Florisil Slurry Cleanup
8.7.1 Place 10 mL of the diluted sample
into a 20-mL n'arrow-mouth screw-cap
container. AddjO.25 g of Florisil. Seal
with a Teflon-lined screw-cap and shake
for one minute.
8.7.2 Allow the Florisil to settle then
decant the treated solution into a second
container. Analyze according to Section
7.4.
9. Calibration
9.1 Single Point Calibrations — Prepare
calibration standards from standard stock
solutions in hexane that are close to the
unknown in composition and in
concentration. If when using an
electrolytic conductivity detector the
sample response is in the low level
nonlinear detection area, the calibration
point must thep be within 20% of the
sample. The ECD must be operated only
within its linear response range.
9.2 As an alternative to Section 9.1,
prepare a calibration curve for each
Aroclor or PCB| detected in the sample.
The standard curve must contain at least
three points, two of which must bracket
the sample concentration. When using an
electrolytic conductivity detector, if the
sample response is in a low level
nonlinear area; of the calibration curve,
two of the calibration points must be
within 20% of the unknown. The
calibration curve must be checked daily,
using the LCS,: Section 5.7. If the
calibration curve is not within 15% of the
LCS, recalibrate the instrument. If an ECD
is used then it will be necessary to
correct the LCS value for recovery (See
Section 3.4). Use the recovery value
determined the same day the calibration
curve was generated. The correct value
must be within 15% of the spike value,
otherwise the instrument must be
recalibrated. \
10. Precision and Accuracy
10.1 Each laboratory using this method
is required to operate a formal quality
control program. The minimum
requirements of this program consist of
an initial demonstration of laboratory
capability and the analysis of spiked
samples as a continuing check on
performance. The laboratory is required
to maintain performance records to
define the quality of data that is
generated. After January 1, 1983,
ongoing performance checks must be
compared with established performance
criteria to determine if the results of
analyses are within accuracy and
precision limits expected of the method.
10.1.1 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 10.2.
10.1.2 In recognition of the rapid
advances occurring in chromatography,
the analyst is permitted certain options to
improve the separations or lower the cost
of measurements. Each time such
modifications are made to the method,
the analyst is required to repeat the
procedure in Section 10.2.
10.1.3 The laboratory must spike and
analyze a minimum of 10% of all samples
to monitor continuing laboratory
performance. This procedure is described
in Section 10.4.
10.2 To establish the ability to generate
acceptable accuracy and precision in the
use of this method, the analyst must
perform the following operations.
10.2.1 For each commercial PCB
mixture or individual PCB isomer
normally measured, prepare a PCB
spiking concentrate, in isooctane within
the range of 40 to 60 mg/mL.
10.2.2 Using a microsyringe, add 100
fjL of the PCB concentrate to each of a
minimum of four 100 g aliquots of PCB-
free oil. A representative waste oil may
be used in place of the clean oil, but one
or more additional aliquots must be
analyzed to determine the PCB
background level, 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 7.
10.2.3 Calculate the average percent
recovery, (R), and the relative standard
deviation (s) of the concentration found.
Waste oil background corrections must be
made before R calculations are
performed.
10.2.4 Using the appropriate data from
Tables 1, 2, and 3, determine the
recovery and single operator precision
expected for the method and compare
these results to the values calculated in
Section 10.2.3. If the data are not
comparable, the analyst must review and
remedy potential problem areas and
repeat the test.
-------
10.2.5 After January 1, 1983, the
values for R and s must meet method
performance criteria provided by the
USEPA, Environmental Monitoring and
Support Labortory, Cincinnati, Ohio
45268, before any samples may be
analyzed.
10.3 The analyst must calculate
method performance of the laboratory for
each spike concentration and parameter
being measured.
10.3.1 Calculate upper and lower
control limits for method performance:
Upper Control Limit (UCL) = R + 3 s
Lower Control Limit (LCL) = R - 3 s
where R and s are calculated as in
Section 10.2.3. The UCL and LCL can be
used to construct control charts5 that are
useful in observing trends in
performance. After January 1, 1983, the
control limits above must be replaced by
method performance criteria provided by
the USEPA.
1O.3.2 The laboratory must develop and
maintain separate accuracy statements of
laboratory performance for waste oil
samples. An accuracy statement for the
method is defined as R ± s. The accuracy
statement should be developed by the
analysis of 4 aliquots of waste oil, as
described in Section 10.2.2, followed by
the calculation of R and s. Alternately, the
analyst may use. four waste oil data
points gathered through the requirement
for continuing qualitV'Control in Section
10.4. The accuracy statements should be
updated regularly.
10.4 The laboratory is required to
collect a portion of their samples in
duplicate to monitor spike recoveries. The
frequency of spiked sample analysis must
be at least 10% of all samples or one
sample per month, whichever is greater.
One aliquot of the sample must be spiked
and analyzed, as described in Section
10.2.2, at two times the background level.
If the recovery for a particular parameter
does not fall within the control limits for
method performance,, the results reported
for the parameter in all samples
processed as part of the same set must
be qualified, as described in Section 11.9.
The laboratory should monitor the
frequency of data so qualified to ensure
that it remains at or below 5%.
10.5 Before processing any samples,
the analyst should demonstrate through
the analysis of a PCB-free oil sample, that
all glassware and reagents are free of
interferences. Each time a set of samples
is analyzed or there is a change in
reagents, a laboratory reagent blank
should be processed as a safeguard
against contamination.
10.6 It is recommended that the
laboratory adopt additional quality
assurance practices for use with this
method. The most productive, specific
practices depend upon the needs of the
laboratory and the nature of the samples.
Field duplicates may be analyzed to
monitor the precision of the sampling
technique. When doubt exists regarding
the identification of a peak on the
chromatogram, confirmatory techniques
such as GC with a dissimilar column,
specific element detector, or MS must be
used. Whenever possible, the laboratory
should perform analysis of standard
reference materials and participate in
relevant performance evaluation studies.
10.7 Analyze the LCS, Section 5.7,
daily before any samples are analyzed.
Instrument status checks, calibration
curve validation and long-term precision
are obtained from these data. In addition,
response data obtained from the LCS can
be used to estimate the concentration of
the unknowns. From this information, the
appropriate standard dilutions can be
determined for single-point calibrations.
10.8 Analyze on a quarterly basis a
Quality Control Sample (Section 5.4.8.) of
PCBs in oil or whenever new standard
dilutions are prepared.
10.8.1 The results of the Quality
Control Sample should agree within 1 5%
of the true value. If they do not, the
analyst must check each step in the
standard preparation procedure to resolve
the problem.
11. Calculations
11.1 Locate each PCB in the sample
chromatogram by comparing the
retention time of the suspect peak to the
retention data gathered from analyzing
standards and interference-free Quality
Control Samples. The width of the
retention time window used to make
identifications should be based upon
measurement of actual retention time
variations 'of standards over the course of
a day. Three times the standard deviation
of a retention time for each PCB can be
used to calculate a suggested window
size; however, the experience of the
analyst should weigh heavily in the
interpretation of chromatograms.
11.2 If the response for any PCB peak
exceeds the working range of the system,
dilute according to Section 7.3.5.
11.3 If accurate measurement of the
peaks in the PCB elution area of the
chromatogram is prevented by the
presence of interferences, further
cleanup is required.
11.4 If the parent Aroclors or PCBs are
identified in the sample, calibrate
according to Section 9. The concentration
of the PCBs in the sample is calculated by
comparing the sum of the responses for
each PCB in the standard to the sum of
all of the PCBs in the sample. This is
particularly important as sample
concentrations approach within 20% of
50 mg/kg or any other EPA-regulated
concentration. If calculations are based
upon a single PCB peak or upon a small
percentage of the total PCB peaks,
serious errors may result. Peaks
comprising less than 50% of the total can
be disregarded only if (1) interference
problems persist after cleanup, (2) the
source of PCBs is obvious, or (3) the
concentration of PCBs is not within ±20%
of an EPA-controlled value such as 50
mg/kg.
11.4.1 Measure the peak height or
peak area of each peak identified as a
PCB (Section 11.1) in both the sample
and the standard.
11.4.2 Use the following formula to
calculate the concentration of PCBs in the
sample:
B x V
Concentration mg/kg = .-—rr*-
where:
A =
B =
Sum of standard
Peak Heights (areas)
ng of standard injected
Sum of sample.
Peak Heights (areas)
= mm/ng
= mm/fjL
pL injected
Vt = dilution volume of sample in mL
W = weight of the sample in grams
11.5 If the parent Aroclors or source of
PCBs is not apparent, calculate the
concentration according to the procedure
of Webb and McCall.6 The concentration
of the PCBs in each peak is determined
individually then added together to
determine the total PCB content of the
sample. Each PCB identified in the
-------
sample must be included in these
calculations.
11.5.1 Small variations between
Aroclor batches make it necessary to
obtain standards prepared from a specific
source of Aroclors. Primary dilutions of
these reference Aroclors will be available
in 1981 from the USEPA, Environmental
Monitoring and Support Laboratory,
Quality Assurance Branch, Cincinnati,
Ohio 45268.
11.5.2 Analyze a standard mixture of
Aroclors 1242, 1254, and 1260 under the
conditions shown in Figures 3, 5, and 6.
Analyze the sample under the same
conditions. Compare the resulting
standard chromatograms to those shown
in Figures 3, 5, and 6. Each PCB peak
must be resolved as well or better than
those shown in the figures. Determine
the relative retention time (RRT) of each
peak in the standards with respect to
p,p'-DDE or assign the RRT shown in the
figures to the corresponding peak in the
standard. Identify the RRT of each PCB in
the sample by comparing the sample
chromatogram to the standard
chromatograms.
11.5.3 Identify the most likely Aroclors
present in the sample, using the
identification Flow Chart, Figure 8.
11.5.4 Analyze standards according to
Section 9, using the appropriate Aroclors.
71.5.5 Determine the instrument
response factor (A) for each individual
PCB, using the following formula:
A =
Peak Height (area)
gix mean weight %
100
where:
Ngi = Ng of Aroclor standard injected
(mean weight percent is obtained
from Tables 4 through 9).
11.5.6 Calculate the concentration of
each PCB in the sample, using the
following formula:
p y W
Concentration rng/kg = A x w
where:
A = Response factor from 11.5.5
Peak Height (areas) of sample mm/yuL
B=-
fjL injected
Vt = dilution volume of sample in mL
W = weight of sample in grams
The concentration of each PCB must be
calculated and added together to obtain
the total amount of PCBs present.
11.6 Report all data in mg/kg.
11.7 Round off all data to two
significant figures.
11.8 Add all Aroclors and report what
was used as the standard. For example,
57 mg/kg measured as Aroclor 1260 or
57 mg/kg measured as Aroclors 1242
and 1260.
11.9 Data for the affected parameters
of samples processed as part of a set
where the laboratory spiked sample
recovery falls outside the control limits in
Section 10.4 must be labeled as suspect.
11.10 Determine the actual recovery
for electron capture analyses of each
sample in the jjncorrected 40- to 50-
mg/kg concentration range (See Section
3.4). Report th|e corrected value and the
recovery.
12. Precision and Accuracy
12.1 The dafa shown in Tables 1
through 3 were generated using the
recommended'procedures described in
this method to analyze both spiked and
nonspiked oil samples of varying degrees
of complexity. [Data for both the HED and
ECD were generated by the USEPA,
Environmental Monitoring and Support
Laboratory, Physical and Chemical
Methods Branch, Cincinnati, Ohio 45268.
t
References^
1. Federal Register, 40 CFR, Part 761,
July 1,1981.
i
2. Eichelberger, J. W., L. E. Harris, and
W. L. Budde. Anal. Chem., 46, 227
(1974). i
i
i
3. Federal Register, 40 CFR, Sections
136.4 and 136.5, July 1, 1981.
4. White, L. D., et al., AIHA Journal, 31,
22S, (197()).
5. Handbookjof Analytical Quality
Control in [Water and Wastewater
Laboratories. EPA-600/4-79-019.
6.
USEPA, Environmental Monitoring
and Support Laboratory, Cincinnati,
Ohio 45268, March 1979.
Webb, R. G. and A. C. McCall. J.
Chrom. Sci., 11, 366 (1973).
8
-------
Table 1. Accuracy and precision using
Dilution ' Method
Ratio Detector Cleanup
100:1 HED
100:1 ECD
100.1 HED
1OO:1 ECD
100:1 HED
ECD
HED
ECD
HED
ECD
HED
ECD
HED
ECD
HED
ECD
HED
ECD
HED
ECD
HED
ECD
HED
ECD
HED
ECD
HED
ECD
None
None
None
None
8.1
8.1
8.1
8.1
8.2
8.2
8.2
8.2
8.3
8.3
8.3
8.3
8.4
8.4
8.4
8.4
8.5
8.5
8.5
8.5
8.6
8.6
8.6
8.6
spiked motor oil'
Spike A roc lor
mg/kg Spiked
30.3
30.3
31.1
31.1
3O.3
30.3
31.1
31.1
30.3
30.3
31.1
31.1
30.3
30.3
31.1
31.1
30.3
30.3
31.1
31.1
30.3
30.3
31.1
31.1
30.3
31.1
30.3
31.1
1242
1242
1260
126O
1242
1242
1260
1260
1242
1242
1260
1260
1242
1242
1260
1260
1242
1242
1260
1260
1242
1242
1260
1260
1242
1242
1260
1260
Avg.
Cone.
Found
mg/kg
28.2
26. 71
27.2
23.5
28.4
25. 4 1
28.1
24.3
30.7
27.31
30.9
31.0
30.3
25.3'
23.5
30.5
23.4
26.41
23.4
23.5
31.9
23.4^
33.6
30.9
34.4
23.4'
23.7
27. 0
(Precision)
fie/. Std.
Deviation
%
4.2
5.7
2.0
2.2
11.5
6.1
8.0
7.8
2.4
10.2
3.6
8.6
8.6
5.0
4.7
6.5
5.8
5.3
5.2
4.5
8.5
3.0
9.2
5.5
3.8
4.4
4.2
4.6
(Accuracy)
Percent
Recovered
93.1
88.1
87.5
76.8
93.7
83.8
90.3
78.1
101.
90.1
99.4
99.7
100.
95.4
95.8
99.0
97.0
87.1
94.5
105.
75.9
77.2
108.
99.4
107.
77.2
96.7
86.7
Number
of
Dilutions
5
3
5
3
3
3
3
3
4
4
4
4
3
3
3
3
3
3
3
3
3
2
3
3
4
4
4
4
1 Severe interference problems in elution area of 1242. Measurement based upon only 3 of the 10 normally resolved major peaks.
Cleanup technique. Sections 8.1, 8.2, 8.3, 8.4, 8.5, and 8.6 did not improve the quality of the 1242 chromatogram. If this were an
unknown sample, it would be impossible to qualitatively identify the presence ofAroclor 1242 using ECD. The HED provided an
interference-free chromatogram.
-------
i
Table 2. Accuracy and precision using waste transformer fluids
Dilution
Sample ' Ratio
A 100:1
A
A
A
A
A
A
A
A
A
A
A
A
A
B 1000:1
B
B
B
C 1000:1
C
C "
C
1 A - dark waste oil
Method
Detector Cleanup
ECD None
HED None
ECD 8. 1
HED 8. 1
ECD 8.2
HED 8.2
ECD 8.3
HED 8.3
ECD 8.4
HED 8.4
ECD 8.5
HED 8.5
ECD None
HED None
ECD None
HED
ECD
HED
ECD None
HED
ECD
HED
1260 Avg.(D)
Spike Cone.
mg/kg Found
22.6
27.0
22.8
29.7
22.4
28.2
22.7
27.8
20.9
30.2
23.8
28.6
27.0 45.0
27.0 55.2
452
471
455 875
455 916
284
300
300 607
300 686
(Precision)
Rel. Std.
Deviation
%
3.6
1.7
2.5
1.4
1.0
2.2
1.3
2.8
__
0.3
4.1
3.3
1.5
0.8
1.2
0.5
2.0
1.2
1.4
3.6
3.9
• (Accuracy}
Percent
Recovered
__
__
__
....
—
-.
—
__
__
__
..
91
102
..
96
99
__
104
114
Number
of
Dilutions
72
72
72
7
32
32
32
32
1
1
72
72
7
72
72
7
72
72
7
7
72
7
B - black waste oil with suspended so/ids \
C - clear waste oil
D - all samples contained Arocfor 1260
2 Duplicate analyses made
at each dilution
10
-------
Table 3. A ccuracy and precision and limit of detection data results of analyses of
Shell transformer fluid spiked with PCBs at 5.0 and 27 mg/kg
Electron Capture Detector
(100:1 dilution)
A roc lor
1221
1242
1254
1260
Spike
(mg/kg)
5.0
5.0
5.0
5.0
Number of
Analyses
7
14
7
14
Electrolytic
Avg.
(mg/kg)
7.5
3.8
4.1
4.7
Standard
Deviation
0.43
0.18
0.08
0.18
Percent
Recovery
150
76
82
94
MDL*
(mg/kg)
1.4
0.5
0.2
0.5
Conductivity Detector
(100:1 dilution)
Aroclor
1221
1242
1254
1260
Spike
(mg/kg)
5.0
5.0
5.0
5.0
Number of
Analyses
6
7
6
7
Avg.
(mg/kg)
7.5
5.9
5.8
5.4
Standard
Deviation
0.23
0.17
0.16
0.10
Percent
Recovery
150
118
116
108,
Mm i
(mg/kg)
0.7
0.5
0.5
0.3
Shell Transformer Oil + 27 ppm Aroclor 1260
(100:1 dilution)
Spike Number of Avg. Rel. Std. Percent
Detector (mg/kg) Analyses (mg/kg) Deviation, % Recovery
ECD
HED
27
27
14
7
24.0
28.3
.70
2.1
89
105
1 MDL = Method Detection Limit at 9.9% confidence that the value is not zero.
Note: At these values it would be impossible to identify Aroclor patterns with
any degree of confidence. 1 mg/kg appears to be a reasonable MDL.
MDL = f (n=1,.99)
where:
MDL = the method detection limit
(n-1,.99) = the students' t value appropriate for a 99%
confidence level and a standard deviation
estimate with n-1 degrees of freedom.
S = standard deviation of the replicate analyses
Table 4. Composition of Aroclor 7227'
Mean
Weight Relative Number of
RRTZ Percent Std. Dev.s Chlorines*
11
14
16
19
21
28
32
r37
Uo
Total
31.8
19.3
10.1
2.8
20.8
5.4
1.4
1.7
93.3
15.8
9.1
9.7
9.7
9.3
13.9
30.1
48.8
1
1
2
2
2
2-1 85%
3J 75%
2-1 70%
3-190%
3
3
1 Data obtained from Webb and McCall.e
2 Retention time relative to p.p'-DDE=1 OO.
Measured from first appearance
of solvent. Overlapping peaks that are
quantitated as one peak are bracketed.
3 Relative standard deviation of 17 analyses
(as percentages of the mean of the results).
4 From GC/MS data. Peaks containing
mixtures of isomers of different chlorine
numbers are bracketed.
11
-------
Table 5. Composition ofAroclor 12321
Mean
RRT*
11
14
16
r20
L27
28
32
37
40
47
54
58
70
78
Total
Weight
Percent
16.2
9.9
7.1
17.8
9.6
3.9
6.8
6.4
4.2
3.4
2.6
4.6
1.7
94.2
Relative
Std. Dev.s
3.4
2.5
6.8
2.4
3.4
4.7
2.5
2.7
4.1
3.4
3.7
3.1
7.5
Number of
Chlorines 4
/
7
2
2
2
2-i
3J
3
3
3
4
3-i
4\
4
4~\
5-1
4
40%
60%
33%
67%
90%
10%
, Data obtained from Webb and McCall.6
z Retention time relative to p,p'-DDE=100. Measured from first appearance
of solvent. Overlapping peaks that are quantitated as one peak are bracketed.
3 Relative standard deviation of four analyses fas percentages \}f the mean of the results).
4 From GC/MS data. Peaks containing mixtures of isomers of [different chlorine numbers
are bracketed.
•
Table 6. Composition ofAroclor 1242' \
RRn
11
16
21
28
32
37
40
47
54
58
70
78
84
98
104
Mean
Weight
Percent
1.1
2.9
11.3
11.0
6.1
11.5
11.1
8.8
6.8
5.6
10.3
3.6
2.7
1.5
2.3
[
i
Relative \
Std. Dev.3 \
35.7
4.2 !
3.0
5.0
I
4.7 '
5.7 \
6.2 \
4.3 |
2.9 \
3.3 i
2.8 ;
4.2 \
9.7 I
9.4 I
16.4 i
Number of
Chlorines*
1
2
2
2-1 25%
3-1 75%
3
3
3
4
3-i 33%
4-167%
4
4-i 90%
5J 70%
4
5
5
5
125
146
Total
1.6
J.O
98.5
20.4
19.9
i 55%
I 75%
I 75%
' Data obtained from Webb and McCall.6
2 Retention time relative to p,p'-DDE= 100. Measured from fftst appearance of solvent.
3 Relative standard deviation of six analyses (as percentages of the mean of the results).
4 From GC/MS data. Peaks containing mixtures of isomers of different chlorine
numbers are bracketed. \
12
-------
Table 7.
RRT2
27
28
32
47
40
47
54
58
70
78
84
98
104
1 72
725
146
Total
Composition of Aroc/or 724S1
Mean
Weight
Percent
7.2
5.2
3.2
8.3
8.3
15.6 .
9.7
9.3
19.0
6.6
4.9
3.2
3.3
1.2
2.6
1.5
103.1
Relative
Std. Dev.3
23.9
3.3
3.8
3.6
3.9
1.1
6.0
5.8
1.4
2.7
2.6
3.2
3.6
6.6
5.9
10.0
Number of
- Chlorines*
2
3
3
3
3-i 85%
4-1 15%
4
3-i 70%
4
4-t 80%
5J 20%
4
5
5
4-i 70%
5J90%
5
5-i 90%
ffJ70%
5-1 55%
6J75%
1 Data obtained from Webb and McCall.e
2 Retention time relative to p,p'-DDE=100. Measured from first appearance of solvent.
3 Relative standard deviation of six analyses (as percentages of the mean of the results).
4 From GC/MS data. Peaks containing mixtures of isomers of different numbers
are bracketed.
TableS. Composition of Aroc/or 72541
Mean
RRT*
47
54
58
70
84
98
104
125
146
16O
174
160
174
203
232
Weight
Percent
6.2
2.9
1.4
13.2
17.3
7.5
13.6
15.0
1O.4
1.3
8.4
1.3
8.4
1.8
1.0
Relative
Std. Dev.3
3.7
2.6
2.8
2.7
1.9
5.3
3.8
2.4
2.7
8.4
5.5
8.4
5.5
18.6
26.1
Number of
Chlorines'1'
4
4
4
4-, 25%
5J 75%
5
5
5
5-1 70%
ffJ 30%
5-1 30%
ffJ 70%
6
6
6
6
6
7
Total 700.0
1 Data obtained from Webb and
1 Data obtamea rrom weoo ana iviu^aii.-
2 Retention time relative to p,p'-DDE=100. Measured from first appearance of solvent.
3 Relative standard deviation of six analyses (as percentages of the mean of the results).
4 From GC/MS data. Peaks containing mixtures of isomers of different chlorine
numbers'are bracketed.
13
-------
Table9. Composition of Aroclor 72601
/?/?p
70
84
f-98
i*W4
117
125
146
160
174
203
r232
1-244
280
332
372
448
528
Total
Mean
Weight
Percent
2.7
4.7
3.8
3.3
12.3
14.1
4.9
12.4
9.3
9.8
11.0
4.2
4.0
.6
1.5
98.6
\
Relative
Std. Dev.3 \
6.3
1.6 \
3.5
6.7 i
3.3
3.6 i
2.2 \
2.7
4.0
3.4 \
2.4
5.0 ;
8.6 \
25.3
10.2
Number of
Chlorines*
5
5
6-l
5 50%
6^40%
6
5-i 15%
6-185%
6
6-t 50%
7-150%
6
6-] 10%
7-1 90%
5T 70%6
7-1 90%
7
7
8
8
8
1 Data obtained from Webb and McCall.5
3 Retention time relative to p.p'-DDE=10O. Measured fromfirst appearance of solvent.
Overlapping peaks that are quantitated as one peak are bracketed.
3 Relative standard deviation of six analyses (as percentages oft the mean of the results).
4 From GC/MS data. Peaks containing mixtures of isomers of different chlorine
numbers are bracketed. [ •
6 Composition determined at the center of peak 104. \
8 Composition determined at the center of peak 232. \
21
Column: 3% OV-1
Detector:
Electron Capture
Column Temperature:
150°C.
21
37
Column: 3% OV-1
Detector: Electron Capture
Column Temperature: 150°C.
0 4 8 O
Time, min.
Figure 1. Gas chromatogram of Aro-
clor 1221. Figure 2.
_L
2 4
Time. min.
i
Gas chromatogram of Aroclor 1232.
14
-------
37
Column: 3% OV-1
Detector: Electron Capture
Column Temperature: J7O°C.
_L
8
Time, min.
12
Figure 3. Gas chromatogram of Aroclor 1242.
16
70
Column: 3% OV-1
Detector: Electron Capture,
Column Temperature: 170°C.
0 4 8 12
Time, min.
Figure 4. Gas chromatogram of Aroclor 1248.
16
20
15
-------
Column: 3% OV-1
Detector: Electron Capture,
Column Temperature: 170°C.
12 16
Time, min.
Figure 5. Gas chromatogram ofAroclor 1254.
Column: 3% OV-1
Detector: Electron Capture,
Column Temperature: 170°C.
0 4
Figure 6.
8 12 16 2O 24 28\ 32 36 4O 44
Time, min.
Gas chromatogram ofAroclor 1260.
16
48 52 56 6O 64
-------
Column: 3% OV-1
Detector: Hall 70O-A
Program: 120°C. -6°/Minute to 22O°C.
146
O
Q
04 8 12 16 20 24
Time, min.
Figure 7. Gas chromatogram of PCB locator mixture.
28
32
17
-------
RRT of first peak < 47?
YES
NO
Is there a distinct
peak with RRT 78?
RRT47r58?
YES
I V
YES
NO
Use 1242 for
peaks < RRT84
Use 1242 for
peaks < RRT 70
Is there a distinct
peak with RRT 117?
YES
NO
Use 1254 for all
peaks < RRT174
Use 1260 for
all other peaks
Figure 8. Chromatogram division flowchart.
18
Use 1254
for\peaks
-------
-------
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