G U I D E L I N E S F O R E N V I R O N M E N TA L M A N A G E M E N T

DETERMINATION OF
POLYCHLORINATED
BIPHENYLS (PCBs) IN WASTE
OILS BY GAS
CHROMATOGRAPHY WITH
ELECTRON CAPTURE
DETECTOR
EPA VICTORIA METHOD NUMBER: 6013
 GUIDELINES FOR ENVIRONMENTAL MANAGEMENT

D E T E R M I N AT I O N O F P O LY C H L O R I N AT E D B I P H E N Y L S ( P C B s ) I N
W A S T E O I L S B Y G A S C H R O M AT O G R A P H Y W I T H E L E C T R O N
CAPTURE DETECTOR
EPA Victoria Method Number: 6013

EPA Victoria
40 City Road, Southbank
Victoria 3006 AUSTRALIA

Publication 886.1
ISBN 0 7306 7629 3

October 2003
CONTENTS

1 BACKGROUND ............................................................................................................................................... 1

2 SCOPE .......................................................................................................................................................... 1

3 SUMMARY..................................................................................................................................................... 1

4 INTERFERENCES............................................................................................................................................. 1

5 APPARATUS.................................................................................................................................................. 2

6 REAGENTS.....................................................................................................................................................3

7 SAMPLE COLLECTION, PRESERVATION, AND HANDLING ................................................................................. 6

7.1 SAMPLE BOTTLE PREPARATION....................................................................................................................... 6
7.2 SAMPLE PRESERVATION. .............................................................................................................................. 6
7.3 SAMPLE COLLECTION. ................................................................................................................................. 6
8 CHROMATOGRAPHIC OPERATING CONDITIONS .............................................................................................. 6
8.1 DB5 OR EQUIVALENT COLUMN. ..................................................................................................................... 6
8.2 DB608 OR EQUIVALENT COLUMN. ................................................................................................................. 6
9 PROCEDURE ..................................................................................................................................................7
9.1 SAMPLE PREPARATION .................................................................................................................................7
9.2 REMOVAL OF INTERFERENCES .........................................................................................................................7
9.3 COLUMN ADSORPTION CHROMATOGRAPHY CLEANUP ............................................................................................ 9
9.4 CALIBRATION ...........................................................................................................................................10
9.5 RETENTION TIME WINDOWS ........................................................................................................................ 12
9.6 GAS CHROMATOGRAPHIC ANALYSIS OF SAMPLE EXTRACTS................................................................................... 12
9.7 CALCULATION .......................................................................................................................................... 14
10 REPORTING RESULTS ............................................................................................................................... 15

11 QUALITY CONTROL .................................................................................................................................. 15

11.1 INITIAL GENERATION OF ACCURACY AND PRECISION DATA ................................................................................. 15
11.2 CALIBRATION VERIFICATION...................................................................................................................... 16
11.3 MATRIX SPIKE, SURROGATE RECOVERIES AND DUPLICATES............................................................................... 17
APPENDIX I PREPARATION OF CLEAN TRANSFORMER OIL ......................................................................................18

APPENDIX II SULFUR CLEANUP METHODS ............................................................................................................18

APPENDIX III EXAMPLE AROCLOR® CHROMATOGRAMS........................................................................................ 20

APPENDIX IV REFERENCES...................................................................................................................................27
 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

1 BACKGROUND 4 INTERFERENCES

Methods that have been developed for the analysis Most waste oils will consist of a complex mixture of
of polychlorinated biphenyls (PCBs) in used hydrocarbons such as n-alkanes, isoalkanes,
insulating oil are not usually applicable to the naphthenes and paraffins. These matrix
analysis of PCBs in waste oil. This method is to components will most likely interfere with the PCB
serve specifically as a method for the analysis of determination and a sample preparation procedure,
PCBs in waste oil. The method is applicable to the consisting of least an acid cleanup followed by
determination of commercial mixtures of PCBs in adsorption chromatography, is required before
hydrocarbon based waste oils using gas analysis and quantification.
chromatography (GC) with capillary columns. The
Sources of interference include:
method is based on US EPA methods SW846 8082A
4.1 Contaminated solvent, reagents or sample
[1] and EPA-600/4/81-045 [2].
processing hardware.

4.2 Contaminated GC carrier gas, parts, column

2 SCOPE
surfaces, or detector surfaces.
This method sets out a procedure for the
determination of polychlorinated biphenyls (PCBs), 4.3 Compounds which are extracted from the
®
as Aroclors , in extracts from waste oil by GC using sample matrix to which the detector responds, such
capillary columns with electron capture detectors as single-component chlorinated pesticides,
(ECD). The method is intended for use to determine including dichlorodiphenyltrichloroethane (DDT)
whether waste oils contain PCBs at the regulatory analogues dichlorodiphenylethylene (DDE) and
decision level of 2mg/kg. dichlorodiphenyldichloroethane (DDD).

4.4 Phthalate esters introduced during sample

3 SUMMARY
preparation. Phthalate esters are easily extracted
The sample is diluted with solvent. The resulting from common flexible plastics. They can be
solution is treated to remove interfering substances minimised by avoiding contact between the samples
using a combination of acid cleanup and adsorption and any plastic materials.
chromatography. A small volume of the resulting
4.5 Cross-contamination of clean glassware.
solution is injected into a capillary gas
Glassware must be scrupulously cleaned by rinsing
chromatographic column equipped with an electron
with the last solvent used, followed by detergent
capture detector and recorded as a chromatogram.
washing with hot water and rinses with tap water
The test method is made quantitative by comparing
and organic free reagent water. Drain the glassware,
the sample chromatogram with a chromatogram of a
and dry it in an oven at 130°C for several hours.
known quantity of one or more standard Aroclors®,
obtained under the same conditions.

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

4.6 Sulfur (S8) (usually present in crude oils) can 5.2 Beakers.
cause chromatographic interferences. An additional
Appropriate sizes.
sulfur removal step may be required when using the
cleanup steps described in this method. Refer to
5.3 Concentrator tube.
Appendix II for information on how to remove sulfur
10mL graduated. Calibration must be checked.
interferences.
Ground glass stopper is used to prevent evaporation
The sensitivity of ECD detectors is reduced by
of solvent.
mineral oils due to quenching of the detector
response by high boiling hydrocarbons. The degree
5.4 Erlenmeyer flasks.
of error is matrix dependent and is not predictable
Appropriate sizes.
for samples of unknown origin. Retention time
shifts for individual congeners have also been found
5.5 Evaporative flask.
to occur in the presence of mineral oil.
500mL. Attach to concentrator tube with springs.
All calibration solutions must contain PCB-free
transformer oil at the same concentration as the
5.6 Gas chromatograph.
concentration of waste oil that is expected in the
sample solutions that are injected into the GC (i.e. An analytical system complete with gas
PCB-free transformer oil must be diluted with the chromatograph suitable for on-column and spilt-
solvent to the same extent that the waste oil matrix splitless injection and all required accessories
is diluted) including syringes, analytical columns, gases,
electron capture detector (ECD) and
recorder/integrator or data system.
5 APPARATUS
The gas lines (carrier gas and make up gas) shall be
fitted with water vapour and oxygen traps.
5.1 Adsorption Column:

400 mm long x 19 mm ID; with Pyrex® glass wool at

5.7 GC Columns.
the bottom and a teflon stopcock.
Two columns are used, the DB-5 is used for primary
Fritted glass disks are difficult to decontaminate
analysis and the DB608 or DB1701 for confirmation.
after highly contaminated extracts have been passed
Columns of other dimensions may be used.
through. Columns without frits may be purchased.
A fused-silica capillary column chemically bonded
Use a small pad of Pyrex® glass wool to retain
with DB-5 or equivalent.
adsorbent. Prewash the glass wool pad with 50 mL
of acetone followed by 50 mL of elution solvent prior Length = 30m
Internal diameter = 0.25 or 0.32mm
to packing the column with adsorbent.
Film thickness = 1µm

EPA Victoria
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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

A fused-silica capillary column chemically bonded 5.13 Vials.

with 35 percent phenyl methylpolysiloxane (DB608)
With aluminium or polytetrafluoroethylene (PTFE)-
or equivalent.
lined caps and various pipettes and beakers for
Length = 30m making dilutions.
Internal diameter = 0.25mm
Film thickness = 1µm
5.14 Volumetric glassware.

A fused-silica capillary column chemically bonded Appropriate for making dilutions (tolerance better
with 14percent cyanopropylmethylsiloxane (DB1701) than ± 0.4%).
or equivalent.

Length = 30m 6 REAGENTS

Internal diameter = 0.53mm
Film thickness = 1µm
All reagents and materials, including those for
5.8 Kudeerna-Danish. cleanup, shall be free from PCB contamination and
compounds that respond to the ECD.
(K-D) evaporative concentrator apparatus.

6.1 Concentrated sulfuric acid.

5.9 Muffle Furnace
(96% to 98%) Analytical grade.
5.10 Reagent bottles.
6.2 Florosil® cartridges.
Appropriate sizes.
40µm particles, 60Å pores. Single use one gram
5.11 Vacuum manifold. cartridges are used in this method but larger
cartridges may be used. Recovery data must be
Consisting of glass vacuum basin, collection rack
developed for any size cartridges that are used.
and funnel, collection vials, replaceable stainless
steel delivery tips, built in vacuum bleed valve and
6.3 Granular Florosil®
gauge. The system is connected to a vacuum pump
or water aspirator through a vacuum trap made from (PR grade or equivalent). Activate the Florosil® by
a 500 mL sidearm flask fitted with a one-hole heating in a glass container loosely covered with
stopper and glass tubing. aluminium foil in an oven at 130°C overnight. Cool
the Florosil® in a dessicator before use.
5.12 Vials.
6.4 Insulating oil.
Glass of appropriate volume with teflon-lined screw-
caps or crimp tops. Fresh, unused and PCB free. A portion of the oil
diluted in solvent must be analysed to determine if it
is free of PCBs and compounds that interfere with

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

PCBs. The oil may have to be subjected to a cleanup 6.9 Solvents.

to remove inteferences to PCBs. The method of
Hexane or isooctane (2,2,4-trimethylpentane).
cleanup is left to the discretion of the analyst. An
All solvents should be pesticide quality or
example of a cleanup method is given in Appendix I.
equivalent, and each lot of solvent should be
determined to be free of phthalates.
6.5 Reagent water.
The choice of solvent is left to the analyst and,
All references to water in this method refer to
unless specified, any reference to solvent in this
organic-free reagent water.
method means either hexane or iso-octane.

6.6 Silica cartridges.

6.10 Stock standard solutions.
40µm particles, 60Å pores. Single use one gram
(1000mg/L) each of Aroclor® 1016, Aroclor® 1221,
cartridges are used in this method but larger
Aroclor® 1232, Aroclor® 1242, Aroclor® 1248,
cartridges may be used. Recovery data must be
Aroclor® 1254, Aroclor® 1260. These may be
developed for any size cartridges that are used.
prepared from pure standard materials or purchased
as certified standard solutions.
6.7 Silica gel.
Prepare stock standard solutions by accurately
100/200 mesh (Davison Chemical grade 923 or
weighing 0.0100 g of pure compound. Dissolve the
equivalent). Before use, activate for at least 16
compound in solvent and dilute to volume in a 10mL
hours at 130°C in a shallow glass tray, loosely
volumetric flask.
covered with foil. Deactivate it to 3.3% by adding
3.3 g of reagent water to 100 g of silica gel in a Commercially prepared stock solutions may be used
500mL glass jar. Mix the contents thoroughly and at any concentration if they are certified by the
allow to equilibrate for six hours. Store the manufacturer or an independent source.
deactivated silica gel in a sealed glass jar inside a
dessicator. 6.11 Calibration Solutions

A standard containing a mixture of Aroclor® 1016

6.8 Sodium sulfate.
and 1260 will include many of the peaks represented
(Granular, anhydrous), Na2SO4. Purify by heating at in the other five Aroclor® mixtures. As a result a
400°C for four hours in a shallow tray, or by multi-point initial calibration employing a mixture of
precleaning the sodium sulfate with Aroclors® 1016 and 1260 at five concentrations
dichloromethane. A method blank must be should be sufficient to demonstrate the linearity of
analysed in order to demonstrate that there is no the detector response without the necessity of
interference from sodium sulfate. performing multi-point initial calibrations for each of
the possible Aroclors®. In addition such a mixture
can be used to demonstrate by the absence of peaks

EPA Victoria
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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

that a sample does not contain peaks that represent Prepare separate standards of Aroclors® 1221, 1232,
either Aroclor® 1016 or Aroclors® 1260. This 1242, 1248 and 1254. The concentrations of each
standard can also be used to determine the Aroclor® should correspond to the decision level
concentrations of either Aroclor® 1016 or Aroclor® PCB concentration in waste oils of 2mg/kg.
1260, should they be present in the sample.
Store the standard solutions in the dark at 4°C in
The lowest concentration calibration standard glass containers sealed with a PTFE lid. When a
establishes the method quantitation limit based on batch of standards is prepared, it is recommended
the final volume of extract (or sample). At least one that aliquots of that batch be stored in individual
of the calibration standards should correspond to a small vials. All stock standards must be replaced
concentration below that necessary to meet the after one year, or sooner if routine quality control
regulatory compliance limit of 2mg/kg. checks indicate a problem. All other standard
solutions must be replaced after one month, or
All calibration solutions must contain PCB free
sooner if routine quality control checks indicate a
insulating oil at the same concentration as the
problem.
concentration of waste oil that is expected in the
sample solutions that are injected into the GC.
6.12 Surrogate standards

6.11.1 Initial calibration solutions. The performance of the method should be monitored
using surrogate compounds. Surrogate standards
Prepare a minimum of five calibration standards
should be added to all samples, method blanks,
containing equal concentrations (w/v) of both
matrix spikes, and calibration standards.
Aroclor® 1016 and Aroclor® 1260 by dilution of stock
standard with solvent. The concentration should Decachlorobiphenyl (C209) must be used as a
correspond to the expected range of concentrations surrogate, and is added to each sample prior to
found in real samples and should bracket the linear extraction. Prepare a solution of C209 in solvent.
range of the detector. The recommended spiking solution concentration is
0.1 mg/L.
6.11.2 Individual Aroclor® standard solutions.
Prepare a minimum of five calibration standards
Single standards of each of the other five Aroclors® containing C209 in solvent. The concentration
(1221, 1232, 1242, 1248 and 1254) are necessary for should correspond to the expected range of
pattern recognition. When employing the model of concentrations added to samples and should
linear calibration through the origin, these bracket the linear range of the detector. Each
standards are also used to determine a single-point surrogate standard solution must contain PCB free
®
calibration factor for each Aroclor , assuming the insulating oil at the same concentration as the
Aroclor® 1016/1260 mixture has been used to concentration of waste oil that is expected in the
demonstrate the linearity of the detector. sample solutions that are injected into the GC.

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

6.13 Laboratory control standard. 7.3 Sample collection.

Prepare a laboratory control standard (LCS) by If practical, mix the waste oil in the sample source
spiking a PCB free oil typical of the matrix normally prior to sampling. Fill a large container, such as a
analysed such as used lubricating oil, with PCBs at a 500mL beaker, from a representative portion of the
concentration 2.0 mg/kg. Use a PCB mixture typical sample source. Mix the oil in the 500mL beaker. Fill
of those normally found in samples, such as a minimum of two 20mL sample bottles
®
Aroclor 1260. approximately 80 percent full from the 500mL
beaker.

7 SAMPLE COLLECTION,
PRESERVATION, AND 8 CHROMATOGRAPHIC
HANDLING OPERATING CONDITIONS

Sample containers should have a volume of 20mL or The chromatographic operating conditions given
more, and have PTFE lined screw caps. here are to serve as a guide only. Variations
between columns and GCs may necessitate
7.1 Sample bottle preparation. alterations in the conditions described to produce
suitable results.
Wash all sample bottles and cap seals in detergent
solution. Rinse first with tap water and then with
8.1 DB5 or equivalent column.
distilled water. Allow the bottles and seals to drain
and dry in a contaminant-free area. Then rinse the Carrier gas (He 16 psi
or H2)
seals with hexane and allow to air dry.
Injector 225°C
temperature
Heat sample bottles to 400°C for 15 to 20 minutes or
Detector 300°C
rinse with pesticide grade hexane and allow to air temperature
Initial 100°C, hold 2 minutes
dry.
temperature
Temperature 100°C to 160°C at
Store the clean bottles inverted or sealed until use.
program 15°C/min, followed by
160°C to 270°C at 5°C/min
Final 270°C
7.2 Sample preservation.
temperature
Make up flow 60mL/min
The samples should be stored in a cool, dry, dark
(N2)
area until analysis. Storage times in excess of four
weeks are not recommended for unknown or
8.2 DB608 or equivalent column.
undefined sample matrices.
Carrier gas (He 20 psi
Extracts should be stored under refrigeration in the or H2)
Injector 225°C
dark and should be analysed within 40 days of
temperature
extraction. Detector 300°C
temperature

EPA Victoria
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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

Initial 160°C, hold 2 minutes Alternative clean-up methods to those specified here
temperature
may be used with approval from EPA. When seeking
Temperature 160°C to 290°C at 5°C/min
program approval from EPA, validation of the proposed
Final 290°C, hold 1 min
method must be demonstrated before approval can
temperature
Make up flow 60mL/min be granted. The procedures that should be followed
(N2)
for method validation are available in NATA
Technical Note No. 17, “Requirements for the Format
and Content of Test Methods and Recommended
9 PROCEDURE
Procedures for the Validation of Chemical Test
Methods.” [3]
9.1 Sample preparation
9.2.1 Acid treatment.
Weigh approximately 1g of the test sample to the
nearest 0.001g into a 10mL volumetric flask. Add the Due to the complex nature of waste oils the
surrogate standard to give a suitable concentration procedures and information given here serve only as
in the diluted sample. Make to volume with solvent. a guide. The analyst may need to conduct more
This solution is designated solution A. extensive acid cleanup for more difficult samples.

An alternative approach is to add 1g of test sample Either of the two following acid cleanup procedures
into a disposable glass vial. Ten mL of solvent may be used as an initial treatment to remove
containing surrogate standard at a suitable interferences. Alternative acid cleanup methods may
concentration is then added to the vial. A final also be used.
volume of 11mL can be assumed with reasonable
accuracy. This approach enables the use of 9.2.1.1 Sulfuric Acid Treatment [4]
disposable glassware reducing the risk of cross
For some waste oils this procedure has been found
contamination.
to result in the formation of emulsions that have
Any water present in the sample has to be removed prevented further analysis. In such cases it is
which can be done by the addition of an appropriate recommended that the silica gel/sulfuric acid
quantity of sodium sulfate to Solution A. procedure described in Section 9.2.1.2 is used.

Extended acid treatment may degrade some of the

9.2 Removal of interferences
less chlorinated PCBs. Sulfuric acid should not be
Reference materials, field-contaminated samples, or allowed to remain in contact with the extract at
spiked samples should be used to verify the elevated temperatures for longer than necessary to
applicability of the selected clean-up technique. complete the analysis.
When other materials are not available and spiked
Add a 5mL portion of solution A into a 40mL narrow
samples are used, the Aroclor® 1016/1260 mixture
mouth screw cap bottle. Add 2.5mL of concentrated
may be an appropriate choice for spiking.
sulfuric acid into the bottle. Seal the bottle with a

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

Teflon lined screw cap and shake or vortex mix for Depending on the mass of silica gel/sulfuric acid
one minute. Depending on the degree of required greater or smaller quantities of silica gel
contamination the colour of the acid layer will range and sulfuric acid can be used, provided the mass
from yellow to dark brown. ratio of silica gel to sulfuric acid remains the same.

Allow the phases to separate (centrifuge if Put 4.0 ± 0.05g of the silica gel/sulfuric acid mixture
necessary), transfer the sample (upper phase) to a into a suitable size adsorption column. Add 1g of
clean narrow mouth screw cap bottle. Some loss of anhydrous sodium sulfate to the top of the silica
extract may occur during the acid cleanup; however gel/sulfuric acid.
this should not change the concentration of the
The mass of silica gel/sulfuric acid mixture used will
analytes in the sample. Do not bring up to original
depend on the type of waste oil to be cleaned up.
volume after clean-up as this will cause a dilution of
Four grams has been found to produce a satisfactory
the original concentration. Repeat the process until
result for most waste oils. Greater or smaller
no change in colour of either layer is seen. This
quantities of silica gel/sulfuric acid can be used to
solution is designated solution B.
meet the cleanup needs of the sample matrix.
It may be necessary to wash the solvent layer with
Pre-elute the column three times with 5mL of
several portions of reagent water until the wash
hexane. Stop the hexane eluate flow just prior to the
water is neutral to pH paper. This step can extend
exposure of the soldium sulfate to air. Discard the
the life of the GC column and detector.
eluate.

Transfer 1mL of solution A onto the column. Bring

9.2.1.2 Silica Gel/Sulfuric Acid cleanup [5]
the solvent level to just above the sodium sulfate to
The silica gel/sulfuric acid procedure described here
distribute the sample evenly over the packing. Wait
serves as a guide and must be verified before use. A
at least 5 minutes before elution.
recovery check must be performed using a waste oil
Elute the column twice with 4mL aliquots of hexane.
spiked with a known concentration of Aroclor® 1016
The elution must be carried out at a maximum flow
and Aroclor® 1260. Commercial cartridges
rate of 2mL/min and the column eluted each time
containing silica gel/sulfuric acid can also be used.
until the solvent level is just above the top of the
Weigh 28 ± 1 g chromatographic grade activated
adsorbent (except for the final elution).
silica gel (particle size 100 – 200µm) and 22 ± 1g of
Collect the eluates in a 15mL graduated centrifuge
sulfuric acid (96 – 98%) into a 200mL Erlenmeyer
tube. Reduce the volume of the eluate to 1mL under
flask. Shake until any lumps have disappeared. The
nitrogen prior to further chromatographic cleanup.
mixture will heat up considerably. Store the mixture
This solution is designated solution B.
in a closed dessicator over P2O5. The silica
gel/sulfuric acid mixture should be used within one The silica gel/sulfuric acid mixture can also be
week. added directly to the top of adsorption columns
containing other packings enabling acid cleanup

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

and adsorption cleanup in a single step. If this is 9.3.1 Standard column cleanup procedure [6, 2]
done the analyst must verify that the analytes of
Variations between batches of silica or Florosil® may
interest are being quantitatively recovered and that
affect the volume of solvent needed to elute all of
interferences are sufficiently removed before
the PCBs from the adsorption column. For this
applying the method to actual samples.
reason, the volume of solvent required to completely
elute all of the PCBs must be verified by the analyst.
9.3 Column adsorption chromatography
Silica Gel Florosil®
cleanup
M 3 20
VI 10 70
An acid cleanup alone does not usually remove all of
Vii 80 225
the PCB inteferences that occur in waste oil samples. Viii 0 25
An additional cleanup involving the use of
adsorption chromatography must also be used. Transfer M g of adsorption media into a 10mm ID
Either or both of the chromatographic cleanup glass chromatographic column and top it with 2 -
procedures described may be used. 3cm of anhydrous sodium sulfate.

The analyst may use other adsorption Add VimL of hexane to the top of the column to wet
chromatography methods provided validation and rinse the sodium sulfate and adsorption media.
proves that interferences to PCBs are effectively Just prior to exposure of the sodium sulfate layer to
removed. air, stop the hexane eluate flow by closing the
stopcock on the adsorption column. Discard the
The methods described here are examples of
eluate.
traditional column chromatography techniques and
solid-phase cartridge extraction. Generally, the Transfer 1mL of solution B onto the column. Rinse
traditional column chromatography techniques use the extract vial twice with 1 -2mL of hexane and add
larger amounts of adsorbent and therefore, have a each rinse to the column. Elute the column with
greater cleanup capacity. ViimL of hexane at a rate of 5mL/min. Collect and
discard the first Viii mL of the eluate. Collect the rest
A reagent blank should be prepared and analysed
of the eluate in a collection flask.
for PCBs prior to the use of these chromatographic
cleanup methods. The level of inteferences must be Remove the collection flask and reduce the volume
below the method detection limit before the method of hexane to provide a concentration of PCB in the
is performed on actual samples. final extract that falls within the range of the
calibration curve. This solution is designated
Phthalate ester contamination may be a problem
solution C.
with certain cartridges. The more inert the column
and/or cartridge material (i.e., glass or teflon), the
9.3.2 Cartridge cleanup procedure [6, 7]
less problem with phthalates.
Arrange the 1g silica or Florosil® cartridges on the
manifold in the closed-valve position.

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

Condition the cartridges by adding 4mL of hexane to 1016/1260 standard solutions. Once linearity
each cartridge. Close the valves and allow the through the origin is established using the Aroclor
solvent to soak the entire sorbent bed for five 1016/1260 standard solutions, quantification of
minutes. Do not turn off the vacuum. PCBs can be performed using one point calibration
curves of the other Aroclor® standard solutions.
Slowly open the cartridge valves to allow hexane to
pass through the cartridges. Close the cartridge Set up the GC at the conditions specified. Optimise
valves when there is still at least 1mm of solvent the instrumental conditions for resolution of the
above the sorbent bed. Do not allow the cartridges target compounds and sensitivity. A final
to become dry. If cartridges become dry, repeat the temperature of 240-275°C may be required to elute
conditioning step. C209. The use of injector pressure programming will
improve the chromatography of late eluting peaks.
Transfer 1mL of solution B onto the cartridge. Open
Once established, the same operating conditions
the cartridge valve and allow the extract to pass
must be used for both calibrations and sample
through the cartridge bed at approximately
analysis.
2mL/min.
A 2µL injection of each of the initial calibration
When the entire extract has passed through the
solutions is recommended. Other injection volumes
cartridges, but before the cartridge becomes dry,
may be employed, provided that the analyst can
add an additional 0.5mL of hexane to the cartridge.
demonstrate adequate sensitivity for the
Add 5mL of hexane to the cartridge. Allow the
compounds of interest.
solvent to soak the sorbent bed for one minute or
Record the peak area (or height) for each
less. Slowly open the cartridge valve and collect the
characteristic Aroclor® peak to be used for
eluate into the collection vial. Close the cartridge
quantitation in the initial calibration solution. A
valve.
minimum of three and preferably five peaks that are
Adjust the final volume of the collected fraction to a
at least 25per cent of the area (or height) of the
known volume that will result in a PCB concentration
largest Aroclor® peak should be used in the
appropriate for the analysis. This solution is
calculation. At least one peak should be chosen that
designated Solution C.
is unique to the Aroclor® that is to be used for
quantification.
9.4 Calibration
Example chromatograms obtained on a DB5
Prepare calibration standards as described in Sec.
equivalent column are shown for each Aroclor® in
6.11
Appendix III.

Calculate the calibration factor (CF) for each

9.4.1 Initial Calibration [1,8]
characteristic Aroclor® peak in each of the initial
The initial calibration involves establishing the
calibration standards using the equation below.
linearity of the calibration curve using the Aroclor®

EPA Victoria
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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

Peak Area (or Height) of the congener in the Standard

CF =
Total Mass of the Standard Injected (in nanograms)

Using the equation above, a calibration factor will where n is the number of calibration standards and
be determined for each characteristic peak, using RSD is expressed as a percentage.
®
the total mass of the Aroclor injected. These
If the RSD of the calibration factors for each
individual calibration factors are used to quantitate
characteristic Aroclor® peak is less than of equal to
sample results by applying the factor for each
20% over the calibration range, then linearity
individual peak to the area or height of that peak.
through the origin may be assumed, and the average
For a five point calibration, five sets of calibration calibration factor may be used to determine sample
factors will be generated for the initial calibration concentrations.
solutions, each set consisting of the calibration
If the RSD of the calibration factors is greater than
factors for each of the five (or more) peaks chosen
20per cent over the calibration range then linearity
for this mixture,for example, there will be at least 25
through the origin cannot be assumed. In these
separate calibration factors for the mixture. The
cases a linear calibration using a least squares
single standard for each of the other Aroclors® will
regression may be used for each characteristic
generate at least three calibration factors, one for
Aroclor® peak. A five point calibration needs to be
each selected peak.
performed for each Aroclor® that is to be used for
The calibration factors from the initial calibration are quantification purposes when a least squares
used to evaluate the linearity of the initial regression .is used.
calibration. This involves the calculation of the
The regression will produce the slope and intercept
mean calibration factor (C̄F̄ ), the standard deviation
terms for a linear equation in the form:
(SD), and the relative standard deviation (RSD) for
each Aroclor® peak using the equations below. y = ax + b

n where:
∑ CFi y = Instrument response (peak area or height)
CF = i =1

n
a = Slope of the line

x = Concentration of the calibration standard

∑ (CF )
n 2

i − CF b = Intercept
SD = i =1

n-1 When using a regression the analyst must not force

the line through the origin or include the origin as a
SD
RSD = × 100 data point, but have an intercepted line calculated
CF

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

from the five data points. The intercept value must standard deviation of the mean absolute retention
be less than five percent of the response of the time established during the 72-hour period.
decision level standard to be used for quantitative
Establish the centre of the retention time window for
purposes.
each congener and surrogate by using the absolute
The regression calculation will generate a correlation retention time for each congener and surrogate from
coefficient (r) that is a measure of the ’goodness of the calibration verification standard at the beginning
fit‘ of the regression line to the data. To be used for of each analytical shift. For samples run during the
quantitative purposes, r must be greater than or same shift as an initial calibration, use retention
equal to 0.99. time of the mid-point standard of the initial
calibration.
9.5 Retention Time Windows [1,8]
Retention time windows must be calculated for each
Absolute retention times are generally used for chromatographic column and instrument that the
compound identification. When absolute retention analysis is to be performed on. New retention time
times are used, retention time windows are crucial to windows must be established when a new GC
the identification of target compounds. Other column is installed.
approaches to the one described here may be used
The surrogate retention time may be useful in
but they must be documented by the analyst.
tracking retention time shifts. Whenever the
Before establishing retention time windows, ensure observed retention time of the surrogate is outside
that the chromatographic system is operating of the established retention time window, the
reliably and that the system has been optimised for analyst must determine the cause and correct the
PCBs. problem before continuing analyses.

Make five injections of each of the Aroclor®

9.6 Gas Chromatographic Analysis of Sample
standards and surrogate over a 72 hour period.
Extracts
Record the retention time (in minutes) for each of
The same GC operating conditions used for the
the three to five congeners that are to be used for
initial calibration must be employed for the analysis
quantification and surrogate to three decimal places
of samples.
(e.g. 0.007 min). Calculate the mean and standard
deviation of the five absolute retention times for Calibration verification must be performed
relevant congener and surrogate. periodically during sample analysis. Further
information on how to perform calibration
If the standard deviation of the retention times is
verification is described in Section 11.2.
0.000 minutes, then use a default standard
deviation of 0.01 minutes. Inject a measured aliquot of Solution C into the GC.
A 2µL aliquot is suggested, however the same
The width of the retention time windows for each
injection volume must be used for both the
congener and surrogate is defined as ± 3 times the

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

calibration standards and the sample extracts. GC/MS confirmation may be used if the
Record the volume injected and the resulting peak concentration is sufficient for detection by GC/MS.
size in area or height units. Refer to SW846 Method 8082A Sec. 7.10 [1] for
further information.
9.6.1 Qualitative Identification
9.6.2 Quantitation of PCBs
The identification of PCBs as Aroclor® is based on
the agreement between the retention times of the The quantitation of PCB residues as Aroclors® is
peaks in the sample chromatogram with the accomplished by comparison of the sample
retention time windows established through the chromatogram to that of the most similar Aroclor®
analysis of the standards of the target analytes. standard. A choice must be made as to which
Aroclor® is most similar to that of the residue and
Tentative identification of an analyte occurs when a
whether that standard is truly representative of the
peak from a sample extract falls within the
PCBs in the sample.
established retention time window for a specific
target analyte. Confirmation is necessary when the Use the Aroclor® 1221, 1232, 1242, 1248, and 1254
sample composition is not well characterised. That standards to determine the peak pattern of these
®
is, if the Aroclor present in the sample cannot be Aroclors®. The patterns for Aroclor® 1016 and 1260
unambiguously identified or if suspect interference will be evident in the mixed calibration standards.
peaks appear in the chromatogram, confirmation on
Once the Aroclor® pattern has been identified,
a second column is necessary.
compare the responses of three to five major peaks
Confirmation is performed using a second GC in the single point calibration standard for that
column of dissimilar stationary phase. The analyst Aroclor® with the peaks observed in the sample
should check the agreement between the extract.
quantitative results on both columns once the
The amount of Aroclor® is calculated using the
identification has been confirmed.
individual calibration factor for each of the three to
Retention time windows must have been five characteristic peaks. Those three to five
established for the second GC column in order to be concentrations are then averaged to determine the
used for confirmation. In addition the analyst must concentration of that Aroclor®.
demonstrate the sensitivity of the second column
If the chromatographic pattern contains mixed
analysis. This demonstration must include the
Aroclors®, compare the response of three to five
analysis of a standard of the target analyte at a
major peaks in the single point calibration standard
concentration at least as low as the concentration
for each Aroclor® in the mixture with the peaks
estimated for the primary analysis. The standard
observed in the sample extract of each Aroclor®. It
®
may be either the individual Aroclor or the Arolcor
is essential that the peaks used for quantification
1016/1260 mixture.
are unique to the Aroclor® and do not overlap with
any other Aroclor® peaks in the mixture.

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If the chromatographic pattern of the sample extract rerunning the sample on another instrument to
does not contain a recognisable Aroclor® pattern determine if the problem results from analytical
then measure the total area of the PCB pattern and hardware of the sample matrix.
®
quantitate on the basis of the Aroclor standard that
is most similar to the sample . Any peaks that are 9.7 Calculation [8]
not identifiable on the basis of retention times
The concentration of each characteristic Aroclor®
should be subtracted from the total area. When
peak is calculated as follows:
quantitation is performed in this manner, the
A sD
problems should be fully described for the data user Concentration (mg/kg) =
and the specific procedures employed by the CFVi Ws
analyst should be thoroughly documented.
where:

As = Area (or height) of the Aroclor® peak.

If the responses in the sample chromatogram
D = Total dilution of the sample (mL).
exceed the calibration range of the system, dilute
C̄F̄ = Mean calibration factor from the initial
the extract and reanalyse. Dilute the extract using a
calibration (area or height pre ng).
solvent containing clean transformer oil at a
concentration equivalent to that in the standards. Vi = Volume of the extract injected (µL).
Peak height measurements are recommended when
Ws = Weight of the sample diluted (g).
overlapping peaks cause errors in area integration.
If a linear calibration that does not pass through the
If peak response is less than 2.5 times the baseline
origin has been used, then the regression equation
noise level, the validity of the quantitative result
is rearranged to solve for x as follows:
may be questionable. The analyst should consult
y-b
with the source of the sample to determine whether x=
a
further concentration of the sample is warranted.
where:
Use the calibration standards analysed during the
y = Instrument response (peak area or height)
sequence to evaluate retention time stability. If any
a = Slope of the line
of the standards fall outside their daily retention
x = Concentration of the calibration standard
time windows, the system is out of control.
b = Intercept
Determine the cause of the problem and correct it.
When using this equation it is the analysts
If compound identification or quantification is
responsibility to ensure the calculation takes into
precluded due to interferences (for example broad,
account the weight of the original sample and the
rounded peaks or ill-defined baselines are present),
dilution factor.
corrective action is warranted. Cleanup of the extract
or replacement of the capillary column or detector
may be necessary. The analyst may begin by

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

10 REPORTING RESULTS 11 QUALITY CONTROL [1,2,8]

a Report all data in mg/kg. A formal quality control program is an integral part
of this method. In addition before processing any
b Report the results obtained for each Aroclor®
samples the analyst should demonstrate through
identified.
the analysis of a PCB-free oil sample, that all
c If an Aroclor® was not detected report the result as
glassware and reagents are free of interferences.
non-detect quoting the detection limit in mg/kg.
Each time a set of samples is analysed or there is a
®
d. If an Aroclor result is below the reporting limit
change in reagents, a laboratory reagent blank
but greater than the detection limit report the result
should be processed as a safeguard against
obtained noting that the result is below the
contamination.
reporting limit.

e. Add the results of all Aroclors® detected and 11.1 Initial Generation of Accuracy and
report a total PCB concentration. A note should be Precision Data
included on the report that total PCB concentration
Before performing any analyses, the analyst must to
refers to the sum of the Aroclors® analysed for.
generate accuracy and precision data with this
f. If the sample extract contained an unrecognisable method by analysing four separate samples of
Aroclor® pattern report a total PCB concentration representative waste oil spiked with PCBs in the
and what was used as the standard. For example concentration range from 1 to 3mg/kg. A mixture of
2.2mg/kg measured as Aroclor® 1242. Aroclor® 1016 and 1260 can be used for this
purpose.
g. If Aroclors® are not detected in the sample
extract report non-detect for the total PCB result An aliquot of the representative waste oil sample
and quote a total detection limit. The total must be analysed prior to spiking to determine the
detection limit can be calculated by adding half the PCB background level. The spike level must exceed
detection limits of all the Aroclors® used for twice the background level for the test to be valid.
quantification.
Calculate the average per cent recovery (R) and the
h Report results with the associated uncertainty. relative standard deviation (s) of the concentration
The uncertainty should be calculated according to found. Waste oil background corrections must be
the ISO GUM method [9] or equivalent. For example made before R calculations are performed.
2.2 ± 0.3 mg/kg (95% confidence level).
The laboratory must develop and maintain separate
i For results in the 1.7 to 2mg/kg range report the accuracy statements of laboratory performance for
recovery data. waste oil samples. An accuracy statement for the
method is defined as R±s. The accuracy statement
should be developed by the analysis of four aliquots
of waste oil followed by the calculation of R and s.

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

Alternatively, the analyst may use four waste oil data Calculated concentration - Theoretical concentration
% Drift = × 100
Theoreticalconcentration
points gathered through the requirements of
continuing quality control. The accuracy statements
If the percentage difference or percentage drift is
should be updated regularly.
less than ±15% then the initial calibration is
considered valid and the analyst may continue to
11.2 Calibration Verification
use the initial calibration values to quantitate
Verify calibration at least at the beginning and end samples.
of an analysis sequence. For sequences with more
If the percentage difference or percentage drift is
than 10 samples verify calibration once each 12 hour
greater than ±15% then the no sample analyses may
shift or every 10 samples whichever is more
take place until the calibration has been verified or a
frequent. Calibration verification is done by injecting
new initial calibration is performed.
an Aroclor® 1016/1260 calibration standard.
Calibration verification must be performed using the When a calibration verification standard fails to

concentration standard corresponding to a PCB meet the QC criteria, all samples that were injected

concentration in waste oil of 2mg/kg. The calibration after the last standard that meet the QC criteria must

verification process does not require analysis of the be evaluated to prevent misquantitations and

other Aroclor® standards used for pattern possible false negative results, and re-injection of

recognition, but the analyst may wish to include a the sample extracts may be required.

standard for one of these Aroclors® after the If an analyte was not detected in the sample and the
1016/1260 mixture used for calibration verification standard response is more than 15per cent below
throughout the analytical sequence. the initial calibration response, then re-injection is

If a linear calibration curve through the origin has necessary. The purpose of this re-injection is to

been used, calibration verification involves the ensure that the analyte could be detected, if

calculation of the percent difference of the present, despite the change in the detector

instrument response between initial calibration and response, for example, to protect against a false

each subsequent analysis of the verification negative result.

standard. If an analyte was not detected in the sample and the

standard response is greater than 15per cent above
CF − CF
% Difference = × 100 the initial calibration response, then re-injection is
CF
not necessary.
If a linear calibration curve using the least square
Sample injections may continue for as long as the
regression has been used, calibration verification
calibration verification standards meet the
involves the calculation of the percent drift of the
instrument QC requirements. It is required that
instrument response between initial calibration and
standards be analysed every 10 samples. The
each subsequent analysis of the verification
sequence ends when the full set of samples has
standard.

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CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

been injected or when qualitative or quantitative QC must be at least 10per cent of all samples or one
criteria are met. sample per sequence, whichever is greater. One
aliquot of sample must be spiked and analysed at a
11.3 Matrix Spike, Surrogate Recoveries and PCB concentration of 2mg/kg. The LCS recovery
Duplicates data may be used instead of the matrix spike
recovery data if the matrix spike recovery is invalid
At least 10per cent of the samples analysed must be
due to high background levels
analysed in duplicate. The duplicate can be an
unspiked sample or a matrix spike duplicate. The A laboratory control sample should be included with
decision on which to use must be based on each analytical batch. When the results of the matrix
knowledge of the sample batch and whether target spike analysis indicative a potential problem due to
analytes are expected to be present or not. the sample matrix itself, the LCS results are used to
verify that the laboratory can perform the analysis in
The laboratory is required to collect a portion of their
a clean matrix.
samples in duplicate to monitor spike recoveries. If
samples are not expected to contain target analytes The laboratory must also evaluate surrogate
the Aroclor® 1016/1260 mixture can be used for recovery data from individual samples versus the
®
spiking. If specific Aroclors are known to be surrogate control limits.
present , the specific Aroclors® should be used for
Matrix spike and surrogate recovery is calculated as
spiking. The frequency of spiked sample analysis
follows:

Conc. (or amount) found - Conc.(or amount)in unspiked sample

Recovery (%) = × 100
Conc. (or amount) added

If recovery is not within the limits described in Sec Calculate the upper and lower control limit for each
11.3.1, corrective action is necessary. matrix spike or surrogate compound:

If no problem is found, the sample should be re- Upper control limit = p + 3s

Lower control limit = p – 3s
extracted and re-analysed. If, upon re-analysis the
recovery is again not within limits, report the data as Calculate warning limits as:
an ‘estimated concentration.’ If the recovery is
Upper warning limit = p + 2s
within the limits in the re-analysis, provide the re- Lower warning limit = p – 2s
analysis data to the data user.
Any results outside the control limits require
evaluation by the laboratory.
11.3.1 Performance criteria for matrix spike and
surrogate recoveries.

Calculate the average percentage recovery (p) and

the standard deviation (s) for the surrogate after the
analysis of 15 to 20 field samples.

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
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APPENDIX I PREPARATION OF CLEAN II.1.1.3 12mL Centrifuge tubes calibrated

TRANSFORMER OIL
II.1.2 Reagents

Add a 15 mL portion of the clean transformer oil into II.1.2.1 Dilute Nitric acid, HNO3 II.1.2.2 Organic free
a 40mL narrow mouth screw cap bottle. Add 15mL of reagent water
concentrated sulfuric acid into the bottle. Seal the
II.1.2.3 Acetone
bottle with a Teflon lined screw cap and shake or
Pesticide quality or equivalent
vortex mix for one minute. Depending on the degree
of contamination the colour of the acid layer will II.1.2.4 Copper powder
range from yellow to dark brown.
(fine granular Mallinckrodt 4649 or equivalent)
Allow the phases to separate (centrifuge if Remove oxides by treating with dilute nitric acid,
necessary), remove the lower acid layer. Repeat the rinse with reagent water to remove all traces of acid,
process until no change in colour of either layer is rinse with acetone and dry under a stream of
seen. nitrogen.

Wash the oil layer with several 15mL portions of II.1.3 Procedure
reagent water until the wash water is neutral to pH
Concentrate the sample extract to a known volume.
paper.
Add approximately 2 g of cleaned copper powder to
A check must be made before adding the cleaned the centrifuge tube. Vigorously mix the extract and
transformer oil to the standard solutions to copper powder for at least 1 minute. Allow the
determine if there are any chromatographic peaks phases to separate.
that will interfere with the PCB analysis.
Separate the extract from the copper by drawing off
the extract with a pipette and transfer to a clean vial
APPENDIX II SULFUR CLEANUP for further cleanup or analysis.
METHODS
II.2 Copper Strip Procudure

II.1 Copper Powder Procedure [10] II.2.1 Reagents

This technique requires the copper powder to be II.2.1.1 Nitric acid, HNO3 20%
very reactive, as evidenced by a bright shiny
II.2.1.2 Organic free reagent water
appearance.
II.2.1.3 Acetone
II.1.1 Apparatus and Materials
Pesticide quality or equivalent.
II.1.1.1 Mechanical shaker or mixer
II.2.1.4 Copper foil
Vortex Genie or equivalent.
(Analar-BDH or equivalent) Cut foil into strips
II.1.1.2 Pipettes, disposable
approximately 30 mm x 3 mm. React copper with
Pasteur type. 20% nitric acid solution briefly until gas evolution is

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

established and the solution turns a pale blue.

Remove from acid and quickly, rinse the foil with
water, then acetone, then hexane. Use immediately.

II.2.2 Procedure

Concentrate the sample extract to a known volume.

Add two copper strips to the extract and allow to
react for 1 to 2 hours. If the strips are blackened
during this time, add further strips and treat again,
until no further blackening occurs. Remove the
strips, rinsing with hexane and adjust the solution
volume to the original volume with a stream of high
purity nitrogen. Use the extract for further cleanup or
analysis.

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
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APPENDIX III EXAMPLE AROCLOR® CHROMATOGRAMS

Norm.
200

300

400

500

600

700
5

(
)
10

10.946

11.715
12.064
12.260

12.959
13.219 - Congener 30
13.777 13.701
14.077
14.376

15.079 14.980
15

15.278 15.332
15.689
15.965
16.164
16.455 16.564
16.863 16.730

17.468 17.338
17.790
18.110
18.629
18.761
18.928
20
25
30

33.422 - Congener 209

min

Figure III.1. Example GC/ECD chromatogram of Aroclor® 1016 analysed on a BP5 column (30 m x 0.32 mm, 0.5 µm
film thickness). Temperature program: 100°C (2 min hold) to 160°C at 15°C/min, to 270°C at 5°C/min (10 min
hold). Congener 30 and 209 added to standard as reference peaks.

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
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Norm.
200

300

400

500

600

700
5

(
9.089

)
10

10.256
10.922

11.693
12.041
12.237

13.196 - Congener 30
13.565
13.681 13.758
14.357
15

15.315
15.670
15.949

18.919

19.747
20

21.128
25
30

33.418 - Congener 209

min

Figure III.2. Example GC/ECD chromatogram of Aroclor® 1221 analysed on a BP5 column (30 m x 0.32 mm, 0.5 µm
film thickness). Temperature program: 100°C (2 min hold) to 160°C at 15°C/min, to 270°C at 5°C/min (10 min
hold). Congener 30 and 209 added to standard as reference peaks.

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
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Norm.
200

300

400

500

600

700
5

(
9.091

)
10

10.259
10.925

11.696
12.045
12.241

13.201 - Congener 30
13.569 13.684
13.761
14.060
14.360
14.965
15

15.065
15.26415.319
15.675
15.952
16.150
16.550
16.852 16.717
17.456 17.326
17.777
18.096
18.617 18.748
18.899
19.533
19.749
19.962
20

20.576
20.759
20.929
21.129
21.571
22.070

23.072

23.940
25

26.793
30

33.422 - Congener 209

min

Figure III.3. Example GC/ECD chromatogram of Aroclor® 1232 analysed on a BP5 column (30 m x 0.32 mm, 0.5 µm
film thickness). Temperature program: 100°C (2 min hold) to 160°C at 15°C/min, to 270°C at 5°C/min (10 min
hold). Congener 30 and 209 added to standard as reference peaks.

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Norm.
200

300

400

500

600

700
5

(
)
10

10.930

11.701
12.050
12.246

12.946
13.207 - Congener 30
13.766 13.690
14.065
14.365

15.06814.970
15

15.268 15.322
15.678
15.957
16.153
16.446 16.556
16.859 16.721

17.458 17.331
17.782
18.101
18.621 18.752
18.903
19.176
19.539
19.753
19.965
20

20.581
20.935 20.764
21.134
21.575
22.078

22.909 23.074

23.944

24.969
25
30

33.421 - Congener 209

min

Figure III.4. Example GC/ECD chromatogram of Aroclor® 1242 analysed on a BP5 column (30 m x 0.32 mm, 0.5 µm
film thickness). Temperature program: 100°C (2 min hold) to 160°C at 15°C/min, to 270°C at 5°C/min (10 min
hold). Congener 30 and 209 added to standard as reference peaks.

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
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Norm.
200

300

400

500

600

700
5

(
)
10

12.248

13.206 - Congener 30
13.766 13.689

14.365
14.972
15

15.268
15.322
15.682
15.956
16.154
16.445 16.555
16.849 16.720

17.462 17.330
17.780
18.102
18.475 18.620 18.753
18.905
19.173
19.536
19.752
19.965
20

20.385
20.580
20.933 20.764
21.134
21.576
21.755
21.893
22.079
22.504
22.908 23.077

23.945

24.972
25
30

33.427 - Congener 209

min

Figure III.5. Example GC/ECD chromatogram of Aroclor® 1248 analysed on a BP5 column (30 m x 0.32 mm, 0.5 µm
film thickness). Temperature program: 100°C (2 min hold) to 160°C at 15°C/min, to 270°C at 5°C/min (10 min
hold). Congener 30 and 209 added to standard as reference peaks.

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Norm.
200

300

400

500

600

700

800

900
5

(
)
10

13.205 - Congener 30
13.691

14.370
15

15.269
15.681

16.556
16.872 16.722

17.462 17.330
17.783
18.100
18.621 18.753
18.933
19.175
19.546
19.756
19.965
20

20.386
20.581
20.935 20.765
21.135
21.580
21.894 21.753
22.075
22.441
22.603 22.686
22.910
23.067
23.481 23.382
23.651
23.745
24.036 23.943
24.254
24.558
24.747
24.971
25

25.427
25.628
25.807
26.025
26.173
26.412

27.502
30

33.426 - Congener 209

min

Figure III.6. Example GC/ECD chromatogram of Aroclor® 1254 analysed on a BP5 column (30 m x 0.32 mm, 0.5 µm
film thickness). Temperature program: 100°C (2 min hold) to 160°C at 15°C/min, to 270°C at 5°C/min (10 min
hold). Congener 30 and 209 added to standard as reference peaks.

Guidelines for Environmental Management

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 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

Norm.
1000

1100
200

300

400

500

600

700

800

900
5

(
)
10

13.207 - Congener 30
15

15.324

16.879

17.798

18.936
19.547
19.760
19.967
20

20.624
20.766
21.053
21.135
21.584
21.752
22.031
22.440
22.686
23.047 22.911
23.480 23.383
23.747
23.940
24.253
24.557
24.746
24.971
25

25.145
25.425
25.628
25.796
26.036
26.173
26.412
26.668
26.895
27.504
27.686 27.803
28.002

29.159
29.427
29.959
30

30.204

31.743

33.429 - Congener 209

min

Figure III.7. Example GC/ECD chromatogram of Aroclor® 1260 analysed on a BP5 column (30m x 0.32mm, 0.5µm
film thickness). Temperature program: 100°C (2 min hold) to 160°C at 15°C/min, to 270°C at 5°C/min (10 min
hold). Congener 30 and 209 added to standard as reference peaks.

EPA Victoria
26
 DETERMINATION OF PCBs IN WASTE OILS BY GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTOR

APPENDIX IV REFERENCES

[1] SW 846 Method 8082A, Polychlorinated Biphenyls (PCBs) by Gas Chromatography, United States
Environmental Protection Agency, November 2000.

[2] EPA-600/4-81-045, The Determination of Polychlorinated Biphenyls in Transformer Fluid and Waste Oils,
United States Environmental Protection Agency, September 1982.

[3] NATA Technical Note No. 17, Requirements for the Format and Content of Test Methods and Recommended
Procedures for the Validation of Chemical Test Methods, 1997.

[4] SW846 Method 3665A, Sulfuric Acid/Permanganate Cleanup, United States Environmental Protection
Agency, December 1996.

[5] AS 1767.2.7-1999, Insulating Liquids Part 2: Test Methods, Method 2.7: Determination of PCB
contamination in Insulating Liquids by Capillary Column Gas Chromatography – Identification of
Congeners, Standards Australia, 1999.

[6] SW846 Method 3630C, Silica Gel Cleanup, United States Environmental Protection Agency, December
1996.

[7] SW846 Method 3620B, Florosil® Cleanup, United States Environmental Protection Agency, December 1996.

[8] SW846 Method 8000B, Determinative Chromatographic Separations, United States Environmental
Protection Agency, December 1996.

[9] Guide to the Expression of Uncertainty in Measurement . ISO, Geneva, 1993. (ISBN 92-67-10188-9)

[10] SW846 Method 3660B, Sulfur Cleanup, United States Environmental Protection Agency.

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