EUROPEAN STANDARD EN 12766-1

NORME EUROPÉENNE
EUROPÄISCHE NORM March 2000

ICS 75.080; 75.100

English version

Petroleum products and used oils - Determination of PCBs and

related products - Part 1: Separation and determination of
selected PCB congeners by gas chromatography (GC) using an
electron capture detector (ECD)

Produits pétroliers et huiles usagées - Détermination des
PCBs et produits connexes - Partie 1: Séparation et
dosage d'une sélection de congénères de PCB par
chromatographie en phase gazeuse (CG) avec utilisation
d'un détecteur à capture d'électrons (ECD)
Mineralölerzeugnisse und Gebrauchtöle - Bestimmung von
PCBs und verwandten Produkten - Teil 1: Trennung und
Bestimmung von ausgewählten PCB Congeneren mittels
Gaschromatographie (GC) unter Verwendung eines
Elektroneneinfang-Detektors (ECD)

This European Standard was approved by CEN on 20 January 2000.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national
standards may be obtained on application to the Central Secretariat or to any CEN member.

This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the official
versions.

CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece,
Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION

COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG

Central Secretariat: rue de Stassart, 36 B-1050 Brussels

© 2000 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 12766-1:2000 E
worldwide for CEN national Members.
Page 2
EN 12766-1:2000

Foreword

This European Standard has been prepared by Technical Committee CEN/TC 19 "Petroleum products, lubricants and related
products", the secretariat of which is held by NNI.

This European Standard shall be given the status of a national standard, either by publication of an identical text or by
endorsement, at the latest by September 2000, and conflicting national standards shall be withdrawn at the latest by
September 2000.

According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are
bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece,
Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom.

In this standard, annexes A and B are normative, annexes C, D and E are informative.

This European Standard is one of a series of standards as listed below.

EN 12766, Petroleum products and used oils - Determination of PCBs1) and related products

Part 1: Separation and determination of selected PCB congeners by gas chromatography (GC) using an electron capture
detector (ECD)

Part 2: Quantification of PCB content in analyzed samples2

Part 3: Determination and calculation of PCB related products3

1) PCBs as defined in:

Council directive 95/59/EC of 1996-09-16 on the disposal of polychlorinated biphenyls and polychlorinated terphenyls. The definition
includes PCBs proper, PCTs and also PCBTs (polychlorinated benzyltoluenes), tradename “Ugilec”.
2
Part 2 of EN 12766 is under development.
3
Part 3 of EN 12766 is under development
 Page 3
EN 12766-1:2000

1 Scope

This European Standard specifies a method to determine the concentration of up to 12 individual or defined unresolved small
groups of polychlorinated biphenyl (PCB) congeners in petroleum products and related materials by means of a specified
gaschromatographic separation procedure. The gas chromatographic separation is valid for the different quantification
procedures described in Part 2 of this European Standard.

This European Standard is applicable to unused, used and treated (e.g. dechlorinated) petroleum products including synthetic
lubricating oils, and to petroleum products and synthetic lubricating oils suitably recovered from other materials, e.g. from
waste materials.
NOTE 1 The nominal application range does depend on precision, the lower limit per single congener is about 0,2 mg/kg.

NOTE 2 For the purposes of this European Standard, the terms “% (V/V)” and “% (m/m)” are used to represent respectively the mass
fraction and the volume fraction.
This European Standard does not apply to insulating liquids, for which a different method (EN 61619) is available. Depending
on current legislation, it may be necessary to measure either total or individual PCB congeners. EN 61619 may be followed as
an alternative method for the determination of total PCBs, using the clean-up stage described in clause 8 of this standard.

WARNING : The use of this standard can involve hazardous materials, operations and equipment. This standard does not
purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to
establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

2 Normative references

This European standard incorporates, by dated or undated reference, provisions form other publications. These normative
references are cited at the appropriate places in the text and the publications are listed hereafter. For dated references,
subsequent amendments to or revisions of any of these publications apply to this European Standard only when incorporated in
it by amendment of revision. For undated references the latest edition of the publication referred to applies.

EN ISO 3696, Water for analytical laboratory use - Specification and test methods. (ISO 3696:1987)

EN ISO 3170, Petroleum liquids - Manual sampling. (ISO 3170:1988, including Amendment 1:1998)

EN ISO 3171, Petroleum liquids - Automatic pipeline sampling. (ISO 3171:1988)

3 Terms and definitions

For the purposes of part 1 of this standard, the following definitions apply:

3.1

polychlorinated biphenyl
PCB
biphenyl substituted by one to 10 chlorine atoms
NOTE For legal purposes, congeners with one, two or ten chlorine atoms can be excluded from this definition.

3.2

congener
all the chlorine derivatives of biphenyl, irrespective of the number of chlorine atoms
NOTE There are 209 possible PCB congeners. The congener numbers (see annex C) are for easy identification; they do not represent
the order of chromatographic elution.
Page 4
EN 12766-1:2000

3.3

resolution
ratio of the distance between the maxima of two peaks to the average of their peak widths at the base, calculated
2 ∆t
as: where
t, Ya and Yb are as indicated in figure 1.
Ya + Yb

Figure 1 — Quantities for determination of the resolution

4 Principle

A sample preparation (clean up) procedure is used to remove most of the impurities likely to interfere with the determination.
The clean up procedure is chosen according to the type of sample. The PCB congeners are determined by gas chromatography
using a high efficiency narrow-bore capillary column, an electron capture detector and an internal standard.

The PCB congeners are separated into single or small groups of overlapping congeners. Single congeners and unresolved
groups are identified using a standard test mixture prepared from Aroclors4 and the gas chromatogram shown in annex A.1.
Experimental relative retention times (ERRTs [clause 11]) are calculated. Calibration and quantification of the identified peaks
are achieved using individual congeners and an internal standard.
NOTE 1 PCB congener 138 cannot be separated on the specified GC column (6.3) from congener 163. Overlaps of
25 - 35 % can be analysed in technical mixtures. The concentration of congener 138 determined by this method includes concentration of
congener 163 evaluated by using the response factor of congener 138.

NOTE 2 It should be verified that congener 101 is completely resolved from congener 84 on the column (6.3) used in this method.

5 Reagents and materials

Use only reagents of recognized analytical grade and water conforming to grade 3 of EN ISO 3696.

4 The industrial use of PCB containing products is now generally forbidden. Aroclors are the only PCB containing products still available,
and only for use as a reference material in testing. This information is given for convenience of the users of this European Standard and does
not constitute an endorsement by CEN of these products.
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EN 12766-1:2000

5.1 General provisions

All reagents and materials including those for clean up (clause 8 and annex B) shall be free from PCB contamination and
compounds interfering in the ECD.

Where preparations of solutions etc. are expressed volumetrically, such preparations may alternatively be conducted
gravimetrically.
5.2 Reagents and materials for the sample preparation (clean up)

5.2.1 Solvent, high purity, free from PCB contamination and low in compounds that respond in the ECD. Heptane is
preferred but hexane, cyclohexane or 2,2,4-trimethylpentane may also be used.
5.2.2 Sodium sulfate, granular, anhydrous.
5.2.3 Sulfuric acid, of purity 96 % (m/m) to 98 % (m/m).
5.2.4 Separation material, silica gel, active, particle size 100 µm to 200 µm.
5.2.5 Columns, for solid phase extraction, of the types given in a) and b):
a) 3 ml silica gel column, of adsorbent mass 500 mg, particle size 40 µm;
b) 3 ml benzenesulfonic acid column, of adsorbent mass 500 mg, particle size 40 µm.

5.2.6 Column adapter, for joining two columns

5.2.7 Vacuum manifold column processor (optional).

5.3 Reagents and materials for the GC analysis

5.3.1 Hexachlorobenzene, of purity greater than 99 % (V/V).

5.3.2 Carrier gas, either helium or hydrogen.
5.3.3 Make up gas, either nitrogen, or a mixture of argon and methane in the volume ratio of 95 % : 5 %.

NOTE The purity of all the gases should be at least 99,99 % (V/V). The gas line should be fitted with a moisture filter and an oxygen
absorber cartridge.

5.4 Standards

NOTE The standards specified in this clause can be purchased as solutions of known concentration (precision ± 5 %) in hydrocarbon
solvent (5.2.1) prepared from pure materials (purity greater than 99 % (m/m)); or prepared by the user from pure materials.
5.4.1 Congener 30 solution, of nominal concentration 10 mg/l.
5.4.2 Congener 209 (DCB) solution, of nominal concentration 10 mg/l.
5.4.3 Internal standard solution, comprising 2 mg/l congener 30 and 2 mg/l congener 209, prepared by pipetting 5 ml of
solution (5.4.1) and 5 ml of solution (5.4.2) in a 25 ml volumetric flask and filling up to the mark with solvent (5.2.1).
5.4.4 Certified calibration mixture solution, in solvent (5.2.1) including the 14 selected PCB congeners containing congener
18, 28, 31, 44, 52, 101, 118, 138, 149, 153, 170, 180, 194, and 209 at a concentration of 10 mg/l each, as recommended for this
method (Annex D.3).

NOTE 1 Depending on the type of quantification, some of these congeners may not be required.

NOTE 2 Congener 170 is only used if the PCB content is evaluated according to part 2, method A.
5.4.5 Commercial Aroclors, in solvent (5.2.1):
a) Aroclor 1242 solution, 1 g/l concentration;
b) Aroclor 1254 solution, 1 g/l concentration;
c) Aroclor 1260 solution, 1 g/l concentration.

5.4.6 Test mixture solution, made up as follows:

A solution is prepared containing 0,5 mg/l of Aroclor 1242, 0,25 mg/l of Aroclor 1254 and Aroclor 1260 each, and 0,02 mg/l
of congener 30 and congener 209 each in solvent (5.2.1).
Page 6
EN 12766-1:2000

5.5 Base oil, unused, free from PCB.

NOTE The following oil has been found suitable; RL 110 technical white oil, boiling range 370 °C to 570 °C (CEC L-33-T-82 RL
110).

6 Apparatus

6.1 General provisions

All parts of the apparatus coming into contact with the sample, especially the packed columns for the liquid chromatographic
clean up, shall be free from PCB and interfering compounds. The glassware shall be cleaned with solvent (5.2.1).
The apparatus shall be usual laboratory apparatus and glassware, together with the following:
6.2 Gas chromatograph

High resolution, with accurately reproducible oven temperature control, capable, when used with the appropriate column and
conditions, of resolving the test mixture (5.4.6) at least as well as shown in figure A.1 (at least 90 peaks to be observed) and of
reproducing the experimental relative retention time (ERRT) to within ± 0,0015.

The injector shall be either an on-column injector, or a split/splitless injector.

NOTE 1 When a split/splitless injector is used it is necessary to operate it in the splitless mode (9.2).
The gas chromatograph shall be equipped with ECD and gas supply systems as specified in the manufacturer's manuals.
NOTE 2 The ECD requires type approval in accordance with the national Regulations on Radiation Protection.

6.3 Columns

Each comprising a 5 % phenyl-methyl silicone stationary phase coated onto fused silica capillary column or an equivalent
chemically bonded phase column. Their dimensions shall be as follows:

length: 50 m to 60 m
internal diameter: 0,2 mm to 0,25 mm
film thickness: 0,1 µm to 0,25 µm
NOTE For suitable columns and manufacturers see annex D.2.

7 Sampling and sample preparation

Unless otherwise specified in the commodity specification, samples shall be taken as described in EN ISO 3170 or
EN ISO 3171, and/or in accordance with the requirements of national standards or regulations for the sampling of the product
under test.

Only glass or metal vessels shall be used for sampling, for storing samples and for determination.
NOTE 1 Pipette tips and columns made of plastics material are permitted.
The sample preparation method described below shall be used for liquid samples without a recognizable free water phase.
NOTE 2 If emulsified water is perceived as opacity in the sample solution, it can be ad- sorbed by adding anhydrous sodium sulfate in
portions and shaking until a clear solution is obtained.
If the samples have a free water phase, it shall be separated from the oil phase prior to further analysis, e.g. by centrifuging and
with the aid of a separating funnel. Petroleum products mixed with solids shall be separated beforehand by suitable means, e.g.
by centrifugation and by extraction of the solids with the solvent.

Homogenize the sample using a high-speed stirrer or an ultrasonic bath; or shake the sample by hand for 3 min.
NOTE 3 The sample can, if desired, be heated slightly beforehand.
Weigh approximately 1,0 g to the nearest 1 mg of the homogenized sample into a 10 ml volumetric flask. Add approximately 8
ml of solvent (5.2.1) and mix well. Add 1 ml of the internal standard solution (5.4.3) and make up to the mark with solvent
(5.2.1).
 Page 7
EN 12766-1:2000

8 Clean-up procedure

8.1 In general, the relatively simple procedure given in 8.2 to 8.4 and illustrated by figure 2 shall be used before GC analysis
of the sample solution. If this clean-up is unsatisfactory the alternative clean-up procedure given in annex B.1 can be used.
Additional clean-up steps are given in annex B.2 to B.5.

NOTE 1 A clean-up of the prepared sample solution is necessary to avoid contamination of the GC-system and to remove compounds
which interfere with the determination of PCB congeners. For complex sample compositions like waste oils, there is no general clean-up
procedure available for all possible interfering compounds.

NOTE 2 Halogenated aromatic compounds like tetrachlorobenzyltoluenes are not removed by the clean-up procedures given in this
standard. Interferences as reported in annex E (figure E.1) can result.
To determine the recovery of specified PCB congeners, submit solutions of standards in solvent (5.2.1) to the clean-up
procedure and compare the results obtained with those obtained with similar solutions not submitted to the clean-up procedure.
The calculated recovery of specified PCB congeners shall be greater than 95 % at a level of 1 µg/g each.

The above procedure does not take account of any oil present in the sample influencing the recovery from the clean-up
columns. If this is suspected, recoveries shall be determined using standard solutions containing in addition either unused base
oil (5.5) or a PCB free sample of the same oil as present in the sample at a concentration of approximately 10 % oil to solvent.

The specified solvent quantities for elution of the PCB from the columns (see 8.4 or annex B) shall be checked and if necessary
optimized by determining the recovery when a new batch of materials is used.
NOTE 3 The recovery is not taken into account when the results are stated. If solvents other than heptane are used, then the elution
volumes can differ.

8.2 Preparation of the silica gel/sulfuric acid separation material.

Activate the silica gel separation material (5.2.4) at 180 °C for 3 h before use.

Weigh (28 ± 1) g silica gel separation material (5.2.4) and (22 ± 1) g sulfuric acid (5.2.3), into a 200 ml conical flask, and
shake until any lumps have disappeared.

WARNING: Wear face protection and gloves, because the mixture will become hot.

Store the mixture in a closed desiccator. The mixture shall be used within one week.
8.3 Preparation of the combined benzenesulfonic acid/sulfuric acid column

Directly prior to the sample preparation procedure, put (0,5 ± 0,05) g of the silica gel/sulfuric acid separation material prepared
in accordance with 8.2 onto the top frit of the 3 ml benzenesulfonic acid/sulfuric acid column.
8.4 Preparation of the test solution

Set up the combined benzenesulfonic acid/sulfuric acid column on a 3 ml silica gel separating column with the aid of an
adapter. Elute the two columns three times with 2 ml solvent (5.2.1) in order to purify the stationary phases, then use vacuum
assisted drying.

Transfer 250 µl of the sample solutions prepared as described in clause 6, onto the silica gel/sulfuric acid stationary phase of
the upper column, and flush with 0,5 ml solvent (5.2.1).

Apply the sample to the packing of the upper column e.g. by reducing pressure slightly. The sample shall be distributed evenly
over the packing of the upper column. Elute the upper column twice with 1 ml solvent (5.2.1) after a period of at least 30 s.
Remove the upper column.

Elute the silica gel separation column twice with approximately 0,5 ml solvent (5.2.1), and transfer the eluate to a 5 ml
volumetric flask. Make up to the mark with solvent (5.2.1).

If necessary, determination of PCB shall be repeated at different dilutions of the sample with oil (5.5) to bring the measurement
within the linear range of the ECD.
Page 8
EN 12766-1:2000

25 mg sample
in 250 µl solvent solution

2,5 ml solvent

0,5 g SiO2/H2SO4 Removal of hetero com-

+ pounds, polyaromatic
0,5 g benzenesulfonic acid phase hydrocarbons and bases

2 x 0,5 ml solvent

Removal of polar com-pounds

0,5 g SiO2-phase and aromatics

make up 5,0 ml with solvent

GC

Figure 2 — Clean-up procedure

9 Gaschromatographic operating conditions

9.1 Setting up the GC apparatus

The operating conditions indicated in 9.2 to 9.5 have been found adequate but should be optimised with each GC system so that
gas chromatograms similar to that shown in annex A.1 are obtained from dilutions of the test mixture 5.4.6. In the example
given, hydrogen is used. Other carrier gases give different retention times.
9.2 Injectors

Set up the injector in accordance with the manufacturer's instructions.

NOTE Typical setting for this analysis are as follows:
a) for the split/splitless injector:

splitless mode: T = 240 °C to 280 °C

split valve closed between: 0,5 min to 1,5 min
split mode: T = 250 °C to 280 °C
split ratio: 5:1

b) for the on-column injector: T: 50 °C to 110 °C depending on the solvent used.

 Page 9
EN 12766-1:2000

9.3 Oven temperature programme

The oven temperature programme shall be selected to obtain a suitable chromatogram.

NOTE Typical settings are as follows:

initial isothermal period 1 min or 0,5 min

initial temperature 50 °C or 70 °C

temperature programme 50 °C to 168 °C at or 70 °C to 130 °C at

50 °C/min 40 °C/min

168 °C to 310 °C at 130 °C to 290 °C at

4,0 °C/min 2,5 °C/min

isothermal period 10 min or 5 min

cool down to 50 °C or 70 °C

These settings may be varied to obtain the required chromatogram.

The initial temperature and initial isothermal period shall be varied depending on the solvent and injection technique.
9.4 Carrier gas flow rate

Adjust the inlet pressure to give a flow rate through the column of 1 ml/min at 130 °C, e.g. 270 kPa for helium.
NOTE Hydrogen carrier gas is effective in reducing column pressure head analysis time.

9.5 Electron capture detector settings

The temperature shall be 300 °C to 350 °C.

Use the manufacturer's recommended settings to give the best conditions for linearity of the detector.

The flow rate of the make up gas shall be between 20 ml/min and 40 ml/min, and shall be selected to give the best sensitivity to
PCBs.

10 Check on instrumental performance

10.1 General provisions

When initially implementing this method and after major repairs and replacement of critical instrumentation components
(specifically EC detector and GC column), each laboratory that uses this method shall operate a performance control
programme. This should include verification of sensitivity, resolution and linearity range. It is recommended to monitor the
performance routinely at appropriate time intervals.
10.2 Sensitivity check

The ECD shall have sufficient sensitivity to give a signal to noise ratio (S/N) greater than 20 for one picogram of
hexachlorobenzene (5.3.1) injected on to the column, using the specified operating conditions (see clause 9).
10.3 Linearity check

The response of the electron capture detector (ECD) is proportional to the quantity of PCBs injected only within a limited
range; if the quantities of PCBs passing through the detector become excessive, the response will cease to be linear.

Determine the linear range as given in 10.3.1 to 10.3.3.

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EN 12766-1:2000

10.3.1 Dilute standard (5.4.4) in suitable steps with solvent (5.2.1) until a linear response is obtained as shown in figure 3, e.g.
20, 50, 200, 1000, 5000, 10 000 times dilution.
Add congener 30 (5.4.1) as internal standard to the dilutions to give a final concentration of 10 ng/ml. Inject a suitable quantity
into the GC (the same each time) into the GC according to the injection system using the chromatographic conditions in
clause 9.

10.3.2 Measure the peak area or height (Rj) for the specified 12 congeners and congener 209 and calculate the injected
amount (mj) of each congener in picogram for each dilution. Use the area or height of the congener 30 to check that the correct
volume has been injected. The area/height of the congener 30 peak for the series of injections should not vary by more than 5%
of the average for that series of injections. Tests that fall outside of this range shall be repeated.
Calculate the sensitivity factor (Sj) for each congener and each dilution using the following equation:
Rj
Sj =
mj
Where Sj, Rj and mj are as indicated above.

Plot Sj versus mj (see figure 3).

Figure 3 — Linearity check

10.3.3 The linearity plot is a line through the data points (figure 3). The upper limit of the linear range is the point where the
plot crosses the - 5 % envelope and the lower limit level where the plot crosses the + 5 % envelope.
The linear range of the detector is defined in fig. 3.
NOTE A nonlinear calibration can be used applying the same criteria of a ± 5 % envelope as shown in fig. 3.

10.4 Resolution check

Using the standard chromatographic parameters run a suitable dilution of test mixture (5.4.6) in the linear range. Identify the
peaks by comparison with the chromatogram in annex A.1.

The resolution of the pair of congener 28 and congener 31 shall be 0,5 (i.e. 50 %) or greater, for the pair of congeners 141/179
0,8 (i.e. 80 %) or greater, and for the pair of congeners 118/149 0,5 (i.e. 50 %) or greater.
 Page 11
EN 12766-1:2000

10.5 Blank check

Run each new batch of solvent and a blank test portion prepared with unused base oil (5.5) to ensure that there are no spurious
peaks from the solvent or the GC. Run a blank test portion with every batch of samples and at least every 20 samples.

11 Calibration

NOTE 1 The gas chromatograph is calibrated in the linear range of the ECD. The calibration solution should contain an amount of
mineral oil similar to the final analysis solution so that the ECD interferences are comparable with both injections.
Make a calibration standard by adding 1 ml of the calibration mixture solution (5.4.4) and 1 ml of the congener 30 solution
(5.4.1) to 5 g of a suitable oil (5.5), which has been weighed to an accuracy of 5 mg in a 50 ml volumetric flask and filling up to
the mark with solvent (5.2.1).

Submit 250 µl of the calibration standard to the clean-up procedure (see clause 8) and if necessary submit it to the optional
clean-up procedures given in annex B.

Inject the calibration standard solution into the GC, and run the GC in accordance with 9.3 and 10.3.

Identify the peaks as given in table 1 by comparison with the example in annex A.2 and calculate the experimental relative
retention times, ERRT, for each peak as follows:
ti − t 30
ERRTi =
t 209 − t 30
where:
i is the chosen peak
30 is congener 30
209 is congener 209
t is the retention time from injection

ERRTs shall be determined and entered into the data files for each individual GC system. The system should be recalibrated if
there are any changes in GC conditions (e.g. temperature program, etc.).
NOTE 2 Congener 30 and congener 209 are chosen as reference peaks for the determination of ERRT as they are at each end of the
chromatogram (test mixture) isolated from congeners occuring in commercial mixtures and enable accurate repeatable values of ERRTs to be
obtained.
Calculate the experimental relative response factors ERRFi for each of the reference PCB congeners from the mass
concentrations ßi and ßst and the associated peak responses Ri and Rst, using the following equations:
βst × Ri
ERRFi =
Rst × βi
where:

i is the mass concentration of PCB congener in nanogram per millilitre;

st is the mass concentration of internal standard (congener 209) in nanogram per millilitre.

Compile a calibration table as in table 1, listing the ERRTs and ERRFs for each congener.
Page 12
EN 12766-1:2000

Table 1 — Congeners for calibration

Congener number ERRT (examples) ERRF (examples)

30 0,0000 0,72
18 0,0284 0,27
31 0,1144 0,49
28 0,1165 0,74
52 0,1850 0,41
44 0,2254 0,46
101 0,3557 0,58
149 0,4743 0,57
118 0,4769 0,76
153 0,5210 0,68
138 0,5744 0,72
180 0,7034 1,13
194 0,8767 1,64
209 1,0000 1,00

12 Determination

Inject of the prepared test solution (8.4) the same volume as used for calibration onto the GC. Record the chromatogram with
the same setting of the gas chromatograph as was used in the calibration procedure given in clause 11.

The applied quantities of the PCB compounds which are to be determined and of the internal standard shall be within the
calibrated, linear response range of the detector. If necessary, the determination procedure shall be repeated with different
dilutions or sample sizes.

Calibration standard solutions shall be run with every batch of samples, or at least once every day.

13 Calculation

NOTE Calculation of total PCB content is based on part 2 (3.1 method A).
Identify the peaks by their experimental relative retention times (ERRT) as calculated for each peak using the
equation given in clause 10, and the PCB distribution pattern of the example in Annex A.1.
There shall be no interferences with the selected PCBs.The internal standard method is used for the quantitative calculation of
the chromatogram.

Calculate the proportion by mass of calibrated PCB congener wi(PCB) in milligrams per kilogram using the following equation:
Ri × mst
wi(PCB) =
Rst × mp × ERRFi
where:
Ri is the peak response (area or height) of PCB;
Rst is the peak response (area or height) of internal standard (congener 209);
ERRFi is the relative response factor of PCB;
mst is the mass of the internal standard used in sample solution preparation (clause 6) in nanograms;
mp is the mass of sample (weighed portion) in milligrams.

Determine the blank value in accordance with 10.5. Correct the calculation by taking into account the peak areas or heights of
the blank value for each individual peak of the reference PCB congeners.

14 Expression of results

Report the content of each individual congener determined, to the nearest 0,1 mg/kg.
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EN 12766-1:2000

15 Precision

15.1 Repeatability

The difference between two test results, obtained by the same operator with the same apparatus under constant operating
conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the
values given in table 2 only in one case in twenty.
15.2 Reproducibility

The difference between two single and independent results, obtained by different operators working in different laboratories on
identical test material, would in the long run, in the normal and correct operation of the test method, exceed the values given in
table 2 only in one case in twenty.

Table 2 — Repeatability and reproducibility

Massfraction per single congener Repeatability Reproducibility

mg/kg mg/kg mg/kg
0,2 0,04 0,1
0,5 0,08 0,2
1,0 0,1 0,5
1,5 0,2 0,7
2,0 0,2 1,0

16 Test report

The test report shall include at least the following information:

a) the type and identification of the sample under test;
b) a reference to this European Standard;
c) the sampling procedure used (see clause 7);
d) the clean-up procedure used (see clause 8);
e) the results of the test (see clause 14);
f) any deviation from the procedure described and any unusual features noted during the determinations;
g) the date of the test.
Page 14
EN 12766-1:2000

Annex A
(normative)

Identification PCB peaks

A.1 Identification of peaks of technical PCB mixtures

The chromatogram obtained shall be compared with those obtained for the test mixture solution (5.4.6) given in figure A.1.

The ERRT values in table A.1 are examples determined from the chromatogram as shown in figure A.1 and shall not be used in
the method. ERRT values shall be determined for the individual GC system being used (clause 9.1.).

Values appearing in parenthesis are calculated values for peaks (congeners) that do not appear in the test mixture solution
(5.4.6), e.g. ERRT (peak 44) = (0,3220)

All probables: Only PCB congeners present in detectable amounts in technical PCB products are recorded.
All possibles: All possible PCB congeners are recorded.

Figure A.1 — Chromatogram of test mixture solution (5.4.6) (determined with hydrogen)
(Aroclor 1242/1254/1260 (2:1:1) plus congener 30 and congener 209)
 Page 15
EN 12766-1:2000

Figure. A. 1 (continued)
Page 16
EN 12766-1:2000

A.2 Identification of peaks of calibration standard solution (see clause 11)

Figure A.2 — Chromatogram of calibration standard solution (see clause 11)

 Page 17
EN 12766-1:2000

A.3 Identification of PCB peaks of Aroclor test mixture solution (5.4.6)

The ERRT values in table A.1 are examples determined from the chromatogram as shown in figure A.1 and shall not be used in
the method. ERRT values shall be determined for the individual GC system being used (clause 9).
Values appearing in parenthesis are calculated values for peaks (congeners) that do not appear in the test mixture solution
(5.4.6), e.g. ERRT (peak 44) = (03220)
All probables: Only PCB congeners present in detectable amounts in technical PCB products are recorded.
All possibles: All possible PCB congeners are recorded.
Table A.1 — Congeners and congener groups present in peaks from technical PCB products

Calibration Congener number

Peak nr. ERRT (example) All probables All possibles

(IUPAC nr.) (IUPAC nr.)
1 (-0,2227) - 1
2 (-0,1271) 2,3 2,3
3 -0,1241 4,10 4,10
4 -0,0816 7,9 7,9
5 -0,0620 6 6
6 -0,0516 5,8 5,8
7 (-0,0323) - 14
8 -0,0138 19 19
9 0,0000 - 30
10 (0,0057) - 11
11 (0,0134) - 12,13
12 0,0284 18 18
13 0,0318 15,17 15,17
14 0,0482 24,27 24,27
15 0,0644 16,32 16,32
16 (0,0724) - 23
17 0,0818 34 34,54
18 0,0886 29 29
19 0,0988 26 26
20 0,1019 25 25
21 (0,1104) - 50
22 0,1144 31 31
23 0,1165 28 28
24 0,1360 20,33,53 20,21,33,53
25 0,1444 21 21
26 0,1509 22,51 22,51
27 0,1587 45 45
28 0,1769 46 46
29 0,1850 52 39,52,69,73
30 0,1934 49 38,43,49
31 0,1994 47,48,75 47,48,62,65,75
32 (0,2164) 35 35,104
33 0,2254 44 44
34 0,2317 37,42,59 37,42,59
35 0,2411 71,72 71,72
36 0,2494 41,64 41,64
37 0,2550 96 68,96
38 0,2658 40 40,57,103
39 (0,2832) 67,100 67,100
40 0,2867 63 58,63
41 0,2942 74 61,74,94
42 0,3020 70 70,76,96
Page 18
EN 12766-1:2000

Calibration Congener number

Peak nr. ERRT (example) All probables All possibles

(IUPAC nr.) (IUPAC nr.)
43 0,3101 66,95 66,80,88,93,95,102
44 (0,3220) 121 121
45 0,3232 91 55,91
46 0,3424 56,60 56,60,155
47 (0,3457) 92 92
48 0,3529 84 84
49 0,3557 101 89,90,101
50 0,3659 99 79,99,113
51 0,3779 119 112,119,150
52 0,3881 83 78,83,109
53 0,3980 97 86,97,152
54 0,4079 87,115 81,87,111,115,116,
117,125,145
55 0,4156 85 85
56 0,4222 136 120,136,148
57 0,4274 77,110 77,110
58 (0,4482) 82 82,154
59 0,4509 151,82 151,82
60 0,4600 135 124,135,144
61 0,4678 107 107,108,147
62 0,4743 149 106,123,149
63 0,4769 118 118,139,140
64 0,4949 134 134,143
65 0,4988 114 114
66 0,5030 122,131 122,131,133,142
67 0,5095 146 146,161,165,188
68 0,5210 132,153 132,153,184
69 0,5283 105,132 105,127,168
70 0,5457 141 141
71 0,5496 179 179
72 0,5588 130 130
73 0,5640 137,176 137,176
74 0,5744 138,160 138,160,163,164
75 0,5786 158 158,186
76 0,5903 126,129,178 126,129,178
77 0,6013 175 166,175
78 0,6070 187 159,182,187
79 0,6161 183 162,183
80 0,6268 128 128
81 0,6364 167 167
82 (0,6414) 185 185
83 0,6515 174 174,181
84 0,6617 177 177
85 (0,6695) 202 202
86 0,6711 156,171 156,171
87 0,6826 201*,157,173 201*,157,173
88 0,6912 172 172,204
89 0,6964 197 172,192,197
90 0,7034 180 180
91 0,7081 193 193
92 0,7159 191 191
93 0,7269 200* 200*
94 0,7362 169 169
95 0,7589 170,190 170,190
96 0,7686 198 198
 Page 19
EN 12766-1:2000

Calibration Congener number

Peak nr. ERRT (example) All probables All possibles

(IUPAC nr.) (IUPAC nr.)
97 0,7751 199* 199*
98 0,7845 196,203 196,203
99 0,8116 189 189
100 0,8376 195,208 195,208
101 0,8522 207 207
102 0,8767 194 194
103 0,8848 205 205
104 0,9447 206 206
105 1,0000 209 (int. Std.) 209 (Int. Std.)

NOTE *) Ballschmitter and Zell numbering as follows:

199 (IUPAC) = 201 (Ballschmitter)
200 (IUPAC) = 199 (Ballschmitter)
201 (IUPAC) = 200 (Ballschmitter)
Page 20
EN 12766-1:2000

A.4 Elution order of PCBs

Table A.2 gives the relative retention times of PCB congeners obtained from a high performance column, using crosslinked 5
% phenyl methyl silicone gum phase; 50 m x 0,2 mm i.d. column with 0,11 m film thickness.

Table A.2 — Relative retention times of PCB congeners to congener 209

Congener Number Relative Retention Time Congener Number Relative Retention Time
(IUPAC) to DCB (IUPAC) to DCB
1 0,1471 48 0,4431
2 0,1845 65 0,4450
3 0,1882 62 0,4464
10 0,2137 35 0,4514
4 0,2139 104 0,4532
7 0,2445 44 0,4604
9 0,2448 37 0,4628
6 0,2581 59 0,4630
8 0,2651 42 0,4640
5 0,2653 72 0,4748
14 0,2832 71 0,4753
19 0,2901 41 0,4754
30 0,3015 64 0,4763
11 0,3085 68 0,4802
12 0,3142 96 0,4818
13 0,3158 40 0,4861
18 0,3218 103 0,4899
15 0,3227 57 0,4911
17 0,3237 100 0,4966
24 0,3342 67 0,4968
27 0,3355 58 0,5018
16 0,3454 63 0,5040
32 0,3464 61 0,5079
23 0,3592 94 0,5079
34 0,3603 74 0,5089
54 0,3620 70 0,5151
29 0,3639 76 0,5152
26 0,3726 98 0,5159
25 0,3751 102 0,5174
50 0,3818 93 0,5180
31 0,3834 66 0,5190
28 0,3840 80 0,5206
21 0,3940 95 0,5206
33 0,3966 88 0,5227
20 0,3973 121 0,5257
53 0,3989 91 0,5287
51 0,4041 55 0,5299
22 0,4065 155 0,5398
45 0,4129 56 0,5408
36 0,4168 60 0,5408
46 0,4240 92 0,5471
39 0,4276 84 0,5473
69 0,4297 89 0,5506
73 0,4339 90 0,5539
52 0,4342 101 0,5541
43 0,4370 113 0,5585
38 0,4376 99 0,5602
49 0,4392 79 0,5615
47 0,4420 119 0,5686
75 0,4424 150 0,5687
 Page 21
EN 12766-1:2000

Congener Number Relative Retention Time Congener Number Relative Retention Time
(IUPAC) to DCB (IUPAC) to DCB
112 0,5703 130 0,6940
109 0,5732 176 0,6960
78 0,5739 137 0,6983
83 0,5744 160 0,7046
152 0,5775 163 0,7046
97 0,5812 164 0,7049
86 0,5816 138 0,7053
116 0,5842 186 0,7065
125 0,5852 158 0,7078
81 0,5858 129 0,7146
145 0,5858 126 0,7157
117 0,5859 178 0,7181
115 0,5879 166 0,7214
87 0,5883 175 0,7251
111 0,5891 182 0,7291
85 0,5930 187 0,7292
148 0,5948 159 0,7293
120 0,5960 183 0,7355
136 0,5961 162 0,7371
77 0,5997 128 0,7394
110 0,6016 167 0,7445
154 0,6049 185 0,7477
82 0,6148 174 0,7589
151 0,6192 181 0,7591
135 0,6253 177 0,7651
144 0,6293 171 0,7707
124 0,6273 202 0,7707
147 0,6296 156 0,7722
108 0,6313 173 0,7767
107 0,6315 157 0,7797
123 0,6343 201 0,7810
149 0,6357 204 0,7829
106 0,6364 192 0,7878
118 0,6377 172 0,7887
139 0,6390 197 0,7901
140 0,6390 180 0,7967
143 0,6468 193 0,8000
134 0,6475 191 0,8048
114 0,6505 200 0,8093
142 0,6524 169 0,8217
131 0,6529 170 0,8327
122 0,6546 190 0,8327
133 0,6546 198 0,8427
165 0,6593 199 0,8456
188 0,6593 196 0,8516
146 0,6626 203 0,85161
161 0,6639 189 0,8710
184 0,6684 208 0,8880
132 0,6702 195 0,8880
153 0,6703 207 0,8978
105 0,6716 194 0,9165
168 0,6734 205 0,9221
127 0,6743 206 0,9626
141 0,6863 209 1,000
179 0,6864
Page 22
EN 12766-1:2000

Annex B
(normative)

Alternative and additional clean-up procedures

An alternative clean-up procedure is given in B.1. This method gives cleaner extracts than obtained by the method given in
clause 8, but is a more time consuming method.

The methods given in B.2, B.3, B.4, and B.5 may be used in addition to the methods given in clause 8 or in B.1.

B.1 Alternative clean-up procedure

B.1.1 Principle

The greater part of the oil matrix (especially the naphthenes) is removed by impregnated aluminium oxide. The dark brown
matter present in waste oil is removed by silica gel and this also eliminates the interference which appears in the later part of
the chromatogram, but it fails to eliminate early eluting interferences. Chlorinated paraffines also appear to be removed by the
combination of both columns.
B.1.2 Apparatus

B.1.2.1 Normal laboratory apparatus.

B.1.2.2 Homogenizer / Roller apparatus
B.1.2.3 Vibrator (e.g. Chrompack 8480).
B.1.2.4 Concentrator, e.g. Kuderna-Danish with Snyder columns.

B.1.3 Reagents and materials

B.1.3.1 Potassium hydroxide, p.a. saturated bidest aqueous solution.

B.1.3.2 Sodium sulfate, p.a., anhydrous.
B.1.3.3 Aluminium oxide (Woelm), basic, activity I.
B.1.3.4 Silica gel, p.a. 70 to 230 mesh.
B.1.3.5 Nitrogen, technical grade.
B.1.3.6 Desiccant, e.g. phosphorus pentoxide.
B.1.3.7 Chromatographic column 1 (aluminium oxide), glass, 320 mm x 6 mm ID (see fig. B.1)
B.1.3.8 Chromatographic column 2 (silicagel), glass, 400 mm x 9 mm ID (see fig. B.2)

B.1.4 Sample clean-up by basic aluminium oxide

B.1.4.1 Preparation of the clean-up column (B.1.3.7)

Transfer the aluminium oxide, directly from the original container, to a petri dish and activate in a drying oven at 200/C for at
least 4 h. Transfer the hot petri dish with the aluminium oxide to a desiccator containing a desiccant, and allow to cool.
Transfer a part of the newly activated material to a container, record the mass on a balance and add 20 % (m/m) of the
saturated potassium hydroxide solution, evenly distributed over the aluminium oxide surface.

Stopper the container and homogenise the material in a homogeniser. Transfer a plug of glass wool into the chromatography
column 1. Transfer 3 g of the homogenised impregnated aluminium oxide to a chromatography column 1. Accomplish a proper
packing using a vibrator. Place an additional layer of anhydrous sodium sulfate of 1 cm height on top of the aluminium oxide
and vibrate again.
 Page 23
EN 12766-1:2000

Elute the column with 10 ml solvent (5.2.1). Ensure the column does not run dry.

B.1.4.2 Optimization of the fractionation

Place a calibrated tube below the column. Quantitatively transfer 1,0 ml of the sample solution, prepared in accordance to
clause 6, to the column and elute until the meniscus touches the surface of the sodium sulfate. Rince twice with 1 ml solvent.
Add 10 ml solvent to the column and elute with a flow of approximate 1 ml/min. Collect the eluate. Concentrate this fraction
under a gentle stream of nitrogen to approximately 1 ml.

B.1.5 Sample fractionating by silica gel

B.1.5.1 Preparation of the fractionation column (B.1.3.8)

Transfer the silica gel, directly from the original container, into a petri dish and activate in a drying oven at 150/C for at least 4
h. Transfer the hot petri dish with the silica gel to a desiccator containing a desiccant, and allow to cool. Transfer a part of the
newly activated material to a container, record the mass on a balance and add 0,5 % (m/m) double distilled water, evenly
distributed over the silicagel surface.

Stopper the container and homogenise the material in a homogeniser. Transfer a plug of glass wool into chromatograph column
2. Transfer 2 g of the homogenised deactivated silica gel to chromatographic column 2. Accomplish a proper packing, eg.
using a vibrator. Place an additional layer of anhydrous sodium sulfate of 1 cm height on top of the sicila gel and vibrate again.

Elute the column with 10 ml solvent (5.2.1). Ensure the column does not run dry.

B.1.5.2 Optimization of the fractionation.

Place a calibrated tube below the column. Transfer the extract obtained in B.1.4.2 quantitatively to the top of column 2
prepared in accordance with B.1.5.1 and elute until the meniscus touches the sodium sulfate surface. Add 25 ml solvent to the
column and elute with a flow of appoximately 1 ml/min. Collect a first fraction of 5 ml. Replace the calibrated tube by a
second one and collect another 5 ml. Repeat this twice more. Concentrate all fractions collected in calibrated tubes to 0,5 ml
under a gentle stream of nitrogen, and make up to 1 ml with solvent.

Determine the presence of PCB in all fractions by successive injection and analysis of 1 µl of each fraction into the gas
chromatograph. Collect further fractions, in case the last fraction still contains any PCB. Finally, determine the total volume
necessary to elute all PCB.

B.1.5.3 Preparation of the test solution

Clean the concentrated extract obtained in B.1.4.2 in accordance with B.1.5.2 by collecting a volume corresponding to the
optimum total volume determined in B.1.5.2. Concentrate the eluate,eg in a Kuderna Danish concentrator, to a few millilitres.
Concentrate the remaining raction under a gentle stream of nitrogen to 1 ml.
NOTE Further information can be obtained from the following publications:
- RIVM (1989). Werkdocument rondzending analyses van PCB's in afvalolie volgens de IvM methode, Rijksinstituut
voor Volksgezondheid en Milieuhygiene, Bilthoven.
- Wegener, J.W.M., P. de Voogt en H. Govers (1987).
Voorschrift voor de bepaling van polychloorbifenylen in minerale olien, IvM 87-17, Instituut voor Milieuvraagstukken,
Vrije Universiteit van Amsterdam.
Page 24
EN 12766-1:2000

Figure B.1 Figure B.2

Chromatographic Column 1 for the clean up and Chromatographic Column 2 for the clean up and
fractionation of the extract (B.1.3.7) fractionation of the extract (B.1.3.8)
 Page 25
EN 12766-1:2000

B.2 Sulfuric acid treatment

This treatment is recommended if sulfoniable compounds are present.

Face shields, gloves and protective clothing shall be worn.

1 ml of the sample solution (section 6 of this standard) is transferred into a convenient stoppered glass vial. Add 19 ml of
solvent 5.2.1. Pour in 5 ml of concentrated sulfuric acid and shake vigourously at intervals for 5 minutes.

Allow to separate completely (about 15 min).

If necessary, transfer to a centrifuge tube and centrifuge to separate the layers.

Take a portion of the upper solvent layer for GC analysis.

B.3 Copper treatment

This treatment is recommended to remove free sulfur from waste oils with high free-sulfur content.

Preclean copper foil or granules by rinsing with, and washing with hydrochloric acid solution 6 mole HCl followed by pure
acetone and then solvent 5.2.1. Shake the solution from the column clean up (procedure specified in clause 8) with the copper
foil or granules to remove free sulfur.

Submit the solution to GC analysis.

B.4 Non-destructive sulfur removing treatment

This treatment is recommended for environmental samples (e.g. sludge or soil).

B.4.1 TBA-sulfite reagents

A solution of 3,39 g (0,01 mole) tetrabutylammonium hydrogen sulfate in 100 ml of water is extracted with 3 x 20 ml of solvent
5.2.1 (to remove impurities) and then saturated with sodium sulfite 25 g (0,2 mol) analytical grade.
B.4.2 Removal of sulfur

2 ml of sample solution (section 6 of this standard) is shaken with 1 ml isopropanol and 1 ml TBA-reagent for at least 1 minute.
If the precipitated sodium sulphite disappears, more is added in 10 mg portions until a solid residue remains after repeated
shaking. Water (5 ml) is added and the test tube is shaken for another minute, followed by centrifugation, and the solvent phase
is transferred to a test tube for GC analysis.

B.5 Thermal shock pretreatment

B.5.1 General

Thermal shock pretreatment shall be used when the other clean-up methods cannot remove interferences, e.g. chlorinated
waxes.
B.5.2 Apparatus

B.5.2.1 Analytical balance, capable of weighing to 1 kg to the nearest with an accuracy of 0,1 g.

B.5.2.2 Two-necked round-bottomed 500 ml flask in glass (central neck and one side neck to hold the thermometer) with
either conical ground joints or smooth glass joints.

B.5.2.3 Suitable heating mantle for flask, with regulator.

B.5.2.4 Thermometer, measuring 0 °C to 500 °C in 1 °C intervals.

Page 26
EN 12766-1:2000

B.5.2.5 Male ground joint in glass with a screw plastics cap bored to carry the thermometer or smoothed glass joints.

B.5.2.6 Bulb condenser with ground joint, or smooth glass joint.

B.5.2.7 Aeration tube to permit the introduction of a controlled flow of nitrogen into the flask.
B.5.3 Procedure

Introduce 100 g of sample weighed to an accuracy of 0,1 g into the round-bottomed flask (B.5.2.2).

Install the round flask into the heating mantle (B.5.2.3), which is placed in a fume cupboard.

Connect the thermometer (B.5.2.4) into the side neck, and the aeration tube (B.5.2.7) to the central neck and regulate the
nitrogen flow to 2 l/min.
NOTE The nitrogen permits the evaporation of water during the dehydration.
Apply heat to the flask until the temperature reaches 150 °C and until no drops of water remain on the top of the flask.

Allow the flask to cool to room temperature, remove the thermometer and weigh the flask and contents to determine the mass
of water evaporated.

Replace the flask in the mantle, replace the thermometer and fit the bulb condenser. Apply heat until the temperature reaches
370 °C, and continue heating for approximately 15 min.

Allow the flask to cool to room temperature, remove the condenser and continue the sample preparation.
Consider the contents of the flask to be the initial sample (Annex E, figure E.2.b).
 Page 27
EN 12766-1:2000

Annex C
(informative)

Systematic numbering of PCB compounds

Table C.1 — Systematic numbering of PCB compounds.

The number is used as a synonym for the corresponding PCB compound in tables and figures
Nr. Structure Nr. Structure Nr. Structure Nr. Structure
Monochlorobiphenyls Tetrachlorobiphenyls Pentachlorobiphenyls Hexachlorobipenyls
1 2 51 2,2’,4,6’ 106 2,3,3’,4,5 161 2,3,3’,4,5’,6
2 3 52 2,2’,5,5’ 107 2,3,3’,4’,5, 162 2,3,3’,4’,5,5’
3 4 53 2,2’,5,6’ 108 2,3,3’,4,5’ 163 2,3,3’,4’,5,6
Dichlorobiphenyls 54 2,2’,6,6’ 109 2,3,3’,4,6 164 2,3,3’,4’,5’,6
4 2,2’ 55 2,3,3’,4 110 2,3,3’,4’,6 165 2,3,3’,5,5’,6
5 2,3 56 2,3,3’,4’ 111 2,3,3’,5,5’ 166 2,3,4,4’,5,6
6 2,3’ 57 2,3,3’,5 112 2,3,3’,5,6 167 2,3’,4,4’,5,5’
7 2,4 58 2,3,3’,5’ 113 2,3,3’,5’,6 168 2,3’,4,4’,5’,6
8 2,4’ 59 2,3,3’,6 114 2,3,4,4’,5 169 3,3’,4,4’,5,5’
9 2,5 60 2,3,4,4’ 115 2,3,4,4’,6 Heptachlorobiphenyls
10 2,6 61 2,3,4,5 116 2,3,4,5,6 170 2,2’,3,3’,4,4’,5
11 3,3’ 62 2,3,4,6 117 2,3,4’,5,6 171 2,2’,3,3’,4,4’,6
12 3,4 63 2,3,4’,5 118 2,3’,4,4’,5 172 2,2’,3,3’,4,5,5’
13 3,4’ 64 2,3,4’,6 119 2,3’,4,4’,6 173 2,2’,3,3’,4,5,6
14 3,5 65 2,3,5,6 120 2,3’,4,5,5’ 174 2,2’,3,3’,4,5,6’
15 4,4’ 66 2,3’,4,4’ 121 2,3’,4,5’,6 175 2,2’,3,3’,4,5’,6
Trichlorobiphenyls 67 2,3’,4,5 122 2’,3,3’,4,5 176 2,2’,3,3’,4,6,6’
16 2,2’,3 68 2,3’,4,5’ 123 2’,3,4,4’,5 177 2,2’,3,3’,4’,5,6
17 2,2’,4 69 2,3’,4,6 124 2’,3,4,5,5’ 178 2,2’,3,3’,5,5’,6
18 2,2’,5 70 2,3’,4’,5 125 2’,3,4,5,6’ 179 2,2’,3,3’,5,6,6’
19 2,2’,6 71 2,3’,4’,6 126 3,3’,4,4’,5 180 2,2’,3,4,4’,5,5’
20 2,3,3’ 72 2,3’,5,5’ 127 3,3’,4,5,5’ 181 2,2’,3,4,4’,5,6
21 2,3,4 73 2,3’,5’,6’ Hexachlorobiphenyls 182 2,2’,3,4,4’,5,6’
22 2,3,4’ 74 2,4,4’,5 128 2,2’,3,3’,4,4’ 183 2,2’,3,4,4’,5’,6
23 2,3,5 75 2,4,4’,6 129 2,2’,3,3’,4,5 184 2,2’,3,4,4’,6,6’
24 2,3,6 76 2’,3,4,5 130 2,2’,3,3’,4,5’ 185 2,2’,3,4,5,5’,6
25 2,3’,4 77 3,3’,4,4’ 131 2,2’,3,3’,4,6 186 2,2’,3,4,5,6,6’
26 2,3’,5 78 3,3’,4,5 132 2,2’,3,3’,4,6’ 187 2,2’,3,4’,5,5’,6
27 2,3’,6 79 3,3’,4,5’ 133 2,2’,3,3’,5,5’ 188 2,2’,3,4’,5,6,6’
28 2,4,4’ 80 3,3’,5,5’ 134 2,2’,3,3’,5,6 189 2,3,3’,4,4’,5,5’
29 2,4,5 81 3,4,4’,5 135 2,2’,3,3’,5,6’ 190 2,3,3’,4,4’,5,6
30 2,4,6 Pentachlorobiphenyls 136 2,2’,3,3’,6,6’ 191 2,3,3’,4,4’,5’,6
31 2,4’,5 82 2,2’,3,3’,4 137 2,2’,3,4,4’,5 192 2,3,3’,4,5,5’,6
32 2,4’,6 83 2,2’,3,3’,5 138 2,2’,3,4,4’,5’ 193 2,3,3’,4’,5,5’,6
33 2’,3,4 84 2,2’,3,3’,6 139 2,2’,3,4,4’,6 Octachlorobiphenyls
34 2’,3,5 85 2,2’,3,4,4’ 140 2,2’,3,4,4’,6’ 194 2,2’,3,3’,4,4’,5,5’
35 3,3’,4 86 2,2’,3,4,5 141 2,2’,3,4,5,5’ 195 2,2’,3,3’,4,4’,5,6
36 3,3’,5 87 2,2’,3,4,5’ 142 2,2’,3,4,5,6 196 2,2’,3,3’,4,4’,5,6’
37 3,4,4’ 88 2,2’,3,4,6 143 2,2’,3,4,5,6’ 197 2,2’,3,3’,4,4’,6,6’
38 3,4,5 89 2,2’,3,4,6’ 144 2,2’,3,4,5’,6 198 2,2’,3,3’,4,5,5’,6
39 3,4’,5 90 2,2’,3,4’,5 145 2,2’,3,4,6,6’ 199 2,2’,3,3’,4,5,6,6’
Tetrachlorobiphenyls 91 2,2’,3,4’,6 146 2,2’,3,4’,5,5’ 200 2,2’,3,3’,4,5’,6,6’
40 2,2’,3,3’ 92 2,2’,3,5,5’ 147 2,2’,3,4’,5,6 201 2,2’,3,3’,4,5,5’,6
41 2,2’,3,4 93 2,2’,3,5,6 148 2,2’,3,4’,5,6’ 202 2,2’,3,3’,5,5’,6,6’
42 2,2’,3,4’ 94 2,2’,3,5,6’ 149 2,2’,3,4’,5’,6 203 2,2’,3,4,4’,5,5’,6
Page 28
EN 12766-1:2000

Nr. Structure Nr. Structure Nr. Structure Nr. Structure

43 2,2’,3,5 95 2,2’,3,5’,6 150 2,2’,3,4’,6,6’ 204 2,2’,3,4,4’,5,6,6’
44 2,2’,3,5’ 96 2,2’,3,6,6’ 151 2,2’,3,5,5’,6 205 2,3,3’,4,4’,5,5’,6
45 2,2’,3,6 97 2,2’,3’,4,5 152 2,2’,3,5,6,6’ Nonachlorobiphenyls
46 2,2’,3,6’ 98 2,2’,3’,4,6 153 2,2’,4,4’,5,5’ 206 2,2’,3,3’,4,4’,5,5’,6
47 2,2’,4,4’ 99 2,2’,4,4’,5 154 2,2’,4,4’,5,6’ 207 2,2’,3,3’,4,4’,5,6,6’
48 2,2’,4,5 100 2,2’,4,4’,6 155 2,2’,4,4’,6,6’ 208 2,2’,3,3’,4,5,5’,6,6’
49 2,2’,4,5’ 101 2,2’,4,5,5’ 156 2,3,3’,4,4’,5 Decachlorobiphenyls
50 2,2’,4,6 102 2,2’,4,5,6’ 157 2,3,3’,4,4’,5’ 209 2,2’,3,3’,4,4’,5,5’,6,6’
103 2,2’,4,5’,6 158 2,3,3’,4,4’,6
104 2,2’,4,6,6’ 159 2,3,3’,4,5,5’
105 2,3,3’,4,4’ 160 2,3,3’,4,5,6

NOTE 1 This table is taken from K. Ballschmitter, W. Schaefer, and H. Bechert, Fresenius’ Zeitschrift für Analytische Chemie, 326,
(1987), 253.

NOTE 2 The numbers differ from the IUPAC rules as follows:

199 (Ballschmitter) = 200 (IUPAC)
200 (Ballschmitter) = 201 (IUPAC)
201 (Ballschmitter) = 199 (IUPAC)
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EN 12766-1:2000

Annex D
(informative)

Tradenames and manufacturers

D.1 Commercial PCBs

Producer Country Tradename

Monsanto USA and Britain Aroclor
Bayer Germany Clophen
Prodelec France Phenclor and Pyralene
Kanegafuchi Japan Santotherm
Mitsubishi Japan Santotherm
Caffaro Italy Fenclor/Apirolio

D.2 Suitable GC columns

Column Manufacturer
RTx5 Restex
DB5 J&W
SPB-5 Supelco
OV-5 Ohio Valley
HP-5, Ultra-Z Hewlett Packard
RSL-200 Alltech
CP SIL 8CB Chrompack
BP5 SGE
007-2 Quadrex
TRB-5 Teknokroma

D.3 Suitable calibration standards

Certified calibration mixture in solvent (5.2.1) containing, at least, the following PCB congeners at a concentration of 10 mg/l
each: 18, 28, 31, 44, 52, 101, 118, 138, 149, 153, 170, 180, 194 and 209.

The calibration mixture shall not contain congener 30 and other congeners which are not resolved from the selected congeners
on the specified column (6.3).

The following standards have been proved suitable:

- Standard CLB-1, supplied by the National Research Council of Canada, Institute for Marine Biosciences, Marine
Analytical Chemistry Standards Program, 1411 Oxford Street, Halifax, Nova Scotia, Canada B3H 3Z1.
- 15 congener mix supplied by Supelco (does not contain Congener 209)
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EN 12766-1:2000

Annex E
(informative)

Determination of TCBTs

NOTE Tetrachlorobenzyltoluenes (trade name "Ugilec 141") are produced for electrotechnical and mining applications. If not properly
discharged, these products can contaminate waste oil samples

Figure E.1 - Tetrachlorobenzyltoluene in mineral oil

50 mg/kg + Internal Standard (5.4.3) / GC conditions as in clause 9
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EN 12766-1:2000

Figure E.2.a - Gaschromatogram of waste oil containing chlorinated wax

(normal clean-up; clause 8)

Figure E.2.b - As figure E.2.a but with thermal shock clean-up

Figure E.2 - Thermal shock clean-up of waste oil
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EN 12766-1:2000

Figure E.3 - Examples of gaschromatograms of Aroclor