Journal of Hazardous Materials B137 (2006) 15141522

Levels of polychlorinated biphenyls (PCBs)

in transformer oils from Korea
Sun Kyoung Shin , Tae Seung Kim
National Instituted of Environmental Research, Sudokwon Landll 2-1 Environmental Complex, Kyungseodong, Seogu, Incheon 404-170, Korea
Received 10 October 2005; received in revised form 20 April 2006; accepted 20 April 2006
Available online 28 April 2006

Abstract
Using Korean waste official method, polychlorinated biphenyls (PCBs) were analyzed from 33 transformer oils collected under National Institute
of Environmental Research (NIER) in Republic of Korea (ROK) and their emission rate in Korea was estimated. Practical quantification limits
analyzed by this method were in the ranges of 0.02 and 0.05 mg L1 , and recovery of samples was in the ranges of 7797%. The analytical results
showed that PCBs in the transformer oils were identified as Aroclor 1242, 1254 or 1260. Twenty-nine samples were determined to contain PCBs
of >0.05 mg L1 and among these samples, nine samples contained to have >2 mg kg1 which is limit of Waste Control Act (WCA) with regard to
PCBs in transformer oil from Korea. The concentrations of PCBs in transformer oils were between N.D. (not detected) and 48.33 mg kg1 . PCBs
concentrations did not exceed 50 mg kg1 which is generally accepted limit for the definition of waste in POPs Guideline of Basel Convention.
2006 Elsevier B.V. All rights reserved.

Keywords: Transformer oil; PCBs; Korean waste official method; Aroclor; Peak pattern; GC/ECD

1. Introduction sistency and toxicity. The toxic effects are compounded by the
hydrophobicity of PCBs, which causes them to bio-accumulate
Polychlorinated biphenyls (PCBs) are a class of 209 con- in the fatty tissues of animals [8,9]. Actually, PCBs do not
geners that were widely used in a wide variety of applications, readily decompose or biodegrade in the environment, which
including dielectric fluid in transformers and large capacitors, is one of the major reasons for the PCBs contamination of
heat transfer fluids, hydraulic fluids, lubricating and cutting oils, environment. In these senses, United States Environmental
and as additives in pesticides, paints, adhesives, sealants, and Protection Agency (USEPA) has identified remediation of
plastics. Complex mixtures of PCBs were commercially pro- PCB-contaminated soil as a high priority. Furthermore, it
duced during 1929 to early 1970s. The commercial names of was reported that the recycled transformer oils were often
PCBs are known by a variety of trade names, such as Aroclor contaminated with trace amount of PCBs (UNEP Chemicals,
(USA), Phenoclor (France), Kanechlor (Japan), Sovol (Russia), 1999).
Chlophen (Germany), and so on [14]. In 1999, ROK the Environmental Law [10] regarding PCBs in
PCBs were produced in the United States from 1929 to 1977, transformer oil limit was changed from 50 to 2 mg L1 for liquid
when concern over adverse environmental effects led to a ban waste [7]. According to the Stockholm Convention on Persistent
on their industrial manufacture was under the Toxic Substances Organic Pollutants (POPs) entered into force on May seven-
Control Act of 1976 (TSCA) [3,5]. During this period global teenth 2004, the Ministry of Environment in Korea started new
production of PCBs was approximately 1.3 million tons with survey on PCBs concentration existing transformers at Power
625,000 t generated in the United States and 75,000 t exported Station, and launched an initiative to set up a project on environ-
to other countries [57]. The widespread release of PCBs into mental sound management of end-of-life transformer oils with
the environment presents a serious problem due to their per- regard to the elimination of the use of PCBs in equipment by
2015. In response to new regulation, the Ministry of Environ-
ment revised the Waste Official Testing Method (WOTM) by
Corresponding author. Tel.: +82 32 560 7185; fax: +82 32 568 2039. adding the quality control concept to regulate the waste man-
E-mail address: shinsun@me.go.kr (S.K. Shin). agement [11].

0304-3894/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2006.04.031
 S.K. Shin, T.S. Kim / Journal of Hazardous Materials B137 (2006) 15141522 1515

PCBs is analyzed with capillary column GC-ECD [1113],

quadrupole low-resolution GC/MS and double-focus high res-
olution GC/MS. All the analytical techniques have accuracy
problems in PCBs detection, which are attributed to deterioration
in sensitivity and baseline of chromatogram induced by inter-
fering components from sample matrix. It is difficult to separate
PCBs from the interfering components derived from the mineral
oil because of their similar physical and chemical properties.
Analytical techniques with high sensitivity such as high resolu-
tion GC/MS require pre-treatment which uses more advanced
separation techniques such as multilayer chromatography.
In this study, PCBs analytical methods of US EPA 8082 [13],
Canada [12] and Korea [7,11] were compared on quantification
peaks selection, and 33 transformer oils were analyzed to deter-
mine the release patterns of PCBs based on Guideline for PCBs
analytical method of transformer oil in Korea.

2. Experimental method

2.1. Sample collection

Thirty-three samples of transformer oils from various regions

Fig. 1. Flow chart for pre-treatment procedure of PCBs in transformer oil. of Power Station were collected by NIER in Republic of Korea
(ROK). Sampling activities were conducted in accordance with

Fig. 2. Quantification method for PCBs in transformer oil: (a) comparison the sample pattern with Aroclor standard; (b) confirmation of the Aroclor mixture pattern;
(c) quantification of the confirmed peaks using calibration peaks.
1516 S.K. Shin, T.S. Kim / Journal of Hazardous Materials B137 (2006) 15141522

Fig. 2. (Continued ).

procedures presented in sampling method [7,11]. Before sam- formed. Flow chart for pre-treatment procedure of PCBs in
pling the transformer oil, the working zone with proper signs and transformer oil is shown in Fig. 1.
disconnecting power by electrician were established. Also, prior
to sampling, transformers were inventoried. The transformer 2.2.2. Chromatographic operating conditions
valve opened, and collected about 40 mL of sample in amber vial Analyses were conducted on an Agilent 6890N GC equipped
with septum open top cap. When the sample container is filled with electron capture detector (ECD). An HP-five type GC col-
above half of bottle, the transformer valve was closed carefully. umn (30 m 0.25 mm i.d., 0.25 mm) was used for the analysis of
Finally, the sample container was capped tightly and labeled the oil extracts. The temperature program of the column was started
sample bottle with an appropriate sample label, addressing all at 100 C (hold 2 min); 15 C min1 until 160 C, 5 C min1
the categories or parameters. Samples were transported back to until 280 C (hold 10 min). A 1 L of extract was injected in
the laboratory and stored at 4 C. splitless mode (1 min). Injector port temperature was set at
240 C. ECD temperature was set at 300 C with nitrogen flow
2.2. PCBs analysis rate 1 mL min1 .

Aroclor 1242, 1248, 1254, and 1260 standards (Supelco Co.) 2.2.3. Calibration
were used in this study. The analytical method of this study was Five calibration standards were prepared in graduated
based on the Korean waste official method and Guideline for amounts to cover the optimum performance range that is
PCBs analytical method of transformer oil in Korea, which is 0.210 mg L1 . Each standard solution was injected to 1 L
described in Fig. 1. [11]. under same GC conditions. Each characteristic Aroclor peaks
were used for quantitation in the initial calibration solution. For
2.2.1. Pre-treatment procedure quantification of Aroclors, Peaks with intensities higher than
Alkali treatment, liquidliquid extraction, sulfuric acid treat- 25% of the largest one in the chromatogram of each Aroclor
ment, silica gel clean-up and instrumental analysis were per- standard mixture were considered for quantitative purposes and
 S.K. Shin, T.S. Kim / Journal of Hazardous Materials B137 (2006) 15141522 1517

individual congeners of IUPAC No. 18, 28, 31, 44, 52, 101, clor 1242, 1248, 1254, 1260 on free-PCB matrix of each batch.
118, 138, 149, 153, 170, 180, 194 were also included. If sam- For recovery test, 100200 ng of decachlorobiphenyl (IUPAC
ple extract showed two Aroclor mixture pattern, peaks that is No. 209) was spiked to the every sample.
not overlapped with main peak of each single Aroclor was cho-
sen for calibration. The identification of PCBs as Aroclor was
based on the agreement between the retention times of the peaks 3. Results and discussion
in the sample chromatogram and the retention time windows
established through the analysis of the standards of the target 3.1. Survey result
Aroclors as shown in Fig. 2.
The transformer survey results of the electric power station,
2.2.4. Quality assurance including information regarding transformer type, manufac-
Calibration verification was performed in order to assess to tures name, country of manufacture and year of manufacture,
drift of the instrument response between initial calibration and are presented in Table 1.
each subsequent analysis. Continuing calibration verification The manufactured countries of transformers indicated that
was conducted with 100200 ng calibration solution of Aroclor 16 of transformers were made in Korea. It was 48.5% of total
1242, 1248, 1254, and 1260 before analysis of each batch sam- transformer at Power Station. The Republic of Korea, however,
ple. If the drift percentage was less than 15%, then the initial did not produce the pure PCBs to use in dielectric fluid for elec-
calibration was considered to valid and proceeds for quantifi- trical equipment and for other uses. About 29276412 tons of
cation. If the percentage drift was greater than 15%, a new PCBs were probably imported to be used as the commercial
calibration solution was prepared and validated. One matrix products from USA and Japan [5,7]. Nine transformers were
blank was included in 10 oil samples. No PCBs were found manufactured by America, and remaining seven transformers
above the practical quantification limits in the method blank. were manufactured by Japan. One transformer did not have
Laboratory control sample was spiked with 100200 ng of Aro- information on manufactured country, company, and year.

Table 1
Transformer survey results
Year Number Manufacture year Company Nation Sample list

1960 1 1966 FUJI Japan A-60S-01

2 1966 FUJI Japan A-60S-02
3 1968 General Electric USA A-60S-03
4 1968 General Electric USA A-60S-04
5 1968 General Electric USA A-60S-05
6 1969 ASGEN USA A-60S-06
7 1969 HITACHI Japan A-60S-07
8 1969 TOSHIBA Japan A-60S-08
1970 9 1970 ASA USA B-70S-01
10 1971 General Electric USA B-70S-02
11 1975 ALSTHOM USA B-70S-03
12 1976 General Electric USA B-70S-04
13 1977 General Electric USA B-70S-05
14 1978 HITACHI Japan B-70S-06
15 1978 FUJI Japan B-70S-07
16 1978 FUJI Japan B-70S-08
1980 17 1981 No record No record C-80S-01
18 1981 EWHA Electric Korea C-80S-02
19 1983 HYOSUNG Korea C-80S-03
20 1983 HYOSUNG Korea C-80S-04
21 1985 HYOSUNG Korea C-80S-05
22 1985 HYOSUNG Korea C-80S-06
1990 23 1991 HYOSUNG Korea D-90S-01
24 1991 HYUNDAI Korea D-90S-02
25 1991 HYUNDAI Korea D-90S-03
26 1994 Icheon Electric Korea D-90S-04
27 1994 Korea Cottrell Korea D-90S-05
28 1998 HYUNDAI Korea D-90S-06
29 1998 HYOSUNG Korea D-90S-07
30 1998 HYOSUNG Korea D-90S-08
31 1998 HYOSUNG Korea D-90S-09
32 1999 HYUNDAI Korea D-90S-10
33 1999 EWHA Electric Korea D-90S-11
1518 S.K. Shin, T.S. Kim / Journal of Hazardous Materials B137 (2006) 15141522

Manufactured year of transformers were shown as Fig. 3.

These results indicated that eight (24.0%) of transformer were
manufactured between 1971 and 1980. Among then, eleven
(33.3%) of transformer was manufactured between 1991 and
1999.

3.2. Analytical results

The transformer oil samples were analyzed at NIER of Seoul,

Korea. This project was performed to measure the release pat-
tern of existing PCBs in transformer oil. The survey included
analysis of 33 samples, six duplicate sample for quality control,
and 12 quality assurance transformer oil samples from various Fig. 3. Manufactured year of survey transformer.
locations.
Practical quantification limits analyzed by our method were
0.02 mg L1 for Aroclor 1242 and 0.05 mg L1 for Aroclor levels. Average recoveries over 90% and relative standard devi-
1248, 1254, and 1260. The oil weighed as mass unit was con- ations below 10% were achieved. In view of these results, data
verted to volume unit by measuring the density of the each trans- for real polluted samples were not corrected for recovery.
former oil to satisfy the Korean regulation limit of 2 mg L1 (unit The calibration solution of Aroclor 1242, 1248, 1254 and
is not mg kg1 ). Quantification units in the results were recorded 1260 standard, respectively, was prepared five concentrations,
as mg L1 . Recoveries of the sample preparation method were and the linearity of Aroclor by GC-ECD was above 0.99. Con-
evaluated using an oil sample spiked with a mixture of Aro- tinuing calibration verification was checked with 100200 ng of
clors (1242:1248,1254 and 1260) at three different concentration Aroclor 1242, 1248, 1254, and 1260 calibration solution before

Table 2
Analytical results of survey transformer oil
Number Sample list Patterns Recoverya (%) Concentration

1 A-60S-01 Arol254 81 <2 ppm

2 A-60S-02 Arol254 83 <2 ppm
3 A-60S-03 Arol254:1260 = 1:1 83 <2 ppm
4 A-60S-04 Arol254 84 >2 ppm
5 A-60S-05 Arol242 95 >2 ppm
6 A-60S-06 Arol260 80 >2 ppm
7 A-60S-07 Arol242:1254 = 1:1 85 >2 ppm
8 A-60S-08 Arol242:1260 = 3:2 87 >2 ppm
9 B-70S-01 Arol260 95 <2 ppm
10 B-70S-02 Arol254 89 >2 ppm
11 B-70S-03 Arol260 89 >2 ppm
12 B-70S-04 Arol242:1254:1260 = l:l:l 77 <2 ppm
13 B-70S-05 N.D. 86 N.D.
14 B-70S-06 Arol260 84 <2 ppm
15 B-70S-07 Arol254 91 <2 ppm
16 B-70S-08 Arol242:1254 = 1:1 93 <2 ppm
17 C-80S-01 Arol242:1254:1260 = l:l:l 82 <2 ppm
18 C-80S-02 Arol260 97 <2 ppm
19 C-80S-03 Aro 1242:1254 = 5:1 96 <2 ppm
20 C-80S-04 Aro 1242:1254 = 5:1 96 >2 ppm
21 C-80S-05 Aro 1242:1254 = 5:1 73 <2 ppm
22 C-80S-06 Aro 1242:1254 = 5:1 92 <2 ppm
23 D-90S-01 N.D. 92 N.D.
24 D-90S-02 N.D. 95 N.D.
25 D-90S-03 Aro1260 93 <2 ppm
26 D-90S-04 Aro1260 87 <2 ppm
27 D-90S-05 Aro1254 91 <2 ppm
28 D-90S-06 Aro 1254:1260 = 2:1 86 <2 ppm
29 D-90S-07 Aro 1242:1254 = 2:1 85 <2 ppm
30 D-90S-08 Aro1260 85 <2 ppm
31 D-90S-09 Aro 1242:1254 = 2:1 82 <2 ppm
32 D-90S-10 N.D. 85 N.D.
33 D-90S-11 Arol242:1254:1260 = l:l:l 81 >2 ppm
a Average of 23 times duplicate analytical results.
 S.K. Shin, T.S. Kim / Journal of Hazardous Materials B137 (2006) 15141522 1519

analyzing each batch sample to ensure that the calibration has chromatograms corresponded to the different types of PCBs
not drifted. Surrogate recovery of all samples were 7797% and mixtures. On the chromatograms of the 15 samples, the peaks
all results of quality control by our analytical method, such as corresponding to the pure Aroclor 1242, 1254 and 1260 were
laboratory control sample, matrix spike sample, sample dupli- observed. Others contained the different commercial mixtures
cate were within these limits. These results were satisfied to the as shown in Figs. 4 and 5. In this study, various kinds of PCBs
recovery ranges of 75120% in presenting the Korean waste patterns were present in about 42.2% of analyzed samples.
official method. The total PCBs concentration was determined by a peak pat-
Pattern identification of PCBs in transformer samples were tern matching and summation the selected peaks to obtain a total
performed by comparison of chromatograms of purified extracts amount. Among 33 transformer oil samples, 29 samples were
with those obtained from standard solution of commercial mix- determined to contain the PCBs above 0.05 mg L1 and nine
tures. The presence of PCBs is indicated when pattern of peaks samples were greater than 2 mg kg1 which is limit of ROK
resembles that observed in standard solution chromatogram. the Environmental Law [10] regarding PCBs in transformer oil.
Retention times must be agreed closely within 0.1 min and Fig. 6 showed the total PCBs content of transformer sample
relative peak type must be similar. Fig. 4 showed a typical chro- containing more than 2 mg kg1 of PCBs.
matogram of oil extract with various peak patterns. The levels of PCBs in transformer oils were in between N.D.
The results of peak pattern analysis have explained that 4 and 48.33 mg kg1 . The PCBs concentrations did not exceed
from 33 transformer oils were not contaminated with PCBs as 50 mg kg1 which is a generally accepted limit for the definition
present in Table 2. Other analyzed samples contained on the of waste in POPs Guideline of Basel Convention [14,15].

Fig. 4. Sample chromatograms of the single Aroclor commercial product contained.

1520 S.K. Shin, T.S. Kim / Journal of Hazardous Materials B137 (2006) 15141522

Fig. 5. Sample chromatograms of the mixed Aroclor commercial product contained.

3.3. Comparison the analytical results were compared to the USA EPA 8082 and Canada method using
different index peaks for quantification.
The collected samples were analyzed using the quantifica- The quantification has been performed with three calibration
tion methods of Korean waste official methods. Also, the results standard solution. The peak height should be within the sensitiv-
ity range of the ECD. Extracts from of oil samples, prepared as
described in Fig. 1, were quantified using US EPA, Canada and
Korea official methods. In EPA 8082 method, three to five index
peaks selected to calculate PCBs concentration, and the three to
five main peaks and some minor peaks were selected in Canada
method (Fig. 7). In Korean method, however, the total peaks at
least 25% of the height of the largest peaks were selected.
The PCBs concentrations of two samples (B-70S-08 and D-
90S-03) were compared. The analyzed sample of P-030415-12
showed a concentration range from 1.30 to 1.34 mg L1 , and
from 1.93 to 1.94 mg L1 for P-030415-42. The each method
selected the different peaks to calculate the concentration the
Fig. 6. Total PCBs content of transformer samples exceeding the regulation
samples. As the results by analyzing the Korean official method
value. showed the similar results of other PCBs analytical methods.
 S.K. Shin, T.S. Kim / Journal of Hazardous Materials B137 (2006) 15141522 1521

Fig. 7. Quantification peaks of US EPA 8082 and Canada analytical methods using in this study.

4. Conclusion the 15 samples, the peaks corresponding to the pure Aroclor

1242, 1254 and 1260 were observed. In this study, different
Thirty-three transformer oils were analyzed as a main source PCBs mixtures were present in about 42.2% of analyzed sam-
of PCBs emission into environments and collected by NIER ples. Nine samples were greater than 2 mg kg1 which is limit
in Republic of Korea. The method used to analyze the trans- of the Environmental Law [10] regarding PCBs in transformer
former oil samples was Korean waste official method (KWOM) oil. The levels of PCBs in transformer oils are ranged from
of Environment Ministry for PCB analysis. Practical quantifi- N.D. to 48.33 mg kg1 . The PCBs concentrations did not exceed
cation limits analyzed by our method were 0.020.05 mg L1 , 50 mg kg1 which is a generally accepted limit for the defini-
and the recovery of all samples were 7797%. The analysis tion of waste in POPs Guideline of Basel Convention. As the
results showed that PCB in the transformer oils was identified results of comparing the analytical concentration using several
as Aroclor 1242, 1254 or 1260. Some of PCBs were mixture quantification methods, the results by analyzing the Korean offi-
of Aroclor 1242 and 1260, 1254 and 1260, 1242 and 1254 or cial method showed the similar results of other PCBs analytical
1242, 1254, and 1260. On the start from chromatograms of methods.
1522 S.K. Shin, T.S. Kim / Journal of Hazardous Materials B137 (2006) 15141522

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