Persistent, Bioaccumulative, and Toxic Chemicals I - American

Chapter 6

Polychlorinated Biphenyls in Poland: History, Fate, and Occurrence

Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on May 28, 2018 | https://pubs.acs.org Publication Date: January 15, 2000 | doi: 10.1021/bk-2001-0772.ch006

Janina Lulek Department of Inorganic and Analytical Chemistry, Karol Marcinkowski University of Medical Sciences, Poznań, Poland

The review presents the polychlorinated biphenyls (PCBs) regulatory history and sources of their emission into Polish environment. The levels of these xenobiotics determined in different environmental matrices from Poland (air, water, sediments, soil and biota) are compared with data obtained in other regions of world. The concentrations of PCBs detected in several classes of Polish food are discussed.

Polychlorinated biphenyls (PCBs) are a class of 209 individual chemical compounds in which 1 to 10 chlorine atoms are substituted onto a biphenyl nucleus. Since 1929, PCBs were commercially produced as complex mixtures with different trade names (Aroclors - U S A ; Clophens - Germany; Kanechlors -Japan etc.). These industrial formulations have been widely marketed for a variety of uses, including dielectric fluids in capacitors and transformers because of their chemical stability and high resistance to thermal breakdown (1,2). However, a mass food poisoning which occurred in western Japan in 1968 and the discovery of PCBs in environmental matrices in late 1960s, prompted some industrial countries to take legislative measures for controlling the flux of these pollutants into the environment (3,4). The paper concerns the P C B problem in Poland. It presents the regulatory measures adapted in Polish legislation as well as gives a brief discussion on the environmental, food and human levels of PCBs detected in Polish matrices.

© 2001 American Chemical Society Lipnick et al.; Persistent, Bioaccumulative, and Toxic Chemicals I ACS Symposium Series; American Chemical Society: Washington, DC, 2000.

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Regulatory History In Poland, the problem of PCBs was mentioned for the first time in the mid 1970s, when Falandysz (5) commented on their solubility in lipids and their presence in food products. Nearly at the same time Strojny (6) reported on toxicological activity of PCBs mixtures used in Poland in C type electrical capacitors. Since 1982, the use of Baltic cod liver oils for medical purposes in Poland has been restricted, in response to the high total PCBs concentrations (9.1 - 18.0 μg/g fat basis), determined by Falandysz (7) and Kannan et al (8) in these matrices, collected during 1971-80. In 1983, as a consequence of high PCBs and D D T levels detected in fresh cod livers, the Minister of Health and Social Welfare (9) forbade their transformation to food products. Recently, the problem of regulatory measures concerning PCBs has become more urgent because of the necessity to conform Polish environmental legislation to the requirements of the European Union. Table I summarizes the recent PCBs regulations defined in Polish governmental acts.

Table I. P C B s Regulations Deadline of institute 31.03.1993

2.09.1993

1.01.1996

27.09.1998

1999

Legal Acts Dz.U.R.P. 22/223 -1993 Ordinance of the Minister of the Health and Social Welfare Dz.U.R.P. 76/362 - 1993 Ordinance of the Minister of Environmental Protection, Natural Resources and Forestry Dz.U.R.P. 153/775 -1995 Ordinance of the Cabinet Dz.U. R.P. 79/513 - 1998 Ordinance of the Minister of Work and Social Policy Project of the Ordinance of the Minister of the Health and Social Welfare

PCBs Regulations Maximal Acceptable Concentration of PCBs in cod l i v e r - 5 . 0 μg/gfat PCBs are included in the register of hazardous waste

P C B s are included in I class of pollutants, air emission is punished by fine Workplace threshold limit Values of PCBs - lmg/m [Aroclor 1242] Maximal Acceptable Concentration of PCBs in drinking water - 0.5 μg/l 3

Table II reviews standard methods of PCBs determination in different matrices. These methods will be instituted in Poland in 2000 or later. The majority of them are based on European Standard Methods and include the determination of some individual PCBs in cleaned up extracts by capillary gas chromatography.

Lipnick et al.; Persistent, Bioaccumulative, and Toxic Chemicals I ACS Symposium Series; American Chemical Society: Washington, DC, 2000.

87 Table II. PCBs Standards in Poland


No of standard

Subject

PN-IEC 997:1998 Determination of polychlorinated biphenyls (PCBs) by gas chromatography method PrPN-C-04579-1 Investigation of content of selected polychlorinated biphenyls (PCB). Determination of P C B No 28,52,101, 118,138,153 and 180 in water by gas chromatography E N 1528-1:1996 Determination of pesticides and polychlorinated biphenyls (PCB). General requirements E N 1528-2:1996 Determination of pesticides and polychlorinated biphenyls (PCB). Extraction of lipids, pesticides and polychlorinated biphenyls and determination of lipids E N 1528-3:1996 Determination of pesticides and polychlorinated biphenyls (PCB). Clean up methods E N 1528-4:1996 Determination of pesticides and polychlorinated biphenyls (PCB). Determination and confirmation tests P r E N 12766-1 Determination of polychlorinated biphenyls. Separation and determination of selected P C B congeners by gas chromatography

Matrix Electroinsulating oils Water and wastewater

Deadline of institute Instituted

Project

Fat food

2000

Fat food

2000

Fat food

2000

Fat food.

2000

Petroleum products and used oils

2001

Production, Use and Sources Although the production of PCBs in Poland was not of major significance on the world market, however Poland produced two original P C B formulations: Chlorofen and Tarnol. Moreover, Poland imported commercial PCBs mixtures from the former Czechoslovakia and USSR (10). N o data are available on the quantity of production, manufacture time and usage of P C B formulations in Poland. Determination of P C B isomer and congener composition in technical Chlorofen, using the high resolution gas chromatography-electron capture detector (HRGCECD) and H R G C - low resolution mass spectrometry (LRMS) techniques, was performed by Falandysz et al (11). A comparison of PCBs group congeners in Chlorofen, Clophen A60 and Aroclor 1262 is shown in F i g . l .


88

Su bstitu tion C hlorofen Aroclor 1262 Clophen A 6 0

nonaocta-


hepta-

5

10

15

20

25

30

35

C h l o r i n e c o n t e n t by m a s s

40

45

50

[%]

Figure 1. Composition of Chlorofen, Clophen A 60 and Aroclor 1262. (Data from references 11 and 12.) The presented data indicate that Chlorofen contains larger proportion of nonaand octa-chorobiphenyls and less of penta- and hexa-substituted congeners than Aroclor 1242 and Clophen A60 formulations. According to the results of analyses of individual congeners, Chlorofen also incorporates the largest percent contribution of P C B 180 (2,2\3,4,4\5,5'-Heptachloro biphenyl) (77). Since 1993, the PCBs have been included in the list of hazardous substances (Table 1), but until now the problem of the disposal and/or destruction of waste containing these xenobiotics has not been regulated. The available data (72) indicate that in national power plant installations about 14001 of transformer and capacitor oils are being used. In 1995-1997, a detailed stock-taking of technical installations which could be using products containing PCBs was made in the southwestern Poland. The results proved that the high-voltage transformers, with few exceptions, are filled with Polandmade oils which do not contain PCBs (13). The results of the inventory concerning the contents of capacitors and low-voltage transformers are given in Table III.

Table III. Inventory of P C B s Equipment in Southwestern Regions of Poland Type of Equipment Low voltage transformers Capacitors

No of controlled installations 24 674 34 055

No of equipment containing PCBs 69 11 004

% detected

NOTE: Data are from Reference 13.


0.28 32.3

89


The results indicate condensers as a possible source of P C B emissions to the environment. Unfortunately, no data are available on the contents of PCBs in electroinsulating oils used in many installations not mentioned above (e.g. hydraulic and heat transfer systems, vacuum pumps, etc). The P C B levels determined by Lulek (14) and Cçckiewicz (15) in randomly collected samples of used oils (Table IV) do not confirmed the data presented by Gurgacz (16), that Polish spent oils do not contain the PCBs.

Table I V . Level of P C B s in Some Used Oils Matrix Motor oils Transformer oils Mineral oil

Year of collection 1995 1995 N.A.

No of samples 13 13 1

% detected 46 46

-

Concentration range 2.88 - 53.42 2.33 - 30.67 96

NOTE: Data are from References 14 and 15. N.A. Not data available.

However it is worth to note that the P C B concentrations determined in examined oils did not exceed 50 μg/g oil (except two samples) which is a generally accepted limit for the definition of special waste in U S A and most of countries of Western Europe (17).

Environmental Occurrence PCBs are one of several "global" environmental pollutants, including mercury, lead and certain pesticides. Since the early 1970s, they have been found consistently in many environmental matrices (1,2, 18-22). The first determinatiOon of PCBs in environmental matrices in Poland were performed in the mid-1970s by Falandysz (cod liver oil) (5). In the 1980s the same author reported data on P C B levels in certain species of wild birds, marine fish and wild animals (23). However, the presence of PCBs in environmental matrices in Poland has attracted real interest since the mid-1990s, which was evidenced among others, by undertaking a monitoring of seven PCBs congeners (28, 52, 101, 118, 138, 153 and 180) in water of selected Polish rivers. Unfortunately, at present the results of this monitoring are not available. Table V summarizes selected P C B levels determined by different authors in the samples of air, water, river sediments and soils collected in Poland. The atmosphere is considered an efficient pathway of transportation and dispersion of semivolatile organohalogenated pollutants, including PCBs, in the environment at the global scale (1). The only available data concerning the content of PCBs in the air in Poland, were provided by Falandysz et al. (Table V ) . The mean concentration of total PCBs determined in the ambient air of the coastal city Gdansk, was 0.36±0.28 ng/m and 3


90 Table V. PCB occurrence in Polish Environment Matrix

Year of collection

Air Water


1991-92 1991-92 1997-98 Sediment 1993-94 1997-98 Soil

1992 1990-94 1994 1997 1998

Location or soil type

No of samples

Range of PCB content

Ref

11 12 23 20 3 13

0.12-1.10 0.12- 0.30

Persistent, Bioaccumulative, and Toxic Chemicals I - American

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