PCB - Case Studies
Heidelore Fiedler
Bavarian Institute for Waste Research - BIfA GmbH
Am Mittleren Moos 46a, D86167 Augsburg, Germany
After the impact of PCB on the environment was recognised, the most prominent producers Monsanto and Bayer voluntarily stopped their PCB production in 1977 and 1983, respectively (DFG 1988). A ban on the marketing of PCB for use in open systems was imposed as early as 1978 by the Tenth Ordinance under the Federal Immission Control Act. Since the beginning of 1984, PCB are no longer used in the Federal Republic of Germany in new electrical equipment (capacitors, transformers). The placing on the market of PCB for use in closed systems was prohibited by EC Directive 85/467/EEC of 1985, which was transferred into national law by the PCB Prohibition Ordinance of 1989. In 1993, the PCB Prohibition Ordinance was superseded by the Chemicals Prohibition Ordinance.
In 1979, a ban on commercial PCB production was implemented by the U.S. Environmental Protection Agency and the use of PCB was restricted to completely enclosed systems (Allen 1990).
In Germany exist a number of regulations concerning handling, transport, and disposal of PCB-containing waste. The basis for most of these regulations is the ordinance banning the production and use of PCB, PCT and vinyl chloride (VC) from 1989 [PCB/PCT/VC]. This ordinance also prohibits the sale of products containing more than 50 mg PCB/kg and it limits the use of PCB in large condensers (>1 liter) until Dec. 31, 1993 and in transformers until Dec. 31, 1999. The import of PCB-containing hydraulic fluids for use in coal mining, which in 1983 still amounted to 1,000 t, was terminated in 1988. The most recent one is the guideline of the European Union on disposal of polychlorinated biphenyls and polychlorinated terphenyls of Sept. 16, 1996 [EU-PCB]. In the last ten years there was a continuous update of various regulations. In this paper, an attempt is made to list all relevant regulation currently in effect. With regard to these regulations PCB is defined as
Mixtures, formulations and products are considered 'PCB-containing', when the PCB concentration is >50 mg/kg. Products which consist of different materials are considered 'PCB-containing', if the PCB concentration of 50 mg/kg is exceeded in any one fraction (e.g. in cables). When the PCB concentration is less than 50 mg PCB/kg, waste is considered 'PCB-free'. This limit value for a 'PCB-free' waste does, however not apply to used oil, where historically a specific regulation exists (Altölverordnung [AltÖlV]). Used oils containing more than 20 mg PCB/kg is treated more or less like other PCB-containing waste with more than 50 mg PCB/kg.
The PCB concentration is determined by analysing for six indicator compounds (according to DIN 51 527 [DIN]) and multiplying the sum of these six congeners by a factor of 5:
PCB = [PCB28] + [PCB52] + [PCB101] + [PCB138] + [PCB153] + [PCB180] · 5
Electrical area
Mining area
Other areas
In Germany, disposal of PCB and PCB-containing wastes are allowed only in facilities which are specifically commissioned for this purpose. Currently, there are the following possibilities for disposal of PCB-containing waste:
In Germany, only four hazardous waste incinerators are allowed to dispose of PCB and PCB-containing waste at temperatures of 1,200 °C (Bayer AG, BASF AG, GSB Ebenhausen, and AGR Herten). The combined annual capacity of these facilities is probably around 6,000 t. The HIM in Biebesheim is allowed to incinerate PCB-containing waste only. One hydrogenation facility is allowed to dispose of PCB and PCB-containing waste (Kohleoel-Anlage Bottrop). For underground disposal one salt mine is commissioned in Germany (Herfa-Neurode). Solvents containing PCB should be distilled for solvent recovery, decreasing the volume of PCB-containing waste.
Transformers with PCB-containing dielectric fluid are allowed to be operated only until Dec. 31, 1999. Until then they must be disposed of or measures have to be completed to render the fluid PCB-free either by refilling with a PCB-free fluid, destruction of PCB or cleaning the transformer with a solvent.
Condensers with a dielectric fluid volume of more than 1 liter had to be disposed of until Dec. 31, 1993. Small condensers are disposed of in an underground salt mine.
For handling, transport and storage of PCB-containing waste, a specific permit is required and regulated by several ordinances e.g. TRGS 518 and ordinances for transport of dangerous goods (GefStoffV I+II]).
The disposal method invariably depends on the PCB content. For the disposal of transformers, the PCB content in the cooling fluid is the decisive criterion.
Not all amounts of PCB produced and used were disposed of properly, nor is this the case today. Those used in most of the open applications have, in part, already reached the environment via various disposal routes. Part of the problem is that not pure PCB are to be disposed of, but PCB are constituents of equipment and materials. This means that the quantity of PCB-containing wastes yet to be disposed of is considerably higher than the quantity of PCB used. According to the time limits provided for by the Chemicals Prohibition Ordinance [ChemG], it is expected that 200,000 t of PCB-containing waste per year can arise in Germany between 1996 and 2000. Work done in 1993 to allocate quantities to the prescribed disposal methods, namely hazardous-waste incineration and underground depositing, showed the following results (Table 1 and Table 2):
Table 1: PCB liquid wastes in Germany
Origin/Stock West Ger. East Ger. Total (t)
(t) (t)
Askarel transformers 14,000 40 14,040
Mineral oil transformers (PCB>1,000 110,000 100 110,100
ppm)
Capacitors, large 550 1,400 1,950
Hydraulic gear, mining 1,000 - 1,000
Post 40 - 40
Railroad (West Germany) 1,900 - 1,900
Railroad (East Germany) - 20 20
Army (West) 500 - 500
Army (East) - ? ?
Other electric appliances 1,500 ? min. 1,500
Sum ca. 130,000 ca. 2,000 ca. 132,000
Table 2: PCB solid wastes in the Federal Republic of Germany
Origin/Stock West Ger. East Ger. Total (t)
(t) (t)
Drained Askarel transformers (PCB <1,000 32,000 100 32,100
ppm)
Drained mineral oil transformers 32,500 100 32,600
Drained capacitors, large 7,000 12,000 19,000
Drained capacitors, small 5,000 7,000 12,000
Mining equipment 1,000 - 1,000
Post 130 95 225
Railroad (West Germany) 720 - 720
Railroad (East Germany) - 380 380
Army 1,200 50 1,250
High tension cables 10 3,000 3,010
Other electric appliances 3,000 200 3,200
Sealants 20,000 - 20,000
Sum ca. ca. 23,000 ca.
100,000 125,000
According to the ordinance on sewage sludge [AbfKlärV], there is a limit value for sludges applied on agricultural land:
Table 3: Limit values for PCB and PCDD/PCDF in sewage sludg applied on agricultural [AbfklärV]. d.m.= dry matter
Substance Limit Value-Unit PCB 28, PCB 52, PCB 101, PCB 138, PCB 153, PCB 0.2 mg/kg d.m. per 180 congener Sum of the above PCB-congeners 1.0 mg/kg d.m. PCDD/PCDF 100 ng ITEQ/kg
In compost the limiting values for agricultural application are 1/6 of the above given concentrations.
According to the ordinance on maximum concentrations of toxic substances in food [SHMV] limiting concentrations exist in meat, milk, fish eggs and products thereof for the following individual PCB-congeners
PCB 28, PCB 52, PCB 101, PCB 180; e.g. in milk 0.04 mg/kg fat for each congener
PCB 138, PCB 153; e.g. in milk 0.05 mg/kg fat for each congener.
Acceptable concentrations in indoor air and levels above which sanitation is required are regulated in the guidelines for assessment and rehabilitation of PCB-contaminated building material. In this guideline a maximum concentration for indoor air is set at 300 ng PCB/m³.
These concentrations are considered long-term tolerable (preventive value) when between 300 and 3,000 ng/m³: It is recommended to identify the source of the higher PCB levels, and, if possible under proportionate conditions, to eliminate the source. Otherwise thorough cleaning and regular ventilation should minimise the air concentration.
Indoor air concentrations >3,000 ng PCB/m³: Sanitation is recommended. The sanitation measures should assure a PCB level after sanitation <300 ng PCB/m³ [Roßkamp 1996].
Analysis for PCB is carried out on the basis of the six indicator congeners according to DIN 51 527 [DIN], multiplying their sum by a factor of 5 as described for PCB-containing waste.
In drinking water, the PCB-concentration is limited according to the ordinance on drinking water [TWVO]. The six PCB indicator congeners (PCB 28, PCB 52, PCB 101, PCB 138, PCB 153, PCB 180) are each limited to 0.0001 mg/L and a total sum of 0.0005 mg/L. In Germany, PCB concentrations in drinking water are steadily below the detection level.
Closed systems are those from which PCB can be retrieved. Large, long-lived products in which PCB are used in enclosed units and in quantities high enough to warrant complete retrieval can also be considered as closed systems.
Such closed-system applications mainly comprise:
The PCB-containing transformers still in operation in Germany are officially registered individually. The Chemicals Prohibition Ordinance provides that PCB-containing transformers be scrapped by the year 2000, irrespective of whether or not they are in working order.
The chemical and physical properties of PCB made them nearly ideal for use as dielectric impregnants for capacitors. Their use is restricted to the following applications: discharge lamps, electric drive, thermoelectric plants and power capacitors (prohibited in 1995; now disposal is required).
Fluorescent lamps are a typical example of the main application of capacitors, namely discharge lamps, and are, at the same time, the main application of small capacitors. Such capacitors may no longer be used after 1999. See also section 2.
On 8 August 1956, a mine accident occurred at the Bois de Cazier colliery near Marcinelle, France, in which 262 miners died in the fumes of a fire. It was the mineral-oil-based hydraulic oil used for the mining machinery that caused the rapid spread of the fire.
Provisions requiring that only hydraulic fluids approved by the Land Mines Inspectorate be used in enclosed spaces and areas in which there is a risk of the occurrence of a fire and/or an explosion were subsequently incorporated in the regulations governing coal, ore, mineral salt and non-metallic minerals mining.
Low chlorinated PCB did not satisfy the extremely stringent safety requirement in all respects, so that higher chlorinated PCB were used. In French and German mines, PCB were used in hydraulic fluids together with additives imparting ageing stability, corrosion protection, wear resistance and improved foaming behaviour.
In the mid 1980s, analysis of sediment samples revealed a PCB contamination caused by a nearby abandoned waste dump. Historical evaluation of the waste site identified approximately 50,000 small capacitors which were disposed of in the dump during the 1960s and 1970s as the source. As the waste dump did not have any liners and in addition, the groundwater streams passed through the waste body from time to time, PCB was released into the water stream and transported downstream. Below the waste dump, a brewery took the water for cooling purposes. As a consequence, monitoring programs were established to screen for potential PCB contamination. Observation wells were drilled and from time to time, samples were taken. PCB couldn't be detected in the water samples, however, whenever water was pumped and thus, fine sediment particles were mobilised, PCB could be analysed. In the samples from Teningen, a total of 17 PCB congeners (di- through pentachlorinated) were identified, see Table 4 [Ketterer et al. 1993]. Higher chlorinated PCB could not be detected. Based on these results, it was assumed that the PCB contamination was due to Clophen A30.
Table 4: PCB congeners identified in environmental samples around the Teningen waste dump
PCB IUPAC Number dichloroCB PCB 6 and 8 trichloroCB PCB 18, 20+33, 28, 31, and 37 tetrachloroCB PCB 42, 44, 47, 49, 52, 53, 60, and 70 pentachloroCB PCB 95 and 110
Downstream the PCB-Contaminated waste dump Teningen, fishes were analysed for PCB. In August 1993, only very low concentrations could be detected. The guideline concentration was not exceeded. To obtain a clearer picture of the situation at Teningen, the agencies determined to include fish from upstream and downstream the dump into their analytical program. The results are shown in Table 5. The gravel pit below the dump is fed by groundwater passing through the waste dump.
Table 5: PCB concentrations in fish samples above and below (mg/kg fresh weight)
Guidelin Gravel Pit Above Dump Gravel Pit Below Dump
e
Eel Brachse Carp Eel Perch Carp
PCB 8 - ND ND ND 0.001 <0.001 0.004
PCB 18 - ND ND ND 0.008 0.002 0.035
PCB 28 0.2 0.002 ND 0.0005 0.073 0.008 0.017
PCB 52 0.2 0.03 0.0005 0.0009 0.2 0.008 0.03
PCB 101 0.2 0.036 0.001 0.0008 0.025 0.001 0.004
PCB 153 0.3 0.217 0.005 0.001 0.116 0.002 0.005
PCB 138 0.3 0.18 0.002 0.0006 0.081 0.001 0.004
PCB 180 0.2 0.045 0.001 ND 0.023 <0.001 0.001
PCB Sum 0.51 0.0095 0.0038 0.518 0.02 0.061
PCB concentrations between 1 and 3 µg/m³ were detected in indoor air of an office building in Kiel, Germany [Pitulle et al. 1995]. The 15-floor house where approximately 300 employees work every day was constructed from prefabricated concrete in 1969 and contained Thiokol® sealants (a sulphur-containing polymer) which known to contain 140% of PCB (Clophen A30, A40 and A50).
Table 6: PCB concentrations in indoor air of the Kiel office building (ng/m³). Measurements from 45 rooms in 1990/91 [Benthe et al. 1992]
PCB PCB 28 PCB 52 PCB 101 PCB 153 PCB 138 PCB 180 PCB * Mean 26 26 18 5 4 0.5 440 SD 24 21 16 5 4 0.2 355 Maximum 111 90 76 19 18 2 1251
* Calculated as (PCB 28 + PCB 52 + PCB 101 + PCB 138) · 6
Measurement were very sensitive to ambient air temperatures outside the building (maximum concentration = 2,700 ng PCB/m³). Thus it was concluded that especially the lower chlorinated PCB degas at elevated temperatures. In other buildings, PCB concentrations up to 7,000 ng PCB/m³ were measured; however, PCDF (polychlorinated dibenzofurans) could not be detected. PCB levels found in the Kiel office building were above the background concentration of 530 ng PCB/m³ and much above contaminations found after smaller fires involving PCB containing transformers or smaller accidents involving destruction of neon bulbs. Of the 97 cases, PCB levels were always < 700 ng/m³ [Benthe et al. 1992]. Besides the Thiokol, there were additional PCB sources in the office building such as leaky capacitors in neon lamps, floor coverings and wall paper which had a surface contamination of 50100 mg PCB/m². Decontamination of the building could only be achieved when all sealants were removed.
The authorities in Kiel set a concentration for remediation of 300 ng PCB/m³ which is comparable to the NIOSH value of 500 ng PCB/m³. Based on an ADI (acceptable daily intake) of 1 µg PCB/(kg bw·d) as proposed by the Federal Health Office and a residence time of 24 h per day, indoor air concentrations were derived (see Table 7).
Table 7: Proposed guideline concentrations of PCB in indoor air [Benthe et al.1992]
3000 ng/m³ Action level (100% of ADI) 300 ng/m³ Prevention level (10% of ADI) 30 ng/m³ Target concentration
Allen T.K. (1990): Developments in the Federal Regulation of PCBs since October 1987. In: Proceedings: 1989 EPRI PCB Seminar, G. Addis (ed.) Electric Power Research Institute. Palo Alto (CA), USA
Benthe C., B. Heinzow, H. Jessen, S. Mohr, and W. Rotard (1992): Polychlorinated Biphenyls: Indoor Air Concentrations Due to ThiokolRubber Sealants in an Office Building. Chemosphere 25, 14811486
Ketterer S., J. Michel, and W. Holzwarth (1993): Verhalten von polychlorierten Biphenylen (PCB) in der wasserungesättigten und wassergesättigten Bodenzone eines kontaminierten Standorts. Ecoinforma 2, 237-249
Pitulle H., S. Mohr, C. Benthe, and B. Heinzow (1995): Sanitation of a PCB-Contaminated Building. Organohalogen Compd. 26, 435439
Roßkamp E. (1992): Polychlorierte Biphenyle in der Innenraumluft - Sachstand. Bundesgesundhbl. 9/92, 434
German and International Regulations
Information on PCB regulation in Germany was taken from manuscripts authored by H. Hagenmaier, University of Tübingen, Tübingen (Germany) and Hans W. Jakobi, German Federal Environment Agency, Berlin (Germany) delivered for a PCB Workshop in Tokyo, Japan, 1996.
AbfBestV: Ordinance on the determination of waste. Verordnung zur Bestimmung von Abfällen nach § 2 Abs. 2 des Abfallgesetzes (Abfallbestimmungsverordnung - AbfBestV) 3. April 1990
AbfG: Law on the avoidance and disposal of waste. Gesetz über die Vermeidung und Entsorgung von Abfällen (Abfallgesetz - AbfG) 27. Aug. 1986
AbfKlärV: Klärschlammverordnung (AbfKlärV) vom 15.04.1992. Bundesgesetzblatt, Jahrgang 1992, Teil 1, 912-934
AbfVerbringVO: Ordinance of the EU on the control of transport of waste within and outside of European Union. Verordnung (EWG) Nr. 259/93 des Rates zur Überwachung und Kontrolle der Verbringung von Abfällen in der, in die und aus der Europäischen Gemeinschaft, 1. Feb. 1993
AltÖlV: Used oil ordinance. Altölverordnung (AltölV) 27. Okt. 1987
AbRestÜberwV: Ordinance on collection, transport and control of waste and residual materials. Verordnung über das Einsammeln und Befördern sowie die Oberwachung von Abfällen und Reststoffen (Abfall- und Reststoffüberwachungsverordnung - AbRestÜberwV) 3. April 1990
BImSchG: Law on the protection from harmful environmental effects by air pollutants. Gesetz zum Schutz vor schädlichen Umwelteinwirkungen durch Luftverunreinigungen, Geräusche, Erschütterungen und ähnliche Vorgänge (Bundes-Immissionsschutzgesetz -BImSchG) 14. Mai 1990
ChemVerbotsV: Ordinance on the ban and limitations for use of dangerous substances. Verordnung über Verbote und Beschränkungen des lnverkehrbringens gefährlicher Stoffe, Zubereitungen und Erzeugnisse nach dem Chemikaliengesetz (Chemikalien-Verbotsverordnung - ChemVerbotsV) 14. Okt. 1993
DIN: DIN 51 527, part 1: Determination of the concentration of polychlorinated biphenyls in mineral oil. Prüfung von Mineralölerzeugnissen, Bestimmung des Gehaltes an polychlorierten Biphenylen (PCB)
EU-689: Ordinance on dangerous waste. Richtlinie über gefährliche Abfälle (91/689/EWG) 12. Dec. 1991
EU-904: Resolution of the EU on a list of dangerous waste. Entscheidung des Rates über ein Verzeichnis gefährlicher Abfälle (94/904/EG) 22. Dec. 1991
EU-PCB: Guideline of the European Union on disposal of polychlorinated biphenyls and polychlorinated terphenyls. Richtlinie 96/59/EG des Rates über die Beseitigung polychlorierter Biphenyle und polychlorierter Terphenyle, Sept. 16, 1996.
GefStoffV I: Ordinance on protection from dangerous substances. Verordnung zum Schutz vor gefährlichen Stoffen (Gefahrstoffverordnung - GefStoffV) 26. Okt. 1993, § 15, Anhang IV Nr. 14 Abs. 1, Nr. 18 Abs. 1
GefStoffV II: Ordinance on protection from dangerous substances. Verordnung zum Schutz vor gefährlichen Stoffen (Gefahrstoffverordnung - GefStoffV) 26. Okt. 1993, § 54 Abs. 4
PCB/PCT/VC: Ordinance on the ban of PCB and PCT. Verordnung zum verbot von polychlorierten Biphenylen, polychlorierten Terphenylen und zur Beschränkung von Vinylchlorid (PCB, PCT, VC-Verbotsverordnung) 18. Juli 1989
RestBestV: Ordinance on the determination of resiudual material. Verordnung zur Bestimmung von Reststoffen nach § 2 Abs. 3 des Abfallgesetzes (Reststoffbestimmungsverordnung - RestBestV) 3. April 1990
SHMV: Ordinance on maximum concentrations of toxic substances in food. Verordnung über Höchstmengen an Schadstoffen in Lebensmitteln (Schadstoff-Höchstmengenverordnung SMHV), 23. März 1988
TRGS: Ordinance on the law on chemicals; technical rules for dangerous substances. Verordnungen zum Chemikaliengesetz; technische Regeln für Gefahrstoffe, TRGS 518: Elektroisolierflüssigkeiten, die mit PCDD oder PCDF verunreinigt sind.
TrinkwV: Ordinance on drinking water. Verordnung über Trinkwasser und Wasser für Lebensmittelbetrieb (Trinkwasserverordnung TWVO), 12. Dez. 1990