29. Safe Management of PCBs and Case Studies

Heidelore Fiedler
Bavarian Institute for Waste Research - BIfA GmbH
Am Mittleren Moos 46a, D-86167 Augsburg, Germany

  1. Regulations and Management of PCBs in Germany
    1. German Regulations for PCB-Containing Waste

After the impact of PCBs on the environment was recognised, the most prominent producers Monsanto and Bayer voluntarily stopped their PCBs production in 1977 and 1983, respectively (DFG 1988). A ban on the marketing of PCBs 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, PCBs are no longer used in the Federal Republic of Germany in new electrical equipment (capacitors, transformers). The placing on the market of PCBs 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 In 1993, the PCB Prohibition Ordinance was superseded by the Chemicals Prohibition Ordinance.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 PCBs 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 PCBs 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

      1. Definitions
      2. 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

      3. Origin of PCB-containing Waste

Electrical area

Mining area

Other areas

      1. Possibilities of Disposal

In Germany, disposal of PCBs 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 PCBs 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 PCBs and PCB-containing waste (Kohleoel-Anlage Bottrop). For underground disposal one salt mine is commissioned in Germany (Herfa-Neurode). Solvents containing PCBs should be distilled for solvent recovery, decreasing the volume of PCB-containing waste.

      1. Cleaning and Disposal of Transformers with PCB-containing Dielectric Fluids
      2. 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 PCBs 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 PCBs 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 PCBs are to be disposed of, but PCBs 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 PCBs 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. (t)

        East Ger. (t)

        Total (t)

        Askarel transformers 14,000 40 14,040
        Mineral oil transformers (PCB>1,000 ppm) 110,000 100 110,100
        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. (t) East Ger. (t) Total (t)
        Drained Askarel transformers (PCB <1,000 ppm) 32,000 100 32,100
        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. 100,000 ca. 23,000 ca. 125,000
      3. Other Regulations Addressing PCBs
        1. Sewage Sludge and Compost
        2. According to the ordinance on sewage sludge [AbfKlärV], there is a limit value for sludges applied on agricultural land:

          Table 3: Limit values for PCBs and PCDD/PCDFs in sewage sludge applied on agricultural [AbfklärV]. d.m.= dry matter

          Substance Limit Value-Unit
          PCB 28, PCB 52, PCB 101, PCB 138, PCB 153, PCB 180 0.2 mg/kg d.m. per congener
          Sum of the above PCB-congeners 1.0 mg/kg d.m.
          PCDD/PCDF 100 ng I-TEQ/kg

          In compost the limiting values for agricultural application are 1/6 of the above given concentrations.

        3. Food
        4. 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.

        5. lndoor Air
        6. 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 PCBs 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.

        7. Drinking Water

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.

    1. Use of PCBs

Closed systems are those from which PCBs can be retrieved. Large, long-lived products in which PCBs 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:

      1. Transformers and Electrical Capacitors
      2. 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 PCBs 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.

      3. Hydraulic Oil

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 PCBs were used. In French and German mines, PCBs were used in hydraulic fluids together with additives imparting ageing stability, corrosion protection, wear resistance and improved foaming behaviour.

  1. Teningen Waste Dump
  2. 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, PCBs were 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. PCBs couldn’t be detected in the water samples, however, whenever water was pumped and thus, fine sediment particles were mobilised, PCBs 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 PCBs 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 PCBs. 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)

    Guideline

    Gravel Pit Above Dump

    Gravel Pit Below Dump

    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
  3. Indoor Air Problem
  4. 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 1-40% of PCBs (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]

    PCBs PCB 28 PCB 52 PCB 101 PCB 153 PCB 138 PCB 180 S 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 PCBs 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 5-30 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 50-100 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 PCBs 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
  5. References

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 Thiokol-Rubber Sealants in an Office Building. Chemosphere 25, 1481-1486

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, 435-439

Roßkamp E. (1992): Polychlorierte Biphenyle in der Innenraumluft - Sachstand. Bundesgesundhbl. 9/92, 434

German and International Regulations

AbfBestV: Verordnung zur Bestimmung von Abfällen nach § 2 Abs. 2 des Abfallgesetzes (Abfallbestimmungsverordnung - AbfBestV) 3. April 1990. Ordinance on the determination of waste.

AbfG: Gesetz über die Vermeidung und Entsorgung von Abfällen (Abfallgesetz - AbfG) 27. Aug. 1986. Law on the avoidance and disposal of waste

AbfKlärV: Klärschlammverordnung (AbfKlärV) vom 15.04. 1992. Bundesgesetzblatt, Jahrgang 1992, Teil 1, 912-934. Sewage sludge ordinance

AbfVerbringVO: 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. Ordinance of the EU on the control of transport of waste within and outside of European Union

AltÖlV: Altölverordnung (AltölV) 27. Okt. 1987. Used oil ordinance

AbRestÜberwV: Verordnung über das Einsammeln und Befördern sowie die Überwachung von Abfällen und Reststoffen (Abfall- und Reststoffüberwachungsverordnung - AbRestÜberwV) 3. April 1990. Ordinance on collection, transport and control of waste and residual materials.

BImSchG: Gesetz zum Schutz vor schädlichen Umwelteinwirkungen durch Luftverunreinigungen, Geräusche, Erschütterungen und ähnliche Vorgänge (Bundes-Immissionsschutzgesetz -BImSchG) 14. Mai 1990. Law on the protection from harmful environmental effects by air pollutants.

ChemVerbotsV: Verordnung über Verbote und Beschränkungen des lnverkehrbringens gefährlicher Stoffe, Zubereitungen und Erzeugnisse nach dem Chemikaliengesetz (Chemikalien-Verbotsverordnung - ChemVerbotsV) 14. Okt. 1993. Ordinance on the ban and limitations for use of dangerous substances.

DIN: DIN 51 527, Prüfung von Mineralölerzeugnissen, Bestimmung des Gehaltes an polychlorierten Biphenylen (PCB. Part 1: Determination of the concentration of polychlorinated biphenyls in mineral oil.

EU-689: Richtlinie über gefährliche Abfälle (91/689/EWG) 12. Dec. 1991. Ordinance on dangerous waste.

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: Verordnung zum Verbot von polychlorierten Biphenylen, polychlorierten Terphenylen und zur Beschränkung von Vinylchlorid (PCB-, PCT-, VC-Verbotsverordnung) 18. Juli 1989. Ordinance on the ban of PCB and PCT.

RestBestV: Verordnung zur Bestimmung von Reststoffen nach § 2 Abs. 3 des Abfallgesetzes (Reststoffbestimmungsverordnung - RestBestV) 3. April 1990. Ordinance on the determination of residual material.

SHMV: Verordnung über Höchstmengen an Schadstoffen in Lebensmitteln (Schadstoff-Höchstmengenverordnung - SMHV), 23. März 1988. Ordinance on maximum concentrations of toxic substances in food

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: Verordnung über Trinkwasser und Wasser für Lebensmittelbetrieb (Trinkwasserverordnung -TWVO), 12. Dez. 1990. Ordinance on drinking water.