by Dr. Heidi Fiedler

1. Introduction

This paper briefly summarizes German regulations and guidelines addressing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF). Actions taken to reduce formation, emissions and exposure of PCDD/PCDF give a retrospective view of dioxin issues that occurred in Germany in the past.

2. Legally binding regulations
1. Indirect Measures

As PCDD/PCDF were never produced intentionally on an industrial scale or for any commercial application, the production of dioxins cannot be prohibited or ceased out regulated by law. Therefore, indirect measures have been taken to reduce new inputs of PCDD/PCDF into the environment. The first laws addressed the ban of chemicals known to be contaminated with PCDD/PCDF (ppb to ppm-range I-TEQ): Ban of polychlorinated biphenyls (PCB) of July 18, 1989 (PCB 1989) and the ban of the production and use of pentachlorophenol (PCP) of December 12, 1989 (PCP 1989). It was estimated that an environmental contamination of more than 4 kg TEQ per year was caused by the use of PCB and of more than 1 kg TEQ per year was caused by PCP (Basler 1995).

The First Ordinance on the Prohibition of Certain Chemicals has set stringent limit values for eight PCDD/PCDF in substances, preparations and articles placed on the market. This regulation was amended in 1994 and 1996 (ChemVerbotsV 1996) and sets limit values for all seventeen 2,3,7,8-chlorine substituted congeners (in addition, limit values were established for eight 2,3,7,8-bromine substituted dibenzo-p-dioxins and dibenzofurans, PBDD/PBDF). According to the law, substances, preparations and/or articles are not allowed to be placed on the market:

• if the sum of the concentrations of the congeners listed in column 1 under No. 1 of column 1 (Table 2) exceeds a value of 1 µg/kg, or
• if the sum of the concentrations of the congeners listed in column 1 under Nos. 1 and 2 exceeds a value of 5 µg/kg, or
• if the sum of the concentrations of the congeners listed in column 1 under Nos. 1, 2 and 3 (= all congeners substituted in 2,3,7,8-position), exceeds a value of 100 µg/kg.

The Ordinance is in force since July 5, 1994; last amendment in 1996. However, transition periods of three to five years were set inter alia for anthraquinone pigments, dyes and pigments which are produced from chloranil as intermediate product, as well as for chloranil itself if it is used as a catalyst in the production of dyes and pigments. The Ordinance does not apply to intermediate substances or to certain products which are already regulated by other legislation, e.g. drugs, pesticides, foodstuffs or marketing for a proper waste disposal and for purposes of research or testing of properties or as a control substance for analytical investigations.

1. Regulation on Incineration and Combustion

On December 1, 1990, the Ordinance on Waste Incineration Plants (17^th BImSchV 1990) entered into force setting a limit value of 0.1 ng TEQ/m³ for PCDD/PCDF emissions from incinerators for waste and similar combustible materials. According to this Ordinance, new plants had to comply with the emission limit of 0.1 ng TEQ/m³ immediately, existing plants by 1994 or 1996 at the latest. In the past, the average dioxin concentration in the stack gases from municipal solid waste incinerators (MSWI) was 8 ng I-TEQ/m³. As a result, the 47 MSWI in western Germany emitted a total of about 400 g I-TEQ per year into the atmosphere. With the new regulation, the dioxin emissions were reduced to more than 99% (since 1996, the 50 MSWI in Germany emit less than 4 g I-TEQ/a).

The same emission limit value for waste incinerators exists in Austria and the Netherlands as well as a guideline in Sweden. In addition, the Directive of the European Community sets a limit value of 0.1 ng I-TEQ/m³ for hazardous waste incinerators for all fifteen member states of the European Union.

Due to very high concentrations of PCDD/PCDF (>100 ng I-TEQ(m³) in the off-gases from cable smouldering plants, the last cable smouldering plant was shut down in 1990 in Germany. Today, only cold cable-stripping processes are in use. Due to high dioxin emissions, hospital waste incinerators were closed as well in the beginning of the 1990s.

In 1997, a dioxin limit value of 0.1 ng I-TEQ/m³ and a minimum temperature of 850 °C for crematories was set by law (27^th BImSchV 1997).

Presently, there is ongoing work to evaluate if the limit value for waste incinerators of 0.1 ng TEQ/m³ can also apply to other thermal plants, e.g. plants for metallurgical treatment of iron ore, melting plants of secondary aluminum, and others.

Table 3: Summary on dioxin related laws in Germany and some European countries
(d.m. = dry matter)

Waste Incinerators Austria, The Netherlands, Germany Guideline value in Sweden	0.1 ng I-TEQ/m³ 0.1 ng Eadon-TEQ/m³
EU: Hazardous Waste Incinerators	0.1 ng I-TEQ/m³
Crematoria (Germany)	0.1 ng I-TEQ/m³
Sewage Sludge Ordinance (Germany) (max. load: 5 tons per hectare in 3 years)	100 ng I-TEQ/kg d.m
Compost Ordinance (State of Baden-Württemberg in Germany)	17 ng I-TEQ/kg d.m.

2. Further Regulations

To stop the impact of dioxins into the environment from use of so-called scavengers, e.g. dichloroethane or dibromoethane as additives, in leaded gasoline, a ban of the use scavengers was passed in 1992 (19^th BImSchV 1992). The annual emissions during combustion, especially of brominated and mixed-halogenated dibenzodioxins and -furans, were estimated to be in the range of 50 g I-TEQ per year in Germany (Basler 1995).

The Ordinance on Sewage Sludge (AbfKlärV 1992) in its revised version set a limit value of 100 ng I-TEQ/kg dry matter for sewage sludges used as fertilizer in agriculture, horticulture or forestry. In addition, the law sets a freight limit for 5 tons of dry matter of sewage sludge per hectare once within three years. Application of sewage sludge on pasture is forbidden by law.

Similarly, there exists a recommendation for use of compost. The limit value is 17 ng I-TEQ/kg d.m. In the State of Baden-Württemberg, this limit value is confirmed in a law.

1. Recommendations by Established by the Joint Working Group on Dioxins

In Germany, a Joint Working Group on Dioxins was established. So far, two reports were published giving recommendations and reference values for PCDD/PCDF concentrations in soil and cow milk.

Still today, all the proposed measures are recommendations for action, but they are not legally binding. Nevertheless, they are a basis for political decisions to protect men and the environment. In some cases, e.g. accidents such as a fire at a plastic store, these recommendations for actions were taken for decision making.

1. Levels in Soil

The first report of Joint Working Group was published in 1992 and contained the reference values and recommended action for agricultural and horticultural land uses (Table 4, BLAG 1992).

• For preventive reasons and on a long-term objective the dioxin concentrations of soil used for agricultural purposes should be reduced to below 5 ng TEQ per kg.
• Cultivation of foodstuffs is not restricted in the case the soil contains 5-40 ng per kg. However, critical land uses, for example grazing management, should be avoided if increased dioxin levels were found in foodstuffs grown on such soils.
• Limitations on the cultivation of certain feedstuffs and foodstuffs might be necessary if the dioxin contamination were above 40 ng TEQ per kg soil. However, unlimited cultivation is allowed for plants with minimum dioxin transfer, e.g. corn.

Guideline values were established for measures to be taken on children playgrounds and in residential areas (Table 4):

• Remediation of contaminated soil is required in playgrounds if the soil contains more than 100 ng TEQ per kg. Remediation means sealing, decontamination or exchange of soil.
• In residential areas, such action should be taken if the soil is contaminated with more than 1,000 ng TEQ per kg.
• In industrial areas, the limit value was set to 10,000 ng TEQ per kg.

The recommendations have been translated into governmental decrees in a number of Länder (Federal States in Germany).

1. Levels in Cow Milk

The second report of the Joint Working Group was published in 1993 and was a documentation on the dioxin contamination of food (BLAG 1993). Moreover, guidelines and maximum values for milk and dairy products together with recommendations for action were deduced. The dioxin content on milk and milk products varied between 0.14 pg TEQ/g milk fat and 5.61 pg TEQ/g milk fat with a mean value of 1.09 pg TEQ/g fat.

The limit values as given in Table 5 were derived as follows:

• Based on an TDI (total daily intake) value of 10 pg 2,3,7,8-TCDD/kg body weight and day, the maximum dioxin concentration in milk should not exceed 5.0 pg TEQ/g milk fat. Thus, milk and dairy products should not be out on the market if the dioxin contamination exceeds this value. However, as from the existing data it was obvious, that a limit value of 5 pg TEQ/g milk fat would cut off only a few cases of extreme contamination, this limit value was considered not to have any consequences at all and would not improve the consumer’s situation.
• To reduce the human impact via consumption of dairy products, a limit value of 3 pg TEQ/g fat was set. If such concentration were exceeded, the dioxin source should be identified and emission-reducing measures taken. Moreover, it was recommended that direct supply to the consumer be stopped for milk and dairy products containing more than 3 pg TEQ/g fat.
• Finally, an orientation value of 0.9 pg TEQ/g milk fat, based on the principle of precaution, was set. This concentration was derived from a TDI of 1 pg TEQ/kg body weight and day. The value of 0.9 pg TEQ/g milk fat can only be regarded as target value to be achieved as the data from Germany and other European countries showed that more than 50% of all dioxin concentrations in milk would exceed this value. To reach this target, it is necessary to further reduce the dioxin release into the environment.

1. Self-Commitment

The possibility of the formation of dioxins and furans in the pulp industry during chlorine bleaching is known. Based on the knowledge of the migration of PCDD/PCDF from filter paper into coffee and from paperboard into milk, the paper manufacturers reduced the dioxin levels in paperboard cartons to less than 1 ppt TEQ. Today, the formation and occurrence of dioxins due to production of pulp in Germany is only of minor importance. All mills in Germany use the sulfite process for pulping and almost no chlorinated substances for bleaching. Therefore, the formation of PCDD/PCDF in the Germany pulp industry is negligible.

1. European Dioxin Emission Inventory

On behalf of the European Commission, Directorate General XI (DGXI), the State Environmental Agency North Rhine-Westphalia published the results of a two year research program on information available with regard to emissions of PCDD/PCDF (LUA 1997). The report covers the 15 member states of the European Union and additionally includes Norway and Switzerland. The report covers PCDD/PCDF emissions to air, via waste, and residual matter for the reference period 1993 to 1995. Although over the last years, the knowledge on PCDD/PCDF emissions in European countries has improved considerable, the national inventories seem far away from being complete. Analyses of basic documents obtained from the 17 European countries gave total PCDD/PCDF emissions into the air from known sources of approximately 3,300 g I-TEQ/a (see ).

2. Ambient Air COncentrations in Germany

Recently, 223 ambient air samples were obtained from two sampling areas in Bavaria during 2½ years (winter 1993/94 until summer 1996) around two municipal solid waste incinerators located in Augsburg and in Burgkirchen. These results were compared with the same sampling locations in the Augsburg network for the time period summer 1992-winter 1992/93, before the start of the MWI (Fiedler et al. 1997).

A graphical sketch of the ambient air concentrations during the 2½ year sampling period in the Augsburg and the Burgkirchen networks is shown in Figure 1. As can be seen, a strong seasonal trend for PCDD/PCDF was found in both locations with higher concentrations during the winter months and up to 10fold lower concentrations during the summer months. The PCB concentrations exhibit a different behavior: Lower concentrations were found in the winter time and higher levels during the summer months. Note: The PCB concentrations (sum of 6 congeners) are three orders of magnitude higher than the PCDD/PCDF concentrations (reported as I-TEQ)!

AbfKlärV: Klärschlammverordnung (AbfKlärV) vom 15.04.1992. Bundesgesetzblatt, Jahrgang 1992, Teil 1, 912-934 (Sewage Sludge Ordinance)

Basler A. (1995): Dioxins and Related Compounds - Status and Regulatory Aspects in Germany. ESPR - Environ. Sci. & Pollut. Res. 2, 117-121

BImSchV (1990): 17. Verordnung zur Durchführung des Bundesimmissionsschutzgesetzes vom 23.1.1990 (Verordnung über Verbrennungsanlagen für Abfälle und ähnliche brennbare Stoffe - 17. BImSchV). Bundesgesetzblatt Teil I, Jahrgang 1990, 2832. (Ordinance for waste incinerators)

BImSchV (1992): 19. Verordnung zur Durchführung des Bundesimmissionsschutzgesetzes vom 24.07.1992 (Verordnung über Chlor- und Bromverbindungen als Kraftstoffzusatz-19. BImSchV). Bundesgesetzblatt Teil 1, Jahrgang 1992, 75 (Ordinance on ban of halogenated scavengers)

BImSchV (1997): Siebenundzwanzigste Verordnung zur Durchführung des Bundes-Immissionsschutzgesetzes (Verordnung über Anlagen zur Feuerbestattung - 27. BImSchV) vom 19. März 1997. BGBl. I, S. 545. (Ordinance for crematories)

BLAG (1992): Umweltpolitik: Bericht der Bund/Länder-Arbeitsgruppe DIOXINE. Rechtsnormen, Richtwerte, Handlungsempfehlungen, Meßprogramme, Meßwerte und Forschungsprogramme. Bundesminister für Umwelt, Naturschutz und Reaktorsicherheit (Hrsg.), Bonn, Januar 1992.

BLAG (1993): Umweltpolitik: 2. Bericht der Bund/Länder-Arbeitsgrupe DIOXINE. November 1993, Bonn.

ChemVerbotsV (1996): Verordnung über Verbote und Beschränkungen des Inverkehrbringens gefährlicher Stoffe, Zubereitungen und Erzeugnisse nach dem Chemikaliengesetz (Chemikalien-Verbotsverordnung - ChemVerbotsV) vom 19. Juli 1996. BGBl. I 1996, S. 1151, BGBl. I S. 1498 (Chemical’s Law).

Fiedler H., M. Swerev, H. Nordsieck, G. Dörr, and O. Hutzinger (1997): Long-term Ambient Air Measurements of PCDD/PCDF in Southern Germany (1993-1996). Organohalogen Compd. 33, 93-98.

LUA (1997): Identification of Relevant Industrial Sources of Dioxins and Furans in Europe. Materialien No. 43. Landesumweltamt Nordrhein-Westfalen, Essen, 1997.

PCB/PCT/VC (1989):. Verordnung zum Verbot von polychlorierten Biphenylen, polychlorierten Terphenylen und zur Beschränkung von Vinylchlorid (PCB-, PCT-, VC-Verbotsverordnung) 18. Juli 1989. BGBl. I, S. 1482 (Ordinance on the ban of PCB and PCT).

PCP (1989): Pentachlorphenol-Verbotsverordnung vom 12.12.1989, BGBl. I, S. 2235 (Ban of pentachlorophenol).