The status of the Baltic Sea marine environment in terms of contamination by hazardous substances is assessed using several core indicators. Each indicator focuses on one important aspect of the complex issue. In addition to providing an indicator-based evaluation of the status of the Baltic Sea in terms of concentrations of PCBs, dioxins and furans in the marine environment, this indicator along with the other hazardous substances core indicators is used to develop an overall assessment of contamination status.
The "ICES 7" non-dioxin like PCBs (non-dl-PCBs) and dioxin like PCBs (dl-PCBs) , i.e. congeners CB-28, CB-52, CB-101, CB-118, CB-138, CB-153 and CB-180, are listed as mandatory contaminants that should be analysed and reported within both HELCOM and OSPAR, and are classed as priority POPs under the Stockholm Convention. In the proposed revised guidelines for OSPARCOM (1996) the congeners CB-105 and CB-156 are added to this list. Non-dioxin like PCBs are not included in the Water Framework Directive (WFD) priority substance lists, but they are included in the Marine Strategy Framework Directive (MSFD).
The Helsinki Convention (1974, 1992) has recommended special bans and restrictions on transport, trade, handling, use and disposal of PCBs. The Ministerial Declaration from 1998, within HELCOM and the 1995 Declaration of the Fourth international conference of the protection of the North Sea called for measures against toxic, persistent, bioaccumulating substances like PCBs to cease their inputs to the environment completely by the year 2020.
Dioxins and furans (PCDD/Fs) are included in several international agreements, of which the Stockholm Convention and the Convention on Long Range Transboundary Air are among the most important for the control and reduction of sources to the environment. World health organization (WHO) and Food and Agriculture Organization of the United Nations (FAO) have jointly established a maximum tolerable human intake level of dioxins via food, and within the EU there are limit values for dioxins in food and feed stuff (EC 2006). Several other EU legislations regulate dioxins, e.g. the plan for integrated pollution prevention and control (IPPC 2010/75/EC) and directives on waste incineration (EC, 2000, 2008). The EU has also adopted a Community Strategy for dioxins, furans and PCBs (EC 2001). PCDD/Fs are currently not included in the Water Framework Directive but are on the list of substances to be revised for adoption in the near future. HELCOM has listed PCDD/Fs and dl-PCBs as prioritized hazardous substances of specific concern for the Baltic Sea (HELCOM 2010), like OSPAR on the List of Chemicals for Priority Action (OSPAR 2010b).
Under the Stockholm Convention, releases of unintentionally produced by-products listed in Annex C4, including dioxins and dl-PCBs, are subject to continuous minimization with the ultimate goal of elimination where feasible. The main tool for this is a National Action Plan which should cover the source inventories and release estimates as well as plans for release reductions. At the EU level, a Strategy for dioxins and PCBs was adopted in 2001. The Strategy includes actions in the area of feed and food contamination and actions related to the environment, including release reduction. Over the past decade, important legislation has been adopted to reduce the emissions of PCDD/Fs, in particular in the areas of waste incineration and integrated pollution prevention and control. Releases of POPs, including dioxins, from industrial installations have been regulated by the IPPC Directive and the Waste Incineration Directive, the former requiring Member States to establish permit conditions based on the Best Available Techniques (BAT) for a wide variety of industry sectors, and the latter setting maximum permissible limit values for PCDD/F emissions to air and water from waste incineration. Currently these releases of these substances are regulated by the Directive on industrial emissions (IED, 2010/75/EU). The proper and timely implementation and enforcement of the IED remains a key priority in order to ensure the necessary reduction of emissions from major industrial sources. However, at present or in the near future, non-industrial sources are likely to exceed those from industrial ones (Quass et al. 2004).
Polychlorinated biphenyls (PCBs) and PCDD/Fs (dioxins and furans) are persistent organic pollutants (POPs) that can cause severe, long-term impacts on wildlife, ecosystems and human health. The substance groups are characterized by low water solubility and low vapour pressure. Due to their persistent and hydrophobic properties, the substances accumulate in sediments and organisms in the aquatic environment. In the environment, dioxins can undergo photolysis, however, they are generally very resistant to chemical and biological degradation.
Polychlorinated biphenyls (PCBs) consist of two linked benzene rings with chlorine atoms substituted for one or more hydrogen atoms. Theoretically, 209 congeners are possible, but only around 130 are found in commercial mixtures. Some PCBs are called dioxin-like (dl-PCBs) because they have a co-planar structure very similar to that of dioxins and have dioxin-like effects (i.e. four non-ortho substituted PCBs: CB-77, CB-81, CB-126, CB-169, IUPAC and eight mono-ortho substituted: CB-105, CB-118, CB-156, CB-157, CB-167, CB-114, CB-123, CB-189, IUPAC) (Burreau et al. 2006).
The name 'dioxin' refers to polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) compounds, i.e. two benzene rings with one (furans) or two (dioxins) oxygen bridges and substituted with 1–8 chlorine atoms. Of the 210 possible congeners, the 17 compounds (10 furans, 7 dioxins) substituted in positions 2, 3, 7 and 8 are considered to be of highest toxicological importance.
The non-dl-PCBs included in this core indicator report are essentially the 7 PCB congeners (with exception for CB-118 that is included in the dioxin like-PCBs) that have been monitored since the beginning of the HELCOM and OSPARCOM monitoring programmes. These PCBs are carefully selected mainly by ICES working groups due to their relatively uncomplicated identification and quantification in gas chromatograms and as they usually contribute a very high proportion of the total PCB content in environmental samples. These are the 'ICES 7': CB-28, CB-52, CB-101, CB-118, CB-138, CB-153 and CB-180.
Long-term effects of PCBs from human and laboratory mammal studies include increased risk of cancer, infections, reduced cognitive function accompanied by adverse behavioural effects, as well as giving birth to infants of lower than normal birth weight (Carpenter 1998, Carpenter 2006). There are also indications that PCBs are associated with reproductive disorders in marine top predators. PCBs are also assumed, together with p,p'-DDE, to cause eggshell thinning and reduced number of offspring in white-tailed eagles and uterine leioymas in grey seal in the Baltic Sea (Helander et al 2002, Bäcklin et al. 2010).
The most relevant toxic effects of PCDD/Fs are developmental toxicity, carcinogenity and immunotoxicity. The sensitivity of various species to the toxic effects of PCDD/Fs varies significantly. 2,3,7,8-TCDD is the most toxic and well-studied congener and is used as a reference for all other related chemicals. Each of the 17 relevant congeners is assigned a toxic equivalency factor (TEF), where 2,3,7,8-TCDD equals 1 (Van den Berg et al., 1998; Van den Berg et al., 2006). Dioxin concentrations are commonly reported as toxic or TCDD equivalents (TEQ), which is the sum of the individual congener concentrations multiplied with its specific TEF.
Substances, litter and energy
- Input of other substances (e.g. synthetic substances, non-synthetic substances, radionuclides) – diffuse sources, point sources, atmospheric deposition, acute events
PCBs are synthetic chemicals and do not occur naturally in the environment. Due to their properties, PCBs have been used in a wide variety of applications and manufacturing processes, especially as plasticizers, insulators and flame-retardants. They are widely distributed in the environment through, for example, inappropriate handling of waste material or leakage from transformers, condensers and hydraulic systems. According to some estimates, the total global production of PCBs from 1930 until the bans that were implemented in most countries by the 1980s had already been in the order of 1.5 million tons.
Dioxins (PCDD/Fs) were never produced intentionally, but they are minor impurities in several chlorinated chemicals (e.g., PCBs, chlorophenols, hexachlorophene, etc.), and are formed in several industrial processes and from most combustion processes, such as municipal waste incineration and small-scale burning under poorly controlled conditions. Formerly, pulp bleaching using chlorine gas was an important source of PCDD/Fs.
Numerous recent reports and papers have shown differences in PCDD/F and dl-PCB concentrations in Baltic herring, sprat and salmon between the Baltic Sea basins (e.g., Bignert et al. 2017; Karl et al. 2010). Higher concentrations have been detected in the northern basins where dioxin and dl-PCB levels in herring exceed established maximum limit concentrations for human consumption. Regional variation within a sub-basin has been found in the Swedish coastal region of the Bothnian Sea (Bignert et al. 2007), where the concentrations are higher than in other Swedish areas (Bignert et al. 2017). Since the atmospheric deposition pattern (lowest in the north) is different compared to the patterns detected in the concentrations in fish (generally highest in the north), other factors or sources than atmospheric deposition are thus likely to be involved. The reasons remain unclear, but higher historical PCDD/F discharges from point sources in the northern basins have been suggested. In general, the contribution from the dl-PCBs to the TEQ is substantial and seems to increase the further south in the Baltic region the samples are collected.