Dioxins in the environment - science for health Gdynia, 17-18th Sep 2013

1. Dioxins in the environment - science for health Gdynia, 17-18th Sep 2013 DioxinsProblem of the Baltic Sea? Matti Verta Finnish Environment Institute (SYKE) Centre for Sustainable Consumption and Production

2. This presentation • Problem • Trends • Sources • Point, atmospheric, country contributions • Predictions • What more to do?

3. Background • Baltic Sea: high loads and levels of dioxins (DLC), PCBs etc POPs • EU dioxin strategy evolving due also to other (food) dioxin concerns; no marketing high-dioxin fish (Baltic herring, Salmon) • Risks associated with dioxins/DLCs in Baltic fish? Modeled ΣPCB sea conc (MSCE)

4. Problem/humans? Herring comprise most of Finnish and Swedish commercial total fish catch In 2002-2010, nearly 60% of herring individuals for total catch processed to human consumption had WHOtotal-TEq higher than the maximum limit set by EU Permanent derogation to use fish with high levels, but not allowed to sell to third EU countries (Finland, Sweden, Latvia) Effects to humans? - immune system, hormonal system and reproductive functions, carcinogenity, nervous system? Problem/ecosystems? Fish-eating seabirds and mammals (seals) Fish?

5. FISH STUDIES Example Finland:PCDD/Fs and PCBs in domestic fish Ref: Hallikainen ym., 2011

6. Risks and management of DLCs in BS fishKEY FINDINGS – RISK ASSESSMENT(Assmuth and Jalonen 2005) • Sources partly poorly known • Inconclusive proof for ’severe’ human effects • Variation in risks (in time, space, populations) • Concurrent benefits from consuming contaminated fatty sea fish • Ecosystems: probable past disorders in fish-eating sea birds and seals (dl PCBs), other contaminants contribute • Present effects to wildlife not known

7. Endocrine Disrupting Chemicals(L. Birnbaum, DIOXIN 2013) HERBICIDES 2,4,-D 2,4,5,-T Alachlor Amitrole Atrazine Linuron Metribuzin Nitrofen Trifluralin FUNGICIDES Benomyl Ethylene thiourea Fenarimol Hexachlorobenzene Mancozeb Maneb Metiram - complex Tri-butyl-tin Vinclozolin Zineb METALS INSECTICIDES Aldicarb beta-HCH Carbaryl Chlordane Chlordecone DBCP Dicofol Dieldrin DDT andmetabolites Endosulfan Heptachlor / H-epoxide Lindane (gamma-HCH) Malathion Methomyl Methoxychlor Oxychlordane Parathion Synthetic pyrethroids Transnonachlor Toxaphene INDUSTRIAL CHEMICALS Bisphenol - A Polycarbonates Butylhydroxyanisole (BHA) Cadmium Chloro- & Bromo-diphenyl Dioxins Furans Lead Manganese Methyl mercury Nonylphenol Octylphenol PBDEs PCBs Pentachlorophenol Penta- to Nonylphenols Perchlorate PFOA p-tert-Pentylphenol Phthalates Styrene Testosterone synthesis inhibitorEstrogen receptor agonist Thyroid hormone disruptor Androgen receptor antagonist

8. Small doses may affect more than high doses • Our endocrine system: tiny amounts of hormones with profound effects on development and normal health • Chemical exposures, even at low doses, can disrupt delicate endocrine system and create a mechanism for disease • For some endocrine disruptors, biological changes can be seen at low doses, but not at high doses

9. Temporal development of DLCs and PCBs in Baltic herring and its consumers (straight lines), and hypothetical courses of biological responses (curves) Possible human effects Potential human effects from in utero exposure

10. Health effectsMineralisation defects caused by dioxins (Alaluusua et al. 2002) Effectseen with normalbackgroundexposurelevel • Firstmolarmineralisationdefect • Found in Finland in early 1990’s • Effectdisapperswhilecominglate 1990’s

11. Dioxin concentrations in fishermen and in average population in Finland (J. Tuomisto, THL)

12. Health benefit and risk comparison (Turunen et al. 2008) Fishermen mortality

13. Health benefit and risk comparison (Turunen et al. 2008) Fishermen mortality • Fishermen consume more fish than average population • They are exposed to higher levels of POPs • They get more omega-3-FA than average population • POP exposure doesn’t increase their mortality compared to average population

14. sPCB 9 % /yr 1969 - 2003 Chemical analyses, Department of Environmental Chemistry, Umeå University

15. Dioxins in herring- Swedish coast(Wiberg et al. 2013)

16. Dioxins and other POPs in herring – Finish coast (Airaksinen et al. in prep.)

17. TREND STUDIES WITH BREAST MILKLevels of PCDD/Fs and PCBs and PBDEs going down in Finnish breast milk(Kiviranta 2013) Most of the recent decrease in human breast milk is caused by dietary change, not a decrease in fish concentartions

18. Where do PCDD/Fs come from? • Old Identified POINT SOURCES • Pulp mills (G.of Bothnia, Swedish east coast), Kaliningrad?, TCDF • VCM-production (Sköldvik, Finland) OCDF • Chlorophenol production and use (HpCDF) • Kymijoki at present largest identified point source • Metal smelters, MWI, etc. (air) • Pesticide use in catchment • Note! • No major 23478-PeCDF or 12378-PCDD source identified among point sources other than in air emissions • Most major point emissions stopped in EU countries • Atmospheric sources still exist

19. Example of major old point source – cholophenol production plant in river Kymijoki (Verta et al. 2007) • Total dioxins/furans • (I-TEQ): • Kymijoki effect clear • 2,3,4,7,8-PeCDF: • Main congener in herring and salmon • NO regional trends • Mainly atmospheric?

20. Main PCDD/F congeners from I-TEQ in different environmental media (data from Finnish monitoring)

21. PCA analysis from sediment, sedimenting material, zooplankton and fish (Peltonen et al. in prep.) • Sediment shows change from point source to atmospheric signal • Zooplankton and fish show different direction but point source signal can be seen in zoopl.

22. Sediment profiles (Wiberg et al. 2013) • 50% or less decrease from late 1980’s • Clear chlorophenol signal in GB and in GF • Atmospheric/combustion signal dominates in Baltic Proper

23. AIR EMISSIONS (Gusev et al. 2013) 1990 2011

24. Air concentrations (Gusev etal.2013) 1990 2011

26. Concentrations of PCDD/Fs in air 2006-2007 (Sellström et al.) 2009)

27. MSC-East (Gusev et al. 2013) • PCDD/F pollution levels in the EMEP countries have decreased from 1990 to 2011 by 55%. • Total deposition of PCDD/Fs to the EMEP countries reduced by half during this period • Secondaryemissionscancontributemore than 50% to total PCDD/F deposition. • There is need to take into account emissions of PCDD/Fs to soil and water compartments

28. Baltic-POPs

29. Modeling PCDD/F in the Bothnian Sea (g TEQ), time trends with different options (Armitage et al. 2009)Resuspension probably underestimated Present deposition: Concentrtions in water, sediment (and probably in fish) will decrease by 50 %, but slowly 90% reductions will have a major effect within a decade

30. Are emission reductions enough? A mass balance approach • Emissions to air in 2005 (Gusev et al. 2009) • EMEP-countries 6 800 g (TEQ) • HELCOM countries <1 400 g • Deposition to Baltic Sea in 2005 • 200g I-TEQ (Gusev et al. 2008 , Armitage et al. 2009) • <100 g PeCDF • No reliable estimate of riverine load • Kymijoki 44 gI-TEQ • But only < 0.25 g PeCDF • Estimated burden in fish biomass • 5 g (max 10 g) • Mainly in herring and in sprat QUESS: The present load is enough to keep concentrations high for several decades!

31. Other means to fasten dioxin decrease in fish? • Extensivefishing of herring/sprat? • Removal of substantialamount of oldfishindividuals and DL compounds • Remaningstockyounger, fishgrowfaster, accumulateless DL OCs • Restoration of predativefishpopulations? • Codfisheries management These options should be looked at!

32. Modeling PCDD/F bioaccumulation(Peltonen et al. in prep) Growth rate most influential biological parameter on herring dioxin concentrations in the Baltic Proper the and Bothnian Sea • 2005 growth leads to double PCDD/F concentration in 30 g herring • Fish biology and ecological interactions are impending decreases and influencing spatial variation.

34. BS BSC Secondary sources such as resuspension and long range transport can be important up to 60% of the total load

35. Emission reduction measures

36. Comparison of Measures

37. Conclusions Measures of PCCD/F emission reduction identified in COHIBA project are in line with changes in European legislative and International Conventions Implementation processes of existing EU regulations e.g waste management, revision of BATand its implementation in industrial activities, have and will have a further impact on emission reduction New and planned regulations and requirements concerning industrial emissions will have a further impact on reduction from small and medium installations in industrial sectors and energy production facilities Emission reduction from the residential sector can be achieved in a longer perspective through a complex mix of measures: cultural social and economical changes Moreover, it should be tailored to regional problems including awareness raising,financial support schemes, strengthening regulations and enforcement Further understanding of the controled and uncontroled sources is needed

38. THANK YOU! Janusz Krupanek Riikka Airaksinen Karin Wiberg Hannu Kiviranta Ian Cousins Jouko Tuomisto Linda Birnbaum Jaakko Mannio Simo Salo Heikki Peltonen

39. Thank You! Terho Ovaska, Helsingin Sanomat, Jan 27 2005