ANAN INTEGRATEDINTEGRATED APPROACHAPPROACH FORFOR THETHE REMEDIATIONREMEDIATION OFOF AA CATCHMENTCATCHMENT IMPACTEDIMPACTED BYBY FORMERFORMER MERCURYMERCURY MININGMINING Milena Horvat and co-workers Department of Environmental Sciences, Jožef Stefan Institute, Ljubljana, Slovenia [email protected] CoCo--workersworkers Jože Kotnik, Darija, Gibičar, Vesna Fajon, Nives Ogrinc, Nataša Nolde, David Kocman, Suzana Žižek, Branko Kontić- Department of Environmental Sciences, Jožef Stefan Institute, Ljubljana Alfred B. Kobal, Tatjana Dizdarević - Mercury Mine, Idrija Joško Osredkar - ICCB, University Medical Center, Ljubljana Jadran Faganeli - Marine Biological Station, National Institute of Biology, Piran Rudolf Rajar, Dušan Žagar, Gregor Petkovšek - Faculty of Civil Engineering and Geodesy, University of Ljubljana Damjana Drobne, Mihael Toman, Suzana Žižek - Faculty of Biology, University of Ljubljana Stefano Covelli –UniversityofTrieste, Italy Fabio Barbone – University of Udine, Italy Institute Jožef Stefan EU - Hg strategy January 2005, the Commission sent to the Council and to the European Parliament a communication on a Community strategy on mercury (doc. 5999/05), adopted on 24.June, 2005. Reducing mercury emissions Cutting supply and demand Looking for long-term solutions for mercury surpluses and reservoirs Protecting against mercury exposure Improving understanding of the mercury problem Supporting and promoting international action on mercury. Institute Jožef Stefan EU Hg strategy International action International initiative on production and supply Bilateral support UNEP Mercury Programme UNDP/GEF/UNIDO Global Mercury Programme UNECE Convention on Long-Range Transboundary Air Pollution EU Hg conference, Brussels, 26 – 27. October 2006 WhyWhy MediterraneanMediterranean?? LOCATIONS OF MERCURY MINES IN THE MEDITERRANEAN MERCURY IN THE MEDITERRANEAN FISH Total Hg in Sardina pilchardus Total Hg in Thunnus thynnus 0,5 5,0 4,0 n 0,4 ea an rr ite ed M 0,3 3,0 n nea rra e FW) (mg/kg, 2,0 (mg/kg, FW) 0,2 t i Concentration Concentration d Me 0,1 1,0 Atlantic Atlantic 0 0 0 20 40 60 0 100 200 300 400 Body weight (g) Body weight (kg) Bernhard et al., 1990 StudyStudy areaarea::interaction between the catchment and coastal environments the catchment and coastal environments Past: - 500 years of Hg mining (1490-1990) - 127.000 tons of Hg extracted - >37.000 tons lost into the environment - >12.000 tons entered the river system Today: - About 2500 kg/y enters the river system - About 1500 kg/y transported to the Gulf of Trieste Catchment area: 3300 km2 3 Soča at the mouth: 170 m /s 3 (extreme 3000– 4000 m /s) Precipitation: 1500 mm/y 0.3 Mio inhabitants Institute Jožef Stefan Mercury cycle Hgo in the wider Industrial 2+ + Idrija Hg CH3 Hg wastes region and the in CH3 HgCH3 Gulf of TriesteE s t u a r y ADVECTION and DIFFUSION 2+ o + Hg Hg CH3 Hg Contaminated sediments 2+ + DAM ,,Hg CH3 Hg , CH3HgCH3 Estuarine contaminated sediment I:I: ASSESMENTASSESMENT OFOF THETHE CURRRENTCURRRENT SITUATIONSITUATION MercuryMercury inin riverriver waterwater 400 5 0.8 Soca River Idrija River 4 300 0.6 Total Hg MeHg 3 200 0.4 2 Percent MeHg Percent MeHg (ng/L) Marine Total Hg (ng/L) Soca River Marine 100 Idrija River 0.2 1 0 0 0.0 10987654321 D6 AA CZ 1 2 3 4 5 6 7 8 9 10 D6 AA CZ Sampling Site (not to scale) Sampling Site (not to scale) MercuryMercury inin marinemarine sedimentssediments Total Hg MeHg 45.80 Monfalcone Is o n Sistiana z o 45.75 Hg (ppm) ITALY > 14.00 45.70 12.00 Grado 10.00 45.65 8.00 Trieste 6.00 4.00 45.60 3.00 2.00 45.55 Koper 1.00 < 0.50 Piran 45.50 SLOVENIA 45.45 13.35 13.40 13.45 13.50 13.55 13.60 13.65 13.70 13.75 13.80 13.85 MercuryMercury fluxflux intointo thethe GulfGulf ofof TriesteTrieste MassMass balancebalance ofof HgHg inin thethe GulfGulf ofof TriesteTrieste OccupationalOccupational mercurymercury intoxicationsintoxications inin IdrijaIdrija MercuryMercury MineMine fromfrom 1946 to 1977 1946 to 1977 Biological monitoring U.Erzen Idrija mercury mine - Department of Occupational Medicine, Alfred Bogomir Kobal Idrija: Mercury in air Kanomljica Spodnja Idrija K anomljica Spodnja Idrija Kanomljica Spodnja Idrija Idrijca Idrijca Idrijca Smelting Hg Smelting Hg Smelting Hg plant ng/m3 plant ng/m3 plant ng/m3 IDRIJA 1264 IDRIJA 2367 IDRIJA 2367 250 250 250 200 200 200 a ova ikov va Nik 150 N 150 Niko 150 Antonov 100 Antonov 100 Antonov 100 rov rov rov 75 75 75 50 50 50 40 40 40 30 30 30 20 20 20 10 10 10 Hg concentration in air 7.5 Hg concentration in air Hg concentration in air 3. Nov. 2003 7.5 7.5 30. Oct. 2003 3. Nov. 2003 13:30 - 15:50 5 9:10 - 15:30 5 9:10 - 15:30 5 No wind, 6°C, slight rain Slight S wind, 8°C, sunny Slight S wind, 8°C, sunny 2.5 2.5 0 500 1000m 2.5 0 500 1000 m 0 0 0 500 1000m 0 T-Hg concentration (mean, range) in selected vegetables ng/g 600 (520 - 1500) 866 (57 - 782) Idrija 400 420 reference 300 200 (22 - 386) 137 100 (13 - 103) 50 63.7 1.0 1.0 1.0 1.0 14 2.0 0 CARROTS PARSLEY LEAVES CHICORY CABBAGE LlETTUCE Mean (SD) T-Hg concentrations in river fish of the Idrijca river (Salmo sp.) and in marine fish (Conger conger) of the Gulf of Trieste ng/g fresh weight 800 610 680 (230) (870) 600 410 (450) 400 UrošEržen 200 100 (80) Kozarska above Idrija in Idrija grapa Gulf of Trieste Contaminated food and fish is the main source of exposure EstimatedEstimated dailydaily intakesintakes ofof HgHg inin humanshumans expresseexpressedd inin µµgHg/day/kggHg/day/kgbw 60 kg body weight Idrija Coastal area T-Hg MeHg T-Hg MeHg Air 0.05- 0.10 - 0.001 - .005 - Fish (50/100g/day) 0.20 - 3.33 0.09 – 1.60 0.18 - 1.35 0.17 - 1.33 Other food 0.66 0.132 0.05 0.01 US EPA recommended RfD: 0.1 µgHg/day/kgbw WHO/JECFA recommended RfD: 0.23 µgHg/day/kgbw Mercury mine Idrija, Slovenia Inhaled vs. ingested Hg in roe deer Hg intake into roe deer Location Inhalation Ingestion Inhalation: ingestion Hg Hg Ratio (µg/kg/day) (µg/kg/day) (%) Idrija – Zone A 0.10 109 0.09 Zone B 0.30 435 0.07 Near 4.0 2520 0.16 smelter Podljubelj 0.07 36.5 0.19 Controls 0.007 4.2 0.17 Gnamus and Horvat, 2001 II. Modelling tools Interaction between the models Input data Boundary conditions Meso-scale aquatic models •Mediterranean - Local scale models Regional scale aquatic models • sources • Idrijca and Soča River • erosion • Gulf of Trieste Institute Jožef Stefan Models Erosion model (Idrija region): Hg release 2.500 kg/year River model (Idrijca and Soča): transport and transformations Marine model (GulfofTrieste): Hg input 1500 kg/year Institute Jožef Stefan EROSION MODEL and Hg release GIS-layer based model A i Data – layers: topography, geology, pedology, land cover, land use, slope, precipitation, r e iv R runoff. a jc ri Measurements: Hg Id junction(J) Results: input data for the river model possible remediation measures Institute Jožef Stefan Modelling results for PT scenario Institute Jožef Stefan Results and findings from EROSION MODEL Present situation: annual Hg release to Idrijca River: 2500 kg PT scenario: change in land use and elimination of hot spots: decrease of annual Hg release to 1445 kg Possible reduction: 42 % Cost: 28 mil. € •ELOISE 2004 Institute Jožef Stefan 1-D model MeRiMod structure WASP5 - mass balance equations (advective and diffusive transport) - concentrations of various pollutants RIVMOD - bed load concentrations MERC4 - suspended load conc. - hydrodynamics - mercury speciation and - sediment transport kinetic transformation - velocities - concentrations of inorganic - depth mercury (HgII) - shear stress - concentrations of mono- methyl mercury (MMHg) already used for the Carson River (NV, USA) adapted for Idrijca and Soča Rivers (parameters – measurements) real time unsteady-state simulations •ELOISE 2004 Institute Jožef Stefan CONCEPT OF THE 3D WATER MODELING SYSTEM (MARINE ENVIRONMENT) • air-water exchange • methylation Hg MODULE demethylation PCFLOW3D • reduction • oxydation ADVECTION-DISPERSION MODEL FOR • exchange with the MERCURY with transformations bottom sediment river loads sea currents PCFLOW3D-ST sea bottom processes SEDIMENTATION MODEL PCFLOW3D-HD thermohaline forcing wind HYDRODYNAMIC MODEL tidal forcing river inflow momentum Institute Jožef Stefan Evasion 30 t To the Gulf 2160 t Sedimentation 1830 t 15.000 tons Institute Jožef Stefan III. WHAT WE CAN DO It is generally accepted that the formation and bioaccumulation of MeHg is the most critical point of environmental quality in mercury contaminated sites. The reduction of MeHg in seafood can therefore be defined as the priority objective with regard to the mercury contamination problem in the wider Idrija area and in the Gulf of Trieste. Institute Jožef Stefan POSSIBLE MEASURES to reduce toxic effect of MeHg in the area Reducing Hg transport within the river system: diminish erosion near Idrija (forestation, elimination of hot spots) dredging of sediments along both rivers construction of new reservoirs (?) – or elimination (?) Reducing methylation (conditions): to improve water quality in the river sytem and the Gulf – WW treatment, reducing mariculture, aeration (?) dredging of bottom sediment to reduce the source of MMHg - technically possible, very expensive, where to put Hg contaminated sediment (?) Administrative measures – prohibition of fishing, mariculture… Institute Jožef Stefan A conceptual Institute Jožef Stefan Institute Jožef SCENARIOS MANAGEMENT OPTIONS (BAU, POT, DG) Drivers-Pressure-State-Impact-Response Gains & losses POLICY RESPONSE Reduction of emissions, reduce erosion, control MeHg production Energy efficiency, taxes,saving programmes, Waste management, agriculture, fisheries, etc. Fossil fuelsconsumption, Increasing demand of energy, transport, transport, energy, of demand Increasing Waste production,Mi in species abundence and distribution abundence in species Hg concentrations in air,water,biota Emissions of Hg to the atmosphere, the Hgto of Emissions aquatic andterrestrialecosystems aquatic agriculture and fisheries, fisheries, agriculture and waste.