1. NATO-CCMS, IMS-Antwerp-TG, 1Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved WELCOME: Integrated Management System for Antwerp Harbor and Polish landfill site Ludo Diels 1 W. Dejonghe 1, J. Bronders 1, K. Vanbroekhoven 1, S. Van Roy 1,A. Szewczyk 2, M. Zabochnicka-Swiatek 2, J. Szdzuj 3, G. Malina 2 1. Flemish Institute for Technological Research, VITO, Mol, Belgium 2. Czestochowa University of Technology, TUC, Czestochowa, Poland 3. Institute for Ecology of Industrial Areas, IETU, Katowice, Poland NATO – CCMS meeting, Ottawa, 12 – 15 June, 2005

2. NATO-CCMS, IMS-Antwerp-TG, 2Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved WELCOME: Integrated Management System for Antwerp Harbor and Polish landfill site IMS: reminder Antwerp Harbor Site Tarnowskie Gory Landfill Site Conclusions

3. NATO-CCMS, IMS-Antwerp-TG, 3Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved IMS: Reminder 1.Megasite 1.Definition of the site as a megasite 2.Regulations and boundary conditions 3.Definition of the organisatorial role and management of the megasite 2.Risks and risk reduction 1.Megasite conceptual model 2.Regional risk approach by clustering 3.Risk reducing measures per risk cluster 3.Management scenarios or conceptual model 1.Risk reduction scenarios at megasite scale 2.Effects and uncertainties of the risk scenarios 3.Cost effective calculation of the selected scenarios 4.Priorities of the scenarios 4.Long term planning and management of a megasite 1.Technical implementation and monitoring plan 2.Long term audit of the IMS

4. NATO-CCMS, IMS-Antwerp-TG, 4Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Source-path-receptor model Antwerp harbour Planes of compliance

5. NATO-CCMS, IMS-Antwerp-TG, 5Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Selection of study area among 16 clusters Selection of example area for IMS application Clusters based on: –type of activity –availability of data –location of the area (docks)

6. NATO-CCMS, IMS-Antwerp-TG, 6Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved GIS data :Groundwater + type of investigation groundwaterlevel preliminary investigation descriptive investigation no investigation carried out

7. NATO-CCMS, IMS-Antwerp-TG, 7Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved concentration lower than back ground level (BGL) concentration higher than BGL but lower than soil remediation criteria concentration higher than SRC concentration higher than 10 X SRC concentration lower than back ground level (BGL) concentration higher than BGL but lower than soil concentration higher than SR GIS interpretation of benzene in groundwater

8. NATO-CCMS, IMS-Antwerp-TG, 8Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Source – path – receptor evaluation 32 1 Example area 1, 2 + 3 : flow lines

9. NATO-CCMS, IMS-Antwerp-TG, 9Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Source – path – receptor evaluation: flux calculation flow line 2  peak flow to dock = 60 g benzene /day After dilution: 1.9 10 -4 µg benzene/l surface water flow line 1 Time (years)

10. NATO-CCMS, IMS-Antwerp-TG, 10Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Conclusions and Actions IMS can be used on the harbor of Antwerp Integration of GIS data from Port of Antwerp and OVAM Management of pollution over time and prioritisation Document on the IMS for Antwerp, agreed by different stakeholders, to the ministry of Environment Discussions about implementation in legislation are planned In the mean time a second case ‘Kempen area’ heavy metal contaminated megasite (> 300 km²)

11. NATO-CCMS, IMS-Antwerp-TG, 11Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Tarnowskie Góry site Main pollutants: Cd, Zn, Cu, Ba, B, Sr, As: 100-250 000 ppb  Diffuse pollution * Soil: metal dust via the wind * Surface water: groundwater + rain water infiltration  Source pollution: * From waste heaps and old landfills * Into groundwater, Quaternary and Triassic aquifer Objectives of our study: 1. General approach to manage the risks of heavy metals in contaminated areas 2. Passive remediation measures: lab scale tests

12. NATO-CCMS, IMS-Antwerp-TG, 12Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Conceptual Model for the Tarnowskie Góry Megasite (Poland) Q – Quaternary aquifer Tr – Triassic aquifer DW – drinkwater well Sa,b – source of contamination 2 3 5 1 4 DW

13. NATO-CCMS, IMS-Antwerp-TG, 13Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation options for Tarnowskie Góry Megasite Q – Quaternary aquifer Tr – Triassic aquifer DW – drinking well Sa,b – source of contamination 2 5 31 4 DW

14. NATO-CCMS, IMS-Antwerp-TG, 14Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the unsaturated zone Q – Quaternary aquifer Tr – Triassic aquifer DW – drinking well Sa,b – source of contamination 2 1 DW Plants? Additives?

15. NATO-CCMS, IMS-Antwerp-TG, 15Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the unsaturated zone 1. Soil + dolomite: - Reduced leaching Zn - No reduced leaching Sr and Ba 2. Soil + diatomeaus earth: - Release metals 3. Soil + zeolites, Metasorb: - Reduced leaching of Zn - Limited leaching of Sr and Ba Soil + dolomite soil

16. NATO-CCMS, IMS-Antwerp-TG, 16Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the unsaturated zone Measured with BIOMET ® -sensor Soil + waste products: - D olomites - Diatomeaous earth - Zeolites Soil% bioavailable Zn Diatomeaous earth ~ 100 Dolomite~ 90 Zeolites~ 67

17. NATO-CCMS, IMS-Antwerp-TG, 17Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Evaluation of In situ treatment options for the Tarnowskie Gory megasite Installation of Reactive zones or Permeable Reactive Barriers based on: - Adsorption - In situ bioprecipitation process

18. NATO-CCMS, IMS-Antwerp-TG, 18Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the saturated zone Q – Quaternary aquifer Tr – Triassic aquifer DW – drinking well Sa,b – source of contamination 2 31 DW Plants Additives Sorption? ISBP?

19. NATO-CCMS, IMS-Antwerp-TG, 19Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the saturated zone Quaternary aquifer Element /Metal ZVICompostZeoliteMetasorb Sr--++ B---+ (1) Ba-+++ Zn+ND++ Cd++++ Cu++++ +: good removal; -: no removal (1): special anionic Metasorb ZVI: Zero Valent Iron Groundwater flow Sorption barrier Source Plume

20. NATO-CCMS, IMS-Antwerp-TG, 20Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the saturated zone C 3 H 6 O 3 + SO 4 2- ↔ CH3COO- + S 2- S 2- + Me 2+ ↔ MeS (immobilisation) (1) Using different aquifer types: - sand (Pr6 and Pr4) - clay (Pr2 and Pr5) (2) Using different C-sources: - molasses - HRC ® (Regenesis) - M RC® (Regenesis) - acetate Groundwater flow direction Plume Source Reactive zone: ISBP

21. NATO-CCMS, IMS-Antwerp-TG, 21Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved +++: very fast; ++: fast; ± removal; - no removal; S: sand; C: clay MetalSand NA Clay NA Formal- dehyde Sand + HRC ®, acetate Clay + HRC ®, acetate Sand + molasses Clay + molasses SO 4 ±±-++++++++++ Sr-----Release- B----- - Ba-----release- Zn±±-+++++ Cu±±-+++++ Remediation measures at the saturated zone Quaternary aquifer

22. NATO-CCMS, IMS-Antwerp-TG, 22Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the saturated zone Quaternary aquifer 1. Molecular technique: Detection SRB by PCR dsrB gene 2. Sequential extraction: - Immobilisation Zn and Cu - Not for Ba, B, and Sr

23. NATO-CCMS, IMS-Antwerp-TG, 23Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the saturated zone Triassic aquifer Q – Quaternary aquifer Tr – Triassic aquifer DW – drinking well Sa,b – source of contamination 2 3 5 1 4 DW Plants Additives Sorption ISBP Sorption + ISBP?

24. NATO-CCMS, IMS-Antwerp-TG, 24Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the saturated zone Triassic aquifer Immobilisation metals by: 1. Stimulation ISBP by different C- sources: - Molasses - HRC ® (Regenesis) - MRC ® (Regenesis) - Lactate 2. Precipitation metals by different adsorbents: - Zeolite - Dolomite - Diatomeaous earth

25. NATO-CCMS, IMS-Antwerp-TG, 25Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the saturated zone Triassic aquifer Zeolite + molasses Zeolite + HRC ®

26. NATO-CCMS, IMS-Antwerp-TG, 26Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Remediation measures at the saturated zone Triassic aquifer + removal; - no removal Metal No additionHRC ®, MRC ®, lactate, molasse C-source + dolomite, diat. earth C-source + zeolite SO 4 -++(+) Zn-++(+) Sr---+ B--- + (>35 %) Ba---+ C-source: molasse or HRC ®

27. NATO-CCMS, IMS-Antwerp-TG, 27Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Conclusions on remediation measures at the Tarnowskie Góry Megasite Unsaturated zone - Evaluation of plants  Toxicity towards plants  Selection of low-uptake plants to prevent spreading heavy metals: grass - Immobilization with additives  Control by - BIOMET ® -test - Plant uptake tests - Leaching tests  Zn immobilisation by dolomite and zeolite; release by diatomeaus earth  Sr and Ba immobilisation by zeolites and Metasorb  B immobilisation by combination of ApX-As and Metasorb-anionic)

28. NATO-CCMS, IMS-Antwerp-TG, 28Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Conclusions on remediation measures at the Tarnowskie Góry Megasite (II) Saturated zone - Quaternary aquifer * Adsorption on adsorbents in a Permeable Reactive Barrier All metals removed by zeolite except B B removal ↔ Metasorb (arsenate) + Apeyron adsorbent * In situ bioprecipitation Difficult for B, Sr and Ba More mobile metals as Zn and Cu very well removed but stimulation by C-sources (NOT molasse!) necessary Molecular technique: unravelling microbial populations - Triassic zone * In situ bioprecipitation in combination with additives ISBP for Zn but C-sources needed Zeolite + HRC ® or molasse for B, Ba and Sr but some inhibition ISBP! Confirmation necessary of adsorbents + C-sources

29. NATO-CCMS, IMS-Antwerp-TG, 29Ottawa, October 11, 2014 confidential – © 2005, VITO NV – all rights reserved Integrated Management System: applicable on -Harbor sites -Large industrial sites Possibilities for passive treatment systems -Metallurgical sites -Mining areas -Surface treatment -…  ISBP: www.vito.be  IMS: www.euwelcome.nl