NorthPestClean a Large-Scale Demonstration Project showcasing a New Remediation Method Based on In Situ Alkaline Hydrolysis

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1 NorthPestClean a Large-Scale Demonstration Project showcasing a New Remediation Method Based on In Situ Alkaline Hydrolysis By Morten Bondgaard, Børge Hvidberg, Loren Ramsay, Scott Warner Kirsten Rügge and Torben Højbjerg Jørgensen Monterey, CA, USA

2 Chemical dumpsite Dumpsite (Groyne 42) Chemical Manufacturing plant

3

4 History In situ Alkaline hydrolysis Remediation (encapsulation) Remediation (partial excavation) Remediation (partial excavation) 1960 Dumping of chemicals

5 Principle sketch

6 Primary contaminants, insecticides S P N 2 Parathion, 170 tons S P N 2 Methyl-parathion, 55 tons S P S Malathion, 18 tons S S P P Sulfotep, 7 tons

7 The principle of alkaline hydrolysis S P N 2 NaH (ph 12) P S Na Na N 2 Parathion Water-soluble hydrolysis products,-diethyl para-nitrophenol phosphorothioate (Degradation by nucleophilic substitution)

8 Pilot test area Test cells Test pipes

9 Initial charaterisation of test cells

10 Initial charaterisation of test cells Distribution in soil Mass calculations (kg) - test cells TC1 TC2 TC3 Parathion Methyl parathion Malathion Sulfotep Hg

11 Initial charaterisation of test cells Test cell Parathion (EP3) distribution

12 Start of demonstration experiment Draining the test cells

13 Caustic soda infiltration (ph 13)

14 Monitoring of hydrolysis progress Water sampling ph13 (NaH treated) ph 6 untreated

15 Results monitoring (6 months) Test cell 2 (well 9, screen 1) 3000,0 2500,0 2000,0 1500,0 1000,0 PNP EP2-acid MP2-acid N2 Na P Conc. [mg/l] 500,0 0, S Na

16 Results - pesticide degraded after 2½ months treatment Parathion Mass parathion hydrolysed: 5-25% Methyl parathion Mass methyl-parathion hydrolysed: 50-80%

17 Is the hydrolysis underestimated?? EP2-acid 3000,0 2500,0 2000,0 P S - Na + NaH P H S - Na + + H 1500,0 1000,0 500,0 0, PNP N 2 N - N + H N H PNP EP2-acid N N H H 4- nitrophenol (PNF) 4-nitrosophenol H 4,4'-dihydroxy-azoxy-benzene H 4,4'-dihydroxy-azobenzene (mørkrød farve) NH 2 H HN NH H 4-aminophenol H 4,4'-dihydroxy-hydrazo-benzene

18 Results - monitoring of mercury in water Total-Hg in water Hg (ug/l) Test cell 1 Test cell 2 Test cell 3 Before NaoH addition 2½ months after NaH addition Increase > 1000 factor!!

19 Conclusion in situ alkaline hydrolysis Main conclusions the 1 st round of experiments 5-25% of parathion is hydrolysed after 2½ months 50-80% of methyl-parathion is hydrolysed after 2½ months Hydrolysis is underestimated Mobilisation of Hg in the groundwater ph kept for > 7 months

20 Next steps 1 st experiment- finalization (may-june 2012) Water samples (monitoring) -> for estimation of pesticides hydrolyzed Soil sampling -> for estimation of pesticide mass reducing in soil 2 nd experiment ( ) Contact enhancement methods to boost the effect of caustic soda Acoustic vibration Surfactant Recirculation Results in

21 Perspective The future Decision-basis (December 2013) Political decision on full-scale remediation ( ) Full-scale remediation ???

22 Acknowledgements Funding NorthPestClean European Commissions LIFE+ programme Danish Environmental Protection Agency Central Denmark Region Participants Anja Melvej, Børge Hvidberg, Hans Fredborg, Kaspar Rüegg, Lars Ernst, Thomas Damgaard, (Central Denmark Region, Denmark) Kirsten Rügge, Torben Jørgensen, Lars Nissen (CWI, Denmark) Lars R. Bennedsen (Rambøll, Denmark) Freddy Steen Pedersen (Kogsgaard Miljø, Denmark) Jens Muff (Aalborg University, Esbjerg, Denmark) Leah MacKinnon, Erik Petrovskis, Neal D. Durant (Geosyntec, USA) Kurt Pennel (Tufts University, USA) Eric Vogler (NASUS Water Treatment Technologies, USA) Bo Breinbjerg (Cheminova, Denmark) Loren Ramsay (NIRAS, Denmark) Scott Warner (Amec, USA)

23 Thank you for your attention! For more information visit

24 Concept for full-scale remediation

25 NorthPestClean Demonstration project in situ alkaline hydrolysis bjectives: In situ alkaline hydrolysis documentation of efficiency Enhancement technologies (delivery and contact) Stop-criteria for clean-up Final output : Political decision-basis for full-scale remediation

26 Initial charaterisation of test cells % of contaminants found as sorbed and DNAPL

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