A Case-study on the Persistence of Perchlorate Following a Firework Display

1. A Case-study on the Persistence of Perchlorate Following a Firework Display A Case-study on the Persistence of Perchlorate Following a Firework Display Columbia Lake, Waterloo, Ontario, Canada Columbia Lake, Waterloo, Ontario, Canada Michelle J. Sabourin Supervisors Dr. Carol Ptacek and Dr. David Blowes Michelle J. Sabourin Supervisors Dr. Carol Ptacek and Dr. David Blowes

2. Overview Overview Introduction: Background Uses for perchlorate Behaviour: Persistence Co-existing contaminants Case-Study: Columbia Lake Canada Day fireworks Results: Water chemistry Soil chemistry Summary / Next Steps Introduction: Background Uses for perchlorate Behaviour: Persistence Co-existing contaminants Case-Study: Columbia Lake Canada Day fireworks Results: Water chemistry Soil chemistry Summary / Next Steps

3. Introduction – Background • Increasing concern • Widespread perchlorate contamination • Contamination reports escalated with improved analytical methods • Prior to 1997 only detected 100–400 µg/L(Motzer, 2001) • Safe level undetermined • U.S. : range 1-18 µg/L (USEPA, 1999) • Canada: approx. 6 µg/L (Health Canada, 2004)

4. Introduction – Background • Health risks : • Affects thyroid • Concerns mostly pregnant women and infants (ITRC, 2005) • Hypothyroidism / Hyperthyroidism • Dose-response effects need to be evaluated (Cherminisinoff, 2001.) • Ecological concerns: • Toxicological effects

5. Introduction – Background • Contaminant locations: • Common in South-West U.S. • California • Nevada • Utah • Present in: • Drinking water • Milk • Lettuce • Wine (USEPA, 2004)

6. Natural Occurs naturally in brines Atacama Desert in Chile(Jackson, 2005) Introduction – Uses for perchlorate VS. • Anthropogenic • Fertilizers • Textile Industry • Mining Industry • Military Use • Rocket Propellant • Fireworks

7. Behaviour - Persistence • Perchlorate salts have very high solubility • Anion (ClO4-) • chemically stable • exceedingly mobile(Logan, 1998) • Results in persistence for decades in water systems

8. Case-study – Columbia Lake Goals of the Project: • Assess concentrations of perchlorate before and after a fireworks display • Evaluate relationship with concentrations of co-contaminants • Determine sources of perchlorate • eg. background levels (agriculture)

9. Case-study – Columbia Lake Description of Columbia Lake: • Constructed in 1967 • Maximum depth of 2.8 m • Located 2 km downstream from Laurel Creek Reservoir • Reservoir acts as flood control • Columbia and Silver Lakes mostly for recreational purposes (Shantz, 2004)

10. Case-study – Columbia Lake Lake Description (Cont’d) • Land use varies: • Agricultural fields, woodlots, wetlands upstream • Highly developed commercial and residential areas downstream Canada Day Fireworks • Size of display: • $15,000 budget • Significantly less than other displays

11. Case-study – Canada Day Fireworks Sampling • Locations • Five sampling locations • Schedule • Weekly • Increased frequency for fireworks display 1.Upstream 2. Inflow 3. Outflow 4. Downstream 5. Silver Lake

12. Results – Water Chemistry • Perchlorate - Background • Generally: ~0.05 μg/L

13. Results – Water Chemistry • Perchlorate - Fireworks • Upstream and Inflow: ~0.05 μg/L • Outflow : 22.1 μg/L

14. Results – Water Chemistry • Iodide • Generally: ~0.1 to 0.2 μg/L • Peaks: ~1.0 μg/L • Nitrate • Generally: ~0.2 to 0.5 mg/L • Peaks : Up to 3.0 mg/L

15. Results – Water Chemistry

16. Results – Water Chemistry

17. Results – Water Chemistry • Perchlorate - Downstream • After the fireworks: 0.08 to 0.1 μg/L • Returns to background levels (~0.05 μg/L) after 4 weeks.

18. Results – Soil Chemistry • Soil samples: • Collected within area of detonation • Before and after display • Fireworks: • Shot in S-W direction • Propagation estimated at ~470m

19. Results – Soil chemistry

20. Relation to Co-contaminants Surface Water Soil Iodide Nitrate

21. Method of Analysis • Recently developed method • IC coupled to tandem MS • 0.1 ml injection • Separation / suppresion performed with Ion Chromatograph • Quantification performed with Mass Spectrometer • Allows detection of perchlorate at levels as low as 0.05 µg/L (NWRI, 2005)

22. Summary • Following fireworks display, elevated concentrations of perchlorate were observed: • As high as 22 μg/L in the surface water • As high as 68 μg/kg in soils • Safe drinking water concentration for perchlorate in Canada is 6 μg/L • Iodide and nitrate concentrations allowed differentiation of fertilizer related and naturally occurring perchlorate from that of firework-derived perchlorate • Residence time in surface waters was 4 weeks • Bulk of the perchlorate had dissipated within a week.

23. Next Steps • Sample for isotopes and cations and integrate this data with observed lake chemistry • Evaluate processes controlling fate of perchlorate • Potential for supporting laboratory work

24. Acknowledgements Acknowledgements • Supervisors Dr. Carol Ptacek and Dr. David Blowes • Sue Brown and company at NWRI • Research group at the University of Waterloo • Department of Geography at the University of Waterloo • Supervisors Dr. Carol Ptacek and Dr. David Blowes • Sue Brown and company at NWRI • Research group at the University of Waterloo • Department of Geography at the University of Waterloo

25. References References Cheremisinoff, N.P., 2001. National Defense Programs. Pollutions Engineering, Aug. 2001: 38-43 Health Canada, 2005. http://www.hc-sc.gc.ca/ewh-semt/water-eau/drink-potab/perchlorate_e.html Interstate Technology & Regulatory Council, 2005. Perchlorate: Overview of Issues, Status and Remedial Options. ITRC Technological Overview, September 2005. pp 90 Motzer, W.E., 2001. Perchlorate: Problems, Detection, and Solutions. Environmental Forensics, 2: 301-311 Jackson, W.A. et al., 2005. Perchlorate Occurrence in the Texas Southern High Plains Aquifer System. Ground Water Monitoring & Remediation, 25: 137-149 Shantz, M. et al., 2004. The Effect of Drawdown on Suspended Solids and Phosphorus Export From Columbia Lake, Waterloo, Canada. Hydrological Processes, 18: 865-878 US Environmental Protection Agency, 2005. http://www.epa.gov/safewater/ccl/perchlorate/perchlorate.html Cheremisinoff, N.P., 2001. National Defense Programs. Pollutions Engineering, Aug. 2001: 38-43 Health Canada, 2005. http://www.hc-sc.gc.ca/ewh-semt/water-eau/drink-potab/perchlorate_e.html Interstate Technology & Regulatory Council, 2005. Perchlorate: Overview of Issues, Status and Remedial Options. ITRC Technological Overview, September 2005. pp 90 Motzer, W.E., 2001. Perchlorate: Problems, Detection, and Solutions. Environmental Forensics, 2: 301-311 Jackson, W.A. et al., 2005. Perchlorate Occurrence in the Texas Southern High Plains Aquifer System. Ground Water Monitoring & Remediation, 25: 137-149 Shantz, M. et al., 2004. The Effect of Drawdown on Suspended Solids and Phosphorus Export From Columbia Lake, Waterloo, Canada. Hydrological Processes, 18: 865-878 US Environmental Protection Agency, 2005. http://www.epa.gov/safewater/ccl/perchlorate/perchlorate.html