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

Overview Overview Introduction: Background 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

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)

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

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

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

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

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)

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)

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

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

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

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

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

Results – Water Chemistry

Results – Water Chemistry

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.

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

Results – Soil chemistry

Relation to Co-contaminants Surface Water Soil Iodide Nitrate

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)

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.

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

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

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