1. 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 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. 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

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
1. Upstream
Sampling
Locations
Five sampling locations
Schedule
Weekly
Increased frequency for fireworks display
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., National Defense Programs. Pollutions Engineering, Aug. 2001: 38-43
Health Canada,
Interstate Technology & Regulatory Council, Perchlorate: Overview of Issues, Status and Remedial Options. ITRC Technological Overview, September pp 90
Motzer, W.E., Perchlorate: Problems, Detection, and Solutions. Environmental Forensics, 2: Jackson, W.A. et al., Perchlorate Occurrence in the Texas Southern High Plains Aquifer System. Ground Water Monitoring & Remediation, 25:
Shantz, M. et al., The Effect of Drawdown on Suspended Solids and Phosphorus Export From Columbia Lake, Waterloo, Canada. Hydrological Processes, 18:
US Environmental Protection Agency,
Cheremisinoff, N.P., National Defense Programs. Pollutions Engineering, Aug. 2001: 38-43
Health Canada,
Interstate Technology & Regulatory Council, Perchlorate: Overview of Issues, Status and Remedial Options. ITRC Technological Overview, September pp 90
Motzer, W.E., Perchlorate: Problems, Detection, and Solutions. Environmental Forensics, 2: Jackson, W.A. et al., Perchlorate Occurrence in the Texas Southern High Plains Aquifer System. Ground Water Monitoring & Remediation, 25:
Shantz, M. et al., The Effect of Drawdown on Suspended Solids and Phosphorus Export From Columbia Lake, Waterloo, Canada. Hydrological Processes, 18:
US Environmental Protection Agency,