a case-study on the persistence of perchlorate following a firework display columbia lake, waterloo,...
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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, CanadaColumbia Lake, Waterloo, Ontario, Canada
Michelle J. SabourinSupervisors Dr. Carol Ptacek and Dr. David Blowes
Michelle J. SabourinSupervisors Dr. Carol Ptacek and Dr. David Blowes
Introduction: BackgroundUses for perchlorate
Behaviour: PersistenceCo-existing contaminants
Case-Study: Columbia LakeCanada Day fireworks
Results: Water chemistrySoil chemistry
Summary / Next Steps
OverviewOverview
Introduction: BackgroundUses for perchlorate
Behaviour: PersistenceCo-existing contaminants
Case-Study: Columbia LakeCanada Day fireworks
Results: Water chemistrySoil 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
Sampling• Locations
• Five sampling locations
• Schedule• Weekly
• Increased frequency for fireworks display
1. Upstream
2. Inflow
3. Outflow
4. Downstream
5. Silver Lake
Results – Water Chemistry
Columbia Lake Outflow Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0
1
2
3
4
515
20
Perchlorate
Columbia Lake Inflow Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate
Upstream from Columbia Lake Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate Perchlorate - Background• Generally: ~0.05 μg/L
Results – Water Chemistry
Columbia Lake Outflow Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Per
chlo
rate
, Io
did
e (
g/L
)
0
1
2
3
4
515
20
Perchlorate
Perchlorate - Fireworks• Upstream and Inflow: ~0.05 μg/L
• Outflow : 22.1 μg/L
Upstream from Columbia Lake Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate
Columbia Lake Inflow Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate
Results – Water Chemistry
Columbia Lake Outflow Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0
1
2
3
4
515
20
Perchlorate Iodide
Nit
rate
(m
g/L
)
0
1
2
3
4
5
Nitrate
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
Upstream from Columbia Lake Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate Iodide
Nit
rate
(m
g/L
)
0.0
0.5
1.0
1.5
2.0
Nitrate
Columbia Lake Inflow Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate Iodide
Nit
rate
(m
g/L
)
0.0
0.5
1.0
1.5
2.0
Nitrate
Results – Water Chemistry
Columbia Lake Outflow Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0
1
2
3
4
515
20
Perchlorate Iodide
Nit
rate
(m
g/L
)
0
1
2
3
4
5
Nitrate
Upstream from Columbia Lake Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate Iodide
Nit
rate
(m
g/L
)
0.0
0.5
1.0
1.5
2.0
Nitrate
Columbia Lake Inflow Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate Iodide
Nit
rate
(m
g/L
)
0.0
0.5
1.0
1.5
2.0
Nitrate
Results – Water Chemistry
Columbia Lake Outflow Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0
1
2
3
4
515
20
Perchlorate Iodide
Nit
rate
(m
g/L
)
0
1
2
3
4
5
Nitrate
Upstream from Columbia Lake Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate Iodide
Nit
rate
(m
g/L
)
0.0
0.5
1.0
1.5
2.0
Nitrate
Columbia Lake Inflow Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate Iodide
Nit
rate
(m
g/L
)
0.0
0.5
1.0
1.5
2.0
Nitrate
Results – Water ChemistryPerchlorate - Downstream• After the fireworks: 0.08 to 0.1 μg/L
• Returns to background levels (~0.05 μg/L) after 4 weeks.
Downstream from Columbia Lake Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate Iodide
Nit
rate
(m
g/L
)
0.0
0.5
1.0
1.5
2.0
Nitrate
Gazebo at Silver Lake Sampling Point
Date01-Jun-05 01-Jul-05 01-Aug-05
Pe
rch
lora
te,
Iod
ide
( g
/L)
0.0
0.5
1.0
1.5
2.0
Perchlorate Iodide
Nit
rate
(m
g/L
)
0.0
0.5
1.0
1.5
2.0
Nitrate
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
Soil Chemistry at Site A
Per
chlo
rate
( g
/kg
)
0
20
40
60
80Perchlorate BeforePerchlorate After
Iod
ide
(g
/kg
)
0
1
2
3
Iodide BeforeIodide After
Before After
Soil Chemistry at Site B
Per
chlo
rate
( g
/kg
)
0
20
40
60
80Perchlorate BeforePerchlorate After
Iod
ide
(g
/kg
)
0
1
2
3
Iodide After
Before After
Soil Chemistry at Site C
Per
chlo
rate
( g
/kg
)
0
20
40
60
80Perchlorate BeforePerchlorate After
Iod
ide
(g
/kg
)
0
1
2
3
Iodide BeforeIodide After
Before After
Soil Chemistry at Site D
Per
chlo
rate
( g
/kg
)
0
20
40
60
80Perchlorate BeforePerchlorate After
Iod
ide
(g
/kg
)
0
1
2
3
Iodide BeforeIodide After
Before After
Soil Chemistry at Site E
Per
chlo
rate
( g
/kg
)
0
20
40
60
80Perchlorate BeforePerchlorate After
Iod
ide
(g
/kg
)0
1
2
3
Iodide BeforeIodide After
Before After
Relation to Co-contaminants
Outflow - Perchlorate vs. Iodide
Perchlorate (g/L)0 5 10 15 20 25
Iod
ide
( g
/L)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Before FireworksAfter Fireworks
Soils - Perchlorate vs. Iodide
Perchlorate (g/kg)0 20 40 60 80
Iod
ide
( g
/kg
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Before FireworksAfter Fireworks
Surface Water SoilIo
did
eN
itra
te
Outflow - Perchlorate vs. Nitrate
Perchlorate (g/L)0 5 10 15 20 25
Nit
rate
(m
g/L
)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Before FireworksAfter Fireworks
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
• 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
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
ReferencesReferencesCheremisinoff, 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