a case-study on the persistence of perchlorate following a firework display columbia lake, waterloo,...

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