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Improving Our Understanding of Contaminated
Environments Using Nuclear Magnetic
Resonance
James Longstaffe
Assistant Professor of Environmental Chemistry
School of Environmental Sciences
Ontario Agricultural College
University of Guelph
Canada
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1) NMR as an analytical tool to understand what is present in
the environment?
2) NMR as a physical property tool to understand behavior?
Improved Understanding Environmental Risk & Behavior
The Road Towards Practical Applications
of NMR in the Environmental Sciences
Improved Remediation & Environmental Protection
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1) NMR as an analytical tool to
characterize complex
contaminated environments
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1.69% of the water on Earth is groundwater
In the US, groundwater supplies:39% of the public water supply37% of irrigation water supply54% of livestock water supply
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Source: Liu, Emma. On notice for a drinking water crisis in Canada, 2015.
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1H NMR of Contaminated Groundwater
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Non-Aqueous Phase Liquids
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• NAPLs are formed from free-flowing liquid contaminants (usually solvents).• Complex NAPL mixtures present at many legacy sites are difficult to characterize
using traditional, serparation-based methods that require significant dilution ofthe sample prior to analysis.
• At may sites, much of the composition of NAPL is uncharacterized.
Non-Aqueous Phase Liquids (NAPL)
Site A
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1H NMR spectrum of a complex
NAPL
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19F NMR of a Complex NAPL
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1H DOSY of a Complex NAPL
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2) NMR as a physical tool to
understand contaminant
attenuation in the environment
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The mechanisms of contaminant
attenuation in the environment are poorly
understood at the molecular-level
?
Simple Partitioning (foc)
Binding to soils &
sediments
influences:
•Sequestration
•Bioavailability &
Bioaccesibliity
•Apparent Toxicity
•Mobility
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Goal: Direct observation
of intermolecular interactions
in soils & sediments
Towards a Molecular-Level
Understanding of Contaminant
Attenuation in the Environment
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Using NMR to Probe Intermolecular
Interactions in Soils
Fluorine-19 nuclei
Hydrogen-1 nuclei
Magnetic Dipole
Interaction
Soil Organic Matter
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Identifying Binding Sites in Soil Organic Matter using 1H{19F} STD NMR
Protein
(Albumin)
Lignin
-111 9 7 5 3 1
Humic Acid
Protein &
Lignin
-111 9 7 5 3 1
Longstaffe, J. G. et al. Environ. Sci. Technol. 2010, 44 (14), 5476-5418.
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Time Domain NMR of Metals in Soil
-2.5
-1.875
-1.25
-0.625
0.
0. 125. 250. 375. 500.
ln (
I/Io
)
Delay (s)
Clay Soil
(Mostly Bound)
R2 = 0.9486
Clay Soil
(Partially Bound)
R2 = 0.9027
Sand
(Mostly Free)
R2 = 0.9898
Solution (Free)
R2 = 0.9864
113Cadmium NMRT2 Measurements (CPMG)
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Thanks, & Acknowledgments