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Temperature Dependence of Dissolved Organic Matter Fluorescence
Garrett McKay1, Julie A Korak1, Fernando L Rosario-Ortiz1
1Department of Civil, Environmental, and Architectural Engineering , University of Colorado , Boulder , Colorado 80309 , United States.
The fluorescence of organic matter is temperature-dependent, with activation energies (Ea) indicating a consistent radiationless decay mechanism across diverse samples. This finding aids in correcting fluorescence sensors for temperature variations.
Area of Science:
- Environmental Chemistry
- Photochemistry
- Spectroscopy
Background:
- Organic matter fluorescence is a key indicator in environmental monitoring.
- Temperature significantly influences fluorescence measurements, necessitating corrections.
- Understanding the photophysics of organic matter is crucial for accurate analysis.
Purpose of the Study:
- To measure the temperature dependence of organic matter fluorescence apparent quantum yields (Φf).
- To determine apparent activation energies (Ea) for radiationless decay processes.
- To provide a physical basis for correcting fluorescence sensors for temperature effects.
Main Methods:
- Measured temperature-dependent Φf for diverse organic matter isolates and whole water samples.
- Calculated Ea using steady-state fluorescence data and the Arrhenius equation.
- Analyzed Ea variation with excitation wavelength.
Main Results:
- Aquatic-derived isolates and whole water samples showed temperature-dependent Φf with Ea values from 5.4 to 8.4 kJ mol⁻¹ at 350 nm.
- Soil humic acid isolates exhibited minimal temperature dependence.
- Observed a narrow range of Ea values across diverse samples, suggesting a common photophysical mechanism.
Conclusions:
- A consistent photophysical mechanism governs non-radiative decay in excited singlet states of organic matter.
- Temperature-dependent fluorescence analysis offers a fundamental, physical basis for sensor correction.
- This approach improves the accuracy of fluorescence-based environmental monitoring.
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