Qualitative and Quantitative Analysis of CO 2 and CH 4 Dissolved in Water and Seawater Using Laser Raman Spectroscopy

Abstract

Laboratory experiments have been performed using laser Raman spectroscopy to analyze carbon dioxide (CO₂) and methane (CH₄) dissolved in water and seawater. Dissolved CO₂ is characterized by bands at ∼1275 and 1382 Δcm⁻¹. Dissolved CH₄ is characterized by a dominant band at ∼2911 Δcm⁻¹. The laboratory instrumentation used for this work is equivalent to the sea-going Raman instrument, DORISS (Deep Ocean Raman In Situ Spectrometer). Limits of quantification and calibration curves were determined for each species. The limits of quantification are ∼10 mM for CO₂ and ∼4 mM for CH₄. A ratio technique is used to obtain quantitative information from Raman spectra: the gas bands are referenced to the O–H stretching band of water. The calibration curves relating band height ratios to gas concentration are linear and valid for a range of temperatures, pressures, and salinities. Current instrumentation is capable of measuring the highest dissolved gas concentration observed in end-member hydrothermal fluids. Further development work is needed to improve sensitivity and optimize operational configurations.

Keywords

Dissolved gases Raman Spectroscopy Methane Carbon dioxide Hydrothermal vents

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