Development and deployment of a deep-sea Raman probe for measurement of pore water geochemistry

We have developed, deployed, and tested a novel probe for study of the geochemistry of sediment pore waters based upon Raman spectroscopy. The Raman technique has already been used successfully for in situ measurements of targets of scientific interest including gas and hydrothermal vents and complex gas hydrates, but sediment geochemistry has so far been an intractable problem since the sediments themselves are strongly fluorescent and typically only very small sample volumes are obtainable. The 35 cm long probe extracts pore fluids through a 10 μm sintered metallic frit and draws the sample through a 2 mm diameter channel into a sapphire windowed optical cell within which the laser beam is focused and the spectrum recorded. The dead volume of the system is ∼1 ml and the instrument is ROV deployable with activation of probe insertion and sample withdrawal under direct operator control. The unique features of this mode of detection include observation of the sulfate gradient in marine pore waters as an indicator of diagenesis, direct measurement of the dissolved sulfide species H2S and HS−, and measurement of dissolved methane; all of which are of primary geochemical interest. Quantitative analysis is achieved by area ratio to known water peaks and from standard calibration curves with a precision of ±5%. We find only very small fluorescence from pore waters measured in situ, but observe rapid increases in fluorescence from cores returned to the surface and exposed to oxygen.