Development of an In Situ Raman Probe for Pore Water Geochemistry

Scientists and engineers at the Monterey Bay Aquarium Research Institute have developed a ROV-deployable sampling probe utilizing laser Raman spectroscopy for study of sediment pore water geochemistry. The Raman technique has already been used with deep sea ROV platforms successfully performing in situ measurement on targets of scientific interest including gas and hydrothermal vent fluids, and complex gas hydrates. However, in situ measurement of sediment pore water geochemistry by laser Raman methods has so far been an intractable problem because sediment particles strongly fluorescence and insufficient amounts of pore water can be extracted before filters become occluded by sediment particles. Our design incorporates a series of novel elements into a slender 35-cm-long probe that can be inserted into sediment using an ROV manipulator to obtain concentration profiles. Pore water is drawn through a 10-μm stainless steel filter that forms the probe tip into a low volume sample chamber (0.1 mL) using a small hydraulic pump controlled by the ROV. The pump is also used for flushing and clearing filter surfaces. The sampling process is repeated as we proceed incrementally deeper into the sediment. Light (532 nm) from a Raman laser system mounted on the ROV is conveyed by a fiber optic cable to the probe head and focused within the center of the sample chamber through a sapphire-windowed optical cell. Control of the Raman system and spectra acquisition are performed onboard the ship via a laptop computer in the ROV control room. Advantages of this rapid mode of detection include measurement of sulfate gradients in near-seafloor sediments at a vertical scale not easily obtainable using traditional coring and extraction techniques, direct measurement of the dissolved sulfide species H2S and HS-, and measurement of dissolved methane without incurring substantial degassing during core recovery. The chemical measurements are made quantitative by calculating an intensity ratio relative to known water spectra bands. Comparison of sulfate concentration profiles obtained in situ with those for pore water extracted from recovered cores and analyzed by conventional analytical methods shows excellent correlation. A double peak observed for the H2S species has the potential for direct measurement of sulfide speciation. We observe very small amounts of fluorescence emitted by in situ pore water, but pore water fluorescence increases dramatically when sediment cores are brought to the surface and exposed to oxygen.