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Oceanic gas hydrates have been measured near the seafloor for the first time using a seagoing Raman spectrometer at Hydrate Ridge, Oregon, where extensive layers of hydrates have been found to occur near the seafloor. All of the hydrates analyzed were liberated from the upper meter of the sediment column near active gas venting sites in water depths of 770-780 m.Hydrate properties, such as structure and composition, were measured with significantly less disturbance to the sample than would be realized with core recovery. The natural hydrates measured were sI, with methane as the predominant guest component, and minor/trace amounts of hydrogen sulfide present in three of the twelve samples measured. Methane large-to-small cage occupancy ratios of the hydrates varied from 1.01 to 1.30, in good agreement with measurements of laboratory synthesized and recovered natural hydrates Although the samples visually appeared to be solid, varying quantities of free methane gas were detected, indicating the presence of occluded gas a hydrate bubble fabric and/or partial hydrate dissociation in the under-saturated seawater.

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[1] The Deep Ocean Raman In Situ Spectrometer (DORISS) instrument was deployed at the Sea Cliff Hydrothermal Field and Hydrate Ridge in July 2004. The first in situ Raman spectra of hydrothermal minerals, fluids, and bacterial mats were obtained. These spectra were analyzed and compared to laboratory Raman measurements of standards and samples collected from the site. Spectra of vent fluid ($294°C at the orifice) at $2700 m depth were collected with noncontact and immersion sampling optics. Compared to spectra of ambient ($2°C) seawater, the vent fluid spectra show changes in the intensity and positions of the water O-H stretch bands due to the elevated temperature. The sulfate band observed in seawater spectra is reduced in vent fluid spectra as sulfate is removed from vent fluid in the subseafloor. Additional components of hydrothermal fluid are present in concentrations too low to be detected with the current Raman system. A precision underwater positioner (PUP) was used to focus the laser spot on opaque samples such as minerals and bacterial mats. Spectra were obtained of anhydrite from actively venting chimneys, and of barite deposits in hydrothermal crusts. Laboratory analysis of rock samples collected in the vent field also detected the presence of gypsum. Spectra of bacterial mats revealed the presence of elemental sulfur (S 8 ) and the carotenoid beta-carotene. Challenges encountered include strong fluorescence from minerals and organics and insufficient sensitivity of the instrument. The next generation DORISS instrument addresses some of these challenges and holds great potential for use in deep-sea vent environments.

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a b s t r a c tTo enable detailed investigations of early stage hydrothermal plume formation and abiotic and biotic plume processes we developed a new oceanographic tool. The Suspended Particulate Rosette sampling system has been designed to collect geochemical and microbial samples from the rising portion of deep-sea hydrothermal plumes. It can be deployed on a remotely operated vehicle for sampling rising plumes, on a wire-deployed water rosette for spatially discrete sampling of non-buoyant hydrothermal plumes, or on a fixed mooring in a hydrothermal vent field for time series sampling. It has performed successfully during both its first mooring deployment at the East Pacific Rise and its first remotely-operated vehicle deployments along the Mid-Atlantic Ridge. It is currently capable of rapidly filtering 24 discrete large-watervolume samples (30-100 L per sample) for suspended particles during a single deployment (e.g. 490 L per sample at 4-7 L per minute through 1 mm pore diameter polycarbonate filters). The Suspended Particulate Rosette sampler has been designed with a long-term goal of seafloor observatory deployments, where it can be used to collect samples in response to tectonic or other events. It is compatible with in situ optical sensors, such as laser Raman or visible reflectance spectroscopy systems, enabling in situ particle analysis immediately after sample collection and before the particles alter or degrade.

Abstract. Requirements for understanding the relationships between ocean color and suspended and dissolved materials within the water column, and a rapidly emerging photonics and materials technology base for performing optical based analytical techniques have generated a diverse offering of commercial sensors and research prototypes that perform optical measurements in water. Through inversion, these tools are now being used to determine a diverse set of related biogeochemical and physical parameters. Techniques engaged include measurement of the solar radiance distribution, absorption, scattering, stimulated fluorescence, flow cytometry, and various spectroscopy methods. Selective membranes and other techniques for material isolation further enhance specificity, leading to sensors for measurement of dissolved oxygen, methane, carbon dioxide, common nutrients and a variety of other parameters. Scientists are using these measurements to infer information related to an increasing set of parameters and wide range of applications over relevant scales in space and time.