a b s t r a c tSpectroscopy is emerging as a technique that can expand the envelope of modern oceanographic sensors. The selectivity of spectroscopic techniques enables a single instrument to measure multiple components of the marine environment and can form the basis for versatile tools to perform in situ geochemical analysis. We have developed a deep-sea laser-induced breakdown spectrometer (ChemiCam) and successfully deployed the instrument from a remotely operated vehicle (ROV) to perform in situ multi-element analysis of both seawater and mineral deposits at depths of over 1000 m. The instrument consists of a long-nanosecond duration pulse-laser, a spectrometer and a high-speed camera. Power supply, instrument control and signal telemetry are provided through a ROV tether. The instrument has two modes of operation. In the first mode, the laser is focused directly into seawater and spectroscopic measurements of seawater composition are performed. In the second mode, a fiberoptic cable assembly is used to make spectroscopic measurements of mineral deposits. In this mode the laser is fired through a 4 m long fiber-optic cable and is focused onto the target's surface using an optical head and a linear stage that can be held by a ROV manipulator. In this paper, we describe the instrument and the methods developed to process its measurements. Exemplary measurements of both seawater and mineral deposits made during deployments of the device at an active hydrothermal vent field in the Okinawa trough are presented. Through integration with platforms such as underwater vehicles, drilling systems and subsea observatories, it is hoped that this technology can contribute to more efficient scientific surveys of the deep-sea environment.

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The reason for the significant advantage offered by long-pulse (150 ns) irradiation in underwater laser-induced breakdown spectroscopy (LIBS) is investigated from the point of view of the behavior of nascent cavitation bubbles. Shadowgraphs of nascent bubbles generated by pulsed laser irradiation of Cu targets in water were observed for two different pulse widths, 20 ns and 150 ns. It is clearly seen that the nascent bubble is formed at the leading edge of the laser pulse profile, regardless of the pulse width. Bubbles generated by a 20-ns pulse are characterized by a flat-shape filled with dense matter with intense optical emission, which is in contrast to more hemispherical low-density bubbles observed under the irradiation by a 150-ns pulse. The behavior of the nascent bubbles is consistent with the behavior of the later plasma in the bubbles, which is crucial for observation of well-defined atomic spectral lines for underwater LIBS.

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