| Two novel spectroscopic applications, with the common theme of remote spectroscopy are described. In one application, laser-induced breakdown spectroscopy (LIBS) is investigated for deep ocean measurements of hydrothermal vent chemistry. This technique is demonstrated for the first time for solution measurements at pressures corresponding to those found at hydrothermal vent sites, at ocean depths of one to three kilometers. In the other application, Raman spectroscopy is investigated for stand-off detection of high explosive (HE) materials. We demonstrate several HE materials in silica can be measured at 50-meter range under ambient light conditions, a new record for this application.;Chapters one through three of this dissertation contain published and recently submitted articles describing LIBS for in situ multi-elemental detection in high-pressure aqueous environments such as the deep ocean. Initial work shows the potential of single-pulse LIBS (SP-LIBS) to measure dissolved elements (e.g., Na, Ca, Li, K, and Mn) at the part-per-million level in aqueous solutions at pressures exceeding 276 bar. Dual-pulse LIBS (DP-LIBS) of high-pressure aqueous solutions is also presented. We show significant DP-LIBS enhancements are achieved through excitation of a vapor bubble formed by laser-induced breakdown of the solution with a previous laser pulse, thereby increasing the sensitivity of LIBS and allowing additional elements to be measured. Preliminary findings show that increasing solution pressure has a detrimental effect on DP-LIBS emission intensities, such that little if any DP-LIBS emission was observed above approximately 100 bar. Recent results suggest a direct relationship exists between the size of the bubble and the resulting DP-LIBS emission, and that reduction in bubble size and lifetime at elevated pressure lead to the decreased DP-LIBS emission.;Chapter four contains published work examining the potential of stand-off Raman spectroscopy for remote HE detection. A small, transportable, telescope-based standoff Raman system is demonstrated for detection of HE materials, including RDX, TNT, and PETN, and simulants at distances up to 50 meters in ambient light conditions. Possible detection limits on the hundreds of parts-per-million level and detection ranges of hundreds of meters are suggested. Merits of pulsed laser excitation sources and intensified charge-coupled devices (ICCD) for detection are discussed. |
