Underwater inverse LIBS (iLIBS) for marine archaeology

In recent years there have been enormous advances in nautical archaeology through developments in SONAR technologies as well as in manned and robotic submersible vehicles. The number of sunken vessel discoveries has escalated in many of the seas of the world in response to the widespread application of these and other new tools. Customarily, surviving artifacts within the debris field of a wreck are collected and then moved to laboratories, centers, or institutions for analyses and possible conservation. Frequently, the conservation phase involves chemical treatments to stabilize an artefact to standard temperature, pressure, and humidity instead of an undersea environment. Many of the artefacts encountered at an underwater site are now characterized and restored in-situ in accordance with modern trends in art conservation. Two examples of this trend are exemplified by the resting place of the wreck of the Titanic in the Atlantic and the Cancun Underwater Park in the Caribbean Sea. These two debris fields have been turned into museums for diving visitors. Several research groups have investigated the possibility of adapting the well-established analytical tool Laser Induced Breakdown Spectroscopy (LIBS) to in-situ elemental analyses of underwater cultural, historic, and archaeological artefacts where discovered, rather than as a phase of a salvage operation. As the underwater laser ablation associated with LIBS generates a “snowplough” shockwave within the aqueous matrix, the atomic emission spectrum is usually severely attenuated in escaping from the target. Consequently, probative experiments to date generally invoke a submerged air chamber or air jet to isolate water from the interaction zone as well as employ more complex double-pulse lasers. These measures impose severe logistical constraints on the examination of widely dispersed underwater artefacts. In order to overcome this constraint we report on water-immersion LIBS experiments performed with oblique laser irradiation and spectral detection at the complementary angle so as to view emission from behind the shockwave. Targets of silver, gold, and copper have been studied. It is found that this approach enables LIBS detection in water both in emission and in absorption. It appears that underwater inverse LIBS may be especially useful in underwater archaeology.