Accurate detection and quantification of hydrogen isotopes in solid materials are vital for diverse applications, including fusion energy, hydrogen storage, and tritium production. Laser-induced breakdown spectroscopy (LIBS) is a well-established, rapid, standoff method for this purpose, but it faces challenges related to the analytical merits required for isotopic analyses. In this study, we enhance the analytical and detection capabilities of traditional single-pulse LIBS by implementing an orthogonal double pulsing approach, focusing on the analysis of a range of 2H concentrations in Zircaloy-4 substrates (acting as a proxy for 3H). The double-pulse experiments employed an orthogonal re-heating configuration with two nanosecond Nd:YAG lasers. We systematically evaluated critical parameters affecting the signal intensity in double-pulse LIBS, including interpulse delay, ambient gas pressure, and heating laser energy. Our results demonstrate that employing an orthogonal double-pulse scheme significantly enhances 2Hα emission while minimizing line broadening and self-absorption, ultimately improving the technique's analytical capabilities.