The infrared spectroscopic properties of selected defects involving one proton and one nearby M3+ (M=Al, Cr, Fe) substitution in orthoenstatite are investigated by first-principles calculations. Based on the theoretical results, the absorption bands experimentally observed on synthetic samples with high crystalline quality and low doping levels can be assigned to specific defect configurations. Most of them correspond to Mg vacancies at M2 sites locally compensated by one proton and one M3+ cation at a nearby M1 site. This confirms that the M3+ + H+ = 2 Mg2+ exchange mechanism is the dominant hydrogen incorporation mechanism at the lowest concentration levels in doped enstatite. At higher concentration levels, more complex incorporation mechanisms could become dominant in Al-bearing samples.