CaO was added to the $MgAlCrO_4$ spinel, a main component of the mag-chro refractroies, by 0, 1, 5 and 10 mol% before sintering at 135$0^{circ}C$ in air. The X-ray diffraction analysis produced an additional X-ray diffraction pattern of 8CaO.$6Al_2O_3$.$2CrO_3$ besides that of $MgAlCrO_4$. The formation of 8CaO.$6Al_2O_3$.$2CrO_3$ was interpreted as due to the presence of CaO.8CaO.$6Al_2O_3$.$2CrO_3$ was unstable and easily vaporized. It was concluded that formation of the unstable pollutant 8CaO.$6Al_2O_3$.$2CrO_3$ could be prevented in reducing atmospheres. It was found that the basic refractories containing $Al_2 O_3 -CaO-Cr_2 O_3$ system would be more stable and much less toxic in reducing at mospheres than in oxidizing stmosphere.