The behavior of the combustion pressures and luminous intensities plotted in Figure 7 became quite different after the maximum around 20 CAD ATDC. For gasoline, the luminous signal decreased until a local minimum and then increased in the late combustion phase, while the pressure signal rapidly decreased. The diffusion-controlled flames greatly influenced the evolution of luminous signal, but their contribution to the combustion pressure was negligible. The diffusion flame intensity was higher for closed-valve injection than for open-valve due to the higher fuel amount deposition. For both conditions, the maximum was detected around 70 to 80 CAD ATDC. Previous investigations for gasoline fuel [37] showed that the diffusion-controlled flames were characterized by the optical markers of carbonaceous structures. Figure 8c reports typical spectra detected in the combustion chamber in the late combustion phase. The spectra presented a strong continuous contribution that increased with the wavelength in the visible range; this was representative of blackbody-like emission of soot precursors. Different levels of visible wavelength luminous intensity in the late combustion phase were related to different soot concentrations in the combustion chamber. The results confirmed those reported in the works of Witze and Green [36] and Kayes et al. [45] that assigned to the fuel deposition burning the cause of the volatile organic carbon compounds and ultrafine particles emission at the SI PFI exhaust. Regarding the temporal behavior of luminous signal, it should be noted that the spectra detected in the late combustion in Figure 8c showed a well-resolved signal due to OH radical that featured the soot oxidation phase [46]. OH emission was comparable for both fuel injection conditions. As a consequence, the open-valve condition showed not only a different spatial distribution of diffusion-controlled flame if compared to the closed-valve condition but also a more efficient soot oxidation phase. For butanol blends, the resulting integral luminosities in Figure 7 were less intense, demonstrating a lower particulate amount produced than gasoline with stronger soot reduction. This was more evident for BU40 due to higher oxygen content in the fuel. Even for butanol blends, higher particulate concentration was detected for closed valve than for open one, as expected. At the exhaust valve opening, the soot reduction rate was not sufficient to complete the oxidation; thus, part of the particulate matter formed in the combustion chamber was emitted in the exhaust line. This result partially agrees with the opacity values measured at the undiluted exhaust and reported in Table 4. The discrepancy could be due to the sensitivity of the opacimeter to gaseous species such as heavy HC and NO2 that have high absorption cross section [47, 48] in the visible wavelength range that corresponds to the opacimeter working spectral region. It should be stressed that the absence of a catalyst device determined very high concentrations of HC and NOx, and these can contribute to opacity value. Anyway, for all the tested fuels, HC in OV condition resulted higher than in CV. This occurred because, even if open-valve injection greatly reduces the amount of intake port wetting, it also induced larger in-cylinder wall wetting due to the direct fuel impingement. Experiments [49] showed that the many droplets associated with open-valve injection survived to the crank angle of ignition. This induced an inhomogeneous charge with poorer flame-front propagation that is responsible for reduction in performance and higher HC emission than closed-valve injection. Moreover, for small n-butanol blending (BU20), HC emissions were included among those of gasoline and BU40. The reduction with respect to gasoline was due to the decrease of the hydrocarbon fraction that led to the decrease of HC formation. The increase with BU40 could be due to the higher latent heat of vaporization than BU20. As reported in the work by Gu et al. [50], increasing butanol concentration in the blend with gasoline led to a decrease in the HC oxidation during expansion and exhaust processes.