The bluish appearance of veins located immediately beneath the skin has long been a topic of interest for biomedical optics researchers. Despite this interest, a thorough identification of the specific optical processes responsible for this phenomenon remains to be achieved. We employ controlled in silico experiments to address this enduring open problem. Our experiments, which are supported by measured data available in the scientific literature, are performed using first-principles models of light interaction with human skin and blood. Using this investigation approach, we quantitatively demonstrate that Rayleigh scattering caused by collagen fibrils present in the papillary dermis, a sublayer of the skin, can play a pivotal role in the bluish appearance of veins as suggested by previous works in this area. Moreover, also taking color perception aspects into account, we systematically assess the effects of variations in fibril radius and papillary dermis thickness on the coloration of veins under different illuminants. Notably, this assessment indicates that Rayleigh scattering elicited by reticulin fibrils, another type of fibril found in the papillary dermis, is unlikely to significantly contribute to the bluish appearance of veins. By strengthening the current understanding of light attenuation mechanisms affecting the appearance of skin and blood, our investigation contributes to the development of more effective technologies aimed at the noninvasive measurement of the physiological properties of these tissues.