Total pore volume and pore size distribution are indicators of the degree of post-mortem modification of bone. Direct measurements of pore size distribution in archaeological bones using mercury intrusion porosimetry (HgIP) and back scattered scanning electron microscopy (BSE-SEM) reveal a common pattern in the changes seen in degraded bone as compared to modern samples. The estimates of pore size distribution from HgIP and direct measurement from the BSE-SEM images show remarkable correspondence. The coupling of these two independent approaches has allowed the diagenetic porosity changes in human archaeological bone in the >0.01 µm range to be directly imaged, and their relationship to pre-existing physiological pores to be explored. The increase in porosity in the archaeological bones is restricted to two discrete pore ranges. The smaller of these two ranges (0.007–0.1 µm) lies in the range of the collagen fibril (0.1 µm diameter) and is presumably formed by the loss of collagen, whereas the larger pore size distribution is evidence of direct microbial alteration of the bone. HgIP has great potential for the characterization of microbial and chemical alteration of bone. Copyright © 2002 John Wiley & Sons, Ltd.