When dealing with full spectrum images in which each pixel is characterized by a full spectrum, i.e. spectral images, standard segmentation methods, such as k-means or hierarchical clustering might be either inapplicable or inappropriate ; one aspect being the multi-GB size of such data set leading to very expensive computations. In the present contribution, we propose an approach to spectral image segmentation combining hierarchical clustering and spatial constraints. On the one hand spatial constraints allow to implement an algorithm with a reasonable computation time to obtain a segmentation and with a certain level of robustness with respect to the signal-to-noise ratio since the prior knowledge injected by the spatial constraint partially compensates for the increase in noise level. On the other hand hierarchical clustering provides a statistically sound and known framework that allows accurate reporting of the instrument noise model. In terms of applications, this segmentation problem is encountered particularly in the study of ancient materials that benefits from the wealth of information provided by the acquisition of spectral images.In the last few years, data collection has been considerably accelerated, enabling the characeterization of the sample with a high dynamic range in both the spatial dimensions and composition and leading to an average size of a single data set in the tens of GB range. Hence we also considered computational and memory complexity when developing the herein proposed algorithm. Taking on this application domain, we illustrate the proposed algorithm on a X-ray fluorescence spectral image collected on an ca. 100 Myr fossil fish, as well as on simulated data to assess the sensitivity of the results to the noise level. For such experiment, the lower sensitivity to noise simultaneously lead to an increase in the spatial definition of the collected spectral image, thanks to the faster acquisition time, and to a reduction in the potentially harmful radiation dose density to which the samples are subjected.