Direct mercury (Hg) speciation was assessed for soil samples with a Hg concentration ranging from 7 up to 240 mg kg1. Hg chemical forms were identified and quantified by sequential extractions and bulk and micro-analytical techniques exploiting synchrotron generated X-rays. In particular, microspectroscopic techniques such as m-XRF, m-XRD and m-XANES were necessary to solve bulk Hg speciation, in both soil fractions <2 mm and <2 mm. The main Hg-species found in the soil samples were metacinnabar (b-HgS), cinnabar (a-HgS), corderoite (Hg3S2Cl2), and an amorphous phase containing Hg bound to chlorine and sulfur. The amount of metacinnabar and amorphous phases increased in the fraction <2 mm. No interaction among Hg-species and soil components was observed. All the observed Hg species originated from the slow weathering of an inert Hg-containing waste material (K106, U.S. EPA) dumped in the area several years ago, which is changing into a relatively more dangerous source of pollution.