Water cycle plays a major role in global energy/mass cycling connecting the abiotic environment with the bio- and anthropo-spheres,
thus governing the distribution and diversity of life on the planet and fate of chemical elements among different reservoirs. In this
context river systems are emblematic both from the perspective of geosphere-anthroposphere interactions as well as from the
perspective of the system complexity. Surface water system responds quickly to external forcing and has profound interactions with
a key natural resource as groundwater. A key objective is to link, in a multidimensional space, two sources of information: one
concerning the geochemistry of water, sediments and suspended load and the other concerning the external influencing factors. This
would permit to describe the system state, its dynamics, variability nature, and resilience, identification of potential cause-effect
relationships between the changes of the geochemical landscapes and the main environmental drivers. A discrimination between
those capable to trigger ephemeral or permanent regime shifts, and those capable to control gradual but continuous changes is
expected. Instability and resilience conditions at different scales and the presence of positive/negative feedback mechanisms might
be intercepted as early warning signals, also in the light of climatic changes. The large river catchment of Tiber River is considered
as pilot case study considering the: 1) wide spatial extent of the basin, covering a wide range of environmental (e.g., climate,
geology, etc.) and anthropic settings (e.g., land use, urbanization density, etc.); 2) knowledge level gained by previous research,
including a recent PhD project (DST), which permitted to outline the complexity and variability of the geochemistry of waters and
sediments. To fully exploit the information content of the already available geodatabase there is the need to extend the analysis on
two fronts: 1) possibility to link various geochemical compositions to potential external forcings represented by different features of