The biogeochemistry of soil organic matter (SOM), as a highly complex and dynamic soil property, is of vital importance for the health and ecological functioning of ecosystems, including managed and natural ones. Dominantly composed of carbon (C), SOM functions in global C cycling, including C sequestration and emission (e.g. soil respiration). Mediterranean agroecosystems especially, due to favourable climate conditions for mineralisation of SUM, are expected to go through enhanced SOM decomposition (i.e. C emission) under the ongoing global warming and related climatic change and variability (frequent heat waves, fires and extreme water disturbances). The relatively stable (humified) SOM components, especially in the organically-enriched topsoil layers, due to their specific physical chemistry (strongly charged interface) may have a significant role in biogeochemistry of charged (in)organic nutrients and/or contaminants such as toxic metal ions and persistent organic pollutants. The recent studies show that some natural vulnerabilities of Mediterranean regions (such as high risk of the erosion-driven processes) can increase movement of some hazardous pedospheric constituents (e.g. pesticides) to water bodies and/or into the air, thus influencing the whole ecosystem health. A majority of recent surveys confirm depletion of SUM and spatially variable distribution of metal contamination in the Mediterranean topsoils. Using the advanced geochemical prediction approaches in combination with the relevant soil databases, we characterised organo-mineral and organo-metal complexation and its effect on speciation and sorption of trace metals in karstified Mediterranean agroecosystems. Metal biogeochemistry was found to vary markedly under relatively constant pedosphere conditions, depending on organo-mineral soil components and pH, which may significantly impact metal mobility/availability in the soil-plant continuum. The knowledge of the SOM spatial distribution and dynamics and its interactions with other pedovariables is essential for sustainable management of SOM and control of contaminant mobility to avoid degradation processes in (agro)ecosystems. (C) 2018 Elsevier B.V. All rights reserved.