An evaluation of the seasonal dynamics of metal (Cd, Cr, Cu, Pb and Zn) phase distribution and speciation, along with different hydrogeochemical facies, was conducted along the entire stretch of a perennial tropical (Brahmaputra) River. Water samples were collected from twelve locations during the monsoon, post-monsoon and pre-monsoon seasons. A characteristic trend in bioavailability was observed in the sequence of Zn > Cu > Pb > Cr > Cd, reflecting non-significant seasonal changes in dissolved and particulate phase metal fractions at all twelvelocations. Partition (or distribution) coefficients (Kds) for Cu (5.30–6.50), Zn (4.47–6.44), Pb (3.69–4.97) and Cr (3.25–5.15), reflect the influences of anionic inorganic constitutents (aqua ion complexes), environmental variables, and river hydrology. MINTEQA2 calculations showed that metal forms complexes with other inorganic ions such as Cl−, SO42−, HCO3− and strong binding as organic complexes (for Cu and Pb) reduces their leaching potential to groundwater system. High log Kd values (≥5.3) and significant spatial variations at locations R3 to R8 of Pb, Cu, and Zn during pre-monsoon period may be explained by the formation of complexes with organic ligands in sewage and domestic wastes (humic and fulvic acids). Multivariate statistical analysis revealed multi-metal co-contamination, mainly of Zn, Cu, Cd and Pb and dissolved nutrients, loading in different clusters, emphasizing the importance of climatic, anthropogenic, terrigenous and lithological sources as controlling factors for seasonal metal dynamics in the river water.