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Determination of distribution and chemical speciation of arsenic and heavy metals in five acidic springs and in the receiving river near Srebrenica (Bosnia and Herzegovina) was carried out. These waters were used for centuries, and continue to be used, for health-care purposes. The composition and properties of all springs and the river water (after all inputs) resembled that of an acid mine drainage. Very low pH (<3.3), high sulphate concentration and extremely high contents of most of the measured elements (25) are found in all springs (e.g. arsenic and iron maximal concentration of 6.6 and 500 mg L(-1), respectively). Although of small discharge, spring waters caused the decrease of the receiving river pH (from 7.3 to 3.4) and the considerable increase of the concentrations of elements. The enrichment factor for the studied elements ranged from 1.2 for Sr up to 425 for As. In acidic spring waters, all elements were predominantly present in dissolved form. Elements associated to freshly-formed hydrous ferric oxide were prevailing in particulate forms only at the two most upstream sites in the river with pH>7. Geochemical speciation modelling (PHREEQC and WHAM-VI) revealed that As was mainly present as As(V), and Fe as Fe(III). Complexation of dissolved metals by organic matter was predicted to be significant only for the two river sites with neutral pH., (Copyright © 2012 Elsevier B.V. All rights reserved.)