Rhenium distribution and behaviour in the salinity gradient of a highly stratified estuary and pristine riverine waters

Abstract

The abundance and distribution of dissolved Re (DRe) has been determined in the freshwater part of the Krka River (Croatia), draining the karstic carbonate landscape, as well as in the salinity gradient of its highly stratified estuary. Due to low DRe concentration, the batch procedure consisting of pre-concentration step using an anion exchange resin (Dovex) and analysis of DRe in 8 M HNO 3 eluate using a high resolution inductively coupled plasma mass spectrometry (HR ICP-MS) was adopted. Due to the potential inconsistent recoveries, ranging from 60% to 87%, the quantification was performed by using the isotope dilution (ID) technique. The DRe concentration in the Krka River basically increased in the downstream direction, with the 6.2 pM at the spring site, reaching 11.9 pM before the estuarine region. The weathering of the surrounding carbonate lithology is assumed as the source of natural Re. The two specific anomalies were registered: a strong increase in DRe concentration due to the anthropogenic input near the town of Knin (27.5 pM) and a decrease at downstream site caused by the subterranean input of freshwater of the Zrmanja River leading to relatively low DRe concentration (8.5 pM). In the estuarine segment, a near-conservative behavior of DRe was found in the salinity gradient of the upper surface layer, with the DRe concentration ranging from 18 to 38 pM. An anthropogenic supply was suggested within the estuarine segment close to the urban area causing a small positive deviation from the conservative line. In the bottom seawater layer, a minor decrease of DRe concentration in the most upstream estuarine regions was evidenced, implying a potential weak scavenging of Re.