Anomalous Gadolinium, Cerium, and Yttrium contents in the Adige and Isarco River waters and in the water of their tributaries (Provinces Trento and Bolzano/Bozen, NE Italy)

Rare earth patterns of surface and groundwaters near big cities often show anthropogenic Gd (Gd_ant) anomalies in addition to geogenic Ce and Y anomalies. The Gd_ant anomaly is caused by very stable organic complexes, one of which is gadopentetic acid, Gd-DTPA. Derivatives of this and similar compounds are used as contrast agents in magnetic resonance imaging (MRI) of the human blood system. The organic Gd complexes are stable enough to pass nearly unaffected through sewage treatment plants and are, thereafter, discharged into surface water systems. Water of the rapidly flowing Isarco/Eisack and Adige/Etsch rivers (Provinces of Trento and Bolzano/Bozen, NE Italy) and their tributaries show remarkable variations in anthropogenic Gd contents (Gd_ant). Low Gd_ant values are found on Monday and Tuesday, whereas high values are observed during the remaining weekdays. Reliable Gd_ant balances are calculated for the river system at the confluence of the Adige and its tributaries. At two places local decrease of Gd_ant indicates exfiltration of groundwater. It is demonstrated that Gd_ant can be used as a reliably conservative tracer to study the water budget in rapidly flowing alpine river systems. The studied different river waters show considerable negative Ce and positive Y anomalies. Negative Ce anomalies are caused by scavenging of Ce(III) by FeO(OH) precipitates and subsequent oxidation to CeO₂. Y anomalies are attributed to less sorption of Y than REE onto particulate matter. Thus, Y moves faster than REE. Both, Ce and Y anomalies, are of geogenic origin.