Utilize gadolinium as environmental tracer for surface water-groundwater interaction in Karst

The rare earth element (REE) group is widely used for geochemical prospection and the hydrochemical differentiation of waters. Most of the currently applied methods use normalized REE patterns to determine enrichments or depletions of certain REE in comparison to standard materials, which are caused by specific environmental conditions. Contrast agents containing Gadolinium (Gd), which are used for magnetic resonance imaging (MRI), have been emitted into surface waters since the 1980s. Patients excrete these contrast agents shortly after ambulant medication in hospitals or at home. Sewage treatment is currently unable to hold back Gd from this anthropogenic source. Therefore, the Gd concentration in the receiving channel increases significantly and creates a Gd peak in the REE pattern. This anthropogenic peak propagates into adjacent groundwater bodies. In a karst aquifer showing a connection between a river/ponor (input) and three springs (output), such an anthropogenic Gd anomaly has been traced, the local Gd background quantified, and surface water groundwater interaction evaluated. In two sampling campaigns, water samples were taken every day at the input and output side during one week in February and three weeks in May. Sampling of springs and brooks in the vicinity of the karst aquifer proved excessive Gd from anthropogenic sources. The evaluation of concentration, mass flow and total mass of Gd show that Gd can be an environmental tracer to monitor surface water-groundwater interaction as well as the anthropogenic influence on water bodies. Further anthropogenic pollutants - diclofenac, carbamazepine, galaxolide, caffeine, and acesulfame-K - representing different classes of common organic substances were tested as co-indicators to Gd. However, out of these only acesulfame-K was detected and is related with the Gd-anomaly. Our results indicate that Gd is a more powerful indicator of surface water- groundwater interaction than most organic pollutants.