The general perception has long been that lake eutrophication is driven by anthropogenic sources of phosphorus (P) and that P is immobile in the subsurface and in aquifers. Combined investigation of the current water and P budgets of a 70 ha lake (Nørresø, Fyn, Denmark) in a clayey till-dominated landscape and of the lake’s Holocene trophic history demonstrates a potential significance of geogenic (natural) groundwater-borne P. Nørresø receives water from nine streams, a groundwater-fed spring located on a small island, and precipitation. The lake loses water by evaporation and via a single outlet. Monthly measurements of stream, spring, and outlet discharge, and of tracers in the form of temperature, δ18O and δ2H of water, and water chemistry were conducted. The tracers indicated that the lake receives groundwater from an underlying regional confined glaciofluvial sand aquifer via the spring and one of the streams. In addition, the lake receives a direct groundwater input (estimated as the water balance residual) via the lake bed, as supported by the artesian conditions of underlying strata observed in piezometers installed along the lake shore and in wells tapping the regional confined aquifer. The groundwater in the regional confined aquifer was anoxic, ferrous, and contained 4–5 µmol/L dissolved inorganic orthophosphate (DIP). Altogether, the data indicated that groundwater contributes from 64% of the water-borne external DIP loading to the lake, and up to 90% if the DIP concentration of the spring, as representative for the average DIP of the regional confined aquifer, is assigned to the estimated groundwater input. In support, paleolimnological data retrieved from sediment cores indicated that Nørresø was never P-poor, even before the introduction of agriculture at 6000 years before present. Accordingly, groundwater-borne geogenic phosphorus can have an important influence on the trophic state of recipient surface water ecosystems, and groundwater-borne P can be a potentially important component of the terrestrial P cycle.

This study explores the under-investigated issue of groundwater-borne geogenic phosphorus (P) as the potential driving factor behind accumulation of P in lake sediment. The annual internally released P load from the sediment of the shallow, hypereutrophic and groundwater-fed lake, Nørresø, Denmark, was quantified based on total P (TP) depth profiles. By comparing this load with previously determined external P loadings entering the lake throughout the year 2016–2017, it was evident that internal P release was the immediate controller of the trophic state of the lake. Nevertheless, by extrapolating back through the Holocene, assuming a groundwater P load corresponding to the one found at present time, the total groundwater P input to the lake was found to be in the same order of magnitude as the total deposit P in the lake sediment. This suggests that groundwater-transported P was the original source of the now internally cycled P. For many lakes, internal P cycling is the immediate controller of their trophic state. Yet, this does not take away the importance of the external and possibly geogenic origin of the P accumulating in lake sediments, and subsequently being released to the water column.

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The ability to identify the origin of phosphorus is essential to effectively mitigate 14 eutrophication of freshwater ecosystems. The oxygen isotope composition of orthophosphate (δ 18 Op) 15has been suggested to have a significant prospective as a tracer for P entering freshwater ecosystems. 16The δ 18 Op tracing method is, however, still in its preliminary stages and has proven challenging to 17 implement for new practitioners. In order to achieve progress in developing the application of δ 18 Op 18 signatures as a tracing tool, there is a need to eliminate the methodological challenges involved in 19 accurately determining δ 18 Op. This technical note describes the various steps needed to concentrate 20 and isolate orthophosphate in freshwater samples into an adequately pure analyte (Ag3PO4), without 21isotopic alteration during processing. The protocol compiles the disperse experiences from previous 22 studies, combined with our own experience. 23 24 25