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.

Quantitative assessments of long-term, national-scale responses of groundwater quality to pesticide applications are essential to evaluate the effectiveness of pesticide regulations. Retardation time in the unsaturated zone (R_u) was estimated for selected herbicides (atrazine, simazine, and bentazon) and degradation products (desethylatrazine (DEA), desisopropylatrazine (DIA), desethyldesisopropylatrazine (DEIA), and BAM) using a multidecadal time series of groundwater solute chemistry (∼30 years) and herbicide sales (∼60 years). The sampling year was converted to recharge year using groundwater age. Then, R_u was estimated using a cross-correlation analysis of the sales and the frequencies of detection and exceedance of the drinking water standard (0.1 μg/L) of each selected compound. The results showed no retardation of the highly polar, thus mobile, parent compounds (i.e., bentazon), while R_u of the moderately polar compounds (i.e., simazine) was about a decade, and their degradation products showed even longer R_u. The temporal trends of the degradation products did not mirror those of the sale data, which were attributed to the various sale periods of the parent compounds, sorption of the parent compounds, and complex degradation pathways. The longer R_u in clayey/organic sediments than in sandy sediments further confirmed the role of soil-specific retardation as an important factor to consider in groundwater protection.

Determining natural background levels (NBLs) is a fundamental step in assessing the chemical status of groundwater bodies in the EU, as stipulated by the Water Framework and Groundwater Directives. The major challenges in deriving NBLs for trace metals are understanding the interaction of natural and anthropogenic processes and identifying the boundary between pristine and polluted groundwater. Thus, the purpose of this paper is to present a roadmap guiding the process of method selection for setting meaningful NBLs of trace metals in groundwater. To develop the roadmap, we compared and critically assessed how three methods for excluding polluted sampling points affect the NBLs for As, Cd, Cr, Cu, Ni, and Zn in Danish aquifers. These methods exclude sampling points based on (1) the primary use of the well (or sampling purpose), (2) the dominating anthropogenic pressure in the vicinity of the well, or (3) a combination of pollution indicators (NO₃, pesticides, organic micropollutants). Except for Ni, the NBLs derived from the three methods did not differ significantly, indicating that the data pre-selection based on the primary use of the wells is an important step in assuring the removal of anthropogenically influenced points. However, this pre-selection could limit the data representativity with respect to the different groundwater types. The roadmap (a step-by-step guideline) can be used at the national scale in countries with varying data availability.

Cost-efficient targeted nitrogen (N) regulation of agriculture with low impact on the environment is the new N regulation paradigm. It requires detailed knowledge on the geological and geochemical conditions of the subsurface that is crucial for assessing the nitrate flowpaths and reduction processes. An integral part of this is analysis of the subsurface redox structures to determine the locations of nitrate reduction. This knowledge has so far not been easy to access because of lacking technology. Here we present a new concept consisting of integration and interpretation of data from the geophysical towed transient electromagnetic method, borehole information on lithology, sediment colour descriptions, geochemistry and groundwater chemistry. The concept is demonstrated in three small first-order hydrological catchments. National GIS screening analyses show that the new concept is highly needed in large parts of Denmark where the redox structures are complicated e.g. in marine landscape types and in glacial moraine landscapes but less needed in areas dominated by homogeneous meltwater plains. Providing subsurface knowledge for locally targeted N regulation of agriculture is paramount in many developed countries with intensive agriculture to lower the environmental impact, and it could also be critical in developing countries to support sustainable economic and environmental development.