Eutrophication of water bodies has been a problem causing severe degradation of water quality in cities. To gain mechanistic understanding of the temporal dynamics of nitrogen (N) and phosphorus (P) in a groundwater-fed lowlying urban polder, we applied high-frequency monitoring in Geuzenveld, a polder in the city of Amsterdam. The highfrequency monitoring equipment was installed at the pumping station where water leaves the polder. From March 2016 to June 2017, total phosphorus (TP), ammonium (NH4), turbidity, electrical conductivity (EC), and water temperature were measured at intervals of less than 20 min. This paper discusses the results at three timescales: Annual scale, rain event scale, and single pumping event scale. Mixing of upwelling groundwater (main source of N and P) and runoff from precipitation on pavements and roofs was the dominant hydrological process governing the temporal pattern of the EC, while N and P fluxes from the polder were also regulated by primary production and iron transformations. In our groundwater-seepage controlled catchment, NH4 appeared to be the dominant form of N with surface water concentrations in the range of 2-6 mgNL-1, which stems from production in an organic-rich subsurface. The concentrations of NH4 in the surface water were governed by the mixing process in autumn and winter and were reduced down to 0.1 mgNL-1 during the algal growing season in spring. The depletion of dissolved NH4 in spring suggests uptake by primary producers, consistent with high concentrations of chlorophyll a, O2, and suspended solids during this period. Total P and turbidity were high during winter (range 0.5-2.5 mg P L-1 and 200-1800 FNU, respectively, where FNU represents Formazin Nephelometric Unit) due to the release of P and reduced iron from anoxic sediment to the water column, where Fe2C was rapidly oxidized and precipitated as iron oxides which contributed to turbidity. In the other seasons, P is retained in the sediment by sorption to precipitated iron oxides. Nitrogen is exported from the polder to the receiving waters throughout the whole year, mostly in the form of NH4 but in the form of organic N in spring. P leaves the polder mainly during winter, primarily associated with Fe(OH)3 colloids and as dissolved P. Based on this new understanding of the dynamics of N and P in this low-lying urban catchment, we suggested management strategies that may effectively control and reduce eutrophication in urban polders and receiving downstream waters.

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Urban areas in coastal lowlands host a significant part of the world's population. In these areas, cities have often expanded to unfavorable locations that have to be drained or where excess rain water and groundwater need to be pumped away in order to maintain dry feet for its citizens. As a result, groundwater seepage influences surface water quality in many of such urban lowland catchments. This study aims at identifying the flow routes and mixing processes that control surface water quality in the groundwater-influenced urban catchment Polder Geuzenveld, which is part of the city of Amsterdam. Geuzenveld is a highly paved urban area with a subsurface rain water collection system, a groundwater drainage system, and a main surface water system that receive runoff from pavement and roofs, shallow groundwater and direct groundwater seepage, respectively. We conducted a field survey and systematic monitoring to identify the spatial and temporal variations in water quality in runoff, ditch water, drain water, and shallow and deep groundwater. We found that Geuzenveld receives a substantial inflow of deep, O ₂ -depleted groundwater, which is enriched in ammonium and phosphorus due to the subsurface mineralization of organic matter under sulfate-reducing conditions. This groundwater is mixed in the ditches during wet periods with O ₂ -rich runoff, and iron- and phosphate-rich drain water. Unlike natural catchments, the newly created, separated urban flow routes lead to mixing of water in the main surface water itself, shortcutting much of the soil and shallow subsurface. This leads to low O ₂ and high ammonia concentrations in dry periods, which might be mitigated by water level management or artificially increasing O ₂ levels by water inlet or artificially aeration of the main water canals. Further research is necessary how to optimize artificial urban systems to deliver a better ecological and chemical status of the surface water.

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The Amsterdam area, a highly manipulated delta area formed by polders and reclaimed lakes, struggles with high nutrient levels in its surface water system. The polders receive spatially and temporally variable amounts of water and nutrients via surface runoff, groundwater seepage, sewer leakage, and via water inlets from upstream polders. Diffuse anthropogenic sources, such as manure and fertiliser use and atmospheric deposition, add to the water quality problems in the polders. The major nutrient sources and pathways have not yet been clarified due to the complex hydrological system in lowland catchments with both urban and agricultural areas. In this study, the spatial variability of the groundwater seepage impact was identified by exploiting the dense groundwater and surface water monitoring networks in Amsterdam and its surrounding polders. A total of 25 variables (concentrations of total nitrogen (TN), total phosphorus (TP), NH₄, NO₃, HCO₃, SO₄, Ca, and Cl in surface water and groundwater, N and P agricultural inputs, seepage rate, elevation, land-use, and soil type) for 144 polders were analysed statistically and interpreted in relation to sources, transport mechanisms, and pathways. The results imply that groundwater is a large source of nutrients in the greater Amsterdam mixed urban-agricultural catchments. The groundwater nutrient concentrations exceeded the surface water environmental quality standards (EQSs) in 93% of the polders for TP and in 91%for TN. Groundwater outflow into the polders thus adds to nutrient levels in the surface water. High correlations (R² up to 0.88) between solutes in groundwater and surface water, together with the close similarities in their spatial patterns, confirmed the large impact of groundwater on surface water chemistry, especially in the polders that have high seepage rates. Our analysis indicates that the elevated nutrient and bicarbonate concentrations in the groundwater seepage originate from the decomposition of organic matter in subsurface sediments coupled to sulfate reduction and possibly methanogenesis. The large loads of nutrient-rich groundwater seepage into the deepest polders indirectly affect surface water quality in the surrounding area, because excess water from the deep polders is pumped out and used to supply water to the surrounding infiltrating polders in dry periods. The study shows the importance of the connection between groundwater and surface water nutrient chemistry in the greater Amsterdam area. We expect that taking account of groundwater-surface water interaction is also important in other subsiding and urbanising deltas around the world, where water is managed intensively in order to enable agricultural productivity and achieve water-sustainable cities.

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Compound-specific stable isotope analysis (CSIA) has, in combination with model-assisted interpretation, proven to be a valuable approach to quantify the extent of organic contaminant degradation in groundwater systems. CSIA data may also provide insights into the origin and transformation of diffuse pollutants, such as pesticides and nitrate, at the catchment scale. While CSIA methods for pesticides have increasingly become available, they have not yet been deployed to interpret isotope data of pesticides in surface water. We applied a coupled subsurface-surface reactive transport model (HydroGeoSphere) at the hillslope scale to investigate the usefulness of CSIA in the assessment of pesticide degradation. We simulated the transport and transformation of a pesticide in a hypothetical but realistic two-dimensional hillslope transect. The steady-state model results illustrate a strong increase of isotope ratios at the hillslope outlet, which resulted from degradation and long travel times through the hillslope during average hydrological conditions. In contrast, following an extreme rainfall event that induced overland flow, the simulated isotope ratios dropped to the values of soil water in the pesticide application area. These results suggest that CSIA can help to identify rainfall-runoff events that entail significant pesticide transport to the stream via surface runoff. Simulations with daily rainfall and evapotranspiration data and one pesticide application per year resulted in small seasonal variations of concentrations and isotope ratios at the hillslope outlet, which fell within the uncertainty range of current CSIA methods. This implies a good reliability of in-stream isotope data in the absence of transport via surface runoff or other fast transport routes, since the time of measurement appears to be of minor importance for the assessment of pesticide degradation. The analysis of simulated isotope ratios also allowed quantification of the contribution of two different reaction pathways (aerobic and anaerobic) to overall degradation, which gave further insight into the transport routes in the modelled system. The simulations supported the use of the commonly applied Rayleigh equation for the interpretation of CSIA data, since this led to an underestimation of the real extent of degradation of less than 12% at the hillslope outlet. Overall, this study emphasizes the applicability and usefulness of CSIA in the assessment of diffuse river pollution, and represents a first step towards a theoretical framework for the interpretation of CSIA data in agricultural catchments.@en