In river basins, soils, groundwater, riparian zones and floodplains, streams, rivers, lakes and reservoirs act as successive filters in which the hydrology, ecology and biogeochemical processing are strongly coupled and together act to retain a significant fraction of the nutrients transported. This paper compares existing river ecology concepts with current approaches to describe river biogeochemistry, and assesses the value of these concepts and approaches for understanding the impacts of interacting global change disturbances on river biogeochemistry. Through merging perspectives, concepts, and modeling techniques, we propose integrated model approaches that encompass both aquatic and terrestrial components in heterogeneous landscapes. In this model framework, existing ecological and biogeochemical concepts are extended with a balanced approach for assessing nutrient and sediment delivery, on the one hand, and nutrient in-stream retention on the other hand.

The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

Enhanced weathering of olivine has been suggested as a measure to lower the atmospheric CO2 level and it might also mitigate ocean acidification. This study aimed to characterise how olivine can weather in seawater, to elucidate the role of secondary precipitation and to ascertain the efficiency in terms of molar CO2 removal per mole of olivine dissolution. Geochemical thermodynamic equilibrium modelling was used, which considered both the variable mineralogical composition of olivine and the kinds of secondary precipitates that may be formed. The advantage is that such an approach is independent from local or regional factors as temperature, related kinetics, mineralogy, etc. The results show that the efficiency falls when secondary precipitates are formed. When Fe-bearing olivine undergoes weathering in an oxic environment, Fe(III) hydroxides will inevitably be formed, and as a result of this acidifying process, CO2 could be released to the atmosphere. This might also enhance ocean acidification when Fe-rich olivine becomes used. Ocean alkalinisation only happens when more than 1mol/kgH2O Mg-rich olivine weathers. Maintenance of supersaturation for calcite or aragonite as holds in seawater reduces the efficiency by about a factor of two compared to the efficiency without secondary precipitation. Precipitation of sepiolite as Mg silicate reduces the efficiency even more. Magnesite precipitation has a similar effect to Ca carbonate precipitation, but according to the literature magnesite precipitation is improbable at ambient conditions and relatively low supersaturation. When less than 0.05mmololivine/kg(seawater) weathers the efficiency is slightly different than at higher intensities, due to strong buffering by seawater alkalinity.

No single spatial interpolation method reigns supreme for modelling the precise spatial distribution of groundwater quality data. This study addresses this challenge by evaluating and comparing several commonly used geostatistical methods: Local Polynomial Interpolation (LPI), Ordinary Kriging (OK), Simple Kriging (SK), Universal Kriging (UK), and Empirical Bayesian Kriging (EBK). We applied these methods to a vast dataset of 3033 groundwater records encompassing a substantial area (11,100 km²) in the coastal lowlands of the western Netherlands. To our knowledge, no prior research has investigated these interpolation methods in this specific hydrogeological setting, exhibiting a range of groundwater qualities, from fresh to saline, often anoxic, with high natural concentrations of PO₄ and NH₄. The prediction performance of the interpolation methods was assessed through statistical indicators such as root means square error. The findings indicated that EBK outperforms the other geostatistical methods in forecasting groundwater quality for the five variables considered: Cl, SO₄, Fe, PO₄, and NH₄. In contrast, SK performed worst for the species except for SO₄. We recommend not using SK to interpolate groundwater quality species unless the data exhibit low spatial variation, high sample density, or evenly distributed sampling.

Many agriculture-dominated lowland water systems worldwide suffer from eutrophication caused by high nutrient loads. Insight in the hydrochemical functioning of embanked polder catchments is highly relevant for improving the water quality in such areas or for reducing export loads to downstream water bodies. This paper introduces new insights in nutrient sources and transport processes in a polder in the Netherlands situated below sea level using high-frequency monitoring technology at the outlet, where the water is pumped into a higher situated lake, combined with a low-frequency water quality monitoring programme at six locations within the drainage area. Seasonal trends and short-scale temporal dynamics in concentrations indicated that the NO₃ concentration at the pumping station originated from N loss from agricultural lands. The NO₃ loads appear as losses via tube drains after intensive rainfall events during the winter months due to preferential flow through the cracked clay soil. Transfer function-noise modelling of hourly NO₃ concentrations reveals that a large part of the dynamics in NO₃ concentrations during the winter months can be related to rainfall. The total phosphorus (TP) concentration and turbidity almost doubled during operation of the pumping station, which points to resuspension of particulate P from channel bed sediments induced by changes in water flow due to pumping. Rainfall events that caused peaks in NO₃ concentrations did not results in TP concentration peaks. The rainfall induced and NO₃ enriched quick interflow, may also be enriched in TP but retention of TP due to sedimentation of particulate P then results in the absence of rainfall induced TP concentration peaks. Increased TP concentrations associated with run-off events is only observed during a rainfall event at the end of a freeze–thaw cycle. All these observations suggest that the P retention potential of polder water systems is primarily due to the artificial pumping regime that buffers high flows. As the TP concentration is affected by operation of the pumping station, timing of sampling relative to the operating hours of the pumping station should be accounted for when calculating P export loads, determining trends in water quality, or when judging water quality status of polder water systems.