Bas van der Grift

Model-based integration and analysis of biogeochemical and isotopic dynamics in a nitrate-polluted pyritic aquifer

Leaching of nitrate from agricultural land to groundwater and the resulting nitrate pollution are a major environmental problem worldwide. Its impact is often mitigated in aquifers hosting sufficiently reactive reductants that can promote autotrophic denitrification. In the case of pyrite acting as reductant, however, denitrification is associated with the release of sulfate and often also with the mobilization of trace metals (e.g., arsenic). In this study, reactive transport modeling was used to reconstruct, quantify and analyze the dynamics of the dominant biogeochemical processes in a nitrate-polluted pyrite-containing aquifer and its evolution over the last 50 years in response to changing agricultural practices. Model simulations were constrained by measured concentration depth profiles. Measured (3)H/(3)He profiles were used to support the calibration of flow and conservative transport processes, while the comparison of simulated and measured sulfur isotope signatures acted as additional calibration constraint for the reactive processes affecting sulfur cycling. The model illustrates that denitrification largely prevented an elevated discharge of nitrate to surface waters, while sulfate discharges were significantly increased, peaking around 15 years after the maximum nitrogen inputs.

Modeling diffusive Cd and Zn contaminant emissions from soils to surface waters

Modeling contaminant transport of diffusive contaminants is generally difficult, as most contaminants are located in the top soil where soil properties will vary strongly with depth and often a strong gradient in contaminant concentrations exists. When groundwater periodically penetrates the contaminated layers, stationary models (like most 3D models) cannot adequately describe contaminant transport. Therefore we have combined a hydrological instationary model using a 1D distributed column approach with a simple geochemical model to describe contaminant transport in the soil. Special to this model is that it includes lateral drainage from the soil column to different types of surface waters, which makes it possible to calculate surface water emissions especially for fluctuating groundwater tables. To test this model approach, we used it to quantify surface water emissions from soils in a catchment in the Kempen area which has been diffusively contaminated with Cd and Zn by zinc smelters. We ran the model for the period 1880-2000, starting with an uncontaminated soil in 1880. The model could describe both water discharge, surface water concentrations and current soil contents of Cd and Zn well. Further the model calculations showed that a stationary approach would underestimate leaching to surface waters considerably.

Chapter 10.2:Modelling Reactive Transport of Diffuse Contaminants: Identifying the Groundwater Contribution to Surface Water Quality

The European Union (EU) Water Framework Directive1 stimulates an integrated approach of the whole soil–groundwater–surface water system. Transport models are potentially very useful to improve insight into the dominant processes which control present and future water quality and to quantitatively ev...

Forms of phosphorus in suspended particulate matter in agriculture-dominated lowland catchments: Iron as phosphorus carrier

The fate and environmental effects of phosphorus (P) in natural waters depend on its chemical forms. The particulate P (PP) concentration is dominant over the dissolved P concentration in agriculture-dominated headwaters in the Netherlands. Routine water quality monitoring programmes do not include the chemical fractionation of PP. To quantify the chemical forms of PP under various conditions in six agriculture-dominated lowland catchments in the Netherlands, a sequential chemical extraction method was applied to suspended particulate matter (SPM) samples collected by centrifugation or filtration. Centrifuge samples had lower values for the sum of the PP fractions compared with the filtration samples due to lower contents from PP fractions other than the Fe-P pool. With an average value of 8.8mgg-1, internationally high P contents of the SPM were found. Ferric iron-bound P was the most important PP fraction in SPM samples (38-95%; median 74%), followed by organic P (2-38%; median 15%). Exchangeable P ranged from 0.2 to 27%, with a median of 4.4%, Ca-P ranged from 0.1 to 11% with a median of 3.9% and detrital P was present in only a small fraction (0-6%; median 1.1%). Ferric iron-bound P was the dominant PP pool throughout the entire range of watercourses (from headwater ditches to catchment outlets) and in samples taken during winter months as well as those taken during summer months. Furthermore, the PP fraction distribution did not change markedly when flow conditions were altered from low to high discharge. The dominance of the Fe-P pool denotes the presence of Fe(III) precipitates in SPM that originate from exfiltration of anoxic Fe-bearing groundwater. These Fe(III) precipitates are a major fraction of the total SPM concentration (4 to 67% as Fe(OH)3; median 18%). Although not measured directly, our results suggest that formation of authigenic Fe(III) precipitates causes a rapid transformation of dissolved P in groundwater to PP in surface water. We advise including sequential chemical extraction of SPM monitoring programmes because the composition of particles is critical for P bioavailability, which is a key driving factor for eutrophication.

Challenges of Reducing Phosphorus Based Water Eutrophication in the Agricultural Landscapes of Northwest Europe

In this paper, we outline several recent insights for the priorities and challenges for future research for reducing phosphorus (P) based water eutrophication in the agricultural landscapes of Northwest Europe. We highlight that new research efforts best be focused on headwater catchments as they are a key influence on the initial chemistry of the larger river catchments, and here many management interventions are most effectively made. We emphasize the lack of understanding on how climate change will impact on P losses from agricultural landscapes. Particularly, the capability to disentangle current and future trends in P fluxes, due to climate change itself, from climate driven changes in agricultural management practices and P inputs. Knowing that, future climatic change trajectories for Western Europe will accelerate the release of the most bioavailable soil P. We stress the ambiguities created by the large varieties of sources and storage/transfer processes involved in P emissions in landscapes and the need to develop specific data treatment methods or tracers able to circumvent them, thereby helping catchment managers to identify the ultimate P sources that most contribute to diffuse P emissions. We point out that soil and aqueous P exist not only in various chemical forms, but also in range of less considered physical forms e. g., dissolved, nanoparticulate, colloidal and other particulates, all affected differently by climate as well as other environmental factors, and require bespoke mitigation measures. We support increased high resolution monitoring of headwater catchments, to not only help verify the effectiveness of catchments mitigation strategies, but also add data to further develop new water quality models (e.g., those include Fe-P interactions) which can deal with climate and land use change effects within an uncertainty framework. We finally conclude that there is a crucial need for more integrative research efforts to deal with our incomplete understanding of the mechanisms and processes associated with the identification of critical source areas, P mobilization, delivery and biogeochemical processing, as otherwise even highintensity and high-resolution research efforts will only reveal an incomplete picture of the full global impact of the terrestrial derived P on downstream aquatic and marine ecosystems.