Anaerobic Respiration in the Unsaturated Zone of Agricultural Soil Mobilizes Phosphorus and Manganese.

Anaerobic conditions mobilize phosphorus (P) in soils and sediments. The role of anaerobic microsites in well-drained soil on P migration is unknown. This study aimed to identify mechanisms that control field-scale vertical P mobility as affected by organic fertilizers that may trigger variable redox conditions. Soils were sampled at different depths in a well-drained Luvisol after 19 years of application of organic fertilizers. The concentrations of P and manganese (Mn) in 0.45-µm-filtered extracts (10-3 M CaCl2) of field-moist soil samples were strongly correlated (r = + 0.95), and both peaked in and below the compacted plough pan, suggesting that reductive processes mobilize P. Waterlogged soil incubations confirmed that anaerobic respiration comobilizes Mn and P and that this leads to the release of colloidal P and iron (Fe). The long-term applications of farmyard manure and immature compost enhanced the concentrations of Mn, Fe, and aluminum (Al) in the soil solution of subsurface samples, whereas less such effect was found under the application of more stable organic fertilizers. Farmyard manure application significantly enhanced soil P stocks below the plough layer despite a small P input. Overall, multiple lines of evidence confirm that anaerobic respiration, sparked by labile organic matter, mobilizes P in this seemingly well-drained soil.

Investigating regionalization techniques for large-scale hydrological modelling.

This work investigates regionalization techniques for large-scale model applications in the frame of a pan-European assessment of water resources covering approx. 740,000 km2 in Western Europe. Using the SWAT platform, four variants of the similarity based regionalization approach were compared. The first two involved unsupervised clustering to define hydrological regions before performing hydrological model calibration, whereas the last two involved supervised clustering after performing calibration. Similarity is defined using Partial Least Squares Regression (PLSR) analysis that identifies watershed physiographic characteristics that are most relevant for the selected hydrological response indices. The PLSR results indicate that typically available watershed characteristics such as geomorphology, land-use, climate, and soil properties describe reasonably well the average hydrological conditions but poorly the extreme events. Regionalization variants considering unsupervised clustering and supervised clustering performed similarly well when using all available information. However, results indicate that supervised clustering uses data more efficiently and may be more suitable when data are scarce. It is demonstrated that parsimonious use of available data can be achieved using both regionalization techniques. Finally, model performance consistently becomes acceptable by calibrating watersheds covering only 10% of the model domain, thus, making the calibration task affordable in terms of time and computational resources required.

Internal Loading and Redox Cycling of Sediment Iron Explain Reactive Phosphorus Concentrations in Lowland Rivers.

The phosphate quality standards in the lowland rivers of Flanders (northern Belgium) are exceeded in over 80% of the sampling sites. The factors affecting the molybdate reactive P (MRP) in these waters were analyzed using the data of the past decade (>200 000 observations). The average MRP concentration in summer exceeds that winter by factor 3. This seasonal trend is opposite to that of the dissolved oxygen (DO) and nitrate concentrations. The negative correlations between MRP and DO is marked (r = -0.89). The MRP concentrations are geographically unrelated to erosion sensitive areas, to point-source P-emissions or to riverbed sediment P concentration. Instead, MRP concentrations significantly increase with increasing sediment P/Fe concentration ratio (p < 0.01). Laboratory static sediment-water incubations with different DO and temperature treatments confirmed suspected mechanisms: at low DO in water (<4 mg L-1), reductive dissolution of ferric Fe oxides was associated with mobilization of P to the water column from sediments with a molar P/Fe ratio >0.4. In contrast, no such release was found from sediments with lower P/Fe irrespective of temperature and DO treatments. This study suggests that internal loading of the legacy P in the sediments explains the MRP concentrations which are most pronounced at low DO concentrations and in regions where the P/Fe ratio in sediment is large.

Large-scale hydrological simulations using the soil water assessment tool, protocol development, and application in the danube basin.

The Water Framework Directive of the European Union requires member states to achieve good ecological status of all water bodies. A harmonized pan-European assessment of water resources availability and quality, as affected by various management options, is necessary for a successful implementation of European environmental legislation. In this context, we developed a methodology to predict surface water flow at the pan-European scale using available datasets. Among the hydrological models available, the Soil Water Assessment Tool was selected because its characteristics make it suitable for large-scale applications with limited data requirements. This paper presents the results for the Danube pilot basin. The Danube Basin is one of the largest European watersheds, covering approximately 803,000 km and portions of 14 countries. The modeling data used included land use and management information, a detailed soil parameters map, and high-resolution climate data. The Danube Basin was divided into 4663 subwatersheds of an average size of 179 km. A modeling protocol is proposed to cope with the problems of hydrological regionalization from gauged to ungauged watersheds and overparameterization and identifiability, which are usually present during calibration. The protocol involves a cluster analysis for the determination of hydrological regions and multiobjective calibration using a combination of manual and automated calibration. The proposed protocol was successfully implemented, with the modeled discharges capturing well the overall hydrological behavior of the basin.

Impact of dry-wet and freeze-thaw events on pesticide mineralizing populations and their activity in wetland ecosystems: A microcosm study.

Riparian wetlands are proposed to mitigate diffuse pollution of surface water by pesticides in agricultural landscapes. Wetland ecosystems though are highly dynamic environments and seasonal disturbances such as freezing and drying can affect microbial population sizes in the sediment and their functionality including pesticide biodegradation, which has hardly been studied. This study examined the effect of artificially induced dry-wet or freeze-thaw events on the mineralization of the pesticides isoproturon (IPU) and 2-methoxy-4-chlorophenoxy acetic acid (MCPA) in wetland microcosms, either without or with prior enrichment of IPU/MCPA degrading populations. Without prior enrichment, mineralization of IPU and MCPA was significantly reduced after exposure to especially freeze-thaw events, as evidenced by lower mineralization rates and longer lag times compared to non-exposed microcosms. However, herbicide mineralization kinetics correlated poorly with cell numbers of herbicide mineralizers as estimated by a most probable number (MPN) approach and the number of IPU and MCPA mineralizers was unexpectedly higher in freeze-thaw and dry-wet cycle exposed setups compared to the control setups. This suggested that the observed effects of season-bound disturbances were due to other mechanisms than decay of pesticide mineralizers. In addition, in systems in which the growth of pesticide mineralizing bacteria was stimulated by amendment of IPU and MCPA, exposure to a freeze-thaw or dry-wet event only marginally affected the herbicide mineralization kinetics. Our results show that season bound environmental disturbances can affect pesticide mineralization kinetics in wetlands but that this effect can depend on the history of pesticide applications.

Phosphorus losses from agricultural land to natural waters are reduced by immobilization in iron-rich sediments of drainage ditches.

Redox reactions involving iron (Fe) strongly affect the mobility of phosphorus (P) and its migration from agricultural land to freshwater. We studied the transfer of P from groundwater to open drainage ditches in an area where, due to Fe(II) rich groundwater, the sediments of these ditches contain accumulated Fe oxyhydroxides. The average P concentrations in the groundwater feeding two out of three studied drainage ditches exceeded environmental limits for freshwaters by factors 11 and 16, but after passing through the Fe-rich sediments, the P concentrations in the ditch water were below these limits. In order to identify the processes which govern Fe and P mobility in these systems, we used diffusive equilibration in thin films (DET) to measure the vertical concentration profiles of P and Fe in the sediment pore water and in the ditchwater. The Fe concentrations in the sediment pore water ranged between 10 and 200 mg L(-1) and exceeded those in the inflowing groundwater by approximately one order of magnitude, due to reductive dissolution of Fe oxyhydroxides in the sediment. The dissolved P concentrations only marginally increased between groundwater and sediment pore water. In the poorly mixed ditchwater, the dissolved Fe concentrations decreased towards the water surface due to oxidative precipitation of fresh Fe oxyhydroxides, and the P concentrations decreased more sharply than those of Fe. These observations support the view that the dynamics of Fe and P are governed by reduction reactions in the sediment and by oxidation reactions in the ditchwater. In the sediment, reductive dissolution of P-containing Fe oxyhydroxides causes more efficient solubilization of Fe than of P, likely because P is buffered by adsorption on residual Fe oxyhydroxides. Conversely, in the ditchwater, oxidative precipitation causes more efficient immobilization of P than of Fe, due to ferric phosphate formation. The combination of these processes yields a natural and highly efficient sink for P. It is concluded that, in Fe-rich systems, the fate of P at the sediment-water interface is determined by reduction and oxidation of Fe.

Dissolved phosphorus transport from soil to surface water in catchments with different land use.

Diffuse phosphorus (P) export from agricultural land to surface waters is a significant environmental problem. It is critical to determine the natural background P losses from diffuse sources, but their identification and quantification is difficult. In this study, three headwater catchments with differing land use (arable, pasture and forest) were monitored for 3 years to quantify exports of dissolved (<0.45 µm) reactive P and total dissolved P. Mean total P exports from the arable catchment ranged between 0.08 and 0.28 kg ha(-1) year(-1). Compared with the reference condition (forest), arable land and pasture exported up to 11-fold more dissolved P. The contribution of dissolved (<0.45 µm) unreactive P was low to negligible in every catchment. Agricultural practices can exert large pressures on surface waters that are controlled by hydrological factors. Adapting policy to cope with these factors is needed for lowering these pressures in the future.

Inverse modeling of pesticide degradation and pesticide-degrading population size dynamics in a bioremediation system: parameterizing the Monod model.

Pesticide degradation models are compared which simulate the response of biofilters for treatment of pesticide-contaminated waste water to time-irregular pesticide supply in which the pesticide is used for growth and mineralized. Biofilter microcosms containing a mixture of straw, peat and soil and harboring micropopulations which uses the herbicide linuron for growth, were irrigated with linuron for 28 weeks with a stop in its supply between week 12 and 17. Matrix samples were regularly taken to assay linuron mineralization. A first-order approximation of the Monod model was used to simulate the observed mineralization data, while an inverse modeling framework combining a sensitivity analysis (Morris Sensitivity Analysis) with an inverse modeling approach (Shuffled Complex Evolution Metropolis) adopted to parameterize the model. Lag times in linuron mineralization decreased during the initial weeks of linuron irrigation but increased after supply of linuron ceased. The model well-simulated the lag time dynamics which were related to the dynamics of the predicted linuron-degrading population size in the microcosms. It was predicted that the population size decreased at a rate of 0.031 d(-1) after pesticide supply ceased to reach its initial population size after 25 weeks. We conclude that modeling pesticide degradation in biofilters should incorporate biomass dynamics in case the pesticide is used as C-source. First-order approaches without incorporating biomass dynamics could lead to underestimation of the risk of pesticide leaching.