A hillslope-scale aquifer-model to determine past agricultural legacy and future nitrate concentrations in rivers.

The long-term fate of agricultural nitrate depends on rapid subsurface transfer, denitrification and storage in aquifers. Quantifying these processes remains an issue due to time varying subsurface contribution, unknown aquifer storage and heterogeneous denitrification potential. Here, we develop a parsimonious modelling approach that uses long-term discharge and river nitrate concentration time-series combined with groundwater age data determined from chlorofluorocarbons in springs and boreholes. To leverage their informational content, we use a Boussinesq-type equivalent hillslope model to capture the dynamics of aquifer flows and evolving surface and subsurface contribution to rivers. Nitrate transport was modelled with a depth-resolved high-order finite-difference method and denitrification by a first-order law. We applied the method to three heavily nitrate loaded catchments of a crystalline temperate region of France (Brittany). We found that mean water transit time ranged 10-32 years and Damköhler ratio (transit time/denitrification time) ranged 0.12-0.55, leading to limited denitrification in the aquifer (10-20%). The long-term trajectory of nitrate concentration in rivers appears determined by flows stratification in the aquifer. The results suggest that autotrophic denitrification is controlled by the accessibility of reduced minerals which occurs at the base of the aquifer where flows decrease. One interpretation is that denitrification might be an interfacial process in zones that are weathered enough to transmit flows and not too weathered to have remaining accessible reduced minerals. Consequently, denitrification would not be controlled by the total aquifer volume and related mean transit time but by the proximity of the active weathered interface with the water table. This should be confirmed by complementary studies to which the developed methodology might be further deployed.

Evidence of colloids as important phosphorus carriers in natural soil and stream waters in an agricultural catchment.

Colloids (1-1,000 nm) are important phosphorus (P) carriers in agricultural soils. However, most studies are based on colloids from soil waters extracted in the laboratory, thus limiting the understanding of the natural transfer of colloidal P along the soil-to-stream continuum. Here, we conducted a field study on the colloidal P in both natural soil waters and their adjacent stream waters in an agricultural catchment (Kervidy-Naizin, western France). Soil waters (10-15 cm, Albeluvisol) of two riparian wetlands and the adjacent stream waters were sampled monthly during wet seasons of the 2015-2016 hydrological year (seven dates in total). Ultrafiltration at three pore sizes (5 kDa, 30 kDa, and 0.45 µm) was combined with inductively coupled plasma mass spectrometry (ICP-MS) to investigate variability in colloidal P concentration and its concomitant elemental composition. Results showed that colloidal P represented, on average, 45 and 30% of the total P (<0.45 µm) in the soil waters and stream waters, respectively. We found that colloidal P was preferentially associated with (a) organic carbon in the fine nanoparticle fraction (5-30 kDa) and (b) iron-oxyhydroxides and organic carbon in the coarse colloidal fraction (30 kDa-0.45 µm). The results confirmed that colloidal P is an important component of total P in both soil waters and stream waters under field conditions, suggesting that riparian wetlands are hotspot zones for the production of colloidal P at the catchment scale, which has the potential to be transported to adjacent streams.

River network alteration of C-N-P dynamics in a mesoscale agricultural catchment.

The majority of freshwater ecosystems worldwide suffer from eutrophication, particularly because of agriculture-derived nutrient sources. In the European Union, a discrepancy exists between the scale of regulatory assessment and the size of research catchments. The Water Framework Directive sets water quality objectives at the mesoscale (50-500 km2), a scale at which both hillslope and in-stream processes influence carbon (C), nitrogen (N) and phosphorus (P) dynamics. Conversely, research catchments focus on headwaters to investigate hillslope processes while minimising the influence of river processes on C-N-P dynamics. Because hillslope and river processes have common hydro-climatic drivers, the relative influence of each on C-N-P dynamics is difficult to disentangle at the mesoscale. In the present study, we used repeated synoptic sampling throughout the river network of a 300 km2 intensively farmed catchment, spatial stochastic modelling and mass balance calculations to analyse this mesoscale conundrum. The main objective was to quantify how river processes altered C-N-P hydrochemical dynamics in different flow, concentration and temperature conditions. Our results show that flow was the main control of alterations of C-N-P dynamics in the river network, while temperature and source concentration had little or no influence. The influence of river processes peaked during low flow, with up to 50% of dissolved organic carbon (DOC) production, up to 100% of nitrate (NO3) retention and up to 50% of total phosphorus (TP) retention. Despite high percentages of river processes at low flow, their influence on annual loads was low for NO3 (median of -10%) and DOC (median of +25%) but too variable to draw conclusions for TP. Because of the differing river alteration rates among carbon and nutrients, stoichiometric ratios varied greatly from headwaters to the outlet, especially during the eutrophication-sensitive low-flow season.

Improving nitrate load estimates in an agricultural catchment using Event Response Reconstruction.

Low-frequency grab sampling cannot capture fine dynamics of stream solute concentrations, which results in large uncertainties in load estimates. The recent development of high-frequency sensors has enabled monitoring solute concentrations at sub-hourly time scales. This study aimed to improve nitrate (NO3) load estimates using high-resolution records (15-min time interval) from optical sensors to capture the typical concentration response to storm events. An empirical model was developed to reconstruct NO3 concentrations during storm events in a 100-km2 agricultural catchment in Germany. Two years (Jan 2002 to Dec 2002 and Oct 2005 to Sep 2006) of high-frequency measurements of NO3 concentrations, discharge and precipitation were used. An Event Response Reconstruction (ERR) model was developed using NO3 concentration descriptor variables and predictor variables calculated from discharge and precipitation records. Fourteen events were used for calibration, and 27 events from four periods of continuous records of high-frequency measurement were used for validation. During all selected storm events, NO3 concentration decreased during flow rise and increased during the recession phase of the hydrograph. Three storm descriptor variables were used to describe these dynamics: relative change in concentration between initial and minimum NO3 concentrations (rdN), time to maximum change in NO3 concentration (TdN) and time to 50% recovery of NO3 concentration (TN rec ). The ERR consisted of building linear models of discharge and precipitation to predict these three descriptors. The ERR approach greatly improved NO3 load estimates compared to linear interpolation of grab sampling data (error decreased from 10 to 1%) or flow-weighted estimation of load (error is 7%). This study demonstrated that ERR based on a few months of high-resolution data enables accurate load estimates from low-frequency NO3 data.

Influence of hydroclimatic variations on solute concentration dynamics in nested subtropical catchments with heterogeneous landscapes.

Despite global efforts to monitor water quality in catchments worldwide, tropical and subtropical zones still lack data to study the influence of human activities and climate variations on solute dynamics. In this study, we monitored ten solutes every two weeks for six years (2010-2015) in three nested catchments (2 to30 km2), which contained heterogeneous landscapes composed of forests and agricultural land, and one small neighboring forested catchment (0.4 km2). Data analysis revealed that i) rainfall, discharge and solute concentrations displayed no clear seasonal patterns, unlike many catchments of the temperate zone; ii) solute concentrations in the agricultural area were higher than those in the forested area, but both areas displayed similar temporal patterns due to a common hydroclimatic driver; iii) all four catchments displayed a chemostatic export regime for most of the solutes, similar to catchments of the temperate zone; and iv) a positive correlation was observed between anion concentrations and ENSO (El Niño-Southern Oscillation) index. ENSO appeared to influence both hydroclimatic and anion dynamics in these subtropical catchments.

The role of mobilisation and delivery processes on contrasting dissolved nitrogen and phosphorus exports in groundwater fed catchments.

Diffuse transfer of nitrogen (N) and phosphorus (P) in agricultural catchments is controlled by the mobilisation of sources and their delivery to receiving waters. While plot scale experiments have focused on mobilisation processes, many catchment scale studies have hitherto concentrated on the controls of dominant flow pathways on nutrient delivery. To place mobilisation and delivery at a catchment scale, this study investigated their relative influence on contrasting nitrate-N and soluble P concentrations and N:P ratios in two shallow groundwater fed catchments with different land use (grassland and arable) on the Atlantic seaboard of Europe. Detailed datasets of N and P inputs, concentrations in shallow groundwater and concentrations in receiving streams were analysed over a five year period (October 2010-September 2015). Results showed that nitrate-N and soluble P concentrations in shallow groundwater give a good indication of stream concentrations, which suggests a dominant control of mobilisation processes on stream exports. Near-stream attenuation of nitrate-N (-30%), likely through denitrification and dilution, and enrichment in soluble P (+100%), through soil-groundwater interactions, were similar in both catchments. The soil, climate and land use controls on mobilisation were also investigated. Results showed that grassland tended to limit nitrate-N leaching as compared to arable land, but grassland could also contribute to increased P solubilisation. In the context of land use change in these groundwater fed systems, the risk of pollution swapping between N and P must be carefully considered, particularly for interactions of land use with soil chemistry and climate.

Release of dissolved phosphorus from riparian wetlands: Evidence for complex interactions among hydroclimate variability, topography and soil properties.

In agricultural landscapes, establishment of vegetated buffer zones in riparian wetlands (RWs) is promoted to decrease phosphorus (P) emissions because RWs can trap particulate P from upslope fields. However, long-term accumulation of P risks the release of dissolved P, since the unstable hydrological conditions in these zones may mobilize accumulated particulate P by transforming it into a mobile dissolved P species. This study evaluates how hydroclimate variability, topography and soil properties interact and influence this mobilization, using a three-year dataset of molybdate-reactive dissolved P (MRDP) and total dissolved P (TDP) concentrations in soil water from two RWs located in an agricultural catchment in western France (Kervidy-Naizin), along with stream P concentrations. Two main drivers of seasonal dissolved P release were identified: i) soil rewetting during water-table rise after dry periods and ii) reductive dissolution of soil Fe (hydr)oxides during prolonged water saturation periods. These mechanisms were shown to vary greatly in space (according to topography) and time (according to intra- and interannual hydroclimate variability). The concentration and speciation of the released dissolved P also varied spatially depending on soil chemistry and local topography. Comparison of sites revealed a similar correlation between soil P speciation (percentage of organic P ranging from 35-70%) and the concentration and speciation of the released P (MRDP from <0.10 to 0.40mgl-1; percentage of MRDP in TDP from 25-70%). These differences propagated to stream water, suggesting that the two RWs investigated were the main sources of dissolved P to streams. RWs can be critical areas due to their ability to biogeochemically transform the accumulated P in these zones into highly mobile and highly bioavailable dissolved P forms. Hydroclimate variability, local topography and soil chemistry must be considered to decrease the risk of remobilizing legacy soil P when establishing riparian buffer zones in agricultural landscapes.

Disentangling the influence of hydroclimatic patterns and agricultural management on river nitrate dynamics from sub-hourly to decadal time scales.

Despite extensive efforts to reduce nitrate transfer in agricultural areas, limited response is often observed in the nitrate concentration in rivers. To investigate the reasons for this limited response, nitrate dynamics in a 100km(2) agricultural catchment in eastern Germany was analysed from sub-hourly to decadal time-scales. Sub-hourly analysis of storm event dynamics during a typical hydrological year (2005-2006) was performed to identify periods of the year with high leaching risk and to link the latter to agricultural management practices in the catchment. Dynamic Harmonic Regression analysis of a 32-year (1982-2014) record of nitrate and discharge revealed that i) the long-term trend in nitrate concentration was closely related to that in discharge, suggesting that large-scale weather and climate patterns were masking the effect of improved nitrogen management on nitrate trends; ii) a persistent seasonal pattern with winter concentration maxima and summer minima could be observed, which was interpreted in terms of a dynamic nitrate concentration profile in the soil and subsoil; and iii) the catchment progressively changed from chemodynamic to more chemostatic behaviour over the three decades of study, which is a sign of long-term homogenisation of nitrate concentrations distribution over depth. This study shows that detailed physical understanding of nitrate dynamics across time scales can be obtained only through combined analysis of long-term records and high-resolution sensor data. Hence, a joint effort is advocated between environmental authorities, who usually perform long-term monitoring, and scientific programmes, which usually perform high-resolution monitoring.

Groundwater control of biogeochemical processes causing phosphorus release from riparian wetlands.

Because of the high sorption affinity of phosphorus (P) for the soil solid phase, mitigation options to reduce diffuse P transfer usually focus on trapping particulate P delivered via surface flow paths. Therefore, placing riparian buffers between croplands and watercourses has been promoted worldwide, sometimes in wetland areas. To investigate the risk of P-accumulating riparian wetlands (RWs) releasing dissolved P into streams, we monitored molybdate-reactive P (MRP) in the soil pore water of two RWs in an agricultural watershed. Two main mechanisms released MRP under the control of groundwater dynamics. First, soil rewetting after the dry summer period was associated with the presence of a pool of mobile P, limited in size. Its mobilization started under water saturated conditions caused by a rise in groundwater. Second, anoxic conditions at the end of winter caused reductive dissolution of Fe (hydr)oxides along with a release of MRP. Comparison of sites revealed that the first MRP release occurred only in RWs with P-enriched soils, whereas the second was observed even in RWs with low soil P status. Seasonal variations in stream MRP concentrations were similar to concentrations in RW soils. Hence, RWs can act as a key component of the P transfer continuum in agricultural landscapes by converting particulate P from croplands into MRP transferred to streams.

Geographical modeling of exposure risk to cyanobacteria for epidemiological purposes.

The cyanobacteria-derived neurotoxin ß-methylamino-L-alanine (BMAA) represents a plausible environmental trigger for amyotrophic lateral sclerosis (ALS), a debilitating and fatal neuromuscular disease. With the eutrophication of water bodies, cyanobacterial blooms and their toxins are becoming increasingly prevalent in France, especially in the Brittany region. Cyanobacteria are monitored at only a few recreational sites, preventing an estimation of exposure of the human population. By contrast, phosphorus, a limiting nutrient for cyanobacterial growth and thus considered a good proxy for cyanobacteria exposure, is monitored in many but not all surface water bodies. Our goal was to develop a geographic exposure indicator that could be used in epidemiological research. We considered the total phosphorus (TP) concentration (mg/L) of samples collected between October 2007 and September 2012 at 179 monitoring stations distributed throughout the Brittany region. Using readily available spatial data, we computed environmental descriptors at the watershed level with a Geographic Information System. Then, these descriptors were introduced into a backward stepwise linear regression model to predict the median TP concentration in unmonitored surface water bodies. TP concentrations in surface water follow an increasing gradient from West to East and inland to coast. The empirical concentration model included five predictor variables with a fair coefficient of determination (R(2) = 0.51). The specific total runoff and the watershed slope correlated negatively with the TP concentrations (p = 0.01 and p< 10(-9), respectively), whereas positive associations were found for the proportion of built-up area, the upstream presence of sewage treatment plants, and the algae volume as indicated by the Landsat red/green reflectance ratio (p < 0.01, p < 10(-6) and p < 0.01, respectively). Complementing the monitoring networks, this geographical modeling can help estimate TP concentrations at the watershed level, delivering a proxy for cyanobacteria exposure that can be used along with other risk factors in further ALS epidemiologic case-control studies.

Assessing N emissions in surface water at the national level: comparison of country-wide vs. regionalized models.

Many countries are developing models to estimate N emissions in rivers as part of national-scale water quality assessments. Generally, models are applied with national databases, while at the regional scale, more detailed databases are sometimes available. This paper discusses pros and cons of developing regionalized models versus applying countrywide models. A case study is used to support the discussion. The model used, called Nutting-N (NUTrient Transfer modelING-Nitrogen), relies on a statistical approach linking nitrogen sources and watershed land and river characteristics and aims to evaluate the risk of water bodies failing to reach quality objectives defined by national and federal policies. After calibration and evaluation at the national scale (France), the predictive quality of the model was compared with two regionalized models in a crystalline massif (Brittany, western France, 27,000 km(2)) and in a sedimentary basin (Seine, Paris basin, 78,000 km(2)), where detailed regional databases are available. The national-scale model provided robust predictions in most conditions encountered in France (efficiency=0.69). Terrestrial retention was related mainly to specific runoff, and its median value was estimated at 49% of the N surplus, whereas median river retention represented 18% of incoming N discharge. Regionalizing the model generally improved goodness-of-fit, as the root mean squared error was reduced by 6-24%. However, precision of parameter estimates degraded when too few monitoring basins were available or when variability in land and river characteristics was too low in the calibration dataset. Hence, regional-scale models should be advocated only after the trade-off between improvement of fit and degradation of parameter estimates is examined.

Predicting phosphorus losses with the PLEASE model on a local scale in Denmark and the Netherlands.

To reduce losses from agricultural soils to surface water, mitigation options have to be implemented as a local scale. For a cost-effective implementation of these measures, an instrument to identify critical areas for P leaching is indispensable. In many countries, P-index methods are used to identify areas as risk for P losses to surface water. In flat areas, where losses by leaching are dominant, these methods have their limitations because leaching is often not described in detail, PLEASE, is a simple mechanistic model designed to stimulate P Losses by leaching at the field scale using a limited amount of local field data. In this study, PLEASE, was applied to 17 lowland sites in Denmark and 14 lowland sites in the Netherlands. Results show that the simple model simulated measured fluxes and concentrations in water from pipe drains, suction cups, and groundwater quite well. The modeling efficiency ranged from 0.92 for modeling total-P fluxes to 0.36 fr modeling concentrations in groundwater. Poor results were obtained for heavy clay soils and eutrophic peat soils, where fluxes and concentration were strongly underestimated by the model. The poot performance for the heavy clay soil can be explained by the transport of P through macropores to the drain pipes and the underestimation of overland flow on this heavy-textured soil. In the eutrophic peat soils, fluxes were underestimated due to the release of P from deep soil layers.