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A natural method of resolving the problem of cyclic job shop scheduling that has linear constraints is presented. The genetic algorithm proposes a priority order for jobs on the machines.

The profound influence of climate change on the hydrological cycle raises concerns about its potential impacts on water quality, particularly in agricultural catchments. Here, we analysed 200 storm events monitored for nitrate and total phosphorus (TP) at sub-hourly intervals from 2016 to 2023 in the Kervidy-Naizin catchment (north-western France). Using Extreme Value theory, we identified storm events with extreme concentrations and compared their hydroclimatic characteristics to those of non-extreme events. We hypothesised that extreme concentration events occurred under extreme hydroclimatic conditions, which are projected to become more frequent in the future. The extreme events identified showed dilution patterns for nitrate, with concentrations decreasing by up to 41 %, and accretion patterns for TP, with concentrations increasing by up to 1400 % compared to non-extreme events. Hydroclimatic conditions during extreme concentration events were characterised by high rainfall intensities and low antecedent discharge, but no particular conditions for mean discharge. During non-extreme events, nitrate concentration-discharge relationships exhibited primarily clockwise hysteresis, whereas TP displayed an equal mix of clockwise and anticlockwise loops. In contrast, extreme events showed more anticlockwise hysteresis for nitrate and weak hysteresis for TP. We interpreted these dynamics and their hydroclimatic controls as the result of infiltration-excess overland flow diluting nitrate-rich groundwater and exporting large amounts of TP during intensive rainfall events following droughts, while groundwater fluctuations in the riparian zone and streambed remobilization control nutrient exports during non-extreme events. Given the increasing frequency and intensity of hydroclimatic extremes, such retrospective analyses can provide valuable insights into future nutrient dynamics in streams draining agricultural catchments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

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 km 2 ), 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 km 2 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 (NO 3 ) 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 NO 3 (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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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., (© 2020 The Authors. Journal of Environmental Quality © 2020 American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.)

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 km 2 ), which contained heterogeneous landscapes composed of forests and agricultural land, and one small neighboring forested catchment (0.4 km 2 ). 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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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 (NO 3 ) 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 NO 3 concentrations during storm events in a 100-km 2 agricultural catchment in Germany. Two years (Jan 2002 to Dec 2002 and Oct 2005 to Sep 2006) of high-frequency measurements of NO 3 concentrations, discharge and precipitation were used. An Event Response Reconstruction (ERR) model was developed using NO 3 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, NO 3 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 NO 3 concentrations (rdN), time to maximum change in NO 3 concentration (TdN) and time to 50% recovery of NO 3 concentration (TN rec ). The ERR consisted of building linear models of discharge and precipitation to predict these three descriptors. The ERR approach greatly improved NO 3 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 NO 3 data.

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., (Copyright © 2017 Elsevier B.V. All rights reserved.)

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., (Copyright © 2017 Elsevier B.V. All rights reserved.)

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

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., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The cyanobacteria-derived neurotoxin β-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., (Copyright © 2015 Elsevier Ltd. All rights reserved.)