Large-stream nitrate retention patterns shift during droughts: Seasonal to sub-daily insights from high-frequency data-model fusion.

High-frequency nitrate-N (NO3--N) data are increasingly available, while accurate assessments of in-stream NO3--N retention in large streams and rivers require a better capture of complex river hydrodynamic conditions. This study demonstrates a fusion framework between high-frequency water quality data and hydrological transport models, that (1) captures river hydraulics and their impacts on solute signal propagation through river hydrodynamic modeling, and (2) infers in-stream retention as the differences between conservatively traced and reactively observed NO3--N signals. Using this framework, continuous 15-min estimates of NO3--N retention were derived in a 6th-order reach of the lower Bode River (27.4 km, central Germany), using long-term sensor monitoring data during a period of normal flow from 2015 to 2017 and a period of drought from 2018 to 2020. The unique NO3--N retention estimates, together with metabolic characteristics, revealed insightful seasonal patterns (from high net autotrophic removal in late-spring to lower rates, to net heterotrophic release during autumn) and drought-induced variations of those patterns (reduced levels of net removal and autotrophic nitrate removal largely buffered by heterotrophic release processes, including organic matter mineralization). Four clusters of diel removal patterns were identified, potentially representing changes in dominant NO3--N retention processes according to seasonal and hydrological conditions. For example, dominance of autotrophic NO3--N retention extended more widely across seasons during the drought years. Such cross-scale patterns and changes under droughts are likely co-determined by catchment and river environments (e.g., river primary production, dissolved organic carbon availability and its quality), which resulted in more complex responses to the sequential droughts. Inferences derived from this novel data-model fusion provide new insights into NO3- dynamics and ecosystem function of large streams, as well as their responses to climate variability. Moreover, this framework can be flexibly transferred across sites and scales, thereby complementing high-frequency monitoring to identify in-stream retention processes and to inform river management.

Stream restoration can reduce nitrate levels in agricultural landscapes.

The EU Water Framework Directive (WFD) has emphasized that altered stream/river morphology and diffuse pollution are the two major pressures faced by European water bodies at catchment scales. Increasing efforts have been directed toward restoration to meet WFD standards for ecological health, but this work has achieved limited success. One challenge is that little is known about how morphological changes (i.e., re-meandering) may affect nitrate retention within whole stream networks. We investigated this issue in the well-monitored Bode catchment (3200 km2) in central Germany. First, we implemented a fully distributed process-based mHM-Nitrate model, exploring its performance over the period from 2015 to 2018. Second, we simulated the effects of restoring more natural stream morphology (i.e., increasing sinuosity) on nitrate retention. The mHM-Nitrate model performed well in replicating daily discharge and nitrate concentrations (median Kling-Gupta values of 0.78 and 0.74, respectively). Within the stream network, mean and standard deviation (SD) of gross nitrate retention efficiency was 5.1 ± 0.61 % and 74.7 ± 23.2 % in the winter and summer, respectively; this measure took into account both denitrification and assimilatory uptake. In the summer, the denitrification rate was about twice as high in a lowland sub-catchment dominated by agricultural lands as in a mountainous sub-catchment dominated by forested areas (median ± SD of 204 ± 22.6 and 102 ± 22.1 mg N m-2 d-1, respectively). Similarly, in the same season, the assimilatory uptake rate was approximately five times higher in streams surrounded by lowland agricultural areas than in streams in higher-elevation, forested areas (median ± SD of 200 ± 27.1 and 39.1 ± 8.7 mg N m-2 d-1, respectively). This suggests that restoration strategies targeted at lowland agricultural areas may have a greater potential for increasing nitrate retention. In our simulation, restoring stream sinuosity was found to increase net nitrate retention efficiency by up to 25.4 ± 5.3 %; greater effects were seen in small streams. Taken together, our results indicate that restoration efforts should consider augmenting stream sinuosity to increase nitrate retention and decrease nitrate concentrations at the catchment scale.

The role of endosonography in cardiology: case series and literature review.

Aims: Endosonography (EUS) is the diagnostic tool with the highest resolution for the local staging of gastrointestinal tumours and, due to the detailed visualization of the wall layers, is recommended in current guidelines for cancer management. In addition, an endoscope has an ultrasound tip design and balloon insufflation control design, and a 120° bending mechanism to deflect the endoscope tip. These advantages could be beneficial and valuable while investigating the cardiovascular structures during routine gastrointestinal procedures using this diagnostic tool. Methods and results: We present six cases of incidentally diagnosed cardiac pathologies (pulmonary thromboembolism of the main pulmonary artery, patent foramen oval with right to left shunt under Valsalva, left atrial appendage thrombus, aortic dissection, moderate aortic valve stenosis, mitral and aortic valve endocarditis) during routine gastrointestinal endosonographic procedures. These diagnoses influenced changes in management strategies in four cases. Conclusion: The introduction of EUS in cardiovascular medicine allows for a real-time high-resolution assessment of cardiovascular structures and allows early detection of silent cardiac pathologies during routine gastrointestinal procedures. It is the diagnostic tool with the highest resolution for accurate definition of variable gastrointestinal anatomy. Thus, help for accurate definitions of cardiovascular anatomy and pathology, which could influence optimal management strategies with improved safety, efficacy, and economic outcomes.

Reservoir water quality deterioration due to deforestation emphasizes the indirect effects of global change.

Deforestation is currently a widespread phenomenon and a growing environmental concern in the era of rapid climate change. In temperate regions, it is challenging to quantify the impacts of deforestation on the catchment dynamics and downstream aquatic ecosystems such as reservoirs and disentangle these from direct climate change impacts, let alone project future changes to inform management. Here, we tackled this issue by investigating a unique catchment-reservoir system with two reservoirs in distinct trophic states (meso­ and eutrophic), both of which drain into the largest drinking water reservoir in Germany. Due to the prolonged droughts in 2015-2018, the catchment of the mesotrophic reservoir lost an unprecedented area of forest (exponential increase since 2015 and ca. 17.1% loss in 2020 alone). We coupled catchment nutrient exports (HYPE) and reservoir ecosystem dynamics (GOTM-WET) models using a process-based modeling approach. The coupled model was validated with datasets spanning periods of rapid deforestation, which makes our future projections highly robust. Results show that in a short-term time scale (by 2035), increasing nutrient flux from the catchment due to vast deforestation (80% loss) can turn the mesotrophic reservoir into a eutrophic state as its counterpart. Our results emphasize the more prominent impacts of deforestation than the direct impact of climate warming in impairment of water quality and ecological services to downstream aquatic ecosystems. Therefore, we propose to evaluate the impact of climate change on temperate reservoirs by incorporating a time scale-dependent context, highlighting the indirect impact of deforestation in the short-term scale. In the long-term scale (e.g. to 2100), a guiding hypothesis for future research may be that indirect effects (e.g., as mediated by catchment dynamics) are as important as the direct effects of climate warming on aquatic ecosystems.

Impact of medication on blood transcriptome reveals off-target regulations of beta-blockers.

BACKGROUND: For many drugs, mechanisms of action with regard to desired effects and/or unwanted side effects are only incompletely understood. To investigate possible pleiotropic effects and respective molecular mechanisms, we describe here a catalogue of commonly used drugs and their impact on the blood transcriptome. METHODS AND RESULTS: From a population-based cohort in Germany (LIFE-Adult), we collected genome-wide gene-expression data in whole blood using in Illumina HT12v4 micro-arrays (n = 3,378; 19,974 gene expression probes per individual). Expression profiles were correlated with the intake of active substances as assessed by participants' medication. This resulted in a catalogue of fourteen substances that were identified as associated with differential gene expression for a total of 534 genes. As an independent replication cohort, an observational study of patients with suspected or confirmed stable coronary artery disease (CAD) or myocardial infarction (LIFE-Heart, n = 3,008, 19,966 gene expression probes per individual) was employed. Notably, we were able to replicate differential gene expression for three active substances affecting 80 genes in peripheral blood mononuclear cells (carvedilol: 25; prednisolone: 17; timolol: 38). Additionally, using gene ontology enrichment analysis, we demonstrated for timolol a significant enrichment in 23 pathways, 19 of them including either GPER1 or PDE4B. In the case of carvedilol, we showed that, beside genes with well-established association with hypertension (GPER1, PDE4B and TNFAIP3), the drug also affects genes that are only indirectly linked to hypertension due to their effects on artery walls or their role in lipid biosynthesis. CONCLUSIONS: Our developed catalogue of blood gene expressions profiles affected by medication can be used to support both, drug repurposing and the identification of possible off-target effects.

Lagrangian profiles of riverine autotrophy, organic matter transformation, and micropollutants at extreme drought.

On their way from inland to the ocean, flowing water bodies, their constituents and their biotic communities are exposed to complex transport and transformation processes. However, detailed process knowledge as revealed by Lagrangian measurements adjusted to travel time is rare in large rivers, in particular at hydrological extremes. To fill this gap, we investigated autotrophic processes, heterotrophic carbon utilization, and micropollutant concentrations applying a Lagrangian sampling design in a 600 km section of the River Elbe (Germany) at historically low discharge. Under base flow conditions, we expect the maximum intensity of instream processes and of point source impacts. Phytoplankton biomass and photosynthesis increased from upstream to downstream sites but maximum chlorophyll concentration was lower than at mean discharge. Concentrations of dissolved macronutrients decreased to almost complete phosphate depletion and low nitrate values. The longitudinal increase of bacterial abundance and production was less pronounced than in wetter years and bacterial community composition changed downstream. Molecular analyses revealed a longitudinal increase of many DOM components due to microbial production, whereas saturated lipid-like DOM, unsaturated aromatics and polyphenols, and some CHOS surfactants declined. In decomposition experiments, DOM components with high O/C ratios and high masses decreased whereas those with low O/C ratios, low masses, and high nitrogen content increased at all sites. Radiocarbon age analyses showed that DOC was relatively old (890-1870 years B.P.), whereas the mineralized fraction was much younger suggesting predominant oxidation of algal lysis products and exudates particularly at downstream sites. Micropollutants determining toxicity for algae (terbuthylazine, terbutryn, isoproturon and lenacil), hexachlorocyclohexanes and DDTs showed higher concentrations from the middle towards the downstream part but calculated toxicity was not negatively correlated to phytoplankton. Overall, autotrophic and heterotrophic process rates and micropollutant concentrations increased from up- to downstream reaches, but their magnitudes were not distinctly different to conditions at medium discharges.

Genome-wide association analysis of pulse wave velocity traits provide new insights into the causal relationship between arterial stiffness and blood pressure.

BACKGROUND: The pathophysiology of arterial stiffness is not completely understood. Pulse wave velocity (PWV) is an established marker for arterial stiffness. We compare genetics of three PWV modes, namely carotid-femoral PWV (cfPWV), brachial-ankle (baPWV) and brachial-femoral (bfPWV), reflecting different vascular segments to analyse association with genetic variants, heritability and genetic correlation with other biological traits. Furthermore we searched for shared genetic architecture concerning PWV, blood pressure (BP) and coronary artery disease (CAD) and examined the causal relationship between PWV and BP. METHODS AND RESULTS: We performed a genome-wide association study (GWAS) for cfPWV, baPWV and bfPWV in LIFE-Adult (N = 3,643-6,734). We analysed the overlap of detected genetic loci with those of BP and CAD and performed genetic correlation analyses. By bidirectional Mendelian Randomization, we assessed the causal relationships between PWV and BP. For cfPWV we identified a new locus with genome-wide significance near SLC4A7 on cytoband 3p24.1 (lead SNP rs939834: p = 2.05x10-8). We replicated a known PWV locus on cytoband 14q32.2 near RP11-61O1.1 (lead SNPs: rs17773233, p = 1.38x10-4; rs1381289, p = 1.91x10-4) For baPWV we estimated a heritability of 28% and significant genetic correlation with hypertension (rg = 0.27, p = 6.65x10-8). We showed a positive causal effect of systolic blood pressure on PWV modes (cfPWV: p = 1.51x10-4; bfPWV: p = 1.45x10-3; baPWV: p = 6.82x10-15). CONCLUSIONS: We identified a new locus for arterial stiffness and successfully replicated an earlier proposed locus. PWV shares common genetic architecture with BP and CAD. BP causally affects PWV. Larger studies are required to further unravel the genetic determinants and effects of PWV.

Nutrient mitigation under the impact of climate and land-use changes: A hydro-economic approach to participatory catchment management.

Excessive nutrient loadings into rivers are a well-known ecological problem. Implemented mitigation measures should ideally be cost-effective, but perfectly ranking alternative nutrient mitigation measures according to cost-effectiveness is a difficult methodological challenge. Furthermore, a particularly practical challenge is that cost-effective measures are not necessarily favoured by local stakeholders, and this may impede their successful implementation in practice. The objective of this study was to evaluate the cost-effectiveness of mitigation measures using a methodology that includes a participatory process and social learning to ensure their successful implementation. By combining cost data, hydrological modelling and a bottom-up approach for three different European catchment areas (the Latvian Berze, the Swedish Helge and the German Selke rivers), the cost-effectiveness of 16 nutrient mitigation measures were analysed under current conditions as well as under selected scenarios for future climate and land-use changes. Fertiliser reduction, wetlands, contour ploughing and municipal wastewater treatment plants are the measures that remove nutrients with the highest cost-effectiveness in the respective case study context. However, the results suggest that the cost-effectiveness of measures not only depends on their design, specific location and the conditions of the surrounding area, but is also affected by the future changes the area may be exposed to. Climate and land-use changes do not only affect the cost-effectiveness of measures, but also shape the overall nutrient loads and potential target levels in a catchment.

Balancing indicators for sustainable intensification of crop production at field and river basin levels.

Adequate tools for evaluating sustainable intensification (SI) of crop production for agro-hydrological system are not readily available. Building on existing concepts, we propose a framework for evaluating SI at the field and river basin levels. The framework serves as a means to assess and visualise SI indicator values, including yield, water-use efficiency and nitrogen-use efficiency (NUE), alongside water and nitrogen surpluses and their effects on water quantity and quality. To demonstrate the SI assessment framework, we used empirical data for both the field level (the Static Fertilization Experiment at Bad Lauchstädt) and the river basin level (the Selke basin, 463 km2) in central Germany. Crop yield and resource use efficiency varied considerably from 1980 to 2014, but without clear trends. NUE frequently fell below the desirable range (<50%), exposing the environment to a large N surplus (>80 kg N ha-1). For the catchment as a whole, the average nitrate-N concentration (3.6 mg L-1) was slightly higher than the threshold of 2.5 mg L-1 nitrate-N in surface water. However, weather and climate-related patterns, due to their effects on transport capacity and dilution, influenced water quantity and quality indicators more than agronomic practices. To achieve SI of crop production in the Selke basin, irrigation and soil moisture management are required to reduce yield variability and reduce N surpluses at field level. In addition, optimum application of fertiliser and manure could help to reduce the nitrate-N concentration below the set water quality standards in the Selke basin. In this way, there is scope for increase in yields and resource use efficiencies, and thus potential reduction of environmental impacts at basin level. We conclude that the framework is useful for assessing sustainable production, by simultaneously considering objectives related to crop production, resource-use efficiency and environmental quality, at both field and river basin levels.

Limited nitrogen retention in an urban river receiving raw sewage and wastewater treatment plant effluent.

Excessive dissolved inorganic nitrogen (DIN) added to urban river systems by point-source (PS) inputs, including raw sewage and wastewater treatment plant (WWTP) effluent, constitutes a water-quality problem of growing concern worldwide. However, the quantification of their impacts on DIN retention capacity and pathways in receiving water still remains partial. In this study, a spatially intensive water quality monitoring campaign was conducted to support the application of a water quality model to a PS-impacted urban river in Hefei City, China. The DIN retention capacities and pathway of a reference upstream Reach A, a raw-sewage-impacted Reach B and a WWTP-effluent-dominated Reach C were quantified using the model results after a Bayesian approach for parameter estimation and uncertainty analysis. The results showed that the raw sewage discharge elevated the assimilatory uptake rate but lowered its efficiency in Reach B, while the WWTP effluent discharge elevated both the denitrification rate and efficiency and made Reach C a denitrification hotspot with an increased nitrate concentration and hypoxic environment. The effects of the PS inputs on the DIN retention pathways (assimilatory uptake vs. denitrification) were regulated by their impacts on river metabolism. Despite different pathways, the total DIN retention ratios of Reaches A, B and C under low-flow conditions were 30.3% km-1, 14.3% km-1 and 6.5% km-1, respectively, which indicated that the instream DIN retention capacities were significantly impaired by the PS inputs. This result suggests that the DIN discharged from PS inputs to urban rivers will be transported with the potential to create long-term ecological implications not only locally but also more distant downstream.

Autotrophic nitrate uptake in river networks: A modeling approach using continuous high-frequency data.

High-frequency sensor measurements enable calculation of continuous autotrophic nitrate uptake rate based on its intrinsic relationship with gross primary production (GPP). The spatiotemporally available data offer prospects to advance process understandings across scales. We used continuous 15-min data (2011-2015) from a forest upstream reach and an agricultural downstream reach of the Selke River, Germany. Based on the high-frequency data, we developed a parsimonious approach for regionalizing the autotrophic uptake rate, considering effects of global radiation and riparian shading. For networked modeling, we integrated this approach into the fully distributed mesoscale hydrological nitrate model (mHM-Nitrate). Daily GPP-based uptake rate calculations showed distinct seasonal patterns and ranges in the agricultural and forest streams (mean values were 80.9 and 15.5 mgNm-2d-1, respectively). Validation in the two streams showed acceptable performance (R2 = 0.47 and 0.45, respectively) and spatial transferability of the regionalization approach, given its parsimony. Networked modeling results showed high spatiotemporal variability in nitrate transport and uptake throughout the river network. The magnitude of gross uptake increased, whereas uptake efficiency decreased significantly along stream order. Longitudinal analysis in the main stem of the Selke River revealed that riparian shading and inter-annual hydrochemical variations strongly influenced daily dynamics of the uptake efficiency. This study provides a parsimonious and transferable procedure for regionalizing in-stream autotrophic nitrate uptake based on high-frequency data at reach scale. Integrating this approach in the mHM-Nitrate model allows detailed nitrate transport and in-stream uptake processes to be investigated throughout river networks.

Modeling the effect of land use and climate change on water resources and soil erosion in a tropical West African catch-ment (Dano, Burkina Faso) using SHETRAN.

This study investigates the effect of land use and land cover (LULC) and climate change on catchment hydrology and soil erosion in the Dano catchment in south-western Burkina Faso based on hydrological and soil erosion modeling. The past LULC change is studied using land use maps of the years 1990, 2000, 2007 and 2013. Based on these maps future LULC scenarios were developed for the years 2019, 2025 and 2030. The observed past and modeled future LULC are used to feed SHETRAN, a hydrological and soil erosion model. Observed and modeled climate data cover the period 1990-2030. The isolated influence of LULC change assuming a constant climate is simulated by applying the seven LULC maps under observed climate data of the period 1990-2015. The isolated effect of climate scenarios (RCP4.5 and 8.5 of CCLM4-8) is studied by applying the LULC map of 1990 to the period 1990-2032. Additionally, we combined past modeled climate data and past observed LULC maps. Two chronological and continuous simulations were used to estimate the impact of LULC in the past and in the future by gradually applying the LULC maps. These simulations consider the combined impact of LULC and climate change. The simulations that assumed a constant climate and a changing LULC show increasing water yield (3.6%-46.5%) and mainly increasing specific sediment yield (-3.3%-52.6%). The simulations that assume constant LULC and climate as changing factor indicate increases in water yield of 24.5% to 46.7% and in sediment yield of 31.1% to 54.7% between the periods 1990-2005 and 2006-2032. The continuous simulations signal a clear increase in water yield (20.3%-73.4%) and specific sediment yield (24.7% to 90.1%). Actual evapotranspiration is estimated to change by between -7.3% (only LUCC) to +3.3% (only climate change). When comparing observed LULC and climate change alone, climate change has a larger impact on discharge and sediment yield, but LULC amplifies climate change impacts strongly. However, future LULC (2019-2030) will have a stronger impact as currently observed.

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.

A parsimonious approach to estimate PAH concentrations in river sediments of anthropogenically impacted watersheds.

The contamination of riverine sediments and suspended matter with hydrophobic pollutants is typically associated with urban land use. However, it is rarely related to the sediment supply of the watershed, because sediment yield data are often missing. We show for a suite of watersheds in two regions of Germany with contrasting land use and geology that the contamination of suspended particles with polycyclic aromatic hydrocarbons (PAH) can be explained by the ratio of inhabitants residing within the watershed and the watershed's sediment yield. The modeling of sediment yields is based on the Revised Universal Soil Loss Equation (RUSLE2015, Panagos et al., 2015) and the sediment delivery ratio (SDR). The applicability of this approach is demonstrated for watersheds ranging in size from 1.4 to 3000km2. The approach implies that the loading of particles with PAH can be assumed as time invariant. This is indicated by additional long-term measurements from sub-watersheds of the upper River Neckar basin, Germany. The parsimonious conceptual approach allows for reasonable predictions of the PAH loading of suspended sediments especially at larger scales. Our findings may easily be used to estimate the vulnerability of river systems to particle-associated urban pollutants with similar input pathways as the PAH or to indicate if contaminant point sources such as sites of legacy pollution exist in a river basin.

Sensors in the Stream: The High-Frequency Wave of the Present.

New scientific understanding is catalyzed by novel technologies that enhance measurement precision, resolution or type, and that provide new tools to test and develop theory. Over the last 50 years, technology has transformed the hydrologic sciences by enabling direct measurements of watershed fluxes (evapotranspiration, streamflow) at time scales and spatial extents aligned with variation in physical drivers. High frequency water quality measurements, increasingly obtained by in situ water quality sensors, are extending that transformation. Widely available sensors for some physical (temperature) and chemical (conductivity, dissolved oxygen) attributes have become integral to aquatic science, and emerging sensors for nutrients, dissolved CO2, turbidity, algal pigments, and dissolved organic matter are now enabling observations of watersheds and streams at time scales commensurate with their fundamental hydrological, energetic, elemental, and biological drivers. Here we synthesize insights from emerging technologies across a suite of applications, and envision future advances, enabled by sensors, in our ability to understand, predict, and restore watershed and stream systems.

Discharge Driven Nitrogen Dynamics in a Mesoscale River Basin As Constrained by Stable Isotope Patterns.

Nitrate loads and corresponding dual-isotope signatures were used to evaluate large scale N dynamics and trends in a river catchment with a strong anthropogenic gradient (forest conservation areas in mountain regions, and intensive agriculturally used lowlands). The Bode River catchment with an area of 3200 km(2) in the Harz Mountains and central German lowlands was investigated by a two years monitoring program including 133 water sampling points each representing a subcatchment. Based on discharge data either observed or simulated by the mesoscale hydrological model (mHM) a load based interpretation of hydrochemical and isotope data was conducted. Nitrate isotopic signatures in the entire catchment are influenced by (I) the contribution of different nitrogen sources, (II) by variable environmental conditions during the formation of nitrate, and (III) by a minor impact of denitrification. For major tributaries, a relationship between discharge and nitrate isotopic signatures is observed. This may in part be due to the fact, that during periods of higher hydrologic activity a higher wash out of isotopically lighter nitrate formed by bacterial nitrification processes of reduced or organic soil nitrogen occurs. Beyond that, in-stream denitrification seems to be more intense during periods of low flow.

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.

Continuous In-Stream Assimilatory Nitrate Uptake from High-Frequency Sensor Measurements.

Recently developed in situ NO3­ sensors provide new opportunities to measure changes in stream concentration at high temporal frequencies that historically have not been feasible. In this study, we used multiparameter sensor measurements to relate assimilatory NO3­ uptake to metabolic rates and calculate continuous uptake rates for two stream reaches and a whole stream network. Two years of continuous 15 min data from a forest and agricultural reach of the Selke river (456 km2) revealed a strong correlation between assimilatory NO3­ uptake and growth primary production (GPP) for the forest (r2 = 0.72) and agricultural (r2 = 0.56) stream reach. The slopes of these regressions were in agreement with predicted assimilatory N-uptake based on additional metabolic data. Mean yearly assimilatory NO3­ uptake rates (Ua) were 7.4 times higher in the agricultural stream reach (mean 78.3 mg N m­2 d­1, max 270 mg N m­2 d­1) than in the forest stream reach (mean 10.7 mg N m­2 d­1, max 97.5 mg N m­2 d­1). Nitrate uptake velocities (Vf,a) tended to decrease with increasing nitrate concentrations for periods with high light availability. Percentage daily assimilatory NO3­ uptake peaked at 47.4% of the daily NO3­ loading input to the stream network across the entire watershed, whereas the percentage yearly assimilatory NO3­ uptake was 9.0% of nitrogen loading to the stream network. This is a maximum because uptake can be revered by mineralization processes. The percentage yearly assimilatory NO3­ uptake was lower in the forest-dominated upstream subwatershed (4.8%) than in the lower agriculture dominated subwatershed (13.4%).

Source identification of fine-grained suspended sediment in the Kharaa River basin, northern Mongolia.

Fine sediment inputs into river systems can be a major source of nutrients and heavy metals and have a strong impact on water quality and ecosystem functions of rivers and lakes, including those in semiarid regions. However, little is known to date about the spatial distribution of sediment sources in most large scale river basins in Central Asia. Accordingly, a sediment source fingerprinting technique was used to assess the spatial sources of fine-grained (<10 µm) sediment in the 15 000 km(2) Kharaa River basin in northern Mongolia. Variation in geochemical composition (e.g. in Ti, Sn, Mo, Mn, As, Sr, B, U, Ca and Sb) was used for sediment source discrimination with geochemical composite fingerprints based on Genetic Algorithm (GA)-driven Discriminant Function Analysis, the Kruskal-Wallis H-test and Principal Component Analysis. All composite fingerprints yielded a satisfactory GOF (>0.97) and were subsequently used for numerical mass balance modelling with uncertainty analysis. The contributions of the individual sub-catchment spatial sediment sources varied from 6.4% (the headwater sub-catchment of Sugnugur Gol) to 36.2% (the Kharaa II sub-catchment in the middle reaches of the study basin), generally showing higher contributions from the sub-catchments in the middle, rather than the upstream, portions of the study area. The importance of river bank erosion is shown to increase from upstream to midstream tributaries. The source tracing procedure provides results in reasonable accordance with previous findings in the study region and demonstrates the applicability and associated uncertainties of the approach for fine-grained sediment source investigation in large scale semi-arid catchments.

Assessment of heavy metals in sediment of Aguamilpa Dam, Mexico.

The Aguamilpa Dam is part of the reservoir cascade system formed by four reservoirs in the middle and lower part of the Santiago River. For decades, this system has received urban and industrial wastewater from the metropolitan area of Guadalajara and the runoff of agricultural fields located in the river basin. The present study was carried out to obtain a preliminary assessment on the concentration distribution of heavy metals (Al, Ba, Cd, Cr, Cu, Fe, Hg, Mg, Ni, Pb, and Zn) in surface sediments of the Aguamilpa reservoir collected from 10 sampling stations. The metal concentrations (mg kg(-1)) in the sampling stations ranged as follows: Al, 27,600-7760; Ba, 190.0-15.9; Cd, 0.27-0.02; Cr, 18.30-0.22; Cu, 60.80-0.79; Fe, 15,900-4740; Hg, 0.04-0.01; Mg, 7590-8.05; Ni, 189.00-0.24; Pb, 13.6-1.64; and Zn, 51.8-14.8. Significant spatial variation in concentrations was observed for Al, Fe, and Pb. Sediment pollution was evaluated using the enrichment factor, the geo-accumulation index, the pollution load index, and sediment quality guidelines. Based on geo-accumulation and pollution load indexes, Aguamilpa sediments were found, in some sampling stations, as unpolluted to moderately polluted with Ni, Cd, Cu, and Mg. Enrichment factors showed that Cd is highly related to agricultural activities that take place in the surrounding areas of the Aguamilpa reservoir. Despite these results, none of the heavy metals evaluated exceeded international concentrations limits, indicating that the Aguamilpa reservoir surface sediments are not contaminated.