Stratification of reactivity determines nitrate removal in groundwater.

Biogeochemical reactions occur unevenly in space and time, but this heterogeneity is often simplified as a linear average due to sparse data, especially in subsurface environments where access is limited. For example, little is known about the spatial variability of groundwater denitrification, an important process in removing nitrate originating from agriculture and land use conversion. Information about the rate, arrangement, and extent of denitrification is needed to determine sustainable limits of human activity and to predict recovery time frames. Here, we developed and validated a method for inferring the spatial organization of sequential biogeochemical reactions in an aquifer in France. We applied it to five other aquifers in different geological settings located in the United States and compared results among 44 locations across the six aquifers to assess the generality of reactivity trends. Of the sampling locations, 79% showed pronounced increases of reactivity with depth. This suggests that previous estimates of denitrification have underestimated the capacity of deep aquifers to remove nitrate, while overestimating nitrate removal in shallow flow paths. Oxygen and nitrate reduction likely increases with depth because there is relatively little organic carbon in agricultural soils and because excess nitrate input has depleted solid phase electron donors near the surface. Our findings explain the long-standing conundrum of why apparent reaction rates of oxygen in aquifers are typically smaller than those of nitrate, which is energetically less favorable. This stratified reactivity framework is promising for mapping vertical reactivity trends in aquifers, generating new understanding of subsurface ecosystems and their capacity to remove contaminants.

Stream Dissolved Organic Matter in Permafrost Regions Shows Surprising Compositional Similarities but Negative Priming and Nutrient Effects.

Permafrost degradation is delivering bioavailable dissolved organic matter (DOM) and inorganic nutrients to surface water networks. While these permafrost subsidies represent a small portion of total fluvial DOM and nutrient fluxes, they could influence food webs and net ecosystem carbon balance via priming or nutrient effects that destabilize background DOM. We investigated how addition of biolabile carbon (acetate) and inorganic nutrients (nitrogen and phosphorus) affected DOM decomposition with 28-day incubations. We incubated late-summer stream water from 23 locations nested in seven northern or high-altitude regions in Asia, Europe, and North America. DOM loss ranged from 3% to 52%, showing a variety of longitudinal patterns within stream networks. DOM optical properties varied widely, but DOM showed compositional similarity based on Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis. Addition of acetate and nutrients decreased bulk DOM mineralization (i.e., negative priming), with more negative effects on biodegradable DOM but neutral or positive effects on stable DOM. Unexpectedly, acetate and nutrients triggered breakdown of colored DOM (CDOM), with median decreases of 1.6% in the control and 22% in the amended treatment. Additionally, the uptake of added acetate was strongly limited by nutrient availability across sites. These findings suggest that biolabile DOM and nutrients released from degrading permafrost may decrease background DOM mineralization but alter stoichiometry and light conditions in receiving waterbodies. We conclude that priming and nutrient effects are coupled in northern aquatic ecosystems and that quantifying two-way interactions between DOM properties and environmental conditions could resolve conflicting observations about the drivers of DOM in permafrost zone waterways.

Unexpected spatial stability of water chemistry in headwater stream networks.

Understanding how water and solutes enter and propagate through freshwater landscapes in the Anthropocene is critical to protecting and restoring aquatic ecosystems and ensuring human water security. However, high hydrochemical variability in headwater streams, where most carbon and nutrients enter river networks, has hindered effective modelling and management. We developed an analytical framework informed by landscape ecology and catchment hydrology to quantify spatiotemporal variability across scales, which we tested in 56 headwater catchments, sampled periodically over 12 years in western France. Unexpectedly, temporal variability in dissolved carbon, nutrients and major ions was preserved moving downstream and spatial patterns of water chemistry were stable on annual to decadal timescales, partly because of synchronous variation in solute concentrations. These findings suggest that while concentration and flux cannot be extrapolated among subcatchments, periodic sampling of headwaters provides valuable information about solute sources and subcatchment resilience to disturbance.

Long-term fate of nitrate fertilizer in agricultural soils.

Increasing diffuse nitrate loading of surface waters and groundwater has emerged as a major problem in many agricultural areas of the world, resulting in contamination of drinking water resources in aquifers as well as eutrophication of freshwaters and coastal marine ecosystems. Although empirical correlations between application rates of N fertilizers to agricultural soils and nitrate contamination of adjacent hydrological systems have been demonstrated, the transit times of fertilizer N in the pedosphere-hydrosphere system are poorly understood. We investigated the fate of isotopically labeled nitrogen fertilizers in a three-decade-long in situ tracer experiment that quantified not only fertilizer N uptake by plants and retention in soils, but also determined to which extent and over which time periods fertilizer N stored in soil organic matter is rereleased for either uptake in crops or export into the hydrosphere. We found that 61-65% of the applied fertilizers N were taken up by plants, whereas 12-15% of the labeled fertilizer N were still residing in the soil organic matter more than a quarter century after tracer application. Between 8-12% of the applied fertilizer had leaked toward the hydrosphere during the 30-y observation period. We predict that additional exports of (15)N-labeled nitrate from the tracer application in 1982 toward the hydrosphere will continue for at least another five decades. Therefore, attempts to reduce agricultural nitrate contamination of aquatic systems must consider the long-term legacy of past applications of synthetic fertilizers in agricultural systems and the nitrogen retention capacity of agricultural soils.

Deep denitrification: Stream and groundwater biogeochemistry reveal contrasted but connected worlds above and below.

Excess nutrients from agricultural and urban development have created a cascade of ecological crises around the globe. Nutrient pollution has triggered eutrophication in most freshwater and coastal ecosystems, contributing to a loss in biodiversity, harm to human health, and trillions in economic damage every year. Much of the research conducted on nutrient transport and retention has focused on surface environments, which are both easy to access and biologically active. However, surface characteristics of watersheds, such as land use and network configuration, often do not explain the variation in nutrient retention observed in rivers, lakes, and estuaries. Recent research suggests subsurface processes and characteristics may be more important than previously thought in determining watershed-level nutrient fluxes and removal. In a small watershed in western France, we used a multi-tracer approach to compare surface and subsurface nitrate dynamics at commensurate spatiotemporal scales. We combined 3-D hydrological modeling with a rich biogeochemical dataset from 20 wells and 15 stream locations. Water chemistry in the surface and subsurface showed high temporal variability, but groundwater was substantially more spatially variable, attributable to long transport times (10-60 years) and patchy distribution of the iron and sulfur electron donors fueling autotrophic denitrification. Isotopes of nitrate and sulfate revealed fundamentally different processes dominating the surface (heterotrophic denitrification and sulfate reduction) and subsurface (autotrophic denitrification and sulfate production). Agricultural land use was associated with elevated nitrate in surface water, but subsurface nitrate concentration was decoupled from land use. Dissolved silica and sulfate are affordable tracers of residence time and nitrogen removal that are relatively stable in surface and subsurface environments. Together, these findings reveal distinct but adjacent and connected biogeochemical worlds in the surface and subsurface. Characterizing how these worlds are linked and decoupled is critical to meeting water quality targets and addressing water issues in the Anthropocene.

Ferrous iron phosphorus in sediments: development of a quantification method through 2,2'-bipyridine extraction.

The role of ferrous iron in the phosphorus cycle of an aquatic ecosystem is poorly understood because of a lack of suitable methods to quantitatively evaluate ferrous iron phosphorus (FIP) phases. Using sediments sampled from Fubao Bay of Dianchi Lake in China, a novel extraction method for FIP using 2,2'-bipyridine was explored. Total phosphorus and iron in the sediments ranged from 1.0 to 5.0 mg/g (dry weight) and 28.5 to 90.6 mg/g, respectively. Organic content (as indicated by loss on ignition or LOI) and iron(II) ranged from 3.1 to 27.0% and 26.5 to 64.9 mg/g, respectively. The dissolution dynamics of FIP extraction with a low solid/liquid ratio (1:25) indicated that a single application of 0.2% 2,2'-bipyridine extracted both iron(II) (Fe(II)) and phosphorus (as PO4(3-)) in sediments with different organic contents with low efficiency. The extraction efficiency of Fe(II) was improved by alteration of the solid/liquid ratio, but the effect was limited. However, addition of a 1:1000 solid/liquid ratio of 0.5 M potassium chloride to a 0.2% 2,2'-bipyridine solution significantly accelerated extraction of FIP with the release of Fe(II) and phosphorus toward equilibrium at approximately 150 hours. Further investigation demonstrated that 2,2'-bipyridine exhibited a higher selectivity in distinguishing FIP from phosphorus bound to ferric (Fe(III)) oxides or precipitated by calcium (Ca2+). Air-drying sediments significantly decreased the amount of extracted FIP, which indicates that fresh, wet sediment should be used in this type of FIP extraction. Based on experimental results using the proposed extraction protocol, (1) FIP in sediments of Fubao Bay had a predominant status in the lake sediment and accounted for 23.4 to 39.8% of total phosphorus, and (2) Fe(II)(FIP) released in the extraction is directly proportional to phosphorus(FIP) (Fe(II)(FIP) = 2.84 x P(FIP) + 0.0007; R2 = 0.97) with an average molar ratio of Fe(II)(FIP)/P(FIP) of 2.7. This study shows that FIP extraction with 2,2'-bipyridine is a robust method for releasing ferrous iron associated with phosphorus. Further, the high percentage of FIP in total phosphorus (40%) measured in the study site using this extraction method suggests that FIP might have been often underestimated in previous studies.

Large-scale controls on potential respiration and denitrification in riverine floodplains.

Restoration measures of deteriorated river ecosystems generally aim at increasing the spatial heterogeneity and connectivity of these systems in order to increase biodiversity and ecosystem stability. While this is believed to benefit overall ecological integrity, consequences of such restoration projects on biogeochemical processes per se (i.e. ecosystem functioning) in fluvial systems are rarely considered. We address these issues by evaluating the characteristics of surface water connection between side arms and the main river channel in a former braided river section and the role and degree of connectivity (i.e. duration of surface water connection) on the sediment biogeochemistry. We hypothesized that potential respiration and denitrification would be controlled by the degree of hydrological connectivity, which was increased after floodplain restoration. We measured potential microbial respiration (SIR) and denitrification (DEA) and compared a degraded floodplain section of the Danube River with a reconnected and restored floodplain in the same river section. Re-establishing surface water connection altered the controls on sediment microbial respiration and denitrification ultimately impacting potential microbial activities. Meta-variables were created to characterize the effects of hydrology, morphology, and the available carbon and nutrient pools on potential microbial processing. Mantel statistics and path analysis were performed and demonstrate a hierarchy where the effects of hydrology on the available substrates and microbial processing are mediated by the morphology of the floodplain. In addition, these processes are highest in the least connected sites. Surface water connection, mediated by morphology regulates the potential denitrification rate and the ratio of N2O to N2 emissions, demonstrating the effects of restoration in floodplain systems.

Modelling highly variable environmental factors to assess potential microbial respiration in complex floodplain landscapes.

The hydrological exchange conditions strongly determine the biogeochemical dynamics in river systems. More specifically, the connectivity of surface waters between main channels and floodplains is directly controlling the delivery of organic matter and nutrients into the floodplains, where biogeochemical processes recycle them with high rates of activity. Hence, an in-depth understanding of the connectivity patterns between main channel and floodplains is important for the modelling of potential gas emissions in floodplain landscapes. A modelling framework that combines steady-state hydrodynamic simulations with long-term discharge hydrographs was developed to calculate water depths as well as statistical probabilities and event durations for every node of a computation mesh being connected to the main river. The modelling framework was applied to two study sites in the floodplains of the Austrian Danube River, East of Vienna. Validation of modelled flood events showed good agreement with gauge readings. Together with measured sediment properties, results of the validated connectivity model were used as basis for a predictive model yielding patterns of potential microbial respiration based on the best fit between characteristics of a number of sampling sites and the corresponding modelled parameters. Hot spots of potential microbial respiration were found in areas of lower connectivity if connected during higher discharges and areas of high water depths.

What do we need to predict groundwater nitrate recovery trajectories?

Nitrate contamination affects many of the Earth's aquifers and surface waters. Large-scale predictions of groundwater nitrate trends normally require the characterization of multiple anthropic and natural factors. To assess different approaches for upscaling estimates of nitrate recovery, we tested the influence of hydrological, historical, and biological factors on predictions of future nitrate concentration in aquifers. We tested the factors with a rich hydrogeological dataset from a fractured bedrock catchment in western France (Brittany). A sensitivity analysis performed on a calibrated model of groundwater flow, denitrification, and nitrogen inputs revealed that trends in nitrate concentration can effectively be approximated with a limited number of key parameters. The total mass of nitrate that entered the aquifer since the beginning of the industrial period needs to be characterized, but the shape of the historical nitrogen input time series can be largely simplified without substantially altering the predictions. Aquifer flow and transport processes can be represented by the mean and standard deviation of the residence time distribution, offering a tractable tool to make reasonable predictions at watershed to regional scales. Apparent sensitivity to denitrification rate was primarily attributable to time lags in oxygen depletion, meaning that denitrification can be simplified to an on/off process, defined only by the time needed for nitrate to reach the hypoxic reactive layer. Obtaining these key parameters at large scales is still challenging with currently available information, but the results are promising regarding our future ability to predict nitrate concentration with integrated monitoring and modeling approaches.

The rise of research on futures in ecology: rebalancing scenarios and predictions.

Concern about the ecological consequences of global change has increasingly stimulated ecologists to examine the futures of ecological systems. Studying futures is not only a crucial element of the interaction between science, management and decision making, but also a critical research challenge per se, especially because futures cannot be observed or experimented on. In addition, researchers can encounter methodological and theoretical difficulties, which make interpretations and predictions problematic. In the literature which deals with futures of ecological systems two main lines of research can be distinguished: a predictive approach, which dominates the literature, can be contrasted with a rarer number of studies that elaborate potential scenarios for ecological systems. Scenario approaches currently concern mainly contacts with stakeholders or decision makers, or the use of climate scenarios to derive projections about ecological futures. We argue that a new direction for ecological futures research could be explored by using ecological scenarios in combination with predictive models to further fundamental ecological research, in addition to enhancing its applied value.

Eutrophication: A new wine in an old bottle?

Eutrophication is one of the most common causes of water quality impairment of inland and marine waters. Its best-known manifestations are toxic cyanobacteria blooms in lakes and waterways and proliferations of green macro algae in coastal areas. The term eutrophication is used by both the scientific community and public policy-makers, and therefore has a myriad of definitions. The introduction by the public authorities of regulations to limit eutrophication is a source of tension and debate on the activities identified as contributing or having contributed decisively to these phenomena. Debates on the identification of the driving factors and risk levels of eutrophication, seeking to guide public policies, have led the ministries in charge of the environment and agriculture to ask for a joint scientific appraisal to be conducted on the subject. Four French research institutes were mandated to produce a critical scientific analysis on the latest knowledge of the causes, mechanisms, consequences and predictability of eutrophication phenomena. This paper provides the methodology and the main findings of this two years exercise involving 40 scientific experts.

Dating groundwater with dissolved silica and CFC concentrations in crystalline aquifers.

Estimating intermediate water residence times (a few years to a century) in shallow aquifers is critical to quantifying groundwater vulnerability to nutrient loading and estimating realistic recovery timelines. While intermediate groundwater residence times are currently determined with atmospheric tracers such as chlorofluorocarbons (CFCs), these analyses are costly and would benefit from other tracer approaches to compensate for the decreasing resolution of CFC methods in the 5-20 years range. In this context, we developed a framework to assess the capacity of dissolved silica (DSi) to inform residence times in shallow aquifers. We calibrated silicate weathering rates with CFCs from multiple wells in five crystalline aquifers in Brittany and in the Vosges Mountains (France). DSi and CFCs were complementary in determining apparent weathering reactions and residence time distributions (RTDs) in shallow aquifers. Silicate weathering rates were surprisingly similar among Brittany aquifers, varying from 0.20 to 0.23 mg L-1 yr-1 with a coefficient of variation of 7%, except for the aquifer where significant groundwater abstraction occurred, where we observed a weathering rate of 0.31 mg L-1 yr-1. The silicate weathering rate was lower for the aquifer in the Vosges Mountains (0.12 mg L-1 yr-1), potentially due to differences in climate and anthropogenic solute loading. Overall, these optimized silicate weathering rates are consistent with previously published studies with similar apparent ages range. The consistency in silicate weathering rates suggests that DSi could be a robust and cheap proxy of mean residence times for recent groundwater (5-100 years) at the regional scale. This methodology could allow quantification of seasonal groundwater contributions to streams, estimation of residence times in the unsaturated zone and improve assessment of aquifer vulnerability to anthropogenic pollution.

Spatial and seasonal variations in the composition of dissolved organic matter in a tropical catchment: the Lower Kinabatangan River, Sabah, Malaysia.

Dissolved organic matter (DOM) was characterised in water samples sampled in the Lower Kinabatangan River Catchment, Sabah, Malaysia between October 2009 and May 2010. This study aims at: (i) distinguishing between the quality of DOM in waters draining palm oil plantations (OP), secondary forests (SF) and coastal swamps (CS) and, (ii) identifying the seasonal variability of DOM quantity and quality. Surface waters were sampled during fieldwork campaigns that spanned the wet and dry seasons. DOM was characterised optically by using the fluorescence Excitation Emission Matrix (EEM), the absorption coefficient at 340 nm and the spectral slope coefficient (S). Parallel Factor Analysis (PARAFAC) was undertaken to assess the DOM composition from EEM spectra and five terrestrial derived components were identified: (C1, C2, C3, C4 and C5). Components C1 and C4 contributed the most to DOM fluorescence in all study areas during both the wet and dry seasons. The results suggest that component C4 could be a significant (and common) PARAFAC signal found in similar catchments. Peak M (C2 and C3) was dominant in all samples collected during wet and dry seasons, which could be anthropogenic in origin given the active land use change in the study area. In conclusion, there were significant seasonal and spatial variations in DOM which demonstrated the effects of land use cover and precipitation amounts in the Kinabatangan catchment.

An innovative approach for sequential extraction of phosphorus in sediments: Ferrous iron P as an independent P fraction.

Accurate identification of phosphorus (P) forms is crucially important for understanding the geochemical cycle of P; however, until now the role of ferrous iron P (Fe(II)-P) buried in sediments has been completely ignored in nearly all sequential extraction procedures developed. Using sediment cores sampled from Donghu Lake in Wuhan, China, this study explored a modified version of widely used sequential P extraction method (SEDEX; Ruttenberg, 1992) in which Fe(II)-P was identified as an independent fraction. Based on the high selectivity of the extractant (0.2% 2,2'-bipyridine+0.1 M KCl) and the dissolution equilibrium of P, procedures for extracting Fe(II)-P were optimized using a 1:100 solid:liquid ratio and extraction at 50 ± 1 °C for 24 h. The sedimentary P extracted was divided into five fractions: loosely-bound P, Fe(II)-P, CDB-P, Ca-P and O-P. Fe(II)-P was the predominant fraction in fresh sediments in Donghu Lake, accounting for 15.7-49.9% of TP, with a mean of 31.6%. The mean values of Ca-P, O-P, CDB-P and loosely-bound P were 28.4%, 22.7%, 17.1% and 4.3%, respectively. Combined with component analysis of extracts and recovery experiments of standard reference minerals (vivianite, Fe3(PO4)2·8H2O) in natural sediments, extraction of Fe(II)-P with 0.2% 2,2-bipridine and 0.1 M KCl was robust, with a good recovery rate (88.7-100.6%) and little of the Ca-P dissolved. It is possible to use this innovative SEDEX not only to distinguish the contribution of different P matrices in fresh sediments, but also to investigate the transformation of sedimentary P under different redox conditions. Therefore, greater focus on Fe(II)-P is necessary, because it is a major sink for the geochemical process of sedimentary P.

Controls on the distribution of rare earth elements in shallow groundwaters.

Shallow groundwater samples (<0.22 microm) collected from a small catchment in Western France (Petit Hermitage catchment) were analyzed for their rare earth elements (REE), dissolved organic carbon (DOC) and trace-element (Fe, Mn, Th and U) contents, with the aim to investigate the controlling factors of REE signatures. Two spatially distinct water types are recognized in this catchment based on changes of REE concentrations and variations of Ce anomalies. These include (i) DOC-poor groundwater flowing below the hillslope domains; this type has low REE contents and records conspicuous negative Ce anomalies; (ii) DOC-rich groundwater from the wetland domains, close to the river network; this type displays much higher REE concentrations, and typically lack negative Ce anomalies. Temporal REE concentration variations were assessed in wetland waters. Results show a marked increase of the REE content at the winter-spring transition, along with variations of DOC, Fe and Mn contents and redox potential changes. Using the above data set in conjunction with previously published results on comparable shallow groundwaters, we demonstrate that factors such as aquifer-rock composition or anthropogenic input probably play a minor role in determining the REE signatures of shallow groundwaters. Most likely, the two dominant factors involved are the organic matter content and the redox status of the waters. We suggest that topography might be the ultimate key parameter by its ability to control the DOC content of groundwater at a catchment scale.

Seasonal dynamics of denitrification along topohydrosequences in three different riparian wetlands.

We investigated the seasonal patterns of denitrification rates and potentials in soil profiles along the topohydrosequence formed at the upland-wetland interface in three riparian wetlands with different vegetation cover (i.e., forest, understory vegetation, and grass). Denitrification was measured using the acetylene inhibition method on soil cores and slurries, which provided a means of comparing the relative activity of this process in different locations. We evaluated, on a seasonal basis, the respective importance of the vegetative cover and the hydromorphic gradient as factors limiting denitrification. Regardless of the season, vegetation type, or lateral position along each topohydrosequence in the riparian wetlands, strong significant gradients of both in situ and potential denitrification rates were measured within a soil profile. Results confirm that the upper organic soil horizon is the most active, when in contact with the ground water. In deeper soil horizons, denitrification activity was low (from 0.004 to 0.5 mg N kg(-1) dry soil d(-1)), but contributed significantly to the reduction of ground water NO3- load along the riparian ground water flowpath (from 9.32 to 0.98 mg NO3-N L(-1)). Along the soil topohydrosequence, the denitrifying community of the upper soil horizons did not vary significantly on a seasonal basis despite the large seasonal ground water fluctuations. Along each topohydrosequence, the denitrification-limiting factor gradually shifted from anaerobiosis to NO3- supply. In situ denitrification rates in the forested, understory vegetation and grass sites were not significantly different. This result emphasizes the importance of the topography of the valley rather than the vegetation cover in controlling denitrification activity in riparian wetlands.

Evaluation of global change impacts on diffuse pollution.

In a global change context, several recent advances in the field of hydrology and biogeochemistry suggest that a move from a riparian to a river drainage basin perspective is necessary to reframe research and thus provide a more integrated scientific understanding to inform water- and land-use management and policy. We explore this assertion using the control of diffuse pollution as an exemplar.

Basic principles and ecological consequences of changing water regimes on nitrogen cycling in fluvial systems.

Understanding the environmental consequences of changing water regimes is a daunting challenge for both resource managers and ecologists. Balancing human demands for fresh water with the needs of the environment for water in appropriate amounts and at the appropriate times are shaping the ways by which this natural resource will be used in the future. Based on past decisions that have rendered many freshwater resources unsuitable for use, we argue that river systems have a fundamental need for appropriate amounts and timing of water to maintain their biophysical integrity. Biophysical integrity is fundamental for the formulation of future sustainable management strategies. This article addresses three basic ecological principles driving the biogeochemical cycle of nitrogen in river systems. These are (1) how the mode of nitrogen delivery affects river ecosystem functioning, (2) how increasing contact between water and soil or sediment increases nitrogen retention and processing, and (3) the role of floods and droughts as important natural events that strongly influence pathways of nitrogen cycling in fluvial systems. New challenges related to the cumulative impact of water regime change, the scale of appraisal of these impacts, and the determination of the impacts due to natural and human changes are discussed. It is suggested that cost of long-term and long-distance cumulative impacts of hydrological changes should be evaluated against short-term economic benefits to determine the real environmental costs.