•Storms stream flow, turbidity, NO3 and DOC concentrations and groundwater levels were described.•A set of functional descriptors was proposed to identify and interpret storm patterns.•Groundwater ...dynamics control seasonality of storm responses via sources connectivity.
The response of stream chemistry to storm is of major interest for understanding the export of dissolved and particulate species from catchments. The related challenge is the identification of active hydrological flow paths during these events and of the sources of chemical elements for which these events are hot moments of exports. An original four-year data set that combines high frequency records of stream flow, turbidity, nitrate and dissolved organic carbon concentrations, and piezometric levels was used to characterize storm responses in a headwater agricultural catchment. The data set was used to test to which extend the shallow groundwater was impacting the variability of storm responses. A total of 177 events were described using a set of quantitative and functional descriptors related to precipitation, stream and groundwater pre-event status and event dynamics, and to the relative dynamics between water quality parameters and flow via hysteresis indices. This approach led to identify different types of response for each water quality parameter which occurrence can be quantified and related to the seasonal functioning of the catchment. This study demonstrates that high-frequency records of water quality are precious tools to study/unique in their ability to emphasize the variability of catchment storm responses.
Cerium anomaly development in natural waters is commonly related to the mechanism of oxidative scavenging of tetravalent cerium by iron and/or manganese oxides. In this study, a new mechanism for the ...development of Ce anomalies is described, which combines the oxidation of Ce at high pH by carbonate and the preferential adsorption of Ce(IV) to humic acids. This new mechanism was experimentally elucidated by studying the competition between carbonate and humic acids for complexing rare earth elements (REE). These experiments showed that above pH 8.2, 8.6 or 8.7 (with decreasing alkalinity from 10
−
2
to 10
−
3
mol L
−
1
), Ce(III) is readily oxidized into Ce(IV), which is then preferentially adsorbed onto humic acids. This preferential uptake of Ce results in the development of a negative Ce anomaly (as low as 0.05) in the “truly” dissolved part of the solution (i.e., <
5 kDa), and a complementary positive anomaly (up to 1.22) occurs in the organic colloidal fraction. The positive and negative Ce anomalies remained hidden until the organic and inorganic fractions of the solution were separated. Therefore, Ce anomalies became apparent only after ultrafiltration of the waters and the subsequent isolation of the two fractions. The Ce anomaly is thus more likely to be a proxy of redox conditions in ultrafiltered waters than in unfiltered waters or in waters filtered to <
0.2 µm. The removal (e.g., by coagulation and/or flocculation) of organic molecules in organic-rich alkaline waters might lead to the development of a negative Ce anomaly in the resulting organic-poor waters. In contrast, some organic-poor alkaline waters may develop positive Ce anomalies due to preferential complexation of Ce(IV) by dissolved carbonate.
As a phenomenon integrating climate conditions and hydrological control of the connection between streams and terrestrial dissolved organic carbon (DOC) sources, groundwater dynamics control patterns ...of stream DOC characteristics (concentrations and fluxes). Influence of intra‐annual variations in groundwater level, discharge and climatic factors on DOC concentrations and fluxes were assessed over 13 years at the headwater watershed of Kervidy‐Naizin (5 km2) in western France. Four seasonal periods were delineated within each year according to groundwater fluctuations (A: rewetting, B: high flow, C: recession, and D: drought). Annual and seasonal base flow versus stormflow DOC concentrations were defined based on daily hydrograph readings. High interannual variability of annual DOC fluxes (5.4–39.5 kg ha−1 yr−1) indicates that several years of data are required to encompass variations in water flux to evaluate the actual DOC export capacity of a watershed. Interannual variability of mean annual DOC concentrations was much lower (4.9–7.5 mg C L−1), with concentrations decreasing within each year from ca. 9.2 mg C L−1 in A to ca. 3.0 mg C L−1 in C. This indicates an intra‐annual pattern of stream DOC concentrations controlled by DOC source characteristics and groundwater dynamics very similar across years. Partial least squares regressions combined with multiple linear regressions showed that the dry season characteristics (length and drawdown) determine the mean annual DOC concentration while annual runoff determines the annual flux. Antagonistic mechanisms of production‐accumulation and dilution‐depletion combined with an unlimited DOC supply from riparian wetland soils can mitigate the response of stream concentrations to global changes and climatic variations.
Key Points:
Groundwater fluctuations divide time series into hydrological seasons
Dry season length increases production and accumulation of DOC in soils
Runoff depletes the DOC stored in watershed soils during wet seasons
Monitoring the isotopic composition (δ13CDOC) of dissolved organic carbon (DOC) during flood events can be helpful for locating DOC sources in catchments and quantifying their relative contribution ...to stream DOC flux. High-resolution (< hourly basis) δ13CDOC data were obtained during six successive storm events occurring during the high-flow period in a small headwater catchment in western France. Intra-storm δ13CDOC values exhibit a marked temporal variability, with some storms showing large variations (> 2 ‰), and others yielding a very restricted range of values (< 1 ‰). Comparison of these results with previously published data shows that the range of intra-storm δ13CDOC values closely reflects the temporal and spatial variation in δ13CDOC observed in the riparian soils of this catchment during the same period. Using δ13CDOC data in conjunction with hydrometric monitoring and an end-member mixing approach (EMMA), we show that (i) > 80% of the stream DOC flux flows through the most superficial soil horizons of the riparian domain and (ii) the riparian soil DOC flux is comprised of DOC coming ultimately from both riparian and upland domains. Based on its δ13C fingerprint, we find that the upland DOC contribution decreases from ca.~30% of the stream DOC flux at the beginning of the high-flow period to < 10% later in this period. Overall, upland domains contribute significantly to stream DOC export, but act as a size-limited reservoir, whereas soils in the wetland domains act as a near-infinite reservoir. Through this study, we show that δ13CDOC provides a powerful tool for tracing DOC sources and DOC transport mechanisms in headwater catchments, having a high-resolution assessment of temporal and spatial variability.
Agriculture affects the biogeochemical cycles of carbon, nitrogen, and phosphorus, leading to a deterioration of surface water quality. The increasing magnitude of climate change raises questions ...about potential additional or mitigating effects of climate change on this deterioration. One way to understand these potential effects is to cross‐analyze the dynamics of nutrient concentrations and hydroclimatic variables at multiple time scales. Here, we used a 16‐year data set, from a 5 km2 agricultural watershed in France with a temperate oceanic climate, that contains a daily record of nutrient concentrations and hydroclimatic variables from 2002–2017. We calculated Mann‐Kendall and Theil‐Sen tests, Fourier transforms, and daily hydroclimatic distributions associated with extreme stream concentrations to investigate long‐term trends, seasonal dynamics and their interannual variations, and the daily time scale, respectively. Dynamics of dissolved organic carbon (DOC) and nitrate (NO3) concentrations displayed opposite patterns at the three temporal scales, while soluble reactive phosphorus concentrations showed decoupled dynamics, related more to extreme hydrological events. Climate and past agricultural changes seem to have a synergetic effect that leads to long‐term NO3 decrease and DOC increase. Precipitation and, to a greater extent, watershed wetness controlled seasonal and event‐driven dynamics.
Key Points
We analysed 16 years of daily hydroclimatic and water chemistry variables in a 5 km2 agricultural watershed
Opposite temporal patterns were observed for nitrate and DOC, independent of SRP variations, at interannual, seasonal, and event time scales
Agricultural pressures and climate drive long‐term trends, while watershed wetness controls shorter‐term variations
Protecting water quality at catchment scales is complicated by the high spatiotemporal variability in water chemistry. Consequently, determining pollutant sources requires costly monitoring ...strategies to diagnose causes and guide management solutions. However, recent studies have shown that spatial patterns in water chemistry can be persistent at catchment scales, potentially allowing identification of pollution sources and sinks with just a few sampling campaigns. Here, we tested a new method to quantify spatial persistence (SP) of water chemistry patterns with data from synoptic samplings in 22 headwater subcatchments within a 375 km2 catchment in western France (March 2018 to July 2019). This new method to quantify SP reduces dependence on long‐term metrics such as flow‐weighted concentrations, which are usually uncertain or unavailable. We applied the method to 16 ecologically relevant water quality parameters, including soluble reactive phosphorus, nitrate, and dissolved organic carbon. The results showed an average SP of 0.68 among parameters during the study period. For most parameters, SP was higher during the high‐flow winter period but lower and more variable during the low‐flow summer period. We found that the SP ultimately depended on the ratio between the temporal and spatial coefficients of variation (variance explained: 70%) rather than the temporal synchrony among subcatchments (variance explained: 4%). These results demonstrate that in these temperate catchments, synoptic sampling during the high‐flow winter period allows efficient identification of source and sink subcatchments, while more frequent samplings are needed to characterize ecological conditions at low flow.
Key Points
We found high spatial persistence of water chemistry, despite high spatiotemporal variability in water chemistry
Spatial persistence of water chemistry is primarily determined by the ratio between spatial and temporal variability
A single synoptic sampling during the high‐flow season allows efficient identification of source and sink subcatchments
The transfer of dissolved organic matter (DOM) at soil–river interfaces controls the biogeochemistry of micropollutants and the equilibrium between continental and oceanic C reservoirs. Understanding ...the mechanisms controlling this transfer is fundamental to ecology and geochemistry. DOM delivery to streams during storms is assumed to come from the flushing of preexisting soil DOM reservoirs mobilized by the modification of water flow paths. We tested this hypothesis by investigating the evolution of the composition of stream DOM during inter-storm conditions and five storm events monitored with high-frequency sampling. The composition of DOM was analyzed using thermally assisted hydrolysis and methylation (THM) with tetramethylammonium hydroxide (TMAH) coupled to a gas chromatograph and mass spectrometer. In inter-storm conditions, stream DOM is derived from the flushing of soil DOM, while during storm events, the modification of the distribution of chemical biomarkers allows the identification of three additional mechanisms. The first one corresponds to the destabilization of microbial biofilms due to the increase in water velocity, resulting in the fleeting export of a microbial pool. The second mechanism corresponds to the erosion of soils and river banks, leading to a partition of organic matter between particulate and dissolved phases. The third mechanism is linked to the increase in water velocity in soils that could induce the erosion of macropore walls, leading to an in-soil partition between soil microparticles and dissolved phase. The contribution of this in-soil erosive process would be linked to the magnitude of the hydraulic gradient following the rise of the water table and could persist after the recession, which could explain why the return to inter-storm composition of DOM does not follow the same temporal scheme as the discharge. These results are the most important factors in understanding the transfer of nutrients and micropollutants at the soil–river interfaces during the hot moments that are storm events.
Fecal contaminations of inland and coastal waters induce risks to human health and economic losses. To improve water management, specific markers have been developed to differentiate between sources ...of contamination. This study investigates the relative decay of fecal indicator bacteria (FIB, Escherichia coli and enterococci) and six human-associated markers (two bacterial markers: Bacteroidales HF183 (HF183) and Bifidobacterium adolescentis (BifAd); one viral marker: genogroup II F-specific RNA bacteriophages (FRNAPH II); three chemical markers: caffeine and two fecal stanol ratios) in freshwater and seawater microcosms seeded with human wastewater. These experiments were performed in darkness, at 20 °C and under aerobic conditions. The modeling of the decay curves allows us (i) to compare FIB and markers and (ii) to classify markers according to their persistence in seawater (FRNAPH II < HF183, stanol ratios < BifAd, caffeine) and in freshwater (HF183, stanol ratios < FRNAPH II < BifAd < caffeine). Although those results depend on the experimental conditions, this study represents a necessary step to develop and validate an interdisciplinary toolbox for the investigation of the sources of fecal contaminations.
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