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Dams are a globally relevant source of greenhouse gases (GHG), which impairs their function as a source of green energy. High burial rates of organic carbon (OC) in dam sediments may partly or fully offset the emissions. We argue that only the burial of carbon fixed in the timespan of dam operation changes the GHG balance. Here, we took sediment cores from a temperate dam. We analyzed radiocarbon age and OC molecular composition by laser desorption ionization mass spectrometry in the bulk OC and in four chemical extract fractions. The bulk samples contained modern OC, fixed after 1950. However, the extracted OC was of different ages (modern to 1900 years BP). Fractions with OC measured as old (>960 years BP) accounted for 57% of total sediment OC. Correlations of molecular composition with extract age suggest that these older fractions contained insignificant amounts of modern OC. We conclude that a substantial proportion of buried carbon did not originate from the contemporary atmosphere and cannot be offset against recent GHG emissions.

Dams are a globally relevant source of greenhouse gases (GHG), which impairs their function as a source of green energy. High burial rates of organic carbon (OC) in dam sediments may partly or fully offset the emissions. We argue that only the burial of carbon fixed in the timespan of dam operation changes the GHG balance. Here, we took sediment cores from a temperate dam. We analyzed radiocarbon age and OC molecular composition by laser desorption ionization mass spectrometry in the bulk OC and in four chemical extract fractions. The bulk samples contained modern OC, fixed after 1950. However, the extracted OC was of different ages (modern to 1900 years BP). Fractions with OC measured as old (>960 years BP) accounted for 57% of total sediment OC. Correlations of molecular composition with extract age suggest that these older fractions contained insignificant amounts of modern OC. We conclude that a substantial proportion of buried carbon did not originate from the contemporary atmosphere and cannot be offset against recent GHG emissions.

Soluble reactive phosphorus concentrations (SRP) in agricultural headwaters can display pronounced seasonal variability at low flow, with the highest concentrations occurring in summer. These SRP concentrations often exceed eutrophication levels but their main sources, spatial distribution, and temporal dynamics are often unknown. The purpose of this study is therefore to differentiate between potential SRP losses and releases from soil drainage, anoxic riparian wetlands and stream sediments in an agricultural headwater. To identify the dominant SRP sources we carried out three longitudinal stream sampling campaigns on SRP fluxes. We used salt dilution tests and 222Rn to determine water fluxes in different sections of the stream, and carried out specific sampling for SRP, iron and 14C-DOC to examine possible redox-mediated mobilization from riparian wetlands and stream sediments. The results indicate that a single short section in the upper headwater reach was responsible for most SRP losses to the stream. Analysis of samples taken under summer low flow conditions revealed that the stream-water SRP concentrations, SRP-fraction for dissolved P (DP) and DOC radiocarbon ages matched those in the groundwater entering the gaining section. We argue that the seasonal variation of SRP concentrations was mainly caused by variations in the proportion of groundwater present in the streamflow, and was thus highest during summer low flow periods. Stream-sediment pore water showed evidence of reductive mobilization of SRP but the exchange fluxes were probably too small to contribute substantially to SRP stream concentrations. Examination of the combined results of this campaign and previous monitoring confirms that groundwater is also the main long-term contributor of SRP at low flow and that seepage from agricultural phosphorous is largely buffered in the soil zone. In this headwater, stream SRP loading during low flow is therefore mainly geogenic, while agricultural sources pla

Fe(III) hydroxides stabilize organic carbon (OC) and P in soils. Observations of rising stream Fe concentrations are controversially posited to result from a flushing of iron-rich deeper soil layers or a decrease of competing electron acceptors inhibiting Fe reduction (NO3- and SO42-). Here, we argue that catchment topography constrains the release of Fe, OC, and P to streams. We therefore incubated organic topsoil and mineral subsoil and modified the availability of NO3-. We found that Fe leaching was highest in topsoil. Fe, OC, and P released at quantities proportional to their ratios in the source soil. Supply of NO3- reduced Fe leaching to 18% and increased pore water OC:Fe and P:Fe ratios. Subsoil, however, was an insignificant Fe source (<0.5%). Here, the leached quantities of Fe, OC and P were highly disproportionate to the soil source with an excess of released OC and P. We tested if experimental findings scale up using data from 88 German catchments representing gradients in NO3- concentration and topography. Average stream Fe concentrations increased with decreasing NO3- and were high in catchments with shallow topography where high groundwater levels support reductive processes and topsoils are hydrologically connected to streams; but Fe concentrations were low in catchments with steep topography where flow occurs primarily through subsoils. OC:Fe and P:Fe ratios in the streams similarly varied by NO3- and topography. This corroborates the findings from the laboratory experiment and suggests that catchment topography and competing electron acceptors constrain the formation of Fe-reducing conditions and control the release of Fe, OC, and P to streams. © 2022. The Authors.

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

Rivers transport carbon from continents to oceans. Surprisingly, this carbon has often been found to be centuries old, not originating from contemporary plant biomass. This can be explained by anthropogenic disturbance of soils or discharge of radiocarbon–depleted wastewater. However, land enclosure and channel bypassing transformed many rivers from anabranching networks to single–channel systems with overbank sediment accumulation and lowered floodplain groundwater tables. We hypothesized that human development changed the fluvial carbon towards older sources by changing the morphology of watercourses. We studied radiocarbon in the Elbe, a European, anthropogenically–transformed lowland river at discharges between low flow and record peak flow. We found that the inorganic carbon, dissolved organic carbon (DOC) and particulate organic carbon was aged and up to 1850 years old. The ∆14C values remained low and invariant up to median discharges, indicating that the sources of modern carbon (fixed after 1950) were disconnected from the river during half of the time. The total share of modern carbon in DOC export was marginal (0.04%), 72% of exported DOC was older than 400 years. This was in contrast to undisturbed forested subcatchments, 72% of whose exported DOC was modern. Although population density is high, mass balances showed that wastewater did not significantly affect the ∆14C-DOC in the Elbe river. We conclude that wetlands and other sources of contemporary carbon were decoupled from the anthropogenically transformed Elbe stream network with incised stream bed relative to overbank sediments, shifting the sources of fluvial carbon in favor of aged stores.

Die Charakterisierung und Quantifizierung von Phytoplankton­Gemeinschaften sind ein wesentlicher Aspekt der Gütebeurteilung von Standgewässern. In dieser Arbeit wird eine neue Herangehensweise hergeleitet und demonstriert, welche die klassische, taxonomisch­orientierte Methodik durch einen funktionalen Ansatz ergänzt, der auf den physiologischen und ökologischen Eigenschaften der Taxa (Traits) beruht. Kern des Ansatzes bildet der sogenannte Trait­Schlüssel, mit dem eine taxonomische Information in eine funktionale Information übersetzt werden kann. Die Aussagekraft und Potenziale des Verfahrens warden anhand von Langzeitdaten (50 Jahre) der Phytoplankton­Gemeinschaft der Rappbode­Talsperre exemplarisch demonstriert. Die Trait­basierte Analyse reduziert die Komplexität der Daten und ermöglicht eine quantitative Analyse der beobachteten Veränderungen auf der Basis von statistischen Methoden, die auf den klassischen taxonomischen Ansatz nicht anwendbar sind. Sowohl hinsichtlich der saisonalen Sukzession als auch der langfristigen Trends lassen die funktionalen Eigenschaften Rückschlüsse auf die maßgeblichen Umweltfaktoren zu. Für die wasserwirtschaftliche Praxis erweitert sich damit der Informationsgehalt und die Interpretierbarkeit der vorhandenen Daten. Diese Aufwertung der Ergebnisse kann ohne Mehraufwand erhalten werden. Von besonderem Interesse sind hierbei Kausalanalysen signifikanter Langzeittrends oder von sprunghaften Veränderungen in der Phytoplankton­Entwicklung, die hiermit in einen kausalen und systemanalytischen Zusammenhang gestellt werden können. Characterising and quantifying phytoplankton communities is a key element in assessing the lake quality. This article comes up with and demonstrates a new approach in which traditional taxonomy-based methodologies are complemented by a functional approach based on the taxa’s physiological and ecological characteristics (traits). The centrepiece of this approach is a trait key that can translate taxonomic inform

Understanding and explaining the structure of communities in response to environmental gradients is a central goal in ecology. Trait‐based approaches are promising but yet rarely applied to understand community dynamics in response to changing environmental conditions.Here we investigate seasonal succession patterns of functional traits in phytoplankton communities and how nutrient reductions (oligotrophication) alter these patterns. We used phytoplankton data from 40 years of observation from the Rappbode Reservoir (Germany), which underwent a strong shift in trophic conditions, and translated taxonomic composition into functional traits by assigning trait values compiled from the literature.All studied traits (morphological, behavioral and physiological traits) responded to changing environmental conditions and showed consistent, reoccurring seasonal developments. The seasonal succession of phytoplankton communities was shaped by a trade‐off between small celled, fast growing species that are able to rapidly incorporate existing resources (r‐strategists) and large celled species with more complex and efficient mechanisms to exploit scarce mineral nutrients or acquire previously unexploited nutrient pools (k‐strategists). In summer, when nutrients were scarce, the k‐strategy was prevailing (important traits: phosphate affinity, nitrogen fixation, motility and mixotrophy). During the rest of the year, nutrients and turbulence were high and r‐strategists dominated (important traits: maximum growth rate, light affinity). A comparison between eutrophic and oligotrophic years revealed that the main features of functional trait succession were largely preserved, but intra‐annual fluctuations from spring to summer were stronger during eutrophic years. Nutrient reductions mainly affected functional traits and biomass in spring, while in summer the functional community composition changed little.Synthesis. This study provides for the first time a quantitatively supported fu

Elevated concentration and high variance of dissolved organic carbon (DOC) in surface waters are a challenge for the production of drinking water. Past studies have indicated a dominant role of wetlands in DOC mobilization, but have mainly been focused on boreal and oceanic catchments. Here we analyze the observational DOC time series from 89 temperate humid catchments which drain into German drinking water reservoirs. We characterize the DOC concentration median and variability and utilize partial least squares regression in order to quantify the relation to catchment characteristics such as land use, climate, and topography. We found that the long-term median DOC concentration in the catchment is well predicted by the 90th percentile of the distribution of the topographic wetness index (0.9P TWI) over the entire catchment area. The 0.9P TWI can be directly connected to the abundance of riparian wetlands in the catchments. DOC concentration variability (represented as the ratio of the interquartile range and the median concentrations) was also found to be well predictable. Concentration variability was highest in cold and wet catchments with a high 0.9P TWI. Here we also found stronger correlations between DOC concentrations and discharge, with positive concentration-discharge patterns. Catchments with elevated DOC-concentration variance also exhibited the most severe long-term increases in concentrations. Our results thus indicate that, in temperate climates, riparian wetlands can be the dominant source zones of DOC and control the hydrological mobilization and potentially also the spatial difference in long-term concentration trends observed in surface waters. We conclude that the dominance of topography and climatic conditions in controlling spatio-temporal patterns in DOC concentrations leads to very limited management options.

To counteract the severe consequences of eutrophication on water quality and ecosystem health, nutrient inputs have been reduced in many lakes and reservoirs during the last decades. Contrary to expectations, in some lakes phytoplankton biomass did not decrease in response to oligotrophication (nutrient reduction). The underlying mechanisms preventing a decrease in biomass in these lakes are the subject of ongoing discussion. We used a hitherto unpublished long‐term data set ranging from 1961 until 2016 from a German drinking water reservoir (Rappbode Reservoir) to investigate the underlying mechanisms preventing a decrease in biomass. Total phosphorus (TP) concentrations in the Rappbode Reservoir dropped abruptly in 1990 from 0.163 to 0.027 mg/L within three consecutive years, as a result of banning phosphate‐containing detergents. Despite substantial reductions in TP, total annual phytoplankton biomass did not decline in the long‐run, and therefore, the yield of total phytoplankton biomass per unit phosphorus largely increased. Regression analysis revealed a positive association between the yield and potentially phagotrophic mixotrophs (R2 = .465, p < .001). We infer that by ingesting bacteria, mixotrophic species were capable of exploiting additional P sources that are not accessible to obligate autotrophic phytoplankton, eventually preventing a decrease in algal biomass after TP reductions. Long‐term epilimnetic phosphorus concentrations during the winter mixing period decreased to a greater degree than summer phosphorus concentrations. Apparently, TP losses over the season were less intense. Spring diatom biomass also markedly decreased after oligotrophication. In fact, spring diatom biomass was positively related to the TP loss over the season suggesting diatoms play an important role in P reduction. However, this intraannual P processing was not the primary factor when focusing on the average yearly yield, w

A common assumption in phosphorus (P) load apportionment studies is that P loads in rivers consist of flow independent point source emissions (mainly from domestic and industrial origins) and flow dependent diffuse source emissions (mainly from agricultural origin). Hence, rivers dominated by point sources will exhibit highest P concentration during low-flow, when flow dilution capacity is minimal, whereas rivers dominated by diffuse sources will exhibit highest P concentration during high-flow, when land-to-river hydrological connectivity is maximal. Here, we show that Soluble Reactive P (SRP) concentrations in three forested catchments free of point sources exhibited seasonal maxima during the summer low-flow period, i.e. a pattern expected in point source dominated areas. A load apportionment model (LAM) is used to show how point sources contribution may have been overestimated in previous studies, because of a biogeochemical process mimicking a point source signal. Almost twenty-two years (March 1995 – September 2016) of monthly monitoring data of SRP, dissolved iron (Fe) and nitrate-N (NO3) were used to investigate the underlying mechanisms: SRP and Fe exhibited similar seasonal patterns and opposite to that of NO3. We hypothesise that Fe oxyhydroxide reductive dissolution might be the cause of SRP release during the summer period, and that NO3 might act as a redox buffer, controlling the seasonality of SRP release. We conclude that LAMs may overestimate the contribution of P point sources, especially during the summer low-flow period, when eutrophication risk is maximal.

Drinking water reservoirs in the Northern Hemisphere are largely affected by the decadal-long increase in riverine dissolved organic carbon (DOC) concentrations. The removal of DOC in drinking water treatment is costly and predictions are needed to link DOC removal efficiency to its mobilization in catchments, both of which are determined by the molecular composition. To study the effect of hydrological events and land use on the molecular characteristics of dissolved organic matter (DOM), 36 samples from three different catchment areas in the German low mountain ranges, with DOC concentrations ranging from 3 to 32 mg L−1, were examined. Additionally, nine pairs of samples from downstream drinking water reservoirs were analyzed before and after flocculation. The molecular composition and the age of DOM were analyzed using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and radiocarbon (14C) analysis. At elevated discharge in a forested catchment comparatively younger, more oxygenated and unsaturated molecules of higher molecular weight were preferentially mobilized, likely linked to the reductive mobilization of iron. DOM with highly similar molecular characteristics (O/C ratio > 0.5, m/z > 500) could also be efficiently removed through flocculation in drinking water treatment. The proportion of DOM removed through flocculation ranged between 43% and 73% of DOC and was highest at elevated discharge. In catchment areas with a higher percentage of grassland and agriculture a higher proportion of DOM molecules containing sulfur and nitrogen was detected, which in turn could be less efficiently flocculated. Altogether, it was shown that DOM that is released during large hydrological events can be efficiently flocculated again, suggesting a reversal of similar chemical mechanisms in both processes. Since the occurrence of heavy rainfall events is predicted to i

We welcome the comment by Kalbitz et al. (2017) on our recent paper in which we examined long-term time series of concentrations of dissolved organic carbon (DOC) and phosphate from 110 streams in Germany. We concluded that increasing concentrations of both DOC and phosphate were governed by the reduction of iron(III)-minerals in riparian soils and the associated release of the adsorbed compounds. We explained the decreasing stability of the iron minerals by declining nitrogen depositions and thus decreasing nitrate redox buffers in riparian wetland soils (Musolff et al., 2017).

Sediments from the north basin of Lake 111, a small but very well studied lake resulting from lignite mining in Lusatia, show a pronounced fine layering. This layering can be found in several lignite pit lakes, but  mechanisms to explain it have not been investigated with respect to the specific hydrology and chemistry of acid pit lakes.The north basin of Lake 111 is flat-bottomed, dimictic, and bioturbation can be neglected. Physical and chemical characteristics, sedimentation rates and composition of settling material have been monitored over two years and large thin sections of sediment cores were analysed microscopically to identify fine sediment layering as annual.Total sedimentation rate was highest in winter, partly due to storms, while sedimentation of particulate organic matter showed peaks in May. Sedimentation of chrysophyte cysts occurred mainly in summer and autumn. Regular bands of chrysophyte cysts were detected, and comparison with the documented history of the lake substantiated that the observed lamination formed annually. To the best of our knowledge, this is the first report on varve formation in an extremely acidic lake which is not governed by fumaroles at the lake bottom.

Reductions in emissions have successfully led to a regional decline in atmospheric nitrogen depositions over the past 20 years. By analyzing long-term data from 110 mountainous streams draining into German drinking water reservoirs, nitrate concentrations indeed declined in the majority of catchments. Furthermore, our meta-analysis indicates that the declining nitrate levels are linked to the release of dissolved iron to streams likely due to a reductive dissolution of iron(III) minerals in riparian wetland soils. This dissolution process mobilized adsorbed compounds, such as phosphate, dissolved organic carbon and arsenic, resulting in concentration increases in the streams and higher inputs to receiving drinking water reservoirs. Reductive mobilization was most significant in catchments with stream nitrate concentrations <6 mg L−1. Here, nitrate, as a competing electron acceptor, was too low in concentration to inhibit microbial iron(III) reduction. Consequently, observed trends were strongest in forested catchments, where nitrate concentrations were unaffected by agricultural and urban sources and which were therefore sensitive to reductions of atmospheric nitrogen depositions. We conclude that there is strong evidence that the decline in nitrogen deposition toward pre-industrial conditions lowers the redox buffer in riparian soils, destabilizing formerly fixed problematic compounds, and results in serious implications for water quality.

Enhanced concentrations of dissolved organic matter (DOM) in freshwaters are an increasing problem in drinking water reservoirs. In this study we investigated bacterial DOM degradation rates in the tributaries of the reservoirs and tested the hypotheses that (1) DOM degradation is high enough to decrease DOM loads to reservoirs considerably, (2) DOM degradation is affected by stream hydrology, and (3) phosphorus addition may stimulate bacterial DOM degradation. Bacterial biomass production, which was used as a measure of DOM degradation, was highest in summer, and was usually lower at upstream than at downstream sites. An important proportion of bacterial production was realized in epilithic biofilms. Production of planktonic and biofilm bacteria was related to water temperature. Planktonic production weakly correlated to DOM quality and to total phosphorus concentration. Addition of soluble reactive phosphorus did not stimulate bacterial DOM degradation. Overall, DOM was considerably degraded in summer at low discharge levels, whereas degradation was negligible during flood events (when DOM load in reservoirs was high). The ratio of DOM degradation to total DOM release was negatively related to discharge. On annual average, only 0.6–12% of total DOM released by the catchments was degraded within the tributaries.