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Natural organic matter (NOM) is often still a black box considering its isomeric composition. From the analytical point of view the highest resolution of NOM can be achieved by Fourier-transform ion cyclotron resonance mass spectroscopy (FT-ICR-MS). This analytical tool generates elemental compositions of thousands of NOM components (molecular formulas, MFs) which can be extracted from aqueous samples (e.g., via solid phase extraction) and which are ionizable (e.g. via electrospray ionization). The comparison of NOM quality in waters of different ecosystems has generated useful insights about ecosystem-specific molecular differences. However, NOM is not an inert mixture of compounds and can undergo chemical changes by photochemical or microbial reactions or adsorptive fractionation. By following the relative intensity changes of single MFs during simple experiments close to nature or monitoring, elucidation of the reactivity of the underlying NOM compounds is possible.We have combined a photochemical degradation experiment close to nature with monitoring results from two German drinking water reservoirs with the perspective to disentangle photochemical and microbial reactions in the reservoirs. Bacterial induced transformations were widely excluded in the photo degradation experiment by filtration of the sample water before irradiation. During the reservoir monitoring, both microbial and photochemical reactions can be suggested from relative intensity differences of single MFs during lake stratification (between epi- and hypolimnion). MFs show intensity changes both in the photo experiment and in the lake monitoring are regarded as photo labile or photo products. Those MFs with intensity differences only in the lake monitoring can be regarded as microbial reactive.A great number of highly reactive MFs were found to be present in all samples of both the photo degradation experiment and the lake monitoring. MFs like C9H12O6, C10H14O6, C10H14O7, C11H16O5 were photo products, MFs like C20H16O14, C19H14O13, C18H12O12 were photo degraded. MFs like C10H10O7 and C9H10O7 could be suggested to be microbial products because they showed elevated intensity in epilimnetic waters but minor reactivity in the photo experiment.Our studies (1, 2, 3) provide the attempt to follow NOM reactivity by visualization of single MFs relative intensities versus time and / or space.1) Wilske, C.et al.,Water MDPI (2020) 12 (2).2) Herzsprung P. et al., Environ. Sci. Technol. (2020), 54, 13556-135653) Wilske C. et al., Water MDPI (2021), 13, 1703.

Nutrient and carbon dynamics within the river-estuary-coastal water systems are key processes to understand the matter fluxes from the terrestrial environment to the ocean. In a large-scale study we analysed those dynamics with the focus of the prevailing low water conditions by following a sampling approach based on the travel time of water.We started with a nearly Lagrangian sampling along the River Elbe (German part; 580 km within 8 days travel time). After a subsequent investigation of the estuary, the plume of the river was followed by raster sampling the German Bight (North Sea) using three ships simultaneously. In the river, intensive growth of phytoplankton was determined connected with high oxygen saturation and pH values as well as under-saturation of CO2, whereas concentrations of dissolved nutrients declined. In the estuary, the Elbe shifted from an autotrophic to a heterotrophic system: Phytoplankton died off upstream of the salinity gradient causing minima in oxygen saturation and pH, supersaturation of CO2, and a release of nutrients. In the coastal region, phytoplankton and nutrient concentrations were low, oxygen close to saturation, and pH in a typical marine range. We detected a positive relationship between pH values and oxygen saturation and a negative one between pCO2 and oxygen saturation. Corresponding to the significant particulate nutrient flux via phytoplankton, flux rates of dissolved nutrients from the river into the estuary were low and determined by depleted concentrations. In contrast, fluxes from the estuary to the coastal waters were higher and the pattern was determined by tidal currents.Overall, the presented observation approach is appropriate to better understand land-ocean fluxes, particularly if it is performed under different hydrological conditions including extremes and seems to be suitable to investigate the impact of such events in freshwater on coastal systems in future.The study was conducted within the frame of the Helmholtz MOSES initiative (Modular Observation Solutions for Earth Systems) targeting processes and impacts of hydrological extremes.

Dissolved organic matter (DOM) is ubiquitous in aquatic systems. Discharge of DOM to reservoirs via shallow ground and surface waters from the catchment poses major problems for drinking water production. Knowledge had been generated about mobilization and discharge of DOM in catchments based on the bulk parameter dissolved organic carbon (DOC) (1-3) or on bulk optical parameters describing its quality (4). The decomposition of DOC in catchments and reservoir waters was reported using DOC, bulk optical and carbon isotope analysis (5, 6).For drinking water treatment, removal of humic substances by coagulation / flocculation and the formation of disinfection byproducts are the most pressing challenges. The treatment success depends strongly on the chemical quality of DOM, which probably consists of thousands or even millions of different molecules. The identification of the isomeric structure of each molecule is still far from any instrumental analytical realization. From the analytical point of view the highest resolution of DOM can be achieved by Fourier Transform-Ion Cyclotron Resonance Mass Spectroscopy (FTICR-MS). This analytical tool generates elemental compositions of thousands of DOM components which are water extractable (solid phase extractable DOM, SPE-DOM) and which are ionizable (electrospray ionization, ESI).Using FTICR-MS, knowledge has been generated about the formation potential of disinfection byproducts and its composition (7) and about the flocculation behavior as function of the raw water DOM quality (8).Only few knowledge exists about DOM quality variations in the reservoirs and their catchments based on sum formulas from FTICR-MS analysis (8 - 11). Also little is known about transformations of drinking water treatment relevant sub fractions within the complex DOM in catchments and reservoir waters.As a first result of FTICR-MS measurements we observed that few components (sum formulas) showed high abundance differences as function of depth during reservoir stratification. Some poly-phenol-like components (relevant for flocculation) declined in the epilimnion of a drinking water reservoir potentially due to photo degradation. Some of the (more aliphatic) photo products, which were enriched in the epilimnion, are suspected to be disinfection byproduct precursors. This knowledge can be used to investigate the adaptation of the raw water subtraction depth in the reservoir. 1) Blaurock K et al., Hydrol. Earth Sys. Sci. Disc. (2021), https://doi.org/10.5194/hess2) Werner BJ et al., Biogeosci. (2019), 16, 4497-45163) Musolff A et al., J. Hydrol. (2018), 566, 205-2154) Da Silva MP et al., Biogeosci. (2020), 17, 5355-53645) Kamjunke N et al., Sci. Tot. Environ. (2016), 548-549, 51-596) Morling K et al., Sci. Tot. Environ. (2017), 577, 329-3397) Phungsai P et al., Environ. Sci. Technol. (2018), 52, 3392-34018) Raeke J et al., Wat. Res. (2017), 113, 149-1599) Da Silva MP et al., J. Geophys. Res. Biogeosci. (2021), 126, e2021JG00642510) Herzsprung P et al., Environ. Sci. Technol. (2020), 54, 13556-1356511) Wilske C et al., Water MDPI (2021), 13, 1703

Biofilms in river sediments play a key role in P retention in aquatic ecosystems. Most studies in freshwater ecosystems focus mainly on the autotrophic component of biofilms but little is known about the role of heterotrophic components on P removal. It is known that DOC in some streams is of low bioavailability, hence, resulting in severe DOC and P co-limitation of heterotrophic biofilm growth which could then constrain P removal efficiency. How DOC limitation affects P removal efficiency in the benthic zone and how it modifies P thresholds (i.e. concentration from which the removal efficiency decreases) are still open questions.We performed an experiment in the MOBICOS (Streamside Mobile Mesocosms) in the Holtemme River (Germany) to study the role of labile DOC on P thresholds in P retention in the bed-sediment biofilm community. Our flume experiment followed a BACI design (before: no DOC addition; after: labile DOC addition at C:P molar ratios >100; control: basal P and DOC concentrations; impact: P concentrations ranging from 25 µg P/L to 420 µg P/L).Our results show that labile DOC increases the P removal efficiency of the system (i.e. P water mass balances in the flumes) and shifts P thresholds for P removal towards higher P concentrations meaning that at a given P concentration higher P removal efficiency is achieved if the system is supplied with labile DOC. Labile DOC activated the heterotrophic component in the flumes and benthic biofilms receiving labile DOC show higher bacterial density and higher P accumulation compared to the ones not receiving labile DOC.Our results demonstrate that the heterotrophic biofilm community plays a key role in in-stream phosphorus retention. As it relies on availability of labile DOC, the interaction of DOC and P dynamics need consideration in models for stream nutrient processing and retention.

Modular Observation Solutions of Earth Systems (MOSES) is a novel observation system that is specifically designed to unravel the impact of distinct, dynamic events on the long-term development of environmental systems. Hydrometeorological extremes such as the recent European droughts or the floods of 2013 caused severe and lasting environmental damage. Modeling studies suggest that abrupt permafrost thaw events accelerate Arctic greenhouse gas emissions. Short-lived ocean eddies seem to comprise a significant share of the marine carbon uptake or release. Although there is increasing evidence that such dynamic events bear the potential for major environmental impacts, our knowledge on the processes they trigger is still very limited. MOSES aims at capturing such events, from their formation to their end, with high spatial and temporal resolution. As such, the observation system extends and complements existing national and international observation networks, which are mostly designed for long-term monitoring. Several German Helmholtz Association centers have developed this research facility as a mobile and modular “system of systems” to record energy, water, greenhouse gas, and nutrient cycles on the land surface, in coastal regions, in the ocean, in polar regions, and in the atmosphere—but especially the interactions between the Earth compartments. During the implementation period (2017–21), the measuring systems were put into operation and test campaigns were performed to establish event-driven campaign routines. With MOSES’s regular operation starting in 2022, the observation system will then be ready for cross-compartment and cross-discipline research on the environmental impacts of dynamic events., Bulletin of the American Meteorological Society, 103 (2), ISSN:0003-0007, ISSN:1520-0477

Benthic biofilms are often assumed to control terrestrially-derived dissolved organic carbon (tDOC) uptake in streams. We tested this by comparing 13C-enriched ryegrass leachate uptake in an agricultural and a forest stream, hypothesizing that a greater abundance of autotrophic biofilms in the agricultural stream would cause its whole-stream tDOC uptake to be comparatively low. We measured whole-stream and biofilm tDOC tracer uptake, metabolism, bacterial and algal diversity, and nutrient status of benthic epilithic biofilms, and assessed whole-stream hydromorphology. Whole-stream uptake of tDOC was six times lower in the agricultural (3.0 mg m−2 day−1) than in the forest (19.0 mg m−2 day−1) stream, and tDOC uptake velocity indicated lower tDOC demand in the agricultural (1.2 mm min−1) than in the forest (1.9 mm min−1) stream. The agricultural stream differed from the forest stream by slightly lower transient storage capacity and higher benthic biofilm bacterial abundance and production, lower biofilm biomass and lower biofilm molar C:N, C:P, and N:P ratios. Changes in epilithic biofilms contributed little to the differences in whole-stream tDOC tracer uptake between streams, as biofilm tDOC uptake only amounted to 4% and 13% of whole-stream uptake in the forest and agricultural stream, respectively. This comparison of a forest and an agricultural stream suggests that agricultural stressors have the potential to diminish both whole-stream tDOC uptake and uptake efficiency. Furthermore, the weak link between biofilm and whole-stream tDOC uptake implies that benthic biofilms characteristics are poor predictors for human impacts on tDOC uptake in agricultural streams and that hot spots of tDOC uptake are likely situated in the hyporheic zone or in the stream water column.

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.

Understanding river-sea-systems requires a thorough understanding of processes that span different Earth system compartments. To overcome issues related to the interaction of different scientific disciplines and compartments, such as different measurement and calibration standards, quality control approaches and data formats for specific environmental parameters, joint measurement campaigns have been initiated within the Helmholtz Association’s MOSES (Modular Observation Solutions for Earth Systems) project. Following multiple senor comparison and intercalibration campaigns in 2019, MOSES’ Hydrological Extremes event chain working group initiated joint field campaigns in summer 2020 covering the Elbe river from the Czech-German border to the tidal Elbe and further on into the estuary and the German Bight.The fundamental objective was to establish scientifically sound and resilient multi-ship applicable sampling procedures and to create reference data for the main environmental parameters for future investigation of extreme events such as flooding and drought and their overall impact on the catchment region and the adjacent estuarine area of a large European fresh water / marine system. The campaign involved four research vessels, four research centers and spanned nearly two months. Measurements included standard hydrological and oceanographic parameters, as well as quantities relevant to the nutrient and carbonate system. Furthermore, selected water quality indicators and atmospheric measurements were performed. In the fresh water section of the Elbe river measurements were taken while drifting with the water mass. In the tidal section of the river sampling was done against the ebb current while in the North Sea a grid covering a large part of the German exclusive economic zone (EEZ) was sampled.We detected a longitudinal increase of phytoplankton biomass along the 585 km freshwater part of the river towards the tidal system. In contrast, concentrations of dissolved nitrate and phosphate decreased to low values due the uptake by planktonic algae. The concentration of dissolved CO2 decreased caused by increasing photosynthesis while the concentration of methane increased along the river stretch, particularly in the most downstream part when sedimentation of phytoplankton increased the organic load of sediments. The tidal part of the transect showed a strong influence of Hamburg harbor on almost all quantities, while downstream towards the estuary, the effects of the tidal cycle dominated variabilities. In the marine area, elevated chlorophyll concentrations were mainly found near the west coast of Schleswig-Holstein, probably mostly influenced by the Eider river outflow or the adjacent tidal flats. While most of the measured parameters showed an expected behavior relative to their individual compartments, the transfer of quantities between the compartments revealed rather complex and sometimes difficult to understand behaviors and patterns, especially when considering a functional quantitative analysis. The first results of this trans-compartment campaign showed that a quantitative understanding of the fate and dynamics of water constituents across compartments from the spring to the sea needs enhanced scientific collaboration and awareness to finally come to a better integrated understanding of physical, biogeochemical and biological processes from the local to the global scale.

Surface waters are known to be significant sources of greenhouse gases (CH4 and CO2), but our understanding of large scale patterns is still incomplete. The greenhouse gases in rivers originate both from in-stream processes and interactions with the catchment. For coastal seas, rivers are suspected to be one of the main source of greenhouse gases, while the role of the interjacent tidal flats is still ambiguous. Especially the reaction of the entire system on terrestrial hydrological extremes such as low flow situations are still under consideration. The functional understanding of such events and their impacts on the water chemistry along its transition pathway in the terrestrial and limnic compartment as well as in the coastal marine environment is crucially needed for the evaluation of its relevance in the Earth system. As part of a MOSES campaign (Modular Observation Solutions for Earth Systems) spanning disciplines as well as earth system compartments we investigated the aquatic as well as the atmospheric compartemt in and above the Elbe River from inland waters through the tidal section of the river and the estuary to the North Sea with the goal to explore spatial heterogeneity of CO2 and CH4 concentrations in the water and in ambient air above the water during a low water period in summer 2020. Overall, dissolved CH4 concentrations ranged over three orders of magnitude. Along the freshwater part of the transect, dissolved CH4 increased and weirs and harbors appeared to be hot spots of elevated CH4 concentrations both for the dissolved and atmospheric phase. We observed a longitudinal gradient of CO2 in the river which was closely linked to primary production. In the estuary and the marine part, dissolved CH4 concentrations of the transect were determined by the variability of temperature and salinity. Correlations with other water parameters revealed the complex regulation of dissolved CH4 concentrations along the freshwater-seawater continuum. For atmospheric CH4 above the North Sea, wind direction and wind speed proved to be crucial. Besides the typical diurnal fluctuations of atmospheric CO2 and CH4, an observed link between dissolved and atmospheric concentrations has to be further clarified.

Despite elaborate regulation of agricultural pesticides, their occurrence in non-target areas has been linked to adverse ecological effects on insects in several field investigations. Their quantitative role in contributing to the biodiversity crisis is, however, still not known. In a large-scale study across 101 sites of small lowland streams in Central Europe, Germany we revealed that 83% of agricultural streams did not meet the pesticide-related ecological targets. For the first time we identified that agricultural nonpoint-source pesticide pollution was the major driver in reducing vulnerable insect populations in aquatic invertebrate communities, exceeding the relevance of other anthropogenic stressors such as poor hydro-morphological structure and nutrients. We identified that the current authorisation of pesticides, which aims to prevent unacceptable adverse effects, underestimates the actual ecological risk as (i) measured pesticide concentrations exceeded current regulatory acceptable concentrations in 81% of the agricultural streams investigated, (ii) for several pesticides the inertia of the authorisation process impedes the incorporation of new scientific knowledge and (iii) existing thresholds of invertebrate toxicity drivers are not protective by a factor of 5.3 to 40. To provide adequate environmental quality objectives, the authorisation process needs to include monitoring-derived information on pesticide effects at the ecosystem level. Here, we derive such thresholds that ensure a protection of the invertebrate stream community.

The science of the total environment 769, 144324 (2021). doi:10.1016/j.scitotenv.2020.144324, Published by Elsevier Science, Amsterdam [u.a.]

Dissolved organic matter plays an important role in aquatic ecosystems and poses a major problem for drinking water production. However, our understanding of DOM reactivity in natural systems is hampered by its complex molecular composition. Here, we used Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and data from two independent studies to disentangle DOM reactivity based on photochemical and microbial-induced transformations. Robust correlations of FT-ICR-MS peak intensities with chlorophyll a and solar irradiation were used to define 9 reactivity classes for 1277 common molecular formulas. Germany's largest drinking water reservoir was sampled for 1 year, and DOM processing in stratified surface waters could be attributed to photochemical transformations during summer months. Microbial DOM alterations could be distinguished based on correlation coefficients with chlorophyll a and often shared molecular features (elemental ratios and mass) with photoreactive compounds. In particular, many photoproducts and some microbial products were identified as potential precursors of disinfection byproducts. Molecular DOM features were used to further predict molecular reactivity for the remaining compounds in the data set based on a random forest model. Our method offers an expandable classification approach to integrate the reactivity of DOM from specific environments and link it to molecular properties and chemistry.

Dissolved organic matter (DOM) plays important roles in aquatic ecosystems but can interfere with drinking water production. However, its highly complex composition and chemical diversity makes it difficult to understand molecular reactivity in natural systems. Here we used ultra-high resolution mass spectrometry (FT-ICR-MS) and data from two independent studies (a lake monitoring and a photo-irradiation experiment) to disentangle DOM reactivity based on photochemical and microbial induced transformations.Monitoring in Germany’ largest drinking water reservoir (Rappbode reservoir, Harz Mountains) was conducted over one year on seven dates using water from nine depths. Water chemistry and limnological parameters, including chlorophyll a (chl a) concentration were determined. Stratification of the lake allowed to determine depths and periods, where an accumulation of chl a corresponded with an accumulation of DOM compounds. Chl a served as a surrogate for microbially (i.e. primary) produced DOM. In addition, we used data from a photodegradation experiment using river water from a catchment with similar land use (tributary to Muldenberg reservoir in the Ore Mountains, Germany). The water had been irradiated for 6 days in triplicates using natural sunlight. Thirteen time points had been sampled and used to determine the photochemical reactivity of DOM compounds.We used robust rank correlations to establish relationships between predictor (chl a concentration or cumulated sunlight irradiation) and response variables (normalized FT-ICR mass peak intensities) for each dataset. Combining the resulting data further allowed for an orthogonal classification of 1277 molecular formulas, which were present in all samples. Using this approach, we could identify 11 reactivity groups and attributed chemical properties to these groups based on molecular information. Photodegradation was observed for high molecular weight molecules - similar to microbial degradation - whereas photo products were aliphatic and oxygen rich. We found that in the lake studied, DOM turnover was dominated by photochemical processes. Exclusively microbial products were comparably low in number and of small molecular weight compounds.Based on the molecular-property-reactivity-relationships, we trained a random forest model and predicted the molecular reactivity for the remainder of molecular formulas, for which insufficient data were initially available.The approach presented here offers an expandable tool to integrate reactivity of DOM from specific environments and link it to its molecular properties and chemistry. This will lead to enhanced understanding of the ecological function and biogeochemical cycling of DOM.

Large rivers play a relevant role in the nutrient turnover from land to ocean. Here, highly dynamic planktonic processes are more important compared to streams making it necessary to link the dynamics of nutrient turnover to control mechanisms of phytoplankton. We investigated the basic conditions leading to high phytoplankton biomass and corresponding nutrient dynamics in the eutrophic River Elbe (Germany). In a first step, we performed six Lagrangian samplings in the lower river part at different hydrological conditions. While nutrient concentration remained high at low algal densities in autumn and at moderate discharge in summer, high algal concentrations occurred at low discharge in summer. Under these conditions, concentrations of silica and nitrate decreased and rates of nitrate assimilation were high. Soluble reactive phosphorus was depleted and particulate phosphorus increased inversely. Rising molar C:P ratios of seston indicated a phosphorus limitation of phytoplankton. Global radiation combined with discharge had a strong predictive power to explain maximum chlorophyll concentration. In a second step, we estimated nutrient turnover exemplarily for N during the campaign with the lowest discharge. Mass balance calculations revealed a total nitrate uptake of 455 mg N m-2d-1 which was clearly dominated by assimilatory phytoplankton uptake whereas denitrification and other benthic processes were only of minor importance. Phytoplankton density, which showed a sigmoidal longitudinal development, dominantly explained gross primary production, related assimilatory nutrient uptake and respiration. Chlorophyll a concentration and bacterial abundance affected the composition of dissolved organic matter and were positively related to a number of CHO and CHNO components with high H/C and low O/C ratios but negatively to several CHOS surfactants. In conclusion, nutrient uptake in the large river strongly depends on the growth conditions for phytoplankton, which are favored during summer drought conditions.

Photochemical processing is a major transformation pathway for allochthonous and autochthonous dissolved organic matter (DOM). DOM consists of thousands or even millions of different molecules and the isomer-resolved identification molecular structures is still far from any analytical realization. The highest analytical resolution of DOM can be achieved on a molecular mass basis via Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). With this technique, the molecular elemental compositions of thousands of DOM components can be assessed, given that they are extractable from water (via e.g. solid phase extraction, SPE-DOM) and ionizable (e.g. via electrospray ionization).Increasing levels of DOC in drinking water reservoirs pose serious challenges for drinking water processing. Photochemical processes potentially influence the DOM quality in the reservoir water. The photo degradation and / or the photo production of DOM components in surface freshwater as function of cumulated radiation was rarely investigated. In order to fill this gap we performed an irradiation experiment with water from a shaded forest stream flowing into a large reservoir (Muldenberg, Germany). DOC concentration, UV absorption, excitation-emission-matrices (EEMs) including calculated PARAFAC components and fluorescence indices, and FT-ICR MS derived molecular formulas of SPE-DOM were recorded at 13 different time points. The cumulated radiation was recorded during six days of solar irradiation (sunny days in August at 50.401847 deg. latitude and 12.380528 deg. longitude). Changes in relative peak intensity of DOM components as function of cumulated radiation were evaluated both by Spearman`s rank correlation and linear regression.We found components with different types of photo reaction behavior. Relative aliphatic components like C9H12O5 were identified as photo products showing a monotonous mass peak intensity increase with irradiation time. Highly unsaturated and oxygen-rich components like C15H6O8 showed a more or less monotonous intensity decrease indicating photo degradation. Many similar components were positively correlated to the humic-like fluorescence intensity and the humification index (HIX). The strong degradation of these components can explain the high loss of fluorescence intensity and the drop of the HIX in our experiment. As a result of the high temporal resolution in our experiment (i.e. intensity change as function of cumulated irradiation) we found another type of photo reaction. Components like C15H16O8 showed first increasing and then decreasing intensity indicating the formation of intermediate products.In general, the river DOM from the forested catchment area showed high potential for photochemical transformations which probably occur in the sunlight exposed predam of the drinking water reservoir.

Photochemical processing is an important way to transform terrestrial dissolved organic matter (DOM) but was rarely investigated by ultra-high resolution mass spectrometry. We performed an irradiation experiment with water from a shaded forest stream flowing into a lit reservoir. Bacterial activity explained only 1% of dissolved organic carbon (DOC) decline in a combined bacterial and photodegradation approach. Photodegradation decreased the DOC concentration by 30%, the specific ultraviolet (UV) absorption by 40%&ndash, 50%, and fluorescence intensity by 80% during six days. The humification index (HIX) decreased whereas the fluorescence index (FI) did not change. Two humic-like components identified by parallel factor analysis (PARAFAC) of excitation&ndash, emission matrices followed the decrease of fluorescent DOM. Changes of relative peak intensities of Fourier transform-ion cyclotron resonance mass spectroscopy (FT-ICR MS) elemental formula components as a function of cumulated radiation were evaluated both by Spearman&rsquo, s rank correlation and linear regression. The FT-ICR MS intensity changes indicate that high aromatic material was photochemically converted into smaller non-fluorescent molecules or degraded by the release of CO2. This study shows the molecular change of terrestrial DOM before the preparation of drinking water from reservoirs.

A large part of the organic carbon in streams is transported by pulses of terrestrial dissolved organic carbon (tDOC) during hydrological events, which is more pronounced in agricultural catchments due to their hydrological flashiness. The majority of the literature considers stationary benthic biofilms and hyporheic biofilms to dominate uptake and processing of tDOC. Here, we argue for expanding this viewpoint to planktonic bacteria, which are transported downstream together with tDOC pulses, and thus perceive them as a less variable resource relative to stationary benthic bacteria. We show that pulse DOC can contribute significantly to the annual DOC export of streams and that planktonic bacteria take up considerable labile tDOC from such pulses in a short time frame, with the DOC uptake being as high as that of benthic biofilm bacteria. Furthermore, we show that planktonic bacteria efficiently take up labile tDOC which strongly increases planktonic bacterial production and abundance. We found that the response of planktonic bacteria to tDOC pulses was stronger in smaller streams than in larger streams, which may be related to bacterial metacommunity dynamics. Furthermore, the response of planktonic bacterial abundance was influenced by soluble reactive phosphorus concentration, pointing to phosphorus limitation. Our data suggest that planktonic bacteria can efficiently utilize tDOC pulses and likely determine tDOC fate during downstream transport, influencing aquatic food webs and related biochemical cycles.

Long-term changes in dissolved organic matter (DOM) quality, especially in humic-rich raw waters, may lead to intensive adaptions in drinking-water processing. However, seasonal DOM quality changes in standing waters are poorly understood. To fill this gap, the DOM quality of a German drinking water reservoir was investigated on a monthly basis by Fourier-transform ion cyclotron resonance mass spectrometry (FTICR MS) measurements and 2D fluorescence for 18 months. FTICR MS results showed seasonal changes of molecular formula (MF) intensities, indicating photochemical transformation of DOM as a significant process for DOM quality variation. For an assessment of the two humic-like components, identified by parallel factor analysis (PARAFAC) of excitation–emission matrices (EEM), their loadings were Spearman’s rank-correlated with the intensities of the FTICR MS-derived MF. One of the two PARAFAC components correlated to oxygen-rich and relatively unsaturated MF identified as easily photo-degradable, also known as coagulants in flocculation processes. The other PARAFAC component showed opposite seasonal fluctuations and correlated with more saturated MF identified as photo-products with some of them being potential precursors of disinfection byproducts. Our study indicated the importance of elucidating both the chemical background and seasonal behavior of DOM if raw water-quality control is implemented by bulk optical parameters.

Fluvial networks are globally relevant for the processing of dissolved organic matter (DOM). To investigate the change in molecular DOM diversity along the river course, high-field FTICR mass spectrometry and NMR spectroscopy of riverine DOM as well as bacterial abundance and activity were measured in a third order stream along a land-use gradient from pristine, agricultural to urban landscapes. DOM composition showed a clear evolution along the river course with an initial decrease of average oxidation and unsaturation followed by an increased relative abundance of CHNO and CHOS compounds introduced by agriculture and waste water, respectively. DOM composition was dominated by rather unsaturated CHO compounds (H/C ≤ 1) in headwaters and by more aliphatic molecules at downstream sites. Oxygenated functional groups shifted from aromatic ethers and hydroxyl groups to aliphatic carboxylic acids and aliphatic hydroxyl groups. This massive dislocation of oxygen significantly increased the diversity of atomic environments in branched aliphatic groups from headwater to downstream DOM. Mass spectra of DOM enabled the detection of compositional relationships to bacterial abundance and activity which was positively related to more aliphatic components (H/C > 1) and negatively related to unsaturated components. FTICR mass and NMR spectra corroborated the initial decline in DOM molecular diversity predicted by the River Continuum Concept (RCC) but demonstrated an anthropogenic increase in the molecular diversity of DOM further downstream. While the high DOM molecular diversity in first order headwater streams was the result of small scale ecosystem plurality, agriculture and waste water treatment introduced many components in the lower reaches. These anthropogenic influences together with massive bacterial oxidation of DOM contributed to a growth of molecular diversity of downstream DOM whose composition and structure differed entirely from those found in pristine headwaters.

A method for recovering CO2 respired by bacterioplankton for analysis of carbon isotopes was adapted for use with standard laboratory equipment without a technically demanding harvest line. The recovered CO2 was more depleted in (14)C than the dissolved organic carbon (DOC) source, which suggests a selective respiration of older carbon.

Aquacultures are of great economic importance worldwide but pollute pristine headwater streams, lakes, and estuaries. However, there are no in-depth studies of the consequences of aquacultures on dissolved organic matter (DOM) composition and structure. We performed a detailed molecular level characterization of aquaculture DOM quality and its bacterial degradation using four salmon aquacultures in Chile. Fluorescence measurements, ultrahigh-resolution mass spectrometry, and nuclear magnetic resonance spectroscopy of the DOM revealed specific and extensive molecular alterations caused by aquacultures. Aquacultures released large quantities of readily bioavailable metabolites (primarily carbohydrates and peptides/proteins, and lipids), causing the organic matter downstream of all the investigated aquacultures to deviate strongly from the highly processed, polydisperse and molecularly heterogeneous DOM found in pristine rivers. However, the upstream individual catchment DOM signatures remained distinguishable at the downstream sites. The benthic algal biovolume decreased and the bacterial biovolume and production increased downstream of the aquacultures, shifting stream ecosystems to a more heterotrophic state and thus impairing the ecosystem health. The bacterial DOM degradation rates explain the attenuation of aquaculture DOM within the subsequent stream reaches. This knowledge may aid the development of improved waste processing facilities and may help to define emission thresholds to protect sensitive stream ecosystems.

This article provides an overview about the Bode River catchment that was selected as the hydrological observatory and main region for hydro-ecological research within the TERrestrial ENvironmental Observatories Harz/Central German Lowland Observatory. It first provides information about the general characteristics of the catchment including climate, geology, soils, land use, water quality and aquatic ecology, followed by the description of the interdisciplinary research framework and the monitoring concept with the main components of the multi-scale and multi-temporal monitoring infrastructure. It also shows examples of interdisciplinary research projects aiming to advance the understanding of complex hydrological processes under natural and anthropogenic forcings and their interactions in a catchment context. The overview is complemented with research work conducted at a number of intensive research sites, each focusing on a particular functional zone or specific components and processes of the hydro-ecological system.

Microbial decomposition of terrestrial carbon may be enhanced by the addition of easily decomposable compounds, a phenomenon referred to as priming effect. We investigated the microbial decomposition of terrestrial dissolved organic carbon (DOC) in one-stage and two-stage flow-through cultures (chemostats) in the absence and presence of growing phytoplankton as phytoplankton-derived organic matter might facilitate the mineralization of more refractory terrestrial compounds. Peat water and soil leachate were used as terrestrial substrates, and only slight DOC decomposition was observed in the absence of phytoplankton for both substrates. A priming effect was revealed via 14C data. Priming was more pronounced for the peat water substrate than for the soil leachate. The total DOC concentrations increased for both substrates in the presence of phytoplankton due to exudation and cell lysis. Samples from the soil leachate experiments were analyzed using ultra-high-resolution mass spectrometry (FT-ICR MS). Predominantly, the same saturated, aliphatic molecules with H/C ratios >1.5 were completely decomposed in the absence and in the presence of phytoplankton. The decomposition of more stable molecules differed in their intensity. Oxidized and unsaturated molecules with H/C ratios 0.4 were more strongly decomposed in phytoplankton presence (i.e., under priming). We conclude that an aquatic priming effect is not easily detectable via net concentration changes alone, and that qualitative investigations of the DOC processed by bacterial decomposition are necessary to detect aquatic priming.

Pre-dams are small reservoirs constructed upstream of the main drinking water reservoirs and are used for nutrient removal and sediment trapping. Little is known about the role of pre-dams regarding the production and decomposition of dissolved organic carbon (DOC) in relation to discharge and how this affects the quality of DOC in the water. We combined quantitative and qualitative investigations under different hydrological conditions at three pre-dams exhibiting a gradient from oligotrophic/high-DOC to eutrophic/low-DOC. All pre-dams were mainly autotrophic in their upper water layers. The ratio of OC production to total gained OC (i.e. OC import+OC production) decreased with increasing discharge. On average, 0-30% of the total gained OC was produced within the pre-dams. The amount of microbially decomposed DOC increased with the average water residence time (WRT) and with the trophic status of the pre-dams. Radiocarbon analyses of respired CO2 revealed that heterotrophic bacteria preferentially utilized old DOC components (195-395years before present) under base flow conditions, whereas younger components (modern, i.e. OC produced after 1950) were utilized at high discharge. DOC quality changed significantly over the year within the pre-dams: High proportions of algae-derived DOC were observed during base flow in summer, and the freshness index (β/α ratio) decreased significantly with higher discharges. DOC production and quality changes in response to hydrological conditions should be considered for future water quality management in reservoirs, as climate scenarios for temperate regions predict decreased runoffs leading to longer WRT and increased eutrophication and production of algae-derived OC.

Dissolved organic carbon (DOC) constitutes the bulk of organic carbon in aquatic environments. The importance of DOC utilization by mixotrophic algae is unclear since heterotrophic bacteria are regarded as more efficient users. We tested the hypothesis that algae decrease the DOC concentration in the light to lower levels than in darkness resulting in competitive exclusion of heterotrophic bacteria according to the mechanistic competition theory. We investigated (a) the uptake kinetics of glucose as a model substrate by two cultured algae and mixed bacteria populations, (b) the competition for glucose between algae and bacteria in chemostats, (c) the effect of discontinuous glucose supply in chemostats, and (d) the minimum glucose concentrations achieved in cultures of algae and bacteria. Bacteria showed higher specific-glucose-uptake rates than algae. In chemostats, algae became extinct in the dark and coexisted in the light where they decreased bacteria to lower densities. Discontinuous glucose supply promoted the algae compared to continuous substrate addition. Several algae consumed glucose to lower concentrations in the dark than in the light and showed lower or equal residual glucose concentrations than bacteria. Residual concentrations were not related to allometric traits (cell volume) and photosynthetic potential (chl content). Overall, the hypothesis was not supported, and mechanisms of competition for DOC obviously differed from those for particulate prey. However, since some algae showed lower or equal residual glucose concentrations than bacteria, algal dark uptake of DOC may be important in deep layers of many waters.

Aquatic bacteria are considered to exhibit a paradoxical behaviour. They luxuri-ously consume phosphorus, the element often restricting the abundance of algae,which provide the organic substrates maintaining bacterial growth. Here, we testthe hypothesis that bacteria can limit their uptake of phosphorus and increase theavailability of phosphorus to algae. The physiological costs for bacteria must becompensated for by a surplus of photosynthetic exudates facilitating higherbiomass production. To test the potential of such an economic behaviour, we useda new differential equation model that was parameterized by independent experi-ments. Model results indicate that this potential does exist. As a consequence, weconducted continuous growth chemostat experiments. Bacteria did not leave morephosphorus to, “high exudation” algae compared with algae with low release.Therefore, the hypothesis was not supported by the experiments. However, bac-teria significantly increased production 1.4–1.8-fold in cultures with “high exud-ation” algae. This was explained by an increase in conversion of organic carbonfrom growth medium into bacteria biomass. Algal exudates were quantitativelynegligible but could act as growth factors. The results show that biomass of algaeand bacteria cannot be predicted solely by mineral nutrients and carbon asassumed by the classical theory.KEYWORDS: bacteria; phytoplankton; exudation; phosphorus; differentialequation model

To investigate the consequences of increased temperature and enhanced input of dissolved organic matter (DOM) into lakes for heterotrophicic bacteria and for mixotrophic algae which use DOM in addition to photosynthesis, the hypotheses were tested whether (1) both bacteria and mixotrophic algae benefit from increased input of DOM, or (2) increased DOM input enhances bacterial biomass and thereby decreases algal biomass. Growth experiments in batch cultures, exudation measurements, and competition experiments in chemostats were performed at two temperature levels. Increased temperature stimulated the autotrophic growth rate of Chlorella protothecoides. Bacteria and Chlorella increased their heterotrophic growth rates at higher DOM concentration at lower temperature whereas enhanced DOM concentration hardly stimulated their growth at higher temperature. In chemostats, enhanced input of soil extract increased both bacterial and algal biomass at lower temperature whereas bacterial biomass increased only slightly and algal biomass decreased at higher temperature. Thus, the temperature determines the response of microorganisms to enhanced DOM concentration.

Acidic mining lakes (pH

Algae of various taxonomic groups are capable of assimilating dissolved organic carbon (DOC) from their environments (mixotrophy). Recently, we reported that, with increasing biomass of mixotrophs, heterotrophic bacteria did not increase. We hypothesized that algal uptake of external DOC may outweigh their release of DOC by exudation (H1). Here, we addressed an alternative hypothesis that algae did not assimilate external DOC but constrained the release of DOC (H2). In chemostat experiments, we cultured the mixotrophic Chlamydomonas acidophila Negoro together with heterotrophic bacteria. As external substrates, we used glucose, which was potentially available for both bacteria and algae, or fructose, which was available only for bacteria. We increased the biomass of algae by the stepwise addition of phosphorus. Bacterial biomass did not increase in experiments using glucose or when fructose was offered, suggesting that mechanisms other than algal mixotrophy (H1) kept concentrations of bacteria low. Measured exudation rates (percent extracellular release, PER) of mixotrophic algae (Cd. acidophila, Chlorella protothecoides W. Kruger) were very low and ranged between 1.0% and 3.5% at low and moderately high phosphorus concentrations. In contrast, an obligately phototrophic alga (Chlamydomonas segnis H. Ettl) showed higher exudation rates, particularly under phosphorus limitation (70%). The results support H2. If mixotrophy is considered as a mechanism to recycle organic exudates from near the cell surface, this would explain why algae retained mixotrophic capabilities although they cannot compete with bacteria for external organic carbon.

Terrestrial-derived dissolved organic carbon (DOC) contributes significantly to the energetic basis of many aquatic food webs. Although heterotrophic bacteria are generally considered to be the sole consumers of DOC, algae and cyanobacteria of various taxonomic groups are also capable of exploiting this resource. We tested the hypothesis that algae can utilise DOC in the presence of bacteria if organic resources are supplied in intervals by photolysis of recalcitrant DOC. In short-term uptake experiments, we changed irradiation in the range of minutes. As model substrates, polymers of radiolabelled coumaric acid (PCA) were used, which during photolysis are known to release aromatic compounds comparable to terrestrial-derived and refractory DOC. Three cultured freshwater algae readily assimilated PCA photoproducts equivalent to a biomass-specific uptake of 5-60% of the bacterial competitors present. Algal substrate acquisition did not depend on whether PCA was photolysed continuously or in intervals. However, the data show that photoproducts of terrestrial DOC can be a significant resource for osmotrophic algae. In long-term growth experiments, interval light was applied one hour per day. We allowed cultured Chlamydomonas to compete for ambient DOC of low concentration. We found higher abundances of Chlamydomonas when cultures were irradiated intermittently rather than continuously. These data suggest that photolysis of DOC supports algal heterotrophy, and potentially facilitates growth, when light fluctuations are large, as during the diurnal light cycle. We concluded that osmotrophic algae can efficiently convert terrestrial carbon into the biomass of larger organisms of aquatic food webs.

It is now widely accepted that many surface waters receive more terrestrial carbon than assumed in the past, and that aquatic food webs are largely based on the supply of external dissolved organic carbon. However, very little information is available on how efficiently external carbon is utilized by microorganisms and transported to consumers of higher trophic levels. To address this issue, we prepared and tested polymers of 14C-p-coumaric acid (PCA) as a model substrate for terrestrial organic carbon. Photodegradation products that can be considered potential substrates for microorganisms were identified using hyphenated techniques, including gas chromatography-mass spectrometry (GC/MS) and ion chromatography-electrospray ionization mass spectrometry (IC/MS). Photolysis of PCA released monomeric phenol derivatives, e.g. 4-hydroxybenzaldehyde. The photolysis products observed were similar to those characteristic for natural organic carbon. Both a heterotrophic bacteria assemblage and a cultured algae strain exhibiting heterotrophic capabilities proved capable of utilizing the model substrate. Irradiation of PCA increased the uptake rate approximately eight times for the bacteria, but no significant increase was observed for the algae. Potential sources of interferences, e.g. the uptake of 14CO2 released by photolysis, were addressed. It was concluded that PCA is a suitable substrate to study the metabolism of terrestrial DOC within aquatic communities.

Dissolved organic carbon (DOC) constitutes the bulk of organic carbon in aquatic environments. The importance of DOC utilization by mixotrophic algae is unclear since heterotrophic bacteria are regarded as more efficient users. We tested the hypothesis that algae decrease the DOC concentration in the light to lower levels than in darkness resulting in competitive exclusion of heterotrophic bacteria according to the mechanistic competition theory. We investigated (a) the uptake kinetics of glucose as a model substrate by two cultured algae and mixed bacteria populations, (b) the competition for glucose between algae and bacteria in chemostats, (c) the effect of discontinuous glucose supply in chemostats, and (d) the minimum glucose concentrations achieved in cultures of algae and bacteria. Bacteria showed higher specific-glucose-uptake rates than algae. In chemostats, algae became extinct in the dark and coexisted in the light where they decreased bacteria to lower densities. Discontinuous glucose supply promoted the algae compared to continuous substrate addition. Several algae consumed glucose to lower concentrations in the dark than in the light and showed lower or equal residual glucose concentrations than bacteria. Residual concentrations were not related to allometric traits (cell volume) and photosynthetic potential (chl content). Overall, the hypothesis was not supported, and mechanisms of competition for DOC obviously differed from those for particulate prey. However, since some algae showed lower or equal residual glucose concentrations than bacteria, algal dark uptake of DOC may be important in deep layers of many waters.

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.

As benthic biofilms mediate essential functions in stream ecosystems (e.g., carbon flux, storage of nutrients and other substances), the element-specific regulation of the biofilm composition is of great interest. We tested whether (1) the elemental composition of biofilms is related to that of the water column and (2) there are different accumulation patterns from the dissolved phase (adsorption) and the particulate phase (incorporation of suspended matter). We analysed biomass parameters, nutrients and metals in biofilms and surface waters at 28 sites within a stream network (Bode catchment, Germany). Algal biomass in biofilms was dominated by diatoms. The P/C ratio in biofilms was positively related to total phosphorus of surface water (and to the proportion of agricultural area in the catchment) indicating phosphorus limitation of biofilms, whereas the N/C ratio was not related to nitrate levels of surface water, and neither the P/C nor the N/C ratio to the concentration of dissolved organic carbon (DOC) of surface water. Biofilms were enriched in metals compared to their concentrations in water. The metals in biofilms were positively related to the concentration of dissolved metals in surface water for iron and strontium (but not for manganese, copper, zinc, arsenic or lead) and to the concentrations of particle-associated metals of surface waters for strontium and lead. Manganese and arsenic were the metals with a negative effect on the biomasses of biofilm diatoms and cyanobacteria. Overall, we observed element-specific accumulation patterns in biofilms with selected elements being related to the water column while others were probably subject to biofilm-internal processes.

Chile is the second largest producer of salmonids worldwide. The first step in the production of salmonids takes place in land-based aquacultures. However, the effects of the discharge from these aquacultures on stream dissolved organic matter (DOM) content, molecular composition and degradability are unknown. The aim of this study was thus to investigate the inputs of anthropogenic DOM from land-based aquaculture to the predominantly pristine river systems of North Patagonia. We hypothesized, that i) DOM exported from land-based aquaculture mainly consists of protein-like fluorescence (tyrosine and tryptophan) released from fish feces and food remains, and that ii) this DOM is highly degradable and therefore rapidly turned-over within the receiving streams. In the North Patagonian region we conducted a screening of ten land-based aquacultures and an intensive sampling campaign for one aquaculture. This was combined with longitudinal transects and a degradation experiment in order to couple the composition of DOM exported from land-based aquacultures to its degradability in streams. We measured dissolved organic carbon (DOC) concentration by high-temperature catalytic oxidation and DOM composition by fluorescence spectroscopy and parallel factor analysis. In the effluent of the ten screened aquacultures and in the repeated sampling of one aquaculture, we consistently found an increase of DOC concentrations and a dominance of protein-like fluorescence. The protein-like fluorescence rapidly disappeared downstream of the aquacultures, and in the degradation experiment. 21 % of the DOC export from the repeatedly sampled aquaculture resulted from food addition and 76% from fish production. We conclude that large amounts of degradable DOM are exported from land-based aquacultures. This probably has strong effects on the ecological structure and function of North Patagonian streams, and similarly affected streams worldwide.

The acidic mining lakes of Eastern Germany are characterized by their extremely low pH and high iron concentrations. Low concentrations of CO2 in the epilimnion due to the low pH and reduced light transmission due to dissolved ferric iron potentially limit phytoplankton primary production (PP), whereas dissolved organic carbon (DOC) may promote heterotrophic production of bacteria (HP). We, therefore, tested whether HP exceeds PP in three lakes differing in pH and iron concentration (mean pH 2.3-3.0, 23-500 mg Fe L(-1)). Bacterial biomass and HP achieved highest values in the most acidic, most iron-rich lake, whereas PP was highest in the least acidic lake. HP was often higher than PP (ratio HP/PP up to 11), indicating that planktonic PP was not the main carbon source for the bacteria. HP was not related to PP and DOC, but HP as well as bacterial biomass increased with decreasing pH. Light stimulated the formation of ferrous iron, changed the DOC composition, and increased the HP in laboratory experiments, suggesting that iron photoreduction caused DOC degradation. This may explain why we found the highest HP in the most acidic and most rich lake. Overall, the importance of bacteria in the cycling of matter and as a basis for the whole food web seemed to increase in more acidic lakes with higher iron concentrations.

Vertical differences in food web structure were examined in an extremely acidic, iron-rich mining lake in Germany (Lake 111; pH 2.6, total Fe 150 mg L -1 ) during the period of stratification. We tested whether or not the seasonal variation of the plankton composition is less pronounced than the differences observed over depth. The lake was strongly stratified in summer, and concentrations of dissolved organic carbon and inorganic carbon were consistently low in the epilimnion but high in the hypolimnion. Oxygen concentrations declined in the hypolimnion but were always above 2 mg L -1 . Light attenuation did not change over depth and time and was governed by dissolved ferric iron. The plankton consisted mainly of single-celled and filamentous bacteria, the two mixotrophic flagellates Chlamydomonas sp. and Ochromonas sp., the two rotifer species Elosa worallii and Cephalodella hoodi, and Heliozoa as top predators. We observed very few ciliates and rhizopods, and no heterotrophic flagellates, crustaceans or fish. Ochromonas sp., bacterial filaments, Elosa and Heliozoa dominated in the epilimnion whereas Chlamydomonas sp., single-celled bacteria and Cephalodella dominated in the hypolimnion. Single-celled bacteria were controlled by Ochromonas sp. whereas the lack of large consumers favoured a high proportion of bacterial filaments. The primarily phototrophic Chlamydomas sp. was limited by light and CO 2 and may have been reduced due to grazing by Ochromonas sp. in the epilimnion. The distribution of the primarily phagotrophic Ochromonas sp. and of the animals seemed to be controlled by prey availability. Differences in the plankton composition were much higher between the epilimnion and hypolimnion than within a particular stratum over time. The food web in Lake 111 was extremely species-poor enabling no functional redundancy. This was attributed to the direct exclusion of species by the harsh environmental conditions and presumably enforced by competitive exclusion. The latter was promoted by the low diversity at the first trophic level which, in turn was attributed to relatively stable growth conditions and the independence of resource availability (inorganic carbon and light) from algal density. Ecological theory suggests that low functional redundancy promotes low stability in ecosystem processes which was not supported by our data.

Herbivorous fish feed on cyanobacteria. Digestability differs, however, between cyanobacteria species without mucous cover and mucilaginous genera such as Microcystis. The latter can pass fish guts almost undamaged, and it has been hypothesized that they can take up nutrients during gut passage. Here we tested whether live Microcystis, as food for juvenile roach labeled with 33P, indeed showed higher radioactivity after gut passage as compared to gut contents in control experiments with fish fed heated Microcystis. Microcystis showed high viability after passage through roach guts, and live colonies had a significantly higher radioactivity than dead ones. We conclude that Microcystis is protected against digestion in roach guts and can directly use the phosphorus supplied in the fish guts during passage.