Complete exhaustion of dissolved nutrients in a large lowland river.

Riverine phytoplankton takes up phosphate, dissolved silicate, and nitrate. We investigated which nutrients are depleted during a Lagrangian sampling in the free-flowing part of the River Elbe in 2023. As part of this study, we tested the hypotheses that nutrient depletion might be caused by (1) above-average phytoplankton biomass or by (2) decreased nutrient load of the river during previous years. Phytoplankton biomass increased up to 350 km in rivers and stopped increasing exactly when soluble reactive phosphorus had been completely consumed, and molar carbon to phosphorus ratios of seston indicated the beginning phosphorus limitation. The concentrations of dissolved silicate and nitrate dropped below the detection limit as well. In contrast to the results from eight previous longitudinal samplings taken in 2018-2022, nitrate exhaustion was detected for the first time in 2023 within the transect. This was caused neither by an above-average phytoplankton biomass nor by a declined overall nutrient load of the river in 2018-2023. Instead, denitrification appears to be the most plausible explanation for the downstream decrease of nitrate and the loss of total nitrogen which was supported by enrichment of nitrate stable isotopes and a decreasing ratio of nitrate 15N/18O.

Improved Understanding of Dissolved Organic Matter Processing in Freshwater Using Complementary Experimental and Machine Learning Approaches.

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.

Tracing Aquatic Priming Effect During Microbial Decomposition of Terrestrial Dissolved Organic Carbon in Chemostat Experiments.

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 <1.0 and O/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.

Effects of light and autochthonous carbon additions on microbial turnover of allochthonous organic carbon and community composition.

The fate of allochthonous dissolved organic carbon (DOC) in aquatic systems is primarily controlled by the turnover of heterotrophic bacteria. However, the roles that abiotic and biotic factors such as light and DOC release by aquatic primary producers play in the microbial decomposition of allochthonous DOC is not well understood. We therefore tested if light and autochthonous DOC additions would increase allochthonous DOC decomposition rates and change bacterial growth efficiencies and community composition (BCC). We established continuous growth cultures with different inocula of natural bacterial communities and alder leaf leachates (DOCleaf) with and without light exposure before amendment. Furthermore, we incubated DOCleaf together with autochthonous DOC from lysed phytoplankton cultures (DOCphyto). Our results revealed that pretreatments of DOCleaf with light resulted in a doubling of bacterial growth efficiency (BGE), whereas additions of DOCphyto or combined additions of DOCphyto and light had no effect on BGE. The change in BGE was not accompanied by shifts in the phylogenetic structure of the BCC, but BCC was influenced by the DOC source. Our results highlight that a doubling of BGE is not necessarily accompanied by a shift in BCC and that BCC is more strongly affected by resource properties.

Relationship between the elemental composition of stream biofilms and water chemistry-a catchment approach.

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.

Biogeochemical patterns in a river network along a land use gradient.

The Bode catchment (Germany) shows strong land use gradients from forested parts of the National Park (23% of total land cover) to agricultural (70%) and urbanised areas (7%). It is part of the Terrestrial Environmental Observatories of the German Helmholtz association. We performed a biogeochemical analysis of the entire river network. Surface water was sampled at 21 headwaters and at ten downstream sites, before (in early spring) and during the growing season (in late summer). Many parameters showed lower concentrations in headwaters than in downstream reaches, among them nutrients (ammonium, nitrate and phosphorus), dissolved copper and seston dry mass. Nitrate and phosphorus concentrations were positively related to the proportion of agricultural area within the catchment. Punctual anthropogenic loads affected some parameters such as chloride and arsenic. Chlorophyll a concentration and total phosphorus in surface waters were positively related. The concentration of dissolved organic carbon (DOC) was higher in summer than in spring, whereas the molecular size of DOC was lower in summer. The specific UV absorption at 254 nm, indicating the content of humic substances, was higher in headwaters than in downstream reaches and was positively related to the proportion of forest within the catchment. CO2 oversaturation of the water was higher downstream compared with headwaters and was higher in summer than in spring. It was correlated negatively with oxygen saturation and positively with DOC concentration but negatively with DOC quality (molecular size and humic content). A principle component analysis clearly separated the effects of site (44%) and season (15%), demonstrating the strong effect of land use on biogeochemical parameters.

Data evaluation strategy for identification of key molecular formulas in dissolved organic matter as proxies for biogeochemical reactivity based on abundance differences from ultrahigh resolution mass spectrometry.

The molecular composition of dissolved organic matter (DOM) is of relevance for global carbon cycling and important for drinking water processing also. The detection of variation of DOM composition as function of time and space from a methodological viewpoint is essential to observe DOM processing and was addressed so far. High resolution concerning DOM quality was achieved with Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS). However almost none of the existing FTICR-MS data sets were evaluated addressing the fate of single mass features / molecular formulas (MFs) abundance during experiments. In contrast to former studies we analyze the function of MF abundance of time and space for such MFs which are present in all samples and which were formerly claimed as recalcitrant in not all but a great number of studies. For the first time the reactivity of MFs was directly compared by their abundance differences using a simple equation, the relative intensity difference (δRI). Search strategies to find out the maximum δRI values are introduced. The corresponding MFs will be regarded as key MFs (KEY-MFs). In order to test this new approach data from a recent photo degradation experiment were combined with monitoring surveys conducted in two drinking water reservoirs. The δRI values varied over one order of magnitude (more than five-fold). MFs like C9H12O6 and C10H14O6 revealed high biogeochemical reactivity as photo products. Some of the KEY-MFs were identical with MFs identified as disinfection byproducts precursors in recent studies. Other KEY-MFs were oxygen-rich and relatively unsaturated (poly-phenol-like) and hence relevant to flocculation procedures.

Large-scale nutrient and carbon dynamics along the river-estuary-ocean continuum.

Nutrient and carbon dynamics within the river-estuary-coastal water systems are key processes in understanding the flux of matter from the terrestrial environment to the ocean. Here, we analysed those dynamics by following a sampling approach based on the travel time of water and an advanced calculation of nutrient fluxes in the tidal part. We started with a nearly Lagrangian sampling of the river (River Elbe, Germany; 580 km within 8 days). After a subsequent investigation of the estuary, we followed the plume of the river by raster sampling the German Bight (North Sea) using three ships simultaneously. In the river, we detected intensive longitudinal growth of phytoplankton connected with high oxygen saturation and pH values and an undersaturation 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 shelf region, phytoplankton and nutrient concentrations were low, oxygen was close to saturation, and pH was within a typical marine range. Over all sections, oxygen saturation was positively related to pH and negatively to pCO2. Corresponding to the significant particulated nutrient flux via phytoplankton, flux rates of dissolved nutrients from river into 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 current. Overall, the approach is appropriate to better understand land-ocean fluxes, particularly to illuminate the importance of these fluxes under different seasonal and hydrological conditions, including flood and drought events.

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

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

Pesticides are the dominant stressors for vulnerable insects in lowland streams.

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.

Disentangling multiple chemical and non-chemical stressors in a lotic ecosystem using a longitudinal approach.

Meeting ecological and water quality standards in lotic ecosystems is often failed due to multiple stressors. However, disentangling stressor effects and identifying relevant stressor-effect-relationships in complex environmental settings remain major challenges. By combining state-of-the-art methods from ecotoxicology and aquatic ecosystem analysis, we aimed here to disentangle the effects of multiple chemical and non-chemical stressors along a longitudinal land use gradient in a third-order river in Germany. We distinguished and evaluated four dominant stressor categories along this gradient: (1) Hydromorphological alterations: Flow diversity and substrate diversity correlated with the EU-Water Framework Directive based indicators for the quality element macroinvertebrates, which deteriorated at the transition from near-natural reference sites to urban sites. (2) Elevated nutrient levels and eutrophication: Low to moderate nutrient concentrations together with complete canopy cover at the reference sites correlated with low densities of benthic algae (biofilms). We found no more systematic relation of algal density with nutrient concentrations at the downstream sites, suggesting that limiting concentrations are exceeded already at moderate nutrient concentrations and reduced shading by riparian vegetation. (3) Elevated organic matter levels: Wastewater treatment plants (WWTP) and stormwater drainage systems were the primary sources of bioavailable dissolved organic carbon. Consequently, planktonic bacterial production and especially extracellular enzyme activity increased downstream of those effluents showing local peaks. (4) Micropollutants and toxicity-related stress: WWTPs were the predominant source of toxic stress, resulting in a rapid increase of the toxicity for invertebrates and algae with only one order of magnitude below the acute toxic levels. This toxicity correlates negatively with the contribution of invertebrate species being sensitive towards pesticides (SPEARpesticides index), probably contributing to the loss of biodiversity recorded in response to WWTP effluents. Our longitudinal approach highlights the potential of coordinated community efforts in supplementing established monitoring methods to tackle the complex phenomenon of multiple stress.

Similar bacterial community composition in acidic mining lakes with different pH and lake chemistry.

As extreme environmental conditions strongly affect bacterial community composition (BCC), we examined whether differences in pH-even at low pH-and in iron and sulfate concentrations lead to changes in BCC of acidic mining lakes. Thereby, we tested the following hypotheses: (1) diversity of the bacterial community in acidic lakes decreases with reducing pH, (2) BCC differs between epilimnion and hypolimnion, and (3) BCC in extremely acidic environments does not vary much over time. Therefore, we investigated the BCC of three acidic lakes with different pH values (2.3, 2.7, and 3.2) by denaturing gradient gel electrophoresis (DGGE) and subsequent sequencing of DGGE bands as well as catalyzed reporter deposition-FISH (CARD-FISH). BCC did not significantly vary among the studied lakes nor differ much between water layers. In contrast, BCC significantly changed over time, which is contradictory to our hypotheses. Bacterial communities were dominated by Alpha-, Beta-, and Gammaproteobacteria, whereas Actino- and Acidobacteria rarely occurred. Cell numbers of both free and attached bacteria were positively related to DOC concentration. Overall, low pH and extreme chemical conditions of the studied lakes led to similar assemblages of bacteria with pronounced temporal differences. This notion indicates that temporal changes in environmental conditions including food web structure also affect unique communities of bacteria thriving at low pH.

Lake morphometry and wind exposure may shape the plankton community structure in acidic mining lakes.

Acidic mining lakes (pH <3) are specific habitats exhibiting particular chemical and biological characteristics. The species richness is low and mixotrophy and omnivory are common features of the plankton food web in such lakes. The plankton community structure of mining lakes of different morphometry and mixing type but similar chemical characteristics (Lake 130, Germany and Lake Langau, Austria) was investigated. The focus was laid on the species composition, the trophic relationship between the phago-mixotrophic flagellate Ochromonas sp. and bacteria and the formation of a deep chlorophyll maximum along a vertical pH-gradient. The shallow wind-exposed Lake 130 exhibited a higher species richness than Lake Langau. This increase in species richness was made up mainly by mero-planktic species, suggesting a strong benthic/littoral - pelagic coupling. Based on the field data from both lakes, a nonlinear, negative relation between bacteria and Ochromonas biomass was found, suggesting that at an Ochromonas biomass below 50 µg C L(-1), the grazing pressure on bacteria is low and with increasing Ochromonas biomass bacteria decline. Furthermore, in Lake Langau, a prominent deep chlorophyll maximum was found with chlorophyll concentrations ca. 50 times higher than in the epilimnion which was build up by the euglenophyte Lepocinclis sp. We conclude that lake morphometry, and specific abiotic characteristics such as mixing behaviour influence the community structure in these mining lakes.

Molecular change of dissolved organic matter and patterns of bacterial activity in a stream along a land-use gradient.

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.

Polymerized coumaric acid as a model substrate for terrestrial-derived dissolved organic carbon utilized by aquatic microorganisms.

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.

Going with the flow: Planktonic processing of dissolved organic carbon in streams.

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.

Discharge determines production of, decomposition of and quality changes in dissolved organic carbon in pre-dams of drinking water reservoirs.

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 (ß/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.

A new approach for evaluating transformations of dissolved organic matter (DOM) via high-resolution mass spectrometry and relating it to bacterial activity.

Streams are important sites of transformation of dissolved organic matter (DOM). The molecular characterization of DOM-quality changes requires sophisticated analytical evaluation techniques. The goal of our study was to link molecular DOM transformation with bacterial activity. We measured the degradation of leaf leachate over a gradient of bacterial production obtained by different rates of percolation of sediments in seven experimental flumes on five sampling dates. We developed a new strategy for evaluating molecular formula data sets obtained by ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS), in which the time-dependent change of component abundance was fitted by a linear regression model after normalization of mass peak intensities. All components were categorized by calculating the slope (change of percent intensity per day) in each of the seven flumes. These slopes were then related to cumulative bacterial production. The concentration of DOM decreased quickly in all flumes. Bacterial activity was higher in flumes with percolated sediment than in those without percolation, whereas plankton bacterial activity was higher in flumes without percolation or without sediment. There were no differences in molecular-DOM characteristics between flumes, but there were distinct changes over time. Positive slopes, i.e. increasing intensities over time, were found for small molecules (MW < 450 Da) and high O/C ratios, whereas decreasing intensities were observed less often and only for large molecules and low O/C ratios. The positive slopes of produced components showed a positive relationship to bacterial production for small and for oxygen-rich components. The negative slopes of degraded components were negatively related to bacterial production for large and for oxygen-deficient molecules. Overall, the approach provided new insights into the transformation of specific molecular DOM components.

Land-based salmon aquacultures change the quality and bacterial degradation of riverine dissolved organic matter.

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.