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.

High temperature noble gas thermometry in Lake Kivu, East Africa.

Due to their biological and chemical inertness, noble gases in natural waters are widely used to trace natural waters and to determine ambient temperature conditions during the last intensive contact with the atmosphere (equilibration). Noble gas solubilities are strong functions of temperature, with higher temperatures resulting in lower concentrations. Thus far, only common environmental conditions have been considered, and hence investigated temperatures have almost never exceeded 35 °C, but environmental scenarios that generate higher surface-water temperatures (such as volcanism) exist nonetheless. Recently published measurements of noble gas concentrations in Lake Kivu, which sits at the base of the Nyiragongo volcano in East Africa, unexpectedly show that the deep waters are strongly depleted in noble gases with respect to in-situ conditions, and so far no quantitative explanation for this observation has been provided. We make use of recently published noble gas solubility data at higher temperatures to investigate our hypothesis that unusually high equilibration temperatures could have caused the low measured noble gas concentrations by applying various approaches of noble gas thermometry. Noble gas concentration ratios and least squares fitting of individual concentrations indicate that the data agrees best with the assumption that deep water originates from groundwater formed at temperatures of about 65 °C. Thus, no form of degassing is required to explain the observed noble gas depletion: the deep water currently contained in Lake Kivu has most probably never experienced a large scale degassing event. This conclusion is important as limnic eruptions were feared to threaten the lives of the local population.

Unravelling winter diatom blooms in temperate lakes using high frequency data and ecological modeling.

In temperate lakes, it is generally assumed that light rather than temperature constrains phytoplankton growth in winter. Rapid winter warming and increasing observations of winter blooms warrant more investigation of these controls. We investigated the mechanisms regulating a massive winter diatom bloom in a temperate lake. High frequency data and process-based lake modeling demonstrated that phytoplankton growth in winter was dually controlled by light and temperature, rather than by light alone. Water temperature played a further indirect role in initiating the bloom through ice-thaw, which increased light exposure. The bloom was ultimately terminated by silicon limitation and sedimentation. These mechanisms differ from those typically responsible for spring diatom blooms and contributed to the high peak biomass. Our findings show that phytoplankton growth in winter is more sensitive to temperature, and consequently to climate change, than previously assumed. This has implications for nutrient cycling and seasonal succession of lake phytoplankton communities. The present study exemplifies the strength in integrating data analysis with different temporal resolutions and lake modeling. The new lake ecological model serves as an effective tool in analyzing and predicting winter phytoplankton dynamics for temperate lakes.

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.

No increasing risk of a limnic eruption at Lake Kivu: Intercomparison study reveals gas concentrations close to steady state.

Lake Kivu, East Africa, is well known for its huge reservoir of dissolved methane (CH4) and carbon dioxide (CO2) in the stratified deep waters (below 250 m). The methane concentrations of up to ~ 20 mmol/l are sufficiently high for commercial gas extraction and power production. In view of the projected extraction capacity of up to several hundred MW in the next decades, reliable and accurate gas measurement techniques are required to closely monitor the evolution of gas concentrations. For this purpose, an intercomparison campaign for dissolved gas measurements was planned and conducted in March 2018. The applied measurement techniques included on-site mass spectrometry of continuously pumped sample water, gas chromatography of in-situ filled gas bags, an in-situ membrane inlet laser spectrometer sensor and a prototype sensor for total dissolved gas pressure (TDGP). We present the results of three datasets for CH4, two for CO2 and one for TDGP. The resulting methane profiles show a good agreement within a range of around 5-10% in the deep water. We also observe that TDGP measurements in the deep waters are systematically around 5 to 10% lower than TDGP computed from gas concentrations. Part of this difference may be attributed to the non-trivial conversion of concentration to partial pressure in gas-rich Lake Kivu. When comparing our data to past measurements, we cannot verify the previously suggested increase in methane concentrations since 1974. We therefore conclude that the methane and carbon dioxide concentrations in Lake Kivu are currently close to a steady state.

The formation of a metalimnetic oxygen minimum exemplifies how ecosystem dynamics shape biogeochemical processes: A modelling study.

Metalimnetic oxygen minima are observed in many lakes and reservoirs, but the mechanisms behind this phenomena are not well understood. Thus, we simulated the metalimnetic oxygen minimum (MOM) in the Rappbode Reservoir with a well-established two-dimensional water quality model (CE-QUAL-W2) to systematically quantify the chain of events leading to its formation. We used high-resolution measured data to calibrate the model, which accurately reproduced the physical (e.g. water level and water temperature), biogeochemical (e.g. nutrient and oxygen dynamics) and ecological (e.g. algal community dynamics) features of the reservoir, particularly the spatial and temporal extent of the MOM. The results indicated that around 60% of the total oxygen consumption rate in the MOM layer originated from benthic processes whereas the remainder originated from pelagic processes. The occurrence of the cyanobacterium Planktothrix rubescens in the metalimnion delayed and slightly weakened the MOM through photosynthesis, although its decaying biomass ultimately induced the MOM. Our research also confirmed the decisive role of water temperature in the formation of the MOM since the water temperatures, and thus benthic and pelagic oxygen consumption rates, were higher in the metalimnion than in the hypolimnion. Our model is not only providing novel conclusions about the drivers of MOM development and their quantitative contributions, it is also a new tool for understanding and predicting ecological and biogeochemical water quality dynamics.

High frequency data provide new insights into evaluating and modeling nitrogen retention in reservoirs.

Freshwater ecosystems including lakes and reservoirs are hot spots for retention of excess nitrogen (N) from anthropogenic sources, providing valuable ecological services for downstream and coastal ecosystems. Despite previous investigations, current quantitative understanding on the influential factors and underlying mechanisms of N retention in lentic freshwater systems is insufficient due to data paucity and limitation of modeling techniques. Our ability to reliably predict N retention for these systems therefore remains uncertain. Emerging high frequency monitoring techniques and well-developed ecosystem modeling shed light on this issue. In the present study, we explored the retention of NO3-N during a five-year period (2013-2017) in both annual and weekly scales in a highly flushed reservoir in Germany. We found that annual-averaged NO3-N retention efficiency could be up to 17% with an overall retention efficiency of ∼4% in such a system characterized by a water residence time (WRT) of ∼4 days. On the weekly scale, the reservoir displayed negative retention in winter (i.e. a source of NO3-N) and high positive retention in summer (i.e. a sink for NO3-N). We further identified the critical role of Chl-a concentration together with the well-recognized effects from WRT in dictating NO3-N retention efficiency, implying the significance of biological processes including phytoplankton dynamics in driving NO3-N retention. Furthermore, our modeling approach showed that an established process-based ecosystem model (PCLake) accounted for 58.0% of the variance in NO3-N retention efficiency, whereas statistical models obtained a lower value (40.5%). This finding exemplified the superior predictive power of process-based models over statistical models whenever ecological processes were at play. Overall, our study highlights the importance of high frequency data in providing new insights into evaluating and modeling N retention in reservoirs.

Metalimnetic oxygen minimum and the presence of Planktothrix rubescens in a low-nutrient drinking water reservoir.

Dissolved oxygen is a key player in water quality. Stratified water bodies show distinct vertical patterns of oxygen concentration, which can originate from physical, chemical or biological processes. We observed a pronounced metalimnetic oxygen minimum in the low-nutrient Rappbode Reservoir, Germany. Contrary to the situation in the hypolimnion, measurements of lateral gradients excluded the sediment contact zone from the major sources of oxygen depletion for the metalimnetic oxygen minimum. Instead, the minimum was the result of locally enhanced oxygen consumption in the open water body. A follow-up monitoring included multiple chlorophyll a fluorescence sensors with high temporal and vertical resolution to detect and document the evolution of phytoplankton. While chlorophyll fluorescence sensors with multiple channels detected a mass development of the phycoerythrin-rich cyanobacterium Planktothrix rubescens in the metalimnion, this species was overlooked by the commonly used single-channel chlorophyll sensor. The survey indicated that the waning P. rubescens fluorescence was responsible for the oxygen minimum in the metalimnion. We hypothesize that pelagic processes, i.e., either oxygen use through decomposition of dead organic material originating from P. rubescens or P. rubescens extending its respiration beyond its photosynthetic activity, induced the metalimnetic oxygen minimum. The deeper understanding of the oxygen dynamics is mandatory for optimizing reservoir management.

Methane storage and ebullition in monimolimnetic waters of polluted mine pit lake Vollert-Sued, Germany.

Reliable gas measurements from supersaturated deep waters still remain a challenge. However, good information is mandatory to investigate the limnic carbon cycle, assess the endangerment through limnic eruptions and evaluate a potential source of exploitable energy. We addressed these three points in a heavily polluted mine pit lake in Germany. We quantified the ebullition of methane from deep waters and the sediment below. Exposed to continuous percolation of gas bubbles, the deep (monimolimnetic) water had accumulated high concentrations of gas: directly measured gas pressures indicated the proximity to spontaneous ebullition. Consequently, the possibility of a limnic eruption was assessed by initiating a self-sustained flow through a vertical pipe. Despite the high gas pressures, the flow was slow and the endangerment was considered low. A sampling strategy with bags was developed to achieve a reliable measurement of gas content and gas composition in the monimolimnion. As a result, directly measured gas pressures could be confirmed and were nearly exclusively attributed to methane and nitrogen. Contrary to lakes that had shown limnic eruptions, carbon dioxide played a much subordinate role, and hence the driving force for a violent outburst of gases was missing. Nevertheless the amount of dissolved methane was remarkably high. This investigation closes with some estimates of the commercial value of the deposit and limiting conditions for a possible exploitation.

Quantifying, assessing and removing the extreme gas load from meromictic Guadiana pit lake, Southwest Spain.

High gas charges in deep waters of lakes can represent a hazard to the lives of human beings and animals in the surrounding. As this danger was feared, we quantified the amount of dissolved gas in Guadiana pit lake (Las Herrerías, Huelva; southwest Spain) and documented the temporal evolution over a period of two years. Gas pressure due to dissolved gases, such as carbon dioxide, methane and nitrogen was measured. Based on these data, we assessed the risk and the associated danger of limnic eruptions from the lake and concluded that the present situation cannot be considered safe. By deploying a vertical pipe, the updraft of degassing water was tested and demonstrated: the pilot plant provided enough energy to drive a self-sustained flow. Such a system could be implemented to remove the extreme gas pressure from the deep water. Measurements of discharges could be extrapolated to indicate the size for an efficient plant for the gas removal. The construction of such a system would be technically and economically viable. A reintroduction of degassed water into the monimolimnion would be advisable.

Extreme carbon dioxide concentrations in acidic pit lakes provoked by water/rock interaction.

We quantify the gas pressure and concentration of a gas-charged acidic pit lake in SW Spain. We measured total dissolved gas pressure, carbon dioxide (CO2) concentration, major ion concentration, isotopic composition of dissolved inorganic carbon (δ(13)C(DIC)), and other physicochemical parameters. CO2 is the dominant dissolved gas in this lake and results mainly from carbonate dissolution during the interaction of acidic water with wall rocks, followed by diffusive and advective transport through the water column. The δ(13)C(DIC) values suggest that the biological contribution is comparatively small. Maximum CO2 concentrations higher than 0.1 M (∼5000 mg/L) have been measured, which are only comparable to those found in volcanic crater lakes. The corresponding gas pressures of CO2 alone (pCO2 ∼3.6 bar) imply 60% saturation relative to local pressure at 50 m depth. High CO2 concentrations have been observed in other pit lakes of the region. We recommend gas-specific monitoring in acidic pit lakes and, if necessary, the design of feasible degassing strategies.

Complementary ecophysiological strategies combine to facilitate survival in the hostile conditions of a deep chlorophyll maximum.

In the deep, cooler layers of clear, nutrient-poor, stratified water bodies, phytoplankton often accumulate to form a thin band or "deep chlorophyll maximum" (DCM) of ecological importance. Under such conditions, these photosynthetic microorganisms may be close to their physiological compensation points and to the boundaries of their ecological tolerance. To grow and survive any resulting energy limitation, DCM species are thought to exhibit highly specialised or flexible acclimation strategies. In this study, we investigated several of the adaptable ecophysiological strategies potentially employed by one such species, Chlamydomonas acidophila: a motile, unicellular, phytoplanktonic flagellate that often dominates the DCM in stratified, acidic lakes. Physiological and behavioural responses were measured in laboratory experiments and were subsequently related to field observations. Results showed moderate light compensation points for photosynthesis and growth at 22°C, relatively low maintenance costs, a behavioural preference for low to moderate light, and a decreased compensation point for photosynthesis at 8°C. Even though this flagellated alga exhibited a physiologically mediated diel vertical migration in the field, migrating upwards slightly during the day, the ambient light reaching the DCM was below compensation points, and so calculations of daily net photosynthetic gain showed that survival by purely autotrophic means was not possible. Results suggested that strategies such as low-light acclimation, small-scale directed movements towards light, a capacity for mixotrophic growth, acclimation to low temperature, in situ exposure to low O(2), high CO(2) and high P concentrations, and an avoidance of predation, could combine to help overcome this energetic dilemma and explain the occurrence of the DCM. Therefore, corroborating the deceptive ecophysiological complexity of this and similar organisms, only a suite of complementary strategies can facilitate the survival of C. acidophila in this DCM.

Water column anammox and denitrification in a temperate permanently stratified lake (Lake Rassnitzer, Germany).

We studied microbial N(2) production via anammox and denitrification in the anoxic water column of a restored mining pit lake in Germany over an annual cycle. We obtained high-resolution hydrochemical profiles using a continuous pumping sampler. Lake Rassnitzer is permanently stratified at ca. 29m depth, entraining anoxic water below a saline density gradient. Mixed-layer nitrate concentrations averaged ca. 200 micromol L(-1), but decreased to zero in the anoxic bottom waters. In contrast, ammonium was <5 micromol L(-1) in the mixed layer but increased in the anoxic waters to ca. 600 micromol L(-1) near the sediments. In January and October, (15)N tracer measurements detected anammox activity (maximum 504 nmol N(2)L(-1)d(-1) in (15)NH(4)(+)-amended incubations), but no denitrification. In contrast, in May, N(2) production was dominated by denitrification (maximum 74 nmol N(2)L(-1)d(-1)). Anammox activity in May was significantly lower than in October, as characterized by anammox rates (maximum 6 vs. 16 nmol N(2)L(-1)d(-1) in incubations with (15)NO(3)(-)), as well as relative and absolute anammox bacterial cell abundances (0.56% vs. 0.98% of all bacteria, and 2.7x10(4) vs. 5.2x10(4)anammox cells mL(-1), respectively) (quantified by catalyzed reporter deposition-fluorescence in situ hybridization (CARD-FISH) with anammox bacteria-specific probes). Anammox bacterial diversity was investigated with anammox bacteria-specific 16S rRNA gene clone libraries. The majority of anammox bacterial sequences were related to the widespread Candidatus Scalindua sorokinii/brodae cluster. However, we also found sequences related to Candidatus S. wagneri and Candidatus Brocadia fulgida, which suggests a high anammox bacterial diversity in this lake comparable with estuarine sediments.