Deconstructing Methane Emissions from a Small Northern European River: Hydrodynamics and Temperature as Key Drivers.

Methane (CH4) emissions from small rivers and streams, particularly via ebullition, are currently under-represented in the literature. Here, we quantify the methane effluxes and drivers in a small, Northern European river. Methane fluxes are comparable to those from tropical aquatic systems, with average emissions of 320 mg CH4 m-2 d-1. Two important drivers of methane flux variations were identified in the studied system: 1) temperature-driven sediment methane ebullition and 2) flow-dependent contribution suspected to be hydraulic exchange with adjacent wetlands and small side-bays. This flow-dependent contribution to river methane loading is shown to be negligible for flows less than 4 m3 s-1 and greater than 50% as flows exceed 7 m3 s-1. While the temperature-ebullition relationship is comparable to other systems, the flow rate dependency has not been previously demonstrated. In general, we found that about 80% of the total emissions were due to methane bubbles. Applying ebullition rates to global estimates for fluvial systems, which currently are not considered, could dramatically increase emission rates to ranges from lakes or wetlands. This work illustrates that small rivers can emit significant methane and highlights the need for further studies on the link between hydrodynamics and connected wetlands.

Effect of Sediment Gas Voids and Ebullition on Benthic Solute Exchange.

The presence of free gas in sediments and ebullition events can enhance the pore water transport and solute exchange across the sediment-water interface. However, we experimentally and theoretically document that the presence of free gas in sediments can counteract this enhancement effect. The apparent diffusivities (Da) of Rhodamine WT and bromide in sediments containing 8-18% gas (Da,YE) were suppressed by 7-39% compared to the control (no gas) sediments (Da,C). The measured ratios of Da,YE:Da,C were well within the range of ratios predicted by a theoretical soil model for gas-bearing soils. Whereas gas voids in sediments reduce the Da for soluble species, they represent a shortcut for low-soluble species such as methane and oxygen. Therefore, the presence of even minor amounts of gas can increase the fluxes of low-soluble species (i.e., gases) by several factors, while simultaneously suppressing fluxes of dissolved species.

Enhancing surface methane fluxes from an oligotrophic lake: exploring the microbubble hypothesis.

Exchange of the greenhouse gases carbon dioxide (CO2) and methane (CH4) across inland water surfaces is an important component of the terrestrial carbon (C) balance. We investigated the fluxes of these two gases across the surface of oligotrophic Lake Stechlin using a floating chamber approach. The normalized gas transfer rate for CH4 (k600,CH4) was on average 2.5 times higher than that for CO2 (k600,CO2) and consequently higher than Fickian transport. Because of its low solubility relative to CO2, the enhanced CH4 flux is possibly explained by the presence of microbubbles in the lake's surface layer. These microbubbles may originate from atmospheric bubble entrainment or gas supersaturation (i.e., O2) or both. Irrespective of the source, we determined that an average of 145 L m(­2) d(­1) of gas is required to exit the surface layer via microbubbles to produce the observed elevated k600,CH4. As k600 values are used to estimate CH4 pathways in aquatic systems, the presence of microbubbles could alter the resulting CH4 and perhaps C balances. These microbubbles will also affect the surface fluxes of other sparingly soluble gases in inland waters, including O2 and N2.

Sediment trapping by dams creates methane emission hot spots.

Inland waters transport and transform substantial amounts of carbon and account for ∼18% of global methane emissions. Large reservoirs with higher areal methane release rates than natural waters contribute significantly to freshwater emissions. However, there are millions of small dams worldwide that receive and trap high loads of organic carbon and can therefore potentially emit significant amounts of methane to the atmosphere. We evaluated the effect of damming on methane emissions in a central European impounded river. Direct comparison of riverine and reservoir reaches, where sedimentation in the latter is increased due to trapping by dams, revealed that the reservoir reaches are the major source of methane emissions (∼0.23 mmol CH4 m(-2) d(-1) vs ∼19.7 mmol CH4 m(-2) d(-1), respectively) and that areal emission rates far exceed previous estimates for temperate reservoirs or rivers. We show that sediment accumulation correlates with methane production and subsequent ebullitive release rates and may therefore be an excellent proxy for estimating methane emissions from small reservoirs. Our results suggest that sedimentation-driven methane emissions from dammed river hot spot sites can potentially increase global freshwater emissions by up to 7%.

Evaluation of the methane paradox in four adjacent pre-alpine lakes across a trophic gradient.

Contrasting the paradigm that methane is only produced in anoxic conditions, recent discoveries show that oxic methane production (OMP, aka the methane paradox) occurs in oxygenated surface waters worldwide. OMP drivers and their contribution to global methane emissions, however, are not well constrained. In four adjacent pre-alpine lakes, we determine the net methane production rates in oxic surface waters using two mass balance approaches, accounting for methane sources and sinks. We find that OMP occurs in three out of four studied lakes, often as the dominant source of diffusive methane emissions. Correlations of net methane production versus chlorophyll-a, Secchi and surface mixed layer depths suggest a link with photosynthesis and provides an empirical upscaling approach. As OMP is a methane source in direct contact with the atmosphere, a better understanding of its extent and drivers is necessary to constrain the atmospheric methane contribution by inland waters.

Contribution of oxic methane production to surface methane emission in lakes and its global importance.

Recent discovery of oxic methane production in sea and lake waters, as well as wetlands, demands re-thinking of the global methane cycle and re-assessment of the contribution of oxic waters to atmospheric methane emission. Here we analysed system-wide sources and sinks of surface-water methane in a temperate lake. Using a mass balance analysis, we show that internal methane production in well-oxygenated surface water is an important source for surface-water methane during the stratified period. Combining our results and literature reports, oxic methane contribution to emission follows a predictive function of littoral sediment area and surface mixed layer volume. The contribution of oxic methane source(s) is predicted to increase with lake size, accounting for the majority (>50%) of surface methane emission for lakes with surface areas >1 km2.

The phantom midge menace: Migratory Chaoborus larvae maintain poor ecosystem state in eutrophic inland waters.

Chaoborus spp. (phantom midge) are prevalent in eutrophic inland waters. In Lake Soppen, Switzerland, C. flavicans larvae diurnally migrate between the methane-rich, oxygen-depleted hypolimnion and sediments, and the methane-poor, oxygen-rich epilimnion. Using a combination of experiments and system modelling, this study demonstrated that the larvae's burrowing activities in and out of the sediment perturbed the sediment and re-introduced sequestered phosphorus into the overlying water at a rate of 0.022 µg P ind-1 d-1, thereby exacerbating internal nutrient loading in the water column. Fluxes of sediment methane and other reduced solutes enhanced by the larval bioturbation would consume oxygen and sustain the hypoxic/anoxic condition below the thermocline. In addition to increasing diffusive fluxes, migrating larvae also directly transported methane in their gas vesicles from the deep water and release it in the surface water at a rate of 0.99 nmol CH4 ind-1 d-1, potentially contributing to methane emission to air. As nutrient pollution and climate warming persist or worsen in the coming decades, proliferation of Chaoborus could intensify this positive feedback loop and delay lake recovery.

Porewater methane transport within the gas vesicles of diurnally migrating Chaoborus spp.: An energetic advantage.

Diurnally-migrating Chaoborus spp. reach populations of up to 130,000 individuals m-2 in lakes up to 70 meters deep on all continents except Antarctica. Linked to eutrophication, migrating Chaoborus spp. dwell in the anoxic sediment during daytime and feed in the oxic surface layer at night. Our experiments show that by burrowing into the sediment, Chaoborus spp. utilize the high dissolved gas partial pressure of sediment methane to inflate their tracheal sacs. This mechanism provides a significant energetic advantage that allows the larvae to migrate via passive buoyancy rather than more energy-costly swimming. The Chaoborus spp. larvae, in addition to potentially releasing sediment methane bubbles twice a day by entering and leaving the sediment, also transport porewater methane within their gas vesicles into the water column, resulting in a flux of 0.01-2 mol m-2 yr-1 depending on population density and water depth. Chaoborus spp. emerging annually as flies also result in 0.1-6 mol m-2 yr-1 of carbon export from the system. Finding the tipping point in lake eutrophication enabling this methane-powered migration mechanism is crucial for ultimately reconstructing the geographical expansion of Chaoborus spp., and the corresponding shifts in the lake's biogeochemistry, carbon cycling and food web structure.

The Chaoborus pump: Migrating phantom midge larvae sustain hypolimnetic oxygen deficiency and nutrient internal loading in lakes.

Hypolimnetic oxygen demand in lakes is often assumed to be driven mainly by sediment microbial processes, while the role of Chaoborus larvae, which are prevalent in eutrophic lakes with hypoxic to anoxic bottoms, has been overlooked. We experimentally measured the respiration rates of C. flavicans at different temperatures yielding a Q10 of 1.44-1.71 and a respiratory quotient of 0.84-0.98. Applying the experimental data in a system analytical approach, we showed that migrating Chaoborus larvae can significantly add to the water column and sediment oxygen demand, and contribute to the observed linear relationship between water column respiration and depth. The estimated phosphorus excretion by Chaoborus in sediment is comparable in magnitude to the required phosphorus loading for eutrophication. Migrating Chaoborus larvae thereby essentially trap nutrients between the water column and the sediment, and this continuous internal loading of nutrients would delay lake remediation even when external inputs are stopped.

Aquatic eddy correlation: quantifying the artificial flux caused by stirring-sensitive O2 sensors.

In the last decade, the aquatic eddy correlation (EC) technique has proven to be a powerful approach for non-invasive measurements of oxygen fluxes across the sediment water interface. Fundamental to the EC approach is the correlation of turbulent velocity and oxygen concentration fluctuations measured with high frequencies in the same sampling volume. Oxygen concentrations are commonly measured with fast responding electrochemical microsensors. However, due to their own oxygen consumption, electrochemical microsensors are sensitive to changes of the diffusive boundary layer surrounding the probe and thus to changes in the ambient flow velocity. The so-called stirring sensitivity of microsensors constitutes an inherent correlation of flow velocity and oxygen sensing and thus an artificial flux which can confound the benthic flux determination. To assess the artificial flux we measured the correlation between the turbulent flow velocity and the signal of oxygen microsensors in a sealed annular flume without any oxygen sinks and sources. Experiments revealed significant correlations, even for sensors designed to have low stirring sensitivities of ~0.7%. The artificial fluxes depended on ambient flow conditions and, counter intuitively, increased at higher velocities because of the nonlinear contribution of turbulent velocity fluctuations. The measured artificial fluxes ranged from 2-70 mmol m(-2) d(-1) for weak and very strong turbulent flow, respectively. Further, the stirring sensitivity depended on the sensor orientation towards the flow. For a sensor orientation typically used in field studies, the artificial flux could be predicted using a simplified mathematical model. Optical microsensors (optodes) that should not exhibit a stirring sensitivity were tested in parallel and did not show any significant correlation between O2 signals and turbulent flow. In conclusion, EC data obtained with electrochemical sensors can be affected by artificial flux and we recommend using optical microsensors in future EC-studies.

Predicting diffused-bubble oxygen transfer rate using the discrete-bubble model.

A discrete-bubble model that predicts the rate of oxygen transfer in diffused-bubble systems is evaluated. Key inputs are the applied gas flow rate and the initial bubble size distribution. The model accounts for changes in the volume of individual bubbles due to transfer of oxygen and nitrogen (and hence changing partial pressure), variation in hydrostatic pressure, and changes in temperature. The bubble-rise velocity and mass-transfer coefficient, both known functions of the bubble diameter, are continually adjusted. The model is applied to predict the results of diffused-bubble oxygen transfer tests conducted in a 14-m deep tank at three air flow rates. All of the test data are predicted to within 15%. The range of bubble diameters (0.2-2 mm) spans the region of greatest variation in rise velocity and mass-transfer coefficient. For simplicity, the Sauter-mean diameter is used rather than the full bubble size distribution without loss of accuracy. The model should prove useful in the design and optimization of hypolimnetic oxygenation systems, as well as other diffused-bubble applications.

Predicting oxygen transfer and water flow rate in airlift aerators.

Water flow rate, gas-phase holdup, and dissolved oxygen (DO) profiles are measured in a full-scale airlift aerator as a function of applied air flow rate. A model that predicts oxygen transfer based on discrete-bubble principles is applied. The riser DO profiles are used to calculate the initial bubble size. The range of calculated bubble diameters obtained using the model is 2.3-3.1 mm. The Sauter-mean diameter of bubbles measured in the laboratory ranged from 2.7 to 3.9 mm. The riser and downcomer DO profiles and gas holdups predicted by the model are in close agreement with the experimental results. A model that predicts water flow rate based on an energy balance is used to calculate Kt, the frictional loss coefficient for the air-water separator. Excluding the data at the very lowest air flow rate, the range of calculated values for Kt (3-8) is close to a literature value of 5.5 proposed for hydrodynamically similar external airlift bioreactors. The models should prove useful in the design and optimization of airlift aerators.

Extreme methane emissions from a Swiss hydropower reservoir: contribution from bubbling sediments.

Methane emission pathways and their importance were quantified during a yearlong survey of a temperate hydropower reservoir. Measurements using gas traps indicated very high ebullition rates, but due to the stochastic nature of ebullition a mass balance approach was crucial to deduce system-wide methane sources and losses. Methane diffusion from the sediment was generally low and seasonally stable and did not account for the high concentration of dissolved methane measured in the reservoir discharge. A strong positive correlation between water temperature and the observed dissolved methane concentration enabled us to quantify the dissolved methane addition from bubble dissolution using a system-wide mass balance. Finally, knowing the contribution due to bubble dissolution, we used a bubble model to estimate bubble emission directly to the atmosphere. Our results indicated that the total methane emission from Lake Wohlen was on average >150 mg CH(4) m(-2) d(-1), which is the highest ever documented for a midlatitude reservoir. The substantial temperature-dependent methane emissions discovered in this 90-year-old reservoir indicate that temperate water bodies can be an important but overlooked methane source.

Linking crenarchaeal and bacterial nitrification to anammox in the Black Sea.

Active expression of putative ammonia monooxygenase gene subunit A (amoA) of marine group I Crenarchaeota has been detected in the Black Sea water column. It reached its maximum, as quantified by reverse-transcription quantitative PCR, exactly at the nitrate maximum or the nitrification zone modeled in the lower oxic zone. Crenarchaeal amoA expression could explain 74.5% of the nitrite variations in the lower oxic zone. In comparison, amoA expression by gamma-proteobacterial ammonia-oxidizing bacteria (AOB) showed two distinct maxima, one in the modeled nitrification zone and one in the suboxic zone. Neither the amoA expression by crenarchaea nor that by beta-proteobacterial AOB was significantly elevated in this latter zone. Nitrification in the suboxic zone, most likely microaerobic in nature, was verified by (15)NO(2)(-) and (15)N(15)N production in (15)NH(4)(+) incubations with no measurable oxygen. It provided a direct local source of nitrite for anammox in the suboxic zone. Both ammonia-oxidizing crenarchaea and gamma-proteobacterial AOB were important nitrifiers in the Black Sea and were likely coupled to anammox in indirect and direct manners respectively. Each process supplied about half of the nitrite required by anammox, based on (15)N-incubation experiments and modeled calculations. Because anammox is a major nitrogen loss in marine suboxic waters, such nitrification-anammox coupling potentially occurring also in oceanic oxygen minimum zones would act as a short circuit connecting regenerated ammonium to direct nitrogen loss, thus reducing the presumed direct contribution from deep-sea nitrate.