Integrating terrestrial and aquatic ecosystems to constrain estimates of land-atmosphere carbon exchange.

In this Perspective, we put forward an integrative framework to improve estimates of land-atmosphere carbon exchange based on the accumulation of carbon in the landscape as constrained by its lateral export through rivers. The framework uses the watershed as the fundamental spatial unit and integrates all terrestrial and aquatic ecosystems as well as their hydrologic carbon exchanges. Application of the framework should help bridge the existing gap between land and atmosphere-based approaches and offers a platform to increase communication and synergy among the terrestrial, aquatic, and atmospheric research communities that is paramount to advance landscape carbon budget assessments.

Large-scale sampling of the freshwater microbiome suggests pollution-driven ecosystem changes.

Freshwater microbes play a crucial role in the global carbon cycle. Anthropogenic stressors that lead to changes in these microbial communities are likely to have profound consequences for freshwater ecosystems. Using field data from the coordinated sampling of 617 lakes, ponds, rivers, and streams by citizen scientists, we observed linkages between microbial community composition, light and chemical pollution, and greenhouse gas concentration. All sampled water bodies were net emitters of CO2, with higher concentrations in running waters, and increasing concentrations at higher latitudes. Light pollution occurred at 75% of sites, was higher in urban areas and along rivers, and had a measurable effect on the microbial alpha diversity. Genetic elements suggestive of chemical stress and antimicrobial resistances (IntI1, blaOX58) were found in 85% of sites, and were also more prevalent in urban streams and rivers. Light pollution and CO2 were significantly related to microbial community composition, with CO2 inversely related to microbial phototrophy. Results of synchronous nationwide sampling indicate that pollution-driven alterations to the freshwater microbiome lead to changes in CO2 production in natural waters and highlight the vulnerability of running waters to anthropogenic stressors.

Modeling the spatial and temporal variability in surface water CO2 and CH4 concentrations in a newly created complex of boreal hydroelectric reservoirs.

Hydroelectric reservoirs emit carbon dioxide (CO2) and methane (CH4) to the atmosphere, yet there is still much uncertainty concerning the magnitude and drivers of these greenhouse gas (GHG) emissions. This uncertainty is particularly large over the initial years after flooding and in complex, cascade reservoir systems where studies are rare. We assessed the spatial and temporal patterns of CO2 and CH4 concentrations in the newly created La Romaine complex, which is composed of three consecutive reservoirs (RO1, RO2, RO3) along the La Romaine River. Dissolved CO2 and CH4 concentrations were intensively measured over three seasons for four years. Results show elevated CH4 and especially CO2 concentrations in surface waters of all three reservoirs upon flooding, with strong seasonality and high spatial heterogeneity within reservoirs. There was a strong seasonal decoupling of surface water CO2 and CH4 concentrations. Contrary to expectations, surface water CO2 and CH4 concentrations were relatively stable over the initial years of flooding, with exception of the decrease in CO2 concentrations in the shallower RO1 reservoir. Further, individual reservoir characteristics, notably reservoir morphometry and pre-flood land cover, together with climatic factors were the main drivers of CO2 and CH4 concentrations, and the reservoir position in the cascade played a minor role. Models differed for CO2 and CH4, and also between reservoirs highlighting the need to capture these specificities in reservoir functioning. We establish a modeling framework to effectively fill the spatial and temporal gaps that inevitably exist in the sampling coverage of large and heterogeneous reservoirs, which combined with appropriately modeled gas transfer velocities, will serve as a platform to derive robust estimates of diffusive fluxes. This modeling framework can be transposed to other reservoirs, and will contribute to more accurate and representative estimates of diffusive carbon emissions from hydroelectric reservoirs.

Collaborative Projects: Unleashing Early Career Scientists' Power.

Collaborative research projects exclusively targeted to early career researchers (ECRs) have been initiated in Europe. So far, the first two collaborative projects have united more than 80 ECRs. We describe the structure and benefits of such initiatives for the ECRs and highlight the positive influence on the whole scientific community.

Methane dynamics and thermal response in impoundments of the Rhine River, Germany.

River impoundments have been identified as important emission hot spots of the greenhouse gas methane. In this study, we investigated methane dynamics of five river impoundments within a two year period using a variety of methods ranging from sediment incubations for measuring methane formation rates (MF), automatic bubble-traps and echo-sounding surveys to assess ebullition fluxes, and estimated diffusive methane fluxes via dissolved concentrations in the water and calculated transport coefficients via wind speed. MF was found to be predominantly acetoclastic, and higher porewater acetate concentrations were associated with higher MF. Moreover, sediment MF showed consistent depth profiles, and when depth-integrated, MF was comparable to bubble-trap ebullition time-series measurements. Thermal response analysed for our systems and a wide range of literature data demonstrated a consistent mean value, but a large range of temperature coefficient Q10 (1.6 to 7.0) for different studies. Annual mean ebullition rates varied over more than one order of magnitude from site to site (0.03 to 1.85 mgCH4 l-1 d-1), demonstrating that river impoundments are not all hot-spots. Future work should investigate the role of sediment delivery, deposition patterns and management on methane emissions by ebullition.

Correction: Measuring CO2 and CH4 with a portable gas analyzer: Closed-loop operation, optimization and assessment.

[This corrects the article DOI: 10.1371/journal.pone.0193973.].

Cleaning and sampling protocol for analysis of mercury and dissolved organic matter in freshwater systems.

Mercury (Hg), and in particular its methylated form (methylmercury, MeHg), is a hazardous substance with the potential to produce significant adverse neurological and other health effects. Enhanced anthropogenic emissions and long-range transport of atmospheric Hg have increased Hg concentrations above background levels in aquatic systems. In this context, the Minamata Convention, a global legally binding agreement that seeks to prevent human exposure to Hg, was signed and enforced by 128 countries, and today more than 90 Parties have ratified it. All these Parties have committed to develop Hg monitoring programs to report the effectiveness of the convention. For this purpose, we provide a standardized cleaning and water sampling protocol for the determination of total-Hg and MeHg in freshwaters at ambient levels. As Hg and organic matter are tightly bound, the protocol also describes sample collection for dissolved organic carbon (DOC) concentration and characterization of dissolved organic matter (DOM) composition by fluorescence spectroscopy. This protocol is highly useful to non-experts without a prior background in Hg sampling and analysis, and can serve as a useful basis for national monitoring programs. Furthermore, this protocol should help increase quantitative inventories of DOC, inorganic-Hg (IHg) and MeHg concentrations and DOM composition in freshwater, which are severely lacking at a global scale. •Provides a standardized method to collect water samples for IHg, MeHg, DOC and DOM composition from freshwater ecosystems.

The interplay between total mercury, methylmercury and dissolved organic matter in fluvial systems: A latitudinal study across Europe.

Large-scale studies are needed to identify the drivers of total mercury (THg) and monomethyl-mercury (MeHg) concentrations in aquatic ecosystems. Studies attempting to link dissolved organic matter (DOM) to levels of THg or MeHg are few and geographically constrained. Additionally, stream and river systems have been understudied as compared to lakes. Hence, the aim of this study was to examine the influence of DOM concentration and composition, morphological descriptors, land uses and water chemistry on THg and MeHg concentrations and the percentage of THg as MeHg (%MeHg) in 29 streams across Europe spanning from 41°N to 64 °N. THg concentrations (0.06-2.78 ng L-1) were highest in streams characterized by DOM with a high terrestrial soil signature and low nutrient content. MeHg concentrations (7.8-159 pg L-1) varied non-systematically across systems. Relationships between DOM bulk characteristics and THg and MeHg suggest that while soil derived DOM inputs control THg concentrations, autochthonous DOM (aquatically produced) and the availability of electron acceptors for Hg methylating microorganisms (e.g. sulfate) drive %MeHg and potentially MeHg concentration. Overall, these results highlight the large spatial variability in THg and MeHg concentrations at the European scale, and underscore the importance of DOM composition on mercury cycling in fluvial systems.

Measuring CO2 and CH4 with a portable gas analyzer: Closed-loop operation, optimization and assessment.

The use of cavity ring-down spectrometer (CRDS) based portable greenhouse gas analyzers (PGAs) in closed-loop configuration to measure small sample volumes (< 1 l) for CH4 and CO2 concentrations is increasing and offers certain advantages over conventional measurement methods in terms of speed as well as the ability to measure directly in field locations. This first systematic assessment of the uncertainties, problems and issues associated with achieving reliable and repeatable measurement with this technique presents the adaptation, measurement range, calibration and maintenance, accuracy and issues of efficient operation, for one example instrument. Regular open-loop calibration, a precise loop volume estimate, leak free system, and a high standard of injection practices are necessary for accurate results. For 100 µl injections, measured values ranging from 4.5 to 9 x104 ppm (CH4), and 1000 ppm to 1 x106 ppm (CO2) are possible with uncertainties ±5.9% and ±3.0%, respectively, beyond 100 ppm CH4 correction may be necessary. Uncertainty arising from variations water vapour content and atmospheric pressure are small (0.24% and -0.9% to +0.5%, respectively). With good practice, individual operator repeatability of 1.9% (CH4) and 2.48% (CO2) can be achieved. Between operator injection error was around 3% for both gases for four operators. Slow syringe plunger operation (> 1s) is recommended; generally delivered more (ca. 3-4%) sample into the closed instrument loop than did rapid operation. Automated value retrieval is recommended; we achieved a 3 to 5-fold time reduction for each injection cycle (ca. <2 min), and operator reading, recording, and digitization errors are eliminated.

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.

Carbon dynamics and their link to dissolved organic matter quality across contrasting stream ecosystems.

Streams represent active components of the carbon cycle as emitters of carbon dioxide (CO2) and methane to the atmosphere at a global scale. However, the mechanisms and governing factors of these emissions are still largely unknown, especially concerning the effect of land use. We compared dissolved and gaseous carbon dynamics in streams bordered by contrasting types of land use, specifically agriculture and forest. Carbon dioxide and methane partial pressures (pCO2 and pCH4, respectively) in the water body and carbon emissions via both gases were studied for 24h during four field expeditions. pCH4 did not differ between the two system types. pCO2 was constantly oversaturated in all streams and significantly higher in agricultural streams (annual mean 4282 ppm) compared to forest streams (annual mean 2189 ppm) during all seasons. However, emissions of CO2 were not significantly different between the stream types due to significantly higher gas transfer velocity in forest compared to agricultural streams. pCO2 was significantly positively correlated to the concentrations of dissolved organic carbon, dissolved nitrogen and soluble reactive phosphorus in the water. Furthermore, pCO2 was correlated to optical parameters of dissolved organic matter (DOM) quality, e.g., it increased with indicators of molecular size and an allochthonous fluorescent component identified by Parallel Factor Analysis (PARAFAC). This study demonstrates that different forms of land use may trigger a cascade of effects on the carbon production and emission of streams linked to changes in DOM quality.

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.