Summer greenhouse gas fluxes in different types of hemiboreal lakes.

Lakes are considered important regulators of atmospheric greenhouse gases (GHG). We estimated late summer open water GHG fluxes in nine hemiboreal lakes in Estonia classified under different lake types according to the European Water Framework Directive (WFD). We also used the WFD typology to provide an improved estimate of the total GHG emission from all Estonian lakes with a gross surface area of 2204 km2 representing 45,227 km2 of hemiboreal landscapes (the territory of Estonia). The results demonstrate largely variable CO2 fluxes among the lake types with most active emissions from Alkalitrophic (Alk), Stratified Alkalitrophic (StratAlk), Dark Soft and with predominant binding in Coastal, Very Large, and Light Soft lakes. The CO2 fluxes correlated strongly with dissolved CO2 saturation (DCO2) values at the surface. Highest CH4 emissions were measured from the Coastal lake type, followed by Light Soft, StratAlk, and Alk types; Coastal, Light Soft, and StratAlk were emitting CH4 partly as bubbles. The only emitter of N2O was the Alk type. We measured weak binding of N2O in Dark Soft and Coastal lakes, while in all other studied lake types, the N2O fluxes were too small to be quantified. Diversely from the common viewpoint of lakes as net sources of both CO2 and CH4, it turns out from our results that at least in late summer, Estonian lakes are net sinks of both CO2 alone and the sum of CO2 and CH4. This is mainly caused by the predominant CO2 sink function of Lake Peipsi forming ¾ of the total lake area and showing negative net emissions even after considering the Global Warming Potential (GWP) of other GHGs. Still, by converting CH4 data into CO2 equivalents, the combined emission of all Estonian lakes (8 T C day-1) is turned strongly positive: 2720 T CO2 equivalents per day.

Cross-continental importance of CH4 emissions from dry inland-waters.

Despite substantial advances in quantifying greenhouse gas (GHG) emissions from dry inland waters, existing estimates mainly consist of carbon dioxide (CO2) emissions. However, methane (CH4) may also be relevant due to its higher Global Warming Potential (GWP). We report CH4 emissions from dry inland water sediments to i) provide a cross-continental estimate of such emissions for different types of aquatic systems (i.e., lakes, ponds, reservoirs, and streams) and climate zones (i.e., tropical, continental, and temperate); and ii) determine the environmental factors that control these emissions. CH4 emissions from dry inland waters were consistently higher than emissions observed in adjacent uphill soils, across climate zones and in all aquatic systems except for streams. However, the CH4 contribution (normalized to CO2 equivalents; CO2-eq) to the total GHG emissions of dry inland waters was similar for all types of aquatic systems and varied from 10 to 21%. Although we discuss multiple controlling factors, dry inland water CH4 emissions were most strongly related to sediment organic matter content and moisture. Summing CO2 and CH4 emissions revealed a cross-continental average emission of 9.6 ± 17.4 g CO2-eq m-2 d-1 from dry inland waters. We argue that increasing droughts likely expand the worldwide surface area of atmosphere-exposed aquatic sediments, thereby increasing global dry inland water CH4 emissions. Hence, CH4 cannot be ignored if we want to fully understand the carbon (C) cycle of dry sediments.

Detecting Climate Driven Changes in Chlorophyll-a Using High Frequency Monitoring: The Impact of the 2019 European Heatwave in Three Contrasting Aquatic Systems.

The frequency of heatwave events in Europe is increasing as a result of climate change. This can have implications for the water quality and ecological functioning of aquatic systems. We deployed three spectroradiometer WISPstations at three sites in Europe (Italy, Estonia, and Lithuania/Russia) to measure chlorophyll-a at high frequency. A heatwave in July 2019 occurred with record daily maximum temperatures over 40 °C in parts of Europe. The effects of the resulting storm that ended the heatwave were more discernable than the heatwave itself. Following the storm, chlorophyll-a concentrations increased markedly in two of the lakes and remained high for the duration of the summer while at one site concentrations increased linearly. Heatwaves and subsequent storms appeared to play an important role in structuring the phenology of the primary producers, with wider implications for lake functioning. Chlorophyll-a peaked in early September, after which a wind event dissipated concentrations until calmer conditions returned. Synoptic coordinated high frequency monitoring needs to be advanced in Europe as part of water management policy and to improve knowledge on the implications of climate change. Lakes, as dynamic ecosystems with fast moving species-succession, provide a prism to observe the scale of future change.

Summer depth distribution profiles of dissolved CO2 and O2 in shallow temperate lakes reveal trophic state and lake type specific differences.

Knowledge about dissolved oxygen (DO) and carbon dioxide (CO2) distribution in lakes has increased considerably over the last decades. However, studies about high resolution dynamics of dissolved CO2 in different types of lakes over daily or weekly time scales are still very scarce. We measured summertime vertical DO and CO2 profiles at sub-hourly intervals during one week in eight Estonian lakes representing different lake types according to European Water Framework Directive. The lakes showed considerable differences in thermal stratification and vertical distribution of dissolved oxygen and CO2 as well as different diurnal dynamics over the measurement period. We observed a continuous CO2 supersaturation in the upper mixed layer of the alkalitrophic (calcareous groundwater-fed) lake and the dark soft-water lake showing them as CO2 emitting "chimneys" although with different underlying mechanisms. In three lake types strong undersaturation with CO2 occurred in the surface layer characterising them as CO2 sinks for the measurement period while in another three types the surface layer CO2 was mostly in equilibrium with the atmosphere. Factor analysis showed that DO% in the surface layer and the strength of its relationship with CO2% were positively related to alkalinity and negatively to trophic state and DOC gradients, whereas deeper lakes were characterised by higher surface concentration but smaller spatial and temporal variability of CO2. Multiple regression analysis revealed lake area, maximum depth and the light attenuation coefficient as variables affecting the largest number of gas regime indicators. We conclude that the trophic status of lakes in combination with type specific features such as morphometry, alkalinity and colour (DOC) determines the distribution and dynamics of dissolved CO2 and DO, which therefore may indicate functional differences in carbon cycling among lakes.

Role of a productive lake in carbon sequestration within a calcareous catchment.

For a long time, lakes were considered unimportant in the global carbon (C) cycle because of their small total area compared to the ocean. Over the last two decades, a number of studies have highlighted the important role of lakes in both sequestering atmospheric C and modifying the C flux from the catchment by degassing CO2 and methane and burying calcite and organic matter in the sediment. Based on a full C mass balance, high frequency measurements of lake metabolism and stable isotope analysis of a large shallow eutrophic lake in Estonia, we assess the role alkaline lakes play in augmenting the strength of terrestrial carbonate weathering as a temporary CO2 sink. We show that a large part of organic C buried in the sediments in this type of lakes originates from the catchment although a direct uptake from the atmosphere during periods of intensive phytoplankton growth in eutrophic conditions contributes to the carbon sink.

Brønsted basicities of diamines in the gas phase, acetonitrile, and tetrahydrofuran.

A comprehensive basicity study of alpha,omega-alkanediamines and related bases has been carried out. Basicities in acetonitrile (AN, pK(a) values), tetrahydrofuran (THF, pK(alpha) values), and gas phase (GP, GB values), were measured for 16, 14, and 9 diamine bases and for several related monoamines. In addition the gas-phase basicities and equilibrium geometries were computed for 19 diamino bases and several related monoamines at the DFT B3LYP 6-311+G** level. The effects of the different factors (intrinsic basicity of the amino groups, formation of intramolecular hydrogen bonds, and molecular strain) determining the diamine basicities were estimated by using the method of isodesmic reactions. The results are discussed in terms of molecular structure and solvation effects. The GP basicity is determined by the molecular size and polarizability, the extent of alkylation, and the energy effect of intramolecular hydrogen bond formation in the protonated base. The basicity trends in the solvents differ very much from those in GP: 1) The solvents severely compress the basicity range of the bases studied (3.5 times for the 1,3-propanediamine family in AN, and 7 times in THF), and 2) while stepwise alkylation of the basicity center leads to a steady basicity increase in the gas phase, the picture is complex in the solvents. Significant differences are also evident between THF and AN. The high hydrogen bond acceptor strength of THF leads to this solvent favoring the bases with "naked" protonation centers. In particular, the basicity order of N-methylated 1,3-propanediamines is practically inverse to that in the gas phase. The picture in AN is intermediate between that of GP and THF.

Experimental gas-phase basicity scale of superbasic phosphazenes.

Seventeen superbasic phosphazenes and two Verkade's bases were used to supplement and extend the experimental gas-phase basicity scale in the superbasic region. For 19 strong bases the gas-phase basicity values (GB) were determined for the first time. Among them are such well-known bases as BEMP (1071.2 kJ/mol), Verkade's Me-substituted base (1083.8 kJ/mol), Et-N=P(NMe2)2-N=P(NMe2)3 (Et-P2 phosphazene, 1106.9 kJ/mol), and t-Bu-N=P(NMe2)3 (t-Bu-P1 phosphazene, 1058.0 kJ/mol). For the first time experimental GB values were determined for P2 phosphazenes. Together with our previous results self-consistent experimental gas-phase basicity scale between 1020 and 1107 kJ/mol is now established. This way an important region of the gas-phase basicity scale, which was earlier dominated by metal hydroxide bases, is now covered also with organic bases making it more accessible for further studies. The GB values for several superbases were calculated using density functional theory at the B3LYP/6-311+G** level. For the phosphazene family the standard deviation of the correlation between the experimental and theoretical values was 6.5 kJ/mol.

Acid-base equilibria in nonpolar media. 3. Expanding the spectrophotometric acidity scale in heptane.

The UV-vis spectrophotometric ion-pair acidity scale in heptane has been significantly expanded: it includes now 21 bulky CH and NH indicator acids and spans for about 10 pKip units. The phosphazene base t-Bu-P4 was used for deprotonating. The correlations between acidities in heptane versus gas-phase acidities or acidities in DMSO or 1,2-dimethoxyethane have been made for some compounds. It was demonstrated that the substituent effects on the acidity of the studied CH acids are attenuated ca. 1.24 times when the gas phase is substituted for the nonpolar solvent, heptane. In its turn, for the series of NH acids, the latter is found to be a somewhat more differentiating solvent than DMSO.