Browsing by Subject "EXCHANGE"

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  • Osterwalder, S.; Fritsche, J.; Alewell, C.; Schmutz, M.; Nilsson, M. B.; Jocher, G.; Sommar, J.; Rinne, J.; Bishop, K. (2016)
    The fate of anthropogenic emissions of mercury (Hg) to the atmosphere is influenced by the exchange of elemental Hg with the earth surface. This exchange holds the key to a better understanding of Hg cycling from local to global scales, which has been difficult to quantify. To advance research about land-atmosphere Hg interactions, we developed a dual-inlet, single detector relaxed eddy accumulation (REA) system. REA is an established technique for measuring turbulent fluxes of trace gases and aerosol particles in the atmospheric surface layer. Accurate determination of gaseous elemental mercury (GEM) fluxes has proven difficult due to technical challenges presented by extremely small concentration differences (typically <0.5 ngm(-3)) between updrafts and downdrafts. We present an advanced REA design that uses two inlets and two pairs of gold cartridges for continuous monitoring of GEM fluxes. This setup reduces the major uncertainty created by the sequential sampling in many previous designs. Additionally, the instrument is equipped with a GEM reference gas generator that monitors drift and recovery rates. These innovations facilitate continuous, autonomous measurement of GEM flux. To demonstrate the system performance, we present results from field campaigns in two contrasting environments: an urban setting with a heterogeneous fetch and a boreal peatland during snowmelt. The observed average emission rates were 15 and 3 n gm(-2) h(-1), respectively. We believe that this dual-inlet, single detector approach is a significant improvement of the REA system for ultra-trace gases and can help to advance our understanding of long-term land-atmosphere GEM exchange.
  • Katul, Gabriel; Mammarella, Ivan; Grönholm, Tiia; Vesala, Timo (2018)
    Two ideas regarding the structure of turbulence near a clear air-water interface are used to derive a waterside gas transfer velocity k(L) for sparingly and slightly soluble gases. The first is that k(L) is proportional to the turnover velocity described by the vertical velocity structure function D-ww(r), where r is separation distance between two points. The second is that the scalar exchange between the air-water interface and the waterside turbulence can be suitably described by a length scale proportional to the Batchelor scale l(B) = Sc-1/2, where Sc is the molecular Schmidt number and eta is the Kolmogorov microscale defining the smallest scale of turbulent eddies impacted by fluid viscosity. Using an approximate solution to the von Karman-Howarth equation predicting D-ww(r) in the inertial and viscous regimes, prior formulations for k(L) are recovered including (i) kL = root 2/15Sc(-1/2)v(K), v(K) is the Kolmogorov velocity defined by the Reynolds number v(K)eta/nu = 1 and nu is the kinematic viscosity of water; (ii) surface divergence formulations; (iii) k(L) alpha Sc(-1/2)u(*), where u(*) is the waterside friction velocity; (iv) k(L) alpha Sc-1/2 root g nu/u(*) for Keulegan numbers exceeding a threshold needed for long-wave generation, where the proportionality constant varies with wave age, g is the gravitational acceleration; and (v) k(L) = root 2/15Sc(-1/2) (nu g beta(o)q(o))(1/4) in free convection, where q(o) is the surface heat flux and beta(o) is the thermal expansion of water. The work demonstrates that the aforementioned k(L) formulations can be recovered from a single structure function model derived for locally homogeneous and isotropic turbulence.
  • Keronen, Petri; Reissell, Anni; Chevallier, Frederic; Siivola, Erkki; Pohja, Toivo; Hiltunen, Veijo; Hatakka, Juha; Aalto, Tuula; Rivier, Leonard; Ciais, Philippe; Jordan, Armin; Hari, Pertti; Viisanen, Yrjo; Vesala, Timo (2014)
  • Arroyo-Mora, J. Pablo; Kalacska, Margaret; Soffer, Raymond J.; Moore, Tim R.; Roulet, Nigel T.; Juutinen, Sari; Ifimov, Gabriela; Leblanc, George; Inamdar, Deep (2018)
    Peatlands cover a large area in Canada and globally (12% and 3% of the landmass, respectively). These ecosystems play an important role in climate regulation through the sequestration of carbon dioxide from, and the release of methane to, the atmosphere. Monitoring approaches, required to understand the response of peatlands to climate change at large spatial scales, are challenged by their unique vegetation characteristics, intrinsic hydrological complexity, and rapid changes over short periods of time (e.g., seasonality). In this study, we demonstrate the use of multitemporal, high spatial resolution (1 m(2)) hyperspectral airborne imagery (Compact Airborne Spectrographic Imager (CASI) and Shortwave Airborne Spectrographic Imager (SASI) sensors) for assessing maximum instantaneous gross photosynthesis (PGmax) in hummocks, and gravimetric water content (GWC) and carbon uptake efficiency in hollows, at the Mer Bleue ombrotrophic bog. We applied empirical models (i.e., in situ data and spectral indices) and we derived spatial and temporal trends for the aforementioned variables. Our findings revealed the distribution of hummocks (51.2%), hollows (12.7%), and tree cover (33.6%), which is the first high spatial resolution map of this nature at Mer Bleue. For hummocks, we found growing season PGmax values between 8 mu mol m(-2) s(-1) and 12. tmol m(-2) s(-1) were predominant (86.3% of the total area). For hollows, our results revealed, for the first time, the spatial heterogeneity and seasonal trends for gravimetric water content and carbon uptake efficiency for the whole bog.
  • Savijärvi, Hannu; McConnochie, Timothy H.; Harri, Ari-Matti; Paton, Mark (2019)
    Local column precipitable water contents (PWC) for more than a martian year from 113 Curiosity ChemCam passive-mode sky scans were used to force a column model with subsurface adsorption. ChemCam volume mixing ratios (vmr) and T, RH and vmr from REMS-H were compared with model results. The REMS-H observations point to decrease of vmr (i.e. depletion of near-surface water vapor) during every evening and night throughout the year. The model's pre-dawn results are quite similar to the REMS-H observations, if adsorption is allowed. The indicated porosity is about 30% and the night depletion ratio about 0.25. If adsorption is not allowed, RH and vmr become excessive during every night at all seasons, leading to ground frost between Ls 82 degrees-146 degrees; frost has not been observed. As brine formation is unlikely along the Curiosity track, adsorption thus appears to be the depleting process. During daytime the ChemCam vmr is in general close to surface values from the Mars Climate Database (MCD) vmr profiles for the Curiosity site when those profiles are scaled to match the ChemCam PWC. Our simulated daytime surface-vmr is in turn close to the ChemCam vmr when moisture is assumed well-mixed to high altitudes, whereas a low moist layer (15 km) leads to overestimates, which are worse during the warm season. Increased TES-like regional PWC also leads to large overestimates of daytime surface-vmr. Hence the crater appears to be drier than the region surrounding Gale and the results support a seasonally varying vertical distribution of moisture with a dry lower atmosphere (by Hadley circulation), as suggested by MCD and other GCM experiments.
  • Raivonen, Maarit; Joensuu, Johanna; Keronen, Petri; Altimir, Nuria; Kolari, Pasi (2014)
  • Reischl, Bernhard; Raiteri, Paolo; Gale, Julian D.; Rohl, Andrew L. (2019)
    Advances in atomic force microscopy (AFM) in water have enabled the study of hydration layer structures on crystal surfaces, and in a recent study on dolomite (CaMg(CO3)(2)), chemical sensitivity was demonstrated by observing significant differences in force-distance curves over the calcium and magnesium ions in the surface. Here, we present atomistic molecular dynamics simulations of a hydration layer structure and dynamics on the (10 (1) over bar4) surfaces of dolomite, calcite (CaCO3), and magnesite (MgCO3), as well as simulations of AFM imaging on these three surfaces with a model silica tip. Our results confirm that it should be possible to distinguish between water molecules coordinating the calcium and magnesium ions in dolomite, and the details gleaned from the atomistic simulations enable us to clarify the underlying imaging mechanism in the AFM experiments.
  • Mera-Adasme, Raul; Xu, Wen-hua; Sundholm, Dage; Mendizabal, Fernando (2016)
    Solar power is a strong alternative to the currently used fossil fuels in order to satisfy the world's energy needs. Among them, dye-sensitized solar cells (DSSC) represent a low-cost option. Efficient and cheap dyes are currently needed to make DSSCs competitive. Computational chemistry can be used to guide the design of new light-absorbing chromophores. Here, we have computationally studied the lowest excited states of ZnPBAT, which is a recently synthesized porphyrinoid chromophore with high light-absorption efficiency. The calculations have been performed at ab initio correlated levels of theory employing second-order coupled clusters (CC2) and algebraic diagrammatic construction using second order (ADC(2)) methods and by performing density functional theory (DFT) calculations using the time-dependent DFT (TDDFT) approach for excitation energies. The ultraviolet-visible (UV-vis) spectrum calculated at the ADC(2) and CC2 levels agrees well with the experimental one. The calculations show that ZnPBAT has six electronic transitions in the visible range of the absorption spectrum. The ab initio correlated calculations and previously reported experimental data have been used to assess the performance of several well-known density functionals that have been employed in the present TDDFT study. Solvent effects have been estimated by using the conductor-like screening model (COSMO). The influence of the addition of a TiO2 cluster to the chromophore systems has also been investigated. The results indicate that both CAM-B3LYP and Becke's "half-and-half'' (BHLYP) density functionals are appropriate for the studies of excitation energies in the blue range of the visible spectrum for these kinds of porphyrinoid chromophores, whereas the excitation energies of the Q band calculated at the ab initio correlated level are more accurate than those obtained in the present TDDFT calculations. The inclusion of solvent effects has a modest influence on the spectrum of the protonated form of the studied chromophores, whereas solvent models are crucial when studying the absorption spectrum of the anionic chromophore. The calculated UV-vis spectrum for the chromophore anion is not significantly affected by attaching a TiO2 cluster to it.
  • Koster, Egle; Koster, Kajar; Berninger, Frank; Aaltonen, Heidi; Zhou, Xuan; Pumpanen, Jukka (2017)
    Forest fires are one of the most important natural disturbances in boreal forests, and their occurrence and severity are expected to increase as a result of climate warming. A combination of factors induced by fire leads to a thawing of the near-surface permafrost layer in subarctic boreal forest. Earlier studies reported that an increase in the active layer thickness results in higher carbon dioxide (CO2) and methane (CH4) emissions. We studied changes in CO2, CH4 and nitrous oxide (N2O) fluxes in this study, and the significance of several environmental factors that influence the greenhouse gas (GHG) fluxes at three forest sites that last had fires in 2012, 1990 and 1969, and we compared these to a control area that had no fire for at least 100 years. The soils in our study acted as sources of CO2 and N2O and sinks for CH4. The elapsed time since the last forest fire was the only factor that significantly influenced all studied GHG fluxes. Soil temperature affected the uptake of CH4, and the N2O fluxes were significantly influenced by nitrogen and carbon content of the soil, and by the active layer depth. Results of our study confirm that the impacts of a forest fire on GHGs last for a rather long period of time in boreal forests, and are influenced by the fire induced changes in the ecosystem. (C) 2017 Elsevier B.V. All rights reserved.
  • Parkkinen, Pauli; Xu, Wen-Hua; Solala, Eelis; Sundholm, Dage (2018)
    Density functional theory within the Kohn-Sham density functional theory (KS-DFT) ansatz has been implemented into our bubbles and cube real-space molecular electronic structure framework, where functions containing steep cusps in the vicinity of the nuclei are expanded in atom-centered one-dimensional (1D) numerical grids multiplied with spherical harmonics (bubbles). The remainder, i.e., the cube, which is the cusp-free and smooth difference between the atomic one-center contributions and the exact molecular function, is represented on a three-dimensional (3D) equidistant grid by using a tractable number of grid points. The implementation of the methods is demonstrated by performing 3D numerical KS-DFT calculations on light atoms and small molecules. The accuracy is assessed by comparing the obtained energies with the best available reference energies.
  • Sabbatini, Simone; Mammarella, Ivan; Arriga, Nicola; Fratini, Gerardo; Graf, Alexander; Hoertriagl, Lukas; Ibrom, Andreas; Longdoz, Bernard; Mauder, Matthias; Merbold, Lutz; Metzger, Stefan; Montagnani, Leonardo; Pitacco, Andrea; Rebmann, Corinna; Sedlak, Pavel; Sigut, Ladislav; Vitale, Domenico; Papale, Dario (2018)
    The eddy covariance is a powerful technique to estimate the surface-atmosphere exchange of different scalars at the ecosystem scale. The EC method is central to the ecosystem component of the Integrated Carbon Observation System, a monitoring network for greenhouse gases across the European Continent. The data processing sequence applied to the collected raw data is complex, and multiple robust options for the different steps are often available. For Integrated Carbon Observation System and similar networks, the standardisation of methods is essential to avoid methodological biases and improve comparability of the results. We introduce here the steps of the processing chain applied to the eddy covariance data of Integrated Carbon Observation System stations for the estimation of final CO2, water and energy fluxes, including the calculation of their uncertainties. The selected methods are discussed against valid alternative options in tenns of suitability and respective drawbacks and advantages. The main challenge is to warrant standardised processing for all stations in spite of the large differences in e.g. ecosystem traits and site conditions. The main achievement of the Integrated Carbon Observation System eddy covariance data processing is making CO2 and energy flux results as comparable and reliable as possible, given the current micrometeorological understanding and the generally accepted state-of-the-art processing methods.
  • Mendizabal, Fernando; Mera-Adasme, Raul; Xu, Wen-Hua; Sundholm, Dage (2017)
    Dye-sensitized solar-cell (DSSC) systems have been investigated by calculating light-absorption and electron-injection processes of the LD13 ([5,15-bis(2,6-(1,1-dimethylethyl)-phenyl)-10-4-dimethylaminophenylethynyl-20-4-carboxy phenylethynyl porphyrinato]zinc-(II)) and YD2-o-C8 ([5,15bis( 2,6-dioctoxyphenyl)-10-(bis(4-hexylphenyl)amino-20-4-carboxyphenylethynyl)porphyrinato]zinc-(II)) dyes adsorbed on a TiO2 cluster simulating the semiconductor. The binding energy of the dyes with the TiO2 clusters has been calculated at the density functional theory (DFT) level using the B3LYP and CAM-B3LYP functionals. The electronic excitation energies have been calculated at the time-dependent DFT (TDDFT) level for the dyes in the gas and solvent phase employing the B3LYP, CAM-B3LYP and BHLYP functionals. The calculated excitation energies have been compared to values obtained at the algebraic diagrammatic construction through second order (ADC(2)) level of theory. The TDDFT calculations with the B3LYP in tetrahydrofuran solvent with the dye and dye-TiO2 models yield excitation energies that agree well with the transitions in the experimental absorption spectra. Changes in the free energy for electron injection support the better performance of the dyes on the TiO2 clusters.
  • Dukat, Paulina; Ziemblinska, Klaudia; Olejnik, Janusz; Malek, Stanislaw; Vesala, Timo; Urbaniak, Marek (2021)
    The accurate estimation of an increase in forest stand biomass has remained a challenge. Traditionally, in situ measurements are done by inventorying a number of trees and their biometric parameters such as diameter at the breast height (DBH) and height; sometimes these are complemented by carbon (C) content studies. Here we present the estimation of net primary productivity (NPP) over a two years period (2019-2020) at a 25-year-old Scots pine stand. Research was based on allometric equations made by direct biomass analysis (tree extraction) and carbon content estimations in individual components of sampled trees, combined with a series of stem diameter increments recorded by a network of band dendrometers. Site-specific allometric equations were obtained using two different approaches: using the whole tree biomass vs DBH (M1), and total dry biomass-derived as a sum of the results from individual tree components' biomass vs DBH (M2). Moreover, equations for similar forest stands from the literature were used for comparison. Gross primary productivity (GPP) estimated from the eddy-covariance measurements allowed the calculation of carbon use efficiency (CUE = NPP/GPP). The two investigated years differed in terms of the sum and patterns of precipitation distribution, with a moderately dry year of 2019 that followed the extremely dry 2018, and the relatively average year of 2020. As expected, a higher increase in biomass was recorded in 2020 compared to 2019, as determined by both allometric equations based on in situ and literature data. For the former approach, annual NPP estimates reached ca. 2.0-2.1 t C ha(-1) in 2019 and 2.6-2.7 t C ha(-1) in 2020 depending on the "in situ equations" (M1-M2) used, while literature-derived equations for the same site resulted in NPP values ca. 20-30% lower. CUE was higher in 2020, which resulted from a higher NPP total than in 2019, with lower summer and spring GPP in 2020. However, the CUE values were lower than those reported in the literature for comparable temperate forest stands. A thorough analysis of the low CUE value would require a full interpretation of interrelated physiological responses to extreme conditions.
  • Arriga, Nicola; Rannik, Ullar; Aubinet, Marc; Carrara, Arnaud; Vesala, Timo; Papale, Dario (2017)
    Footprint models, which simulate source area for scalar fluxes, are fundamental tools for a correct interpretation of micromoeteorological flux measurements and ecosystem exchange inferred from such data. Over the last two decades models of varying complexity have been developed, but all of them suffer from a significant lack of experimental validation. In this study two different experimental tests have been conducted with the aim of offering validation: a manipulation of the vegetation cover and an artificial tracer emission. In the first case the extension of the flux source has been changed progressively by successive cuts of vegetation, while in the second case by varying the distance of a tracer emission line respect to the measurement point. Results have been used to validate two analytical and a numerical footprint models. The experimental data show a good agreement with footprint models and indicate a limited extension of the flux source area, with approximately 75% of the sources confined within a range of 10-20 times the effective measurement height, i.e. the measurement height above the zero plane displacement. Another interesting result was the strong dependence on the surface roughness of both experimental estimates and numerical simulations of footprint. The effect of surface roughness on experimental results and models outputs was comparable to the effect of atmospheric stability. This indicates that surface roughness and turbulence conditions may play a significant role in source area location, in particular above inhomogeneous surfaces with change in roughness, as in the case of the manipulation experiment. Consequently a careful site specific quantification of these parameters seems to be fundamental to obtain realistic footprint estimates and significantly improve eddy covariance flux interpretation at complex sites.
  • Mander, Ulo; Krasnova, Alisa; Escuer-Gatius, Jordi; Espenberg, Mikk; Schindler, Thomas; Machacova, Katerina; Parn, Jaan; Maddison, Martin; Megonigal, J. Patrick; Pihlatie, Mari; Kasak, Kuno; Niinemets, Ulo; Junninen, Heikki; Soosaar, Kaido (2021)
    Riparian forests are known as hot spots of nitrogen cycling in landscapes. Climate warming speeds up the cycle. Here we present results from a multi-annual high temporal-frequency study of soil, stem, and ecosystem (eddy covariance) fluxes of N2O from a typical riparian forest in Europe. Hot moments (extreme events of N2O emission) lasted a quarter of the study period but contributed more than half of soil fluxes. We demonstrate that high soil emissions of N2O do not escape the ecosystem but are processed in the canopy. Rapid water content change across intermediate soil moisture was a major determinant of elevated soil emissions in spring. The freeze-thaw period is another hot moment. However, according to the eddy covariance measurements, the riparian forest is a modest source of N2O. We propose photochemical reactions and dissolution in canopy-space water as reduction mechanisms.
  • Rotkirch, Anna; Lyons, Minna; David-Barrett, Tamas; Jokela, Markus (2014)
  • Aberg, Susanne C.; Korkka-Niemi, Kirsti; Rautio, Anne; Salonen, Veli-Pekka; Aberg, Annika K. (2019)
    Areas of groundwater-surface water interaction in riverbanks and open mires are important habitats for groundwater-dependent species. In order to preserve these ecosystems, the planning and development of mining operations on such locations require a fundamental understanding of the groundwater discharge-recharge and flow patterns. In this study. 3D flow modelling and a TIR survey were used to define the groundwater discharge. Simultaneously, the flow modelling and groundwater table fluctuation were used for defining groundwater recharge at a mining development site in northern Finland. The results indicated flow towards the River Kitinen and the discharge of groundwater in the banks of the river. The discharge also occurred within the mire area, which may provide suitable habitats for groundwater-dependent plant species. The modelling results and stable isotope variations indicated complex flow patterns and a potential groundwater connection from the Viiankiaapa mire through possible bedrock fractures to the river. Recharge mainly occurred in the sorted sediment accumulations of the riverbanks and partly also in the mire area.
  • Humborg, Christoph; Geibel, Marc. C.; Sun, Xiaole; McCrackin, Michelle; Mörth, Carl-Magnus; Stranne, Christian; Jakobsson, Martin; Gustafsson, Bo; Sokolov, Alexander; Norkko, Alf; Norkko, Joanna (2019)
    The summer heat wave in 2018 led to the highest recorded water temperatures since 1926 – up to 21 C – in bottom coastal waters of the Baltic Sea, with implications for the respiration patterns in these shallow coastal systems. We applied cavity ring-down spectrometer measurements to continuously monitor carbon dioxide (CO2) and methane (CH4) surface-water concentrations, covering the coastal archipelagos of Sweden and Finland and the open and deeper parts of the Northern Baltic Proper. This allowed us to i) follow an upwelling event near the Swedish coast leading to elevated CO2 and moderate CH4 outgassing, and ii) to estimate CH4 sources and fluxes along the coast by investigating water column inventories and air-sea fluxes during a storm and an associated downwelling event. At the end of the heat wave, before the storm event, we found elevated CO2 (1583 µatm) and CH4 (70 nmol/L) concentrations. During the storm, a massive CO2 sea-air flux of up to 274 mmol m-2 d-1 was observed. While water-column CO2 concentrations were depleted during several hours of the storm, CH4 concentrations remained elevated. Overall, we found a positive relationship between CO2 and CH4 wind-driven sea-air fluxes, however, the highest CH4 fluxes were observed at low winds whereas highest CO2 fluxes were during peak winds, suggesting different sources and processes controlling their fluxes besides wind. We applied a box-model approach to estimate the CH4 supply needed to sustain these elevated CH4 concentrations and the results suggest a large source flux of CH4 to the water column of 2.5 mmol m-2 d-1. These results are qualitatively supported by acoustic observations of vigorous and widespread outgassing from the sediments, with flares that could be traced throughout the water column penetrating the pycnocline and reaching the sea surface. The results suggest that the heat wave triggered CO2 and CH4 fluxes in the coastal zones that are comparable with maximum emission rates found in other hot spots, such as boreal and arctic lakes and wetlands. Further, the results suggest that heat waves are as important for CO2 and CH4 sea-air fluxes as the ice break up in spring.
  • Kittler, Fanny; Eugster, Werner; Foken, Thomas; Heimann, Martin; Kolle, Olaf; Göckede, Mathias (2017)
    This study aimed at quantifying potential negative effects of instrument heating to improve eddy-covariance flux data quality in cold environments. Our overarching objective was to minimize heating-related bias in annual CO2 budgets from an Arctic permafrost system. We used continuous eddy-covariance measurements covering three full years within an Arctic permafrost ecosystem with parallel sonic anemometers operation with activated heating and without heating as well as parallel operation of open- and closed-path gas analyzers, the latter serving as a reference. Our results demonstrate that the sonic anemometer heating has a direct effect on temperature measurements while the turbulent wind field is not affected. As a consequence, fluxes of sensible heat are increased by an average 5 W m(-2) with activated heating, while no direct effect on other scalar fluxes was observed. However, the biased measurements in sensible heat fluxes can have an indirect effect on the CO2 fluxes in case they are used as input for a density-flux WPL correction of an open-path gas analyzer. Evaluating the self-heating effect of the open-path gas analyzer by comparing CO2 flux measurements between open- and closed-path gas analyzers, we found systematically higher CO2 uptake recorded with the open-path sensor, leading to a cumulative annual offset of 96 g Cm-2, which was not only the result of the cold winter season but also due to substantial self-heating effects during summer. With an inclined sensor mounting, only a fraction of the self-heating correction for vertically mounted instruments is required.
  • Tang, Xuguang; Li, Hengpeng; Desai, Ankur R.; Nagy, Zoltan; Luo, Juhua; Kolb, Thomas E.; Olioso, Albert; Xu, Xibao; Yao, Li; Kutsch, Werner; Pilegaard, Kim; Köstner, Barbara; Ammann, Christof (2014)