Assessment of field monitoring of plant fluxes of oxidized nitrogen with two types of detectors

Peer reviewe

Calibrating the sqHIMMELI v1.0 wetland methane emission model with hierarchical modeling and adaptive MCMC

Estimating methane (CH4) emissions from natural wetlands is complex, and the estimates contain large uncertainties. The models used for the task are typically heavily parameterized and the parameter values are not well known. In this study, we perform a Bayesian model calibration for a new wetland CH4 emission model to improve the quality of the predictions and to understand the limitations of such models. The detailed process model that we analyze contains descriptions for CH4 production from anaerobic respiration, CH4 oxidation, and gas transportation by diffusion, ebullition, and the aerenchyma cells of vascular plants. The processes are controlled by several tunable parameters. We use a hierarchical statistical model to describe the parameters and obtain the posterior distributions of the parameters and uncertainties in the processes with adaptive Markov chain Monte Carlo (MCMC), importance resampling, and time series analysis techniques. For the estimation, the analysis utilizes measurement data from the Siikaneva flux measurement site in southern Finland. The uncertainties related to the parameters and the modeled processes are described quantitatively. At the process level, the flux measurement data are able to constrain the CH4 production processes, methane oxidation, and the different gas transport processes. The posterior covariance structures explain how the parameters and the processes are related. Additionally, the flux and flux component uncertain-ties are analyzed both at the annual and daily levels. The parameter posterior densities obtained provide information regarding importance of the different processes, which is also useful for development of wetland methane emission models other than the square root HelsinkI Model of MEthane buiLd- up and emIssion for peatlands (sqHIMMELI). The hierarchical modeling allows us to assess the effects of some of the parameters on an annual basis. The results of the calibration and the cross validation suggest that the early spring net primary production could be used to predict parameters affecting the annual methane production. Even though the calibration is specific to the Siikaneva site, the hierarchical modeling approach is well suited for larger-scale studies and the results of the estimation pave way for a regional or global- scale Bayesian calibration of wetland emission models.Peer reviewe

Peat macropore networks – new insights into episodic and hotspot methane emission

Peatlands are important natural sources of atmospheric methane (CH4) emissions. The production and emission of CH4 are strongly influenced by the diffusion of oxygen into the soil and of CH4 from the soil to the atmosphere, respectively. This diffusion, in turn, is controlled by the structure of macropore networks. The characterization of peat pore structure and connectivity through complex network theory approaches can give conceptual insight into how the relationship between the microscale pore space properties and CH4 emissions on a macroscopic scale is shaped. The evolution of the pore space that is connected to the atmosphere can also be conceptualized through a pore network modeling approach. Pore regions isolated from the atmosphere may further develop into anaerobic pockets, which are local hotspots of CH4 production in unsaturated peat. In this study, we extracted interconnecting macropore networks from three-dimensional X-ray micro-computed tomography (µCT) images of peat samples and evaluated local and global connectivity metrics for the networks. We also simulated the water retention characteristics of the peat samples using a pore network modeling approach and compared the simulation results with measured water retention characteristics. The results showed large differences in peat macropore structure and pore network connectivity between vertical soil layers. The macropore space was more connected and the flow paths through the peat matrix were less tortuous near the soil surface than at deeper depths. In addition, macroporosity, structural anisotropy, and average pore throat diameter decreased with depth. Narrower and more winding air-filled diffusion channels may reduce the rate of gas transport as the distance from the peat layer to the soil–air interface increases. The network analysis also suggests that both local and global network connectivity metrics, such as the network average clustering coefficient and closeness centrality, might serve as proxies for assessing the efficiency of gas diffusion in air-filled pore networks. However, the applicability of the network metrics was restricted to the high-porosity near-surface layer. The spatial extent and continuity of the pore network and the spatial distribution of the pores may be reflected in different network metrics in contrasting ways. The hysteresis of peat water content between wetting and drying was found to affect the evolution of the volume of connected air-filled pore space in unsaturated peat. Thus, the formation of anaerobic pockets may occur in a smaller soil volume and methanogenesis may be slower when the peat is wetting compared to in drying conditions. This hysteretic behavior might explain the hotspots and episodic spikes of CH4 emissions, and therefore, it should be taken into account in biogeochemical models.Peer reviewe

Temporal Variation of Ecosystem Scale Methane Emission From a Boreal Fen in Relation to Temperature, Water Table Position, and Carbon Dioxide Fluxes

We have analyzed decade-long methane flux data set from a boreal fen, Siikaneva, together with data on environmental parameters and carbon dioxide exchange. The methane flux showed seasonal cycle but no systematic diel cycle. The highest fluxes were observed in July-August with average value of 73 nmol m(-2) s(-1). Wintertime fluxes were small but positive, with January-March average of 6.7 nmol m(-2) s(-1). Daily average methane emission correlated best with peat temperatures at 20-35 cm depths. The second highest correlation was with gross primary production (GPP). The best correspondence between emission algorithm and measured fluxes was found for a variable-slope generalized linear model (r(2) = 0.89) with peat temperature at 35 cm depth and GPP as explanatory variables, slopes varying between years. The homogeneity of slope approach indicated that seasonal variation explained 79% of the sum of squares variation of daily average methane emission, the interannual variation in explanatory factors 7.0%, functional change 5.3%, and random variation 9.1%. Significant correlation between interannual variability of growing season methane emission and that of GPP indicates that on interannual time scales GPP controls methane emission variability, crucially for development of process-based methane emission models. Annual methane emission ranged from 6.0 to 14 gC m(-2) and was 2.7 +/- 0.4% of annual GPP. Over 10-year period methane emission was 18% of net ecosystem exchange as carbon. The weak relation of methane emission to water table position indicates that space-to-time analogy, used to extrapolate spatial chamber data in time, may not be applicable in seasonal time scales.Peer reviewe

Role of needle surface waxes in dynamic exchange of mono- and sesquiterpenes

Biogenic volatile organic compounds (BVOCs) produced by plants have a major role in atmospheric chemistry. The different physicochemical properties of BVOCs affect their transport within and out of the plant as well as their reactions along the way. Some of these compounds may accumulate in or on the waxy surface layer of conifer needles and participate in chemical reactions on or near the foliage surface. The aim of this work was to determine whether terpenes, a key category of BVOCs produced by trees, can be found on the epicuticles of Scots pine (Pinus sylvestris L.) and, if so, how they compare with the terpenes found in shoot emissions of the same tree. We measured shoot-level emissions of pine seedlings at a remote outdoor location in central Finland and subsequently analysed the needle surface waxes for the same compounds. Both emissions and wax extracts were clearly dominated by monoterpenes, but the proportion of sesquiterpenes was higher in the wax extracts. There were also differences in the terpene spectra of the emissions and the wax extracts. The results, therefore, support the existence of BVOC associated to the epicuticular waxes. We briefly discuss the different pathways for terpenes to reach the needle surfaces and the implications for air chemistry.Peer reviewe

HIMMELI v1.0 : HelsinkI Model of MEthane buiLd-up and emIssion for peatlands

Wetlands are one of the most significant natural sources of methane (CH4) to the atmosphere. They emit CH4 because decomposition of soil organic matter in waterlogged anoxic conditions produces CH4, in addition to carbon dioxide (CO2). Production of CH4 and how much of it escapes to the atmosphere depend on a multitude of environmental drivers. Models simulating the processes leading to CH4 emissions are thus needed for upscaling observations to estimate present CH4 emissions and for producing scenarios of future atmospheric CH4 concentrations. Aiming at a CH4 model that can be added to models describing peatland carbon cycling, we composed a model called HIMMELI that describes CH4 build-up in and emissions from peatland soils. It is not a full peatland carbon cycle model but it requires the rate of anoxic soil respiration as input. Driven by soil temperature, leaf area index (LAI) of aerenchymatous peat-land vegetation, and water table depth (WTD), it simulates the concentrations and transport of CH4, CO2, and oxygen (O-2) in a layered one-dimensional peat column. Here, we present the HIMMELI model structure and results of tests on the model sensitivity to the input data and to the description of the peat column (peat depth and layer thickness), and demonstrate that HIMMELI outputs realistic fluxes by comparing modeled and measured fluxes at two peatland sites. As HIMMELI describes only the CH4-related processes, not the full carbon cycle, our analysis revealed mechanisms and dependencies that may remain hidden when testing CH4 models connected to complete peatland carbon models, which is usually the case. Our results indicated that (1) the model is flexible and robust and thus suitable for different environments; (2) the simulated CH4 emissions largely depend on the prescribed rate of anoxic respiration; (3) the sensitivity of the total CH4 emission to other input variables is mainly mediated via the concentrations of dissolved gases, in particular, the O-2 concentrations that affect the CH4 production and oxidation rates; (4) with given input respiration, the peat column description does not significantly affect the simulated CH4 emissions in this model version.Peer reviewe

The consolidated European synthesis of CH4 and N2O emissions for the European Union and United Kingdom : 1990-2019

Funding Information: We thank Aurélie Paquirissamy, Géraud Moulas and the ARTTIC team for the great managerial support offered during the project. FAOSTAT statistics are produced and disseminated with the support of its member countries to the FAO regular budget. Annual, gap-filled and harmonized NGHGI uncertainty estimates for the EU and its member states were provided by the EU GHG inventory team (European Environment Agency and its European Topic Centre on Climate change mitigation). Most top-down inverse simulations referred to in this paper rely for the derivation of optimized flux fields on observational data provided by surface stations that are part of networks like ICOS (datasets: 10.18160/P7E9-EKEA , Integrated Non-CO Observing System, 2018a, and 10.18160/B3Q6-JKA0 , Integrated Non-CO Observing System, 2018b), AGAGE, NOAA (Obspack Globalview CH: 10.25925/20221001 , Schuldt et al., 2017), CSIRO and/or WMO GAW. We thank all station PIs and their organizations for providing these valuable datasets. We acknowledge the work of other members of the EDGAR group (Edwin Schaaf, Jos Olivier) and the outstanding scientific contribution to the VERIFY project of Peter Bergamaschi. Timo Vesala thanks ICOS-Finland, University of Helsinki. The TM5-CAMS inversions are available from https://atmosphere.copernicus.eu (last access: June 2022); Arjo Segers acknowledges support from the Copernicus Atmosphere Monitoring Service, implemented by the European Centre for Medium-Range Weather Forecasts on behalf of the European Commission (grant no. CAMS2_55). This research has been supported by the European Commission, Horizon 2020 Framework Programme (VERIFY, grant no. 776810). Ronny Lauerwald received support from the CLand Convergence Institute. Prabir Patra received support from the Environment Research and Technology Development Fund (grant no. JPMEERF20182002) of the Environmental Restoration and Conservation Agency of Japan. Pierre Regnier received financial support from the H2020 project ESM2025 – Earth System Models for the Future (grant no. 101003536). David Basviken received support from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (METLAKE, grant no. 725546). Greet Janssens-Maenhout received support from the European Union's Horizon 2020 research and innovation program (CoCO, grant no. 958927). Tuula Aalto received support from the Finnish Academy (grants nos. 351311 and 345531). Sönke Zhaele received support from the ERC consolidator grant QUINCY (grant no. 647204).Peer reviewedPublisher PD

UV-säteilyn aiheuttamat reaktiivisten typpiyhdisteiden emissiot männyn oksien kaasunvaihtoa mittaavissa kammioissa: niiden alkuperä ja merkitys

VäitöskirjaselosteSeloste väitöskirjasta: Raivonen, M. 2008. UV-induced Noy emissions in gas-exchange chambers enclosing Scots pine shoots: an analysis on their origin and significance. Dissertationes Forestales 71

UV-induced NOy emissions in gas-exchange chambers enclosing Scots pine shoots : an analysis on their origin and significance

It is essential to have a thorough understanding of the sources and sinks of oxidized nitrogen (NOy) in the atmosphere, since it has a strong influence on the tropospheric chemistry and the eutrophication of ecosystems. One unknown component in the balance of gaseous oxidized nitrogen is vegetation. Plants absorb nitrogenous species from the air via the stomata, but it is not clear whether plants can also emit them at low ambient concentrations. The possible emissions are small and difficult to measure. The aim of this thesis was to analyse an observation made in southern Finland at the SMEAR II station: solar ultraviolet radiation (UV) induced NOy emissions in chambers measuring the gas exchange of Scots pine (Pinus sylvestris L.) shoots. Both measuring and modelling approaches were used in the study. The measurements were performed under noncontrolled field conditions at low ambient NOy concentrations. The chamber blank i.e. artefact NOy emissions from the chamber walls, was dependent on the UV irradiance and increased with time after renewing the Teflon film on chamber surfaces. The contribution of each pine shoot to the total NOy emissions in the chambers was determined by testing whether the emissions decrease when the shoots are removed from their chambers. Emissions did decrease, but only when the chamber interior was exposed to UV radiation. It was concluded that also the pine shoots emit NOy. The possible effects of transpiration on the chamber blank are discussed in the summary part of the thesis, based on previously unpublished data. The possible processes underlying the UV-induced NOy emissions were reviewed. Surface reactions were more likely than metabolic processes. Photolysis of nitrate deposited on the needles may have generated the NOy emissions; the measurements supported this hypothesis. In that case, the emissions apparently would consist mainly of nitrogen dioxide (NO2), nitric oxide (NO) and nitrous acid (HONO). Within studies on NOy exchange of plants, the gases most frequently studied are NO2 and NO (=NOx). In the present work, the implications of the emissions for the NOx exchange of pine were analysed with a model including both NOy emissions and NOy absorption. The model suggested that if the emissions exist, pines can act as an NOx source rather than a sink, even under relatively high ambient concentrations.Maapallon ilmakehästä noin 78% on typpikaasua (N2). Esimerkiksi teollisuuden polttoprosessien kuumuudessa N2 voi hapettua. Hapettumisen tuloksena syntyy ensin typen oksideita (NO ja NO2, joihin viitataan yhteisesti lyhenteellä NOx) ja näistä edelleen muita hapettuneita typpiyhdisteitä, esimerkiksi typpihappoa ja erilaisia nitraatteja, joihin NOx mukaanlukien viitataan lyhenteellä NOy. Typen oksidien merkittävimmät lähteet ovat fossiilisten polttoaineiden käyttö, biomassan poltto, maaperän pieneliöiden toiminta ja salamointi. NOy-yhdisteet ovat ilmansaasteita. Suurina pitoisuuksina niistä on haittaa esimerkiksi ihmisen hengityselimistölle. Pienempinä määrinä NOy-yhdisteet ovat tärkeitä, koska ne osallistuvat olennaisiin ilmakemiallisiin reaktioihin. NOx vaikuttaa suoraan mm. haitallisen alailmakehän otsonin syntyyn. Hapettunut typpi poistuu ilmasta laskeutumalla maan pinnoille sateen mukana ja kuivalaskeumana. Tämä toisaalta lannoittaa ja lisää kasvien kasvua eli rehevöittää ekosysteemejä, toisaalta myös happamoittaa maaperää. Eräs tuntematon tekijä NOy:n kiertokulussa on kasvillisuus. Kasvien tiedetään ottavan ilmasta kaasumaisia typpiyhdisteitä ilmarakojensa kautta, kun yhdisteen pitoisuus ilmassa on riittävän korkea. Kasvien toiminnasta matalissa pitoisuuksissa ei sen sijaan ole varmuutta. Jotkut tutkijat ovat havainneet, että kasveista voi silloin vapautua NOx:a, mutta tätä ei havaita aina. Asia on vaikea selvittää, koska reaktiivisten NOx- ja NOy- yhdisteiden pienet pitoisuudet ja vuot on hankala mitata. Tämän tutkimuksen tarkoitus oli tarkastella ilmiötä, joka havaittiin Hyytiälässä SMEAR II mittausasemalla: auringon ultraviolettisäteily vapautti NOy-yhdisteitä kammioissa, joilla mitattiin männyn oksien kaasunvaihtoa. Hyytiälässä ilman NOy-pitoisuudet ovat yleisesti hyvin matalia. Männyn kaasunvaihtoa tutkittaessa oksa suljettiin kammioon, ja mitattiin, miten kaasupitoisuudet kammiossa muuttuivat kasvin toiminnan seurauksena. Tutkimuksessa havaittiin UV-säteilyn vapauttavan NOy-yhdisteitä mittakammioiden sisäpinnoilta, mutta myös männyn oksilta. Olennainen osa väitöskirjatyötä oli selvittää, miten nämä kammion seinien ja männyn oksien NOy-emissiot saadaan erotettua toisistaan. Emissiot eivät vaikuttaneet olevan peräisin puun aineenvaihdunnasta vaan neulasten pinnoilta. Työssä esitettiin, että ilmasta neulasille laskeutuneen nitraatin hajoaminen UV-valossa aiheutti havaitut emissiot. Tämä ilmiö on merkityksellinen kasvien NOx- ja NOy-vaihdon tutkimuksen kannalta. Pintareaktiot ovat haitaksi, kun halutaan selvittää kasvin aineenvaihduntaa, mutta toisaalta ne ovat erottamaton osa kasvillisuuden NOy-vuota luonnossa, ja tulisi siksi huomioida. Kasvien kaasunvaihdon osalta yleisesti tutkituin typpiyhdiste on ollut NOx. Tässä työssä havaittujen UV-säteilyn aiheuttamien emissioiden merkitystä männyn NOx-vaihdolle tarkasteltiin mallilla, joka kuvasi verson NOy-emissioita ja NOy:n ottoa. Malli ennusti, että mikäli emissiota tapahtuu, männyt toimivat pikemminkin NOx:n lähteenä kuin nieluna jopa suhteellisen korkeissa ilman NOx-pitoisuuksissa