5 Naturwissenschaften und Mathematik
Impact of extreme hydrological conditions on belowground carbon cycling and redox dynamics in peat soils from a northern temperate fen
Cristian Estop Aragonés
- Peatlands have an important role in the global carbon cycle and constitute the largest pool of carbon stored in terrestrial ecosystems due to their disproportionally high areal soil carbon density. This globally relevant carbon stock is the result of a process mostly initiated after the last glaciation period. A key factor for this long term carbon accumulation is the relative low decomposition of organic matter in these predominantly water logged ecosystems. Hydrological conditions play thus a fundamental role in peatlands and the feedback of carbon cycling in these ecosystems in response to climate change is under debate. Peatlands are important CO2 sinks but also constitute global sources of CH4. The atmospheric exchange and production rates of these greenhouse gases are strongly influenced by the hydrological regime. An increased frequency of extreme meteorological conditions resulting in drying and flooding events is predicted to occur in the future.
The major issue regarding the climate change debate at the global scale is how rapid these greenhouse gases are being released to the atmosphere. Despite the general consensus regarding the broad effects of drying and flooding on CO2 and CH4 exchange, belowground processes producing such greenhouse gases and their response to water table dynamics is underrepresented and usually simplified or overgeneralized. Temperature, moisture, oxygen content and nutrient content are among the major environmental controls for organic matter decomposition rates in peat soils. Another important and intrinsic control is peat quality or humification degree of organic matter. The interrelation and relevance of all these factors vary among sites and with hydrological condition in a temporal and spatial scale.
This work presents investigations focusing on belowground redox processes aiming to witness the dynamic interrelation of soil physical and chemical (soil gas and pore water chemistry) variables, and evaluates the relevance of some controls of organic matter decomposition during a wide range of hydrological conditions. Most of this work shows information under in situ conditions and complementary laboratory experiments were performed minding the in situ observations. The findings contribute to general knowledge by providing raw data in fen peats under fluctuating and contrasting water table conditions in a relatively high spatiotemporal resolved scale. Dryings led to increased air filled porosity, O2 intrusion, CO2 degassing, inhibition of methanogenesis and renewal of electron acceptors. The opposite trend occurred upon rewetting with pulses of iron and sulphate reduction and delayed methane production to a variable extent. Upon flooding, continued anaerobic conditions stimulated the accumulation of reduced products, methanogenic precursors (acetate and hydrogen) and CH4.
The general assumption that the water table directly controls the oxygen content in peat was relativized. This work shows that such relation is greatly influenced by peat physical properties, which partially control the changes in moisture. Based on these findings, the mineral content and the degree of compaction in organic soils can be implemented to more accurately represent the dynamics of aeration in peats upon water table changes. Another general assumption is that drying events, i.e. temporary decline of water table below mean position, lead to increased CO2 production and emission from peat soils to the atmosphere. Such statement was also relativized and must account for the depth distribution of respiration rates in relation to the mean water table of the peat deposit. Based on these findings, the high relative contribution of upper peat layers already exposed above the water table mask the effects of increased CO2 production in deeper peat upon water table drop. Additionally, the role of moisture was shown to be little for aerobic respiration. This work also evaluates the importance of drought severity by accounting for the post drought effects on methane production. More intense and prolonged drying events led to a greater regeneration of electron acceptors in peat soil, which broadly suppressed or limited methane production upon rewetting. This relation was not simple and several factors such as water table position, post drought water table fluctuations, temperature and organic matter content contributed to the recovery of methane production after drying. The provision of substrates by fermentation processes limited peat respiration during shallow water table and drying. In contrast, accumulation of acetate and hydrogen was observed during flooding indicating a decoupling of fermentation from terminal metabolism and favouring the co-occurrence of iron reduction, sulphate reduction and methanogenesis.
Mineral sequestration of CO2 by reaction with alkaline residues
- With the onset of industrialization within the last 150 years, a significant increase in the concentration of the greenhouse gas carbon dioxide (CO2) is recorded in the atmosphere. According to current scientific understanding the rising atmospheric CO2 levels can be linked with high probability to the observed phenomenon of global warming. Consequently, the reduction of anthropogenic greenhouse gas emissions has become a global challenge of environmental research and policy.
In this thesis, a novel approach to achieve a long-term mineral sequestration of CO2 was studied, using alkaline residue materials. This study examined for the first time a process that allows for rapid removal of CO2 from flue gas through reaction with lignite fly ashes in aqueous solution.
In this process the basicity of the residues is utilized for mineral trapping of CO2 by precipitating stable calcite. Lignite fly ashes are a cheap, inexpensive, highly reactive byproduct of coal combustion. Due to the exposure to heat, these waste streams generally contain high amounts of reactive Ca/Mg (hydr)oxides and thus offer a high alkalinity. The alkaline residues were therefore not considered as an environmental problem, but rather as useful reactants for technical CO2 neutralization in the context of combustion processes.
Carbonates are end-products of weathering processes at the earth surface and mineral carbonation is thus assessed to be a permanent and safe storage option of CO2. Compared to alternative forms of carbon storage (e.g. the injection into gas reservoirs) cost-intensive monitoring programs for safety reasons can be omitted. Also, the carbonation generally leads to heavy metal fixation in the residues, allowing for an environmentally less problematic disposal of the products or even their industrial re-use (e.g. road construction, cement industry). Due to the common high reactivity of alkaline fly ashes no pre-treatment (e.g. grinding, using chemical additives) is needed compared to the use of natural silicate minerals as feedstock material. For these reasons mineral carbonation of alkaline residues can be considered as a process with low costs and low energy consumption, thus making it an interesting CO2 reduction pathway from an economical point of view.
In Chapter 1, the mechanisms and rates of reactions between alkaline lignite fly ash and CO2 in aqueous suspensions were evaluated. Aqueous laboratory experiments showed that CO2 from flue gas can be bound directly as carbonate. Additionally, solutions with high dissolved inorganic carbon content are formed, which can be injected into aquifers for mineral CO2 sequestration. As the dissolution rates of the alkaline mineral phases are high, gas phase CO2 transfer into the aqueous phase is mostly the limiting factor for the overall carbonation process. CO2 dissolution is controlled by the solution pH, by the available surface area of the gas/water interface and by the gradient at that interface.
The maximum conversion of 5.2 moles of CO2 per kg fly ash (≈ 0.23 kg kg-1) obtained at 75 °C demonstrates the high potential of alkaline fly ashes to sequester CO2. This value accounts for a CO2 sequestration capacity of nearly 3.5 million t of CO2 in Germany alone based on the available lignite fly ash, which corresponds to 2 percents of the CO2 emissions from lignite power combustion (168 million t a-1 in 2009).
In Chapter 2, laboratory carbonation experiments are described, which were carried out with the individual mineral phases CaO and MgO in aqueous solution. The process showed parallels with the reactions observed during carbonation of lignite fly ashes, suggesting that Ca and Mg (hydr)oxides can be used as proxies to estimate alkaline waste reaction with CO2 in general.
The carbonation of CaO happens fast, occurs at high pH values > 12 and is controlled at the mineral surface by the dissolution of Ca(OH)2. As long as Ca(OH)2 is available CO2 uptake by the system is high and leads to the simultaneous precipitation of calcite (CaCO3). Under similar conditions MgO carbonation is a slower and much more complex process. In the presence of MgO an initial pH of ~ 10.8, indicating solubility equilibrium, was reached. Subsequently, TDIC concentrations and EC increased almost linearly. The pool of MgO based alkalinity can be made available for mineral trapping if the kinetic restrictions for precipitation of Mg-carbonate can be overcome, e. g. by running the processes at higher temperature (> 50 °C) and higher s/l-ratio. Corresponding to related work the precipitation of hydromagnesite (Mg5(CO3)4 (OH)2 ∙ 4H2O) is found for temperatures above 50 ° C already at a suspended amount of 4 g L-1. Precipitation of nesquehonite (MgCO3 ∙ 3H2O)) starts upon a suspended amount of MgO of more than 10 g L-1 at 25 ° C.
In Chapter 3 the setup and the results of a model are shown, which was used to simulate and evaluate the process of alkaline material carbonation over time. Experimentally derived specific dissolution rates for CaO/MgO and CO2 are used for the development of a kinetic geochemical model based on the freely available PHREEQC algorithm. The software offers the access to databases, which containing thermodynamic constants of all common dissolved species in natural and industrial processes.
Experimental assays conducted in an aqueous carbonation reactor (see Chapter 1 and 2) were used as reference to test the model and evaluate its robustness and sensitivity.
The reaction course of the experiments based on the use of the pure phases (CaO and MgO) was successfully reproduced by our simulations. The developed model may thus be used as a valuable tool for the optimization of technical scenarios/facilities for CO2 sequestration. In order to study different mineral sequestration scenarios for calcite precipitation, we used the simulation to test the variation of process parameters and the addition of chemical additives (CaCl2, CaSO4). Finally, the simulation of the carbonation of lignite fly ash was tested using our simplified model based on CaO, MgO, calcite, anhydrite as kinetic reactants. It was shown that advanced techniques to determine the exact mineralogy of combustion residues and the extension of the availability of thermodynamic data of specific mineral phases are necessary to improve geochemical modelling in future work.
In Chapter 4, the potential contribution of lignite fly ash to mineral CO2 trapping in a high anhydrite (CaSO4) containing aquifer were analyzed. The study examined the possibility of combining underground CO2 storage and geothermal heat/energy production from an anhydrite rich aquifer. In such a scenario Ca2+ for the precipitation of calcite could be provided from the dissolution of the calcium sulfate. The dissolution of anhydrite concurrently releases acid, being counterproductive with respect to the formation of carbonates. The possibility of pH buffering by the addition of alkaline lignite fly ash is therefore appraised to optimize the conditions of carbonate precipitation.
The performed laboratory experiments, as basis for thermodynamic simulations with PHREEC, confirmed that the buffering capacity derived from the fly ashes is essential for calcite precipitation in such a system. Already with an addition of 0.1 weight percent of fly ash per volume of the injection solution the amount of precipitated calcite was maximized. The dissolution of anhydrite is associated with a concurrent increase in pore space and can balance the porespace reduction by precipitation of carbonates and secondary silicates in the geothermal reservoir.
Quantifying water use by temperate deciduous forests in South Korea: roles of species diversity, canopy structure, and complex terrain
- About seventy percent of South Korea is covered with forests, most of which are found in the mountain regions since mountains receive more rainfall and are difficult terrains not suitable for agriculture. Because mountains are important water sources for cities and human population downstream, performing water balance for forest catchments has become a research priority. The ongoing shift from coniferous to species-rich deciduous forests due to a changing government policy and the anticipated changes in future climate, associated with increasing amount of rainfall and temperature will also impact forest water use, calling for an urgent need to understand how forests, in their current status, use water. The knowledge is vital for predicting water requirements for the future forest. The warm-deciduous temperate forests found in South Korea, however, have a high diversity of tree species, have multi-layered canopies and are mostly located on rugged mountainous terrains, which make it difficult to quantify forest water use, a basic requirement for catchment water budgeting. The main objectives of this study were to: (1) identify the roles of species diversity in tree and forest water use, (2) examine the impact of canopy structure on forest transpiration, and (3) evaluate the influence of terrain on forest water use.
Site-specific studies were carried out in three different natural deciduous forests, namely, Gyebang (GB), Gwangneung (GN) and Haean (HA) forest sites, representing the general structure of S. Korean forests. GB site is known for its high species diversity, GN site is an old forest growth at climax, with clearly defined understory and overstory canopy layers while the HA site was located with in a catchment, with strong elevation changes within short horizontal distances, rising from 400 to 1,000 m a.s.l., and in different aspects. Four locations with varying elevations and aspects were chosen in the HA site. Tree water use (TWU) and canopy transpiration (EC) were estimated from sap flux density measured with thermal dissipation probes. Understory transpiration (EU) was measured using stem heat balance while ecosystem evapotranspiration (Eeco) was determined using eddy covariance technique. Air temperatures (Ta), precipitation, solar radiation, vapor pressure deficit (VPD), wind speed were measured from weather stations and soil water content was measured from frequency domain reflectometry (FDR) sensors at the respective study sites. Vegetation surveys, including diameter at breast height (DBH), tree density, species composition, sapwood area (AS), and leaf area index were performed in all the sites. Canopy conductance (GC) and stomatal sensitivity to VPD were assessed based on transpiration and microclimate measured at each site.
A functional allometric relationship was established between AS and DBH, and also between TWU and DBH for all the study sites; first for single species and then combining all the species either in a single site or in all the sites. Irrespective of tree species, AS and maximum TWU were significantly correlated with DBH in a power function for AS (R2 = 0.77, P <0.0001) and both in power (R2 = 0.63, P <0.0001) and sigmoid functions (R2 = 0.66, P <0.0001) for TWU, for the co-occurring species as well as across the sites, suggesting that DBH can be a good predictor of stand AS and maximum TWU, based on the established allometric functions.
Early bud break and development of the understory compared to the overstory canopy resulted in an earlier onset of forest transpiration, with EU contributing 22% and 14% between April and May to the total forest transpiration. This high contribution was favored by high radiation and VPD in the understory, since the overstory was still undeveloped and open. Despite diminishing VPD and light conditions in the understory between June and August, the understory continued to transpire a substantial amount of water, contributing 10% of the total transpiration. The seasonal patterns of both EO and EU were synchronized to canopy development, while VPD and radiation determined daily trends. EO and EU accounted for 80% of Eeco in spring but only 60% during the monsoon period due to lowered radiation input, VPD, and plant area index (PAI). Thus, Eeco is largely influenced by transpiration rate and its seasonal variation and also canopy structure.
Early saturation of EC at relatively low VPD and also a rapid decrease in GC with increasing VPD were observed in the forest stand located at the highest elevation studied (950 m) in the HA site, compared to the GN and the other forest stands in HA. These differences in transpiration rates and stomatal response can be explained by greater stomatal sensitivity to VPD of 0.83 found at the 950 m site compared to 0.63–0.66 in the other study sites. However, the main controlling factor of the change in stomatal sensitivity at the 950 m stand is uncertain. Although maximum daily EC were correlated with AS of the forest stands at different sites (R2 = 0.78, P <0.01), annual EC declined with increasing elevation, i.e., 176 >175 >110 >90 mm year−1 at 340 >450 >650 >950 m, respectively. Decline in total EC was due to the decline in annual Ta, daytime VPD, and length of growing season at higher elevations. The GB site, which was located at 960 m elevation, however, did not display a same response pattern as those observed at the 950 m site. It is likely because these sites were under different environmental conditions, i.e., GB site is exposed to higher Ta and higher humidity, and is sheltered (lower wind speeds). These observations emphasize the complexity associated with estimation of transpiration in rugged terrains, since general principles do not always apply and the spatial patterns of forest transpiration are complex.
Complexity arising from multiple tree species composition when estimating forest water use can be reduced by applying functional allometric relationship linking tree size and water use. Forest canopy structure and physical location should be taken into account since they influence the way forests use water resources by altering microclimate and plant physiology. Based on our findings, estimation of forest water use on rugged terrains require repeated measurements at relatively small spatial scales since the driving factors change rapidly over very narrow vertical distances.
Umsetzung verschiedener didaktischer Theorien im außerschulischen Unterricht: Potentiale und Grenzen des wiederentdeckten Lernorts Bauernhof
- Die Entfremdung von Lebensmittelproduktion und landwirtschaftlicher Praxis sowie das Unwissen über enge Verflechtungen zwischen Umwelt und Landwirtschaft der heranwachsenden Generation (Ernst & Theimer, 2011; Hubert, Frank, & Igo, 2000; Tal, 2008) sind ein allgemeines gesellschaftliches Problem, dem man mit Bildung begegnen kann und sollte (Harms, King, & Francis, 2009). Um diese Themen, im Sinne einer Bildung für nachhaltige Entwicklung, zu vermitteln und so innerhalb der Gesellschaft zu festigen, scheint sich am besten situationsbezogenes und kontext-orientiertes Lernen am außerschulischen Lernort Bauernhof zu eignen (Knobloch, Ball, & Allen, 2007). Kontext-orientiertes Lernen ermöglicht den Schülerinnen und Schülern das in der Schule Gelernte auf den Alltag zu übertragen und so effektiver zu lernen (Bennett, Lubben, & Hogarth, 2007).
Das in dieser Studie entwickelte agrarische Umweltbildungsprojekt unterscheidet sich bewusst von bestehenden, zum Teil mehrtägigen und erlebnisorientierten Projekten, indem es Schulpraxisrelevanz für sich beansprucht: Es wird auf Ansprüche und Anforderungen des Lehrplans (fachliche Inhalte, Kompetenzvermittlung, kurze Projektdauer), der Lehrer (einfache Organisation und Durchführbarkeit) und der Schüler (schülerzentrierte und kooperative Lernmethode) Rücksicht genommen und diese bestmöglich umgesetzt.
Die Zielsetzungen der Promotionsstudie waren zum einen genauere Untersuchungen zur Naturverbundenheit von Kindern (Teilarbeit A), die Erziehung zu umweltfreundlicherem Konsumverhalten (Teilarbeit B) und eine kognitive Wissensvermittlung durch das entwickelte Projekt (Teilarbeit C). Darüber hinaus wurden noch Schülervorstellungen zur landwirtschaftlichen Praxis am Anfang und Ende der Sekundarstufe I erhoben (Teilarbeit D), um die Wahrnehmung von Landwirtschaft bei Kindern und Jugendlichen in einer modernen Industriegesellschaft besser beurteilen zu können. Das Wissen dieser Vorstellungen ist als Basis zur Erarbeitung effizienter Bildungsmaßnahmen in diesem Bereich erforderlich.
Teilarbeit A zeigt sowohl einen negativen Zusammenhang zwischen dem Alter (untersucht wurde der Zeitraum vor dem Einsetzen der Pubertät (9 – 13 Jahre)) als auch einen positiven Zusammenhang zwischen den kognitiven Fähigkeiten (Indikatorvariable: Schulform) und dem Grad der Naturverbundenheit.
Frühere Studien (Davis, 2011; Schultz, 2002) zeigten einen engen Zusammenhang zwischen Naturverbundenheit und umweltfreundlichem Verhalten. Dennoch hat sich in Teilarbeit B herausgestellt, dass Naturverbundenheit bei den Bildungsprojekt-Teilnehmern (Durchschnittsalter: 11,5 Jahre) keinen wichtigen Beitrag zur Intention für umweltfreundlicheres Konsumverhalten leistete, ebenso wenig wie das neu hinzugewonnene Wissen. Signifikant hingegen waren die Korrelationen mit situationsbedingten Lernemotionen, die direkt im Anschluss an die Unterrichtseinheit gemessen wurden. Jedoch war das Konsumverhalten nach sieben Wochen wieder auf dem vor der Intervention gemessenem Ausgangsniveau.
Wissensvermittlung, die Hauptintention der meisten Bildungsprojekte, erwies sich in Teilstudie C für die teilnehmenden Schüler insgesamt, unabhängig vom Lernort (Klassenzimmer vs. Bauernhof), als erfolgreich. Schlüsselt man die einzelnen Wissensbereiche weiter auf, so ergab sich ein signifikanter mittelfristiger Lernzuwachs bei Mädchen zum Thema Ernährung, und ein signifikanter kurz- und mittelfristiger Lernzuwachs für das Themengebiet Landwirtschaft bei beiden Geschlechtern.
Schließlich wurde in Teilstudie D Schülervorstellungen zu den Aufgaben eines Landwirts erhoben. Hierzu wurden Schüler am Anfang der Sekundarstufe I (5./6. Jahrgangsstufe) und am Ende (10. Jahrgangsstufe) befragt. Bei der induktiven Kategorienbildung der qualitativen Inhaltsanalyse nach Mayring (2007) ergaben sich kaum Unterschiede zwischen den Altersgruppen, jedoch lag der Schwerpunkt der Arbeitsaufgaben für die jüngeren Schüler bei den Tieren und für die Älteren bei den Pflanzen. Lediglich ein geringer Anteil der Zehntklässler nannte ökologische Aufgabenbereiche, bei den Jüngeren fehlt dieser Aspekt völlig. Generell zeigten sich sehr stereotype und einfache Vorstellungen bei den teilnehmenden Schülern.
Kurze, schülerzentrierte Bildungsmaßnahmen im Bereich der Landwirtschaft und Ernährung können kurz- und mittelfristig Wissen vermitteln, Anregungen für umweltfreundlichere Verhaltensweisen schaffen und positive Lernemotionen stärken, die sich jedoch stark auf das Antwortverhalten der Schüler auswirken können. Zusammenfassend kann man sagen, dass das entwickelte Bildungsprojekt gut geeignet ist, Grundlagen der agrarischen Umweltbildung schülergerecht zu vermitteln. Die Inhalte des Projekts sollten wiederholt in der Schullaufbahn aufgegriffen und altersgerecht vertieft werden, um den Schülern agricultural literacy(Frick et al., 1991) und damit ein realeres Bild über die moderne landwirtschaftliche Praxis zu vermitteln.