OPUS 4 | Geowissenschaften

Biogeochemical Investigations in Old Growth and Disturbed Forest Sites at Mount Kilimanjaro (2004)

Marion Schrumpf

Areas covered by mountain rainforests in East Africa have important functions as catchment areas for the streams in the savannah. Still, little is known about the biogeochemical processes in these often threatened ecosystems. The current study aims to present basic information on soils and different parameters of the water and nutrient cycle in intact as well as disturbed tropical mountain rainforest sites at Mt. Kilimanjaro in order to assess the long term effects of forest dissection on biogeochemical parameters. For this purpose, the chemical and physical soil properties, soil water tension, rainfall, throughfall, litter percolate and soil solution were determined on twelve study sites in mature forest, secondary forest and elder clearings between 2100 and 2300 m a.s.l. on the southwestern slopes of the mountain. The soil water tension was monitored from May 2000 to August 2002. The simultaneously collected water samples were combined to form fortnight samples and subsequently analysed for their content of K, Mg, Ca, Na, NO3-N, NH4-N, TOC, TON, TOS and TOP. The soils, which comprised of several buried horizons, were Andisols with high C and N stocks, some hydromorphic properties and comparatively low pH values. The latter led to very small ECEC values and low base saturation. Consequently, the retention of cationic nutrients in the soil was considered to be poor. Rainfall amounts were slightly less at the higher sampling sites where the mature forest was located and differed between the study years (2600 mm and 2480 mm at 2100 m, 2210 mm and 1960 mm at 2250 m). Rainfall interception was close to zero in the clearings, but reached up to 30% of incident rainfall in both studied forest types. The analyses of the soil water tension revealed the driest conditions to be under secondary forests. The reason for this was probably a combination of the topographic position of the secondary forest sites and the forest fragmentation. Since the secondary forest sites and the clearings had higher sand contents, the water holding capacity of these sites was lower than in the mature forest. With the exception of NO3-N in the forests, all nutrients in rainfall were increased upon passage through the forest canopy, but nutrient fluxes in rainfall as well as throughfall were still low compared to other mountain rainforests, especially for Mg, Ca and K. Considering the lower biomass of the clearings compared to the forest, the amount of nutrients leached from the vegetation of the clearings was relatively high. Since NO3-N was not assimilated by the vegetation of the clearings, NO3-N throughfall fluxes were higher in the clearings as were the K fluxes, which was probably attributable to different leaf properties of the vegetation at the different sites. In the mature forest, the highest concentrations of nutrients were found in the litter percolate, followed by a pronounced decline in the soil solution. This was especially the case for K. NO3-N was an exception since it exhibited the highest concentrations only in the topsoil solution. Nutrient concentrations in litter percolate and the topsoil solution were usually higher in the clearings than in both forest types. This probably resulted in higher belowground nutrient fluxes since greater water amounts reached the ground surface in the clearings. The high belowground nutrient concentrations were likely the result of the higher mineralisation rates in the clearings induced by higher temperatures and the greater nutrient contents of the litter. With increasing soil depths, nutrient concentrations in seepage water below the clearings declined so that the differences among sites were not significant at deeper soil layers. The contribution of organically bound nutrients to the total concentrations of respective nutrients was highest in throughfall water and lowest in the soil solution, in which OM concentrations were overall lower than in other mountain forests. This was most likely attributable to the adsorption of organically bound nutrients to the mineral phase of the Andisols studied. Again, the highest concentrations in seepage water were measured in the clearings. The results show that mature forests at Mt. Kilimanjaro exhibit a more closed nutrient cycle, especially for basic cations, while the nutrient cycle in the clearings is more open. This probably reflects the different nutrient usage and conservation strategies of the pioneer and the late successional vegetation. Therefore, the forest disturbance on Mt. Kilimanjaro leads to long term changes in biogeochemical cycles. The opening of the forest at lower elevations, which resulted in the formation of large clearings with impeded regeneration and highly fragmented secondary forest patches, led to a higher spatial and seasonal variability of soil moisture and nutrient contents in seepage water. The large scale effects of these forest conversions on water yields and nutrient outputs need to be tested in the future.

Verhalten von Arsen und Chrom in einem mit Holzschutzmitteln belasteten Boden (2005)

Maria Luisa Hopp

In dieser Arbeit wird eine umfassende Charakterisierung von Mechanismen, die die Bindung und den Transport von Arsen und Chrom in einem durch den Eintrag von arsen- und chromhaltigen Holzschutzmitteln stark belasteten Boden kontrollieren, präsentiert. Der Einsatz vielfältiger Methoden erlaubte darüber hinaus eine Evaluierung von Versuchsansätzen zur Abschätzung der Mobilität von Arsen und Chrom. Die Untersuchungen fanden auf dem Lagerplatz eines ehemaligen Holzimprägnierwerkes statt. Der Lagerplatz weist zwei Besonderheiten auf: (1) Eine stark hydrophobe Bodenoberfläche bewirkt eine nur punktuelle Infiltration. (2) Mitte der achtziger Jahre wurde einmalig Fe(II)-Sulfat auf der Bodenoberfläche ausgebracht, um Cr(VI) durch Reduktion zu immobilisieren. Der Boden, ein Podsol aus Flugsanden, wurde bis in eine Tiefe von 200 cm beprobt. Festphasenkonzentrationen von As und Cr wurden in Mischproben bestimmt. Die für eine Bindung relevanten Festphasen wurden in selektiven Extraktionen mit Oxalat- und Dithionitlösungen untersucht. Die Mobilisierung von Arsen und Chrom aus der Festphase wurde in verschiedenen standardisierten Elutionsversuchen (z.B. Bodensättigungsextrakt, BoSE), in einem Säulenversuch und durch die kontinuierliche Beprobung von Bodensickerwasser über einen Zeitraum von zehn Monaten charakterisiert. Zu den Freilandarbeiten gehörten weiterhin die Untersuchung der Hydrophobizität des Bodens und die Durchführung eines Farbtracer-Experiments zur Visualisierung dominierender Fließmuster. Die Entnahme von Grundwasser erfolgte über den Zeitraum von zehn Wochen. Simulationen mit einem numerischen 2D-Transportmodell evaluierten die Konsequenzen der hydrophoben Bodenoberfläche für den Stofftransport. Gesamtgehalte von As und Cr nahmen mit der Tiefe ab und lagen zwischen 103 – 384 mg/kg As und 168 – 1086 mg/kg Cr innerhalb der obersten 65 cm. Die Eisengehalte nahmen von 3,5 g/kg in der obersten Schicht bis auf 0,5 g/kg unterhalb 65 cm ab. Diese für einen Podsol untypische Fe-Verteilung wurde auf die durch die Applikation von Fe(II)-Sulfat erfolgte Anreicherung von Fe im Oberboden zurückgeführt. Die selektiven Extraktionen wiesen auf die Dominanz von geringkristallinen Fe(III)-Festphasen hin. Die Bodenbehandlung mit Fe(II)-Sulfat hatte somit zwei Effekte, die Immobilisierung von Chromat und die Entstehung zusätzlicher Adsorbenten. Aluminium wies die höchsten Gehalte mit 7,3 g/kg in dem Bs-Horizont des Podsols auf und lag hier höchstwahrscheinlich in schwach kristallinen Aluminosilikaten vor, die sich durch ein hohes Anionensorptionsvermögen auszeichnen. Der Boden verfügt daher vor allem in den obersten 65 cm über Bindungskapazität. Cr wurde entweder als Cr(VI) bis in das Grundwasser verlagert oder zu Cr(III) innerhalb der obersten Bodenschichten reduziert. Es bildeten sich nachfolgend Cr(III)-Festphasen bzw. bei der Verfügbarkeit von Fe(II) Cr/Fe-Mischphasen. Die Ausfällung einer reaktiven Cr(III)-haltigen Festphase bedeutete eine Erhöhung des Bindungsvermögens des Bodens. As lag als As(V) adsorbiert an Fe- und Cr-Hydroxiden vor. In den selektiven Extraktionen wurde eine enge Assoziation zwischen As und Al im Bs-Horizont deutlich. Sowohl in den Elutionsversuchen als auch in den Säulenexperimenten zeigte sich eine hohe Auslaugbarkeit von As und Cr über das gesamte beprobte Profil. Die Konzentrationen im BoSE lagen zwischen 68-412 µg/L As und 295-915 µg/L Cr. Die im Säulenversuch beobachteten Maximalkonzentrationen bewegten sich in dem im BoSE ermittelten Bereich. Der Stoffaustrag aus den Bodensäulen konnte für As mit einem linearen Modell und für Cr mit einer asymptotisch verlaufenden Funktion beschrieben werden. Die Beprobung des Sickerwassers bestätigte die hohe Mobilität der beiden Elemente auch im Freiland; die mittleren Konzentrationen betrugen 167 µg/L As und 62 µg/L Cr. Die Sickerwasserkonzentrationen variierten räumlich um zwei bis drei Größenordnungen. Sowohl der BoSE als auch der Säulenversuch waren geeignet, die in-situ auftretenden Maximalkonzentrationen abzuschätzen. Das Farbtracer-Experiment offenbarte einen stark präferenziellen Wasserfluss in diesem Boden, der durch die ausgeprägte Hydrophobizität der Bodenoberfläche verursacht wird. Die räumliche Variabilität der Sickerwasserkonzentrationen kann laut Simulationsstudie dem präferenziellen Transportregime zugeschrieben werden. Der präferenzielle Fluss bewirkt in der jetzigen Phase, in der kein Stoffeintrag mehr stattfindet, dass belastete Bodenzonen effektiv umflossen und vor einer Auswaschung geschützt werden. Hinsichtlich einer Verlagerung bis in das Grundwasser stellt Cr nach wie vor ein Problem an diesem Standort dar. Die Chromkonzentrationen im Grundwasser lagen zwischen 53 und 326 µg/L, während As in nur geringen Konzentrationen (< 10 µg/L) gemessen wurde. Auch nach der Stilllegung von Holzimprägnierwerken kann das Risiko einer Grundwasserkontamination durch Stoffeinträge aus der ungesättigten Bodenzone für viele Jahre fortbestehen.

On the determination of the ground heat flux in micrometeorology and its influence on the energy balance closure (2005)

Claudia Liebethal

The ground heat flux (heat exchange between the atmosphere and the soil), plays a major role in micrometeorology. This is especially true for bare soils in the morning hours, but also for agricultural sites at any time of the day. Thus, this dissertation focuses on three issues: firstly, to establish a reliable and accurate measurement method for the ground heat flux. Secondly, to assess the quality of parameterisation approaches. And thirdly, to study the impact of the ground heat flux on the energy balance closure at the earth's surface. Regarding the measurement of the ground heat flux, different methods are tested. It is concluded that the safest way to determine the ground heat flux is calorimetry (to calculate the ground heat flux as the temporal change in the soil heat storage). The second best so-lution is to directly measure or to calculate the soil heat flux at several decimeters depth (the deeper the better) and to apply calorimetry to the soil layer above. All of the tested approaches strongly react to errors in soil temperature measurements; hence, it is ge-nerally recommended to calibrate, install and maintain soil thermometers as accurately as possible. The measurement approaches for the ground heat flux also require knowledge about soil properties characterising the heat transport within the soil. These can be de-termined either indirectly (from other soil properties) or directly (using e.g. heated sen-sors). Generally, the direct measurement revealed several difficulties during the tests presented in this thesis. Their application is only recommended with restrictions. Whenever the ground heat flux cannot be measured directly with the methods identified as accurate, parameterising is the second-best choice. Here, six different para-meterisation approaches are tested. The main finding is that acceptable quality of ground heat flux data can only be achieved with parameterisations including at least some measurements made directly in the soil. All other approaches, relying only on at-mospherical data such as the sensible heat flux or net radiation, exhibit severe drawbacks in the comparison. Finally, the impact of ground heat flux determination on the closure of the energy balance at the earth's surface is found to be large. On the one hand, a correct determination of the ground heat flux cannot solve the problem of energy imbalance; even with the highest quality of ground heat flux data, a considerable lack in the energy balance re-mains. On the other hand, this must not lead to the conclusion that an exact determination of the ground heat flux is unimportant. Using data from simplified determination methods results in an additional energy imbalance. Taking into account all the results of this thesis, three main conclusions can be drawn: firstly, a correct determination of the ground heat flux is possible and easily applicable to experimental data sets. Secondly, a parameterisation exclusively relying on meteorological data and delivering high quality data for the ground heat flux could not be found. For an accurate estimation, at least some soil data are required. And thirdly, determining the ground heat flux accurately plays a major role in closing the energy balance with measured data. Still, the ground heat flux alone cannot explain the energy imbalance of experimental data sets.

Freisetzung und Transport von polyzyklischen aromatischen Kohlenwasserstoffen aus / in kontaminiertem Bodenmaterial:Säulenversuche und Lysimeterstudie (2004)

Florian Storck

Polyzyklische aromatische Kohlenwasserstoffe (PAK) stellen ein besonderes Risiko für Mensch und Umwelt dar. Auf zahlreichen Flächen, vor allem ehemaligen Industriestandorten wie Gas- und Teerwerken, finden sich mit PAK kontaminierte Böden. Mit Hilfe von Säulen- und Lysimeterversuchen wird in dieser Arbeit der Einfluß der Temperatur sowie Fließgeschwindigkeit und Ionenstärke der Perkolationslösung auf die Freisetzung und den Transport von PAK unter wassergesättigten Bedingungen untersucht. Untersuchungsmaterial ist ein sandig-lehmiger Schluff, der mit Mineralöl und PAK belastet ist. In ihrem grundsätzlichen Aufbau entsprechen die Säulenversuche den Anforderungen der Vornorm prEN 14405 [CEN, 2002] und den Entwürfen DIN V 19736:2001-11 [DIN, 2001] sowie ISO/TC190WG6 [ISO, 2001]. Säulenexperimente wurden bei 15 und 25 °C mit zwei unterschiedlichen Fließgeschwindigkeiten und Flußunterbrechungen zur Identifizierung ratenlimierter Freisetzung durchgeführt. Um den Einfluß der Ionenstärke zu prüfen, wurde mit NaClO4-Lösung (0,02 mol/L, stellvertretend für eine Bodenlösung) und entsalztem Wasser (nach den Vorschriften der Normenentwürfe bzw. stellvertretend für Regenwasser) perkoliert. Die Lysimeterstudie stand unter natürlichem Temperaturregime des Versuchsortes Bayreuth. Von sonstigen atmosphärischen Einflüssen abgeschirmt, wurde das Lysimeter mit den gleichen Perkolationslösungen, die für die Säulenversuche Verwendung fanden, künstlich beregnet. Als bedeutsam für PAK-Transport und -Freisetzung erwies sich die Temperaturerhöhung um 10 °C. Bei hohen Fließgeschwindigkeiten stiegen die Konzentration im Eluat und die Quellstärke toxischer und cancerogener PAK um bis zu 500 % an. Damit erweist sich die in den Normentwürfen festgelegte Temperaturspanne für Säulenexperimente als zu groß. Noch weit stärker wirkt sich der Wechsel der Perkolationslösungen aus. Perkolation mit entsalztem Wasser führte bei hohen Fließgeschwindigkeiten, wie sie etwa bei Starkregenereignissen zu erwarten sind, zu einem Anstieg der Kolloidfreisetzung und der Eluatkonzentration und Quellstärke aller betrachteten PAK. Hervorzuheben ist hier die Zunahme von cancerogenem und für Wasserorganismen hochtoxischem BaPYR und Bbjk-FLA um den Faktor 400 bei hoher Fließgeschwindigkeit. Generell scheint sich mit höherer Fließgeschwindigkeit auch die Quellstärke zu erhöhen. Ergebnisse des Lysimeterversuches und der Säulenexperimente sprechen dafür, daß sich unter den gewählten experimentellen Bedingungen der PAK-Austrag fast ausschließlich auf Kolloide bzw. Partikel mit einem Durchmesser größer 0,7 Mikrometer beschränkt und DOC als Lösungsvermittler eine geringe Rolle spielt. Ratenlimitierte Freisetzung konnte in den Säulenexperimenten für DOC, nicht jedoch für PAK nachgewiesen werden.

Influence of natural organic matter on the mobility of arsenic in aquatic systems, soils and sediments (2008)

Markus Florian Bauer

The element As is today recognized as one of the most dangerous inorganic contaminants and threats for the world’s water resources. Arsenic is ubiquitious in the earth crust and humans are especially affected through As polluted drinking water supplies. The occurrence of high As groundwater concentrations is often caused by geogenic processes of As release from the solid phase and accumulation in the water phase. Many contaminated aquifers are also characterized by high concentrations of natural organic matter (NOM). Previous studies showed that NOM presence may affect As mobility, but we are lacking evidence about the reactions pathways and about the importance As-DOM interactions in the environment. We therefore focussed on studying reactions between NOM and As, including redox reactions, complexation, colloid formation and sorption competition in laboratory experiments. Moreover we also studied As behaviour in columns experiments and wetland soils rich in organic matter. Arsenic mobility strongly depends on its redox state. Dissolved organic matter was previously found to be redox active but its redox properties are only poorly understood. In laboratory experiments we therefore elucidated the electron transfer characteristics of different DOM samples. The results showed the high potential of humic substances to chemically reduce different Fe(III) complexes and oxidize H2S and metallic Zn. Reactions occurred over short periods of time with reaction rates in the range from 0.03 to 27 h-1. Under otherwise identical conditions rising DOC concentrations caused higher total electron transfer. This supports the assumption that functional groups of DOM, such as quinones, were indeed the redox active moieties involved in the redox reactions. The calculated electron transfer capacities (ETC) ranged from 0.07 to 6.2 mequiv (g C)-1. The wide range of observed reaction rates and ETC values could be related to the different redox potential of the inorganic reactants used. This suggests that DOM molecules contain redox active moieties with different redox potential and that they possibly represent a redox ladder with the capacity to buffer electrons over a wide range of redox conditions. Humic substances also influenced the As redox speciation as dissolved H3AsO4 was - either chemically or microbially- reduced to H3AsO3 in DOM solution. No oxidation of As(III) to As(V) was found in these experiments. The presence of organic matter thus changes the redox speciation of As as well as that of other environmentally relevant elements like Fe or S. This possibly also contributes to a higher mobility of As due to the presence of reduced As and Fe species. The formation of complexes on mineral surfaces is one of the most important immobilization processes for As in soils or sediments. DOM strongly interfered with this As sequestration mechanism due to aqueous and surface complexation reactions. Humic substances were found to prevent the precipitation and sedimentation of iron oxide minerals and promote the formation of DOM and Fe containing colloids at aqueous molar Fe/C ratios of up to 0.1. This impeded the co-precipitation and sedimentation of As with Fe mineral structures and increased the amount of mobile As. Arsenic and Fe content were correlated in the different particle size classes was, suggesting As binding to Fe e.g. in cation bridging complexes or DOM stabilized Fe oxide colloids. DOM sorption on synthetic goethite and natural soil and sediment samples also caused a release of As from these solid phases due to sorption competition for mineral binding sites. Especially the weakly adsorbed fraction of As in the natural samples was affected by this process. Both the formation of aqueous complexes or colloids and the sorption competition in the presence of DOM lead to higher As concentration in the water phase and demonstrate the potential of humic substances to increase As mobility. In the studied laboratory columns As redox transformation and complexation by DOM could not be identified. Instead As mobilization was dominated by microbial processes in these experiments. At DOM input concentrations between 5 and 100 mg L-1 the release of As occurred mainly due to the reductive dissolution of the Fe oxide sorbent phase during microbial respiration. The occurrence of sulfate reduction and the precipitation of sulfide minerals at the highest DOM concentrations did not represent a substantial immobilization mechanism. The studied wetland soils represent natural sinks for geogenic As. Fe oxides were the main As sorbents, which is surprising as both soils were temporarily water saturated and likely under reducing conditions. Moreover, the high porewater DOC concentrations and the high organic carbon content in the solid phase apparently did not interfere with As sorption on the iron phases in these soils. Chemical extractions also showed that smaller As fractions were associated with solid phase organic matter pool and with a not identified residual pool, likely sulfide minerals. However, as most As was bound to Fe oxides its fate was strongly affected by changing redox conditions. Fast As immobilization sorption occurred under dry conditions when Fe was oxidized and precipitated, while short-term mobilization of As and Fe in their reduced form was observed upon rewetting. These soils therefore are As sinks as long as oxic conditions are maintained but may turn into As sources when reducing conditions prevail for longer periods of time. Organic molecules influence the redox state and the complexation of As and are able to shift As partitioning in favour of the solute phase. Our results showed that especially the association of As with aqueous complexes and colloids has a strong potential to reduce As retention and increase As mobility. This has to be considered in future studies of As behaviour in aquifers, surface waters, soils or sediments rich in organic substances. Peatland soils were found to represent sinks for geogenic As, showing that the presence of organic matter not necessarily prevents As immobilization. It also depends on the biogeochemical conditions whether an organic matter rich system will accumulate or release As.

Aluminium stabilizes dissolved organic matter by precipitation (2008)

Thorsten Scheel

It is well known that carbon mineralization in acidic forest soils can be reduced by large Al concentrations. Precipitation of dissolved organic matter (DOM) by dissolved Al could contribute substantially to C retention in acidic forest soils. However, no information is available on the properties of precipitated organic matter (OM) and its stability against microbial decay although that might be an important mechanism for long-term carbon storage in soils. Therefore, I investigated the influence of (i) the DOM composition, (ii) the pH of precipitation, and (iii) the Al/C ratio in solution on the amount of OM precipitated, the associated changes in its composition, and the resulting stability of precipitated OM against microbial decay. Between 13 and 84% of the C in solution was precipitated, depending on pH, Al/C ratio, and the composition of DOM. I observed preferential precipitation of aromatic compounds and enrichment of carboxylic C in precipitated OM, being associated by depletion in N and enrichment in P. The type of bonds between OM functional groups and the Al cations was independent of pH, Al/C ratios and solution composition. FTIR spectra indicated ligand exchange as possible binding mechanism. Furthermore, exoenzymes were present in a functional state in precipitated OM. Carbon mineralization of DOM was up to 28 times larger than that of the respective precipitated OM. Only 0.5-7.7% of precipitated C was mineralized during 7 weeks of incubation. When precipitated OM remained in solution the reduction in C degradation by precipitation amounted up to 65%. This increase in stability by precipitation was significantly correlated with the amount of C precipitated. Thus, the bonds between Al and carboxylic groups of aromatic compounds with low N contents resulted in a reduced bioavailability of C. I found no indication for toxic effects of Al. The enzyme activity found in precipitates significantly increased the percentage of C mineralized of precipitated OM. However, after eight weeks of incubation the correlations between enzyme activity and C mineralization disappeared, despite substantial enzyme activity and C being still present. Thus, degradation of precipitated OM seems to be governed by enzyme activity during the first degradation phase, but the long term stability of precipitated OM is probably related to its chemical properties and structure, e.g. floc size. The Al cations linked a large number of molecules of OM up to floc sizes of 110 µm in diameter, with smaller sizes on average at pH 3.8 (16.6 µm) than at pH 4.5 (27.6 µm). For a floc of 10 µm about 80 million molecules needed to be spatially aggregated. Thus, the spatial accessibility of OM was considerably reduced in these flocs leading to additional stabilization, besides the intrinsic stability of the organic compounds and the complexation by Al. The observation that only a certain fraction of precipitated OM is prone to degradation by enzymes supports this. I conclude that precipitation of DOM is an important mechanism for the long-term carbon stabilization in mineral horizons of acidic forest soils. Changing environmental conditions can affect both the amount of OM precipitated and the degradability of the precipitate. Thus, more focus should be laid on the influence of OM precipitation on C retention and sequestration in acidic forest soils.

Characterization of reactive and non reactive trace gas fluxes in and above soil (2010)

Anika Bargsten

Nitrogen is one of the most important compounds on earth. All organisms need nitrogen to live and grow. Even the majority (78.08%) of the atmosphere (and so the air we breathe) is dinitrogen. Over the last century, human activities have dramatically increased emissions and removal of nitrogen to the global atmosphere by as much as three to five fold. Nitrous oxide is the fourth largest single contributor to positive radiative forcing, and serves as the only long-lived atmospheric tracer of human perturbations of the global nitrogen cycle. Nitrogen oxides belong to the so called indirect greenhouse gases. These indirect greenhouse gases control the abundances of direct greenhouse gases through atmospheric chemistry and contribute on this way to the greenhouse effect. For a better understanding of these feedback mechanisms it is necessary to know the source strength of nitric oxide and nitrous oxide. Thus, the knowledge about exchange processes of nitrogen is of interest and importance for scientist and policy makers, likewise. This thesis contributes the understanding of processes in the nitrogen cycle. The thesis is addressed on nitric and nitrous oxide emissions. Nitric oxide emissions were measured on soil samples using an automated laboratory system. Nitrous oxide emissions were measured directly on the field site using a closed chamber technique. The laboratory measurements were compared with field measurements of NO (modified Bowen ratio method) at a grass land site. The field NO fluxes were always around 1.8 ng m 2 s-1 while the laboratory derived NO fluxes were between 2.1 and 5,2 ng m-2 s-1. The agreement between the two data sets is considered to be quite good. The laboratory derived NO fluxes exceeded the field NO fluxes by a factor of 1.5 to 2.5. Most studies of nitric oxide (NO) emission potentials up to now have investigated mineral soil layers only. In this thesis soil organic matter was sampled for laboratory measurements under different understory types (moss, grass, spruce, blueberries) in a humid mountainous Norway spruce forest plantation in the Fichtelgebirge (Germany). In this thesis the response of net potential NO fluxes on physical and chemical soil conditions (water content and temperature, bulk density, particle density, pH, C/N ratio, organic C, soil ammonium, soil nitrate) was determined. Net potential NO fluxes (in terms of mass of N) from soil samples taken under the different understories ranged from 1.7 - 9.8 ng m 2 s-1 (soil sampled under grass and moss cover), 55.4 - 59.3 ng m-2 s-1 (soil sampled under spruce cover), and 43.7 - 114.6 ng m 2 s-1 (soil sampled under blueberry cover) at optimum water content and a soil temperature of 10°C. Effects of soil physical and chemical characteristics on the net potential NO flux were statistically significant (0.01 probability level) only for NH4+. Therefore, as an alternative explanation for the differences in soil biogenic NO emission we consider more biological factors like understory vegetation type, amount of roots, and degree of mycorrhization; they provide a potential explanation of the observed differences of net potential NO fluxes. Also, soil nitrous oxide (N2O) emissions in an unmanaged, old growth beech forest in the Hainich National Park, Germany, were measured at 15 plots over a one-year period (November 2005 to November 2006). The annual field N2O flux rate was 0.46±0.32 kg ha 1 yr 1. The N2O emissions showed a background emission pattern with two event based N2O peaks. A correlation analysis showed that the distance between plots (up to 380 m) was secondary for their flux correlations. Annual N2O fluxes obtained from a standard model (Forest-DNDC) parameterized with soil parameters as well as daily temperature and precipitation substantially overestimated the actual field N2O fluxes and also did not describe their actual temporal and spatial variabilities. Temporal variability was described well by the model only at plots with higher soil organic carbon and the modelled N2O fluxes increased during freezing periods only were soil organic carbon was larger than 0.06 kg-1 C kg. The results indicate that the natural background of nitrous oxide emissions may be lower than previously thought and also lower than assumed in standard modelling. This suggests a higher anthropogenic contribution to N2O emissions.

Role of Dissolved Organic Nitrogen in the Soil Nitrogen Cycle of Forest Ecosystems (2010)

Bettina Schmidt

In the last years, dissolved organic N (DON) has been shown to be a crucial part of the soil N cycle in forest ecosystems. Despite this, information on its dynamics, sources and fate is still lacking. Especially data from (sub)tropical forest ecosystems are scarce. Therefore, this study investigated (i) the magnitude and drivers of DON fluxes in a subtropical montane forest, (ii) the biodegradability of DON from forest floors, (iii) the abiotic formation mechanism for DON in forest floors as postulated by the Ferrous Wheel Hypothesis and (iv) the link between DON and dissolved organic C (DOC) dynamics. In a field study (2005-2008), average DON fluxes in forest floor percolates and seepage (60 cm) of a subtropical montainous cypress forest (16 and 8 kg N ha-1 yr-1, respectively) were similar to fluxes in other (sub)tropical ecosystems, and dominated total N fluxes. Dissolved organic N concentrations in the soil were independent of the water flux (meaning that no dilution effect was visible). This implies that first, the pool size of potentially soluble DON is variable and second, that this pool is hard to deplete. In contrast, the linear relationship between soil organic solute and water fluxes was positive, showing that precipitation is an important driver for DON losses in this ecosystem. Although this has also been reported from temperate ecosystems, this relationship did not hold when analyzing the combined data from various (sub)tropical and temperate forest ecosystems. The biodegradability of DON was highest in inoculated spruce-Oi water extracts in a 21-day incubation experiment, while in extracts from beech-Oi and Oa horizons, DON concentrations only slightly decreased. Dissolved organic N was recalcitrant in spruce-Oa and cypress-Oa extracts, indicating that this DON could add to the formation of stable soil N pools. As various additions of NO3- never influenced DON biodegradation, it is concluded that microbes do not necessarily prefer mineral N over DON as substrate. Mineralization was always more important than microbial uptake in samples without NO3- additions, and denitrification only played a minor role in spruce-Oi samples (as indicated by a negative balance of all N species after 21 days). Fluorescence excitation-emission spectroscopy and subsequent parallel factor analysis identified four groups of fluorophores in the extracts. The initial concentration of two of these so-called factors was correlated with DON biodegradation, but protein-like fluorescence (which has been suggested as a proxy for dissolved organic matter biodegradation) was shown to be independent of DON biodegradation due to similar excitation-emission-maxima of recalcitrant compounds. Therefore, these factors might not always be suitable to predict DON biodegradation. The abiotic reaction of NO2- with DOC (as postulated by the last step of the Ferrous Wheel Hypothesis) was tested in a second incubation experiment in extracts with varying DOC concentrations and qualities and NO2- additions under oxic conditions. Concentrations of added NO2- never decreased within 60 min, indicating, that no DON formation from added NO2- took place. The results show, that the last step of the Ferrous Wheel Hypothesis (which has been suggested to be fast) is unlikely to occur in forest floors. Dissolved organic N and C fluxes were both highly dependent on precipitation at the cypress site, suggesting a strong link between these two classes of compounds. This assumption was supported by the first incubation experiment, where both DON and DOC biodegradation were not influenced by NO3- additions. Moreover, DOC dynamics closely resembled DON dynamics, which suggests that DON biodegradation could be driven by microbial C demand. Therefore, the often used separation of DON and DOC into functionally different compound classes is not always warranted. In conclusion, this study emphasized the need to include DON in biogeochemical N studies of both temperate and (sub)tropical ecosystems, and provided new and important insights regarding DON biodegradation, possible DON sources in forest floors and the link between DON and DOC dynamics in forest ecosystems.

Proceedings of the International Conference of "Atmospheric Transport and chemistry in Forest Ecosystems" Castle of Thurnau, Germany Oct 5 to Oct 8, 2009 (2009)

Johannes Lüers Thomas Foken

no abstract

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