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Gross N turnover and soil solution chemistry as influenced by fluctuations of soil water potential and water table in a Podzol and a fen soil (2011)

Yao-Te Chen

Given the climate scenarios, the higher frequency of drying/rewetting cycles of soils in the future can be expected. These changes of the meteorological conditions likely result in an increasing frequent and intensive drought periods in summer, causing irregular and extreme drought stress in forest soils or a drawdown of water table in wetland ecosystems, which may influence the turnover of nutrients in soils to a larger extend than previously thought. The question arises how these climate changes will influence N and C turnover in forest and fen soils. A growing number of laboratory studies on drying/rewetting of soils have been published during past decades, but many studies used either disturbed soil samples or intact soil cores in laboratory. Although soil drying is a frequent phenomenon in the field, the long-term effects of drying/rewetting and irrigation on in situ fluxes and concentrations of solutes in forest and fen soils are unclear. Several studies have investigated the influence of soil water content on net N turnover rather than gross rates. Net ammonification and nitrification include two major processes: gross ammonification and gross nitrification on the one side and microbial immobilization on the other side. To identify the response of specific processes to soil drying, gross rates need to be measured. This thesis focused on the impact of changing water potential or water table level on gross N turnover rates and soil solution chemistry in two different ecosystems in South-Eastern Germany. In a Norway spruce forest, the effects of decreasing water potential and prolonged periods of summer drought on soil gross N turnover were investigated by laboratory and field experiments. Soil solutions and throughfall were collected and the cumulative in situ fluxes of DIN, DON and DOC with forest floor percolates were calculated. In a minerotrophic fen, we studied the response of N and C mineralization and soil solution chemistry to water table fluctuations in a laboratory experiment. In the field, we collected the soil pore water in 3 depths to clarify the long-term effects of water table level on the concentrations of solutes. Homogenized soil samples of the Oi+Oe, Oa and EA horizons were taken and adjusted to 6 different water potentials in the laboratory. In the field experiment, throughfall exclusion and irrigation plots were established to simulate different precipitation patterns of a dry and wet growing season. Gross N turnover rates were determined in undisturbed soil cores from Oi+Oe and Oa+EA horizons during the drying period and after rewetting. Soil drying decreased gross ammonification rates in the O horizon. The lowest rates were found at the throughfall exclusion plots but the differences to the irrigation and control plots were not statistically significant. A substantial ammonification rate of 14 mg N kg-1 soil day-1 was observed at 3.2 MPa (pF 4.5). The laboratory study showed that gross nitrification decreased with decreasing water potential and was more sensitive to drying than ammonification in the Oa horizon; however, this was not found in the field experiment. The latter might result from the low rates and huge spatial variation, indicating the difference between disturbed samples and intact soil cores. No rewetting pulse of gross ammonification was observed, probably due to its short duration or due to the slow changes of the water potential during the natural rewetting. Although the in situ fluxes of DIN increased at the throughfall exclusion plots after rewetting, the cumulative DIN flux at the throughfall exclusion plots did not significantly exceed that at the control plots. The lowest fluxes of DON and DOC were observed at the throughfall exclusion plots because of the reduction of input with throughfall. In the studies presented here, extended drought periods caused a reduction of gross N turnover in forest soils but gross ammonification continued at considerable rates at low water potential. The hypothesis of increased N turnover and fluxes of DIN, DON and DOC as a consequence of drying/rewetting was not confirmed. In the fen site, undisturbed soil cores were taken and divided to two treatments of water table: permanently flooded and fluctuated. The later was subjected to flooding, drawdown and re-flooding. The permanently flooding enhanced gross ammonification after a lag phase of about 30 days while CO2 emissions were constantly low. The water table drawdown also increased gross ammonification, but again after a lag phase of about 30 days. The first peak of CO2 emissions appeared immediately after water table drawdown, followed by a decrease and a second peak. The ratio of CO2 emission/gross ammonification were close to 2 under anoxic condition which seems to be caused by fast N turnover in the microbial biomass-N pool and low rates of CO2 production. The changes induced by water table drawdown on the N and C turnover were found reversible after re-flooding. Drainage increases SO42- but decrease Fe, DON and DOC concentrations and vice versa when the soils were flooded. Release of DON and DOC was inhibited by increasing SO42- concentrations. Under field conditions, neither drainage nor flooding had an effect on dissolved inorganic N due to the low concentration, indicating the rapid consumption of mineralized N in the field. In the absence of plant uptake and runoff in the laboratory experiment, however, NH4+ increased during the flooding period. Soil desiccation affects the upper soil layers with largest rates of N turnover. While gross N turnover is reduced by soil desiccation, a substantial rate of ammonification was observed even at low water potentials. Nitrification was found more sensitive to desiccation than ammonification which might change the NH4/NO3 ratio of available N under dry conditions. Rewetting of dry soil does not induce a pulse of N turnover and fluxes of DIN, DON and DOC. Overall, an increasing frequency of drying/rewetting cycles seem to have only moderate effect on the N turnover and on N solute fluxes in forest soils. Fluctuations of water table play an important role for the organic matter mineralization, soil solution chemistry and inorganic N availability in minerotrophic fen soils. Acidification by oxidation of S to SO42- can be expected after water table drawdown, causing inhibition of DON and DOC release. The effect of drainage and flooding on gross mineralization and solute concentrations is reversible within a month period. The effect of changing water table regime on N and C turnover in fen soils seems to depend largely on the time scale of the fluctuations. Short term fluctuations at a daily scale will have little effect on N turnover as compared to longer term changes on a monthly scale, while short term changes seem to trigger C losses by CO2.

Documentation and Instruction Manual for the Horizontal Mobile Measuring System (HMMS) (2011)

Jörg Hübner Johannes Olesch Hubert Falke Franz X. Meixner Thomas Foken

Halogens and trace elements in subduction zones (2011)

Diego Bernini

This thesis concentrates on solubilities and incorporation mechanisms of halogens and trace elements in minerals and aqueous fluids at high temperatures and pressures. The solubility of fluorine and chlorine in upper mantle minerals (forsterite, enstatite and pyrope) and halogen partitioning between aqueous fluids and these minerals were investigated by piston-cylinder experiments at 1100 °C and 2.6 GPa. Chlorine solubility in forsterite, enstatite and pyrope is below the ppm level, and it is independent of fluid salinity. The fluid-mineral partition coefficient of chlorine is 103-106, indicating extreme incompatibility of chlorine in nominally anhydrous silicates. The fluorine solubility in enstatite and pyrope is two orders of magnitude higher than for Cl, with no dependence on fluid salinity. Forsterite dissolves 246-267 ppm up to a fluid salinity of 1.6 wt. % F. At higher fluorine contents in the system, forsterite is replaced by the minerals of the humite group, which host fluorine in the hydroxyl site. The fluid-mineral partition coefficient of fluorine ranges from 101 to 103. Due to the extreme incompatibility of Cl in a peridotite mineral assemblage, fluid flow from a subducting slab through the mantle wedge will lead to more efficient sequestration of H2O (when compared to Cl) into minerals, thus inducing a gradual increase in the fluid salinity. Mass balance calculations reveal that rock-fluid ratios of (1.3-4)∙103 are required to produce the characteristic Cl/H2O signature of primitive arc magmas. This indicates that fluid flow from subducting slabs into the melting regions in the overlying mantle is not confined to narrow channels but it is sufficient to pervasively metasomatize the bulk wedge. Energetics of fluorine incorporation in forsterite and forsterite-humite chemical equilibria were explored in the system Mg2SiO4-MgF2 by first principles computations. The pressure-volume equations of state and ground-state energies were determined for orthorhombic Mg2SiO4-Mg2F4 solutions, fluorine-bearing end-members of the humite group, and sellaite (MgF2). Humite group minerals and sellaite are energetically more stable than their equivalent solid solution compounds, hence they can act as buffers of fluorine solubility in forsterite. Compressibility increases systematically with the F content for both solid solution compounds and stable minerals. Nevertheless, end member solids are systematically less compressible than the respective solid solution compounds. The pressure-volume equations of state, internal energies, configurational and excess properties were used to set up a thermodynamic model of fluorine solubility in forsterite buffered by humite-group minerals up to 1900 K and 12 GPa. Humite is the stable F buffer in the investigated pressure and temperature range. The fluorine solubility in forsterite increases with temperature, from 0.01 ppm F at 500 K up to 0.33 wt. % F at 1900 K and 0 GPa. By contrast, the effect of pressure on the fluorine solubility is small, leading to its minor decrease as pressure rises to 12 GPa. These results demonstrate that partition coefficients of fluorine between forsterite and aqueous fluid (or silicate melt) are expected to increase with increasing temperature and decreasing pressure. When fluids or melts pass through the mantle wedge, fluorine will most efficiently be stored in the high-temperature portions of the wedge, promoting mantle metasomatism beneath the arc, and it will be released when the metasomatized mantle is advected to colder regions or to higher pressures. The mobility of high field strength elements in aqueous fluids in subduction zones was addressed by in-situ zircon solubility measurements in a hydrothermal diamond anvil cell. The zircon solubilities in aqueous fluids at 865-1025 oC and 6-20 kbar buffered by quartz are very low, ranging from 1.0 to 3.3 ppm Zr, and solubilities weakly increase with temperature and pressure. Experimental results were fitted to a density model: , where c is the Zr concentration in the fluid (ppm), T is temperature (K) and rho is the fluid density (g cm-3). Additional experiments have shown that Zr solubility increases with a decrease in silica activity and with the presence of NaCl and albite due to Zr-Cl or alkali-Zr complexing but it still remains very low. Therefore, the low Zr content observed in arc magmas is due to a very low mobility of Zr in aqueous fluid.

ExchanGE processes in mountainous Regions (EGER)- Documentation of the Intensive Observation Period (IOP3) June, 13th to July, 26th 2011 (2011)

Andrei Serafimovich Fabian Eder Jörg Hübner Eva Falge Linda Voß Matthias Sörgel Andreas Held Qianqian Liu Rafael Eigenmann Kilian Huber Henrique F. Duarte Peter Werle Eckhard Gast Stanislaw Cieslik Liu Heping Thomas Foken

Reconstruction of the Late and Mid-Pleistocene climate and landscape history in SE-Central Europe - A paleopedological and geochemical multi-proxy approach in loess-paleosol studies. (2011)

Björn Buggle

Loess-paleosol sequences (LPSS) potentially are valuable archives for past environmental conditions. In SE-Central European lowlands thick loess plateaus can be found comprising several glacial-interglacial cycles. This work focuses on key sections in the middle and lower Danube Basin to i) investigate the origin of the loess and archive genesis, ii) to set up a reliable chronostratigraphy and iii) to contribute to the reconstruction of the Mid- and Late Pleistocene climate and landscape history of the region by a paleopedological – geochemical multi-proxy approach. Furthermore, methodological investigations aim to evaluate the validity of various paleoenvironmental proxies especially geochemically based weathering indices, as well as biomarker and stable isotope approaches in LPSS research. The results from geochemical analyses reveal that alluvial material of the Danube and its tributaries represent major sources for the loess in the middle and lower Danube Basin. From the geochemical point of view the studied loess can be regarded as a representative sample of the upper continental crust altered by at least one sedimentary cycle. The chronostratigraphy of the studied sections is based on the correlation of characteristic patterns of the magnetic susceptibility to the delta 18O record of benthic foraminifera from the Ocean Drilling Program site 677, a proxy record for the global ice volume. This is supplemented by correlating magnetic susceptibility fingerprints and pedostratigraphic marker horizons to previously established chronostratigraphies from profiles in the region as well as in China. The results show that the Batajnica/Stari Slankamen LPSS (Serbia) and Mircea Voda LPSS (Romania) comprise at least the last 700.000 years of climate history i.e. the last 17 marine isotope stages. The multi-proxy approach for paleoenvironmental reconstruction involves micromorphological parameters, silicate weathering intensity as given by element composition, grain size proxies for pedogenic clay formation and wind strength, as well as determination of sedimentation rates. As most suitable proxy for silicate weathering in calcareous sediments, the molar ratio Al2O3/(Na2O + Al2O3) × 100 is introduced as Chemical Proxy of Alteration (CPA) to loess paleosol research. Moreover, diffuse reflectance spectroscopy, soil color proxies and rock magnetic proxies are applied to gain paleoenvironmental information from the concentration and assemblage of iron minerals. Focusing on the warm periods, these proxies reveal a progressive decrease of interglacial weathering and soil formation intensity over the Mid - and Late Pleistocene. Also soil forming milieu was less oxidative as reflected by the iron mineralogical composition. These findings suggest cooling and a decline of rainfall linked to a change in seasonality from a Mediterranean type of climate to a more continental steppe climate. Results from n-alkane biomarkers support that summer dryness limiting the expansion of trees was a persistent feature of interglacial climate in SE-European lowlands. In the obtained proxy dataset, increase of wind strength, gradual cooling as well as decrease of rainfall since the early Mid-Pleistocene is also evident for glacial periods. After evaluation of potential triggers, this general climatic trend is proposed to be related to Pleistocene uplift of Eurasian mountain ranges. Changes in atmospheric circulation and rain shadow effects due to mountain uplift (Himalaya, Alps, Carpathians) would provide an explanation for the westward expansion of the Eurasian steppe belt into SE-Central Europe. Future studies on LPSS may also involve highly innovative proxies such as n-alkane biomarker and their D/H isotope signature. However, the methodological investigations on modern soil profiles and samples from litterbag experiments suggest that in a LPSS these proxies might be biased by microbial reworking. Procedures for correcting n-alkane ratios based on the odd over even predominance as reworking indicator have been developed. Hence, these studies highlight the limitations but also the persisting potential of innovative approaches from organic and isotope geochemistry in paleoenvironmental investigations of loess-paleosol sequences.

Formation of secondary organic aerosol and its processing by atmospheric halogen species – A spectroscopic study (2011)

Johannes Ofner

Atmospheric aerosols play an important role in the global climate system. Through their physicochemical properties, they contribute in various ways to climate change and radiative forcing. Those properties can be considerably changed by processing the aerosols, which is especially significant for organic aerosols processed with atmospheric trace gases like halogens released through sea-salt activation or from other sources. Based on aerosol smog-chamber experiments, the formation of secondary organic aerosols (SOA) from predominantly aliphatic (α-pinene) or aromatic (catechol and guaiacol) precursors and the processing of those model SOAs with simulated molecular and naturally released halogens were studied. Different physicochemical methods were used to study the transformation of those organic aerosols. Infrared and UV/VIS spectroscopy allowed the determination of functional and structural changes during aerosol formation and processing. Using electron microscopy and measurement of the particle size distribution, the formation of the morphology and geometry of the particles was investigated. Temperature-programmed pyrolysis mass spectroscopy and ultra-high-resolution mass spectroscopy delivered detailed information on functional groups, extent of halogenation, and the macromolecular structure. Organic aerosols are significantly influenced by atmospheric halogens. Halogen species from different sources change the aerosol size distribution, the presence of functional groups, and the optical properties. Furthermore, they even form halogenated species in the solid phase of the organic aerosol.

The carbon speciation in the Earth’s interior as function of pressure, temperature and oxygen fugacity (2011)

Vincenzo Stagno

The redox state of the Earth’s interior will influence the speciation of volatile elements both in the mantle and in mantle derived magmas. Carbon is one of the principal elements to be affected in this way because under reducing conditions it forms graphite or diamond, and under oxidizing conditions carbonate (or CO2-bearing) minerals and melts. The cycling and residence time of carbon in the mantle can be strongly effected by the oxygen fugacity because reduced phases such as diamond and graphite are immobile and likely to remain within the mantle and potentially within subducting slabs, while at more oxidizing conditions CO2-rich fluids or melts can migrate and escape from the interior. The carbon cycle in the Earth may therefore depend on the redox state of mantle rocks. Conversely, an influx of CO2-rich fluids or melts may act to oxidize the mantle as an additional aspect of metasomatism. In the first part of this study experiments were performed to measure the oxygen fugacity at which carbon (graphite or diamond) oxidises to carbonate minerals or melts within mantle peridotite assemblages between 2.5 and 11 GPa at 1100-1600 °C. The experiments were performed up to temperatures where carbonate melts evolve towards more silicate-rich compositions. The dilution of the carbonate melt component was found to lower the relative fo2, expanding the melt stability field with respect to reduced carbon. The results allow the fo2 of the diamond formation process to be determined both as a function of pressure, temperature and melt CO2 concentration. These results also have implications for the onset of melting within up welling mantle material. Several studies have indicated that the mantle may become more reduced with depth. This means that the oxidation of elemental carbon (graphite or diamond) may occur in up welling rocks where the oxidized product is a carbonate bearing magma. When the experimental data are compared with current estimates for the fo2 of mantle rocks the implication is that peridotitic mantle will remain in the diamond stability field up to at least 100-150 km depth. Only at depths shallower than 150 km would Fe3+ in mantle silicates react with graphite to produce carbonate rich melts in a redox melting process. Redox melting should limit the depth interval over which carbonate-rich melts can form beneath ridges. Further experiments were performed to determine the fo2 at which diamond oxidises to carbonate in the transition zone and lower mantle. Experiments at 45 GPa were performed using the MADONNA D-DIA (1500 tons) apparatus with sintered diamond anvils installed at the Geodynamics Research Centre, Ehime University in Japan. The measured oxygen fugacity was found to be approximately 3 log units above the iron-wüstite oxygen buffer (deltaIW+3). As the oxygen fugacity of the transition zone and lower mantle is most likely at or below the IW buffer this confines the stability of solid carbonate to the upper mantle or to unusually oxidized regions of the deeper mantle. The oxygen fugacity at which magnesite and diamond coexist showed a slight decrease with pressure, however, implying the possibility that magnesite may become the stable host for carbon at the very base of the lower mantle. The oxygen fugacity at which mantle xenoliths equilibrated can be determined using oxy-thermobarometry equilibria. For garnet-peridotite rocks the only calibrated and tested oxy-barometer employs the equilibrium, 2Fe3Fe23+Si3O12 = 4Fe2SiO4 + 2FeSiO3 + O2 Garnet Olivine Orthopyroxene In the final section of this thesis Fe3+/ΣFe ratios of garnets produced in a peridotite assemblage in equilibrium with carbon and carbonate melts were measured between 3 and 7 GPa. The oxygen fugacity in these experiments was also constrained, which allowed a test of this widely used oxy-barometer to be made at pressures much higher than previously performed. The results indicate that the pressure dependence of this oxy-barometer may be in error and a preliminary recalibration implies that cratonic lithosphere may not be as reduced as previously considered.

Soil-Landscape Modelling in an Andean Mountain Forest Region in Southern Ecuador (2010)

Mareike Ließ

Soil-landscapes are diverse and complex due to the interaction of pedogenetic, geo-morphological and hydrological processes. The resulting soil profile reflects the balance of these processes in its properties. Early conceptual models have by now resulted into quantitative soil-landscape models including soil variation and its unpredictability as a key soil attribute. Soils in the Andean mountain rainforest area of southern Ecuador are influenced by hillslope processes and landslides in particular. The lack of knowledge on the distribution of soils and especially physical soil properties to understand slope failure, resulted in the study of this particular soil-landscape by means of statistical models relating soil to terrain attributes, i.e. predictive soil mapping. A 24 terrain classes comprising sampling design for soil investigation in mountainous areas was developed to obtain a representative dataset for statistical modelling. The soils were investigated by 56 profiles and 315 auger points. The Reference Soil Groups (RSGs) Histosol, Stagnosol, Umbrisol, Cambisol, Leptosol and Regosol were identified according to the World Reference Base for Soil Resources (WRB). While soil profiles and auger points were described in their horizon composition, thickness, soil cohesion, bulk density and texture were analysed in soil profiles only. The prediction of soil parameters was carried out with Classification and regression tree (CART) and Random Forest (RF) method. At this, prediction uncertainty was addressed with hundredfold model runs based on different random Jackknife partitions. Problems with the prediction of the RSGs, likely caused by inconsequence within the WRB (absolute and relative values as decision criteria), resulted in the proposal of “incomplete soil classification”, which relates the thickness of the diagnostic WRB horizons to the upper 100 soil centimetres. Histosol and Stagnosol have been distinguished as dominant RSGs within the inves-tigation area. While Histosol probability depended on hydrological parameters; highest Stagnosol probability was predicted on slopes < 40° and above 2146 m a.s.l. Whether the first mineral soil horizon displays stagnic properties or not, likely depends on physical soil properties in addition to terrain parameters. Incomplete soil classification resulted in histic and stagnic soil parts dominating the first 100 cm of the soil volume for most of the research area. Comparing CART and Random Forest (RF) in their model performance to predict topsoil texture and bulk density as well as mineral soil thickness by hundredfold model runs with random Jackknife partitions, RF predictions resulted more powerful. Altitude a.s.l. was the most important predictor for all three soil parameters. Increasing sand/ clay ratios with increasing altitude, on steep slopes and with overland flow distance to the channel network are caused by shallow subsurface flow removing clay particles downslope. Deeper soil layers are not influenced by the same process and therefore showed different texture properties. Terrain parameters could only explain the spatial distribution of topsoil properties to a limited extent, subsoil properties could not be predicted at all. Other parameters that likely influence soil properties within the investigation area are parent material and landslides. Strong evidence was found that topsoil horizons did not form from the bedrock underlying the soil profile. Parent material changes within short distance and often within one soil profile. Landslides have a strong influence on soil-landscape formation in shifting soil and rock material. Soil mechanical and hydrological properties in addition to terrain steepness were hypothesized to be the major factors in causing soil slides. Thus, the factor of safety (FS) was calculated as the soil shear ratio that is necessary to maintain the critical state equilibrium on a potential sliding surface. The depth of the failure plane was assumed at the lower boundary of the stagnic soil layer or complete soil depth, depending on soils being stagnic or non-stagnic. The FS was determined in dependence of soil wetness referring to 0.001, 0.01, 0.1 and 3 mm/h net rainfall rate. Sites with a FS ≥ 1 at 3 mm/h (complete saturation) were classified as unconditionally stable, sites with a FS < 1 at 0.001 mm/h as unconditionally unstable. The latter coincided quite well with landslide scars from a recent aerial photograph.

Exotic Species Invasion and Biodiversity in Bangladesh Forest Ecosystems (2011)

Mohammad Belal Uddin

Both, biological invasion by exotic plant species and biodiversity including spatial patterns and drivers are two major issues in tropical forest ecosystems. This dissertation deals with these two issues in a tropical forest ecosystem in Bangladesh. Considering the first issue, it comprises two manuscripts: a systematic review and a field survey in Bangladesh forest ecosystem. The review was done based on a formalized literature search in order to summarize the approaches that were hitherto applied as well as to mark gaps in tropical invasion research. A considerable number of primary research papers focused on invasion by plants in tropical forests were reviewed. The results identified ample gaps of research. Adressing these gaps may generate promising future research to understand and mitigate this great challenge in different types of tropical forests. Then a case study was conducted to examine the invasiveness and invasibility characteristics in a forest ecosystem of Bangladesh. This study seeks to find out the characteristics of exotic species and relationships between native species richness, environmental variables, disturbances and exotic plant invasion in this ecosystem. Boosted Regression Trees and Detrended Correspondence Analysis are used to determine these relationships. Most exotics are trees followed by shrubs and herbs. Fabaceae and Asteraceae contribute a large proportion of exotic species. Most of them originated from other tropical areas. Native species richness was found to be the best predictor for the number and percentage of exotic species in the study area. However, a unimodal relationship was found. Multiple other factors also influence the success of exotic species. The number and the percentage of exotic species are positively correlated with frequency of disturbances and with soil attributes (phosphorus and bulk density) but negatively correlated with topography (elevation) and conservation patterns (protection). Considering the biodiversity issue, it encompases another two manuscripts based on a case study conducting a systematic field work in the same forest ecosystem of Bangladesh. They are the first spatially explicit analysis of drivers and patterns of biodiversity in this terrestrial ecosystem based on multivariate approaches, similarity analysis and variation partitioning. One manuscript assesses the relationships between landscape and habitat characteristics, conservation patterns, and plant diversity in this tropical forest ecosystem. This study analyses the effects of soils, topographic conditions, disturbances and nature protection on plant species richness and species composition. The results reveal that biodiversity patterns in the study area are positively correlated with protection and elevation. These patterns are, however, negatively correlated with disturbances. The other manuscript focuses on the stand characteristics and spatial patterns of biodiversity as they are rarely studied in the tropics in general and in Bangladesh in particular. Data on tree species are used as they are the most conspicuous element of these ecosystems. Tree species composition was recorded in a systematic plot design and diameter was measured at breast height for each individual tree. Distance-decay approach was applied to analyze the spatial pattern of biodiversity for the whole study area and two subsamples from Satchari National Park and Satchari Reserve Forest. Analyses showed that biomass increased significantly with protection status. Plots in the Reserve Forest were associated with higher species turnover than in the National Park. This dissertation identifyies, for the first time in a systematic approach, the major drivers for invasion and biodiversity pattern in a forested area in Bangladesh. In conclusion, both, biological invasion by exotic plant species as well as biodiversity are strongly related to the disturbance regime and nature protection.

The reactivity of ferric (hydr)oxides towards dissolved sulphide (2010)

Katrin Hellige

Ferric (hydr)oxides are ubiquitous with different characteristics such as stability, reactivity and surface properties and play an important role in redox reactions in many environments such as soils, marine sediments, lakes, and ground water. Under anoxic conditions, ferric (hydr)oxides are reduced by dissolved sulphide or by microorganisms. This reaction generates Fe(II) which may precipitate as iron hydroxide, adsorb to the ferric (hydr)oxide surfaces and transform the ferric (hydr)oxides into more stable minerals, or precipitate as iron sulphide. During the reductive dissolution adsorbed species like arsenic may be released from the oxide surfaces to solution. Furthermore, the generation of ferrous iron in ground water systems, their transport through the groundwater-surface water interface, and subsequent iron oxidation and precipitation contribute to the acidification of lakes or sediments as a result of both mining activities and natural processes. Hence, the redox reactions between dissolved sulphide and ferric (hydr)oxides are of fundamental importance for the elemental cycles of sulphur and iron and in particular for the carbon and electron flow in groundwater, soil, and lake systems. The overall chemical pathway of the reactions and their kinetics are reasonably understood. There is less knowledge on the transient stages and the electron transfer processes during the reactions which involve the formation of amorphous or disordered, as well as, nucleation of (metastable) crystalline phases at the reacting interface as a function of time. Furthermore, the interaction between dissolved sulphide and ferric (hydr)oxides can be regard as a key reaction ultimately leading to pyrite formation in both marine and freshwater sediments. However, the knowledge on the pathways and on the controlling factors of pyrite formation is still limited. Therefore this work focused on anoxic abiotic kinetic batch and flow-through experiments with various ferric (hydr)oxides and dissolved sulphide at pH 4 and pH 7. TEM, X-ray diffraction, Mössbauer spectroscopy, and wet chemistry were used to explore the nanocrystalline products which formed over time during the reaction. Furthermore, these experiments should be contribute to the elucidation of the role of Fe2+ regarding the iron sulphide formation and the transformation of Fe(III) oxides. The electron transfer reaction between dissolved sulphide and ferric (hydr)oxides and the deeper insight into the processes occurring at the ferric (hydr)oxides surfaces were investigated in chapter 2 and 3. Batch experiments with dissolved sulphide and ferrihydrite, lepidocrocite, and goethite were performed under well-defined conditions at pH 7 and at room temperature in a glove box with a special emphasis on the characterization of nanocrystalline products forming at different time steps over a reaction time of 14 days. The temporal evolution of the chemical species and the solid phases indicate that the reaction progress was highly dynamic. After two weeks we observed the formation of secondary minerals and pyrite in all experiments as a result of excess-Fe(II) formation. Ferrihydrite was transformed completely via dissolution-precipitation processes into more stable minerals such as magnetite, hematite, pyrite, and into minor amounts of goethite. In the experimental solution with lepidocrocite and goethite the host mineral remained and we detected only pyrite as new mineral. Small amounts of goethite were transformed to hematite while the pyrite formation in the experimental solution with lepidocrocite was accompanied by traces of magnetite. In chapter 4, the reaction kinetic of dissolved sulphide and ferric (hydr)oxides were studied under abiotic, anoxic, and flow-through conditions at pH 4 and 7 and at room temperature over a time period of 6 hours. Various synthetic Fe(III) (hydr)oxides with a broad range of crystallinity and different surface and bulk properties were used in order to assess how variations in these properties influence the kinetics of chemical Fe(III) (hydr)oxide reduction. These experiments showed, as well as, the batch experiments, that the formation of Fe(II) and S(0) was decoupled. In the presence of ferrihydrite and lepidocrocite the generated Fe(II) due to the reaction with dissolved sulphide adsorbed to their surfaces and was accompanied by an electron transfer which led to the formation of excess-Fe(II). These processes seem to be accelerating the reductive dissolution of ferrihydrite and lepidocrocite by dissolved sulphide. Goethite behaved differ: the adsorption of Fe(II) onto the goethite surface occurred without an electron transfer. Thus, the generated Fe(II) controls the reductive dissolution of various ferric (hydr)oxides by dissolved sulphide.

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