Geowissenschaften
Refine
Year of publication
- 2016 (80)
- 2010 (59)
- 2014 (53)
- 2015 (53)
- 2008 (52)
- 2011 (52)
- 2009 (48)
- 2013 (46)
- 2020 (46)
- 2019 (45)
- 2017 (35)
- 2012 (33)
- 2005 (27)
- 2018 (27)
- 2007 (25)
- 2021 (22)
- 2003 (20)
- 2006 (19)
- 2002 (17)
- 2023 (17)
- 2022 (16)
- 2001 (13)
- 2004 (13)
- 2024 (11)
- 2000 (7)
- 1998 (5)
- 1999 (5)
- 1913 (2)
- 1914 (2)
- 1919 (2)
- 1976 (2)
- 1907 (1)
- 1909 (1)
- 1918 (1)
- 1920 (1)
- 1921 (1)
- 1922 (1)
- 1925 (1)
- 1964 (1)
- 1969 (1)
- 1971 (1)
- 1973 (1)
- 1974 (1)
- 1978 (1)
- 1980 (1)
- 1990 (1)
- 1995 (1)
- 1996 (1)
- 1997 (1)
Document Type
- Article (593)
- Doctoral Thesis (139)
- Book (25)
- Contribution to a Periodical (21)
- Conference Proceeding (19)
- Working Paper (19)
- Part of Periodical (10)
- Diploma Thesis (8)
- diplomthesis (7)
- Preprint (6)
Is part of the Bibliography
- no (872)
Keywords
- climate change (13)
- Climate change (5)
- Geochemistry (5)
- Klimaänderung (5)
- Atmospheric chemistry (4)
- Boden (4)
- Deutschland (4)
- Klima (4)
- Modellierung (4)
- Stratosphäre (4)
Institute
- Geowissenschaften (872)
- Senckenbergische Naturforschende Gesellschaft (59)
- Präsidium (49)
- Biodiversität und Klima Forschungszentrum (BiK-F) (45)
- Geographie (26)
- Biowissenschaften (15)
- Medizin (11)
- Physik (7)
- Institut für Ökologie, Evolution und Diversität (6)
- Biochemie und Chemie (5)
Attribution and detection of anthropogenic climate change using a backpropagation neural network
(2002)
The climate system can be regarded as a dynamic nonlinear system. Thus traditional linear statistical methods are not suited to describe the nonlinearities of this system which renders it necessary to find alternative statistical techniques to model those nonlinear properties. In addition to an earlier paper on this subject (WALTER et al., 1998), the problem of attribution and detection of the observed climate change is addressed here using a nonlinear Backpropagation Neural Network (BPN). In addition to potential anthropogenic influences on climate (CO2-equivalent concentrations, called greenhouse gases, GHG and SO2 emissions) natural influences on surface air temperature (variations of solar activity, volcanism and the El Niño/Southern Oscillation phenomenon) are integrated into the simulations as well. It is shown that the adaptive BPN algorithm captures the dynamics of the climate system, i.e. global and area weighted mean temperature anomalies, to a great extent. However, free parameters of this network architecture have to be optimized in a time consuming trial-and-error process. The simulation quality obtained by the BPN exceeds the results of those from a linear model by far; the simulation quality on the global scale amounts to 84% explained variance. Additionally the results of the nonlinear algorithm are plausible in a physical sense, i.e. amplitude and time structure. Nevertheless they cover a broad range, e.g. the GHG-signal on the global scale ranges from 0.37 K to 1.65 K warming for the time period 1856-1998. However the simulated amplitudes are situated within the discussed range (HOUGHTON et al., 2001). Additionally the combined anthropogenic effect corresponds to the observed increase in temperature for the examined time period. In addition to that, the BPN succeeds with the detection of anthropogenic induced climate change on a high significance level. Therefore the concept of neural networks can be regarded as a suitable nonlinear statistical tool for modeling and diagnosing the climate system.
Atmospheric observation-based global SF6 emissions - comparison of top-down and bottom-up estimates
(2009)
Emissions of sulphur hexafluoride (SF6), one of the strongest greenhouse gases on a per molecule basis, are targeted to be collectively reduced under the Kyoto Protocol. Because of its long atmospheric lifetime (≈3000 years), the accumulation of SF6 in the atmosphere is a direct measure of its global emissions. Examination of our extended data set of globally distributed high-precision SF6 observations shows an increase in SF6 abundance from near zero in the 1970s to a global mean of 6.7 ppt by the end of 2008. In-depth evaluation of our long-term data records shows that the global source of SF6 decreased after 1995, most likely due to SF6 emission reductions in industrialised countries, but increased again after 1998. By subtracting those emissions reported by Annex I countries to the United Nations Framework Convention of Climatic Change (UNFCCC) from our observation-inferred SF6 source leaves a surprisingly large gap of more than 70–80% of non-reported SF6 emissions in the last decade.
Atmospheric nanoaerosols have extensive effects on the Earth’s climate and human health. This cumulative work focuses on the development and characterization of instrumentation for measuring various parameters of atmospheric nanoaerosols, and its use to understand new particle formation from organic precursors. The principal research question is, how the chemical composition of nanoaerosol particles can be measured and how atmospheric chemistry influences aerosol processes, especially new particle formation and growth. Therefore, nanoaerosols are investigated under various aspects. More specifically, an instrument is developed to analyze nanoparticles, and field as well as chamber studies are conducted.
The main project is the instrument development of the Thermal Desorption Differential Mobility Analyzer (TD-DMA, project 1, Wagner et al. (2018)). This instrument analyzes the chemical composition of small aerosol particles. By characterization and testing in chamber experiments, it is proven to be suitable for the analysis of freshly nucleated particles.
The second project (Wagner et al. (2017)) applies a broad spectrum of aerosol measurement instruments for the characterization of aerosol particles produced by a skyscraper blasting. A comprehensive picture of the particle population emitted by the demolition is obtained.
Project 3 (K¨urten et al. (2016)) is also an ambient aerosol measurement, focusing of new particle formation in a rural area in central Germany, and the ability of a negative nitrate CI-APi-TOF to detect various substances in atmosphere. Project 4 (Heinritzi et al. (2016)) is a characterization of the negative nitrate CI-APi-TOF used in projects 1, 3, 5, 6, 7 and 8. The following projects focus on understanding new particle formation from atmospherically abundant organic precursors. Key instruments comprise the negative nitrate CI-APiTOF for gas-phase measurements of the nucleating species, and various sizing and counting instruments for quantifying the particle formation and growth. Project 5 (Kirkby et al. (2016)) shows that biogenic organic compounds formed from alpha-pinene can nucleate on their own without the influence of e.g. sulfuric acid. Project 6 (Tr¨ostl et al. (2016)) describe the subsequent growth of these particles. Project 7 (Stolzenburg et al. (2018)) covers the temperature dependence of this growth and in project 8 (Heinritzi et al. (2018)), the suppressing influence of isoprene on the new particle formation is assessed.
Explosive volcanism affects weather and climate. Primary volcanic ash particles which act as ice nuclei (IN) can modify the phase and properties of cold tropospheric clouds. During the Eyjafjallajökull volcanic eruption we have measured the highest ice nucleus number concentrations (>600 L) in our record of 2 years of daily IN measurements in central Germany. Even in Israel, located about 5000 km away from Iceland, IN were as high as otherwise only during desert dust storms. These measurements are the only ones available on the properties of IN in the Eyjafjallajökull plume. The measured high concentrations and high activation temperature (−8 °C) point to an important impact of volcanic ash on microphysical and radiative properties of clouds through enhanced glaciation.
We have sampled atmospheric ice nuclei (IN) and aerosol in Germany and in Israel during spring 2010. IN were analyzed by the static vapor diffusion chamber FRIDGE, as well as by electron microscopy. During the Eyjafjallajökull volcanic eruption of April 2010 we have measured the highest ice nucleus number concentrations (>600 l−1) in our record of 2 yr of daily IN measurements in central Germany. Even in Israel, located about 5000 km away from Iceland, IN were as high as otherwise only during desert dust storms. The fraction of aerosol activated as ice nuclei at −18 °C and 119% rhice and the corresponding area density of ice-active sites per aerosol surface were considerably higher than what we observed during an intense outbreak of Saharan dust over Europe in May 2008.
Pure volcanic ash accounts for at least 53–68% of the 239 individual ice nucleating particles that we collected in aerosol samples from the event and analyzed by electron microscopy. Volcanic ash samples that had been collected close to the eruption site were aerosolized in the laboratory and measured by FRIDGE. Our analysis confirms the relatively poor ice nucleating efficiency (at −18 °C and 119% ice-saturation) of such "fresh" volcanic ash, as it had recently been found by other workers. We find that both the fraction of the aerosol that is active as ice nuclei as well as the density of ice-active sites on the aerosol surface are three orders of magnitude larger in the samples collected from ambient air during the volcanic peaks than in the aerosolized samples from the ash collected close to the eruption site. From this we conclude that the ice-nucleating properties of volcanic ash may be altered substantially by aging and processing during long-range transport in the atmosphere, and that global volcanism deserves further attention as a potential source of atmospheric ice nuclei.
has been demonstrated in climate models that both the Indian and East Asian summer monsoons (ISM and EASM) are strengthened by the uplift of the entire Asian orography or Tibetan Plateau (TP) (i.e. bulk mountain uplift). Such an effect is widely perceived as the major mechanism contributing to the evolution of Asian summer monsoons in the Neogene. However, geological evidence suggests more diachronous growth of the Asian orography (i.e. regional mountain uplift) than bulk mountain uplift. This demands a re-evaluation of the relation between mountain uplift and the Asian monsoon in the geological periods. In this study, sensitivity experiments considering the diachronous growth of different parts of the Asian orography are performed using the regional climate model COSMO-CLM to investigate their effects on the Asian summer monsoons. The results show that, different from the bulk mountain uplift, the regional mountain uplift can lead to an asynchronous development of the ISM and EASM. While the ISM is primarily intensified by the thermal insulation (mechanical blocking) effect of the southern TP (Zagros Mountains), the EASM is mainly enhanced by the surface sensible heating of the central, northern and eastern TP. Such elevated surface heating can induce a low-level cyclonic anomaly around the TP that reduces the ISM by suppressing the lower tropospheric monsoon vorticity, but promotes the EASM by strengthening the warm advection from the south of the TP that sustains the monsoon convection. Our findings provide new insights to the evolution of the Asian summer monsoons and their interaction with the tectonic changes in the Neogene.
A realistic simulation of the atmospheric boundary layer (ABL) depends on an accurate representation of the land–atmosphere coupling. Land surface temperature (LST) plays an important role in this context and the assimilation of LST can lead to improved estimates of the boundary layer and its processes. We assimilated synthetic satellite LST retrievals derived from a nature run as truth into a fully coupled, state‐of‐the‐art land–atmosphere numeric weather prediction model. As assimilation system a local ensemble transform Kalman filter was used and the control vector was augmented by the soil temperature and humidity. To evaluate the concept of the augmented control vector, two‐day case‐studies with different control vector settings were conducted for clear‐sky periods in March and August 2017. These experiments with hourly LST assimilation were validated against the nature run and overall, the RMSE of atmospheric and soil temperature of the first‐guess (and analysis) were reduced. The temperature estimate of the ABL was particularly improved during daytime as was the estimate of the soil temperature during the whole diurnal cycle. The best impact of LST assimilation on the soil and the ABL was achieved with the augmented control vector. Through the coupling between the soil and the atmosphere, the assimilation of LST can have a positive impact on the temperature forecast of the ABL even after 15 hr because of the memory of the soil. These encouraging results motivate further work towards the assimilation of real satellite LST retrievals.
It is common practice to use a 30-year period to derive climatological values, as recommended by the World Meteorological Organization. However this convention relies on important assumptions, of which the validity can be examined by deriving the uncertainty inherent to using a limited time-period for deriving climatological values. In this study a new method, aiming at deriving this uncertainty, has been developed with an application to precipitation for a station in Europe (Westdorpe) and one in Africa (Gulu). The weather generator framework is used to produce synthetic daily precipitation time-series that can also be regarded as alternative climate realizations. The framework consists of an improved Markov model, which shows good performance in reproducing the 5-day precipitation variability. The sub-seasonal, seasonal and the inter-annual signals are introduced in the weather generator framework by including covariates. These covariates are derived from an empirical mode decomposition analysis with an improved stability and significance assessment. Introducing covariates was found to substantially improve the monthly precipitation variability for Gulu. From the weather generator, 1,000 synthetic time-series were produced. The divergence between these time-series demonstrates an uncertainty, inherent to using a 30-year period for mean precipitation, of 11 % for Westdorpe and 15 % for Gulu. The uncertainty for precipitation 10-year return levels was found to be 37 % for both sites.
Assessment of ecologically relevant hydrological change in China due to water use and reservoirs
(2008)
As China’s economy booms, increasing water use has significantly affected hydro-geomorphic processes and thus the ecology of surface waters. A large variety of hydrological changes arising from human activities such as reservoir construction and management, water abstraction, water diversion and agricultural land expansion have been sustained throughout China. Using the global scale hydrological and water use model WaterGAP, natural and anthropogenically altered flow conditions are calculated, taking into account flow alterations due to human water consumption and 580 large reservoirs. The impacts resulting from water consumption and reservoirs have been analyzed separately. A modified “Indicators of Hydrologic Alteration” approach is used to describe the human pressures on aquatic ecosystems due to anthropogenic alterations in river flow regimes. The changes in long-term average river discharge, average monthly mean discharge and coefficients of variation of monthly river discharges under natural and impacted conditions are compared and analyzed. The indicators show very significant alterations of natural river flow regimes in a large part of northern China and only minor alterations in most of southern China. The detected large alterations in long-term average river discharge, the seasonality of flows and the inter-annual variability in the northern half of China are very likely to have caused significant ecological impacts.
In this study we show how size-resolved measurements of aerosol particles and cloud condensation nuclei (CCN) can be used to characterize the supersaturation of water vapor in a cloud. The method was developed and applied during the ACRIDICON-Zugspitze campaign (17 September to 4 October 2012) at the high-Alpine research station Schneefernerhaus (German Alps, 2650 m a.s.l.). Number size distributions of total and interstitial aerosol particles were measured with a scanning mobility particle sizer (SMPS), and size-resolved CCN efficiency spectra were recorded with a CCN counter system operated at different supersaturation levels.
During the evolution of a cloud, aerosol particles are exposed to different supersaturation levels. We outline and compare different estimates for the lower and upper bounds (Slow, Shigh) and the average value (Savg) of peak supersaturation encountered by the particles in the cloud. A major advantage of the derivation of Slow and Savg from size-resolved CCN efficiency spectra is that it does not require the specific knowledge or assumptions about aerosol hygroscopicity that are needed to derive estimates of Slow, Shigh, and Savg from aerosol size distribution data. For the investigated cloud event, we derived Slow ≈ 0.07–0.25%, Shigh ≈ 0.86–1.31% and Savg ≈ 0.42–0.68%.
In this study we show how size-resolved measurements of aerosol particles and cloud condensation nuclei (CCN) can be used to characterize the supersaturation of water vapor in a cloud. The method was developed and applied for the investigation of a cloud event during the ACRIDICON-Zugspitze campaign (17 September to 4 October 2012) at the high-alpine research station Schneefernerhaus (German Alps, 2650 m a.s.l.). Number size distributions of total and interstitial aerosol particles were measured with a scanning mobility particle sizer (SMPS), and size-resolved CCN efficiency spectra were recorded with a CCN counter system operated at different supersaturation levels.
During the evolution of a cloud, aerosol particles are exposed to different supersaturation levels. We outline and compare different estimates for the lower and upper bounds (Slow, Shigh) and the average value (Savg) of peak supersaturation encountered by the particles in the cloud. For the investigated cloud event, we derived Slow ≈ 0.19–0.25%, Shigh ≈ 0.90–1.64% and Savg ≈ 0.38–0.84%. Estimates of Slow, Shigh and Savg based on aerosol size distribution data require specific knowledge or assumptions of aerosol hygroscopicity, which are not required for the derivation of Slow and Savg from the size-resolved CCN efficiency spectra.
This study aims to assess the skill of regional climate models (RCMs) at reproducing the climatology of Mediterranean cyclones. Seven RCMs are considered, five of which were also coupled with an oceanic model. All simulations were forced at the lateral boundaries by the ERA-Interim reanalysis for a common 20-year period (1989–2008). Six different cyclone tracking methods have been applied to all twelve RCM simulations and to the ERA-Interim reanalysis in order to assess the RCMs from the perspective of different cyclone definitions. All RCMs reproduce the main areas of high cyclone occurrence in the region south of the Alps, in the Adriatic, Ionian and Aegean Seas, as well as in the areas close to Cyprus and to Atlas mountains. The RCMs tend to underestimate intense cyclone occurrences over the Mediterranean Sea and reproduce 24–40 % of these systems, as identified in the reanalysis. The use of grid nudging in one of the RCMs is shown to be beneficial, reproducing about 60 % of the intense cyclones and keeping a better track of the seasonal cycle of intense cyclogenesis. Finally, the most intense cyclones tend to be similarly reproduced in coupled and uncoupled model simulations, suggesting that modeling atmosphere–ocean coupled processes has only a weak impact on the climatology and intensity of Mediterranean cyclones.
This paper is a contribution to the special issue on Med-CORDEX, an international coordinated initiative dedicated to the multi-component regional climate modelling (atmosphere, ocean, land surface, river) of the Mediterranean under the umbrella of HyMeX, CORDEX, and Med-CLIVAR and coordinated by Samuel Somot, Paolo Ruti, Erika Coppola, Gianmaria Sannino, Bodo Ahrens, and Gabriel Jordà.
This study examines the urban heat island (UHI) of Brussels, for both current (2000–2009) and projected future (2060–2069) climate conditions, by employing very high resolution (250 m) modelling experiments, using the urban boundary layer climate model UrbClim. Meteorological parameters that are related to the intensity of the UHI are identified and it is investigated how these parameters and the magnitude of the UHI evolve for two plausible trajectories for future climate conditions. UHI intensity is found to be strongly correlated to the inversion strength in the lowest 100 m of the atmosphere. The results for the future scenarios indicate that the magnitude of the UHI is expected to decrease slightly due to global warming. This can be attributed to the increased incoming longwave radiation, caused by higher air temperature and humidity values. The presence of the UHI also has a significant impact on the frequency of extreme temperature events in the city area, both in present and future climates, and exacerbates the impact of climate change on the urban population as the amount of heat wave days in the city increases twice as fast as in the rural surroundings.
Brachiopod shells are the most widely used geological archive for the reconstruction of the temperature and the oxygen isotope composition of Phanerozoic seawater. However, it is not conclusive whether brachiopods precipitate their shells in thermodynamic equilibrium. In this study, we investigated the potential impact of kinetic controls on the isotope composition of modern brachiopods by measuring the oxygen and clumped isotope compositions of their shells. Our results show that clumped and oxygen isotope compositions depart from thermodynamic equilibrium due to growth rate-induced kinetic effects. These departures are in line with incomplete hydration and hydroxylation of dissolved CO2. These findings imply that the determination of taxon-specific growth rates alongside clumped and bulk oxygen isotope analyses is essential to ensure accurate estimates of past ocean temperatures and seawater oxygen isotope compositions from brachiopods.
Cheilostome Bryozoa Anoteropora latirostris, a colonial marine invertebrate, constructs its skeleton from calcite and aragonite. This study presents firstly correlated multi-scale electron microscopy, micro-computed tomography, electron backscatter diffraction and NanoSIMS mapping. We show that all primary, coarse-grained platy calcitic lateral walls are covered by fine-grained fibrous aragonite. Vertical lateral walls separating autozooid chambers have aragonite only on their distal side. This type of asymmetric mineralization of lateral walls results from the vertical arrangement of the zooids at the growth margins of the colony and represents a type of biomineralization previously unknown in cheilostome bryozoans. NanoSIMS mapping across the aragonite-calcite interface indicates an organic layer between both mineral phases, likely representing an organic template for biomineralization of aragonite on the calcite layer. Analysis of crystallographic orientations show a moderately strong crystallographic preferred orientation (CPO) for calcite (7.4 times random orientation) and an overall weaker CPO for aragonite (2.4 times random orientation) with a high degree of twinning (45%) of the aragonite grains. The calculated Young’s modulus for the CPO map shows a weak mechanical direction perpendicular to the colony’s upper surface facilitating this organism’s strategy of clonal reproduction by fragmentation along the vertical zooid walls.
The mechanisms of transfer of crustal material from the subducting slab to the overlying mantle wedge are still debated. Mélange rocks, formed by mixing of sediments, oceanic crust, and ultramafics along the slab-mantle interface, are predicted to ascend as diapirs from the slab-top and transfer their compositional signatures to the source region of arc magmas. However, the compositions of melts that result from the interaction of mélanges with a peridotite wedge remain unknown. Here we present experimental evidence that melting of peridotite hybridized by mélanges produces melts that carry the major and trace element abundances observed in natural arc magmas. We propose that differences in nature and relative contributions of mélanges hybridizing the mantle produce a range of primary arc magmas, from tholeiitic to calc-alkaline. Thus, assimilation of mélanges into the wedge may play a key role in transferring subduction signatures from the slab to the source of arc magmas.
The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). Experiments were performed at 10 and −10 °C, on acidic (sulfuric acid) and on partially to fully neutralised (ammonium sulfate) seed aerosol. Clouds were generated by performing an adiabatic expansion – pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and −10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system can be well represented by using accepted rate constants, based on bulk measurements. To the best of our knowledge, these are the first laboratory-based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rate constants to temperatures below 0 °C is correct.
The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). Experiments were performed at 10 and −10 °C, on acidic (sulfuric acid) and on partially to fully neutralised (ammonium sulfate) seed aerosol. Clouds were generated by performing an adiabatic expansion – pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and −10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system can be well represented by using accepted rate constants, based on bulk measurements. To the best of our knowledge, these are the first laboratory-based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rate constants to temperatures below 0 °C is correct.
We present the application of Time-of-Flight Mass Spectrometry (TOF MS) for the analysis of halocarbons in the atmosphere, after cryogenic sample preconcentration and gas chromatographic separation. For the described field of application, the Quadrupole Mass Spectrometer (QP MS) is the state-of-the-art detector. This work aims at comparing two commercially available instruments, a QP MS and a TOF MS with respect to mass resolution, mass accuracy, sensitivity, measurement precision and detector linearity. Both mass spectrometers are operated on the same gas chromatographic system by splitting the column effluent to both detectors. The QP MS had to be operated in optimised Single Ion Monitoring (SIM) mode to achieve a sensitivity which could compete with the TOF MS. The TOF MS provided full mass range information in any acquired mass spectrum without losing sensitivity. Whilst the QP MS showed the performance already achieved in earlier tests, the sensitivity of the TOF MS was on average higher than that of the QP MS in the "operational" SIM mode by a factor of up to 3 reaching detection limits of less than 0.2 pg. Measurement precision determined for the whole analytical system was up to 0.2% depending on substance and sampled volume. The TOF MS instrument used for this study displayed significant non-linearities of up to 10% for two third of all analysed substances.
This study presents an evaluation of a pulse height condensation particle counter (PH-CPC) and an expansion condensation particle counter (E-CPC) in terms of measuring ambient and laboratory-generated molecular and ion clusters. Ambient molecular cluster concentrations were measured with both instruments as they were deployed in conjunction with an ion spectrometer and other aerosol instruments in Hyytiälä, Finland at the SMEAR II station between 1 March and 30 June 2007. The observed cluster concentrations varied and ranged from some thousands to 100 000 cm -3. Both instruments showed similar (within a factor of ~5) concentrations. An average size of the detected clusters was approximately 1.8 nm. As the atmospheric measurement of sub 2-nm particles and molecular clusters is a challenging task, we conclude that most likely we were unable to detect the smallest clusters. Nevertheless, the reported concentrations are the best estimates to date for minimum cluster concentrations in a boreal forest environment.
The ambient and laboratory molecular and ion clusters were investigated. Here we present data on the ambient concentrations of both charged and uncharged molecular clusters as well as the performance of a pulse height condensation particle counter (PH-CPC) and an expansion condensation particle counter (E-CPC). The ambient molecular cluster concentrations were measured using both instruments, and they were deployed in conjunction with ion spectrometers and other aerosol instruments in Hyytiälä, Finland at the SMEAR II station during 1 March to 30 June 2007. The observed cluster concentrations varied and were from ca. 1000 to 100 000 cm−3. Both instruments showed similar concentrations. The average size of detected clusters was approximately 1.8 nm. As the atmospheric measurements at sub 2-nm particles and molecular clusters are a challenging task, and we were most likely unable to detect the smallest clusters, the reported concentrations are our best estimates for minimum cluster concentrations in boreal forest environment.
The oxidation state of sulfur in slab fluids is controversial, with both dominantly oxidized and reduced species proposed. Here we use in situ X-ray absorption spectroscopy analysis of sulfur-in-apatite to monitor changes in the oxidation state of sulfur during high-P metasomatism by slab fluids in the subduction channel. Our samples include a 73 cm continuous transect of reaction zones between a metagabbroic eclogite block and serpentinite matrix from a mélange zone on the island of Syros, Greece. The block core consists of garnet, omphacite, phengite, paragonite, epidote-clinozoisite, and rutile. In this region, apatite is only observed as elongate inclusions in omphacite cores. From the core outwards micas are increasingly replaced by epidote-clinozoisite, garnets are smaller and more frequent, pyrite + bornite is observed as inclusions in recrystallized omphacite, and apatite is increasingly abundant in the matrix and inclusions in garnet. A major transition at 48 cm separates an assemblage of Ca-Na amphibole, omphacite, chlorite, pyrite, and apatite from the inner garnet-bearing eclogite assemblages. Omphacite disappears from the assemblage at ~56 cm and amphibole compositions sharply transition to tremolite at 59 cm. Finally, the assemblage tremolite + talc + pyrite is observed after ~70 cm.Apatites in the eclogite assemblages exclusively display S6+ peaks in their absorption spectra. This includes apatite inclusions in omphacite in the least altered lithology, as well as matrix apatite and isolated apatite inclusions in garnet in the outermost metasomatized eclogite zone. In the intermediate pyrite-rich (~1-5 vol %) amphibole + omphacite + chlorite zone, apatite displays a strong S1- absorption peak in most grains, with rare analyses showing mixed S1- and S6+. Finally, apatite in the outermost tremolite-bearing assemblages only displays a S6+ peak. The pyrite-rich zone at 48 cm occurs at the initial interface between the serpentinite matrix and eclogite block, characterized by a dramatic decrease in Na content and Mg#. Our data suggest that reduction of S6+ in infiltrating fluids to S1- in pyrite became focused as Fe diffused across the steep Mg# gradient, resulting in pyrite precipitation. In contrast, S reduction in the Mg-rich tremolite-dominant portions of the transect was limited by a lack of Fe, resulting in low modes of pyrite and fluid buffered S6+ in apatite. Finally, S6+-bearing apatite is also observed in reaction zone lithologies from elsewhere on Syros, suggesting our observations are not isolated.Two important conclusions are drawn from these data and observations: (1) In the case of Syros, slab fluids at eclogite-facies conditions carried oxidized S6+, and (2) The interaction of these fluids with eclogites composed of ferrous-Fe silicates resulted in extensive sulfide precipitation.
Die Induzierte Polarisation (IP) ist ein geoelektrisches Verfahren und wurde ursprünglich zur Exploration von Erzvorkommen entwickelt. Neben metallischen Leitern, tragen auch Tonminerale, der Porenraum und die chemische Zusammensetzung der Porenlösung zur Polarisierbarkeit eines Unter-grundes bei. Die spektrale Induzierte Polarisation (SIP) untersucht die Polarisierbarkeit in einem Frequenzbereich von 1 mHz bis 1 kHz und nutzt diese aufgezeichneten Spektren zur Unterscheidung von Materialien. Früher mit einem enormen messtechnischen Aufwand verbunden, führte der gerätetechnische Fort-schritt in den letzten beiden Jahrzehnten dazu, dass die SIP vermehrt in der Umweltgeophysik zum Einsatz kommt. Zu den Fragestellungen gehören die Detektion von Altlasten und der Grundwasser-schutz. In der Archäologie ist die Induzierte Polarisation bislang ein kaum verwendetes Verfahren. Im Rahmen des Graduiertenkollegs „Archäologische Analytik“ der J. W. Goethe- Universität wurde die Entwicklung einer Multielektroden-Apparatur SIP-256 begonnen. Ziel der vorliegenden Arbeit war die Fortführung dieser Entwicklung. Da sich die wissenschaftliche Fragestellung während dieser Promotion auf die Erkundung archäologischer Objekte beschränkt, galt es zunächst automatisierte Messabläufe zu realisieren, die es erlauben, die komplexe elektrische Leitfähigkeit kleinräumiger 2D- bzw. 3D-Strukturen zu erfassen. Die Verwendung der SIP-256 führte zu einer erheblichen Ver-kürzung der Messzeit und war entscheidend für die Realisierung dieser Arbeit. Den zweiten Schwerpunkt der Arbeit bildet die Suche nach Anwendungsgebieten für die SIP innerhalb der archäologischen Prospektion. Basierend auf den Ursachen von Polarisationseffekten werden im Rahmen dieser Arbeit drei Anwendungsgebiete vorgestellt. Das erste Anwendungsgebiet nutzt die Vorteile der SIP bei der Prospektion von Erzen. Auf einem mittelalterlicher Verhüttungsplatz bei Seesen am Harz konnten im Vergleich zu einer konventionellen Widerstandsmessung mehr Schlackegruben lokalisiert werden. Während einer deutsch-bulgarischen Grabungskampagne in Pliska (Bulgarien) 1999 gelang es, durch eine flächenhafte Anwendung der IP einen Siedlungshorizont über Lehmablagerungen nachzuweisen. Die Überreste eines Gebäudes erzeugten einen messbaren Polarisationseffekt. Die frühmittelalterlichen Siedlungsreste befinden sich mit 2 bis 3 m in relativ großer Tiefe und konnten bei einer anschließenden Ausgrabung freigelegt werden. Eine Kernfrage war, ob Holzobjekte mit Hilfe der SIP zu detektieren sind. Mit Hilfe von Labormessungen an der TU Clausthal konnte geklärt werden, dass Holz ein polarisierbares Material ist. Zu den untersuchten Proben gehören Hölzer aus einem bronzezeitlichen Bohlenweg, die von Ausgrabungen im Federseemoor (Kreis Biberach) stammen. Durch die Untersuchungen im Labor motiviert, folgte eine Feldmessung über dem Bohlenweg. Es gelang, erstmals ein Holzobjekt mit spektraler Induzierter Polarisation zu detektieren. Holz spielt durch die dendrochronologische Datierung von Fundstellen eine wichtige Rolle, konnte aber bislang noch mit keiner geophysikalischen Methode zufriedenstellend prospektiert werden. Abschließend kann gesagt werden, dass sich die spektrale Induzierte Polarisation als wertvolle Methode in der archäologischen Prospektion etablierte. Strukturen, welche mit einer konventionellen Widerstandsmessung nicht zu erkennen waren, konnten durch die SIP eindeutig identifiziert werden. Natürlich müssen die vorliegenden Ergebnisse noch durch weitere Messungen bestätigt werden, jedoch zeichnet sich ab, dass sich mit der fortschreitenden gerätetechnischen Entwicklung, welche zu schnelleren Messabläufen führt, wichtige Zusatzinformationen durch die spektrale Induzierte Polarisation gewinnen lassen.
In the past sixty years, excessive water consumption and dam construction have significantly influenced natural flow regimes and surface freshwater ecosystems throughout China, and thus resulted in serious environmental problems. In order to balance the competing water demands between human and environment and provide knowledge on sustainable water management, assessments on anthropogenic flow alterations and their impacts on aquatic and riparian ecosystems in China are needed.
In this study, the first evaluation on quantitative relationships between anthropogenic flow alterations and ecological responses in eleven river basins and watersheds in China was performed based on the data that could be obtained from published case studies. Quantitative relationships between changes in average annual discharge, seasonal low flow and seasonal high flow and changes in ecological indicators (fish diversity, fish catch and vegetation cover, etc.) were analyzed. The results showed that changes in riparian vegetation cover as well as changes in fish diversity and fish catch were strongly correlated with the changes in flow magnitude (r = 0.77, 0.66), especially with changes in average annual river discharge. In addition, more than half of the variations in vegetation cover could be explained by changes in average annual river discharge (r² = 0.63) and roughly 50 % changes in fish catch in arid and semi-arid region and 60% changes of fish catch in humid region could be related to alterations in average annual river discharge (r² = 0.53, 0.58).
In a supplementary analysis of this study, the first estimation on quantitative relationships between decreases in native fish species richness and anthropogenic flow alterations in 34 river basins and sub-basins in China was conducted. Linear relationships between losses of native fish species and five ecologically relevant flow indicators were analyzed by single and multiple regression models. For the single regression analysis, significant linear relationships were detected for the indicators of long-term average annual discharge (ILTA) and statistical low flow Q90 (IQ90). For the multiple regressions, no indicator other than ILTA has significant relationships with changes in number of fish species mainly due to collinearity. Two conclusions emerged from the analysis: 1) losses of fish species were positively correlated with changes in ILTA in China and 2) indicator of ILTA was dominant over other flow indicators included in this research for the given dataset. These results provide a guideline for the sustainable water resources management in rivers with high risk of fish extinction in China.
The East African Rift System (EARS) was initiated in the Eocene epoch between 50 and 21 Ma probably due to the influence of mantle plumes that caused volcanism, flood basalts and rifting extensions in Ethiopa and the Afar region. As a result of magmatic intrusions and adiabatic decompression melting within the lithosphere caused by the impact of the Kenya plume, there was a southward propagation of the EARS of about 30 – 15 Ma from Ethiopia to Kenya, which coincide with the occurrence of volcanism. The EARS developed towards the south along the margins of the Tanzania Craton between 15 and 8 Ma. Previous findings of low-velocity anomalies within the upper mantle and the mantle transition zone indicate an upwelling of hot mantle material in the vicinity of the Afar region and the East African Rift. This study includes the analysis of P- and S-receiver functions in order to determine further impacts on the lithosphere from below. The aim was to determine the topographic undulations of further boundary layers and to identify their variability owing to the rifting processes and the formation of the EARS. The study area included the Tanzania Craton and the surrounding rift branches of the East African Rift System.
The region of the Rwenzori Mountains can be analysed in detail because of the large dataset of the RiftLink project. The use of the P-receiver function technique and the H-K stacking method enabled to determine different vP /vS ratios depending on the tectonic setting in the Rwenzori region: Rift shoulders (vP /vS =1.74), Albert Rift segment (vP /vS =1.80), Edward Rift segment (vP /vS =1.87) and Rwenzori Mountains (vP /vS =1.86). To determine the topography of the Moho, it is necessary to take into account the thickness of the sedimentary layer, the surface topography, the azimuthal variations in crustal thickness and the impact of local anomalies. After correcting these effects on the Moho depths, significant variations in Moho topography could be determined. The Moho depths range from 29 to 39 km beneath the rift shoulders of the Albertine Rift. Within the rift valley, the crustal thickness varies between 25 – 31 km in the Edward Rift segment and 22 – 30 km in the Albert Rift segment. An averaged crustal thickness of about 26 km within the rift valley indicates the lack of the crustal root beneath the Rwenzoris. Similar variations in crustal thickness were determined by using an automatic procedure for analysing S-receiver functions that was developed in this study.
The S-receiver functions are created by applying a rotation criterion in order to rotate the Z, N and E components into the L, Q and T components. It is necessary to perform trial rotations using different incident and azimuth angles to determine the correct rotation angles. The latter are identified by the use of the rotation criterion, including the amplitude ratio of the converted Moho signal to the direct S/SKS-wave signal. The L component is rotated correctly in the direction of the incident shear wave in the case of the maximum amplitude ratio. After analysing the frequency content of the receiver functions in order to sort out harmonic and long-periodic traces, the individual Moho signals are checked for consistency in order to remove atypic signals. To increase the signal-to-noise ratios on the traces, the S-receiver functions are stacked. For this purpose, the signals of the direct shear waves must originate from similar epicenters. On the basis of similar ray paths, the receiver functions show comparable waveforms and converted signals. To perform the stacking procedure, it is necessary to merge the datasets of the adjacent stations in order to obtain a sufficient number of receiver functions. This analysis is based on the assumption that the incident seismic waves arriving at the adjacent stations penetrate to some extent the same underground structures in the case of similar wave propagation paths. This approach accounts for the fact that the converted signals do not result exclusively from the piercing points at the boundary layers. Further signals originate from the conversions at the boundary layer within the Fresnel Zone. The piercing points are derived from the significant signals in the receiver functions. Depending on the order of arrival of the converted phases on the traces, the signals are attributed to the theoretical discontinuities DIS1, DIS2, DIS3 and DIS4. However, partly due to the low signal-to-noise ratios on the traces, it is difficult to identify the real conversions on the traces and to ensure that the converted signals are attributed to the correct boundary layers. For this reason, it is necessary to check the consistency of the conversion depths among each other. In the case of inconsistent conversion depths, the corresponding signals are either adjusted to another seismic boundary layer or removed from the dataset. To verify the functionality of the automatic procedure and to determine the resolvability with respect to two boundary layers, several models are tested including horizontal and dipping discontinuities. To resolve distinct discontinuities, their depths must differ by at least 60 km, otherwise, due to similar depth ranges of the different boundary layers, the converted signals cannot be separated from each other. As a consequence, the converted signals that originate from different discontinuities are attributed to a single one. Further tests including break-off edges of seismic discontinuities are performed to check the attributions of the converted signals to the discontinuities. Owing to the varying number of boundary layers, the converted signals cannot be attributed to the discontinuities according to the order of their arrivals on the traces. It is necessary to correct their attributions to the seismic discontinuities in order to resolve the boundary layers.
The crust-mantle boundary and further discontinuities within the lithospheric mantle are investigated by applying this automatic procedure. Depending on the tectonic setting, the conversion depths of the Moho range from about 30 – 45 km beneath the western rift shoulder to 20 – 35 km within the rift valley up to 30 – 40 km beneath the eastern rift shoulder. The long wavelengths of the shear waves hamper the correct identification of the converted phases in the S-receiver functions. With respect to the relative differences in conversion depth, the topographic undulations of the crust-mantle boundary are consistent with the Moho depths derived from P-receiver functions. In contrast to the Rwenzori region, it is difficult to resolve completely the trend of the Moho in the remaining area of the East African Rift due to the small dataset provided by IRIS. The results exibit an increase in crustal thickness to up to 45 km in the region of the Cenozoic volcanics such as Virunga, Kivu, Rungwe and Kenya. The greatest Moho depths of more than 50 km are located near Mount Kilimanjaro. In addition to the Moho, the analysis of the S-receiver functions revealed two further boundary layers at depths of 60 – 140 km and 110 – 260 km, which are associated with a mid-lithospheric discontinuity and the lithosphere-asthenosphere boundary, respectively. The shallowest conversion depths of the LAB are focussed to small-scale regions within the rift branches, namely the northern Albertine Rift, the Chyulu Hills and the Mozambique Belt, which are located around the Tanzania Craton. The larger thickness of the lithosphere beneath the cratonic terrain indicates that the Tanzania Craton is not significantly eroded. However, there are indications that the lithosphere beneath the craton and the rift branches is penetrated by ascending asthenospheric melts to depths of up to 140 and 60 km, respectively. The top of the ascending melts is associated with the occurrence of the mid-lithospheric discontinuity. The shallowest conversion depths of this boundary layer (60 – 90 km) are related to the rifted areas of the EARS and the Cenozoic volcanic provinces, which are located along the Albertine Rift, the Kenya Rift and the Rukwa-Malawi rift zones. The deepest conversion depths of up to 140 km are related to the Rwenzori Belt, the Ugandan Basement Complex and the interior of the Tanzania Craton.
Ziel der Arbeit war es, die Flugzeitmassenspektrometrie als neue Analysemethode für die instrumentelle Analytik halogenierter Spurengase in der Luft zu etablieren. Die grundle-gende Motivation dafür ist, dass anthropogene Emissionen vieler Vertreter dieser Sub-stanzklasse einen negativen Einfluss auf die Umwelt zeigen: in der Atmosphäre agieren die Substanzen bzw. ihre Abbauprodukte als Katalysatoren für den stratosphärischen Ozonab-bau und verstärken den Strahlungsantrieb der Erde durch Absorption elektromagnetischer Strahlung im sogenannten atmosphärischen Fenster. Um diese Effekte und deren Auswir-kung quantifizieren zu können, ist es notwendig, Konzentrationen und Trends der Substan-zen in der Atmosphäre zu überwachen. Nur so können Gegenmaßnahmen wie Produktions-reglementierungen geplant und bewertet werden. In Kombination mit inverser Modellie-rung können zudem Rückschlüsse über tatsächlich emittierten Mengen gezogen werden. Dies stellt den Anspruch an die Analytik, sehr geringe Mengen dieser Gase sehr präzise quantifizieren zu können, um auch schwache Trends zu erkennen. Zudem muss die Analy-semethode die Möglichkeit zu bieten, mit der wachsenden Anzahl bekannter und zu über-wachender Substanzen Schritt zu halten. Besonders für letzteren Aspekt bietet die Flug-zeitmassenspektrometrie einen entscheidenden Vorteil gegenüber der „konventionellen“ Methode, der Quadrupolmassenspektrometrie: sie zeichnet das gesamten Massenspektrum auf ohne dadurch an Empfindlichkeit einzubüßen. Um das atmosphärische Mischungsver-hältnis von Substanzen im Bereich von pmol mol−1 bis fmol mol−1 bestimmen zu können, muss das Quadrupolmassenspektrometer im Single Ion Monitoring Modus betrieben wer-den – so wird zwar eine hohe Sensitivität erreicht, es wird aber auch nur die Intensität eines bestimmten Masse zu Ladungsverhältnisses (kurz: Masse) zu einem Zeitpunkt aufgezeich-net. Ein Flugzeitmassenspektrometer hingegen extrahiert Ionen mit einer Frequenz im Ki-loherzbereich und zeichnet für jede Extraktion das vollständige Flugzeitspektrum und da-mit Massenspektrum auf.
Aufgabe dieser Arbeit war es, ein Flugzeitmassenspektrometer mit vorgeschalteter Pro-benanreicherungseinheit sowie Gaschromatograph zur Trennung des Subtanzgemisches vor der Detektion aufzubauen und Werkzeuge zur Datenauswertung zu entwickeln. Um einen zukünftigen Feldeinsatz vorzubereiten, sollte der Aufbau möglichst kompakt, mobil und vollständig automatisiert sein. Anschließend sollte Empfindlichkeit, Präzision und dynami-scher Messbereich geprüft, optimiert und die Anwendbarkeit zur Analyse halogenierter Spurengase gezeigt werden. Die Ergebnisse aus der in der vorliegenden Arbeit präsentier-ten Geräteentwicklung finden sich in drei Publikationen wieder, welche in thematischer Reihenfolge die Probenanreicherung (Obersteiner et al., 2016b), den Vergleich von Quadrupol- und Flugzeitmassenspektrometrie (Hoker et al., 2015) sowie Eigenschaften und Anwendung des neuen Aufbaus (Obersteiner et al., 2016a) behandeln. Mit den genannten Aufsätzen ist die Arbeitsgruppe Engel weltweit die erste, welche hochpräzise Analytik ha-logenierter Spurengase routinemäßig mittels Flugzeitmassenspektrometrie durchführt. Der nächste Schritt ist der Übergang von der Laboranwendung zur Feldmessung, z.B. in Form von bodenbasierter in situ Analyse troposphärischer Luftmassen am Taunus Observatorium auf dem Kleinen Feldberg. Da es bisher keine Messstation für die hier beschriebene analy-tische Fragestellung in Deutschland gibt, könnte eine deutliche Verbesserung der Überwa-chung halogenierter Treibhausgase und ozonzerstörender Substanzen in Europa erzielt wer-den. Weiterhin wäre eine Flugzeugapplikation in Zukunft denkbar, welche neben der durch das Flugzeitmassenspektrometer abgedeckten Substanzbandbreite auch von dessen hoher möglicher Spektrenrate profitieren könnte. In Kombination mit Hochgeschwindigkeitsgas-chromatographie könnte eine bisher unerreichte Zeitauflösung der Beprobung der Atmo-sphäre mittels Gaschromatographie-Massenspektrometrie erzielt werden.
Vor dem Hintergrund des globalen Klimawandels und der Diskussion menschlicher Einflussnahme („anthropogener Treibhauseffekt“) ist anhand von Beobachtungsdaten der bodennahen Lufttemperatur und des Niederschlags untersucht worden, welche Strukturen die Klimaveränderungen in Hessen erkennen lassen. Dabei umfasst das betrachtete Gebiet den Bereich 49°- 52° Nord / 7°-11° Ost und schließt somit auch Teilgebiete der angrenzenden Bundesländer mit ein. Zeitlich lag der Schwerpunkt der Betrachtung auf dem Intervall 1951-2000, da aus dieser Zeit bei weitem die meisten Daten verfügbar sind (Temperatur 53, Niederschlag 674 Stationen). Darüber hinaus wurden aber auch Untersuchungen für die Zeit 1901 bis 2000 bzw. 2003 sowie für 30-jährige Subintervalle durchgeführt. Die Analysemethodik umfasst die Berechnung linearer Trends, einschließlich ihrer räumlichen Strukturen (Trendkarten), Aufdeckung von Fluktuationen (spektrale Varianzanalyse), Extremwertanalysen und die Diskussion natürlicher bzw. anthropogener Einflussfaktoren (Signalanalyse mittels multipler schrittweiser Regression). Die aus Tages-, Monats-, jahreszeitlichen und jährlichen Daten gewonnenen Ergebnisse sind überaus vielfältig und heterogen. Für das Flächenmittel Hessen ergibt sich 1951-2000 insgesamt (Jahresdaten) ein Temperaturanstieg von 0,9 °C mit dem Schwerpunkt im Winter (1,6 °C) und der geringsten Erwärmung im Herbst (0,2 °C). 1901-2003 liegen an den erfassten Stationen die jährlichen Erwärmungen bei 0,7 bis 1,8 °C; 30-jährig treten zum Teil auch Abkühlungen auf, insbesondere wenn die regional-jahreszeitlichen bzw. monatlichen Strukturen erfasst werden. Diese Strukturen sind beim Niederschlag noch weit ausgeprägter. Im Flächenmittel Hessen beträgt 1951-2000 der jährliche Niederschlagsanstieg 8,5 %, mit Maxima im Herbst (25 %) und Winter (22 %; Frühling 20%), während im Sommer ein Rückgang um 18 % eingetreten ist (mit Schwerpunkten im Juni und insbesondere August). Bei den Fluktuationen dominieren mittlere Perioden von ca. 2,2, 3,3, 5,5 und 7,5-8 Jahren, beim Niederschlag auch ca. 4,5 Jahre. Der Sonnenfleckenzyklus spiegelt sich in den analysierten Klimadaten nicht wider. Zusammen mit den Extremwerten sorgen diese Fluktuationen für zeitliche Instabilitäten der Klimatrends, insbesondere wenn relativ kurze (z.B. 30-jährige) Zeitabschnitte betrachtet werden. Die wiederum sehr vielfältigen und unterschiedlichen Ergebnisse der Extremwertanalyse spiegeln bei der Temperatur weitgehend die Trends wider, da sich die Streuung der Daten kaum verändert hat: d.h. Zunahme der Überschreitungswahrscheinlichkeit extrem warmer Ereignisse (insbesondere Frühling, überwiegend auch Sommer und Winter, am wenigsten im Herbst) und Abnahme der Unterschreitungswahrscheinlichkeit extrem kalter Ereignisse (dies im Winter bei den Tagesdaten jedoch sehr uneinheitlich). Beim Niederschlag sind die Abnahme extrem feuchter Monate im Sommer und die Zunahme extrem feuchter Tage im Herbst und Winter am auffälligsten. Langfristig folgen daraus ganz markante Änderungen der Jährlichkeiten. So ist beispielsweise 1901-2001 in Alsfeld die Jährlichkeit eines extrem feuchten Winters von 100 auf 5,6 Jahre zurückgegangen, die entsprechende Jährlichkeit eines extrem feuchten Sommers in Bad Camberg dagegen fast bis zur Unmöglichkeit angestiegen. Bei der Ursachendiskussion lässt sich in den Temperaturdaten ein deutlicher anthropogener Einfluss („Treibhauseffekt“) ausfindig machen. Abschließend wird diskutiert, inwieweit es sinnvoll ist, die beobachteten Trends, im Vergleich mit Modellprojektionen, in die Zukunft zu extrapolieren.
The crude oil constituents benzene, toluene, ethylbenzene, and the three xylene isomers (BTEX) are the dominating groundwater contaminants originating from surface spill accidents by oil production facilities and with gasoline and jet fuel. Thereby BTEX posing a threat to the world´s scarce drinking water resources due to their water solubility and toxicity. An active remediation cleanup involving a BTEX event proves not only to be very expensive but almost impossible when it comes to the complete removal of contaminants from the subsurface. A favoured and common practice is combining an active remediation process focussing on the source of contamination coupled together with the monitoring of the residual contamination in the subsurface (monitored natural attenuation; MNA). MNA include all naturally occuring biological, chemical and physical processes in the subsurface. The general goal of this work was to improve the knowledge of biodegradation of aromatic hydrocarbons under anaerobic conditions in groundwater. For this groundwater and soil at the former military underground storage tank (UST) site Schäferhof – Süd near Nienburg/Weser (Niedersachsen, Germany) were sampled and analysed. The investigations were done in collaboration of the Umweltbundesamt, the universitys of Frankfurt and Bremen and the alphacon GmbH Ganderkesee. To investigate the extent of groundwater contamination, the terminal electron acceptor processes (TEAPs) and the metabolites of BTEX degradation in groundwater, six observation wells were sampled at regular intervals between January 2002 and September 2004. The wells were positioned in order to cover the upstream, the source area and the downstream of the presumed contamination source. Additionally, vertical sediment profiles were sampled and investigated with respect to spreading and concentration of BTEX in the subsurface. A large residual contamination involving BTEX is present in soil and groundwater at the studied locality. Maximum BTEX concentration values of 17 mg/kg were recorded in analysing sediment in the unsaturated zone. In the capillary fringe, values of 450 mg/kg were recorded (October 2004) and in the saturated zone maximum values of 6.7 mg/kg BTEX were detected. The groundwater samples indicate increasing BTEX concentrations in the groundwater flow direction (from 532 µg/l up to 3300 µg/l (mean values)). Biodegradation of aromatic hydrocarbons under anaerobic conditions in the sub surface at contaminated sites is characterised by generation of metabolites. From the monoaromatic hydrocarbons BTEX metabolites such as benzoic acid (BA) and the methylated homologs and C1-and C2-benzyl-succinic acids (BSA) are generated as intermediates. A solid-phase extraction method based on octadecyl-bonded silica sorbent has been developed to concentrate such metabolite compounds from water samples followed by derivatization and gas chromatography/mass spectrometry (GC/MS) of the extracts. The recovery rate range between 75 and 97%. The method detection limit was 0.8 µg/l. Organic acids were identified as metabolic by-products of biodegradation. Benzoic acid, C1-, C2- and C3-benzoic acid were determined in all contaminated wells with considerable concentrations. Furthermore, the depletion of the dominant terminal electron acceptors (TEAs) oxygen, nitrate, and sulphate and the production of dissolved ferrous iron and methane in groundwater indicate biological mediated processes in the plume evidently proving the occurrence of NA. A large overlap of different redox zones at the studied part of the plume has been observed. A important finding in this study is the strong influence of groundwater level fluctuations on the BTEX concentration in groundwater. A very dry summer in 2003 was recorded during the monitoring period, resulting on site in a drop of the groundwater level to 1.7 m and a concomitant increase of BTEX concentrations from 240 µg/l to 1300 µg/l. The groundwater level fluctuations, natural degradation and retention processes essentially influence BTEX concentrations in the groundwater. Groundwater level fluctuations have by far a stronger influence than the influence of biological degradation. Increasing BTEX concentrations are hence not a consequence of limited biological degradation. Another part of the study was to observe the isotopic fractionation of the electron acceptor Fe(III), due to biologically mediated reduction of Fe(III) to the watersoluble Fe(II) at the site and first field data are presented. Both groundwater and sediment samples were analysed with respect to their Fe isotopic compositions using high mass resolution Multi Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS). The delta56Fe -values of groundwater samples taken from observation wells located downstream of the source area were isotopically lighter than delta56Fe -values obtained from groundwater in the uncontaminated well. The Fe isotopic composition of most parts of the sediment profile was similar to the Fe isotopic composition of uncontaminated groundwater. Thus, a significant iron isotope fractionation can be observed between sediment and groundwater downstream of the BTEX contamination.
Production and use of many synthetic halogenated trace gases are regulated internationally due to their contribution to stratospheric ozone depletion or climate change. In many applications they have been replaced by shorter-lived compounds, which have become measurable in the atmosphere as emissions increased. Non-target monitoring of trace gases rather than targeted measurements of well-known substances is needed to keep up with such changes in the atmospheric composition. We regularly deploy gas chromatography (GC) coupled to time-of-flight mass spectrometry (TOF-MS) for analysis of flask air samples and in situ measurements at the Taunus Observatory, a site in central Germany. TOF-MS acquires data over a continuous mass range that enables a retrospective analysis of the dataset, which can be considered a type of digital air archive. This archive can be used if new substances come into use and their mass spectrometric fingerprint is identified. However, quantifying new replacement halocarbons can be challenging, as mole fractions are generally low, requiring high measurement precision and low detection limits. In addition, calibration can be demanding, as calibration gases may not contain sufficiently high amounts of newly measured substances or the amounts in the calibration gas may have not been quantified. This paper presents an indirect data evaluation approach for TOF-MS data, where the calibration is linked to another compound which could be quantified in the calibration gas. We also present an approach to evaluate the quality of the indirect calibration method, select periods of stable instrument performance and determine well suited reference compounds. The method is applied to three short-lived synthetic halocarbons: HFO-1234yf, HFO-1234ze(E), and HCFO-1233zd(E). They represent replacements for longer-lived hydrofluorocarbons (HFCs) and exhibit increasing mole fractions in the atmosphere.
The indirectly calibrated results are compared to directly calibrated measurements using data from TOF-MS canister sample analysis and TOF-MS in situ measurements, which are available for some periods of our dataset. The application of the indirect calibration method on several test cases can result in uncertainties of around 6 % to 11 %. For hydro(chloro-)fluoroolefines (denoted H(C)FOs), uncertainties up to 23 % are achieved. The indirectly calculated mole fractions of the investigated H(C)FOs at Taunus Observatory range between measured mole fractions at urban Dübendorf and Jungfraujoch stations in Switzerland.
Highlights
• We find DBrfluid/melt = 1.19 to 3.92 for experimental Br degassing from basalt magma into aqueous fluids.
• D <1 under almost dry conditions propose only little Br degassing for dry intra-plate volcanism relative to volcanic arcs.
• An annual global Br flux of 23.5–72.9 × 109 g/y into the atmosphere was calculated.
Abstract
We present the first in-situ partitioning data for bromine between a natural basaltic melt and a coexisting fluid. For this study hydrothermal diamond anvil cell experiments at pressures up to 1.7 GPa were conducted. We combined laser heating to melt the basalt glass with external heating to lower the temperature gradient in the cell and to initiate circulation for the aqueous fluid. Bromine concentrations were measured in-situ with X-ray fluorescence in the basaltic melts, glasses, and in the fluid. From the results we calculated partition coefficients of DBrfluid/melt = 1.19 to 3.92 in the range of 0.4 to 1 GPa for aqueous fluids. Experiments with neon as the surrounding fluid (DBrfluid/melt = 0.38 ± 0.01 at 1.1 GPa) suggest that Br-release from a basalt into volatiles that have no bonding affinity with Br is weak. This should be the case for dry intra-plate volcanic eruptions. From the experimentally gained partition coefficients and from global Br concentration values in melt inclusions of arc magmas, we calculated an annual global Br flux of 23.5–72.9 × 109 g/y.
Knowledge about the initial tectonic and depositional dynamics, as well as the influence of early rifting on climate and environmental evolution remains speculative to a large extent, because sediments are usually deeply buried. Within the East African Rift System, inversion tectonics uplifted a few of these successions to the surface hence presenting rare windows into the pre-rift depositional history. One such example, an exceptional 700 m long and up to 60 m high fresh road cut provided the opportunity to study in detail initial rift successions of the southern Albertine Rift (Western Uganda). This focusses on the basal and poorly known Middle to Late Miocene in order to unravel the climatic, environmental, hydrological and tectonic evolution of the initial Albertine Rift. A large and robust multi-proxy dataset was gathered comprising 169 m of stratigraphic thickness, which spans from 14.5 to 4.9 Ma according to a revised lithostratigraphic model. Fieldwork comprised logging of the sedimentary record, spectral gamma ray, magnetic susceptibility and 2D wall mapping with photomosaics. Additionally, the sections were sampled for bulk mineral and clay mineral analysis. The succession exposes a suite of lithofacies and architectural elements detailing the evolution of a fluvio-lacustrine system. Five depositional environments were identified which show an overall back-stepping trend from an alluvial plain to a delta plain and finally palustrine/shallow lacustrine conditions. Mesoscale base-level cycles, preservation potential of architectural elements, and stacking pattern exhibit limited accommodation space. However, it increases over time. This overall trend indicates increasing tectonic subsidence, which can be explained by flexural downwarp within the pre-rift phase and in the upper part grading into fault-controlled crustal extension of the syn-rift phase, which more and more disrupted a large-scale river system. From the Middle Miocene up to the early Pliocene, this study revealed that palaeoclimate trends become marked by increasing and more fluctuating Th concentrations, loss of feldspar, intercalated lenses of hydroxosulphate minerals, and a shift from smectite-dominated to kaolinite-dominated clays. These signals are all interpreted as detrital except for the hydroxosulphates, and they mirror the increasing intensity of chemical weathering and stripping of soils in the catchment. A trend towards increasing humidity is supported by an increase in lacustrine sediment facies and a lake-level rise. Nevertheless, intercalation of hydroxosulphate, ferricretes and pedogenised horizons prove ongoing seasonality and dry intervals. Finally, based on a revised stratigraphic model a sequence stratigraphic correlation of the outcrop's depositional cycles with basin-scale cycles is presented. According to these cycles, transition from the pre-rift to the syn-rift stage is marked by an unconformity and a tectonic pulse in the latest Miocene. However, the response of fluvial supply, the depositional system as well as climate conditions are less punctuated and characterised by gradual trends and temporal delays. The long pre-rift phase (ca 10 Myr) and the gradual transition to the syn-rift phase is in accordance with the active rifting model, which is based on thermal thinning of the lithosphere by asthenospheric upwelling.
A primordial state of matter consisting of free quarks and gluons that existed in the early universe a few microseconds after the Big Bang is also expected to form in high-energy heavy-ion collisions. Determining the equation of state (EoS) of such a primordial matter is the ultimate goal of high-energy heavy-ion experiments. Here we use supervised learning with a deep convolutional neural network to identify the EoS employed in the relativistic hydrodynamic simulations of heavy ion collisions. High-level correlations of particle spectra in transverse momentum and azimuthal angle learned by the network act as an effective EoS-meter in deciphering the nature of the phase transition in quantum chromodynamics. Such EoS-meter is model-independent and insensitive to other simulation inputs including the initial conditions for hydrodynamic simulations.
Highlights
• Full automatized analysis of teleseismic XKS shear wave splitting.
• Rapid analysis of large seismological data sets.
• Automated window selection and quality classification.
• Application to the USArray Transportable Array including expansion to Alaska.
• Improved statistical evidence and objectivity of derived effective splitting.
Abstract
Recent technological advances have led to community wide use of large-scale seismic experiments which produce seismic data on previously impossible scales. Standard processing procedures thus require automatization to facilitate a fast and objective analysis of the data. Among these, XKS-splitting is an important tool to derive first insights into the Earth's deformation regimes at depth by studying seismic anisotropy. Most often, shear-wave splitting is interpreted to represent crystallographic preferred orientation (CPO) of mantle minerals like olivine as dominating feature and can thus be used as a proxy of mantle flow processes. Here, we introduce an addition to the MATLAB®-based SplitRacer tool box (Reiss and Rümpker 2017) which automatizes the entire XKS-splitting procedure. This is achieved by the automatization of 1) choosing a time window based on spectral analyses and 2) categorization of results based on three different XKS-splitting methods (energy minimization, rotation correlation and splitting intensity). This provides effective and objective results for splitting as well as null-measurement results. This extension allows to use SplitRacer without a graphical interface and introduces a bootstrapping statistics as error estimate of the single layer joint splitting method. The procedures are designed to allow a fast and more objective analysis of a vast amount of data, as produced by recent seismic deployments (e.g. USArray, AlpArray). We test this automatization by applying the analysis to the USArray data set, which has approximately 1900 stations with between two to fifteen years of data. We can reproduce the general pattern of the results from former studies with the more objective automatic analysis. Based on a joint-splitting approach, we approximate the splitting effect at individual stations by a single anisotropic layer. As we include null-measurements as well as a larger data set as previous studies, we can provide improved statistical evidence for these effective splitting parameters.
We present the characterization and application of a new gas chromatography time-of-flight mass spectrometry instrument (GC-TOFMS) for the quantitative analysis of halocarbons in air samples. The setup comprises three fundamental enhancements compared to our earlier work (Hoker et al., 2015): (1) full automation, (2) a mass resolving power R = m/Δm of the TOFMS (Tofwerk AG, Switzerland) increased up to 4000 and (3) a fully accessible data format of the mass spectrometric data. Automation in combination with the accessible data allowed an in-depth characterization of the instrument. Mass accuracy was found to be approximately 5 ppm in mean after automatic recalibration of the mass axis in each measurement. A TOFMS configuration giving R = 3500 was chosen to provide an R-to-sensitivity ratio suitable for our purpose. Calculated detection limits are as low as a few femtograms by means of the accurate mass information. The precision for substance quantification was 0.15 % at the best for an individual measurement and in general mainly determined by the signal-to-noise ratio of the chromatographic peak. Detector non-linearity was found to be insignificant up to a mixing ratio of roughly 150 ppt at 0.5 L sampled volume. At higher concentrations, non-linearities of a few percent were observed (precision level: 0.2 %) but could be attributed to a potential source within the detection system. A straightforward correction for those non-linearities was applied in data processing, again by exploiting the accurate mass information. Based on the overall characterization results, the GC-TOFMS instrument was found to be very well suited for the task of quantitative halocarbon trace gas observation and a big step forward compared to scanning, quadrupole MS with low mass resolving power and a TOFMS technique reported to be non-linear and restricted by a small dynamical range.
We present the characterization and application of a new gas chromatography time-of-flight mass spectrometry instrument (GC-TOFMS) for the quantitative analysis of halocarbons in air samples. The setup comprises three fundamental enhancements compared to our earlier work (Hoker et al., 2015): (1) full automation, (2) a mass resolving power R = m/Δm of the TOFMS (Tofwerk AG, Switzerland) increased up to 4000 and (3) a fully accessible data format of the mass spectrometric data. Automation in combination with the accessible data allowed an in-depth characterization of the instrument. Mass accuracy was found to be approximately 5 ppm in mean after automatic recalibration of the mass axis in each measurement. A TOFMS configuration giving R = 3500 was chosen to provide an R-to-sensitivity ratio suitable for our purpose. Calculated detection limits are as low as a few femtograms by means of the accurate mass information. The precision for substance quantification was 0.15 % at the best for an individual measurement and in general mainly determined by the signal-to-noise ratio of the chromatographic peak. Detector non-linearity was found to be insignificant up to a mixing ratio of roughly 150 ppt at 0.5 L sampled volume. At higher concentrations, non-linearities of a few percent were observed (precision level: 0.2 %) but could be attributed to a potential source within the detection system. A straightforward correction for those non-linearities was applied in data processing, again by exploiting the accurate mass information. Based on the overall characterization results, the GC-TOFMS instrument was found to be very well suited for the task of quantitative halocarbon trace gas observation and a big step forward compared to scanning, quadrupole MS with low mass resolving power and a TOFMS technique reported to be non-linear and restricted by a small dynamical range.
This work describes the development and characterization of two instruments and their data evaluation, which contributes to a better understanding of new particle formation and growth, as well as their interactions with clouds. Both instruments were characterized at the Cosmics Leaving Outdoor Droplets (CLOUD) experiment at the European Center for Nuclear Research (CERN).
Atmospheric new particle formation is a general phenomenon observed over coniferous forests. So far nucleation is described as a function of gaseous sulfuric acid concentration only, which is unable to explain the observed seasonality of nucleation events at different measurement sites. Here we introduce a new nucleation parameter including ozone and water vapor concentrations as well as UV-B radiation as a proxy for OH radical formation. Applying this new parameter to field studies conducted at Finnish and German measurement sites it is found capable to predict the occurrence of nucleation events and their seasonal and annual variation indicating a significant role of organics. Extrapolation to possible future conditions of ozone, water vapor and organic concentrations leads to a significant potential increase in nucleation event number.
AirCore-HR: a high resolution column sampling to enhance the vertical description of CH₄ and CO₂
(2016)
An original and innovative sampling system called AirCore was presented by NOAA in 2010 (Karion et al., 2010). It consists of a long (> 100 m) and narrow (< 1 cm) stainless steel tube that can retain a profile of atmospheric air. The captured air sample has then to be analyzed with a gas analyzer for trace mole fraction. In this study, we introduce a new AirCore aiming at improved resolution along the vertical with the objectives to: (i) better capture the vertical distribution of CO2 and CH4, (ii) provide a tool to compare AirCores and validate the estimated vertical resolution achieved by AirCores. This AirCore-HR (high resolution) consists of a 300 m tube, combining 200 m of 1/8 in. (3.175 mm) tube and a 100 m of 1/4 in. (6.35 mm) tube. This new configuration allows to achieve a vertical resolution of 300 m up to 15 km and better than 500 m up to 22 km (if analysis of the retained sample is performed within 3 hours). The AirCore-HR was flown for the first time during the annual StratoScience campaign from CNES in August 2014 from Timmins (Ontario, Canada). High-resolution vertical profiles of CO2 and CH4 up to 25 km were successfully retrieved. These profiles revealed well defined transport structures in the troposphere (also seen in CAMS-ECMWF high resolution forecasts of CO2 and CH4 profiles) and captured the decrease of CO2 and CH4 in the stratosphere. The multi-instruments gondola from the flight carried two other low-resolution AirCore-GUF that allowed to perform direct comparisons and study the underlying processing method used to convert the sample of air to greenhouse gases vertical profiles. In particular, degrading the AirCore-HR derived profiles to the low resolution of AirCore-GUF yields an excellent match between both sets of CH4 profiles, and shows a good consistency between vertical structures of CO2 and CH4. These results fully validate the theoretical vertical resolution achievable by AirCores. Finally, the uncertainties associated with the measurements are assessed, yielding an average uncertainty below 3 ppb for CH4 and 0.25 ppm for CO2 with the major source of uncertainty coming from the potential loss of air sample on the ground and the choice of the starting and ending point of the collected air sample inside the tube. In an ideal case where the sample would be fully retained, it would be possible to know precisely the pressure at which air was sampled last and thus to improve the overall uncertainty to about 0.1 ppm for CO2 and 2 ppb for CH4.
AirCore-HR : a high-resolution column sampling to enhance the
vertical description of CH₄ and CO₂
(2017)
An original and innovative sampling system called AirCore was presented by NOAA in 2010 (Karion et al., 2010). It consists of a long ( > 100 m) and narrow (< 1 cm) stainless steel tube that can retain a profile of atmospheric air. The captured air sample has then to be analyzed with a gas analyzer for trace mole fraction. In this study, we introduce a new AirCore aiming to improve resolution along the vertical with the objectives to (i) better capture the vertical distribution of CO2 and CH4, (ii) provide a tool to compare AirCores and validate the estimated vertical resolution achieved by AirCores. This (high-resolution) AirCore-HR consists of a 300 m tube, combining 200 m of 0.125 in. (3.175 mm) tube and a 100 m of 0.25 in. (6.35 mm) tube. This new configuration allows us to achieve a vertical resolution of 300 m up to 15 km and better than 500 m up to 22 km (if analysis of the retained sample is performed within 3 h). The AirCore-HR was flown for the first time during the annual StratoScience campaign from CNES in August 2014 from Timmins (Ontario, Canada). High-resolution vertical profiles of CO2 and CH4 up to 25 km were successfully retrieved. These profiles revealed well-defined transport structures in the troposphere (also seen in CAMS-ECMWF high-resolution forecasts of CO2 and CH4 profiles) and captured the decrease of CO2 and CH4 in the stratosphere. The multi-instrument gondola also carried two other low-resolution AirCore-GUF that allowed us to perform direct comparisons and study the underlying processing method used to convert the sample of air to greenhouse gases vertical profiles. In particular, degrading the AirCore-HR derived profiles to the low resolution of AirCore-GUF yields an excellent match between both sets of CH4 profiles and shows a good consistency in terms of vertical structures. This fully validates the theoretical vertical resolution achievable by AirCores. Concerning CO2 although a good agreement is found in terms of vertical structure, the comparison between the various AirCores yields a large and variable bias (up to almost 3 ppm in some parts of the pro- files). The reasons of this bias, possibly related to the drying agent used to dry the air, are still being investigated. Finally, the uncertainties associated with the measurements are assessed, yielding an average uncertainty below 3 ppb for CH4 and 0.25 ppm for CO2 with the major source of uncertainty coming from the potential loss of air sample on the ground and the choice of the starting and ending point of the collected air sample inside the tube. In an ideal case where the sample would be fully retained, it would be possible to know precisely the pressure at which air was sampled last and thus to improve the overall uncertainty to about 0.1 ppm for CO2 and 2 ppb for CH4
The African continent is regularly portrayed as an indolent space with a well-known reputation as a chaotic continent. Viewed as lacking vision, means and capacities, Africa is perceived at best as a place that is marked by a permanent status quo, stagnation, or in worst case scenarios, as a declining continent. Various references to the continent are synonymous with famine, poverty, war, etc. Such portrayals are all the more intriguing given that the continent is known for its abundant natural resources, such as timber, oil, natural gas, minerals, etc., whose reserves are, moreover, not well known both by the African people and their leaders. As a result, there is still much progress to be made in tapping into the resources in order to improve the daily lives of African citizens.
In such a context dominated by infantile carelessness throughout the continent, the interventions of actors from outside the continent are the only hopes of bringing some vitality to this continent which is cloaked in "la grande nuit – the great darkness" (Mbembé 2013). Thus during the main sequences of recent history, representing different forms of Western penetration and activity on the African continent (slavery, imperialism, colonization), all the Western world’s contributions have obviously not sufficed to boost Africa and take it out of its never ending childhood. It has remained just as passive and apathetic today as it was yesterday.
The attraction of Asian actors to the continent is even more recent. And consistent with its abovementioned indolence, Africa is seen as an easy and defenceless prey for the Korean, Japanese, Indian, Malaysian, or Chinese conquerors. In the latter case, the insatiable appetite for natural resources whose reserves are being rapidly depleted is the cornerstone of their foreign aid policy. This led China to colonize the continent, showing a preference for Pariah Regimes which held no appeal for the West, by sending an army of workers to extract those resources (Lum et al. 2009), in defiance of all national and international regulations and based on completely opaque contracts.
Although the concept of African Agency was rapidly developed in several African countries, the aim of this study was more specific to Cameroon’s mining sector in which different entrepreneurs from abroad got involved over time. The thesis investigates whether indigenous citizens took part in any way in the development of mining projects in the country. Thus, the work assesses and analyses actions and reactions initiated and undertaken by local people in the context of China’s presence within Cameroon’s mining sector to promote and advance their interests over those of foreign investors. In addition, the author has no knowledge of any other study investigating African Agency in the mining sector as a whole in Cameroon.
In conducting this study, a multi-method research framework was developed including a series of methods used to collect data and analyse concepts of African Agency associated Political Ecology as they developed within Cameroon’s mining sector. Specifically, those methods comprised quantitative research when it came to collecting data using a positivist and empirical approach constructed by deducing evidence from statistical data collected by means of the 167 questionnaire surveys administered to local inhabitants and workers randomly selected on mining sites and in riparian communities. The questionnaires helped to capture Cameroonians' perceptions of the recent phenomenon of the gradual but significant influx of international actors and precisely Chinese players in the mining sector on the one hand, and on the other hand, observational data was collected across the GVC as developed in the Betare-Oya region. As a complement to the former technique, qualitative methods helped to study and deepen understanding of human behaviour and the social world in a holistic perspective through individual interviews, focus groups, and direct observations on the ground. In addition, the spatial analysis method based on the land use classification technique served to detect changes to land use/land cover that have been brought on by mechanised mining activities undertaken in this region. The sequencing of data collected and their processing from a ground theory perspective led to the formulation and specification of Cameroon’s Ecological Agency theory.
One of the earliest steps of this work consisted in a literature review and in placing the African Agency concept in a broader context. It then led to the state of the art, specifications about research content of the work and the main theories undergirding this thesis. Before examining developments that emerged during the last decade, a historical perspective was provided to the topic in order to show how African societies started mining operations and how they dealt with foreign partners interested in their mining resources. The aim was to show that while Western imperialism presented a challenge for the sector, it did not erase local participation, even despite the constraints associated with such involvement.
...
Processes occurring in the tropical upper troposphere (UT), the Tropical Transition Layer (TTL), and the lower stratosphere (LS) are of importance for the global climate, for stratospheric dynamics and air chemistry, and for their influence on the global distribution of water vapour, trace gases and aerosols. In this contribution we present aerosol and trace gas (in-situ) measurements from the tropical UT/LS over Southern Brazil, Northern Australia, and West Africa. The instruments were operated on board of the Russian high altitude research aircraft M-55 "Geophysica" and the DLR Falcon-20 during the campaigns TROCCINOX (Araçatuba, Brazil, February 2005), SCOUT-O3 (Darwin, Australia, December 2005), and SCOUT-AMMA (Ouagadougou, Burkina Faso, August 2006). The data cover submicron particle number densities and volatility from the COndensation PArticle counting System (COPAS), as well as relevant trace gases like N2O, ozone, and CO. We use these trace gas measurements to place the aerosol data into a broader atmospheric context. Also a juxtaposition of the submicron particle data with previous measurements over Costa Rica and other tropical locations between 1999 and 2007 (NASA DC-8 and NASA WB-57F) is provided. The submicron particle number densities, as a function of altitude, were found to be remarkably constant in the tropical UT/LS altitude band for the two decades after 1987. Thus, a parameterisation suitable for models can be extracted from these measurements. Compared to the average levels in the period between 1987 and 2007 a slight increase of particle abundances was found for 2005/2006 at altitudes with potential temperatures, theta, above 430 K. The origins of this increase are unknown except for increases measured during SCOUT-AMMA. Here the eruption of the Soufrière Hills volcano in the Caribbean caused elevated particle mixing ratios. The vertical profiles from Northern hemispheric mid-latitudes between 1999 and 2006 also are compact enough to derive a parameterisation. The tropical profiles all show a broad maximum of particle mixing ratios (between theta ~ 340 K and 390 K) which extends from below the TTL to above the thermal tropopause. Thus these particles are a "reservoir" for vertical transport into the stratosphere. The ratio of non-volatile particle number density to total particle number density was also measured by COPAS. The vertical profiles of this ratio have a maximum of 50% above 370 K over Australia and West Africa and a pronounced minimum directly below. Without detailed chemical composition measurements a reason for the increase of non-volatile particle fractions cannot yet be given. However, half of the particles from the tropical "reservoir" contain compounds other than sulphuric acid and water. Correlations of the measured aerosol mixing ratios with N2O and ozone exhibit compact relationships for the tropical data from SCOUT-AMMA, TROCCINOX, and SCOUT-O3. Correlations with CO are more scattered probably because of the connection to different pollution source regions. We provide additional data from the long distance transfer flights to the campaign sites in Brazil, Australia, and West-Africa. These were executed during a time window of 17 months within a period of relative volcanic quiescence. Thus the data represent a "snapshot picture" documenting the status of a significant part of the global UT/LS fine aerosol at low concentration levels 15 years after the last major (i.e., the 1991 Mount Pinatubo) eruption. The corresponding latitudinal distributions of the measured particle number densities are presented in this paper to provide data of the UT/LS background aerosol for modelling purposes.
Processes occurring in the tropical upper troposphere and lower stratosphere (UT/LS) are of importance for the global climate, for the stratospheric dynamics and air chemistry, and they influence the global distribution of water vapour, trace gases and aerosols. The mechanisms underlying cloud formation and variability in the UT/LS are of scientific concern as these still are not adequately described and quantified by numerical models. Part of the reasons for this is the scarcity of detailed in-situ measurements in particular from the Tropical Transition Layer (TTL) within the UT/LS. In this contribution we provide measurements of particle number densities and the amounts of non-volatile particles in the submicron size range present in the UT/LS over Southern Brazil, West Africa, and Northern Australia. The data were collected in-situ on board of the Russian high altitude research aircraft M-55 "Geophysica" using the specialised COPAS (COndensation PArticle counting System) instrument during the TROCCINOX (Araçatuba, Brazil, February 2005), the SCOUT-O3 (Darwin, Australia, December 2005), and SCOUT-AMMA (Ouagadougou, Burkina Faso, August 2006) campaigns. The vertical profiles obtained are compared to those from previous measurements from the NASA DC-8 and NASA WB-57F over Costa Rica and other tropical locations between 1999 and 2007. The number density of the submicron particles as function of altitude was found to be remarkably constant (even back to 1987) over the tropical UT/LS altitude band such that a parameterisation suitable for models can be extracted from the measurements. At altitudes corresponding to potential temperatures above 430 K a slight increase of the number densities from 2005/2006 results from the data in comparison to the 1987 to 2007 measurements. The origins of this increase are unknown. By contrast the data from Northern hemispheric mid latitudes do not exhibit such an increase between 1999 and 2006. Vertical profiles of the non-volatile fraction of the submicron particles were also measured by a COPAS channel and are presented here. The resulting profiles of the non-volatile number density fraction show a pronounced maximum of 50% in the tropical TTL over Australia and West Africa. Below and above this fraction is much lower attaining values of 10% and smaller. In the lower stratosphere the fine particles mostly consist of sulphuric acid which is reflected in the low numbers of non-volatile residues measured by COPAS. Without detailed chemical composition measurements the reason for the increase of non-volatile particle fractions cannot yet be given. The long distance transfer flights to Brazil, Australia and West-Africa were executed during a time window of 17 months within a period of relative volcanic quiescence. Thus the data measured during these transfers represent a "snapshot picture" documenting the status of a significant part of the global UT/LS aerosol (with sizes below 1 μm) at low concentration levels 15 years after the last major (i.e., the 1991 Mount Pinatubo) eruption. The corresponding latitudinal distributions of the measured particle number densities are also presented in this paper in order to provide input on the UT/LS background aerosol for modelling purposes.
In 1998 the German Universities of Kassel and Giessen organised a workshop on water and solute transport in large drainage basins. The workshop focused on analysing and summarising the state of research, existing problems and perspectives in this research area. It was the second of a series of annual workshops since 1997 that became an important discussion forum for the German-speaking research community in the field of hydrological modelling. Now the 11th Workshop on Large-scale Hydrological Modelling referred to the same questions as posed in 1998 in order to evaluate the developments and advances of the last ten years. Based on keynote presentations, the workshop focused on discussion in working groups where also posters were presented. This volume of "Advances in Geosciences" comprises seven papers referring to the poster contributions. At the end of the volume, an overview paper summarises the outcome of the workshop presentations and discussions (Doll et al.). ...
Large-scale hydrological modelling has become increasingly wide-spread during the last decade. An annual workshop series on large-scale hydrological modelling has provided, since 1997, a forum to the German-speaking community for discussing recent developments and achievements in this research area. In this paper we present the findings from the 2007 workshop which focused on advances and visions in large-scale hydrological modelling. We identify the state of the art, difficulties and research perspectives with respect to the themes "sensitivity of model results", "integrated modelling" and "coupling of processes in hydrosphere, atmosphere and biosphere". Some achievements in large-scale hydrological modelling during the last ten years are presented together with a selection of remaining challenges for the future.
A twentieth century-long coupled atmosphere-ocean regional climate simulation with COSMO-CLM (Consortium for Small-Scale Modeling, Climate Limited-area Model) and NEMO (Nucleus for European Modelling of the Ocean) is studied here to evaluate the added value of coupled marginal seas over continental regions. The interactive coupling of the marginal seas, namely the Mediterranean, the North and the Baltic Seas, to the atmosphere in the European region gives a comprehensive modelling system. It is expected to be able to describe the climatological features of this geographically complex area even more precisely than an atmosphere-only climate model. The investigated variables are precipitation and 2 m temperature. Sensitivity studies are used to assess the impact of SST (sea surface temperature) changes over land areas. The different SST values affect the continental precipitation more than the 2 m temperature. The simulated variables are compared to the CRU (Climatic Research Unit) observational data, and also to the HOAPS/GPCC (Hamburg Ocean Atmosphere Parameters and Fluxes from Satellite Data, Global Precipitation Climatology Centre) data. In the coupled simulation, added skill is found primarily during winter over the eastern part of Europe. Our analysis shows that, over this region, the coupled system is dryer than the uncoupled system, both in terms of precipitation and soil moisture, which means a decrease in the bias of the system. Thus, the coupling improves the simulation of precipitation over the eastern part of Europe, due to cooler SST values and in consequence, drier soil.
Rationale: Potassium (K) is a major component of several silicate minerals and seawater, and, therefore, constraining past changes in the potassium cycle is a promising way of tracing large-scale geological processes on Earth. However, [K] measurement using inductively coupled plasma mass spectrometry (ICP-MS) is challenging due to an ArH+ interference, which may be of a similar magnitude to the K+ ion beam in samples with <0.1% m/m [K].
Methods: In this work, we investigated the effect of the ArH+ interference on K/Ca data quality by comparing results from laser-ablation (LA)-ICP-MS measured in medium and high mass resolution modes and validating our LA results via solution ICP-optical emission spectroscopy (OES) and solution ICP-MS measurements. To do so, we used a wide range of geological reference materials, with a particular focus on marine carbonates, which are potential archives of past changes in the K cycle but are typically characterised by [K] < 200 μg/g. In addition, we examine the degree to which trace-element data quality is driven by downhole fractionation during LA-ICP-MS measurements.
Results: Our results show that medium mass resolution (MR) mode is sufficiently capable of minimising the effect of the ArH+ interference on K+. However, the rate of downhole fractionation for Na and K varies between different samples as a result of their differing bulk composition, resulting in matrix-specific inaccuracy. We show how this can be accounted for via downhole fractionation corrections, resulting in an accuracy of better than 1% and a long-term reproducibility (intermediate precision) of <6% (relative standard deviation) in JCp-1NP using LA-ICP-MS in MR mode.
Conclusion: Our [K] measurement protocol is demonstrably precise and accurate and applicable to a wide range of materials. The measurement of K/Ca in relatively low-[K] marine carbonates is presented here as a key example of a new application opened up by these advances.
We evaluate the near-surface representation of thermally driven winds in the Swiss Alps in a numerical weather prediction model at km-scale resolution. In addition, the influence of grid resolution (2.2 km and 1.1 km), topography filtering, and land surface datasets on the accuracy of the simulated valley winds is investigated. The simulations are evaluated against a comprehensive set of surface observations for an 18-day fair-weather summer period in July 2006. The episode is characterized by strong diurnal wind systems and the formation of shallow convection over the mountains, which transitions to precipitating convection in some areas. The near-surface winds (10 m above ground level) follow a typical diurnal pattern with strong daytime up-valley flow and weaker nighttime down-valley flow. At a 2.2 km resolution the valley winds are poorly simulated for most stations, while at a 1.1 km resolution the diurnal cycle of the valley winds is well represented in most large (e.g., Rhein valley at Chur and Rhone valley at Visp) and medium-sized valleys (e.g., Linth valley at Glarus). In the smaller valleys (e.g., Maggia valley at Cevio), the amplitude of the valley wind is still significantly underestimated, even at a 1.1 km resolution. Detailed sensitivity experiments show that the use of high-resolution land surface datasets, for both the soil characteristics as well as for the land cover, and reduced filtering of the topography are essential to achieve good performance at a 1.1 km resolution