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New U–Pb ages of detrital and igneous zircons of the Uppermost Unit of Crete shed light on its provenance and on Eohellenic to Eoalpine imprints in the eastern Mediterranean. The detrital zircons of all nappes show Variscan ages and are characterized by a Minoan-type age spectrum, which is typical for the NE margin of Gondwana. Parts of the metasedimentary rocks are unexpectedly young. Their detrital zircon ages continue via the Permian until the Late Triassic, Middle Jurassic and Early Cretaceous. The high-grade metamorphic rocks of the Asterousia crystalline complex are likely equivalents of the low-grade metamorphic trench and fore-arc deposits of the Vatos nappe pointing to Late Cretaceous slab roll back. The presence of both late Permian detrital zircons and Late Cretaceous arc-type granitoids suggest that the Uppermost Unit of Crete is derived from the late Permian/Late Cretaceous magmatic belt situated north of the Sava–Vardar–Izmir–Ankara Suture in the Strandja–Rhodope area. To achieve their recent position on Crete, the nappes had to travel more than 500 km. The traveling path is well tracked by rocks of the Upper Cycladic Unit, which are similar to those of the Uppermost Unit of Crete. The large displacement of the Cretan nappes was controlled not only by nappe transport, but probably also by dextral strike–slip along the North Anatolian Fault Zone and related counterclockwise rotation of the Anatolian block since the Eocene.
"High-aluminous coal" is an important coal kind and widely distributed in North China in age of Permo-Carboniferous period. To explore their occurrence state, a total of 15 harmful elements (Li, Ga, In, Cd, Cr, Pb, Be, Mn, Zn, Ag, Co, Ni, Cu, Ba and U) in the No.9 coal and No.11 coal collected from Pingshuo mining district were determined by inductively coupled plasma mass spectrometry (ICP-MS) and scanning electron microscope with energy spectrum (SEM-EDX). The results showed that the content of Li, Ga, In, Pb, Ag and U were all exceed the world hard coal. In view of the result of clustering analysis within trace elements, it was found that Co, Ni, Zn, Cu, Ag and Cr were mainly associated with sulfide minerals due to their common sulfophilic property. Manganese was mainly occurred in carbonate minerals, while Ba, Cd and U were mainly associated with total minerals. In addition, Pb was related to sulfides and Be is mainly distributed in clay minerals. The enrichment of such harmful elements in Pingshuo coal was caused by the combined effect of transgression and input of terrestrial materials in the peat accumulation stage. Li, Ga, In and Ag have reached the harmful grade.
Trace elemental concentrations of bivalve shells content a wealthy of environmental and climatic information of the past, and therefore the studies of trace elemental distributions in bivalve shells gained increasing interest lately. However, after more than half century of research, most of the trace elemental variations are still not well understood and trace elemental proxies are far from being routinely applicable. This dissertation focuses on a better understanding of the trace elemental chemistry of Arctica islandica shells from Iceland, and paving the way for the application of the trace elemental proxies to reconstruct the environmental and climatic changes. Traits of trace elemental concentrations on A. islandica shells were explored and evaluated. Then based the geochemical traits of the shells, four non-environmental/climatic controlling is indentified. (1) Trace elemental concentrations of bivalve shells are effected by early diagenesis by the leach or exchange of elemental ions, especially in shell tip part, even with the protection of periostrucum; (2) The analytical methods also affect the results of trace elemental concentrations, especially for the element, such as Mg, which is highly enriched in organic matrices; (3) Shell organic matrices are found play a dominating role on the concentration of trace elements on A. islandica shells. Most trace elements only occurred in insoluble organic matrices (IOM), although others are only found in the carbonate fraction. IOM of A. islandica shells is significantly enriched in Mg, while Li and Na are more deplete in IOM, but enriched in shell carbonate. Ba is more or less even contented in IOM and shell carbonate. The concentrations of certain elements vary between primary layer and secondary layer; (4) The vital /physiological controlling on trace elemental distributions of bivalve shells is also confirmed. Six elemental (B, Na, Mg, Mn, Sr, and Ba) concentrations show significant correlation (exponential functions) with ontogenetic age and shell grow rates (logarithmic equations). It is worthy to remark that B, Mg, Sr and Ba concentrations are negatively correlated with shell growth rate, positive with ontogenetic age, while the concentrations of Na and Mn show the opposite trends. At last, all the controlling described above can be taken into account and corrected to extract the environmental and climatic signal by a kind of standardization. The derived six exponential functions of the high correlations between six trace elemental concentrations and ontogenetic year are applied to make the standardization of these element-Ca ratios. The gotten standardized indices are compared with the variations of environmental and climatic parameters in this region, and many correlations are found. Standardized indices of Sr/Ca ratios are strongly related to the sun spot number, autumn NAO, autumn Europe surface air temperature (SAT) and Arctic sea surface temperature anomaly (TA), and those of Mg/Ca ratios are strongly associated with Arctic TA, Europe SAT and Solar variation (irradiance). The variations of autumn Europe SAT demonstrated more similarity with standardized indices of B/Ca than other parameters. Except for the SAT index of Arctic, the standardized indices of Na/Ca showed no distinct relation to temperature. European precipitation and the Arctic sea level pressure index compared well the Na/Ca ratios of the shells, and so did the autumn NAO. Standardized indices of Mn/Ca were correlated with the number of hurricanes in the North Atlantic, Northern Europe SAT and sun spot number.
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 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.
Ob Klimawandel oder Luftverschmutzung: Die chemischen und physikalischen Prozesse in der Atmosphäre haben wichtige Auswirkungen auf die menschliche Gesundheit und Ökosysteme. Dabei ist die Atmosphäre mehr als ein Gemisch aus Stickstoff, Sauerstoff, Wasserdampf, Helium und Kohlenstoffdioxid. Es gibt zahlreiche Spurengase, deren Gesamtanteil am Volumen weniger als 1 % ausmacht. In dieser Arbeit werden Stickstoffoxide, Schwefeldioxid, Kohlenstoffmonoxid und Schwefelsäure näher betrachtet, die im Rahmen der flugzeugbasierten Messkampagne Chemistry of the Atmosphere: field experiment in Europe (CAFE-EU)/BLUESKY gemessen wurden.
Die Stickstoffoxide NO und NO2, als NOx zusammengefasst, besitzen hauptsächlich anthropogene Quellen, allen voran fossile Verbrennung und industrielle Prozesse. Zwischen NO und NO2 besteht ein photochemisches Gleichgewicht, sodass in der Atmosphäre vor allem NO2 in relevanten Konzentrationen vorkommt; dies wirkt aufgrund der Bildung von Salpetersäure, HNO3, in wässriger Lösung beim Einatmen ätzend und ist entsprechend gesundheitsschädlich. Troposphärisches Ozon, O3, wesentlicher Bestandteil von Sommersmog, wird hauptsächlich durch die Reaktion von NO mit Peroxiden (HO2 und RO2) gebildet. In der Stratosphäre entstehen NOx hauptsächlich durch die Photodissoziation von Lachgas, N2O, das aufgrund seiner langen Lebenszeit von der Tropo- in die Stratosphäre transportiert werden kann und dort die wichtigste Stickstoffquelle darstellt. In der Stratosphäre tragen NOx zum katalytischen Abbaumechanismus des Ozons bei (Bliefert, 2002; Seinfeld and Pandis, 2016).
Schwefeldioxid, SO2, ist ein toxisches Gas, dessen atmosphärische Quellen hauptsächlich anthropogen sind, nämlich fossile Verbrennung und industrielle Prozesse; Senken sind trockene und feuchte Deposition, wobei letztere zu saurem Regen führen kann. Seit den 1980ern sinken die globalen SO2-Emissionen. SO2 kann in der Atmosphäre zu Sulfat und Schwefelsäure oxidiert werden, was Hauptbestandteil des Wintersmogs ist. Der wichtigste Mechanismus ist die Oxidation mit dem Hydroxylradikal, OH˙, unter Beteiligung von Wasserdampf. In der Stratosphäre ist Carbonylsulfid, OCS, die wichtigste Schwefelquelle, da es analog zum N2O dank seiner langen Lebenszeit von der Tropo- in die Stratosphäre transportiert werden kann (Bliefert, 2002; Seinfeld und Pandis, 2016). Typische Konzentrationen von Schwefelsäure sind 105 cm–3 nachts und 107 cm–3 tagsüber in der Troposphäre sowie 105 cm–3 tagsüber in der Stratosphäre (Clarke et al., 1999; Weber et al., 1999; Fiedler et al., 2005; Arnold, 2008; Kürten et al., 2016; Berresheim et al., 2000).
Kohlenstoffmonoxid, CO, ist ein toxisches Gas, das zu gleichen Teilen durch direkte Emissionen (v.a. Biomasseverbrennung und fossile Verbrennung) und In-situ-Oxidation (v.a. von Methan, Isopren und industriellen Kohlenwasserstoffen) in die Atmosphäre gelangt. Die Hauptsenke ist die Reaktion mit OH˙ in der Troposphäre. Seit 2000 sinkt die globale CO-Konzentration (Bliefert, 2002).
Doch neben Gasen sind auch Aerosolpartikel fester Bestandteil des Gemisches Luft, welche luftgetragene feste oder flüssige Teilchen sind. Primäre Aerosolpartikel werden direkt als solche in die Atmosphäre emittiert, während sekundäre Aerosolpartikel in der Atmosphäre gebildet werden, indem gasförmige Vorläufersubstanzen mit geringer Flüchtigkeit auf primären Partikeln kondensieren oder durch Zusammenclustern und Anwachsen komplett neue Partikel bilden. Aerosolpartikel ermöglichen als Wolkenkondensationskeime erst die Bildung von Wolken und wirken somit – neben ihrem direkten reflektierenden Effekt – durch Änderung der Wolkenbedeckung und -eigenschaften insgesamt kühlend aufs Klima und beeinflussen die lokalen und globalen Wasserkreisläufe. Doch sie haben auch negative Auswirkungen auf die menschliche Gesundheit und sind für eine Verkürzung der durchschnittlichen Lebensdauer in Regionen mit hohen Feinstaubbelastungen verantwortlich (Seinfeld und Pandis, 2016; Bellouin et al., 2020; World Health Organization, 2016).
Neben den bisher betrachteten neutralen, also ungeladenen Gasen und Partikeln sind Ionen in der Gasphase sowie geladene Partikel ebenfalls Bestandteil der Atmosphäre. Sie spielen bei vielen atmosphärischen Prozessen eine wichtige Rolle, wie etwa bei Gewittern, Radiowellenübertragung und ionen-induzierter Nukleation von Aerosolpartikeln. Die Hauptquellen für Ionisation in der Tropo- und Stratosphäre ist die galaktische kosmische Strahlung, die entgegen ihrem Namen hauptsächlich aus Protonen und α-Partikeln (primäre Partikel genannt) besteht und in der Erdatmosphäre durch Kollision mit Luftmolekülen Teilchenschauer von sekundären Partikeln (u.a. Myonen, Pionen und Neutrinos) hervorruft. Die primären und sekundären Partikel können die Luftmoleküle ionisieren unter Entstehung von N+, N2+, O+, O2+ und Elektronen. Sauerstoff reagiert rasch mit letzteren zu O– und O2–. Diese Kationen und Anionen reagieren weiter, bis Ionenclustern der Summenformeln (HNO3)n(H2O)mNO3– und H+(H2O)n(B)m gebildet werden, wobei B Basen wie Methanol, Aceton, Ammoniak oder Pyridin sind. Weitere Ionisationsquellen sind der Zerfall des Radioisotops 222Rn in Bodennähe und ionisierende Solarstrahlung oberhalb der Stratosphäre. Atmosphärische Ionen haben zwei wichtige Senken: die Wiedervereinigung, auch Rekombination genannt, bei der sich ein Kation und ein Anion gegenseitig neutralisieren sowie das Anhaften an Aerosolpartikeln. Letztere Senke ist vor allem in der Troposphäre aufgrund der relativ hohen Konzentration an Aerosolpartikeln relevant (Arnold, 2008; Viggiano und Arnold, 1995; Bazilevskaya et al., 2008; Hirsikko et al., 2011).
One of the major problems in evolutionary biology is to elucidate the relationships between historical events and the tempo and mode of lineage divergence. The development of relaxed molecular clock models and the increasing availability of DNA sequences resulted in more accurate estimations of taxa divergence times. However, finding the link between competing historical events and divergence is still challenging. Here we investigate assigning constrained-age priors to nodes of interest in a time-calibrated phylogeny as a means of hypothesis comparison. These priors are equivalent to historic scenarios for lineage origin. The hypothesis that best explains the data can be selected by comparing the likelihood values of the competing hypotheses, modelled with different priors. A simulation approach was taken to evaluate the performance of the prior-based method and to compare it with an unconstrained approach. We explored the effect of DNA sequence length and the temporal placement and span of competing hypotheses (i.e. historic scenarios) on selection of the correct hypothesis and the strength of the inference. Competing hypotheses were compared applying a posterior simulation analogue of the Akaike Information Criterion and Bayes factors (obtained after calculation of the marginal likelihood with three estimators: Harmonic Mean, Stepping Stone and Path Sampling). We illustrate the potential application of the prior-based method on an empirical data set to compare competing geological hypotheses explaining the biogeographic patterns in Pleurodeles newts. The correct hypothesis was selected on average 89% times. The best performance was observed with DNA sequence length of 3500-10000 bp. The prior-based method is most reliable when the hypotheses compared are not temporally too close. The strongest inferences were obtained when using the Stepping Stone and Path Sampling estimators. The prior-based approach proved effective in discriminating between competing hypotheses when used on empirical data. The unconstrained analyses performed well but it probably requires additional computational effort. Researchers applying this approach should rely only on inferences with moderate to strong support. The prior-based approach could be applied on biogeographical and phylogeographical studies where robust methods for historical inferences are still lacking.
In dieser Dissertation wird die Parametrisierung von subgitterskaligen (SGS) Prozessen in Atmosphärenmodellen untersucht. Die Arbeit befasst sich mit den stochastisch angetriebenen Flachwassergleichungen, im ersten Teil in einer räumlichen Dimension und im zweiten Teil in zwei Dimensionen. Die Einteilung in aufgelöste und SGS-Variable erfolgt in beiden Fällen über lokale räumliche Mittel der Ursprungsvariable und deren Abweichungen vom lokalen Mittel.
Im eindimensionalen Fall liegt zwischen den Variablen eine deutliche Separation der charakteristischen Zeitskalen vor, wodurch die Anwendung der stochastischen Moden Reduktion (SMR) ermöglicht wird. Die SMR generiert ein reduziertes Modell der aufgelösten Variable mit einer stochastischen SGS-Parametrisierung, im Folgenden auch Schließung genannt. Die SMR-Schließung basiert auf den Grundgleichungen des Flachwassermodells und ist numerisch effizient einsetzbar, da sie nur eine geringe Anzahl von benachbarten Zellen koppelt. Sie verbessert die Ergebnisse des reduzierten Modells und übertrifft die Ergebnisse zweier zum Vergleich untersuchter empirischer stochastischer Schließungen. Den größten Zugewinn liefert sie im Energiespektrum, insbesondere für kleine Skalen. Das Ergebnis der SMR-Schließung kann verbessert werden, indem die Amplitude der stochastischen Schließungskomponente gedämpft wird. Die SMR-Schließung ist skalenabhängig im Sinne der räumlichen Modellauflösung. Untersucht wird die Schließung bei Halbierung und Viertelung der räumlichen Auflösung, wo sie ihre Überlegenheit gegenüber den empirischen Schließungen wiederholt bestätigt.
Im Unterschied zum eindimensionalen Fall ist in zwei Dimensionen auch die Corioliskraft enthalten und eine räumliche Divergenz der Schwerewellen möglich. Zwischen der aufgelösten und der SGS-Variable kommt es erneut zu einer Separation der charakteristischen Zeitskalen. Die Separation ist allerdings weniger stark ausgeprägt als im eindimensionalen Fall. Grund hierfür ist das Auftreten einer lang korrelierten geostrophisch balancierten Mode, welche auch auf die SGS-Variable projiziert. Das Vorgehen zur Bestimmung der SMR-Schließung für das zweidimensionale Modell verläuft analog zum eindimensionalen Fall. Es werden die Ergebnisse des hoch aufgelösten Referenzmodells und zweier Modelle ohne SGS-Schließung verglichen.
This paper presents an analysis of the recent tropospheric molecular hydrogen (H2) budget with a particular focus on soil uptake and surface emissions. A variational inversion scheme is combined with observations from the RAMCES and EUROHYDROS atmospheric networks, which include continuous measurements performed between mid-2006 and mid-2009. Net H2 surface flux, soil uptake distinct from surface emissions and finally, soil uptake, biomass burning, anthropogenic emissions and N2 fixation-related emissions separately were inverted in several scenarios. The various inversions generate an estimate for each term of the H2 budget. The net H2 flux per region (High Northern Hemisphere, Tropics and High Southern Hemisphere) varies between −8 and 8 Tg yr−1. The best inversion in terms of fit to the observations combines updated prior surface emissions and a soil deposition velocity map that is based on soil uptake measurements. Our estimate of global H2 soil uptake is −59 ± 4.0 Tg yr−1. Forty per cent of this uptake is located in the High Northern Hemisphere and 55% is located in the Tropics. In terms of surface emissions, seasonality is mainly driven by biomass burning emissions. The inferred European anthropogenic emissions are consistent with independent H2 emissions estimated using a H2/CO mass ratio of 0.034 and CO emissions considering their respective uncertainties. To constrain a more robust partition of H2 sources and sinks would need additional constraints, such as isotopic measurements.