A hypothesis for the geochemical anomaly in the North Creek Watershed /

A regional geochemical reconnaissance by bottom stream sediment sampling, has delineated an area of high metal content in the north central sector of the North Creek Watershed. Development of a geochemical model, relating to the relative chemical concentrations derived from the chemical analyses of bottom sediments, suspended sediments, stream waters and well waters collected from the north central sector, was designed to discover the source of the anomaly. Samples of each type of material were analysed by the A.R.L. Direct Reading Multi-element Emission Spectrograph Q.A. 137 for elements: Na, K, Ca, Sr, Si, As, Pb, Zn, Cd, Ni, Ti, Ag, Mo, Be, Fe, AI, Mn, Cu, Cr, P and Y. Anomalous results led to the discovery of a spring, the waters of which carried high concentrations of Zn, Cd, Pb, As, Ni, Ti, Ag, Sr and Si. In addition, the spring waters had high concentrations of Na, Ca, Mg, 504 , alkalinity, N03' and low concentrations of K, Cl and NH3. Increased specific conductivity (up to 2500 ~mho/cm.) was noted in the spring waters as well as increased calculated total dissolved solids (up to 2047 mg/l) and increased ionic strength (up to 0.06). On the other hand, decreases were noted in water temperature (8°C), pH (pH 7.2) and Eh (+.154 volts). Piezometer nests were installed in the anomalous north central sector of the watershed. In accordance with the slope of the piezometric surface from wells cased down to the till/bedrock interface, groundwater flow is directed from the recharge area (northwest of the anomaly) towards the artesian spring via the highly fractured dolostone aquifer of the Upper Eramosa Member. The bedrock aquifer is confined by the overlying Halton till and the underlying Lower Eramosa Member (Vinemount Shale). The oxidation of sphalerite and galena and the dissolution of gypsum, celestite, calcite, and dolomite within the Eramosa Member, contributed its highly, dissolved constituents to the circulating groundwaters, the age of which is greater than 20 years as determined by tritium dating. Groundwater is assumed to flow along the Vinemount Shale and discharge as an artesian spring where the shale unit becomes discontinuous. The anomaly is located on a topographic low where bedrock is close to the surface. Thermodynamic evaluation of the major ion speciation from the anomalous spring and surface waters, showed gypsum to be supersaturated in these spring waters. Downstream from the spring, the loss of carbon dioxide from the spring waters resulted in the supersaturation with respect to calcite, aragonite, magnesite and dolomite. This corresponded with increases in Eh (+.304 volts) and pH (pH 8.5) in the anomalous surface waters. In conclusion, the interaction of groundwaters within the highly, mineralized carbonate source (Eramosa Member) resulted in the characteristic Ca*Mg*HC03*S04 spring water at the anomalous site, which appeared to be the principle effect upon controlling the anomalous surface water chemistry.

Petrography, Geochemistry and Diagenesis of Coral Deposits of Kavaratti and Minicoy Islands, Lakshadweep, India

In the present thesis the petrographic, geochemical and digenetic variability of the sediments in the islands of Kavaratti and Minicoy has been investigated .The beach profile studies show that in the Kavaratti lagoon beach, the slope is steeper in the southern and south central part than in the northern end’s marginal deposition is taking place in the northern end of the Kavaratti island, whereas a marginal erosion is observed at the southern end. In Minicoy the slope of the lagoon beach is gentle in the south and is slightly steeper at the northern part of the beach. The southern and northern beach sections show a marginal deposition. Based on the mineralogical and geochemical studies it is concluded that the main digenetic changes observed is the transformation of aragonite to LMC.The transformation takes place mainly in the vadose zone and is caused by the abundance of fresh water infiltration.

Hiatal surfaces from the Miocene Globigerina Limestone Formation of Malta: Biostratigraphy, sedimentology, trace fossils and early diagenesis

The Miocene Globigerina Limestone of the Maltese islands contains widespread omission surfaces with very different characteristics and origins. The terminal Lower Globigerina Limestone hardground (TLGLHg) formed during a period of falling sea level. Coccolith assemblages suggest shallowness. Sedimentary structures and trace fossil assemblages, indicate increasing frequency of storm events and erosional episodes, towards the surface. Calcite cementation which took place around Thalassinoides burrows and formed irregular nodules was followed by dissolution of aragonite. It is suggested that lithification was linked to microbial reactions involving organic matter. In contrast two later surfaces, the terminal Middle Globigerina Limestone omissionground (TMGLOg), which marks the Lower to Middle Miocene boundary, and the Fomm-ir-Rih local hardground (FiRLHg) both contain early diagenetic dolomite. Lithification took place in two phases. The dolomite is interpreted to have formed beneath the sea floor: it was subsequently exhumed and partially corroded as the precipitation of calcitic and phosphatic cements took place around burrows open to the circulation of sea water. (C) 2008 Elsevier B.V. All rights reserved.

Record of natural and anthropogenic changes in reef environments (Barbados West Indies) using laser ablation ICP-MS and sclerochronology on coral cores

Coral growth rate can be affected by environmental parameters such as seawater temperature, depth, and light intensity. The natural reef environment is also disturbed by human influences such as anthropogenic pollutants, which in Barbados are released close to the reefs. Here we describe a relatively new method of assessing the history of pollution and explain how these effects have influenced the coral communities off the west coast of Barbados. We evaluate the relative impact of both anthropogenic pollutants and natural stresses. Sclerochronology documents framework and skeletal growth rate and records pollution history (recorded as reduced growth) for a suite of sampled Montastraea annularis coral cores. X-radiography shows annual growth band patterns of the corals extending back over several decades and indicates significantly lower growth rate in polluted sites. Results using laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on the whole sample (aragonite, organic matter, trapped particulate matter, etc.), have shown contrasting concentrations of the trace elements (Cu, Sn, Zn, and Pb) between corals at different locations and within a single coral. Deepwater corals 7 km apart, record different levels of Pb and Sn, suggesting that a current transported the metal pollution in the water. In addition, the 1995 hurricanes are associated with anomalous values for Sn and Cu from most sites. These are believed to result from dispersion of nearshore polluted water. We compared the concentrations of trace elements in the coral growth of particular years to those in the relevant contemporaneous seawater. Mean values for the concentration factor in the coral, relative to the water, ranged from 10 for Cu and Ni to 2.4 and 0.7 for Cd and Zn, respectively. Although the uncertainties are large (60-80%), the coral record enabled us to demonstrate the possibility of calculating a history of seawater pollution for these elements from the 1940s to 1997. Our values were much higher than those obtained from analysis of carefully cleaned coral aragonite; they demonstrate the incorporation of more contamination including that from particulate material as well as dissolved metals.

A molluscan perspective on hydrological cycle dynamics in northwestern Europe

Shell aragonite δ18O values of unionid freshwater mussels are applied as a proxy for past river discharges in the rivers Rhine and Meuse, using a set of nine shells from selected climatic intervals during the late Holocene. A single Meuse shell derives from the Subboreal and its δ18O values are similar to modern values. The Rhine specimens represent the Subboreal, the Roman Warm Period and the Medieval Warm Period (MWP). These shells also show averages and ranges of aragonite δ18O values similar to modern specimens. This indicates that environmental conditions such as Rhine river dynamics, Alpine meltwater input and drought severity during these intervals were similar to the 20th century. These shells do not record subtle centennial to millennial climatic variation due to their relatively short lifespan and the large inter-annual and intra-seasonal variation in environmental conditions. However, they are very suitable for studying seasonal to decadal scale climate variability. The two shells with the longest lifespan appear to show decadal scale variability in reconstructed water δ18O values during the MWP, possibly forced by the North Atlantic Oscillation (NAO), which is the dominant mode of variability influencing precipitation regimes over Europe.

Can shells of freshwater mussels (Unionidae) be used to estimate low summer discharge of rivers and associated droughts?

This paper examines if shell oxygen isotope ratios (d18Oar) of Unio sp. can be used as a proxy of past discharge of the river Meuse. The proxy was developed from a modern dataset for the reference time interval 1997–2007, which showed a logarithmic relationship between discharge and measured water oxygen isotope ratios(d18Ow). To test this relationship for past time intervals,d18Oar values were measured in the aragonite of the growth increments of four Unio sp. shells; two from a relatively wet period and two from a very dry time interval (1910–1918 and 1969–1977, respectively). Shell d18Oar records were converted into d18Ow values using existing water temperature records. Summer d18Ow values, reconstructed from d18Oar of 1910–1918, showed a similar range as the summer d18Ow values for the reference time interval 1997–2007, whilst summer reconstructed d18Ow values for the time interval 1969–1977 were anomalously high. These high d18Ow values suggest that the river Meuse experienced severe summer droughts during the latter time interval. d18Ow values were then applied to calculate discharge values. It was attempted to estimate discharge from the reconstructed d18Ow values using the logarithmic relationship between d18Ow and discharge. A comparison of the calculated summer discharge results with observed discharge data showed that Meuse low-discharge events below a threshold value of 6 m3/s can be detected in the reconstructed d18Ow records, but true quantification remains problematic.

Incorporation of lead into calcium carbonate granules secreted by earthworms living in lead contaminated soils

The influence of soil organisms on metal mobility and bioavailability in soils is not currently fully understood. We conducted experiments to determine whether calcium carbonate granules secreted by the earthworm Lumbricus terrestris could incorporate and immobilise lead in lead- and calcium- amended artificial soils. Soil lead concentrations were up to 2000 mg kg-1 and lead:calcium ratios by mass were 0.5-8. Average granule production rates of 0.39 + 0.04 mgcalcite earthworm-1 day-1 did not vary with soil lead concentration. The lead:calcium ratio in granules increased significantly with that of the soil (r2 = 0.81, p = 0.015) with lead concentrations in granules reaching 1577 mg kg-1. X-ray diffraction detected calcite and aragonite in the granules with indications that lead was incorporated into the calcite at the surface of the granules. In addition to the presence of calcite and aragonite X-ray absorption spectroscopy indicated that lead was present in the granules mainly as complexes sorbed to the surface but with traces of lead-bearing calcite and cerussite. The impact that lead-incorporation into earthworm calcite granules has on lead mobility at lead-contaminated sites will depend on the fraction of total soil lead that would be otherwise mobile.

Carbonate cements in contemporaneous beachrocks, Jaguaribe beach, Itamaracá island, northeastern Brazil: petrographic, geochemical and isotopic aspects

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Contribuição dos sedimentos e ictiólitos para a identificação do ambiente de formação do Sambaqui do Moa (Saquarema-RJ)

O Sambaqui do Moa é um sítio arqueológico localizado em Itaúna, Saquarema, litoral do Estado do Rio de Janeiro. Três momentos de ocupação foram reconhecidos neste sítio: o estrato 3 na base correspondente ao início da ocupação deste sítio; o 2, intermediário, aponta para uma ocupação mais intensa, com grande concentração de carapaças de moluscos, ossos de peixes e sepultamentos humanos; e o 1, o mais superficial, relacionado à última ocupação. Para identificar as condições ambientais de desenvolvimento do Sambaqui do Moa foram coletadas amostras de sedimentos e material zooarqueológico nestes três estratos. O material zooarqueológico está representado por restos microscópicos de peixes (ictiólitos), compostos por microdentes com diferentes morfologias: caninos, incisivos e molares. Os sedimentos segundo análises por DRX são constituídos além de quartzo e caulinita, calcita, aragonita e por fluorapatita. Este último é o principal mineral do material zooarqueológico, enquanto calcita e aragonita refletem os restos de conchas contidos neles, abundantes no sítio. As análises mineralógicas foram confirmadas pelas análises químicas, em que os teores elevados de P₂O₅, CaO e PF (H₂O, CO₂), respondem pela fluorapatita, calcita e aragonita. Modificações químicas representadas pelas variações nos conteúdos de C e P nos microdentes sugerem que estes experimentaram mineralização, num processo inicial de fossilização, pósdeposição. Os dados de isótopos estáveis ¹³C e ¹⁵N permitiram definir a fonte de matéria orgânica do sambaqui do Moa como marinha/salobra, em que a vegetação representava-se, predominantemente, por plantas do tipo C3 de floresta tropical. As razões ⁸⁷Sr/⁸⁶Sr nos ictiólitos confirmam que o ambiente no entorno do sambaqui tenha sido estuarino. A morfologia dentária permitiu reconhecer cinco famílias até então não registradas para o sítio, como Labridae, Serranidae, Ariidae, Erythrinidae e Characidae, que confirmam o ambiente estuarino. A idade do sambaqui do Moa por datação radiocarbono a partir dos sedimentos mostrou perturbação no estrato 2, ocasionando a inversão das idades entre os estratos o que pode ser justificado por processos de formação e/ou mudanças dos rios que modificaram as configurações geológico-geomorfológicas da área. Outra explicação poderia ser a interferência humana, devido ao grande número de enterramentos (mais de 30), tenha perturbado a ordem dos momentos de ocupação do sambaqui do Moa, além de possíveis processos erosivos. O sambaqui do Moa se instalou, portanto, em uma área de transição marinho-estuarina.

Geologia e paleontologia do biohermito da Formação Pirabas (Mioceno Inferior)

O presente trabalho compreende o estudo geológico e paleontológico detalhado da litofácies recifal da Formação Pirabas, Estado do Pará, aflorante na Praia do Maçarico, município de Salinópolis, como um corpo pequeno, isolado e lenticular, que deve ter se desenvolvido na rampa interna da plataforma do Mar de Pirabas. O conteúdo biótico é rico e variado, composto por três grupos de algas coralíneas, poríferos, corais, briozoários, equinoides, foraminíferos, ostracodes, e moluscos. Foram reconhecidos neste recife em mancha três estágios de sucessão ecológica, estabilização, colonização e diversificação, onde as finas crostas micríticas reconhecidas na parte superior do estágio diversificação indicam degradação das condições ambientais favoráveis à acreção recifal, provavelmente devido a continentalização do sítio deposicional. O exame petrográfico revelou apenas uma microfácies deposicional, biomicrito, sem consideráveis variações texturais e composicionais. A cimentação marinha é predominante, representada por massas microcristalinas e cimentos micríticos, localmente neomorfisados para bioesparito, e detritos carbonáticos advindos do fluxo biogênico inconsolidado, resultantes principalmente da dispersão de cristais de aragonita dos fragmentos algálicos, acumulados sob a forma de lama micrítica. Para a gênese da bioconstrução as algas foram fundamentais na consolidação e modelagem do arcabouço, principalmente as macroalgas vermelhas, decisivas para a proteção e cimentação dos demais organismos.

Depósitos carbonáticos de Tangará da Serra (MT): uma nova ocorrência de capa carbonática neoproterozóica no sul do Cráton Amazônico

Capas carbonáticas se traduzem num dos mais importantes depósitos relacionados ao final das glaciações globais neoproterozóicas. Na região de Tangará da Serra, margem sul do Cráton Amazônico, foi descrita uma sucessão carbonática neoproterozóica de aproximadamente 20 m de espessura que inclui o topo da Formação Mirassol d'Oeste e a base da Formação Guia, respectivamente as capas dolomítica e calcária da base do Grupo Araras. A capa dolomítica é composta por dolograisntones peloidais rosados com laminação plano paralela e truncamentos de baixo ângulo, interpretados como registros de uma plataforma rasa a moderadamente profunda. A capa calcária consiste em siltitos maciços e laminados e calcários finos cristalinos com acamamento de megamarcas onduladas, interpretados como depósitos de plataforma mista moderadamente profunda dominada por ondas. Calcários finos cristalinos com laminação ondulada/marcas onduladas e leques de cristais (pseudomorfos de aragonita) intercalados com folhelhos foram interpretados como depósitos de plataforma profunda e supersaturada em CaCO₃. Calcários com estruturas de escorregamento (slump), laminações convolutas e falhas sin-sedimentares caracterizam depósitos de talude e diques neptunianos, preenchidos por brechas calcárias, e camadas deformadas isoladas sugerem atividade sísmica durante a sedimentação. A sucessão carbonática de Tangará da Serra estende a ocorrência de capas carbonáticas no sul do Cráton Amazônico e corrobora com a presença de uma extensa plataforma carbonática formada durante a transgressão após a glaciação Puga correlata ao evento Marinoano.

Carbonate system in the water masses of the Southeast Atlantic sector of the Southern Ocean during February and March 2008

[EN]Carbonate system variables were measured in the South Atlantic sector of the Southern Ocean along a transect from South Africa to the southern limit of the Antarctic Circumpolar Current (ACC) from February to March 2008. Eddies detached from the retroflection of the Agulhas Current increased the gradients observed along the fronts. Minima in the fugacity of CO2, fCO2, and maxima in pH on either side of the frontal zone were observed, noting that within the frontal zone fCO2 reached maximum values and pH was at a minimum.Vertical distributions of water masses were described by their carbonate system properties and their relationship to CFC concentrations. Upper Circumpolar Deep Water (UCDW) and Lower Circumpolar Deep Water (LCDW) offered pHT,25 values of 7.56 and 7.61, respectively. The UCDW also had higher concentrations of CFC-12 (>0.2 pmol kg?1) as compared to deeper waters, revealing that UCDW was mixed with recently ventilated waters. Calcite and aragonite saturation states ( ) were also affected by the presence of these two water masses with high carbonate concentrations. The aragonite saturation horizon was observed at 1000m in the subtropical area and north of the Subantarctic Front. At the position of the Polar Front, and under the influence of UCDW and LCDW, the aragonite saturation horizon deepened from 800m to 1500m at 50.37_ S, and reached 700m south of 57.5_ S. High latitudes proved to be the most sensitive areas to predicted anthropogenic carbon increase. Buffer coefficients related to changes in [CO2], [H+] and with changes in dissolved inorganic carbon (CT)and total alkalinity (AT) offered minima values in the Antarctic IntermediateWater and UCDWlayers. These coefficients suggest that a small increase in CT will sharply decrease the status of pH and carbonate saturation. Here we present data that suggest that south of 55_ S, surface water will be under-saturated with respect to aragonite within the next few decades.

Studio di macromolecole associate alla calcificazione in organismi marini

Lo studio riportato in questa tesi ha come scopo l’osservazione e la comprensione dei processi molecolari associati alla deposizione di CaCO3 nei polimorfi di calcite e aragonite nel mollusco gasteropode Haliotis rufescens. In particolare l’attenzione si è focalizzata sullo strato glicoproteico (green layer) che si trova inserito all’interno dell’ipostraco o strato madreperlaceo. Studi precedenti suggeriscono l’ipotesi che il green layer sia una struttura polifunzionale che svolge un ruolo attivo nell’induzione di crescita dei cristalli di carbonato di calcio nella conchiglia. All’analisi microscopica il green layer si presenta come un foglietto trilaminato. Sugli strati esterni è depositata aragonite nella forma prismatica da una parte e sferulitica dall’altra. All’interno è racchiuso un core proteico, formato da glicoproteine e ricco di chitina. Questa struttura tripartita conferisce al guscio calcareo nuove proprietà meccaniche, come la resistenza alle fratture molto maggiore rispetto al minerale naturale. Il green layer è stato trattato in ambiente alcalino, l’unico in grado di solubilizzarlo. È stato ottenuto del materiale proteico che è stato caratterizzato utilizzando SDS-PAGE, colorato con Blu Comassie e all’argento per visualizzarne la componente peptidica. Il green layer è fluorescente, sono state quindi eseguite analisi spettroscopiche sull’estratto peptidico per determinarne le proprietà chimo fisiche (dipendenza dal pH dell’intensità di fluorescenza). Sono stati eseguiti esperimenti di crescita dei cristalli di CaCO3 in ambiente saturo di CaCl2 in assenza e presenza del peptide e in assenza e presenza di Mg++. I cristalli sono stati osservati al microscopio elettronico a scansione (SEM) e al microscopio confocale. Da un punto di vista spettroscopico si osserva che, eccitando l’estratto alcalino del green layer a 280 nm e 295 nm, lunghezze d’onda caratteristiche degli aminoacidi aromatici, si ottiene uno spettro di emissione che presenta una forte banda centrata a 440 nm e una spalla a circa 350 nm, quest’ultima da ascrivere all’emissione tipica di aminoacidi aromatici. L’emissione di fluorescenza dell’estratto dal green layer dipende dal pH per tutte le bande di emissione; tale effetto è particolarmente visibile per lo spettro di emissione a 440 nm, la cui lunghezza d’onda di emissione e l’intensità dipendono dalla ionizzazione di aminoacidi acidi (pKa = 4) e dell’istidina (pKa = 6.5 L’emissione a 440 nm proviene invece da un’eccitazione il cui massimo di eccitazione è centrato a 350 nm, tipica di una struttura policiclica aromatica. Poiché nessun colorante estrinseco viene isolato dalla matrice del green layer a seguito dei vari trattamenti, tale emissione potrebbe derivare da una modificazione posttraduzionale di aminoacidi le cui proprietà spettrali suggeriscono la formazione di un prodotto di dimerizzazione della tirosina: la ditirosina. Questa struttura potrebbe essere la causa del cross-link che rende resistente il green layer alla degradazione da parte di agenti chimici ed enzimatici. La formazione di ditirosina come fenomeno post-traduzionale è stato recentemente acquisito come un fenomeno di origine perossidativa attraverso la formazione di un radicale Tyr ed è stato osservato anche in altri organismi caratterizzati da esoscheletro di tipo chitinoso, come gli insetti del genere Manduca sexta. Gli esperimenti di cristallizzazione in presenza di estratto di green layer ne hanno provato l’influenza sulla nucleazione dei cristalli. In presenza di CaCl2 avviene la precipitazione di CaCO3 nella fase calcitica, ma la conformazione romboedrica tipica della calcite viene modificata dalla presenza del peptide. Inoltre aumenta la densità dei cristalli che si aggregano a formare strutture sferiche di cristalli incastrati tra loro. Aumentando la concentrazione di peptide, le sfere a loro volta si uniscono tra loro a formare strutture geometriche sovrapposte. In presenza di Mg++, la deposizione di CaCO3 avviene in forma aragonitica. Anche in questo caso la morfologia e la densità dei cristalli dipendono dalla concentrazione dello ione e dalla presenza del peptide. È interessante osservare che, in tutti i casi nei quali si sono ottenute strutture cristalline in presenza dell’estratto alcalino del green layer, i cristalli sono fluorescenti, a significare che il peptide è incluso nella struttura cristallina e ne induce la modificazione strutturale come discusso in precedenza. Si osserva inoltre che le proprietà spettroscopiche del peptide in cristallo ed in soluzione sono molto diverse. In cristallo non si ha assorbimento alla più corta delle lunghezze d’onda disponibili in microscopia confocale (405 nm) bensì a 488 nm, con emissione estesa addirittura sino al rosso. Questa è un’indicazione, anche se preliminare, del fatto che la sua struttura in soluzione e in cristallo è diversa da quella in soluzione. In soluzione, per un peptide il cui peso molecolare è stimato tra 3500D (cut-off della membrana da dialisi) e 6500 D, la struttura è, presumibilmente, totalmente random-coil. In cristallo, attraverso l’interazione con gli ioni Ca++, Mg++ e CO3 -- la sua conformazione può cambiare portando, per esempio, ad una sovrapposizione delle strutture aromatiche, in modo da formare sistemi coniugati non covalenti (ring stacking) in grado di assorbire ed emettere luce ad energia più bassa (red shift).

Self assembled monolayers for engineering of structured inorganic materials in the micrometer and submicrometer range

Deutsch:In der vorliegenden Arbeit konnten neue Methoden zur Synthese anorganischer Materialien mit neuartiger Architektur im Mikrometer und Nanometer Maßstab beschrieben werden. Die zentrale Rolle der Formgebung basiert dabei auf der templatinduzierten Abscheidung der anorganischen Materialien auf selbstorganisierten Monoschichten. Als Substrate eignen sich goldbedampfte Glasträger und Goldkolloide, die eine Mittelstellung in der Welt der Atome bzw. Moleküle und der makroskopischen Welt der ausgedehnten Festkörper einnehmen. Auf diesen Substraten lassen sich Thiole zu einer monomolekularen Schicht adsorbieren und damit die Oberflächeneigenschaften des Substrates ändern. Ein besonderer Schwerpunkt bei dieser Arbeit stellt die Synthese speziell auf die Bedürfnisse der jeweiligen Anwendung ausgerichteten Thiole dar.Im ersten Teil der Arbeit wurden goldbedampfte Glasoberflächen als Template verwendet. Die Abscheidung von Calciumcarbonat wurde in Abhängigkeit der Schichtdicke der adsorbierten Monolage untersucht. Aragonit, eine der drei Hauptphasen des Calciumcarbonat Systems, wurde auf polyaromatischen Amid - Oberflächen mit Schichtdicken von 5 - 400 nm Dicke unter milden Bedingung abgeschieden. Die einstellbaren Parameter waren dabei die Kettenlänge des Polymers, der w-Substituent, die Bindung an die Goldoberfläche über Verwendung verschiedener Aminothiole und die Kristallisationstemperatur. Die Schichtdickeneinstellung der Polymerfilme erfolgte hierbei über einen automatisierten Synthesezyklus.Titanoxid Filme konnten auf Oberflächen strukturiert werden. Dabei kam ein speziell synthetisiertes Thiol zum Einsatz, das die Funktionalität einer Styroleinheit an der Oberflächen Grenze als auch eine Möglichkeit zur späteren Entfernung von der Oberfläche in sich vereinte. Die PDMS Stempeltechnik erzeugte dabei Mikrostrukturen auf der Goldoberfläche im Bereich von 5 bis 10 µm, die ihrerseits über die Polymerisation und Abscheidung des Polymers in den Titanoxid Film überführt werden konnten. Drei dimensionale Strukturen wurden über Goldkolloid Template erhalten. Tetraethylenglykol konnte mit einer Thiolgruppe im Austausch zu einer Hydroxylgruppe monofunktionalisiert werden. Das erhaltene Molekül wurde auf kolloidalem Gold selbstorganisiert; es entstand dabei ein wasserlösliches Goldkolloid. Die Darstellung erfolgte dabei in einer Einphasenreaktion. Die so erhaltenen Goldkolloide wurden als Krstallisationstemplate für die drei dimensionale Abscheidung von Calciumcarbonat verwendet. Es zeigte sich, dass Glykol die Kristallisation bzw. den Habitus des krsitalls bei niedrigem pH Wert modifiziert. Bei erhöhtem pH Wert (pH = 12) jedoch agieren die Glykol belegten Goldkolloide als Template und führen zu sphärisch Aggregaten. Werden Goldkolloide langkettigen Dithiolen ausgesetzt, so führt dies zu einer Aggregation und Ausfällung der Kolloide aufgrund der Vernetzung mehrer Goldkolloide mit den Thiolgruppen der Alkyldithiole. Zur Vermeidung konnte in dieser Arbeit ein halbseitig geschütztes Dithiol synthetisiert werden, mit dessen Hilfe die Aggregation unterbunden werden konnte. Das nachfolgende Entschützten der Thiolfunktion führte zu Goldkolloiden, deren Oberfläche Thiol funktionalisiert werden konnte. Die thiolaktiven Goldkolloide fungierten als template für die Abscheidung von Bleisulfid aus organisch/wässriger Lösung. Die Funktionsweise der Schutzgruppe und die Entschützung konnte mittels Plasmonenresonanz Spektroskopie verdeutlicht werden. Titanoxid / Gold / Polystyrol Komposite in Röhrenform konnten synthetisiert werden. Dazu wurde ein menschliches Haar als biologisches Templat für die Formgebung gewählt.. Durch Bedampfung des Haares mit Gold, Assemblierung eines Stryrolmonomers, welches zusätzlich eine Thiolfunktionalität trug, Polymerisation auf der Oberfläche, Abscheidung des Titanoxid Films und anschließendem Auflösen des biologischen Templates konnte eine Röhrenstruktur im Mikrometer Bereich dargestellt werden. Goldkolloide fungierten in dieser Arbeit nicht nur als Kristallisationstemplate und Formgeber, auch sie selbst wurden dahingehend modifiziert, dass sie drahtförmige Agglormerate im Nanometerbereich ausbilden. Dazu wurden Template aus Siliziumdioxid benutzt. Zum einen konnten Nanoröhren aus amorphen SiO2 in einer Sol Gel Methode dargestellt werden, zum anderen bediente sich diese Arbeit biologischer Siliziumoxid Hohlnadeln aus marinen Schwämmen isoliert. Goldkolloide wurden in die Hohlstrukturen eingebettet und die Struktur durch Ausbildung von Kolloid - Thiol Netzwerken mittels Dithiol Zugabe gefestigt. Die Gold-Nanodrähte im Bereich von 100 bis 500 nm wurden durch Auflösen des SiO2 - Templates freigelegt.

Climate signatures in corals of the tropical-temperate transition zone (Late Miocene, Crete/Greece)

The present study describes a Late Miocene (early Tortonian - early Messinian) transitional carbonate system that combines elements of tropical and cool-water carbonate systems (Irakleion Basin, island of Crete, Greece). As documented by stratal geometries, the submarine topography of the basin was controlled by tilting blocks. Coral reefs formed by Porites and Tarbellastrea occurred in a narrow clastic coastal belt along a „central Cretan landmass“, and steep escarpments formed by faulting. Extensive covers of level-bottom communities existed in a low-energy environment on the gentle dip-slope ramps of the blocks that show the widest geographical distribution within the basin. Consistent patterns of landward and basinward shift of coastal onlap in all outcrop studies reveal an overriding control of 3rd and 4th order sea level changes on sediment dynamics and facies distributions over block movements. An increasingly dry climate and the complex submarine topography of the fault block mosaic kept sediment and nutrient discharge at a minimum. The skeletal limestone facies therefore reflects oligotrophic conditions and a sea surface temperature (SST) near the lower threshold temperature of coral reefs in a climatic position transitional between the tropical coral reef belt and the temperate zone. Stable isotope records (δ18O, δ13C) from massiv, exceptionally preserved Late Miocene aragonite coral skeletons reflect seasonal changes in sea surface temperature and symbiont autotrophy. Spectral analysis of a 69 years coral δ18O record reveals significant variance at interannual time scales (5-6 years) that matches the present-day eastern Mediterranean climate variability controlled by the Arctic Oscillation/North Atlantic Oscillation (AO/NAO), the Northern Hemisphere’s dominant mode of atmospheric variability. Supported by simulations with a complex atmospheric general circulation model coupled to a mixed-layer ocean model, it is suggested, that climate dynamics in the eastern Mediterranean and central Europe reflect atmospheric variability related to the Icelandic Low 10 million years ago. Usually, Miocene corals are transformed in calcite spar in geological time and isotope values are reset by diagenetic alteration. It is demonstrated that the relicts of growth bands represent an intriguing source of information for the growth conditions of fossil corals. Recrystallized growth bands were measured systematically in massive Porites from Crete. The Late Miocene corals were growing slowly with 2-4 mm/yr, compatible with present-day Porites from high latitude reefs, a relationship that fits the position of Crete at the margin of the Miocene tropical reef belt. Over Late Miocene time (Tortonian - early Messinian) growth rates remained remarkably constant, and if the modern growth temperature relationship for massive Porites applies to the Neogene, minimum (winter) SST did not exceed 19-21°C.