Chemistry of fluid inclusions in rock samples from Dronning Maud Land

Dense, CO2-rich fluid inclusions hosted by plagioclases, An45 to An54, of the O.-v.-Gruber- Anorthosite body, central Dronning Maud Land, East Antarctica, contain varying amounts of small calcite, paragonite and pyrophyllite crystals detected by Raman microspectroscopy. These crystals are reaction products that have formed during cooling of the host and the original CO2-rich H2O-bearing enclosed fluid. Variable amounts of these reaction products illustrates that the reaction did not take place uniformly in all fluid inclusions, possibly due to differences in kinetics as caused by differences in shape and size, or due to compositional variation in the originally trapped fluid. The reaction albite + 2anorthite + 2H2O + 2CO2 = pyrophyllite + paragonite + 2calcite was thermodynamically modelled with consideration of different original fluid compositions. Although free H2O is not detectable in most fluid inclusions, the occurrence of OH-bearing sheet silicates indicates that the original fluid was not pure CO2, but contained significant amounts of H2O. Compared to an actual fluid inclusion it is obvious, that volume estimations of solid phases can be used as a starting point to reverse the retrograde reaction and recalculate the compositional and volumetrical properties of the original fluid. Isochores for an unmodified inclusion can thus be reconstructed, leading to a more realistic estimation of P-T conditions during earlier metamorphic stages or fluid capturing.

De la isla de Menorca a las costas sur y este de Inglaterra: análisis del prototipo de torre Martello = From the island of Minorca to the south and east coasts of England: analysis of the prototype of the Martello tower

Esta tesis doctoral desarrolla una investigación original sobre las torres defensivas de Menorca y las torres Martello de las costas sur y este de Inglaterra. Con respecto a las torres menorquinas, se distinguen las de Alcaufar y Punta Prima, construidas por ingenieros militares españoles, en 1786; de las levantadas por el ejército británico durante su último periodo de dominación de la isla, entre 1798 y 1802. Estos ingenieros reales británicos construyen las torres Martello en las costas inglesas, entre 1805 y 1812; y otras, semejantes a ellas, en el resto de su Imperio, hasta mediados del siglo XIX. La falta de estudios que relacionen las torres defensivas de Menorca y las Martello inglesas dentro del marco disciplinario de la construcción, ha constituido la justificación de esta investigación. La hipótesis de trabajo plantea un objetivo principal: el estudio y análisis comparativo entre ellas, que se desarrolla en varios niveles de análisis: morfológico, físico-constructivo, de visibilidades; pero también territorial, histórico y poliorcético. Esta tesis cuestiona, en consecuencia, la idea tradicionalmente aceptada de que las torres Martello tomaran la torre de Mortella, en Córcega, o cualquiera de las denominadas torres "preMartello", como referencia para crear su prototipo. La metodología empleada combina los trabajos de gabinete con una intensa labor de campo, en la que se documentaron cincuenta y siete torres, catorce en Menorca y cuarenta y tres en Inglaterra. Se han redactado sus correspondientes fichas de datos, que incluyen aspectos generales - morfológicos y constructivos -, así como documentación fotográfica. Se han elaborado los levantamientos morfológicos de siete de estas torres, aquellas que por sus particularidades constructivas, o bien representan un determinado tipo de torre, o bien se distinguen del resto. Del mismo modo, se han desarrollado los levantamientos físico-constructivos y la caracterización de materiales de las cuatro torres más relevantes para este estudio: las menorquinas Alcaufar y Punta Prima, y las torres 24 y C, que ejemplifican, respectivamente, las levantadas en las costas sur y este de Inglaterra. El sistemático método de trabajo llevado a cabo ha favorecido la investigación y ha ayudado a obtener conclusiones que verifican la hipótesis planteada en la tesis y cumplen los objetivos establecidos al comienzo de la misma. ABSTRACT This doctoral thesis develops an original research on the defensive towers of Minorca, and the Martello towers on the south and east coasts of England. Regarding the Minorcan towers, Alcaufar and Punta Prima, built by the Spanish military engineers in 1786, must be distinguished from those erected by the British Army during its last period of domination of the island between 1798 and 1802. These Royal Engineers build the Martello towers on the English coasts between 1805 and 1812; and others, similar to them, in the rest of their Empire until the middle of the 19th century. The lack of studies linking these Minorcan and English towers, within the disciplinary framework of construction, has been the justification for this research. The hypothesis poses a main goal: the study and comparative analysis of them, which takes place at several levels of analysis: morphological, constructive, of visibilities; but also territorial, historical and poliorcetic. Consequently, this thesis questions the traditionally accepted notion that the Martello towers took the Corsican Mortella Tower, or any of the so-called “preMartello” towers as a reference to create their prototype. The methodology combines the cabinet works with significant fieldwork, in which fifty seven towers were documented, fourteen in Minorca and forty three in England. The corresponding data sheets were drafted including general aspects - morphological and constructive-, and photographic documentation. Morphological survey plans were developed for seven of these towers due to their construction peculiarities, which either denote a specific type of tower or makes it stand out from the rest. Likewise, constructive survey plans and material characterisation sheets of the four more relevant towers in this study were developed: the Minorcan Alcaufar and Punta Prima, and towers 24 and C, both respectively exemplifying those built on the south and east coasts of England. The systematic method of work encouraged the research and helped to draw conclusions that both confirm the hypothesis raised in the thesis and meet the objectives established at the beginning of it.

Chemistry and fluid inclusions of the sheeted dike comples of ODP Holes 137-504B and 140-504B

Fluid inclusions in variably altered diabase recovered from Ocean Drilling Program Legs 137 and 140 at Hole 504B, Costa Rica Rift, exhibit fluid salinities up to 3.7 times that of seawater values (11.7 wt% NaCl equivalent) and exhibit uncorrected homogenization temperatures of 125°C to 202°C. The liquid-dominated inclusions commonly are entrapped in zones of secondary plagioclase and may be primary in origin. Fluid salinities are similar to compositions of fluids venting on the seafloor (0.4-7.0 wt% NaCl) and overlap with those measured in metabasalt samples recovered from near the Kane Fracture Zone on the Mid-Atlantic Ridge and from the Troodos ophiolite, Cyprus. The salinity variations may reflect hydration reactions involving formation of secondary mineral assemblages under rock-dominated conditions, which modify the ionic strength of hydrothermal fluids by consuming or liberating water and chloride ion. Rare CO2-CH4-bearing inclusions, subjacent to zones where talc after olivine becomes an important secondary mineral phase (1700 mbsf), may have formed due to local interaction of seawater and olivine at low water to rock ratios. Corrected average fluid inclusion homogenization temperatures exhibit a gradient from 159°C at a depth of 1370 mbsf to 183°C at a depth of 1992 mbsf and are in apparent equilibrium with the present conductive downhole temperatures. These data indicate that fluid inclusions may be used to estimate downhole temperatures if logging data are unavailable. The compositional and thermal evolution of the diabase-hosted fluids may reflect late-stage, off-axis circulation and conductive heating of compositionally modified seawater in the sheeted dike complex at Hole 504B.

Technical note: how accurate can stalagmite formation temperatures be determined using vapour bubble radius measurements in fluid inclusions?

Stalagmites are natural archives containing detailed information on continental climate variability of the past. Microthermometric measurements of fluid inclusion homogenisation temperatures allow determination of stalagmite formation temperatures by measuring the radius of stable laser-induced vapour bubbles inside the inclusions. A reliable method for precisely measuring the radius of vapour bubbles is presented. The method is applied to stalagmite samples for which the formation temperature is known. An assessment of the bubble radius measurement accuracy and how this error influences the uncertainty in determining the formation temperature is provided. We demonstrate that the nominal homogenisation temperature of a single inclusion can be determined with an accuracy of ±0.25 °C, if the volume of the inclusion is larger than 105 μm3. With this method, we could measure in a proof-of-principle investigation that the formation temperature of 10–20 yr old inclusions in a stalagmite taken from the Milandre cave is 9.87 ± 0.80 °C, while the mean annual surface temperature, that in the case of the Milandre cave correlates well with the cave temperature, was 9.6 ± 0.15 °C, calculated from actual measurements at that time, showing a very good agreement. Formation temperatures of inclusions formed during the last 450 yr are found in a temperature range between 8.4 and 9.6 °C, which corresponds to the calculated average surface temperature. Paleotemperatures can thus be determined within ±1.0 °C.

Triple isotope (δD, δ17O, δ18O) study on precipitation, drip water and speleothem fluid inclusions for a central European cave (NW Switzerland)

Deuterium (dD) and oxygen (d18O) isotopes are powerful tracers of the hydrological cycle and have been extensively used for paleoclimate reconstructions as they can provide information on past precipitation, temperature and atmospheric circulation. More recently, the use of 17Oexcess derived from precise measurement of d17O and d18O gives new and additional insights in tracing the hydrological cycle whereas uncertainties surround this proxy. However, 17Oexcess could provide additional information on the atmospheric conditions at the moisture source as well as about fractionations associated with transport and site processes. In this paper we trace water stable isotopes (dD, d17O and d18O) along their path from precipitation to cave drip water and finally to speleothem fluid inclusions for Milandre cave in northwestern Switzerland. A two year-long daily resolved precipitation isotope record close to the cave site is compared to collected cave drip water (3 months average resolution) and fluid inclusions of modern and Holocene stalagmites. Amount weighted mean dD, d18O and d17O are �71.0‰, �9.9‰, �5.2‰ for precipitation, �60.3‰, �8.7‰, �4.6‰ for cave drip water and �61.3‰, �8.3‰, �4.7‰ for recent fluid inclusions respectively. Second order parameters have also been derived in precipitation and drip water and present similar values with 18 per meg for 17Oexcess whereas d-excess is 1.5‰ more negative in drip water. Furthermore, the atmospheric signal is shifted towards enriched values in the drip water and fluid inclusions (D of ~ þ 10‰ for dD). The isotopic composition of cave drip water exhibits a weak seasonal signal which is shifted by around 8e10 months (groundwater residence time) when compared to the precipitation. Moreover, we carried out the first d17O measurement in speleothem fluid inclusions, as well as the first comparison of the d17O behaviour from the meteoric water to the fluid inclusions entrapment in speleothems. This study on precipitation, drip water and fluid inclusions will be used as a speleothem proxy calibration for Milandre cave in order to reconstruct paleotemperatures and moisture source variations for Western Central Europe.

P-T-Fluid evolution and graphite deposition during retrograde metamorphism in Ribeira Fold Belt, SE Brazil: Oxygen fugacity, fluid inclusions and C-O-H isotopic evidence

Combined fluid inclusion (FI) microthermometry, Raman spectroscopy, X-ray diffraction, C-O-H isotopes and oxygen fugacities of granulites from central Ribeira Fold Belt, SE Brazil, provided the following results: i) Magnetite-Hematite fO(2) estimates range from 10(-11.5) bar (QFM + 1) to 10(-18.3) bar (QFM - 1) for the temperature range of 896 degrees C-656 degrees C, implying fO(2) decrease from metamorphic peak temperatures to retrograde conditions; ii) 5 main types of fluid inclusions were observed: a) CO(2) and CO(2)-N(2) (0-11 mol%) high to medium density (1.01-0.59 g/cm(3)) FI; b) CO(2) and CO(2)-N(2) (0-36 mol%) low density (0.19-0.29 g/cm(3)) FI; c) CO(2) (94-95 mol%)-N(2) (3 mol%)-CH(4) (2-3 mol%)-H(2)O (water phi(v) (25 degrees C) = 0.1) FI; d) low-salinity H(2)O-CO(2) FI; and e) late low-salinity H(2)O FI; iii) Raman analyses evidence two graphite types in khondalites: an early highly ordered graphite (T similar to 450 degrees C) overgrown by a disordered kind (T similar to 330 degrees C); iv) delta(18)O quartz results of 10.3-10.7 parts per thousand, imply high-temperature CO(2) delta(18)O values of 14.4-14.8 parts per thousand, suggesting the involvement of a metamorphic fluid, whereas lower temperature biotite delta(18)O and delta D results of 7.5-8.5 parts per thousand and -54 to -67 parts per thousand respectively imply H(2)O delta(18)O values of 10-11 parts per thousand and delta D(H2O) of -23 to -36 parts per thousand suggesting delta(18)O depletion and increasing fluid/rock ratio from metamorphic peak to retrograde conditions. Isotopic results are compatible with low-temperature H(2)O influx and fO(2) decrease that promoted graphite deposition in retrograde granulites, simultaneous with low density CO(2), CO(2)-N(2) and CO(2)-N(2)-CH(4)-H(2)O fluid inclusions at T = 450-330 degrees C. Graphite delta(13)C results of -10.9 to -11.4 parts per thousand imply CO(2) delta(13)C values of -0.8 to -1.3 parts per thousand suggesting decarbonation of Cambrian marine carbonates with small admixture of lighter biogenic or mantle derived fluids. Based on these results, it is suggested that metamorphic fluids from the central segment of Ribeira Fold Belt evolved to CO(2)-N(2) fluids during granulitic metamorphism at high fO(2), followed by rapid pressure drop at T similar to 400-450 degrees C during late exhumation that caused fO(2) reduction induced by temperature decrease and water influx, turning carbonic fluids into CO(2)-H(2)O (depleting biotite delta(18)O and delta D values), and progressively into H(2)O. When fO(2) decreased substantially by mixture of carbonic and aqueous fluids, graphite deposited forming khondalites. (C) 2010 Elsevier Ltd. All rights reserved.

Test sperimentali e modellazione di una torre di lavaggio per la filtrazione di particolato sottile in impianti di combustione delle biomasse

This study investigates biomass and particulate matter also known as PM produced from the combustion of a domestic boiler powered by mais and how to separate PM from the stream of smoke output from the boiler using wet scrubber with structured packing. Sperimentations show the inefficiency of the separator used, so we provide an optimization of the structured packing changing geometric parameters as angle of the bend or thickness of the channels. In order to obtain a higher separation efficiency we remove the structured packinkg and introduce a packed bed composed of spheres of polyethylene with a diameter of 3 mm.