Ultrasonic and X-ray computed tomography characterization of progressive fracture damage in low-porous carbonate rocks

This paper studies the fracturing process in low-porous rocks during uniaxial compressive tests considering the original defects and the new mechanical cracks in the material. For this purpose, five different kinds of rocks have been chosen with carbonate mineralogy and low porosity (lower than 2%). The characterization of the fracture damage is carried out using three different techniques: ultrasounds, mercury porosimetry and X-ray computed tomography. The proposed methodology allows quantifying the evolution of the porous system as well as studying the location of new cracks in the rock samples. Intercrystalline porosity (the smallest pores with pore radius < 1 μm) shows a limited development during loading, disappearing rapidly from the porosimetry curves and it is directly related to the initial plastic behaviour in the stress–strain patterns. However, the biggest pores (corresponding to the cracks) suffer a continuous enlargement until the unstable propagation of fractures. The measured crack initiation stress varies between 0.25 σp and 0.50 σp for marbles and between 0.50 σp and 0.85 σp for micrite limestone. The unstable propagation of cracks is assumed to occur very close to the peak strength. Crack propagation through the sample is completely independent of pre-existing defects (porous bands, stylolites, fractures and veins). The ultrasonic response in the time-domain is less sensitive to the fracture damage than the frequency-domain. P-wave velocity increases during loading test until the beginning of the unstable crack propagation. This increase is higher for marbles (between 15% and 30% from initial vp values) and lower for micrite limestones (between 5% and 10%). When the mechanical cracks propagate unstably, the velocity stops to increase and decreases only when rock damage is very high. Frequency analysis of the ultrasonic signals shows clear changes during the loading process. The spectrum of treated waveforms shows two main frequency peaks centred at low (~ 20 kHz) and high (~ 35 kHz) values. When new fractures appear and grow the amplitude of the high-frequency peak decreases, while that of the low-frequency peak increases. Besides, a slight frequency shift is observed towards higher frequencies.

Los mármoles comerciales “Marrón Imperial” y “Marrón Emperador” (S.E. España). Caracterización petrológica y criterios de exploración

Los mármoles comerciales "Marrón Imperial" y "Marrón Emperador" son dolomías brechoides que de acuerdo con la clasificación del MIA pertenece al Grupo C de mármoles comerciales. Se determinan sus parámetros petrofísicos según la norma UNE. Sus rasgos petrológicos se estudian mediante microscopio petrográfico de luz transmitida y microscopio electrónico de barrido (MEB) (en modo de electrones secundarios y electrones retrodispersados). Estas rocas son básicamente dolomías mesocristalinas con abundantes vénulas calcíticas politexturales relacionadas con procesos de brechificación y de dolomitización. Rasgos kársticos aumentan la complejidad petrológica de estas rocas ornamentales cuyo litosoma son las dolomías masivas del Cretácico Superior (¿Turoniense?) del dominio Prebético Externo. El material explotado pertenece a una alineación morfoestructural que va desde Jumilla hasta el NE de Caudete y está relacionado con la falla Jumilla-Yecla-Caudete-Font de la Figuera. La relación entre esta falla y las dolomías turonienses son el principal criterio de exploración de estas rocas ornamentales.

Structural Analysis with ANSYS on Stone Constructions in the Historical Spanish Heritage

According to the importance of rehabilitation and recovery of Architectural Heritage in the live of people, this paper is aimed to strengthen the traditional methods of stone vaults calculation taking advantage of the technological characteristics of the powerful program ANSYS Workbench. As an example of this, it could find out the possible pathologies that could arise during the construction history of the building. To limit this research, the upper vault of the main chapel of the Santiago parish church in Orihuela -Alicante- is selected as a reference which is a Jeronimo Quijano´s important building work in the XVI century in the Renaissance. Moreover, it is an innovative stone masonry vault that consists of 8 double intercrossed arches with each other and braced by severies. During the seventeenth century there was a lantern in the central cap and it is unknown why it was removed. Its construction could justify the original constructive solution with intercrossed arches that freed the center to create a more enlightened and comfortable presbytery. By similarity with other Quijano’s works, it is considered a small lantern drilling the central spherical cap. It is proposed to carry out a comparative study of it with different architectural solutions from the same period and based on several common parameters such as: a vault of square plant with spherical surround, intercrossed arches, a possible lantern, the dimension of the permitted space, similar states of loads and compact limestone masonry. The three solutions are mainly differentiated by their size and the type of lantern and its comparison lets us know which one is the most resistant and stable. The other two building works maintain some connection with the Quijano's professional scope. It has selected the particular case of the Communion chapel of the Basilica in Elche (a large prismatic lantern with a large cylindrical drum that starts from the own arches and an upper hemispherical dome), for its conservation, its proximity to Orihuela and its implementation during the century XVIII. Finally, a significant Dome Spanish Renaissance complete the selection: a cross vault of the Benavides Chapel of the Saint Francisco Convent in Baeza - Jaén-, designed by Andres of Vandelvira in the sixteenth century (a large hemispherical dome that starts from the own arcs). To simplify the calculation and standardize the work that have to be contrasted, all of them were considered with some similar characteristics: 30 cm constant thickness, the intercrossed arches were specifically analyzed and had identical loads, Young's modulus and Poisson's ratio. Regarding the calculation solutions, in general terms, the compressive stresses predominate, influencing on it the joint collaboration of the filling material on the vault, the vault itself, the thick side walls, the buttresses and the top cover weight . In addition, the three solutions are suitable, being the Orihuela one the safest and the Baeza one the riskiest for its large dimensions. Thus, the idea of intercrossed arches with suitable thickness would allow carry out the heaviest lantern and this would confirm it as a Renaissance architectural typology built in stone.

Colour changes by laser irradiation of reddish building limestones

We have used X-ray photoelectron spectroscopy (XPS) as a novel method to investigate the causes of colour changes in a reddish limestone under irradiation by a Q-switched Nd:YAG 1064 nm laser. We irradiated clean dry and wet surfaces of Pidramuelle Roja, a building stone frequently used in the Asturian heritage, at fluences ranging from 0.12 to 1.47 J cm−2. We measured the colour coordinates and undertook XPS analysis of the state of oxidation of iron both before and after irradiation. Visible colour changes and potential aesthetic damage occurred on dry surfaces from a fluence of 0.31 J cm−2, with the stone showing a greening effect and very intense darkening. The colour change on dry surfaces was considerably higher than on wet surfaces, which at the highest fluence (1.47 J cm−2) was also above the human visual detection threshold. The use of XPS demonstrated that the change in colour (chroma and hue) is associated with a reduction in the iron oxidation state on dry surfaces during laser irradiation. This points out to a potential routinary use of XPS to analyse causes of colour changes during laser cleaning in other types of coloured building stones.

Metodologias utilizadas no estudo do escoamento em aquíferos cársicos e o caso prático da captação do Olho de Mira (Maciço Calcário Estremenho)

Tese de mestrado em Geologia Aplicada, apresentada à Universidade de Lisboa, através da Faculdade de Ciências, 2016

Palaeoenvironmental and palaeoceanographic changes during the lower to middle Jurassic (Toarcian-Aalenian, ~183-171 Ma). : new evidences from calcareous nannofossils of the Lusitanian Basin

Tese de doutoramento (co-tutela), Geologia (Paleontologia e Estratigrafia), Faculdade de Ciências da Universidade de Lisboa, Université Claude Bernard Lyon 1, 2016

Miocene palaeoclimate reconstructions from the North Alpine Foreland Basin in Germany

Early- and Middle-Miocene sediments of the North Alpine Foreland Basin (NAFB) in Southern Germany contain one of the world richest regional records of silicified wood. Here we analyze over 1,000 identifiable samples, belonging to 80 wood anatomical taxa from 61 stratigraphically well-dated localities using principally the Coexistence Approach. The samples investigated originate from fluvial sediments representing periods of intensified surface runoff in the NAFB and therefore represent and provide information pertaining to the wet end-member of the fluctuating climate system. The dry end of the climate system is represented in the profiles either by hiatuses or palaeosoils. The dataset is split into four xylofloras: (I) the Ortenburg xyloflora (Late Ottnangian; ~17.5 to 17.3 Ma) originating from a paratropical evergreen Carapoxylon (Xylocarpus) forest; (II) the Southern Franconian Alb xyloflora (Late Karpatian; 17.0 to ~16.3 Ma) originating from a subtropical semideciduous limestone forest; (III) the upper Older Series xyloflora (Early Badenian; ~16.3 to ~15.3 Ma) originating from a subtropical oak-laurel forest; and (IV) the upper Middle Series xyloflora (Middle Badenian; 14.3 to ~13.8 Ma) originating from a subtropical dry deciduous forest.

Organic properties of sediments and amino acids in iterstitial waters of ODP Holes 111-677A and 111-678B

The basement at Ocean Drilling Program (ODP) Sites 677 and 678 originated from the Galapagos spreading center of the Costa Rica Rift and has moved about 200 km over the last 6 m.y. (Fig. 1) (Shipboard Scientific Party, 1987, 1988; Scientific Drilling Party, 1987). Sediments about 300 m thick cover basement so young that basal sediments at Sites 677 and 678 have been reheated up to 60?-70?C at Site 677 and altered to limestone and/or chert (Shipboard Scientific Party, 1988). Sediments from both sites indicate (1) a high sedimentation rate (about 48 m/m.y.) and (2) biogenic silica and carbonate as the main constituents of sediments (Table 1) (Shipboard Scientific Party, 1988). Heatflow observations and measurements of interstitial water chemistry around the sites show that Site 677 is in a lower heatflow zone (166 mW/m**2; 1°12.14'N, 83°44.22'W) whereas Site 678 is located in a zone of higher heat flow (250 mW/m**2; 1°13.01'N, 83°43.39'W) (Langseth et al., 1988; Shipboard Scientific Party, 1988). In the flank hydrothermal systems, circulating solution is moving upward through the sedimentary column in zones of higher heat flow while it is moving downward in zones of lower heat flow (Anderson and Skilbeck, 1981). The chemistry of the interstitial waters is modified by several processes such as (1) diagenetic reactions and (2) advective and (3) diffusive transports of dissolved constituents. Analyses of Ca2+ and Mg2+ in interstitial waters from Sites 677 and 678 show that their profiles are mainly controlled by advective transport (Shipboard Scientific Party, 1988). In contrast, the interstitial-water profiles for NH4+, Si, and PO4[3-] are highly affected by reactions in the sediments. Site 677 offers a good opportunity to investigate amino acids in the interstitial waters because sediments of similar compositions have been deposited at constant rates of sedimentation. There are few previous works on amino acid distributions in interstitial waters (Henrichs and Parrington, 1979; Michaelis et al., 1982; Henrichs et al., 1984; Henrichs and Farrington, 1987; Ishizuka et al., 1988). In this chapter, we report (1) Rock-Eval analysis and (2) the composition of total hydrolyzable and dissolved free amino acids (THAA and DFAA, respectively) in the interstitial waters. Our objectives are to discuss (1) the possible origin of organic materials, (2) the characteristics of THAA and DFAA, and (3) their relationships in interstitial waters.

(Table 1) Elements at DSDP Section 93-605-66-1

The oldest sediments cored at Site 605 are upper Maestrichtian argillaceous limestone (Hole 605, Subunit VB). The terrigeneous silt content of the uppermost Maestrichtian is quite low, averaging about 3%, whereas the carbonate content is high, usually greater than 60%; the silt contains only traces of glauconite (Site 605 chapter, this volume). Within Subunit VB a K/T boundary was defined by planktonic foraminifers. It was expected to be spread over an extended vertical interval because of the continental margin depositional setting. Examination by the shipboard party showed that the K/T boundary occurs in Section 605-66-1, between 70 and 75 cm. At the contact, the foraminiferal Globigerina pseudobulloides Zone (PIc) and the Coccolith Cruciplacolithus primus Subzone (CPla) overlie, respectively, the Abathomphalus mayaroensis and Nephrolithus frequens zones (Site 605). However, the thin K/T boundary clay, which is always present in complete sections, was not found, indicating either that the K/T boundary clay was not present or, more likely, that it was washed away during the coring operation.

In situ measurements of hydrogen sulfide, oxygen, and temperature in diffuse fluids of the ultramafic-hosted Logatchev hydrothermal vent field (Mid-Atlantic Ridge)

The Logatchev hydrothermal vent field (14°45'N, Mid-Atlantic Ridge) is located in a ridge segment characterized by mantle-derived ultramafic outcrops. Compared to basalt-hosted vents, Logatchev high temperature fluids are relatively low in sulfide indicating that the diffuse, low temperature fluids of this vent field may not contain sufficient sulfide concentrations to support a chemosymbiotic invertebrate community. However, the high abundances of bathymodiolin mussels with bacterial symbionts related to free-living sulfur oxidizing bacteria suggested that bioavailable sulfide is present at Logatchev. To clarify if diffuse fluids above mussel beds of Bathymodiolus puteoserpentis provide the reductants and oxidants needed by their symbionts for aerobic sulfide oxidation, in situ microsensor measurements of dissolved hydrogen sulfide and oxygen were combined with simultaneous temperature measurements. High temporal fluctuations of all three parameters were measured above the mussel beds. H2S and O2 co-existed with mean concentrations between 9-31 µM (H2S) and 216-228 µM (O2). Temperature maxima (<= 7.4°C) were generally concurrent with H2S maxima (<= 156 µM) and O2 minima (>= 142 µM). Long-term measurements for 250 days using temperature as a proxy for oxygen and sulfide concentrations indicated that the mussels were neither oxygen- nor sulfide-limited. Our in situ measurements at Logatchev indicate that sulfide may also be bioavailable in diffuse fluids from other ultramafic-hosted vents along slow- and ultraslow-spreading ridges.

Chronostratigraphic summary and raw counts of selected dinoflagellate cysts and architarch taxa of ODP Hole 151-907A

A detailed dinoflagellate cyst investigation of the almost continuous Middle Miocene through Pliocene of Ocean Drilling Program Hole 907A in the Iceland Sea has been conducted at 100-kyr resolution. The investigated section is well constrained by magnetostratigraphy, providing for the first time an independent temporal control on a succession of northern high-latitude dinoflagellate cyst bioevents. Based on the highest/lowest occurrences (HO/LO) and highest common occurrence (HCO) of 20 dinoflagellate cyst taxa and one acritarch species, 26 bioevents have been defined and compared with those recorded at selected DSDP, ODP, and IODP sites from the North Atlantic and contiguous seas, and in outcrops and boreholes from the onshore and offshore eastern U.S.A., and the North Sea and Mediterranean basins. Comparisons reveal near-synchronous HOs of the dinoflagellate cysts Batiacasphaera micropapillata (3.8-3.4 Ma, mid-Pliocene) and Reticulatosphaera actinocoronata (4.8-4.2 Ma, Lower Pliocene) across the Nordic Seas and North Atlantic, highlighting their value on a supraregional scale. This probably applies also to Hystrichosphaeropsis obscura (upper Tortonian), when excluding ODP Hole 907A where its sporadic upper stratigraphic range presumably relates to cooling in the early Tortonian. Over a broader time span within the upper Tortonian, the HO of Operculodinium piaseckii likely also permits correlation across the Nordic Seas and North Atlantic, and the HO of Labyrinthodinium truncatum appears useful in the Labrador and Nordic Seas. Biostratigraphic markers useful for regional rather than supraregional correlation are the HOs of Batiacasphaera hirsuta (c. 8.4 Ma, upper Tortonian) and Unipontidinium aquaeductus (c. 13.6-13.9 Ma, upper Langhian), the HCO of the acritarch Decahedrella martinheadii (c. 6.7-6.3 Ma, Messinian), and possibly the LO of Cerebrocysta irregulare sp. nov. (c. 13.8 Ma, uppermost Langhian) across the Nordic Seas. Since Habibacysta tectata, B. micropapillata, R. actinocoronata and D. martinheadii have been observed in the Arctic Ocean, they are potentially useful for high latitude correlations in the polar domain. The LOs of Habibacysta tectata and Unipontidinium aquaeductus suggest a mid- to late Langhian age (15.1-13.7 Ma) for deposits at the base of Hole 907A, thus providing new constraints on the age of basalts at the base of ODP Hole 907A. The stratigraphically important dinoflagellate cysts Cerebrocysta irregulare sp. nov., and Impagidinium elongatum sp. nov. are formally described.

(Table 1) Age and depth of reflectors of the 3.5-kHz and airgun seismic record and their corresponding depth of ash layers, carbonate peaks, and transition zones from DSDP Hole 83-504B

DSDP cores from areas of low (Site 505) and high heat flow (Site 504 B) near the Costa Rica Rift, together with seismic profiles from the Panama Basin, have been studied to determine the relationship between: (1) carbonate content and physical and acoustic properties; and (2) carbonate content, carbonate diagenesis and acoustic stratigraphy. Except for ash and chert layers, bulk density correlates strongly and linearly with carbonate content. Velocity is uniform downcore and only small variations at a small scale are measured. Thus an abrupt change in carbonate content will cause abrupt changes in acoustic impedance and should cause reflectors that can be detected acoustically. A comparison of seismic profiler reflection records with physical properties, carbonate content and reflection coefficients indicates that the main reflectors can be identified with ash layers, diagenetic boundaries, and carbonate content variations. Diagenesis of carbonate sediments is present at Site 504B in a 260 m-thick ooze-chalk-limestone/chert sequence. These diagenetic sequences occur in areas of higher heat flow (200 mW/m**2). Seismic profiler records can be used to map the extent and depth of these diagenetic boundaries.

Chemical composition and solubility of ocean phosphatized rocks in seawater

In order to elucidate possibility of limestone phosphatization during contact with seawater two sets of experiments were carried out: that of solubility of natural phosphates in seawater and that of deposition of phosphorus onto calcareous phase. Concentration of phosphorus in seawater used for solubility experiments varied from 39 to 338 µ/l, temperature was 5.5-17.5°C and pH 7.8-7.9. The lowest solubility was characteristic of ancient crystallized samples. The deposition experiments showed that in case when concentration of dissolved phosphate in seawater reaches 3 mg/l it might be sorbed on solid CaCO3 phase without forming its own mineral. The latter is able to form rapidly but only if magnesium is not present in solution. In magnesium-free water calcium phosphates precipitate when concentration of dissolved phosphorus is higher than 0.9-1.2 mg/l. These results show that phosphatization of limestones in marine environment takes place during their contact with pore water but not with marine bottom water.