Mineralogical, petrographic and geochemical characterisation of white and coloured Iberian marbles in the context of the provenancing of some artefacts from Thamusida (Kenitra, Morocco)

A multi-analytical study has been carried out on a collection of white and coloured Iberian marbles. A total of 135 marble specimens were collected in Spain and Portugal from the Betic chain (Alhaurin de la Torre, Mijas, Macael), Ossa Morena (Alconera, Almaden de la Plata and Viana do Alentejo), and the Estremoz Anticline (Bencatel, Borba and Estremoz) areas. X-ray diffractometry and carbon and oxygen stable isotope analysis were carried out on these samples; 38 samples were also investigated by optical and scanning electron microscopy. The results provide a set of diagnostic parameters that allow discriminating the sampled marble quarries. The carbonate minerals composition is distinctive for the Mijas and Alhaurin de la Torre marbles; the isotopic analysis allows discriminating also between these two dolomitic marble quarries. The Ossa Morena and Estremoz Anticline marbles share a similar stable isotope composition; the accessory mineral content, the maximum grain size (MGS) and the fabric are particularly useful in the distinction between them. In the framework of archaeometric provenance studies on Thamusida (Kenitra, Morocco) Roman marble artefacts, a specific comparison between this new Iberian database and archaeological findings has been carried out. The hypothesis of commercial exchanges between the Iberian regions and Roman Morocco is supported by the results of the provenance study, which suggested the Almaden de la Plata and Mijas quarries as possible sources of raw materials for the production of archaeological artefacts.

Carbon and oxygen isotope study of hydrothermal carbonates in the zinc-lead deposits of the San Vicente district, central Peru: A quantitative modeling on mixing processes and CO2 degassing

Carbon and oxygen isotope studies of the host and gangue carbonates of Mississippi Valley-type zinc-lead deposits in the San Vicente District hosted in the Upper Triassic to Lower Jurassic dolostones of the Pucara basin (central Peru) were used to constrain models of the ore formation. A mixing model between an incoming hot saline slightly acidic radiogenic (Pb, Sr) fluid and the native formation water explains the overall isotopic variation (delta(13)C = - 11.5 to + 2.5 parts per thousand relative to PDB and delta(18)O = + 18.0 to + 24.3 parts per thousand relative to SMOW) of the carbonate generations. The dolomites formed during the main ore stage show a narrower range (delta(13)C = - 0.1 to + 1.7 parts per thousand and delta(18)O = + 18.7 to + 23.4 parts per thousand) which is explained by exchange between the mineralizing fluids and the host carbonates combined with changes in temperature and pressure. This model of fluid-rock interaction explains the pervasive alteration of the host dolomite I and precipitation of sphalerite I. The open-space filling hydrothermal white sparry dolomite and the coexisting sphalerite II formed by prolonged fluid-host dolomite interaction and limited CO2 degassing. Late void-filling dolomite III (or calcite) and the associated sphalerite III formed as the consequence of CO2 degassing and concomitant pH increase of a slightly acidic ore fluid. Widespread brecciation is associated to CO2 outgassing. Consequently, pressure variability plays a major role in the ore precipitation during the late hydrothermal events in San Vicente. The presence of native sulfur associated with extremely carbon-light calcites replacing evaporitic sulfates (e.g., delta(13)C = - 11.5 parts per thousand), altered native organic matter and heavier hydrothermal bitumen (from - 27.0 to - 23.0 parts per thousand delta(13)C) points to thermochemical reduction of sulfate and/or thiosulfate. The delta(13)C- and delta(18)O-values of the altered host dolostone and hydrothermal carbonates, and the carbon isotope composition of the associated organic matter show a strong regional homogeneity. These results coupled with the strong mineralogical and petrographic similarities of the different MVT occurrences perhaps reflects the fact that the mineralizing processes were similar in the whole San Vicente belt, suggesting the existence of a common regional mineralizing hydrothermal system with interconnected plumbing.

Stratigraphical discontinuities, tropical landscape evolution and soil distribution relationships in a case study in SE-Brazil

On a regional summit surface in the county of Piracicaba (SP) within the Peripheric Depression of São Paulo, formed of discontinued flattened tops, there is an abrupt transition between a Typic Hapludox and a Kandiudalfic Eutrudox, together with two stoneline layers. Using stratigraphical, mineralogical, and cartographic studies, this transition and the soil distribution of this surface were studied, correlating them with the different parent materials and the morphoclimatic model of landscape evolution in Southeastern Brazil. The Typic Hapludox was formed on a sandy Cenozoic deposit (Q) that overlies a pellitic deposit of the Iratí formation (Pi), representing a regional erosive discordance. Westwards to the Piracicaba River, this sequence is interrupted by a diabase sill overlain by a red clayey material which gave origin to the Kandiudalfic Eutrudox. Two post-Permian depositional events were identified by the two stonelines and stratigraphical discontinuities. The first event generated the deposition of a sandy sediment in the form of levelled alveoluses on regional barriers, most of these formed by dikes and diabase sills, probably during a drier phase. The second depositional event, leading to the deposition of the red clay was probably the dissection of the previously formed pediplane during a humid climate, followed by another pedimentation process during a later, drier period.

Relationship between soil oxidizable carbon and physical, chemical and mineralogical properties of umbric ferralsols

The occurrence of Umbric Ferralsols with thick umbric epipedons (> 100 cm thickness) in humid Tropical and Subtropical areas is a paradox since the processes of organic matter decomposition in these environments are very efficient. Nevertheless, this soil type has been reported in areas in the Southeast and South of Brazil, and at some places in the Northeast. Aspects of the genesis and paleoenvironmental significance of these Ferralsols still need a better understanding. The processes that made the umbric horizons so thick and dark and contributed to the preservation of organic carbon (OC) at considerable depths in these soils are of special interest. In this study, eight Ferralsols with a thick umbric horizon (UF) under different vegetation types were sampled (tropical rain forest, tropical seasonal forest and savanna woodland) and their macromorphological, physical, chemical and mineralogical properties studied to detect soil characteristics that could explain the preservation of high carbon amounts at considerable depths. The studied UF are clayey to very clayey, strongly acidic, dystrophic, and Al-saturated and charcoal fragments are often scattered in the soil matrix. Kaolinites are the main clay minerals in the A and B horizons, followed by abundant gibbsite and hydroxyl-interlayered vermiculite. The latter was only found in UFs derived from basalt rock in the South of the country. Total carbon (TC) ranged from 5 to 101 g kg-1 in the umbric epipedon. Dichromate-oxidizable organic carbon represented nearly 75 % of TC in the thick A horizons, while non-oxidizable C, which includes recalcitrant C (e.g., charcoal), contributed to the remaining 25 % of TC. Carbon contents were not related to most of the inorganic soil variables studied, except for oxalate-extractable Al, which individually explained 69 % (P < 0.001) of the variability of TC in the umbric epipedon. Clay content was not suited as predictor of TC or of the other studied C forms. Bulk density, exchangeable Al3+, Al saturation, ECEC and other parameters obtained by selective extraction were not suitable as predictors of TC and other C forms. Interactions between organic matter and poorly crystalline minerals, as indicated by oxalate-extractable Al, appear to be one of the possible organic matter protection mechanisms of these soils.

Chemical and mineralogical changes in a Brazilian Rhodic Paleudult under different land use and managements

Changes in land use and management can affect the dynamic equilibrium of soil systems and induce chemical and mineralogical alterations. This study was based on two long-term experiments (10 and 27 years) to evaluate soil used for no-tillage maize cultivation, with and without poultry litter application (NTPL and NTM), and with grazed native pasture fertilized with cattle droppings (GrP), on the chemical and mineralogical characteristics of a Rhodic Paleudult in Southern Brazil, in comparison with the same soil under native grassland (NGr). In the four treatments, soil was sampled from the 0.0-2.5 and 2.5-5.0 cm layers. In the air-dried fine soil (ADFS) fraction (∅ < 2 mm), chemical characteristics of solid and liquid phases and the specific surface area (SSA) were evaluated. The clay fraction (∅ < 0.002 mm) in the 0.0-2.5 cm layer was analyzed by X-ray diffraction (XRD) after treatments for identification and characterization of 2:1 clay minerals. Animal waste application increased the total organic C concentration (COT) and specific surface area (SSA) in the 0.0-2.5 cm layer. In comparison to NGr, poultry litter application (NTPL) increased the concentrations of Ca and CECpH7, while cattle droppings (GrP) increased the P and K concentrations. In the soil solution, the concentration of dissolved organic C was positively related with COT levels. With regard to NGr, the soil use with crops (NTM and NTPL) had practically no effect on the chemical elements in solution. On the other hand, the concentrations of most chemical elements in solution were higher in GrP, especially of Fe, Al and Si. The Fe and Al concentrations in the soil iron oxides were lower, indicating reductive/complexive dissolution of crystalline forms. The X-ray diffraction (XRD) patterns of clay in the GrP environment showed a decrease in intensity and reflection area of the 2:1 clay minerals. This fact, along with the intensified Al and Si activity in soil solution indicate dissolution of clay minerals in soil under cattle-grazed pasture fertilized with animal droppings.

A contribution to the study of post-depositional alterations of pottery using TL dating analysis

In luminescence dating, the potassium concentration significantly contributes to the dose rate value in the age estimation. Within this study, fine-grain thermoluminescence dating has been applied on sherds of calcareous pottery of known age, excavated at a Roman site in Mallorca, Spain. For those of the samples that showed signs of severe potassium leaching, according to chemical and mineralogical examination, the thermoluminescence analysis provided overestimated dates. By using the known archaeological age of the samples, a corrected dose rate value can be estimated which provides the potassium concentration averaged for the burial period. Finally, a step-like model can then be used to estimate the fraction of the burial period after which most of the alteration effects took place.

Mineralogical alteration of artificial meteorites during atmospheric entry. The STONE-5 experiment

The generic concept of the artificial meteorite experiment STONE is to fix rock samples bearing microorganisms on the heat shield of a recoverable space capsule and to study their modifications during atmospheric re-entry. The STONE-5 experiment was performed mainly to answer astrobiological questions. The rock samples mounted on the heat shield were used (i) as a carrier for microorganisms and (ii) as internal control to verify whether physical conditions during atmospheric re-entry were comparable to those experienced by "real" meteorites. Samples of dolerite (an igneous rock), sandstone (a sedimentary rock), and gneiss impactite from Haughton Crater carrying endolithic cyanobacteria were fixed to the heat shield of the unmanned recoverable capsule FOTON-M2. Holes drilled on the back side of each rock sample were loaded with bacterial and fungal spores and with dried vegetative cryptoendoliths. The front of the gneissic sample was also soaked with cryptoendoliths. <p>The mineralogical differences between pre- and post-flight samples are detailed. Despite intense ablation resulting in deeply eroded samples, all rocks in part survived atmospheric re-entry. Temperatures attained during re-entry were high enough to melt dolerite, silica, and the gneiss impactite sample. The formation of fusion crusts in STONE-5 was a real novelty and strengthens the link with real meteorites. The exposed part of the dolerite is covered by a fusion crust consisting of silicate glass formed from the rock sample with an admixture of holder material (silica). Compositionally, the fusion crust varies from silica-rich areas (undissolved silica fibres of the holder material) to areas whose composition is "basaltic". Likewise, the fusion crust on the exposed gneiss surface was formed from gneiss with an admixture of holder material. The corresponding composition of the fusion crust varies from silica-rich areas to areas with "gneiss" composition (main component potassium-rich feldspar). The sandstone sample was retrieved intact and did not develop a fusion crust. Thermal decomposition of the calcite matrix followed by disintegration and liberation of the silicate grains prevented the formation of a melt.</p> <p>Furthermore, the non-exposed surface of all samples experienced strong thermal alterations. Hot gases released during ablation pervaded the empty space between sample and sample holder leading to intense local heating. The intense heating below the protective sample holder led to surface melting of the dolerite rock and to the formation of calcium-silicate rims on quartz grains in the sandstone sample. (c) 2008 Elsevier Ltd. All rights reserved.</p>

Chemical and mineralogical alteration of ceramics from a Late Bronze Age kiln at Kommos, Crete: the effect on the formation of a reference group

The formation of reference groups comprises an important procedure in chemical provenance studies of archaeological pottery. Material from ancient kilns is thought to be especially suitable for reference groups, as it comprises a definite unit of past production. Pottery from the Late Minoan IA kiln excavated at Kommos, Crete was analysed in order to produce a reference group in this important area of Minoan ceramic production. The samples were characterized by a combination of techniques providing information on the chemistry, mineralogy and microstructure of the ceramic body. Initially, the study was unable to establish, in a straightforward manner, a chemical reference group. Different ceramic pastes and a range of selective alterations and contaminations, affected by variable firing temperatures and burial environment, were shown to be responsible for the compositional variability. Procedures are described to compensate for such alterations and the perturbations in the data that they produce.

Systematic stratigraphic study of cenozoic sediments of Kerala with Special reference to warkalli and quilon formations

Quaternary stratigraphy of the Kerala coast and the genetic aspects of the sediments are discussed. The age of limeshells, and peaty sediments determined by radio carbon dating have been used for reconstruction of sea level changes. Evolution of red sands occurring in some parts of the coastal tract of Kerala is also discussed, based on textural parameters and quartz grain morphology.

Mineralogical And Sedimentological Studies Of Innershelf And Beach Sediments Along The Coast Between Paravur And Kovalam, South Kerala, India

Continental shelf is of particular significance in marine geology , because it links the two basically different structural zones in the earth's crust; the continents and ocean basins. The shelf area has much wider importance in many fields of activity such as scientific, economic, social, political and strategic. The pace of development has ultimately put pressure on mankind to look for exploitable resources and accessibility to the continental shelf area and beyond. Added to the above, the developmental activities in the coastal area would readily and directly influence the innershelf sediments. This situation demands a thorough geological knowledge of the continental shelf area. Moreover, a successful management of the continental shelf zone requires an optimum data base on the physico-chemical nature of the shelf sediments. Although sedimentological studies were carried out along the western continental shelf of India, a well documented systematic study of the inner shelf off Trivandrum coast is still found to be lacking. Considering the physiographic settings and the vicinity of two renowned placer deposits at Chavara and Manavalakurichi, such a sedimetological inventory has become all the more vital. In view of the above, a research programme has been drawn up to account the salient sedimentological and mineralogical aspects of the innershelf and beach sediments between Paravur and Kovalam, Trivandrum district, Kerala (latitudes 8° 7'00" to 8° 47'45" and longitudes 76°43'00" to 77° 40'45"). The findings are presented in six chapters formatted to address the aim of this research.

A study on mitigating the effect of sulphates in lime stabilised Cochin marine clays

Soft clays known for their high compressibility, low stiffness and low shear strength are always associated with large settlement. In place soil treatment using calcium-based stabilizers like lime and cement is a feasible solution to readdress strength deficiencies and problematic shrink/swell behaviour of unstable subgrade soils. Out of these, lime has been proved unambiguously as the most effective and economical stabilising agent for marine clays. Lime stabilisation creates long-term chemical changes in unstable clay soils to create strong, but flexible, permanent structural layers in foundations and other pavement systems. Even though calcium-based stabilizers can improve engineering properties of soft clays, problems can arise when they are used in soils rich in sulphates. It is possible for marine clays to be enriched with sulphates, either by nature or due to the discharge of nearby industrial wastes containing sulphates. The presence of sulphates is reported to adversely affect the cation exchange and pozzolanic reactions of cement and lime treated soil systems. The anions of sulphates may combine with the available calcium and alumina, and form insoluble ettringite in the soil system. Literature on sulphate attack in lime treated marine clays reports that formation of ettringite in lime-sodium sulphate-clay system is capable of adversely affecting the engineering behavior of marine clays. Only very few studies have been conducted on soft marine clays found along the coastal belt of Kerala and that too, is limited to Cochin marine clays. The studies conducted also have the limitation that the strength behaviour of lime stabilised clay was investigated only for one year. Practically no data pertaining to long term adverse effects likely to be brought about by sulphates on the strength and compressibility characteristics of Cochin marine clays is available. The overriding goal of this investigation was thus to examine the effectiveness of lime stabilisation in Cochin marine clays under varying sulphate contents. The study aims to reveal the changes brought about by varying sulphate contents on both physical and engineering properties of these clays stabilised by lime and the results for various curing periods up to two years is presented in this thesis. Quite often the load causing an unacceptable settlement may be less than the load required to cause shear failure and therefore attempt has been made in this research to highlight sulphate induced changes in both the compressibility and strength characteristics of lime treated Cochin marine clays. The study also aimed at comparing the available IS methods for sulphate quantification and has attempted to determine the threshold level of sulphate likely make these clays vulnerable by lime stabilisation. Clays used in this study were obtained from two different sites in Kochi and contained sulphate in two different concentrations viz., 0.5% and 0.1%. Two different lime percentages were tried out, 3% and 6%. Sulphate content was varied from 1% to 4% by addition of reagent grade sodium sulphate. The long term influence of naturally present sulphate is also investigated. X-ray diffraction studies and SEM studies have been undertaken to understand how the soil-lime reactions are affected in the presence of sodium sulphate. Natural sulphate content of 0.1% did not seem to have influenced normal soil lime reactions but 0.5% sulphate could induce significant changes adversely in both compressibility and strength behaviour of lime treated clays after long duration. Compressibility is seen to increase drastically with increasing sulphate content suggesting formation of ettringite on curing for longer periods. Increase in compression index and decrease in bond strength with curing period underlined the adverse effects induced in lime treated marine clays by the presence of sulphates. Presence of sulphate in concentrations ranging from 0.5 % to 4% is capable of adversely affecting the strength of lime treated marine clays. Considerable decrease is observed with increasing concentrations of sulphate. Ettringite formation due to domination of sodium ions in the system was confirmed in mineralogical studies made. Barium chloride and barium hydroxide is capable of bringing about beneficial changes both in compressibility and strength characteristics of lime treated Cochin marine clays in the presence of varying concentrations of sulphate and is strongly influenced by curing time. Clay containing sodium sulphate has increased strength values when either of barium compounds was used with lime ascompared with specimens treated with lime only. Barium hydroxide is observed to remarkably increase the strength as compared to barium chloride,when used in conjunction with lime to counteract the effect of sulphate.

Mineralogical characterization of clays used in the structural ceramic industry in west of S. Paulo State, Brazil

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

Podzolization as a deferralitization process: a study of an Acrisol-Podzol sequence derived from Palaeozoic sandstones in the northern upper Amazon Basin

Morphological, geochemical and mineralogical studies were carried out in a representative soil catena of the low-elevation plateaux of the upper Amazon Basin to interpret the steps and mechanisms involved in the podzolization of low-activity clay soils. The soils are derived from Palaeozoic sandstones. They consist of Hydromorphic Podzols under tree savannah in the depressions of the plateaux and predominantly of Acrisols covered by evergreen forest elsewhere.Incipient podzolization in the uppermost Acrisols is related to the formation of organic-rich A and Bhs horizons slightly depleted in fine-size particles by both mechanical particle transfer and weathering. Weathering of secondary minerals by organic acids and formation of organo-metallic complexes act simultaneously over short distances. Their vertical transfer is limited. Selective dissolution of aluminous goethite, then gibbsite and finally kaolinite favour the preferential cheluviation of first Fe and secondly Al. The relatively small amount of organo-metallic complexes produced is related to the quartzitic parent materials, and the predominance of Al over Fe in the spodic horizons is due to the importance of gibbsite in these low-activity clay soils.Morphologically well-expressed podzols occur in strongly iron-depleted topsoils of the depression. Mechanical transfer and weathering of gibbsite and kaolinite by organic acids is enhanced and leads to residual accumulation of sands. Organo-metallic complexes are translocated in strongly permeable sandy horizons and impregnate at depth the macro-voids of embedded soil and saprolite materials to form the spodic Bs and 2BCs horizons. Mechanical transfer of black particulate organic compounds devoid of metals has occurred later within the sandy horizons of the podzols. Their vertical transfer has formed well-differentiated A and Bh horizons. Their lateral removal by groundwater favours the development of an albic E horizon. In an open and waterlogged environment, the general trend is therefore towards the removal of all the metals that have initially accumulated as a response to the ferralitization process and have temporarily been sequestrated in organic complexes in previous stages of soil podzolization.

Geochemical Study of the Itabirite Iron Ores of the Alegria Mine - Quadrilátero Ferrífero, Minas Gerais, Brazil

The iron ores of Alegria mine are composed of itabirites enclosing minor bodies of high-grade ores. The itabirites are classified according to mineralogical composition in five types: martite-rich, goethite-rich, specularite-rich, magnetite-rich and anphibolite-rich ores. The hematites are martite-rich, magnetite-rich, specularite-rich and more rarely, amphibolite-rich. Other classification criteria of the ores are based on the physical properties and the degree of compaction. As such, the itabirites and hematites can be classified as hard, friable and soft types. The mineralogical/textural evolution of the ores is linked to the pressure and temperature conditions that accompanied the tectonic processes in anphibolite facies and the different degrees of subsequent surficial weathering processes. Petrographic and microstructural studies indicate that the magnetite and amphibole bearing itabirites represent the parent rocks that created the other itabirites and that the specularite itabirites and the hard martite types are related to silica dissolution and redeposition in zones of high and low strain. Most of itabirites ores correspond to chert oxide facies banded iron formation, except the goethite and amphibole bearing itabirite that resemble a silicate or oxide-silicate facies with minor carbonate impurities. The great mass and pods of soft martite itabirites are probably shaley oxide facies BIFs with little volcanic contribution. Trace element contents of the Alegria's itabirites show strong dissimilarities with BIFs associated with volcanism (Algoma type), but closely ressemble to the Lake Superior type, with high content in Cr, Co and low V, Ni, Cu and Zn. Although the absolute contents of REE present in the Alegria's itabirites are, in general very low, the pattern when normalised by NASC is similar to the great majority of the Archean and Paleoproterozoic BIFs elsewhere in the world, and characterised by positive Eu anomaly.

Radarfacies and sedimentological analysis: study of sedimentary substrate from an archaeological site (shell mound), southern Brazil

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