Trace Elements Distribution in Red Soils under Semiarid Mediterranean Environment

This study states the potential trace elements (TE’s) content of red soils located at the centre region of Spain, characterized by low rainfall and slight acidity over prolonged weathering periods. For this purpose, three soil profiles from a catena were described, sampled and analyzed. The most notable characteristics are the low organic matter content and the predominantly acidic pH. Illite and kaolinite are the predominant clay minerals. The fertility of the soils is sufficient to provide most of the nutrients required, with very suitable potassium levels. The geochemical characters of this soil are: only few elements remain almost invariable across the profiles and over time, however the majority of them were directly linked with the clay content. These soils are characterized by relatively low levels of some trace elements such as Sr (64.35 mg?kg–1), Ba (303.67 mg?kg–1) and Sc (13.14 mg?kg–1); high levels of other trace elements such as V (103.92 mg?kg–1), Cr (79.9 mg?kg–1), Cu (15.18 mg?kg–1), Hf (10.26 mg?kg–1), Ni (38 mg?kg–1) and Zr (337 mg?kg–1); while the levels for rare earth elements (REE’s) such as La (48.36 mg?kg–1), Ce (95.07 mg?kg–1), Th (13.33 mg?kg–1) and Nd (42.65 mg?kg–1) are significantly high. The distribution of mayor and trace elements was directly re- lated to weathering processes, parent material and anthropogenic activities.

La habitación subterránea en la Península Ibérica : investigación geológica

La habitación rupestre en la Península Ibérica conforma un amplio conjunto de manifestaciones cuyos orígenes son difíciles de dilucidar. Existen conjuntos primitivos, posiblemente horadados durante la Antigüedad Clásica y Tardía, y otros que probablemente se originaron y excavaron en la Alta Edad Media, en los que se mezclan grupos de origen religioso y otros de probable uso defensivo. El conjunto peninsular es sin duda el más variado de Europa Occidental, pues recibió influencias árabes y usos de la cristiandad antigua, importados de Oriente Próximo, que por tanto relacionan estas manifestaciones con otras del arco mediterráneo. La supervivencia del uso de las cuevas a lo largo de la Baja Edad Media -una vez afianzada la Reconquista- es una incógnita, pero los usos rupestres volvieron a generalizarse en ciertos sectores de la Península durante la Edad Moderna, toda vez que el hábitat cuevero manifestó una eclosión relacionada con la peripecia de los moriscos, primero desterrados de sus habitaciones en el Sur y Este peninsular y luego expulsados en los albores del siglo XVII. Los que quedaron, nominalmente conversos, debieron habitar de nuevo cuevas en sus lugares de origen. Esos núcleos son los más abundantes, particularmente en la provincia de Granada y aledañas. Este substrato fue seguramente el punto de apoyo para la proliferación de las cuevas de habitación a partir del siglo XIX, en el cual un creciente proletariado agrícola y urbano necesitó de alojamientos baratos y no hizo sino imitar usos preexistentes, que se pueden rastrear en muchos de los núcleos rupestres que sobrevivieron mayoritariamente hasta bien entrado el siglo XX, y que se abandonaron gradualmente a partir de los años 60 de esa centuria. Para entonces, existían barrios de cuevas extensos en muchas provincias, destacando, aparte de las andaluzas, ciertas zonas de la Cuenca del Ebro (aragonesa, navarra y riojana), del arco periurbano de Valencia, del Sur de Madrid, de la Mancha toledana, o de las provincias de Albacete, Guadalajara, Murcia e incluso de Palencia. Los núcleos antiguos se excavaron -en razón de su origen dedicado a defensa y refugio- en lugares poco accesibles, que mayoritariamente se dan en relieves anfractuosos, en las orlas marginales detríticas y carbonatadas de las cuencas terciarias y en terrenos más antiguos de la geológicamente denominada Cuenca Vasco Cantábrica, en las cuales florecieron centros de eremitismo del primitivo condado de Castilla. También son lugares inaccesibles los riscos asomados a cantiles fluviales, cuya regularización morfológica natural ha sido causa de la ruina de múltiples hipogeos que se labraron con las mismas intenciones de refugio, defensa o retiro espiritual. Los núcleos modernos se han excavado ya en terrenos más propicios (los que componen las cuencas terciarias o "España arcillosa", mayoritariamente), y por ello observamos cómo abundan las litologías sedimentarias, que son aquellas en las que se horadaron casi todas las "colmenas" de habitación moderna en la Península. En unos casos y otros, existen rasgos comunes en lo relativo a la litología y comportamiento de los materiales excavados, y también en lo relativo a su evolución, meteorización y conservación. Se han estudiado por ello estas pautas comunes -como un posible avance para el establecimiento futuro de estudios de geoconservación del patrimonio rupestre habitado-, que se traducen en la determinación de los procesos de meteorización más característicos en los antros de la Península Ibérica -sean modernos o antiguos- y en la determinación de las relaciones más habituales entre geomorfología y tipología de las cuevas de habitación. También se exponen algunas conclusiones relativas a la resistencia de los tipos pétreos en relación a la antigüedad de los emplazamientos. Esta relación se explica bien si tenemos en cuenta que las cuevas antiguas trataban de ser lugares apartados en los que dominan rocas más resistentes -como se ha explicado- y que en las modernas se ha buscado la habitación permanente, en los materiales más blandos ocupan las depresiones terciarias del Centro, Este y Sur de la Península, colonizados no ya como refugios sino de modo seguro, y ya en arrabales "extramuros" de las ciudades. Geomorfológicamente, esta razón histórica tiene consecuencias sobre la posición de las cuevas, sobre su organización, y sobre su conservación. La extensión del dominio estudiado obliga prácticamente a bosquejar algunas de estas conclusiones geológicas, pero permite a su vez proporcionar una visión global acerca del patrimonio troglodítico desde una perspectiva geológica, y en ello radica la principal novedad de la investigación. Cave dwelling in the Iberian Peninsula comprises a great deal of examples whose origins are sometimes difficult to elucidate. There are primitive groups of caves, probably belonging to Classical and Late Antiquity, and other settlements that appear to have been created and excavated in the Early Middle Ages. Some of them are due to religious reasons and some others may probably have served for defensive uses. The Peninsular group is very likely the most diverse in Western Europe, for it was not only influenced by Arabs, but it also assimilated uses from the Antique Christendom, imported from the Middle East. In this sense, Iberian cave dwellings connect with those of the Mediterranean area. There is not total certainty about the survival of caves serving for dwelling throughout the Late Middle Ages, once the Reconquista was a fact. However, underground excavations for human habitation were once again dispread in certain zones of the Peninsula during the Early Modern period. This growth of underground habitats appears in connexion with Morisco’s vicissitudes; first of all, their removal from their settlements in South and Eastern Peninsula, and finally their expulsion from Spanish territory at the very beginning of XVII th century. Those of them who rested in Spain –and that were nominally “converts”- seem to have returned to cave dwelling in their places of origin, particularly in the province of Granada and its neighbouring zones. This substrate may have been the toehold for a new spreading of cave dwellings since XIX th century, when the increasing rural and urban proletariat returned to the pre-existent uses of caves in order to solve the necessity of affordable housing. This fact can still be detected in many of the rock settlements that have survived during a great part of the XX th century and which were gradually abandoned from the 60´s onwards. There were important cave dwelling districts in many Spanish territories by that time, and not only in Andalusia. We also find them in certain areas of the Ebro basin (those of Aragon, Navarra and La Rioja), in the peri-urban arc of Valencia, in the South of Madrid province and also in the provinces of Toledo (the so called “Mancha toledana”), Albacete, Guadalajara, Murcia or even Palencia as well. Due to their defensive and refuge uses, primitive underground habitats were dug in hardly accessible places. The majority of them are located in mountainous and rough areas, when not in the marginal borders of Tertiary basins, where coarse detritic and carbonate formations outcrop. Cave dwellings can also be found in more ancient rock masses, such as those of the Basque Cantabrian Mesozoic Basin, which is the area where hermit centres of the primitive County of Castile first flourished. Cliffs surrounding fluvial valleys are as well inaccessible places, but here we find that geological evolution has caused the destruction of many rock sanctuaries and cliff dwellings that were originally dug with the same purposes of defence, refuge and spiritual retreat. Later modern cave settlements were dug in quite more favourable terrains, mainly in the soils that compose the Tertiary basins, generally known as “España arcillosa” or “Clayey Spain”. Therefore, we find abundant sedimentary fine and medium grained lithologies, which are the ones that have hosted the majority of Modern Era warren cave dwellings in the Iberian Peninsula. Actually, both types of cave dwelling share some standards regarding the lithology of the excavated materials, and they share as well certain patterns that affect to their evolution, weathering and preservation. These common patterns have been studied here in order to determine the most characteristic weathering processes that affect the majority of the Iberian caves, both Antique and Modern. And also with a view to establish the most habitual relationships between geomorphology and typology of cave dwellings. The study may as well provide a first basis for future studies on geo-preservation of cave dwellings heritage. We also reach some conclusions about the strength of different rocks concerning the antiquity of the sites. As we have already pointed out, this relation comes from the fact that ancient caves were placed in remote or isolated locations, where harder rocks outcrop, while more modern ones result from people´s search of permanent dwelling. In this sense, the softer rocks of the Tertiary Basins of Middle, East and South Peninsula provided a secure colonization to this second and modern group. And moreover, considering geomorphological features, this historical reason has had an effect not only on the position and location of the caves, but also on their organisation/structure/distribution and preservation. The huge extension of our domain of interest almost forces to sketch out some of these geological conclusions. But at the same time it gives a global panorama of Spanish troglodyte heritage, seen from a geological perspective. And here is the main novelty of this research.

Caracterización de los depósitos miocenos de la isla de Nueva Tabarca (Alicante) y su empleo como material de construcción en el patrimonio local

El presente trabajo muestra la caracterización en detalle de la secuencia estratigráfica de los depósitos miocenos de la isla de Nueva Tabarca, el empleo de estos materiales en el patrimonio arquitectónico de la isla y su comportamiento frente la degradación. En la serie miocena, a grandes rasgos, se definen tres tramos. El tramo inferior, rico en clastos dolomíticos, muestra una alternancia de arenitas y calcarenitas. El tramo intermedio corresponde a una sucesión de niveles de calcirruditas con laminación cruzada cuya parte superior está representada por un nivel de grandes bioclastos, rodolitos y arenitas de grano fino. El comienzo del último tramo está marcado por la presencia de varias superficies arenosas más litificadas sobre las que se sitúa un banco de arenitas de grano fino y laminación paralela. Si bien las canteras extraían sillares de todas estas litofacies, existe una mayor extracción de los últimos niveles de la serie. Estas rocas presentan una durabilidad moderada-baja, degradándose fácilmente mediante arenización, escamación y/o alveolización.

Compositional signatures of the Cenozoic sedimentary succesions of the Malaguide Complex (Betic Cordillera, Spain)

The studied Cenozoic sedimentary successions consist of deposits from continental/shallow-water to deep-marine environments of the Malaguide Complex (Betic Cordillera) outcropping in the Sierra Espuña area (SE Spain). The aim of this study is to characterize the composition, source area(s) provenance and weathering processes of these sedimentary successions from the pre-orogenic (Paleocene-Early Oligocene) to the syn-orogenic (Late Oligocene-Early Miocene) stage using petrological and geochemical methodologies. The studied sandstones are mainly quartzolithic with abundant metamorphic and sedimentary lithic fragments. In particular, the composition of samples from the pre-orogenic cycle is mainly carbonate with important siliciclastic components that occur within the medium to fine grained arenites. The composition of samples from the syn-orogenic cycle is characterized by a sharp change from carbonate to siliciclastic terms. Thus, the composition of the overall sandstone samples is very heterogeneous and suggests a source area mainly characterized by the Malaguide basement and lower units of the Internal Betic Zone, that partially compose the Mesomediterranean Microplate. The geochemical proxies suggest a provenance mainly from felsic source area with a minor supply from mafic rocks in some samples of the syn-orogenic stage. Furthermore, palaeoweathering indices indicate low to moderate weathering conditions for the sources. The Cenozoic sedimentary successions of the Malaguide Complex played an important role in the geodynamic evolution of the Betic Cordillera that represents the key tectonic element of the western domains of the Mesomediterranean Microplate.

Rhenium and osmium concentrations and isotopic compositions in altered ocean crust rocks at ODP Site 185-801

Re and Os concentrations and Os isotopic ratios were determined for composite samples prepared from volcanoclastics (VCL) and basaltic flows (FLO) from Jurassic oceanic crust (Ocean Drilling Program Leg 185, Site 801 in the western Pacific), with the aim of determining the effect of seafloor weathering on the Re-Os budget. A supercomposite sample, prepared from a proportionate mixture of the various composite powders, served to represent the average composition of the altered oceanic crust [Kelley, K.A., Plank, T., Ludden, J. and Staudigel, H., (2003). Composition of altered oceanic crust at ODP Sites 801 and 1149, Geochem. Geophys. Geosyst. 4(6) 8910, doi:10.1029/2002GC000435.]. Re contents vary from 0.2 to 1.3 ng/g, and from 2.2 to 3.1 ng/g in the VCL and FLO composites respectively. Os contents vary from 0.005 to 0.047 ng/g in the VCL, and from 0.008 to 0.027 ng/g in the FLO composites. The FLO composites have much higher Re/Os ratios and thus have more radiogenic Os compositions (187Os/188Os = 1.38 to 8.48) than the VCL composites (187Os/188Os = 0.32 to 4.40). The VCL composite from the upper section of the crust shows evidence for substantial Re loss and Os uptake, consistent with oxidative weathering processes. However, Re uptake during weathering processes under more reducing conditions, evident in the FLO samples from throughout the section and to a lesser extent in the lower VCL samples, more than compensates for this Re loss in the upper VCL. Os concentrations were essentially unchanged by these reductive processes. Model age calculations suggest that Re uptake continued for tens of millions of years after crust formation. Abundant secondary pyrite is found throughout the altered Hole 801C crust in zones of restricted seawater flow, and this may have accommodated an important part of the input Re. The Re content of the supercomposite (~2.2 ng/g) is about 1 ng/g higher than would be expected on the basis of its Yb content. If the results from Hole 801C are typical, they suggest that the Re concentration of at least the upper part of the oceanic crust may be nearly doubled during seafloor alteration. Such large extents of Re uptake would have a significant effect on the oceanic Re budget. Furthermore, assuming that they survive passage through the subduction zone, these elevated Re contents would greatly decrease the proportion of subducted oceanic crust required in the source region to explain the radiogenic Os compositions of many ocean island basalts.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

(Table 1) Neodymium and Strontium measurements from sediment core MD01-2451

In the nineties, cold-water coral mounds were discovered in the Porcupine Seabight (NE Atlantic, west of Ireland). A decade later, this discovery led to the drilling of the entire Challenger cold-water coral mound (Eastern slope, Porcupine Seabight) during IODP Expedition 307. As more than 50% of the sediment within Challenger Mound consists of terrigenous material, the terrigenous component is equally important for the build-up of the mound as the framework-building corals. Moreover, the terrigenous fraction contains important information on the dynamics and the conditions of the depositional environment during mound development. In this study, the first in-depth investigation of the terrigenous sediment fraction of a cold-water coral mound is performed, combining clay mineralogy, sedimentology, petrography and Sr-Nd-isotopic analysis on a gravity core (MD01-2451G) collected at the top of Challenger Mound. Sr- and Nd-isotopic fingerprinting identifies Ireland as the main contributor of terrigenous material in Challenger Mound. Besides this, a variable input of volcanic material from the northern volcanic provinces (Iceland and/or the NW British Isles) is recognized in most of the samples. This volcanic material was most likely transported to Challenger Mound during cold climatic stages. In three samples, the isotopic ratios indicate a minor contribution of sediment deriving from the old cratons on Greenland, Scandinavia or Canada. The grain-size distributions of glacial sediments demonstrate that ice-rafted debris was deposited with little or no sorting, indicating a slow bottom-current regime. In contrast, interglacial intervals contain strongly current-sorted sediments, including reworked glacio-marine grains. The micro textures of the quartz-sand grains confirm the presence of grains transported by icebergs in interglacial intervals. These observations highlight the role of ice-rafting as an important transport mechanism of terrigenous material towards the mound during the Late Quaternary. Furthermore, elevated smectite content in the siliciclastic, glaciomarine sediment intervals is linked to the deglaciation history of the British-Irish Ice Sheet (BIIS). The increase of smectite is attributed to the initial stage of chemical weathering processes, which became activated following glacial retreat and the onset of warmer climatic conditions. During these deglaciations a significant change in the signature of the detrital fraction and a lack of coral growth is observed. Therefore, we postulate that the deglaciation of the BIIS has an important effect on mound growth. It can seriously alter the hydrography, nutrient supply and sedimentation processes, thereby affecting both sediment input and coral growth and hence, coral mound development.

Sediment microstructures of ODP Leg 105 holes

Possible genetic relationships between syn- and post-depositional processes and sediment microstructure were investigated. Samples from cores at Sites 646 and 647 of Ocean Drilling Program (ODP) Leg 105 included examples of bottom current deposition (contourites), turbidity current deposition, consolidation, and diagenesis. Examination of nearly 200 micrographs of 14 samples from Site 646 and 13 samples from Site 647 leads to the conclusion that sedimentation processes do not appear to have an obvious influence on fabric. The effects of post-depositional processes, such as bioturbation, coring disturbance, and even remolding, appear to be less significant than one might expect as a result of the relatively coarse grain size of the sediments studied. Consolidation resulting from increased overburden stress results in increased particle alignment and compression of fabric elements with depth. The transition from open, random fabric in shallow samples to preferred orientation at depth represents the only change in these sediments that can be ascribed directly to a specific depositional or post-depositional process. Mineralogical variations, owing to changes in weathering processes and growth of authigenic/diagenetic minerals, also have a pronounced effect on sediment fabric.

(Table 1) Sample locations, Hf and Nd isotopic compositions and concentrations of Atlantic seawater samples with hydrographic details

The first full water column hafnium isotopic compositions of Atlantic seawater have been obtained at seven locations from the Labrador Sea to the Drake Passage. Despite subpicomolar concentrations in seawater, a precision of the Hf isotopic measurements of <0.7 epsilon-Hf units was achieved. An overall epsilon-Hf range between -3.1 in the Labrador Sea and +4.4 in Antarctic bottom water was determined, the distribution of which broadly reflects continental weathering inputs. Within particular water column profiles, significant differences of up to 4 epsilon-Hf units occur. Combined with Nd isotope data of the same samples, it is evident that the Hf isotopic composition of seawater is too radiogenic for a given Nd isotopic composition and that the largest difference between expected and measured Hf isotopic compositions in seawater occurs near the oldest continental crust in the Labrador Sea. This corroborates the previous proposition, which was mainly based on ferromanganese crust data, that the Hf isotopic composition of seawater is controlled by incongruent weathering of continental crust and possibly, to some extent, by hydrothermal contributions. Hafnium concentrations in the ocean do not increase along the deep ocean conveyer indicating an oceanic residence time of only a few hundred years, which is significantly shorter than previously assumed. The Hf isotopic composition of past seawater can therefore serve as a proxy for short distance, basin scale mixing processes and the regime and intensity of nearby continental weathering processes.

Carbonate and Thorium concentrations of South Atlantic sediments

Rates of sedimentation of pelagic sediments in the South Atlantic have been determined using the ionium/thorium methodology. Values of the order of several millimeters per thousand years for sediments were found in the deposits in the valleys of the mid-Atlantic ridge. The equatorial deposits showed higher rates of accumulation than the corresponding deposits at higher latitudes, probably reflecting the added influx of materials to the sea floor from tropical rivers through the equatorial current systems. The deposits in the ridge valleys showed marked changes in sedimentation rates at about 115,000 years ago, at which time the present rates changed from higher to lower values. The ridge sediments were composed primarily of continentally derived materials, and there were no indications of solid phases being derived from the weathering of the ridge itself or from volcanic activity. The equatorial samples have mineral assemblages which are distinctly different from those in deposits at higher latitudes and which probably are indicative of contributions of materials from tropical weathering processes.

(Table DR1) Argon isotope data and dating for individual >63 µm amphibole grains from Labrador Sea sediments, ODP Hole 105-647A

Variations of global and regional silicate weathering rates and paleo-ocean circulation patterns are estimated by using radiogenic isotope records, but the effects of changes in provenance are generally ignored. Here sediment provenance has been constrained through the use of Ar-Ar ages for individual detrital minerals from the Labrador Sea, which can be compared directly to the radiogenic isotope compositions from the same core material. Dramatic changes in the radiogenic isotope composition of North Atlantic Deep Water through the Quaternary Period are shown to reflect discrete changes in both sources and weathering processes accompanying Northern Hemisphere glaciation. Changes in the different radiogenic isotope systems reflect the influence of source, physical weathering, and chemical weathering, and not simply changes in the underlying weathering rate or ocean circulation patterns that are typically inferred.

A petrographic investigation into the durability of common replacement sandstones to the crystallisation of de-icing salts

Scottish sandstone buildings are now suffering the long-term effects of salt-crystallisation damage, owing in part to the repeated deposition of de-icing salts during winter months. The use of de-icing salts is necessary in order to maintain safe road and pavement conditions during cold weather, but their use comes at a price. Sodium chloride (NaCl), which is used as the primary de-icing salt throughout the country, is a salt known to be damaging to sandstone masonry. However, there remains a range of alternative, commercially available de-icing salts. It is unknown however, what effect these salts have on porous building materials, such as sandstone. In order to protect our built heritage against salt-induced decay, it is vital to understand the effects of these different salts on the range of sandstone types that we see within the historic buildings of Scotland. Eleven common types of sandstone were characterised using a suite of methods in order to understand their mineralogy, pore structure and their response to moisture movement, which are vital properties that govern a stone’s response to weathering and decay. Sandstones were then placed through a range of durability tests designed to measure their resistance to various weathering processes. Three salt crystallisation tests were undertaken on the sandstones over a range of 16 to 50 cycles, which tested their durability to NaCl, CaCl2, MgCl2 and a chloride blend salt. Samples were primarily analysed by measuring their dry weight loss after each cycle, visually after each cycle and by other complimentary methods in order to understand their changing response to moisture uptake after salt treatment. Salt crystallisation was identified as the primary mechanism of decay across each salt, with the extent of damage in each sandstone influenced by environmental conditions and pore-grain properties of the stone. Damage recorded in salt crystallisation tests was ultimately caused by the generation of high crystallisation pressures within the confined pore networks of each stone. Stone and test-specific parameters controlled the location and magnitude of damage, with the amount of micro-pores, their spatial distribution, the water absorption coefficient and the drying efficiency of each stone being identified as the most important stone-specific properties influencing salt-induced decay. Strong correlations were found between the dry weight loss of NaCl treated samples and the proportion of pores <1µm in diameter. Crystallisation pressures are known to scale inversely with pore size, while the spatial distribution of these micro-pores is thought to influence the rate, overall extent and type of decay within the stone by concentrating crystallisation pressures in specific regions of the stone. The water absorption determines the total amount of moisture entering into the stone, which represents the total amount of void space for salt crystallisation. The drying parameters on the other hand, ultimately control the distribution of salt crystallisation. Those stones that were characterised by a combination of a high proportion of micro-pores, high water absorption values and slow drying kinetics were shown to be most vulnerable to NaCl-induced decay. CaCl2 and MgCl2 are shown to have similar crystallisation behaviour, forming thin crystalline sheets under low relative humidity and/or high temperature conditions. Distinct differences in their behaviour that are influenced by test specific criteria were identified. The location of MgCl2 crystallisation close to the stone surface, as influenced by prolonged drying under moderate temperature drying conditions, was identified as the main factor that caused substantial dry weight loss in specific stone types. CaCl2 solutions remained unaffected under these conditions and only crystallised under high temperatures. Homogeneous crystallisation of CaCl2 throughout the stone produced greater internal change, with little dry weight loss recorded. NaCl formed distinctive isometric hopper crystals that caused damage through the non-equilibrium growth of salts in trapped regions of the stone. Damage was sustained as granular decay and contour scaling across most stone types. The pore network and hydric properties of the stones continually evolve in response to salt crystallisation, creating a dynamic system whereby the initial, known properties of clean quarried stone will not continually govern the processes of salt crystallisation, nor indeed can they continually predict the behaviour of stone to salt-induced decay.

Avaliação da contaminação por elementos metálicos dos sedimentos do Estuário Santos - São Vicente

Three approaches were applied to evaluate metal contamination in 41 sediment samples from the Santos - São Vicente Estuarine System: normalization to Al, statistical analysis and sediment quality guidelines (SQGs). The results showed increases in the concentrations of Zn, Ni, Pb, Cd, Cr and Hg, which seemed to be associated with human activities. The levels of Al, Fe and Co probably were associated with crustal material or natural weathering processes. About 45% of the samples presented concentrations exceeding TEL-ERL, levels occasionally associated with adverse biological effects. Four of these samples presented concentrations above PEL-ERM, levels frequently associated with adverse biological effects.

贵州碳酸盐岩风化壳形成地球化学过程、对比及年代学研究Geochemical Processes, Comparison and Dating for the Weathering Crusts in Karst Regions of Guizhou Province

由于缺乏相应的沉积地层，贵州新生代地质、环境演化恢复一直是学术界的难点问题。夷平面研究的兴起，为陆地地壳抬升、地貌演变等反演提供了理论基础，而风化壳正是夷平面研究的重要替代对象，尤其是对各类沉积地层不发育的地区。因而，贵州高原各级台地上发育有较为广泛的红色风化壳自然地、就成了主要研究载体。然而一与其它岩类不同，碳酸盐岩风化成土作用过程研究并没有得到同等重视，其研究范围和程度均很不充分。显然，要想利用碳酸盐岩风化壳进行夷平面等地质、地貌意义研究，就必需详细了解贵州或中国南方碳酸盐岩风化成土的基本过程。也只有如此，才能明确各种对比指标的使用条件和范围，才能明确各种测年结果的具体意义，才能真正地通过贵州碳酸盐岩风化壳获取全省地质、环境演化信息。本论文通过对贵州省岩溶台地碳酸盐岩石灰土、红色风化壳剖面形成地球化学过程的剖析，开展石灰土与红色风化壳之间的关联和差异性综合对比、红色风化壳之间发育程度的比较，以及风化壳剖面尝试性的侧年等方面研究，取得了以下儿点认识：1、石灰土形成地球化学过程及对比通过矿物组成、粒度分布特征、地球化学方法判别，确定了本文所选石灰土剖面物质来源于下伏碳酸盐岩中的酸不溶物，是碳酸盐岩风化后酸不溶物原地残余堆积的结果。石灰土形成的地球化学过程都遵循碳酸盐岩风化成土之两阶段模式：母岩－酸不溶物，大量可溶性物质Ca、Mg、Mn、P、Na淋失，而Si、K·Fe、Al、Ti则相对富集。该过程的矿物组成变化表现为，伴随碳酸盐矿物（方解石、白云石等）的溶解、迁移，硅酸盐相矿物（长石、2:1型粘土矿物等）残余、累积。酸不溶物，土层或土层的演化，K、Si（长石、伊利石）不断淋失，而Al（伊利石、高岭石、三水铝石）、Fe（针铁矿、赤铁矿等）逐渐富集，体现出脱硅、富铝（铁）过程。我们强调碳酸盐岩风化成土分为两个阶段，但也认识到风化作用是综合的、复杂的：在碳酸盐矿物大量淋失过程中，同时也进行着酸不溶物的风化。石灰土分为原生和次生两种成因类型。原生石灰土的风化程度总体较低，剖面中还残留一定量的CaCO3，剖面从下到上矿物组成、地球化学各种指标具有逐渐演化的过渡特征。原生石灰上土层演化过程显示出正风化序列，从下到上风化程度逐渐增大、可溶性物质逐渐减少、稳定和相对稳定组分（Al、Fe．、REE）含量不断增大。另外，主量元素的质量迁移系数在剖面中的变化与风化程度呈明显的相关性。而次生石灰土不但具有很高的风化程度，而且剖面无过渡特征，显示可能是由遭受强烈风化作用的物质直接转变形成的。剖面中也含有一定量后期加入的碳酸盐，但与高CIA值特征不相匹配；SiO2、Al2O3、Fe2O3组分具有不同的变化特征，与）成化程度无明显关联；REE在剖面岩一上界面出现富集层。2、碳酸盐岩红色风化壳形成地球化学过程及其与石灰土的对比红色风化壳形成的地球化学过程也遵循碳酸盐岩风化成土之两阶段模式：母岩一酸不溶物，大量可溶性物质Ca、Mg、Mn、P、Na淋失，而Si、K、Fe、Al、Ti则相对富集。该过程的矿物组成变化表现为，伴随碳酸盐矿物（方解石、白云石等）的溶解、迁移，硅酸盆相矿物（长石、2:1型粘土矿物等）残余、累积。酸不济物一土层或上层的演化，K、Si（长石、伊利石）不断淋失，而Al（伊利石、高岭石、三水铝石）、Fe（针铁矿、赤铁矿等）逐渐富集，体现出脱硅、富铝（铁）过程。石灰土与红色风化壳之间既存在共性，又有一定的差异性。红色风化壳与原生石灰土一样都具有过渡特征，但后者仅在剖面下部出现一定的过渡层位；原生石灰士的城化程度远低于红色风化壳，仅与后者底部土层相当；原生石灰土不具有红色风化壳之岩-土REE（超常）富集层。总体上，原生石灰土可以作为红色风化壳的前身。次生石灰土与红色风化壳在矿物组成、风化程度等各种地球化学指标等都十分接近（略低），显示与红色风化壳之间存在某种关联：由红色风化壳物质直接转变，或由酸不溶物已强烈风化的（白云岩）岩粉、碎裂岩风化形成。3、碳酸盐岩风化成土母岩差异性碳酸盐岩风化成土存在母岩差异性，石灰土母岩差异性较为明显，而红色风化壳的母岩差异性较弱，体现出红色风化壳的均一化特征。石灰土母岩差异性体现为：母岩为灰岩的石灰土剖面主量元素含量变化特征较为一致，而白云岩则具有不同的变化；灰岩石灰土Fe3＋、Al具有不同的富集、亏损特征，且具有富集层的补偿亏损层，而白云岩石灰上两组分都呈现无补偿层位的相同富集态势；灰岩石灰土剖面出现负Eu异常和具以Gd为中心的倒“V”型MREE稀土富集特征（母岩标准化），而白云岩石灰土无明显Eu异常和具L既E或HREE稀士．富集特征；灰岩和白云岩石灰土的微量元素富集、亏损特征也有所不同，前者从上到下逐渐富集，而后者无明显变化趋势。红色风化壳形成的基本过程、主量元素地球化学行为无明显的母岩相关性，没有如石灰土剖面灰岩和白云岩之间存在的差异性，显示出红土化作用的均一化过程；微量元素中受重矿物影响的元素与母岩类型有一定的关联，但大多数元素的亏损、富集等与具体剖面的微环境关系密切。4、碳酸盐岩红色风化壳发育程度的对比及意义多利指标对比显示所选红色风化壳的风化程度有一定的强弱差别：平坝剖面＞湖潮剖面＞天龙剖面、大兴剖面＞花溪剖面、新蒲剖面，但这种差异性不足以否定各剖面隶属于贵州山盆期广泛夷平面的基本推测。各剖面之间的微弱差异是红色风化壳形成时纬度分带和垂向分带的体现。低纬度的平坝、湖潮、天龙剖面经历的风化作用强于高纬度的新蒲、大兴剖面；高海拔的新蒲剖面风化程度低于海拔低的大兴剖面。5、红色风化壳次生石英裂变径迹测年红色风化壳次生石英裂变径迹方法测年尝试，得到一定的结果和认识：晶形相对较好的石英，是次生的，与母岩中碎屑及成岩阶段没有关联；各剖面上部与中、下部次生石英的诱发裂变径迹的密度有着明显的区别，可能暗示它们的形成环境不同；名一剖面石英的形成或退火年龄分布较为分散，1.2-25.2Ma，同一剖面的石英年龄也不均一，变化较大；从下到上，年龄值呈现出逐渐减小的规律性，与风化作用的正常序列相反。如果能确切其成因，次生石英裂变径迹年代学研究将是确定风化壳形成时代及揭示主要风化作用信，却钩有利武器。