Organofilização de uma Mg-bentonita da bacia do Parnaíba-Sul do Maranhão e sua utilização em poli (metacrilato de metila)

Bentonitas são argilas que tem como seu principal constituinte argilominerais do grupo da esmectita, predominantemente montmorillonita. De acordo com o cátion predominante no espaço intercamada da esmectita, a bentonita pode ser classificada como sódica, cálcica ou magnesiana. Essas argilas possuem vasta aplicação industrial, como fluidos de perfuração, pelotização, moldes de fundição, dentre outros. Para algumas aplicações mais específicas e que agregam maior valor ao produto final, como na síntese de nanocompósitos polímero/argila, faz-se necessário à intercalação de íons orgânicos na intercamada do argilomineral. No Brasil, a produção industrial de argilas organofílicas é pequena e voltada para os mercados de tintas, graxas e resinas de poliéster. Empresas do setor de bentonitas, que ainda não estão produzindo esse tipo de material, vêm mostrando crescente interesse nesta aplicação. Dentro desse contexto, este trabalho buscou avaliar o potencial da Bentonita Formosa, uma Mg-bentonita recentemente descrita e relativamente abundante no nordeste do Brasil, na produção de argilas organofílicas e sua aplicação em síntese de nanocompósitos polímero/argila. Para isso, foram realizadas sínteses variando a concentração dos íons surfactantes hexadeciltrimetilamônio (HDTMA⁺) e dodeciltrimetilamônio (DTMA⁺) em 0,7, 1,0 e 1,5 vezes o valor de CEC, com tempo de reação de 12 horas e variação de temperatura de 25 ºC e 80 ºC. A Mg-Bentonita in natura e ativada com carbonato de sódio foi utilizada como material de partida. Tanto o material de partida como as argilas organofílicas obtidas foram caracterizadas por DRX, DTA/TG e IV. As argilas que apresentaram melhores resultados de intercalação foram utilizadas nas proporções de 1%, 3% e 10% para a síntese de nanocompósitos poli(metacrilato de metila) (PMMA)/argila. As análises de DRX confirmaram a intercalação dos íons orgânicos no espaço intercamada da Mg-esmectita com e sem ativação. Com os resultados de IV foi possível observar que a razão de confôrmeros gauche/trans diminui com o aumento do espaçamento basal. Os resultados de DTA/TG confirmaram a estabilidade térmica das argilas organofílicas à temperatura máxima de 200 °C, o que possibilita a utilização desse material em síntese de nanocompósitos polímero/argila obtidos por processo de fusão. A análise de DRX confirmou a intercalação do PMMA no espaço intercamada da Mg-esmectita em todos os nanocompósitos produzidos. Com as análises de DSC foi possível observar o aumento da temperatura de transição vítrea para todos os nanocompósitos, quando comparados com PMMA puro. Com isso, é possível concluir que a Mg-Bentonita pode ser intercalada com íons alquilamônio, sem a necessidade prévia de ativação sódica, formando argilas organofílicas, assim como sua utilização em síntese de nanocompósitos. Essa possibilidade de utilização da Mg-bentonita in natura pode representar uma importante diferença em termos de custos de processo, na comparação com as bentonitas cálcicas existentes no Brasil, ou mesmo as importadas, que precisam ser ativadas durante o beneficiamento. Finalmente, acredita-se que a pesquisa deve avançar com a avaliação das propriedades mecânicas dos nanocompósitos produzidos neste trabalho, visando as diferentes possibilidades de aplicações desses materiais.

Soil mineral genesis and distribution in a saline lake landscape of the Pantanal Wetland, Brazil

The origin of the saline lakes in the Pantanal wetland has been classically attributed to processes occurring in past periods. However, recent studies have suggested that saline water is currently forming from evaporative concentration of fresh water, which is provided annually by seasonal floods. Major elements (Ca, Mg, K) and alkalinity appear to be geochemically controlled during the concentration of waters and may be involved in the formation of carbonates and clay minerals around the saline lakes. The mineralogy of soils associated with a representative saline lake was investigated using XRD, TEM-EDS, and ICP-MS in order to identify the composition and genesis of the secondary minerals suspected to be involved in the control of major elements. The results showed that Ca, Mg, and K effectively undergo oversaturation and precipitation as the waters become more saline. These elements are incorporated in the authigenically formed carbonates, smectites, and micas surrounding the saline lake. The control of Ca occurs by precipitation of calcite and dolomite in nodules while Mg and K are mainly involved in the neoformation of Mg-smectites (stevensitic and saponitic minerals) and, probably, iron-enriched micas (ferric-illite) in surface and subsurface horizons. Therefore, our study confirms that the salinity of Pantanal, historically attributed to inheritance from former regimes, has a contribution of current processes. (C) 2009 Elsevier B.V. All rights reserved.

MINERALOGY AND GENESIS OF SMECTITES IN AN ALKALINE-SALINE ENVIRONMENT OF PANTANAL WETLAND, BRAZIL

Smectite formation in alkaline-saline environments has been attributed to direct precipitation from solution and/or transformation from precursor minerals, but these mechanisms are not universally agreed upon in the literature. The objective of this work was to investigate the mineralogy of smectites in the soils surrounding a representative alkaline-saline lake of Nhecolandia, a sub-region of the Pantanal wetland, Brazil, and then to identify the mechanisms of their formation. Soils were sampled along a toposequence and analyzed by X-ray diffraction, transmission electron microscopy-energy dispersive X-ray analysis, and inductively coupled plasma-mass spectrometry. Water was collected along a transect involving the studied toposequence and equilibrium diagrams were calculated using the databases PHREEQC and AQUA. The fine-clay fraction is dominated by smectite, mica, and kaolinite. Smectites are concentrated at two places in the toposequence: an upper zone, which includes the soil horizons rarely reached by the lake-level variation; and a lower zone, which includes the surface horizon within the area of seasonal lake-level variation. Within the upper zone, the smectite is dioctahedral, rich in Al and Fe, and is classified as ferribeidellite. This phase is interstratified with mica and vermiculite and has an Fe content similar to that of the mica identified. These characteristics suggest that the ferribeidellite originates from transformation of micas and that vermiculite is an intermediate phase in this transformation. Within the lower zone, smectites are dominantly trioctahedral, Mg-rich, and are saponitic and stevensitic minerals. In addition, samples enriched in these minerals have much smaller rare-earth element (REE) contents than other soil samples. The water chemistry shows a geochemical control of Mg and saturation with respect to Mg-smectites in the more saline waters. The REE contents, water chemistry, and the presence of Mg-smectite where maximum evaporation is expected, suggest that saponitic and stevensitic minerals originate by chemical precipitation from the water column of the alkaline-saline lake.

Mineralogy and geochemistry of alteration products in DSDP Leg 81 Holes

Alteration products of basalts from the four holes drilled during Leg 81 were studied and found to be characterized by the widespread occurrence of trioctahedral clay minerals (Mg smectite to chlorite). In some cases zeolites (analcite, chabazite) are associated with the saponite. A more oxidizing stage is marked by a saponite-celadonite association, presenting the geochemical characteristics of hydrothermal processes. Later stages of alteration are represented by palagonitization and subaerial weathering at two sites. These different alteration processes of basalts from Leg 81 record the paleoenvironment during the first opening stages of the Northeast Atlantic Ocean in the Paleocene-Eocene periods.

Chemistry of low-temperature hydrothermal altered basement of ODP Site 129-801

Low-temperature hydrothermal alteration of basement from Site 801 was studied through analyses of the mineralogy, chemistry, and oxygen isotopic compositions of the rocks. The more than 100-m section of 170-Ma basement consists of 60 m of tholeiitic basalt separated from the overlying 60 m of alkalic basalts by a >3-m-thick Fe-Si hydrothermal deposit. Four alteration types were distinguished in the basalts: (1) saponite-type (Mg-smectite) rocks are generally slightly altered, exhibiting small increases in H2O, d18O, and oxidation; (2) celadonite-type rocks are also slightly altered, but exhibit uptake of alkalis in addition to hydration and oxidation, reflecting somewhat greater seawater/rock ratios than the saponite type; (3) Al-saponite-type alteration resulted in oxidation, hydration, and alkali and 18O uptake and losses of Ca and Na due to the breakdown of plagioclase and clinopyroxene; and (4) blue-green rocks exhibit the greatest chemical changes, including oxidation, hydration, alkali uptake, and loss of Ca, Na, and Mg due to the complete breakdown of plagioclase and olivine to K-feldspar and phyllosilicates. Saponite- and celadonite-type alteration of the tholeiite section occurred at a normal mid-ocean ridge basalt spreading center at temperatures <20°C. Near- or off-axis intrusion of an alkali basalt magma at depth reinitiated hydrothermal circulation, and the Fe-Si hydrothermal deposit formed from cool (<60°C) distal hydrothermal fluids. Focusing of fluid flow in the rocks immediately underlying the deposit resulted in the extensive alteration of the blue-green rocks at similar temperatures. Al-saponite alteration of the subsequent alkali basalts overlying the deposit occurred at relatively high water/rock ratios as part of the same low-temperature circulation system that formed the hydrothermal deposit. Abundant calcite formed in the rocks during progressive "aging" of the crust during its long history away from the spreading center.

Nutrientes (K, P, Ca, Na, Mg e Fe) em sedimentos (solos aluviais) e cultivares (feijão e milho) de praias e barrancos de rios de água branca: a bacia do purus no estado do Acre, Brasil

The present research highlights the macronutrient abundance in the sediments of beaches and cliffs and cultivates in the river Purus and flowing, southwest of Amazon. The concentrations found in leaves and bean seeds and corn leaves reflect the mineralogical and chemical nature of those rich sediments in K2O and Na2O, which are formed by smectite, illite and K-feldspar. The factors of transfer of the elements in the corn leaves and bean (Ca>K>Na) and bean seeds (Na>K>Ca) demonstrate that the nutrient needs of the cultivate were found appropriately in the sediments (soils) of the beaches and cliffs.

Estudo comparativo das argilas das olarias dos municípios de Alfenas e Areado, MG

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Nutrientes (K, P, Ca, Na, Mg e Fe) em sedimentos (solos aluviais) e cultivares (feijão e milho) de praias e barrancos de rios de água branca: a bacia do purus no estado do Acre, Brasil

The present research highlights the macronutrient abundance in the sediments of beaches and cliffs and cultivates in the river Purus and flowing, southwest of Amazon. The concentrations found in leaves and bean seeds and corn leaves reflect the mineralogical and chemical nature of those rich sediments in K₂O and Na₂O, which are formed by smectite, illite and K-feldspar. The factors of transfer of the elements in the corn leaves and bean (Ca>K>Na) and bean seeds (Na>K>Ca) demonstrate that the nutrient needs of the cultivate were found appropriately in the sediments (soils) of the beaches and cliffs.

Chemistry of smectite and volcanic glass of ODP Site 159-959

The Ocean Drilling Program (ODP) Site 959 was drilled in the northern border of the Côte d'Ivoire-Ghana Ridge at a water depth of 2100 m. Pleistocene total thickness does not exceed 20 m. Winnowing processes resulted in a low accumulation rate and notable stratigraphic hiatuses. During the Late Pleistocene, bottom circulation was very active and controlled laminae deposition (contourites) which increased the concentration of glauconitic infillings of foraminifera, and of volcanic glass and blue-green grains more rarely, with one or several subordinate ferromagnesian silicates. Volcanic glass generally was X-ray amorphous and schematically classified as basic to intermediate (44-60% SiO2). Opal-A or opal-CT suggested the beginning of the palagonitisation process, and previous smectitic deposits may have been eroded mechanically. The blue-green grains presented two main types of mineralogic composition: (1) neoformed K, Fe-smectite associated with zeolite (like phillipsite) and unequal amounts of quartz and anorthite; (2) feldspathic grains dominated by albite but including quartz, volcanic glass and smectites as accessory components. They were more or less associated with the volcanic glass. On the basis of their chemical composition, the genetic relationship between the blue-green grains and the volcanic glass seemed to be obvious although some heterogeneous grains seemed to be primary ignimbrite and not the result of glass weathering. The most reasonable origin of these pyroclastic ejecta would be explosive events from the Cameroon Volcanic Ridge, especially from the Sao Thome and Principe Islands and Mount Cameroon area. This is supported both by grain geochemistry and the time of volcanic activity, i.e. Pleistocene. After westward wind transport (some 1200 km) and ash fall-out, the subsequent winnowing by bottom currents controlled the concentration of the volcanic grains previously disseminated inside the hemipelagic sediment. Palagonitisation, and especially phillipsite formation, may result from a relatively rapid reaction during burial diagenesis (<1 m.y.), in deep-sea deposits at relatively low sedimentation rate. However, it cannot be excluded that the weathering had begun widely on the Cameroon Ridge before the explosive event.

Supplementary material: XRF core scanning data, CaCO3 values, foraminiferal carbon and oxygen isotope data, Mg/Ca data, clay mineralogy and helium isotope results

The Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) is associated with abrupt climate change, carbon cycle perturbation, ocean acidification, as well as biogeographic shifts in marine and terrestrial biota that were largely reversed as the climatic transient waned. We report a clear exception to the behavior of the PETM as a reversing climatic transient in the eastern North Atlantic (Deep-Sea Drilling Project Site 401, Bay of Biscay) where the PETM initiates a greatly prolonged environmental change compared to other places on Earth where records exist. The observed environmental perturbation extended well past the d13C recovery phase and up to 650 kyr after the PETM onset according to our extraterrestrial 3He-based age-model. We observe a strong decoupling of planktic foraminiferal d18O and Mg/Ca values during the PETM d13C recovery phase, which in combination with results from helium isotopes and clay mineralogy, suggests that the PETM triggered a hydrologic change in western Europe that increased freshwater flux and the delivery of weathering products to the eastern North Atlantic. This state change persisted long after the carbon-cycle perturbation had stopped. We hypothesize that either long-lived continental drainage patterns were altered by enhanced hydrological cycling induced by the PETM, or alternatively that the climate system in the hinterland area of Site 401 was forced into a new climate state that was not easily reversed in the aftermath of the PETM.

Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

Composition of bentonite-, smectite-rich- and ash beds from DSDP Leg 19 holes

Late Cenozoic ash deposits cored in Deep Sea Drilling Project Leg 19 in the far northwest Pacific and in the Bering Sea have altered to bentonite beds. Some bentonite layers were subsequently replaced by carbonate beds. A significant part of the Neogene volcanic history of land areas adjacent to the far north Pacific is represented by these diagenetic deposits. Bentonite beds are composed of authigenic smectite and minor amounts of clinoptilolite. Authigenic smectite has fewer illite layers than detrital smectite. Opal-A and opal-CT, abundant in Bering Sea sediment, are not found in ash or bentonite layers. The percentage of smectite in the total clay-mineral assemblage of ash beds is greater than that for adjacent terrigenous sediment, but the total amount of clay minerals in ash sequences is less than in surrounding deposits. Morphology of the 17-Å peak of smectite found in ash may represent newly formed, poorly crystalline smectite. Smectite becomes better crystallized as bentonite layers form. The percentage of smectite of the total clay-mineral assemblage in bentonite beds is greater than that in surrounding sediment, and, in contrast to ash beds, the total amount of clay minerals (mostly smectite) in bentonite layers is greater than in adjacent terrigenous sediment. Apparently, silica is not mobilized when volcanic ash layers transform to bentonite beds. Saponite-nontronite varieties of smectite and high Fe/Al and Ti/Al ratios distinguish bentonite beds derived from basaltic parent material from those beds formed from more silicic volcanic ash. These silicic ash beds produce bentonite composed mostly of montmorillonite. The basal sediment section at site 192 is rich with bentonite beds. Smectite in the upper part of this section (Eocene) was formed by low-temperature diagenesis of volcanic debris of intermediate or more silicic composition derived from arc or Pacific volcanoes. In contrast, smectite from the lowest 10 to 20 m of the sedimentary section (Cretaceous) is formed from either low-temperature or hydrothermal alteration of the underlying basaltic basement and associated pyroclastic debris. This near-basement smectite contains Mg and K acquired from sea water and Si, Al, Fe, Ti, and Mn released from the volcanic material.