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.

Geochemistry on smectites in sediment cores CRP-1 and CRP-2 from the Ross Sea, Antarctica

TEM (transmission electron microscopy) observations and microanalyses on smectite microparticles in the sediments of the CRP-2A core were carried out to determine their origin (authigenic or detrital) and the source rocks. Smectites are dioctahedral and are Fe-rich members of the nontronite-beidellite series. They generally display both flaky and hairy shapes, but no large compositional difference between the two forms was observed. Flaky smectites are detrital while hairy smectites probably formed in situ through the reorganisation of previous flaky particles. The source rocks for smectites are probably represented by the McMurdo Volcanic Group to the south, but also by the Ferrar Dolerites and Kirkpatrick Basalts in the Transantarctic Mountains. CRP-2A smectites are Fe and Mg richer than those of the coeval or not coeval levels of the CIROS-I, DSDP 270 and 274 cores. The average compositions of smectite in CRP-1 and CRP-2A cores show a downcore trend toward more alluminiferous terms, which might reflect the increase of the chemical weathering processes on the continent.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Geochemistry of altered smectites

In basalts and volcanogenic sediments from the Indian Ocean, the successive stages of submarine alteration of volcanic rocks and glasses give rise to the incorporation or the relative increase of iron in smectite lattices. During the first stage, the Mg-smectites are the most abundant; they are occasionally associated with Al-smectites. Afterwards, they are gradually replaced by iron-rich smectites. The REE distribution follows the same trend as the mineralogical changes. During the f'trst stage of alteration, REE distribution in clay minerals is the same as in the fresh glasses but, when the iron-rich smectites increase, the Ce has a specific behaviour. The Ce shows a positive anomaly in iron-rich smectites formed early in palagonitized glasses, and a negative one in authigenic smectites formed later from solutions in equilibrium with seawater.

Chemical composition and dated ages of detrital smectites in sediments at DSDP Legs 43, 48 and 50

Mineralogical, morphological and isotopic (Rb-Sr and K-Ar) determinations were made on some detrital smectites of Palaeocene and Cenomanian ages from DSDP. drillings in the Atlantic Ocean. These minerals are not inert in their depositional environment; authigenic laths grow on detrital sheets with sharp borders. This authigenesis could occur slightly after deposition in a closed system, for some of these smectites. It has been tentatively quantified by the Rb-Sr and K-Ar isotopic methods, which seem also well suited to evaluate the chemical extent of this authigenesis. At least, no preferential loss of 40Ar vs. 87Sr could be detected in the minerals, even in those which are smaller than 0.2 ?m.

Isotope ratios of smectites, calcites and whole rocks from DSDP Legs 51 and 52, Atlantic Ocean

Delta180 and 87Sr/86Sr isotopic data from smectites, calcites, and whole rocks, together with published isotopic age determinations, alkali element concentration data and petrographic observations suggest a sequential model of ocean floor alteration. The early stage lasts about 3 m.y. and is characterized by palagonite and smectite formation, and solutions with a large basaltic component, increasing with temperature which varies from 15° to 80° C at DSDP site 418A. Most carbonates are deposited after this stage from solutions with a negligible basaltic Sr component and temperatures of 15° to 40° C. Water of seawater Sr and O isotopic composition is shown to percolate to at least 500 m into the basaltic basement. No evidence was found for continuing exchange of strontium or oxygen after 3 m.y.