Analysis of the correlations between freeze–thaw and salt crystallization tests

Two of the most popular weathering tests used for dimension stone are EN 12371 freeze–thaw (FT) and EN 12370 Salt Crystallization (SC). These tests are used to assign a durability value to the rocks. Both tests are based on the cyclical growth of crystals in the porous system of the rock, which causes structural stress on the rock matrix that may affect its integrity. The weathering mechanism is the same in both tests although the rate of volume increase is higher for the salt crystals. Due to this similarity, the two tests provide complementary information. The EN (European Norms) recommend evaluating the results together, but do not establish correlations between the results of these two tests for different types of rocks. Knowing these relationships would improve the understanding of the results and the response to weathering of the rock once placed in a building. In this work, several ornamental rocks (sandstones, limestones, dolostones, and a travertine) from the Iberian Peninsula were submitted to FT and SC tests. Rocks were mineralogically and petrographically characterized, and their porous systems were defined by a combination of techniques (scanning electronic microscopy, digital images analysis, and mercury porosimetry). The results of the tests were quantified numerically to compare them. The velocity of propagation of ultrasonic waves was measured before and after the tests. After the statistical analysis, significant correlations were found between the FT and SC tests, and between the connected porosity and the durability index of the rocks.     

Komsomolskaya diamondiferous eclogites: evidence for oceanic crustal protoliths

The Komsomolskaya kimberlite is one of numerous (>1,000) kimberlite pipes that host eclogite xenoliths on the Siberian craton. Eclogite xenoliths from the adjacent Udachnaya kimberlite pipe have previously been geochemically well characterized; however, data from surrounding diamond-bearing kimberlite pipes from the center of the craton are relatively sparse. Here, we report major- and trace-element data, as well as oxygen isotope systematics, for mineral separates of diamondiferous eclogite xenoliths from the Komsomolskaya kimberlite, suggesting two distinct subgroups of a metamorphosed, subducted oceanic crustal protolith. Using almandine contents, this suite can be divided into two subgroups: group B1, with a high almandine component (>20 mol%) and group B2, with a low almandine component (<20 mol%). Reconstructed REE profiles for B1 eclogites overlap with typical oceanic basalts and lack distinct Eu anomalies. In addition, elevated oxygen isotope values, which are interpreted to reflect isotopic exchange with seawater at low temperatures (<350 °C), are consistent with an upper-oceanic crustal protolith. Reconstructed REE profiles for B2 eclogites are consistent with oceanic gabbros and display distinct Eu anomalies, suggesting a plagioclase-rich cumulate protolith. In contrast to B1, B2 eclogites do not display elevated oxygen isotope values, suggesting an origin deep within the crustal pile, where little-to-no interaction with hydrothermal fluids has occurred. Major-element systematics were reconstructed based on mineral modes; group B1 eclogites have higher MgO wt% and lower SiO₂ wt%, with respect to typical oceanic basalts, reflecting a partial melting event during slab subduction. Calculated residues from batch partial melt modeling of a range of Precambrian basalts overlap with group B1 trace-element chemistry. When taken together with the respective partial melt trajectories, these melting events are clearly linked to the formation of Tonalite–Trondhjemite–Granodiorite (TTG) complexes. As a result, we propose that many, if not all, diamondiferous eclogite xenoliths from Komsomolskaya represent mantle ‘restites’ that preserve chemical signatures of Precambrian oceanic crust.     

Adsorption of copper and zinc onto natural clay in single and binary systems

Calcareous and smectitic clay samples from the Coniacian–Lower Campanian system, Tunisia, were used as adsorbents for the removal of copper and zinc from aqueous solutions in single and binary systems. Calcareous clay sample was treated with acetic acid to obtain carbonate-free sample that was also used for metals removal. The adsorption of metal ions onto natural clay was tested in a batch method by mixing 1 g/L of each sample with a metal ion solution of zinc (300 μmol/L) and/or copper 600 μmol/L under the operating pH of 6, and agitation speed of 200 rpm within the equilibrium time of 60 min at 25 °C for single and binary systems. Our results showed that natural clay samples were mainly composed of silica, alumina, iron, and magnesium oxides. Adsorption data showed that the studied clay samples removed substantial amounts of heavy metals in single and mixed systems. Initial solution pH and carbonates contents enhanced the removal capacities of the studied clay samples, confirming their strong influencing effects. Thermodynamic parameters indicated an endothermic adsorption for metals removal by calcareous clay, but exothermic process for the smectitic sample. These results suggest that the Late Cretaceous clays, Tunisia, can be effectively used as natural adsorbents for the removal of toxic heavy metals in aqueous systems.     

Evaluation,characterization and analytical application of a new composite material for removing metal ions from wastewater

A new organic/inorganic composite based on polyacrylonitrile and stannic molybdophosphate (PAN–SMP) as an adsorbent was synthesized under various conditions. The physicochemical properties of this material were specified by elemental analysis, scanning electron microscopy, infrared spectroscopy and thermogravimetry studies. The synthesized material was found to be stable in demineralized water, in dilute acids, under gamma radiation up to the total radiated of 100 kGy doses and in high temperature up to 500 °C. Ion exchange capacity of the synthesized composite and its distribution coefficient (K _d) for several metal ions were determined. The results showed that PAN–SMP has a great affinity toward some metal ions such as T^l+, Sr²⁺, Ba²⁺, UO₂ ²⁺ and La⁴⁺. Based on the determined K _d values, two binary quantitative separations of metal ions (Cr⁶⁺ from Cu²⁺ and Pb²⁺ from Cu²⁺) have been achieved on columns of this ion exchanger. The ability of PAN–SMP to decontaminate low-level liquid waste was also investigated.     

Distribution of isomorphous cations within octahedral sheets in montmorillonite from Camp-Bertaux

 Ni-saturated montmorillonite from Camp-Bertaux heated at different temperatures has been studied by X-ray powder diffraction, X-ray absorption (EXAFS) and vibration IR spectroscopy. Analysis of the experimental data has shown that heating of samples at temperatures higher than 150° C was accompanied by migration of Ni cations into vacant cis-octahedra of 2:1 layers. In the octahedral sheet the Ni cation has two “heavy” (Fe) and four “light” (Al and Mg) nearest octahedral cations. A model for the octahedral cation distribution in Camp-Bertaux montmorillonite was proposed in which Fe and Mg octahedral cations are segregated in small clusters. Received July 7, 1996 / Revised, accepted August 23, 1996     

Short-term sedimentation dynamics in the Rhône River Delta. France: The importance of riverine pulsing

Short-term sedimentation patterns were evaluated from August 1992 to May 1993 in different wetland habitats characteristic of the Rhône Delta, including impounded and seasonally-dry saline Arthrocnemum marshes, brackish Juncus, Phragmites, and Scirpus riverine wetlands directly connected to the Rhône River, and Arthrocnemum-dominated marine marshes influenced by the Mediterranean. Short-term sedimentation was measured as sediment accumulation on paper filters which had been placed on the soil surface for several weeks. Total sedimentation and material lost on ignition was significantly related to individual sampling periods, reflecting the importance of short-term processes. High sedimentation at riverine sites (up to 22 g m^?2 d^?1) was related to a combination of river stage and wind events. Marine and impounded wetlands of the Rhône Delta experienced low sedimentation throughout the period of study. Sedimentation rates averaged over the study period were 0.8 g m^?2 d^?1, 1.8 g m^?2 d^?1, and 5.4 g m^?2 d^?1 for marine, impounded, and riverine sites, respectively. Percent material lost on ignition was low in all habitats (average 15%) and followed a seasonal trend with a minimum in late fall and winter (1%). Soil percent organic matter was also low in the top several centimeters (13%), suggesting that inorganic sedimentation is very important for accretion on these wetland surfaces. Coastal flooding was not a significant mechanism for sedimentation in the marine sites during the period of study. Sedimentation is an important factor in elevation change, and this study shows that impounded habitats, the most common “natural environment“ left in the delta, may become vulnerable to sea-level rise in the future if management practices continue to isolate these wetlands from riverine sources of sediment.     

Experimental analysis of arsenic precipitation during microbial sulfate and iron reduction in model aquifer sediment reactors

Microbial SO₄²⁻ reduction limits accumulation of aqueous As in reducing aquifers where the sulfide that is produced forms minerals that sequester As. We examined the potential for As partitioning into As- and Fe-sulfide minerals in anaerobic, semi-continuous flow bioreactors inoculated with 0.5% (g mL⁻¹) fine-grained alluvial aquifer sediment. A fluid residence time of three weeks was maintained over a ca. 300-d incubation period by replacing one-third of the aqueous phase volume of the reactors with fresh medium every seven days. The medium had a composition comparable to natural As-contaminated groundwater with slightly basic pH (7.3) and 7.5 μM aqueous As(V) and also contained 0.8 mM acetate to stimulate microbial activity. Medium was delivered to a reactor system with and without 10 mmol L⁻¹ synthetic goethite (α-FeOOH). In both reactors, influent As(V) was almost completely reduced to As(III). Pure As-sulfide minerals did not form in the Fe-limited reactor. Realgar (As₄S₄) and As₂S₃(am) were undersaturated throughout the experiment. Orpiment (As₂S₃) was saturated while sulfide content was low (∼50 to 150 μM), but precipitation was likely limited by slow kinetics. Reaction-path modeling suggests that, even if these minerals had formed, the dissolved As content of the reactor would have remained at hazardous levels. Mackinawite (Fe_1 + xS; x ? 0.07) formed readily in the Fe-bearing reactor and held dissolved sulfide at levels below saturation for orpiment and realgar. The mackinawite sequestered little As (<0.1 wt.%), however, and aqueous As accumulated to levels above the influent concentration as microbial Fe(III) reduction consumed goethite and mobilized adsorbed As. A relatively small amount of pyrite (FeS₂) and greigite (Fe₃S₄) formed in the Fe-bearing reactor when we injected a polysulfide solution (Na₂S₄) to a final concentration of 0.5 mM after 216, 230, 279, and 286 days. The pyrite, and to a lesser extent the greigite, that formed did sequester As from solution, containing 0.84 and 0.23 wt.% As on average, respectively. Our results suggest that As precipitation during Fe-sulfide formation in nature occurs mainly in conjunction with pyrite formation. Our findings imply that the effectiveness of stimulating microbial SO₄²⁻ reduction to remediate As contamination may be limited by the rate and extent of pyrite formation and the solubility of As-sulfides.     

Factors controlling the development of prism faces in granite zircons: a microprobe study

Based on microprobe work, we present arguments that the size relations of the two common prisms {100} and {110} of accessory granite zircons are strongly influenced by chemical factors. Magmatic growth zoning patterns, which we have studied by means of backscattered electron imaging in special zircon sections orientated perpendicular to the c-axis, do not support previous models which assumed temperature or the degree of ZrSiO₄ supersaturation to be the primary prism-form-directing factors. The element U, which usually occupies the Zr-sites of granite zircoms to some degree, is strongly suspected of producing an (adsorptive) growth-blocking effect for {110}-type faces thus creating crystals with {110}-dominated prism morphology. A second independent mechanism that is likely to form zircons with large {110} prisms is the common substitution Zr⁴⁺+Si⁴⁺ versus Y(REE) and P contents (relative to Zr) are, according to our model, predestinated to produce zircons with large {100} prisms and vice versa.Dedicated to Prof. Günther Frasl on the occasion of his seventieth birthday     

Les laves du mont Bangou : une première manifestation volcanique éocène, à affinité transitionnelle,de la Ligne du Cameroun

Mount Bangou, an Eocene volcano (⁴⁰K–⁴⁰Ar ages between 44.7 and 43.1 ± 1 Ma) is the oldest dated volcano of the Cameroon Line. In this region, two magmatic series, evolving by fractional crystallization, show transitional affinities that are exceptionally known in this sector. Mineral compositions of basaltic rocks (scarce modal olivine and occurrence of normative hypersthene) as well as geochemical characteristics (low Ba, La, Ta contents and high Y/Nb ratios) are in agreement with this trend. The succession of magmas evolving in time from transitional to more typical alkaline compositions is evidenced in a continental setting. To cite this article: J. Fosso et al., C. R. Geoscience 337 (2005).     

The Correlation of the Upper Cretaceous Zonal Schemes of the Eastern European Platform Based on Foraminifera,Radiolaria, and Nannoplankton

This article proposes a biostratigraphic scheme for the Upper Cretaceous of the East European Platform on the basis of the distribution in the sections of three groups of microfossils: foraminifera (both planktonic and benthic), radiolarians, and nannoplankton. Most of the stage and substage boundaries are confirmed by macropaleontological data. The most divided units are those distinguished based on benthic foraminifers and nannoplankton. The diversity of these microfossils and their constant presence allowed us to identify zones and subzones, while it is possible to subdivide only the beds by planktonic foraminifers and radiolarians. The most favorable stages in the development of plankton biota can be considered the Turonian–Coniacian interval when the basins of the East European Platform experienced an intensive influence from warm waters of the Tethys Ocean. The global Campanian cooling is clearly recorded, which affected the taxonomic diversity of all microfossil groups.