María Dolores Ruiz Cruz

THERMAL BEHAVIOR OF THE KAOLINITE-HYDRAZINE INTERCALATION COMPLEX

The intercalation complex of a low-defect (“well-crystallized”) kaolinite from Cornwall, England, with hydrazine was studied by high-temperature X-ray diffraction (HTXRD), differential thermal analysis (DTA), and thermogravimetry (TG). The X-ray pattern at room temperature indicated that intercalation of hydrazine into kaolinite causes an increase of the basal spacing from 7.14 to 10.4 A, as previously reported. Heating between 25-200°C produces a structural rearrangement of the complex, which initially causes a contraction of the basal spacing from 10.4 to 9.6 A. In a second stage, the basal spacing reduces to 8.5 A. Finally, in a third stage, a reduction in spacing occurs through a set of intermediate phases, interpreted as interstratifications of intercalated and non-intercalated 1:1 layers. Evidence for these changes was observed by DTA, where three endothermic reactions are observed at low temperature. This behavior suggests that intercalated molecules occupy several well-defined sites in the in-terlayer of the kaolinite complex. The intercalated molecules deintercalate in an ordered fashion, which explains the successive and discontinuous contraction of the basal spacing of the complex. Heating between 200-400°C caused a limited increase in stacking order of the kaolinite structure, whereas dehy-droxylation of kaolinite and the disappearance of its X-ray reflections occurred between 450-640°C.

Hydrothermal synthesis of Mg-rich and Mg-Ni-rich kaolinite

Mg-rich kaolinite and Mg+Ni-rich kaolinite have been synthesized in hydrothermal experiments (200 and 400°C) from poorly crystalline kaolinite and Mg- and Mg+Ni-bearing solutions. Al-rich serpentine and Al-rich chlorite were obtained as sub-products of the reactions. The formation of these phases occurred through a dissolution-precipitation mechanism that led to spherical kaolinite after short reaction times. A morphological evolution towards platy particles and stacks occurred at increasing run times.Identification of the several phases was carried out using a combination of X-ray diffraction and transmission/analytical electron microscopy. Analytical data indicate that the Mg content in kaolinite increased as a function of the reaction time and temperature, reaching up to 0.46 atoms per half formula unit (a.p.h.f.u.). The measured (Mg+Ni) content reached up to 0.56 a.p.h.f.u.. Both the gradual increase of the b-cell parameter of kaolinite at increasing Mg contents and the presence of new bands on the FTIR spectra of the synthesized kaolinite point to a Mg-for-Al replacement in the octahedral sheet rather than to the presence of serpentine-like layers interstratified in the kaolinite structure.

Garnet variety and zircon ages in UHP meta-sedimentary rocks from the Jubrique zone (Alpujárride Complex, Betic Cordillera, Spain): evidence for a pre-Alpine emplacement of the Ronda peridotite

The Ronda peridotite is a group of lherzolite slabs (1.5 to 2 km thick) in southern Spain. Despite clear evidence that pre-Alpine events affected pre-Permo-Triassic units from the Alborán domain (internal zone of the Betic-Rif Cordillera, Spain, and Morocco), numerous papers continue to emphasize Alpine metamorphic and structural evolution. Here, we evaluate the pre-Cenozoic evolution of the Ronda peridotite by reporting new petrographic and U–Pb SHRIMP zircon dating of meta-sedimentary rocks from the Jubrique zone (Alpujárride Complex, Betic Cordillera, Spain) directly overlying the Ronda peridotite. Field inspection and petrographical study revealed generalized migmatitic textures and a gradual transition mainly defined by garnet content (from ~30 to <3 wt.%) and size (from 1.5 cm to <0.5 mm) in the overlying granulite-gneiss sequence, suggesting that most garnet grew as a consequence of the peridotite emplacement. Garnet shows notable variations in composition and inclusion types, which are interpreted as reflecting different stages of garnet growth. Diamond-bearing garnets are only well-preserved in gneisses from the uppermost part of the sequence, whereas the large garnets from rocks overlying the peridotite mainly record later thermal events. SHRIMP zircon dating indicates two age peaks at 330 ± 9 and 265 ± 4 Ma. The oldest age characterizes rims overgrowing detrital cores and reflects an early Hercynian metamorphism; the younger age characterizes zircon with magmatic oscillatory zoning, reflecting anatexis. On the basis of these data and of previous dating of monazite included in the large garnets, we conclude that the peridotite was emplaced either shortly before or during early Hercynian times, ~330 Ma.

Thermal decomposition of a dickite-hydrazine intercalation complex.

The intercalation complex of a low-defect dickite from Tarifa, Spain, with hydrazine was studied by high-temperature X-ray diffraction (HTXRD). differential thermal analysis (DTA), and ther-mogravimetry (TG). The X-ray diffraction (XRD) pattern obtained at room temperature indicated that the intercalation of hydrazine and H2O into dickite caused an increase of the basal spacing from 7.08 to 10.24 A, which is slightly lower than the 10.4-Å spacing commonly observed after intercalation into kaolinite. Heating between 25–50°C produced a structural rearrangement of the complex, which decreased the basal spacing from 10.24 to 9.4 A, and the resulting 9.4-Å complex was stable between 50–90°C. Heating between 90–300°C caused a gradual reduction in spacing, which occurred through a set of intermediate phases. These phases were interpreted to be interstratifications of intercalated and non-intercalated layers. These changes were also observed by DTA and TG. Two main endothermic reactions and two main stages of mass loss, respectively, were indicated in the DTA and the TG curves in the temperature range 25–200°C. This behavior suggests that intercalated molecules, hydrazine and H2O, occupied well-defined sites in the interlayer of the dickite. The intercalated molecules were lost in an ordered fashion as confirmed by the infrared analysis of the decomposition products; H2O was lost in the first stage and ammonia was identified in the second stage. Above 300°C, complete removal of the intercalated molecules restored the basal spacing of the dickite. However, the basal reflections were broadened, the relative intensities were changed, and changes in the dehydroxylation temperature indicated that the intercalation-desorption process induced some stacking disorder in the dickite structure.

SYNTHESIS OF Ni-RICH 1:1 PHYLLOSILICATES

Rapid dissolution of partly amorphized kaolinite in the systems kaolinite + NiCl2, kaolinite + Ni(OH)2, and kaolinite + NiCl2 + Ni(OH)2, at a temperature of 200°C and at pH between 5.3 and 7.4, leads to the precipitation of Ni-poor kaolinite, Ni-rich kaolinite and Al-Ni-serpentine. Identification of the phases was carried out using a combination of X-ray diffraction and transmission/analytical electron microscopy. Ni-bearing kaolinite shows variable morphologies in the systems studied: stacks of kaolinite with relatively small Ni contents and fine-grained curved particles of Ni-rich kaolinite dominate in the Cl-bearing system; spherical particles with a disordered structure and relatively uniform Ni contents (in the order of 0.15 atoms per formula unit (a.p.f.u.)) and platy particles of Al-Ni-serpentine characterize the products formed in the Ni(OH)2-richest systems. The presence of Ni(OH)2 in the systems (with and without Cl) favors the dissolution process as well as rapid precipitation of spherical particles, and the formation of serpentine. A difference from Mg systems studied previously is a well defined phase intermediate in composition between kaolinite and serpentine which originated in the Ni-bearing systems. Increasing Ni content is clearly reflected in the parallel increase in the b cell parameter of kaolinite. The average composition of the coexisting Al-Ni-serpentine is: (Al1.24Ti0.01Fe0.02Ni1.31) (Si1.58Al0.42)O5(OH,Cl)2.

Metamorphic evolution of Triassic rocks from the transition zone between the Maláguide and Alpujárride complexes (Betic Cordilleras, Spain).

A complete sequence of mineral assemblages ranging from late diagenesis to the epizone has been identified in Triassic rocks from “intermediate units” between the Alpujarride and the Malaguide complexes (Betic Cordillera, Spain). These units appear as a set of tectonic slices, the uppermost showing lithological characteristics similar to the Malaguide complex, which change as depth increases, towards lithologies typical of the Alpujarride complex. The study was carried out by X-ray diffraction, optical microscopy, electron microprobe and X-ray fluorescence. The mineralogical composition shows a clear vertical evolution: A dickite-bearing assemblage, characteristic of the upper slices is replaced by sudoite ± pyrophyllite-bearing assemblages, these by trioctahedral chlorite-rich assemblages, and finally by paragonite-bearing assemblages. Examination of bulk-rock chemistries indicates that most of the mineralogical changes are the result of the increasing metamorphic grade, with the exception of chloritoid; its growth does appear to be partly controlled by the rocks chemistry (it is Al 2 O 3 dependent). The evolution of the metamorphic assemblages occurred prior to emplacement of the slices by thrusting and reveals a progressive transition in metamorphic grade between both complexes, although some discontinuities in the KI values between consecutive slices are observed.

COMPOSITIONAL AND STRUCTURAL VARIATION OF SUDOITE FROM THE BETIC CORDILLERA (SPAIN): A TEM/AEM STUDY

Sudoite from diagenetic to very low-grade metaclastites of the Betic Cordillera was studied by X-ray diffraction and transmission/analytical electron microscopy. Sudoite formed directly from dickite, the assemblage dickite + sudoite + illite being replaced at increasing metamorphic grade by the assemblage pyrophyllite + sudoite + illite. Sudoite ranges in composition from Mg-rich to Fe-rich chemistries. In addition, a wide variety of mixed-layered structures (illite-sudoite, pyrophyllite-sudoite, and dickite-sudoite) was also identified. Mg-rich sudoite shows a mean chemical composition of (Al2.91Fe0.252+Mg1.80)(Si3.10Al0.90)O10(OH)8, and a IIb ordered structure with b = 9.055 Å. Intermediate Fe-Mg sudoite exhibits a very variable composition, the Fe-rich phases having a mean composition of (Al2.09Fe0.613+Fe0.872+Mg1.44)(Si3.31Al0.69O10(OH)8. These are disordered polytypes with b values ranging from 9.070 to 9.101 Å. Fe occurs in both octahedral sheets, according to two types of substitutions: Fe3+ for Al in the dioctahedral sheet and Fe2+ for Mg in the trioctahedral sheet. Sudoite with such a composition has not been described previously.

Suhailite, a new ammonium trioctahedral mica

A new ammonium-bearing trioctahedral mica (suhailite) has been found in gneisses from the Betic Cordillera (Spain). Suhailite appears as aggregates of golden grains unoriented with respect to the main foliation. It shows weak pleochroism from light to darker yellow and low birefringence (0.028). X-ray data indicate the presence of two compositional variations: a NH4-rich phase (with a basal spacing of 10.40–10.44 Å) and a NH4-K intermediate phase (with basal spacing of 10.20–10.26 Å). Average composition, as deduced from analyses obtained at the scale of the scanning electron microscope is [Ca0.04Na0.07K0.35(NH4)0.55](Al0.42Ti0.22Fe1.33Mn0.01Mg0.71)Σ=2.70(Si2.67Al1.33)O10(OH)2. Thermal data indicate that maximum NH4 detachment occurs at 502 °C, suggesting a thermal stability similar to tobelite. Textural data indicate that unoriented golden grains consist of fine intergrowths of annite and suhailite and suggest that suhailite formed from primary red annite during the annite to fibrolite transformation.

Petrology of microdiamond-bearing schists from the Torrox unit, Betic Cordillera, Spain

Microdiamond inclusions in garnet have been identified in pre-Triassic schists of unknown age from the Torrox unit in the Alpujarride complex, Internal Zone of the Betic Cordillera, Spain. Prior to this, ultrahigh-pressure (UH P ) phases have been identified in granulites and gneisses associated with peridotites in the western zone of the Cordillera and in the NW of the Rif Mountains. This new finding reveals that the UH P metamorphism affected a crustal sequence notably thicker than previously assumed. In contrast with granulites and gneisses, in which only the UH P event and the local thermal effect of the peridotite emplacement have been identified, schists record a complex poly-metamorphic history, which contrasts with previous interpretations based on an exclusively Alpine metamorphic scenario. In addition to the UH P event, the schists show clear signals of two later metamorphic events, recorded by several stages of garnet growth, by staurolite–andalusite parageneses, and by matrix micas. In this study the metamorphic sequence is established, but the timing of the different metamorphic events remains uncertain.

Metamorphic chlorite and “vermiculitic” phases in mafic dikes from the Maláguide Complex (Betic Cordillera, Spain)

Low-grade metamorphic mineral associations present in mafic dikes from the Malaguide Complex were examined by X-ray diffraction (XRD) analysis, electron microprobe analysis (EMPA) and transmission-analytical electron microscopy (TEM/AEM). The low-grade phyllosilicates occur both as pseudomorphs after pyroxene and as matrix phases of the rock. The metamorphic phyllosilicate assemblage is formed either by chlorite + muscovite or by the association chlorite + randomly ordered chlorite/vermiculite mixed-layers + 1:1 regular chlorite/vermiculite mixed-layers + vermiculite (or Na-biotite). Chemical changes observed from chlorite to vermiculitic phases include: 1) increase of the Si/Al ratio; 2) decrease of Mg+Fe; and 3) presence of variable amounts of Ca+alkali. Later alteration of the second assemblage originates Al-smectite, which forms from chlorite-, mixed-layers- and low-charge biotite (vermiculite) packets. Excluding the alteration products, the mineral associations observed in dikes are similar, as studied by XRD, to those observed in metaclastites from this Complex, suggesting a common metamorphic event. Nevertheless, both EMPA and TEM/AEM analyses reveal chemical differences, which are probably related to differences in bulk-chemistry between metaclastites and dikes.