Disequilibrium for Ca during growth of pelitic garnet

Compositional zoning in hundreds of almandine-rich garnets in amphibolite by facies micaceous quartzites from the Picuris Range, north-central New Mexico USA, indicates that although Mn, Mg and Fe achieve chemical equilibrium at hand-sample scale during garnet growth, Ca does not. Instead, Ca concentrations at the surface of growing garnets appear to depend strongly on kinetic factors that govern the local chemical environment, yielding disequilibrium for Ca at scales larger than the region immediately surrounding an individual porphyroblast. Detailed zoning profiles were obtained for 371 garnet crystals in a small volume of a single sample of garnetiferous quartzite, and core analyses were made of 97 additional crystals. Each analysis was made on a section that passed precisely through the morphological centre of the crystal, located by means of 3-D imagery from computed X-ray tomography. The data reveal strong correlations between crystal size and concentrations of Mn, Mg and Fe (but not Ca) in garnet cores; a relationship between crystal size and isolation; rigorous cross-correlations among concentrations of Mn, Mg and Fe (but not Ca); and systematic variations in Ca concentrations as a function of crystal size and core composition that are anomalous in comparison to the behaviour of the other divalent cations. We interpret these observations as the result of thermally accelerated diffusion-controlled garnet growth, in circumstances that promoted rapid intergranular diffusion and thus rock-wide equilibration of Mn, Mg and Fe, but that prevented equilibration at similar scale for Ca because of its more sluggish intergranular diffusion. The anomalous behaviour of Ca is made evident in these garnets by the presence of sharp spikes in Ca concentration, which are demonstrably not a consequence of any simultaneous rock-wide event, such as a change in pressure, temperature, or some other intensive parameter. Instead, Ca concentrations probably reflect the local extent of reaction in the immediate vicinity of each porphyroblast. To the degree that such kinetic factors introduce departures from chemical equilibrium for Ca, thermobarometric estimates that involve grossular contents of pelitic garnet will be in error.     

UV Laser Ablation ICP-MS: Some Applications in the Earth Sciences

This study reports a series of applications of UV laser ablation ICP-MS in the geological sciences. The advantages and disadvantages of the PQ "S" option and the use of nitrogen in the carrier gas are discussed. A general problem common to all ablation techniques is the calibration technique and experiments involving synthetic calibration samples are covered. Zircon geochemistry and geochronology by LA-ICP-MS are discussed and data are presented for REE, Hf and U for a standard zircon (91500) as well as a series of zircons from Zimbabwe. The potential of using Ce and Eu anomalies in petrologic studies is illustrated by zircons from a fractionated gabbroic-granite in the Urals. The potential of the LA-ICP-MS method to utilise standard X-ray fluorescence glass discs is demonstrated as a useful semi-quantitative tool in determining REE patterns. LA-ICP-MS is a powerful tool in the analysis of the platinum group elements (and Re) and some examples are given in the successful application of the technique to partitioning in iron meteorites.     

Comparative studies of the kinetic parameters of various algaenans and kerogens via open-system pyrolyses

Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (E_a) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in E_a distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad E_a distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma⁻¹ and the generation rate curves and cumulative yield curves thus obtained were compared.     

Redetermination of the transformation enthalpies of the xanthoconite–proustite, pyrostilpnite–pyrargyrite and trechmannite–smithite phase transitions

 We report here refined values of the transformation enthalpy for xanthoconite to proustite (54.81 kJ/mol) and pyrostilpnite to pyrargyrite (40.32 kJ/mol). Additionally, the enthalpy for the transformation of trechmannite to smithite (5.82 kJ/mol) has been determined. The refinement was possible by taking into account a previously unknown dependence of electrochemical signals on the amount of substance undergoing the reduction process. Received December 21, 1995/Revised, accepted June 29, 1996     

A short range interaction model applied to illite/smectite mixed-layer minerals

We present a solid solution model, able to take into account short-range interactions up to the third nearest neighbor. This model has been applied to illite/smectite mixed-layer clay minerals and tests the relative thermodynamic stability of each illite/smectite stacking sequence. The non-ideal energy terms have been calculated, showing a strong decrease of the interaction energy as the distance between elements grows. From ΔG _m calculations the model predicts the following succession in I/S stacking sequences as X _i tends to 1:R1, R2 and then R3. This succession agrees well with some mineralogical observations in natural series. Received: July 12, 1996 / Revised, accepted: March 21, 1997     

ELNES spectroscopy of mixed Si coordination minerals

 Si K- and L-edge ELNES spectroscopy and multiple-scattering (MS) calculations are used to examine mixed Si coordination compounds varying in Si^VI:Si^IV ratio. As in previous studies, the edges are influenced mainly by silicon coordination (tetrahedral vs. octahedral), as supported by the MS calculations. We demonstrate two methods semi-quantitatively to extract the value of Si^VI/(Si^VI+Si^IV): (1) A linear relationship between the L_2,3-L₁ splitting and Si^VI/(Si^VI+Si^IV) is observed, (2) a fitting method based on the coaddition of reference tetrahedral and octahedral Si spectra is applied to both Si K- and L-edge ELNES spectra. Received: February 10, 1997 / Revised, accepted: May 23, 1997     

Ccte d'Ivoire-Ghana margin: seismic imaging of passive rifted crust adjacent to a transform continental margin

During May 1990 and January-February 1991, an extensive geophysical data set was collected over the Côte d'Ivoire-Ghana continental margin, located along the equatorial coast of West Africa. The Ghana margin is a transform continental margin running subparallel to the Romanche Fracture Zone and its associated marginal ridge—the Côte d'Ivoire-Ghana Ridge. From this data set, an explosive refraction line running ∼ 150 km, ENE-WSW between 3°55'N, 3°21'W and 4°23'N, 2°4'W, has been modelled together with wide-angle airgun profiles, and seismic reflection and gravity data. This study is centred on the Côte d'Ivoire Basin located just to the north of the Côte d'Ivoire-Ghana Ridge, where bathymetric data suggest that a component of normal rifting occurred, rather than the transform motion observed along the majority of the equatorial West African margin.
Traveltime and amplitude modelling of the ocean-bottom seismometer data shows that the continental Moho beneath the margin rises in an oceanward direction, from ∼ 24 km below sea level to ∼ 17 km. In the centre of the line where the crust thins most rapidly, there exists a region of anomalously high velocity at the base of the crust, reaching some 8 km in thickness. This higher-velocity region is thought to represent an area of localized underplating related to rifting. Modelling of marine gravity data, collected coincident with the seismic line, has been used to test the best-fitting seismic model. This modelling has shown that the observed free-air anomaly is dominated by the effects of crustal thickness, and that a region of higher density is required at the base of the crust to fit the observed data. This higher-density region is consistent in size and location with the high velocities required to fit the seismic data.     

Periodicity of magnetic intensities in magnetic anomaly profiles: the Cenozoic of the South Atlantic

Spectral analyses of several published magnetic anomaly profiles from Candé & Kent (1992a) were undertaken prior to analysing, in the same way, raw magnetic anomaly data from similar parts of the South Atlantic. It was found that similar and distinct medium and short wavelengths were present in both the published and raw data. When these are converted into the time domain using the average rate of spreading for each profile, these periodicities appear similar, possibly identical, to those expected from the long-term eccentricity orbital parameters (Fischer, DeBoer & Premoli Silva 1990). While such correlations are not necessarily causative, they suggest that magnetohydro-dynamical processes near the core-mantle boundary may be affected by gravitational changes due to planetary orbital perturbations.