Petrological characterization of the source components of potassic magmas: geochemical and experimental constraints

The source mineralogy and conditions of origin of the three main groups of ultrapotassic rocks are outlined by combining experimental constraints and an abstraction of evidence from whole-rock chemistry (including volatiles), tectonic setting and xenolith contents. Lamproites originate from a depleted source rock which was strongly re-enriched at a later stage, thus producing mica-harzburgite. Melting conditions are H₂O-rich and in most cases strongly reducing. Kamafugites originate from a clinopyroxene-reich source, also with abundant mica, in more oxidizing, CO₂-rich conditions. Members of the third group form in a relatively fertile spinel-peridotite also containing abundant clinopyroxene and mica. Contrasting effects of variation in (i) pressure of melting and (ii) oxygen fugacity, emphasize the importance of these parameters in the sources of ultrapotassic rocks.

Currently popular models for the origin of ultrapotassic melts by partial melting of phlogopite-bearing lherzolite are inconsistent with the now extensive array of liquidus experimental results on ultapotassic rock compositions. The discrepancy between partial melting models and liquidus results is attributed to the implicit, invalid assumption in the partial melting models that incompatible elements are homegeneously distributed on a large scale. Non-peridotitic assemblages rich in mica and pyroxenes which may be completely free of olivine must have an important role in the genesis of potassic rocks as spatially restricted components of inhomogeneous source regions.     

Using geovisual analytics to compare the performance of geographically weighted discriminant analysis versus its global counterpart,linear discriminant analysis

Geographically weighted spatial statistical methods are a family of spatial statistical methods developed to address the presence of non-stationarity in geographical processes, the so-called spatial heterogeneity. While these methods have recently become popular for analysis of spatial data, one of their characteristics is that they produce outputs that in themselves form complex multi-dimensional spatial data sets. Interpretation of these outputs is therefore not easy, but is of high importance, since spatial and non-spatial patterns in the results of these methods contain clues to causes of underlying non-stationarity. In this article, we focus on one of the geographically weighted methods, the geographically weighted discriminant analysis (GWDA), which is a method for prediction and analysis of categorical spatial data. It is an extension of linear discriminant analysis (LDA) that allows the relationship between the predictor variables and the categories to vary spatially. This produces a very complex data set of GWDA results, which include on top of the already complex discriminant analysis outputs (e.g. classifications and posterior probabilities) also spatially varying outputs (e.g. classification function parameters). In this article, we suggest using geovisual analytics to visualise results from LDA and GWDA to facilitate comparison between the global and local method results. For this, we develop a bespoke visual methodology that allows us to examine the performance of global and local classification method in terms of quality of classification. Furthermore, we are also interested in identifying the presence (or absence) of non-stationarity through comparison of the outputs of both methods. We do this in two ways. First, we visually explore spatial autocorrelation in both LDA and GWDA misclassifications. Second, we focus on relationships between the classification result and the independent variables and how they vary over space. We describe our visual analytic system for exploration of LDA and GWDA outputs and demonstrate our approach on a case study using a data set linking election results with a selection of socio-economic variables.     

Fe-rich Dunite Xenoliths from South African Kimberlites: Cumulates from Karoo Flood Basalts

Fe-rich dunite xenoliths within the Kimberley kimberlites compriseolivine neoblasts with minor elongated, parallel-oriented ilmenite,and rarely olivine porphyroclasts and spinel. Compared withtypical mantle peridotites, olivines in the Fe-rich duniteshave lower forsterite (Fo_87–89) and NiO contents (1300–2800ppm), which precludes a restitic origin for the dunites. Chrome-richspinels are remnants of a metasomatic reaction that producedilmenite and phlogopite. Trace element compositions differ betweenporphyroclastic and neoblastic olivine, the latter having higherTi, V, Cr and Ni and lower Zn, Zr and Nb contents, documentingtheir different origins. The dunites have high ¹⁸⁷Os/ ¹⁸⁸Osratios (0·11–0·15) that result in youngmodel ages for most samples, whereas three samples show isotopicmixtures between Phanerozoic neoblasts and ancient porphyroclasticmaterial. Most Fe-rich dunite xenoliths are interpreted to berecrystallized cumulates related to fractional crystallizationof Jurassic Karoo flood basalt magmatism, whereas the porphyroclastsare interpreted to be remnants from a much earlier (probablyArchaean Ventersdorp) magmatic episode. The calculated parentalmagma for the most primitive olivine neoblasts in the Fe-richdunites is similar to low-Ti Karoo basalts. Modelling the crystalfractionation of the inferred parental magma with pMELTS yieldselement fractionation trends that mirror the element variationof primitive low-Ti Karoo basalts. KEY WORDS: dunite xenoliths; fractional crystallization; Karoo; large igneous province; pMELTS; Re–Os; trace elements     

Internal Differentiation of the Archean Continental Crust: Fluid-Controlled Partial Melting of Granulites and TTG-Amphibolite Associations in Central Finland

Fault bound blocks of granulite and enderbite occur within upperamphibolite-facies migmatitic tonalitic–trondhjemitic–granodioritic(TTG) gneisses of the Iisalmi block of Central Finland. Theseunits record reworking and partial melting of different levelsof the Archean crust during a major tectonothermal event at2·6–2·7 Ga. Anhydrous mineral assemblagesand tonalitic melts in the granulites formed as a result ofhydrous phase breakdown melting reactions involving amphiboleat peak metamorphic conditions of 8–11 kbar and 750–900°C.A nominally fluid-absent melting regime in the granulites issupported by the presence of carbonic fluid inclusions. Thegeochemical signature of light rare earth element (LREE)-depletedmafic granulites can be modelled by 10–30 wt % partialmelting of an amphibolite source rock leaving a garnet-bearingresidue. The degree of melting in intermediate granulites isinferred to be less than 10 wt % and was restricted by the availabilityof quartz. Pressure–temperature estimates for the TTGgneisses are significantly lower than for the granulites at660–770°C and 5–6 kbar. Based on the P–Tconditions, melting of the TTG gneisses is inferred to haveoccurred at the wet solidus in the presence of an H₂O-rich fluid.A hydrous mineralogy, abundant aqueous fluid inclusions andthe absence of carbonic inclusions in the gneisses are in accordancewith a water-fluxed melting regime. Low REE contents and strongpositive Eu anomalies in most leucosomes irrespective of thehost rock composition suggest that the leucosomes are not meltcompositions, but represent plagioclase–quartz assemblagesthat crystallized early from felsic melts. Furthermore, similarplagioclase compositions in leucosomes and adjacent mesosomesare not a ‘migmatite paradox’, as both record equilibrationwith the same melt phase percolating along grain boundaries. KEY WORDS: Archean continental crust; fluid inclusion; granulite; migmatite; partial melting     

The effect of crystal orientation on the wetting behaviour of silicate melts on the surfaces of spinel peridotite minerals

. The effect of crystal anisotropy on wetting angles of equilibrium silicate melts on crystal faces of spinel, diopside, enstatite and olivine has been determined experimentally by the sessile melt drop technique. The anisotropy, Ãg_SL{\rm \~A}\gamma _{{\rm SL}} , of solid-liquid interfacial energies (%_SL(max)-%_SL(min)) can be related to the wetting angles, N, by Ãg_SL μ | cosy(max)  - cosy(min) | = Pw_{( [(A)\tilde]gSL )}{\rm \~A}\gamma _{{\rm SL}} \propto \left| {\cos \psi (\max )\; - \cos \psi (\min )} \right| = Pw_{\left( {{\rm \tilde A}\gamma _{{\rm SL}} } \right)} . Normalising to the smallest wetting angle gives values of Pw for diopside=0.0728, olivine=0.0574, orthopyroxene=0.0152, and spinel=0.0075. Crystal anisotropy influences grain-scale morphology of small-degree partial melts, permeability and the melt connectivity threshold, J_C. Results show that, at sufficient melt fractions, diopside should increase permeability in a peridotitic matrix, whereas enstatite should lower it. Despite its low anisotropy, spinel contributes positively to permeability and J_C because of its high surface energies. These results suggest that harzburgitic mineral matrices typical of the subcratonic mantle should impede the movement of low-degree partial melts, whereas melts should flow more easily through spinel lherzolites.     

The early differentiation history of Mars from W-Nd isotope systematics in the SNC meteorites

We report here the results of an investigation of W and Nd isotopes in the SNC (Shergottite-Nakhlite-Chassignite (martian)) meteorites. We have determined that ε¹⁸²W values in the nakhlites are uniform within analytical uncertainties and have an average value of ∼3. Also, while ε¹⁸²W values in the shergottites have a limited range (from 0.3-0.7), their ε¹⁴²Nd values vary considerably (from −0.2-0.9). There appears to be no correlation between ε¹⁸²W and ε¹⁴²Nd in the nakhlites and shergottites. These results shed new light on early differentiation processes on Mars, particularly on the timing and nature of fractionation in silicate reservoirs. Assuming a two-stage model, the metallic core is estimated to have formed at ∼12 Myr after the beginning of the solar system. Major silicate differentiation established the nakhlite source reservoir before ∼4542 Ma and the shergottite source reservoirs at 4525 Ma. These ages imply that, within the uncertainties afforded by the ¹⁸²Hf-¹⁸²W and ¹⁴⁶Sm-¹⁴²Nd chronometers, the silicate differentiation events that established the source reservoirs of the nakhlites and shergottites may have occurred contemporaneously, possibly during crystallization of a global magma ocean. The distinct ¹⁸²W-¹⁴²Nd isotope systematics in the nakhlites and the shergottites imply the presence of at least three isotopically distinct silicate reservoirs on Mars, two of which are depleted in incompatible lithophile elements relative to chondrites, and the third is enriched. The two depleted silicate reservoirs most likely reside in the Martian mantle, while the enriched reservoir could be either in the crust or the mantle. Therefore, the ¹⁸²W-¹⁴²Nd isotope systematics indicate that the nakhlites and the shergottites originated from distinct source reservoirs and cannot be petrogenetically related. A further implication is that the source reservoirs of the nakhlites and shergottites on Mars have been isolated since their establishment before ∼4.5 Ga. Therefore, there has been no giant impact or efficient global mantle convection to thoroughly homogenize the Martian mantle following the establishment of the SNC source reservoirs.     

Distinct site preferences for heavy and light REE in amphibole and the prediction of Amph/LDREE

New experimental amphibole/melt partition coefficients from a variety of geologically relevant amphibole (pargasite, kaersutite, and K-richterite) and melt compositions obtained under conditions of interest to upper-mantle studies are combined with the results of X-ray single-crystal structure refinement. The ideal cation radii (r₀), calculated using the lattice-site elastic-strain model of Blundy and Wood (1994) under the hypothesis of complete REE (rare earth elements) ordering at ^[8]M4, mostly differ significantly from those obtained from both the structure refinement and the ionic radius of ^[8]Ca²⁺. Heavier REE may also strongly deviate from the parabolic trends defined by the other REE. On the basis of the crystal-chemical knowledge of major-element site-preference in amphibole and the occurrence of two sites with different co-ordination within the M4 cavity (M4 for Ca and Na, M4′ for Fe²⁺ and Mg), we propose a new model for REE incorporation. LREE order at the ^[8]M4 site, whereas HREE prefer the M4′ site with lower co-ordination in amphiboles with a significant cummingtonite component, and may also enter the M2 octahedron, at least in richterite. This more complex model is consistent with the observed ^Amph/LD, and drops the usual assumption that REE behave as a homogeneous group and order at the M4 site. The availability of multiple crystal-chemical mechanisms for REE³⁺ incorporation explains why measured and estimated ^Amph/LD_HREE may differ by up to one order of magnitude. When REE enter two different sites within the same cavity, a fit performed on the basis of a single curve may appear correct, but the values obtained for r₀ are biased towards those of the dominant site, and the Young's modulus is underestimated. When REE are incorporated in multiple sites in different cavities, the observed pattern cannot be reduced to a single curve, and the partition coefficients of heavy REE would be strongly underestimated by a single-site fit. The simplistic assumption that REE occupy a single site within the amphibole structure can thus substantially bias predictive models based on the elastic-strain theory. Our combined approach allows linkage between fine-scale site preference and the macroscopic properties of minerals and provides more reliable predictive models for mineral/melt partitioning. After the possible site-assignments have been identified, the shape of the Onuma curves constructed from accurately determined ^Amph/LD_REE now allows the active mechanisms for REE incorporation in amphiboles to be recognised even where site populations are not available. The REE preference for polyhedra with smaller size and lower co-ordination than those occupied by Ca invalidates the general idea that Ca acts as a “carrier” for REE. Received: 17 March 1999 / Accepted: 11 June 1999     

Nanoscale Chemical Imaging by Photo‐Induced Force Microscopy: Technical Aspects and Application to the Geosciences

Photo‐induced force microscopy (PiFM) is a new‐frontier technique that combines the advantages of atomic force microscopy with infrared spectroscopy and allows for the simultaneous acquisition of 3D topographic data with molecular chemical information at high spatial (~ 5 nm) and spectral (~ 1 cm^?1) resolution at the nanoscale. This non‐destructive technique is time efficient as it requires only conventional mirror‐polishing and has fast mapping rates on the order of a few minutes that allow the study of dynamic processes via time series. Here, we review the method’s historical development, working principle, data acquisition, and evaluation, and provide a comparison with traditional geochemical methods. We review PiFM studies in the areas of materials science, chemistry and biology. In addition, we provide the first applications for geochemical samples including the visualization of faint growth zonation in zircons, the identification of fluid speciation in high‐pressure experimental samples, and of nanoscale organic phases in biominerals. We demonstrate that PiFM analysis is a time‐ and cost‐efficient technique combining high‐resolution surface imaging with molecular chemical information at the nanoscale and, thus, complements and expands traditional geochemical methods.     

A comment on: ‘TitaniQ under pressure: the effect of pressure and temperature on the solubility of Ti in quartz’, by Jay B. Thomas,E. Bruce Watson,Frank S. Spear,Philip T. Shemella,Saroj K. Nayak and Antonio Lanzirotti

Trace concentrations of Ti in quartz are used to indicate the pressure and temperature conditions of crystallization in the ‘TitaniQ’ geothermobarometer of Thomas et al. (Contrib Miner Petrol 160:743–759, 2010). It utilises the partitioning of Ti into quartz as an indicator of the pressures and/or temperatures of crystal growth. For a given value of TiO₂ activity in the system, if temperatures are inferred to ±20 °C, pressure is constrained to ±1 kbar and vice versa. There are significant contrasts, however, between the conclusions from TitaniQ and those for natural quartz (as well as other mineral phases) in volcanic rocks. Application of the TitaniQ model to quartz from the 27 ka Oruanui and 760 ka Bishop high-silica rhyolites, where the values of T, P and TiO₂ activity are constrained by other means (Fe–Ti oxide equilibria, melt inclusion entrapment pressures in gas-saturated melts, melt and amphibole compositions), yields inconsistent results. If realistic values are given to any two of these three parameters, then the value of the third is wholly unrealistic. The model yields growth temperatures at or below the granite solidus, pressures in the lower crust or upper mantle, or TiO₂ activities inconsistent with the mineralogical and chemical compositions of the magmas. CL imagery and measurements of Ti (and other elements) in quartz are of great value in showing the growth histories and changes in conditions experienced by crystals, but direct linkages to P, T conditions during crystal growth cannot be achieved.     

MicroRaman spectroscopy of diamond and graphite in Almahata Sitta and comparison with other ureilites

This work is the first detailed study of carbon phases in the ureilite Almahata Sitta (sample #7). We present microRaman data for diamond and graphite in Almahata Sitta, seven unbrecciated ureilites, and two brecciated ureilites. Diamond in Almahata Sitta was found to be distinct from that in unbrecciated and brecciated ureilites, although diamond in unbrecciated and brecciated ureilites is indistinguishable. Almahata Sitta diamond shows a peak center range of 1318.5–1330.2 cm^?1 and a full width at half maximum (FWHM) range of 6.6–17.4 cm^?1, representing a shock pressure of at least 60 kbar. The actual peak shock pressure may be higher than this due to postshock annealing, if shock synthesis is the source of ureilite diamonds. Diamond in unbrecciated and brecciated ureilites have peak center wave numbers closer to terrestrial kimberlite diamond, but show a wider range of FWHM than Almahata Sitta. The larger peak shift observed in Almahata Sitta may indicate the presence of lonsdaleite. Alternatively, the lower values in brecciated ureilites may be evidence of an annealing step either following the initial diamond‐generating shock or as a consequence of heating during reconsolidation of the breccia. Graphite in Almahata Sitta shows a G‐band peak center range of 1569.1–1577.1 cm^?1 and a G‐band FWHM range of 24.3–41.6 cm^?1 representing a formation temperature of 990 ± 120 °C. Amorphous carbon was also found. We examine the different theories for diamond formation in ureilites, such as chemical vapor deposition and shock origin from graphite, and explore explanations for the differences between Almahata Sitta and other ureilites.