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SDLRC - Scientific Articles all years by Author - Mar-Mh
The Sheahan Diamond Literature Reference Compilation
The Sheahan Diamond Literature Reference Compilation is compiled by Patricia Sheahan who publishes on a monthly basis a list of new scientific articles related to diamonds as well as media coverage and corporate announcementscalled the Sheahan Diamond Literature Service that is distributed as a free pdf to a list of followers. Pat has kindly agreed to allow her work to be made available as an online digital resource at Kaiser Research Online so that a broader community interested in diamonds and related geology can benefit. The references are for personal use information purposes only; when available a link is provided to an online location where the full article can be accessed or purchased directly. Reproduction of this compilation in part or in whole without permission from the Sheahan Diamond Literature Service is strictly prohibited. Return to Diamond Resource Center
Sheahan Diamond Literature Reference Compilation - Scientific Articles by Author for all years
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American Mineralogist, Vol. 105, pp. 1662-1671. pdf
Mantle
melting
Abstract: Zircon is the most frequently used mineral for dating terrestrial and extraterrestrial rocks. However, the system of zircon in mafic/ultramafic melts has been rarely explored experimentally and most existing models based on the felsic, intermediate and/or synthetic systems are probably not applicable for prediction of zircon survival in terrestrial shallow asthenosphere. In order to determine the zircon stability in such natural systems, we have performed high-temperature experiments of zircon dissolution in natural mid-ocean ridge basaltic and synthetic haplobasaltic melts coupled with in situ electron probe microanalyses of the experimental products at high current.
Taking into account the secondary fluorescence effect in zircon glass pairs during electron microprobe analysis, we have calculated zirconium diffusion coefficient necessary to predict zircon survival in asthenospheric melts of tholeiitic basalt composition. The data imply that typical 100 micron zircons dissolve rapidly (in 10 hours) and congruently upon the reaction with basaltic melt at mantle pressures. We observed incongruent (to crystal ZrO2 and SiO2 in melt) dissolution of zircon in natural mid-ocean ridge basaltic melt at low pressures and in haplobasaltic melt at elevated pressure. Our experimental data raise questions about the origin of zircons in mafic and ultramafic rocks, in particular, in shallow oceanic asthenosphere and deep lithosphere, as well as the meaning of the zircon-based ages estimated from the composition of these minerals. Large size zircon megacrysts in kimberlites, peridotites, alkali basalts and other magmas suggest the fast transport and short interaction between zircon and melt.The origin of zircon megacrysts is likely related to metasomatic addition of Zr into mantle as any mantle melting episode should obliterate them.
Journal of South American Earth Sciences, Vol. 79, pp. 431-442.
South America, Brazil
craton
Abstract: The study of the crust using receiver functions can provide valuable geological information, such as average crustal composition, its formation dynamics and the tectonic evolution of a region, as well as serve as an initial reference for the generation of seismic wave velocity models to improve earthquake location. To fill in gaps in information on the crust of the Amazonian Craton and adjacent provinces in Brazil, we used receiver functions and H-k stacking to estimate crustal thicknesses and the VP/VS ratios. The results indicate that the crust of the study region is predominantly felsic, with an average VP/VS around 1.73 and an average thickness of 38.2 km, with a range of 27.4-48.6 km. Minimum curvature interpolation of the crustal thickness values has made it possible to delimitate of the Amazonian Craton, which corresponds to the area with an average thickness equal to or greater than 39 km. In addition, it was possible to identify its potential cratonic blocks, as well as the Paranapanema Block of Paraná Basin. The geometry of the craton, defined by its crustal thickness, is corroborated by the distribution of natural seismicity that accompanies its edges. These are related to suture zones between the Amazonian, São Francisco/Congo and Paranapanema paleocontinents. The sedimentary basins that have undergone rifting processes have a thinner crust, usually less than 37 km thick. Due to the great variability of the results, it was not possible to determine a characteristic value of c
Abstract: Field evidence from the Pilbara craton (Australia) and Kaapvaal craton (South Africa) indicate that modern tectonic processes may have been operating at ca. 3.2 Ga, a time also associated with a high density of preserved Archaean impact indicators. Recent work has suggested a causative association between large impacts and tectonic processes for the Hadean. However, impact flux estimates and spherule bed characteristics suggest impactor diameters of <100 km at ca. 3.5 Ga, and it is unclear whether such impacts could perturb the global tectonic system. In this work, we develop numerical simulations of global tectonism with impacting effects, and simulate the evolution of these models throughout the Archaean for given impact fluxes. We demonstrate that moderate-size (~70 km diameter) impactors are capable of initiating short-lived subduction, and that the system response is sensitive to impactor size, proximity to other impacts, and also lithospheric thickness gradients. Large lithospheric thickness gradients may have first appeared at ca. 3.5-3.2 Ga as cratonic roots, and we postulate an association between Earth’s thermal maturation, cratonic root stability, and the onset of widespread sporadic tectonism driven by the impact flux at this time.
Diamond exploration in the Peace River Arch, Alberta
The Canadian Mining and Metallurgical Bulletin (CIM Bulletin) , Annual Meeting Abstracts approximately 10 lines, Vol. 86, No. 968, March POSTER ABSTRACT p. 68.
Devriese, S.G.R., Corcoran, N., Cowan, D., Davis, K., Bild-Enkin, D., Fournier, D., Heagy, L., Kang, S., Marchant, D., McMillan, M.S., Mitchell, M., Rosenkjar, G., Yang, D., Oldenburg, D.W.
Magnetic inversion of three airborne dat a sets over the Tli Kwi Cho kimberlite complex.
SEG Annual Meeting Denver, pp. 1790-1794 extended abstract
Fournier, D., Heagy, L., Corcoran, N., Devriese, S.G.R., Bild-Enkin, D., Davis, K., Kang, S., Marchant, D., McMillan, M.S., Mitchell, M., Rosenkjar, G., Yang, D., Oldenburg, D.W.
Multi-EM systems inversion - towards a common conductivity model for Tli Kwi Cho complex.
SEG Annual Meeting Denver, pp. 1795-1798. Extended abstract
Devriese, S.G.R., Corcoran, N., Cowan, D., Davis, K., Bild-Enkin, D., Fournier, D., Heagy, L., Kang, S., Marchant, D., McMillan, M.S., Mitchell, M., Rosenkjar, G., Yang, D., Oldenburg, D.W.
Abstract: The magnetic and electromagnetic responses from airborne systems at Tli Kwi Cho, a kimberlite complex in the Northwest Territories, Canada, have received considerable attention over the last two decades but a complete understanding of the causative physical properties is not yet at hand. Our analysis is distributed among three papers. In the first, we find a 3D magnetic susceptibility model for the area; in the second, we find a 3D conductivity model; and in the third paper, we find a 3D chargeability model. Our goal is to explain all the geophysical results within a geologic framework. In this first paper, we invert three independent airborne magnetic data sets flown over the Tli Kwi Cho kimberlite complex located in the Lac de Gras kimberlite field in Northwest Territories, Canada. The complex consists of two kimberlites known as DO-27 and DO-18. An initial airborne DIGHEM survey was flown in 1992 and AeroTEM and VTEM data subsequently acquired in 2003 and 2004, respectively. In this paper, we invert each magnetic data set in three dimensions. Both kimberlites are recovered in each model, with DO-27 as a more susceptible body than DO-18. Our goal is to simultaneously invert the three data sets to generate a single susceptibility model for Tli Kwi Cho. This project is part of a larger, on-going investigation by UBC-GIF on inverting magnetic, electromagnetic, and induced polarization data from the Tli Kwi Cho area.
Fournier, D., Heagy, L., Corcoran, N., Cowan, D., Devriese, S.G.R., Bild-Enkin, D., Davis, K., Kang, S., Marchant, D., McMillan, M.S., Mitchell, M., Rosenkjar, G., Yang, D., Oldenburg, D.W.
Abstract: The magnetic and electromagnetic responses from airborne systems at Tli Kwi Cho, a kimberlite complex in the Northwest Territories, Canada, have received considerable attention over the last two decades but a complete understanding of the causative physical properties is not yet at hand. Our analysis is distributed among three posters. In the first we find a 3D magnetic susceptibility model for the area; in the second we find a 3D conductivity model; and in the third we find a 3D chargeability model that can explain the negative transient responses measured over the kimberlite pipes. In this second paper we focus upon the task of finding a conductivity model that is compatible with three airborne data sets flown between 1992 and 2004: one frequency-domain data set (DIGHEM) and two time-domain systems (AeroTEM and VTEM). The goal is to obtain a 3D model from which geologic questions can be answered, but even more importantly, to provide a background conductivity needed to complete the 3D IP inversion of airborne EM data. We begin by modifying our pre-existing 1D frequency and time domain inversion codes to produce models that have more lateral continuity. The results are useful in their own right but we have also found that 1D analysis is often very effective in bringing to light erroneous data, assisting in estimating noise floors, and providing some starting information for developing a background model for the 3D EM inversion. Here we show some results from our Laterally Constrained Inversion (LCI) framework. The recovered conductivity models seem to agree on the general location of the kimberlite pipes but disagree on the geometry and conductivity values at depth. The complete 3D inversions in time and frequency, needed to resolved these issues, are currently in progress.
Devriese, S.G.R., Corcoran, N., Cowan, D., Davis, K., Bild-Enkin, D., Fournier, D., Heagy, L., Kang, S., Marchant, D., McMillan, M.S., Mitchell, M., Rosenkjar, G., Yang, D., Oldenburg, D.W.
Abstract: The magnetic and electromagnetic responses from airborne systems at Tli Kwi Cho, a kimberlite complex in the Northwest Territories, Canada, have received considerable attention over the last two decades but a complete understanding of the causative physical properties is not yet at hand. Our analysis is distributed among three papers. In the first, we find a 3D magnetic susceptibility model for the area; in the second, we find a 3D conductivity model; and in the third paper, we find a 3D chargeability model. Our goal is to explain all the geophysical results within a geologic framework. In this first paper, we invert three independent airborne magnetic data sets flown over the Tli Kwi Cho kimberlite complex located in the Lac de Gras kimberlite field in Northwest Territories, Canada. The complex consists of two kimberlites known as DO-27 and DO- 18. An initial airborne DIGHEM survey was flown in 1992 and AeroTEM and VTEM data subsequently acquired in 2003 and 2004, respectively. In this paper, we invert each magnetic data set in three dimensions. Both kimberlites are recovered in each model, with DO-27 as a more susceptible body than DO-18. Our goal is to simultaneously invert the three data sets to generate a single susceptibility model for Tli Kwi Cho. This project is part of a larger, on-going investigation by UBC-GIF on inverting magnetic, electromagnetic, and induced polarization data from the Tli Kwi Cho area.
Fournier, D., Heagy, L., Corcoran, N., Cowan, D., Devriese, S.G.R., Bild-Enkin, D., Davis, K., Marchant, M., McMillan, M.S., Mitchell, M., Rosenkjar, G., Yang, D., Oldenburg, D.W.
Abstract: The magnetic and electromagnetic responses from airborne systems at Tli Kwi Cho, a kimberlite complex in the Northwest Territories, Canada, have received considerable attention over the last two decades but a complete understanding of the causative physical properties is not yet at hand. Our analysis is distributed among three posters. In the first we find a 3D magnetic susceptibility model for the area; in the second we find a 3D conductivity model; and in the third we find a 3D chargeability model that can explain the negative transient responses measured over the kimberlite pipes. In this second paper we focus upon the task of finding a conductivity model that is compatible with three airborne data sets flown between 1992 and 2004: one frequency-domain data set (DIGHEM) and two time-domain systems (AeroTEM and VTEM). The goal is to obtain a 3D model from which geologic questions can be answered, but even more importantly, to provide a background conductivity needed to complete the 3D IP inversion of airborne EM data. We begin by modifying our pre-existing 1D frequency and time domain inversion codes to produce models that have more lateral continuity. The results are useful in their own right but we have also found that 1D analysis is often very effective in bringing to light erroneous data, assisting in estimating noise floors, and providing some starting information for developing a background model for the 3D EM inversion. Here we show some results from our Laterally Constrained Inversion (LCI) framework. The recovered conductivity models seem to agree on the general location of the kimberlite pipes but disagree on the geometry and conductivity values at depth. The complete 3D inversions in time and frequency, needed to resolved these issues, are currently in progress.
Moscow University Geology Bulletin, Vol. 72, 5, pp. 299-304.
Mantle
perovskite
Abstract: Semi-empirical and quantum chemical studies of Al atom energy in CaSiO3 and MgSiO3 with the perovskite-type structure at pressures and temperatures of the Earth’s mantle are reported. The phase diagram for CaSiO3 is reproduced and refined. Probable mechanisms of Al incorporation in the structures studied are considered. According to the results of the calculations, Al is preferably incorporated into MgSiO3, rather than into CaSiO3. Evaluation of the isomorphic capacity of perovskite phases in relation to Al shows that the Al content in MgSiO3 may reach 2.4 mol % at 120 GPa and 2400 K. CaSiO3 cannot be a source of Al atoms in the Earth’s mantle.
Abstract: Trace elements play a significant role in interpretation of different processes in the deep Earth. However, the systematics of interphase rare-earth element (REE) partitioning under the conditions of the uppermost lower mantle are poorly understood. We performed high-pressure experiments to study the phase relations in key solid-phase reactions CaMgSi2O6 = CaSiO3-perovskite + MgSiO3-bridgmanite and (Mg,Fe)2SiO4-ringwoodite = (Mg,Fe)SiO3-bridgmanite + (Mg,Fe)O with addition of 1 wt % of REE oxides. Atomistic modeling was used to obtain more accurate quantitative estimates of the interphase REE partitioning and displayed the ideal model for the high-pressure minerals. HREE (Er, Tm, Yb, and Lu) are mostly accumulated in bridgmanite, while LREE are predominantly redistributed into CaSiO3. On the basis of the results of experiments and atomistic modeling, REE in bridgmanite are clearly divided into two groups (from La to Gd and from Gd to Lu). Interphase REE partition coefficients in solid-state reactions were calculated at 21.5 and 24 GPa for the first time. The new data are applicable for interpretation of the trace-element composition of the lower mantle inclusions in natural diamonds from kimberlite; the experimentally determined effect of pressure on the interphase (bridgmanite/CaSiO3-perovskite) REE partition coefficients can be a potential qualitative geobarometer for mineral inclusions in super-deep diamonds.
Abstract: The phases of CaAl2O4 and Ca2Al6O11 were synthesized at 15 GPa and 1600 °C. Microprobe data gave formulae Ca1.003Al1.998O4 and Ca2.05Al5.97O11, on the basis of 4 and 11 oxygen atoms. The crystal structures have been refined by single-crystal X-ray diffraction. Orthorhombic unitcell parameters for CaAl2O4 are a = 8.8569(10) Å; b = 2.8561(4) Å; c = 10.2521(11) Å; V = 259.34(5) Å3; Z = 8 (space group Pnma). The Ca2Al6O11 phase was obtained for the first time. It crystallizes with a space group P42/mnm and has lattice parameters a = b = 11.1675(4) Å; c = 2.83180(10) Å; V = 353.16(2) Å3; Z = 2. A Raman spectrum was obtained for a new phase for the first time. Our results suggest that both studied phases are stable under the condition of the transition zone and can be considered as potential aluminum concentrators in the Earth's deep geospheres.
Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights in situ sulphides....
Contributions to Mineralogy and Petrology, Vol. 159, 3, pp. 315-330.
Gonzalez-Jimienez, J.M., Marchesi, C., Griffin, W.L., Gutierrez-Narbona, R., Lorand, J-P., O'Reilly, S.Y., Garrido, C.J., Gervilla, F., Pearson, N.J., Hidas, K.
Transfer of Os isotopic signatures from peridotite to chromitite in the subcontinental mantle: insights from in situ analysis of platinum-group and base metal minerals (Ojen peridotite massif, southern Spain.
Comptes Rendus Geoscience, in press available 11p.
Africa, Morocco
Peridotite
Abstract: The Beni Bousera peridotite contains a diversity of pyroxenite layers. Several studies have postulated that at least some of them represent elongated strips of oceanic lithosphere recycled in the convective mantle. Some pyroxenites were, however, ascribed to igneous crystal segregation or melt-rock reactions. To further constrain the origin of these rocks, we collected 171 samples throughout the massif and examined their variability in relation with the tectono-metamorphic domains. A major finding is that all facies showing clear evidence for a crustal origin are concentrated in a narrow corridor of mylonitized peridotites, along the contact with granulitic country rocks. These peculiar facies were most likely incorporated at the mantle-crust boundary during the orogenic events that culminated in the peridotite exhumation. The other pyroxenites derive from a distinct protolith that was ubiquitous in the massif before its exhumation. They were deeply modified by partial melting and melt-rock reactions associated with lithospheric thinning.
Journal of Petrology, Vol. 57, 11-12, pp. 2251-2270.
Africa, Morocco
Deposit - Beni Bousera
Abstract: Correlations between major and minor transition elements in tectonically emplaced orogenic peridotites have been ascribed to variable degrees of melt extraction and melt-rock reaction processes, leading to depletion or refertilization. To elucidate how such processes are recorded in the subcontinental lithospheric mantle, we processed a large geochemical dataset for peridotites from the four tectono-metamorphic domains of the Beni Bousera orogenic massif (Rif Belt, northern Morocco). Our study reveals that variations in bulk-rock major and minor elements, Mg-number and modal mineralogy of lherzolites, as well as their clinopyroxene trace element compositions, are inconsistent with simple partial melting and mainly resulted from different reactions between melts and depleted peridotites. Up to 30% melting at <3 GPa and cryptic metasomatism can account for the geochemical variations of most harzburgites. In Grt-Sp mylonites, melting and melt-rock reactions are masked by tectonic mixing with garnet pyroxenites and subsolidus re-equilibration. In the rest of the massif, lherzolites were mostly produced by refertilization of a refractory protolith (Mg-number = 91, Ol = 70%, Cpx/Opx = 0.4) via two distinct near-solidus, melt- rock reactions: (1) clinopyroxene and orthopyroxene precipitation and olivine consumption at melt/rock ratios <0.75 and variable mass ratio between crystallized minerals and infiltrated melt ®, which are recorded fairly homogeneously throughout the massif; (2) dissolution of orthopyroxene and precipitation of clinopyroxene and olivine at melt/rock ratios <1 and R = 0.2-0.3, which affected mainly the Arie` gite-Seiland and Seiland domains. The distribution of secondary lherzolites in the massif suggests that the first refertilization reaction occurred prior to the differentiation of the Beni Bousera mantle section into petro-structural zones, whereas the second reaction was associated with the development of the tectono-metamorphic domains. Our data support a secondary, refertilization-related origin for most lherzolites in orogenic peridotite massifs.
Abstract: The Beni Bousera peridotite contains a diversity of pyroxenite layers. Several studies have postulated that at least some of them represent elongated strips of oceanic lithosphere recycled in the convective mantle. Some pyroxenites were, however, ascribed to igneous crystal segregation or melt–rock reactions. To further constrain the origin of these rocks, we collected 171 samples throughout the massif and examined their variability in relation with the tectono-metamorphic domains. A major finding is that all facies showing clear evidence for a crustal origin are concentrated in a narrow corridor of mylonitized peridotites, along the contact with granulitic country rocks. These peculiar facies were most likely incorporated at the mantle–crust boundary during the orogenic events that culminated in the peridotite exhumation. The other pyroxenites derive from a distinct protolith that was ubiquitous in the massif before its exhumation. They were deeply modified by partial melting and melt–rock reactions associated with lithospheric thinning.
Geochimica et Cosmochimica Acta, Vol. 232, pp. 303-328.
Africa, Morocco, Europe, Spain
UHP
Abstract: We present an integrated geochemical study of ultra-high pressure (UHP) garnet pyroxenites from the Ronda and Beni Bousera peridotite massifs (Betic-Rif Belt, westernmost Mediterranean). Based on their Sr-Nd-Pb-Hf isotopic systematics, we classify UHP garnet pyroxenites into three groups: Group A pyroxenites (Al 2 O 3 : 15-17.5 wt. %) have low initial 87 Sr/ 86 Sr, relatively high ? Nd , ? Hf and 206 Pb/ 204 Pb ratios, and variable 207 Pb/ 204 Pb and 208 Pb/ 204 Pb. Group B pyroxenites (Al 2 O 3 < 14 wt. %) are characterized by high initial 87 Sr/ 86 Sr and relatively low ? Nd , ? Hf and 206 Pb/ 204 Pb ratios. Group C pyroxenites (Al 2 O 3 ~ 15 wt. %) have depleted radiogenic signatures with relatively low initial 87 Sr/ 86 Sr and 206 Pb/ 204 Pb, high ? Nd and ? Hf , and their 207 Pb/ 204 Pb and 208 Pb/ 204 Pb ratios are similar to those of Group B pyroxenites. The major and trace element and isotopic compositions of UHP garnet pyroxenites support their derivation from ancient (1.5-3.5 Ga) oceanic crust recycled into the mantle and intimately stirred with peridotites by convection. However, the genesis of these pyroxenites requires also the involvement of recycled continental lower crust with an isotopic composition akin to the lower crustal section of the lithosphere where these UHP garnet pyroxenites now reside in. These oceanic and continental crustal components were stirred in different proportions in the convective mantle, originating pyroxenites with a more marked geochemical imprint of either oceanic (Group A) or continental lower crust (Group B), or hybrid compositions (Group C). The pyroxenite protoliths likely underwent several melting events, one of them related to the formation of the subcontinental lithospheric mantle and continental crust, generating restitic UHP garnet pyroxenites now preserved in the Ronda and Beni Bousera orogenic peridotites. The extent of melting was mostly 3 controlled by the bulk Mg-number (Mg#) of the pyroxenite protoliths, where protoliths with low Mg# experienced higher degrees of partial melting than sources with higher Mg#. Positive Eu and Sr anomalies in bulk rocks, indicative of their origin from cumulitic crustal gabbros, are preserved mostly in high Mg# pyroxenites due to their higher melting temperatures and consequent lower partial melting degrees. The results of this study show that the genesis of UHP garnet pyroxenites in orogenic peridotites requires a new recipe for the marble cake mantle hypothesis, combining significant recycling and stirring of both oceanic and continental lower crust in the Earth's mantle. Furthermore, this study establishes a firm connection between the isotopic signatures of UHP pyroxenite heterogeneities in the mantle and the continental lower crust.
Geochimica et Cosmochimica Acta, Vol. 232, pp. 303-328.
Mantle
deposit - Ronda, Beni Bousera
Abstract: We present an integrated geochemical study of ultra-high pressure (UHP) garnet pyroxenites from the Ronda and Beni Bousera peridotite massifs (Betic-Rif Belt, westernmost Mediterranean). Based on their Sr-Nd-Pb-Hf isotopic systematics, we classify UHP garnet pyroxenites into three groups: Group A pyroxenites (Al2O3: 15-17.5?wt.%) have low initial 87Sr/86Sr, relatively high eNd, eHf and 206Pb/204Pb ratios, and variable 207Pb/204Pb and 208Pb/204Pb. Group B pyroxenites (Al2O3?
Abstract: Subduction-Transform Edge Propagator (STEP) faults are the locus of continual lithospheric tearing at slab edges, resulting in sharp changes in the lithospheric and crustal thickness and triggering lateral and/or near-vertical mantle flow. However, the mechanisms at the lithospheric mantle scale are still poorly understood. Here, we present the microstructural study of olivine-rich lherzolite, harzburgite and wehrlite mantle xenoliths from the Oran volcanic field (Tell Atlas, NW Algeria). This alkali volcanic field occurs along a major STEP fault responsible for the Miocene westward slab retreat in the westernmost Mediterranean. Mantle xenoliths provide a unique opportunity to investigate the microstructures in the mantle section of a STEP fault system. The microstructures of mantle xenoliths show a variable grain size ranging from coarse granular to fine-grained equigranular textures uncorrelated with modal variations. The major element composition of the mantle peridotites provides temperature estimates in a wide range (790-1165?°C) but in general, the coarse-grained and fine-grained peridotites suggest deeper and shallower provenance depth, respectively. Olivine grain size in the fine-grained peridotites depends on the size and volume fraction of the pyroxene grains, which is consistent with pinning of olivine grain growth by pyroxenes as second phase particles. In the coarse-grained peridotites, well-developed olivine crystal preferred orientation (CPO) is characterized by orthorhombic and [100]-fiber symmetries, and orthopyroxene has a coherent CPO with that of olivine, suggesting their coeval deformation by dislocation creep at high-temperature. In the fine-grained microstructures, along with the weakening of the fabric strength, olivine CPO symmetry exhibits a shift towards [010]-fiber and the [010]- and [001]-axes of orthopyroxene are generally distributed subparallel to those of olivine. These data are consistent with deformation of olivine in the presence of low amounts of melts and the precipitation of orthopyroxenes from a melt phase. The bulk CPO of clinopyroxene mimics that of orthopyroxene via a topotaxial relationship of the two pyroxenes. This observation points to a melt-related origin of most clinopyroxenes in the Oran mantle xenoliths. The textural and geochemical record of the peridotites are consistent with interaction of a refractory harzburgite protolith with a high-Mg# melt at depth (resulting in the formation of coarse-grained clinopyroxene-rich lherzolite and wehrlite), and with a low-Mg# evolved melt in the shallow subcontinental lithospheric mantle (forming fine-grained harzburgite). We propose that pervasive melt-peridotite reaction - promoted by lateral and/or near-vertical mantle flow associated with lithospheric tearing - resulted in the synkinematic crystallization of secondary lherzolite and wehrlite and played a key effect on grain size reduction during the operation of the Rif-Tell STEP fault. Melt-rock reaction and secondary formation of lherzolite and wehrlite may be widespread in other STEP fault systems worldwide.
Abstract: The highly siderophile elements (HSE: Os, Ir, Ru, Rh, Pt, Pd, Re, Au) exist in solid solution in accessory base-metal sulfides (BMS) as well as nano-to-micron scale minerals in rocks of the subcontinental lithospheric mantle (SCLM). The latter include platinum-group minerals (PGM) and gold minerals, which may vary widely in morphology, composition and distribution. The PGM form isolated grains often associated with larger BMS hosted in residual olivine, located at interstices in between peridotite-forming minerals or more commonly in association with metasomatic minerals (pyroxenes, carbonates, phosphates) and silicate glasses in some peridotite xenoliths. The PGM found inside residual olivine are mainly Os-, Ir- and Ru-rich sulfides and alloys. In contrast, those associated with metasomatic minerals or silicate glasses of peridotite xenoliths consist of Pt, Pd, and Rh bonded with semimetals like As, Te, Bi, and Sn. Nanoscale observations on natural samples along with the results of recent experiments indicate that nucleation of PGM is mainly related with the uptake of HSE by nanoparticles, nanominerals or nanomelts at high temperature (> 900?°C) in both silicate and/or sulfide melts, regardless of the residual or metasomatic origin of their host minerals. A similar interpretation can be assumed for gold minerals. Our observations highlight that nanoscale processes play an important role on the ore-forming potential of primitive mantle-derived magmas parental to magmatic-hydrothermal deposits enriched in noble metals. The metal inventory in these magmas could be related with the physical incorporation of HSE-bearing nanoparticles or nanomelts during processes of partial melting of mantle peridotite and melt migration from the mantle to overlying continental crust.
Abstract: Impact cratering was a dominant geologic process in the early Solar System that probably played an active role in the crustal evolution of the young terrestrial planets. The Earth’s interior during the Hadean, 4.56 to 4 billion years ago, may have been too hot to sustain plate tectonics. However, whether large impacts could have triggered tectonism on the early Earth remains unclear. Here we conduct global-scale tectonic simulations of the evolution of the Earth through the Hadean eon under variable impact fluxes. Our simulations show that the thermal anomalies produced by large impacts induce mantle upwellings that are capable of driving transient subduction events. Furthermore, we find that moderate-sized impacts can act as subduction triggers by causing localized lithospheric thinning and mantle upwelling, and modulate tectonic activity. In contrast to contemporary subduction, the simulated localized subduction events are relatively short-lived (less than 10?Myr) with relatively thin, weak plates. We suggest that resurgence in subduction activity induced by an increased impact flux between 4.1 and 4.0 billion years ago may explain the coincident increase in palaeointensity of the magnetic field. We further suggest that transient impact-driven subduction reconciles evidence from Hadean zircons for tectonic activity with other lines of evidence consistent with an Earth that was largely tectonically stagnant from the Hadean into the Archaean.
Abstract: The presence and speciation of volatile C-H-O elements in the silicate systems play an important role in the genesis of magmas on the Earth’s mantle, due to the fact that these elements, mainly in the form of H2O, CO2, CH4 and CxHy, decrease the solidi temperatures of source rocks, making magmatism possible in Earth’s present day thermal conditions [1]. Among those elements, carbon is the only element that changes its valence according to the oxygen fugacity (fO2) conditions of the environment, resulting in different speciation, as: CO3 -2, CO2, Cgraphite/diamond, CH4 or heavier hydrocarbons. In the present work, we are determining phase stability of minerals, water, CO2 and CH4 in the system Nefeline-Kalsilite-Diopside. Our experiments are conducted under 4.0 GPa and temperatures up to 1300°C, using a 1000 tonf hydraulic press coupled with toroidal chambers. Preliminary experiments performed at 1300°C and 4.0GPa (initial composition in the Olivine-Quartz- Kalsalite/Nepheline system: 40mol% Ol90, 40mol% Nph50Kls50 and 20mol% Qz, PH2O,CO2=Ptotal) resulted in the formation of forsterite (Fo90) in equilibrium with phlogopite (Phl), melt and volatile phases (CO2 and CH4). Closer to the Diopside vertice, the addition of CO3 to the sample resulted in a imisibility of a carbonatitic and a silicatic melt, in which the carbonititic melt is enriched in sodium, while the silcate melt is enriched in potassium. Appart from that, experiments in different parts of the diagram suggest compositions from nephelinite-kalsilitite to lamproites composition for the silicate melt in equilibrium with diopside (solid solution with omphacite) and phlogopite. This work is a continuation of previous work in the anhydrous diagram and future works will provide the addition of CH4 as the volatile phase
Earth and Planetary Science Letters, Vol. 506, pp. 1-7.
Mantle
geodynamics
Abstract: We present a theoretical investigation, based on ab initio calculations and the quasi-harmonic approximation, on the stability properties of magnesium (MgCO3) and calcium (CaCO3) carbonates at high temperatures and pressures. The results indicate that those carbonates should be stable in the Earth's lower mantle, instead of dissociating into other minerals, in chemical environments with excess of SiO2, MgO, or MgSiO3. Therefore, considering the lower mantle chemical composition, consisting mostly of the MgSiO3 and MgO minerals, calcium and magnesium carbonates are the primary candidates as carbon hosts in that region. For the thermodynamic conditions of the mantle, the results also indicate that carbon should be primarily hosted on MgCO3, contrasting with what was found by other theoretical studies, which neglected temperature effects. Finally, the results indicate that carbon, in the form of free CO2, is unlikely in the lower mantle.
Lithospheric detachment and slab breakoff under the Variscan collisional orogen: keys to the origin of diamond bearing crustal rocks in the Bohemmian Massif.
18th. International Mineralogical Association Sept. 1-6, Edinburgh, abstract p.218.
Modification of mineral inclusions in garnet under high pressure conditions: experimental simulation and application to carbonate silicate rocks of Kokchetetav
Russian Geology and Geophysics, Vol. 50, 12, pp. 1153-1168.
Abstract: Heat flow and heat production data complement seismic information and provide strong constraints on crustal composition, thickness and evolution. They have helped understand the nature of the Mohorovicic discontinuity and the variations in seismic velocities below the Moho. Notably, heat flow studies have delineated the vertical distribution of heat producing elements throughout the crust and in the upper most mantle lithosphere. Analysis of global data sets on heat flow and crustal thickness demonstrate that there is no correlation between these two variables. This is due to the large spatial variations in crustal composition and heat production that exist within a single geological province. For a given crustal thickness, the Moho temperature varies within a wide range (˜ 300 K) depending on surface heat flux and crustal heat production. Thus one cannot use generic models based on a “type” crustal column to calculate crustal geotherms. In stable regions, lower crustal temperatures depend on the amount and vertical distribution of heat producing elements in the crust. These temperatures determine the conditions of crustal stability and impose a limit on the maximum thickness of a stabilized crust.
Geochemistry International, Vol. 56, 13, pp. 1289-1321.
Mantle
geophysics
Abstract: The generation of crustal material and the formation of continental crust with a thickness of ˜40 km involve different physical mechanisms operating over different time-scales and length-scales. This review focusses on the building of a thick crustal assemblage and on the vertical dimension where the consequences of gravity-driven processes are expressed most clearly. Continental crustal material is produced by a sequence of crust and mantle mlelting, fractionation of basaltic melts and sinking of dense mafic cumulates. The repeated operation of these mechanisms over tens of million years leads to a thick stably stratified crust. We evaluate the main mechanisms involved from a physics perspective and identify the key controls and constraints, with special attention to thermal requirements. To form magma reservoirs able to process significant magma volumes and to allow the foundering of mafic cumulates, melt must be fed locally at rates that are larger than that of average crustal growth. This requires the temporary focussing of magmatic activity in a few centers. In some cases, foundering of dense cumulates does not go to completion, leaving a deformed residual body bearing tell-tale traces of the process. Crust must be thicker than a threshold value in a 30-45 km range for mafic cumulates to sink into the mantle below the crust. Once that threshold thickness has been reached, further additions lead to increase the proportion of felsic material in the crust at the expense of mafic lithologies which disappear from the crust. This acts to enhance radiogenic heat production in the crust. One consequence is that crustal temperatures can be kept at high values in times of diminished melt input and also when magmatic activity stops altogether, which may lead to post-orogenic intracrustal melting and differentiation. Another consequence is that the crust becomes too weak mechanically to withstand the elevation difference with neighbouring terranes, which sets a limit on crustal thickening. The thermal structure of the evolving crust is a key constraint on the overall process and depends strongly on radiogenic heat production, which is surely one of the properties that make continental crust very distinctive. In the Archean Superior Province, Canada, the formation of juvenile continental crust and its thermal maturation 2.7 Gy ago can be tracked quite accurately and reproduced by calculations relying on the wealth of heat flow and heat production data available there. Physical models of magma ascent and storage favour the formation of magma reservoirs at shallow levels. This suggests that crustal growth proceeds mostly from the top down, with material that gets buried to increasingly large depths. Vertical growth is accompanied by lateral spreading in two different places. Within the crust, magma intrusions are bound to extend in the horizontal direction. Deeper down, lateral variations of Moho depth that develop due to the focussing of magmatic activity get relaxed by lower crustal flow. This review has not dealt with processes at the interface between the growing crust and the mantle, which may well be where dikes get initiated by mechanisms that have so far defied theoretical analyses. Research in this particular area is required to further our understanding of continental crust formation.
Abstract: Permian dikes, sills, and diatremes in southern Illinois and northwestern Kentucky (the Omaha, Wildcat Hills, Cottage Grove, Will Scarlet, Williams, Grant, and Clay Lick intrusions) share similar geochemistry and are classified as ultramafic lamprophyres. Major element compositions are 30-35 wt% SiO2, 6-7% Al2O3, 12-14% FeOt, 16-19% MgO, 3-5% TiO2, 11-16% CaO, 0.1-0.7% Na2O, 1.2-2.7% K2O, and 0.4-1.3% P2O5. The Grant Intrusive Breccia is an exception, with lower SiO2, Al2O3, FeOt, MgO, TiO2, and higher CaO. Typically, these rocks are fine grained, with phlogopite, serpentinized olivine ( Fo88), diopside, perovskite, Fe-Ti-spinel, apatite, and calcite. Blocky and lath-shaped pseudomorphs in some samples probably represent melilite, which would make the rocks alnöites. The Grant and Williams diatremes contain sedimentary and igneous clasts (including amphibole megacrysts) within a carbonate-rich matrix. The Grant exhibits pelletal lapilli and is characterized as a lamprophyre-carbonatite tuffisite. Trace element patterns exhibit enrichment of LREE, strong REE fractionation, and relative depletions of K, Sr, Zr, and Hf, closely matching those of the mela-aillikites of Aillik Bay, Labrador. The Grant Intrusive exhibits even greater REE enrichment and notable peaks at Nb, La, and Ce. Geochemical characteristics, including distributions of 143Nd/144Nd and 87Sr/86Sr, are consistent with near-primary melts from a metasomatized peridotite source containing phlogopite-rich veins. Derivation of the lamprophyres from carbonate-rich parental melts similar to the Grant Intrusive could be achieved by separation of carbonatite. A narrow range of initial 87Sr/86Sr (0.70301-0.70449), and initial eNd (3.7-5.1), suggests a uniform mantle source close to Bulk Earth. T-depleted mantle model ages range from 540 to 625 Ma, and might correlate with timing of enrichment of a lithospheric mantle source during the breakup of Rodinia.
Mineralogy and geochemistry of perovskite- rich pyroxenites
Geological Association of Canada (GAC)/Mineralogical Association of Canada (MAC) Vancouver 90 Program with Abstracts, Held May 16-18, Vol. 15, p. A83. Abstract
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 65-74.
Global
Carbonatite
Abstract: For nearly 50 years, carbonatites have been the primary sources of niobium and rare earth elements (REEs), particularly the light REEs including La, Ce, Pr, and Nd. In addition, carbonatites may be enriched in other critical elements and have the potential to be future sources. Currently, only fi ve of the more than 500 known carbonatites in the world are being mined for REEs: Bayan Obo (Inner Mongolia, China); Maoniuping (Sichuan, China); Dalucao (or Daluxiang, Sichuan, China); and Mountain Pass (California, USA), and the carbonatite-derived laterite at Mount Weld (Australia). To achieve ore-grade REE enrichment, initial carbonatitic magmas require an adequate endowment of REEs and need to evolve in ways for these elements to concentrate in REE-bearing mineral phases. Radiogenic isotope studies of carbonatites clearly point to a mantle origin, but a wide range in isotopic compositions has led to contrasting views about the specifi c mantle reservoir(s) that sourced carbonatites. In this study we use the neodymium and strontium isotopic compositions of a suite of mineralized carbonatites to establish the nature of the source magmas. We examine samples that span a wide range in age (~23 Ma to 1385 Ma), Nd concentrations (3720 to 32,900 ppm), and Sr concentrations (2290 to 167,900 ppm). Our Nd and Sr isotopic data include multiple samples from Mountain Pass (USA; eNd i = -3.1 to -5.4, Sri = 0.70512 to 0.70594), Elk Creek (USA; ~eNd i = 1.7, Sri = 0.7035), and Maoniuping (China; eNd i = -4.1 and -4.2, Sri = 0.70627 and 0.70645), and one sample each from Bear Lodge (USA; eNd i = 0.1, Sri = 0.70441), Kangankunde (Malawi; eNd i = 3.3, Sri = 0.70310), Adiounedj (Mali; eNd i = -0.1, Sri = 0.70558), and Mushgai Khudag (Mongolia; eNd i = -1.3, Sri = 0.70636). Isotopic data from two producing carbonatite REE deposits (Mountain Pass and Maoniuping) have broadly similar isotopic compositions (eNd i = -3.1 to -5.4 and Sri = 0.7051 to 0.7065), and these compositions point to a carbonated source in the lithospheric mantle. Mineralized but unmined carbonatites have higher Nd initial isotopic compositions (eNd i = -1.3 to 3.3) and a wider range in Sr isotopic compositions (Sri = 0.70310 to 0.70637), but these data are consistent with a lithospheric mantle reservoir.
Mineralogical Magazine Open access special publication Critical metal mineralogy and ore genesis, Vol. 82 (S1) pp. S115-S131.
Europe, Norway
carbonatite
Abstract: The Fen Complex in Norway consists of a ~583 Ma composite carbonatite-ijolite-pyroxenite diatreme intrusion. Locally, high grades (up to 1.6 wt.% total REE) of rare-earth elements (REE) are found in a hydrothermally altered, hematite-rich carbonatite known as rødbergite. The progressive transformation of primary igneous carbonatite to rødbergite was studied here using scanning electron microscopy and inductively coupled plasma-mass spectrometry trace-element analysis of 23 bulk samples taken along a key geological transect. A primary mineral assemblage of calcite, dolomite, apatite, pyrite, magnetite and columbite with accessory quartz, baryte, pyrochlore, fluorite and REE fluorocarbonates was found to have transformed progressively into a secondary assemblage of dolomite, Fe-dolomite, baryte, Ba-bearing phlogopite, hematite with accessory apatite, calcite, monazite-(Ce) and quartz. Textural evidence is presented for REE fluorocarbonates and apatite breaking down in igneous carbonatite, and monazite-(Ce) precipitating in rødbergite. The importance of micro-veins, interpreted as feeder fractures, containing secondary monazite and allanite, is highlighted. Textural evidence for included relics of primary apatite-rich carbonatite are also presented. These acted as a trap for monazite-(Ce) precipitation, a mechanism predicted by physical-chemical experiments. The transformation of carbonatite to rødbergite is accompanied by a 10-fold increase in REE concentrations. The highest light REE (LREE) concentrations are found in transitional vein-rich rødbergite, whereas the highest heavy REE (HREE) and Th concentrations are found within the rødbergites, suggesting partial decoupling of LREE and HREE due to the lower stability of HREE complexes in the aqueous hydrothermal fluid. The hydrothermal fluid involved in the formation of rødbergite was oxidizing and had probably interacted with country-rock gneisses. An ore deposit model for the REE-rich rødbergites is presented here which will better inform exploration strategies in the complex, and has implications for carbonatite-hosted REE resources around the world.
Abstract: The São Francisco Craton, in Brazil, together with adjacent orogenic systems formed during Gondwana assemblage, are well-suited for the study of crustal growth processes. The region's geological history is marked by a series of complete tectono-metamorphic cycles, from the Archean to late Neoproterozoic, comprising arc-related magmatism followed by continental collisions and ultimately post-tectonic igneous events and rifting. In this contribution, a comprehensive isotopic database was compiled from the literature, composed mainly of high-quality U-Pb magmatic and metamorphic ages (ca. 1000), together with Lu-Hf (ca. 1300) and Sm-Nd (ca. 300) data. Using this database, combined with a tectonic/geochemical synthesized review of the region, it is possible to test which of the available contending models can better explain the apparent periodicity in the formation of the continental crustal. Some interpreted the peaks and troughs in the crustal age record as periods of increased magmatic production, controlled by periodic mantellic events. Another hypothesis is that subduction-related rocks are shielded from tectonic erosion after continental amalgamation, the peaks thus reflecting enhanced preservation potential. The latter hypothesis is favored, as the variability regarding the timing of arc-related peak magmatic production (U-Pb age peaks) from different tectonic provinces around the globe and in the considered regions, coupled to the fact that peak arc-production is always closely followed in time by major continental amalgamations (supercontinent formation), precludes a unified global causation effect, such as mantellic overturns or slab avalanches, and supports the preservation bias hypothesis. Furthermore, the worldwide (including the São Francisco Craton) occurrence of plume-related magmatism is concentrated during the periods of supercontinent break-up (i.e. after major collisions), which better relates to a top-down control on mantle convection and opposes most of the models that advocate for the primary periodicity of magmatic production, which predict enhanced plume activity slightly prior or concomitant to supercontinent formation events.
Abstract: Using IR-Fourier spectrometry (FTIR) and simultaneous thermal analysis combined with quadrupole mass spectrometry of thermal decomposition products (STA + QMS), olivines and clinopyroxene from xenolites of spinel and garnet lherzolites contained in kimberlites and alkaline basalts were studied to confirm the occurrence of hydrogen and carbon within the structure of the minerals, as well as to specify the forms of H and C. The presence of hydroxyl ions (OH-) and molecules of crystal hydrate water (H2Ocryst) along with CO2, CH, CH2, and CH3 groups was detected, which remained within the structures of mantle minerals up to 1300°C (by the data of both techniques). The total water (OH-and H2Ocryst) was the prevailing component of the C-O-H system.
The Extractive Industries and Society, Vol. 4, pp. 172-179.
Africa, Zimbabwe
artisanal mining
Abstract: The deployment of soldiers’ in diamond mining areas in Zimbabwe is beginning to receive much scholarly attention, partly because scholars researching on such issues are mainly driven by the meta-narratives of ‘artisanal miners’, popularly known as "magweja" in the Zimbabwean context. In many cases soldiers are presented as perpetrators of violence within deployed areas, with magweja and villagers, as victims of military deployment. While this is not untrue, this article explores the ways in which soldiers developed mutual relationships with magweja, friendships and interactions with villagers, including sexual relationships in the communities surrounding the diamond area. However, we assert that these relationships were always implicitly characterised by unequal power dynamics in which the authority of deployed soldiers was ominously present and fear sometimes informed the actions of villagers. Soldiers’ power was always materially represented by the authority vested in them by a powerful demagogic state. It was visibly represented through their combat uniforms, and the gun as part of their daily standing orders, including other soldiering routines such as patrols, and guard duties. We argue that even beyond these circumscribed conditions of relations building, the people behind the combat uniforms had their own agencies that never always resonated with that of the state. Their actions were informed by the chain of command and the consequences wrought by failing to abide by standing orders. In this article, we illuminate those hidden narratives and expose the manner in which the dictatorial state instrumentalises its armed forces despite the disparate personal agencies of those soldiers which are suppressed by the very nature of military service. The paper is based on interviews with soldiers, "magweja" and villagers.
Abstract: Our discovery of moissanite grains in a peralkaline syenite from the Água de Pau Volcano (São Miguel, Azores Islands, Portugal) represents the first report of this mineral in present day oceanic geodynamic settings. Raman spectroscopy and single-crystal X-ray diffraction show the presence of both the 6H and 4H polytypes with the predominance of the first one. The distribution of trace elements is homogeneous, except for Al and V. Azorean moissanite often hosts rounded inclusions of metallic Si and other not yet identified metallic alloys. A process involving a flushing of CH4-H2 ultra-reducing fluids in the alkaline melts might be considered as a possible mechanism leading to the formation of natural SiC, thus calling for strongly reducing conditions that were locally met in the crust-mantle beneath the São Miguel Island.
Marker, A., Friedrich, G., Carvalho, A., Melfi, A.
Control of the distribution of Manganese, Cobalt, Zinc, Zrirconium, Titanium and REEs during the evolution of lateritic covers above ultramafic complexes
Journal of Geochemical Exploration, Special Publications Geochemical, Vol. 40, No. 1-3, pp. 361-384
Abstract: Engineering coherent systems is a central goal of quantum science. Color centers in diamond are a promising approach, with the potential to combine the coherence of atoms with the scalability of a solid-state platform. We report a color center that shows insensitivity to environmental decoherence caused by phonons and electric field noise: the neutral charge state of silicon vacancy (SiV0). Through careful materials engineering, we achieved >80% conversion of implanted silicon to SiV0. SiV0 exhibits spin-lattice relaxation times approaching 1 minute and coherence times approaching 1 second. Its optical properties are very favorable, with ~90% of its emission into the zero-phonon line and near -transform-limited optical linewidths. These combined properties make SiV0 a promising defect for quantum network applications.
Marks, M.A.W., Rudnick, R.L., McCammon, C., Vennemann, T., Markl, G.
Arrested kinetic Li isotope fractionation at the margin of the Ilimaussaq complex: evidence for open system processes during final cooling peralkaline igneous rocks
Marks, M.A.W., Neukirchen, F., Vennemann, T., Markl, G.
Textural, chemical and isotopic effects of late magmatic carbonatitic fluids in the carbonatite syenite Tamazeght complex, High Atlas Mountains, Morocco.
Kohler, J., Schonenberger, J., Upton, B., Markl, G.
Halogen and trace element chemistry in the Gardar Province, South Greenland: subduction related mantle metasomatism and fluid exsolution from alkalic melts.
Mangler, M.F., Marks, M.A.W., Zaitsev, A.N., Eby, G.N., Markl, G.
Halogens (F, Cl and Br) at Oldoinyo Lengai volcano ( Tanzania): effects of magmatic differentiation, silicate, natrocarbonatite melt seperation and surface alteration of natrocarbonatite.
Abstract: Textural and compositional variations of apatite from four intrusions with different characteristic features of the rift-related alkaline Gardar Province were investigated: dyke rocks that belong to the most primitive rocks of the Province (Isortoq), nepheline-syenites associated with a carbonatite (Grønnedal-Ika), SiO2-saturated and SiO2-oversaturated syenites (Puklen) and nepheline-syenites displaying the transition from miaskitic to agpaitic mineral assemblages (Motzfeldt, Fig.1). Additionally, apatites from these intrusions were compared with other apatites of the Gardar Province. These include apatites from the Older Giant Dyke Complex, the Younger Giant Dyke Complex (both from the Tugtutôq region) and a narsarsukite-bearing trachytic dyke (Igdlutalik), as well as apatites from the Kûngnât, the North Qôroq and the Ilímaussaq intrusive complexes. This results in a complete overview of rift-related magmatites of the Gardar Province, ranging from primitive to highly evolved rocks. Backscattered electron images reveal the presence of various types of apatite textures including (i) growth zonation (concentric and oscillatory) that formed during magmatic differentiation and (ii) overgrowth and secondary textures (rounded cores, patchy zonation and overgrowth rims) due to fluid/melt induced metasomatic overprint and intracrystalline diffusion (Fig.2). Additionally, apatite compositions were analyzed with wavelength-dispersive electron microprobe analyses. During the crystallization history of the different intrusions, as well as within samples (documented by zoning patterns), increasing concentrations are observed for Si, REE, Na and F, whereas Cl shows a decreasing trend. However, for F, Cl and Na these trends are only observed in dyke rocks. Compositional variation of the investigated apatites is mainly due to substitution of Ca and P by variable amounts of Si, Na and REE. This study reveals that variations in the chemical composition of apatite are useful tools to obtain geochemical information about the host magma and its magmatic evolution. Here, Si and REE were found to be reliable petrogenetic indicators, whereas Na, F and Cl are only applicable in fast cooling systems to avoid redistribution of those elements.
Abstract: The 2060 Ma old Palabora Carbonatite Complex (PCC), South Africa, comprises diverse REE mineral assemblages formed during different stages and reflects an outstanding instance to understand the evolution of a carbonatite-related REE mineralization from orthomagmatic to late-magmatic stages and their secondary post-magmatic overprint. The 10 rare earth element minerals monazite, REE-F-carbonates (bastnäsite, parisite, synchysite), ancylite, britholite, cordylite, fergusonite, REE-Ti-betafite, and anzaite are texturally described and related to the evolutionary stages of the PCC. The identification of the latter five REE minerals during this study represents their first described occurrences in the PCC as well as in a carbonatite complex in South Africa. The variable REE mineral assemblages reflect a multi-stage origin: (1) fergusonite and REE-Ti-betafite occur as inclusions in primary magnetite. Bastnäsite is enclosed in primary calcite and dolomite. These three REE minerals are interpreted as orthomagmatic crystallization products. (2) The most common REE minerals are monazite replacing primary apatite, and britholite texturally related to the serpentinization of forsterite or the replacement of forsterite by chondrodite. Textural relationships suggest that these two REE-minerals precipitated from internally derived late-magmatic to hydrothermal fluids. Their presence seems to be locally controlled by favorable chemical conditions (e.g., presence of precursor minerals that contributed the necessary anions and/or cations for their formation). (3) Late-stage (post-magmatic) REE minerals include ancylite and cordylite replacing primary magmatic REE-Sr-carbonates, anzaite associated with the dissolution of ilmenite, and secondary REE-F-carbonates. The formation of these post-magmatic REE minerals depends on the local availability of a fluid, whose composition is at least partly controlled by the dissolution of primary minerals (e.g., REE-fluorocarbonates). This multi-stage REE mineralization reflects the interplay of magmatic differentiation, destabilization of early magmatic minerals during subsequent evolutionary stages of the carbonatitic system, and late-stage fluid-induced remobilization and re-/precipitation of precursor REE minerals. Based on our findings, the Palabora Carbonatite Complex experienced at least two successive stages of intense fluid–rock interaction.
Abstract: Pyrochlore from the Kaiserstuhl volcanic complex (SW Germany) shows textural and compositional differences between various coarse-grained calcite-carbonatite bodies (Badberg, Degenmatt, Haselschacher Buck, Orberg) and extrusive carbonatites (Henkenberg, Kirchberg). Oscillatory-zoned F-rich pyrochlore with up to 69?wt% Nb2O5 is common in all coarse-grained calcite-carbonatite bodies and probably formed during magmatic conditions. However, only in some of the samples from the Badberg, partly resorbed U- and Ta-enriched pyrochlore cores with up to 22?wt% UO2 and 9?wt% Ta2O5 have been identified, which are interpreted as being inherited from underlying nosean syenites. Pyrochlore data from a drill core penetrating the Badberg indicate increasing contents of REE, U, and Ta with depth, while Nb, F and Na contents decrease. This may reflect the combined effects of fractional crystallization and assimilation (AFC) or indicates a multi-stage emplacement of the carbonatitic magma. Patchy-zoned ceriopyrochlore and REE- and Th-enriched pyrochlore with up to 19?wt% total REE2O3 and 6.5?wt% ThO2 is largely restricted to samples from the Orberg and probably formed during hydrothermal conditions. This can be related to the relatively evolved character of the Orberg carbonatites, based on their relatively high whole-rock Nb/Ta and Zr/Hf mass ratios. This study demonstrates that the textural and compositional variation of pyrochlore in carbonatites is a powerful tool to distinguish magmatic, hydrothermal and weathering processes in carbonatitic systems.
Abstract: A detailed electron microprobe study has been carried out on the compositional variations of mica and apatite from carbonatites, phoscorites and associated pyroxenites (and fenites) of the Loolekop deposit, Palabora Carbonatite Complex (South Africa). Mica in pyroxenites and fenites is Mg-rich biotite, whilst micas in carbonatites and phoscorites are compositionally diverse including phlogopite, Ba-rich phlogopite (up to 30% kinoshitalite component), IVAl-rich phlogopite (up to 30% eastonite component) and tetraferriphlogopite. The various types of phlogopites are interpreted as orthomagmatic phases, whereas tetraferriphlogopite precipitation was a late-magmatic to hydrothermal process that additionally introduced REE into the system. Orthomagmatic apatite is generally REE- and Sr-poor fluorapatite and does not show large compositional differences between rock types. Apatite associated with the late-stage tetraferriphlogopite mineralization reaches higher levels of REE (up to 4.9?wt%), Si (up to 1.5?wt% SiO2), Sr (up to 2.6?wt% SrO) and Na (up to 1.0?wt% Na2O). The compositional variation of micas and apatites, which is affiliated with distinct rock types, reflects the multi-stage evolution of the Loolekop deposit and provides detailed insight into the relationships of the carbonatite-phoscorite assemblage. The obtained data support the separation of phoscorite and carbonatite by immiscibility from a common parental magma, which may happen due to a decrease of temperature and/or pressure during the ascent of the magma. This results in a density contrast between the carbonatitic and phoscoritic components that will lead to descending phoscorite accumulations at the outer zones of the magma channel and a jet-like ascent (further promoted by its extremely low viscosity) of the carbonatite magma. The genetic model deduced here explains the peculiar association of carbonatites, phoscorites and silicate rocks in many alkaline complexes worldwide.
Abstract: A detailed electron microprobe study has been carried out on the compositional variations of mica and apatite from carbonatites, phoscorites and associated pyroxenites (and fenites) of the Loolekop deposit, Palabora Carbonatite Complex (South Africa). Mica in pyroxenites and fenites is Mg-rich biotite, whilst micas in carbonatites and phoscorites are compositionally diverse including phlogopite, Ba-rich phlogopite (up to 30% kinoshitalite component), IVAl-rich phlogopite (up to 30% eastonite component) and tetraferriphlogopite. The various types of phlogopites are interpreted as orthomagmatic phases, whereas tetraferriphlogopite precipitation was a late-magmatic to hydrothermal process that additionally introduced REE into the system. Orthomagmatic apatite is generally REE- and Sr-poor fluorapatite and does not show large compositional differences between rock types. Apatite associated with the late-stage tetraferriphlogopite mineralization reaches higher levels of REE (up to 4.9?wt%), Si (up to 1.5?wt% SiO2), Sr (up to 2.6?wt% SrO) and Na (up to 1.0?wt% Na2O). The compositional variation of micas and apatites, which is affiliated with distinct rock types, reflects the multi-stage evolution of the Loolekop deposit and provides detailed insight into the relationships of the carbonatite-phoscorite assemblage. The obtained data support the separation of phoscorite and carbonatite by immiscibility from a common parental magma, which may happen due to a decrease of temperature and/or pressure during the ascent of the magma. This results in a density contrast between the carbonatitic and phoscoritic components that will lead to descending phoscorite accumulations at the outer zones of the magma channel and a jet-like ascent (further promoted by its extremely low viscosity) of the carbonatite magma. The genetic model deduced here explains the peculiar association of carbonatites, phoscorites and silicate rocks in many alkaline complexes worldwide.
Abstract: Alkaline complexes consist of variable mantle-derived silicate rocks, ranging from primitive alkali basalts, melilitites, nephelinites and basanites towards tephrites and more evolved phonolites, respectively their plutonic equivalents. This lithological variance is also expressed by a wide range of redox conditions that vary by several log units around the synthetic fayalite-magnetite-quartz (FMQ) buffer. However, only some of these complexes are characterized by the occurrence of carbonatites which must be related to specific formation conditions. Based on textural, mineralogical and geochemical observations, we calculated the redox conditions of carbonatites and associated silicate rocks for seven alkaline complexes (Kaiserstuhl, Sokli, Kovdor, Palabora, Magnet Cove, Oka, Jacupiranga) which are considered to represent typical carbonatite-alkaline silicate rock associations. In combination with a comprehensive literature review, we demonstrate that carbonatite-bearing alkaline complexes formed under highly oxidized conditions and hence, belong to the most oxidized alkaline rocks at all. This is consistent with the prerequisite of a carbonated mantle as the source region for carbonatite complexes, which requires redox conditions distinctively above that for mean lithospheric or asthenospheric mantle. Carbonatitemetasomatized peridotites also show high redox conditions and might not only reflect an interaction between peridotite and carbonatitic melts/fluids, but at least partly represent the carbonated mantle source for crustally emplaced carbonatite complexes. We therefore suggest that the oxidation state of carbonatites and associated silicate rocks provides direct information about an extraordinary oxidized parental mantle source.
Abstract: A detailed electron microprobe study has been carried out on the compositional variations of mica and apatite from carbonatites, phoscorites and associated pyroxenites (and fenites) of the Loolekop deposit, Palabora Carbonatite Complex (South Africa). Mica in pyroxenites and fenites is Mg-rich biotite, whilst micas in carbonatites and phoscorites are compositionally diverse including phlogopite, Ba-rich phlogopite (up to 30% kinoshitalite component), IVAl-rich phlogopite (up to 30% eastonite component) and tetraferriphlogopite. The various types of phlogopites are interpreted as orthomagmatic phases, whereas tetraferriphlogopite precipitation was a late-magmatic to hydrothermal process that additionally introduced REE into the system. Orthomagmatic apatite is generally REE- and Sr-poor fluorapatite and does not show large compositional differences between rock types. Apatite associated with the late-stage tetraferriphlogopite mineralization reaches higher levels of REE (up to 4.9?wt%), Si (up to 1.5?wt% SiO2), Sr (up to 2.6?wt% SrO) and Na (up to 1.0?wt% Na2O). The compositional variation of micas and apatites, which is affiliated with distinct rock types, reflects the multi-stage evolution of the Loolekop deposit and provides detailed insight into the relationships of the carbonatite-phoscorite assemblage. The obtained data support the separation of phoscorite and carbonatite by immiscibility from a common parental magma, which may happen due to a decrease of temperature and/or pressure during the ascent of the magma. This results in a density contrast between the carbonatitic and phoscoritic components that will lead to descending phoscorite accumulations at the outer zones of the magma channel and a jet-like ascent (further promoted by its extremely low viscosity) of the carbonatite magma. The genetic model deduced here explains the peculiar association of carbonatites, phoscorites and silicate rocks in many alkaline complexes worldwide.
Abstract: Contamination of carbonatites with crustal or cogenetic intrusive rocks is generally not considered to play an important role during carbonatite magmatism, because carbonatitic melts have low densities and viscosities, enabling them to rapidly ascend. Potential contamination by silicate rocks in carbonatites cannot easily be detected by means of radiogenic isotope data (such as Sr, Nd and Pb isotope data) as carbonatites often show high concentrations of these elements and their isotope systems are thereby “buffered” against contamination with silicate rocks. Textural, mineralogical and geochemical observations in carbonatites from the Kaiserstuhl (Germany) provide evidence for the interaction of carbonatitic magma with previously emplaced nosean syenites. This caused replacement of alkali feldspar by haüyne and recrystallization of garnet and clinopyroxene in the xenoliths, which released larger amounts of K, Al, Si and Fe. As a result, blackwall-like mica seams around the xenoliths formed and and compositionally distinct mica and clinopyroxene crystallized in the surrounding carbonatite. Moreover, the local increase of silica activity during contamination enabled strong REE enrichment in apatite via a coupled substitution involving Si, which demonstrates the potential influence of Si contamination on REE mineralization in carbonatites. We further suggest that the presence and composition of clinopyroxene and mica in carbonatites may be useful indicators for contamination processes during their emplacement. Mass-balance calculations based on experimental constraints for the solubility of Al and Si in carbonatitic magmas suggest that only minor amounts of mica can form from carbonatitic melt. Therefore, larger amounts of mica and mica-dominated lithologies (glimmerites) as observed in many carbonatite complexes suggest that some Si and Al in carbonatites may be sourced from surrounding host rocks. We hypothesize that assimilation and contamination processes in carbonatites may be the rule rather than an exception.
Abstract: Studies on fluid inclusions in carbonatitic rocks are essential to understand the physicochemical processes involved in carbonatite-related hydrothermal ore mineralization. Although little is known about the composition of carbonatite-derived fluids. We investigated fluid inclusions in the Kaiserstuhl carbonatites, SW Germany [1,2] and identified four different types typically known from carbonatitic systems worldwide [3]: (I): Vapor-poor H2O-NaCl fluids with <50 wt.% salinity. (II): Vapor-rich H2O-NaCl-CO2 fluids with <5 wt.% salinity. (III): Multi-component fluids with high salinity and CO2. (IV): Multi-component fluids with high salinity, no CO2. Homogenization temperatures (156 to 530°C) of all fluid types generally show a wide range [this study, 2]. Primary type I fluid inclusions occur in early magmatic olivine/monticellite, as well as paragenetically later apatites and calcites [2]. This indicates a ubiquitous existence of a saline brine, which does not reach saturation with respect to halite, during early to late crystallization stages. Liquidus surface modelling based quantifications for fluid type III suggest that carbonatite melts predomonantly exsolve Na-K-sulfate-carbonate/bicarbonate-chloride brines (type III or IV, respectively). Such fluid inclusions, with type III (CO2-free) on one side and type IV (and II, both CO2-rich) on the other side, may represent immiscible fluids that were trapped after segregation by boiling from a parental highly saline brine (type I). Fluid boiling, in turn, is probably triggered by a rapid pressure release during “pneumatic hammer-like,” discontinuous melt ascent.
Earth and Planetary Science Letters, Vol. 533, 11p. Pdf
Mantle
carbonatite
Abstract: A detailed investigation on seven carbonatites and associated alkaline rock complexes (Kaiserstuhl, Sokli, Kovdor, Palabora, Oka, Magnet Cove, Jacupiranga), together with a world-wide comparison between carbonatites, alkaline silicate rocks and mantle xenoliths, implies peculiar redox conditions for carbonatite-bearing alkaline complexes: Carbonatites and associated alkaline rocks in continental settings crystallize from relatively oxidized magmas, on average 1.4 log units () and 1.3 log units () above the synthetic fayalite-magnetite-quartz (FMQ) buffer. In contrast, alkaline rocks in continental settings that lack associated carbonatites reveal rather reduced conditions (mean ; ). The calculated redox conditions for carbonatites and associated silicate rocks demonstrate that these crystallize from relatively oxidized mantle-derived melts compared to the general range found for alkaline rocks in continental settings.
Geochimica et Cosmochimica Acta, Vol. 277, pp. 224-242. pdf
Europe, Germany
carbonatite
Abstract: Studies of fluid inclusions in carbonatitic rocks are essential for understanding physicochemical processes involved in carbonatite-related hydrothermal ore mineralization and fenitization. However, the composition of many carbonatite-derived fluids is challenging to quantify, which hampers their detailed interpretation. Here, we present a systematic study of microthermometry of fluid inclusions found in carbonatites from the Kaiserstuhl (SW Germany), and a simple numerical model to estimate the compositions of such fluids, which are typical of numerous carbonatites worldwide. Four types of fluid inclusions have been identified in the Kaiserstuhl carbonatites: (I) vapor-poor H2O-NaCl fluids with <50?wt.% salinity; (II) vapor-rich H2O-NaCl-CO2 fluids with <5?wt.% salinity; (III) multi-component fluids with high salinity and high CO2 contents; and (IV) multi-component fluids with high salinity but little to no CO2. At present, it is only possible to quantify fluid compositions for types I and II. For the complex types III and IV, we conducted predictive modeling of the liquidus surface based on the Margules equations. The results suggest that carbonatite melts predominantly exsolve Na-K-sulfate-carbonate/bicarbonate-chloride brines (types III or IV). Such fluid inclusions may represent immiscible fluids that were trapped after segregation by boiling from a parental highly saline brine (type I). Fluid boiling, in turn, was probably triggered by a rapid pressure release during melt ascent. The present model enables quantification of fluid compositions associated with carbonatitic magmatism.
Abstract:
This study reports halogen contents (F and Cl) of amphibole and phlogopite derived from mantle xenoliths and one peridotite massif, for amphibole and phlogopite megacrysts and ultramafic magmatic cumulates (hornblendites) found in alkaline volcanic rocks from 12 localities in Europe and Africa. Amphibole and phlogopite contain more F than Cl with F/Cl ratios reaching about 160 in phlogopites and 50 in amphiboles. Phlogopites are higher in F (median of 3400 µg/g) than amphibole (median of 1000 µg/g), while median Cl contents are higher in amphibole (290 µg/g) compared to phlogopite (180 µg/g). The Cl contents and the F/Cl ratios in amphibole and phlogopite from mantle xenoliths exhibit large differences between samples of the same region, recording very large variations of halogen contents in the continental lithosphere. We suggest that the halogen content in such samples largely depends on the initial composition of percolating melts and fluids in the continental lithosphere. During reaction of these agents with peridotitic wall-rocks, Cl is preferentially retained in the fluid as it is much more incompatible compared to water and F. This desiccation effect continuously increases salinity (Cl content) and decreases the F/Cl ratio in the agent with time, causing variable Cl contents and F/Cl ratios in amphibole and phlogopite at a specific locality. Subsequent partial melting processes may then sequester and re-distribute, especially Cl among amphibole, phlogopite and melts/fluids as a result of its strong incompatibility, whereas F is much less affected as it behaves slightly compatible. The impact of even small amounts of amphibole and mica on the total halogen budget in the continental lithosphere is significant and both minerals can effectively contribute to the high halogen contents typical of alkaline melts.
Geochimica et Cosmochimica Acta, Vol. 277, pp. 224-242. pdf
Europe, Germany
deposit - Kaiserstuhl
Abstract: Studies of fluid inclusions in carbonatitic rocks are essential for understanding physicochemical processes involved in carbonatite-related hydrothermal ore mineralization and fenitization. However, the composition of many carbonatite-derived fluids is challenging to quantify, which hampers their detailed interpretation. Here, we present a systematic study of microthermometry of fluid inclusions found in carbonatites from the Kaiserstuhl (SW Germany), and a simple numerical model to estimate the compositions of such fluids, which are typical of numerous carbonatites worldwide. Four types of fluid inclusions have been identified in the Kaiserstuhl carbonatites: (I) vapor-poor H2O-NaCl fluids with <50?wt.% salinity; (II) vapor-rich H2O-NaCl-CO2 fluids with <5?wt.% salinity; (III) multi-component fluids with high salinity and high CO2 contents; and (IV) multi-component fluids with high salinity but little to no CO2. At present, it is only possible to quantify fluid compositions for types I and II. For the complex types III and IV, we conducted predictive modeling of the liquidus surface based on the Margules equations. The results suggest that carbonatite melts predominantly exsolve Na-K-sulfate-carbonate/bicarbonate-chloride brines (types III or IV). Such fluid inclusions may represent immiscible fluids that were trapped after segregation by boiling from a parental highly saline brine (type I). Fluid boiling, in turn, was probably triggered by a rapid pressure release during melt ascent. The present model enables quantification of fluid compositions associated with carbonatitic magmatism.
Russian Journal of Pacific Geology, Vol. 12, 5, pp. 408-418.
Russia, Kamchatka
picrites
Abstract: The mineral and chemical compositions of the layered subvolcanic ultrabasic rocks formed through fluid-silicate (liquid) separation of the ultrabasic magma into high-potassium and low-potassium fractions are characterized by the example of the layered picritic sill from the Late Cretaceous ultrabasic volcanic complex of Eastern Kamchatka. It is determined that the main potassium concentrator in the picrites from the high-potassium layers is a residual volcanic glass containing up to 8-9 wt % K2O, which is unique for ultrabasic melts.
Society of Economic Geology Geoscience and Exploration of the Argyle, Bunder, Diavik, and Murowa Diamond Deposits, Special Publication no. 20, pp. 425-
Marks, M.A.W., Rudnick, R.L., McCammon, C., Vennemann, T., Markl, G.
Arrested kinetic Li isotope fractionation at the margin of the Ilimaussaq complex: evidence for open system processes during final cooling peralkaline igneous rocks
Marks, M.A.W., Neukirchen, F., Vennemann, T., Markl, G.
Textural, chemical and isotopic effects of late magmatic carbonatitic fluids in the carbonatite syenite Tamazeght complex, High Atlas Mountains, Morocco.
Mangler, M.F., Marks, M.A.W., Zaitsev, A.N., Eby, G.N., Markl, G.
Halogens (F, Cl and Br) at Oldoinyo Lengai volcano ( Tanzania): effects of magmatic differentiation, silicate, natrocarbonatite melt seperation and surface alteration of natrocarbonatite.
Abstract: Textural and compositional variations of apatite from four intrusions with different characteristic features of the rift-related alkaline Gardar Province were investigated: dyke rocks that belong to the most primitive rocks of the Province (Isortoq), nepheline-syenites associated with a carbonatite (Grønnedal-Ika), SiO2-saturated and SiO2-oversaturated syenites (Puklen) and nepheline-syenites displaying the transition from miaskitic to agpaitic mineral assemblages (Motzfeldt, Fig.1). Additionally, apatites from these intrusions were compared with other apatites of the Gardar Province. These include apatites from the Older Giant Dyke Complex, the Younger Giant Dyke Complex (both from the Tugtutôq region) and a narsarsukite-bearing trachytic dyke (Igdlutalik), as well as apatites from the Kûngnât, the North Qôroq and the Ilímaussaq intrusive complexes. This results in a complete overview of rift-related magmatites of the Gardar Province, ranging from primitive to highly evolved rocks. Backscattered electron images reveal the presence of various types of apatite textures including (i) growth zonation (concentric and oscillatory) that formed during magmatic differentiation and (ii) overgrowth and secondary textures (rounded cores, patchy zonation and overgrowth rims) due to fluid/melt induced metasomatic overprint and intracrystalline diffusion (Fig.2). Additionally, apatite compositions were analyzed with wavelength-dispersive electron microprobe analyses. During the crystallization history of the different intrusions, as well as within samples (documented by zoning patterns), increasing concentrations are observed for Si, REE, Na and F, whereas Cl shows a decreasing trend. However, for F, Cl and Na these trends are only observed in dyke rocks. Compositional variation of the investigated apatites is mainly due to substitution of Ca and P by variable amounts of Si, Na and REE. This study reveals that variations in the chemical composition of apatite are useful tools to obtain geochemical information about the host magma and its magmatic evolution. Here, Si and REE were found to be reliable petrogenetic indicators, whereas Na, F and Cl are only applicable in fast cooling systems to avoid redistribution of those elements.
Abstract: The 2060 Ma old Palabora Carbonatite Complex (PCC), South Africa, comprises diverse REE mineral assemblages formed during different stages and reflects an outstanding instance to understand the evolution of a carbonatite-related REE mineralization from orthomagmatic to late-magmatic stages and their secondary post-magmatic overprint. The 10 rare earth element minerals monazite, REE-F-carbonates (bastnäsite, parisite, synchysite), ancylite, britholite, cordylite, fergusonite, REE-Ti-betafite, and anzaite are texturally described and related to the evolutionary stages of the PCC. The identification of the latter five REE minerals during this study represents their first described occurrences in the PCC as well as in a carbonatite complex in South Africa. The variable REE mineral assemblages reflect a multi-stage origin: (1) fergusonite and REE-Ti-betafite occur as inclusions in primary magnetite. Bastnäsite is enclosed in primary calcite and dolomite. These three REE minerals are interpreted as orthomagmatic crystallization products. (2) The most common REE minerals are monazite replacing primary apatite, and britholite texturally related to the serpentinization of forsterite or the replacement of forsterite by chondrodite. Textural relationships suggest that these two REE-minerals precipitated from internally derived late-magmatic to hydrothermal fluids. Their presence seems to be locally controlled by favorable chemical conditions (e.g., presence of precursor minerals that contributed the necessary anions and/or cations for their formation). (3) Late-stage (post-magmatic) REE minerals include ancylite and cordylite replacing primary magmatic REE-Sr-carbonates, anzaite associated with the dissolution of ilmenite, and secondary REE-F-carbonates. The formation of these post-magmatic REE minerals depends on the local availability of a fluid, whose composition is at least partly controlled by the dissolution of primary minerals (e.g., REE-fluorocarbonates). This multi-stage REE mineralization reflects the interplay of magmatic differentiation, destabilization of early magmatic minerals during subsequent evolutionary stages of the carbonatitic system, and late-stage fluid-induced remobilization and re-/precipitation of precursor REE minerals. Based on our findings, the Palabora Carbonatite Complex experienced at least two successive stages of intense fluid–rock interaction.
Abstract: Carbonatites and alkaline-silicate rocks are the most important sources of rare earth elements (REE) and niobium (Nb), both of which are metals imperative to technological advancement and associated with high risks of supply interruption. Cooling and crystallizing carbonatitic and alkaline melts expel multiple pulses of alkali-rich aqueous fluids which metasomatize the surrounding country rocks, forming fenites during a process called fenitization. These alkalis and volatiles are original constituents of the magma that are not recorded in the carbonatite rock, and therefore fenites should not be dismissed during the description of a carbonatite system. This paper reviews the existing literature, focusing on 17 worldwide carbonatite complexes whose attributes are used to discuss the main features and processes of fenitization. Although many attempts have been made in the literature to categorize and name fenites, it is recommended that the IUGS metamorphic nomenclature be used to describe predominant mineralogy and textures. Complexing anions greatly enhance the solubility of REE and Nb in these fenitizing fluids, mobilizing them into the surrounding country rock, and precipitating REE- and Nb-enriched micro-mineral assemblages. As such, fenites have significant potential to be used as an exploration tool to find mineralized intrusions in a similar way alteration patterns are used in other ore systems, such as porphyry copper deposits. Strong trends have been identified between the presence of more complex veining textures, mineralogy and brecciation in fenites with intermediate stage Nb-enriched and later stage REE-enriched magmas. However, compiling this evidence has also highlighted large gaps in the literature relating to fenitization. These need to be addressed before fenite can be used as a comprehensive and effective exploration tool.
Abstract: Pyrochlore from the Kaiserstuhl volcanic complex (SW Germany) shows textural and compositional differences between various coarse-grained calcite-carbonatite bodies (Badberg, Degenmatt, Haselschacher Buck, Orberg) and extrusive carbonatites (Henkenberg, Kirchberg). Oscillatory-zoned F-rich pyrochlore with up to 69?wt% Nb2O5 is common in all coarse-grained calcite-carbonatite bodies and probably formed during magmatic conditions. However, only in some of the samples from the Badberg, partly resorbed U- and Ta-enriched pyrochlore cores with up to 22?wt% UO2 and 9?wt% Ta2O5 have been identified, which are interpreted as being inherited from underlying nosean syenites. Pyrochlore data from a drill core penetrating the Badberg indicate increasing contents of REE, U, and Ta with depth, while Nb, F and Na contents decrease. This may reflect the combined effects of fractional crystallization and assimilation (AFC) or indicates a multi-stage emplacement of the carbonatitic magma. Patchy-zoned ceriopyrochlore and REE- and Th-enriched pyrochlore with up to 19?wt% total REE2O3 and 6.5?wt% ThO2 is largely restricted to samples from the Orberg and probably formed during hydrothermal conditions. This can be related to the relatively evolved character of the Orberg carbonatites, based on their relatively high whole-rock Nb/Ta and Zr/Hf mass ratios. This study demonstrates that the textural and compositional variation of pyrochlore in carbonatites is a powerful tool to distinguish magmatic, hydrothermal and weathering processes in carbonatitic systems.
Abstract: A detailed electron microprobe study has been carried out on the compositional variations of mica and apatite from carbonatites, phoscorites and associated pyroxenites (and fenites) of the Loolekop deposit, Palabora Carbonatite Complex (South Africa). Mica in pyroxenites and fenites is Mg-rich biotite, whilst micas in carbonatites and phoscorites are compositionally diverse including phlogopite, Ba-rich phlogopite (up to 30% kinoshitalite component), IVAl-rich phlogopite (up to 30% eastonite component) and tetraferriphlogopite. The various types of phlogopites are interpreted as orthomagmatic phases, whereas tetraferriphlogopite precipitation was a late-magmatic to hydrothermal process that additionally introduced REE into the system. Orthomagmatic apatite is generally REE- and Sr-poor fluorapatite and does not show large compositional differences between rock types. Apatite associated with the late-stage tetraferriphlogopite mineralization reaches higher levels of REE (up to 4.9?wt%), Si (up to 1.5?wt% SiO2), Sr (up to 2.6?wt% SrO) and Na (up to 1.0?wt% Na2O). The compositional variation of micas and apatites, which is affiliated with distinct rock types, reflects the multi-stage evolution of the Loolekop deposit and provides detailed insight into the relationships of the carbonatite-phoscorite assemblage. The obtained data support the separation of phoscorite and carbonatite by immiscibility from a common parental magma, which may happen due to a decrease of temperature and/or pressure during the ascent of the magma. This results in a density contrast between the carbonatitic and phoscoritic components that will lead to descending phoscorite accumulations at the outer zones of the magma channel and a jet-like ascent (further promoted by its extremely low viscosity) of the carbonatite magma. The genetic model deduced here explains the peculiar association of carbonatites, phoscorites and silicate rocks in many alkaline complexes worldwide.
Abstract: A detailed electron microprobe study has been carried out on the compositional variations of mica and apatite from carbonatites, phoscorites and associated pyroxenites (and fenites) of the Loolekop deposit, Palabora Carbonatite Complex (South Africa). Mica in pyroxenites and fenites is Mg-rich biotite, whilst micas in carbonatites and phoscorites are compositionally diverse including phlogopite, Ba-rich phlogopite (up to 30% kinoshitalite component), IVAl-rich phlogopite (up to 30% eastonite component) and tetraferriphlogopite. The various types of phlogopites are interpreted as orthomagmatic phases, whereas tetraferriphlogopite precipitation was a late-magmatic to hydrothermal process that additionally introduced REE into the system. Orthomagmatic apatite is generally REE- and Sr-poor fluorapatite and does not show large compositional differences between rock types. Apatite associated with the late-stage tetraferriphlogopite mineralization reaches higher levels of REE (up to 4.9?wt%), Si (up to 1.5?wt% SiO2), Sr (up to 2.6?wt% SrO) and Na (up to 1.0?wt% Na2O). The compositional variation of micas and apatites, which is affiliated with distinct rock types, reflects the multi-stage evolution of the Loolekop deposit and provides detailed insight into the relationships of the carbonatite-phoscorite assemblage. The obtained data support the separation of phoscorite and carbonatite by immiscibility from a common parental magma, which may happen due to a decrease of temperature and/or pressure during the ascent of the magma. This results in a density contrast between the carbonatitic and phoscoritic components that will lead to descending phoscorite accumulations at the outer zones of the magma channel and a jet-like ascent (further promoted by its extremely low viscosity) of the carbonatite magma. The genetic model deduced here explains the peculiar association of carbonatites, phoscorites and silicate rocks in many alkaline complexes worldwide.
Abstract: Security of supply of “hi-tech” raw materials (including the rare earth elements (REE) and some high-field-strength elements (HFSEs)) is a concern for the European Union. Exploration and research projects mostly focus on deposit- to outcrop-scale description of carbonatite- and alkaline igneous-associated REE-HFSE mineralization. The REE-HFSE mineral system concept and approach are at a nascent stage, so developed further here. However, before applying the mineral system approach to a chosen REE-HFSE metallogenic province its mineral system extent first needs defining and mapping. This shifts a mineral system project’s foundation from the mineral system concept to a province’s mineral system extent. The mapped extent is required to investigate systematically the pathways and potential trap locations along which the REE-HFSE mass may be distributed. A workflow is presented to standardize the 4-D definition of a REE-HFSE mineral system at province-scale: (a) Identify and hierarchically organize a mineral system’s genetically related sub-divisions and deposits, (b) map its known and possible maximum extents, (c) name it, (d) discern its size (known mineral endowment), and (e) assess the favorability of the critical components to prioritize further investigations. The workflow is designed to generate process-based perspective and improve predictive targeting effectiveness along under-evaluated plays of any mineral system, for the future risking, comparing and ranking of REE-HFSE provinces and plays.
Abstract: Alkaline complexes consist of variable mantle-derived silicate rocks, ranging from primitive alkali basalts, melilitites, nephelinites and basanites towards tephrites and more evolved phonolites, respectively their plutonic equivalents. This lithological variance is also expressed by a wide range of redox conditions that vary by several log units around the synthetic fayalite-magnetite-quartz (FMQ) buffer. However, only some of these complexes are characterized by the occurrence of carbonatites which must be related to specific formation conditions. Based on textural, mineralogical and geochemical observations, we calculated the redox conditions of carbonatites and associated silicate rocks for seven alkaline complexes (Kaiserstuhl, Sokli, Kovdor, Palabora, Magnet Cove, Oka, Jacupiranga) which are considered to represent typical carbonatite-alkaline silicate rock associations. In combination with a comprehensive literature review, we demonstrate that carbonatite-bearing alkaline complexes formed under highly oxidized conditions and hence, belong to the most oxidized alkaline rocks at all. This is consistent with the prerequisite of a carbonated mantle as the source region for carbonatite complexes, which requires redox conditions distinctively above that for mean lithospheric or asthenospheric mantle. Carbonatitemetasomatized peridotites also show high redox conditions and might not only reflect an interaction between peridotite and carbonatitic melts/fluids, but at least partly represent the carbonated mantle source for crustally emplaced carbonatite complexes. We therefore suggest that the oxidation state of carbonatites and associated silicate rocks provides direct information about an extraordinary oxidized parental mantle source.
Abstract: A detailed electron microprobe study has been carried out on the compositional variations of mica and apatite from carbonatites, phoscorites and associated pyroxenites (and fenites) of the Loolekop deposit, Palabora Carbonatite Complex (South Africa). Mica in pyroxenites and fenites is Mg-rich biotite, whilst micas in carbonatites and phoscorites are compositionally diverse including phlogopite, Ba-rich phlogopite (up to 30% kinoshitalite component), IVAl-rich phlogopite (up to 30% eastonite component) and tetraferriphlogopite. The various types of phlogopites are interpreted as orthomagmatic phases, whereas tetraferriphlogopite precipitation was a late-magmatic to hydrothermal process that additionally introduced REE into the system. Orthomagmatic apatite is generally REE- and Sr-poor fluorapatite and does not show large compositional differences between rock types. Apatite associated with the late-stage tetraferriphlogopite mineralization reaches higher levels of REE (up to 4.9?wt%), Si (up to 1.5?wt% SiO2), Sr (up to 2.6?wt% SrO) and Na (up to 1.0?wt% Na2O). The compositional variation of micas and apatites, which is affiliated with distinct rock types, reflects the multi-stage evolution of the Loolekop deposit and provides detailed insight into the relationships of the carbonatite-phoscorite assemblage. The obtained data support the separation of phoscorite and carbonatite by immiscibility from a common parental magma, which may happen due to a decrease of temperature and/or pressure during the ascent of the magma. This results in a density contrast between the carbonatitic and phoscoritic components that will lead to descending phoscorite accumulations at the outer zones of the magma channel and a jet-like ascent (further promoted by its extremely low viscosity) of the carbonatite magma. The genetic model deduced here explains the peculiar association of carbonatites, phoscorites and silicate rocks in many alkaline complexes worldwide.
Abstract: The mineralogy and mineral chemistry of the four major sövite bodies (Badberg, Degenmatt, Haselschacher Buck and Orberg), calcite foidolite/nosean syenite xenoliths (enclosed in the Badberg sövite only) and rare extrusive carbonatites of the Kaiserstuhl Volcanic Complex in Southern Germany provide evidence for contamination processes in the carbonatitic magma system of the Kaiserstuhl. Based on textures and composition, garnet and clinopyroxene in extrusive carbonatites represent xenocrysts entrained from the associated silicate rocks. In contrast, forsterite, monticellite and mica in sövites from Degenmatt, Haselschacher Buck and Orberg probably crystallized from the carbonatitic magma. Clinopyroxene and abundant mica crystallization in the Badberg sövite, however, was induced by the interaction between calcite foidolite xenoliths and the carbonatite melt. Apatite and micas in the various sövite bodies reveal clear compositional differences: apatite from Badberg is higher in REE, Si and Sr than apatite from the other sövite bodies. Mica from Badberg is biotite- and comparatively Fe2+-rich (Mg# = 72-88). Mica from the other sövites, however, is phlogopite (Mg# up to 97), as is typical of carbonatites in general. The typical enrichment of Ba due to the kinoshitalite substitution is observed in all sövites, although it is subordinate in the Badberg samples. Instead, Badberg biotites are strongly enriched in IVAl (eastonite substitution) which is less important in the other sövites. The compositional variations of apatite and mica within and between the different sövite bodies reflect the combined effects of fractional crystallization and carbonatite-wall rock interaction during emplacement. The latter process is especially important for the Badberg sövites, where metasomatic interaction released significant amounts of K, Fe, Ti, Al and Si from earlier crystallized nosean syenites. This resulted in a number of mineral reactions that transformed these rocks into calcite foidolites. Moreover, this triggered the crystallization of compositionally distinct mica and clinopyroxene crystals around the xenoliths and within the Badberg sövite itself. Thus, the presence and composition of clinopyroxene and mica in carbonatites may be useful indicators for contamination processes during their emplacement. Moreover, the local increase of silica activity during contamination enabled strong REE enrichment in apatite via a coupled substitution involving Si, which demonstrates the influence of contamination on REE mineralization in carbonatites.
Abstract: Contamination of carbonatites with crustal or cogenetic intrusive rocks is generally not considered to play an important role during carbonatite magmatism, because carbonatitic melts have low densities and viscosities, enabling them to rapidly ascend. Potential contamination by silicate rocks in carbonatites cannot easily be detected by means of radiogenic isotope data (such as Sr, Nd and Pb isotope data) as carbonatites often show high concentrations of these elements and their isotope systems are thereby “buffered” against contamination with silicate rocks. Textural, mineralogical and geochemical observations in carbonatites from the Kaiserstuhl (Germany) provide evidence for the interaction of carbonatitic magma with previously emplaced nosean syenites. This caused replacement of alkali feldspar by haüyne and recrystallization of garnet and clinopyroxene in the xenoliths, which released larger amounts of K, Al, Si and Fe. As a result, blackwall-like mica seams around the xenoliths formed and and compositionally distinct mica and clinopyroxene crystallized in the surrounding carbonatite. Moreover, the local increase of silica activity during contamination enabled strong REE enrichment in apatite via a coupled substitution involving Si, which demonstrates the potential influence of Si contamination on REE mineralization in carbonatites. We further suggest that the presence and composition of clinopyroxene and mica in carbonatites may be useful indicators for contamination processes during their emplacement. Mass-balance calculations based on experimental constraints for the solubility of Al and Si in carbonatitic magmas suggest that only minor amounts of mica can form from carbonatitic melt. Therefore, larger amounts of mica and mica-dominated lithologies (glimmerites) as observed in many carbonatite complexes suggest that some Si and Al in carbonatites may be sourced from surrounding host rocks. We hypothesize that assimilation and contamination processes in carbonatites may be the rule rather than an exception.
Abstract: Studies on fluid inclusions in carbonatitic rocks are essential to understand the physicochemical processes involved in carbonatite-related hydrothermal ore mineralization. Although little is known about the composition of carbonatite-derived fluids. We investigated fluid inclusions in the Kaiserstuhl carbonatites, SW Germany [1,2] and identified four different types typically known from carbonatitic systems worldwide [3]: (I): Vapor-poor H2O-NaCl fluids with <50 wt.% salinity. (II): Vapor-rich H2O-NaCl-CO2 fluids with <5 wt.% salinity. (III): Multi-component fluids with high salinity and CO2. (IV): Multi-component fluids with high salinity, no CO2. Homogenization temperatures (156 to 530°C) of all fluid types generally show a wide range [this study, 2]. Primary type I fluid inclusions occur in early magmatic olivine/monticellite, as well as paragenetically later apatites and calcites [2]. This indicates a ubiquitous existence of a saline brine, which does not reach saturation with respect to halite, during early to late crystallization stages. Liquidus surface modelling based quantifications for fluid type III suggest that carbonatite melts predomonantly exsolve Na-K-sulfate-carbonate/bicarbonate-chloride brines (type III or IV, respectively). Such fluid inclusions, with type III (CO2-free) on one side and type IV (and II, both CO2-rich) on the other side, may represent immiscible fluids that were trapped after segregation by boiling from a parental highly saline brine (type I). Fluid boiling, in turn, is probably triggered by a rapid pressure release during “pneumatic hammer-like,” discontinuous melt ascent.
Earth and Planetary Science Letters, Vol. 533, 11p. Pdf
Mantle
carbonatite
Abstract: A detailed investigation on seven carbonatites and associated alkaline rock complexes (Kaiserstuhl, Sokli, Kovdor, Palabora, Oka, Magnet Cove, Jacupiranga), together with a world-wide comparison between carbonatites, alkaline silicate rocks and mantle xenoliths, implies peculiar redox conditions for carbonatite-bearing alkaline complexes: Carbonatites and associated alkaline rocks in continental settings crystallize from relatively oxidized magmas, on average 1.4 log units () and 1.3 log units () above the synthetic fayalite-magnetite-quartz (FMQ) buffer. In contrast, alkaline rocks in continental settings that lack associated carbonatites reveal rather reduced conditions (mean ; ). The calculated redox conditions for carbonatites and associated silicate rocks demonstrate that these crystallize from relatively oxidized mantle-derived melts compared to the general range found for alkaline rocks in continental settings.
Geochimica et Cosmochimica Acta, Vol. 277, pp. 224-242. pdf
Europe, Germany
carbonatite
Abstract: Studies of fluid inclusions in carbonatitic rocks are essential for understanding physicochemical processes involved in carbonatite-related hydrothermal ore mineralization and fenitization. However, the composition of many carbonatite-derived fluids is challenging to quantify, which hampers their detailed interpretation. Here, we present a systematic study of microthermometry of fluid inclusions found in carbonatites from the Kaiserstuhl (SW Germany), and a simple numerical model to estimate the compositions of such fluids, which are typical of numerous carbonatites worldwide. Four types of fluid inclusions have been identified in the Kaiserstuhl carbonatites: (I) vapor-poor H2O-NaCl fluids with <50?wt.% salinity; (II) vapor-rich H2O-NaCl-CO2 fluids with <5?wt.% salinity; (III) multi-component fluids with high salinity and high CO2 contents; and (IV) multi-component fluids with high salinity but little to no CO2. At present, it is only possible to quantify fluid compositions for types I and II. For the complex types III and IV, we conducted predictive modeling of the liquidus surface based on the Margules equations. The results suggest that carbonatite melts predominantly exsolve Na-K-sulfate-carbonate/bicarbonate-chloride brines (types III or IV). Such fluid inclusions may represent immiscible fluids that were trapped after segregation by boiling from a parental highly saline brine (type I). Fluid boiling, in turn, was probably triggered by a rapid pressure release during melt ascent. The present model enables quantification of fluid compositions associated with carbonatitic magmatism.
Abstract:
This study reports halogen contents (F and Cl) of amphibole and phlogopite derived from mantle xenoliths and one peridotite massif, for amphibole and phlogopite megacrysts and ultramafic magmatic cumulates (hornblendites) found in alkaline volcanic rocks from 12 localities in Europe and Africa. Amphibole and phlogopite contain more F than Cl with F/Cl ratios reaching about 160 in phlogopites and 50 in amphiboles. Phlogopites are higher in F (median of 3400 µg/g) than amphibole (median of 1000 µg/g), while median Cl contents are higher in amphibole (290 µg/g) compared to phlogopite (180 µg/g). The Cl contents and the F/Cl ratios in amphibole and phlogopite from mantle xenoliths exhibit large differences between samples of the same region, recording very large variations of halogen contents in the continental lithosphere. We suggest that the halogen content in such samples largely depends on the initial composition of percolating melts and fluids in the continental lithosphere. During reaction of these agents with peridotitic wall-rocks, Cl is preferentially retained in the fluid as it is much more incompatible compared to water and F. This desiccation effect continuously increases salinity (Cl content) and decreases the F/Cl ratio in the agent with time, causing variable Cl contents and F/Cl ratios in amphibole and phlogopite at a specific locality. Subsequent partial melting processes may then sequester and re-distribute, especially Cl among amphibole, phlogopite and melts/fluids as a result of its strong incompatibility, whereas F is much less affected as it behaves slightly compatible. The impact of even small amounts of amphibole and mica on the total halogen budget in the continental lithosphere is significant and both minerals can effectively contribute to the high halogen contents typical of alkaline melts.
Geochimica et Cosmochimica Acta, Vol. 277, pp. 224-242. pdf
Europe, Germany
deposit - Kaiserstuhl
Abstract: Studies of fluid inclusions in carbonatitic rocks are essential for understanding physicochemical processes involved in carbonatite-related hydrothermal ore mineralization and fenitization. However, the composition of many carbonatite-derived fluids is challenging to quantify, which hampers their detailed interpretation. Here, we present a systematic study of microthermometry of fluid inclusions found in carbonatites from the Kaiserstuhl (SW Germany), and a simple numerical model to estimate the compositions of such fluids, which are typical of numerous carbonatites worldwide. Four types of fluid inclusions have been identified in the Kaiserstuhl carbonatites: (I) vapor-poor H2O-NaCl fluids with <50?wt.% salinity; (II) vapor-rich H2O-NaCl-CO2 fluids with <5?wt.% salinity; (III) multi-component fluids with high salinity and high CO2 contents; and (IV) multi-component fluids with high salinity but little to no CO2. At present, it is only possible to quantify fluid compositions for types I and II. For the complex types III and IV, we conducted predictive modeling of the liquidus surface based on the Margules equations. The results suggest that carbonatite melts predominantly exsolve Na-K-sulfate-carbonate/bicarbonate-chloride brines (types III or IV). Such fluid inclusions may represent immiscible fluids that were trapped after segregation by boiling from a parental highly saline brine (type I). Fluid boiling, in turn, was probably triggered by a rapid pressure release during melt ascent. The present model enables quantification of fluid compositions associated with carbonatitic magmatism.
Abstract: Palaeogeography is the representation of the past surface of the Earth. It provides the spatial context for investigating how the Earth evolves through time, how complex processes interact and the juxtaposition of spatial information. In hydrocarbon exploration, palaeogeographies have been used to map and investigate the juxtaposition, distribution and quality of play elements (source, reservoir, seal and trap), as boundary conditions for source-to-sink analysis, climate modelling and lithofacies retrodiction, but most commonly as the backdrop for presentations and montages. This paper demonstrates how palaeogeography has been and can be used within an exploration workflow to help mitigate exploration risk. A comprehensive workflow for building palaeogeographies is described which is designed to provide a standard approach that can be applied to a range of tasks in exploration and academia. This is drawn from an analysis of the history of palaeogeography and how it has been applied to exploration in the past and why. Map applications, resolution and content depend on where in the exploration and production (E&P) cycle the map is used. This is illustrated here through three case studies, from the strategic decisions of global new ventures exploration to the more detailed basin and petroleum analyses of regional asset teams evaluating basins and plays. Through this, the paper also addresses three commonly asked questions: (1) How can I use palaeogeography in my workflow? (2) How reliable are the maps? (3) How do I build a palaeogeography?
Abstract: The West African Craton is highly endowed in minerals, and their spatial and temporal distribution varies from single to multi-phase mineralization events. They are broadly related to three major tectono-metallogenic elements and formed during distinct mineral epochs: (1) In both Archean Shields (Kénéma-Man and Reguibat) and Paleoproterozoic domains (Baoulé-Mossi, Eglab). These are characterized by giant iron ore deposits that formed between ca. 2.5-2.3 Ga, nearly all gold, porphyry copper, lead-zinc and sedimentary manganese ore that developed between 2.2 and 2.1 Ga, and primary diamonds that formed between two intervals at ca. 2.2-2.0 Ga and in the Mesozoic. (2) Across Pan-African and Variscan belts. These are distinguished by major Precambrian IOCG's, copper-gold that formed at ca. 2.1 Ga and approximately 680 Ma, and Neoproterozoic sedimentary iron ore and phosphate deposits. (3) Within intracratonic and coastal basins. These include the development of Cenozoic lateritic bauxites over Mesozoic dolerites, Tertiary/Quaternary mineral sands deposits, oolitic iron ore and sedimentary phosphate deposits. Geological, spatial and temporal correlations using the multi-commodity West African Mineral Deposit Database highlight that gold and non-gold commodities formed in multiple phases. This commenced in the Liberian Orogeny (2.9-2.8 Ga) with the enrichment of iron ore, nickel sulphides, diamonds and gold in the earth's crust. The pre-Eburnean or Tangaean-EoEburnean-Eburnean I Event yielded gold, and the major Eburnean Orogeny yielded gold, iron ore, manganese, diamonds, magmatic nickel sulphides, copper-gold, lead-zinc, and REE minerals. Throughout the Pan-African event sedimentary manganese deposits, lead-zinc, REE minerals, sedimentary phosphates, and again gold were formed. Primary diamonds and magmatic nickel sulphides are related to the break-up of Gondwana, followed by an intense lateritic weathering period that formed bauxite deposits along the craton margin.
Abstract: The West African Craton hosts major resources of gold, iron ore, aluminium ore, diamonds, phosphates and manganese. This portfolio of ore deposits is linked to the formation of Archean -Paleoproterozoic greenstone belts, Jurassic rifting and extended periods of Mesozoic to Cenozoic weathering and erosion. We give a brief overview of the temporal and spatial distribution patterns of West African ore deposits with emphasis on the main commodity types. The oldest ore forming processes generated major resources in iron ore and gold in the Kénéma -Man and Reguibat Shields during the Neo-Archean. The majority of gold, porphyry copper, lead -zinc and sedimentary manganese deposits formed during the Paleoproterozoic, dominantly within the Baoulé-Mossi domain. At the same time diamond-bearing kimberlites developed in Ghana. Another distinct diamond event has been recognized in the Mesozoic of the Kénéma -Man shield. Isolated occurrences of IOCG's as well as copper -gold and gold formed in Pan-African/Variscan belts. During the Neoproterozoic, the majority of mineralization consists of sedimentary iron ore and phosphate deposits located within intracratonic basins. During the Phanerozoic aluminium ore, phosphates and mineral sands concentrated along the margins of the coastal and intracratonic basins.
Abstract: Diamonds form from fluids or melts circulating at depth in the Earth's mantle. Analysis of these fluids is possible if they remain entrapped in the diamond during its growth, but this is rarely observed in gem-quality stones. We provide the first evidence that typical mineral inclusions in gem-quality diamonds from the Siberian and Kaapvaal cratons are surrounded by a thin film of hydrous silicic fluid of maximum thickness 1.5 µm. The fluid contains Si2O(OH)6, Si(OH)4, and molecular H2O and was identified using confocal micro-Raman spectroscopy and synchrotron-based X-ray tomographic microscopy. As the solid mineral inclusions have both peridotitic and eclogitic affinities and occur in two cratonic regions, our results demonstrate the strong connection between water-rich fluids and the growth of gem-quality lithospheric diamonds. The presence of the fluid films should be taken into account for a proper evaluation of H2O contents in the mantle based on H2O contents in solid inclusions and for a robust assessment of diamond formation pressures based on the residual pressures of the inclusions.
PluS One, Vol. 13, 8, doi:10.1371/journal.pone.0200351
Asia, Thailand
garnets
Abstract: Garnets from disparate geographical environments and origins such as oxidized soils and river sediments in Thailand host intricate systems of microsized tunnels that significantly decrease the quality and value of the garnets as gems. The origin of such tunneling has previously been attributed to abiotic processes. Here we present physical and chemical remains of endolithic microorganisms within the tunnels and discuss a probable biological origin of the tunnels. Extensive investigations with synchrotron-radiation X-ray tomographic microscopy (SRXTM) reveal morphological indications of biogenicity that further support a euendolithic interpretation. We suggest that the production of the tunnels was initiated by a combination of abiotic and biological processes, and that at later stages biological processes came to dominate. In environments such as river sediments and oxidized soils garnets are among the few remaining sources of bio-available Fe2+, thus it is likely that microbially mediated boring of the garnets has trophic reasons. Whatever the reason for garnet boring, the tunnel system represents a new endolithic habitat in a hard silicate mineral otherwise known to be resistant to abrasion and chemical attack.
Abstract: Super-deep diamonds (SDDs) are those that form at depths between ~300 and ~1000 km in Earth’s mantle. They compose only 1% of the entire diamond population but play a pivotal role in geology, as they represent the deepest direct samples from the interior of our planet. Ferropericlase, (Mg,Fe)O, is the most abundant mineral found as inclusions in SDDs and, when associated with low-Ni enstatite, which is interpreted as retrogressed bridgmanite, is considered proof of a lower-mantle origin. As this mineral association in diamond is very rare, the depth of formation of most ferropericlase inclusions remains uncertain. Here we report geobarometric estimates based on both elasticity and elastoplasticity theories for two ferropericlase inclusions, not associated with enstatite, from a single Brazilian diamond. We obtained a minimum depth of entrapment of 15.7 (±2.5) GPa at 1830 (±45) K (~450 [±70] km depth), placing the origin of the diamond-inclusion pairs at least near the upper mantle-transition zone boundary and confirming their super-deep origin. Our analytical approach can be applied to any type of mineral inclusion in diamond and is expected to allow better insights into the depth distribution and origin of SDDs.
Contributions to Mineralogy and Petrology, Vol. 174, p. 29- 13p.
Russia, Siberia
deposit - Udachnaya
Abstract: We have studied by X-ray diffractometry the crystallographic orientation relationships (CORs) between magnesiochromite (mchr) inclusions and their diamond hosts in gem-quality stones from the mines Udachnaya (Siberian Russia), Damtshaa (Botswana) and Panda (Canada); in total 36 inclusions in 23 diamonds. In nearly half of the cases (n?=?17), [111]mchr is parallel within error to [111]diamond, but the angular misorientation for other crystallographic directions is generally significant. This relationship can be described as a case of rotational statistical COR, in which inclusion and host share a single axis (1 df). The remaining mchr-diamond pairs (n?=?19) have a random COR (2 df). The presence of a rotational statistical COR indicates that the inclusions have physically interacted with the diamond before their final incorporation. Of all possible physical processes that may have influenced mchr orientation, those driven by surface interactions are not considered likely because of the presence of fluid films around the inclusions. Mechanical interaction between euhedral crystals in a fluid-rich environment is therefore proposed as the most likely mechanism to produce the observed rotational COR. In this scenario, neither a rotational nor a random COR can provide information on the relative timing of growth of mchr and diamond. Some multiple, iso-oriented inclusions within single diamonds, however, indicate that mchr was partially dissolved during diamond growth, suggesting a protogenetic origin of these inclusions.
Diamonds and Related Materials, in press available 36p. Pdf
Africa, Ghana
deposit - Akwatia
Abstract: Magnetic mineral inclusions, as iron oxides or sulfides, occur quite rarely in natural diamonds. Nonetheless, they represent a key tool not only to unveil the conditions of formation of host diamonds, but also to get hints about the paleointensity of the geomagnetic field present at times of the Earth's history otherwise not accessible. This possibility is related to their capability to carry a remanent magnetization dependent on their magnetic history. However, comprehensive experimental studies on magnetic inclusions in diamonds have been rarely reported so far. Here we exploit X-ray diffraction, Synchrotron-based X-ray Tomographic Microscopy and Alternating Field Magnetometry to determine the crystallographic, morphological and magnetic properties of ferrimagnetic Fe-oxides entrapped in diamonds coming from Akwatia (Ghana). We exploit the methodology to estimate the natural remanence of the inclusions, associated to the Earth's magnetic field they experienced, and to get insights on the relative time of formation between host and inclusion systems. Furthermore, from the hysteresis loops and First Order Reversal Curves we determine qualitatively the anisotropy, size and domain state configuration of the magnetic grains constituting the inclusions.
Abstract: Magnetic mineral inclusions, as iron oxides or sulfides, occur quite rarely in natural diamonds. Nonetheless, they represent a key tool not only to unveil the conditions of formation of host diamonds, but also to get hints about the paleointensity of the geomagnetic field present at times of the Earth's history otherwise not accessible. This possibility is related to their capability to carry a remanent magnetization dependent on their magnetic history. However, comprehensive experimental studies on magnetic inclusions in diamonds have been rarely reported so far. Here we exploit X-ray diffraction, Synchrotron-based X-ray Tomographic Microscopy and Alternating Field Magnetometry to determine the crystallographic, morphological and magnetic properties of ferrimagnetic Fe-oxides entrapped in diamonds coming from Akwatia (Ghana). We exploit the methodology to estimate the natural remanence of the inclusions, associated to the Earth's magnetic field they experienced, and to get insights on the relative time of formation between host and inclusion systems. Furthermore, from the hysteresis loops and First Order Reversal Curves we determine qualitatively the anisotropy, size and domain state configuration of the magnetic grains constituting the inclusions.
Alvaro, M., Mazzucchelli, M.L., Angel, R.J., Murri, M., Campmenosi, N., Scambelluri, M., Nestola, F., Korsakov, A., Tomilenko, A.A., Marone, F., Morana, M.
Abstract: Metamorphic rocks are the records of plate tectonic processes whose reconstruction relies on correct estimates of the pressures and temperatures (P-T) experienced by these rocks through time. Unlike chemical geothermobarometry, elastic geobarometry does not rely on chemical equilibrium between minerals, so it has the potential to provide information on overstepping of reaction boundaries and to identify other examples of non-equilibrium behavior in rocks. Here we introduce a method that exploits the anisotropy in elastic properties of minerals to determine the unique P and T of entrapment from a single inclusion in a mineral host. We apply it to preserved quartz inclusions in garnet from eclogite xenoliths hosted in Yakutian kimberlites (Russia). Our results demonstrate that quartz trapped in garnet can be preserved when the rock reaches the stability field of coesite (the high-pressure and high-temperature polymorph of quartz) at 3 GPa and 850 °C. This supports a metamorphic origin for these xenoliths and sheds light on the mechanisms of craton accretion from a subducted crustal protolith. Furthermore, we show that interpreting P and T conditions reached by a rock from the simple phase identification of key inclusion minerals can be misleading.
Earth and Planetary Science Letters, Vol. 498, pp. 77-87.
Mantle
geophysics - seismic
Abstract: Earth's transition zone at depths between 410 km and 660 km plays a key role in Earth's deep water cycle since large amounts of hydrogen can be stored in the nominally anhydrous minerals wadsleyite and ringwoodite, . Previous mineral physics experiments on iron-free wadsleyite proposed low seismic velocities as an indicative feature for hydration in the transition zone. Here we report simultaneous sound wave velocity and density measurements on iron-bearing wadsleyite single crystals with 0.24 wt-% . By comparison with earlier studies, we show that pressure suppresses the velocity reduction caused by higher degrees of hydration in iron-bearing wadsleyite, ultimately leading to a velocity cross-over for both P-waves and S-waves. Modeling based on our experimental results shows that wave speed variations within the transition zone as well as velocity jumps at the 410-km seismic discontinuity, both of which have been used in previous work to detect mantle hydration, are poor water sensors. Instead, the impedance contrast across the 410-km seismic discontinuity that is reduced in the presence of water can serve as a more robust indicator for hydrated parts of the transition zone.
Earth and Planetary Science Letters, Vol. 498, pp. 9-16.
Mantle
water
Abstract: Ringwoodite, the dominant mineral at depths between 520 km and 660 km, can store up to 2-3 wt.% of water in its crystal structure, making the Earth's transition zone a plausible water reservoir that plays a central role in Earth's deep water cycle. Experiments show that hydration of ringwoodite significantly reduces elastic wave velocities at room pressure, but the effect of pressure remains poorly constrained. Here, a novel experimental setup enables a direct quantification of the effect of hydration on ringwoodite single-crystal elasticity and density at pressures of the Earth's transition zone and high temperatures. Our data show that the hydration-induced reduction of seismic velocities almost vanishes at conditions of the transition zone. Seismic data thus agree with a wide range of water contents in the transition zone.
Abstract: Majoritic garnet has been predicted to be a major component of peridotite and eclogite in Earth's deep upper mantle (>250 km) and transition zone. The investigation of mineral inclusions in diamond confirms this prediction, but there is reported evidence of other majorite-bearing lithologies, intermediate between peridotitic and eclogitic, present in the mantle transition zone. If these lithologies are derived from olivine-free pyroxenites, then at mantle transition zone pressures majorite may form monomineralic or almost monomineralic garnetite layers. Since majoritic garnet is presumably the seismically fastest major phase in the lowermost upper mantle, the existence of such majorite layers might produce a detectable seismic signature. However, a test of this hypothesis is hampered by the absence of sound wave velocity measurements of majoritic garnets with relevant chemical compositions, since previous measurements have been mostly limited to synthetic majorite samples with relatively simple compositions. In an attempt to evaluate the seismic signature of a pyroxenitic garnet layer, we measured the sound wave velocities of three natural majoritic garnet inclusions in diamond by Brillouin spectroscopy at ambient conditions. The chosen natural garnets derive from depths between 220 and 470 km and are plausible candidates to have formed at the interface between peridotite and carbonated eclogite. They contain elevated amounts (12-30%) of ferric iron, possibly produced during redox reactions that form diamond from carbonate. Based on our data, we model the velocity and seismic impedance contrasts between a possible pyroxenitic garnet layer and the surrounding peridotitic mantle. For a mineral assemblage that would be stable at a depth of 350 km, the median formation depth of our samples, we found velocities in pyroxenite at ambient conditions to be higher by 1.9(6)% for shear waves and 3.3(5)% for compressional waves compared to peridotite (numbers in parentheses refer to uncertainties in the last given digit), and by 1.3(13)% for shear waves and 2.4(10)% for compressional waves compared to eclogite. As a result of increased density in the pyroxenitic layer, expected seismic impedance contrasts across the interface between the monomineralic majorite layer and the adjacent rocks are about 5-6% at the majorite-eclogite-interface and 10-12% at the majoriteperidotite-boundary. Given a large enough thickness of the garnetite layer, velocity and impedance differences of this magnitude could become seismologically detectable.
Abstract: Diamonds form from fluids or melts circulating at depth in the Earth's mantle. Analysis of these fluids is possible if they remain entrapped in the diamond during its growth, but this is rarely observed in gem-quality stones. We provide the first evidence that typical mineral inclusions in gem-quality diamonds from the Siberian and Kaapvaal cratons are surrounded by a thin film of hydrous silicic fluid of maximum thickness 1.5 µm. The fluid contains Si2O(OH)6, Si(OH)4, and molecular H2O and was identified using confocal micro-Raman spectroscopy and synchrotron-based X-ray tomographic microscopy. As the solid mineral inclusions have both peridotitic and eclogitic affinities and occur in two cratonic regions, our results demonstrate the strong connection between water-rich fluids and the growth of gem-quality lithospheric diamonds. The presence of the fluid films should be taken into account for a proper evaluation of H2O contents in the mantle based on H2O contents in solid inclusions and for a robust assessment of diamond formation pressures based on the residual pressures of the inclusions.
Abstract: In this study, we report the first direct evidence for water-bearing fluids in the uppermost lower mantle from natural ferropericlase crystal contained within a diamond from São Luíz, Brazil. The ferropericlase exhibits exsolution of magnesioferrite, which places the origin of this assemblage in the uppermost part of the lower mantle. The presence of brucite-Mg(OH)2 precipitates in the ferropericlase crystal reflects the later-stage quenching of H2O-bearing fluid likely in the transition zone, which has been trapped during the inclusion process in the lower mantle. Dehydration melting may be one of the key processes involved in transporting water across the boundary between the upper and lower mantle.
Physics and Chemistry of Minerals, Vol. 45, 2, pp. 139-172.
Mantle
olivines
Abstract: Interfaces in rocks, especially grain boundaries in olivine dominated rocks, have been subject to about 40 years of studies. The grain boundary structure to property relation is fundamental to understand the diverging properties of polycrystalline samples compared to those of single crystals. The number of direct structural observations is small, i.e. in range of 100 micrographs, and the number of measurements of properties directly linked to structural observations is even smaller. Bulk aggregate properties, such as seismic attenuation, rheology and electrical conductivity, are sensitive to grain size, and seem to show influences by grain boundary character distributions. In this context we review previous studies on grain boundary structure and composition and plausible relations to bulk properties. The grain boundary geometry is described using five independent parameters; generally, their structural width ranges between 0.4-1.2 nm and the commonly used 1 nm seems a good approximation. This region of enhanced disorder is often enriched in elements that are incompatible in the perfect crystal lattice. The chemical composition of grain boundaries depends on the bulk rock composition. We determined the 5 parameter grain boundary character distribution (GBCD) for polycrystaline Fo90 and studied structure and chemistry at the nm-scale to extend previous measurements. We find that grain boundary planes close to perpendicular to the crystallographic c-direction dominate the grain boundary network. We conclude that linking grain boundary structure in its full geometric parameter space to variations of bulk rock properties is now possible by GBCD determination using EBSD mapping and statistical analyses.
Earth and Planetary Science Letters, Vol. 498, pp. 9-16.
Mantle
water
Abstract: Ringwoodite, the dominant mineral at depths between 520 km and 660 km, can store up to 2-3 wt.% of water in its crystal structure, making the Earth's transition zone a plausible water reservoir that plays a central role in Earth's deep water cycle. Experiments show that hydration of ringwoodite significantly reduces elastic wave velocities at room pressure, but the effect of pressure remains poorly constrained. Here, a novel experimental setup enables a direct quantification of the effect of hydration on ringwoodite single-crystal elasticity and density at pressures of the Earth's transition zone and high temperatures. Our data show that the hydration-induced reduction of seismic velocities almost vanishes at conditions of the transition zone. Seismic data thus agree with a wide range of water contents in the transition zone.
Proceedings of the National Academy of Sciences, pnas.org/cgi/doi.10.1073 /pnas.2004269117 7p. Pdf
Mantle
diamond inclusions
Abstract: The recent discovery in high-pressure experiments of compounds stable to 24-26 GPa with Fe4O5, Fe5O6, Fe7O9, and Fe9O11 stoichiometry has raised questions about their existence within the Earth’s mantle. Incorporating both ferric and ferrous iron in their structures, these oxides if present within the Earth could also provide insight into diamond-forming processes at depth in the planet. Here we report the discovery of metallic particles, dominantly of FeNi (Fe0.71Ni0.24Cu0.05), in close spatial relation with nearly pure magnetite grains from a so-called superdeep diamond from the Earth’s mantle. The microstructural relation of magnetite within a ferropericlase (Mg0.60Fe0.40)O matrix suggests exsolution of the former. Taking into account the bulk chemistry reconstructed from the FeNi(Cu) alloy, we propose that it formed by decomposition of a complex metal M oxide (M4O5) with a stoichiometry of (Fe3+2.15Fe2+1.59Ni2+0.17Cu+0.04)S = 3.95O5. We further suggest a possible link between this phase and variably oxidized ferropericlase that is commonly trapped in superdeep diamond. The observation of FeNi(Cu) metal in relation to magnetite exsolved from ferropericlase is interpreted as arising from a multistage process that starts from diamond encapsulation of ferropericlase followed by decompression and cooling under oxidized conditions, leading to the formation of complex oxides such as Fe4O5 that subsequently decompose at shallower P-T conditions.
Journal of South American Earth Sciences, Vol. 80, pp. 1-17.
South America, Brazil
carbonatite
Abstract: We present results of U-Pb dating (by MC-ICP-MS) of zircons from samples that cover all of the known lithotypes in the Seis Lagos Carbonatite Complex and associated lateritic mineralization (the Morro dos Seis Lagos Nb deposit). The host rock (gneiss) yielded an age of 1828 ± 09 Ma interpreted as the crystallization time of this unit. The altered feldspar vein in the same gneiss yielded an age of 1839 ± 29 Ma. Carbonatite samples provided 3 groups of ages. The first group comprises inherited zircons with ages compatible with the gneissic host rock: 1819 ± 10 Ma (superior intercept), 1826 ± 5 Ma (concordant age), and 1812 ± 27 Ma (superior intercept), all from the Orosirian. The second and the third group of ages are from the same carbonatite sample: the superior intercept age of 1525 ± 21 Ma (MSWD ¼ 0.77) and the superior intercept age of 1328 ± 58 Ma (MSWD ¼ 1.4). The mineralogical study indicates that the ~1.3 Ga zircons have affinity with carbonatite. It is, however, a tendence rather than a well-defined result. The data allow state that the age of 1328 ± 58 Ma represents the maximum age of the carbonatite. Without the same certainty, we consider that the data suggest that this age may be the carbonatite age, whose emplacement would have been related to the evolution of the K'Mudku belt. The best age obtained in laterite samples (a superior intercept age of 1828 ± 12 Ma) is considered the age of the main source for the inherited zircons related to the gneissic host rock.
Sanatmaria-Perez, D., Ruiz-Fuertes, J., Pena-Alvarez, M., Chulia-Jordan, R., Marquerno, T., Zimmer, D., Guterrez-Cano, V., Macleod, S., Gregoryanz, E., Popescue, C., Rodriguez-Herandez, P., Munoz, A.
Abstract: Calcium carbonate is a relevant constituent of the Earth’s crust that is transferred into the deep Earth through the subduction process. Its chemical interaction with calcium-rich silicates at high temperatures give rise to the formation of mixed silicate-carbonate minerals, but the structural behavior of these phases under compression is not known. Here we report the existence of a dense polymorph of Ca5(Si2O7)(CO3)2 tilleyite above 8 GPa. We have structurally characterized the two phases at high pressures and temperatures, determined their equations of state and analyzed the evolution of the polyhedral units under compression. This has been possible thanks to the agreement between our powder and single-crystal XRD experiments, Raman spectroscopy measurements and ab-initio simulations. The presence of multiple cation sites, with variable volume and coordination number (6-9) and different polyhedral compressibilities, together with the observation of significant amounts of alumina in compositions of some natural tilleyite assemblages, suggests that post-tilleyite structure has the potential to accommodate cations with different sizes and valencies.
The Mozambique Belt in northern Mozambique: Neoproterozoic 1100-850 Macrustal growth and tectogenesis and superimposed Pan-African 800-550 MatectonisM.
Precambrian Research, Vol. 62, No. 1-2, April pp. 1-60
Abstract: Early and Late Cretaceous alkaline and alkaline-carbonatitic complexes from southern Brazil are located along the main tectonic lineaments of the South America Platform. Calcium-, magnesium-, and ferrocarbonatites are well represented and frequently associated even in the same complex. Primary carbonates present significant variations in C-O isotopic compositions, which are mainly due to isotope exchange with H2O-CO2-rich hydrothermal fluids, whereas fractional crystallization or liquid immiscibility probably affects the d18O and d13C values by no more than 2d‰ Our isotope exchange model implies that the most significant isotopic variations took place in a hydrothermal environment, e.g., in the range 400-80°C, involving fluids with the CO2/H2O ratio ranging from 0.8 to 1. Sr-Nd-Pb isotope systematics highlight heterogeneous mixtures between HIMU and EMI mantle components, similar to the associated alkaline rocks and the flood tholeiites from southern Brazil. In spite of the strong variation shown by C-O isotopes, Sr-Nd-Pb-Os isotopic systematics could be related to an isotopically enriched source where the chemical heterogeneities reflect a depleted mantle "metasomatized" by small-volume melts and fluids rich in incompatible elements. These fluids are expected to have promoted crystallization of K-rich phases in the mantle, which produced a veined network variously enriched in LILE and LREE. The newly formed veins (enriched component) and peridotite matrix (depleted component) underwent a different isotopic evolution with time as reflected by the carbonatites. These conclusions may be extended to the whole Paraná-Etendeka system, where isotopically distinct parent magmas were generated following two main enrichment events of the subcontinental lithospheric mantle at 2.0-1.4 and 1.0-0.5?Ga, respectively, as also supported by Re-Os systematics. The mantle sources preserved the isotopic heterogeneities over a long time, suggesting a nonconvective lithospheric mantle beneath different cratons or intercratonic regions. Overall, the data indicate that the alkaline-carbonatitic magmatism originated from a locally heterogeneous subcontinental mantle.
Heibron, H. et al. eds. Sao Francisco Craton, eastern Brazil, Regional geology reviews., Chapter 3, pdf
South America, Brazil
Geology
Abstract: We overview the Archean tectonic framework the São Francisco craton based on geologic constraints, integrated geochronologic interpretation and isotopic-geochemical evidence of basement rocks. U-Pb provenance studies of Archean and Paleoproterozoic supracrustal sequences are also used to provide additional inferences about the geodynamic scenario. The Archean rocks crop out mainly in two large areas in the southern and northern portions of the craton, surrounded and/or in tectonic contact with Paleoproterozoic orogenic belts. The ancient substratum is essentially composed of medium- to high-grade gneissic-migmatitic rocks including TTG suites and coeval granite-greenstone associations that collectively provide an isotopic record as old as 4.1 Ga. The combined U-Pb and Sm-Nd TDM age peaks coupled with U-Pb inherited ages in detrital zircons from the supracrustal sequences indicate that very ancient continental crust (?3.5 Ga) exist, particularly in the northern portion of the craton. Mesoarchean events are episodic between 3.6-3.3 and 3.2-2.9 Ga, as for the Neoarchean (2.8-2.6 Ga) in both cratonic portions. This isotopic record indicates a protracted Archean history for the São Francisco craton, highlighted by peculiar tectonic-metamorphic histories of the basement rocks. From a tectonic point of view the compiled data concur with a diachronic evolution from Paleo- to Neoarchean times by means of juvenile accretion/differentiation events characterized by multiple TTG plutonism in genetic association with greenstone belts, coupled with partial melting events of earlier-formed material. All ancient basement complexes and/or continental blocks assembled diachronically during the Late Neoarchean by convergence-related processes akin to plate dynamics. Late-tectonic K-rich granitoids, mafic-ultramafic complexes and mafic dikes collectively mark the Neoarchean thickening and final cratonization of the continental crust.
Contributions to Mineralogy and Petrology, Vol. 175, 107, 17p. Pdf
Russia
deposit - Udachnaya
Abstract: The formation of diamonds within eclogitic rocks has been widely linked to the fate of carbon during subduction and, therefore, referred to conditions of pressure, temperature, and oxygen fugacity (fo2). Mantle-derived eclogite xenoliths from Udachnaya kimberlite pipes represent a unique window to investigate the formation of carbon-free, graphite-diamond-bearing and diamond-bearing rocks from the Siberian craton. With this aim, we exploited oxy-thermobarometers to retrieve information on the P-T-fo2 at which mantle eclogites from the Siberian craton equilibrated along with elemental carbon. The chemical analyses of coupled garnet and omphacitic clinopyroxene were integrated with data on their iron oxidation state, determined both by conventional and synchrotron 57Fe Mössbauer spectroscopy. The calculated fo2s largely vary for each suite of eclogite samples from 0.10 to - 2.43 log units (?FMQ) for C-free eclogites, from - 0.01 to - 2.91 (?FMQ) for graphite-diamond-bearing eclogites, and from - 2.08 to - 3.58 log units (?FMQ) for diamond-bearing eclogites. All eclogite samples mostly fall in the fo2 range typical of diamond coexisting with CO2-rich water-bearing melts and gaseous fluids, with diamondiferous eclogites being more reduced at fo2 conditions where circulating fluids can include some methane. When uncertainties on the calculated fo2 are taken into account, all samples essentially fall within the stability field of diamonds coexisting with CO2-bearing melts. Therefore, our results provide evidence of the potential role of CO2-bearing melts as growth medium on the formation of coexisting diamond and graphite in mantle eclogites during subduction of the oceanic crust.
Science, Vol. 369, 6507, pp. 110-1113. doi. 10.1126/ science.aba.1948
Mantle
water
Abstract: The abundances of Earth's chemical elements and their isotopic ratios can indicate which materials formed Earth. Enstatite chondrite (EC) meteorites provide a good isotopic match for many elements but are expected to contain no water because they formed in the hot inner Solar System. This would require Earth's water to be from a different source, such as comets. Piani et al. measured hydrogen contents and deuterium/hydrogen ratios (D/H) in 13 EC meteorites (see the Perspective by Peslier). They found far more hydrogen than is commonly assumed, with D/H close to that of Earth's mantle. Combining these data with cosmochemical models, they show that most of Earth's water could have formed from hydrogen delivered by EC meteorites.
Canadian diamond exploration.. high risk.. high reward. Background-historical and overview of current northwest Territories play to date June 11, 1993.
Bunting Warburg Inc. Research Report, June 11, 23p.
Abstract: In this study, we show how veined lithospheric mantle is involved in the genesis of ultrapotassic magmatism in cratonic settings. We conducted high pressure experiments to simulate vein + wall rock melting within the Earth's lithospheric mantle by reacting assemblages of harzburgite and phlogopite-rich hydrous mantle xenoliths. These comprised a mica-, amphibole-, rutile-, ilmenite-, diopside (MARID) assemblage at 3-5 GPa and 1325-1450 °C. Melting of the MARID assemblages results in infiltration of melt through the harzburgite, leading to its chemical alteration. At 3 and 4 GPa, melts are high in K2O (> 9 wt%) with K2O/Na2O > > 2 comparable to anorogenic lamproites. Higher pressures and temperatures (5 GPa/1450 °C) lead to increasing MgO contents of the melt and to some extent lower K2O contents (5-7 wt%) at equally high K2O/Na2O ratios. Our experiments provide insights into the role of alkalis in nickel-partitioning (DNi) between olivine and ultrapotassic melt. We observe that the high contents of Na, K, and Al are indicative of high DNi values, implying that the melt polymerization is the dominant factor influencing the olivine/melt nickel partitioning. The change of DNi as a function of melt composition results in a pressure independent, empirical geothermometer: Element oxides represent the composition of the glass (in wt%), and DNi is the liquid/olivine Ni-partitioning coefficient. We propose that this geothermometer is applicable to all natural silicate melts that crystallized olivine in a temperature interval between 1000 and 1600 °C. Application to glass-olivine pairs from calc-alkaline settings (Mexico), MORB (East Pacific Rise), and OIB (Hawaii) yielded reasonable values of 996-1199 °C, 1265 °C, and 1330 °C, respectively.
Abstract: Alkaline lavas occur globally in subduction-related volcanic arcs. Conventional models for the origin of these lavas typically invoke a multi-stage process in which mantle wedge peridotite, enriched in phlogopite and/or amphibole due to prior metasomatism, partially melts during infiltration by fluids and melts derived from subducted oceanic lithosphere. However, geochemical systematics in the majority of subduction-related alkaline lavas require physical mixing of subducted components and peridotite prior to partial melting. This can be explained by the mélange diapir model, which predicts the generation of arc magmas during advection of buoyant material from the slab-wedge interface into the mantle wedge below arcs. Here we report results from experiments in which natural mélange materials were partially melted at upper mantle conditions to produce alkaline magmas. Partial melts produced in our experiments have trace-element abundance patterns that are typical of alkaline arc lavas, such as enrichment in large ion lithophile elements (LILEs) and depletion in Nb and Ta. These results favor generation of alkaline magmas in the arc and backarc regions of subduction zones by partial melting of mélange materials rather than previously metasomatized peridotite.
Abstract: Diamonds growing in the Earth’s mantle often trap inclusions of fluids that are highly saline in composition. These fluids are thought to emerge from deep in subduction zones and may also be involved in the generation of some of the kimberlite magmas. However, the source of these fluids and the mechanism of their transport into the mantle lithosphere are unresolved. Here, we present experimental results showing that alkali chlorides are stable solid phases in the mantle lithosphere below 110 km. These alkali chlorides are formed by the reaction of subducted marine sediments with peridotite and show identical K/Na ratios to fluid inclusions in diamond. At temperatures >1100°C and low pressures, the chlorides are unstable; here, potassium is accommodated in mica and melt. The reaction of subducted sediments with peridotite explains the occurrence of Mg carbonates and the highly saline fluids found in diamonds and in chlorine-enriched kimberlite magmas.
Abstract: Across much of North America, the contact between Precambrian basement and Paleozoic strata is the Great Unconformity, a surface that represents a >0.4 b.y.-long hiatus. A digital elevation model (DEM) of this surface visually highlights regional-scale variability in the character of basement topography across the United States cratonic platform. Specifically, it delineates Phanerozoic tectonic domains, each characterized by a distinct structural wavelength (horizontal distance between adjacent highs) and/or structural amplitude (vertical distance between adjacent lows and highs). The largest domain, the Midcontinent domain, includes long-wavelength epeirogenic basins and domes, as well as fault-controlled steps. The pronounced change in land-surface elevation at the Rocky Mountain Front coincides with the western edge of the Midcontinent domain on the basement DEM. In the Rocky Mountain and Colorado Plateau domains, west of the Rocky Mountain Front, structural wavelength is significantly shorter and structural amplitude significantly higher than in the Midcontinent domain. The Bordering Basins domain outlines the southern and eastern edges of the Midcontinent domain. As emphasized by the basement DEM, several kilometers of structural relief occur across the boundary between these two domains, even though this boundary does not stand out on ground-surface topography. A plot of epicenters on the basement DEM supports models associating intraplate seismicity with the Midcontinent domain edge. Notably, certain changes in crustal thickness also coincide with distinct changes in basement depth.
Earth and Planetary Science Letters, Vol. 481, pp. 223-235.
United States, Illinois, Indiana, Kentucky
geophysics - seismics Reelfoot Rift
Abstract: Seismic discontinuities between the Moho and the inferred lithosphere-asthenosphere boundary (LAB) are known as mid-lithospheric discontinuities (MLDs) and have been ascribed to a variety of phenomena that are critical to understanding lithospheric growth and evolution. In this study, we used S-to-P converted waves recorded by the USArray Transportable Array and the OIINK (Ozarks-Illinois-Indiana-Kentucky) Flexible Array to investigate lithospheric structure beneath the central U.S. This region, a portion of North America's cratonic platform, provides an opportunity to explore how terrane accretion, cratonization, and subsequent rifting may have influenced lithospheric structure. The 3D common conversion point (CCP) volume produced by stacking back-projected Sp receiver functions reveals a general absence of negative converted phases at the depths of the LAB across much of the central U.S. This observation suggests a gradual velocity decrease between the lithosphere and asthenosphere. Within the lithosphere, the CCP stacks display negative arrivals at depths between 65 km and 125 km. We interpret these as MLDs resulting from the top of a layer of crystallized melts (sill-like igneous intrusions) or otherwise chemically modified lithosphere that is enriched in water and/or hydrous minerals. Chemical modification in this manner would cause a weak layer in the lithosphere that marks the MLDs. The depth and amplitude of negative MLD phases vary significantly both within and between the physiographic provinces of the midcontinent. Double, or overlapping, MLDs can be seen along Precambrian terrane boundaries and appear to result from stacked or imbricated lithospheric blocks. A prominent negative Sp phase can be clearly identified at 80 km depth within the Reelfoot Rift. This arrival aligns with the top of a zone of low shear-wave velocities, which suggests that it marks an unusually shallow seismic LAB for the midcontinent. This boundary would correspond to the top of a region of mechanically and chemically rejuvenated mantle that was likely emplaced during late Precambrian/early Cambrian rifting. These observations suggest that the lithospheric structure beneath the Reelfoot Rift may be an example of a global phenomenon in which MLDs act as weak zones that facilitate the removal of cratonic lithosphere that lies beneath.
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 251-264.
Technology
Rare earths
Abstract: Fluorite (CaF2) belongs to the isometric system, with a cubic, face-centred lattice. Fluorite commonly forms cubes or octahedrons, less commonly dodecahedrons and, rarely, tetrahexahedrons, trapezohedrons, trisoctahedrons, hexoctahedrons, and botyroidal forms. Fluorite is transparent to translucent, and has vitreous luster. It occurs in a variety of colours including purple, green, blue, or yellow, however it can also be colourless, and can exhibit colour zoning, (Staebler et al., 2006). Fluorite from many localities is fl uorescent (Verbeek, 2006). Fluorite density varies from 3.0-3.6 g/cm3, depending to a large extent on inclusions and impurities in the crystal lattice (Staebler et al., 2006), and its hardness is 4 on Mohs scale (Berry et al., 1983). Many single fl uorite crystals display sector zoning, refl ecting preferential substitution and incorporation of trace elements along successive crystal surfaces (Bosce and Rakovan, 2001). The Ca2+ ion in the fl uorite crystal structure can be substituted by Li+, Na+, K+, Mg2+, Mn2+, Fe2+,3+, Zn2+, Sr2+, Y3+, Zr4+, Ba2+, lanthanides ions, Pb2+, Th4+, and U4+ ions (Bailey et al., 1974; Bill and Calas, 1978, Gagnon et al., 2003; Schwinn and Markl, 2005; Xu et al., 2012; Deng et al., 2014). Concentrations of these impurities do not exceed 1% (Deer, 1965) except in yttrofl uorite (Ca,Y)F2-2.33 and cerfl uorite (Ca,Ce)F2-2.33 (Sverdrup, 1968). Fluorite occurs in a variety of rocks, as an accessory and as a gangue mineral in many metalliferous deposits and, in exceptional cases, as the main ore constituent of economic deposits (Simandl, 2009). Good examples of fl uorite mines are Las Cuevas, Encantada-Buenavista (Mexico); St. Lawrence pluton-related veins and the Rock Candy Mine (Canada); El Hamman veins (Morocco) and LeBurc Montroc -Le Moulinal and Trebas deposits (France) as documented by Ruiz et al. (1980), Grogan and Montgomery (1975), González-Partida et al. (2003), Munoz et al. (2005), and Fulton III and Miller (2006). Fluorite also commonly occurs adjacent to or within carbonatites and alkaline complexes (Kogut et al., 1998; Hagni,1999; Alvin et al., 2004; Xu et al., 2004; Salvi and Williams-Jones, 2006); Mississippi Valley-type (MVT) Pb- Zn-F-Ba deposits; F-Ba-(Pb-Zn) veins (Grogan and Bradbury, 1967 and 1968; Baxter et al., 1973; Kesler et al., 1989; Cardellach et al., 2002; Levresse et al., 2006); hydrothermal Fe (±Au, ±Cu) and rare earth element (REE) deposits (Borrok et al., 1998; Andrade et al., 1999; Fourie, 2000); precious metal concentrations (Hill et al., 2000); fl uorite/metal-bearing skarns (Lu et al., 2003); Sn-polymetallic greissen-type deposits (Bettencourt et al., 2005); and zeolitic rocks and uranium deposits (Sheppard and Mumpton, 1984; Cunningham et al., 1998; Min et al., 2005). Ore deposit studies that document the trace element distribution in fl uorite are provided by Möller et al. (1976), Bau et al. (2003), Gagnon et al. (2003), Schwinn and Markl (2005), and Deng et al. (2014). The benchmark paper by Möller et al. (1976) identifi ed variations in the chemical composition of fl uorites according their origin (sedimentary, hydrothermal, or pegmatitic). Recently, Makin et al. (2014) compiled trace-element compositions of fl uorite from MVT, fl uorite-barite veins, peralkaline-related, and carbonatite-related deposits. They showed that fl uorite from MVT and carbonatite deposits can be distinguished through trace element concentrations, and that the REE concentration of fl uorite from veins is largely independent of the composition of the host rock. Based on the physical and chemical properties of fl uorite, its association with a variety of deposit types, and previous studies, it is possible that fl uorite can be used as a proximal indicator mineral to explore for a variety of deposit types. Unfortunately, the compilation by Makin et al. (2014) contained chemical analyses performed at different laboratories using different analytical techniques (including laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), electron microprobe, neutron activation, and ICP-MS), and precision and accuracy varied accordingly. As an orientation survey, herein we present data from fi ve deposits, with two samples from the Rock Candy deposit (British Columbia), and one sample from each of Kootenay Florence (British Columbia), Eaglet (British Columbia), Eldor (Quebec), and Hastie quarry (Illinois) deposits (Table 1). The main objectives of this study are to: 1) assess variations in chemical composition of fl uorite in the samples and deposit types; 2) evaluate relations between analyses made using laser ablation-inductively coupled plasma mass spectrometry on individual grains [LA-ICP-MS(IG)], and those made using laser ablation-inductively coupled plasma mass spectrometry on fused beads [LA-ICP-MS(FB)] and X-ray fl uorescence (XRF); 3) test the use of stoichiometric Ca content as an internal fl uorite standard, such has been done by Gagnon et al. (2003) and Schwinn and Markl, (2005); 4) select the elements that are commonly present in concentrations above the lower limit of detection of LA-ICP-MS and available for constructing discrimination diagrams; 5) consider if our results agree with the preliminary discrimination diagrams of Makin et al. (2014).
Abstract: Plutons associated with a 1.4 Ga magmatic event intrude across southwestern Laurentia. The tectonic setting of this major magmatic province is poorly understood. Proposed melting models include anorogenic heating from the mantle, continental arc or transpressive orogeny, and anatexis from radiogenic heat buildup in thickened crust. Re-Os analyses of refractory mantle xenoliths from the Navajo volcanic field (NVF; central Colorado Plateau) yield Re depletion ages of 2.1–1.7 Ga, consistent with the age of the overlying Yavapai and Mazatzal crust. However, new Sm-Nd isotope data from clinopyroxene in peridotite xenoliths from NVF diatremes show a subset of xenoliths that plot on a ca. 1.4 Ga isochron, which likely reflects mantle melt production and isotopic resetting at 1.4 Ga. This suggests that Paleoproterozoic subcontinental lithospheric mantle was involved in the 1.4 Ga magmatic event. Our constraints support a subduction model for the generation of the 1.4 Ga granites but are inconsistent with rifting and anorogenic anatexis models, both of which would require removal of ancient lithosphere.
Abstract: Subducting serpentinized lithosphere has distinct dD and d18O values compared to normal mantle. Slab-derived fluids that infiltrate the mantle wedge can alter its oxygen and hydrogen isotope composition, raising or lowering the d18O and dD values depending on the nature of the subducted components. Hydrous minerals in peridotite xenoliths from the Colorado Plateau (southwestern USA) have dD values (up to -33‰) much higher than average mantle (-80‰), but similar to dD values of olivine-hosted melt inclusions within arc basalts, suggesting a slab-derived fluid source. Oxygen isotope ratios of olivine from these xenoliths are similar to average mantle, yet display a strong negative correlation with clinopyroxene Ce/Sm, a proxy of metasomatism. This correlation is most simply explained by metasomatism from fluids derived from the serpentinized portion of the Farallon slab. Although d18O values of mantle minerals span a narrow range, integration of stable isotope data with other geochemical tracers can provide new constraints on modern and ancient subduction-related processes, potentially providing a method for probing Archean lithospheric mantle for evidence of early subduction.
Abstract: The H/C ratio in earth’s exosphere is higher than it is in the source region of primitive basalts, suggesting an enriched carbon reservoir in the mantle[1]. A plausible explanation is that subduction of carbon may have enriched the mantle in recycled carbon over time. Average basaltic crust contains ~ 2 wt.% CO2 [2], and modeling of slab devolatilisation suggests that subducted carbonate may survive to be transported deeper into the mantle [3]. Carbonated oceanic crust should melt in the transition zone along most subduction geotherms due to a deep trough in the carbonated basalt solidus, and mineral inclusions in superdeep diamonds testify to carbonate melt in their formation [4]. Along cool subduction geotherms carbonate may subduct into the lower mantle, potentially enriching the deep mantle in carbon. Here we report on laser-heated diamond anvil cell experiments in the CaO-MgO-SiO2-CO2 and FeO-MgO-SiO2-CO2 systems at lower mantle pressures where we investigate the stability of carbonate in oceanic crust, and test for decarbonation and diamond forming reactions involving carbonate and coexisiting free silica. We find that carbonate reacts with silica to form bridgmanite ± Ca-perovskite + CO2 at pressures in the range of ~50 to 70 GPa. These decarbonation reactions form an impenetrable barrier to subduction of carbonate into the deeper lower mantle, however, slabs may carry solid CO2 (Phase V) into the deeper lower mantle. We also identify reactions where carbonate or CO2 dissociate to form diamond plus oxygen. We suggest that the deep lower mantle may become enriched in carbon in the form of diamond over time due to subduction of carbonate and solid CO2 and its eventual dissociation to form diamond plus oxygen. Release of oxygen during diamond formation may also provide a mechanism for locally oxidizing the deep mantle.
Earth and Planetary Science Letters, Vol. 499, pp. 219-229.
United States, Colorado Plateau
metasomatism
Abstract: In magmatic settings, water behaves as an incompatible species and should be depleted during melting and enriched during metasomatism. Previous studies have identified correlations between nominally anhydrous mineral (NAM) water content ([H2O]) and indices of metasomatism or melt extraction, seemingly confirming this behavior in the mantle. However in detail, these correlations are ambiguous and do not reflect robust controls on NAM [H2O]. We measured orthopyroxene (opx) and clinopyroxene (cpx) [H2O] in variably hydrated and metasomatized peridotite xenoliths from the Navajo volcanic field (NVF) that sample the Colorado Plateau subcontinental lithospheric mantle (SCLM), an endmember of SCLM hydration and metasomatism. These xenoliths span a wide range of pyroxene [H2O] (opx from 50 to 588 ppm wt. H2O; cpx from 38 to 581 ppm wt. H2O), but NAM [H2O] does not correlate with either indices of melt depletion or metasomatism. Growth of hydrous minerals suggests higher water activity than in anhydrous peridotites, and therefore hydrous-mineral-bearing xenoliths and anhydrous xenoliths should have different NAM [H2O] and water activities. However, when the two groups are compared no significant differences can be found in either NAM [H2O] or water activity. We propose that the high diffusivity of hydrogen in the mantle allows for equilibration of water activity in the mantle over sub-kilometer length scales over geologic time. Such diffusive equilibration reduces water activity variability and results in the blurring and destruction of correlations between NAM [H2O] and indices of metasomatism or melt extraction. As a result of diffusive equilibration of water, there is a large difference in the variability of concentration between NAM [H2O] (spanning ~2 orders of magnitude) and similarly incompatible elements such as Ce in the same peridotites (spanning ~4 orders of magnitude). This difference in behavior explains why H2O/Ce ratios in mantle peridotites are highly variable relative to those of basalts.
Resource estimation and valuation of alluvial diamond deposits.
Proceedings of the 10th. International Kimberlite Conference, Vol. 2, Special Issue of the Journal of the Geological Society of India,, Vol. 2, pp. 281-288.
De Wit, M., Bhebhe, Z., Davidson, J., Haggerty, S.E., Hundt, P., Jacob, J., Lynn, M., Marshall, T.R., Skinner, C., Smithson, K., Stiefenhofer, J., Robert, M., Revitt, A., Spaggiari, R., Ward, J.
Abstract: From the discovery of diamonds in South Africa in 1866 until the end of 2013, Africa is estimated to have produced almost 3.2 Bct out of a total global production of 5.03 Bct, or 63.6% of all diamonds that have ever been mined. In 2013 African countries ranked 2nd (Botswana), 3rd (DRC), 6th (Zimbabwe), 7th (Angola), 8th (South Africa), and 9th (Namibia), in terms of carat production and 1st (Botswana), 4th (Namibia), 5th (Angola), 6th (South Africa), 7th (Zimbabwe), and 9th (DRC), in terms of value of the diamonds produced. In 2013 Africa produced 70.6 Mct out of a global total of 130.5 Mct or 54.1%, which was valued at US$ 8.7 billion representing 61.5% of the global value of US$ 14.1 billion.
IN: Deep carbon: past to present, Orcutt, Daniel, Dasgupta eds., pp. 237-275.
Mantle
carbon
Abstract: This chapter provides a summary of the flux of carbon through various oceanic volcanic centers such as mid-ocean ridges and intraplate settings, as well as what these fluxes indicate about the carbon content of the mantle. By reviewing methods used to measure the carbon geochemistry of basalts and then to estimate fluxes, the chapter provides insight into how mantle melting and melt extraction processes are estimated. The chapter discusses how the flux of carbon compares with other incompatible trace elements and gases. From there, the chapter discusses whether the budget of carbon in the ocean mantle can be explained by primordial carbon or whether carbon recycling is required to balance the budget.
Gems & Gemology, Vol. 56, 2, summer pp. 230-257. pdf
South America, Columbia
deposit - Chivor
Abstract: The history of the Chivor emerald mine in Colombia is a saga with countless twists and turns, involving parties from across the globe. Indigenous people initially exploited the property, followed by the Spanish in the sixteenth and seventeenth centuries, before abandonment set in for 200 years. The mine was rediscovered by Francisco Restrepo in the 1880s, and ownership over the ensuing decades passed through several Colombian owners and eventually to an American company, the Colombian Emerald Syndicate, Ltd., with an intervening but unsuccessful attempt by a German group organized by Fritz Klein to take control. With the Colombian Emerald Syndicate succumbing to bankruptcy in 1923, the property was sold and then transferred in 1924 to another American firm, the Colombia Emerald Development Corporation. Under the new ownership, stock market speculation played a far more prominent role in the story than actual mining. Nonetheless, periods of more productive mining operations did take place under managers Peter W. Rainier and Russell W. Anderton. Yet these were not enough to prevent the company, renamed Chivor Emerald Mines, Inc. in 1933, from entering insolvency in 1952 and being placed into receivership. Leadership by Willis Frederick Bronkie enabled the firm to regain independence in 1970 and shortly thereafter to be sold in a series of transactions, with Chivor gradually being returned to Colombian interests.
International Journal of Earth Science, Vol. 109, 4, pp. 1487-1500.
Africa, Madagascar
tectonics
Abstract: This study uses gravimetric data integrated with recent seismic data published on south Madagascar to investigate geometry of crust-mantle interface. The regional tectonic framework of Madagascar is characterised by anastomosing network of up to 15-km-wide, 600-km-long and north-oriented high-strain zones, which originated during Neoproterozoic convergence. The studied Bouguer anomalies obtained from the International Gravimetric Bureau were high-pass filtered to emphasise short-wavelength gravimetric variations (shorter than 200 km). The Pan-African high-strain zones coincide with the positive gravimetric anomalies suggesting a link with deep seated high-density material. Considering the present-day thickness of the crust (35 km) and its seismic velocity record, the gravimetric anomalies can be visualised as narrow vertical tabular bodies located at the base of the Moho. Modelling further confirmed that such narrow vertical bodies could be stable over geologic time scale since these structures are relatively small (10 to 30 km wide). The vertical tabular bodies possibly reflect material transfer such as vertical motion of sub-crustal weak and possibly partially molten mantle along vertical deformation zones. It is proposed that these structures were initiated by folding of weak mantle-crust interface characterised by low-viscosity contrast between weak mantle and stronger granulitized lower crust during bulk pure shear-dominated horizontal shortening. It is proposed that the cuspate-lobate "mullion-type" geometry mimics rheological inversions of mafic and felsic rocks and shape of folds of variable scale observed in southern Madagascar. The formation of such mega-mullion structures is possibly an expression of "crème brulée" rheological model, where the deformation of the lithosphere is governed by stronger granulitic lower crust and weaker partially molten and/or hydrated mantle.
Feneyrol, J., Giuliani, G., Demaiffe, D., Ohenstetter, D., Fallick, A.E., Dubessy, J., Martelet, J-E., Rakotondrazafy, A.F.M., Omito, E., Ichangi, D., Nyamai, C., Wamunyu, W.
Abstract: The genetic model previously proposed for tsavorite- (and tanzanite-) bearing mineralization hosted in the Neoproterozoic Metamorphic Mozambique Belt (stretching from Kenya through Tanzania to Madagascar) is refined on the basis of new Sm-Nd age determinations and detailed Sr-O-S isotope and fluid-inclusion studies. The deposits are hosted within meta-sedimentary series composed of quartzites, graphitic gneisses, calc-silicate rocks intercalated with meta-evaporites, and marbles. Tsavorite occurs either in nodules (also called “boudins”) oriented parallel to the metamorphic foliation in all of the deposits in the metamorphic belt or in quartz veins and lenses located at the hinges of anticlinal folds (Lelatema fold belt and Ruangwa deposits, Tanzania). Gem tanzanite occurs in pockets and lenses in the Lelatema fold belt of northern Tanzania. The Sm-Nd isotopic data for tsavorites and tanzanites hosted in quartz veins and lenses from Merelani demonstrate that they formed at 600 Ma, during the retrograde metamorphic episode associated with the East African Orogeny. The tsavorites hosted in nodules do not provide reliable ages: their sedimentary protoliths had heterogeneous compositions and their Sm-Nd system was not completely rehomogenized, even at the local scale, by the fluid-absent metamorphic recrystallization. The initial 87Sr/86Sr isotopic ratios of calcite from marble and tanzanites from Merelani fit with the strontium isotopic composition of Neoproterozoic marine carbonates. Seawater sediment deposition in the Mozambique Ocean took place around 720 Ma. The quartz-zoisite O-isotopic thermometer indicates a temperature of formation for zoisite between 385 and 448 °C. The sulfur isotopic composition of pyrite (between –7.8 and –1.3‰ V-CDT) associated with tsavorite in the Lelatema fold belt deposits suggests the contribution of reduced marine sulfate. The sulfur in pyrite in the marbles was likely derived from bacterial sulfate reduction which produced H2S. Fluid inclusion data from tsavorite and tanzanite samples from the Merelani mine indicate the presence of a dominant H2S-S8±(CH4)±(N2)±(H2O)-bearing fluid. In the deposits in Kenya and Madagascar, the replacement of sulfate by tsavorite in the nodules and the boron isotopic composition of tourmaline associated with tsavorite are strong arguments in favor of the participation of evaporites in garnet formation.
Society of Economic Geology Geoscience and Exploration of the Argyle, Bunder, Diavik, and Murowa Diamond Deposits, Special Publication no. 20, pp. 379-402.
Journal of Volcanology and Geothermal Research, Vol. 357, pp. 68-91.
Mantle
volcanism
Abstract: Volcanic stratigraphy is a fundamental component of geological mapping in volcanic areas as it yields the basic criteria and essential data for identifying the spatial and temporal relationships between volcanic products and intra/inter-eruptive processes (earth-surface, tectonic and climatic), which in turn provides greater understanding of the geological evolution of a region. Establishing precise stratigraphic relationships in volcanic successions is not only essential for understanding the past behaviour of volcanoes and for predicting how they might behave in the future, but is also critical for establishing guidelines for exploring economic and energy resources associated with volcanic systems or for reconstructing the evolution of sedimentary basins in which volcanism has played a significant role. Like classical stratigraphy, volcanic stratigraphy should also be defined using a systematic methodology that can provide an organised and comprehensive description of the temporal and spatial evolution of volcanic terrain. This review explores different methods employed in studies of volcanic stratigraphy, examines four case studies that use differing stratigraphic approaches, and recommends methods for using systematic volcanic stratigraphy based on the application of the concepts of traditional stratigraphy but adapted to the needs of volcanological environment.
Role of iron and reducing conditions on the stability of dolomite + coesite between 4.25 and 6 GPa - a potential mechanism for diamond formation during subduction
European Journal of Mineralogy, Vol. 23, 1, pp. 5-16.
Martin, A.M., Laporte, D., Koga, K.T., Kawamoto, T., Hammouda, T.
Experimental study of the stability of a dolomite + coesite assemblage in contact with peridotite: implications for sediment-mantle interaction and diamond formation during subduction.
Martin, A.M., Laporte, D., Koga, K.T., Kawamoto, T., Hammouda, T.
Experimental stidy of the stability of a dolomite + coesite assembalge in contact with peridotite: implications for sediment-mantle interaction and diamond formation during subduction.
Abstract: The lithospheric mantle beneath West Antarctica has been characterized using petrology, whole-rock and mineral major element geochemistry, whole-rock trace element chemistry and Mössbauer spectroscopy data obtained on a suite of peridotite (lherzolite and harzburgite) and pyroxenite xenoliths from the Mount Morning eruptive centre, Southern Victoria Land. The timing of pyroxenite formation in Victoria Land overlaps with subduction of the Palaeo-Pacific plate beneath the Gondwana margin and pyroxenite is likely to have formed when fluids derived from, or modified by, melting of the subducting, eclogitic, oceanic crustal plate percolated through peridotite of the lithospheric mantle. Subsequent melting of lithospheric pyroxenite veins similar to those represented in the Mount Morning xenolith suite has contributed to the enriched trace element (and isotope) signatures seen in Cenozoic volcanic rocks from Mount Morning, elsewhere in Victoria Land and Zealandia. In general, the harzburgite xenoliths reflect between 20 and 30% melt depletion. Their depleted element budgets are consistent with Archaean cratonization ages and they have mantle-normalized trace element patterns comparable with typical subcontinental lithospheric mantle. The spinel lherzolite mineral data suggest a similar amount of depletion to that recorded in the harzburgites (20-30%), whereas plagioclase lherzolite mineral data suggest <15% melt depletion. The lherzolite (spinel and plagioclase) xenolith whole-rocks have compositions indicating <20% melt depletion, consistent with Proterozoic to Phanerozoic cratonization ages, and have mantle-normalized trace element patterns comparable with typical depleted mid-ocean ridge mantle. All peridotite xenoliths have undergone a number of melt-rock reaction events. Melting took place mainly in the spinel peridotite stability field, but one plagioclase peridotite group containing high-sodium clinopyroxenes is best modelled by melting in the garnet field. Median oxygen fugacity estimates based on Mössbauer spectroscopy measurements of spinel and pyroxene for spinel-facies conditions in the rifted Antarctic lithosphere are -0·6 ?log fO2 at Mount Morning and –1·0 ± 0·1 (1s) ?log fO2 for all of Victoria Land, relative to the fayalite-magnetite-quartz buffer. These values are in good agreement with a calculated global median value of -0·9 ± 0·1 (1s) ?log fO2 for mantle spinel-facies rocks from continental rift systems.
Abstract: We present the first regional in-situ zircon U-Pb-Hf isotopic data from metaigneous and metasedimentary rocks from the Paleo- to Mesoproterozoic Rio Apa Terrane (RAT), a crustal fragment outcropping in the central-western Brazil and north-eastern Paraguay. These new ages and Hf isotopic data delineate three magmatic events, which record the construction of the temporally and isotopically distinct Western and Eastern Terranes of the RAT. The Western Terrane comprises the 2100-1940 Ma Porto Murtinho Complex and the 1900-1840 Ma Amoguijá Belt, which both define a crustal reworking array in eHfT-time space evolving from a precursor source with Hf TDM age of ca. 2700 Ma. The 1800-1720 Ma Caracol Belt constitutes the Eastern Terrane and yields suprachondritic eHfT signatures up to +7.1, indicating significant juvenile input. The metasedimentary Amolar Group and Rio Naitaca Formation in the Western Terrane have maximum depositional ages of 1850-1800 Ma and subchondritic eHfT signatures down to -5.7, similar to the underlying basement of the Amoguijá Belt. In the Eastern Terrane, the Alto Tererê Formation has a maximum depositional age of 1750 Ma and mostly suprachondritic eHfT signatures, similar to magmatic rocks of the underlying Caracol Belt. Together, the new igneous and detrital zircon age and Hf isotopic data record a temporal and spatial transition from 2100 to 1840 Ma crustal reworking in the west to more juvenile magmatism at 1800-1720 Ma in the east. This transition is interpreted to reflect convergent margin magmatism associated with periods of subduction zone advance and retreat in an accretionary orogenic setting. Comparison of the eHfT-time signature of the RAT with the Amazonian Craton suggest penecontemporaneous development, with the Western and Eastern Terranes of the RAT being correlative with the Ventuari-Tapajós and Rio Negro-Juruena Province of the Amazonian Craton, respectively. Our new data also reveal that the eHfT signatures of the RAT are distinct from the Maz terrane, which refutes the MARA Block hypothesis.
Abstract: Moissanite (SiC) occurs in mantle and mantle-generated rocks from different tectonic settings. SiC is stable only at low oxygen fugacity (ƒO2) ?IW. Israeli SiC is assiociated with corundum, Fe globules, native V and other phases in Cretaceous pyroclastic rocks from Mt Carmel and associated alluvial deposits[1]. The SiC grains contain inclusions of Si metal, FeSi2, FeTiSi2, FeAlSi2 and CaSi2+xSi2-x, which were liquids before being trapped during SiC crystallization. SiC has been found included in corundum, associated with Fe-Ti silicides, connecting the formation of SiC, reduced melts in corundum and conrundum itself. All grains are of the 6H polytype. d13C ranges from - 32.1 to -24.5‰ and d30Si from -0.68 to +1.42‰. These SiC grains are one product of the interaction of basaltic magma and mantle methane in a volcanic plumbing system. SiC crystallized from metallic melts that became immiscible during the reduction of the magma. Its low d13C may reflect Rayleigh fractionation under reduced conditions; the variation in Si isotopes may reflect fractionation between SiC and immiscible metallic melts. SiC samples from the Udachnaya and Mir kimberlite pipes contain inclusions of Si metal, FeSi2, FeSi, FeTiSi2, Si(N,O). The SiC has d13C ranging from -28.5 to -24.8‰, and d30Si from -1.72 to +1.42‰. SiC from harzburgites, chromitites and pyroxenites of the Tibetan Zedang ophiolites have inclusions of Si metal and unmixed Fe-Ni-Ti-Si alloy. Their d13C ranges from -30.6 to -24.7‰ and d30Si from -0.85 to +1.26‰. SiC samples from these different settings show very similar characteristics, implying that they may be formed in similar mantle conditions, where the flux of mantle methane gradually reduces magmas and interacts with them to produce different reduced phases at different stages.
Earth and Planetary Science Letters, Vol. 497, 1, pp. 181-192.
Mantle
metasomatism
Abstract: At convergent margins fluids liberated from subducting slabs metasomatise the overlying mantle wedge, enriching it in volatiles, incompatible elements and possibly ore-forming metals. Despite the genetic link between this process, the genesis of arc magmas, and formation of porphyry Cu-Au deposits, there is currently little understanding of the behaviour of chalcophile and siderophile elements during subduction-related mantle metasomatism. In this study, we report sulfur isotopic compositions and PGE concentrations of sulfides in a suite of garnet peridotites from the Western Gneiss Region of Norway, sampling mantle wedge from ~100 to ~250 km depth. Sulfides hosted in metasomatised samples have deviated from typical mantle values, ranging between -10.0 and +5.4‰, indicating derivation of sulfur from subducted crust. Sulfides in pervasively metasomatised samples have atypical PGE signatures, with strong enrichment in Os and Ru relative to Ir, whereas channelised fluid flow produced sulfides extremely enriched in Pd, up to 700 times the concentration found in non-metasomatised samples. These signatures are reconcilable with a high oxidation state of the metasomatising agents and demonstrate that subduction can recycle chalcophile and siderophile elements into and within the mantle, along with sulfur. We further show that because the solubility of Os and Ru in fluids is redox sensitive, and Pd is more soluble than the I-PGE, ratios such as Os/Ir, Ru/Ir plotted against Pd/Ir can be used to trace the metasomatic oxidation of mantle samples, mantle-derived magmas and porphyry Cu±Au deposits. This geochemical insight is used to show that Au-rich porphyry Cu deposits are derived from more oxidised mantle wedge than Au-poor porphyry deposits.
Geochimica et Cosmochimica Acta, in press available, 19p.
Africa, South Africa, Canada, South America, Brazil
deposit - Lac de Gras, Paranaiba
Abstract: Kimberlites are the deepest melts produced on Earth that are erupted at the surface and can therefore provide unique insights into the composition and evolution of the mantle. Radiogenic isotopes provide ambiguous evidence for the occurrence of recycled crustal material in kimberlite sources. Oxygen isotopes can fractionate significantly only in the shallow crust, and thus represent a powerful tracer of subducted material in the sources of kimberlite. To constrain the oxygen isotope composition of kimberlite melts, we have examined olivine grains in eleven Cretaceous to Eocene archetypal kimberlites from southern Africa, Lac de Gras (Canada) and Alto Paranaiba (Brazil), which exhibit radiogenic isotope evidence for recycled crustal material in their sources including highly radiogenic Pb isotopes and Nd-Hf isotope compositions deviating below the mantle array. Olivine grains are commonly zoned between a mantle-derived xenocrystic core and one or more magmatic overgrowths, i.e. occasional internal zones, ubiquitous rims and rare rinds (moving outward from the core). The oxygen isotope composition of different olivine zones was determined in situ within separated olivine grains by secondary ion mass spectrometry (SIMS) after point selection using back-scattered electron (BSE) images combined with major and minor element analyses. With the exception of a few cores, the d18O values of different olivine zones do not deviate from typical mantle olivine values of 5.18?±?0.28‰ (Mattey et al., 1994). There are no correlations between oxygen isotopes and major/minor element compositions for internal zones and rims from individual localities or in the entire dataset. This indicates that the oxygen isotope composition of kimberlite melts is not affected by melt differentiation to the point of olivine rim crystallisation. However, olivine rinds from the Koala kimberlite (Canada) display an inverse correlation between d18O and Mn-Ca concentrations, with d18O values extending below the mantle range, which is probably due to carbonate fractionation, CO2 degassing and/or assimilation of serpentine-rich material after kimberlite emplacement in the upper crust. The mantle-like d18O composition of olivine internal zones and rims suggests that assimilation of mantle material and liberation of a CO2-rich phase during ascent in the mantle do not significantly modify the original d18O signature of kimberlite melts. Modelling of oxygen isotope fractionation shows that up to 15 wt% of CO2 can be lost by kimberlites en route to the upper crust. Our results combined with mass balance calculations indicate that only a limited amount (<5-10 wt%) of recycled crustal material could occur in the source of kimberlites from southern Africa, Lac de Gras and Alto Paranaiba, or that the recycled material had an oxygen isotope composition similar to the mantle.
Abstract: Pyrochlore from the Kaiserstuhl volcanic complex (SW Germany) shows textural and compositional differences between various coarse-grained calcite-carbonatite bodies (Badberg, Degenmatt, Haselschacher Buck, Orberg) and extrusive carbonatites (Henkenberg, Kirchberg). Oscillatory-zoned F-rich pyrochlore with up to 69?wt% Nb2O5 is common in all coarse-grained calcite-carbonatite bodies and probably formed during magmatic conditions. However, only in some of the samples from the Badberg, partly resorbed U- and Ta-enriched pyrochlore cores with up to 22?wt% UO2 and 9?wt% Ta2O5 have been identified, which are interpreted as being inherited from underlying nosean syenites. Pyrochlore data from a drill core penetrating the Badberg indicate increasing contents of REE, U, and Ta with depth, while Nb, F and Na contents decrease. This may reflect the combined effects of fractional crystallization and assimilation (AFC) or indicates a multi-stage emplacement of the carbonatitic magma. Patchy-zoned ceriopyrochlore and REE- and Th-enriched pyrochlore with up to 19?wt% total REE2O3 and 6.5?wt% ThO2 is largely restricted to samples from the Orberg and probably formed during hydrothermal conditions. This can be related to the relatively evolved character of the Orberg carbonatites, based on their relatively high whole-rock Nb/Ta and Zr/Hf mass ratios. This study demonstrates that the textural and compositional variation of pyrochlore in carbonatites is a powerful tool to distinguish magmatic, hydrothermal and weathering processes in carbonatitic systems.
Sr Na REE titanates of the crichtonite group from a fenitized megaxenolith, Khibin a alkaline complex, Kola Peninsula, Russia: first occurrence and implications.
European Journal of Mineralogy, Vol. 18, 4, August pp. 493-502.
Abstract: A prominent dike of camptonite cuts the Middle Ordovician Tétreauville Formation of the Trenton Group in the Montréal-Est quarry operated by Lafarge Canada Inc. The “Lafarge” dike is strikingly porphyritic, with largely anhedral macrocrysts of unzoned calcic amphibole up to 13 cm across. The macrocrysts are rimmed with ferri-kaersutite resembling the amphibole in the fine-grained matrix of the camptonite. The magnesio-hastingstite macrocrysts have virtually the same composition as the matrix; they thus grew without much of a boundary layer. The magma crystallized in a disequilibrium way as a pseudo-unary system. The macrocrysts are unusually enriched in Fe3+ (approximately 44% of the total iron), yet locally enclose globules of immiscible sulfide melt. The magma became oxygenated owing to preferential loss of hydrogen upon the dissociation of aqueous gas bubbles. The amygdaloidal macrocrysts have a relatively high dD value because of this loss of H2; the values of d18O are typical of an upper mantle source. Camptonite dikes are very common on Mont Royal. Like the Lafarge dike, they likely arose by the disequilibrium crystallization of batches of the parental melt of asthenospheric origin.
Abstract: We have investigated a locality very well known to mineral collectors, the Yates U-Th prospect near Otter Lake, Québec. There, dikes of orange to pink calcite enclose euhedral prisms of fluorapatite, locally aligned. Early investigators pointed out the importance of micro-inclusions in the prisms. We describe and image the micro-inclusions in two polished sections of fluorapatite prisms, one of them with a millimetric globule of orange calcite similar to that in the matrix. We interpret the globule to have been an inclusion of melt trapped during growth. Micro-globules disseminated in the fluorapatite are interpreted to have crystallized in situ from aliquots of the boundary-layer melt enriched in constituents rejected by the fluorapatite; the micro-globules contain a complex jigsawed assemblage of carbonate, silicate, and sulfate minerals. Early minerals to crystallize are commonly partly dissolved and partly replaced by lower-temperature phases. Such jigsawed assemblages seem to be absent in the carbonate matrix sampled away from the fluorapatite prisms. The pressure and temperature attained at the Rigolet stage of the Grenville collisional orogeny were conducive to the anatexis of marble in the presence of H2O. The carbonate melt is considered to have become silicocarbonatitic by assimilation of the enclosing gneisses, which were also close to their melting point. Degassing was important, and the melt froze quickly. The evidence points to a magmatic origin for the carbonate dikes and the associated clinopyroxenite, rather than a skarn-related association.
Journal of Volcanology and Geothermal Research, Vol. 354, pp. 87-101.
Mantle
magmatism
Abstract: Volcanic eruptions are fed by plumbing systems that transport magma from its source to the surface, mostly fed by dykes. Here we present laboratory experiments that model dyke ascent to eruption using a tank filled with a crust analogue (gelatine, which is transparent and elastic) that is injected from below by a magma analogue (dyed water). This novel experimental setup allows, for the first time, the simultaneous measurement of fluid flow, sub-surface and surface deformation during dyke ascent. During injection, a penny-shaped fluid-filled crack is formed, intrudes, and traverses the gelatine slab vertically to then erupt at the surface. Polarised light shows the internal stress evolution as the dyke ascends, and an overhead laser scanner measures the surface elevation change in the lead-up to dyke eruption. Fluorescent passive-tracer particles that are illuminated by a laser sheet are monitored, and the intruding fluid's flow dynamics and gelatine's sub-surface strain evolution is measured using particle image velocimetry and digital image correlation, respectively. We identify 4 previously undescribed stages of dyke ascent. Stage 1, early dyke growth: the initial dyke grows from the source, and two fluid jets circulate as the penny-shaped crack is formed. Stage 2, pseudo-steady dyke growth: characterised by the development of a rapidly uprising, central, single pseudo-steady fluid jet, as the dyke grows equally in length and width, and the fluid down-wells at the dyke margin. Sub-surface host strain is localised at the head region and the tail of the dyke is largely static. Stage 3, pre-eruption unsteady dyke growth: an instability in the fluid flow appears as the central fluid jet meanders, the dyke tip accelerates towards the surface and the tail thins. Surface deformation is only detected in the immediate lead-up to eruption and is characterised by an overall topographic increase, with axis-symmetric topographic highs developed above the dyke tip. Stage 4 is the onset of eruption, when fluid flow is projected outwards and focused towards the erupting fissure as the dyke closes. A simultaneous and abrupt decrease in sub-surface strain occurs as the fluid pressure is released. Our results provide a comprehensive physical framework upon which to interpret evidence of dyke ascent in nature, and suggest dyke ascent models need to be re-evaluated to account for coupled intrusive and extrusive processes and improve the recognition of monitoring signals that lead to volcanic eruptions in nature.
Methods and Applications in Flouresence, Vol. 8, 1, 01404 htpp:dx.doi.org/10.1088/2050-6120/ab4eac
Global
luminescence
Abstract: We report a multidimensional luminescence microscope providing hyperspectral imaging and time-resolved (luminescence lifetime) imaging for the study of luminescent diamond defects. The instrument includes crossed-polariser white light transmission microscopy to reveal any birefringence that would indicate strain in the diamond lattice. We demonstrate the application of this new instrument to detect defects in natural and synthetic diamonds including N3, nitrogen and silicon vacancies. Hyperspectral imaging provides contrast that is not apparent in conventional intensity images and the luminescence lifetime provides further contrast.
Recovery of non-magnetic minerals with a gravity magnetic seperator
American Institute of Mining, Metallurgical, and Petroleum Engineers (AIME) Preprint, Annual Meeting held Phoenix Arizona Feb. 24-27th. 1992, Preprint No. 92-65, 6p
Mangas, J., Perez-Torrado, F.J., Reguilon, R., Martin-Izard, A.
Geological characteristics of alkaline rocks and carbonatites of Fuerteventura (Canary Islands, Spain) and their rare earth elements (REE) ore potential.
Terra Abstracts, IAGOD International Symposium on mineralization related to mafic, Vol. 5, No. 3, abstract supplement p. 32.
Journal of South American Earth Sciences, Vol. 94, 102208 13p. Pdf
South America, Brazil
carbonatite
Abstract: Carbonatites are peculiar igneous rocks, consisting mainly of greater than 50% carbonate minerals, which arouse an economic interest due to the potentiality of high phosphate content and Light Rare Earth Elements (LREE) associated with their occurrence. The Passo Feio Carbonatite (PFC) is located 17?km Southwest of Caçapava do Sul city and constitutes NW dipping body, which is interposed with Passo Feio Formation metamorphic rocks. The PFC varies texturally from massive to foliated, being mainly composed of calcites and dolomites and on a smaller scale by apatites, phlogopites and tremolites. The opaque minerals correspond to hematites, magnetites, pyrites and barites, while the accessory minerals are represented by zircons, monazites- (Ce) and aeschynites- (Ce). Probably those REE mineral phases correspond to a hydrothermal stage, with the REE remobilization from apatites into those latter REE-rich mineral phases - this hypothesis is corroborated by geochemistry, mineral chemistry and microtextures found. Considering the results of mineral chemistry and taking into account the textural criteria, it was possible to classify carbonatite as an alvikite, with geochemical patterns that do not indicate economic potential for REE. However, soil geochemistry showed an important enrichment in REE, reflecting a probable concentration of monazites- (Ce) and aeschynites- (Ce), and because of this, it was possible to establish a zone in which the Passo Feio Carbonatite would probably be extended. In the stable isotope analyzes, the d13C values varied between -4.14 and -3.89‰ while those of d18O between 10.01 and 11.32‰ which can be attributed to the cooling of the magma itself, without suggesting metamorphic processes or subsequent changes. The deformation found in this carbonatite was probably developed in late-magmatic conditions, guided by tectonics associated with horizontal movements in shear zones. Thus, this work suggests that this carbonatite was the product of the reactivation of mantle sources, within a post-collision magmatic context of the Sul-Riograndense Shield.
