Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
To constrain the crystallization of alkaline and volatile-rich lavas present in intraplate settings, we studied the petrological features and the geochemical composition of major, trace, and volatile elements of mineral and bulk-rock of two sodalite-bearing phonolites: (1) haüyne-plagioclase-bearing Si-K-rich phonolite from Laacher See (Germany) and (2) nosean-nepheline-bearing Si-poor phonolite from Saghro (Morocco). In haüyne-bearing phonolites (55–59 wt% SiO2, K > Na, Na+K/Al = 0.96–1.08), we found that the low silica and low sodium activity promoted the early crystallization of S-rich haüyne (13.7–13.9 wt% SO3, 0.4 wt% Cl) + S-rich apatite (0.7–0.9 wt% SO3), titanite, and rare pyrrhotite followed by clinopyroxene-plagioclase-sanidine at relatively low pressure and temperature (P = 250 MPa and T = 850 °C) and oxidized condition (ΔNNO-NNO+1, where NNO is nickel-nickel oxide buffer). The crystallization of haüyne occurred at fluid-undersaturated conditions from a silicate melt with 6 wt% H2O, 0.17–0.23 wt% Cl, 0.11–0.4 wt% S, and 0.07–0.14 wt% F. Nosean-bearing phonolites from Saghro are silica-poor and peralkaline (52–54 wt% SiO2, Na > K, Na+K/Al = 1.2) and crystallized at higher P and T (300 MPa and 950 °C) and more reduced conditions (NNO) compared to haüyne-bearing phonolites. The incongruent reaction to form nosean requires high silica and Na2O activity. The mineral assemblage and composition suggest early crystallization of nepheline followed by nosean (7.8–8.8 wt% SO3; 1–1.1 wt% Cl). The sequence of crystallization is: clinopyroxene + nepheline + S-poor apatite (<0.04 wt% SO3) + pyrrhotite followed by nosean and titanite. Nosean-bearing magmas are fluid-undersaturated with relatively low volatile content (4 wt% H2O, <0.25 wt% Cl, <0.056 wt% S, 0.08–0.1 wt% F), although Cl may have exsolved during ascent and formed a fluid phase (NaCl-bearing).Both haüyne- and nosean-bearing phonolites are last equilibrated at relatively low pressure and high temperature. Haüyne and nosean crystallized at oxidized and volatile-rich pre-eruptive conditions. They record the volatile concentrations at depth and may be used as oxybarometer. The incongruent reactions involved to form haüyne and nosean suggest that phonolitic magmas became more oxidized during crystallization. The initial volatile concentrations in basanite/nephelinite magmas, from partial melting of volatile-bearing K2O-rich mantle rock, should have been one important factor influencing the crystallization of haüyne-bearing Si-K-rich phonolite and nosean-bearing Si-poor phonolite in intracontinental setting.
ISSN: 0003-004X

hal-01278067
https://hal.archives-ouvertes.fr/hal-01278067
DOI : 10.2138/am-2015-5318

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A suite of eclogite xenoliths from the Roberts Victor kimberlite (South Africa) is remarkable for its high abundances of base metal sulfides (BMS; up to 2 modal %). However, while sulfides are nearly ubiquitous in Type I eclogites (garnet > 0.07% Na2O), Type II eclogites (garnet < 0.07% Na2O) systematically lack sulfides. Two different sulfide assemblages are recognised within the Type I xenolith suite. Both populations are polyphase Cu-Ni-Fe sulfides, one characterised by the pyrrhotite (Po) + pentlandite (Pn) + chalcopyrite (Cp) assemblage and the other by the smythite/violarite (Smy/Vi) + (Ni)pyrite (Py) + Cp assemblage. The latter is the most abundant assemblage and reflects the supergene alteration of the "primary" Po + Pn + Cp assemblage. This process overprints the original composition of the sulfides by remobilising elements such as S, Fe, Ni, Se and Te. In the Type I eclogites, BMS occur as inclusions within silicates (garnet and clinopyroxene) and as interstitial grains. No chemical differences were observed between enclosed and interstitial sulfides. However, their relative abundances are correlated, indicating a similar origin. The Po + Pn + Cp assemblage is identical to eclogitic sulfides previously described in some Roberts Victor diamonds. Silicate-enclosed sulfides could appear to be early phases, but they are restricted to the outer parts of the silicate grains, suggesting a late incorporation during partial recrystallisation of silicate phases, induced by fluid-rock percolation-reaction during a metasomatic event. Positive whole-rock correlations between Se and (La/Sm)N⁎ and between Cu and ΣLREEN⁎ indicate a direct link between sulfide content and the enrichment of Mg + incompatible elements in the Type I eclogites, further supporting a metasomatic origin of the sulfide component. Similarly, a negative correlation between ΣLREEN⁎ and Cucpx implies that the metasomatic agent was at least partially composed of S-rich fluid (e.g. H2S, SO2) that reacted with the rock and leached Cu out of the silicates. The coupling between sulfides and LREE in the Type I eclogites, as well as the absence of sulfides and metasomatic features (e.g. unequilibrated grain boundaries, melt pockets, fluid inclusions, phlogopite) in the Type II eclogites, demonstrate that Type II eclogites did not undergo such a metasomatic event and therefore may represent the less-modified protoliths of Type I eclogites.
ISSN: 0009-2541

hal-00903856
https://hal.archives-ouvertes.fr/hal-00903856
DOI : 10.1016/j.chemgeo.2013.06.015

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Orogenic lherzolites exhibit a specific (although reproducible) platinum-group element signature characterized by slight positive deviations of Pd/Ir, Rh/Ir and Ru/Ir ratios from the canonical chondritic model. Such a signature was alternatively considered to be a compositional feature of the primitive upper mantle or resulting from sulfide melt addition by refertilisation reactions in the continental lithosphere. To shed additional light on this conundrum, the distribution of PGE in FON B 93, an unserpentinized, fertile (3.24% Al2O3) orogenic lherzolite (French Pyrenees) used as in-house standard by our group, has been studied to different scales, from the bulk rock to trace minerals. In addition to new ICPMS analyses after separation into Nis and Te coprecipitation, its whole-rock PGE concentrations were redetermined by three different laboratories using very precise ID-ICP-MS methods after digestion of the sample in Carius tube at T=250 degrees C and 320 degrees C or in high-pressure asher (HPA-S). The four methods produce reproducible Ru, Rh and Pd contents (7.1 +/- 0.18 ppb; 1.43 +/- 0.05 ppb; 7.1 +/- 0.30 ppb) whereas the non-ID NiS-fire assay method underestimates the Os and Ir concentrations by c.a. 10 and 15% compared to ID-ICP-MS analyses (4.40 +/- 0.07 and 4.00 +/- 0.17 ppb, respectively). Platinum was the most difficult to analyse. If performed on powder aliquots smaller than 3 g, the ID-ICP-MS analyses generate strong nugget effects while the non-ID NiS-fire assay method yields statistically lower (but highly reproducible) Pt concentrations (6.92 +/- 0.26 ppb). These features reflect the strong partitioning of Pt into trace phases that SEM and laser ablation-ICP-MS analyses on thin sections identify as both high-temperature Pt-Ir-Os alloys and Pt-(Pd) tellurides of likely subsolidus origin; ten to fifteen grains ranging in maximum dimension from a few micrometres to a few hundreds of nanometers, were identified by standard polished thin section. LA-ICP-MS data on base metal sulfides (25 grains analysed), coupled with the whole-rock S concentration (277 +/- 10 ppm) and modal composition of the BMS (90% pentlandite+accessory pyrite and secondary pyrrhotite + 10% chalcopyrite) allowed the contribution of the BMS phase to the PGE budget of FON B 93 to be estimated. Except Pt that exhibits a 95% deficit in the BMS phase, the PGE concentrations measured by ID-ICP-MS can be balanced by BMS while Al-spinel is a negligible contributor, accounting for less than 0.5% of the Ru budget. The occurrence of Pt in trace phases may bias the whole-rock Pt concentrations because 1) mechanical collection of Pt-rich trace phases remains problematic with the Nis button, and 2) Pt-Ir-Os alloys may be prone to digestion problems in conventional Carius tube procedures. Since they could be stable at mantle depth, such refractory alloys that contain Os and Ir may also have enhanced the heavy PGEs/light PGEs fractionation. Our observations likely pertain to orogenic lherzolites as a whole because BMS assemblages in these mantle rocks record evolution at low sulfur fugacity, which prevents Pt-Ir-Os alloy from entering the Mss in the mantle; moreover, at subsolidus temperature, pentlandite, the major BMS, cannot accommodate 0 valence state Pt.
ISSN: 0009-2541

hal-00411486
https://hal.archives-ouvertes.fr/hal-00411486
DOI : 10.1016/j.chemgeo.2007.06.030

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
The composition of S-rich apatite, of volatile-rich glass inclusions in apatite, and of interstitial glasses in alkaline xenoliths from the 1949 basanite eruption in La Palma has been investigated to constrain the partitioning of volatiles between apatite and alkali-rich melts. The xenoliths are interpreted as cumulates from alkaline La Palma magmas. Apatite contains up to 0.89 wt% SO3 (3560 ppm S), 0.31 wt% Cl, and 0.66 wt% Ce2O3. Sulfur is incorporated in apatite via several independent exchange reactions involving (P5+, Ca2+) vs. (S6+, Si4+, Na+, and Ce3+). The concentration of halogens in phonolitic to trachytic glasses ranges from 0.15 to 0.44 wt% for Cl and from < 0.07 to 0.65 wt% for F. The sulfur concentration in the glasses ranges from 0.06 to 0.23 wt% SO3 (sulfate-saturated systems). The chlorine partition coefficients (D (Cl) (apatite/glass) ) range from 0.4 to 1.3 (average D (Cl) (apatite/glass) = 0.8), in good agreement with the results of experimental data in mafic and rhyolitic system with low Cl concentrations. With increasing F in glass inclusions D (F) (apatite/glass) decreases from 35 to 3. However, most of our data display a high partition coefficient (similar to 30) close to D (F) (apatite/glass) determined experimentally in felsic rock. D (S) (apatite/glass) decreases from 9.1 to 2.9 with increasing SO3 in glass inclusions. The combination of natural and experimental data reveals that the S partition coefficient tends toward a value of 2 for high S content in the glass (> 0.2 wt% SO3). D (S) (apatite/glass) is only slightly dependent on the melt composition and can be expressed as: SO3 apatite (wt%) = 0.157 * ln SO3 glass (wt%) + 0.9834. The phonolitic compositions of glass inclusions in amphibole and hauyne are very similar to evolved melts erupted on La Palma. The lower sulfur content and the higher Cl content in the phonolitic melt compared to basaltic magmas erupted in La Palma suggest that during magma evolution the crystallization of hauyne and pyrrhotite probably buffered the sulfur content of the melt, whereas the evolution of Cl concentration reflects an incompatible behavior. Trachytic compositions similar to those of the (water-rich) glass inclusions analyzed in apatite and clinopyroxene are not found as erupted products. These compositions are interpreted to be formed by the reaction between water-rich phonolitic melt and peridotite wall-rock.
ISSN: 0010-7999

hal-00644803
https://hal.archives-ouvertes.fr/hal-00644803
DOI : 10.1007/s00410-011-0606-7

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
Despite a relatively 'uniform' fertile composition (Al2O3 = 2 center dot 19-4 center dot 47 wt %; Fo% = 89 center dot 2 +/- 0 center dot 3%; Cr#(Spl) = 8 center dot 9 +/- 1 center dot 5%), the Montferrier peridotite xenoliths show a wide range of S contents (22-590 ppm). Most sulphides are interstitial and show peculiar pyrrhotite-pentlandite intergrowths and low abundances of Cu-rich phases. Sulphide-rich samples are characterized by strong enrichment in the light rare earth elements and large ion lithophile elements without concomitant enrichment of the high field strength elements. Such trace-element fractionation is commonly ascribed to metasomatism by volatile-rich melts and/or carbonatitic melts. S and Se (11-67 ppb), as well as S/Se (up to approximate to 12 000), are correlated with La/Sm. Cu, however, remains broadly constant (30 +/- 5 ppm). These features strongly suggest that the percolation-reaction of such volatile-rich fluids has led to sulphide enrichment with an atypical signature marked by strong fractionation of the chalcophile elements (i.e. S vs Se and Cu). S-rich xenoliths are also characterized by high (Pd/Ir)(N) (1 center dot 2-1 center dot 9; where subscript N indicates normalized to chondrite), (Pd/Pt)(N) between 1 center dot 5 and 2 center dot 2, and (Os/Ir)(N) up to 1 center dot 85. Despite the relative uniform fertile composition of the xenoliths, Re/Os ranges between 0 center dot 02 and 0 center dot 18. Os-187/Os-188 is extremely variable even within a single sample and can be as high as 0 center dot 1756 for the most S-rich samples. Sulphides show highly fractionated and variable abundances of the highly siderophile elements (HSE) [0 center dot 03 (Pd/Ir)(N) < 1283] and Re-Os isotopic composition (0 center dot 115 < Os-187/Os-188 < 0 center dot 172). Such variation can be observed at the thin-section scale. Whole-rock and in situ sulphide data demonstrate that chalcophile and HSE systematics and the Os isotopic composition of the upper mantle could be significantly modified through metasomatism, even with volatile-rich fluids. These features highlight the complex behaviour of the HSE in fluid-rock percolation-reaction models and suggest a complex interplay between sulphide addition (crystallization or sulphidation) and partial equilibration of pre-existing sulphide. The specific fractionations observed in chemical proxies such as S and Se, Os and Ir, and Pd and Pt, as well as the low abundance of Cu-rich sulphides, suggest that sulphide addition may not have occurred via sulphide melts. Rather, we infer that S was present as a dissolved species in a (supercritical) oxidizing, volatile-rich fluid (C-O-H-S +/- Cl) along with other chalcophile and siderophile elements such as Os, Pd, Re and Au. The highly radiogenic Os composition of this fluid ( Os-187/ Os-188 > 0 center dot 17) would imply that such fluids are derived from an uncommon type of mantle source possibly related to carbonatite melts.
ISSN: 0022-3530

hal-00644524
https://hal.archives-ouvertes.fr/hal-00644524
DOI : 10.1093/petrology/egr038

Éditeur(s) : HAL CCSD Mineralogical Society
Résumé : The diagenetic evolution of the magnetic minerals during burial in sedimentary basins has been recently proposed. In this study, we provide new data from the Grès d’Annot basin, SE France. We analyze fine-grained clastic rocks that suffered a burial temperature from ~60 to >250 °C, i.e., covering oil and gas windows. Low temperature magnetic measurements (10–300 K), coupled with vitrinite reflectance data, aim at defining the magnetic mineral evolution through the burial history. Magnetite is documented throughout the entire studied transect. Goethite, probably occurring as nanoparticles, is found for a burial temperature <80 °C. Micron-sized pyrrhotite is highlighted for a burial temperature >200 °C below the Alpine nappes and the Penninic Front. A model of the evolution of the magnetic assemblage from 60 to >250 °C is proposed for clastic rocks, containing iron sulfides (pyrite) and organic matter. This work provides the grounds for a better understanding of the magnetic properties of petroleum plays.
ISSN: 0009-8558

hal-01122812
https://hal.archives-ouvertes.fr/hal-01122812
DOI : 10.3390/min4030667

Éditeur(s) : HAL CCSD Mineralogical Society
Résumé : International audience
Almost all magmas contain sulfide- or sulfate-bearing phases. In most natural samples the sulfur-bearing phase is a sulfide, which typically is pyrrhotite (Fe1−xS) or pyrite (FeS2) although chalcopyrite (CuFeS2), pentlandite ((Fe,Ni)9S8), sphalerite (ZnS) or molybdenite (MoS2) may be present as well. Sulfate minerals are rare at magmatic conditions, and anhydrite (CaSO4) is the most common. Other magmatic SO4-bearing minerals include the sodalite group minerals (haüyne simplified formula: (Na,Ca)4-8(Al6Si6(O,S)24)(SO4,Cl)1-2), scapolite minerals (silvialite: (Ca,Na)4Al6Si6O24(SO4,CO3)), and S-bearing apatite (Ca5(PO4)3(F, Cl, OH)). Barite (BaSO4) has been mentioned in rare cases (Marchev 1991). Sulfur-bearing minerals usually constitute a negligible fraction of the mineral assemblage in magmatic rocks and thus can be classified as accessory minerals. The crystallization of sulfide, sulfate, and S-bearing minerals strongly depends on melt composition, temperature and pressure, and the S speciation in melt which, in turn, is strongly dependent on the prevailing oxygen fugacity (Baker and Moretti 2011, this volume; Wilke et al. 2011, this volume). Irrespectively of the low abundance of S-bearing minerals, the evolution of sulfur in magmas may be evaluated from the occurrence of sulfides and sulfates. These minerals are critical for estimating the activity of various sulfur-bearing species in magmas and can be used to constrain the oxygen fugacity and the S concentration in the melt (e.g., pre-eruptive sulfur concentration in melts). The presence of either sulfide or sulfate in silicate melt indicates that the predominant dissolved sulfur species in the melt are S2− or S6+, respectively. Typically one of these species is dominant, but there are conditions where S2− ...
ISSN: 1529-6466

hal-00644580
https://hal.archives-ouvertes.fr/hal-00644580
DOI : 10.2138/rmg.2011.73.10

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
North Tanzanian Divergence is the first stage of continental break-up of East African Rift (<6 Ma) and is one of the most concentrated areas of carbonatite magmatism on Earth, with singular Oldoinyo Lengai and Kerimasi volcanoes. Hanang volcano is the southernmost volcano in the North Tanzanian Divergence and the earliest stage of rift initiation. Hanang volcano erupted silica-undersaturated alkaline lavas with zoned clinopyroxene, nepheline, andradite-schorlomite, titanite, apatite, and pyrrhotite. Lavas are low MgO-nephelinite with low Mg# and high silica content (Mg# = 22.4–35.2, SiO2 = 44.2–46.7 wt%, respectively), high incompatible element concentrations (e.g. REE, Ba, Sr) and display Nb–Ta fractionation (Nb/Ta = 36–61). Major elements of whole rock are consistent with magmatic differentiation by fractional crystallization from a parental melt with melilititic composition. Although fractional crystallization occurred at 9–12 km and can be considered as an important process leading to nephelinite magma, the complex zonation of cpx (e.g. abrupt change of Mg#, Nb/Ta, and H2O) and trace element patterns of nephelinites recorded magmatic differentiation involving open system with carbonate–silicate immiscibility and primary melilititic melt replenishment. The low water content of clinopyroxene (3–25 ppm wt. H2O) indicates that at least 0.3 wt% H2O was present at depth during carbonate-rich nephelinite crystallization at 340–640 MPa and 1050–1100 °C. Mg-poor nephelinites from Hanang represent an early stage of the evolution path towards carbonatitic magmatism as observed in Oldoinyo Lengai. Paragenesis and geochemistry of Hanang nephelinites require the presence of CO2-rich melilititic liquid in the southern part of North Tanzanian Divergence and carbonate-rich melt percolations after deep partial melting of CO2-rich oxidized mantle source.
ISSN: 0010-7999

hal-01467390
https://hal.archives-ouvertes.fr/hal-01467390
DOI : 10.1007/s00410-016-1273-5

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
New structural, geochronological and paleomagnetic data were obtained on dolerite dikes of the Nola region (Central African Republic) at the northern border of the Congo craton. In this region metavolcanic, successions were thrust southward onto the craton during the Panafrican orogenic events. Our structural data reveal at least two structural klippes south of the present-day limits of the Panafrican nappe suggesting that it has once covered the whole Nola region, promoting the pervasive hydrothermal green-schist metamorphism observed in the underlying cratonic basement and also in the intrusive dolerite dikes. Paleomagnetic measurements revealed a stable dual-polarity low-inclination magnetization component in nine dikes (47 samples), carried by pyrrhotite and magnetite. This component corresponds to a paleopole at 304.8 degrees E and 61.8 degrees S (dp = 5.4, dm = 10.7) graded at 2 = 6. Both metamorphism and magnetic resetting were dated by the Ar-40/Ar-39 method on amphibole grains separated from the dikes at 571 +/- 6 Ma. The Nola pole is the first well-dated paleomagnetic pole for the Congo craton between 580 and 550 Ma. It marks a sudden change in direction of the Congo craton apparent polar wander path at the waning stages of the Panafrican orogenic events.
ISSN: 0301-9268

hal-00321120
https://hal.archives-ouvertes.fr/hal-00321120
DOI : 10.1016/j.precamres.2008.05.005

Éditeur(s) : HAL CCSD
Résumé : International audience
The Achmmach tin mineralization (NE of theMoroccan Central Massif) is associated with tourmaline-richalteration halos, veins, and faults hosted in sandstones andmetapelites of the Upper Visean-Namurian. These depositsare reported to be late Hercynian in age and related to theemplacement of late-orogenic granite not outcropping in thestudied area. Structural and paragenetic studies of theAchmmach tin deposit were conducted in order to establisha general model of the mineralization. From field constraints,the late Hercynian phase is marked by a transition fromtranspression to extension with deformation conditions evolvingfrom ductile to brittle environments. The transpression(horizontal shortening direction roughly trending E-W) is coevalwith the emplacement of the first tourmaline halos alongseveral conjugated trends (N070, N020, and N120).Thereafter, a tourmaline-rich breccia formed in response tothe fracturing of early tourmaline-altered rocks.Subsequently, during the extensional phase, these structureswere reactivated as normal faults and breccias, allowing theformation of the main tin mineralization (cassiterite) associatedwith a wide variety of sulfides (arsenopyrite, chalcopyrite,sphalerite, galena, pyrrhotite, bismuthinite, pyrite, and stannite). This evolution ends with fluorite and carbonate deposition.The hydrothermal fluid flow velocity, calculated byapplying statistical measures on the tourmaline growth bands,varies with the lithology. Values are lower in metapelites andhigher in breccia. In the general evolution model proposedhere, tourmaline alteration makes the rock more competent,allowing for brittle fracturing and generation of open spacewhere the main Sn mineralization was precipitated.
Mineralium Deposita

insu-01240481
https://hal-insu.archives-ouvertes.fr/insu-01240481
DOI : 10.1007/s00126-015-0613-0