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"Colás, Vanessa"
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Compositional effects on the solubility of minor and trace elements in oxide spinel minerals; insights from crystal-crystal partition coefficients in chromite exsolution
by
Pearson, Norman J
,
O'Reilly, Suzanne Y
,
Padrón-Navarta, José Alberto
in
Ablation
,
Argentina
,
cations
2016
Chromite from Los Congos and Los Guanacos in the Eastern Pampean Ranges of Cordoba (Argentinian Central Andes) shows homogenous and exsolution textures. The composition of the exsolved phases in chromite approaches the end-members of spinel (MgAl2O4; Spl) and magnetite (Fe2+Fe23+O4; Mag) that define the corners of the spinel prism at relatively constant Cr3+/R3+ ratio (where R3+ is Cr+Al+Fe3+). The exsolution of these phases from the original chromite is estimated to have accounted at ≥600 °C on the basis of the major element compositions of chromite with homogenous and exsolution textures that are in equilibrium with forsterite-rich olivine (Fo95). The relatively large size of the exsolved phases in chromite (up to ca. 200 µm) provided, for the first time, the ability to conduct in situ analysis with laser ablation-inductively coupled plasma-mass spectrometry for a suite of minor and trace elements to constrain their crystal-crystal partition coefficient between the spinel-rich and magnetite-rich phases (DiSpl/Mag). Minor and trace elements listed in increasing order of compatibility with the spinel-rich phase are Ti, Sc, Ni, V, Ge, Mn, Cu, Sn, Co, Ga, and Zn. DiSpl/Mag values span more than an order of magnitude, from DTiSpl/Mag = 0.30 ± 0.06 to DZnSpl/Mag = 5.48 ± 0.63. Our results are in remarkable agreement with data available for exsolutions of spinel-rich and magnetite-rich phases in other chromite from nature, despite their different Cr3+/R3+ ratio. The estimated crystal-crystal partitioning coefficients reflect the effect that crystal-chemistry of the exsolved phases from chromite imposes on all investigated elements, excepting Cu and Sc (and only slightly for Mn). The observed preferential partitioning of Ti and Sc into the magnetite-rich phase is consistent with high-temperature chromite/melt experiments and suggests a significant dependence on Fe3+ substitution in the spinel structure. A compositional effect of major elements on Ga, Co, and Zn is observed in the exsolved phases from chromite but not in the experiments; this might be due to crystal-chemistry differences along the MgFe-1-Al2Fe-23+ exchange vector, which is poorly covered experimentally. This inference is supported by the strong covariance of Ga, Co, and Zn observed only in chromite from layered intrusions where this exchange vector is important. A systematic increase of Zn and Co coupled with a net decrease in Ga during hydrous metamorphism of chromitite bodies cannot be explained exclusively by compositional changes of major elements in the chromite (which are enriched in the magnetite component). The most likely explanation is that the contents of minor and trace elements in chromite from metamorphosed chromitites are controlled by interactions with metamorphic fluids involved in the formation of chlorite.
Journal Article
Thermal metamorphism of mantle chromites and the stability of noble-metal nanoparticles
2015
The Loma Baya complex in south-western Mexico is a volume of chromitite-bearing oceanic mantle that records a complex metamorphic history, defined by a first stage of hydrous metamorphism overprinted by a short-lived thermal event associated with an Eocene granite intrusion. During the hydrous metamorphism, the primary magmatic chromite–olivine assemblage was replaced by a secondary, porous intergrowth of Fe
2+
-rich chromite and chlorite. The heat supplied by an Eocene-age granite intrusion reversed the hydration reaction, producing chromite rims with perfectly developed crystal faces. This third-generation chromite is in equilibrium with highly magnesian (neoformed) olivine and defines a chemical trend analogous to the original magmatic one. The preservation of both reactions in the Loma Baya chromitite provides compelling evidence that the hydration of chromite can be reversed by either prograde metamorphism or any heating event, confirming previous thermodynamic predictions. Understanding these complex features is of particular interest due to the fact that changes in temperature and variable degrees of fluid/rock interaction during metamorphism and intrusion have also significantly affected the chromite-hosted IPGE carrier phases. Here, we propose that the metamorphic fluids involved in the hydrous metamorphism have caused the desulphurization of laurite RuS
2
, releasing minute particles of Ru–Os–Ir alloys <50 nm in diameter. The following short-lived thermal event that promoted dehydration in the chromitite had the opposite effect on nanoparticle stability, producing a significant coarsening of metal nanoparticles to dimensions larger than a micron. Based on such observations, we argue that IPGE nanoparticles can be exsolved and grown (or coarsen) from sulphide matrices during prograde metamorphism or heating and not exclusively upon cooling under magmatic conditions as it has been previously suggested. These results provide new insights on the relevant role of temperature and nanoparticle–host interaction phenomena in natural systems, shedding new light on the kinetic controls of nano- to micron-scale IPGE particle distributions during metamorphism.
Journal Article
Metamorphic fingerprints of Fe-rich chromitites from the Eastern Pampean Ranges, Argentina
by
Camprubí, Antoni
,
O'Reilly, Suzanne Y
,
Gervilla, Fernando
in
Geology
,
Geosciences, Multidisciplinary
2020
Chromitites hosted in the serpentinized harzburgite bodies from Los Congos and Los Guanacos (Eastern Pampean Ranges, north Argentina) record a complex metamorphic evolution. The hydration of chromitites during the retrograde metamorphism, their subsequent dehydration during the prograde metamorphism and the later-stage cooling, have resulted in a threefold alteration of chromite: i) Type I is characterized by homogeneous Fe3+- and Cr-rich chromite; ii) Type II chromite contains exsolved textures that consist in blebs and fine lamellae of a magnetite-rich phase hosted in a spinel-rich phase; iii) Type III chromite is formed by variable proportions of magnetite-rich and spinel-rich phases with symplectitic texture. Type I chromite shows lower Ga and higher Co, Zn and Mn than magmatic chromites from chromitites in suprasubduction zone ophiolites as a consequence of the redistribution of these elements between Fe3+-rich non-porous chromite and silicates during the prograde metamorphism. Whereas, the spinel-rich phase in Type III chromite is enriched in Co, Zn, Sc, and Ga, but depleted in Mn, Ni, V and Ti with respect to the magnetite-rich phase, due to the metamorphic cooling from high-temperature conditions. The pseudosection calculated in the fluid-saturated FCrMACaSH system, and contoured for Cr# and Mg#, allows us to constrain the temperature of formation of Fe3+-rich non-porous chromite by the diffusion of magnetite in Fe2+-rich porous chromite at <500 ºC and 20 kbar. The subsequent dehydration of Fe3+-rich non-porous chromite by reaction with antigorite and chlorite formed Type I chromite and Mg-rich olivine and pyroxene at >800 ºC and 10 kbar. The ultimate hydration of silicates in Type I chromite and the exsolution of Type II and Type III chromites would have started at ~600 ºC. These temperatures are in the range of those estimated for ocean floor serpentinization (<300 ºC and <4 kbar), the regional prograde metamorphism in the granulite facies (800 ºC and <10 kbar), and subsequent retrogression to the amphibolite facies (600 ºC and 4-6.2 kbar) in the host ultramafic rocks at Los Congos and Los Guanacos. A continuous and slow cooling from granulite to amphibolite facies produced the exsolution of spinel-rich and magnetite-rich phases, developing symplectitic textures in Type III chromite. However, the discontinuous and relatively fast cooling produced the exsolution of magnetite-rich phase blebs and lamellae within Type II chromite. The P-T conditions calculated in FCrMACaSH system and the complex textural and geochemical fingerprints showed by Type I, Type II and Type III chromites leads us to suggest that continent-continent collisional orogeny better records the fingerprints of prograde metamorphism in ophiolitic chromitites.
Journal Article
Geology, mineralogy, and cassiterite geochronology of the Ayawilca Zn-Pb-Ag-In-Sn-Cu deposit, Pasco, Peru
2022
The Ayawilca deposit in Pasco, Peru, represents the most significant recent base-metal discovery in the central Andes and one of the largest undeveloped In resources globally. As of 2018, it hosts an 11.7 Mt indicated resource grading 6.9% Zn, 0.16% Pb, 15 g/t Ag, and 84 g/t In, an additional 45.0 Mt inferred resource grading 5.6% Zn, 0.23% Pb, 17 g/t Ag, and 67 g/t In, and a separate Sn-Cu-Ag inferred resource of 14.5 Mt grading 0.63% Sn, 0.21% Cu, and 18 g/t Ag. Newly obtained U–Pb dates for cassiterite by LA-ICP-MS (22.77 ± 0.41 and 23.05 ± 2.06 Ma) assign the Ayawilca deposit to the Miocene polymetallic belt of central Peru. The polymetallic mineralization occurs as up to 70-m-thick mantos hosted by carbonate rocks of the Late Triassic to Early Jurassic Pucará Group, and subordinately, as steeply dipping veins hosted by rocks of the Pucará Group and overlying Cretaceous sandstones-siltstones of the Goyllarisquizga Group. Relicts of a distal retrograde magnesian skarn and cassiterite (stage pre-A) were identified in the deepest mantos. The volumetrically most important mineralization at Ayawilca comprises a low-sulfidation assemblage (stage A) with quartz, pyrrhotite, arsenopyrite, chalcopyrite, Fe-rich sphalerite, and traces of stannite and herzenbergite. Stage A sphalerite records progressive Fe depletion, from 33 to 10 mol% FeS, which is compatible with the observed transition from low- to a subsequent intermediate-sulfidation stage (B) marked by the crystallization of abundant pyrite and marcasite. Finally, during a later intermediate-sulfidation stage (C) sphalerite (up to 11 mol% FeS), galena, native bismuth, Cu-Pb-Ag sulfosalts, siderite, Mn-Fe carbonates, kaolinite, dickite, and sericite were deposited. This paragenetic evolution shows striking similarities with that at the Cerro de Pasco Cordilleran-type polymetallic deposit, even if at Ayawilca stage C did not reach high-sulfidation conditions. The occurrence of an early retrograde skarn assemblage suggests that the manto bodies at Ayawilca formed at the transition between distal skarn and skarn-free (Cordilleran-type) carbonate-replacement mineralization. Mineral assemblages define a T-fS2 evolutionary path close to the pyrrhotite-pyrite boundary. Buffering of hydrothermal fluids by underlying Devonian carbonaceous phyllites of the Excelsior Group imposed highly reduced conditions during stage A mineralization (logfO2 < − 30 atm). The low fO2 favored efficient Sn mobility during stages pre-A and A, in contrast to other known ore deposits in the polymetallic belt of central Peru, in which the occurrence of Sn minerals is minor. Subsequent cooling, progressive sealing of vein walls, and decreasing buffering potential of the host rocks promoted the shift from low- (stage A) to intermediate-sulfidation (stages B and C) states. LA-ICP-MS analyses reveal significant In contents in Fe-rich sphalerite (up to 1.7 wt%), stannite (up to 1908 ppm), and chalcopyrite (up to 1185 ppm). The highest In content was found in stage A sphalerite that precipitated along with chalcopyrite and stannite, thus pointing to the early, low-sulfidation assemblage as prospective for this high-tech metal in similar mineral systems. Indium was likely incorporated into the sphalerite crystal lattice via Cu+ + In3+ ↔ 2 Zn2+ and (Sn, Ge)4+ + (Ga, In)3+ + (Cu + Ag)+ ↔ 4 Zn2+ coupled substitutions. Indium incorporation mechanisms into the stannite and chalcopyrite crystal lattices remain unclear.
Journal Article
The Pliocene Xoconostle high sulfidation epithermal deposit in the Trans-Mexican Volcanic Belt: Preliminary study
2020
The Xoconostle prospect in northeastern Michoacán state, south-central Mexico, is constituted by high sulfidation epithermal breccias and stockworks with Au and Hg prospective anomalies. The mineralization is hosted by latest Miocene to Pliocene rocks grouped into the El Terrero ignimbrite and the Siete Cruces dome complex and a stock of intermediate composition and undetermined (Pliocene?) age. Two alunite samples from deep hypogene advanced argillic alteration assemblages within the deposit yielded 40Ar/39Ar ages at 5.57 ± 0.44 (Messinian) and 3.67 ± 0.20 Ma (Zanclean). Such ages are in good agreement with those of volcanic rocks at a semi-regional scale, especially those associated with the nearby Amealco caldera. Assuming that the formation of Xoconostle deposit could be genetically related to any of the eruptive units in this caldera, it would be associated with dacitic-andesitic rocks at ~4.7 Ma or with bimodal andesite-basalt volcanism at ~3.7 Ma, with which rhyolites at the southwest rim of the caldera (nearer to the epithermal deposit) are contemporaneous. The obtained ages are also in good agreement with those determined for the youngest stages in the evolution of the Trans-Mexican Volcanic Belt (TMVB). In addition, such ages compare well with those established for the E-W striking Morelia-Acambay normal fault zone (or Acambay graben). The occurrence of E-W structural features in the study area support their correlation with those in the Acambay graben. Although the metallogenesis of the TMVB needs further endeavours that contribute to its understanding, the Xoconostle prospect adds up to other dated magmatic-hydrothermal deposits that may collectively constitute a Pliocene metallogenic province whose inception was geologically circumscribed to this volcanic arc. However, this and its companion papers in this issue confirm the metallogenic potential of the TMVB in most of its stages of evolution, particularly in the late Miocene-Pliocene stage of acid and bimodal volcanism.
Journal Article
The Pliocene Ixtacamaxtitlán low sulfidation epithermal deposit (Puebla, Mexico): A case of fossil fungi consortia in a steam-heated environment
by
Camprubí, Antoni
,
Ortega-Larrocea, Pilar
,
Gabites, Janet
in
Geology
,
Geosciences, Multidisciplinary
2020
The Ixtacamaxtitlán area in northern Puebla (central Mexico) contains middle Miocene Cu-Mo-Au porphyry/skarn and Pliocene low-sulfidation Au-Ag epithermal deposits that are geologically associated with the evolution of the Trans-Mexican Volcanic Belt (TMVB). In this paper, a new 40Ar/39Ar age (2.87 ± 0.41 Ma) is provided for rhombohedral alunite from a kaolinite + alunite ± opal ± cristobalite ± smectite advanced argillic alteration assemblage. This age contributes to the definition of a metallogenic province that is confined to the TMVB, a relevant feature for regional exploration. A ~12 My gap is established between the formation of the Cu-Mo-Au porphyry/skarn and low-sulfidation Au-Ag epithermal deposits, which rules out the possibility that their overlapping was the result of telescoping. Advanced argillic alteration is conspicuous throughout the mineralized area. This alteration assemblage consists of a widespread kaolinite-rich blanket that underlies silica sinters, polymictic hydrothermal breccias, and an alunite-rich spongy layer that consists of vertical tubular structures that are interpreted as the result of gas venting in a subaerial environment. The above indicate a shallow hypogene origin for the advanced argillic alteration assemblage—that is, formation by the partial condensation within a phreatic paleoaquifer of acidic vapors that were boiled-off along fractures that host epithermal veins at depth. The formation of the spongy alunite layer and silica sinters is interpreted to have been synchronous. Within the alunite-rich spongy layer, tubular structures hosted microbial consortia dominated by fungi and possible prokaryote (Bacteria or Archaea) biofilms. Such consortia were developed on previously formed alunite and kaolinite and were preserved due to their replacement by opal, kaolinite, or alunite. This means that the proliferation of fungi and prokaryotes occurred during a lull in acidic gas venting during which other organisms (i.e., algae) might have also prospered. Periodic acidic gas venting is compatible with a multi-stage hydrothermal system with several boiling episodes, a feature typical of active geothermal systems and of low-sulfidation epithermal deposits. The microstructures, typical for fungi, are mycelia, hyphae with septa, anastomoses between branches, and cord-like groupings of hyphae. Possible evidence for skeletal remains of prokaryote biofilms is constituted by cobweb-like microstructures composed of <1 µm thick interwoven filaments in close association with hyphae (about 2.5 µm thick). Bioweathering of previously precipitated minerals is shown by penetrative biobrecciation due to extensive dissolution of kaolinite by mycelia and by dissolution grooves from hyphae on alunite surfaces. Such bioweathering was possibly predated by inorganically driven partial dissolution of alunite, which suggests a lull in acidic gas venting that allowed living organisms to thrive. This interpretation is sustained by the occurrence of geometrical dissolution pits in alunite covered by hyphae. Fungal bioweathering is particularly aggressive on kaolinite due to its relatively poor nutrient potential. Such delicate microstructures are not commonly preserved in the geological record. In addition, numerous chalcopyrite microcrystals or microaggregates are found within the alunite layer, which could be related to sulfate reduction due to bacterial activity from the sulfate previously released by fungal bioweathering of alunite. Hydrogeochemical modeling constrains pH to between ~3.2 and ~3.6 and temperature to between 53 and 75 °C during the stage in which fungi and other organisms thrived. These waters were cooler and more alkaline than in earlier and later stages, which were characterized dominantly by steam-heated waters. The most likely process to account for this interlude would be mixing with meteoric water or with upwelling mature water that did not undergo boiling.
Journal Article
Metamorphic fingerprints of Fe-rich chromitites from the Eastern Pampean Ranges, Argentina
2020
Chromitites hosted in the serpentinized harzburgite bodies from Los Congos and Los Guanacos (Eastern Pampean Ranges, north Argentina) record a complex metamorphic evolution. The hydration of chromitites during the retrograde metamorphism, their subsequent dehydration during the prograde metamorphism and the later-stage cooling, have resulted in a threefold alteration of chromite: i) Type I is characterized by homogeneous Fe3+- and Cr-rich chromite; ii) Type II chromite contains exsolved textures that consist in blebs and fine lamellae of a magnetite-rich phase hosted in a spinel-rich phase; iii) Type III chromite is formed by variable proportions of magnetite-rich and spinel-rich phases with symplectitic texture. Type I chromite shows lower Ga and higher Co, Zn and Mn than magmatic chromites from chromitites in suprasubduction zone ophiolites as a consequence of the redistribution of these elements between Fer-rich non-porous chromite and silicates during the prograde metamorphism. Whereas, the spinel-rich phase in Type III chromite is enriched in Co, Zn, Sc, and Ga, but depleted in Mn, Ni, V and Ti with respect to the magnetite-rich phase, due to the metamorphic cooling from high-temperature conditions. The pseudosection calculated in the fluid-saturated FCrMACaSH system, and contoured for Cr# and Mg#, allows us to constrain the temperature of formation of Fe3+-rich non-porous chromite by the diffusion of magnetite in Fe2+-rich porous chromite at <500 ºC and 20 kbar. The subsequent dehydration of Fe3+-rich non-porous chromite by reaction with antigorite and chlorite formed Type I chromite and Mg-rich olivine and pyroxene at >800 ºC and 10 kbar. The ultimate hydration of silicates in Type I chromite and the exsolution of Type II and Type III chromites would have started at ~600 ºC. These temperatures are in the range of those estimated for ocean floor serpentinization (<300 ºC and <4 kbar), the regional prograde metamorphism in the granulite facies (800 ºC and <10 kbar), and subsequent retrogression to the amphibolite facies (600 ºC and 4-6.2 kbar) in the host ultramafic rocks at Los Congos and Los Guanacos. A continuous and slow cooling from granulite to amphibolite facies produced the exsolution of spinel-rich and magnetite-rich phases, developing symplectitic textures in Type III chromite. However, the discontinuous and relatively fast cooling produced the exsolution of magnetite-rich phase blebs and lamellae within Type II chromite. The P-T conditions calculated in FCrMACaSH system and the complex textural and geochemical fingerprints showed by Type I, Type II and Type III chromites leads us to suggest that continent-continent collisional orogeny better records the fingerprints of prograde metamorphism in ophiolitic chromitites.
Las cromititas incluidas en los cuerpos de harzburgita serpentinizada de Los Congos y Los Guanacos (Sierras Pampeanas Orientales, norte de Argentina) registran una evolución metamórfica compleja. La hidratación de las cromititas durante el metamorfismo retrógrado, su posterior deshidratación durante el metamorfismo prógrado y el subsecuente enfriamiento ha dado como resultado la formación de tres tipos de cromita alterada: i) Tipo I, caracterizada por una cromita homogénea y rica en Fe3+ y Cr; ii) cromita Tipo II, con texturas de exsolución que consisten en gránulos y lamelas finas de una fase rica en magnetita alojada en una fase rica en espinela; iii) cromita Tipo III, formada por proporciones variables de las fases ricas en magnetita y espinela con textura simplectítica. La cromita Tipo I muestra menor Ga pero mayor Co, Zn y Mn que las cromitas magmáticas de las cromititas ofiolíticas en zonas de suprasubducción como consecuencia de la redistribución de estos elementos entre la cromita no porosa rica en Fe3+ y los silicatos durante el metamorfismo prógrado. En cambio, la fase rica en espinela en la cromita Tipo III está enriquecida en Co, Zn, Sc y Ga, pero empobrecida en Mn, Ni, V y Ti respecto a la fase rica en magnetita debido al enfriamiento metamórfico desde condiciones de alta temperatura. La pseudosección calculada en el sistema FCrMACaSH saturado de agua y contorneada para el #Cr y #Mg, nos permite restringir la temperatura de formación de la cromita no porosa rica en Fe3+ debido a la difusión de la magnetita en la cromita porosa rica en Fe2+ a <500 ºC y 20 kbar. La posterior deshidratación de la cromita no porosa rica en Fe3+ formó por reacción con antigorita y clorita, cromita Tipo I y olivino y piroxeno ricos en Mg a >800 ºC y 10 kbar. La hidratación final de los silicatos en la cromita Tipo I y la exsolución de las cromitas Tipo II y Tipo III pudo haber comenzado a ~600 ºC. Estas temperaturas están en el rango de las estimadas para la serpentinización de fondo oceánico (<300 ºC y <4 kbar), el metamorfismo regional prógrado en facies de granulita (800 ºC y <10 kbar), y la posterior retrogresión a facies de anfibolita (600 ºC y 4-6.2 kbar) de las rocas ultramáficas encajantes en Los Congos y Los Guanacos. Un enfriamiento continuo y lento de facies de granulita a anfibolita produjo la exsolución de las fases ricas en espinela y magnetita, desarrollando texturas simpléctíticas en la cromita Tipo III. Sin embargo, el enfriamiento discontinuo y relativamente rápido produjo la exsolución de los gránulos y las lamelas de la fase rica en magnetita dentro de la cromita Tipo II. Las condiciones P-T calculadas en el sistema FCrMACaSH y las complejas texturas y firmas geoquímicas mostradas por las cromitas Tipo I, Tipo II y Tipo III nos permiten sugerir que las orogenias que implican la colisión continente-continente registran mejor las firmas del metamorfismo prógrado en las cromititas ofiolíticas.
Journal Article
The Pliocene Ixtacamaxtitlán low sulfidation epithermal deposit (Puebla, Mexico)
2020
The Ixtacamaxtitlán area in northern Puebla (central Mexico) contains middle Miocene Cu-Mo-Au porphyry/skarn and Pliocene low-sulfidation Au-Ag epithermal deposits that are geologically associated with the evolution of the Trans-Mexican Volcanic Belt (TMVB). In this paper, a new 40Ar/39Ar age (2.87 ± 0.41 Ma) is provided for rhombohedral alunite from a kaolinite + alunite ± opal ± cristobalite ± smectite advanced argillic alteration assemblage. This age contributes to the definition of a metallogenic province that is confined to the TMVB, a relevant feature for regional exploration. A ~12 My gap is established between the formation of the Cu-Mo-Au porphyry/skarn and low-sulfidation Au-Ag epithermal deposits, which rules out the possibility that their overlapping was the result of telescoping. Advanced argillic alteration is conspicuous throughout the mineralized area. This alteration assemblage consists of a widespread kaolinite-rich blanket that underlies silica sinters, polymictic hydrothermal breccias, and an alunite-rich spongy layer that consists of vertical tubular structures that are interpreted as the result of gas venting in a subaerial environment. The above indicate a shallow hypogene origin for the advanced argillic alteration assemblage—that is, formation by the partial condensation within a phreatic paleoaquifer of acidic vapors that were boiled-off along fractures that host epithermal veins at depth. The formation of the spongy alunite layer and silica sinters is interpreted to have been synchronous.
Within the alunite-rich spongy layer, tubular structures hosted microbial consortia dominated by fungi and possible prokaryote (Bacteria or Archaea) biofilms. Such consortia were developed on previously formed alunite and kaolinite and were preserved due to their replacement by opal, kaolinite, or alunite. This means that the proliferation of fungi and prokaryotes occurred during a lull in acidic gas venting during which other organisms (i.e., algae) might have also prospered. Periodic acidic gas venting is compatible with a multi-stage hydrothermal system with several boiling episodes, a feature typical of active geothermal systems and of low-sulfidation epithermal deposits. The microstructures, typical for fungi, are mycelia, hyphae with septa, anastomoses between branches, and cord-like groupings of hyphae. Possible evidence for skeletal remains of prokaryote biofilms is constituted by cobweb-like microstructures composed of <1 μm thick interwoven filaments in close association with hyphae (about 2.5 μm thick). Bioweathering of previously precipitated minerals is shown by penetrative biobrecciation due to extensive dissolution of kaolinite by mycelia and by dissolution grooves from hyphae on alunite surfaces. Such bioweathering was possibly predated by inorganically driven partial dissolution of alunite, which suggests a lull in acidic gas venting that allowed living organisms to thrive. This interpretation is sustained by the occurrence of geometrical dissolution pits in alunite covered by hyphae. Fungal bioweathering is particularly aggressive on kaolinite due to its relatively poor nutrient potential. Such delicate microstructures are not commonly preserved in the geological record. In addition, numerous chalcopyrite microcrystals or microaggregates are found within the alunite layer, which could be related to sulfate reduction due to bacterial activity from the sulfate previously released by fungal bioweathering of alunite. Hydrogeochemical modeling constrains pH to between ~3.2 and ~3.6 and temperature to between 53 and 75 °C during the stage in which fungi and other organisms thrived. These waters were cooler and more alkaline than in earlier and later stages, which were characterized dominantly by steam-heated waters. The most likely process to account for this interlude would be mixing with meteoric water or with upwelling mature water that did not undergo boiling.
El área de Ixtacamaxtitlán en el norte de Puebla (México central) contiene depósitos de tipo pórfido/skarn de Cu-Mo-Au del Mioceno medio y depósitos epitermales de baja sulfuración de Au-Ag del Plioceno, que están geológicamente asociados a la evolución de la Faja Volcánica Trans-Mexicana (FVTM). En este trabajo se presenta una nueva edad 40Ar/39Ar (2.87 ± 0.41 Ma) en alunita romboédrica procedente de una asociación de alteración argílica avanzada constituida por kaolinita + alunita ± ópalo ± cristobalita ± esmectita. Esta edad contribuye a la definición de una provincia metalogenética circunscrita a la FVTM, lo cual constituye un rasgo relevante para la exploración regional. Se ha determinado un lapso de ~12 millones de años entre la formación de los depósitos de tipo pórfido/skarn de Cu-Mo-Au y los depósitos epitermales de baja sulfuración de Au-Ag, lo cual invalida la posibilidad de que la superposición existente entre dichos depósitos constituya un auténtico telescopaje, contrariamente a interpretaciones previas. Además, dentro de dicho lapso se produjo la formación de un estratovolcán en el área de estudio, que habría interferido en cualquier actividad hidrotermal existente. La asociación de alteración argílica avanzada es reconocible en un área extensa de la zona mineralizada. Dicha asociación consiste en un amplio cuerpo subhorizontal rico en kaolinita que subyace a sínteres silícicos, brechas hidrotermales polimícticas, y un horizonte de aspecto esponjoso rico en alunita que consiste en estructuras verticales tubulares que se interpretan en este trabajo como debidas al escape de gases en un ambiente subaéreo. Tales características son compatibles con un ambiente de formación hipogénico somero para la asociación de alteración argílica avanzada—esto es, formación en terrenos calentados por vapor derivados de la condensación parcial en un paleoacuífero freático de vapores ácidos generados por ebullición a lo largo de fracturas que eventualmente alojaron vetas epitermales en profundidad. Se interpreta que la formación del horizonte esponjoso de alunita y de los sínteres silícicos fue sincrónica.
En el interior de las estructuras tubulares de alunita se desarrollaron consorcios dominados por hongos que también incluyen posibles biofilmes de procariontes (bacterias o arqueas). Dichos consorcios se desarrollaron sobre alunita y kaolinita previamente precipitadas, y fueron preservados debido a su reemplazamiento por ópalo, kaolinita o alunita. Ello conlleva que la proliferación de hongos y procariontes se produjo en periodos de pausa en la emanación de gases ácidos, durante los cuales otros organismos (i.e., algas) pudieron haber igualmente prosperado. Este rasgo es compatible con un sistema hidrotermal multiepisódico con diversas etapas con ebullición, lo cual concuerda con el ambiente de formación de los depósitos epitermales de baja sulfuración. Las microestructuras observadas típicas de hongos son micelios, hifas septadas, anastomosis entre ramificaciones, y agrupaciones de hifas en forma de cable o cordón. La posible evidencia de restos esqueléticos de biofilmes de procariontes la constituyen microestructuras semejantes a telarañas formadas por el entramado de filamentos con grosores <1 μm, que se encuentran íntimamente asociadas a hifas (éstas, con grosores del orden de ~2.5 μm). La biometeorización de minerales previamente precipitados se muestra en forma de biobrechificación penetrativa debida a la extensa disolución de kaolinita generada por micelios y por el desarrollo de surcos de disolución generados por hifas en la superficie de los cristales de alunita. Dicha biometeorización vino antecedida por la disolución parcial de la alunita, posiblemente de origen inorgánico, lo cual denota la instalación de un ambiente más benéfico (menos ácido) para el desarrollo de organismos vivos y, por tanto, de un periodo de pausa en la exhalación de gases. Dicha interpretación se argumenta con la presencia de mellas geométricas de disolución en alunita, cubiertas por hifas. La biometeorización fúngica es particularmente agresiva en kaolinita debido a su relativamente pobre potencial nutritivo. Estos tipos de microestructuras delicadas no se preservan habitualmente en el registro geológico. Asimismo, se encuentran numerosos microcristales y microagregados de calcopirita en el horizonte de alunita, que pueden ser hipotéticamente asociados a reducción de sulfatos debida a actividad bacteriana, a partir del sulfato previamente liberado por medio de la biometeorización de alunita. El modelado hidrogeoquímico permitió constreñir el pH entre ~3.2 y ~3.6 y la temperatura entre 53° and 75 °C durante el estadio en que los hongos y otros organismos prosperaron en asociación con aguas más frías y alcalinas que en los estadios precedente y posterior, que se caracterizaron por la presencia dominante de aguas calentadas por vapor. Tales variaciones en temperatura y pH con respecto a los fluidos precedentes pudieron haber sido consecuencia de la mezcla entre éstos y otros fluidos de nueva incorporación. Los candidatos más verosímiles para permitir dicho interludio serían el agua meteórica o agua ascendente madura que no experimentó ebullición.
Journal Article
Evaluation of the novel TSPO radiotracer 18F VUIIS1008 in a preclinical model of cerebral ischemia in rats
by
Pulagam, Krishna R.
,
Padro, Daniel
,
Plaza-García, Sandra
in
[18F] DPA-714
,
[18F] VUIIS1008
,
Brain
2017
Background
In vivo positron-emission tomography (PET) imaging of transporter protein (TSPO) expression is an attractive and indispensable tool for the diagnosis and therapy evaluation of neuroinflammation after cerebral ischemia. Despite several radiotracers have shown an excellent capacity to image neuroinflammation, novel radiotracers such as [
18
F] VUIIS1008 have shown promising properties to visualize and quantify the in vivo expression of TSPO.
Methods
Longitudinal in vivo magnetic resonance (MRI) and PET imaging studies with the novel TSPO radiotracer 2-(5,7-diethyl-2-(4-(2-[
18
F] fluoroethoxy) phenyl) pyrazolo [1,5-a] pyrimidin-3-yl)-N, N-diethylacetamide ([
18
F] VUIIS1008), and (N, N-diethyl-2-(2-[4-(2-fluoroethoxy)-phenyl]-5,7-dimethyl-pyrazolo [1,5-a] yrimidin-3-yl)-acetamide ([
18
F] DPA-714) were carried out before and at days 1, 3, 7, 14, 21, and 28 following the transient middle cerebral artery occlusion (MCAO) in rats.
Results
MRI images showed the extension and evolution of the brain infarction after ischemic stroke in rats. PET imaging with [
18
F] VUIIS1008 and [
18
F] DPA714 showed a progressive increase in the ischemic brain hemisphere during the first week, peaking at day 7 and followed by a decline from days 14 to 28 after cerebral ischemia. [
18
F] DPA714 uptake showed a mild uptake increase compared to [
18
F] VUIIS1008 in TSPO-rich ischemic brain regions. In vivo [
18
F] VUIIS1008 binding displacement with VUIIS1008 was more efficient than DPA714. Finally, immunohistochemistry confirmed a high expression of TSPO in microglial cells at day 7 after the MCAO in rats.
Conclusions
Altogether, these results suggest that [
18
F] VUIIS1008 could become a valuable tool for the diagnosis and treatment evaluation of neuroinflammation following ischemic stroke.
Journal Article
Endometrial cancer PDX-derived organoids (PDXOs) and PDXs with FGFR2c isoform expression are sensitive to FGFR inhibition
by
Rogers, Rebecca
,
Chetty, Naven
,
Moiola, Cristian P.
in
631/1647/664/1257
,
631/67/70
,
692/308/575
2023
Endometrial cancer (EC) patients with metastatic/recurrent disease have limited treatment options and poor survival outcomes. Recently, we discovered the FGFR2c splice isoform is associated with poor prognosis in EC patients. Here we report the establishment of 16 EC patient-derived xenografts (PDX)-derived organoids (PDXOs) with or without FGFR2c expression. In vitro treatment of 5 EC PDXOs with BGJ398 showed significant cell death in 3 models with FGFR2c expression. PDXs with high/moderate FGFR2c expression showed significant tumour growth inhibition (TGI) following 21-day treatment with FGFR inhibitors (BGJ398 or pemigatinib) and significantly prolonged survival in 4/5 models. Pemigatinib + cisplatin combination therapy (
n
= 5) resulted in significant TGI and prolonged survival in one of two p53abn PDXs. All five models treated with cisplatin alone showed de novo resistance and no survival benefit. Seven-day treatment with BGJ398 revealed a significant reduction in angiogenesis and CD206 + M2 macrophages. These data collectively support the evaluation of FGFR inhibitors in a clinical trial.
Journal Article