Alteration Phases Research Articles

Nebular thermal processing of accretionary fine-grained rims in the Paris CM chondrite

Fine-grained rims (FGRs) are ubiquitous in chondrites. They consist of unequilibrated mineral assemblages that surround chondrules and refractory inclusions. As such, they carry information about the material that was accreted onto chondrules. To decipher the nature and the formation mechanism of FGRs and compare them to adjacent matrix material, we investigated their composition, mineralogy, density and texture in the pristine Paris CM chondrite. We coupled a new method at the SEM scale (ACADEMY) that allows high-resolution quantitative petrology and an analytical TEM study.Significant differences in modal abundance, grain size and porosity are observed between the FGRs and their adjacent matrix. Amorphous silicates domains embedding nanosulfides are indicative of a high preservation degree. They are less abundant in the matrix than in the rims. In contrast, secondary alteration phases (phyllosilicates, carbonates and tochilinites) are more abundant in the matrix and associated with larger and fewer sulfides grains. The similar composition of the amorphous silicate in the rims and the matrix attests for a close relationship between the two reservoirs. However, matrix underwent more aqueous alteration. We interpret it as the result of the accretion of material with a higher water/rock ratio in the matrix, leading to a more aqueously altered microenvironment. We also find that coarse-grained anhydrous silicates (olivine and pyroxene) are present in the matrix but not in the FGRs, likely as a result of a chondrule fragmentation episode that occurred after FGR but before matrix accretion.Most of the time, FGRs display distinct inner and outer layers. The inner part is compact and displays larger sulfide grains than the outer part, which is more porous (porosity ∼ 45%) and altogether more pristine. These mineral and textural differences are not easily explained by differential aqueous alteration. Instead, a pre-accretion thermal process that preferentially affected the inner rim could have induced loss of porosity, compaction of the amorphous silicate domains as well as sulfides growth. We therefore suggest that FGRs acquired their characteristics in the nebula before matrix accretion and discuss possible mechanisms such as dust heating in the chondrule formation environment or secondary heating episode of the previously rimmed chondrule.

Arsenian Pyrite and Cinnabar from Active Submarine Nearshore Vents, Paleochori Bay, Milos Island, Greece

Active, shallow-water (2–10 m below sea level) and low temperature (up to 115 °C) hydrothermal venting at Paleochori Bay, nearshore Milos Island, Greece, discharges CO2 and H2S rich vapors (e.g., low-Cl fluid) and high-salinity liquids, which leads to a diverse assemblage of sulfide and alteration phases in an area of approximately 1 km2. Volcaniclastic detritus recovered from the seafloor is cemented by hydrothermal pyrite and marcasite, while semi-massive to massive pyrite-marcasite constitute mounds and chimney-like edifices. Paragenetic relationships indicate deposition of two distinct mineralogical assemblages related to the venting of high-Cl and low-Cl fluids, respectively: (1) colloform As- and Hg-bearing pyrite (Py I), associated with marcasite, calcite, and apatite, as well as (2) porous and/or massive As-rich pyrite (Py II), associated with barite, alunite/jarosite, and late-stage hydrous ferric oxides. Mercury, in the form of cinnabar, occurs within the As-rich pyrite (Py I) layers, usually forming distinct cinnabar-enriched micro-layers. Arsenic in colloform pyrite I shows a negative correlation with S indicating that As1− dominates in the pyrite structure suggesting formation from a relatively reducing As-rich fluid at conditions similar to low-sulfidation epithermal systems. On the contrary, As3+ dominates in the structure of porous to massive pyrite II suggesting deposition from a sulfate-dominated fluid with lower pH and higher fO2. Bulk sulfide data of pyrite-bearing hydrothermal precipitates also show elevated As (up to 2587 ppm) together with various epithermal-type elements, such as Sb (up to 274 ppm), Tl (up to 513 ppm), and Hg (up to 34 ppm) suggesting an epithermal nature for the hydrothermal activity at Paleochori Bay. Textural relationships indicate a contemporaneous deposition of As and Hg, which is suggested to be the result of venting from both high-salinity, liquid-dominated, as well as CO2- and H2S-rich vapor-dominated fluids that formed during fluid boiling. The CO2- and H2S-rich vapor that physically separated during fluid boiling from the high-salinity liquid led to calcite formation upon condensation in seawater together with the precipitation of As- and Hg-bearing pyrite I. This also led to the formation of sulfuric acid, thereby causing leaching and dissolution of primary iron-rich minerals in the volcaniclastic sediments, finally resulting in pyrite II precipitation in association with alunite/jarosite. The Paleochori vents contain the first documented occurrence of cinnabar on the seafloor in the Mediterranean area and provide an important link between offshore hydrothermal activity and the onshore mercury and arsenic mineralizing system on Milos Island. The results of this study therefore demonstrate that metal and metalloid precipitation in shallow-water continental arc environments is controlled by epithermal processes known from their subaerial analogues.

Quantifying the effects of alteration and acid treatment for whole-rock basalt 40Ar/39Ar geochronology

The presence of secondary phases (carbonates, zeolites, clay minerals, etc.) in volcanic rocks and subabyssal intrusive units (sills and dykes) often pose obstacles for high resolution 40Ar/39Ar geochronology as these phases may promote loss of radiogenic argon, production of interfering isotopes, or trapping of excessive atmospheric argon contents. Acid treatment is used to remove alteration products before sample irradiation and analysis. In an effort to assess and quantify the effects of alteration and the removal of alteration products by acid treatment on the accuracy and precision of 40Ar/39Ar analysis, three basalt samples from the Paraná large igneous province previously dated in triplicate without acid treatment were dated again without and with acid treatment. Despite the presence of 14–28% clay minerals in the samples, which results in up to 67% atmospheric component in the total amount of 40Ar extracted from untreated grains, the presence of alteration phases and their removal by acid treatment have no significant role on the accuracy of 40Ar/39Ar step-heating ages. The only quantifiable effect is an ~0.1% increase in age precision for the acid-treated aliquots. The results reveal that effective separation of atmospheric and radiogenic gases in properly designed and sufficiently detailed step-heating experiments successfully obviates deleterious effects associated with some types of alteration phases, and it suffices to produce high-resolution ages. Therefore, acid treatment is a desirable but not essential step in high-resolution 40Ar/39Ar geochronology. Characterizing alteration phases, however, is an essential step as some secondary products (e.g., sericite, albite), if present, will not be leached during acid treatment and will significantly affect the accuracy of geochronological results either with or without acid treatment.

Mineralogical and Leaching Characteristics of Altered Ilmenite Beach Placer Sands

In order to have a good understanding of the treatment process and improvement on the market value of ilmenite beach placer sands, knowledge of its mineral composition and phase distribution is fundamental. In this study, a combination of characterization techniques including high-resolution scanning electron microscopy (HR-SEM), high-resolution transmission electron (HR-TEM) microscope, and X-ray diffraction (XRD) techniques was used to understand the mineralogical characteristics of ilmenite beach placer sands obtained from Richards Bay, South Africa. The mineral phase constituents of the ilmenite beach placer sands were studied before pre-oxidation and additive leaching in a chloride environment. During observations using XRD and HR-SEM, the ilmenite beach placer sands exhibited signature rhombohedral crystal form and crescentic pits with evidence of alteration phases. The characterized pre-oxidized ilmenite showed the presence of a ferric oxide film deposit of the particles. The leaching characteristics of both raw and pre-oxidized ilmenite was studied in the presence of additives. The leaching efficiency of the pre-oxidized ilmenite in the presence of additives increased by 20% at atmospheric conditions. The characterized residues show the improved amenability of pre-oxidized leach in chloride media. The formation of new phases containing pseudo-rutile indicated crystallographic disintegration by the movement of atoms during dissolution. Some particles retained the crescentic pit and the subangular grain structure; however, the phase changes were observed at the grain boundaries and grain edges. The leached residue’s EDS results still indicated the presence of pseudo-rutile and some minor unreacted oxides such as SiO2, Al2O3, and other trace metals. The trace metals impurities present in the as-received ilmenite were reduced by 80% in the final residue after the leaching.

Nepheline solid solution compositions: stoichiometry revisited, reviewed, clarified and rationalised

AbstractMolecular formulae used to recalculate nepheline analyses generally have different numbers of oxygens (e.g. NaAlSiO4(Ne), KAlSiO4,(Ks), CaAl2Si2O8(An) and SiO2(Q)). A 32 oxygen cell has 16 T cations and 8 cavity sites, but ideal nepheline stoichiometry is not necessarily followed. Ca end-member □CaCaAl2Si2O4(CaNe) and excess silica end-member □SiSi2O4(Q’) calculation requires inclusion of both vacancy species as cavity cation values. Q’ parameter calculations can involve different assumptions and four parameters are described: Qxs; QSi; Q(Si–Al); and Qcavity; these should have closely similar values for high-quality, stoichiometric analyses.Representative published compositions are recalculated to assess whether authors followed ideal nepheline stoichiometry. Phenocrysts from peralkaline rocks and nephelinites typically exhibit Al deficiencies reflected in negative Δ(Al – cavity cation) parameters (ΔAlcc), negative ‘normative’ corundum (Al2O3,Cn), and anomalously low or negative Qxsparameters; for such rock types Q(Si–Al)provides a better estimate of excess silica contents. A ΔT-site (cation charge) parameter (ΔTcharge), is closely coupled to ΔAlccand end-member NaAlSiO4has a ΔAlcc/ΔTchargeratio of 1.4296; the derivation of this value is controlled by strict stuffed-tridymite, unit-cell constraints. Natural nephelines all contain excess silica with a mean ΔAlcc/ΔTchargeof ~1.134 reflecting their Si/Al ratio being > 1.Nepheline analyses with relatively low Al and Si and high Na (also Ca) contents are common; this might reflect the presence of small amounts (up to ~5%) of cancrinite as an alteration phase or perhaps even in solid solution. The compositions of alteration lamellae of Ca-rich cancrinite in altered nepheline phenocrysts in phonolites from the Marangudzi alkaline complex, Zimbabwe, are used to define diagnostic parameters for recognising such non-stoichiometry. These alteration lamellae formed hydrothermally from Ca-rich and K-poor fluids.An EXCEL file is provided to help researchers to standardise calculation of nepheline end-member molecular proportions.

Magnetic Properties of Ferritchromite and Cr‐Magnetite and Monitoring of Cr‐Spinels Alteration in Ultramafic and Mafic Rocks

AbstractSpinel is a ubiquitous mineral in mafic/ultramafic rocks. Spinel cores chemistry is extensively used as a petrogenetic proxy while their alteration phases, ferritchromite, and Cr‐magnetite, are used as metamorphic grade indicators. However, the magnetic properties and composition of these phases are still ill‐defined and no consensus exists concerning the metamorphic conditions involved in their formation. Here, we use the magnetic properties of these Cr‐spinel alteration phases, via field‐dependent parameters and observations with a magnetic microscope coupled with mineral chemistry and Mössbauer spectroscopy, to better constrain their composition. We identify Cr‐magnetite by a Curie point of ca. 520°C. We show that it is characterized by an n between 0.1 and 0.2 in the Fe‐Cr spinel formula [Fe2+(Fe1−nCrn)2O4], which corresponds to 6–13 wt.% of Cr2O3. The abundance of Cr‐magnetite indicates a strong alteration of Cr‐spinels that could reflect a significant hydrothermal activity rather than a high metamorphism grade. Normalized variation curves of the magnetic susceptibility during heating allow a relative quantification of the contributions of different magnetic phases to the magnetic susceptibility. This highlights a link between ferritchromite destabilization into maghemite at ca. 130°C followed by the destabilization of this maghemite starting at 300°C. We identify specific covariation trends between these two magnetic species characterizing different alteration processes. This study opens the door to magnetic monitoring of the Cr‐spinel alteration state in mafic and ultramafic rocks. It constitutes a new, fast, and weakly destructive way to study the petrological history of both terrestrial and extraterrestrial rocks.

High-Temperature Thermodynamics of Cerium Silicates, A-Ce2Si2O7, and Ce4.67(SiO4)3O

Lanthanide disilicates and oxyapatites have potential roles in high-temperature applications as thermal (TBC) and environmental barrier coatings (EBC) or possible alteration phases in geological nuclear waste repositories. However, those Ce3+-bearing silicates have only been limitedly studied. In this work, we performed detailed structural and thermodynamic investigations on A-Ce2Si2O7 (tetragonal, P41) and Ce4.67(SiO4)3O (hexagonal, P63/m). The high-temperature structural behaviors and coefficients of thermal expansion were determined by in situ high-temperature synchrotron X-ray diffraction (HT-XRD) implemented with Rietveld analysis and thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC). A-Ce2Si2O7 was found to be stable in N2 and air up to ∼1483 K with an isotropic thermal expansion along the a- and c-axes (αa = 12.3 × 10–6 K–1 and αc= 12.4 × 10–6 K–1). Ce4.67(SiO4)3O had a slow partial oxidation between 533 and 873 K to a new nonstoichiometric phase Ce3+1.67-xCe4+xCe3+3(SiO4)3O1+0.5x, followed by a thermal decomposition to CeO2 and SiO2 at ∼1000 K in air. By using high temperature oxide melt solution calorimetry at 973 K with lead borate as the solvent, the standard enthalpy of formation was determined for A-Ce2Si2O7 (−3825.1 ± 6.0 kJ/mol) and Ce4.67(SiO4)3O (−7391.3 ± 9.5 kJ/mol). These thermodynamic parameters were compared with those of CeO2, CeSiO4, and other silicate oxyapatites for examining their chemical stability in high-temperature environments relevant for aeronautical applications, mineral formation, and nuclear fuel cycle

Mid-infrared reflectance spectroscopy of carbonaceous chondrites and Calcium–Aluminum-rich inclusions

We obtained mid-infrared reflectance spectra of powdered size fractions (0–25 ​μm, 25–63 ​μm, 63–125 ​μm and 125–250 ​μm) of 5 carbonaceous chondrites HaH 280 (CK4), Allende (CV3), NWA 10574 (CM2) and Murchison (CM2), and C2 (ungrouped) Tagish Lake. In addition, in-situ micro-FTIR reflectance spectra of CAIs in Allende, Ornans and Vigarano have been made.These spectra are part of a database for the comparison with remote sensing data of asteroids and planetary bodies, but also for laboratory studies of meteorites.Carbonaceous chondrites HaH 280 (CK4), Allende (CV3) and NWA 10574 (CM2) show mid-IR spectra with Reststrahlen bands (RB) dominated by forsterite and pyroxene features. The transparency features (TF) are at 12.1 ​μm–12.9 ​μm and the Christiansen features (CF) at 8.5 ​μm–9.3 ​μm.Murchison (CM2) and ungrouped Tagish Lake (C2) show mainly phyllosilicate features in their spectra. The CF is between 8.6 ​μm and 9.0 ​μm.Micro-FTIR spectra of CAIs from Allende, Vigarano, and Ornans have spinel features between 14.1 ​μm and 14.3 ​μm. In addition, melilite was identified in the Vigarano and Ornans samples with characteristic features at 11.7 ​μm and 12.4 ​μm.Nepheline and sodalite features have been identified around 14 ​μm in the Allende CAI as alteration phases resulting from thermal metamorphism.A band shift in spinel with increasing Fe content from thermal metamorphism could be spectral indicator for parent body metamorphism.A comparison with other bulk samples from the same meteorites/type shows high similarity.Comparison of the finest size fractions modelled in emissivity with remote sensing data of asteroids shows some similarity between a linear mixture of Allende and Murchison and the spectra of asteroid 253 Mathilde. However, the main 10 ​μm plateau is clearly shifted by 0.5 ​μm between asteroid and meteorite spectra. Also, the general band shapes are different. Differences between asteroidal environment (e.g. fairy castle structure) and laboratory make direct comparisons difficult.

Abundant extraterrestrial amino acids in the primitive CM carbonaceous chondrite Asuka 12236

AbstractThe Asuka (A)‐12236 meteorite has recently been classified as a CM carbonaceous chondrite of petrologic type 3.0/2.9 and is among the most primitive CM meteorites studied to date. Here, we report the concentrations, relative distributions, and enantiomeric ratios of amino acids in water extracts of the A‐12236 meteorite and another primitive CM chondrite Elephant Moraine (EET) 96029 (CM2.7) determined by ultra‐high‐performance liquid chromatography time‐of‐flight mass spectrometry. EET 96029 was highly depleted in amino acids and dominated by glycine, while a wide diversity of two‐ to six‐carbon aliphatic primary amino acids were identified in A‐12236, which had a total amino acid abundance of 360 ± 18 nmol g−1, with most amino acids present without hydrolysis (free). The amino acid concentrations of A‐12236 were double those previously measured in the CM2.7 Paris meteorite, consistent with A‐12236 being a highly primitive and unheated CM chondrite. The high relative abundance of α‐amino acids in A‐12236 is consistent with formation by a Strecker‐cyanohydrin dominated synthesis during a limited early aqueous alteration phase on the CM meteorite parent body. The presence of predominantly free glycine, a near racemic mixture of alanine (d/l ~0.93–0.96), and elevated abundances of several terrestrially rare non‐protein amino acids including α‐aminoisobutyric acid (α‐AIB) and racemic isovaline indicate that these amino acids in A‐12236 are extraterrestrial in origin. Given a lack of evidence for biological amino acid contamination in A‐12236, it is possible that some of the l‐enantiomeric excesses (lee ~34–64%) of the protein amino acids, aspartic and glutamic acids and serine, are indigenous to the meteorite; however, isotopic measurements are needed for confirmation. In contrast to more aqueously altered CMs of petrologic types ≤2.5, no l‐isovaline excesses were detected in A‐12236. This observation strengthens the hypothesis that extensive parent body aqueous activity is required to produce or amplify the large l‐isovaline excesses that cannot be explained solely by exposure to circularly polarized radiation or other chiral symmetry breaking mechanisms prior to incorporation into the asteroid parent body.

Mineralogy and Genesis of the Kihabe Zn-Pb-V Prospect, Aha Hills, Northwest Botswana

The Kihabe Zn-Pb-V > (Cu-Ag-Ge) prospect is located at the boundary between Namibia and Botswana (Aha Hills, Ngamiland District) in a strongly deformed Proterozoic fold belt, corresponding to the NE extension of the Namibian Damara Orogen. The Kihabe prospect contains Zn-Pb resources of 14.4 million tonnes at 2.84% zinc equivalent, Ag resources of 3.3 million ounces, and notable V-Ge amounts, still not evaluated at a resource level. The ores are represented by a mixed sulfide–nonsulfide mineralization. Sulfide minerals consist mainly of sphalerite, galena and pyrite in a metamorphic quartzwacke. Among the nonsulfide assemblage, two styles of mineralization occur in the investigated samples: A first one, characterized by hydrothermal willemite and baileychlore, and a second one consisting of supergene smithsonite, cerussite, hemimorphite, Pb-phosphates, arsenates and vanadates. Willemite is present in two generations, which postdate sulfide emplacement and may also form at their expenses. These characteristics are similar to those observed in the willemite occurrences of the nearby Otavi Mountainland, which formed through hydrothermal processes, during the final stages of the Damara Orogeny. The formation of the Kihabe willemite is likely coeval. Baileychlore is characterized by textures indicating direct precipitation from solutions and dissolution–crystallization mechanisms. Both processes are typical of hydrothermal systems, thus suggesting a hydrothermal genesis for the Kihabe Zn-chlorite as well. Baileychlore could represent an alteration halo possibly associated either with the sulfide or with willemite mineralization. The other nonsulfide minerals, smithsonite, cerussite, various Pb-phosphates and vanadates, are clearly genetically associated with late phases of supergene alteration, which overprinted both the sulfide and the willemite- and baileychlore-bearing mineralizations. Supergene alteration probably occurred in this part of Botswana from the Late Cretaceous to the Miocene.

Hydrothermal alteration associated with the Chicxulub impact crater upper peak-ring breccias

The 66 Ma, ∼180 km Chicxulub impact structure in the northern Yucatán peninsula and southern Gulf of Mexico is the best-preserved large impact crater on Earth with a well-developed peak ring. The most recent drilling campaign took place offshore during the joint International Ocean Discovery Program – International Continental Scientific Drilling Program (IODP–ICDP) Expedition 364 at site M0077A (21.45°N, 89.95°W) and recovered ∼830 m of continuous core. Initial examination revealed that the peak-ring comprises four main lithological units (from the base upwards): crystalline basement granitoid rocks (Unit 4); a thin layer of impact melt rocks (Units 3A and B); melt-bearing breccias (Units 2A–C); and post-impact sedimentary rocks (Unit 1). Preliminary analysis of the drill core indicated that hydrothermal alteration has affected all lithologies and is especially pervasive in the melt-bearing breccias of Unit 2 (721.6 to 617.33 meters below sea floor, mbsf). Here we present the first detailed investigation of hydrothermal alteration within the melt-bearing breccias. Alteration phases are predominantly Fe-Mg clay minerals, zeolites, alkali feldspars, calcite and minor sulfides, sulfates, opal and Fe-Ti oxides. Alteration is especially intense proximal to lithologic contacts, particularly at the base of subunit 2B where there is an abrupt increase in host rock porosity ∼30 m above the impact melt rocks. The pervasiveness of clay minerals and zeolites is attributed to the high amounts of devitrified silicate glass throughout Unit 2. The phases preserved here are consistent with the findings of previous hydrothermal studies in other areas of the Chicxulub structure, and suggest an evolving water-rock system that was alkaline-saline, comparable to seawater-volcanic glass alteration.

Evaluation of crystallization conditions and porphyry Cu Mineralization potential of the Gheshlagh-Aftabrow pluton, central part of the Urumieh-Dokhtar magmatic belt, Iran

Gheshlagh-Aftabrow granodiorite (GAG) is emplaced within Eocene volcanic rocks in the central part of the Urumieh-Dokhtar magmatic belt (UDMB) of Iran and comprises of host granodiorites and associated mafic microgranular enclaves (MMEs). The Al-in-hornblende barometry and the amphibole–plagioclase thermometer are applied to calculate pressure and temperature. The host granodiorite yields crystallization temperatures and pressures varying from 635 to 715 °C (with an average of 670 °C) and from 0.5 to 1.8 kbar (with an average of 1.3 kbar, equivalent to a depth of 4.5 km), respectively. The mafic enclave shows a slightly higher crystallization temperature (690–720 °C, with an average of 705 °C) and pressure (1.1–1.8 kbar, with an average of 1.4 kbar), equivalent to a depth of 5 km. The estimated ƒO2 contents by amphibole chemistry in the host rocks and their mafic enclaves range − 11.2 to − 13.3 and − 11.5 to − 12.8, respectively, indicating that these rocks probably crystallized at relatively oxidizing conditions above the nickel–nickel oxide (NNO) buffer, yielding an overall range between NNO + 1.1 and NNO + 2.6, that is consistent with the general presence of magnetite and corresponds to their calc-alkaline affinity and the formation of the rocks in the subduction environment. The granodiorites and associated MMEs yield broadly similar water contents of 2.5–3.7 wt% and 2.6–3.7 wt%, respectively. The calculated densities of the host granitic magmas vary from 2319 to 2353 kg/m3, which are different from the determined densities of the mafic magma from which the enclaves are derived (2500–2626 kg/m3). The minimum calculated solidification time for the Gheshlagh-Aftabrow intrusion is about 20 × 104 years, and for the enclaves, it is less than 0.2 to 14 h that could not be enough time for pervasive mixing. Most of the amphiboles have Mg# value between 0.5 and 0.7, that together with low difference in densities of the magmas forming host rocks and enclaves may indicate that mantle–crust mixing was significant in the GAG generation. However, some geochemical signatures together with high ƒO2 content in the GAG samples indicate that these rocks are essentially comparable to granitoids associated with porphyry copper deposits, but according to the field evidences, the lack of extensive alteration, whole-rock chemistry (e.g., low Sr/Y and high Zr/Hf), plagioclase geochemistry, low water contents, and mineralogical evidences (e.g., lack of the common alteration phases in porphyry systems), it can be concluded that the studied pluton is barren regarding porphyry Cu mineralization.

Two episodes of REEs mineralization at the Sin Quyen IOCG deposit, NW Vietnam

The Sin Quyen iron oxide-copper–gold (IOCG) deposit in northwestern Vietnam contains a proven reserve of 52.8 Mt ores at 14% Fe, 0.91% Cu, 0.7% REEs (rare earth elements), and 0.44 g/t Au. REEs mineralization is hosted within Ca-silicate alteration zone and associated with Fe-Cu ore bodies in the gneiss, mica schist, and marble of the Upper Sin Quyen Formation. Two mineralization episodes are identified based on the field and petrographic relations. The first episode includes sodic alteration (stage I-1), calcic alteration and associated REE mineralization (stage I-2), and localized K-Fe alteration (stage I-3). The second episode is main stage mineralization and contains four main stages of alteration: pre-ore Na alteration (stage II-1), Ca-Fe alteration and the associated Fe-REE mineralization (stage II-2), K-Fe alteration and associated Cu-Au mineralization (stage II-3), and the final carbonate stage of quartz-carbonate veins (stage II-4) crosscutting the above-mentioned alteration phases and ores.Primary allanite and type 1 titanite (Tnt-1) from episode 1 yield weighted mean 206Pb/238U ages of 882 ± 3 Ma and 881 ± 8 Ma (2σ), respectively, which are interpreted as the timing of REE mineralization in episode 1. Secondary allanite and type 2 titanite (Tnt-2) associated with iron-oxide and Cu-Au ores, however, have U-Pb ages of 840 ± 7 Ma and 838 ± 5 Ma (2σ), respectively. These ages are hence considered to represent the timing of polymetallic IOCG mineralization in episode 2. ~880 Ma titanite grains have εNd(t) values ranging from −7.00 to −5.43, which are intermediate between the Neoproterozoic felsic intrusions and ore-hosting meta-sedimentary rocks in the region and likely reflect interaction between magmatic fluids and ore-hosting rocks. In contrast, ~840 Ma titanite have εNd(t) values ranging from −4.31 to −1.97, similar to those of the Neoproterozoic felsic intrusions, indicating a possible magmatic fluid source for the episode II IOCG mineralization. Multiple episodes of mineralization at Sin Quyen were likely formed during the prolonged tectonothermal events related to backarc extension during the Neoproterozoic subduction along the western margin of the Yangtze Block.

Temporal variation of titanite morphology and chemistry in a long-lived shear zone: The Clarke Head syenite in the Minas Fault Zone, Nova Scotia

The mineral chemistry of titanite has been studied in hydrothermally altered syenite preserved as blocks in a salt wall within a regional intracontinental shear zone. The study focusses on the controls on temporal variation in REEs, Zr, Nb, U and Th. Several generations of titanite are recognised on the basis of morphology, chemistry, and relationship to other secondary minerals. Magmatic euhedral to subhedral titanite has Ti and Zr contents characteristic of magmatic titanite in other studies, but does not have a magmatic abundance of REE. Rather, it is 102–104 times depleted in LREE and only slightly depleted in HREE. The leaching of LREE began during a regionally recognised phase of potassic alteration, as amphibole and biotite in gabbro and diorite recrystallized along shear zones and released K, Ca, and F. Later, some 15 Ma after emplacement, the alkali feldspar in the syenite was largely altered to scapolite and analcime by interaction with adjacent halite and gypsum deposits. Titanite formed at that time, from dissolution-reprecipitation reactions in large rutile crystals, is less depleted in LREE, as a result of the dominance of Cl− in hydrothermal waters. Following that event, F−-dominated hydrothermal waters prevailed again, resulting in more LREE depletion in previously formed titanite and in neoformed hydrothermal titanite. At that time, there was also depletion in Zr and U. The trace elements in hydrothermal titanite are thus very informative on the hydrothermal history of the rocks. A combination of morphology and trace-element signature allows different hydrothermal stages to be distinguished.

Simulation of Natural Iron Oxide Alteration in Soil: Conversion of Synthetic Ferrihydrite to Hematite Without Artificial Dopants, Observed With Magnetic Methods

AbstractWe present new results on the conversion of pure, undoped synthetic ferrihydrite, wet‐annealed at pH 6.56 and 90°C without stabilizing ligands, to nanophase goethite, hematite, and an intermediate magnetic phase, nanophase maghemite. Our analyses included magnetic field and temperature‐dependent properties and characterization by powder X‐ray diffraction, Mössbauer spectra, and high‐resolution transmission electron microscopy. We sampled alteration products after 0.5 hr, and then in a geometric progression to 32 hr, yielding a detailed examination of the earliest alteration phases. There are many similarities to the latest studies of pure ferrihydrite alteration but with a significant difference: We observe early appearance of oriented nanophase goethite along with a soft magnetic contribution, while rhombohedral hematite crystals form later, as reported in previous studies. Our observations attest to the non‐uniqueness of the magnetic enhancement process and to its strong dependence on environmental conditions, with important implications for use of the hematite/goethite ratio as a paleoprecipitation proxy.

Lead-Free Perovskite Variant Solid Solutions Cs2 Sn1- x Tex Cl6 : Bright Luminescence and High Anti-Water Stability.

Underwater lighting is important for the exploration of the underwater world in different areas. It is of great significance for developing underwater emitters with high penetrability, high luminous efficiency, good anti-water stability, and environmental friendliness. Stable lead-free perovskite luminescent materials, represented by vacancy-ordered double perovskites, are worthy of research because they can almost meet the above requirements. Here, lead-free perovskite variant solid solutions with the formula of Cs2 Sn1- x Tex Cl6 are reported. Upon the exchange of Sn/Te ions, strong Jahn-Teller distortion of octahedra occurs in the lattice structure. The combination of Te luminescent center and Jahn-Teller-like self-trapped excitons gives this material yellow-green luminescence with a wavelength of 580 nm and a high photoluminescence quantum yield of 95.4%. Moreover, these solid solutions can withstand the extreme conditions of immersion in water probably due to the formation of amorphous alteration phase. Such good anti-water stability is also supported by the molecule dynamics simulation result that no reaction occurs on the water/Cs2 SnCl6 interface. The high luminous, suitable wavelength, and good anti-water stability enable the solid solutions suitable for the application for underwater lighting.

Experimental alteration of granitic rocks: Implications for the evolution of geothermal brines in the Upper Rhine Graben, Germany

Geothermal energy exploitation in the Upper Rhine Graben (URG) chiefly has targeted faults and fractures within or connected with the crystalline basement, where hot fluids of c. 200 °C circulate at depths of c. 5 km. Formation fluids of the crystalline basement are highly saline, NaCl-dominated brines, whereas shallow crystalline basement water (< 500 m) is only weakly mineralized. In order to contribute to a better understanding of redistribution of elements in fluids and alteration phases during fluid-rock interaction processes we conducted leaching and alteration experiments with granites and monzonites from the Schwarzwald at 70 °C (rock powder, pure water) and 200 °C (texturally intact rock cylinders, 2m-NaCl), respectively, inspired by the P-T-x conditions reported for the URG.The trace element concentrations of the leachates are hereby related to the composition and stability of minerals in the rocks and can be directly linked to the proposed and observed dissolution processes at the different temperatures. In experiments with pure water at 70 °C, representing the recharge or infiltration conditions, water-rock interaction mobilized K, Cl, Fe, Mn, Mg, Cu, Zn, Cr, Sc, V, and Li (dissolution of biotite/chlorite) and Si, Al, K, Ca, Na, Ba, Sc, Pb, Sr, Rb, and Eu (dissolution of plagioclase, K-feldspar, and quartz) into the fluid. According to calculated activity diagrams, alteration at these temperatures may result in the formation of illite, kaolinite, Ca-beidellite, and stilbite. In experiments at higher temperatures of 200 °C, according to reservoir conditions, the net output of most elements was increased, but especially of those contained in feldspar, i.e. K, Ca, Al, Si, Ba, Rb, Cs, and Pb, suggesting that fluid-rock interaction is dominated by feldspar dissolution. This alteration is followed by albitization of feldspar surfaces, chloritization of biotite, and precipitation of illite and hematite. In Si-poor samples, analcime occurs in and around porous reaction zones, in agreement with calculated activity diagrams.The amount of dissolution mainly depends on the temperature and the mineralogy of the rock types, in particular on the anorthite-component of plagioclase. Certain elements (e.g., Na, Fe, Mg, Al) were subsequently incorporated into the solids precipitated during the experiments and thus cannot be considered as conservative.

Wettability alteration and mitigating aqueous phase trapping damage in tight gas sandstone reservoirs using mixed cationic surfactant/nonionic fluoro-surfactant solution

During drilling, completion and fracturing operations, aqueous phase from working fluids can invade into rock formations and engender phase trapping damage in the near well region. This formation damage can diminish the gas relative permeability and hinder the gas well productivity in tight gas sandstone reservoirs. In this study, we investigated the mixed surfactants system of cationic surfactant (SDCSA-1) and nonionic fluorinated surfactant (FC-0) at varied mixing mole ratios and concentrations to reduce the formation damage. Results showed that the minimum surface tension of mixed surfactants solution was relatively low with around 20 mN/m. In addition, surfactant mixtures altered the wettability of sandstone rock from water wetting to intermediate wetting condition. An optimal mixed system was obtained when the concentration is 10-4 mol/L and mole ratio of individual surfactants is 1:1. The mechanism of wettability alteration of surfactants to liquid/rock interface was further determined by adsorption experiments, atomic force microscopy(AFM) tests, and energy dispersive spectrum(EDS) tests. Two sets of spontaneous imbibition experiments were conducted including parallel imbibition tests and sequential imbibition tests. We observed that mixed surfactants solution can prominently prevent liquid invasion into sandstone rocks. We further calculated the capillary pressure to quantitatively examine the capillary effects of different imbibed fluids. When sandstone sample was treated by mixed surfactants, the capillary pressure decreased from 7.81 MPa to 0.97 MPa. Core displacement tests revealed that the liquid saturation of core sample filled with surfactants mixture decreased from 100% to 35.48% and the its gas permeability recovered to 72.86% of the core without liquid after gas flooding. NMR tests also confirmed that surfactant mixtures can be more easily drained than brine from pores in tight sandstone. Consequently, we proposed an improved method to mitigate water blocking damage based on wettability alteration by mixed cationic surfactant and nonionic fluoro-surfactant system.

Mineralogy of Silicate-Natrophosphate Immiscible Inclusion in Elga IIE Iron Meteorite

Rare type of silicate inclusions found in the Elga iron meteorite (group IIE) has a very specific mineral composition and shows silicate (≈90%)–natrophosphate (≈10%) liquid immiscibility due to meniscus-like isolation of Na-Ca-Mg-Fe phosphates. The 3 mm wide immiscible inclusion has been first studied in detail using optical microscopy, scanning electron microscopy, electron microprobe analysis and Raman spectroscopy. The silicate part of the inclusion contains fine-grained quartz-feldspar aggregate and mafic minerals. The relationships of feldspars indicate solid decay of initially homogenous K-Na-feldspar into albite and K-feldspar with decreasing of temperature. Some mafic minerals in the silicate part are exotic in composition: the dominant phase is an obertiite-subgroup oxyamphibole (amphibole supergroup), varying from ferri-obertiite NaNa2Mg3Fe3+Ti[Si8O22]O2 to hypothetical NaNa2Mg3Fe2+0.5Ti1.5[Si8O22]O2; minor phases are the aenigmatite-subgroup mineral (sapphirine supergroup) with composition close to median value of the Na2Fe2+5TiSi6O18O2-Na2Mg5TiSi6O18O2 join, orthopyroxene (enstatite), clinopyroxene of the diopside Ca(Mg,Fe)Si2O6–kosmochlor NaCrSi2O6-Na(Mg,Fe)0.5Ti0.5Si2O6 series and chromite. The alteration phases are represented by Fe-dominant chlorite, goethite and hydrated Na2O-rich (2.3–3.3 wt.%) Fe-phosphate close to vivianite. Natrophosphate part consists of aggregate of three orthophosphates (brianite, czochralskiite, marićite) and minor Na-Cr-Ti-clinopyroxene, pentlandite, rarely taenite. Czochralskiite Na4Ca3Mg(PO4)4 is rich in FeO (2.3–5.1 wt.%) and MnO (0.4–1.5 wt.%). Brianite Na2CaMg(PO4)2 contains FeO (3.0–4.3 wt.%) and MnO (0.3–0.7 wt.%) and marićite NaFe(PO4) bears MnO (5.5–6.2 wt.%), MgO (5.3–6.2 wt.%) and CaO (0.5–1.5 wt.%). The contact between immiscible parts is decorated by enstatite zone in the silicate part and diopside–kosmochlor clinopyroxene zone in the natrophosphate ones. The mineralogy of the studied immiscible inclusion outlines three potentially new mineral species, which were first identified in meteorites: obertiite–related oxyamphibole NaNa2Mg3Fe2+0.5Ti1.5[Si8O22]O2, Mg-analog of aenigmatite Na2Mg5TiSi6O18O2 and Na-Ti-rich clinopyroxene Na(Mg,Fe)0.5Ti0.5Si2O6.

Hydrous olivine alteration on Mars and Earth

AbstractHydrous alteration of olivine macrocrysts in a Martian olivine phyric basalt, NWA 10416, and a terrestrial basalt from southern Colorado are examined using SEM, EPMA, TEM, and µXRD techniques. The olivines in the meteorite contain linear nanotubes of hydrous material, amorphous areas, and fluid dissolution textures quite distinct from alteration identified in other Martian meteorites. Instead, they bear resemblance to terrestrial deuteric alteration features. The presence of the hydrous alteration phase Mg‐laihunite within the olivines has been confirmed by µXRD analysis. The cores of the olivines in both Martian and terrestrial samples are overgrown by unaltered rims whose compositions match those of a separate population of groundmass olivines, suggesting that the core olivines are xenocrysts whose alteration preceded crystallization of the groundmass. The terrestrial sample is linked to deep crustal metasomatism and the “ignimbrite flare‐up” of the Oligocene epoch. The comparison of the two samples suggests the existence of an analogous relatively water‐rich magmatic reservoir on Mars.