End-member Compositions Research Articles

The tetrahedrite group: Nomenclature and classification

AbstractThe classification of the tetrahedrite group minerals in keeping with the current IMA-accepted nomenclature rules is discussed. Tetrahedrite isotypes are cubic, with space group symmetry I43m. The general structural formula of minerals belonging to this group can be written as M(2)A6M(1)(B4C2)X(3) D4S(1)Y12S(2)Z, where A = Cu+, Ag+, ☐ (vacancy), and (Ag6)4+ clusters; B = Cu+, and Ag+; C = Zn2+, Fe2+, Hg2+, Cd2+, Mn2+, Cu2+, Cu+, and Fe3+; D = Sb3+, As3+, Bi3+, and Te4+; Y = S2– and Se2–; and Z = S 2–, Se2–, and ☐. The occurrence of both Me+ and Me2+ cations at the M(1) site, in a 4:2 atomic ratio, is a case of valency-imposed double site-occupancy. Consequently, different combinations of B and C constituents should be regarded as separate mineral species. The tetrahedrite group is divided into five different series on the basis of the A, B, D, and Y constituents, i.e., the tetrahedrite, tennantite, freibergite, hakite, and giraudite series. The nature of the dominant C constituent (the so-called “charge-compensating constituent”) is made explicit using a hyphenated suffix between parentheses. Rozhdestvenskayaite, arsenofreibergite, and goldfieldite could be the names of three other series. Eleven minerals belonging to the tetrahedrite group are considered as valid species: argentotennantite-(Zn), argentotetrahedrite-(Fe), kenoargentotetrahedrite-(Fe), giraudite-(Zn), goldfieldite, hakite-(Hg), rozhdestvenskayaite-(Zn), tennantite-(Fe), tennantite-(Zn), tetrahedrite-(Fe), and tetrahedrite-(Zn). Furthermore, annivite is formally discredited. Minerals corresponding to different end-member compositions should be approved as new mineral species by the IMA-CNMNC following the submission of regular proposals. The nomenclature and classification system of the tetrahedrite group, approved by the IMA-CNMNC, allows the full description of the chemical variability of the tetrahedrite minerals and it is able to convey important chemical information not only to mineralogists but also to ore geologists and industry professionals.

Quenching in Mn4+-Complex Fluoride Phosphors: Initial Relationships Based upon NaKSiF6:Mn4+

Mn4+-doped complex fluoride compositions are an important class of phosphors that provide narrow-band 2E→4A2 red emission for liquid crystal display (LCD) backlighting and illumination light emitting diodes (LEDs). In this report, we discuss the high temperature quenching in these phosphors, focusing on the NaKSiF6:Mn4+ phase that has a lower quenching temperature by >75K versus the two end-member compositions, K2SiF6:Mn4+ and Na2SiF6:Mn4+. Measurements of the 2E electron-phonon coupling through line shift versus temperature measurements do not give significant differences between NaKSiF6:Mn4+ and other Mn4+-doped complex fluoride phosphors with higher quenching temperatures. We tentatively attribute the stronger quenching in NaKSiF6:Mn4+ to additional distortion in the excited 4T2 state that is thermally populated from the 2E level at high temperatures. In addition, we discuss potential trade-offs between high temperature luminescence quenching and faster 2E→4A2 emission lifetimes.

Reactive iron isotope signatures of the East Asian dust particles: Implications for iron cycling in the deep North Pacific

Iron released from wind-blown dust has been widely suggested to be an important nutrient source for oceanic primary productivity. Once introduced into the seawater, the reactive Fe might get dissolved and impart its isotope signature into the water column. Characterization of the reactive iron isotope signatures of eolian dust will thus help to understand the budget of Fe in the global ocean. Yet, there are few systematic studies on the Fe isotope systematics of the dust sources across large spatial scale. Here, we report Fe isotope data from HCl leaching experiment on surficial samples from deserts and loess deposits of different locations spanning >3000 km spatially in east Asia, one of the most important dust source regions. Our data suggest most of the samples have relatively similar leaching signatures (δ56Fe = –0.09±0.07‰, n=9, 2 SD). To understand the kinetics of Fe release during proton promoted leaching of natural particles, a synthetic model taking into account of different dissolution dynamics of easily dissolvable Fe and silicate Fe was developed. The model was tested by continuous leaching of two representative pelagic sediment samples recovered from core LL44-GPC3 in the North Pacific. When introducing only one tunable parameter (i.e., the initial dissolution rate of Fe from hydro(oxides), with other parameters constrained by the dissolution kinetics), the model successfully reproduces leachate δ56Fe evolution and agrees reasonably well with Fe speciation in the studied marine sediment samples. We thus suggest that the leaching process can be well characterized by our kinetic model, while Fe isotopes in the initial leachates of the samples are dominated by endmember composition of the easily dissolvable Fe species. The small but distinct fractionation of Fe isotopes in the desert/loess samples from the parental upper continental silicate materials are suggested to record signatures of the secondary Fe species produced during weathering in the oxic environment. The significantly lighter Fe isotope compositions in the initial leachates of the North Pacific pelagic sediment samples compared to the east Asian desert/loess deposits indicate apparent isotope exchange of the dust reactive components with seawater dissolved species. The sedimentary light reactive Fe isotope signatures in turn point toward the contribution of sources characterized by low δ56Fe to the deep North Pacific and/or preferential uptake of 56Fe by seawater ligands from the dust reactive components particularly at the seawater-sediment interface.

Compositional Constraints for Lucy Mission Trojan Asteroids via Near-infrared Spectroscopy

Abstract We report near-infrared (0.7–2.5 μm) reflectance spectra for each of the six target asteroids of the forthcoming NASA Discovery-class mission Lucy. Five Jupiter Trojans (the binary (617) Patroclus system, (3548) Eurybates, (21900) Orus, (11351) Leucus, and (15094) Polymele) are well characterized, with measurable spectral differences. We also report a survey-quality spectrum for main-belt asteroid (52246) Donaldjohanson. We measured a continuum of spectral slopes including “red” (Orus, Leucus), “less red” (Eurybates, Patroclus-Menoetius), and intermediate (Polymele), indicating a range of compositional end-members or geological histories. We perform radiative transfer modeling of several possible surface compositions. We find that the mild-sloped spectra and low albedo of Patroclus and Eurybates imply similar compositions. Eurybates (∼7 wt.% water ice) and Patroclus (∼4 wt.% water ice) are consistent with a hydrated surface. Models for Orus and Leucus are consistent with each other and require a significantly more reddening agent (e.g., iron-rich silicates or tholin-like organics). Polymele has a linear spectrum like Patroclus, but a higher albedo more closely aligned with Orus/Leucus, defying simple grouping. Solar system formation models generally predict that the Jovian Trojans accreted in the outer solar system. Our observations and analysis are generally consistently with this expectation, although not uniquely so.

Mineralogical and lithological unmixing with radiative transfer modelling in the open-pit context of Mine Canadian Malartic

In this study, Hapke's radiative transfer model is used to verify the feasibility of retrieving the composition and grain-size of the ground in an open-pit mine, seen as a regolith. Such a tool could be useful for dust surveys and thus preventing potential environmental risks such as acid mine drainage. As the true compositional endmembers of the medium are not retrieved but rather chosen from spectral libraries and the range of grain sizes (a few to hundreds of micrometers) and porosities (0.22 to 0.52 for the filling factor) vary greatly in an open-pit mine, we show that the mineralogical unmixing results are not reliable. Too many combinations of different relative abundances, grain sizes and porosities lead to fits between modelled and measured spectra under 0.3% in reflectance. To tackle this issue, we explore a lithological unmixing approach. Considering lithologies as endmembers, as opposed to considering minerals, reduces the variability in the solutions as fewer endmembers are used. The results show that the studied samples with multi-component grains behave spectrally as expected for mono-mineral grains. With no root mean square errors higher than 5%, the relative abundances retrieved are sufficiently precise to consider mapping lithologies with this method.

Near end-member shenzhuangite, NiFeS2, found in Muong Nong-type tektites from Laos

Abstract Australasian Muong Nong-type tektites from the locality centered at 16.46150° N, 106.48917° E in Laos contain sporadic spherical heterogeneous sulfide inclusions less than 10 μm in diameter, which have been identified by electron probe microanalyzer and electron backscatter diffraction to represent a mixture of rare mineral shenzhuangite with a pyrrhotite polytype (possibly troilite). Contrary to type shenzhuangite found in the shocked L6 chondrite Suizhou, the mineral embedded in the tektite glass is nearly free of copper, making the composition close to its expected end-member that has not yet been found in nature; the empirical formula closest to ideal end-member composition based on four atoms per formula unit is Ni1.007Fe0.998Cu0.016Co0.058S1.922. The described occurrence also represents the first find of shenzhuangite in terrestrial material. Presented is the Raman spectrum for shenzhuangite with the tentative assignment of spectral bands based on the analogy with synthetic chalcopyrite-structured phases. The chemical composition of shenzhuangite close to NiFeS2 is not consistent with any stable phase in the Fe–Ni–S system up to melting temperature. Available data so far on phase relations in this system do not allow unambiguous interpretation of conditions under which the sulfide association within inclusions had formed.

Quantifying Riverine Recharge Impacts on Redox Conditions and Arsenic Release in Groundwater Aquifers Along the Red River, Vietnam.

Widespread contamination of groundwater with geogenic arsenic is attributed to microbial dissolution of arsenic-bearing iron (oxyhydr)oxides minerals coupled to the oxidation of organic carbon. The recharge sources to an aquifer can influence groundwater arsenic concentrations by transport of dissolved arsenic or reactive constituents that affect arsenic mobilization. To understand how different recharge sources affect arsenic contamination-in particular through their influence on organic carbon and sulfate cycling-we delineated and quantified recharge sources in the arsenic affected region around Hanoi, Vietnam. We constrained potential end-member compositions and employed a novel end-member mixing model using an ensemble approach to apportion recharge sources. Groundwater arsenic and dissolved organic carbon concentrations are controlled by the dominant source of recharge. High arsenic concentrations are prevalent regardless of high dissolved organic carbon or ammonium levels, indicative of organic matter decomposition, where the dominant recharge source is riverine. In contrast, high dissolved organic carbon and significant organic matter decomposition are required to generate elevated groundwater arsenic where recharge is largely nonriverine. These findings suggest that in areas of riverine recharge, arsenic may be efficiently mobilized from reactive surficial environments and carried from river-aquifer interfaces into groundwater. In groundwaters derived from nonriverine recharge areas, significantly more organic carbon mineralization is required to obtain equivalent levels of arsenic mobilization within inland sediments. This method can be broadly applied to examine the connection between hydrology, geochemistry and groundwater quality.

Assessing the preservation and provenance of Sr and Nd isotopic signatures in Cretaceous volcanic ash beds

Bentonite, a claystone formed from the devitrification of volcanic ash, demonstrates varying amounts of alteration in elemental concentrations through the transition from glass to clay. Many studies have sought to characterize and correlate bentonites using various elemental signatures, but the information garnered from this can be misleading since 1) volcanoes produce highly variable compositions during single events, making tephra classifications reliant on the position within the bed and the distance from the source, and 2) the elemental concentrations may vary significantly due to devitrification. Strontium and neodymium isotopic signatures offer a powerful dataset to supplement these efforts, but the extent to which the isotopic ratio is preserved during devitrification and post-depositional diagenesis is not well documented. Here we perform a detailed isotopic, geochemical, and mineralogical examination of sixteen bentonites preserved in Cenomanian and Campanian strata (Late Cretaceous) from South Dakota in order to characterize the diagenetic factors that may influence the ash geochemistry, while checking for the fidelity of the isotopic signatures to the magmatic source. A mixing model between the isotopic composition of bentonite and seawater can be generated to determine the original endmember composition of each deposit, since Sr was likely derived from both sources during devitrification. Initial 87Sr/86Sr ratios from Cenomanian samples ranged higher than the Campanian, demonstrating a negative correlation with εNd values that point towards magmatic signatures with the influence of crustal assimilation. X-Ray diffraction was utilized to determine the speciation of the clay mineral and sedimentary input, displaying a complete lack of smectite illitization that would indicate the presence of a hydrothermal influence. Bentonite isotopic chemistry, therefore, is reliably traced to the magmatic source under the appropriate diagenetic conditions. With careful consideration for diagenesis, the isotopic composition of the Cretaceous bentonites can be used for provenance identification and points towards magmatic emplacement within an evolved crustal source on the Laurentian craton. This isolates the most likely provenance of Cenomanian bentonites as being the Idaho batholith, while Campanian bentonites were likely derived from the Elkhorn Volcanic complex.

Compressibility of synthetic Mg-Al tourmalines to 60 GPa

AbstractHigh-pressure single-crystal X-ray diffraction patterns on five synthetic Mg-Al tourmalines with near end-member compositions [dravite NaMg3Al6Si6O18(BO3)3(OH)3OH, K-dravite KMg3Al6Si6O18(BO3)3(OH)3OH, magnesio-foitite □(Mg2Al)Al6Si6O18(BO3)3(OH)3OH, oxy-uvite CaMg3Al6Si6O18(BO3)3(OH)3O, and olenite NaAl3Al6Si6O18(BO3)3O3OH, where □ represents an X-site vacancy] were collected to 60 GPa at 300 K using a diamond-anvil cell and synchrotron radiation. No phase transitions were observed for any of the investigated compositions. The refined unit-cell parameters were used to constrain third-order Birch-Murnaghan pressure-volume equation of states with the following isothermal bulk moduli (K0 in GPa) and corresponding pressure derivatives (K0′ = ∂K0/∂P)T: dravite K0 = 97(6), K0′ = 5.0(5); K-dravite K0 = 109(4), K0′ = 4.3(2); oxy-uvite K0 = 110(2), K0′ = 4.1(1); magnesio-foitite K0 = 116(2), K0′ = 3.5(1); olenite K0 = 116(6), K0′ = 4.7(4). Each tour-maline exhibits highly anisotropic behavior under compression, with the c axis 2.8–3.6 times more compressible than the a axis at ambient conditions. This anisotropy decreases strongly with increasing pressure and the c axis is onlŷ14% more compressible than the a axis near 60 GPa. The octahedral Y- and Z-sites' composition exerts a primary control on tourmaline's compressibility, whereby Al content is correlated with a decrease in the c-axis compressibility and a corresponding increase in K0 and K0′. Contrary to expectations, the identity of the X-site-occupying ion (Na, K, or Ca) does not have a demonstrable effect on tourmaline's compression curve. The presence of a fully vacant X site in magnesio-foitite results in a decrease of K0′ relative to the alkali and Ca tourmalines. The decrease in K0′ for magnesio-foitite is accounted for by an increase in compressibility along the a axis at high pressure, reflecting increased compression of tourmaline's ring structure in the presence of a vacant X site. This study highlights the utility of synthetic crystals in untangling the effect of composition on tourmaline's compression behavior.

Discrepancy between bulk-rock and zircon Hf isotopes accompanying Nd-Hf isotope decoupling

Abstract Zircon is an important accessory mineral for studying the crust-mantle interaction and crustal growth through time because zircon crystals not only allow precise dating but also record initial Hf isotope ratios of the host magma. Our study on a suite of gabbronorite, mafic diorite cumulate, diorite and granite from the Kekeli Batholith in the North Qilian Orogenic Belt, Northern Tibetan Plateau, shows (1) a significant Hf isotope discrepancy between zircon and their bulk rocks; and (2) bulk-rock Nd-Hf isotope decoupling. These observations thus demonstrate that zircons do not always capture the full history of magmatic system. The significant positive correlation between bulk-rock Hf isotope ratios and TiO2 content (R2 = 0.94) indicates that Ti-rich minerals (e.g., ilmenite, amphibole) are likely important Hf hosts. The early-formed Ti-rich minerals possibly record different Hf isotopes from those of zircons crystallized subsequently, thus causing discrepancy between zircon and bulk-rocks and leading to bulk-rock Nd-Hf isotope decoupling. Correlations between bulk-rock TiO2 content, Mg isotopes and Hf isotopes indicate a mixing process, with granite and gabbronorite representing two compositional endmembers. Because Ti minerals have higher crystallization temperatures than zircons, when the mixing melts have contrasting isotopes (or from heterogeneous sources/have a strong crustal contamination), the bulk-rock and zircon Hf isotope discrepancies reflect mineral crystallization sequence during mafic and felsic magma mixing. It is thus imperative to consider early formed minerals such as Ti-rich minerals and the bulk rock composition, not just zircons, when using Hf isotopes to track melt evolution and precisely constrain mantle contribution to granitoid petrogenesis.

Mercury isotopic signatures of tailings from artisanal and small-scale gold mining (ASGM) in southwestern Ecuador

Artisanal and small-scale gold mining (ASGM) is currently one of the largest anthropogenic sources of mercury (Hg) to the atmosphere and a significant source to downstream terrestrial aquatic systems. Given the potential toxicity of Hg when it is released to aquatic ecosystems, both scientific and regulatory communities have interest in the development of tools and methods for understanding the fate and transport of Hg in the environment. Although Hg isotopes are applied extensively to trace other anthropogenic point sources of Hg in aquatic ecosystems, few studies have used isotopic analyses to investigate the downstream impacts of ASGM. Furthermore, these studies are currently limited by relatively sparse Hg isotopic analyses on ASGM materials. In this study, ASGM samples from Portovelo-Zaruma (Ecuador), representing various stages of the processing of low-grade gold-bearing ores, were analyzed for Hg concentrations and stable isotope ratios. These data were used to assess the isotopic variability of the ASGM endmember and confirm the results of prior isotopic analyses of ASGM materials and downstream sediments from Portovelo-Zaruma. While the Hg concentrations of the ASGM samples varied significantly, isotopic analyses revealed a limited range of signatures that was characterized by relatively heavy mass-dependent fractionation (MDF) with little to no significant mass-independent fractionation (MIF). The signatures of ASGM samples analyzed in this study matched well with previously reported ASGM samples from Portovelo-Zaruma as well as downstream sediments (for up to 120 km). Furthermore, the overall Hg isotopic compositions of potential ASGM endmembers are distinct from typical compositions observed in freshwater ecosystems (e.g., from soil erosion, atmospheric deposition), allowing Hg isotopes to be a powerful tool in tracing downstream Hg contamination from ASGM.

Pseudo-binary and pseudo-ternary diffusion couple methods for estimation of the diffusion coefficients in multicomponent systems and high entropy alloys

ABSTRACTThe benefits of using the pseudo-binary and pseudo-ternary diffusion couple methods in multicomponent inhomogeneous systems are demonstrated by estimating different types of composition-dependent diffusion coefficients. These are important for understanding the basic atomic mechanism of diffusion and complex compositional evolutions. These were otherwise considered impossible during the last many decades. Without any options previously, sometimes the average values over a composition range of random choice were estimated, which are not the material constants but depend on the composition range and also the end member compositions. The steps and analyses for utilising the pseudo-binary and pseudo-ternary methods are first described in the Ni-Co-Fe-Mo system by producing the ideal diffusion profiles fulfilling the concepts behind these methods. Following, the discussion is extended to the systems related to medium (Ni-Co-Cr) and high (Ni-Co-Fe-Mn-Al) entropy alloys. In fact, this is the first report showing a correct experimental method that should be followed for the estimation of the interdiffusion and intrinsic diffusion coefficients in inhomogeneous high entropy alloys. In the end, the limitations of following these methods because of the generation of non-ideal diffusion profiles are discussed based on experimental results. The steps are also suggested to avoid such complications. These methods are easy to adopt for research engineers. Most importantly, these give an opportunity to validate the data estimated following newly proposed numerical methods by different groups with experimentally estimated diffusion coefficients, which were not possible earlier.

In situ Viscometry of Primitive Lunar Magmas at High Pressure and High Temperature

Understanding the dynamics of the magmatic evolution of the interior of the Moon requires accurate knowledge of the viscosity () of lunar magmas at high pressure (P) and high temperature (T) conditions. Although the viscosities of terrestrial magmas are relatively well documented, and their relation to magma composition well studied, the viscosities of lunar titano-silicate melts are not well known. Here, we present an experimentally measured viscosity dataset for three end member compositions, characterized by a wide range of titanium contents, at lunar-relevant pressure-temperature range of 1.1 – 2.4 GPa and 1830 - 2090 K. In-situ viscometry using the falling sphere technique shows that the viscosity of lunar melts varies between  0.13 and 0.87 Pa-s depending on temperature, pressure and composition. Viscosity decreases with increasing temperature with activation energies for viscous flow of Ea = 201 kJ/mol and Ea = 106 kJ/mol for low-titanium (Ti) and high-Ti melts, respectively. Pressure is found to mildly increase the viscosity of these intermediate polymerized melts by a factor of  1.5 between 1.1 and 2.4 GPa. Viscosities of low-Ti and high-Ti magmas at their respective melting temperatures are very close. However at identical P-T conditions ( 1.3 GPa,  1840 K) low-Ti magmas are about a factor of three more viscous than high-Ti magmas, reflecting structural effects of Si and Ti on melt viscosity. Measured viscosities differ significantly from empirical models based on measurements of the viscosity of terrestrial basalts, with largest deviations observed for the most Ti-rich and Si-poor composition. Viscosity coefficients for these primitive lunar melts are found to be lower than those of common terrestrial basalts, giving them a high mobility throughout the lunar mantle and onto the surface of the Moon despite their Fe and Ti-rich compositions.

Long-lived compositional heterogeneities in magma chambers, and implications for volcanic hazard

Magmas discharged during individual volcanic eruptions commonly display compositional variations interpreted as new arrivals at shallow depth of more primitive, hotter, volatile-rich magma batches mixing with resident, colder, partially degassed magma. Heterogeneities in eruption products are often interpreted as evidence of short times of order tens of hours from new magma arrival to eruption, raising concerns for emergency planning. We show here, through numerical simulations, that magma convection and mixing in a shallow magma chamber can result in long-lived, dynamically stable configurations with coexistence of magmas from nearly pure to variably mixed end-member compositions. Short mixing time scales may therefore relate to sin-eruptive processes, as heterogeneities found in the eruptive products are not necessarily the fingerprint of new magma arrival shortly preceding or triggering the eruption.

Age and Origin of Monazite Symplectite in an Iron Oxide-Apatite Deposit in the Adirondack Mountains, New York, USA: Implications for Tracking Fluid Conditions

Monazite crystals, intergrown with allanite, fluorapatite, and quartz from the Cheever Mine iron oxide-apatite (IOA-type) deposit in Essex County, New York, USA, display rare symplectite textures. Electron probe wavelength-dispersive spectrometry (WDS) mapping and major and trace element characterization of these features reveal a natural experiment in fluid-mediated monazite recrystallization. Two types of monazite with symplectite intergrowths have been recognized (Type I and II). Both types of symplectite development are associated with a decrease in HREE, Si, Ca, Th, and Y, but an increase in both La and Ce in monazite. Electron microprobe Th-U-total Pb analysis of Type I monazite with suitable ThO2 concentrations yielded a weighted mean age of 980 ± 5.8 Ma (MSWD: 3.3), which is interpreted as the age of monazite formation and the onset of symplectite development. Both types of monazite formed during a series of reactions from fluorapatite, and possibly britholite, to produce the final assemblage of monazite, allanite, and fluorapatite. Monazite formation was likely a response to evolving fluid conditions, which favored monazite stability over fluorapatite at ca. 980 Ma, possibly a NaCl brine. A subsequent transition to a Ca-dominated fluid may have then promoted the consumption of monazite to produce another generation of allanite and fluorapatite. Our results indicate that recrystallized monazite formed during fluid-mediated processes that, over time, trended towards an increasingly pure end-member composition. Regionally, these data are consistent with a magmatic-origin followed by fluid-mediated remobilization of select phases at subsolidus conditions for the Adirondack IOA deposits.

Age and origin of Researcher Ridge and an explanation for the 14° N anomaly on the Mid-Atlantic Ridge by plume-ridge interaction

Researcher Ridge is a 400 km long, WNW-ESE oriented chain of volcanic structures, located on ~20 to 40 Ma old oceanic crust on the western flank of the Mid-Atlantic Ridge (MAR) at ~15° N. Researcher Ridge has been little studied, and its age and origin are currently unclear. At roughly the same latitude (14–15° N), the MAR axis is bathymetrically elevated and geochemically enriched (hereafter referred to as the 14° N MAR anomaly). This study presents 40Ar/39Ar age data, major and trace elements, and Sr-Nd-Pb-Hf isotopic compositions of volcanic rocks dredged from several seamounts of the Researcher Ridge. In addition, new geochemical data of MORBs from two 13–14° N dredge sites on the MAR are also presented. The results reveal that Researcher Ridge lavas have geochemically enriched ocean island basalt compositions (chondrite-normalized [La/Sm]N = 1.7–5.0, and [Ce/Yb]N = 1.58–11.3) with isotopic signatures (143Nd/144Nd = 0.51294–0.51316, 87Sr/86Sr = 0.70266–0.70405, 206Pb/204Pb = 19.14–19.93, 207Pb/204Pb = 15.57–15.63, 208Pb/204Pb = 38.82–39.17, and 176Hf/177Hf = 0.28307–0.28312) trending towards the FOZO or HIMU mantle end member composition. Based on the new age and geochemical data, Researcher Ridge is interpreted as a classic hotspot track, albeit formed by a relatively weak melting anomaly. The lavas from the 14° N MAR anomaly have an enriched E-MORB type composition ([La/Sm]N = 1.81–2.29, [Ce/Yb]N = 1.6–3.9). Their isotopic compositions (143Nd/144Nd = 0.51298–0.51313, 87Sr/86Sr = 0.70250–0.70282, 206Pb/204Pb = 18.90–19.31, 207Pb/204Pb = 15.52–15.58, 208Pb/204Pb = 38.45–38.95, 176Hf/177Hf = 0.28315–0.28320) plot at the enriched end of the local MORB array and partly overlap the Researcher Ridge lava compositions, suggesting a genetic relationship. We propose that the 14° N MAR anomaly is caused by deflection of upwelling Researcher Ridge plume material towards the westward migrating MAR, causing the production of E-MORBs with similar isotopic compositions to the Researcher Ridge lavas. Once the plume was captured by the spreading ridge, off-axis hotspot track volcanism ceased, resulting in a seamount gap between the eastern end of the Researcher Ridge and the 14° N MAR anomaly.

Provenance Studies of Ilmenite from Red Sediments, Bhimunipatnam Coast, East Coast of India

Abstract Mineral chemistry of the ilmenites, drawn from the red sediments along the Bhimunipatnam coast, Andhra Pradesh, India was determined by EPMA technique. The major constituents are TiO2 and FeO, and the value of Ti/(Ti + Fe) < 0.5 of these ilmenites indicate that they are relatively fresh ‘ferrian ilmenites’ and were contributed recently to the red sediments in the study area. Using the mineral chemical data, the end-member composition of the analyzed ilmenites was calculated, which reveals that they are of ‘ilmenite - hematite’ and ‘ilmenite - geikielite - hematite’ composition, derived from calc-alkaline magma-sourced charnockites and metapelitic khondalite suite of rocks respectively of the Eastern Ghats granulite belt. The TiO2 content and Mn/Mg ratio of the study ilmenites indicate that these rocks constitute their provenance in the Gosthani river basin. Their back scattered electron (BSE) and scanning electron (SEM) images show their prominent sub-angular to sub-rounded shape, corroborating the study under microscope, with some preserving signatures of exsolution intergrowth, earlier deformation and rounded shape, all of which are attributed to their transportation by the Gosthani river, after their liberation from their provenance rocks.

Metal cycling in Mesoproterozoic microbial habitats: Insights from trace elements and stable Cd isotopes in stromatolites

Reconstructing the environmental conditions that supported early life on Earth relies on well-preserved geochemical archives in the rock record. However, many geochemical tracers either lack specificity or they are affected by post-depositional alteration. We present a data set of major and trace element abundances and Cd isotope compositions of dome-shaped and conophyton-type stromatolites of the Late Mesoproterozoic Paranoá Group (Brazil), showing distinct values with unprecedented resolution at the lamina scale.The studied stromatolites consist of dolomite with a high purity and a negligible content of immobile elements (e.g., <0.66 ppm Zr), indicating that elemental compositions are not influenced by detrital contamination. Even though the carbonates have experienced different extent of recrystallization, the measured elemental and isotopic compositions do not correlate with fluid mobile elements. The stromatolites thus represent prime archives for geochemical proxies to reconstruct paleo-environmental conditions.Two endmember compositions can be distinguished by multiple proxy analysis, reflecting the contrasting depositional environments of the two types of stromatolites: Shale-normalized rare earth elements including yttrium (REYSN) patterns of domal stromatolites show a light REYSN (LREY) enrichment (YbSN/PrSN < 0.84), slightly super-chondritic Y/Ho ratios (33.6–39.3) and unfractionated Cd isotopes relative to upper continental crust. This indicates that the stromatolites formed in a shallow-water environment that was episodically influenced by seawater. Their REY and Cd compositions are dominated by dissolved elements that were delivered via weathering and erosion processes from the ambient continent.In contrast, REYSN patterns of the conophyta are parallel those of modern seawater with an LREYSN depletion relative to HREYSN (YbSN/PrSN = 2.1 to 3.9), positive GdSN anomalies (1.1 to 1.4) and strong super-chondritic Y/Ho ratios (37.9 to 46.2), suggesting a microbial habitat that was dominated by seawater. Cd isotopes correlate negatively with Cd and U, but positively with Mn and Ce concentrations, reflecting authigenic carbonate formation at different depths within a redox gradient of the ancient microbial mat. ε112/110Cddol values increase from −3.52 at the mat surface to +3.46 in the interior of the mat, due to the effect of kinetic fractionation during Cd-uptake, e.g. by adsorption onto organic matter or by precipitation of sulfides, in addition to incorporation into carbonate minerals. Hence, our multi-proxy approach including Cd isotopes bears a high potential to shed light on environmental conditions in ancient microbial habitats and the activity of microbial life on Early Earth.

Influence of Oil Sands Composition on Bitumen Quality During Non‐Aqueous Bitumen Extraction from the Athabasca Deposit

ABSTRACTThe aim of the present work is to identify the most important species affecting a non‐aqueous bitumen extraction process and bitumen quality. This investigation was carried out on four petrologic end member samples from Syncrude's North Mine collected in 2012 (NM12), i.e., marine claystone (MC), marine sand (MS), estuarine claystone (EC), and estuarine sand (ES). Each end member was separately mixed with cyclohexane at a ratio of 40:60 (cyclohexane:end member), and the bitumen‐cyclohexane solutions were collected at different settling times (1–30 min). These solutions were analyzed to determine the amount, particle size distribution, and mineralogical composition of suspended fine solids (SFS), water content, as well as the bitumen content using a focused beam reflectance measurement (FBRM) particle size analyzer, Karl Fischer (KF) titration, x‐ray diffraction (XRD), quantitative XRD (QXRD), and elemental analysis. The SFS was composed of mainly illite and kaolinite after cyclohexane extraction from MC, MS, EC, and ES. Although mixed layer expandable clay minerals (i.e., illite‐smectite and kaolinite‐smectite) were identified in the original clay, end members (EC and MC), illite‐smectite, and kaolinite‐smectite were not observed in the SFS of the bitumen‐cyclohexane solutions obtained from the four petrologic end members. The SFS content and bitumen quality of the bitumen product were affected slightly but significantly by the end member composition and settling time, respectively. Illite and kaolinite were identified as the main minerals in the SFS of the bitumen products after relatively long settling times.

Alteration trends and geochemical source region characteristics preserved in the fluviolacustrine sedimentary record of Gale crater, Mars

Abstract The Mars Science Laboratory’s Chemistry and Camera (ChemCam) instrument suite on-board the Curiosity rover has analysed ∼1200 sedimentary targets during the mission up to sol 1482. These targets have included sedimentary rock, diagenetic features (e.g., fracture-associated alteration halos, mineral veins, nodules, and erosion resistant raised ridges), active aeolian fines, soils and float. We have isolated ChemCam geochemical trends relating to diagenetic features and alteration products from those of the sedimentary rock in order to identify the compositional characteristics of Gale crater’s sediment source regions. The effects of grain size variation on sedimentary unit geochemistry have been taken into account by grouping and analysing geological units according to grain size. With obvious diagenetic features removed from the database, and predominately isochemical aqueous alteration inferred for the Mt Sharp Group samples, we propose that source region composition is a stronger source of geochemical change between the Bradbury and Mt Sharp Groups than open-system alteration. Additionally, a lack of correlation between the Chemical Index of Alteration (CIA) values and SiO2, MgO or FeOT indicates that the slight increase in chemical weathering of the Mt Sharp Group sediments was insufficient to overprint sediment source compositional signatures. This has led to the identification of five unique igneous endmember compositions which we hypothesise to have contributed to Gale crater’s stratigraphic record. These endmembers are: (1) a subalkaline basalt, compositionally similar to the tholeiitic Adirondack Class basalts of Gusev crater, and dominant within the finer grained units up to the base of Mt Sharp; (2) a trachybasalt, mostly identified within conglomerate units from the Darwin waypoint to the base of Mt Sharp; (3) a potassium-rich volcanic source, determined from strong potassium enrichment and a high abundance of sanidine that is most dominant in the fluvial sandstones and conglomerates of the Kimberley formation; (4) a highly evolved, silica-rich igneous source that correlates with the presence of tridymite, and is recorded in the lacustrine mudstone of Mt Sharp’s Marias Pass locality; and, (5) a fractionated, relatively SiO2-rich subalkaline basalt, seen to have influenced the composition of mudstone deposited in the lower part of the Mt Sharp Group. Endmembers (1), (2), (3), and (4) have previously been identified at specific waypoints along the rover’s traverse, but we show that their influence extends throughout Gale’s stratigraphic record. The occurrence of detected endmembers is also strongly correlated with stratigraphic position, which suggests changing sediment source regions with time. We conclude that Gale sediment provenances were much more varied than suggested by the largely homogenous, globally-distributed Martian basalt inferred from orbit, showing that complex magmatic assemblages exist within the ancient highland crust surrounding Gale.