Whole-body PET image denoising for reduced acquisition time

This paper evaluates the performance of supervised and unsupervised deep learning models for denoising positron emission tomography (PET) images in the presence of reduced acquisition times. Our experiments consider 212 studies (56908 images), and evaluate the models using 2D (RMSE, SSIM) and 3D (SUVpeak and SUVmax error for the regions of interest) metrics. It was shown that, in contrast to previous studies, supervised models (ResNet, Unet, SwinIR) outperform unsupervised models (pix2pix GAN and CycleGAN with ResNet backbone and various auxiliary losses) in the reconstruction of 2D PET images. Moreover, a hybrid approach of supervised CycleGAN shows the best results in SUVmax estimation for denoised images, and the SUVmax estimation error for denoised images is comparable with the PET reproducibility error

Mineralogy and Geochemistry of Mud Volcanic Ejecta: A New Look at Old Issues (A Case Study from the Bulganak Field, Northern Black Sea)

We characterise the mineralogy and geochemistry of Oligo-Miocene Maykopian shales that are currently extruded by onshore mud volcanoes of the Kerch-Taman Province (the Northern Black Sea) from the depths of ~2.5–3 km. The ejected muds are remarkable by highly diverse authigenic mineralogy that comprises glauconite, apatite, siderite, mixed Fe–Mg–Mn–(Ca) and Mn–Ca–Fe-carbonates, pyrite, marcasite, sphalerite, cinnabar, chalcopyrite, nukundamite, akantite, native Cu, Au and Au–Ag alloys. Precise geochemical techniques and high-resolution methods are applied to study the composition of bulk rocks, sulphide and carbonate fractions, as well as individual mineral species, including trace element and isotopic compositions of carbonates (C, O) and pyrite (S). Mineralogy of clastic and heavy fractions is used as a provenance tracer. Oxygen-deficient to weakly sulphuric deposition conditions are inferred for the parent sediments proceeding from trace element partitioning between carbonate, sulphide, and metallic phases. The main conclusion of the study is that onshore mud volcanoes of the region only transport buried sedimentary material and authigenic minerals they store to the ground surface

The impact of sulfur on the transfer of platinum group elements by geological fluids

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The Role of Te, As, Bi, and Sb in the Noble Metals (Pt, Pd, Au, Ag) and Microphases during Crystallization of a Cu-Fe-S Melt

Quasi-equilibrium directional crystallization was performed on a melt composition (at. %): 18.50 Cu, 32.50 Fe, 48.73 S, 0.03 Pt, Pd, Ag, Au, Te, As, Bi, Sb, and Sn, which closely resembles the Cu-rich massive ores found in the platinum-copper-nickel deposits of Norilsk. Base metal sulfides (BMS) such as pyrrhotite solid solution (Fe,Cu)S1±δ (Poss), non-stoichiometric cubanite Cu1.1Fe1.9S3 (Cbn*), and intermediate solid solution Cu1.0Fe1.2S2.0 (Iss) are progressively precipitated from the melt during the crystallization process. The content of noble metals and semimetals in the structure of BMS is below the detection limit of SEM-EDS analysis. Only tin exhibits significant solubility in Cbn* and Iss, meanwhile Pt, Pd, Au, Ag, As, Bi, Sb, and Te are present as discrete composite inclusions, comprising up to 11 individual phases, within their matrices. These microphases correspond to native Au, native Bi, hessite Ag2Te, sperrylite Pt(As,S)2, hedleyite Bi2Te, michenerite PdTeBi, froodite PdBi2, a solid solution of sudburite-sobolevskite-kotulskite Pd(Sb, Bi)xTe1−x, geversite PtSb2, and a multicomponent solid solution based on geversite Me(TABS)2, where Me = Σ(Pt, Pd, Fe, Cu) and TABS = Σ(Te, As, Bi, Sb, Sn). Most of the inclusions occur as thin layers between BMS grain boundaries or appear drop-shaped and subhedral to isometric grains within the sulfide matrix. Only a small fraction of the trace elements form mineral inclusions of sizes ≤ 0.5 μm in Poss, most likely including PtAs2 and (Pt,Pd)S. It is likely that the simultaneous presence of noble metals (Pt, Pd, Au, Ag) and semimetals (As, Te, Bi, Sb) in the sulfide melt leads to the appearance of liquid droplets in the parent sulfide melt after pyrrhotite crystallization. The solidification of droplets during the early stages of Cbn* crystallization may occur simultaneously with the cooling of later fractions of the sulfide melt, resulting in the formation of Iss. In addition, abundant gas voids containing micro-inclusions were observed in Cbn* and Iss. These inclusions showed similar chemical and mineral compositions to those in BMS matrices, i.e., the presence of gas bubbles did not affect the main features of noble metal fractionation and evolution. Therefore, it is reasonable to assume that ore particles suspended in the melt are either trapped by defects at the crystallization front or transported towards gas bubbles via the Marangoni effect

Platinum group elements and sulfur in hydrothermal fluids: a love story told by in situ spectroscopy, molecular dynamics, and thermodynamics

International audienceKnowledge of Platinum Group Elements (PGE) speciation in hydrothermal fluids is essential to better understanding the transport of these metals in the Earth's crust and to identifying potential hydrothermal deposits where PGE may be present in economic grades. Existing data on aqueous chloride, sulfate, and hydroxide complexes of PGEs indicate extremely low metal contents (< ppt to ppb) in fluids from most geological settings [1-3] that cannot explain multiple instances of PGE concentration and mobilization in hydrothermal systems, thus appealing to an important role of sulfide (HS–) and, potentially, trisulfur (S3–) ligands [4] in PGE transport. To quantify the effect of sulfur on the solubility of platinum and palladium in hydrothermal fluids, we combined in situ solubility (Fig. 1A) and X-ray absorption spectroscopy (XAS; Fig. 1B) measurements with molecular dynamics (MD; Fig. 1C) and thermodynamic (TD) simulations [5]. Our results show that two main complexes transport these metals in hydrothermal fluids across a wide pH range (4–8), temperature and pressure (up to at least 350 °C and 1000 bar): Pt(HS)42– and Pd(HS)42– in H2S/HS– solutions, Pt(HS)2(S3)22– and Pd(HS)2(S3)22– in H2S/SO42–/S3– solutions. The role of the trisulfur ion in PGE hydrothermal transport thus appears to be particularly crucial [5,6], with solubilities (10s ppm Pt, Pd) up to 10,000 times higher than those of the ‘traditional’ complexes with H2S/HS–. Our results offer perspectives for the exploration of new PGE resources, their extraction and recycling, and hydrothermal synthesis of PGE-based nanomaterials. Future research on other metals in fluid-mineral systems will benefit from the combined approach implemented in this study, as well as an open-access database of XAS spectra of Pt reference compounds acquired in our work [7].[1] Bazarkina et al. (2014), GCA 146, 107–131; [2] Kokh et al. (2017), GCA 197, 433–466; [3] Tagirov et al. (2019), GCA 254, 86–101; [4] Pokrovski and Dubessy (2015), EPSL 411, 298–309; [5] Laskar et al. (2022), GCA 336, 407–422; [6] Pokrovski et al. (2021), PNAS 118, e2109768118; [7] Laskar et al. (2022), Minerals 12, 1602

Exploring Platinum Speciation with X-ray Absorption Spectroscopy under High-Energy Resolution Fluorescence Detection Mode

International audienceCritical to interpreting platinum chemical speciation using X-ray absorption spectroscopy (XAS) is the availability of reference spectra of compounds with known Pt redox and coordination. Here we compare different techniques for Pt LIII-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectral regions for a large set of Pt-O-Cl-S reference compounds of known structures. The measurements were conducted in HERFD (high-energy resolution fluorescence detection, high-resolution or HR) mode, as well as in two conventional modes such as transmission (TR) and nominal-resolution total fluorescence yield (TFY or NR). Samples analyzed here included Pt0 (TR), PtIIS (HR), PtIVS2 (TR), K2PtIICl4 (HR + TR), K2PtIVCl6 (HR + TR), PtIVO2 (HR + TR), C6H12N2O4PtII (HR + TR), and aqueous solutions of K2PtIICl4 and H2PtIVCl6 (NR + TR), as well as (NH4)2PtIV(S5)3 (HR + TR). XANES spectra in HERFD mode offer a better energy resolution than in conventional modes, allowing a more accurate identification of Pt redox state and coordination geometry. EXAFS spectra in all three modes for a given compound yield identical within errors values of Pt-neighbor interatomic distances and mean square relative displacement (MSRD, σ2) parameters. In contrast, both TR and NR spectra on the one hand and HR spectra on the other hand yield distinct amplitude reduction factor (S02) values, 0.76 ± 0.04 and 0.99 ± 0.07 (1 standard error), respectively. This study contributes to the development of an open-access XAS database SSHADE

Mineralogical Diversity of Ca2SiO4-Bearing Combustion Metamorphic Rocks in the Hatrurim Basin: Implications for Storage and Partitioning of Elements in Oil Shale Clinkering

This is the first attempt to provide a general mineralogical and geochemical survey of natural Ca2SiO4-bearing combustion metamorphic (CM) rocks produced by annealing and decarbonation of bioproductive Maastrichtian oil shales in the Hatrurim Basin (Negev Desert, Israel). We present a synthesis of data collected for fifteen years on thirty nine minerals existing as fairly large grains suitable for analytical examination. The Hatrurim Ca2SiO4-bearing CM rocks, which are natural analogs of industrial cement clinker, have been studied comprehensively, with a focus on several key issues: major- and trace-element compositions of the rocks and their sedimentary precursors; mineral chemistry of rock-forming phases; accessory mineralogy; incorporation of heavy metals and other trace elements into different phases of clinker-like natural assemblages; role of trace elements in stabilization/destabilization of Ca2SiO4 polymorphic modifications; mineralogical diversity of Ca2SiO4-bearing CM rocks and trace element partitioning during high-temperature–low-pressure anhydrous sintering. The reported results have implications for mineral formation and element partitioning during high-temperature–low-pressure combustion metamorphism of trace element-loaded bituminous marine chalky sediments (“oil shales”) as well as for the joint effect of multiple elements on the properties and hydration behavior of crystalline phases in industrial cement clinkers

The trisulfur radical ion S 3 •− controls platinum transport by hydrothermal fluids

International audiencePlatinum group elements (PGE) are considered to be very poorly soluble in aqueous fluids in most natural hydrothermal–magmatic contexts and industrial processes. Here, we combined in situ X-ray absorption spectroscopy and solubility experiments with atomistic and thermodynamic simulations to demonstrate that the trisulfur radical ion S 3 •− forms very stable and soluble complexes with both Pt II and Pt IV in sulfur-bearing aqueous solution at elevated temperatures (∼300 °C). These Pt-bearing species enable (re)mobilization, transfer, and focused precipitation of platinum up to 10,000 times more efficiently than any other common inorganic ligand, such as hydroxide, chloride, sulfate, or sulfide. Our results imply a far more important contribution of sulfur-bearing hydrothermal fluids to PGE transfer and accumulation in the Earth’s crust than believed previously. This discovery challenges traditional models of PGE economic concentration from silicate and sulfide melts and provides new possibilities for resource prospecting in hydrothermal shallow crust settings. The exceptionally high capacity of the S 3 •− ion to bind platinum may also offer new routes for PGE selective extraction from ore and hydrothermal synthesis of noble metal nanomaterials

The nature and partitioning of invisible gold in the pyrite-fluid system

International audienceThe most characteristic feature of hydrothermal deposits of gold is its intimate association with pyrite. Microscopically visible gold occurs in pyrite ore as metal particles of >0.1 µm in size, together with so called “invisible” gold, undetectable by conventional microscopic methods. The chemical, redox and structural state of this invisible gold and the mechanisms of its incorporation into pyrite remain both inconsistent and controversial since the dawn of economic geology. To clarify these issues, we performed laboratory experiments to simulate interactions of gold-bearing sulfur-rich hydrothermal fluids with arsenic-free pyrite at temperatures from 350 to 450 °C and pressures from 400 to 700 bar, typical of the formation conditions of many types of gold deposits. Gold solubility was measured in these fluids as a function of sulfur speciation and acidity. Gold redox and structural state in pyrite was characterized by high-energy resolution fluorescence-detected x-ray absorption spectroscopy (HERFD-XAS), together with more traditional analytical techniques such as scanning electron microscopy (SEM), x-ray diffraction (XRD), electron probe micro analysis (EPMA), laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), and inductively coupled plasma atomic emission spectrometry (ICP-AES). Results show that dissolved Au in sulfide-sulfate solutions forms complexes with hydrogen sulfide, and tri- and di-sulfur radical ions whose amounts depend mostly on the fluid pH and total sulfur concentration. Invisible gold in pyrite occurs as Au metal submicron- to nano-sized particles and chemically bound Au(I) in the form of (poly)sulfide clusters composed on S-Au-S linear units, similar to those in aqueous complexes. Our findings contest the common belief that Au(I) substitutes for Fe and/or S in the structure of As-poor pyrite. The partition coefficient of Au(I) between pyrite and the fluid, Dpy/fl, is determined to be 0.15 ± 0.07 at 450 °C in a wide range of Au fluid phase concentrations (10–1000 ppm), but much higher Dpy/fl values, between 10 and 50, are found at 350 °C. These Au partitioning trends coupled with the new data on Au molecular environment in pyrite suggest a control of Au(I) incorporation in the mineral by a chemisorption step. Extrapolated to Au contents of hydrothermal fluids of the Earth’s crust which are typically below 1 ppm, our Dpy/fl values reproduce fairly well the natural Au tenors in As-poor pyrites (∼0.1–1 ppm Au), which are 100–1000 times lower than those typically observed in arsenian pyrites and arsenopyrites (10–1000 ppm Au at As tenors of 0.01–10 wt%). Our results thus indirectly highlight a key role played by arsenic in gold enrichment in As-bearing iron sulfide ore, a role that yet remains to be fully understood and quantified