Machine Learning Applied to K-Bentonite Geochemistry for Identification and Correlation: The Ordovician Hagan K-Bentonite Complex Case Study

Altered tephras (K-bentonites) are of great importance for calibration of the geologic time scale, for local, regional, and global correlations, and paleoenvironmental reconstructions. Thus, definitive identification of individual tephras is critical. Single crystal geochemistry has been used to differentiate tephra layers, and apatite is one of the phenocrysts commonly occurring in tephras that has been widely used. Here, we use existing and newly acquired analytical datasets (electron probe micro-analyzer [EPMA] data and laser ablation ICP-MS [LA-ICP-MS] data, respectively) of apatite in several Ordovician K-bentonites that were collected from localities about 1200 km apart (Minnesota/Iowa/Wisconsin and Alabama, United States) to test the use of machine-learning (ML) techniques to identify with confidence individual tephra layers. Our results show that the decision tree based on EPMA data uses the elemental concentration patterns of Mg, Mn, and Cl, consistent with previous studies that emphasizes the utility of these elements for distinguishing Ordovician K-bentonites. Differences in the experimental setups of the analyses, however, can lead to offsets in absolute elemental concentrations that can have a significant impact on the correct identification and correlation of individual K-bentonite beds. The ML model using LA-ICP-MS data was able to identify several K-bentonites in the southern Appalachians and establish links to K-bentonites samples from the Upper Mississippi Valley. Furthermore, the ML model identified individual layers of multiphase eruptions, thus illustrating very well the great potential of applying ML techniques to tephrochronology.

Supplemental Material: Eocene thickening without extra heat in a collisional orogenic belt: A record from Eocene metamorphism in mafic dike swarms within the Tethyan Himalaya, southern Tibet

Table S1: EPMA data of minerals compositions for garnet amphibolite; Table S2: Zircon U-Pb SHRIMP data for garnet amphibolite T0526; Table S3: Major and trace element compositions of garnet amphibolites.

Supplemental Material: Eocene thickening without extra heat in a collisional orogenic belt: A record from Eocene metamorphism in mafic dike swarms within the Tethyan Himalaya, southern Tibet

Table S1: EPMA data of minerals compositions for garnet amphibolite; Table S2: Zircon U-Pb SHRIMP data for garnet amphibolite T0526; Table S3: Major and trace element compositions of garnet amphibolites.

Arrheniusite-(Ce), CaMg[(Ce7Y3)Ca5](SiO4)3(Si3B3O18)(AsO4)(BO3)F11, a New Member of the Vicanite Group, from the Östanmossa Mine, Norberg, Sweden

ABSTRACT Arrheniusite-(Ce) is a new mineral (IMA 2019-086) from the Östanmossa mine, one of the Bastnäs-type deposits in the Bergslagen ore region, Sweden. It occurs in a metasomatic F-rich skarn, associated with dolomite, tremolite, talc, magnetite, calcite, pyrite, dollaseite-(Ce), parisite-(Ce), bastnäsite-(Ce), fluorbritholite-(Ce), and gadolinite-(Nd). Arrheniusite-(Ce) forms anhedral, greenish-yellow translucent grains, exceptionally up to 0.8 mm in diameter. It is optically uniaxial (–), with ω = 1.750(5), ε = 1.725(5), and non-pleochroic in thin section. The calculated density is 4.78(1) g/cm3. Arrheniusite-(Ce) is trigonal, space group R3m, with unit-cell parameters a = 10.8082(3) Å, c = 27.5196(9) Å, and V = 2784.07(14) Å3 for Z = 3. The crystal structure was refined from X-ray diffraction data to R1 = 3.85% for 2286 observed reflections [Fo > 4σ(Fo)]. The empirical formula for the fragment used for the structural study, based on EPMA data and results from the structure refinement, is: (Ca0.65As3+0.35)Σ1(Mg0.57Fe2+0.30As5+0.10Al0.03)Σ1[(Ce2.24Nd2.13La0.86Gd0.74Sm0.71Pr0.37)Σ7.05(Y2.76Dy0.26Er0.11Tb0.08Tm0.01Ho0.04Yb0.01)Σ3.27Ca4.14]Σ14.46(SiO4)3[(Si3.26B2.74)Σ6O17.31F0.69][(As5+0.65Si0.22P0.13)Σ1O4](B0.77O3)F11; the ideal formula obtained is CaMg[(Ce7Y3)Ca5](SiO4)3(Si3B3O18)(AsO4)(BO3)F11. Arrheniusite-(Ce) belongs to the vicanite group of minerals and is distinct from other isostructural members mainly by having a Mg-dominant, octahedrally coordinated site (M6); it can be considered a Mg-As analog to hundholmenite-(Y). The threefold coordinated T5 site is partly occupied by B, like in laptevite-(Ce) and vicanite-(Ce). The mineral name honors C.A. Arrhenius (1757–1824), a Swedish officer and chemist, who first discovered gadolinite-(Y) from the famous Ytterby pegmatite quarry.

A Raman spectroscopic study of the natural carbonophosphates Na3MCO3PO4 (M = Mn, Fe, and Mg)

<p>Along with some other Na-minerals, carbonophosphates indicate a high initial Na activity in carbonatite and kimberlite melts, which is beneficial for petrological reconstructions. Because carbonophosphates are capable of incorporating large-ion lithophile and rare earth elements (REEs) in their structure, they can participate in the transport of these elements. Moreover, due to the presence of both [PO<sub>4</sub>]<sup>3−</sup> and [CO<sub>3</sub>]<sup>2− </sup>groups in carbonophosphates, these mineral phases play an important role in the Earth's global carbon and phosphate cycles. With all these properties, carbonophosphates have long attracted the attention of geologists. Raman spectroscopy appears to be one of the most suitable tools for their diagnosis, since they commonly present in rocks as small inclusions in other mineral grains. Despite this profit, only a few publications contain Raman characteristics of either natural or synthetic carbonophosphates.</p><p>We studied and compared Raman spectra of three natural carbonophosphate phases (sidorenkite, bonshtedtite, and bradleyite) with the general formula Na<sub>3</sub>MCO<sub>3</sub>PO<sub>4</sub> (M = Mn, Fe, and Mg, correspondingly). These spectra showed from 21 to 24 vibrational bands, of which the two most intense (963±5 cm<sup>-1</sup> и 1074±3 cm<sup>-1</sup>) correspond to the ν1(P–O) and ν1(C–O) modes. These two bands split due to the occurrence of isomorphic impurities. It was found that the crystallographic orientation of the sample influences the intensity of most bands. A natural increase in the Raman shift was observed for most bands assigned to the same vibrations (the smallest shift in the spectrum is characteristic of sidorenkite, an intermediate - of bonshtedtite, and the largest - of bradleyite).</p><p>We propose the following algorithm for the diagnosis of carbonophosphates:</p><ul><li>Checking minerals for belonging to the group of carbonophosphates by the main bands and the characteristic profile of the spectrum;</li> <li>Testing the hypothesis that the mineral of question is bradleyite based on the analysis of the estimated shift of the main bands;</li> <li>Diagnosis of a mineral species by peaks located between the main bands;</li> <li>Validation of the diagnostics by considering the position of the bands at 185±9 cm<sup>-1</sup>, 208±7 cm<sup>-1</sup>, 255±5 cm<sup>-1</sup>, and 725±6 cm<sup>-1</sup>.</li> </ul><p>The proposed algorithm allows one to perform Raman diagnostics of carbonophosphates in inclusions even in the absence of EPMA data. In the study of carbonatites, kimberlites, and other rocks, the diagnostics of the mineral species of the carbonophosphate group can be important in the petrological aspect.</p><p>This research was funded by the Russian Science Foundation, grant number 19-77-10039.</p>

The origin of Ti-oxide minerals below and within the eastern Athabasca Basin, Canada

Titanium oxide minerals along the P2 fault in the eastern Athabasca Basin are characterized to constrain their origin and the geological history of the area. Two types of rutile are recognized in the basement rocks. Early rutile is disseminated in graphitic metapelite and quartzite, and it formed during regional metamorphism and post-metamorphic hydrothermal activity. Late rutile occurs as a needle-like alteration product of mica and likely formed during retrogression of the basement. In graphitic metapelite, early rutile commonly occurs with an assemblage of oxy-dravite, quartz, graphite, zircon, pyrite, biotite, and muscovite. In quartzite, rutile occurs with quartz, sillimanite, muscovite, and zircon. Metamorphic rutile is characterized by high Nb/Ta ratios (up to 47) with high concentrations of U (up to 126 ppm) and V4+ (up to 1.44 wt%; V valance calculated from EPMA data). Hydrothermal rutile contains distinctly low Nb/Ta (as low as 4.80) with high Ta (≤3050 ppm), and relatively low V (as V 3+; as low as 0.02 wt%) and U (as low as 9.06 ppm), reflecting fluids in reduced oxidation conditions. Anatase forms small anhedral (rarely coarse and euhedral) grains in the basal sandstones and altered basement rocks. In sandstones, anatase occurs with the late diagenetic mineral assemblage, whereas in basement rocks it commonly occurs with the clay-sized minerals related to uranium mineralization. In both rocks, anatase likely formed through the dissolution of rutile and/or other Ti-bearing minerals. Anatase is characterized by variably high Fe (up to 0.99 wt%; possibly contributed by hematite micro-or nanoinclusions) and U (up to 180 ppm). The mineral assemblages and composition of anatase suggest its protracted crystallization from relatively low temperature, oxidizing, acidic, uraniferous fluids of the sandstones during late diagenesis and hydrothermal activity. Therefore, the occurrence of anatase records the incursion of basin fluids into the basement, and the interaction of basement rocks with fluids responsible for the formation of the McArthur River uranium deposit. The results of this study confirm that Ti-oxides are useful in unraveling the geological history of an area that underwent prolonged hydrothermal activity.

A case for the growth of ancient ooids within the sediment pile

ABSTRACT In modern ooid-forming environments in the Caribbean, aerobic respiration of organic matter below the sediment–water interface drives an increase in pCO2 and a corresponding decrease in carbonate saturation state (Ω) that creates shallow sediment porewater that is neutral or slightly caustic to carbonate. The locus of ooid growth, therefore, is presumed to be in the water column during suspension, where supersaturation with respect to calcium carbonate is the norm. In the past, however, during conditions of low aqueous O2, high Ω, or low organic-matter input, the shallow sub-sediment marine burial environment was conducive to carbonate precipitation. Here we present petrographic and electron probe microanalyzer (EPMA) data from exquisitely preserved oolites through time that suggests that some ancient ooids may have grown within the sediment pile. We propose that each increment of ooid cortical growth originated as incipient isopachous marine cement formed during shallow burial within migrating ooid dunes. After a period of burial (∼ weeks to months), ooids were remobilized and rounded during bedload transport. This “bedform model” for ooid growth explains: 1) why ancient ooids are not limited by the precipitation–abrasion balance that appears to prohibit modern tangential Caribbean ooids from achieving grain sizes larger than coarse sand, 2) the radial crystal fabric that defines the internal structure of many ancient ooids, and 3) the first-order correlation of the abundance of large and giant ooids in the rock record to periods with predicted high porewater Ω. This model implies that photosynthetic microbes were unimportant for growth of large and giant ooid but it remains agnostic to the effect of other microbes. The physical and chemical milieu of modern marine ooid-forming environments is perhaps not the best analogue for ancient ooid-forming environments; this should be considered when using ancient ooids to reconstruct secular trends in ocean chemistry.

Abstract title; Geology and geochemical characteristics of coal-bearing source rocks in Nariin sukhait deposit, southern Mongolia

<p>The Nariin Sukhait mine is located in the southwest of Umnugobi province 50 kilometers from Mongolia's border with China at Shivee Khuren within the Nariin Sukhait deposit, which has relatively complex geological features. The most prominent feature relating to the Nariin Sukhait coal deposit is the arcuate, east-west trending Nariin Sukhait fault. The coal-bearing section, interpreted to be middle Jurassic in age, is exposed primarily in a window adjacent to this fault.</p><p>The chemical composition of whole indicates (variable composition, values of the ratio Th/U > 3.8-4.2, values Th/Sc 0.3-0.8, values LaN/YbN > 5 and values Eu/Eu* 0.6-0.9) indicates components derived from the active continental margin type. The low CIA values (50–60) indicate the absence or poor chemical weathering in the source area.</p><p>SEM-CL-imaging of sandstone quartz from Nariin sukhait show three types of quartz:  early Q1 cementation has gray to slightly grey luminescences, postdated compaction, and reduced intergranular porosity associated with illite formed during eogenesis. Q2 is characterized by dark luminescence overgrowths and is more voluminous in the thinly bedded sandstones than in the thickly bedded sandstones filling most of the remaining pore space during mesogenesis. Q3 was formed during the early telogenesis stage fully cementing the sandstones and the fractures were filled by hydrothermal chlorite and sulfides. Significant amounts of trace elements Al, Ti, Ca, K and Fe has been detected in quartz overgrowths. Al varies consistently between each cement with averages of 1324, 1523, and 1352 ppm for the Q1, Q2, and Q3 generations, respectively.</p><p>The geochemical, SEM-CL imaging and EPMA data results suggest a relatively igneous source, whit felsic composition. The sedimentary environment of the sandstone and argillite of these sedimentary rocks was the poor chemical weathering in the source area.</p>

New Insights into the Mineralogy and Geochemistry of Sb Ores from Greece

Antimony is a common metalloid occurring in the form of Sb-sulfides and sulfosalts, in various base and noble metal deposits. It is also present in corresponding metallurgical products (concentrates) and, although antimony has been considered a penalty element in the past, recently it has gained interest due to its classification as a critical raw material (CRM) by the European Union (EU). In the frame of the present paper, representative ore samples from the main Sb-bearing deposits of Greece (Kilkis prefecture, Chalkidiki prefecture (Kassandra Mines), and Chios Isl.) have been investigated. According to optical microscopy and electron probe microanalysis (EPMA) data, the Greek ores contain stibnite (Sb2S3), boulangerite (Pb5Sb4S11), bournonite (PbCuSbS3), bertherite (FeSbS4), and valentinite (Sb2O3). Bulk analyses by inductively coupled plasma mass spectrometry (ICP-MS) confirmed, for the first time published, the presence of a significant Hg content in the Kilkis Sb-ore. Furthermore, Kassandra Mines ores are found to contain remarkable amounts of Bi, As, Sn, Tl, and Se (excluding Ag, which is a bonus element). The above findings could contribute to potential future exploration and exploitation of Sb ores in Greece.