The role of hydrothermal activity in the formation of karst-hosted manganese deposits of the Postmasburg Mn Field, Northern Cape Province, South Africa

The Postmasburg Manganese Field (PMF), Northern Cape Province, South Africa, once represented one of the largest sources of manganese ore worldwide. Two belts of manganese ore deposits have been distinguished in the PMF, namely the Western Belt of ferruginous manganese ores and the Eastern Belt of siliceous manganese ores. Prevailing models of ore formation in these two belts invoke karstification of manganese-rich dolomites and residual accumulation of manganese wad which later underwent diagenetic and low-grade metamorphic processes. For the most part, the role of hydrothermal processes and metasomatic alteration towards ore formation has not been adequately discussed. Here we report an abundance of common and some rare Al-, Na-, K- and Ba-bearing minerals, particularly aegirine, albite, microcline, banalsite, sérandite-pectolite, paragonite and natrolite in Mn ores of the PMF, indicative of hydrothermal influence. Enrichments in Na, K and/or Ba in the ores are generally on a percentage level for most samples analysed through bulk-rock techniques. The presence of As-rich tokyoite also suggests the presence of As and V in the hydrothermal fluid. The fluid was likely oxidized and alkaline in nature, akin to a mature basinal brine. Various replacement textures, particularly of Na- and K- rich minerals by Ba-bearing phases, suggest sequential deposition of gangue as well as ore-minerals from the hydrothermal fluid, with Ba phases being deposited at a later stage. The stratigraphic variability of the studied ores and their deviation from the strict classification of ferruginous and siliceous ores in the literature, suggests that a re-evaluation of genetic models is warranted. New Ar-Ar ages for K-feldspars suggest a late Neoproterozoic timing for hydrothermal activity. This corroborates previous geochronological evidence for regional hydrothermal activity that affected Mn ores at the PMF but also, possibly, the high-grade Mn ores of the Kalahari Manganese Field to the north. A revised, all-encompassing model for the development of the manganese deposits of the PMF is then proposed, whereby the source of metals is attributed to underlying carbonate rocks beyond the Reivilo Formation of the Campbellrand Subgroup. The main process by which metals are primarily accumulated is attributed to karstification of the dolomitic substrate. The overlying Asbestos Hills Subgroup banded iron formation (BIF) is suggested as a potential source of alkali metals, which also provides a mechanism for leaching of these BIFs to form high-grade residual iron ore deposits

Effects of fluid-rock interaction on 40Ar/39Ar geochronology in high-pressure rocks (Sesia-Lanzo Zone, Western Alps)

Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 126 (2014):475-494, doi:10.1016/j.gca.2013.10.023.in situ UV laser spot 40Ar/39Ar analyses of distinct phengite types in eclogite-facies rocks from the Sesia-Lanzo Zone (Western Alps, Italy) were combined with SIMS boron isotope analyses as well as boron (B) and lithium (Li) concentration data to link geochronological information with constraints on fluid-rock interaction. In weakly deformed samples, apparent 40Ar/39Ar ages of phengite cores span a range of ∼20 Ma, but inverse isochrons define two distinct main high-pressure (HP) phengite core crystallization periods of 88-82 Ma and 77-74 Ma, respectively. The younger cores have on average lower B contents (∼36 mg/g) than the older ones (∼43-48 mg/g), suggesting that loss of B and resetting of the Ar isotopic system were related. Phengite cores have variable d11B values (-18 to -10 ‰), indicating the lack of km scale B homogenization during HP crystallization. Overprinted phengite rims in the weakly deformed samples generally yield younger apparent 40Ar/39Ar ages than the respective cores. They also show variable effects of heterogeneous excess 40Ar incorporation and Ar loss. One acceptable inverse isochron age of 77.1 ±1.1 Ma for rims surrounding older cores (82.6 ±0.6 Ma) overlaps with the second period of core crystallization. Compared to the phengite cores, all rims have lower B and Li abundances but similar d11B values (-15 to -9 ‰), reflecting internal redistribution of B and Li and internal fluid buffering of the B isotopic composition during rim growth. The combined observation of younger 40Ar/39Ar ages and boron loss, yielding comparable values of both parameters only in cores and rims of different samples, is best explained by a selective metasomatic overprint. In low permeability samples, this overprint caused recrystallization of phengite rims, whereas higher permeability in other samples led to complete recrystallization of phengite grains. Strongly deformed samples from a several km long, blueschist-facies shear zone contain mylonitic phengite that forms a tightly clustered group of relatively young apparent 40Ar/39Ar ages (64.7 to 68.8 Ma), yielding an inverse isochron age of 65.0 ±3.0 Ma. Almost complete B and Li removal in mylonitic phengite is due to leaching into a fluid. The B isotopic composition is significantly heavier than in phengites from the weakly deformed samples, indicating an external control by a high-d11B fluid (d11B = +7 ±4 ‰). We interpret this result as reflecting phengite recrystallization related to deformation and associated fluid flow in the shear zone. This event also caused partial resetting of the Ar isotope system and further B loss in more permeable rocks of the adjacent unit. We conclude that geochemical evidence for pervasive or limited fluid flow is crucial for the interpretation of 40Ar/39Ar data in partially metasomatized rocks.Funding of this work by the Deutsche Forschungsgemeinschaft (grant KO-3750/2-1) is gratefully acknowledged

Local high relief at the southern margin of the Andean plateau by 9 Ma: evidence from ignimbritic valley fills and river incision

A valley-filling ignimbrite re-exposed through subsequent river incision at the southern margin of the Andean (Puna) plateau preserves pristine geological evidence of pre-late Miocene paleotopography in the northwestern Argentine Andes. Our new 40Ar/39Ar dating of the Las Papas ignimbrites yields a plateau age of 9.24 ± 0.03 Ma, indicating valley relief and orographic-barrier conditions comparable to the present-day. A later infill of Plio- Pleistocene coarse conglomerates has been linked to wetter conditions, but resulted in no additional net incision of the Las Papas valley, considering that the base of the ignimbrite remains unexposed in the valley bottom. Our observations indicate that at least 550 m of local plateau margin relief (and likely >2 km) existed by 9 Ma at the southern Puna margin, which likely increased the efficiency of the orographic barrier to rainfall along the eastern and southeastern flanks of the Puna and caused aridity in the plateau interior.Fil: Montero Lopez, Maria Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Salta. Instituto de Bio y Geociencias del Noroeste Argentino; ArgentinaFil: Strecker, Manfred R.. Universitat Potsdam; AlemaniaFil: Schildgen, Taylor F.. Universitat Potsdam; AlemaniaFil: Hongn, Fernando Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Salta. Instituto de Bio y Geociencias del Noroeste Argentino; ArgentinaFil: Guzman, Silvina Raquel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Salta. Instituto de Bio y Geociencias del Noroeste Argentino; ArgentinaFil: Bookhagen, Bodo. Universitat Potsdam; AlemaniaFil: Sudo, Masafumi. Universitat Potsdam; Alemani

Evolution of diagenetic conditions and burial history in Buntsandstein Gp. fractured sandstones (Upper Rhine Graben) from in-situ δ¹⁸O of quartz and ⁴⁰Ar/³⁹Ar geochronology of K-feldspar overgrowths

In-situ δ¹⁸O measured in the quartz overgrowths help identify temperature and fluid origin variations responsible for cementation of the pore network (matrix and fracture) in the Buntsandstein Gp. sandstone reservoirs within the Upper Rhine Graben. The overgrowths record two types of the evolution of δ¹⁸O: 1) a monotonous decrease of the δ¹⁸Oovergrowth interpreted as linked to an increasing burial temperature and 2) random fluctuations, interpreted as pointing out the injection of allochthonous fluids in faulted areas, on the cementation processes of the pore network (both intergranular and fracture planes). Fluids causing the quartz cementation are either autochthonous buffered in ¹⁸O from clay illitisation; or allochthonous fluids of meteoric origin with δ¹⁸O below − 5%. These allochthonous fluids are in thermal disequilibrium with the host sandstone. The measured signal of δ¹⁸Oovergrowth measured from samples and calculated curves testing hypothetic δ¹⁸Ofluid are compared to T–t evolution during burial. This modelling proposes the initiation of quartz cementation during the Jurassic and is validated by the in-situ ⁴⁰Ar/³⁹Ar dating results obtained on the feldspar overgrowths predating quartz overgrowths. A similar diagenetic history is recorded on the graben shoulders and in the buried parts of the basin. Here, the beginning of the pore network cementation predates the structuration in blocks of the basin before the Cenozoic graben opening

Label-free multiphoton excitation imaging as a promising diagnostic tool for breast cancer

Histopathological diagnosis is the ultimate method of attaining the final diagnosis; however, the observation range is limited to the two-dimensional plane, and it requires thin slicing of the tissue, which limits diagnostic information. To seek solutions for these problems, we proposed a novel imaging-based histopathological examination. We used the multiphoton excitation microscopy (MPM) technique to establish a method for visualizing unfixed/unstained human breast tissues. Under near-infrared ray excitation, fresh human breast tissues emitted fluorescent signals with three major peaks, which enabled visualizing the breast tissue morphology without any fixation or dye staining. Our study using human breast tissue samples from 32 patients indicated that experienced pathologists can estimate normal or cancerous lesions using only these MPM images with a kappa coefficient of 1.0. Moreover, we developed an image classification algorithm with artificial intelligence that enabled us to automatically define cancer cells in small areas with a high sensitivity of ≥0.942. Taken together, label-free MPM imaging is a promising method for the real-time automatic diagnosis of breast cancer.This is the pre-peer reviewed version of the following article:Matsui T., Iwasa A., Mimura M., et al. Label-free multiphoton excitation imaging as a promising diagnostic tool for breast cancer. Cancer Science 113, 2916 (2022), which has been published in final form at https://doi.org/10.1111/cas.15428. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving

Age of Izu-Bonin-Mariana arc basement

Documenting the early tectonic and magmatic evolution of the Izu–Bonin–Mariana (IBM) arc system in the Western Pacific is critical for understanding the process and cause of subduction initiation along the current convergent margin between the Pacific and Philippine Sea plates. Forearc igneous sections provide firm evidence for seafloor spreading at the time of subduction initiation (52 Ma) and production of “forearc basalt”. Ocean floor drilling (International Ocean Discovery Program Expedition 351) recovered basement-forming, low-Ti tholeiitic basalt crust formed shortly after subduction initiation but distal from the convergent margin (nominally reararc) of the future IBM arc (Amami Sankaku Basin: ASB). Radiometric dating of this basement gives an age range (49.3–46.8 Ma with a weighted average of 48.7 Ma) that overlaps that of basalt in the present-day IBM forearc, but up to 3.3 m.y. younger than the onset of forearc basalt activity. Similarity in age range and geochemical character between the reararc and forearc basalts implies that the ocean crust newly formed by seafloor spreading during subduction initiation extends from fore- to reararc of the present-day IBM arc. Given the age difference between the oldest forearc basalt and the ASB crust, asymmetric spreading caused by ridge migration might have taken place. This scenario for the formation of the ASB implies that the Mesozoic remnant arc terrane of the Daito Ridges comprised the overriding plate at subduction initiation. The juxtaposition of a relatively buoyant remnant arc terrane adjacent to an oceanic plate was more favourable for subduction initiation than would have been the case if both downgoing and overriding plates had been oceanic.OI and YK appreciate JAMSTEC and J-DESC for their funding to join the expedition and post cruise research. IPS thanks UK-NERC for support for participation of the IODP cruise and part of the postcruise research. OI also used Grant-in-Aid (B) (No. 25287133) for shore-based research

Age of Izu-Bonin-Mariana arc basement

Documenting the early tectonic and magmatic evolution of the Izu–Bonin–Mariana (IBM) arc system in the Western Pacific is critical for understanding the process and cause of subduction initiation along the current convergent margin between the Pacific and Philippine Sea plates. Forearc igneous sections provide firm evidence for seafloor spreading at the time of subduction initiation (52 Ma) and production of “forearc basalt”. Ocean floor drilling (International Ocean Discovery Program Expedition 351) recovered basement-forming, low-Ti tholeiitic basalt crust formed shortly after subduction initiation but distal from the convergent margin (nominally reararc) of the future IBM arc (Amami Sankaku Basin: ASB). Radiometric dating of this basement gives an age range (49.3–46.8 Ma with a weighted average of 48.7 Ma) that overlaps that of basalt in the present-day IBM forearc, but up to 3.3 m.y. younger than the onset of forearc basalt activity. Similarity in age range and geochemical character between the reararc and forearc basalts implies that the ocean crust newly formed by seafloor spreading during subduction initiation extends from fore- to reararc of the present-day IBM arc. Given the age difference between the oldest forearc basalt and the ASB crust, asymmetric spreading caused by ridge migration might have taken place. This scenario for the formation of the ASB implies that the Mesozoic remnant arc terrane of the Daito Ridges comprised the overriding plate at subduction initiation. The juxtaposition of a relatively buoyant remnant arc terrane adjacent to an oceanic plate was more favourable for subduction initiation than would have been the case if both downgoing and overriding plates had been oceanic

Calibration of a new Ar analytical system for the K-Ar dating method and analytical results of K-Ar age known samples

A new Ar analytical system at Kyoto University by sensitivity method which is suitable for dating of Neogene to Quaternary volcanic and tectonic events has been constructed and calibrated. Calibration has been performed using biotite mineral standard, Soni 93, in which the amount of radiogenic 40Ar is known. The system consists of a VG Isotech 3600 mass spectrometer and the main sample handling system both for the extraction by tantalum resistance furnace and for the purification of sample gases. The errors of 40Ar intensity, 40Ar/36Ar and 38Ar/36Ar of the system have been estimated to be 1.5%, 0.16% and 0.53%, respectively, by repeated standard air Ar analyses. The duplicate analyses have been done by the system using six K-Ar age mineral standards or K-Ar age known samples whose ages belong to Neogene or Quaternary. Most obtained K-Ar ages agree well with those in the literatures. There are no systematic errors among them. The ages of four Neogene samples (Bern4B, Bern4M, Baba Tuff biotite and NST30 biotite) has been obtained within about ±2-3% errors and that of one Quaternary sample (YZ1) within about ±25-30% errors. These implies that the Ar analytical system may be sufficiently useful for K-Ar dating of geological samples with younger ages than Neogene age