Morpho-Mineralogical and Bio-Geochemical Description of Cave Manganese Stromatolite-Like Patinas (Grotta del Cervo, Central Italy) and Hints on Their Paleohydrological-Driven Genesis

Caves are dark subsurface environments with relatively constant temperatures that allow studying bio-mineralization processes and paleoenvironmental or climate changes in optimal conditions. In the extreme and oligotrophic cave environment, manganese patinas having stromatolite-like features are uncommon. Here we provide the first detailed mineralogical, geochemical, and microbiological investigation of fine-grained and poorly crystalline MnFe stromatolite-like wall patinas formed in a deep-cave environment in Italy. These mineralizations, about 3 mm thick, consist of an alternation of Mn-layers and Fe-lenses. We show that the microbial communities' composition is dominated by Mn-oxidizing bacteria, such as Bacillus, Flavobacterium, and Pseudomonas. Our multidisciplinary investigation, integrating data from different analytical techniques (i.e., optical microscopy, SEM-EDS, μXRF, XRPD, FT-IR, Raman spectroscopy, and DNA sequencing), revealed peculiar chemical, mineralogical, and biological features: 1) A cyclical oscillation of Mn and Fe along the growth of the patinas. We propose that this oscillation represents the shift between oxic and suboxic conditions related to different phases occurring during paleo-flood events; 2) A typical spatial distribution of mineralogy and oxidation state of Mn, bacterial imprints, detrital content, and stromatolite-like morphologies along the Mn-layers. We propose that this distribution is controlled by the local hydraulic regime of the paleo-floods, which, in turn, is directly related to the morphology of the wall surface. Under less turbulent conditions, the combination of clay mineral catalysis and biological oxidation produced vernadite, a poor-crystalline phyllomanganate with a low average oxidation state of Mn, and branched columnar stromatolite-like morphologies. On the other hand, under more turbulent conditions, the sedimentation of clay minerals and microbial communities' development are both inhibited. In this local environment, a lower oxidation rate of Mn2+ favored the formation of todorokite and/or ranciéite, two compounds with a high average oxidation state of Mn, and flat-laminated or columnar stromatolite-like morphologies.

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Tunable Mn Oxidation State and Redox Potential of Birnessite Coexisting with Aqueous Mn(II) in Mildly Acidic Environments

Minerals ◽

10.3390/min10080690 ◽

2020 ◽

Vol 10 (8) ◽

pp. 690

Author(s):

Juan Liu ◽

Yixiao Zhang ◽

Qian Gu ◽

Anxu Sheng ◽

Baogang Zhang

Keyword(s):

Oxidation State ◽

Organic Pollutant ◽

Equilibrium Concentration ◽

Aquatic Environments ◽

Oxidation Potentials ◽

Average Oxidation State ◽

Subsurface Environments ◽

Equilibrium Concentrations ◽

Kinetics Of ◽

Manganese Oxide Mineral

As the dominant manganese oxide mineral phase in terrestrial and aquatic environments, birnessite plays an important role in many biogeochemical processes. The coexistence of birnessite with aqueous Mn2+ is commonly found in the subsurface environments undergoing Mn redox cycling. This study investigates the change in Mn average oxidation state (AOS) of birnessite after reaction with 0.1–0.4 mM Mn2+ at pH 4.5–6.5, under conditions in which phase transformation of birnessite by Mn2+ was not detectable. The amount of Mn2+ uptake by birnessite and the equilibrium concentration of Mn(III) proportionally increased with the initial concentration of Mn2+. The Mn AOS of birnessite particles became 3.87, 3.75, 3.64, and 3.53, respectively, after reaction with 0.1, 0.2, 0.3, and 0.4 mM Mn2+ at pH 5.5. Oxidation potentials (Eh) of birnessite with different AOS values were estimated using the equilibrium concentrations of hydroquinone oxidized by the birnessite samples, indicating that Eh was linearly proportional to AOS. The oxidation kinetics of bisphenol A (BPA), a model organic pollutant, by birnessite suggest that the logarithms of surface area-normalized pseudo-first-order initial rate constants (log kSA) for BPA degradation by birnessite were linearly correlated with the Eh or AOS values of birnessite with AOS greater than 3.64.

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Application of an image management system in microscopy

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100129899 ◽

1992 ◽

Vol 50 (2) ◽

pp. 1052-1053

Author(s):

Richard S. Chemock

Keyword(s):

Data Storage ◽

Cost Savings ◽

Image Data ◽

Analytical Techniques ◽

Operational Mode ◽

Fine Grained ◽

Image Recording ◽

Primary Output ◽

Capacity Data ◽

Image Management System

One of the most common tasks in a typical analysis lab is the recording of images. Many analytical techniques (TEM, SEM, and metallography for example) produce images as their primary output. Until recently, the most common method of recording images was by using film. Current PS/2R systems offer very large capacity data storage devices and high resolution displays, making it practical to work with analytical images on PS/2s, thereby sidestepping the traditional film and darkroom steps. This change in operational mode offers many benefits: cost savings, throughput, archiving and searching capabilities as well as direct incorporation of the image data into reports.The conventional way to record images involves film, either sheet film (with its associated wet chemistry) for TEM or PolaroidR film for SEM and light microscopy. Although film is inconvenient, it does have the highest quality of all available image recording techniques. The fine grained film used for TEM has a resolution that would exceed a 4096x4096x16 bit digital image.

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Investigation of low- and high-resistance Ni–Ge–Au ohmic contacts to n+ GaAs using electron microbeam and surface analytical techniques

Journal of Materials Research ◽

10.1557/jmr.1996.0159 ◽

1996 ◽

Vol 11 (5) ◽

pp. 1244-1254 ◽

Cited By ~ 7

Author(s):

Nancy E. Lumpkin ◽

Gregory R. Lumpkin ◽

K. S. A. Butcher

Keyword(s):

Electron Microscopy ◽

Ohmic Contacts ◽

Analytical Electron Microscopy ◽

Depth Profiling ◽

Analytical Techniques ◽

Two Phase ◽

Low Resistance ◽

Fine Grained ◽

Multiphase Microstructure ◽

Transmission Electron

A process for the formation of low-resistance Ni–Ge–Au ohmic contacts to n+ GaAs has been refined using multivariable screening and response surface experiments. Samples from the refined, low-resistance process (which measure 0.05 ± 0.02 Ω · mm) and the unrefined, higher resistance process (0.17 ± 0.02 Ω · mm) were characterized using analytical electron microscopy (AEM), transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and x-ray photoemission spectroscopy (XPS) depth profiling methods. This approach was used to identify microstructural differences and compare them with electrical resistance measurements. Analytical results of the unrefined ohmic process sample reveal a heterogeneous, multiphase microstructure with a rough alloy-GaAs interface. The sample from the refined ohmic process exhibits an alloy which is homogeneous, smooth, and has a fine-grained microstructure with two uniformly distributed phases. XPS analysis for the refined ohmic process sample indicates that the Ge content is relatively depleted in the alloy (relative to the deposited Ge amount) and enriched in the GaAs. This is not evidenced in the unrefined ohmic process sample. Our data lead us to conclude that a smooth, uniform, two-phase microstructure, coupled with a shift in Ge content from the post-alloy metal to the GaAs, is important in forming low-resistance ohmic contacts.

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Yearly microbial cycle of human exposed surfaces in show caves

Subterranean Biology ◽

10.3897/subtbiol.31.34490 ◽

2019 ◽

Vol 31 ◽

pp. 1-14

Author(s):

Silviu Bercea ◽

Ruxandra Năstase-Bucur ◽

Oana Teodora Moldovan ◽

Marius Kenesz ◽

Silviu Constantin

Keyword(s):

Microbial Communities ◽

Rapid Test ◽

Coliform Bacteria ◽

Culturable Bacteria ◽

Indirect Contact ◽

Cave Environment ◽

Show Caves ◽

High Concentrations ◽

Bacteria And Fungi ◽

High Level

The human impact upon the subterranean microbiomes is not only a peril to the cave environment but might also affect future visitors. We focused on the changes that humans induced on the surfaces they came in direct or indirect contact with inside two intensely visited Romanian show caves, by means of commercially available microbial rapid test kits and molecular identification. Overall culturable bacteria abundance in the caves maintained high levels year-round while Enterobacteriaceae, coliform bacteria and Escherichiacoli levels peaked during the touristic season, reaching levels that could pose a threat to the health of the visitors. Culturable fungi abundance usually peaked in the spring, remained at a high level in the summer and started to slowly decrease towards the winter months. Differences were observed between the direct and indirect exposed surfaces, as the later had lower overall levels of bacteria and fungi, with increased Enterobacteriaceae loads. Most of the taxa identified are known biodeteriorants of subterranean surfaces and were previously associated with human altered caves. A Dothideomycete sp. previously unknown to the cave environments was detected. This was the first study to analyse the dynamics of the microbial communities of delicate subterranean surfaces in show caves through the use of commercially available test kits. We revealed that exposed surfaces in show caves, in direct or indirect contact with tourists, are host to high concentrations of cultivable microbes. The touristic activity was shown to influence the abundance and dynamics of the microbial communities inhabiting surfaces of show caves.

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Submarine groundwater discharge and alkaline earth element dynamics in a deltaic coastal setting

Hydrology Research ◽

10.2166/nh.2016.285 ◽

2016 ◽

Vol 48 (5) ◽

pp. 1169-1176 ◽

Cited By ~ 2

Author(s):

Daniel J. Coleman ◽

Alexander S. Kolker ◽

Karen H. Johannesson

Keyword(s):

Mississippi River ◽

Submarine Groundwater Discharge ◽

Alkaline Earth ◽

Groundwater Discharge ◽

Local Environment ◽

Estuarine Water ◽

Fine Grained ◽

Alkaline Earth Element ◽

Submarine Groundwater ◽

End Members

Submarine groundwater discharge is a process that is often considered negligible in deltaic systems given their low gradient and fine-grained sediment. However, hydrologic budgets and radon surveys indicate that it may be a significant component of the Mississippi River Delta system. To more concretely indicate groundwater's contribution to the local environment, we conducted an analysis of estuarine water chemistry. We focused on the mid-weight alkaline earth metals, which differ significantly in the system's three end-members: river, ocean, and groundwater. We found an anomaly of barium in the estuaries, which could not be completely explained by desorption. Through the construction of a three-end-member mixing model, groundwater was estimated to comprise 14–28% of Terrebonne and Barataria Bay estuarine water, which corresponds to a combined discharge of 160–480 m3/s. This groundwater discharge helps explain the hydrologic budget of the system, and could influence the chemistry of these large deltaic estuaries.

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Rapid determination of the Mn average oxidation state of Mn oxides with a novel two-step colorimetric method

Analytical Methods ◽

10.1039/c6ay02472f ◽

2017 ◽

Vol 9 (1) ◽

pp. 103-109 ◽

Cited By ~ 14

Author(s):

Yanhua Zhu ◽

Xinran Liang ◽

Huaiyan Zhao ◽

Hui Yin ◽

Mingming Liu ◽

...

Keyword(s):

Trace Metals ◽

Oxidation State ◽

Organic Contaminants ◽

Rapid Determination ◽

Colorimetric Method ◽

Oxidation Processes ◽

Average Oxidation State ◽

Mn Oxides

The Mn average oxidation state (Mn AOS) of Mn oxides has a significant impact on their reactivity towards trace metals and organic contaminants via sorption, catalysis and oxidation processes.

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Global Aromaticity at the Nanoscale

10.26434/chemrxiv.8953565.v2 ◽

2019 ◽

Author(s):

Michel Rickhaus ◽

Michael Jirasek ◽

Lara Tejerina ◽

Henrik Gotfredsen ◽

Martin D. Peeks ◽

...

Keyword(s):

Small Molecules ◽

Organic Semiconductors ◽

Oxidation State ◽

Single Molecule ◽

Ring Current ◽

Electronic Devices ◽

Three Dimensional ◽

Average Oxidation State ◽

Ring Currents ◽

Cyclic Molecule

<div><p>Aromaticity is an important concept for predicting electronic delocalisation in molecules, particularly for designing organic semiconductors and single-molecule electronic devices. It is most simply defined by the ability of a cyclic molecule to sustain a ring current when placed in a magnetic field. Hückel’s rule states that if a ring has [4n+2] π-electrons, it will be aromatic with an induced magnetisation that opposes the external field inside the ring, whereas if it has 4n π-electrons, it will be antiaromatic with the opposite magnetisation. This rule reliably predicts the behaviour of small molecules, typically with circuits of less than about 22 π-electrons (n = 5). It is not clear whether aromaticity has a size limit and whether Hückel’s rule is valid in much larger macrocycles. Here, we present evidence for global aromaticity in a wide variety of porphyrin nanorings, with circuits of up to 162 π-electrons (n = 40; diameter 5 nm). We show that aromaticity can be controlled by changing the molecular structure, oxidation state and three-dimensional conformation. Whenever a global ring current is observed, its direction is correctly predicted by Hückel’s rule. The magnitude of the current is maximised when the average oxidation state of the porphyrin units is around 0.5–0.7, when the system starts to resemble a conductor with a partially filled valence band. Our results show that aromaticity can arise in large macrocycles, bridging the size gap between ring currents in molecular and mesoscopic rings.</p></div>

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Spatio-temporal modeling of the crowding conditions and metabolic variability in microbial communities

PLoS Computational Biology ◽

10.1371/journal.pcbi.1009140 ◽

2021 ◽

Vol 17 (7) ◽

pp. e1009140

Author(s):

Liliana Angeles-Martinez ◽

Vassily Hatzimanikatis

Keyword(s):

Microbial Communities ◽

Extracellular Polymeric Substances ◽

Resource Competition ◽

Local Environment ◽

Microbial Interactions ◽

Relative Fitness ◽

Flux Analysis ◽

Scaled Particle Theory ◽

Spatio Temporal ◽

The Impact

The metabolic capabilities of the species and the local environment shape the microbial interactions in a community either through the exchange of metabolic products or the competition for the resources. Cells are often arranged in close proximity to each other, creating a crowded environment that unevenly reduce the diffusion of nutrients. Herein, we investigated how the crowding conditions and metabolic variability among cells shape the dynamics of microbial communities. For this, we developed CROMICS, a spatio-temporal framework that combines techniques such as individual-based modeling, scaled particle theory, and thermodynamic flux analysis to explicitly incorporate the cell metabolism and the impact of the presence of macromolecular components on the nutrients diffusion. This framework was used to study two archetypical microbial communities (i) Escherichia coli and Salmonella enterica that cooperate with each other by exchanging metabolites, and (ii) two E. coli with different production level of extracellular polymeric substances (EPS) that compete for the same nutrients. In the mutualistic community, our results demonstrate that crowding enhanced the fitness of cooperative mutants by reducing the leakage of metabolites from the region where they are produced, avoiding the resource competition with non-cooperative cells. Moreover, we also show that E. coli EPS-secreting mutants won the competition against the non-secreting cells by creating less dense structures (i.e. increasing the spacing among the cells) that allow mutants to expand and reach regions closer to the nutrient supply point. A modest enhancement of the relative fitness of EPS-secreting cells over the non-secreting ones were found when the crowding effect was taken into account in the simulations. The emergence of cell-cell interactions and the intracellular conflicts arising from the trade-off between growth and the secretion of metabolites or EPS could provide a local competitive advantage to one species, either by supplying more cross-feeding metabolites or by creating a less dense neighborhood.

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The influence of microbial mats on travertine precipitation in active hydrothermal systems (Central Italy)

10.1101/2020.07.29.226266 ◽

2020 ◽

Author(s):

Giovanna Della Porta ◽

Joachim Reitner

Keyword(s):

Microbial Communities ◽

Extracellular Polymeric Substances ◽

Microbial Mats ◽

Central Italy ◽

Hydrothermal Systems ◽

Crystal Nucleation ◽

Anoxygenic Phototrophic Bacteria ◽

Physico Chemical ◽

Slope System ◽

Aluminium Silicates

ABSTRACTThe study of hydrothermal travertines contributes to the understanding of the interaction between physico-chemical processes and the role played by microbial mats and biofilms in influencing carbonate precipitation. Three active travertine sites were investigated in Central Italy to identify the types of carbonate precipitates and the associated microbial mats at varying physico-chemical parameters. Carbonate precipitated fabrics at the decimetre- to millimetre-scale and microbial mats vary with decreasing water temperature: a) at high temperature (55-44°C) calcite or aragonite crystals precipitate on microbial mats of sulphide oxidizing, sulphate reducing and anoxygenic phototrophic bacteria forming filamentous streamer fabrics, b) at intermediate temperature (44-40°C), rafts, coated gas bubbles and dendrites are associated with Spirulina cyanobacteria and other filamentous and rod-shaped cyanobacteria, c) low temperature (34-33°C) laminated crusts and oncoids in a terraced slope system are associated with diverse Oscillatoriales and Nostocales filamentous cyanobacteria, sparse Spirulina and diatoms. At the microscale, carbonate precipitates are similar in the three sites consisting of prismatic calcite (40-100 μm long, 20-40 μm wide) or acicular aragonite crystals organized in radial spherulites, overlying or embedded within biofilm EPS (Extracellular Polymeric Substances). Microsparite and sparite crystal size decreases with decreasing temperature and clotted peloidal micrite dominates at temperatures < 40°C, also encrusting filamentous microbes. Carbonates are associated with gypsum and Ca-phosphate crystals; EPS elemental composition is enriched in Si, Al, Mg, Ca, P, S and authigenic aluminium-silicates form aggregates on EPS.This study confirms that microbial communities in hydrothermal travertine settings vary as a function of temperature. Carbonate precipitate types at the microscale do not vary considerably, despite different microbial communities suggesting that travertine precipitation, driven by CO2 degassing, is influenced by biofilm EPS acting as template for crystal nucleation (EPS-mediated mineralization) and affecting the fabric types, independently from specific microbial metabolism.

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A key continental archive for the last 2 Ma of climatic history of the central Mediterranean region: A pilot drilling in the Fucino Basin, central Italy

Scientific Drilling ◽

10.5194/sd-20-13-2015 ◽

2015 ◽

Vol 20 ◽

pp. 13-19 ◽

Cited By ~ 11

Author(s):

B. Giaccio ◽

E. Regattieri ◽

G. Zanchetta ◽

B. Wagner ◽

P. Galli ◽

...

Keyword(s):

Central Italy ◽

Lacustrine Sediments ◽

Mediterranean Area ◽

Central Mediterranean ◽

Fine Grained ◽

Xrf Scanning ◽

History Of ◽

Sedimentary Succession ◽

Geochemical Analyses ◽

Fucino Basin

Abstract. An 82 m long sedimentary succession was retrieved from the Fucino Basin, the largest intermountain tectonic depression of the central Apennines. The basin hosts a succession of fine-grained lacustrine sediments (ca. 900 m-thick) possibly continuously spanning the last 2 Ma. A preliminary tephrostratigraphy study allows us to ascribe the drilled 82 m long record to the last 180 ka. Multi-proxy geochemical analyses (XRF scanning, total organic/inorganic carbon, nitrogen and sulfur, oxygen isotopes) reveal noticeable variations, which are interpreted as paleohydrological and paleoenvironmental expressions related to classical glacial–interglacial cycles from the marine isotope stage (MIS) 6 to present day. In light of the preliminary results, the Fucino sedimentary succession is likely to provide a long, continuous, sensitive, and independently dated paleoclimatic archive of the central Mediterranean area.

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