A Reliable Method for Determining the Oxidation State of Manganese at the Microscale in Mn Oxides via Raman Spectroscopy     

Simone Bernardini  Fabio Bellatreccia  Giancarlo Della Ventura  Armida Sodo 《Geostandards and Geoanalytical Research》2021,45(1):223-244

Manganese oxides are important geomaterials, widespread in terrestrial and Martian environments. Characterisation of the oxidation state of Mn is a central issue in science; this task has been addressed up to the present by X‐ray spectroscopy or diffraction techniques. The former, however, requires access to synchrotron facilities, while the latter does not provide crystal‐chemical information at the local scale. In this work, we compare a large set of Raman data from well‐characterised samples, already published by the same authors of this paper or as found in the literature. We show a clear correlation between the oxidation state of Mn and the wavenumber of peculiar bands; octahedrally co‐ordinated Mn²⁺ is recognised by a band around 530 cm^?1, Mn³⁺ by a band around 580 cm^?1 and Mn⁴⁺ by a band around 630 cm^?1, while tetrahedrally co‐ordinated Mn²⁺ is recognisable by a band around 650 cm^?1. Strongly distorted Mn³⁺ octahedra are indicated by the appearance of Jahn–Teller modes. Our method allows a reliable, easily accessible tool to characterise the oxidation states of Mn in oxides, also suitable for microscale mapping. It provides a robust analytical basis for the use of these minerals as redox indicators in geology/geochemistry, in exoplanetary research or for monitoring technological processes.  相似文献   

Iron release in aqueous environment by fresh volcanic ash from Mount Etna (Italy) and Popocatépetl (Mexico) volcanoes     

Giancarlo Capitani  Nobuyoshi Miyajima  Roberto Sulpizio  Maria D’Addabbo  Lucia Galimberti  Massimo Guidi  Giovanni B. Andreozzi 《Environmental Earth Sciences》2018,77(13):521

In this study, we performed leaching experiments for timescales of hours-to-months in deionized water on fresh volcanic ash from Mt. Etna (Italy) and Popocatépetl (Mexico) volcanos to monitor Fe release as a function of ash mineral chemistry and size, with the aim of clarifying Fe release mechanisms and eventually evaluating the impact of volcanic ash on marine and lacustrine environments. To define sample mineralogy and Fe speciation, inclusive characterization was obtained by means of XRF, SEM, XRPD, EELS and Mössbauer spectroscopies. For Etna and Popocatépetl samples, glass proportions were quantified at 73 and 40%, Fe₂O₃ total contents at 11.6–13.2 and 5.8 wt%, and Fe³⁺/Fe_Tot ratios at 0.33 and 0.23, respectively. Leaching experiments showed that significant amounts of iron, ~?30 to 150 and ~?750 nmol g^?1 l^?1 for pristine Etna and Popocatépetl samples, respectively, are released within the first 30 min as a function of decreasing particle size (from 1 to 0.125 mm). The Popocatépetl sample showed a very sustained Fe release (up to 10 times Etna samples) all along the first week, with lowest values never below 400 nmol g^?1 l^?1 and a maximum of 1672 nmol g^?1 l^?1 recorded after 5 days. This sample, being composed of very small particles (average particle size 0.125 mm) with large surface area, likely accumulated large quantities of Fe-bearing sublimates that quickly dissolved during leaching tests, determining high Fe release and local pH decrease (that contributed to release more Fe from the glass) at short timescale (hours-to-days). The fractional Fe solubility (Fe_S) was 0.004–0.011 and 0.23% for Etna and Popocatépetl samples, respectively, but no correlation was found between Fe released in solution and either ash Fe content, glass/mineral ratio or mineral assemblage. Results obtained suggest that volcanic ash chemistry, mineralogy and particle size assume a relevant role on Fe release mostly in the medium-to-long timescale, while Fe release in the short timescale is dominated by dissolution of surface sublimates (formed by physicochemical processes occurring within the eruption plume and volcanic cloud) and the effects of such a dissolution on the local pH conditions. For all samples, a moderate to sustained Fe release occurred for leaching times comparable with their residence time within the euphotic zone of marine and lacustrine environments (variable from few minutes to few hours), revealing their possible contribution to increase Fe bioavailability.  相似文献   

Quantitative analysis of H2O and CO2 in cordierite using polarized FTIR spectroscopy     

Giancarlo Della Ventura  Francesco Radica  Fabio Bellatreccia  Andrea Cavallo  Francesco Capitelli  Simon Harley 《Contributions to Mineralogy and Petrology》2012,164(5):881-894

We report a FTIR (Fourier transform infrared) study of a set of cordierite samples from different occurrence and with different H₂O/CO₂ content. The specimens were fully characterized by a combination of techniques including optical microscopy, single-crystal X-ray diffraction, EMPA (electron microprobe analysis), SIMS (secondary ion mass spectrometry), and FTIR spectroscopy. All cordierites are orthorhombic Ccmm. According to the EMPA data, the Si/Al ratio is always close to 5:4; X _Mg ranges from 76.31 to 96.63, and additional octahedral constituents occur in very small amounts. Extraframework K and Ca are negligible, while Na reaches the values up to 0.84 apfu. SIMS shows H₂O up to 1.52 and CO₂ up to 1.11 wt%. Optically transparent single crystals were oriented using the spindle stage and examined by FTIR micro-spectroscopy under polarized light. On the basis of the polarizing behaviour, the observed bands were assigned to water molecules in two different orientations and to CO₂ molecules in the structural channels. The IR spectra also show the presence of small amounts of CO in the samples. Refined integrated molar absorption coefficients were calibrated for the quantitative microanalysis of both H₂O and CO₂ in cordierite based on single-crystal polarized-light FTIR spectroscopy. For H₂O the integrated molar coefficients for type I and type II water molecules (ν₃ modes) were calculated separately and are ^[I]ε?=?5,200?±?700?l?mol^?1?cm^?2 and ^[II]ε?=?13,000?±?3,000?l?mol^?1?cm^?2, respectively. For CO₂ the integrated coefficient is $ \varepsilon_{{{\text{CO}}_{ 2} }} $ ?=?19,000?±?2,000?l?mol^?1?cm^?2.  相似文献   

Induced thermal compaction in cohesive sediments around a borehole heat exchanger: laboratory tests on the effect of pore water salinity     

Giorgia Dalla Santa  Antonio Galgaro  Fabio Tateo  Simonetta Cola 《Environmental Earth Sciences》2016,75(3):181

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Thresholds of Adverse Effects of Macroalgal Abundance and Sediment Organic Matter on Benthic Habitat Quality in Estuarine Intertidal Flats     

Martha Sutula  Lauri Green  Giancarlo Cicchetti  Naomi Detenbeck  Peggy Fong 《Estuaries and Coasts》2014,37(6):1532-1548

Confidence in the use of macroalgae as an indicator of estuarine eutrophication is limited by the lack of quantitative data on the thresholds of its adverse effects on benthic habitat quality. In the present study, we utilized sediment profile imagery (SPI) to identify thresholds of adverse effects of macroalgal biomass, sediment organic carbon (% OC) and sediment nitrogen (% N) concentrations on the apparent Redox Potential Discontinuity (aRPD), the depth that marks the boundary between oxic near-surface sediment and the underlying suboxic or anoxic sediment. At 16 sites in eight California estuaries, SPI, macroalgal biomass, sediment percent fines, % OC, and % N were analyzed at 20 locations along an intertidal transect. Classification and Regression Tree (CART) analysis was used to identify step thresholds associated with a transition from "reference" or natural background levels of macroalgae, defined as that range in which no effect on aRPD was detected. Ranges of 3–15 g dw macroalgae m^?2, 0.4–0.7 % OC and 0.05–0.07 % N were identified as transition zones from reference conditions across these estuaries. Piecewise regression analysis was used to identify exhaustion thresholds, defined as a region along the stress–response curve where severe adverse effects occur; levels of 175 g dw macroalgae m^?2, 1.1 % OC and 0.1 % N were identified as thresholds associated with a shallowing of aRPD to near zero depths. As an indicator of ecosystem condition, shallow aRPD has been related to reduced volume and quality for benthic infauna and alteration in community structure. These effects have been linked to reduced availability of forage for fish, birds and other invertebrates, as well as to undesirable changes in biogeochemical cycling.  相似文献   

Relationships between seep-carbonates,mud volcanism and basin geometry in the Late Miocene of the northern Apennines of Italy: the Montardone mélange     

Stefano Conti  Daniela Fontana  Claudio Corrado Lucente  Gian Andrea Pini 《International Journal of Earth Sciences》2014,103(1):281-295

The Montardone mélange (Mm) is a chaotic, block-in-matrix unit outcropping in the Montebaranzone syncline in the northern Apennines. The Mm occurs in the uppermost part of the Termina Fm, the Middle–Late Miocene interval of a succession deposited in a wedge-top slope basin (Epiligurian succession). The Mm is closely associated with bodies of authigenic carbonates, characterized by negative values of δ¹³C (from ?18.22 to ?39.05 ‰ PDB) and chemosynthetic benthic fauna (lucinid and vesicomyid bivalves). In this paper, we propose that the Mm is a mud volcano originated by the post-depositional reactivation and rising of a stratigraphically lower mud-rich mass transport body (Canossa–Val Tiepido sedimentary mélange or olistostrome) triggered by fluid overpressure. We base our conclusion on (1) the Mm pierces the entire Termina Fm and older Epiligurian units and represents the direct continuation of the underlying Canossa–Val Tiepido mélange; (2) the geometry and facies distribution of the Montebaranzone sandstone body, which are compatible with a confined basin controlled by the rising of the Mm; (3) the systematic presence of large-scale (lateral extension 300–400 m) seep-carbonates associated with the mélange, suggesting a persistent gas-enriched fluid vent from the ascending overpressured mud; (4) blocks and clasts sourced from the Mm, hosted by the authigenic carbonates, conveyed by ascending mud and gas-enriched fluids. The Mm represents one of the few fossil examples of reactivation of a basin-scale sedimentary mélange (olistostrome); a three-stage model showing mechanisms of Mm raising is proposed.  相似文献   

The Monte Orfano Conglomerate revisited: stratigraphic constraints on Cenozoic tectonic uplift of the Southern Alps (Lombardy, northern Italy)   总被引：1，自引：0，他引：1  

Dario Sciunnach  Giancarlo Scardia  Fabrizio Tremolada  Isabella Premoli Silva 《International Journal of Earth Sciences》2010,99(6):1335-1355

The Monte Orfano Conglomerate (MOC), exposed in the foothills of the Southern Alps (northern Italy), is one of the few outcrops of sediments documenting the Cenozoic tectonic evolution of the Alpine retrowedge. Calcareous nannofossil biostratigraphy allowed us to constrain the upper part of the MOC, formerly attributed to the Early-Middle Miocene in the type-locality, to the earliest Miocene (Neogene part of the NN1 nannofossil zone). A likely latest Oligocene age is therefore suggested for the bulk of the underlying conglomerates, whose base is not exposed. Deposition of the MOC can be placed within the post-collisional tectonic uplift of the Alps, documented in the Lake Como area by the Como Conglomerate (CC) at the base of the Gonfolite Lombarda Group, and supports the correlation with Upper Oligocene clastic sediments cropping out further to the East, in the Lake Garda and in the Veneto-Friuli areas (“molassa”). The remarkable difference in petrographic composition between the western (CC) and eastern (MOC) clastics deposited in the Alpine retro-foreland basin highlights the synchronous tectonic activity of two structural domains involving different crustal levels. Whilst the bulk of the CC, that straddles the Oligocene/Miocene boundary, records largely the tectonic exhumation of the Alpine axial chain crystalline complexes, the coeval MOC consists of detritus derived from the superficial crustal section (Triassic to Paleogene sedimentary rocks) of the Alpine retrowedge and constrains the onset of the post-collisional deformation phase of the Southern Alps as not younger than the Late Oligocene.  相似文献