Local structural relaxation around Co2+ along the hardystonite–Co-?kermanite melilite solid solution     

Matteo Ardit  Giuseppe Cruciani  Michele Dondi 《Physics and Chemistry of Minerals》2012,39(9):713-723

Six pure compounds belonging to the hardystonite (Ca₂ZnSi₂O₇)–Co-?kermanite (Ca₂CoSi₂O₇) solid solution were investigated by the combined application of X-ray powder diffraction and electronic absorption spectroscopy. Structural refinements of the XRPD data revealed a negative excess volume of mixing due to the single isovalent substitution of Co for Zn in the tetrahedral site. In agreement with the diffraction data, deconvolution of the optical spectra showed a progressive decreasing of the crystal field strength parameter 10Dq moving toward the Co-?kermanite end-member, meaning that the local cobalt–oxygen bond distance, $ \langle {\text{Co}}{-}{\text{O}}\rangle^{\text{local}} $ , increased along the join with the amount of cobalt. The calculated structural relaxation coefficient around the fourfold coordinated Co²⁺ in the Ca₂(Zn_1?x Co _x )Si₂O₇ join was ε?=?0.69, very far from the one predicted by the Vegard’s law (ε?=?0) and at variance with ε?=?0.47 previously found for tetrahedrally coordinated Co²⁺ in gahnite–Co-aluminate spinel solid solution. This difference is consistent with the largest constraints existing on the spinel structure, based on cubic closest packing, compared to the more flexible layered melilite structure.  相似文献   

Melilite-type and melilite-related compounds: structural variations along the join Sr_2?xBa_xMgSi₂O₇ (0?≤?x?≤?2) and high-pressure behavior of the two end-members     

Matteo Ardit  Michele Dondi  Marco Merlini  Giuseppe Cruciani 《Physics and Chemistry of Minerals》2012,39(3):199-211

The structural variations along the solid solution Sr_2−x Ba _x MgSi₂O₇ (0 ≤ x ≤ 2), combined to the high-pressure characterization of the two end-members, have been studied. A topological change from the tetragonal (melilite-type) to the monoclinic (melilite-related) structure along the join Sr₂MgSi₂O₇ (e.g., P[`4]2₁ m P\bar{4}2_{1} m )–Ba₂MgSi₂O₇ (e.g., C2/c) occurs with a Ba content higher than 1.6 apfu. Favored in the crystallization from a melt, the tetragonal form has a tetrahedral sheet topology exclusively based on five-membered rings, which provide a regular “4 up + 4 down” ligand arrangement. In contrast, the melilite-related structure, favored by solid-state reaction synthesis, is made by alternating six- and four-membered tetrahedral rings, which give an asymmetric arrangement of alternated “5 up + 3 down” and “3 up + 5 down” ligands around Sr or Ba. This latter configuration is characterized by an additional degree of freedom with Ba polyhedra hosted in the interlayer with a more irregular and compact coordination and longer Ba–O bond distances. Further insights into the relationships between the two melilite typologies were achieved by investigating the in situ high-pressure behavior of these systems. The synchrotron high-pressure experiments allowed to calculate the elastic moduli for the Sr melilite-type end-member and for the Ba monoclinic polymorph (Sr₂MgSi₂O₇: K _T0 = 107, K _a=b  = 121, and K _c  = 84 GPa; m-Ba₂MgSi₂O₇: K _T0 = 85, K _a  = 96, K _b  = 72, and K _c  = 117 GPa) and compare them with those reported in the literature for ?kermanite (Ca₂MgSi₂O₇). The results show that, although the volume of Ba polyhedron in tetragonal polymorphs is larger than in the monoclinic forms, the interlayer compressibility is significantly lower in the former structures due to the occurrence of very short Ba–O distances. This unfavored Ba environment also makes tetragonal Ba₂MgSi₂O₇ a metastable phase at room conditions, possibly favored by high pressure. However, no phase transition occurs from monoclinic to tetragonal form due to kinetic hindrance in reconstructing the sheet topology.  相似文献   

Production of amorphous hydrated impure magnesium carbonate through ex situ carbonation     

Andrea Orlando  Matteo Lelli  Luigi Marini 《Applied Geochemistry》2012

The evaluation of the feasibility of ex situ carbonation in landfills utilizing raw natural substances (namely serpentinites as Mg-source and the CO₂-rich fraction of biogas as C-source) was tested through a laboratory procedure comprising three steps. The first step is the acid attack of a serpentinite at 70 °C, by means of HCl 2 M, to get MgCl₂-rich solutions. Attacks of different durations were performed to evaluate the time needed. The second step is the neutralization of the MgCl₂-rich solution by addition of concentrated ammonia. The third (carbonation) step is mixing of the neutralized MgCl₂-rich solution with a solution of ammonium carbonate. This was produced in a landfill by absorption of CO₂ contained in biogas in a solution of ammonia. The neutralization of acid MgCl₂-rich solutions caused the precipitation of ferrihydrite with secondary ammonium carnallite and salammoniac, whereas abundant precipitation of Amorphous Hydrated Impure Magnesium Carbonate (AHIMC), sometimes with minor nesquehonite, occurred in the third step. This solid carbonate acts as a stable CO₂ sink up to 380 °C. The geochemical behavior of some minor elements was also investigated during the experimental processes revealing that Al, Cr and Ni were removed during neutralization (second step), in contrast to Ca which remained in the circumneutral MgCl₂-rich solution and entered into the structure of AHIMC. During the carbonation step, precipitation of artinite, hydromagnesite, lansfordite, magnesite and nesquehonite was thermodynamically impossible as the aqueous phase was undersaturated with respect to these solid phases upon separation of AHIMC.  相似文献   

Mission-constrained design drivers and technical solutions for the MAGIA satellite     

Giorgio Perrotta  M. Stipa  D. Silvi  S. Coltellacci  G. Curti  G. Colonna  T. Formica  V. Casali  T. Fossati  F. Di Matteo  M. Zelli  M. Rinaldi  L. Ansalone  A. Di Salvo 《Experimental Astronomy》2011,32(1):63-82

The Mission MAGIA (Missione Altimetrica Geofisica GeochImica lunAre) was proposed in the framework of the ??Bando per Piccole Missioni?? of ASI (Italian Space Agency) in 2007. The mission was selected for a phase A study by ASI on February 7th 2008. The tight budget allocation, combined with quite ambitious scientific objectives, set challenging requirements for the satellite design. The paper gives a fast overview of the payloads complement and of the mission-constrained design drivers, including cost minimization, risk reduction, and AIT flexibility. The spacecraft architecture is then outlined, along with an overview of the key subsystems and trade-offs. Some details are given of a Moon gravitometric experiment based on a mother?Cdaughter satellite configuration with the daughter being a subsatellite released from the MAGIA satellite and intended to circle the Moon at a very low altitude. Budgets are appended at the end of the paper showing the key study results.  相似文献   

Thermoelastic behavior and dehydration process of cancrinite     

G. D. Gatta  D. Comboni  M. Alvaro  P. Lotti  F. Cámara  M. C. Domeneghetti 《Physics and Chemistry of Minerals》2014,41(5):373-386

The high-temperature thermoelastic behavior of a natural cancrinite has been investigated by in situ single-crystal X-ray diffraction. The unit-cell volume variation as a function of temperature (T) exhibits a continuous trend up to 748 K (hydrous expansion regime). The unit-cell edges expansion clearly shows an anisotropic expansion scheme (α _a  < α _c ). At 748 K, a dehydration process takes place, and a series of unit-cell parameter measurements at constant temperature (748 K) for a period of 12 days indicate that the dehydration process continued for the entire period of time, until the cell parameters were found to be constant. After the dehydration process is completed, the structure expands almost linearly with increasing temperature up to 823 K, where a sudden broadening of the diffraction peaks, likely due to the impending decomposition, did not allow the collection of further data points. Even with a very limited temperature range for the anhydrous regime, we observed that the behavior of the two (i.e., hydrous and anhydrous) high-temperature structures is similar in terms of (1) volume thermal expansion coefficient and (2) thermoelastic anisotropy. The structure refinements based on the data collected at 303, 478 and 748 K (after the dehydration), respectively, showed a change in the mechanism of tilting of the quasi-rigid (Si,Al)O₄ tetrahedra, following the loss of H₂O molecules, ascribable to the high-temperature Na⁺ coordination environment within the cages.  相似文献   

The Rosetta Marbles from Fesleğen, Ören Unit,SW Anatolia     

Franziska Scheffler  Roland Oberhänsli  Amaury Pourteau  Osman Candan  Matteo Di Lucia 《International Journal of Earth Sciences》2014,103(2):485-486

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Natural Cr(VI) contamination of groundwater in the Cecina coastal area and its inner sectors (Tuscany,Italy)     

Matteo Lelli  Sergio Grassi  Michele Amadori  Fabrizio Franceschini 《Environmental Earth Sciences》2014,71(9):3907-3919

A detailed hydrogeochemical study of groundwater in the Cecina coastal plain (Livorno province, Italy) and its inner sectors was undertaken in 2008, as chemical analyses carried out on groundwater since 2006 have revealed Cr(VI) concentrations of up to 49 μg/L (well above the permissible limit of 5 μg/L). Ophiolite outcrops are present throughout the study area, and their fragments likely represent a significant portion of the existing multilayered aquifer skeleton. Waters delivered by the serpentinite outcrops have a typically Mg–HCO₃ composition, whereas those of the coastal plain are prevailingly of the Ca/Mg–HCO₃ type with significant Mg contents. Significant NO₃ contamination characterises the studied coastal plain, and an interesting negative correlation exists between Cr(VI) and both NO₃ and SO₄ deriving from the widespread use of (NH₄)₂SO₄ as a farm fertilizer. Chromium speciation calculations carried out using the EQ3NR code reveal that the prevailing Cr(VI) species in solution is CrO₄ ^2?; however, CaCrO₄° and MgCrO₄° neutral complexes represent significant percentages (up to 42 %). These findings suggest that the mobility and consequently the bioavailability of Cr(VI) can be significantly enhanced by these neutral complexes, which are not considered to be affected by adsorption/desorption processes. The Cr(VI) source, investigated by means of the Mg/SiO₂ molar ratio, seems to be represented mainly by Mg-bearing minerals of the chlorite group. Petrographic observations confirm the occurrence of this mineral group. The interaction between rainwater and the local serpentinite rock was simulated at different $P_{{{\text{CO}}_{ 2} }}$ and $P_{{{\text{O}}_{ 2} }}$ conditions by reaction path modelling using the EQ3/6 software package. $P_{{{\text{O}}_{ 2} }}$ was varied in accordance with the assumption that redox conditions are determined in part by NO₃. Results are in good agreement with experimental data on spring waters and subordinately with data on some coastal plain groundwater, which plot in a rather wide $P_{{{\text{CO}}_{ 2} }}$ and $P_{{{\text{O}}_{ 2} }}$ field. Although the dissolved Cr content is mostly of natural origin, fertilization may affect its fate.  相似文献   

Multi-method characterization of DOM from the Turia river (Spain)     

Sergio Navalon  Mercedes Alvaro  Isabel Alcaina  Hermenegildo Garcia 《Applied Geochemistry》2010

Water concentrates from Turia river (1.5 mg L⁻¹ total organic C) obtained by nanofiltration (membrane mass cut-off 90 Da) were fractioned by non-ionic Amberlite resins (DAX8 and XAD4) to afford three samples termed as hydrophobic acid (50%), transphilic acid (24%) and hydrophobic neutral (12%). If a nanofiltration membrane 270 Da mass cut-off is used then about 50% of dissolved organic matter is not retained. These three fractions were characterized by analytical and spectroscopic techniques (¹H NMR, MALDI–TOF-MS, ESI–API-MS, ESI–MS/MS). Overall, these data are compatible with the presence of oligosaccharides, oligopeptides and fatty acids as the main components of dissolved organic matter. Particularly revealing was the information from MALDI–TOF-MS and ESI–MS/MS where series of compounds differing in the number of hexose units were identified. The three fractions have many spectroscopic similarities and, particularly the hydrophobic and transphilic ones, are really almost identical. This similarity in the fraction composition shows that the conventional fractionation procedure is inefficient as a standard general method for separation of different compound types. The composition of dissolved organic matter was confirmed, and some individual organic compounds identified, by GC–MS analysis of the silylated derivatives obtained by reacting the fractions with a mixture of N,O-bis(trimethylsilyl)trifluoroacetamide with trimethylchlorosilane (10%). Thus, rather surprisingly, the dissolved organic matter of this natural raw water is predominantly composed of a relatively simple mixture of a few types of compounds with molecular weights well below 1100 Da (about six hexose units). These results, particularly the absence of detectable amounts of high molecular weight humic acids and low molecular weight phenolic compounds indicates that trihalomethanes formed in the water disinfection process by Cl₂ really derive from oligosaccharides and oligopeptides. Also, the data suggests alternative strategies to effect a more efficient fractionation of the dissolved organic matter.  相似文献   

“The ESA XMM-Newton Science Operations Centre: Making Basic Space Science Available to the Whole Scientific World”     

Carlos Gabriel  Matteo Guainazzi  Leo Metcalfe 《Astrophysics and Space Science》2006,305(3):315-320

XMM-Newton is a major X-ray observatory of the European Space Agency (ESA). Its observing time is open to astronomers from the whole scientific community on a peer reviewed competitive basis. The Science Operations Centre, located at ESA’s premises in Villafranca del Castillo, Spain, is responsible for the instrument operations, as well as for all the tasks related to facilitating the scientific exploitation of the data which the mission has been producing since its launch in December 1999. Among them, one may list:

•	distribution of scientific data in different formats, from raw telemetry, up to processed and calibrated high-level science products, such as images, spectra, source lists, etc;
•	development and distribution of dedicated science analysis software, as well as of continuously updated instrument calibration;
•	regular organisation of training workshops (free of cost), for potential users of XMM-Newton data, where the procedures and techniques to successfully reduce and analyze XMM-Newton data are introduced;
•	access to the data through state-of-the-art, in-house-developed archival facilities, either through the Internet or via CD-ROM;
•	continuously updated documentation on all aspects of spacecraft and instrument operations, data reduction and analysis;
•	maintenance of a comprehensive set of project web pages;
•	a competent and responsive HelpDesk, providing dedicated support to individual XMM-Newton users.

Everyone can be an XMM-Newton observer. So far, astronomers from 36 countries submitted observing programs. Public data can be accessed by every scientist in the world through the XMM-Newton Science Archive (XSA).Despite all these efforts, one can’t help noticing an asymmetric level of scientific exploitation in the realm of X-ray astronomy between developing and developed countries. The latter have traditionally enjoyed the comparative advantage of deeper know-how, deriving from direct experience in hardware and mission development. The XMM-Newton Science Operations Centre’s efforts act to alleviate this situation through, for example, increasing the usage of the web for data and information dissemination, as well as by supporting actively such initiatives as the COSPAR Capacity-Building Workshops, specifically designed to create long-lasting bridges between researchers in developing and developed countries.  相似文献   

Evidence of gully formation by regional groundwater flow in the Gorgonum-Newton region (Mars)     

Alvaro Márquez  Miguel Ángel de Pablo  Cristóbal Viedma 《Icarus》2005,179(2):398-414

The discovery of gullies on Mars suggests liquid water activity near the surface of the planet in recent times. Since liquid water is unstable under the present-day P-T martian conditions, the formation mechanisms of the gullies, and the source of the putative water, have been a matter of debate for the last years. To provide new insights into these matters, we have approached the problem studying the gullies in relation to their regional setting. A major point in our study relates to the geographic orientation of gullies, an aspect that has been previously regarded as a crucial matter in different models, and has profound implications regarding their origin. We present a comprehensive and detailed survey of the Gorgonum-Newton region, and a study of the Dao and Nirgal Vallis regions. The survey was carried out with the aid of 965 high-resolution MOC images (752 for Gorgonum-Newton, 102 for Nirgal Vallis and 111 for Dao Vallis regions), and MOLA-derived DEMs. We found that gullies display a clear regional pattern, geographically and topographically consistent with a decreasing regional slope. We interpret the results in terms of the existence of several groundwater flow systems operating at different scales, which ultimately may have led to gully formation by seepage at the slopes of craters and canyons. We suggest that aquifers discharging at gully systems may have recharged from the surface, in response to the melting of young partially eroded ice-rich deposits.  相似文献