Scanning electron microscopy with energy dispersive spectroscopy and Raman and infrared spectroscopic study of tilleyite Ca5Si2O7(CO3)2-Y

The mineral tilleyite-Y, a carbonate-silicate of calcium, has been studied by scanning electron microscopy with chemical analysis using energy dispersive spectroscopy (EDX) and Raman and infrared spectroscopy. Multiple carbonate stretching modes are observed and support the concept of non-equivalent carbonate units in the tilleyite structure. Multiple Raman and infrared bands in the OH stretching region are observed, proving the existence of water in different molecular environments in the structure of tilleyite. Vibrational spectroscopy offers new information on the mineral tilleyite.

Thermodynamic properties of Cu-3(CO3)(2)(OH)(2) and the spin-1/2 distorted diamond Heisenberg chain

The thermodynamic properties of the spin-1/2 diamond quantum Heisenberg chain model have been investigated by means of the transfer matrix renormalization group (TMRG) method. Considering different crystal structures, by changing the interactions among different spins and the external magnetic fields, we first investigate the magnetic susceptibility, magnetization, and specific heat of the distorted diamond chain as a model of ferrimagnetic spin systems. The susceptibility and the specific heat show different features for different ferromagnetic (F) and antiferromagnetic (AF) interactions and different magnetic fields. A 1/3 magnetization plateau is observed at low temperature in a magnetization curve. Then, we discuss the theoretical mechanism of the double-peak structure of the magnetic susceptibility and the three-peak structure of the specific heat of the compound Cu-3(CO3)(2)(OH)(2), on which an elegant measurement was performed by Kikuchi [Phys. Rev. Lett. 94, 227201 (2005)]. Our computed results are consistent with the main characteristics of the experimental data. Meanwhile, we find that the double-peak structure of susceptibility can be found in several different kinds of spin interactions in the diamond chain. Moreover, a three-peak behavior is observed in the TMRG results of magnetic susceptibility. In addition, we perform calculations relevant for some experiments and explain the characteristics of these materials. (c) 2007 American Institute of Physics.

Estudo da influência dos íons K+, Mg2+, SO4 2- e CO3 2- na cristalização biomimética de fosfato de cálcio amorfo (ACP) e conversão a fosfato octacálcico (OCP)

The crystallization of hydroxyapatite (HA) in aqueous solution can be described by the mechanism ACP → OCP → HA. In this work, it was studied the influence of K+, Mg2+, SO4 2- AND CO3 2- ions in the formation of ACP and in its conversion to OCP, using biomimetic coatings on metallic substrates of commercially pure titanium (Ti c.p.). The results showed that Mg2+ and CO3 2- ions favored both the formation of ACP and its conversion to OCP. Differently, K+ and SO4 2- ions did not influence the formation of ACP and, consequently, interfered in the conversion to OCP.

Raman spectroscopic study of the magnesium carbonate mineral– hydromagnesite Mg5[(CO3)4(OH)2]•4H2O

Magnesium minerals are important for the understanding of the concept of geosequestration. One method of studying the hydrated hydroxy magnesium carbonate minerals is through vibrational spectroscopy. A combination of Raman and infrared spectroscopy has been used to study the mineral hydromagnesite. An intense band is observed at 1121 cm-1 attributed CO32- ν1 symmetric stretching mode. A series of infrared bands at 1387, 1413, 1474 cm-1 are assigned to the CO32- ν3 antisymmetric stretching modes. The CO32- ν3 antisymmetric stretching vibrations are extremely weak in the Raman spectrum and are observed at 1404, 1451, 1490 and 1520 cm-1. A series of Raman bands at 708, 716, 728, 758 cm-1 are assigned to the CO32- ν2 in-plane bending mode. The Raman spectrum in the OH stretching region is characterised by bands at 3416, 3516 and 3447 cm-1. In the infrared spectrum a broad band is found at 2940 cm-1 assigned to water stretching vibrations. Infrared bands at 3430, 3446, 3511, 2648 and 3685 cm-1 are attributed to MgOH stretching modes.

Raman spectroscopic study of the uranyl carbonate mineral čejkaite and its comparison with synthetic trigonal Na4[UO2(CO3)3]

Raman and infrared spectroscopies were used to characterise two samples of triclinic ejkaite Na4[UO2(CO3)3] and its synthetic trigonal analogue. The v3 (UO2)2+ mode is not Raman active, whereas both the v3 and v1 (UO2)2+ modes are infrared active. U--O bond lengths in uranyls were calculated from the spectra obtained and compared with bond lengths derived from crystal structure analyses. From the higher number of bands related to the uranyl and carbonate vibrations, the presence of symmetrically distinct (UO2)2+ and (CO3)2- units in both structures is proposed.

Raman spectroscopy of decrespignyite (Y,REE)4Cu(CO3)4Cl(OH)5•2(H2O) and in relation with other halogenated carbonates including bastnasite, hydroxybastnasite, parisite and northupite

Raman spectroscopy complimented with infrared spectroscopy has been used to study the rare earth based mineral decrespignyite (Y,REE)4Cu(CO3)4Cl(OH)5•2(H2O) and compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of decrespignyite displays three bands are at 1056, 1070 and 1088 cm-1 attributed to the CO32- symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of CO32- symmetric stretching vibration varies with mineral composition. Raman bands of decrespignyite show bands at 1391, 1414, 1489 and 1547 cm-1. Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 cm-1 assigned to the ν3 (CO3)2- antisymmetric stretching mode. The observation of additional Raman bands for the ν3 modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands are observed at 791, 815, 837 and 849 cm-1and assigned to the (CO3)2- ν2 bending modes. Raman bands are observed for decrespignyite at 694, 718 and 746 cm-1 and are assigned to the (CO3)2- ν4 bending modes. Raman bands are observed for the carbonate ν4 in phase bending modes at 722 cm-1 for bastnasite, 736 and 684 cm-1 for parisite, 714 cm-1 for northupite. Multiple bands are observed in the OH stretching region for decrespignyite, bastnasite and parisite indicating the presence of water and OH units in the mineral structure.

Raman spectroscopic study of the hydroxy-phosphate mineral plumbogummite PbAl3(PO4)2(OH,H2O)6

Plumbogummite PbAl3(PO4)2(OH,H2O)6 is a mineral of environmental significance and is a member of the alunite-jarosite supergroup. The molecular structure of the mineral has been investigated by Raman spectroscopy. The spectra of different plumbogummite specimens differ although there are many common features. The Raman spectra prove the spectral profile consisting of overlapping bands and shoulders. Raman bands and shoulders observed at 971, 980, 1002 and 1023 cm−1 (China sample) and 913, 981, 996 and 1026 cm−1 (Czech sample) are assigned to the ν1 symmetric stretching modes of the (PO4)3−, at 1002 and 1023 cm−1 (China) and 996 and 1026 cm−1 to the ν1 symmetric stretching vibrations of the (O3POH)2− units, and those at 1057, 1106 and 1182 (China) and at 1102, 1104 and 1179 cm−1 (Czech) to the ν3 (PO4)3− and ν3 (PO3) antisymmetric stretching vibrations. Raman bands and shoulders at 634, 613 and 579 cm−1 (China) and 611 and 596 cm−1 (Czech) are attributed to the ν4 (δ) (PO4)3− bending vibrations and those at 507, 494 and 464 cm−1 (China) and 505 and 464 cm−1 (Czech) to the ν2 (δ) (PO4)3− bending vibrations. The Raman spectrum of the OH stretching region is complex. Raman bands and shoulders are identified at 2824, 3121, 3249, 3372, 3479 and 3602 cm−1 for plumbogummite from China, and at 3077, 3227, 3362, 3480, 3518 and 3601 cm−1 for the Czech Republic sample. These bands are assigned to the ν OH stretching modes of water molecules and hydrogen ions. Approximate O–H⋯O hydrogen bond lengths inferred from the Raman spectra vary in the range >3.2–2.62 Å (China) and >3.2–2.67 Å (Czech). The minority presence of some carbonate ions in the plumbogummite (China sample) is connected with distinctive intensity increasing of the Raman band at 1106 cm−1, in which may participate the ν1 (CO3)2− symmetric stretching vibration overlapped with phosphate stretching vibrations.

Infrared and Raman spectroscopic characterization of the carbonate mineral weloganite – Sr3Na2Zr(CO3)6·3H2O and in comparison with selected carbonates

The mineral weloganite Na2Sr3Zr(CO3)6·3H2O has been studied by using vibrational spectroscopy and a comparison is made with the spectra of weloganite with other carbonate minerals. Weloganite is member of the mckelveyite group that includes donnayite-(Y) and mckelveyite-(Y). The Raman spectrum of weloganite is characterized by an intense band at 1082 cm−1 with shoulder bands at 1061 and 1073 cm−1, attributed to the View the MathML source symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of View the MathML source symmetric stretching vibration varies with mineral composition. The Raman bands at 1350, 1371, 1385, 1417, 1526, 1546, and 1563 cm−1 are assigned to the ν3 (CO3)2− antisymmetric stretching mode. The observation of additional Raman bands for the ν3 modes for weloganite is significant in that it shows distortion of the carbonate anion in the mineral structure. The Raman band observed at 870 cm−1 is assigned to the (CO3)2− ν2 bending mode. Raman bands observed for weloganite at 679, 682, 696, 728, 736, 749, and 762 cm−1 are assigned to the (CO3)2− ν4 bending modes. A comparison of the vibrational spectra is made with that of the rare earth carbonates decrespignyite, bastnasite, hydroxybastnasite, parisite, and northupite.

(Table 2) Trace metal ratios of various benthic foraminifera shells

Benthic foraminiferal d13C and Cd/Ca studies suggest that deep Atlantic circulation during the Last Glacial Maximum was very different from today, with high-nutrient (low d13C, high Cd) deep Southern Ocean Water (SOW) penetrating far into the North Atlantic. However, if some glacial d13C values are biased by productivity artifacts and/or air-sea exchange processes, then the existing d13C data may be consistent with the continual dominance of North Atlantic Deep Water (NADW). Cibicidoides wuellerstorfi Cd/Ca results presented here indicate that the glacial North Atlantic was strongly enriched in dissolved Cd below ~2500 m depth. If NADW formation was still vigorous relative to SOW formation, these data could be explained by either increased preformed nutrient levels in the high-latitude North Atlantic or by increased organic matter remineralization within lower NADW. High glacial Zn/Ca values in the same samples, however, are best explained by a substantially increased mixing with Zn-rich SOW. The cause was most likely a partial replacement of NADW by less dense Glacial North Atlantic Intermediate Water. This reorganization also lowered deep North Atlantic [CO3]2- concentrations by perhaps 10 to 15 µmol/kg.

(Tables 2, 3) Element ratios of planktonic foraminifera from western Pacific surface sediments

Accurately quantifying deep-sea calcite dissolution is crucial for understanding the role of the marine carbonate system in regulating atmospheric pCO2 over millennia. We compare a foraminifer-fragmentation-based calcite dissolution proxy (Globorotalia menardii fragmentation index (MFI)) to Mg/Ca, Sr/Ca, and Mg/Sr in several species of deep dwelling planktonic foraminifers. We conducted microfossil and geochemical analyses on the same core top samples taken at different depths on the Ontong Java Plateau to maximize the dissolution signal and minimize the temperature overprint on our data. We also compare elemental ratios from planktonic foraminifer tests to modern bottom water [CO3]2- undersaturation and model-derived estimates of percent calcite dissolved in deep-sea sediments. We find clear linear decreases in Mg/Ca or Mg/Sr in G. menardii and Pulleniatina obliquiloculata with increasing (1) bottom water [CO3]2- undersaturation, (2) percent calcite dissolved in sediments calculated with biogeochemical modeling, (3) MFI, and (4) percent calcite dissolved derived from MFI. These findings lend further support to MFI as a calcite dissolution proxy for deep-sea sediments. In contrast, we find no significant correlation between Sr/Ca and independent dissolution indicators. Our results suggest that Mg/Ca and Mg/Sr from deep dwelling foraminifers could potentially be used as calcite dissolution proxies in combination with independent water temperature estimates. Likewise, establishing the relationship between MFI and dissolution-induced changes in the Mg/Ca of surface-dwelling foraminifers could provide a tool to correct Mg/Ca-derived sea surface temperature reconstructions for calcite dissolution.