Construction of volcanic records from marine sediment cores : a review and case study (Montserrat, West Indies)

Detailed knowledge of the past history of an active volcano is crucial for the prediction of the timing, frequency and style of future eruptions, and for the identification of potentially at-risk areas. Subaerial volcanic stratigraphies are often incomplete, due to a lack of exposure, or burial and erosion from subsequent eruptions. However, many volcanic eruptions produce widely-dispersed explosive products that are frequently deposited as tephra layers in the sea. Cores of marine sediment therefore have the potential to provide more complete volcanic stratigraphies, at least for explosive eruptions. Nevertheless, problems such as bioturbation and dispersal by currents affect the preservation and subsequent detection of marine tephra deposits. Consequently, cryptotephras, in which tephra grains are not sufficiently concentrated to form layers that are visible to the naked eye, may be the only record of many explosive eruptions. Additionally, thin, reworked deposits of volcanic clasts transported by floods and landslides, or during pyroclastic density currents may be incorrectly interpreted as tephra fallout layers, leading to the construction of inaccurate records of volcanism. This work uses samples from the volcanic island of Montserrat as a case study to test different techniques for generating volcanic eruption records from marine sediment cores, with a particular relevance to cores sampled in relatively proximal settings (i.e. tens of kilometres from the volcanic source) where volcaniclastic material may form a pervasive component of the sedimentary sequence. Visible volcaniclastic deposits identified by sedimentological logging were used to test the effectiveness of potential alternative volcaniclastic-deposit detection techniques, including point counting of grain types (component analysis), glass or mineral chemistry, colour spectrophotometry, grain size measurements, XRF core scanning, magnetic susceptibility and X-radiography. This study demonstrates that a set of time-efficient, non-destructive and high-spatial-resolution analyses (e.g. XRF core-scanning and magnetic susceptibility) can be used effectively to detect potential cryptotephra horizons in marine sediment cores. Once these horizons have been sampled, microscope image analysis of volcaniclastic grains can be used successfully to discriminate between tephra fallout deposits and other volcaniclastic deposits, by using specific criteria related to clast morphology and sorting. Standard practice should be employed when analysing marine sediment cores to accurately identify both visible tephra and cryptotephra deposits, and to distinguish fallout deposits from other volcaniclastic deposits.

Chemistry, Raman and infrared spectroscopic characterization of the phosphate mineral reddingite: (MnFe)3(PO4)2(H2O,OH)3, a mineral found in lithium-bearing pegmatite

Detailed investigation of an intermediate member of the reddingite–phosphoferrite series, using infrared and Raman spectroscopy, scanning electron microcopy and electron microprobe analysis, has been carried out on a homogeneous sample from a lithium-bearing pegmatite named Cigana mine, near Conselheiro Pena, Minas Gerais, Brazil. The determined formula is (Mn1.60Fe1.21Ca0.01Mg0.01)∑2.83(PO4)2.12⋅(H2O2.85F0.01)∑2.86 indicating predominance in the reddingite member. Raman spectroscopy coupled with infrared spectroscopy supports the concept of phosphate, hydrogen phosphate and dihydrogen phosphate units in the structure of reddingite-phosphoferrite. Infrared and Raman bands attributed to water and hydroxyl stretching modes are identified. Vibrational spectroscopy adds useful information to the molecular structure of reddingite–phosphoferrite.

Raman spectroscopic study of the metatellurate mineral : Xocomecatlite Cu3TeO4(OH)4

The mineral xocomecatlite is a hydroxy metatellurate mineral with Te6+O4 units. Tellurates may be subdivided according to their formula into three types of tellurate minerals: type (a) (AB)m(TeO4)pZq, type (b) (AB)m(TeO6).xH2O and (c) compound tellurates in which a second anion including the tellurite anion, is involved. The mineral Xocomecatlite is an example of the first type. Raman bands for xocomecatlite at 710, 763 and 796 cm-1 and 600 and 680 cm-1 are attributed to the ν1 (TeO4)2- symmetric and ν3 antisymmetric stretching mode. Raman bands observed at 2867 and 2926 cm-1 are assigned to TeOH stretching vibrations and enable estimation of the hydrogen bond distances of 2.622 Å (2867 cm-1), 2.634 Å (2926 cm-1) involving these OH units. The hydrogen bond distances are very short implying that they are necessary for the stability of the mineral.

Raman spectroscopic study of the mixed anion mineral Yecoraite Bi5Fe3O9(Te4+O3)(Te6+O4)2•9H2O

Tellurates are rare minerals as the tellurate anion is readily reduced to the tellurite ion. Often minerals with both tellurate and tellurite anions in the mineral are found. An example of such a mineral containing tellurate and tellurite is yecoraite. Raman spectroscopy has been used to study this mineral, the exact structure of which is unknown. Two Raman bands at 796 and 808 cm-1 are assigned to the ν1 (TeO4)2- symmetric and ν3 (TeO3)2- antisymmetric stretching modes and Raman bands at 699 cm-1 are attributed to the the ν3 (TeO4)2- antisymmetric stretching mode and the band at 690 cm-1 to the ν1 (TeO3)2- symmetric stretching mode. The intense band at 465 cm-1 with a shoulder at 470 cm-1 is assigned the (TeO4)2- and (TeO3)2- bending modes. Prominent Raman bands are observed at 2878, 2936, 3180 and 3400 cm-1. The band at 3936 cm-1 appears quite distinct and the observation of multiple bands indicates the water molecules in the yecoraite structure are not equivalent. The values for the OH stretching vibrations listed provide hydrogen bond distances of 2.625 Å (2878 cm-1), 2.636 Å (2936 cm-1), 2.697 Å (3180 cm-1) and 2.798 Å (3400 cm-1). This range of hydrogen bonding contributes to the stability of the mineral. A comparison of the Raman spectra of yecoraite with that of tellurate containing minerals kuranakhite, tlapallite and xocomecatlite is made.

A Raman spectroscopic study of the uranyl mineral rutherfordine – revisited

The molecular structure of the uranyl mineral rutherfordine has been investigated by the measurement of the NIR and Raman spectra and complemented with infrared spectra including their interpretation. The spectra of the rutherfordine show the presence of both water and hydroxyl units in the structure as evidenced by IR bands at 3562 and 3465 cm-1 (OH) and 3343, 3185 and 2980 cm-1 (H2O). Raman spectra show the presence of four sharp bands at 3511, 3460, 3329 and 3151 cm-1. Corresponding molecular water bending vibrations were only observed in both Raman and infrared spectra of one of two studied rutherfordine samples. The second rutherfordine sample studied contained only hydroxyl ions in the equatorial uranyl plane and did not contain any molecular water. The infrared spectra of the (CO3)2- units in the antisymmetric stretching region show complexity with three sets of carbonate bands observed. This combined with the observation of multiple bands in the (CO3)2- bending region in both the Raman and IR spectra suggests that both monodentate and bidentate (CO3)2- units may be present in the structure. This cannot be exactly proved and inferred from the spectra; however, it is in accordance with the X-ray crystallographic studies. Complexity is also observed in the IR spectra of (UO2)2+ antisymmetric stretching region and is attributed to non-identical UO bonds. U-O bond lengths were calculated using wavenumbers of the 3 and 1 (UO2)2+ and compared with data from X-ray single crystal structure analysis of rutherfordine. Existence of solid solution having a general formula (UO2)(CO3)1-x(OH)2x.yH2O ( x, y  0) is supported in the crystal structure of rutherfordine samples studied.

Raman spectroscopic study of the mixed anion sulphate-arsenate mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O

The mixed anion mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O has been studied by Raman spectroscopy. Characteristic bands associated with arsenate, sulphate, hydroxyl units are identified. Broad bands are observed and are resolved into component bands. Two intense bands at 859 and 830 cm-1 are assigned to the 1 (AsO4)3- symmetric stretching and 3 (AsO4)3- antisymmetric stretching modes. The comparatively sharp band at 976 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode and a broad spectral profile centered upon 1097 cm-1 is attributed to the ν3 (SO4)2- antisymmetric stretching mode. A comparison of the Raman spectra is made with other arsenate bearing minerals such as carminite, clinotyrolite, kankite, tilasite and pharmacosiderite.

Raman spectroscopic study of the uranyl mineral natrouranospinite (Na2,Ca)[(UO2)(AsO4)]2•5H2O

Raman spectra of natrouranospinite complemented with infrared spectra were studied and related to the structure of the mineral. Observed bands were assigned to the stretching and bending vibrations of (UO2)2+ and (AsO4)3- units and of water molecules. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

Raman spectroscopic study of the uranyl sulphate mineral jáchymovite (UO2)8(SO4)(OH)14•13H2O

Raman spectra of jáchymovite, (UO2)8(SO4)(OH)14•13H2O, were studied, complemented with infrared spectra, and compared with published Raman and infrared spectra of uranopilite, [(UO2)6(SO4)O2(OH)6(H2O)6] •6H2O. Bands related to the stretching and bending vibrations of (UO2)2+, (SO4)2-, (OH)- and water molecules were assigned. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

Raman spectroscopic study of the antimonate mineral brandholzite Mg[Sb(OH)12].6H2O

Raman spectra of brandholzite Mg[Sb(OH)6].6H2O were studied, complemented with infrared spectra, and related to the structure of the mineral. An intense Raman sharp band at 618 cm-1 is attributed to the SbO symmetric stretching mode. The low intensity band at 730 cm-1 is ascribed to the SbO antisymmetric stretching vibration. Low intensity Raman bands were found at 503, 526 and 578 cm-1. Corresponding infrared bands were observed at 527, 600, 637, 693, 741 and 788 cm-1. Four Raman bands observed at 1043, 1092, 1160 and 1189 cm-1 and eight infrared bands at 963, 1027, 1055, 1075, 1108, 1128, 1156 and 1196 cm-1 are assigned to δ SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and hydroxyl units is observed. Raman bands are observed at 3240, 3383, 3466, 3483 and 3552 cm-1, infrared bands at 3248, 3434 and 3565 cm-1. The first two Raman bands and the first infrared band are assigned to water stretching vibrations. The two higher wavenumber Raman bands observed at 3466 and 3552 cm-1 and two infrared bands at 3434 and 3565 cm-1 are assigned to the stretching vibrations of the hydroxyl units. Observed Raman and infrared bands are connected with O-H…O hydrogen bonds and their lengths 2.72, 2.79, 2.86, 2.88 and 3.0 Å (Raman) and 2.73, 2.83 and 3.07 Å (infrared).

Raman spectroscopic study of the uranyl mineral pseudojohannite Cu6.5[(UO2)4O4(SO4)2]2(OH)5.25H2O

Raman spectra of pseudojohannite were studied and related to the structure of the mineral. Observed bands were assigned to the stretching and bending vibrations of (UO2)2+ and (SO4)2- units and of water molecules. The published formula of pseudojohannite is Cu6.5(UO2)8\[O8](OH)5\[(SO4)4].25H2O; however Raman spectroscopy does not detect any hydroxyl units. Raman bands at 805 and 810 cm-1 are assigned to (UO2)2+ stretching modes. The Raman bands at 1017 and 1100 cm-1 are assigned to the (SO4)2- symmetric and antisymmetric stretching vibrations. The three Raman bands at 423, 465 and 496 cm-1 are assigned to the (SO4)2- ν2 bending modes. The bands at 210 and 279 cm-1 are assigned to the doubly degenerate ν2 bending vibration of the (UO2)2+ units. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

Raman spectroscopic study of the uranyl mineral metauranospinite Ca[(UO2)(AsO4)]2.8H2O

Raman spectra of metauranospinite Ca[(UO2)(AsO4)]2.8H2O complemented with infrared spectra were studied. Observed bands were assigned to the stretching and bending vibrations of (UO2)2+ and (AsO4)3- units and of water molecules. U-O bond lengths in uranyl and O-H…O hydrogen bond lengths were calculated from the Raman and infrared spectra.

Optical absorption and EPR studies on tenorite mineral

Optical absorption and EPR studies of the mineral tenorite, a cupric oxide, which originated from Mexico and contains 54.40 wt% of CuO. EPR spectral results indicate two Cu(II) closely interacting ions to give a d2 type structure. The calculated spin Hamiltonian at Rt and LNT are g = 2.160 and D = 125 G . The intensity of resonance line is not the same in low and high field regions. The optical absorption spectrum is due to Cu(II) which three sets of energies indicating Cu(II) in two independent tetragonal C4v symmetry, in addition to d2 structure of octahedral coordination. The octahedral and tetragonal field parameters are compared with those reported for several other copper containing minerals.

Raman spectroscopic study of the antimonate mineral bahianite Al5Sb35+O14(OH)2

Raman spectroscopy has been used to characterise the antimonate mineral bahianite Al5Sb35+O14(OH)2 , a semi-precious gem stone. The mineral is characterised by an intense Raman band at 818 cm-1 assigned to Sb3O1413- stretching vibrations. Other lower intensity bands at 843 and 856 cm-1 are also assigned to this vibration and this concept suggests the non-equivalence of SbO units in the structure. Low intensity Raman bands at 669 and 682 cm-1 are probably assignable to the OSbO antisymmetric stretching vibrations. Raman bands at 1756, 1808 and 1929 cm-1 may be assigned to δ SbOH deformation modes, whilst Raman bands at 3462 and 3495 cm-1 are assigned to AlOH stretching vibrations. Complexity in the low wave number region is attributed to the composition of the mineral.