Rare earth element geochemistry of scleractinian coral skeleton during meteoric diagenesis: A sequence through neomorphism of aragonite to calcite

Rare earth element geochemistry in carbonate rocks is utilized increasingly for studying both modern oceans and palaeoceanography, with additional applications for investigating water–rock interactions in groundwater and carbonate diagenesis. However, the study of rare earth element geochemistry in ancient rocks requires the preservation of their distribution patterns through subsequent diagenesis. The subjects of this study, Pleistocene scleractinian coral skeletons from Windley Key, Florida, have undergone partial to complete neomorphism from aragonite to calcite in a meteoric setting; they allow direct comparison of rare earth element distributions in original coral skeleton and in neomorphic calcite. Neomorphism occurred in a vadose setting along a thin film, with degradation of organic matter playing an initial role in controlling the morphology of the diagenetic front. As expected, minor element concentrations vary significantly between skeletal aragonite and neomorphic calcite, with Sr, Ba and U decreasing in concentration and Mn increasing in concentration in the calcite, suggesting that neomorphism took place in an open system. However, rare earth elements were largely retained during neomorphism, with precipitating cements taking up excess rare earth elements released from dissolved carbonates from higher in the karst system. Preserved rare earth element patterns in the stabilized calcite closely reflect the original rare earth element patterns of the corals and associated reef carbonates. However, minor increases in light rare earth element depletion and negative Ce anomalies may reflect shallow oxidized groundwater processes, whereas decreasing light rare earth element depletion may reflect mixing of rare earth elements from associated microbialites or contamination from insoluble residues. Regardless of these minor disturbances, the results indicate that rare earth elements, unlike many minor elements, behave very conservatively during meteoric diagenesis. As the meteoric transformation of aragonite to calcite is a near worst case scenario for survival of original marine trace element distributions, this study suggests that original rare earth element patterns may commonly be preserved in ancient limestones, thus providing support for the use of ancient marine limestones as proxies for marine rare earth element geochemistry.

Reply to the discussion by Karen Johannesson on “Rare earth element geochemistry of scleractinian coral skeleton during meteoric diagenesis: a sequence through neomorphism of aragonite to calcite” by Webb et al., Sedimentology, 56, 1433-1463

Webb et al. (2009) described a late Pleistocenecoral sample wherein the diagenetic stabilization of original coral aragonite to meteoric calcite was halted more or less mid-way through the process, allowing direct comparison of pre-diagenetic and post-diagenetic microstructure and trace element distributions. Those authors found that the rare earth elements (REEs) were relatively stable during meteoric diagenesis, unlike divalent cations such as Sr,and it was thus concluded that original, in this case marine, REE distributions potentially could be preserved through the meteoric carbonate stabilization process that must have affected many, if not most, ancient limestones. Although this was not the case in the analysed sample, they noted that where such diagenesis took place in laterally transported groundwater, trace elements derived from that groundwater could be incorporated into diagenetic calcite, thus altering the initial REE distribution (Banner et al., 1988). Hence, the paper was concerned with the diagenetic behaviour of REEs in a groundwater-dominated karst system. The comment offered by Johannesson (2011) does not question those research results, but rather, seeks to clarify an interpretation made by Webb et al. (2009) of an earlier paper, Johannesson et al. (2006).

Discriminating stromatolite formation modes using rare earth element geochemistry: Trapping and binding versus in situ precipitation of stromatolites from the Neoproterozoic Bitter Springs Formation, Northern Territory, Australia

Stromatolites consist primarily of trapped and bound ambient sediment and/or authigenic mineral precipitates, but discrimination of the two constituents is difficult where stromatolites have a fine texture. We used laser ablation-inductively coupled plasma-mass spectrometry to measure trace element (rare earth element – REE, Y and Th) concentrations in both stromatolites (domical and branched) and closely associated particulate carbonate sediment in interspaces (spaces between columns or branches) from bioherms within the Neoproterozoic Bitter Springs Formation, central Australia. Our high resolution sampling allows discrimination of shale-normalised REE patterns between carbonate in stromatolites and immediately adjacent, fine-grained ambient particulate carbonate sediment from interspaces. Whereas all samples show similar negative La and Ce anomalies, positive Gd anomalies and chondritic Y/Ho ratios, the stromatolites and non-stromatolite sediment are distinguishable on the basis of consistently elevated light REEs (LREEs) in the stromatolitic laminae and relatively depleted LREEs in the particulate sediment samples. Additionally, concentrations of the lithophile element Th are higher in ambient sediment samples than in stromatolites, consistent with accumulation of some fine siliciclastic detrital material in the ambient sediment but a near absence in the stromatolites. These findings are consistent with the stromatolites consisting dominantly of in situ carbonate precipitates rather than trapped and bound ambient sediment. Hence, high resolution trace element (REE + Y, Th) geochemistry can discriminate fine-grained carbonates in these stromatolites from coeval non-stromatolitic carbonate sediment and demonstrates that the sampled stromatolites formed primarily from in situ precipitation, presumably within microbial mats/biofilms, rather than by trapping and binding of ambient sediment. Identification of the source of fine carbonate in stromatolites is significant, because if it is not too heavily contaminated by trapped ambient sediment, it may contain geochemical biosignatures and/or direct evidence of the local water chemistry in which the precipitates formed.

Infrared and Raman spectroscopic characterization of the carbonate mineral huanghoite - and in comparison with selected rare earth carbonates

Raman spectroscopy complimented with infrared spectroscopy has been used to study the rare earth based mineral huanghoite with possible formula given as BaCe(CO3)2F 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 huanghoite displays three bands are at 1072, 1084 and 1091 cm−1 attributed to the symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of symmetric stretching vibration varies with mineral composition. Infrared spectroscopy of huanghoite show bands at 1319, 1382, 1422 and 1470 cm−1. No Raman bands of huanghoite were observed in these positions. 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 for huanghoite are observed at 687, 704, 718 and 730 cm−1and assigned to the (CO3)2− ν2 bending modes. Raman bands are observed for huanghoite at around 627 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. Raman bands for huanghoite observed at 3259, 3484 and 3589 cm−1 are attributed to water stretching bands. Multiple bands are observed in the OH stretching region for bastnasite and parisite indicating the presence of water and OH units in their mineral structure. Vibrational spectroscopy enables new information on the structure of huanghoite to be assessed.

Trace-element modeling of the magmatic evolution of rare-earth-rich carbonatite from the Miaoya deposit, Central China

Carbonatites are known to contain the highest concentrations of rare-earth elements (REE) among all igneous rocks. The REE distribution of carbonatites is commonly believed to be controlled by that of the rock forming Ca minerals (i.e., calcite, dolomite, and ankerite) and apatite because of their high modal content and tolerance for the substitution of Ca by light REE (LREE). Contrary to this conjecture, calcite from the Miaoya carbonatite (China), analyzed in situ by laser-ablation inductively-coupled-plasma mass-spectrometry, is characterized by low REE contents (100–260 ppm) and relatively !at chondrite-normalized REE distribution patterns [average (La/Yb)CN=1.6]. The carbonatite contains abundant REE-rich minerals, including monazite and !uorapatite, both precipitated earlier than the REE-poor calcite, and REE-fluorocarbonates that postdated the calcite. Hydrothermal REE-bearing !uorite and barite veins are not observed at Miaoya. The textural and analytical evidence indicates that the initially high concentrations of REE and P in the carbonatitic magma facilitated early precipitation of REE-rich phosphates. Subsequent crystallization of REE-poor calcite led to enrichment of the residual liquid in REE, particularly LREE. This implies that REE are generally incompatible with respect to calcite and the calcite/melt partition coefficients for heavy REE (HREE) are significantly greater than those for LREE. Precipitation of REE-fluorocarbonates late in the evolutionary history resulted in depletion of the residual liquid in LREE, as manifested by the development of HREE-enriched late-stage calcite [(La/Yb)CN=0.7] in syenites associated with the carbonatite. The observed variations of REE distribution between calcite and whole rocks are interpreted to arise from multistage fractional crystallization (phosphates!calcite!REE-!uorocarbonates) from an initially REE-rich carbonatitic liquid.

An enhanced procedure for the rapid digestion of high silicate archeological specimens followed by ICP-MS determination of traces of rare earth elements (REE's)

A straightforward procedure for the acid digestion of geological samples with SiO2 concentrations ranging between about 40 to 80%, is described. A powdered sample (200 mesh) of 500 mg was used and fused with 1000 mg spectroflux at about 1000 degreesC in a platinum crucible. The molten was subsequently digested in an aqueous solution of HNO3 at 100 degreesC. Several systematic digestion procedures were followed using various concentrations of HNO3. It was found that a relationship could be established between the dissolution-time and acid concentration. For an acid concentration of 15% an optimum dissolution-time of under 4 min was recorded. To verify that the dissolutions were complete, they were subjected to rigorous quality control tests. The turbidity and viscosity were examined at different intervals and the results were compared with that of deionised water. No significant change in either parameter was observed. The shelf-life of each solution lasted for several months, after which time polymeric silicic acid formed in some solutions, resulting in the presence of a gelatinous solid. The method is cost effective and is clearly well suited for routine applications on a small scale, especially in laboratories in developing countries. ICP-MS was applied to the determination of 13 Rare Earth Elements and Hf in a set of 107 archaeological samples subjected to the above digestion procedure. The distribution of these elements was examined and the possibility of using the REE's for provenance studies is discussed.

Seasonal and spatial variations in rare earth elements to identify inter-aquifer linkages and recharge processes in an Australian catchment

With the aim of elucidating the seasonal behaviour of rare earth elements (REEs), surface and groundwaters were collected under dry and wet conditions in different hydrological units of the Teviot Brook catchment (Southeast Queensland, Australia). Sampled waters showed a large degree of variability in both REE abundance and normalised patterns. Overall REE abundance ranged over nearly three orders of magnitude, and was consistently lower in the sedimentary bedrock aquifer (18ppt<∑REE<477ppt) than in the other hydrological systems studied. Abundance was greater in springs draining rhyolitic rocks (∑REE=300 and 2054ppt) than in springs draining basalt ranges (∑REE=25 and 83ppt), yet was highly variable in the shallow alluvial groundwater (16ppt<∑REE<5294ppt) and, to a lesser extent, in streamwater (85ppt<∑REE<2198ppt). Generally, waters that interacted with different rock types had different REE patterns. In order to obtain an unbiased characterisation of REE patterns, the ratios between light and middle REEs (R(M/L)) and the ratios between middle and heavy REEs (R(H/M)) were calculated for each sample. The sedimentary bedrock aquifer waters had highly evolved patterns depleted in light REEs and enriched in middle and heavy REEs (0.17

Energetics of rare earth manganese perovskites A1-xA ' xMnO3 (A = La, Nd, Y and A ' = Sr, La) systems

High temperature reaction calorimetry using molten lead berate as solvent has been used to study the thermochemistry of NdMnO3, YMnO3, La1-xSrxMnO3 (with 0 < x < 0.5), and Ln(0.5)Ca(0.5)MnO(3) (with Ln = La, Nd, Y), The enthalpies of formation of these multicomponent oxides from their binary constituents have been calculated from the measured enthalpy of drop solution, The energetic stability of the perovskite depends on the size of the A cation, The enthalpy of formation of YMnO3 (smallest A cation) is more endothermic than those of NdMnO3 and LaMnO3. The energetics of the perovskite also depends on the oxidation state of the B site's ions. In the La1-xSrxMnO3 system, the energetic stability of the structure increases with the Mn4+/Mn3+ ratio, The new values of the enthalpies of oxidations, with reliable standard entropies, were used to plot the phase stability diagram of the lanthanum-manganese-oxygen system in the temperature range 300-1100 K, The LaMnO3/MnO phase boundary evaluated in this study agrees with the one published by Atsumi et nl. calculated from thermogravimetric and conductivity measurements.

Giant Magnetoresistance and Related Properties of Rare Earth Manganates and Other Oxide Systems

Giant magnetoresistance (GMR), which was until recently confined to magnetic layered and granular materials, as well as doped magnetic semiconductors, occurs in manganate perovskites of the general formula Ln(1-x)A(x)MnO(3) (Ln = rare earth; A = divalent ion). These manganates are ferromagnetic at or above a certain value of x (or Mn4+ content) and become metallic at temperatures below the curie temperature, T-c. GMR is generally a maximum close to T-c or the insulator-metal (I-M) transition temperature, T-im. The T-c and %MR are markedly affected by the size of the A site cation, [r(A)], thereby affording a useful electronic phase diagram when T-c or T-im is plotted against [r(A)]. We discuss GMR and related properties of manganates in polycrystalline, thin-film, and single-crystal forms and point out certain commonalities and correlations. We also examine some unusual features in the electron-transport properties of manganates, in particular charge-ordering effects. Charge ordering is crucially dependent on [r(A)] or the e(g) band width, and the charge-ordered insulating state transforms to a metallic ferromagnetic state on the application of a magnetic field.

Phase transitions and rare-earth magnetism in hexagonal and orthorhombic $DyMnO_{3}$ single crystals

The floating-zone method with different growth ambiences has been used to selectively obtain hexagonal or orthorhombic DyMnO3 single crystals. The crystals were characterized by x-ray powder diffraction of ground specimens and a structure refinement as well as electron diffraction. We report magnetic susceptibility, magnetization and specific heat studies of this multiferroic compound in both the hexagonal and the orthorhombic structure. The hexagonal DyMnO3 shows magnetic ordering of Mn3+ (S = 2) spins on a triangular Mn lattice at T-N(Mn) = 57 K characterized by a cusp in the specific heat. This transition is not apparent in the magnetic susceptibility due to the frustration on the Mn triangular lattice and the dominating paramagnetic susceptibility of the Dy3+ (S = 9/2) spins. At T-N(Dy) = 3 K, a partial antiferromagnetic order of Dy moments has been observed. In comparison, the magnetic data for orthorhombic DyMnO3 display three transitions. The data broadly agree with results from earlier neutron diffraction experiments, which allows for the following assignment: a transition from an incommensurate antiferromagnetic ordering of Mn3+ spins at T-N(Mn) = 39 K, a lock-in transition at Tlock-in = 16 K and a second antiferromagnetic transition at T-N(Dy) = 5 K due to the ordering of Dy moments. Both the hexagonal and the orthorhombic crystals show magnetic anisotropy and complex magnetic properties due to 4f-4f and 4f-3d couplings.

59Co NMR studies of the spin-state equilibria in rare-earth cobaltites

Hyperfine interaction parameters reveal differences in the nature of spin-state equilibria in the lighter and heavier rare-earth cobaltites; the crystal-field parameter is lower in the lighter cobaltites. Temperature variation of the quadrupolar coupling constant is also more marked in the lighter rare-earth cobaltites, with NdCoO3 showing evidence for a structural phase transition.

An investigation of structural, magnetic and dielectric properties of R2NiMnO6 (R = rare earth, Y)

We have investigated the structure, magnetic and dielectric properties of the double perovskite oxides, R2NiMnO6 (R = Pr, Nd, Sm, Gd, Tb, Dy, Ho and Y). We could refine powder X-ray diffraction patterns of all the phases on the basis of monoclinic (P2(1)/n) double perovskite structure where Ni and Mn atoms are ordered at 2c and 2d sites, respectively. All the phases are ferromagnetic insulators exhibiting relatively low dielectric loss and dielectric constants in the range 15-25. The ferromagnetic ordering temperature of the R2NiMnO6 series seems to correlate better with the radius of R3+ atoms than with the average Ni-O-Mn angle (phi) in the double perovskite structure. These results are consistent with all samples having Mn4+ and Ni2+ With minimal antisite disorder.

Satellites in the X-ray photoelectron spectra of transition-metal and rare-earth compounds

An attempt has been made at synthesis and in resolving some of the uncertainties related to the assignments of charge-transfer satellites in the X-ray photoelectron spectra of transition-metal and rare-earth compounds. New satellites are reported in the ligand core-hole spectra as well as in the metal core-level spectra of oxides of second- and third-row transition metals including rare earths. Satellites in the ligand levels and the metal levels tend to be mutually exclusive, a behaviour that can be understood on the basis of metal-ligand overlap. Systematics in the intensities and energy separations of satellites in the first-row transition-metal compounds have been examined in order to gain an insight into the nature of these satellites. A simple model involving the sudden approximation has been employed to explain the observed systematics in intensities of satellites appearing next to metal and ligand core levels on the basis of metal-ligand overlap.

A Magnetic Susceptibility Study of Spin-state Transitions in Rare-earth TrioxocobaItates( III)

Rare-earth trioxocobaltates(lll), Ln[CoO,], with Ln = Pr, Nd, Tb, Dy. and Yb exhibit low-spin to high-spin transitions of cobalt characterised by a maximum in the Ax-l against temperature plots where Ax is the cobalt contribution to the magnetic susceptibility. The susceptibility behaviour is distinct from that of La[CoO,] which shows a plateau in the x-I-T curve accompanied by a structural transition. The temperature at which the AX- I-T curve shows a maximum increases with the decrease in the size of the rare-earth ion. The susceptibility behavior of solid solutions of La,,Nd,CoO, has been investigated to see how the behaviour characteristic of Nd[CoO,] changes to that of La[CoO,].