Rare-earth elements and high pressures

Praseodymium, under very high pressures, shows a magnetic behavior similar to that of cerium at normal pressure.

Patterns of rare earth and other trace elements in Paleogene and Miocene clayey sediments from the Mondego platform (Central Portugal)

In the present study the origin of clay deposits occurring in an inland platform, in central Portugal, was investigated by their mineralogical and chemical composition. The clay deposits, exploited for ceramic industry are composed of silt-clay facies, the Monteira Member and the Arroça Member, which are assigned to the Coja Formation (Paleogene) and the Campelo Formation (Miocene), respectively. These clayey facies show almost compositional homogeneity, especially concerning texture. The mineralogical composition of the Monteira Member displays slightly higher content in smectite and interstratified clay minerals, which is supported by the chemical composition of samples analyzed. Both members present similar REE patterns, displaying an intense weathering record and little variation in the source area composition. Minor element geochemistry suggests low content in heavy minerals and transition metals. REE patterns and ratios of geochemical parameters support the dominant metasedimentary provenance, with a granite source contribution and also mature recycled sediments of continental origin. The study results’ suggest that the clays of these two members have the same source in terms of lithology and recycled sediments from the Hesperian massif. During the deposition of the Arroça Member, a major remobilization of the Monteira Member is suggested, explaining the geochemical similarity of both facies.

Rare earth elements and neodymium isotopes in world river sediments revisited

Over the past decades, rare earth elements (REE) and their radioactive isotopes have received tremendous attention in sedimentary geochemistry, as tracers for the geological history of the continental crust and provenance studies. In this study, we report on elemental concentrations and neodymium (Nd) isotopic compositions for a large number of sediments collected near the mouth of rivers worldwide, including some of the world’s major rivers. Sediments were leached for removal of non-detrital components, and both clay and silt fractions were retained for separate geochemical analyses. Our aim was to re-examine, at the scale of a large systematic survey, whether or not REE and Nd isotopes could be fractionated during Earth surface processes. Our results confirmed earlier assumptions that river sediments do not generally exhibit any significant grain-size dependent Nd isotopic variability. Most sediments from rivers draining old cratonic areas, sedimentary systems and volcanic provinces displayed similar Nd isotopic signatures in both clay and silt fractions, with ΔεNd (clay-silt) < |1.| A subtle decoupling of Nd isotopes between clays and silts was identified however in a few major river systems (e.g. Nile, Mississippi, Fraser), with clays being systematically shifted towards more radiogenic values. This observation suggests that preferential weathering of volcanic and/or sedimentary rocks relative to more resistant lithologies may occur in river basins, possibly leading locally to Nd isotopic decoupling between different size fractions. Except for volcanogenic sediments, silt fractions generally displayed homogeneous REE concentrations, exhibiting relatively flat shale-normalized patterns. However, clay fractions were almost systematically characterized by a progressive enrichment from the heavy to the light REE and a positive europium (Eu) anomaly. In agreement with results from previous soil investigations, the observed REE fractionation between clays and silts is probably best explained by preferential alteration of feldspars and/or accessory mineral phases. Importantly, this finding clearly indicates that silicate weathering can lead to decoupling of REE between different grain-size fractions, with implications for sediment provenance studies. Finally, we propose a set of values for a World River Average Clay (WRAC) and Average Silt (WRAS), which provide new estimates for the average composition of the weathered and eroded upper continental crust, respectively, and could be used for future comparison purposes.

Effect of rare earth dopants on structural and mechanical properties of nanoceria synthesized by combustion method

Structural characteristics of combustion synthesized, calcined and densified pure and doped nanoceria with tri-valent cations of Er, Y, Gd, Sm and Nd were analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). The results showed that the as-synthesized and calcined nanopowders were mesoporous and calculated lattice parameters were close to theoretical ion-packing model. The effect of dopants on elastic modulus, microhardness and fracture toughness of sintered pure and doped ceria were investigated. It was observed that tri-valent cation dopants increased the hardness of the ceria, whereas the fracture toughness and elastic modulus were decreased.

Thermodynamic Analysis of Rare Earth Chlorination and Bromination Processes

Research funded by the Army Research Laboratory (ARL), the Metallurgical and Materials Engineering Department at Montana Tech investigated various methods of extracting and refining rare earth elements (REEs) from mineral ores and concentrates. Extensive thermodynamic, thermogravimetric and differential thermal analyses were performed to evaluate the relative stabilities of various REE compounds in order to assess potential methods for selective separation and recovery of specific REEs. Conversion of rare earth oxides (REO) to rare earth chlorides or bromides is a possible initial step in pyrometallurgical and hydrometallurgical processing of REEs. REO can be converted to chlorides or bromides by roasting in the presence of a chloridizing or bromidizing reactant. (e.g. NH4Cl and NH4Br).

Determination of rare earth elements in geological samples using the agilent SVDV ICP-OES.

2016

Anomalous electric dipole internal conversion

Electric dipole internal conversion has been experimentally studied for several nuclei in the rare earth region. Anomalies in the conversion process have been interpreted in terms of nuclear structure effects. It was found that all the experimental results could be interpreted in terms of the j ∙ r type of penetration matrix element; the j ∙ ∇ type of penetration matrix element was not important. The ratio λ of the El j ∙ r penetration matrix element to the El gamma-ray matrix element was determined from the experiments to be:

Lu¹⁷⁵,396 keV, λ = - 1000 ± 100;

282 keV, λ = 500 ± 100;

144 keV, λ = 500 ± 250;

Hf¹⁷⁷, 321 keV λ = - 1400 ± 200;

208 keV λ = - 90 ± 40;

72 keV |λ| ≤ 650;

Gd¹⁵⁵, 86 keV λ = - 150 ± 100;

Tm¹⁶⁹, 63 keV λ = - 100 ± 100;

W¹⁸², 152 keV, λ = - 160 ±80;

67 keV, λ = - 100 ± 100.

Predictions for λ are made using the unified nuclear model.

Limestone and speleothem trace element geochemistry as tools for palaeoclimatic reconstruction, Mount Etna region, central-coastal Queensland

This study investigated potential palaeoclimate proxies provided by rare earth element (REE) geochemistry in speleothems and in clay mineralogy of cave sediments. Speleothem and sediment samples were collected from a series of cave fill deposits that occurred with rich vertebrate fossil assemblages in and around Mount Etna National Park, Rockhampton (central coastal Queensland). The fossil deposits range from Plio- Pleistocene to Holocene in age (based on uranium/thorium dating) and appear to represent depositional environments ranging from enclosed rainforest to semi-arid grasslands. Therefore, the Mount Etna cave deposits offer the perfect opportunity to test new palaeoclimate tools as they include deposits that span a known significant climate shift on the basis of independent faunal data. The first section of this study investigates the REE distribution of the host limestone to provide baseline geochemistry for subsequent speleothem investigations. The Devonian Mount Etna Beds were found to be more complex than previous literature had documented. The studied limestone massif is overturned, highly recrystallised in parts and consists of numerous allochthonous blocks with different spatial orientations. Despite the complex geologic history of the Mount Etna Beds, Devonian seawater-like REE patterns were recovered in some parts of the limestone and baseline geochemistry was determined for the bulk limestone for comparison with speleothem REE patterns. The second part of the study focused on REE distribution in the karst system and the palaeoclimatic implications of such records. It was found that REEs have a high affinity for calcite surfaces and that REE distributions in speleothems vary between growth bands much more than along growth bands, thus providing a temporal record that may relate to environmental changes. The morphology of different speleothems (i.e., stalactites, stalagmites, and flowstones) has little bearing on REE distributions provided they are not contaminated with particulate fines. Thus, baseline knowledge developed in the study suggested that speleothems were basically comparable for assessing palaeoclimatically controlled variations in REE distributions. Speleothems from rainforest and semi-arid phases were compared and it was found that there are definable differences in REE distribution that can be attributed to climate. In particular during semiarid phases, total REE concentration decreased, LREE became more depleted, Y/Ho increased, La anomalies were more positive and Ce anomalies were more negative. This may reflect more soil development during rainforest phases and more organic particles and colloids, which are known to transport REEs, in karst waters. However, on a finer temporal scale (i.e. growth bands) within speleothems from the same climate regime, no difference was seen. It is suggested that this may be due to inadequate time for soil development changes on the time frames represented by differences in growth band density. The third part of the study was a reconnaissance investigation focused on mineralogy of clay cave sediments, illite/kaolinite ratios in particular, and the potential palaeoclimatic implications of such records. Although the sample distribution was not optimal, the preliminary results suggest that the illite/kaolinite ratio increased during cold and dry intervals, consistent with decreased chemical weathering during those times. The study provides a basic framework for future studies at differing latitudes to further constrain the parameters of the proxy. The identification of such a proxy recorded in cave sediment has broad implications as clay ratios could potentially provide a basic local climate proxy in the absence of fossil faunas and speleothem material. This study suggests that REEs distributed in speleothems may provide information about water throughput and soil formation, thus providing a potential palaeoclimate proxy. It highlights the importance of understanding the host limestone geochemistry and broadens the distribution and potential number of cave field sites as palaeoclimate information no longer relies solely on the presence of fossil faunas and or speleothems. However, additional research is required to better understand the temporal scales required for the proxies to be recognised.

Luminescent properties of RE3+-activated CaAl2B2O7 (RE = Tb, Ce) in VUV-visible region

RE3+-activated alpha- and beta-CaAl2B2O7 (RE = Tb, Ce) were synthesized with the method of high-temperature solid-state reaction. Their VUV excitation and VUV-excited emission spectra are measured and discussed in the present article. The charge transfer band of Tb3+ and Ce3+ is respectively calculated to be at 151 +/- 2 and 159 +/- 3 nm. All the samples show an activator-independent excitation peak at about 175 nm and an emission peak at 350-360 nm ascribed to the host absorption and emission band, respectively.