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.

Hydrothermal rare earth elements mineralization in the Barra do Itapirapua carbonatite, southern Brazil: behaviour of selected trace elements and stable isotopes (C, O)

The Bura do Itapira pua carbonatite is located in southern Brazil and belongs to the Cretaceous Ponta Grossa alkaline-carbonatitic province related to the opening of the South Atlantic. The carbonatite complex is emplaced in Proterozoic granites and is mainly composed of plutonic magnesio- to ferrocarbonatite, with smaller amounts of subvolcanic magnesiocarbonatite. Hydrothermal alteration of the carbonatite has led to the formation of quartz, apatite, fluorite, rue earth fluorocarbonates, barite and sulfides in variable proportions. Trace element data, delta(13)C and delta(18)O are presented here, with the aim of better understanding the geochemical nature of hydrothermal alteration related to rare earth elements (REE) mineralization. The non-overprinted plutonic carbonatite shows the lowest REE contents, and its primitive carbon and oxygen stable isotopic composition places it in the field of primary igneous carbonatites. Two types of hydrothermally overprinted plutonic carbonatites can be distinguished based on secondary minerals and geochemical composition. Type I contains mainly quartz, rare earth fluorocarbonates and apatite as hydrothermal secondary minerals, and has steep chondrite normalized REE patterns, with Sigma(REE+Y) of up to 3 wt.% (i.e., two orders of magnitude higher than in fresh plutonic samples). In contrast, the Type II overprint contains apatite, fluorite and barite as dominant hydrothermal minerals, and is characterized by heavy REE enrichment relative to the fresh samples, with flat chondrite normalized REE patterns. Carbon and oxygen stable isotope ratios of Types I and II are elevated (delta(18)O + 8 to + 12 parts per thousand; delta(13)C - 6 to - 2 parts per thousand) relative to the fresh samples. Hydrothermally overprinted carbonatites exposed to weathering show even higher delta(18)O values (delta(18)O 13 to 25 parts per thousand) but no additional REE enrichment. The subvolcanic carbonatite has anomalously high delta(13)C of up to + 1 parts per thousand, which suggests crustal contamination through interaction with carbonate-bearing metasediments. (C) 1999 Elsevier B.V. B.V. All rights reserved.

[The effectiveness of rare earth elements as a possible alternative growth promoter for pigs and poultry].

Mixtures of Rare Earth Elements (REE) have been used as animal growth-promoters on a large scale in China during the last 20 years. Numerous studies carried out in China claim it produces quite sensational growth-promoting effects in all categories of farm animals. To explore the question of whether REE's might prove suitable as a growth-promoter under western keeping conditions, feeding experiments were performed on pigs and poultry. The animals received a typical diet, supplemented with REE salts in concentrations between 75 and 300 mg/kg feed. Weight-gain, feed-intake, feed-conversion and (where applicable) laying parameters were observed. It was shown that in pigs receiving feed supplemented with REEs, an increase in daily weight gain of up to 19% and an improvement in feed-conversion of up to 11% can be achieved, whereas, for poultry, no positive effects on growth or productivity of the animals could be observed. Testing of important organs via Neutron Activating Analysis (NAA) showed a minute accumulation of REE, principally in liver and bones. Analysis of the poultry gut-flora, using selective media, showed that the main microorganism populations of the alimentary canal were unaffected by feed-supplementation with REE.

Rare earth elements of modern seeps from the Gulf of Mexico, the Black Sea, and the Congo Fan

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (SumREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the SumREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that SumREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

Rare earth elements in bottom sediments and Fe-Mn nodules of the Black Sea

Distributions of rare earth element contents in surface layer bottom sediments, in vertical sediment section, and in Fe-Mn nodules of the Black Sea have been studied. An inverse relationship of rare earth element contents and CaCO3 contents has been found in the studied sediments. Fe-Mn nodules of the Black Sea do not concentrate rare earth elements, and their rare earth element composition differs from one of host sediments. It is concluded that rare earth elements are bound with clay minerals of bottom sediments.

Concentration of the rare-earth elements in metalliferous sediments from DSDP Leg 92 holes

DSDP Leg 92 drilled at four sites along an east-west transect at 19°S on the western flank of the East Pacific Rise (EPR), in an area where sediments are essentially a mixture of hydrothermal and biogenic components, with only a minimal contribution of clastic material. Rare-earth element (REE) data on the metalliferous (non-carbonate) fraction of samples ranging in age from ~2 to ~27 Ma indicate the existence of two distinct groups of patterns corresponding to two broad age groups, one <=8 Ma, the other >=10 Ma. Within each group, REE patterns have characteristics which are near-uniform, despite large variations in total REE abundances. Sediments of the younger group are enriched in light REE (LREE) relative to deep bottom waters influenced by the hydrothermal plume extending west from the EPR at 19°S. Sediments of the older groups show further relative LREE enrichment and/or heavy REE (HREE) depletion. Surficial sediments deposited beneath the lysocline have high Sum REE concentrations resulting from slow accumulation rates, and patterns resembling older sediments due to early diagenetic effects. A correlation between the mass accumulation rates (MAR) of Sum REE and Fe + Mn suggests that ferromanganese particulate matter supplied by the hydrothermal plume scavenges REE; during this process the LREE are preferentially removed from plume seawater. The MAR of Fe + Mn shows a general decrease with age above basement, whereas Sum REE concentrations in the metalliferous component increase with age above basement. This supports the Ruhlin and Owen model wherein limited scavenging of REE, due to rapid burial of sediment near the palaeo-axis, leads to low concentrations (but high MAR-values) for the REE. Following deposition and burial of the hydrothermal component, further relative flattening of the REE pattern takes place, probably the result of diagenetic reactions over several million years. Phase partitioning data indicate that the proportion of REE residing in more poorly crystalline phases tends to increase with age (from ~45% to 90% of Sum REE). This suggests that as initial ferromanganese precipitates undergo diagenetic recrystallization, REE are transferred to the poorly crystalline phases, and/or are scavenged from pore waters by these phases. Because of the various modifications to REE patterns apparently produced both in the water column and post-depositional settings, the REE patterns of metalliferous sediments will not reflect fine-scale REE variations in associated oceanic water masses.

Rare earth elements from the Atlantic Sector

We present a Rare Earth Elements (REE) record at decadal resolution determined in the EPICA ice core drilled in Dronning Maud Land (EDML) in the Atlantic Sector of the East Antarctic Plateau, covering the transition from the last glacial age (LGA) to the early Holocene (26 600-7500 yr BP). Additionally, samples from potential source areas (PSAs) for Antarctic dust were analysed for their REE characteristics. The dust provenance is discussed by comparing the REE fingerprints in the ice core and the PSAs samples. We find a shift in REE composition at 15 200 yr BP in the ice core samples. Before 15 200 yr BP, the dust composition is very uniform and its provenance was likely to be dominated by a South American source. After 15 200 yr BP, multiple sources such as Australia and New Zealand become relatively more important, albeit South America is possibly still an important dust supplier. A similar change in the dust characteristics was observed in the EPICA Dome C ice core at around ~15 000 yr BP. A return to more glacial dust characteristics between ~8300 and ~7500 yr BP, as observed in the EPICA Dome C core, could not be observed in the EDML core. Consequently, the dust provenance at the two sites must have been different at that time.

Mineral composition, rare earth elements, and trace elements from samples of the northern Congo deep-sea fan

Authigenic carbonates were collected from methane seeps at Hydrate Hole at 3113 m water depth and Diapir Field at 2417 m water depth on the northern Congo deep-sea fan during RV Meteor cruise M56. The carbonate samples analyzed here are nodules, mainly composed of aragonite and high-Mg calcite. Abundant putative microbial carbonate rods and associated pyrite framboids were recognized within the carbonate matrix. The d13C values of the Hydrate Hole carbonates range from -62.5 permil to -46.3 permil PDB, while the d13C values of the Diapir Field carbonate are somewhat higher, ranging from -40.7 permil to -30.7 permil PDB, indicating that methane is the predominant carbon source at both locations. Relative enrichment of 18O (d18O values as high as 5.2 permil PDB) are probably related to localized destabilization of gas hydrate. The total content of rare earth elements (REE) of 5% HNO3-treated solutions derived from carbonate samples varies from 1.6 ppm to 42.5 ppm. The shale-normalized REE patterns all display positive Ce anomalies (Ce/Ce* > 1.3), revealing that the carbonates precipitated under anoxic conditions. A sample from Hydrate Hole shows a concentric lamination, corresponding to fluctuations in d13C values as well as trace elements contents. These fluctuations are presumed to reflect changes of seepage flux.