YREE determination in seawater. Standardization and validation of a new method based on preconcentration techniques

The most interesting attraction of using rare-earth elements and yttrium (YREE) to address geochemical and marine chemical problems consists of their chemical coherence as group of trace elements. These characters allow YREE compositions of rocks and minerals to be extensively used in studies of provenance, petrogenesis and chemical evolution of the geological materials (1). Similarly, YREE compositions in the hydrosphere were used in studies of coagulation, particle-solution reactions and oceanic circulation of water masses (2-4). Unfortunately, very low concentrations of YREE (ng l-1 or sub-ng l-1) associated to high ionic strength of seawater always represented the main difficulty to analyse dissolved YREE in marine environment. The first geochemical investigations of YREE contents in seawater were carried out using neutron activation and isotope dilution mass spectrometry that were almost entirely replaced by inductively coupled plasma supplemented by mass spectrometry (ICP-MS) in recent years. This technique offers many advantages including simultaneous analysis of all the elements of series and their quantitative determination with detection limits of the order of ng l-1 if associated to preconcentration techniques (5). To perform ultra-trace YREE analyses in seawater, we developed a preconcentration method based on CHELEX-100 iminodiacetate resin followed by ICP-MS determination (Ref). In this study the YREE behaviour was quantitatively investigated during interactions with ion chelating resin and estimation of composed measurement uncertainty associated to measurements was evaluated with a rigorous metrological approach based on method validation and quality control of YREE data. These goals were achieved using synthetic seawater where YREE had concentrations as occurring in natural seawater samples. Under these conditions good recovery were obtained along the YREE series, ranging from 75%-85% and 90%-100% for heavy REE and Y and light REE, respectively. Composed measurement uncertainty was expressed in terms of precision, recovery uncertainties, reference material uncertainty and instrumental calibration uncertainty. The obtained results were critically discussed on the basis of the different contributions and confirm the quadrupole ICP-MS technique as highly sensitive to determine very low YREE concentrations. REFERENCES 1. S. R. Taylor, S.M. McLennan, The Continental Crust: its Composition and Evolution. Blackwell Scientific Publications, Oxford, 1985). 2. G.J. Piepgras, G.J. Wasserburg, Science 217 (1982) 207. 3. J. Zhang, Y. Nozaki, Geochim. Cosmochim. Acta 60 (1996) 4631. 4. R.H. Byrne, E. Sholkovitz, In: Gschneidner, J.K.A., Eyring, (Eds.), Handbook on the Physics and Chemistry of Rare Earths. Elsevier, New York, (1996) 498-593. 5. P. M\uf6ller, P. Dulski P., J. Luck, Spectrochim. Acta, 47B, 1379

Discrimination between effects induced by microbial activity and water-rock interactions under hydrothermal conditions according to REE behaviour

Rare earth elements (REE) were investigated in siliceous stromatolites forming in the Specchio di Venere Lake on Pantelleria Island. Chondrite-normalised patterns show significant La enrichments and Eu depletions suggesting that fluids involved in stromatolite growth experienced strong rock-water interactions under hydrothermal conditions. At the same time, enrichments in heavy REE (HREE) with respect to intermediate REE (MREE) suggest that hydrothermal fluids interacted with microbial mats during deposition of the stromatolites. The above-mentioned features suggest that rock-water interactions and bacterial activity were simultaneously recorded in the REE patterns of stromatolites, and can be discriminated in terms of amplitudes of the La anomaly, and the HREE/MREE ratio

A review of carbonatitic magmatism in the Paraná-Angola-Namibia (PAN) system.

Mesozoic to Cenozoic alkaline-carbonatitic complexes from southern Brazil, Angola and Namibia occur along main tectonic lineaments. In general, the alkaline-carbonatite complexes show intrusive/subintrusive, subcircular or oval shaped structures and are indicative of high upwelling energy. Processes of liquid immiscibility from trachytic-phonolitic liquids, starting from parental alkaline mafic magmas are believed to have generated carbonatitic liquids, as suggested by field relationships and geochemical characteristics. Ca-, Mg- and Fe-carbonatites are widespread even in the same complex. The occurrences comprise three main chronogroups, i.e. 1) Early Cretaceous (Eastern Paraguay; Brazil, Ponta Grossa Arch and Anitapolis; Angola and Namibia); 2) Late Cretaceous (Brazil , Ponta Grossa Arch, Lages and Alto Paranaiba. Namibia); 3) Paleogene, Brazil and Namibia Two principal types of associated alkaline rocks are represented, i.e. plagioleucitites l.s. (Eastern Paraguay; Brazil: Ponta Grossa Arch- Angola and Namibia) and kamafugites l.s. (Brazil: alto Paranaiba and Lages; Namibia). Significant variations in O-C isotope compositions are found in primary carbonates , the variations being mainly due to isotope exchange between carbonates and H2O-CO2-rich hydrothermal fluids, whereas magmatic processes, i.e. fractional crystallization or liquid immiscibility, probably affect the delta O-18 and delta C-13 values by not more than 2 delta%.. The isotope exchange model implies that the most significant isotopic variations took place in a hydrothermal environment, e.g. in the range 400-80 degrees C, involving fluids with CO2/H2O ratio ranging from 0.8 to 1. Sr-Nd-Pb isotope systematics highlight heterogeneous mixtures between HIMU and EMI mantle components, similar to the associated alkaline rocks and the flood tholeiites of the Parana-Angola-Etendeka (Namibia) system. This is also consistent with Re-Os systematics on selected mafic samples from the Alto Paranaiba alkaline-carbonatite province. The data relative to the noble gases suggest that the source(s) are similar to other mantle derived magmas (e.g. HIMU and MORB) and that the carbon of carbonatites is unlikely to be subduction-related carbon, and support a C-O fractionation model starting from mantle-derived sources. In spite of the strong variation shown by C-O isotopes, Sr-Nd-Pb-Os isotopic systematics could be related to an isotopically enriched source where the chemical heterogeneities reflect a depleted mantle "metasomatized" by small-volume melts and fluids rich in incompatible elements. These fluids are expected to have promoted crystallization in the mantle of K-rich phases that gave rise to a veined network variously enriched in LILE and LREE (cf. Foley, 1992b). The newly formed veins (enriched component) and peridotite matrix (depleted component) underwent a different isotopic evolution with time as reflected by the carbonatitic rocks. These conclusions may be extended to the whole Parana-Angola-Etendeka system, where isotopically distinct parent magmas were generated following two main enrichment events of the subcontinental lithospheric mantle at 2.0-1.4 and 1.0-0.5 Ga, respectively, as also supported by Re-Os systematics. The mantle sources preserved the isotopic heterogeneities over a long time, suggesting a non-convective lithospheric mantle beneath different cratons or intercratonic regions. Overall the data indicate that the alkaline-carbonatitic magmatism originated from a significant, but small scale heterogeneous subcontinental mantle. In this scenario, the Tristan da Cunha, Walvis Ridge-Rio Grande Rise and Vitoria-Trindade hotspot tracks might reflect the accomodation of stresses in the lithosphere during rifting, rather than continuous magmatic activity induced by mantle plumes beneath the moving lithosphere

Alteration effects of volcanic ash in seawater: Anomalous Y/Ho ratios in coastal waters of the Central Mediterranean sea

This paper presents the results of a study based on data collected during the oceanographic cruise ANSIC 2001 carried out in the Ionian Sea during the explosive activity of Mount Etna in the summer of 2001. Anomalous low values of Y/Ho ratios in seawater suggest extensive scavenging processes on the surfaces of smectitic alteration products, with Y and Ho fractionation controlled by the differences in their electronic configurations and behaviour during solution/surface complexation equilibria. These processes can also be traced through the presence of significant tetrad effects recorded in the chondrite-normalised Rare Earth Elements and Yttrium (YREEs) patterns of suspended particulate matter. This suggests that the preferential Y scavenging from seawater is due to the formation of inner-sphere complexes with OH- groups on montmorillonite crystal surfaces. The preliminary results of kinetic experiments of YREE released from volcanic ash to coexisting seawater, and the related effects on Y/Ho ratios and Ce anomalies, are consistent with the fractionation of Light Rare Earth Elements (LREEs) with respect to Heavy Rare Earth Elements (HREEs) observed in dissolved phase. They suggest a behaviour of Y similar to that reported for LREEs, particularly for Ce and Pr. © 2007 Elsevier Ltd. All rights reserved

Accumulation of rare earth elements in common vine leaves is achieved through extraction from soil and transport in the xylem sap

Rare Earth Elements play a critical role in current clean technologies but face scarcity and environmental challenges in their extraction. Using semi-natural controlled experiments, we tested the ability of V. vinifera L. to accumulate Rare Earth Elements naturally present in the soil. We demonstrate that V. vinifera L. passively transports all Rare Earth Elements from soil to leaves via Xylem-sap mirroring soil conditions. Since this process starts from the fifth month of V. vinifera L. growth without damaging the crops, we. estimate that it is possible to recover 900 milligrams of Rare Earth Elements per hectares from vineyard without harvesting the whole plant. We propose the direct extraction of Rare Earth Elements from leaves overcoming unstainable biomass burning yielding environmental and economic benefits.The pathway for the accumulation of rare earth elements in Vitis vinifera L. leaves is extraction from vineyard soils and subsequent transport in the xylem sap, suggests a semi-natural controlled experiment

Trace elements release from volcanic ashes to seawater. Natural concentrations in Central Mediterranean sea.

Distributions and concentrations of many minor and trace elements in epicontinental basins, as Mediterranean Sea, are mainly driven to atmospheric fallout from surroundings. This mechanism supplies an estimated yearly flux of about 1000 kg km-2 of terrigenous matter of different nature on the whole Mediterranean basin. Dissolution of these materials and processes occurring at solid-liquid interface along the water column drive the distributions of many trace elements as V, Cr, Mn, Co, Cu, and Pb with contents ranging from pmol l-1 (Co, Cd, Pb) to nmol l-1 scale in Mediterranean seawater, with some local differences in the basin. The unwinding of an oceanographic cruise in the coastal waters of Ionian Sea during the Etna’s eruptive activity in summer 2001 led to the almost unique chance to test the effects of large delivery of volcanic ash to a coastal sea water system through the analyses of distribution of selected trace elements along several seawater columns. The collection of these waters and their analyses about V, Cr, Mn, Co, Cu, and Pb contents evidenced trace element concentrations were always higher (about 1 order of magnitude at least) than those measured concentrations in the recent past in Mediterranean seawater, apart from Pb. Progressive increase of concentrations of some elements with depth, sometimes changing in a “conservative” behaviour without any clear reason and the observed higher concentrations required an investigation about interaction processes occurring at solid-liquid interface between volcanic ash and seawater along water columns. This investigation involving kinetic evaluation of trace element leaching to seawater, was carried out during a 6 months time period under laboratory conditions. X-ray investigations, SEM-EDS observations and analyses on freshly-erupted volcanic ash evidenced formation of alteration clay minerals onto glass fraction surfaces. Chemical analyses carried out on coexisting liquid phase demonstrated that trace element leaching occurs through a first quick followed by a slow second step that attaints to an apparent equilibrium after 6 months. Amplitude of kinetic rate constant measured for SiO2 release during the first step and behaviour of Ti/Si and Cr/Si rations in primary volcanic minerals, glass fraction and leaching solutions during the first 1 month stage of the experimental interaction allowed to demonstrate that trace element release mainly occurs from glassy materials and Ti-rich magnetite

Carbonatites from the southern Brazilian Platform: A review. II: Isotopic evidences

Early and Late Cretaceous alkaline and alkaline-carbonatitic complexes from southern Brazil are located along the main tectonic lineaments of the South America Platform. Calcium-, magnesium-, and ferrocarbonatites are well represented and frequently associated even in the same complex. Primary carbonates present significant variations in C-O isotopic compositions, which are mainly due to isotope exchange with H2O-CO2-rich hydrothermal fluids, whereas fractional crystallization or liquid immiscibility probably affects the δ18O and δ13C values by no more than 2δ‰. Our isotope exchange model implies that the most significant isotopic variations took place in a hydrothermal environment, e.g., in the range 400-80°C, involving fluids with the CO2/H2O ratio ranging from 0.8 to 1. Sr-Nd-Pb isotope systematics highlight heterogeneous mixtures between HIMU and EMI mantle components, similar to the associated alkaline rocks and the flood tholeiites from southern Brazil. In spite of the strong variation shown by C-O isotopes, Sr-Nd-Pb-Os isotopic systematics could be related to an isotopically enriched source where the chemical heterogeneities reflect a depleted mantle metasomatized by small-volume melts and fluids rich in incompatible elements. These fluids are expected to have promoted crystallization of K-rich phases in the mantle, which produced a veined network variously enriched in LILE and LREE. The newly formed veins (enriched component) and peridotite matrix (depleted component) underwent a different isotopic evolution with time as reflected by the carbonatites. These conclusions may be extended to the whole Paraná-Etendeka system, where isotopically distinct parent magmas were generated following two main enrichment events of the subcontinental lithospheric mantle at 2.0-1.4 and 1.0-0.5 Ga, respectively, as also supported by Re-Os systematics. The mantle sources preserved the isotopic heterogeneities over a long time, suggesting a nonconvective lithospheric mantle beneath different cratons or intercratonic regions. Overall, the data indicate that the alkaline-carbonatitic magmatism originated from a locally heterogeneous subcontinental mantle