Simultaneous determinations of zirconium, hafnium, yttrium and lanthanides in seawater according to a co-precipitation technique onto iron-hydroxide

Very low concentrations (pg mL 1 or sub-pg mL 1 level) along with the high salinity are the main problems in determining trace metal contents in seawater. This problem is mainly considered for investigations of naturally occurring YLOID (Y and Lanthanides) and Zr and Hf in order to provide precise and accurate results. The inductively coupled plasma mass spectrometry (ICP-MS), both in high and low resolution, offers many advantages including simultaneous analyses of all elements and their quantitative determination with detection limits of the order of pg mL 1. However in the analysis of YLOID in seawater, a better determination needs an efficient combination of ICP-MS measurement with a preconcentration technique. To perform an ultra-trace analysis in seawater, we have validated an analytical procedure involving an improved modified co-precipitation on iron hydroxides to ensure the simultaneous quantitative recovery of YLOID, Zr and Hf contents with measurement by a quadrupole ICP-MS. The validity of the method was assessed through a series of co-precipitation experiments and estimation of several quality control parameters for method validation, namely working range and its linearity, detection limit, quantification limit, precision and spike recoveries, and the methodological blank choice, are introduced, evaluated and discussed. Analysis of NASS-6, is the first report on the latest seawater reference material for YLOID, hafnium and zirconium

Weathering of evaporites: natural versus anthropogenic signature on the composition of river waters

Weathering of evaporites strongly influences the chemistry of continental runoff, making surface waters poorly exploitable for civil uses. In south-central Sicily, this phenomenon is worsened by the occurrence of abandoned landfills of old sulphur and salt mines. The industrial evolution of the Bosco-S. Cataldo mining site leaved two landfills from the early exploitation of a sulphur mine followed by that of a kainite deposit. In particular, the weathering of these landfills leads the dissolved salt (TDS) values up to about 200 g l−1 in the Stincone–Salito Stream waters. This process induces the V, Cr and Fe desorption from sediments and particulates in the aqueous phase under reducing conditions. At the same time, the weathering of salt minerals releases Rb and Cs, originally contained in halite. The overall processes lead to the V, Cr, Fe, Rb and Cs enrichment of waters from the Stincone–Salito Stream system accompanied by a sharp growth of As content, up to about 13 µg l−1, caused by As release from Fe-bearing solids due to the high salinity. Therefore, the scenario of the weathering of Bosco-S. Cataldo mine landfills depicts an environment strongly influenced by effects of the growing salinity and euxinic water conditions where the attained TDS, Eh and pH conditions reduce the natural scavenging capability of the interested river system, favouring a growth of residence time of toxic elements in river waters

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

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

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

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

Geochemistry of REE, Zr and Hf in a wide range of pH and water composition: The Nevado del Ruiz volcano-hydrothermal system (Colombia)

The geochemical behaviour of Rare Earth Elements, Zr and Hf was investigated in the thermal waters of Nevado del Ruiz volcano system. A wide range of pH, between 1.0 and 8.8, characterizes these fluids. The acidicwaters are sulphate dominatedwith different Cl/SO4 ratios. The important role of the pH and the ionic complexes for the distribution of REE, Zr and Hf in the aqueous phase was evidenced. The pH rules the precipitation of authigenic Fe and Al oxyhydroxides producing changes in REE, Zr, Hf amounts and strong anomalies of Cerium. The precipitation of alunite and jarosite removes LREE from the solution, changing the REE distribution in acidic waters. Y-Ho and Zr-Hf (twin pairs) have a different behaviour in strong acidic waterswith respect to the water with pH near-neutral. Yttrium and Ho behave as Zr and Hf in waters with pH near neutral-to-neutral, showing superchondritic ratios. The twin pairs showed to be sensitive to the co-precipitation and/or adsorption onto the surface of authigenic particulate (Fe-, Al-oxyhydroxides), suggesting an enhanced scavenging of Ho and Hf with respect to Y and Zr, leading to superchondritic values. In acidic waters, a different behaviour of twin pairs occurs with chondritic Y/Ho ratios and sub-chondritic Zr/Hf ratios. For the first time, Zr and Hf were investigated in natural acidic fluids to understand the behaviour of these elements in extreme acidic conditions and different major anion chemistry. Zr/Hf molar ratio changes from 4.75 to 49.29 in water with pH < 3.6. In strong acidic waters the fractionation of Zr and Hf was recognized as function of major anion contents (Cl and SO4), suggesting the formation of complexes leading to sub-chondritic Zr/Hf molar ratios