The behaviour of REEs in Thailand's Mae Klong estuary: Suggestions from the Y/Ho ratios and lanthanide tetrad effects

Abstract The concentrations of Rare Earth Elements and yttrium (REY) were measured in dissolved phase, in suspended particulate matter (SPM) and in sediments in seven sampling stations in the Mae Klong estuarine system (Inner Thailand Gulf) in order to study their behaviour and distribution pattern. The analysed samples generally show high Rare Earth Element (REE) content in the dissolved phase, with high Medium Rare Earth Elements (MREEs) and Y enrichments in the shale-normalized pattern (versus PAAS). These chemical features are interpreted in terms of direct influences of weathering processes of REE-rich minerals (e.g., phosphates), which abundantly out-crop in the Mae Klong watershed. T…

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 cond…

Geochemical characteristics of Cretaceous carbonatites from Angola

Abstract The Early Cretaceous (138–130 Ma) carbonatites and associated alkaline rocks of Angola belong to the Parana-Angola-Etendeka Province and occur as ring complexes and other central-type intrusions along northeast trending tectonic lineaments, parallel to the trend of coeval Namibian alkaline complexes. Most of the Angolan carbonatite-alkaline bodies are located along the apical part of the Mocamedes Arch, a structure representing the African counterpart of the Ponta Grossa Arch in southern Brazil, where several alkaline-carbonatite complexes were also emplaced in the Early Cretaceous. Geochemical and isotopic (C, 0, Sr and Nd) characteristics determined for five carbonatitic occurren…

Zirconium–hafnium and rare earth element signatures discriminating the effect of atmospheric fallout from hydrothermal input in volcanic lake water

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 a nd 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…

Rare earths behaviour during the deposition of volcanic sublimates

Abstract In this study, the REE distribution between volcanic fluids and related solids in fumaroles with temperatures ranging from approximately 100 to 421 °C was investigated in different geological scenarios. The treatment of geochemical REE data was carried out by calculating the REE enrichment factors (EF REE ) relative to the volcanic host rocks in studied sites under the assumption that the REE transport takes place as silicate aerosol in volcanic fluids. Shale-normalised REE concentrations in these fluids have been assessed to investigate whether the REE transport as aqueous complexes in water-saturated volcanic gas is reasonable. The REE behaviour in alkaline condensates according …

Potassic and sodic igneous rocks from eastern Paraguay: their origin from the lithospheric mantle and genetic relationships with the associated Paraná flood tholeiites

3 DIPARTIMENTO DI SCIENZE DELLA TERRA, UNIVERSITY OF TRIESTE, VIA E. WEISS 8, I-34127 TRIESTE, ITALY 4 INSTITUTO DE GEOCIENCIAS, UNIVERSIDADE DE SAO PAULO, C.P. 30627, 01051 SAO PAULO, SP, BRAZIL 5 DIPARTIMENTO DI SCIENZE DELLA TERRA, ‘LA SAPIENZA’ UNIVERSITY, PIAZZALE ALDO MORO 5, I-00185, ROME, ITALY 6 ISTITUTO DI MINERALOGIA, PETROGRAFIA E GEOCHIMICA, UNIVERSITY OF PALERMO, VIA ARCHIRAFI 36, I-90100,

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 ma…

Medical Geochemistry

Preface.- How trace element contents in bronchoalveolar lavages can probe the human exposure to inhaled particulates.- Geochemistry and Biochemistry - insights into the fate and transport of Pt-based chemotherapy drugs.- Atmospheric Particulate Matter (PM) in the Middle East: Toxicity, trans-boundary transport and influence of synoptic conditions.- Reaction path modeling: theoretical aspects and applications.- An observation on the composition of urinary calculi: environment influence.- Magnetite minerals in the human brain: what's their role?.- Chemometrics and Medical Geochemistry: A brief tutorial.- Dust, metals and metalloids in the environment: from air to hair.- Metal Geochemistry of …

Variability in the vertical structure of the water column and paleoproductivity reconstruction in the central-western Mediterranean during the Late Pleistocene.

Abstract A sedimentary sequence spanning Marine Isotope Stage (MIS) 6 to MIS 2 in core LC07, recovered in the central Mediterranean, has been investigated in order to produce a high-resolution paleoceanographic reconstruction. The changes in productivity deduced from calcareous plankton relative abundances and independently confirmed by the Ba XS fluctuations are linked to the stability of the water column which is mainly controlled by the water mass temperature. During glacial intervals, productivity was generally enhanced. Oligotrophic and warmer water masses with a deepened seasonal thermocline can be inferred for most of MIS5. The magnetic properties of the sediment show increased occur…

Mineralogical and chemical variability of fluvial sediments: 1. Bedload sand (Ganga–Brahmaputra, Bangladesh)

This study investigates the natural processes that control concentration of detrital minerals and consequently chemical elements in river sand. The novelty of our approach consists in the systematic integration of detailed textural, petrographical, mineralogical and chemical data, and in the quantitative description and modeling of relationships among mineralogical and chemical variables for each sample and each grain-size class in each sample. Bed sediment in transit in the largest sedimentary system on Earth chiefly consists of fine-grained lithofeldspatho quartzose sand including rich amphibole–epidote–garnet suites, mixed with minor very-fine grained-sand to silt subpopulations containi…

Trace element measurements on selected reference materials using HR-ICP-MS after microwave digestion. An application to Cultural Heritage

Zr- Hf Fractionation During Water-Rock Interaction

International audience; Zr and Hf are two elements having same ionic charge and similar ionic size at a given coordination number. Despite the Zr/Hf ratio is considered to be quite constant in meteorites and lithospheric rocks, seawaters collected from the surface down to varying depths of several Pacific Ocean stations reveal that the Zr/Hf ratio increases by one order of magnitude. Very recent studies have shown that, in both ground waters and lake waters, the Zr/Hf ratio is either higher or lower compared to the interacting minerals displaying a large variability in the distribution of these twin elements. In this communication the possible processes responsible for such a large fraction…

Behavior of rare earth elements in an aquifer perturbed by CO2 injection: Environmental implications

International audience; Three cubic-meters of CO2-saturated water was injected into a subsurface fractured aquifer in a post-mined area, using a push-pull test protocol. Groundwater samples were collected before and after CO2-injection to quantify geochemical changes. CO2-injection initially reduced the pH of water from 7.3 to 5.7, led to the enrichment of major ions (Ca2+, Mg2+, and alkalinity), and dissolved trace metals (including Fe, Mn, As, and Zn) in the groundwater. Rare earth elements (REE) and yttrium concentrations were also measured in these samples before and after CO2 perturbation, to evaluate their behavior. An enrichment of total Y plus REE (REY) occurred. REY fractionation w…

Standardization and validation of a new method based on pre-concentration techniques

Geochemistry of Zr, Hf, and REE in a wide spectrum of Eh and water composition: The case of Dead Sea Fault system (Israel)

International audience; Along the Jordan Valley-Dead Sea Fault area several natural waters in springs, wells, and catchments occur. The chemical-physical characters of the studied waters allowed for the first time the investigation of the Zr and Hf geochemical behavior, apart from REE, extended to a wide range of Eh, temperature, salinity, and pH conditions. The results of this study indicate that the dissolved Zr and Hf distribution in natural waters is strongly influenced by redox conditions since these in turn drive the deposition of Fe-oxyhydroxides or pyrite. In oxidizing waters saturated or oversaturated in Fe-oxyhydroxides (Group 1), superchondritic Zr/Hf values are measured. On the …

Relationship between lanthanide contents in aquatic turtles and environmental exposures

International audience; Trace elements released in the environment during agricultural practices can be incorporated and accumulated in biological fluids and tissues of living organisms. The assessment of these exposures were carried out investigating lanthanide distributions in blood and exoskeleton samples collected from Emys trinacris turtle specimens coming from sites with anthropogenic discharge in western and south Sicily, along migration paths of many bird species from Africa to Europe. The data show a significant (Rxy = 0.72; Rxy > 0.67; α = 0.025) linear relationship between the size of turtle specimens and the lanthanide contents in blood lower than 0.4 μg L−1 whereas this relatio…

Carbonatites fron southeastern Brazil: geochemistry, O-C, Sr-Nd-Pb isotopes and relationships with the magmatism from the Paranà-Angola-Namibia Province.

Calcareous nannofossil surface sediment assemblages from the SicilyChannel (central Mediterranean Sea): palaeoceanographic implications.

Quantitative analysis of 67 calcareous nannofossil assemblages from surface sediments recovered in a wide area across the Sicily Channel has been carried out in order to improve the interpretation of palaeontological data based on this planktonic group in a key area for Mediterranean palaeoceanographic studies. The investigation focused on three case studies that demonstrate the high potentiality of such a combined approach, taking into account the recent distribution of taxa or groups of taxa on the sea floor and the palaeontological record. The distribution of reworked specimens over the northern Sicily Channel sea floor validates the role of southern Sicily as a source region for reworke…

YTTRIUM AND REE SIGNATURE RECOGNIZED IN CENTRAL MEDITERRANEAN SEA (ODP SITE 963) DURING THE MIS 6 – MIS 5 TRANSITION

The Mediterranean Sea acts as a miniature ocean with the development of its own conveyor belt. It constitutes an ideal location to study and forecast how the marine environment responds to rapid climatic change. Here we present a palaeoenvironmental study carried out on the sediments of ODP Site 963, recovered in the Sicily Channel, the sill which divides the western from the eastern Mediterranean basin. We focused on the transition between the penultimate glacial (MIS 6) and the last interglacial (MIS 5), between approximately 130 and 115 kyr BP. A novel approach is proposed, taking into account centennial-scale geochemical data on major elements, selected trace elements, and yttrium and R…

Influence of pH and temperature on the early stage of mica alteration

Mineral dissolution and precipitation reactions actively participate in controlling fluid chemistry during water–rock interaction. In this study, the changes in the biotite and muscovite basal surface nano-morphology were evaluated during interaction with fluids of different pH (pH = 1.1, 3.3 and 5.7) at different temperatures (T =2 5, 120, and 200 C). Results show that at the nanometre scale resolution of the atomic force microscope (AFM), dissolution generates etch pits with a stair-shaped pattern over the (0 0 1) surface. The flux of dissolved elements decreases when pH increases. However, at pH 5.7, a change was found in the flux after 42 h of reaction when abundant gibbsite and kaolini…

Textural, chemical and isotopic variations induced by hydrothermal fluids on mesozoic limestones in northwestern Sicily

The results are given of textural and compositional investigations carried out on carbonate materials outcropping in various localities in northwestern Sicily where fluorite, barite and calcite mineralizations of hydrothermal origin occur. Observation of the textural features indicate variations in the degree of calcite recrystallization and silicification that appear to be more marked in rocks that show more evident effects of mineralization. The geochemical behaviour of the minor elements indicate variations in chemical composition (increase of Mn, Fe, and Sr and removal of Mg) as a result of interactions between mineralizing fluids and host-rocks. Comparison between the isotopic composit…

SOURCE RECOGNITION OF INHALED ATMOSPHERIC PARTICLES ACCORDING TO GEOCHEMICAL AND STATISTICAL EVALUATIONS OF TRACE ELEMENT SIGNATURES

During 2001 the Mount Etna had a large eruption producing a large amount of pyroclastic products consisting of a mixture of glass, minerals and soluble salt materials (SAF) encrusting solid particles. Inhalation of the finest of these materials induced pulmonary diseases in people living in subjected areas and gave us the possibility to collect bronchoalveolar lavages (BAL) from people in care in Catania hospitals. Concentrations of several trace elements measured in these BAL fluids (BALF) evidence strong enrichments in several trace elements compared to reference values. Related enrichments factors, calculated with respect to composition of volcanic ejecta (EFASH), show similar values in …

Rare earth elements distribution in seawater and suspended particulate of the Central Mediterranean Sea

Rare earth element (REE) content in suspended and dissolved phases from the Strait of Sicily (Central Mediterranean Sea) has been measured. Vertical profiles of several dissolved REEs along the water column reflect the 3-D oceanographic features of the studied area and identifies the different water masses present there. Shale-normalized REE distribution patterns and derived parameters calculated for the suspended particulate show different atmospheric dust-surface inputs and their interactions with seawater. Finally, combined information from [La/Yb]N, ratios, REE/La ratios and Eu anomalies measured in the suspended particulate suggest an important contribution of volcanic materials from t…

Distribution of Lanthanides in Mediterranean Coastal waters

Distribution and behaviour of the whole lanthanide series and yttrium in both seawater column and suspended particulate matter were investigated in coastal water located in the Central Mediterranean Sea. An area characterized by high anthropic pressure, atmospheric fallout and river input due to drainage of little local watersheds was selected. Water masses were discriminated with respect to both surrounding and depth and in relation to the processes occurring at the solid-liquid interface. We found that yttrium and Rare Earth Elements in the labile fraction of the suspended particulates result from the mixing between lithogenic material from the Sicilian basin and detrital material of Saha…

Trace element fractionation through halite crystallisation: Geochemical mechanisms and environmental implications

Halite is an important mineral for industry, agriculture and food production. It crystallises after water evaporation, while the progressive growth of dissolved metal ions in brines is occurring. Then, halite exploitation may provide the delivery of metal ions in the environment and the mechanism of this trace element accumulation should be studied. In this work we investigate the distribution of lanthanides and Y (hereafter named Rare Earth Elements, REE), Zr and Hf between crystallising halite and brines in the Dead Sea as geochemical tools for recognising the mechanism of metal ion removal from brines and accumulation in halite. Halite forms cubic crystals where octahedral planes sometim…

Zirconium and hafnium fractionation and distribution of Rare Earth Elements in neutral–alkaline waters: Case study of Lake Van hydrothermal system, Turkey

International audience; We investigated the distribution of Zr, Hf, and rare earth elements (REE) as the sum of lanthanides plus Y in the hydrothermal system in the Lake Van area of south-eastern Turkey. This system is characterised by water with variable pH in alkaline conditions resulting from hydrothermal CO2 upraise and neoformation of calcite minerals in near equilibrium with the interacting waters. Zr, Hf, and REE determinations were carried out for aqueous phases and suspended solids in lake water and surrounding thermal springs. We found that dissolved Hf is partitioned relative to Zr during calcite formation and that such fractionation is a function of the Ca2+ activity in warm wat…

Solid-liquid interactions in human lung system enhanced by yttrium and REE distribution in Broncho-alveolar lavages.

How trace element distributions can be used to probe human exposure to atmospheric fallout

Medical literature recognised several effects of human exposure to inhalation of air dispersed particles that could induce pulmonary diseases, but the hypothesis that reactions occurring between inhaled particles and human respiratory fluids could involve trace element leaching was poorly understood and only a scarce literature about in-vitro experiments suggested it. The present research was carried out on a group of volunteer patients exposed to the natural inhalation of atmospheric particles in a highly anthropized area close to Mt. Etna under explosive volcanic eruption in Summer 2001. Collected data shoed, for the first time, that the dissolution of inhaled solids influenced the chemis…

Rare earths and trace elements contents in leaves: A new indicator of the composition of atmospheric dust

The relationship between the trace element distribution in atmospheric particles and leaves of some exposed plants in the environment was recently demonstrated. This indication would suggest that the trace element analysis of leaves in these plants could provide information about the composition, nature and origin of the atmospheric dust dispersed in the environment. In order to corroborate this hypothesis, the distribution of trace elements and Rare Earths were studied in leaves of some endemic plants, in the atmospheric fallout and in soils of rural, urban and industrial ecosystems in Sicily. These elements have been chosen to discriminate the source and nature of different source on atmo…

TRACE ELEMENT BEHAVIOUR IN SEAWATER DURING PYROCLASTIC ETNA'S ACTIVITY IN 2001. CONCURRENT EFFECTS OF NUTRIENTS AND FORMATION OF ALTERATION MINERALS

From July 13 2001 began the most intense Etna's eruptive activity in the last 300 years. While this phenomenon occurred the oceanographic cruise ANSIC 01 was carrying out. Therefore the unique opportunity is arisen to investigate the chemical effects on marine system of delivery of large amount of pyroclastic particles (about 1 g m-2) into seawater. Comparing collected trace element data with those analysed during the oceanographic cruise JUVENILE 99, carried out two years before, large enrichments in V, Cr, Mn, Fe, Co, Cu and Pb contents have been recognised and attributed to leaching of freshly-erupted volcanic ash. Further comparison between to-day and previous collected trace element da…

Carbonatites from the Southern Brazilian platform: I

We present a comprehensive overview of the geochemical characteristics and evolution of the carbonatites from the southern Brazilian Platform (Paraná Basin). The carbonatites from different complexes display large compositional variability in terms of abundances of incompatible and rare earth elements. This is in agreement with an origin from heterogeneous lithospheric sources, as confirmed by isotopic data (see Speziale et al., this issue). The characteristic major and trace element abundances of these carbonatites present compelling evidence for invoking liquid unmixing as the main mechanism of their formation and evolution albeit few exceptions. We propose an evolutionary trend for the B…

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

AbstractRare 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,…

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 wit…

Alkaline complexes from Alto Paraguay Province at the border between Brazil (Mato Grosso do Sul State) and Paraguay.

The behaviour of zirconium and hafnium during water-rock interaction

Abstract Zr and Hf are two elements with same ionic charge and similar ionic size at a given coordination number. Despite the Zr/Hf ratio is quite constant in meteorites and lithospheric rocks, in natural waters can be either higher or lower compared to values of interacting minerals and rocks. Here, we reanalyze very recent published and present new data on continental and brine waters indicating that the Zr and Hf behavior is dependent on the properties of the authigenic phases formed during the water-rock interaction process. Our results show that water pH in the range between 1 and 9 and water ionic strength in the range between 0.001 and 4 mol kg−1 are responsible for the change of the…

CHLORITE/SMECTITE - ALKALI FELDSPAR METASOMATIC XENOLITHS FROM HYBLEAN MIOCENIC DIATREMES (SICILY, ITALY): EVIDENCE FOR EARLY INTERACTION BETWEEN HYDROTHERMAL BRINES AND ULTRAMAFIC/MAFIC ROCKS AT CRUSTAL LEVELS

Upper-Miocene tuff-breccia pipes from the Hyblean area (south-eastern Sicily) bear a number of ultramafic and mafic xenoliths (spinel-peridotites, pyroxenites, gabbroic rocks) whose study has led to conclude that the Meso-Caenozoic carbonatic and volcanic succession stands upon a fossil oceanic core-complex, probably connected with the adjacent Ionian crust. Evidence for hydrothermal metasomatism is common in the Hyblean ultramafic and mafic xenoliths. In some cases, extreme metasomatic transformation and shearing have deleted original mineralogy and textures yielding unusual rocks, hereafter called “metasomatites”. These rocks generally exhibit cataclastic texture, their hydrothermal miner…

Natural gadolinium discharge from volcanic sources

Although a large fraction of chemicals is provided from volcanic fluids to the environment (Oppenheimer et al., 2014) only a scarce literature was focused on the Rare Earth elements (REE) release from high temperature fumaroles (Möller et al., 2003; Gilbert & Williams-Jones, 2008; Zelenski et al., 2013). In order to fill this gap, this research was carried out mainly taking in account the REE partitioning during the emissions of fumarolic fluid between newly-forming sublimates and the remaining gas phase. The latter was collected as alkaline condensates according to Sortino et al. (2006). The investigated high temperature fumaroles (95-450°C) occur in several volcanic systems at Vulcano (Ae…

The behaviour of zirconium, hafnium and rare earth elements during the crystallisation of halite and other salt minerals

Abstract Halite crystals from Messinian and Tortonian evaporites from Sicily and Spain and current precipitated halite crystals and the relative parent brines (active evaporation systems) were investigated in order to evaluate the Zr, Hf and Rare Earth Element (REE) behaviour. Halite crystallisation from evaporating brines fractionates Zr, Hf and REE through a two-step process. During the first step, dissolved complexes of studied elements are scavenged onto the surfaces of crystallising halite. During the second step, elements are co-precipitated into the crystal lattice as it grows. The first step mechanism is determined by the dissolved REE speciation. In saltworks where carbonate-REE co…

Determination of YLOID in soil and grapevine systems (Vitis vinifera L.) by ICP-MS technique: a hopeful proxy for the geographical characterization of food products?

Chemical behavior of YLOID (Y and Lanthanoid) into soil was extensively studied both to evaluate geochemical process. Metal cations can be immobilized onto particle surface of soil due to the formation of stable complexes with organic matter. If environmental conditions change metals can be mobilized and therefore to became bioavailable [1]. In recent years identification of the geographical origin of food has acquired very importance because consumers are more and more interested in knowing the provenance of the food purchased and/or eaten [2]. Then the knowledge of a relationship between the chemistry of the substrates and the food could be an important tool for the quality guarantee of t…

Geochemical behaviour of rare earths in Vitis vinifera grafted onto different rootstocks and growing on several soils.

The geochemical behaviour of lanthanides and yttrium (Rare Earth Elements, REEs) has been investigated mainly in geological systems where these elements represent the best proxies of processes involving the occurrence of an interface between different media. This behaviour is assessed according to features recorded in sequences of REE concentrations along the REE series normalised with respect to a reference material. In this study, the geochemical behaviour of REE was investigated in different parts of Vitis vinifera specimens grown off-soil, on soils of different nature and grafted onto several rootstocks in order to evaluate effects induced by these changes. The results indicated that ro…

Rapid migration of CO2-rich micro-fluids in calcite matrices

International audience; The transport of supercritical fluids is a determining factor for several geological processes and fundamental in predicting natural resource accumulation and distribution. Calcite, ubiquitous in most geological environments, may contain supercritical CO2 trapped under the form of fluid inclusions that may move through grain boundaries affecting the rock physical properties. However, despite macroscopic evidence for this process, until recent it was not possible to characterize this process at the nano-scale due to the difficulty of such observations. In this study, we report nanometer-scale observations on calcite crystal surfaces and demonstrate that stress with ab…

Geochemical characterisation of gases along the dead sea rift: Evidences of mantle-co2 degassing

International audience; The Dead Sea Transform (DST) fault system, where a lateral displacement between the African and Arabian plates occurs, is characterised by anomalous heat flux in the Israeli area close to the border with Syria and Jordan. The concentration of He and CO2, and isotopic composition of He and total dissolved inorganic carbon were studied in cold and thermal waters collected along the DST, in order to investigate the source of volatiles and their relationship with the tectonic framework of the DST. The waters with higher temperature (up to 57.2 °C) are characterised by higher amounts of CO2 and helium (up to 55.72 and 1.91 * 10-2 cc l-1, respectively). Helium isotopic dat…

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 ana…

Distribution of rare earth elements in marine sediments from the Strait of Sicily (western Mediterranean Sea): Evidence of phosphogypsum waste contamination

Concentrations of rare earth elements (REE), Y, Th and Sc were recently determined in marine sediments collected using a box corer along two onshore–offshore transects located in the Strait of Sicily (Mediterranean Sea). The REE + Y were enriched in offshore fine-grained sediments where clay minerals are abundant, whereas the REE + Y contents were lower in onshore coarse-grained sediments with high carbonate fractions. Considering this distribution trend, the onshore sediments in front of the southwestern Sicilian coast represent an anomaly with high REE + Y concentrations (mean value 163.4 lg g 1) associated to high Th concentrations (mean value 7.9 lg g 1). Plot of shale-normalized REE + …

A Multivariate geostatistical approach to the analysis of a sedimentological and petrophysical dataset: a case of study from the port of Naples.

Using the Trace Element Contents in Bronchoalveolar Lavages to Probe the Human Exposure to Inhaled Particulates

Explosive volcanic eruptions eject large volumes of high surface area, metal-rich dust and ash into the atmosphere. In areas near major volcanic eruptions, humans often interact with these materials and may bioaccumulate heavy and toxic metals. To evaluate these interactions, we examine bronchoalveolar lavage samples (BAL) collected from people exposed to the paroxysmal 2001 Etna eruption. BAL samples reveal a strong enrichment of many toxic heavy metals and the capacity for trace elements released from inhaled particles to induce crystallisation of phosphatic microcryst biominerals in intraaveolar spaces. BAL rare earth element (REE) concentration patterns normalised to shale reveal a ‘V-s…

Carbonate precipitation in the alkaline lake Specchio di Venere (Pantelleria Island, Italy) and the possible role of microbial mats

Abstract Alkaline lakes like the hydrothermally affected lake Specchio di Venere (Pantelleria Island, Central Mediterranean) are typical geological settings harbouring calcified microbial mats. The present work is focused on the discrimination between biotic and abiotic processes driving carbonate precipitation in this lake, using hydrochemical, mineralogical and isotopic data. Hydrochemical analyses demonstrate that the lake is nearly 10−fold supersaturated with regard to aragonite and seasonally reaches hydromagnesite supersaturation. Microscopic observations depict organosedimentary laminated structures consisting of microbial communities and aragonitic precipitates, which are rather dis…

Rare-earth elements and yttrium distributions in mangrove coastal water systems: The western Gulf of Thailand

The concentration of rare-earth elements and yttrium (REY) was investigated in dissolved phase, suspended particulate matter, and seafloor sediments of the western coastal area of the Gulf of Thailand. The samples show Eu and Gd positive anomalies in the shale-normalized REY patterns, especially in the suspended particulate matter. On the other hand, a very high REE content was detected in the coastal waters, probably due to the weathering produced by the Mae Klong river waters on rare-earth element (REE)-rich accessory minerals coming from terrains and mineral deposits cropping out in the studied area. The shale-normalized patterns of yttrium and REE estimated for the dissolved phase show …

La geoarcheometria applicata alla Conoscenza e alla Conservazione dei Beni Culurali. Un caso di studio: la facciata della chiesa di S. Nicolò l'Arena a Catania

Alkaline complexes fro Southeastern Bolivia.

Trace element behaviour in seawater during Etna's pyroclastic activity in 2001: Concurrent effects of nutrients and formation of alteration minerals

volcanic ash ; trace element leaching ; kinetic experiments ; chlorophyll-alpha; International audience; The eruption of Etna in Sicily on 13 July 2001 marked the most intense activity of the volcano in the last 300 years. The eruption occurred while the oceanographic cruise ANSIC 01 was being conducted to the east of Sicily, presenting a unique opportunity for the investigation of the chemical effects on the marine system during a period of significant (similar to 1 g m(-2)) ash deposition. Comparison of trace element data with measured concentrations from the oceanographic cruise JUVENILE 99, carried out two years before, indicates large enrichments of V. Cr, Mn, Fe, Co, Cu and Pb. We att…

Alkaline complexes from the Alto Paraguay Province at the border of Brazil (Mato Grosso do Sul State) and Paraguay.

Yttrium and REE signature recognized in Central Mediterranean Sea (ODP Site 963) during the MIS 6–MIS 5 transition

Abstract The Mediterranean Sea acts as a miniature ocean with the development of its own conveyor belt. It constitutes an ideal location to study and forecast how the marine environment responds to rapid climatic change. Here we present a palaeoenvironmental study carried out on the sediments of ODP Site 963, recovered in the Sicily Channel, the sill which divides the western from the eastern Mediterranean basin. We focused on the transition between the penultimate glacial (MIS 6) and the last interglacial (MIS 5), between approximately 130 and 115 kyr BP. A novel approach is proposed, taking into account centennial-scale geochemical data on major elements, selected trace elements, and yttr…

Heavy metals in coastal water systems. A case study from the northwestern Gulf of Thailand.

A geochemical survey of the northwestern part of the Thailand Gulf (Inner Gulf) was carried out in order to define concentrations and distribution patterns of selected heavy metals (V, Cr, Co, Ni, Cu, Zn, and U) in the coastal system and estuarine area of the Mae Klong river. The results indicate the presence of two different sources of heavy metals in the studied environment and allowed us to identify a lithogenic component that significantly influences the composition of coastal waters and suspended particulate matter (SPM). Comparison of the normalized heavy metals concentrations both in the studied samples and in those reported for the Sn–W ores present in the surrounding areas suggests…

Astronomical dating of two Pliocene alkaline volcanic ash layers in the Capo Rossello area (southern Sicily, Italy): implications for the beginning of the rifting in the Sicily Channel

Key-words. - Sicily Channel rift, Biostratigraphy, Astronomical calibration, Pliocene, Volcanic ash layers. Abstract. - Two volcaniclastic ash layers (AL1 and AL2) are intercalated throughout the middle Pliocene sedimentary sequences of Punta Piccola and Capo Rossello exposed along the south coast of Sicily (Italy). Astronomical calibration of the Punta Piccola section provided an age of 2.676 Ma for the deposition of the AL1 layer. The high-resolution bio-cyclostratigraphy of the Capo Rossello section, in combination with detailed correlations with previously astrono- mically calibrated coeval sequences, provided an age of 2.225 Ma for the deposition of the AL2 layer. Mineralogical, petrog…

Calcareous Nannofossil Assemblages from the Central Mediterranean over the last Four Centuries.

Effect of pyroclastic atmospheric fallout on YREE distribution in human bronchial washing solutions

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 pr…

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Authigenic phase formation and microbial activity control Zr, Hf, and rare earth element distributions in deep-sea brine sediments

Abstract. Sediments collected from hypersaline and anoxic deep-sea basins in the eastern Mediterranean (Thetis, Kryos, Medee, and Tyro) were characterised in terms of their mineralogical composition, the distributions of rare earth elements (REE), Zr, and Hf and their content of microbial DNA. We identified two major mineralogical fractions: one fraction of detritic origin was composed of quartz, gypsum, and low-Mg calcite bioclasts (with 0 < Mg < 0.07%) and another fraction of authigenic origin constituted of halite, dolomite, high-Mg calcite (with a Mg content of up to 22%) and rare bischofite and showed a textural evidence of microbial assemblages. We found that in the Medee and Ty…

Influence of dissolved organic matter on rare earth elements and yttrium distributions in coastal waters

International audience; Data collected during this study indicate that dissolved Y and REE (rare earth element) behaviour can be monitored through shale-normalised ratios. Relationships occurring between these ratios suggest that leaching from lithogenic materials is the main source of REE in the studied area. This process involves riverine detrital matter in the inner area of the Gulf of Palermo. Features of shale-normalised patterns and the relationship recognised between dissolved Fe and Y/Ho suggest that REE are released from Fe-rich coatings of atmospheric dust. Observed similarities between dissolved Fe and chlorophyll- content suggest that leaching of Fe-rich atmospheric particulates…

Carbonatites fron southeastern Brazil: a model for the carbon and oxygen isotope variations.

Yttrium and lanthanides in human lung fluids, probing the exposure to atmospheric fallout.

International audience; Inhalation of airborne particles can produce crystallization of phosphatic microcrysts in intraaveolar areas of lungs, sometimes degenerating into pulmonary fibrosis. Results of this study indicate that these pathologies are induced by interactions between lung fluids and inhaled atmospheric dust in people exposed to volcanic dust ejected from Mount Etna in 2001. Here, the lung solid-liquid interaction is evaluated by the distribution of yttrium and lanthanides (YLn) in fluid bronchoalveolar lavages on selected individuals according the classical geochemical approaches. We found that shale-normalised patterns of yttrium and lanthanides have a 'V shaped' feature corre…

Development of a biosensor for copper detection in aqueous solutions using an Anemonia sulcata recombinant GFP.

Fluorescent proteins from marine organisms represent potential candidates for biosensor development. In this paper, we described the isolation of a native green fluorescent protein from Anemonia sulcata and the cloning and purification of its equivalent as a recombinant protein in Escherichia coli. Furthermore, the spectroscopic behaviours of the native and recombinant GFPs were investigated as a function of Cu2+, Cd2+, Pb 2+ and Ni2+ concentration. Our results suggest the high selectivity of both proteins at copper than the other metals and, for the recombinant protein, a great sensitivity at a very low concentration (0.1-1 μM). Moreover, starting from these data, using the combination of …

Possible impacts of volcanic ash emissions of Mount Etna on the primary productivity in the oligotrophic Mediterranean Sea: Results from nutrient-release experiments in seawater

Atmospheric deposition of volcanic ash has recently been recognized as an important nutrient source into the surface ocean. Mount Etna (Italy), one of the world's most active volcanoes, is located in the oligotrophic Mediterranean Sea (MedSea). Despite the active volcanism on Mount Etna, the biogeochemical impacts of volcanic ash fallouts on the marine primary productivity (MPP) remain largely unknown. Here we present the results of seawater nutrient release experiments with volcanic ash samples from Mount Etna that have been collected during different eruptive episodes between 2001 and 2007. Our results show that volcanic ash from Mount Etna releases significant amounts of fixed-N (35-855 …

Zr/Hf ratio and REE behaviour: A coupled indication of lithogenic input in marginal basins and deep-sea brines

Abstract The distribution of dissolved Zr, Hf and Rare Earth Elements (yttrium and lanthanides, hereafter referred to as REE) in the Eastern Mediterranean seawater column was measured in the Kryos basin to evaluate the lithogenic contribution from both Nile River and Sahara and Arabian desert dust. We found dissolved Zr/Hf ratios below the signature of crustal rocks and chondrites; a phenomenon likely driven by the dissolution of the Mn-rich coating of atmospheric dust particles delivered from the desert. In deeper waters, Zr/Hf ratios are clustered close to the signature of crustal rocks and chondrites according to the different Zr and Hf dissolved speciation. The Zr/Hf ratio observed in t…

Alkaline complexes from Velasco and Candelaria, sounteastern Bolivia

Quantitative evaluation of Lanthanide release to seawater during sinking of atmospheric Fe-rich particles

The behavior of Rare-Earth Elements, Zr and Hf during biologically-mediated deposition of silica-stromatolites and carbonate-rich microbial mats

Abstract Venere Lake, in the Pantelleria Island thermal system (Central Mediterranean Sea) consists of a mix of seawater and hydrothermal volcanic fluids containing high levels of dissolved SiO 2 . Close to the lake's thermal springs, siliceous stromatolites are deposed under high bacterial activity conditions whereas roughly interlaminated Ca-carbonates and microbial mats are widely scattered in the lake. The dissolved REE speciation in lake waters is dominated by [REE(CO 3 ) 2 ] − , [REE(CO 3 )] + and [REE(H 3 SiO 4 )] 2 + complexes. On the contrary the most abundant Zr and Hf species are hydroxyl- and fluoride-complexes. The behavior of REE Zr and Hf in the Venere lake waters is controll…

Potassic dyke swarm in the Sapucai Graben, Eastern Paraguay: Petrographical, mineralogical and geochemical outlines.

Abstract The western side of the Parana Basin of Brazil extends to central Paraguay, where repeated and widespread magmatic activity developed from Lower Cretaceous to Oligocene, associated with late Mesozoic crustal extension trending NE-SW. In central Paraguay this trend is characterized by a zone of NW-SE normal faults which formed the Asuncion-Sapucai graben, up to 45 km wide and 200 km long, where alkaline rocks occur as volcanic domes, complexes, lava-flows and dykes. These rocks, 128 Ma aged, are dominantly potassic and ne-normative. A swarm of at least 200, mainley NW-SE trending, dykes occurs in the Sapucai region and seems to be formed by two main lineages: tephrite to phonolite (…

Zr, Hf and REE distribution in river water under different ionic strength conditions

International audience; The Platani River flowing in south-central Sicily, interacting with evaporite rocks, generates a wide range of ionic strength in the water catchment from 0.1 to 5.0 mol kg−1. We sampled 38 river sites and analysed the composition for the dissolved fraction filtered through 0.45 μm, the truly dissolved fraction obtained through ultrafiltration (10 kDa) and the relative included colloidal fraction.This study was focused on the recognition of Zr, Hf and REE behaviour under changing ionic strength conditions, since this is one of parameters responsible for colloid stability in natural waters. In turn, this phenomenon leads to REE release from the colloidal fraction and t…

Recognition of water masses according to geochemical signatures in the Central Mediterranean sea: Y/Ho ratio and rare earth element behaviour

This study reports the results of geochemical investigations carried out in the Strait of Sicily (Central Mediterranean Sea) during the oceanographic cruise BANSIC 2000, focusing on the area around the Pantelleria Island. We evaluate the interface processes between dissolved phase and suspended particulate matter in the water columns on the basis of Y/Ho ratio and rare earth elements and yttrium distributions that are suitable to trace the occurrence of different water layers in Central Mediterranean Area. The main source of trace elements to the sea water system was recognized in the atmospheric fallout, while different scavenging mechanisms among Y and rare earth elements occur. Cation ex…

Lo stato dell’ambiente marino nell’area del Canale di Sicilia in prossimità del SIN di Gela.

Viene illustrata in questa nota l’attuale condizione in cui si trova lo stato dell’ambiente marino nell’area del Canale di Sicilia immediatamente a ridosso della costa merdionale delle Sicilia dal Golfo di Gela alla costa iblea. Lo stato dell’ambiente in oggetto viene valutato in base alla distribuzione di alcuni metalli in tracce normalmente ritenuti fra i più significativi per gli scopi prefissati, esaminati lungo la colonna d’acqua e nei sedimenti superficiali di fondale. I risultati ottenuti, illustrati anche attraverso un’indagine statistica multivariata, indicano un arricchimento superficiale della colonna d’acqua in lantanio che può essere ascritto tanto ad un’origine litogenica, qua…

Behaviour of Zr/Hf and Y/Ho ratios during transition between seawater column and deep-sea brines

Escape of Supercritical-CO2 Fluids Trapped in Calcite Nano-metric Pores

Flow of supercritical CO2-bearing fluids through a rock is a fundamental phenomenon which acts upon a great many geological processes ranging from seismic activity to formation of ore deposits. Atomic Force Microscopy scanning experiments allowed us to infer movement of supercritical CO2-bearing fluids through calcite crystals and relate it to natural decrepitation of nanoscale fluid inclusions. Calculated velocities exceed the rate of diffusion predicated via current vacancy models by several orders of magnitude implying that CO2-rich fluid movement through micro and nano-pore space may presently be greatly underestimated.

The geochemistry of the Barra do Itapirapua carbonatite (Ponta Grossa Arch, Brazil): a multiple stockwork

The Early Cretaceous Barra do Itapirapuā carbonatite, in southern Brazil, belongs to the initial stages of the alkaline carbonatitic magmatism in the Ponta Grossa Arch Province, as related to the opening of the south Atlantic Ocean. The magmatic evolution of the complex comprises four phases of intrusive carbonatite that are composed of medium- to coarse-grained Mg and Fe carbonatites with small volumes of late fine- to very fine-grained Mg carbonatites and show evidence of pervasive hydrothermal events. Drill core samples reveal the existence of silicate rocks of syenitic composition of two different origins. Among the silicate rocks, there are syenites of a likely magmatic origin, as well…

A review of carbonatitic magmatism in the Paraná-Angloa-Etendeka system

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

International audience; 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 acidic waters are sulphate dominated with 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 Z…

Effects of Dissolved Complexation on REE Fate During Interactions between Volcanic Ash and Coexisting Fluids

AbstractThis work analyzes REE behavior during the delivery of volcanic ash into a marine system and highlights the effects induced by dissolved carbonate and humate complexes on REE release. Kinetic experiments were carried out during a 6-month period using a batch method approach. Results show that the highest degree of REE leaching occurs during the early stage. Altered phases that crystallize induce REE sorption and dissolved complexation towards surface complexation, concurrent processes that are enhanced by Y/Ho, La/Yb, and Ce/Ce* changes, whereas dissolved humates and carbonates influence the dissolution rate of ash and the dissolved REE behavior.

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…

Source and Nature of Inhaled Atmospheric Dust from Trace Element Analyses of Human Bronchial Fluids

International audience; Rapid volcanic eruptions quickly ejecting large amounts of dust provoke the accumulation of heavy metals in people living in surrounding areas. Analyses of bronchoalveolar lavage samples (BAL) collected from people exposed to the paroxysmal 2001 Etna eruption revealed a strong enrichment of many toxic heavy metals. Comparing the BAL to the dust composition of southeastern Sicily, we found that only V, Cr, Mn, Fe, Co, and U enrichment could be related to the volcanic event, whereas Ni, Cu, Cd, and Pb contents come from the dissolution of particles of anthropogenic origin. Furthermore, the nature of these inhaled anthropogenic particles was revealed by anomalous La and…

(Table 1) Geochemistry of ODP Site 160-963 sediments

The Mediterranean Sea acts as a miniature ocean with the development of its own conveyor belt. It constitutes an ideal location to study and forecast how the marine environment responds to rapid climatic change. Here we present a palaeoenvironmental study carried out on the sediments of ODP Site 963, recovered in the Sicily Channel, the sill which divides the western from the eastern Mediterranean basin. We focused on the transition between the penultimate glacial (MIS 6) and the last interglacial (MIS 5), between approximately 130 and 115 kyr BP. A novel approach is proposed, taking into account centennial-scale geochemical data on major elements, selected trace elements, and yttrium and R…