Different lead sources in an abandoned uranium mine (Urgeirica - Central Portugal) and its environment impact - isotopic evidence

Different lead sources were identified in a large uranium tailings deposit (5Mton) in the Central Region of Portugal using lead isotopic ratios obtained by ICP-QMS. These ratios helped to clarify the different sources of Pb within the tailings deposit and the impact of the tailings on the surroundings. Ten depth profiles were used for isotopic characterization of the tailings deposit; the lead background signature was evaluated in seven regional rocks (granites) and was defined as being 28 +/- 1 mg kg(-1) for Pb bulk concentration and with isotopic ratios of 1.264(2) for Pb-206/Pb-207 and 1.962(7) for Pb-208/Pb-206. In order to understand Pb isotope distribution within the tailings deposit, simple mixing/mass balance models were used to fit experimental data, involving: (1) the background component; (2) uranium ores (pitchblende) characterized by the ratios Pb-206/Pb-207 of 1.914(3) and Pb-208/Pb-206 of 1.235(2); and (3) an unknown Pb source (named 'Fonte 5') characterized by the ratios Pb-206/Pb-207 of 3.079(7) and Pb-208/Pb-206 of 0.715(1). This unknown source showed high radiogenic ratios found in the water of some tailings depth profiles located in a very specific position in the dump. In terms of isotopic characterization, 69% of the deposit material resulted from the background source, 25% from uranium minerals and only 6% from other uranium mines in the region. Finally, the environment impact revealed that the pollution was focused only in the beginning of the stream and not in the surroundings, nor in the groundwater system. The lead in the water was found only in colloidal form with a clear pitchblende signature. Those data revealed possible remobilization phenomena along the bedside and margins of the watercourse.

Bioelectrical impedance with different equations versus deuterium oxide dilution method for the inference of body composition in healthy older persons

There is no consensus regarding the accuracy of bioimpedance for the determination of body composition in older persons. This study aimed to compare the assessment of lean body mass of healthy older volunteers obtained by the deuterium dilution method (reference) with those obtained by two frequently used bioelectrical impedance formulas and one formula specifically developed for a Latin-American population. A cross-sectional study. Twenty one volunteers were studied, 12 women, with mean age 72 +/- 6.7 years. Urban community, Ribeiro Preto, Brazil. Fat free mass was determined, simultaneously, by the deuterium dilution method and bioelectrical impedance; results were compared. In bioelectrical impedance, body composition was calculated by the formulas of Deuremberg, Lukaski and Bolonchuck and Valencia et al. Lean body mass of the studied volunteers, as determined by bioelectrical impedance was 37.8 +/- 9.2 kg by the application of the Lukaski e Bolonchuk formula, 37.4 +/- 9.3 kg (Deuremberg) and 43.2 +/- 8.9 kg (Valencia et. al.). The results were significantly correlated to those obtained by the deuterium dilution method (41.6 +/- 9.3 Kg), with r=0.963, 0.932 and 0.971, respectively. Lean body mass obtained by the Valencia formula was the most accurate. In this study, lean body mass of older persons obtained by the bioelectrical impedance method showed good correlation with the values obtained by the deuterium dilution method. The formula of Valencia et al., developed for a Latin-American population, showed the best accuracy.

Evaluation of Inductively Coupled Plasma Mass Spectrometry for Determining Ca, Cu, Fe, Mg, Mn, Se and Zn in Bovine Semen Samples using a Simple Sample Dilution Method

A simple and fast method for the determination of Ca, Cu, Fe, Mg, Mn, Se and Zn in bovine semen by quadrupole inductively coupled plasma spectrometry (q-ICP-MS) is described. Prior to analysis, samples (200 mu L) were diluted 1:50 in a solution containing 0.01% v/v Triton (R) X-100 and 0.5% v/v nitric acid and directly analyzed by ICP-MS. The limits of detection of the method are 0.3, 0.03, 0.2, 0.04, 0.04, 0.03 and 0.03 mu g L-1 for Ca-44, Cu-63, Fe-57, Mg-24, Zn-64, Se-82 and Mn-55, respectively. For purposes of comparison and method validation, four ordinary bovine semen samples were directly analyzed by ICP-MS and by flame atomic absorption spectrometry (FAAS) or graphite furnace atomic absorption spectrometry (GF AAS), with no statistical difference between the techniques at the 95% level when applying the t-test. Then, the proposed method was applied in the determinations of Ca, Cu, Fe, Mg, Mn, Se and Zn in collected samples of bovine semen from different breeds, which are used in reproduction programs and artificial insemination.

Evaluation of inductively coupled plasma mass spectrometry for determining Ca, Cu, Fe, Mg, Mn, Se and Zn in bovine semen samples using a simple sample dilution method

A simple and fast method for the determination of Ca, Cu, Fe, Mg, Mn, Se and Zn in bovine semen by quadrupole inductively coupled plasma spectrometry (q-ICP-MS) is described. Prior to analysis, samples (200 µL) were diluted 1:50 in a solution containing 0.01% v/v Triton® X-100 and 0.5% v/v nitric acid and directly analyzed by ICP-MS. The limits of detection of the method are 0.3, 0.03, 0.2, 0.04, 0.04, 0.03 and 0.03 µg L-1 for 44Ca, 63Cu, 57Fe, 24Mg, 64Zn, 82Se and 55Mn, respectively. For purposes of comparison and method validation, four ordinary bovine semen samples were directly analyzed by ICP-MS and by flame atomic absorption spectrometry (FAAS) or graphite furnace atomic absorption spectrometry (GF AAS), with no statistical difference between the techniques at the 95% level when applying the t-test. Then, the proposed method was applied in the determinations of Ca, Cu, Fe, Mg, Mn, Se and Zn in collected samples of bovine semen from different breeds, which are used in reproduction programs and artificial insemination.

Dilution and dispersión of Gran Canaria desalinitation plant brine discharge: influence on seagrass meadows and potential corrective measures

Programa de doctorado en oceanografía

High-resolution stratigraphy of Central and Southern Adriatic Quaternary deposits of sub-Milankovian climate change on Mediterranean circulation

This volume is a collection of the work done in a three years-lasting PhD, focused in the analysis of Central and Southern Adriatic marine sediments, deriving from the collection of a borehole and many cores, achieved thanks to the good seismic-stratigraphic knowledge of the study area. The work was made out within European projects EC-EURODELTA (coordinated by Fabio Trincardi, ISMAR-CNR), EC-EUROSTRATAFORM (coordinated by Phil P. E. Weaver, NOC, UK), and PROMESS1 (coordinated by Serge Bernè, IFREMER, France). The analysed sedimentary successions presented highly expanded stratigraphic intervals, particularly for the last 400 kyr, 60 kyr and 6 kyr BP. These three different time-intervals resulted in a tri-partition of the PhD thesis. The study consisted of the analysis of planktic and benthic foraminifers’ assemblages (more than 560 samples analysed), as well as in preparing the material for oxygen and carbon stable isotope analyses, and interpreting and discussing the obtained dataset. The chronologic framework of the last 400 kyr was achieved for borehole PRAD1-2 (within the work-package WP6 of PROMESS1 project), collected in 186.5 m water depth. The proposed chronology derives from a multi-disciplinary approach, consisting of the integration of numerous and independent proxies, some of which analysed by other specialists within the project. The final framework based on: micropaleontology (calcareous nannofossils and foraminifers’ bioevents), climatic cyclicity (foraminifers’ assemblages), geochemistry (oxygen stable isotope, made out on planktic and benthic records), paleomagnetism, radiometric ages (14C AMS), teprhochronology, identification of sapropel-equivalent levels (Se). It’s worth to note the good consistency between the oxygen stable isotope curve obtained for borehole PRAD1-2 and other deeper Mediterranean records. The studied proxies allowed the recognition of all the isotopic intervals from MIS10 to MIS1 in PRAD1-2 record, and the base of the borehole has been ascribed to the early MIS11. Glacial and interglacial intervals identified in the Central Adriatic record have been analysed in detail for the paleo-environmental reconstruction, as well. For instance, glacial stages MIS6, MIS8 and MIS10 present peculiar foraminifers’ assemblages, composed by benthic species typical of polar regions and no longer living in the Central Adriatic nowadays. Moreover, a deepening trend in the paleo-bathymetry during glacial intervals was observed, from MIS10 (inner-shelf environment) to MIS4 (mid-shelf environment).Ten sapropel-equivalent levels have been recognised in PRAD1-2 Central Adriatic record. They showed different planktic foraminifers’ assemblages, which allowed the first distinction of events occurred during warm-climate (Se5, Se7), cold-climate (Se4, Se6 and Se8) and temperate-intermediate-climate (Se1, Se3, Se9, Se’, Se10) conditions, consistently with literature. Cold-climate sapropel equivalents are characterised by the absence of an oligotrophic phase, whereas warm-temeprate-climate sapropel equivalents present both the oligotrophic and the eutrophic phases (except for Se1). Sea floor conditions vary, according to benthic foraminifers’ assemblages, from relatively well oxygenated (Se1, Se3), to dysoxic (Se9, Se’, Se10), to highly dysoxic (Se4, Se6, Se8) to events during which benthic foraminifers are absent (Se5, Se7). These two latter levels are also characterised by the lamination of the sediment, feature never observed in literature in such shallow records. The enhanced stratification of the water column during the events Se8, Se7, Se6, Se5, Se4, and the concurring strong dilution of shallow water, pointed out by the isotope record, lead to the hypothesis of a period of intense precipitation in the Central Adriatic region, possibly due to a northward shift of the African Monsoon. Finally, the expression of Central Adriatic PRAD1-2 Se5 equivalent was compared with the same event, as registered in other Eastern Mediterranean areas. The sequence of substantially the same planktic foraminifers’ bioevents has been consistently recognised, indicating a similar evolution of the water column all over the Eastern Mediterranean; yet, the synchronism of these events cannot be demonstrated. A high resolution analysis of late Holocene (last 6000 years BP) climate change was carried out for the Adriatic area, through the recognition of planktic and benthic foraminifers’ bioevents. In particular, peaks of planktic Globigerinoides sacculifer (four during the last 5500 years BP in the most expanded core) have been interpreted, based on the ecological requirements of this species, as warm-climate, arid intervals, correspondent to periods of relative climatic optimum, such as, for instance, the Medieval Warm Period, the Roman Age, the Late Bronze Age and the Copper Age. Consequently, the minima in the abundance of this biomarker could correspond to relatively cooler and more rainy periods. These conclusions are in good agreement with the isotopic and the pollen data. The Last Occurrence (LO) of G. sacculifer has been dated in this work at an average age of 550 years BP, and it is the best bioevent approximating the base of the Little Ice Age in the Adriatic. Recent literature reports the same bioevent in the Levantine Basin, showing a rather consistent age. Therefore, the LO of G. sacculifer has the potential to be extended to all the Eastern Mediterranean. Within the Little Ice Age, benthic foraminifer V. complanata shows two distinct peaks in the shallower Adriatic cores analysed, collected hundred kilometres apart, inside the mud belt environment. Based on the ecological requirements of this species, these two peaks have been interpreted as the more intense (cold and rainy) oscillations inside the LIA. The chronologic framework of the analysed cores is robust, being based on several range-finding 14C AMS ages, on estimates of the secular variation of the magnetic field, on geochemical estimates of the activity depth of 210Pb short-lived radionuclide (for the core-top ages), and is in good agreement with tephrochronologic, pollen and foraminiferal data. The intra-holocenic climate oscillations find out in the Adriatic have been compared with those pointed out in literature from other records of the Northern Hemisphere, and the chronologic constraint seems quite good. Finally, the sedimentary successions analysed allowed the review and the update of the foraminifers’ ecobiostratigraphy available from literature for the Adriatic region, thanks to the achievement of 16 ecobiozones for the last 60 kyr BP. Some bioevents are restricted to the Central Adriatic (for instance the LO of benthic Hyalinea balthica , approximating the MIS3/MIS2 boundary), others occur all over the Adriatic basin (for instance the LO of planktic Globorotalia inflata during MIS3, individuating Dansgaard-Oeschger cycle 8 (Denekamp)).

Geochronology, geochemistry and isotopic compositions of the volcanic rocks from oceanic (Hawaii) and continental (Eifel) intra-plate environments

The Eifel volcanism is part of the Central European Volcanic Province (CEVP) and is located in the Rhenish Massif, close to the Rhine and Leine Grabens. The Quaternary Eifel volcanism appears to be related to a mantle plume activity. However, the causes of the Tertiary Hocheifel volcanism remain debated. We present geochronological, geochemical and isotope data to assess the geotectonic settings of the Tertiary Eifel volcanism. Based on 40Ar/39Ar dating, we were able to identify two periods in the Hocheifel activity: from 43.6 to 39.0 Ma and from 37.5 to 35.0 Ma. We also show that the pre-rifting volcanism in the northernmost Upper Rhine Graben (59 to 47 Ma) closely precede the Hocheifel volcanic activity. In addition, the volcanism propagates from south to north within the older phase of the Hocheifel activity. At the time of Hocheifel volcanism, the tectonic activity in the Hocheifel was controlled by stress field conditions identical to those of the Upper Rhine Graben. Therefore, magma generation in the Hocheifel appears to be caused by decompression due to Middle to Late Eocene extension. Our geochemical data indicate that the Hocheifel magmas were produced by partial melting of a garnet peridotite at 75-90 km depth. We also show that crustal contamination is minor although the magmas erupted through a relatively thick continental lithosphere. Sr, Nd and Pb isotopic compositions suggest that the source of the Hocheifel magmas is a mixing between depleted FOZO or HIMU-like material and enriched EM2-like material. The Tertiary Hocheifel and the Quaternary Eifel lavas appear to have a common enriched end-member. However, the other sources are likely to be distinct. In addition, the Hocheifel lavas share a depleted component with the other Tertiary CEVP lavas. Although the Tertiary Hocheifel and the Quaternary Eifel lavas appear to originate from different sources, the potential involvement of a FOZO-like component would indicate the contribution of deep mantle material. Thus, on the basis of the geochemical and isotope data, we cannot rule out the involvement of plume-type material in the Hocheifel magmas. The Ko’olau Scientific Drilling Project (KSDP) has been initiated in order to evaluate the long-term evolution of Ko’olau volcano and obtain information about the Hawaiian mantle plume. High precision Pb triple spike data, as well as Sr and Nd isotope data on KSDP lavas and Honolulu Volcanics (HVS) reveal compositional source variations during Ko’olau growth. Pb isotopic compositions indicate that, at least, three Pb end-members are present in Ko’olau lavas. Changes in the contributions of each component are recorded in the Pb, Sr and Nd isotopes stratigraphy. The radiogenic component is present, at variable proportion, in all three stages of Ko’olau growth. It shows affinities with the least radiogenic “Kea-lo8” lavas present in Mauna Kea. The first unradiogenic component was present in the main-shield stage of Ko’olau growth but its contribution decreased with time. It has EM1 type characteristics and corresponds to the “Ko’olau” component of Hawaiian mantle plume. The second unradiogenic end-member, so far only sampled by Honololu lavas, has isotopic characteristics similar to those of a depleted mantle. However, they are different from those of the recent Pacific lithosphere (EPR MORB) indicating that the HVS are not derived from MORB-related source. We suggest, instead, that the HVS result from melting of a plume material. Thus the evolution of a single Hawaiian volcano records the geochemical and isotopic changes within the Hawaiian plume.

Development of a multi-species method by GC-coupling with inductively coupled plasma isotope dilution mass spectrometry for the simultaneous determination of alkylated lead, mercury and tin compounds

An accurate and sensitive species-specific GC-ICP-IDMS (gas chromatography inductively coupled plasma isotope dilution mass spectrometry) method for the determination of trimethyllead and a multi-species-specific GC-ICP-IDMS method for the simultaneous determination of trimethyllead, methylmercury, and butyltins in biological and environmental samples were developed. They allow the determination of corresponding elemental species down to the low ng g-1 range. The developed synthesis scheme for the formation of isotopically labeled Me3206Pb+ can be used for future production of this spike. The novel extraction technique, stir bar sorptive extraction (SBSE), was applied for the first time in connection with species-specific isotope dilution GC-ICP-MS for the determination of trimethyllead, methylmercury and butyltins. The results were compared with liquid-liquid extraction. The developed methods were validated by the analysis of certified reference materials. The liquid-liquid extraction GC-ICP-IDMS method was applied to seafood samples purchased from a supermarket. The methylated lead fraction in these samples, correlated to total lead, varied in a broad range of 0.01-7.6 %. On the contrary, the fraction of methylmercury is much higher, normally in the range of 80-98 %. The highest methylmercury content of up to 12 µg g-1 has been determined in shark samples, an animal which is at the end of the marine food chain, whereas in other seafood samples a MeHg+ content of less than 0.2 µg g-1 was found. Butyltin species could only be determined in samples, where anthropogenic contaminations must be assumed. This explains the observed broad variation of the butylated tin fraction in the range of <0.3-49 % in different seafood samples. Because all isotope-labelled spike compounds, except trimethyllead, are commercially available, the developed multi-species-specific GC-ICP-IDMS method has a high potential in future for routine analysis.

The contribution of the Finite Volume Point Dilution Method to the determination of solute mass flux in an alluvial aquifer.

Groundwater represents one of the most important resources of the world and it is essential to prevent its pollution and to consider remediation intervention in case of contamination. According to the scientific community the characterization and the management of the contaminated sites have to be performed in terms of contaminant fluxes and considering their spatial and temporal evolution. One of the most suitable approach to determine the spatial distribution of pollutant and to quantify contaminant fluxes in groundwater is using control panels. The determination of contaminant mass flux, requires measurement of contaminant concentration in the moving phase (water) and velocity/flux of the groundwater. In this Master Thesis a new solute flux mass measurement approach, based on an integrated control panel type methodology combined with the Finite Volume Point Dilution Method (FVPDM), for the monitoring of transient groundwater fluxes, is proposed. Moreover a new adsorption passive sampler, which allow to capture the variation of solute concentration with time, is designed. The present work contributes to the development of this approach on three key points. First, the ability of the FVPDM to monitor transient groundwater fluxes was verified during a step drawdown test at the experimental site of Hermalle Sous Argentau (Belgium). The results showed that this method can be used, with optimal results, to follow transient groundwater fluxes. Moreover, it resulted that performing FVPDM, in several piezometers, during a pumping test allows to determine the different flow rates and flow regimes that can occurs in the various parts of an aquifer. The second field test aiming to determine the representativity of a control panel for measuring mass flus in groundwater underlined that wrong evaluations of Darcy fluxes and discharge surfaces can determine an incorrect estimation of mass fluxes and that this technique has to be used with precaution. Thus, a detailed geological and hydrogeological characterization must be conducted, before applying this technique. Finally, the third outcome of this work concerned laboratory experiments. The test conducted on several type of adsorption material (Oasis HLB cartridge, TDS-ORGANOSORB 10 and TDS-ORGANOSORB 10-AA), in order to determine the optimum medium to dimension the passive sampler, highlighted the necessity to find a material with a reversible adsorption tendency to completely satisfy the request of the new passive sampling technique.

Water isotopic ratios from a continuously melted ice core sample

A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a~home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW–SLAP scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on the water concentration in the optical cavity. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1‰ and 0.5‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the field during the 2010 season as part of the NEEM deep ice core drilling project in North Greenland.