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

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

Coordination of passive systems under quantized measurements

In this paper we investigate a passivity approach to collective coordination and synchronization problems in the presence of quantized measurements and show that coordination tasks can be achieved in a practical sense for a large class of passive systems.Comment: 40 pages, 1 figure, submitted to journal, second round of revie

Photopolymerized thermosensitive poly(HPMAlactate)-PEG-based hydrogels : effect of network design on mechanical properties, degradation, and release behavior

Photopolymerized thermosensitive A-B-A triblock copolymer hydrogels composed of poly(N-(2-hydroxypropyl)-methacrylamide lactate) A-blocks, partly derivatizal with methacrylate groups to different extents (10, 20, and 30%) and hydrophilic poly(ethylene glycol) B-blocks of different molecular weights (4, 10, and 20 kDa) were synthesized. The aim of the present study was to correlate the polymer architecture with the hydrogel properties, particularly rheological, swelling, degradation properties and release behavior. It was found that an increasing methacrylation extent and a decreasing PEG molecular weight resulted in increasing gel strength and cross-link density, which tailored the degradation profiles from 25 to more than 300 days. Polymers having small PEG blocks showed a remarkable phase separation into polymer- and water-rich domains, as demonstrated by confocal microscopy. Depending on the hydrophobic domain density, the loaded protein resides in the hydrophilic pores or is partitioned into hydrophilic and hydrophobic domains, and its release from these compartments is tailored by the extent of methacrylation and by PEG length, respectively. As the mechanical properties, degradation, and release profiles can be fully controlled by polymer design and concentration, these hydrogels are suitable for controlled protein release

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

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

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

Effect of high-pass filtering on ECG signal on the analysis of patients prone to atrial fibrillation

The aim of this study was to assess the effect of filtering techniques on the time-domain analysis of the ECG. Multi-lead ECG recordings obtained from chronic atrial fibrillation (AF) patients after successful external cardioversion have been acquired. Several high-pass filtering techniques and three cut-off frequency values were used: Bessel and Butterworth four-pole and two-pole bidirectional and unidirectional filters, at 0.01, 0.05 and 0.5 Hz low cut-off frequency. As a reference, a beat-by-beat linear piecewise interpolation was used to remove baseline wander, on each P-wave. Results show that ECG filtering affects the estimation of P-wave duration in a manner that depends upon the type of filter used: particularly, the bidirectional filters caused negligible variation of P-wave duration, while unidirectional ones provoked an increase higher than 8%

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

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

Basal and stimulated calcitonin for the diagnosis of medullary thyroid cancer: updated thresholds and safety assessment

Purpose Reliable cut-offs for basal (bCT) and calcium stimulated calcitonin (casCT) are needed for an early and accurate diagnosis of medullary thyroid cancer (MTC). Patients and methods Fifty-four new patients with nodular goiter were enrolled and analysed together with those previously published by our group for a total of 135 cases. bCT and casCT were measured by a highly sensitive method and the results compared with histological findings. In a subgroup of patients, cardiac rhythm was recorded before and during the calcium test. Results In both females (F) and males (M), there was a significant correlation between tumor size and bCT levels (P < 0.001). The receiver operating characteristic plot analyses showed that, for bCT, the new cut-off points able to separate non-MTC from MTC patients were > 30 (F) and > 34 pg/mL (M), whereas the best casCT thresholds were > 79 (F) and > 466 pg/mL (M). bCT was shown to harbour a high accuracy, though some cases were diagnosed only upon stimulation test. Importantly, combining bCT, below or above the cut-offs, with casCT above the cut-offs, all the MTC cases were correctly identified. A reversible sinus bradycardia was observed in 9% of cases during the test. Conclusions Refined cut-offs for bCT and casCT in patients with nodular goiter are reported. Sensitive bCT was shown to have a high accuracy, but the combination with casCT data was needed to identify all MTC cases. The reliability and safety of calcium test strongly favour the routine use of CT determination in nodular thyroid disease