Isotope determination of sulfur by mass spectrometry in soil samples

Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S) with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS) in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-)), which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2-) concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms) was carried out by isotope ratio mass spectrometry (IRMS). In this work, the labeled material (K2(34)SO4) was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.

Major environmental change and bonebed genesis prior to the Triassic-Jurassic mass extinction

We present new geochemical and sedimentological data from marginal marine strata of Penarth Bay, south Wales (UK) to elucidate the origin of widespread but enigmatic concentrations of vertebrate hard parts (bonebeds) in marine successions of Rhaetian age (late Triassic). Sedimentological evidence shows that the phosphatic constituents of the bonebeds were subjected to intense phosphatization in shallow current-dominated settings and subsequently reworked and transported basinward by storms. Interbedded organic-rich strata deposited under quiescent and poorly oxygenated conditions record enhanced phosphorus regeneration from sedimentary organic matter into the water column and probably provided the main source of phosphate required for heavy bonebed clast phosphatization. The stratigraphically limited interval showing evidence for oxygen depletion and accelerated P-cycling coincides with a negative 4% organic carbon isotope excursion, which possibly reflects supra-regional changes in carbon cycling and clearly predates the 'initial isotope excursion' characterizing many Triassic-Jurassic boundary strata. our data indicate that Rhaetian bonebeds are the lithological signature of profound, climatically driven changes in carbon cycling and redox conditions and support the idea of a multi-pulsed environmental crisis at the end of the Triassic, possibly linked to successive episodes of igneous activity in the central Atlantic Magmatic Province.

Simultaneous quantification of selective serotonin reuptake inhibitors and metabolites in human plasma by liquid chromatography-electrospray mass spectrometry for therapeutic drug monitoring.

A simple and sensitive liquid chromatography-electrospray ionization mass spectrometry method was developed for the simultaneous quantification in human plasma of all selective serotonin reuptake inhibitors (citalopram, fluoxetine, fluvoxamine, paroxetine and sertraline) and their main active metabolites (desmethyl-citalopram and norfluoxetine). A stable isotope-labeled internal standard was used for each analyte to compensate for the global method variability, including extraction and ionization variations. After sample (250μl) pre-treatment with acetonitrile (500μl) to precipitate proteins, a fast solid-phase extraction procedure was performed using mixed mode Oasis MCX 96-well plate. Chromatographic separation was achieved in less than 9.0min on a XBridge C18 column (2.1×100mm; 3.5μm) using a gradient of ammonium acetate (pH 8.1; 50mM) and acetonitrile as mobile phase at a flow rate of 0.3ml/min. The method was fully validated according to Société Française des Sciences et Techniques Pharmaceutiques protocols and the latest Food and Drug Administration guidelines. Six point calibration curves were used to cover a large concentration range of 1-500ng/ml for citalopram, desmethyl-citalopram, paroxetine and sertraline, 1-1000ng/ml for fluoxetine and fluvoxamine, and 2-1000ng/ml for norfluoxetine. Good quantitative performances were achieved in terms of trueness (84.2-109.6%), repeatability (0.9-14.6%) and intermediate precision (1.8-18.0%) in the entire assay range including the lower limit of quantification. Internal standard-normalized matrix effects were lower than 13%. The accuracy profiles (total error) were mainly included in the acceptance limits of ±30% for biological samples. The method was successfully applied for routine therapeutic drug monitoring of more than 1600 patient plasma samples over 9 months. The β-expectation tolerance intervals determined during the validation phase were coherent with the results of quality control samples analyzed during routine use. This method is therefore precise and suitable both for therapeutic drug monitoring and pharmacokinetic studies in most clinical laboratories.

Optimization of the sampling scheme for maps of physical and chemical properties estimated by kriging

The sampling scheme is essential in the investigation of the spatial variability of soil properties in Soil Science studies. The high costs of sampling schemes optimized with additional sampling points for each physical and chemical soil property, prevent their use in precision agriculture. The purpose of this study was to obtain an optimal sampling scheme for physical and chemical property sets and investigate its effect on the quality of soil sampling. Soil was sampled on a 42-ha area, with 206 geo-referenced points arranged in a regular grid spaced 50 m from each other, in a depth range of 0.00-0.20 m. In order to obtain an optimal sampling scheme for every physical and chemical property, a sample grid, a medium-scale variogram and the extended Spatial Simulated Annealing (SSA) method were used to minimize kriging variance. The optimization procedure was validated by constructing maps of relative improvement comparing the sample configuration before and after the process. A greater concentration of recommended points in specific areas (NW-SE direction) was observed, which also reflects a greater estimate variance at these locations. The addition of optimal samples, for specific regions, increased the accuracy up to 2 % for chemical and 1 % for physical properties. The use of a sample grid and medium-scale variogram, as previous information for the conception of additional sampling schemes, was very promising to determine the locations of these additional points for all physical and chemical soil properties, enhancing the accuracy of kriging estimates of the physical-chemical properties.

Comparison between detailed digital and conventional soil maps of an area with complex geology

Since different pedologists will draw different soil maps of a same area, it is important to compare the differences between mapping by specialists and mapping techniques, as for example currently intensively discussed Digital Soil Mapping. Four detailed soil maps (scale 1:10.000) of a 182-ha sugarcane farm in the county of Rafard, São Paulo State, Brazil, were compared. The area has a large variation of soil formation factors. The maps were drawn independently by four soil scientists and compared with a fifth map obtained by a digital soil mapping technique. All pedologists were given the same set of information. As many field expeditions and soil pits as required by each surveyor were provided to define the mapping units (MUs). For the Digital Soil Map (DSM), spectral data were extracted from Landsat 5 Thematic Mapper (TM) imagery as well as six terrain attributes from the topographic map of the area. These data were summarized by principal component analysis to generate the map designs of groups through Fuzzy K-means clustering. Field observations were made to identify the soils in the MUs and classify them according to the Brazilian Soil Classification System (BSCS). To compare the conventional and digital (DSM) soil maps, they were crossed pairwise to generate confusion matrices that were mapped. The categorical analysis at each classification level of the BSCS showed that the agreement between the maps decreased towards the lower levels of classification and the great influence of the surveyor on both the mapping and definition of MUs in the soil map. The average correspondence between the conventional and DSM maps was similar. Therefore, the method used to obtain the DSM yielded similar results to those obtained by the conventional technique, while providing additional information about the landscape of each soil, useful for applications in future surveys of similar areas.

Cross section of a resonant-mass detector for scalar gravitational waves

Gravitationally coupled scalar fields, originally introduced by Jordan, Brans and Dicke to account for a non-constant gravitational coupling, are a prediction of many non-Einsteinian theories of gravity not excluding perturbative formulations of string theory. In this paper, we compute the cross sections for scattering and absorption of scalar and tensor gravitational waves by a resonant-mass detector in the framework of the Jordan-Brans-Dicke theory. The results are then specialized to the case of a detector of spherical shape and shown to reproduce those obtained in general relativity in a certain limit. Eventually we discuss the potential detectability of scalar waves emitted in a spherically symmetric gravitational collapse.

Molecular dynamics study of the longitudinal modes in disparate-mass binaryliquid mixtures.

A series of molecular dynamics simulations of simple liquid binary mixtures of soft spheres with disparate-mass particles were carried out to investigate the origin of the marked differences between the dynamic structure factors of some liquid binary mixtures such as the Li0.7Mg0.3 and Li0.8Pb0.2 alloys. It is shown that the facility for observing peaks associated with fast-propagating modes in the partial Li-Li dynamic structure factor of Li0.8Pb0.2 should be mainly attributed to the structure of this alloy, which is characterized by an incipient ABAB ordering as found in molten salts. The longitudinal dispersion relations at intermediate wave vectors obtained from the longitudinal current spectra are very similar for the two alloys and reflect the existence of both fast-and slow-propagating modes of kinetic character associated with light and heavy particles, respectively. The influence of the hardness of the repulsive potential cores as well as the composition of the mixture on the longitudinal collective modes is also discussed.

Microfabricated dual sprayer for on-line mass tagging of phosphopeptides.

Phosphopeptides tagging reactions by dinuclear zinc(II) complexes (1,3-bis[bis(2-pyridylmethyl)amino]-propan-2-olato dizinc(II)3+, called tag) were performed with a dual-channel microsprayer in electrospray ionization mass spectrometry. The reaction is first studied ex situ and analyzed with a commercial electrospray source. In situ reactions (i.e., inside the Taylor cone) were achieved with a dual-channel microsprayer both with the tag synthesized chemically before the experiments and with the tag electrogenerated by in situ oxidation of a zinc electrode, also used to apply the electrospray current. The device consists of a polyimide microchip with two microchannels (20 microm x 50 microm x 1 cm) etched on each side of the structure and connecting only at the tip of the microchip. We demonstrate here that mixing two solutions with different physicochemical properties inside the Taylor cone can be used to selectively tag target molecules.

Strange nonchaotic attractors in Harper maps

We study the existence of strange nonchaotic attractors (SNA) in the family of Harper maps. We prove that for a set of parameters of positive measure, the map possesses a SNA. However, the set is nowhere dense. By changing the parameter arbitrarily small amounts, the attractor is a smooth curve and not a SNA.

Periodic points of holomorphic maps via Lefschetz numbers

In this paper we study the set of periods of holomorphic maps on compact manifolds, using the periodic Lefschetz numbers introduced by Dold and Llibre, which can be computed from the homology class of the map. We show that these numbers contain information about the existence of periodic points of a given period; and, if we assume the map to be transversal, then they give us the exact number of such periodic orbits. We apply this result to the complex projective space of dimension n and to some special type of Hopf surfaces, partially characterizing their set of periods. In the first case we also show that any holomorphic map of CP(n) of degree greater than one has infinitely many distinct periodic orbits, hence generalizing a theorem of Fornaess and Sibony. We then characterize the set of periods of a holomorphic map on the Riemann sphere, hence giving an alternative proof of Baker's theorem.

Bio-electrical impedance analysis for estimation of fat-free mass and muscle mass in cystic fibrosis patients.

The nutritional status of cystic fibrosis (CF) patients has to be regularly evaluated and alimentary support instituted when indicated. Bio-electrical impedance analysis (BIA) is a recent method for determining body composition. The present study evaluates its use in CF patients without any clinical sign of malnutrition. Thirty-nine patients with CF and 39 healthy subjects aged 6-24 years were studied. Body density and mid-arm muscle circumference were determined by anthropometry and skinfold measurements. Fat-free mass was calculated taking into account the body density. Muscle mass was obtained from the urinary creatinine excretion rate. The resistance index was calculated by dividing the square of the subject's height by the body impedance. We show that fat-free mass, mid-arm muscle circumference and muscle mass are each linearly correlated to the resistance index and that the regression equations are similar for both CF patients and healthy subjects.

Improved segmentation of deep brain grey matter structures using magnetization transfer (MT) parameter maps.

Basal ganglia and brain stem nuclei are involved in the pathophysiology of various neurological and neuropsychiatric disorders. Currently available structural T1-weighted (T1w) magnetic resonance images do not provide sufficient contrast for reliable automated segmentation of various subcortical grey matter structures. We use a novel, semi-quantitative magnetization transfer (MT) imaging protocol that overcomes limitations in T1w images, which are mainly due to their sensitivity to the high iron content in subcortical grey matter. We demonstrate improved automated segmentation of putamen, pallidum, pulvinar and substantia nigra using MT images. A comparison with segmentation of high-quality T1w images was performed in 49 healthy subjects. Our results show that MT maps are highly suitable for automated segmentation, and so for multi-subject morphometric studies with a focus on subcortical structures.