iCONVERT: an integrated device for the UV-assisted determination of H2S via mid-infrared gas sensors

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Online analysis of H2S and SO2 via advanced mid-Infrared gas sensors

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Mid-Pleistocene benthic foraminiferal record in the Southwest Pacific

Benthic foraminiferal faunas from three bathyal sequences provide a proxy record of oceanographic changes through the mid-Pleistocene transition (MPT) on either side of the Subtropical Front (STF), east of New Zealand. Canonical correspondence analyses show that factors related to water depth, latitude and climate cycles were more significant than oceanographic factors in determining changes in faunal assemblage composition over the last 1 Ma. Even so, mid-Pleistocene faunal changes are recognizable and can be linked to inferred palaeoceanographic causes. North of the largely stationary STF the faunas were less variable than to the south, perhaps reflecting the less extreme glacial-interglacial fluctuations in the overlying Subtropical Surface Water. Prior to Marine Isotope Stage (MIS) 21 and after MIS 15, the northern faunas had fairly constant composition, but during most of the MPT faunal composition fluctuated in response to climate-related food-supply variations. Faunal changes through the MPT suggest increasing food supply and decreasing dissolved bottom oxygen. South of the STF, beneath Subantarctic Surface Water, mid-Pleistocene faunas exhibited strong glacial-interglacial fluctuations, inferred to be due to higher interglacial nutrient supply and lower oxygen levels. The most dramatic faunal change in the south occurred at the end of the MPT (MIS 17- 12). with an acme of Abditodentrix pseudothalmanni, possibly reflecting higher carbon flux and lower bottom oxygen. This study suggests that the mid-Pleistocene decline and extinction of a group of elongate, cylindrical deep-sea foraminifera may have been related to decreased bottom oxygen concentrations as aresult of slower deep-water currents.

Precious metals and volatiles in rocks of the Mid-Atlantic Ridge near 15°20'N

Distribution patterns of gold, platinum group metals (PGE), and volatile components are studied in the main rock types of the Mid-Atlantic Ridge lithosphere (ultrabasites, gabbro, and basalts) from the transform fracture zone at 15°20'N. It is ascertained that PGE content depends on the reduction degree of fluids, on rock types, and on their formation conditions. It is noted that concentrations of refractory elements (Os, Ir, Rh) decrease, while those of fusible elements (Pt, Pd, Au) increase with depth. The chondrite type of distribution is only noted in the ultrabasite rocks. Increase in water and CO2 contents and in oxidation degree of fluids occurs with transition from basalts to ultrabasites, as well as from normal magmatic systems to fluid-enriched anomalous systems.

Geochemical composition and crystallization conditions of melts from the Mid Atlantic Ridge near Ascension Island (7-11°S)

Phase equilibria simulations were performed on naturally quenched basaltic glasses to determine crystallization conditions prior to eruption of magmas at the Mid-Atlantic Ridge (MAR) east of Ascension Island (7°11°S).The results indicate that midocean ridge basalt (MORB) magmas beneath different segments of the MAR have crystallized over a wide range of pressures (100-900MPa). However, each segment seems to have a specific crystallization history. Nearly isobaric crystallization conditions (100-300MPa) were obtained for the geochemically enriched MORB magmas of the central segments, whereas normal (N)-MORB magmas of the bounding segments are characterized by polybaric crystallization conditions (200-900MPa). In addition, our results demonstrate close to anhydrous crystallization conditions of N-MORBs, whereas geochemically enriched MORBs were successfully modeled in the presence of 0.4-1wt% H2O in the parental melts.These estimates are in agreement with direct (Fourier transform IR) measurements of H2O abundances in basaltic glasses and melt inclusions for selected samples. Water contents determined in the parental melts are in the range 0.04-0.09 and 0.30-0.55 wt% H2O for depleted and enriched MORBs, respectively. Our results are in general agreement (within ±200MPa) with previous approaches used to evaluate pressure estimates in MORB. However, the determination of pre-eruptive conditions of MORBs, including temperature and water content in addition to pressure, requires the improvement of magma crystallization models to simulate liquid lines of descent in the presence of small amounts of water. KEY WORDS: MORB; Mid-Atlantic Ridge; depth of crystallization; water abundances; phase equilibria calculations; cotectic crystallization; pressure estimates; polybaric fractionation

Mineral composition of mid-ocean-ridge basalts from ODP Leg 187 sites

The chemical compositions of olivine, plagioclase, pyroxene, and spinel in lavas collected during Ocean Drilling Program Leg 187 in the Australian Antarctic Discordance, Southeast Indian Ridge (41°-46°S, 126°-135°E) were analyzed, and modeling of the theoretical equilibrium petrogenetic conditions between olivine and melt was conducted. The cores of larger olivine phenocrysts, particularly in the isotopic Indian-type mid-ocean-ridge basalt (MORB), are not equilibrated with melt compositions and are considered to be xenocrystic. Larger plagioclase phenocrysts with compositionally reversed zonation are also xenocrystic. The compositions of primary magma were calculated using a "maximum olivine fractionation" model for primitive MORB that should fractionate only olivine. Olivine compositions equilibrated with calculated primary magma and compositions of calculated primary magma suggest that (1) isotopic Pacific-type MORB is more fractionated than Indian-type MORB, (2) Pacific-type MORB was produced by higher degrees of partial melting than Indian-type MORB, and (3) primary magma for Indian-type MORB was segregated from mantle at 10 kbar (~30 km depth), whereas that for Pacific-type MORB was segregated at 15 kbar (~45 km depth).

A 18-years long (1993-2011) snow and meteorological dataset from a mid-altitude mountain site (Col de Porte, France, 1325 altitude)

A quality-controlled snow and meteorological dataset spanning the period 1 August 1993-31 July 2011 is presented, originating from the experimental station Col de Porte (1325 m altitude, Chartreuse range, France). Emphasis is placed on meteorological data relevant to the observation and modelling of the seasonal snowpack. In-situ driving data, at the hourly resolution, consist of measurements of air temperature, relative humidity, windspeed, incoming short-wave and long-wave radiation, precipitation rate partitioned between snow- and rainfall, with a focus on the snow-dominated season. Meteorological data for the three summer months (generally from 10 June to 20 September), when the continuity of the field record is not warranted, are taken from a local meteorological reanalysis (SAFRAN), in order to provide a continuous and consistent gap-free record. Data relevant to snowpack properties are provided at the daily (snow depth, snow water equivalent, runoff and albedo) and hourly (snow depth, albedo, runoff, surface temperature, soil temperature) time resolution. Internal snowpack information is provided from weekly manual snowpit observations (mostly consisting in penetration resistance, snow type, snow temperature and density profiles) and from a hourly record of temperature and height of vertically free ''settling'' disks. This dataset has been partially used in the past to assist in developing snowpack models and is presented here comprehensively for the purpose of multi-year model performance assessment. The data is placed on the PANGAEA repository (doi:10.1594/PANGAEA.774249) as well as on the public ftp server ftp://ftp-cnrm.meteo.fr/pub-cencdp/.

Spectrophotometric study in the near-ir of a sample of MIPS selected galaxies at Z~2

Our main objective is to determine what kind of galaxies dominate the cosmic SFR density at z~2. Our sample consists of 24 galaxies in Chandra Deep Field South, a unique field for the study of galaxy evolution (12 observed with GNIRS/GEMINI and 12 with ISAAC/VLT). We use H alpha together with the already merged X-ray, ultraviolet, optical, near and mid-infrared imaging data to obtain estimations of SFRs, metallicities, stellar and dynamical masses, AGN activity, and extinction properties. We have obtained 15 Hα detections, 4 rotation curves, and SFR relationship for 7 galaxies. The metallicities obtained for 8 galaxies of the sample are compatible with the metallicities of local galaxies.

The SCUBA HAlf degree extragalactic survey - III. Identification of radio and mid-infrared counterparts to submillimetre galaxies

Determining an accurate position for a submillimetre (submm) galaxy (SMG) is the crucial step that enables us to move from the basic properties of an SMG sample - source counts and 2D clustering - to an assessment of their detailed, multiwavelength properties, their contribution to the history of cosmic star formation and their links with present-day galaxy populations. In this paper, we identify robust radio and/or infrared (IR) counterparts, and hence accurate positions, for over two-thirds of the SCUBA HAlf-Degree Extragalactic Survey (SHADES) Source Catalogue, presenting optical, 24-μm and radio images of each SMG. Observed trends in identification rate have given no strong rationale for pruning the sample. Uncertainties in submm position are found to be consistent with theoretical expectations, with no evidence for significant additional sources of error. Employing the submm/radio redshift indicator, via a parametrization appropriate for radio-identified SMGs with spectroscopic redshifts, yields a median redshift of 2.8 for the radio-identified subset of SHADES, somewhat higher than the median spectroscopic redshift. We present a diagnostic colour-colour plot, exploiting Spitzer photometry, in which we identify regions commensurate with SMGs at very high redshift. Finally, we find that significantly more SMGs have multiple robust counterparts than would be expected by chance, indicative of physical associations. These multiple systems are most common amongst the brightest SMGs and are typically separated by 2-6 arcsec, similar to 15-20/sin i kpc at z~ 2, consistent with early bursts seen in merger simulations.

Continuous statistical modelling for rapid detection of adulteration of extra virgin olive oil using mid infrared and Raman spectroscopic data

The main objective of this work was to develop a novel dimensionality reduction technique as a part of an integrated pattern recognition solution capable of identifying adulterants such as hazelnut oil in extra virgin olive oil at low percentages based on spectroscopic chemical fingerprints. A novel Continuous Locality Preserving Projections (CLPP) technique is proposed which allows the modelling of the continuous nature of the produced in-house admixtures as data series instead of discrete points. The maintenance of the continuous structure of the data manifold enables the better visualisation of this examined classification problem and facilitates the more accurate utilisation of the manifold for detecting the adulterants. The performance of the proposed technique is validated with two different spectroscopic techniques (Raman and Fourier transform infrared, FT-IR). In all cases studied, CLPP accompanied by k-Nearest Neighbors (kNN) algorithm was found to outperform any other state-of-the-art pattern recognition techniques.

Thermomechanical sensitivity of microcantilever in the mid-infrared spectral region

This paper reports the thermomechanical sensitivity of bimaterial cantilevers over a mid-infrared (IR) spectral range (5-10 µm) that is critical both for chemical analysis via vibrational spectroscopy and for direct thermal detection in the 300-700 K range. Mechanical bending sensitivity and noise were measured and modeled for six commercially available microcantilevers, which consist of either an aluminum film on a silicon cantilever or a gold film on a silicon nitride cantilever. The spectral sensitivity of each cantilever was determined by recording cantilever deflection when illuminated with IR light from a monochromator. Rigorous modeling and systematic characterization of the optical system allowed for a quantitative estimate of IR energy incident upon the cantilever. Separately, spectral absorptance of the cantilever was measured using Fourier transform infrared (FT-IR) microscopy, which was compared with analytical models of radiation onto the cantilever and heat flow within the cantilever. The predictions of microcantilever thermomechanical bending sensitivity and noise agree well with measurements, resulting in a ranking of these cantilevers for their potential use in IR measurements.

Core-valence Correlation Effects On Ir Calculations: The Bf3 And Bcl3 Cases.

The first theoretical results of core-valence correlation effects are presented for the infrared wavenumbers and intensities of the BF3 and BCl3 molecules, using (double- and triple-zeta) Dunning core-valence basis sets at the CCSD(T) level. The results are compared with those calculated in the frozen core approximation with standard Dunning basis sets at the same correlation level and with the experimental values. The general conclusion is that the effect of core-valence correlation is, for infrared wavenumbers and intensities, smaller than the effect of adding augmented diffuse functions to the basis set, e.g., cc-pVTZ to aug-cc-pVTZ. Moreover, the trends observed in the data are mainly related to the augmented functions rather than the core-valence functions added to the basis set. The results obtained here confirm previous studies pointing out the large descrepancy between the theoretical and experimental intensities of the stretching mode for BCl3.

Changes In Liver Cell Dna Methylation Status In Diabetic Mice Affect Its Ft-ir Characteristics.

Lower levels of cytosine methylation have been found in the liver cell DNA from non-obese diabetic (NOD) mice under hyperglycemic conditions. Because the Fourier transform-infrared (FT-IR) profiles of dry DNA samples are differently affected by DNA base composition, single-stranded form and histone binding, it is expected that the methylation status in the DNA could also affect its FT-IR profile. The DNA FT-IR signatures obtained from the liver cell nuclei of hyperglycemic and normoglycemic NOD mice of the same age were compared. Dried DNA samples were examined in an IR microspectroscope equipped with an all-reflecting objective (ARO) and adequate software. Changes in DNA cytosine methylation levels induced by hyperglycemia in mouse liver cells produced changes in the respective DNA FT-IR profiles, revealing modifications to the vibrational intensities and frequencies of several chemical markers, including νas -CH3 stretching vibrations in the 5-methylcytosine methyl group. A smaller band area reflecting lower energy absorbed in the DNA was found in the hyperglycemic mice and assumed to be related to the lower levels of -CH3 groups. Other spectral differences were found at 1700-1500 cm(-1) and in the fingerprint region, and a slight change in the DNA conformation at the lower DNA methylation levels was suggested for the hyperglycemic mice. The changes that affect cytosine methylation levels certainly affect the DNA-protein interactions and, consequently, gene expression in liver cells from the hyperglycemic NOD mice.

Fluorescence, Aggregation Properties And Ft-ir Microspectroscopy Of Elastin And Collagen Fibers.

Histological and histochemical observations support the hypothesis that collagen fibers can link to elastic fibers. However, the resulting organization of elastin and collagen type complexes and differences between these materials in terms of macromolecular orientation and frequencies of their chemical vibrational groups have not yet been solved. This study aimed to investigate the macromolecular organization of pure elastin, collagen type I and elastin-collagen complexes using polarized light DIC-microscopy. Additionally, differences and similarities between pure elastin and collagen bundles (CB) were investigated by Fourier transform-infrared (FT-IR) microspectroscopy. Although elastin exhibited a faint birefringence, the elastin-collagen complex aggregates formed in solution exhibited a deep birefringence and formation of an ordered-supramolecular complex typical of collagen chiral structure. The FT-IR study revealed elastin and CB peptide NH groups involved in different types of H-bonding. More energy is absorbed in the vibrational transitions corresponding to CH, CH2 and CH3 groups (probably associated with the hydrophobicity demonstrated by 8-anilino-1-naphtalene sulfonic acid sodium salt [ANS] fluorescence), and to νCN, δNH and ωCH2 groups of elastin compared to CB. It is assumed that the α-helix contribution to the pure elastin amide I profile is 46.8%, whereas that of the B-sheet is 20% and that unordered structures contribute to the remaining percentage. An FT-IR profile library reveals that the elastin signature within the 1360-1189cm(-1) spectral range resembles that of Conex-Toray aramid fibers.