Chemical evolution of the Galactic bulge as traced by microlensed dwarf and subgiant stars III. Detection of lithium in the metal-poor bulge dwarf MOA-2010-BLG-285S

Context. To study the evolution of Li in the Galaxy it is necessary to observe dwarf or subgiant stars. These are the only long-lived stars whose present-day atmospheric chemical composition reflects their natal Li abundances according to standard models of stellar evolution. Although Li has been extensively studied in the Galactic disk and halo, to date there has only been one uncertain detection of Li in an unevolved bulge star. Aims. Our aim with this study is to provide the first clear detection of Li in the Galactic bulge, based on an analysis of a dwarf star that has largely retained its initial Li abundance. Methods. We performed a detailed elemental abundance analysis of the bulge dwarf star MOA-2010-BLG-285S using a high-resolution and high signal-to-noise spectrum obtained with the UVES spectrograph at the VLT when the object was optically magnified during a gravitational microlensing event (visual magnification A similar to 550 during observation). The Li abundance was determined through synthetic line profile fitting of the (7)Li resonance doublet line at 670.8 nm. The results have been corrected for departures from LTE. Results. MOA-2010-BLG-285S is, at [Fe/H] = -1.23, the most metal-poor dwarf star detected so far in the Galactic bulge. Its old age (12.5 Gyr) and enhanced [alpha/Fe] ratios agree well with stars in the thick disk at similar metallicities. This star represents the first unambiguous detection of Li in a metal-poor dwarf star in the Galactic bulge. We find an NLTE corrected Li abundance of log epsilon(Li) = 2.16, which is consistent with values derived for Galactic disk and halo dwarf stars at similar metallicities and temperatures. Conclusions. Our results show that there are no signs of Li enrichment or production in the Galactic bulge during its earliest phases. Observations of Li in other galaxies (omega Cen) and other components of the Galaxy suggest further that the Spite plateau is universal.

Chemical evolution models for spiral disks: the Milky Way, M31, and M33

Context. The distribution of chemical abundances and their variation with time are important tools for understanding the chemical evolution of galaxies. In particular, the study of chemical evolution models can improve our understanding of the basic assumptions made when modelling our Galaxy and other spirals. Aims. We test a standard chemical evolution model for spiral disks in the Local Universe and study the influence of a threshold gas density and different efficiencies in the star formation rate (SFR) law on radial gradients of abundance, gas, and SFR. The model is then applied to specific galaxies. Methods. We adopt a one-infall chemical evolution model where the Galactic disk forms inside-out by means of infall of gas, and we test different thresholds and efficiencies in the SFR. The model is scaled to the disk properties of three Local Group galaxies (the Milky Way, M31 and M33) by varying its dependence on the star formation efficiency and the timescale for the infall of gas onto the disk. Results. Using this simple model, we are able to reproduce most of the observed constraints available in the literature for the studied galaxies. The radial oxygen abundance gradients and their time evolution are studied in detail. The present day abundance gradients are more sensitive to the threshold than to other parameters, while their temporal evolutions are more dependent on the chosen SFR efficiency. A variable efficiency along the galaxy radius can reproduce the present day gas distribution in the disk of spirals with prominent arms. The steepness in the distribution of stellar surface density differs from massive to lower mass disks, owing to the different star formation histories. Conclusions. The most massive disks seem to have evolved faster (i.e., with more efficient star formation) than the less massive ones, thus suggesting a downsizing in star formation for spirals. The threshold and the efficiency of star formation play a very important role in the chemical evolution of spiral disks. For instance, an efficiency varying with radius can be used to regulate the star formation. The oxygen abundance gradient can steepen or flatten in time depending on the choice of this parameter.

The chemical evolution of IC 10

Context. Dwarf irregular galaxies are relatively simple unevolved objects where it is easy to test models of galactic chemical evolution. Aims. We attempt to determine the star formation and gas accretion history of IC 10, a local dwarf irregular for which abundance, gas, and mass determinations are available. Methods. We apply detailed chemical evolution models to predict the evolution of several chemical elements (He, O, N, S) and compared our predictions with the observational data. We consider additional constraints such as the present-time gas fraction, the star formation rate (SFR), and the total estimated mass of IC 10. We assume a dark matter halo for this galaxy and study the development of a galactic wind. We consider different star formation regimes: bursting and continuous. We explore different wind situations: i) normal wind, where all the gas is lost at the same rate and ii) metal-enhanced wind, where metals produced by supernovae are preferentially lost. We study a case without wind. We vary the star formation efficiency (SFE), the wind efficiency, and the time scale of the gas infall, which are the most important parameters in our models. Results. We find that only models with metal-enhanced galactic winds can reproduce the properties of IC 10. The star formation must have proceeded in bursts rather than continuously and the bursts must have been less numerous than similar to 10 over the whole galactic lifetime. Finally, IC 10 must have formed by a slow process of gas accretion with a timescale of the order of 8 Gyr.

Chemical abundances of 11 bulge stars from high-resolution, near-IR spectra

Context. It is debated whether the Milky Way bulge has characteristics more similar to those of a classical bulge than those of a pseudobulge. Detailed abundance studies of bulge stars are important when investigating the origin, history, and classification of the bulge. These studies provide constraints on the star-formation history, initial mass function, and differences between stellar populations. Not many similar studies have been completed because of the large distance and high variable visual extinction along the line-of-sight towards the bulge. Therefore, near-IR investigations can provide superior results. Aims. To investigate the origin of the bulge and study its chemical abundances determined from near-IR spectra for bulge giants that have already been investigated with optical spectra. The optical spectra also provide the stellar parameters that are very important to the present study. In particular, the important CNO elements are determined more accurately in the near-IR. Oxygen and other alpha elements are important for investigating the star-formation history. The C and N abundances are important for determining the evolutionary stage of the giants and the origin of C in the bulge. Methods. High-resolution, near-infrared spectra in the H band were recorded using the CRIRES spectrometer mounted on the Very Large Telescope. The CNO abundances are determined from the numerous molecular lines in the wavelength range observed. Abundances of the alpha elements Si, S, and Ti are also determined from the near-IR spectra. Results. The abundance ratios [O/Fe], [Si/Fe], and [S/Fe] are enhanced to metallicities of at least [Fe/H] = -0.3, after which they decline. This suggests that the Milky Way bulge experienced a rapid and early burst of star formation similar to that of a classical bulge. However, a similarity between the bulge trend and the trend of the local thick disk seems to be present. This similarity suggests that the bulge could have had a pseudobulge origin. The C and N abundances suggest that our giants are first-ascent red-giants or clump stars, and that the measured oxygen abundances are those with which the stars were born. Our [C/Fe] trend does not show any increase with [Fe/H], which is expected if W-R stars contributed substantially to the C abundances. No ""cosmic scatter"" can be traced around our observed abundance trends: the measured scatter is expected, given the observational uncertainties.

Chemical similarities between Galactic bulge and local thick disk red giants: O, Na, Mg, Al, Si, Ca, and Ti

Context. The formation and evolution of the Galactic bulge and its relationship with the other Galactic populations is still poorly understood. Aims. To establish the chemical differences and similarities between the bulge and other stellar populations, we performed an elemental abundance analysis of alpha- (O, Mg, Si, Ca, and Ti) and Z-odd (Na and Al) elements of red giant stars in the bulge as well as of local thin disk, thick disk and halo giants. Methods. We use high-resolution optical spectra of 25 bulge giants in Baade's window and 55 comparison giants (4 halo, 29 thin disk and 22 thick disk giants) in the solar neighborhood. All stars have similar stellar parameters but cover a broad range in metallicity (-1.5 < [Fe/H] < +0.5). A standard 1D local thermodynamic equilibrium analysis using both Kurucz and MARCS models yielded the abundances of O, Na, Mg, Al, Si, Ca, Ti and Fe. Our homogeneous and differential analysis of the Galactic stellar populations ensured that systematic errors were minimized. Results. We confirm the well-established differences for [alpha/Fe] at a given metallicity between the local thin and thick disks. For all the elements investigated, we find no chemical distinction between the bulge and the local thick disk, in agreement with our previous study of C, N and O but in contrast to other groups relying on literature values for nearby disk dwarf stars. For -1.5 < [Fe/H] < -0.3 exactly the same trend is followed by both the bulge and thick disk stars, with a star-to-star scatter of only 0.03 dex. Furthermore, both populations share the location of the knee in the [alpha/Fe] vs. [Fe/H] diagram. It still remains to be confirmed that the local thick disk extends to super-solar metallicities as is the case for the bulge. These are the most stringent constraints to date on the chemical similarity of these stellar populations. Conclusions. Our findings suggest that the bulge and local thick disk stars experienced similar formation timescales, star formation rates and initial mass functions, confirming thus the main outcomes of our previous homogeneous analysis of [O/Fe] from infrared spectra for nearly the same sample. The identical a-enhancements of thick disk and bulge stars may reflect a rapid chemical evolution taking place before the bulge and thick disk structures we see today were formed, or it may reflect Galactic orbital migration of inner disk/bulge stars resulting in stars in the solar neighborhood with thick-disk kinematics.

Seasonal Variation, Chemical Composition and Antioxidant activity of Brazilian Propolis Samples

Total phenolic contents, antioxidant activity and chemical composition of propolis samples from three localities of Minas Gerais state (southeast Brazil) were determined. Total phenolic contents were determined by the Folin-Ciocalteau method, antioxidant activity was evaluated by DPPH, using BHT as reference, and chemical composition was analyzed by GC/MS. Propolis from Itapecerica and Paula Candido municipalities were found to have high phenolic contents and pronounced antioxidant activity. From these extracts, 40 substances were identified, among them were simple phenylpropanoids, prenylated phenylpropanoids, sesqui- and diterpenoids. Quantitatively, the main constituent of both samples was allyl-3-prenylcinnamic acid. A sample from Virginopolis municipality had no detectable phenolic substances and contained mainly triterpenoids, the main constituents being alpha-and beta-amyrins. Methanolic extracts from Itapecerica and Paula Candido exhibited pronounced scavenging activity towards DPPH, indistinguishable from BHT activity. However, extracts from Virginopolis sample exhibited no antioxidant activity. Total phenolic substances, GC/MS analyses and antioxidant activity of samples from Itapecerica collected monthly over a period of 1 year revealed considerable variation. No correlation was observed between antioxidant activity and either total phenolic contents or contents of artepillin C and other phenolic substances, as assayed by CG/MS analysis.

Cloud condensation nuclei in pristine tropical rainforest air of Amazonia: size-resolved measurements and modeling of atmospheric aerosol composition and CCN activity

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. We have measured and characterized CCN at water vapor supersaturations in the range of S=0.10-0.82% in pristine tropical rainforest air during the AMAZE-08 campaign in central Amazonia. The effective hygroscopicity parameters describing the influence of chemical composition on the CCN activity of aerosol particles varied in the range of kappa approximate to 0.1-0.4 (0.16+/-0.06 arithmetic mean and standard deviation). The overall median value of kappa approximate to 0.15 was by a factor of two lower than the values typically observed for continental aerosols in other regions of the world. Aitken mode particles were less hygroscopic than accumulation mode particles (kappa approximate to 0.1 at D approximate to 50 nm; kappa approximate to 0.2 at D approximate to 200 nm), which is in agreement with earlier hygroscopicity tandem differential mobility analyzer (H-TDMA) studies. The CCN measurement results are consistent with aerosol mass spectrometry (AMS) data, showing that the organic mass fraction (f(org)) was on average as high as similar to 90% in the Aitken mode (D <= 100 nm) and decreased with increasing particle diameter in the accumulation mode (similar to 80% at D approximate to 200 nm). The kappa values exhibited a negative linear correlation with f(org) (R(2)=0.81), and extrapolation yielded the following effective hygroscopicity parameters for organic and inorganic particle components: kappa(org)approximate to 0.1 which can be regarded as the effective hygroscopicity of biogenic secondary organic aerosol (SOA) and kappa(inorg)approximate to 0.6 which is characteristic for ammonium sulfate and related salts. Both the size dependence and the temporal variability of effective particle hygroscopicity could be parameterized as a function of AMS-based organic and inorganic mass fractions (kappa(p)=kappa(org) x f(org)+kappa(inorg) x f(inorg)). The CCN number concentrations predicted with kappa(p) were in fair agreement with the measurement results (similar to 20% average deviation). The median CCN number concentrations at S=0.1-0.82% ranged from N(CCN,0.10)approximate to 35 cm(-3) to N(CCN,0.82)approximate to 160 cm(-3), the median concentration of aerosol particles larger than 30 nm was N(CN,30)approximate to 200 cm(-3), and the corresponding integral CCN efficiencies were in the range of N(CCN,0.10/NCN,30)approximate to 0.1 to N(CCN,0.82/NCN,30)approximate to 0.8. Although the number concentrations and hygroscopicity parameters were much lower in pristine rainforest air, the integral CCN efficiencies observed were similar to those in highly polluted megacity air. Moreover, model calculations of N(CCN,S) assuming an approximate global average value of kappa approximate to 0.3 for continental aerosols led to systematic overpredictions, but the average deviations exceeded similar to 50% only at low water vapor supersaturation (0.1%) and low particle number concentrations (<= 100 cm(-3)). Model calculations assuming aconstant aerosol size distribution led to higher average deviations at all investigated levels of supersaturation: similar to 60% for the campaign average distribution and similar to 1600% for a generic remote continental size distribution. These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the information and parameterizations presented in this paper should enable efficient description of the CCN properties of pristine tropical rainforest aerosols of Amazonia in detailed process models as well as in large-scale atmospheric and climate models.

Dynamic transitions in a three dimensional associating lattice gas model

The aggregation of interacting Brownian particles in sheared concentrated suspensions is an important issue in colloid and soft matter science per se. Also, it serves as a model to understand biochemical reactions occurring in vivo where both crowding and shear play an important role. We present an effective medium approach within the Smoluchowski equation with shear which allows one to calculate the encounter kinetics through a potential barrier under shear at arbitrary colloid concentrations. Experiments on a model colloidal system in simple shear flow support the validity of the model in the concentration range considered. By generalizing Kramers' rate theory to the presence of shear and collective hydrodynamics, our model explains the significant increase in the shear-induced reaction-limited aggregation kinetics upon increasing the colloid concentration.

KINETICS VERSUS HYDRODYNAMICS: GENERALIZATION OF LANDAU/COOPER-FRYE PRESCRIPTION FOR FREEZE-OUT

The problem of spectra formation in hydrodynamic approach to A + A collisions is considered within the Boltzmann equations. It is shown analytically and illustrated by numerical calculations that the particle momentum spectra can be presented in the Cooper-R-ye form despite freeze-out is not sharp and has the finite temporal width. The latter is equal to the inverse of the particle collision rate at points (t(sigma) (r, p), r) of the maximal emission at a fixed momentum p. The set of these points forms the hypersurfaces t(sigma)(r,p) which strongly depend on the values of p and typically do not enclose completely the initially dense matter. This is an important difference from the standard Cooper-Frye prescription (CFp), with a common freeze-out hypersurface for all p, that affects significantly the predicted spectra. Also, the well known problem of CFp as for negative contributions to the spectra from non-space-like parts of the freeze-out hypersurface is naturally eliminated in this improved prescription.

A quasiclassical trajectory study of the OH plus SO reaction: The role of rotational energy

A full dimensional quasiclassical trajectory study of the OH+SO reaction is presented with the aim of investigating the role of the reactants rotational energy in the reactivity. Different energetic combinations with one and both reactants rotationally excited are studied. A passive method is used to correct zero-point-energy leakage in the classical calculations. The reactive cross sections, for each combination, are calculated and fitted to a capturelike model combined with a factor accounting for recrossing effects. Reactivity decreases as rotational energy is increased in any of both reactants. This fact provides a theoretical support for the experimental dependence of the rate constant on temperature.

Chemical and in vitro study of the potential of 3-(aryl)-2-sulfanylpropenoic acids and their Zn(II) complexes as protective agents against cadmium toxicity

The free H(2)xspa ligands [xspa = pspa, Clpspa, tspa or fspa where p = 3-(phenyl), Clp = 3-(2-chlorophenyl), t = 3-(2-thienyl), f = 3-(2-furyl) and spa = 2-sulfanylpropenoato], their Zn(II) complexes of formula [HQ](2)[Zn(xspa)(2)] (HQ=diisopropylammonium) and the Cd(II) equivalents were prepared and characterized by elemental analysis and by IR, Raman and NMR ((1)H, (13)C) spectroscopy. X-Ray studies of the crystal structures of [HQ](2)[Zn(pspa)(2)], [HQ](2)[Zn(Clpspa)2], [HQ](2)[Zn(tspa)(2)] and [HQ](2)[Zn(fspa)(2)] show that the zinc atom is coordinated to two O atoms and two S atoms of the ligands in a distorted tetrahedral ZnO(2)S(2) environment. In the structures of [HQ](2)[Cd(pspa)(2)] and [HQ](2)[Cd(Clpspa)(2)] the cadmium atom is coordinated to three S atoms and two carboxylato O atoms of the ligands in a distorted trigonal bipyramidal environment. The interchange of ligands between Zn( II) and Cd( II) was studied by (113)Cd NMR spectroscopy. The in vitro protective effect of H(2)xspa and their Zn( II) complexes against Cd toxicity was investigated using the human hepatocarcinoma HepG2 cell line and the pig renal proximal tubule LLC-PK1 cell line. The incorporation of Zn( II) was found to be relevant in the case of H(2)pspa, with an increase observed in the cell viability of the LCC-PK1 cells with respect to the value for the free ligand.

Direct evidence of singlet molecular oxygen generation from peroxynitrate, a decomposition product of peroxynitrite

The decomposition of peroxynitrite to nitrite and dioxygen at neutral pH follows complex kinetics, compared to its isomerization to nitrate at low pH. Decomposition may involve radicals or proceed by way of the classical peracid decomposition mechanism. Peroxynitrite (ONOOH/ONOO(-)) decomposition has been proposed to involve formation of peroxynitrate (O(2)NOOH/O(2)NOO(-)) at neutral pH (D. Gupta, B. Harish, R. Kissner and W. H. Koppenol, Dalton Trans., 2009, DOI: 10.1039/b905535e, see accompanying paper in this issue). Peroxynitrate is unstable and decomposes to nitrite and dioxygen. This study aimed to investigate whether O(2)NOO(-) formed upon ONOOH/ONOO(-) decomposition generates singlet molecular oxygen [O(2) ((1)Delta(g))]. As unequivocally revealed by the measurement of monomol light emission in the near infrared region at 1270 nm and by chemical trapping experiments, the decomposition of ONOO(-) or O(2)NOOH at neutral to alkaline pH generates O(2) ((1)Delta(g)) at a yield of ca. 1% and 2-10%, respectively. Characteristic light emission, corresponding to O(2) ((1)Delta(g)) monomolecular decay was observed for ONOO(-) and for O(2)NOOH prepared by reaction of H(2)O(2) with NO(2)BF(4) and of H(2)O(2) with NO(2)(-) in HClO(4). The generation of O(2) ((1)Delta(g)) from ONOO(-) increased in a concentration-dependent manner in the range of 0.1-2.5 mM and was dependent on pH, giving a sigmoid pro. le with an apparent pK(a) around pD 8.1 (pH 7.7). Taken together, our results clearly identify the generation of O(2) ((1)Delta(g)) from peroxynitrate [O(2)NOO(-) -> NO(2)(-) + O(2) ((1)Delta(g))] generated from peroxynitrite and also from the reactions of H(2)O(2) with either NO(2)BF(4) or NO(2)(-) in acidic media.

Studies on the Electrocatalytic Reduction of Hydrogen Peroxide on a Glassy Carbon Electrode Modified With a Ruthenium Oxide Hexacyanoferrate Film

The electrocatalytic reduction of hydrogen peroxide on a glassy carbon (GC) electrode modified with a ruthenium oxide hexacyanoferrate (RuOHCF) was investigated using rotating disc electrode (RDE) voltammetry aiming to improve the performance of the sensor for hydrogen peroxide detection. The influence of parameters such as rotation speed, film thickness and hydrogen peroxide concentration indicated that the rate of the cross-chemical reaction between Ru(II) centres immobilized into the film and hydrogen peroxide controls the overall process. The kinetic regime could be classified as LSk mechanism, according to the diagnostic table proposed by Albery and Hillman, and the kinetic constant of the mediated process was found to be 706 mol(-1) cm(3) s(-1). In the LSk case the reaction layer is located at a finite layer close to the modifier layer/solution interface

Full-dimensional analytical ab initio potential energy surface of the ground state of HOI

Extensive ab initio calculations using a complete active space second-order perturbation theory wavefunction, including scalar and spin-orbit relativistic effects with a quadruple-zeta quality basis set were used to construct an analytical potential energy surface (PES) of the ground state of the [H, O, I] system. A total of 5344 points were fit to a three-dimensional function of the internuclear distances, with a global root-mean-square error of 1.26 kcal mol(-1). The resulting PES describes accurately the main features of this system: the HOI and HIO isomers, the transition state between them, and all dissociation asymptotes. After a small adjustment, using a scaling factor on the internal coordinates of HOI, the frequencies calculated in this work agree with the experimental data available within 10 cm(-1). (C) 2011 American Institute of Physics. [doi: 10.1063/1.3615545]

Chemical analyses confirm a rare case of seed dispersal by bees

It has been suggested that dispersal of seeds of Coussapoa asperifolia magnifolia could have endozoochoric dispersal by frugivorous birds and monkeys because the fruits are red when ripe, or exozoochoric dispersal, because the exocarp is mucilaginous and sticky. However, our field observations showed only stingless bees collecting the exocarp with seeds of C. asperifolia magnifolia, which are used for building and repairing their nests, from which the plants sprout. This paper aimed to determine the fruit chemical composition, since we postulated that C. asperifolia magnifolia is neither consumed by birds nor monkeys due to being very sticky and apparently resinous. Apolar extract analyses revealed the fruits are not resinous but extremely rich in waxes ( mainly esterified triglycerides), and polar extract analyses revealed the sugar content to be close to the sensorial minimum level. This probably accounts for why only stingless bees are seen visiting fruits and dispersing seeds.