Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds

Asymmetric emission profiles of the stereoisomers of plant-derived volatile organic compounds vary with season, geography, plant type, and stress factors. After oxidation of these compounds in the atmosphere, the low-vapor pressure products ultimately contribute strongly to the particle-phase material of the atmosphere. In order to explore the possibility of stereochemical transfer to atmospheric aerosol particles during the oxidation of biogenic volatile organic compounds, second-order coherent vibrational spectra were recorded of the particle-phase organic material produced by the oxidation of different stereoisomeric mixes of alpha-pinene. The spectra show that the stereochemical configurations are not scrambled but instead are transferred from the gas-phase molecular precursors to the particle-phase molecules. The spectra also show that oligomers formed in the particle phase have a handed superstructure that depends strongly and nonlinearly on the initial stereochemical composition of the precursors. Because the stereochemical mix of the precursors for a material can influence the physical and chemical properties of that material, our findings suggest that chirality is also important for such properties of plant-derived aerosol particles. Citation: Ebben, C. J., S. R. Zorn, S.-B. Lee, P. Artaxo, S. T. Martin, and F. M. Geiger (2011), Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds, Geophys. Res. Lett., 38, L16807, doi: 10.1029/2011GL048599.

Characterization of the optical properties of atmospheric aerosols in Amazonia from long-term AERONET monitoring (1993-1995 and 1999-2006)

We present a new climatology of atmospheric aerosols (primarily pyrogenic and biogenic) for the Brazilian tropics on the basis of a high-quality data set of spectral aerosol optical depth and directional sky radiance measurements from Aerosol Robotic Network (AERONET) Cimel Sun-sky radiometers at more than 15 sites distributed across the Amazon basin and adjacent Cerrado region. This network is the only long-term project (with a record including observations from more than 11 years at some locations) ever to have provided ground-based remotely-sensed column aerosol properties for this critical region. Distinctive features of the Amazonian area aerosol are presented by partitioning the region into three aerosol regimes: southern Amazonian forest, Cerrado, and northern Amazonian forest. The monitoring sites generally include measurements from the interval 1999-2006, but some sites have measurement records that date back to the initial days of the AERONET program in 1993. Seasonal time series of aerosol optical depth (AOD), angstrom ngstrom exponent, and columnar-averaged microphysical properties of the aerosol derived from sky radiance inversion techniques (single-scattering albedo, volume size distribution, fine mode fraction of AOD, etc.) are described and contrasted for the defined regions. During the wet season, occurrences of mineral dust penetrating deep into the interior were observed.

Chemical bonding and composition of silicon nitride films prepared by inductively coupled plasma chemical vapor deposition

Thin silicon nitride films were prepared at 350 degrees C by inductively coupled plasma chemical vapor deposition on Si(100) substrates under different NH(3)/SiH(4) or N(2)/SiH(4) gas mixture. The chemical composition and bonding structure of the deposited films were investigated as a function of the process parameters, such as the gas flow ratio NH(3)/SiH(4) or N(2)/SiH(4) and the RF power, using X-ray photoelectron spectroscopy (XPS). The gas flow ratio was 1.4, 4.3, 7.2 or 9.5 and the RF power, 50 or 100 W. Decomposition results of Si 2p XPS spectra indicated the presence of bulk Si, under-stoichiometric nitride, stoichiometric nitride Si(3)N(4), oxynitride SiN(x)O(y), and stoichiometric oxide SiO(2), and the amounts of these compounds were strongly influenced by the two process parameters. These results were consistent with those obtained from N 1s XPS spectra. The chemical composition ratio N/Si in the film increased with increasing the gas flow ratio until the gas flow ratio reached 4.3, reflecting the high reactivity of nitrogen, and stayed almost constant for further increase in gas flow ratio, the excess nitrogen being rejected from the growing film. A considerable and unexpected incorporation of contaminant oxygen and carbon into the depositing film was observed and attributed to their high chemical reactivity. (C) 2010 Elsevier B.V. All rights reserved.

X-ray photoelectron spectroscopy analysis of zirconium nitride-like films prepared on Si(100) substrates by ion beam assisted deposition

Thin zirconium nitride films were prepared on Si(l 00) substrates at room temperature by ion beam assisted deposition with a 2 keV nitrogen ion beam. Arrival rate ratios ARR(N/Zr) used were 0.19, 0.39, 0.92, and 1.86. The chemical composition and bonding structure of the films were analyzed with X-ray photoelectron spectroscopy (XPS). Deconvolution results for Zr 3d, Zr 3p(3/2), N 1s, O 1s, and C 1s XPS spectra indicated self-consistently the presence of metal Zr-0, nitride ZrN, oxide ZrO2, oxymnide Zr2N2O, and carbide ZrC phases, and the amounts of these compounds were influenced by ARR(N/Zr). The chemical composition ratio N/Zr in the film increased with increasing ARR(N/Zr) until ARR(N/Zr) reached 0.92, reflecting the high reactivity of nitrogen in the ion beam, and stayed almost constant for ARR(N/Zr) >= 1, the excess nitrogen being rejected from the growing film. A considerable incorporation of contaminant oxygen and carbon into the depositing film was attributed to the getter effect of zirconium. (C) 2007 Elsevier B.V. All rights reserved.

Classical simulation of deposition of thiophene oligomers on TiO(2)-anatase: Relevance of long-range electrostatic interactions

We performed classical molecular dynamics simulations of the vapor-deposition of alpha-T4 oligomers on the TiO(2)-anatase (101) surface, comparing different sets of charges associated with the atoms of the model. The potential energy surfaces for alpha-T4 and TiO(2) were described by re-parametrizations of the Universal force field with charges given by the charge equilibration (QEq) scheme, or with fixed charges obtained by an ab initio method using the Hirshfeld partition. The two sets of charges lead to completely different results for the interface formation, and for the characteristics of the organic film, with a clearly defined alpha-T4 contact layer in the QEq case, and a more homogeneous molecular distribution when using Hirshfeld charges. The main reason for the discrepancy was found to be the incorrect charge assignment given by QEq to the sulfur and alpha-carbon atoms in thiophenes, and highlight the relevance of long-range interactions in the organization of molecular films. (C) 2009 Elsevier B.V. All rights reserved.

Ion beam assisted deposition of an organic light emitting diode electrode

This work presents the electro-optical characterization of metal-organic interfaces prepared by the Ion Beam Assisted Deposition (IBAD) method. IBAD applied in this work combines simultaneously metallic film deposition and bombardment with an independently controlled ion beam, allowing different penetration of the ions and the evaporated metallic elements into the polymer. The result is a hybrid, non-abrupt interface, where polymer, metal and ion coexists. We used an organic light emitting diode, which has a typical vertical-architecture, for the interface characterization: Glass/Indium Tin Oxide (ITO)/Poly[ethylene-dioxythiophene/poly{styrenesulfonicacid}]) (PEDOT:PSS) /Emitting Polymer/Metal. The emitting polymer layer comprised of the Poly[(9,9-dioctyl-2,7-divinylenefluorenylene)-alt-co-{2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene}] (PFO) and the metal layer of aluminum prepared with different Ar(+) ion energies varying in the range from 0 to 1000 eV. Photoluminescence, Current-Voltage and Electroluminescence measurements were used to study the emission and electron injection properties. Changes of these properties were related with the damage caused by the energetic ions and the metal penetration into the polymer. Computer simulations of hybrid interface damage and metal penetration were confronted with experimental data. (C) 2010 Elsevier B.V. All rights reserved.

Atmospheric effects on extensive air showers observed with the surface detector of the Pierre Auger observatory

Atmospheric parameters, Such as pressure (P), temperature (T) and density (rho proportional to P/T), affect the development of extensive air showers initiated by energetic cosmic rays. We have Studied the impact of atmospheric variations on extensive air showers by means of the surface detector of the Pierre Auger Observatory. The rate of events shows a similar to 10% seasonal modulation and similar to 2% diurnal one. We find that the observed behaviour is explained by a model including the effects associated with the variations of P and rho. The former affects the longitudinal development of air showers while the latter influences the Moliere radius and hence the lateral distribution of the shower particles. The model is validated with full simulations of extensive air showers using atmospheric profiles measured at the site of the Pierre Auger Observatory. (C) 2009 Elsevier B.V. All rights reserved.

Electrophoretic deposition of Ba0.77Ca0.23TiO3 nanopowders

Ba0.77Ca0.23TiO3 (BCT23) nanometric powders, synthesized by the modified Pechini method, were used as precursor to produce thick films (50-130 mu m) employing the electrophoretic deposition (EPD) technique. The BCT23 powder presented a single crystalline phase with an average particle size and a crystallite size of similar to 60 nm and similar to 20 nm, respectively, when calcined at 800 degrees C/2h. BCT23 thick films were deposited on platinum substrates starting from different suspensions prepared by dispersion of the powder into: isopropyl alcohol (IPA) or a mixture of acetylacetone (Acac) and ethanol (EtOH) (1:1, volumetric ratio). A milling process was used to deagglomerate the powders in order to increase the suspension stability and improving the deposition. Dense and crack free thick films with uniform microstructure were obtained after sintering at 1300 degrees C/2 h from Acac+EtOH solution. (C) 2007 Elsevier B.V. All rights reserved.

Insights into the dynamics and sources of atmospheric lead and particulate matter in Sao Paulo, Brazil, from high temporal resolution sampling

We present the first results of a study investigating the processes that control concentrations and sources of Pb and particulate matter in the atmosphere of Sao Paulo City Brazil Aerosols were collected with high temporal resolution (3 hours) during a four-day period in July 2005 The highest Pb concentrations measured coincided with large fireworks during celebration events and associated to high traffic occurrence Our high-resolution data highlights the impact that a singular transient event can have on air quality even in a megacity Under meteorological conditions non-conducive to pollutant dispersion Pb and particulate matter concentrations accumulated during the night leading to the highest concentrations in aerosols collected early in the morning of the following day The stable isotopes of Pb suggest that emissions from traffic remain an Important source of Pb in Sao Paulo City due to the large traffic fleet despite low Pb concentrations in fuels (C) 2010 Elsevier BV All rights reserved

P-T-Fluid evolution and graphite deposition during retrograde metamorphism in Ribeira Fold Belt, SE Brazil: Oxygen fugacity, fluid inclusions and C-O-H isotopic evidence

Combined fluid inclusion (FI) microthermometry, Raman spectroscopy, X-ray diffraction, C-O-H isotopes and oxygen fugacities of granulites from central Ribeira Fold Belt, SE Brazil, provided the following results: i) Magnetite-Hematite fO(2) estimates range from 10(-11.5) bar (QFM + 1) to 10(-18.3) bar (QFM - 1) for the temperature range of 896 degrees C-656 degrees C, implying fO(2) decrease from metamorphic peak temperatures to retrograde conditions; ii) 5 main types of fluid inclusions were observed: a) CO(2) and CO(2)-N(2) (0-11 mol%) high to medium density (1.01-0.59 g/cm(3)) FI; b) CO(2) and CO(2)-N(2) (0-36 mol%) low density (0.19-0.29 g/cm(3)) FI; c) CO(2) (94-95 mol%)-N(2) (3 mol%)-CH(4) (2-3 mol%)-H(2)O (water phi(v) (25 degrees C) = 0.1) FI; d) low-salinity H(2)O-CO(2) FI; and e) late low-salinity H(2)O FI; iii) Raman analyses evidence two graphite types in khondalites: an early highly ordered graphite (T similar to 450 degrees C) overgrown by a disordered kind (T similar to 330 degrees C); iv) delta(18)O quartz results of 10.3-10.7 parts per thousand, imply high-temperature CO(2) delta(18)O values of 14.4-14.8 parts per thousand, suggesting the involvement of a metamorphic fluid, whereas lower temperature biotite delta(18)O and delta D results of 7.5-8.5 parts per thousand and -54 to -67 parts per thousand respectively imply H(2)O delta(18)O values of 10-11 parts per thousand and delta D(H2O) of -23 to -36 parts per thousand suggesting delta(18)O depletion and increasing fluid/rock ratio from metamorphic peak to retrograde conditions. Isotopic results are compatible with low-temperature H(2)O influx and fO(2) decrease that promoted graphite deposition in retrograde granulites, simultaneous with low density CO(2), CO(2)-N(2) and CO(2)-N(2)-CH(4)-H(2)O fluid inclusions at T = 450-330 degrees C. Graphite delta(13)C results of -10.9 to -11.4 parts per thousand imply CO(2) delta(13)C values of -0.8 to -1.3 parts per thousand suggesting decarbonation of Cambrian marine carbonates with small admixture of lighter biogenic or mantle derived fluids. Based on these results, it is suggested that metamorphic fluids from the central segment of Ribeira Fold Belt evolved to CO(2)-N(2) fluids during granulitic metamorphism at high fO(2), followed by rapid pressure drop at T similar to 400-450 degrees C during late exhumation that caused fO(2) reduction induced by temperature decrease and water influx, turning carbonic fluids into CO(2)-H(2)O (depleting biotite delta(18)O and delta D values), and progressively into H(2)O. When fO(2) decreased substantially by mixture of carbonic and aqueous fluids, graphite deposited forming khondalites. (C) 2010 Elsevier Ltd. All rights reserved.

A geochemical and lead isotopic record from a small pond in a remote equatorial island, Fernando de Noronha, Brazil

A 72 cm long core was collected from Lagoa da Viracao (LV), a small poind in the Fernando de Noronha island, northern Brazil. Sediments from the lower section of the core (20-72 cm depth) contain essentially mineral matter, while in the upper section (0-20 cm depth) mineral matter is mixed with organic matter. Lithogenic conservative elements - Si, Al, Fe, Ti, Co, Cr, Cu, Ba, Ga, Hf, Nb, Ni, Y, V, Zn, Zr and REE - exhibit remarkably constant values throughout the core, with concentrations similar to those of the bedrock. The vertical distribution of soluble elements - Ca, Mg, Na, K, P, Mn and Sr - is also homogeneous, but these elements are systematically depleted in relation to the bedrock. LOI, TOC, Br, Se, Hg and Pb, although showing nearly constant values in the lower section of the core, are significantly enriched in the upper section. The concentration profiles of Br and Se suggest that they may be accounted for by natural processes, related to the slight affinity of these elements for organic matter. On the other hand, the elevated levels of Hg and Pb in recent sediments may be explained by their long-range atmospheric transport and deposition. Furthermore, the isotopic composition of Pb clearly indicates that anthropogenic sources contributed to the Pb burden in the uppermost pond sediments.

Detection and Characterization of Cholesterol-Oxidized Products Using HPLC Coupled to Dopant Assisted Atmospheric Pressure Photoionization Tandem Mass Spectrometry

Oxidation of cholesterol (Ch) by a variety of reactive oxygen species gives rise mainly to hydroperoxides and aldehydes. Despite the growing interest in Ch-oxidized products, the detection and characterization of these products is still a matter of concern. In this work, the main Ch-oxidized products, namely, 3 beta-hydroxycholest-5-ene-7 alpha-hydroperoxide (7 alpha-OOH), 3 beta-5 alpha-cholest-6-ene-5-hydroperoxide (5 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 alpha-hydroperoxide (6 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 beta-hydroperoxide (6 beta-OOH), and 3 beta-hydroxy-5 beta-hydroxy-B-norcholestane-6 beta-carboxaldehyde (ChAld), were detected in the same analysis using high-performance liquid chromatography (HPLC) coupled to dopant assisted atmospheric pressure photoionization tandem mass spectrometry. The use of selected reaction monitoring mode (SRM) allowed a sensitive detection of each oxidized product, while the enhanced product ion mode (EPI) helped to improve the confidence of the analyses. Isotopic labeling experiments enabled one to elucidate mechanistic features during fragmentation processes. The characteristic fragmentation pattern of Ch-oxidized products is the consecutive loss of 1120 molecules, yielding cationic fragments at m/z 401, 383, and 365. Homolytic scissions of the peroxide bond are also seen. With (18)O-labeling approach, it was possible to establish a fragmentation order for each isomer. The SRM transitions ratio along with EPI and (18)O-labeled experiments give detailed information about differences for water elimination, allowing a proper discrimination between the isomers:Phis is of special interest considering the emerging role of Ch-oxidized products in the development of diseases.

Versatile microanalytical system with porous polypropylene capillary membrane for calibration gas generation and trace gaseous pollutants sampling applied to the analysis of formaldehyde, formic acid, acetic acid and ammonia in outdoor air

The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the mu g m(-3) range) and their variations with sampling site and time In this work a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE) a quick separation technique that requires nothing more than some nanoliters of sample and when combined with capacitively coupled contactless conductometric detection (C(4)D) is particularly favorable for ionic species that do not absorb in the UV-vis region like the target analytes formaldehyde formic acid acetic acid and ammonium The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry s constant such as formaldehyde and carboxylic acids or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8 3 nLs(-1)) while the sample was aspirated through the annular gap of the concentric tubes at 25 mLs(-1) A second unit in all similar to the CMDS was operated as a capillary membrane diffusion emitter (CMDE) generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS The fluids of the system were driven with inexpensive aquarium air pumps and the collected samples were stored in vials cooled by a Peltier element Complete protocols were developed for the analysis in air of NH(3) CH(3)COOH HCOOH and with a derivatization setup CH(2)O by associating the CMDS collection with the determination by CE-C(4)D The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot s reaction Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW) All techniques and methods of this work are in line with the green analytical chemistry trends (C) 2010 Elsevier B V All rights reserved

Determination of anthropogenic and biogenic compounds on atmospheric aerosol collected in urban, biomass burning and forest areas in Sao Paulo, Brazil

This study was conducted at three sites of different characteristics in Sao Paulo State Sao Paulo (SPA), Piracicaba (PRB) and Mate Atlantica Forest (MAT) PM(10), n-alkanes. pristane and phytane, PAHs, water-soluble ions and biomass burning tracers like levoglucosan and retene, were determined in quartz fiber filters. Samplings occurred on May 8th to August 8th, 2007 at the MAT site; on August 15th to 29th in 2007 and November 10th to 29th in 2008 at the PRB site and, March 13th to April 4th in 2007 and August 7th to 29th in 2008 at the SPA site Aliphatic compounds emitted biogenically were less abundant at the urban sites than at the forest site, and its distribution showed the influence of tropical vascular plants Air mass transport front biomass burning regions is likely to impact the sites with specific molecular markers The concentrations of all species were variable and dependent of seasonal changes In the most dry and polluted seasons, n-alkane and canon total concentrations were similar between the megacity and the biomass burning site PAHs and inorganic ion abundances were higher at Sao Paulo than Piracicaba, yet, the site influenced by biomass burning seems lobe the most impacted by the organic anion abundance in the atmosphere Pristane and phytane confirm the contamination by petroleum residues at urban sites, at the MAT site, biological activity and long range transport of pollutants might influence the levels of pristane (C) 2010 Elsevier B V All rights reserved

Platinum nanoparticle-modified electrodes, morphologic, and electrochemical studies concerning electroactive materials deposition

The present work describes the synthesis of platinum nanoparticles followed by their electrophoretic deposition onto transparent fluorine-doped tin oxide electrodes. The nano-Pt-modified electrodes were characterized by voltammetric studies in acidic solutions showing a great electrocatalytic behavior towards H(+) reduction being very interesting for fuel cell applications. Morphological characterization was performed by atomic force microscopy on different modified electrodes showing a very rough surface which can be tuned by means of time of deposition. Also, nickel hydroxide thin films were galvanostatically grown onto these electrodes showing an interesting electrochemical behavior as sharper peaks, indicating a faster ionic exchange from the electrolyte to the film.