In-situ comparison of the NOy instruments flown in MOZAIC and SPURT

Two aircraft instruments for the measurement of total odd nitrogen (NOy) were compared side by side aboard a Learjet A35 in April 2003 during a campaign of the AFO2000 project SPURT (Spurengastransport in der Tropopausenregion). The instruments albeit employing the same measurement principle (gold converter and chemiluminescence) had different inlet configurations. The ECO-Physics instrument operated by ETH-Zürich in SPURT had the gold converter mounted outside the aircraft, whereas the instrument operated by FZ-Jülich in the European project MOZAIC III (Measurements of ozone, water vapour, carbon monoxide and nitrogen oxides aboard Airbus A340 in-service aircraft) employed a Rosemount probe with 80 cm of FEP-tubing connecting the inlet to the gold converter. The NOy concentrations during the flight ranged between 0.3 and 3 ppb. The two data sets were compared in a blind fashion and each team followed its normal operating procedures. On average, the measurements agreed within 7%, i.e. within the combined uncertainty of the two instruments. This puts an upper limit on potential losses of HNO3 in the Rosemount inlet of the MOZAIC instrument. Larger transient deviations were observed during periods after calibrations and when the aircraft entered the stratosphere. The time lag of the MOZAIC instrument observed in these instances is in accordance with the time constant of the MOZAIC inlet line determined in the laboratory for HNO3.

A methodology for in-situ and remote sensing of microphysical and radiative properties of contrails as they evolve into cirrus

Contrails and especially their evolution into cirrus-like clouds are thought to have very important effects on local and global radiation budgets, though are generally not well represented in global climate models. Lack of contrail parameterisations is due to the limited availability of in situ contrail measurements which are difficult to obtain. Here we present a methodology for successful sampling and interpretation of contrail microphysical and radiative data using both in situ and remote sensing instrumentation on board the FAAM BAe146 UK research aircraft as part of the COntrails Spreading Into Cirrus (COSIC) study.

In-situ spatio-temporal measurements of the detailed azimuthal substructure of the substorm current wedge

The substorm current wedge (SCW) is a fundamental component of geomagnetic substorms. Models tend to describe the SCW as a simple line current flowing into the ionosphere towards dawn and out of the ionosphere towards dusk, linked by a westward electrojet. We use multi-spacecraft observations from perigee passes of the Cluster 1 and 4 spacecraft during a substorm on 15 Jan 2010, in conjunction with ground-based observations, to examine the spatial structuring and temporal variability of the SCW. At this time, the spacecraft travelled east-west azimuthally above the auroral region. We show that the SCW has significant azimuthal sub-structure on scales of 100~km at altitudes of 4,000-7,000~km. We identify 26 individual current sheets in the Cluster 4 data and 34 individual current sheets in the Cluster 1 data, with Cluster 1 passing through the SCW 120-240~s after Cluster 4 at 1,300-2,000~km higher altitude. Both spacecraft observed large-scale regions of net upward and downward field-aligned current, consistent with the large-scale characteristics of the SCW, although sheets of oppositely directed currents were observed within both regions. We show that the majority of these current sheets were closely aligned to a north-south direction, in contrast to the expected east-west orientation of the pre-onset aurora. Comparing our results with observations of the field-aligned current associated with bursty bulk flows (BBFs) we conclude that significant questions remain for the explanation of SCW structuring by BBF driven ``wedgelets". Our results therefore represent constraints on future modelling and theoretical frameworks on the generation of the SCW.

Clouds, aerosols, and precipitation in the marine boundary layer: an ARM Mobile Facility Deployment

The Clouds, Aerosol, and Precipitation in the Marine Boundary Layer (CAP-MBL) deployment at Graciosa Island in the Azores generated a 21-month (April 2009–December 2010) comprehensive dataset documenting clouds, aerosols, and precipitation using the Atmospheric Radiation Measurement Program (ARM) Mobile Facility (AMF). The scientific aim of the deployment is to gain improved understanding of the interactions of clouds, aerosols, and precipitation in the marine boundary layer. Graciosa Island straddles the boundary between the subtropics and midlatitudes in the northeast Atlantic Ocean and consequently experiences a great diversity of meteorological and cloudiness conditions. Low clouds are the dominant cloud type, with stratocumulus and cumulus occurring regularly. Approximately half of all clouds contained precipitation detectable as radar echoes below the cloud base. Radar and satellite observations show that clouds with tops from 1 to 11 km contribute more or less equally to surface-measured precipitation at Graciosa. A wide range of aerosol conditions was sampled during the deployment consistent with the diversity of sources as indicated by back-trajectory analysis. Preliminary findings suggest important two-way interactions between aerosols and clouds at Graciosa, with aerosols affecting light precipitation and cloud radiative properties while being controlled in part by precipitation scavenging. The data from Graciosa are being compared with short-range forecasts made with a variety of models. A pilot analysis with two climate and two weather forecast models shows that they reproduce the observed time-varying vertical structure of lower-tropospheric cloud fairly well but the cloud-nucleating aerosol concentrations less well. The Graciosa site has been chosen to be a permanent fixed ARM site that became operational in October 2013.

The partial oxidation of methane over Pd/Al2O3 catalyst nanoparticles studied in-situ by near ambient-pressure x-ray photoelectron spectroscopy

Near ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) is used to study the chemical state of methane oxidation catalysts in-situ. Al2O3{supported Pd catalysts are prepared with different particle sizes ranging from 4 nm to 10 nm. These catalysts were exposed to conditions similar to those used in the partial oxidation of methane (POM) to syn-gas and simultaneously monitored by NAP-XPS and mass spectrometry. NAP-XPS data show changes in the oxidation state of the palladium as the temperature in- creases, from metallic Pd0 to PdO, and back to Pd0. Mass spectrometry shows an increase in CO production whilst the Pd is in the oxide phase, and the metal is reduced back under presence of newly formed H2. A particle size effect is observed, such that CH4 conversion starts at lower temperatures with larger sized particles from 6 nm to 10 nm. We find that all nanoparticles begin CH4 conversion at lower temperatures than polycrystalline Pd foil.

Holocene Climatic Optimum centennial-scale paleoceanography in the NE Aegean (Mediterranean sea)

Combined micropaleontological and geochemical analyses of the high-sedimentation gravity core M-4G provided new centennial-scale paleoceanographic data for sapropel S1 deposition in the NE Aegean Sea during the Holocene Climatic Optimum. Sapropel layer S1a (10.2–8.0 ka) was deposited in dysoxic to oxic bottom waters characterized by a high abundance of benthic foraminiferal species tolerating surface sediment and/or pore water oxygen depletion (e.g., Chilostomella mediterranensis, Globobulimina affinis), and the presence of Uvigerina mediterranea, which thrives in oxic mesotrophic-eutrophic environments. Preservation of organic matter (OM) is inferred based on high organic carbon as well as loliolide and isololiolide contents, while the biomarker record and the abundances of eutrophic planktonic foraminifera document enhanced productivity. High inputs of terrigenous OM are attributed to north Aegean borderland riverine inputs. Both alkenone-based sea surface temperatures (SSTs) and δO18G. bulloides records indicate cooling at 8.2 ka (S1a) and ~7.8 ka (S1 interruption). Sapropelic layer S1b (7.7–6.4 ka) is characterized by rather oxic conditions; abundances of foraminiferal species tolerant to oxygen depletion are very low compared with the U. mediterranea rise. Strongly fluctuating SSTs demonstrate repeated cooling and associated dense water formation, with a major event at 7.4 ka followed by cold spells at 7.0, 6.8, and 6.5 ka. The prominent rise of the carbon preference index within the S1b layer indicates the delivery of less degraded terrestrial OM. The increase of algal biomarkers, labile OM-feeding foraminifera and eutrophic planktonic species pinpoints an enhanced in situ marine productivity, promoted by more efficient vertical convection due to repeated cold events. The associated contributions of labile marine OM along with fresher terrestrial OM inputs after ~7.7 ka imply sources alternative/additional to the north Aegean riverine borderland sources for the influx of organic matter in the south Limnos Basin, plausibly related to the inflow of highly productive Marmara/Black Sea waters.

High frequency of immature dendritic cells and altered in situ production of interleukin-4 and tumor necrosis factor-alpha in lung cancer

Introduction Antigen-presenting cells, like dendritic cells (DCs) and macrophages, play a significant role in the induction of an immune response and an imbalance in the proportion of macrophages, immature and mature DCs within the tumor could affect significantly the immune response to cancer. DCs and macrophages can differentiate from monocytes, depending on the milieu, where cytokines, like interleukin (IL)-4 and granulocyte-macrophage colony-stimulating factor (GM-CSF) induce DC differentiation and tumor necrosis factor (TNF)-alpha induce DC maturation. Thus, the aim of this work was to analyze by immunohistochemistry the presence of DCs (S100+ or CD1a+), macrophages (CD68+), IL-4 and TNF-alpha within the microenvironment of primary lung carcinomas. Results Higher frequencies of both immature DCs and macrophages were detected in the tumor-affected lung, when compared to the non-affected lung. Also, TNF-alpha-positive cells were more frequent, while IL-4-positive cells were less frequent in neoplastic tissues. This decreased frequency of mature DCs within the tumor was further confirmed by the lower frequency of CD14-CD80+ cells in cell suspensions obtained from the same lung tissues analyzed by flow cytometry. Conclusion These data are discussed and interpreted as the result of an environment that does not oppose monocyte differentiation into DCs, but that could impair DC maturation, thus affecting the induction of effective immune responses against the tumor.

Microgranitic Enclaves as Products of Self-mixing Events: a Study of Open-system Processes in the Maua Granite, Sao Paulo, Brazil, Based on in situ Isotopic and Trace Elements in Plagioclase

Felsic microgranular enclaves with structures indicating that they interacted in a plastic state with their chemically similar host granite are abundant in the Maua Pluton, SE Brazil. Larger plagioclase xenocrysts are in textural disequilibrium with the enclave groundmass and show complex zoning patterns with partially resorbed An-rich cores (locally with patchy textures) surrounded by more sodic rims. In situ laser ablation-(multi-collector) inductively coupled plasma mass spectrometry trace element and Sr isotopic analyses performed on the plagioclase xenocrysts indicate open-system crystallization; however, no evidence of derivation from more primitive basic melts is observed. The An-rich cores have more radiogenic initial Sr isotopic ratios that decrease towards the outermost part of the rims, which are in isotopic equilibrium with the matrix plagioclase. These profiles may have been produced by either (1) diffusional re-equilibration after rim crystallization from the enclave-forming magma, as indicated by relatively short calculated residence times, or (2) episodic contamination with a decrease of the contaminant ratio proportional to the extent to which the country rocks were isolated by the crystallization front. Profiles of trace elements with high diffusion coefficients would require unrealistically long residence times, and can be modeled in terms of fractional crystallization. A combination of trace element and Sr isotope data suggests that the felsic microgranular enclaves from the Maua Pluton are the products of interaction between end-member magmas that had similar compositions, thus recording `self-mixing` events.

Effect of Calcium Pre-rinse and Fluoride Dentifrice on Enamel and on Dental Plaque Formed In Situ

Purpose: The aim of this in situ double-blind randomised crossover study was to investigate the effect of calcium (Ca) pre-rinse on the composition of plaque and on enamel prior to the use of fluoride (F) dentifrice. Materials and Methods: During four phases (14 days each) of this study, 10 volunteers had agreed to wear dental appliances containing two healthy bovine enamel blocks. A fresh solution containing 20% weight/volume (w/v) sucrose was dripped on the enamel blocks ex vivo for 5 min three times a day. Subsequently, the appliances were replaced in the mouth, and the volunteers rinsed their mouth with 10 mL of a Ca (150 mmol/L) or a placebo rinse (1 min). In sequence, a slurry (1:3 w/v) of F (1030 ppm) or placebo dentifrice was dripped onto the blocks ex vivo for 1 min. During this time, the volunteers brushed their teeth with the respective dentifrice. The appliances were replaced in the mouth, and the volunteers rinsed their mouth with water. The plaque formed on the blocks was analysed for F and Ca. The enamel demineralisation as well as the incorporation of F on enamel was evaluated by cross-sectional microhardness and alkali-soluble F analysis, respectively. Data were tested using analysis of variance (P < 0.05). Results: The Ca pre-rinse prior to the use of the F dentifrice led to a three- and sixfold increase in the plaque F and Ca concentrations, respectively. It also did not have any additive effect on the F content on the enamel and the demineralisation of the enamel, in comparison with the use of F dentifrice alone. Conclusions: A Ca lactate rinse used prior to the F dentifrice was able to change the mineral content in the plaque, but it was unable to prevent enamel demineralisation.

PtSnCe/C electrocatalysts for ethanol oxidation: DEFC and FTIR ""in-situ"" studies

The ethanol oxidation reaction (EOR) was investigated using PtSnCe/C electrocatalysts in different mass ratios (72:23:5, 68:22:10 and 64:21:15) that were prepared by the polymeric precursor method. Transmission electron microscopy (TEM) showed that the particles ranged in size from approximately 2 to 5 nm. Changes in the net parameters observed for Pt suggest the incorporation of Sn and Ce into the Pt crystalline network with the formation of an alloy between Pt, Sn and/or Ce. Among the PtSnCe catalysts investigated, the 68:22:10 composition showed the highest activity toward ethanol oxidation, and the current time curves obtained in the presence of ethanol in acidic media showed a current density 50% higher than that observed for commercial PtSn/C (E-Tek). During the experiments performed on single direct ethanol fuel cells, the power density for the PtSnCe/C 68:22:10 anode was nearly 40% higher than the one obtained using the commercial catalyst. Data from Fourier transform infrared (FTIR) spectroscopy showed that the observed behavior for ethanol oxidation may be explained in terms of a double mechanism. The presence of Sn and Ce seems to favor CO oxidation, since they produce an oxygen-containing species to oxidize acetaldehyde to acetic acid. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

In Situ Infrared (FTIR) Study of the Mechanism of the Borohydride Oxidation Reaction on Smooth Pt Electrode

Although Pt has been thoroughly studied regarding its activity for the borohydride oxidation reaction (BOR), the BOR mechanism at Pt remains unclear: Depending on the applied potential, spontaneous BH(4)(-) hydrolysis can compete with the direct BOR. The goal of the present work is to provide more insight into the behavior of smooth Pt electrodes toward the BOR, by coupling in situ infrared reflectance spectroscopy with electrochemistry. The measurements were performed on a Pt electrode in 1 M NaOH/1 M NaBH(4), so as to detect the reaction intermediate species generated as a function of the applied potential. Several bands were monitored in the B-H ((v) over bar approximate to 1180, 1080, and 972 cm(-1)) and B-O ((v) over bar = 1325 and similar to 1425 cm(-1)) bond regions upon increased electrode polarization. These absorption bands, which appear sequentially and were already detected for similar measurements on Au electrodes, are assigned to BH(3), BH(2), and BO(2)(-) species. In light of these experimental data and previous results obtained in our group for Pt- or Au-based electrodes, possible initial elementary steps of the BOR on platinum electrodes are proposed and discussed according to the relevant literature data.

Construção de um aparato experimental para monitoramento in situ da deposição de filmes finos de titânio por magnetron sputtering

The technique of surface coating using magnetron sputtering is one of the most widely used in the surface engineering, for its versatility in obtaining different films as well as in the micro / nanometric thickness control. Among the various process parameters, those related to the active species of the plasma are of the most fundamental importance in the mechanism and kinetics of deposition. In order to identify the active species of the plasma, parameters such as gas flow, pressure and density of electric power were varied during titanium coating on glass substrate. By flowing argon gas of 10, 20, 30, 40 and 50 sccm (cubic centimeters per minute) for each gas flow a sequential scan of the electric current of 0.10, 0.20, 0.30, 0.40 , 0.50 A. The maximum value of 0.50 A was chosen based both on literature data and on limitations of the equipment. The monitoring of plasma species present during the deposition was carried out in situ by the technique of optical emission spectroscopy (OES) through the spectrometer Ocean Optics USB2000 Series. For this purpose, an apparatus was developed to adapt the OES inside the plasma reactor to stay positioned closest to the target. The radiations emitted by the species were detected by an optical fiber placed behind the glass substrate and their intensities as a function of wavelength were, displayed on a monitor screen. The acquisition time for each condition of the plain parameters was related to the minima of spectral lines intensities due to the film formed on the substrate. The intensities of different emission lines of argon and titanium were then analyzed as a function of time, to determine the active species and estimate the thickness of the deposited films. After the deposition, the coated glasses thin films were characterized by optical transmittance through an infrared laser. It was found that the thickness and deposition rate determined by in situ analysis were consistent with the results obtained by laser transmittance

Degradação in situ da matéria seca e da fração fibrosa do capim marandu obtido por diferentes métodos de amostragem, no período seco do ano

Este trabalho foi realizado na Faculdade de Ciências Agrárias Veterinárias - Unesp - Jaboticabal e foi conduzido, com o objetivo de avaliar a influência do método de amostragem do pasto sobre a degradabilidade in situ da matéria seca e da fração fibrosa de capim Marandu, colhido no período seco dos anos de 2003 e 2005. O experimento foi instalado em delineamento de blocos casualizados com parcela subdividida, com três repetições, representadas pelos piquetes amostrados. Nas parcelas, foram avaliados cinco métodos de amostragens de forragem (método do quadrado metálico; método de avaliação através de extrusa de bovino da raça Nelore; método de avaliação por meio de extrusa de bovino Cruzado (Red Angus x Nelore); método de avaliação por meio do pastejo, simulando bovino da raça Nelore; método de avaliação por meio do pastejo, simulando bovino Cruzado (Red Angus x Nelore) e as subparcelas foram constituídas pelos anos de amostragem, 2003 e 2005. Foram determinadas as frações da cinética ruminal: solúvel A; insolúvel potencialmente degradável B; taxa de degradação Kd; degradação potencial (DP) e fração não degradável C da MS e degradação potencial (DP), fração não degradável C e taxa de degradação Kd da FDN e da FDA. de acordo com os resultados obtidos, observou-se que o método do quadrado metálico subestimou as características da degradação do capim. Os métodos do pastejo simulado se assemelharam muito ao das extrusas, no entanto, a prática do simulador é que assegurou a amostragem eficiente, conforme foi constatado pelos dados obtidos no ano de 2003 e 2005.

Fission track and U-Pb in situ dating applied to detrital zircon from the Vale do Rio do Peixe Formation, Bauru Group, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Impact of the in situ formed salivary pellicle on enamel and dentine erosion induced by different acids

Objective. To investigate and compare the protective impact of the in situ formed salivary pellicle on enamel and dentine erosion caused by different acids at pH 2.6. Methods. Bovine enamel and dentine samples were exposed for 120 min in the oral cavity of 10 healthy volunteers. Subsequently, enamel and dentine pellicle-covered specimens were extraorally immersed in 1 ml hydrochloric, citric or phosphoric acid (pH 2.6, 60 s, each acid n=30 samples). Pellicle-free samples (each acid n=10) served as controls. Calcium release into the acid was determined by atomic absorption spectroscopy. The data were analysed by two-way ANOVA and Tukey's test (alpha=0.05). Results. Pellicle-covered samples showed significantly less calcium loss compared to pellicle-free samples in all acid groups. The mean (SD) pellicle protection (% reduction of calcium loss) was significantly better for enamel samples [60.9 (5.3)] than for dentine samples [30.5 (5.0)], but revealed no differences among the acids. Conclusion. The efficacy of the in situ pellicle in reducing erosion was 2-fold better for enamel than for dentine. Protection of the pellicle was not influenced by the kind of acid when enamel and dentine erosion was performed at pH 2.6.