High signal to noise ratio THz spectroscopy with ASOPS and signal processing schemes for mapping and controlling molecular and bulk relaxation processes

Asynchronous Optical Sampling has the potential to improve signal to noise ratio in THz transient sperctrometry. The design of an inexpensive control scheme for synchronising two femtosecond pulse frequency comb generators at an offset frequency of 20 kHz is discussed. The suitability of a range of signal processing schemes adopted from the Systems Identification and Control Theory community for further processing recorded THz transients in the time and frequency domain are outlined. Finally, possibilities for femtosecond pulse shaping using genetic algorithms are mentioned.

Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone

We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB) based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007). K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations. From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an approximate upper limit of similar to 10(-11) cm(2) s(-1) for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (carbon-carbon double bonds) can reach chemical lifetimes of many hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (< 10(-10) cm(2) s(-1)). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas–particle interactions (P¨oschl et al., 5 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface 10 concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory stud15 ies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical lifetimes of 20 multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (10−10 cm2 s−1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB 25 as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Palaeoenvironmental changes during the Valanginian: new insights from variations in phosphorus contents and bulk- and clay mineralogies in the western Tethys

Paleoenvironmental and paleoclimatic changes during the Valanginian carbon isotopic excursion (CIE) have been investigated in the western Tethys. For this purpose, bulk-rock and clay mineralogies, as well as phosphorus (P) contents were evaluated in a selection of five sections located in the Vocontian Basin (Angles, SE France; Alvier, E Switzerland; Malleval, E France), and the Lombardian Basin (Capriolo, N Italy; Breggia, S Switzerland). Within the CIE interval, bulk-rock and clay mineralogies are inferred to reflect mostly climate change. The onset of the CIE (Busnardoites campylotoxus ammonite Zone) is characterized by higher detrital index (DI: sum of the detrital minerals divided by calcite contents) values and the presence of kaolinite in their clay-mineral assemblages. In the late Valanginian (from the Saynoceras verrucosum Zone up to the end of the Valanginian), the samples show relatively variable DI and lower values or the absence of kaolinite. The variation in the mineralogical composition is interpreted as reflecting a change from a climate characterized by optimal weathering conditions associated with an increase in terrigenous input on the southern European margin during the CIE towards an overall unstable climate associated with drier conditions in the late Valanginian. This is contrasted by a dissymmetry (proximal vs distal) along the studied transect, the northern Tethyan margin being more sensitive to changes in continental input compared to the distal environments. P accumulation rates (PAR) present similar features. In the Vocontian basin, P content variations are associated with changes in terrigenous influx, whereas in the Lombardian basin (i.e. Capriolo and Breggia), PAR values are less well correlated. This is mainly because the deeper part of the Tethys was less sensitive to changes in continental inputs. The onset of the CIE (top of the B. campylotoxus Zone) records a general increase in PAR suggesting an increase in marine nutrient levels. This is linked to higher continental weathering rates and the enhanced influx of nutrients into the ocean. In the period corresponding to the shift itself, P contents show a dissymmetry between the Vocontian and Lombardian basins (proximal vs distal). For the sections of Malleval, Alvier and Angles, a decrease in P concentrations associated to a decrease in detrital input is observed. In Capriolo and Breggia, PAR show maximum values during the plateau, indicating a more complex interaction between different P sources. The time interval including the top of S. verrucosum Zone up to the end of the Valanginian is characterized by variable PAR values, suggesting variable nutrient influxes. These changes are in agreement with an evolution towards seasonally contrasted conditions in the late Valanginian.

Transatlantic flight times and climate change

Aircraft do not fly through a vacuum, but through an atmosphere whose meteorological characteristics are changing because of global warming. The impacts of aviation on climate change have long been recognised, but the impacts of climate change on aviation have only recently begun to emerge. These impacts include intensified turbulence and increased take-off weight restrictions. Here we investigate the influence of climate change on flight routes and journey times. We feed synthetic atmospheric wind fields generated from climate model simulations into a routing algorithm of the type used operationally by flight planners. We focus on transatlantic flights between London and New York, and how they change when the atmospheric concentration of carbon dioxide is doubled. We find that a strengthening of the prevailing jet-stream winds causes eastbound flights to significantly shorten and westbound flights to significantly lengthen in all seasons. Eastbound and westbound crossings in winter become approximately twice as likely to take under 5 h 20 min and over 7 h 00 min, respectively. For reasons that are explained using a conceptual model, the eastbound shortening and westbound lengthening do not cancel out, causing round-trip journey times to increase. Even assuming no future growth in aviation, the extrapolation of our results to all transatlantic traffic suggests that aircraft will collectively be airborne for an extra 2000 h each year, burning an extra 7.2 million gallons of jet fuel at a cost of US$ 22 million, and emitting an extra 70 million kg of carbon dioxide, which is equivalent to the annual emissions of 7100 average British homes. Our results provide further evidence of the two-way interaction between aviation and climate change.

Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 nanostructured silica in the simultaneous determination of divalent lead, copper and mercury ions

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol in the simultaneous determination of Pb(II), Cu(II) and Hg(II) ions in natural water and sugar cane spirit (cachaca) is described. Pb(II), Cu(II) and Hg(II) were pre-concentrated on the surface of the modified electrode by complexing with 2-benzothiazolethiol and reduced at a negative potential (-0.80 V). Then the reduced products were oxidised by DPASV procedure. The fact that three stripping peaks appeared on the voltammograms at the potentials of -0.48 V (Pb2+), -0.03 V (Cu2+) and +0.36 V (Hg2+) in relation to the SCE, demonstrates the possibility of simultaneous determination of Pb2+, Cu2+ and Hg2+. The best results were obtained under the following optimised conditions: 100 mV pulse amplitude, 3 min accumulation time, 25 mV s(-1) scan rate in phosphate solution pH 3.0. Using such parameters, calibration graphs were linear in the concentration ranges of 3.00-70.0 x 10(-7) mol L-1 (Pb2+), 8.00-100.0 X 10(-7) mol L-1 (Cu2+) and 2.00-10.0 x 10(-6) mol L-1 (Hg2+). Detection limits of 4.0 x 10(-8) mol L-1 (Pb2+), 2.0 x 10(-7) mol L-1 (Cu2+) and 4.0 x 10(-7) mol L-1 (Hg2+) were obtained at the signal noise ratio (SNR) of 3. The results indicate that this electrode is sensitive and effective for simultaneous determination of Pb2+, Cu2+ and Hg2+ in the analysed samples. (C) 2008 Published by Elsevier B.V.

Soybean compressibility and bulk density

The objective of this project was to study the influence of surcharge pressure and moisture content on the compressive behavior and bulk density of soybeans. Three varieties were selected with varying dimensions and shapes. Moisture contents of 10.5, 15.0, and 20% were tested at nine surcharge pressures in the range from 0 to 82.8 kPa. Results indicated that the bulk densities of different soybean varieties have similar behavior with respect to pressure level and moisture content but that the magnitude of bulk density was influenced by variety, Bulk density was influenced by both pressure level and moisture content. The four-element Burger model was found to adequately describe the bulk density of soybeans as a function of pressure for all varieties and moisture levels.

Surface dental enamel lead levels and antisocial behavior in Brazilian adolescents

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

Combined cycle versus one thousand diesel power plants: pollutant emissions, ecological efficiency and economic analysis

The increase in the use of natural gas in Brazil has stimulated public and private sectors to analyse the possibility of using combined cycle systems for generation of electrical energy. Gas turbine combined cycle power plants are becoming increasingly common due to their high efficiency, short lead times, and ability to meet environmental standards. Power is produced in a generator linked directly to the gas turbine. The gas turbine exhaust gases are sent to a heat recovery steam generator to produce superheated steam that can be used in a steam turbine to produce additional power. In this paper a comparative study between a 1000 MW combined cycle power plant and 1000 kW diesel power plant is presented. In first step, the energetic situation in Brazil, the needs of the electric sector modification and the needs of demand management and integrated means planning are clarified. In another step the characteristics of large and small thermoelectric power plants that use natural gas and diesel fuel, respectively, are presented. The ecological efficiency levels of each type of power plant is considered in the discussion, presenting the emissions of particulate material, sulphur dioxide (SO2), carbon dioxide (CO2) and nitrogen oxides (NOx). (c) 2006 Elsevier Ltd. All rights reserved.

Fluvial transport of lead, zinc and copper contents in polluted mining regions

Ore mines installed in the lower-middle portion of Ribeira de Iguape River (São Paulo State, southeastern Brazil), together with the Panelas Plant are responsible for the contamination of the Iguape-Cananeia-Paranagua lagoon-estuarine complex. The lower-middle portion of Grande Creek Basin, located in the district of Adrianopolis (Parana State, southern Brazil) is under environmental impact because of mining activities. The mines of Perau, at Perau Creek, Canoas at Canoas Creek, and Barrinha at Barrinha Creek and Laranjal Creek have been paralyzed. The transport of lead in fluvial sediments is mainly associated with organic matter, carbonates, the residual fraction, and adsorbables, whereas the transport of zinc is associated with the organic and residual fraction, oxides and hydroxides of iron and manganese, carbonate, and adsorbables. The transport of copper is associated with the residual fraction and oxides and hydroxides of iron and manganese, organic matter, carbonate, and adsorbables.

Relationship between grain-boundary capacitance and bulk shallow donors in SnO2 polycrystalline semiconductor

The relationship between grain-boundary capacitance and extrinsic shallow donors caused by Nb addition to SnO2 center dot COO binary polycrystalline system has been investigated by means of combined techniques such as I-V characteristic response, complex impedance and capacitance analysis and electrostatic force microscopy. The estimated role of the Nb doping is to increase the concentration of shallow donors that are capable of enhancing the electronic donation to grain-boundary acceptors. This effect leads to the formation of potential barriers at grain boundaries with a simultaneous increase of grain-boundary capacitance and non-Ohmic features of the polycrystalline device doped with Nb atoms.

Anodic Stripping Voltammetric Determination of Lead (II) and Cadmium (II) by Using a Carbon Nanotubes Paste Electrode Modified with Ion Exchange Synthetic Resin

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)