Why join a carbon club?: a study of the banks participating in the Brazilian “Business for Climate Platform”

Why do firms that present low levels of (direct) carbon emissions participate in “carbon clubs”, which have the goal of managing and reducing greenhouse gas (GHG) emissions? In order to answer this question, we collected data from both primary and secondary sources from firms operating in the Brazilian banking sector, which are members of the Businesses for Climate Platform (Plataforma Empresas pelo Clima e EPC). We first looked for answers in the institutional theory and resource based view of the firm (RBV). By confronting the arguments presented by these streams of scientific enquiry with empirical data, we worked on theory testing. In particular, we analyzed the institutional pressures and resources and capabilities of the focus companies, in order to understand the rationales for proactive sustainability management. We found evidences of the arguments presented by both the institutional theory and the RBV. By studying an industry that is not a frequent subject to research on socio-environmental issues e for not being considered of high impact e in an emerging market economy, the research contributes to both the further development of the institutional theory and the advancement of sustainability management in corporations.

Paleoambiente e proveniência da formação cabeças da bacia do Parnaíba: evidências da glaciação famenniana e implicações na potencialidade do reservatório

O histórico de prospecção de hidrocarbonetos da Bacia Paleozoica do Parnaíba, situada no norte-nordeste do Brasil, sempre foi considerado desfavorável quando comparado aos super-reservatórios estimados do Pré-Sal das bacias da Margem Atlântica e até mesmo interiores, como a Bacia do Solimões. No entanto, a descoberta de gás natural em depósitos da superseqüência mesodevoniana-eocarbonífera do Grupo Canindé, que incluem as formações Pimenteiras, Cabeças e Longá, impulsionou novas pesquisas no intuito de refinar a caracterização paleoambiental, paleogeográfica, bem como, entender o sistema petrolífero, os possíveis plays e a potencialidade do reservatório Cabeças. A avaliação faciológica e estratigráfica com ênfase no registro da tectônica glacial, em combinação com a geocronologia de zircão detrítico permitiu interpretar o paleoambiente e a proveniência do reservatório Cabeças. Seis associações de fácies agrupadas em sucessões aflorantes, com espessura máxima de até 60m registram a evolução de um sistema deltaico Devoniano influenciado por processos glaciais principalmente no topo da unidade. 1) frente deltaica distal, composta por argilito maciço, conglomerado maciço, arenito com acamamento maciço, laminação plana e estratificação cruzada sigmoidal 2) frente deltaica proximal, representada pelas fácies arenito maciço, arenito com laminação plana, arenito com estratificação cruzada sigmoidal e conglomerado maciço; 3) planície deltaica, representada pelas fácies argilito laminado, arenito maciço, arenito com estratificação cruzada acanalada e conglomerado maciço; 4) shoreface glacial, composta pelas fácies arenito com marcas onduladas e arenito com estratificação cruzada hummocky; 5) depósitos subglaciais, que englobam as fácies diamictito maciço, diamictito com pods de arenito e brecha intraformacional; e 6) frente deltaica de degelo, constituída pelas fácies arenito maciço, arenito deformado, arenito com laminação plana, arenito com laminação cruzada cavalgante e arenito com estratificação cruzada sigmoidal. Durante o Fammeniano (374-359 Ma) uma frente deltaica dominada por processos fluviais progradava para NW (borda leste) e para NE (borda oeste) sobre uma plataforma influenciada por ondas de tempestade (Formação Pimenteiras). Na borda leste da bacia, o padrão de paleocorrente e o espectro de idades U-Pb em zircão detrítico indicam que o delta Cabeças foi alimentado por áreas fonte situadas a sudeste da Bacia do Parnaíba, provavelmente da Província Borborema. Grãos de zircão com idade mesoproterozóica (~ 1.039 – 1.009 Ma) e neoproterozóica (~ 654 Ma) são os mais populosos ao contrário dos grãos com idade arqueana (~ 2.508 – 2.678 Ma) e paleoproterozóica (~ 2.054 – 1.992 Ma). O grão de zircão concordante mais novo forneceu idade ²⁰⁶Pb/²³⁸U de 501,20 ± 6,35 Ma (95% concordante) indicando idades de áreas-fonte cambrianas. As principais fontes de sedimentos do delta Cabeças na borda leste são produto de rochas do Domínio Zona Transversal e de plútons Brasilianos encontrados no embasamento a sudeste da Bacia do Parnaíba, com pequena contribuição de sedimentos oriundos de rochas do Domínio Ceará Central e da porção ocidental do Domínio Rio Grande do Norte. No Famenniano, a movimentação do supercontinente Gondwana para o polo sul culminou na implantação de condições glaciais concomitantemente com o rebaixamento do nível do mar e exposição da região costeira. O avanço das geleiras sobre o embasamento e depósitos deltaicos gerou erosão, deposição de diamictons com clastos exóticos e facetados, além de estruturas glaciotectônicas tais como plano de descolamento, foliação, boudins, dobras, duplex, falhas e fraturas que refletem um cisalhamento tangencial em regime rúptil-dúctil. O substrato apresentava-se inconsolidado e saturados em água com temperatura levemente abaixo do ponto de fusão do gelo (permafrost quente). Corpos podiformes de arenito imersos em corpos lenticulares de diamicton foram formados pela ruptura de camadas pelo cisalhamento subglacial. Lentes de conglomerados esporádicas (dump structures) nos depósitos de shoreface sugere queda de detritos ligados a icebergs em fases de recuo da geleira. A elevação da temperatura no final do Famenniano reflete a rotação destral do Gondwana e migração do polo sul da porção ocidental da América do Sul e para o oeste da África. Esta nova configuração paleogeográfica posicionou a Bacia do Parnaíba em regiões subtropicais iniciando o recuo de geleiras e a influência do rebound isostático. O alívio de pressão é indicado pela geração de sills e diques clásticos, estruturas ball-and-pillow, rompimento de camadas e brechas. Falhas de cavalgamento associadas à diamictitos com foliação na borda oeste da bacia sugerem que as geleiras migravam para NNE. O contínuo aumento do nível do mar relativo propiciou a instalação de sedimentação deltaica durante o degelo e posteriormente a implantação de uma plataforma transgressiva (Formação Longá). Diamictitos interdigitados com depósitos de frente deltaica na porção superior da Formação Cabeças correspondem a intervalos com baixo volume de poros e podem representar trapas estratigráficas secundárias no reservatório. As anisotropias primárias subglaciais do topo da sucessão Cabeças, em ambas as bordas da Bacia do Parnaíba, estende a influência glacial e abre uma nova perspectiva sobre a potencialidade efetiva do reservatório Cabeças do sistema petrolífero Mesodevoniano-Eocarbonífero da referida bacia.

Thermodynamics of a bouncer model: A simplified one-dimensional gas

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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)

Impact of the Manaus urban plume on trace gas mixing ratios near the surface in the Amazon Basin: Implications for the NO-NO2-O-3 photostationary state and peroxy radical levels

We measured the mixing ratios of NO, NO2, O-3, and volatile organic carbon as well as the aerosol light-scattering coefficient on a boat platform cruising on rivers downwind of the city of Manaus (Amazonas State, Brazil) in July 2001 (Large-Scale Biosphere-Atmosphere Experiment in Amazonia-Cooperative LBA Airborne Regional Experiment-2001). The dispersion and impact of the Manaus plume was investigated by a combined analysis of ground-based (boat platform) and airborne trace gas and aerosol measurements as well as by meteorological measurements complemented by dispersion calculations (Hybrid Single-Particle Lagrangian Integrated Trajectory model). For the cases with the least anthropogenic influence (including a location in a so far unexplored region similar to 150 km west of Manaus on the Rio Manacapuru), the aerosol scattering coefficient, sigma(s), was below 11 Mm(-1), NOx mixing ratios remained below 0.6 ppb, daytime O-3 mixing ratios were mostly below 20 ppb and maximal isoprene mixing ratios were about 3 ppb in the afternoon. The photostationary state (PSS) was not established for these cases, as indicated by values of the Leighton ratio, Phi, well above unity. Due to the influence of river breeze systems and other thermally driven mesoscale circulations, a change of the synoptic wind direction from east-northeast to south-southeast in the afternoon often caused a substantial increase of ss and trace gas mixing ratios (about threefold for sigma(s), fivefold for NOx, and twofold for O-3), which was associated with the arrival of the Manaus pollution plume at the boat location. The ratio F reached unity within its uncertainty range at NOx mixing ratios of about 3 ppb, indicating "steady-state" conditions in cases when radiation variations, dry deposition, emissions, and reactions mostly involving peroxy radicals (XO2) played a minor role. The median midday/afternoon XO2 mixing ratios estimated using the PSS method range from 90 to 120 parts per trillion (ppt) for the remote cases (sigma(s) < 11 Mm(-1) and NOx < 0.6 ppb), while for the polluted cases our estimates are 15 to 60 ppt. These values are within the range of XO2 estimated by an atmospheric chemistry box model (Chemistry As A Box model Application-Module Efficiently Calculating the Chemistry of the Atmosphere (CAABA/MECCA)-3.0).

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

Radiation metabolomics. 3. Biomarker discovery in the urine of gamma-irradiated rats using a simplified metabolomics protocol of gas chromatography-mass spectrometry combined with random forests machine learning algorithm

Abstract Radiation metabolomics employing mass spectral technologies represents a plausible means of high-throughput minimally invasive radiation biodosimetry. A simplified metabolomics protocol is described that employs ubiquitous gas chromatography-mass spectrometry and open source software including random forests machine learning algorithm to uncover latent biomarkers of 3 Gy gamma radiation in rats. Urine was collected from six male Wistar rats and six sham-irradiated controls for 7 days, 4 prior to irradiation and 3 after irradiation. Water and food consumption, urine volume, body weight, and sodium, potassium, calcium, chloride, phosphate and urea excretion showed major effects from exposure to gamma radiation. The metabolomics protocol uncovered several urinary metabolites that were significantly up-regulated (glyoxylate, threonate, thymine, uracil, p-cresol) and down-regulated (citrate, 2-oxoglutarate, adipate, pimelate, suberate, azelaate) as a result of radiation exposure. Thymine and uracil were shown to derive largely from thymidine and 2'-deoxyuridine, which are known radiation biomarkers in the mouse. The radiation metabolomic phenotype in rats appeared to derive from oxidative stress and effects on kidney function. Gas chromatography-mass spectrometry is a promising platform on which to develop the field of radiation metabolomics further and to assist in the design of instrumentation for use in detecting biological consequences of environmental radiation release.

Porosity, gas permeability and grain density of ODP Leg 194 sites

We report analyses of porosity and permeability of core samples from Site 1193 in the Northern Marion Platform, Sites 1196 and 1199 in the Southern Marion Platform, and Sites 1194, 1195, 1197, and 1198 from the slopes of these platforms. The samples include 415 horizontal 1-in plugs, 290 vertical 1-in plugs, and 23 whole-core pieces. Porosity and permeability analyses were possible for most, but not all, samples. Grain density measurements were also obtained for the horizontal plugs. Representative photomicrographs are provided of thin sections from 139 of the horizontal plugs and the 23 whole-core pieces.

(Table 1) Isotopic and geochemical parameters of gas phase from underground fluids of the Baikal rift and its framing

Results of studying isotopic composition of helium in underground fluids of the Baikal-Mongolian region during the last quarter of XX century are summarized. Determinations of 3He/4He ratio in 139 samples of gas phase from fluids, collected at 104 points of the Baikal rift zone and adjacent structures are given. 3He/4He values lie within the range from 1x10**-8 (typical for crustal radiogenic helium) to 1.1x10**-5 (close to typical MORB reservoir). Repeated sampling in some points during more than 20 years showed stability of helium isotopic composition in time in each of them at any level of 3He/4He values. There is no systematic differences of 3He/4He in samples from surface water sources and deeper intervals of boreholes in the same areas. Universal relationship between isotopic composition of helium and general composition of gas phase is absent either, but the minimum 3He/4He values occurred in methane gas of hydrocarbon deposits, whereas in nitrogen and carbon dioxide gases of helium composition varied (in the latter maximum 3He/4He values have been measured). According to N2/Ar_atm ratio nitrogen gases are atmospheric. In carbonic gas fN2/fNe ratio indicates presence of excessive (non-atmogenic) nitrogen, but the attitude CO2/3He differs from one in MORB. Comparison of helium isotopic composition with its concentration and composition of the main components of gas phase from fluids shows that it is formed under influence of fractionation of components with different solubility in the gas-water system and generation/consumption of reactive gases in the crust. Structural and tectonic elements of the region differ from the spectrum of 3He/4He values. At the pre-Riphean Siberian Platform the mean 3He/4He = (3.6+/-0.9)x10**- 8 is very close to radiogenic one. In the Paleozoic crust of Khangay 3He/4He = (16.3+/-4.6)x10**-8, and the most probable estimate is (12.3+/-2.9)x10**-8. In structures of the eastern flank of the Baikal rift zone (Khentei, Dauria) affected by the Mz-Kz activization 3He/4He values range from 4.4x10**-8 to 2.14x10**-6 (average 0.94x10**-6). Distribution of 3He/4He values across the strike of the Baikal rift zone indicates advective heat transfer from the mantle not only in the rift zone, but also much further to the east. In fluids of the Baikal rift zone range of 3He/4He values is the widest: from 4x10**-8 to 1.1x10**-5. Their variations along the strike of the rift zone are clearly patterned, namely, decrease of 3He/4He values in both directions from the Tunka depression. Accompanied by decrease in density of conductive heat flow and in size of rift basins, this trend indicates decrease in intensity of advective heat transfer from the mantle to peripheral segments of the rift zone. Comparing this trend with data on other continental rift zones and mid-ocean ridges leads to the conclusion about fundamental differences in mechanisms of interaction between the crust and the mantle in these environments.