924 resultados para emission of hydrogen sulfide into the gas phase
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Purpose: This paper aims to describe an investigation into how company performance can be improved by integrating internal and external customers and technology. The approach was developed, implemented and evaluated in the operations of the building components industry. The research was carried out in the precast concrete division of a Singapore company. Design/methodology/ approach: For the purpose of undertaking the investigation an exploratory case study approach was used. This was divided into conceptual and action research stages. The action research was also used to implement the changes in the company. Questionnaire surveys were carried out among company employees and external customers to assess the effect of these changes. Results of the investigation were derived using content and statistical analysis. Triangulation between three sources was used for validating the data. Findings: The exploratory case study strategy resulted in rich research data, which provided evidence of the changes taking place and integration happening, leading to improved performance. The action research approach proved a powerful tool where the uncertainty of outcomes makes it near impossible to make accurate forecasts. Another output of the research was the development of an "integrated customer orientation" (ICO) model. Research limitations/implications: The research in this paper used a single site action research investigation so should be interpreted within the specific company and industry context. There are implications for theory and practice in a number of areas of production and marketing as well as contributions to understanding about productivity improvement and organisational development. The investigation also fulfils the dual objectives of action research by contributing to both knowledge and practice. Originality/value: The paper describes a unique approach towards improving productivity, quality and service through the use of action research to implement changes, as well as providing the research evidence to evaluate both the process of implementation and results achieved. © Emerald Group Publishing Limited.
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This study investigated the socialization of adjunct faculty into the academic culture of a community college campus. Because of the increased utilization of adjunct faculty, the need to socialize them to effectively function within the organizational culture has become more acute. A review of the literature revealed that when employees are socialized, they are more committed to the goals and welfare of the organization, are less likely to leave the organization, and are more productive and innovative. Therefore, it is important that administrators have programs and practices in place that would help to integrate adjunct faculty into the academic culture. The model of organizational socialization (Chao, O'Leary-Kelly, Wolf, Klein, & Gardner, 1994) formed the framework for this study, which was guided by the following research questions: How do adjunct faculty members describe their socialization into the culture of their college campus? How do administrators describe their roles and that of the organization in the socialization of adjunct faculty members? What organizational programs and activities are in place for the socialization of adjunct faculty? The North Campus of Miami Dade College was the site for this study, as it is a campus with a long history of utilizing adjunct faculty members and one that has a clearly-stated mission of adjunct faculty socialization. A qualitative case study method was used, and data collection included interviews and the review and analysis of institutional documents. The participants included 11 adjunct faculty members, 4 department chairpersons, the campus president, and the college training and development coordinator. The study revealed that there were structured and consistent professional development programs, but these conflicted with the schedules of adjunct faculty. Overall, adjunct faculty found support from the leadership; however, they revealed a need for more mentoring, more interactions with full-time faculty, and more input in decision making concerning textbooks and curricula. Implications and recommendations for practice include making professional development more accessible and relevant to adjunct faculty, developing a formal mentoring program where full-time faculty and veteran adjunct faculty mentor novice adjunct faculty, and involving adjuncts in decisions regarding curriculum and textbook selection.
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Antarctic krill (Euphausia superba), a key species of Southern Ocean food webs plays a central role in ecosystem processes, community dynamics of apex predators and as a commercial fishery target. A decline in krill abundance during the late 20th century in the SW Atlantic sector has been linked to a concomitant decrease in sea ice, based on the hypothesis that sea ice acts as a feeding ground for overwintering larvae. However, evidence supporting this hypothesis has been scarce due to logistical challenges of collecting data in austral winter. Here we report on a winter study that involved diver observations of larval krill in their under-ice environment, ship-based studies of krill, sea ice physical characteristics, and biophysical model analyses of krill-ocean-ice interactions. We present evidence that complex under-ice topography is vital for larval krill in terms of dispersal and advection into high productive nursery habitats, rather than the provision by the ice environment of food. Further, ongoing changes in sea ice will lead to increases in sea-ice regimes favourable for overwintering larval krill but shifting southwards. This will result in ice-free conditions in the SW Atlantic, which will be conducive for enhancing food supplies due to sufficient light and iron availability, thus enhancing larvae development and growth. However, the associated impact on dispersal and advection may lead to a net shift in krill from the SW Atlantic to regions further east by the eastward flowing ACC and the northern branch of the Weddell Gyre, with profound consequences for the Southern Ocean pelagic ecosystem.
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We report a study of the phase behavior of multiple-occupancy crystals through simulation. We argue that in order to reproduce the equilibrium behavior of such crystals it is essential to treat the number of lattice sites as a constraining thermodynamic variable. The resulting free-energy calculations thus differ considerably from schemes used for single-occupancy lattices. Using our approach, we obtain the phase diagram and the bulk modulus for a generalized exponential model that forms cluster crystals at high densities. We compare the simulation results with existing theoretical predictions. We also identify two types of density fluctuations that can lead to two sound modes and evaluate the corresponding elastic constants.
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Relief shown pictorially.
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Relief shown pictorially.
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The Amazon river prawn (Macrobrachium amazonicum) is a native species with great potential for aquaculture, based on promising results obtained from experimental culture trials in Brazil. The influence of different stocking densities on the development of prawns reared in cages in the nursery phase as well as on their growth when transferred to grow-out net pens at lower densities was evaluated. In the nursery phase, juveniles I (0.157 +/- 0.014 g, 47 days old) were stocked in 0.5 m(-2) cages at densities of 400, 800 and 1200 m(-2). After 71 days, prawns were transferred to grow-out net pens of 2.0 m(-2), at a density of 20 juveniles II m(-2). The treatments were determined by the mean weights registered for the prawns (118 days old) previously stocked at 400, 800 and 1200 juveniles I m(-2) in the nursery phase: 0.94 +/- 0.07 g (T1), 0.61 +/- 0.04 g (T2) and 0.48 +/- 0.07 g (T3), respectively. In the nursery phase, mean survival was above 96%, whereas mean weights were significantly higher (P<0.05) for the density of 400 prawns m(-2). The highest biomass (276.7 g) and productivity (1152 juveniles II m(-2)) were registered at the density of 1200 prawns m(-2), differing significantly (P<0.05) from the lower densities. One month after the transfer of the animals to the net pens, there was recovery in the specific growth rate (SGR) of prawns in all treatments which was significantly higher (P<0.05) in T3 (4.01 +/- 0.36% day(-1)) and T2 (3.60 +/- 0.18% day(-1)). The feed conversion efficiency (FCE) in the first month after the transfer was also significantly higher (P<0.05) in T3 (78.2 +/- 19.1%) when compared to T1 (39.8 +/- 9.5%). These results suggest the occurrence of a compensatory growth in M. amazonicum after transferring them to lower densities, which can point out high densities for nursery cages as a viable practice. After 277 days of grow-out phase in net pens in the cold season, survival, mean weight and biomass did not differ significantly among the treatments, indicating the viability of using net pens in stocking prawns during autumn and winter, since the minimum temperature does not drop below 17 degrees C. Influence of stocking density during the nursery phase on the grow-out of prawns was not observed. The population structure in prawns reared in net-pens was similar to that observed in earthen ponds. (C) 2012 Elsevier B.V. All rights reserved.
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Abstract Background Non-steroidal antiinflammatory drugs (NSAIDs) are the most commonly prescribed agents for arthritic patients, although gastric effects limit their long-term use. Considering the reported gastric safety of hydrogen sulfide (H2S)-releasing NSAIDs, in addition to the anti-inflammatory effects of H2S administration to rats with synovitis, we decided to evaluate the effects of the H2S-releasing naproxen derivative ATB-346 in this animal model. Methods Male Wistar rats were anesthetized with inhalatory halothane and pre-treated with equimolar oral doses of either naproxen (0.3, 1, 3 or 10 mg/kg) or ATB-346 (0.48, 1.6, 4.8, or 16 mg/kg) 30 min before the i.art. injection of 7.5 mg of carrageenan (CGN) into the right knee joint cavity. Joint swelling and pain score were assessed after 1, 3 and 5 h, and tactile allodynia after 2 and 4 h. After the last measurement, the joint cavity lavages were performed for counting of the recruited leukocytes. The drugs (at the highest doses) were also tested for their gastric effects by evaluating macroscopical damage score and neutrophil recruitment (measured as myeloperoxidase – MPO activity) in the stomachs 5 h after administration of the drugs. In addition, the serum naproxen pharmacokinetic profiles of both compounds, administered at the highest equimolar doses, were obtained during the first 6 h after dosing. Results At the two highest tested doses, both naproxen and ATB-346 reduced edema and pain score (measured 3 and 5 h after CGN; P < 0.001). Tactile allodynia was similarly inhibited by ~45% 4 h after CGN by both naproxen (at 1, 3 and 10 mg/kg) and ATB-346 (at 1.6 and 4.8 mg/kg; P < 0.001), as well as leukocyte infiltration. Naproxen (but not ATB-346) induced significant gastric damage and, despite the increased gastric MPO activity by ~130% in the naproxen-, but not in the ATB-346-treated rats, this effect was of no statistical significance. Conclusion The presence of a H2S-releasing moiety in the ATB-346 structure does not impair the antiinflammatory activity of the parent compound in rats with CGN-induced synovitis. In addition, released H2S may account for the absence of deleterious gastric effects, thus making of ATB-346 a potentially useful therapeutic alternative to traditional naproxen for treatment of patients with arthritis.
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BACKGROUND: Non-steroidal antiinflammatory drugs (NSAIDs) are the most commonly prescribed agents for arthritic patients, although gastric effects limit their long-term use. Considering the reported gastric safety of hydrogen sulfide (H2S)-releasing NSAIDs, in addition to the anti-inflammatory effects of H2S administration to rats with synovitis, we decided to evaluate the effects of the H2S-releasing naproxen derivative ATB-346 in this animal model. METHODS: Male Wistar rats were anesthetized with inhalatory halothane and pre-treated with equimolar oral doses of either naproxen (0.3, 1, 3 or 10 mg/kg) or ATB-346 (0.48, 1.6, 4.8, or 16 mg/kg) 30 min before the i.art. injection of 7.5 mg of carrageenan (CGN) into the right knee joint cavity. Joint swelling and pain score were assessed after 1, 3 and 5 h, and tactile allodynia after 2 and 4 h. After the last measurement, the joint cavity lavages were performed for counting of the recruited leukocytes. The drugs (at the highest doses) were also tested for their gastric effects by evaluating macroscopical damage score and neutrophil recruitment (measured as myeloperoxidase - MPO activity) in the stomachs 5 h after administration of the drugs. In addition, the serum naproxen pharmacokinetic profiles of both compounds, administered at the highest equimolar doses, were obtained during the first 6 h after dosing. RESULTS: At the two highest tested doses, both naproxen and ATB-346 reduced edema and pain score (measured 3 and 5 h after CGN; P < 0.001). Tactile allodynia was similarly inhibited by ~45% 4 h after CGN by both naproxen (at 1, 3 and 10 mg/kg) and ATB-346 (at 1.6 and 4.8 mg/kg; P < 0.001), as well as leukocyte infiltration. Naproxen (but not ATB-346) induced significant gastric damage and, despite the increased gastric MPO activity by ~130% in the naproxen-, but not in the ATB-346-treated rats, this effect was of no statistical significance. CONCLUSION: The presence of a H2S-releasing moiety in the ATB-346 structure does not impair the antiinflammatory activity of the parent compound in rats with CGN-induced synovitis. In addition, released H2S may account for the absence of deleterious gastric effects, thus making of ATB-346 a potentially useful therapeutic alternative to traditional naproxen for treatment of patients with arthritis.
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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).
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The gas phase degradation reactions of the chemical warfare agent (CWA) simulant, dimethyl methylphosphonate (DMMP), with the hydroperoxide anion (HOO(-)) were investigated using a modified quadrupole ion trap mass spectrometer. The HOO(-) anion reacts readily with neutral DMMP forming two significant product ions at m/z 109 and m/z 123. The major reaction pathways correspond to (i) the nucleophilic substitution at carbon to form \[CH(3)P(O)(OCH(3))O](-) (m/z 109) in a highly exothermic process and (ii) exothermic proton transfer. The branching ratios of the two reaction pathways, 89% and 11% respectively, indicate that the former reaction is significantly faster than the latter. This is in contrast to the trend for the methoxide anion with DMMP, where proton transfer dominates. The difference in the observed reactivities of the HOO(-) and CH(3)O(-) anions can be considered as evidence for an a-effect in the gas phase and is supported by electronic structure calculations at the B3LYP/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory that indicate the S(N)2(carbon) process has an activation energy 7.8 kJ mol(-1) lower for HOO(-) as compared to CH(3)O(-). A similar alpha-effect was calculated for nucleophilic addition-elimination at phosphorus, but this process an important step in the perhydrolysis degradation of CWAs in solution - was not observed to occur with DMMP in the gas phase. A theoretical investigation revealed that all processes are energetically accessible with negative activation energies. However, comparison of the relative Arrhenius pre-exponential factors indicate that substitution at phosphorus is not kinetically competitive with respect to the S(N)2(carbon) and deprotonation processes.