Application of cellulose modified with p-aminobenzoic groups in preconcentration system for determination of Cu, Fe, Ni, and Zn in fuel ethanol samples by flame atomic absorption spectrometry

Cellulose chemically modified with p-aminobenzoic groups, abbreviated as Cel-PAB, was used for preconcentration of copper, iron, nickel, and zinc from ethanol fuel, normally used in Brazil as engine fuel. The surface characteristics and the surface area of the cellulose were obtained before and after chemical modification using FT-IR, elemental analysis, and surface area analysis (B.E.T.). The retention and recovery of the analyte elements were studied by applying batch and column techniques.

Determination of Copper, Iron, Nickel and Zinc in fuel kerosene by FAAS after adsorption and pre-concentration on 2-aminothiazole-modified silica gel

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

ASSESSMENT of POLYATOMIC INTERFERENCES ELIMINATION USING A COLLISION REACTION INTERFACE (CRI) FOR INORGANIC ANALYSIS of FUEL ETHANOL BY ICP-QMS

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

Straightforward systematic approach for fuel efficiency and emissions assessment in automotive systems

At this time, each major automotive market bares its own standards and test procedures to regulate the vehicle green house gases emissions and, thus, fuel consumption. Hence, much are the ways to evaluate the overall efficiency of motor vehicles. The majority of such standards rely on dynamometer cycle tests that appraise only the vehicle as a whole, but fail to assess emissions for each component or sub-system. Once the amount of work generated by the power source of an ICE vehicle to overcome the driving resistance forces is proportional to the energy contained in the required amount of fuel, the power path of the vehicle can be straightforwardly modeled as a set of mechanical systems, and each sub-system evaluated for its share on the total fuel consumption and green house gases emission. This procedure enables the estimation of efficiency gains on the system due to improvement of particular elements on the vehicle's driveline. In this work a simple systematic mechanical model of an arbitrary smallsized hatch back was assembled and total required energy calculated for different regulatory cycles. All the modeling details of the energy balance throughout the system are presented. Afterward, each subsystem was investigated for its role on the fuel consumption and the generated emission quantified. Furthermore, the application of the modeling technique for different sets of sub-systems was introduced. Copyright © 2011 SAE International.

Renewable energy sources in Latin America and the Caribbean: situation and policy proposals

Includes bibliography

Whole-genome sequencing of the efficient industrial fuel-ethanol fermentative Saccharomyces cerevisiae strain CAT-1

The Saccharomyces cerevisiae strains widely used for industrial fuel-ethanol production have been developed by selection, but their underlying beneficial genetic polymorphisms remain unknown. Here, we report the draft whole-genome sequence of the S. cerevisiae strain CAT-1, which is a dominant fuel-ethanol fermentative strain from the sugarcane industry in Brazil. Our results indicate that strain CAT-1 is a highly heterozygous diploid yeast strain, and the similar to 12-Mb genome of CAT-1, when compared with the reference S228c genome, contains similar to 36,000 homozygous and similar to 30,000 heterozygous single nucleotide polymorphisms, exhibiting an uneven distribution among chromosomes due to large genomic regions of loss of heterozygosity (LOH). In total, 58 % of the 6,652 predicted protein-coding genes of the CAT-1 genome constitute different alleles when compared with the genes present in the reference S288c genome. The CAT-1 genome contains a reduced number of transposable elements, as well as several gene deletions and duplications, especially at telomeric regions, some correlated with several of the physiological characteristics of this industrial fuel-ethanol strain. Phylogenetic analyses revealed that some genes were likely associated with traits important for bioethanol production. Identifying and characterizing the allelic variations controlling traits relevant to industrial fermentation should provide the basis for a forward genetics approach for developing better fermenting yeast strains.

Seasonal Distribution of Airborne Trace Elements and Water-Soluble Ions in Sao Paulo Megacity, Brazil

This study deals with the seasonal distribution of Al, Ca, Cu, Fe, K, Mg, Na, Pb and Zn and water soluble ions (Cl-, PO43-, NO3-, SO42-, HCOO-, CH3COO-, oxalate, succinate, Na+, NH4+, K+, Mg2+ and Ca2+) found in PM10 samples (particulate matter less than 10 mu m in diameter) Sao Paulo City, Brazil, (April 2003-May 2004). Higher atmospheric levels were found for SO42-, NO3-, Cl- and PO43- while the main organic anions were oxalate and formate. Atmospheric levels for elements were: Fe > Al > Ca > K > Na > Mg > Zn > Cu > Pb. Some sources were predominant for some species: (i) fuel burning and/or biomass burning (NO3-, HCOO-, C2O42-, K+, Mg2+, Ca2+, Fe, Pb, Zn, Al, Ca, K and Mg), (ii) gas-to-particle conversion (SO42- and NH4+) and (iii) sea salt spray (Cl-, Na+ and Na).

Seasonal distribution of airborne trace elements and water-soluble ions in São Paulo Megacity, Brazil

This study deals with the seasonal distribution of Al, Ca, Cu, Fe, K, Mg, Na, Pb and Zn and water soluble ions (Cl-, PO4(3-), NO3-, SO4(2-), HCOO-, CH3COO-, oxalate, succinate, Na+, NH4+, K+, Mg2+ and Ca2+) found in PM10 samples (particulate matter less than 10 mm in diameter) São Paulo City, Brazil, (April 2003-May 2004). Higher atmospheric levels were found for SO4(2-), NO3-, Cl- and PO4(3-) while the main organic anions were oxalate and formate. Atmospheric levels for elements were: Fe > Al > Ca > K > Na > Mg > Zn > Cu > Pb. Some sources were predominant for some species: (i) fuel burning and/or biomass burning (NO3-, HCOO-, C2O4(2-), K+, Mg2+, Ca2+, Fe, Pb, Zn, Al, Ca, K and Mg), (ii) gas-to-particle conversion (SO4(2-) and NH4+) and (iii) sea salt spray (Cl-, Na+ and Na).

Massenspektrometrische Untersuchungen des Komplexierungsverhaltens von Actinid-Ionen in Lösung

Da die Langzeit-Radiotoxizität von abgebrannten Kernbrennstoffen von Plutonium und den minoren Actiniden dominiert wird, sind diese Elemente im Fokus der Untersuchungen bezüglich der Entsorgung der radioaktiven Abfälle.rnUm ein besseres Verständnis der Selektivität der Partitioning-Liganden BTP und BTBP bezüglich der Extraktion von trivalenten Actiniden zu erlangen, wurden die Komplexe, die diese mit Lanthaniden in octanolischer Lösung bilden charakterisiert. Das unterschiedliche Extraktionsverhalten der Lanthaniden untereinander konnte dabei auf unterschiedliche Präferenz zur Bildung von Ln(BTP)3-Komplexen abhängig vom Ionenradius der Lanthaniden zurückgeführt werden. Darüber hinaus konnte gezeigt werden, dass abhängig vom sterischen Anspruch der BTBP-Liganden in Eu(BTBP)2-Komplexen Nitratliganden in der ersten Koordinationssphäre gebunden werden. rnDa das Verhalten von Plutonium unter geochemischen Bedingungen von besonderem Interesse für die Risikoabschätzung von nuklearen Endlagern ist, widmet sich der zweite Teil der Arbeit dem Hydrolyse- und Kolloidbildungsverhalten von wässrigen Plutoniumlösungen in den Oxidationsstufen IV bis VI. Daher wurden die Lösungsspezies von sowohl Zirconium(IV) als Analogon für Plutonium(IV), als auch die von Uran(VI) und Plutonium(VI) direkt mittels massenspektrometrischer Methoden charakterisiert und quantifiziert. Darüber hinaus wurde die kinetische Hemmung der Reduktion von Pu(V) zu Pu(IV) und nachfolgender Kolloidbildung untersucht, welche sich durch oberflächeninduzierte Reduktion an kolloidalen Kristallisationskeimen deutlich beschleunigen lässt.rn

Speziation von Plutonium bei der Sorption und Diffusion in Opalinuston

Die vorliegende Arbeit wurde im Rahmen des BMWi-Verbundprojektes Wechselwirkung und Transport von Aktiniden im natürlichen Tongestein unter Berücksichtigung von Huminstoffen und Tonorganika – Wechselwirkung von Neptunium und Plutonium mit natürlichem Tongestein“ durchgeführt. Um die langfristige Sicherheit der nuklearen Endlager beurteilen zu können, muss eine mögliche Migration der radiotoxischen Abfälle in die Umwelt betrachtet werden. Wegen seiner langen Halbwertszeit (24000 a) leistet Pu-239 einen wesentlichen Beitrag zur Radiotoxizität abgebrannter Kernbrennstoffe in einem Endlager. Das redox-sensitive Pu tritt in Lösung unter umweltrelevanten Bedingungen in den Oxidationsstufen +III bis +VI auf und kann nebeneinander in bis zu vier Oxidationsstufen vorliegen. Tonsteinformationen werden als mögliches Wirtsgestein für Endlager hoch-radioaktiver Abfälle betrachtet. Deshalb sind ausführliche Informationen zur Mobilisierung und Immobilisierung des Pu durch/in das Grundwasser aus einem Endlager von besonderer Bedeutung. In dieser Arbeit wurden neue Erkenntnisse über die Wechselwirkung zwischen Pu und dem natürlichen Tongestein Opalinuston (OPA, Mont Terri, Schweiz) mit Hinblick auf die Endlagerung wärmeentwickelnder radioaktiver Abfälle in einem geologischen Tiefenlager gewonnen.rnDer Fokus der Arbeit lag dabei auf der Bestimmung der Speziation von Pu an der Mineraloberfläche nach Sorptions- und Diffusionsprozessen mittels verschiedener synchrotronbasierter Methoden (µ-XRF, µ-XANES/EXAFS, µ-XRD, XANES/EXAFS). rnDie Wechselwirkung zwischen Pu und OPA wurde zunächst in Batch- und Diffusionsexperimenten in Abhängigkeit verschiedener experimenteller Parameter (u.a. pH, Pu-Oxidationsstufe) untersucht. In Sorptionsexperimenten konnte gezeigt werden, dass einige Parameter (z.B. Temperatur, Huminsäure) einen deutlichen Einfluss auf die Sorption von Pu haben.rnDie Speziationsuntersuchungen wurden zum einen an Pulverproben aus Batchexperimenten und zum anderen an OPA-Dünnschliffen bzw. Diffusionsproben in Abhängigkeit verschiedener experimenteller Parameter durchgeführt. Die EXAFS-Messungen an der Pu LIII-Kante der Pulverproben ergaben, dass eine innersphäriche Sorption von Pu(IV) an Tongestein unabhängig von dem Ausgangsoxidationszustand des Plutoniums in Lösung stattgefunden hat. Durch die Kombination der ortsaufgelösten Methoden wurde erstmalig mittels μ-XRF die Verteilung von Pu und anderen in OPA enthaltenen Elementen bestimmt. µ-XANES-Spektren an Pu-Anreicherungen auf OPA-Dünnschliffen und in Diffusionsproben bestätigen, dass das weniger mobile Pu(IV) die dominierende Spezies nach den Sorptions- und Diffusionsprozessen ist. Darüber hinaus wurde zum ersten Mal ein Diffusionsprofil von Pu in OPA mittels µ-XRF gemessen. Die Speziationsuntersuchungen mittels μ-XANES zeigten, dass das eingesetzte Pu(V) entlang seines Diffusionspfades zunehmend zu Pu(IV) reduziert wird. Mit µ-XRD wurde Illit als dominierende Umgebung, in der Pu angereichert wurde, identifiziert und Siderit als eine redoxaktive Phase auftreten kann. Die Ergebnisse dieser Arbeit zeigen, dass die Sicherheit von OPA als Wirtsgestein eines Endlagers hoch-radioaktiver Abfälle positiv zu bewerten ist. rn

MODEL UPDATING AND STRUCTURAL HEALTH MONITORING OF HORIZONTAL AXIS WIND TURBINES VIA ADVANCED SPINNING FINITE ELEMENTS AND STOCHASTIC SUBSPACE IDENTIFICATION METHODS

Wind energy has been one of the most growing sectors of the nation’s renewable energy portfolio for the past decade, and the same tendency is being projected for the upcoming years given the aggressive governmental policies for the reduction of fossil fuel dependency. Great technological expectation and outstanding commercial penetration has shown the so called Horizontal Axis Wind Turbines (HAWT) technologies. Given its great acceptance, size evolution of wind turbines over time has increased exponentially. However, safety and economical concerns have emerged as a result of the newly design tendencies for massive scale wind turbine structures presenting high slenderness ratios and complex shapes, typically located in remote areas (e.g. offshore wind farms). In this regard, safety operation requires not only having first-hand information regarding actual structural dynamic conditions under aerodynamic action, but also a deep understanding of the environmental factors in which these multibody rotating structures operate. Given the cyclo-stochastic patterns of the wind loading exerting pressure on a HAWT, a probabilistic framework is appropriate to characterize the risk of failure in terms of resistance and serviceability conditions, at any given time. Furthermore, sources of uncertainty such as material imperfections, buffeting and flutter, aeroelastic damping, gyroscopic effects, turbulence, among others, have pleaded for the use of a more sophisticated mathematical framework that could properly handle all these sources of indetermination. The attainable modeling complexity that arises as a result of these characterizations demands a data-driven experimental validation methodology to calibrate and corroborate the model. For this aim, System Identification (SI) techniques offer a spectrum of well-established numerical methods appropriated for stationary, deterministic, and data-driven numerical schemes, capable of predicting actual dynamic states (eigenrealizations) of traditional time-invariant dynamic systems. As a consequence, it is proposed a modified data-driven SI metric based on the so called Subspace Realization Theory, now adapted for stochastic non-stationary and timevarying systems, as is the case of HAWT’s complex aerodynamics. Simultaneously, this investigation explores the characterization of the turbine loading and response envelopes for critical failure modes of the structural components the wind turbine is made of. In the long run, both aerodynamic framework (theoretical model) and system identification (experimental model) will be merged in a numerical engine formulated as a search algorithm for model updating, also known as Adaptive Simulated Annealing (ASA) process. This iterative engine is based on a set of function minimizations computed by a metric called Modal Assurance Criterion (MAC). In summary, the Thesis is composed of four major parts: (1) development of an analytical aerodynamic framework that predicts interacted wind-structure stochastic loads on wind turbine components; (2) development of a novel tapered-swept-corved Spinning Finite Element (SFE) that includes dampedgyroscopic effects and axial-flexural-torsional coupling; (3) a novel data-driven structural health monitoring (SHM) algorithm via stochastic subspace identification methods; and (4) a numerical search (optimization) engine based on ASA and MAC capable of updating the SFE aerodynamic model.

Origin and patterns of distribution of trace elements in street dust. Unleaded petrol and urban lead

The elemental composition, patterns of distribution and possible sources of street dust are not common to all urban environments, but vary according to the peculiarities of each city. The common features and dissimilarities in the origin and nature of street dust were investigated through a series of studies in two widely different cities, Madrid (Spain) and Oslo (Norway), between 1990 and 1994. The most comprehensive sampling campaign was carried out in the Norwegian capital during the summer of 1994. An area of 14 km2, covering most of downtown Oslo and some residential districts to the north of the city, was divided into 1 km2 mapping units, and 16 sampling increments of approximately 150 g were collected from streets and roads in each of them. The fraction below 100 μm was acid-digested and analysed by ICP-MS. Statistical analyses of the results suggest that chemical elements in street dust can be classified into three groups: “urban” elements (Ba, Cd, Co, Cu, Mg, Pb, Sb, Ti, Zn), “natural” elements (Al, Ga, La, Mn, Na, Sr, Th, Y) and elements of a mixed origin or which have undergone geochemical changes from their original sources (Ca, Cs, Fe, Mo, Ni, Rb, Sr, U). Soil resuspension and/or mobilisation appears to be the most important source of “natural” elements, while “urban” elements originate primarily from traffic and from the weathering and corrosion of building materials. The data for Pb seem to prove that the gradual shift from leaded to unleaded petrol as fuel for automobiles has resulted in an almost proportional reduction in the concentration of Pb in dust particles under 100 μm. This fact and the spatial distribution of Pb in the city strongly suggest that lead sources other than traffic (i.e. lead accumulated in urban soil over the years) may contribute as much lead, if not more, to urban street dust.

The intermediate pyrolysis and catalytic steam reforming of brewers spent grain

Brewers spent grain (BSG) is a widely available feedstock representing approximately 85% of the total by-products generated in the brewing industry. This is currently either disposed of to landfill or used as cattle feed due to its high protein content. BSG has received little or no attention as a potential energy resource, but increasing disposal costs and environmental constraints are now prompting the consideration of this. One possibility for the utilisation of BSG for energy is via intermediate pyrolysis to produce gases, vapours and chars. Intermediate pyrolysis is characterised by indirect heating in the absence of oxygen for short solids residence times of a few minutes, at temperatures of 350-450 °C. In the present work BSG has been characterised by chemical, proximate, ultimate and thermo-gravimetric analysis. Intermediate pyrolysis of BSG at 450 °C was carried out using a twin coaxial screw reactor known as Pyroformer to give yields of char 29%, 51% of bio-oil and 19% of permanent gases. The bio-oil liquid was found to separate in to an aqueous phase and organic phase. The organic phase contained viscous compounds that could age over time leading to solid tars that can present problems in CHP application. The quality of the pyrolysis vapour products before quenching can be upgraded to achieve much improved suitability as a fuel by downstream catalytic reforming. A Bench Scale batch pyrolysis reactor has then been used to pyrolyse small samples of BSG under a range of conditions of heating rate and temperature simulating the Pyroformer. A small catalytic reformer has been added downstream of the reactor in which the pyrolysis vapours can be further cracked and reformed. A commercial reforming nickel catalyst was used at 500, 750 and 850 °C at a space velocity about 10,000 L/h with and without the addition of steam. Results are presented for the properties of BSG, and the products of the pyrolysis process both with and without catalytic post-processing. Results indicate that catalytic reforming produced a significant increase in permanent gases mainly (H2 and CO) with H2 content exceeding 50 vol% at higher reforming temperatures. Bio-oil yield decreased significantly as reforming temperature increased with char remaining the same as pyrolysis condition remained unchanged. The process shows an increase in heating value for the product gas ranging between 10.8-25.2 MJ/m as reforming temperature increased. © 2012 Elsevier B.V. All rights reserved.

Solid biofuel production by mechanical pre-treatment of brewers' spent grain

The brewing industry produces large amounts of by-products and wastes like brewers' spent grain (BSG). In Germany, each year approximately 2.1 million tonnes of BSG are generated. During the last years conventional routes of BSG utilization face a remarkable change, such as the decline in the demand as animal feed. Due to its high content of organic matter energetic utilization may create an additional economic value for breweries. Furthermore, in the recent past breweries tend to shift their energy supply towards more sustainable concepts. Although, a decent number of research projects were carried out already, still no mature strategy is available. However, one possible solution can be the mechanical pretreatment of BSG. This step allows optimized energy utilization by the fractionation of BSG. Due to the transfer of digestible components, such as protein, to the liquid phase, the solid phase will largely consist of combustible components. That represents an opportunity to produce a solid biofuel with lower fuelnitrogen content compared to only thermal dried BSG. Therefore, two main purposes for the mechanical pre-treatment were determined, (1) to reduce the moisture content to at least 60 % (w/w) and (2) to diminish the protein content of the solid phase by 30 %. Moreover, the combustion trials should demonstrate whether stable processes and flue gas emissions within the legal limits in Germany are feasible. The results of the mechanical pre-treatment trials showed that a decrease of the moisture and protein content has been achieved. With regard to the combustion trials inconsistent outcomes were found. On the one hand a stable combustion was realized. On the other hand the legal emission levels of NOx (500 mgm -3) and dust (50 mgm-3) could not be kept during all trials. The further research steps will focus on the optimization of the air/fuel ratio by reducing the primary and secondary air conditions. Copyright © 2014,AIDIC Servizi S.r.l.

Thermochemical conversion of Brewers Spent Grain combined with catalytic reforming of pyrolysis vapours

The brewing process is an energy intensive process that uses large quantities of heat and electricity. To produce this energy requires a high, mainly fossil fuel consumption and the cost of this is increasing each year due to rising fuel costs. One of the main by-products from the brewing process is Brewers Spent Grain (BSG), an organic residue with very high moisture content. It is widely available each year and is often given away as cattle feed or disposed of to landfill as waste. Currently these methods of disposal are also costly to the brewing process. The focus of this work was to investigate the energy potential of BSG via pyrolysis, gasification and catalytic steam reforming, in order to produce a tar-free useable fuel gas that can be combusted in a CHP plant to develop heat and electricity. The heat and electricity can either be used on site or exported. The first stage of this work was the drying and pre-treatment of BSG followed by characterisation to determine its basic composition and structure so it can be evaluated for its usefulness as a fuel. A thorough analysis of the characterisation results helps to better understand the thermal behaviour of BSG feedstock so it can be evaluated as a fuel when subjected to thermal conversion processes either by pyrolysis or gasification. The second stage was thermochemical conversion of the feedstock. Gasification of BSG was explored in a fixed bed downdraft gasifier unit. The study investigated whether BSG can be successfully converted by fixed bed downdraft gasification operation and whether it can produce a product gas that can potentially run an engine for heat and power. In addition the pyrolysis of BSG was explored using a novel “Pyroformer” intermediate pyrolysis reactor to investigate the behaviour of BSG under these processing conditions. The physicochemical properties and compositions of the pyrolysis fractions obtained (bio-oil, char and permanent gases) were investigated for their applicability in a combined heat power (CHP) application.