Análise bayesiana para características de carcaça avaliadas por ultrassonografia de bovinos da raça Nelore Mocho, criados em bioma Cerrado

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

In situ selective determination of methylmercury in river water by diffusive gradient in thin films technique (DGT) using baker's yeast (Saccharomyces cerevisiae) immobilized in agarose gel as binding phase

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

Caracterização mineralógica e química das fontes de poeira e sua influência na atmosfera da região do polo cerâmico de Santa Gertrudes (SP)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Study of combustion of different biomass and its atmospheric emissions

One of the energy alternatives that provide utility, flexibility, cleanliness and economy is biomass, such as forest waste (wood) and agricultural (sugarcane bagasse, rice husks, coffee pods, etc.). However, with its increasing supply and use grows also the concern of industries to invest in monitoring and control of emissions into the atmosphere, because during biomass burning are emitted as exhaust gases, fine particles known as particulates, which greatly contribute to the triggering of serious health problems to humans, in addition to the environmental damage. With that, this work aimed to conduct a monitoring of particulate and gaseous pollutants emissions to the atmosphere from the burning of various types of biomass used by industries. The equipment used for sampling were the optical monitor DataRAM 4 and the Unigas3000 + gas sampler. The results showed that biomass coffee pods presented the greatest concentration of particulates (485119 μg m-3) with particle diameters between 0.0602 μm and 0.3502 μm, i.e. the most ultrafine particles, harmful to human health and the environment. The largest emissions of CO and NOx were observed, respectively, for the coffee pods (3500 ppm) and for the rice husk (48 ppm). As for the superior calorific value (PCS), the best of fuel, with higher PCS, was the Eucalyptus grandis.

Vertical distribution of benthic invertebrate larvae during an upwelling event along a transect off the tropical Brazilian continental margin

Abundance and composition of marine benthic communities have been relatively well studied in the SE Brazilian coast, but little is known on patterns controlling the distribution of their planktonic larval stages. A survey of larval abundance in the continental margin, using a Multi-Plankton Sampler, was conducted in a cross-shelf transect off Cabo Frio (23 degrees S and 42 degrees W) during a costal upwelling event. Hydrographic conditions were monitored through discrete CDT casts. Chlorophyll-a in the top 100 m of the water column was determined and changes in surface chlorophyll-a was estimated using SeaWiFS images. Based on the larval abundances and the meso-scale hydrodynamics scenario, our results suggest two different processes affecting larval distributions. High larval densities were found nearshore due to the upwelling event associated with high chlorophyll a and strong along shore current. On the continental slope, high larval abundance was associated with a clockwise rotating meander, which may have entrapped larvae from a region located further north (Cabo de Sao Tome, 22 degrees S and 41 degrees W). In mid-shelf areas, our data suggests that vertical migration may likely occur as a response to avoid offshore transport by upwelling plumes and/or cyclonic meanders. The hydrodynamic scenario observed in the study area has two distinct yet extremely important consequences: larval retention on food-rich upwelling areas and the broadening of the tropical domain to southernmost subtropical areas. (C) 2009 Elsevier B.V. All rights reserved.

Particle emission from heavy-duty engine fuelled with blended diesel and biodiesel

In this study, particulate matter (PM) were characterized from a place impacted by heavy-duty vehicles (Bus Station) fuelled with diesel/biodiesel fuel blend (B3) in the city of Londrina, Brazil. Sixteen priority polycyclic aromatic hydrocarbons (PAH) concentrations were analyzed in the samples by their association with atmospheric PM, mass size distributions and major ions (fluorite, chloride, bromide, nitrate, phosphate, sulfate, nitrite, oxalate; fumarate, formate, succinate and acetate; lithium, sodium, potassium, magnesium, calcium and ammonium). Results indicate that major ions represented 21.2% particulate matter mass. Nitrate, sulfate, and ammonium, respectively, presented the highest concentration levels, indicating that biodiesel may also be a significant source for these ions, especially nitrate. Dibenzo[a,h]anthracene and indeno[1,2,3,-cd]pyrene were the main PAH found, and a higher fraction of PAH particles was found in diameters lower than 0.25 mu m in Londrina bus station. The fine and ultrafine particles were dominant among the PM evaluated, suggesting that biodiesel decreases the total PAH emission. However, it does also increase the fraction of fine and ultrafine particles when compared to diesel.

Characterization of atmospheric aerosols in the city of So Paulo, Brazil: comparisons between polluted and unpolluted periods

The objective of this study was to determine the size and composition of atmospheric aerosols in the downtown area of the city of So Paulo, Brazil, for a polluted and an unpolluted period. Aerosols were sampled with a portable air sampler (PAS), Micro-Orifice Uniform Deposit Impactor (MOUDI), and Scanning Mobility Particle Sizer. At the study site, air quality is poor, especially during the winter, high concentrations of pollutants being emitted primarily by the light- and heavy-duty vehicle fleet. We analyzed mass, black carbon (BC), Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sn, Zr, and Pb. During the polluted period, diurnal PM(10) was higher than nocturnal PM(10), whereas the inverse was true during the unpolluted period. The FPM was rich in BC, S, and Pb, whereas CPM was rich in Al, Si, Ca, Ti, and Fe. Mass balance was performed by category: ammonium sulfate, sodium chloride, crustal material, BC, and other. The PAS-determined FPM was mainly BC. The MOUDI-determined FPM crustal material explained more mass than did ammonium sulfate and BC during the polluted period, whereas ammonium sulfate had the largest mass during the unpolluted period. Crustal material was the major CPM component, followed by ammonium sulfate and BC. During the unpolluted period, FPM concentrations were lower, whereas those of ammonium sulfate were relatively higher, especially at night, and particle number was inversely proportional to particle size. Aerosol growth was more intense during the polluted period.

Aerosol and precipitation chemistry measurements in a remote site in Central Amazonia: the role of biogenic contribution

In this analysis a 3.5 years data set of aerosol and precipitation chemistry, obtained in a remote site in Central Amazonia (Balbina, (1A degrees 55' S, 59A degrees 29' W, 174 m a.s.l.), about 200 km north of Manaus) is discussed. Aerosols were sampled using stacked filter units (SFU), which separate fine (d < 2.5 mu m) and coarse mode (2.5 mu m < d < 10.0 mu m) aerosol particles. Filters were analyzed for particulate mass (PM), Equivalent Black Carbon (BCE) and elemental composition by Particle Induced X-Ray Emission (PIXE). Rainwater samples were collected using a wet-only sampler and samples were analyzed for pH and ionic composition, which was determined using ionic chromatography (IC). Natural sources dominated the aerosol mass during the wet season, when it was predominantly of natural biogenic origin mostly in the coarse mode, which comprised up to 81% of PM10. Biogenic aerosol from both primary emissions and secondary organic aerosol dominates the fine mode in the wet season, with very low concentrations (average 2.2 mu g m(-3)). Soil dust was responsible for a minor fraction of the aerosol mass (less than 17%). Sudden increases in the concentration of elements as Al, Ti and Fe were also observed, both in fine and coarse mode (mostly during the April-may months), which we attribute to episodes of Saharan dust transport. During the dry periods, a significant contribution to the fine aerosols loading was observed, due to the large-scale transport of smoke from biomass burning in other portions of the Amazon basin. This contribution is associated with the enhancement of the concentration of S, K, Zn and BCE. Chlorine, which is commonly associated to sea salt and also to biomass burning emissions, presented higher concentration not only during the dry season but also for the April-June months, due to the establishment of more favorable meteorological conditions to the transport of Atlantic air masses to Central Amazonia. The chemical composition of rainwater was similar to those ones observed in other remote sites in tropical forests. The volume-weighted mean (VWM) pH was 4.90. The most important contribution to acidity was from weak organic acids. The organic acidity was predominantly associated with the presence of acetic acid instead of formic acid, which is more often observed in pristine tropical areas. Wet deposition rates for major species did not differ significantly between dry and wet season, except for NH4+, citrate and acetate, which had smaller deposition rates during dry season. While biomass burning emissions were clearly identified in the aerosol component, it did not present a clear signature in rainwater. The biogenic component and the long-range transport of sea salt were observed both in aerosols and rainwater composition. The results shown here indicate that in Central Amazonia it is still possible to observe quite pristine atmospheric conditions, relatively free of anthropogenic influences.

Validação de novo amostrador de furos de desmonte para fins de reconciliação

Mining operations around the world make extensive use of blasthole sampling for short-term planning, which has two undisputed advantages: (1) blastholes are closely spaced providing relatively high sampling density per ton, and (2) there is no additional cost since the blastholes must be drilled anyway. However, blasthole sampling usually presents poor sampling precision, and the inconstant sampling bias caused by particle size and density segregation is an even more serious problem, generally precluding representativeness. One of the main causes of this bias is a highly varying loss of fines, which can lead to both under- and over-estimation of grade depending on the ore type and the gangue. This study validates a new, modified sectorial sampler, designed to reduce the loss of fines and thereby increase sampling accuracy for narrow-diameter blasthole sampling. First results show a significantly improved estimation of gold grade as well as the minimization of the loss of fines.

Diversity of Ephemeroptera (Insecta) of the Serra da Mantiqueira and Serra do Mar, southeastern Brazil

Diversity of Ephemeroptera (Insecta) of the Serra da Mantiqueira and Serra do Mar, southeastern Brazil. The aim of this study was to inventory the mayfly fauna, based on nymphal and alate stages, in Serra da Mantiqueira and in Serra do Mar, Sao Paulo State, as well as to present information about habitats used by the genera. Nymphs were collected in several streams and mesohabitats with a Surber sampler and the winged stages with light attraction methods, entomological nets, and Malaise traps. In all, eight families and 33 genera were recorded, representing a very significant portion of the Brazilian fauna (80% of families and 49% of genera). Furthermore, it was possible to identify 11 species, of which two are new records for the state: Tricorythodes santarita Traver and Caenis reissi Malzacher. Despite the high diversity recorded, the accumulation curves presented an ascending form, indicating an increase in the number of genera with additional sampling effort. The high richness found in these areas are in agreement with the high biodiversity of the Atlantic Forest biome and the sampling effort employed, which included the use of different methods, the collection of both nymphs and winged stages, and the sampling of a large area with diverse streams and habitats.

Genetic relationship between growth and reproductive traits in Nellore cattle

The objective of this study was to evaluate the genetic relationship between postweaning weight gain (PWG), heifer pregnancy (HP), scrotal circumference (SC) at 18 months of age, stayability at 6 years of age (STAY) and finishing visual score at 18 months of age (PREC), and to determine the potential of these traits as selection criteria for the genetic improvement of growth and reproduction in Nellore cattle. The HP was defined as the observation that a heifer conceived and remained pregnant, which was assessed by rectal palpation at 60 days. The STAY was defined as whether or not a cow calved every year up to the age of 6 years, given that she was provided the opportunity to breed. The Bayesian linear-threshold analysis via the Gibbs sampler was used to estimate the variance and covariance components applying a multitrait model. Posterior mean estimates of direct heritability were 0.15 +/- 0.00, 0.42 +/- 0.02, 0.49 +/- 0.01, 0.11 +/- 0.01 and 0.19 +/- 0.00 for PWG, HP, SC, STAY and PREC, respectively. The genetic correlations between traits ranged from 0.17 to 0.62. The traits studied generally have potential for use as selection criteria in genetic breeding programs. The genetic correlations between all traits show that selection for one of these traits does not imply the loss of the others.

Isocyanates and Amines – Sampling and Analytical Procedures

This thesis covers sampling and analytical procedures for isocyanates (R-NCO) and amines (R-NH2), two kinds of chemicals frequently used in association with the polymeric material polyurethane (PUR). Exposure to isocyanates may result in respiratory disorders and dermal sensitisation, and they are one of the main causes of occupational asthma. Several of the aromatic diamines associated with PUR production are classified as suspected carcinogens. Hence, the presence of these chemicals in different exposure situations must be monitored. In the context of determining isocyanates in air, the methodologies included derivatisation with the reagent di-n-butylamine (DBA) upon collection and subsequent determination using liquid chromatography (LC) and mass spectrometric detection (MS). A user-friendly solvent-free sampler for collection of airborne isocyanates was developed as an alternative to a more cumbersome impinger-filter sampling technique. The combination of the DBA reagent together with MS detection techniques revealed several new exposure situations for isocyanates, such as isocyanic acid during thermal degradation of PUR and urea-based resins. Further, a method for characterising isocyanates in technical products used in the production of PUR was developed. This enabled determination of isocyanates in air for which pure analytical standards are missing. Tandem MS (MS/MS) determination of isocyanates in air below 10-6 of the threshold limit values was achieved. As for the determination of amines, the analytical methods included derivatisation into pentafluoropropionic amide or ethyl carbamate ester derivatives and subsequent MS analysis. Several amines in biological fluids, as markers of exposure for either the amines themselves or the corresponding isocyanates, were determined by LC-MS/MS at amol level. In aqueous extraction solutions of flexible PUR foam products, toluene diamine and related compounds were found. In conclusion, this thesis demonstrates the usefulness of well characterised analytical procedures and techniques for determination of hazardous compounds. Without reliable and robust methodologies there is a risk that exposure levels will be underestimated or, even worse, that relevant compounds will be completely missed.

Solid-phase Microextraction and Detection of Organophosphate Triesters in Indoor air

In the work underlying this thesis solid-phase microextraction (SPME) was evaluated as a passive sampling technique for organophosphate triesters in indoor air. These compounds are used on a large scale as flame-retarding and plastizicing additives in a variety of materials and products, and have proven to be common pollutants in indoor air. The main objective of this work was to develop an accurate method for measuring the volatile fraction. Such a method can be used in combination with active sampling to obtain information regarding the vapour/particulate distribution in different indoor environments. SPME was investigated under both equilibrium and non-equilibrium conditions and parameters associated with these different conditions were estimated. In Paper I, time-weighted average (TWA) SPME under dynamic conditions was investigated in order to obtain a fast air sampling method for organophosphate triesters. Among the investigated SPME coatings, the absorptive PDMS polymer had the highest affinity for the organophosphate triesters and was consequently used in all further work. Since the sampling rate is dependent on the agitation conditions, the linear airflow rates had to be carefully considered. Sampling periods as short as 1 hour were shown to be sufficient for measurements in the ng-μg m-3 range when using a PDMS 100-μm fibre and a linear flow rate above 7 cm s-1 over the fibre. SPME under equilibrium conditions is rather time-consuming, even under dynamic conditions, for slowly partitioning compounds such as organophosphate triesters. Nevertheless, this method has some significant advantages. For instance, the limit of detection is much lower compared to 1 h TWA sampling. Furthermore, the sampling time can be ignored as long as equilibrium has been attained. In Paper II, SPME under equilibrium conditions was investigated and evaluated for organophosphate triester vapours. Since temperature and humidity are closely associated with the distribution constant a simple study of the effect of these parameters was performed. The obtained distribution constants were used to determine the air levels in a common indoor environment. SPME and parallel active sampling on filters yielded similar results, indicating that the detected compounds were almost entirely associated with the vapour phase To apply dynamic SPME method in the field a sampler device, which enables controlled linear airflow rates to be applied, was constructed and evaluated (Paper III). This device was developed for application of SPME and active sampling in parallel. A GC/PICI-MS/MS method was developed and used in combination with active sampling of organophosphate triesters in indoor air (Paper IV). The combination of MS/MS and the soft ionization achieved with methanol as reagent gas yielded high selectivity and detection limits comparable to those provided by GC with nitrogen-phosphorus detection (NPD). The method limit of detection, when sampling 1.5 m3 of air, was in the range 0.1-1.4 ng m-3. In Paper V, the developed MS method was used in combination with SPME for indoor air measurements. The levels detected in the investigated indoor environments range from a few ng to μg m-3. Tris(2-chloropropyl) phosphate was detected at a concentration as high as 7 μg m-3 in a newly rebuilt lecture room.

Applications of High Speed Configurable Logic Devices in Modern Particle Physics Experiments

Several activities were conducted during my PhD activity. For the NEMO experiment a collaboration between the INFN/University groups of Catania and Bologna led to the development and production of a mixed signal acquisition board for the Nemo Km3 telescope. The research concerned the feasibility study for a different acquisition technique quite far from that adopted in the NEMO Phase 1 telescope. The DAQ board that we realized exploits the LIRA06 front-end chip for the analog acquisition of anodic an dynodic sources of a PMT (Photo-Multiplier Tube). The low-power analog acquisition allows to sample contemporaneously multiple channels of the PMT at different gain factors in order to increase the signal response linearity over a wider dynamic range. Also the auto triggering and self-event-classification features help to improve the acquisition performance and the knowledge on the neutrino event. A fully functional interface towards the first level data concentrator, the Floor Control Module, has been integrated as well on the board, and a specific firmware has been realized to comply with the present communication protocols. This stage of the project foresees the use of an FPGA, a high speed configurable device, to provide the board with a flexible digital logic control core. After the validation of the whole front-end architecture this feature would be probably integrated in a common mixed-signal ASIC (Application Specific Integrated Circuit). The volatile nature of the configuration memory of the FPGA implied the integration of a flash ISP (In System Programming) memory and a smart architecture for a safe remote reconfiguration of it. All the integrated features of the board have been tested. At the Catania laboratory the behavior of the LIRA chip has been investigated in the digital environment of the DAQ board and we succeeded in driving the acquisition with the FPGA. The PMT pulses generated with an arbitrary waveform generator were correctly triggered and acquired by the analog chip, and successively they were digitized by the on board ADC under the supervision of the FPGA. For the communication towards the data concentrator a test bench has been realized in Bologna where, thanks to a lending of the Roma University and INFN, a full readout chain equivalent to that present in the NEMO phase-1 was installed. These tests showed a good behavior of the digital electronic that was able to receive and to execute command imparted by the PC console and to answer back with a reply. The remotely configurable logic behaved well too and demonstrated, at least in principle, the validity of this technique. A new prototype board is now under development at the Catania laboratory as an evolution of the one described above. This board is going to be deployed within the NEMO Phase-2 tower in one of its floors dedicated to new front-end proposals. This board will integrate a new analog acquisition chip called SAS (Smart Auto-triggering Sampler) introducing thus a new analog front-end but inheriting most of the digital logic present in the current DAQ board discussed in this thesis. For what concern the activity on high-resolution vertex detectors, I worked within the SLIM5 collaboration for the characterization of a MAPS (Monolithic Active Pixel Sensor) device called APSEL-4D. The mentioned chip is a matrix of 4096 active pixel sensors with deep N-well implantations meant for charge collection and to shield the analog electronics from digital noise. The chip integrates the full-custom sensors matrix and the sparsifification/readout logic realized with standard-cells in STM CMOS technology 130 nm. For the chip characterization a test-beam has been set up on the 12 GeV PS (Proton Synchrotron) line facility at CERN of Geneva (CH). The collaboration prepared a silicon strip telescope and a DAQ system (hardware and software) for data acquisition and control of the telescope that allowed to store about 90 million events in 7 equivalent days of live-time of the beam. My activities concerned basically the realization of a firmware interface towards and from the MAPS chip in order to integrate it on the general DAQ system. Thereafter I worked on the DAQ software to implement on it a proper Slow Control interface of the APSEL4D. Several APSEL4D chips with different thinning have been tested during the test beam. Those with 100 and 300 um presented an overall efficiency of about 90% imparting a threshold of 450 electrons. The test-beam allowed to estimate also the resolution of the pixel sensor providing good results consistent with the pitch/sqrt(12) formula. The MAPS intrinsic resolution has been extracted from the width of the residual plot taking into account the multiple scattering effect.

GC/MS-Meßsystem für Nicht-Methan-Kohlenwasserstoffe

Im Rahmen der Projekte CARIBIC ('Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container') und INDOEX ('Indian Ocean Experi-ment') wurde ein Gaschromatograph mit Massenspektrometer zur Analyse von Luftproben auf Nicht-Methan-Kohlenwasserstoffe (NMKW) im ppb- und ppt-Bereich entwickelt. Während INDOEX erfolgte die Probennahme auf dem Forschungsschiff Ronald Brown, während CARIBIC mit einem automatischen Probensammler an Bord eines Passagierflugzeuges (Boeing 767-ER, LTU). Die NMKW-Meßergebnisse wurden zusammen mit Ergebnissen von Mes-sungen von Kohlenmonoxid (CO, einschließlich Isotopenzusam-mensetzung), Ozon (O3), Methan (CH4), Kohlendioxid (CO2), Distickstoffmonoxid (N2O), Schwefelhexafluorid (SF6) und Aerosoleigenschaften sowie meteorologischen Daten inter-pretiert. Während INDOEX (Februar / März 1999) wurde in der maritimen Grenzschicht (MBL) des Indischen Ozeans (IO) eine starke Variabilität diverser Spurengase beobachtet, die teilweise durch regionale Emissionen hervorgerufen wurde, die stärkste Variabilität war jedoch durch Langstrecken-transport aus mittleren Breiten der Nordhemisphäre bedingt. Aufgrund der Abweichungen vom klimatologischen Mittel, sollten regionale Quellen die MBL des IO im allgemeinen stärker beeinflussen. Die Einteilung des IO in meteorologi-sche Luftmassenregime wurde bestätigt. Starke Spurengasgra-dienten an der innertropischen Konvergenzzone (ITCZ) zeigen, daß die ITCZ in erster Linie den Austausch von Luftmassen zwischen den Hemisphären behindert. Bei CARIBIC werden Messungen von Spurengasen (ein-(schließlich NMKW) und Aerosoleigenschaften auf Flügen in der oberen Troposphäre / unteren Stratosphäre durchgeführt. Während eines Flug über Afrika wurden der Einfluß von durch Konvektion in die obere Troposphäre eingebrachten, frischen Abgasen aus Biomassenverbrennung nachgewiesen. Andere Luft-massen wurden durch Emissionen von Erdgas bzw. durch die Stratosphäre beeinflußt.