Voltammetric analysis of mancozeb and its degradation product ethylenethiourea

The purpose of this work was to develop a reliable alternative method for the determination of the dithiocarbamate pesticide mancozeb (MCZ) in formulations. Furthermore, a method for the analysis of MCZ's major degradation product, ethylenethiourea (ETU), was also proposed. Cyclic voltammetry was used to characterize the electrochemical behavior of MCZ and ETU, and square-wave adsorptive stripping voltammetry (SWAdSV) was employed for MCZ quantification in commercial formulations. It was found that both MCZ and ETU are irreversibly reduced (− 0.6 V and − 0.5 V vs Ag/AgCl, respectively) at the surface of a glassy carbon electrode in a mainly diffusion-controlled process, presenting maximum peak current intensities at pH 7.0 (in phosphate buffered saline electrolyte). Several parameters of the SWAdSV technique were optimized and linear relationships between concentration and peak current intensity were established between 10–90 μmol L− 1 and 10–110 μmol L− 1 for MCZ and ETU, respectively. The limits of detection were 7.0 μmol L− 1 for MCZ and 7.8 μmol L− 1 for ETU. The optimized method for MCZ was successfully applied to the quantification of this pesticide in two commercial formulations. The developed procedures provided accurate and precise results and could be interesting alternatives to the established methods for quality control of the studied products, as well as for analysis of MCZ and ETU in environmental samples.

Stochastic modeling of the thermal and catalytic degradation of polyethylene using simultaneous DSC/TG analysis

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Earth mortars from pre-historic habitat settlements in south Portugal. Case studies

J. Iberian Archaeology 13 (2010), 51-67

Gastrointestinal symbionts of chimpanzees in Cantanhez National Park, Guinea-Bissau with respect to habitat fragmentation

One of the major factors threatening chimpanzees (Pan troglodytes verus) in Guinea-Bissau is habitat fragmentation. Such fragmentation may cause changes in symbiont dynamics resulting in increased susceptibility to infection, changes in host specificity and virulence. We monitored gastrointestinal symbiotic fauna of three chimpanzee subpopulations living within Cantanhez National Park (CNP) in Guinea Bissau in the areas with different levels of anthropogenic fragmentation. Using standard coproscopical methods (merthiolate-iodine formalin concentration and Sheather's flotation) we examined 102 fecal samples and identified at least 13 different symbiotic genera (Troglodytella abrassarti, Troglocorys cava, Blastocystis spp., Entamoeba spp., Iodamoeba butschlii, Giardia intestinalis, Chilomastix mesnili, Bertiella sp., Probstmayria gombensis, unidentified strongylids, Strongyloides stercoralis, Strongyloides fuelleborni, and Trichuris sp.). The symbiotic fauna of the CNP chimpanzees is comparable to that reported for other wild chimpanzee populations, although CNP chimpanzees have a higher prevalence of Trichuris sp. Symbiont richness was higher in chimpanzee subpopulations living in fragmented forests compared to the community inhabiting continuous forest area. We reported significantly higher prevalence of G. intestinalis in chimpanzees from fragmented areas, which could be attributed to increased contact with humans and livestock.

On the way towards the understanding of suberin degradation by Aspergillus nidulans

Dissertation presented to obtain the Ph.D degree in Biochemistry.

Influence of the molecular weight in mechanical properties and degradation kinetics of chitosan inverted colloidal crystals

Tissue engineering arises from the need to regenerate organs and tissues, requiring the development of scaffolds, which can provide an optimum environment for tissue growth. In this work, chitosan with different molecular weights was used to develop biodegradable 3D inverted colloidal crystals (ICC) structures for bone regeneration, exhibiting uniform pore size and interconnected network. Moreover, in vitro tests were conducted by studying the influence of the molecular weight in the degradation kinetics and mechanical properties. The production of ICC included four major stages: fabrication of microspheres; assembly into a cohesive structure, polymeric solution infiltration and microsphere removal. Chitosan’s degree of deacetylation was determined by infrared spectroscopy and molecular weight was obtained via capillary viscometry. In order to understand the effect of the molecular weight in ICC structures, the mass loss and mechanical properties were analyzed after degradation with lysozyme. Structure morphology observation before and after degradation was performed by scanning electron microscopy. Cellular adhesion and proliferation tests were carried out to evaluate ICC in vitro response. Overall, medium molecular weight ICC revealed the best balance in terms of mechanical properties, degradation rate, morphology and biological behaviour.

Photochemical degradation of triclosan: a comparison between different light sources

New emerging contaminants could represent a danger to the environment and Humanity with repercussions not yet known. One of the major worldwide pharmaceutical and personal care productions are antimicrobials products, triclosan, is an antimicrobial agent present in most products. Despite the high removal rate of triclosan present in wastewater treatments, triclosan levels are on the rise in the environment through disposal of wastewater effluent and use of sewage sludge in land application. Regulated in the EC/1272/2008 (annex VI, table 3.1), this compound is considered very toxic to aquatic life and it has been reported that photochemical transformation of triclosan produces dioxins. In the current work it was defined three objectives; determination of the most efficient process in triclosan degradation, recurring to photochemical degradation methods comparing different sources of light; identification of the main by-products formed during the degradation and the study of the influence of the Fenton and photo-Fenton reaction. Photochemical degradation methods such as: photocatalysis under florescent light (UV), photocatalysis under visible light (sunlight), photocatalysis under LEDs, photo-Fenton and Fenton reaction have been compared in this work. The degradation of triclosan was visualized through gas chromatography/mass spectrometry (GC/MS). In this study photo-Fenton reaction has successfully oxidized triclosan to H2O and CO2 without any by-products within 2 hours. Photocatalysis by titanium dioxide (TiO2) under LEDs was possible, having a degradation rate of 53% in an 8 hours essay. The degradation rate of the Fenton reaction, UV light and sunlight showed degradation between 90% and 95%. The results are reported to the data observed without statistic support, since this was not possible during the work period. Hydroquinone specie and 2,4-dichlorophenol by-products were identified in the first hour of photocatalysis by UV. A common compound, possibly identified has C7O4H , was present at the degradation by UV, sunlight and LEDs and was concluded to be a contaminant. In the future more studies in the use of LEDs should be undertaken given the advantages of long durability and low consumption of energy of these lamps and that due to their negative impact on the environment fluorescent lamps are being progressively made unavailable by governments, requiring new solutions to be found. Fenton and photo-Fenton reactions can also be costly processes given the expensive reagents used.

Genome-scale metabolic network reconstruction of Polaromonas sp. strain JS666: analysis of cDCE degradation rates and design of experiments for bioremediation improvement

Release of chloroethene compounds into the environment often results in groundwater contamination, which puts people at risk of exposure by drinking contaminated water. cDCE (cis-1,2-dichloroethene) accumulation on subsurface environments is a common environmental problem due to stagnation and partial degradation of other precursor chloroethene species. Polaromonas sp. strain JS666 apparently requires no exotic growth factors to be used as a bioaugmentation agent for aerobic cDCE degradation. Although being the only suitable microorganism found capable of such, further studies are needed for improving the intrinsic bioremediation rates and fully comprehend the metabolic processes involved. In order to do so, a metabolic model, iJS666, was reconstructed from genome annotation and available bibliographic data. FVA (Flux Variability Analysis) and FBA (Flux Balance Analysis) techniques were used to satisfactory validate the predictive capabilities of the iJS666 model. The iJS666 model was able to predict biomass growth for different previously tested conditions, allowed to design key experiments which should be done for further model improvement and, also, produced viable predictions for the use of biostimulant metabolites in the cDCE biodegradation.

Repartição do Habitat entre Psitacídeos Simpátricos no Sul da Amazônia

Estudaram-se de agosto de 1977 a junho de 1979 16 espécies de Psitacídeos na região do Núcleo Pioneiro Humboldt (10019' S, 590 12' W), alto rio Aripuanã, MT, Brasil. Verificou-se que diferentes tamanhos de corpo e peso dão acesso a espectros alimentares diferentes. Com respeito ao peso, as 16 espécies podem ser divididas em quatro grupos:55 até 110g: Tuit huetii, Pyrrhura picta, Brotogeris chrysopterus, Pyrrhura rhodogaster, Aratinga weddellii.140 até 300g: Aratinga leucophthalmus, Pionopsitta barrabandi, Pionus menstruus, Deroptyus accipitrinus.360 até 600g: Ara severa, Ara manilata, Amazona ochrocephala, Amazona farinosa.950 até 1350g: Ara ararauna, Ara macao, Ara chloroptera.As estratégias alimentares variam dentro de cada grupo de peso: Ara manilata é especialista puro, Tuit huetti, Brotogeris chrysopterus, Pionopsitta barrabandi, Ara severa e Ara ararauna são especialistas parciais. Os especialistas parciais têm bicos relativamente compridos e estreitos. Com respeito às proporções do bico, Brotogerischrysopterus é mais especializado do que Tuit huetii no mesmo grupo de peso.As espécies muito próximas morfologicamente, como Ara chloroptera e Ara macao ou Pyrruhura rhodogaster e Pyrrhura picta, podem ser reconhecidas principalmente pelo modo com que exploram o habitat. Ara chloroptera se encontra nas estratos superiores da floresta, junto às copas de árvores muito altas, com maior freqüência do que Ara macao. Pyrrhura rhodogaster visita mais freqüentemente matas densas e vegetação secundária do que Pyrrhura picta. Diferenças sazonais de abundância e épocas diferentes de reprodução separam as duas espécies de Amazona. Amazona ochrocephala é mais comum e inclusive cria os seus filhotes na época seca, enquanto que Amazona farinosa reproduz e se torna mais comum na época chuvosa.

Habitat preferences, diet, feeding strategy and social organization of the black spider monkey [Ateles paniscus paniscus Linnaeus 1758] in Surinam

A Socioecological Field Study.This monograph reports on a 26 month socioecological study of black spider monkeys (Ateles paniscus paniscus)in the Raleigh-vallen — Voltzberg Nature Reserve, Surinam. It recognizes the fundamental importance of food to the behavior and the regulation of population density fox this primate. It clarifies the complex temporal and spatial effects of tropical rain forest food sources on the behavior of a group of spider monkeys, concentrating on food category, food plant identity and phenology, and quantity, density and dispersion of the most important food sources. In addition, the present study describes habitat choice, optimal feeding strategy and sexual behavior of the spider monkey, and discusses implications of diet for social behavior. This study is also fundamental to conservation. Specialized in eating mature fruits, the spider monkey is a very important dispersal agent for many trees and lianes, particularly canopy species. However, the spider monkey is probably the most vulnerable monkey species in Surinam and it is disappearing rapidly throughout the remainder of its range. Unfortunately, it is large and noisy and can be easily tracked and hunted. It is largely restricted to undisturbed high forest, and consequently habitat destruction has more effect on it than on most other species. Together with its slow reproductive rate (a female gives birth only once every four or five years), this means that the species is poorly adapted to recover from exploitation. In order to implement proper measures for conservation, data on forest type preferences, diet and social behavior of the species, or on closely related species, in undisturbed areas, such as the one described in this monograph, are essential tools for assessing the potential of proposed protected areas.

Produtividade sazonal da floresta e atividade de forrageamento animal em habitat de terra firme da Amazônia

Durante 13 meses (de janeiro de 1986 a janeiro de 1987), quatro trilhas, de aproximadamente 2,5 km de comprimento cada uma, cortando diferentes ambientes de mata de terra firme, foram seguidas diariamente por um mínimo de dois pesquisadores para observar animais forrageando no chão o em diferentes estratos da floresta. O local de estudo foi em porção de floresta protegida em Tucuruí, estado do Pará. Foram investigadas por observação contínua no campo as tendências sazonais de utilização de ítens de alimentos preferidos demonstrados por quelôneos: os jabutis Geochelone carbonaria, G. denticulata e a aperema Platemys platicephala; por roedores: o quatipuru Sciurus gilvigularis e a cutia Dasyprocta aguti; por cervídeos: o veado-mateiro Mazama americana e o veado fuboca Mazama guazoubira; e por primatas: o macaco-prego Cebus apella, o guariba Alouatta belzebul, o cuxiú Chiropotes satanas , o macaco-mão-de-ouro Saimiri sciureus, e o sagui preto Saguinus midas. Todos esses animais foram estudados através de observação contínua nessas trilhas de transectos, estabelecidas na mata de terra firme. As observações foram feitas pela manhã entre 06:00 e 10:00 horas e à tarde, entre 15:00 e 19 horas. O estudo demonstrou que as dietas dessas espécies animais de habitat de terra firme depende da disponibilidade de alimento na floresta na estação do ano. A importância desses ítens de alimento é demonstrada pela mudança sazonal da atividade de forrageamento, dependendo do ítem alimentar em oferta. Os jabtutis (Geochelone carbonaria e G. denticulata) alimentam-se basicamente de frutos disponíveis entre setembro e janeiro, sendo esses mesmo frutos compatilhados por cutia (Dasyprocta aguti), enquanto o macaco-prego (Cebus apella) expande sua dieta baseada em frutas, em dois picos, um entre janeiro e março, com um máximo de atividade em fevereiro, e outro pico entre julho e dezembro. Essas mesmas frutas são também compartilhadas por Chiropotes satanas. Embora o guariba (Alouatta belzebul) seja observado comendo grande porcentagem de folhas, nas estações de produção de frutos, porém, durante os dois picos anuais, (fevereiro e dezembro) tornam-se oportunisticamente frugívoros.

On occurrence, habitat specificity and natural history of adult tiger beetles (Coleoptera: Carabidae: Cicindelinae) near Manaus, Central Amazonia, and key to the larvae of tiger beetle genera

Over a seven year period from 1991 to 1997, 22 species of tiger beetles, representing nine genera, were recorded near Manaus, Brazil. In the Whitewaterfloodplains along the Rio Solimões-Amazonas (Ilha de Marchantaria), three diurnal species inhabit inundation forests and six species (two diurnal, four nocturnal) live in open areas. Data on their natural history and adaptation to living conditions in floodplains are presented. Fifteen species were located on non-flooded uplands (Reserva Florestal A. Ducke). Five diurnal species inhabit the forest floor, two species are canopy dwellers, and eight species (seven diurnal, one nocturnal) live in open areas on whitesand or laterite. Only one species, Pentacomia lacordairei, was found in both floodplain and upland forests. A key to the larvae of tiger beetle genera located near Manaus is presented.

Moisture-induced degradation of interfacial bond in FRP-strengthened masonry

Externally bonded strengthening of masonry structures using Fiber Reinforced Polymers (FRPs) has been accepted as a promising technique. Although the effectiveness of FRPs in improving the performance of masonry components has been extensively investigated, their long-term performance and durability remain poorly addressed. This paper, tackling one of the aspects related to durability of these systems, presents an experimental investigation on the effect of long-term (one year) water immersion on the performance of GFRP-strengthened bricks. The tests include materials' mechanical tests, as well as pull-off and single-lap shear bond tests, to investigate the changes in material properties and bond behavior with immersion time, respectively. The effect of mechanical surface treatment on the durability of the strengthened system as well as the reversibility of the degradation upon partial drying are also investigated. The experimental results are presented and critically discussed.

Effects of residues on the degradation of PHA produced from mixed microbial cultures and processed in extrusion

Thermal degradation upon melting is one of the major drawbacks reported for polyhydroxyalkanoates (PHA). However, the role of residues originating from the fermentation and the extraction steps on the thermal stability of this class of biopolymers still needs to be clarified. In the particular case of PHA produced from mixed microbial cultures (MMC), this topic is even less documented in the literature. Here, two polyhydroxy(butyrate-co-valerate) (PHBV) produced from MMC enriched in PHA accumulating organisms and fed with cheese whey were studied. A micro extrusion line is used to produce filaments and assess the processability and the degradation of processed PHBV. The prototype micro extrusion line allows for studying grams of materials. The two PHBV contain 18 mol% HV. PHBV was recovered with 11 wt% residues, and further submitted to a purification procedure resulting in a second biopolyester containing less than 2 wt% impurities. The thermorheological characterization of the two PHBV is first presented, together with their semicrystalline properties. Then the processing windows of the two biopolyesters are presented. Finally, the properties of extruded filaments are reported and the thermomechanical degradation of PHBV is extensively studied. The structure was assessed by wide angle X-ray diffraction, mechanical and rheological properties are reported, thermal properties are studied with differential scanning calorimetry and thermogravimetric analysis, whereas Fourier Transform Infrared spectroscopy was used to assess the impact of the extrusion on PHBV chemical structure. All results obtained with the two PHBV are compared to assess the effects of residues on both PHBV processability and degradation.

Princípios para a reabilitação sustentável low cost de edifícios antigos: estudo de um quarteirão no centro da cidade do Porto

Dissertação de mestrado em Construção e Reabilitação Sustentável