Minimization of the experimental workload for the prediction of pollutants propagation in rivers. Mathematical modelling and knowledge re-use

The present thesis in focused on the minimization of experimental efforts for the prediction of pollutant propagation in rivers by mathematical modelling and knowledge re-use. Mathematical modelling is based on the well known advection-dispersion equation, while the knowledge re-use approach employs the methods of case based reasoning, graphical analysis and text mining. The thesis contribution to the pollutant transport research field consists of: (1) analytical and numerical models for pollutant transport prediction; (2) two novel techniques which enable the use of variable parameters along rivers in analytical models; (3) models for the estimation of pollutant transport characteristic parameters (velocity, dispersion coefficient and nutrient transformation rates) as functions of water flow, channel characteristics and/or seasonality; (4) the graphical analysis method to be used for the identification of pollution sources along rivers; (5) a case based reasoning tool for the identification of crucial information related to the pollutant transport modelling; (6) and the application of a software tool for the reuse of information during pollutants transport modelling research. These support tools are applicable in the water quality research field and in practice as well, as they can be involved in multiple activities. The models are capable of predicting pollutant propagation along rivers in case of both ordinary pollution and accidents. They can also be applied for other similar rivers in modelling of pollutant transport in rivers with low availability of experimental data concerning concentration. This is because models for parameter estimation developed in the present thesis enable the calculation of transport characteristic parameters as functions of river hydraulic parameters and/or seasonality. The similarity between rivers is assessed using case based reasoning tools, and additional necessary information can be identified by using the software for the information reuse. Such systems represent support for users and open up possibilities for new modelling methods, monitoring facilities and for better river water quality management tools. They are useful also for the estimation of environmental impact of possible technological changes and can be applied in the pre-design stage or/and in the practical use of processes as well.

Sustainable Waste-to-Energy Production: Performance Evaluation of Distributed Generation fuelled by Landfill Gas

The environmental impact of landfill is a growing concern in waste management practices. Thus, assessing the effectiveness of the solutions implemented to alter the issue is of importance. The objectives of the study were to provide an insight of landfill advantages, and to consolidate landfill gas importance among others alternative fuels. Finally, a case study examining the performances of energy production from a land disposal at Ylivieska was carried out to ascertain the viability of waste to energy project. Both qualitative and quantitative methods were applied. The study was conducted in two parts; the first was the review of literatures focused on landfill gas developments. Specific considerations were the conception of mechanism governing the variability of gas production and the investigation of mathematical models often used in landfill gas modeling. Furthermore, the analysis of two main distributed generation technologies used to generate energy from landfill was carried out. The review of literature revealed a high influence of waste segregation and high level of moisture content for waste stabilization process. It was found that the enhancement in accuracy for forecasting gas rate generation can be done with both mathematical modeling and field test measurements. The result of the case study mainly indicated the close dependence of the power output with the landfill gas quality and the fuel inlet pressure.

Fontes vegetais naturais de antioxidantes

Growing knowledge on the health-promoting impact of antioxidants in everyday foods, combined with the assumption that a number of common synthetic preservatives may have hazardous side effects has led to increased investigations in the field of natural antioxidants, principally those found in plants. Food industries normally discard plant residues that could benefit the human health and diminish undesirable environmental impact. Once estimated the content of antioxidants in these residues, advantageous economical and social alternatives to the discard are possible, for example, their use for preparation of nutraceuticals to be offered to low-income populations. We present here a broad, although not complete, account of the continuously growing knowledge on the antioxidant capacity of whole fruits, seeds and peels, cereals, vegetal oils and aromatic plants, at several physical forms, as well as a description of the usual methods for evaluating their antioxidant capacity and examples of agroindustrial processes that could be harnessed for the production of antioxidant supplement food, along with research perspectives in the area.

Avaliação da qualidade de sedimentos - estudo de caso: sub-bacia do Ribeirão Espírito Santo, afluente do Rio São Francisco

This study evaluated the environmental impact resulting from surface water and sediment contamination by metals in a watershed affected by a tailing basin that controls effluents coming from a zinc-ore beneficiation plant. The studies combined assessments of sediment chemistry (exceedances of sediment quality guidelines), benthic assemblage structure and acute and chronic ecotoxicity. The results showed that the levels of metal contamination in sediments are not yet enough to cause deleterious effects to the biota. However, the ecotoxicity tests indicated the occurrence of chronic effects, demonstrating that other factors, as the use of fertilizers, could also be a source of contamination.

Tintas anti-incrustantes de terceira geração: novos biocidas no ambiente aquático

Antifouling agents have been used on vessels and boats since ancient civilizations. Thus, a brief history on the three generations of antifouling paints was provided in the present review. Additionally, information about physic-chemical properties, environmental levels, toxicology and analytical methods was discussed for the 16 "new" booster biocides used as third-generation antifouling paints. The main problems, limitations and future trends related to this subject were also presented. Finally, actions were suggested in order to appraise the current status of the environmental impact caused by these compounds in South America.

Ocorrência, comportamento e impactos ambientais provocados pela presença de antimicrobianos veterinários em solos

Antimicrobials, among other veterinary drugs, are used worldwide in industry and agriculture to protect animal health and prevent economic loss. In recent years, they have been detected in various environmental compartments, including soil, surface and groundwater and have become a topic of research interest. Emphasizing this class of compounds, this review presents the different pathways which veterinary drugs enter in the environment, in particular contaminate soils. Also are presented regulatory aspects and guidelines, adsorption/desorption and degradation of these compounds in soils and the consequences of its dispersal in the environment.

Química Sem Fronteiras: o desafio da energia

Coal, natural gas and petroleum-based liquid fuels are still the most widely used energy sources in modern society. The current scenario contrasts with the foreseen shortage of petroleum that was spread out in the beginning of the XXI century, when the concept of "energy security" emerged as an urgent agenda to ensure a good balance between energy supply and demand. Much beyond protecting refineries and oil ducts from terrorist attacks, these issues soon developed to a portfolio of measures related to process sustainability, involving at least three fundamental dimensions: (a) the need for technological breakthroughs to improve energy production worldwide; (b) the improvement of energy efficiency in all sectors of modern society; and (c) the increase of the social perception that education is a key-word towards a better use of our energy resources. Together with these technological, economic or social issues, "energy security" is also strongly influenced by environmental issues involving greenhouse gas emissions, loss of biodiversity in environmentally sensitive areas, pollution and poor solid waste management. For these and other reasons, the implementation of more sustainable practices in our currently available industrial facilities and the search for alternative energy sources that could partly replace the fossil fuels became a major priority throughout the world. Regarding fossil fuels, the main technological bottlenecks are related to the exploitation of less accessible petroleum resources such as those in the pre-salt layer, ranging from the proper characterization of these deep-water oil reservoirs, the development of lighter and more efficient equipment for both exploration and exploitation, the optimization of the drilling techniques, the achievement of further improvements in production yields and the establishment of specialized training programs for the technical staff. The production of natural gas from shale is also emerging in several countries but its production in large scale has several problems ranging from the unavoidable environmental impact of shale mining as well as to the bad consequences of its large scale exploitation in the past. The large scale use of coal has similar environmental problems, which are aggravated by difficulties in its proper characterization. Also, the mitigation of harmful gases and particulate matter that are released as a result of combustion is still depending on the development of new gas cleaning technologies including more efficient catalysts to improve its emission profile. On the other hand, biofuels are still struggling to fulfill their role in reducing our high dependence on fossil fuels. Fatty acid alkyl esters (biodiesel) from vegetable oils and ethanol from cane sucrose and corn starch are mature technologies whose market share is partially limited by the availability of their raw materials. For this reason, there has been a great effort to develop "second-generation" technologies to produce methanol, ethanol, butanol, biodiesel, biogas (methane), bio-oils, syngas and synthetic fuels from lower grade renewable feedstocks such as lignocellulosic materials whose consumption would not interfere with the rather sensitive issues of food security. Advanced fermentation processes are envisaged as "third generation" technologies and these are primarily linked to the use of algae feedstocks as well as other organisms that could produce biofuels or simply provide microbial biomass for the processes listed above. Due to the complexity and cost of their production chain, "third generation" technologies usually aim at high value added biofuels such as biojet fuel, biohydrogen and hydrocarbons with a fuel performance similar to diesel or gasoline, situations in which the use of genetically modified organisms is usually required. In general, the main challenges in this field could be summarized as follows: (a) the need for prospecting alternative sources of biomass that are not linked to the food chain; (b) the intensive use of green chemistry principles in our current industrial activities; (c) the development of mature technologies for the production of second and third generation biofuels; (d) the development of safe bioprocesses that are based on environmentally benign microorganisms; (e) the scale-up of potential technologies to a suitable demonstration scale; and (f) the full understanding of the technological and environmental implications of the food vs. fuel debate. On the basis of these, the main objective of this article is to stimulate the discussion and help the decision making regarding "energy security" issues and their challenges for modern society, in such a way to encourage the participation of the Brazilian Chemistry community in the design of a road map for a safer, sustainable and prosper future for our nation.

EXTRAÇÃO DE POLI(3-HIDROXIBUTIRATO), PRODUZIDO POR Cupriavidus necator, COM CARBONATO DE PROPILENO

The environmental impact of plastic waste has attracted worldwide attention. Amid the current context of increasing concern for the environment, biodegradable plastics have been widely studied as a replacement for synthetic plastics. Poly(3-hydroxybutyrate) (P(3HB)) is a biopolymer stored as an intracellular energy and reserve source in many microorganisms. Because it is an intracellular product, P(3HB) must be extracted from the cells at the end of the culture. The purpose of this study was to investigate the effect of extraction time, heating temperature, first standing time (after filtration and extraction), second standing time (after P(3HB) precipitation) and solvent amount, during the process of extracting P(3HB) from Cupriavidus necator DSM 545, using propylene carbonate as solvent. The extraction kinetic of P(3HB) with propylene carbonate from thermally treated biomass was evaluated at different temperatures. The physical properties of the P(3HB) obtained were also evaluated. In this case, P(3HB) obtained at optimal conditions of recovery (98%) and purity (99%) was used. Results showed that temperature was the most important factor in these responses for the range of values studied (110-150 ºC).

PYROLIGNEOUS LIQUOR PRODUCED FROM ACACIA MEARNSII DE WILD WOOD UNDER CONTROLLED CONDITIONS AS A RENEWABLE SOURCE OF CHEMICALS

Acacia mearnsii de Wild (black wattle) is one of the most important trees planted in Southern Brazil for tannin extraction and charcoal production. The pyrolysis of the black wattle wood used for obtaining charcoal is performed in brick ovens, with the gas fraction being sent directly into the environment. The present study examines the condensable compounds present in the liquor produced from black wattle wood at different thermal degradation conditions, using gas chromatography coupled with mass spectrometry (GC/MS). Branches of black wattle were thermally degraded at controlled ambient and temperature conditions. Overall, a higher variety of compounds were obtained under atmospheric air pressure than under synthetic air pressure. Most of the tentatively identified compounds, such as carboxylic acids, phenols, aldehydes, and low molecular mass lignin fragments, such as guayacol, syringol, and eugenol, were products of lignin thermoconversion. Substituted aromatic compounds, such as vanillin, ethyl vanillin, and 2-methoxy-4-propeny-phenol, were also identified. At temperatures above 200 ºC, furan, 2-acetylfuran, methyl-2-furoate, and furfural, amongst others, were identified as polysaccharide derivatives from cellulose and hemicellulose depolymerization. This study evidences the need for adequate management of the condensable by-products of charcoal production, both for economic reasons and for controlling their potential environmental impact.

Painovoimaisen kemiallisen vesienkäsittelymenetelmän soveltuvuus pienille turvetuotantoalueille

Turvetuotannon suurimpana ympäristövaikutuksena pidetään tuotantoalueiden valuma-vesistä johtuvia ympäristövaikutuksia. Tiukentunut ympäristölainsäädäntö edellyttää uusilta turvetuotantoalueilta parhaan käyttökelpoisen tekniikan käyttöä valumavesien-käsittelyssä. Parhaaksi käyttökelpoiseksi tekniikaksi luetaan pintavalutus- ja kasvilli-suuskentän sekä kemikaloinnin käyttö valumavesien puhdistuksessa. Tämän tutkimuksen tarkoituksena oli selvittää painovoimaisen kemiallisen vesienkäsit-telymenetelmän soveltuvuutta pienille turvetuotantoalueille. Tutkimuskohteena oli Lep-pisuo Luumäen kunnassa, jonne rakennettiin 2010 painovoimaisen kemikaloinnin koe-laitteisto. Laitteiston puhdistustulosta tarkasteltiin kemikalointiin tulevan ja lähtevän veden sekä taustanäytepisteiden tarkkailutulosten avulla. Laitteiston toimivuutta arvioi-tiin kemikaalin annostelun ja toimintavarmuuden avulla. Vuoden 2010 tarkkailutuloksista saatiin keskimääräisiksi erotustehokkuuksiksi koko-naisfosforin osalta 65,2 %, kokonaistypen osalta 28,1 % ja CODMn osalta 65,5 %. Ke-mikaloinnista lähtevän veden kokonaisfosforipitoisuus oli 7,7 μg/l, kokonaistyppipitoi-suus 656 μg/l ja CODMn 5,5 mg/l O2. Ferrisulfaatin annostelu oli keskimäärin 81 mg/l, vaihteluvälillä 25–268 mg/l.

Operational characteristics of four metering systems for agricultural fertilizers and amendments

The use of fertilizers and solid amendments in agriculture generates special interest for their effect on crop productivity, as well as for their environmental impact. The efficient use of these products demands knowing their physical and mechanical properties, the storing conditions effect and the operational characteristics of the metering systems used in the fertilizing equipment. In this context, the present study was developed with the purpose of evaluating the operational characteristics of different fertilizing metering systems and to determine the adequate metering system-product operational parameters, using powder lime, powder gypsum, granular 10-30-10 (N-P-K), and granular urea. Operational differences were established among four types of commercial fertilizer metering systems, including wire auger, star-shaped feed wheel, feed screw and ridged traction wheel. The study found that the unloading rate depends directly on the fertilizer metering system's rotating speed and is affected by particle size, repose angle, bulk density and moisture content of the applied product. The wire auger and star-shaped feed wheel metering systems were adequate for the distribution of powder products and the feed screw for granulated fertilizers. Furthermore, theoretical and experimental characteristic equations were established, defining curves for calibration and handling of the products plus the rotating speed range in which a better distributing behavior was achieved.

Anaerobic biodigestion of pigs feces in the initial, growing and finishing stages fed with diets formulated with corn or sorghum

The objective of this study was to evaluate the quality and the production of biogas and biofertilizer obtained from biodigester supplied with pig feces in the initial, growing and finishing stages, fed with diets formulated based on corn or sorghum. Twenty bench biodigesters were used with hydraulic retention time of 30 days and daily loads that contained 4 to 6% of total solids (TS) and 3.6 to 5.2% of volatile solids (VS). In the effluent of the biodigesters, mean levels of TS were observed ranging between 1.6 and 2.0% and of VS between 1.2 and 1.6%. The mean reductions of TS were 57.7 to 64.7% and of VS from 61.7 to 69.0%, and there was only difference in the finishing phase, in which the major averages reductions were produced by the biodigesters supplied with feces from animals fed with diets based on corn. In biodigesters supplied with feces from animals in the initial and growing stages fed with diets based on corn, were observed higher average productions of biogas and the greatest average potentials of biogas production. The average potentials obtained were 0.033; 0.181; 0.685; 0.788 and 1.132 m³ per kg of affluent, manure, TS added, VS added and VS reduced, respectively. No differences were found on the average content of methane in the biogas between diets and stages. The average concentrations of nutrients N, P, K, Ca, Mg, Na, Fe, Mn, Zn and Cu in the biodigester affluent and effluent, ranged between diets and stages.

Characterization and use of swine deep bedding ashes in cementitious composites

The deep bedding is a swine alternative production, especially in the finishing phase, whose byproduct can be recycled, reducing the environmental impact. The objectives of this study were to characterize the ash coming from the controlled burning of the swine deep bedding (SDBA) based on rice husk, and to evaluate their performance in composites as a partial substitute for Portland cement (PC). To measure the differences between SDBA and rice husk ash (RHA) as a reference, we have characterized: particle size distribution, real specific density, x-ray diffraction, electrical conductivity, scanning electron microscopy, chemical analysis and loss on ignition. Samples were prepared for two experimental series: control, and another one with the partial replacement of 30% of SDBA in relation to the mass of the Portland cement. According to the results obtained for physical and mechanical characterization, the composites with SDBA can be used as a constructive element in the rural construction.

Selection of microorganisms producer of lipase for fat removal from biodiesel purification water

The objective this study has been the selection of lipase productor microorganism, for removal of oils and grease, in the pre-treatment of biodiesel wastewater washing. For this, analyses of the physicist-chemistries characteristics had been made with the wastewater of the biodiesel washing, and then it had been isolated and chosen, by means of determinations of the lipase activity. Following, it was made a test of fat biodegradation, in the conditions: pH (5.95), temperature (35 ºC), rotation (180 rpm) and ammonium sulfate as nitrogen source (3 g L-1) and establishing as variable the two microorganism preselected and the time (24; 48; 72; 96 and 120 h). The biodiesel purification wastewater had presented high potential of environmental impact, presenting a concentration of O of 6.76 g L-1. From the six isolated microbiological cultures, two microorganisms (A and B) had been selected, with enzymatic index of 0.56 and 0.57, respectively. The treatment of the wastewater using the isolated microorganism (Klebsiella oxytoca) had 80% of the fatty removal in 48 h.

Precision agriculture in Australia: present status and recent developments

A brief account of the present status of Precision Agriculture (PA) in Australia is presented, and areas of opportunity in the grains, sugar and wine industries are identified. In particular, these relate to the use of spatially-distributed experimentation to fine-tune management so as to achieve production efficiencies, reduced risk of environmental impact and enhanced food security, and the management of crop quality through selective harvesting and product streaming. The latter may be an important avenue by which farmers can take a more active role in the off-farm part of agricultural value chains. The important role of grower groups in facilitating PA adoption is also discussed.