A exportação do mel português: um estudo exploratório sobre as motivações, barreiras e estratégias

Dissertação de Mestrado apresentado ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Empreendedorismo e Internacionalização, sob orientação de Professor Doutor António Correia de Barros

Nanofiltration of Cork Wastewaters and Their Possible Use in Leather Industry as Tanning Agents

Cork processing wastewater is a very complex mixture of vegetal extracts and has, among other natural compounds, a very high content of phenolic/tannic colloidal matter that is responsible for severe environmental problems. In the present work, the concentration of this wastewater by nanofiltration was investigated with the aim of producing a cork tannin concentrate to be utilized in tanning. Permeation results showed that the permeate fluxes are controlled by both osmotic pressure and fouling/gel layer phenomena, leading to a rapid decrease of permeate fluxes with the concentration factor. The rejection coefficients to organic matter were higher than 95%, indicating that nanofiltration has a very good ability to concentrate the tannins and produce a permeate stream depleted from organic matter. The cork tannin concentrate obtained by nanofiltration and evaporation had total solids concentration of 34.8 g/l. The skins tanned by this concentrate were effectively converted to leather with a shrinking temperature of 7 degrees C.

Cork industry wastewater partition by ultra/nanofiltration: A biodegradation and valorisation study

Wastewater from cork processing industry present high levels of organic and phenolic compounds, such as tannins, with a low biodegradability and a significant toxicity. These compounds are not readily removed by conventional municipal wastewater treatment, which is largely based on primary sedimentation followed by biological treatment. The purpose of this work is to study the biodegradability of different cork wastewater fractions, obtained through membrane separation, in order to assess its potential for biological treatment and having in view its valorisation through tannins recovery, which could be applied in other industries. Various ultrafiltration and nanofiltration membranes where used, with molecular weight cut-offs (MWCO) ranging from 0.125 to 91 kDa. The wastewater and the different permeated fractions were analyzed in terms of Total Organic Carbon (TOC), Chemical Oxygen Demand (COD), Biochemical Oxygen Demand (BOD), Total Phenols (TP), Tannins, Color, pH and Conductivity. Results for the wastewater shown that it is characterized by a high organic content (670.5-1056.8 mg TOC/L, 2285-2604 mg COD/L, 1000-1225 mg BOD/L), a relatively low biodegradability (0.35-0.38 for BODs/COD and 0.44-0.47 for BOD20/COD) and a high content of phenols (360-410 mg tannic acid/L) and tannins (250-270 mg tannic acid/L). The results for the wastewater fractions shown a general decrease on the pollutant content of permeates, and an increase of its biodegradability, with the decrease of the membrane MWCO applied. Particularly, the permeated fraction from the membrane MWCO of 3.8 kDa, presented a favourable index of biodegradability (0.8) and a minimized phenols toxicity that enables it to undergo a biological treatment and so, to be treated in a municipal wastewater treatment plant. Also, within the perspective of valorisation, the rejected fraction obtained through this membrane MWCO may have a significant potential for tannins recovery. Permeated fractions from membranes with MWCO lower than 3.8 kDa, presented a particularly significant decline of organic matter and phenols, enabling this permeates to be reused in the cork processing and so, representing an interesting perspective of zero discharge for the cork industry, with evident environmental and economic advantages. (C) 2010 Elsevier Ltd. All rights reserved.

Cork industry wastewater characterization assessment of the biodegradability, reuse and of the relationship between BOD, COD and tannins with TOC

Cork processing involves a boiling step to make the cork softer, which consumes a high volume of water and generates a wastewater with a high organic content, rich in tannins. An assessment of the final wastewater characteristics and of the boiling water composition along the boiling process was performed. The parameters studied were pH, color, total organic carbon (TOC), chemical and biochemical oxygen demands (COD, BOD5, BOD20), total suspended solids (TSS), total phenols and tannins (TP, TT). It was observed that the water solutes extraction power is significantly reduced for higher quantities of cork processed. Valid relationships between parameters were established not only envisaging wastewater characterization but also to provide an important tool for wastewater monitoring and for process control/optimization. Boiling water biodegradability presented decreasing values with the increase of cork processed and for the final wastewater its value is always lower than 0.5, indicating that these wastewaters are very difficult to treat by biological processes. The biodegradability was associated with the increase of tannin content that can rise up to 0.7 g/L. These compounds can be used by other industries when concentrated and the clarified wastewater can be reused, which is a potential asset in this wastewater treatment.

The problems of the european union film industry: an evolution from "subsidy trap" to the advent of "virtual print fee" model

Dissertação de Mestrado, Gestão de Empresa (MBA), 16 de Julho de 2013, Universidade dos Açores.

Integration of biomonitoring and instrumental techniques to assess the air quality in an industrial area located in the coastal of Central Asturias, Spain

Throughout the world, epidemiological studies were established to examine the relationship between air pollution and mortality rates and adverse respiratory health effects. However, despite the years of discussion the correlation between adverse health effects and atmospheric pollution remains controversial, partly because these studies are frequently restricted to small and well-monitored areas. Monitoring air pollution is complex due to the large spatial and temporal variations of pollution phenomena, the high costs of recording instruments, and the low sampling density of a purely instrumental approach. Therefore, together with the traditional instrumental monitoring, bioindication techniques allow for the mapping of pollution effects over wide areas with a high sampling density. In this study, instrumental and biomonitoring techniques were integrated to support an epidemiological study that will be developed in an industrial area located in Gijon in the coastal of central Asturias, Spain. Three main objectives were proposed to (i) analyze temporal patterns of PM10 concentrations in order to apportion emissions sources, (ii) investigate spatial patterns of lichen conductivity to identify the impact of the studied industrial area in air quality, and (iii) establish relationships amongst lichen conductivity with some site-specific characteristics. Samples of the epiphytic lichen Parmelia sulcata were transplanted in a grid of 18 by 20 km with an industrial area in the center. Lichens were exposed for a 5-mo period starting in April 2010. After exposure, lichen samples were soaked in 18-MΩ water aimed at determination of water electrical conductivity and, consequently, lichen vitality and cell damage. A marked decreasing gradient of lichens conductivity relative to distance from the emitting sources was observed. Transplants from a sampling site proximal to the industrial area reached values 10-fold higher than levels far from it. This finding showed that lichens reacted physiologically in the polluted industrial area as evidenced by increased conductivity correlated to contamination level. The integration of temporal PM10 measurements and analysis of wind direction corroborated the importance of this industrialized region for air quality measurements and identified the relevance of traffic for the urban area.

Modelação do transporte e dispersão atmosférica de poluentes produzidos por uma refinaria: estudo de caso

Mestrado em Engenharia Química.Ramo Tecnologias de Protecção Ambiental

Valorização de subprodutos da vinha e do vinho: impacto do tempo e métodos de preservação nas suas características

Os polifenóis constituem um grupo biologicamente relevante de compostos naturais, que têm gerado um crescente interesse por parte dos consumidores e das indústrias alimentar, farmacêutica e de cosméticos. Os compostos fenólicos exibem uma vasta gama de propriedades fisiológicas, tais como anti-alérgica, anti-aterogénica, anti-inflamatória, anti-microbiana, antioxidante, anti-trombótica, possuindo efeitos cardio-protetores e vasodilatadores. Por conseguinte, o interesse na obtenção deste compostos ativos de uma forma fácil, barata e rápida tem vindo a aumentar. Uma das fontes de polifenóis são os subprodutos agrícolas, tais como os produtos derivados do vinho e/ou processamento de uvas. As folhas, os caules e os resíduos obtidos durante o processo de produção do vinho têm sido subutilizados, apesar de representarem uma boa fonte de compostos antioxidantes e bioativos. Portugal é um dos mais importantes países produtores de vinho, onde todos os anos são geradas várias toneladas de subprodutos associados a esta indústria. A extração, caracterização, quantificação e avaliação da atividade antioxidante de compostos bioativos extraídos destes subprodutos são, pois, tarefas importantes a fim de avaliar o potencial de utilização destes produtos como novas fontes de compostos antioxidantes. O objetivo deste trabalho foi quantificar e avaliar os teores de polifenóis de extratos preparados a partir de folhas e caules de videira, e bagaço, engaço e grainha de uva. Os parâmetros experimentais da extração foram otimizados, incluindo a proporção de solvente de extração (água/etanol), a temperatura e o tempo de extração. A quantificação dos polifenóis (como fenóis totais e flavonoides) foi efetuada por espetrofotometria de UV/Vis. Verificou-se que a melhor razão de solventes extratores foi de 50/50 (v/v) em água/etanol para todos os subprodutos estudados. No caso dos subprodutos folhas e caules, as condições ideais de extração foram obtidas quando se usou uma temperatura de 40ºC e um tempo de extração de 30 min. Para o bagaço, a temperatura ideal foi de 55ºC durante 5 min. Para o engaço e grainha a utilização de uma temperatura de 40ºC durante 5 min e 30 min, respetivamente, revelou-se o ideal para se obter os compostos. Com este trabalho conclui-se que os subprodutos da vinha e do vinho efetivamente possuem compostos de elevado valor e com capacidade antioxidante.

Public health and the knowledge industry

Knowledge plays an important role in health care. The production and diffusion of health-related knowledge are increasingly under the control of private commercial interests, which are characterized by conflicts of interests that result in abuses of power. Considerable research has been done on the medical-industrial complex and its role in the production of power imbalances and the consequent abuses, but little attention has been dedicated to the role played by the publishing industry, which can be subject to the same problems. The widely diffused idea that "frequent and major changes" occur in medicine, albeit unsupported by clearcut evidence, is an effective marketing tool for both the pharmaceutical and publishing industries, who feed and thrive on physicians' insecurities. The production and distribution of knowledge should be addressed as a strategic component of public health.

Development of a SPME-GC-ECD methodology for selected pesticides in must and wine samples

A method for the determination of some pesticide residues in must and wine samples was developed using solid-phase microextraction (SPME) and gas chromatography – electron capture detection (GC/ECD). The procedure only needs dilution as sample pre-treatment and is therefore simple, fast and solvent-free. Eight fungicides (vinclozolin, procymidone, iprodione, penconazole, fenarimol, folpet, nuarimol and hexaconazole), one insecticide (chlorpyriphos) and two acaricides (bromopropylate and tetradifon) can be quantified. Good linearity was observed for all the compounds in the range 5–100 µg/L. The reproducibility of the measurements was found acceptable (with RSD’s below 20%). Detection limits of 11 µg/L, on average, are sufficiently below the proposed maximum residue limits (MRL’s) for these compounds in wine. The analytical method was applied to the determination of these compounds in Portuguese must and wine samples from the Demarcated Region of Alentejo, where any residues could be detected.

Fast growing fungi: a problem to be solved to achieve characterization of occupational exposure to fungi in cork industry

Chrysonilia sitophila is a common mould in cork industry and has been identified as a cause of IgE sensitization and occupational asthma. This fungal species have a fast growth rate that may inhibit others species’ growth causing underestimated data from characterization of occupational fungal exposure. Aiming to ascertain occupational exposure to fungi in cork industry, were analyzed papers from 2000 about the best air sampling method, to obtain quantification and identification of all airborne culturable fungi, besides the ones that have fast-growing rates. Impaction method don’t allows the collection of a representative air volume, because even with some media that restricts the growth of the colonies, in environments with higher fungal load, such as cork industry, the counting of the colonies is very difficult. Otherwise, impinger method permits the collection of a representative air volume, since we can make dilution of the collected volume. Besides culture methods that allows fungal identification trough macro- and micro-morphology, growth features, thermotolerance and ecological data, we can apply molecular biology with the impinger method, to detect the presence of non-viable particles and potential mycotoxin producers’ strains, and also to detect mycotoxins presence with ELISA or HPLC. Selection of the best air sampling method in each setting is crucial to achieve characterization of occupational exposure to fungi. Information about the prevalent fungal species in each setting and also the eventual fungal load it’s needed for a criterious selection.

Multiresidue method for the determination of organophosphorus pesticides in still wine and fortified wine using solid-phase microextraction and gas chromatography – Tandem mass spectrometry

A SPME-GC-MS/MS method for the determination of eight organophosphorus pesticides (azinphos-methyl, chlorpyriphos, chlorpyriphos-methyl, diazinon, fenitrothion, fenthion, malathion, and methidathion) in still and fortified wine was developed. The extraction procedure is simple, solvent free, and without any sample pretreatment. Limits of detection (LOD) and quantitation (LOQ) values in the range 0.1–14.3 lg/L and 0.2–43.3 lg/L, respectively, were obtained. The LOQ values are below the maximum residue levels (MRLs) established by European Regulation for grapes, with the exception of methidathion. Coefficients of correlation (R2) higher than 0.99 were obtained for the majority of the pesticides, in all different wines analyzed.

Assessment of workers’ exposure to Aflatoxin B1 in a Portuguese waste industry

Aflatoxin B1 (AFB1) is considered by different International Agencies as a genotoxic and potent hepatocarcinogen. However, despite the fact that the fungi producing this compound are detected in some work environments, AFB1 is rarely monitored in occupational settings. The aim of the present investigation was to assess exposure to AFB1 of workers from one Portuguese waste company located in the outskirt of Lisbon. Occupational exposure assessment to AFB1 was done with a biomarker of internal dose that measures AFB1 in the serum by enzyme-linked immunosorbent assay. Forty-one workers from the waste company were enrolled in this study (26 from sorting; 9 from composting; 6 from incineration). A control group (n = 30) was also considered in order to know the AFB1 background levels for the Portuguese population. All the workers showed detectable levels of AFB1 with values ranging from 2.5ng ml−1 to 25.9ng ml−1 with a median value of 9.9±5.4ng ml−1. All of the controls showed values below the method’s detection limit. Results obtained showed much higher (8-fold higher) values when compared with other Portuguese settings already studied, such as poultry and swine production. Besides this mycotoxin, other mycotoxins are probably present in this occupational setting and this aspect should be taken into consideration for the risk assessment process due to possible synergistic reactions. The data obtained suggests that exposure to AFB1 occurs in a waste management setting and claims attention for the need of appliance of preventive and protective safety measures.

Screening of grapes and wine for azoxystrobin, kresoxim-methyl and trifloxystrobin fungicides by HPLC with diode array detection

The Quinone outside Inhibitors (QoI) are one of the most important and recent fungicide groups used in viticulture and also allowed by Integrated Pest Management. Azoxystrobin, kresoxim-methyl and trifloxystrobin are the main active ingredients for treating downy and powdery mildews that can be present in grapes and wines. In this paper, a method is reported for the analysis of these three QoI-fungicides in grapes and wine. After liquid–liquid extraction and a clean-up on commercial silica cartridges, analysis was by isocratic HPLC with diode array detection (DAD) with a run time of 13 min. Confirmation was by solid-phase micro-extraction (SPME), followed by GC/MS determination. The main validation parameters for the three compounds in grapes and wine were a limit of detection up to 0.073mg kg-1, a precision not exceeding 10.0% and an average recovery of 93% ±38.