Production of polyhydroxyalkanoates from oil-containing substrates

Different oil-containing substrates, namely, used cooking oil (UCO), fatty acids-byproduct from biodiesel production (FAB) and olive oil deodorizer distillate (OODD) were tested as inexpensive carbon sources for the production of polyhydroxyalkanoates (PHA) using twelve bacterial strains, in batch experiments. The OODD and FAB were exploited for the first time as alternative substrates for PHA production. Among the tested bacterial strains, Cupriavidus necator and Pseudomonas resinovorans exhibited the most promising results, producing poly-3-hydroxybutyrate, P(3HB), form UCO and OODD and mcl-PHA mainly composed of 3-hydroxyoctanoate (3HO) and 3-hydroxydecanoate (3HD) monomers from OODD, respectively. Afterwards, these bacterial strains were cultivated in bioreactor. C. necator were cultivated in bioreactor using UCO as carbon source. Different feeding strategies were tested for the bioreactor cultivation of C. necator, namely, batch, exponential feeding and DO-stat mode. The highest overall PHA productivity (12.6±0.78 g L-1 day-1) was obtained using DO-stat mode. Apparently, the different feeding regimes had no impact on polymer thermal properties. However, differences in polymer‟s molecular mass distribution were observed. C. necator was also tested in batch and fed-batch modes using a different type of oil-containing substrate, extracted from spent coffee grounds (SCG) by super critical carbon dioxide (sc-CO2). Under fed-batch mode (DO-stat), the overall PHA productivity were 4.7 g L-1 day-1 with a storage yield of 0.77 g g-1. Results showed that SCG can be a bioresource for production of PHA with interesting properties. Furthermore, P. resinovorans was cultivated using OODD as substrate in bioreactor under fed-batch mode (pulse feeding regime). The polymer was highly amorphous, as shown by its low crystallinity of 6±0.2%, with low melting and glass transition temperatures of 36±1.2 and -16±0.8 ºC, respectively. Due to its sticky behavior at room temperature, adhesiveness and mechanical properties were also studied. Its shear bond strength for wood (67±9.4 kPa) and glass (65±7.3 kPa) suggests it may be used for the development of biobased glues. Bioreactor operation and monitoring with oil-containing substrates is very challenging, since this substrate is water immiscible. Thus, near-infrared spectroscopy (NIR) was implemented for online monitoring of the C. necator cultivation with UCO, using a transflectance probe. Partial least squares (PLS) regression was applied to relate NIR spectra with biomass, UCO and PHA concentrations in the broth. The NIR predictions were compared with values obtained by offline reference methods. Prediction errors to these parameters were 1.18 g L-1, 2.37 g L-1 and 1.58 g L-1 for biomass, UCO and PHA, respectively, which indicates the suitability of the NIR spectroscopy method for online monitoring and as a method to assist bioreactor control. UCO and OODD are low cost substrates with potential to be used in PHA batch and fed-batch production. The use of NIR in this bioprocess also opened an opportunity for optimization and control of PHA production process.

The use of bone bridges in transtibial amputations

We sought to describe the bone bridge technique in adults, and present a variation for use in children, as well as to present its applicability as an option in elective transtibial amputations. This paper presents a prospective study of 15 transtibial amputations performed between 1992 and 1995 in which the bone bridge technique was employed. The patients' ages ranged from 8 to 48 years, with an average of 22.5 years. This technique consisted of the preparation of a cylinder of periosteum extracted from the tibia and with cortical bone fragments attached to it to promote a tibiofibular synostosis on the distal extremity of the amputation stump. We noted that the cortical bone fragments were dispensable when the technique was employed in children, due to the increased osteogenic capacity of the periosteum. This led to a variation of the original technique, a bone bridge without the use of the cortical bone fragments. RESULTS: The average time spent with this procedure, without any significant variation between adults and children, was 171 minutes. The adaptation to the definitive prosthesis was accomplished between 20 and 576 days, with an average of 180 days. Revision of the procedure was necessary in 3 amputations. CONCLUSIONS: This technique may be employed in transtibial amputations in which the final length of the stump lies next to the musculotendinous transition of the gastrocnemius muscle, as well as in the revision of amputation stumps in children, where the procedure has been shown to be effective in the prevention of lesions due to excessive bone growth.

Optimization of wastewater quality in the Sines refinery

In order to address and resolve the wastewater contamination problem of the Sines refinery with the main objective of optimizing the quality of this stream and reducing the costs charged to the refinery, a dynamic mass balance was developed nd implemented for ammonia and polar oil and grease (O&G) contamination in the wastewater circuit. The inadequate routing of sour gas from the sour water stripping unit and the kerosene caustic washing unit, were identified respectively as the major source of ammonia and polar substances present in the industrial wastewater effluent. For the O&G content, a predictive model was developed for the kerosene caustic washing unit, following the Projection to Latent Structures (PLS) approach. Comparison between analytical data for ammonia and polar O&G concentrations in refinery wastewater originating from the Dissolved Air Flotation (DAF) effluent and the model predictions of the dynamic mass balance calculations are in a very good agreement and highlights the dominant impact of the identified streams for the wastewater contamination levels. The ammonia contamination problem was solved by rerouting the sour gas through an existing clogged line with ammonia salts due to a non-insulated line section, while for the O&G a dynamic mass balance was implemented as an online tool, which allows for prevision of possible contamination situations and taking the required preventive actions, and can also serve as a basis for establishing relationships between the O&G contamination in the refinery wastewater with the properties of the refined crude oils and the process operating conditions. The PLS model developed could be of great asset in both optimizing the existing and designing new refinery wastewater treatment units or reuse schemes. In order to find a possible treatment solution for the spent caustic problem, an on-site pilot plant experiments for NaOH recovery from the refinery kerosene caustic washing unit effluent using an alkaline-resistant nanofiltration (NF) polymeric membrane were performed in order to evaluate its applicability for treating these highly alkaline and contaminated streams. For a constant operating pressure and temperature and adequate operating conditions, 99.9% of oil and grease rejection and 97.7% of chemical oxygen demand (COD) rejection were observed. No noticeable membrane fouling or flux decrease were registered until a volume concentration factor of 3. These results allow for NF permeate reuse instead of fresh caustic and for significant reduction of the wastewater contamination, which can result in savings of 1.5 M€ per year at the current prices for the largest Portuguese oil refinery. The capital investments needed for implementation of the required NF membrane system are less than 10% of those associated with the traditional wet air oxidation solution of the spent caustic problem. The operating costs are very similar, but can be less than half if reusing the NF concentrate in refinery pH control applications. The payback period was estimated to be 1.1 years. Overall, the pilot plant experimental results obtained and the process economic evaluation data indicate a very competitive solution through the proposed NF treatment process, which represents a highly promising alternative to conventional and existing spent caustic treatment units.

Os médicos do trabalho e a nova organização da saúde e segurança do trabalho : quais as consequências na prática profissional? António de Sousa Uv

RESUMO - Em 1994/1995 o modelo legal de organização de serviços de Medicina do Trabalho instituído na década de 1960 foi substituído por uma nova superestrutura de serviços de Segurança, Higiene e Saúde dos Trabalhadores (SHST) nos locais de trabalho. O presente estudo pretende descrever e analisar em que medida o novo enquadramento jurídico de SHST, iniciado em 1994/1995 e correspondente genericamente à fase da Nova Saúde Ocupacional, foi acompanhado de alterações: (1) na percepção do grau de satisfação dos médicos do trabalho quanto ao seu papel e estatuto profissionais e (2) nas repercussões na sua prática profissional. O presente estudo (empírico, descritivo e comparativo) abrangeu um grupo de médicos do trabalho diplomados pela Escola Nacional de Saúde Pública (n = 153), de quem se recolheu, através de um questionário aplicado em 1993 e 2000, a opinião sobre as mudanças organizacionais da SHST. O papel e funções dos médicos do trabalho e as garantias de exercício profissional não se alteraram de forma importante, tendo a prática profissional da medicina do trabalho na modalidade «medicina do trabalho de empresa» (serviços internos e externos) diminuído, apesar de continuar a ser a forma de exercício predominante dos médicos do trabalho. O tempo dedicado à sua actividade situou-se num valor médio próximo das 20 horas semanais, sem alterações importantes entre 1993 e 2000. Concluiu-se que, no essencial, a publicação da nova legislação sobre organização de cuidados de MT/SHST/SO em 1994 e 1995 não reforçou significativamente as condições gerais de exercício da medicina do trabalho.

Reinvigorating and redesigning early intervention in psychosis services for young people in Auckland

RESUMO: Auckland tem sido pioneira na implementação de modelos de Intervenção Precoce em Psicose. No entanto, esta organização do serviço não mudou nos últimos 19 anos. Segundo os dados obtidos da utilização do serviço, no período de 1996 -2012 foram atendidos 997 doentes, que tinham um número médio de 89 contactos (IQR: 36-184), com uma duração média de 62 horas de contactos (IQR: 24-136). Estes doentes passaram um número médio de 338 dias (IQR: 93-757) em contacto com o programa. 517 doentes (52%) não necessitaram de internamento no hospital, e os que foram internados, ficaram uma mediana de 124 dias no hospital (IQR: 40-380). Os doentes asiáticos tiveram um aumento de 50% de probabilidade de serem internados no hospital. Este relatório inclui 15 recomendações para orientar as reformas para o serviço e, nomeadamente, delinear a importância de uma visão organizacional e dos seus componentes-chave. As recomendações incluem o reforço da gestão e da liderança numa estrutura de equipe mais integrada, com recursos dedicados a melhorar a consciencialização da comunidade, a educação e deteção precoce, bem como a capacidade de receber referenciações diretas. Os Indicadores Chave de Desempenho devem ser estabelecidos, mas os Exames de Estado Mental em risco, devem ser removidos. Auckland deve manter a faixa etária alvo atual. A duração do serviço deve ser aumentada para um mínimo de três anos, com a opção de aumentá-la para cinco anos. A proporção de gestor de cuidados para os doentes deve ser preconizada em 1:15, enquanto o pessoal de apoio não-clínico deve ser aumentado. Os psiquiatras devem ter uma carga de trabalho de cerca de 80 doentes por equivalente de tempo completo. Um serviço local de prestação de cuidados deve ser desenvolvido com, nomeadamente, intervenções culturais para responder às necessidades da população multicultural de Auckland. A capacidade de investigação deve ser incorporada no Serviço de Intervenção Precoce em Psicoses. Qualquer alteração deverá envolver contacto com todas as partes interessadas, e a Administração Regional de Saúde deve comprometer-se em tempo, recursos humanos e políticos para apoiar e facilitar a mudança do sistema, investindo de forma significativa para melhor servir a comunidade Auckland.----------------------------------- ABSTRACT: Auckland has been pioneering in the adoption of Early Intervention in Psychosis models but the design of the service has not changed in 19 years. In service utilisation data from 997 patients seen from 1996 -2012, patients had a median number of 89 contacts (IQR: 36-184), with a median duration of 62 hours of contact (IQR: 24-136). Patients spent a median number of 338 days (IQR: 93-757) in contact with the program. 517 patients (52%) did not require admission to hospital, and those who did spent a median of 124 days in hospital (IQR: 40-380). Asian patients had a 50% increased chance of being admitted to hospital. This report includes 15 recommendations to guide reforms to the service, including outlining the importance of vision and key components. It recommends strengthened managerial leadership and a more integrated team structure with dedicated resources for improved community awareness, education and early detection as well as the capacity to take direct referrals. Key Performance Indicators (KPIs) should be established but At Risk Mental States should be excluded. Auckland should maintain the current target age range. The duration of service should be increased to a minimum of three years, with the option to extend this to five years. The ratio of care co-ordinator to patients should be capped at 1:15 whilst non-clinical supporting staff should be increased. Psychiatrists should have a caseload of about 80 per FTE. A local Service Delivery framework should be developed, as should cultural interventions to meet the needs of the multicultural population of Auckland. Research capacity should be incorporated into the fabric of Early Intervention in Psychosis Services. Any changes should involve consultation with all stakeholders, and the DHB should commit to investing time, human and political resources to support and facilitate meaningful system change to best serve the Auckland community.

Segurança e criminalidade organizada

Globalization brought some deep changes to the world (dis)order. Nowadays, more than in other moment in history, we are closer to the ones physically far, living in “global village” called by Marshall McLuhan (1962). The concepts and premises built in this new order, have totally broken with the ones that “came out from Westphalia”, which had last to the end of the cold war, like, for example, the concept of security. Since then, security has been facing one of its biggest transformations ever, completely disrupting the state border based idea and starting to be extended to other domains, as human, economic, environmental and IT security, among others. In this global and interdependent environment, “new” threats and risks have raised, which are demanding a comprehensive approach from the States, international organizations and other actors, to allow the analysis and understanding its impacts on the various society sectors and orders. Inside the enormous challenges to the global security, it is important to regard the organized crime, which covers, by itself, a set of threats and risks, enhanced by its connection to other types of criminality, such as terrorism. The goals pursued and the tactics used by criminal organizations during the perpetration of illegal activities, specially the drug smuggling, have impact in an wide spectrum of the social, economic financial and politic dimensions, which should not be underestimated, otherwise our own security may be compromised. Therefore, the current investigation intends to be an important catalyst to the idea debate inside security scope, through the analysis of the organized crime and the drug smuggling, adding to a discussion of this issue, which should be deeper and holistic, aiming a better understanding of the challenges provided by our society.

Understanding impact readiness in Portugal’s social sector and designing a framework for capacity-building for social impact

This project is based on the theme of capacity-building in social organisations to improve their impact readiness, which is the predictability of delivering intended outcomes. All organisations which have a social mission, non-profit or for-profit, will be considered to fall within the social sector for the purpose of this work. The thesis will look at (i) what is impact readiness and what are the considerations for building impact readiness in social organisations, (ii) what is the international benchmark in measuring and building impact readiness, (iii) understand the impact readiness of Portuguese social organisations and the supply of capacity building for social impact in Portugal currently, and (iv) provide recommendations on the design of a framework for capacity building for impact readiness adapted to the Portuguese context. This work is of particular relevance to the Social Investment Laboratory, which is a sponsor of this project, in its policy work as part of the Portuguese Social Investment Taskforce (the “Taskforce”). This in turn will inform its contribution to the set-up of Portugal Inovação Social, a wholesaler catalyst entity of social innovation and social investment in the country, launched in early 2015. Whilst the output of this work will be set a recommendations for wider application for capacity-building programmes in Portugal, Portugal Inovação Social will also clearly have a role in coordinating the efforts of market players – foundations, corporations, public sector and social organisations – in implementing these recommendations. In addition, the findings of this report could have relevance to other countries seeking to design capacity building frameworks in their local markets and to any impact-driven organisations with an interest in enhancing the delivery of impact within their work.

Ergonomic evaluation of office workplaces with Rapid Office Strain Assessment (ROSA)

The regular use of the computer in the office contributed to the appearance of many risk factors related with work-related musculoskeletal disorders (WRMSD) such as maintaining static sitting postures for long time and awkward postures of the head, neck and upper limbs, leading to increased muscle activity in the cervical spine and shoulders. The objective of this study was to evaluate the presence of risk factors for WRMSD in an office using the Rapid Assessment Office Strain method (ROSA). Based on the results of this ergonomic evaluation, an occupational gym program was designed and implemented. Thirty-eight workplaces were evaluated using the observation of the tasks and pictures records in order to characterize those tasks in more detail. The ROSA tool was applied by an observer, who selected the appropriate score based on the worker's posture as well as the time spent in each posture. Scores were recorded for the sections of the method, specifically Chair, Monitor and Mouse and Keyboard and Telephone. The scores were recorded in a sheet developed for the method. The mean ROSA final score was 3.61 ± 0.64, for Chair section was 3.45 ± 0.55, to Monitor and Telephone section was 3.11 ± 0.61, and to Mouse and Keyboard section was 2.11 ± 0.31. The results led to understand that the analyzed tasks represent situations of risk of discomfort and, according to the methods guidelines, further research and modifications of the workplace may be necessary. It should be emphasized that these scores may not be related to the poor available equipment but with the need to optimize their use by the workers. It was noticed also that the interaction of workers with the tasks and the adopted sitting posture at the computer throughout the day have effects at a muscular level, essentially for the cervical area and shoulders. ROSA tool is an useful and easy method to assess several risk factors associated with WRMSD, also allowing the design of specific occupational gym programs.

Using the GPU to design complex profile extrusion dies

In the present work the benefits of using graphics processing units (GPU) to aid the design of complex geometry profile extrusion dies, are studied. For that purpose, a3Dfinite volume based code that employs unstructured meshes to solve and couple the continuity, momentum and energy conservation equations governing the fluid flow, together with aconstitutive equation, was used. To evaluate the possibility of reducing the calculation time spent on the numerical calculations, the numerical code was parallelized in the GPU, using asimple programing approach without complex memory manipulations. For verificationpurposes, simulations were performed for three benchmark problems: Poiseuille flow, lid-driven cavity flow and flow around acylinder. Subsequently, the code was used on the design of two real life extrusion dies for the production of a medical catheter and a wood plastic composite decking profile. To evaluate the benefits, the results obtained with the GPU parallelized code were compared, in terms of speedup, with a serial implementation of the same code, that traditionally runs on the central processing unit (CPU). The results obtained show that, even with the simple parallelization approach employed, it was possible to obtain a significant reduction of the computation times.

Development of a new U 200 pultrusion die to produce GRP composite profiles using different thermosetting resins

In this work, a steel heated pultrusion die was designed, developed and manufactured to produce U200 glass fibre reinforced thermosetting matrix (GRP) profiles. The finite element analysis (FEA) was used to predict and optimise the developed die heating by using cylindrical electrical powered cartridges. To assess the new die performance it was mounted in the 120 kN pultrusion line of the Portuguese company Vidropol SA and used to produce continuously U200 profiles able to meet all requirements specified for the E23 grade accordingly to the European Standard EN 13706: 2002. After setting up the type, orientation and sequence of layers in laminate, orthophthalic, isophthalic and bisphenolic unsaturated polyester as well as vinylester resins were used to produce glass fibre reinforced U 200 composite profiles. An appropriated catalyst system was selected and the processing variables optimised for each case, namely, pultrusion pull-speed and die temperature. Finally, the produced U200 profiles were submitted to visual inspection, calcination and mechanical tests, namely, flexural, tensional and interlaminar shear strength (ILSS) tests, to assess their accomplishment with the EN 13706 requirements.

Using a new developed die and different types of thermosetting resins to produce U200 profiles by pultrusion

In this work, a new steel heated pultrusion die was designed, developed and manufactured to produce U200 glass fibre reinforced thermosetting matrix (GRP) profiles. The finite element analysis (FEA) was used to predict and optimise the developed die heating by using cylindrical electrical powered cartridges. To assess the new die performance it was mounted in the 120 kN pultrusion line of the Portuguese company Vidropol SA and used to produce continuously U200 profiles able to meet all requirements specified for the E23 grade accordingly to the European Standard EN 13706: 2002. After setting up the type, orientation and sequence of layers in the U 200 laminate, different types of thermosetting resins were used in its production. Orthophthalic, isophthalic and bisphenolic unsaturated polyester as well as vinylester resins were used to produce glass fibre reinforced U 200 composite profiles. All applied resins were submitted to SPI gel tests in order to select the more appropriated catalyst system and optimise the processing variables to be used in each case, namely, pultrusion pull-speed and die temperature. The best pultrusion operational conditions were selected by varying and monitoring the pull-speed and die temperature and, at the same time, measuring the temperature on the manufactured U 200 profile during processing. Finally, the produced U200 profiles were submitted to visual inspection, calcination and mechanical tests, namely, flexural, tensional and interlaminar shear strength (ILSS) tests, to assess their accomplishment with the EN 13706 requirements.

O "ser português" e o "outro": Revisitar a história de Portugal no diálogo com a civilização chinesa - O caso Tomás Pereira

Tese de Doutoramento em Ciências da Cultura - Especialidade em Culturas do Extremo Oriente

Contribution of the evaluation strategy and the use of hearing protection for the uncertainty associated with occupational exposure to noise

Doctoral Thesis for PhD degree in Industrial and Systems Engineering

Momentos de inovação e mudança na terapia cognitivo comportamental para a bulimia nervosa

Dissertação de mestrado em Psicologia Aplicada

Implementação de ferramentas Lean numa empresa de componentes para calçado

Dissertação de mestrado em Engenharia Industrial