Full-scale biological phosphorus removal: quantification of storage polymers, microbial performance and metabolic modelling

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

While the crisis proceeds: A world redistribution of economic power?

The crisis has drawn attention to the fact that not only emerging powers but other regions of the world as well may be offering different development models and may constitute into alternative, in some dimensions more positive agents, in the conduct of the present stage of globalisation. Notwithstanding, the traditional western powers have not lost a large amount of control of the world economy. And the crisis proceeds, reallocating world power as in a Hobbesian anarchy. It is difficult to foresee smooth developments in the near future. On the contrary, multilateralism seems to be losing ground to unilateral action or bilateral arrangements. More or less disguised currency wars may lead to serious disequilibria, and turf wars may become more frequent, with motives ranging from securing captive markets to control of specific commodities and energy goods, or targeted regulatory frameworks. As economic policy becomes even more involved with defence and security affairs, the feedbacks from each side to the other seem likely to keep dissent and animosity high, rather than contributing to peaceful and constructive approaches. A more trouble-prone world may be easily expected.

Understanding the microbial ecology and ecophysiology of enhanced biological phosphorus removal processes through metabolic modelling and experimental studies

Dissertation to obtain the degree of Master in Chemical and Biochemical Engineering

Malnutrição em idosos na admissão hospital actuação perante a sua elevado prevalência

RESUMO: Ao longo das últimas décadas a redistribuição etária da população mundial tem vindo a apresentar um aumento do número de pessoas com 65 ou mais anos, integrando um grupo populacional comummente designado por população idosa. Importa aprofundar mecanismos fisiológicos que conduzem ao envelhecimento e de que forma podem condicionar não só aspetos clínicos, como também nutricionais, entre outros, com a perspetiva da sua origem no aparecimento de doenças crónicas. Com esse enfoque, a desnutrição na pessoa idosa é hoje considerada pela European Nutrition for Health Alliance(ENHA) um problema de saúde pública. Está descrito que a sua prevalência ronda os 60% a nível de instituições hospitalares, 40% em unidades residenciais e 5 a 10% na pessoa idosa a residir em domicílio próprio ou de familiares, e na sua maioria permanece por diagnosticar e tratar. Assim, foi objetivo deste estudo caracterizar e estimar a prevalência da desnutrição e do risco de desnutrição na pessoa idosa, nas primeiras 72 horas de admissão hospitalar. Aplicou-se um estudo observacional, analítico, transversal, quantitativo e correlacional, cujos dados foram recolhidos por entrevista ao próprio e por observação. O estudo desenvolveu-se em duas vertentes de investigação, uma focada na caracterização da desnutrição em pessoas idosas institucionalizadas em hospitais portugueses da zona centro e sul do Continente e Madeira, nos períodos de julho/agosto de 2009, abril/junho de 2010, maio/julho de 2011, através do MNA®. A outra, uma avaliação nutricional detalhada, efetuada no Centro Hospitalar de Lisboa Central – Hospital de Santa Marta, EPE, entre o início de janeiro de 2009 e o fim de janeiro de 2010, sendo a amostra recrutada de entre os idosos de ambos os sexos, internados. Foram estudados dados sociodemográficos, de saúde e feita uma avaliação nutricional extensa. A avaliação nutricional constou de colheita de parâmetros laboratoriais (hematológicos e bioquímicos) e antropométricos (índice de massa corporal (IMC), prega cutânea tricipital(PCT), prega cutânea subescapular (PCSE), perímetro braquial (PB), adequação do perímetro braquial (APB), área muscular braquial (AMB) e perímetro Geminal (PG), análise da composição corporal (Massa Gorda Corporal (MGC), Massa Isenta de Gordura (MIG)),caracterização de um dia alimentar tipo e questionário Mini Nutritional Assessment Long Form®– MNA LF®. Dos dados obtidos em hospitais portugueses, destaca-se que dos 402 idosos avaliados, 53% eram do sexo masculino, tinham uma idade média de 75,8 + 6,52 (65 – 100) e segundo o MNA® 57,5% encontravam-se Desnutridos ou em Risco de Desnutrição.Na amostra, dos dados obtidos, a nível sociodemográfico salienta-se que 50% dos doentes eram do sexo masculino, a idade média rondava os 75,5 + 7,22 (65 – 100) anos, 55% eram naturais de Lisboa e 80% residiam em Lisboa e Vale do Tejo, 38% não tiveram estudos formais e 43% fizeram-no apenas até ao 4º ano de escolaridade. Em relação aos dados de saúde, a maioria dos doentes foi admitida através do Serviço de Urgência do Centro Hospitalar de Lisboa Central – Hospital de São José e foram internados no Serviço de Medicina (38%) e no Serviço de Cardiologia (30%), por patologia médica (38%) e patologia do sistema circulatório (56%). Nos hábitos de vida, quanto à mobilidade, um terço dos doentes estavam acamados e os restantes deambulavam ou tinham uma mobilidade normal, 74% não apresentaram hábitos etanólicos regulares, 19% apresentavam um consumo elevado (> 30g de etanol/dia); 95% dos doentes não apresentavam hábitos tabágicos. Relativamente à caracterização nutricional, os valores médios encontrados em relação aos parâmetros laboratoriais revelaram-se inferiores aos valores padrão para a idade e sexo e eram inferiores no sexo feminino. Na caracterização antropométrica verificaram-se os seguintes achados: o cálculo do IMC mostrou-se pouco sensível na identificação de doentes desnutridos; a PCT e a PCSE revelaram valores de massa gorda dentro do intervalo considerado normal;segundo o PB, 88% não apresentavam valor indicativo de desnutrição e 8% estavam desnutridos; a APB identificou 50% de doentes desnutridos; a AMB, revelou que 97% dos homens e 95% das mulheres apresentavam deficit da massa magra e segundo o PG, 18% apresentavam um valor inferior a 31cm descritor de desnutrição. Na análise da composição corporal verificou-se que ambos os sexos apresentavam uma percentagem de MGC classificada como demasiado alta e que esta era superior nas mulheres em relação aos homens. Ao analisar a ingestão nutricional verificou-se que esta era inferior às Dietary Reference Intakes (DRIs) para a ingestão hídrica (p=0,00), energética (p=0,00), proteica (p=0,00), lipídica (p=0,01), MUFA (p=0,00), PUFA (p=0,00), e glícidos (p=0,00), fibra (p=0,02), potássio (p=0,00), cálcio (p=0,00), magnésio (p=0,00), fósforo (p=0,00), zinco (p=0,00), vitamina D (p=0,00), vitamina E (p=0,00) e folato (p=0,00). No que diz respeito ao MNA®, a sua aplicação permitiu identificar 62% de situações de risco nutricional ou de desnutrição já instalada. Valores de MNA® indicativos de desnutrição ou risco estavam associados a níveis de escolaridade mais baixos (r=0,32; p=0,00). Verificou-se correlação entre o MNA® e a PCT (r=0,30;p=0,00), PCSE (r=0,19;p=0,03) e PG (r=0,27;p=0,00). Na análise da amostra por sexo e escalão etário, apenas se distinguiram as mulheres mais velhas, que apresentaram situação de IMC indicador de risco de desnutrição (IMC <23,5 + 2,9, (r=0,42;p=0,02)), e de valores médios de PB de 25,6+3,84cm (r=0,42;p=0,01), em situações de menor mobilidade caraterizados pelo MNA®. Os homens maisvelhos apresentaram correlação entre o MNA® e PCSE (r=0,41;p=0,02), APMB (r=0,57;p=0,00)e PG (r=0,55;p=0,00), e as mulheres mais velhas apenas com a PCT (r=0,39;p=0,02). A análise multivariada do MNA® em função do sexo e do escalão etário, revelou que estes são independentes. Os homens apresentaram valores médios de MNA® superiores às mulheres e à medida que a idade aumenta, os valores de MNA® em ambos os sexos diminuem, sendo indicativos de risco de desnutrição. Consideramos que, tendo em conta a natureza e objetivos do presente estudo, foi possível caracterizar e estimar a prevalência da desnutrição e do risco de desnutrição em pessoas idosas nas primeiras 72 horas de admissão hospitalar. Os resultados obtidos sinalizam a sua elevada prevalência e alertam para a necessidade de procedimentos protocolados de avaliação e intervenção nutricional da população idosa na admissão hospitalar. Para este efeito a aplicação do MNA® provou a sua aplicabilidade, assim como a medição e cálculo da AMB, que poderão ser muito precocemente aplicados e contribuir para potenciar melhorias do estado de saúde e diminuir o tempo de internamento, nomeadamente de pessoas idosas. Em relação ao padrão alimentar, este estudo contribuiu para uma chamada de atenção dos profissionais de saúde que a população idosa pode apresentar carências nutricionais na admissão, e que estas se não forem devidamente sinalizadas e colmatadas tendem a agravar-se durante o internamento podendo contribuir para o aumento da morbilidade.-------------ABSTRACT:Over the last decades the age redistribution group of the population worldwide has been presenting an increasing number of people aged 65 years or more, incorporating a population group commonly referred to as the elderly population. It´s important to further analyze the physiological mechanisms that lead to aging and how they might influence not only clinical aspects, but also nutritional, among others, with the perspective of their origin in the onset of chronic diseases. With this approach, malnutrition in the elderly is now considered by the European Nutrition for Health Alliance (ENHA) a public health problem. It is reported that its prevalence is around 60% at the level of hospital units, 40% in residential units and 5 to 10% in the elderly living in their own home or family's, and mostly remains to diagnose and treat. The aim of this study was to characterize and estimate the prevalence of malnutrition and risk of malnutrition in the elderly, in the first 72 hours of hospital admission. We applied an observational, analytical, cross-sectional and correlacional quantitative type of study and data were collected by interview and observation itself. The study was developed in two lines of research: one focused on the characterization of malnutrition in elderly institutionalized in Portuguese hospitals, in the central and southern mainland and Madeira, in the periods between July - August 2009, April - June 2010, May - July 2011, through the MNA®; and the other: a detailed nutritional assessment, conducted in Hospital Lisbon Center - Hospital de Santa Marta, EPE, between early January 2009 and late January 2010, and the sample was recruited from among the elderly of both sexes at hospital admission. We studied intensively sociodemographic, health and nutritional assessment done extensive. Nutritional evaluation consisted of harvesting different parameters: hematological, biochemical and anthropometric (body mass index (BMI), triceps skinfold (TSF), sub-scapular skinfold (SSF), arm circumference (AC), arm muscle area (AMA), geminal perimeter (GP), analysis of body composition (Fat Mass (FM), Fat Free Mass (FFM)), characterization of a daily food type and Mini Nutritional Assessment Long Form® questionnaire - MNA LF®. Form the data obtained in Portuguese hospitals, it is noteworthy that of the 402 patients included, 53% were male, had a mean age of 75,8 + 6,52 (65 - 100) and, according to the MNA®, 57,5% were malnourished or at risk of malnutrition. In the sample, from the sociodemographic data obtained, we saw that 50% of patients were male, the average age was around 75,5 + 7,22 years (65-100), 55% were from Lisbon and 80 %lived in Lisbon, 38% had no formal education and 43% did so only until the 4th grade. Regarding health data, the majorities of patients were admitted through the ER of Hospital Lisbon Center - S. José Hospital - and were admitted to the Medicine Unit (38%) and to the Cardiology Unit (30%), by medical pathology (38%) and circulatory system disease (56%). In regard to lifestyle, and considering mobility, one third of patients were bedridden and the rest were ambulating or had a normal mobility. 74% had no regular ethanol habits, 19% had a high intake (> 30 g ethanol / day); 95% of the patients had no smoking habits. Regarding nutritional assessment, the mean values for laboratory parameters proved inferior to standard values for age and sex and were lower in females. In anthropometric assessment these were the findings: BMI calculation showed to be scarcely sensitive in the identification of undernourished patients; the TSF and SSF revealed values of fat mass within the normal range; in AC, 88% did not have an indicative value of malnutrition and 8% were malnourished; in AMA, 97% of men and 95% women had a deficit of lean mass and in GP, 18% had a value of less than the 31cm malnutrition descriptor. In body composition analysis found that both sexes showed a percentage of FM ranked too high and this was higher in women compared to men. By analyzing the nutritional intake was found that this was less than the Dietary Reference Intakes (DRIs) for water intake (p=0,00), energy (p=0,00), protein (p=0,00), lipid (p=0,01), MUFA (p=0,00), PUFA (p=0,00), carbohydrates (p=0,00), fiber (p=0,02), potassium (p=0,00), calcium (p=0,00), magnesium (p=0,00), phosphorus (p=0,00), zinc (p=0,00), vitamin D (p=0,00), vitamin E (p=0,00) and folate (p=0,00). Regarding MNA®, its application identified 62% of cases of nutritional risk or malnutrition already installed. MNA® values indicative of malnutrition or risk were associated with lower levels of education (r=0,32; p=0,00). There was a correlation between the MNA ® and TSF (r =0,30, p = 0,00), SFF (r = 0,19, p = 0,03) and GP (r=0,27, p = 0,00). In the analysis of the sample by gender and age group, the highlight was in older women who had BMI status indicator of malnutrition risk (BMI <23,5 + 2,9 (r=0,42;p=0,02)) and mean values of AC 25,6 +3,84cm (r=0,42; p=0,01), in situations characterized by low mobility MNA®. Older men showed a correlation between the MNA® and SFF (r = 0,41; p = 0,02), AMA (r = 0,57; p = 0,00) and GP (r=0,55;p=0,00), and in older women only TSF showed a correlation(r = 0,39; p =0,02). Multivariate analysis of the MNA® by gender and age group, revealed that they are independent. The men had MNA® mean superior to women, and as the age increases, the values of MNA® in both sexes declined, being indicative of risk of malnutrition. We believe that, given the nature and objectives of the present study, it allowed us to characterize and estimate the prevalence of risk of malnutrition and malnutrition in older people during the first 72 hours of hospital admission. The results indicate a high prevalence and point to the need for protocol procedures of nutritional assessment and intervention in the elderly population at hospital admission. For this purpose the application of MNA® has proved its applicability, as well as measuring and calculating AMA, which may be applied in early stages thus contributing to enhance health state improvements and to shorten the time of hospitalization, particularly in elderly people. In relation to dietary pattern, this study contributed to call of attention from health professionals that the elderly may have nutritional deficiencies on admission, and that these are not properly marked and addressed tend to worsen during hospitalization may contribute to increased morbidity.

The effect of key process operational conditions on enhanced biological phosphorus removal from wastewater

Enhanced biological phosphorus removal (EBPR) is the most economic and sustainable option used in wastewater treatment plants (WWTPs) for phosphorus removal. In this process it is important to control the competition between polyphosphate accumulating organisms (PAOs) and glycogen accumulating organisms (GAOs), since EBPR deterioration or failure can be related with the proliferation of GAOs over PAOs. This thesis is focused on the effect of operational conditions (volatile fatty acid (VFA) composition, dissolved oxygen (DO) concentration and organic carbon loading) on PAO and GAO metabolism. The knowledge about the effect of these operational conditions on EBPR metabolism is very important, since they represent key factors that impact WWTPs performance and sustainability. Substrate competition between the anaerobic uptake of acetate and propionate (the main VFAs present in WWTPs) was shown in this work to be a relevant factor affecting PAO metabolism, and a metabolic model was developed that successfully describes this effect. Interestingly, the aerobic metabolism of PAOs was not affected by different VFA compositions, since the aerobic kinetic parameters for phosphorus uptake, polyhydroxyalkanoates (PHAs) degradation and glycogen production were relatively independent of acetate or propionate concentration. This is very relevant for WWTPs, since it will simplify the calibration procedure for metabolic models, facilitating their use for full-scale systems. The DO concentration and aerobic hydraulic retention time (HRT) affected the PAO-GAO competition, where low DO levels or lower aerobic HRT was more favourable for PAOs than GAOs. Indeed, the oxygen affinity coefficient was significantly higher for GAOs than PAOs, showing that PAOs were far superior at scavenging for the often limited oxygen levels in WWTPs. The operation of WWTPs with low aeration is of high importance for full-scale systems, since it decreases the energetic costs and can potentially improve WWTP sustainability. Extended periods of low organic carbon load, which are the most common conditions that exist in full-scale WWTPs, also had an impact on PAO and GAO activity. GAOs exhibited a substantially higher biomass decay rate as compared to PAOs under these conditions, which revealed a higher survival capacity for PAOs, representing an advantage for PAOs in EBPR processes. This superior survival capacity of PAOs under conditions more closely resembling a full-scale environment was linked with their ability to maintain a residual level of PHA reserves for longer than GAOs, providing them with an effective energy source for aerobic maintenance processes. Overall, this work shows that each of these key operational conditions play an important role in the PAO-GAO competition and should be considered in WWTP models in order to improve EBPR processes.

Optimization of the electrodialytic phosphorus recovery from sewage sludge ash

Phosphorus (P) is becoming a scarce element due to the decreasing availability of primary sources. Therefore, recover P from secondary sources, e.g. waste streams, have become extremely important. Sewage sludge ash (SSA) is a reliable secondary source of P. The use of SSAs as a direct fertilizer has very restricted legislation due to the presence of inorganic contaminants. Furthermore, the P present in SSAs is not in a plant-available form. The electrodialytic (ED) process is one of the methods under development to recover P and simultaneously remove heavy metals. The present work aimed to optimize the P recovery through a 2 compartment electrodialytic cell. The research was divided in three independent phases. In the first phase, ED experiments were carried out for two SSAs from different seasons, varying the duration of the ED process (2, 4, 6 and 9 days). During the ED treatment the SSA was suspended in distilled water in the anolyte, which was separated from the catholyte by a cation exchange membrane. From both ashes 90% of P was successfully extracted after 6 days of treatment. Regarding the heavy metals removal, one of the SSAs had a better removal than the other. Therefore, it was possible to conclude that SSAs from different seasons can be submitted to ED process under the same parameters. In the second phase, the two SSAs were exposed to humidity and air prior to ED, in order to carbonate them. Although this procedure was not successful, ED experiments were carried out varying the duration of the treatment (2 and 6 days) and the period of air exposure that SSAs were submitted to (7, 14 and 30 days). After 6 days of treatment and 30 days of air exposure, 90% of phosphorus was successfully extracted from both ashes. No differences were identified between carbonated and non-carbonated SSAs. Thus, SSAs that were exposed to the air and humidity, e.g. SSAs stored for 30 days in an open deposit, can be treated under the same parameters as the SSAs directly collected from the incineration process. In the third phase, ED experiments were carried out during 6 days varying the stirring time (0, 1, 2 and 4 h/day) in order to investigate if energy can be saved on the stirring process. After 6 days of treatment and 4 h/day stirring, 80% and 90% of P was successfully extracted from SSA-A and SSA-B, respectively. This value is very similar to the one obtained for 6 days of treatment stirring 24 h/day.

Electrokinetic treatment of environmental matrices. Contaminants removal and phosphorus recovery

There is a need to develop viable techniques for removal and recovery organic and inorganic compounds from environmental matrices, due to their ecotoxicity, regulatory obligations or potential supplies as secondary materials. In this dissertation, electro –removal and –recovery techniques were applied to five different contaminated environmental matrices aiming phosphorus (P) recovery and/or contaminants removal. In a first phase, the electrokinetic process (EK) was carried out in soils for (i) metalloids and (ii) organic contaminants (OCs) removal. In the case of As and Sb mine contaminated soil, the EK process was additionally coupled with phytotechnologies. In a second phase, the electrodialytic process (ED) was applied to wastes aiming P recovery and simultaneous removal of (iii) toxins from membrane concentrate, (iv) heavy metals from sewage sludge ash (SSA), and (v) OCs from sewage sludge (SS). EK enhanced phytoremediation showed to be viable for the remediation of soils contaminated with metalloids, as although remediation was low, it combines advantages of both technologies while allowing site management. EK also proved to be an effective remediation technology for the removal and degradation of emerging OCs from two types of soil. Aiming P recovery and contaminants removal, different ED cell set-ups were tested. For the membrane concentrates, the best P recovery was achieved in a three compartment (3c) cell, but the highest toxin removal was obtained in a two compartment (2c) cell, placing the matrix in the cathode end. In the case of SSA the best approach for simultaneous P recovery and heavy metals removal was to use a 2c-cell placing the matrix in the anode end. However, for simultaneous P recovery and OCs removal, SS should be placed in the cathode end, in a 2c-cell. Overall, the data support that the selection of the cell design should be done case-by-case.

Electrodialytic recovery of phosphorus and organic contaminants removal from sewage sludge

Phosphorus is a macronutrient essential to life which comes from phosphate rock, a non-renewable resource. Sewage sludge from wastewater treatment plants (WWTP) is a secondary resource rich in phosphorus that can be valorized. However, organic compounds are detected in sewage sludge, due to its non-polar and hydrophobic character, being considered an environmental risk. The present dissertation aims to study the efficiency of the electrodialytic process (ED) when applied to sewage sludge aiming phosphorus recovery and organic contaminants removal. Four organic compounds were analyzed: 17α-ethynylestradiol (EE2), bisphenol A (BPA), caffeine (Caf) and oxybenzone (MBPh). The experiments took place in an ED cell with two compartments and an anion exchange membrane, with the sludge in the cathode compartment. The experiments were carried out for three days with spiked sewage sludge (six assays). One control experiment was done without current, three experiments were carried out applying a constant current of 50, 75, and 100 mA and two experiments were carried out applying sequential currents: 50 mA, 75 mA and 100 mA and the opposite (100-75-50 mA). A qualitative and quantitative analysis of microorganisms existing in the samples was also done. At the end, the pH increased in the sewage sludge favoring phosphorus recovery. In terms of phosphorus, the highest recovery was achieved in the experiment run with 100 mA, where 70.3±2.0% of total phosphorus was recovered in the electrolyte. Generally, compounds degradation was favored by the current. Caf and MBPh achieved degradation percentages of 96.2±0.2% and 84.8±1.3%, respectively, in 100 mA assay. EE2 (83.1±1.7%) and BPA (91.8±4.6%) degradations were favored by 50 mA current. A total of 35 taxa from four different groups were identified, totalizing between 81,600-273,000 individuals per gram of initial sludges. After ED, microbial community population decreased between 47-98%. Arcella gibbosa represented 61% of the total observed organisms and revealed to be more tolerant to medium changes.