Ferulates and lignin structural composition in cork

The structure of lignin and suberin, and ferulic acid (FA) content in cork from Quercus suber L. were studied. Extractive-free cork (Cork), suberin, desuberized cork (Cork(sap)), and milled-cork lignins (MCL) from Cork and Cork(sap) were isolated. Suberin composition was determined by GC-MS/FID, whereas the polymers structure in Cork, Corksap, and MCL was studied by Py-TMAH and 2D-HSQC-NMR. Suberin contained 94.4% of aliphatics and 3.2% of phenolics, with 90% of omega-hydroxyacids and alpha,omega-diacids. FA represented 2.7% of the suberin monomers, overwhelmingly esterified to the cork matrix. Py-TMAH revealed significant FA amounts in all samples, with about 3% and 6% in cork and cork lignins, respectively. Py-TMAH and 2D-HSQC-NMR demonstrated that cork lignin is a G-lignin (>96% G units), with a structure dominated by beta-O-4' alkyl-aryl ether linkages (80% and 77% of all linkages in MCL and MCLsap, respectively), followed by phenylcoumarans (18% and 20% in MCL and MCLsap, respectively), and smaller amounts of resinols (ca. 2%) and dibenzodioxocins (1%). HSQC also revealed that cork lignin is heavily acylated (ca. 50%) exclusively at the side-chain gamma-position. Ferulates possibly have an important function in the chemical assembly of cork cell walls with a cross-linking role between suberin, lignin and carbohydrates.

Potential pathogenic fungi assessment through molecular biology in cork industry

Portugal has been the world leader in the cork sectr in terms of exports, employing ten thousands of workers. In this working activity, the permanent contact with cork may lead to the exposure to fungi raising concerns as occupational hazards in cork industry. A study was developed aiming at assessing fungal contamination due to Aspergillus fumigatus complex and Penicillium glabrum complex by molecular methods in three cork industries in the outskirt of Lisbon city. The chosen fungal species are the ones most frequently associated with respiratory problems in workers from these industries.

Accessing occupational exposure to fungi in a cork industry

Different forms of fungal diseases affecting the nose and paranasal sinuses are recognized, including invasive and non-invasive fungal rhinosinusitis. Penicillium glabrum complex is associated with respiratory diseases such as suberosis, a typical disease of cork industry workers. In addition, Chrysonilia sitophila has been described as causing occupational asthma, associated to prolonged exposure to high counts of spores. In this study we aimed to access fungal exposure in workers from one cork industry through the mycological analysis of their nasal exudate and the environmental fungal contamination of their surroundings as well.

Design of experiments to optimized the determination of TDIs in agglomerated cork stoppers

Isocyanates are included into a class with an extreme commercial importance because their use in the manufacture of polyurethanes. Polyurethanes are used in several applications such as adhesives, coatings, foams, thermoplastics resins, printing inks, foundry moulds and rubbers. Agglomerated cork stoppers are currently used for still wines, semi-sparkle and gaseous wines, beer and cider. Methylene diphenyl diisocyanate (MDI) is presently the isocyanate used in the production of polyurethane based adhesive in use due to its lowest toxicity comparing with toluene diisocyanate (TDI) previously employed. However, free monomeric TDI or MDI, depending on the based polyurethane, can migrate from agglomerated cork stoppers to beverages therefore it needs to be under control. The presence of these compounds are usually investigated by HPLC with Fluorescence or UV-Vis detector depending on the derivatising agent. Ultra Performance Liquid Chromatography with Diode Array Detector (UPLC-DAD) method is replacing HPLC. The objective of this study is to determine which method is better to analyze isocyanates from agglomerated cork stoppers, essentially TDI to quantify its monomer. A Design of Experiments (DOE) with three factors, column temperature, flow and solvent, at two levels was done. Eight experiments with three replications and two repetitions were developed. Through an ANOVA the significance of the factors was evaluated and the best level’s factors were selected. As the TDI has two isomers and in this method these two isomers were not always separated an ANOVA with results of resolution between peaks was performed. The Design of Experiments reveals to be a suitable statistical tool to determine the best conditions to quantified free isocyanates from agglomerated cork stoppers to real foodstuff. The best level’s factors to maximize area was column temperature at 30ºC, flow to 0,3 mL/min and solvent 0,1% Ammonium Acetate, to maximize resolution was the same except the solvent that was 0,01% Ammonium Acetate.

New approach to study the real exposure to fungi in cork industry: nasal swabs mycobiota investigation coupled with screening on fungal resistance to azoles

The permanent contact with cork may lead to constant exposure to fungi, raising awareness as a potential occupational hazard in the cork industry.The presence of fungi belonging to the Penicillium glabrum complex has been associated with the development of respiratory diseases such as suberosis, one of the most prevalent diseases among workers from cork industries, besides occupational asthma. Azoles are used as pesticides but also the first line therapy in the treatment of Aspergillus infections; azole-resistance as been described as to have also an environmental source and is considered an emerging public health problem.The aim of this work was to characterize fungal distribution and to evaluate the presence of azole-resistant Aspergillus isolates in nose swab samples from the cork industry workers.

Simulating the effects of vegetation and landscape structure on fire behavior in northeastern Portugal: the case of holm oak (Quercus rotundifolia)

O fogo é um processo frequente nas paisagens do norte de Portugal. Estudos anteriores mostraram que os bosques de azinheira (Quercus rotundifolia) persistem após a passagem do fogo e ajudam a diminuir a sua intensidade e taxa de propagação. Os principais objetivos deste estudo foram compreender e modelar o efeito dos bosques de azinheira no comportamento do fogo ao nível da paisagem da bacia superior do rio Sabor, localizado no nordeste de Portugal. O impacto dos bosques de azinheira no comportamento do fogo foi testado em termos de área e configuração de acordo com cenários que simulam a possível distribuição destas unidades de vegetação na paisagem, considerando uma percentagem de ocupação da azinheira de 2.2% (Low), 18.1% (Moderate), 26.0% (High), e 39.8% (Rivers). Estes cenários tiveram como principal objetivo testar 1) o papel dos bosques de azinheira no comportamento do fogo e 2) de que forma a configuração das manchas de azinheira podem ajudar a diminuir a intensidade da linha de fogo e área ardida. Na modelação do comportamento do fogo foi usado o modelo FlamMap para simular a intensidade de linha do fogo e taxa de propagação do fogo com base em modelos de combustível associados a cada ocupação e uso do solo presente na área de estudo, e também com base em fatores topográficos (altitude, declive e orientação da encosta) e climáticos (humidade e velocidade do vento). Foram ainda usados dois modelos de combustível para a ocupação de azinheira (áreas interiores e de bordadura), desenvolvidos com base em dados reais obtidos na região. Usou-se o software FRAGSATS para a análise dos padrões espaciais das classes de intensidade de linha do fogo, usando-se as métricas Class Area (CA), Number of Patches (NP) e Large Patches Index (LPI). Os resultados obtidos indicaram que a intensidade da linha de fogo e a taxa de propagação do fogo variou entre cenários e entre modelos de combustível para o azinhal. A intensidade média da linha de fogo e a taxa média de propagação do fogo decresceu à medida que a percentagem de área de bosques de azinheira aumentou na paisagem. Também foi observado que as métricas CA, NP e LPI variaram entre cenários e modelos de combustível para o azinhal, decrescendo quando a percentagem de área de bosques de azinheira aumentou. Este estudo permitiu concluir que a variação da percentagem de ocupação e configuração espacial dos bosques de azinheira influenciam o comportamento do fogo, reduzindo, em termos médios, a intensidade da linha de fogo e a taxa de propagação, sugerindo que os bosques de azinhal podem ser usados como medidas silvícolas preventivas para diminuir o risco de incêndio nesta região.

Degradation of compounds present in cork boiling water by gamma radiation

Cork boiling water is an aqueous and complex dark liquor with high concentration of phenolic compounds such as phenolic acids and tannins [1, 2], which are considered biorecalcitrants [2]. Ionizing radiation has been widely studied as an alternative technology for the degradation of organic contaminants without the addition of any other (e.g.: Fenton technologies). The aim of this work was to identify the compounds present in cork boiling water and further evaluate the resulting stable degradation products after gamma irradiation. The irradiation experiments of standard solutions were carried out at room temperature using a Co-60 experimental equipment. The applied absorbed doses were 20 and 50 kGy at a dose rate of 1.5 kGy/h, determined by routine dosimeters [3]. The identification of radiolytic products was carried out by HPLC-DAD-ESI/MS. The phenolic compounds were identified by comparing their retention times and UV–vis and mass spectra with those obtained from standard compounds, when available, as well as by comparing the obtained information with available data reported in the literature. Concerning the obtained results and the literature review, the main cork wastewater components are: quinic, gallic, protocatechuic, vanillic, syringic and ellagic acids. Based on this, we used protocatechuic, vanillic and syringic acids as model compounds to study their degradation by gamma radiation in order to identify the corresponding radiolytic products. Standard aqueous solutions were irradiated and the derivatives of each model compound are represented in figure 1. The obtained results seem to demonstrate that the derivatives of the parent compounds could also be phenolic acids, since it was observed the loss of 44 u (CO2) from the [M-H]- ions. Gallic and protocatechuic acids are identified as derivatives of vanillic and syringic acids, and gallic acid as a protocatechuic acid derivative. Compound 5 ([M-H]- at m/z 169) was tentatively identified as 2,4,6-trihydroxybenzoic acid, since its fragmentation pattern (m/z 151, 125 and 107) is similar to that previously reported in literature [4]. The structure of compound 7 was proposed based on the molecular ion and its fragmentation and compound 6 remains unknown.

Cork structural characteristics and their influence on the oxygen ingress through wine stoppers

Doutoramento em Engenharia Florestal e dos Recursos Naturais - Instituto Superior de Agronomia - UL

Equity Research - Cork Supply Portugal

Mestrado em Finanças

Development of the composition of oak wood during seasoning and its impact on wine

Mestrado Vinifera Euromaster - Instituto Superior de Agronomia - UL

GENETIC VARIATION, LOCAL ADAPTATION AND POPULATION STRUCTURE IN NORTH AMERICAN RED OAK SPECIES, QUERCUS RUBRA L. AND Q. ELLIPSOIDALIS E. J. HILL

Forest trees, like oaks, rely on high levels of genetic variation to adapt to varying environmental conditions. Thus, genetic variation and its distribution are important for the long-term survival and adaptability of oak populations. Climate change is projected to lead to increased drought and fire events as well as a northward migration of tree species, including oaks. Additionally, decline in oak regeneration has become increasingly concerning since it may lead to decreased gene flow and increased inbreeding levels. This will in turn lead to lowered levels of genetic diversity, negatively affecting the growth and survival of populations. At the same time, populations at the species’ distribution edge, like those in this study, could possess important stores of genetic diversity and adaptive potential, while also being vulnerable to climatic or anthropogenic changes. A survey of the level and distribution of genetic variation and identification of potentially adaptive genes is needed since adaptive genetic variation is essential for their long-term survival. Oaks possess a remarkable characteristic in that they maintain their species identity and specific environmental adaptations despite their propensity to hybridize. Thus, in the face of interspecific gene flow, some areas of the genome remain differentiated due to selection. This characteristic allows the study of local environmental adaptation through genetic variation analyses. Furthermore, using genic markers with known putative functions makes it possible to link those differentiated markers to potential adaptive traits (e.g., flowering time, drought stress tolerance). Demographic processes like gene flow and genetic drift also play an important role in how genes (including adaptive genes) are maintained or spread. These processes are influenced by disturbances, both natural and anthropogenic. An examination of how genetic variation is geographically distributed can display how these genetic processes and geographical disturbances influence genetic variation patterns. For example, the spatial clustering of closely related trees could promote inbreeding with associated negative effects (inbreeding depression), if gene flow is limited. In turn this can have negative consequences for a species’ ability to adapt to changing environmental conditions. In contrast, interspecific hybridization may also allow the transfer of genes between species that increase their adaptive potential in a changing environment. I have studied the ecologically divergent, interfertile red oaks, Quercus rubra and Q. ellipsoidalis, to identify genes with potential roles in adaptation to abiotic stress through traits such as drought tolerance and flowering time, and to assess the level and distribution of genetic variation. I found evidence for moderate gene flow between the two species and low interspecific genetic differences at most genetic markers (Lind and Gailing 2013). However, the screening of genic markers with potential roles in phenology and drought tolerance led to the identification of a CONSTANS-like (COL) gene, a candidate gene for flowering time and growth. This marker, located in the coding region of the gene, was highly differentiated between the two species in multiple geographical areas, despite interspecific gene flow, and may play a role in reproductive isolation and adaptive divergence between the two species (Lind-Riehl et al. 2014). Since climate change could result in a northward migration of trees species like oaks, this gene could be important in maintaining species identity despite increased contact zones between species (e.g., increased gene flow). Finally I examined differences in spatial genetic structure (SGS) and genetic variation between species and populations subjected to different management strategies and natural disturbances. Diverse management activities combined with various natural disturbances as well as species specific life history traits influenced SGS patterns and inbreeding levels (Lind-Riehl and Gailing submitted).

Comparative analysis of volatile and phenolic composition of alternative wood chips from cherry, acacia and oak for potential use in enology.

The aim of present work was to investigate the phenolic and volatile composition of cherry, acacia, and oak (from different species) wood chips. By the use of HPLC-DAD 18 different phenolic compounds were detected and quantified while for volatile composition, 33 different compounds were detected by GC-MS. In general, wood samples from oak species showed the higher number of phenolic compounds detected, while cherry wood samples showed the lowest levels. In addition, some individual phenolic compounds were detected, specifically in some wood samples, such as robinetin in acacia woods and naringenin in cherry wood. For volatile composition, cherry wood chips samples showed the lowest volatile composition followed by increasing order by acacia, French, Portuguese and American wood chip samples. Oak wood chip samples from American species showed the highest volatile content, as a result of high levels of several specific compounds (furfural, 5-methyfurfural, β-methyl-γ-octalactones, guaiacol, vanillin and siringaldehyde).

Work, class and conflict: a comparative study of three Cork factories, incorporating oral testimony

This dissertation presents a comparative study of three factories in Cork Harbour area, Sunbeam Wolsey (1927-90), Irish Steel (1939-2001) and the Ford Marina Plant (1917-84). All three factories were significant industrial employers in both a domestic (Irish) and a local (Cork) context and are broadly representative of the Irish manufacturing industry that was developed under the policies of tariff protection introduced in the 1930s and gradually phased out between the late 1950s and the mid-1980s. Sunbeam Wolsey was a textile and clothing concern located on the north side of Cork City that possessed a borderline monopoly within its economic sector and was among the largest private employers of female labour in twentieth century Ireland. Irish Steel was the country’s only steel mill, located on Haulbowline island, a brief ferry-ride from the seaside town of Cobh, and was unusual in being one of the few manufacturing concerns operated as a nationalised industry under the auspices of the state. The Ford Marina plant predated the introduction of protectionism by more than a decade and began as the centre of the Ford empire’s tractor manufacturing business, before switching to the production of private motor vehicles for the Irish market in 1932. All three industries were closed or sold off when the state withdrew support, either in the form of tariff protection (Ford, Sunbeam) or direct funding (Irish Steel). While devoting much attention to the three firms, the central concern of this dissertation is not the companies themselves (though the economic history portion of the dissertation is substantial), but the workers they employed, examining the lives of these individuals both as members of the Irish working class, and, more specifically, as employees of the three factories under consideration. The project can be best described as a comparative factory study, comparing and contrasting the three workforces, focusing primarily on industrial relation and the experience of work. This dissertation utilises both documentary evidence and a significant quantity of oral testimony, breaking new ground by making the workplace the central focus of its investigation. The principal aims of the study are: 1. To document the lives of those who worked in these factories, capturing through oral testimony their subjective experiences of social class and factory life, as well as differences among narrators in terms of gender and status. In achieving this aim, the study will provide a broader social context for its detailed analysis of work and industrial relations in each firm. 2. To analyse the three workplaces and determine how and why each developed such distinct systems of industrial relations at the factory level, as well as to compare and contrast these systems. 3. To examine the nature of work in each factory and to determine how work and industrial relations in each firm developed over time, relating these changes both to internal and external factors. Additionally, the project will provide a comparative analysis of these changes.

Rural change south of the river Bride in counties Cork and Waterford: the surveyors' evidence 1716–1851

Estate studies in Irish historical geography have been often designed to confirm or contrast local trends of development with those previously identified at the regional or sub-regional level. To date, little attention has been awarded to estate maps in studies of rural landscape change. It is a theme of this paper that the results yielded from a careful study of such estate maps can throw light on the results of the activities of the majority of estate residents. In this regard, it is fortunate that at Lismore surveys of the estate in 1716–17 and 1773–4 have survived, and a nineteenth century dimension is added by an analysis of the Valuation Office maps for 1851. This work is focused on a study of critical indicators of change, notably leasing arrangements, farm size, rate and type of enclosure, infrastructural development and settlement growth. These changes are reviewed within the framework of the dialectic that developed between landlord or landlord-inspired management policies and the forces released locally by the vast bulk of the population. Broadly this analysis indicates some of the potential rewards which may be secured by detailed scrutiny of estate maps in conjunction with other estate records.