Rozprawy doktorskie na temat „Chemical and physicochemical properties of groundwater”

Microfibrillated cellulose (MFC) films have gained a lot of industrial interest lately dueto their good barrier properties and good mechanical strength. In this study it wasinvestigated whether rheological characteristics and conductivity of MFC dispersionscomprised of different MFC grades could be correlated to tensile properties of the MFCfilms produced from the corresponding MFC dispersion. A rheological characterizationmethod was developed for MFC dispersions with 3 wt% MFC and a secret additiveusing a dynamic rotational rheometer and a smooth “plate to plate” geometry. Themethod consisted of an amplitude sweep, a frequency sweep, and a controlled shearrate measurement. Two predicting OPLS models were created in SIMCA: model 1correlated values from rheological measurements and ionic conductivity to tensileproperties and model 2 correlated MFC grades to tensile properties. A slight correlationbetween MFC rheology and tensile properties could be observed, but due to the lowpredictive ability of model 1 (Q2=0.47) it was deemed that the model was insufficientas a tool for facilitated predictions of new samples. It was concluded that tensileproperties are more correlated to the composition of MFC dispersions than whatrheological characteristics and ionic conductivity the dispersions display, based on thegood predictive ability of model 2 (Q2=0.59).

Proteins play a major role in living systems and present a wide spectrum of functionalities. Many different types of proteins are involved into biological processes, such as the catalysis of biochemical reactions, cellular membrane transport, immune system response and DNA replication. However, some proteins and peptides might become harmful to living organisms; for example, their abnormal aggregation causes neurodegenerative disorders including Alzheimer disease (AD). One of the causes of AD is the presence of amyloid beta peptides Aβ(1-42), Aβ(1-40), which self-assemble into insoluble fibrils and plaques, which surround neuronal cells impeding synapsis. The number of AD patients is increasing, but a cure has not been founded yet. Therefore, it is crucial to investigate the mechanisms underlying amyloid aggregation and screening for compounds able to prevent this irreversible process. Microfluidics permits characterising the physicochemical properties of proteins, investigate their aggregation and study their interactions with other molecules. Chemical kinetics allows studying the microscopic events occurring during protein self-assembly. The combination of these two techniques provides a powerful tool for the identification of compounds inhibiting the aggregation process. In this thesis by using microfluidics, chemical kinetics and other biophysical assays, I have investigated the proteins isoelectric point (pI) and the inhibition of aberrant Aβ(1-42) self-assembly process. Firstly, I describe the development of a microfluidic platform allowing for the measurement of the protein pI, in a gradient-free manner. This approach overcomes a fundamental limitation of convectional techniques that is the achievement of a stable and well-controlled pH gradient. Secondly, I investigate the inhibiting effect of llama nanobodies on Aβ(1-42) aggregation. The findings from this study show that nanobodies target monomeric species with high affinity whereas interactions with fibril surfaces are weak. Finally, I discuss the use of other compounds inhibiting specific nucleation stages. These include the chaperones clusterin and brichos, as well as soot and pure carbon nanoparticles. Importantly, the addition of both chaperones to Aβ(1-42) solutions has an additive inhibitory effect on aggregation. My findings will improve the characterization of the physicochemical properties of proteins as well as providing promising candidates for the inhibition of specific stages of amyloid beta aggregation opening the way to possible cures for AD disease.

Doctor of Philosophy
Department of Grain Science and Industry
Xiuzhi Susan Sun
Soy protein is one of the most promising bio-degradable adhesives, with great potential as alternatives synthetic petroleum based adhesives for wood composite industries. However, its intrinsic drawbacks such as low water resistance, high viscosity, and short shelf life still limit its broad application. In this research, soy protein was further modified and characterized to improve adhesion properties, flow-ability, water resistance, and long shelf life, which could facilitate the industrialization of soy protein based adhesives. In this study, we exploited the in situ sodium bisulfite (NaHSO3) modification on soy protein in soy flour-water extracts, and then the modified soy protein was obtained through acid precipitation. First, different concentrations of NaHSO3 were used to modify soy flour slurry, then glycinin-rich and β-conglycinin-rich fractions were precipitated at pH 5.4 (SP 5.4) and pH 4.5 (SP 4.5), respectively. Unmodified sample SP 5.4 and SP 4.5 showed clay-like properties and viscoelastic properties, respectively; whereas with addition of NaHSO3 in range of 2-8 g/L, both SP 5.4 and SP 4.5 had the viscous cohesive phase with good handability and flow-ability. The overall adhesion performance of SP 4.5 was better than SP 5.4; the wet strength of these two fractions was in the range of 2.5-3.2 MPa compared to 1.6 MPa of control soy protein isolate. Then soy protein with various β-conglycinin/glycinin (7S/11S) ratios were extracted from soy flour slurry and characterized for adhesion properties based on the different solubility of 7S and 11S globulins. Seven glycinin-rich soy protein fractions and six β- conglycinin-rich soy protein fractions were obtained. According to the morphology, viscosity, and particle size results, we proposed that proper protein-protein interaction, hydration capacity (glycinin-rich fractions), and certain 7S/11S ratios (β-conglycinin-rich fractions) in modified soy protein are crucial to continuous protein phase formation. The viscous cohesive samples were stable for up to several months without phase separation at room temperature, with the wet adhesion strength of 2.0-2.8 MPa. The soy protein modified with NaHSO3 showed good compatibility with commercial glues applied on plywood and paper labeling fields. The modified soy protein made some functional groups, carboxylic (-COOH), hydroxyl (-OH) and amino groups (-NH2) available, which cross-linked with hydroxymethyl groups (-CH2-OH) from urea formaldehyde (UF) wood glue. The modified soy protein (MSP) with pH 4.8 also acted as an acidic catalyst for the self-polymerization of UF based resin. The wet adhesion strength of MSP/UF blends (40/60) was 6.4 MPa with 100% wood cohesive failure, as compared to 4.66 MPa of UF. As to the paper labeling application, peel strength of MSP on glass substrate increased rapidly, with curing time much shorter than commercial polyvinyl acetate based adhesives (PVAc). And the MSP/ PVAc blends showed shorter curing time, higher water resistance and lower viscosity than pure PVAc. Chemical modification could also enhance the adhesion strength of MSP. 2-octen-1- ylsuccinic anhydride (OSA) was proved to be grafted on soy protein through reaction between amine, hydroxyl groups of protein and anhydride groups. The oily nature and hydrophobic long alkyl chains of OSA mainly contributed to the significant water resistance improvement of MSP.

Kyoto University (京都大学)
0048
新制・論文博士
博士(農学)
乙第11587号
論農博第2547号
新制||農||903(附属図書館)
学位論文||H17||N3991(農学部図書室)
22886
UT51-2004-U484
(主査)教授 井上 國世, 教授 安達 修二, 教授 伏木 亨
学位規則第4条第2項該当

In this study SBA-15 mesoporous silica template was synthesized and used as a sacrificial template in the preparation of ordered mesoporous carbon material. A chemical vapour deposition (CVD) technique using LPG or alternatively sucrose, pyrolyzed upon a mesoporous Si matrix were used to produce nanostructured ordered mesoporous carbon (OMC) with graphitic character after removing the Si template. The sucrose method was found to be a suitable route for preparing OMC. The OMC was used as a conductive three dimensional porous support for depositing catalytic nanophase Pt metal. Deposition of Pt nanoparticles on OMC was accomplished using a CVD method with Pt(acac)2 as a precursor. The synthesized nano-composite materials were characterized by several techniques such as, HRTEM, HRSEM, EDS, XRD, BET, TGA, FT-IR and CV.

The physicochemical properties and chemical reactivity of dissolved organic matter (DOM) are of tremendous practical significance in both natural and engineered aquatic and terrestrial systems. DOM is frequently extracted, fractionated, and concentrated from environmental samples using a variety of operationally defined physical and chemical processes in order to facilitate study of specific physicochemical properties and aspects of its chemical reactivity. This study was conducted to systematically examine the influence of operationally defined physical and chemical characterization methods on observed DOM physicochemical properties and reactivity with aqueous chlorine. The effects of chemical separation were evaluated by applying an existing resin adsorption based procedure which simultaneously extracts and fractionates DOM and inorganic constituents into hydrophobic and hydrophilic acid, base, and neutral dissolved material matrix (DMM) fractions. Physical separation based on DOM apparent molecular weight (AMW) was also evaluated using batch ultrafiltration (UF) data in conjunction with a suitable membrane permeation model. Linear independence of membrane solute transport was theoretically described using non-equilibrium thermodynamics and experimentally demonstrated for AMICON® YC/YM series UF membranes. Mass balances on DMM fraction constituents in untreated and previously coagulated natural waters indicated that quantitative recovery (100 ± 2%) of DOM constituents was achieved, while recovery of inorganic constituents such as iron and aluminum was substantially incomplete (30%-74%). Comparison of whole-water DOM properties with those mathematically reconstituted from DMM fractions demonstrated a marked shift in DOM properties toward lower AMW. Evidence of pH induced partial hydrolysis of protein, polysaccharide, and ester DOM components was also observed. Decreased specific Cl2 demand (mmol DCl2/ mmol DOM) and specific trihalomethane formation (mmol THM/mmol DOM) following chemical fractionation were attributed to increased molar DOM concentration and decreased DOM association with colloidal iron oxide surfaces. Collectively, the results of this research indicate that operational characterization methods result in alteration of DOM physicochemical properties and reactivity with aqueous chlorine, and caution is therefore advisable when interpreting the results of studies conducted using chemically extracted or fractionated DOM.
Ph. D.

Biochar is a product of biomass pyrolysis, by which bioenergy is produced. It has been suggested that biochar can be used as a soil amendment agent to improve soil physical (e.g. particle size distribution, bulk density and water retention), chemical (e.g. pH and cation exchange capacity) and biological (e.g. microbial community and enzyme activities) properties. Biochar can also increase soil carbon (C) inventory as a means of carbon storage and nitrogen (N) retention, improve plant growth, and reduce greenhouse gas emissions. Meanwhile, nitrous oxide (N2O) is a potent greenhouse gas with ca. 310 times that of carbon dioxide (CO2) and also a serious ozone depleting compound, contributing greatly to the global warming. To meet the challenges associated with climate change, greenhouse gas (particularly, N2O) emissions have to be reduced. Hence, studies on how biochar incorporation into soil affects N2O emission are of great significance. An increasing number of studies have shown that biochar amendment decreased the soil N2O emissions, while some other studies indicated no change or an increase in the N2O emission in biochar-amended soils. Various physical, chemical and molecular mechanisms have been proposed to describe the processes responsible for soil N2O emission, such as reduced N availability, decreased abundance of some denitrifying genes, accelerated the electron transfer to facilitate the last step of denitrification (N2O to N2), and increased adsorption of N2O. However, little direct evidence has been presented to support these mechanisms as biochar effect varies with soil type, biochar type (feedstock, pyrolysis temperature), plant species as well as environmental conditions.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
Griffith School of Environment
Science, Environment, Engineering and Technology
Full Text

Introduction: The aim of this study was to evaluate some of the physico-chemical properties of a new root canal sealer. Methodology: The sealers tested were Sealer Plus (MKLife, Porto Alegre, Rio Grande do Sul, Brazil), compared as AH Plus (Dentsply, DeTrey GmbH, Konstanz, Alemanha). For the radiopacity, flow, solubility and fabrication of test specimens relative to setting times the ANSI/ADA No. 57 (2000) and ISO 6876 (2012) specifications were followed. To measure the initial and final setting times the ASTM C266/2008 standard was used. pH was evaluated in the time intervals of 3, 24, 72 and 168 hours). Statistical tests were applied to the results obtained at a level of significance of 5%. Results: The results demonstrated that the Sealer Plus sealer showed a lower radiopacity value than AH Plus sealer (p<0.05), however, this was higher than the minimum value recommended by the specifications; that is 3 mm Al. Relative to flow, the value for Sealer Plus was 19.19 mm and for AH Plus, 19.81 mm (p>0.05). Sealer plus presented initial and final setting times of 138 min. and 210 min., respectively, while the values for AH Plus were 437 min. and 849 min., respectively, (p<0.05). Relative to solubility, Sealer Plus presented 0.21% and AH Plus, 0.27% (p>0.05). None of the sealers showed a significant increase in pH (p>0.05). Conclusion: Sealer Plus sealer presented physico-chemical properties in accordance with ANSI/ADA (2000) No.57 and ISO 6876 (2012) specifications.
Introdução: Este estudo objetivou avaliar algumas propriedades físico-químicas de um novo cimento obturador de canais radiculares. Metodologia: Para os testes de radiopacidade, escoamento, solubilidade e confecção dos corpos de prova para os tempos de presa foram seguidas as especificações nº57 da ANSI/ADA (2000) e ISO 6876 (2012). Para a medição dos tempos de presa, inicial e final, foi empregada a norma ASTM C266/2008. O pH foi avaliado nos períodos de 3, 24, 72 e 168 horas. Sobre os resultados foram aplicados testes estatísticos com nível de significância de 5%. Resultados: Os resultados demonstraram que o cimento Sealer Plus apresentou menor radiopacidade do que o cimento AH Plus (p<0.05), porém, superior ao mínimo recomendado pelas especificações, ou seja, de 3 mm de Al. Com relação ao escoamento, o do Sealer Plus foi 19,19 mm e do AH Plus 19,81 mm (p>0.05). O Sealer Plus apresentou tempos de presa inicial e final de 138 min. e 210 min., respectivamente, enquanto o AH Plus, 437 min. e 849 min., respectivamente, (p<0.05). Em relação à solubilidade, o Sealer Plus apresentou 0,21% e o AH Plus 0,27% (p>0.05). Nenhum dos cimentos apresentou aumento significativo do pH (p>0.05). Conclusão: O cimento Sealer Plus apresentou propriedades físico-químicas de acordo com as especificações nº 57 da ANSI/ADA (2000) e ISO 6876 (2012).

Aerosol particle properties and their impact on air quality, clouds, and the hydrologic cycle remain a critically important factor for the understanding of our atmosphere. Particle hygroscopic growth leads to impacts on direct and indirect radiative forcing properties, the likelihood for particles to act as cloud condensation nuclei, and aerosol-cloud interactions. Current instruments measuring hygroscopic growth have a number of limitations, lacking either the ability to measure size-resolved particles or process samples at a fast enough resolution to be suitable for airborne deployment. Advanced in-situ airborne particle retrieval and measurements of aerosol hygroscopic growth and scattering properties are analyzed and discussed.To improve the analysis of cloud nuclei particles, an updated counterflow virtual impact inlet was characterized and deployed during the 2011 E-PEACE field campaign. Theoretical and laboratory based cut size diameters were determined and validated against data collected from an airborne platform. In pursuit of higher quality aerosol particle hygroscopicity measurements, a newer instrument, the differential aerosol sizing and hygroscopicity probe (DASH-SP) has been developed in the recent past and only flown on a handful of campaigns. It has been proven to provide quality, rapid, size-resolved hygroscopic growth factor data, but was further improved into a smaller form factor making it easier for deployment on airborne platforms. It was flown during the 2013 SEAC4RS field campaign and the data was analyzed to composite air mass based hygroscopicity and refractive index (real portion only) statistics. Additionally, a comparison of bulk and size-resolved hygroscopic growth measurements was conducted. Significant findings include a potential particle size bias on bulk scattering measurements as well as a narrow range of ambient real portion of refractive index values. An investigation into the first reported ambient hygroscopicity measurements of particle shrinkage, or "sub-1" growth is conducted. Possible explanations, including particle restructuring, measurement sensitivity to refractive index, evaporative loss, and influence of ambient external mixtures on data processing are examined.

Orientador: Mário Tanomaru Filho
Abstract: Tricalcium silicate cements associated with radiopacifiers are used as repair materials. Publication 1: Evaluation of tricalcium silicate-based cements (TCS) associated with zirconium oxide (ZrO2), calcium tungstate (CaWO4) or niobium oxide (Nb2O5) radiopacifiers compared to MTA Repair HP (MTA HP). Publication 2: Evaluation of tricalcium silicate-based cements (TCS) associated with zirconium oxide (ZrO2) radiopacifier with 10% or 20% of Biosilicate (TCS ZrO2 + 10% Biosilicate and TCS ZrO2 + 20% Biosilicate) compared to Biodentine. Setting Time (ST) and radiopacity were evaluated based on ISO 6876/2002 standard. Solubility was evaluated according to the method proposed by Carvalho-Júnior et al. (2007) modified. pH was measured at 3, 12 and 24 hours and 7, 14 and 21 days after immersion in distilled water. Cellular cytotoxicity and bioactivity were evaluated by methyltetrazolium (MTT), neutral red (NR), alkaline phosphatase (ALP), alizarin red (ARS) and real time PCR (qPCR) (Publication 1) assays in different periods of contact with eluates of the materials in Saos-2 cells. Antibacterial activity was evaluated by direct contact on Enterococcus faecalis in the planktonic form. For the physico-chemical and ARS tests, the data were submitted to ANOVA and Tukey tests; for MTT, NR and ALP tests the data were analyzed by the Two-Way ANOVA and Bonferroni tests; the antibacterial activity, were submitted to Kruskall-Wallis and Dunn tests (α = 0.05). Publication 1: TCS + CaWO4 presented... (Complete abstract click electronic access below)
Resumo: Cimentos de silicato tricálcico com radiopacificadores são utilizados como materiais reparadores. Publicação 1: Avaliação de cimento à base de silicato tricálcico (STC) associado aos radiopacificadores óxido de zircônio (ZrO2), tungstato de cálcio (CaWO4) ou óxido de nióbio (Nb2O5) em comparação ao MTA Repair HP (MTA HP). Publicação 2: Avaliação de material à base de silicato tricálcico (STC) e radiopacificador óxido de zircônio (ZrO2) e 10% ou 20% de Biosilicato (STC ZrO2 + 10% de Biosilicato e STC ZrO2 + 20% de Biosilicato) em comparação ao Biodentine. Tempo de presa e a radiopacidade foram avaliados seguindo ISO 6876/2002. A solubilidade foi avaliada de acordo com o método proposto por Carvalho-Júnior et al. (2007) modificado. pH foi avaliado 3, 12 e 24 horas, 7, 14 e 21 dias após imersão em água destilada. A citotoxidade e bioatividade celular foram avaliadas pelos testes metiltetrazólio (MTT), vermelho neutro (VN), atividade de fosfatase alcalina (ALP), ensaio de vermelho de alizarina (ARS) e PCR em tempo real (qPCR) (Publicação1), em diferentes períodos de contato com eluídos dos materiais em células Saos-2. Atividade antimicrobiana dos materiais foi avaliada por meio do teste de contato direto com Enterococcus faecalis na forma planctônica. Para os testes físicoquímicos e ARS, os dados foram submetidos aos testes ANOVA e Tukey; para os ensaios do MTT, VN e ALP e qPCR os dados foram analisados aos testes Two Way ANOVA e Bonferroni; os dados da atividade antimicrobiana f... (Resumo completo, clicar acesso eletrônico abaixo)
Mestre

In petroleum refining industries, the fracturing process allows for the cracking of long-chain hydrocarbons into a mixture of small olefin and paraffin molecules that are then separated via the energetically and monetarily demanding cryogenic distillation process. In an attempt to mitigate both energetic and capital consumptions, selective sorption of light hydrocarbons by tunable sorbents, such as metal-organic frameworks (MOFs), appears to be the most promising alternative for a more efficient gas separation process. MOFs are novel porous materials assembled from inorganic bricks connected by organic linkers. From a crystal engineering stand point, MOFs are advantageous in creating a range of microporous (0.2–2.0 nm) to mesoporous (>50 nm) void cavities, presenting unique opportunities for the functionalization of both the organic linkers and the void. Of significant importance is the MOF-74-M family (M = metal), characterized by a high density of open metal sites, that is not fully coordinated metal centers. This family of MOF is also known as CPO-27-M. MOF-74 have demonstrated more separation potential than other known MOFs and zeolites. Density functional theory (DFT), as implemented within a linear combination of atomic orbital (LCAO) approach, has been used to investigate the selective sorption of C1-C4 hydrocarbons in MOF-74-Mg/Zn. The study was first implemented by adopting a molecular cluster approach, and later by applying periodic boundary conditions (PBC). While both modellistic approaches agree in showing significant differences in binding energies between olefins and paraffins adsorbed at the MOFs’ open metal sites, results reported at the molecular cluster level show underestimation when compared to those obtained at the PBC level. The use of PBC models allow for the correcting of binding energies for basis set superposition error (BSSE), molecular lateral interaction (LI), zero-point energy (ZPE), and thermal energy (TE) contributions. As such, results obtained at the PBC level are directly comparable to experimental calorimetric values (i.e., heat of adsorptions). This work discusses, for the first time, the origin of the fictitious agreement between binding energies obtained with molecular clusters and experimental heats of adsorption, identifying its origin as due to compensation of errors. Spectroscopy studies based on the intensities and frequency shifts with respect to the molecules in the gas phase are presented as a further investigation of the interaction of the small hydrocarbons (C₁-C ₂) with the open metal sites in MOF-74-Mg. In an attempt to provide a more comprehensive description of the behavior of the hydrocarbon molecules, results from diffusion mechanism studies are also presented. The investigations of the diffusion mechanisms are based on the use of climbing-image nudge elastic band (CI-NEB) simulations, coupled with van der Waals functional (vdW-DF) and ultra-soft pseudopotentials as implemented within the plane-wave (PW) DFT approach. The CI-NEB studies showed that paraffin molecules are more energetically favored to diffuse within and along the cavity of MOF-74-Mg with respect to their olefin counterparts.

Pre-clinical and clinical trials suggest that pre-treatment with dexamethasone (Dex) may facilitate enhanced uptake of subsequently administered chemotherapeutic agents. To reduce the side effects associated with systemic administration of Dex, solid lipid nanoparticles (SLNs) containing dexamethasone palmitate (Dex-P) were prepared as a means of achieving tumor-targeted drug delivery. These studies were aimed at evaluating the physicochemical properties and both the physiological and storage stability of the SLNs. SLNs were prepared using nanotemplate engineering technology. Stearyl alcohol (SA) was used as the lipid phase with Brij® 78 and Polysorbate 60 as surfactants and PEG6000 monostearate as a long-chain PEGylating agent. Both formulations exhibited a small particle size, ellipsoidal shape, and low polydispersity. 1H-NMR spectroscopy confirmed that SLNs have the expected solid core and PEGylated surface. Analysis of the bulk materials indicated that a number of complex interactions are present among the SLN components, including a eutectic between SA and Brij® 78. Dex-P could be incorporated in SLNs at 10-30% w/w SA with encapsulation efficiencies >85%. A preferential interaction with the SA-Brij® 78 eutectic was identified, indicating a possible interfacial localization. For comparison, SLNs were also prepared with ascorbyl palmitate (AP) and curcumin. Higher drug loads were achieved with both palmitate-containing prodrugs than curcumin, though all appeared to align differently within the SLNs. SLNs undergo a concentration-dependent particle size growth when incubated at physiological temperature. However, they appear to remain intact with over 85% of the added Dex-P retained at 24 h in conditions mimicking human plasma. In the presence of carboxylesterase, SLNs became turbid and showed a reduction in particle size as compared to controls. This instability was shown to be a result of the hydrolysis of PEG6000 monostearate and Polysorbate 60. To enhance storage stability, a lyophilization protocol designed to minimize changes in the physicochemical properties of SLNs was developed. During a 3 month period, lyophilized SLNs stored at 4°C demonstrated the greatest stability, showing a consistent particle size and an encapsulation efficiency >80%. Overall, these results indicate that Dex-P loaded SLNs possess the physicochemical properties and stability desirable for development as a tumor-targeted drug delivery system.

A compostagem pode ser definida como o processo de biodegradação de resíduos orgânicos realizado por comunidades microbianas em condições aeróbias, sendo uma forma sustentável de gerir estes resíduos no contexto de uma economia mais circular. Neste trabalho foi analisado um sistema de compostagem a uma escala comunitária. Para cada pilha, as matérias-primas e os compostos foram pesados e as temperaturas monitorizadas semanalmente. Os parâmetros físico-químicos foram analisados, bem como o teor de inertes, e foram realizados testes fitotóxicos. Os resultados mostraram que as amostras de composto cumpriam a maioria dos requisitos definidos pelas normas legais portuguesas em relação à qualidade dos mesmos, exceto no teor de humidade e de pedras. No entanto, os testes de maturação indicaram que todos os produtos finais estavam consistentemente maturados. Os resultados obtidos demonstraram que é possível gerir os resíduos orgânicos dos espaços verdes através da compostagem local, com benefícios ao nível ecológico e social; Composting is the biodegradation process of organic substrates carried out by microbial communities, under aerobic conditions. It is a sustainable way to manage biodegradable waste within a context of a more circular economy. In this work, a community-scale green waste composting system was under study. For each pile, feedstocks and composts were weighted and temperatures were monitored weekly. Physicochemical parameters were analysed, phytotoxic tests were performed and the inert material content was assessed. Results showed that the compost samples fulfilled the majority of the requirements set by the Portuguese statutory standards for compost quality, except for moisture and stone content. However, maturity tests indicated all final products as consistently mature. Additionally, the particle size dimensions of the final composts were suitable for both of the main uses. The results showed that is possible to manage organic waste from the green areas through local composting with ecological and social benefits associated.

Doutoramento em Química
During the last years, the use of high hydrostatic pressure (HHP) as a non-thermal technology for preservation or aging of wine has increased substantially in the academic community. However, HHP treated wine has been only analysed after the pressure treatment, with no knowledge available on the effects of HHP during subsequent storage. The results presented in this thesis showed that HHP treatments influence the chemical and sensorial properties of wine during storage. The application of high hydrostatic pressure treatments in winemaking for wine preservation, as an alternative to sulphur dioxide, was evaluated studying the effect of HHP in the physicochemical and sensorial properties of red and white wines during bottle storage. High pressure treatments with 5 min of processing time and pressures of 425 and 500 MPa were shown to influence on both red and white wine physicochemical and sensorial characteristics. However, the effects were only perceptible after, at least, 6 months of storage. The alterations that occurred on the pressurized red wine characteristics, such as the more orange-red colour and the lower antioxidant activity (15-27% less), total phenolic content (9% less), and anthocyanins content (45–61% less), were due to an increase of condensation reactions of phenolic compounds. The increase of these condensation reactions lead to the formation of compounds with higher degree of polymerisation that became insoluble along storage, increasing consequently the amount of wine deposits in the pressurized wines. In terms of white wines, pressurized wines showed, after one year of storage, a more brownish colour and a lower antioxidant activity (15% less) and total content of phenolic compounds (10% less) when compared to the unpressurized wines. These results, together with the lower content of free amino acids (15-20% less) and higher content of furans (up to 70% more), present in the pressurized wines after nine months of storage, led to propose an effect of HHP treatments in the acceleration of Maillard reactions that occur during the wine storage period. Therefore, contrary to the pressurized sulphur dioxide-free red wine, the pressurized white wines were not considered suitable for commercialization as table wines due to the higher brownish colour and cooked fruit aroma, characteristics of an aged or thermally treated wine.Additionally, the impact of the pressure treatments on the volatile composition of sulphur dioxide-free red and white wines, during bottle storage, was evaluated. More than 160 volatile compounds, distributed by 12 chemical groups, were identified in both wines. At the end of storage, the pressurized wines presented a higher content of furans, aldehydes, ketones, and acetals when compared to the unpressurized wines. These results indicate that pressure influences the white and red wine long term volatile composition, being this particularly evident for longer storage periods. The changes on the volatile composition of the pressurized wines, indicated that the HHP treatments accelerate the Maillard reactions, and the oxidation of alcohols and fatty acids, leading to wines with a volatile composition network approaching the characteristic of faster aged and/or thermally treated wines. The acceleration of Maillard reactions and phenolic compounds condensation by HHP treatments was also studied in model wine solutions (hydro alcoholic solution at acidic pH). The results showed that the high pressure treatment accelerated the Maillard reaction and this effect was quantifiable, mainly, after 6 months of storage. Pressurized model solutions presented higher concentration of 2-furfural, phenylacetaldehyde and benzaldehyde, when compared to the controls. In terms of phenolic compounds condensation reactions, the pressurized model wine solutions showed no relevant differences, when compared to controls. Therefore, it seems that the pressure treatment had a higher impact in terms of kineticks of reactions and in less extent in terms of different compounds formed. Lastly, the application of HHP treatments in winemaking to improve the properties of young wines was evaluated. For this propose, the effect of HHP treatments in the phenolic composition of a red wine was studied and compared with the effect of different oenological practices. Wines pressurized at 500 MPa for 5 min, and 600 MPa for 20 min, at 20 ºC, showed, after 5 months of storage, a lower monomeric anthocyanins (8-14%), phenolic acids (8-11%) and flavonols (14-22%) content, when compared to the unpressurized ones. The wine pressurized at 500 MPa presented a flavanols content and a degree of polymerization very similar to the wines treated by traditional aging processes. In terms of sensorial properties, the pressure treatments increased the cooked fruit aroma and decreased the floral and fruit odours and, in the case of the 600 MPa treatment, increased the bitterness. Therefore, the HHP treatments seem to promote reactions that are similar to those observed in wines treated with wood aging processes. In conclusion, the results presented in this thesis showed that HHP treatments accelerated the Maillard reaction and the polymerization reactions between phenolic compounds present in the wine, influencing the chemical and sensorial properties of wine. HHP can be potentially used to preserve or accelerate the wine aging process, producing wines with pleasant and distinct characteristics.
Durante os últimos anos, o uso de alta pressão hidrostática (APH) como tecnologia não-térmica para a preservação ou envelhecimento de vinho tem aumentado substancialmente na comunidade académica. No entanto, os vinhos tratados por APH têm sido analisados após o tratamento de pressão, não havendo referências sobre as suas propriedades durante o armazenamento. Os resultados apresentados nesta tese mostram que a aplicação de tratamentos de APH altera as propriedades químicas e sensoriais de vinhos ao longo do armazenamento. Os tratamentos de alta pressão hidrostática foram aplicados na vinificação para a preservação de vinho, como alternativa ao dióxido de enxofre, sendo o seu efeito avaliado nas propriedades físico-químicas e sensoriais de vinhos tintos e brancos durante o armazenamento em garrafa. Os tratamentos de alta pressão com 5 min de processamento e pressões de 425 e 500 MPa mostraram influenciar as características físico-químicas e sensoriais de vinhos tintos e brancos. No entanto, o efeito foi apenas percetível após pelo menos 6 meses de armazenamento. As alterações que ocorreram nas características do vinho tinto pressurizado, tais como a cor mais laranja-vermelho, menor atividade antioxidante (menos 15 a 27%), menor conteúdo de compostos fenólicos totais (menos 9%) e menor teor de antocianinas (menos 45-61%), foram devidas a um aumento das reacções de condensação de compostos fenólicos. O aumento destas reações de condensação levou à formação de compostos com maior grau de polimerização que se tornaram insolúveis no vinho ao longo do armazenamento, aumentando consequentemente a quantidade de depósito nos vinhos pressurizados. Em relação ao vinho branco, os vinhos pressurizados mostraram, depois de um ano de armazenamento, uma cor mais acastanhada, menor atividade antioxidante (menos 15%) e menor teor de compostos fenólicos totais (menos 10%) comparando com os vinhos não pressurizados. Estes resultados, juntamente com o baixo teor de aminoácidos livres (menos 15 a 20%) e um maior teor de furanos (até 70% mais) para os vinhos pressurizados após nove meses de armazenamento, levam a propor que os tratamentos de APH aceleraram as reações de Maillard que ocorrem durante o período de armazenamento do vinho. No entanto, ao contrário dos vinhos tintos pressurizados, os vinho brancos pressurizados não foram considerados adequados para comercialização como vinhos de mesa, visto que apresentavam uma cor acastanhada e um elevado aroma a fruta cozida, características estas de vinhos envelhecidos ou tratados termicamente.Adicionalmente, foi avaliado o impacto dos tratamentos de APH sobre a composição volátil dos vinhos tintos e brancos sem dióxido de enxofre durante o armazenamento em garrafas. Mais de 160 compostos voláteis, distribuídos por 12 grupos químicos, foram identificados em ambos os vinhos. No final do armazenamento, os vinhos pressurizados apresentaram um teor mais elevado de furanos, aldeídos, cetonas e acetais quando comparados com os vinhos não pressurizados. Estes resultados indicam que os tratamentos de APH influenciam a composição volátil de vinhos brancos e tintos, , sendo mais evidente em longos períodos de armazenamento. As mudanças na composição volátil dos vinhos indicaram que os tratamentos de APH aceleraram as reações de Maillard e também a oxidação de álcoois e ácidos gordos, originando vinhos com uma composição volátil próxima de vinhos com envelhecimento acelerado ou tratados termicamente. A aceleração das reações de Maillard e de polimerização dos compostos fénolicos causada pelos tratamentos de APH foi também estudada em soluções modelo de vinho (solução hidroalcoólica com pH ácido). Os resultados mostraram que o tratamento de APH acelera a reação de Maillard , sendo este efeito quantificado, apenas, após 6 meses de armazenamento. As soluções modelo de vinho pressurizadas apresentaram concentrações mais elevadas de 2-furfuraldeído, fenilacetaldeído e benzaldeído, em comparação com os controlos. Em termos de polimerização dos compostos fénolicos, as soluções modelo pressurizadas não apresentaram diferenças relevantes, em comparação com os controlos. Por conseguinte, os tratamentos de APH aparentem ter mais impacto em termos de modificações nas cineticas de reação do que na formação de novos compostos. Por último, a aplicação de tratamentos de APH foi estudada para melhorar as propriedades de vinhos jovens. Para este propósito, o efeito de tratamentos de APH na composição fenólica de um vinho tinto foi estudado e comparado com o efeito de diferentes práticas enológicas. Vinhos pressurizados a 500 MPa durante 5 min e a 600 MPa durante 20 min, a 20 ºC, mostraram depois de 5 meses de armazenamento um menor teor de antocianinas monoméricas (8-14%), ácidos fenólicos (8-11%) e flavonóis (14 -22%), quando comparados com os vinhos não-pressurizados. O vinho pressurizado a 500 MPa apresentou um teor de flavonóis e um grau de polimerização de taninos muito semelhante aos vinhos tratados por processos de envelhecimento tradicionais. Em termos de propriedades sensoriais, os tratamentos de pressão aumentaram o aroma de fruta cozida e diminuiram os aromas florais e frutados, tendo no caso do tratamento de 600 MPa sido verificado também um aumento da amargura. Assim sendo, os tratamentos de APH parecem promover reações que são semelhantes às observadas em vinhos tratados com processos de envelhecimento em madeira. Em conclusão, os resultados apresentados nesta tese mostram que a aplicação de tratamentos de APH acelera as reações de Maillard e a polimerização dos compostos fenólicos presentes no vinho, ao longo do armazenamento, alterando assim as propriedades químicas e sensoriais dos vinhos. A APH pode ser potencialmente utilizada para preservar ou acelerar o processo de envelhecimento de vinho tinto produzindo vinhos com características agradáveis e distintas.

Le but de ce travail était d'essayer de comprendre dans quelles mesures les non-sucres présents dans les sirops de sucre ont un effet néfaste sur la cristallisation du saccharose et sur la qualité du sucre obtenu. Pour réaliser cette étude nous avons étudié comparativement différents échantillons industriels de différents origines. Cette étude a nécessité la mise en œuvre d'un certain nombre de techniques de séparation et de fractionnement (ultrafiltration, dialyse, chromatographie d'échange d'ions et d'exclusion stérique. . . ). La combinaison de ces méthodes nous a permis de montrer que l'EP2 danois contient davantage de polyosides de poids moléculaire supérieur à 10000 daltons à caractère non chargés que l'EP2 d'Eppeville. En revanche les fractions moléculaires comprises entre 2000 et 10000 daltons ne semblent pas montrer de différences significatives. On notera que les produits traités industriellement par des résines reminéralisantes et décolorantes ne comportent pratiquement plus de macromolécules. Le relargage à l'alcool des substances colloïdales est un test classique de contrôle, nous avons tenté de l'appliquer aux différents produits sucrés industriels. Nous avons ainsi pu montrer que les non-sucres des EP2 danois sont globalement moins hydrophile que ceux de la sucrerie française qui nous a servi de référence, ce résultat est intéressant car le sucre roux danois obtenu à partir de cet EP2 est de bien meilleure qualité que le sucre roux d'Eppeville. Les macromolécules présentes dans les sirops proviennent en partie de la dégradation des polysaccharides de la betterave qui ont échappé à l'épuration calco-carbonique industrielle, pour comprendre ce phénomène, nous avons montré que la dégradation alcaline des pulpes touche essentiellement les pectines, en revanche hémicelluloses et cellulose résistent bien aux pH basiques. Ce résultat est intéressant pour un approfondissement ultérieur de la connaissance de ces macromolécules. Enfin, dans un but d'application industrielle, nous nous sommes intéressés à l'étude de la valorisation des pulpes de betteraves (décoloration et prévention de l'oxydation des lipides présents) ainsi qu'à l'étude de différentes propriétés fonctionnelles du produit obtenu

O desafio das indústrias de alimentos na substituição da gordura trans em diversos produtos reside no desenvolvimento de formulações e processos que apresentem funcionalidade equivalente e viabilidade econômica. A interesterificação química representa uma opção tecnológica importante para a produção de gorduras visando diversas aplicações comerciais, sem a formação de ácidos graxos trans. O óleo de palma contém quantidades aproximadamente iguais de ácidos graxos saturados e insaturados e pelo seu fracionamento obtêm-se duas frações: a estearina (fração sólida) e a oleína (fração líquida). A estearina e oleína de palma são opções interessantes para a produção de grande variedade de produtos como margarinas e shortenings. Assim, o objetivo deste trabalho foi modificar as propriedades físico-químicas de misturas de estearina e oleína de palma pelo uso da interesterificação química. As amostras foram analisadas quanto à composição em ácidos graxos e triacilgliceróis, distribuição regioespecífica dos ácidos graxos nos triacilgliceróis, índice de iodo, pontos de amolecimento e de fusão, conteúdo de gordura sólida, consistência e estrutura cristalina. Os ácidos graxos saturados são predominantes na estearina (71,9%), sendo que 65,5% correspondem ao ácido palmítico. A oleína tem como principal constituinte o ácido oléico, que representa 45,4%. À medida que aumenta a proporção de oleína de palma nas misturas, aumentam a quantidade de ácidos graxos insaturados e o índice de iodo e diminui a quantidade de ácidos graxos saturados. Após a interesterificação química, os pontos de fusão e amolecimento, a consistência e o conteúdo de gordura sólida aumentaram nas misturas que apresentavam maior proporção de oleína em função do aumento no teor de triacilgliceróis trissaturados. Por outro lado, estas propriedades não se modificaram nas misturas com maior proporção de estearina. Este comportamento se deve à distribuição aleatória dos ácidos graxos nos triacilgliceróis após a interesterificação, que forma triacilgliceróis em proporções diferentes das existentes originalmente. Os principais triacilgliceróis nas misturas foram PPP, PPO e POO. Antes da interesterificação os ácidos graxos saturados foram encontrados principalmente nas posições sn-1,3. Mudanças significativas na composição dos ácidos graxos na posição sn-2 após a interesterificação química foram encontradas em misturas com mais de 60% de oleína de palma. A mistura e a interesterificação permitiram obter gorduras com diferentes graus de plasticidade, aumentando as possibilidades de uso das frações estearina e oleína de palma.
The challenge of the food industries for the replacement of trans fat in various products lies in the development of formulations and processes which have equivalent functionality and economic viability. The chemical interesterification of palm stearin and palm olein is an important technological option for the production of fats targeting commercial applications, without formation of trans fatty acids Palm oil contains similar amounts of saturated and unsaturated fatty acids. After fractionation two fractions are obtained: stearin (solid fraction) and olein (liquid fraction). Palm stearin and palm olein are alternatives for the production of many products, such as margarines and shortenings. The objective of this work was to modify the physical and chemical properties of mixtures of palm stearin and palm olein by using chemical interesterification. The following properties were analyzed: fatty acid and triacylglycerol compositions, regiospecific distribution of fatty acids in triacylglycerols, iodine value, softening and melting points, solid fat content, consistency and crystal microstructure. Saturated fatty acids are predominant in palm stearin (71.9%), which corresponds to 65.5% of palmitic acid. Palm olein has as its main constituent the oleic acid, which represents 45.4% of the unsaturated fatty acids. The increase of the proportion of palm olein in the mixture causes increase on the amount of unsaturated fatty acids and iodine value and decrease on the content of saturated fatty acids. After chemical interesterification, melting and softening points, consistency and solid fat content increased in the blends that had higher proportion of palm olein, as a consequence of the increase in the trisaturated triacylglycerols. On the other hand, these properties did not alter in the blends with higher proportion of palm stearin. This behavior is due to the random distribution of fatty acids in triacylglycerols after interesterification, which forms triacylglycerols in proportions that are different from those originally present. The major triacylglycerols in the blends were PPP, PPO and POO. Before interesterification the saturated fatty acids were found mainly in the sn-1,3 positions. Significant changes in the fatty acid composition in the sn-2 position after chemical interesterification were found in blends with more than 60 % of palm olein. Blending and interesterification of fats resulted in structured lipids with different degrees of plasticity, increasing the possibilities of use of stearin and olein fractions.

La gomme arabique exsudée par Acacia senegal est un polymère naturel hétéropolymoléculaire parfaitement hydrophile. L'étude physico-chimique d'exsudats d'Acacia senegal, bien identifiés botaniquement, issus de populations artificielles du Nord Ferlo (Sénégal) permet d'établir la variabilité des valeurs de viscosité, de pouvoir rotatoire et de teneur en azote. Nous avons cherché des corrélations des différents paramètres entre eux et des paramètres physico-chimiques avec les conditions climatiques et édaphotopographiques de la gommeraie. Afin d'améliorer les propriétés émulsifiantes de la gomme arabique, nous avons modifié chimiquement ses chaînes en accentuant le caractère hydrophobe. La caractérisation des produits greffés et de la gomme arabique a été réalisée par des mesures de tension superficielle, de conductimétrie et de viscosimétrie de cisaillement. De même, le comportement en émulsion de chacune des gommes a été étudié

Les prelevements sur l'etna (1978-86) et le momotombo (1985-86) sont effectues a l'aide d'impacteurs en cascade fractionnant l'aerosol en 6 classes granulometriques puis analyses par pixe et sfx. Le comportement en fonction de l'activite volcanique des elements constitutifs et des elements volatiles est etudie. La modelisation thermochimique dynamique realisee permet de conclure sur les mecanismes de generation d'origine haute temperature et la modelisation thermodynamique avec ou sans apport d'air permet de conclure sur les principales voies de condensation du gaz de haute temperature evoluant naturellement

En conditions de plein champ après retournement d'une prairie permanente, on compare pendant cinq ans l'évolution des propriétés d'un sol brun entre deux parcelles, l'une exempte de tout traitement chimique, l'autre désherbée à l'atrazine. On observe au cours du temps une diminution de la stabilité structurale (-30%) et de la teneur en matière organique (- 20%), ainsi qu'une augmentation du rapport isotopique ¹³C/¹²C, du taux d'humification et de l'extractibilité des acides humiques. Toutefois, l'étude des caractéristiques chimiques de la matière organique ne révèle pas de différence majeure entre les deux parcelles tout au long des cinq années. Un fractionnement des agrégats à 50 [micro]m permet de mettre en évidence une plus grande richesse en carbone de la fraction grossière (50-2000 [micro]m) du sol non désherbé par rapport au sol traité, qui peut être attribuée aux importants retours de matière organique fraiche par les adventices. Ces derniers n'affectent cependant pas les caractéristiques qualitatives des matières organiques totales ; ainsi le rapport C/N reste constant et identique dans les deux parcelles. L'analyse en spectroscopie d'absorption infra-rouge des acides humiques et fulviques extraits montre que les groupements fonctionnels des composés humifiés ne sont affectés de façon majeure ni par l'évolution générale du sol ni par le traitement à l'atrazine. Cependant, l'étude de la cinétique d'adsorption de l'atrazine met en évidence une diminution de la vitesse de mise à l'équilibre entre les échantillons les plus anciens et les plus récents. Par ailleurs, la comparaison de l'adsorption entre la fraction fine (0-50 [micro]m) et la fraction grossière (50-200 [micro]m) d'un même échantillon de sol montre que l'adsorption est moins rapide mais également moins réversible sur la fraction grossière. Ces différences de comportement rendent compte de variations très fines de la réactivité des matières organiques, et sont commentées en relation avec la structure hypothétique du complexe argilo-humique

L'acquisition du fer et l'echange de ce metal entre deux siderophores sont des processus biologiques majeurs. Des etudes preliminaires ont montre l'existence de complexes ternaires intermediaires lors de l'echange de ligand. Nous presentons une approche structurale des complexes ternaires par le biais de nouveaux ligands de syntheses. Quatre ligands ont ete prepares, deux comportent des structures mixtes : deux sortes de sous-unites regroupees sur une charpente tripodale. Deux voies de syntheses ont ete envisagees. Dans la premiere, la charpente tripodale etait obtenue par alkylation d'une amine secondaire. La seconde voie selectionnee implique le couplage des sous-unites sur un espaceur tripodal, le tris-(1,2-aminoethylamine) ou tren. Les intermediaires clefs de cette synthese sont des molecule possedant un groupe amine primaire sur l'un des bras de l'espaceur. Les ligands ont ete rendus hydrosolubles par sulfonation controlee du systeme aromatique des sous-unite chelatantes. En absence de cristaux, les etudes des complexes ont ete realisees par spectrometrie de masse electrospray, par spectrophotometrie uv-visible, et par etudes rmn des complexes de gallium iii correspondants. Les etudes physico-chimiques nous ont permis de determiner le comportement de ces modeles de siderophores lors de la complexation du fer (iii) : par les mesures de pka, des courbes de distribution des especes en fonction du ph et des constantes thermodynamiques de complexation. L'activite biologique des ligands a ete evaluee par mesure de leur capacites nutritives sur des cultures cellulaires de plantes. Un de nos complexe c'est avere etre plus efficace que les complexes de l'edta, traditionnellement employes comme source de fer dans les milieux de culture.

Cette these se situe dans le cadre des modelisations chimiques de proteines fer-soufre, plus particulierement les proteines fer-soufre a haut potentiel (hipip). L'objectif est de synthetiser des centres 4fe-4s dans les deux etats d'oxydation physiologiques 4fe-4s#2+ et 4fe-4s#3+ et de les caracteriser d'un point de vue physico-chimique. L'hypothese a partir de laquelle le sujet a ete aborde consiste a supposer qu'il est necessaire d'etablir une zone steriquement encombree et hydrophobe autour de l'agregat afin de proteger le centre 4fe-4s#3+ d'une degradation oxydante. Pratiquement, un tel environnement encombre et hydrophobe a ete realise grace a l'utilisation de ligands thiolates riches en noyaux aromatiques et tres encombres. Pour chaque ligand utilise, le centre 4fe-4s#2+ a ete synthetise et caracterise par les spectroscopies uv-visible, rmn et mossbauer, et l'etude de sa susceptibilite magnetique a aussi ete effectuee. Dans un deuxieme temps, des etudes d'oxydation sont realisees sur ces nouveaux composes modeles 4fe-4s#2+ dans le but d'obtenir des centres 4fe-4s#3+. Des phenythiolates d'une part et des benzylhtiolates d'autre part, tous tres hydrophobes, ont ete utilises comme ligands. Dans chacun des cas, un nouveau modele de hipip a ete obtenu et completement caracterise dans les deux etats redox. Celui avec le ligand de type benzylthiolate est un meilleur modele chimique de ces proteines car il utilise des ligands plus biomimetiques. Par ailleurs, l'influence exercee par l'encombrement sterique a ete etudiee de facon systematique. En utilisant une serie de ligands encombres de facon croissante, il a pu etre montre tres clairement que la presence d'un environnement encombre (et toujours tres hydrophobe) au voisinage immediat de l'agregat assure la protection du centre 4fe-4s#3+ vis-a-vis des degradations ulterieures. L'ensemble des resultats obtenus autorisent a conclure sur la validite de l'hypothese de depart, laquelle preconisait l'emploi de ligands encombres pour l'obtention de tels modeles stables. Ce travail permet alors egalement de confirmer l'hypothese sur les proteines qui consiste a dire que l'hydrophobicite est un critere fondamental pour qu'une proteine a 4fe-4s fonctionne comme une hipip plutot que comme une ferredoxine

L'agent actif considéré a été l'éthoprophos, principe nématicide utilisé en agrochimie, mais dans un premier temps, l'aniline a été utilisé comme agent simulant. Les processus d'absorption et de désorption dans l'eau, ont été modélisés, dans le cas d'un granulé composé d'EVA pur, à l'aide d'une solution analytique de l'équation de Fick. Un modèle mathématique basé sur une méthode numérique a été construit pour décrire les transferts à travers un granulé composé par un noyau et une enveloppe

The objective of this work was to investigate the physicochemical nature of an exogenous surfactant Infasurf and ascertain its effects on an oscillating bubble system. Knowledge of the pulmonary surfactant properties such as adsorption, desorption and diffusivity is important in accurate modelling of pulmonary mechanics in cases of airway collapse and reopening which occur in disease states such as respiratory distress syndrome (RDS). We divided the project into experimental, analytical, and parameter matching methods to describe the physicochemistry of Infasurf We used a pulsating bubble surfactometer (PBS) to investigate constant- and oscillating-area dynamic surface tension responses of Infasurf . The hysteresis loops were compared using several measured loop characteristics, which provide insight into the controlling surfactant transport phenomena. The characteristics are highly dependent on the bulk concentration and oscillation rate. The loop characteristics also served as the point of comparison between experiments and theoretical models for our parameter matching With high bulk concentrations, successive oscillations in the PBS compress the monolayer to collapse. Here, the hysteresis loops displayed two nearly constant surface tension plateaus during expansion and compression, implicating collapse and respreading as the primary mechanisms responsible for the shape and size of these hysteresis loops Our models emulated the experimental protocols: constant area, oscillating bubble with a monolayer, and oscillating bubble with a multilayer. The dynamic surface tension data was compared with model output to determine the values of the physicochemical parameters (sorption rates, diffusivity, surface packing states, etc.). We used an equation of state, derived from Langmuir trough compressions, which coupled Frumkin kinetics to a curve-fit region at the lowest surface tensions Parameter matching was used to evaluate the physicochemical properties of surfactants. The most striking result is that the existence of the multilayer depends heavily on the primary layer sorption properties. If the primary layer cannot saturate during compression, collapse will never be reached. We also found that although Infasurf is slowly diffusing, at sufficiently high bulk concentrations the model may be simplified by neglecting surfactant diffusion. The protocols developed herein may be useful for evaluating surfactant physicochemical properties used in surfactant replacement therapy of infants with RDS
acase@tulane.edu

The mechanism of molecular mass transport processes such as solubilization and Ostwald ripening in surfactant stabilized oil-in-water emulsions and the effect on their bulk physicochemical properties was investigated. Solubilization was slightly influenced by the initial emulsion droplet size. The smaller the droplets were, the faster the oil molecules were incorporated into surfactant micelles. During solubilization, the droplet size of the emulsion increased. This increase was more pronounced for emulsions with low oil droplet concentrations and small droplet sizes. Solubilization was influenced by the nature of the dispersed phase. Small molecular weight n-hydrocarbons were rapidly solubilized. Triglycerides could not be incorporated in micelles due to their large molecular weight. The nature and concentration of surfactant micelles; also influenced solubilization kinetics. Surfactant micelles with HLB numbers close to seven incorporated more oil more rapidly than surfactants with larger HLB numbers. The growth of oil droplets in surfactant stabilized emulsions during solubilization experiments was due to Ostwald ripening. Ostwald ripening depended on the nature of the oil droplets. Low molecular weight hydrocarbons had a higher solubility in the aqueous phase and therefore aged more quickly than high molecular weight compounds. Ostwald ripening was accelerated by the presence of surfactant micelles that acted as carriers between emulsion droplets. A larger number of surfactant micelles therefore resulted in increased Ostwald ripening rates. Surfactants that were highly surface-active and consequently had a higher diffusion coefficient accelerated Ostwald ripening strongly. Both Ostwald ripening and solubilization were accelerated in emulsions were surfactant micelles were present. In comparison, solubilization proceeded faster than Ostwald ripening. Finally, the effect of mass transport processes emulsion rheology and color was investigated. Ostwald ripening influenced the rheology of emulsions. Emulsions made with n-hexadecane exhibited a rapid solid-liquid. like transition whereas the rheological properties of n-octadecane emulsion droplets did not change significantly during the course of the experiment. Ostwald ripening also influenced the color of emulsions that contained a red dye in the aqueous phase. Aging experiments conducted on n-hexadecane emulsion droplets did show significant color changes with time whereas n-octadecane emulsion droplets retained their color during the course of the experiment.

博士
臺灣大學
生物產業機電工程學研究所
98
This study developed an analytical method to detect the spatial changes of sugar and lycopene content in tomatoes and sugar content in bananas during ripening process by using CSI technique. An algorithm was developed to correct the image artifact due to field inhomogeneity, and thus to visualize the internal spatial distribution of sugar and lycopene content of the same tomatoes and sugar content of bananas before and after ripening. The experiments were performed to acquire tomato images with the same imaging parameters at mature green and red ripe stages and banana images on different days after ethylene treatment. The spatial distribution of sugar and lycopene content in tomatoes and sugar content in bananas were compared before and after ripening process. After comparing the maximum PSNR, SNR, and linewidth of water phantom in 3T and 7T CSI data with the same imaging parameters, we found the imaging indexes in 7T CSI -- the maximum PSNR 3371, the maximum SNR 810, and the maximum linewidth 0.214 ppm -- are almost twice those in 3T CSI. This demostrates that CSI image quality in 7T is better than in 3T. On the other hand, when comparing the concentration of sugar solutions and CSI intensity, we found that a linear relationship exists between them. Using the linear relationship, the sugar content of tomatoes and bananas was quantitatively analyzed. After comparing the sugar content and lycopene content in a tomato with CSI and HPLC analyses, the sugar content was found to have slightly decreased, and the lycopene content had increased after ripening process. We further compared the sugar content in bananas using CSI and HPLC analyses. The sugar content in the pulp quickly increased during the first 4 days after ethylene treatment, and there were little change in the peel. In this study, results from the CSI analyses of sugar and lycopene in tomato or banana fruits were consistent with that of the HPLC analyses. Therefore, the non-destructive CSI technique may become an efficient tool for physiological analyses in the future.

Hollow fiber ultrafiltration is a viable low cost alternative technology for the concentration or separation of protein solutions. However, membrane fouling and solute build up in the vicinity of the membrane surface decrease the performance of the process by lowering the permeate flux. Major efforts have been devoted to study membrane fouling and design more efficient ultrafiltration membrane systems. The complexity of membrane fouling, however, has limited the progress to better understand and predict the occurrence of fouling. This work was motivated by the desire to develop a microscopic Computational Fluid Dynamics (CFD) model to capture the complexity of the membrane fouling during hollow fiber ultrafiltration of protein solutions. A CFD model was developed to investigate the transient permeate flux and protein concentration and the spatial fouling behavior during the concentration of electroacidified (pH 6) and non- electroacidified (pH 9) soy protein extracts by membrane ultrafiltration. Electroacidification of the soy protein to pH 6 was found to decrease the permeate flux during UF which resulted in longer filtration time. Lower electrostatic repulsion forces between the proteins at pH 6 (near the protein isoelectric point) resulted in a tighter protein accumulation on the membrane surface suggested to be responsible for the lower permeate flux observed in the UF of the electroacidified soy protein extract. A new transient two-component fouling resistance model based on the local pressure difference, permeate velocity and protein concentration was implemented in the resistance-in-series flux model to describe the dynamics of the reversible and irreversible fouling during the filtration and the effect of pH on the membrane fouling. Good agreement between the experimental data and the model predictions was observed. Mathematical modeling was performed to estimate the osmotic pressure and diffusion coefficient of the proteins bovine serum albumin (BSA) and soy glycinin, one of the major storage proteins in soy, as a function of protein concentration, pH, and ionic strength. Osmotic pressure and diffusion coefficient of proteins play vital roles in membrane filtration processes because they control the distribution of particles in the vicinity of the membrane surface, often influencing the permeation rate. Therefore, understanding the behavior of these properties is of great importance in addressing questions about membrane fouling. An artificial neural network was developed to analyze the estimated data in order to find a simple relation for osmotic pressure as a function of protein concentration, pH, and ionic strength. For both proteins, the osmotic pressure increased as pH diverged from the protein isoelectric point. Increasing the ionic strength, however, reversed the effect by shielding charges and thereby decreasing the osmotic pressure. Osmotic pressure of glycinin was found lower than that of BSA. Depending on how much pH was far from the isoelectric point of the protein, osmotic pressure of BSA could be up to three times more than the glycinin’s. Two different trends for diffusion coefficient at specified pH and ionic strength were observed for both proteins; diffusion coefficient values that decreased with protein concentration and diffusion coefficient values that passed through a maximum. A rigorous CFD model based on a description of protein interactions was developed to predict membrane fouling during ultrafiltration of BSA. BSA UF was performed in a total recycle operation mode in order to maintain a constant feed concentration. To establish a more comprehensive model and thereby alleviate the shortcomings of previous filtration models in literature, this model considered three major phenomena causing the permeate flux decline during BSA ultrafiltration: osmotic pressure, concentration polarization, and protein adsorption on the membrane surface. A novel mathematical approach was introduced to predict the concentration polarization resistance on the membrane. The resistance was estimated based on the concentration and thickness profile of the polarization layer on the membrane obtained from the solution of the equation of motion and continuity equation at a previous time step. Permeate flux was updated at each time step according to the osmotic pressure, concentration polarization resistance, and protein adsorption resistance. This model had the ability to show how microscopic phenomena such as protein interactions can affect the macroscopic behaviors such as permeate flux and provided detailed information about the local characteristics on the membrane. The model estimation was finally validated against experimental permeate flux data and good agreement was observed.

A novel approach for the production of soy protein isolates was investigated integrating electroacidification and membrane ultrafiltration. The effect of electroacidification on the ultrafiltration performance and physicochemical properties of the soy protein extracts was obtained by comparing an electroacidified (pH 6) and a non-electroacidified (pH 9) soy protein extract. The effect of membrane fouling on the permeate flux decline was studied in a hollow fiber and a dead end ultrafiltration system. Due to more significant membrane fouling, the permeate flux was always lower for the electroacidified extract, resulting in at least 1.5-fold increase in the total fouling resistance compared to the non-electroacidified extract. The total amount of protein deposited on the membrane surface during unstirred dead-end ultrafiltration was comparable (about 7 mg/cm2) for both soy protein extracts. The discrepancy between the total fouling resistance and the protein deposition estimates was attributed to the formation of denser (less permeable) fouling deposit for the electroacidified extract, which was supported by scanning electron microscopy studies of fouled membranes. The removal of carbohydrates and minerals was evaluated for direct ultrafiltration and two-stage discontinuous diafiltration using a hollow fiber system. The carbohydrate removal results were always consistent with the theoretical predictions, indicating that the carbohydrates were freely permeable across the membrane. In contrast, the minerals were partially retained by the membrane, but to a higher extent for the non-electroacidified extract, which demonstrated that the electroacidification pretreatment enhanced the mineral removal during the ultrafiltration. Incorporation of the diafiltration step improved the ash (mineral) and carbohydrate removal. Stronger electrostatic interactions between soy proteins, calcium/magnesium, and phytic acid (antinutrient) at alkaline pH resulted in less efficient removal of calcium, magnesium, and phytic acid during the ultrafiltration of the non-electroacidified extract compared to the electroacidified extract. Consequently, the soy protein isolates produced by electroacidification and the hollow fiber ultrafiltration had a lower mineral and phytic acid content. The protein content was at least 88 % (dry basis), with or without the electroacidification pretreatment. The study of the viscosity revealed that the electroacidification pretreatment reduced the viscosity of the soy protein extract, which resulted in a lower axial pressure drop increase during the ultrafiltration of the electroacidified extract compared to the non-electroacidified extract. Adjusting the pH of the electroacidified extract to 9 and the pH of the non-electroacidified extract to 6 had a great impact on the particle size distribution but only a marginal effect on the viscosity of the pH adjusted extracts. This indicated that the pH and the particle size distribution were not responsible for the viscosity difference between the electroacidified and the non-electroacidified soy protein extracts. It was proposed that the electroacidification pretreatment had some impact on the water hydration capacity of the soy proteins, which consequently affected the viscosity.

Flaxseed (Linum usitatissimum L.) gum (FG) is a material with many potential food and non-food applications. Consistent performance is critical for FG utilization and this is possible through selection of genotype, characterization and optimization of constituents, and chemical modification. Physico-chemical and functional properties of FG aqueous solutions from six Canadian flaxseed cultivars were investigated. FG yield, carbohydrate composition, protein content, and zeta potential (ζ) varied among these cultivars. FG solution properties were also affected by temperature, solution pH, NaCl concentration, and sucrose concentration. Detailed studies were conducted on CDC Bethune FG (FGB) proteins that were separated by 2D-gel electrophoresis. Conlinin was identified as the major protein. Protease treatment decreased FGB solution emulsification properties suggesting that conlinin might enhance emulsification. Formation of BSA-FGB coacervates was monitored by turbidimetric analysis as a function of solution pH, biopolymer mixing ratio, NaCl and urea. Coacervates were stabilized primarily by attractive electrostatic forces and secondarily by hydrogen bonds. Further, anionic carboxymethyl ether moieties were introduced to FGB structure through ether forming reactions using monochloroacetic acid (MCA) to produce products with uniform properties. The highest degree of substitution (DS) was obtained at 70 °C, 7.0 M NaOH, and a molar ratio of MCA to FGB of 10:1 over 3 h. Carboxymethylated FGB (CMFG) exhibited both modified surface morphology and thermal behaviour. Solutions of CMFG demonstrated shear-thinning behaviour and apparent viscosity decreased with increased DS. A more liquid-like flow behaviour was observed for CMFG as DS increased. Findings here will introduce and expand FG applications in food or related fields with targeted performance.

碩士
國立中興大學
食品科學系
89
Two waxy rice varieties, Tai Gang Waxy 1(TGW1) and Taichung Waxy 70(TCW 70), and one non-waxy high amylose rice variety, Tainung Sen 17(TnuS17), of second crop of 1999 were used as test samples. Centrifugal filtration was used to investigate the difference in physicochemical properties of wet-milled rice flours. The eating qualities of it’s rice cakes were also examined. Centrifuge dehydration, it performed three layers of filter cake with different color after centrifuging. The data showed that there were differences in particle size and leached out amount of rice flour between different layers. Rice flour which located in the inside-layer showed highest protein, ash and fat content, highest amylase activity and lowest viscosity, white index and enthalpy(ΔH). Rice flour which located in the intermediate-layer showed lowest amylase activity, protein, ash and fat content and highest viscosity, white index and enthalpy(ΔH). In rice flour products, the physical properties of nein-kau, the results found that nein-kau prepared by inside layer had lowest value in springiness, cohesiveness and chewness. Nein-kau prepared by outside layer showed highest springiness, cohesiveness and chewness. Concerning the eating quality of rice cup cake, rice cup cake prepared by different layers of TNuS17 also showed differences in texture. Rice cup cake prepared by inside layer showed lowest hardness, adhesiveness and chewness. Rice cup cake prepared by outside layer showed highest hardness, adhesiveness and chewness.

A research report submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in partial fulfilment of the requirements for the degree of Master of Science. Johannesburg, South Africa, 2015.
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碩士
國立宜蘭大學
環境工程學系碩士班
103
In eastern Taiwan, serpentine is generally founded because of collision accompanied by volcanic activity. Such topography after weathering, easy to form a high chromium and nickel content of the soil. As a result, there are some places chromium(VI) concentration will exceeds the control standard for drinking water (50 μg/L) by the WHO. This study is aim at chromium and nickel high risk potential areas in Hualien where demonstrated by EPA for investigation to soil and groundwater chemical properties, and established a background content of chromium and nickel in soil to clarify the study area for hazardous environment of chromium and nickel as according to the study area in the future use. This study selected a region of chromium and nickel high risk potential area in Hualien, and chose three soil from Wanrong village and twenty four soil from Zhangqiao village with chemical properties of chromium and nickel. We also selected eighteen samples drilling by collection of soil from Hualien EPB set a groundwater monitoring well at Zhuoqing Elementary School as this research soil geological chemical properties reference compared. Experimental results indicated that three of soil samples from Wanrong village with total Ca/Mg ratio is much lower than 1.0 and Cr and Ni concentrations were consistent with EPA findings. There are five of soils selected of six soils by XRF screen from Zhangqiao village with total ratio is much lower than 1.0 that confirm characteristics of serpentine soil, and total Cr and Ni are consistent with the soil pollution control standards but some of sample concentration slightly higher than the natural content of heavy metals of farmland in Taiwan. This shows there is no worry of Cr and Ni contamination that effected smaller by serpentine in Zhangqiao village. There are some soils that concentration of total Cr and Ni are much higher than the soil pollution control standards in Zhuoqing Elementary School. There is a characteristic with soil derived from serpentine that is total Ca/Mg ratio will decrease when the concentration to rise of total Cr and Ni. The soils in study with sequence extraction method can be divided into exchangeable form, carbonate bonding form, iron and manganese oxide bonding form, organic bonding form, and residual form five species distribution type. The results indicated that the chemical form of chromium in soils mainly in residual form (at least 85%). Nickel can be found outside of the percentage of residual form is up to 50%, this result indicating that the mobility and harmfulness of Ni are more dangerous than Cr. This study conduct water quality statistics and simulation of groundwater chemical models with groundwater monitoring stations water quality investigate data and clarifying effect with high Cr and Ni content of heavy metals in soil to groundwater. The Piper diagram indicates that in most part of study area, the chemical character of water is dominated by two types, Ca-HCO3 and Mg-HCO3. The groundwater chemistry simulation results show that the study area of nickel mineral will not precipitation showed with saturation index is much less than 0 and chromium mineral will precipitation showed with saturation index is greater than 0 and sedimentation were mainly of Cr2O3.

The moisture content of residual soils above the water table, and near ground surface (≤ 6 m) is influenced by the environmental relative humidity (RH). The focus of this thesis is to examine the physico-chemical and physical mechanisms of moisture retention and moisture loss in unsaturated residual soils in response to environmental RH and the implications of such changes on the engineering behavior of soils. The physicochemical drivers of moisture retention include forces and energy responsible for adsorption and desorption of water molecules on soil particle surfaces and capillaries, while the micro-structural features include, tortuosity and pore structure in influencing moisture retention and transport in unsaturated soils. In this study, laboratory experiments were performed with representative fraction of residual soil collected from Indian Institute of Science Campus, Bengaluru and five different saturated salt solutions were used to maintain environmental RH of 97%, 76%, 64.4%, 33% and 7% in the desiccators. The thermodynamics of moisture loss from the residual soil specimens were explored by performing experiments with moist powder soil specimens that were exposed to environmental RH of 33 to 97% at various constant temperatures (16 to 35°C). Distribution constant (Kc) is employed to account for the affinity of desorption of water molecules from soil particles. Analysis of laboratory results revealed that moisture desorption is an endothermic process associated with positive entropy changes and the trend of ΔGo (free energy change) variations indicated that moisture desorption is most favored at low environmental RH. Similar to SWRC (soil water retention curves), the ability of GAB (Guggenheim- Anderson-de Boer) isotherm to characterize the equilibrium soil moisture content - RH relations of compacted residual soil specimens along the drying path were explored and was successful in predicting the equilibrium water contents inspite of the variations in initial compaction conditions. The preferential desorption of water molecules from monoand multi-layers at low relative humidity required relatively larger (1.68 to 3.42 kJ/mol) desorption energy, while, from capillary condensation layer at higher relative humidity required lesser (0.08 to 0.5 kJ/mol) desorption energy. The influence of controlled environmental RH on the moisture loss behavior of compacted residual soil specimens was explored. As the RH of water in soil pores was in excess of the environmental RH of the desiccator, moisture desorption occurred from the compacted soil specimens exhibiting a falling rate segment. The moisture loss under RH gradients caused rapid increase in total suction of the specimens during the falling rate segment. Although the void ratios of the compacted specimens were unaffected by moisture loss, the micro-structure of the soils were affected; increase in very fine (< 0.002 μm) and fine pore (0.002 to 0.01 μm) contents at the expense of medium pores (0.01 to 6.0 μm) content was exhibited by most specimens. Analysis of the moisture loss - exchange period data showed that moisture loss from the compacted soil specimens is driven by diffusion and prevalence of lower RH in the environment facilitates speedier diffusion of moisture from soil pores. The thesis also develops an approach to select appropriate tortuosity (τ) equation based on dominant mode of moisture transport (liquid water or vapor) for correct prediction of moisture flux from the unsaturated soil when using Fick’s equation. Analysis of the laboratory results revealed that during the moisture loss process, as long as θ (volumetric water content) remains greater than a critical water content (θcr) value, capillary controlled flow of water dominates the moisture loss process and the τ is dependent on θ. When θ becomes less than θcr, vapor diffusion through connected air-filled pores becomes important and τ is dependent on air-filled porosity (θa). Knowledge of the final water content (wf) achieved by the unsaturated soil specimen during moisture loss under controlled environmental RH defines θcr for the soil. Good agreement is obtained between predicted and experimental moisture flux (qv) obtained by using τ values based on the dominant mode of moisture transport. Lastly, the thesis examines the influence of moisture loss under controlled environmental RH on compressive strength and collapse behavior of compacted residual soil specimens. Comparing the influence of moisture loss across specimens, it is observed that the initial water content and initial dry density had profound influence on magnitude of strength gain and stiffness respectively. The gain in strength and stiffness upon moisture loss is temporary as the improved strength and stiffness of the compacted specimens are lost on soaking. Examination of critical state stress ratios of compacted specimens upon moisture loss revealed that the critical state stress ratio for changes in net mean stress (Ma) and changes in matric suction (Mb) are strongly influenced by moisture loss. At Sr (degree of saturation) values < 1, Ma exceeds Ms (critical stress ratio at saturation) as particle aggregation at lower Sr causes the soil to behave in a coarser manner. In comparison, the Mb values are less than Ms at Sr < 1 as lowering the Sr causes the water phase to recede into the fine pores of the aggregates and the capillary bonds do not strengthen the aggregate - aggregate contact during shear. Exposure to environmental RH influences the swell and collapse tendency of the compacted residual soil specimens. At a given vertical pressure, exposure to lower RH renders the specimen more collapsible. The increased collapse potential upon moisture loss is attributed to existence of high matric suction in the unsoaked state that stabilizes the inter granular contacts; loss of inter-granular contacts on wetting leads to collapse of soil. In addition to suction, the wetting load to swell pressure ratio also influences the nature of wetting induced volumetric strains. At ratios < unity, the compacted specimen swells and at ratios > unity, the compacted specimen collapse. Further for wetting load < swell pressure ratio, the specimen with lower ratio swells more. Likewise, for wetting load > swell pressure ratio, the specimen with larger ratio collapses more.

Celem badań przeprowadzonych w latach 2012-2015 była ocena wpływu pasterstwa na właściwości fizykochemiczne i stan sanitarno-bakteriologiczny wód podziemnych w rejonach pastwisk owiec zlokalizowanych na obszarze Pienin i Beskidu Sądeckiego w południowej Polsce. W rejonie Pienin zrealizowano dotychczas wiele prac naukowych z dziedziny nauk przyrodniczych, w tym geologicznych i hydrogeologicznych, które obejmowały badania wpływu pasterstwa owiec na roślinność, zwierzęta, gleby i wody powierzchniowe, nie dokonano jednak szczegółowego rozpoznania wpływu pasterstwa owiec na jakość wód podziemnych. Badaniami objęto dziesięć poligonów badawczych usytuowanych na obszarze pienińskiego pasa skałkowego oraz zewnętrznych Karpat fliszowych, gdzie prowadzony jest wypas o zróżnicowanej intensywności. Do badań wytypowano łącznie 25 źródeł, które poddano systematycznym badaniom okresowym przeprowadzonym w trzech sezonach badawczych: wiosną, latem i jesienią. Badania terenowe polegały na wykonaniu pomiarów temperatury wód, odczynu pH, przewodności elektrolitycznej właściwej, zawartości związków azotu i fosforanów oraz wydajności źródła. Pobierano również próbki wód podziemnych do laboratoryjnych analiz chemicznych w celu określenia stężeń jonów głównych i podrzędnych oraz mikroskładników, a także do badań sanitarnobakteriologicznych obejmujących oznaczenie ogólnej liczby drobnoustrojów, liczbę bakterii z grupy coli, w tym Escherichia coli, liczbę kolonii bakterii Shigella sp. i Salmonella sp. Oznaczenia fizykochemiczne (poza zawartością mikroskładników) oraz mikrobiologiczne wykonano własnoręcznie, korzystając z laboratoriów Wydziału Geologii Uniwersytetu Warszawskiego. Dodatkowo, pobrano próbki utworów podglebowych dla określenia wartości współczynnika filtracji przy użyciu przepuszczalnościomierza laboratoryjnego. W toku przeprowadzonych badań uzyskano bardzo bogaty zbiór danych, który poddano szczegółowej analizie w oparciu o dostępne materiały kartograficzne, publikacje hydrogeologiczne i dane archiwalne dotyczące pasterstwa owiec. Tematyka badań ma charakter interdyscyplinarny z pogranicza hydrogeologii, ochrony środowiska i mikrobiologii sanitarnej.
The purpose of the research carried out from 2012 to 2015 was to assess the influence of grazing on the physicochemical properties and the sanitary and bacteriological condition of groundwater in the vicinity of sheep pastures located in Pieniny and Beskid Sądecki region in southern Poland. In the Pieniny region, many scientific works were carried out in the field of natural sciences, including geological and hydrogeological, covering studies on the influence of sheep grazing on vegetation, animals, soils and surface waters. However, no detailed diagnosis has yet been made to determine the influence of sheep grazing on groundwater quality. The research covered ten research areas located in the Pieniny Klippen Belt and the outer Flysch Carpathians, each differing in the intensity of sheep grazing. A total of 25 springs were selected for the study, which were subjected to systematic periodic tests conducted in three research seasons: spring, summer and autumn. Seasonal field investigations consisted of measuring water temperature, water reaction, electrical conductivity of water, nitrogen and phosphate content and spring discharge. Groundwater samples were also collected for laboratory chemical analyzes to determine the concentrations of major ions, subordinate and minor elements, as well as for sanitary and bacteriological tests including the determination of the total bacterial count, the count of bacteria from the coli group, including Escherichia coli, the count of Shigella sp. and Salmonella sp. Physicochemical (except for minor elements) and microbiological determinations were made by hand using the laboratories of the Faculty of Geology at the University of Warsaw. In addition, soil samples were taken to determine the value of the coefficient of permeability using a laboratory permeability meter. In the course of the study, a very rich set of data was obtained, which was subjected to detailed analysis based on available cartographic materials, hydrogeological publications and archival data on sheep grazing. Research topics are interdisciplinary, from the border of several branches of science, such as hydrogeology, environmental protection and sanitary microbiology.