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Dermal and respiratory exposure to nickel in a packaging section of a base metal refinery / Hendrik Johannes ClaassensClaassens, Hendrik Johannes January 2013 (has links)
Nickel is one of the most commonly known sensitisers and has been classified by the International Agency for Research on Cancer (IARC) as a possible carcinogen to humans (group 2B). Workers at a South African base metal refinery packaging area are potentially exposed to many hazardous chemicals that include nickel.
Aims and Objectives: The aim and objectives of this study were to assess dermal and respiratory exposure of workers exposed to nickel in a packaging section at a South African base metal refinery and to assess the change in skin barrier function during a work shift by measuring percentage change in trans epidermal water loss (TEWL), skin hydration and skin surface pH. Skin health was established with a skin questionnaire. Surfaces that workers may come into contact with were also assessed.
Method: Respiratory and dermal exposure assessment was done concurrently. Respiratory exposure was assessed and analysed by using the National Institute for Occupational Safety and Health (NIOSH) method 7300. The Institute of Occupational Medicine (IOM) inhalable aerosol sampler was used for personal air sampling. The TEWL index, skin hydration and skin surface pH of the index finger, palm, forearm and forehead were measured before and at the end of the shift with a Derma Measurement Unit, EDS 12 and Skin-pH-Meter® pH 905. These measurements were reported as percentage change in skin barrier function during the shift. Dermal exposure samples were collected with Ghostwipes™ from the index finger and palm of the dominant hand before, during and at the end of the shift, while samples from the forearm and forehead were only collected before and after the shift. Surface sampling was collected and all wipes were analysed for nickel according the NIOSH method 9102, using inductively coupled plasma-atomic emission spectrometry.
Results: Respiratory exposure for the whole group of workers in a packaging section was well below the eight hour Time Weighted Average (TWA) respiratory Occupational Exposure Limit (OEL) of 0.5 mg m-3 for nickel. Dermal nickel loading was detected for all the job categories on all the anatomical areas even before the shift had commenced. During the shift more nickel was detected on the index finger and palm of the hand. Levels on the forearm and forehead were much lower in comparison with the index finger and the palm of the hand. Workplace surfaces, which workers may come into contact with on a daily basis, were also contaminated with nickel. Forklift drivers showed high exposure on the index finger and palm of their hands, and this can be attributed to them not wearing any gloves for hand protection. An increase in percentage change for TEWL was seen for most of the job categories on all anatomical areas measured during the shift. Percentage change in skin surface pH and skin hydration varied among job categories.
Conclusion: The research addressed the problem statement, with the stated objectives. It was hypothesised that workers at a packaging section of a base metal refinery are exposed to quantifiable levels of nickel through the dermal exposure route. The hypothesis was accepted and control measures together with future studies were recommended.
The results confirmed that all workers at a base metal refinery are exposed to quantifiable levels of nickel through the dermal exposure route. Dermal exposure was evident on all anatomical areas for all job categories before the shift had commenced. Personal protective equipment was provided to all employees, but forklift drivers did not wear gloves when operating the forklift. Respirable exposure to nickel was below the OEL. Changes in TEWL and to a lesser extent skin hydration, suggest a deterioration in skin barrier function during the shift. Forklift drivers as well as plate washers may be the highest risk job categories in developing allergic contact dermatitis. Several measures to lower respiratory and dermal exposure to nickel are also recommended. / MSc (Occupational Hygiene), North-West University, Potchefstroom Campus, 2014
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Dermal exposure and skin barrier function of workers exposed to copper sulphate at a chemical industry / Christa SteynbergSteynberg, Christa January 2013 (has links)
Copper exposure is known to be a rare cause of skin irritation and allergic reactions and
according to our knowledge occupational dermal exposure to copper sulphate has not yet been
characterised. As a result, the objectives of this study were to assess the dermal exposure of
workers at a chemical industry to copper sulphate and to characterise the change in the their skin
barrier function from before to the end of the work shift, as the skin’s barrier function can greatly
influence the permeation of chemical substances.
Methods: The change in skin barrier function of reactor workers, crystal and powder packaging
workers at the chemical industry were assessed by measuring their dominant hand’s palm, back
and wrist as well as their foreheads’ skin hydration, transepidermal water loss (TEWL) and skin
surface pH before and at the end of the work shift. Commercial GhostwipesTM were used to
collect dermal exposure samples from the same four anatomical areas before and at the end of
the shift. Additional dermal exposure samples were collected from the palm and back of hand,
prior to breaks 1 and 2. Surface wipe sampling was also conducted at several work and
recreational areas of the chemical industry. Wipe samples were analysed by an accredited
analytical laboratory, according to NIOSH method 9102 by means of Inductively Coupled
Plasma-Atomic Emission Spectrometry.
Results: Changes in skin hydration of the workers and anatomical areas at the end of the work
shift were highly variable, while in general TEWL increased and skin surface pH decreased.
Copper was collected from the skin of all workers before the shift commenced, and dermal
exposure increased throughout the work shift. All of the work and recreational areas from which
surface samples were taken, were contaminated with copper.
Conclusion: As a result of intermittent use of inadequate protective gloves and secondary skin
contact with contaminated surfaces and work clothing, workers at the chemical industry are
exposed to copper sulphate via the dermal exposure route. The decrease in the workers’ skin
barrier function (increased TEWL) and skin surface pH is most likely the result of their dermal exposure to sulphuric acid, and may lead to enhanced dermal penetration. The low account of
skin irritation or reaction incidences among these workers is contributed to their ethnicity as well
as to the low sensitisation potential of copper. Recommendations on how to lower dermal
exposure and improve workers’ skin barrier function are made. / MSc (Occupational Hygiene), North-West University, Potchefstroom Campus, 2014
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Short-term effects of selected barrier creams on skin barrier function / Amanda VermaakVermaak, Amanda January 2014 (has links)
Background: Barrier creams are applied to the surface of the skin to form a barrier that aims to prevent the penetration of irritants and allergens through the skin surface. Several inconsistencies and controversies exist in literature regarding the effect that barrier creams may have on skin barrier function. Various skin surface parameters are used to evaluate the effect that the barrier creams have on skin barrier function. These parameters include transepidermal water loss (TEWL), skin hydration and skin surface pH. Total skin thickness may be assessed as a variable on its own. Differences may exist in skin surface parameters when comparing African participants with Caucasian participants.
Aim: The specific aim of this research was to evaluate the short-term1 effects of selected barrier creams on skin barrier function.
Note 1: The words short-term are used in this study as each barrier cream is only tested over a period of 8 hours and not tested over a long term period of months or years.
Method: Forty two non-smoking participants were included and tested in this study, of which 21 were African and the rest Caucasian. TEWL, skin hydration and skin surface pH were used to evaluate the differences in the effect of two different barrier creams (Reinol Solvgard and Momar Chex) on skin barrier function. TEWL was measured by making use of a closed chamber Vapometer (Deflin Technology Ltd., Kuopio, Finland), skin hydration using a Corneometer® CM 825 and skin surface pH using a pH meter probe (Courage and Khazaka Electronic Kӧln, Germany). A micro-pipette was used to drip a standard volume of 20 μl of ultrapure water on the skin surface before the researcher placed the pH meter probe onto the skin surface. Total skin thickness was measured by making use of ultrasound (Ultrascan 22 - TBS0061B) (Courage and Khazaka Electronic Kӧln, Germany). Three consecutive measurements were taken on the mid-forearm and the palm of the experimental arm. After baseline values were measured, 5 ml of the selected barrier cream was applied to the experimental arm. The barrier cream (selected for the day) was reapplied after 2, 4 and 6 hours and measurements were taken every 2, 4, 6 and 8 hours. The total skin thickness was measured at time zero and at 8 hours.
Results:
TEWL: For both barrier creams, statistical significant differences (p ≤ 0.05) were found between TEWL on the palms of African participants and Caucasian participants.
Skin hydration: Statistically significant differences (p ≤ 0.05) were obtained with regard to mid-forearm skin hydration when comparing Reinol Solvgard with Momar Chex (this was applicable to both racial groups). A statistically significant difference (p ≤ 0.05) was obtained with regard to mid-forearm skin hydration when comparing African participants with Caucasian participants (this was only applicable to Reinol Solvgard). Statistical significant differences (p ≤ 0.05) were obtained with regard to skin hydration palm when comparing Reinol Solvgard with Momar Chex (this was applicable to both racial groups). Statistically significant differences (p ≤ 0.05) were obtained with regards to skin hydration palm when comparing African participants with Caucasian participants (this was applicable to both barrier creams).
Skin surface pH: A statistically significant difference (p ≤ 0.05) was obtained with regard to pH of the mid-forearm when comparing Reinol Solvgard with Momar Chex (this was applicable to only the African participants). A statistical significance (p ≤ 0.05) was obtained with regards to skin surface pH mid-forearm when comparing African participants with Caucasian participants (this was applicable to Momar Chex barrier cream only). A statistically significant difference (p ≤ 0.05) was obtained with regards to the pH of the palm when comparing Reinol Solvgard with Momar Chex (this was only applicable to the African racial group).
Conclusion: Using skin surface parameters, it can be concluded that Momar Chex barrier cream elicited more positive effects on skin barrier function than Reinol Solvgard barrier cream. This may be ascribed to the fact that both barrier creams lowered TEWL (positive effect), Reinol Solvgard lowered skin hydration (negative effect) whereas, Momar Chex increased the skin hydration (positive effect) and both barrier creams increased skin surface pH (negative effect). Furthermore, the objectives of this study were reached as (a) short-term effects on skin surface parameters were identified between African versus Caucasian participants, (b) significances were observed between the two barrier creams (Momar Chex and Reinol Solvgard) by making use of skin surface parameters and (c) general increases and or decreases were observed in skin surface parameters over a short term period of 8 hours. / MSc (Occupational Hygiene), North-West University, Potchefstroom Campus, 2015
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Dermal and respiratory exposure to nickel in a packaging section of a base metal refinery / Hendrik Johannes ClaassensClaassens, Hendrik Johannes January 2013 (has links)
Nickel is one of the most commonly known sensitisers and has been classified by the International Agency for Research on Cancer (IARC) as a possible carcinogen to humans (group 2B). Workers at a South African base metal refinery packaging area are potentially exposed to many hazardous chemicals that include nickel.
Aims and Objectives: The aim and objectives of this study were to assess dermal and respiratory exposure of workers exposed to nickel in a packaging section at a South African base metal refinery and to assess the change in skin barrier function during a work shift by measuring percentage change in trans epidermal water loss (TEWL), skin hydration and skin surface pH. Skin health was established with a skin questionnaire. Surfaces that workers may come into contact with were also assessed.
Method: Respiratory and dermal exposure assessment was done concurrently. Respiratory exposure was assessed and analysed by using the National Institute for Occupational Safety and Health (NIOSH) method 7300. The Institute of Occupational Medicine (IOM) inhalable aerosol sampler was used for personal air sampling. The TEWL index, skin hydration and skin surface pH of the index finger, palm, forearm and forehead were measured before and at the end of the shift with a Derma Measurement Unit, EDS 12 and Skin-pH-Meter® pH 905. These measurements were reported as percentage change in skin barrier function during the shift. Dermal exposure samples were collected with Ghostwipes™ from the index finger and palm of the dominant hand before, during and at the end of the shift, while samples from the forearm and forehead were only collected before and after the shift. Surface sampling was collected and all wipes were analysed for nickel according the NIOSH method 9102, using inductively coupled plasma-atomic emission spectrometry.
Results: Respiratory exposure for the whole group of workers in a packaging section was well below the eight hour Time Weighted Average (TWA) respiratory Occupational Exposure Limit (OEL) of 0.5 mg m-3 for nickel. Dermal nickel loading was detected for all the job categories on all the anatomical areas even before the shift had commenced. During the shift more nickel was detected on the index finger and palm of the hand. Levels on the forearm and forehead were much lower in comparison with the index finger and the palm of the hand. Workplace surfaces, which workers may come into contact with on a daily basis, were also contaminated with nickel. Forklift drivers showed high exposure on the index finger and palm of their hands, and this can be attributed to them not wearing any gloves for hand protection. An increase in percentage change for TEWL was seen for most of the job categories on all anatomical areas measured during the shift. Percentage change in skin surface pH and skin hydration varied among job categories.
Conclusion: The research addressed the problem statement, with the stated objectives. It was hypothesised that workers at a packaging section of a base metal refinery are exposed to quantifiable levels of nickel through the dermal exposure route. The hypothesis was accepted and control measures together with future studies were recommended.
The results confirmed that all workers at a base metal refinery are exposed to quantifiable levels of nickel through the dermal exposure route. Dermal exposure was evident on all anatomical areas for all job categories before the shift had commenced. Personal protective equipment was provided to all employees, but forklift drivers did not wear gloves when operating the forklift. Respirable exposure to nickel was below the OEL. Changes in TEWL and to a lesser extent skin hydration, suggest a deterioration in skin barrier function during the shift. Forklift drivers as well as plate washers may be the highest risk job categories in developing allergic contact dermatitis. Several measures to lower respiratory and dermal exposure to nickel are also recommended. / MSc (Occupational Hygiene), North-West University, Potchefstroom Campus, 2014
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Dermal exposure and skin barrier function of workers exposed to copper sulphate at a chemical industry / Christa SteynbergSteynberg, Christa January 2013 (has links)
Copper exposure is known to be a rare cause of skin irritation and allergic reactions and
according to our knowledge occupational dermal exposure to copper sulphate has not yet been
characterised. As a result, the objectives of this study were to assess the dermal exposure of
workers at a chemical industry to copper sulphate and to characterise the change in the their skin
barrier function from before to the end of the work shift, as the skin’s barrier function can greatly
influence the permeation of chemical substances.
Methods: The change in skin barrier function of reactor workers, crystal and powder packaging
workers at the chemical industry were assessed by measuring their dominant hand’s palm, back
and wrist as well as their foreheads’ skin hydration, transepidermal water loss (TEWL) and skin
surface pH before and at the end of the work shift. Commercial GhostwipesTM were used to
collect dermal exposure samples from the same four anatomical areas before and at the end of
the shift. Additional dermal exposure samples were collected from the palm and back of hand,
prior to breaks 1 and 2. Surface wipe sampling was also conducted at several work and
recreational areas of the chemical industry. Wipe samples were analysed by an accredited
analytical laboratory, according to NIOSH method 9102 by means of Inductively Coupled
Plasma-Atomic Emission Spectrometry.
Results: Changes in skin hydration of the workers and anatomical areas at the end of the work
shift were highly variable, while in general TEWL increased and skin surface pH decreased.
Copper was collected from the skin of all workers before the shift commenced, and dermal
exposure increased throughout the work shift. All of the work and recreational areas from which
surface samples were taken, were contaminated with copper.
Conclusion: As a result of intermittent use of inadequate protective gloves and secondary skin
contact with contaminated surfaces and work clothing, workers at the chemical industry are
exposed to copper sulphate via the dermal exposure route. The decrease in the workers’ skin
barrier function (increased TEWL) and skin surface pH is most likely the result of their dermal exposure to sulphuric acid, and may lead to enhanced dermal penetration. The low account of
skin irritation or reaction incidences among these workers is contributed to their ethnicity as well
as to the low sensitisation potential of copper. Recommendations on how to lower dermal
exposure and improve workers’ skin barrier function are made. / MSc (Occupational Hygiene), North-West University, Potchefstroom Campus, 2014
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Modification et validation de la technique de l'anneau piézoélectrique pour mesurer la prise et le durcissement des matériaux à base de ciment / Modification and validation of piezoelectric ring actuator technique to monitor setting and hardening of cement-based materialsSoliman, Nancy Ahmed January 2010 (has links)
A period of cement hydration is one of critical in the life span of concrete structures. One of the reasons of collapse of concrete structural elements during and after construction is the error in determining the concrete characteristics at early age. Recently, non-destructive test emerged as a popular way to evaluate the properties of cement-based materials. This test offers continuous measurements of concrete properties as well as ability to monitor any changes in the current state of structural materials. In the existing research, some of these methods fail to capture well properties of the materials in the plastics stage. A new piezoelectric pulse testing device (Piezoelectric Ring Actuators Technique), (P-RAT ) was initially developed at the University of Sherbrook as a non-destructive test (NDT ) for soil. This technique is considered a completely new, versatile, advanced and accurate. The development of the new technique (P-RAT ) was done on two main bases: the first was the development of piezoelectric ring actuators set-up and the second is the development of the interpretation method. The setup is composed of two main units; emitter and receiver, and is capable of measuring shear and compression wave velocities in specimens. With this technique, many problems of pulse tests, which make interpretation of results difficult and ambiguous, were solved in soil. The P-RAT overcomes wave reflections at boundaries (end-caps and sides), sample disturbance, weak shear coupling between soil and device (interaction) as well as the fixation problems, low resonant frequency and limited input voltage of the existing device. The previous method is exploited forward to measure the hydration properties of cement-based material. To apply this test method, it is necessary to determine how the evolution of shear wave velocity can be related and sensitive to the hydration of cement-based materials. Validation of the P-RAT with four conventional test setups that can be used to monitor early setting and hydration of cement-based materials is carried out. These tests include penetration resistance to monitor initial and final setting respectively, calorimetric to monitor heat of hydration, electrical conductivity to monitor change in continuity of the pore structure and compressive strength at 24 hours. The phase one of this investigation included trial tests to investigate the possibility of employing the original setup used for soil (P-RAT ) to determine setting and hardening properties of cement-based material. Based on the results of the preliminary test, two modifications were conducted to the previous test device to fit with cement based material and to obtain adequate resonant frequency for cement-based materials. These modifications are the design of the container and changing the dimensions of the rings. The resultant version of P-RAT after the modification was referred to be as P-RAT2 . Calibration of the P-RAT2 with water specimen was undertaken using the compression wave velocity and resulted in 99.33% accuracy. One paste mixture was tested three times to determine the experimental error of the P-RAT2 . The repeatability carried out on the P-ART2 proved the ability of this setup to capture accurate results of the shear wave velocity. This relative error is limited to 9 %. A number of series of validation was performed on cement paste and mortar mixtures proportioned with various water cement ratios (w/cm ) as well as chemical admixtures. The w/cm ratio ranged between (0.35 and 0.50). The investigated chemical admixtures comprise of high-range water-reducing agent, viscosity-modifying agent, set-accelerating agent, and set-retarding agent. The presented validations examine the ability of a P-RAT2 to monitor the hydration of the cement-based materials. The hydration is characterized by setting time, heat of hydration, electrical conductivity, and compressive strength at 24 hours. The results obtained using the P-RAT2 was correlated to those obtained using the conventional tests and strength measurement. The results enable to validate the ability of P-RAT2 to accurately detect variations in the hydration of cement-based materials. In addition, the initial and final time of setting can be determined from the derivation of velocity vs. time curve. The results show that conductivity, resistivity, has a bilinear relationship to shear wave velocity. The compressive strength at 24 hours was correlated to both the shear wave velocity and shear modulus obtained using the P-RAT2 . Furthermore, analytical model was derived to estimate the w/cm in mortar mixture by measuring the shear wave velocity (V[subscript s] ) and the corresponding time (t )||Résumé : La période d'hydratation du ciment est l'une des périodes clé du cycle de vie des structures en béton. L'une des raisons de l'effondrement d'éléments structuraux en béton pendant et après la construction peut être attribuée à une détermination des caractéristiques au jeune âge erronée. Depuis quelques années, l’auscultation des structures est devenue une méthode très populaire pour évaluer les propriétés des matériaux cimentaires. Cette méthode permet d'obtenir les propriétés du béton en continue et possibilité un suivi de changements dans I'état des matériaux structuraux. Dans I'état actuel de la recherche dans ce domaine, certaines méthodes ne sont pas adéquates pour bien mesurer les propriétés des matériaux à I'état plastique. Un nouvel appareil d'essai à impulsions piezoélectriques (Piezoelectric Ring Actuators technique), (P-RAT) a initialement été développé à l’Université de Sherbrooke comme technique d'auscultation des sols. Cette technique est considérée complètement nouvelle, polyvalente, évoluée et précise. Le développement de cette nouvelle technique (P-RAT) a été effectué en deux volets : la première sole est le développement du dispositif de vérin de commande annulaire piezoélectrique et le deuxième est le développement d'une méthode d'interprétation. Le dispositif d'essai est composé de deux unités principales, un émetteur et un récepteur. Et permet de mesurer la vitesse de propagation des ondes de cisaillement et de compression. Grâce à cette technique, plusieurs des problèmes associés aux dispositifs d'essais par impulsion des ondes, qui rendent les résultats ambigus et difficiles à interpréter, ont été résolu pour les sols. Le dispositif P-RAT surmonte les problèmes de réflexion des ondes aux limites (embouts et côtés), la perturbation de l’échantillon, le couplage de cisaillement faible entre le sol et l'appareil (interaction) ainsi que les problèmes de fixation, la faible résonnance des fréquences et le voltage d'entrée limité du dispositif. La méthode décrite a été utilisée pour mesurer les propriétés d'hydratation des matériaux cimentaires. Pour pouvoir appliquer cette méthode, il faut déterminer comment l’évolution de la propagation des ondes de cisaillement peut être reliée à l'hydratation des matériaux cimentaires et être sensible à ces dernières. La validation de la méthode P-RAT est réalisée, à l'aide de quatre configurations conventionnelles que l’on peut utiliser pour faire le suivi de la prise et de l'hydratation des matériaux cimentaires. Ces essais consistent à la résistance à la pénétration afin de pouvoir déterminer la prise initiale et finale, la calorimétrie pour suivre l’evolution de la chaleur d'hydratation, la conductivité électrique pour effectuer le suivi de la structure des pores et la résistance à la compression à 24 heures. La phase 1 de l'étude comprend des essais pour évaluer la possibilité d'utiliser la configuration originale utilisée pour les sols (P-RAT) pour déterminer les propriétés de prise et de durcissement des matériaux cimentaires. Selon les résultats des essais préliminaires, deux modifications ont été effectuées à l'appareil original pour permettre son utilisation avec des matériaux cimentaires et pour obtenir une fréquence de résonnance raisonnable sur les matériaux cimentaires. Les modifications effectuées sont la conception du contenant et un changement de la dimension des anneaux. La version modifiée du P-RAT est designée P-RAT2. La calibration du P-RAT2 à l'aide d'échantillon liquide sous propagation d'ondes de compression a été menée, avec des résultats d'une précision de 99,33 %. Un mélange a été testé trois fois pour déterminer l'erreur expérimentale du P-RAT2. La répétitivité des essais sur le PART2 a démontré la capacité de cet appareil à produire des résultats de cisaillement de propagation des ondes de cisaillement très précis. L'erreur relative se limite à 9 %. Une série d'essais de validation a été menée sur des mélanges de pâte de ciment et de mortier de rapport eau/ciment variés (e/c) ainsi qu'avec des adjuvants. Le rapport e/c variait entre 0,35 et 0,50. Les adjuvants utilisés étaient des supers plastiflants (réducteur d'eau), des agents de viscosité, des agents accélérateurs de prise et des agents retardateurs de prise. Les validations présentées ont pour but de valider la capacité du P-RAT2 à suivre l'hydratation des matériaux cimentaires. L'hydratation est caractérisée par le temps de prise, la chaleur d'hydratation, la conductivité électrique et la résistance à la compression à 24 heures. Les résultats obtenus à l'aide du P-RAT2 ont été comparés à ceux obtenus à l'aide d'essais de mesure des caractéristiques physiques et de résistance traditionnels. Ces résultats permettent de valider la capacité du P-RAT2 à détecter avec précision les variations dans l'hydratation des matériaux cimentaires. De plus, le dispositif P-RAT2 peut avoir une correction avec mesure obteniez avec les appareils traditionnels. II est aussi possible de déterminer le temps de prise initial et final à l'aide d'une courbe de propagation vs le temps. Les résultats montrent que la conductivité et la résistivité ont une relation bilinéaire à la propagation des ondes de cisaillement. La résistance à la compression à 24 heures a été comparee à la fois à la propagation des ondes de cisaillement et au module de cisaillement obtenus avec le P-RAT2. De plus, un modèle analytique a été établi pour estimer le rapport e/c dans le mélange de mortier en mesurant la propagation des ondes de cisaillement (V) correspondant au temps (t).
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Effects of tree species diversity and soil drought on productivity, water consumption and hydraulic functioning of five temperate broad-leaved tree speciesLübbe, Torben 15 July 2015 (has links)
No description available.
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Kidney Hyaluronan : Regulatory Aspects During Different States of Body Hydration, Nephrogenesis & DiabetesRügheimer, Louise January 2008 (has links)
<p>The kidney regulates the excretion of water and electrolytes, which maintains homeostasis and enables control of arterial blood pressure. Hyaluronan, a large negatively charged interstitial glucosaminoglycan, is heterogeneously distributed within the kidney, primarily found in the medulla.</p><p>Medullary hyaluronan content changes depending on the state of body hydration and plays a part in fluid regulation through its water binding and viscoelastic properties. </p><p>The aim of this thesis was to provide new insight into the regulation of intrarenal hyaluronan during different states of body hydration, during completion of kidney development, and during diabetes mellitus.</p><p>Dehydration reduces medullary interstitial hyaluronan in parallel with reduced hyaluronan synthase 2 gene expression and increased urinary hyaluronidase activity. Acute hydration results in an increase in medullary hyaluronan, an increase that requires nitric oxide and prostaglandins. Urinary hyaluronidase activity decreases during hydration. The elevation of hyaluronan is important for reducing water permeability of the interstitium i.e. favoring diuresis.</p><p>Changes in hyaluronan concentration constitute a morphoregulatory pathway that plays a key role in nephrogenesis. The reduction in neonatal hyaluronan depended on an angiotensin II mediated process that does not appear dependent on lymph vessel formation. If angiotensin II is blocked with an ACE inhibitor, hyaluronan accumulates, which results in structural and functional abnormalities in the kidney. </p><p>Renomedullary hyaluronan is elevated during uncontrolled diabetes, which coincides with induction of hyaluronan synthase 2 mRNA, hyperglycemia, glucosuria, proteinuria and overt diuresis. The levels of hyaluronan are probably at a <i>terminus ad quem</i> as no further response was seen during hydration. The higher interstitial expression of hyaluronan during diabetes may be involved in the progression of diabetic nephropathy.</p><p>This thesis in physiology provides new mechanistic insights into the regulation of renal hyaluronan during various aspects of fluid handling.</p>
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Challenges in Computational Biochemistry: Solvation and Ligand BindingCarlsson, Jens January 2008 (has links)
<p>Accurate calculations of free energies for molecular association and solvation are important for the understanding of biochemical processes, and are useful in many pharmaceutical applications. In this thesis, molecular dynamics (MD) simulations are used to calculate thermodynamic properties for solvation and ligand binding.</p><p>The thermodynamic integration technique is used to calculate p<i>K</i><sub>a</sub> values for three aspartic acid residues in two different proteins. MD simulations are carried out in explicit and Generalized-Born continuum solvent. The calculated p<i>K</i><sub>a</sub> values are in qualitative agreement with experiment in both cases. A combination of MD simulations and a continuum electrostatics method is applied to examine p<i>K</i><sub>a</sub> shifts in wild-type and mutant epoxide hydrolase. The calculated p<i>K</i><sub>a</sub> values support a model that can explain some of the pH dependent properties of this enzyme.</p><p> Development of the linear interaction energy (LIE) method for calculating solvation and binding free energies is presented. A new model for estimating the electrostatic term in the LIE method is derived and is shown to reproduce experimental free energies of hydration. An LIE method based on a continuum solvent representation is also developed and it is shown to reproduce binding free energies for inhibitors of a malaria enzyme. The possibility of using a combination of docking, MD and the LIE method to predict binding affinities for large datasets of ligands is also investigated. Good agreement with experiment is found for a set of non-nucleoside inhibitors of HIV-1 reverse transcriptase.</p><p>Approaches for decomposing solvation and binding free energies into enthalpic and entropic components are also examined. Methods for calculating the translational and rotational binding entropies for a ligand are presented. The possibility to calculate ion hydration free energies and entropies for alkali metal ions by using rigorous free energy techniques is also investigated and the results agree well with experimental data.</p>
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Comportement des ciments pétroliers au jeune âge et intégrité des puits / Early age behavior of oil-well cement paste and wells integrityAgofack, Nicolaine 06 March 2015 (has links)
Lors du forage des puits d'hydrocarbure, une pâte de ciment est coulée dans l'espace annulaire entre le cuvelage en acier et les formations géologiques traversées. Pompée à l'état liquide, cette pâte de ciment fait sa prise le long du puits sous différentes conditions de température et de pression. La gaine de ciment ainsi mise en place a pour principales fonctions de promouvoir l'étanchéité pour protéger le casing contre la corrosion, de fournir le support mécanique pour assurer la stabilité du puits et d'isoler les différents fluides dans les couches traversées. Au cours de sa vie dans le puits, depuis le forage à la complétion et de la production à l'abandon, la gaine de ciment est soumise à différentes sollicitations mécaniques et thermiques qui peuvent l'endommager et altérer ses principales fonctions. La réponse de la pâte de ciment soumis à ces sollicitations dépend non seulement des conditions d'hydratation mais aussi de l'histoire des chargements précédemment appliqués. La prédiction du comportement de la gaine de ciment doit donc se faire à l'aide d'une modélisation numérique qui nécessite une loi de comportement pour la pâte de ciment. Le but de cette thèse est d'établir une loi de comportement de la pâte de ciment en cours d'hydratation pendant le jeune-âge (les 144 premières heures). Pour ce faire, des essais calorimétriques, de mesures de vitesse des ondes et des essais œdométriques ont été réalisés sur une pâte de ciment pétrolier classe G (w/c = 0,44) en cours de prise. Les conditions d'hydratation explorées vont de 7 à 30°C pour les températures et de 0,3 à 45MPa pour les pressions. Les résultats expérimentaux ont montré que les déformations volumiques de la pâte de ciment dues à son hydratation (retrait macroscopique) sont considérablement influencées par la contrainte sous laquelle la pâte de ciment s'hydrate. Plus la contrainte d'hydratation est élevée, plus élevé est le retrait macroscopique à 144 heures. Inversement, les déformations irréversibles dues à un cycle de chargement mécanique à cet âge sont moins importantes pour les contraintes plus élevées. Les résultats ont également montrés qu'au cours de la prise du ciment, il existe un temps critique à partir duquel l'application des cycles de chargement mécanique crée des déformations résiduelles dans la pâte de ciment. Ce temps critique arrive à un degré d'hydratation relativement constant, compris entre 0,18 et 0,20. Le modèle « Boundary Nucleation and Growth » a été utilisé pour étudier la dépendance de ce temps critique à la pression et à la température. Pour la modélisation du retrait macroscopique et de la réponse contrainte – déformation de la pâte de ciment, un modèle élasto-plastique chemo-poro-mécanique couplé, prenant en compte la désaturation du milieu, a été développé. Ce modèle utilise une surface de charge fermée de type Cam-Clay et une loi plastique associée. La loi d'écrouissage dépend des déformations volumiques plastiques et du degré d'hydratation. Les paramètres du modèle ont été évalués pour simuler le retrait macroscopique de la pâte de ciment hydratée sous différentes contraintes et températures. A un degré d'hydratation donnée, le modèle permet également de simuler la réponse contrainte-déformation due à un chargement mécanique / When drilling oil & gas well, cement slurry is pumped between the casing and the rock formation. This cement slurry sets at different conditions of temperature and pressure. The role of this cement sheath is to provide zonal isolation of different fluid along the well, to protect the casing against corrosion and to provide mechanical support. During the life of the well, from drilling to completion, production and P&A (plug and abandonment), the cement sheath is submitted to various mechanical and thermal loading that can potentially damage its properties and alter its performance. The behavior of cement paste submitted to theses solicitations depends both on the hydration condition and the loadings previously applied on the cement paste. The prediction of cement sheath behavior should be done by numerical modeling, which needs a constitutive law for cement paste. The purpose of the present work is to establish a constitutive law of cement paste during its hydration at early age (first 144 hours). The approach is based on combined calorimetric, wave velocities and oedometric tests on an oil-well class G cement paste with water-to-cement ratio equals 0.44. The hydration conditions explored are 7 to 30°C for temperature and 0.3 to 45MPa for pressure. The experimental results showed that the volumetric strain due to cement hydration (macroscopic shrinkage) depends considerably on the hydration pressure. At 144 hours of hydration, the macroscopic shrinkage increases with the hydration pressure increase. But, the residual strain due to application of mechanical cycle at this age is less for cement hydrated under higher pressure. The experimental results revealed that during the hydration there is a critical time after which, the application of mechanical loading can potentially induce residual strain in cement paste. This time is reached at constant hydration degree between 0.18 and 0.20. The Boundary Nucleation and Growth model was used to model the pressure and temperature dependence of this critical time. A coupled elasto-plastic chemo-poro-mechanical model is developed to simulate the macroscopic shrinkage of cement paste hydrated at different conditions of temperature and pressure. A modified Cam-Clay type yield surface with associate flow rule is used. The hardening law depends both on the degree of hydration and on the plastic volumetric strain. At constant degree of hydration, the developed model permits to simulate the stress – strain behavior of cement paste due to the mechanical loading
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