Quantitative characterization of physico-chemical properties of the active layers of reverse osmosis and nanofiltration membranes, and their relation to membrane performance

The main objectives of this dissertation were: (i) to develop experimental and analytical procedures to quantify different physico-chemical properties of the ultra-thin (~ 100 nm) active layers of reverse osmosis (RO) and nanofiltration (NF) membranes and their interactions with contaminants; (ii) to use such procedures to evaluate the similarities and differences between the active layers of different RO/NF membranes; and (iii) to relate characterization results to membrane performance. Such objectives were motivated by the current limited understanding of the physico-chemical properties of active layers as a result of traditional characterization techniques having limitations associated with the nanometer-scale spatial resolution required to study these ultra-thin films. Functional groups were chosen as the main active layer property of interest. Specific accomplishments of this study include the development of procedures to quantify in active layers as a function of pH: (1) the concentration of both negatively and positively ionized functional groups; (2) the stoichiometry of association between ions (i.e., barium) and ionized functional groups (i.e., carboxylate and sulfonate); and (3) the steric effects experienced by ions (i.e., barium). Conceptual and mathematical models were developed to describe experimental results. The depth heterogeneity of the active layer physico-chemical properties and interactions with contaminants studied in this dissertation was also characterized. Additionally, measured concentrations of ionized functional groups in the polyamide active layers of several commercial RO/NF membranes were used as input in a simplified RO/NF transport model to predict the rejection of a strong electrolyte (i.e., potassium iodide) and a weak acid (i.e., arsenious acid) at different pH values based on rejection results at one pH condition. The good agreement between predicted and experimental results showed that the characterization procedures developed in this study serve as useful tools in the advancement of the understanding of the properties and structure of the active layers of RO/NF membranes, and the mechanisms of contaminant transport through them.

Gait analysis of the hind limb in Labrador Retrievers with and without cranial cruciate ligament disease

Cranial cruciate ligament (CCL) deficiency is the leading cause of lameness affecting the stifle joints of large breed dogs, especially Labrador Retrievers. Although CCL disease has been studied extensively, its exact pathogenesis and the primary cause leading to CCL rupture remain controversial. However, weakening secondary to repetitive microtrauma is currently believed to cause the majority of CCL instabilities diagnosed in dogs. Techniques of gait analysis have become the most productive tools to investigate normal and pathological gait in human and veterinary subjects. The inverse dynamics analysis approach models the limb as a series of connected linkages and integrates morphometric data to yield information about the net joint moment, patterns of muscle power and joint reaction forces. The results of these studies have greatly advanced our understanding of the pathogenesis of joint diseases in humans. A muscular imbalance between the hamstring and quadriceps muscles has been suggested as a cause for anterior cruciate ligament rupture in female athletes. Based on these findings, neuromuscular training programs leading to a relative risk reduction of up to 80% has been designed. In spite of the cost and morbidity associated with CCL disease and its management, very few studies have focused on the inverse dynamics gait analysis of this condition in dogs. The general goals of this research were (1) to further define gait mechanism in Labrador Retrievers with and without CCL-deficiency, (2) to identify individual dogs that are susceptible to CCL disease, and (3) to characterize their gait. The mass, location of the center of mass (COM), and mass moment of inertia of hind limb segments were calculated using a noninvasive method based on computerized tomography of normal and CCL-deficient Labrador Retrievers. Regression models were developed to determine predictive equations to estimate body segment parameters on the basis of simple morphometric measurements, providing a basis for nonterminal studies of inverse dynamics of the hind limbs in Labrador Retrievers. Kinematic, ground reaction forces (GRF) and morphometric data were combined in an inverse dynamics approach to compute hock, stifle and hip net moments, powers and joint reaction forces (JRF) while trotting in normal, CCL-deficient or sound contralateral limbs. Reductions in joint moment, power, and loads observed in CCL-deficient limbs were interpreted as modifications adopted to reduce or avoid painful mobilization of the injured stifle joint. Lameness resulting from CCL disease affected predominantly reaction forces during the braking phase and the extension during push-off. Kinetics also identified a greater joint moment and power of the contralateral limbs compared with normal, particularly of the stifle extensor muscles group, which may correlate with the lameness observed, but also with the predisposition of contralateral limbs to CCL deficiency in dogs. For the first time, surface EMG patterns of major hind limb muscles during trotting gait of healthy Labrador Retrievers were characterized and compared with kinetic and kinematic data of the stifle joint. The use of surface EMG highlighted the co-contraction patterns of the muscles around the stifle joint, which were documented during transition periods between flexion and extension of the joint, but also during the flexion observed in the weight bearing phase. Identification of possible differences in EMG activation characteristics between healthy patients and dogs with or predisposed to orthopedic and neurological disease may help understanding the neuromuscular abnormality and gait mechanics of such disorders in the future. Conformation parameters, obtained from femoral and tibial radiographs, hind limb CT images, and dual-energy X-ray absorptiometry, of hind limbs predisposed to CCL deficiency were compared with the conformation parameters from hind limbs at low risk. A combination of tibial plateau angle and femoral anteversion angle measured on radiographs was determined optimal for discriminating predisposed and non-predisposed limbs for CCL disease in Labrador Retrievers using a receiver operating characteristic curve analysis method. In the future, the tibial plateau angle (TPA) and femoral anteversion angle (FAA) may be used to screen dogs suspected of being susceptible to CCL disease. Last, kinematics and kinetics across the hock, stifle and hip joints in Labrador Retrievers presumed to be at low risk based on their radiographic TPA and FAA were compared to gait data from dogs presumed to be predisposed to CCL disease for overground and treadmill trotting gait. For overground trials, extensor moment at the hock and energy generated around the hock and stifle joints were increased in predisposed limbs compared to non predisposed limbs. For treadmill trials, dogs qualified as predisposed to CCL disease held their stifle at a greater degree of flexion, extended their hock less, and generated more energy around the stifle joints while trotting on a treadmill compared with dogs at low risk. This characterization of the gait mechanics of Labrador Retrievers at low risk or predisposed to CCL disease may help developing and monitoring preventive exercise programs to decrease gastrocnemius dominance and strengthened the hamstring muscle group.

The interpersonal and mental health implications of the coherence of coming out narratives for a sample of gay men in committed romantic relationships

The coming out process has been conceptualized as a developmental imperative for those who will eventually accept their same-sex attractions. It is widely accepted that homophobia, heterosexism, and homonegativity are cultural realities that may complicate this developmental process for gay men. The current study views coming out as an extra-developmental life task that is at best a stressful event, and at worst traumatic when coming out results in the rupture of salient relationships with parents, siblings, and/or close friends. To date, the minority stress model (Meyer, 1995; 2003) has been utilized as an organizing framework for how to empirically examine external stressors and mental health disparities for lesbians, gay men, and bisexual individuals in the United States. The current study builds on this literature by focusing on the influence of how gay men make sense of and represent the coming out process in a semi-structured interview, more specifically, by examining the legacy of the coming out process on indicators of wellness. In a two-part process, this study first employs the framework well articulated in the adult attachment literature of coherence of narratives to explore both variation and implications of the coming out experience for a sample of gay men (n = 60) in romantic relationships (n = 30). In particular, this study employed constructs identified in the adult attachment literature, namely Preoccupied and Dismissing current state of mind, to code a Coming Out Interview (COI). In the present study current state of mind refers to the degree of coherent discourse produced about coming out experiences as relayed during the COI. Multilevel analyses tested the extent to which these COI dimensions, as revealed through an analysis of coming out narratives in the COI, were associated with relationship quality, including self-reported satisfaction and observed emotional tone in a standard laboratory interaction task and self-reported symptoms of psychopathology. In addition, multilevel analyses also assessed the Acceptance by primary relationship figures at the time of disclosure, as well as the degree of Outness at the time of the study. Results revealed that participant’s narratives on the COI varied with regard to Preoccupied and Dismissing current state of mind, suggesting that the AAI coding system provides a viable organizing framework for extracting meaning from coming out narratives as related to attachment relevant constructs. Multilevel modeling revealed construct validity of the attachment dimensions assessed via the COI; attachment (i.e., Preoccupied and Dismissing current state of mind) as assessed via the Adult Attachment Interview (AAI) was significantly correlated with the corresponding COI variables. These finding suggest both methodological and conceptual convergence between these two measures. However, with one exception, COI Preoccupied and Dismissing current state of mind did not predict relationship outcomes or self-reported internalizing and externalizing symptoms. However, further analyses revealed that the degree to which one is out to others moderated the relationship between COI Preoccupied and internalizing. Specifically, for those who were less out to others, there was a significant and positive relationship between Preoccupied current state of mind towards coming out and internalizing symptoms. In addition, the degree of perceived acceptance of sexual orientation by salient relationship figures at the time of disclosure emerged as a predictor of mental health. In particular, Acceptance was significantly negatively related to internalizing symptoms. Overall, the results offer preliminary support that gay men’s narratives do reflect variation as assessed by attachment dimensions and highlights the role of Acceptance by salient relationship figures at the time of disclosure. Still, for the most part, current state of mind towards coming out in this study was not associated with relationship quality and self-reported indicators of mental health. This finding may be a function of low statistical power given the modest sample size. However, the relationship between Preoccupied current state of mind and mental health (i.e., internalizing) appears to depend on degree of Outness. In addition, the response of primary relationships figures to coming out may be a relevant factor in shaping mental health outcomes for gay men. Limitations and suggestions for future research and clinical intervention are offered.