A novel population balance model for the dilute acid hydrolysis of hemicellulose

Acid hydrolysis is a popular pretreatment for removing hemicellulose from lignocelluloses in order to produce a digestible substrate for enzymatic saccharification. In this work, a novel model for the dilute acid hydrolysis of hemicellulose within sugarcane bagasse is presented and calibrated against experimental oligomer profiles. The efficacy of mathematical models as hydrolysis yield predictors and as vehicles for investigating the mechanisms of acid hydrolysis is also examined. Experimental xylose, oligomer (degree of polymerisation 2 to 6) and furfural yield profiles were obtained for bagasse under dilute acid hydrolysis conditions at temperatures ranging from 110C to 170C. Population balance kinetics, diffusion and porosity evolution were incorporated into a mathematical model of the acid hydrolysis of sugarcane bagasse. This model was able to produce a good fit to experimental xylose yield data with only three unknown kinetic parameters ka, kb and kd. However, fitting this same model to an expanded data set of oligomeric and furfural yield profiles did not successfully reproduce the experimental results. It was found that a ``hard-to-hydrolyse'' parameter, $\alpha$, was required in the model to ensure reproducibility of the experimental oligomer profiles at 110C, 125C and 140C. The parameters obtained through the fitting exercises at lower temperatures were able to be used to predict the oligomer profiles at 155C and 170C with promising results. The interpretation of kinetic parameters obtained by fitting a model to only a single set of data may be ambiguous. Although these parameters may correctly reproduce the data, they may not be indicative of the actual rate parameters, unless some care has been taken to ensure that the model describes the true mechanisms of acid hydrolysis. It is possible to challenge the robustness of the model by expanding the experimental data set and hence limiting the parameter space for the fitting parameters. The novel combination of ``hard-to-hydrolyse'' and population balance dynamics in the model presented here appears to stand up to such rigorous fitting constraints.

Rejected! The harmful effects of workgroup mistreatment and the moderating role of organisational norms

This program of research investigated the harmful effects of mistreatment by the workgroup, and the role of perceived rejection as a critical mediator linking mistreatment and outcomes. This research program had three primary purposes. First, the research aimed to examine the important role of workgroup mistreatment as an independent predictor of negative outcomes, over and above the influence of supervisor mistreatment. Second, the research aimed to examine the effect of perceived rejection as an explanatory variable linking workgroup mistreatment and outcomes. Finally, the moderating effect of organizational norms on the relationship between workgroup mistreatment and perceived rejection was examined. The relationships of interest were examined over four studies, using multiple methods of data collection, across part-time and full-time working samples. In Study 1 (Chapter 2), the independent role of workgroup mistreatment and the mediating role of perceived rejection were examined. One hundred and forty two part-time working participants took part in the study. The participants completed a questionnaire on workplace behaviors in their organizations. The results of hierarchical regression analyses revealed a strong harmful effect of workgroup mistreatment, independent of mistreatment by the supervisor. In addition, the results showed that perceived rejection fully mediated the relationship between workgroup mistreatment and depression and organizational based self esteem. The study highlighted that perceived rejection acts as a key underlying psychological mechanism involved in the effect of workgroup mistreatment. This study has been published in the Journal of Occupational Health Psychology. Study 2 and Study 3 were presented as one paper in Chapter 3. The aims of these two studies was to explore the effects of workgroup mistreatment on a wider range of individual and organizational level outcomes, and to provide further evidence of the mediating role of perceived rejection as observed in Study 1. The results from both studies demonstrated that workgroup mistreatment had a significant and independent role in predicting negative individual and organizational level outcomes, providing support for the findings of Study 1. In the first study, 189 participants received scenarios manipulating workgroup mistreatment and supervisor mistreatment. The results of hierarchical regression analyses revealed that workgroup mistreatment harmfully affected participants, over and above that of the supervisor. The results also demonstrated that perceived rejection mediated the positive relationships between workgroup mistreatment and depression and organizational deviance, and also the negative relationships between workgroup mistreatment and organizational based self esteem and organizational citizenship behaviors. The second study included an additional aim, to examine the moderating role of supportive organizational norms. Two hundred and twenty nine participants read scenarios that manipulated workgroup mistreatment, supervisor mistreatment and organizational norms. The results of hierarchical regression analyses revealed the significant harmful effects of workgroup mistreatment, over and above the influence of supervisor mistreatment. The results also revealed the mediating role of perceived rejection. The direct effect of positive organizational norms also emerged, consistent with previous research. In addition, the result revealed that employees who experienced supportive organizational norms were more likely to reconcile with their workgroup members after experiencing mistreatment compared to employees who experienced hostile organizational norms. Finally, an unexpected pattern on the key affective variables of depression and organizational based self esteem emerged, such that mistreatment led to more negative outcomes in the supportive norms condition than in the hostile condition, where employees appeared to be desensitized. This paper is currently under review at the Journal of Applied Social Psychology. In Study 4 (Chapter 4), the overall model of workplace mistreatment was tested on a sample of full-time workers in an applied setting. One hundred and seventy two adults took part in the study. Participants were required to evaluate their workplace regarding mistreatment and organizational norms and to report their own psychological, behavioral and organizational outcomes. The results revealed that workgroup mistreatment was associated with increased depression, stress and avoidance, over and above supervisor mistreatment. In addition, the results revealed that perceived rejection acted as an explanatory variable linking workgroup mistreatment to a number of outcomes. Furthermore, the moderating role of hostile organizational norms emerged on depression, stress, reconciliation and avoidance. This paper is currently under review at the Journal of Occupational Health Psychology. Overall, the four studies provided empirical support for the majority of the hypotheses. The effects were demonstrated for a range of psychological, behavioral, and organizational level outcomes, using multiple methods of data collection, across part-time and full-time workers. At the conclusion of the thesis (Chapter 5), an overall summary is provided of the findings across all four studies, practical and theoretical implications and research directions.

Back to normal: A retrospective, cross-sectional study of the multi-factorial determinants of normal birth in Queensland, Australia

Background Currently, care providers and policy-makers internationally are working to promote normal birth. In Australia, such initiatives are being implemented without any evidence of the prevalence or determinants of normal birth as a multidimensional construct. This study aimed to better understand the determinants of normal birth (defined as without induction of labour, epidural/spinal/general anaesthesia, forceps/vacuum, caesarean birth, or episiotomy) using secondary analyses of data from a population survey of women in Queensland, Australia. Methods Women who birthed in Queensland during a two-week period in 2009 were mailed a survey approximately three months after birth. Women (n=772) provided retrospective data on their pregnancy, labour and birth preferences and experiences, socio-demographic characteristics, and reproductive history. A series of logistic regressions were conducted to determine factors associated with having labour, having a vaginal birth, and having a normal birth. Findings Overall, 81.9% of women had labour, 66.4% had a vaginal birth, and 29.6% had a normal birth. After adjusting for other significant factors, women had significantly higher odds of having labour if they birthed in a public hospital and had a pre-existing preference for a vaginal birth. Of women who had labour, 80.8% had a vaginal birth. Women who had labour had significantly higher odds of having a vaginal birth if they attended antenatal classes, did not have continuous fetal monitoring, felt able to ‘take their time’ in labour, and had a pre-existing preference for a vaginal birth. Of women who had a vaginal birth, 44.7% had a normal birth. Women who had a vaginal birth had significantly higher odds of having a normal birth if they birthed in a public hospital, birthed outside regular business hours, had mobility in labour, did not have continuous fetal monitoring, and were non-supine during birth. Conclusions These findings provide a strong foundation on which to base resources aimed at increasing informed decision-making for maternity care consumers, providers, and policy-makers alike. Research to evaluate the impact of modifying key clinical practices (e.g., supporting women׳s mobility during labour, facilitating non-supine positioning during birth) on the likelihood of a normal birth is an important next step.