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This study first examined the kinetic changes of fiber carboxyl group content in bulk fiber, polysaccharide, and residual lignin of oxygen delignified pulps during one-stage oxygen delignification of a low kappa (32.5) kraft pulp. The carboxyl group contents determined in different chemical components of oxygen delignified pulps was used to establish the distribution of carboxyl groups in lignin and pulp polysaccharide and decouple the responses from residual lignin and polysaccharide. Following this study, two high kappa (~ 49.0) SW kraft pulps prepared were delignified through two-stage oxygen delignification. Fiber carboxyl group profiles of these pulps were elucidated to investigate the effect of lignin content of incoming unbleached kraft pulps on fiber carboxyl group formation. Due to a limitation to enhance fiber carboxyl groups only by parameter optimization during one- and two- stage oxygen delignification, a catalytic oxidation program was developed to enhance fiber carboxyl groups by 52.2 116.0 % employing 0.10 - 0.18% of a bismuth ruthenium pyrochlore oxide catalyst during oxygen delignification. The mechanism of fiber carboxyl group formation through the catalytic oxidation was proposed. The main factor on carboxyl group formation in pulp carbohydrate was identified to follow the order: NaOH > oxygen pressure> reaction temperature through a 3-factor at 3-level (L933) orthogonal experimental design and the optimal conditions were found at 2.5% NaOH, 85-100 oC, and 800-960 kPa O2 during the catalytic oxidation. ECF bleaching study was also conducted on these pulps with higher amount of fiber carboxyl group enhanced at early pulping and oxygen delignification processes. The bleaching results demonstrated that the early-stage enhanced fiber carboxyl groups were partially retained through ECF bleaching. Additionally, fiber carboxyl groups of fully bleached kraft pulps were ~ 20% different from typical bleaching protocols, depending on bleaching chemicals used and the bleaching sequences such as DEDED, (D+C)EDED, ODEDD, and OQPZP. This study finally demonstrated that an increase of fiber carboxyl groups by 17.4-62.1% through chemical oxidation resulted in reduced fiber curl, increased fiber WRVs, 4.3-25.5 % increase in paper tensile index at comparable pulp viscosity; and 4.4 -30.1% increase in paper dry tensile stiffness.

No description available.

<p>This thesis addresses the mechanisms involved in cellulosedegradation in general and Totally Chlorine Free (TCF) bleachingof pulp in particular. The thesis shows that the cellulosedegradation during high consistency ozone bleaching is explainedby free radical chain reactions.</p><p>By simulation, it has been shown that the number, weight andviscosity average of liner polymer chain length can be used tocalculate the number of random scissions in a linear polymer ofany molecular weight distribution, provided that there is acalibrated Mark-Houwink equation. A model describing partialdegradation of molecular weight distributions of linear polymersmeasured with viscometry was developed and verifiedexperimentally. The model predicts viscometric measurement ofchemical cellulose degradation by a rapidly reacting reagent tobe strongly dependent on cellulose accessibility.</p><p>The role of free radical reactions in cellulose degradationwas studied by varying the amount of ferrous ions and ozone addedto the cotton linters. The result was compared to the resultsobtained from cellulose of lower crystallinity (cellulose beads)by measuring average chain length. When a ferryl ion reacted withcotton linters in the presence of ozone, the very formation ofone glycosidic radical was more significant to degradation thanthe final step of forming one oxidised glycoside. The inefficientdegradation observed of the oxidation step is explainable by theamount of accessible glycosides being too small to influenceviscometry. The efficient degradation observed in associationwith the glycosidic radical formation is explained by initiationof free radical chain reactions that are propagated as long asthere is ozone in the system. As none of these phenomena werefound in the less crystalline cellulose, cellulose structureappears to be important for how free radical mediated cellulosedegradation develops.</p><p>The theory of free radical chain reactions coupled withdiffusion suggests a concentric expansion of the chain reactionsoutwards from the initial site of radical formation duringozonation of carbohydrates. This was confirmed by demonstratingfree radical chain reactions spreading from a spot of initiationoutwards during ozonation of a filter paper, using a pH-indicatorto monitor acid formation. Furthermore, the interior and exteriorof cellulose fibres doped with initiator were shown to bepermeated by small holes after ozonation.</p><p>Ethylene glycol was shown to improve the selectivity duringozone bleaching of oxygen bleached kraft pulp at pH 3. Optimalconditions were obtained at pH 3 for 25 wt% ethylene glycol. Theinfluence of ethylene glycol on selectivity is explained by aproportion of the free radical chain reactions being carried bythe ethylene glycol instead of the cellulose during ozonebleaching. The observations were summarised in the form of amodel where the observed degradations for pulp, bleached pulp andcotton fibres during both ozone bleaching and ethylene glycolassisted ozone bleaching were shown to agree with each other.</p><p>From g-irradiation of ozonised aqueous solutions of alcohol,the rate constant of superoxide formation from the peroxylradical of methanol was estimated to be 10 s^-1. Rate constants of the reactions between ozone andalkylperoxyl radicals were determined to be around 10⁴M^-1s^-1. The possibility of the reaction betweenalkylperoxyl radicals and ozone contributing significantly tofree radical chain reactions during ozonation of carbohydratesand alcohols could therefore be ruled out.</p><p>Cellulose, degradation, free radical, ozone, selectivity,ethylene glycol, alcohol, bleaching, kraft pulp, cotton linters,delignification, fibre, fibril, crystallinity, ferryl ion, freeradical chain reactions, TCF, viscometry, molecular weightdistributions, random scissions.</p>

Thesis (Ph. D.)--Institute of Paper Chemistry, 1958. / Includes bibliographical references (p. 87-90).

The variability of water-column absorption due to colored dissolved organic matter (CDOM) and phytoplankton in coral reef regions is the focus of this study. Hydrographic and CDOM absorption measurements made on the Bahamas Banks and in Exuma Sound during the spring of 1999 and 2000 showed that values of salinity and CDOM absorption at 440nm were higher on the banks (37.18 psu, 0.06 m^-1), compared to Exuma Sound (37.04 psu, 0.03 m^-1). Spatial patterns of CDOM absorption in Exuma Sound revealed that plumes of CDOM-rich water flow into Exuma Sound from the surrounding banks. To examine absorption variability in reef regions throughout the world, a thirteen-year time series of satellite-derived estimates of water-column absorption due to CDOM and phytoplankton were created from Sea-viewing Wide Field-of-view Sensor (SeaWiFS) and Moderate Resolution Imaging Spectroradiometer (MODIS) data. Time series data extracted adjacent to coral reef regions showed that variability in absorption depends on oceanographic conditions such as circulation patterns and winds as well as proximity to sources of light-absorbing materials that enter the water column, such as from terrestrial runoff. Waters near reef regions are generally clear, exhibiting a lower "baseline" level of CDOM absorption of approximately 0.01 m^-1 at 443nm. The main differences between regions lie in the periods during the year when increased levels of absorption are observed, which can be triggered by inputs of terrestrially-derived material, as in the Great Barrier Reef lagoon, or wind-driven upwelling as in the Andaman Sea and eastern Pacific Ocean near Panama. The lowest CDOM absorption levels found were approximately 0.003 m^-1 at 443nm near the islands of Palau and Yap, which are removed from sources of colored materials. The highest absorption levels near reefs were associated with wind-driven upwelling during the northeast monsoon on the Andaman coast of Thailand where values of CDOM absorption at 443nm reached 0.7 m^-1. Simulations of the underwater light field based on satellite-derived absorption values revealed that changes in absorption have a strong influence on light levels to which corals are exposed, particularly in the ultraviolet region of the spectrum, where CDOM is the primary absorber of light. Episodes of coral bleaching during 1998 and 2002 were found to be associated with elevated seawater temperatures as well as decreased levels of CDOM absorption, indicating that corals were exposed to light stress along with thermal stress during periods of bleaching.

Coral reefs are greatly impacted by the physical characteristics of the water surrounding them. Incidence and severity of mass coral bleaching and mortality events are increasing worldwide due primarily to increased water temperature, but also in response to other stressors. This decline in reef health demands clearer understanding of the compounding effects of multiple stressors, as well as widespread assessment of coral reef health in near-real time. Satellites offer a means by which some of the physical stressors on coral reefs can be measured. The synoptic spatial coverage and high repeat sampling frequency of such instruments allow for a quantity of data unattainable by in situ measurements. Unfortunately, errors in cloudmasking algorithms contaminate satellite derived sea surface temperature (SST) measurements, especially during anomalously cold events. Similarly, benthic interference of satellite-derived reflectance signals has resulted in large errors in derivations of water quality or clarity in coral reef environments. This work provides solutions to these issues for the coral reef environments of the Florida Keys. Specifically, improved SST cloudmasking algorithms were developed for both Advanced Very High Resolution Radiometer (AVHRR; Appendix A) and Moderate Resolution Imaging Spectroradiometer (MODIS) data (Appendix B). Both of these improved algorithms were used to reveal the extent and severity of a January 2010 cold event that resulted in widespread mortality of Florida Keys corals. Applied to SST data from 2010, the improved MODIS cloudmasking algorithm also showed improved quantity of SST retrievals with minimal sacrifice in data quality. Two separate algorithms to derive water clarity from MODIS measurements of optically shallow waters were developed and validated, one focusing on the diffuse downwelling attenuation coefficient (Kd, m-1) in visible bands (Appendix C), the other on Kd in the ultraviolet (Appendix D). The former utilized a semi-analytical approach to remove bottom influence, modified from an existing algorithm. The latter relied on empirical relationships between an extensive in situ training dataset and variations in MODIS-derived spectral shape, determined using a stepwise principal components regression. Both of these algorithms showed satisfactory validation statistics, and were used to elucidate spatiotemporal patterns of water clarity in the Florida Keys. Finally, an approach was developed to use Landsat data to detect concurrent MODIS-derived reflectance anomalies with over 90% accuracy (Appendix E). Application of this approach to historical Landsat data allowed for long-term, synoptic assessment of the water environment of the Florida Keys ecosystem. Using this approach, shifts in seagrass density, turbidity increases, black water events, and phytoplankton blooms were detected using Landsat data and corroborated with known environmental events. Many of these satellite data products were combined with in situ reports of coral bleaching to determine the specific environmental parameters individually and synergistically contributing to coral bleaching. As such, SST and visible light penetration were found to be parsimoniously explaining variance in bleaching intensity, as were the interactions between SST, wind and UV penetration. These relationships were subsequently used to create a predictive model for coral bleaching via canonical analysis of principal coordinates. Leave-one-out-cross-validation indicated that this model predicted `severe bleaching' and `no bleaching' conditions with 64% and 60% classification success, respectively, nearly 3 times greater than that predicted by chance. This model also showed improvement over similar models created using only temperature data, further indicating that satellite assessment of coral bleaching based only on SST data can be improved with other environmental data. Future work should further supplement the environmental parameters considered in this research with databases of other coral stressors, as well as improved quantification of the temperature at the depth of corals, in order to gain a more complete understanding of coral bleaching in response to environmental stress. Overall, this dissertation presents five new algorithms to the field of satellite oceanography research. Although validated primarily in the Florida Keys region, most of these algorithms should be directly applicable for use in other coastal environments. Identification of the specific environmental factors contributing to coral bleaching enhances understanding of the interplay between multiple causes of reef decline, while the predictive model for coral bleaching may provide researchers and managers with widespread, near real-time assessments of coral reef health.