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Thesis (M.S.)--West Virginia University, 2010. / Title from document title page. Document formatted into pages; contains viii, 109 p. : col. ill., col. maps. Includes abstract. Includes bibliographical references (p. 54-62).

Ocean salinity is a renewable energy source that has not been recognized and could provide an opportunity to capture significant amount of clean energy when it mixes with river water. One of the processes emerging as a sustainable method for capturing energy from seawater is reverse electrodialysis (RED), which generates power via the transport of the positive and negative ions in the water through selective ion exchange membranes (IEMs). RED power generation is relatively close to commercialization, but its application is often limited by system power efficiency in natural water conditions. Although various types of salt ions exist in environmental saline water, most efforts have been focused on sodium chloride as a single ionic source in the water and the effects of other common multivalent ions (e.g., magnesium and sulfate) on power generation remain unexplored. Moreover, the commercial feasibility of RED is highly challenged by the absence of specialized RED membranes. Currently available IEMs are not optimized for RED power conversion systems, but successful operation is highly dependent on the membranes used. Major advances in manufacturing of proper IEMs will be a critical pathway to accelerate large-scale energy conversion by RED. Therefore, this study aimed at advancing our understanding of the RED power system for efficient and stable salinity gradient energy generation. Specifically, it is comprised of three parts. First, a mathematical model is developed for three different monovalent and multivalent ion combinations to determine the effect of different ionic compositions of the feed solution on the power density. Efforts are further made to optimize the RED system with respect to improving power density by investigating the sensitivity of key response parameters such as flow rate ratios and intermembrane distance ratios. Second, novel organic-inorganic nanocomposite cation exchange membranes (CEMs) are synthesized for RED application by introducing functionalized inorganic materials into an organic polymer matrix. The effect of inorganic particle filler loading within the organic polymer matrix on physico- and electrochemical performance is investigated. The results revealed that the increase of functionalized nanoparticle loading controls the effective ion transport in the membrane structure and there exists an optimum amount of nanoparticles (i.e., charged groups), which performs the best in selectively exchanging counter-ions, while excluding co-ionic species. Third, the membrane structure modification is demonstrated to enhance ion transport while maintaining large surface-charged functional groups in the polymer matrix. We have synthesized custom nanocomposite CEMs to tailor porous membrane structures of various thicknesses, aging (evaporation) time, and inorganic nanoparticle loadings. We have further tailored the membrane structure by incorporating different inorganic particle filler sizes. These engineered design approaches are found to be highly effective in obtaining desired physico- and electrochemical properties, which allowed higher ionic current flow throughout the system. Furthermore, for the first time we showed the successful application of tailor-made nanocomposite CEMs in a RED stack and achieved superb power density, which exceeds the power output obtained with the commercially available membranes. In summary, this dissertation has advanced our understanding of salinity gradient energy generation using RED technique. Specifically, computational modeling and simulation study investigates the development and optimization approaches of the RED process for practical application of RED using natural water conditions. Furthermore, the RED membranes developed in this dissertation focuses on fabrication, characterization, and optimization of cation exchange membranes. Overall, the results of this study are anticipated to benefit the future optimization of energy-capturing mechanisms in RED and provide the better pathway for the sustainable salinity gradient power generation.

Petroleum and Geosystems Engineering / Low salinity waterflooding is an emerging enhanced oil recovery (EOR) technique in which the salinity of the injected water is substantially reduced to improve oil recovery over conventional higher salinity waterflooding. Although there are many low salinity experimental results reported in the literature, publications on modeling this process are rare. While there remains some debate about the mechanisms of low salinity waterflooding, the geochemical reactions that control the wetting of crude oil on the rock are likely to be central to a detailed description of the process. Since no comprehensive geochemical-based modeling has been applied in this area, we decided to couple a state-of-the-art geochemical package, IPhreeqc, developed by the United States Geological Survey (USGS) with UTCOMP, the compositional reservoir simulator developed at the Center for Petroleum and Geosystems Engineering in The University of Texas at Austin. A step-by-step algorithm is presented for integrating IPhreeqc with UTCOMP. Through this coupling, we are able to simulate homogeneous and heterogeneous (mineral dissolution/precipitation), irreversible, and ion-exchange reactions under non-isothermal, non-isobaric and both local-equilibrium and kinetic conditions. Consistent with the literature, there are significant effects of water-soluble hydrocarbon components (e.g., CO2, CH4, and acidic/basic components of the crude) on buffering the aqueous pH and more generally, on the crude oil, brine, and rock reactions. Thermodynamic constrains are used to explicitly include the effect of these water-soluble hydrocarbon components. Hence, this combines the geochemical power of IPhreeqc with the important aspects of hydrocarbon flow and compositional effects to produce a robust, flexible, and accurate integrated tool capable of including the reactions needed to mechanistically model low salinity waterflooding. The geochemical module of UTCOMP-IPhreeqc is further parallelized to enable large scale reservoir simulation applications. We hypothesize that the total ionic strength of the solution is the controlling factor of the wettability alteration due to low salinity waterflooding in sandstone reservoirs. Hence, a model based on the interpolating relative permeability and capillary pressure as a function of total ionic strength is implemented in the UTCOMP-IPhreeqc simulator. We then use our integrated simulator to match and interpret a low salinity experiment published by Kozaki (2012) (conducted on the Berea sandstone core) and the field trial done by BP at the Endicott field (sandstone reservoir). On the other hand, we believe that during the modified salinity waterflooding in carbonate reservoirs, calcite is dissolved and it liberates the adsorbed oil from the surface; hence, fresh surface with the wettability towards more water-wet is created. Therefore, we model wettability to be dynamically altered as a function of calcite dissolution in UTCOMP-IPhreeqc. We then apply our integrated simulator to model not only the oil recovery but also the entire produced ion histories of a recently published coreflood by Chandrasekhar and Mohanty (2013) on a carbonate core. We also couple IPhreeqc with UTCHEM, an in-house research chemical flooding reservoir simulator developed at The University of Texas at Austin, for a mechanistic integrated simulator to model alkaline/surfactant/polymer (ASP) floods. UTCHEM has a comprehensive three phase (water, oil, microemulsion) flash calculation package for the mixture of surfactant and soap as a function of salinity, temperature, and co-solvent concentration. Similar to UTCOMP-IPhreeqc, we parallelize the geochemical module of UTCHEM-IPhreeqc. Finally, we show how apply the integrated tool, UTCHEM-IPhreeqc, to match three different reaction-related chemical flooding processes: ASP flooding in an acidic active crude oil, ASP flooding in a non-acidic crude oil, and alkaline/co-solvent/polymer (ACP) flooding. / text

Four clones of jojoba, Simmondsia chinensis (link, Schneider, were used to study the effects of salinity on the growth and physiological processes of jojoba. The vegetative growth as measured by shoot elongation, new branch development, node number, leaf expansion, new leaf production, and defoliation was studied using an iso-molar mixture of NaCl + CaCl₂ at -2, -4, -8, and -16 bars. Physiological processes including chlorophyll concentrations, CO₂ exchange rates, stomatal resistances, leaf water potentials, relative water content, leaf succulence, specific leaf weight, proline accumulation, and protein concentrations were measured at weekly intervals after the addition of salts. Twenty four days after exposure to salinity, plants were transferred to control solution in order to study the reversibility of the salt effects on jojoba. The inhibitory effects of salinity on shoot elongation was evident at -16 bars after 23 days of exposure to salinity. The number of new branches developed during the treatment period did not differ, however, the number of nodes formed on the new branches was less than that of the control. Leaf expansion was inhibited at -4, -8 and -16 bars. Leaf production was significantly reduced at -16 bars and it recovered during stress-release period. Leaf drop (defoliation) increased with increasing salinity. The inhibitory effects of salinity on jojoba's growth was reversible except for leaf expansion. Total chlorophyll concentrations were significantly reduced at 4 salinity levels and chlorophyll synthesis did not recover at -4, -8 and -16 bars during the stress-release period. CO₂ exchange processes including apparent photosynthesis, dark respiration, light respiration, and gross photosynthesis were not significantly affected up to -8 bars. However, at -16 bars, apparent photosynthesis and gross photosynthesis were reduced. Dark respiration was not affected significantly, however, light respiration was reduced at -4, -8, and -16 bars after 16 days of exposure to salinity. This reduction was due to the loss of the post-illumination burst of CO₂. It was concluded that the theory of growth suppression due to accelerated respiration is not true for jojoba. Therefore, the decreased rate of apparent photosynthesis could be attributed to the increased stomatal resistances which increased dramatically at -16 bars. Leaf water potentials were markedly reduced at -16 bars for 23 days which indicated a possible osmotic adjustment and jojoba's ability to tolerate higher salinity levels. Although the leaves produced during the treatment period did not show severe damage symptoms, however, frequent tip burn of the younger leaves at -16 bars indicated that -16 bars was near the salinity limit for jojoba. Leaf relative water content was reduced markedly at -8 and -16 bars which was correlated with leaf water potentials. Leaf succulence based on the ratio of fresh weight/dry weight and specific leaf weight were significantly increased at -16 bars. Increases in specific leaf weight which correlated with succulence, indicates that it was a function of increased leaf succulence and water accumulation. Free proline accumulated in response to salinity. However, there was no significant increase in proline levels until 23 days of exposure to -16 bars. Proline levels rapidly decreased to the control level during the stress-release period. It is believed that the accumulation of proline in jojoba does not function in osmotic regulation because of its low accumulation. Total protein concentrations were found to decrease due to high salinity levels (-16 bars). Although protein synthesis increased during the stress-release period, however, at -16 bars, no significant recovery was evident which indicated that the inhibition of protein synthesis rather than its breakdown was caused by high salt concentrations.

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This thesis uses a range of different size spectra to compare contrasting benthic habitats in the aquatic realm. Temporal and spatial variation in benthic size spectra were investigated across a full salinity gradient (i.e. from freshwater, through estuarine to marine) in the River Yealm, south Devon, in order to gauge the influence of large differences in taxonomy and evolutionary history. Abundance and biomass size spectra showed a similar pattern among sites in all seasons but winter, suggesting that the size structure of benthic communities may be similar in sites with very different community compositions. A subsequent study comparing size spectra across salinity by employing artificial substrata suggested that substratum type also had little effect on the size structure of these benthic communities. A technique was developed for obtaining microbial size distributions for benthic communities and showed that microbial size structures were also similar between the marine and freshwater sites within the Yealm system. A final study demonstrated that the shape of size spectra was clearly affected by metal contamination. Size spectra across a salinity gradient -(i.e. from freshwater to lower estuary) in the highly contaminated Fal system were very different to those in the uncontaminated Yealm, due mostly to the low macrofaunal abundance in the former. This thesis is the first to assess patterns in benthic size spectra across a full salinity range in the same system. It is hoped that it will provide a base line for further studies in this exciting research area in macroecology and that biomass spectra might also prove useful as metrics for biomonitoring.

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Wild Hordeum species, from the four genome groups of X, H, I and Y, were assessed for physiological traits associated with tolerance to salinity and waterlogging. When grown in saline conditions, a number of wild Hordeum species had exceptional ‘exclusion’ of Na+ and Cl- from the young leaves, and also maintained tissue K+ concentrations, compared with Hordum vulgare ssp. vulgare (cv. ‘Golf’). For example, at 150 mol m-3 NaCl, the K+:Na+ in youngest, fully expanded leaf blades of wild Hordeum species averaged 5.2, compared with 0.8 in H. vulgare. H. marinum was more salt tolerant than H. vulgare, with a relative growth rate 30% higher than H. vulgare at 150 mol m-3 NaCl. At 300 mol m-3 NaCl, glycinebetaine plus proline contributed to 15% of πsap in expanding leaf blades of H. marinum, compared with 8% in H. vulgare. When grown in stagnant conditions, 16 accessions (approximately half of those evaluated) formed a barrier to radial O2 loss (ROL) in basal zones of adventitious roots. In the Triticeae, this trait had previously only been described in one species, H. marinum. The barrier to ROL occurred only in accessions from wetland or intermediate habitats, and was also related to genome type, being present in accessions with the X or the H genome (Hordeum vulgare has the I genome). In stagnant conditions, aerenchyma formed was, on average; 22% in accessions with the X genome; 19% in those with the H genome; and 15 and 16% in those with the I or the Y genomes, respectively. The combination of a barrier to ROL and aerenchyma enhances longitudinal O2 movement in adventitious roots, permitting roots to penetrate deeper into anaerobic substrates. In H. marinum, induction of the barrier to ROL was associated with a 97% reduction in apparent O2 diffusivity across the external layers of the basal zones of roots, compared with near the root tip. The barrier results from physical resistance to radial O2 movement, although when roots were cooled to suppress respiration some additional leakage of O2 was detected, indicating respiration also contributes to the low rates of ROL from the basal regions of roots. Low radial O2 permeability in the roots of stagnantly-treated H. marinum was associated with secondary thickening, putatively lignin or suberin deposits, in the hypodermis. These changes in root structure, however, did not influence root hydraulic conductivity, assessed for individual adventitious roots and whole root systems. Thus, diversity amongst Hordeum species in expression of traits for tolerance to waterlogging (an inducible barrier to ROL and aerenchyma) and salinity (Na+ and Cl- ‘exclusion’) were documented in this study. Traits for root aeration did not compromise the capacity of roots to take up water, presumably being of importance for growth in soils with fluctuating water levels (i.e. wet/dry cycles). The high degree of salinity tolerance in several Hordeum species, and especially in H. marinum, is consistent with field observations that these species occur in salt affected areas