Short-term temporal and spatial variations in physical, optical and biogeochemical parameters in June of 2013 in Alfacs Bay (NW Mediterranean)

With the aim of analyzing the complex physical and biogeochemical interactions at high temporal and spatial resolution in the complex estuarine waters of Alfacs Bay, a beam attenuation-based approach was used as optical proxy of different biogeochemical variables. Thus, the dataset contains the attenuation proxies as well as laboratory results from the analysis of water samples, which were used to validate our approach. In addition, the major physical forcing in the Bay was also measured.

(Table 3, page 8) Chemical composition and physical cahracteristics of manganese nodules from the Pacific Ocean

This paper reviews the state of the art in processing and extraction of ocean floor manganese nodules. It briefly reviews the mining sites where the abundant rich nodules occur and also discusses the metal distribution in nodules in view of economical processing and extraction of these metal values. The paper discloses in a detailed manner the physical and chemical characteristics of nodules, including porosity, surface area, water content and the effect of temperature on crystal structure of major constituents of nodules. In the extraction aspect of nodules, the paper reviews two different extraction schemes revealed in the literature, namely hydrometallurgical treatment and pyrometallurgical treatment. The hydrometallurgical treatments include acid leaching, ammonia leaching, leaching with reducing agents and leaching after high temperature pre-treatments such as in sulfating rousting, while the pyrometallurgical processes include smelting, chlorination-vaporization and segregation. The paper also covers metal recovery processes from leach liquor. An economic survey of processing nodules has been made in terms of problems associated with metal-marketing, and impact of metal production from nodules on mineral industries.

Impact of natural and/or chemical stressors on the freeze-tolerant and euryhaline enchytraeid, Enchytraeus albidus

Rapid climatic changes are taking place in Arctic, subarctic and cold temperate regions, where predictions point to an increase in freeze-thaw events, changes in precipitation, evaporation and salinity patterns. Climate change may therefore result in large impacts in ecosystem functioning and dynamics, especially in the presence of contaminants due to intense anthropogenic activities. Even though multiple stress approaches have received increasing interest in the last decades, the number of such studies is limited. In particular, knowledge on the effect of freezethaw events and salinity fluctuations on ecotoxicology of soil invertebrates is lacking, especially important when considering supralittoral species. Therefore, the aim of this thesis was to investigate the effects of low temperature and salinity fluctuations, singly and in combination with contaminants, in the freeze-tolerant and euryhaline enchytraeid Enchytraeus albidus. The assessment of population level endpoints (survival and reproduction), along with physiological and biochemical parameters such as levels of cryoprotectants, ice/water content, oxidative stress biomarkers, cellular energy allocation, and tissue concentration of chemicals (when applied), provided new and valuable knowledge on the effects of selected physical and chemical stressors in E. albidus, and allowed the understanding of adjustments in the primary response mechanisms that enable worms to maintain homeostasis and survival in harsh environments such as polar and temperate-cold regions. The presence of moderate levels of salinity significantly increased freeze-tolerance (mainly evaluated as survival, cryoprotection and ice fraction) and reproduction of E. albidus. Moreover, it contributed to the readjustments of cryoprotectant levels, restoration of antioxidant levels and changed singnificantly the effect and uptake of chemicals (copper cadmium, carbendazim and 4-nonylphenol). Temperature fluctuations (simulated as daily freeze-thaw cycles, between -2ºC and -4ºC) caused substancial negative effect on survival of worms previsouly exposed to non-lethal concentrations of 4-nonylphenol, as compared with constant freezing (-4ºC) and control temperature (2ºC). The decrease in cryoprotectants, increase in energy consumption and the highest concentration of 4-nonylphenol in the tissues have highlighted the high energy requirements and level of toxicity experienced by worms exposed to the combined effect of contaminants and freezing-thawing events. The findings reported on this thesis demonstrate that natural (physical) and chemical stressors, singly or in combination, may alter the dynamics of E. albidus, affecting not only their survival and reproduction (and consequent presence/distribution) but also their physiological and biochemical adaptations. These alterations may lead to severe consequences for the functioning of the ecosystems along the Arctic, subarctic and cold temperate regions, where they play an important role for decomposition of dead organic matter. This thesis provides a scientific basis for improving the setting of safety factors for natural soil ecosystems, and to underline the integration of similar investigations in ecotoxicology, and eventually in risk assessment of contaminants.

Effects of electron-beam irradiation on chemical and antioxidation parameters of wild Macrolepiota procera dried samples

Mushrooms are very perishable foods due to their high susceptibility to moisture loss, changes in color and texture, or microbiological spoilage. Drying is considered as the most appropriate method to prevent these alterations, but it has some limitations, such as shrinkage, enzymatic and non-enzymatic browning reactions, and oxidation of lipids and vitamins. Irradiation might effectively attenuate the undesirable changes caused by drying process, ensuring also higher shelf-life of mushrooms and their decontamination [I]. In the present work, the combined effects of electron-beam irradiation (at 0, 0.5, 1 and 6 kGy doses) and storage time (at 0, 6 and 12 months) were evaluated and compared. Macrolepiota procera (Scop.) Singer wild samples were obtained in Tnis-os-Montes, in the Northeast of Portugal, and dried at 30 •c in an oven. Subsequently, the samples were divided in four groups: control (non-irradiated, 0 kGy); sample 1 (0.5 kGy); sample 2 (1 kGy) and sample 3 (6 kGy). The irradiation was performed at the lNCTInstitute of Nuclear Chemistry and Technology (lNCT), in Warsaw, Poland. Moisture, protein, fat, carbohydrates and ash were determined following standard procedures. Free sugars and tocopherols were determined by high performance liquid chromatography coupled to a refraction index detector (HPLC-RI) and a fluorescence detector, respectively; fatty acids were determined by gas-liquid chromatography with flame ionization detection (GC-FID). Antioxidant activity was evaluated in the methanolic extracts by in vitro assays measuring DPPH (1,1-diphenyl-2- picrylhydrazyl) radical scavenging activity, reducing power, inhibition of ~-carotene bleaching and inhibition oflipid peroxidation using thiobarbituric acid reactive substances (TBARS) assay. Total phenolics were also determined by the Folin-Ciocalteu assay. All the parameters showed a decrease tendency with storage time. Trehalose and y-tocopherol were preserved with 1 kGy dose. Electron-beam irradiation did not impart additional changes to most of the chemical and antioxidant parameters of M. procera dried samples. This is a very promising result, since electron-beam irradiation might attenuate most unwanted changes caused by drying, maintaining its long-term effectiveness.

INVESTIGATIVE COMPARISON OF TANK AND RECOVERED ASPHALT SAMPLES THROUGH PHYSICAL PERFORMANCE TESTING AND CHEMICAL ANALYSIS

Despite the development of improved performance test protocols by renowned researchers, there are still road networks which experience premature cracking and failure. One area of major concern in asphalt science and technology, especially in cold regions in Canada is thermal (low temperature) cracking. Usually right after winter periods, severe cracks are seen on poorly designed road networks. Quality assurance tests based on improved asphalt performance protocols have been implemented by government agencies to ensure that roads being constructed are at the required standard but asphalt binders that pass these quality assurance tests still crack prematurely. While it would be easy to question the competence of the quality assurance test protocols, it should be noted that performance tests which are being used and were repeated in this study, namely the extended bending beam rheometer (EBBR) test, double edge-notched tension test (DENT), dynamic shear rheometer (DSR) test and X-ray fluorescence (XRF) analysis have all been verified and proven to successfully predict asphalt pavement behaviour in the field. Hence this study looked to probe and test the quality and authenticity of the asphalt binders being used for road paving. This study covered thermal cracking and physical hardening phenomenon by comparing results from testing asphalt binder samples obtained from the storage ‘tank’ prior to paving (tank samples) and recovered samples for the same contracts with aim of explaining why asphalt binders that have passed quality assurance tests are still prone to fail prematurely. The study also attempted to find out if the short testing time and automated procedure of torsion bar experiments can replace the established but tedious procedure of the EBBR. In the end, it was discovered that significant differences in performance and composition exist between tank and recovered samples for the same contracts. Torsion bar experimental data also indicated some promise in predicting physical hardening.

A study into the permeability and compressibility of Australian bagasse pulp

This is an experimental study into the permeability and compressibility properties of bagasse pulp pads. Three experimental rigs were custom-built for this project. The experimental work is complemented by modelling work. Both the steady-state and dynamic behaviour of pulp pads are evaluated in the experimental and modelling components of this project. Bagasse, the fibrous residue that remains after sugar is extracted from sugarcane, is normally burnt in Australia to generate steam and electricity for the sugar factory. A study into bagasse pulp was motivated by the possibility of making highly value-added pulp products from bagasse for the financial benefit of sugarcane millers and growers. The bagasse pulp and paper industry is a multibillion dollar industry (1). Bagasse pulp could replace eucalypt pulp which is more widely used in the local production of paper products. An opportunity exists for replacing the large quantity of mainly generic paper products imported to Australia. This includes 949,000 tonnes of generic photocopier papers (2). The use of bagasse pulp for paper manufacture is the main application area of interest for this study. Bagasse contains a large quantity of short parenchyma cells called ‘pith’. Around 30% of the shortest fibres are removed from bagasse prior to pulping. Despite the ‘depithing’ operations in conventional bagasse pulp mills, a large amount of pith remains in the pulp. Amongst Australian paper producers there is a perception that the high quantity of short fibres in bagasse pulp leads to poor filtration behaviour at the wet-end of a paper machine. Bagasse pulp’s poor filtration behaviour reduces paper production rates and consequently revenue when compared to paper production using locally made eucalypt pulp. Pulp filtration can be characterised by two interacting factors; permeability and compressibility. Surprisingly, there has previously been very little rigorous investigation into neither bagasse pulp permeability nor compressibility. Only freeness testing of bagasse pulp has been published in the open literature. As a result, this study has focussed on a detailed investigation of the filtration properties of bagasse pulp pads. As part of this investigation, this study investigated three options for improving the permeability and compressibility properties of Australian bagasse pulp pads. Two options for further pre-treating depithed bagasse prior to pulping were considered. Firstly, bagasse was fractionated based on size. Two bagasse fractions were produced, ‘coarse’ and ‘medium’ bagasse fractions. Secondly, bagasse was collected after being processed on two types of juice extraction technology, i.e. from a sugar mill and from a sugar diffuser. Finally one method of post-treating the bagasse pulp was investigated. The effects of chemical additives, which are known to improve freeness, were also assessed for their effect on pulp pad permeability and compressibility. Pre-treated Australian bagasse pulp samples were compared with several benchmark pulp samples. A sample of commonly used kraft Eucalyptus globulus pulp was obtained. A sample of depithed Argentinean bagasse, which is used for commercial paper production, was also obtained. A sample of Australian bagasse which was depithed as per typical factory operations was also produced for benchmarking purposes. The steady-state pulp pad permeability and compressibility parameters were determined experimentally using two purpose-built experimental rigs. In reality, steady-state conditions do not exist on a paper machine. The permeability changes as the sheet compresses over time. Hence, a dynamic model was developed which uses the experimentally determined steady-state permeability and compressibility parameters as inputs. The filtration model was developed with a view to designing pulp processing equipment that is suitable specifically for bagasse pulp. The predicted results of the dynamic model were compared to experimental data. The effectiveness of a polymeric and microparticle chemical additives for improving the retention of short fibres and increasing the drainage rate of a bagasse pulp slurry was determined in a third purpose-built rig; a modified Dynamic Drainage Jar (DDJ). These chemical additives were then used in the making of a pulp pad, and their effect on the steady-state and dynamic permeability and compressibility of bagasse pulp pads was determined. The most important finding from this investigation was that Australian bagasse pulp was produced with higher permeability than eucalypt pulp, despite a higher overall content of short fibres. It is thought this research outcome could enable Australian paper producers to switch from eucalypt pulp to bagasse pulp without sacrificing paper machine productivity. It is thought that two factors contributed to the high permeability of the bagasse pulp pad. Firstly, thicker cell walls of the bagasse pulp fibres resulted in high fibre stiffness. Secondly, the bagasse pulp had a large proportion of fibres longer than 1.3 mm. These attributes helped to reinforce the pulp pad matrix. The steady-state permeability and compressibility parameters for the eucalypt pulp were consistent with those found by previous workers. It was also found that Australian pulp derived from the ‘coarse’ bagasse fraction had higher steady-state permeability than the ‘medium’ fraction. However, there was no difference between bagasse pulp originating from a diffuser or a mill. The bagasse pre-treatment options investigated in this study were not found to affect the steady-state compressibility parameters of a pulp pad. The dynamic filtration model was found to give predictions that were in good agreement with experimental data for pads made from samples of pretreated bagasse pulp, provided at least some pith was removed prior to pulping. Applying vacuum to a pulp slurry in the modified DDJ dramatically reduced the drainage time. At any level of vacuum, bagasse pulp benefitted from chemical additives as quantified by reduced drainage time and increased retention of short fibres. Using the modified DDJ, it was observed that under specific conditions, a benchmark depithed bagasse pulp drained more rapidly than the ‘coarse’ bagasse pulp. In steady-state permeability and compressibility experiments, the addition of chemical additives improved the pad permeability and compressibility of a benchmark bagasse pulp with a high quantity of short fibres. Importantly, this effect was not observed for the ‘coarse’ bagasse pulp. However, dynamic filtration experiments showed that there was also a small observable improvement in filtration for the ‘medium’ bagasse pulp. The mechanism of bagasse pulp pad consolidation appears to be by fibre realignment. Chemical additives assist to lubricate the consolidation process. This study was complemented by pulp physical and chemical property testing and a microscopy study. In addition to its high pulp pad permeability, ‘coarse’ bagasse pulp often (but not always) had superior physical properties than a benchmark depithed bagasse pulp.

Modulation of depth-dependent properties in tissue-engineered cartilage with a semi-permeable membrane and perfusion : a continuum model of matrix metabolism and transport

The functional properties of cartilaginous tissues are determined predominantly by the content, distribution, and organization of proteoglycan and collagen in the extracellular matrix. Extracellular matrix accumulates in tissue-engineered cartilage constructs by metabolism and transport of matrix molecules, processes that are modulated by physical and chemical factors. Constructs incubated under free-swelling conditions with freely permeable or highly permeable membranes exhibit symmetric surface regions of soft tissue. The variation in tissue properties with depth from the surfaces suggests the hypothesis that the transport processes mediated by the boundary conditions govern the distribution of proteoglycan in such constructs. A continuum model (DiMicco and Sah in Transport Porus Med 50:57-73, 2003) was extended to test the effects of membrane permeability and perfusion on proteoglycan accumulation in tissue-engineered cartilage. The concentrations of soluble, bound, and degraded proteoglycan were analyzed as functions of time, space, and non-dimensional parameters for several experimental configurations. The results of the model suggest that the boundary condition at the membrane surface and the rate of perfusion, described by non-dimensional parameters, are important determinants of the pattern of proteoglycan accumulation. With perfusion, the proteoglycan profile is skewed, and decreases or increases in magnitude depending on the level of flow-based stimulation. Utilization of a semi-permeable membrane with or without unidirectional flow may lead to tissues with depth-increasing proteoglycan content, resembling native articular cartilage.

Stochastic chemical kinetics and the quasi-steady-state assumption : application to the stochastic simulation algorithm and chemical master equation

Recently the application of the quasi-steady-state approximation (QSSA) to the stochastic simulation algorithm (SSA) was suggested for the purpose of speeding up stochastic simulations of chemical systems that involve both relatively fast and slow chemical reactions [Rao and Arkin, J. Chem. Phys. 118, 4999 (2003)] and further work has led to the nested and slow-scale SSA. Improved numerical efficiency is obtained by respecting the vastly different time scales characterizing the system and then by advancing only the slow reactions exactly, based on a suitable approximation to the fast reactions. We considerably extend these works by applying the QSSA to numerical methods for the direct solution of the chemical master equation (CME) and, in particular, to the finite state projection algorithm [Munsky and Khammash, J. Chem. Phys. 124, 044104 (2006)], in conjunction with Krylov methods. In addition, we point out some important connections to the literature on the (deterministic) total QSSA (tQSSA) and place the stochastic analogue of the QSSA within the more general framework of aggregation of Markov processes. We demonstrate the new methods on four examples: Michaelis–Menten enzyme kinetics, double phosphorylation, the Goldbeter–Koshland switch, and the mitogen activated protein kinase cascade. Overall, we report dramatic improvements by applying the tQSSA to the CME solver.

Role of particle size and composition in metal adsorption by solids deposited on urban road surfaces

Despite common knowledge that the metal content adsorbed by fine particles is relatively higher compared to coarser particles, the reasons for this phenomenon has gained little research attention. The research study discussed in the paper investigated the variations in metal content for different particle sizes of solids associated with pollutant build-up on urban road surfaces. Data analysis confirmed that parameters favourable for metal adsorption to solids such as specific surface area, organic carbon content, effective cation exchange capacity and clay forming minerals content decrease with the increase in particle size. Furthermore, the mineralogical composition of solids was found to be the governing factor influencing the specific surface area and effective cation exchange capacity. There is high quartz content in particles >150µm compared to particles <150µm. As particle size reduces below 150µm, the clay forming minerals content increases, providing favourable physical and chemical properties that influence adsorption.

Theoretical evidence and chemical origin of the magnetism-dependent electrostructural coupling in La2NiMnO6

Using first-principles density-functional calculations, we determine and analyze the Born effective charges Z(*) that describe the coupling between electric field and atomic displacements for ferromagnetic double-perovskite compound, La2NiMnO6. We find that th Born effective charge matrix of Ni in La2NiMnO6, has an anomalously large antisymmetric component, whose magnitude reduces substantially upon change in the magnetic ordering between Ni and Mn, showing it to be a magnetism-dependent electrostructural coupling. We use a local picture of the electronic structure obtained with Wannier functions, along with its band-by-band decomposition to determine its electronic origin.

Mode of Coordination and Chemical Reactivity of Alpha-Imine Hydrasone Ligands

Interaction of nickel(I1) and copper(I1) complexes of 4,9-dimethy1-5,8-diazadodeca-4,8diene-2,1 ldione, Ni(baen) and 4,6,9-trimethyl-5, 8diazadodeca-4,8-diene-2,ll-dione, Ni(bapn), with arene diazonium chlorides in buffered solutions of methanol yielded metal derivatives of glyoxaliminearylhydrazones. This typical electrophilic addition at the 3-carbon of the complex occurs owing to the pseudo aromatic behaviour of the chelate ring. A mechanism which predicts the attack of the diazonium cation through the coordination shell of the metal is well documented from the available experimental evidences. The chemical reactivity of a few complexes with a single residual non-substituted y-carbon is reasonably manifested by their reaction with phenyl isocyanate.

Quantifying differences between treated and untreated coir substrate

The aim of this project was to quantify differences between treated and untreated coir (coconut industrial residues) products and to identify differences in growth, yield and quality of cut flowers grown in different coir products. This has been brought about largely by the concern that some coir products, washed in low quality (saline) water may have detrimental effects on plant productivity and quality. There is concern in the flower production industry and among media suppliers, that lower quality products are favoured due to price alone, which as this project shows is a false economy. Specifically the project examined: • Differences in physical and chemical properties of treated and untreated coir along with another commonly used growing media in the flower industy; • Potential improvements in yield and quality of Gerbera (Gerbera jamesonii); • Potential differences in vase life of Gerbera as a result of the different growing media; and • Cost-benefit implications of treated (more expensive) coir substrate products versus untreated (less expensive) coir including any subsequent differences in yield and quality. By first examining the physical and some chemical properties of different coir substrates and other industry standard media, the researchers have been able to validate the concerns raised about the potential quality issues in coir based growing media. There was a great deal of variation in both the electrical conductivity and sodium contents. Physical properties were also variable as expected since manufacturers are able to target the specific physical preferences of plants through manipulation of the particle size distribution. A field trial was conducted under protected cropping practices in which three growing media were compared in terms of total productivity and also flower quality parameters such as stem length, flower diameter and vase life. The trial was a completely randomised design with the three growing media comprising treated coir discs, untreated coir discs and a pine bark coir mix. Four cultivars of Gerbera were assessed: Balance®; Carambole®; Dune® and Picobello®, all new products from Florist de Kwakel B.V., Denmark. Initial expansion from tissue culture was conducted at the Highsun Express Facility, Ormiston, Queensland. The trial included 12 replications of each cultivar in each media (a total of 144 plants) to ensure all data collected, and the derived conclusions were statistically rigorous. The coir supplied with no pre-treatment or buffering produced significantly less flowers than those grown in a pine bark coir mix or the pre-treated coir. Interestingly, the pine bark coir mix produced a greater number of flowers. However, the flowers produced in the pine bark coir mix were generally a shorter length stem. Productivity data, combined with flower quality data and component costs were all analysed through a cost/benefit economic model which showed that the greater revenue from better stem length outweighed the stem numbers, giving a cost benefit ratio of 2.58 for treated coir, 2.49 for untreated coir and 2.52 for pine bark coir mix. While this does not seem a large difference, when considering the number of plants a producer maintains can be upwards of 50,000 the difference in revenue would be, at a minimum $60,000 in this example. In conclusion, this project has found that there are significant effects on plant health, growth, yield and quality between those grown in treated and untreated coir. The outcome being growers can confidently invest in more expensive treated products with the assurance that benefits will outweigh initial cost. It is false economy to favour untreated coir products based on price alone. Producers should ensure they fully understand the production processes when purchasing growing media. Rather than targeting lower priced materials, it is recommended that quality be the highest priority in making this management decision. In making recommendations for future research and development it was important to consider conclusions from other researchers as well as those of the current project. It has been suggested that the media has greater longevity, which although not captured in this study could also lead to further cost efficiencies. Assessment of the products over a longer time period, and using a wider range of plant species are the major recommendations for further research to ensure greater understanding as to the importance in choosing the right growing media to meet specific needs.

Tracking and identifying wastewater toxicants and assessing their biodegradation products

Screening of wastewater effluents from municipal and industrial wastewater treatment plants with biotests showed that the treated wastewater effluents possess only minor acute toxic properties towards whole organisms (e.g. bacteria, algae, daphnia), if any. In vitro tests (sub-mitochondrial membranes and fish hepatocytes) were generally more susceptible to the effluents. Most of the effluents indicated the presence of hormonally active compounds, as the production of vitellogenin, an egg yolk precursor protein, was induced in fish hepatocytes exposed to wastewater. In addition, indications of slight genotoxic potential was found in one effluent concentrate with a recombinant bacteria test. Reverse electron transport (RET) of mitochondrial membranes was used as a model test to conduct effluent assessment followed by toxicant characterisations and identifications. Using a modified U.S. EPA Toxicity Identification Evaluation Phase I scheme and additional case-specific methods, the main compound in a pulp and paper mill effluent causing RET inhibition was characterised to be an organic, relatively hydrophilic high molecular weight (HMW) compound. The toxicant could be verified as HMW lignin by structural analyses using nuclear magnetic resonance. In the confirmation step commercial and in-house extracted lignin products were used. The possible toxicity related structures were characterised by statistical analysis of the chemical breakdown structures of laboratory-scale pulping and bleaching effluents and the toxicities of these effluents. Finally, the biological degradation of the identified toxicant and other wastewater constituents was evaluated using bioassays in combination with chemical analyses. Biological methods have not been used routinely in establishing effluent discharge limits in Finland. However, the biological effects observed in this study could not have been predicted using only routine physical and chemical effluent monitoring parameters. Therefore chemical parameters cannot be considered to be sufficient in controlling effluent discharges especially in case of unknown, possibly bioaccumulative, compounds that may be present in small concentrations and may cause chronic effects.