Organic reactions in ionic liquids:A new method for the synthesis of alkyl aryl sulfones by alkylation of sodium arenesulfinates with unactivated alkyl chlorides

A new method is reported for the synthesis of alkyl aryl sulfones by alkylation of sodium arenesulfinates with unactivated alkyl chlorides using ionic liquid based on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF 4) mixed with water (2:1) as reaction media. The ionic liquid can be reused and the procedure gives the sulfones in moderate yields.

Hydro-physical characterization of media used in agricultural systems to develop the best management practices for operation of an environmentally sustainable agricultural enterprise

Florida is the second leading horticulture state in the United States with a total annual industry sale of over $12 Billion. Due to its competitive nature, agricultural plant production represents an extremely intensive practice with large amounts of water and fertilizer usage. Agrochemical and water management are vital for efficient functioning of any agricultural enterprise, and the subsequent nutrient loading from such agricultural practices has been a concern for environmentalists. A thorough understanding of the agrochemical and the soil amendments used in these agricultural systems is of special interest as contamination of soils can cause surface and groundwater pollution leading to ecosystem toxicity. The presence of fragile ecosystems such as the Everglades, Biscayne Bay and Big Cypress near enterprises that use such agricultural systems makes the whole issue even more imminent. Although significant research has been conducted with soils and soil mix, there is no acceptable method for determining the hydraulic properties of mixtures that have been subjected to organic and inorganic soil amendments. Hydro-physical characterization of such mixtures can facilitate the understanding of water retention and permeation characteristics of the commonly used mix which can further allow modeling of soil water interactions. The objective of this study was to characterize some of the locally and commercially available plant growth mixtures for their hydro-physical properties and develop mathematical models to correlate these acquired basic properties to the hydraulic conductivity of the mixture. The objective was also to model the response patterns of soil amendments present in those mixtures to different water and fertilizer use scenarios using the characterized hydro-physical properties with the help of Everglades-Agro-Hydrology Model. The presence of organic amendments helps the mixtures retain more water while the inorganic amendments tend to adsorb more nutrients due to their high surface area. The results of these types of characterization can provide a scientific basis for understanding the non-point source water pollution from horticulture production systems and assist in the development of the best management practices for the operation of environmentally sustainable agricultural enterprise

Effects of Natural Organic Matter on the Dissolution Kinetics and Bioavailability of Metal Oxide Nanoparticles

The rapid development of nanotechnology and wider applications of engineered nanomaterials (ENMs) in the last few decades have generated concerns regarding their environmental and health risks. After release into the environment, ENMs undergo aggregation, transformation, and, for metal-based nanomaterials, dissolution processes, which together determine their fate, bioavailability and toxicity to living organisms in the ecosystems. The rates of these processes are dependent on nanomaterial characteristics as well as complex environmental factors, including natural organic matter (NOM). As a ubiquitous component of aquatic systems, NOM plays a key role in the aggregation, dissolution and transformation of metal-based nanomaterials and colloids in aquatic environments.

The goal of this dissertation work is to investigate how NOM fractions with different chemical and molecular properties affect the dissolution kinetics of metal oxide ENMs, such as zinc oxide (ZnO) and copper oxide (CuO) nanoparticles (NPs), and consequently their bioavailability to aquatic vertebrate, with Gulf killifish (Fundulus grandis) embryos as model organisms.

ZnO NPs are known to dissolve at relatively fast rates, and the rate of dissolution is influenced by water chemistry, including the presence of Zn-chelating ligands. A challenge, however, remains in quantifying the dissolution of ZnO NPs, particularly for time scales that are short enough to determine rates. This dissertation assessed the application of anodic stripping voltammetry (ASV) with a hanging mercury drop electrode to directly measure the concentration of dissolved Zn in ZnO NP suspensions, without separation of the ZnO NPs from the aqueous phase. Dissolved zinc concentration measured by ASV ([Zn]ASV) was compared with that measured by inductively coupled plasma mass spectrometry (ICP-MS) after ultracentrifugation ([Zn]ICP-MS), for four types of ZnO NPs with different coatings and primary particle diameters. For small ZnO NPs (4-5 nm), [Zn]ASV was 20% higher than [Zn]ICP-MS, suggesting that these small NPs contributed to the voltammetric measurement. For larger ZnO NPs (approximately 20 nm), [Zn]ASV was (79±19)% of [Zn]ICP-MS, despite the high concentrations of ZnO NPs in suspension, suggesting that ASV can be used to accurately measure the dissolution kinetics of ZnO NPs of this primary particle size.

Using the ASV technique to directly measure dissolved zinc concentration, we examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg-C L-1) for Suwannee River humic acid (SRHA), Suwannee River fulvic acid and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. NOM isolates with higher SUVA were also more effective at enhancing the colloidal stability of the NPs; however, the NOM-promoted dissolution was likely due to enhanced interactions between surface metal ions and NOM rather than smaller aggregate size.

Based on the above results, we designed experiments to quantitatively link the dissolution kinetics and bioavailability of CuO NPs to Gulf killifish embryos under the influence of NOM. The CuO NPs dissolved to varying degrees and at different rates in diluted 5‰ artificial seawater buffered to different pH (6.3-7.5), with or without selected NOM isolates at various concentrations (0.1-10 mg-C L-1). NOM isolates with higher SUVA and aromatic carbon content (such as SRHA) were more effective at promoting the dissolution of CuO NPs, as with ZnO NPs, especially at higher NOM concentrations. On the other hand, the presence of NOM decreased the bioavailability of dissolved Cu ions, with the uptake rate constant negatively correlated to dissolved organic carbon concentration ([DOC]) multiplied by SUVA, a combined parameter indicative of aromatic carbon concentration in the media. When the embryos were exposed to CuO NP suspension, changes in their Cu content were due to the uptake of both dissolved Cu ions and nanoparticulate CuO. The uptake rate constant of nanoparticulate CuO was also negatively correlated to [DOC]×SUVA, in a fashion roughly proportional to changes in dissolved Cu uptake rate constant. Thus, the ratio of uptake rate constants from dissolved Cu and nanoparticulate CuO (ranging from 12 to 22, on average 17±4) were insensitive to NOM type or concentration. Instead, the relative contributions of these two Cu forms were largely determined by the percentage of CuO NP that was dissolved.

Overall, this dissertation elucidated the important role that dissolved NOM plays in affecting the environmental fate and bioavailability of soluble metal-based nanomaterials. This dissertation work identified aromatic carbon content and its indicator SUVA as key NOM properties that influence the dissolution, aggregation and biouptake kinetics of metal oxide NPs and highlighted dissolution rate as a useful functional assay for assessing the relative contributions of dissolved and nanoparticulate forms to metal bioavailability. Findings of this dissertation work will be helpful for predicting the environmental risks of engineered nanomaterials.

Organic Surveillance: Security and Myth in the Rural

This project looks at the ways Northeastern Ontario citizens in rural communities regulate their private property through traditional and contemporary surveillance means. Through art and objects, this project allows viewers the opportunity to experience surveillance in rural areas through visual and creative ways that encourage interaction and critique. This project defines organic surveillance by looking at the ways ruralists in Markstay Ontario practice surveillance and deterrence which is influenced by characteristics of land, risks and other determining factors such as psychology, resourcefulness, sustainability, technology and private property. Organic surveillance argues that surveillance and deterrence is prevalent far beyond datamining, GPS tracking and social media. Surveillance and deterrence as methods of survival are found everywhere, even in the farthest, most “wild” and forested areas.

Ultrasound-assisted electrochemical treatment of wastewaters containing organic pollutants by using novel Ti/Ta2O5-SnO2 electrodes

Advanced oxidation processes (AOPs) are modern methods using reactive hydroxyl radicals for the mineralization of organic pollutants into simple inorganic compounds, such as CO2 and H2O. Among AOPs electrochemical oxidation (EO) is a method suitable for coloured and turbid wastewaters. The degradation of pollutants occurs on electrocatalytic electrodes. The majority of electrodes contain in their structure either expensive materials (diamond and Pt-group metals) or are toxic for the environment compounds (Sb or Pb). One of the main disadvantages of electrochemical method is the polarization and contamination of electrodes due to the deposition of reaction products on their surface, which results in diminishing of the process efficiency. Ultrasound combined with the electrochemical degradation process eliminates electrode contamination because of the continuous mechanical cleaning effect produced by the formation and collapse of acoustic cavitation bubbles near to the electrode surface. Moreover, high frequency ultrasound generates hydroxyl radicals at water sonolysis. Ultrasound-assisted EO is a non-selective method for oxidation of different organic compounds with high degradation efficiencies. The aim of this research was to develop novel sustainable and cost-effective electrodes working as electrocatalysts and test their activity in electrocatalytic oxidation of organic compounds such as dyes and organic acids. Moreover, the goal of the research was to enhance the efficiency of electrocatalytic degradation processes by assisting it with ultrasound in order to eliminate the main drawbacks of a single electrochemical oxidation such as electrodes polarization and passivation. Novel Ti/Ta2O5-SnO2 electrodes were developed and found to be electrocatalytically active towards water (with 5% Ta content, 10 oxide film layers) and organic compounds oxidation (with 7.5% Ta content, 8 oxide film layers) and therefore these electrodes can be applicable in both environmental and energy fields. The synergetic effect of combined electrolysis and sonication was shown while conducting sonoelectrochemical (EO/US) degradation of methylene blue (MB) and formic acid (FA). Complete degradation of MB and FA was achieved after 45 and 120 min of EO/US process respectively in neutral media. Mineralization efficiency of FA over 95% was obtained after 2 h of degradation using high frequency ultrasound (381, 863, 1176 kHz) combined with 9.1 mA/cm2 current density. EO/US degradation of MB provided over 75% mineralization in 8 h. High degradation kinetic rates and mineralization efficiencies of model pollutants obtained in EO/US experiments provide the preconditions for further extrapolation of this treatment method to pilot scale studies with industrial wastewaters.

Non chemical natural organic matter removal with a contact TiO2 process

Dissertação de Mestrado, Tecnologia dos Alimentos, Instituto Superior de Engenharia, Universidade do Algarve, 2014

Integrating social media tools in a web portal

Benefitting from Web 2.0 features, Social Media allows organisations to be where the users are, creating proximity, talking to them, and knowing what they want. Going viral and word-of-mouth become easier, as these platforms allow us to share, to like, and to use multimedia and convergence – as they can interact with each other, communicating on a large scale. Given that online portals provide for a highly competitive environment, players strive to get more visits, better search rankings, and even aspire to be the homepage for the Web universe. We discuss the integration of Social Media tools in a Web Portal, and explore how using these together may improve the competitiveness of a Web Portal. A large Web Portal was selected to develop this case study. We found that, although for this particular Web Portal conditions were created to accommodate and integrate the chosen Social Media platforms, this was done in an organic and fluid way, with great focus on community construction and less focus on absorptive capacity. Based on the findings of this case study, we propose a dynamic cycle of benefits for integrating Social Media tools in a Web Portal.

Optical actuation of inorganic/organic interfaces: comparing peptide-azobenzene ligand reconfiguration on gold and silver nanoparticles

Photoresponsive molecules that incorporate peptides capable of material-specific recognition provide a basis for biomolecule-mediated control of the nucleation, growth, organization, and activation of hybrid inorganic/organic nanostructures. These hybrid molecules interact with the inorganic surface through multiple noncovalent interactions which allow reconfiguration in response to optical stimuli. Here, we quantify the binding of azobenzene-peptide conjugates that exhibit optically triggered cis-trans isomerization on Ag surfaces and compare to their behavior on Au. These results demonstrate differences in binding and switching behavior between the Au and Ag surfaces. These molecules can also produce and stabilize Au and Ag nanoparticles in aqueous media where the biointerface can be reproducibly and reversibly switched by optically triggered azobenzene isomerization. Comparisons of switching rates and reversibility on the nanoparticles reveal differences that depend upon whether the azobenzene is attached at the peptide N- or C-terminus, its isomerization state, and the nanoparticle composition. Our integrated experimental and computational investigation shows that the number of ligand anchor sites strongly influences the nanoparticle size. As predicted by our molecular simulations, weaker contact between the hybrid biomolecules and the Ag surface, with fewer anchor residues compared with Au, gives rise to differences in switching kinetics on Ag versus Au. Our findings provide a pathway toward achieving new remotely actuatable nanomaterials for multiple applications from a single system, which remains difficult to achieve using conventional approaches.

Optical actuation of inorganic/organic interfaces: comparing peptide-azobenzene ligand reconfiguration on gold and silver nanoparticles

Photoresponsive molecules that incorporate peptides capable of material-specific recognition provide a basis for biomolecule-mediated control of the nucleation, growth, organization, and activation of hybrid inorganic/organic nanostructures. These hybrid molecules interact with the inorganic surface through multiple noncovalent interactions which allow reconfiguration in response to optical stimuli. Here, we quantify the binding of azobenzene-peptide conjugates that exhibit optically triggered cis-trans isomerization on Ag surfaces and compare to their behavior on Au. These results demonstrate differences in binding and switching behavior between the Au and Ag surfaces. These molecules can also produce and stabilize Au and Ag nanoparticles in aqueous media where the biointerface can be reproducibly and reversibly switched by optically triggered azobenzene isomerization. Comparisons of switching rates and reversibility on the nanoparticles reveal differences that depend upon whether the azobenzene is attached at the peptide N- or C-terminus, its isomerization state, and the nanoparticle composition. Our integrated experimental and computational investigation shows that the number of ligand anchor sites strongly influences the nanoparticle size. As predicted by our molecular simulations, weaker contact between the hybrid biomolecules and the Ag surface, with fewer anchor residues compared with Au, gives rise to differences in switching kinetics on Ag versus Au. Our findings provide a pathway toward achieving new remotely actuatable nanomaterials for multiple applications from a single system, which remains difficult to achieve using conventional approaches.

Selective sensing of pyrophosphate in physiological media using zinc( ii )dipicolylamino-functionalised peptides

A series of linear peptide based anion receptors, in which the distance between the bis[zinc(II)dipicolylamine] binding sites and the peptide backbone was varied systematically, was prepared and their anion binding ability was investigated using indicator displacement assays. Shortening the distance between the binding site and the peptide backbone was found to enhance both the receptor affinity and selectivity for pyrophosphate over other organic polyphosphate anions in Krebs buffer with the maximum selectivity and affinity observed with a spacer length of two methylene units. The suitability of these receptors for the determination of pyrophosphate concentrations in Krebs buffer and in artificial urine was examined.

Hydro-Physical Characterization of Media Used in Agricultural Systems to Develop the Best Management Practices for operation of an Environmentally Sustainable Agricultural Enterprise

Florida is the second leading horticulture state in the United States with a total annual industry sale of over $12 Billion. Due to its competitive nature, agricultural plant production represents an extremely intensive practice with large amounts of water and fertilizer usage. Agrochemical and water management are vital for efficient functioning of any agricultural enterprise, and the subsequent nutrient loading from such agricultural practices has been a concern for environmentalists. A thorough understanding of the agrochemical and the soil amendments used in these agricultural systems is of special interest as contamination of soils can cause surface and groundwater pollution leading to ecosystem toxicity. The presence of fragile ecosystems such as the Everglades, Biscayne Bay and Big Cypress near enterprises that use such agricultural systems makes the whole issue even more imminent. Although significant research has been conducted with soils and soil mix, there is no acceptable method for determining the hydraulic properties of mixtures that have been subjected to organic and inorganic soil amendments. Hydro-physical characterization of such mixtures can facilitate the understanding of water retention and permeation characteristics of the commonly used mix which can further allow modeling of soil water interactions. The objective of this study was to characterize some of the locally and commercially available plant growth mixtures for their hydro-physical properties and develop mathematical models to correlate these acquired basic properties to the hydraulic conductivity of the mixture. The objective was also to model the response patterns of soil amendments present in those mixtures to different water and fertilizer use scenarios using the characterized hydro-physical properties with the help of Everglades-Agro-Hydrology Model. The presence of organic amendments helps the mixtures retain more water while the inorganic amendments tend to adsorb more nutrients due to their high surface area. The results of these types of characterization can provide a scientific basis for understanding the non-point source water pollution from horticulture production systems and assist in the development of the best management practices for the operation of environmentally sustainable agricultural enterprise

Sensible use of primary energy in organic greenhouse production.

This document addresses the direct and indirect use of energy in European organic greenhouse horticulture (OGH) with the aim of reviewing available means for making it more environmental friendly and identifying knowledge gaps that should be addressed to attain this aim. The first observation is that there is no common regulation for energy use in OGH, which is not unexpected, since the need for climatisation is not uniformly distributed in the EU (and outside). Accordingly, the EU directive on organic agriculture does not set limitations on the use of energy, but rather promotes the responsible use of energy and of natural resources. The restrictions and rules of most private standards are slightly more stringent. Some standards have specific restrictions on the amount and sources of energy and/or on the seasonal use of energy for heating. Some standards also address processes that may affect (in)direct energy use, such as cultivation methods, mulching, lighting and growing media or substrates. However, most private standards have no or little restrictions or regulations on energy use. Accordingly, it should not surprise that very little quantitative information is available about energy use in OGH. In the present document we have filled the gaps with data with estimates drawn on energy use in conventional greenhouses. With respect to ongoing research, whereas many of the present research results about energy use and saving in conventional greenhouses are relevant (and also applied) in OGH, little research is devoted to address the energy use that is peculiar to OGH, particularly energy use for humidity control. In short, there are still a lot of knowledge gaps to improve quality and to lower energy use in organic greenhouses. The purpose of this document is a summary of present relevant knowledge about energy use and energy saving and of the perspective for improvement. In particular, the goal is to make an overview on the methods and technologies which can be used to reduce the energy use in OGH. We start from the assumption that methods and technologies that are used for reducing direct and indirect energy in conventional greenhouses can also be applied in organic greenhouses. Research on reducing energy use in conventional greenhouses is also more widely available because the area of conventional greenhouse horticulture is much larger than the area of OGH. When implementing these methods and techniques we should take into account the specific characteristics of organic agriculture like soil-based cultivation, use of organic fertilizers and the limited use of crop protection products. This document is organised as follows: first we report the results of a survey about energy use and relevant standards in the countries participating to the COST action (chapter 1); then we review the energy use for climatisation: heating (chapter 2) and humidity (chapter 3). In chapter 4 we review the available design and management means that would either reduce energy use and/or increase energy use efficiency by increasing productivity of OGH. In chapter 5 we present a short summary of existing information on indirect energy use, that is the energy required to manufacture production means (greenhouse structure and cover, fertilisers, equipment etc.) and for crop protection, particularly steaming, and briefly discuss possible savings. Finally (chapter 6) we review briefly the potential for application of renewable energy sources in OGH.