A Land-Use and Water-Quality History of White Rock Lake Reservoir, Dallas, Texas, Based on Paleolimnological Analyses

White Rock Lake reservoir in Dallas, Texas contains a 150-cm sediment record of silty clay that documents land-use changes since its construction in 1912. Pollen analysis corroborates historical evidence that between 1912 and 1950 the watershed was primarily agricultural. Land disturbance by plowing coupled with strong and variable spring precipitation caused large amounts of sediment to enter the lake during this period. Diatoms were not preserved at this time probably because of low productivity compared to diatom dissolution by warm, alkaline water prior to burial in the sediments. After 1956, the watershed became progressively urbanized. Erosion decreased, land stabilized, and pollen of riparian trees increased as the lake water became somewhat less turbid. By 1986 the sediment record indicates that diatom productivity had increased beyond rates of diatom destruction. Neither increased nutrients nor reduced pesticides can account for increased diatom productivity, but grain size studies imply that before 1986 diatoms were light limited by high levels of turbidity. This study documents how reservoirs may relate to land-use practices and how watershed management could extend reservoir life and improve water quality.

Introducing education for sustainable development in the undergraduate laboratory: quantitative analysis of bioethanol fuel and its blends with gasoline by using solvatochromic dyes

The concept of Education for Sustainable Development, ESD, has been introduced in a period where chemistry education is undergoing a major change, both in emphasis and methods of teaching. Studying an everyday problem, with an important socio-economic impact in the laboratory is a part of this approach. Presently, the students in many countries go to school in vehicles that run, at least partially, on biofuels; it is high time to let them test these fuels. The use of renewable fuels is not new: since 1931 the gasoline sold in Brazil contains 20 to 25 vol-% of bioethanol; this composition is being continually monitored. With ESD in mind, we have employed a constructivist approach in an undergraduate course, where UV-vis spectroscopy has been employed for the determination of the composition of two fuel blends, namely, bioethanol/water, and bioethanol/gasoline. The activities started by giving a three-part quiz. The first and second ones introduced the students to historical and practical aspects of the theme (biofuels). In the third part, we asked them to develop a UV-vis experiment for the determination of the composition of fuel blends. They have tested two approaches: (i) use of a solvatochromic dye, followed by determination of fuel composition from plots of the empirical fuel polarity versus its composition; (ii) use of an ethanol-soluble dye, followed by determination of the blend composition from a Beer's law plot; the former proved to be much more convenient. Their evaluation of the experiment was highly positive, because of the relevance of the problem; the (constructivist) approach employed, and the bright colors that the solvatochromic dye acquire in these fuel blends. Thus ESD can be fruitfully employed in order to motivate the students; make the laboratory "fun", and teach them theory (solvation). The experiments reported here can also be given to undergraduate students whose major is not chemistry (engineering, pharmacy, biology, etc.). They are low-cost and safe to be introduced at high-school level.

Use of levoglucosan, potassium, and water-soluble organic carbon to characterize the origins of biomass-burning aerosols

Three chemical species related to biomass burning, levoglucosan, potassium and water-soluble organic carbon (WSOC), were measured in aerosol samples collected in a rural area on the outskirts of the municipality of Ourinhos (Sao Paulo State, Brazil). This region is representative of the rural interior of the State, where the economy is based on agro-industrial production, and the most important crop is sugar cane. The manual harvesting process requires that the cane be first burned to remove excess foliage, leading to large emissions of particulate materials to the atmosphere. Most of the levoglucosan (68-89%) was present in small particles (<1.5 mu m), and its concentration in total aerosol ranged from 25 to 1186 ng m(-3). The highest values were found at night, when most of the biomass burning occurs. In contrast, WSOC showed no diurnal pattern, with an average concentration of 5.38 +/- 2.97 mu g m(-3) (n = 27). A significant linear correlation between levoglucosan and WSOC (r = 0.54; n = 26; p < 0.0001) confirmed that biomass burning was in fact an important source of WSOC in the study region. A moderate (but significant) linear correlation between levoglucosan and potassium concentrations (r = 0.62; n = 40; p < 0.0001) was indicative of the influence of other sources of potassium in the study region, such as soil resuspension and fertilizers. When only the fine particles (<1.5 pm; typical of biomass burning) were considered, the linear coefficient increased to 0.91 (n = 9). In this case, the average levoglucosan/K+ ratio was 0.24, which may be typical of biomass burning in the study region. This ratio is about 5 times lower than that previously found for Amazon aerosol collected during the day, when flaming combustion prevails. This suggests that the levoglucosan/K+ ratio may be especially helpful for characterization of the type of vegetation burned (such as crops or forest), when biomass-burning is the dominant source of potassium. The relatively high concentrations of WSOC (and inorganic ions) suggest an important influence on the formation of cloud condensation nuclei, which is likely to affect cloud formation and precipitation patterns. (C) 2012 Elsevier Ltd. All rights reserved.

Influence of land use changes on water chemistry in streams in the State of Sao Paulo, southeast Brazil

Streamwater is affected by several processes in the watershed including anthropogenic activities that result in changes in water quality as well as in the functioning of these stream ecosystems. Therefore, this work aims to evaluate the concentration of major ions (Ca2+, Mg2+, Na+, K+, NH4+, NO3-, NO2-, Cl-, SO42-, PO43-, HCO3-) in streams in the state of Sao Paulo (southeast Brazil). The sampling sites are located at undisturbed (ombrophilus dense forest, semideciduous forest and savanna - cerrado) and disturbed areas (pasture, urbanization and sugar cane crops). Streamwater chemistry varied according to land use change and, in general, was higher in disturbed sites. Streams located in undisturbed sites at Ribeira de Iguape/Alto Paranapanema watershed (streams 1, 2 and 3) seem to be regulated by soil characteristics, as the disturbed streams located at the same watershed covered by pasture (stream 7) showed high concentration for the most of the variables. Exception to streams located at Pontal do Paranapanema watershed where both disturbed (stream 8) and undisturbed streams (stream 4 and 5) presented similar patterns for almost all variables measured.

Glycerol as a by-product of biodiesel production in Brazil: Alternatives for the use of unrefined glycerol

On January 1 2008, Brazil included yet another element into its energy matrix: biodiesel. The predominant biodiesel production process involves a phase of transesterification that yields glycerol as a by-product. The use of this glycerol is limited since it is considered an unrefined raw material that must be refined for its various types of use. Several studies have addressed identification of possible uses for unrefined glycerol. Given the diversity of uses, an overview is necessary. The purpose of this work is to present alternatives currently being considered for the use of unrefined glycerol as a by-product of biodiesel production, aiming to contribute to the sustainable consolidation of the biofuel market. Exploratory research was carried out to identify these viable alternatives for the use of this by-product. The possibilities include the production of chemical products, fuel additives, production of hydrogen, development of fuel cells, ethanol or methanol production, animal feed, co-digestion and co-gasification, and waste treatment among others. The present research reveals that there are promising possibilities for the use of unrefined glycerol, which may help consolidate the sustainability of the biofuel market. (C) 2012 Elsevier Ltd. All rights reserved.

Application of MALDI-MS analysis of Rainforest chemodiversity: a keystone for biodiversity conservation and sustainable use

FAPESP/BIOTA

Influence of land use changes on water chemistry in streams in the State of São Paulo, southeast Brazil

Streamwater is affected by several processes in the watershed including anthropogenic activities that result in changes in water quality as well as in the functioning of these stream ecosystems. Therefore, this work aims to evaluate the concentration of major ions (Ca2+, Mg2+, Na+, K+, NH4+, NO3-, NO2-, Cl-, SO4(2-), PO4(3-), HCO3-) in streams in the state of São Paulo (southeast Brazil). The sampling sites are located at undisturbed (ombrophilus dense forest, semideciduous forest and savanna - cerrado) and disturbed areas (pasture, urbanization and sugar cane crops). Streamwater chemistry varied according to land use change and, in general, was higher in disturbed sites. Streams located in undisturbed sites at Ribeira de Iguape/Alto Paranapanema watershed (streams 1, 2 and 3) seem to be regulated by soil characteristics, as the disturbed streams located at the same watershed covered by pasture (stream 7) showed high concentration for the most of the variables. Exception to streams located at Pontal do Paranapanema watershed where both disturbed (stream 8) and undisturbed streams (stream 4 and 5) presented similar patterns for almost all variables measured.

"Water users must be efficient producers". Women's access to and use of land in Chókwè irrigation scheme, Mozambique

The irrigation scheme Eduardo Mondlane, situated in Chókwè District - in the Southern part of the Gaza province and within the Limpopo River Basin - is the largest in the country, covering approximately 30,000 hectares of land. Built by the Portuguese colonial administration in the 1950s to exploit the agricultural potential of the area through cash-cropping, after Independence it became one of Frelimo’s flagship projects aiming at the “socialization of the countryside” and at agricultural economic development through the creation of a state farm and of several cooperatives. The failure of Frelimo’s economic reforms, several infrastructural constraints and local farmers resistance to collective forms of production led to scheme to a state of severe degradation aggravated by the floods of the year 2000. A project of technical rehabilitation initiated after the floods is currently accompanied by a strong “efficiency” discourse from the managing institution that strongly opposes the use of irrigated land for subsistence agriculture, historically a major livelihood strategy for smallfarmers, particularly for women. In fact, the area has been characterized, since the end of the XIX century, by a stable pattern of male migration towards South African mines, that has resulted in an a steady increase of women-headed households (both de jure and de facto). The relationship between land reform, agricultural development, poverty alleviation and gender equality in Southern Africa is long debated in academic literature. Within this debate, the role of agricultural activities in irrigation schemes is particularly interesting considering that, in a drought-prone area, having access to water for irrigation means increased possibilities of improving food and livelihood security, and income levels. In the case of Chókwè, local governments institutions are endorsing the development of commercial agriculture through initiatives such as partnerships with international cooperation agencies or joint-ventures with private investors. While these business models can sometimes lead to positive outcomes in terms of poverty alleviation, it is important to recognize that decentralization and neoliberal reforms occur in the context of financial and political crisis of the State that lacks the resources to efficiently manage infrastructures such as irrigation systems. This kind of institutional and economic reforms risk accelerating processes of social and economic marginalisation, including landlessness, in particular for poor rural women that mainly use irrigated land for subsistence production. The study combines an analysis of the historical and geographical context with the study of relevant literature and original fieldwork. Fieldwork was conducted between February and June 2007 (where I mainly collected secondary data, maps and statistics and conducted preliminary visit to Chókwè) and from October 2007 to March 2008. Fieldwork methodology was qualitative and used semi-structured interviews with central and local Government officials, technical experts of the irrigation scheme, civil society organisations, international NGOs, rural extensionists, and water users from the irrigation scheme, in particular those women smallfarmers members of local farmers’ associations. Thanks to the collaboration with the Union of Farmers’ Associations of Chókwè, she has been able to participate to members’ meeting, to education and training activities addressed to women farmers members of the Union and to organize a group discussion. In Chókwè irrigation scheme, women account for the 32% of water users of the familiar sector (comprising plot-holders with less than 5 hectares of land) and for just 5% of the private sector. If one considers farmers’ associations of the familiar sector (a legacy of Frelimo’s cooperatives), women are 84% of total members. However, the security given to them by the land title that they have acquired through occupation is severely endangered by the use that they make of land, that is considered as “non efficient” by the irrigation scheme authority. Due to a reduced access to marketing possibilities and to inputs, training, information and credit women, in actual fact, risk to see their right to access land and water revoked because they are not able to sustain the increasing cost of the water fee. The myth of the “efficient producer” does not take into consideration the characteristics of inequality and gender discrimination of the neo-liberal market. Expecting small-farmers, and in particular women, to be able to compete in the globalized agricultural market seems unrealistic, and can perpetuate unequal gendered access to resources such as land and water.

Use of solvents and environmental friendly materials for applications in Green Chemistry

The present Thesis studies three alternative solvent groups as sustainable replacement of traditional organic solvents. Some aspects of fluorinated solvents, supercritical fluids and ionic liquids, have been analysed with a critical approach and their effective “greenness” has been evaluated from the points of view of the synthesis, the properties and the applications. In particular, the attention has been put on the environmental and human health issues, evaluating the eco-toxicity, the toxicity and the persistence, to underline that applicability and sustainability are subjects with equal importance. The “green” features of fluorous solvents and supercritical fluids are almost well-established; in particular supercritical carbon dioxide (scCO2) is probably the “greenest” solvent among the alternative solvent systems developed in the last years, enabling to combine numerous advantages both from the point of view of industrial/technological applications and eco-compatibility. In the Thesis the analysis of these two classes of alternative solvents has been mainly focused on their applicability, rather than the evaluation of their environmental impact. Specifically they have been evaluated as alternative media for non-aqueous biocatalysis. For this purpose, the hydrophobic ion pairing (HIP), which allows solubilising enzymes in apolar solvents by an ion pairing between the protein and a surfactant, has been investigated as effective enzymatic derivatisation technique to improve the catalytic activity under homogeneous conditions in non conventional media. The results showed that the complex enzyme-surfactant was much more active both in fluorous solvents and in supercritical carbon dioxide than the native form of the enzyme. Ionic liquids, especially imidazolium salts, have been proposed some years ago as “fully green” alternative solvents; however this epithet does not take into account several “brown” aspects such as their synthesis from petro-chemical starting materials, their considerable eco-toxicity, toxicity and resistance to biodegradation, and the difficulty of clearly outline applications in which ionic liquids are really more advantageous than traditional solvents. For all of these reasons in this Thesis a critical analysis of ionic liquids has been focused on three main topics: i) alternative synthesis by introducing structural moieties which could reduce the toxicity of the most known liquid salts, and by using starting materials from renewable resources; ii) on the evaluation of their environmental impact through eco-toxicological tests (Daphnia magna and Vibrio fischeri acute toxicity tests, and algal growth inhibition), toxicity tests (MTT test, AChE inhibition and LDH release tests) and fate and rate of aerobic biodegradation in soil and water; iii) and on the demonstration of their effectiveness as reaction media in organo-catalysis and as extractive solvents in the recovery of vegetable oil from terrestrial and aquatic biomass. The results about eco-toxicity tests with Daphnia magna, Vibrio fischeri and algae, and toxicity assay using cultured cell lines, clearly indicate that the difference in toxicity between alkyl and oxygenated cations relies in differences of polarity, according to the general trend of decreasing toxicity by decreasing the lipophilicity. Independently by the biological approach in fact, all the results are in agreement, showing a lower toxicity for compounds with oxygenated lateral chains than for those having purely alkyl lateral chains. These findings indicate that an appropriate choice of cation and anion structures is important not only to design the IL with improved and suitable chemico-physical properties but also to obtain safer and eco-friendly ILs. Moreover there is a clear indication that the composition of the abiotic environment has to be taken into account when the toxicity of ILs in various biological test systems is analysed, because, for example, the data reported in the Thesis indicate a significant influence of salinity variations on algal toxicity. Aerobic biodegradation of four imidazolium ionic liquids, two alkylated and two oxygenated, in soil was evaluated for the first time. Alkyl ionic liquids were shown to be biodegradable over the 6 months test period, and in contrast no significant mineralisation was observed with oxygenated derivatives. A different result was observed in the aerobic biodegradation of alkylated and oxygenated pyridinium ionic liquids in water because all the ionic liquids were almost completely degraded after 10 days, independently by the number of oxygen in the lateral chain of the cation. The synthesis of new ionic liquids by using renewable feedstock as starting materials, has been developed through the synthesis of furan-based ion pairs from furfural. The new ammonium salts were synthesised in very good yields, good purity of the products and wide versatility, combining low melting points with high decomposition temperatures and reduced viscosities. Regarding the possible applications as surfactants and biocides, furan-based salts could be a valuable alternative to benzyltributylammonium salts and benzalkonium chloride that are produced from non-renewable resources. A new procedure for the allylation of ketones and aldehydes with tetraallyltin in ionic liquids was developed. The reaction afforded high yields both in sulfonate-containing ILs and in ILs without sulfonate upon addition of a small amount of sulfonic acid. The checked reaction resulted in peculiar chemoselectivity favouring aliphatic substrates towards aromatic ketones and good stereoselectivity in the allylation of levoglucosenone. Finally ILs-based systems could be easily and successfully recycled, making the described procedure environmentally benign. The potential role of switchable polarity solvents as a green technology for the extraction of vegetable oil from terrestrial and aquatic biomass has been investigated. The extraction efficiency of terrestrial biomass rich in triacylglycerols, as soy bean flakes and sunflower seeds, was comparable to those of traditional organic solvents, being the yield of vegetable oils recovery very similar. Switchable polarity solvents as been also exploited for the first time in the extraction of hydrocarbons from the microalga Botryococcus braunii, demonstrating the efficiency of the process for the extraction of both dried microalgal biomass and directly of the aqueous growth medium. The switchable polarity solvents exhibited better extraction efficiency than conventional solvents, both with dried and liquid samples. This is an important issue considering that the harvest and the dewatering of algal biomass have a large impact on overall costs and energy balance.

Demersal communities in the Mediterranean Sea: a case study of Triglidae (Osteichthyes, Scorpaeniformes) on the conservation and sustainable use of marine resources

An appropriate management of fisheries resources can only be achieved with the continuous supply of information on the structure and biology of populations, in order to predict the temporal fluctuations. This study supports the importance of investigating the bio-ecology of increasingly exploited and poorly known species, such as gurnards (Osteichthyes, Triglidae) from Adriatic Sea (Mediterranean), to quantify their ecological role into marine community. It also focuses on investigate inter and intra-specific structuring factor of Adriatic population. These objectives were achieved by: 1) investigating aspects of the population dynamics; 2) studying the feeding biology through the examination of stomach contents; 3) using sagittal otoliths as potential marker of species life cycle; 4) getting preliminary data on mDNA phylogeny. Gurnards showed a specie-specific “critical size” coinciding with the start of sexual maturity, the tendency to migrate to greater depths, a change of diet from crustaceans to fish and an increase of variety of food items eaten. Distribution of prey items, predator size range and depth distribution were the main dimensions that influence the breadth of trophic niche and the relative difference amongst Adriatic gurnards. Several feeding preferences were individuated and a possible impact among bigger-size gurnards and other commercial fishes (anchovy, gadoids) and Crustacea (such as mantis prawn and shrimps) were to be necessary considered. Otolith studies showed that gurnard species have a very fast growth despite other results in other areas; intra-specific differences and the increase in the variability of otolith shape, sulcus acusticus shape, S:O ratios, sulcus acusticus external crystals arrangement were shown between juveniles and adults and were linked to growth (individual genetic factors) and to environmental conditions (e.g. depth and trophic niche distribution). In order to facilitate correct biological interpretation of data, molecular data were obtained for comparing morphological distance to genetic ones.

Sustainable improvement of water networks : to achieve best decisions for rehabilitation plans using advanced GIS and statistical techniques

Many of developing countries are facing crisis in water management due to increasing of population, water scarcity, water contaminations and effects of world economic crisis. Water distribution systems in developing countries are facing many challenges of efficient repair and rehabilitation since the information of water network is very limited, which makes the rehabilitation assessment plans very difficult. Sufficient information with high technology in developed countries makes the assessment for rehabilitation easy. Developing countries have many difficulties to assess the water network causing system failure, deterioration of mains and bad water quality in the network due to pipe corrosion and deterioration. The limited information brought into focus the urgent need to develop economical assessment for rehabilitation of water distribution systems adapted to water utilities. Gaza Strip is subject to a first case study, suffering from severe shortage in the water supply and environmental problems and contamination of underground water resources. This research focuses on improvement of water supply network to reduce the water losses in water network based on limited database using techniques of ArcGIS and commercial water network software (WaterCAD). A new approach for rehabilitation water pipes has been presented in Gaza city case study. Integrated rehabilitation assessment model has been developed for rehabilitation water pipes including three components; hydraulic assessment model, Physical assessment model and Structural assessment model. WaterCAD model has been developed with integrated in ArcGIS to produce the hydraulic assessment model for water network. The model have been designed based on pipe condition assessment with 100 score points as a maximum points for pipe condition. As results from this model, we can indicate that 40% of water pipeline have score points less than 50 points and about 10% of total pipes length have less than 30 score points. By using this model, the rehabilitation plans for each region in Gaza city can be achieved based on available budget and condition of pipes. The second case study is Kuala Lumpur Case from semi-developed countries, which has been used to develop an approach to improve the water network under crucial conditions using, advanced statistical and GIS techniques. Kuala Lumpur (KL) has water losses about 40% and high failure rate, which make severe problem. This case can represent cases in South Asia countries. Kuala Lumpur faced big challenges to reduce the water losses in water network during last 5 years. One of these challenges is high deterioration of asbestos cement (AC) pipes. They need to replace more than 6500 km of AC pipes, which need a huge budget to be achieved. Asbestos cement is subject to deterioration due to various chemical processes that either leach out the cement material or penetrate the concrete to form products that weaken the cement matrix. This case presents an approach for geo-statistical model for modelling pipe failures in a water distribution network. Database of Syabas Company (Kuala Lumpur water company) has been used in developing the model. The statistical models have been calibrated, verified and used to predict failures for both networks and individual pipes. The mathematical formulation developed for failure frequency in Kuala Lumpur was based on different pipeline characteristics, reflecting several factors such as pipe diameter, length, pressure and failure history. Generalized linear model have been applied to predict pipe failures based on District Meter Zone (DMZ) and individual pipe levels. Based on Kuala Lumpur case study, several outputs and implications have been achieved. Correlations between spatial and temporal intervals of pipe failures also have been done using ArcGIS software. Water Pipe Assessment Model (WPAM) has been developed using the analysis of historical pipe failure in Kuala Lumpur which prioritizing the pipe rehabilitation candidates based on ranking system. Frankfurt Water Network in Germany is the third main case study. This case makes an overview for Survival analysis and neural network methods used in water network. Rehabilitation strategies of water pipes have been developed for Frankfurt water network in cooperation with Mainova (Frankfurt Water Company). This thesis also presents a methodology of technical condition assessment of plastic pipes based on simple analysis. This thesis aims to make contribution to improve the prediction of pipe failures in water networks using Geographic Information System (GIS) and Decision Support System (DSS). The output from the technical condition assessment model can be used to estimate future budget needs for rehabilitation and to define pipes with high priority for replacement based on poor condition. rn

New and More Sustainable Processes for the Synthesis of Phenolics: 2-phenoxyethanol and hydroxytyrosol

The research work has dealt with the study of new catalytic processes for the synthesis of fine chemicals belonging to the class of phenolics, namely 2-phenoxyethanol and hydroxytyrosol. The two synthetic procedures investigated have the advantages of being much closer to the Green Chemistry principles than those currently used industrially. In both cases, the challenge was that of finding catalysts and methods which led to the production of less waste, and used less hazardous chemicals, safer solvents, and reusable heterogeneous catalysts. In the case of 2-phenoxyethanol, the process investigated involves the use of ethylene carbonate (EC) as the reactant for phenol O-hydroxyethylation, in place of ethylene oxide. Besides being a safer reactant, the major advantage of using EC in the new synthesis is the better selectivity to the desired product achieved. Moreover, the solid catalyst based on Na-mordenite was fully recyclable. The reaction mechanism and the effect of the Si/Al ratio in the mordenite were investigated. In the case of hydroxytyrosol, which is one of the most powerful natural antioxidants, a new synthetic procedure was investigated; in fact, the method currently employed, the hydrolysis of oleuropein, an ester extracted from the waste water processing of the olive, makes use of large amounts of organic solvents (hexane, ethyl acetate), and involves several expensive steps of purification. The synthesis procedure set up involves first the reaction between catechol and 2,2-dimethoxyacetaldehyde, followed by the one-pot reduction of the intermediate to give the desired product. Both steps were optimized, in terms of catalyst used, and of reaction conditions, that allowed to reach ca 70% yield in each step. The reaction mechanism was investigated and elucidated. During a 3-month period spent at the University of Valencia (with Prof. A. Corma’s group), a process for the production of diesel additives (2,5-bis(propoxymethyl)furan) from fructose has been investigated.