Sílica mesoporosa como suporte sólido para o ancoramento da molécula 4-amino-3-hidrazino-5-mercapto-1,2,4-triazole e aplicação na adsorção de Cu(II), Cd(II), Ni(II), Pb(II) e Co(II) em amostras aquosas

Pós-graduação em Química - IQ

Oxidação e remoção de ferro e manganês em águas para fins de abastecimento público ou industrial: uma abordagem geral

The iron and manganese ions are present in a high frequency in water source in Brazil. Despite of the frequency in which such problems occur, the way the problem is faced is still traditional, i.e. focusing on oxidative process instead of solid-liquid separation. The treatment can be very simple, in groundwater, or very complex, when metals are present together with organic matter in water. This article presents a review of principal works besides some important aspects about iron and manganese in natural water, occurrence, forms in natural water, organic complexes, oxidation and removal applying solid/liquid separation processes. Further, a new strategy for iron and manganese removal is presented. The information described does not exhaust the matter, so a large bibliography was cited at the end of the article.

Avaliação das áreas de conflito de uso em APP da microbacia do alto água fria, Bofete (SP)

The misuse of land by man and is causing serious problems to the environment, resulting in ecological imbalance and depletion of natural resources, especially when it comes to areas of permanent preservation, that ecosystems are essential for balance and water conservation importance . Conflicts of land use is a major cause of silting of rivers and water bodies, causing significant losses in soil and decaying natural water resources both in quantity and in quality. Within this scenario, the planning becomes essential for the control of environmental impacts to the environment factor. This study aimed to evaluate land use conflicts in permanent preservation areas of the stream Água Fria watershed, Bofete (SP) using Geographic Information System and satellite image of LANDSAT - 5 of 2010, scale 1:50000. The results show that 51.16% of the permanent preservation areas of the watershed are conflicting, especially for pasture (88.94%) and reforestation with eucalyptus (11.06%). The GIS IDRISI Selva and Cartalinx along with GIS techniques demonstrated speed and efficiency in identifying, measuring and editing maps of land use, preservation and ongoing conflicts in areas of permanent preservation.

Enzymatic Solid-Phase Reactor Based on Silica Organofunctionalized with p-Phenylenediamine for Electrochemical Detection of Phenolic Compounds

A new biomaterial, based on silica organofunctionalized with p-phenylenediamine (p-PDA) and the enzyme peroxidase, was used in the development of an enzymatic solid-phase reactor. The analytical techniques used in the characterization showed that the organic ligand was incorporated into the silica matrix. Thus, the silica modified with p-PDA allowed the incorporation of peroxidase by the electrostatic interaction between the carboxylic groups present in the enzyme molecules and the amino groups attached to the silica. The enzymatic solid-phase reactor was used for chemical oxidation of phenols in 1, 4-benzoquinone that was then detected by chronoamperometry. The system allowed the analysis of hydroquinone with a detection limit of 83.6 nmol L-1. Thus, the new material has potential in the determination of phenolic compounds river water samples.

Evaluation of the detection and quantification limits in electroanalysis using two popular methods: application in the case study of paraquat determination

In this work, the reduction reaction of paraquat herbicide was used to obtain analytical signals using electrochemical techniques of differential pulse voltammetry, square wave voltammetry and multiple square wave voltammetry. Analytes were prepared with laboratory purified water and natural water samples (from Mogi-Guacu River, SP). The electrochemical techniques were applied to 1.0 mol L-1 Na2SO4 solutions, at pH 5.5, and containing different concentrations of paraquat, in the range of 1 to 10 mu mol L-1, using a gold ultramicroelectrode. 5 replicate experiments were conducted and in each the mean value for peak currents obtained -0.70 V vs. Ag/AgCl yielded excellent linear relationships with pesticide concentrations. The slope values for the calibration plots (method sensitivity) were 4.06 x 10(-3), 1.07 x 10(-2) and 2.95 x 10(-2) A mol(-1) L for purified water by differential pulse voltammetry, square wave voltammetry and multiple square wave voltammetry, respectively. For river water samples, the slope values were 2.60 x 10(-3), 1.06 x 10(-2) and 3.35 x 10(-2) A mol(-1) L, respectively, showing a small interference from the natural matrix components in paraquat determinations. The detection limits for paraquat determinations were calculated by two distinct methodologies, i.e., as proposed by IUPAC and a statistical method. The values obtained with multiple square waves voltammetry were 0.002 and 0.12 mu mol L-1, respectively, for pure water electrolytes. The detection limit from IUPAC recommendations, when inserted in the calibration curve equation, an analytical signal (oxidation current) is smaller than the one experimentally observed for the blank solution under the same experimental conditions. This is inconsistent with the definition of detection limit, thus the IUPAC methodology requires further discussion. The same conclusion can be drawn by the analyses of detection limits obtained with the other techniques studied.

Consolidation properties and strength characteristics of ODP Site 204-1244 sediments

Eight whole-core samples from Ocean Drilling Program Site 1244, Hydrate Ridge, Cascadia continental margin, were provided to Massachusetts Institute of Technology (Cambridge, Massachusetts, USA) for geotechnical characterization. The samples were collected from depths ranging from 5 to 136 meters below seafloor (mbsf). Seven of the eight whole-core samples were located within the gas hydrate stability zone, whereas the eighth sample was located in the free gas zone. Atterberg limits testing showed that the average liquid limit of the soil is 81% and the average plastic limit is 38%, giving an average plasticity index of 43%. The liquid limit is sensitive to oven drying, shown by a drop in liquid limit to 64% when tests were performed on an oven-dried sample. Loss on ignition averages 5.45 wt%. Constant rate of strain consolidation (CRSC) tests were performed to obtain the compression characteristics of the soil, as well as to determine the stress history of the site. CRSC tests also provided hydraulic conductivity and coefficient of consolidation characteristics for these sediments. The compression ratio (Cc) ranges from 0.340 to 0.704 (average = 0.568). Cc is fairly constant to a depth of 79 mbsf, after which Cc decreases downhole. The recompression ratio (Cr) ranges from 0.035 to 0.064 (average = 0.052). Cr is constant throughout the depth range. In situ hydraulic conductivity varies between 1.5 x 10**-7 and 3 x 10**-8 cm/s and shows no trend with depth. Ko-consolidated undrained compression/extension (CKoUC/E) tests were also performed to determine the peak undrained shear strength, stress-strain curve, and friction angle. The normalized undrained strength ranges from 0.29 to 0.35. The friction angle ranges from 27 to 37. Because of the limited amount of soil, CRSC and CKoUC/E tests were also conducted on resedimented specimens.

Characterization cement pastes degraded in lanoratory solutions and physiochemical parameters employed for modeling the process

Previously degradation studies carried out, over a number of different mortars by the research team, have shown that observed degradation does not exclusively depend on the solution equilibrium pH, nor the aggressive anions relative solubility. In our tests no reason was found that could allow us to explain, why same solubility anions with a lower pH are less aggressive than others. The aim of this paper is to study cement pastes behavior in aggressive environments. As observed in previous research, this cement pastes behaviors are not easily explained only taking into account only usual parameters, pH, solubility etc. Consequently the paper is about studying if solution physicochemical characteristics are more important in certain environments than specific pH values. The paper tries to obtain a degradation model, which starting from solution physicochemical parameters allows us to interpret the different behaviors shown by different composition cements. To that end, the rates of degradation of the solid phases were computed for each considered environment. Three cement have been studied: CEM I 42.5R/SR, CEM II/A-V 42.5R and CEM IV/B-(P-V) 32.5 N. The pastes have been exposed to five environments: sodium acetate/acetic acid 0.35 M, sodium sulfate solution 0.17 M, a solution representing natural water, saturated calcium hydroxide solution and laboratory environment. The attack mechanism was meant to be unidirectional, in order to achieve so; all sides of cylinders were sealed except from the attacked surface. The cylinders were taking out of the exposition environments after 2, 4, 7, 14, 30, 58 and 90 days. Both aggressive solution variations in solid phases and in different depths have been characterized. To each age and depth the calcium, magnesium and iron contents have been analyzed. Hydrated phases evolution studied, using thermal analysis, and crystalline compound changes, using X ray diffraction have been also analyzed. Sodium sulphate and water solutions stabilize an outer pH near to 8 in short time, however the stability of the most pH dependent phases is not the same. Although having similar pH and existing the possibility of forming a plaster layer near to the calcium leaching surface, this stability is greater than other sulphate solutions. Stability variations of solids formed by inverse diffusion, determine the rate of degradation.

Indicadores de sostenibilidad de la gestión integral de las aguas de lluvia en los entornos urbanos : aplicación a la ciudad de Zaragoza

En un contexto de rápido crecimiento de la población urbana y de cambio climático global, la consecución de un modelo de desarrollo sostenible pasa inevitablemente por construir ciudades más sostenibles. Basado en una intensiva impermeabilización de los suelos, el modelo actual de desarrollo urbano modifica profundamente el ciclo natural del agua en las ciudades. La drástica reducción de la capacidad de infiltración del terreno hace que gran parte de la precipitación se transforme en escorrentía superficial, que se concentra rápidamente originando grandes caudales punta. Además, el lavado de las superficies urbanas aporta altas cargas de contaminación a la escorrentía que producen importantes impactos en los medios receptores. Esta realidad motiva la realización de la presente tesis doctoral cuyo objetivo general es contribuir a la consecución de ciudades sostenibles a través de la gestión integral de las aguas de lluvia en los entornos urbanos. Con el objetivo prioritario de minimizar los riesgos de inundación, el enfoque convencional del drenaje urbano desarrolló las primeras soluciones en relación a los caudales punta, centralizando su gestión en el sistema de saneamiento e incorporando la escorrentía al mismo tan rápido como fuera posible. Pero en episodios de lluvias intensas la sobrecarga tanto hidráulica como de contaminación del sistema provoca un incremento de la vulnerabilidad de la población a las inundaciones, una falta de garantía de salud pública y graves impactos sobre los medios receptores. La aprobación en 1987 del CleanWaterAct en Estados Unidos, en el que se reconoció por primera vez el problema de la contaminación aportada por la escorrentía urbana, fue el punto de partida de un nuevo enfoque que promueve un conjunto de técnicas de drenaje que integran aspectos como cantidad de agua, calidad de agua y servicio a la sociedad. Estas técnicas, conocidas como Sistemas de Drenaje Sostenible (SUDS), son consideradas como las técnicas más apropiadas para gestionar los riesgos resultantes de la escorrentía urbana así como para contribuir a la mejora medioambiental de la cuenca y de los ecosistemas receptores. La experiencia internacional apunta a que la efectiva incorporación de los SUDS como sistemas habituales en el desarrollo urbano debe basarse en tres elementos clave: El desarrollo de un marco normativo, la aplicación de instrumentos económicos y la participación ciudadana activa en el proceso. Además se identifica como una de las líneas estratégicas para avanzar en la resolución de la problemática el desarrollo y aplicación de metodologías que apoyen el proceso de toma de decisiones basadas en indicadores cuantificables. Convergiendo con esta línea estratégica la presente tesis doctoral define unos indicadores de sostenibilidad focalizados en una temática no desarrollada hasta el momento, la gestión integral de las aguas de lluvia. Para ello, se aplica el marco analítico Presión-Estado–Respuesta bajo un enfoque que rebasa el sistema de saneamiento, enmarcando la gestión de las aguas de lluvia en las múltiples y complejas interrelaciones del sistema urbano. Así se determinan indicadores de presión, de estado y de respuesta para cada elemento del sistema urbano (Medio Receptor – Cuenca Urbana – Sistema de Saneamiento), definiendo para cada indicador el objetivo específico, la unidad de medición, la tendencia deseada de evolución y la periodicidad de seguimiento recomendada. La validez de la metodología propuesta se comprueba en el estudio de caso de la ciudad de Zaragoza. La determinación de los indicadores permite realizar un diagnóstico y definir unas líneas estratégicas de actuación que contemplan mejoras no sólo en el sistema de saneamiento y drenaje urbano, sino también en el marco normativo, urbanístico, económico, social y ambiental. Finalmente, se concluye que la integración de la gestión de las aguas de lluvia en las políticas de ordenación del territorio, el desarrollo de mecanismos de coordinación institucional, la mejora del marco normativo y la aplicación de instrumentos económicos son elementos clave para la gestión integral de las aguas de lluvia y el consecuente desarrollo de ciudades más sostenibles en España. In a context of rapid urbanization and global climate change, coping with sustainable development challenges requires the development of sustainable cities. Based on an intensive soil permeability reduction, the current development model deeply modifies the natural water cycle in the urban environment. Reduction of soil infiltration capacity turns most of the rainwater into surface runoff, rapidly leading to heavy peak flows which are highly contaminated due to the flushing of the urban surface. This is the central motivation for this thesis, which aspires to contribute to the attainment of more sustainable cities through an integrated management of rainwater in urban environments. With the main objective of minimizing floods, the conventional approach of drainage systems focused on peak flows, centralizing their management on the sewage system and incorporating flows as fast as possible. But during heavy rains the hydraulic and contamination overcharge of the sewage system leads to an increase in the vulnerability of the population, in regards to floods and lack of public health, as well as to severe impacts in receiving waters. In 1987, the United States’Clean Water Act Declaration, which firstly recognized the problem of runoff contamination, was the starting point of a new approach that promotes a set of techniques known as Sustainable Drainage Systems (SUDS)that integrates issues such as quantity of water, quality of water and service to society. SUDS are considered the most suitable set of techniques to manage the risks resulting from urban runoff, as well as to contribute to the environmental enhancement of urban basins and of the aquatic ecosystems. International experience points out that the effective adoption of SUDS as usual systems in urban development must be based on three key elements: The enhancement of the legal frame, the application of economic tools and the active public participation throughout the process. Additionally, one of the strategic actions to advance in the resolution of the problem is the development and application of methodologies based in measurable indicators that support the decision making process. In that line, this thesis defines a set of sustainability indicators focused in integrated management of rainwater. To that end, the present document applies the analytical frame Pressure – State – Response under an approach that goes beyond the sewage system and considers the multiple and complex interrelations within urban systems. Thus, for the three basic elements that interact in the issue (Receiving Water Bodies – Urban Basin – Sewage System) a set of Pressure – State – Response indicators are proposed, and the specific aim, the measurement unit, the desired evolution trend and the regularity of monitoring are defined for each of the indicators. The application of the proposed indicators to the case study of the city of Zaragoza acknowledged their suitability for the definition of lines of action that encompass not only the enhancement of the performance of sewage and drainage systems during rain events, but also the legal, urban, economic, social and environmental framework. Finally, this thesis concludes that the inclusion of urban rainwater management issues in the definition of regional planning policies, the development of mechanisms to attain an effective institutional coordination, the enhancement of the legal framework and the application of economic tools are key elements in order to achieve an integrated rainwater management and the subsequent sustainability of urban development in Spain.

Aplicación de un modelo geográfico con información climática para el cálculo del balance hídrico de la comarca de la Marina Baja (Alicante)

Este trabajo analiza las nuevas tendencias en la creación y gestión de información geográfica, para la elaboración de modelos inductivos basados exclusivamente en bases de datos geográficas. Estos modelos permiten integrar grandes volúmenes de datos de características heterogéneas, lo que supone una gran complejidad técnica y metodológica. Se propone una metodología que permite conocer detalladamente la distribución de los recursos hídricos naturales en un territorio y derivar numerosas capas de información que puedan ser incorporadas a estos modelos «ávidos de datos» (data-hungry). La zona de estudio escogida para aplicar esta metodología es la comarca de la Marina Baja (Alicante), para la que se presenta un cálculo del balance hídrico espacial mediante el uso de herramientas estadísticas, geoestadísticas y Sistemas de Información Geográfica. Finalmente, todas las capas de información generadas (84) han sido validadas y se ha comprobado que su creación admite un cierto grado de automatización que permitirá incorporarlas en análisis de Minería de Datos más amplios.

Evaluation of semi-passive treatment technologies for septic lagoon capacity expansion

In Canada, increases in rural development has led to a growing need to effectively manage the resulting municipal and city sewage without the addition of significant cost- and energy- expending infrastructure. Storring Septic Service Limited is a family-owned, licensed wastewater treatment facility located in eastern Ontario. It makes use of a passive waste stabilization pond system to treat and dispose of waste and wastewater in an environmentally responsible manner. Storring Septic, like many other similar small-scale wastewater treatment facilities across Canada, has the potential to act as a sustainable eco-engineered facility that municipalities and service providers could utilize to manage and dispose of their wastewater. However, it is of concern that the substantial inclusion of third party material could be detrimental to the stability and robustness of the pond system. In order to augment the capacity of the current facility, and ensure it remains a self-sustaining system with the capacity to safely accept septage from other sewage haulers, it was hypothesized that pond effluent treatment could be further enhanced through the incorporation of one of three different technology solutions, which would allow the reduction of wastewater quality parameters below existing regulatory effluent discharge limits put in place by Ontario’s Ministry of the Environment and Climate Change (MOECC). Two of these solutions make use of biofilm technologies in order to enhance the removal of wastewater parameters of interest, and the third utilizes the natural water filtration capabilities of zebra mussels. Pilot-scale testing investigated the effects of each of these technologies on treatment performance under both cold and warm weather operation. This research aimed to understand the important mechanisms behind biological filtration methods in order to choose and optimize the best treatment strategy for full-scale testing and implementation. In doing so, a recommendation matrix was elaborated provided with the potential to be used as a universal operational strategy for wastewater treatment facilities located in environments of similar climate and ecology.

Recursos hídricos superficiais vs subterrâneos na Várzea da Nazaré : implicações na qualidade da água

Tese de doutoramento, Geologia (Hidrogeologia), Universidade de Lisboa, Faculdade de Ciências, 2016

Factors affecting the growth of Cladophora in relation to river pollution

Nuisance growths of Cladophora have been associated with eutrophication. A review of the literature, however, reveals a scarcity of relevant experimental growth studies. Sampling experimental streams reveals that the addition of sewage effluent to good quality water alters the flora from that dominated by Potamogetan crispus to one dominated by CLadophora. Spatial and temporal differences in biomass of taxa present are discussed in the context of accompanying physicochemical data. In laboratory batch culture, growth of unialgal C. glomerata was accompanied by elevation of medium pH - considered largely responsible for the poor growth in such culture. However, appropriate experimental conditions and indices of growth were selected and the effects of various herbicides assessed. Diquat and terbutryne were shown to possess algicidal activity towards Cladophora. A closed continuous culture apparatus was developed: growth proceeded through lag, logarithmic and linear phases. Inoculum size and medium flow rate had significant effects on growth, and were standardized. In continuous culture, specific growth rate increased linearly with increased duration of light per day, up to 24 hours, and increased light intensity, up to 6000 lux - the highest intensity tested. Comparison of field and laboratory results suggests that ammonia toxicity is attributable to the undissociated form. In the laboratory, 185 µg/1 undissociated ammoniacal nitrogen reduced specific growth rate to 50% of that at 10 µg/1 undissociated ammcniacal nitrogen. 0.077-1.057 mg/1 NO2-N had no significant effect on growth. 7.2-15.2 mg/1 NO3-N had no significant effect on specific growth rate. Neither was any nitrate/phosphate interaction significant. At 4.9 mg/1 PO4-1, specific growth rate was only 48% of that at 1.9 g/1 P04-P. The critical medium PO4-P concentration was <0.1 mg/i. Specific growth rate was reduced to 50% of that in natural water by 0.036 mgCu/l, 0.070 mgzn/1 and 1.03 mgPb/l. Metal uptake was evaluated.

Novel methodology for in situ carbon dioxide enrichment of benthic ecosystems

Future climate change will likely represent a major stress to shallow aquatic and coastal marine communities around the world. Most climate change research, particularly in regards to increased pCO2 and ocean acidification, relies on ex situ mesocosm experimentation, isolating target organisms from their environment. Such mesocosms allow for greater experimental control of some variables, but can often cause unrealistic changes in a variety of environmental factors, leading to “bottle effects.” Here we present an in situ technique of altering dissolved pCO2within nearshore benthic communities (e.g., macrophytes, algae, and/or corals) using submerged clear, open-top chambers. Our technique utilizes a flow-through design that replicates natural water flow conditions and minimizes caging effects. The clear, open-top design additionally ensures that adequate light reaches the benthic community. Our results show that CO2 concentrations and pH can be successfully manipulated for long durations within the open-top chambers, continuously replicating forecasts for the year 2100. Enriched chambers displayed an average 0.46 unit reduction in pH as compared with ambient chambers over a 6-month period. Additionally, CO2 and HCO3 – concentrations were all significantly higher within the enriched chambers. We discuss the advantages and disadvantages of this technique in comparison to other ex situ mesocosm designs used for climate change research.

Composition of a protein-like fluorophore of dissolved organic matter in coastal wetland and estuarine ecosystems

This study demonstrates the compositional heterogeneity of a protein-like fluorescence emission signal (T-peak; excitation/emission maximum at 280/325 nm) of dissolved organic matter (DOM) samples collected from subtropical river and estuarine environments. Natural water samples were collected from the Florida Coastal Everglades ecosystem. The samples were ultrafiltered and excitation–emission fluorescence matrices were obtained. The T-peak intensity correlated positively with N concentration of the ultrafiltered DOM solution (UDON), although, the low correlation coefficient (r2=0.140, p<0.05) suggested the coexistence of proteins with other classes of compounds in the T-peak. As such, the T-peak was unbundled on size exclusion chromatography. The elution curves showed that the T-peak was composed of two compounds with distinct molecular weights (MW) with nominal MWs of about >5×104 (T1) and ∼7.6×103 (T2) and with varying relative abundance among samples. The T1-peak intensity correlated strongly with [UDON] (r2=0.516, p<0.001), while T2-peak did not, which suggested that the T-peak is composed of a mixture of compounds with different chemical structures and ecological roles, namely proteinaceous materials and presumably phenolic moieties in humic-like substances. Natural source of the latter may include polyphenols leached from senescent plant materials, which are important precursors of humic substances. This idea is supported by the fact that polyphenols, such as gallic acid, an important constituent of hydrolysable tannins, and condensed tannins extracted from red mangrove (Rhizophora mangle) leaves exhibited the fluorescence peak in the close vicinity of the T-peak (260/346 and 275/313 nm, respectively). Based on this study the application of the T-peak as a proxy for [DON] in natural waters may have limitations in coastal zones with significant terrestrial DOM input.

Mangrove tannins in aquatic ecosystems: Their fate and possible influence on dissolved organic carbon and nitrogen cycling

We describe the fate of mangrove leaf tannins in aquatic ecosystems and their possible influence on dissolved organic nitrogen (DON) cycling. Tannins were extracted and purified from senescent yellow leaves of the red mangrove (Rhizophora mangle) and used for a series of model experiments to investigate their physical and chemical reactivity in natural environments. Physical processes investigated included aggregation, adsorption to organic matter-rich sediments, and co-aggregation with DON in natural waters. Chemical reactions included structural change, which was determined by excitation–emission matrix fluorescence spectra, and the release of proteins from tannin–protein complexes under solar-simulated light exposure. A large portion of tannins can be physically eliminated from aquatic environments by precipitation in saline water and also by binding to sediments. A portion of DON in natural water can coprecipitate with tannins, indicating that mangrove swamps can influence DON cycling in estuarine environments. The chemical reactivity of tannins in natural waters was also very high, with a half-life of less than 1 d. Proteins were released gradually from tannin–protein complexes incubated under light conditions but not under dark conditions, indicating a potentially buffering role of tannin– protein complexes on DON recycling in mangrove estuaries. Although tannins are not detected at a significant level in natural waters, they play an important ecological role by preserving nitrogen and buffering its cycling in estuarine ecosystems through the prevention of rapid DON export/loss from mangrove fringe areas and/or from rapid microbial mineralization.