Influência da radiação ionizante natural no açude do boqueirão (RN): avaliação de risco saúde/ambiente

The contamination of water bodies with toxic substances causes a decrease in water quality, representing a risk to public health. In this context, human activities are generally seen as the main sources of water degradation. However, elements found naturally in the environment can also compromise water quality. Thus, the Boqueirão‘s dam, located in the municipality of Parelhas (RN, Brazil), was chosen as area for the development of this study, as its geological region is rich in the emission of natural ionizing radiation that produces byproducts like lead and Radon. Moreover, the area has a strong human influence that enhances the risks of pollutant discharge in this body of water.Thus, the objectives of this study were centered (i) in the analysis of risk perception in the city of Parelhas (RN/Brasil) due to the use of the water from the Boqueirão Dam; and (ii) in the assessment of water quality in the Dam using methods that quantify, mainly, heavy metals and radiation levels, as well as these toxics potential of inducing mutations on genetic material. The analysis of risk perception showed that the population in the city of Parelhas can perceive a risk in using the water from the dam and that they can recognize factors that influence the water quality. Regarding the second objective, the set of data point to the contamination of the Dam by heavy metals, as well as levels of radioactive parcicles and Radon – also present in high concentrations in outdoor air and on soil. Thus, it is possible to infer that the population residing in this area is subjected to injuries caused by exposure to natural and anthropogenic contamination. Our findings corroborate with the perception of the population regarding the risks associated with the use of the Dam for several types of activities. It is expected that the information gathered in this study can substantiate activities and future researches in this semiarid region in the Rio Grande do Norte/Brazil. Also, that the set of data can enable a better understanding of the specific toxicological scenario of risk found for the population and the effect of the contamination for the biota, which aids the development of a future risk assessment and a consequent management of this local issue.

Remoção de metais utilizando o hexadecanoato de sódio

Industrial activities like mining, electroplating and the oil extraction process, are increasing the levels of heavy metals such as Cu, Fe, Mg and Cd in aquatic ecosystems. This increase is related to the discharge of effluents containing trace of this elements above the maximum allowed by law. Methods such as ion exchange, membrane filtration and chemical precipitation have been studied as a means of treatment of these metals contamination. The precipitation of metals using anionic surfactants derived from carboxylic acids emerged as an alternative for the removal of metals from industrial effluents. The reaction between bivalent ions and these types of surfactants in aqueous solution leads to the formation of metal carboxylates, which can precipitate in the form of flakes and are subsequently removed by a process of decantation or simple filtration. In this work the metals extraction is performed by using the surfactant sodium hexadecanoate as extracting agent. The main purpose was to study the effect of temperature, solution pH, and concentration of surfactant in the metal removal process. The statistical design of the process showed that the process is directly dependent to changes in pH and concentration of surfactant, but inversely proportional and somewhat dependent to temperature variation, with the latter effect being considered negligible in most cases. The individual study of the effect of temperature showed a strong dependence of the process with the Kraft point, both for the surfactant used as extracting agent, as for the surfactant obtained after the reaction of this surfactant with the metal. From data of temperatures and concentrations of the surfactant was possible to calculate the equilibrium constant for the reaction between sodium hexadecanoate and copper ions. Later, thermodynamic parameters were determined, showing that the process is exothermic and spontaneous.

Estudo da eficiência eletroquímica para tratamento de chorume gerado em aterro sanitário brasileiro

This work was performing effluent degradation studies by electrochemical treatment. The electrochemical oxidation (EO) hydroquinone (H2Q) was carried out in acid medium, using PbO2 electrode by galvanostatic electrolysis, applying current densities of 10 and 30 mA/cm2 . The concentration of H2Q was monitored by differential pulse voltammetry (DPV). The experimental results showed that the galvanostatic electrolysis process performance significantly depends on the applied current density, achieving removal efficiencies of 100% and 80 % and 10 applying 30 mA/cm2 , respectively. Furthermore, the electroanalytical technique was effective in H2Q be used as a detection method. In order to test the efficiency of PbO2 electrode, the electrochemical treatment was conducted in an actual effluent, leachate from a landfill. The liquid waste leachate (600ml effluent) was treated in a batch electrochemical cell, with or without addition of NaCl by applying 7 mA/cm2 . The efficiency of EO was assessed against the removal of thermo-tolerant coliforms, total organic carbon (TOC), total phosphorus and metals (copper, cobalt, chromium, iron and nickel). These results showed that efficient removal of coliforms was obtained (100%), and was further decrease the concentration of heavy metals by the cathode processes. However, results were not satisfactory TOC, achieving low total removal of dissolved organic load. Because it is considered an effluent complex were developed other tests with this effluent to monitor a larger number of decontamination parameters (Turbidity, Total Solids, Color, Conductivity, Total Organic Carbon (TOC) and metals (barium, chromium, lithium, manganese and Zinc), comparing the efficiency of this type of electrochemical treatment (EO or electrocoagulation) using a flow cell. In this assay was compared to electro streaming. In the case of the OE, Ti/IrO2-TaO5 was used as the anode, however, the electrocoagulation process, aluminum electrodes were used; applying current densities of 10, 20 and 30 mA/cm2 in the presence and absence of NaCl as an electrolyte. The results showed that EO using Ti/IrO2–TaO5 was anode as efficient when Cl- was present in the effluent. In contrast, the electrocoagulation flow reduces the dissolved organic matter in the effluent, under certain experimental conditions.

Caracterização e separação física de placas de circuito impresso de computadores obsoletos

The unbridled consumption of electronic equipment associated with fast immersion of new technologies on the market leads to the accelerated growth of electronic waste. Such waste mostly contains printed circuit boards in its structure. Printed circuit boards have many metals, including heavy metals, being highly toxic. Electronic waste is discarded improperly and indiscriminately, usually without any previous treatment and with other municipal waste, contaminating the environment and causing serious problems to human health. Beyond these metals, there are also precious metals and high value-added basis, that can be recovered and recycled, reducing the exploration of natural resources. Thus, due to the high growth potential and reuse of these waste treatment processes, characterization and separation were applied to the printed circuit boards. The printed circuit boards were subjected to physical treatments such as dismantling, crushing, sizing separation, magnetic separation and chemical treatments such as pyrolysis and leaching. Through characterization process (pyrolysis and leaching) the proportions of the components of the granulometric range were determined: 46,08% of metals; 23,32% of polymers and 30,60% of ceramics. It was also observed by particle size separation that metal components tend to concentrate in coarse fractions, while polymeric and ceramic components in fine fractions. From the magnetic separation process was obtained 12,08% of magnetic material and 82,33% of non-magnetic material.

Sedimentology, geochemistry and ostracodes from Lake Ohrid

Ancient Lake Ohrid, located in the southern Balkan Peninsula in Macedonia and Albania is characterized by a high degree of endemism and it is considered to be the oldest lake in Europe. But its exact age (between one and ten million years) and also its origin are so far not known. To unravel these uncertainties an ICDP (International Continental Scientific Drilling Program) drilling project (Scientific Collaboration On Past Speciation Conditions in Ohrid (SCOPSCO)), started in April 2013. In addition to the investigations about the age and origin, other paleolimnological studies, e.g., the reconstruction of past climate and of past lake level changes, should be performed with the drilled cores. Used proxies in such paleolimnological studies are, e.g., ostracodes because they respond sensitively to environmental changes but an accurate knowledge of their preferences and tolerances to specific environmental conditions is necessary for this purpose. So far, this knowledge about the, mostly endemic, Ohrid ostracodes was limited. Thus, within the framework of this thesis, ostracodes and a multiplicity of environmental data were collected in Lake Ohrid and its adjacent waters during four field campaigns. In a total of 47 ostracode species could be detected in the entire study area and 32 of them were found alive in Lake Ohrid. Multivariate statistic identified that water depth, salinity, conductivity, pH, and dissolved oxygen were the main determining factors for ostracode distribution in the entire study area. In Lake Ohrid, the distribution was mainly controlled by water depth, water temperature, and pH. Some ostracodes were identified as strong indicator species for important environmental variables, e.g., water temperature and water depth. A distinctive feature of Lake Ohrid was the finding of the ostracode genus Amnicythere whose species normally inhabit oligo-(meso-)haline waters and this could point to a marine origin of the lake. So far, the specialized endemic ostracodes show the highest abundances and the greatest spatial distribution in Lake Ohrid but during the sampling eight widespread species were found for the first time in the lake. They inhabited mainly the northern part of the lake, where two cities are located and industry and agriculture play a major role, and they were limited to water depths above 50 m and this could be an evidence for an increasing anthropogenic pressure because widespread ostracode species often replace endemic species. To unravel the human impact on Lake Ohrid during the last decades short sediment cores were taken and the multi-proxy study indicated that the lake productivity between the early 1920s and the late 1980s was relatively low. Diatom assemblages indicate a rising productivity in the southern part of Lake Ohrid since the mid 1970s and geochemical proxies and ostracodes point to an increasing productivity since the late 1980s in the southern and in the northern part. A slight increase in the productivity continued until 2009. Noticeable is the fact that since the early 1990s, the increasing productivity and the increasing concentrations of heavy metals correspond to a decreasing number of ostracodes in the northern part of Lake Ohrid. Perhaps, this indicates that living conditions in this lake part became less favorable for the mostly endemic ostracode species. Furthermore, the sediment samples from the cores show relatively high concentrations of arsenic, iron, and nickel. Fluctuations in ostracode assemblages from three longer sediment cores, the longest spans approximately 136 ka, taken in Lake Ohrid, correspond to fluctuations in the productivity, in the carbonate content, of the lake level, and of climate changes. Between the marine isotope stage (MIS) 6 and MIS 2 the number of ostracode valves is very low or the valves were completely absent. This corresponds to a low lake productivity, a low carbonate content, and a low lake level. At the onset of the Holocene, the number of valves increased markedly and this correlates with an increased productivity and carbonate content and a warmer climate. But during the Little Ice Age (LIA), the number of valves dropped again and species which prefer warmer waters disappeared completely. This drop corresponds also to a low productivity. After the LIA, the number of species increased again but since 1895 AD a strong and abrupt decrease is visible. A reason for this could be an increase in the heavy metal concentrations.

Experimental data from column and batch samples

The presented thesis was written in the frame of a project called 'seepage water prognosis'. It was funded by the Federal Ministry for Education and Science (BMBF). 41 German institutions among them research institutes of universities, public authorities and engineering companies were financed for three years respectively. The aim was to work out the scientific basis that is needed to carry out a seepage water prognosis (Oberacker und Eberle, 2002). According to the Federal German Soil Protection Act (Federal Bulletin, 1998) a seepage water prognosis is required in order to avoid future soil impacts from the application of recycling products. The participants focused on the development of either methods to determine the source strength of the materials investigated, which is defined as the total mass flow caused by natural leaching or on models to predict the contaminants transport through the underlying soil. Annual meetings of all participants as well as separate meetings of the two subprojects were held. The department of Geosciences in Bremen participated with two subprojects. The aim of the subproject that resulted in this thesis was the development of easily applicable, valid, and generally accepted laboratory methods for the determination of the source strength. In the scope of the second subproject my colleague Veith Becker developed a computer model for the transport prognosis with the source strength as the main input parameter.

Geochemistry, carbon isotope ratio and radiocarbon ages of sediment core GIK1093-2 from Bornholm Basin, Baltic Sea

Concentrations of Cd, Pb, Zn, Cu, Co, Ni, Fe, and Al203, water content, the amounts of organic carbon, the ratio of 13C/12C and the 14C-activity of the organic fraction were determined with sediment depth from a 34 cm long box-core from the Bornholm Basin (Baltic Sea). The average sedimentation rate was 2.4 mm/yr. The upper portion of the core contained increasing amounts of 14C-inactive organic carbon, and above 3 cm depth, man-made 14C from atomic bomb tests. The concentrations of the heavy metals Cd, Pb, Zn, and Cu increase strongly towards the surface, while other metals, as Fe, Ni and Co remain almost unchanged. This phenomenon is attributed to anthropogenic influences. A comparison of the Kieler Bucht, the Bornholm and the Gotland Basins shows that today the anthropogenic addition of Zn is about 100 mg/m**2 yr in all three basins. The beginning of this excess of Zn, however, is delayed by about 20 years in, the Bornholm Basin and by about 40 years in the Gotland Basin. It is suggested that SW-NE transport of these anthropogenically mobilized metals may be related to periodic bottom water renewal in the Baltic Sea sedimentary basins.

RELATIONSHIP BETWEEN PHYSICAL AND CHEMICAL PROPERTIES OF STRAIGHT AND RECOVERED ASPHALT BINDERS FROM ONTARIO

Thermal and fatigue cracking are the major pavement distresses that contribute to a drastic reduction of the pavement’s service life and performance in Ontario. Chemical oxidation and hardening of asphalt binders deteriorates its physical properties since physical properties of asphalts depend on its chemical composition. This thesis is aimed to establish a relationship between physical and chemical properties of asphalt binders. A secondary objective is to show the strong correlation between CTOD and temperature. All recovered and straight Ministry of Transportation of Ontario (MTO) samples were investigated using conventional Superpave® test method dynamic shear rheometer (DSR) as well as improved MTO test methods such as extended bending beam rheometer (eBBR) and double-edge-notched tension (DENT) test. DENT test was conducted for all Ontario contract samples at three different temperatures based on their performance grade after three hours of thermal conditioning and compared the results in terms of essential work of fracture, plastic work of fracture and CTOD at different temperatures. Good correlation exists between CTOD and temperature according to the DENT data. X-ray fluorescence (XRF) analysis was conducted to detect the presence of heavy metals such as zinc and molybdenum believed to have originated from waste engine oil. Fourier transform infra-red spectroscopy (FTIR) was performed to determine the abundance of functional groups such as carbonyl, sulfoxides, polyisobutylene, etc. XRF and FTIR analysis confirmed that most of the samples contain waste engine oil and/or oxidized residues, which is believed to be a root cause of premature pavement failures.

Upper-Pleistocene terrace deposits in Mediterranean climate: geomorphological and source-rock control on mineral and geochemical signatures (Betic Cordillera, SE Spain)

Mineral and chemical composition of alluvial Upper-Pleistocene deposits from the Alto Guadalquivir Basin (SE Spain) were studied as a tool to identify sedimentary and geomorphological processes controlling its formation. Sediments located upstream, in the north-eastern sector of the basin, are rich in dolomite, illite, MgO and KB2BO. Downstream, sediments at the sequence base are enriched in calcite, smectite and CaO, whereas the upper sediments have similar features to those from upstream. Elevated rare-earth elements (REE) values can be related to low carbonate content in the sediments and the increase of silicate material produced and concentrated during soil formation processes in the neighbouring source areas. Two mineralogical and geochemical signatures related to different sediment source areas were identified. Basal levels were deposited during a predominantly erosive initial stage, and are mainly composed of calcite and smectite materials enriched in REE coming from Neogene marls and limestones. Then the deposition of the upper levels of the alluvial sequences, made of dolomite and illitic materials depleted in REE coming from the surrounding Sierra de Cazorla area took place during a less erosive later stage of the fluvial system. Such modification was responsible of the change in the mineralogical and geochemical composition of the alluvial sediments.

Spatial Variations of the Methanogenic Communities in the Sediments of Tropical Mangroves

Methane production by methanogens in mangrove sediments is known to contribute significantly to global warming, but studies on the shift of methanogenic community in response to anthropogenic contaminations were still limited. In this study, the effect of anthropogenic activities in the mangrove sediments along the north and south coastlines of Singapore were investigated by pyrosequencing of the mcrA gene. Our results showed that hydrogenotrophic, acetoclastic and methylotrophic methanogens coexist in the sediments. The predominance of the methylotrophic Methanosarcinales reflects the potential for high methane production as well as the possible availability of low acetate and high methylated C-1 compounds as substrates. A decline in the number of acetoclastic/methylotrophic methanogens in favor of hydrogenotrophic methanogens was observed along a vertical profile in Sungei Changi, which was contaminated by heavy metals. The diversity of methanogens in the various contaminated stations was significantly different from that in a pristine St. John’s Island. The spatial variation in the methanogenic communities among the different stations was more distinct than those along the vertical profiles at each station. We suggest that the overall heterogeneity of the methanogenic communities residing in the tropical mangrove sediments might be due to the accumulated effects of temperature and concentrations of nitrate, cobalt, and nickel.

Vermiculitas tratadas quimicamente na obtenção de sólidos microporosos como precursores para híbridos inorgânico-orgânicos com aplicações adsortivas

ALVES, Ana paula Melo. Vermiculitas tratadas quimicamente na obtenção de sólidos microporosos como precursores para híbridos inorgânico-orgânicos com aplicações adsortivas. 2009. 124 f. Tese (Doutorado em Quimica) - Centro de Ciências Exatas e da Natureza, Universidade Federal da Paraíba, João Pessoa, PB, 2009.

Traitement du ruissellement routier chargé en sels de déglaçage et en métaux lourds par un marais épurateur construit et adapté

Depuis la construction de l’autouroute 40 dans les années 70 (tronçon Félix-Leclerc), le lac Saint-Augustin s’est grandement enrichi en sels de déglaçage et en métaux lourds. Un marais épurateur construit et adapté (MECA), dans lequel ont été intégrées des plantes halophytes, a donc été implanté afin traiter une partie des eaux de ruissellement provenant de l’autouroute. Le comportement et l’efficacité de ce dernier ont été évalués afin de déterminer si cette technologie était en mesure de pallier à la problématique de contamination. Les observations et les analyses ont permis d’établir que les plantes halophytes sont mal adaptées aux conditions environnementales du MECA et que seulement environ 1% des sels sont emmagasinés dans les plantes. Les concentrations mesurées dans les eaux ont montré que le MECA est efficace pour emmagasiner du sel de déglaçage, principalement en période de temps sec, mais que les quantités accumulées sont peu significatives par rapport aux quantités introduites.

Chemistry of potassium halides and their role in corrosion in biomass and waste firing

Compared to the use of traditional fossil fuels (coal, oil, natural gas), combustion of biomass and waste fuels has several environmental and economic advantages for heat and power generation. However, biomass and waste fuels might contain halogens (Cl, Br, F), alkali metals (Na, K) and heavy metals (Zn, Pb), which may cause harmful emissions and corrosion problems. Hightemperature corrosion occurs typically on furnace waterwalls and superheaters. The corrosion of the boiler tube materials limits the increase of thermal efficiency of steam boilers and leads to costly shutdowns and repairs. In recent years, some concerns have been raised about halogen (Cl, Br, and F)-related hightemperature corrosion in biomass- and waste-fired boilers. Chlorine-related high-temperature corrosion has been studied extensively. The presence of alkali chlorides in the deposits is believed to play a major role in the corrosion observed in biomass and waste fired boilers. However, there is much less information found in literature on the corrosion effect of bromine and fluorine. According to the literature, bromine is only assumed to play a role similar to chlorine; the role of fluorine is even less understood. In this work, a series of bubbling fluidized bed (BFB) bench-scale tests were carried out to characterize the formation and sulfation behaviors of KCl and KBr in BFB combustion conditions. Furthermore, a series of laboratory tests were carried out to investigate the hightemperature corrosion behaviors of three different superheater steels (10CrMo9-10, AISI 347 and Sanicro 28) exposed to potassium halides in ambient air and wet air (containing 30% H2O). The influence of H2O and O2 on the high-temperature corrosion of steels both with and without a salt (KCl) in three gas atmospheres (2% H2O-30% O2-N2, 2% H2O-2% O2-N2 and 30% H2O-2% O2-N2) was also studied. From the bench-scale BFB combustion tests, it was found that HBr has a clearly higher affinity for the available K forming KBr than HCl forming KCl. The tests also indicated that KCl has a higher tendency for sulfation than KBr. From the laboratory corrosion tests in ambient air (also called “dry air” in Paper III and Paper IV), it was found that at relatively low temperatures (≤ 550 °C) the corrosivity of KBr and KF are similar to KCl. At 600 °C, KF showed much stronger corrosivity than KBr and KCl, especially for 10CrMo9-10 and AISI 347. When exposed to KBr or KF, 10CrMo9-10 was durable at least up to 450 °C, while AISI 347 and Sanicro 28 were durable at least up to 550 °C. From the laboratory corrosion tests in wet air (30% H2O), no obvious effect of water vapor was detected at 450 °C. At 550 °C, the influence of water vapor became significant in some cases, but the trend was not consistent. At 550 °C, after exposure with KBr, 10CrMo9-10 suffered from extreme corrosion; after exposure with KF and KCl, the corrosion was less severe, but still high. At 550 °C, local deep pitting corrosion occurred on AISI 347 and Sanicro 28 after exposure with KF. Some formation of K2CrO4 was observed in the oxide layer. At 550 °C, AISI 347 and Sanicro 28 suffered from low corrosion (oxide layer thickness of < 10 μm) after exposure with KBr and KCl. No formation of K2CrO4 was observed. Internal oxidation occurred in the cases of AISI 347 with KBr and KCl. From the laboratory corrosion tests in three different gas atmospheres (2% H2O-30% O2-N2, 2% H2O-2% O2-N2 and 30% H2O-2% O2-N2), it was found that in tests with no salt, no corrosion occurred on AISI 347 and Sanicro 28 up to 600 °C in both the “O2-rich” (2% H2O-30% O2-N2) and “H2O-rich” (30% H2O-2% O2-N2) gas atmospheres; only 10CrMo9-10 showed increased corrosion with increasing temperature. For 10CrMo9-10 in the “O2-rich” atmosphere, the presence of KCl significantly increased the corrosion compared to the “no salt” cases. For 10CrMo9-10 in the “H2O-rich” atmosphere, the presence or absence of KCl did not show any big influence on corrosion. The formation of K2CrO4 was observed only in the case with the “O2-rich” atmosphere. Considering both the results from the BFB tests and the laboratory corrosion tests, if fuels containing Br were to be combusted, the corrosion damage of superheaters would be expected to be higher than if the fuels contain only Cl. Information generated from these studies can be used to help the boiler manufacturers in selecting materials for the most demanding combustion systems.

Vermiculitas tratadas quimicamente na obtenção de sólidos microporosos como precursores para híbridos inorgânico-orgânicos com aplicações adsortivas

ALVES, Ana paula Melo. Vermiculitas tratadas quimicamente na obtenção de sólidos microporosos como precursores para híbridos inorgânico-orgânicos com aplicações adsortivas. 2009. 124 f. Tese (Doutorado em Quimica) - Centro de Ciências Exatas e da Natureza, Universidade Federal da Paraíba, João Pessoa, PB, 2009.