Analytical procedures for determining Pb and Sr isotopic compositions in water samples by ID-TIMS

Few articles deal with lead and strontium isotopic analysis of water samples. The aim of this study was to define the chemical procedures for Pb and Sr isotopic analyses of groundwater samples from an urban sedimentary aquifer. Thirty lead and fourteen strontium isotopic analyses were performed to test different analytical procedures. Pb and Sr isotopic ratios as well as Sr concentration did not vary using different chemical procedures. However, the Pb concentrations were very dependent on the different procedures. Therefore, the choice of the best analytical procedure was based on the Pb results, which indicated a higher reproducibility from samples that had been filtered and acidified before the evaporation, had their residues totally dissolved, and were purified by ion chromatography using the Biorad® column. Our results showed no changes in Pb ratios with the storage time.

Química Sem Fronteiras: o desafio da energia

Coal, natural gas and petroleum-based liquid fuels are still the most widely used energy sources in modern society. The current scenario contrasts with the foreseen shortage of petroleum that was spread out in the beginning of the XXI century, when the concept of "energy security" emerged as an urgent agenda to ensure a good balance between energy supply and demand. Much beyond protecting refineries and oil ducts from terrorist attacks, these issues soon developed to a portfolio of measures related to process sustainability, involving at least three fundamental dimensions: (a) the need for technological breakthroughs to improve energy production worldwide; (b) the improvement of energy efficiency in all sectors of modern society; and (c) the increase of the social perception that education is a key-word towards a better use of our energy resources. Together with these technological, economic or social issues, "energy security" is also strongly influenced by environmental issues involving greenhouse gas emissions, loss of biodiversity in environmentally sensitive areas, pollution and poor solid waste management. For these and other reasons, the implementation of more sustainable practices in our currently available industrial facilities and the search for alternative energy sources that could partly replace the fossil fuels became a major priority throughout the world. Regarding fossil fuels, the main technological bottlenecks are related to the exploitation of less accessible petroleum resources such as those in the pre-salt layer, ranging from the proper characterization of these deep-water oil reservoirs, the development of lighter and more efficient equipment for both exploration and exploitation, the optimization of the drilling techniques, the achievement of further improvements in production yields and the establishment of specialized training programs for the technical staff. The production of natural gas from shale is also emerging in several countries but its production in large scale has several problems ranging from the unavoidable environmental impact of shale mining as well as to the bad consequences of its large scale exploitation in the past. The large scale use of coal has similar environmental problems, which are aggravated by difficulties in its proper characterization. Also, the mitigation of harmful gases and particulate matter that are released as a result of combustion is still depending on the development of new gas cleaning technologies including more efficient catalysts to improve its emission profile. On the other hand, biofuels are still struggling to fulfill their role in reducing our high dependence on fossil fuels. Fatty acid alkyl esters (biodiesel) from vegetable oils and ethanol from cane sucrose and corn starch are mature technologies whose market share is partially limited by the availability of their raw materials. For this reason, there has been a great effort to develop "second-generation" technologies to produce methanol, ethanol, butanol, biodiesel, biogas (methane), bio-oils, syngas and synthetic fuels from lower grade renewable feedstocks such as lignocellulosic materials whose consumption would not interfere with the rather sensitive issues of food security. Advanced fermentation processes are envisaged as "third generation" technologies and these are primarily linked to the use of algae feedstocks as well as other organisms that could produce biofuels or simply provide microbial biomass for the processes listed above. Due to the complexity and cost of their production chain, "third generation" technologies usually aim at high value added biofuels such as biojet fuel, biohydrogen and hydrocarbons with a fuel performance similar to diesel or gasoline, situations in which the use of genetically modified organisms is usually required. In general, the main challenges in this field could be summarized as follows: (a) the need for prospecting alternative sources of biomass that are not linked to the food chain; (b) the intensive use of green chemistry principles in our current industrial activities; (c) the development of mature technologies for the production of second and third generation biofuels; (d) the development of safe bioprocesses that are based on environmentally benign microorganisms; (e) the scale-up of potential technologies to a suitable demonstration scale; and (f) the full understanding of the technological and environmental implications of the food vs. fuel debate. On the basis of these, the main objective of this article is to stimulate the discussion and help the decision making regarding "energy security" issues and their challenges for modern society, in such a way to encourage the participation of the Brazilian Chemistry community in the design of a road map for a safer, sustainable and prosper future for our nation.

Thermodynamic quantities of solvation and dilution for some acetanilide derivatives in octanol and water mutually saturateds

Based on published thermodynamic quantities for solution, partitioning and sublimation of acetanilide (ACN), acetaminophen (ACP) and Phenacetin (PNC), the thermodynamic quantities for drugs solvation in octanol-saturated water (W(ROH)) and water-saturated octanol (ROH(W)) as well as the drugs dilution in ROH(W) were calculated. The Gibbs energies of solvation were favourable in all cases. The respective enthalpies and entropies were negative indicating an enthalpy-driving for the solvation process in all cases. On the other hand, the Gibbs energies of dilution were favourable for ACP and PNC but unfavourable for ACN, whereas the respective enthalpies and entropies were negative for ACP and PNC but positive for ACN indicating enthalpy-driving for the dilution process in the case of the former drugs and entropy-driving for the latter. From the obtained values for the transfer processes, an interpretation based on solute-solvent interactions was developed.

APROS model validation in case of fast transients in a boiling water reactor

This Master´s thesis investigates the performance of the Olkiluoto 1 and 2 APROS model in case of fast transients. The thesis includes a general description of the Olkiluoto 1 and 2 nuclear power plants and of the most important safety systems. The theoretical background of the APROS code as well as the scope and the content of the Olkiluoto 1 and 2 APROS model are also described. The event sequences of the anticipated operation transients considered in the thesis are presented in detail as they will form the basis for the analysis of the APROS calculation results. The calculated fast operational transient situations comprise loss-of-load cases and two cases related to a inadvertent closure of one main steam isolation valve. As part of the thesis work, the inaccurate initial data values found in the original 1-D reactor core model were corrected. The input data needed for the creation of a more accurate 3-D core model were defined. The analysis of the APROS calculation results showed that while the main results were in good accordance with the measured plant data, also differences were detected. These differences were found to be caused by deficiencies and uncertainties related to the calculation model. According to the results the reactor core and the feedwater systems cause most of the differences between the calculated and measured values. Based on these findings, it will be possible to develop the APROS model further to make it a reliable and accurate tool for the analysis of the operational transients and possible plant modifications.

Raw water use charge reduction for the rural sector in the PCJ Watershed

The deficient environmental preservation on agricultural properties has reflected in great soil losses for erosion and the high rate of sedimentation. Therefore, this work brings the application of software to demonstrate that planters can get benefits by the conservationist practices. The benefits will be obtained from the environment aspect (erosion and sedimentation control), as well as economical aspect (financial incentives). A proposal has been created by the Technical Chamber of Rural Water Use and Conservation (CT-Rural) to estimate the reduction in raw water use charge for the rural water users of the PCJ Watershed - this reduction is being possible since January 2007, at the PCJ Committee. The software develops a simple relationship, so that if the rural conservationist action goes more efficient, such as if the conserved rural area goes larger, then the reduction value will bring better benefits for the rural water users. Within the purposes of this study, there is the idealization of mechanisms that may support specific management matters related to the water users of federal rivers from the rural sector of PCJ Watershed.

Influences of two CO2 concentrations and water availability on bean crop

This study was carried out to determine some physiological and phenological responses of the bean under high [CO2] and drought stress. The experiment was conducted from April to July 2009 in Viçosa, Brazil. The open-top chambers were used to enrich the air with CO2, whereas the drought stress was applied between the flowering and the ripening. The randomized block design was used, with four replicates in the subplots. The following plots were [CO2] at 700ppm (F1) and [CO2] environmental (F2) and the subplots were well watering (S1) and drought stress (S2). The results were subjected to Anova and the Tukey test (P < 0.05). For the treatments F1S1 and F1S2 the photosynthetic rate showed increments of 59% and the transpiration reduction of 12%. The yield, leaf temperature and stomatal conductance were not significant different to high [CO2], different from the dry matter, who showed increment of 20% (F1S1) and the water use efficiency who showed increase of 90% for high [CO2]. The osmotic potential was lower in plants under drought stress (F2S2 and F1S2), followed by plants under high [CO2] (F1S1). Despite the increment in photosynthesis, high [CO2] does not guarantee higher yield.

Water requirement and yield of fig trees under different drip irrigation management

This work aimed to study the effect of drip irrigation management on growth and yield of the 'Roxo de Valinhos' fig tree (Ficus carica L.), at three years old, and to determine crop coefficients (Kc) and its water requirement (ETc) under Baixada Fluminense climate and soil conditions, state of Rio de Janeiro, Brazil. The study was carried out in the experimental area of SIPA (Sistema Integrado de Produção Agroecológica) in Seropédica, Rio de Janeiro State, from July 2011 to May 2012. The experimental area was divided in two blocks, named B1 (sandy clay loam texture) and B2 (loamy sand texture). In each block, irrigation frequencies (IF) of two (T1) and four days (T2) were evaluated, as well as the irrigation absence (T3). Irrigation management and water consumption determination were performed through the soil water balance, using the TDR technique. Plant growth was not affected by IF, differing only in the number of produced internodes. For both soil textures, the mean Kc was 0.60, with a significant difference (p<0.05) only for IF. The estimated mean yield showed no significant differences between both textural classes, ranging from 6,612 kg ha-1 (T3) to 8,554 kg ha-1 (T1). This study indicates the importance of irrigation frequency in the irrigation management of fig trees cultivated in soils with different physical characteristics.

Application of artificial neural networks as an alternative to volumetric water balance in drip irrigation management in watermelon crop

Precision irrigation seeks to establish strategies which achieve an efficient ratio between the volume of water used (reduction in input) and the productivity obtained (increase in production). There are several studies in the literature on strategies for achieving this efficiency, such as those dealing with the method of volumetric water balance (VWB). However, it is also of great practical and economic interest to set up versatile implementations of irrigation strategies that: (i) maintain the performance obtained with other implementations, (ii) rely on few computational resources, (iii) adapt well to field conditions, and (iv) allow easy modification of the irrigation strategy. In this study, such characteristics are achieved when using an Artificial Neural Network (ANN) to determine the period of irrigation for a watermelon crop in the Irrigation Perimeter of the Lower Acaraú, in the state of Ceará, Brazil. The Volumetric Water Balance was taken as the standard for comparing the management carried out with the proposed implementation of ANN. The statistical analysis demonstrates the effectiveness of the proposed management, which is able to replace VWB as a strategy in automation.

Greenhouse crisphead lettuce grown with mulching and under different soil water tensions

ABSTRACT Proper irrigation management is important both to enable adequate water supply and to minimize problems with diseases, nutrient leaching and unnecessary water and power wastes. Thus, this study aimed at improving irrigation management in greenhouses. For that reason, we assessed the effect of various water tensions on yield performance of crisphead lettuce, Raider-Plus cv. , grown with mulching. The experiment was conducted in greenhouse at the Federal University of Lavras. Treatments constituted five different soil water tensions, namely 12, 25, 35, 45, and 70 kPa. The results showed that irrigation must be carried out at water soil tension of around 12 kPa to reach satisfying commercial values for both total and commercial yield, 66 and 50 t ha-1, as well as keeping good vegetable quality. At this tension, total water consumption was of 167.25 mm. The water use efficiency demonstrated quadratic response to treatments, with high water consumption efficiency found in intermediate treatments (35 and 45 kPa), achieving values of 579.87 and 471.71 kg ha -1mm-1, respectively.

Pasvik Water Quality Report Environmental Monitoring Programme in the Norwegian, Finnish and Russian Border Area

The Pasvik monitoring programme was created in 2006 as a result of the trilateral cooperation, and with the intention of following changes in the environment under variable pollution levels. Water quality is one of the basic elements of the Programme when assessing the effects of the emissions from the Pechenganikel mining and metallurgical industry (Kola GMK). The Metallurgic Production Renovation Programme was implemented by OJSC Kola GMK to reduce emissions of sulphur and heavy metal concentrated dust. However, the expectations for the reduction in emissions from the smelter in the settlement Nikel were not realized. Nevertheless, Kola GMK has found that the modernization programme’s measures do not provide the planned reductions of sulfur dioxide emissions. In this report, temporal trends in water chemistry during 2000–2009 are examined on the basis of the data gathered from Lake Inari, River Pasvik and directly connected lakes, as well as from 26 small lakes in three areas: Pechenganikel (Russia), Jarfjord (Norway) and Vätsäri (Finland). The lower parts of the Pasvik watercourse are impacted by both atmospheric pollution and direct wastewater discharge from the Pechenganikel smelter and the settlement of Nikel. The upper section of the watercourse, and the small lakes and streams which are not directly linked to the Pasvik watercourse, only receive atmospheric pollution. The data obtained confirms the ongoing pollution of the river and water system. Copper (Cu), nickel (Ni) and sulphates are the main pollution components. The highest levels were observed close to the smelters. The most polluted water source of the basin is the River Kolosjoki, as it directly receives the sewage discharge from the smelters and the stream connecting the Lakes Salmijarvi and Kuetsjarvi. The concentrations of metals and sulphates in the River Pasvik are higher downstream from the Kuetsjarvi Lake. There has been no fall in the concentrations of pollutants in Pasvik watercourse over the last 10 years. Ongoing recovery from acidification has been evident in the small lakes of the Jarfjord and Vätsäri areas during the 2000s. The buffering capacity of these lakes has improved and the pH has increased. The reason for this recovery is that sulphate deposition has decreased, which is also evident in the water quality. However, concentrations of some metals, especially Ni and Cu, have risen during the 2000s. Ni concentrations have increased in all three areas, and Cu concentrations in the Pechenganickel and Jarfjord areas, which are located closer to the smelters. Emission levels of Ni and Cu did not fall during 2000s. In fact, the emission levels of Ni compounds even increased compared to the 1990s.

Developing Service-based Solutions for Water Treatment in Finnish Mining Industry

The aim of this master’s thesis is to analyze the mining industry customers' current and future needs for the water treatment services and discover new business development opportunities in the context of mine water treatment. In addition, the study focuses on specifying service offerings needed and evaluate suitable revenue generation models for them. The main research question of the study is: What kind of service needs related to water treatment can be identified in the Finnish mining industry? The literature examined in the study focused on industrial service classification and new service development process as well as the revenue generation of services. A qualitative research approach employing a case study method was chosen for the study. The present study uses customer and expert interviews as primary data source, complemented by archival data. The primary data was gathered by organizing total of 13 interviews, and the interviews were analyzed by using qualitative content analysis. The abductive-logic was chosen as the way of conducting scientific reasoning in this study. As a result, new service proposals were developed for Finnish mine industry suppliers. The main areas of development were on asset efficiency services and process support services. The service needs were strongly associated with suppliers’ know-how of water treatment process optimization, cost-effectiveness as well as on alternative technologies. The study provides an insight for managers that wish to pursue a water treatment services as a part of their business offering.

Turbulent shallow-water model for orographic subgrid-scale perturbations

A parallel pseudo-spectral method for the simulation in distributed memory computers of the shallow-water equations in primitive form was developed and used on the study of turbulent shallow-waters LES models for orographic subgrid-scale perturbations. The main characteristics of the code are: momentum equations integrated in time using an accurate pseudo-spectral technique; Eulerian treatment of advective terms; and parallelization of the code based on a domain decomposition technique. The parallel pseudo-spectral code is efficient on various architectures. It gives high performance onvector computers and good speedup on distributed memory systems. The code is being used for the study of the interaction mechanisms in shallow-water ows with regular as well as random orography with a prescribed spectrum of elevations. Simulations show the evolution of small scale vortical motions from the interaction of the large scale flow and the small-scale orographic perturbations. These interactions transfer energy from the large-scale motions to the small (usually unresolved) scales. The possibility of including the parametrization of this effects in turbulent LES subgrid-stress models for the shallow-water equations is addressed.

Modified nano- and microcellulose based adsorption materials in water treatment

In recent decades, industrial activity growth and increasing water usage worldwide have led to the release of various pollutants, such as toxic heavy metals and nutrients, into the aquatic environment. Modified nanocellulose and microcellulose-based adsorption materials have the potential to remove these contaminants from aqueous solutions. The present research consisted of the preparation of five different nano/microcellulose-based adsorbents, their characterization, the study of adsorption kinetics and isotherms, the determination of adsorption mechanisms, and an evaluation of adsorbents’ regeneration properties. The same well known reactions and modification methods that were used for modifying conventional cellulose also worked for microfibrillated cellulose (MFC). The use of succinic anhydride modified mercerized nanocellulose, and aminosilane and hydroxyapatite modified nanostructured MFC for the removal of heavy metals from aqueous solutions exhibited promising results. Aminosilane, epoxy and hydroxyapatite modified MFC could be used as a promising alternative for H2S removal from aqueous solutions. In addition, new knowledge about the adsorption properties of carbonated hydroxyapatite modified MFC as multifunctional adsorbent for the removal of both cations and anions ions from water was obtained. The maghemite nanoparticles (Fe3O4) modified MFC was found to be a highly promising adsorbent for the removal of As(V) from aqueous solutions due to its magnetic properties, high surface area, and high adsorption capacity . The maximum removal efficiencies of each adsorbent were studied in batch mode. The results of adsorption kinetics indicated very fast removal rates for all the studied pollutants. Modeling of adsorption isotherms and adsorption kinetics using various theoretical models provided information about the adsorbent’s surface properties and the adsorption mechanisms. This knowledge is important for instance, in designing water treatment units/plants. Furthermore, the correspondence between the theory behind the model and properties of the adsorbent as well as adsorption mechanisms were also discussed. On the whole, both the experimental results and theoretical considerations supported the potential applicability of the studied nano/microcellulose-based adsorbents in water treatment applications.

Role of angiotensin II and vasopressin receptors within the supraoptic nucleus in water and sodium intake induced by the injection of angiotensin II into the medial septal area

In this study we investigated the effects of the injection into the supraoptic nucleus (SON) of non-peptide AT1- and AT2-angiotensin II (ANG II) receptor antagonists, DuP753 and PD123319, as well as of the arginine-vasopressin (AVP) receptor antagonist d(CH2)5-Tyr(Me)-AVP, on water and 3% NaCl intake induced by the injection of ANG II into the medial septal area (MSA). The effects on water or 3% NaCl intake were assessed in 30-h water-deprived or in 20-h water-deprived furosemide-treated adult male rats, respectively. The drugs were injected in 0.5 µl over 30-60 s. Controls were injected with a similar volume of 0.15 M NaCl. Antagonists were injected at doses of 20, 80 and 180 nmol. Water and sodium intake was measured over a 2-h period. Previous administration of the AT1 receptor antagonist DuP753 into the SON decreased water (65%, N = 10, P<0.01) and sodium intake (81%, N = 8, P<0.01) induced by the injection of ANG II (10 nmol) into the MSA. Neither of these responses was significantly changed by injection of the AT2-receptor antagonist PD123319 into the SON. On the other hand, while there was a decrease in water intake (45%, N = 9, P<0.01), ANG II-induced sodium intake was significantly increased (70%, N = 8, P<0.01) following injection of the V1-type vasopressin antagonist d(CH2)5-Tyr(Me)-AVP into the SON. These results suggest that both AT1 and V1 receptors within the SON may be involved in water and sodium intake induced by the activation of ANG II receptors within the MSA. Furthermore, they do not support the involvement of MSA AT2 receptors in the mediation of these responses.

Zinc and water intake in rats: investigation of adrenergic and opiatergic central mechanisms

We have demonstrated that central administration of zinc in minute amounts induces a significant antidipsogenic action in dehydrated rats as well as in rats under central cholinergic and angiotensinergic stimulation. Here we show that acute third ventricle injections of zinc also block water intake induced by central ß-adrenergic stimulation in Wistar rats (190-250 g). Central inhibition of opioid pathways by naloxone reverses the zinc-induced antidipsogenic effect in dehydrated rats. After 120 min, rats receiving third ventricle injections of isoproterenol (160 nmol/rat) exhibited a significant increase in water intake (5.78 ± 0.54 ml/100 g body weight) compared to saline-treated controls (0.15 ± 0.07 ml/100 g body weight). Pretreatment with zinc (3.0, 30.0 and 300.0 pmol/rat, 45 min before isoproterenol injection) blocked water intake in a dose-dependent way. At the highest dose employed a complete blockade was demonstrable (0.54 ± 0.2 ml/100 g body weight). After 120 min, control (NaAc-treated) dehydrated rats, as expected, exhibited a high water intake (7.36 ± 0.39 ml/100 g body weight). Central administration of zinc blocked this response (2.5 ± 0.77 ml/100 g body weight). Naloxone pretreatment (82.5 nmol/rat, 30 min before zinc administration) reverted the water intake to the high levels observed in zinc-free dehydrated animals (7.04 ± 0.56 ml/100 g body weight). These data indicate that zinc is able to block water intake induced by central ß-adrenergic stimulation and that zinc-induced blockade of water intake in dehydrated rats may be, at least in part, due to stimulation of central opioid peptides.