A primeira lei da termodinâmica dos processos homogêneos

Thermodynamics of homogeneous processes, which corresponds to the very special situation in thermodynamics of continuous media, is used to discuss the first law. An important part of this work is the exposition of some typical mathematical errors, frequently found in the traditional presentation of thermodynamics. The concepts of state and process functions are discussed, as well as reverse and reversible processes, temporality and its implications on thermodynamics, energy reservoirs and symmetry. Our proposal is to present the first law by using a time dependent viewpoint coherent with mechanics and the foundations of that viewpoint.

Avaliação de NO2 na atmosfera de ambientes externos e internos na cidade de Araraquara, São Paulo

The seasonal behavior of NO2 concentration shows a maximum occurring during sugarcane crop and this suggests that the biomass burning is significant source of emission at this time of the year. Along the day, the variation of the NO2 showed a decrease during the increased sunlight and an increase thereafter, caused by occurrence of photochemical reactions. Measurements of NO2 were done inside of residential and industrial kitchens and also inside of a parking garage located in the underground of a supermarket building. The indoor concentrations of NO2 were significantly higher than the concentrations of the external atmosphere and it shows the importance of the sources of internal emissions.

Uma análise do coeficiente de remoção de poluentes em função do espectro de gotas de chuva em diferentes localidades no Brasil e Alemanha

The pollutant transference among reservoirs atmosphere-hydrosphere, relevant to the atmospheric chemistry, depends upon scavenging coefficient (Λ) calculus, which depends on the raindrop size distribution as well as on the rainfall systems, both different to each locality. In this work, the Λ calculus will be evaluated to gas SO2 and particulate matter fine and coarse among five sites in Germany and two in Brazil. The results show three possible classifications in function of Λ, comparable to literature, however with a greater range due to the differences of rainfall system sites. This preliminary study supports future researches

Fluxos de nutrientes associados às descargas de água subterrânea para a Lagoa Mangueira (Rio Grande do Sul, Brasil)

This study assesses the importance of groundwater discharge to dissolved nutrient levels in Mangueira Lagoon. A transect of an irrigation canal in the margin of Lagoon demonstrated a strong geochemical gradient due to high groundwater inputs in this area. Using 222Rn as a quantitative groundwater tracer, we observed that the flux of dissolved inorganic nitrogen (DIN), silicate and phosphate (1178 and 1977; 26190 and 35652; 167 and 188 mol d-1 for winter and summer, respectively) can continually supply/sustain primary production. The irrigation canals act as an artificial underground tributary and represent a new source of nutrients to coastal lagoons.

Processos naturais de biodegradação do petróleo em reservatórios

Petroleum biodegradation in reservoirs is a process caused by different microorganisms affecting many oil deposits which modifies the oil composition in a quasi-stepwise process starting from n-alkanes and isoprenoids through to diasteranes. This causes oil souring and increased viscosity, sulfur and metal content, having a direct impact on oil production and refining costs.

Fatores químicos e físicos que afetam a contaminação por chumbo e cobre em água potável: uma abordagem para o estudo de caso em química analítica

Lead and copper concentrations in drinking water increase considerably on going from municipality reservoirs to the households sampled in Ribeirão Preto (SP-Brazil). Flushing of only 3 liters of water reduced metal concentrations by more than 50%. Relatively small changes in water pH rapidly affected corrosion processes in lead pipes, while water hardness appeared to have a long-term effect. This approach aims to encourage University teachers to use its content as a case study in disciplines of Instrumental Analytical Chemistry and consequently increase knowledge about drinking water contamination in locations where no public monitoring of trace metals is in place.

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.

Terpanos pentacíclicos como indicadores de heterogeneidades composicionais em reservatório de petróleo biodegradado

Reservoir geochemistry has been effectively used to evaluate compositional heterogeneity in petroleum reservoirs by employing oil fingerprinting technique to assess reservoir continuity, primarily in paraffin oil accumulations. In-reservoir biodegradation has resulted in vast deposits of heavy oils globally; therefore, the application of reservoir geochemistry to such accumulations becomes necessary. We recommend the use of pentacyclic terpanes instead of lower molecular compounds, which are less resistant to biodegradation. Using oil fingerprinting technique in this novel way enabled the differentiation of oil composition among sedimentary facies of tar sands (Pirambóia Formation, Paraná Basin).

Sedimentação de nutrientes e material particulado em reservatório sob influência de atividades de piscicultura no semiárido do Rio Grande do Norte

Nutrient levels in water reservoirs have been increasing over the years worldwide and fish farming is one of the activities with the potential to cause negative impacts on these environments. Thus, the sedimentation of the main nutrients was evaluated in a reservoir as well as the contribution of aquaculture in raising these rates. The results indicated a significant difference for all nutrients, with higher concentrations in areas near the fish farming, and lower levels in more distant regions. Therefore, assessments that focus only on the water column do not reflect the true impact of this activity.

Pequisas físicas e químicas do sistema hidrográfico da região lagunar de Cananéia: I - Cursos de águas

The present elaboration is a "previous note" about two watercourses, Maria Rodrigues and Baguaçú, belonging to Hydrografic System of the Cananeas Lagoon Region in the Southern Part of it he Coast of the Estado de São Paulo, Brazil, which is the objete of our physical and chemical researches. It is based on the first results obtained from our contact with that region, ttfie studies of which are being continued and will still have to confirm or not the previous conclusions, which we are presenting in this "provisional paper". We studied the Maria Rodrigues and the Baguacu under the discussion whether they are to be clasified as a river in the poper sense ot the word or waUer-courses of any other origin. For this purpose we established observatory-stations along their whole course where we collected quantities of water to be analised. The data included in the table nº 1 and 2 refer to the physical and chemical properties of these portions of water. These physical and chemical properties were discussed and compared one with the other according to the observatory-stations, at the same moment and the tide predominating on that occasion. The physical and chemical datas were obtained according to the norms recommended by the Conseil International permanent pour l'Exploration de la Mer, Copenhague. We also presented a sketch of both; we described their relations with regard to the Mar de Cananéia; we inserted comprehensible histograms of the distribution of the observatory-stations, each of them with the respective indices, and at last we tried to correlate the occurrence of the "plancton" with the physical and chemical properties of water as well in the Maria Rodrigues as in the Baguacú. From these researches result the following previous conclusions: 1 - By the data obtained up to now nothing could be formulated as to a cyclical or "seasonal" aspect. 2 - By the comparison of the phenomena which present the rivers in the proper sense of the word and those observed in the Maria Rodrigues and the Baguacú, we are convinced that both are water-courses of the classical type "marigot,". 3 - Their channels are maintained open by the effect of the tide and, more perphaps, by the infiltration-water deriving from the underground-water level owing to the type of the soil of that region, which in mean shows an elevation of 2-4 meters over sea-level. 4 - From tables 1 and 2 and histograms 2 and 3 we stated that the water, not only of the Maria Rodrigues but also of the Baguacú, conserve more or less the same physical and chemical properties, provided that: 1) the localities to be compared are the mouths or equidistant points from them in the lower course, and 2) the moment and tide must be the same. Tables 3a and 3b show sufficiently this supposition.

Solanum americanum: reservoir for Potato virus Y and Cucumber mosaic virus in sweet pepper crops

Weeds can act as important reservoirs for viruses. Solanum americanum (Black nightshade) is a common weed in Brazil and samples showing mosaic were collected from sweet pepper crops to verify the presence of viruses. One sample showed mixed infection between Cucumber mosaic virus (CMV) and Potato virus Y (PVY) and one sample showed simple infection by PVY. Both virus species were transmitted by plant extract and caused mosaic in tomato (Solanum lycopersicum cv. Santa Clara), sweet pepper (Capsicum annuum cv. Magda), Nicotiana benthamiana and N. tabaccum TNN, and local lesions on Chenopodium quinoa, C. murale and C. amaranticolor. The coat protein sequences for CMV and PVY found in S. americanum are phylogenetically more related to isolates from tomato. We conclude that S. americanum can act as a reservoir for different viruses during and between sweet pepper crop seasons.

Estimation of evaporation in the Banabuiú dam, in the state of Ceará, Brazil, by different combined methods, derived from the Penman equation

The state of Ceará, Brazil, has 75% of its area covered by Brazilian semiarid, with its peculiar features. In this state, the dams are constituted in water structure of strategic importance, ensuring, both in time and space, the development and supply of water to population. However, construction of reservoirs results in various impacts that should be carefully observed when deciding on their implementation. One of the impacts identified as negative is the increased evaporation, which constitutes a major component of water balance in reservoirs, especially in arid regions. Several methods for estimating evaporation have been proposed over time, many of them deriving from the Penman equation. This study evaluated six different methods for estimating evaporation in order to determine the most suitable for use in hydrological models for water balance in reservoirs in the state of Ceará. The tested methods were proposed by Penman, Kohler-Nordenson-Fox, Priestley-Taylor, deBruim-Keijman, Brutsaert-Stricker and deBruim. The methods presented good performance when tested for water balance during the dry season, and the Priestley-Taylor was the most appropriate, since the data from de simulated water balance with evaporation estimated by this method were the closest of the water balance data observed from measures of reservoir level and the elevation-volume curve provided by the Company of Management of Water Resources of the state of Ceará - COGERH.

Silting in the dense reservoir network of the Pereira de Miranda catchment

This study aims to analyze the impacts of the reservoir network within Pereira de Miranda - CE catchment (also called Pentecoste) over sediment transport and storage capacity of the system. The survey of the "damming" was carried out using satellite images. We identified 502 erosion units, derived from overlaying maps of the Universal Soil Loss Equation parameters, which allowed the estimation of localized erosion in the basin and identification of areas potentially generating sediment. In order to estimate silting in Pentecoste reservoir, different system structure scenarios were considered. An average erosion rate of 59 t ha-1year-1 was estimated. According to the model, the silting of Pentecoste reservoir may vary from 1.1 to 2.6% per decade, depending on the scenario considered. It is also observed that the reservoirs upstream can retain up to 58% of the sediment that would reach the Pentecoste reservoir. Very small reservoirs with a capacity of up to 100,000 m³, although representing only 1.83% of the system water availability, are able to retain almost 8% of total sediment produced.

Evaluation of sediment production and siltation in a small earth dam in Fernandópolis, SP

The siltation is a natural process, but can be accelerated by human actions and results in major problems for the reservoirs, reducing its useful volume for irrigation. An example of this problem was the reduction of the area of mirror water of Fernandópolis municipal dam in 48.3% during 20 years. Therefore, this study aimed to evaluate the production of sediments and siltation of Fernandópolis municipal dam from a methodology that can be applied to small earth dams for agricultural purposes. For this, it was monitored, monthly throughout the year, the volume of sediment deposited in the reservoir. The percentage of retention sediment in Fernandópolis municipal dam ranged from 53.9 to 94.5%, that associated with a high specific sediment yield, will cause its full silting in at most 57 years. It is recommended to minimize this process the restoration of permanent preservation areas and the removal of 17,500 m³ of sediment from the riverbed of the dam.

Distribution of water in sandy soil applied by drip

The search for the use of water with high levels of efficiency has motivated the use of drip irrigation in several agricultural systems. However, for the efficiency be ensured, it is necessary that the water distribution in the soil profile must to be known in more details. As it is a highly variable process, function of the local characteristics, is essential the study of each case. The objective of this research was evaluating the water distribution in the soil profile, from drippers installed in surface and 0.15 m below the soil surface. The experiment was realized in the Technical Center of Irrigation (TCI) of the State University of Maringá - PR. The water monitoring in the soil profile was done with TDR probes installed in a box containing sandy soil, at the depths from 0.05 to 0.80 m; and 0.05 to 0.35 m of lateral spacing, at intervals of 0.05 m, totalizing 30 probes. The treatments were differentiated in relation of the installation depth of the emitters (0.0 and 0.15 m) and flow (1, 2, 4, 6, and 8 L h-1). The irrigation time was 8 hours continuous with reading of the TDR probes each 30 minutes. The results allowed concluding that the wet area with the emitter positioned on the soil surface was directly proportional to the flow increase. For the underground dripper, this area was substantially smaller and the water losses by percolation were higher, mainly to the flows higher than 4 L h-1, which provided to unacceptable water losses that should be avoided.