Prediction of Crude Oil Properties and Chemical Composition by Means of Steady-State and Time-Resolved Fluorescence

Steady-state and time-resolved fluorescence measurements are reported for several crude oils and their saturates, aromatics, resins, and asphaltenes (SARA) fractions (saturates, aromatics and resins), isolated from maltene after pentane precipitation of the asphaltenes. There is a clear relationship between the American Petroleum Institute (API) grade of the crude oils and their fluorescence emission intensity and maxima. Dilution of the crude oil samples with cyclohexane results in a significant increase of emission intensity and a blue shift, which is a clear indication of the presence of energy-transfer processes between the emissive chromophores present in the crude oil. Both the fluorescence spectra and the mean fluorescence lifetimes of the three SARA fractions and their mixtures indicate that the aromatics and resins are the major contributors to the emission of crude oils. Total synchronous fluorescence scan (TSFS) spectral maps are preferable to steady-state fluorescence spectra for discriminating between the fractions, making TSFS maps a particularly interesting choice for the development of fluorescence-based methods for the characterization and classification of crude oils. More detailed studies, using a much wider range of excitation and emission wavelengths, are necessary to determine the utility of time-resolved fluorescence (TRF) data for this purpose. Preliminary models constructed using TSFS spectra from 21 crude oil samples show a very good correlation (R(2) > 0.88) between the calculated and measured values of API and the SARA fraction concentrations. The use of models based on a fast fluorescence measurement may thus be an alternative to tedious and time-consuming chemical analysis in refineries.

Evaluation of the effect of ammonium carbamate on the stability of proteins

BACKGROUND: The use of the volatile salt ammonium carbamate in protein downstream processing has recently been proposed. The main advantage of using volatile salts is that they can be removed from precipitates and liquid effluents through pressure reduction or temperature increase. Although previous studies showed that ammonium carbamate is efficient as a precipitant agent, there was evidence of denaturation in some enzymes. In this work, the effect of ammonium carbamate on the stability of five enzymes was evaluated. RESULTS: Activity assays showed that alpha-amylase (1,4-alpha-D-glucan glucanohydrolase, EC 3.2.1.1), lysozyme (1,4-beta-N-acetylmuramoylhydrolase, EC 3.2.1.17) and lipase (triacyl glycerol acyl hydrolase, EC 3.1.1.3) did not undergo activity loss in ammonium carbamate solutions with concentrations from 1.0 to 5.0 mol kg(-1), whereas cellulase complex (1,4-(1,3 : 14)-beta-D-glucan 4-glucano-hydrolase, EC 3.2.1.4) and peroxidase (hydrogen peroxide oxidoreductase, EC 1.11.1.7) showed an average activity loss of 55% and 44%, respectively. Precipitation assays did not show enzyme denaturation or phase separation for alpha-amylase and lipase, while celullase and peroxidase precipitated with some activity reduction. Analysis of similar experiments with ammonium and sodium sulfate did not affect the activity of enzymes. CONCLUSION: Celullase and peroxidase were denatured by ammonium carbamate. While more systematic studies are not available, care must be taken in designing a protein precipitation with this salt. The results suggest that the generally accepted idea that salts that denature proteins tend to solubilize them does not hold for ammonium carbamate. (C) 2010 Society of Chemical Industry

Toluene and naphthalene sorption by iron oxide/clay composites

Commercial bentonite (BFN) and organoclay (WS35), as well as iron oxide/clay composite (Mag_BFN) and iron/oxide organoclay composite (Mag_S35) were prepared for toluene and naphthalene sorption. Mag_BFN and Mag_S35 were obtained, respectively, by the precipitation of iron oxide hydrates onto sodium BFN and S35 clay particles. The materials were characterized by powder X-ray diffraction (XRD), X-ray Fluorescence (XRF), and TG and DTA. From XRF results and TG data on calcined mass basis, a quantitative method was developed to estimate the iron compound contents of the composites, as well as the organic matter content present in WS35 and Mag_S35.

Functional characterization of the oxaloacetase encoding gene and elimination of oxalate formation in the beta-lactam producer Penicillium chrysogenum

Penicillium chrysogenum is widely used as an industrial antibiotic producer, in particular in the synthesis of g-lactam antibiotics such as penicillins and cephalosporins. In industrial processes, oxalic acid formation leads to reduced product yields. Moreover, precipitation of calcium oxalate complicates product recovery. We observed oxalate production in glucose-limited chemostat cultures of P. chrysogenum grown with or without addition of adipic acid, side-chain of the cephalosporin precursor adipoyl-6-aminopenicillinic acid (ad-6-APA). Oxalate accounted for up to 5% of the consumed carbon source. In filamentous fungi, oxaloacetate hydrolase (OAH; EC3.7.1.1) is generally responsible for oxalate production. The P. chrysogenum genome harbours four orthologs of the A. niger oahA gene. Chemostat-based transcriptome analyses revealed a significant correlation between extracellular oxalate titers and expression level of the genes Pc18g05100 and Pc22g24830. To assess their possible involvement in oxalate production, both genes were cloned in Saccharomyces cerevisiae, yeast that does not produce oxalate. Only the expression of Pc22g24830 led to production of oxalic acid in S. cerevisiae. Subsequent deletion of Pc22g28430 in P. chrysogenum led to complete elimination of oxalate production, whilst improving yields of the cephalosporin precursor ad-6-APA. (C) 2011 Elsevier Inc. All rights reserved.

Use of SECM to study the electrochemical behavior of DIN 1.4575 superferritic stainless steel aged at 475 degrees C

In order to lower the excessive costs of metallic prosthesis materia Is alternatives to Ti and Ti alloys have been searched. in this study, the corrosion resistance of the DIN 1.4575 superferritic stainless steel, either solution annealed or solution annealed and aged at 475 degrees C for periods varying from 100 to 1080 h, was investigated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization methods in Hanks` solution. The solution annealed and the aged for 1080 h samples were also tested using scanning electrochemical microscopy (SECM) in a 0.1 mol/L NaCl solution at 25 degrees C. The EIS results showed that the corrosion resistance of the DIN 1.4575 steel decreases with heat treatment time at 475 degrees C probably due to alpha prime formation. Besides the diminution of the overall impedance values, the low frequency limit of the Nyquist diagrams show a progressive change from an almost capacitive response to a resistive behavior as the heat treatment time increases. Pitting corrosion resistance also decreased with aging time at 475 degrees C.

On the solubility of proteins as a function of pH: Mathematical development and application

Thermodynamic relations between the solubility of a protein and the solution pH are presented in this work. The hypotheses behind the development are that the protein chemical potential in liquid phase can be described by Henry`s law and that the solid-liquid equilibrium is established only between neutral molecules. The mathematical development results in an analytical expression of the solubility curve, as a function of the ionization equilibrium constants, the pH and the solubility at the isoelectric point. It is shown that the same equation can be obtained either by directly calculating the fraction of neutral protein molecules or by integrating the curve of the protein average charge. The methodology was successfully applied to the description of the solubility of porcine insulin as a function of pH at three different temperatures and of bovine beta-lactoglobulin at four different ionic strengths. (C) 2011 Elsevier B.V. All rights reserved.

Structure and properties of an austenitic stainless steel AISI 316L grade ASTM F138 after low temperature plasma nitriding

Austenitic stainless steels cannot be conventionally nitrided at temperatures near 550 degrees C due to the intense precipitation of chromium nitrides in the diffusion zone. The precipitation of chro-mium nitrides increases the hardness but severely impairs corrosion resistance. Plasma nitriding allows introducing nitrogen in the steel at temperatures below 450 degrees C, forming pre-dominantly expanded austenite (gamma(N)), with a crystalline structure best represented by a special triclin-ic lattice, with a very high nitrogen atomic concentration promoting high compressive residual stresses at the surface, increasing substrate hardness from 4 GPa up to 14 GPa on the nitrided case.

The influence of environmental variables on capybara (Hydrochoerus hydrochaeris: Rodentia, Hydrochoeridae) detectability in anthropogenic environments of southeastern Brazil

Capybaras were monitored weekly from 1998 to 2006 by counting individuals in three anthropogenic environments (mixed agricultural fields, forest and open areas) of southeastern Brazil in order to examine the possible influence of environmental variables (temperature, humidity, wind speed, precipitation and global radiation) on the detectability of this species. There was consistent seasonality in the number of capybaras in the study area, with a specific seasonal pattern in each area. Log-linear models were fitted to the sample counts of adult capybaras separately for each sampled area, with an allowance for monthly effects, time trends and the effects of environmental variables. Log-linear models containing effects for the months of the year and a quartic time trend were highly significant. The effects of environmental variables on sample counts were different in each type of environment. As environmental variables affect capybara detectability, they should be considered in future species survey/monitoring programs.

PCJ River Basins` Water Availability Caused by Water Diversion Scenarios to Supply Metropolitan Areas of So Paulo

A dynamic systems simulation model of water resources was developed as a tool to help analyze alternatives to water resources management for the Piracicaba, Capivari and Jundiai River Water Basins (RB-PCJ), and used to run six 50-year simulations from 2004 to 2054. The model estimates water supply and demand, as well as contamination load by several consumers. Six runs were performed using a constant mean precipitation value, changing water supply and demand and different volumes diverted from RB-PCJ to RB-Alto Tiet. For the Business as Usual scenario, the Sustainability Index went from 0.44 in 2004 to 0.20 by 2054. The Water Sustainability Index changed from 74% in 2004 to 131% by 2054. The Falkenmark Index changed from 1,403 m(3) person (-aEuro parts per thousand 1) year (-aEuro parts per thousand 1) in 2004 to 734 m(3) person (-aEuro parts per thousand 1) year (-aEuro parts per thousand 1) by 2054. We concluded that sanitation is one of the major problems for the PCJ River Basins.

The impact of El Nino Southern Oscillation phases on off-season maize yield for a subtropical region of Brazil

In recent years, maize has become one of the main alternative crops for the autumn winter growing season in the central-western and southeastern regions of Brazil. However, water deficits, sub-optimal temperatures and low solar radiation levels are common problems that are experienced during this growing season by local farmers. One methodology to assess the impact of variable weather conditions on crop production is the use of crop simulation models. The goal of this study was to evaluate the effect of climate variability on maize yield for a subtropical region of Brazil. Specific objectives for this study were (1) to analyse the effect of El Nino Southern Oscillation (ENSO) on precipitation and air temperature for four locations in the state of Sao Paulo and (2) to analyse the impact of ENSO on maize grown off-season for the same four locations using a crop simulation model. For each site, historical weather data were categorised as belonging to one of three phases of ENSO: El Nino (warm sea surface temperature anomalies in the Pacific), La Nina (cool sea surface temperature anomalies) or neutral, based on an index derived from observed sea surface temperature anomalies. During El Nino, there is a tendency for an increase in the rainfall amount during May for the four selected locations, and also during April, mainly in three of the locations, resulting in an increase in simulated maize yield planted between February 15 and March 15. In general, there was a decrease in the simulated yield for maize grown off-season during neutral years. This study showed how a crop model can be used to assess the impact of climate variability on the yield of maize grown off-season in a subtropical region of Brazil. The outcomes of this study can be very useful for both policy makers and local farmers for agricultural planning and decision making. Copyright (C) 2009 Royal Meteorological Society

WATER RESOURCES SITUATION AT PIRACICABA, CAPIVARI AND JUNDIAI WATERSHEDS USING A DYNAMIC SYSTEMS MODEL

Using a dynamic systems model specifically developed for Piracicaba, Capivari and Jundia River Water Basins (BH-PCJ) as a tool to help to analyze water resources management alternatives for policy makers and decision takers, five simulations for 50 years timeframe were performed. The model estimates water supply and demand, as well as wastewater generation from the consumers at BH-PCJ. A run was performed using mean precipitation value constant, and keeping the actual water supply and demand rates, the business as usual scenario. Under these considerations, it is expected an increment of about similar to 76% on water demand, that similar to 39% of available water volume will come from wastewater reuse, and that waste load increases to similar to 91%. Falkenmark Index will change from 1,403 m(3) person(-1) year(-1) in 2004, to 734 m(3) P(-1) year(-1) by 2054, and the Sustainability Index from 0.44 to 0.20. Another four simulations were performed by affecting the annual precipitation by 90 and 110%; considering an ecological flow equal to 30% of the mean daily flow; and keeping the same rates for all other factors except for ecological flow and household water consumption. All of them showed a tendency to a water crisis in the near future at BH-PCJ.

CORRELATION BETWEEN FLOWERING, FRUCTIFICATION AND ENVIRONMENTAL VARIABLES IN Solanum lycocarpum A. St.-Hil, SOLANACEAE

Solanum lycocarpum (lobeira) is a typical and abundant species of brazilian Cerrado, which occupies mainly surrounding disturbed areas. It has interesting characteristics from the point of view of reproductive biology, that probably are favoring the large occupation of habitats by the species. Based on the fact that the species produces flowers and fruit during all the year, the present study had the purpose to verify the association between flower and fruit production with environmental variables (temperature, relative humidity and precipitation), aiming to support future studies referring to reproductive biology and ecology of plant species from Cerrado biome. A population of S. lycocarpum composed of 34 plants in reproductive phase, situated in Morrinhos, south of the State of Goias, Brazil,, was evaluated. All the plants were geographically referenced with a GPS receptor. Observations were made monthly during 13 months (June, 2005 to July, 2006) quantifying open flowers and fruits produced in the intervals between the observations. It was possible suggest high conversion of flowers in fruits. The Spearman rank correlation showed positive correlation of flower number with precipitation and relative humidity. Fruit number was not correlated with the environmental variables.

Leaf area index estimation with MODIS reflectance time series and model inversion during full rotations of Eucalyptus plantations

The leaf area index (LAI) of fast-growing Eucalyptus plantations is highly dynamic both seasonally and interannually, and is spatially variable depending on pedo-climatic conditions. LAI is very important in determining the carbon and water balance of a stand, but is difficult to measure during a complete stand rotation and at large scales. Remote-sensing methods allowing the retrieval of LAI time series with accuracy and precision are therefore necessary. Here, we tested two methods for LAI estimation from MODIS 250m resolution red and near-infrared (NIR) reflectance time series. The first method involved the inversion of a coupled model of leaf reflectance and transmittance (PROSPECT4), soil reflectance (SOILSPECT) and canopy radiative transfer (4SAIL2). Model parameters other than the LAI were either fixed to measured constant values, or allowed to vary seasonally and/or with stand age according to trends observed in field measurements. The LAI was assumed to vary throughout the rotation following a series of alternately increasing and decreasing sigmoid curves. The parameters of each sigmoid curve that allowed the best fit of simulated canopy reflectance to MODIS red and NIR reflectance data were obtained by minimization techniques. The second method was based on a linear relationship between the LAI and values of the GEneralized Soil Adjusted Vegetation Index (GESAVI), which was calibrated using destructive LAI measurements made at two seasons, on Eucalyptus stands of different ages and productivity levels. The ability of each approach to reproduce field-measured LAI values was assessed, and uncertainty on results and parameter sensitivities were examined. Both methods offered a good fit between measured and estimated LAI (R(2) = 0.80 and R(2) = 0.62 for model inversion and GESAVI-based methods, respectively), but the GESAVI-based method overestimated the LAI at young ages. (C) 2010 Elsevier Inc. All rights reserved.

THE MONTHLY RAINFALL IN THE RIO DE JANEIRO STATE, BRAZIL: SEASONALITY AND TREND

The objective of this work was to carry a descriptive analysis in the monthly precipitation of rainfall stations from Rio de Janeiro State, Brazil, using data of position and dispersion and graphical analyses, and to verify the presence of seasonality and trend in these data, with a study about the application of models of time series. The descriptive statistics was to characterize the general behavior of the series in three stations selected which present consistent historical series. The methodology of analysis of variance in randomized blocks and the determination of models of multiple linear regression, considering years and months as predictors variables, disclosed the presence of seasonality, what allowed to infer on the occurrence of repetitive natural phenomena throughout the time and absence of trend in the data. It was applied the methodology of multiple linear regression to removal the seasonality of these time series. The original data had been deducted from the estimates made by the adjusted model and the analysis of variance in randomized blocks for the residues of regression was preceded again. With the results obtained it was possible to conclude that the monthly rainfall present seasonality and they don`t present trend, the analysis of multiple regression was efficient in the removal of the seasonality, and the rainfall can be studied by means of time series.

Tree-ring formation, radial increment periodicity, and phenology of tree species from a seasonal semi-deciduous forest in southeast Brazil

Many tropical tree species produce growth rings in response to seasonal environmental factors that influence the activity of the vascular cambium. We applied the following methods to analyze the annual nature of treering formation of 24 tree species from a seasonal semi-deciduous forest of southeast Brazil: describing wood anatomy and phenology, counting tree rings after cambium markings, and using permanent dendrometer bands. After 7 years of systematic observations and measurements, we found the following: the trees lost their leaves during the dry season and grew new leaves at the end of the same season; trunk increment dynamics corresponded to seasonal changes in precipitation, with higher increment (active period) during the rainy season (October-April) and lower increment (dormant period) during the dry season (May-September); the number of tree rings formed after injuries to the cambium coincided with the number of years since the extraction of the wood samples. As a result of these observations, it was concluded that most study trees formed one growth ring per year. This suggests that tree species from the seasonal semi-deciduous forests of Brazil have an annual cycle of wood formation. Therefore, these trees have potential for use in future studies of tree age and radial growth rates, as well as to infer ecological and regional climatic conditions. These future studies can provide important information for the management and conservation of these endangered forests.