Modeling soil organic carbon dynamics in Oxisols of Ibiruba (Brazil) with the Century Model

introduction of conservation practices in degraded agricultural land will generally recuperate soil quality, especially by increasing soil organic matter. This aspect of soil organic C (SOC) dynamics under distinct cropping and management systems can be conveniently analyzed with ecosystem models such as the Century Model. In this study, Century was used to simulate SOC stocks in farm fields of the Ibiruba region of north central Rio Grande do Sul state in Southern Brazil. The region, where soils are predominantly Oxisols, was originally covered with subtropical woodlands and grasslands. SOC dynamics was simulated with a general scenario developed with historical data on soil management and cropping systems beginning with the onset of agriculture in 1900. From 1993 to 2050, two contrasting scenarios based on no-tillage soil management were established: the status quo scenario, with crops and agricultural inputs as currently practiced in the region and the high biomass scenario with increased frequency of corn in the cropping system, resulting in about 80% higher biomass addition to soils. Century simulations were in close agreement with SOC stocks measured in 2005 in the Oxisols with finer texture surface horizon originally under woodlands. However, simulations in the Oxisols with loamy surface horizon under woodlands and in the grassland soils were not as accurate. SOC stock decreased from 44% to 50% in fields originally under woodland and from 20% to 27% in fields under grasslands with the introduction of intensive annual grain crops with intensive tillage and harrowing operations. The adoption of conservation practices in the 1980s led to a stabilization of SOC stocks followed by a partial recovery of native stocks. Simulations to 2050 indicate that maintaining status quo would allow SOC stocks to recover from 81% to 86% of the native stocks under woodland and from 80% to 91 % of the native stocks under grasslands. Adoption of a high biomass scenario would result in stocks from 75% to 95% of the original stocks under woodlands and from 89% to 102% in the grasslands by 2050. These simulations outcomes underline the importance of cropping system yielding higher biomass to further increase SOC content in these Oxisols. This application of the Century Model could reproduce general trends of SOC loss and recovery in the Oxisols of the Ibiruba region. Additional calibration and validation should be conducted before extensive usage of Century as a support tool for soil carbon sequestration projects in this and other regions can be recommended. (C) 2009 Elsevier B.V. All rights reserved.

Pyrolysis-Gas Chromatography/Mass Spectrometry of Soil Organic Matter Extracted from a Brazilian Mangrove and Spanish Salt Marshes

The soil organic matter (SOM) extracted under different vegetation types from a Brazilian mangrove (Pai Matos Island, Sao Paulo State) and from three Spanish salt marshes (Betanzos Ria and Corrubedo Natural Parks, Galicia, and the Albufera Natural Park, Valencia) was investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The chemical variation was larger in SOM from the Spanish marshes than in the SOM of the Brazilian mangroves, possibly because the marshes included sites with both tidal and nontidal variation, whereas the mangrove forest underwent just tidal variation. Thus, plant-derived organic matter was better preserved under permanently anoxic environments. Moreover, given the low number of studied profiles and sedimentary-vegetation sequences in both areas, depth trends remain unclear. The chemical data also allow distinction between the contributions of woody and nonwoody vegetation inputs. Soil organic matter decomposition was found to cause: (i) a decrease in lignin contents and a relative increase in aliphatics; (ii) an increase in short-chain aliphatics at the expense of longer ones; (iii) a loss of odd-over-even dominance in alkanes and alkenes; and (iv) an increase in microbial products, including proteins, sterols, short-chain fatty acids, and alkanes. Pyrolysis-gas chromatography/mass spectrometry is a useful tool to study the behavior and composition of SOM in wetland environments such as mangroves and salt marshes. Additional profiles need to be studied for each vegetation type, however, to improve the interpretability of the chemical data.

Soil Organic Carbon Stocks of Rio Grande do Sul, Brazil

Robust and accurate regional estimates of C storage in soils are currently an important research topic because of ongoing debate about human-induced changes in the terrestrial C cycle. Widely available geoprocessing tools were applied to estimate native soil organic C (SOC) stocks of Rio Grande do Sul state in southern Brazil to a depth of 30 cm from previously sampled soil pedons under undisturbed vegetation. The study used a statewide comprehensive soil survey comprising a small-scale soil map, a climate map, and a soil pedon database. Soil organic C stocks under native vegetation were calculated with two different approaches: the Tier 1 method of the Intergovernmental Panel on Climate Change (IPCC) and a refined method based on actual field measurements derived from soil profile data. Highest SOC stocks occurred in Neossolos Quartzarenico hidromorfico (Aquents), Organossolos Tiomorficos (Hemists), Latossolos Brunos (Udox), and Vertissolos Ebanicos (Uderts) soil classes. Before human use of soils, most C was stored in the Latossolos Vermelhos (Udox) and Neossolos Regoliticos (Orthents), which occupy a large area of Rio Grande do Sul. Generally, IPCC default reference SOC stocks compared well with SOC stocks calculated from soil pedons. The total SOC stock of Rio Grande do Sul was estimated at 1510.3 Tg C (5.8 kg C m(-2)) by the IPPC method and 1597.5 +/- 363.9 Tg C (7.4 +/- 1.9 kg C m(-2)) calculated from soil pedons. The SOC digital map and SOC database developed in this study provide crucial background information for state-level contemporary assessment of C stocks and soil C sequestration programs and initiatives.

Contribution of soil organic carbon to the ion exchange capacity of tropical soils

Highly weathered soils represent about 3 billion ha of the tropical region. Oxisols represent about 60% of the Brazilian territory (more than 5 million km 2), in areas of great agricultural importance. Soil organic carbon (SOC) can be responsible for more than 80% of the cation exchange capacity (CEC) of highly weathered soils, such as Oxisols and Ultisols. The objective of this study was to estimate the contribution of the SOC to the CEC of Brazilian soils from different orders. Surface samples (0.0 to 0.2 m) of 30 uncultivated soils (13 Oxisols, 6 Ultisols, 5 Alfisols, 3 Entisols, I Histosol, 1 Inceptisol. and I Molisol), under native forests and from reforestation sites from Sao Paulo State, Brazil, were collected in order to obtain a large variation of (electro)chemical, physical, and mineralogical soil attributes. Total content of SOC was quantified by titulometric and colorimetric methods. Effective cation exchange capacity (ECEC) was obtained by two methods: the indirect method-summation-estimated the ECECi from the sum of basic cations (Ca+ Mg+ K+ Na) and exchangeable Al; and the direct ECECd obtained by the compulsive exchange method, using unbuffered BaCl2 solution. The contribution of SOC to the soil CEC was estimated by the Bennema statistical method. The amount of SOC var ied from 6.6 g kg(-1) to 213.4 g kg(-1). while clay contents varied from 40 g kg(-1) to 716 g kg(-1). Soil organic carbon contents were strongly associated to the clay contents, suggesting that clay content was the primary variable in controling the variability of SOC contents in the samples. Cation exchange capacity varied from 7.0 mmol(c) kg(-1) to 137.8 mmol(c) kg(-1) and had a positive Correlation with SOC. The mean contribution (per grain) of the SOC (1.64 mmol(c)) for the soil CEC was more than 44 times higher than the contribution of the clay fraction (0.04 mmol(c),). A regression model that considered the SOC content as the only significant variable explained 60% of the variation in the soil total CEC. The importance of SOC was related to soil pedogenetic process, since its contribution to the soil CEC was more evident in Oxisols with predominance of Fe and Al (oxihydr)oxides in the mineral fraction or in Ultisols, that presented illuviated clay. The influence of SOC in the sign and in the magnitude of the net charge of soils reinforce the importance of agricultural management systems that preserve high levels of SOC, in order to improve their sustainability.

Greenhouse gases emission from soil contaminated with automobile industry residue in Brazil

Solid waste of the automobile industry containing large amounts of heavy metals might affect the emission of greenhouse gases (GHG) when applied to the soil. Accumulation of inorganic chemical elements in the environment generally occurs due to human activity (industry, agriculture, mining and waste landfills). Residues from human activities may release heavy metals to the soil solution, causing toxicity to plants and other soil organisms. Heavy metals may also be adsorbed to clay minerals and/or complexed by the soil organic matter, becoming a potential source of pollutants. Not much is known about the behavior of solid wastes in tropical soil as regarded as source of greenhouse gases (GHG). The emission of GHG (CO(2), CH(4) and N(2)O) was evaluated in incubated soil samples collected in an area contaminated with a solid residue from an automobile industry. Samples were randomly collected at 0 to 0.2 m (a mix of soil and residue), 0.2 to 0.4 m (only residue) and 0.4 to 0.6 m (only soil). A contiguous uncontaminated area, cultivated with sugarcane, was also sampled following the same protocol. Canonical Discriminant Analysis and Principal Component Analysis were applied to the data to evaluate the GHG emission rates. Emission rates of GHG were greater in the samples from the contaminated than the sugarcane area, particularly high during the first days of incubation. CO(2) emissions were greater in samples collected at the upper layer for both areas, while CH(4) and N(2)O emissions were similar in all samples. The emission rates of CH(4) were the most efficient variables to differentiate contaminated and uncontaminated areas.

Method development and optimization for the determination of selenium in bean and soil samples using hydride generation electrothermal atomic absorption spectrometry

The present investigation is the first part of an initiative to prepare a regional map of the natural abundance of selenium in various areas of Brazil, based on the analysis of bean and soil samples. Continuous-flow hydride generation electrothermal atomic absorption spectrometry (HG-ET AAS) with in situ trapping on an iridium-coated graphite tube has been chosen because of the high sensitivity and relative simplicity. The microwave-assisted acid digestion for bean and soil samples was tested for complete recovery of inorganic and organic selenium compounds (selenomethionine). The reduction of Se(VI) to Se(IV) was optimized in order to guarantee that there is no back-oxidation, which is of importance when digested samples are not analyzed immediately after the reduction step. The limits of detection and quantification of the method were 30 ng L(-1) Se and 101 ng L(-1) Se, respectively, corresponding to about 3 ng g(-1) and 10 ng g(-1), respectively, in the solid samples, considering a typical dilution factor of 100 for the digestion process. The results obtained for two certified food reference materials (CRM), soybean and rice, and for a soil and sediment CRM confirmed the validity of the investigated method. The selenium content found in a number of selected bean samples varied between 5.5 +/- 0.4 ng g(-1) and 1726 +/- 55 ng g(-1), and that in soil samples varied between 113 +/- 6.5 ng g(-1) and 1692 +/- 21 ng g(-1). (C) 2011 Elsevier B.V. All rights reserved.

Novel deoxy-selenylconduritols: chemoenzymatic synthesis and biological evaluation

The first synthesis of two selenyldeoxycyclitols (4-bromo-2-phenylselenyl conduritol F and 6-phenylselenylconduritol F) is reported via a chemoenzymatic enantioselective route. The key step of the synthesis is the selenolysis of a vinyl epoxide. The new compounds were evaluated for their capacity to inhibit the growth of different microorganisms using a modification of the agar diffusion technique with thin layer chromatography plates as support. (C) 2009 Elsevier Ltd. All rights reserved.

Broad spectrum bioactive sunscreens

The development of sunscreens containing reduced concentration of chemical UV filters, even though, possessing broad spectrum effectiveness with the use of natural raw materials that improve and infer UV absorption is of great interest. Due to the structural similarities between polyphenolic compounds and organic UV filters, they might exert photoprotection activity. The objective of the present research work was to develop bioactive sunscreen delivery systems containing rutin, Passiflora incarnata L. and Plantago lanceolata extracts associated or not with organic and inorganic UV filters. UV transmission of the sunscreen delivery system films was performed by using diffuse transmittance measurements coupling to an integrating sphere. In vitro photoprotection efficacy was evaluated according to the following parameters: estimated sun protection factor (SPF); Boot`s Star Rating category; UVA/UVB ratio; and critical wavelength (lambda(c)). Sunscreen delivery systems obtained SPF values ranging from 0.972 +/- 0.004 to 28.064 +/- 2.429 and bioactive compounds interacted with the UV filters positive and negatively. This behavior may be attributed to: the composition of the delivery system: the presence of inorganic UV filter and quantitative composition of the organic UV filters; and the phytochemical composition of the P. incarnate L and P. lanceolato extracts. Among all associations of bioactive compounds and UV filters, we found that the broad spectrum sunscreen was accomplished when 1.68% (w/w) P incarnata L. dry extract was in the presence of 7.0% (w/w) ethylhexyl methoxycinnamate, 2.0% (w/w) benzophenone-3 and 2.0% (w/w) TiO(2). It was demonstrated that this association generated estimated SPF of 20.072 +/- 0.906 and it has improved the protective defense against UVA radiation accompanying augmentation of the UVA/UVB ratio from 0.49 to 0.52 and lambda(c) from 364 to 368.6 nm. (c) 2008 Elsevier B.V. All rights reserved.

Physical, physicochemical and chemical characterization of turf, sulphur mud and fango for cosmetic application

Focusing on the therapeutic and cosmetic potentials of the thermal water, several processes were developed to achieve a raw material known as fango which presents in its constitution water, clay and organic soil. This research work aimed at characterizing turf, sulphur mud and fango from Araxa, MG, Brazil, through physical, physicochemical, inorganic and organic assessments for cosmetic and topical product proposes. The characterization permitted the determination of relevant parameters to suggest the efficacy (presence, of ions) and safety (absence of toxic metals) of those raw materials for cosmetic and pharmaceutical utilization.

Synthesis of unnatural cyclitols via a combined enzymatic-palladium catalysis approach

The Suzuki-Miyaura cross-coupling reaction of a hydroxylated vinyl bromide obtained by a chemoenzymatic approach with a diverse range of potassium organotrifluoroborates has been accomplished catalyzed by Pd(PPh(3))(4) in satisfactory yields. A variety of functional groups are tolerated in the nucleophilic partner. (C) 2008 Elsevier B.V. All rights reserved.

Phase diagrams of a CTAB/organic solvent/buffer system applied to extraction of enzymes by reverse micelles

A partial pseudo-ternary phase diagram has been studied for the cethyltrimethylammonium bromide/isooctane:hexanol:butanol/potassium phosphate buffer system, where the two-phase diagram consisting of the reverse micelle phase (L-2) in equilibrium with the solvent is indicated. Based on these diagrams two-phase systems of reverse micelles were prepared with different compositions of the compounds and used for extraction and recovery of two enzymes, and the percentage of enzyme recovery yield monitored. The enzymes glucose-6-phosphate dehydrogenase (G6PD) and xylose redutase (XR) obtained from Candida guilliermondii yeast were used in the extraction procedures. The recovery yield data indicate that micelles having different composition give selective extraction of enzymes. The method can thus be used to optimize enzyme extraction processes. (c) 2007 Elsevier B.V. All rights reserved.

EVALUATION OF THE INFLUENCE OF THE PROTEINIC QUALITY OF THE GENETICALLY MODIFIED AND ORGANIC SOY BEANS IN THE GROWTH OF TWO GENERATIONS OF RATS WISTAR

Feijo, T.S., Cardozo, SX, Daleprane, J.B., Sabaa Srur, A.U.O. & Boaventura, G.T. [Evaluation of the influence of the proteinic quality of the genetically modified and organic soy beans in the growth of two generations of rats Wistar.] Avaliacao da influencia da qualidade proteica da soja geneticamente modificada e organica no crescimento de duas geracoes de ratos Wistar. Revista Brasileira de Medicina Veterinaria, 31(3):139-144, 2009. Programa de Pos-Graduacao em Patologia, Hospital Universitario Antonio Pedro. Centro de Ciencias Medicas, Universidade Federal Fluminense. Rua Marques do Parana, 303, Niteroi, RJ 24030-210, Brasil. E-mail: sergian@ufnj.br Sixty four Wistar rats, male of two consecutive generations determined as F(0) and F(1) were used to study the cumulative effect of two variety soy beans, cultivated with organic seasoning and genetically modified, The animals of each generation were divided into three groups of eight rats each fed on diets consisted of organic soy, soy genetically modified and casein respectively. All the animals received water and the diet ad libitum for period of 28 days. Where the diet consumption and the animals weight were evaluated. After statistic analysis of the results no expressive differences were observed on diet consumption, weight variation, protein efficient ratio and food efficiency ratio on same group of animals in the different generations. On the other hand, significant difference was found on final proteinic retention on animal descendants of the same groups; however of different generations. With this, the supplementation of organic soy with L-cistin provided better avail of this protein in relation to the protein of the soy genetically modified. However, this supplementation did not reveal efficiency in keeping the proteinic employment from one generation to another one, since soy varieties presented better performance on F(0) generation when compared with F(1).

Methylmercury and inorganic mercury determination in blood by using liquid chromatography with inductively coupled plasma mass spectrometry and a fast sample preparation procedure

Despite the necessity to differentiate chemical species of mercury in clinical specimens, there area limited number of methods for this purpose. Then, this paper describes a simple method for the determination of methylmercury and inorganic mercury in blood by using liquid chromatography with inductively coupled mass spectrometry (LC-ICP-MS) and a fast sample preparation procedure. Prior to analysis, blood (250 mu L) is accurately weighed into 15-mL conical tubes. Then, an extractant solution containing mercaptoethanol, L-cysteine and HCI was added to the samples following sonication for 15 min. Quantitative mercury extraction was achieved with the proposed procedure. Separation of mercury species was accomplished in less than 5 min on a C18 reverse-phase column with a mobile phase containing 0.05% (v/v) mercaptoethanol, 0.4% (m/v) L-cysteine, 0.06 mol L(-1) ammonium acetate and 5% (v/v) methanol. The method detection limits were found to be 0.25 mu g L(-1) and 0.1 mu Lg L(-1) for inorganic mercury and methylmercury, respectively. Method accuracy is traceable to Standard Reference Material (SRM) 966 Toxic Metals in Bovine Blood from the National Institute of Standards and Technology (NIST). The proposed method was also applied to the speciation of mercury in blood samples collected from fish-eating communities and from rats exposed to thimerosal. With the proposed method there is a considerable reduction of the time of sample preparation prior to speciation of Hg by LC-ICP-MS. Finally, after the application of the proposed method, we demonstrated an interesting in vivo ethylmercury conversion to inorganic mercury. (C) 2009 Elsevier B.V. All rights reserved.

Determination of total and inorganic mercury in whole blood by cold vapor inductively coupled plasma mass spectrometry (CV ICP-MS) with alkaline sample preparation

A simple method with a fast sample preparation procedure for total and inorganic mercury determinations in blood samples is proposed based on flow injection cold vapor inductively coupled plasma mass spectrometry (FI-CVICP-MS). Aliquots of whole blood (500 mL) are diluted 1 + 1 v/v with 10.0% v/v tetramethylammonium hydroxide (TMAH) solution, incubated for 3 h at room temperature and then further diluted 1 + 4 v/v with 2.0% v/v HCl. The inorganic Hg was released by online addition of L-cysteine and then reduced to elemental Hg by SnCl(2). On the other hand, total mercury was determined by on-line addition of KMnO(4) and then reduced to elemental Hg by NaBH(4). Samples were calibrated against matrix-matching. The method detection limit was found to be 0.80 mu g L(-1) and 0.08 mu g L(-1) for inorganic and total mercury, respectively. Sample throughput is 20 samples h(-1). The method accuracy is traceable to Standard Reference Material (SRM) 966 Toxic Metals in Bovine Blood from the National Institute of Standards and Technology (NIST). For additional validation purposes, human whole blood samples were analyzed by the proposed method and by an established CV AAS method, with no statistical difference between the two techniques at 95% confidence level on applying the t-test.

Synthesis and characterization of ternary hybrid material based on poly-o-methoxyaniline and poly(ethylene oxide) in mesostructured V(2)O(5)

New hybrid composites based on mesostructured V(2)O(5) containing intercalated poly(ethylene oxide), poly-o-methoxyaniline and poly(ethylene oxide)/poly-o-methoxyaniline were prepared. The results suggest that the polymers were intercalated into the layers of the mesostructured V(2)O(5). Electrochemical studies showed that the presence of both polymers in the mesostructured V(2)O(5) (ternary hybrid) leads to an increase in total charge and stability after several cycles compared with binary hybrid composites. This fact makes this material a potential component as cathode for lithium ion intercalation and further, a promising candidate for applications in batteries.