Evaluation of monolithic columns for determination of formaldehyde and acetaldehyde in sugar cane spirits by High-Performance Liquid Chromatography

High-Performance Liquid Chromatography (HPLC) conditions are described for separation of 2,4-dinitrophenylhydrazone (2,4-DNPH) derivatives of carbonyl compounds in a 10 cm long C-18 reversed phase monolithic column. Using a linear gradient from 40 to 77% acetonitrile (acetonitrile-water system), the separation was achieved in about 10 min-a time significantly shorter than that obtained with a packed particles column. The method was applied for determination of formaldehyde and acetaldehyde in Brazilian sugar cane spirits. The linear dynamic range was between 30 and 600 mu g L-1, and the detection limits were 8 and 4 mu g L-1 for formaldehyde and acetaldehyde, respectively.

Physical Vapor Deposited Thin Films of Lignins Extracted from Sugar Cane Bagasse: Morphology, Electrical Properties, and Sensing Applications

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 x 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan delta of 3.9 x 10(-3)) and conductivity of 1.75 x 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being reversible. AFM images conducted directly onto the sensing units (Au IDE coated with 120 nm lignin PVD film) before and after the sensing experiments showed a decrease in the PVD film roughness from 5.8 to 3.2 nm after exposing to aniline.

Amino acids profile of sugar cane spirit (cachaca), rum, and whisky

An analytical procedure for the separation and quantification of 20 amino acids in cachacas has been developed involving C18 solid phase cleanup, derivatization with o-phthalaldehyde/2-mercaptoethanol, and reverse phase liquid chromatography with fluorescence detection. The detection limit was between 0.0050 (Cys) and 0.25 (Ser) mg L-1, whereas the recovery index varies from 69.5 (Lys) to 100 (Tyr)%. Relative standard deviations vary from 1.39 (Trp) to 13.4 (Glu)% and from 3.08 (Glu) to 13.5 (His) for the repeatability and intermediate precision, respectively. From the quantitative profile of amino acids in 41 cachacas, 5 turns, and 12 whisky samples, the following order of amino acids in significant quantities is observed: Gly = Ser < Cys < Ile < His < Pro = Asp < Asn < Tyr for cachaca; Phe < Glu = Gln = Val = Ala < His = Gly Thr = Arg = Tyr < Asn Ser = Lys = Pro < Cys = Asp for rum; and Ala = Asn < Trp < Gln = His = Met = Ile = Cys < Thr < Asp Leu < Phe = Lys < Ser = Gly = Tyr = Val < Glu = Pro < Arg for whisky samples. (C) 2007 Elsevier Ltd. All rights reserved.

Formation of Dextran Deposits in Brazilian Sugar Cane Spirits

The formation of dextran deposits in sugared Brazilian cachaca was studied as a function of the time considering the effects of temperature, molecular weight (M(w)), visible light, pH, and the presence of Ca, Mg, Cu, and Fe ions in the concentrations at which they are usually present in this beverage. At 25 degrees C and pH 4.4, the experimental half-lives (t(1/2)) for precipitation are 73 and 124 days for dextrans with M(w) 5.9 x 10(6) and 2.1 x 10(6) Da, respectively. For dextrans with M(w) 5.0 x 10(5) and 4.0 x 10(4) Da, the experimental t(1/2) values are >180 days. For a dextran with M(w) 2.1 x 10(6) Da a change in pH from 4.4 to 5.5 at 25 degrees C resulted in a t(1/2) decrease from 124 to 25 days. At pH 4.4 the visible light and the presence of metal ions in average concentrations usually found in cachacas do not exhibit noticeable influence on the rate of dextran precipitation.

Sliding wear of weld layers with application to cane mill shaft rebuilding

Three welding procedures used to rebuild worn shafts in sugar cane mills were analysed: two submerged arc welding processes and one flux cored arc welding (FCAW) process. Sliding wear tests were in accordance with ASTM G 77 standard, using rings of welding material, blocks of bronze SAE 67, and oil as lubricant. The worn surfaces of rings and blocks were analysed by scanning electron microscopy to determine the wear mechanisms. High contact pressure, high operating temperature, and low relative speed were applied in sliding wear tests to match the conditions in sugar cane mills. Transferred material and evidence of adhesive junctions were detected. Additionally, hardened fragments produced abrasive grooves on the worn surfaces. The welding deposits that presented strong adhesion on the worn surface showed higher mass loss than the materials that presented more abrasive characteristics. Plastic mechanical properties were measured and related to the mass loss. The tested materials presented similar hardness but different yield stress and hardening coefficient. A relationship between wear, strain hardening coefficient, and yield stress was found. The welding deposit that presented the highest hardening coefficient showed the highest mass loss, with evidence of severe adhesion on the worn surface.

Molecular mass distribution of dextran in Brazilian sugar and insoluble deposits of cachaca

The dextran molecular mass distribution profile in 77 sugar samples from Brazil and twelve insoluble deposits (alcoholic flocks) samples from sugared cachacas (Brazilian sugar cane spirit) is described in terms of number-average molecular mass M,,, weight-average molecular mass M(w), Z-average molecular mass M,, and polydispersity. The analyses were performed by size-exclusion chromatography, using a refractive index detector. In most of the sugar samples, it was possible to identify two major groups of dextrans with Mw averages of 5 x 10(6) and 5 x 10(4) Da. Based on the evaluated parameters, the dextran distribution profile is about the same in samples analyzed over five seasons, and, therefore, it is likely that the Brazilian product pattern will not change very much over the years. In insoluble deposits from sugared cachacas, dextrans with Mw values in the order of the 10(5) Da were the most frequent ones, being present in 58% of the samples. (c) 2008 Elsevier Ltd. All rights reserved.

Metabolismo mineral em bubalinos com ingestões de diferentes níveis de fósforo

Objetivou-se avaliar os efeitos da ingestão diária de quatro níveis de fósforo (8, 12, 15 e 18 g) sobre o metabolismo de macrominerais (P, Ca, Mg, Na, K e S), incluindo a ingestão, a concentração no rúmen, a taxa de passagem do líquido ruminal, a excreção nas fezes e a disponibilidade aparente. Utilizaram-se quatro bubalinos adultos com fístulas ruminais em delineamento quadrado latino (4 × 4) com dieta total constituída de cana-de-açúcar como volumoso (85%) e concentrado formulado com um dos níveis de fósforo. Os níveis de fósforo não ocasionaram diferença significativa na concentração mineral no rúmen de nenhum mineral estudado. A concentração média de fósforo no conteúdo ruminal foi de 0,98% na matéria seca, enquanto o teor de fósforo nas rações variou de 0,12 a 0,34%, comprovando alta reciclagem de fósforo pela saliva. Níveis crescentes de fósforo na dieta, variando de 8 a 18 g/animal/dia, não influenciam as disponibilidades de cálcio e magnésio. Com o nível de fósforo de 15 g/dia, houve melhor utilização do fósforo da dieta. A ingestão de níveis crescentes de fósforo em g/kg0,75 (X) promoveu aumento linear na excreção fecal desse mineral em g/kg0,75 (Y) e baixos valores de disponibilidade do fósforo, que pode ser estimado pela equação Y = 0,03 + 0,610X, o que indica deficiência desse elemento mineral na dieta para o metabolismo animal.

Effects of dietary energy and nitrogen supplements on rumen fermentation and protozoa population in buffalo and zebu cattle

The effects were assessed of two energy sources in concentrate (ground grain corn vs. citrus pulp) and two nitrogen sources (soybean meal vs. urea) on rumen metabolism in four buffaloes and four zebu cattle (Nellore) with rumen cannula and fed in a 4 × 4 Latin square design with feeds containing 60% sugar cane. Energy supplements had no effect on the rumen ammonia concentration in cattle, but ground grain corn promoted higher ammonia level than citrus pulp in buffalo. Urea produced higher ammonia level than soybean meal in both animal species. On average, the buffaloes maintained a lower rumen ammonia concentration (11.7 mg/dL) than the cattle (14.5 mg/dL). Buffaloes had lower production of acetic acid than cattle (58.7 vs. 61.6 mol/100 mol) and higher of propionic acid (27.4 vs. 23.6 mol/100 mol). There was no difference in the butyric acid production between the buffaloes (13.6 mol/100 mol) and cattle (14.8 mol/100 mol) and neither in the total volatile fatty acids concentration (82.5 vs. 83.6 mM, respectively). The energy or nitrogen sources had no effect on rumen protozoa count in either animal species. The zebu cattle had higher rumen protozoa population (8.8 × 10(5)/mL) than the buffaloes (6.1 × 10(5)/mL). The rumen protozoa population differed between the animal species, except for Dasytricha and Charonina. The buffaloes had a lower Entodinium population than the cattle (61.0 vs 84.9%, respectively) and a greater percentage of species belonging to the Diplodiniinae subfamily than the cattle (28.6 vs. 1.4%, respectively). In cattle, ground corn is a better energy source than citrus pulp for use by Entodinium and Diplodiniinae. In the buffaloes, the Entodinium are favored by urea and Diplodiniinae species by soybean meal.

Utilização de levedura íntegra e seus derivados em dietas para juvenis de tilápia do Nilo

Neste trabalho, avaliou-se a adição de células íntegras de levedura e seus derivados em dietas para juvenis de tilápia do Nilo. Foram utilizados 144 juvenis machos de tilápia (peso médio de 52,1g) distribuídos em 12 tanques de fibra de vidro (250L), em delineamento inteiramente casualizado, composto por quatro tratamentos e três repetições. Os peixes foram alimentados ad libitum, duas vezes ao dia durante 60 dias, com dietas isoproteicas (28% PB) e isocalóricas (2.900kcal de ED kg-1) contendo levedura íntegra de cana-de-açúcar (LI), levedura autolisada (LA) e parede celular (PC) adicionados na proporção de 25% da proteína bruta total, comparadas com uma dieta controle (CO), sem adição de levedura. Não foram observadas diferenças significativas para conversão alimentar aparente e taxa de eficiência protéica. No entanto, o ganho em peso foi melhor nos peixes alimentados com as dietas LA (114,70g) e PC (131,03g), assim como em relação à taxa de crescimento específico (LA=1,79 e PC=1,93%), à proteína bruta no ganho de peso (LA=14,45 e PC=15,62%) e ao conteúdo corporal proteico (LA=14,89 e PC=15,67g 100g-1). As frações, a parede celular e a levedura autolisada de cana-de-açúcar podem ser utilizadas em dietas para juvenis de tilápia.

Albedo à superfície a partir de imagens Landsat 5 em áreas de cana-de-açúcar e cerrado

Propôs-se, neste trabalho, estimar dados de albedo à superfície terrestre usando-se o sensor Thematic Mapper (TM) do satélite LANDSAT 5 e compará-lo com dados de duas estações agrometeorológicas localizadas em região de Cerrado e a outra em cultivo da cana-de-açúcar. A região de estudo está localizada no município de Santa Rita do Passa Quatro, SP, Brasil. Para a realização do estudo obtiveram-se seis imagens orbitais do satélite Landsat 5 sensores TM, na órbita 220 e ponto 75, nas datas de 22/02, 11/04, 29/05, 01/08, 17/08 e 21/11, todas do ano de 2005, a que correspondem os dias juliano de 53, 101, 149, 213, 229 e 325, respectivamente. As correções geométricas para as imagens foram realizadas e geradas as cartas de albedo. O algoritmo SEBAL estimou satisfatoriamente os valores de albedo de superfícies sobre áreas de cerrado e de cana-de-açúcar, na região de Santa Rita do Passa Quatro, SP, consistentes com observações realizadas do albedo à superfície.

Biomassa e energia

Biomass was the dominating source of energy for human activities until the middle 19th century, when coal, oil, gas and other energy sources became increasingly important but it still represents ca. 10% of the worldwide energy supply. The major part of biomass for energy is still "traditional biomass" used as wood and coal extracted from native forests and thus non-sustainable, used with low efficiency for cooking and home heating, causing pollution problems. This use is largely done in rural areas and it is usually not supported by trading activities. There is now a strong trend to the modernization of biomass use, especially making alcohol from sugar cane thus replacing gasoline, or biodiesel to replace Diesel oil, beyond the production of electricity and vegetable coal using wood from planted forests. As recently as in 2004, sustainable "modern biomass" represented 2% of worldwide energy consumption. This article discusses the perspectives of the "first" and "second" technology generations for liquid fuel production, as well as biomass gaseification to make electricity or syngas that is in turn used in the Fischer-Tropsch process.

Hidrocarbonetos policíclicos aromáticos (HPAS) em cachaça, rum, uísque e álcool combustível

The concentration of 15 polycyclic aromatic hydrocarbons (PAHs) in 57 samples of distillates (cachaça, rum, whiskey, and alcohol fuel) has been determined by HPLC-Fluorescence detection. The quantitative analytical profile of PAHs treated by Partial Least Square - Discriminant Analysis (PLS-DA) provided a good classification of the studied spirits based on their PAHs content. Additionally, the classification of the sugar cane derivatives according to the harvest practice was obtained treating the analytical data by Linear Discriminant Analysis (LDA), using naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, benz[b]fluoranthene, and benz[g,h,i]perylene, as a chemical descriptors.

Teores de carbamato de etila em aguardentes de cana e mandioca: parte II

Herein, we report the concentration of ethyl carbamate (EC) and copper in 380 samples of sugar-cane spirit and 45 samples of manioc spirit as determined by GC-MS and FAAS respectively. The cyanide content determined spectrophotometrically is reported for the manioc spirit. Sugar cane spirit produced by alembic distillation (70,0 µg L-1) shown a lower content of EC than samples produced by column distillation (270 µg L-1). No simple correlation between the content of EC and copper for sugar cane spirit as well among the concentration of EC, copper, and cyanide for manioc spirit could be observed.

Formação de carbamato de etila em aguardentes recém-destiladas: proposta para seu controle

The commercial sugar cane spits redistillation decreased up to 92,5% their ethyl carbamate (EC) original content. Quantitative analysis of EC in 15 samples of sugar cane spirit (alembic and column), fresh distilled and collected in situ demonstrated that the urethane is formed mostly after distillation. The average time to achieve the complete EC formation is independent of the diffuse light presence and of the distillation apparatus used. The k obs for urethane formation at 25 ºC was calculate as (3,3 ± 0,5) x 10-5/s and the activation parameters are: ΔH‡ 34 kcal/mol; ΔS‡ - 69 cal/mol K; and ΔG‡ 54 kcal/mol.

Heterogeneidade de álcoois secundários em aguardentes brasileiras de diversas origens e processos de fabricação

Secondary alcohol concentrations in sugar cane spirits from different origins were determined by gas chromatography. A great variation in the concentration of the secondary alcohols was found in these spirits. Of the 33 brands analyzed, 8 of them were found to be out of conformity with the legislation. Sec butanol, for which the maximum allowed concentration level is 100 mg.L-1 in absolute ethanol, was found within a concentration range between 5 mg.L-1, the limit of quantitation (LQ) and 408 mg.L-1 in absolute ethanol. Sugar cane samples from Salinas, MG, were the only ones that exhibited self similarity because of the low concentrations of n-butanol and n-amylic alcohol (< limit of detection LD).