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The vinasse is a residue of ethanol production with the potential for methane production, requiring an allochthonous inoculum. Several microorganisms act in the different phases of anaerobic digestion, and the identification of these microbial communities is essential to optimize the process. The characterization of the microbiota involved in the biodigestion of vinasse was observed in the initial stage (IS), at the peak of methane production (MS) and the end of the process (FS) of the best performance assay by high-throughput sequencing. The highest methane production was 0.78 mmolCH4.gVS.h−1 at 243.7 h in the substrate/inoculum ratio of 1.7, with consumption partial of acetic, propionic and isobutyric acids and an 82% reduction of chemical oxygen demand. High microbial diversity was found. The genera Clostridium, Acinetobacter, Candidatus Cloacamonas, Bacteroides, Syntrophomonas, Kosmotoga, the family Porphyromonadaceae and the class Bacteroidia were the most abundant in the maximum methane production. Methane production was driven by Methanobacterium and Methanosaeta, suggesting the metabolic pathways used were hydrogenotrophic and acetoclastic. HIGHLIGHTS The AD of vinasse with allochthonous inoculum reached 82% reduction in COD.; The increase of OLR provided the highest methanogenic activity (0.78 mmol CH4.gVS.h−1).; Clostridium, Candidatus Cloacamonas and Acinetobacter predominated in CH4 production.; Methanobacterium and Methanosaeta drove the methane production.

Sugarcane cultivation is suitable for the exploitation of organic waste products. However, minimum complementary mineral input is necessary for optimal fertilisation. Control mineral fertilisation treatments with mulch (MCM) or without mulch (MC) were compared with two organic waste treatments, a pig slurry with mulch (PSM) and without mulch (PS), and a sugarcane vinasse with mulch (SVM) and without mulch (SV) on a Nitisol in French Reunion Island. The sugarcane yields obtained with the different treatments differed each year. However, no trend was observed and no significant and recurrent effect of the presence of mulch or of the different treatments was identified over the course of the 4 year experiment. Soil pHw and pH KCl measured in the different treatments increased from year 3 in with the treatments including organic waste products (PS, PSM, SV and SVM) but remained constant with the treatments including only mineral fertilisation (MC and MCM). With the exception of PS and PSM, which were significantly higher in year 4, soil organic carbon content was not modified by the treatments. Soil cation exchange capacity increased only slightly with the PS and PSM treatments from year 3 on. The differences in yields and soil properties can be explained by the nature of the organic waste products, the accumulation of nutrients after several applications, and the specific characteristics of the sugarcane crop. The improvement in soil properties from the third year on was not reflected in the yield of sugarcane because it was too weak, and the crop explores a much larger volume of soil.

Made available in DSpace on 2021-06-25T10:48:20Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-03-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação Cearense de Apoio ao Desenvolvimento Científico e Tecnológico Sugarcane bagasse, vinasse and a mixture of sugarcane bagasse and vinasse were hydrothermally carbonized (HTC), with and without the addition of phosphoric acid, in order to propose new applications of sucroenergetic industry by-products on soil. Detailed information on the composition and properties of hydrochars has been obtained through elemental composition, thermogravimetric analysis, nuclear magnetic resonance and, thermochemolysis GC-MS. The soluble acidic fraction from the hydrochar samples were applied to maize seeds to evaluate the agronomic potential as biostimulants and relate the molecular features with maize seed germination. The HTC treatment converted polysaccharide-based biomasses into hydrochars with hydrophobic characteristics (C-Aryl and C-Akyl). Furthermore, the addition of phosphoric acid further increased the overall hydrophobicity and shifted the thermal degradation of the hydrochars to higher temperatures. Biomass influenced the hydrochars that formed, in which the molecular features of sugarcane bagasse determined the formation of more polar hydrochar, due to the preservation of lignin and phenolic components. Meanwhile, the HTC of vinasse resulted in a more hydrophobic product with an enrichment of condensed and recalcitrant organic fractions. The germination assay showed that polar structures of bagasse may play a role in improving the maize seeds germination rate (increase of ~11%), while the hydrophobic domains showed negative effects. The responses obtained in germination seems to be related to the molecular characteristics that organic extracts can present in solution. Laboratório de Estudos Em Ciências Ambientais (LECA) Instituto de Biociências Letras e Ciências Exatas UNESP Universidade Estadual Paulista Departamento de Química e Ciências Ambientais São José Do Rio Preto Centro Interdipartimentale di Ricerca Sulla Risonanza Magnetica Nucleare per L'Ambiente L'Agroalimentare Ed I Nuovi Materiali (CERMANU) Università di Napoli Federico II, Portici Dipartimento di Farmacia (DIFARMA) Università Degli Studi di Salerno Laboratório de Materiais Funcionais Avançados (LaMFA) Departamento de Física Universidade Federal Do Ceará Laboratório de Estudos Em Ciências Ambientais (LECA) Instituto de Biociências Letras e Ciências Exatas UNESP Universidade Estadual Paulista Departamento de Química e Ciências Ambientais São José Do Rio Preto FAPESP: 17/05575–2 FAPESP: 17/17991–0 FAPESP: 18/15733–7 CAPES: 183995 CNPq: 303377/2019–4 Fundação Cearense de Apoio ao Desenvolvimento Científico e Tecnológico: PRONEX PR2-0101-00006.01.00/15

Made available in DSpace on 2020-12-12T02:38:51Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-07-20 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) The generation of large volumes of vinasse during the production of biofuel ethanol is a challenging problem since inappropriate application of the byproduct as an agro-fertigant can give rise to contamination of soil and watercourses and cause harm to aquatic life. The aims of the study were(i) to evaluate an alternative strategy involving the generation of biogas by anaerobic digestion of sugarcane vinasse in two-stage upflow anaerobic sludge blanket (UASB) reactors (R1 and R2 connected in series), and (ii) to determine the ethanol content and fermentation efficiency of mashes prepared by diluting sugarcane molasses with deionized water, fresh vinasse and effluents from R1 or R2, both before and after submission to the Fenton reaction. The highest percentages of ethanol were obtained with fermentation mashes prepared from molasses diluted with Fenton-treated R1 (5.1%) or R2 effluents (5.7%) or with non-treated R2 effluent (5.7%). The corresponding fermentation efficiencies of these processes were 88.5, 92.1 and 89.3%. The proposed combination of biofuel and biogas production would provide a sustainable source of energy, contribute to the safe disposal of large quantities of vinasse and help to reduce the volume of freshwater employed by the sugarcane processing industry. Paula Souza Center Technology College Laboratory of Environmental Sanitation Department of Rural Engineering São Paulo State University (UNESP) School of Agricultural and Veterinarian Sciences Graduate Program in Agricultural and Livestock Microbiology São Paulo State University (UNESP) School of Agricultural and Veterinarian Sciences Laboratory of Environmental Sanitation Department of Rural Engineering São Paulo State University (UNESP) School of Agricultural and Veterinarian Sciences Graduate Program in Agricultural and Livestock Microbiology São Paulo State University (UNESP) School of Agricultural and Veterinarian Sciences CAPES: 2015/05567-4 CNPq: 312093/2016-0 CNPq: 456426/2014-0

Made available in DSpace on 2020-12-12T02:29:30Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-12-01 This paper reports on a sensitive and selective electrochemical sensor for lactic acid. The sensor is based on molecularly imprinted polymers (MIP), obtained on glassy carbon electrode (GCE) modified with reduced graphene oxide and gold nanoparticles. The MIP was obtained by electropolymerization of the o-phenylenediamine (o-PD) on the modified surface of the GCE in the presence of lactic acid. The steps involving the GCE modification and MIP construction were characterized by cyclic voltammetry, electrochemical impedance spectroscopy, scanning electron microscopy and atomic force microscopy. The results were evaluated using differential pulse voltammetry, using the hexacyanoferrate redox system as an electrochemical probe. Under optimized experimental conditions, the imprinted sensor has a linear response in the 0.1 nM to 1.0 nM lactic acid concentration range, with detection limit of 0.09 nM. The sensor exhibits excellent selectivity in the presence of molecules of similar chemical structure. It was applied for the selective determination of lactic acid in sugarcane vinasse. The recovery values ranged from 97.7 to 104.8%. [Figure not available: see fulltext.]. Institute of Chemistry São Paulo State University (UNESP) Bioenergy Research Institute São Paulo State University (UNESP) Institute of Chemistry São Paulo State University (UNESP) Bioenergy Research Institute São Paulo State University (UNESP)

Polyhydroxyalkanoates (PHA) are fully biodegradable biopolymers of microbial origin, with physicochemical characteristics similar to those of conventional synthetic plastics. However, their current production is highly expensive mainly due to the substrate or culture medium employed. In this research, a mixture of cane molasses and residual vinasse from the alcohol industry was evaluated as a substrate using the reference strain Ralstonia eutropha ATCC 17699 to produce PHAs. The results showed the potential of the mixture as a culture medium, after reaching polymer concentrations of 3.17 g/L in MSM medium and 2.71 g/L in M/V medium with a molasses/vinasse ratio of 25/75. There was a sugar (sucrose, fructose, and glucose) consumption yield of 70.7%, and a biopolymer accumulation of 97.8% with respect to the biomass produced. The biopolymer characterization showed a correlation with the standard polyhydroxybutyrate sample - PHB of 99.25%. Resumen Los Polihidroxialcanoatos (PHAs) son biopolímeros de origen microbiano totalmente biodegradables con características físicoquímicas similares a los plásticos sintéticos convencionales, sin embargo, su producción actual es altamente costosa debido principalmente al sustrato o medio de cultivo. En esta investigación se evaluó como sustrato, una mezcla de melaza de caña y vinaza residuales de la industria licorera empleando la cepa referencia Ralstonia eutropha ATCC 17699 para la producción de PHAs. Los resultados obtenidos mostraron potencial en el uso de este medio de cultivo, alcanzando concentraciones de polímero de 3,17 g/L en medio MMS y de 2,71 g/L en el medio M/V con una relación melaza/vinaza de 25/75. El rendimiento de consumo de azucares (sacarosa, fructosa y glucosa) fue del 70,7% y una acumulación del biopolímero del 97,8% respecto a la biomasa producida. La caracterización del biopolímero presento una correlación con la muestra patrón de polihidroxibutirato - PHB del 99,25%.

Made available in DSpace on 2018-12-11T17:36:11Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-07-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Technical, economic and environmental aspects of implementing two-phase anaerobic digestion (AD), i.e., acidogenic + methanogenic systems, in sugarcane biorefineries for the treatment of vinasse were assessed based on different strategies to using the hydrogen-rich biogas (biogas-H2) generated via acidogenesis. Phase separation greatly enhanced the bioenergy recovered from vinasse AD compared with single-phase systems (methanogenic phase exclusively). The best results for generating electric energy were observed in combined cycle-based power plants that utilized biohythane (10.8 MW + 5.5 MW for the harvest and inter-harvest, respectively), which is the gaseous biofuel from blending biogas-H2 with the methane-rich stream from the methanogenic phase (biogas-CH4). Moreover, the results of this study indicated that scaling up two-phase AD systems is economically feasible for the treatment of sugarcane vinasse (net present value = USD 208.58–219.86 million) because a better or equivalent economic performance was attained compared with single-phase processes. Optimizing the alkalinization of methanogenic reactors strongly affected both the economic and environmental performance of the process, with better results observed with the use of low sodium hydroxide dosages (4 g NaOH kg−1COD). In summary, our results highlighted that two-phase biodigestion may enhance energy production from vinasse by 20–30% without impairing the profitability of the biorefinery and could lead to slight improvements in the environmental performance of the ethanol production chain via the use of an optimized alkalinization strategy. Biological Processes Laboratory (LPB) São Carlos School of Engineering (EESC) University of São Paulo (USP), Av. João Dagnone, 1100, Santa Angelina Laboratório Nacional de Ciência e Tecnologia do Bioetanol (CTBE) Centro Nacional de Pesquisa em Energia e Materiais (CNPEM), Rua Giuseppe Máximo Scolfaro, 10000, Polo II de Alta Tecnologia, P.O. Box 6170 São Paulo State University (UNESP) Institute of Geosciences and Exact Sciences (IGCE), Campus of Rio Claro. Av. 24-A, 1515, Bela Vista São Paulo State University (UNESP) Institute of Geosciences and Exact Sciences (IGCE), Campus of Rio Claro. Av. 24-A, 1515, Bela Vista FAPESP: 2009/15984-0 FAPESP: 2012/15606-9

Made available in DSpace on 2021-06-25T10:59:50Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-06-01 This work reports the development of a fast and reliable amperometric sensor for the detection of amino acids. The detector was constructed using copper nanoparticles (CuNPs) supported on reduced graphene oxide (RGO) modified glassy carbon electrode (CuNPs-RGO/GCE) and based on the application of high performance anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD). Under optimized isocratic HPAEC-PAD conditions (using 40 mmol L−1 NaOH as mobile phase, flow rate of 0.30 mL min−1 and detection potential of 0.45 V vs. Pd/PdO), the linear dynamic ranges of the concentration of amino acids obtained were 0.50–50 µmol L−1 for lysine, 1.0–100 µmol L−1 for alanine, glycine and serine, and 5.0–100 µmol L−1 for leucine. The limits of detection (S/N = 3) obtained ranged from 0.10 (for lysine and leucine) to 0.50 µmol L−1 (for alanine, glycine and serine) and sensitivity varied from 6.1 (for leucine) to 21.5 nA µmol−1 L (for serine). The average recovery percentages ranged from 97% (for glycine) to 102% (for leucine and serine). The results obtained showed that the CuNPs-RGO/GCE has good long-term stability, repeatability and reproducibility; this makes the device suitable for application as an electrochemical detector. The successful application of the proposed method for the analysis of sugarcane vinasse demonstrates its suitability for separation and determination of amino acids in complex matrices. Analytical Chemistry Department Institute of Chemistry São Paulo State University (UNESP) Bioenergy Research Institute São Paulo State University (UNESP) Analytical Chemistry Department Institute of Chemistry São Paulo State University (UNESP) Bioenergy Research Institute São Paulo State University (UNESP)

International audience; The activated sludges and the sugarcane distillery wastewater (vinasse) are two different types of liquid wastes generated throughout the domestic wastewater treatment and sugarcane molasses fermentation and distillation respectively. In Reunion Island, sludge is currently discarded in landfills. Regarding the vinasse, a part of the production is treated by anaerobic digestion process. However, the remaining part is diluted then discharged into the sea 900 m of the coast. In this study, the mesophilic biochemical methane potential (BMP) test, with different inoculum to substrate (I/S) ratios, are presented in this paper as well as the methane production and kinetic results. The BMP is modelled by both the first order linear regression and the modified Gompertz model. In a future study, we will propose an alternative solution in order to treat both wastes simultaneously while producing energy with the co-digestion of the vinasse and the activated sludges in semi-industrial scale.

This work evaluated the degradation of sugarcane vinasse with the production of biomass by Pleurotus sajor-caju CCB020, considering the combination of temperature and pH effects, using surface response methodology (RSM). A 22 complete central factorial composite experiment was used to analyze the results. The optimum temperature and pH values were respectively 27°C and 5.6 for maximum decolorization yield and 20°C and 6.8 for maximum biomass production. In parallel, scale-up experiments under conditions of 30°C and initial pH 5.0 were evaluated in two different air-lift bioreactors of 7.0L. Under these conditions, reductions of 53% and 58% in chemical oxygen demand (COD) and 71% and 58% in biological oxygen demand (BOD) were obtained respectively with the concentric tube type air-lift bioreactor with an increased degassing zone and without an increased degassing zone. Under these conditions, this study concluded that the systematic combination of P. sajor-caju and vinasse can be applied in the biodegradation process of refractory compounds contained in vinasse, concomitant to obtaining biomass and laccase and manganese peroxidase enzymes. Due to the good performance of the air-lift bioreactors, they can be used in scale studies in future industrial vinasse applications, besides it is possible to emphasize that different configurations in the bioreactor can affect the efficiency of the process., Supplementary data to this article can be found online at: https://doi.org/10.1016/j.chemosphere.2019.125432., info:eu-repo/semantics/publishedVersion

Made available in DSpace on 2018-11-26T17:45:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-01-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) A reversed-phase liquid chromatographic separation with pulsed amperometric detection of phenolic acids at a glassy carbon electrode is described. Chromatographic separation was carried out in isocratic conditions using 0.20 mol.L-1 acetic acid (pH 5.0)/water (80 : 20, v/v) as mobile phase under constant working potential mode of 0.80 V. Chromatographic peaks presented high resolution and separation. Calibration curves exhibited excellent correlation coeffcients, above 0.995. Linear ranges of the analytes, in mg L-1, were of 0.018-18 (gallic acid), 0.146-19 (vanillic acid), 0.13-17 (caffeic acid), 0.016-16 (ferulic acid), and 0.008-17 (p-coumaric acid), respectively. Limits of detection ranged from 1.6 to 97 mu g.L-1 and precision varied in 1.73-3.78% interval. Concentrations of 19 +/- 0.51mg.L-1 and 7.8 +/- 2.5 mg.L-1 were found for vanillic and caffeic acids, respectively, in a sugarcane vinasse sample. Gallic, ferulic, and p-coumaric acids were not detected. Recovery results demonstrated that the proposed method is accurate, and it can be used to detect and quantify phenolic acids in sugarcane vinasse without any influence of interferents. Univ Fed Vicosa, Ctr Ciencias Exatas & Tecnol, Dept Tecnol Alimentos, Av Peter Henry Rolfs S-N, Vicosa, MG, Brazil Univ Estadual Paulista, Inst Quim IQ CAr, Dept Quim Anal, R Prof Francisco Degni 55, BR-14800060 Araraquara, SP, Brazil Univ Fed Fluminense, Escola Engn Ind & Met Volta Redonda, Av Trabalhadores 420, Volta Redonda, RJ, Brazil Univ Estadual Paulista, Inst Quim IQ CAr, Dept Quim Anal, R Prof Francisco Degni 55, BR-14800060 Araraquara, SP, Brazil FAPESP: 2014/23846-5

Submitted by JOSÉ LUIZ DA SILVA null (silva_jluiz@yahoo.com.br) on 2017-11-28T13:51:22Z No. of bitstreams: 1 Tese - José Luiz da Silva.pdf: 19589352 bytes, checksum: e95d258564c255525a7e798dcde82ff0 (MD5) Submitted by JOSÉ LUIZ DA SILVA null (silva_jluiz@yahoo.com.br) on 2017-11-28T14:22:45Z No. of bitstreams: 1 Tese - José Luiz da Silva.pdf: 19589352 bytes, checksum: e95d258564c255525a7e798dcde82ff0 (MD5) Submitted by JOSÉ LUIZ DA SILVA null (silva_jluiz@yahoo.com.br) on 2017-11-28T14:31:57Z No. of bitstreams: 1 Tese - José Luiz da Silva.pdf: 19589352 bytes, checksum: e95d258564c255525a7e798dcde82ff0 (MD5) Submitted by JOSÉ LUIZ DA SILVA null (silva_jluiz@yahoo.com.br) on 2017-11-28T14:37:46Z No. of bitstreams: 1 Tese - José Luiz da Silva.pdf: 19589352 bytes, checksum: e95d258564c255525a7e798dcde82ff0 (MD5) Submitted by JOSÉ LUIZ DA SILVA null (silva_jluiz@yahoo.com.br) on 2017-11-28T19:04:28Z No. of bitstreams: 1 Tese - José Luiz da Silva.pdf: 19589352 bytes, checksum: e95d258564c255525a7e798dcde82ff0 (MD5) Approved for entry into archive by Ana Carolina Gonçalves Bet null (abet@iq.unesp.br) on 2017-11-28T20:14:27Z (GMT) No. of bitstreams: 1 silva_jl_dr_araiq_par.pdf.pdf: 1404379 bytes, checksum: 946a158b4fa2955d501cf9d4990be358 (MD5) Made available in DSpace on 2017-11-28T20:14:27Z (GMT). No. of bitstreams: 1 silva_jl_dr_araiq_par.pdf.pdf: 1404379 bytes, checksum: 946a158b4fa2955d501cf9d4990be358 (MD5) Previous issue date: 2017-11-14 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) A vinhaça de cana-de-açúcar é um coproduto gerado a partir da produção de etanol através da fermentação de carboidratos por leveduras em indústrias de álcool e açúcar, com alto poder poluente (cerca de cem vezes maior do que o esgoto doméstico) e requer alta demanda química de oxigênio. Estima-se que a produção de vinhaça de cana-de-açúcar no Brasil seja entre 265,1 e 370,3 bilhões de litros na safra 2017/2018. O desenvolvimento de métodos para determinação da composição química da vinhaça é de extrema importância para agregar maior valorização a esse coproduto industrial. Com o intuito de avaliar novos processos de aplicação, produção ou extração de aminoácidos a partir da vinhaça, é de fundamental importância a caracterização precisa da composição química desse coproduto. Neste trabalho, foram investigados detectores nanoestruturados de óxido de grafeno reduzido (RGO) contendo nanopartículas de óxidos metálicos de níquel, cobre e prata para detecção e determinação de aminoácidos em vinhaça de cana-de-açúcar utilizando cromatografia líquida de alta eficiência (HPLC) acoplada com detecção eletroquímica. Os eletrodos modificados construídos foram caracterizados por voltametria cíclica (CV), espectroscopias de impedância eletroquímica (EIS), fotoemissão de raios X (XPS), Raman e energia dispersiva de raios X (EDX), e microscopias eletrônica de varredura de alta resolução (SEM) e eletrônica de transmissão (TEM). A oxidação eletrocatalítica dos aminoácidos em meio alcalino foi estudada por CV com velocidade de varredura de 100 mV s-1. Os resultados mostraram que os aminoácidos estudados não foram oxidados na superfície modificada com RGO. No entanto, os analitos foram oxidados irreversivelmente nas superfícies dos eletrodos modificados com RGO contendo nanopartículas de óxidos metálicos de níquel, cobre e prata. As separações cromatográficas foram realizadas empregando uma coluna de troca-iônica acoplada com uma pré-coluna e eluição isocrática. Foram avaliados os efeitos do hidróxido, acetato de sódio e água como fase móvel. As separações dos aminoácidos foram completas dentro de 30 min. As respostas dos métodos desenvolvidos melhoraram devido à aplicação de RGO e nanopartículas de óxidos metálicos como modificadores de eletrodo. Os parâmetros analíticos do método desenvolvido foram avaliados. As soluções foram preparadas com concentrações na gama de 1,0×10-8 a 1,0×10-3 mol L-1. Sob as condições cromatográficas otimizadas, os métodos desenvolvidos utilizando os eletrodos modificados apresentaram uma relação linear com as concentrações dos aminoácidos em duas ordens de grandeza com limites de detecção inferiores a 2,0×10-5 mol L-1, sensibilidades maiores do que 3,3×105 nA mol-1 L e excelente coeficiente de correlação ≥ 0,9991. Os métodos analíticos propostos utilizando eletrodos modificados com RGO contendo NiNPs e CuNPs foram aplicados na detecção de aminoácidos em amostra de vinhaça de cana-de-açúcar com recuperações variando de 95 ± 5 a 102 ± 3 %. A estabilidade e a repetibilidade dos eletrodos modificados foram investigadas. A excelente estabilidade a longo prazo e a repetibilidade dos eletrodos construídos os tornam atraentes como detectores eletroquímicos. Os resultados mostraram que os detectores desenvolvidos podem ser empregados para detecção e quantificação de aminoácidos, livre de interferentes e com precisão em amostras de vinhaça de cana-de-açúcar. Sugarcane vinasse is a co-product generated from ethanol production from yeast fermentation of carbohydrates in sugar and ethanol plants, with high pollutant power (about a hundred times higher than domestic sewage) and requires high chemical oxygen demand (COD). It is estimated that the sugarcane vinasse production in Brazil will be between 265.1 and 370.3 billion litres in 2017/2018 harvest. The methods development for determining the chemical composition of vinasse is extremely important to add value to this co-product and bioenergy applications. In order to evaluate new application processes, production or extraction of amino acids from vinasse, is fundamental to accurate characterization of the chemical composition of this co-product. In this work, we investigated reduced graphene oxide (RGO) containing nickel, copper and silver metal oxide nanoparticles nanostructured detectors for amino acids detection and determination in sugarcane vinasse using high performance liquid chromatography (HPLC) coupled to electrochemical detection. The modified electrodes constructed were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray photoemission spectroscopy (XPS), Raman spectroscopy, energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrocatalytic oxidation of the amino acids in alkaline medium was studied by CV with scan rate of 100 mV s-1. The results showed that the amino acids studied were not oxidized on the surface modified with RGO. However, the analytes were irreversibly oxidized on the electrode surfaces modified with RGO containing nickel, copper and silver metal oxides nanoparticles. Chromatographic separations were performed employing an ion exchange column coupled to a pre-column and isocratic elution. The effects of sodium hydroxide, sodium acetate, and water as mobile phase were evaluated. Separations of amino acids were complete within 30 min. The electrochemical response and sensitivity of the developed methods improved due to the application of RGO and metal oxides nanoparticles as electrode modifiers. The analytical parameters of the developed method were evaluated. Solutions were prepared with concentrations in range of 1.0×10-8 to 1.0×10-3 mol L-1. Under optimized chromatographic conditions, the methods developed using the modified electrodes showed a linear relationship towards the amino acid concentrations in two orders of magnitude with detection limits of less than 2.0×10-5 mol L-1, sensitivities greater than 3.3×105 nA mol-1 L and excellent correlation coefficient ≥ 0.9991. The analytical methods proposed using modified electrodes with RGO containing NiNPs and CuNPs were applied in the amino acids detection in sugarcane vinasse samples with recoveries varying from 95 ± 5 to 102 ± 3%. The stability and repeatability of the modified electrodes were investigated. The excellent long-term stability and repeatability of the prepared modified electrodes make them attractive as electrochemical detectors. The results showed that the developed detectors could be used for amino acids detection and quantification, free of interferences and with precision in sugarcane vinasse samples.

Made available in DSpace on 2018-12-11T17:30:48Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-01-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) This study considered the application of anaerobic digestion (AD) with phase separation combined with the use of an anaerobic structured-bed reactor (ASTBR) as the methanogenic phase for the treatment of sugarcane vinasse, a high-strength wastewater resulting from ethanol production. Two combined thermophilic acidogenic-methanogenic systems formed by one single acidogenic reactor followed by two methanogenic reactors operated in parallel were compared, namely, a conventional UASB reactor and an upflow ASTBR reactor. Increasing organic loading rate (OLR) conditions (15–30 kg COD m−3d−1) were applied to the methanogenic reactors. The results highlighted the feasibility of applying the ASTBR to vinasse, indicating a global COD removal higher than 80%. The ASTBR exhibited a stable long-term operation (240 days), even for OLR values as high as 30 kg COD m−3d−1. The application of similar conditions to the UASB reactor indicated severe performance losses, leading to the accumulation of acids for every increase in the OLR. An energetic potential of 181.5 MJ for each cubic meter of vinasse was estimated from both hydrogen and methane. The provision of bicarbonate alkalinity proved to be a key factor in obtaining stable performance, offsetting the limitations of relatively low hydraulic retention times (

Made available in DSpace on 2018-11-26T17:20:53Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-01-20 FEDER national funds through FCT - Fundacaip para a Ciencia e a Tecnologia LEPABE Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) The post-treatment of biodigested sugarcane vinasse was envisaged in the present study following three different approaches: i) coagulation/flocculation - Approach 1; ii) combination of coagulation/flocculation with photo-Fenton reaction Approach 2; iii) coagulation/flocculation followed by biological degradation and photo-Fenton reaction - Approach 3. The coagulation/flocculation per se provided a slight increase in effluent's biodegradability, a decrease in toxicity and turbidity, and provided moderate removals of total organic carbon (TOC), biochemical oxygen demand (BOD5) and chemical oxygen demand (COD). The operating costs associated with chemicals consumption are low (5.7 R$/m(3) approximate to 1.4 (SDC)/m(3)). The second and third treatment approaches allowed to reach a nontoxic effluent, improved the biodegradability and led to similar high global organics removal efficiencies. The combined treatment consisting of coagulation/flocculation plus photo-Fenton oxidation (Approach 2) revealed to be a promising solution for treating this wastewater, in order to be recirculated into the high rate anaerobic reactor. Additionally, this solution provides smaller costs (84.9 R$/m(3) approximate to 20.2 (SIC)/m(3)) associated with chemicals and energy consumption, which are however very high. Nonetheless, this cost can be reduced by about 40% if solar radiation is used in the photo-Fenton process. (C) 2016 Elsevier Ltd. All rights reserved. Univ Porto, Fac Engn, Dept Engn Quim, LEPABE, P-4200465 Oporto, Portugal Fac Tecnol Jaboticabal, Av Eduardo Zambianchi 31, BR-14883130 Jaboticabal, SP, Brazil Univ Estadual Paulista, Fac Ciencias Agr & Vet, Dept Engn Rural, Lab Saneamento Ambiental,UNESP, Campus Jaboticabal, BR-14884900 Jaboticabal, SP, Brazil Univ Porto, Fac Engn, Lab Associado LSRE LCM, LSRE Lab Proc Separacao & Reacao,Dept Engn Quim, P-4200465 Oporto, Portugal Univ Estadual Paulista, Fac Ciencias Agr & Vet, Dept Engn Rural, Lab Saneamento Ambiental,UNESP, Campus Jaboticabal, BR-14884900 Jaboticabal, SP, Brazil FEDER: POCI-01-0145-FEDER-006939 CAPES: PNPD-3137/2010 CNPq: 483118/2011-7 CNPq: 456426/2014-0

An experiment on Fenton degradation of sugarcane vinasse was carried out to determine its effect on the wastewater characteristics. Vinasse, a by-product of distillation in the bioethanol industry, contains high organic matter, as the value of chemical oxygen demand (COD) is &gt, 100,000 mg/L and BOD5 is 31,250 mg/L. The Fenton reaction is one of the advanced oxidation process (AOP) methods which has been widely applied for the treatment of wastewater containing organic pollutants and contaminants. This method utilizes hydroxyl radical (&bull, OH) produced from the catalyzing reaction between Fe2+ or Fe3+ and hydrogen peroxide. The effect of pH, the ratio of [H2O2] and [COD], and the ratio of [H2O2] to [Fe3+] were studied in this research to evaluate the Fenton reaction. Results from this experiment showed that treatment of vinasse using the Fenton reaction decreased the COD value to 48.10%, and its biodegradability enhanced almost two times at a pH value of 3.8, a ratio of [H2O2] to [COD] of 0.62, and a ratio of [H2O2] to [Fe3+] of 50 (g/g), which demonstrated that the Fenton treatment was effective to reduce organic matter of sugarcane vinasse. Three kinetic models (first order, second order, and Behnajad&ndash, Modirshahla&ndash, Ghanbery (BMG) kinetic model) were used to evaluate the degradation of the COD value. On the basis of the value of R2 (coefficient of determination), we suggested that BMG represented the best kinetic model. This study finds that the Fenton treatment is able to mitigate the environmental impacts of sugarcane vinasse.

Vinasse is a key by-product of the ethanol manufacturing industry. Several processes have been studied for the first time in order to treat sugarcane vinasse. Removals of the absorbances (220, 254 and 410 nm) and nutrients (Ca, Mg, P, N, K and Na)≤36% were achieved in the H2SO4 precipitation with the production of a low sludge volume (rich in organic matter and magnesium). A nominal chemical oxygen demand (COD) decline = 12% was also noted when using H2SO4 precipitation, owing to the presence of soluble organic acids in vinasse. Operating pH in the Ca(OH)2 precipitation affected the removal of COD, absorbances and nutrients, obtaining high efficiencies (COD = 51%, absorbances = 88–100%, Mg = 91%, N = 74%, K = 37%, P = 95%, Na = 20%) for high precipitation pH (12–12.5). High depletions in the Ca(OH)2 precipitation can be explained by the formation of insoluble species and polymerization and precipitation of fatty acids, producing a sludge rich in Ca, P, K and Mg. Comparable results were attained for the thermocalcic precipitation. NaOH precipitation treatability for the vinasse decontamination was based on the removals of Ca (80%), P (74%), Mg (64%), N (24%), K (19%), generating a sludge rich in organic matter and nutrients (Mg, K, P and Na). The supernatant produced in the Ca(OH)2 precipitation, under optimal conditions, was subjected to: 1) a coagulation-flocculation step with FeCl3 addition (1 g L−1), improving the removals of absorbance at 410 nm, COD, phosphorus and volatile solids (VS); and 2) a novel green technology (natural carbonation) for the atmospheric CO2 mitigation with treatment and neutralization of the effluent.

Submitted by GRAZIELA CRISTINA SEDENHO null (grasedenho@yahoo.com.br) on 2016-02-12T19:43:04Z No. of bitstreams: 1 Dissertação_Graziela Cristina Sedenho.pdf: 4075574 bytes, checksum: 8d8fa0c583e32e2f42a6d7092c393844 (MD5) Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-02-16T15:44:23Z (GMT) No. of bitstreams: 1 sedenho_gc_me_araiq_par.pdf: 955629 bytes, checksum: 812d933588fa4febf4bd052f9afbeddf (MD5) Made available in DSpace on 2016-02-16T15:44:23Z (GMT). No. of bitstreams: 1 sedenho_gc_me_araiq_par.pdf: 955629 bytes, checksum: 812d933588fa4febf4bd052f9afbeddf (MD5) Previous issue date: 2016-01-07 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) O etanol é um importante componente da matriz energética brasileira, sendo produzido a partir da cana-de-açúcar. Nesse processo de produção, é produzida vinhaça como subproduto, a qual para cada 1 L de etanol gera-se de 12 L a 18 L. A vinhaça é constituída principalmente de sais de potássio, cálcio e magnésio e compostos orgânicos. Dentre estes, os ácidos carboxílicos tornam-se importantes por estarem presentes em concentrações significativas na vinhaça de cana-de-açúcar e por apresentarem expressiva importância industrial. Sendo assim, nesse trabalho foi desenvolvido um detector eletroquímico baseado em eletrodos de diamante dopado com boro quimicamente modificados com nanopartículas de níquel (NiNPs-BDD) e de cobre (CuNPs-BDD) para determinação dos ácidos lático, málico e tartárico em vinhaça de cana-de-açúcar utilizando a técnica de cromatografia líquida de alta eficiência (CLAE) de troca iônica. Imagens de microscopia eletrônica de varredura e espectros de raios X por dispersão em energia, em conjunto com os experimentos eletroquímicos, mostraram que os eletrodos de BDD foram efetivamente modificados com nanopartículas de óxido-hidróxido de níquel e óxido de cobre com diâmetros médios de 89 nm e 91 nm, respectivamente. Os estudos voltamétricos mostraram que as oxidações dos ácidos lático, málico e tartárico, em meio básico, se dão em potenciais em torno de 0,50 V (vs. Ag/AgCl) e 0,73 V (vs. Ag/AgCl), nos eletrodos NiNPs-BDD e CuNPs-BDD, respectivamente, e são mediadas pelas espécies Ni3+ e Cu3+. O eletrodo de NiNPs-BDD foi utilizado em CLAE com detecção amperométrica pulsada. A coluna de troca aniônica CarboPac PA1 foi utilizada para separação dos ácidos carboxílicos em vinhaça. Empregou-se como fase móvel água deionizada e 0,10 mol L-1 de NaOH em 0,25 mol L-1 de CH3COONa, sob fluxo de 1,0 mL min-1. O potencial de detecção empregado foi 0,48 V vs. Pd. O eletrodo de NiNPs-BDD apresentou boa estabilidade nas condições cromatográficas, tornando viável a sua utilização como detector amperométrico em CLAE. O tempo de análise foi de 27 min e não foi necessário um procedimento complexo e dispendioso de preparo de amostra. As sensibilidades analíticas foram 7,5 × 103 nA L mol-1, 3,5 × 104 nA L mol-1 e 5,4 × 105 nA L mol-1 para os ácidos lático, málico e tartárico, respectivamente. Os limites de detecção foram 1,2 × 10-4 mol L-1, 6,1 × 10-5 mol L-1 e 2,8 × 10-5 mol L-1, respectivamente. As concentrações dos ácidos carboxílicos em vinhaça de cana-de-acúcar foram determinadas pelo método de adição de padrão como sendo (1,2 ± 0,3) × 10-1 mol L-1, (2,7 ± 0,6) × 10-3 mol L-1 e (9,9 ± 1,0) × 10-4 mol L-1 para os ácidos lático, málico e tartárico, respectivamente. Ensaios de recuperação mostraram que o método analítico desenvolvido possui boa exatidão e precisão, podendo ser considerado adequado para a detecção e quantificação dos ácidos lático, málico e tartárico em vinhaça de cana-de-açúcar. O eletrodo de CuNPs-BDD foi empregado na célula amperométrica do cromatógrafo, no entanto não apresentou boa estabilidade nas condições cromatográficas, o que impossibilitou sua utilização na determinação dos compostos de interresse na vinhaça de cana-de-açúcar. Ethanol is an important component of the Brazilian energy matrix, being produced from sugarcane. In this producing procedure, vinasse is produced as by-product, which for every 1 L of ethanol is generated from 12 L to 18 L. The vinasse is basically composed by salts of potassium, calcium and magnesium and organic compounds. Among these, carboxylic acids are important because they are present in significant concentrations in the sugar cane vinasse and show significant industrial importance. Thus, in this work it was developed an electrochemical detector based on boron-doped diamond electrodes chemically modified with nickel nanoparticles (NiNPs-BDD) and copper nanoparticles (CuNPs-BDD) for the determination of lactic acid, malic acid and tartaric acid in vinasse from sugarcane using high-performance liquid chromatography (HPLC) by ion exchange. Images of scanning electron microscopy and spectra of energy-dispersive X-ray in conjuction with electrochemical experiments showed the electrodes of BDD were effectively modified with nickel oxide-hydroxide nanoparticles and copper oxide nanoparticles with diameters of 89 nm and 91 nm, respectively. The voltammetric studies showed the oxidations of lactic acid, malic acid and tartaric acid, in basic medium, tooke place at potentials around 0.50 V (vs. Ag/AgCl) and 0.73 V (vs. Ag/AgCl) at NiNPs-BDD and CuNPs-BDD electrodes, respectively, and they are mediated by Ni3+ and Cu3+ species. NiNPs-BDD electrode was used in HPLC with pulsed amperometric detection. The anion exchange column CarboPac PA1 was used for separation of carboxylic acids in vinasse. It was employed as mobile phase deionized water and 0.10 mol L-1 NaOH in 0.25 mol L-1 CH3COONa under flow of 1.0 mL min-1. The detection potential was 0.48 V vs. Pd. The NiNPs-BDD electrode showed good stability under chromatographic conditions, becoming feasible its use as amperometric detector for HPLC. The analysis time was 27 min and no complex and expensive sample preparation procedure was required. The analytical sensitivities were 7.5 × 103 nA mol-1 L, 3.5 × 104 L mol-1 nA and 5.4 × 105 L mol-1 nA for lactic, malic and tartaric acids. The detection limits were 1.2 × 10-4 mol L-1, 6.1 × 10-5 mol L-1 and 2.8 × 10-5 mol L-1, respectively. The concentrations of the carboxylic acids in sugar cane vinasse were determined by the standard addition method to be (1.2 ± 0.3) × 10-1 mol L-1, (2.7 ± 0.6) × 10-3 mol L-1 and (9.9 ± 1.0) × 10-4 mol L-1 for lactic acid, malic acid and tartaric acid, respectively. Recovery tests showed the analytical method has good accuracy, being considered suitable for the detection and quantification of lactic acid, malic acid and tartaric acid in sugarcane vinasse. CuNPs-BDD electrode was used in the amperometric cell of the chromatograph, however it did not show good stability in the chromatographic conditions, and it could not be employed in the determination of compounds of interest in sugarcane vinasse. FAPESP: 2013/09833-5 FAPESP: 2014/10391-0

Most of the metals released from industrial activity, among them are cadmium (Cd) and nickel (Ni), inhibit the productivity of cultures and affect microbial metabolism. In this context, the aim of this work was to investigate the capacity of sugar cane vinasse to mitigate the adverse effects of Cd and Ni on cell growth, viability, budding rate and trehalose content of Saccharomyces cerevisiae, likely because of adsorption and chelating action. For this purpose, the yeast was grown batch-wise in YED medium supplemented with selected amounts of vinasse and Cd or Ni. The negative effects of Cd and Ni on S. cerevisiae growth and the mitigating one of sugar cane vinasse were quantified by an exponential model. Without vinasse, the addition of increasing levels of Cd and Ni reduced the specific growth rate, whereas in its presence no reduction was observed. Consistently with the well-proved toxicity of both metals, cell viability and budding rate progressively decreased with increasing their concentration, but in the presence of vinasse the situation was remarkably improved. The trehalose content of S. cerevisiae cells followed the same qualitative behavior as cell viability, even though the negative effect of both metals on this parameter was stronger. These results demonstrate the ability of sugar cane vinasse to mitigate the toxic effects of Cd and Ni.

Made available in DSpace on 2018-12-11T17:04:01Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-10-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) The efficiency of individual and integrated processes applied to organic matter reduction and biodegradability improvement of a biodigested sugarcane vinasse wastewater was assessed. Strategies considered were Fenton's oxidation (Strategy 1), coagulation/flocculation (Strategy 2) and the combination of both processes (coagulation/flocculation followed by Fenton's reaction) – Strategy 3. It was found that Fenton's oxidation per se allowed reducing the organic matter, increasing the wastewater biodegradability and a non-toxic effluent was generated; however the cost of treatment was very high (86.6 R$/m3 – 21.2 €/m3). Under optimized conditions, coagulation/flocculation provided a slight increase in effluent's biodegradability, toxicity towards Vibrio fischeri was also eliminated and moderate removals of total organic carbon – TOC – (30.5%), biological oxygen demand – BOD5 – (27.9%) and chemical oxygen demand – COD – (43.6%) were achieved; however, the operating costs are much smaller. The use of dissolved iron resulting from coagulation/flocculation (270 mg/L) as catalyst in the second stage – Fenton's oxidation – was shown to be an innovative and economically attractive strategy. Under optimal conditions overall removals of 51.6% for TOC, 45.7% for BOD5 and 69.2% for COD were achieved, and a biodegradable (BOD5:COD ratio = 0.54) and non-toxic effluent was obtained. In order to increase the efficiency of the process but using less hydrogen peroxide, the Fenton's oxidation was performed by gradually adding the oxidant. This procedure allowed to obtain the highest organic matter removal efficiency (as compared with the addition of all hydrogen peroxide at the beginning of the reaction). This way it was possible to minimize the reagent consumption and, consequently, reduce the treatment cost. LEPABE – Laboratório de Engenharia de Processos Ambiente Biotecnologia e Energia Departamento de Engenharia Química Faculdade de Engenharia Universidade do Porto, R. Dr. Roberto Frias Faculdade de Tecnologia de Jaboticabal “Nilo Stéfani”, Av. Eduardo Zambianchi, 31, Vila Industrial Laboratório de Saneamento Ambiental Departamento de Engenharia Rural Faculdade de Ciências Agrárias e Veterinárias UNESP Universidade Estadual Paulista, Av. Prof. Paulo Donato Castallene, km 5 LSRE – Laboratório de Processos de Separação e Reação Laboratório Associado LSRE/LCM Departamento de Engenharia Química Faculdade de Engenharia Universidade do Porto, R. Dr. Roberto Frias Laboratório de Saneamento Ambiental Departamento de Engenharia Rural Faculdade de Ciências Agrárias e Veterinárias UNESP Universidade Estadual Paulista, Av. Prof. Paulo Donato Castallene, km 5 CNPq: 483118/2011-7 CAPES: PNPD-3137/2010