A method to pretreatment of biomasses using glycerol as a green solvent was developed. Optimization of organosolv pretreatment was performed using a 23 factorial design, investigating synergism among the variables particle size (from < 0.85 to > 2.0 mm), FeCl3 concentration (0.025-0.175 mol L-1), and temperature (160-220 °C). Although the effects of the variables differed according to the type of lignocellulose, it was nonetheless possible to find an optimal condition in common (< 0.85 mm; 0.025 mol L-1; 220 °C), which was economically and environmentally sustainable, employing a small amount of catalyst. The biomasses pretreated using this combination of factors exhibited enzymatic digestibility exceeding 93% after 48 h, reflecting efficient reduction of recalcitrance as a result of high removal of hemicellulose (ca. 90%), provided by the use of FeCl3, together with substantial delignification. There was low formation of inhibitors in the hydrolysate, indicating that it could be directly fermented. The lignin removed to liquors could be easily recovered by centrifugation. Tests carried out under the optimal condition revealed that after the pretreatment the biomass could be directly used in enzymatic hydrolysis, without washing and wet. Furthermore, after simple treatment, crude glycerol was as effective as commercial glycerol.

Polycyclic aromatic hydrocarbons (PAHs) are an important environmental issue and the identification of new biocatalysts for an efficient biodegradation of these compounds is essential for bioremediation. Therefore, fungi strains isolated for the first time from a tropical peat at Santo Amaro das Brotas (Brazil) were studied for fluoranthene biodegradation. Fusarium sp. AC-7, Penicillium sp. AC-1 and Penicillium sp. AC-6 were isolated using fluoranthene as sole carbon source. All strains were tested for biodegradation of 100 mg L−1 fluoranthene during 14 and 28 days. After 28 days of biodegradation, 64 ± 3, 60 ± 4 and 51 ± 2% biodegradation was observed for Penicillium sp. AC-1, Penicillium sp. AC-6 and Fusarium sp. AC-7, respectively. Analysis of the obtained compounds enabled the identification of four metabolites, which were common to the three employed strains: anthrone, anthraquinone, 9-methoxyanthracene and cyclopropa[1]phenanthrene. It is important to note that control experiments were performed. The obtained results clearly demonstrated the efficiency of tropical peat fungi in the transformation of fluoranthene. These findings showed the potential of tropical peats for isolation of fungi and indicated that these strains can be applied for bioremediation processes of areas contaminated with fluoranthene and other PAHs.

This work describes the removal of pesticides from water using activated and magnetized biochars produced from exhausted husk, and dry tannin from barks of black wattle (Acacia mearnsii De Wild.). These materials were characterized using chemical, spectroscopic, thermal, solid structure and surface area techniques. The activated and magnetized biochars were effective in removing the pesticides thiacloprid and thiamethoxam from both ultrapure water and Marcela Water Reservoir, Itabaiana, Sergipe State, Brazil. At the longest time examined, the amounts of thiacloprid and thiamethoxam adsorbed per gram of activated biochar adsorbent were 1.02 and 0.97 mg, respectively, while values of 0.73 mg (thiacloprid) and 0.40 mg (thiamethoxam) were obtained using magnetized biochar. A pseudo-second order model correctly described the kinetics of adsorption of both pesticides (R(2) ≥ 0.922). Desorption experiments revealed that the spent biochars could not be easily regenerated, which indicated that the forces holding the adsorbed fluid molecules to the solid surface were relatively strong.

Este trabalho descreve a síntese e caracterização de um novo adsorvente mesoporoso que consiste o MCM-41 funcionalizado com o ácido p-aminobenzóico modificado (PABA-Si). A síntese foi realizada pelo método hidrotermal/co-condensação. O PABA-MCM-41 foi caracterizado usando FTIR, SAXS, adsorção/desorção de N2, MEV e TG. Os experimentos em batelada foram utilizados para determinar os efeitos da concentração inicial do adsorbato, tempo de contato e temperatura. A adsorção do benzo[a]pireno (B[a]P) alcançou o equilíbrio depois de 90 min (q e = 27,2 µg g-1) e concentrações mais altas do adsorbato foram associadas com o aumento, em ambos, da percentagem de remoção (71,0-95,7%) e no valor de q e (20,1-27,1 µg g-1). A adsorção seguiu o modelo cinético de pseudo-segunda ordem, e se ajustou ao modelo de isoterma de Langmuir. Foi verificado em temperaturas mais altas um aumento na taxa inicial de adsorção e na constante cinética. Os parâmetros termodinâmicos indicaram que o processo foi espontâneo, endotérmico e com uma tendência para desordem.

This work describes the synthesis and characterization of a new mesoporous adsorbent consisting of MCM-41 functionalized with modified p-aminobenzoic acid (PABA-Si). The synthesis was performed by a hydrothermal/co-condensation method. The PABA-MCM-41 was characterized using FTIR, SAXS, N2 adsorption/desorption, SEM, and TG. Batch experiments were employed to determine the effects of initial adsorbate concentration, contact time, and temperature. The adsorption of benzo[a]pyrene (B[a]P) reached equilibrium after ca. 90 min (q e = 27.2 µg g-1), and higher adsorbate concentrations were associated with increases in both the percentage removal (71.0-95.7%) and the value of q e (20.1-27.1 µg g-1). The adsorption followed pseudo-second order kinetics, and was fitted using the Langmuir isotherm model. At higher temperatures, there were increases in the initial rate of adsorption and the kinetic constant. The thermodynamic parameters indicated that the process was spontaneous, endothermic, and with a tendency to disorder.

O fracionamento por tamanho molecular da matéria orgânica natural (MON) de amostras de água do Parque Nacional Serra de Itabaiana (Brasil) foi utilizado para caracterização temporal da complexação de íons metálicos. Um sistema de ultrafiltração em cinco estágios foi usado para separar a MON em seis frações (F1: > 100; F2: 100-50; F3: 50-30; F4: 30-10; F5: 10-5; F6: < 5 kDa). A distribuição obtida, inicialmente para amostra in natura, mostrou que metais (Al, Ba, Cr, Cu, Fe, Mn, Ni, Pb e Sr) foram complexados, preferencialmente, pela fração F1, a qual continha maior concentração de carbono orgânico dissolvido (COD). A seguinte ordem decrescente de distribuição de carbono foi obtida: F1 >> F3 > F2 = F4 > F6 > F5. As frações F2 e F5 foram as mais humificadas e F6 a menos humificada. Após 30 dias com adição de elevadas concentrações de metais nas amostras filtradas novas distribuições de COD e metais foram observadas. Maior COD ainda foi encontrado na F1 com teores de carbono decrescendo na seguinte ordem: F1 > F2 > F3 > F4 > F5 > F6. Os metais apresentaram distribuições similares e homogêneas em todas as frações. Valores de log K foram similares para as amostras in natura e para aquelas de 30 dias após a adição dos metais (7,1 e 7,0; 6,6 e 6,9; e 7,2 e 7,0 para Al, Cu e Fe-MON, respectivamente), indicando uma nova condição de equilíbrio na distribuição dos metais após 30 dias. As espécies formadas entre MON e os metais adicionados mostraram um modelo de distribuição que mudou em função do tempo de complexação, indicando uma transformação dos sítios de ligação da MON, sugerindo que o efeito coletivo das frações é mais importante que as propriedades individuais e confirmando que as frações mais humificadas exercem grande influência na complexação de metais em ambientes aquáticos.

Molecular size fractionation of the natural organic matter (NOM) in water samples from the Serra de Itabaiana National Park (Brazil) was used to characterize the temporal behavior of metal ion complexation. A special five-stage tangential-flow ultrafiltration device was used to separate NOM in six size fractions (F1: > 100; F2: 100-50; F3: 50-30; F4: 30-10; F5: 10-5; F6: < 5 kDa). The distribution patterns obtained for one in natura sample showed that metals (Al, Ba, Cr, Cu, Fe, Mn, Ni, Pb and Sr) were preferentially complexed by the F1 fraction, which contained higher concentration of dissolved organic carbon (DOC). The following decreasing order of carbon distribution in the different fractions was obtained: F1 >> F3 > F2 = F4 > F6 > F5. Fractions F2 and F5 were the most humified, and F6 the least. New distributions of DOC and metals were observed after 30 days when high concentrations of metals were added to filtered samples. Highest DOC was still found in F1, with carbon contents decreasing in the following order: F1 > F2 > F3 > F4 > F5 > F6. The studied metals presented similar and homogeneous distributions in all fractions. Values of log K were similar for samples in natura and 30 days after addition of metals (7.1 and 7.0, 6.6 and 6.9, and 7.2 and 7.0 for Al, Cu and Fe-NOM, respectively), indicating a new dynamic equilibrium in the metals distribution after 30 days. The species formed between NOM and spiked metals showed distribution patterns that changed as a function of complexation time, indicating a transformation of the NOM binding sites, suggesting that the collective effect of the fractions is more important than individual site properties, and confirming that the most humified fractions exert a large influence on the complexation of metals in aquatic environments.

A turfa natural foi testada na extração em fase sólida de acefato, clorprofam, pirimicarbe, bifentrina, tetradifona e fosalona da planta medicinal Cordia salicifolia, utilizando cromatografia a gás acoplada a espectrometria de massas no modo de monitoramento de íons selecionados. Considerando que a legislação brasileira não estabelece limites máximos de resíduos para plantas medicinais, a recuperação foi avaliada em dois níveis de concentração (0,5 e 1,0 mg kg-1), resultando em valores de recuperação entre 64% e 118%, com coeficientes de variação entre 5,6% e 26,4% para a turfa. Os limites de detecção variaram entre 0,10 e 0,15 mg kg-1, enquanto que os limites de quantificação, entre 0,15 e 0,25 mg kg-1 para os pesticidas estudados. O método desenvolvido foi linear no intervalo de 0,1 a 5,0 μg g-1, com coeficientes de correlação entre 0,9975 e 0,9986. A comparação entre a turfa natural e o sorbente convencional (alumina neutra) apresentou desempenho similar da turfa na recuperação dos seis pesticidas.

Natural peat was tested for solid-phase extraction of acephate, chlorpropham, pirimicarb, bifenthrin, tetradifon and phosalone from the medicinal plant Cordia salicifolia, using gas chromatography-mass spectrometry with selected ion monitoring (GC/MS, SIM). Considering that there are no Brazilian regulations concerning maximum permissible pesticide residue concentrations in medicinal herbs, recovery experiments were carried out (three replicates) at two arbitrary fortification levels (0.5 and 1.0 mg kg-1), resulting in recoveries ranging from 64% to 118% and relative standard deviations between 5.6% and 26.4% for peat sorbent. Detection and quantification limits for herb ranged from 0.10 to 0.15 mg kg-1 and from 0.15 to 0.25 mg kg-1, respectively, for the different pesticides studied. The developed method was linear over the range assayed, 0.1-5.0 μg g-1, with correlation coefficients ranging from 0.9975 to 0.9986 for all pesticides. Comparison between natural peat and conventional sorbent (neutral alumina) showed similar performance of peat for the six pesticides tested.

Amostras de turfa (SAO e ITA) coletadas no Estado de Sergipe, Brasil, foram caracterizadas por diferentes técnicas: análise térmica e elementar, infravermelho, espectroscopia de ressonância magnética nuclear de 13C (NMR), microscopia eletrônica de varredura (SEM), microscopia eletrônica de varredura ambiental (ESEM), difratometria de raios X (XRD) e comparadas com outras amostras de turfa (SAP) coletadas no Estado de São Paulo, Brasil. As razões mais baixas O/C, E4/E6 e as curvas de análise térmica diferencial (DTA) da amostra de Santo Amaro (SAO) indicaram que esta possui o mais alto grau de decomposição. Resultados da espectroscopia na região do infravermelho mostraram que as amostras de Itabaiana (ITA) e São Paulo (SAP) apresentam pico predominante a 1086 cm-1 atribuídos a presença de Si-O diferente da amostra de Santo Amaro (SAO). Esta mostrou dois picos intensos a 2920 cm-1 e 2850 cm-1 corroborando com dados de RMN 13C e análise termogravimétrica em que houve maior abundância dos grupos C-alquila. A difratometria de raios X (XRD) da amostra de SAO apresentou características de material amorfo. Entretanto, as amostras de SAP e ITA revelam maior presença de quartzo mineral. A microscopia eletrônica de varredura (SEM) e a microscopia eletrônica de varredura ambiental (ESEM) mostraram que a superfície das amostras de turfa possui grânulos porosos de matéria orgânica. As amostras de turfa de ITA e SAP são semelhantes enquanto a de SAO possui alto teor de matéria orgânica. Apenas a amostra de SAO apresenta características de turfa. Os resultados deste estudo mostraram que as amostras são muito diferentes devido aos teores variáveis de material orgânico e inorgânico.

Peat was taken from the Sergipe State, Brazil and characterized by several techniques: elemental and thermal analyses; Fourier infrared (FTIR) and solid state 13C nuclear magnetic resonance (NMR) spectroscopies; scanning electron microscopy (SEM), environmental scanning electron microscopy (ESEM) and X-ray diffractometry (XRD). Also, the Sergipe State peat samples were compared with other peat sample from later from Sao Paulo State, Brazil. The lowest O/C and E4/E6 ratios and differential thermal analysis (DTA) curves of the Santo Amaro (SAO) sample indicated that this sample had the highest degree of decomposition. FTIR results showed that Itabaiana (ITA) and São Paulo (SAP) samples presented more prominent peak at 1086 cm-1 attributed the presence of Si-O than SAO sample spectra. The SAO sample showed two more intense peaks at 2920 cm-1 and 2850 cm-1. These results were corroborated by 13C NMR and thermal gravimetric (TG) where the relative abundance of the alkyl-C groups was greater in the SAO sample. The X-ray diffractometry (XRD) of SAO sample is characteristic of amorphous matter however, the SAP and ITA samples revealed the large presence of quartz mineral. The scanning electron microscopy (SEM) and environmental scanning electron microscopy (ESEM) showed that the surface of peat samples have porous granules of organic material. The ITA and SAP peat samples are alike while SAO peat sample is richer in organic material. Only the SAO sample has truthful characteristics of peat. The results of this study showed that the samples are very different due to variable inorganic and organic material contents.