AnSBBR Applied to the Treatment of Metalworking Fluid Wastewater: Effect of Organic and Shock Load

An investigation was performed regarding the application of a mechanically stirred anaerobic sequencing batch biofilm reactor containing immobilized biomass on inert polyurethane foam (AnSBBR) to the treatment of soluble metalworking fluids to remove organic matter and produce methane. The effect of increasing organic matter and reactor fill time, as well as shock load, on reactor stability and efficiency have been analyzed. The 5-L AnSBBR was operated at 30 A degrees C in 8-h cycles, agitation of 400 rpm, and treated 2.0 L effluent per cycle. Organic matter was increased by increasing the influent concentration (500, 1,000, 2,000, and 3,000 mg chemical oxygen demand (COD)/L). Fill times investigated were in the batch mode (fill time 10 min) and fed-batch followed by batch (fill time 4 h). In the batch mode, organic matter removal efficiencies were 87%, 86%, and 80% for influent concentrations of 500, 1,000, and 2,000 mgCOD/L (1.50, 3.12, and 6.08 gCOD/L.d), respectively. At 3,000 mgCOD/L (9.38 gCOD/L.d), operational stability could not be achieved. The reactor managed to maintain stability when a shock load twice as high the feed concentration was applied, evidencing the robustness of the reactor to potential concentration variations in the wastewater being treated. Increasing the fill time to 4 h did not improve removal efficiency, which was 72% for 2,000 mgCOD/L. Thus, gradual feeding did not improve organic matter removal. The concentration of methane formed at 6.08 gCOD/L was 5.20 mmolCH(4), which corresponded to 78% of the biogas composition. The behavior of the reactor during batch and fed-batch feeding could be explained by a kinetic model that considers organic matter consumption, production, and consumption of total volatile acids and methane production.

Application of molecular techniques to evaluate the methanogenic archaea and anaerobic bacteria in the presence of oxygen with different COD : sulfate ratios in a UASB reactor

In this paper, the microbial characteristics of the granular sludge in the presence of oxygen (3.0 +/- 0.7 mg O-2 1(-1)) were analyzed using molecular biology techniques. The granules were provided by an upflow anaerobic sludge blanket (UASB) operated over 469 days and fed with synthetic substrate. Ethanol and sulfate were added to obtain different COD/SO42- ratios (3.0, 2.0, and 1.6). The results of fluorescent in situ hybridization (FISH) analyses showed that archaeal cells, detected by the ARC915 probe, accounted for 77%, 84%, and 75% in the COD/SO42- ratios (3.0, 2.0, and 1.6, respectively). Methanosaeta sp. was the predominant acetoclastic archaea observed by optical microscopy and FISH analyses, and confirmed by sequencing of the excised bands of the DGGE gel with a similarity of 96%. The sulfate-reducing bacterium Desulfovibrio vulgaris subsp. vulgaris (similarity of 99%) was verified by sequencing of the DGGE band. Others identified microorganism were similar to Shewanella sp. and Desulfitobacterium hafniense, with similarities of 95% and 99%, respectively. These results confirmed that the presence of oxygen did not severely affect the metabolism of microorganisms that are commonly considered strictly anaerobic. We obtained mean efficiencies of organic matter conversion and sulfate reducing higher than 74%. (C) 2008 Elsevier Ltd. All rights reserved.

Evaluation of natural and synthetic compounds according to their antioxidant activity using a multivariate approach

The antioxidant activity of natural and synthetic compounds was evaluated using five in vitro methods: ferric reducing/antioxidant power (FRAP), 2,2-diphenyl-1-picrylhydradzyl (DPPH), oxygen radical absorption capacity (ORAL), oxidation of an aqueous dispersion of linoleic acid accelerated by azo-initiators (LAOX), and oxidation of a meat homogenate submitted to a thermal treatment (TBARS). All results were expressed as Trolox equivalents. The application of multivariate statistical techniques suggested that the phenolic compounds (caffeic acid, carnosic acid, genistein and resveratrol), beyond their high antioxidant activity measured by the DPPH, FRAP and TBARS methods, showed the highest ability to react with the radicals in the ORAC methodology, compared to the other compounds evaluated in this study (ascorbic acid, erythorbate, tocopherol, BHT, Trolox, tryptophan, citric acid, EDTA, glutathione, lecithin, methionine and tyrosine). This property was significantly correlated with the number of phenolic rings and catecholic structure present in the molecule. Based on a multivariate analysis, it is possible to select compounds from different clusters and explore their antioxidant activity interactions in food products.

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.

Characterization of Brazilian lager and brown ale beers based on color, phenolic compounds, and antioxidant activity using chemometrics

BACKGROUND: Epidemiological studies have shown that beer has positive effects on inhibiting atherosclerosis, decreasing the content of serum low-density lipoprotein cholesterol and triglycerides, by acting as in vivo free radical scavenger. In this research, the antioxidant activity of commercial Brazilian beers (n = 29) was determined by the oxygen radical absorbance capacity (ORAC) and 1,1 -diphenyl-2-picrylhydrazyl (DPPH(center dot)) assays and results were analyzed by chemometrics. RESULTS: The brown ale samples (n = 11) presented higher (P < 0.05) flavonoids (124.01 mg L(-1)), total phenolics (362.22 mg L(-1)), non-flavonoid phenolics (238.21 mg L(-1)), lightness (69.48), redness (35.75), yellowness (55.71), color intensity (66.86), hue angle (59.14), color saturation (0.9620), DPPH(center dot) values (30.96% inhibition), and ORAC values (3,659.36 mu mol Trolox equivalents L(-1)), compared to lager samples (n = 18). Brown ale beers presented higher antioxidant properties (P < 0.05) measured by ORAC (1.93 times higher) and DPPH (1.65 times higher) compared to lager beer. ORAC values correlated well with the content of flavonoids (r = 0.47; P = 0.01), total phenolic compounds (r = 0.44; P < 0.01) and DPPH (r = 0.67; P < 0.01). DPPH values also correlated well to the content of flavonoids (r = 0.69; P < 0.01), total phenolic compounds (r = 0.60; P < 0.01), and non-flavonoid compounds (r = 0.46; P = 0.01). CONCLUSION: The results suggest that brown ale beers, and less significantly lager beers, could be sources of bioactive compounds with suitable free radical scavenging properties. (C) 2010 Society of Chemical Industry

Homocoupling reactions of alkynes, alkenes and alkyl compounds

FAPESP[07/5904-2]

Synergism on antioxidant activity between natural compounds optimized by response surface methodology

Despite the increase in the use of natural compounds in place of synthetic derivatives as antioxidants in food products, the extent of this substitution is limited by cost constraints. Thus, the objective of this study was to explore the synergism on the antioxidant activity of natural compounds, for further application in food products. Three hydrosoluble compounds (x(1) = caffeic acid, x(2) = carnosic acid, and x(3) = glutathione) and three liposoluble compounds (x(1) = quercetin, x(2) = rutin, and x(3) = genistein) were mixed according to a ""centroid simplex design"". The antioxidant activity of the mixtures was analyzed by the ferric reducing antioxidant power (FRAP) and oxygen radical absorbance capacity (ORAL) methodologies, and activity was also evaluated in an oxidized mixed micelle prepared with linoleic acid (LAOX). Cubic polynomial models with predictive capacity were obtained when the mixtures were submitted to the LAOX methodology ((y) over cap = 0.56 x(1) + 0.59 x(2) + 0.04 x(3) + 0.41 x(1)x(2) - 0.41 x(1)x(3) - 1.12 x(2)x(3) - 4.01 x(1)x(2)x(3)) for the hydrosoluble compounds, and to FRAP methodology ((y) over cap = 3.26 x(1) + 2.39 x(2) + 0.04 x(3) + 1.51 x(1)x(2) + 1.03 x(1)x(3) + 0.29 x(1)x(3) + 3.20 x(1)x(2)x(3)) for the liposoluble compounds. Optimization of the models suggested that a mixture containing 47% caffeic acid + 53% carnosic acid and a mixture containing 67% quercetin + 33% rutin were potential synergistic combinations for further evaluation using a food matrix.

Effect of chloride concentration on the electrochemical treatment of a synthetic tannery wastewater

The electrochemical treatment of a synthetic tannery wastewater prepared with 30 compounds used in animal skin processing was studied. Electrolyses were performed in a one-compartment flow cell at a current density of 20 mA cm(-2), using a dimensionally stable anode (DSA (R)) of composition Ti/Ir(0.10)Sn(0.90)O(2) as the working electrode. Effects of chloride concentration and presence of sulfate were evaluated. Variation in the concentration of phenolic compounds as a function of electrolysis time revealed a first-order exponential decay; faster phenol removals were obtained with increasing chloride concentration in the wastewater. Lower phenol removals were obtained in the presence of sulfate. Higher chloride concentrations led to a faster decrease in total organic carbon (TOC), chemical oxygen demand (COD), and absorbance values at 228 nm. Faster wastewater color removal, higher current efficiency and lower energy consumption were also obtained. This electrochemical treatment was also able to reduce the wastewater toxicity for Daphnia similis. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis of new amphiphilic chlorin derivatives from protoporphyrin-IX dimethyl ester

A simple synthesis of new amphiphilic chlorin derivatives from protoporphyrin-IX dimethyl ester is reported.The preparation Of Such compounds is based in a straightforward methodology, which involves the Diels-Alder reaction of protoporphyrin-IX dimethyl ester with maleic anhydride followed by addition of nucleophilic species to the initially formed cycloadducts, a transformation, which is highly regioselective. Preliminary photophysical studies with the new compounds show that they meet adequate features for PDT applications. (c) 2008 Elsevier Ltd. All rights reserved.

Electrochemical oxidation of synthetic tannery wastewater in chloride-free aqueous media

The electrochemical treatment of a synthetic tannery wastewater, prepared with several compounds used by finishing tanneries, was studied in chloride-free media. Boron-doped diamond (Si/BDD), antimony-doped tin dioxide (Ti/SnO(2)-Sb), and iridium-antimony-doped tin dioxide (Ti/SnO(2)-Sb-Ir)were evaluated as anode. The influence of pH and current density on the treatment was assessed by means of the parameters used to measure the level of organic contaminants in the wastewater; i.e., total phenols, chemical oxygen demand (COD), total organic carbon (TOC), and absorbance. Results showed that faster decrease in these parameters occurred when the Si/BDD anode was used. Good results were obtained with the Ti/SnO(2)-Sb anode, but its complete deactivation was reached after 4h of electrolysis at 25 mA cm(-2), indicating that the service life of this electrode is short. The Ti/SnO(2)-Sb-Ir anode is chemically and electrochemically more stable than the Ti/SnO(2)-Sb anode, but it is not suitable for the electrochemical treatment under the studied conditions. No significant changes were observed for electrolyses performed at different pH conditions with Si/BDD, and this electrode led to almost complete mineralization after 4 h of electrolysis at 100mAcm(-2). The increase in current density resulted in faster wastewater oxidation, with lower current efficiency and higher energy consumption. Si/BBD proved to be the best electrodic material for the direct electrooxidation of tannery wastewaters. (C) 2010 Elsevier B.V. All rights reserved.

Electrochemical oxidation of acid black 210 dye on the boron-doped diamond electrode in the presence of phosphate ions: Effect of current density, pH, and chloride ions

The electrochemical oxidation of acid black 210 dye (AB-210) on the boron-doped diamond (BDD) was investigated under different pH conditions. The best performance for the AB-210 oxidation occurred in alkaline phosphate solution. This is probably due to oxidizing agents such as phosphate radicals and peroxodiphosphate ions, which can be electrochemically produced with good yields on the BDD anode, mainly in alkaline solution. Under this condition, the COD (chemical oxygen demand) removal was higher than that obtained from the model proposed by Comninellis. Electrolyses performed in phosphate buffer and in the presence of chloride ions resulted in faster COD and color removals in acid and neutral solutions, but in alkaline phosphate solution, a better performance in terms of TOC removal was obtained in the absence of chloride. Moreover, organochloride compounds were detected in all electrolyses performed in the presence of chloride. The AB-210 electrooxidation on BDD using phosphate as supporting electrolyte proved to be interesting since oxidizing species generated from phosphate ions were able to completely degrade the dye without producing organochloride compounds. (C) 2009 Elsevier Ltd. All rights reserved.

Potentially bioavailable metals in sediment from a tropical polymictic environment-Rio Grande Reservoir, Brazil

Background, aim and scope Although many recent studies have focused on sediment potential toxicity, few of them were performed in tropical shallow aquatic environments. Those places can suffer short-time variations, especially due to water column circulations generated by changes in temperature and wind. Rio Grande reservoir is such an example; aside from that, it suffers various anthropogenic impacts, despite its multiple uses. Materials and methods This work presents the first screening step for understanding sediment quality from Rio Grande reservoir by comparing metal content using three different sediment quality guidelines. We also aimed at verifying any possible spatial heterogeneity. Results and discussion We found spatial heterogeneity varying according to the specific metal. Results showed a tendency for metals to remain as insoluble as metal sulfide (potentially not bioavailable), since sulfide was in excess and sediment physical-chemical characteristics contribute to sulfide maintenance (low redox potential, neutral pH, low dissolved oxygen, and high organic matter content). On the other hand, metal concentrations were much higher than suggested by Canadian guidelines and regional background values, especially Cu, which raises the risk of metal remobilization in cases of water circulation. Further study steps include the temporal evaluation of AVS/SEM, a battery of bioassays and the characterization of organic compounds.

Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin

Submicron atmospheric particles in the Amazon Basin were characterized by a high-resolution aerosol mass spectrometer during the wet season of 2008. Patterns in the mass spectra closely resembled those of secondary-organic-aerosol (SOA) particles formed in environmental chambers from biogenic precursor gases. In contrast, mass spectral indicators of primary biological aerosol particles (PBAPs) were insignificant, suggesting that PBAPs contributed negligibly to the submicron fraction of particles during the period of study. For 40% of the measurement periods, the mass spectra indicate that in-Basin biogenic SOA production was the dominant source of the submicron mass fraction, contrasted to other periods (30%) during which out-of-Basin organic-carbon sources were significant on top of the baseline in-Basin processes. The in-Basin periods had an average organic-particle loading of 0.6 mu g m(-3) and an average elemental oxygen-to-carbon (O:C) ratio of 0.42, compared to 0.9 mu g m(-3) and 0.49, respectively, during periods of out-of-Basin influence. On the basis of the data, we conclude that most of the organic material composing submicron particles over the Basin derived from biogenic SOA production, a finding that is consistent with microscopy observations made in a concurrent study. This source was augmented during some periods by aged organic material delivered by long-range transport. Citation: Chen, Q., et al. (2009), Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin, Geophys. Res. Lett., 36, L20806, doi: 10.1029/2009GL039880.

On the catalytic hydrogenation of polycyclic aromatic hydrocarbons into less toxic compounds by a facile recoverable catalyst

Here we present the catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) to less toxic mixtures of saturated and partial unsaturated polycyclic hydrocarbons under mild reaction conditions using a magnetically recoverable rhodium catalyst and molecular hydrogen as the exclusive H source. The catalyst is easily recovered after each reaction by placing a permanent magnet on the reactor wall and it can be reused in successive runs without any significant loss of catalytic activity. As an example, anthracene was totally converted into the saturated polycyclic hydrocarbon form (ca. 60%) and the partially hydrogenated form, 1,2,3,4,5,6,7,8-octahydroanthracene (ca. 40%). The catalyst operates in a broad range of temperature and H(2) pressure in both organic and aqueous/organic solutions of anthracene and it also exhibits significant activity at low substrate concentrations (20 ppm). This can be an efficient recycling process for hydrogenation of PAHs present in contaminated fluid waste streams. (C) 2009 Elsevier B.V. All rights reserved.

On the Nucleophilicity of Boryllithium Compounds. A Theoretical Study

Boron compounds are widely used in synthetic chemistry. The synthesis of the compounds is relatively easy, presenting thermodynamic stability and synthetic versatility. Almost all of them show electrophilic reactivity. Recently, some boryllithium species have been reported as a base or a nucleophile in reaction with organic electrophiles in S(N)2 reactions. In the present work, the proton affinity (PA) of boryllithium compounds was calculated. These values can be useful as theoretical reference values and to provide valuable complementary information for the interpretation and discussion of the basicity of these compounds. The proton affinity was calculated using a theoretical method based on density functional theory and high-level theoretical methods through MP2 and G2MP2 levels of theory. In addition, some global and local reactivity indexes based on density functional theory (DFT) on boryllithium compounds were studied. In order to compare and discuss the chemical reactivity of these compounds, some analogues and electrophilic boron compounds were also studied. Our results showed a local and global nucleophilic reactivity of the boryllithium molecules in agreement with the experimental. reactivity. The boryllithium compounds revealed to be strong bases in comparison to other analogue compounds studied in this work.