A mechanistic approach to methylene blue sorption on two vegetable wastes: Cork bark and grape stalks

Two vegetable wastes, cork bark and grape stalks, were investigated for the removal of methylene blue from aqueous solution. The effects of contact time, dye concentration, pH, and temperature on sorption were studied relative to adsorption on a commercially-activated carbon. The highest adsorption yield was obtained within the pH range 5 to 10 for grape stalks and 7 to 10 for cork bark. The sorption kinetics of dye onto activated carbon and grape stalks was very fast. Kinetics data were fitted to the pseudo-first and second order kinetic equations, and the values of the pseudo-second-order initial rate constants were found to be 1.69 mg g-1 min-1 for activated carbon, 2.24 mg g-1 min-1 for grape stalks, and 0.90 mg g-1 min-1 for cork bark. Langmuir maximum sorption capacities for activated carbon, grape stalks, and cork bark for methylene blue estimated by the Orthogonal Distance Regression method (ODR) were 157.5 mg g-1, 105.6 mg g-1, and 30.52 mg g-1, respectively. FTIR spectra indicated that carboxylic groups and lignin play a significant role in the sorption of methylene blue. Electrostatic forces, n-p interactions, cation-p, and p-p stacking interactions contribute to methylene blue sorption onto grape stalks and cork bark. Grape stalks can be considered an efficient biosorbent and as a viable alternative to activated carbon and ion-exchange resins for the removal of methylene blue

Remediação de drenagem ácida de mina usando zeólitas sintetizadas a partir de cinzas leves de carvão

Zeolitic material was synthesized from coal fly ashes (baghouse filter fly ash and cyclone filter fly ash) by hydrothermal alkaline activation. The potential application of the zeolitic product for decontamination of waters from acid mine drainage was evaluated. The results showed that a dose of 30 g L-1 of zeolitic material allowed the water to reach acceptable quality levels after treatment. Both precipitation and cation-exchange processes accounted for the reduction in the pollutant concentration in the treated waters.

Triggering the generation of an iron(IV)-oxo compound and its reactivity toward sulfides by RuII photocatalysis

The preparation of [FeIV(O)(MePy2tacn)]2+ (2, MePy2tacn = N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane) by reaction of [FeII(MePy2tacn)(solvent)]2+ (1) and PhIO in CH3CN and its full characterization are described. This compound can also be prepared photochemically from its iron(II) precursor by irradiation at 447 nm in the presence of catalytic amounts of [Ru II(bpy)3]2+ as photosensitizer and a sacrificial electron acceptor (Na2S2O8). Remarkably, the rate of the reaction of the photochemically prepared compound 2 toward sulfides increases 150-fold under irradiation, and 2 is partially regenerated after the sulfide has been consumed; hence, the process can be repeated several times. The origin of this rate enhancement has been established by studying the reaction of chemically generated compound 2 with sulfides under different conditions, which demonstrated that both light and [Ru II(bpy)3]2+ are necessary for the observed increase in the reaction rate. A combination of nanosecond time-resolved absorption spectroscopy with laser pulse excitation and other mechanistic studies has led to the conclusion that an electron transfer mechanism is the most plausible explanation for the observed rate enhancement. According to this mechanism, the in-situ-generated [RuIII(bpy)3] 3+ oxidizes the sulfide to form the corresponding radical cation, which is eventually oxidized by 2 to the corresponding sulfoxide

Distribuição de mercúrio em diferentes solos da Bacia do médio Rio Negro-AM: influência da matéria orgânica no ciclo biogeoquímico do mercúrio

Soils play an important role in the biogeochemical cycle of mercury as a sink for and source of this metallic species to atmospheric and hydrological compartments. In the study reported here, various types of soil were evaluated to ascertain the influence of parameters such as pH, organic matter content, Fe, Al, sand, silt, clay, C/H, C/N, C/O atomic ratios, and cation exchange capacity on the distribution of Hg in Amazonia's mid-Negro River basin. The data obtained were interpreted by multivariate exploratory analyses (hierarchical cluster analysis and principal component analysis), which indicated that organic matter plays an important role in mercury uptake in the various soils studied. The soils in floodable areas were found to contain 1.5 to 2.8-fold higher Hg concentrations than those in non-floodable areas. Since these soils are flooded almost year-round, they are less available to participate in redox processes at the soil/atmosphere interface. Hence, floodable areas, which comprise humic-rich soils, accumulate more mercury than non-floodable soils, thus playing an important role in the biogeochemical cycle of Hg in Amazonia's mid-Negro River basin.

Argilas especiais: argilas quimicamente modificadas - uma revisão

The simultaneous use of the specific values of some structural and chemical properties of clay minerals, such as kaolinite, montmorillonite and talc, allows the development of new properties for these materials, especially in relation to the external and internal microcrystal surfaces. These developments are very diversified for montmorillonite, due to the high specific surface area, expansible basal spacings, easy intercalation inside the 2:1 structural layers and a reversible and high cation exchance capacity. The review presents examples of chemical modifications on kaolins, montmorillonites (bentonites) and talcs.

A relevante potencialidade dos centros básicos nitrogenados disponíveis em polímeros inorgânicos e biopolímeros na remoção catiônica

This review reports the application of inorganic and organic polymeric materials for cation removal by using nitrogenated basic centers. The data demonstrate the importance of the desired groups when free or immobilized on natural or synthesized inorganic polymers through silanol groups. Thus, the most studied silica gel is followed by natural crysotile and talc polymers, and the synthesized mesopore silicas, talc-like, silicic acids, phosphates and phyllosilicates. The organic natural biopolymeric chitin and cellulose were chemically modified to improve the availability of the amine groups or the reactivity with desirable molecules to enlarge the content of basic centers. The cation removal takes place at the solid/liquid interface and some interactive effects have their thermodynamic data determined.

Multi-Eruption Solar Energetic Particle Events Observed by SOHO/ERNE

In the last two decades of studying the Solar Energetic Particle (SEP) phenomenon, intensive emphasis has been put on how and when and where these SEPs are injected into interplanetary space. It is well known that SEPs are related to solar flares and CMEs. However, the role of each in the acceleration of SEPs has been under debate since the major role was taken from flares ascribed to CMEs step by step after the skylab mission, which started the era of CME spaceborn observations. Since then, the shock wave generated by powerful CMEs in between 2-5 solar radii is considered the major accelerator. The current paradigm interprets the prolonged proton intensity-time profile in gradual SEP events as a direct effect of accelerated SEPs by shock wave propagating in the interplanetary medium. Thus the powerful CME is thought of as a starter for the acceleration and its shock wave as a continuing accelerator to result in such an intensity-time profile. Generally it is believed that a single powerful CME which might or might not be associated with a flare is always the reason behind such gradual events.

In this work we use the Energetic and Relativistic Nucleus and Electrons ERNE instrument on board Solar and Heliospheric Observatory SOHO to present an empirical study to show the possibility of multiple accelerations in SEP events. In the beginning we found 18 double-peaked SEP events by examining 88 SEP events. The peaks in the intensity-time profile were separated by 3-24 hours. We divided the SEP events according to possible multiple acceleration into four groups and in one of these groups we find evidence for multiple acceleration in velocity dispersion and change in the abundance ratio associated at transition to the second peak. Then we explored the intensity-time profiles of all SEP events during solar cycle 23 and found that most of the SEP events are associated with multiple eruptions at the Sun and we call those events as Multi-Eruption Solar Energetic Particles (MESEP) events. We use the data available by Large Angle and Spectrometric Coronograph LASCO on board SOHO to determine the CME associated with such events and YOHKOH and GOES satellites data to determine the flare associated with such events. We found four types of MESEP according to the appearance of the peaks in the intensity-time profile in large variation of energy levels. We found that it is not possible to determine whether the peaks are related to an eruption at the Sun or not, only by examining the anisotropy flux, He/p ratio and velocity dispersion. Then we chose a rare event in which there is evidence of SEP acceleration from behind previous CME. This work resulted in a conclusion which is inconsistent with the current SEP paradigm. Then we discovered through examining another MESEP event, that energetic particles accelerated by a second CME can penetrate a previous CME-driven decelerating shock. Finally, we report the previous two MESEP events with new two events and find a common basis for second CME SEPs penetrating previous decelerating shocks. This phenomenon is reported for the first time and expected to have significant impact on modification of the current paradigm of the solar energetic particle events.

Hidrólise parcial da superfície do polyethylene terephthalate (PET): transformando um rejeito em um material de troca catiônica para aplicação ambiental

In this work it is proposed a simple and versatile undergraduate chemical experiment in polymer and environmental technology based on the process of polyethylene terephthalate (PET) hydrolysis. Polyethylene terephthalate from post-consume bottles is submitted to a controlled partial hydrolysis which allows the students to follow the reaction by a simple procedure. The students can explore the reaction kinetics, the effect of catalysts and the exposed polyethylene terephthalate surface area on the hydrolysis reaction. The second and innovative part of this experiment is the technological and environmental application of the hydrolyzed polyethylene terephthalate as a material with cation exchange properties. The surface hydrolyzed polyethylene terephthalate can be used as adsorbent for cationic contaminants.

Mecanismos químicos e mineralógicos de transformação da magnesioferrita de solo derivado de tufito, da região do Alto Paranaíba, MG

Magnetic soils forming on tuffite of the region of Alto Paranaíba, Minas Gerais, Brazil, usually contain iron-rich spinels exceptionally rich in magnesium and titanium. In this work, samples of the magnetically separated portion from the sand fraction of a Brunizém (Chernossolo) and from its mother-rock material were analyzed with synchrotron X-ray diffraction and 57Fe-Mössbauer spectroscopy. Magnesioferite (MgFe2O4) and maghemite (its pure non-stoichiometric spinel structure, Fe8/3 ⊕ 1/3 O4, where ⊕ = cation vacancy, corresponds to γFe2O3) were the magnetic iron oxides so identified. Basing on these data, a consistent chemical-mineralogical model is proposed for the main transformation steps involving these iron oxides in the pedosystem, starting on magnesioferrite to finally render hematite (αFe2O3), passing through maghemite as an intermediate specie.

Preparação e propriedades de zeólitas faujasita contendo cátions amônio

Sodium faujasite zeolites with Si/Al ratio of 1.4 and 2.5 were exchanged with methylammonium cations. The influence of framework aluminum and ion exchange degree in their basic properties were evaluated. These properties were assessed in the Knoevenagel catalytic condensation. The sodium ion exchange was restricted to the supercavity and the exchange degree depended on the cation volume and on the Si/Al ratio. The higher catalytic activity is achieved for the zeolite with the lower Si/Al ratio exchanged with the monomethylammonium cation. The best performance of this catalyst is attributed to the higher basicity in combination with elevated micropore volume.

Efecto del catión, del anión y del co-ión sobre la agregación de líquidos iónicos en solución acuosa

The aggregation behavior of thirteen 1-alkyl-3-methylimidazolium based ionic liquids in aqueous solution is presented, considering variations of the alkyl side chain length as well as the anionic moiety. Cation and anion molecular volumes are selected as appropriate molecular descriptors. Additionally, the existing relationship between critical micelle concentration (CMC) and electrolyte concentration in solution is established, aiming to clarify ion effects. CMC values were obtained by measuring electrical conductivity and surface tension. It was confirmed that aggregation of ionic liquids in aqueous solution and in presence of inorganic salts is affected by the factors developed in this study.

Foodstuffs and medicines as legal categories in the EU and China. Functional foods as a borderline case

The thesis discusses the regulation of foodstuffs and medicines, and particularly the regulation of functional foods. Legal systems investigated are the EU and China. Both are members of the WTO and Codex Alimentarius, which binds European and Chinese rules together. The study uses three Chinese berries as case examples of how product development faces regulation in practice. The berries have traditional uses as herbal medicines. Europe and China have similar nutrition problems to be resolved, such as obesity, cardiovascular disease, and diabetes. The three berries might be suitable raw materials for functional foods. Consumer products with health-enhancing functions, such as lowering blood pressure, might legally be classifi ed either as foodstuffs or medicines. The classifi cation will depend on functions and presentation of the product. In our opinion, food and medicine regulation should come closer together so the classifi cation issue would no longer be an issue. Safety of both foodstuffs and medicines is strictly regulated. With medicines, safety is a more relative concept, where benefi ts of the product are compared to side-effects in thorough scientifi c tests and trials. Foods, on the other hand, are not allowed to have side-effects. Hygiene rules and rules on the use of chemicals apply. In China, food safety is currently at focus as China has had several severe food scandals. Newly developed foods are called novel foods, and are specifi cally regulated. The current European novel food regulation from 1997 treats traditional third country products as novel. The Chinese regulation of 2007 also defi nes novel foods as something unfamiliar to a Chinese consumer. The concepts of novel food thus serve a protectionist purpose. As regards marketing, foods are allowed to bear health claims, whereas medicines bear medicinal claims. The separation is legally strict: foods are not to be presented as having medicinal functions. European nutrition and health claim regulation exists since 2006. China also has its regulation on health foods, listing the permitted claims and how to substantiate them. Health claims are allowed only on health foods. The European rules on medicines include separate categories for herbal medicines, traditional herbal medicines, and homeopathic medicines, where there are differing requirements for scientifi c substantiation. The scientifi c and political grounds for the separate categories provoke criticism. At surface, the Chinese legal system seems similar to the European one. To facilitate trade, China has enacted modern laws. Laws are needed as the country moves from planned economy to market economy: ‘rule of law’ needs to replace ‘rule of man’. Instead of being citizens, Chinese people long were subordinates to the Emperor. Confucius himself advised to avoid confl ict. Still, Chinese people do not and cannot always trust the legal system, as laws are enforced in an inconsistent manner, and courts are weak. In China, there have been problems with confl icting national and local laws. In Europe, the competence of the EU vs. the competence of the Member States is still not resolved, even though the European Commission often states that free trade requires harmonisation. Food and medicine regulation is created by international organisations, food and medicine control agencies, standards agencies, companies and their organisations. Regulation can be divided in ‘hard law’ and ‘soft law’. One might claim that hard law is in crisis, as soft law is gaining importance. If law is out of fashion, regulation certainly isn’t. In the future, ‘law’ might mean a process where rules and incentives are created by states, NGOs, companies, consumers, and other stakeholders. ‘Law’ might thus refer to a constant negotiation between public and private actors. Legal principles such as transparency, equal treatment, and the right to be heard would still be important.

Application of ftir in the determination of acrylate content in poly(sodium acrylate-co-acrylamide) superabsorbent hydrogels

Hydrogels have been prepared by free-radical solution copolymerization of acrylamide and sodium acrylate (NaAc), with molar ratio ranging from 25/75 to 80/20, respectively, using methylene bisacrylamide as the crosslinking agent. A FTIR spectroscopy procedure to determine the acrylate/acrylamide ratio in these hydrogels was proposed based on absorbance at 1410 cm-1 (nCOO-) and 2940 cm-1 (nCH and nCH2). A straight line with a good linear correlation coefficient (0.998) was obtained by plotting the acrylate content (Ac%) versus relative absorbance (Arel = A1410/A2940). Results were confirmed by the amount of sodium cation released in acid medium determined by atomic absorption spectrometry.

Processo de estabilização de resíduos orgânicos: vermicompostagem versus compostagem

Two processes are used to stabilize organic wastes: composting and vermicomposting.There are no studies in the literature showing which process is most effective over the short term. In this study, 3 organic wastes were composted and vermicomposted for 90 days, and the parameters pH, effective cation exchange capacity, total organic carbon, total Kjeldahl nitrogen, Ptotal, E4/E6 ratio, hydrophobicity and aromaticity indexes were determined. In all experiments, vermicomposted materials showed higher stability, proving a superior tool for stabilization of these organic wastes.

Syntheses, characterization and antifungal activity of tris(1,10-phenanthroline)iron(ii) bis(n-r-sulfonyldithiocarbimate)zincate(ii)

Four new compounds with the general formula [Fe(phen)3][Zn(RSO2N=CS2)2], where phen = 1,10-phenanthroline, R = 4-FC6H4 (1), 4-ClC6H4 (2), 4-BrC6H4 (3) and 4-IC6H4 (4), respectively, were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO2N=CS2K2) and tris(1,10-phenanthroline)iron(II) sulfate, with zinc(II) acetate dihydrate in dimethylformamide. The elemental analyses and the IR data were consistent with the formation of the expected complexes salts. The ¹H and 13C NMR spectra showed the signals for the cationic iron(II) complex and dithiocarbimate moieties. The molar conductance data were consistent with the 1:1 cation:anion complexes in 1-4. The antifungal activities of the compounds were tested in vitro against Candida albicans, Candida tropicalis and Colletotrichum gloeosporioides.