Estudo de equilíbrio e cinética da biossorção de cobre (II) por Rhizopus Microsporus.

A poluição relacionada a metais pesados tem recebido uma atenção especial devido a sua alta toxicidade, não biodegradabilidade e tendência de acumular-se na cadeia alimentar. Apesar disso, metais pesados também são considerados recursos valiosos, portanto a sua remoção em conjunto com a sua recuperação torna-se ainda mais importante. Este caso aplica-se aos rejeitos de mineração de cobre, os quais oferecem a possibilidade de recuperação do metal e de sua contenção de maneira segura do meio ambiente. Tais rejeitos se caracterizam por ocuparem enormes áreas inundadas e abrigarem soluções diluídas de cobre (II), porém, muitas vezes, acima dos limites seguros. Diversos processos tradicionais de tratamento mostram-se disponíveis para remover o cobre de tais soluções, no entanto, em certas aplicações eles podem ser ineficientes ou muito onerosos. Nesse contexto, a biossorção é uma alternativa interessante. Nesse processo, certos microrganismos, como fungos, bactérias e algas, ligam-se passivamente ao cobre na forma íons ou outras moléculas em soluções. No presente trabalho foi avaliado o potencial de biossorção de íons cobre (II) pela biomassa do fungo Rhizopus microsporus, coletado e isolado da área de rejeitos da Mina do Sossego, na região norte do Brasil. Isotermas de biossorção foram determinadas experimentalmente em bateladas sob temperatura de 25°C, agitação de 150 rpm, concentração de biomassa de 2,0 a 2,5 g/L e tempo de contato mínimo de 4 horas. O pH mostrou ser um fator importante no equilíbrio da biossorção, sendo o valor máximo da capacidade de biossorção de 33,12 mg de cobre / g biomassa encontrado em pH 6. Valores sucessivamente menores são encontrados pela acidificação da solução, sendo o pH 1 considerado adequado para o processo de dessorção, correspondendo a uma capacidade de biossorção de 1,95 mg/g. Modelos de adsorção de Langmuir e de Freundlich ajustaram-se adequadamente às isotermas tanto com pH controlado quanto não controlado. Foi constatado que a troca iônica é um dos mecanismos envolvidos na biossorção do cobre com Rhizopus microsporus. Tanto o modelo de pseudo-primeira ordem quanto o de pseudo-segunda ordem ajustaram-se aos dados cinéticos da biossorção, sendo que o equilíbrio ocorre em aproximadamente 4 horas. A biomassa conservou a capacidade de biossorção ao operar repetidamente em três ciclos de sorção-dessorção. A biomassa viável e a morta não apresentaram diferença estatisticamente significativa na capacidade de biossorção.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid–liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid–liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Lithium isotopic composition of pore fluids and sediments in the Costa Rica subduction zone

Pore fluid and sediment Li concentrations and isotopic ratios provide important insights on the hydrology, sediment contribution to the arc volcanoes and fluid-sediment reactions at the dominantly non-accretionary Costa Rica subduction zone. Ocean Drilling Program Site 1039 in the trench axis provides a reference section of 400 m of the incoming sediments, and Site 1040, situated arcward from the trench, consists of a deformed sedimentary wedge and apron sediments, the décollement, and the partially dewatered underthrust sediment section. At the reference site, pore fluids show important isotopic variations (delta6Li=-21.7 to -37.8 per mil), reflecting the interplay of in situ alteration of volcanic material and ion exchange with clay minerals. In the basal section, a reversal of Li concentration and delta6Li toward seawater values is observed, providing supporting evidence for a lateral seawater flow system in the upper oceanic basement underlying this sediment section. At Site 1040, pore fluid of the lower deformed wedge sediments and within the décollement is enriched in Li and the isotopic compositions are relatively light, suggesting infiltration of a deep-seated fluid. The delta6Li value of -22 per mil of this Li-enriched fluid (261 µM), when compared with the delta6Li value of the subducted sediment section (-11 per mil), suggests that the deep source fluid originates from mineral fluid dehydration and transformation reactions at temperatures of 100 to 150°C, consistent with the temperature range of the up-dip seismogenic zone and of transformation of smectite to illite. The distribution of Li and its isotopes in the underthrust section are similar to those at the reference site, indicating near complete subduction of the incoming sediments and that early dewatering of the underthrust sediments occurs predominantly by lateral flow into the ocean. The hemipelagic clay-rich sediment section of the subducting plate carries most of the Li into this subduction zone, and the pelagic diatomaceous and nannofossil calcareous oozes contain little Li. The Li isotopes of both the clay-rich hemipelagic sediments and of the pelagic oozes are, however, similar, with delta6Li values of -9 to -12 per mil. The observations that (1) the delta6Li values of the underthrust sediments are distinctly lower than that of the mantle, and (2) the lavas of the Costa Rican volcanoes are enriched in Li and 7Li, provide an approximation of the contribution of the subducted sediments to the arc volcanoes. A first order mass balance calculation suggests that approximately half of the Li flux delivered by subducted sediments and altered oceanic crust into the Middle American Trench is recycled to the Costa Rican arc and at most a quarter of sedimentary Li is returned into the ocean through thrust faults, primarily the décollement thrust.

Trace element abundance, and Sr and Nd isotope ratios of dust samples in the Pacific Ocean (Table 2)

Eolian dust preserved in deep-sea sediment cores provides a valuable indicator of past atmospheric circulation and continental paleoclimate. In order to identify the provenance of eolian dust, Nd and Sr isotopic compositions and Rb, Sr and rare earth element (REE) concentrations have been determined for the silicate fractions of deep-sea sediments from the north and central Pacific Ocean. Different regions of the Pacific Ocean are characterized by distinct air-borne inputs, producing a large range in epsolin-Nd (-10 to +1), 87Sr/86Sr (0.705-0.721), La/Yb (5-15), EuN/EuN* (0.6-1.0) and Sr/Nd (4-33). The average Nd isotopic composition of Pacific deep-sea sediments (epsilon-Nd = -6), is more radiogenic than the average from the Atlantic (epsilon-Nd = -8). In contrast, the average147Sm/144Nd ratio for Pacific sediments (0.114) is identical to that of Atlantic sediments and to that of global average riverine suspended material. The values of epsilon-Nd and147Sm/144Nd are positively correlated for the Pacific samples but negatively correlated for Atlantic samples, reflecting a fundamental difference between the dominant components in the end members with radiogenic Nd (island-arc components in the Pacific and LREE-enriched intraplate ocean island components in the Atlantic). Samples from the north central Pacific have distinctive unradiogenic epsilon-Nd values of -10, 87Sr/86Sr > 0.715, high La/Yb (> 12), and low EuN/EuN* (0.6) and Sr/Nd (3-6). These data are virtually identical to the values for loess from Asia and endorse the use of these sediments as indicators of Asian paleoclimate and paleowind directions. Island-arc contributions appear to dominate in the northwest Pacific, resulting in higher epsilon Nd (-1 to +1) and lower 87Sr/86Sr (~ 0.705) and La/Yb (~ 5). Sediments from the eastern Pacific tend to have intermediate Sr and Nd isotopic compositions but regionally variable Sr/Nd and REE patterns; they appear to be derived from the west margin of the North and South American continents, rather than from Asia. Our results confirm that dust provenance can be constrained by isotopic and geochemical analyses, which will facilitate reconstructions of past atmospheric circulation and continental paleoclimate.

Element analyses and isotopic composition of basalts from the western Pacific

New Sr- Nd- and Pb-isotopic and trace element data are presented on basalts from the Sulu and Celebes Basins, and the submerged Cagayan Ridge Arc (Western Pacific), recently sampled during Ocean Drilling Program Leg 124. Drilling has shown that the Sulu Basin developed about 18 Ma ago as a backarc basin, associated with the now submerged Cagayan Ridge Arc, whereas the Celebes Basin was generated about 43 Ma ago, contemporaneous with a general plate reorganisation in the Western Pacifc, subsequently developing as an open ocean receiving pelagic sediments until the middle Miocene. In both basins, a late middle Miocene collision phase and the onset of volcanic activity on adjacent arcs in the late Miocene are recorded. Covariations between 87Sr/86Sr and 143Nd/144Nd show that the seafoor basalts from both the Sulu and Celebes Basins are isotopically similar to depleted Indian mid-ocean ridge basalts (MORB), and distinct from East Pacifc Rise MORB, defining a single negative correlation. The Cagayan Arc volcanics are different, in that they have distinctly lower epsilon-Ne(T) for a given epsilon-Sr(T), compared to Sulu and Celebes basalts. In the 207Pb/204Pb and 208Pb/204Pb versus 206Pb/204Pb diagrams, the Celebes, Sulu and Cagayan rocks all plot distinctly above the Northern Hemisphere Reference Line, with high Delta 7/4 Pb (5.3-9.3) and Delta 8/4 Pb (46.3-68.1) values. They define a single trend of radiogenic lead enrichment from Celebes through Sulu to Cagayan Ridge, within the Indian Ocean MORB data field. The data suggest that the overall chemical and isotopic features of the Sulu, Cagayan and Celebes rocks may be explained by partial melting of a depleted asthenospheric N-MORB-type ("normal") mantle source with isotopic characteristics similar to those of the Indian Ocean MORB source. This asthenospheric source was slightly heterogeneous, giving rise to the Sr-Nd isotopic differences between the Celebes and Sulu basalts, and the Cagayan Ridge volcanics. In addition, a probably slab-derived component enriched in LILE and LREE is required to generate the elemental characteristics and low Ne(T) of the Cagayan Ridge island arc tholeiitic and calcalkaline lavas, and to contribute to a small extent in the backarc basalts of the Sulu Sea. The results of this study confirm and extend the widespread Indian Ocean MORB signature in the Western Pacifc region. This signature could have been inherited by the Indian Ocean mantle itself during the rupture of Gondwanaland, when fragments of this mantle could have migrated towards the present position of the Celebes, Sulu and Cagayan sources.

Use of anion clay hydrotalcite to remove coloured organics from aqueous solutions

Anion clay hydrotalcite sorbents were prepared to investigate their adsorption capabilities in the removal of coloured organic substances from various aqueous systems. Anion clay hydrotalcite was found to be particularly effective at removing negatively charged species. Its excellent uptake levels of anionic species can be accounted for by its high surface area and anion exchange ability. That is, coloured substances can be adsorbed on the surface or enter the interlayer region of the clay by anion exchange. In the adsorption of Acid Blue 29 on the anion clay hydrotalcite, an equilibrium time of 1 h with dye removal exceeding 99% was obtained. The hydrotalcite was found to have an adsorption capacity marginally below that of commercial activated carbon. It should be noted that the spent sorbents can be regenerated easily by heating at 723 K to remove all adsorbed organics. The reused sorbents displayed greater adsorption capabilities than the newly prepared hydrotalcite. Hence, the anion clay hydrotalcite is easily recoverable and reusable such that it is a promising sorbent for environmental and purification purposes. (C) 2002 Elsevier Science B.V. All rights reserved.