Approach combining on-line metal exchange and tangential-flow ultrafiltration for in-situ characterization of metal species in humic hydrocolloids

This paper deals with the development and optimization of an analytical procedure using ultrafiltration and a flow-injection system, and its application in in-situ experiments to characterize the lability and availability of metal species in humic-rich hydrocolloids. The on-line system consists of a tangential flow ultrafiltration device equipped with a 3-kDa filtration membrane. The concentration of free ions in the filtrate was determined by atomic-absorption spectrometry, assuming that metals not complexed by aquatic humic substances (AHS) were separated from the complexed species (M-AHS) retained by the membrane. For optimization, exchange experiments using Cu(II) solutions and AHS solutions doped with the metal ions Ni(II), Mn(II), Fe(III), Cd (II), and Zn(II) were carried out to characterize the stability of the metal-AHS complexes. The new procedure was then applied in-situ at a tributary of the Ribeira do Iguape river (Iguape, São Paulo State, Brazil) and evaluated using the ions Fe(III) and Mn(II), which are considered to be essential constituents of aquatic systems. From the exchange between metal-natural organic matter (M-NOM) and the Cu(II) ions it was concluded that Cu(II) concentrations > 485 mu g L(-1) were necessary to obtain maximum exchange of the complexes Mn-NOM and Fe-NOM, corresponding to 100% Mn and 8% Fe. Moreover, the new analytical procedure is simple and opens up new perspectives for understanding the complexation, transport, stability, and lability of metal species in humic-rich aquatic environments.

Development of a simple and versatile ultrafiltration system for the fractionation of aquatic humic substances

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanopore size growth and ultrafiltration performance of SnO2 ceramic membranes prepared by sol-gel route

Supported ceramic membranes have been produced by the sol-casting procedure from aqueous colloidal suspensions prepared by the sol-gel route. Coatings on a tubular alumina support have been successfully performed leading to crack free layers. Samples have been sintered at 400, 500 and 600 degreesC, and the effect of heating treatment on the nanostructure and on the ultrafiltration properties are analyzed. The characterization has been done by high resolution scanning electron microscopy, nitrogen adsorption-desorption isotherms, water permeation and cut-off determination using polyethylene glycol standard solutions. The micrographs have revealed that grains and pore size increase with the temperature, whereas their shape remains invariant. This results is in agreements with N-2 adsorption-desorption analyses, which have revealed that the mean pore size diameter increases from 4 to 10 nm as the sintering temperature increases from 400 to 600 degreesC, while the total porosity remains constant. Furthermore, the tortuosity, calculated from water permeability, is essentially invariant with the sintering temperatures. The membranes cut-off, determined with a retention rate equal to 95%, are 3500, 6500 and 9000 g . mol(-1) for 400, 500 and 600 degreesC, respectively, showing that the permeation properties of SnO2 ultrafiltration membranes can easily be controlled by sintering condition.

Tangential-flow ultrafiltration: a versatile methodology for determination of complexation parameters in refractory organic matter from Brazilian water and soil samples

In this work the copper(II) complexation parameters of aquatic organic matter, aquatic and soil humic substances from Brazilian were determined using a new versatile approach based on a single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods. The results regarding the copper(II) complexation capacity and conditional stability constants obtained for humic materials were compared with those obtained using direct potentiometry with a copper-ion-selective electrode. The analytical procedure based on ultrafiltration is a good alternative to determine the complexation parameters in natural organic material from aquatic and soil systems. This approach presents additional advantages such as better sensibility, applicability for multi-element capability, and its possible to be used under natural conditions when compared with the traditional ion-selective electrode.

Use of diffusive gradients in thin films and tangential flow ultrafiltration for fractionation of Al(III) and Cu(II) in organic-rich river waters

Diffusive gradients in thin films (DGT) and tangential-flow ultrafiltration (TF-UF) were combined for fractionation of Al and Cu in river water containing high content of dissolved organic carbon. A procedure based on ultrafiltration data is proposed to determine diffusion coefficients of the analytes in water samples and model solutions containing both free metal (M) and complex (metal - humic substance). Aiming to evaluate the accuracy of the proposed approach, the DGT results were compared with those from a protocol for determination of labile Al and Cu based on solid phase extraction (SPE). Good agreement between data from DGT and SPE were attained for model solutions. For analysis of real organic-rich water samples, differences between DGT and SPE measurements were consistent with the time-scales of the techniques. The concentration of labile Al determined by DGT were lower than the total dissolved concentrations (determined by inductively coupled plasma mass spectrometry) and exceeded the ultrafiltered concentration, indicating that inorganic Al species (species small enough to pass through 1 kDa membrane) were minor species as compared with Al organic complexes. For both Al and Cu, there were species not measured by DGT as they are not sufficiently labile. (C) 2007 Elsevier B.V. All rights reserved.

Influence of membrane-solution interface on the selectivity of SnO2 ultrafiltration membranes

SnO2 supported membranes, presenting 3.0 nm average pore size, have been produced by sol casting on alumina tubular substrate using aqueous colloidal suspensions prepared by sol-gel route. The selectivity and flux throughout SnO2 membrane were analyzed by permeation experiments, using a laboratory tangential filtration pilot equipped with a monotubular membrane. To evaluate the effect of the surface charge at the membrane-solution interface, aqueous salt solutions (NaCl, Na2SO4, CaCl, and CaSO4) of different ionic strength have been filtered and the results correlated with the values of zeta potential measured at several pH. The results show that the retention coefficient is dependent on the electrolyte present in aqueous solution decreasing as: (dication, monoanion) > (monocation, monoanion) approximate to (monocation, dianion) > (dication, dianion). The surface charge and the cation adsorption capacity play a determinant role in these selectivity sequences. (C) 2001 Elsevier B.V. B.V. All rights reserved.

An ultrafiltration membrane, prepared with MSU-type mesoporous silica: Preparation and specific filtration behavior

We report preparation and the singular filtration properties of an ultrafiltration membrane made with MSU-type mesoporous silica that exhibits cylindrical pores aligned mostly normal to the support. This membrane supported on tubular commercial macroporous alumina supports was prepared by the interfacial growth mechanism between stable silica-surfactant hybrid micelles made of the association of silica oligomers with polyethyleneoxide-based (PEO) surfactants and sodium fluoride, a well-known silica condensation catalyst. It appears that the combined effect of the silica nature of the membrane, whose surface charge can be easily adjusted by changing the pH and the non-connected cylindrical shape of the pores provides a new behavior in the retention properties, as proved by the filtration of polyoxyethylene polymers (PEO) with different molecular weights. Depending on the filtration conditions, a rejection rate of 80 % and a steep cut-off at 2,000 Da can be obtained or, on the reverse, polymers three times bigger than the pore diameter can diffuse through the membrane. This new filtration mechanism, which opens up new modes of separation modes, is explained in the light of both topology of the porous network and pH-dependent interactions between PEO polymers and silica porous media. © 2005 Elsevier B.V. All rights reserved.

Encapsulation of Local Anesthetic Bupivacaine in Biodegradable Poly(DL-lactide-co-glycolide) Nanospheres: Factorial Design, Characterization and Cytotoxicity Studies

Local anesthetic agents cause temporary blockade of nerve impulses productiong insensitivity to painful stimuli in the area supplied by that nerve. Bupivacaine (BVC) is an amide-type local anesthetic widely used in surgery and obstetrics for sustained peripheral and central nerve blockade. in this study, we prepared and characterized nanosphere formulations containing BVC. To achieve these goals, BVC loaded poly(DL-lactide-co-glycolide) (PLGA) nanospheres (NS) were prepared by nanopreciptation and characterized with regard to size distribution, drug loading and cytotoxicity assays. The 2(3-1) factorial experimental design was used to study the influence of three different independent variables on nanoparticle drug loading. BVC was assayed by HPLC, the particle size and zeta potential were determined by dynamic light scattering. BVC was determined using a combined ultrafiltration-centrifugation technique. The results of optimized formulations showed a narrow size distribution with a polydispersivity of 0.05%, an average diameter of 236.7 +/- 2.6 nm and the zeta potential -2.93 +/- 1,10 mV. In toxicity studies with fibroblast 3T3 cells, BVC loaded-PLGA-NS increased cell viability, in comparison with the effect produced by free BVC. In this way, BVC-loaded PLGA-NS decreased BVC toxicity. The development of BVC formulations in carriers such as nanospheres could offer the possibility of controlling drug delivery in biological systems, prolonging the anesthetic effect and reducing toxicity.

Characterization of the Interactions between Endocrine Disruptors and Aquatic Humic Substances from Tropical Rivers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Anaerobic bio-digestion of concentrate obtained in the process of ultra filtration of effluents from tilapia processing unit

The objective of the present study was to evaluate the efficiency of the process of biodigestion of the protein concentrate resulting from the ultrafiltration of the effluent from a slaughterhouse freezer of Nile tilapia. Bench digesters were used with excrements and water (control) in comparison with a mixture of cattle manure and effluent from the stages of filleting and bleeding of tilapias. The effluent obtained in the continuous process (bleeding + filleting) was the one with highest accumulated population from the 37th day, as well as greatest daily production. Gases composition did not differ between the protein concentrates, but the gas obtained with the use of the effluent from the filleting stage presented highest methane gas average (78.05%) in comparison with those obtained in the bleeding stage (69.95%) and in the continuous process (70.02%) or by the control method (68.59%).

Cyclodextrin glycosyltransferase from Bacillus licheniformis: Optimization of production and its properties

Cyclodextrin glycosyltransferase (EC 2.4.1.19) is an enzyme that produces cyclodextrins from starch via an intramolecular transglycosylation reaction. An alkalophilic Bacillus strain, isolated from cassava peels, was identified as Bacillus licheniformis. CGTase production by this strain was better when potato starch was used as carbon source, followed by cassava starch and amylopectin. Glucose and amylose, on the other hand, acted as synthesis repressors. When the cultivation was supplemented with sodium ions and had the pH adjusted between 6.0 and 9.0, the microorganism maintained the growth and enzyme production capacity. This data is interesting because it contradicts the concept that alkalophilic microorganisms do not grow in this pH range. After ultrafiltration-centrifugation, one protein of 85.2 kDa with CGTase activity was isolated. This protein was identified in plates with starch and phenolphthalein. Determination of the optimum temperature showed higher activities at 25 degrees C and 55 degrees C, indicating the possible presence of more than one CGTase in the culture filtrate. Km and Vmax values were 1.77 mg/mL and 0.0263 U/mg protein, respectively, using potato starch as substrate.

Avaliação da remoção de matéria orgânica carbonácea e nitrogenada de águas residuárias em biorreator de membranas

O presente trabalho objetivou a avaliação da remoção de matéria orgânica carbonácea e nitrogenada, bem como a determinação do fluxo crítico, em biorreator de membranas, com zona pré-anóxica, tratando águas residuárias industriais da produção de aminoácidos. O reator foi operado sob carga orgânica volumétrica de 1,91 kg.DQO.m-3.d-1 e 0,18 kg.NTK.m-3.d-1; a recirculação do reator aeróbio para o reator anóxico foi de quatro vezes a vazão afluente. O reator apresentou médias de remoção de DQO, NTK e NT de 97, 98 e 92%, respectivamente. O sistema de ultrafiltração foi testado em vários fluxos entre 25 e 37 L.m-2.h-1 e determinou-se o fluxo crítico de 28 L.m-2.h-1 quando operado com 11,4 g.L-1 de SST e 35 dias de tempo de retenção celular. Os resultados mostraram que houve viabilidade técnica no uso de biorreator de membranas para remoção de matéria orgânica de águas residuárias industriais da produção de aminoácidos.

High-Volume Peritoneal Dialysis in Acute Kidney Injury: Indications and Limitations

Background and objectives Peritoneal dialysis is still used for AKI in developing countries despite concerns about its limitations. The objective of this study was to explore the role of high-volume peritoneal dialysis in AM patients in relation to metabolic and fluid control, outcome, and risk factors associated with death.Design, setting, participants, & measurements A prospective study was performed on 204 AKI patients who were assigned to high-volume peritoneal dialysis (prescribed Kt/V=0.60/session) by flexible catheter and cycler; 150 patients (80.2%) were included in the final analysis.Results Mean age was 63.8 +/- 15.8 years, 70% of patients were in the intensive care unit, and sepsis was the main etiology of AKI (54.7%). BUN and creatinine levels stabilized after four sessions at around 50 and 4 mg/dl, respectively. Fluid removal and nitrogen balance increased progressively and stabilized around 1200 ml and -1 g/d after four sessions, respectively. Weekly delivered Kt/V was 3.5 +/- 0.68. Regarding AKI outcome, 23% of patients presented renal function recovery, 6.6% of patients remained on dialysis after 30 days, and 57.3% of patients died. Age and sepsis were identified as risk factors for death. In urine output, increase of 1 g in nitrogen balance and increase of 500 ml in ultrafiltration after three sessions were identified as protective factors.Conclusions High-volume peritoneal dialysis is effective for a selected AKI patient group, allowing adequate metabolic and fluid control. Age, sepsis, and urine output as well as nitrogen balance and ultrafiltration after three high-volume peritoneal dialysis sessions were associated significantly with death. Clin J Am Soc Nephrol 7: 887-894, 2012. doi: 10.2215/CJN.11131111

Desenvolvimento de um modelo experimental de hemodiálise em cães

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)