Copper and lead isotope records from an electroplating activity in sediments and biota from Sepetiba Bay (southeastern Brazil).

An old electroplating plant in Sepetiba Bay discharged metal-enriched wastes into the surrounding mangroves for 30 years (from the 1960s to 1990s), resulting in a hotspot zone of legacy sediments highly concentrated in toxic trace metals. This study applies Cu and Pb isotope systems to investigate the contributions of past punctual sources relative to emerging modern diffuse sources. The electroplating activity imprinted particular isotopic signatures (average δ65CuSRM-976: 0.4 ‰ and 206Pb/207Pb: 1.14) distinct from the natural baseline and urban fluvial sediments. The isotopic compositions of tidal flat sediments show intermediate isotope compositions reflecting the mixing of Cu and Pb from the hotspot zone and terrigenous materials carried by rivers. Oyster isotope fingerprints match legacy sediments, attesting that anthropogenic Cu and Pb are bioavailable to the biota. These findings confirm the interest in combining two or more metal isotope systems to discriminate between modern and past metal source emissions in coastal environments.

Copper removal kinetic from electroplating industry wastewater using pulsed electrodeposition technique.

This study presents a kinetic determination of copper removal from a real jewelry industry wastewater, with removal reaching 82.49% at 37°C, using fast galvanic pulse electrochemical technique in a process lasting 115 min. In the temperature range from 20 to 40°C, the mathematical model of the pseudo-first-order irreversible rate equation, with a correlation coefficient of 0.99, described the process behaviour. In this same temperature range, the Arrhenius' equation described the system, in which the temperature increase favoured the reaction kinetics. The scanning electron microscope (SEM), with energy-dispersive X-ray detector (EDX), X-ray photoelectron spectroscopy (XPS) results, and the mathematical model fitting at the temperatures of 10 and 50°C indicated the formation of copper oxide I.

Nickel Nanopillar Arrays Electrodeposited on Silicon Substrates Using Porous Alumina Templates.

Nickel nanopillar arrays were electrodeposited onto silicon substrates using porous alumina membranes as a template. The characterization of the samples was done by scanning electron microscopy, X-ray diffraction, and alternating force gradient magnetometry. Ni nanostructures were directly grown on Si by galvanostatic and potentiostatic electrodeposition techniques in three remarkable charge transfer configurations. Differences in the growth mechanisms of the nanopillars were observed, depending on the deposition method. A high correlation between the height of the nanopillars and the charge synthesis was observed irrespective of the electrochemical technique. The magnetization measurements demonstrated a main dependence with the height of the nanopillars. The synthesis of Ni nanosystems with a controllable aspect ratio provides an effective way to produce well-ordered networks for wide scientific applications.

Changes in Cd and Zn distribution in sediments after closure of an electroplating industry, Sepetiba bay, Brazil.

The spatiotemporal attenuation of Cd and Zn concentrations was assessed in sediments from Sepetiba Bay, which is a coastal system that has been historically impacted by industrial wastes. The evolution of contamination over the years shortly before and after cessation of electroplating industry activities, by the end of 1990's, was elucidated by reviewing the existing datasets for the whole bay area. Metal concentrations exceed Brazilian Sediment Quality Guidelines in most regions, corresponding to concentrations 3 to 4 orders of magnitude higher than background levels and Enrichment Factors reaching values significantly higher than 40 for both elements. In the second decade after electroplating industry closure, the levels of Cd and Zn lowered in most regions of the bay. However, an increase in the relative importance of diffuse sources can mislead the current and future identification of Cd and Zn input, bringing new challenges for environmental monitoring and management for Sepetiba bay.

14-3-3ε protein-immobilized PCL-HA electrospun scaffolds with enhanced osteogenicity.

Adipose-derived mesenchymal stem cells (ASCs) accelerate the osteointegration of bone grafts and improve the efficiency in the formation of uniform bone tissue, providing a practical and clinically attractive approach in bone tissue regeneration. In this work, the effect of nanofibrous biomimetic matrices composed of poly(ε-caprolactone) (PCL), nanometric hydroxyapatite (nHA) particles and 14-3-3 protein isoform epsilon on the initial stages of human ASCs (hASCs) osteogenic differentiation was investigated. The cells were characterized by flow cytometry and induction to differentiation to adipogenic and osteogenic lineages. The isolated hASCs were induced to differentiate to osteoblasts over all scaffolds, and adhesion and viability of the hASCs were found to be similar. However, the activity of alkaline phosphatase (ALP) as early osteogenic marker in the PCL-nHA/protein scaffold was four times higher than in PCL-nHA and more than five times than the measured in neat PCL.

Biosorption of nickel(II) and copper(II) ions from synthetic and real effluents by alginate-based biosorbent produced from seaweed Sargassum sp.

In this study, the alginate-based biosorbent produced from seaweed Sargassum sp. was used in biosorption of Ni2+ and Cu2+ ions from synthetic solutions and real electroplating effluents. Biosorption kinetics, isotherms, pH effect, thermodynamic parameters, and sorption/desorption cycles were also evaluated. Kinetic studies show the sorption equilibrium can be obtained within 180 min for Ni2+ ions and 360 min for Cu2+ ions, and the adsorption kinetics data are well described by the pseudo-second order and diffusion in spherical adsorbents. Langmuir model can be well used to describe the biosorption isotherm data. The maximum sorption capacity (qmax) and Langmuir constant (b) were up to 1.147 mmol g-1 and 1.139 L mmol-1 for Ni2+ ions and 1.640 mmol g-1 and 4.645 L mmol-1 for Cu2+ ions. The calculated thermodynamic parameters (ΔG°, ΔH°, and ΔS°) showed that the biosorption of Ni2+ and Cu2+ ions are predominantly a chemical phenomenon of endothermic nature, favorable, and spontaneous at the temperature ranges of 293-313 K. Partial desorption of the Ni2+ and Cu2+ ions on the biosorbent was achieved using acidic and saline eluents, allowing the biosorbent to be used in new sorption/desorption cycles. EDX analysis suggests an ion exchange mechanism between calcium ions on the biosorbent and target metals. Biosorption of Ni2+ and Cu2+ from real electroplating effluents with high concentrations of light metals becomes highly competitive, decreasing the amount of Ni2+ and Cu2+ ions biosorbed due to the ionic strength effect.

Electrospun poly(ε-caprolactone) matrices containing silver sulfadiazine complexed with ß-cyclodextrin as a new pharmaceutical dosage form to wound healing: preliminary physicochemical and biological evaluation.

Cooperation between researchers in the areas of medical, pharmaceutical and materials science has facilitated the development of pharmaceutical dosage forms that elicit therapeutic effects and protective action with a single product. In addition to optimizing pharmacologic action, such dosage forms provide greater patient comfort and increase success and treatment compliance. In the present work, we prepared semipermeable bioactive electrospun fibers for use as wound dressings containing silver sulfadiazine complexed with ß-cyclodextrin in a poly(Ɛ-caprolactone) nanofiber matrix aiming to reduce the direct contact between silver and skin and to modulate the drug release. Wound dressings were prepared by electrospinning, and were subjected to ATR-FT-IR and TG/DTG assays to evaluate drug stability. The hydrophilicity of the fibrous nanostructure in water and PBS buffer was studied by goniometry. Electrospun fibers permeability and swelling capacity were assessed, and a dissolution test was performed. In vitro biological tests were realized to investigate the biological compatibility and antimicrobial activity. We obtained flexible matrices that were each approximately 1.0 g in weight. The electrospun fibers were shown to be semipermeable, with water vapor transmission and swelling indexes compatible with the proposed objective. The hydrophilicity was moderate. Matrices containing pure drug modulated drug release adequately during 24 h but presented a high hemolytic index. Complexation promoted a decrease in the hemolytic index and in the drug release but did not negatively impact antimicrobial activity. The drug was released predominantly by diffusion. These results indicate that electrospun PCL matrices containing ß-cyclodextrin/silver sulfadiazine inclusion complexes are a promising pharmaceutical dosage form for wound healing.

Mesenchymal stem cell cultivation in electrospun scaffolds: mechanistic modeling for tissue engineering.

Tissue engineering is a multidisciplinary field of research in which the cells, biomaterials, and processes can be optimized to develop a tissue substitute. Three-dimensional (3D) architectural features from electrospun scaffolds, such as porosity, tortuosity, fiber diameter, pore size, and interconnectivity have a great impact on cell behavior. Regarding tissue development in vitro, culture conditions such as pH, osmolality, temperature, nutrient, and metabolite concentrations dictate cell viability inside the constructs. The effect of different electrospun scaffold properties, bioreactor designs, mesenchymal stem cell culture parameters, and seeding techniques on cell behavior can be studied individually or combined with phenomenological modeling techniques. This work reviews the main culture and scaffold factors that affect tissue development in vitro regarding the culture of cells inside 3D matrices. The mathematical modeling of the relationship between these factors and cell behavior inside 3D constructs has also been critically reviewed, focusing on mesenchymal stem cell culture in electrospun scaffolds.

Modification of titanium alloys surface properties by plasma electrolytic oxidation (PEO) and influence on biological response.

Surface characteristics can mediate biological interaction improving or affecting the tissue integration after implantation of a biomaterial. Features such as topography, wettability, surface energy and chemistry can be key determinants for interactions between cells and materials. Plasma electrolytic oxidation (PEO) is a technique used to control this kind of parameters by the addition of chemical species and the production of different morphologies on the surfaces of titanium and its alloys. With the purpose to improve the biological response, surfaces of c.p titanium and Ti6Al4V were modified by using PEO. Different electrolytes, voltages, current densities and anodizing times were tested in order to obtain surfaces with different characteristics. The obtained materials were characterized by different techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and glow discharge optical emission spectroscopy (GDOES). Wettability of the obtained surfaces were measured and the corresponding surface energies were calculated. Superhydrophilic surfaces with contact angles of about 0 degrees were obtained without any other treatment but PEO and this condition in some cases remains stable after several weeks of anodizing; crystal phase composition (anatase-rutile) of the anodic surface appears to be critical for obtaining this property. Finally, in order to verify the biological effect of these surfaces, osteoblast were seeded on the samples. It was found that cell behavior improves as SFE (surface free energy) and coating porosity increases whereas it is affected negatively by roughness. Techniques for surface modification allow changes in the coatings such as surface energy, roughness and porosity. As a consequence of this, biological response can be altered. In this paper, surfaces of c.p Ti and Ti6Al4V were modified by using plasma electrolytic oxidation (PEO) in order to accelerate the cell adhesion process.

A spectroscopic sensing platform for MARCKS protein monolayers.

We developed a highly sensitive silicon platform, suitable to assess the molecular organization of protein samples. Prototype platforms were obtained using different electrochemical protocols for the electrodeposition of Ag-nanoparticles onto the hydrogenated silicon surface. A platform with high Surface Enhanced Raman Scattering efficiency was selected based on the surface coverage and the number density of particles size distribution. The performance of the platform was determined by studying the interaction of Myristoylated Alanine-Rich C Kinase Substrate (MARCKS) protein with the substrate according to its molecular organization. The chemical and structural characteristics of MARCKS molecules were examined under two configurations: i) a disordered distribution given by a MARCKS solution drop deposited onto the platform and, ii) a compact monolayer transferred to the platform by the Langmuir-Blodgett method. Raman spectra show vibrational bands of Phenylalanine and Lysine residues specific for the protein effector domain, and evidence the presence of alpha helix structure in both configurations. Moreover, we distinguished the supramolecular order between the compact monolayer and random molecular distribution. The platforms containing Ag-nanoparticles are suitable for studies of protein structure and interactions, advancing a methodological strategy for our long term goal, which is to explore the interaction of proteins with model membranes.

Electrospun ultrathin PBAT/nHAp fibers influenced the in vitro and in vivo osteogenesis and improved the mechanical properties of neoformed bone.

Combining polyester scaffolds with synthetic nanohydroxyapatite (nHAp), which is bioactive and osteoconductive, is a plausible strategy to improve bone regeneration. Here, we propose the combination of PBAT [poly(butylene-adipate-co-terephthalate)] and synthetic nHAp (at 3 and 5wt%). PBAT is a relatively a new polymer with low crystallinity and attractive biodegradability and mechanical properties for orthopedic applications, however, with a still underexplored potential for in vivo applications. Then, we performed a careful biological in vitro and in vivo set of experiments to evaluate the influence of PBAT containing two different nHAp loads. For in vitro assays, osteoblast-like MG63 cells were used and the bioactivity and gene expression related to osteogenesis were evaluated by qRT-PCR. For in vivo experiments, twenty-four male rats were used and a tibial defect model was applied to insert the scaffolds. Micro-computed tomography (Micro-CT) and histological analysis were used to assess e bone neoformation after 6 weeks of implantation. Three point flexural tests measured the mechanical properties of the neoformed bone. All scaffolds showed promising in vitro properties, since they were not cytotoxic against MG-63 cells and promoted high cell proliferation and formation of mineralized nodules. From a mechanistic point-of-view, nHAp loading increased hydrophilicity, which in turn allowed for a better adsorption of proteins and consequent changes in the phenotypic expression of osteoblasts. nHAp induced better cellular responses on/in the scaffolds, which was mainly attributed to its osteoconductive and osteoinductive properties. Micro-CT images showed that nHAp at 3% and 5wt% led to more effective bone formation, presenting the highest bone volume after 6 weeks of implantation. Considering the three point flexural tests, 5wt% of nHAp positively influenced the flexural mode of the neoformed bone, but the stiffiness was similar between the 3% and 5wt% groups. In summary, this investigation demonstrated great potential for the application of these novel scaffolds towards bone regeneration and, thus, should be further studied.

An ultrasensitive human cardiac troponin T graphene screen-printed electrode based on electropolymerized-molecularly imprinted conducting polymer.

A nano-molecularly imprinted polymer (N-MIP) assembled on a screen-printed electrode for the cardiac troponin T (cTnT) was developed. The biomimetic surface was obtained by a co-polymer matrix assembled on the reduced graphene oxide (RGO) electrode surface. The cTnT active sites were engineered using pyrrole and carboxylated pyrrole that was one-step electropolymerized jointly with cTnT by cyclic voltammetry. The stepwise preparation of the biomimetic surface was characterized by cyclic and differential pulse voltammetries using the ferrocyanide/ferricyanide as redox probe. Structural and morphological characterization was also performed. The optimal relation of pyrrole and pyrrole-3-acid carboxylic to perform the cTnT biomimetic nanosurface was obtained at 1:5 ratio. The analytical performance of cTnT N-MIP performed by differential pulse voltammetry showed a linear range from 0.01 to 0.1 ngmL(-1) (r=0.995, p«0.01), with a very low limit of detection (0.006 ngmL(-1)). The synergic effect of conductive polymer and graphene forming 3D structures of reactive sites resulted in a N-MIP with excellent affinity to cTnT binding (KD=7.3 10(-13) molL(-1)). The N-MIP proposed is based on a simple method of antibody obtaining with a large potential for point-of-care testing applications.

Toxicity effects of nickel electroplating effluents treated by photoelectrooxidation in the industries of the Sinos River Basin.

The Sinos river Basin is an industrial region with many tanneries and electroplating plants in southern Brazil. The wastewater generated by electroplating contains high loads of salts and metals that have to be treated before discharge. After conventional treatment, this study applied an advanced oxidative process to degrade organic additives in the electroplating bright nickel baths effluent. Synthetic rinsing water was submitted to physical-chemical coagulation for nickel removal. The sample was submitted to ecotoxicity tests, and the effluent was treated by photoelectrooxidation (PEO). The effects of current density and treatment time were evaluated. The concentration of total organic carbon (TOC) was 38% lower. The toxicity tests of the effluent treated using PEO revealed that the organic additives were partially degraded and the concentration that is toxic for test organisms was reduced.

Toxicity effects of nickel electroplating effluents treated by photoelectrooxidation in the industries of the Sinos River Basin / Avaliação do efeito tóxico de efluentes oriundos da indústria galvânica na região da Bacia do Rio dos Sinos após o tratamento pelo processo de fotoeletrooxidação

The Sinos river Basin is an industrial region with many tanneries and electroplating plants in southern Brazil. The wastewater generated by electroplating contains high loads of salts and metals that have to be treated before discharge. After conventional treatment, this study applied an advanced oxidative process to degrade organic additives in the electroplating bright nickel baths effluent. Synthetic rinsing water was submitted to physical-chemical coagulation for nickel removal. The sample was submitted to ecotoxicity tests, and the effluent was treated by photoelectrooxidation (PEO). The effects of current density and treatment time were evaluated. The concentration of total organic carbon (TOC) was 38% lower. The toxicity tests of the effluent treated using PEO revealed that the organic additives were partially degraded and the concentration that is toxic for test organisms was reduced. (AU)

A Bacia do Rio dos Sinos é uma região do Sul do Brasil que sedia um importante pólo da indústria coureiro-calçadista incluindo, desde o beneficiamento das peles, em curtumes, à fabricação dos acessórios, em indústrias metalúrgicas e de galvanoplastia. O efluente gerado por processos galvânicos contém carga elevada de sais e metais que devem ser tratados antes do descarte. Neste artigo foi avaliada a aplicação de um processo oxidativo avançado após o tratamento convencional do efluente, visando degradar os aditivos orgânicos presentes nos efluentes dos banhos de eletrodeposição de níquel brilhante. Um efluente sintético foi tratado pelo processo físico-químico de coagulação para a remoção do níquel. A amostra foi, então, submetida a testes de ecotoxicidade e, em seguida, o efluente foi tratado pelo processo de fotoeletrooxidação (FEO). A influência da densidade de corrente e o tempo de tratamento foram avaliados. Foi verificada uma redução de carbono orgânico total superior a 38%. Os ensaios de ecotoxicidade para o efluente tratado por fotoeletroxidação indicaram que a FEO degradou parcialmente os aditivos orgânicos e reduziu a concentração que provoca efeitos tóxicos para os organismos teste. (AU)

Toxicity effects of nickel electroplating effluents treated by photoelectrooxidation in the industries of the Sinos River Basin / Avaliação do efeito tóxico de efluentes oriundos da indústria galvânica na região da Bacia do Rio dos Sinos após o tratamento pelo processo de fotoeletrooxidação

The Sinos river Basin is an industrial region with many tanneries and electroplating plants in southern Brazil. The wastewater generated by electroplating contains high loads of salts and metals that have to be treated before discharge. After conventional treatment, this study applied an advanced oxidative process to degrade organic additives in the electroplating bright nickel baths effluent. Synthetic rinsing water was submitted to physical-chemical coagulation for nickel removal. The sample was submitted to ecotoxicity tests, and the effluent was treated by photoelectrooxidation (PEO). The effects of current density and treatment time were evaluated. The concentration of total organic carbon (TOC) was 38% lower. The toxicity tests of the effluent treated using PEO revealed that the organic additives were partially degraded and the concentration that is toxic for test organisms was reduced.

A Bacia do Rio dos Sinos é uma região do Sul do Brasil que sedia um importante pólo da indústria coureiro-calçadista incluindo, desde o beneficiamento das peles, em curtumes, à fabricação dos acessórios, em indústrias metalúrgicas e de galvanoplastia. O efluente gerado por processos galvânicos contém carga elevada de sais e metais que devem ser tratados antes do descarte. Neste artigo foi avaliada a aplicação de um processo oxidativo avançado após o tratamento convencional do efluente, visando degradar os aditivos orgânicos presentes nos efluentes dos banhos de eletrodeposição de níquel brilhante. Um efluente sintético foi tratado pelo processo físico-químico de coagulação para a remoção do níquel. A amostra foi, então, submetida a testes de ecotoxicidade e, em seguida, o efluente foi tratado pelo processo de fotoeletrooxidação (FEO). A influência da densidade de corrente e o tempo de tratamento foram avaliados. Foi verificada uma redução de carbono orgânico total superior a 38%. Os ensaios de ecotoxicidade para o efluente tratado por fotoeletroxidação indicaram que a FEO degradou parcialmente os aditivos orgânicos e reduziu a concentração que provoca efeitos tóxicos para os organismos teste.

Bioactivity behaviour of nano-hydroxyapatite/freestanding aligned carbon nanotube oxide composite.

Bioactive and low cytotoxic three dimensional nano-hydroxyapatite (nHAp) and aligned carbon nanotube oxide (a-CNTO) composite has been investigated. First, freestanding aligned carbon nanotubes porous scaffold was prepared by large-scale thermal chemical vapour deposition and functionalized by oxygen plasma treatment, forming a-CNTO. The a-CNTO was covered with plate-like nHAp crystals prepared by in situ electrodeposition techniques, forming nHAp/a-CNTO composite. After that nHAp/a-CNTO composite was immersed in simulated body fluid for composite consolidation. This novel nanobiomaterial promotes mesenchymal stem cell adhesion with the active formation of membrane projections, cell monolayer formation and high cell viability.

Improved tribo-mechanical behavior of CaP-containing TiO2 layers produced on titanium by shot blasting and micro-arc oxidation.

The combination of shot blasting (SB) and micro-arc oxidation (or anodic oxidation--AO) in titanium surfaces was shown to provide enhanced conditions for cell differentiation and osseointegration than those provided by SB or AO alone. This study associated both methods aiming to attain titania layers on Ti with adequate tribo-mechanical features for bone implants. SB was performed using alumina particles, and titania layers were grown by AO using a CaP-based electrolyte. Mechanical properties and scratch resistance were characterized at nanoscale by instrumented indentation and nanoscratch, and correlated with morphological and microstructural changes (XRD, SEM, EDS, AFM, and profilometry). Analytical methods were employed to correct roughness and substrate effects on the indentation results. CaP-containing TiO2 layers were produced on AO and SB + AO. The latter presented small pore size and inhomogeneous layer thickness and Ca/P ratios, caused by the non-uniform surface straining by SB that affects the oxide growth kinetics in the electrochemical process. Elastic modulus of SB + AO layer (37 GPa) were lower than the AO one (45 GPa); both of them were smaller than bulk Ti (130 GPa) and close to bone values. The hardness profiles of AO and SB + AO were similar to the substrate ones. Because of the improved load bearing capacity and unique layer features, the critical load to remove the SB + AO titania coating in scratch tests was three times as much or higher than in AO. Results indicate improved mechanical biocompatibility and tribological strength of anodic titania layers grown on sand blasted Ti surfaces.

Inertization of heavy metals present in galvanic sludge by DC thermal plasma.

Galvanic sludge results from the treatment of effluents generated by the industrial metal surface treatment of industrial material, which consists in the deposition of a metal on a surface or a metal surface attack, for example, electrodeposition of conductors (metals) and non conductive, phosphate, anodizing, oxidation and/or printed circuit. The treatment proposed here is exposure of the galvanic sludge to the high temperatures provided by thermal plasma, a process which aims to vitrify the galvanic sludge and render metals (iron, zinc, and chromium) inert. Two different plasma reactors were assembled: with a DC transferred arc plasma torch and with a DC nontransferred arc plasma torch. In this way it was possible to verify which reactor was more efficient in the inertization of the metals and also to investigate whether the addition of quartzite sand to the sludge influences the vitrification of the material. Quantification of water content and density of the galvanic raw sludge were performed, as well as analyzes of total organic carbon (TOC) and identify the elements that make up the raw sludge through spectroscopy X-ray fluorescence (XRF). The chemical composition and the form of the pyrolyzed and vitrified sludge were analyzed by scanning electron microscopy with energy-dispersive X-ray spectrometer (SEM-EDS) analysis, which it is a analysis that shows the chemical of the sample surface. The inertization of the sludge was verified in leaching tests, where the leachate was analyzed by flame atomic absorption spectroscopy (FAAS). The results of water content and density were 64.35% and 2.994 g.cm(-3), respectively. The TOC analysis determined 1.73% of C in the sample of galvanic raw sludge, and XRF analysis determined the most stable elements in the sample, and showed the highest peaks (higher stability) were Fe, Zn, and Cr. The efficiency of the sludge inertization was 100% for chromium, 99% for zinc, and 100% for iron. The results also showed that the most efficient reactor was that with the DC transferred arc plasma torch and quartzite sand positively influenced by the vitrification during the pyrolysis of the galvanic sludge.