Fecal Sterols in Estuarine Sediments as Markers of Sewage Contamination in the Cubatao Area, São Paulo, Brazil

Sterol biomarkers serve as an alternative method for detecting sewage pollution. Sterols were extracted from samples of surface sediment collected in Cubato (the Vila dos Pescadores and Vila Esperan double dagger a communities) and quantified using GC-MS after Soxhlet extraction, cleanup, and derivatization. Fecal contamination was evaluated based on the concentration of coprostanol and the ratio of the selected sterols. The most abundant sterol was cholestanol, followed by coprostanol. The concentrations of coprostanol in surface sediments ranged from a minimum of 4.21 mu g g(-1) dry sediment (Vila dos Pescadores station) to a maximum of 8.32 mu g g(-1) dry sediment (Vila Esperan double dagger a station). A coprostanol concentration of about 10 mu g g(-1) was found, indicating areas of high sewage contamination. Coprostanol levels at sewage stations were higher than in other Brazilian coastal areas, which may be attributed to the fraction of the population without sanitation services.

Seed and seedling surface-sterilization for in vitro culture of tillandsia gardneri (Bromeliaceae)

Tillandsia gardneri is a bromeliad with ornamental value and a wide geographical distribution over Brazil. However, due to habitat loss and illegal overcollection in the wild it is included as a vulnerable species in the official list of endangered plants of the State of Rio Grande do Sul, Brazil. The development of a protocol for T. gardneri seed propagation in vitro may be useful for reintroducing plants in their natural habitats, and for germplasm conservation. A difficult problem encountered during the establishment of an in vitro culture is explants disinfection, especially when working with endangered species, from which explant availability is restricted. Thus, the establishment of a sterilization protocol is crucial for the initiation and success of a micropropagation system for T. gardneri. The objective of this study was to evaluate the effect of sodium hypochlorite concentration and exposure time in seed and seedling surface disinfection, tissue sensitivity and development. Sodium hypochlorite solutions (10 or 20%/5, 10 or 15 min; 25%/5 or 10 min; and 50%/5 min) were effective in eliminating seed superficial contaminants. There was no significant difference among the effective sterilization treatments in relation to seed germination (%), and seedling length and number of leaves, after 120 days in vitro. Also, no damage to seed and seedling tissues were observed. Surface sterilization of seedlings, for initiation of an in vitro culture, required higher concentrations of sodium hypochlorite (25%/15 min; 20 or 50%/5, 10 or 15 min; and 40%/5 and 10 min) for controlling fungal and yeast contamination, compared to seed sterilization. No significant differences among these treatments were found in relation to seedling length and number of leaves, after 60 days in vitro.

Geochemical and ecotoxicological assessment for estuarine surface sediments from Southern Brazil

Sediments from Guaratuba Bay (PR, Brazil), a marine protected area, were collected and evaluated for geochemistry and toxicity. High levels of P and acute toxicity were observed in some samples. Concentrations of Cu, Cd, Pb and Zn were relatively low; however, Cd levels eventually exceeded Threshold Effect Level. Toxicities were associated to nutrients and metals enrichment. Results suggest that impacts are incipient and occur only at specific sites, associated to multiple contamination sources. Despite sediments quality seems to range between good and fair, attention is required to land-use planning around Guaratuba Bay and controlling local pollution sources. © 2013 Elsevier Ltd. All rights reserved.

Disinfection protocols to prevent cross-contamination between dental offices and prosthetic laboratories

Control of cross-contamination between dental offices and prosthetic laboratories is of utmost importance to maintain the health of patients and dental office staff. The purpose of this study was to evaluate disinfection protocols, considering antimicrobial effectiveness and damage to the structures of prostheses. Solutions of 1% sodium hypochlorite, 2% chlorhexidine digluconate, 50% vinegar and sodium perborate were evaluated. Specimens were contaminated in vitro with standardized suspensions of Candida albicans, Streptococcus mutans, Escherichia coli, Staphylococcus aureus and Bacillus subtilis spores. Disinfection by immersion for 10. min was performed. Final counts of microorganisms were obtained using the plating method. Results were statistically compared by Kruskal-Wallis ANOVA and Dunn's test. The surface roughness of 40 specimens was analyzed before and after 10 disinfection cycles, and results were compared statistically using Student's t test. The solution of 50% vinegar was as effective as 1% sodium hypochlorite and 2% chlorhexidine against C. albicans, E. coli and S. mutans. The sodium perborate solution showed the lowest antimicrobial effectiveness. Superficial roughness increased after cycles in 1% sodium hypochlorite (p=0.02). Solutions of 1% sodium hypochlorite, 2% chlorhexidine and 50% vinegar were effective for the disinfection of heat-polymerized acrylic specimens. Sodium hypochlorite increased the superficial roughness. © 2013 King Saud Bin Abdulaziz University for Health Sciences.

Effect of Surface Conditioning Modalities on the Repair Bond Strength of Resin Composite to the Zirconia Core / Veneering Ceramic Complex

Purpose: This study evaluated the effect of different surface conditioning protocols on the repair strength of resin composite to the zirconia core / veneering ceramic complex, simulating the clinical chipping phenomenon.Materials and Methods: Forty disk-shaped zirconia core (Lava Zirconia, 3M ESPE) (diameter: 3 mm) specimens were veneered circumferentially with a feldspathic veneering ceramic (VM7, Vita Zahnfabrik) (thickness: 2 mm) using a split metal mold. They were then embedded in autopolymerizing acrylic with the bonding surfaces exposed. Specimens were randomly assigned to one of the following surface conditioning protocols (n = 10 per group): group 1, veneer: 4% hydrofluoric acid (HF) (Porcelain Etch) + core: aluminum trioxide (50-mu m Al2O3) + core + veneer: silane (ESPE-Sil); group 2: core: Al2O3 (50 mu m) + veneer: HF + core + veneer: silane; group 3: veneer: HF + core: 30 mu m aluminum trioxide particles coated with silica (30 mu m SiO2) + core + veneer: silane; group 4: core: 30 mu m SiO2 + veneer: HF + core + veneer: silane. Core and veneer ceramic were conditioned individually but no attempt was made to avoid cross contamination of conditioning, simulating the clinical intraoral repair situation. Adhesive resin (VisioBond) was applied to both the core and the veneer ceramic, and resin composite (Quadrant Posterior) was bonded onto both substrates using polyethylene molds and photopolymerized. After thermocycling (6000 cycles, 5 degrees C-55 degrees C), the specimens were subjected to shear bond testing using a universal testing machine (1 mm/min). Failure modes were identified using an optical microscope, and scanning electron microscope images were obtained. Bond strength data (MPa) were analyzed statistically using the non-parametric Kruskal-Wallis test followed by the Wilcoxon rank-sum test and the Bonferroni Holm correction (alpha = 0.05).Results: Group 3 demonstrated significantly higher values (MPa) (8.6 +/- 2.7) than those of the other groups (3.2 +/- 3.1, 3.2 +/- 3, and 3.1 +/- 3.5 for groups 1, 2, and 4, respectively) (p < 0.001). All groups showed exclusively adhesive failure between the repair resin and the core zirconia. The incidence of cohesive failure in the ceramic was highest in group 3 (8 out of 10) compared to the other groups (0/10, 2/10, and 2/10, in groups 1, 2, and 4, respectively). SEM images showed that air abrasion on the zirconia core only also impinged on the veneering ceramic where the etching pattern was affected.Conclusion: Etching the veneer ceramic with HF gel and silica coating of the zirconia core followed by silanization of both substrates could be advised for the repair of the zirconia core / veneering ceramic complex.

Rainwater toxicity and contamination study from So Paulo Metropolitan Region, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Assessment of the Removal Capacity, Tolerance, and Anatomical Adaptation of Different Plant Species to Benzene Contamination

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Detection of hormones in surface and drinking water in Brazil by LC-ESI-MS/MS and ecotoxicological assessment with Daphnia magna

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Speciation of butyltin derivatives in surface sediments of three southern Brazilian harbors

For the first time, organotin compounds were determined in surface sediment samples collected from Sao Francisco do Sul, Itajai-Navegantes and Imbituba Harbors, located in Santa Catarina State, Brazil. Butyltins (BTs) were determined by gas chromatography with a pulsed flame photometric detector (GC-PFPD) after being modified using the Grignard derivatization method. The concentrations of BTs derivatives ranged from n.d. to 1136.6 ng (Sn) g(-1) of dry weight (dw) sediment for tributyltin (TOT), n.d. to 394.4 ng (Sn)g(-1) dw for dibutyltin (DOT) and n.d. to 312.2 ng (Sn)g(-1) dw for monobutyltin (MBT). The highest concentration of total BTs was found at the Itajai-Acu River dockyard, indicating intense inputs of antifouling paints to the environment. The relative difference in the BTs levels is a particular characteristic of sediments from harbors and may be related to the shipyards and the boat traffic which still use TBT-based antifouling paints.

Occurrence and behavior of butyltins in intertidal and shallow subtidal surface sediments of an estuarine beach under different sampling conditions

Contamination by butyltin compounds (BTs) has been reported in estuarine environments worldwide, with serious impacts on the biota of these areas. Considering that BTs can be degraded by varying environmental conditions such as incident light and salinity, the short-term variations in such factors may lead to inaccurate estimates of BTs concentrations in nature. Therefore, the present study aimed to evaluate the possibility that measurements of BTs in estuarine sediments are influenced by different sampling conditions, including period of the day (day or night), tidal zone (intertidal or subtidal), and tides (high or low). The study area is located on the Brazilian southeastern coast, Sao Vicente Estuary, at Pescadores Beach, where BT contamination was previously detected. Three replicate samples of surface sediment were collected randomly in each combination of period of the day, tidal zone, and tide condition, from three subareas along the beach, totaling 72 samples. BTs were analyzed by GC-PFPD using a tin filter and a VF-5 column, by means of a validated method. The concentrations of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) ranged from undetectable to 161 ng Sn g(-1) (d.w.). In most samples (71%), only MBT was quantifiable, whereas TBTs were measured in only 14, suggesting either an old contamination or rapid degradation processes. DBT was found in 27 samples, but could be quantified in only one. MBT concentrations did not differ significantly with time of day, zones, or tide conditions. DBT and TBT could not be compared under all these environmental conditions, because only a few samples were above the quantification limit. Pooled samples of TBT did not reveal any difference between day and night. These results indicated that, in assessing contamination by butyltin compounds, surface-sediment samples can be collected in any environmental conditions. However, the wide variation of BTs concentrations in the study area, i.e., over a very small geographic scale, illustrates the need for representative hierarchical and composite sampling designs that are compatible with the multiscalar temporal and spatial variability common to most marine systems. The use of such sampling designs will be necessary for future attempts to quantitatively evaluate and monitor the occurrence and impact of these compounds in nature

Herbicides in the upper Poxim River, Sergipe, and the risk of contamination of water resources

Increased agricultural activity in watershed areas has been causing concern over contamination by herbicides in agricultural areas. The problem becomes more important when contamination can affect water for human consumption, as happens with water from the Poxim river, which supplies the city of Aracaju, capital of the State of Sergipe. The aim of this study was to evaluate the risk of contamination by herbicides to both surface and groundwater in the upper sub-basin of the Poxim River, and to detect the presence of the active ingredients Diuron and Ametrine up-river from the sugar-cane plantations. Risk analysis was carried out using criteria from the Environmental Protection Agency (EPA), the GUS index, and the GOSS method. It was observed that several active ingredients are at risk of leaching, demonstrating the importance of monitoring the river to control both the quality of water and the frequency and volume of herbicides used in the region. Based on the results, monitoring was carried out bi-monthly from July 2009 to July 2010 at two sampling points. Water samples were analyzed in the laboratory, where the presence of Diuron and Ametrine was noted. Water quality in the Sub-basin of the Rio Poxim is being influenced by the use of herbicides in the region. There was an increase in herbicide concentration in the surface water during the rainy season, possibly caused by soil runoff.

Supramolecular hybrid organic-inorganic multicomponent architectures in solution and on surface

Supramolecular architectures can be built-up from a single molecular component (building block) to obtain a complex of organic or inorganic interactions creating a new emergent condensed phase of matter, such as gels, liquid crystals and solid crystal. Further the generation of multicomponent supramolecular hybrid architecture, a mix of organic and inorganic components, increases the complexity of the condensed aggregate with functional properties useful for important areas of research, like material science, medicine and nanotechnology. One may design a molecule storing a recognition pattern and programming a informed self-organization process enables to grow-up into a hierarchical architecture. From a molecular level to a supramolecular level, in a bottom-up fashion, it is possible to create a new emergent structure-function, where the system, as a whole, is open to its own environment to exchange energy, matter and information. “The emergent property of the whole assembly is superior to the sum of a singles parts”. In this thesis I present new architectures and functional materials built through the selfassembly of guanosine, in the absence or in the presence of a cation, in solution and on the surface. By appropriate manipulation of intermolecular non-covalent interactions the spatial (structural) and temporal (dynamic) features of these supramolecular architectures are controlled. Guanosine G7 (5',3'-di-decanoil-deoxi-guanosine) is able to interconvert reversibly between a supramolecular polymer and a discrete octameric species by dynamic cation binding and release. Guanosine G16 (2',3'-O-Isopropylidene-5'-O-decylguanosine) shows selectivity binding from a mix of different cation's nature. Remarkably, reversibility, selectivity, adaptability and serendipity are mutual features to appreciate the creativity of a molecular self-organization complex system into a multilevelscale hierarchical growth. The creativity - in general sense, the creation of a new thing, a new thinking, a new functionality or a new structure - emerges from a contamination process of different disciplines such as biology, chemistry, physics, architecture, design, philosophy and science of complexity.

Safety by design: production of engineering surface modified nanomaterials

This PhD thesis focused on nanomaterial (NM) engineering for occupational health and safety, in the frame of the EU project “Safe Nano Worker Exposure Scenarios (SANOWORK)”. Following a safety by design approach, surface engineering (surface coating, purification process, colloidal force control, wet milling, film coating deposition and granulation) were proposed as risk remediation strategies (RRS) to decrease toxicity and emission potential of NMs within real processing lines. In the first case investigated, the PlasmaChem ZrO2 manufacturing, the colloidal force control applied to the washing of synthesis rector, allowed to reduce ZrO2 contamination in wastewater, performing an efficient recycling procedure of ZrO2 recovered. Furthermore, ZrO2 NM was investigated in the ceramic process owned by CNR-ISTEC and GEA-Niro; the spray drying and freeze drying techniques were employed decreasing NM emissivity, but maintaining a reactive surface in dried NM. Considering the handling operation of nanofibers (NFs) obtained through Elmarco electrospinning procedure, the film coating deposition was applied on polyamide non-woven to avoid free fiber release. For TiO2 NF the wet milling was applied to reduce and homogenize the aspect ratio, leading to a significant mitigation of fiber toxicity. In the Colorobbia spray coating line, Ag and TiO2 nanosols, employed to transfer respectively antibacterial or depolluting properties to different substrates, were investigated. Ag was subjected to surface coating and purification, decreasing NM toxicity. TiO2 was modified by surface coating, spray drying and blending with colloidal SiO2, improving its technological performance. In the extrusion of polymeric matrix charged with carbon nanotube (CNTs) owned by Leitat, the CNTs used as filler were granulated by spray drying and freeze spray drying techniques, allowing to reduce their exposure potential. Engineered NMs tested by biologists were further investigated in relevant biological conditions, to improve the knowledge of structure/toxicity mechanisms and obtain new insights for the design of safest NMs.

Influence of blood contamination on bond strength of a self-etching system.

OBJECTIVES: To detect the influence of blood contamination (BC) on the bond strength (BS) of a self-etching bonding system (SES) to enamel and dentine. METHODS: 25 human molars were longitudinally sectioned on the mesio-distal axis in order to obtain 50 specimens, which were embedded in acrylic resin. At first, the specimens were ground to expose a flat surface of enamel, and a bond strength test was performed. Afterwards, the samples were ground again in order to obtain a flat surface of dentine. Ten groups (total: n=100) were assigned according to substrate (enamel and dentine), step in the bonding sequence when contamination occurred (before the acidic primer and after the bonding resin), and contamination treatment (dry or rinse and dry procedure). Fresh human blood was introduced either before or after SES application (Clearfil SE Bond) and treated with air drying, or by rinsing and drying following application. Composite resin (Filtek Z-250,3M ESPE) was applied as inverted, truncated cured cones that were debonded in tension. RESULTS: The mean tensile BS values (MPa) for enamel/dentine were 19.4/23.0 and 17.1/10.0 for rinse-and-dry treatment (contamination before and after SES, respectively); while the measurements for the dry treatment, 16.2/23.3 and 0.0/0.0 contamination before and after SES, respectively. CONCLUSIONS: It was determined that blood contamination impaired adhesion to enamel and dentine when it occurred after bond light curing. Among the tested contamination treatments, the rinse-and-dry treatment produced the highest bond strength with BC after SES application, but it was not sufficient to recover the BS in the contamination-free group.