Environmental effects in kelvin force microscopy of modified diamond surfaces

We have explored the effects of atmospheric environment on Kelvin force microscopy (KFM) measurements of potential difference between different regions of test polycrystalline diamond surfaces. The diamond films were deposited by microwave plasma-assisted chemical vapor deposition, which naturally produces hydrogen terminations on the surface of the films formed. Selected regions were patterned by electron-beam lithography and chemical terminations of oxygen or fluorine were created by exposure to an oxygen or fluorine plasma source. For KFM imaging, the samples were mounted in a hood with a constant flow of helium gas. Successive images were taken over a 5-h period showing the effect of the environment on KFM imaging. We conclude that the helium flow removes water molecules adsorbed on the surface of the samples, resulting in differences in surface potential between adjacent regions. The degree of water removal is different for surfaces with different terminations. The results highlight the importance of taking into account the atmospheric environment when carrying out KFM analysis. (C) 2012 Wiley Periodicals, Inc.

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrode

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm(-2). Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k(ap)p close to 3.2 x 10(-2) min(-1). The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities >= 150 mA cm(-2). The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis of carbon nanomaterials from corn waste (DDGS)

Syntesis of carbon nanomaterials from corn waste (DDGS). The world's largest ethanol producer (USA) uses corn as feedstock. DDGS (distillers dried grains with solubles) is the main waste generated from this process (around 32 million t/year). DDGS samples were pyrolyzed at 1000 degrees C in a furnace with controlled atmosphere. The effluent was channeled to a second furnace, in which catalyst substrates were placed. Chromatographic analysis was used to evaluate the gaseous effluents, showing that the catalyst reduced hydrocarbon emissions. The solid products formed were analyzed by SEM and TEM. Graphitic structures and carbon nanofibers, 50 mu m in length and with diameters of 80-200 nm, were formed.

Toward the Optimization of an e-Tongue System Using Information Visualization: A Case Study with Perylene Tetracarboxylic Derivative Films in the Sensing Units

The wide variety of molecular architectures used in sensors and biosensors and the large amount of data generated with some principles of detection have motivated the use of computational methods, such as information visualization techniques, not only to handle the data but also to optimize sensing performance. In this study, we combine projection techniques with micro-Raman scattering and atomic force microscopy (AFM) to address critical issues related to practical applications of electronic tongues (e-tongues) based on impedance spectroscopy. Experimentally, we used sensing units made with thin films of a perylene derivative (AzoPTCD acronym), coating Pt interdigitated electrodes, to detect CuCl(2) (Cu(2+)), methylene blue (MB), and saccharose in aqueous solutions, which were selected due to their distinct molecular sizes and ionic character in solution. The AzoPTCD films were deposited from monolayers to 120 nm via Langmuir-Blodgett (LB) and physical vapor deposition (PVD) techniques. Because the main aspects investigated were how the interdigitated electrodes are coated by thin films (architecture on e-tongue) and the film thickness, we decided to employ the same material for all sensing units. The capacitance data were projected into a 2D plot using the force scheme method, from which we could infer that at low analyte concentrations the electrical response of the units was determined by the film thickness. Concentrations at 10 mu M or higher could be distinguished with thinner films tens of nanometers at most-which could withstand the impedance measurements, and without causing significant changes in the Raman signal for the AzoPTCD film-forming molecules. The sensitivity to the analytes appears to be related to adsorption on the film surface, as inferred from Raman spectroscopy data using MB as analyte and from the multidimensional projections. The analysis of the results presented may serve as a new route to select materials and molecular architectures for novel sensors and biosensors, in addition to suggesting ways to unravel the mechanisms behind the high sensitivity obtained in various sensors.

Effect of amino-terminated substrates onto surface properties of cellulose esters and their interaction with lectins

Films of cellulose acetate butyrate (CAB) and carboxymethylcellulose acetate butyrate (CMCAB) were deposited from ethyl acetate solutions onto bare silicon wafers (Si/SiO2) or amino-terminated surfaces (APS) by means of equilibrium adsorption. All surfaces were characterized by means of ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The presence of amino groups on the support surface favored the adsorption of CAB and CMCAB, inducing the orientation almost polar groups to the surface and the exposition of alkyl group to the air. Such molecular orientation caused increase of the dispersive component of surface energy (gamma(d)(s)) and decrease of the polar component of surface energy (gamma(p)(s)) of cellulose esters in comparison to those values determined for films deposited onto bare Si/SiO2 wafers. Adsorption behavior of jacalin or concanavalin A onto CAB and CMCAB films was also investigated. The adsorbed amounts of lectins were more pronounced on cellulose esters with high (gamma(p)(s)) and total surface energy (gamma(t)(s)) values. (C) 2011 Elsevier B.V. All rights reserved.

Influence of the Substrate and Precursor on the Magnetic and Magneto-transport Properties in Magnetite Films

We have investigated the magnetic and transport properties of nanoscaled Fe3O4 films obtained from Chemical Vapor Deposition (CVD) technique using [(FeFe2III)-Fe-II(OBut)(8)] and [Fe-2(III)(OBut)(6)] precursors. Samples were deposited on different substrates (i.e., MgO (001), MgAl2O4 (001) and Al2O3 (0001)) with thicknesses varying from 50 to 350 nm. Atomic Force Microscopy analysis indicated a granular nature of the samples, irrespective of the synthesis conditions (precursor and deposition temperature, T-pre) and substrate. Despite the similar morphology of the films, magnetic and transport properties were found to depend on the precursor used for deposition. Using [(FeFe2III)-Fe-II(OBut)(8)] as precursor resulted in lower resistivity, higher M-S and a sharper magnetization decrease at the Verwey transition (T-V). The temperature dependence of resistivity was found to depend on the precursor and T-pre. We found that the transport is dominated by the density of antiferromagnetic antiphase boundaries (AF-APB's) when [(FeFe2III)-Fe-II(OBut)(8)] precursor and T-pre = 363 K are used. On the other hand, grain boundary-scattering seems to be the main mechanism when [Fe-2(III)(OBut)(6)] is used. The Magnetoresistance (MR(H)) displayed an approximate linear behavior in the high field regime (H > 796 kA/m), with a maximum value at room-temperature of similar to 2-3 % for H = 1592 kA/m, irrespective from the transport mechanism.

Influence of the deposition parameters on the morphology and electrical conductivity of PANI/PSS self-assembled films

The influence of deposition parameters, namely polymer concentration and pH of the deposition solution, cleaning, and drying steps on the morphology and electrical characteristics of polyaniline and sulfonated polystyrene (PANI/PSS) nanostructured films deposited by the self-assembly technique is evaluated by UV-Vis spectroscopy, optical and atomic force microscopy, and electrical resistance measurements. It is found that stirring the cleaning solution during the cleaning step is crucial for obtaining homogenous films. Stirring of the cleaning solution also influences the amount of PANI adsorbed in the films. In this regard, the drying process seems to be less critical since PANI amount and film thickness are similar in films dried with N-2 flow or with an absorbent tissue. It is observed, however, that drying with N-2 flow results in rougher films. As an additional point, an assessment of the influence of the deposition method (manual versus mechanical) on the film characteristics was carried out. A significant difference on the amount of PANI and film thickness between films prepared by different human operators and by a homemade mechanical device was observed. The variability in film thickness and PANI adsorbed amount is smaller in films mechanically assembled. (c) 2007 Elsevier B.V. All rights reserved.

Temporal variation in egg-capsule deposition by Nassarius vibex (Gastropoda: Nassariidae)

The morphology and the deposition periods of egg capsules by the bruised nassa Nassarius vibex were investigated on two beaches located on the southeast coast of Brazil. The nassariids were associated with the charru mussel Mytella charruana, which forms beds on soft mud-bottoms. A total of 1558 capsules were collected, only from the fronds of the green alga Ulva lactuca, 859 for Camaroeiro Beach and 699 for Cidade Beach. The mean sizes of the egg capsules and numbers of eggs or larvae per capsule were similar on the two beaches, as were the periods of capsule deposition. At Camaroeiro Beach, capsules first appeared in May 2006, reached a peak in August 2006, and disappeared in December 2006. At Cidade Beach, the first capsules were recorded in July 2006, with a peak in August 2006. A second peak was also observed at this beach between January 2007 and April 2007. The two periods of deposition recorded at the latter beach may indicate two periods of recruitment in the same year for N. vibex. Regarding the influence of intertidal level on capsule deposition, there was a significant difference in the number of capsules between the levels at Camaroeiro Beach (F= 7.445, p<0.05), and for the second capsule-deposition peak at Cidade Beach (F= 6.382, p<0.05). This study revealed a selective pattern of capsule deposition, with individuals of N. vibex using only fronds of U. lactuca. This process was influenced by the morphodynamics of the two beaches, with the nassariids maximizing the survival of embryos by depositing more capsules and more eggs per capsule in better-protected parts of the mytilid beds.

Color-space distortions following long-term occupational exposure to mercury vapor

Color vision was examined in subjects with long-term occupational exposure to mercury (Hg) vapor. The color vision impairment was assessed by employing a quantitative measure of distortion of individual and group perceptual color spaces. Hg subjects (n = 18; 42.1 +/- 6.5 years old; exposure time = 10.4 +/- 5.0 years; time away from the exposure source = 6.8 +/- 4.6 years) and controls (n = 18; 46.1 +/- 8.4 years old) were examined using two arrangement tests, D-15 and D-15d, in the traditional way, and also in a triadic procedure. From each subject`s `odd-one-out` choices, matrices of inter-cap subjective dissimilarities were derived and processed by non-metric multidimensional scaling (MDS). D-15d results differed significantly between the Hg-group and the control group (p < 0.05), with the impairment predominantly along the tritan axis. 2D perceptual color spaces, individual and group, were reconstructed, with the dimensions interpreted as the red-green (RG) and the blue-yellow (BY) systems. When color configurations from the Hg-group were compared to those of the controls, they presented more fluctuations along both chromatic dimensions, indicating a statistically significant difference along the BY axis. In conclusion, the present findings confirm that color vision impairments persist in subjects that have received long-term occupational exposure to Hg-vapor although, at the time of testing, they were presenting mean urinary concentration within the normal range for non-exposed individuals. Considering the advantages of the triadic procedure in clinical evaluation of acquired color vision deficiencies, further studies should attempt to verify and/or improve its efficacy.

Preliminary Findings on the Effects of Occupational Exposure to Mercury Vapor Below Safety Levels on Visual and Neuropsychological Functions

Objective: To evaluate whether there are visual and neurophysical decrements in workers with low exposure to Hg vapor. Methods: Visual fields, contrast sensitivity, color vision, and neuropsychological functions were measured in 10 workers (32.5 +/- 8.5 years) chronically exposed to Hg vapor (4.3 +/- 2.8 years; urinary Hg concentration 22.3 +/- 9.3 mu g/g creatinine). Results: For the worst eyes, we found altered visual field thresholds, lower contrast sensitivity, and color discrimination compared with controls (P < 0.05). There were no significant differences between Hg-exposed subjects and controls on. neuropsychological tests. Nevertheless, duration of exposure was statistically correlated to verbal memory and depression scores. Conclusions: Chronic exposure to Hg vapor at currently accepted safety levels was found to be associated with visual losses but not with neuropsychological dysfunctions in the sample of workers studied. (J Occup Environ Med. 2009,51:1403-1412)

Irreversible color vision losses in patients with chronic mercury vapor intoxication

This longitudinal study addresses the reversibility of color vision losses in subjects who had been occupationally exposed to mercury vapor. Color discrimination was assessed in 20 Hg-exposed patients (mean age = 42.4 +/- 6.5 years; 6 females and 14 males) with exposure to Hg vapor during 10.5 +/- 5.3 years and away from the work place (relative to 2002) for 6.8 +/- 4.2 years. During the Hg exposure or up to one year after ceasing it, mean urinary Hg concentration was 47 +/- 35.4 mu g/g creatinine. There was no information on Hg urinary concentration at the time of the first tests, in 2002 (Ventura et al., 2005), but at the time of the follow-up tests, in 2005, this value was 1.4 +/- 1.4 mu g/g creatinine for patients compared with 0.5 +/- 0.5 mu g/g creatinine for controls (different group from the one in Ventura et al. (2005)). Color vision was monocularly assessed using the Cambridge Colour Test (CCT). Hg-exposed patients had significantly worse color discrimination (p < 0.02) than controls, as evaluated by the size of MacAdam`s color discrimination ellipses and color discrimination thresholds along protan, deutan, and tritan confusion axes. There were no significant differences between the results of the study in Ventura et al. (2005) and in the present follow-up measurements, in 2005, except for worsening of the tritan thresholds in the best eye in 2005. Both chromatic systems, blue-yellow and red-green, were affected in the first evaluation (Ventura et al., 2005) and remained impaired in the follow-up testing, in 2005. These findings indicate that following a long-term occupational exposure to Hg vapor, even several years away from the source of intoxication, color vision impairment remains irreversible.

Visual field losses in workers exposed to mercury vapor

Visual field losses associated with mercury (Hg) exposure have only been assessed in patients exposed to methylmercury. Here we evaluate the automated visual field in 35 ex-workers (30 males; 44.20+/-5.92 years) occupationaly exposed to mercury vapor and 34 controls (21 males; 43.29+/-8.33 years). Visual fields were analyzed with the Humphrey Field Analyzer II (model 750i) using two tests: the standard automated perimetry (SAP, white-on-white) and the short wavelength automated perimetry (SWAP, blue-on-yellow) at 76 locations within a 27 degrees central visual field. Results were analyzed as the mean of the sensitivities measured at the fovea, and at five successive concentric rings, of increasing eccentricity, within the central field. Compared to controls, visual field sensitivities of the experimental group measured using SAP were lower for the fovea as well as for all five eccentricity rings (p<0.05). Sensitivities were significantly lower in the SWAP test (p<0.05) for four of the five extra-foveal eccentricity rings; they were not significant for the fovea (p = 0.584) or for the 15 degrees eccentricity ring (p = 0.965). These results suggest a widespread reduction of sensitivity in both visual field tests. Previous reports in the literature describe moderate to severe concentric constriction of the visual field in subjects with methylmercury intoxication measured manually with the Goldman perimeter. The present results amplify concerns regarding potential medical risks of exposure to environmental mercury sources by demonstrating significant and widespread reductions of visual sensitivity using the more reliable automated perimetry. (C) 2007 Elsevier Inc. All rights reserved.

Electrophysiological evidence for impairment of contrast sensitivity in mercury vapor occupational intoxication

Contrast sensitivity (CS) was evaluated in 41 former workers from a lamp manufacturing plant who were on disability retirement due to exposure to mercury and 14 age-matched controls. The CS was measured monocularly using the sweep visual evoked potential (sVEP) paradigm at 6 spatial frequencies (0.2, 0.8, 2.0, 4.0, 15.0, and 30 cpd). Statistical difference (p < 0.05) was found between the controls and the patient right and left eyes for 2.0 and 4.0 cpd. According the results in those spatial frequencies the eyes were classified in best and worst. Statistical differences were found between the controls and the best eyes for 2.0 and 4.0 cpd and for 0.8, 2.0, and 4.0 cpd for their worst eyes. No correlation was found between CS results and the time of exposure (mean 8.9 yr +/- 4.1), time away from the mercury source (mean = 6.0 yr +/- 3.9), urinary mercury level at the time of work (mean = 40.6 mu g/g +/-36.3) or with the mercury level at the CS measurement time (mean = 1.6 mu g/g +/-1.1). We show the first evidence of a permanent impairment in CS measured objectively with the sVEP. Our data complement the previous psychophysical works reporting a diffuse impairment in the CS function showing a CS reduction in the low to middle spatial frequencies. In conclusion, non-reversible CS impairment was found in occupational exposure to mercury vapor. We suggest that CS measurement should be included in studies of the mercury effects of occupational exposure. (C) 2007 Elsevier Inc. All rights reserved.

Faeces deposition on Amazonian Anthrosols as assessed from 5 beta-stanols

In the Amazon Basin, within a landscape of infertile soils, fertile Anthrosols of pre-Columbian origin occur (Amazonian Dark Earths or terra preta de Indio). These soils are characterized by high amounts of charred organic matter (black carbon, biochar) and high nutrient stocks. Frequently, they were considered as sign for intensive landscape domestication by way of sedentary agriculture and as sign for large settlements in pre-Columbian Amazonia. Beyond the archaeological interest in Amazonian Dark Earths, they increasingly receive attention because it is assumed that they could serve as a model for sustainable agriculture in the humid tropics (terra preta nova). Both questions lack information about the pre-Columbian practices which were responsible for the genesis of Amazonian Dark Earths. It has often been hypothesized that deposition of faeces could have contributed to the high nutrient stocks in these soils, but no study has focussed on this question yet. We analyzed the biomarkers for faeces 5 beta-stanols as well as their precursors and their 5 alpha-isomers in Amazonian Dark Earths and reference soils to investigate the input of faeces into Amazonian Dark Earths. Using Amazonian Dark Earths as example, we discuss the application of threshold values for specific stanols to evaluate faeces deposition in archaeological soils and demonstrate an alternative approach which is based on a comparison of the concentration patterns of 5 beta-stanols with the concentration patterns of their precursors and their 5 alpha-isomers as well as with local backgrounds. The concentration patterns of sterols show that faeces were deposited on Amazonian Dark Earths. (C) 2011 Elsevier Ltd. All rights reserved.

Archaeofacies Analysis: Using Depositional Attributes to Identify Anthropic Processes of Deposition in a Monumental Shell Mound of Santa Catarina State, Southern Brazil

In the coast of Santa Catarina State (southern Brazil), a large population of monumental shell mounds characterizes a highly dynamic coastal setting. In this paper, sedimentary facies analysis was adapted for description, sampling, and interpretation of shell mound complex and repetitive archaeostratigraphic successions. Archaeofacies identification in the field, according to depositional attributes, is tested by contrasting field description with multi-element chemical analyses, total carbon and nitrogen determinations, and micromorphological descriptions. Two vertical sequences at the black deposit of Jabuticabeira II shell mound were studied and preliminary results showed that: (1) depositional attributes are a reliable base for archaeofacies identification in the field, (2) the formation process of this site involved a sequence of anthropic depositional processes, where burned refuse was redeposited over the shell mound following a ritual construction pattern, and (3) the black deposit includes a double palimpsest that refers to provenance and meaning of mound construction material. (C) 2009 Wiley Periodicals, Inc.