Gold is not a Faradaic-Efficient Borohydride Oxidation Electrocatalyst: An Online Electrochemical Mass Spectrometry Study

Direct borohydride fuel cells are promising high energy density portable generators. However, their development remains limited by the complexity of the anodic reaction: The borohydride oxidation reaction (BOR) kinetics is slow and occurs at high overvoltages, while it may compete with the heterogeneous hydrolysis of BH(4)(-). Nevertheless, one usually admits that gold is rather inactive toward the heterogeneous hydrolysis of BH(4)(-) and presents some activity regarding the BOR, therefore yielding to the complete eight-electron BOR. In the present paper, by coupling online mass spectrometry to electrochemistry, we in situ monitored the H(2) yield during BOR experiments on sputtered gold electrodes. Our results show non-negligible H(2) generation on Au on the whole BOR potential range (0-0.8 V vs reversible hydrogen electrode), thus revealing that gold cannot be considered as a faradaic-efficient BOR electrocatalyst. We further propose a relevant reaction pathway for the BOR on gold that accounts for these findings.

Evaluation of Several Carbon-Supported Nanostructured Ni-Doped Manganese Oxide Materials for the Electrochemical Reduction of Oxygen

Physical and electrochemical properties of nanostructured Ni-doped manganese oxides (MnO(x)) catalysts supported on different carbon powder substrates were investigated so as to characterize any carbon substrate effect toward the oxygen reduction reaction (ORR) kinetics in alkaline medium. These NiMnO(x)/C materials were characterized using physicochemical analyses. Small insertion of Ni atoms in the MnO(x) lattice was observed, which consists of a true doping of the manganese oxide phase. The corresponding NiMnO(x) phase is present in the form of needles or agglomerates, with crystallite sizes in the order of 1.5-6.7 nm (from x-ray diffraction analyses). Layered manganite (MnOOH) phase has been detected for the Monarch 1000-supported NiMnO(x) material, while different species of MnO(x) phases are present at the E350G and MM225 carbons. Electrochemical studies in thin porous coating active layers in the rotating ring-disk electrode setup revealed that the MnO(x) catalysts present better ORR kinetics and electrochemical stability upon Ni doping. The ORR follows the so-called peroxide mechanism on MnO(x)/C catalysts, with the occurrence of minority HO(2)(-) disproportionation reaction. The HO(2)(-) disproportionation reaction progressively increases with the Ni content in NiMnO(x) materials. The catalysts supported on the MM225 and E350G carbons promote faster disproportionation reaction, thus leading to an overall four-electron ORR pathway. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3528439] All rights reserved.

Complex Oscillatory Response of a PEM Fuel Cell Fed with H(2)/CO and Oxygen

Oscillatory kinetics is commonly observed in the electrocatalytic oxidation of most species that can be used in fuel cell devices. Examples include formic acid, methanol, ethanol, ethylene glycol, and hydrogen/carbon monoxide mixtures, and most papers refer to half-cell experiments. We report in this paper the experimental investigation of the oscillatory dynamics in a proton exchange membrane (PEM) fuel cell at 30 degrees C. The system consists of a Pt/C cathode fed with oxygen and a PtRu (1:1)/C anode fed with H(2) mixed with 100 ppm of CO, and was studied at different cell currents and anode flow rates. Many different states including periodic and nonperiodic series were observed as a function of the cell current and the H(2)/CO flow rate. In general, aperiodic/chaotic states were favored at high currents and low flow rates. The dynamics was further characterized in terms of the relationship between the oscillation amplitude and the subsequent time required for the anode to get poisoned by carbon monoxide. Results are discussed in terms of the mechanistic aspects of the carbon monoxide adsorption and oxidation. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3463725] All rights reserved.

Imidazole-imidazolium picrate monohydrate

The asymmetric unit of the title compound, C(3)H(5)N(2)(+)center dot C(6)H(2)N(3)O(7)(-)center dot C(3)H(4)N(2)center dot H(2)O or H(C(3)H(4)N(2))(2)(+)center dot C(6)H(2)N(3)O(7)(-)center dot H(2)O, contains a diimidazolium cationic unit, one picrate anion and one molecule of water. In the crystal, the components are connected by N-H center dot center dot center dot O, N-H center dot center dot center dot N and O-H center dot center dot center dot O hydrogen bonds, forming a two-dimensional network parallel to (001). In addition, weak intermolecular C-H center dot center dot center dot O hydrogen bonds lead to the formation of a three-dimensional network featuring R(5)(5)(19) rings.

Effect of sugarcane harvesting systems on soil carbon stocks in Brazil: an examination of existing data

Agricultural management practices that promote net carbon (C) accumulation in the soil have been considered as an important potential mitigation option to combat global warming. The change in the sugarcane harvesting system, to one which incorporates C into the soil from crop residues, is the focus of this work. The main objective was to assess and discuss the changes in soil organic C stocks caused by the conversion of burnt to unburnt sugarcane harvesting systems in Brazil, when considering the main soils and climates associated with this crop. For this purpose, a dataset was obtained from a literature review of soils under sugarcane in Brazil. Although not necessarily from experimental studies, only paired comparisons were examined, and for each site the dominant soil type, topography and climate were similar. The results show a mean annual C accumulation rate of 1.5 Mg ha-1 year-1 for the surface to 30-cm depth (0.73 and 2.04 Mg ha-1 year-1 for sandy and clay soils, respectively) caused by the conversion from a burnt to an unburnt sugarcane harvesting system. The findings suggest that soil should be included in future studies related to life cycle assessment and C footprint of Brazilian sugarcane ethanol.

Net greenhouse gas fluxes in Brazilian ethanol production systems

Biofuels are both a promising solution to global warming mitigation and a potential contributor to the problem. Several life cycle assessments of bioethanol have been conducted to address these questions. We performed a synthesis of the available data on Brazilian ethanol production focusing on greenhouse gas (GHG) emissions and carbon (C) sinks in the agricultural and industrial phases. Emissions of carbon dioxide (CO(2)) from fossil fuels, methane (CH(4)) and nitrous oxide (N(2)O) from sources commonly included in C footprints, such as fossil fuel usage, biomass burning, nitrogen fertilizer application, liming and litter decomposition were accounted for. In addition, black carbon (BC) emissions from burning biomass and soil C sequestration were included in the balance. Most of the annual emissions per hectare are in the agricultural phase, both in the burned system (2209 out of a total of 2398 kg C(eq)), and in the unburned system (559 out of 748 kg C(eq)). Although nitrogen fertilizer emissions are large, 111 kg C(eq) ha-1 yr-1, the largest single source of emissions is biomass burning in the manual harvest system, with a large amount of both GHG (196 kg C(eq) ha-1 yr-1). and BC (1536 kg C(eq) ha-1 yr-1). Besides avoiding emissions from biomass burning, harvesting sugarcane mechanically without burning tends to increase soil C stocks, providing a C sink of 1500 kg C ha-1 yr-1 in the 30 cm layer. The data show a C output: input ratio of 1.4 for ethanol produced under the conventionally burned and manual harvest compared with 6.5 for the mechanized harvest without burning, signifying the importance of conservation agricultural systems in bioethanol feedstock production.

Near infrared spectroscopy for soil bulk density assessment

P>Soil bulk density values are needed to convert organic carbon content to mass of organic carbon per unit area. However, field sampling and measurement of soil bulk density are labour-intensive, costly and tedious. Near-infrared reflectance spectroscopy (NIRS) is a physically non-destructive, rapid, reproducible and low-cost method that characterizes materials according to their reflectance in the near-infrared spectral region. The aim of this paper was to investigate the ability of NIRS to predict soil bulk density and to compare its performance with published pedotransfer functions. The study was carried out on a dataset of 1184 soil samples originating from a reforestation area in the Brazilian Amazon basin, and conventional soil bulk density values were obtained with metallic ""core cylinders"". The results indicate that the modified partial least squares regression used on spectral data is an alternative method for soil bulk density predictions to the published pedotransfer functions tested in this study. The NIRS method presented the closest-to-zero accuracy error (-0.002 g cm-3) and the lowest prediction error (0.13 g cm-3) and the coefficient of variation of the validation sets ranged from 8.1 to 8.9% of the mean reference values. Nevertheless, further research is required to assess the limits and specificities of the NIRS method, but it may have advantages for soil bulk density predictions, especially in environments such as the Amazon forest.

Individual-level diet variation in four species of Brazilian frogs

Many natural populations exploiting a wide range of resources are actually composed of relatively specialized individuals. This interindividual variation is thought to be a consequence of the invasion of `empty` niches in depauperate communities, generally in temperate regions. If individual niches are constrained by functional trade-offs, the expansion of the population niche is only achieved by an increase in interindividual variation, consistent with the `niche variation hypothesis`. According to this hypothesis, we should not expect interindividual variation in species belonging to highly diverse, packed communities. In the present study, we measured the degree of interindividual diet variation in four species of frogs of the highly diverse Brazilian Cerrado, using both gut contents and delta(13)C stable isotopes. We found evidence of significant diet variation in the four species, indicating that this phenomenon is not restricted to depauperate communities in temperate regions. The lack of correlations between the frogs` morphology and diet indicate that trade-offs do not depend on the morphological characters measured here and are probably not biomechanical. The nature of the trade-offs remains unknown, but are likely to be cognitive or physiological. Finally, we found a positive correlation between the population niche width and the degree of diet variation, but a null model showed that this correlation can be generated by individuals sampling randomly from a common set of resources. Therefore, albeit consistent with, our results cannot be taken as evidence in favour of the niche variation hypothesis.

Wavelet analysis of MODIS time series to detect expansion and intensification of row-crop agriculture in Brazil

Since 2000, the southwestern Brazilian Amazon has undergone a rapid transformation from natural vegetation and pastures to row-crop agricultural with the potential to affect regional biogeochemistry. The goals of this research are to assess wavelet algorithms applied to MODIS time series to determine expansion of row-crops and intensification of the number of crops grown. MODIS provides data from February 2000 to present, a period of agricultural expansion and intensification in the southwestern Brazilian Amazon. We have selected a study area near Comodoro, Mato Grosso because of the rapid growth of row-crop agriculture and availability of ground truth data of agricultural land-use history. We used a 90% power wavelet transform to create a wavelet-smoothed time series for five years of MODIS EVI data. From this wavelet-smoothed time series we determine characteristic phenology of single and double crops. We estimate that over 3200 km(2) were converted from native vegetation and pasture to row-crop agriculture from 2000 to 2005 in our study area encompassing 40,000 km(2). We observe an increase of 2000 km(2) of agricultural intensification, where areas of single crops were converted to double crops during the study period. (C) 2007 Elsevier Inc. All rights reserved.

BORON UPTAKE AND DISTRIBUTION IN FIELD GROWN CITRUS TREES

In low fertility tropical soils, boron (B) deficiency impairs fruit production. However, little information is available on the efficiency of nutrient application and use by trees. Therefore, this work verified the effects of soil and foliar applications of boron in a commercial citrus orchard. An experiment was conducted with fertigated 4-year-old `Valencia` sweet orange trees on `Swingle` citrumelo rootstock. Boron (isotopically-enriched 10B) was supplied to trees once or twice in the growing season, either dripped in the soil or sprayed on the leaves. Trees were sampled at different periods and separated into different parts for total B contents and 10B/11B isotope ratios analyses. Soil B applied via fertigation was more efficient than foliar application for the organs grown after the B fertilization. Recovery of labeled B by fruits was 21% for fertigation and 7% for foliar application. Residual effects of nutrient application in the grove were observed in the year after labeled fertilizer application, which greater proportions derived from the soil supply.

ACCUMULATION AND TRANSLOCATION OF SILICON IN RICE AND BEAN PLANTS USING THE 30SI STABLE ISOTOPE

The 30Si silicon isotope stable was used for assessing the accumulation and translocation of Si in rice and bean plants grown in labeled nutritive solution. The isotopic silicon composition in plant materials was determined by mass spectrometry (IRMS) using the method based on SiF4 formation. Considering the total-Si added into nutritive solutions, the quantity absorbed by plants was near to 51% for rice and 15% for bean plants. The accumulated amounts of Si per plant were about 150g in rice and 8.6g in bean. Approximately 70% of the total-Si accumulated was found in leaves. At presented experimental conditions, the results confirmed that once Si is accumulated in the old parts of rice and bean plant tissues it is not redistributed to new parts, even when Si is not supplied to plants from nutritive solution.

Effects of Molybdenum, Nickel, and Nitrogen Sources on the Mineral Nutrition and Growth of Rice Plants

Upland rice plants, cultivar `IAC 202,` were grown in nutrient solution until full tillering. Treatments consisted of ammonium nitrate (AN) or urea (UR) as nitrogen (N) source plus molybdenum (Mo) and/or nickel (Ni): AN + Mo + Ni, AN + Mo - Ni, AN - Mo + Ni, UR + Mo + Ni, UR + Mo - Ni, and UR - Mo + Ni. The experiment was carried out to better understand the effect of these treatments on dry-matter yield, chlorophyll, net photosynthesis rate, nitrate (NO3 --N), total N, in vitro activities of urease and nitrate reductase (NR), and Mo and Ni concentrations. In UR-grown plants, Mo and Ni addition increased yield of dry matter. Regardless of the N source, chlorophyll concentration and net photosynthesis rate were reduced when Mo or Ni were omitted, although not always significantly. The omission of either Mo or Ni led to a decrease in urease activity, independent of N source. Nitrate reductase activity increased in nutrient solutions without Mo, although NO3 --N increased. There was not a consistent variation in total N concentration. Molybdenum and Ni concentration in roots and shoots were influenced by their supply in the nutrient solution. Molybdenum concentration was not influenced by N sources, whereas Ni content in both root and shoots was greater in ammonium nitrate-grown plants. In conclusion, it can be hypothesized that there is a relationship between Mo and Ni acting on photosynthesis, although is an indirect one. This is the first evidence for a beneficial effect of Mo and Ni interaction on plant growth.

Description of the Immatures of Workers of the Ant Linepithema micans Forel (Hymenoptera: Formicidae)

Linepithema micans Forel is a poorly studied species that is now considered a pest in vineyards in South Brazil. Larval characters have been used in a few phylogenetic studies, and their importance greatly depends in the amount of available information on different species. This study presents a complete panorama on the external morphology of the immatures of L. micans based on observations by light and scanning electron microscopy. The number of larval instars was estimated as three based on the frequency distribution of head widths of 965 larvae. Larvae of L. micans were similar to other Linepithema Mayr in the general format of body and mandibles, presenting a dorsal abdominal protuberance, nine pairs of spiracle, and unbranched hairs. On the other hand, L. micans was unique for having shorter hairs, predominantly denticulate, intraspecific variation in the number of antennal sensilla and in the types of sensilla on the labial palps were reported. Microsc. Res. Tech. 74:337-342, 2011. (C) 2010 Wiley-Liss, Inc.

Direct Solid-Phase Optical Measurements in Flow Systems: A Review

Measurements based on absorption, reflectance, or luminescence of molecular species or complex ions can be carried out directly on a solid support simultaneously to the retention of the analyte. The use of this strategy in flow-based systems is advantageous in view of the reproducible handling of solutions in retention and elution steps of the analyte. This approach can be exploited to increase sensitivity, minimize reagent consumption as well as waste generation, improve selectivity or for simultaneous determination based on selective retention or differences in sorption rates of the analytes. This review focuses on the main characteristics of direct solid-phase measurements in flow systems, including the discussion of advantages and limitations and practical guidelines to the successful implementation of this approach. Selected applications in diverse fields, such as pharmaceutical, food, and environmental analysis are discussed.

Coexistence of forest and savanna in an Amazonian area from a geological perspective

Question: How can the coexistence of savanna and forest in Amazonian areas with relatively uniform climates be explained? Location: Eastern Marajo Island, northeast Amazonia, Brazil. Methods: The study integrated floristic analysis, terrain morphology, sedimentology and delta(13)C of soil organic matter. Floristic analysis involved rapid ecological assessment of 33 sites, determination of occurrence, specific richness, hierarchical distribution and matrix of floristic similarity between paired vegetation types. Terrain characterization was based on analysis of Landsat images using 4(R), 5(G) and 7(B) composition and digital elevation model (DEM). Sedimentology involved field descriptions of surface and core sediments. Finally, radiocarbon dating and analysis of delta(13)C of soil profile organic matter and natural ecotone forest-savanna was undertaken. Results: Slight tectonic subsidence in eastern Marajo Island favours seasonal flooding, making it unsuitable for forest growth. However, this area displays slightly convex-up, sinuous morphologies related to paleochannels, covered by forest. Terra-firme lowland forests are expanding from west to east, preferentially occupying paleochannels and replacing savanna. Slack, running water during channel abandonment leads to disappearance of varzea/gallery forest at channel margins. Long-abandoned channels sustain continuous terra-firme forests, because of longer times for more species to establish. Recently abandoned channels have had less time to become sites for widespread tree development, and are either not vegetated or covered by savanna. Conclusion: Landforms in eastern Marajo Island reflect changes in the physical environment due to reactivation of tectonic faults during the latest Quaternary. This promoted a dynamic history of channel abandonment, which controlled a set of interrelated parameters (soil type, topography, hydrology) that determined species location. Inclusion of a geological perspective for paleoenvironmental reconstruction can increase understanding of plant distribution in Amazonia.