The role of the steps in the cleavage of the C-C bond during ethanol oxidation on platinum electrodes

Ethanol oxidation has been studied on stepped platinum single crystal electrodes in acid media using electrochemical and Fourier transform infrared (FTIR) techniques. The electrodes used belong to two different series of stepped surfaces: those having (111) terraces with (100) monoatomic steps and those with (111) terraces with (110) monoatomic steps. The behaviors of the two series of stepped surfaces for the oxidation of ethanol are very different. On the one hand, the presence of (100) steps on the (111) terraces provides no significant enhancement of the activity of the surfaces. On the other hand, (110) steps have a double effect on the ethanol oxidation reaction. At potentials below 0.7 V, the step catalyzes the C-C bond cleavage and also the oxidation of the adsorbed CO species formed. At higher potentials, the step is not only able to break the C-C bond, but also to catalyze the oxidation of ethanol to acetic acid and acetaldehyde. The highest catalytic activity from voltammetry for ethanol oxidation was obtained with the Pt(554) electrode.

Autocatalysis in the open circuit interaction of alcohol molecules with oxidized Pt surfaces

We studied the open circuit interaction of methanol and ethanol with oxidized platinum electrodes using in situ infrared spectroscopy. For methanol, it was found that formic acid is the main species formed in the initial region of the transient and that the steep decrease of the open circuit potential coincides with an explosive increase in the CO(2) production, which is followed by an increase in the coverage of adsorbed CO. For ethanol, acetaldehyde was the main product detected and only traces of dissolved CO(2) and adsorbed CO were found after the steep potential decay. In both cases, the transients were interpreted in terms of (a) the emergence of sub-surface oxygen in the beginning of the transient, where the oxide content is high, and (b) the autocatalytic production of free platinum sites for lower oxide content during the steep decay of the open circuit potential.

Complex kinetics, high frequency oscillations and temperature compensation in the electro-oxidation of ethylene glycol on platinum

Despite the fact that the majority of the catalytic electro-oxidation of small organic molecules presents oscillatory kinetics under certain conditions, there are few systematic studies concerning the influence of experimental parameters on the oscillatory dynamics. Of the studies available, most are devoted to C1 molecules and just some scattered data are available for C2 molecules. We present in this work a comprehensive study of the electro-oxidation of ethylene glycol on polycrystalline platinum surfaces and in alkaline media. The system was studied by means of electrochemical impedance spectroscopy, cyclic voltammetry, and chronoamperometry, and the impact of parameters such as applied current, ethylene glycol concentration, and temperature were investigated. As in the case of other parent systems, the instabilities in this system were associated with a hidden negative differential resistance, as identified by impedance data. Very rich and robust dynamics were observed, including the presence of harmonic and mixed mode oscillations and chaotic states, in some parameter region. Oscillation frequencies of about 16 Hz characterized the fastest oscillations ever reported for the electro-oxidation of small organic molecules. Those high frequencies were strongly influenced by the electrolyte pH and far less affected by the EG concentration. The system was regularly dependent on temperature under voltammetric conditions but rather independent within the oscillatory regime.

Effects of drill cuttings discharge on meiofauna communities of a shelf break site in the southwest Atlantic

The present study investigates the effects of drill cutting discharges on the structure of meiofauna communities in an area of the shelf break at Campos Basin, Southeast Brazil. Drilling activities were operated, in a first phase, with water-based fluid and, in a second phase, with synthetic fluid paraffin-based (NAF-III). A total of 135 samples taken at a pre-drilling situation (MS1) and two post-drilling moments (MS2 and MS3-3 and 22 months post-drilling, respectively) were analyzed. Effects on meiofauna were dependent on two main factors: 1-the impact received during drilling operation, if water-based or synthetic/water-based drilling fluid and 2-the background state, if it already presented signs of previous drilling activities or not. Based on univariate and multivariate analysis, there were evidences that the most affected area after drilling was those under the influence of synthetic-based fluid and that already had signs of previous drillings activities. The region impacted only by water-based fluid was less affected and the only one that completely recovered after 22 months. Nematodes and copepods had different responses to the impact. While copepods flourish in the impacted area and recovered 22 months after drilling, nematodes were adversely affected shortly after drilling and the community structure only recovered where hydrocarbons had been depleted.

Greenhouse gas emissions from alternative futures of deforestation and agricultural management in the southern Amazon

The Brazilian Amazon is one of the most rapidly developing agricultural areas in the world and represents a potentially large future source of greenhouse gases from land clearing and subsequent agricultural management. In an integrated approach, we estimate the greenhouse gas dynamics of natural ecosystems and agricultural ecosystems after clearing in the context of a future climate. We examine scenarios of deforestation and postclearing land use to estimate the future (2006-2050) impacts on carbon dioxide (CO(2)), methane (CH(4)), and nitrous oxide (N(2)O) emissions from the agricultural frontier state of Mato Grosso, using a process-based biogeochemistry model, the Terrestrial Ecosystems Model (TEM). We estimate a net emission of greenhouse gases from Mato Grosso, ranging from 2.8 to 15.9 Pg CO(2)-equivalents (CO(2)-e) from 2006 to 2050. Deforestation is the largest source of greenhouse gas emissions over this period, but land uses following clearing account for a substantial portion (24-49%) of the net greenhouse gas budget. Due to land-cover and land-use change, there is a small foregone carbon sequestration of 0.2-0.4 Pg CO(2)-e by natural forests and cerrado between 2006 and 2050. Both deforestation and future land-use management play important roles in the net greenhouse gas emissions of this frontier, suggesting that both should be considered in emissions policies. We find that avoided deforestation remains the best strategy for minimizing future greenhouse gas emissions from Mato Grosso.

Soil carbon stocks under no-tillage mulch-based cropping systems in the Brazilian Cerrado: An on-farm synchronic assessment

No-tillage mulch-based (NTM) cropping systems have been widely adopted by farmers in the Brazilian savanna region (Cerrado biome). We hypothesized that this new type of management should have a profound impact on soil organic carbon (SOC) at regional scale and consequently on climate change mitigation. The objective of this study was thus to quantify the SOC storage potential of NTM in the oxisols of the Cerrado using a synchronic approach that is based on a chronosequence of fields of different years under NTM. The study consisted of three phases: (1) a farm/cropping system survey to identify the main types of NTM systems to be chosen for the chronosequence; (2) a field survey to identify a homogeneous set of situations for the chronosequence and (3) the characterization of the chronosequence to assess the SOC storage potential. The main NTM system practiced by farmers is an annual succession of soybean (Glycine max)or maize (Zea mays) with another cereal crop. This cropping system covers 54% of the total cultivated area in the region. At the regional level, soil organic C concentrations from NTM fields were closely correlated with clay + silt content of the soil (r(2) = 0.64). No significant correlation was observed (r(2) = 0.07), however, between these two variables when we only considered the fields with a clay + silt content in the 500-700 g kg(-1) range. The final chronosequence of NTM fields was therefore based on a subsample of eight fields, within this textural range. The SOC stocks in the 0-30 cm topsoil layer of these selected fields varied between 4.2 and 6.7 kg C m(-2) and increased on average (r(2) = 0.97) with 0.19 kg C m(-2) year(-1). After 12 years of NTM management, SOC stocks were no longer significantly different from the stocks under natural Cerrado vegetation (p < 0.05), whereas a 23-year-old conventionally tilled and cropped field showed SOC stocks that were about 30% below this level. Confirming our hypotheses, this study clearly illustrated the high potential of NTM systems in increasing SOC storage under tropical conditions, and how a synchronic approach may be used to assess efficiently such modification on farmers` fields, identifying and excluding non desirable sources of heterogeneity (management, soils and climate). (C) 2010 Elsevier B.V. All rights reserved.

Land-Water interactions in the amazon

Biogeochemistry is hosting this special thematic issue devoted to studies of land-water interactions, as part of the Large-scale Biosphere-Atmosphere Experiment in Amaznia (LBA). This compilation of papers covers a broad range of topics with a common theme of coupling land and water processes, across pristine and impacted systems. Findings highlighted that hydrologic flowpaths are clearly important across basin size and structure in determining how water and solutes reach streams. Land-use changes have pronounced impacts on flowpaths, and subsequently, on stream chemistry, from small streams to large rivers. Carbon is produced and transformed across a broad array of fluvial environments and wetlands. Surface waters are not only driven by, but provide feedback to, the atmosphere.

Changes in soil organic carbon storage under different agricultural management systems in the Southwest Amazon Region of Brazil

The Cerrado and Amazon regions of Brazil are probably the largest agricultural frontier of the world, and Could be a sink or source for C depending on the net effect of land use change and subsequent management on soil organic C pools. We evaluated the effects of agricultural management systems on soil organic C (SOC) stocks in the Brazilian states of Rondonia and Mato Grosso, and derived regional specific factors for soil C stock change associated with different management systems. We used 50 observations (data points) in this study, including 42 dealing with annual cropping practices and 8 dealing with perennial cropping, and analyzed the data in linear mixed-effect models. No tillage (NT) systems in Cerrado areas increased SOC Storage by 1.08 +/- 0.06 relative to SOC stocks under native conditions, while SOC storage increased by a modest factor of 1.01 +/- 0.17 in Cerradao and Amazon Forest conditions. Full tillage (FT) had negative effect on SOC storage relative to NT, decreasing SOC stocks by a factor of 0.94 +/- 0.04. but did not significantly reduce SOC stocks relative to native levels when adopted in the Cerrado region. Perennial cropping had a minimal impact on SOC stocks, estimated at a factor Value of 0.98 +/- 0.14, suggesting these systems maintain about 98% of the SOC stock found under native vegetation. The results Suggest that NT adoption may be increasing SOC with land use change from native vegetation to cropland management in the Cerrado region of Brazil. (C) 2009 Elsevier B.V. All rights reserved.

Soil Carbon Turnover Measurement by Physical Fractionation at a Forest-to-Pasture Chronosequence in the Brazilian Amazon

The effect of conversion from forest-to-pasture upon soil carbon stocks has been intensively discussed, but few studies focus on how this land-use change affects carbon (C) distribution across soil fractions in the Amazon basin. We investigated this in the 20 cm depth along a chronosequence of sites from native forest to three successively older pastures. We performed a physicochemical fractionation of bulk soil samples to better understand the mechanisms by which soil C is stabilized and evaluate the contribution of each C fraction to total soil C. Additionally, we used a two-pool model to estimate the mean residence time (MRT) for the slow and active pool C in each fraction. Soil C increased with conversion from forest-to-pasture in the particulate organic matter (> 250 mu m), microaggregate (53-250 mu m), and d-clay (< 2 mu m) fractions. The microaggregate comprised the highest soil C content after the conversion from forest-to-pasture. The C content of the d-silt fraction decreased with time since conversion to pasture. Forest-derived C remained in all fractions with the highest concentration in the finest fractions, with the largest proportion of forest-derived soil C associated with clay minerals. Results from this work indicate that microaggregate formation is sensitive to changes in management and might serve as an indicator for management-induced soil carbon changes, and the soil C changes in the fractions are dependent on soil texture.

Total soil carbon and chemical attributes under different land uses in the Brazilian savanna

Total soil carbon and chemical attributes under different land uses in the Brazilian savanna. The Brazilian savanna region (Cerrado) is one of the largest cultivated areas of the world. The different land uses in the region can effectively change the quantities of soil organic matter and the cycling of nutrients. I-lie objective of this study was to evaluate the effect of different land use management systems on the relationship between soil organic carbon and the soil chemical attributes of a Red Latosol (Oxisol) under Cerrado in Rio Verde (Goias state). The treatments studied were native vegetation (cerrado), low-productivity pasture, conventional tillage with soybean, and no-tillage with soybean and maize. The smallest values for pH, available P, K, Ca and Mg were observed for the Cerradao treatment, even if the relatively high C levels increased the potential soil cation exchange capacity. The pasture, conventional tillage and no-tillage treatments showed higher K, Ca, Mg, available 13, and S concentrations in the soil. In the areas where soil tillage did not take place and lime and fertilizers were applied superficially, the stratification of the soil organic carbon provides the retention of the elements near to the surface, with significance correlations with the soil chemicals attributes.

Carbon sequestration in agricultural soils in the Cerrado region of the Brazilian Amazon

The introduction of crop management practices after conversion of Amazon Cerrado into cropland influences soil C stocks and has direct and indirect consequences on greenhouse gases (GHG) emissions. The aim of this study was to quantify soil C sequestration, through the evaluation of the changes in C stocks, as well as the GHG fluxes (N(2)O and CH(4)) during the process of conversion of Cerrado into agricultural land in the southwestern Amazon region, comparing no-tillage (NT) and conventional tillage (CT) systems. We collected samples from soils and made gas flux measurements in July 2004 (the dry season) and in January 2005 (the wet season) at six areas: Cerrado, CT cultivated with rice for 1 year (1CT) and 2 years (2CT), and NT cultivated with soybean for 1 year (1NT), 2 years (2NT) and 3 years (3NT), in each case after a 2-year period of rice under CT. Soil samples were analyzed in both seasons for total organic C and bulk density. The soil C stocks, corrected for a mass of soil equivalent to the 0-30-cm layer under Cerrado, indicated that soils under NT had generally higher C storage compared to native Cerrado and CT soils. The annual C accumulation rate in the conversion of rice under CT into soybean under NT was 0.38 Mg ha(-1) year(-1). Although CO(2) emissions were not used in the C sequestration estimates to avoid double counting, we did include the fluxes of this gas in our discussion. In the wet season, CO(2) emissions were twice as high as in the dry season and the highest N(2)O emissions occurred under the NT system. There were no CH(4) emissions to the atmosphere (negative fluxes) and there were no significant seasonal variations. When N(2)O and CH(4) emissions in C-equivalent were subtracted (assuming that the measurements made on 4 days were representative of the whole year), the soil C sequestration rate of the conversion of rice under CT into soybean under NT was 0.23 Mg ha(-1) year(-1). Although there were positive soil C sequestration rates, our results do not present data regarding the full C balance in soil management changes in the Amazon Cerrado. (C) 2008 Elsevier B.V. All rights reserved.

Dissolved carbon in an urban area of a river in the Brazilian Amazon

The main objective of this study was to evaluate dissolved organic and inorganic carbon dynamics along upstream and downstream reaches of the Acre River draining the city of Rio Branco, in the state of Acre, Brazil. Dissolved organic carbon (DOC) concentrations in the Acre River were significantly higher during the wet season, ranging from 385 +/- A 160 to 430 +/- A 131 mu M among the stations, with no difference in upstream and downstream concentrations. Dissolved inorganic carbon (DIC) showed an inverse pattern, with higher concentrations in the dry season, ranging from 816 +/- A 215 to 998 +/- A 754 mu M among the stations, as well as no difference in upstream and downstream DIC concentrations. Bicarbonate was the dominant DIC fraction and was mainly observed during the dry season. Due to lower pH values during the wet season, CO(2) partial pressure (pCO(2)) in the Acre River was higher in the wet season, with values ranging from 4,567 +/- A 1,813 to 4,893 +/- A 837 ppm among the stations. Our results indicate that, although the Acre River drains a large city with significant sewage disposal into the river, seasonal hydrological processes are the main driver of dissolved carbon dynamics, even in the downstream study reach directly influenced by urbanization.

Small rivers in the southwestern Amazon and their role in CO(2) outgassing

A recent estimate of CO(2) outgassing from Amazonian wetlands suggests that an order of magnitude more CO(2) leaves rivers through gas exchange with the atmosphere than is exported to the ocean as organic plus inorganic carbon. However, the contribution of smaller rivers is still poorly understood, mainly because of limitations in mapping their spatial extent. Considering that the largest extension of the Amazon River network is composed of small rivers, the authors` objective was to elucidate their role in air-water CO(2) exchange by developing a geographic information system ( GIS)- based model to calculate the surface area covered by rivers with channels less than 100 m wide, combined with estimated CO(2) outgassing rates at the Ji-Parana River basin, in the western Amazon. Estimated CO(2) outgassing was the main carbon export pathway for this river basin, totaling 289 Gg C yr(-1), about 2.4 times the amount of carbon exported as dissolved inorganic carbon ( 121 Gg C yr(-1)) and 1.6 times the dissolved organic carbon export ( 185 Gg C yr(-1)). The relationships established here between drainage area and channel width provide a new model for determining small river surface area, allowing regional extrapolations of air - water gas exchange. Applying this model to the entire Amazon River network of channels less than 100 m wide ( third to fifth order), the authors calculate that the surface area of small rivers is 0.3 +/- 0.05 million km(2), and it is potentially evading to the atmosphere 170 +/- 42 Tg C yr(-1) as CO(2). Therefore, these ecosystems play an important role in the regional carbon balance.

Intra and interannual variability in the Madeira River water chemistry and sediment load

Concentrations of cations (Na(+), Ca(2+), Mg(2+), K(+), NH(4) (+)), anions (HCO(3) (-), Cl(-), NO(3) (-), SO(4) (2-), PO(4) (3-)) and suspended sediments in the Madeira River water were determined near the city of Porto Velho (RO), in order to assess variation in water chemistry from 2004 to 2007. Calcium and bicarbonate were the dominant cation and anion, respectively. Significant seasonal differences were found, with highest concentrations occurring during the dry season, as expected from the drainage of Andean carbonate-rich substratum. Interannual variations were also observed, but became significant only when annual average discharge was 25% less than normal. Under this atypical discharge condition, bicarbonate was replaced by sulfate, and higher suspended sediment concentrations and loads were also observed. Compared to previously published studies, it appears that no significant changes in water chemistry have occurred during the last 20-30 years, although differences in approaches and sampling designs among this and previous studies may not allow detection of modest changes. The calculated suspended sediment load reported here is close to the values presented elsewhere, reinforcing the relative importance of this river as a sediment supplier for the Amazon Basin. Seasonality has a significant control on the chemistry of Madeira River waters, and severe decrease in discharge due to anthropogenic changes, such as construction of reservoirs or the occurrence of drier years-a plausible consequence of global climate change-may lead to modification in the chemical composition as well in the sediment deliver to the Amazon River.

Effects of land cover on chemical characteristics of streams in the Cerrado region of Brazil

The Cerrado is the second largest Brazilian biome and contains the headwaters of three major hydrological basins in Brazil. In spite of the biological and ecological relevance of this biome, there is little information about how land use changes affect the chemistry of low-order streams in the Cerrado. To evaluate these effects streams that drain areas under natural, rural, and urban land cover were sampled near Brasilia, Brazil. Water samples were collected between September 2004 and December 2006. Chemical concentrations generally followed the pattern of Urban > Rural > Natural. Median conductivity of stream water of 21.6 (interquartile: 22.7) mu S/cm in urban streams was three and five-fold greater relative to rural and natural areas, respectively. In the wet season, despite of increasing discharge, concentration of many solutes were higher, particularly in rural and natural streams. Streams also presented higher total dissolved N (TDN) loads from natural to rural and urban although DIN:DON ratios did not differ significantly. In natural and urban streams TDN was 80 and 77% dissolved organic N, respectively. These results indicate that alterations in land cover from natural to rural and urban are changing stream water chemistry in the Cerrado with increasing solute concentrations, in addition to increased TDN output in areas under urban cover, with potential effects on ecosystem function.