Reações de ozonólise de olefinas em fase gasosa

Biogenic emissions of volatile organic compounds play a fundamental role in the atmospheric chemistry, vegetation being one of their major sources. Amongst the VOCs emitted by plants, olefins and terpenoids are the most abundant. These compounds, due to the presence of two or more double bonds and other structural features, are very reactive in the atmosphere and act as precursors of the photochemical smog and aerosols. This article presents a review of the reactions of olefins and terpenoids with ozone, in the gas phase, with emphasis toward the mechanisms and kinetic aspects.

Observations of air composition in Brazil between the Equator and 20°s during the dry season.

Field measurement programs in Brazil during the dry season months of August and September in 1979 and 1980 have demonstrated the great importance of the continental tropics in global air chemistry. Especially in the mixed layer, the air composition over land is much different from that over the ocean and the land areas are clearly longe scale sources of many inportant trace gases. During the dry season much biomass, burning takes place especially in the cerrado regions leading to substantial emission of air pollutants, such as CO, NOx, N2O, CH4 and other hydrocarbons. Ozone concentrations are alsoenhanced due to photochemical reactions. Biogenic organic emissions from tropical forests play likewise an important role in the photochemistry of the atmosphere. Carbon monoxide was found to be present in high concentrations in the boundary layer of the tropical forest, but ozone concentrations were much lower than in the cerrado.

Extraction and concentration of biogenic calcium oxalate from plant leaves

The objective of this study was to extract and concentrate calcium oxalate (CaOx) crystals from plant leaves that form the above mentioned crystals. The chemical and physical studies of CaOx from plant to be performed depend on an adequate amount of the crystals. The plant used in this study was croton (Codiaeum variegatum). The leaves were ground in a heavy duty blender and sieved through a 0.20 mm sieve. The suspension obtained was suspended in distilled water. The crystals were concentrated at the bottom of a test tube. The supernatant must be washed until it is free of plant pigments and other organic substances. Biogenic CaOx crystals have well-defined and sharp peaks, indicating very high crystallinity. Moreover, the CaOx crystals were not damaged during the extraction procedure, as can be seen on the scanning electron microscope images. The porposed method can be considered efficient to extract and concentrate biogenic calcium oxalate.

Postharvest nitrous oxide emissions from a subtropical oxisol as influenced by summer crop residues and their management

Nitrous oxide (N2O) is the most important non-CO2 greenhouse gas and soil management systems should be evaluated for their N2O mitigation potential. This research evaluated a long-term (22 years) experiment testing the effect of soil management systems on N2O emissions in the postharvest period (autumn) from a subtropical Rhodic Hapludox at the research center FUNDACEP, in Cruz Alta, state of Rio Grande do Sul. Three treatments were evaluated, one under conventional tillage with soybean residues (CTsoybean) and two under no-tillage with soybean (NTsoybean) and maize residues (NTmaize). N2O emissions were measured eight times within 24 days (May 2007) using closed static chambers. Gas flows were obtained based on the relations between gas concentrations in the chamber at regular intervals (0, 15, 30, 45 min) analyzed by gas chromatography. After soybean harvest, accumulated N2O emissions in the period were approximately three times higher in the untilled soil (164 mg m-2 N) than under CT (51 mg m-2 N), with a short-lived N2O peak of 670 mg m-2 h-1 N. In contrast, soil N2O emissions in NT were lower after maize than after soybean, with a N2O peak of 127 g m-2 h-1 N. The multivariate analysis of N2O fluxes and soil variables, which were determined simultaneously with air sampling, demonstrated that the main driving variables of soil N2O emissions were soil microbial activity, temperature, water-filled pore space, and NO3- content. To replace soybean monoculture, crop rotation including maize must be considered as a strategy to decrease soil N2O emissions from NT soils in Southern Brazil in a Autumn.

Mitigation of methane and nitrous oxide emissions from flood-irrigated rice by no incorporation of winter crop residues into the soil

Winter cover crops are sources of C and N in flooded rice production systems, but very little is known about the effect of crop residue management and quality on soil methane (CH4) and nitrous oxide (N2O) emissions. This study was conducted in pots in a greenhouse to evaluate the influence of crop residue management (incorporated into the soil or left on the soil surface) and the type of cover-crop residues (ryegrass and serradella) on CH4 and N2O emissions from a flooded Albaqualf soil cultivated with rice (Oryza sativa L.). The closed chamber technique was used for air sampling and the CH4 and N2O concentrations were analyzed by gas chromatography. Soil solution was sampled at two soil depths (2 and 20 cm), simultaneously to air sampling, and the contents of dissolved organic C (DOC), NO3-, NH4+, Mn2+, and Fe2+ were analyzed. Methane and N2O emissions from the soil where crop residues had been left on the surface were lower than from soil with incorporated residues. The type of crop residue had no effect on the CH4 emissions, while higher N2O emissions were observed from serradella (leguminous) than from ryegrass, but only when the residues were left on the soil surface. The more intense soil reduction verified in the deeper soil layer (20 cm), as evidenced by higher contents of reduced metal species (Mn2+ and Fe2+), and the close relationship between CH4 emission and the DOC contents in the deeper layer indicated that the sub-surface layer was the main CH4 source of the flooded soil with incorporated crop residues. The adoption of management strategies in which crop residues are left on the soil surface is crucial to minimize soil CH4 and N2O emissions from irrigated rice fields. In these production systems, CH4 accounts for more than 90 % of the partial global warming potential (CH4+N2O) and, thus, should be the main focus of research.

Long-term C-CO2 emissions and carbon crop residue mineralization in an oxisol under different tillage and crop rotation systems

Soil C-CO2 emissions are sensitive indicators of management system impacts on soil organic matter (SOM). The main soil C-CO2 sources at the soil-plant interface are the decomposition of crop residues, SOM turnover, and respiration of roots and soil biota. The objectives of this study were to evaluate the impacts of tillage and cropping systems on long-term soil C-CO2 emissions and their relationship with carbon (C) mineralization of crop residues. A long-term experiment was conducted in a Red Oxisol in Cruz Alta, RS, Brazil, with subtropical climate Cfa (Köppen classification), mean annual precipitation of 1,774 mm and mean annual temperature of 19.2 ºC. Treatments consisted of two tillage systems: (a) conventional tillage (CT) and (b) no tillage (NT) in combination with three cropping systems: (a) R0- monoculture system (soybean/wheat), (b) R1- winter crop rotation (soybean/wheat/soybean/black oat), and (c) R2- intensive crop rotation (soybean/ black oat/soybean/black oat + common vetch/maize/oilseed radish/wheat). The soil C-CO2 efflux was measured every 14 days for two years (48 measurements), by trapping the CO2 in an alkaline solution. The soil gravimetric moisture in the 0-0.05 m layer was determined concomitantly with the C-CO2 efflux measurements. The crop residue C mineralization was evaluated with the mesh-bag method, with sampling 14, 28, 56, 84, 112, and 140 days after the beginning of the evaluation period for C measurements. Four C conservation indexes were used to assess the relation between C-CO2 efflux and soil C stock and its compartments. The crop residue C mineralization fit an exponential model in time. For black oat, wheat and maize residues, C mineralization was higher in CT than NT, while for soybean it was similar. Soil moisture was higher in NT than CT, mainly in the second year of evaluation. There was no difference in tillage systems for annual average C-CO2 emissions, but in some individual evaluations, differences between tillage systems were noticed for C-CO2 evolution. Soil C-CO2 effluxes followed a bi-modal pattern, with peaks in October/November and February/March. The highest emission was recorded in the summer and the lowest in the winter. The C-CO2 effluxes were weakly correlated to air temperature and not correlated to soil moisture. Based on the soil C conservation indexes investigated, NT associated to intensive crop rotation was more C conserving than CT with monoculture.

Uncertainties in the prediction of spatial variability of soil CO2 emissions and related properties

The soil CO2 emission has high spatial variability because it depends strongly on soil properties. The purpose of this study was to (i) characterize the spatial variability of soil respiration and related properties, (ii) evaluate the accuracy of results of the ordinary kriging method and sequential Gaussian simulation, and (iii) evaluate the uncertainty in predicting the spatial variability of soil CO2 emission and other properties using sequential Gaussian simulations. The study was conducted in a sugarcane area, using a regular sampling grid with 141 points, where soil CO2 emission, soil temperature, air-filled pore space, soil organic matter and soil bulk density were evaluated. All variables showed spatial dependence structure. The soil CO2 emission was positively correlated with organic matter (r = 0.25, p < 0.05) and air-filled pore space (r = 0.27, p < 0.01) and negatively with soil bulk density (r = -0.41, p < 0.01). However, when the estimated spatial values were considered, the air-filled pore space was the variable mainly responsible for the spatial characteristics of soil respiration, with a correlation of 0.26 (p < 0.01). For all variables, individual simulations represented the cumulative distribution functions and variograms better than ordinary kriging and E-type estimates. The greatest uncertainties in predicting soil CO2 emission were associated with areas with the highest estimated values, which produced estimates from 0.18 to 1.85 t CO2 ha-1, according to the different scenarios considered. The knowledge of the uncertainties generated by the different scenarios can be used in inventories of greenhouse gases, to provide conservative estimates of the potential emission of these gases.

N2O emissions from a cultivated mollisol: optimal time of day for sampling and the role of soil temperature

The correct use of closed field chambers to determine N2O emissions requires defining the time of day that best represents the daily mean N2O flux. A short-term field experiment was carried out on a Mollisol soil, on which annual crops were grown under no-till management in the Pampa Ondulada of Argentina. The N2O emission rates were measured every 3 h for three consecutive days. Fluxes ranged from 62.58 to 145.99 ∝g N-N2O m-2 h-1 (average of five field chambers) and were negatively related (R² = 0.34, p < 0.01) to topsoil temperature (14 - 20 ºC). N2O emission rates measured between 9:00 and 12:00 am presented a high relationship to daily mean N2O flux (R² = 0.87, p < 0.01), showing that, in the study region, sampling in the mornings is preferable for GHG.

Biochar and soil nitrous oxide emissions

The objective of this work was to evaluate the effect of biochar application on soil nitrous oxide emissions. The experiment was carried out in pots under greenhouse conditions. Four levels of ground commercial charcoal of 2 mm (biochar) were evaluated in a sandy Albaqualf (90% of sand): 0, 3, 6, and 9 Mg ha-1. All treatments received 100 kg ha-1 of N as urea. A cubic effect of biochar levels was observed on the N2O emissions. Biochar doses above 5 Mg ha-1 started to mitigate the emissions in the evaluated soil. However, lower doses promote the emissions.

Origem e implicações dos ácidos carboxílicos na atmosfera

A general overview about the ambient levels of low molecular weight carboxylic acids and their possible emission sources, as well as the implication of them in the atmosphere is presented. Carboxylic acids are considered to be one of the dominant classes of organic compounds found in the atmosphere in a variety of phases, such as in rainwater, snow and ice, on aerosol particles and gas phase. They may be originated from biogenic and anthropogenic direct emissions and by photochemical reaction in situ. Emission sources and formation mechanisms of organic acids in the atmosphere are discussed.

Nitrous oxide emissions from an intermittent aeration activated sludge system of an urban wastewater treatment plant

This study investigated the emission of N2O during the sequential aerated (60-min) and non-aerated (30-min) stages of an intermittent aeration cycle in an activated sludge wastewater treatment plant (WWTP). N2O emission occurred during both stages; however, emission was much higher during aeration. Air stripping is the major factor controlling transfer of N2O from the sewage to the atmosphere. The N2O emissions exclusively from the aeration tank represented 0.10% of the influent total nitrogen load and the per capita emission factor was almost 3 times higher than that suggested by the IPCC for inventories of N2O emission from WWTPs.

Crop residues on short-term CO2 emissions in sugarcane production areas

The proper management of agricultural crop residues could produce benefits in a warmer, more drought-prone world. Field experiments were conducted in sugarcane production areas in the Southern Brazil to assess the influence of crop residues on the soil surface in short-term CO2 emissions. The study was carried out over a period of 50 days after establishing 6 plots with and without crop residues applied to the soil surface. The effects of sugarcane residues on CO2 emissions were immediate; the emissions from residue-covered plots with equivalent densities of 3 (D50) and 6 (D100) t ha-1 (dry mass) were less than those from non-covered plots (D0). Additionally, the covered fields had lower soil temperatures and higher soil moisture for most of the studied days, especially during the periods of drought. Total emissions were as high as 553.62 ± 47.20 g CO2 m-2, and as low as 384.69 ± 31.69 g CO2 m-2 in non-covered (D0) and covered plot with an equivalent density of 3 t ha-1 (D50), respectively. Our results indicate a significant reduction in CO2 emissions, indicating conservation of soil carbon over the short-term period following the application of sugarcane residues to the soil surface.

Control of ammonia emissions in naturally ventilated dairy cattle facilities in Portugal

We conducted a study of the processes associated to NH3 emission in naturally ventilated dairy cattle facilities, having described factors that regulate NH3 emission, as well as methodologies for measuring these emissions at these facilities. Appropriate techniques to mitigate NH3 emission in facilities located in regions with warm climates were also identified. The most effective mitigation techniques with simple implementation include strategies associated to: (i) installation design and flooring, which lead to reduced emissions, (ii) excreta pre-excretion, namely the use of diets with optimized crude protein content and increased milk production at farm level; and (iii) excreta post-excretion, particularly by changing the conditions of environmental monitoring within the premises, practice introduction or additive application in the management of excreta deposited on floors.

Emissão por folhas de Ficus benjamina L. (Moraceae) de compostos orgânicos voláteis oxigenados

A vegetação é a fonte de aproximadamente 90% de todos os compostos orgânicos voláteis na atmosfera global. Alguns hidrocarbonetos oxigenados emitidos por plantas reagem com radicais livres, tais como nitrato e hidroxila, e ozônio em taxas comparáveis com aquelas dos compostos antropogênicos mais reativos e podem contribuir para a formação de ozônio em áreas urbanas. Apesar do papel importante dos hidrocarbonetos naturais na formação fotoquímica dos oxidantes, pouco se sabe sobre as espécies químicas dos compostos orgânicos voláteis emitidos por plantas. Nesse trabalho, foi estudada a emissão de compostos orgânicos voláteis por Ficus benjamina, espécie comumente encontrada na região da cidade de São Paulo. Os gases emitidos pelas folhas da F. benjamina foram coletados em sistemas fechados e vários compostos orgânicos voláteis oxigenados, tais como ácidos orgânicos (ácido fórmico e ácido acético), aldeídos (formaldeído, acetaldeído e hexanal) e álcoois (mentol, 1- butanol, 1-pentanol, 2-penten-1-ol, 4-penten-2-ol e linalool), foram identificados através de técnicas cromatográficas.

Changes in the biogenic amine content of the prefrontal cortex, amygdala, dorsal hippocampus, and nucleus accumbens of rats submitted to single and repeated sessions of the elevated plus-maze test

It has been demonstrated that exposure to a variety of stressful experiences enhances fearful reactions when behavior is tested in current animal models of anxiety. Until now, no study has examined the neurochemical changes during the test and retest sessions of rats submitted to the elevated plus maze (EPM). The present study uses a new approach (HPLC) by looking at the changes in dopamine and serotonin levels in the prefrontal cortex, amygdala, dorsal hippocampus, and nucleus accumbens in animals upon single or double exposure to the EPM (one-trial tolerance). The study involved two experiments: i) saline or midazolam (0.5 mg/kg) before the first trial, and ii) saline or midazolam before the second trial. For the biochemical analysis a control group injected with saline and not tested in the EPM was included. Stressful stimuli in the EPM were able to elicit one-trial tolerance to midazolam on re-exposure (61.01%). Significant decreases in serotonin contents occurred in the prefrontal cortex (38.74%), amygdala (78.96%), dorsal hippocampus (70.33%), and nucleus accumbens (73.58%) of the animals tested in the EPM (P < 0.05 in all cases in relation to controls not exposed to the EPM). A significant decrease in dopamine content was also observed in the amygdala (54.74%, P < 0.05). These changes were maintained across trials. There was no change in the turnover rates of these monoamines. We suggest that exposure to the EPM causes reduced monoaminergic neurotransmission activity in limbic structures, which appears to underlie the "one-trial tolerance" phenomenon.