Downwelling solar irradiance in the biomass burning region of the southern Amazon: Dependence on aerosol intensive optical properties and role of water vapor

The sensitivity of solar irradiance at the surface to the variability of aerosol intensive optical properties is investigated for a site (Alta Floresta) in the southern portion of the Amazon basin using detailed comparisons between measured and modeled irradiances. Apart from aerosol intensive optical properties, specifically single scattering albedo (omega(o lambda)) and asymmetry parameter (g(lambda)), which were assumed constant, all other relevant input to the model were prescribed based on observation. For clean conditions, the differences between observed and modeled irradiances were consistent with instrumental uncertainty. For polluted conditions, the agreement was significantly worse, with a root mean square difference three times larger (23.5 Wm(-2)). Analysis revealed a noteworthy correlation between the irradiance differences (observed minus modeled) and the column water vapor (CWV) for polluted conditions. Positive differences occurred mostly in wet conditions, while the differences became more negative as the atmosphere dried. To explore the hypothesis that the irradiance differences might be linked to the modulation of omega(o lambda) and g(lambda) by humidity, AERONET retrievals of aerosol properties and CWV over the same site were analyzed. The results highlight the potential role of humidity in modifying omega(o lambda) and g(lambda) and suggest that to explain the relationship seen between irradiances differences via aerosols properties the focus has to be on humidity-dependent processes that affect particles chemical composition. Undoubtedly, there is a need to better understand the role of humidity in modifying the properties of smoke aerosols in the southern portion of the Amazon basin.

Fluxes of CO(2) above a plantation of Eucalyptus in southeast Brazil

Eddy-covariance measurements of net ecosystem exchange of CO(2) (NEE) and estimates of gross ecosystem productivity (GEP) and ecosystem respiration (R(E)) were obtained in a 2-4 year old Eucalyptus plantation during two years with very different winter rainfall In the first (drier) year the annual NEE GEP and RE were lower than the sums in the second (normal) year and conversely the total respiratory costs of assimilated carbon were higher in the dry year than in the normal year Although the net primary production (NPP) in the first year was 23% lower than that of the second year the decrease in the carbon use efficiency (CUE = NPP/GEP) was 11% and autotrophic respiration utilized more resources in the first dry year than in the second normal year The time variations in NEE were followed by NPP because in these young Eucalyptus plantations NEE is very largely dominated by NPP and heterotrophic respiration plays only a relatively minor role During the dry season a pronounced hysteresis was observed in the relationship between NEE and photosynthetically active radiation and NEE fluxes were inversely proportional to humidity saturation deficit values greater than 0 8 kPa Nighttime fluxes of CO(2) during calm conditions when the friction velocity (u) was below the threshold (0 25 ms(-1)) were estimated based on a Q(10) temperature-dependence relationship adjusted separately for different classes of soil moisture content which regulated the temperature sensitivity of ecosystem respiration (C) 2010 Elsevier B V All rights reserved

Atmosphere and hydrological controls of the evapotranspiration over a floodplain forest in the Bananal Island region, Amazonia

This article discusses seasonal and interannual variations of the evapotranspiration (ET) rates in Bananal Island floodplain, Brazil. Measurements included ET and sensible heat flux using the eddy covariance method, atmospheric forcings (net radiation, Rn, vapor pressure deficit, VPD, wind speed and air temperature), soil moisture profiles, groundwater level and flood height, taken from November 2003 to December 2006. For the hydrological years (October-September) of 2003/2004, 2004/2005 and 2005/2006, the accumulated precipitation was 1692, 1471, 1914 mm and the accumulated ET was 1361, 1318 and 1317 mm, respectively. Seasonal analyses indicated that ET decreased in the dry season (average 3.7 mm day(-1)), despite the simultaneous increase in Rn, air temperature and VPD. The increase of ET in the wet season and particularly in the flood period (average 4.1 mm day(-1)) showed that the free water surface evaporation strongly influenced the energy exchange. Soil moisture, which was substantially depleted during the dry season, and adaptative vegetation mechanisms such as leaf senescence contributed to limit the dry season ET. Strong drainage within permeable sandy soils helped to explain the soil moisture depletion. These results suggest that the Bananal flooding area shows a different pattern in relation to the upland Amazon forests, being more similar to the savanna strictu senso areas in central Brazil. For example, seasonal ET variation was not in phase with Rn; the wet season ET was higher than the dry season ET; and the system stored only a tiny memory of the flooding period, being sensitive to extended drought periods.

Patterns of water and heat flux across a biome gradient from tropical forest to savanna in Brazil

We investigated the seasonal patterns of water vapor and sensible heat flux along a tropical biome gradient from forest to savanna. We analyzed data from a network of flux towers in Brazil that were operated within the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA). These tower sites included tropical humid and semideciduous forest, transitional forest, floodplain (with physiognomies of cerrado), and cerrado sensu stricto. The mean annual sensible heat flux at all sites ranged from 20 to 38 Wm(-2), and was generally reduced in the wet season and increased in the late dry season, coincident with seasonal variations of net radiation and soil moisture. The sites were easily divisible into two functional groups based on the seasonality of evaporation: tropical forest and savanna. At sites with an annual precipitation above 1900 mm and a dry season length less than 4 months (Manaus, Santarem and Rondonia), evaporation rates increased in the dry season, coincident with increased radiation. Evaporation rates were as high as 4.0 mm d(-1) in these evergreen or semidecidous forests. In contrast, ecosystems with precipitation less than 1700 mm and a longer dry season (Mato Grosso, Tocantins and Sao Paulo) showed clear evidence of reduced evaporation in the dry season. Evaporation rates were as low as 2.5 mm d(-1) in the transitional forests and 1 mm d(-1) in the cerrado. The controls on evapotranspiration seasonality changed along the biome gradient, with evaporative demand (especially net radiation) playing a more important role in the wetter forests, and soil moisture playing a more important role in the drier savannah sites.

Observational Characterization of the Downward Atmospheric Longwave Radiation at the Surface in the City of Sao Paulo

This work describes the seasonal and diurnal variations of downward longwave atmospheric irradiance (LW) at the surface in Sao Paulo, Brazil, using 5-min-averaged values of LW, air temperature, relative humidity, and solar radiation observed continuously and simultaneously from 1997 to 2006 on a micrometeorological platform, located at the top of a 4-story building. An objective procedure, including 2-step filtering and dome emission effect correction, was used to evaluate the quality of the 9-yr-long LW dataset. The comparison between LW values observed and yielded by the Surface Radiation Budget project shows spatial and temporal agreement, indicating that monthly and annual average values of LW observed in one point of Sao Paulo can be used as representative of the entire metropolitan region of Sao Paulo. The maximum monthly averaged value of the LW is observed during summer (389 +/- 14 W m(-2): January), and the minimum is observed during winter (332 +/- 12 W m(-2); July). The effective emissivity follows the LW and shows a maximum in summer (0.907 +/- 0.032; January) and a minimum in winter (0.818 +/- 0.029; June). The mean cloud effect, identified objectively by comparing the monthly averaged values of the LW during clear-sky days and all-sky conditions, intensified the monthly average LW by about 32.0 +/- 3.5 W m(-2) and the atmospheric effective emissivity by about 0.088 +/- 0.024. In August, the driest month of the year in Sao Paulo, the diurnal evolution of the LW shows a minimum (325 +/- 11 W m(-2)) at 0900 LT and a maximum (345 12 W m-2) at 1800 LT, which lags behind (by 4 h) the maximum diurnal variation of the screen temperature. The diurnal evolution of effective emissivity shows a minimum (0.781 +/- 0.027) during daytime and a maximum (0.842 +/- 0.030) during nighttime. The diurnal evolution of all-sky condition and clear-sky day differences in the effective emissivity remain relatively constant (7% +/- 1%), indicating that clouds do not change the emissivity diurnal pattern. The relationship between effective emissivity and screen air temperature and between effective emissivity and water vapor is complex. During the night, when the planetary boundary layer is shallower, the effective emissivity can be estimated by screen parameters. During the day, the relationship between effective emissivity and screen parameters varies from place to place and depends on the planetary boundary layer process. Because the empirical expressions do not contain enough information about the diurnal variation of the vertical stratification of air temperature and moisture in Sao Paulo, they are likely to fail in reproducing the diurnal variation of the surface emissivity. The most accurate way to estimate the LW for clear-sky conditions in Sao Paulo is to use an expression derived from a purely empirical approach.

Cloud condensation nuclei in pristine tropical rainforest air of Amazonia: size-resolved measurements and modeling of atmospheric aerosol composition and CCN activity

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. We have measured and characterized CCN at water vapor supersaturations in the range of S=0.10-0.82% in pristine tropical rainforest air during the AMAZE-08 campaign in central Amazonia. The effective hygroscopicity parameters describing the influence of chemical composition on the CCN activity of aerosol particles varied in the range of kappa approximate to 0.1-0.4 (0.16+/-0.06 arithmetic mean and standard deviation). The overall median value of kappa approximate to 0.15 was by a factor of two lower than the values typically observed for continental aerosols in other regions of the world. Aitken mode particles were less hygroscopic than accumulation mode particles (kappa approximate to 0.1 at D approximate to 50 nm; kappa approximate to 0.2 at D approximate to 200 nm), which is in agreement with earlier hygroscopicity tandem differential mobility analyzer (H-TDMA) studies. The CCN measurement results are consistent with aerosol mass spectrometry (AMS) data, showing that the organic mass fraction (f(org)) was on average as high as similar to 90% in the Aitken mode (D <= 100 nm) and decreased with increasing particle diameter in the accumulation mode (similar to 80% at D approximate to 200 nm). The kappa values exhibited a negative linear correlation with f(org) (R(2)=0.81), and extrapolation yielded the following effective hygroscopicity parameters for organic and inorganic particle components: kappa(org)approximate to 0.1 which can be regarded as the effective hygroscopicity of biogenic secondary organic aerosol (SOA) and kappa(inorg)approximate to 0.6 which is characteristic for ammonium sulfate and related salts. Both the size dependence and the temporal variability of effective particle hygroscopicity could be parameterized as a function of AMS-based organic and inorganic mass fractions (kappa(p)=kappa(org) x f(org)+kappa(inorg) x f(inorg)). The CCN number concentrations predicted with kappa(p) were in fair agreement with the measurement results (similar to 20% average deviation). The median CCN number concentrations at S=0.1-0.82% ranged from N(CCN,0.10)approximate to 35 cm(-3) to N(CCN,0.82)approximate to 160 cm(-3), the median concentration of aerosol particles larger than 30 nm was N(CN,30)approximate to 200 cm(-3), and the corresponding integral CCN efficiencies were in the range of N(CCN,0.10/NCN,30)approximate to 0.1 to N(CCN,0.82/NCN,30)approximate to 0.8. Although the number concentrations and hygroscopicity parameters were much lower in pristine rainforest air, the integral CCN efficiencies observed were similar to those in highly polluted megacity air. Moreover, model calculations of N(CCN,S) assuming an approximate global average value of kappa approximate to 0.3 for continental aerosols led to systematic overpredictions, but the average deviations exceeded similar to 50% only at low water vapor supersaturation (0.1%) and low particle number concentrations (<= 100 cm(-3)). Model calculations assuming aconstant aerosol size distribution led to higher average deviations at all investigated levels of supersaturation: similar to 60% for the campaign average distribution and similar to 1600% for a generic remote continental size distribution. These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the information and parameterizations presented in this paper should enable efficient description of the CCN properties of pristine tropical rainforest aerosols of Amazonia in detailed process models as well as in large-scale atmospheric and climate models.

Physical controls on carbon dioxide transfer velocity and flux in low-gradient river systems and implications for regional carbon budgets

Outgassing of carbon dioxide (CO(2)) from rivers and streams to the atmosphere is a major loss term in the coupled terrestrial-aquatic carbon cycle of major low-gradient river systems (the term ""river system"" encompasses the rivers and streams of all sizes that compose the drainage network in a river basin). However, the magnitude and controls on this important carbon flux are not well quantified. We measured carbon dioxide flux rates (F(CO2)), gas transfer velocity (k), and partial pressures (p(CO2)) in rivers and streams of the Amazon and Mekong river systems in South America and Southeast Asia, respectively. F(CO2) and k values were significantly higher in small rivers and streams (channels <100 m wide) than in large rivers (channels >100 m wide). Small rivers and streams also had substantially higher variability in k values than large rivers. Observed F(CO2) and k values suggest that previous estimates of basinwide CO(2) evasion from tropical rivers and wetlands have been conservative and are likely to be revised upward substantially in the future. Data from the present study combined with data compiled from the literature collectively suggest that the physical control of gas exchange velocities and fluxes in low-gradient river systems makes a transition from the dominance of wind control at the largest spatial scales (in estuaries and river mainstems) toward increasing importance of water current velocity and depth at progressively smaller channel dimensions upstream. These results highlight the importance of incorporating scale-appropriate k values into basinwide models of whole ecosystem carbon balance.

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.

Effect of bituminous impregnation on nonwoven geotextiles tensile and permeability properties

Geosynthetics interlayer systems are effective techniques to control reflective cracking in damaged pavements. It comprises the inclusion of nonwoven geotextiles between the damaged layer and the new overlay of the pavement to reduce the propagation of cracks and to extend pavement life. However, the success of this technique depends directly on the understanding of the geotextile`s behavior when impregnated with asphalt This paper evaluates different nonwoven geotextiles frequently used in anti-reflective cracking systems, focusing on initial stiffness gain and permeability reduction after asphalt impregnation. Fresh and impregnated samples of polyester and polypropylene nonwoven geotextiles were tested. Cationic rapid setting emulsified asphalt was used as asphalt binder. Wide-width tensile tests were carried out based on the specification of ABNT - NBR 12824 (1993). Water vapor transmission tests were conducted according to ASTM E 96M (2005). Results of tensile tests on impregnated geotextiles showed a significant increase on tensile strength values, probably due to the inter contact of the fibers. Results also showed high increase in strength values at strain levels less than 0.05% and decrease on stiffness gains with increase of strains. Water vapor transmission tests demonstrated that cationic asphalt emulsion applied on nonwoven geotextiles allows a drastic reduction in permeability values to turn nonwoven geotextiles into a low permeability barrier. (C) 2010 Elsevier Ltd. All rights reserved.

Electrospray MS-based characterization of beta-carbolines - mutagenic constituents of thermally processed meat

The beta-carbolines 1-methyl-9H-pyrido [3,4-b]indole and 9H-pyrido[3,4b]indole have been implicated as having causative roles in a number of human diseases, such as Parkinson`s disease and cancer. As they can be formed during the heating of protein-rich food, a number of analytical methodologies have been proposed for their detection and quantification in foodstuff For this purpose, LC-MS and LC-MS/MS have emerged as the most specific analytical methods, and the quantification is based on the occurrence of unusual ions, such as [M+H-(H(center dot))](+) and [M + H-2H](+). In this study, we have investigated the formation of these ions by accurate-mass electrospray MS/MS and demonstrated that these ions are formed from gas-phase ion-molecule reactions between water vapor present in the collision cell and the protonated molecule of 1-methyl-9H-pyrido [3,4-b]indole and 9H-pyrido[3,4b]indole. Although this reaction has been previously described for heterocyclic amine ions, it has been overlooked in the most of recent LC-MS and LC-MS/MS studies, and no complete data of the fragmentation are reported. Our results demonstrate that additional attention should be given with respect to eliminating water vapor residues in the mass spectrometer when analysis of beta-carbolines is performed, as this residue may affect the reliability in the results of quantification.

Effect of the Maillard reaction on properties of casein and casein films

The use of biodegradable natural polymers has increased due to the over-solid packaging waste. In this study, a chemical modification of the casein molecule was performed by Maillard reaction, and the modified polymer was evaluated by polyacrylamide gel electrophoresis (PAGE), thermogravimetry/derivative thermogravimetry (TG/DTG), FT-IR, and (1)H-NMR spectroscopy. Subsequently, films based on the modified casein were obtained and characterized by mechanical analysis, water vapor transmission, and erosion behavior. The PAGE results suggested an increase of molecular mass of the modified polymer, and FT-IR spectroscopy data indicated inclusion of C-OH groups into this molecule. The TG/DTG curves of modified casein presented a different thermal decomposition profile compared to the individual compounds. Mechanical tests showed that the chemical modification of the casein molecules provided higher elongation rates (45.5%) to the films, suggesting higher plasticity, than the original molecules (13.4%). The modified casein films presented higher permeability (0.505 +/- A 0.006 mu g/h mm(3)) than the original polymer (0.387 +/- A 0.006 mu g/h mm(3)) films at 90% relative humidity (RH). In pH 1.2, modified casein films presented higher erosion rates (32.690 +/- A 0.692%) than casein films (19.910 +/- A 2.083%) after 8 h, suggesting an increased sensibility for erosion of the modified casein films in acid environment. In water (pH 7.0), the films erosion profiles were similar. Those findings indicate that the modification of molecule by Maillard reaction provided films more plastic, hydrophilic, and sensitive to erosion in acid environment, suggesting that a new polymer with changed properties was founded.

Effect of surfactants on the functional properties of gelatin-based edible films

The aim of this research was to evaluate the plasticizing effect of natural surfactants lecithin or yucca extract from Yucca schidigera on gelatin-based films Films containing yucca extract showed higher tensile strength values (similar to 90-40 MPa) and moisture contents (similar to 15%) and less elongation (similar to 5%) and water vapor permeability values (similar to 0 22-009 g mm m(-2) h(-1) kPa(-1)) compared to films containing lecithin Soluble films (similar to 20-50%) were obtained when yucca extract was used while lecithin produced low soluble films (<10%) The opacity of the films (similar to 14 5-16 2%) was similar for both surfactants and the film surface morphologies were continuous and homogeneous X-ray diffraction indicated that the addition of surfactants produced amorphous films compared to gelatin-based films and FT-Infrared spectroscopy showed no evidence of association between the surfactants and the gelatin The plasticizing effect was not obtained after surfactants addition and casting technique (C) 2010 Elsevier Ltd All rights reserved

Natural antimicrobial ingredients incorporated in biodegradable films based on cassava starch

Biodegradable films based on cassava starch and with addition of natural antimicrobial ingredients were prepared using the casting technique. The tensile properties tensile strength (TS) [MPa] and percent elongation (E) at break [%] and the water vapor transmission (WVT) of the biodegradable films were evaluated and compared with the control (without antimicrobial ingredients). The evaluation of the Colony Forming Units per gram [CFU/g] of pan bread slices packed with the best biodegradable films, in terms of packaging performance, was also determined. The addition onto the matrix of only clove and cinnamon powders could reduce the films WVT when compared to the control, however TS and E were lower than the control and the effect of cinnamon was milder regarding this property. Since water activity of the pan bread slices packed with the biodegradable films increased considerably during the storage period, the antimicrobial effect could not be clearly determined. (C) 2010 Published by Elsevier Ltd.

Gelatin-based films containing hydrophobic plasticizers and saponin from Yucca schidigera as the surfactant

The aim of this study was to evaluate the incorporation of hydrophobic plasticizers (acetyltributyl citrate - ATB, tributyl citrate - TB and acetyltriethyl citrate - ATC) in a matrix of gelatin, using the saponin extracted from Yucca schidigera (yucca) as emulsifier, in the production of biodegradable emulsified films using the casting technique. High levels of hydrophobic plasticizers were incorporated, reaching up to 75% of plasticizer in relation to the protein (w/w) for ATB and TB, and up to 60% for ATC. The minimum values of water vapor permeability were 0.08, 0.07 and 0.06 g mm m(-2) h(-1) kPa(-1) for ATB, TB and ATC respectively, with no significant differences (p > 0.05). The water solubility of the films ranged from 21% to 59.5%. Although the WVP decreased, both scanning electron microscopy and laser scanning confocal microscopy indicated that the incorporation of the hydrophobic plasticizers did not occur homogeneously in the film matrix. (C) 2010 Elsevier Ltd. All rights reserved.

Optimization of amaranth flour films plasticized with glycerol and sorbitol by multi-response analysis

The optimal formulation for the preparation of amaranth flour films plasticized with glycerol and sorbitol was obtained by a multi-response analysis. The optimization aimed to achieve films with higher resistance to break, moderate elongation and lower solubility in water. The influence of plasticizer concentration (Cg, glycerol or Cs, sorbitol) and process temperature (Tp) on the mechanical properties and solubility of the amaranth flour films was initially studied by response surface methodology (RSM). The optimized conditions obtained were Cg 20.02 g glycerol/100 g flour and Tp 75 degrees C, and Cs 29.6 g sorbitol/100 g flour and Tp 75 degrees C. Characterization of the films prepared with these formulations revealed that the optimization methodology employed in this work was satisfactory. Sorbitol was the most suitable plasticizer. It furnished amaranth flour films that were more resistant to break and less permeable to oxygen, due to its greater miscibility with the biopolymers present in the flour and its lower affinity for water. (C) 2011 Elsevier Ltd. All rights reserved.