Sources of carbonaceous aerosol in the Amazon basin

The quantification of sources of carbonaceous aerosol is important to understand their atmospheric concentrations and regulating processes and to study possible effects on climate and air quality, in addition to develop mitigation strategies. In the framework of the European Integrated Project on Aerosol Cloud Climate Interactions (EUCAARI) fine (D(p) < 2.5 mu m) and coarse (2.5 mu m < Dp < 10 mu m) aerosol particles were sampled from February to June (wet season) and from August to September (dry season) 2008 in the central Amazon basin. The mass of fine particles averaged 2.4 mu g m(-3) during the wet season and 4.2 mu g m(-3) during the dry season. The average coarse aerosol mass concentration during wet and dry periods was 7.9 and 7.6 mu g m(-3), respectively. The overall chemical composition of fine and coarse mass did not show any seasonality with the largest fraction of fine and coarse aerosol mass explained by organic carbon (OC); the average OC to mass ratio was 0.4 and 0.6 in fine and coarse aerosol modes, respectively. The mass absorbing cross section of soot was determined by comparison of elemental carbon and light absorption coefficient measurements and it was equal to 4.7 m(2) g(-1) at 637 nm. Carbon aerosol sources were identified by Positive Matrix Factorization (PMF) analysis of thermograms: 44% of fine total carbon mass was assigned to biomass burning, 43% to secondary organic aerosol (SOA), and 13% to volatile species that are difficult to apportion. In the coarse mode, primary biogenic aerosol particles (PBAP) dominated the carbonaceous aerosol mass. The results confirmed the importance of PBAP in forested areas. The source apportionment results were employed to evaluate the ability of global chemistry transport models to simulate carbonaceous aerosol sources in a regional tropical background site. The comparison showed an overestimation of elemental carbon (EC) by the TM5 model during the dry season and OC both during the dry and wet periods. The overestimation was likely due to the overestimation of biomass burning emission inventories and SOA production over tropical areas.

Synergistic interaction between gold nanoparticles and nickel phthalocyanine in layer-by-layer (LbL) films: evidence of constitutional dynamic chemistry (CDC)

The concept of constitutional dynamic chemistry (CDC) based on the control of non-covalent interactions in supramolecular structures is promising for having a large impact on nanoscience and nanotechnology if adequate nanoscale manipulation methods are used. In this study, we demonstrate that the layer-by-layer (LbL) technique may be used to produce electroactive electrodes with ITO coated by tetrasulfonated nickel phthalocyanine (NiTsPc) alternated with poly(allylamine hydrochloride) (PAH) incorporating gold nanoparticles (AuNP), in which synergy has been achieved in the interaction between the nanoparticles and NiTsPc. The catalytic activity toward hydrogen peroxide (H(2)O(2)) in multilayer films was investigated using cyclic voltammetry, where oxidation of H(2)O(2) led to increased currents in the PAH-AuNP/NiTsPc films for the electrochemical processes associated with the phthalocyanine ring and nickel at 0.52 and 0.81 V vs. SCE, respectively, while for PAH/NiTsPc films (without AuNP) only the first redox process was affected. In control experiments we found out that the catalytic activity was not solely due to the presence of AuNP, but rather to the nanoparticles inducing NiTsPc supramolecular structures that favored access to their redox sites, thus yielding strong charge transfer. The combined effects of NiTsPc and AuNP, which could only be observed in nanostructured LbL films, point to another avenue to pursue within the CDC paradigm.

Stability of biomass-derived black carbon in soils

Black carbon (BC) may play ail important role in the global C budget, due to its potential to act as a significant sink of atmospheric CO(2). In order to fully evaluate the influence of BC oil the global C cycle, in understanding of the stability of BC is required. The biochemical stability of BC was assessed in a chronosequence of high-BC-containing Anthrosols from the central Amazon, Brazil, using a range of spectroscopic and biological methods. Results revealed that the Anthrosols had 61-80% lower (P < 0.05) CO(2) evolution per unit C over 532 days compared to their respective adjacent soils with low BC contents. No significant (P > 0.05) difference in CO(2) respiration per unit C was observed between Anthrosols with contrasting ages of BC (600-8700 years BP) Lind soil textures (0.3-36% clay). Similarly, the molecular composition of the core regions of micrometer-sized BC particles quantified by synchrotron-based Near-Edge X-ray Fine Structure (NEXAFS) spectroscopy coupled to Scanning Transmission X-ray Microscopy (STXM) remained similar regardless of their ages and closely resembled the spectral characteristics or fresh BC. BC decomposed extremely slowly to ail extent that it was not possible to detect chemical changes between Youngest and oldest samples, as also confirmed by X-ray Photoelectron Spectroscopy (XPS). Deconvolution of NEXAFS spectra revealed greater oxidation oil the surfaces of BC particles with little penetration into the core of the particles. The similar C mineralization between different BC-rich soils regardless of soil texture underpins the importance of chemical recalcitrance for the stability of BC, in contrast to adjacent soils which showed the highest mineralization in the sandiest soil. However, the BC-rich Anthrosols had higher proportions (72-90%) of C in the more stable organo-mineral fraction than BC-poor adjacent soils (2-70%), Suggesting some degree of physical stabilization. (c) 2008 Elsevier Ltd. All rights reserved.

Forest structure and live aboveground biomass variation along an elevational gradient of tropical Atlantic moist forest (Brazil)

Live aboveground biomass (AGB) is an important source of uncertainty in the carbon balance from the tropical regions in part due scarcity of reliable estimates of live AGB and its variation across landscapes and forest types. Studies of forest structure and biomass stocks of Neotropical forests are biased toward Amazonian and Central American sites. In particular, standardized estimates of aboveground biomass stocks for the Brazilian Atlantic forest are rarely available. Notwithstanding the role of environmental variables that control the distribution and abundance of biomass in tropical lowland forests has been the subject of considerable research, the effect of short, steep elevational gradients on tropical forest structure and carbon dynamics is not well known. In order to evaluate forest structure and live AGB variation along an elevational gradient (0-1100 m a.s.l.) of coastal Atlantic Forest in SE Brazil, we carried out a standard census of woody stems >= 4.8 cm dbh in 13 1-ha permanent plots established on four different sites in 2006-2007. Live AGB ranged from 166.3 Mg ha(-1) (bootstrapped 95% CI: 1444,187.0) to 283.2 Mg ha(-1) (bootstrapped 95% CI: 253.0,325.2) and increased with elevation. We found that local-scale topographic variation associated with elevation influences the distribution of trees >50 cm dbh and total live AGB. Across all elevations, we found more stems (64-75%) with limited crown illumination but the largest proportion of the live AGB (68-85%) was stored in stems with highly illuminated or fully exposed crowns. Topography, disturbance and associated changes in light and nutrient supply probably control biomass distribution along this short but representative elevational gradient. Our findings also showed that intact Atlantic forest sites stored substantial amounts of carbon aboveground. The live tree AGB of the stands was found to be lower than Central Amazonian forests, but within the range of Neotropical forests, in particular when compared to Central American forests. Our comparative data suggests that differences in live tree AGB among Neotropical forests are probably related to the heterogeneous distribution of large and medium-sized diameter trees within forests and how the live biomass is partitioned among those size classes, in accordance with general trends found by previous studies. In addition, the elevational variation in live AGB stocks suggests a large spatial variability over coastal Atlantic forests in Brazil, clearly indicating that it is important to consider regional differences in biomass stocks for evaluating the role of this threatened tropical biome in the global carbon cycle. (C) 2010 Elsevier B.V. All rights reserved.

Biomass burning in Brazil`s Amazonian ""arc of deforestation"": Burning efficiency and charcoal formation in a fire after mechanized clearing at Feliz Natal, Mato Grosso

Estimates of greenhouse-gas emissions from deforestation are highly uncertain because of high variability in key parameters and because of the limited number of studies providing field measurements of these parameters. One such parameter is burning efficiency, which determines how much of the original forest`s aboveground carbon stock will be released in the burn, as well as how much will later be released by decay and how much will remain as charcoal. In this paper we examined the fate of biomass from a semideciduous tropical forest in the ""arc of deforestation,"" where clearing activity is concentrated along the southern edge of the Amazon forest. We estimated carbon content, charcoal formation and burning efficiency by direct measurements (cutting and weighing) and by line-intersect sampling (LIS) done along the axis of each plot before and after burning of felled vegetation. The total aboveground dry biomass found here (219.3 Mg ha(-1)) is lower than the values found in studies that have been done in other parts of the Amazon region. Values for burning efficiency (65%) and charcoal formation (6.0%, or 5.98 Mg C ha(-1)) were much higher than those found in past studies in tropical areas. The percentage of trunk biomass lost in burning (49%) was substantially higher than has been found in previous studies. This difference may be explained by the concentration of more stems in the smaller diameter classes and the low humidity of the fuel (the dry season was unusually long in 2007, the year of the burn). This study provides the first measurements of forest burning parameters for a group of forest types that is now undergoing rapid deforestation. The burning parameters estimated here indicate substantially higher burning efficiency than has been found in other Amazonian forest types. Quantification of burning efficiency is critical to estimates of trace-gas emissions from deforestation. (C) 2009 Elsevier B.V. All rights reserved.

Dynamics of carbon, biomass, and structure in two Amazonian forests

Amazon forests are potentially globally significant sources or sinks for atmospheric carbon dioxide. In this study, we characterize the spatial trends in carbon storage and fluxes in both live and dead biomass (necromass) in two Amazonian forests, the Biological Dynamic of Forest Fragments Project (BDFFP), near Manaus, Amazonas, and the Tapajos National Forest (TNF) near Santarem, Para. We assessed coarse woody debris (CWD) stocks, tree growth, mortality, and recruitment in ground-based plots distributed across the terra firme forest at both sites. Carbon dynamics were similar within each site, but differed significantly between the sites. The BDFFP and the TNF held comparable live biomass (167 +/- 7.6 MgC.ha(-1) versus 149 +/- 6.0 MgC.ha(-1), respectively), but stocks of CWD were 2.5 times larger at TNF (16.2 +/- 1.5 MgC.ha(-1) at BDFFP, versus 40.1 +/- 3.9 MgC.ha(-1) at TNF). A model of current forest dynamics suggests that the BDFFP was close to carbon balance, and its size class structure approximated a steady state. The TNF, by contrast, showed rapid carbon accrual to live biomass (3.24 +/- 0.22 MgC.ha(-1).a(-1) in TNF, 2.59 +/- 0.16 MgC.ha(-1).a(-1) in BDFFP), which was more than offset by losses from large stocks of CWD, as well as ongoing shifts of biomass among size classes. This pattern in the TNF suggests recovery from a significant disturbance. The net loss of carbon from the TNF will likely last 10 - 15 years after the initial disturbance (controlled by the rate of decay of coarse woody debris), followed by uptake of carbon as the forest size class structure and composition continue to shift. The frequency and longevity of forests showing such disequilibruim dynamics within the larger matrix of the Amazon remains an essential question to understanding Amazonian 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.

Green Chemistry-Sensitive Analytical Procedure for Photometric Determination of Orthophosphate in River and Tap Water by Use of a Simple LED-Based Photometer

In the current work a Green Analytical Chemistry (GAC) procedure for photometric determination of orthophosphate in river water at mu g L-1 concentration level is described. The flow system module and the LED-based photometer were assembled together to constitute a compact unit in order to allow that a flow cell with optical path-length of 100mm was coupled to them. The photometric procedure based on the molybdenum blue method was implemented employing the multicommuted flow injection analysis approach, which provided facilities to allow reduction of reagent consumption and as well as waste generation. Aiming to prove the usefulness of the system, orthophosphate in river and tap waters was determined. Accuracy was ascertained by spiking samples with orthophosphate solution yielding recoveries ranging from 96% up to 107%. Other profitable features such as a wide linear response range between 10 to 800 mu g L-1 [image omitted]; a detection limit (3 sigma criterion) of 2.4 mu g L-1 [image omitted]; a relative standard deviation (n=7) of 2% using a typical water sample with concentration of 120 mu g L-1 [image omitted]; reagent consumption of 3.0mg ammonium molybdate, 0.3mg hydrazine sulfate, and 0.03mg stannous chloride per determination; a waste generation of 2.4mL per determination; and a sampling throughput of 20 determination per hours were also achieved.

Sources of particulate matter: emission profile of biomass burning

Biomass burning is an important source of atmospheric Particulate Matter (PM) in Brazil: the burning of forests in the northwest and of sugar cane plantations in the southeast are important examples. The objective of this work is the measurement of the PM emission profile of burning of sugar cane and other characteristic vegetative burning in the region of Sao Carlos-SP/Brazil. Samples of PM(10) and PM(2.5) were collected in different conditions, including small laboratory controlled burnings and real ones. The samples were analysed by X-Ray Fluorescence (XRF) and 14 chemical elements quantified. t-Student tests were performed to compare the obtained profiles, using as a reference a vegetative burn profile taken from the USEPA data bank SPECIATE. All measured profiles presented significant amounts of Cl and K, which are confirmed as tracers of sugar cane foliage burning.

Assessing land availability to produce biomass for energy: The case of Brazilian charcoal for steel making

The paper discusses the availability of biomass in Brazil to supply charcoal to the steel industry on the bases of an initial global assessment of land potentially available for plantations and of Brazilian data that allows refining the assessment and specifying the issue of practical availability. Technical potentials are first assessed through a series of simple rules against direct competition with agriculture, forests and protected areas, and of quantitative criteria, whether geo-climatic (rainfall), demographic (population density) or legal (reserves). Institutional, social and economic factors are then identified and discussed so as to account for the practical availability of Brazilian biomass through six criteria. The ranking of nine Brazilian States according to these criteria brings out the necessary trade-offs in the selection of land for plantations that would efficiently supply charcoal to the steel industry. (C) 2008 Elsevier Ltd. All rights reserved.

A study on chemical constituents and sugars extraction from spent coffee grounds

Spent coffee grounds (SCG) the residual materials obtained during the processing of raw coffee powder to prepare instant coffee are the main coffee Industry residues In the present work this material was chemically characterized and subsequently submitted to a dilute acid hydrolysis aiming to recover the hemicellulose sugars Reactions were performed according to experimental designs to verify the effects of the variables H(2)SO(4) concentration liquid-to-solid ratio temperature and reaction time on the efficiency of hydrolysis SCG was found to be rich in sugars (45 3% w/w) among of which hemicellulose (constituted by mannose galactose and arabinose) and cellulose (glucose homopolymer) correspond to 367% (w/w) and 8 6% (w/w) respectively Optimal conditions for hemicellulose sugars extraction consisted in using 100 mg acid/g dry matter 10g liquid/g solid at 163 degrees C for 45 min Under these conditions hydrolysis efficiencies of 100% 774% and 895% may be achieved for galactan mannan and arabinan respectively corresponding to a hemicellulose hydrolysis efficiency of 874% (C) 2010 Elsevier Ltd All rights reserved

TOXICITY EVALUATION AS A TOOL TO ASSES THE PERFORMANCE OF AN ANAEROBIC IMMOBILIZED BIOMASS REACTOR

Effluents from pulp mill are usually toxic and mutagenic. This characteristic is mainly a consequence of xenobiotic compounds that are formed during the process. Global parameters such as chemical oxidation demand, total organic carbon and others, do not permit identify whether the toxic potential was remedied by the treatments or not. The objective of this research was to evaluate the performance of an horizontal-flow anaerobic immobilized biomass reactor (HAIB) treating the bleaching effluent from a Kraft pulp mill using toxicological (Daphnia similis - Ceriodaphnia sdvestrii) mutagenicity and citotoxicological assays (Allium cepa L). The results showed high sensibility of the test-organisms and capability of the anaerobic reactor to remove compounds that are exerting toxic and mutagenic effects. The bioassays represented an attractive alternative to water quality analyzes and the performance evaluation of treatments.

Nitrogen removal in a sequencing batch biofilm reactor with liquid circulation: Effect of feed strategy and carbon source in the denitrifying step

Ammonium nitrogen removal from a synthetic wastewater by nitrification and denitrification processes were performed in a sequencing batch biofilm reactor containing immobilized biomass on polyurethane foam with circulation of the liquid-phase. It was analyzed the effect of four external carbon sources (ethanol, acetate, carbon synthetic medium and methanol) acting as electron donors in the denitrifying process. The experiments were conducted with intermittent aeration and operated at 30+/-1 degrees C in 8-h cycles. The synthetic wastewater (100 mgCOD/L and 50 mgNH(4)(+)-N/L) was added batch-wise, while the external carbon sources were added fed-batch-wise during the periods where aeration was suspended. Ammonium nitrogen removal efficiencies obtained were 95.7, 94.3 and 97.5% for ethanol, acetate and carbon synthetic medium, respectively. As to nitrite, nitrate and ammonium nitrogen effluent concentrations, the results obtained were, respectively: 0.1, 5.7 and 1.4 mg/L for ethanol; 0.2, 4.1 and 1.8 mg/L for acetate and 0.2, 6.7 and 0.8 for carbon synthetic medium. On the other hand using methanol, even at low concentrations (50% of the stoichiometric value calculated for complete denitrification), resulted in increasing accumulation of nitrate and ammonium nitrogen in the effluent over time.

Treatment of linear alkylbenzene sulfonate in a horizontal anaerobic immobilized biomass reactor

Linear alkylbenzene sulfonate (LAS) is an anionic surfactant widely used to manufacture detergents and found in domestic and industrial wastewater. LAS removal was evaluated in a horizontal anaerobic immobilized biomass reactor. The system was filled with polyurethane foam and inoculated with sludge that was withdrawn from an up flow anaerobic sludge blanket reactor that is used to treat swine wastewater. The reactor was fed with easily degradable substrates and a solution of commercial LAS for 313 days. The hydraulic retention time applied was 12 h. The system was initially operated without detergent and resulted to 94% reduction of demand. The mass balance in the system indicated that the LAS removal efficiency was 45% after 180 days. From the 109th day to the 254th day, a removal efficiency of 32% was observed. The removal of LAS was approximately 40% when 1500 mg of LAS were applied in the absence of co-substrates suggesting that the LAS molecules were used selectively. Microscopic analyses of the biofilm revealed diverse microbial morphologies and denaturing gradient gel electrophoresis profiling showed variations in the total bacteria and sulfate-reducing bacteria populations. 16S rRNA sequencing and phylogenetic analyses demonstrated that members of the order Clostridiales were the major components of the bacterial community in the last step of the reactor operation. (c) 2009 Elsevier Ltd. All rights reserved.

Performance and molecular evaluation of an anaerobic system with suspended biomass for treating wastewater with high fat content after enzymatic hydrolysis

The effect of a lipase-rich fungal enzymatic preparation, produced by a Penicillium sp. during solid-state fermentation, was evaluated in an anaerobic digester treating dairy wastewater with 1200 mg of oil and grease/L The oil and grease hydrolysis step was carried out with 0.1% (w/v) of solid enzymatic preparation at 30 degrees C for 24 h, and resulted in a final free acid concentration eight times higher than the initial value. The digester operated in sequential batches of 48 h at 30 degrees C for 245 days, and had high chemical oxygen demand (COD) removal efficiencies (around 90%) when fed with pre-hydrolyzed wastewater. However, when the pre-hydrolysis step was removed, the anaerobic digester performed poorly (with an average COD removal of 32%), as the oil and grease accumulated in the biomass and effluent oil and grease concentration increased throughout the operational period. PCR-DGGE analysis of the Bacteria and Archaea domains revealed remarkable differences in the microbial profiles in trials conducted with and without the pre-hydrolysis step, indicating that differences observed in overall parameters were intrinsically related to the microbial diversity of the anaerobic sludge. (C) 2009 Elsevier Ltd. All rights reserved.