Sources of atmospheric acidity in an agricultural-industrial region of São Paulo State, Brazil

[1] Surface-based measurements of atmospheric formic acid (HCOOH), acetic acid (CH3COOH), sulfur dioxide (SO2), hydrogen chloride (HCl), and nitric acid (HNO3) were made in central São Paulo State, Brazil, between April 1999 and March 2000. Mean concentrations were 9.0 ppb (HCOOH), 1.3 ppb (CH3COOH), 4.9 ppb (SO2), 0.3 ppb (HCl), and 0.5 ppb (HNO3). Concentrations in sugar cane burning plumes were 1160-4230 ppb (HCOOH), 360-1750 ppb (CH3COOH), 10-630 ppb (SO2), 4-210 ppb (HCl), and 14-90 ppb (HNO3). Higher ambient concentrations of SO2, HCl and HNO3 were measured during the burning season (May-November). Concentrations of SO2 and HCl increased during the evening, and of HCOOH and CH3COOH were lowest in the morning, with peak levels in the afternoon. Ratios obtained between different species showed either nighttime maxima (SO2/HCOOH, SO2/CH3COOH, SO2/HNO3, CH3COOH/HNO3, SO2/HCl and HCOOH/HNO3), daytime maxima (HCOOH/HCl, CH3COOH/HCl and HNO3/HCl), or no clear trends (HCOOH/CH3COOH). Correlation analysis showed that SO2 and HCl were primary emissions from biomass burning and road transport; HCOOH, HNO3 and CH3COOH were products of photochemistry; HCOOH and CH3COOH were emitted directly during combustion as well as from biogenic sources. Biomass burning affected atmospheric acidity on a regional scale, while vehicular emissions had greater impact in urban and adjacent areas. Atmospheric ammonia levels were insufficient to neutralize atmospheric acidity, which was mainly removed by deposition to the surface.

Precipitation chemistry in semi-arid areas of Southern Africa: A case study of a rural and an industrial site

Experimental data on the precipitation chemistry in the semi-arid savanna of South Africa is presented in this paper. A total of 901 rainwater samples were collected with automatic wet-only samplers at a rural site, Louis Trichardt, and at an industrial site, Amersfoort, from July 1986 to June 1999. The chemical composition of precipitation was analysed for seven inorganic and two organic ions, using ion chromatography. The most abundant ion was SO(4)(2-) and a large proportion of the precipitation is acidic, with 98% of samples at Amersfoort and 94% at Louis Trichardt having a pH below 5.6 ( average pH of 4.4 and 4.9, respectively). This acidity results from a mixture of mineral and organic acids, with mineral acids being the primary contributors to the precipitation acidity in Amersfoort, while at Louis Trichardt, organic and mineral acids contribute equal amounts of acidity. It was found that the composition of rainwater is controlled by five sources: marine, terrigenous, nitrogenous, biomass burning and anthropogenic sources. The relative contributions of these sources at the two sites were calculated. Anthropogenic sources dominate at Amersfoort and biomass burning at Louis Trichardt. Most ions exhibit a seasonal pattern at Louis Trichardt, with the highest concentrations occurring during the austral spring as a result of agricultural activities and biomass combustion, while at Amersfoort it is less pronounced due to the dominance of relatively constant industrial emissions. The results are compared to observations from other African regions.

Precipitation chemistry and wet deposition in Kruger National Park, South Africa

The chemical composition, as well as the sources contributing to rainwater chemistry have been determined at Skukuza, in the Kruger National Park, South Africa. Major inorganic and organic ions were determined in 93 rainwater samples collected using an automated wet-only sampler from July 1999 to June 2002. The results indicate that the rain is acidic and the averaged precipitation pH was 4.72. This acidity results from a mixture of mineral acids (82%, of which 50% is H2SO4) and organic acids (18%). Most of the H2SO4 component can be attributed to the emissions of sulphur dioxide from the industrial region on the Highveld. The wet deposition of S and N is 5.9 kgS.ha(-1).yr(-1) and 2.8 kgN.ha(-1).yr(-1), respectively. The N deposition was mainly in the form of NH4+. Terrigenous, sea salt component, nitrogenous and anthropogenic pollutants have been identified as potential sources of chemical components in rainwater. The results are compared to observations from other African regions.

Influence of sugar cane burning on aerosol soluble ion composition in Southeastern Brazil

Seasonal variability in the major soluble ion composition of atmospheric particulate matter in the principal sugar cane growing region of central São Paulo State indicates that pre-harvest burning of sugar cane plants is an important influence on the regional scale aerosol chemistry. Samples of particulate matter were collected between April 1999 and February 2001 in coarse (> 3.5 mum) and fine (< 3.5 mum) fractions, and analysed for HCOO-, CH3COO-, C2C42-, SO42- . Results indicated that the principal sources of the aerosols investigated NO3-, Cl-, Na+, K+, NH4+, Mg2+ and Ca2+ were local or regional in nature (scale of tens to a few hundreds of km), and that differences between air masses of varying origins were small. Fine particles were typically acidic, containing secondary nitrates, sulphates and organic species. Coarse fraction concentrations were mainly influenced by physical parameters (wind speed, movement of vehicles and surface condition) affecting rates of re-suspension, although secondary nitrate and sulphate were also present in the larger particles.Concentrations of all measured species except sodium and chloride were higher during the burning season. Although concentrations were lower than often found in polluted urban environments, the massive increases during much of the year, due to a single anthropogenic activity (sugar cane burning) are indicative of a very large perturbation of the lower troposphere in the region relative to the natural condition. These aerosols are suspected of promoting respiratory disease. They also represent an important mechanism for the tropospheric transport of species relevant to surface acidification (sulphates, nitrates, ammonium and organic acids) and soil nutrient status (potassium, nitrogen, ammonium, calcium), so their impact on fragile natural ecosystems (following deposition) needs to be considered. (C) 2004 Elsevier Ltd. All rights reserved.

Aerosol and precipitation chemistry measurements in a remote site in Central Amazonia: the role of biogenic contribution

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Full-color phosphors from amine-functionalized crosslinked hybrids lacking metal activator ions

Sol-gel derived hybrids that contain OCH2CH2 (polyethylene glycol, PEG) repeat units grafted onto a siliceous backbone by urea, -NHC(=O)NH-, or urethane, -NHC(=O)O-, bridges have been prepared. It is demonstrated that the white light PL of these materials results from an unusual convolution of a longer lived emission that originates in the NH groups of the urea/urethane bridges with shorter lived electron-hole recombinations occurring in the nanometer-sized siliceous domains. The PL efficiencies reported here (maximum quantum yields at room temperature of ≈ 0.20 ± 0.02 at a 400 nm excitation wavelength) are in the same range as those for tetramethoxysilane-formic acid, and APTES-acetic acid, sol-gel derived phosphors. The high quantum yields combined with the possibility of tuning the emission to colors across the chromaticity diagram present a wide range of potential applications for these hybrid materials.

Solar photodegradation of dichloroacetic acid and 2,4-dichlorophenol using an enhanced photo-Fenton process

The photo-Fenton process using potassium ferrioxalate as a mediator was investigated for the photodegradation of dichloracetic acid (DCA) and 2,4-dichlorophenol (DCP) in aqueous medium using solar light as source of irradiation. The influence of the solution depth, the light intensity and the effect of stirring the solution during irradiation process were evaluated using DCA as a model compound. A negligible influence of stirring the solution was observed when the concentration of ferrioxalate (FeOx) was 0.8 mM and solution depth was 4.5 or 14 cm. The optimum FeOx concentration determined for solution depths between 4.5 and 14 cm was 0.8 mM considering total organic carbon (TOC) removal during DCA irradiation. The high efficiency of the photo-Fenton process was demonstrated on summer days, when only 10 min of exposition (around noon) were sufficient to completely destroy the organic carbon of a 1.0 mM DCA solution in the presence of 0.8 mM FeOx and 6.0 mM H2O2 using a solution depth of 4.5 cm. It was observed that the photodegradation efficiency increases linearly with the solar light intensity up to values around 15 Wm-2 but this linear relationship does not hold above this value showing a square root dependence. The photodegradation of a solution of DCP/FeOx showed a lower TOC removal rate than that observed for DCA/FeOx, achieving ∼90% after 35 min irradiation under 19 Wm-2, while under this light intensity, the same TOC removal of DCA/FeOx was achieved in only 10 min irradiation. © 2002 Elsevier Science Ltd. All rights reserved.

Effect of compatibilizer in acrylonitrile-butadiene-styrene toughened nylon 6 blends: Ductile-brittle transition temperature

The ductile-brittle transition temperatures were determined for compatibilized nylon 6/acrylonitrile-butadiene-styrene (PA6/ABS) copolymer blends. The compatibilizers used for those blends were methyl methacrylate-co-maleic anhydride (MMA-MAH) and MMA-co-glycidyl methacrylate (MMA-GMA). The ductile-brittle transition temperatures were found to be lower for blends compatibilized through maleate modified acrylic polymers. At room temperature, the PA6/ABS binary blend was essentially brittle whereas the ternary blends with MMA-MAH compatibilizer were supertough and showed a ductile-brittle transition temperature at -10°C. The blends compatibilized with maleated copolymer exhibited impact strengths of up to 800 J/m. However, the blends compatibilized with MMA-GMA showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures.

Assessment of the diet of 0- to 6-year-old children in municipal schools in a Brazilian city

Diet control is one of the important factors in the prevention of dental caries because food functions as substratum for fermentation and, consequently, for the formation of the organic acids that demineralize the tooth surface. This study aims to descriptively assess school diet and the associated caries-preventive methods applied to children in all municipal nursery schools of a Brazilian city (Aragatuba/SP). For this, a questionnaire with open and closed questions was used. The results showed that all schools serve school meal, which is composed mainly of sugar, carbohydrates, and proteins. The students enjoy the meal very much because for most of them, the meal served at school is the only source of food. It was observed that 90% of the schools offer other kinds of food besides the main school meal. The snacks served such as cakes, white hominy, and milk fudge are composed of sweet and highly cariogenic foods. It was also verified that in 13.30% of the schools, the daily supervised dental hygiene, an important procedure that should not be neglected, is not carried out. This procedure introduces the children to healthy habits that are added to those acquired in the family environment. It was concluded that the school diet is potentially cariogenic and, in association with the lack of daily dental hygiene, this potential may become even higher.

Developing new radiotherapy techniques using linac based gamma radiation sources

A major challenge in cancer radiotherapy is to deliver a lethal dose of radiation to the target volume while minimizing damage to the surrounding normal tissue. We have proposed a model on how treatment efficacy might be improved by interfering with biological responses to DNA damage using exogenous electric fields as a strategy to drastically reduce radiation doses in cancer therapy. This approach is demonstrated at this Laboratory through case studies with prokaryotes (bacteria) and eukaryotes (yeast) cells, in which cellkilling rates induced by both gamma radiation and exogenous electric fields were measured. It was found that when cells exposed to gamma radiation are immediately submitted to a weak electric field, cell death increases more than an order of magnitude compared to the effect of radiation alone. This finding suggests, although does not prove, that DNA damage sites are reached and recognized by means of long-range electric DNA-protein interaction, and that exogenous electric fields could destructively interfere with this process. As a consequence, DNA repair is avoided leading to massive cell death. Here we are proposing the use this new technique for the design and construction of novel radiotherapy facilities associated with linac generated gamma beams under controlled conditions of dose and beam intensity.

The mechanism of dephosphorylation of bis(2,4-dinitrophenyl) phosphate in mixed micelles of cationic surfactants and lauryl hydroxamic acid

(Figure Presented) Mixed micelles of cetyltrimethylammonium bromide (CTABr) or dodecyltrimethylammonium bromide (DTABr) and the α-nucleophile, lauryl hydroxamic acid (LHA) accelerate dephosphorylation of bis(2,4-dinitrophenyl) phosphate (BDNPP) over the pH range 4-10. With a 0.1 mole fraction of LHA in DTABr or CTABr, dephosphorylation of BDNPP is approximately 10 4-fold faster than its spontaneous hydrolysis, and monoanionic LHA - is the reactive species. The results are consistent with a mechanism involving concurrent nucleophilic attack by hydroxamate ion (i) on the aromatic carbon, giving an intermediate that decomposes to undecylamine and 2,4-dinitrophenol, and (ii) at phosphorus, giving an unstable intermediate that undergoes a Lossen rearrangement yielding a series of derivatives including N,N-dialkylurea, undecylamine, undecyl isocyanate, and carbamyl hydroxamate. © 2009 American Chemical Society.

Suplementação de acidificantes em rações de leitões desmamados: Desempenho e digestibilidade

In two experimental assays it was evaluated the diet acidifier supplementation effect on performance (assay 1) and on nutrient apparent digestibility coefficients (assay 2). During 42 days in assay 1, 120 piglets weaned at 21-days years old were allotted in8eight experimental block design with3three pigs per experimental unit. The treatments were a control and4four acidified diets. In assay 2,0ten piglets with an average weight of 16,4 kg were allotted in two experimental block design receiving two treatments under five replications (control diet without acidifier or supplied with 1,0% fumaric acid). On performance study the fumaric acid inclusion in the diet permitted a feed intake increase from 0 to 15 days, and weight gain from 0 to 32 days and from 0 to 42 days. In assay 2, the diet 1,0% of fumaric acid inclusion did not modified the apparent digestibility coefficients of dry matter and moreover diet chemical compounds. The similar apparent digestibility coefficient of dietetic nutrients with the acidifier inclusio, probabl, occurred due to the short period of evaluation. The fumaric acid inclusion in weaned piglet diets improved performance of piglets.

Ultra-structural mapping of sugarcane bagasse after oxalic acid fiber expansion (OAFEX) and ethanol production by Candida shehatae and Saccharomyces cerevisiae

Background: Diminishing supplies of fossil fuels and oil spills are rousing to explore the alternative sources of energy that can be produced from non-food/feed-based substrates. Due to its abundance, sugarcane bagasse (SB) could be a model substrate for the second-generation biofuel cellulosic ethanol. However, the efficient bioconversion of SB remains a challenge for the commercial production of cellulosic ethanol. We hypothesized that oxalic-acid-mediated thermochemical pretreatment (OAFEX) would overcome the native recalcitrance of SB by enhancing the cellulase amenability toward the embedded cellulosic microfibrils. Results: OAFEX treatment revealed the solubilization of hemicellulose releasing sugars (12.56 g/l xylose and 1.85 g/l glucose), leaving cellulignin in an accessible form for enzymatic hydrolysis. The highest hydrolytic efficiency (66.51%) of cellulignin was achieved by enzymatic hydrolysis (Celluclast 1.5 L and Novozym 188). The ultrastructure characterization of SB using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy, Fourier transform-near infrared spectroscopy (FT-NIR), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) revealed structural differences before and after OAFEX treatment with enzymatic hydrolysis. Furthermore, fermentation mediated by C. shehatae UFMG HM52.2 and S. cerevisiae 174 showed fuel ethanol production from detoxified acid (3.2 g/l, yield 0.353 g/g; 0.52 g/l, yield, 0.246 g/g) and enzymatic hydrolysates (4.83 g/l, yield, 0.28 g/g; 6.6 g/l, yield 0.46 g/g). Conclusions: OAFEX treatment revealed marked hemicellulose degradation, improving the cellulases ability to access the cellulignin and release fermentable sugars from the pretreated substrate. The ultrastructure of SB after OAFEX and enzymatic hydrolysis of cellulignin established thorough insights at the molecular level. © 2013 Chandel et al; licensee BioMed Central Ltd.

Kinetic parameters for thermal decomposition of supramolecular polymers derived from diclofenac-meglumine supramolecular adducts

Meglumine is an aminocarbohydrate able to form supramolecular adducts with organic acids. The recognition is based on hydrogen bonds and the structures resulting from the complexation have high solubility in water. This property has been exploited by the pharmaceutical industry in the improvement of existing drugs, and the successful example of this approach involves the poorly soluble non-steroidal anti-inflammatory drugs (NSAIDs). Investigation of the thermal behavior of adduct obtained from meglumine and the NSAID diclofenac revealed that a polymer-like material is formed from the self-assembly of diclofenac-meglumine adducts in the melt. This polymer showed a high molecular weight around 2.0×105kDa. The kinetic parameters for the thermal decomposition step of the polymer were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and heating rates of 5, 10, 15 and 20°Cmin-1, the Eα and Bα terms could be determined, and consequently the pre-exponential factor, Aα, as well as the kinetic model, g(α). © 2012 Elsevier B.V.

Biossolubilização da calcopirita na presença dos íons cloreto e ácidos orgânicos

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)