Polar organic marker compounds in atmospheric aerosols during the LBA-SMOCC 2002 biomass burning experiment in Rondonia, Brazil: sources and source processes, time series, diel variations and size distributions

Measurements of polar organic marker compounds were performed on aerosols that were collected at a pasture site in the Amazon basin (Rondonia, Brazil) using a high-volume dichotomous sampler (HVDS) and a Micro-Orifice Uniform Deposit Impactor (MOUDI) within the framework of the 2002 LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazonia - Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate) campaign. The campaign spanned the late dry season (biomass burning), a transition period, and the onset of the wet season (clean conditions). In the present study a more detailed discussion is presented compared to previous reports on the behavior of selected polar marker compounds, including levoglucosan, malic acid, isoprene secondary organic aerosol (SOA) tracers and tracers for fungal spores. The tracer data are discussed taking into account new insights that recently became available into their stability and/or aerosol formation processes. During all three periods, levoglucosan was the most dominant identified organic species in the PM(2.5) size fraction of the HVDS samples. In the dry period levoglucosan reached concentrations of up to 7.5 mu g m(-3) and exhibited diel variations with a nighttime prevalence. It was closely associated with the PM mass in the size-segregated samples and was mainly present in the fine mode, except during the wet period where it peaked in the coarse mode. Isoprene SOA tracers showed an average concentration of 250 ng m(-3) during the dry period versus 157 ng m(-3) during the transition period and 52 ng m(-3) during the wet period. Malic acid and the 2-methyltetrols exhibited a different size distribution pattern, which is consistent with different aerosol formation processes (i.e., gas-to-particle partitioning in the case of malic acid and heterogeneous formation from gas-phase precursors in the case of the 2-methyltetrols). The 2-methyltetrols were mainly associated with the fine mode during all periods, while malic acid was prevalent in the fine mode only during the dry and transition periods, and dominant in the coarse mode during the wet period. The sum of the fungal spore tracers arabitol, mannitol, and erythritol in the PM(2.5) fraction of the HVDS samples during the dry, transition, and wet periods was, on average, 54 ng m(-3), 34 ng m(-3), and 27 ng m(-3), respectively, and revealed minor day/night variation. The mass size distributions of arabitol and mannitol during all periods showed similar patterns and an association with the coarse mode, consistent with their primary origin. The results show that even under the heavy smoke conditions of the dry period a natural background with contributions from bioaerosols and isoprene SOA can be revealed. The enhancement in isoprene SOA in the dry season is mainly attributed to an increased acidity of the aerosols, increased NO(x) concentrations and a decreased wet deposition.

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.

Measurement of the underground atmospheric muon charge ratio using the MINOS Near Detector

The magnetized MINOS Near Detector, at a depth of 225 mwe, is used to measure the atmospheric muon charge ratio. The ratio of observed positive to negative atmospheric muon rates, using 301 days of data, is measured to be 1.266 +/- 0.001(stat)(-0.014)(+0.015)(syst). This measurement is consistent with previous results from other shallow underground detectors and is 0.108 +/- 0.019(stat + syst) lower than the measurement at the functionally identical MINOS Far Detector at a depth of 2070 mwe. This increase in charge ratio as a function of depth is consistent with an increase in the fraction of muons arising from kaon decay for increasing muon surface energies.

Optimisation of environmental gas cleaning routes for solid wastes cogeneration systems. Part II - Analysis of waste incineration combined gas/steam cycle

In the first paper of this paper (Part I), conditions were presented for the gas cleaning technological route for environomic optimisation of a cogeneration system based in a thermal cycle with municipal solid waste incineration. In this second part, an environomic analysis is presented of a cogeneration system comprising a combined cycle composed of a gas cycle burning natural gas with a heat recovery steam generator with no supplementary burning and a steam cycle burning municipal solid wastes (MSW) to which will be added a pure back pressure steam turbine (another one) of pure condensation. This analysis aims to select, concerning some scenarios, the best atmospheric pollutant emission control routes (rc) according to the investment cost minimisation, operation and social damage criteria. In this study, a comparison is also performed with the results obtained in the Case Study presented in Part I. (c) 2007 Elsevier Ltd. All rights reserved.

Atmospheric impacts of the life cycle emissions of fuel ethanol in Brazil: based on chemical exergy

An assessment is made of the atmospheric emissions from the life cycle of fuel ethanol coupled with the cogeneration of electricity from sugarcane in Brazil. The total exergy loss from the most quantitative relevant atmospheric emission substances produced by the life cycle of fuel ethanol is 3.26E+05 kJ/t of C(2)H(5)OH, Compared with the chemical exergy of 1 t of ethanol (calculated as 34.56E + 06 kJ). the exergy loss from the life cycle`s atmospheric emission represents 1.11% of the product`s exergy. The activity that most contributes to atmospheric emission chemical exergy losses is the harvesting of sugarcane through the methane emitted in burning. Suggestions for improved environmental quality and greater efficiency of the life cycle of fuel ethanol with cogenerated energy are: harvesting the sugarcane without burning, renewable fuels should be used in tractors, trucks and buses instead of fossil fuel and the transportation of products and input should be logistically optimized. (C) 2009 Elsevier Ltd. All rights reserved.

A systemic approach for optimal cooling tower operation

The thermal performance of a cooling tower and its cooling water system is critical for industrial plants, and small deviations from the design conditions may cause severe instability in the operation and economics of the process. External disturbances such as variation in the thermal demand of the process or oscillations in atmospheric conditions may be suppressed in multiple ways. Nevertheless, such alternatives are hardly ever implemented in the industrial operation due to the poor coordination between the utility and process sectors. The complexity of the operation increases because of the strong interaction among the process variables. In the present work, an integrated model for the minimization of the operating costs of a cooling water system is developed. The system is composed of a cooling tower as well as a network of heat exchangers. After the model is verified, several cases are studied with the objective of determining the optimal operation. It is observed that the most important operational resources to mitigate disturbances in the thermal demand of the process are, in this order: the increase in recycle water flow rate, the increase in air flow rate and finally the forced removal of a portion of the water flow rate that enters the cooling tower with the corresponding make-up flow rate. (C) 2009 Elsevier Ltd. All rights reserved.

Thermodynamics of aqueous solutions of polyelectrolytes: Experimental results for the activity of water in aqueous solutions of (a single synthetic polyelectrolyte and sodium chloride)

Experimental results for the activity of water in aqueous solutions of 10 single, synthetic polyelectrolytes (polysodium acrylate, polysodium methacrylate, polyammonium acrylate, polysodium ethylene sulfonate, and polysodium styrene sulfonate) and sodium chloride at 298.2 K are presented. The experimental work was performed by applying the isopiestic method with sodium chloride as a reference substance. As expected, the activity of water decreases when the concentration of a polyelectrolyte and/or sodium chloride increases. At constant concentration of a polyelectrolyte and sodium chloride, the activity of water depends on the monomer unit and the molecular mass of the polyelectrolyte. The new data are to be used in future work to develop and test models for the Gibbs excess energy of aqueous solutions of polyelectrolytes.

Thermodynamics of aqueous solutions of polyelectrolytes: Experimental results for the activity of water in aqueous solutions of some single synthetic polyelectrolytes

Experimental results for the activity of water in aqueous solutions of 10 single polyelectrolytes (two polysodium acrylates, two polysodium methacrylates, three polyammonium acrylates, two polysodium ethylene sulfonates, and one polysodium styrene sulfonate) at (298.2 and 323.2) K are reported. The isopiestic method was employed in these experiments with aqueous solutions of sodium chloride as references. The polyelectrolytes were characterized by three averaged molecular masses determined by gel permeation chromatography. Furthermore, the density and the refractive index increments of the aqueous polyelectrolyte solutions are reported. Although a similar pattern for the activity of water was observed for all systems (i.e., the osmotic coefficient increases with rising polyelectrolyte concentration), the experimental results show that this property depends on the monomer type as well as on the size of the polymer chain. The temperature (varied from (298.2 to 323.2) K) has only a small influence on the activity of water.

Anomalous compressibility of ferropericlase throughout the iron spin cross-over

The thermoelastic properties of ferropericlase Mg(1-x)Fe(x)O (x = 0.1875) throughout the iron high-to-low spin cross-over have been investigated by first principles at Earth`s lower mantle conditions. This cross-over has important consequences for elasticity such as an anomalous bulk modulus (K(S)) reduction. At room temperature the anomaly is somewhat sharp in pressure but broadens with increasing temperature. Along a typical geotherm it occurs across most of the lower mantle with a more significant K(S) reduction at approximate to 1,400-1,600 km depth. This anomaly might also cause a reduction in the effective activation energy for diffusion creep and lead to a viscosity minimum in the mid-lower mantle, in apparent agreement with results from inversion of data related with mantle convection and postglacial rebound.

Atmospheric Absorption of Fluoride by Cultivated Species. Leaf Structural Changes and Plant Growth

Fluoride (F) is an air pollutant that causes phytotoxicity. Besides the importance of this, losses of agricultural crops in the vicinity of F polluting industries in Brazil have been recently reported. Injuries caused to plant leaf cell structures by excess F are not well characterized. However, this may contribute to understanding the ways in which plant physiological and biochemical processes are altered. A study evaluated the effects of the atmospheric F on leaf characteristics and growth of young trees of sweet orange and coffee exposed to low (0.04 mol L(-1)) or high (0.16 mol L(-1)) doses of HF nebulized in closed chamber for 28 days plus a control treatment not exposed. Gladiolus and ryegrass were used as bioindicators in the experiment to monitor F exposure levels. Fluoride concentration and dry mass of leaves were evaluated. Leaf anatomy was observed under light and electron microscopy. High F concentrations (similar to 180 mg kg(-1)) were found in leaves of plants exposed at the highest dose of HF. Visual symptoms of F toxicity in leaves of citrus and coffee were observed. Analyses of plant tissue provided evidence that F caused degeneration of cell wall and cytoplasm and disorganization of bundle sheath, which were more evident in Gladiolus and coffee. Minor changes were observed for sweet orange and ryegrass. Increase on individual stomatal area was also marked for the Gladiolus and coffee, and which were characterized by occurrence of opened ostioles. The increased F absorption by leaves and changes at the structural and ultrastructural level of leaf tissues correlated with reduced plant growth.

A correct enthalpy relationship as thermal comfort index for livestock

Researchers working with thermal comfort have been using enthalpy to measure thermal energy inside rural facilities, establishing indicator values for many situations of thermal comfort and heat stress. This variable turned out to be helpful in analyzing thermal exchange in livestock systems. The animals are exposed to an environment which is decisive for the thermoregulatory process, and, consequently, the reactions reflect states of thermal comfort or heat stress, the last being responsable for problems of sanity, behavior and productivity. There are researchers using enthalpy as a qualitative indicator of thermal environment of livestock such as poultry, cattle and hogs in tropical regions. This preliminary work intends to check different enthalpy equations using information from classical thermodynamics, and proposes a direct equation as thermal comfort index for livestock systems.

Quantification of free mycophenolic acid by high-performance liquid chromatography-atmospheric pressure chemical ionisation tandem mass spectrometry

To facilitate the investigation of free mycophenolic acid concentrations we developed a high-performance liquid chromatography tandem mass spectrometry method using indomethacin as an internal standard. Free drug was isolated from plasma samples (500 mul) using ultrafiltration, The analytes were extracted from the ultrafiltrate (200 mul) using C-18 solid-phase extraction. Detection was by selected reactant monitoring of mycophenolic acid (m/z 318.9-->190.9) and the internal standard (m/z 356.0-->297.1) with an atmospheric pressure chemical ionisation interface. The total chromatographic analysis time was 12 min. The method was found to be linear over the range investigated, 2.5-200 mug/l (r>0.990, n=6). The relative recovery of the method for the control samples studied (7.5, 40.0 and 150 mug/l) ranged from 95 to 104%. The imprecision of the method, expressed in terms of intra- and inter-day coefficients of variation, was

Atmospheric corrosion of copper at Heron Island

Atmospheric corrosion tests have been conducted at Heron Island, Queensland, a low SO2 marine environment. The corrosion rates for copper followed the linear bi-logarithmic law. X-ray diffraction identified atacamite (basic copper chloride) and cuprite (cuprous oxide) as the predominant corrosion products. Biogenic and anthropogenic sources of pollution did not have a measurable influence.

Atmospheric pollutants monitoring by analysis of epiphytic lichens

The Canoparmelia texana epiphytic lichenized fungi was used to monitor atmospheric pollution in the Sao Paulo metropolitan region, SP, Brazil. The cluster analysis applied to the element concentration values confirmed the site groups of different levels of pollution due to industrial and vehicular emissions. In the distribution maps of element concentrations, higher concentrations of Ba and Mn were observed in the vicinity of industries and of a petrochemical complex. The highest concentration of Co found in lichens from the Sao Miguel Paulista site is due to the emissions from a metallurgical processing plant that produces this element. For Br and Zn, the highest concentrations could be associated both to vehicular and industrial emissions. Exploratory analyses revealed that the accumulation of toxic elements in C. texana may be of use in evaluating the human risk of cardiopulmonary mortality due to prolonged exposure to ambient levels of air pollution. (c) 2007 Elsevier Ltd. All rights reserved.

Phase equilibria and thermodynamics of zinc fuming slags

A range of materials is treated in zinc fuming processes to recover metal values and produce benign slag waste products. The selection of the optimum process conditions in these various technologies can be greatly assisted by the use of a chemical thermodynamic model of the system. In this paper the effects of slag chemistry on the liquidus temperatures, subliquidus phase equilibria and thermodynamic properties are described by the F*A*C*T computer package with the new thermodynamic database of the ZnO-PbO-FeO-Fe2O3-CaO-SiO2 system. The implications of these findings for plant practice are discussed.