Climatic simulations of the eastern Andes low-level jet and its dependency on convective parameterizations

The South American low level jet (SALLJ) of the Eastern Andes is investigated with Regional Climate Model version 3 (RegCM3) simulations during the 2002-2003 austral summer using two convective parameterizations (Grell and Emanuel). The simulated SALLJ is compared with the special observations of SALLJEX (SALLJ Experiment). Both the Grell and Emanuel schemes adequately simulate the low level flow over South America. However, there are some intensity differences. Due to the larger (smaller) convective activity, the Emanuel (Grell) scheme simulates more intense (weaker) low level wind than analysis in the tropics and subtropics. The objectives criteria of Sugahara (SJ) and Bonner (BJ) were used for LLJ identification. When applied to the observations, both criteria suggest a larger frequency of the SALLJ in Santa Cruz, followed by Mariscal, Trinidad and Asuncin. In Mariscal and Asuncin, the diurnal cycle indicates that SJ occurs mainly at 12 UTCs (morning), while the BJ criterion presents the SALLJ as more homogenously distributed. The concentration into two of the four-times-a-day observations does not allow conclusions about the diurnal cycle in Santa Cruz and Trinidad. The simulated wind profiles result in a lower than observed frequency of SALLJ using both the SJ and BJ criteria, with fewer events obtained with the BJ. Due to the stronger simulated winds, the Emanuel scheme produces an equal or greater relative frequency of SALLJ than the Grell scheme. However, the Grell scheme using the SJ criterion simulates the SALLJ diurnal cycle closer to the observed one. Although some discrepancies between observed and simulated mean vertical profiles of the horizontal wind are noted, there is large agreement between the composites of the vertical structure of the SALLJ, especially when the SJ criterion is used with the Grell scheme. On an intraseasonal scale, a larger southward displacement of SALLJ in February and December when compared with January has been noted. The Grell and Emanuel schemes simulated this observed oscillation in the low-level flow. However, the spatial pattern and intensity of rainfall and circulation anomalies simulated by the Grell scheme are closer to the analyses than those obtained with the Emanuel scheme.

Cloud condensation nuclei from biomass burning during the Amazonian dry-to-wet transition season

Aircraft measurements of cloud condensation nuclei (CCN) during the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA) were conducted over the Southwestern Amazon region in September-October 2002, to emphasize the dry-to-wet transition season. The CCN concentrations were measured for values within the range 0.1-1.0% of supersaturation. The CCN concentration inside the boundary layer revealed a general decreasing trend during the transition from the end of the dry season to the onset of the wet season. Clean and polluted areas showed large differences. The differences were not so strong at high levels in the troposphere and there was evidence supporting the semi-direct aerosol effect in suppressing convection through the evaporation of clouds by aerosol absorption. The measurements also showed a diurnal cycle following biomass burning activity. Although biomass burning was the most important source of CCN, it was seen as a source of relatively efficient CCN, since the increase was significant only at high supersaturations.

Numerical study of the atmospheric flow over a coastal cliff

This work presents a numerical method suitable for the study of the development of internal boundary layers (IBL) and their characteristics for flows over various types of coastal cliffs. The IBL is an important meteorological occurrence for flows with surface roughness and topographical step changes. A two-dimensional flow program was used for this study. The governing equations were written using the vorticity-velocity formulation. The spatial derivatives were discretized by high-order compact finite differences schemes. The time integration was performed with a low storage fourth-order Runge-Kutta scheme. The coastal cliff (step) was specified through an immersed boundary method. The validation of the code was done by comparison of the results with experimental and observational data. The numerical simulations were carried out for different coastal cliff heights and inclinations. The results show that the predominant factors for the height of the IBL and its characteristics are the upstream velocity, and the height and form (inclination) of the coastal cliff. Copyright (C) 2010 John Wiley & Sons, Ltd.

Atmospheric effects on extensive air showers observed with the surface detector of the Pierre Auger observatory

Atmospheric parameters, Such as pressure (P), temperature (T) and density (rho proportional to P/T), affect the development of extensive air showers initiated by energetic cosmic rays. We have Studied the impact of atmospheric variations on extensive air showers by means of the surface detector of the Pierre Auger Observatory. The rate of events shows a similar to 10% seasonal modulation and similar to 2% diurnal one. We find that the observed behaviour is explained by a model including the effects associated with the variations of P and rho. The former affects the longitudinal development of air showers while the latter influences the Moliere radius and hence the lateral distribution of the shower particles. The model is validated with full simulations of extensive air showers using atmospheric profiles measured at the site of the Pierre Auger Observatory. (C) 2009 Elsevier B.V. All rights reserved.

Predicting new molecular species of potential interest to atmospheric chemistry: The isomers HSI and HIS

Structural, vibrational, and energetic properties of new molecular species, HSI and HIS are investigated for the first time using a state-of-the-art theoretical approach. These molecules can be easily differentiated by their geometric parameters and vibrational spectra. HSI is much more stable, and a direct unimolecular isomerization is very unlikely. Kinetics estimates predict that only at low temperatures there is a possibility of isolating HIS. For HS-I, we estimate a bond dissociation energy of 46.25 kcal/mol, and a heat of formation at 298.15 K of 12.84 kcal/mol. For the H(2)S + I(2) -> HSI + HI reaction enthalpy, we found 8.40 kcal/ mol. (C) 2008 Elsevier B.V. All rights reserved.

New Molecular Species of Potential Interest to Atmospheric Chemistry: Isomers on the [H, S(2), Br] Potential Energy Surface

This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.

Atmospheric pressure photoionization mass spectrometry as a tool for the investigation of the hydrolysis reaction mechanisms of phosphite antioxidants

The hydrolysis reaction mechanism of phosphite antioxidants is investigated by liquid chromatography-mass spectrometry (LC/MS). The phosphites were chosen because they differed in chemical structure and phosphorus content. Dopant assisted-atmospheric pressure photoionization (DA-APPI) is chosen as the ion source for (lie ionization of the compounds. [it our previous work, DA-APPI was shown to offer an attractive alternative to atmospheric pressure chemical ionization (APCI) since it provided background-ion free mass spectra and higher sensitivity [M. Papanastasiou, et al., Polymer Degradation and Stability 91 (11) (2006) 2675-2682]. In positive ion mode, the molecules are generally detected in their protonated form. In negative ion mode, the phosphites are unstable and only fragment ions are observed: these however, are characteristic of each phosphite and may be used for the identification of the analytes in complex mixtures. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites, with phenol substituents producing very hydrolytically stable structures. Alkanox P24 and PEP-36 follow a similar hydrolytic pathway via the scission of the first and then the second P-O-phenol bonds, eventually leading to the formation of phenol, Phosphorous acid and pentaerythritol as end products. HP-10 exhibits a rather different Structure and the products detected suggest scission of either the P-O-hydrocarbon or one of the P-O-phenol bonds. A phenomenon similar to that of autocatalysis is observed for all phosphites and is attributed to the formation of dialkyl phosphites as intermediate products. (C) 2008 Elsevier B.V. All rights reserved.