Fourier transform infrared studies of the reaction of Cl atoms with PAN,PPN, CH3OOH,HCOOH, CH3COCH3 and CH3COC2H5 at 295±2 K

The relative rate technique has been used to measure rate constants for the reaction of chlorine atoms with peroxyacetylnitrate (PAN), peroxypropionylnitrate (PPN), methylhydroperoxide, formic acid, acetone and butanone. Decay rates of these organic species were measured relative to one or more of the following reference compounds; ethene, ethane, chloroethane, chloromethane, and methane. Using rate constants of 9.29×10^–11, 5.7×10^–11, 8.04×10^–12, 4.9×10^–13, and 1.0×10^–13 cm³ molecule^–1 sec^–1 for the reaction of Cl atoms with ethene, ethane, chloroethane, chloromethane, and methane respectively, the following rate constants were derived, in units of cm³ molecule^–1 s^–1: PAN, <7×10^–15; PPN, (1.14±0.12)×10^–12; HCOOH, (2.00±0.25)×10^–13; CH₃OOH, (5.70±0.23)×10^–11; CH₃COCH₃, (2.37±0.12)×10^–12; and CH₃COC₂H₅, (4.13±0.57)×10^–11. Quoted errors represent 2 and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295±2 K and 700 torr total pressure of nitrogen or synthetic air. The results are discussed with respect to the previous literature data and to the modelling of nonmethane hydrocarbon oxidation in the atmosphere.In recent discussions with Dr. R. A. Cox of Harwell Laboratory, UKAEA, we learnt of a preliminary value for the rate constant of the reaction of Cl with acetone of (2.5±1.0)×10^–12 cm³ molecule^–1 sec^–1 measured by R. A. Cox, M. E. Jenkin, and G. D. Hayman using molecular modulation techniques. This value is in good agreement with our results.     

Development of regional future climate change scenarios in South America using the Eta CPTEC/HadCM3 climate change projections: climatology and regional analyses for the Amazon, S?o Francisco and the Paraná River basins

The objective of this study is to assess the climate projections over South America using the Eta-CPTEC regional model driven by four members of an ensemble of the Met Office Hadley Centre Global Coupled climate model HadCM3. The global model ensemble was run over the twenty-first century according to the SRES A1B emissions scenario, but with each member having a different climate sensitivity. The four members selected to drive the Eta-CPTEC model span the sensitivity range in the global model ensemble. The Eta-CPTEC model nested in these lateral boundary conditions was configured with a 40-km grid size and was run over 1961–1990 to represent baseline climate, and 2011–2100 to simulate possible future changes. Results presented here focus on austral summer and winter climate of 2011–2040, 2041–2070 and 2071–2100 periods, for South America and for three major river basins in Brazil. Projections of changes in upper and low-level circulation and the mean sea level pressure (SLP) fields simulate a pattern of weakening of the tropical circulation and strengthening of the subtropical circulation, marked by intensification at the surface of the Chaco Low and the subtropical highs. Strong warming (4–6°C) of continental South America increases the temperature gradient between continental South America and the South Atlantic. This leads to stronger SLP gradients between continent and oceans, and to changes in moisture transport and rainfall. Large rainfall reductions are simulated in Amazonia and Northeast Brazil (reaching up to 40%), and rainfall increases around the northern coast of Peru and Ecuador and in southeastern South America, reaching up to 30% in northern Argentina. All changes are more intense after 2040. The Precipitation–Evaporation (P–E) difference in the A1B downscaled scenario suggest water deficits and river runoff reductions in the eastern Amazon and S?o Francisco Basin, making these regions susceptible to drier conditions and droughts in the future.