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This study evaluates nine Planetary Boundary Layer (PBL) turbulence parameterization schemes from the Weather Research and Forecasting (WRF) mesoscale meteorological model, comparing hourly values of meteorological variables observed and simulated at the surface of the Metropolitan Region of São Paulo (MRSP). The numerical results were objectively compared with high-quality observations carried out on three micrometeorological platforms representing typical urban, suburban, and rural land use areas of the MRSP, during the 2013 summer and winter field campaigns as part of the MCITY BRAZIL project. The main objective is to identify which PBL scheme best represents the diurnal evolution of conventional meteorological variables (temperature, relative and specific humidity, wind speed, and direction) and unconventional (sensible and latent heat fluxes, net radiation, and incoming downward solar radiation) on the surface. During the summer field campaign and over the suburban area of the MRSP, most PBL scheme simulations exhibited a cold and dry bias and overestimated wind speed. They also overestimated sensible heat flux, with high agreement index and correlation values. In general, the PBL scheme simulations performed well for latent heat flux, displaying low mean bias error and root square mean error values. Both incoming downward solar radiation and net radiation were also accurately simulated by most of them. The comparison of the nine PBL schemes indicated the local Mellor-Yamada-Janjic (MYJ) scheme performed best during the summer period, particularly for conventional meteorological variables for the land use suburban in the MRSP. During the winter field campaign, simulation outcomes varied significantly based on the site's land use and the meteorological variable analyzed. The MYJ, Bougeault-Lacarrère (BouLac), and Mellor-Yamada Nakanishi-Niino (MYNN) schemes effectively simulated temperature and humidity, especially in the urban land use area. The MYNN scheme also simulated net radiation accurately. There was a tendency to overestimate sensible and latent heat fluxes, except for the rural land use area where they were consistently underestimated. However, the rural area exhibited superior correlations compared to the urban area. Overall, the MYJ scheme was deemed the most suitable for representing the convectional and nonconventional meteorological variables on the surface in all urban, suburban, and rural land use areas of the MRSP. [ABSTRACT FROM AUTHOR]

The chemical composition of rainwater samples collected from March 2002 to February 2003 in downtown São Paulo city (Universidade Presbiteriana Mackenzie) is presented. Potentiometric and conductimetric measurements were used to evaluate the [H+] and the total ionic content. Major anions and cations were determined by ion chromatography with conductivity detection. The rainwater was acidic with a mean pH of 4.99. The volume weighted means, VWM, of the anions nitrate, acetate and sulfate were, respectively, 21.2, 16.9 and 12.4 µmol L-1. Ammonium was the most abundant ion with a VWM of 37.6 µmol L-1. The contribution of each anion to the free acidity potential decreases in the following order: SO4(2-) (28.8%), CH3COO- (24.7%), NO3- (22.8%), Cl- (13.4%), HCOO- (7.7%) and C2O4(2-) (2.5%). The relative contribution of the weak organic acids to the free acidity was significant, 34.9%.

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