17th International Conference on Harmonisation within Atmospheric Dispersion Modelling for Regulatory Purposes 9-12 May 2016, Budapest, Hungary

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17th International Conference on Harmonisation within Atmospheric Dispersion Modelling for Regulatory Purposes 9-12 May 2016, Budapest, Hungary INVESTIGATION OF THE TRANSPORT OF POLLUTANTS FROM THE METROPOLITAN AREA OF SÃO PAULO AND FROM THE INDUSTRIAL CITY OF CUBATÃO TO NEARBY AREAS Atenágoras Souza Silva 1, Américo A F S Kerr 1,Simone Gioia 2 and Marly Babinskky 3 1 Instituto de Física, Universidade de São Paulo (USP), São Paulo, Brazil 2 Centro Tecnológico da Marinha de São Paulo, São Paulo, Brazil 3 Centro de Pesquisas Geocronológicas, Instituto de Geociências, Universidade de São Paulo, São Paulo, Brazil Abstract: The mesoscale meteorological model BRAMS and the Lagrangian dispersion model SPRAY were used to discuss the transport of pollutant inside, between, and nearby the Metropolitan Area of São Paulo and Mogi Valley, at an industrial town from Cubatão city. The acceptable agreement between simulated and measured data showed the models skill to represent meteorology and air pollution dispersion in these areas. Two winter episodes were studied and, in general, the local emissions dominated the local air quality levels, although transport was significant to some localized places. Key words: São Paulo air Pollution, Cubatão air pollution, Dispersion Modeling, SPRAY, BRAMS INTRODUCTION The Metropolitan Area of São Paulo (MASP) has more than 20 million inhabitants and above 7 million vehicles. In the coast, 40 km farther, there are a strong industrial city, named Cubatão, with 23 big industrial plants and tenths of small and middle size ones. In the winter of 2006 an experiment was conduced in these areas, collecting the fine and coarse atmospheric aerosol in four stations, every 12h, for one week (Gioia, S., 2006). One stations was in a small city, Juquitiba, a remote border area of the MASP, rounded by native vegetation, other was slightly more inside the MASP area, another in an almost central point of the MASP, and the lat one at the industrial area of Cubatão. Samples was analyzed by PIXE and ID-TIMS, respectively to identify chemical elements (atomic number>10) and Pb isotopes concentrations and ratios, to characterize the aerosol, to study they sources and to get some information of pollutant transport among the sampled areas. In the present work, we used the mesoscale atmospheric model BRAMS and SPRAY, a Lagrangian Stochastic Model (LSM), to improve the discussion about pollutant dispersion in and around the area of this experiment. An inventory of the particulate emitted by five fertilizer plants from Cubatão, and, of the CO emitted by the vehicular fleet from MASP, was used in the simulations, providing reliable concentrations values and images for the pollutant transport during two winter episodes for PM 10. METHODS The modeling system BRAMS & SPRAY The LSM SPRAY basis and development (ENEL, ICG/CNR, and Arianet) are described by Tinarelli et al. 1994 and 2000, among other references. It uses the generalized Langevin equation to simulate the dispersion of inert gases; the key input is the Eulerian PDF of the turbulent velocities, used in the corresponding Fokker-Planck equation to determine the value of the drift coefficient of the Langevin equation. In this work, for instance, the Gram-Charlier PDF truncated to the third order moment was used in the vertical, and in the horizontal direction the PDF was Gaussian.

The meteorological parameters needed by SPRAY were provided by BRAMS (Brazilian developments on the Regional Atmospheric Modelling System-RAMS), version 4.2 (Fazenda et al. 2007). It is a shared development of ATMET, IME/USP, IAG/USP, and CPTEC/INPE, with the aims of provide a new RAMS version, improved for tropics. Historical development and theoretical basis for BRAMS is well described in BRAMS, 2013. Time Modulation for Congonhas CO & PM10 0.07 0.06 0.05 Fraction 0.04 0.03 0.02 0.01 0 1 6 11 16 21 CO Fraction (2006) PM10 Fraction (2006) time (h) Figure 1. Time modulation for CO and PM 10 concentrations at Congonhas' in 2006. They showed a good correlation. An assumption used in the work was that CO to PM 10 ratio at Congonhas (40.7) was a first approximation of this vehicular emission ratio at MASP. Grid Grid center (lat/lon) Table 1. Resolution and boundary conditions for simulation areas Grid Grid area Latitude limits resolution (Km x Km) (deg) (m) Longitude limits ( deg) 1 23.077⁰S / 46.345⁰E 12000 456 x 456 20.985⁰S - 25.141⁰S 48.579⁰W - 44.049⁰W 2 23.293⁰S / 46.342⁰E 3000 403 x 360 22.231⁰S - 24.344⁰S 47.713⁰W - 44.949⁰W 3 23.714⁰S / 46.615⁰E 1000 346 x 267 23.284⁰S - 24.143⁰S 47.199⁰W - 46.028⁰W Table 2. Meteorological and/or CO measuring s Latitude Longitude Number Name (S, Degree) (W, Degree) 1 Ibirapuera 23.591 46.629 2 Cubatão Centro 23.879 46.418 3 Cubatão Vale do Mogi 23.832 46.37 4 Cubatão Vila Parisi 23.849 46.388 5 Pinheiros 23.561 46.702 6 Santo Amaro 23.655 46.71 7 São Caetano 23.617 46.556 8 São José dos Campos 23.187 45.871 9 Osasco 23.527 46.792 10 Sorocaba 23.502 47.479 11 Santo André 23.646 46.536 12 Pedro II 23.544 46.66 13 Taboão da Serra 23.609 46.758 14 IAG 23.649 46.625

BRAMS uses a two ways nesting procedure, allowing coherence between large to small grids data processing. Three nested grids were used in this case (Table-1) to simulate meteorological parameters in the areas studied, between days 23 and 29 August 2006. The model was initialized with CPTEC (Centro de Previsão de Tempo e Estudos Climáticos, a Brazilian Weather Forecast Center) global files (time resolution of 12h, and Lat-Lon resolution of 0.9375º, with 28 vertical levels). SPRAY simulated the dispersion of the CO emitted by the MASP's vehicular fleet using the meteorological data from Grid-2 (3 km resolution). In the other hand, the transport of PM 10 emitted by 5 Fertilizer Plants at Cubatão, a complex terrain area, was analyzed using the better resolution (1 km) of Grid-1 (sources' position and emission rates at Kerr et all., 2000). The CO vehicular area emission at MASP, with 5 km² resolution, was estimated considering the fleet composition and traffic flow, estimated by Kerr, A., et al., 2005, for the year 2000 at MASP (a total of 1.69x10⁶ t.y ¹). A reduction factor of 1.5 was applied considering 2000 to 2006 CO concentrations ratio at Congonhas' station (CETESB, 2001 and 2007). The time modulation of CO concentrations was also associated to the pattern observed at this station in the year 2006 (Figure 1). An assumption was that this station is representative of the vehicular CO emission, because it is very close to a typical high traffic MASP avenue. In the same way, the CO to PM 10 average ratio at this station in 2006 (40.7) was taken as representing, in a first approximation, the vehicular CO to PM 10 concentration ratio at MASP in this year. Arianet provided GAP (Grid Adaptator) and SurfPro softwares to adapt the simulated BRAMS' meteorological data grid for SPRAY and, added to USGS landuse data, evaluate also the turbulence information to be used by SPRAY RESULTS AND ANALYSIS Statistical comparisons for Meteorological and Pollutants dispersion simulations Table 2 shows the position of 13 stations from the São Paulo State environmental agency (CETESB, 2007), measuring air pollutants and/or meteorological parameters, and one meteorological station from the Institute of Astronomy, Geophysics and Atmospheric Sciences of the University of São Paulo IAG. Meteorological and/or CO data comparisons were performed in every station were these data are available with acceptable number of miss values. Tables 3 to 5 show the comparisons between observed and simulated values for wind, temperature, and relative humidity. The columns r report the observed to simulated data correlation (index u and v indicate the two horizontal wind components) and P is the significance level of the correlation; the σ are standard deviations (index o and s, refer to observed and simulated data, respectively), and σ(u,v) is equal to (σ u ²+σ v ²) -0.5, accounting for both, u and v, standard deviations; RMSE is the Root Mean Square Error (RMSVE is used for vector variables); N is the number of compared points. Table 3. Comparisons between observed and simulated horizontal wind at 10 m (N from 120 to 167) (u,v) (u,v) RMSVE r u r v P (for the worse r) 1 2.25 1.90 1.65 0.5590 0.8214 <0.001 3 2.98 3.16 3.12 0.2317 0.7439 <0.005 4 2.57 2.54 2.73 0.2448 0.6354 <0.005 5 2.29 2.18 1.61 0.6739 0.8279 <0.001 6 2.49 2.42 1.43 0.7896 0.8667 <0.001 7 2.64 1.95 2.10 0.6968 0.7640 <0.001 8 2.25 1.90 1.65 0.5590 0.8214 <0.001 9 2.75 2.12 1.66 0.7359 0.8595 <0.001 10 2.37 2.11 1.93 0.5099 0.8006 <0.001 14 2.60 2.46 2.79 0.4452 0.4608 <0.001

Table 4. Relative Humidity Comparison between measured and simulated values (N=167) RMSE r P <RH>o <RH>s 1 28 20 17 0.81 <0.001 72.4 67.3 2 17 11 30 0.43 <0.001 86.2 61.1 5 28 21 19 0.85 <0.001 58.0 67.0 7 26 22 17 0.88 <0.001 71.4 66.9 14 26 24 16 0.77 <0.001 71.0 67.8 Table 5. Air Temperature - Comparison between measured and simulated values (N=167) RMSE r P <T> o <T> s 1 7.1 5.3 3.8 0.86 <0.001 18.9 17.4 2 6.6 6.6 3.6 0.78 <0.001 17.4 17.2 5 7.3 6.8 3.7 0.87 <0.001 18.8 17.6 7 4.3 4.8 3.0 0.8 <0.001 17.4 17.2 14 6.5 7.1 3.4 0.89 <0.001 18.9 17.3 Horizontal wind at 10 m are correlated at high level of significance, while RMSVE and (u,v) values are lower or similar to the observed (u,v), all indicating a good BRAMS skill for simulating the 10 m wind. The same could be inferred for humidity and temperature in tables 4 and 5, except for humidity at station 2, probably because this station is settled at the ground of the Mogi Valley, which walls are steep, and fast growing from sea level till 600 to 1200 m heights, limiting the Model s ability to capture such variability. Comparisons between simulated and observed CO concentrations (Table 6) show correlations with good significance level (stations 5, 7, 11and 13), while RMSE and are less or not much higher than for stations 7, 11 and 13. Finally, the ratio of simulated to observed CO averages in the last stations differs by less than 37%, corroborating to qualify their good data agreement. s 5 and 12 showed acceptable significance level for the data correlation, although the other parameters do not show fair results. Data for station 1, otherwise, showed high discrepancies, being the simulated average CO concentration 3.51 times greater than the observed values, probably because this station is settled in a large park inside the MASP, and the model resolution was not able to capture the dilution produced by the park. The two selected images of simulations at Figure 2 show the significative amount of pollutant transported down (from São Paulo), and up the mountain range (from Cubatão) following the shore line. Figure 2. CO transport and concentration related with two episodes.

Although not exceeding the 8h standard (10x10³μg.m -3 or 9.0 ppm) the CO plume contours show the CO transport, with 1 h values relatively high in remote and forested areas of the MASP. Table 6. CO concentrations - Comparison between observed and simulated values (N from 53 to 93) (x10² μg.m ³) (x10² μg.m ³) RMSE r P <CO> o (x10² μg.m ³) <CO> s (x10² μg.m ³) N 1 35.4 7.81 45.5 0.30 <0,002 13.4 46.9 91 3.51 5 36.7 14.0 42.2 0.37 <0,001 22.7 49.9 93 2.2 7 12.6 17.1 11.8 0.77 <0,001 19.9 17.0 53 0.86 11 7.7 8.90 8.7 0.54 <0,001 13.8 10.7 91 0.78 12 48.3 11.8 68.5 0.27 <0,01 15.2 65.2 75 4.28 13 25.7 19.6 27.5 0.30 <0,01 22.8 31.4 84 1.37 s/o Table 7. PM 10 exceedance of World Health Organization daily guide lines (50 μg.m ³, WHO, 2005). City Measure period Start date Finish date <PM 10 > (μg.m ³) Cubatão daytime 25/08/2006 25/08/2006 107 São Paulo daytime 25/08/2006 25/08/2006 57 Cubatão night time 25/08/2006 26/08/2006 73 Juquitiba night time 25/08/2006 26/08/2006 81 São Paulo night time 25/08/2006 26/08/2006 84 CONCLUSION The Couple BRAMS/SPRAY meteorological and diffusion simulation modeling systems was able to simulate reliable concentration fields for vehicular CO emitted in the MASP, as well as the PM 10 emitted by fertilizer plants at Cubatão. Pollutant transport between some zones of these areas, highly populated and comporting forested reserves may arrive to significant intensity. In the next steps of this work, this dispersion simulations system, chemical analysis of the measured PM 10, and receptor modeling will be put together to better understand the sources' role and air pollution transport among these areas. REFERENCES BRAMS, 2013, CPTEC, http://www.cptec.inpe.br/brams/f_time.shtml, visited in 03/28/2013. CETESB, 2001 and 2007: Relatório de Qualidade do Ar no Estado de São Paulo. Secretaria de Estado de Meio Ambiente. São Paulo, SP, Brazil, http://ar.cetesb.sp.gov.br/publicacoes-relatorios/, visited in 03/20/2006. Fazenda, L. A, D.S. Moreira, E.H. Enari, J. Panetta, L.F. Rodrigues, 2007: First Time User's Guide, (BRAMS Version 4.0), CPTEC, http://www.cptec.inpe.br/brams/f_time.shtml, visited in 03/28/2013. Gioia, S., 2006: Estudo da Composição dos Aerossóis e da assinatura isotópica de Pb como traçador das fontes da poluição atmosférica da cidade de São Paulo., post-doc work. Kerr, A. A. F. S., ANFOSSI, Domenico, CASTELLI, Silvia Trini, NASCIMENTO, S. A.,2000. Investigation of Inhalable Aerossol at Cubatão by means of a Modeling System for Complex Terrain, Hybrid Methods in Engineering, 2, 389-407. Kerr, A., Landmann, M. C., Carvalho, J., 2005: Investigation of CO dispersion from São Paulo Metropolis by means of modelling system for complex terrain. 9 Th Harmonisation, 2005. Tinarelli, G., D. Anfossi, G. Brusasca, E. Ferreiro, Giostra U., M.G. Morselli, Moussafir J., Tampieri F., Trombetti F., 1994: Lagrangian Particle Simulation of Tracer Dispersion in the Lee of a schematic Two-Dimensional Hill. Journal of Applied Meteorology, 33, 744-756. Tinarelli, G., D. Anfossi, M. Bider, E. Ferrero, S. Trini Castelli, 2000: A new high performance version of the Lagrangian particle dispersion dispersion model SPRAY, some case studies. Air Pollution Modelling and its Applications XII, S.E. Gryning and E. Batchvarova, eds, Kluwer Academic/Plenum Press. New York, 499-507. WHO - World Health Organization, 2005. Air quality guidelines for particulate matter, ozone, nitrogen dioxide and sulfur dioxide.