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Trace Metals and Pahs in Topsoils of the University Campus in the Megacity of São Paulo, Brazil

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Trace Metals and Pahs in Topsoils of the University Campus in the Megacity of São Paulo, Brazil Anais da Academia Brasileira de Ciências (2019) 91(3): e20180334 (Annals of the Brazilian Academy of Sciences) Printed version ISSN 0001-3765 / Online version ISSN 1678-2690 http://dx.doi.org/10.1590/0001-3765201920180334 www.scielo.br/aabc | www.fb.com/aabcjournal Trace metals and PAHs in topsoils of the University campus in the megacity of São Paulo, Brazil CHRISTINE L.M. BOUROTTE1, LUCY E. SUGAUARA2, MARY R.R. DE MARCHI2 and CARLOS E. SOUTO-OLIVEIRA1 1Instituto de Geociências, Universidade de São Paulo, Rua do Lago, 562, 05508-080 São Paulo, SP, Brazil 2Grupo de Estudo em Saúde Ambiental e Contaminantes Orgânicos, Departamento de Química Analítica, Instituto de Química, Universidade Estadual Paulista “Júlio de Mesquisa Filho”/UNESP, Campus Araraquara, Rua Prof. Francisco Degni, 55, 14800-970 Araraquara, SP, Brazil Manuscript received on April 5, 2018; accepted for publication on October 17, 2018 How to cite: BOUROTTE CLM, SUGAUARA LE, MARCHI MRR AND SOUTO-OLIVEIRA CE. 2019. Trace metals and PAHs in topsoils of the University campus in the megacity of São Paulo, Brazil. An Acad Bras Cienc 91: e20180334. DOI 10.1590/0001-3765201920180334. Abstract: The aim of this study is to discuss the concentration distribution, composition and possible sources of trace metals and 13 PAHs in topsoils of the University campus, in the city of São Paulo, the largest city of South America. Mineralogy and granulometry of topsoils (0-10 cm) samples, were determined and As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Sb, V, Zn, Hg, Pt, Pd and PAHs concentrations were quantified in the bulk fraction. The average clay content of soils was 221±61.8 g kg-1 and total carbon was low (mean of 25 g kg-1). Concentrations of metals were generally lower than the reference value established by the São Paulo State Environmental Agency and other studies in the São Paulo urban area, except for Cd, Ni, Pb, Cr and Zn. The mean concentration of the sum of 13 PAHs was 0.33 mg kg-1 and fluorene, indeno(1,2,3-cd) pyrene, anthracene, pyrene and benzo(ghi)perylene were the most abundant compounds. PAHs and trace metals variability were constrained in PMF analysis and showed an association with exhaust and non- exhaust vehicular emissions. The results also pointed out a spatial pattern in the campus area related to traffic conditions and intensity and terrain slope. Key words: urban topsoils, trace metals, PAHs, PMF. INTRODUCTION world’s population is living in urban areas and is exposed to a complex mixture of pollutants. Soils in The urban environment is a worldwide concern since urban areas are submitted to intense anthropogenic the concentration distribution and the geochemistry activities related to civil construction, industrial of contaminants in urban environment (atmosphere, activities and vehicular traffic that are responsible dust, soil, water and vegetation) need a better for their degradation and chemical contamination understanding (Wong et al. 2006). According to by direct disposal of contaminant to the soils. Dry the United Nations (2014), more than half of the and wet atmospheric deposition is also an important source for contaminants in urban soils and street Correspondence to: Christine Laure Marie Bourotte E-mail: [email protected] dust (Tanner et al. 2008). Soil pollution by metals ORCid: https://orcid.org/0000-0002-2821-1059 and other compounds such as Polycyclic Aromatic EARTH SCIENCES An Acad Bras Cienc (2019) 91(3) CHRISTINE L.M. BOUROTTE et al. TRACE METALS AND PAHS IN SÃO PAULO TOPSOILS Hydrocarbons (PAHs) has been described in several million inhabitants is in an area of 8,051 km2 of studies and different urban contexts principally which 18.7% are in the municipality of São Paulo performed in northern hemisphere (Werkenthin et (23o32’51”S, 46o38’10”W). The greater portion al. 2014, Orecchio 2010, Nadal et al. 2004, Jensen (66%) of the municipality of São Paulo is an urban et al. 2007, Haugland et al. 2008, Mielke et al. 2004, area and accounts with a population of 11 million Manta et al. 2002, Madrid et al. 2002, Charlesworth of inhabitants and a fleet of 8.5 million of vehicles, et al. 2011, Alekseenko and Alekseenko 2014) and composed of 70.5% of cars, 13% of light trucks, Asia (Zhang et al. 2006, Zuo et al. 2007, Chung 3% of trucks and buses and 13.5% of motorcycles et al. 2007, Ray et al. 2008, Agarwal 2009, Jiang (DETRAN 2017). The climate is humid subtropical, et al. 2009, Liu et al. 2010). In South America, with a dry season during winter (June-August) and fewer studies have been published in urban areas a wet season during summer (December-February), (Morton et al. 2001, Morcelli et al. 2005, Ribeiro an annual temperature average of 18.7oC and an et al. 2012, Figueiredo et al. 2011, Fujiwara et al. annual average precipitation of 1410 mm (IAG- 2011, Bourotte et al. 2009, Netto et al. 2006). USP 2016). Toxic substances such as trace metals or The sampling site is located in the western persistent organic pollutants like PAHs in the region of São Paulo city, on the campus of the soil-atmosphere interface are of concern since University of São Paulo, at the left bank of the they accumulate in topsoil horizons and may be Pinheiros river (Figure 1). The campus area can be re-suspended and inhaled causing risk for human divided into two main topographic zones: a flat one health and ecosystems. Wilcke (2007) also in the north, corresponding to the flood plain of the pointed out that PAHs as a complex mixture in Pinheiros river, now channeled, and a steepest one topsoils are originated from two main sources: the at the south with dense vegetal cover. Sedimentary background condition with a biological component formations occur in a great area of the campus: and anthropogenic processes through atmospheric the São Paulo Formation and the Itaquaquecetuba deposition. Since little information exists on the Formation. The first one outcrops at the “prefeitura” occurrence and distribution of metals and PAHs in and the Chemical Institute area. The second one Brazilian soils in urban areas, the aim of this study is occurs in the north part of the campus and close to discuss the distribution of trace metals and PAHs to the Olympic streak. These formations are concentration and their possible sources of topsoils related to fluvial deposits (meandering river and in the campus of the University, a green area of braided fluvial system deposits) and are constituted the São Paulo city. To this end descriptive statistics by conglomerates, sandstones and claystones. and Positive Matrix Factorization (PMF) analysis, Quaternary alluvial deposits occur in the Olympic a statistical approach to identify contaminant streak area. The bedrock is mainly constituted sources, were performed using spatial variability of of granitic rocks, gneisses and migmatites and PAHs and trace metals concentrations. outcrops in the south and southeast areas of the campus where the topography is steeper MATERIALS AND METHODS (790 m) and locally in the northwest area of the STUDY AREA AND SAMPLING SITES campus (Av. Prof. Lineu Prestes, close to IPEN and the universitary Hospital). A more detailed The metropolitan region of São Paulo is the world’s description of the geological aspects of the São fourth largest city and the biggest metropolis Paulo sedimentary basin and campus area can be in South America. This agglomeration of 21 found in Riccomini and Coimbra (1992), Iritani An Acad Bras Cienc (2019) 91(3) e20180334 2 | 23 CHRISTINE L.M. BOUROTTE et al. TRACE METALS AND PAHS IN SÃO PAULO TOPSOILS Figure 1 - Topsoil sampling sites located at the campus (green area) of the University of São Paulo, in the west zone of the São Paulo city. (1993) and Porsani et al. (2004). Natural soils commercial and residential zone of the city and originate from this lithology but have been affected some small manufacturing activities (metallurgy, by anthropogenic activities related to building cement and food manufacturing). Surrounding the and pavement construction. The campus is also campus, arterial streets (speed limit of 50 km/h) a green area (4.3 km2) used as a park for practice and “marginal Pinheiros” (a peripheral road with a and sporting events during weekends or holidays. higher speed limit of 90 km/h) with circulation of Green areas and gardens cover about 25% of the campus area and native vegetation is preserved in a all vehicles types (cars, trucks, buses, motorcycles). reserve forest area of 10ha. Important avenues with On the campus, cars and buses flow all day. During intense traffic of light- and heavy-duty vehicles rush hours, heavy circulation and stop and go-traffic surround the campus. The area is also inside a increase at the three main entrances of the campus. An Acad Bras Cienc (2019) 91(3) e20180334 3 | 23 CHRISTINE L.M. BOUROTTE et al. TRACE METALS AND PAHS IN SÃO PAULO TOPSOILS SAMPLING METHODS AND PREPARATION Analyses of total elemental composition were carried out after hot acid digestion (Aqua Regia) Topsoils (0-10 cm) were sampled in a 5 m2 area of 0.5g of samples and quantified by ICP-MS at where 6 subsamples were mixed to obtain a bulk ACME Analytical Laboratories, accredited by ISO/ sample at each sampling point. The characteristics IEC 17025. The Aqua Regia digestion provides of each area such as proximity of parking areas, partial results for most elements since it not attacks main streets, bus stops and green areas conditioned silicate minerals and it is generally used to estimate the sampling point locations (Figure 1). The the mobility, behavior and element availability distance between the sampling point and the road to plants.
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