Trace metals and PAHs in topsoils of the University campus in the megacity of São Paulo, Brazil

BOUROTTE, CHRISTINE L.M.; SUGAUARA, LUCY E.; MARCHI, MARY R.R. DE; SOUTO-OLIVEIRA, CARLOS E.

doi:10.1590/0001-3765201920180334

CHRISTINE L.M. BOUROTTE

Instituto de Geociências, Universidade de São Paulo, Rua do Lago, 562, 05508-080 São Paulo, SP, Brazil

http://orcid.org/0000-0002-2821-1059

LUCY E. SUGAUARA

Grupo 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

MARY R.R. DE MARCHI

Grupo 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

CARLOS E. SOUTO-OLIVEIRA

Instituto de Geociências, Universidade de São Paulo, Rua do Lago, 562, 05508-080 São Paulo, SP, Brazil

Correspondence to: Christine Laure Marie Bourotte E-mail: chrisbourotte@usp.br ORCid: https://orcid.org/0000-0002-2821-1059

AUTHOR CONTRIBUTIONS

Christine Laure Marie Bourotte contributed to the sampling, and physical and chemical characterization of the samples and all results discussion. Lucy Elaine Sagauara and Mary Rosa Rodrigues de Marchi constributed to the quantification of PAHs in samples and results discussion.Carlos Eduardo Souto-Oliveira contributed to the statistical analysis by PMF and results discussion.

MAJOR ELEMENTS					TRACE ELEMENTS
	mean	sth.	min.	max.		mean	sth.	min.	max.
	(g kg^-1)					(mg kg^-1)
Al	80.5	12.8	43.2	103	As	5.14	1.64	2.10	8.70
Si	305	21.0	274	368	Ba	48.5	14.7	30.8	75.5
Fe	33.1	6.54	18.0	49.4	Cd	0.59	0.60	0.18	2.96
K	6.95	2.30	2.91	11.4	Co	3.73	2.63	1.60	14.6
Ca	2.42	0.97	1.14	4.93	Cr	42.1	23.8	24.6	153
Mg	1.27	0.63	0.66	3.79	Cu	19.5	5.48	11.8	31.3
Na	1.36	0.64	0.67	3.19	Mo	0.91	0.26	0.45	1.59
P	0.45	0.09	0.26	0.61	Ni	11.2	15.3	4.50	66.6
Mn	0.25	0.09	0.16	0.54	Pb	40.8	14.1	17.4	75.9
Ti	5.09	0.86	3.26	6.83	Sb	0.32	0.11	0.13	0.56
					V	63.4	15.7	26.0	91.0
C _tot	25.1	6.30	15.3	39.8	Zn	94.6	50.8	38.5	275
						(µg kg^-1)
					Hg	79.0	40.0	22.0	197
					Pt	2.80	1.87	1.00*	7.00
					Pd	8.04	7.55	5.00*	40.0

	Cd	Cu	Ni	Pb	Zn	Co	Cr	Sb	As	Ba	Mo	V	Pt	Pd
		(mg kg^-1)
(1) World surface soils	1.1	14	18	25	62	6.9	42	0.62	4.7	362	1.8	60	3	2
(2) Brazilian Ferralsols	0.66 ±0.19	65±7.4	18±12	22±9	39±24
(3) Quality Reference Value (CETESB)	0.50	35.0	13.0	17.0	60.0	13.0	40.0	0.50	3.5	75.0	4.0
(4) Serra do Mar natural soils (Cunha)		14.0		9.00		2.00	78.0			170.5		137.5
(4) São Paulo urban forest soils (PEFI)		16.5		10.5	26.0	3.00	65.0		11.5	115.3		148.3
(5) São Paulo urban soils (12 parks)*					81.5		49		9.63	683.3
(6) Marginal Pinheiros soils, São Paulo*					467	7.03	87.1	2.76	10.5	459			11.4	58.6
(7) Roadsoils, São Paulo													0.3-17.0	1.1-58.0
(8) Basement rocks at study site		13.0			83.0	15.0	75.0			1590		72.0
(9) Urban soils, China	0.394	38.2	29.2	45.3	112		76	1.72	11.4
(10) Urban soils, Mexico													3.1-332.7	2.5-101
(11) Urban park soils, Hong Kong	0.36±0.16	16.2±22.6	4.08±2.51	88.1±62.0	103±91.3	3.55±1.6	17.8±5.92
(12) Roadside soils, Perth (Australia)													31-153	14-109
(13) Roadside soils, Melbourne (Australia)	0.06-0.59	4-12	7-20	16-144	10.4-88.8		18-29
(14) Urban soils, Xuzhou (China)			34±3.4	37±19.4	169±106		73±8.4
(15) Urban soils, New Orleans (USA)	2.1	17.6	9.1	174	147		1.9					4.8
(16) Urban soils, Hungria	0.55 ±0.36	59±78.8	22.6±4.7	15.7 ±8.23	80.2 ±30.9	6.09±2.1	31.3±7.2		7.19 ±2.3
(17) Urban soils, Palermo (Italy)		63**		202**	138**							58
(18) Urban soils, Prague	0.26 ±0.04	19.7 ±1.53	11.1 ±1.29	126±8.80	54.8±7.30	2.36±0.6	33±0.62
(19) Urban soils, Seville (Spain)	1.39±0.16	121±74	27.6±6.0	397±325			121±74
(20) Urban soils, Chicago (USA)		59.0**	31.0**	198**	235**						5.0**	82.0**
(21) Urban soils, Toronto (Canada)													8.7	63
(22) Urban soils, Napoli (Italy)													<2-52	<10-110
This study	0.59 ±0.6	19.5 ±5.48	11.2 ±15.3	40.8 ±14.1	94.6 ±50.8	3.73 ±2.6	42.2 ±23.8	0.32 ±0.1	5.14 ±1.6	48.5 ±14.7	0.91 ±0.3	63.4 ±15.7	2.80 ±1.87	8.04 ±7.55

* mean value ** median value.
¹Kabata-Pendias and Mukherjee 2007Kabata-Pendias A and Mukherjee AB. 2007. Trace elements from soil to human, Trace Elements from Soil to Human. Springer Verlag Berlin Heidelberg Ed., 550 p.; ²Campos et al. 2003Campos ML, Pierangeli MAP, Guilherme LRG, Marques JJ and Curi N. 2003. Baseline Concentration of Heavy Metals in Brazilian Latosols. Commun Soil Sci Plant Anal 34: 547-557.; ³ CETESB 2014; ⁴ Bourotte 2009, Licht 2005Licht OAB. 2005. Geoquímica de solos do Estado do Paraná, vol 1/2, Mineropar, Curitiba, Paraná.; ⁵ Figueiredo et al. 2011; ⁶ Ribeiro et al. 2012, Nammoura et al. 2009NAMMOURA NETO GM, FIGUEIREDO AMG, RIBEIRO AP, SILVA NC, TICIANELLI RB and CAMARGO SP. 2009. Metais em solos urbanos: avaliação da concentração em solos adjacentes à marginal do Rio Pinheiros. International Nuclear Atlantic Conference, INAC 2009, Rio de Janeiro, RJ, Brazil, September 27 to October 2, 2009.; ⁷ Morcelli et al. 2005; ⁸ V.A. Janasi (personal communication); ⁹ Cheng et al. 2014Cheng H, Li M, Zhao C, Li K, Peng M, Qin A and Cheng X. 2014. Overview of trace metals in the urban soil of 31 metropolises in China. J Geochem Explor 139: 31-52.; ¹⁰ Morton et al. 2001; ¹¹ Lee et al. 2006Lee CSL, Li X, Shi W, Cheung SCN and Thornton I. 2006. Metal contamination in urban, suburban, and country park soils of Hong Kong: A study based on GIS and multivariate statistics. Sci Total Environ 356: 45-61.; ¹² Whiteley and Murray 2003; ¹³ De Silva et al. 2016De Silva S, Ball AS, Huynh T and Reichman SM. 2016. Metal accumulation in roadside soil in Melbourne, Australia: Effect of road age, traffic density and vehicular speed. Environ Pollut 208: 102-109.; ¹⁴ Wang 2013Wang XS. 2013. Assessment of heavy metal pollution in Xuzhou urban topsoils by magnetic susceptibility measurements. J Appl Geophys 92: 76-83.; ¹⁵ Mielke et al. 2001Mielke HW, Wang G, Gonzales CR, Le B, Quach VN and Mielke PW. 2001. PAH and metal mixtures in New Orleans soils and sediments. Sci Total Environ 281: 217-227.; ¹⁶ Szolnoki et al. 2013SZOLNOKI Z, FARSANG A and PUSKÁS I. 2013. Cumulative impacts of human activities on urban garden soils: Origin and accumulation of metals. Environ Pollut 177: 106-115.; ¹⁷ Manta et al. 2002; ¹⁸ Boruvka et al. 2005Boruvka L, Vacek O and Jehlicka J. 2005. Principal component analysis as a tool to indicate the origin of potentially toxic elements in soils. Geoderma 128: 289-300.; ¹⁹ Madrid et al. 2008Madrid F, Díaz-Barrientos E and Madrid L. 2008. Availability and bio-accessibility of metals in the clay fraction of urban soils of Sevilla. Environ Pollut 156: 605-610.; ²⁰ Cannon and Horton 2009Cannon WF And Horton JD. 2009. Soil geochemical signature of urbanization and industrialization - Chicago, Illinois, USA. Appl Geochem 24: 1590-1601.; ²¹ WisemanWiseman CLS, Hassan Pour Z and Zereini F. 2016. Platinum group element and cerium concentrations in roadside environments in Toronto, Canada. Chemosphere 145: 61-67. et al. 2016; ²² Cicchella et al. 2003Cicchella D, De Vivo B and Lima A. 2003. Palladium and platinum concentration in soils from the Napoli metropolitan area, Italy: Possible effects of catalytic exhausts. Sci Total Environ 308: 121-131..

	PAHs
	n	mean	sth.	min.	max.	Prevention Value*
			(mg kg^-1)			(mg kg^-1)
Acenaphthene (ACE)	6	0.017	0.015	0.003	0.041	-
Fluorene (FLU)	10	0.102	0.076	0.008	0.208	-
Phenanthrene (PHE)	14	0.001	0.001	0.000	0.003	3.6
Anthracene (ANT)	15	0.060	0.058	0.001	0.164	0.3
Fluoranthene (FLT)	8	0.008	0.005	0.002	0.015	-
Pyrene (PYR)	11	0.043	0.063	0.004	0.220	-
Benzo(a)anthracene (BaA)	15	0.020	0.016	0.004	0.046	0.2
Chrysene (CHRY)	14	0.038	0.020	0.003	0.068	1.6
Benzo(b)fluoranthene (BbF)	15	0.008	0.006	0.001	0.023	0.7
Benzo(k)fluoranthene (BkF)	12	0.036	0.063	0.007	0.234	0.8
Benzo(a)pyrene (BaP)	1	0.275	-	0.000	0.275	0.1
Dibenz(a,h)anthracene (DBahA)	8	0.038	0.027	0.012	0.083	0.2
Benzo(ghi)perylene (BghiP)	11	0.041	0.033	0.004	0.109	0.5
Indeno(1,2,3-cd)pyrene (IND)	9	0.067	0.044	0.013	0.160	0.4
∑PAHs	17	0.329	0.325	0.072	1.379
∑Low Molecular Weight PAHs	17	0.120	0.096	0.001	0.322
∑High Molecular Weight PAHs	17	0.209	0.259	0.0000	1.1183
∑Carcinogenic	17	0.157	0.181	0.0000	0.7767
∑2-3 rings	17	1.120	0.096	0.001	0.322
∑4 rings	17	0.080	0.071	0.000	0.318
∑5 rings	17	0.067	0.139	0.000	0.595
∑6 rings	17	0.062	0.072	0.000	0.241

Location	Concentration	Number of PAHs	Area	Reference
São Paulo, Brazil	0.33±0.32 [0.07-1.38]	13	campus of the university (urban green area)	This study
São Paulo, Brazil	0.818	16	urban forest (PEFI)	Bourotte et al. 2009
Cunha, Brazil	0.180	16	natural forest soils	Bourotte et al. 2009
Uberlândia, Brazil	[0.007-0.390]	20	urban	Wilcke et al. 1999
Manaus, Brazil	0.016-0.038	21	Amazonian forest soils	Krauss et al. 2005
Brazil	0.145 [0.015-0.397]	20	Terra Firme, Amazon Basin	Wilcke et al. 2003Wilcke W, Amelung W, Krauss M, Martius C, Bandeira A and Garcia M. 2003. Polycyclic aromatic hydrocarbon (PAH) patterns in climatically different ecological zones of Brazil. Org Geochem 34: 1405-1417.
	0.068 [0.029-0.142]	20	Pantanal
	0.017 [0.0048-0.035]	20	Cerrado central
	0.115 [0.062-0.143]	20	Mata Atlântica
	0.023 [0.0071-0.064]	20	Caatinga
Beijing, China	0.865±0.799		residential	Peng et al. 2013Peng C, Ouyang Z, Wang M, Chen W, Li X and Crittenden JC. 2013. Assessing the combined risks of PAHs and metals in urban soils by urbanization indicators. Environ Pollut 178: 426-432.
Beijing, China	1.285±1.848	16	park	Peng et al. 2011
	1.026±0.726		roadside (heavy traffic)
	0.538±0.340		roadside (light traffic)
	0.811±0.748		residential
Beijing, China	1.803±1.824	16	urban soils	Liu et al. 2010
Dalian, China	4.391±4.370	25	garden	Wang et al. 2009Wang DG, Yang M, Jia HL, Zhou L and Li YF. 2009. Polycyclic sromatic hydrocarbons in urban street dust and surface soil: Comparisons of concentration, profile, and source. Arch Environ Contam Toxicol 56: 173-180.
	3.237±2.735		business/residential
Shangai, China	1.97 [0.083-7.220]	16	urban soils	Wang 2013
Nanjing, China	3.330 [0.059-18]	16	urban soils	Wang et al. 2015Wang C, Wu S, Zhou Sl, Wang H, Li B, Chen H, Yu Y and Shi Y. 2015. Polycyclic aromatic hydrocarbons in soils from urban to rural areas in Nanjing: Concentration, source, spatial distribution, and potential human health risk. Sci Total Environ 527-528: 375-383.
Huizhou, China	[0.0354-0.5345]	16	urban soils	Ma and Zhou 2011Ma J and Zhou Y. 2011. Soil pollution by polycyclic aromatic hydrocarbons: A comparison of two Chinese cities. J Environ Sci 23: 1518-1523.
Zhanjiang, China	[0.0095-6.618]	16	urban soils
Bangkok, Thailand	0.1292	20	urban soils	Wilcke et al. 1999
Shangai, China	6.280	16	roadside soils	Jiang et al. 2009
	2.130	16	park
Hong Kong, China	0.169 [0.007-0.410]	16	urban soils	Zhang et al. 2006
Ulsan, South Korea	0.390 [0.065-1.200]	16	urban soils	Kwon and Choi 2014
	0.220 [0.092-0.450]	16	rural soils
Kumasi, Ghana	0.4425±0.5272	22	urban soils	Bortey-Sam et al. 2014Bortey-Sam N, Ikenaka Y, Nakayama SMM, Akoto O, Yohannes YB, Baidoo E, Mizukawa H and Ishizuka M. 2014. Occurrence, distribution, sources and toxic potential of polycyclic aromatic hydrocarbons (PAHs) in surface soils from the Kumasi Metropolis, Ghana. Sci Total Environ 496: 471-478.
Argentina	0.0075 [0.0017-0.031]	16	soils transect	Wilcke et al. 2014Wilcke W, Bandowe BAM, Lueso MG, Ruppenthal M, del Valle H and Oelmann Y. 2014. Polycyclic aromatic hydrocarbons (PAHs) and their polar derivatives (oxygenated PAHs, azaarenes) in soils along a climosequence in Argentina. Sci Total Environ 473-474: 317-325.
Dehli, India	4.694±3.028 [1.062-9.652]	16	traffic site	Agarwal 2009
Lisbon, Portugal	1.544	16	urban	Cachada et al. 2012Cachada A, Pato P, Rocha-Santos T, da Silva EF and Duarte AC. 2012. Levels, sources and potential human health risks of organic pollutants in urban soils. Sci Total Environ 430: 184-192.
Viseu, Portugal	0.169	16	urban
Bayreuth, Germany	37.3	20	roadside soils	Wilcke et al. 2002Wilcke W, Krauss M and Amelung W. 2002. Carbon isotope signature of polycyclic aromatic hydrocarbons (PAHs): Evidence for different sources in tropical and temperate environments? Environ Sci Technol 36: 3530-3535.
Bergen, Norway	6.780	16	urban soils	Haugland et al. 2008
New Orleans, USA	3.731 [0.647-40.692]	16	urban	Mielke et al. 2001
New Orleans, USA	5.100	17	urban soils	Wang et al. 2008Wang G, Zhang Q, Ma P, Rowden J, Mielke HW, Gonzales C and Powell E. 2008. Sources and Distribution of Polycyclic Aromatic Hydrocarbons in Urban Soils: Case Studies of Detroit and New Orleans. Soil Sediment Contam 17: 547-563.
Detroit, USA	7.843	17	urban soils
London, UK	18	16	urban soils	Vane et al. 2014Vane CH, Kim AW, Beriro DJ, Cave MR, Knights K, Moss-Hayes V and Nathanail PC. 2014. Polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB) in urban soils of Greater London, UK. Appl Geochem 51: 303-314.
Taragona, Spain	0.736	16	urban/residential zone	Nadal et al. 2004
Rouen, France	2.780±0.879	14	urban site	Motelay-Massei et al. 2004Motelay-Massei A, Ollivon D, Garban B, Teil MJ, Blanchard M and Chevreuil M. 2004. Distribution and spatial trends of PAHs and PCBs in soils in the Seine River basin, France. Chemosphere 55: 555-565.
Galsgow, UK	[1.487-51.822]	15	urban	Morillo et al. 2007Morillo E, Romero aS, Maqueda C, Madrid L, Ajmone-Marsan F, Grecman H, Davidson CM, Hursthouse aS and Villaverde J. 2007. Soil pollution by PAHs in urban soils: a comparison of three European cities. J Environ Monitori 9: 1001.
Torino, Italy	[0.148-3.410]	15	urban

[1] Correspondence to: Christine Laure Marie Bourotte E-mail: chrisbourotte@usp.br ORCid: https://orcid.org/0000-0002-2821-1059

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Trace metals and PAHs in topsoils of the University campus in the megacity of São Paulo, Brazil