- Email: [email protected]
Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil
MPB-08459; No of Pages 4 Marine Pollution Bulletin xxx (2017) xxx–xxx
Contents lists available at ScienceDirect
Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul
Baseline
Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil M.W. Lima a, M.L.S. Santos b,⁎, K.C.F. Faial c, E.S. Freitas c, M.O. Lima c, J.A.R. Pereira d, I.P.R.T. Cunha a a
Programa de Pós-Graduação em Aquicultura e Recursos Aquáticos Tropicais, Universidade Federal Rural da Amazônia, Belém, Brazil Instituto Sócio Ambiental e dos Recursos Hídricos, Universidade Federal Rural da Amazônia, Belém, Brazil Seção de Meio Ambiente, Instituto Evandro Chagas, Ananindeua, Brazil d Faculdade de Engenharia Sanitária e Ambiental, Universidade Federal do Pará, Rua Augusto Corrêa, 1, 66075-110, Pará, Brazil b c
a r t i c l e
i n f o
Article history: Received 25 December 2015 Received in revised form 22 February 2017 Accepted 27 February 2017 Available online xxxx Keywords: Vigia Geochemistry Reference environment
a b s t r a c t The Furo of Laura is an economically important river in the Amazon estuary. Thus, in the present study, we evaluated the metal distribution (Al, Cd, Co, Cu, Cr, Fe, Ni, and Mg) in the bottom sediments of this river. The sediments were sampled at four points every 2 months for a year with an Ekman-Birge sampler. After microwave acid digestion, the metal levels were determined by optical emission spectrometry with inductively coupled plasma. The particle size and organic matter content influenced the concentration of the metals. The sediments were not enriched by the analyzed metals; the estuary therefore retained the characteristics of an uncontaminated environment, thus serving as a reference environment for comparison. © 2017 Published by Elsevier Ltd.
Development in Brazil, especially over the last three decades, had considerable environmental impacts that were caused by a high degree of urbanization (Bregunce et al., 2011). The situation is more critical in estuarine environments with port activities and industrial and urban waste deposits (Chakraborty et al., 2014). The Vigia municipality is located in the microregion of “Salgado,” in the northeast of the state of Para. The urbanization process in this location resulted in the removal of riparian forests and discharge of untreated domestic and industrial wastewater that passes through several neighborhoods, arriving at the Furo of Laura estuary (Bentes and Barbosa, 2015). The margin of this estuary currently has approximately 51,705 inhabitants occupying an area of 301 ha (IBGE, 2016). This estuary is considered the main hydrography of the Vigia municipality. The river is a large body of water (approximately 43,686 m in length) consisting of numerous microbasins formed by the tidal effects and the Marajó Bay. The sediments of the estuary are rich in Cu, Cr, Ni, Pb, and Zn in several sectors of the eastern margin, and the origin of these metals is linked to the domestic sewage generated by the city of Belém (Corrêa and Pereira, 2002). In addition, because its main economy is fishing, the municipality hosts several fishing companies; in one of them, the pollution potential corresponds to the load generated by a city of 567 to 653 inhabitants in terms of the organic load (Mello, 2007), reflecting the importance of this study. ⁎ Corresponding author. E-mail address: [email protected] (M.L.S. Santos).
In this study, we evaluated seasonal and spatial distribution of the heavy metals Al, Cd, Co, Cu, Cr, Fe, Ni, and Mg and characterized the particle size fractions and organic matter (OM) content in the bottom sediments of Furo of Laura estuary to create a reliable heavy metal database with which future levels can be compared and evaluated. Sediment samples were obtained at four points in the Furo of Laura estuary (P1: reference area, P2: intermediate area, P3: area under urbanized influence, P4: Marajó Bay influence area) (Fig. 1), one sample at each point, four in each month (September and November 2011 and January, March, May, and July 2012); a total of 24 samples were obtained. Approximately 500 g (wet weight) of bottom sediment was sampled at each point using an Ekman-Birge sampler with the aid of a boat during neap tide. Sediment particle sizes were analyzed according to the method given by Lima et al. (2015) using the laser in the Shimadzu equipment, model SALD - 2201. OM content was analyzed according to the method reported by Loring and Rantala (1992), which is based on the oxidation of organic carbon with potassium dichromate in an acidic medium. The heavy metals were determined from the silt and clay fraction (b0.063 mm). Nitric acid (HNO3), hydrochloric acid (HCl), hydrofluoric acid (HF), and boric acid (H3BO3) were used for the digestion of the sediments; the digestion was performed in a closed system using microwave radiation (MARSX pres, CEM Corp. Matthews, NC, USA). The metals were analyzed by optical emission spectrometry with inductively coupled plasma (ICP-OES, Model Vista- MPXCCD, VARIAN) according to the method by Spectro (1999). To validate the results, we used a reference sample for metals in the soil (SRM 2710, NIST, USA), and the
http://dx.doi.org/10.1016/j.marpolbul.2017.02.073 0025-326X/© 2017 Published by Elsevier Ltd.
Please cite this article as: Lima, M.W., et al., Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil, Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.073
2
M.W. Lima et al. / Marine Pollution Bulletin xxx (2017) xxx–xxx
Fig. 1. Location of the sampling sites in the Furo of Laura.
recovery of the certified values was 76.7% for Al, 86.1% for Cd, 87.6% for Cu, 83.5% for Ni, 100% for Fe, and 74.1% for Mg. The results were compared with the quality reference values using the ERL value to represent a minimal effects range; concentrations equal to and above the ERL value but below the ERM value represent possible effects; concentrations equivalent to and above the ERM value represent frequent occurrence of probable effects (Long et al., 1995). The sediments from Furo of Laura were predominantly sandy, with the mean proportions of sand, silt, and clay being 67.09%, 29.66%, and 3.26%, respectively, in the less rainy season, with an average rain of 75%, 21.59%, and 3.40%, respectively. Regarding the spatial variation (Table 1), there were no fluctuations in the granulometric fractions. The OM had higher average values at the innermost point of the Furo (P1). The highest concentrations of heavy metals occurred more frequently at the point near the Vigia municipality (P2) for Al, Co, Cu, Cr, Ni, and Mg and at the point near Marajó Bay (P1) for Cd and Fe. The lowest concentrations of Cd, Co, Cu, Cr, and Fe occurred at point P2, whereas the concentrations of Al, Ni, and Mg were lower at P4, P3, and P1, respectively. Despite the higher concentrations observed at P1 and P2, the highest averages of all other metals (Al, Cd, Co, Cu, Cr, Ni, and Mg) occurred at the point ahead of the Vigia municipality (P3), with the exception of iron Fe (P1). The variables analyzed revealed the occurrence of seasonal variations in the study area (Table 2) and space.
For the metals, we could verify that that the concentrations of Al, Cu, Cr, and Mg remained higher in the less rainy season and those of Cd, Co, Fe, and Ni were higher in the rainy season. It is noteworthy that although some metals remain at higher concentrations in the rainy season (Cd, Co, Fe, and Ni), the highest average for all metals occurred in the less rainy season (Fig. 2). The largest amount of sand was found at sampling points P3 and P4, which are closest to Marajó Bay (mouth of the river). In the Marajó Bay, the sand fraction is dominant because of the presence of morphological sand banks and bars (França and Souza-Filho, 2006). This prevalence may be due to the influence of the Marajó Bay in the outer region in the Furo of Laura. Erosion of the soil and the micro basins of Vigia and Colares may also contribute to this result. Regarding the seasonal variations of heavy metals, the highest concentrations were found in the less rainy season, and the results at these sampling points reinforces the local geochemical origin of these metals. The low concentrations of Al are caused by the weathering barriers that are made of extensive lateritic coatings containing oxides, hydroxides, and oxyhydroxides of Al and Fe (Espindola and Daniel, 2008), thus explaining their natural origin. Low concentrations of detected Cu and Ni may be related to low levels of OM and clay in the Furo of Laura estuary, which greatly influence the concentration of these metals in the sediments (Chester et al., 1988) as they function as sites of adsorption (Siqueira et al., 2006). Cr is a characteristically terrigenous element. Its source is associated with the formation of weathering barriers,
Table 1 Maximum, minimum, and average values of fractions of sand, silt, clay, and OM (in %) verified in the sampling. Points of collection
Sand % Silt % Clay % OM % a b c
P1
P2
P3
P4
Mina
Maxb
Avgc
Mina
Maxb
Avgc
Mina
Maxb
Avgc
Mina
Maxb
Avgc
63.1 17.4 0.8 5.9
81.0 32.8 6.1 10.7
69.7 26.5 3.9 8.4
61.3 13.5 0.1 4.6
86.4 36.8 5.7 10.2
70.6 26.2 3.2 7.1
64.9 5.6 0.1 6.6
94.3 32.1 3.5 9.8
71.8 25.8 2.4 8.4
66.0 12.4 0.3 4.2
87.2 30.9 11.0 8.6
72.1 24.0 3.8 6.9
Minimum. Maximum. Average.
Please cite this article as: Lima, M.W., et al., Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil, Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.073
M.W. Lima et al. / Marine Pollution Bulletin xxx (2017) xxx–xxx
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Table 2 Maximum (Max), minimum (Min), and average (Avg) values of the metals Al, Cd, Co, Cu, Cr, Ni, Fe, and Mg (in mg·kg−1) detected in the sampling. Points of collection
This study
P1 (reference area)
P2 (intermediate area)
P3 (area under urbanized influence)
P4 (Marajó Bay influence area)
Min Max Avg Min Max Avg Min Max Avg Min Max Avg
Range of low biota effects (ERL)a Range of medium to biota effects (ERM)a Sediments of the estuaryb Sediments of the Bay of Guajará-PA Nonpolluted Sediments, Cardoso Island, Cananéia (SP)c Sediments of the River Formoso estuary (PE)d Port of Mitilini (Greece)e Bay of Moreton (Austrália) Before-industrializationf a b c d e f
Al
Cd
Co
Cu
Cr
Ni
Fe
Mg
9198.3 14,957.5 11,509.5 9999.6 17,752.6 12,800.1 9660.4 14,477.1 13,207.7 7465.6 16,806.6 11,500.3
3.0 5.2 3.8 2.7 4.9 3.9 3.4 4.5 3.9 2.8 3.9 3.3
9.1 13.0 10.2 8.3 13.4 11.2 10.5 12.7 11.6 8.6 11.3 9.7
11.7 15.1 13.3 9.4 16.4 13.1 12.4 15.0 13.8 10.0 13.5 11.9
53.1 62.8 57.2 42.3 71.4 57.8 55.9 63.2 58.6 46.3 60.4 52.4
19.0 21.9 20.5 12.9 24.3 19.5 19.1 22.9 20.8 15.9 20.9 18.4
27,035.2 37,606.8 30,346.6 23,674.8 35,832.5 29,870.2 28,263.6 32,449.6 30,072.2 25,116.9 30,251.2 27,446.2
114,000 194,000 166,000 134,000 259,000 193,000 171,000 215,000 197,000 126,000 232,000 181,000
* * 43,000 49,000 1100–16,200 766–2383 18,600–52,600 5300–14,700
1.2 9.6 * * 0–30.9 0.04–0.11 0.05–0.5 b0.4–0.6
* * * * 4.4–47.3 0.5–1.5 * b1.2–5
34 270 16.5 25.3 0–27.2 1.15–3.71 9.39–67.6 0.5–13
81 370 51.3 55.6 0–88 2.7–7.4 44.6–154 7–72
20.9 51.6 20.1 22.4 * 1,1–3.2 * *
* * 32,000 31,000 1500–22,600 3675–21,807 7700–28,100 1100–117,200
* * * * * 3568–12,420 * *
Long et al. (1995). Oliveira et al. (2015). Semensatto-Jr et al. (2007). Silva et al. (2009). Aloupi and Angelidis (2001). Preda and Cox (2002).
which are characteristic of the Vigia soils (Idesp, 2013), and their low concentrations refer to the geochemical origin. The concentration of Mg was slightly high at sampling points P3 and P4; this may be related to agricultural inputs such as calcareous inputs. Lime (calcium oxide, CaO) is derived from the calcination of limestone or dolomite. It is commonly used for painting homes in the municipality. With regard to the
reference index, all the metals presented values below the threshold for adverse risk to biota. Therefore, the sediments of the Furo of Laura estuary are predominantly sandy, with low OM content, and characterized as a high-energy environment, being slightly influenced by seasonality and the hydrodynamics of Marajó Bay. The particle size, OM content, and local
Fig. 2. Seasonal distribution of (A) granulometric fractions, (B) OM, (C) Al, (D) Cd, (E) Co, (F) Cu, (G) Cr, (H) Fe, (I) Ni, and (J) Mg in the sediments of Furo da Laura.
Please cite this article as: Lima, M.W., et al., Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil, Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.073
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M.W. Lima et al. / Marine Pollution Bulletin xxx (2017) xxx–xxx
geochemistry influence the concentrations of Al, Cd, Cu, Cr, Ni, Fe, and Mg in the bottom sediments. This estuary was not enriched by the metals analyzed, thus making it a reference environment that is uncontaminated by these elements; therefore, the future levels of metals can be evaluated and compared with the present values. Acknowledgments We thank the Coordination of Improvement of Higher Education Personnel (CAPES), Program in Tropical Aquaculture and Aquatic Resources, Environmental Chemistry Laboratories-UFRA, Chemical Oceanography-UFPA, and Toxicology-IEC for performing the analyses. References Aloupi, M., Angelidis, M.O., 2001. Geochemistry of natural and anthropogenic metals in the coastal sediments of the Island of Lesvos, Aegean Sea. Environ. Pollut. 113, 211–219. Bentes, L., Barbosa, E.J.S., 2015. Urban occupation in “bajaadas” in the coastal zone of the State of Pará, case of the stream of Rocinha, city of Vigia of Nazaré. J. Hist. Geog. Inst. Pará (IHGP) 02 (02), 108–119. Brazilian Institute of Geography and Statistics (IBGE), Pará, Vigia, 2016á. Available. http:// cidades.ibge.gov.br/xtras/perfil.php?codmun=150820N (Access on November 14, 2016). Bregunce, D.T., Jordan, E.J., Dziedzic, M., Maranho, L.T., Aparecida Cubas, A.S., 2011. Evaluation of the water quality of the Müller's Ribeirão, Curitiba-PR. Braz. J. Wat. Res. 16, 39–47. Chakraborty, P., Ramteke, D., Chakraborty, S., Nath, B.N., 2014. Changes in metal contamination levels in estuarine sediments around India – an assessment. Mar. Pollut. Bull. 78, 15–25. Chester, R., Thomas, A., Lin, F.J., Basaham, A.S., Jacinto, G.A., 1988. Solid-state copper spectra in water particles and oceanic surface sediments. Mar. Chem. 24, 261–292. Corrêa, J.A.M., Pereira, K.R., 2002. Study of the dispersion of heavy metals in sediments of the border of Belém. Bull. Museu Paraense Emílio Goeldi, Earth Sci. Ser. 14, 79–101.
Espindola, C.R., Daniel, L.A., 2008. Laterite and Lateritic Soils in Brazil. Bulletin Technical of FATECSP BT/24. pp. 21–24. França, C.F., Souza-Filho, P.W.M., 2006. Morphological compartmentalization of the eastern margin of the Island of Marajó: Coastal Zone of the municipalities of Soure and Saving Land - State of Pará. Braz. J. Geomorph. 7, 33–43. Institute of Economic, Social and Environmental Development of Pará-Idesp, 2013t. Municipal Statistics: Watch. Belém-PA. 49 p. http://iah.iec.pa.gov.br/iah/fulltext/ georeferenciamento/vigia.pdf (Accessed on 13 March 2013). Lima, M.W., Santos, M.L.S., Montelo, D.J., Nunes, D.M., Alves, I.C.C., Silva, M.S.F., 2015. Temporal analysis of the granulometric composition of an Amazonian estuary, Pará, Brazil. Scientia Plena 11 (1), 1–11. Loring, D.H., Rantala, R.T.T., 1992. Manual for analyzing the geochemistry of marine sediments and suspended particles. Comments-Earth Science. 32, 235–283. Long, E.R., Macdonald, D.D., Smith, S.L., Calder, F.D., 1995. Incidence of adverse biological effects within ranges of chemical concentration in marine and estuarine sediments. Environ. Manag. 19 (1), 81–97. Mello, V.S.A., 2007. Characterization of the Effluent From the Amazonian Fishing Industry and its Release Into the Receiving Body - Vigia de Nazaré/PA. Master's Dissertation (Master's in Civil Engineering). 220. Federal University of Pará. Oliveira, E.C., Lafon, J.M., Corrêa, J.A.M., Carvalho, J.H.S., Dias, F.F., Taddei, M.H.T., 2015. Distribution of the traces metals in sediments of the hydrographic system of the region of Belém, PA (West bank of Guajará bay and Carnapijó river). Geochim. Bras. 29 (2), 139–153. Preda, M., Cox, M.E., 2002. Trace metal occurrence and distribution in sediments and mangroves, Pumiscestone region, southeat Queensland, Austrália. Environ. Int. 28, 433–449. Semensatto-Jr, D.L., Araújo, G.C.L., Funo, R.H.F., Santa-Cruz, J., Dias-Brito, D., 2007. Metals and non-metals in sediments of a non-polluted mangrove, Cardoso Island, Cananéia (SP). Res. Geosci. 34 (2), 25–31. Silva, N.M.T.N., Neto, J.A.S., Silva, W.L., Valença, L.M.M., 2009. Geochemistry of drainage bottom sediments in tropical estuary, northeastern Brazil. Geol. Stud. 19 (1), 139–159. Siqueira, G.W., Pereira, S.F.P., Aprile, F.M., 2006. Determination of trace elements (Zn, Co and Ni) in sediments of the Amazon Continental Shelf under influence of the Amazon River discharge. Acta Amazônica 36 (3), 321–326. SPECTRO, 1999. User's Guide of Spectro ICP-OES. Manual do Usuário (240 p).
Please cite this article as: Lima, M.W., et al., Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil, Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.073
Contents lists available at ScienceDirect
Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul
Baseline
Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil M.W. Lima a, M.L.S. Santos b,⁎, K.C.F. Faial c, E.S. Freitas c, M.O. Lima c, J.A.R. Pereira d, I.P.R.T. Cunha a a
Programa de Pós-Graduação em Aquicultura e Recursos Aquáticos Tropicais, Universidade Federal Rural da Amazônia, Belém, Brazil Instituto Sócio Ambiental e dos Recursos Hídricos, Universidade Federal Rural da Amazônia, Belém, Brazil Seção de Meio Ambiente, Instituto Evandro Chagas, Ananindeua, Brazil d Faculdade de Engenharia Sanitária e Ambiental, Universidade Federal do Pará, Rua Augusto Corrêa, 1, 66075-110, Pará, Brazil b c
a r t i c l e
i n f o
Article history: Received 25 December 2015 Received in revised form 22 February 2017 Accepted 27 February 2017 Available online xxxx Keywords: Vigia Geochemistry Reference environment
a b s t r a c t The Furo of Laura is an economically important river in the Amazon estuary. Thus, in the present study, we evaluated the metal distribution (Al, Cd, Co, Cu, Cr, Fe, Ni, and Mg) in the bottom sediments of this river. The sediments were sampled at four points every 2 months for a year with an Ekman-Birge sampler. After microwave acid digestion, the metal levels were determined by optical emission spectrometry with inductively coupled plasma. The particle size and organic matter content influenced the concentration of the metals. The sediments were not enriched by the analyzed metals; the estuary therefore retained the characteristics of an uncontaminated environment, thus serving as a reference environment for comparison. © 2017 Published by Elsevier Ltd.
Development in Brazil, especially over the last three decades, had considerable environmental impacts that were caused by a high degree of urbanization (Bregunce et al., 2011). The situation is more critical in estuarine environments with port activities and industrial and urban waste deposits (Chakraborty et al., 2014). The Vigia municipality is located in the microregion of “Salgado,” in the northeast of the state of Para. The urbanization process in this location resulted in the removal of riparian forests and discharge of untreated domestic and industrial wastewater that passes through several neighborhoods, arriving at the Furo of Laura estuary (Bentes and Barbosa, 2015). The margin of this estuary currently has approximately 51,705 inhabitants occupying an area of 301 ha (IBGE, 2016). This estuary is considered the main hydrography of the Vigia municipality. The river is a large body of water (approximately 43,686 m in length) consisting of numerous microbasins formed by the tidal effects and the Marajó Bay. The sediments of the estuary are rich in Cu, Cr, Ni, Pb, and Zn in several sectors of the eastern margin, and the origin of these metals is linked to the domestic sewage generated by the city of Belém (Corrêa and Pereira, 2002). In addition, because its main economy is fishing, the municipality hosts several fishing companies; in one of them, the pollution potential corresponds to the load generated by a city of 567 to 653 inhabitants in terms of the organic load (Mello, 2007), reflecting the importance of this study. ⁎ Corresponding author. E-mail address: [email protected] (M.L.S. Santos).
In this study, we evaluated seasonal and spatial distribution of the heavy metals Al, Cd, Co, Cu, Cr, Fe, Ni, and Mg and characterized the particle size fractions and organic matter (OM) content in the bottom sediments of Furo of Laura estuary to create a reliable heavy metal database with which future levels can be compared and evaluated. Sediment samples were obtained at four points in the Furo of Laura estuary (P1: reference area, P2: intermediate area, P3: area under urbanized influence, P4: Marajó Bay influence area) (Fig. 1), one sample at each point, four in each month (September and November 2011 and January, March, May, and July 2012); a total of 24 samples were obtained. Approximately 500 g (wet weight) of bottom sediment was sampled at each point using an Ekman-Birge sampler with the aid of a boat during neap tide. Sediment particle sizes were analyzed according to the method given by Lima et al. (2015) using the laser in the Shimadzu equipment, model SALD - 2201. OM content was analyzed according to the method reported by Loring and Rantala (1992), which is based on the oxidation of organic carbon with potassium dichromate in an acidic medium. The heavy metals were determined from the silt and clay fraction (b0.063 mm). Nitric acid (HNO3), hydrochloric acid (HCl), hydrofluoric acid (HF), and boric acid (H3BO3) were used for the digestion of the sediments; the digestion was performed in a closed system using microwave radiation (MARSX pres, CEM Corp. Matthews, NC, USA). The metals were analyzed by optical emission spectrometry with inductively coupled plasma (ICP-OES, Model Vista- MPXCCD, VARIAN) according to the method by Spectro (1999). To validate the results, we used a reference sample for metals in the soil (SRM 2710, NIST, USA), and the
http://dx.doi.org/10.1016/j.marpolbul.2017.02.073 0025-326X/© 2017 Published by Elsevier Ltd.
Please cite this article as: Lima, M.W., et al., Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil, Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.073
2
M.W. Lima et al. / Marine Pollution Bulletin xxx (2017) xxx–xxx
Fig. 1. Location of the sampling sites in the Furo of Laura.
recovery of the certified values was 76.7% for Al, 86.1% for Cd, 87.6% for Cu, 83.5% for Ni, 100% for Fe, and 74.1% for Mg. The results were compared with the quality reference values using the ERL value to represent a minimal effects range; concentrations equal to and above the ERL value but below the ERM value represent possible effects; concentrations equivalent to and above the ERM value represent frequent occurrence of probable effects (Long et al., 1995). The sediments from Furo of Laura were predominantly sandy, with the mean proportions of sand, silt, and clay being 67.09%, 29.66%, and 3.26%, respectively, in the less rainy season, with an average rain of 75%, 21.59%, and 3.40%, respectively. Regarding the spatial variation (Table 1), there were no fluctuations in the granulometric fractions. The OM had higher average values at the innermost point of the Furo (P1). The highest concentrations of heavy metals occurred more frequently at the point near the Vigia municipality (P2) for Al, Co, Cu, Cr, Ni, and Mg and at the point near Marajó Bay (P1) for Cd and Fe. The lowest concentrations of Cd, Co, Cu, Cr, and Fe occurred at point P2, whereas the concentrations of Al, Ni, and Mg were lower at P4, P3, and P1, respectively. Despite the higher concentrations observed at P1 and P2, the highest averages of all other metals (Al, Cd, Co, Cu, Cr, Ni, and Mg) occurred at the point ahead of the Vigia municipality (P3), with the exception of iron Fe (P1). The variables analyzed revealed the occurrence of seasonal variations in the study area (Table 2) and space.
For the metals, we could verify that that the concentrations of Al, Cu, Cr, and Mg remained higher in the less rainy season and those of Cd, Co, Fe, and Ni were higher in the rainy season. It is noteworthy that although some metals remain at higher concentrations in the rainy season (Cd, Co, Fe, and Ni), the highest average for all metals occurred in the less rainy season (Fig. 2). The largest amount of sand was found at sampling points P3 and P4, which are closest to Marajó Bay (mouth of the river). In the Marajó Bay, the sand fraction is dominant because of the presence of morphological sand banks and bars (França and Souza-Filho, 2006). This prevalence may be due to the influence of the Marajó Bay in the outer region in the Furo of Laura. Erosion of the soil and the micro basins of Vigia and Colares may also contribute to this result. Regarding the seasonal variations of heavy metals, the highest concentrations were found in the less rainy season, and the results at these sampling points reinforces the local geochemical origin of these metals. The low concentrations of Al are caused by the weathering barriers that are made of extensive lateritic coatings containing oxides, hydroxides, and oxyhydroxides of Al and Fe (Espindola and Daniel, 2008), thus explaining their natural origin. Low concentrations of detected Cu and Ni may be related to low levels of OM and clay in the Furo of Laura estuary, which greatly influence the concentration of these metals in the sediments (Chester et al., 1988) as they function as sites of adsorption (Siqueira et al., 2006). Cr is a characteristically terrigenous element. Its source is associated with the formation of weathering barriers,
Table 1 Maximum, minimum, and average values of fractions of sand, silt, clay, and OM (in %) verified in the sampling. Points of collection
Sand % Silt % Clay % OM % a b c
P1
P2
P3
P4
Mina
Maxb
Avgc
Mina
Maxb
Avgc
Mina
Maxb
Avgc
Mina
Maxb
Avgc
63.1 17.4 0.8 5.9
81.0 32.8 6.1 10.7
69.7 26.5 3.9 8.4
61.3 13.5 0.1 4.6
86.4 36.8 5.7 10.2
70.6 26.2 3.2 7.1
64.9 5.6 0.1 6.6
94.3 32.1 3.5 9.8
71.8 25.8 2.4 8.4
66.0 12.4 0.3 4.2
87.2 30.9 11.0 8.6
72.1 24.0 3.8 6.9
Minimum. Maximum. Average.
Please cite this article as: Lima, M.W., et al., Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil, Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.073
M.W. Lima et al. / Marine Pollution Bulletin xxx (2017) xxx–xxx
3
Table 2 Maximum (Max), minimum (Min), and average (Avg) values of the metals Al, Cd, Co, Cu, Cr, Ni, Fe, and Mg (in mg·kg−1) detected in the sampling. Points of collection
This study
P1 (reference area)
P2 (intermediate area)
P3 (area under urbanized influence)
P4 (Marajó Bay influence area)
Min Max Avg Min Max Avg Min Max Avg Min Max Avg
Range of low biota effects (ERL)a Range of medium to biota effects (ERM)a Sediments of the estuaryb Sediments of the Bay of Guajará-PA Nonpolluted Sediments, Cardoso Island, Cananéia (SP)c Sediments of the River Formoso estuary (PE)d Port of Mitilini (Greece)e Bay of Moreton (Austrália) Before-industrializationf a b c d e f
Al
Cd
Co
Cu
Cr
Ni
Fe
Mg
9198.3 14,957.5 11,509.5 9999.6 17,752.6 12,800.1 9660.4 14,477.1 13,207.7 7465.6 16,806.6 11,500.3
3.0 5.2 3.8 2.7 4.9 3.9 3.4 4.5 3.9 2.8 3.9 3.3
9.1 13.0 10.2 8.3 13.4 11.2 10.5 12.7 11.6 8.6 11.3 9.7
11.7 15.1 13.3 9.4 16.4 13.1 12.4 15.0 13.8 10.0 13.5 11.9
53.1 62.8 57.2 42.3 71.4 57.8 55.9 63.2 58.6 46.3 60.4 52.4
19.0 21.9 20.5 12.9 24.3 19.5 19.1 22.9 20.8 15.9 20.9 18.4
27,035.2 37,606.8 30,346.6 23,674.8 35,832.5 29,870.2 28,263.6 32,449.6 30,072.2 25,116.9 30,251.2 27,446.2
114,000 194,000 166,000 134,000 259,000 193,000 171,000 215,000 197,000 126,000 232,000 181,000
* * 43,000 49,000 1100–16,200 766–2383 18,600–52,600 5300–14,700
1.2 9.6 * * 0–30.9 0.04–0.11 0.05–0.5 b0.4–0.6
* * * * 4.4–47.3 0.5–1.5 * b1.2–5
34 270 16.5 25.3 0–27.2 1.15–3.71 9.39–67.6 0.5–13
81 370 51.3 55.6 0–88 2.7–7.4 44.6–154 7–72
20.9 51.6 20.1 22.4 * 1,1–3.2 * *
* * 32,000 31,000 1500–22,600 3675–21,807 7700–28,100 1100–117,200
* * * * * 3568–12,420 * *
Long et al. (1995). Oliveira et al. (2015). Semensatto-Jr et al. (2007). Silva et al. (2009). Aloupi and Angelidis (2001). Preda and Cox (2002).
which are characteristic of the Vigia soils (Idesp, 2013), and their low concentrations refer to the geochemical origin. The concentration of Mg was slightly high at sampling points P3 and P4; this may be related to agricultural inputs such as calcareous inputs. Lime (calcium oxide, CaO) is derived from the calcination of limestone or dolomite. It is commonly used for painting homes in the municipality. With regard to the
reference index, all the metals presented values below the threshold for adverse risk to biota. Therefore, the sediments of the Furo of Laura estuary are predominantly sandy, with low OM content, and characterized as a high-energy environment, being slightly influenced by seasonality and the hydrodynamics of Marajó Bay. The particle size, OM content, and local
Fig. 2. Seasonal distribution of (A) granulometric fractions, (B) OM, (C) Al, (D) Cd, (E) Co, (F) Cu, (G) Cr, (H) Fe, (I) Ni, and (J) Mg in the sediments of Furo da Laura.
Please cite this article as: Lima, M.W., et al., Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil, Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.073
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M.W. Lima et al. / Marine Pollution Bulletin xxx (2017) xxx–xxx
geochemistry influence the concentrations of Al, Cd, Cu, Cr, Ni, Fe, and Mg in the bottom sediments. This estuary was not enriched by the metals analyzed, thus making it a reference environment that is uncontaminated by these elements; therefore, the future levels of metals can be evaluated and compared with the present values. Acknowledgments We thank the Coordination of Improvement of Higher Education Personnel (CAPES), Program in Tropical Aquaculture and Aquatic Resources, Environmental Chemistry Laboratories-UFRA, Chemical Oceanography-UFPA, and Toxicology-IEC for performing the analyses. References Aloupi, M., Angelidis, M.O., 2001. Geochemistry of natural and anthropogenic metals in the coastal sediments of the Island of Lesvos, Aegean Sea. Environ. Pollut. 113, 211–219. Bentes, L., Barbosa, E.J.S., 2015. Urban occupation in “bajaadas” in the coastal zone of the State of Pará, case of the stream of Rocinha, city of Vigia of Nazaré. J. Hist. Geog. Inst. Pará (IHGP) 02 (02), 108–119. Brazilian Institute of Geography and Statistics (IBGE), Pará, Vigia, 2016á. Available. http:// cidades.ibge.gov.br/xtras/perfil.php?codmun=150820N (Access on November 14, 2016). Bregunce, D.T., Jordan, E.J., Dziedzic, M., Maranho, L.T., Aparecida Cubas, A.S., 2011. Evaluation of the water quality of the Müller's Ribeirão, Curitiba-PR. Braz. J. Wat. Res. 16, 39–47. Chakraborty, P., Ramteke, D., Chakraborty, S., Nath, B.N., 2014. Changes in metal contamination levels in estuarine sediments around India – an assessment. Mar. Pollut. Bull. 78, 15–25. Chester, R., Thomas, A., Lin, F.J., Basaham, A.S., Jacinto, G.A., 1988. Solid-state copper spectra in water particles and oceanic surface sediments. Mar. Chem. 24, 261–292. Corrêa, J.A.M., Pereira, K.R., 2002. Study of the dispersion of heavy metals in sediments of the border of Belém. Bull. Museu Paraense Emílio Goeldi, Earth Sci. Ser. 14, 79–101.
Espindola, C.R., Daniel, L.A., 2008. Laterite and Lateritic Soils in Brazil. Bulletin Technical of FATECSP BT/24. pp. 21–24. França, C.F., Souza-Filho, P.W.M., 2006. Morphological compartmentalization of the eastern margin of the Island of Marajó: Coastal Zone of the municipalities of Soure and Saving Land - State of Pará. Braz. J. Geomorph. 7, 33–43. Institute of Economic, Social and Environmental Development of Pará-Idesp, 2013t. Municipal Statistics: Watch. Belém-PA. 49 p. http://iah.iec.pa.gov.br/iah/fulltext/ georeferenciamento/vigia.pdf (Accessed on 13 March 2013). Lima, M.W., Santos, M.L.S., Montelo, D.J., Nunes, D.M., Alves, I.C.C., Silva, M.S.F., 2015. Temporal analysis of the granulometric composition of an Amazonian estuary, Pará, Brazil. Scientia Plena 11 (1), 1–11. Loring, D.H., Rantala, R.T.T., 1992. Manual for analyzing the geochemistry of marine sediments and suspended particles. Comments-Earth Science. 32, 235–283. Long, E.R., Macdonald, D.D., Smith, S.L., Calder, F.D., 1995. Incidence of adverse biological effects within ranges of chemical concentration in marine and estuarine sediments. Environ. Manag. 19 (1), 81–97. Mello, V.S.A., 2007. Characterization of the Effluent From the Amazonian Fishing Industry and its Release Into the Receiving Body - Vigia de Nazaré/PA. Master's Dissertation (Master's in Civil Engineering). 220. Federal University of Pará. Oliveira, E.C., Lafon, J.M., Corrêa, J.A.M., Carvalho, J.H.S., Dias, F.F., Taddei, M.H.T., 2015. Distribution of the traces metals in sediments of the hydrographic system of the region of Belém, PA (West bank of Guajará bay and Carnapijó river). Geochim. Bras. 29 (2), 139–153. Preda, M., Cox, M.E., 2002. Trace metal occurrence and distribution in sediments and mangroves, Pumiscestone region, southeat Queensland, Austrália. Environ. Int. 28, 433–449. Semensatto-Jr, D.L., Araújo, G.C.L., Funo, R.H.F., Santa-Cruz, J., Dias-Brito, D., 2007. Metals and non-metals in sediments of a non-polluted mangrove, Cardoso Island, Cananéia (SP). Res. Geosci. 34 (2), 25–31. Silva, N.M.T.N., Neto, J.A.S., Silva, W.L., Valença, L.M.M., 2009. Geochemistry of drainage bottom sediments in tropical estuary, northeastern Brazil. Geol. Stud. 19 (1), 139–159. Siqueira, G.W., Pereira, S.F.P., Aprile, F.M., 2006. Determination of trace elements (Zn, Co and Ni) in sediments of the Amazon Continental Shelf under influence of the Amazon River discharge. Acta Amazônica 36 (3), 321–326. SPECTRO, 1999. User's Guide of Spectro ICP-OES. Manual do Usuário (240 p).
Please cite this article as: Lima, M.W., et al., Heavy metals in the bottom sediments of the Furo of Laura estuary, Eastern Amazon, Brazil, Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.073