Avaliação da contaminação por metais pesados em sedimentos por atividades de estaleiros na Baia do Guajará e no canal do Rio Maguari

Abstract

Antifouling paints applied on ships contain high concentrations of metals in their composition, mainly copper and zinc, with concentrations above 50% and 20%, respectively. Despite being essential elements for living beings, in high concentrations it causes problems in cell growth and reproduction of organisms. In the city of Belém, State of Pará, a significant amount of industrial and domestic effluents is released into the Bay of Guajará, one of which is related to activities in shipyards. Previous studies have shown evidence of metal contamination in the sediments in the edge of Belém estuary, however, no work has highlighted contamination from shipyards. Therefore, the objective of this work is to evaluate sediment contamination by activities in shipyards and abandonment of vessels in the edge of Belém city. The three samples of sediments were collected in 5 shipyards in Belém, two of which were collected in the less rainy period (September 2017 and November 2019) and one in the rainy season in May 2018. The sediment was collected up to 10 cm deep, and samples of paint fragments and fragments of the hulls of abandoned vessels were collected. The in situ pH of the interstitial sediment water was measured. In the laboratory, the sediment samples were placed in an oven at 60°C to dry, disaggregated and then sieved (< 63μm). The samples of paint fragments and the hulls of abandoned boats were washed with deionized water and dried in an oven at 60°C, macerated, mixed with the sprayed white area and reserved. A sample of the commercial paint most commonly used in shipyards was placed on a cellulose nitrate membrane in a hood, after which part of the sample was removed and macerated. An aliquot of the sediment samples from each shipyard was used for particle size analysis, using a laser particle analyzer. The mineralogical composition of the sediment samples was determined by X-ray diffraction, powder method. The clay minerals were determined by X-ray diffraction, following Stokes' Law and according to the methodology proposed by Moore & Reynolds Jr (2002). For the determination of total organic carbon, a TOC - VCPH analyzer with a combustion detector was used. To determine the concentrations of Cu, Zn, Pb, Ni, Cr, Ba, V, Li, Fe and Al contained in sediment, commercial paint, paint fragments and hull fragments of abandoned ships, the samples were subjected to chemical extraction with aqua regia and determined through Optical Emission Spectrometry with Inductively Coupled Plasma (ICP-OES). For statistical treatment of the data, Spearman's correlation was applied to determine the relationship between the parameters, and the Principal Component Analysis test to determine the relationship of metals with shipyards, control station and diffuse anthropogenic source station. The Wilcoxon test was also applied to verify if there were significant differences in the metal concentrations of the sediments collected in front of the shipyard with the sediments collected that were in contact with the abandoned vessel. To assess the level of contamination by metals, the geoaccumulation index proposed by Muller (1969) was applied. The sediment granulometry of the Belem shore presents a higher proportion of sand and silt. The sediments are composed of muscovite, illite, kaolinite, quartz and plagioclase. The clay minerals identified were: smectite, kaolinite, illite and quartz. The pH values of the interstitial water of the sediment samples from Baía do Guajará and Furo do Maguari were around 5.2 – 6.7. The total organic carbon of the sediment was around 0.6% to 2.2%. The commercial paint analyzed presented the following concentrations: Fe (21.2%), Cu (18,497 mg kg-1), Zn (16,589 mg kg-1) and Al (1.59%). The highest concentrations found in the composition of paint fragments and in the fragments of the hulls of abandoned vessels were: Fe (69.2 %), Ba (29,583 mg kg-1), Zn (9,350 mg kg-1), Pb (1,406 mg kg-1), Cu (697 mg kg-1) and Cr (548.7 mg kg-1). This result revealed that abandonment of vessels is the biggest source of contamination in shipyard areas in the city of Belém. According to the Sediment Quality Guidelines for Metals in Freshwater Ecosystems by Buchman (2008), only the average concentration of Cu, with 41.0 mg kg-1, in the sediment reached values above the Threshold Effects Level for the amphipod, Hyallela azteca (28.0 mg kg-1) in the ABSS shipyard. The other shipyards had copper averages ranging between 13.3 – 28.3 mg kg-1. The other metals had mean concentrations always below the Threshold Effects Level value. Spatially, the sediments that were collected in front of the ABSS shipyard for most metals had higher concentrations compared to the sediments that were in contact with the hull of the abandoned ship, of this shipyard. However, the sediments that were collected in front of the MS shipyard in general had lower concentrations compared to the sediments that were in direct contact with the abandoned vessel. Those that presented with concentrations of Cu (39.0 mg kg-1), Zn (120.0 mg kg-1) and Cr (32.0 mg kg-1) that exceed the value of Threshold Effects Level for the amphipod. However, the Wilcoxon Rank statistical test did not attest significant differences in the sediment collected in front of the shipyards with the sediment that was in contact with the abandoned vessels. The main elements that make up the antifouling paints: Cu, Zn had a strong positive correlation (r = 0.80; p<0.05). The Principal Component Analysis confirmed contamination by the metals Cu, Zn, Pb, Ni, Li, Fe and Al and has a stronger relationship with shipyard activities and ship abandonment than with diffuse geogenic or anthropogenic sources The geoaccumulation index classified the sediments close to the IS and ABSS shipyards as moderately polluted for copper with indices of 2.0 and 2.5, respectively. The other metals Zn, Ba, Fe and Al in the studied shipyards show an anthropogenic contribution by activities in shipyards and abandonment of vessels, classifying one or more shipyards as being in a situation close to a polluted environment, for one or more studied metals, with geoaccumulation index close to 2. The results can support additional studies of metal contamination through activities in shipyards and abandonment of vessels, and it can assist in the application of waste management in shipyards and ship cemeteries around the world.