Assinatura isotópica de Pb em sedimentos da margem leste da Baía do Guajará (orla de Belém) e rio Maguari

Abstract

Estuarine sediments provide a long-term record of the accumulation of trace metals from riverside, atmospheric and anthropogenic sources. The release of trace metals from point sources is largely controlled by the natural processes of physical and chemical weathering of rocks, in addition to anthropogenic disturbances that can occur on a large scale. In addition to diffuse anthropogenic sources, estuarine sediments can be enriched in trace metals by antifouling paints, with high contents of metals (Cu, Zn, Pb), which are applied to ship hulls and many submerged structures to prevent the growth of fouling organisms such as bacteria, macroalgae, mussels, bivalves, and invertebrates. Pb isotopic signatures are useful tools to investigate the sources and mobility of trace metals in estuarine systems and allow to distinguish between geogenic and anthropogenic source contributions. In recent years, several isotopic Pb studies for this purpose have been conducted in the hydrographic system of Belém. The aim of this work is the application of Pb isotope geochemistry in bottom sediments, suspended particulate matter (MPS), and fragments of vessels with antifouling paint of several shipyards in Guajará Bay and the Maguari River, in the metropolitan area of Belém-PA. It is intended to verify whether the paints used in the shipyards can be considered a point source of contamination by Pb. Bottom sediment samples were collected at 9 stations along the northern and southern waterfront of Belém, at the right margin of the Guajará Bay, and 3 on the Maguari River near shipyards, 6 samples of suspended particulate matter and 4 samples of vessel hull fragments. Samples of bottom sediments at the mouth of the Una Channel (3 samples) and Paracui River (1 sample) were also collected. Finally, a sample of bottom sediments was also sampled on Barra island, in the middle of Guajará Bay, as a reference to the geogenic background. Chemical analyzes of bioavailable Pb were carried out on the bottom sediment samples by inductively coupled plasma optical emission spectrometry (ICP-OES) and Pb isotopic analyzes on all samples by inductively coupled plasma mass spectrometry with magnetic sector and multiple collectors (ICP-MS). In the bottom sediment samples from the shipyards of the Belém waterfront and the Maguari River, important variations of Pb concentrations of the bioavailable fraction occur, from a value similar to the reference point (11 mg kg-1) up to contents of 25 mg kg-1. These variations suggest incipient processes of anthropic action. Even so, the levels are within the range of concentrations found so far and do not show evidence of a significant contribution of Pb linked to the proximity of the shipyards. The similar ranges of bioavailable Pb concentration between the various sectors studied (northern and southern sectors of the waterfront Belém and Maguari River) show that there is no clear pattern of distribution of Pb levels in the sectors studied. These concentrations were shown to be systematically lower than the reference values TEL (35 mg kg-1) and PEL (91.3 mg kg-1), thus indicating that Pb is not causing harmful effects to biota in these areas of the Guajará Bay system. In the northern sector of the waterfront Belém and along the Maguari River, the variations in 206Pb/207Pb isotopic ratios are within the range of the Barra island reference point and the values considered geogenic in previous works (1.189 – 1.197). Only the point identified as “vessel graveyard” presented a lower ratio (206Pb/207Pb= 1.183) and may indicate an increase in Pb anthropogenic contribution due to the deterioration of abandoned vessels and the working shipyard. In the southern sector of the Belém shore, practically all the sediments from the shipyards and the mouth of the Una canal presented lower 206Pb/207Pb isotopic ratios (1.163 and 1.178), indicating an anthropogenic contribution. This diffuse anthropogenic contribution is apparently related to the Una channel and also to the greater concentration of shipyards and other possible sources of metals. In addition, the comparison of the Pb isotopic composition of the sediments at the mouth of the drainage channels in the northern and southern sectors of the Belém waterfront suggests the existence of a relationship between anthropogenic contribution and the size of the drainage basins, population density, and urban activities. No correlation was found between the 206Pb/207Pb isotopic ratios of the bottom sediments and corresponding MPS, however, all points fit a trend line, confirming the mixture between two different sources of Pb for both sediments and suspended material. The isotopic signatures of the hull + paint fragments are positioned along the same trend line established between a geogenic end-member and an anthropogenic end-member (aerosols), for the hydrographic system of Belém, making it impossible to identify a specific anthropogenic source of Pb from the shipyards. The comparison of these signatures of the fragments with the bottom sediments of the shipyards indicates that this possible anthropogenic source enters as one of the subordinate components of the diffuse anthropogenic contribution of Guajará Bay. Finally, based on the data from this study and the works already developed in the hydrographic system of Belém, it is proposed to extend the range of 206Pb/207Pb ratio of the geogenic Pb to 1.189 – 1.204 for the hydrographic system of Belém, as a whole.