Metal concentrations in marine sediments of the Rio de Janeiro Coast (Brazil): A proposal to establish new acceptable levels of contamination.

This work aims to propose new standards to assess the degree of sediment contamination in saline and brackish environments, since the legislation currently used in Brazil is based on Canadian/American regulations, which do not comply with the conditions in Brazil. This study is based on geochemical analyses of 340 surface sediment samples collected in the Green Coast region (Rio de Janeiro, Brazil), including Mangaratiba, Angra dos Reis and Ribeira coves and Ilha Grande and Sepetiba bays. This region is influenced by industrial, harbor, urban and tourist activities and was affected by a dam rupture episode that released contaminated material. The results show heterogeneity in the distribution and range of metal concentrations in the study area depending on the supply of metals from natural and anthropogenic sources. Environmental characteristics such as coastal and tidal currents, water temperature and salinity, local depth, sediment grain size, sedimentary dynamics and biogeochemical processes influence the dispersion or retention of metals. The pollution load index (PLI) suggests that Sepetiba Bay is the region with the most environmental degradation due to anthropogenic contamination. In this context, we propose the establishment of new levels of contamination according to the Cd, Cr, Cu, Mn, Ni, Pb, V and Zn concentrations in sediments of salt and brackish waters, considering I) background level; II) level 1 - with anthropogenic influence; and III) level 2 - contaminated. The results of this work also suggest that, except for zinc, the range of metal concentrations admitted by Brazilian legislation are quite permissive and not adequate for Brazilian coastal environments.

Disentangling natural vs. anthropogenic induced environmental variability during the Holocene: Marambaia Cove, SW sector of the Sepetiba Bay (SE Brazil).

Multiproxy approach based on textural, mineralogical, geochemical, and microfaunal analyses on a 176-cm-long core (SP8) has been applied to reconstruct the Holocene paleoenvironmental changes and disentangling natural vs. anthropogenic variability in Marambaia Cove of the Sepetiba Bay (SE Brazil). Sepetiba Bay became a lagoonal system due to the evolution and development of the Marambaia barrier island during the Holocene and the presence of an extensive river basin. Elemental concentrations from pre-anthropogenic layers from the nearby SP7 core have been used to estimate the baseline elemental concentrations for this region and to determine metals enrichment factors (EF), pollution load index (PLI), and sediment pollution index (SPI). Record of the core SP8 provides compelling evidence of the lagoon evolution differentiating the effects of potentially toxic elements (PTEs) under natural vs. anthropic forcing in the last ~ 9.5 ka BP. The study area was probably part of coastal sand ridges between ≈ 9.5 and 7.8 ka BP (radiocarbon date). Events of wash over deposited allochthonous material and organic matter between ≈ 8.6 and 7.8 ka. Climatic event 8.2 ka BP, in which the South American Summer Monsoon was intensified in Brazil causing higher rainfall and moisture was scored by an anoxic event. Accumulation of organic matter resulted in oxygen depletion and even anoxia in the sediment activating biogeochemical processes that resulted in the retention of potentially toxic elements (PTEs). After ≈ 7.8 ka BP at the onset of the Holocene sea-level rise, a marine incursion flooded the Marambaia Cove area (previously exposed to subaerial conditions). Environmental conditions became favorable for the colonization of benthic foraminifera. The Foram Stress Index (FSI) and Exp(H'bc) indicate that the environmental conditions turned from bad to more favorable since ≈ 7.8 ka BP, with maximum health reached at ≈ 5 ka BP, during the mid-Holocene relative sea-level highstand. Since then, the sedimentological and ecological proxies suggest that the system evolved to an increasing degree of confinement. Since ≈ 1975 AD, a sharp increase of silting, Cd, Zn, and organic matter also induced by anthropic activities caused major changes in foraminiferal assemblages with a significant increase of Ammonia/Elphidium Index (AEI), EF, and SPI values and decreasing of FSI and Exp(H'bc) (ecological indicators) demonstrating an evolution from "moderately polluted" to "heavily polluted" environment (bad ecological conditions), under variable suboxic conditions. Thus, core SP8 illustrates the most remarkable event of anthropogenic forcing on the geochemistry of the sediments and associated pollution loads and its negative effect on benthic organisms.

Long-term eutrophication and contamination of the central area of Sepetiba Bay (SW Brazil).

This work sheds light on the recent evolution (≈1915-2015 AD) of Sepetiba Bay (SB; SE Brazil), a subtropical coastal lagoon on the southwestern Brazilian coast, based on a multiproxy approach. Variations in geochemical proxies as well as textural, mineralogical and geochronological data allow us to reconstruct temporally constrained changes in the depositional environments along the SP3 sediment core collected from the central area of SB. At the beginning of the twentieth century, the substrate of the study site was composed of coarse-grained sediments, largely sourced from felsic rocks of proximal areas and deposited under moderate to strong shallow marine hydrodynamics. Since the 1930s, the study area has undergone silting and received high contributions of materials from mafic rocks sourced by river basins. The SP3 core reveals a shallowing-upward sequence due to human-induced silting with significant eutrophication since the middle of 1970, which was caused by significant enrichment of organic matter that was provided by not only marine productivity but also continental and human waste. In addition, the sediments deposited after 1980 exhibit significant enrichment and are moderately to strongly polluted by Cd and Zn. Metals were dispersed by hydrodynamics from the source areas, but diagenetic processes promoted their retention in the sediments. The potential ecological risk index (PERI) indicates that the level of high (considerable) ecological risk is in sediments deposited in ≈1995 (30-32 cm; subsurface). The applied methodology allowed us to understand the thickness of the bottom sediment affected by eutrophication processes and contaminants. Identical methodologies can be applied in other coastal zones, and can provide useful information to decision makers and stakeholders that manage those areas.