Assessment of anthropogenic pollution in Guanabara Bay (SE Brazil) through biogeochemical data and stable isotope mixing models.

This work intends to identify pollution sources along the margins of Guanabara Bay (GB; SE Brazil) through a multiproxy approach and Bayesian stable isotopic mixture model (BSIMM). For this purpose, 33 surface sediment samples were collected and analyzed for granulometry, geochemistry (heavy metals, total organic carbon-TOC, stable isotopes of carbon and nitrogen-δ13C and δ15N, Rock-Eval pyrolysis parameters-REPP), and physicochemical parameters. Metal concentrations (E) dissolved in water (EW), adsorbed by organic matter (EOM) and by Mn hydroxides (EMn), and total extracted concentrations (ET) were analyzed. Sampling was conducted in 2018 after an oil spill from Reduc Oil Refinery. Potential Ecological risk index (PERI), based on metals, classified 85% of the analyzed stations as having moderate to considerable ecological risk. The metals with the potential to cause the highest ecological risk were CdW, CdOM, PbOM, and HgOM. The combination of BSIMM and REPP data was an effective proxy for oil spill detection by indicating the presence of polycyclic aromatic hydrocarbons (PAHs). Relatively high TOC contents suggested that the analyzed stations are eutrophicated environments. BSIMM discriminated three groups of stations with different sources of organic matter (OM), endorsing the result previously shown by the cluster analysis: (A) Niterói region, Botafogo marina, Glória marina, Fiscal and Fundão islands with diffuse sources of OM, including marine phytoplankton and material of continental origin from highly polluted rivers and domestic sewage; (B) region near Fundão and Governador islands and Mangue Channel outlet with OM (≃70%) supplied by highly polluted streams and a small contribution of PAHs; (C) Duque de Caxias and Botafogo-Urca inlet with significant contributions of PAHs, materials from C-3 plants and rivers polluted by urban sewage. Results of linear regressions in conjunction with BSIMM indicate that HgMn and PbOM mainly affect Group A's stations. Although the eastern margin of GB (Niterói; Group A) showed greater oceanic interaction than the other groups, it presented substantial concentrations of metals, potentially harmful (i.e., Hg and Pb) to marine biota and human health.

Assessment of the ecological quality status of the Sepetiba Bay (SE Brazil): When metabarcoding meets morphology on foraminifera.

In recent years, the region surrounding Sepetiba Bay (SB; SE Brazil) has become a hub of intense urban expansion and economic exploitation in response to ore transport and industrial and port activities. As a result, contaminants have been introduced into the bay, leading to an overall worsening of the environmental quality. The present work applies for the first time a foraminiferal morphology-based approach (M) and eDNA-based metabarcoding sequencing (G), along with geochemical data to assess the ecological quality status (EcoQS) in the SB. Principal component analysis shows that the eDNA and morphospecies diversity as well as most of the taxa relative abundance decline in response to the environmental stress (ES) gradient related to total organic carbon (TOC) and metal pollution. Based on ecological indices, Exp(H'bc) (G), Exp(H'bc) (M), foraminifera ATZI marine biotic index (Foram-AMBI), Foram Stress Index (FSI), and geochemical indices (TOC and Potential Ecological Risk Index), the lowest values of EcoQS (i.e., bad to moderate) are inferred in the innermost part of the SB. Despite minor discrepancies among the six EcoQS indices, an agreement has been found for 63% of the stations. To improve the agreement between the ecological indices, it is necessary to fill the gap in species ecology; information on the ecology of many species is still unknown. This work reinforces the importance of molecular analysis and morphological methods in environmental impact studies and confirms the reliability of foraminiferal metabarcoding in EcoQS assessment. This is the first study evaluating the EcoQS in the South Atlantic by using combined foraminiferal eDNA metabarcoding with morphological data.

Factors driving sediment compositional change in the distal area of the Ria de Vigo (NW Spain): oceanographic processes vs. paleopollution.

We analyze potential Late Holocene metal contamination along a sediment core collected in the distal zone of Ria de Vigo (North Spain). Statistical treatment of the dataset based on a multiproxy approach enabled us to identify and disentangle factors influencing the depositional processes and the preservation of the records of this activity in the area over the last ≈3000 years BP. Some layers of the analyzed core have significant enrichment in Cu and a moderate enrichment in Ag, Mo, As, Sb, S, Zn, Ni, Sn, Cd, Cr, Co, Pb, and Li. The enrichment of these elements in some layers of this core may be related to mining activities that have taken place since classical times in the region. Successive phases of pollution were identified along the core KSGX24 related to the Late Bronze Age (≈3000-2450 years BP), Iron Age (≈2450-1850 years BP), Roman times (≈1850-1550 years BP), Middle Ages (≈1250-500 years BP), and industrial and modern (≈250-0 years BP) anthropic activities. The protection of the Cies Islands, the erosive and transport capacity of the rivers in the region, oscillations of the oceanographic and climatic regime, atmospheric contamination, and diagenetic sedimentary processes might have contributed to the accumulation and preservation of this record in the distal region of the Ria de Vigo. The studied core shows that the industrial and preindustrial anthropic impacts caused an environmental liability and contributed to the presence of moderate to heavy pollution of various metals in surface and subsurface sediment layers in the distal sector of the Ria de Vigo, which could be a hazard to biota.

Trace metals enrichment and potential ecological risk in sediments of the Sepetiba Bay (Rio de Janeiro, SE Brazil).

The Sepetiba Bay (SB; SE Brazil) has been severely affected by growing of urbanization and industrial activity. This work aims to analyze the evolution of contamination by metals of sediments in SB. The results show a marked increasing trend in the concentrations of potentially toxic elements (PTEs), which is consistent with the rapid populational and industrial growth, mostly since 1970 CE. The remobilization and redistribution of sediments by currents have contributed to the dispersion of metals from the main source of pollutants to relatively distant regions. "Moderately to strongly polluted" sediments are also recorded in some sites in deeper sedimentary layers (namely in preindustrial periods), probably due to lithologic sources of the sediments. The concentrations of PTEs in SB are relatively high when compared with those found globally and in other Brazilian water bodies. Samples of high-resolution sediment cores confirmed that potential ecological risk to the coastal system is influenced not only through human actions but also by natural causes.

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.