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.

Inferring the ecological quality status based on living benthic foraminiferal indices in transitional areas of the Guanabara bay (SE Brazil).

Using benthic foraminifera, we evaluate the ecological quality status (EcoQS) of transitional waters of the Guanabara Bay (SE Brazil) by applying the diversity-based index exp (H'bc) and the sensitivity-based Foram-AMBI for the first time in South America. The Guanabara Bay was selected for this study as it is one of the largest transitional ecosystems in the State of Rio de Janeiro and has been severely impacted by anthropogenic activities. Concentrations of potentially toxic elements (PTEs) were assessed by sequential chemical extraction in three phases (i.e., dissolved in water, adsorbed on organic matter, and Mn oxy-hydroxides). Total organic carbon, total nitrogen, and stable isotope (δ13C and δ15N) signatures of organic matter were analyzed to trace environmental stress. The Ammonia/Elphidium ratio suggests hypoxic conditions at most of the sampled sites. Principal component analysis identifies the first component as environmental stress underlying organic matter and PTE enrichment (in all three phases), which is positively related to Foram-AMBI and negatively to exp (H'bc). The exp (H'bc) and Foram-AMBI indices reveal that stations near the Governador Island and Niterói margin have the worst EcoQS, showing medium to extreme pollution. Additionally, Foram-AMBI and exp (H'bc) provide a congruent EcoQS classification for ∼64% of the sites. Although these results are promising, they suggest that a significant effort should be made to obtain better knowledge of foraminiferal ecological requirements to employ benthic foraminifera as a biomonitoring and management method.

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.

Environmental impact of the largest petroleum terminal in SE Brazil: A multiproxy analysis based on sediment geochemistry and living benthic foraminifera.

The Dutos e Terminais do Centro Sul (DTCS) is one of the largest petroleum terminals of the South America located in the São Sebastião Channel (SSC) on the southeastern Brazilian coast. The aims of this study were to compare the sediment quality near the DTCS with that of several sites in the SSC region including the Araçá (AR) domestic sewage outfall and to assess the efficiency of the DTCS wastewater treatment plant. To achieve these goals, textural, geochemical, and living benthic foraminifera results were analyzed for the DTCS, AR, and SSC regions. Sediments in the DTCS area were silty with high concentrations of total organic carbon (1.7-2.4%), total nitrogen (0.2-0.3%), total sulfur (0.4-0.6%), and total (0.12-0.18%) and inorganic phosphorous (0.07-0.11%). These values were higher than those in sediments collected in the SSC and Araçá regions. The sediments' concentrations of As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn in the SSC and AR regions were lower than their corresponding probable effect levels (PELs). However, sediments near the DTCS were enriched with As, Cu, and Ni, whose concentrations exceeded their corresponding threshold effect levels (TELs). Around the DTCS outfall diffusers, living foraminiferal densities and diversities were lower than those for the other areas studied. In the DTCS area, it was necessary to search 50 to 190 cm3 of sediment to find 100 live specimens. In the SSC and Araçá areas, a maximum of 40 cm3 of sediment was enough to locate 100 live specimens. The lower density and diversity of living foraminifera around the DTCS than around the other areas illustrates the impact of the environmental stress caused by the presence of pollutants. These results indicate that the wastewater treatment plant efficiency is low and its discharge of pollutants from petrochemical waste liquids affects the benthic fauna around the DTCS in a potentially harmful manner.