Polycyclic aromatic hydrocarbons in a Natural Heritage Estuary influenced by anthropogenic activities in the South Atlantic: Integrating multiple source apportionment approaches.

Polycyclic aromatic hydrocarbons (PAHs) were analysed in the sediments of one of the most well-preserved estuaries in South Brazil, the Paranaguá Estuarine System (PES), using several source apportionment tools. The ∑PAH ranged from < DL to 125.6 ng g-1 dw (dry weight) (average 29.9 ± 26.1 ng g-1 dw), and the lowest levels detected were similar to those found in other protected areas of the world. In general, the PAH concentrations indicated excellent environmental quality for the entire estuary. Principal component analysis indicated that fine sediments and total organic carbon were the main factors controlling PAH concentrations in the PES. Multiple PAH sources were identified in the study area; biomass burning and fossil fuel combustion predominated but considerable amounts of petrogenic residues were also observed. We identified evidence of a contribution from an adjacent watershed resulting from the construction of interconnections between large rivers and from years of intense deforestation in the local Atlantic Forest.

Historical mercury contamination in a major Latin American industrial and port complex: The case of the Santos estuary, Southeastern Brazil.

The present study determined total mercury (Hg) in four 210Pb dated sediment cores to assess the historical anthropogenic Hg accumulation in the Santos estuary, Southeastern Brazil. Background levels were identified using the deepest sections of the cores, corresponding to pre-industrial ages. Mercury distribution in the sediment cores (0.02-2.64 mg kg-1) presented a large spatial and temporal variation. Contamination is highest in the upper estuary and indicates that the industrial hub, especially a chlor-alkali plant is the primary source of Hg. A contaminant trap effect is observed in this area associated with high fine sediment accumulation and Hg fluxes. The contamination pattern indicates that the regions not affected by direct inputs are influenced by reworking, resuspension, and transport of contaminated sediments by tidal flows. The Hg enrichment in the upper layers of the sediment cores demonstrates that the environmental actions fulfilled in the 1980s were insufficient to control Hg pollution in the Santos estuary.

Trace element fluxes during the "Anthropocene" in a large South American industrial and port area (Santos and São Vicente estuarine system, SE, Brazil).

The worldwide evidence of human activities on the environment led the scientific community to recognize a new geologic time unit known as the "Anthropocene." Since the twentieth century, urbanization and industrialization needs driven by population and economic growth have impacted several ecosystems including the estuaries. To assess the contamination, provenance, and fluxes of trace elements (As, Cr, Cu, Ni, Pb, Sc, V, and Zn) over the last century, a geochemical and chemometric technique was employed in sediment cores of an industrial and port region of international importance, the Santos and São Vicente Estuarine System (SSVES). The results indicated low contamination, with the highest enrichment factors (EFs) for Cu (EF = 3.1), Pb (EF = 2.7), Zn (EF = 2.4), and As (EF = 2.3) found next to the harbor area. The Pre-industrial records confirm the relatively high concentrations of As and its naturally enriched occurrence on the Brazilian shelf. Sediment accumulation rates and trace element fluxes showed a general increase over the years, since the early 1960s, associated with the "Great Acceleration" of the mid-twentieth century. These alterations are human-induced and include urbanization and industrialization. Nonetheless, as the contents and enrichment of trace elements indicate that the region is not severely polluted, we hypothesize that the contamination in the SSVES is likely related to the drainage and erosion of the urbanized adjacent area, rather than direct disposal of inorganic contaminants from the industrial activity.

Microbial perspective on the giant carbonate ridge Alpha Crucis (Southwestern Atlantic upper slope).

Deep-sea carbonate mounds can harbor a wide variety of heterotrophic and chemosynthetic microbial communities, providing biodiversity hotspots among the deep-sea benthic ecosystems. This study examined the bacterial and archaeal diversity and community structure in the water column and sediments associated with a recently described giant carbonate mound named Alpha Crucis Carbonate Ridge (ACCR), located in the Southwestern Atlantic Ocean. Because of the acoustic evidence of gas chimneys from a previous study, we further evaluated the chemosynthetic primary production through in situ-simulated dark carbon fixation rates. Pelagic microbial communities varied significantly with depth, showing a high abundance of photosynthetic groups in surface waters and taxa related to nitrification in intermediate and deep waters. The benthic communities from the top of the ACCR were very similar along with the sediment depth, while those from the base of the ACCR showed a clear stratification pattern, with members in the deep strata mainly related to anoxic and chemosynthetic ecosystems. Dark carbon fixation rates were of the same order of magnitude as those of deep-sea cold seeps and hydrothermal vents. Our study provides the first description of the ACCR microbiome and adds new information to help formulate and implement future conservation and management strategies for vulnerable marine ecosystems.

Historical deposition of PAHs in mud depocenters from the Southwestern Atlantic continental shelf: The influence of socio-economic development and coal consumption in the last century.

Polycyclic aromatic hydrocarbon (PAH) concentrations were determined in four dated sediment cores collected in mud depocenters of the southern Brazilian continental shelf. Core dating results covered the interval between 1925 and 2017. The total PAH concentrations (ΣPAHs) ranged from 44.69 ng g-1 to 305.43 ng g-1 and were similar between the analysed cores. Fine-grained sediments and total organic carbon (TOC) results did not correlate with the ΣPAHs, indicating that the variations in PAH concentrations are mostly related to variations in sources and emissions. PAH source appointment indicated a high input of a natural compound (perylene) and the predominance of anthropogenic PAHs from coal, biomass, and fuel combustion. Alkylated PAHs presented high contributions throughout all cores. The historical deposition of PAHs was associated with different periods of the socio-economic and industrial development of near coastal cities and reflected very well the history of coal production and consumption in the southern region of Brazil. The low levels of ΣPAHs before 1945 in all analysed cores may be related to the beginning of the industrialization process and the lower urbanization degree in the region. Between 1945 and 1965, the gradual ΣPAHs increase reflects the establishment and enlargement of the southern Brazilian industrial sector. The interval between 1965 and 1990 corresponded to the highest ΣPAHs in three of the four analysed cores. After 1990, a relative decrease in the ΣPAHs was observed in most cores and may be related the multiple cuts of incentives to the industrial usage of coal, as well as to Brazil's efforts in environmental regulation for coal extraction and consumption.

The Alpha Crucis Carbonate Ridge (ACCR): Discovery of a giant ring-shaped carbonate complex on the SW Atlantic margin.

Recently acquired bathymetric and high-resolution seismic data from the upper slope of Santos Basin, southern Brazilian margin, reveal a major geomorphological feature in the SW Atlantic that is interpreted as a carbonate ridge - the Alpha Crucis Carbonate Ridge (ACCR). The ACCR is the first megastructure of this type described on the SW Atlantic margin. The ~17 × 11-km-wide ring-shaped ACCR features tens of >100-m-high steep-sided carbonate mounds protruding from the surrounding seabed and flanked by elongated depressions. Comet-like marks downstream of the mound structures indicate that the area is presently influenced by the northward flow of the Intermediate Western Boundary Current (IWBC), a branch of the Subtropical Gyre that transports Antarctic Intermediate Water. Abundant carbonate sands and gravels cover the mounds and are overlain by a biologically significant community of living and dead ramified corals and associated invertebrates. The IWBC acts as a hydrodynamic factor that is responsible for both shaping the bottom and transporting coral larvae. We contend that the ACCR was formed by upward fluid flow along active sub-surface faults and fractures that formed by lateral extension generated by the ascending movement of salt diapirs at depth. The ACCR provides an important modern and accessible analogue for a seabed carbonate build-up related to sub-surface hydrocarbon systems.

A multivariate approach and sediment quality index evaluation applied to Baixada Santista, Southeastern Brazil.

Current studies use indices and chemometric approaches to assess the health quality of estuarine systems to support estuarine management. This study aims to use a multivariate approach and a set of indices to evaluate sediment health quality. Levels of Al, As, Cd, Cr, Cu, Fe, Ni, Pb, Sc, V, and Zn were quantified by ICP-OES, and nine indices were applied and evaluated individually. Most of the indices presented high values of Cu, Pb, and Zn, and the aggregative indices differed from each other in magnitude; however, the spatial distribution demonstrated the same trends. From PCA results, it was possible to differentiate lithogenic from the anthropogenic contribution, especially by Cu, Pb, and Zn. Thus, the integration of geochemical approaches and chemometric tools supported the interpretation of elemental contribution in terms of sources and pathway of heavy metals, which was similar to the results of other studies conducted in the area.

Insights on the evolution of the living Great Amazon Reef System, equatorial West Atlantic.

The Great Amazon Reef (GARS) is an extensive mesophotic reef ecosystem between Brazil and the Caribbean. Despite being considered as one of the most important mesophotic reef ecosystems of the South Atlantic, recent criticism on the existence of a living reef in the Amazon River mouth was raised by some scientists and politicians. The region is coveted for large-scale projects for oil and gas exploration. Here, we add to the increasing knowledge about the GARS by exploring evolutionary aspects of the reef using primary and secondary information on radiocarbon dating from carbonate samples. The results obtained demonstrate that the reef is alive and growing, with living organisms inhabiting the GARS in its totality. Additional studies on net reef growth, habitat diversity, and associated biodiversity are urgently needed to help reconcile economic activities and biodiversity conservation.

Geochemical behavior, environmental availability, and reconstruction of historical trends of Cu, Pb, and Zn in sediment cores of the Cananéia-Iguape coastal system, Southeastern Brazil.

The Cananéia-Iguape system is located in a coastal region of southeastern Brazil, recognized by UNESCO as an Atlantic Forest Biosphere Reserve. This system has suffered substantial environmental impacts due to the opening of an artificial channel and by past intensive mining activities. In this paper was performed the sequential chemical extraction of Cu, Pb, and Zn, on previously described sediment cores, and the statistical treatment of the data, allowing to estimate the remobilization geochemical behavior, the available content and the trend of accumulation between 1926 and 2008. The maximum available level (sum of all mobile fraction) were, in mgkg-1, 18.74 for Cu, 177.55 for Pb and 123.03 for Zn. Considering its environmental availability, Pb remains a concern in the system. It was possible to recognize the anthropic contribution of Pb, being the mining activities considered the only potential source of this metal in the region.

An extensive pockmark field on the upper Atlantic margin of Southeast Brazil: spatial analysis and its relationship with salt diapirism.

We present new evidence for the existence of a large pockmark field on the continental slope of the Santos Basin, offshore southeast Brazil. A recent high-resolution multibeam bathymetric survey revealed 984 pockmarks across a smooth seabed at water depths of 300-700 m. Four patterns of pockmark arrays were identified in the data: linear, network, concentric, and radial. Interpretation of Two-dimensional multi-channel seismic reflection profiles that crosscut the surveyed area shows numerous salt diapirs in various stages of development (e.g. salt domes, walls, and anticlines). Some diapirs were exposed on the seafloor, whereas the tops of others (diapir heads) were situated several hundreds of meters below the surface. Extensional faults typically cap these diapirs and reach shallow depths beneath the seafloor. Our analysis suggests that these pockmark patterns are linked to stages in the development of underlying diapirs and their related faults. The latter may extend above salt walls, take the form of polygonal extensional faults along higher-level salt anticlines, or concentric faults above diapir heads that reach close to the seafloor. Seismic data also revealed buried pockmark fields that had repeatedly developed since the Middle Miocene. The close spatio-temporal connection between pockmark and diapir distribution identified here suggests that the pockmark field extends further across the Campos and Espírito Santo Basins, offshore Brazil. Spatial overlap between the pockmark field topping a large diapir field and a proliferous hydrocarbon basin is believed to have facilitated the escape of fluid/gas from the subsurface to the water column, which was enhanced by halokinesis. This provides a possible control on fossil gas contribution to the marine system over geological time.

Environmental availability of potentially toxic elements in estuarine sediments of the Cananéia-Iguape coastal system, Southeastern Brazil.

The Cananéia-Iguape system is located in a Southeastern Brazilian coastal region, acknowledged by UNESCO as Biosphere Reserve of the Atlantic Rainforest. This system underwent important environmental changes due to the opening of the artificial channel of Valo Grande and by past intensive Pb ore mining activities. In view of this scenario, this study evaluated Cu, Pb and Zn availability in sediments from Cananéia-Iguape system, based on the content associated with the main components of the sediments. Moreover, in order to assess local contamination, the metals' contents were compared to Canadian quality guidelines, the past levels of metals preceding the mining activities and background sediment values. Concerning Cu and Zn in a state of chemical remobilization, both elements would possibly present no harm to the local communities. However, Pb available content exceeded the comparison values in various sampling sites, suggesting the need of monitoring regarding its bioavailability.

Sources and temporal patterns of polychlorinated biphenyls around a large South American grain-shipping port (Paranaguá Estuarine System, Brazil).

The Paranaguá Estuarine System (PES) is an important estuarine environment on the Brazilian coast. The economic importance of the PES is mainly related to industries, fuel terminals, and the main South American grain-shipping port. The aim of this work was to determine the vertical distribution of polychlorinated biphenyls (PCBs) in three sediment cores from the PES. The methods included Soxhlet extraction, clean-up, and quantification by gas chromatography with electron capture detection. The concentrations of total PCBs ranged from lower than the detection limit to 6.65 ng g(-1). Low PCB concentrations were detected in P1 and P3, which were collected far away from direct human activities. In P2, the compositional pattern of PCB congeners showed greater concentrations of tetra- and penta-chlorinated congeners associated with urban and port activities near Paranaguá city. The differences in concentrations between the three sediment cores were attributed to the distance of the sampling points in relation to the possible sources of pollution, which are mostly related to Paranaguá city. The vertical distribution of PCBs in the sediment core P2 was related to historical anthropogenic activities. The highest PCB input was from 1970 to the early 1990s, which coincides with a period of greater use of PCBs in Brazil as well as their greater worldwide production.

137Cs in marine sediments of Admiralty Bay, King George Island, Antarctica.

The radionuclide cesium-137 ((137)Cs) is produced exclusively by anthropogenic processes and primarily by nuclear explosions. This study determined the reference inventory that is (137)Cs associated with the element's original input, and utilized the levels of activity of this radionuclide previously measured in five sediment profiles collected from Admiralty Bay, Antarctica, to investigate the mobility of this element in the environment. (137)Cs has a half-life of 30 years. Because of this, it is environmentally persistent and has been shown to accumulate in marine organisms. The mean reference inventory of this radionuclide in Admiralty Bay sediments, determined using high resolution gamma ray spectrometry, was 20.23±8.94 Bq m(-2), and within the ambient (137)Cs activity range. A model of (137)Cs diffusion-convection was applied to data collected from 1cm intervals in sediment cores with the aim of providing insights with respect to this element's behavior in sediments. Model results showed a significant correlation between measured and modeled values using the concentrations of (137)Cs, and estimated input into the system from the global fallout of past nuclear tests and expected values based on local sedimentation rates. Results highlight the importance of accounting for the vertical diffusion of (137)Cs in marine sediments when used as a tracer for environmental processes and for assessing potential bioavailability.