How did a tailings spill change the distribution of legacy organochlorine compounds in a Southeast Atlantic inner shelf area: Is a hidden danger being transferred to the ocean?

Polychlorinated biphenyls (PCBs) and dichloro-diphenyl-trichloroethane (DDT) were evaluated in water and sediments from the Espírito Santo Inner Shelf (ESIS), Brazil, three years after the Fundão dam failure (FDF). We discuss the levels, sources, fate, and current environmental risks of these contaminants on temporal and spatial scales. In addition, the associated coastal dispersion patterns, water-sediment exchange trends, and environmental alterations were also discussed. Low contributions and no environmental risks were verified for PCBs after FDF. However, the low concentrations and frequency of occurrence in the samples did not allow for further reliable conclusions regarding the source of this contaminant. In contrast, hazard risk has been detected for DDTs in water and sediments. In sediments, there were a significant increase in level (up to 13.42 ng g-1; outlier = 369.6 ng g-1), inventory (maximum = 35.98 ng cm-2) and mean total mass (21.1 ± 39.4 kg) of DDTs after FDF. The integrated assessment of the spatial distribution in water and sediment suggests that DDTs was released from the Doce River, travelled south by the water column, and returned to the mouth region by northward sediment transport, where it accumulated. However, intense rainfall increased the input of DDTs to the ESIS and may have also altered its spatial distribution. Fugacity fraction analysis (ƒƒ) indicated a net flux of DDTs from water to sediment, suggesting that vertical sinking was an important transport process in this area. Finally, the findings indicate that FDF contributed to DDTs input on ESIS by remobilizing contaminated past sediments and soils from the Doce River drainage basin. This contribution is expected to continue since a large amount of tailings is still stored in the river basin and estuary. These results highlight the importance of assessing the indirect impacts of large-scale land disasters on marine environments, and may be helpful in future interpretations of additional local trends and global inventories of legacy pollutants.

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.

Low levels of persistent organic pollutants in sediments of the Doce River mouth, South Atlantic, before the Fundão dam failure.

The Doce River mouth (DRM) was severely impacted by the rupture of the Fundão Dam in 2015, considered the greatest Brazilian environmental tragedy in terms of tailings volume released (>40 million m3) and traveled distance (~600 km until the Atlantic Ocean). Environmental monitoring has been performed since then, but background levels are scarce or absent to Persistent Organic Pollutants (POPs), making impact assessments difficult. In the current study, we presented the baseline levels, inventories, and risk assessment of the POPs polychlorinated biphenyl (PCBs) and organochlorinated pesticides (OCPs), in surface sediment of the DRM. Samples were collected in December 2010 and July 2011, i.e., four years before the Fundão dam failure. The total PCBs and the OCPs (Aldrin, HCHs, and Chlordanes) were detected in both sampling campaigns, with levels up to 9.50 and 1.64, 0.28, and 0.63 ng g-1, respectively. The decrease of the Doce River flow was the main factor contributing to seasonal variations in the spatial distribution, and to a slight decline in the levels and frequency of the analyzed POPs in sediments collected in the dry season (July 2011). Environmental risk assessment, inventories, and total mass results suggest a low potential of PCBs and OCPs accumulation before the dam failure. This is the first POPs assessment in the study area that helped identify some unexpected impacts of the Fundão dam failure and contributed to the understanding of POPs cycles in the Southern Atlantic, data that are still scarce in the region.

Tracking the sources of allochthonous organic matter along a subtropical fluvial-estuarine gradient using molecular proxies in view of land uses.

Sedimentary sterols and linear alkylbenzenes associated with allochthonous organic matter (AOM) inputs were studied in surface sediments along the Tubarão riverbed, South Brazil. These markers were analysed in terms of concentrations, diagnostic ratios and by using multivariate analyses to identify the main organic matter sources. It was necessary to integrate all these factors to distinguish the sources and determine sewage contamination. Phytosterols predominated over faecal sterols, but the contributions of livestock waste along the river (determined in 50% of the sites) were confirmed by the fingerprint analysis. Raw sewage contamination was verified at one site, according to the increased levels of sewage molecular markers and confirmed by the multivariate analyses and diagnostic ratios calibrated to this region. A possible synergistic effect between inorganic nanoparticles from coal mine waste and organic contaminants related to AOM input was suggested and should not be ignored since both activities severely contribute to the environmental changes in much of this fluvial-estuarine gradient from the South Atlantic.

Tracking the historical sewage input in South American subtropical estuarine systems based on faecal sterols and bulk organic matter stable isotopes (δ13C and δ15N).

Faecal sterols and stable isotopes (δ13C and δ15N) from bulk organic matter (OM) were analysed in three sedimentary cores collected in two subtropical bays located in the South Atlantic to evaluate historical trends in the sewage input and to track possible changes in the bulk isotopic composition of OM in recent decades. The values of δ13C and δ15N ranged from -27.4 to -25.0‰ and from 0.5 to 3.9‰, respectively, without a clear trend in the variation over the whole period covered by sediment cores and with no conclusive interpretation of a specific range value typically related to the sewage input for these areas. The maximum coprostanol concentration was 0.19 µg g-1 in the upper 4 cm of one core, which was not considered contaminated by evaluation of the sterols diagnostic ratios. Even at low levels, the coprostanol concentrations followed variations in urban and economical regional development. Baseline values for faecal sterols (in average between 0.03 and 0.05 µg g-1), which may represent a previous non-impacted environment scenarios, were calculated for use in comparative perspectives for future evaluations of the sewage input and contamination.

Hydrocarbon and sewage contamination near fringing reefs along the west coast of Havana, Cuba: A multiple sedimentary molecular marker approach.

Organic contamination is a major environmental concern in coastal regions, and it can be evaluated by the determination of aliphatic hydrocarbons (AHs), polycyclic aromatic hydrocarbons (PAHs), faecal sterols and linear alkylbenzenes (LABs). The concentrations of these organic markers were obtained from nine surface sediment samples to evaluate a possible contamination near a fringing reef on the west coast of Havana, Cuba. The AH levels ranged from 1.24 to 135.6 µg g-1, the PAH levels were up to 2133 ng g-1, the faecal sterol levels ranged from 0.03 to 1.54 µg g-1, and the total LAB levels were up to 22.7 ng g-1. The highest concentrations were obtained at sites close to Havana Bay and at the sources of untreated sewage input. A decreasing concentration gradient was observed from Havana Bay to the outer sites. Although only two sites presented high levels of contamination, untreated sewage discharged close to the fringing reef may affect its environment.

Organic contamination as a driver of structural changes of hydroid's assemblages of the coral reefs near to Havana Harbour, Cuba.

Hydroid assemblage's responses to organic contamination were evaluated using sedimentary sterols as explanatory variables. At seven coral reef sites in the Havana west coast, hydroids were collected along three 10 m × 1 m, 10 m deep transects. Five sterols were analysed, i.e., coprostanol, an indicator of faecal contamination, and cholestanol, cholesterol, stigmasterol and brassicasterol, indicators of biogenic organic matter inputs. The sampling sites were classified by level of contamination. A total of 65 species comprised the hydroid assemblages. Hydroids community abundance and richness decreased in the contaminated sites. Coprostanol had the highest relative importance for these variables and also for Plumularia floridana and Clytia gracilis abundances. Obelia dichotoma and Halecium bermudense were relatively abundant in the contaminated sites. The results indicate that faecal contamination negatively affected the hydroid assemblages, highlighting the importance of integrated biological and chemical indicators to evaluate the environmental conditions of the Havana coral reef.

Insights about sources, distribution, and degradation of sewage and biogenic molecular markers in surficial sediments and suspended particulate matter from a human-impacted subtropical estuary.

The molecular markers sterols and linear alkylbenzenes (LABs) were analyzed in the surficial sediments and suspended particulate matter (SPM) of a subtropical estuary in South Atlantic (Paranaguá Estuarine System). The purpose of this study was identify the spatial distribution of sewage and the input of biogenic organic matter (OM) and to provide comparative insights about their behavior, compositions, and sources. The concentration of coprostanol ranged from < DL (detection limit) to 2.67 µg g-1 in SPM and from < DL to 0.94 µg g-1 in sediments. Total LABs ranged from 43.8 to 480.0 ng g-1 in SPM and from < DL to 21.0 ng g-1 in sediments. LABs homologs composition varied between the two matrices. The local hydrodynamic pattern may promote water column homogenization, dispersion, and dilution of sewage particles, and preferential sedimentation in fluvial and mixture zones. Results suggest that SPM is a good matrix for larger spatial and short time scale evaluation while sediments may help to define hot spot areas of input and final deposition of sewage particles. Marine sterols predominated in SPM while no dominance patterns of marine/terrestrial sterols occurred in surficial sediments. The higher degradation rates of sterols and LABs in the water column must be the main factor for the sharp drop in concentration towards the sediment and the variation of the preferential composition of these markers between compartments.

An integrated evaluation of some faecal indicator bacteria (FIB) and chemical markers as potential tools for monitoring sewage contamination in subtropical estuaries.

Sewage input and the relationship between chemical markers (linear alkylbenzenes and coprostanol) and fecal indicator bacteria (FIB, Escherichia coli and enterococci), were evaluated in order to establish thresholds values for chemical markers in suspended particulate matter (SPM) as indicators of sewage contamination in two subtropical estuaries in South Atlantic Brazil. Both chemical markers presented no linear relationship with FIB due to high spatial microbiological variability, however, microbiological water quality was related to coprostanol values when analyzed by logistic regression, indicating that linear models may not be the best representation of the relationship between both classes of indicators. Logistic regression was performed with all data and separately for two sampling seasons, using 800 and 100 MPN 100 mL-1 of E. coli and enterococci, respectively, as the microbiological limits of sewage contamination. Threshold values of coprostanol varied depending on the FIB and season, ranging between 1.00 and 2.23 µg g-1 SPM. The range of threshold values of coprostanol for SPM are relatively higher and more variable than those suggested in literature for sediments (0.10-0.50 µg g-1), probably due to higher concentration of coprostanol in SPM than in sediment. Temperature may affect the relationship between microbiological indicators and coprostanol, since the threshold value of coprostanol found here was similar to tropical areas, but lower than those found during winter in temperate areas, reinforcing the idea that threshold values should be calibrated for different climatic conditions.

Coupling spectroscopic and chromatographic techniques for evaluation of the depositional history of hydrocarbons in a subtropical estuary.

Spectroscopic and chromatographic techniques can be used together to evaluate hydrocarbon inputs to coastal environments such as the Paranaguá estuarine system (PES), located in the SW Atlantic, Brazil. Historical inputs of aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed using two sediment cores from the PES. The AHs were related to the presence of biogenic organic matter and degraded oil residues. The PAHs were associated with mixed sources. The highest hydrocarbon concentrations were related to oil spills, while relatively low levels could be attributed to the decrease in oil usage during the global oil crisis. The results of electron paramagnetic resonance were in agreement with the absolute AHs and PAHs concentrations measured by chromatographic techniques, while near-infrared spectroscopy results were consistent with unresolved complex mixture (UCM)/total n-alkanes ratios. These findings suggest that the use of a combination of techniques can increase the accuracy of assessment of contamination in sediments.

An integrated evaluation of molecular marker indices and linear alkylbenzenes (LABs) to measure sewage input in a subtropical estuary (Babitonga Bay, Brazil).

Babitonga Bay is a South Atlantic estuary with significant ecological function; it is part of the last remaining areas of mangrove communities in the Southern Hemisphere. The aim of this study was to determine the spatial distribution of the faecal sterols and linear alkylbenzenes (LABs) in surface sediments and to perform an integrated evaluation of several molecular marker indices to assess the sewage contamination status in the study area. The highest observed concentrations of faecal sterols (coprostanol + epicoprostanol) and LABs were 6.65 µg g(-1) and 413.3 ng g(-1), respectively. Several faecal sterol indices were calculated and correlated with coprostanol levels; these analyses showed that the index limits presented in the current literature could underestimate the sewage contamination in this study area. For the overall estuarine system, a low sewage impact may be assumed based on the low total mass inventories calculated for coprostanol (between 1.4% and 4.8%).