Exploratory evaluation of iron and its speciation in surface waters of Admiralty Bay, King George Island, Antarctica.

The determination of dissolved iron concentrations and speciation was conducted for the first time in surface seawater coastline samples collected during the austral summer of 2020 in Admiralty Bay, King George Island, Antarctica. The technique of competitive ligand exchange/adsorptive cathodic stripping voltammetry with 2,3-dihydroxynaphthalene as the competing ligand was evaluated, showing a sensitivity between 14.25 and 21.05 nA nmol L-1 min-1, with an LOD of 14 pmol L-1 and a mean blank contribution of 0.248 nmol L-1. Physicochemical parameters such as pH (7.85 ± 0.2), salinity (32.7 ± 0.8) and dissolved oxygen (51.3 ± 26.6%) were compatible with those of the literature; however, the average temperature (4.2 ± 0.8 °C) was higher, possibly as a reflection of global warming. The dissolved iron mean value was 18.9 ± 6.1 nmol L-1, with a total ligand concentration of 23.6 ± 12.2 nmol L-1 and a conditional stability complex constant of 12.2 ± 0.2, indicating humic substances as possible ligands. On average, the calculated free iron concentrations were 0.7 ± 0.3 pmol L-1. Relatively high concentrations of iron indicate a possible local source of Fe, likely predominantly from upwelling sediments and secondarily from ice-melting waters, which does not limit the growth of the phytoplankton.

A systematic evaluation of polycyclic aromatic hydrocarbons in South Atlantic subtropical mangrove wetlands under a coastal zone development scenario.

Mangrove forests worldwide are threatened environments considered vulnerable to chronic contamination by hydrophobic contaminants such as polycyclic aromatic hydrocarbons (PAHs). These ecosystems have a key role in the dynamics of biogenic and anthropogenic carbon storage and provide proper conditions for accumulation. One of most important subtropical mangrove swamps in the South Atlantic is located in the Paranaguá Estuarine System (PES), the largest bay of South Brazil surrounded by well-preserved Atlantic rainforests; however, the PES is under imminent risks of damage, e.g., due to incidental oil spills during port operations. In this scenario, PAHs were assessed for the first time in the mangrove sediments of the PES. The concentrations of 16 priority PAHs (EPA) (

Urban effluents affect the early development stages of Brazilian fish species with implications for their population dynamics.

The pollution from urban effluents discharged into natural waters is a major cause of aquatic biodiversity loss. Ecotoxicological testing contributes significantly to understand the risk of exposure to the biota and to establish conservation policies. The objective of the current study was to assess the toxicity of a river highly influenced by urban effluents (Atuba River, Curitiba city, Southern Brazil) to the early stages of development in four South American native fish species, investigating the consequences at the population level through mathematical modelling. The species chosen were Salminus brasiliensis, Prochilodus lineatus, Rhamdia quelen, and Pseudoplatystoma corruscans, ecologically important species encompassing different conservation statuses and vulnerability. The embryos were exposed from 8 to 96 h post fertilization to the Atuba River water, collected downstream of the largest wastewater treatment plant in the Metropolitan Region of Curitiba, and their survival rates and deformities were registered. The species S. brasiliensis and P. lineatus presented the highest mortality rates, showing high sensitivity to the pollutants present in the water. According to the individual-based mathematical model, these species showed high vulnerability and risk of extinction under the tested experimental conditions, even when different sensitivity scenarios of juveniles and adults were considered. The other two species, R. quelen and P. corruscans, showed a more resistant condition to mortality, but also presented high frequency and severity of deformities. These results emphasize the importance of testing the sensitivity of different Brazilian native species for the conservation of biodiversity and the application of models to predict the effects of pollutants at the population level.

Ecological risk assessment of sedimentary hydrocarbons in a subtropical estuary as tools to select priority areas for environmental management.

The concentration, distribution, and ecological risk of hydrocarbons, as well as bulk parameters, were determined in surface sediments of the Babitonga Bay, a subtropical human-impacted estuary in South Atlantic. Total aliphatic and polycyclic aromatic hydrocarbons (PAHs) ranged between 0.8 and 201.2 µg g-1 and from 8.7 to 5489 ng g-1, respectively. Saguaçú Lagoon, the region near the ferry boat and the vicinity of São Francisco harbour (SFH), presented high hydrocarbon concentrations. Despite the low accumulation trend in this region, the SFH and city may act as a punctual hydrocarbon source. The inner portion of the estuary had the finest sediment grains and the highest concentrations of carbon, nitrogen, and sulphur, indicating its importance as a depositional and cumulative area. The occurrence of unresolved complex mixture suggested chronic oil contamination. Petrogenic (based on the high percentage of alkylated PAHs) and pyrolytic (according to the diagnostic ratios of PAH isomer pairs) sources were confirmed. Ecological risk assessment was evaluated by the risk quotient (RQ). All samples had at least one priority PAH present at above the negligible concentration, including naphthalene, which was observed in all samples. Only the sites near the ferry boat and at the Saguaçú Lagoon contained compounds with concentrations above their maximum permissible concentrations, while all other sampling sites are classified as "Low-risk." The spatial distribution of RQs coincides with PAHs distribution, indicating that the regions near SFH, ferry-boat, and the Saguaçú Lagoon should be considered to be priority areas when making environmental monitoring policies.

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.

Unraveling sources of hydrocarbons in subtropical estuaries with distinct degrees of protection in the Southwestern Atlantic Ocean, Brazil.

Sedimentary aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) were studied in subtropical estuaries with distinct degrees of legal protection, located in the Southwestern Atlantic Ocean, São Paulo State, Brazil. A multivariate approach was adopted, using the Hierarchical cluster analysis followed by the Principal Matrix Factorization analysis to support the hydrocarbons sources findings using diagnostic ratios. In general, the sites with the highest values of hydrocarbons were in the vicinity of well-urbanized cities, where sewage discharge, harbor and industrial activities take place. Pyrolitic PAHs were the predominant source of PAHs in the sites. The region can be considered not highly contaminated by hydrocarbons; however, specific sites under local anthropogenic impact from sewage and/or urban drainage, presented relatively high hydrocarbons levels. These findings highlight the importance of sources identification as reliable approach to be included in the management plan of protected areas under the inputs of several vectors of contamination.

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.

The Fundão dam failure: Iron ore tailing impact on marine benthic macrofauna.

The Fundão dam failure, the worst environmental disaster in Brazilian history, launched 50 million m3 of iron ore tailings mud through the Doce River, reaching the Atlantic Ocean. Generally, mine tailings increase the sediment inflow, leading to mud burial of epibenthic macrofauna, and the raise of metal(oid)s concentration causing macrofauna long-term changes. After almost four years, tailings mud was still spreading on the Doce River Shelf, while impacts on marine macrofauna were still unknown. Herein, the IMS index (a tracer of Fundão dam tailings mud), sediment variables, organic pollutants, and metal(oid)s were integrated to uncover the drives of macrofauna structure from Costas da Algas to Abrolhos bank MPAs. Tailings mud was present only in Doce River Mouth and Degredo, organic pollutants and metal(oid)s above safety levels were concentrated in those same areas. Tailings mud (IMS index) drastically reduced species richness and diversity, favoring the abundance of opportunistic species. Mud, IMS index and Al, Ba, and V, metal(oid)s linked to dam failure, structured macrofauna composition in this impacted area, dominated by resistant groups as Nuculidae, Spionidae, and Magelonidae. Conversely, an opposite pattern was found for further and deeper sites with high CaCO3 content and total nitrogen that also showed large grain size, in areas known to harbour biogenic structures, sustaining a macrofauna composition distinct from the impacted areas, dominated by Syllidae and Crassatellidae, sensitives to impacts. Macrofauna composition was most structured by sediment variables, followed by the intersection between metal(oid)s-IMS and Mud, both gradients acting almost entirely on a broad spatial scale. Benthic macrofauna at the Doce River Shelf is still impacted by Fundão dam tailings mud, even after almost four years of the disaster, and may continue to, since the influx of tailings does not stop, and sediment resuspension is a recurrent source for those impacts.

Polycyclic aromatic hydrocarbons (PAHs) in sediments of the amazon coast: Evidence for localized sources in contrast to massive regional biomass burning.

The Amazon coastal zone has become contaminated with organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs). However, information about their distribution and sources in this area is scarce, despite increasing deforestation and oil exploitation. Therefore, individual PAHs were analysed in the sediments of the Oyapock estuary, which is located in the Amazon coastal zone. This study provides information about the spatial and short-term temporal distributions of PAHs and discusses the major sources of PAHs to better understand the anthropogenic processes occurring in adjacent areas. The concentrations of all sixteen priority PAHs defined by the US EPA (United States Environmental Protection Agency, ∑16PAHs) ranged from 10.9 to 138.8 ng g-1 with a mean and standard deviation = 37.9 ± 20.5 and indicated that this estuary is not contaminated, while the mean levels were similar to those found in other Amazon regions and pristine areas along the coast of Brazil. No significant differences were found in the sedimentary PAHs levels between the wet and dry sampling campaigns, despite the different climatic conditions. Diagnostic ratios, positive matrix factorization (PMF) and cluster analysis have shown that the majority of the investigated PAHs were derived from combustion processes (at least 55.1%, as estimated by the PMF model). Localized source inputs from oil and its by-products concomitantly with natural/biogenic sources appear to be secondary sources. The PAH contribution from biomass and wood combustion was approximately 13.6% and was relatively lower than other regions of the Amazon that are undergoing massive biomass burning. As the first study of PAHs in this region, this study provides vital information on the healthy state of the estuary and can serve as a baseline for assessing the impacts of acute oil disasters or the chronic input of PAHs as a result of human settlements.

Anthropogenic and natural inputs of polycyclic aromatic hydrocarbons in the sediment of three coastal systems of the Brazilian Amazon.

Polycyclic aromatic hydrocarbons (PAHs) were measured in 32 surface sediment samples collected around three cities (Barcarena, Belém, and Santana) located on the coast of the Brazilian Amazon. The concentration of total PAHs ranged from lower than detection limit to 33,101 ng g-1 in a sample from Barcarena and was related to a large aluminum industrial complex and port activities. In Belém, which is the most populated area in the Amazon region, PAHs were probably derived from untreated sewage discharge and inputs from a large municipal landfill. Pyrogenic PAHs were predominant in both cities, with a smaller contribution of petrogenic PAHs. Low alkylated PAH levels may be associated with small boats and ship traffic. Santana had low total PAH concentrations, with a predominance of unusual alkylated PAHs, probably related to diagenetic transformations of organic matter in the sediment. In general, PAH concentrations in the samples were low and may reflect baseline levels for this Amazon estuarine system.

Sources and depositional changes of aliphatic hydrocarbons recorded in sedimentary cores from Admiralty Bay, South Shetland Archipelago, Antarctica during last decades.

Organic biomarkers, as aliphatic hydrocarbons, are present in sedimentary organic matter and have been largely applied to the evaluation of recent environmental changes in the marine environment around the globe, including the Antarctic continent. Five sediment cores were taken in the Admiralty Bay, South Shetland Archipelago, Antarctica to evaluate changes in the signature of aliphatic hydrocarbons such as n-alkanes (n-C10 to n-C40) and isoprenoids as pristane and phytane, over the last decades. The total n-alkanes concentration ranged from 0.17 to 1.67 µg g-1 (mean = 0.74 ± 0.42) which is considered low and similar to pristine sediments. Aliphatic hydrocarbons present in the sedimentary pool came mostly from terrestrial sources as Antarctic lichens and mosses, and from marine sources as the macroalgae forest debris and emergent macrophytes. Anthropogenic inputs of aliphatic hydrocarbons (e.g., petroleum and their by-products) may be neglected based on the multi-proxy approach used to distinct sources of these organic compounds. In general, no significant changes in the sources of aliphatic hydrocarbons were observed along the sediment cores; however, an increased aliphatic hydrocarbons input registered between 1975 and 1992 may be related to the increase in meltwater runoff and the relatively high abundance of marine producers more adapted to increased sea temperatures.

One century of historical deposition and flux of hydrocarbons in a sediment core from a South Atlantic RAMSAR subtropical estuary.

Levels and fluxes of Polycyclic aromatic hydrocarbons (PAHs) and aliphatic hydrocarbons (AHs), including n-alkanes and petroleum biomarkers (PBMs), were measured in a sedimentary core from a nominated RAMSAR (Guaratuba Bay, Brazil) subtropical estuary experiencing relatively low human impacts, to describe the evolution of anthropogenic activities over the last century. TOC contents varied from 0.80 to 1.25%. No significant correlation between hydrocarbons and TOC with grain size (predominantly sand) was observed. Concentration and flux of total AHs ranged from 65.5 to 195 µg g-1 and 27.6 to 82.0 µg cm-2 y-1, respectively, with the highest levels found in 1960-1966, when access routes to Guaratuba city were improved. Diagnostic ratios based on AH components showed an apparent change in the sources over time, with biogenic origins prevailing until 1966-1971, followed by subsequent increases in petroleum sources. Petroleum tricyclic terpanes were detected in the core (0.40 to 3.0 µg g-1), suggesting the use of lubricating oil in the bay area. Hopanes were mainly attributed to biological sources. Concentration and flux of total PAHs ranged from 8.65 to 35.9 ng g-1 and 3.64 to 15.1 ng cm-2 y-1, respectively, with the highest levels found in the top core section, reflecting recently increased human activity, while a peak PAH concentration at approximately 1977-1983 can be assumed to be a delayed signal of increased human occupation as a consequence of the improvement of access roads to the area, which started in the 1960s. Alkylated were the most abundant group of PAHs throughout the core. Despite relatively low concentrations of hydrocarbon deposition over approximately 90 years, this study highlights the influence of human occupation and slight petroleum contamination in this preserved area, mainly in recent core sections.

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.

Natural archives of long-range transported contamination at the remote lake Letseng-la Letsie, Maloti Mountains, Lesotho.

Naturally accumulating archives, such as lake sediments and wetland peats, in remote areas may be used to identify the scale and rates of atmospherically deposited pollutant inputs to natural ecosystems. Co-located lake sediment and wetland cores were collected from Letseng-la Letsie, a remote lake in the Maloti Mountains of southern Lesotho. The cores were radiometrically dated and analysed for a suite of contaminants including trace metals and metalloids (Hg, Pb, Cu, Ni, Zn, As), fly-ash particles, stable nitrogen isotopes, polycyclic aromatic hydrocarbons (PAHs) and persistent organic pollutants such as polychlorinated biphenyls (PCBs), polybrominated flame retardants (PBDEs) and hexachlorobenzene (HCB). While most trace metals showed no recent enrichment, mercury, fly-ash particles, high molecular weight PAHs and total PCBs showed low but increasing levels of contamination since c.1970, likely the result of long-range transport from coal combustion and other industrial sources in the Highveld region of South Africa. However, back-trajectory analysis revealed that atmospheric transport from this region to southern Lesotho is infrequent and the scale of contamination is low. To our knowledge, these data represent the first palaeolimnological records and the first trace contaminant data for Lesotho, and one of the first multi-pollutant historical records for southern Africa. They therefore provide a baseline for future regional assessments in the context of continued coal combustion in South Africa through to the mid-21st century.

Depositional input of hydrocarbons recorded in sedimentary cores from Deception and Penguin Islands (South Shetland Archipelago, Antarctica).

Polycyclic aromatic hydrocarbons (PAHs) and aliphatic hydrocarbons (AHs), including petroleum biomarkers, were studied in four sediment cores collected around Deception and Penguin Islands, Antarctica. Total PAHs in Deception Island (DCP) samples ranged from 2.0 to 26.8 ng g-1, and in Penguin Island (PGI) varied between 13.2 and 60.3 ng g-1. Multiple sources of PAHs were verified in DCP, with petrogenic-derived compounds being predominant over the last 10 years. In PGI, PAHs related to natural contributions from the erosion of coal deposits were reported. Total AHs in DCP ranged from 4.5 to 19 µg g-1 and in PGI varied between 5.3 and 21.9 µg g-1. In DCP, the n-alkanes distribution pattern showed the presence of petroleum residues in the top sections and both terpanes and hopanes were detected, related to the use of fossil fuels for power generation and in different types of vessels. In PGI, the main source of n-alkanes was marine inputs and only terpanes were detected. The slight increase in hydrocarbon levels observed from 1980 onward in DCP was assumed to be due to the development of tourism in the region and to the scientific station activities. In PGI, anthropogenic-related hydrocarbons were detected in the recent sections and were linked to the development of tourism near the island, scientific activities and the increase in vessel traffic. In general, the concentrations of hydrocarbons found around both islands were comparable to those found in uncontaminated Antarctic regions.

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.

Multiple lines of evidence of sediment quality in an urban Marine Protected Area (Xixová-Japuí State Park, SP, Brazil).

Marine Protected Areas (MPAs) aim to protect habitats, biodiversity, and ecological processes as a conservation tool. These areas have been affected by contamination, which threats the biodiversity and ecological functioning. In this study, we evaluated the sediment quality of Xixová-Japuí State Park (XJSP), an MPA located in an urbanized Bay (Santos, Southeast Brazil) by integrating multiple lines-of-evidence. Six sites were selected within the XJSP and analyzed for sediment chemistry, toxicity, and benthic community descriptors using Sediment Quality Triad approach (SQT). Whole-sediment Toxicity Identification Evaluation (TIE) was employed as a complementary line of evidence to confirm the presence of domestic effluent discharges as a potential stressor. The SQT showed that sediments collected within XJSP are impacted by contaminants, exhibiting chronic toxicity and changes in benthic community. TIE results indicated that trace metals, organic contaminants, and ammonia contributed to the observed effects. Our results also indicate a lack of effectiveness of MPA in protecting the biodiversity due to the contamination sources, which requires efforts to pollution control in order to ensure the environmental conservation and management plan goals.

Petroleum biomarkers as tracers of low-level chronic oil contamination of coastal environments: A systematic approach in a subtropical mangrove.

Petroleum biomarkers (hopanes, terpanes and steranes) are frequently assessed in estuarine sediments as tracers of oil input. In order to compare distinct patterns of hydrocarbon accumulation in mudflats, salt marsh and mangrove, sediments from two transects (control and impacted areas) were sampled in Paranaguá Bay, SW Atlantic. Concentrations of n-alkanes, polycyclic aromatic hydrocarbons (PAHs) and petroleum biomarkers (hopanes, terpanes and steranes) were determined, as well as bulk parameters (TOC, grain size and δ13C). N-alkanes concentrations were similar between control and impacted sites (respectively, 3.03 ±â€¯1.20 µg g-1 and 4.11 ±â€¯3.02 µg g-1) and reflected a high biogenic input. Conversely, PAHs and petroleum biomarker concentrations were three to six times higher in impacted site than the control site (respectively, 60.4 ±â€¯23.3 ng g-1 and 22.0 ±â€¯25.0 ng g-1 for PAHs and 197.7 ±â€¯51.8 ng g-1 and 40.2 ±â€¯32. ng g-1 for hopanes). Despite these differences, concentrations were lower than those reported for highly impacted areas worldwide. Diagnostic ratios and hydrocarbon parameters (e.g. total PAHs and total petroleum biomarkers) helped to distinguish human impact in the ecological zones, suggesting different sources and/or levels of weathering, confirmed by ANOVA tests. TOC played a fundamental role to the concentration of hydrocarbons, showing similar distributions along the transects. Petroleum biomarkers could clearly indicate the preferential sites of deposition and assign different levels of anthropic contamination by hydrocarbons, thus providing clear information about the chronic petroleum pollution in coastal sediments.

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.