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The Paranaguá Estuarine System (PES) is an extensive subtropical estuarine system on the Southern Brazilian coast. It encompasses one of the last preserved areas of the Atlantic Forest and is recognized by UNESCO as a Natural Heritage site. This study evaluates the human impact of rapid and unplanned urbanization, an inefficient sewage system, and two port complexes by using linear alkylbenzenes (LABs) as a molecular marker for sewage input. The LAB analyses included Soxhlet extraction, clean-up, and quantification, which was performed using a gas chromatograph coupled to a mass spectrometer. The concentrations of total LABs (∑LABs) in the dry-weight sediments of PES ranged from below detection limits to 42.7 ng g -1 , with an average of 6.5 ± 7.8 ng g -1 . The primary sources of LABs are rivers surrounding the city of Paranaguá, which receive sewage inputs. In contrast, the input of allochthonous organic carbon and fine sediments is primarily associated with discharges from the Antonina River watershed. The recent unplanned occupation of estuarine margins, with untreated or inadequately treated sewage discharged directly into the environment or cesspools, explains the low degradation levels of LABs found in some sectors of the PES. The current concentrations of LABs, lower than those along the Brazilian coast and in densely populated coastal countries, suggest good sediment quality. This study shows that LABs can serve as a geochemical tool for tracing sources and distinguishing impacts related to population density in one of the largest preserved subtropical estuarine areas in the Southern Hemisphere., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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 δ 13 C). N-alkanes concentrations were similar between control and impacted sites (respectively, 3.03 ± 1.20 μg g -1 and 4.11 ± 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 ± 23.3 ng g -1 and 22.0 ± 25.0 ng g -1 for PAHs and 197.7 ± 51.8 ng g -1 and 40.2 ± 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., (Copyright © 2019. Published by Elsevier Ltd.)

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The feasibility of biomarkers to accurately detect pollution in estuaries and coastal areas appears to be overestimated in the scientific literature, and is likely stemming from a bias towards publishing only positive results. Herein, we test the applicability of antioxidant capacity and lipid peroxidation to detect potential in situ sewage impacts on a subtropical estuary. We experimentally assessed variation in malondialdehyde (MDA, an indicator of lipid peroxidation) and total antioxidant capacity against peroxyl radicals (ACAP) through transplantations of the worm Laeonereis culveri from control to sewage-polluted areas. Variations in biomarkers were more related to natural environmental variability and small-scale heterogeneity among areas than to experimental exposure to sewage. Use of oxidative stress biomarkers is promising but further experimental work under real-life conditions is necessary to further validate and establish their accuracy and feasibility for practical purposes.

The occurrence, distribution, and the total mass of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were studied in surficial sediments of the Paranaguá Estuarine System (PES), a subtropical estuary in Southern Atlantic. Altogether, concentrations and inventories of contaminants ranged from <0.06 to 4.78 ng g -1 and < 0.13 to 10.47 ng cm -2 , respectively. OCPs presented the higher total mass (10.85 kg) and a decreasing trend from the inner estuary towards the adjoining shallow shelf. The occurrence of PCBs was restricted to sites nearby urban and industrial areas, which accumulated ~80% of the total mass of PCBs. Although the level of contamination is low, the results refer to recent years, which mean that the actual values could be greater if sediments from periods of higher usage were analyzed. This study provides the first estimates of POPs (persistent organic pollutants) total mass in the PES, contributing to data for the Southern American inventories., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

This study investigates the impact of repeated diesel spills on the structure of intertidal macrofaunal assemblages of a subtropical estuary. Three frequencies of exposure events were compared against two dosages of oil in a factorial experiment with asymmetrical controls. Hypotheses were tested to distinguish between (i) the overall effect of oil spills, (ii) the effect of diesel dosage via different exposure regimes, and (iii) the effect of time since last spill. Repeated oil spills dramatically altered the overall structure of assemblages and reduced the total density of macrofauna and densities of dominant taxa. Increasing the frequency of oil spills negatively affected macrofauna. In general, frequent low-dosage oil spills were more deleterious than infrequent high-dosage ones. However, increases in densities of some taxa, mainly the gastropod Heleobia australis, were observed in response to infrequent spills. Our results highlight the importance of repeated exposure events in determining the extent of oil impacts., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The composition and seasonal variations of sedimentary organic matter were investigated along the Cotinga sub-estuary, located in Paranaguá Bay, a large South American estuary where urban activities and the primary Brazilian grain shipping port are sources of pollution. Steroids and hydrocarbons were analyzed in surface sediments collected during the austral winter (2008) and summer (2009) in three distinct sectors, along this sub-estuary in a presumed gradient of fecal contamination. Concentrations ranged from 0.28 to 7.33 μgg (-1) (in dry sample weight thereafter),

Babitonga Bay is a large estuary, which has been under pressure from anthropogenic activities coexisting with a natural area of Atlantic rainforest and mangrove systems. The concentration of persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) was determined to evaluate the contamination status and the determine possible pollution sources in the estuary. The ∑ DDT (sum of DDT, DDE and DDD concentrations) was the predominant OCP group, with concentrations ranging from < DL (below detection limit) to 122 ng g − 1 . The exceptionally high concentration of p,p′-DDT (80%) found near São Francisco harbour exceeded SQG limits indicating highly toxic conditions in the area that may be attributed to a recent contamination from some local input. In contrast, other sites in the estuary presented higher concentration of the metabolite p,p′-DDE (34%). The results suggest strongly anthropogenic impact in specific sites of this estuary, which need further investigation. [ABSTRACT FROM AUTHOR]

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. [Display omitted] • PAHs were evaluated with a wide sample network in a Natural World Heritage estuary. • Different approaches were used to estimate the sources of sedimentary PAHs. • The highest levels were related to interbasin transfer, farming, and deforestation. • Long-term monitoring of sedimentary PAHs in the PES is crucial for estuary protection. [ABSTRACT FROM AUTHOR]

Guaratuba Bay, a subtropical estuary located in the SW Atlantic, is under variable anthropogenic pressure throughout the year. Samples of surficial suspended particulate matter (SPM) were collected at 22 sites during three different periods to evaluate the temporal and spatial variability of aliphatic hydrocarbons (AHs) and linear alkylbenzenes (LABs). These compounds were determined by gas chromatography with flame ionization detection (GC-FID) and mass spectrometry (GC/MS). The spatial distributions of both compound classes were similar and varied among the sampling campaigns. Generally, the highest concentrations were observed during the austral summer, highlighting the importance of the increased human influence during this season. The compound distributions were also affected by the natural geochemical processes of organic matter accumulation. AHs were associated with petroleum, derived from boat and vehicle traffic, and biogenic sources, related to mangrove forests and autochthonous production. The LAB composition evidenced preferential degradation processes during the austral summer. [ABSTRACT FROM AUTHOR]

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%). [Copyright &y& Elsevier]

Abstract: The effects of diesel oil on benthic associations from unvegetated tidal flats in a subtropical estuary were experimentally evaluated using a Multivariate Before and After/Control and Impact Model (M-BACI). Impacted treatments were contrasted with controls in 14 successive periods before and after the oil spill. An acute effect was recorded just after the impact, but the recovery to pre-disturbance population levels was extremely fast. The increase in the total density of the benthic community after the disturbance was the result of an increase in the densities of Heleobia australis, oligochaetes, and ostracods, observed in both impacted and control treatments, as a reflection of background variability and not the presence of the contaminant. The experimental spill had little influence on the biological descriptors of the benthic associations, which were resilient or tolerant to oil disturbance at the temporal (147days) and spatial (cm2) scales used in the experiment. [Copyright &y& Elsevier]

This paper reports the reconstruction of the contamination history of a large South American industrial coastal area (Santos Estuary, Brazil) using linear alkylbenzenes (LABs). Three sediment cores were dated by 137Cs. Concentrations in surficial layers were comparable to the midrange concentrations reported for coastal sediments worldwide. LAB concentrations increased towards the surface, indicating increased waste discharges into the estuary in recent decades. The highest concentration values occurred in the early 1970s, a time of intense industrial activity and marked population growth. The decreased LAB concentration, in the late 1970s was assumed to be the result of the world oil crisis. Treatment of industrial effluents, which began in 1984, was represented by decreased LAB levels. Microbial degradation of LABs may be more intense in the industrial area sediments. The results show that industrial and domestic waste discharges are a historical problem in the area. [Copyright &y& Elsevier]

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, ∑ 16 PAHs) 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. Image 1 • The Oyapock estuary is not contaminated with polycyclic aromatic hydrocarbons (PAHs). • PAHs showed no significant differences between the wet and dry seasons. • The highest PAH levels were detected in the sector farthest from the open ocean. • Local sources of PAHs were more important than burning biomass from distant sources. [ABSTRACT FROM AUTHOR]