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The Fundão dam failure, the worst environmental disaster in Brazilian history, launched 50 million m

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.

Made available in DSpace on 2019-10-06T16:13:55Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-06-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Marine Protected Areas (MPAs) represent a tool for conservation that is intended to protect marine and estuarine habitats, biodiversity, and ecological processes. Many MPAs, some of which include estuarine zones, are affected by contamination sources; the discharge of chemicals into aquatic systems results in sediment contamination, risks to benthic systems, and consequent negative effects on ecological function. This study evaluated sediment quality in estuaries located within the Mosaic of Marine Protected Areas of São Paulo State, Brazil (MMPASP) in austral winter and summer: the Verde River (RV), the Una do Prelado River (BU), the Guaraú River (GU), the Preto River (RP), and the Itanhaém River (ITA). Data on sediment chemistry (major and trace metals, as well as hydrocarbons) and whole-sediment toxicity in copepods and amphipods were associated with ecological indices of macrobenthic infaunal organisms in a weight-of-evidence approach meant to estimate the effects at the community level. Results revealed low-to-moderate levels of contamination, with higher concentrations detected at sites influenced by domestic effluent discharges (RP, ITA). Site-specific chemical contamination guidelines were in accordance with biological responses than threshold levels from international benchmarks, indicating a failure of these international criteria to predict effects. Sediments were toxic, and benthic descriptors corroborated these findings. The results reflected a pattern of environmental quality that ranged from relatively good conditions (RV, BU, GU) to poor environmental quality (RP, ITA). We concluded that benthic environments in the estuaries of the Central Shore Marine Protected Area (APAMLC) exhibit a good ecological status in general, but some sites are directly impacted by human activities and exhibit contamination levels associated with biological effects, thereby showing that some portions of these MPAs may be damaged by contamination. Environmental assessments based on the sediment quality triad (SQT) method provide suitable and reliable information on pollution within MPAs and can assist in establishing additional policies to control pollution sources and achieve conservation goals. Núcleo de Estudos em Poluição e Ecotoxicologia Aquática Universidade Estadual Paulista (UNESP), Pça. Infante D. Henrique s/n° 11330-900, São Vicente Centro de Estudos do Mar Universidade Federal do Paraná (UFPR), Av. Beira Mar, s/n° 83255-976, Pontal do Paraná Núcleo de Estudos em Poluição e Ecotoxicologia Aquática Universidade Estadual Paulista (UNESP), Pça. Infante D. Henrique s/n° 11330-900, São Vicente FAPESP: 2013/15482-0 CNPq: 306468/2017-4 CNPq: 311609/2014-7 CNPq: 455280/2014-2

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.

Estuaries are under major impacts from pollution even when managed as conservation units. Here we used multiple biogeochemical indexes of contamination and trophic status, including faecal sterols, biopolymers and trace metals, to determine and compare environmental quality of two tropical estuaries with contrasting conservation status. In the metropolitan estuary, eutrophic/hypereutrophic conditions and high concentrations (>1.0 µg g−1) of coprostanol were spatially correlated to sources of raw sewage input. Unexpected eutrophic sediments were also detected at the estuarine reserve, but with low sewage contamination indicating that high organic availability and burial predominated. The natural or polluted eutrophic sediments were determined by comparing multiple contamination indexes, which indicated sediment contamination within the metropolitan estuary. This study indicates that the long-term conservation of estuarine ecosystems on the Atlantic coast of Brazil are threatened by a typically poor sewage treatment and suggests that estuarine sediment quality need to be evaluated by multiple proxies before estuaries can be included in spatial conservation planning.

Polycyclic aromatic hydrocarbons (PAHs) were measured in 32 surface sediment samples collected around three cities (Barcarena, Belem, 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 Belem, 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.

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.

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.

In this study, we combine the use of Metal/Metal ratios of 134 sediment samples with multivariate analysis to provide the first geochemical mapping of a large subtropical estuary influenced by one of the largest grain-shipping terminals of South America. Together with grain-size data, the results allowed us to efficiently map the different sectors of the estuarine complex, defining its geochemical faciology. Also, potassium-related ratios appeared to be reliable proxies for the identification of point sources of terrigenous sediments. Since there was no evidence of widespread trace metal contamination, the results here presented can be used as a baseline for the area.

The Doce River mouth (DRM) was severely impacted by the rupture of the Fundao 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 Fundao 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 Fundao dam failure and contributed to the understanding of POPs cycles in the Southern Atlantic, data that are still scarce in the region.

The quality of water bodies has been regulated by national environmental agencies and based on faecal indicator bacteria, such as thermotolerant coliforms Escherichia coli and Enterococcus sp. Additionally, faecal sterols (mainly coprostanol) have been used to corroborate sewage discharge in marine environments. In this study, faecal material input was evaluated in two sampling campaigns in transects of two tidal creeks using bacterial and chemical indicators to both compare and establish the water quality in a South Atlantic subtropical estuary. The Itiberê tidal creek (S1) was classified as "contaminated" by faecal material, while the Peças tidal creek (S2) presented variable water quality according to the sampling period and sewage indicators considered in this evaluation. Then, the integrated application of chemical and bacterial indicators was applied for tidal creeks with different sewage contamination levels and under distinct environmental conditions and confirmed that Enterococcus sp. and coprostanol are the most suitable for estuarine environments.

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.

Total phosphorus (TP) records reflect variations in input and burial of organic matter (OM) in coastal and shelf sediments . At Antarctic regions , TP levels are often derived from natural sources; however, with emergent human pressure at these regions, anthropogenic sources of TP may play an important role. At the Antarctic Peninsula , Admiralty Bay attracts great scientific and touristic interest, especially during austral summer months, thus being vulnerable to human activities. Currently, only scarce spatial distributions of TP are available for this key region, whereas no vertical distributions have been determined. To fill this gap, we investigated short ( sediment cores in ten areas along Admiralty Bay for TP contents. We produced the first TP vertical distributions and established site-specific background values (from 492 ± 13 to 932 ± 17 μg g −1 ), which are related to hydrodynamics, sedimentology , and natural inputs of P. We observed a gradual surface TP enrichment at all sites, mainly due to input of fresh OM. Benefiting from our background values, we employ the Phosphorus Pollution Index (PPI) to assess possible human impacts . Generally, the increase of PPI suggests natural inputs of P. However, PPI ≥ 1.3 found at the nearby Comandante Ferraz Research Station (Brazil) can be linked to recent (past 2–3 decades) treated sewage inputs in Martel Inlet. We suggest PPI as a proxy for preliminary assessments of anthropogenic impacts in coastal Antarctic regions experiencing increased human pressure.

Intensive exploitation and transport of oil and derivatives are increasing the risk of coastal contamination by either dramatic disasters or diffuse sources. Tools for monitoring diffuse contamination, such as diesel oil that leaks from marine vessels are much needed. We experimentally tested the efficiency of antioxidant biomarkers as indicators of chronic exposure to diesel oil in a mudflat from the subtropical Bay of Paranagua, in southern Brazil. We examined the effects of three successive diesel oil spills, with two weeks of recovery time between exposures, on the edible clam Anomalocardia flexuosa . Previous studies have highlighted its potential as a bioindicator species for diesel oil contamination in subtropical and tropical ecosystems. Endpoints measured in gill and digestive gland homogenates included the activity of antioxidant enzymes SOD, GPx, GST and levels of lipid peroxides. PAHs concentration in sediments and soft tissue were also quantified. GST and SOD were the most responsive biomarkers to the exposure. There were significant but non–cumulative departures from control levels in organisms from treated samples, which were, in all cases, more common 48 h after each experimental spill. Biomarker responses were more evident in the digestive gland than in gills. This work validated the short–term responsiveness of biomarkers as measures of repeated pulsed in situ exposure to low concentrations of diesel oil. For their routine implementation into monitoring programs for tropical estuaries our general recommendations are 1) to include several reference sites, 2) to analyze biomarker data using a logarithmic–scale and 3) to interpret deviations from “normal” activity as multiplicative interval differences.

Isoprenoidal glycerol dialkyl glycerol tetraethers (isoGDGTs) are archaeal biomarkers. In many settings, the degree of cyclization of isoGDGTs is correlated with temperature, forming the basis of the TEX86 paleothermometer that is widely used to reconstruct sea surface temperature (SST) across a range of time scales. However, the application of TEX86 to the polar regions is relatively limited and there is currently no consensus on which calibration is best suited for polar environments. In addition, application of TEX86 to the polar regions is complicated by uncertainty regarding the source of organic matter input in coastal polar environments. We tested five different calibrations for TEX86 in marine sediments from the Antarctic coastal region of Admiralty Bay near King George Island, using four short cores that span the second half of the 20th century. We also explored the possible sources of organic matter in these cores using sterol biomarkers. Best results for TEX86 were obtained using a quadratic calibration. The TEX86 signal presented a strong seasonal signal and best matched reanalysis temperatures of the austral spring season (Oct-Nov-Dec). The most abundant compounds observed in the sediments were the sterols cholest-5-en-3β-ol and 24-ethylcholest-5-en-3β-ol, the fatty alcohols C16 and phytol, and isoGDGT-0, indicating a dominant marine origin of the organic matter. Differences in their vertical distributions suggests that some compounds (such as cholest-5-en-3β-ol and phytol) may have had different sources over the evaluated period. Together our results indicate that TEX86 can be used to reconstruct SSTs in the Antarctic coastal region.

Urban sewage is a source of major contamination in aquatic systems and contributes to environmental and human health disturbances. This study investigates the effects of sewage-polluted waters from Iguacu River on the health of juvenile Oreochromis niloticus. Two hundred four specimens were exposed to riverine water in four groups: no diluted, 25 and 50 % diluted water and a control group without tested water for 72 days. Biological samples were obtained for histopathological, neurotoxicity, antioxidant defenses, genotoxicity, metallothionines expression and polycyclic aromatic hydrocarbons (PAHs) metabolites. The results showed histopathological alterations in liver and gills, genotoxic alteration in erythrocytes, reduction of acetylcholinesterase activity in brain and muscle, activation of antioxidant defenses in the liver, recruitment of metals by metallothionein and the detection of PAHs metabolites in bile. These results demonstrate that juveniles of O. niloticus are susceptible to Iguacu River exposure water and they can be used as indicator of water quality.

Temporal patterns, fluxes and inventories of polychlorinated biphenyls (PCBs) were assessed in nine sediment cores collected from selected areas of Admiralty Bay off the Antarctic Peninsula. Concentrations of total PCBs were low, but slightly higher in comparison to low-impacted, remote environments in the world, ranging from below the detection limit to 11.9ngg-1 in dry weight. PCB concentrations and inventories suggest a possible minor influence related to the nearby logistic activities, especially in the sediment core collected close to the Ferraz Station. Despite being the most remote and protected area on the planet, the Antarctic continent is no longer a pristine environment.

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 Paranagua 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 ± 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.

Microplastics are important vectors for the transport and accumulation of persistent organic contaminants in coastal and marine environments. We determined the concentration of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) associated with microplastic pellets collected along a 39-km stretch of Brazil's South Atlantic coastline to understand the spatial dynamics and potential risk posed by these contaminants. Total PAH concentrations ranged from 1,454 to 6,002 ng g−1 and regularly exceeded the threshold effect level (TEL) for sediments defined by the United States Environmental Protection Agency. Sampling stations, spaced evenly along the coastline (i.e., 3-km intervals) exhibited a general north-to-south decline in the concentrations of some PAHs, but this spatial gradient was complicated by small-scale differences in the concentrations and composition of associated contaminants. Similarly, analysis of individual isomer ratios revealed further complexity driven by differences in the contribution of petrogenic versus pyrolytic inputs which pose different levels of risk to marine organisms. PCB concentrations ranged from 0.8 to 104.6 ng g−1 and were dominated by low chlorinated congeners likely to have originated from major industrial areas to the north. Overall, this study highlights the challenge of directly linking microplastic pollution with the potential toxicological effects of organic contaminants in coastal waters. We recommend that monitoring programs should explicitly consider both the origin (i.e., pellet sources and dispersal pathways) and nature of organic contamination (i.e., concentration and composition) when assessing the risks for biota and human health.

The wastewater contamination of urban rivers is a concern for biodiversity and a consequence from poor urban conservation policies. In the current study, the impact of urban and industrial activities was investigated in Iguacu river (Southern Brazil) using juvenile Oreochromis niloticus, after trophic and chronic exposure (25, 50 and 100 %), over 81 days. After exposure liver, gills, gonads, brain, muscle, and blood were sampled for chemical, biochemical, histopathological, genotoxic and molecular analyses. Water levels of persistent organic pollutants such as polychlorinated biphenyls, organochlorine pesticides, polycyclic aromatics hydrocarbon (PAHs) and metals were investigated. The redox unbalance, histopathological and increase in vitellogenin expression in fish revealed both the bioavailability of micropollutants and their harmful effects. According to the results, the level of Iguacu river pollution negatively impacts the health of O. niloticus revealing and highlighting the risk of this pollution exposure to biota and human populations.

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.

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) (DL - 234.3 ng g

Terpenoid hydrocarbons are ubiquitous in the marine environment and may be linked to natural synthetic activities after the original carbon skeleton of the biological precursor is retained. The terpenoid profile in pristine environments should have a biogenic signature. However, the widespread use of petroleum-derived products contributes to the inventory of hydrocarbons found in recent sediments, including the introduction of cyclic hydrocarbons with a thermogenic signature. Terpenoid hydrocarbons were examined from the mangrove sediments of the Paranagua Estuarine System (PES), which is a subtropical system in the South Atlantic. Intensive tourism has affected the PES, and it is at high risk of contamination due to extensive urban development and harbour activity. The biogenic compounds (BIO) in the PES were predominantly composed of unsaturated derivatives from higher plants (oleanoids, lupanoids, ursanoids and taraxeroids) with a des-A configuration and bacterial hopanoids. Thermogenic compounds (TRM) were distributed throughout the PES, and the sum of thermogenic and biogenic compounds exhibited a similar distribution, with significant correlations between these compounds. To better assess anthropogenic sources of hydrocarbons in mangrove, a ratio of TRM/BIO was proposed. Ratios higher than 1.0 were found near Paranagua port and in the Paranagua bay area. An important touristic destination, Mel Island, also exhibited ratios higher than 1.0 in two locations. The proposed terpenoids ratio accurately assessed the low-level chronic inputs of anthropogenic hydrocarbons in the study area. This innovative approach may be applied to areas with high biogenic inputs of organic matter, where chronic low-level hydrocarbon contributions are not evident using n-alkanes and polycyclic aromatic hydrocarbons.

Link to publishers version: 10.1007/s11356-016-7280-2 Recent offshore petroleum exploration has increased the risks of oil spills worldwide. We investigated biomarker responses to diesel oil exposure in two tropical and subtropical species, the clam Anomalocardia flexuosa and the polychaete Laeonereis culveri. Animals were exposed to oil-spiked sediment at two different concentrations (0.5 L and 1.0 L m−2). Activities of antioxidant enzymes catalase (CAT), superoxide dismutase (SOD), and glutathione peroxidase (GPx); glutathione transferase (GST); and lipid peroxides (LPO) were assessed in bivalve digestive glands and polychaete whole-body homogenates at 36 and 60 h of exposure. Significant variation in enzymatic antioxidant activity depended on the sampling time after exposure. No similar response patterns, either increases or decreases, were detected for the two target species, and biomarker responses were species-specific. L. culveri showed clearer patterns in its antioxidant response and should be prioritized over other species in biomonitoring studies involving oil exposure. Understanding the temporal variability of these biomarkers is a necessary action before implementing them as indicators measures in oil contamination biomonitoring programs. Our results provide a better understanding of biomarker responses in subtropical species, evidencing their potential use as sentinels of oil contamination.

Lipid biomarkers are potential tools for identifying the sources, diagenesis and reactivity of organic matter (OM) in marine systems, including in Antarctica where the particular environmental characteristics have motivated several studies of organic markers. Sedimentary sterol distributions were determined in two sediment cores (PGI-1 and PGI-2) collected from the marine environment around Penguin Island, Antarctica, during the 2007–08 summer. The cores were sectioned at 1 cm intervals and the sterols were analysed using gas chromatography with flame ionization detection. The results indicate that the sterols were subjected to decades of degradation and transformation with depth in both cores. However, an expected progressive conversion of stenols to stanols (evaluated by 5α-stanols/Δ5-stenols ratio) within the deepest sediment layers was not clear, suggesting low degradation rates. In PGI-1, the deposition of large quantities of penguin guano affected the distribution of sterols and, consequently, primary production was favoured by the ornithogenic soil input. The results contribute to the understanding of the current processes associated with primary sources and transformation of OM in this important region of the Antarctic environment.

Despite the increased and widespread usage of benthic indices for environmental health assessment, some methodological ambiguities remain to be solved. We tested the congruence and consistency of the benthic indices ITI, BO2A, BENTIX, AMBI and M-AMBI in a subtropical estuary (Paranagua Bay, Brazil). Indices were applied to non-vegetated tidal flats increasingly contaminated by sewage to test: (i) correlations with molecular biomarkers of sewage (consistency); and (ii) evaluate the overall agreement/similarity of responses (congruence). The responses of the benthic indexes ITI, AMBI and BO2A were congruent among themselves and consistent with molecular biomarkers values. BENTIX and M-AMBI were less consistent and congruent and possibly need a readjustment of boundaries for subtropical habitats. The indices seemed robust to natural background yearly variations not related to contamination. Faecal sterols associated to nutrient contents suitably supported the validation of indices and could integrate reference conditions for sewage impacted coastal habitats. Benthic indices can successfully integrate management guidelines, but their suitable application demands further research on tolerance shifts of key indicator species.

To better understand variation in sewage-impacted benthic macrofauna from subtropical tidal flats over time and space, we applied a five-factor linear model at a hierarchy of spatial (Condition - Contaminated or Non-Contaminated, Tidal Flat and Plot) and temporal scales (Season and Fortnight). The Contaminated site showed high levels of coprostanol and the presence of Paranais cf frici as markers or indicators of organic enrichment. Differences between Seasons were more pronounced for the faunal variation patterns than for the other parameters, with lower species richness and abundance in summer. There were significant interactions between Fortnight and Tidal Flat for most variables, reflecting marked heterogeneity within Tidal Flats. Benthic community has significantly changed over short periods of time. These rapid changes may lead to erroneous interpretations and mask the true sources of variation. Our results clearly demonstrate the need to better understand benthic temporal variability even at small scales.

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.

We have assessed variation in brittle star distribution patterns along a contamination gradient identified by fecal steroids and aliphatic hydrocarbons in Paranaguá Bay, southern Brazil. A hierarchical design using multiple spatial scales (centimeters-kilometers) was applied. Generalized linear mixed models (GLMMs) were used to investigate the spatial and temporal variability of brittle stars. Main principal components from the contamination and environmental matrices were used to investigate the best explanatory dataset. The abundance of brittle stars was significantly lower in sites with high concentrations of fecal steroids and aliphatic hydrocarbons. The best model fitting always included components from the contamination gradients, which precludes a purely environmental driving of brittle star abundance. Variability in spatial scales lower than kilometers was probably driven by sediment characteristics. We highlighted the importance of a robust multi-scale sampling design for a better biological indication of coastal contamination.

Made available in DSpace on 2020-12-12T01:58:55Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-03-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) The sediment quality of the Protected Cananéia-Iguape-Peruíbe Area (APA-CIP), listed as one of the Wetlands of International Importance (Ramsar Site), was assessed through geochemical and ecotoxicological analyses, in order to determine if organic and inorganic contaminants retained in the sediments were bioavailable to benthic organisms and could trigger negative effects. Lethal (Tiburonella viscana) and sublethal (Lytechinus variegatus and Nitokra sp.) ecotoxicological endpoints were assessed, as well as sediment texture and organic and inorganic contaminants in sediments obtained at six stations distributed along the APA-CIP. Sites under the influence of the maximum turbidity zone and close to the main local urban center (Cananéia city) presented the worst environmental conditions, indicated by sediment toxicities and high contaminants levels. These conditions may be associated to fine-grained sediments. Metal (Pb, Co, Ni and Zn) concentrations exceeded the regional Sediment Quality Guidelines (SQGs) at stations PT and PM, while Pb also exceeded the Canadian Interim Marine Sediment Quality Guidelines (ISQGs). Total Aliphatic Hydrocarbons (AH) were close to threshold sediment contamination values at PT (maximum turbidity zone). These findings indicate that metals from former mining activities reach APA-CIP, in addition to contaminants from local sources (urban centers, docks, fishing wharfs). Contaminants accumulate in low energy regions, where fine particle and organic matter contents are high. Toxicities appeared to be associated to contaminants, suggesting that the multiple local anthropogenic sources can produce ecological risks, indicating the need for multiple efforts to control external and internal contamination sources in this protected estuarine area. Instituto Oceanográfico USP, São Paulo NEPEA Campus do Litoral Paulista Universidade Estadual Paulista Júlio de Mesquita Filho (UNESP), São Vicente Laboratório de Espectrometria Atômica (Labspectro) Departamento de Química Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Rio de Janeiro Laboratório de Avaliação e Promoção da Saúde Ambiental Instituto Oswaldo Cruz, Fundação Oswaldo Cruz, Rio de Janeiro Centro de Estudos do Mar Universidade Federal do Paraná NEPEA Campus do Litoral Paulista Universidade Estadual Paulista Júlio de Mesquita Filho (UNESP), São Vicente FAPESP: #09/52762-6 CNPq: #303620/2008-0 CNPq: #308649/2011 CNPq: #311609/2014-7 CNPq: #479899/2013-4 CNPq: 306468/2017-4 CNPq: 311820/2017-4

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.

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.

Faecal sterols and stable isotopes (δ

Made available in DSpace on 2019-10-06T15:28:23Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-02-20 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) 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. Núcleo de Estudos em Poluição e Ecotoxicologia Aquática Universidade Estadual Paulista (UNESP), Pça. Infante D. Henrique s/n° Centro de Estudos do Mar Universidade Federal do Paraná, Av. Beira Mar, s/n° Núcleo de Estudos em Poluição e Ecotoxicologia Aquática Universidade Estadual Paulista (UNESP), Pça. Infante D. Henrique s/n° CNPq: # 311609/2014-7 FAPESP: #13/15482-0 CNPq: #31552 CNPq: #34449 CNPq: #39038 CNPq: #455280/2014-2

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.

The depositional history of polychlorinated biphenyls (PCBs) was studied from surficial sediments and three sediment cores sampled in the Santos Estuary, an important industrial and urban centre in South America. The maximum concentration (190.7 ng g−1 dry weight) and inventory (295.50 ng cm−2) were detected in sediments related to the 1980s, representing a ten-year delay of the emission peak in Brazil. PCB consumption, the congener patterns, and multivariate statistical analyses indicated that the levels started to increase with the intensification of regional urban and industrial development that continued to interfere in the magnitude of input during the past 50 years. In addition, the risk assessment indicates that levels observed in most of the samples are in a range capable of producing ecological risks to the marine biota. This study provides the first estimates of historic sediments PCB inventories in the Southwestern Atlantic, contributing data for regional and global management and highlighting the role of sediment as a compartment for permanently storing POPs and the risks involved in their resuspension, especially in regions that are constantly dredged such as the Santos Estuary.

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.

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 fromDL (detection limit) to 2.67 μg g

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. Saguacu Lagoon, the region near the ferry boat and the vicinity of Sao 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 Saguacu 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 Saguacu Lagoon should be considered to be priority areas when making environmental monitoring policies.

Persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) have previously been detected in the surface sediments, water, and endemic organisms of Lake Baikal, a UNESCO World Heritage Site. The Selenga River is the primary source of freshwater to Lake Baikal, and transports pollutants accumulating in the Selenga River basin to the lake. Sources of POPs and PAHs in the Selenga River basin grew through the 20th century. In the present study, temporal changes in the concentrations of PAHs and POPs were reconstructed from two lakes in the Selenga River basin over the past 150 years using paleolimnological techniques. Increased concentrations in PAHs and PCBs were recorded initially in the 1930s. The 1940s-1980s was the period of greatest exposure to organic contamination, and concentrations of dichlorodiphenyltrichloroethane (DDT), polychlorinated biphenyls (PCBs), hexachlorocyclohexanes (HCHs) and many PAHs peaked between the 1960s and 1980s in the two lakes. Declines in concentrations and fluxes were recorded for most PAHs and POPs in the 1980s and 1990s. Temporal trends in concentrations of total and individual compounds/congeners of PAH, PCBs, and polybrominated diphenyl ethers (PBDEs) indicate the contribution of both local and regional sources of contamination in the 20th and 21st centuries. Temporal variations in contaminants can be linked to economic and industrial growth in the former USSR after World War II and the economic decline of Russia in the late-1980s and early-1990s, as well as global trends in industrialization and development during the mid-20th century.