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.

Oysters and mussels as equivalent sentinels of microplastics and natural particles in coastal environments.

Filter-feeder organisms such as oyster and mussels are exposed to particles like microplastics (MPs). Although widely used to monitor MPs contamination, little is known about their performance as sentinels, which are biological monitors accumulating contaminants without significant adverse effects. This study comparatively evaluated the quantitative and qualitative accumulation of MPs by oysters (Crassostrea brasiliana) and mussels (Perna perna) along a gradient of contamination in a highly urbanized estuarine system of Brazil. In the most contaminated site, both species presented the worst status of nutrition and health, and also one of the highest MPs levels reported for molluscs to date (up to 44.1 particles·g-1). Despite some inter-specific differences, oysters and mussels were suitable and showed an equivalent performance as sentinels, reflecting the gradient condition demonstrated for other contaminants in the region. The similarity in MPs accumulation was also observed for qualitative aspects (polymer composition, sizes, shapes and colors). Particles were mostly <1000 µm, fibrous, colorless and composed by cellulose and polymethyl methacrylate (PMMA). Thus, despite small variations, the usage of C. brasiliana and P. perna is recommended and provides reliable information for environmental levels of microplastics.

A global snapshot of microplastic contamination in sediments and biota of marine protected areas.

Microplastics (MPs) become ubiquitous contaminants in Marine Protected Areas (MPA) that have been planned as a conservation strategy. The present study provides a comprehensive overview of the occurrence, abundance, and distribution of MPs potentially affecting MPA worldwide. Data on MP occurrence and levels in sediment and biota samples were collected from recent peer-reviewed literature and screened using a GIS-based approach overlapping MP records with MPA boundaries. MPs were found in 186 MPAs, with levels ranging from 0 to 9187.5 items/kg in sediment and up to 17,461.9 items/kg in organisms. Peaked MPs concentrations occurred within multiple-use areas, and no-take MPAs were also affected. About half of MP levels found within MPA fell into the higher concentration quartiles, suggesting potential impacts on these areas. In general, benthic species were likely more affected than pelagic ones due to the higher concentrations of MP reported in the tissues of benthic species. Alarmingly, MPs were found in tissues of two threatened species on the IUCN Red List. The findings denote urgent concerns about the effectiveness of the global system of protected areas and their proposed conservation goals.

Microplastic contamination in seawater across global marine protected areas boundaries.

Despite the relatively rich literature on the omnipresence of microplastics in marine environments, the current status and ecological impacts of microplastics on global Marine Protected Areas (MPAs) are still unknown. Their ubiquitous occurrence, increasing volume, and ecotoxicological effects have made microplastic an emerging marine pollutant. Given the critical conservation roles of MPAs that aim to protect vulnerable marine species, biodiversity, and resources, it is essential to have a comprehensive overview of the occurrence, abundance, distribution, and characteristics of microplastics in MPAs including their buffer zones. Here, extensive data were collected and screened based on 1565 peer-reviewed literature from 2017 to 2020, and a GIS-based approach was applied to improve the outcomes by considering boundary limits. Microplastics in seawater samples were verified within the boundaries of 52 MPAs; after including the buffer zones, 1/3 more (68 MPAs) were identified as contaminated by microplastics. A large range of microplastic levels in MPAs was summarized based on water volume (0-809,000 items/m3) or surface water area (21.3-1,650,000,000 items/km2), which was likely due to discrepancy in sampling and analytical methods. Fragment was the most frequently observed shape and fiber was the most abundant shape. PE and PP were the most common and also most abundant polymer types. Overall, 2/3 of available data reported that seawater microplastic levels in MPAs were higher than 12,429 items/km2, indicating that global MPAs alone cannot protect against microplastic pollution. The current limitations and future directions were also discussed toward the post-2020 Global Biodiversity Framework goals.

Using large amounts of firefighting foams releases per- and polyfluoroalkyl substances (PFAS) into estuarine environments: A baseline study in Latin America.

We analyzed per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs) used to extinguish a major fire in a petrochemical terminal from the Port of Santos (Brazil). Eight AFFFs from seven known commercial brands and one unknown sample (AFFF-1 to AFFF-8) were evaluated. 17 PFAS were identified and quantified using high performance liquid chromatography (LC/MS). The concentrations of Σ17 PFAS in the AFFFs ranged from 500 to 9000 ng/g, with prevalence of short chain PFAS (~85 %), followed by long chain PFAS. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), included in the global treaty of the Stockholm Convention, were also detected. We estimated that at least 635.96 g of PFAS were introduced in the estuary, representing a massive input of these substances. This investigation reports the PFAS composition of AFFFs used in firefighting in the GRULAC Region (Group of Latin American and Caribbean countries).

Levels of hydrocarbons and toxicity of water-soluble fractions of maritime fuels on neotropical invertebrates.

Accidents involving fuels and oil spills are among the main sources of hydrocarbons to the marine ecosystems and often damage the biota. Diesel and bunker oil are two examples of fuels with broad application that release hydrocarbons to the aquatic environment and little is known about their toxicity on tropical organisms. This study aimed to assess the toxicity of the water-soluble fraction (WSF) of diesel and bunker oils to neotropical marine invertebrates. Commercial fuels were purchased for WSF extraction, analyzed for total petroleum hydrocarbons (TPH), and polycyclic aromatic hydrocarbons (PAHs), and acute and chronic toxicity determined. The WSF analyzed contained varied levels of TPH and PAHs mixtures, especially low molecular weight PAHs; bunker WSF presented higher amounts of TPH and PAHs. Both WSFs tested produced significant mortality of the brine shrimp Artemia salina, affected the reproduction rate of the copepod Nitokra sp, and impaired the embryo-larval development of the mussel Perna perna and of the sea urchin Lytechinus variegatus. In general WSF from diesel was more toxic to the organisms tested, but bunker WSF was more toxic to embryos of L. variegatus. Toxicity started from concentrations of 3% WSF, which can be environmentally relevant after an oil spill, indicating that marine biota may be adversely affected in short term.

Sediment contamination and toxicity of Marine Protected Areas in southeastern Brazilian coast: A baseline for management planning.

Recent studies have shown that the effectiveness of establishing Marine Protected Areas (MPAs) is threatened by toxic effects of contaminants. São Paulo is the most economically developed state of Brazil, and its coast is protected by a system of MPAs, including the North Shore Marine Protected Area (NSMPA). The present study provides a first assessment of sediment quality in NSMPA and two reference sites. Concentrations of arsenic (As), metals (Al, Fe, Cd, Cr, Cu, Ni, Pb, and Zn) and polycyclic aromatic hydrocarbons (PAHs) and its sources were determined. Comparisons with sediment quality guidelines indicated low contamination, as confirmed by the Geoaccumulation Index, which classified the results as background levels. Whole-sediment exposures of the amphipod Tiburonella viscana were performed to estimate possible acute effects, but samples exhibited no toxicity. The results presented in this study represent a baseline for further monitoring programs of MPAs, supporting conservation actions of management plans.

Marine litter on a highly urbanized beach at Southeast Brazil: A contribution to the development of litter monitoring programs.

Seasonal distribution of Marine Litter (ML) on Santos beaches was assessed using a citizen science strategy. Plastics and cigarette butts (CB) were the dominant items in all sampling campaigns. Seasonal distribution did not result in significant differences for most items. Plastic and CB amounts were high in summer compared to autumn. For all sampled sites the presence of beach users influenced ML densities. However, results showed that some sites presented an additional influence of local hydrodynamic. Moderate amounts of hazardous items including metal, glass, CB, sanitary waste and plastic tubes used to pack and market illicit drugs represented between 20.8 and 31% of all ML over the seasons. The beaches of Santos were classified as dirty in autumn and spring and as extremely dirty in winter and summer. These findings can serve as a baseline to support mitigating actions by public authorities and start monitoring programs of ML not only in Santos but also in other urbanized beaches.

Dredging impacts on the toxicity and development of sediment quality values in a semi-arid region (Ceará state, NE Brazil).

Sediment dredging impacts coastal environments by promoting the resuspension of fine particles and remobilization of contaminants that may trigger toxic effects. In this study, we evaluated the sediment quality in harbor areas of Mucuripe bay, a semi-arid ecosystem located in Ceará state (Brazil), which is subject to dredging activities. A sampling survey was conducted right after dredging operations and data compared to another survey performed prior dredging. Sediments were analyzed for fine particles, organic carbon, nutrients, metals, hydrocarbons, and tributyltin (TBT). Toxicity of whole-sediment and liquid phase exposures were also determined. The concentrations of Cd, Cr, Cu, and Zn decreased after dredging, which was confirmed by the geoaccumulation index. Levels of TBT dropped while phosphorus, aliphatic and polycyclic aromatic hydrocarbons increased. Toxic effects persisted, indicating a post-dredging recontamination combined with other sources such as urban runoff, wastewater discharges, harbor activities, and antifouling particles. Data from Mucuripe and Pecém harbors were compiled and site-specific sediment quality values (SQVs) were developed by using multivariate methods. The threshold values proposed by our study were lower and more effective to predict toxicity compared to international guidelines, indicating levels of contamination for this tropical region in which toxic effects may occur. Considering the large geographic area with different sediment characteristics of the Brazilian coast, this study represents a significant contribution to sediment toxicity assessment of dredging activities in semi-arid environments.

Data on hydrocarbons in sediment samples, and its body burden levels in tissues of Anomalocardia flexuosa from toxicity testing.

The analysis of hydrocarbons in terms of individual compounds is relevant to understand the origin and source of these substances, as well as its distribution in environmental compartments, including sediments and biota. Hydrocarbons concentrations were determined in sediments and in whole-body soft tissues of the tropical clam Anomalocardia flexuosa in sediment toxicity testing using samples of Mucuripe bay (Ceará State, NE Brazil) collected in 2011 during dredging events [1]. Data of target compounds included aliphatic (AHs) and aromatic hydrocarbons (PAHs), and linear alkylbenzenes (LABs). AHs compounds were determined on gas chromatography with flame ionization detector (GC-FID), while PAHs and LABs were determined on gas chromatography coupled to a mass spectrometer (GC/MS) in a selected ion mode (SIM). The potential of this dataset is baseline information on hydrocarbons contamination in sediments from a semi-arid region and the bioaccumulation of organic contaminants in marine organisms that can be used as models in ecotoxicological studies.

Biomarkers responses of the clam Anomalocardia flexuosa in sediment toxicity bioassays using dredged materials from a semi-arid coastal system.

Few test organisms are employed for sediment toxicity assessments in Tropical regions, including Brazil. We assessed the ability of the clam Anomalocardia flexuosa to respond to contamination in sediment bioassays using dredging materials of a semi-arid region (Ceará State, NE Brazil), with attention to sublethal responses. Sediments were collected during and after dredging (survey 1 and 2, respectively) and animals exposed in laboratory over 28 days, with responses measured at 7 days. Bioaccumulation of contaminants was determined in whole-body soft tissues as a metric of bioavailability, and biomarkers' changes were monitored in terms of enzymes of phase I and II metabolism, acetylcholinesterase (AChE), and antioxidant responses, lipid peroxidation (LPO) and DNA damage (strand breaks). Clams accumulated aliphatic (AHs) and aromatic hydrocarbons (PAHs), and linear alkylbenzenes (LABs) compared to control conditions (day 0), with increased amounts of As, Cd, Cu, and Zn observed in some samples. The enzyme glutathione S-transferase was enhanced in animals exposed to samples, indicating activation of phase II metabolism. Changes observed in glutathione peroxidase (GPx), glutathione reductase (GR), LPO and strand breaks were related to oxidative stress. AChE enzymatic activity also changed, as an indicator of neurotoxicity caused by sediment exposure. The computed integrated biomarker response index (IBR) ranked sites according to the contamination status and proximity to its sources. Correlations found for biomarkers and bioaccumulation of hydrocarbons indicated the influence of harbor activities, effluent discharges, and urban runoff on the sediment pollution of Mucuripe Bay. Data also showed that SQGs are unable to predict bioaccumulation and subchronic effects. Based on our results we consider that biomarkers responses in A. flexuosa are important endpoints to be applied in sediment toxicity bioassays in tropical regions.

Integrating multiple lines of evidence of sediment quality in a tropical bay (Guanabara Bay, Brazil).

The present study evaluated the ecological risk of metal contamination in sediments of Guanabara Bay (GB) by combining multiple lines of evidence (LOEs). Chemical analysis and a set of whole-sediment toxicity assays were conducted with Tiburonella viscana, Kalliapseudes schubartii, Anomalocardia flexuosa, and Nitocra sp. Results were integrated by multivariate analysis and qualitative methods. Additionally, a whole-sediment Toxicity Identification Evaluation technique (TIE) was applied to identify the chemical groups responsible for the effects. Sediments from harbor and industrial areas exhibited toxicity linked to moderate to high concentrations of Zn, Pb, Cu and Cr. The TIE technique confirmed such effects, but it also indicates the contribution of ammonia and organic compounds to the observed toxicity. Our results demonstrate that the combination of multiple LOEs improves the effectiveness of environmental risk assessment of chemical stressors and management of coastal ecosystems in tropical regions.

Sub-lethal Responses of the Polychaete Armandia agilis in Whole-sediment Toxicity Testing.

The present study assessed biochemical responses as sublethal endpoints in the polychaete Armandia agilis exposed to contaminated sediments to in order to assess its potential use as a test organism. Sediment samples from several locations at a dredging site were obtained and used in whole-sediment exposures. Samples were tested with A. agilis to determine the 10-day toxicity of the 100% sample and the enzymatic activity of catalase (CAT), glutathione-S-transferase (GST) and acetylcholinesterase (AChE) biochemical measurements made in whole-body homogenates of a subset of the surviving organisms. Biochemical responses reported in A. agilis were not statistically different from the reference site sediment, however, the integrated analysis demonstrated that contaminants bound to sediment samples influenced the sublethal effects.

Influence of anthropogenic activities and risk assessment on protected mangrove forest using traditional and emerging molecular markers (Ceará coast, northeastern Brazil).

Anthropogenic molecular markers were used to assess chemicals inputs and ecological risks associated from multiple sources to sediments in one of the largest tropical mangrove forests of South America, with a particular focus on lesser studied compounds resulting from rural activities. Total concentrations ranged from 23.4 to 228.2 ng g-1 for polycyclic aromatic hydrocarbons (∑PAHs), 750.4 to 5912.5 ng g-1 for aliphatic hydrocarbons (∑AHs), 32.4 to 696.6 ng g-1 for pesticides (∑pesticides), 23.1 to 2109.7 ng g-1 for coprostanol and sterols (∑sterols), 139.3 to 580.2 ng g-1 for naturals hormones (∑natural hormones) and 334.1 to 823.4 ng g-1 for synthetics hormones (∑synthetic hormones). The PAHs and AHs used as traditional anthropogenic markers showed a mixture between natural and anthropogenic sources, related mainly to inputs from higher plants, phytoplankton and both, biomass and petroleum combustion. Rural activities linked to agricultural pest control are the predominant source of pesticides, although minor inputs from pesticides used in urban public health campaigns and household activities were also detected. Synthetic hormones levels are two to three orders of magnitude greater than natural hormones levels and no correlations were observed between the main sewage markers and synthetic hormone concentrations, rural activities such as animal husbandry, which use drugs in management, may be the predominant anthropogenic sources of these compounds in the region. Traditional markers failed to detect ecological risks in rural areas, where synthetic substances (e.g. pesticides and hormones) are widely used and introduced in the environment.

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.

Changes in thyroid status of Menidia beryllina exposed to the antifouling booster irgarol: Impacts of temperature and salinity.

The triazine-based herbicide irgarol is widely used in antifouling systems as an algicide and has been detected recently in multiple coastal environments. Studies evaluating sub-lethal responses of fish following exposure to irgarol are limited. Moreover, impacts of climate change on fish endocrinology may also contribute to the sublethal toxicity of irgarol. We assessed the effects of irgarol on thyroid endpoints in juveniles of Menidia beryllina under two different treatments of salinity (10 and 20 ‰) and two temperatures (10 and 20°C). Condition factor coefficients (K) of animals were significantly affected by 0.1 to 10 µg/L of irgarol at the higher temperature. Levels of T3 were changed in whole body homogenates from both temperatures at 10‰ following exposure to 1 to 10 µg/L. T4 levels were altered only at 10°C when animals were treated with 1 to 10 µg/L (10 ‰), and in 0.1 and 10 µg/L (20 ‰). Increased transcripts of deiodinase enzymes at 10 °C may be impacted by salinity and alter thyroid hormone homeostasis. Impact on gene expression of thyroid (α and ß) and growth hormone receptors were also determined. Our results highlight the relevance of environmental variable that may impact the ecological risk of irgarol in estuarine systems.

Impacts of Salinity and Temperature on the Thyroidogenic Effects of the Biocide Diuron in Menidia beryllina.

Diuron is a herbicide used in agricultural and urban settings and also as an antifouling agent. Recent studies have indicated sublethal responses of diuron in the endocrine system of fish and amphibians. Given the potential of climate change to also alter fish endocrinology, the combination of environmental stressors with diuron may contribute to its sublethal toxicity. In this study, the effects of temperature and salinity on thyroid targets of diuron were assessed in juveniles of the estuarine fish Menidia beryllina under different conditions of salinity (10 and 20‰) and temperature (10 and 20 °C). Environmentally relevant concentrations of diuron affected the growth, and the higher temperature reduced the condition factor of animals. Increased levels of T3 were observed in fish from all treatments, and at 10 °C, T4 levels were augmented at 10‰ but reduced at 20‰. Increased gene expression of deiodinases at 20‰ in both temperatures suggests the influence of salinity on the regulation of hormone imbalance via deiodination pathway activation. Decreased transcripts of thyroid and growth hormone receptors were also observed following diuron treatment. These results indicate that changes in environmental stressors may have significant impacts on the ecological risk of diuron in estuarine fish.

Effects of novobiocin and methotrexate on the benthic amphipod Ampelisca brevicornis exposed to spiked sediments.

The marine amphipod Ampelisca brevicornis was used as model organism of benthic macrofauna to assess the possible adverse effects of pharmaceuticals bound to sediments. Organisms were exposed to sediment spiked with novobiocin (NOV) and methotrexate (MTX) for 10 days in order to estimate the acute toxicity (lethal effects) produced by the two compounds. The surviving organisms were pooled and analyzed to determine their sublethal responses associated with different phases of metabolism (enzyme activities in phases I and II), oxidative stress (antioxidant enzyme activities and lipid peroxidation), and genotoxicity (DNA damage in the form of strand breaks). No lethal or sublethal effects were observed in the amphipods exposed to NOV. For organisms exposed to sediments spiked with MTX the results were found to calculate the concentration that was lethal to 50% of the organisms exposed in the toxicity tests (LC50 of 30.36 ng/g). MTX also induced the metabolism of enzyme detoxification activities in phases I and II. Oxidative stress and DNA damage in particular were also observed, indicating responses associated with MTX's mechanism of action. Both mortality and the set of applied biomarkers allowed for the assessment of bioavailability, oxidative stress, and genotoxicity of NOV and MTX. The information obtained in this investigation can assist in ecological risk assessment of marine sediments contaminated by pharmaceuticals.

Sediment quality assessment in a tropical estuary: the case of Ceará River, Northeastern Brazil.

The present study aimed to assess the sediment quality in a tropical estuary located in the northeast of Brazil under semi-arid conditions and multiple sources of contamination, using both toxicity bioassays and metal distribution. The metal distribution followed a concentration gradient decreasing one order of magnitude from the inner station toward the outer estuary, with amounts in the following order: Fe > Al > Zn > Cr > Pb > Cu. The index of geoaccumulation indicated a metal enrichment in the Ceará river sediment, mainly at inner sites, considered from moderately to strongly contaminated by Al, Cu, Cr and Zn. Sediment samples were considered toxic by means of whole sediment tests with copepods (reproduction) and amphipods (survival), and also elutriate fraction and sediment-water interface with sea urchin embryos (development). Acute and chronic toxicity did not exhibit a significant correlation with metals, emphasizing the influence of other contaminants mainly related to the pollution sources installed in the mid-estuary.