Chemical contamination affecting filter-feeding bivalves in no-take marine protected areas from Brazil.

Marine protected areas (MPAs) are zones geographically delimited under pre-defined management goals, seeking to reduce anthropogenic threats to biodiversity. Despite this, in recent years reports of MPAs affected by chemical contamination has grown. Therefore, this study addresses this critical issue assessing legacy and current chemical contamination in filter-feeder bivalves obtained in very restrictive no-take MPAs from Brazil. The detected pollutants encompass polycyclic aromatic hydrocarbons (PAHs), linear alkylbenzenes (LABs), and persistent organic pollutants (POPs) like dichlorodiphenyltrichloroethane (DDTs) and polychlorinated biphenyls (PCBs). Despite protective measures, bivalves from nine MPAs exhibited high LABs (13.2-1139.0 ng g-1) and DDTs levels (0.1-62.3 ng g-1). PAHs were present in low concentrations (3.1-29.03 ng g-1), as PCBs (0.7-6.4 ng g-1), hexachlorobenzene (0.1-0.2 ng g-1), and Mirex (0.1-0.3 ng g-1). Regardless of the sentinel species, MPAs and management categories, similar accumulation patterns were observed for LABs, DDTs, PAHs, and PCBs. Based on the limits proposed by Oslo Paris Commission, the measured levels of PAHs, PCBs and were below the environmental assessment criteria. Such findings indicate the no biological effects are expected to occur. However, they are higher considering background conditions typically measured in remote or pristine areas and potential simultaneous exposure. Such findings indicate an influence of anthropogenic sources, emphasizing the urgency for monitoring programs guiding strategic management efforts to safeguard these areas.

Cigarette butts in two urban areas from Brazil: Links among environmental impacts, demography and market.

Environmental impacts are currently linked to smoking cigarette behavior, as cigarette butts (CBs) represent the most common litter item in natural areas. Despite this, even the best ranked Brazilian cities, in terms of urban cleaning, have no information about urban littered CBs. Thus, CBs were monitored in Santos and Niterói cities, aiming to assess contamination, Cigarette Butt Pollution Index (CBPI) and the illegal market size. CBs were collected in 36 walkways considering different land usage types and urban density levels. The CBPI was calculated, and brands were used to identify the size of the illegal market. CBs contamination in Santos (0.25 CBs/m2) was three times higher than Niterói (0.08 CBs/m2) and their occurrence and distribution presented no relationship with land usage types and urban population densities levels. CBPI = 17.6 was severe and the highest so far reported. A total of 28 cigarette brands were found both studied cities. Further, illegal cigarette consumption in Santos and Niteroi was estimated, based on brands of collected CBs, at 25.2% and 36.8%, respectively. Such data may be valuable for implementation of logistic reverse actions seeking to environmentally sustainable and socially resilient cities. Cigarette consumption threatens human life and the environment, and tobacco companies should be accountable for the pollution they generate.

Contamination gradient affects differently carbonic anhydrase activity of mollusks depending on their feeding habits.

Aquatic organisms that inhabit coastal areas are often exposed to several contaminants. It is known that the bioaccumulation of contaminants can be amplified according to the species feeding habits and contaminant properties. As a consequence, species can experience different effects to contaminant exposure even if they inhabit the same area. The present study aimed to investigate the activities of carbonic anhydrase (CA), Ca2+-ATPase, and Mg2+-ATPase in different tissues (soft tissue, mantle, and gill) of three mollusk species (Lottia subrugosa, Stramonita brasiliensis, and Crassostrea brasiliana) with different feeding habits (herbivore, carnivore, and filter-feeder, respectively) which were sampled within a known contamination gradient at Santos Estuarine System (Southeastern Brazil). From the three enzymes tested, only CA was affected by the presence of contaminants within the contamination gradient evaluated. In general, the CA activity from the three species were lower in contaminated sites when compared to the reference site. The contrasting CA activity response observed in S. brasiliensis compared to L. subrugosa and C. brasiliana could be related to the tissue-specificity of this enzyme activity and species feeding habits (filter-feeders can accumulate more contaminants than herbivores and even carnivores). Results indicated that C. brasiliana mantle is the most suitable tissue for the use of CA analysis as a biomarker.

Key issues for bio-based, biodegradable and compostable plastics governance.

Among global efforts facing plastic pollution, their gradual replacement with alternative materials has gained strength during the last decade. We identified five stakeholders and their respective key participation in the chain of bio-based, biodegradable and compostable plastics (BBCP), which have contributed to several flaws on governance of these materials. The widespread unfamiliarity of the consumers about biodegradability concepts has been leading to misguided purchase decisions and disposal practices, along with possible littering behavior. Simultaneously, the adoption of greenwashing practices by stores and manufacturers contribute to disseminating misguided decisions on plastic consumption. Such issues are further aggravated by the lack of certification standards concerning the impact of littering, including the assessment of persistency and toxicity, also covering those made with biodegradable plastics.". Moreover, even though such alternative polymers were originally conceived as a strategy to minimize plastics pollution, the almost inexistence of specific regulatory frameworks in different political scales may convert them in a relevant part of the problem. Therefore, the governance systems and management strategies need to incorporate BBCP as potentially hazardous waste as they do for conventional plastics.

How protected are marine protected areas: A case study of tributyltin in Latin America.

Protected areas (PAs) are dedicated and managed to achieve long-term conservation of nature with associated ecosystem services and cultural values. However, few studies have assessed contamination/pollution, one of the top five biodiversity threats, within these areas. In fact, more than 100,000 molecules used in consumer goods are potentially affecting over 250,000 protected areas distributed worldwide. As a result, chemical appraisal within PAs require specific approaches to be feasible. Herein, an approach for assessment of contamination in marine protected areas (MPAs) spread over large continental and/or global areas was proposed and tested using, as a case study, the impact of tributyltin (TBT) within Latin America. This approach included area delimitation, bibliographic survey, construction of attribute tables, data insertion in a Geographic Information System, overlapping with worldwide shapefiles of PAs, identification of affected PAs and evaluation of impacts using the outcomes against specific environmental quality guidelines/directives. A total of 259 records of TBT occurrence and/or its biological effect within 53 marine protected areas (including biosphere reserves, Ramsar sites and National parks) were gathered. Among affected species, were recorded 18 gastropods exhibiting imposex. In addition, 6 bivalves, 1 crustacean, and 3 fish species presenting TBT residues in tissues were seen in MPAs from Brazil, Argentina, Ecuador, Peru, Chile and Venezuela. Since levels of TBT recorded in several studied MPAs were enough do induce deleterious biological responses over marine biota, it was clear that conservancy goals of some "protected" areas are under threat. Considering that only TBT exposure was appraised, and these areas are likely to be concomitantly exposed to other classes of contaminants, the actual scenario can be even more frightening. Although initially applied as a TBT case study, the present approach enables an overview for other chemicals within protected areas worldwide.

Imposex Incidence in Gastropod Species from Santa Marta Coastal Zone, Colombian Caribbean Sea.

Imposex is a phenomenon widely associated with environmental exposure to organotin compounds which were quite common components of antifouling paints applied on boats and ship hulls. Here we study the incidence of imposex in neogastropods and its relation with water quality and maritime traffic in the coastal strip of Santa Marta, Colombia. Imposex was determined via specialized indexes and related to the organisms' size, somatic conditions, variables of water quality and maritime traffic, in a space-time assessment. There was evidence of imposex in five species Plicopurpura patula, Vasula deltoidea, Stramonita haemastoma, S. floridana, and Gemophos auritulus. Purpura patula and Vasula deltoidea species were found in all sampling sites. The results have proved that imposex is highly influenced by the maritime traffic variable, with greater prevalence during the dry season, and with P. patula being more sensitive than V. deltoidea.

Prepubertal exposure to low doses of sodium arsenite impairs spermatogenesis and epididymal histophysiology in rats.

For the first time, juvenile toxicity of inorganic arsenic (As) was investigated in male rats, focusing on reproductive effects. As is a metalloid naturally occurring in the environment, being the inorganic forms the most toxics. Contaminated drinking water and agricultural products are the main prospectors of intoxication for general population. In the present study, Wistar male rats (21 days old) were distributed into three groups (n = 10/group): control (received vehicle-filtered drinking water), As1 (received AsNaO2 at 0.01 mg L-1 ) and As2 (received AsNaO2 at 10 mg L-1 ). The animals were euthanized on PND 53. Testicular damages increased in As1 and As2 compared to control (ie, presence of vacuolization, acidophilic cells, and epithelium degeneration). Testicular interstitium of As1 and As2 presented fluid's increase and intense inflammatory infiltration. In the epididymis there was reduction of sperm amount in the lumen, besides epithelium areas presenting cribriform aspect in As1 and As2, exfoliation of cells in the light (in As1) and vacuoles (in As2). In epididymis interstitium, inflammatory infiltrates were observed in initial segment of As1 and As2. AsNaO2 changed immunolabeling pattern for androgen receptor in epididymis of As2, although serum testosterone levels was statistically comparable to control. Mass spectrometry revealed higher As concentrations in testis and epididymis of As2 compared to As1 and Control. These results indicate compromise of spermatogenesis and epididymal histophysiology in AsNaO2 -treated animals, possibly impairing sperm quality and fertility in long-term, even at low levels of exposure. Investigations about the reversibility of reproductive damages are necessary to better understand the mechanisms of As reproductive toxicity.

Potential ecotoxicity of metals leached from antifouling paint particles under different salinities.

Antifouling paint particles (APPs) are residues generated during maintenance of vessels. In boat maintenance areas of South America, waste generation and disposal are not completely regulated. Therefore, APPs can enter into the aquatic environment and act as a source of contamination by metals and other biocides. Thus, the aim of the present study was to evaluate the potential ecotoxicity of the metal mixture present in APPs leached under different salinities. Therefore, the copepod Acartia tonsa was exposed to different concentrations of a leachate solution prepared by the addition of APPs (1.25g/L) in artificial saline water (salinities 5, 15 and 30). Thereafter, complexing agents (EDTA and sodium thiosulfate) were added to the experimental media in order to evaluate metal influence in APPs toxicity. APPs leachate solutions were very toxic to A. tonsa, reaching an estimated LC50 of 1% at salinities 5% and 15%, and 2% at salinity 30. The addition of the chelators in leachate solutions showed that metals are the major responsible compounds for the observed toxicity. Moreover, results from the calculated toxic units suggested a slightly synergic effect between Cu and Zn in the paint formulation. A metal speciation modelling showed that Zn was predominant as a free ion at all salinities, therefore, explaining the high leachate toxicity. Furthermore, the release of Zn was observed more at lower salinities, whereas Cu was observed at higher salinities. APPs are frequently released in estuarine systems, under conditions of salinity gradients. Therefore, navigated estuaries might be under the threat of this neglected residue.

Size, season and origin of gastropods matter in imposex assessments.

Through controlled exposure to tributyltin (TBT), the effects of season, size, and population origin were evaluated on imposex incidence in Stramonita brasiliensis. Four experiments were carried out with organisms collected from three different sites on the Brazilian coast (Torres - Rio Grande do Sul, Farol de Santa Marta - Santa Catarina, and Aracruz - Espírito Santo). S. brasiliensis were anesthetized, sexed, measured, classified by size in small (< 30 mm), medium (≥ 30 to ≤ 40 mm), or big (> 40 mm) and injected in the foot muscle with 0.5 µg g-1 of TBT. Organisms were maintained during one month in aquariums with clear marine water under controlled laboratory conditions. One month after injection, the imposex assessments showed that the population from the southeast (tropical) region was more sensitive to TBT than the population from the south of Brazil (the temperate region). A greater sensitivity in the small and medium categories was observed. Females were also more susceptible to TBT when exposed during their reproductive period. Thus, the present study highlighted the need to ensure that intrinsic biological factors related to organisms are considered in such biomonitoring studies to avoid misinterpretation of results.

Evaluation of the use of Olivella minuta (Gastropoda, Olividae) and Hastula cinerea (Gastropoda, Terebridae) as TBT sentinels for sandy coastal habitats.

Tributyltin (TBT) contamination is still recorded in the environment even after its ban in antifouling paints. Since most biomonitors of TBT contamination, through imposex evaluation, are hard-bottom gastropods, the identification of soft-bottom sentinels has become useful for regions where rocky shores and coral reefs are absent. Thus, an evaluation of Olivella minuta and Hastula cinerea as monitors of TBT contamination was performed in two sandy beaches located under influence area of São Sebastião harbor (São Paulo state, Brazil), where previous and simultaneous studies have reported environmental contamination by TBT. In addition, the imposex occurrence in H. cinerea was assessed in an area with low marine traffic (Una beach), also located in São Paulo State. A moderate imposex incidence in O. minuta was detected in Pernambuco (% I = 9.36, RPLI = 4.49 and RPLIstand = 4.27) and Barequeçaba (% I = 2.42, RPLI = 0.36 and RPLIstand = 0.81) beaches, indicating TBT contamination. In contrast, more severe levels of imposex were recorded for H. cinerea in Una beach (% I = 12.45) and mainly in Barequeçaba beach (% I = 98.92, RPLI = 26.65). Our results suggest that O. minuta and H. cinerea have good potential as biomonitors for TBT based on their wide geographical distribution, common occurrence in different coastal sediment habitats, easy collection, and association with TBT-contaminated sediments.

High levels of anthropogenic litter trapped in a mangrove area under the influence of different uses.

The contamination of mangroves by anthropogenic litter has increased in recent decades. Notably, Brazil occupies a prominent status within Latin America, boasting the second-largest mangrove areas globally. In Santos-São Vicente Estuarine System (SESS), mangroves coexist with a preeminent port complex and substantial urbanization rates. Nevertheless, the anthropogenic litter occurrence and distribution in this ecosystem remains unknown. This study aimed to comprehensively assess anthropogenic litter across 13 strategically positioned sites in the SESS. The total litter density (Mean ± SD) was 22.84 ± 36.47 (0.00-142.00) items·m-2, putting the SESS among the top four most contaminated mangrove ecosystems worldwide. Residential zones accumulated more litter than uninhabited areas and significant correlation was seen with human modification index. Plastic was the prevalent material (70.4 %), measuring mostly between 2.5 and 30 cm (41.1 %). It is imperative that local authorities adopt comprehensive strategies to mitigate contamination, while also curtailing the litter inputs to the SSES mangrove ecosystem.

Protective personal equipment on coastal environments: Identifying key drivers at a global scale.

The contamination of coastal ecosystems by personal protective equipment (PPE) emerged as a significant concern immediately following the declaration of the COVID-19 pandemic by the World Health Organization (WHO). Hence, numerous studies have assessed PPE occurrence on beaches worldwide. However, no predictors on PPE contamination was so far pointed out. The present study investigated social and landscape drivers affecting the PPE density in coastal environments worldwide using a meta-analysis approach. Spatial variables such as urban modification levels, coastal vegetation coverage, population density (HPD), distance from rivers (DNR), and poverty degree (GGRDI) were derived from global satellite data. These variables, along with the time elapsed after WHO declared the pandemic, were included in generalized additive models as potential predictors of PPE density. HPD consistently emerged as the most influential predictor of PPE density (p < 0.00001), exhibiting a positive effect. Despite the presence of complex non-linear relationships, our findings indicate higher PPE density in areas with intermediate GGRDI levels, indicative of emerging economies. Additionally, elevated PPE density was observed in areas located further away from rivers (p < 0.001), and after the initial months of the pandemic. Despite the uncertainties associated with the varied sampling methods employed by the studies comprising our database, this study offers a solid baseline for tackling the global problem of PPE contamination on beachesguiding monitoring assessments in future pandemics.

Microplastics in rocky shore mollusks of different feeding habits: An assessment of sentinel performance.

Microplastics (MPs) accumulation in rocky shore organisms has limited knowledge. This study investigated MPs accumulation in filter-feeding oysters, herbivorous limpets and carnivorous snails to assess their performance as sentinel species in the MPs trophic transfer. The samples were obtained along a contamination gradient in the Santos Estuarine System, Brazil. All three studied species showed MPs concentrations related to the contamination gradient, being the oysters the species that showed the highest levels, followed by limpets and snails (average of less and most contaminated sites of 1.06-8.90, 2.28-5.69 and 0.44-2.10 MP g-1, respectively), suggesting that MPs ingestion rates are linked to feeding habits. MPs were mainly polystyrene and polyacetal. The polymer types did not vary among sites nor species. Despite minor differences in percentages and diversity of size, shape, and color classes, the analyzed species were equally able to demonstrate dominance of small, fiber, transparent, black and blue MPs. Thus, oysters, limpets, and snails are proposed as sentinels of MPs in monitoring assessments.

Microplastic in clams: An extensive spatial assessment in south Brazil.

Microplastic pollution is becoming a continuously growing environmental concern, while bivalve mollusks are particularly vulnerable due to their sessile habits and feeding through water filtration processes. Microplastic incidence in soft tissues of the clam Amarilladesma mactroides was assessed along unconsolidated substrates distributed in extensive coastal regions of southern Brazil. Influence of urbanization levels, distance to rivers and local hydrodynamics on microplastic accumulation by the clam was tested. The average concentration of microplastics was high (3.09 ± 2.11 particles.g-1), considering 16 sampled sites. Particles were mainly composed by polyamide, polyethylene and polyethylene terephthalate, while were mainly smaller, fibrous and colorless. High urbanization and closer proximity to rivers insured higher contamination, which is a trend observed globally. No influence of coastal hydrodynamics was seen. Considering obtained findings, A. mactroides presents good potential to be used as a valuable tool to assess microplastic contamination in unconsolidated substrates of beach areas.

PAH residues and toxicity levels two years after an extensive oil spill on the northeast Brazilian coast.

The most extensive oil spill ever recorded in tropical oceans occurred between August 2019 and March 2020, affecting approximately 3000 km of the Brazilian coast. This study assessed the chemical contamination and toxicity of sediments collected from affected reef areas during two sampling surveys conducted 17 and 24 months after the peak of oil slick inputs. Our results indicated that neither PAH levels nor measured toxicity showed a significant contribution from the spilled oil, with concentrations and biological effects indistinguishable from those in unaffected areas. Similarly, no differences were observed between seasons. Furthermore, there was no discernible relationship between sediment toxicity results and the measured PAH concentrations. Therefore, while biological responses indicated toxicity in most assessed areas, these responses are likely related to other local sources. This evidence suggests a natural oil attenuation process contributing to local environmental recovery. Nonetheless, further investigation is needed for other areas affected by oil spills.

Antifouling booster biocides in Latin America and the Caribbean: A 20-year review.

This review summarized booster biocides studies from Latin America and the Caribbean during the last two decades. Studies were focused on six countries, with most of them in Brazil. In water and sediment, diuron and Irgarol were the most abundant and frequent biocides, probably due to their former intense use. Antifouling paint particles were also reported and had mainly DCOIT, which is currently the most used booster biocide. Toxicity of individual booster biocides was tested in laboratory, and most effects were related to chlorothalonil, DCOIT, dichlofluanid, and Irgarol, including, but not limited to DNA damage, fertility decrease, and mortality at different trophic levels. This review highlighted the need for further studies on environmental occurrence of booster biocides in Latin America and Caribbean associated to ecotoxicological studies. Such information is essential to determine the potential ecological risks and to create directives regarding safe limits of booster biocides in aquatic systems.

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.

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.

Toxicity of antifouling biocides on planktonic and benthic neotropical species.

Organotin-based (OTs: TBT and TPT) antifouling paints have been banned worldwide, but recent inputs have been detected in tropical coastal areas. However, there is a lack of studies evaluating the toxicity of both legacy and their substitute antifouling booster biocides (e.g., Irgarol and diuron) on neotropical species. Therefore, the acute toxicity of four antifouling biocides (TBT, TPT, Irgarol, and diuron) was investigated using the marine planktonic organisms Acartia tonsa and Mysidopsis juniae, the estuarine tanaid Monokalliapseudes schubarti (water exposure), and the burrowing amphipod Tiburonella viscana (spiked sediment exposure). Results confirmed the high toxicity of the OTs, especially to planktonic species, being about two orders of magnitude higher than Irgarol and diuron. Toxic effects of antifouling compounds were observed at levels currently found in tropical coastal zones, representing a threat to planktonic and benthic invertebrates. Furthermore, deterministic PNECmarine sediment values suggest that environmental hazards in tropical regions may be higher due to the higher sensitivity of tropical organisms. Since regulations on antifouling biocides are still restricted to a few countries, more ecotoxicological studies are needed to derivate environmental quality standards based on realistic scenarios. The present study brings essential contributions regarding the ecological risks of these substances in tropical and subtropical zones.

Multilevel assessment of chlorothalonil sediment toxicity to Latin American estuarine biota: Effects on biomarkers, reproduction and survival in different benthic organisms.

Chlorothalonil is an organochlorine compound that has long been used in agriculture. In recent years, this compound has been used as an antifouling booster biocide and its presence has been reported in marine coastal environments, especially in navigational areas. Although sediment can be a sink for chlorothalonil due to high affinity to fine particulate matter, toxicity studies with non-target marine and/or estuarine organisms is focused on waterborne exposure only. This study aimed to determine sediment-borne ecotoxicological effects of chlorothalonil on different benthic organisms of the Latin American biota using a integrative multilevel approach. Marine/estuarine organisms were exposed to sediments spiked with chlorothalonil (from 0 to 10.0 µg g-1) and effects at sub-individual (biochemical biomarkers in Anomalocardia flexuosa), individual (lethal effects to Tiburonella viscana and Artemia salina) and subpopulation levels (Nitokra sp. reproduction) were assessed. Increasing chlorothalonil concentrations in sediment caused increasing ecotoxicological effects in different levels of biological organisation, from biochemical to subpopulation levels. The highest exposure concentrations showed increased biomarkers of effects (lipid peroxidation and DNA damage in gills and/or digestive gland of A. flexuosa), lower fecundity and lower survival of the test organisms. GPx activity associated with LPO levels in the digestive gland suggested a response to the oxidant challenge provided by the biocide. At the lowest concentration (0.001 µg g-1), chlorothalonil detoxification mechanisms and defense against its oxidising action, involving GSH and glutathione-dependent enzymes (GST and GPx) were induced. At intermediate concentrations, there was a tendency of decreasing GSH levels, probably due to conjugation with chlorothalonil, which also affected the activities of the glutathione-dependent enzymes. At the highest tested concentration (10.0 µg g-1), chlorothalonil may have restimulated GSH synthesis in the gills of A. flexuosa, although the prooxidant activity has induced effects. This study contributes to assessing the environmental risk of chlorothalonil in sediment for non-target marine and estuarine organisms.