From the depths to the apex: Tracing the organophosphate ester journey through marine food webs.

This study explores the behavior of organophosphate esters (OPEs) in different species within marine ecosystems and their potential for bioaccumulation and biomagnification. The concentrations of OPEs were analyzed in marine species (krill (Meganyctiphanes norvegica), jellyfish (Pelagia noctiluca), European sardine (Sardina pilchardus), European anchovy (Engraulis encrasicolus), European hake (Merluccius merluccius), loggerhead turtle (Caretta caretta), European squid (Loligo vulgaris), fin whale (Balaenoptera physalus) and striped dolphin (Stenella coeruleoalba)) from different trophic levels, to understand their distribution and contamination profiles. The study provides insights into the metabolism of OPEs and their biomagnification on species occupying higher trophic levels. The results show that the differences in OPE concentrations among species are influenced by contamination levels at sampling points, as well as species and trophic level characteristics. The study reveals that the sum of OPEs do not exhibit significant biomagnification within the marine food web, with higher trophic level species showing efficient metabolism of these contaminants. However, biomagnification analysis of individual compounds demonstrates that some OPEs, such as tris(2-ethylhexyl) phosphate (TEP), tris(2-butoxyethyl) phosphate (TBOEP), and tris(2-isopropylphenyl) phosphate (T2IPPP) consistently exhibit biomagnification within marine trophic webs, while other show different behaviors depending on the trophic web. The loggerhead turtle shows higher biomagnification for specific OPEs, indicating the influence of diet and direct plastic waste consumption. Furthermore, OPEs prone to metabolism, such as tri-n-butyl phosphate (TNBP) and TBOEP, are present in multiple species across different trophic levels, suggesting a tendency for bioaccumulation. The study highlights the complexity of OPE behavior and the need to evaluate the biomagnification potential of each compound individually. It also emphasizes the toxic effects associated with OPE exposure and the potential risks to organisms within marine ecosystems.

Microplastic characterization in the stomachs of swordfish (Xiphias gladius) from the western Mediterranean Sea.

In this study, we aimed to quantify the presence of microplastics (MPs) in the stomachs of large pelagic fish (swordfish, Xiphias gladius, Linnaeus, 1758) sampled in the western Mediterranean Sea, and assess temporal trends (2011-2012 vs. 2017-2019) in MP ingestion. MPs were extracted from stomachs and characterized by µ-Fourier transform infrared spectroscopy. Results highlighted the ingestion of MP in 39 out of 49 stomachs analysed. Ingested MPs consisted mostly of small (<1 mm) fibers (88.6 %, mean ± standard deviation = 2.5 ± 6.1 particles per stomach), with a greater frequency of occurrence (FO) in the second period (FO = 90 %, 3.3 ± 8.0 particles per stomach). The predominant colours were purple, black and blue, and polyethylene terephthalate was the most frequently detected polymer. These results are crucial for the development of management actions aimed at the conservation of swordfish in the Mediterranean Sea and the prevention of health risks to humans.

Concentrations of bisphenols and phthalate esters in the muscle of Mediterranean striped dolphins (Stenella coeruleoalba).

Bisphenols (BPs) and phthalate esters (PAEs) are important compounds for the plastics industry, also called "everywhere chemicals" due to their ubiquity in daily use products. Both chemical groups are well-known environmental contaminants, whose presence has been reported in all environmental compartments, and whose effects, mainly associated to endocrine disruption, are detrimental to living organisms. Cetaceans, due to their long life-span, low reproduction rate and high position in the trophic web, are especially vulnerable to the effects of contaminants. However, little is known about BP and PAE concentrations in cetacean tissues, their potential relation to individual biological variables, or their trends over time. Here, the concentration of 10 BPs and 13 PAEs was assessed in the muscle of 30 striped dolphins (Stenella coeruleoalba) stranded along the Spanish Catalan coast (NW Mediterranean) between 1990 and 2018. Six BP and 6 PAE compounds were detected, of which only 4,4'-(cyclohexane-1,1-diyl)diphenol (BPZ) was detected in all the samples, at the highest concentration (mean 16.06 µg g-1 lipid weight). Sex or reproductive condition were largely uninfluential on concentrations: only dimethylphthalate (DMP) concentrations were significantly higher in immature individuals than in adults, and the overall PAE concentrations were significantly higher in males than in females. Temporal variations were only detected in bis(4-hydroxyphenyl)ethane (BPE), diethylphthalate (DEP) and dimethylphthalate (DMP), whose concentrations were lower, and 9,9-Bis(4-hydroxyphenyl)fluorene (BPFL), which were higher, respectively, in samples taken between 2014 and 2018, probably reflecting shifts in the production and use of these chemicals. These results provide the first assessment of concentrations of several BP and PAE compounds in the muscle of an odontocete cetacean.

Detection and quantification of microplastic pollution in the endangered Galapagos sea lion.

Marine debris pollution poses a significant global threat to biodiversity, with plastics being the primary debris type found in oceans due to their low-cost production and high demand worldwide. Microplastics (MPs, <5 mm in size) are highly bioavailable to a wide range of marine taxa, including marine mammals, through direct and indirect ingestion routes (i.e., trophic transfer). Recently, MP pollution has been detected on the Galapagos Marine Reserve, so in this study we developed a baseline framework for MP pollution in the Galapagos sea lion (GSL, Zalophus wollebaeki) through scat-based analysis. We collected 180 GSL scat samples from the southeast region following strict quality assurance/quality control protocols to detect, quantify and characterize physical-chemical properties of MPs through visual observations and µFT-IR spectroscopy. We recovered 81 MPs of varying sizes and colors in 37 % of samples (n = 66/180), consisting mostly of fibers (69 %, x¯ = 0.31 ± 0.57 particles scat-1). The number of particles per gram of sample wet weight ranged from 0.02 to 0.22 (x¯ = 0.04 ± 0.05 particles scat wet g-1). El Malecón and Punta Pitt rookeries at San Cristobal Island had the highest number of MPs (x¯ = 0.67 ± 0.51 and 0.43 ± 0.41 particles scat-1, respectively), and blue-colored particles were the most common in all samples. We identified eleven polymers in 46 particles, consisting mostly of polypropylene-polyethylene copolymer, polypropylene, cellulose, polyethylene, and polyvinyl chloride. The textile, fishing, and packaging industries are likely significant sources of microfibers into this insular ecosystem. Our results suggest that the GSL is exposed to MPs due to anthropogenic contamination that is subsequently transferred through trophic processes. These findings provide an important baseline framework and insights for future research on MP pollution in the region, as well as for management actions that will contribute to the long-term conservation of the GSL.

Biomagnification and temporal trends (1990-2021) of perfluoroalkyl substances in striped dolphins (Stenella coeruleoalba) from the NW Mediterranean sea.

Poly- and Perfluoroalkyl Substances (PFAS) are a well-known class of pollutants which can bioaccumulate and biomagnify with a vast majority being highly persistent. This study aims to determine the biomagnification rates of PFAS in sexually mature striped dolphins and to assess temporal trends on PFAS concentrations over the past three decades (1990-2021) in the North-Western Mediterranean Sea. Thirteen and 17 of the 19 targeted PFAS were detected in the samples of the dolphins' digestive content and liver, respectively, at concentrations ranging between 43 and 1609 ng/g wet weight, and 254 and 7010 ng/g wet weight, respectively. The most abundant compounds in both types of samples were linear perfluorooctanesulfonic acid (n-PFOS) and perfluorooctanesulfonamide (FOSA), which were present in all samples, followed by perfluoroundecanoic acid (PFUnDA), perfluorotridecanoic acid (PFTrDA) and perfluorononanoic acid (PFNA). Long-chain PFAS (i.e., PFCAs C ≥ 7 and PFSAs C ≥ 6) biomagnified to a greater extent than short-chain PFAS, suggesting a potential effect on the health of striped dolphins. Environmental Quality Standards concentrations set in 2014 by the European Union were exceeded in half of the samples of digestive content, suggesting that polluted prey may pose potential health risks for striped dolphins. Concentrations of most long-chain PFAS increased from 1990 to 2004-2009, then stabilized during 2014-2021, possibly following country regulations and industrial initiatives. The current study highlights the persistent presence of banned PFAS and may contribute to future ecological risk assessments and the design of management strategies to mitigate PFAS pollution in marine ecosystems.

Transplacental transfer of plasticizers and flame retardants in fin whales (Balaenoptera physalus) from the North Atlantic Ocean.

Marine mammals are one of the groups of animals most affected by marine pollution including that by organic compounds which, besides bearing recognised harmful effects to adults, they may also affect foetuses through placental transfer. In this study we analysed samples of fin whale (Balaenoptera physalus) females and their foetuses collected in the western Iceland summer feeding grounds in 2018. Three different families of organic pollutants: organophosphate esters (OPEs); halogenated flame retardants (HFRs); and short chain chlorinated paraffins (SCCPs), were analysed and their placental transfer investigated. HFRs were detected in 87.5% of females and 100% of foetus samples with concentrations that ranged between nd-15.4 and 6.37-101 ng/g lipid weight (lw), respectively. OPEs were detected in all samples, both from females (85.8-567 ng/g lw) and foetuses (nq-1130 ng/g lw). SCCPs were detected in 87.5% of female samples and 100% of foetal samples with concentrations that ranged between nd-30.9 and nq-574 ng/g lw, respectively. For OPE compounds, a significant negative correlation was observed between the logarithm maternal transfer ratio and their log Kow, indicating that a high lipophilicity reduced placental transfer rate. Interestingly, the decabromodiphenyl ethane (DBDPE) was the compound with the highest log Kow but also the one that was transferred the most from mothers to foetuses, calling for in-depth research on this pollutant. These results constitute the first evidence of mother-calf transfer of plasticizers and flame retardants in fin whales. Further investigations are needed to determine their potential effects on this species and other groups of animals.

Intrapopulation and temporal differences of phthalate concentrations in North Atlantic fin whales (Balaenoptera physalus).

The fin whale (Balaenoptera physalus) is a migratory filter-feeding species that is susceptible to ingest plastics while lunge feeding across the oceans. Plastic additives, such as phthalates, are compounds that are added to plastics to give them specific characteristics, such as flexibility. These so-called plasticizers are currently raising major concern because of their potential adverse effects on marine fauna. However, little is known about phthalate concentrations in tissues of baleen whales as well as their potential relation with biological variables (i.e., sex, body length and age) and their trends with time. In this study, we assessed the concentration of 13 phthalates in the muscle of 31 fin whales sampled in the feeding grounds off western Iceland between 1986 and 2015. We detected 5 of the 13 phthalates investigated, with di-n-butylphthalate (DBP), diethylphthalate (DEP) and bis(2-ethylhexyl) phthalate (DEHP) being the most abundant. None of the biological variables examined showed a statistically significant relationship with phthalate concentrations. Also, phthalate concentrations did not significantly vary over the 29-year period studied, a surprising result given the global scenario of increasing plastic pollution in the seas. The lack of time trends in phthalate concentration may be due in part to the fact that phthalates also originate from other sources. Although no adverse effects of phthalates on fin whales have been detected to date, further monitoring of these pollutants is required to identify potential toxic effects in the future.

Ingestion of synthetic particles by fin whales feeding off western Iceland in summer.

In this study we aim to assess the daily ingestion rates of synthetic particles by the fin whales (Balaenoptera physalus) that feed off the western coast of Iceland. To do so, we collected and analysed samples from the stomach content of 25 fin whales, consisting solely of northern krill (Meganyctiphanes norvegica). The particles found consisted of fibres and fragments, mainly blue, black and red, with an average size of 1.2 ± 1.3 mm. To confirm the synthetic nature of these particles, we used Micro-Fourier Transform Infrared Spectroscopy and comparison with a polymer library. The mean concentration of synthetic particles in the krill samples found in the stomachs of whales was 0.057 particles per gram, a value much lower than that previously reported for particle uptake by krill. From this concentration in krill, we estimated that the daily intake of synthetic particles for the North Atlantic fin whale would be ranging from 38,646 ± 43,392 to 77,292 ± 86,784 particles per day. Although at this level it is not possible to assess the impact of synthetic particles and their associated chemicals on the North Atlantic fin whale population, concentrations of these contaminants are likely to increase in the future, potentially causing adverse effects on whales and other marine mammals.

Long-term assessment of trace elements in franciscana dolphins from the Río de la Plata estuary and adjacent Atlantic waters.

The estuary of Río de la Plata, in the eastern coast of South America, is a highly anthropized area that brings a high load of contaminants to the surrounding waters, which may have detrimental effects on the local marine fauna. The franciscana dolphin (Pontoporia blainvillei) is a small cetacean species endemic of the southwestern Atlantic Ocean listed as Vulnerable in the IUCN red list. In this study, we assessed the concentrations of 13 trace elements in bone samples from 100 franciscana dolphins that were found stranded dead or incidentally bycaught in the Río de la Plata and adjacent coast between 1953 and 2015. Elements were, in decreasing order of mean concentrations: Zn > Sr > Fe > Al > Mn > Cu > Pb > Cr > Ni > As > Hg > Cd > Se. The concentrations of Al, Cr and Fe were slightly higher in females than in males. The concentrations of As, Ni, and Pb significantly decreased with body length. Throughout the study period, the concentrations of Al, Cr, Cu, Fe, Mn and Ni significantly increased, while the concentrations of As, Pb and Sr significantly decreased. The increasing trends may be due to increased inputs from river discharges, the leather industry and petroleum refineries, while the decrease in Pb may be due to the ban in the use of this element as an additive in gasoline and as component of car batteries. This investigation supports the validity of analysing trace element in bone, a tissue available in scientific collections and museums, to retrospectively examine variation over long temporal scales and thus assess long-term trends in pollution.

Automatic detection and quantification of floating marine macro-litter in aerial images: Introducing a novel deep learning approach connected to a web application in R.

The threats posed by floating marine macro-litter (FMML) of anthropogenic origin to the marine fauna, and marine ecosystems in general, are universally recognized. Dedicated monitoring programmes and mitigation measures are in place to address this issue worldwide, with the increasing support of new technologies and the automation of analytical processes. In the current study, we developed algorithms capable of detecting and quantifying FMML in aerial images, and a web-oriented application that allows users to identify FMML within images of the sea surface. The proposed algorithm is based on a deep learning approach that uses convolutional neural networks (CNNs) capable of learning from unstructured or unlabelled data. The CNN-based deep learning model was trained and tested using 3723 aerial images (50% containing FMML, 50% without FMML) taken by drones and aircraft over the waters of the NW Mediterranean Sea. The accuracies of image classification (performed using all the images for training and testing the model) and cross-validation (performed using 90% of images for training and 10% for testing) were 0.85 and 0.81, respectively. The Shiny package of R was then used to develop a user-friendly application to identify and quantify FMML within the aerial images. The implementation of this, and similar algorithms, allows streamlining substantially the detection and quantification of FMML, providing support to the monitoring and assessment of this environmental threat. However, the automated monitoring of FMML in the open sea still represents a technological challenge, and further research is needed to improve the accuracy of current algorithms.

Floating marine macro-litter in the North Western Mediterranean Sea: Results from a combined monitoring approach.

The aim of the present study was twofold: (i) to validate the drone methodology for floating marine macro-litter (FMML) monitoring, by comparing the results obtained through concurrent drone surveys and visual observations from vessels, and (ii) to assess FMML densities along the North Western Mediterranean Sea using the validated drone surveys. The comparison between monitoring techniques was performed based on 18 concurrent drone/vessel transects. Similar densities of FMML were detected through the two methods (16 items km-2 from the drone method vs 19 items km-2 from the vessel-based visual method). The assessment of FMML densities was done using 40 additional drone transects performed over the waters off the Catalan coast. The densities of FMML observed ranged 0-200 items km-2. These results provide a validation of the use of drones to monitor FMML and contribute to increasing the knowledge about the density of FMML in the North Western Mediterranean Sea.

No evidence of microplastics in Antarctic fur seal scats from a hotspot of human activity in Western Antarctica.

Microplastics are present in almost all seas and oceans, including the Southern Ocean. To the south of the Antarctic Polar Front, microplastics are present mainly west to the Antarctic Peninsula, but information is scarce about their impact on the pelagic food web. Here, we analysed 42 scats of male Antarctic fur seals (Arctocephalus gazella) collected in late summer at Deception Island (South Shetland Islands), which allowed us to assess the presence of microplastics in the pelagic food web of the Bransfield Strait (Western Antarctica). Furthermore, we analysed the hard remains of prey in the scats to characterize the diet of fur seals. Hard remains recovered from the scats revealed that male Antarctic fur seals foraged on krill and myctophid fishes during late summer. Fourier-transform infrared spectroscopy (FT-IR) revealed that none of the seven fragments and three fibres recovered from their scats were microplastics, but rather were silicate minerals and chitin. These results suggest that the levels of microplastic pollution in the pelagic food web of the Bransfield Strait are extremely low.

Assessment of organophosphate flame retardants in Mediterranean Boops boops and their relationship to anthropization levels and microplastic ingestion.

Plastic litter pollution is increasing in the seas and oceans worldwide, raising concern on the potential effects of plasticizer additives on marine fauna. In this study, muscle samples of 30 bogues (Boops boops; Linneaus, 1758) from the North Western Mediterranean Sea were analysed to assess the concentrations of 19 organophosphate flame retardant (OPFR) compounds and to inspect any relationship with microplastic ingestion and relative levels of anthropization. Out of the 19 OPFRs analysed, 6 compounds were detected, being tri-n-butyl phosphate (TNBP), 2-ethylhexyldiphenyl phosphate (EHDPP) and triphenylphosphine oxide (TPPO) the most abundant. As expected, OPFR concentrations were higher in samples collected off the most anthropized area of the city of Barcelona than in those from the Cap de Creus Marine Protected Area, while no significant correlation was detected between OPFR concentrations and microplastic ingestion. The results of this manuscript provide a first evidence of OPFR presence in the muscle of the bogue and identify the coastal area off Barcelona as a possible concentration area for contaminants, further supporting the use of the bogue as an indicator species of plastic pollution in the Mediterranean Sea.

Organophosphate contaminants in North Atlantic fin whales.

Pollution of the marine environment by litter composed of plastics is a growing concern. Chemical additives such as organophosphate flame retardants (OPFRs), which are added to plastics to improve their qualities, are in focus because they allegedly cause adverse effects on marine fauna. Here we analyse OPFR levels in the muscle of fin whales because, as a mysticete, this cetacean obtains its food by filter-feeding and is thus highly vulnerable to marine litter. Moreover, the fin whale performs long-range migrations from low-latitude areas in winter to high-latitude areas in summer, a trait that makes it a potentially good large-scale biomonitor of pollution. We also analyse OPFR levels in its main prey, the krill Meganyctiphanes norvegica, to assess transfer through diet. The samples analysed consisted of muscle tissue from 20 fin whales and whole-body homogenates of 10 krill samples, all collected off West Iceland. From the 19 OPFRs analysed, we detected 7 in the fin whale and 5 in the krill samples. Tri-n-butyl phosphate (TNBP), Isopropylated triphenyl phosphate (IPPP) and Triphenylphosphine oxide (TPPO) were the most abundant compounds found in both species. Mean ∑OPFR concentration, expressed on a lipid weight basis, was 985 (SD = 2239) ng g-1 in fin whale muscle, and 949 (SD = 1090) ng g-1 in krill homogenates. These results constitute the first evidence of the presence of OPFRs in the tissues of fin whales. Furthermore, they seem to support the non-significance of bioaccumulation of OPFRs through lifespan and of biomagnification trough the food web.

Who's better at spotting? A comparison between aerial photography and observer-based methods to monitor floating marine litter and marine mega-fauna.

Pollution by marine litter is raising major concerns due to its potential impact on marine biodiversity and, above all, on endangered mega-fauna species, such as cetaceans and sea turtles. The density and distribution of marine litter and mega-fauna have been traditionally monitored through observer-based methods, yet the advent of new technologies has introduced aerial photography as an alternative monitoring method. However, to integrate results produced by different monitoring techniques and consider the photographic method a viable alternative, this 'new' methodology must be validated. This study aims to compare observations obtained from the concurrent application of observer-based and photographic methods during aerial surveys. To do so, a Partenavia P-68 aircraft equipped with an RGB sensor was used to monitor the waters off the Spanish Mediterranean coast along 12 transects (941 km). Over 10000 images were collected and checked manually by a photo-interpreter to detect potential targets, which were classified as floating marine macro-litter, mega-fauna and seabirds. The two methods allowed the detection of items from the three categories and proved equally effective for the detection of cetaceans, sea turtles and large fish on the sea surface. However, the photographic method was more effective for floating litter detection and the observer-based method was more effective for seabird detection. These results provide the first validation of the use of aerial photography to monitor floating litter and mega-fauna over the marine surface.

Using Boops boops (osteichthyes) to assess microplastic ingestion in the Mediterranean Sea.

This study assesses microplastic ingestion in Boops boops at different geographical areas in the Mediterranean Sea. A total of 884 fish were caught at 20 coastal sites in Spain, France, Italy and Greece and analyzed using a common methodological protocol. Microplastics were found in 46.8% of the sampled fish, with an average number of items per individual of 1.17 ± 0.07. Filaments were the predominant shape type, while polyethylene and polypropylene were indicated by FTIR as the most common polymer types of ingested microplastics. The frequency of occurrence, as well as the abundance and proportion of types (size, shape, color and polymer) of ingested microplastics, varied among geographical areas. The spatial heterogeneity of the abundance of ingested microplastics was mainly related to the degree of coastal anthropogenic pressure at the sampling sites. Our findings further support the suitability of B. boops as bioindicator of microplastic pollution in the Mediterranean Sea.