Research priorities on microplastics in marine and coastal environments: An Australian perspective to advance global action.

Plastic and microplastic contamination in the environment receive global attention, with calls for the synthesis of scientific evidence to inform actionable strategies and policy-relevant practices. We provide a systematic literature review on microplastic research across Australian coastal environments in water, sediment and biota, highlighting the main research foci and gaps in information. At the same time, we conducted surveys and workshops to gather expert opinions from multiple stakeholders (including researchers, industry, and government) to identify critical research directions to meet stakeholder needs across sectors. Through this consultation and engagement process, we created a platform for knowledge exchange and identified three major priorities to support evidence-based policy, regulation, and management. These include a need for (i) method harmonisation in microplastic assessments, (ii) information on the presence, sources, and pathways of plastic pollution, and (iii) advancing our understanding of the risk of harm to individuals and ecosystems.

Strong philopatry in an estuarine-dependent fish.

Understanding fish movement is critical in determining the spatial scales in which to appropriately manage wild populations. Genetic markers provide a natural tagging approach to assess the degree of gene flow and population connectivity across a species distribution. We investigated the genetic structure of black bream Acanthopagrus butcheri across its entire distribution range in Australia, as well as regional scale gene flow across south-eastern Australia by undertaking a comprehensive analysis of the populations in estuaries across the region. We applied genome-wide sampling of single-nucleotide polymorphism (SNP) markers generated from restriction site-associated DNA sequencing. Genetic structure and potential gene flow was assessed using principal component analyses and admixture analyses (STRUCTURE). Using 33,493 SNPs, we detected broad scale genetic structuring, with limited gene flow among regional clusters (i.e. Western Australia, South Australia and western Victoria; and eastern Victoria, Tasmania and New South Wales). This is likely the result of unsuitable habitats, strong ocean currents (e.g. the Leeuwin Current and the East Australian Current), large water bodies (e.g. Bass Strait) and known biogeographical provinces across the continent. Local-scale genetic structuring was also identified across the south-eastern Australian estuaries sampled, reflecting that the coexistence of both migratory and resident individuals within populations (i.e. partial migration), and the movement of fish into coastal waters, still results in strong philopatry across the region. Instances of movement among estuaries at this spatial scale were primarily found between adjacent estuaries and were likely attributed to lone migrants utilising inshore coastal currents for movement beyond nearby habitats. Targeting SNP markers in A. butcheri at this continental scale highlighted how neither spatial proximity of estuaries nor black bream's ability to move into coastal waters reflects increased gene flow. Overall, our findings highlight the importance of location-specific management.

Coastal upwelling influences population structure of dusky grouper Epinephelus marginatus: An integrative approach based on otolith chemistry and muscle stable isotopes.

The dusky grouper (Epinephelus marginatus) is an overfished and threatened fish species with coastal distribution. In the Southwestern Atlantic, it occurs across a broad region influenced by two major oceanographic features: the Cabo Frio (23°S) and the Cabo Santa Marta (28°S) upwelling systems. Along the Brazilian coast, the species may present continuous or discrete populations, depending on the methodological approach used. In this study we combined otolith chemistry and muscle stable isotope analyses to examine the population structure of dusky groupers and its association with the two upwelling systems. Fish were collected in shallow coastal waters of the Southwest Atlantic Ocean, covering the southeastern and southern Brazilian coasts, among Macaé (22°S), Santos (24°S), Florianópolis (27°S), and in Rio Grande (32°S). The results show three statistically well-separated population groups along the region. We named these population groups as North (north of Cabo Frio); Center (between upwelling regions); and South (south of the Cabo Santa Marta system). Our findings allow to suggest that the upwelling systems may influence the distribution of E. marginatus stocks along the Brazilian south-western coast, even though a causal effect may not be attributed at this point. Overall, this combined approach, leveraging information from distinct natural tags, and reflecting variability of water chemistry and food webs with latitude, allowed us to enhance our understanding on how major upwelling systems influence the structuring of fish populations along the southwestern Atlantic Ocean.

Complex interactions of ENSO and local conditions buffer the poleward shift of migratory fish in a subtropical seascape.

Ocean warming is associated with the tropicalization of fish towards higher latitudes. However, the influence of global climatic phenomena like the El Niño Southern Oscillation (ENSO) and its warm (El Niño) and cold (La Niña) phases on tropicalization has been overlooked. Understanding the combined effects of global climatic forces together with local variability on the distribution and abundance of tropical fish is essential for building more accurate predictive models of species on the move. This is particularly important in regions where ENSO-related impacts are known to be major drivers of ecosystem change, and is compounded by predictions that El Niño is becoming more frequent and intense under current ocean warming. In this study, we used long-term time series of monthly standardized sampling (August 1996 to February 2020) to investigate how ocean warming, ENSO and local environmental variability influence the abundance of an estuarine dependent tropical fish species (white mullet Mugil curema) at subtropical latitudes in the southwestern Atlantic Ocean. Our work revealed a significant increasing trend in surface water temperature in shallow waters (<1.5 m) at estuarine and marine sites. However, against our initial expectation, we did not observe an increasing trend in the abundance of this tropical mullet species. Generalized Additive Models revealed complex, non-linear relationships between species abundance and environmental factors operating at large (ENSO's warm and cold phases), regional (freshwater discharge in the coastal lagoon's drainage basin) and local (temperature and salinity) scales across the estuarine marine gradient. These results demonstrate that fish responses to global climate change can be complex and multifaceted. More specifically, our findings suggested that the interaction among global and local driving forces dampen the expected effect of tropicalization for this mullet species in a subtropical seascape.

Elemental and spectral chemometric analyses of Octopus vulgaris beaks as reliable markers of capture location.

The high demand and economic relevance of cephalopods make them prone to food fraud, including related to harvest location. Therefore, there is a growing need to develop tools to unequivocally confirm their capture location. Cephalopod beaks are nonedible, making this material ideal for traceability studies as it can also be removed without a loss of commodity economic value. Within this context, common octopus (Octopus vulgaris) specimens were captured in five fishing areas along the Portuguese coast. Untargeted multi-elemental total X-ray fluorescence analysis of the octopus beaks revealed a high abundance of Ca, Cl, K, Na, S, and P, concomitant with the keratin and calcium phosphate nature of the material. We tested a suite of discrimination models on both elemental and spectral data, where the elements contributing most to discriminate capture location were typically associated with diet (As), human-related pressures (Zn, Se, and Mn), or geological features (P, S, Mn, and Zn). Among the six different chemometrics approaches used to classify individuals to their capture location according to their beaks' element concentration, classification trees attained a classification accuracy of 76.7%, whilst reducing the number of explanatory variables for sample classification and highlighting variable importance for group discrimination. However, using X-ray spectral features of the octopus beaks further improved classification accuracy, with the highest classification of 87.3% found with partial least-squares discriminant analysis. Ultimately, element and spectral analyses of nonedible structures such as octopus beaks can provide an important, complementary, and easily accessible means to support seafood provenance and traceability, whilst integrating anthropogenic and/or geological gradients.

Innovation to limit seafood fraud post-COVID-19.

Seafood is an important source of protein and micronutrients, but fishery stocks are increasingly under pressure from both legitimate and illegitimate fishing practices. Sustainable management of our oceans is a global responsibility, aligning with United Nations Sustainable Development Goal 14, Life Below Water. In a post-COVID-19 world, there is an opportunity to build back better, where locally sourced food via transparent supply chains are ever-more important. This article summarises emerging research of two innovative case studies in detecting and validating seafood provenance; and using alternative supply chains to minimise the opportunity for seafood fraud in a post-COVID-19 world.

Neuroactive pharmaceuticals in estuaries: Occurrence and tissue-specific bioaccumulation in multiple fish species.

Contamination of surface waters by pharmaceuticals is an emerging problem globally. This is because the increased access and use of pharmaceuticals by a growing world population lead to environmental contamination, threatening non-target species in their natural environment. Of particular concern are neuroactive pharmaceuticals, which are known to bioaccumulate in fish and impact a variety of individual processes such as fish reproduction or behaviour, which can have ecological impacts and compromise fish populations. In this work, we investigate the occurrence and bioaccumulation of 33 neuroactive pharmaceuticals in brain, muscle and liver tissues of multiple fish species collected in four different estuaries (Douro, Tejo, Sado and Mira). In total, 28 neuroactive pharmaceuticals were detected in water and 13 in fish tissues, with individual pharmaceuticals reaching maximum concentrations of 1590 ng/L and 207 ng/g ww, respectively. The neuroactive pharmaceuticals with the highest levels and highest frequency of detection in the water samples were psychostimulants, antidepressants, opioids and anxiolytics, whereas in fish tissues, antiepileptics, psychostimulants, anxiolytics and antidepressants showed highest concentrations. Bioaccumulation was ubiquitous, occurring in all seven estuarine and marine fish species. Notably, neuroactive compounds were detected in every water and fish brain samples, and in 95% of fish liver and muscle tissues. Despite variations in pharmaceutical occurrence among estuaries, bioaccumulation patterns were consistent among estuarine systems, with generally higher bioaccumulation in fish brain followed by liver and muscle. Moreover, no link between bioaccumulation and compounds' lipophilicity, species habitat use patterns or trophic levels was observed. Overall, this work highlights the occurrence of a highly diverse suite of neuroactive pharmaceuticals and their pervasiveness in waters and fish from estuarine systems with contrasting hydromorphology and urban development and emphasizes the urgent need for toxicity assessment of these compounds in natural ecosystems, linked to internalized body concentration in non-target species.

Ecotoxicological Effects of the Anionic Surfactant Sodium Dodecyl Sulfate (SDS) in Two Marine Primary Producers: Phaeodactylum tricornutum and Ulva lactuca.

Sodium Dodecyl Sulfate (SDS) is an anionic surfactant, extensively used in detergents, household and personal care products, as well as in industrial processes. The present study aimed to disclose the potential toxicological effects of SDS exposure under environmentally relevant concentrations (0, 0.1, 1, 3, and 10 mg L-1) on the physiology and biochemistry (photosynthesis, pigment, and lipid composition, antioxidative systems, and energy balance) of two marine autotrophs: the diatom Phaeodactylum tricornutum and the macroalgae Ulva lactuca. A growth rate (GR) reduction in P. tricornutum was observed with a classic dose-response effect towards the highest applied concentration, while a GR increase occurred in U. lactuca. Regarding photochemistry, the decrease in the fluorescence of the OJIP curves and laser-induced fluorescence allowed a better separation between SDS treatments in U. lactuca compared with P. tricornutum. Although all pigments significantly decreased in U. lactuca at the highest concentrations (except for antheraxanthin), no significant variations occurred in P. tricornutum. On the other hand, changes in fatty acid content were observed in P. tricornutum but not in U. lactuca. In terms of classical biomarker assessment, a dose-effect relationship of individual biomarkers versus SDS dose applied; U. lactuca displayed a higher number of biomarker candidates, including those in distinct metabolic pathways, increasing its usefulness for ecotoxicological applications. By evaluating the potential application of optical and biochemical traits, it was evident that the fatty acid profiles of the different exposure groups are excellent candidates in P. tricornutum, concomitant with the characteristics of this anionic surfactant. On the other hand, the results presented by laser-induced fluorescence and some parameters of PAM fluorometry in U. lactuca may be an advantage in the field, offering non-invasive, fast, easy-to-use, high-throughput screening techniques as excellent tools for ecotoxicology assessment.

Elemental Fingerprinting of Wild and Farmed Fish Muscle to Authenticate and Validate Production Method.

In the context of expanding fish production and complex distribution chains, traceability, provenance and food safety tools are becoming increasingly important. Here, we compare the elemental fingerprints of gilthead seabream (Sparus aurata) muscle from wild and different aquaculture productions (semi-intensive earth ponds and intensive sea cages from two locations) to confirm their origin and evaluate the concentrations of elements with regulatory thresholds (Cu, Hg, Pb and Zn). Using a chemometric approach based on multi-elemental signatures, the sample origin was determined with an overall accuracy of 90%. Furthermore, in a model built to replicate a real-case scenario where it would be necessary to trace the production method of S. aurata without reliable information about its harvesting location, 27 of the 30 samples were correctly allocated to their original production method (sea-cage aquaculture), despite being from another location. The concentrations of the regulated elements ranged as follows: Cu (0.140-1.139 mg/Kg), Hg (0-0.506 mg/Kg), Pb (0-2.703 mg/Kg) and Zn (6.502-18.807 mg/Kg), with only Pb presenting concentrations consistently above the recommended limit for human consumption. The present findings contribute to establishing elemental fingerprinting as a reliable tool to trace fish production methods and underpin seafood authentication.

Harnessing the Full Power of Chemometric-Based Analysis of Total Reflection X-ray Fluorescence Spectral Data to Boost the Identification of Seafood Provenance and Fishing Areas.

Provenance and traceability are crucial aspects of seafood safety, supporting managers and regulators, and allowing consumers to have clear information about the origin of the seafood products they consume. In the present study, we developed an innovative spectral approach based on total reflection X-ray fluorescence (TXRF) spectroscopy to identify the provenance of seafood and present a case study for five economically relevant marine species harvested in different areas of the Atlantic Portuguese coast: three bony fish-Merluccius merluccius, Scomber colias, and Sparus aurata; one elasmobranch-Raja clavata; one cephalopod-Octopus vulgaris. Applying a first-order Savitzky-Golay transformation to the TXRF spectra reduced the potential matrix physical effects on the light scattering of the X-ray beam while maintaining the spectral differences inherent to the chemical composition of the samples. Furthermore, a variable importance in projection partial least-squares discriminant analysis (VIP-PLS-DA), with k - 1 components (where k is the number of geographical origins of each seafood species), produced robust high-quality models of classification of samples according to their geographical origin, with several clusters well-evidenced in the dispersion plots of all species. Four of the five species displayed models with an overall classification above 80.0%, whereas the lowest classification accuracy for S. aurata was 74.2%. Notably, about 10% of the spectral features that significantly contribute to class differentiation are shared among all species. The results obtained suggest that TXRF spectra can be used for traceability purposes in seafood species (from bony and cartilaginous fishes to cephalopods) and that the presented chemometric approach has an added value for coupling with classic TXRF spectral peak deconvolution and elemental quantification, allowing characterization of the geographical origin of samples, providing a highly accurate and informative dataset in terms of food safety.

Effects of Glyphosate-Based Herbicide on Primary Production and Physiological Fitness of the Macroalgae Ulva lactuca.

The use of glyphosate-based herbicides (GBHs) worldwide has increased exponentially over the last two decades increasing the environmental risk to marine and coastal habitats. The present study investigated the effects of GBHs at environmentally relevant concentrations (0, 10, 50, 100, 250, and 500 µg·L-1) on the physiology and biochemistry (photosynthesis, pigment, and lipid composition, antioxidative systems and energy balance) of Ulva lactuca, a cosmopolitan marine macroalgae species. Although GBHs cause deleterious effects such as the inhibition of photosynthetic activity, particularly at 250 µg·L-1, due to the impairment of the electron transport in the chloroplasts, these changes are almost completely reverted at the highest concentration (500 µg·L-1). This could be related to the induction of tolerance mechanisms at a certain threshold or tipping point. While no changes occurred in the energy balance, an increase in the pigment antheraxanthin is observed jointly with an increase in ascorbate peroxidase activity. These mechanisms might have contributed to protecting thylakoids against excess radiation and the increase in reactive oxygen species, associated with stress conditions, as no increase in lipid peroxidation products was observed. Furthermore, changes in the fatty acids profile, usually attributed to the induction of plant stress response mechanisms, demonstrated the high resilience of this macroalgae. Notably, the application of bio-optical tools in ecotoxicology, such as pulse amplitude modulated (PAM) fluorometry and laser-induced fluorescence (LIF), allowed separation of the control samples and those treated by GBHs in different concentrations with a high degree of accuracy, with PAM more accurate in identifying the different treatments.

Microplastic in oysters: A review of global trends and comparison to southern Australia.

Microplastics have been documented in a plethora of marine environments and organisms. These small plastics threaten ecosystem health, with implications for seafood species' health. Oysters are an important cultural and economic aquaculture species globally. Due to their filter feeding mechanisms, they can act as an indicator species and proxy for environmental contamination. This makes them an ideal organism for investigating microplastic pollution. Here, we first systematically reviewed the global literature investigating microplastic in oysters. Globally, 94.4% of all oysters had microplastics, with an average of 1.41 ± 0.33 per gram of soft tissue wet weight (gww). The review showed that wild-caught oysters contained more than double the amount of microplastic than aquaculture raised specimens, likely reflecting the clean and productive waters in which oyster aquaculture systems are commonly located. Second, we quantified microplastic presence and polymer type in commercially farmed oysters (Crassostrea gigas and Saccostrea glomerata) across a broad spatial scale, covering eight sites in southern Australia. Microplastics were present in 49.4% of all sampled oysters, with specimens from all locations containing microplastics. On average, whole oysters contained 0.83 ± 0.08 microplastics per individual or 0.09 ± 0.01 microplastics gww. Using Fourier-Transform Infrared Spectroscopy, we identified that 62% of the verified microplastics were vexar plastic netting, a low-density polyethylene commonly used in aquaculture production. Understanding the abundance and source of microplastic in these key seafood species is essential to determine if oysters are vulnerable to these contaminants and pose a risk to the oyster aquaculture industry as an important food resource.

Effect Biomarkers of the Widespread Antimicrobial Triclosan in a Marine Model Diatom.

The present-day COVID-19 pandemic has led to the increasing daily use of antimicrobials worldwide. Triclosan is a manmade disinfectant chemical used in several consumer healthcare products, and thus frequently detected in surface waters. In the present work, we aimed to evaluate the effect of triclosan on diatom cell photophysiology, fatty acid profiles, and oxidative stress biomarkers, using the diatom Phaeodactylum tricornutum as a model organism. Several photochemical effects were observed, such as the lower ability of the photosystems to efficiently trap light energy. A severe depletion of fucoxanthin under triclosan application was also evident, pointing to potential use of carotenoid as reactive oxygen species scavengers. It was also observed an evident favouring of the peroxidase activity to detriment of the SOD activity, indicating that superoxide anion is not efficiently metabolized. High triclosan exposure induced high cellular energy allocation, directly linked with an increase in the energy assigned to vital functions, enabling cells to maintain the growth rates upon triclosan exposure. Oxidative stress traits were found to be the most efficient biomarkers as promising tools for triclosan ecotoxicological assessments. Overall, the increasing use of triclosan will lead to significant effects on the diatom photochemical and oxidative stress levels, compromising key roles of diatoms in the marine system.

Microplastics in decapod crustaceans sourced from Australian seafood markets.

Microplastic abundance and characteristics were assessed in five decapod crustaceans purchased from seafood markets and collected in coastal waters around Australia (South Australia, New South Wales, Queensland, Northern Territory, and Western Australia). Three species of prawns (king, banana and tiger prawns) and two species of crabs (blue-swimmer and mud crabs) were analysed. Muscle tissues and gastro-intestinal tracts in prawns, and gastro-intestinal tracts in crabs, were chemically digested, with microplastic identification verified using Fourier Transform Infrared spectroscopy. Forty-eight percent of crustaceans contained microplastics. Prawns and crabs had 0.8 ± 0.1 and 1.6 ± 0.1 pieces per individual, respectively, with spatial patterns evident. Microplastics were predominantly fibres (98%) of blue (58%) and black (24%) colours with polyolefin including polyester the most prevalent polymers. Overall, compared to a systematic review we performed of microplastics in decapod crustaceans worldwide, microplastic loads in crustaceans from Australia were in the lower range of plastic contamination.

Climate-Friendly Seafood: The Potential for Emissions Reduction and Carbon Capture in Marine Aquaculture.

Aquaculture is a critical food source for the world's growing population, producing 52% of the aquatic animal products consumed. Marine aquaculture (mariculture) generates 37.5% of this production and 97% of the world's seaweed harvest. Mariculture products may offer a climate-friendly, high-protein food source, because they often have lower greenhouse gas (GHG) emission footprints than do the equivalent products farmed on land. However, sustainable intensification of low-emissions mariculture is key to maintaining a low GHG footprint as production scales up to meet future demand. We examine the major GHG sources and carbon sinks associated with fed finfish, macroalgae and bivalve mariculture, and the factors influencing variability across sectors. We highlight knowledge gaps and provide recommendations for GHG emissions reductions and carbon storage, including accounting for interactions between mariculture operations and surrounding marine ecosystems. By linking the provision of maricultured products to GHG abatement opportunities, we can advance climate-friendly practices that generate sustainable environmental, social, and economic outcomes.

Low abundance of microplastics in commercially caught fish across southern Australia.

Plastic pollution has increased significantly in the past decades and is now a major global environmental issue. Plastic objects enter the ocean and are broken down into smaller pieces, while wastewater and runoff also carry microplastics (plastics <5 mm) into the ocean. Plastic has been found in over 700 different species of marine wildlife but little research has examined fish sold for human consumption. We determined the microplastic abundance in nine commercially important, wild-caught fish species purchased from seafood markets across 4000 km of Australia (Western Australia, South Australia, Victoria, Tasmania, New South Wales). For microplastic quantification, fish gastro-intestinal tracts were chemically digested and the amount and type of microplastic identified under a microscope and Fourier transform infrared spectrometer. Across all states, an average of 35.5% of fish samples had at least one piece of microplastic in their gastro-intestinal tract. South Australia had the highest percentage of fish with plastic (49%) and Tasmania the lowest (20%). The average microplastic load was 0.94 piece per fish but ranged from 0 to 17 pieces, with polyolefin identified as the dominant polymer group. Overall, the ingestion of microplastic was widespread across species, locations, diets and habitat niches of fish species investigated, but the average plastic ingestion was less than other similar global studies. This study provides novel insights on the use of fish species from seafood markets to assess environmental contamination by microplastic, as well as an important perspective of the potential for microplastic contamination to enter the human food chain.

Environmental risk assessment and bioaccumulation of pharmaceuticals in a large urbanized estuary.

We screened for the presence of 66 different pharmaceutical residues in surface waters and in multiple invertebrate and fish species of the Tejo estuary to produce an environmental risk assessment of individual pharmaceuticals and their mixtures, as well as evaluate the bioaccumulation of pharmaceuticals in one of Europe's largest estuarine systems. Sixteen pharmaceutical residues, from seven therapeutic classes, were detected in estuarine waters, with environmental mixture concentrations ranging from 42 to 1762 ng/L. Environmental risk assessment via the determination of risk quotients, demonstrated high ecological risk for the antibiotic amoxicillin and angiotensin II receptor blockers irbesartan and losartan. Moderate risk was estimated for antidepressants, antiepileptics, anxiolytics and beta-blockers, but the risk quotient of the accumulated mixture of compounds was over 380-fold higher than the no risk threshold, driven by antibiotics and angiotensin II receptor blockers. In biota, higher risk therapeutic groups were found in higher concentrations, with nine pharmaceutical residues detected, including six antibiotics and two neuroactive compounds, and maximum tissue concentrations up to 250 µg/kg. Bioaccumulation was species- and compound-specific, with only two compounds found simultaneously in water and biota, likely a result of the complex dynamics and fate of pharmaceuticals in estuarine waters. Nonetheless, higher detection frequencies were observed in species living directly on or just above the substrate (i.e. benthic and demersal species), underpinning the importance of habitat use, as well the potential role of sediment and diet based routes for pharmaceutical uptake. Ultimately, results support urgent action on managing the impact of pharmaceuticals in coastal environments, striving for improved monitoring schemes tailored to the dynamic nature and ecological diversity of estuaries and coastal ecosystems.

Fatty acid profiles of estuarine macroalgae are biomarkers of anthropogenic pressures: Development and application of a multivariate pressure index.

Transitional ecosystems are among the most degraded ecosystems worldwide, with several groups of organisms investigated for their reliability as biological indicators of human-driven disturbances. Recently non-traditional biochemical biomarkers such as an individual's fatty acids profile have been identified as promising tools for assessing contaminant exposure. In this work, two abundant Atlantic benthic macroalgae (Ulva lactuca and Fucus vesiculosus species) were surveyed in three mudflat areas of the highly urbanized Tejo estuary, with increasing anthropogenic disturbance degrees (Alcochete, Rosário and Seixal mudflats, increasing in contamination by this order) and their fatty acids evaluated as potential biomarkers for exposure to contaminants known to have toxic effects on biota. In terms of contamination the metal pollution index of all the compartments analysed (sediment bioavailable and total metal concentrations and thallus metal concentrations) revealed the same tendencies with lower contamination levels in Alcochete, intermediate in Rosário and high contamination levels in Seixal. In the thallus of U. lactuca thallus could be observed a strong decrease in C18-fatty acids along the contamination gradient, likely due to lipid peroxidation from metal-generated reactive oxygen species. Nevertheless, an increase in stearic and hexadecatrienoic acids in the thallus from the most contaminated site suggested counteractive mechanisms maintain the production of C18-fatty acid pool. A similar response was found in F. vesiculosus but with palmitic acid acting as precursor for the synthesis of stearic acid, allowing the maintenance of oleic and linoleic acids levels in the membranes to counteract oxidative stress. Beyond the physiological interest of these mechanisms, fatty acid profiles were used to develop a novel multivariate pressure index (Multi-PI), that beyond the contaminant concentration would reflect the response of these biomonitor species towards anthropogenic disturbance, through the evaluation of fatty acid profiles, which are also key molecules from a trophic perspective within the estuarine system. The Multi-PI efficiency in responding to different environmental contamination degrees, was substantiated by strong and positive correlations with thallus and sediment contamination. This indicated that fatty acid profiles reflect thallus and benthic habitat contamination and are efficient biomarkers of environmental metal contamination. Therefore, the sessile and abundant nature of benthic macroalgae allied to their fatty acid responses can be leveraged as suitable biomarkers for contaminant monitoring in future impact assessment and ecotoxicology studies.

Study on the efficiency of a covalent organic framework as adsorbent for the screening of pharmaceuticals in estuary waters.

Herein, we demonstrate, for the first time, that covalent organic frameworks (COFs) can be efficient adsorbents for the screening of pharmaceuticals in real water samples, obtaining highly representative data on their occurrence and avoiding the cost of carrying high volume samples and tedious and costly clean-up and preconcentration steps. Of the 23 pharmaceuticals found present in the water samples from the Tagus river estuary using state-of-the-art solid-phase extraction (SPE), 22 were also detected (adsorbed and recovered for analysis) using a COF as the adsorbent material with adsorption efficiency of over 80% for nearly all compounds. In specific cases, acidification of the water samples was identified to lead to a dramatic loss of adsorption efficiency, underlining the effect of sample pre-treatment on the results. The COF efficiently adsorbed (>80%) 19 pharmaceuticals without acid treatment of the sample, highlighting the potential of this class of materials for representative in situ passive adsorption of pharmaceuticals, making this material suitable for being used in water monitoring programs as a simple and cost-efficient sample preparation procedure. In the case of α-hydroxyalprazolam and diclofenac, the COF outperformed the SPE procedure in the recovery efficiency. Although further efforts should be made in tailoring the desorption of the pharmaceuticals from the COF by using different solvents or solvent mixtures, we propose COFs as convenient adsorbent for broad-scope screening and as an efficient adsorbent material to target specific classes of pharmaceuticals. To the best of our knowledge, this is the first study on the use of COFs for contaminant screening in real, naturally contaminated water samples.