Search

Disposable facemasks represent a new form of environmental contamination worldwide. This study aimed at addressing the abundance of facemasks in an overlooked natural environment with high ecological and economic value - the wetlands (Ria de Aveiro, Portugal, as study case), evaluating their potential biodegradation using naturally occurring fungi and assessing the potential ecotoxicity of released microfibres on local bivalves. All masks collected within 6500 m 2 area of Aveiro wetland were 100 % disposable ones (PP-based, confirmed by Fourier transform infrared spectroscopy - FTIR) with an initial abundance of 0.0023 items/m 2 in Sept. 2021, which was reduced by ∼40 % in Apr. 2022 and ∼87 % in Sept. 2022, as a reflection of the government policies. Analysis of the carbonyl index (0.03 to 1.79) underlined their state of degradation, primarily due to sun exposure during low tides. In laboratory conditions, 1 mm 2 microplastics obtained from new disposable facemasks were prone to biodegradation by Penicillium brevicompactum and Zalerion maritimum inferred from microplastics mass loss (∼22 to -26 % and ∼40 to 50 %, respectively) and FTIR spectra (particularly in the hydroxyl and carbonyl groups). In addition, microfibres released from facemasks induced sublethal effects on the clam, Venerupis corrugata, mostly in their UV-aged form when compared to pristine ones, characterised by a decrease in cellular energy allocation (CEA) and an increase in aerobic energy metabolism (ETS). Concomitantly, clams exposed to 1250 items/L of UV-aged microplastics (similar to field-reported concentrations) expressed greater clearance capacity, indicating a need to compensate for the potential energy unbalance. This study provides the first baseline monitoring of facemasks in wetlands while bringing new evidence on their biodegradation and ecotoxicity, considering environmentally relevant conditions and keystone organisms in such environments. Such studies require scientific attention for rapid regulatory action against this emerging and persistent pollutant, also targeting remediation and mitigation strategies considering these items under pandemic scenarios., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

This study investigates the potential of MPs as carriers of pollutants as they can strengthen bioaccumulation of toxic metals on marine organisms. For the first time, the interaction of the metal palladium (Pd) with the widespread MPs, both with increasing concentrations in water environments from anthropogenic sources, was tested. Mytilus galloprovincialis, an important seafood product, was exposed to Pd (24 h) in two ways: water-dissolved and MPs-adsorbed, with depuration followed for 144 h. Quantification of Pd in tissues shown an accumulation 2-3 times higher (59 % of initial Pd) for mussels exposed to MPs-adsorbed Pd and higher in digestive gland than when exposed to water-dissolved Pd (25 %; higher in gills). Additionally, it was demonstrated that Pd induced oxidative stress and altered the feeding behavior of mussels. Therefore, this work support MPs as being vectors of metals (i.e. Pd) to enhance their bioaccumulation on marine organisms which highlights ecological risk of these emerging pollutants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Metal(oid)s concentrations have been quantified in plastic pieces collected from four beaches located in the Mediterranean coast of Spain with different characteristics (i.e. anthropogenic pressure, zone). Metal(oid)s content was also related to selected plastic criteria (i.e. color, degradation status, polymer). The selected elements were quantified with mean concentrations in the sampled plastics with the following order: Fe > Mg > Zn > Mn > Pb > Sr > As > Cu > Cr > Ni > Cd > Co. Moreover, black, brown, PUR, PS, and coastal line plastics concentrated the higher metal(oid)s levels. Local of sampling (influence of mining exploitation) and severe degradation were key factors for uptake of metal(oid)s from water by plastics as modification of surfaces strengths their adsorption capacity. Determined high levels of Fe, Pb and Zn in plastics reflected the pollution degree of the marine areas. Therefore, this study is a contribution for the potential use of plastics as pollution monitors., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Juan Santos Echeandia reports financial support was provided by Spanish State Research Agency (AEI) and the Ministry of Science, Innovation and Universities (MICIU). Teresa Rocha-Santos reports financial support was provided by Portuguese Science Foundation (FCT). Armando Costa Duarte reports financial support was provided by Portuguese Science Foundation (FCT). Joana Patricio Rodrigues reports financial support was provided by Portuguese Science Foundation (FCT)., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Freshwater benthic environments are among the major sinks of microplastics (MPs, < 5 mm) sourced on inland anthropogenic activities. The ecotoxicological effects of MPs on benthic macroinvertebrates have been assessed preferably in collectors, shredders, and filter-feeders, but resulting in insufficient knowledge on the potential trophic transfer and its effects on macroinvertebrates with predator behaviour such as planarians. This work evaluated the behavioural (feeding, locomotion), physiological (regeneration) and biochemical responses (aerobic metabolism, energy reserves, oxidative damage) of the planarian Girardia tigrina after consuming contaminated live prey Chironomus riparius larvae previously exposed to microplastics of polyurethane (PU-MPs; 7-9 μm in size; 375 mg PU-MPs/kg). After the feeding period (3 h), planarians consumed 20 % more contaminated prey than uncontaminated prey, probably related to increased curling/uncurling movements of larvae (that might be more appellative to planarians). Histological analysis revealed planarians' limited intake of PU-MPs, mainly detected near the pharynx. The consumption of contaminated prey (and intake of PU-MPs) did not result in oxidative damage but slightly increased the aerobic metabolism and energy reserves which show that the consumption of more prey was sufficient to cope with the potential adverse effects of internalized MPs. Moreover, no effects were observed in the locomotion of planarians in good agreement with the hypothesis of sufficient energy acquired by the exposed planarians. Despite the previous, it seems that the energy acquired was not allocated for planarians' regeneration since a significant delay in the regeneration of the auricles was observed for planarians feeding on contaminated prey. Therefore, further studies should be performed considering the potential long-term effects (i.e., reproduction/fitness) and the effects of MPs that might result from continuous feeding on contaminated prey, representing a more realistic exposure scenario., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Freshwater provides valuable services and functions to humankind. However, macroinvertebrates that underpin the delivery of many of those ecosystem services and functions are under an additional threat caused by microplastic pollution. Chironomids are one of the most abundant groups of macroinvertebrates in these environments and the most sensitive to microplastics. This investigation addressed the effects of polyurethane (PU-MPs; 7.0-9.0 µm) on the chironomid Chironomus riparius at the organism and sub-organism levels. For this purpose, two assays were carried out: (i) addressing the effects of PU-MPs on C. riparius partial life cycle traits (larval size and emergence parameters) in a 28 d assay considering concentrations up to 750 mg/Kg, and (ii) larvae behaviour (locomotion) as well as the biochemical responses (oxidative damage, aerobic energy production, and energy reserves) in a 10 d assay considering an environmentally relevant concentration with no observed effects on C. riparius previous life history traits (no observed effect concentration; NOEC = (375 mg/kg). Exposure to PU-MPs did not affect C. riparius larval length nor cumulative and time to emergence. Conversely, when exposed to an environmentally relevant concentration for 10 days, contaminated larvae were revealed to be lighter (but not smaller nor less nutritionally affected in terms of energy reserves) and more active when foraging, which was reflected in the activation of their aerobic metabolism when assessing the electron transport chain as a proxy. Notwithstanding, PU-MPs did not originate observable energy costs, either on protein, lipid, or sugar contents on contaminated larvae, which may justify the absence of effects on larval growth and emergence. Therefore, the increased production of energy used for the locomotion and functioning of larvae was at the expense of the fraction of energy that should have been allocated for the weight of the individuals. A long-term exposure involving a multigenerational assessment would bring intel on the potential (cumulative) sub-lethal effects of PU-MPs on C. riparius fitness.

The presence of microplastics in the aquatic ecosystem represents a major issue for the environment and human health. The capacity of organic pollutants to adsorb onto microplastic particles raises additional concerns, as it creates a new route for toxic compounds to enter the food web. Current knowledge on the impact of pristine and/or contaminated microplastics on aquatic organisms remains insufficient, and we provide here new insights by evaluating their biological effects in zebrafish (Danio rerio). Zebrafish larvae were raised in ZEB316 stand-alone housing systems and chronically exposed throughout their development to polyethylene particles of 20-27 μm, pristine (MP) or spiked with benzo[α]pyrene (MP-BaP), supplemented at 1% w/w in the fish diet. While they had no effect at 30 days post-fertilization (dpf), MP and MP-BaP affected growth parameters at 90 and 360 dpf. Relative fecundity, egg morphology, and yolk area were also impaired in zebrafish fed MP-BaP. Zebrafish exposed to experimental diets exhibited an increased incidence of skeletal deformities at 30 dpf as well as an impaired development of caudal fin/scales, and a decreased bone quality at 90 dpf. An intergenerational bone formation impairment was also observed in the offspring of parents exposed to MP or MP-BaP through a reduction of the opercular bone in 6 dpf larvae. Beside a clear effect on bone development, histological analysis of the gut revealed a reduced number of goblet cells in zebrafish fed MP-BaP diet, a sign of intestinal inflammation. Finally, exposure of larvae to MP-BaP up-regulated the expression of genes associated with the BaP response pathway, while negatively impacting the expression of genes involved in oxidative stress. Altogether, these data suggest that long-term exposure to pristine/contaminated microplastics not only jeopardizes fish growth, reproduction performance, and skeletal health, but also causes intergenerational effects., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Microplastics are ubiquitous contaminants of freshwater ecosystems. However, few ecotoxicity assays have been conducted on freshwater organisms using environmentally relevant concentrations of virgin and weathered microplastics. This work assessed the adverse effects of virgin and artificially weathered fragments of polystyrene and polypropylene on the microalga Raphidocelis subcapitata (72 h growth inhibition assay) and on embryos of the fish Danio rerio (96 h fish embryo assay) under environmentally relevant concentrations (2000-200,000 MP L -1 ) and high concentrations (12.5-100 mg L -1 ). Sizes of microplastics were measured as tens (polystyrene) to hundreds (polypropylene) of micrometers, while aging was assessed by measuring the carbonyl index. In the microalga, the tested high concentrations promoted growth, while environmentally relevant concentration induced either growth inhibition or promotion. In zebrafish embryos, environmentally relevant concentrations decreased body length and heart rates. No relevant effects were observed in organisms exposed to high concentrations for mortality, malformations, hatching rates, and swimming bladder inflation. Virgin microplastics presented slightly higher toxicity but direct comparison was hindered by the lack of a linear dose-response curve. Despite the lack of a clear pattern, adverse effects were often observed in the lowest environmentally relevant concentrations, raising concerns over the impacts of microplastics on freshwater ecosystems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The extraction of microplastics from organic-rich freshwater samples is challenging and limited information is available in the literature. This study aims at developing efficient methods for water volume reduction and organic matter removal in freshwater samples, while focusing on the reduction of the economic and environmental costs, maintaining microplastics integrity and avoiding contamination. For the water volume reduction approach, centrifuging freshwater samples (water, sediment, algae, leaves, driftwood, fish tissue) at different speeds (3500, 6000 rpm) and times (5, 10 min) showed that 3500 rpm for 5 min was efficient to settle the mineral and organic material, while preserving the polymers and showing high microplastic recovering rates (93 ± 6%). These recovery rates were significantly higher than the traditional sieving approach (77 ± 22%). The posterior minimal consumption of reagents resulting from the reduction of water volume helped to reduce the economic and environmental costs of the devised methodology, becoming more aligned with green chemistry principles. For biogenic organic matter removal, four digestion solutions were tested on freshwater samples, namely 10% potassium hydroxide, Fenton reagent (30% H 2 O 2  + Fe(II)), 7% and 10% sodium hypochlorite (NaClO), under 3 periods of time (1, 6 and 15 h), at 50 °C. Both 7% and 10% NaClO showed the highest rates of organic matter removal (86 ± 1% and 90 ± 1%, respectively), after 6 h at 50 °C. Exposure of virgin and aged polymers (polyethylene, polypropylene, polystyrene, polyvinyl chloride, nylon, polyethylene terephthalate) to NaClO showed no weight, visual, surface structure, Fourier transform infrared spectra and carbonyl index changes, except for nylon, although not to an extent that affected its identification. This method resulted in high recovery rates of polymers (92 ± 6%). Thus, 7% NaClO at 50 °C for 6 h (or overnight) may be efficiently used for microplastic analysis in organic-rich freshwater samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Marine ecosystems represent major sinks for persistent organic pollutants (POPs). Yet, while their regulations fit localized activity and emissions, POPs are mobile and can persist away from their source. The present review draws an environmental diagnostic of the organic substances studied over the past forty months, which ones accumulated the most, and where. Maximum reported concentration was used as a proxy for the accumulation of contaminants. POPs occurrences studied in the Jan 2018-April 2021 period were recorded into a database, along with (i) the geographical location of the sample and its coastal or offshore origin, (ii) the type of compartment analyzed (water vs sediment), as well as (iii) the POPs and the sample physical-chemical parameters reported. In the articles reviewed, maximum reported concentrations of POPs were in the ng/L range in seawater and in the μg/kg range in sediments. Some hotspots presented concentrations high enough to represent a hazard for sea organisms in the water columns (μg/L range) or in surficial sediments (mg/kg range). On a global scale, offshore (>1 km from the coast) maximum reported concentrations were, for the majority of the POPs, equivalent or higher than coastal ones. Finally, a POP solubility threshold (900 mg/L) was observed above which POPs would not be found in offshore waters, but only in sediments. This review highlights that studying POP accumulation away from their sources is fundamental for the diagnostic of long-lasting marine POPs contaminations. Further, POPs lipophilicity is a good predictor for offshore transport, and an indicator of interest for predicting sediment accumulation. Although POPs fate and transport in oceans is complex and require a finer analysis that this review could provide, the present work is a step forward identifying the hotspots in which POPs could be of particular concern, along with chemical indicators to predict for POPs accumulation in marine reservoirs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Microplastics have been found in fish, but most studies have focused on the digestive system without considering additional organs. Herein, the objective was to assess the presence of microplastics in internal organs (gills, guts, kidney, heart) of the Atlantic horse mackerel (Trachurus trachurus) captured of the coast of Portugal (Northeast Atlantic Ocean). Suspected microplastics were present in all organs, with particles of larger size (i.e., equivalent diameter) found in the gut and those of lower size in the heart and its luminal blood. Suspected microplastics of 1-10 μm were the most abundant (65.4%), more likely to translocate, owing to their minute size, but more difficult to properly characterize. These results highlight the need to expand the analytical work on organs and tissues for assessing microplastics in organisms, but also emphasize the actual need for developing analytical methods that allow for an accurate isolation, identification, and characterization of microplastics in biota., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Currently, the evidence of the ingestion of microplastics (MPs) by organisms or the accumulation in different environmental compartments has been achieved using several methodological procedures. However, its uses have not been standardized across studies. In this study, we aim to assess and validate a protocol that can be useful for optimizing the identification and quantification procedures of polyethylene microplastics (PE MPs) in biological samples. Initially, considering that numerous studies filter samples previously digested in cellulosic membranes for isolation and analysis of MPs, we evaluated whether washing these membranes with different reagents could contribute to the complete detachment of particles, as well as to their dispersion in the obtained solutions. However, none of the tested reagents (dimethyl sulfoxide, acetone, ethyl alcohol and chloroform), including purified water, was able to completely remove the MPs adhered to the membranes or facilitate their dispersion in the solutions. On the other hand, we observed that the digestion of the membranes by acetonitrile constituted a procedure that prevents the loss of particles due to adherence, in addition to promoting good dispersion of MPs. Subsequently, we evaluated the use of Neubauer chambers for the quantification of MPs, having observed a good recovery rate (>92%) and results with insignificant variation, in PE MPs solutions with different concentrations (0.15; 0.075 and 0.0375 mg/mL). Ultimately, the validation of the proposed procedures took place from the evaluation of the accumulation of PE MPs in Astyanax spp. juveniles, having demonstrated the efficiency and sensitivity of the method proposed for this purpose. Subsequently, our study provides a methodological alternative that can optimize MPs quantifications in biological samples and reduce the generation of biased or unreliable results., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The ubiquity of microplastics raises issues regarding contamination control measures and laboratory practices. The objective was to adapt the use of counting chambers and plastic microplates on the ecotoxicity evaluation of microplastics. Counting chambers, originally used to quantify cells, can also be used to count high concentrations of microplastics (<100 μm) used in laboratory assays. By decontaminating the chamber and mixing the test solution with Nile Red (1:1), fluorescent particles can be easily counted under optical microscopy. Microplate wells, due to their composition, can be contaminated or release microplastics to the test medium, which can interfere with the results of ecotoxicity assays or spectroscopy readings. A cleaning method based on ethanol was developed, which effectively removed particles by 91% without interfering with microalgae yield. Besides providing practical applications that can improve ecotoxicity assays, this work intends to raise awareness on the need to adapt laboratory practices when working with microplastics., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Microplastics (MPs) are one of the most significant solid waste pollutants in the marine environment and accumulate in sediments around worldwide. In this study, the pollution level, the type, occurrence, and distribution of MPs in sediments from the southwestern Kerkennah archipelago, Tunisia, were investigated. Sediment samples were collected from 20 adjacent sites through three "lines L1, L2, and L3." MPs were separated from sediment by density flotation (NaCl, 1.2 g cm -3 ) and characterized in terms of shape, size, and color using microscope. The accumulation of toxic chemicals such as trace metals on microplastics was measured by atomic absorption microwave-assisted acid extraction. Polymer types were identified using FTIR-ATR spectroscopy. This study showed that microplastics were found in all samples, which emphasized that their extensive distribution throughout three lines by an average abundance of "MPs" was 611 items/m 2 . Among the shape categories of plastic particles, fiber and fragment were the most dominant frequent shapes (94%). The more frequent colors found were white (52.7%) and transparent (35.1%). Regarding the sizes, the microplastics below 1 mm were the most common accounting for 97% of all plastics. Results of trace metals Zn, Cu, Pb, Cr, and Ni in sediments with concentrations were reported as 3.48 μg/g, 0.41 μg/g, 0.38 μg/g, 0.33 μg/g, and 0.12 μg/g, respectively. Graphical abstract., (© 2020. Springer-Verlag GmbH Germany, part of Springer Nature.)

Many methods have been used to isolate and identify microplastics from biological matrices. In biological samples, Nile Red can stain undigested residues, such as fats, soaps, and gels formed during organic matter removal, hindering the identification of fluorescent microplastics (≥2 μm). Thus, adjustments on sample preparation (e.g., fat removal) are required for the accurate identification of Nile Red stained microplastics. Multiples tests allowed to identify that digestion with 10% KOH at 60 °C for 24 h, followed by treatments with boiling water, acetone, and staining, produced good results in fourteen biological samples, including vertebrates and invertebrates. Digestion efficiencies were 94-100%, except for feces, which were 87%. Recovery rates of spiked microplastics were 97-100%, and few effects were observed in the infrared spectra and carbonyl index of seven polymers, with only the occasional yellowing suggesting surface changes. Filtration rates were improved by reducing the amount of sample. Small fluorescent microplastics could be identified in all samples under the microscope. Overall, the proposed method was efficient in removing natural organic matter from biological samples for Nile Red staining, requiring minimal sample handling, improving sample throughput, and allowing quantification of fluorescent microplastics in biological samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Microplastics contamination is widespread in the environment leading to the exposure of both humans and other biota. While most studies overemphasize direct toxicity of microplastics, particle concentrations, characteristics and exposure conditions being used in these assays needs to be taken into consideration. For instance, toxicity assays that use concentrations over 100,000 times higher than those expected in the environment have limited practical relevance. Thus, adverse effects on animal and human health of current environmental concentrations are identified as a knowledge gap. Conversely, this does not suggest the lack of any significant effects of microplastics on a global scale. The One Health approach provides a novel perspective focused on the intersection of different areas, namely animal, human, and environmental health. This review provides a One Health transdisciplinary approach to microplastics, addressing indirect effects beyond simple toxicological effects. Microplastics can, theoretically, change the abiotic properties of matrices (e.g., soil permeability) and interfere with essential ecosystem functions affecting ecosystem services (e.g., biogeochemical processes) that can in turn impact human health. The gathered information suggests that more research is needed to clarify direct and indirect effects of microplastics on One Health under environmentally relevant conditions, presenting detailed knowledge gaps., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Microplastic (MPs) pollution has been recognized as a serious threat to marine environment with the growing use of plastics. There is no sufficient data on the extent and characteristics of MPs pollution in the beach sediments and sand in the Atlantic Ocean. The coastal area is one of the main tourist zones in Aveiro in Portugal, thus, impacted by both tourism and maritime traffic, which are major sources of MPs. Considering this issue, 33 sediment samples were collected from the Praia da Barra beach in Aveiro. This pilot study showed that large quantities of MPs are accumulated on this beach with a median concentration of 100 MP kg-1 (15-320 MP kg-1), that is dominated by polyethylene (30%), polypropylene (27%), polystyrene (18%), nylon (12%), and polyester (6%). Size <1 mm constituted 99.5% of particles, mostly of transparent or black colors, with highest concentrations closest to the water line., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Beverages, often packaged in plastic, can be a source of microplastics in the human diet. In this study, an improved method for detection of microplastics in white wines capped with synthetic stoppers is explored. Visual quantification in the stereomicroscope or using Nile Red were excluded due to the small size of particles. Quantification in the optical microscope identified up to 5,857 particles.L -1 but lacked chemical characterization. Finally, micro-Raman spectroscopy was used for the first time in complex beverages in the identification of microplastics particles in white wines, allowing identification of at least one synthetic particle for each bottle, except in two cases. Improvements included reduction in volume filtered, selection of aluminum oxide filters, selection of blue laser and lack of H 2 O 2 treatment. Using this method, identification of all particles present in small representative areas of the filter by micro-Raman spectroscopy will allow proper quantification of microplastics in complex beverage matrices., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Widespread contamination of microplastics may lead to internalization in fish. This literature review from March 2019 to March 2020 details that a median of 60% of fish, belonging to 198 species captured in 24 countries, contain microplastics in their organs. Carnivores species ingested more microplastics than omnivores. Only 14% of fish were from aquaculture. Most studies focused on digestive systems, with presence in other organs currently being insufficiently assessed. Based on this assessment, knowledge gaps that should be addressed in future studies were identified., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Plastics and microplastics are ubiquitous contaminants in aquatic ecosystems. This critical review is the first attempt at analyzing sources, concentration, impacts and solutions of (micro)plastic litter in Portugal based on all currently available literature. We found that, besides sea-based sources (e.g. shipping, fishing), 5717 t of mismanaged waste and 4.1 trillion microplastics from wastewater, mostly from untreated wastewater, are released to the environment every year. The highest concentrations are found in the North, Center and Lisbon regions, mostly comprised of consumer products, fishing gear and microplastics (<5 mm), especially fragments and pellets. This contamination has resulted in ingestion of plastics by organisms, including mussels, fishes, birds and turtles. Thus, every Portuguese citizen may consume 1440 microplastics a year based on the consumption of mollusks. Awareness campaigns, improvements in waste management and reductions in the release of untreated wastewater are recommended measures to reduce plastic pollution in Portugal., Competing Interests: Declaration of competing interest The authors declare no competing interest., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Natural organic matter may confound the detection of microplastics, requiring a removal step. However, most available protocols are long and lack information on removal efficiency and polymer degradation. Thus, we have determined the digestion efficiency (%) for a pool of organic matter (algae, driftwood, feathers, fish muscle, paraffin, palm oil) for five digestion solutions, hydrogen peroxide (H 2 O 2 ), hydrogen peroxide with iron catalyst (H 2 O 2  + Fe), potassium hydroxide (KOH), nitric acid (HNO 3 ), and sodium dodecyl sulphate (SDS), under two temperatures (room temperature at 25 °C, 50 °C) and two periods (1, 6 h). H 2 O 2  + Fe and KOH at 50 °C for 1 h had the highest digestion efficiencies, of 65.9% and 58.3% respectively (mostly limited by driftwood and paraffin). Further testing revealed that H 2 O 2  + Fe is more appropriate for plant material and KOH for animal tissue. Weight loss (%), Fourier transform infrared spectrometry and carbonyl index of 9 virgin and 6 weathered polymers (polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, cellulose acetate, nylon) revealed that only identification of cellulose acetate was hindered. Filters were also tested revealing that quartz and glass fibre filters are resistant to these protocols. Thus, a digestion protocol based on H 2 O 2  + Fe or KOH at 50 °C for 1 h may be used on microplastic samples., (Copyright © 2019. Published by Elsevier B.V.)

Despite the increasing interest in microplastic (MP) research, the accurate prevalence, distribution and fate of these materials in the environment is yet poorly known and, consequently, a focus of debate. Hence, to better ascertain the presence of microplastics in specific environments, samples from 35 random sites distributed across a 4200-meter long section from the area of Sidi Mansour, Sfax-Tunisia, were collected and analyzed. MPs were extracted, digested with potassium hydroxide and dyed with Eosin B, for visual microscopy counting and sorting. Polymer composition and surface morphology were identified by FTIR-ATR spectroscopy and SEM microscopy. Total abundances ranged from 252 to-5332 particles per m 2 where fragments and granules were the most frequent types of microplastics. These findings highlight the considerable presence of these materials in the studied harbor region and underscore the density dependence on the distribution and occurrence of MPs and how these tend to accumulate in the sandy sediments., (Copyright © 2019. Published by Elsevier Ltd.)

Microplastics are persistent contaminants accumulating in the environment. Aquatic ecosystems have been studied worldwide, revealing ubiquitous contamination with microplastics. Microalgae, one of the most important primary producers in aquatic ecosystems, could suffer from microplastic contamination, leading to larger impacts on aquatic food webs. Nonetheless, little is known about the toxic effects of microplastics on microalgae populations. Thus, the objective of this review was to identify these effects and the impacts of microplastics on microalgae populations based on currently available literature, also identifying knowledge gaps. Even though microplastics seem to have limited effects on parameters such as growth, chlorophyll content, photosynthesis activity and reactive oxygen species (ROS), current environmental concentrations are not expected to induce toxicity. Even so, microplastics could disrupt population regulation mechanisms, by reducing the availability or absorption of nutrients (bottom-up) or reducing the population of predator species (top-down). Microplastics' properties can also influence the effects on microalgae, with smaller sizes and positive surface charges having higher toxicity. Therefore, more research is needed to better understand the effects of microplastics on microalgae, such as adaptation strategies, effects on population dynamics and microplastics properties influencing toxicity., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Microplastic contamination of aquatic environments has become an increasingly alarming problem. These, defined as particles <5 mm, are mostly formed due to the cracking and embrittlement of larger plastic particles. Recent reports show that the increasing presence of microplastics in the environment could have significant deleterious consequences over the health of marine organisms, but also across the food chain. Herein, we have studied the effects of artificial seawater on polyethylene (PE)-based beads by exposing them up to eight weeks to saltwater in stirred batch reactors in the dark and examined the structural and morphological changes these endured. Electron microscopy observations showed that artificial seawater induces severe microcracking of the pellets' surfaces. Additionally, Fourier transform infrared spectroscopy (FTIR) analyses evidenced the formation of oxidized groups whenever these particles were exposed to water and an increase in organic matter content of the waters in which the pellets were kept was evidenced by Raman spectroscopy. There were also noticeable consequences in the thermal stability of the polyethylene pellets, as determined by thermogravimetric studies (TGA). Furthermore, the parallel exposure of polyethylene pellets to UV radiation yielded less pronounced effects, thus underscoring its lower preponderance in the degradation of this material. These results highlight the importance of determining the mechanisms of degradation of microplastics in marine settings and what the implications may be for the environment. Overall, the herein presented results show that a relatively short period of time of accelerated exposure can yield quantifiable chemical and physical impacts on the structural and morphological characteristics of PE pellets.

This study aimed to explore the efficiency of two adsorbents, cork granules with different granulometry and titanium dioxide nanomaterial, in the removal of chemical oxygen demand (COD), colour and toxicity from a textile effluent. The adsorption assays with cork were unsatisfactory in the removal of chemical parameters however they eliminated the acute toxicity of the raw effluent to Daphnia magna. The assay with TiO 2 NM did not prove to be efficient in the removal of colour and COD even after 240 min of contact; nevertheless it also reduced the raw effluent toxicity. The best approach for complete remediation of the textile effluent has not yet been found however promising findings were achieved, which may be an asset in future adsorption assays.

Risk assessment of pesticides has been based on direct toxic effects on aquatic organisms. Indirect effects data are taken into account but with limitations, as it is frequently difficult to predict their real impacts in the ecosystems. In this context the main aim of this work was to assess how the exposure to the herbicide pendimethalin (Prowl(®)), under environmentally relevant concentrations, may compromise the nutritional composition of food for a relevant group of primary consumers of freshwater food webs-the daphnids, thus affecting their reproduction performance and subsequently the long-term sustainability of active populations of this grazer. Therefore, Daphnia magna individuals were chronically exposed in a clean medium to a control diet (NCF - i.e., non-contaminated green algae Raphidocelis subcapitata) and to a contaminated diet (CF - i.e., the same monoalgal culture grown in a medium enriched with pendimethalin in a concentration equivalent to the EC20 for growth inhibition of algae), during which reproductive endpoints were assessed. The algae were analysed for protein, carbohydrate and fatty acid content. The chemical composition of R. subcapitata in the CF revealed a slight decrease on total fatty acid levels, with a particular decrease of essential ω9 monounsaturated fatty acids. In contrast, the protein content was high in the CF. D. magna exposed to CF experienced a 16% reduction in reproduction, measured as the total number of offspring produced per female. Additionally, an internal pendimethalin body burden of 4.226μgg(-1) was accumulated by daphnids fed with CF. Hence, although it is difficult to discriminate the contribution of the pesticide (as a toxic agent transferred through the food web) from that of the food with a poor quality-compromised by the same pesticide, there are no doubts that, under environmentally relevant concentrations of pesticides, both pathways may compromise the populations of freshwater grazers in the long term, with consequences in the control of the primary productivity of these systems., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Cadmium-based quantum dots (QDs) are increasingly applied in existent and emerging technologies, especially in biological applications due to their exceptional photophysical and functionalization properties. However, they are very toxic compounds due to the high reactive and toxic cadmium core. The present study aimed to determine the toxicity of three different QDs (CdS 380, CdS 480 and CdSeS/ZnS) before and after the exposure of suspensions to sunlight, in order to assess the effect of environmentally relevant irradiation levels in their toxicity, which will act after their release to the environment. Therefore, a battery of ecotoxicological tests was performed with organisms that cover different functional and trophic levels, such as Vibrio fischeri, Raphidocelis subcapitata, Chlorella vulgaris and Daphnia magna. The results showed that core-shell type QDs showed lower toxic effects to V. fischeri in comparison to core type QDs before sunlight exposure. However, after sunlight exposure, there was a decrease of CdS 380 and CdS 480 QD toxicity to bacterium. Also, after sunlight exposure, an effective decrease of CdSeS/ZnS and CdS 480 toxicity for D. magna and R. subcapitata, and an evident increase in CdS 380 QD toxicity, at least for D. magna, were observed. The results of this study suggest that sunlight exposure has an effect in the aggregation and precipitation reactions of larger QDs, causing the degradation of functional groups and formation of larger bulks which may be less prone to photo-oxidation due to their diminished surface area. The same aggregation behaviour after sunlight exposure was observed for bare QDs. These results further emphasize that the shell of QDs seems to make them less harmful to aquatic biota, both under standard environmental conditions and after the exposure to a relevant abiotic factor like sunlight., (Copyright © 2016 Elsevier B.V. All rights reserved.)

This work reports the construction of a fast, disposable, and label-free immunosensor for the determination of atrazine. The immunosensor is based on a field effect transistor (FET) where a network of single-walled carbon nanotubes (SWCNTs) acts as the conductor channel, constituting carbon nanotubes field effect transistors (CNTFETs). Anti-atrazine antibodies were adsorbed onto the SWCNTs and subsequently the SWCNTs were protected with Tween 20 to prevent the non-specific binding of bacteria or proteins. The principle of the immunoreaction consists in the direct adsorption of atrazine specific antibodies (anti-atrazine) to SWCNTs networks. After exposed to increasing concentrations of atrazine, the CNTFETs could be used as useful label-free platforms to detect atrazine. Under the optimal conditions, a limit of detection as low as 0.001 ng mL(-1) was obtained, which is lower than that of other methods for the atrazine detection, and in a working range between 0.001 and 10 ng mL(-1). The average recoveries obtained for real water samples spiked with atrazine varied from 87.3% to 108.0%. The results show that the constructed sensors display a high sensitivity and could be useful tools for detecting pesticides like atrazine at low concentrations. They could be also applied to the determination of atrazine in environmental aqueous samples, such as seawater and riverine water., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Nanomaterials (NMs) are widely recommended for wastewater treatments due to their unique properties. Several studies report the different advantages of nanotechnology in the remediation of wastewaters, but limited research has been directed toward the fate and potential impacts of the solid residues (SRs) produced after the application of such technologies. The present work aimed at investigating the ecotoxicity of SRs resulting from the treatment of three effluents (OOMW, kraft pulp mill, and mining drainage) with two NMs (TiO2 and Fe2O3). The invertebrate Chironomus riparius was selected as test organism and exposed to the residues. The effect on percentage of survival and growth was assessed. Results showed that the SRs from the treatments nano-TiO2(1.0gL(-1))/H2O2(0.5M) and nano-Fe2O3(1.0gL(-1))/H2O2(1.0M) from OOMW and nano-Fe2O3(0.75gL(-1))/H2O2(0.01M) from kraft pulp mill effluent exhibited lethal toxicity to C. riparius. Only the exposure to SRs resulting from the treatment with nano-Fe2O3(0.75gL(-1))/H2O2(0.01M) applied to the kraft pulp mill effluent significantly affected the growth rate based on the head capsule width. In terms of growth rate, based on the body length, it decreased significantly after exposure to the SRs from the treatments nano-TiO2 (1.0gL(-1)) and nano-Fe2O3(0.75gL(-1))/H2O2(0.01M) of kraft paper mill effluent and nano-Fe2O3(1.0gL(-1))/H2O2(1.0M) of OOMW. According to our study the SRs can promote negative effects on C. riparius. However, the effects are dependent on the type of effluent treated as well as on the organic and inorganic compounds attached to the NMs., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The aim of the present study was to assess the toxic effects of a secondary treated effluent from a modern pulp mill processing Eucalyptus globulus on both sexes of goldfish. The effects in the exposed fish were investigated by measuring biomarkers which have been used to assess the effects of BKME on aquatic biota, with particular emphasis in fish. However, few studies have been focused on effluents from pulp mill plants processing eucalyptus. The relative proportion of cytochrome P450 (CYP1A) and vitellogenin (VTG) induction were analyzed in the livers of males and females goldfish, exposed to different concentrations of a bleached Kraft pulp mill (BKPM) effluent. Somatic indices such as HSI (hepatosomatic index) and GSI (gonadosomatic index) were calculated and a significant reduction was found in males GSI. A significant increase of HSI was recorded for both sexes exposed to 50% BKPM effluent. Exposure to BKPM effluent induced CYP1A synthesis in both sexes and decreased VTG synthesis in females according to the different effluent concentrations suggesting that the secondary treated effluent contained compounds that affect fish negatively. The results suggest that BKPM effluent can cause sex-related biochemical changes in xenobiotic metabolism.

Background, Aim and Scope: Pulp and paper mills generate a plethora of pollutants depending upon the type of pulping process. Efforts to mitigate the environmental impact of such effluents have been made by developing more effective biological treatment systems in terms of biochemical oxygen demand, chemical oxygen demand, colour and lignin content. This study is the first that reports an evaluation of the effects of a tertiary treatment by fungi (Pleurotus sajor caju, Trametes versicolor and Phanerochaete chrysosporium and Rhizopus oryzae) on individual organic compounds of a Eucalyptus globulus bleached kraft pulp and paper mill final effluent after secondary treatment (final effluent)., Material and Methods: The tertiary treatment with P. sajor caju, T. versicolor and P. chrysosporium and R. oryzae was performed in batch reactors, which were inoculated with separate fungi species and monitored throughout the incubation period. Samples from effluent after secondary and after tertiary treatment with fungi were analysed for both absorbance and organic compounds. The samples were extracted for organic compounds using solid-phase extraction (SPE) and analysed by gas chromatography-mass spectrometry (GC/MS). The efficiencies of the SPE procedure was evaluated by recovery tests., Results: A total of 38 compounds (carboxylic acids, fatty alcohols, phenolic compounds and sterols) were identified and quantified in the E. globulus bleached kraft pulp mill final effluent after secondary treatment. Recoveries from the extraction procedure were between 98.2% and 99.9%. The four fungi species showed an adequate capacity to remove organic compounds and colour. Tertiary treatment with R. oryzae was able to remove 99% of organic compounds and to reduce absorbance on 47% (270 nm) and 74% (465 nm). P. sajor caju, T. versicolor and P. chrysosporium were able to remove 97%, 92% and 99% of organic compounds, respectively, and reduce 18% (270 nm) to 77% (465 nm), 39% (270 nm) to 58% (465 nm) and 31% (270 nm) to 10% (465 nm) of absorbance, respectively., Discussion: The wide variety of organic compounds found in the final effluent must be due to the degradation of E. globulus wood in pulp and paper mill. The concentrations of organic compounds in the final effluent of E. globulus bleached kraft pulp mill were in residual levels maybe due to the secondary treatment. The recovery tests showed the effectiveness of the extraction procedure, and no losses of analyte were suspected in the analytical determinations. Lignin derivatives such as vanilic acid, syringic acid, guaiacol, syringol and phloroglucinol were totally removed by R. oryzae, but the 47% absorbance reduction obtained at 270 nm suggests that these species were not able to complete degradation of lignin macromolecular compounds., Conclusions: The organic compounds (carboxylic acids, fatty alcohols, phenolic compounds and sterols) were removed more efficiently by tertiary treatment with R. oryzae or P. chrysosporium, followed by P. sajor caju and T. versicolor. Regarding the removal of both colour and organic compounds, the tertiary treatment with R. oryzae was the most efficient., Recommendations and Perspectives: In order to reduce the deleterious impacts of paper mill effluents, efforts have been made to develop more effective advanced tertiary treatments. This study may serve as a basis of characterisation, in terms of organic compounds of E. globulus bleached kraft pulp mill final effluent after secondary treatment and as an effort to understand the effects of tertiary treatments with fungi on low concentrations of organic compounds from biological secondary treatment.

Background, Aim, and Scope: Olive oil mill wastewater (OOMW) environmental impacts minimization have been attempted by developing more effective processes, but no chemical or biological treatments were found to be totally effective to mitigate their impact on receiving systems. This work is the first that reports simultaneously the efficiency of three different approaches: biological treatment by two fungal species (Trametes versicolor or Pleurotus sajor caju), enzymatic treatment by laccase, and chemical treatment by photo-Fenton oxidation on phenols removal., Materials and Methods: Those treatments were performed on OOMW with or without phenol supplement (p-coumaric, vanillin, guaiacol, vanillic acid, or tyrosol). OOMW samples resulted from treatments were extracted for phenols using liquid-liquid extraction and analyzed by gas chromatography coupled to mass spectrometry., Results: Treatment with T. versicolor or P. sajor caju were able to remove between 22% and 74% and between 8% and 76% of phenols, respectively. Treatment by laccase was able to reduce 4% to 70% of phenols whereas treatment by photo-Fenton oxidation was responsible for 100% phenols reduction., Discussion: Range of phenol degradation was equivalent between T. versicolor, P. sajor caju and laccase for p-coumaric, guaiacol, caffeic acid, and tyrosol in supplemented OOMW, which enhances this enzyme role in the biological treatment promoted by these two species., Conclusions: Phenols were removed more efficiently by photo-Fenton treatment than by biological or enzymatic treatments., Recommendations and Perspectives: Use of fungi, laccase, or photo-Fenton presents great potential for removing phenols from OOMW. This should be further assessed by increasing the application scale and the reactor configurations effect on the performance, besides a toxicity evaluation of treated wastewater in comparison to raw wastewater.

The toxicity of bleached Kraft pulp mill effluents (BKME) is usually attributed to chemical compounds which are produced and released throughout various stages of pulp and paper production. The main objective of the present work was to detect sub-lethal responses of goldfish (Carassius auratus) to secondary treated BKME which was treated with Rhizopus oryzae. A total of 96 carps (C. auratus; 11 +/- 3 g) were exposed to different concentrations of the post-treated effluent (0, 1, 10, 25, 50, and 100%), in 28 days semi-static tests. Several biomarkers were then evaluated to assess the toxicological effects: induction of CYP1A (metabolic processes of organic compounds in liver), change in steroid profiles (11-Ketotestosterone, 17beta-estradiol), histopathology of liver and gonads and somatic indices (GSI, HSI) for endocrine disruption and other physiological disturbances. The most significant results show an induction of CYP1A in both sexes and a decrease of 17beta-estradiol concentrations in females. Histopathological changes such as liver tissue degeneration were observed in fish exposed to 50 and 100% of the BKME. Although the BKME was biologically treated there are some chemical compounds in the effluent that are capable to affect fish physiology, however, a clear evidence for endocrine disruption was not found.

Three white-rot fungi (Pleurotus sajor caju, Trametes versicolor and Phanerochaete chrysosporium) and one soft-rot fungi (Rhizopus oryzae) species confirmed their potential for future applications in the biological treatment of effluents derived from the secondary treatment of a bleached kraft pulp mill processing Eucalyptus globulus. Among the four species P. sajor caju and R. oryzae were the most effective in the biodegradation of organic compounds present in the effluent, being responsible for the reduction of relative absorbance (25-46% at 250 nm and 72-74% at 465 nm) and of chemical oxygen demand levels (74 to 81%) after 10 days of incubation. Laccase (Lac), lignin (Lip) and manganese peroxidases (MnP) expression varied among fungal species, where Lac and LiP activities were correlated with the degradation of organic compounds in the effluent treated with P. sajor caju. The first two axes of a principal component analysis explained 88.9% of the total variation among sub-samples treated with the four fungus species, after different incubation periods. All the variables measured contributed positively to the first component except for the MnP enzyme activity which was the only variable contributing negatively to the first component. Absorbances at 465 nm, LiP and Lac enzyme activities were the variables with more weight on the second component. P. sajor caju revealed to be the only species able to perform the biological treatment without promoting an increment in the toxicity of the effluent to the Vibrio fischeri, as it was assessed by the Microtox assay. The opposite was recorded for the treatments with the other three species of fungus. EC(50-5 min) values ranging between 28 and 57% (effluent concentrations) were recorded even after 10 to 13 days of treatment with P. chrysosporium, R. oryzae or with T. versicolor.