Understanding Interface Exchanges for Assessing Environmental Sorption of Additives from Microplastics: Current Knowledge and Perspectives.

Although the impacts of plastic pollution have long been recognized, the presence, pervasiveness, and ecotoxicological consequences of microplastic-i.e., plastic particles < 5 mm-contamination have only been explored over the last decade. Far less focus has been attributed to the role of these materials and, particularly, microplastics, as vectors for a multitude of chemicals, including those (un)intentionally added to plastic products, but also organic pollutants already present in the environment. Owing to the ubiquitous presence of microplastics in all environmental matrices and to the diverse nature of their chemical and physical characteristics, thoroughly understanding the mechanistic uptake/release of these compounds is inherently complex, but necessary in order to better assess the potential impacts of both microplastics and associated chemicals on the environment. Herein, we delve into the known processes and factors affecting these mechanisms. We center the discussion on microplastics and discuss some of the most prominent ecological implications of the sorption of this multitude of chemicals. Moreover, the key limitations of the currently available literature are described and a prospective outlook for the future research on the topic is presented.

An urgent call to think globally and act locally on landfill disposable plastics under and after covid-19 pandemic: Pollution prevention and technological (Bio) remediation solutions.

Landfilling and illegal waste disposal have risen to deal with the COVID-19 potentially infectious waste, particularly in developing countries, which aggravates plastic pollution and inherent environmental threats to human and animal health. It is estimated that 3.5 million metric tonnes of masks (equivalent to 601 TIR containers) have been landfilled worldwide in the first year, with the potential to increase global plastic municipal solid waste by 3.5%, alter biogas composition, and release 2.3 × 1021 microplastics to leachates or adjacent environments, in the coming years. This paper reviews the challenges raised in the pandemic scenario on landfills and discusses the potential environmental and health implications that might drive us apart from the 2030 U.N. sustainable goals. Also, it highlights some innovative technologies to improve waste management (from collection to disposal, waste reduction, sterilization) and mitigates plastic leakage (emission control approaches, application of biotechnological and monitoring/computational tools) that can pave the way to environmental recovery. COVID-19 will eventually subside, but if no action is taken in the short-term towards effective plastic policies, replacement of plastics for sustainable alternatives (e.g., biobased plastics), improvement of waste management streams (prioritising flexible and decentralized approaches), and a greater awareness and responsibility of the general public, stakeholders, industries; we will soon reach a tipping-point in natural environments worldwide.

Increased plastic pollution due to COVID-19 pandemic: Challenges and recommendations.

Plastics have become a severe transboundary threat to natural ecosystems and human health, with studies predicting a twofold increase in the number of plastic debris (including micro and nano-sized plastics) by 2030. However, such predictions will likely be aggravated by the excessive use and consumption of single-use plastics (including personal protective equipment such as masks and gloves) due to COVID-19 pandemic. This review aimed to provide a comprehensive overview on the effects of COVID-19 on macroplastic pollution and its potential implications on the environment and human health considering short- and long-term scenarios; addressing the main challenges and discussing potential strategies to overcome them. It emphasises that future measures, involved in an emergent health crisis or not, should reflect a balance between public health and environmental safety as they are both undoubtedly connected. Although the use and consumption of plastics significantly improved our quality of life, it is crucial to shift towards sustainable alternatives, such as bio-based plastics. Plastics should remain in the top of the political agenda in Europe and across the world, not only to minimise plastic leakage and pollution, but to promote sustainable growth and to stimulate both green and blue- economies. Discussions on this topic, particularly considering the excessive use of plastic, should start soon with the involvement of the scientific community, plastic producers and politicians in order to be prepared for the near future.

COVID-19 Pandemic Repercussions on the Use and Management of Plastics.

Plastics are essential in society as a widely available and inexpensive material. Mismanagement of personal protective equipment (PPE) during the COVID-19 pandemic, with a monthly estimated use of 129 billion face masks and 65 billion gloves globally, is resulting in widespread environmental contamination. This poses a risk to public health as waste is a vector for SARS-CoV-2 virus, which survives up to 3 days on plastics, and there are also broad impacts to ecosystems and organisms. Concerns over the role of reusable plastics as vectors for SARS-CoV-2 virus contributed to the reversal of bans on single-use plastics, highly supported by the plastic industry. While not underestimating the importance of plastics in the prevention of COVID-19 transmission, it is imperative not to undermine recent progress made in the sustainable use of plastics. There is a need to assess alternatives that allow reductions of PPE and reinforce awareness on the proper public use and disposal. Finally, assessment of contamination and impacts of plastics driven by the pandemic will be required once the outbreak ends.

Structural Features and Pro-Inflammatory Effects of Water-Soluble Organic Matter in Inhalable Fine Urban Air Particles.

The impact of inhalable fine particulate matter (PM2.5, aerodynamic diameter <2.5 µm) on public health is of great concern worldwide. Knowledge on their harmful effects are mainly due to studies carried out with whole air particles, with the contribution of their different fractions remaining largely unknown. Herein, a set of urban PM2.5 samples were collected during daytime and nighttime periods in autumn and spring, aiming to address the seasonal and day-night variability of water-soluble organic matter (WSOM) composition. In vitro analysis of the oxidative and pro-inflammatory potential of WSOM samples was carried out in both acute (24 h) and chronic (3 weeks) exposure setups using Raw264.7 macrophages as cell model. Findings revealed that the structural composition of WSOM samples differs between seasons and in a day-night cycle. Cell exposure resulted in an increase in the transcription of the cytoprotective Hmox1 and pro-inflammatory genes Il1b and Nos2, leading to a moderate pro-inflammatory status. These macrophages showed an impaired capacity to subsequently respond to a strong pro-inflammatory stimulus such as bacterial lipopolysaccharide, which may implicate a compromised capacity to manage harmful pathogens. Further investigation on aerosol WSOM could help to constrain the mechanisms of WSOM-induced respiratory diseases and contribute to PM2.5 regulations.

Environmental status of (micro)plastics contamination in Portugal.

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.

Sargassum muticum and Osmundea pinnatifida Enzymatic Extracts: Chemical, Structural, and Cytotoxic Characterization.

Seaweeds, which have been widely used for human consumption, are considered a potential source of biological compounds, where enzyme-assisted extraction can be an efficient method to obtain multifunctional extracts. Chemical characterization of Sargassum muticum and Osmundea pinnatifida extracts obtained by Alcalase and Viscozyme assisted extraction, respectively, showed an increment of macro/micro elements in comparison to the corresponding dry seaweeds, while the ratio of Na/K decreased in both extracts. Galactose, mannose, xylose, fucose, and glucuronic acid were the main monosaccharides (3.2-27.3 mg/glyophilized extract) present in variable molar ratios, whereas low free amino acids content and diversity (1.4-2.7 g/100gprotein) characterized both extracts. FTIR-ATR and 1H NMR spectra confirmed the presence of important polysaccharide structures in the extracts, namely fucoidans from S. muticum or agarans as sulfated polysaccharides from O. pinnatifida. No cytotoxicity against normal mammalian cells was observed from 0 to 4 mglyophilized extract/mL for both extracts. The comprehensive characterization of the composition and safety of these two extracts fulfils an important step towards their authorized application for nutritional and/or nutraceutical purposes.

Degradation of polyethylene microplastics in seawater: Insights into the environmental degradation of polymers.

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.

Recent Progress in Biosensors for Environmental Monitoring: A Review.

The environmental monitoring has been one of the priorities at the European and global scale due to the close relationship between the environmental pollution and the human health/socioeconomic development. In this field, the biosensors have been widely employed as cost-effective, fast, in situ, and real-time analytical techniques. The need of portable, rapid, and smart biosensing devices explains the recent development of biosensors with new transduction materials, obtained from nanotechnology, and for multiplexed pollutant detection, involving multidisciplinary experts. This review article provides an update on recent progress in biosensors for the monitoring of air, water, and soil pollutants in real conditions such as pesticides, potentially toxic elements, and small organic molecules including toxins and endocrine disrupting chemicals.

Review of the ecotoxicological effects of emerging contaminants to soil biota.

In recent years, emerging contaminants (e.g. pesticides and their metabolites, pharmaceuticals, personal and house care products, life-style compounds, food additives, industrial products and wastes, as well as nanomaterials) have become a problem to the environment. In fact, the cumulative use of a panoply of chemical substances in agriculture, industrial activities, in our homes and in health care services has led to their recent appearance in detectable levels in soils, surface, and groundwater resources, with unpredictable consequences for these ecosystems. Few data exist regarding the toxicity and potential for bioaccumulation in biota. When available, data were obtained only for some representatives of the main groups of chemical substances, and for a limited number of species, following non-standard protocols. This makes difficult the calculation of predicted no effect concentrations (PNEC) and the existence of sufficient data to set limits for their release into the environment. This is particularly concerning for the soil compartment, since only recently the scientific community, regulators, and the public have realised the importance of protecting this natural resource and its services to guarantee the sustainability of terrestrial ecosystems and human well-being. In this context, this review paper aims to identify the major groups of soil emerging contaminants, their sources, pathways and receptors, and in parallel to analyse existing ecotoxicological data for soil biota.

Critical overview on the application of sensors and biosensors for clinical analysis.

Sensors and biosensors have been increasingly used for clinical analysis due to their miniaturization and portability, allowing the construction of diagnostic devices for point-of-care testing. This paper presents an up-to-date overview and comparison of the analytical performance of sensors and biosensors recently used in clinical analysis. This includes cancer and cardiac biomarkers, hormones, biomolecules, neurotransmitters, bacteria, virus and cancer cells, along with related significant advances since 2011. Some methods of enhancing the analytical performance of sensors and biosensors through their figures of merit are also discussed.

Transport phenomena of nanoparticles in plants and animals/humans.

The interaction of a plethora nanoparticles with major biota such as plants and animals/humans has been the subject of various multidisciplinary studies with special emphasis on toxicity aspects. However, reports are meager on the transport phenomena of nanoparticles in the plant-animal/human system. Since plants and animals/humans are closely linked via food chain, discussion is imperative on the main processes and mechanisms underlying the transport phenomena of nanoparticles in the plant-animal/human system, which is the main objective of this paper. Based on the literature appraised herein, it is recommended to perform an exhaustive exploration of so far least explored aspects such as reproducibility, predictability, and compliance risks of nanoparticles, and insights into underlying mechanisms in context with their transport phenomenon in the plant-animal/human system. The outcomes of the suggested studies can provide important clues for fetching significant benefits of rapidly expanding nanotechnology to the plant-animal/human health-improvements and protection as well.

Nanoscale copper in the soil-plant system - toxicity and underlying potential mechanisms.

Nanoscale copper particles (nano-Cu) are used in many antimicrobial formulations and products for their antimicrobial activity. They may enter deliberately and/or accidentally into terrestrial environments including soils. Being the major 'eco-receptors' of nanoscale particles in the terrestrial ecosystem, soil-microbiota and plants (the soil-plant system) have been used as a model to dissect the potential impact of these particles on the environmental and human health. In the soil-plant system, the plant can be an indirect non-target organism of the soil-associated nano-Cu that may in turn affect plant-based products and their consumers. By all accounts, information pertaining to nano-Cu toxicity and the underlying potential mechanisms in the soil-plant system remains scanty, deficient and little discussed. Therefore, based on some recent reports from (bio)chemical, molecular and genetic studies of nano-Cu versus soil-plant system, this article: (i) overviews the status, chemistry and toxicity of nano-Cu in soil and plants, (ii) discusses critically the poorly understood potential mechanisms of nano-Cu toxicity and tolerance both in soil-microbiota and plants, and (iii) proposes future research directions. It appears from studies hitherto made that the uncontrolled generation and inefficient metabolism of reactive oxygen species through different reactions are the major factors underpinning the overall nano-Cu consequences in both the systems. However, it is not clear whether the nano-Cu or the ion released from it is the cause of the toxicity. We advocate to intensify the multi-approach studies focused at a complete characterization of the nano-Cu, its toxicity (during life cycles of the least-explored soil-microbiota and plants), and behavior in an environmentally relevant terrestrial exposure setting. Such studies may help to obtain a deeper insight into nano-Cu actions and address adequately the nano-Cu-associated safety concerns in the 'soil-plant system'.

Unraveling the structural features of organic aerosols by NMR spectroscopy: a review.

Our limited understanding of the effect of organic aerosols (OAs) on the climate and human health is largely because of the vast array of formation processes and sources that produce a multitude of molecular structures and physical properties. The need to unravel the enormous complexity and heterogeneity of OAs and thus understand their effects on the climate and human health has led to the development of different off-line methods based on the use of advanced analytical techniques. Within this context, nuclear magnetic resonance (NMR) spectroscopy has become essential for acquiring detailed structural characterization of the complex natural organic matter contained in atmospheric aerosols. In this article, we present a critical review on the application of NMR spectroscopy in OAs (primary and secondary) studies, focusing mainly on the water-soluble organic fraction, and how NMR has impacted our knowledge on atmospheric organic matter. A major emphasis is given on the wealth of chemical information that solid-state and multi-dimensional solution-state NMR can provide, including the sources, formation pathways, seasonal, and regional characterization of atmospheric OAs. Finally, major challenges are discussed and recommendations for future research directions are proposed.

Halimione portulacoides (L.) physiological/biochemical characterization for its adaptive responses to environmental mercury exposure.

This study investigates largely unexplored physiological/biochemical strategies adopted by salt marsh macrophyte Halimione portulacoides (L.) Aellen for its adaptation/tolerance to environmental mercury (Hg)-exposure in a coastal lagoon prototype. To this end, a battery of damage (hydrogen peroxide, H2O2; thiobarbituric acid reactive substances, TBARS; electrolyte leakage, EL; reactive carbonyls; osmolyte, proline) and defense [ascorbate peroxidase, APX; catalase, CAT; glutathione peroxidase, GPX; glutathione sulfo-transferase, GST; glutathione reductase, GR; reduced and oxidized glutathione (GSH and GSSG, respectively), and GSH/GSSG ratio] biomarkers, and polypeptide patterns were assessed in H. portulacoides roots and leaves at reference (R) and the sites with highest (L1), moderate (L2) and the lowest (L3) Hg-contamination gradients. Corresponding to the Hg-burdens, roots and leaves exhibited a differential modulation of damage- and defense-endpoints and polypeptide-patterns. Roots exhibiting the highest Hg-burden (at L3) failed to maintain a coordination among enzymatic-defense endpoint responses which resulted into increased oxidation of reduced glutathione (GSH) pool, lowest GSH/GSSG (oxidized) ratio and partial H2O2-metabolism. In contrast, the highest Hg-burden exhibiting leaves (at L1) successfully maintained a coordination among enzymatic-defense endpoints responses which resulted into decreased GSH-oxidation, enhanced reduced GSH pool and GSH/GSSG ratio and lower extent of damage. Additionally, increased leaf-carotenoids content with increasing Hg-burden implies its protective function. H. portulacoides leaf-polypeptides did not respond as per its Hg-burden but the roots did. Overall, the physiological/biochemical characterization of below (roots)- and above (leaves)-ground organs (studied in terms of damage and defense endpoints, and polypeptides modulation) revealed the adaptive responses of H. portulacoides to environmental Hg at whole plant level which cumulatively helped this plant to sustain and execute its Hg-remediation potential.

The impact of uranium mine contamination of soils on plant litter decomposition.

As part of a tier 3 risk assessment performed for a uranium mining area, the ability of soils with different degrees of metal contamination to degrade organic matter was assessed using litter bags filled with leaves of Quercus robur, Pinus pinaster, Salix atrocinerea, or a mixture of the three species. Litter bags were exposed at different sites within the mine area and at a reference area for 3, 6, 9, and 12 months. Biomass loss, nitrogen (N), phosphorus (P), carbon (C) and total fatty acid, total phenolic, and ergosterol contents were assessed for each litter bag retrieved from the field. The decomposition of litter at each site seemed to be governed by a complex interaction of many different factors. After 12 months of exposure, leaves from the most contaminated sites were distinguishable from those from the reference site. In the reference site, the greatest percentages of biomass loss were attained by Q. robur and P. pinaster leaves. These species displayed the second highest and the lowest C-to-N ratios, respectively. In addition, the high P content of the litter from these two species may have favored microbial colonization. The results suggest that the decomposition of P. pinaster and Q. robur leaves may have been favored at the reference site by the high abundance of both species at this site and the subsequent adaptation of the microbial community to their litter. Our study shows that different species of leaf litter should be used to discriminate between contaminated sites with different levels of contamination.

Dissolved organic and inorganic matter in bulk deposition of a coastal urban area: an integrated approach.

Bulk deposition can remove atmospheric organic and inorganic pollutants that may be associated with gaseous, liquid or particulate phases. To the best of our knowledge, few studies have been carried out, which simultaneously analyse the presence of organic and inorganic fractions in rainwater. In the present work, the complementarity of organic and inorganic data was assessed, through crossing data of some organic [DOC (dissolved organic carbon), absorbance at 250 nm (UV250nm), integrated fluorescence] and inorganic [H(+), NH4(+), NO3(-), non sea salt sulphate (NSS-SO4(2-))] parameters measured in bulk deposition in the coastal urban area of Aveiro. The organic and inorganic parameters analysed were positively correlated (p<0.001) except for H(+), which suggests that a constant fraction of chromophoric dissolved organic matter (CDOM) came from anthropogenic sources. Furthermore, the inverse correlations observed for the organic and inorganic parameters with the precipitation amount suggest that organic and inorganic fractions were incorporated into the rainwater partially by below-cloud scavenging of airborne particulate matter. This is in accordance with the high values of DOC and NO3(-) found in samples associated with marine air masses, which were linked in part to the contribution of local emissions from vehicular traffic. DOC of bulk deposition was the predominant constituent when compared with the constituents H(+), NH4(+), NO3(-) and NSS-SO4(2-), and consequently bulk deposition flux was also highest for DOC, highlighting the importance of DOC and of anthropogenic ions being simultaneously removed from the atmosphere by bulk deposition. However, it was verified that the contribution of anthropogenic sources to the DOC of bulk deposition may be different for distinct urban areas. Thus, it is recommended that organic and inorganic fractions of bulk deposition are studied together.

A multidisciplinary approach to evaluate the efficiency of a clean-up technology to remove mercury from water.

A microporous material denoted ETS-4 was used as the decontaminant agent to treat water with a low level of Hg contamination. The effectiveness of the treatment was evaluated by assessment of the efficiency of Hg removal and ecotoxicological responses. The results showed that under highly competitive conditions the removal of Hg ranged between 58 % and 73 % depending upon the initial Hg concentration, and that Hg removal was reflected in decreased toxicity to some organisms. The ecotoxicological data indicated that the bacterium Vibrio fischeri was the least sensitive organism tested, as no toxicity was observed in either pre- or post-treatment waters. Daphnia magna was highly sensitive to Hg. Mercury removal by ETS-4 was not sufficient to completely remove the toxicity of Hg to D. magna. However, it was effective in the complete reduction of toxicity for the green alga, Pseudokirchneriella subcapitata.

Competitive effects on mercury removal by an agricultural waste: application to synthetic and natural spiked waters.

In this work, the efficiency of a local and highly, available agricultural waste, the raw rice husk, was used to remove mercury (Hg) from synthetic and natural waters, spiked with concentrations that reflect the contamination problems found in the environment. Different operating conditions were tested, including initial pH, ionic strength, the presence of co-ions (cadmium) and organic matter. The sorption efficiency of rice husk was slightly affected by the presence H+ ions (pH range between 3 and 9), but in the presence of NaNO3 and NaCl electrolytes and in binary solutions containing Cd2+ and H2+, the sorption efficiency was dependent on the nature and levels of the interfering ion and on the initial concentration of Hg+ used. Nevertheless, in a situation of equilibrium the effect of those ions was negligible and the removal efficiency ranged between 82% and 94% and between 90% and 96% for an initial Hg2+ concentration of 0.05 mg L(-1) and 0.50 mg L(-1), respectively. In more complex matrices, i.e. in the presence ofhumic substances and in natural river waters, the speciation and dynamics of Hg was changed and a fraction of the metal becomes unavailable in solution. Even then, the values obtained for Hg removal were satisfactory, i.e. between 59% and 76% and 81% and 85% for an initial concentration of Hg2+ of 0.05 and 0.50 mg L(-1), respectively.

Biodegradation of e-waste microplastics by Penicillium brevicompactum.

Electronic and electric waste (e-waste) management strategies often fall short in dealing with the plastic constituents of printed circuit boards (PCB). Some plastic materials from PCB, such as epoxy resins, may release contaminants, but neither potential environmental impact has been assessed nor mitigation strategies have been put forward. This study assessed the biodegradation of microplastics (1-2 mm in size) from PCB by the fungus Penicillium brevicompactum over 28 days, thus contributing to the discussion of mitigation strategies for decreasing the environmental impact of such plastics in the environment. The capacity of P. brevicompactum to induce microplastic fragmentation and degradation has been determined by the increased the number of smaller-sized particles and microplastic mass reduction (up to 75 % within 14 days), respectively. The occurrence of chain scission and oxidation of microplastics exposed to P. brevicompactum when compared with the control conditions (which occurred only after 28 days of exposure) can be observed. Furthermore, Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy performed in dried biomass put in evidence an increase in the absorption intensities in regions that could be attributed to functional groups associated with carbohydrates. The results underline the potential role of the genus Penicillium, particularly P. brevicompactum, in the biodegradation of microplastics from PCB, thus providing the basis for further exploration of its potential for e-waste bioremediation and research on the underlying mechanisms for sustainable approaches to mitigate e-waste pollution.