UV Radiation and Protein Hydrolysates in Bio-Based Films: Impacts on Properties and Italian Salami Preservation.

UV radiation was combined with the incorporation of fish protein hydrolysates to improve the performance of active bio-based films for food packaging. UV radiation was not used previously to enhance the packaging performance of blend films of starch/protein, and fish protein hydrolysates were not incorporated in bio-based polymer surfaces previously. Rice starch and fish proteins (from Whitemouth croaker muscle) were utilized to prepare films by the casting technique, which were UV-radiated under different exposure times (1, 5, and 10 min). The packaging performance of the films was determined according to the mechanical and barrier performance, solubility, and color. Fish protein hydrolysates (from Argentine croaker muscle) were then incorporated into the films (bulk structure or surface). The results showed that UV radiation for 1 min increased the tensile strength and modified the optical properties of films. It also altered the structure of the polymeric matrix, as demonstrated by the microstructure and thermal analysis, in agreement with the data obtained in packaging properties. The evaluation of antioxidant capacity through 2,2-azino-bis-3-ethylbenzthiazoline-6-sulphonic acid (ABTS) and reducing power indicated that incorporating fish protein hydrolysates either in the films' bulk structure or film surface promoted antioxidant properties; control films (produced with rice starch/fish proteins without hydrolysates) also presented antioxidant potential. According to the peroxide value and thiobarbituric acid reactive substance (TBARS) assays, control films and the films containing hydrolysates in their bulk structure or on the surface could prevent the lipid oxidation of Italian salami. Thus, combining UV radiation to shape the characteristics of bio-based materials with fish protein hydrolysates to reduce lipid oxidation contributes to the performance of active bio-based films for food packaging.

Influence of microplastics and biogenic particles on the size spectra of tropical estuarine and marine pelagic ecosystems.

Size spectra analysis has been widely used to study pelagic ecosystems worldwide. It has a solid theoretical and empirical basis and can be used to provide useful information on ecosystem structure and trophic efficiency. The objective of this study was to obtain complete Normalized Biovolume Size Spectra (NBSS), including zooplankton, microplastics, and other suspended particles, along an estuary-shelf gradient. Plankton net samples (300 µm mesh) were obtained in the Rio Formoso Estuary, in Tamandaré Bay and on the continental shelf off Tamandaré, Brazil, during two years (from April/2013 to May/2015). Particles were identified by image analysis (ZooScan) and infrared spectroscopy (FTIR). Generally, NBSS slopes were close to -1 (i.e., between -1.09 and -0.85), except for NBSSz (zooplankton only) in the Estuary (-1.59) and in the Bay (-1.44), where the steepest slopes were observed, due to the importance of small-sized zooplankton in these areas. The NBSSz slope was significantly steeper in the Estuary and in the Bay than on the Shelf. The inclusion of particles into the NBSS (NBSSp) turned the slope significantly less steep in the Estuary and in the Bay. Intercepts were significantly higher in the Estuary than in the other areas, after including particles in the analysis (NBSSp), due to the extremely high total volume of biogenic particles in the estuary. The most relevant impacts of microplastics were detected within the larger size classes (> 2.60 mm Feret length, > 0.58 log10 mm3). In the Estuary, large-sized microplastics were similarly important (in terms of volume) as zooplankton. Large-sized polyethylene and polypropylene were more relevant in the Bay, large-sized nylon fibers on the Shelf (in the rainy season). The present study, a pioneering effort towards a synthetic analysis of zooplankton, microplastics, and other particles, highlights the importance of including non-living particles in size-based studies and ecosystem models.

Assessing the Plastisphere from Floating Plastics in the Northwestern Mediterranean Sea, with Emphasis on Viruses.

Plastics in the ocean create the "plastisphere", a diverse habitat hosting various life forms. Other than the pollution induced by plastics, the co-occurrence of primary producers, symbiotic organisms, decomposers, and pathogens within the plastisphere raises questions about how they influence the dynamics of marine ecosystems. Here, we used a shotgun DNA-sequencing approach to describe the species thriving on floating plastics collected in two Mediterranean sites. Our findings revealed many species of bacteria, eukaryotes, viruses, and archaea on each plastic. Proteobacteria was dominant (70% of reads in the entire dataset), with other groups such as Ascomycota fungi (11%) and Bacteroidetes (9%) also being represented. The community structure was not affected by the polymeric composition or the plastic shape. Notably, pathogenic Vibrio species, including V. campbelli, V. alginolyticus, and V. coralliilyticus, were among the most abundant species. Viruses, despite showing lower relative abundances, occurred in all samples, especially Herpesvirales, Caudovirales, and Poxviridae groups. A significant finding was the presence of the White Spot Syndrome virus (WSSV). This pathogen, responsible for devastating outbreaks in aquaculture systems, had not been previously reported in the marine plastisphere. Our study emphasizes the need for further investigation into the ecological and economic impacts of plastisphere organisms in the ocean.

Influence of UV exposure time and simulated marine environment on different microplastic degradation.

This study investigated the influence of environmental factors (UV radiation and salinity) in the degradative process of microplastics (MPs). MPs derived from polypropylene (PP), polystyrene (PS), and ethylene-vinyl acetate (EVA) were subjected to accelerated photodegradation while being submerged in distilled water or artificial seawater. Depending on the polymer, changes in surface properties, new functional chemical group formation and oxidative index, and thermal characteristics of samples were observed. After photodegradation experiments, EVA-MPs samples showed an increase in their thermal resistance, besides the changes in their surface. PP-MPs crystallinity index increased upon exposure to UV radiation. PS samples showed a higher carbonyl and hydroxyl index after 30 h of UV exposure. The methodology exploited applies to any location in the world and can be comparable once considering the total ultraviolet index (UVI). The saline medium increases the crystallinity index of PP and EVA-MPs samples and intensifies the formation of new carbonyl and hydroxyl bonds in EVA-MPs samples. The results showed that several environmental factors should be considered in interpreting MPs photodegradation.

Floating plastics and their associated biota in the Western South Atlantic.

The lack of information about plastic pollution in many marine regions hinders firm actions to manage human activities and mitigate their impacts. This study conducted for the first time a quali-quantitative evaluation of floating plastics and their associated biota from coastal and oceanic waters in South Brazil. Plastics were collected using a manta net, and were categorized according to their shape, size, malleability and polymer composition. Multi-marker DNA metabarcoding (16S, and 18S V4 and V9 rRNA regions) was performed to identify prokaryotes and eukaryotes associated to plastics. We found 371 likely plastic particles of several sizes, shapes and polymers, and the average concentration of plastics at the region was 4461 items.km-2 (SD ± 3914). Microplastics (0.5 - 5 mm) were dominant in most sampling stations, with fragments and lines representing the most common shapes. Diverse groups of prokaryotes (20 bacteria phyla) and eukaryotes (41 groups) were associated with plastics. Both the community composition and richness of epiplastic organisms were highly variable between individual plastics but, in general, were not influenced by plastic categories. Organisms with potential pathogenicity (e.g. Vibrio species. and Alexandrium tamarense), as well as potential plastic degraders (e.g. Ralstonia, Pseudomonas, and Alcanivorax species), were found. The information generated here is pivotal to support strategies to prevent the input and mitigate the impacts of plastics and their associated organisms on marine environments.

A fresh look at microplastics and other particles in the tropical coastal ecosystems of Tamandaré, Brazil.

Plankton organisms, biogenic particles, inorganic mineral particles, and microplastics are the four main components of particulate organic matter in aquatic ecosystems. We propose a new index, the Relative Microplastics Concentration (RMC, in %), considering that microplastics are more deleterious when food is scarce. A total of 112 plankton net samples were collected in estuarine, coastal and shelf environments of Tamandaré, Brazil. Particles were identified by image analysis (ZooScan) and FTIR. Higher concentrations of total microplastics, PP (Polypropylene) and PE (Polyethylene) in the estuary indicate an oceanward decreasing gradient from terrestrial sources. Higher concentrations of nylon fibres were found offshore. Yet, RMC indicated that the Bay had the most severely impacted ecosystems (RMC: 2.4% in the estuary, 5.1% in the Bay, and 2.0% on the shelf), for total microplastics and PP & PE. Shelf ecosystems were most severely impacted with nylon fibres. RMC analysis provided a new perspective into the impact of microplastics on tropical coastal food webs.

Ingestion of plastic debris by commercially important marine fish in southeast-south Brazil.

Rising concentrations of plastics in the oceans are leading to increasing negative interactions with marine biota, including ingestion by endangered and/or economically important seafood species such as fish. In this paper, we visually evaluated plastic debris ingestion by 965 specimens of eight commercially exploited fish species from different marine habitats off the southeast-south coast of Brazil. All species ingested plastics, with pelagic animals having higher amounts, frequency of occurrence, diversity and sizes of ingested items than demersal-pelagic and demersal animals. Highest frequency of occurrence (FO%) of plastic ingestion (25.8%) was observed for the pelagic skipjack tuna Katsuwonus pelamis (Scombridae), and lowest (5%) for the demersal bluewing searobin Prionotus punctatus (Triglidae). Microplastics predominated in all species, and fibers/lines and fragments were the main items found, possibly derived from fishing materials. The most abundant plastic colors were transparent, black and blue, and the most common polymers were polyamide and polyurethane. With the available data, no relationship between the size of the individuals and amount of ingested plastics was observed. Considering the negative impacts of plastic ingestion on marine fish, and potentially on human health due to their consumption, understanding ingestion patterns is critical for better evaluating their origin and possible causes, and consequently for helping define prevention strategies for this problem.

Plastics in sea surface waters around the Antarctic Peninsula.

Although marine plastic pollution has been the focus of several studies, there are still many gaps in our understanding of the concentrations, characteristics and impacts of plastics in the oceans. This study aimed to quantify and characterize plastic debris in oceanic surface waters of the Antarctic Peninsula. Sampling was done through surface trawls, and mean debris concentration was estimated at 1,794 items.km-2 with an average weight of 27.8 g.km-2. No statistical difference was found between the amount of mesoplastics (46%) and microplastics (54%). We found hard and flexible fragments, spheres and lines, in nine colors, composed mostly of polyurethane, polyamide, and polyethylene. An oceanographic dispersal model showed that, for at least seven years, sampled plastics likely did not originate from latitudes lower than 58°S. Analysis of epiplastic community diversity revealed bacteria, microalgae, and invertebrate groups adhered to debris. Paint fragments were present at all sampling stations and were approximately 30 times more abundant than plastics. Although paint particles were not included in plastic concentration estimates, we highlight that they could have similar impacts as marine plastics. We call for urgent action to avoid and mitigate plastic and paint fragment inputs to the Southern Ocean.

Ingestion of plastic marine litter by sea turtles in southern Brazil: abundance, characteristics and potential selectivity.

The ingestion of plastic marine litter (PML) by sea turtles is widespread and concerning, and the five species that occur in the southwestern Atlantic - green, loggerhead, olive ridley, leatherback and hawksbill - are vulnerable to this pollution. Here, we quantified and characterized PML ingested by these species in southern Brazil, and observed PML ingestion in 49 of 86 sampled individuals (~57.0%). Green turtles presented the highest rates and variety of ingested plastics, and such ingestion has been high at least since 1997. Omnivorous turtles presented higher PML ingestion than carnivorous ones. Loggerheads displayed a negative correlation between body size and number of ingested items. Green turtles ingested mostly flexible transparent and flexible/hard white plastics; loggerheads ate mainly flexible, hard and foam fragments, in white and black/brown colors. These results help us better understand PML ingestion by sea turtles, highlighting the seriousness of this threat and providing information for prevention and mitigation strategies.

UV-Surface Treatment of Fungal Resistant Polyether Polyurethane Film-Induced Growth of Entomopathogenic Fungi.

Synthetic polymers are the cause of some major environmental impacts due to their low degradation rates. Polyurethanes (PU) are widely used synthetic polymers, and their growing use in industry has produced an increase in plastic waste. A commercial polyether-based thermoplastic PU with hydrolytic stability and fungus resistance was only attacked by an entomopathogenic fungus, Metarhiziumanisopliae, when the films were pre-treated with Ultraviolet (UV) irradiation in the presence of reactive atmospheres. Water contact angle, Fourier transform infrared spectroscopy in attenuated total reflection mode (FTIR-ATR), scanning electron microscopy (SEM), and profilometer measurements were mainly used for analysis. Permanent hydrophilic PU films were produced by the UV-assisted treatments. Pristine polyether PU films incubated for 10, 30, and 60 days did not show any indication of fungal growth. On the contrary, when using oxygen in the UV pre-treatment a layer of fungi spores covered the sample, indicating a great adherence of the microorganisms to the polymer. However, if acrylic acid vapors were used during the UV pre-treatment, a visible attack by the entomopathogenic fungi was observed. SEM and FTIR-ATR data showed clear evidence of fungal development: growth and ramifications of hyphae on the polymer surface with the increase in UV pre-treatment time and fungus incubation time. The results indicated that the simple UV surface activation process has proven to be a promising alternative for polyether PU waste management.

Selective Fragmentation of Radiation-Sensitive Novel Polymeric Resist Materials by Inner-Shell Irradiation.

Two key concepts in extreme ultraviolet lithography (EUVL) are important for it to be a candidate for the mass production of future integrated circuits: the polymer formulation and the photofragmentation process. In this work, both concepts were carefully studied. The design and synthesis of radiation-sensitive organic polymeric materials based on the inclusion of a radiation-sensitive tetrahydrothiophenium functional group are outlined. A 1-(4-methacryloyoxy)naphthalene-1-yl)tetrahydro-1H-thiophenium trifluoromethanesulfonate (MANTMS) monomer containing the tetrahydrothiophenium group undergoes homo- and copolymerizations using free-radical polymerization with a 2,2'-azobis(isobutyronitrile) initiator. The surface photodegradation and oxidation of these novel polymeric materials were investigated using highly monochromatized soft X-rays from synchrotron radiation at the carbon K-edge excitation region. An efficient functionalization was observed when the excitation energy was tuned to C 1s → π*C═C. A high rate of defluorination and a loss of sulfonated groups as a result of an increase in the irradiation time for the MANTMS homopolymer thin films were mainly observed under the π*C═C excitation of the naphthyl functional groups. On the contrary, excitation similar to C 1s → π*C═O or C 1s → σ*C-F did not produce important degradation, showing a highly selective process of bond breaking. Additionally, the presence of methyl methacrylate copolymer in the original MANTMS yielded a much higher degree of stability against inner-shell radiation damage. Our results highlight the importance of choosing the right polymer formulation and excitation energy to produce a sensitive material for EUVL without using the concept of chemical amplification.

Radiation-sensitive novel polymeric resist materials: iterative synthesis and their EUV fragmentation studies.

Polymerization of (4-(methacryloyloxy)phenyl)dimethylsulfoniumtriflate (MAPDST), as a key monomer containing the radiation sensitive sulfonium functionality, with various other monomers such as methyl methacrylate (MMA), 4-carboxy styrene (STYCOOH), N-vinyl carbazole (NVK) in different molar ratios via free-radical polymerization method is described. This methodology led to the development of a small chemical library of six different radiation sensitive polymers for lithography applications. Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy identified the reaction products as MAPDST homopolymer and MAPDST-MMA, MAPDST-STYCOOH, MAPDST-NVK copolymers. Molecular weights were obtained from gel permeation chromatography and the decomposition temperature (Td) values were determined using thermogravimetric analysis (TGA). The effect of extreme ultraviolet (EUV) irradiation on a thin poly(MAPDST) film was investigated using monochromatic synchrotron excitation. These new polymeric materials were also exposed to electron-beam lithography (EBL) and extreme ultraviolet lithography (EUVL) to achieve 20-nm line patterns.

Biodegradation improvement of poly(3-hydroxy-butyrate) films by entomopathogenic fungi and UV-assisted surface functionalization.

Ultraviolet (UV)-assisted surface modification in the presence of oxygen was used as initial step to achieve controlled degradation of poly(3-hydroxy-butyrate), PHB, films by entomopathogenic fungi. Treated surfaces were investigated by surface analysis techniques (water contact angle, Fourier Transformed Infrared Spectroscopy in Attenuated Total Reflectance mode, X-ray Photoelectron Spectroscopy, Near-edge X-ray Absorption Fine Structure, Gel Permeation Chromatography, Optical Microscopy, Scanning Electron Microscopy, and weight loss). After the UV-assisted treatments, new carbonyl groups in new chemical environments were detected by XPS and NEXAFS spectroscopy. The oxidizing atmosphere did not allow the formation of CC bonds, indicating that Norrish Type II mechanism is suppressed during or by the treatments. The higher hydrophilicity and concentration of oxygenated functional groups at the surface of the treated films possibly improved the biodegradation of the films. It was observed a clear increase in the growth of this fungus when oxygenated groups were grafted on the polymers surfaces. This simple methodology can be used to improve and control the degradation rate of PHB films in applications that require a controllable degradation rate.