Nitrate Removal by Donnan Dialysis and Anion-Exchange Membrane Bioreactor Using Upcycled End-of-Life Reverse Osmosis Membranes.

This work explores the application of Reverse Osmosis (RO) upcycled membranes, as Anion Exchange Membranes (AEMs) in Donnan Dialysis (DD) and related processes, such as the Ion Exchange Membrane Bioreactor (IEMB), for the removal of nitrate from contaminated water, to meet drinking water standards. Such upcycled membranes might be manufactured at a lower price than commercial AEMs, while their utilization reinforces the commitment to a circular economy transition. In an effort to gain a better understanding of such AEMs, confocal µ-Raman spectroscopy was employed, to assess the distribution of the ion-exchange sites through the thickness of the prepared membranes, and 2D fluorescence spectroscopy, to evaluate alterations in the membranes caused by fouling and chemical cleaning The best performing membrane reached a 56% average nitrate removal within 24 h in the DD and IEMB systems, with the latter furthermore allowing for simultaneous elimination of the pollutant by biological denitrification, thus avoiding its discharge into the environment. Overall, this work validates the technical feasibility of using RO upcycled AEMs in DD and IEMB processes for nitrate removal. This membrane recycling concept might also find applications for the removal and/or recovery of other target negatively charged species.

Microplastics and other anthropogenic particles in Antarctica: Using penguins as biological samplers.

Microplastics (< 5 mm in size) are known to be widespread in the marine environment but are still poorly studied in Polar Regions, particularly in the Antarctic. As penguins have a wide distribution around Antarctica, three congeneric species: Adélie (Pygoscelis adeliae), chinstrap (Pygoscelis antarcticus) and gentoo penguins (Pygoscelis papua) were selected to evaluate the occurrence of microplastics across the Antarctic Peninsula and Scotia Sea. Scat samples (used as a proxy of ingestion), were collected from breeding colonies over seven seasons between 2006 and 2016. Antarctic krill (Euphausia superba), present in scat samples, contributed 85%, 66% and 54% of the diet in terms of frequency of occurrence to the diet of Adélie, gentoo and chinstrap penguins, respectively. Microplastics were found in 15%, 28% and 29% scats of Adélie, chinstrap and gentoo penguin respectively. A total of 92 particles were extracted from the scats (n = 317) and 32% (n = 29) were chemically identified via micro-Fourier Transform Infrared Spectroscopy (µ-FTIR). From all the particles extracted, 35% were identified as microplastics, particularly polyethylene (80%) and polyester (10%). It was not possible to ascertain the identification of the remaining 10% of samples. Other anthropogenic particles were identified in 55% of samples, identified as cellulose fibres. The results show a similar frequency of occurrence of particles across all colonies, suggesting there is no particular point source for microplastic pollution in the Scotia Sea. Additionally, no clear temporal variation in the number of microplastics in penguins was observed. Overall, this study reveals the presence of microplastics across Antarctica, in three penguin species and offers evidence of other anthropogenic particles in high numbers. Further research is needed to better understand the spatio-temporal dynamics, fate and effect of microplastics on these ecosystems, and improve plastic pollution policies in Antarctica.

Pretreatment of Plastic Waste: Removal of Colorants from HDPE Using Biosolvents.

Plastics recycling remains a challenge due to the relatively low quality of the recycled material, since most of the developed recycling processes cannot deal with the additives present in the plastic matrix, so the recycled products end up in lower-grade applications. The application of volatile organic solvents for additives removal is the preferred choice. In this study, pretreatment of plastic packaging waste to remove additives using biosolvents was investigated. The plastic waste used was high-density polyethylene (HDPE) with blue and orange colorants (pigment and/or dye). The first step was to identify the type of colorants present in the HDPE, and we found that both plastics presented only one colorant that was actually a pigment. Then, limonene, a renewable solvent, was used to solubilize HDPE. After HDPE dissolution, a wide range of alcohols (mono-, di-, and tri-alcohols) was evaluated as antisolvents in order to selectively precipitate the polymer and maximize its purity. The use of limonene as solvent for plastic dissolution, in combination with poly-alcohols with an intermediate alkyl chain length and a large number of hydroxyl (OH) groups, was found to work best as an antisolvent (1,2,3-propanetriol and 1,2,4-butanetriol), leading to a removal of up to 94% and 100% of the blue and orange pigments, respectively. Finally, three cycles of extraction were carried out, proving the capability of the solvent and antisolvent to be recovered and reused, ensuring the economic viability and sustainability of the process. This pretreatment provides a secondary source of raw materials and revenue for the recycling process, which may lead to an increase in the quality of recycled polymers, contributing to the development of an economical and sustainable recycling process.

Microplastics in wild fish from North East Atlantic Ocean and its potential for causing neurotoxic effects, lipid oxidative damage, and human health risks associated with ingestion exposure.

Microplastics (MP) pollution has received increased attention over the last few years. However, while the number of studies documentating the ingestion of microplastics by fish has increased, fewer studies have addressed the toxicological effects derived from the ingestion of these small items in wild conditions. Here, MP contamination and effect biomarkers were investigated in three commercially important fish species from the North East Atlantic Ocean. From the 150 analysed fish (50 per species), 49 % had MP. In fish from the 3 species, MP in the gastrointestinal tract, gills and dorsal muscle were found. Fish with MP had significantly (p ≤ 0.05) higher lipid peroxidation levels in the brain, gills and dorsal muscle, and increased brain acetylcholinesterase activity than fish where no MP were found. These results suggest lipid oxidative damage in gills and muscle, and neurotoxicity through lipid oxidative damage and acetylcholinesterase induction in relation to MP and/or MP-associated chemicals exposure. From the 150 fish analysed, 32 % had MP in dorsal muscle, with a total mean (± SD) of 0.054 ± 0.099 MP items/g. Based on this mean and on EFSA recommendation for fish consumption by adults or the general population, human consumers of Dicentrachus labrax, Trachurus trachurus, Scomber colias may intake 842 MP items/year from fish consumption only. Based on the mean of MP in fish muscle and data (EUMOFA, NOAA) of fish consumption per capita in selected European and American countries, the estimated intake of microplastics through fish consumption ranged from 518 to 3078 MP items/year/capita. Considering that fish consumption is only one of the routes of human exposure to microplastics, this study and others in the literature emphasize the need for more research, risk assessment and adoption of measures to minimize human exposure to these particles. Thus, MP pollution and its effects should be further investigated and addressed according to the WHO 'One Health' approach.

Microplastics in gentoo penguins from the Antarctic region.

There is growing evidence that microplastic pollution (<5 mm in size) is now present in virtually all marine ecosystems, even in remote areas, such as the Arctic and the Antarctic. Microplastics have been found in water and sediments of the Antarctic but little is known of their ingestion by higher predators and mechanisms of their entry into Antarctic marine food webs. The goal of this study was to assess the occurrence of microplastics in a top predator, the gentoo penguin Pygoscelis papua from the Antarctic region (Bird Island, South Georgia and Signy Island, South Orkney Islands) and hence assess the potential for microplastic transfer through Antarctic marine food webs. To achieve this, the presence of microplastics in scats (as a proof of ingestion) was investigated to assess the viability of a non-invasive approach for microplastic analyses in Antarctic penguins. A total of 80 penguin scats were collected and any microplastics they contained were extracted. A total of 20% of penguin scats from both islands contained microplastics, consisting mainly of fibers and fragments with different sizes and polymer composition (mean abundance of microplastics: 0.23 ± 0.53 items individual-1 scat, comprising seven different polymers), which were lower values than those found for seabirds in other regions worldwide. No significant differences in microplastic numbers in penguin scats between the two regions were detected. These data highlight the need for further assessment of the levels of microplastics in this sensitive region of the planet, specifically studies on temporal trends and potential effects on penguins and other organisms in the Antarctic marine food web.

Occurrence of microplastics in commercial fish from a natural estuarine environment.

Microplastic ingestion has been reported for several marine species, but the level of contamination in transitional systems and associated biota is less known. The aim of this study was to assess the occurrence of microplastic ingestion in three commercial fish species: the sea bass (Dicentrarchus labrax), the seabream (Diplodus vulgaris) and the flounder (Platichthys flesus) from the Mondego estuary (Portugal). Microplastics were extracted from the gastrointestinal tract of 120 individuals by visual inspection and digestion solution. A total of 157 particles were extracted from 38% of total fish (96% fibers), with 1.67 ±â€¯0.27 (SD) microplastics per fish. Significantly higher amount of ingested microplastics was recorded for D. vulgaris (73%). The dominant polymers identified by µ-FTIR were polyester, polypropylene and rayon (semi-synthetic fiber). It is reported for the first time the presence of this pollutant in fish populations from the Mondego estuary raising concerns on their potential negative effects.

Plastic ingestion in oceanic-stage loggerhead sea turtles (Caretta caretta) off the North Atlantic subtropical gyre.

Juvenile oceanic-stage sea turtles are particularly vulnerable to the increasing quantity of plastic coming into the oceans. In this study, we analysed the gastrointestinal tracts of 24 juvenile oceanic-stage loggerheads (Caretta caretta) collected off the North Atlantic subtropical gyre, in the Azores region, a key feeding ground for juvenile loggerheads. Twenty individuals were found to have ingested marine debris (83%), composed exclusively of plastic items (primarily polyethylene and polypropylene) identified by µ-Fourier Transform Infrared Spectroscopy. Large microplastics (1-5mm) represented 25% of the total number of debris and were found in 58% of the individuals sampled. Average number of items was 15.83±6.09 (±SE) per individual, corresponding to a mean dry mass of 1.07±0.41g. The results of this study demonstrate that plastic pollution acts as another stressor for this critical life stage of loggerhead turtles in the North Atlantic.

Genome sequencing of three bacteria associated to black band disease from a Colombian reef-building coral.

We announce the draft genome sequence of three Gram-negative bacteria isolated from coral tissues affected with the black band disease (BBD), identified with the NCBI's Assembly Database accession numbers: MBQF, MAYB and MBQE. These genome drafts constitute an useful tool for the characterisation of these bacteria and for the understanding of the relationship between the microbial consortia associated with the disease and the onset and progression of the pathology.

A spectroscopic study of Brazilwood paints in medieval books of hours.

In this work, microspectrofluorimetry was for the first time applied to the identification of the red organic lakes that are characteristic of the lavish illuminations found in 15(th) century books of hours. Microspectrofluorimetry identified those red paints, ranging from opaque pink to dark red glazes, as brazilwood lakes. An unequivocal characterization was achieved by comparison with reference paints produced following recipes from the medieval treatise The Book on How to Make Colours, and was further confirmed by fiber optic reflectance spectroscopy (FORS). For these treasured cultural objects, microspectrofluorimetry and FORS proved to be the only techniques that could identify, in situ or in microsamples, the chromophore responsible for the pinkish hues: a brazilein-Al(3+) complex. Additionally, a multi-analytical approach provided a full characterization of the color paints, including pigments, additives, and binders. Microspectroscopic techniques, based on infrared and X-ray radiation, enabled us to disclose the full palette of these medieval manuscripts, including the elusive greens, for which, besides malachite, basic copper sulfates were found; Raman microscopy suggested a mixture of brochantite and langite. Infrared analysis proved invaluable for a full characterization of the additives that were applied as fillers or whites (chalk, gypsum, and white lead) as well as the proteinaceous and polysaccharide binders that were found pure or in mixture.

Characterisation of varnishes used in violins by pyrolysis-gas chromatography/mass spectrometry.

The correct characterisation and a detailed knowledge of the materials originally used in violin varnishes, like natural resins, is crucial for the conservation in museums and for a suitable restoration technique. The study presented here reports on the potential of pyrolysis (Py) coupled with gas chromatography (GC) and mass spectrometry (MS) for the identification of chemical markers of each resin; this technique is very sensitive and selective, it needs a small quantity of sample and does not require chemical treatments. To improve the chromatographic behaviour of polar compounds the derivatising agent tetramethylammonium hydroxide (TMAH) in combination with pyrolysis has been used, in the so-called TMAH thermochemolysis or thermally assisted hydrolysis and methylation (THM), or more simply pyrolysis-methylation. The natural resins studied were colophony, sandarac, manila copal, elemi, amber and benzoin, mainly composed of terpenic compounds, with the exception of the latter, composed of aromatic compounds. Many compounds were identified; in particular, methyl esters of resinous acids that, individually or in a group, can be used as chemical markers. However, through this technique it was not possible to distinguish between the sandarac and manila copal resins because their chromatographic behaviour is very similar. Finally, the procedure applied has been employed in the characterisation of original varnish samples.