Novel ultrasound assisted extraction and d-SPE clean-up for the analysis of multiple legacy and emerging organic contaminants in edible fish.

Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), phthalate esters (PAEs) are pervasive environmental pollutants, posing threats to both ecosystems and human health. Although several analytical methods were developed for these compounds, they are not performed simultaneously. This study addresses the need for a sustainable, novel, analytical approach capable of simultaneously determining these diverse chemical classes in edible fish muscles. Employing ultrasound extraction coupled with dispersive solid-phase extraction (d-SPE) as a cleanup procedure, the method was compared to conventional techniques, revealing significant improvements. Analytical parameters were thoroughly assessed, and the innovative method demonstrated notable advantages, reducing extraction and purification times by approximately 74-80 % and solvent consumption by around 94-97 %. Applied to Mediterranean Sea fish samples, the results underscore the method's potential as a viable, sustainable alternative to traditional approaches, promising enhanced efficiency and reduced environmental impact.

Microplastic occurrence and phthalate ester levels in neuston samples and skin biopsies of filter-feeding megafauna from La Paz Bay (Mexico).

The impacts of microplastics on filter feeders megafauna have recently received increased attention. These organisms are potentially exposed to plastic ingestion and the release of added/sorbed contaminants during feeding activities. An assessment of microplastic abundance and the chemical impact of Phthalates esters (PAEs) were performed in neustonic samples and skin biopsies of Balaenoptera physalus and Rhincodon typus inhabiting the Gulf of California (Mexico). Sixty-eight percent of the net tows contained plastics with a maximum of 0.24 items/m3 mainly composed of polyethylene fragments. PAE levels were detected both in environmental and skin biopsy samples, with the highest values in the fin whale specimens (5291 ng/g d.w). Plasticizer fingerprint showed a similar distribution pattern between neustonic samples and filter-feeding species, with DEHP and MBP having the highest concentrations. The detection of PAE levels confirmed their potential role as plastic tracers and give preliminary information about the toxicological status of these species feeding in La Paz Bay.

Bioplastics on marine sandy shores: Effects on the key species Talitrus saltator (Montagu, 1808).

Talitrid amphipods are an important component of detritus web, playing a key role in the fragmentation of organic matters of marine and terrestrial origin, and it is well known that sandhoppers ingest microplastics. To assess the effective consumption of bioplastics and their effects on survival rate and on pollutants transfer (i.e. phthalates) on supralittoral arthropods, laboratory experiments were conducted by feeding adult T. saltator with two different types of bioplastic commonly used in the production of shopping bags. Groups of about 20 individuals were fed with 10 × 10 cm sample sheets of the two types of bioplastic for four weeks. The results show that amphipods ingest bioplastics even in the absence of microbial film and that ingestion of bioplastic can have effects on talitrid amphipods. Microtomographic analyses of faecal pellets seem consistent with this finding. The high phthalate concentrations in freshly collected individuals suggest the presence in the environment of these compounds, and the ability of amphipods to assimilate them, while the decrease in phthalate concentrations in bioplastic-fed individuals could be attributed to the scavenging effect of virgin plastic, as already observed in a previous study. In summary, the results indicate that different bioplastics may have effects on T. saltator (i.e. survival rate and faecal pellets structure) and confirm a potential role of amphipods in the degradation of bioplastics in supralittoral zone of marine sandy beaches, even when bioplastics are not colonized by bacterial biofilm that seems to improve palatability.

Ingestion of microplastics and textile cellulose particles by some meiofaunal taxa of an urban stream.

Microplastics (MPs) and textile cellulose are globally pervasive pollutants in freshwater. In-situ studies assessing the ingestion of MPs by freshwater meiofauna are few. Here, we evaluated MP and textile cellulose ingestion by some meiofaunal taxa and functional guilds of a first-order stream in the city of Florence (Italy) by using a tandem microscopy approach (fluorescence microscopy and µFTIR). The study targeted five taxa (nematodes, oligochaetes, copepods, ephemeropterans and chironomids), three feeding (scrapers, deposit-feeders, and predators), and three locomotion (crawlers, burrowers, and swimmers) guilds. Fluorescent particles related to both MPs and textile cellulose resulted in high numbers in all taxa and functional guilds. We found the highest number of particles in nematodes (5200 particles/ind.) and deposit-feeders (1693 particles/ind.). Oligochaetes and chironomids (burrowers) ingested the largest particles (medium length: 28 and 48 µm, respectively), whereas deposit-feeders ingested larger particles (medium length: 26 µm) than scrapers and predators. Pellets were abundant in all taxa, except for Chironomidae. Textile cellulose fibers were present in all taxa and functional guilds, while MP polymers (EVA, PET, PA, PE, PE-PP) differed among taxa and functional guilds. In detail: EVA and PET particles were found only in chironomids, PE particles occurred in chironomids, copepods and ephemeropterans, PA particles were found in all taxa except in nematodes, whereas particles made of PE-PP blend occurred in oligochaetes and copepods. Burrowers and deposit-feeders ingested EVA, PET, PA, PE and PE-PP, while crawlers and scrapers ingested PE and PA. Swimmers and predators ingested PE, PA and PE-PP. Our findings suggest a pervasive level of plastic and textile cellulose pollution consistent with an urban stream which propagates in the meiofaunal assemblage of the stream ecosystem.

Assessment of contaminants of emerging concern in European apex predators and their prey by LC-QToF MS wide-scope target analysis.

Apex predators are good indicators of environmental pollution since they are relatively long-lived and their high trophic position and spatiotemporal exposure to chemicals provides insights into the persistent, bioaccumulative and toxic (PBT) properties of chemicals. Although monitoring data from apex predators can considerably support chemicals' management, there is a lack of pan-European studies, and longer-term monitoring of chemicals in organisms from higher trophic levels. The present study investigated the occurrence of contaminants of emerging concern (CECs) in 67 freshwater, marine and terrestrial apex predators and in freshwater and marine prey, gathered from four European countries. Generic sample preparation protocols for the extraction of CECs with a broad range of physicochemical properties and the purification of the extracts were used. The analysis was performed utilizing liquid (LC) chromatography coupled to high resolution mass spectrometry (HRMS), while the acquired chromatograms were screened for the presence of more than 2,200 CECs through wide-scope target analysis. In total, 145 CECs were determined in the apex predator and their prey samples belonging in different categories, such as pharmaceuticals, plant protection products, per- and polyfluoroalkyl substances, their metabolites and transformation products. Higher concentration levels were measured in predators compared to prey, suggesting that biomagnification of chemicals through the food chain occurs. The compounds were prioritized for further regulatory risk assessment based on their frequency of detection and their concentration levels. The majority of the prioritized CECs were lipophilic, although the presence of more polar contaminants should not be neglected. This indicates that holistic analytical approaches are required to fully characterize the chemical universe of biota samples. Therefore, the present survey is an attempt to systematically investigate the presence of thousands of chemicals at a European level, aiming to use these data for better chemicals management and contribute to EU Zero Pollution Ambition.

Making use of apex predator sample collections: an integrated workflow for quality assured sample processing, analysis and digital sample freezing of archived samples.

Using monitoring data from apex predators for chemicals risk assessment can provide important information on bioaccumulating as well as biomagnifying chemicals in food webs. A survey among European institutions involved in chemical risk assessment on their experiences with apex predator data in chemical risk assessment revealed great interest in using such data. However, the respondents indicated that constraints were related to expected high costs, lack of standardisation and harmonised quality criteria for exposure assessment, data access, and regulatory acceptance/application. During the Life APEX project, we demonstrated that European sample collections (i.e. environmental specimen banks (ESBs), research collection (RCs), natural history museums (NHMs)) archive a large variety of biological samples that can be readily used for chemical analysis once appropriate quality assurance/control (QA/QC) measures have been developed and implemented. We therefore issued a second survey on sampling, processing and archiving procedures in European sample collections to derive key quality QA/QC criteria for chemical analysis. The survey revealed great differences in QA/QC measures between ESBs, NHMs and RCs. Whereas basic information such as sampling location, date and biometric data were mostly available across institutions, protocols to accompany the sampling strategy with respect to chemical analysis were only available for ESBs. For RCs, the applied QA/QC measures vary with the respective research question, whereas NHMs are generally less aware of e.g. chemical cross-contamination issues. Based on the survey we derived key indicators for assessing the quality of biota samples that can be easily implemented in online databases. Furthermore, we provide a QA/QC workflow not only for sampling and processing but also for the chemical analysis of biota samples. We focussed on comprehensive analytical techniques such as non-target screening and provided insights into subsequent storage of high-resolution chromatograms in online databases (i.e. digital sample freezing platform) to ultimately support chemicals risk assessment.

Occurrence of Natural and Synthetic Micro-Fibers in the Mediterranean Sea: A Review.

Among microplastics (MPs), fibers are one of the most abundant shapes encountered in the aquatic environment. Growing attention is being focused on this typology of particles since they are considered an important form of marine contamination. Information about microfibers distribution in the Mediterranean Sea is still limited and the increasing evidence of the high amount of fibers in the aquatic environment should lead to a different classification from MPs which, by definition, are composed only of synthetic materials and not natural. In the past, cellulosic fibers (natural and regenerated) have been likely included in the synthetic realm by hundreds of studies, inflating "micro-plastic" counts in both environmental matrices and organisms. Comparisons are often hampered because many of the available studies have explicitly excluded the micro-fibers (MFs) content due, for example, to methodological problems. Considering the abundance of micro-fibers in the environment, a chemical composition analysis is fundamental for toxicological assessments. Overall, the results of this review work provide the basis to monitor and mitigate the impacts of microfiber pollution on the sea ecosystems in the Mediterranean Sea, which can be used to investigate other basins of the world for future risk assessment.

Editorial for the Special Issue "Microplastics in Aquatic Environments: Occurrence, Distribution and Effects".

The large production and widespread daily consumption of plastic materials-which began in the last century-together with the often-inadequate collection and recycling systems, have made plastics and, consequently, microplastics (MPs) ubiquitous pollutants [...].

Occurrence and Quantification of Natural and Microplastic Items in Urban Streams: The Case of Mugnone Creek (Florence, Italy).

The terrestrial environment is an important contributor of microplastics (MPs) to the oceans. Urban streams, strictly interwoven in the city network and to the MPs' terrestrial source, have a relevant impact on the MP budget of large rivers and, in turn, marine areas. We investigated the fluxes (items/day) of MPs and natural fibers of Mugnone Creek, a small stream crossing the highly urbanized landscape of Florence (Italy) and ending in the Arno River (and eventually to the Tyrrhenian Sea). Measurements were done in dry and wet seasons for two years (2019-2020); stream sediments were also collected in 2019. The highest loads of anthropogenic particles were observed in the 2019 wet season (109 items/day) at the creek outlet. The number of items in sediments increased from upstream (500 items/kg) to urban sites (1540 items/kg). Fibers were the dominant shape class; they were mostly cellulosic in composition. Among synthetic items, fragments of butadiene-styrene (SBR), indicative of tire wear, were observed. Domestic wastewater discharge and vehicular traffic are important sources of pollution for Mugnone Creek, especially during rain events. The study of small creeks is of pivotal importance to limit the availability of MPs in the environment.

Hazardous contaminants in plastics contained in compost and agricultural soil.

Macro-, meso- and microplastic (MAP, MEP, MP) occurrence in compost is an environmental issue whose extent and effects are not yet understood. Here, we studied the occurrence of MAPs, MEPs and MPs in compost samples, and the transfer of hazardous contaminants from plastics to compost and soil. MAPs/MEPs and MPs concentrations in compost were 6.5 g/kg and 6.6 ± 1.5 pieces/kg; from common recommendations for compost application, we estimated ∼4-23 × 107 pieces MPs and 4-29 × 104 g MAPs/MEPs ha-1 per year ending into agricultural soils fertilized with such compost. Regarding contaminants, bis(ethylhexyl) phthalate, acetyl tributyl citrate, dodecane and nonanal were extracted in higher concentrations from plastics and plastic-contaminated compost than from compost where MAPs/MEPs had been removed prior to extraction and analysis. However, some contaminants were present even after MAPs/MEPs removal, ascribable to short- and long-term release by MAPs/MEPs, and to the presence of MPs. DEHP concentration was higher in soils where compost was applied than in fields where it was not used. These results, along with estimations of plastic load to soil from the use of compost, show that compost application is a source of plastic pollution into agricultural fields, and that plastic might transfer hazardous contaminants to soil.

Graphene-based nanomaterials in the electroplating industry: A suitable choice for heavy metal removal from wastewater.

The presence of various heavy metal ions in the industrial waste waters has recently been a challenging issue for human health. Since heavy metals are highly soluble in the aquatic environments and they can be absorbed easily by living organisms, their removal is essential from the environmental point of view. Many studies have been devoted to investigating the environmental behaviour of graphene-based nanomaterials as sorbent agents to remove metals from wastewaters arising by galvanic industries. Among the graphene derivates, especially graphene oxide (GO), due to its abundant oxygen functional groups, high specific area and hydrophilicity, is a high-efficient adsorbent for the removal of heavy and precious metals in aquatic environment. This paper reviews the main graphene, GO, functionalized GO and their composites and its applications in the metals removal process. The influencing factors, adsorption capacities and reuse capability are highlighted for the most extensively used heavy metals, including copper, zinc, nickel, chromium, cobalt and precious metals (i.e., gold, silver, platinum, palladium, rhodium, and ruthenium) in the electroplating process.

Determination of 56 per- and polyfluoroalkyl substances in top predators and their prey from Northern Europe by LC-MS/MS.

Per- and polyfluoroalkyl substances (PFAS) are a group of emerging substances that have proved to be persistent and highly bioaccumulative. They are broadly used in various applications and are known for their long-distance migration and toxicity. In this study, 65 recent specimens of a terrestrial apex predator (Common buzzard), freshwater and marine apex predators (Eurasian otter, harbour porpoise, grey seal, harbour seal) and their potential prey (bream, roach, herring, eelpout) from northern Europe (United Kingdom, Germany, the Netherlands and Sweden) were analyzed for the presence of legacy and emerging PFAS, employing a highly sensitive liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) method. 56 compounds from 14 classes were measured; 13 perfluoroalkyl carboxylic acids (PFCAs), 7 perfluoroalkyl sulphonic acids (PFSAs), 3 perfluorooctane sulfonamides (FOSAs), 4 perfluoroalkylphosphonic acids (PFAPAs), 3 perfluoroalkylphosphinic acids (PFPi's), 5 telomer alcohols (FTOHs), 2 mono-substituted polyfluorinated phosphate esters (PAPs), 2 di-substituted polyfluorinated phosphate esters (diPAPs), 6 saturated fluorotelomer acids (FTAS), 3 unsaturated fluorotelomer acids (FTUAs), 2 N-Alkyl perfluorooctane sulfonamidoethanols (FOSEs), 3 fluorotelomer sulphonic acids (FTSAs), 2 perfluoroether carboxylic acids (PFECAs) and 1 chlorinated perfluoroether sulphonic acid (Cl-PFESA). All samples were lyophilized before analysis, in order to enhance extraction efficiency, improve the precision and achieve lower detection limits. The analytes were extracted from the dry matrices through generic methods of extraction, using an accelerated solvent extraction (ASE), followed by clean-up through solid phase extraction (SPE). Method detection limits and method quantification limits ranged from 0.02 to 1.25 ng/g wet weight (ww) and from 0.05 to 3.79 ng/g (ww), respectively. Recovery ranged from 40 to 137%. Method precision ranged from 3 to 20 %RSD. The sum of PFAS concentration in apex predators livers ranged from 0.2 to 20.2 µg/g (ww), whereas in the fish species muscle tissues it ranged from 16 to 325 ng/g (ww). All analyzed specimens were primarily contaminated with PFOS, while the three PFPi's included in this study exhibited frequency of appearance (FoA) 100 %. C9 to C13 PFCAs were found at high concentrations in apex predator livers, while the overall PFAS levels in fish fillets also exceeded ecotoxicological thresholds. The findings of our study show a clear association between the PFAS concentrations in apex predators and the geographical origin of the specimens, with samples that were collected in urban and agricultural zones being highly contaminated compared to samples from pristine or semi-pristine areas. The high variety of PFAS and the different PFAS composition in the apex predators and their prey (AP&P) samples is alarming and strengthens the importance of PFAS monitoring across the food chain.

Occurrence and characterization of microplastic and mesoplastic pollution in the Migliarino San Rossore, Massaciuccoli Nature Park (Italy).

Microplastics pollution is progressively threatening natural parks across the world. In the framework of monitoring this concerning trend, the present study focuses on the occurrence and identification of mesoplastics (MEPs) and microplastics (MPs) in sand samples collected before and after the summer season from the beach of the Nature Park of Migliarino San Rossore Massaciuccoli (Pisa, Italy). Meso- and microplastics were identified using Fourier transform infrared spectroscopy 2D Imaging, and detected in all samples with average concentrations of 207 ± 30 MPs/kg d.w., and 100 ± 44 MEPs/kg d.w., respectively. Seasonal changes of flow of the Arno River, industrial activities, and urban footprint were considered as the major sources of plastic pollution. Our results showed the occurrence of both natural and synthetic polymers including cellulose, polyethylene, polypropylene, polyamides, polyethylene terephthalate, and acrylonitrile.

Microplastics in the Black Sea sediments.

In this study the occurrence, morphology and identification of microplastics in Black Sea sediments collected at different depths (range 22-2131 m) were determined for the first time. The study explored the advantages and limitations of using a non-invasive method consisting of filtration of the supernatant from the mixture of sediment with saturated NaCl solution followed by FTIR 2D imaging for the identification of natural and synthetic polymers. The proposed method confirmed its potential for clear identification of polyethylene, polypropylene, acrylonitrile, polyamides and cellulose-based fibers, but more difficulties when the filter substrate neighboring the fibers exhibits intense absorptions in the 1800-1000 cm-1 range. Microplastics (MPs) were determined in 83% of the investigated sediment samples. The average abundance in all samples was 106.7 items/kg. The highest pollution occurred on the North-Western shelf where the abundance of MPs was 10 times higher than in sediments from the deep sea. The most abundant plastic polymers were polyethylene and polypropylene, followed by acrylate and acrylonitrile copolymers. Polyamide and cellulose-based textile fibers were also found. The most frequent microplastic colors observed were black, blue and clear/transparent, while fibers represented the dominant microplastics in sediments.

Indoor levels of volatile organic compounds at Florentine museum environments in Italy.

Indoor Air Quality monitoring in cultural institutions is of particular concern to protect these places and the cultural heritage content. An indoor monitoring campaign was performed in three museums in Florence (Italy) to determine the occurrence and levels of volatile organic compounds (VOCs). VOCs of interest included BTEX (benzene, toluene, ethylbenzene, xylenes), terpenes, aldehydes, organic acids, and cyclic volatile methyl siloxanes (cVMS). The most abundant VOCs in all samples analyzed were BTEX, which were strictly related to the traffic source, followed by siloxanes and terpenes. Among BTEX, toluene was always the most abundant followed by xylenes, ethylbenzene, and benzene. cVMS in exhibition rooms with the presence of visitors showed higher values compared to samples collected when the museums were closed. Terpenes showed not only the influence of vegetation-biogenic sources surrounding a museum but could also be related to the wood used for the construction of showcases and furniture and the use of cleaning products. Data obtained also showed the presence of organic acids and aldehydes whose source can be traced back to exhibits themselves and wood-based furniture. Assessing the levels of organic acids in museums is important because, over time, it can cause deterioration of the artifacts.

Correction to: Progress on bringing together raptor collections in Europe for contaminant research and monitoring in relation to chemicals regulation.

The correct affiliation of Sabrina Lo Brutto is shown in this paper.

PBDEs and PCBs in terrestrial ecosystems of the Victoria Land, Antarctica.

The Victoria Land (East Antarctica) is characterized by the presence of lakes and ponds where rare water is found during the Summer months. These freshwater ecosystems are an important resource for migrating seabirds that use them and leave there their droppings and feathers, contributing to enrich the water with organic matter. Persistent organic pollutants (POPs) are long-range transported to polar regions and their detection in the Antarctic ecosystems date back to the 1960s. Most studies have been related to POP concentrations in marine environment, and terrestrial ecosystems have been poorly investigated. This study reports the concentration of PBDEs (23 congeners) and PCBs (21 among non-, mono-, di-, and ortho congeners) in lake sediment, soil and vegetation mat (community of algae, cyanobacteria, bryophites) collected close to six lakes in the Victoria Land (74°31'S-74°97'S, 165°07'E-162°51'E): Edmonson Point 14 and 15A, Carezza, Enigma, Tarn Flat 20, Inexpressible Island 10B. The ∑PBDEs averaged 0.09-0.28 ng/g and BDEs 28, 47 and 154 were higher in mat and soils, while BDEs 183 and 47 in sediment samples. PCBs ranged <0.003-0.807 ng/g and congeners nos. 114, 138, and 187 were the most abundant. In addition, TEQs were derived for the non-and mono-ortho PCBs detected and values were very low in each matrix (0.010 pg/g in the soil, 0.012 pg/g in sediment and mat). The long-range atmospheric transport can be confirmed as the most important POP source in Antarctica, although the scientific stations and seabird colonies may be potential local sources and contribute to contaminant release.

Ingested microplastic as a two-way transporter for PBDEs in Talitrus saltator.

The presence and accumulation of plastic waste into the marine environment are well known environmental issues. Microplastics (MPs) end up in sea waters and, due to their hydrophobicity and high surface/volume ratio, POPs tend to sorb and accumulate to their surface. The supralittoral amphipod Talitrus saltator (T. saltator) was selected to study the role of MPs in the transfer of organic pollutants and to investigate if ingested MPs could either transfer contaminants to biota or clean it adsorbing pollutants taken from the diet. T. saltator is an established POPs (Persistent Organic Pollutants) biomonitor in coastal environments and it is able to swallow microplastics in natural condition. Two laboratory experiments were performed and T. saltator was exposed to a labelled polybrominated diphenyl ether (13C-labelled BDE-47) to investigate the opposite gradient role of MPs. X Ray Micro-CT (Micro-Computed Tomography) analyses were also performed on sandhopper samples to evaluate the uptake of MPs via digestive tract. The results showed that MPs ingestion could whether transfer and remove contaminants from T. saltator, indicating a partial balance among positive and negative effects. This study has underlined MP potential double role demonstrating that MP can act both as a carrier and scavenger for the bioaccumulation of organic pollutants (i.e. PBDEs), suggesting that chemicals leaching from MPs could have a limited impact to biota.

Phytoremediation of sewage sludge contaminated by trace elements and organic compounds.

Phytoremediation is a green technique being increasingly used worldwide for various purposes including the treatment of municipal sewage sludge (MSS). Most plants proposed for this technique have high nutrient demands, and fertilization is often required to maintain soil fertility and nutrient balance while remediating the substrate. In this context, MSS could be a valuable source of nutrients (especially N and P) and water for plant growth. The aim of this study was to determine the capacity willow (Salix matsudana, cv Levante), poplar (Populus deltoides × Populus nigra, cv Orion), eucalyptus (Eucalyptus camaldulensis) and sunflower (Helianthus annuus) to clean MSS, which is slightly contaminated by trace elements (TEs) and organic pollutants, and to assess their physiological response to this medium. In particular, we aimed to evaluate the TE accumulation by different species as well as the decrease of TEs and organic pollutants in the sludge after one cropping cycle and the effect of MSS on plant growth and physiology. Since MSS did not show any detrimental effect on the biomass yield of any of the species tested, it was found to be a suitable growing medium for these species. TE phytoextraction rates depended on the species, with eucalyptus showing the highest accumulation for Cr, whereas sunflower exhibited the best performance for As, Cu and Zn. At the end of the trial, some TEs (i.e. Cr, Pb and Zn), n-alkanes and PCBs showed a significant concentration decrease in the sludge for all tested species. The highest Cr decrease was observed in pots with eucalyptus (57.4%) and sunflower (53.4%), whereas sunflower showed the highest Cu decrease (44.2%), followed by eucalyptus (41.2%), poplar (16.2%) and willow (14%). A significant decrease (41.1%) of Pb in the eucalyptus was observed. Zn showed a high decrease rate with sunflower (59.5%) and poplar (52%) and to a lesser degree with willow (35.3%) and eucalyptus (25.4%). The highest decrease in n-alkanes concentration in the sludge was found in willow (98.3%) and sunflower (97.3%), whereas eucalyptus has the lowest PCBs concentration (91.8%) in the sludge compared to the beginning of the trial. These results suggest new strategies (e.g. crop rotation and intercropping) to be adopted for a better management of this phytotechnology.