Search

Phthalates are widely employed plasticizers blended to plastic polymers that, during plastic aging and weathering are prone to leach in the surrounding environment. Thus, phthalates were proposed to indirectly evaluate MPs contamination in marine environments, with still uncertain and scarce data, particularly for wildlife. This study investigates simultaneously microplastics (MPs) and phthalates (PAEs) occurrence in wild Actinia equina and Anemonia viridis, two common and edible sea anemone species. Both species had a 100 % frequency of MPs occurrence, with similar average concentrations. PAEs were detected in 70 % of samples, with concentrations up to 150 ng/g in A. equina and 144.3 ng/g for A. viridis. MPs and PAEs present in sea anemone tissues appear to reflect seawater plastic contamination conditions in the study area. Given the rapid biodegradation of PAEs, occurrence and concentrations of both these additives and their metabolites could be useful tracers of short-term plastic debris-biota interactions.

This study evaluates the effectiveness of microalgal-based carbon-encapsulated iron nanoparticles (ME-nFe) in the removal of pharmaceutical compounds (PhACs) from water solutions and real municipal effluent at a laboratory scale. The investigated PhACs were chosen to represent different classes of synthetic drugs: antibiotics, anti-inflammatory drugs, antihypertensives, antiepileptics, neuroprotectors, and antidepressants. The adsorbent material was produced through hydrothermal carbonization (225 °C for 3 h), using microalgae grown on wastewater as the carbon source. ME-nFe showed heterogeneity in terms of porosity (with both abundance of macro and mesopores), a total pore volume of 0.65 mL g−1, a specific surface area of 117 m2 g−1 and a total iron content of 40%. Laboratory scale adsorption tests (1 g L−1 of nanoparticles with 2 min contact time) showed high removal for the most hydrophobic compounds. Removal efficiencies were high (over 98%) for Irbesartan, Ofloxacin and Diclofenac, promising (over 65–80%) for Clarithromycin, Fluoxetine, Lamotrigine and Metoprolol, but low for Gabapentin-Lactam and Propyphenazone (<20%). Electrostatic interactions between the drugs and the surface of the nanoparticles may account for the observed data, although additional removal mechanisms cannot be ruled out.

The Mediterranean Sea's biodiversity is declining due to climate change and human activities, with plastics and emerging contaminants (ECs) posing significant threats. This study assessed phthalic acid esters (PAEs) and active pharmaceutical ingredients (APIs) occurrence in four anthozoan species (Cladocora caespitosa, Eunicella cavolini, Madracis pharensis, Parazoanthus axinellae) using solid phase microextraction (SPME) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). All specimens were contaminated with at least one contaminant, reaching maximum values of 57.3 ng/g for the ∑PAEs and 64.2 ng/g (wet weight) for ∑APIs, with dibutyl phthalate and Ketoprofen being the most abundant. P. axinellae was the most contaminated species, indicating higher susceptibility to bioaccumulation, while the other three species showed two-fold lower concentrations. Moreover, the potential adverse effects of these contaminants on anthozoans have been discussed. Investigating the impact of PAEs and APIs on these species is crucial, given their key role in the Mediterranean benthic communities.

This study evaluates the effectiveness of a pilot-scale high-rate algae-bacteria pond (HRAP) to remove pharmaceutical compounds (PhACs) from municipal centrate. The studied PhACs belonged to different classes of synthetic active compounds: antihypertensives, antiepileptics, antidepressants, neuroprotectors, and anti-inflammatory drugs. The HRAP, growing a mixed microalgal consortium made of Chlorella spp. and Scenedesmus spp., was operated in continuous mode (6 days hydraulic retention time) from May to November 2021. Removal efficiencies were high (>85 %) for Sulfamethoxazole and Lamotrigine, promising (65–70 %) for Metoprolol, Fluoxetine, and Diclofenac but low (30–40 %) for Amisulpride, Ofloxacin, Carbamazepine, and Clarithromycin. Propyphenazone and Irbesartan were not removed, and their concentrations increased after the treatment. The combination of abiotic and biotic drivers (mostly global radiation and the synergy between microalgae and bacteria metabolisms) fostered photo and biodegradation processes. Overall, results suggest that microalgae-based systems can be a valuable solution to remove PhACs from wastewater.

At present the information regarding the occurrence of human pharmaceuticals (PhaCs) in coral reefs and their potential impacts on the associated fauna is limited. To optimize the collection of data in these delicate environments, we employed a solid-phase microextraction (bioSPME) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) procedure that enabled in vivo determinations in soft corals. Specifically, we researched the antibiotics Ofloxacin Sulfamethoxazole and Clarithromycin, the anti-inflammatory Diclofenac Propyphenazone Ketoprofen and Amisulpride, the neuroactive compounds Gabapentin-lactam, the beta-blocker Metoprolol and the antiepileptic Carbamazepine. Reproducibility was between 2.1% and 9.9% and method detection limits LODs) were between 0.2 and 1.6 ng/g and LOQs between 0.8 and 5.4 mg/g. The method was then applied to establish a baseline for the occurrence of these compounds in the Maldivian archipelago. Colonies of Sarcophyton sp. and Sinularia sp. were sampled along an inner-outer reef transect. Five of the ten targeted PhaCs were identified, and 40% of the surveyed coral colonies showed the occurrence of at least one of the selected compounds. The highest concentrations were found inside the atoll rim. Oxoflacin (9.5 ± 3.9 ng/g) and Ketoprofen (4.5 ± 2.3 ng/g) were the compounds with the highest average concentrations. Outside the atoll rim, only one sample showed contamination levels above the detection limit. No significant differences were highlighted among the two surveyed soft coral species, both in terms of average concentrations and bioconcentration factors (BCFs).

The production of synthetic plastics, especially polyethylene, has reached a crucial level, making highly challenging plastic waste management. This paper aims to elucidate the role of two novel laccase-like multicopper oxidases in polyethylene oxidative degradation based on transcriptomic data from Rhodococcus opacus R7 grown on polyethylene. The purification of the recombinant proteins, LMCO2 and LMCO3 belonging respectively to the three- and two-domains laccase families, showed that they are endowed with different functional features. LMCO2 showed the highest enzyme activity at 65 °C with an optimal pH of 7.0, while LMCO3 exhibited the highest activity at 80 °C at acidic pH. LMCOs showed activity on both phenolic (i.e., 2,6-DMP) and non-phenolic (i.e., ABTS) compounds and they were thermostable. The oxidative activity of LMCO2 and LMCO3 on untreated low-density polyethylene was assessed by combining Fourier transform infrared spectroscopy and gas chromatography coupled with mass spectrometry analyses. Oxidation of PE was recorded within a short time range (24-48 h) and revealed previously not described patterns of alkyl compounds and oxygenated products including ketones, alcohols, and carboxylic acids. Structural analysis of LMCO2 and LMCO3 together with density functional theory calculations allowed to identify structural and electronic elements presumably involved in the oxidation of polyethylene.

Over the past decades, the biodiversity of the Mediterranean Sea has undergone rapid alterations and decline due to climate change and human activities. Marine heat waves, mass mortality events, and increasing pollution in coastal areas, particularly from plastics and emerging contaminants (ECs) disposed in the sea, are among the most significant threats. This problem has become even more pronounced in the aftermath of the recent pandemic. Therefore, the present work aimed to assess, for the first time, the occurrence of phthalic acid esters (PAEs) and pharmaceutical and personal care products (PPCPs) in four key species of Mediterranean benthic anthozoans: Cladocora caespitosa, Eunicella verrucosa, Madracis pharensis, and Parazoanthus axinellae. For PAEs and PPCPs determination in the coral tissue we employed solid phase microextraction (SPME) and liquid chromatography couple to tandem mass spectrometry (LC-MS/MS). All the specimens were found to be contaminated with at least one type of PPCPs, and 18 out of 20 displayed levels of PAEs over the quantification limit. The PAEs displayed an average concentration of 17.23 ± 11.39 ng/g with a maximum value of 44.17 ng/g, while the PPCPs average concentration was 25.89 ± 16.99 ng/g with a maximum value of 57.49 ng/g. The most abundant were DBP (10.35 ± 5.59 ng/g) and ketoprofen (16.97 ± 17.05 ng/g) respectively. Interestingly, they were found in higher concentrations in the same species, P. axinellae, suggesting a higher susceptibility to adsorb both contaminants. Furthermore, the other three species demonstrated an adsorption capacity two-fold lower, possibly due to varying environmental conditions related to depth, currents, and shelter, which exposed them differently to the contaminants. Given the crucial role of these species in forming the habitat of benthic communities along the Mediterranean coastal environment, it is important to investigate the potential human impact in the form of PAEs and PPCPs more thoroughly

Oxidative stress caused by reactive oxygen species (ROS, O2•−, HO•, and H2O2) affects the aging process and the development of several diseases. A new frontier on its prevention includes functional foods with both specific probiotics and natural extracts as antioxidants. In this work, Panax ginseng C.A. Meyer berries extract was characterized for the presence of beneficial molecules (54.3% pectin-based polysaccharides and 12% ginsenosides), able to specifically support probiotics growth (OD600nm > 5) with a prebiotic index of 0.49. The administration of the extract to a probiotic consortium induced the production of short-chain fatty acids (lactic, butyric, and propionic acids) and other secondary metabolites derived from the biotransformation of Ginseng components. Healthy and tumoral colorectal cell lines (CCD841 and HT-29) were then challenged with these metabolites at concentrations of 0.1, 0.5, and 1 mg/mL. The cell viability of HT-29 decreased in a dose-dependent manner after the exposition to the metabolites, while CCD841 vitality was not affected. Regarding ROS production, the metabolites protected CCD841 cells, while ROS levels were increased in HT-29 cells, potentially correlating with the less functionality of glutathione S-transferase, catalase, and total superoxide dismutase enzymes, and a significant increase in oxidized glutathione.

The bioconcentration of dimethyl phthalate (DMP) diethyl phthalate (DEP) dibutyl phthalate (DBP) butyl benzyl phthalate (BBzP), di-(2-ethy hexyl) phthalates (DEHP), mono-butyl phthalate (MBP), mono-benzyl phthalate (MBzP), mono-(2-ethy hexyl) phthalate (MEHP) in the soft corals Coelogorgia palmosa, Sinularia sp., Sarcophyton glaucum, and Lobophytum sp. was investigated. Specimens were cultured in a microcosm environment built-up at the Genova Aquarium and analyses were carried out by in vivo SPME-LC-MS/MS. The distributions of the phthalates among the four surveyed species resulted significantly different. Calculated bioconcentration factors (BCFs) showed values spanning over two orders of magnitude, from a minimum of log10 BCFDEP = 1.0 in Sarcophyton glaucum to a maximum of log10 BCFDBP = 3,9 calculated for Coelogorgia palmosa. Moreover, the calculated BCFs of the long chain phthalates resulted up to three orders of magnitude lower than theoretically predicted (from logKow), whereas BCF of short chain phthalates resulted higher. This, together with the detection of phthalic acid monoesters, suggests the presence of species-specific different metabolic transformation among the surveyed soft coral species that involve DEHP.

Plastic and oil pollution are closely linked to our dependence on petroleum derivatives. Their excessive use and inefficiencies in their management, have led to negative impacts on marine ecosystems since their very introduction. Agglomerates of tar, plastic, paraffins, and other petrochemicals and oil derivatives with naturally occurring materials, are increasingly widespread in coastal environments, stalling as an iconic and readable sign of environmental degradation. Starting from a historical review of the available reports on the occurrence of similar aggregates dating back to 1971, we highlight how most of these observations are based on the morphological description of the petroleum residues with no chemical fingerprinting and are mainly related to materials stranded on the coastline, with few and unclear indications for the open sea. We discuss here a list of scientific questions and knowledge gaps, that need to be examined by future studies.

A new geological formation consisting of plastic debris admixed to petroleum oil residue, termed "plastitar", has been recently described in the Canary Islands. Here, we report its widespread occurrence across the Mediterranean coast and new insights into its biogeochemical composition. Specifically, we found marked differences in the diagenetic stable indicator profiles, suggesting a heterogeneous seeps provenance. Moreover, the 801 plastic particles found in the 1372 g of tar surveyed, with a maximum concentration of 2.0 items/g, showed interesting patterns in the tar mat, with nurdles predominantly layered in the external of the tar mat and lines in the inner core. Overall, the collected observation suggests that tar entraps plastics through a stepwise process and is a sink for them.

Different Light-Absorbing Snow Impurities (LASI) can deposit on snow- and ice-covered surfaces. These particles are able to decrease snow and ice albedo and trigger positive albedo feedback. The aim of this work was to develop a new method to quantify the carbonaceous fractions that are present in snow and ice samples that contribute significantly to their darkening. Currently, in the literature, there is an absence of a unified and accepted method to perform these studies. To set up the method proposed here, snow samples were collected at two Italian locations, Claviere and Val di Pejo (Northern Italy). The samples were analyzed using two main techniques, Total Organic Carbon analysis (TOC analysis) and Thermal Optical analysis in Transmittance mode (TOT), which enabled the speciation of the carbonaceous fraction into organic (OC), inorganic (IC), and elemental carbon (EC), and further into the soluble and insoluble parts. The results highlighted a correlation between the nature of the sample (i.e., location, age, and exposure of the snow) and the experimental results, giving validity to the method. For example, the abundant presence of terrigenous constituents was reflected in high amounts of insoluble IC. Moreover, due to the trend between insoluble IC and Elemental Carbon (EC), the role of IC in TOT analysis was investigated. Indeed, IC turned out to be an interfering agent, suggesting that the two techniques (TOC analysis and TOT) are complementary and therefore need to be used in parallel when performing these studies. Finally, the results obtained indicate that the newly proposed method is suitable for studying the carbonaceous fractions in snow samples.

The integration of microalgae-bacteria consortia within existing wastewater treatment plants as alternative biological treatment could be an interesting option to improve the sustainability of these facilities. However, the fate of the produced biomass is decisive to make that option economically attractive. The present study aimed to valorize the microalgae grown at a pilot scale and used for the treatment of the centrate from municipal sewage sludge, producing microalgal-based iron nanoparticles (ME-nFe), by hydrothermal carbonization. The final product had high carbon content, strong sorbent power, and reducing properties, due to the presence of zerovalent iron. Different synthesis conditions were tested, comparing iron (III) nitrate nonahydrate (Fe (NO3)(3)center dot 9H(2)O) and ammonium iron (III) sulfate dodecahydrate (NH4 Fe (SO4)(2)center dot 12 H2O) as iron sources, four different Fe/C molar ratios (0.02, 0.05, 0.1, 0.2), and three process temperatures (180, 200, 225 degrees C). Based on the characterization of all the prototypes, the best one (having a specific area of 110 m(2)g(-1)) was chosen and tested for the removal of selected heavy metals by Jar tests. The removal of copper, zinc, cadmium, and nickel from the treated effluent from the wastewater treatment plant was 99.6%, 97.8%, 96.4%, and 80.3%, respectively, also for very low starting concentrations (1 mg L-1). The removal of total chromium, on the contrary, was only 12.4%. Thanks to the magnetic properties, the same batch of ME-nFe was recovered and used effectively for three consecutive Jar tests.

Sediment core samples from high tide lines and in submerged zones as well as surface water samples from eight beaches of Tenerife were analysed. Sampling was conducted over a period of one year in intervals of 5 weeks. The majority of particles were found in the high tide sediment (66%), followed by water samples (23%) and finally in sediment from submerged zones (11%). Regarding the particle amount per volume (items/L), accumulation in sediment samples was statistically higher compared to water samples. Mean values of items/L were higher in high tide sediments. In high tide and water samples, mostly white and transparent particles >1 mm were found. More than 70% were represented by fragments. In sediments from submerged zones, yellow and blue microparticles (<1 mm) were predominant and 61.9% consisted of fibres. Larger particles were mainly identified as PP, PE, PS, PTFE and PVC, while polymer types of smaller particles were more variable.

Maitake (Grifola frondosa) is a medicinal mushroom known for its peculiar biological activities due to the presence of functional components, including dietary fibers and glucans, that can improve human health through the modulation of the gut microbiota. In this paper, a Maitake eth-anol/water extract was prepared and characterized through enzymatic and chemical assays. The prebiotic potential of the extract was evaluated by the growth of some probiotic strains and of a selected probiotic consortium. The results revealed the prebiotic properties due to the stimulation of the growth of the probiotic strains, also in consortium, leading to the production of SCFAs, including lactic, succinic, and valeric acid analyzed via GC‐MSD. Then, their beneficials effect were employed in evaluating the vitality of three different healthy and tumoral colorectal cell lines (CCD841, CACO‐2, and HT‐29) and the viability rescue after co‐exposure to different stressor agents and the probiotic consortium secondary metabolites. These metabolites exerted positive effects on colorectal cell lines, in particular in protection from reactive oxygen species.

The published online version contains mistake in the author list for the author “M. Cappelletti” was incorrectly presented.

Nowadays, the increase of the unconventional oil deposit exploitation and the amount of oil sands process-affected waters (OSPW) in tailing ponds emerges the importance of developing bio-monitoring strategies for the restoration of these habitats. The major constituents of such deposits are naphthenic acids (NAs), emerging contaminant mixtures with toxic and recalcitrant properties. With the aim of developing bio-monitoring strategies based on culture-independent approach, we identified genes coding for enzymes involved in NA degradation from Rhodococcus opacus R7 genome, after the evaluation of its ability to mineralize model NAs. R. opacus R7 whole-genome analysis unveiled the presence of pobA and chcpca gene clusters putatively involved in NAs degradation. Gene expression analysis demonstrated the specific induction of R7 aliA1 gene, encoding for a long-chain-fatty-acid-CoA ligase, in the presence of cyclohexanecarboxylic acid (CHCA) and hexanoic acid (HA), selected as representative compounds for alicyclic and linear NAs, respectively. Therefore, aliA1 gene was selected as a molecular marker to monitor the biodegradative potential of slurry-phase sand microcosms in different conditions: spiked with CHCA, in the presence of R. opacus R7, the autochthonous microbial community, and combining these factors. Results revealed that the aliA1-targeting culture-independent approach could be a useful method for bio-monitoring of NA degradation in a model laboratory system.

The integration of microalgae in the municipal wastewater treatment scheme could certainly be an interesting option to reduce the carbon footprint of the process. The obtained microalgae could be valorized through hydrothermal carbonization (HTC), producing a sorbent material to be used as an alternative to activated carbon. However, HTC of microalgae does produce potentially harmful byproducts. The present work aims to investigate the possibility of using the effluent derived from the hydrothermal carbonization of microalgae (HTC-LF), performed to produce microalgal-based carbon encapsulated iron nanoparticles (ME-nFe), as a growth medium for the microalgae. Since this raw effluent was proved to be toxic for Allivibrio fisheri (EC50 = 1.8 %), the microalgal activity was studied also for detoxification. A 20 % dilution of the HTC-LF, using municipal centrate as the diluent, was proved to be suitable for microalgal growth without affecting the photochemical efficiency. In a continuous test, a community made of Chlorella spp. and Euglena gracilis was able to grow with and without CO2 addition, with average productivity of 62 +/- 5 and 43 +/- 8 mg L-1 d(-1), respectively. The treatment led to a 60 % COD removal, suggesting that the HTC-LF was not harmful to the microalgae-bacteria consortia, which was also able to decrease its toxicity. Environmental implications: The liquid byproduct of the hydrothermal carbonization (HTC-LF) is a known toxic for the water compartment. The possibility to exploit its nutrient content for microalgal growth was already proved by different studies using strong dilution with synthetic medium to perform batch cultivations. Here, the HTC-LF was diluted with the blackwater from biosolid dewatering, without adding any microelements or main nutrients to perform a continuous cultivation. A microalgal community was grown, consuming nutrients and the COD, lowering the toxicity. The obtained biomass was used to produce second-generation nano -parti

Due to the Covid-19 pandemic, the use of disposable face masks has been adopted worldwide as a precautionary measure to slow down the transmission of the virus. This has determined an unprecedented rise in the production of these protective equipments, and unfortunately to a new form of environmental contamination due to the improper disposal. To provide a preliminary estimation of the release of microfibers by a surgical mask dumped in the marine environment, we carried out artificial weathering experiments. Results indicated that a single surgical mask submitted to 180 hours UV-light irradiation and vigorous stirring in artificial seawater may release up to 173,000 fibers/ day. Moreover, SEM and micro-FTIR analysis carried out onto surgical masks collected from Italian beaches highlighted the same morphological and chemical degradation signature observed in the masks subjected to the artificially weathering experiments, confirming the risks of a similar microfiber release into the marine environment.

The presence of microplastics (MPs) in the marine environment is a concerning topic due to the ecotoxicological effects and possible seafood contamination. Data is needed to evaluate human exposure and assess risks, in the context of a healthy and beneficial seafood consumption. While microplastic ingestion by wild fish has been reported since the early 70's, farmed fish are rarely investigated. Here, for the first time the presence of microplastics in fish cultivated in the coastal water of Tenerife (Canary Island, Spain) was evaluated. From 83 examined individuals, 65% displayed microplastics in their gastrointestinal tracts, with averages between 0.6 ± 0.8 (SD) and 2.7 ± 1.85 (SD) particles per fish. The total number of microplastics detected was 119. Fibres (81%) and fragments (12%) were the predominant shapes. FTIR analysis showed that fibres were mostly composed by Cellulose (55%) and Nylon (27%), whereas fragments by PE (25%) and PP (25%).

Microalgae are a precious source of polyunsaturated fatty acids (PUFA), however extraction is difficult due to the peculiar microalgae cell structure. Here we describe a new method based on the application of chitosan nanoaggregates as CO2 responsive emulsifier, used to promote the swelling of algae cell wall and the formation of a large oil – ethanol interphase area during the ethanolysis. Tests were carried out with Pseudokirchneriella subcapitata and Nannochloropsis sp. at different biomass/ethanol/chitosan ratios. CO2 was added to trigger demulsification to promote an easy recovery of the lipid fraction. The highest yields in PUFA were obtained with Nannochloropsis sp. (207.9 mg/g of oil) using 0.4% wt of chitosan and 1:10 biomass:ethanol ratio; 43.6 mg/g of linolenic acid were obtained from Pseudokirchneriella subcapitata. Overall, because the method employs ethanol, a generally recognized as safe (GRAS) solvent, and food grade additives, it is suited for the preparation of PUFA supplements.

Due to the increasing presence of plastic and plastic associated contaminants in the aquatic environments, the monitoring of this contamination in fish products and the understanding of possible human health implications is considered urgent. However, data are still relatively scarce, mostly due to the methodological challenges in the chemical analysis: these contaminants are ubiquitous and procedural contamination from the laboratory is frequent. In this work, we compared solid-phase microextraction (SPME) to ultrasonic assisted solvent extraction (UASE) as sample preparation methods for the liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) determination of phthalates in fish fillets. UASE was carried out with an acetone-hexane (1:1) solution and according to a reference procedure aimed to obtain the exhaustive extraction of the target analytes. SPME was carried out by applying C18 fibers in direct immersion mode and by using water/methanol 20:80 mixture to desorb the aliquot required for the analysis. Overall, SPME displayed an improved control of the background contamination and enabled lower LOQs. Precision, calculated as relative standard deviation (RSD) on replicates of a reference sample, was below 24% for both the method. Analysis of real samples purchased from Italian supermarkets showed that SPME might be an efficient tool for estimating the risk associated with fish consumption.

Current approaches to evaluate microplastic contamination of the marine environment include the use of marine organisms as bioindicators and the detection of plastic-associated contaminants in their tissues. Liquid/liquid extraction and/or solid-phase extraction are the usual methods of choice for sample preparation. However, these methods suffer from background contamination, due to the large volume of solvents used and the ubiquity of plasticizers in laboratory environments. Moreover, organisms used in the study may belong to species that are rare or endangered and these should preferably not be sacrificed as a consequence of the relatively sizeable biological material required for exhaustive sample extractions and the destructive nature of mass spectrometry analysis. In this study, we evaluated, as a non-lethal alternative, a procedure involving solid phase microextraction (SPME) coupled with liquid chromatography mass spectrometry (LC/MS) analysis. Two coral reef invertebrates that may be sensitive to microplastic contamination were used for the tests, i.e., the scleractinian Danafungia scruposa and the bivalve mollusk Tridacna maxima. The results showed that the method was effective in quantifying phthalate esters within ten minutes of exposure, offering at the same time an improved control of the background contamination compared to the classical extraction procedure.

This paper describes the development and validation of a new procedure for the determination of phthalates in marine invertebrates, based on biocompatible solid-phase microextraction (BioSPME) followed by liquid chromatography coupled to mass spectrometry. The importance of this application relies on the current use of marine organisms as bioindicators for microplastic contamination through the detection of phthalates in their tissues. Challenges originate from the availability and/or possible restriction on the use of the biological materials, the need for user- friendly procedures for simplifying and speeding up operations in the marine environments, and the ubiquitous presence of phthalates in the laboratory environments that may cause background contamination. BioSPME served as an effective solution to all these issues, owing to the extreme minimization of the sample manipulation. Sampling operations were limited to the direct transfer of small amounts of the biological materials (150 mg) inside glass vials capped with aluminium lids; extractions were carried out by ultrasonication in acetone followed by dilution in ultrapure water and BioSPME clean-up; Electrospray (ESI) LC–MS/MS was employed for the final analytical determinations on the purified extracts. Tests were carried out on samples belonging to three different phyla, namely Cnidaria, Porifera, and Mollusca obtained from Maldivian coral reef environments and used for a current microplastic contamination biomonitoring project. Overall, very good sensitivity and repeatability, with negligible back contamination of the blanks were observed. The limits of detections were between 0.2 and 2.1 ng/g and precision, calculated as relative standard deviation (RSD), was below 14% for all the tested phthalates.

The impact of microplastics (MPs) on reef-building corals are still largely unknown. The scientific literature provides evidence from lab feeding trials that coral may ingest MPs. Several adverse effects, i.e., necrosis and bleaching, have also been highlighted. However, field studies are limited. Here, we investigated for the first time the possible correlation between MP seawater contamination and the presence of phthalic acid esters (PAEs), a class of MP-associated contaminants, in scleractinian corals. The survey was carried out in a remote coral reef atoll in the Indian Ocean located in the Maldivian archipelago, considered as a case study. MPs and PAEs were monitored in subsurface neustonic tow samples and scleractinian corals across twelve sampling sites. The results showed widespread MP contamination and the presence of appreciable levels of PAEs in the scleractinian corals sampled inside the atoll rim near an inhabited island, which correlated with the highest MP concentration.

BACKGROUND: Marine lipids are widely recognized as supplements beneficial to health in the human diet. Bluefin tuna, as most migrating fish, may have high and variable marine lipid contents in their tissues. The viscera of the specimens caught in the Mediterranean Sea are generally discarded. Only ovaries are (locally) used for artisanal seafood preparations. RESULTS: A multi-analytical approach carried out using infrared (IR), nuclear magnetic resonance (NMR) and mass spectrometry (MS) revealed that the perigonadal fats usually discarded during bluefin tuna evisceration are characterized by a high relative abundance of polyunsaturated triacylglycerols (76.2% of dry mass), with docosahexaenoic (DHA, 22:6) and eicosapentaenoic (EPA, 20:5) acids preferentially located at the sn-2 position of the glycerol backbone. By contrast, in fats from the ovarian tissues, no wax esters and phospholipids were evidenced. Cholesterol was found in very low amounts (84 mg/100 g ovarian tissue). In vitro assays showed that this fatty material is rapidly hydrolyzed by lipase and is prone to auto-oxidation, especially if compared to the stable wax esters contained in the ovary. CONCLUSION: The results show that the perigonadal fats of bluefin tuna, traditionally wasted after evisceration, may be an interesting source for the preparation of marine lipid supplements that do not require complex fractionation processes. © 2019 Society of Chemical Industry

This study focused on the characterization of microbial communities during the desulfurization of ground tire rubber (GTR) by two bacterial strains i) Gordonia desulfuricans DSM 44462T, and ii) Rhodococcus sp. AF21875. Automated ribosomal inter-genic spacer analysis (ARISA), and high throughput sequencing of 16S rRNA gene amplicons were used to analyze samples collected from the bioreactors over time to detect the persistence of the inoculated bacteria within the autochthonous communities, and to compare communities in the bioreactors. Furthermore, the abundance of total bacteria (16S rRNA gene) and biodesulfurization potential (dszA) were estimated using qPCR, in the bioreactors and on GTR before the treatment. ARISA showed that G. desulfuricans DSM 44462T was able to persist, while there is no clear evidence of Rhodococcus sp. AF21875 persistence into the bioreactor due to the presence of matching ARISA fragments in the untreated GTR. In both bioreactors, a high abundance of genus Gordonia and Rhodococcus was observed, with an increase of dszA copy numbers over time. Vulcanizates containing biodesulfurized GTRs showed better mechanical and rheological properties than an untreated GTR vulcanizate and even comparable with a natural rubber reference.

Microplastics are recognized as a growing threat for the marine environment that may even affect areas generally considered pristine. In this work we surveyed the microplastic contamination in the Faafu Atoll (Maldives, Indian Ocean) across twelve sampling station, located either inside or outside the reef rim. Sediments and seawater samples were collected. Despite the remoteness of the atoll, the scarce local population and low touristic annual afflux, the detected average abundance were 0.32 ± 0.15 particles/m3 in the surface water and 22.8 ± 10.5 particles/m2 in the beach sediments. Polymers identified through Fourier-Transform Infrared spectroscopy were mostly polyethylene, polypropylene, polystyrene, polyvinylchloride, polyethyleneterephtalate, and polyamide. Elastomeric residues and charred microparticles were also found. In particular, the charred microparticles were prevalently located nearby the inhabited island and they might be considered a peculiarity of the area, related to local practice of burning plastic waste at the shoreline.

This study investigates the effect of technologies for heavy metal stabilization on the concentration of PolyChlorinatedDibenzo-p-Dioxins (PCDD) and PolyChlorinatedDibenzoFurans (PCDF), abbreviated PCDD/F, in Municipal Solid Waste Incineration (MSWI) fly ash. We determined the variation of the Total Organic Carbon (TOC) and PCDD/F concentration between raw and stabilized material. The technologies, that already proved to be very promising for heavy metal entrapment, showed encouraging results also for PCDD/F detoxification. This result could be very impacting on the management of MSWI fly ash: at the best of our knowledge, there are no methods, in literature, that can provide good results in stabilization of heavy metals, and abatement of chlorinated organic pollutants contained in the same matrix.

Environmentally persistent free radicals (EPFRs) are toxic products deriving from incomplete combustion and are able to generate DNA damage and pulmonary dysfunction. They are formed on particulate matter through interaction with aromatic hydrocarbons, catalyzed by transition metal oxides, and produce reactive oxygen species (ROS) in aquatic media. The processes are already described for substituted aromatic molecules, for example, phenol, but not for unsubstituted aromatic systems, such as benzene. This Article reports on the reaction of benzene with molecular oxygen in the presence of CuxO/SiO2, suggesting a mechanism based on cluster and periodic computational models. The activation of O2 by interaction with silica coordinated Cu(I) centers leads to a peroxy species that yields the phenoxy radical upon reaction with benzene. Dissociation of OH• radical eventually allows for the recovery of the catalyst. The experimental characterization of the CuxO/SiO2 catalyst regarded morphology, crystal structure, copper electronic state, and crystal field around Cu(II). Electron paramagnetic resonance (EPR) spectroscopy revealed the formation of phenoxy radical entrapped in the catalyst upon reaction between benzene and CuxO/SiO2. Moreover, EPR investigation of ROS in aqueous solution evidenced the generation of OH• radicals by benzene-contacted CuxO/SiO2. All of the experimental results nicely fit the outcomes of the computational models.

In the ancient world beeswax and honey were of crucial importance not only for nutrition, but also for a range of activities including various artisanal practices. A rich body of iconographic and literary evidence has proven very informative, but archaeological data are strongly underrepresented in studies on ancient beekeeping. A multidisciplinary excavation project of the Etruscan trade center of Forcello near Bagnolo San Vito (Mantua province), led to the discovery of charred honeycombs in a workshop dated to 510-495 BCE. Morphoscopical, palynological and chemical analyses (IR, LC-MS, GC-MS) were conducted on these honeycombs and their associated materials (bee-breads and a mixture of melted honeycombs) in order to reconstruct beekeeping practices and the local environment. Palynological data indicate that honeybees were feeding on plants from both aquatic and ruderal landscapes. The palynological record from the bee-breads suggests the practice of itinerant beekeeping along rivers, an activity described by Pliny the Elder (Natural History, XXI.43.73) a few centuries later in relation to the town of Ostiglia (Mantua province) ca. 20 km downstream the investigated site. Hence, confirming the historical source, beekeeping in Iron Age Northern Italy appears to be characterized by a remarkably high degree of specialization. In addition, the pollen content of the melted honeycombs provides evidence for an unprecedented Vitis vinifera (grapevine) honey. The pollination syndrome suggests that bees fed on nectar of pre-domesticated or early-domesticated varieties of Vitis vinifera, confirming the archaeobotanical record of pips from Iron Age Northern Italy.

Nanoparticles of zero-valent iron (nZVI) represent a promising agent for environmental remediation. This is due to their core-shell structure which presents the characteristics of both metallic and oxidised iron, leading to sorption and reductive precipitation of metal ions. Nevertheless, nZVI application presents some limitations regarding their rapid oxidation and aggregation in the media which leads to the delivery of the ions after some hours (the "aging effect"). To address these issues, modifications of nZVI structure and synthesis methods have been developed in the last years. The aging problem was solved by using nZVI encapsulated inside carbon spheres (CE-nZVI), synthetized through Hydrothermal Carbonization (HTC). Results showed high heavy metals removal percentage. Furthermore, CE-nZVI were activated with nitrogen in order to increase the metallic iron content. The aim of this study was to test CE-nZVI post-treated with nitrogen at different temperatures in heavy metals removal, demonstrating that the influence of the temperature was negligible in nanoparticles removal efficiency.

The general aim of this study is the valorisation of Automotive Shredder Residue (ASR) via pyrolysis. Tar, the condensable gases obtained in the pyrolysis process, is an interesting alternative fuel. Thus, the pyrolysis process was investigated in order to maximize the tar yield. The design of experiment approach was used to plan a series of experiments and to identify which operating variables influence the yield of the process. Temperature and carrier gas flow proved to be significant factors affecting the yield, while the influence of ASR light fraction amount pyrolysed was negligible. In the experimental domain, the maximum response was obtained at 500 °C and 100 mL/min

A 13-years study shows that a careful design of the flue gas cleaning system of a full scale secondary aluminium refining plant results in a minimized and very stable emission of Polychlorinated Dibenzo–p–Dioxins (PCDD), Polychlorinated Dibenzo Furans (PCDF) and dioxin-like Polychlorinated Biphenyls (PCB). The value of equivalent toxicity of PCDD/F in the emission was definitely of an order of magnitude less than the regulation limit. In the initial flue gas cleaning system, the PCB mean fingerprint after the slow cooling of the flue gas was typical of de novo synthesis. Instead, in the presence of quenching, there was evidence that the fast cooling of flue gas prevented the PCB de novo synthesis. In fact, the PCB profile was similar to that in the air collected from the aspiration hoods for the quenching. The gas-phase and solid-phase partitioning of PCBs, before and after the fabric filters, highlights the predominant role of the vapor phase with respect to the total removal efficiency. The polycyclic aromatic hydrocarbons breakdown could be an additional de novo formation pathway even in industrial plants.

The general aim of this study is the recovery of Automotive Shredder Residue (ASR). The ASR light fraction, or car fluff, that was collected at an Italian shredding plant was pyrolysed at various temperatures (500–800 °C) in a lab-scale reactor. The condensable gases (tar) and solid residue yields increased with decreasing temperature, and these products were characterized to suggest a potential use to reclaim them. The higher heating value (HHV) of tar was 34–37 MJ/kg, which is comparable with those of fossil fuels. Furthermore, the ash content was low (0.06–4.98%). Thus, tar can be used as an alternative fuel. With this prospect, the concentrations of polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in tar were determined. The toxicity of tar changes with temperature (1–5 ng I-TEQ/g), and the PCDFs significantly contribute to tar toxicity, which was 75–100% with a maximum of 99.6% at 700 °C. Regarding the characterization of the solid residue, the low HHV (2.4–3.3 MJ/kg) does not make it suitable for energy recovery. Regarding material recovery, we considered its use as a filler in construction materials or a secondary source for metals. It shows a high metal concentration (280,000–395,000 mg/kg), which is similar at different pyrolysis temperatures. At 500 °C, polycyclic aromatic hydrocarbons (PAHs) were not detected in the solid residue, whereas the maximum total PAH concentration (19.41 ng/g, 700 °C) was lower than that in fly ash from MSWI. In conclusion, 500 °C is a suitable pyrolysis temperature to obtain valuable tar and solid residue.

We developed a phenomenological approach to explain the kinetic experimental data of PCDD/F formation/destruction based on a reaction mechanism model at the congener group level. In the present work, we investigated the formation and destruction of PCDD/F on fly ash as a function of time at 280 °C, chlorine mass balance, evolution of the total equivalent toxicity and kinetic modelling. We determined that the volatilization process is negligible and that the reactive processes at short reaction times only become important above 300 °C. The results provide a substantial improvement on existing studies. We experimentally demonstrated, for the first time, that there is a correlation between the oxidative breakdown of native carbon and PCDD/F de novo synthesis. Data processing by our kinetic model showed that the formation of oxygen complexes C(O) was the determining step for de novo synthesis of PCDD/F. Indeed, the calculated reaction time at which the PCDD/F concentration was at a maximum (850 min) was greater than that calculated for the oxygen complexes C(O) (435 min). Moreover, the experimental carbon conversion efficiency for PCDD/F production (0.0032% at 600 min maximum) was in a very good agreement with the theoretical conversion (0.0041%).

The ultrasonic devulcanization of a ground tire rubber in a co-rotating twin-screw extruder was studied and optimized using the response surface methodology based on an experimental design. This approach allowed evaluating the influence on the process of four variables (ultrasonic amplitude, temperature, screw speed and flow rate). The devulcanization process was investigated using several responses, including crosslink density, gel fraction, complex viscosity of the devulcanizates and tensile strength, modulus and elongation at break of the revulcanizates. Regression models and response surfaces were obtained for each response. The results predicted by these models showed good agreement with experimental values. The ultrasonic amplitude was found to be the most effective variable influencing the devulcanization process and mechanical properties. In addition, an optimization was carried out through a desirability function approach, in order to define the combination of process parameters that maximizes the mechanical properties and minimizes the degradation of the tire rubber.

In the recent past we reported the investigation of different devulcanization processes of a ground tire rubber (GTR) such as supercritical fluid, ultrasonic and biological technologies. Each of these techniques had been previously optimized, focusing on the experimental combination of parameters providing the best devulcanization conditions. The present study aims to extensively compare the optimal conditions of these three different techniques for the devulcanization of a GTR. In particular the GTR and the devulcanizates by each technique were blended into raw natural rubber at a concentration of 10 phr. The rheological and mechanical properties of their vulcanizates were investigated and compared to find out the rubber providing the highest compatibility for compounding and revulcanization. In addition, a comparison of these results was made with the ones of raw natural rubber compound and vulcanizate.