Carbon dot/polylactic acid nanofibrous membranes for solar-mediated oil absorption/separation: Performance, environmental sustainability, ecotoxicity and reusability.

Carbon dots (CDs) are promising photothermal nanoparticles that can be utilized in environmental treatments. They exhibit favorable physicochemical properties, including low toxicity, physical and chemical stability, photo-dependant reversible behaviour, and environmentally friendly synthesis using benign building blocks. Here, we synthesized innovative CDs/polylactic acid (PLA) electrospun composite membranes for evaluating the removal of hydrophobic compounds like long-chain hydrocarbons or oils in biphasic mixtures with water. The ultimate goal was to develop innovative and sustainable solar-heated oil absorbents. Specifically, we fabricated PLA membranes with varying CD contents, characterized their morphology, thermal, and mechanical properties, and assessed the environmental impact of membrane production according to ISO 14040 and 14044 standards in a preliminary "cradle-to-gate" life cycle assessment study. Solar radiation experiments demonstrated that the CDs/PLA composites exhibited greater uptake of hydrophobic compounds compared to pure PLA membranes, ascribable to the CDs-induced photothermal effect. The adsorption and regeneration capacity of the new CDs/PLA membrane was demonstrated through multiple uptake/release cycles. Ecotoxicity analyses confirmed the safety profile of the new adsorbent system towards freshwater microalgae, further emphasizing its potential as an environmentally friendly solution for the removal of hydrophobic compounds in water treatment processes.

A rare case of radiation-induced breast angiosarcoma: a case report.

We describe a rare case of a 77-year-old woman with radiation-induced breast angiosarcoma (RIAS) in whom radical surgery with negative margins determined that at 14-month of follow-up there is no evidence of either local or systemic recurrence without having to resort to adjuvant chemotherapy.

Comparative evaluation using PRO of an algorithm of one-stage immediate alloplastic breast reconstruction versus two-stage reconstruction.

BACKGROUND: One-stage direct-to-implant (DTI) immediate breast reconstruction has proven to be an oncologically safe technique, but there are some conditions that do not allow its performance. The introduction of new surgical techniques and the recent COVID-19 pandemic have pushed us to introduce a breast reconstruction algorithm in our clinical practice. This allows a one-stage immediate reconstruction for all patients, regardless of their anatomical characteristics, the type of implants used, and the need for postoperative radiotherapy. METHODS: A total of 40 patients were recruited and divided into two cohorts, 20 patients underwent immediate one-stage breast reconstruction in the period between October 2019 and January 2021, and 20 patients completed the two-stage reconstructive process in the period prior to October 2019. During the follow-up at 6 months, all patients who had completed the reconstructive process filled out the Breast-Q Reconstruction Module Pre and Postoperative scales questionnaire. The outcomes of the questionnaires were compared between the two cohorts, and statistical analysis was carried out using SPSS Statistics 20 (IBM Corporation, Armonk, NY, USA). RESULTS: The analysis of patient-reported outcomes showed that patients from the one-stage group reported better outcomes in all items evaluated. We did not find statistically significant differences concerning the rate of complications and length of hospital stay between the two groups. CONCLUSIONS: The analysis of the results shows that the outcomes reported by patients who completed breast reconstruction according to our algorithm are statistically better than those with the two-stage technique.

Allelopathic interactions between phytobenthos and meiofaunal community in an Adriatic benthic ecosystem: Understanding the role of aldehydes and macroalgal structural complexity.

Macroalgae produce several allelopathic substances, including polyunsaturated aldehydes (PUAs), which may inhibit photosynthesis and growth rates of other algal species, and grazing. Additionally, macroalgal structural complexity is an important factor in determining abundance patterns and size structure of epiphytic organisms. In this study the PUAs production of two Mediterranean macroalgae, Dictyopteris polypodioides, (DP, Phaeophyceae, Dictyotales) and Cystoseira compressa (CC, Phaeophyceae, Fucales), was characterized to clarify the relationships between the meiobenthic and microphytobenthic communities. Results showed a higher PUAs production and a diverse qualitative profile for DP, which reported long-chain compounds (i.e. C14-C16) as main aldehydes, than CC, with the short-chain C6:2 as the main compound, as well as variability among sampling times. A clear separation of the meiofauna and microphytobenthos assemblages was found for the macroalgae, but with different temporal trends. Dissimilarities were due to five microalgal orders, namely Naviculales, Lyrellales, Gonyaulacales (i.e. Ostreopsis), Bacillariales, and Licmophorales, and to the meiofaunal groups nematodes, copepods, and copepod nauplii, which were more abundant on DP than on CC. Results indicate that macroalgal complexity is a major determinant of the meiofaunal community structure (accounting for 26% of the variation), rather than PUAs production itself (17%). PUAs effects seem species-specific, thus affecting some grazers instead of the entire community. Conversely, microphytobenthos affected the meiofauna assemblages, particularly harpacticoids, confirming the role of these organisms as the primary food source of all marine food chain producers. Since PUAs are produced also by several epiphytic diatoms, the understanding of their effects on the community structure and on the relationships among taxa in the field is complicated and requires further in-depth investigations in simplified systems (i.e. microcosms).

Historical record of polychlorinated biphenyls (PCBs) in the continental shelf of the Korea Strait.

The vertical distribution of PCBs was measured in a dated core from the continental shelf of the Korea Strait. The historical trend of deposition and fluxes of individual and total PCB agreed well with the dynamics of historical tendencies of PCBs consumption in South Korea up to mid-1980 and a peak of total PCBs of 810 ng kg-1 was recorded at the turn of the 1960s. A second period of deposition, when concentrations of total PCB up to 1007 ng kg-1 were reached, was evidenced between 1989 and 2010 after the ban of PCBs. Sediments deposited in 1990s-2010, and sediments deposited in the period of maximum PCBs use (1956-1983) are both enriched in the less chlorinated homologue groups (tri- and tetrachlorobyphenyls) and congener PCB 118. However, the ratio of dioxin-like PCBs, and dichloro- and hexachloro homologue groups disclosed compositional variations between the two time periods. Source analysis suggested that PCBs in the sediment record mainly originated from Kanechlor 300, Kanechlor 400 and Aroclor 1242 technical mixtures overlapped by secondary/unintentional combustion sources from regional steel making processes in the last decades (1990s-2010).

Assessing the environmental hazard of individual and combined pharmaceuticals: acute and chronic toxicity of fluoxetine and propranolol in the crustacean Daphnia magna.

Pharmaceuticals are widespread emerging contaminants and, like all pollutants, are present in combination with others in the ecosystems. The aim of the present work was to evaluate the toxic response of the crustacean Daphnia magna exposed to individual and combined pharmaceuticals. Fluoxetine, a selective serotonin re-uptake inhibitor widely prescribed as antidepressant, and propranolol, a non-selective ß-adrenergic receptor-blocking agent used to treat hypertension, were tested. Several experimental trials of an acute immobilization test and a chronic reproduction test were performed. Single chemicals were first tested separately. Toxicity of binary mixtures was then assessed using a fixed ratio experimental design. Five concentrations and 5 percentages of each substance in the mixture (0, 25, 50, 75, and 100%) were tested. The MIXTOX model was applied to analyze the experimental results. This tool is a stepwise statistical procedure that evaluates if and how observed data deviate from a reference model, either concentration addition (CA) or independent action (IA), and provides significance testing for synergism, antagonism, or more complex interactions. Acute EC50 values ranged from 6.4 to 7.8 mg/L for propranolol and from 6.4 to 9.1 mg/L for fluoxetine. Chronic EC50 values ranged from 0.59 to 1.00 mg/L for propranolol and from 0.23 to 0.24 mg/L for fluoxetine. Results showed a significant antagonism between chemicals in both the acute and the chronic mixture tests when CA was adopted as the reference model, while absence of interactive effects when IA was used.

Chemical and ecotoxicological properties of three bio-oils from pyrolysis of biomasses.

In view of the potential use of pyrolysis-based technologies, it is crucial to understand the environmental hazards of pyrolysis-derived products, in particular bio-oils. Here, three bio-oils were produced from fast pyrolysis of pine wood and intermediate pyrolysis of corn stalk and poultry litter. They were fully characterized by chemical analysis and tested for their biodegradability and their ecotoxicity on the crustacean Daphnia magna and the green alga Raphidocelis subcapitata. These tests were chosen as required by the European REACH regulation. These three bio-oils were biodegradable, with 40-60% of biodegradation after 28 days, and had EC50 values above 100mgL(-1) for the crustacean and above 10mgL(-1) for the alga, showing low toxicity to the aquatic life. The toxic unit approach was applied to verify whether the observed toxicity could be predicted from the data available for the substances detected in the bio-oils. The predicted values largely underestimated the experimental values.

Tigriopus fulvus: The interlaboratory comparison of the acute toxicity test.

The paper reports the results of an interlaboratory comparison involving 11 laboratories, with the objectives of apply and validate a new standardized ecotoxicological method on marine crustacean Tigriopus fulvus. Copper was chosen as reference toxicant as indicated in the official method. The results of two independent tests performed by all the participants, demonstrated that the new method is simple, fast and easy to learn. This is confirmed even by the values of z-score index calculated for each laboratory and the relative coefficient of variation (CV) which are 6.32% after 24h, 6.56 after 48h and 35.3% after 96h, mentioned in the ISO standards for the precision of interlaboratory assays. Therefore its use could be recommended in environmental studies and monitoring.

Does the exposure mode to ENPs influence their toxicity to aquatic species? A case study with TiO2 nanoparticles and Daphnia magna.

Recent studies suggest that the ecotoxicity of engineered nanoparticles (ENPs) is dependent upon the treatment of ENPs in suspensions (e.g. sonication or use of solvents) and on the mode of exposure to test organisms. We conducted several bioassays with Daphnia magna in order to determine how adverse effects of TiO2 nanoparticles (n-TiO2) are influenced by experimental set-up. Several treatments were applied, including three test media, several treatments of n-TiO2 suspensions (stirring, sonication) and different exposure modes (exposure duration and volume of test suspension). No adverse effects were observed when D. magna were exposed to 50 mL of suspension, regardless of TiO2 concentration (up to 250 mg/L) and exposure duration. Conversely, adverse effects were observed when D. magna were exposed to 2 mL of suspension for 96 h with a 50 % effect concentration EC50 values ranging from 32 mg/L to 82 mg/L. Test media had no significant influence on the outcome of all treatments. For a better mechanistic understanding of the experimental set-up at which adverse effects were observed, the particle size of n-TiO2 in the test media was characterized throughout the test duration. These measurements revealed a fast and strong agglomeration with a secondary particle size in the order of magnitude of micrometers. Our study describes how the effects of n-TiO2 on D .magna are influenced by the duration of exposure and volume of media, highlighting the need for standardization of experimental methods.

Freshwater ecotoxicity characterisation factor for metal oxide nanoparticles: a case study on titanium dioxide nanoparticle.

The Life Cycle Assessment (LCA) methodology is widely applied in several industrial sectors to evaluate the environmental performance of processes, products and services. Recently, several reports and studies have emphasized the importance of LCA in the field of engineered nanomaterials. However, to date only a few LCA studies on nanotechnology have been carried out, and fewer still have assessed aspects relating to ecotoxicity. This is mainly due to the lack of knowledge in relation on human and environmental exposure and effect of engineered nanoparticles (ENPs). This bottleneck is continued when performing Life Cycle Impact Assessment, where characterization models and consequently characterization factors (CFs) for ENPs are missing. This paper aims to provide the freshwater ecotoxicity CF for titanium dioxide nanoparticles (nano-TiO2). The USEtox model has been selected as a characterisation model. An adjusted multimedia fate model has been developed which accounts for nano-specific fate process descriptors (i.e. sedimentation, aggregation with suspended particle matter, etc.) to estimate the fate of nano-TiO2 in freshwater. A literature survey of toxicity tests performed on freshwater organism representative of multiple trophic levels was conducted, including algae, crustaceans and fish in order to collect relevant EC50 values. Then, the toxic effect of nano-TiO2 was computed on the basis of the HC50 value. Thus, following the principle of USEtox model and accounting for nano-specific descriptors a CF for the toxic impact of freshwater ecotoxicity of 0.28 PAFdaym(3)kg(-1) is proposed.

Spatial patterns of metals, PCDDs/Fs, PCBs, PBDEs and chemical status of sediments from a coastal lagoon (Pialassa Baiona, NW Adriatic, Italy).

The European Water Framework Directive (WFD) establishes a framework for the protection and improvement of all water bodies including transitional waters; its final objective is to achieve at least 'good status' by 2015. In the present work, a hierarchical sampling design was applied to analyze the influence of anthropogenic inputs on the spatial distribution of metals, polychlorinated dibenzo-p-dioxins (PCDDs) dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediment at four areas in Pialassa Baiona coastal lagoon. In order to assess the chemical status, levels of priority substances and other pollutants were compared with the recently developed national Environmental Quality Standards (EQS) and site specific background levels for metals. Levels of mercury and PCBs were particularly high and exceeded their national EQS values at all sampled areas, thus not contributing to the achievement of a good chemical status of this transitional water body according to the WFD classification.

Introduction of oxygenated side chain into imidazolium ionic liquids: evaluation of the effects at different biological organization levels.

The biological effects of a class of oxygenated imidazolium ionic liquids were studied in comparison with alkyl imidazolium salts (BMIM BF4 and BMIM N(CN)2).The cellular and subcellular effects were evaluated on rat pheochromocytoma PC12 cell lines, through MTT test, lactate dehydrogenase release and acetylcholinesterase inhibition; the eco-toxicological responses were assessed through the acute toxicity tests towards Daphnia magna and Vibrio fischeri. The introduction of ethoxy moieties in the lateral chain of imidazolium cations reduced the biological effects in all the tests. The acute toxicity towards D. magna was not affected by the number of ethoxy units, but the crustacean seemed to be sensitive to the type of anion; on the contrary, a further addition of ethoxy moieties increased the toxicity towards V. fischeri, M(OE)4MIM N(CN)2 being the most toxic oxygenated ionic liquid. In the cytotoxicity assays the salts with oxygenated cations resulted ineffective compared to BMIMs, independently from the anion and the number of ethoxy units in the lateral chain. In order to estimate the influence on membrane fluidity, an analysis of fluorescence anisotropy was done and it indicated that BMIM BF4, the most toxic ionic liquid among the tested ones, led to a destabilization of the model membranes at any molarity.

Acute toxicity of oxygenated and nonoxygenated imidazolium-based ionic liquids to Daphnia magna and Vibrio fischeri.

Room-temperature ionic liquids (RTILs) recently have generated great interest as a result of their potential commercial applications. In particular, because of their negligible vapor pressure and low inflammability, they have been suggested as green alternatives to traditional organic solvents. The toxicity and potential environmental risk of this heterogeneous class of chemicals, however, are poorly understood. An alkyl-substituted RTIL, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]), is one of the most widely used cations of RTILs, and information regarding its toxicity is relatively extensive. On the other hand, oxygenated chain-substituted ionic liquids, 1-methoxyethyl-3-methylimidazolium salts (moemims), are a new class of RTILs that have been poorly studied. Here, we compared the acute toxicity of [bmim][BF(4)] and moemims to the crustacean Daphnia magna (end point, 48-h immobilization) and the bacterium Vibrio fischeri (end point, 15-min inhibition of bioluminescence). The concentrations of [bmim][BF(4)] resulting in 50% of the maximum adverse effect (EC50s) for D. magna and V. fischeri were 5.18 and 300 mg/L, respectively, and were consistent with previously published values. The EC50s of the two moemims for D. magna are very similar, ranging from 209 to 222 mg/L in different experimental trials, and are higher by two orders of magnitude than the EC50 of [bmim][BF(4)]. The EC50s of 1-methoxyethyl-3-methylimidazolium tetrafluoroborate ([moemim][BF(4)]) and 1-methoxyethyl-3-methylimidazolium dicyanamide ([moemim][dca]) for V. fischeri are 3,196 and 2,406 mg/L, respectively. Results indicate that introduction of an oxygenated side chain in the imidazolium cation can greatly reduce the toxicity of RTILs and that these RTILs are less toxic than commonly used chlorinated solvents, such as tricloromethane, but are more toxic than nonchlorinated solvent, such as methanol and acetone.

Acetylcholinesterase activity in the earthworm Eisenia andrei at different conditions of carbaryl exposure.

Recent reports have stressed the need for a better understanding of earthworm biomarker responses. We aimed at investigating acethylcholinesterase (AChE) activity in the earthworm Eisenia andrei after exposure to carbaryl or its commercial formulation Zoril 5 under different in vitro and in vivo experiments. In addition, lysosome membrane stability was assessed by neutral red retention assay in the same experimental conditions. AChE basal Km and Vm values were about 0.16 mM and 41 nmol min(-1) mg protein(-1), respectively. Carbaryl dose-dependently decreased Vmax, while not affecting Km values. Carbaryl reduced earthworm AChE activity within 1 day of in vivo exposure to contaminated filter paper. Tested on soil, carbaryl inhibited AChE with the maximum effect after 3 days; in contrast, lysosome membrane stability of coelomocytes indicated a maximum toxicity after one day, followed by a recovery. AChE inhibition by Zoril 5 was highest after one day, while lysosome membrane stability declined progressively. In all cases, carbaryl dose-dependently decreased Vmax while not affecting Km values. In conclusion, E. andrei AChE activity assessed in vitro is dose-dependently inhibited by the carbamate compound carbaryl, which acts as a pure competitive inhibitor. In vivo experiments suggested that pure and co-formulated carbaryl have different time and/or dose dependent effects on earthworms. Our results further support the use of AChE inhibition as an indicator of pesticide contamination, to be included in a battery of biomarkers for monitoring soil toxicity.

Toxicity of copper-spiked sediments to Tubifex tubifex (Oligochaeta, Tubificidae): a comparison of the 28-day reproductive bioassay with a 6-month cohort experiment.

Results from a 28-day adult reproductive bioassay using the aquatic oligochaete Tubifex tubifex (Müller, 1774) are compared with life table statistics obtained from a 6-month experiment on cohorts of the same species. This was done by simultaneously performing the two tests on copper spiked sediments. Five concentrations and a control were tested. The 28-day bioassay was performed 3 times in succession. Several endpoints were considered for each test and LOEC, IC10 and IC50 were calculated. IC50 estimates for the number of young produced in the 28-day bioassay range from 81 to 107 mg/kg; IC50 estimates for different endpoints of the cohort experiment ranged from 88 to 106 mg/kg. The 28-day bioassay showed essentially the same sensitivity as the cohort experiment to copper. This suggests that the 28-day reproductive bioassay does provide information that is relevant in assessing long-term toxic effects at the population level.