Risk assessment of natural and synthetic fibers in aquatic environment: A critical review.

Marine microplastics, categorized as primary and secondary, including synthetic microfibers like polyethylene terephthalate (PET), polypropylene (PP) and acrylic (PC), represent a potential environmental concern. The complex classification of these fibers, originating from diverse sources such as textiles and many others commercial goods, prompts a need for understanding their impact on aquatic organisms. This study assesses the ecological risks associated with both natural and synthetic fibers in aquatic ecosystems, focusing on toxicity data and their effects on taxonomic groups like Mollusca, Arthropoda, Echinodermata, Cnidaria, and Chordata. To carry out species sensitivity distribution (SSD) curves, a comprehensive analysis of scientific literature was conducted, collecting toxicity data related to various fibers. The resulting SSDs provide insights into the relative sensitivity of different taxonomic groups. The potential ecological risks were evaluated by comparing measured concentrations in diverse aquatic environments with Predicted No-Effect Concentration (PNEC) values. The calculation of Risk Quotient (RQ) allowed to indicate areas where fibers abundance poses a potential threat to aquatic organisms. The study reveals that nylon fibers can pose the highest toxicity risk, especially in Atlantic and Pacific Ocean, Arabian Gulf and VietNam river. Mollusca emerged as particularly sensitive to different fiber types, likely due to their body structure facilitating the accumulation of microfibers. The research emphasizes the urgent need for further studies to get data to human health risk analysis and to address comprehensive environmental management strategies to address the global issue of microfiber pollution.

Effect of biodegradable polymers upon grazing activity of the sea urchin Paracentrotus lividus (Lmk) revealed by morphological, histological and molecular analyses.

In the last years biodegradable polymers (BPs) were largely used as real opportunity to solve plastic pollution. Otherwise, their wide use in commercial products, such as packaging sector, is causing a new pollution alarm, mainly because few data reported about their behaviour in the environment and toxicity on marine organisms. Our previous results showed that embryos of the sea urchin Paracentrotus lividus (Lmk) exposed to poly(ε-caprolactone) (PCL), poly(3-hydroxybutyrate) (PHB) and poly(lactic acid) (PLA) showed delay of their development and morphological malformations, also affecting at the molecular levels the expression of several genes involved in different functional responses. In the present work for the first time, we tested the effects of five microplastics (MPs) obtained from BPs such as PBS, poly(butylene succinate), PBSA, poly(butylene succinate-co-butylene adipate), PCL, PHB and PLA, upon grazing activity of the sea urchin revealed by: i. histological analysis seeing at the gonadic tissues; ii. morphological analysis of the deriving embryos; iii. molecular analyses on these embryos to detect variations of the gene expression of eighty-seven genes involved in stress response, detoxification, skeletogenesis, differentiation and development. All these results will help in understanding how MP accumulated inside various organs in the adult sea urchins, and more in general in marine invertebrates, could represent risks for the marine environment.

Levels of rare earth elements on three abandoned mining sites of bauxite in southern Italy: A comparison between TXRF and ICP-MS.

The essential utilization of rare earth elements (REEs) for the production of several electronic devices is making the demand for them being increased all the time. This extensive use of these elements has also increased concern about human and environmental health. Previous studies have shown that REE levels are higher in environmental samples near mining sites, and they are highly possible to be transferred to biota. In this study, REE levels were determined in environmental samples collected from three abandoned mining sites of bauxite (Gargano, Otranto, and Spinazzola) in the region of Puglia, Southern Italy. The samples were digested and analyzed by two different techniques, Total X-Ray Fluorescence (TXRF) and Inductively Coupled Plasma - Mass Spectroscopy (ICP-MS) to investigate which technique is the most suitable for analysis of the REE content in samples from abandoned mining sites of bauxite. Only 6 REEs could be detected by TXRF, while all REEs were detected in all the samples by ICP-MS. Spinazzola is the richest site and Ce the most abundant REE in all three regions. REE levels are correlated between the soil and biota samples in many cases, although the calculation of the bioconcentration factor showed that REEs are not bioaccumulative. ICP-MS seems to be a more suitable technique for analysis of the whole REE content in environmental samples from abandoned mining sites of bauxite.

Uptake of cyclic C6O4 in maize and tomato: Results from a greenhouse study.

Cyclic C6O4 (cC6O4, CAS number 1190931-27-1) is a perfluoralkyl ether used as a polymerization aid in the synthesis of fluoropolymers and produced since 2011 as substitute of PFOA. This work reports the first data on bioaccumulation of cC6O4 on terrestrial plants (maize and tomato). In general, the observed accumulation and translocation of cC6O4 in plants is low or negligible. For maize a bioconcentration factor (BCFdw/dw) of about 39 was observed in the root compartment and much lower (BCFdw/dw = 12) in the aboveground tissues. In tomato the observed BCFs are substantially lower, with a maximum of 2.5 in leaves. The differences observed between the uptake and distribution of cC6O4 in maize and tomato plants are probably due to differences in plant physiology (but also in the experimental design of the tests). Maize plants grown at different concentrations in this study did not show relevant differences in term of biomass and growth, while tomato plants exposed to cC6O4 were subject to a delay in the ripening of the fruits (and relative biomass). The overall results are discussed in comparison with literature data available for legacy PFASs but the comparison is difficult due to differences in the experimental design. It is relevant to note that the concentrations tested in this study are significantly higher than expected environmental concentrations.

Toxicity and bioaccumulation of the fluorosurfactant cC6O4 in the earthworm Eisenia foetida (Savigny, 1826).

Cyclic C6O4 (cC6O4, CAS number 1190931-27-1) is a perfluoralkyl ether PFAS used as a polymerization aid in the synthesis of fluoropolymers and produced in Italy since 2011 as substitute of PFOA. To date, available ecotoxicological information on cC6O4 is related to regulatory requirements and limited to data on aquatic organisms, while the information on the effects for terrestrial organisms is completely lacking. This work reports the first ecotoxicological data of cC6O4 on terrestrial invertebrates: short- and long-term toxicity of cC6O4 on Eisenia foetida (Savigny, 1826), exposed to spiked soil under laboratory conditions, was investigated evaluating the earthworm survival and growth (observed after 7, 14 and 28 days of exposure), and reproduction (observed after an exposure period of 56 days). Furthermore, also bioaccumulation was investigated (28 days of exposure); overall results are discussed in comparison with literature data available for legacy PFAS. cC6O4 did not cause significant mortality on earthworms, for any of the tested concentrations and exposure periods (NOEC: > 1390 mg/kg d.w.), while the reproduction (measured as juveniles production) appears to be a more sensitive endpoint (EC50: 10.4 mg/kg d.w., EC10: 0.8 mg/kg d.w.). The observed adverse effects occur at levels significantly higher than realistic soil concentrations and cC6O4 appears to be less toxic than PFOA and PFOS. As for bioaccumulation, the results indicate a negligible bioaccumulation potential of cC6O4, whose Biota-Soil Bioaccumulation Factors (BSAF) are significantly lower than all other considered PFAS.

The under-investigated plastic threat on seagrasses worldwide: a comprehensive review.

Marine plastic pollution is a well-recognised and debated issue affecting most marine ecosystems. Despite this, the threat of plastic pollution on seagrasses has not received significant scientific attention compared to other marine species and habitats. The present review aims to summarise the scientific data published in the last decade (January 2012-2023), concerning the evaluation of plastic pollution, of all sizes and types, including bio-based polymers, on several seagrass species worldwide. To achieve this goal, a comprehensive and critical review of 26 scientific papers has been carried out, taking into consideration the investigated areas, the seagrass species and the plant parts considered, the experimental design and the type of polymers analysed, both in field monitoring and in laboratory-controlled experiments. The outcomes of the present review clearly showed that the dynamics and effects of plastic pollution in seagrass are still under-explored. Most data emerged from Europe, with little or no data on plastic pollution in North and South America, Australia, Africa and Antarctica. Most of the studies were devoted to microplastics, with limited studies dedicated to macroplastics and only one to nanoplastics. The methodological approach (in terms of experimental design and polymer physico-chemical characterisation) should be carefully standardised, beside the use of a model species, such as Zostera marina, and further laboratory experiments. All these knowledge gaps must be urgently fulfilled, since valuable and reliable scientific knowledge is necessary to improve seagrass habitat protection measures against the current plastic pollution crisis.

UV light assisted degradation of acid orange azo dye by ZVI-ZnS and effluent toxicity effects.

Azo dyes, the most common synthetic dyes used in the textile industry, are known xenobiotic compounds and recalcitrant to conventional degradation treatments. As consequence, such contaminants are often discharged into the effluents, treating aquatic ecosystems. Among several processes, the use of zero valent iron (ZVI) represents a suitable alternative to degrade organic molecules containing azo bonds. However, its applications are limited by corrosion and loss of reactivity over the time. To overcome these constraints, ZVI has been coupled to a suitable semiconductor (ZnS) to get a catalytic composite (ZVI-ZnS) active under UV light. The present work deals with the degradation of acid orange (AO7), used as model azo dye, by UV/ZVI-ZnS, as one step treatment and in combination with an adsorption process by biochar. The influence of ZVI-ZnS concentration (0.25, 0.5, 1 and 2 g/L) and reaction time (0-160 min) on degradation of AO7 were investigated. Intermediates formation was monitored by ESI-FT-ICR-MS analysis and the effluent toxicity was assessed by using Artemia franciscana. The experimental results showed that the UV/ZVI-ZnS process at 1 g/L of catalyst allowed to achieve a removal of AO7 up to 97% after 10 min. An increase of the dye relative concentrations as well as the toxicity related to intermediates formations has been observed for treatment time higher than 10 min. The total removal of AO7 together with effluent toxicity reduction was obtained only after the combined treatment (UV/ZVI-ZnS + biochar).

Catalytic Activity of Rare Earth Elements (REEs) in Advanced Oxidation Processes of Wastewater Pollutants: A Review.

In recent years, sewage treatment plants did not effectively remove emerging water pollutants, leaving potential threats to human health and the environment. Advanced oxidation processes (AOPs) have emerged as a promising technology for the treatment of contaminated wastewater, and the addition of catalysts such as heavy metals has been shown to enhance their effectiveness. This review focuses on the use of rare earth elements (REEs) as catalysts in the AOP process for the degradation of organic pollutants. Cerium and La are the most studied REEs, and their mechanism of action is based on the oxygen vacancies and REE ion concentration in the catalysts. Metal oxide surfaces improve the decomposition of hydrogen peroxide to form hydroxide species, which degrade the organics. The review discusses the targets of AOPs, including pharmaceuticals, dyes, and other molecules such as alkaloids, herbicides, and phenols. The current state-of-the-art advances of REEs-based AOPs, including Fenton-like oxidation and photocatalytic oxidation, are also discussed, with an emphasis on their catalytic performance and mechanism. Additionally, factors affecting water chemistry, such as pH, temperature, dissolved oxygen, inorganic species, and natural organic matter, are analyzed. REEs have great potential for enhancing the removal of dangerous organics from aqueous solutions, and further research is needed to explore the photoFenton-like activity of REEs and their ideal implementation for wastewater treatment.

Effects of biodegradable-based microplastics in Paracentrotus lividus Lmk embryos: Morphological and gene expression analysis.

Plastic pollution is a remarkable environmental issue. In fact, plastic is widespread in the lifetime and serious environmental problems are caused by the improper management of plastic end of life, being plastic litter detected in any environment. Efforts are put to implement the development of sustainable and circular materials. In this scenario, biodegradable polymers, BPs, are promising materials if correctly applied and managed at the end of life to minimize environmental problems. However, a lack of data on BPs fate and toxicity on marine organisms, limits their applicability. In this research, the impact of microplastics obtained from BPs, BMPs, were analyzed on Paracentrotus lividus. Microplastics were produced from five biodegradable polyesters at laboratory scale by milling the pristine polymers, under cryogenic conditions. Morphological analysis of P. lividus embryos exposed to polycaprolactone (PCL), polyhydroxy butyrate (PHB) and polylactic acid (PLA) showed their delay and malformations, which at molecular level are due to variation in expression levels of eighty-seven genes involved in various cellular processes, such as skeletogenesis, differentiation and development, stress, and detoxification response. Exposure to poly(butylene succinate) (PBS) and poly(butylene succinate-co-adipate) (PBSA) microplastics showed no detectable effects on P. lividus embryos. These findings contribute with important data on the effect of BPs on the physiology of marine invertebrates.

Synergistic, antagonistic, and additive effects of naphthalene, phenanthrene, fluoranthene and benzo(k)fluoranthene on Artemia franciscana nauplii and adult.

Polycyclic aromatic hydrocarbons (PAHs) are widespread across the globe and can be highly toxic for the marine environment. This research investigated the short-term (48 h of exposure) effects of PAHs mixtures on the nauplii and adult of crustacean Artemia franciscana considering the impact in term of toxicity and changes in gene expression. Results showed that all combinations caused additive or synergic effects with the exception of naphthalene + phenanthrene (NAP + PHE; Combination Index (CI) = 22.3), while naphthalene + benzo(k)fluoranthene (NAP + BkF; CI = 7.8) mixture evidenced an antagonistic effect. Real-time qPCR showed that all mixtures impacted the expression level of the five known genes involved in Artemia stress response. The effects of PAHs at environmental concentrations on both adult and nauplii suggested the need for further investigations about the impact of such contaminants on the marine biota considering that crustaceans can accumulate PAHs at concentrations comparable to those assessed in the present study.

Biodegradation of Plastics Induced by Marine Organisms: Future Perspectives for Bioremediation Approaches.

Plastic pollution is a distinctive element of the globalized world. In fact, since the 1970s the expansion and use of plastics, particularly in the consumer and commercial sectors, has given this material a permanent place in our lives. The increasing use of plastic products and the wrong management of end-of-life plastic products have contributed to increasing environmental pollution, with negative impacts on our ecosystems and the ecological functions of natural habitats. Nowadays, plastic pollution is pervasive in all environmental compartments. As aquatic environments are the dumping points for poorly managed plastics, biofouling and biodegradation have been proposed as promising approaches for plastic bioremediation. Known for the high stability of plastics in the marine environment, this represents a very important issue to preserve marine biodiversity. In this review, we have summarized the main cases reported in the literature on the degradation of plastics by bacteria, fungi, and microalgae and the degradation mechanisms involved, to highlight the potential of bioremediation approaches to reduce macro and microplastic pollution.

Geospatial pattern of topsoil pollution and multi-endpoint toxicity in the petrochemical area of Augusta-Priolo (eastern Sicily, Italy).

The present study was aimed at identifying geospatial patterns of pollutants including concentrations and toxicity as complex environmental mixtures, in topsoil samples close to petrochemical facilities in the heavily industrialized area of Augusta and Priolo in south-eastern Sicily (Italy). Elemental analysis of soil was conducted by ICP-MS for 23 metals and 16 rare earth elements (REEs). Organic analyses were primarily focused on polycyclic aromatic hydrocarbons (PAHs) (16 parent homologs) and total aliphatic hydrocarbons (C10 - C40). Topsoil samples were tested for toxicity in multiple bioassay models including: 1) developmental defects and cytogenetic anomalies in sea urchin Sphaerechinus granularis early life stages; 2) growth inhibition of diatom Phaeodactylum tricornutum; 3) mortality in nematode Caenorhabditis elegans; and 4) induction of mitotic abnormalities in onion Allium cepa. Samples collected at sites closest to defined petrochemical facilities were highest in select pollutants and correlated with biological effects in different toxicity endpoints. A noteworthy finding was the increased level of total REEs in sites closest to petrochemical facilities, suggesting their contributions to identifying petrochemical sources of pollutants to the environment. The combined data obtained in the different bioassays allowed exploration of geospatial patterns of effect in biota as a function of contaminant levels. In conclusion, this study provides consistent data of soil toxicity, metal and REE contamination at Augusta-Priolo sampling sites, and may provide an appropriate baseline for epidemiological studies on high incidences of congenital birth defects in the area and identification of at-risk localities.

Individual and combined effects of amoxicillin and carbamazepine to the marine copepod Tigriopus fulvus.

Pharmaceuticals can be considered a global threat to aquatic ecosystems due to their pseudo-persistence and their potential toxicity towards non-target species. Amoxicillin (AMX) and carbamazepine (CBZ) and their mixture (1:1) were investigated on the marine copepod Tigriopus fulvus (Fischer, 1860) considering both acute and chronic endpoints. While acute and chronic exposure did not directly affect survival, reproductive endpoints were affected like the mean egg hatching time that was significantly longer than the negative control for treatments with AMX (0.789 ± 0.079 µg/L), CBZ (8.88 ± 0.89 µg/L), and AMX and CMZ as a mixture (1.03 ± 0.10 µg/L and 0.941 ± 0.094 µg/L), in that order.

Air quality trends and implications pre and post Covid-19 restrictions.

Air pollution causes millions of premature deaths every year. Thus, air quality assessment is essential to preserve human health and support authorities to identify proper policies. In this study, concentration levels of 6 air contaminants (benzene, carbon monoxide, nitrogen dioxide, ground level ozone, particulate matters) as monitored in 2019, 2020 and 2021 by 37 stations, located in Campania (Italy) were analysed. Particular attention has been paid to March-April 2020 period to get clues on the possible effects of the lockdown regulations, imposed in Italy from March 9th to May 4th to limit COVID-19 spread, on atmospheric pollution. Air Quality Index (AQI), an algorithm developed by the United States Environmental Protection Agency (US-EPA), allowed us to classify the air quality from moderately unhealthy to good for sensitive groups. The evaluation of air pollution impact on human health by using the AirQ+ software evidenced a significant decrement of adult mortality in 2020 respect to 2019 and 2021. Among the six pollutants considered, PM10 and PM2.5 resulted the less affected by the lockdown restrictions. Finally, a comparison between NO2 ground level concentration and the reprocessed Level 2 NO2 tropospheric column concentration obtained from satellite surveys highlighted as concentration measured at the ground level stations can be strongly influenced by the station position and its surroundings.

Hormetic Effects of Cerium, Lanthanum and Their Combination at Sub-micromolar Concentrations in Sea Urchin Sperm.

Rare earth elements (REEs) cerium (Ce) and lanthanum (La) and their combination were tested across a concentration range, from toxic (10-4 to 10-5 M) to lower concentrations (10-6 to 10-8 M) for their effects on sea urchin (Sphaerechinus granularis) sperm. A significantly decreased fertilization rate (FR) was found for sperm exposed to 10-5 M Ce, La and their combination, opposed to a significant increase of FR following 10-7 and 10-8 M REE sperm exposure. The offspring of REE-exposed sperm showed significantly increased developmental defects following sperm exposure to 10-5 M REEs vs. untreated controls, while exposure to 10-7 and 10-8 M REEs resulted in significantly decreased rates of developmental defects. Both of observed effects-on sperm fertilization success and on offspring quality-were closely exerted by Ce or La or their combination.

In situ microcosm remediation of polyaromatic hydrocarbons: influence and effectiveness of Nano-Zero Valent Iron and activated carbon.

Nano-zero-valent iron (nZVI) and activated carbon (AC) addition are ongoing techniques for the remediation of hydrophobic organic compound-contaminated sediment and water, but with still unexplored eco(toxico)logical implications, especially when applied in situ. In this study, we investigated AC and nZVI as remediation methods for marine contaminated sediment and water, including chemical and toxicity (Artemia franciscana survival and genotoxicity) surveys. The removal efficiency of AC and nZVI (about 99%) was similar in both sediment and seawater, while the survival of nauplii and adults was mainly impacted by nZVI than AC. At the molecular level, the nZVI-addition induced down-regulation in the expression of two stress and one developmental genes, whereas AC was able to up-regulated only one gene involved in stress response. Results suggested that the use of AC is safer than nZVI that requires further investigation and potential optimization to reduce secondary undesired effects.

Genotoxicity in Artemia spp.: An old model with new sensitive endpoints.

Artemia spp. represent models species widely used in ecotoxicological studies due to its simple and fast manipulation in laboratory conditions that makes this crustacean well adaptable to several methodological approaches. Although cysts hatching, swimming behavior, reproductive success and mortality are the main endpoints used for the determination of toxicity, the detection of slight alterations induced by certain substances found at low concentrations in the environment may require more sensitive biomarkers. For this reason, the identification of DNA or chromosomal damages has been proposed as an additional and appreciable endpoint for the ecotoxicological assessment of environmental chemicals. Concerning Artemia models, only few studies indicated that the exposure to organic and inorganic compounds (i.e. pesticides, nanoparticles, bacterial products or heavy metals) can reduce the survival and fitness through the onset of DNA breaks or the dysregulation of key genes. In contrast, literature research revealed a lot of works primarily focusing on the mortality and hatching rates of Artemia nauplii and cysts despite the well-known low sensitivity of these species. The present review reports the current state of knowledge concerning the effects induced by various chemicals, including organic and inorganic compounds, on the common parameters and genotoxicity in both Artemia franciscana and Artemia salina. Advantages and limitations of Artemia spp. models in eco-toxicological investigations together with the most used classes of compounds are briefly discussed. Moreover, a mention is also addressed to scarce availability of literature data focusing on genotoxic effects and the great reliability of molecular approaches observed in this poorly sensitive model organism. Thus, the opportunity to take advantage of genotoxic analyses has also been highlighted, by suggesting this approach as a novel endpoint to be used for the eco-toxicological assessment of several stressors.

Octocrylene: From Sunscreens to the Degradation Pathway during Chlorination Processes: Formation of Byproducts and Their Ecotoxicity Assessment.

Octocrylene is an organic sunscreen whose main action is to absorb UVB radiation and short UVA wavelengths; it is used in various cosmetic products in order to provide an adequate sun-protection factor or to protect the cosmetic formulations themselves from UV radiation. This filter is believed to be a possible endocrine disruptor and is also questioned due to its allergic and/or photoallergic potential. However, it continues to be widely used, and it has been found in various environments, not least those of swimming pools, where it is evidently released by consumers, to the point that it is now considered an emerging micropollutant. The present investigation presents the possible chemical fate of octocrylene in the typical chlorination conditions of wastewater or swimming pools. A total of 11 disinfection byproducts were identified, and 6 were identified for the first time, and separated by HPLC. These products were identified through careful mass spectrometry studies and 1D and 2D NMR experiments. A formation mechanism has been proposed that justifies the chemical structures of all of the compounds identified. The ecotoxicological assessment of octocrylene and their products was carried out by employing Phaeodactylum tricornutum, Brachionus plicatilis and Aliivibrio fischeri as bioindicators. The ecotoxicity results reveal that toxic byproducts might be generated during the oxidation process, increasing the potential risk to the marine environment.

Antimicrobial Effectiveness of Innovative Photocatalysts: A Review.

Waterborne pathogens represent one of the most widespread environmental concerns. Conventional disinfection methods, including chlorination and UV, pose several operational and environmental problems; namely, formation of potentially hazardous disinfection by-products (DBPs) and high energy consumption. Therefore, there is high demand for effective, low-cost disinfection treatments. Among advanced oxidation processes, the photocatalytic process, a form of green technology, is becoming increasingly attractive. A systematic review was carried out on the synthesis, characterization, toxicity, and antimicrobial performance of innovative engineered photocatalysts. In recent decades, various engineered photocatalysts have been developed to overcome the limits of conventional photocatalysts using different synthesis methods, and these are discussed together with the main parameters influencing the process behaviors. The potential environmental risks of engineered photocatalysts are also addressed, considering the toxicity effects presented in the literature.

Nature-based coagulants for drinking water treatment: An ecotoxicological overview.

The intensive human activities extensively contaminated water sources making its treatment a problem of paramount importance, especially with the increasing of global population and water scarcity. The application of natural coagulants has become a promising and environmentally friendly alternative to conventional ones. This study was aimed at evaluating the efficiency of four plant extracts namely Agave americana, Carpobrotus acinaciformis, Austrocylindropuntia subulate, and Senicio anteuphorbium as natural coagulants to remove Microcystis aeruginosa cyanobacterium from water. The effects of pH (4, 5, 6, 7, 8 9, and 10) and coagulant dose (5, 10, 15, 20, 25, and 30 mg/L) on the coagulation efficiency were investigated. Results showed that plant-based extracts exhibited high coagulant abilities significantly contributing to the removal of M. aeruginosa cells up to 80% on a case-by-case basis. The ecotoxicity (Daphnia magna, Aliivibrio fischeri, Raphidocelis subcapitata, and Sorghum saccharatum) was absent or presented very slight acute toxicity up to 12.5 mg/L being S. anteuphorbium the least toxic. PRACTITIONER POINTS: Nature-based plant extracts showed removal rates up to 80%. Lower pH and A. subulate and S. anteuphorbium were the most efficient coagulants Toxicity effects were plant extracts-based and dose function. A. subulate and S. anteuphorbium were the least toxic extracts.