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.

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.

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.

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.

Chronic sublethal effects of ZnO nanoparticles on Tigriopus fulvus (Copepoda, Harpacticoida).

This study investigated for the first time the effects of ZnO nanoparticle (NP) chronic exposure (28 days) on Tigriopus fulvus. Acute toxicity (48 h) of three Zn chemical forms was assessed as well including the following: (a) ZnO nanoparticles (NPs), (b) Zn2+ from ZnO NP suspension after centrifugation (supernatant) and (c) ZnSO4 H2O. Physical-chemical and electronic microscopies were used to characterize spiked exposure media. Results showed that the dissolution of ZnO NPs was significant, with a complete dissolution at lowest test concentrations, but nano- and micro-aggregates were always present. Acute test evidenced a significant higher toxicity of Zn2+ and ZnSO4 compared to ZnO NPs. The chronic exposure to ZnO NPs caused negative effects on the reproductive traits, i.e. brood duration, brood size and brood number at much lower concentrations (≥ 100 µg/L). The appearance of ovigerous females was delayed at higher concentrations of ZnO NPs, while the time required for offspring release and the percentage of non-viable eggs per female were significantly increased. ZnO NP subchronic exposure evidenced its ability to reduce T. fulvus individual reproductive fitness, suggesting that ZnO NPs use and release must be carefully monitored. Graphical abstract Graphical Abstract.

Crystal violet and toxicity removal by adsorption and simultaneous photocatalysis in a continuous flow micro-reactor.

A continuous flow micro-reactor irradiated by UV-LEDs was employed to treat coloured wastewater by adsorption and simultaneous photocatalysis. Zinc oxide (ZnO) immobilized on commercial zeolites pellets in spherical shape (ZEO) was used as catalytic material in a micro-reactor maximizing the photocatalyst exposition to light sources, irradiating uniformly the entire solution volume and improving the mass transfer phenomena. Experimental tests were carried out on crystal violet dye (CV) as one of the main dying agent present in textile wastewater. The comparison between adsorption and adsorption/photocatalytic tests showed that UV irradiation can achieve a steady state CV concentration value corresponding to an equilibrium condition between adsorption and photocatalytic oxidation. The higher removal efficiency (i.e. 93%) was observed with a liquid flow rate of 1.1 mL/min (contact time = 4.7 min; CV = 10 mg/L) under UV light irradiation. In the steady state, CV removal remained constant for the overall testing time. Bioassays evidenced that toxicity was not completely removed (i.e. final effluent ranked as "slight acute toxic") from wastewater suggesting its suitability for sewage collection discharge. A Dubinin Radushkevich (D-R) isotherm model was applied for studying the adsorption behaviour of ZnO/ZEO sample. CV adsorption constants were evaluated from experimental data carried out in dark conditions in a batch system. Kinetic expression of CV removal and the D-R adsorption were incorporated in the CV mass balance estimating the kinetic parameter. The model was validated comparing the calculated CV conversion with the experimental tests collected at different CV inlet concentration.

Simulating the fate of indigenous antibiotic resistant bacteria in a mild slope wastewater polluted stream.

The fate of indigenous surface-water and wastewater antibiotic resistant bacteria in a mild slope stream simulated through a hydraulic channel was investigated in outdoor experiments. The effect of (i) natural (dark) decay, (ii) sunlight, (iii) cloudy cover, (iv) adsorption to the sediment, (v) hydraulic conditions, (vi) discharge of urban wastewater treatment plant (UWTP) effluent and (vii) bacterial species (presumptive Escherichia coli and enterococci) was evaluated. Half-life time (T1/2) of E. coli under sunlight was in the range 6.48-27.7min (initial bacterial concentration of 105CFU/mL) depending on hydraulic and sunlight conditions. E. coli inactivation was quite similar in sunny and cloudy day experiments in the early 2hr, despite of the light intensity gradient was in the range of 15-59W/m2; but subsequently the inactivation rate decreased in the cloudy day experiment (T1/2=23.0min) compared to sunny day (T1/2=17.4min). The adsorption of bacterial cells to the sediment (biofilm) increased in the first hour and then was quite stable for the remaining experimental time. Finally, when the discharge of an UWTP effluent in the stream was simulated, the proportion of indigenous antibiotic resistant E. coli and enterococci was found to increase as the exposure time increased, thus showing a higher resistance to solar inactivation compared to the respective total populations.

Toxicity assessment within the application of in situ contaminated sediment remediation technologies: A review.

Polluted sediment represents a great problem for aquantic environments with potential direct acute and chronic effects for the biota and can be tackled with both in situ and ex situ treatments. Once dredging activities are not compulsory, sediment can be kept in place and managed with techniques involving the use of amendment and/or capping. Before their application, the assessment of their potential impact to the target environment cannot ignore the safe-by-design approach. The role of toxicity in in situ sediment remediation was reviewed discussing about how it can be used for the selection of amendments and the monitoring of treatment technologies. Results evidenced that capping technology coupled to activated carbon (AC) is the most frequently applied approach with effects varying according to the rate of contamination in treated sediment, the amount of AC used (% v/v), and target biological models considered. Little data are available for zerovalent iron as well as other minor amending agents such as hematite, natural zeolite, biopolymers and organoclays. Current (eco-)toxicological information for in situ sediment remediation technologies is fragmentary and incomplete or entirely missing, making also the interpretation of existing data quite challenging. In situ sediment remediation represents an interesting potentially effective approach for polluted sediment recovering. As its application in some lab-based and field studies reported to induce negative effects for target organisms, amendments and capping agents must be attentively evaluated for short- and long-term environmental effects, also in the perspective of the remediated site monitoring and maintenance.

Biomonitoring of nutrient and toxic element concentrations in the Sarno River through aquatic plants.

The Sarno River is considered the most polluted river in Europe and one of the ten most polluted rivers in the world. So far, its quality has been usually evaluated by water and sediment analyses of either inorganic or organic pollutants. However, a biomonitoring approach would be of paramount importance in the evaluation of river quality, since it integrates pollutant temporal fluctuations, as in the case of discontinuous inputs from urban, industrial and agricultural activities. To this end, a passive biomonitoring study of the Sarno River was carried out, using two native aquatic plants accumulators of inorganic pollutants. The spring area was monitored analysing the roots of the semi-submerged Apium nodiflorum, whereas the whole river course was monitored analysing the shoots of the submerged Potamogeton pectinatus. The information on the four macronutrient (Ca, K, Mg, P), the six micronutrient (Cu, Fe, Mn, Na, Ni, Zn) and the four toxic element (Cd, Cr, Pb, V) concentrations were separately combined in the Nemerow Pollution Index. Results evidenced a severe pollution degree of the Sarno River, attributable to toxic elements > micronutrients > macronutrients. In particular, the spring area showed high K concentrations, as well as high concentrations of several micronutrients and toxic elements. A generalized Zn contamination and a progressive macronutrient (above all Ca and P), micronutrient (above all Ni, Cu and Fe) and toxic element (above all Cr and Pb) accumulation toward the mouth was related to pollution from agricultural and urban activities. Industrial sources, especially tanneries along the Solofrana tributary, accounted for high Mn concentrations, whereas the volcanic origin of the substrate accounted for a generalized V contamination.

Antibiotic effects on seed germination and root development of tomato (Solanum lycopersicum L.).

Antibiotics are emerging pollutants released into the environment through wastewater and manure or effluents from livestock plants. Compared to the wide literature on the effects of antibiotics on the development of drug-resistant bacteria and on the adverse effects on animals and human beings, the effects on plants are less investigated. Here we evaluated the effects of four antibiotics (cloramphenicol: CAP, spiramycin: SPR, spectinomycin: SPT, vancomycin: VAN) belonging to different chemical groups, on seed germination and root development of tomato (Solanum lycopersicum L. cv. San Marzano). Specifically, seed germination and root elongation kinetics, as well as the number of mithotic figures in root apical meristem, were studied in relation to different concentrations of each antibiotic (0, 0.1, 1, 10, 100, 1000mgL-1) for 10 and 7 days, respectively. Results showed that seed germination was not affected, but root development (root elongation kinetics and cell division) was impaired at concentrations from 10mgL-1 (SPT) and 100mgL-1 (CAP) to 1000mgL-1 (SPR and VAN).

Polymer functionalized nanocomposites for metals removal from water and wastewater: An overview.

Pollution by metal and metalloid ions is one of the most widespread environmental concerns. They are non-biodegradable, and, generally, present high water solubility facilitating their environmental mobilisation interacting with abiotic and biotic components such as adsorption onto natural colloids or even accumulation by living organisms, thus, threatening human health and ecosystems. Therefore, there is a high demand for effective removal treatments of heavy metals, making the application of adsorption materials such as polymer-functionalized nanocomposites (PFNCs), increasingly attractive. PFNCs retain the inherent remarkable surface properties of nanoparticles, while the polymeric support materials provide high stability and processability. These nanoparticle-matrix materials are of great interest for metals and metalloids removal thanks to the functional groups of the polymeric matrixes that provide specific bindings to target pollutants. This review discusses PFNCs synthesis, characterization and performance in adsorption processes as well as the potential environmental risks and perspectives.

Metals and tributyltin sediment contamination along the Southeastern Tyrrhenian Sea coast.

Anthropogenic pressures can adversely affect the quality of coastal sediment posing at risk human health and the ecosystem. The Southeastern Tyrrhenian Sea (STS) coast (Italy) is still largely unexplored under this point of view. This study investigated for the first time in the area the seasonal variation and potential impact of selected metals (Cd, Cr, Cu, Ni, and Pb) and tributyltin (TBT) from sediment samples collected along the STS coast (Casalvelino Marina, Casalvelino Bay, Acciaroli Marina and Acciaroli Bay) in the perspective of Water Framework Directive and Marine Strategy Framework Directive. Data were compared to the contamination background levels of Punta Licosa reference site considering elemental enrichment factors (EFs) and single substance- and mixture-based risk characterisation ratios. Further, data were discussed considering the review of Southern Tyrrhenian Sea sediment quality. Results evidenced an increase of contamination levels from March to October showing that marinas are more impacted than bays. Sediment EFs highlighted that contamination levels were always greater than the reference site like risk characterisation ratios, suggesting the presence of potential threats. The sediment quality database generated after literature review revealed a similar situation for the whole Southern Tyrrhenian Sea.

Photocatalytic degradation of the antibiotic chloramphenicol and effluent toxicity effects.

Chloramphenicol sodium succinate (CAP, C15H15Cl2N2 Na2O8) is a broad-spectrum antibiotic exhibiting activity against both Gram-positive and Gram-negative bacteria as well as other groups of microorganisms only partially removed by conventional activated sludge wastewater treatment plants. Thus, CAP and its metabolites can be found in effluents. The present work deals with the photocatalytic degradation of CAP using TiO2 as photocatalyst. We investigated the optimization of reaction contact time and concentration of TiO2 considering CAP and its by-products removal as well as effluent ecotoxicity elimination. Considering a CAP real concentration of 25mgL(-1), kinetic degradation curves were determined at 0.1, 0.2, 0.4, 0.8, 1.6 and 3.2gL(-1) TiO2 after 5, 10, 30, 60 and 120min reaction time. Treated samples were checked for the presence of by-products and residual toxicity (V. fischeri, P. subcapitata, L. sativum and D. magna). Results evidenced that the best combination for CAP and its by-products removal could be set at 1.6gL(-1) of TiO2 for 120min with an average residual toxicity of approximately 10%, that is the threshold set for negative controls in most toxicity tests for blank and general toxicity test acceptability.

Which lesson can be learnt from a historical contamination analysis of the most polluted river in Europe?

The Sarno River trend analysis during the last 60 years was traced focusing on the socio-economic and environmental issues. The river, originally worshiped as a god by Romans, is affected by an extreme level of environmental degradation, being sadly reputed as the most polluted river in Europe. This is the "not to be followed" example of the worst way a European river can be managed. Data about water, sediment, soil, biota and air contamination were collected from scientific papers, monitoring surveys, and technical reports depicting a sick river. Originally, the river was reputed as a source of livelihood, now it is considered a direct threat for human health. Wastewater can still flow through the river partially or completely untreated, waste production associated with the manufacture of metal products and leather tanning continues to suffer from the historical inadequacy of regional wastewater treatment plants (WWTPs), associated with the partial or no reuse of effluents. All efforts should be devoted to solving the lack of wastewater and waste management, the gap in land planning, improving the capacity of existing WWTPs also via the construction of new sewer sections, restoring Sarno River minimum vital-flow, keeping to a minimum uncontrolled discharges as well as supporting river contracts. The 2015 goal stated by the Water Framework Directive (2000/60/EC) is still far to be reached. The lesson has not been learnt yet.

Genetically biodiverse potato cultivars grown on a suitable agricultural soil under compost amendment or mineral fertilization: yield, quality, genetic and epigenetic variations, soil properties.

The use of compost for soil amendment is a promising agricultural practice environmentally and economically viable. In the framework of a wide research project designed to evaluate the effects of soil amendment with municipal solid waste compost in comparison with traditional mineral fertilization practices, 54 different cultivars (Cvs) of potatoes were AFLP (amplified fragment length polymorphism) molecularly fingerprinted. The seven most genetically biodiverse potato Cvs were used to establish an experimental field in southern Italy. The field area was divided into two portions fertilized with compost (20 Mg ha(-1)) or with ammonium sulphate (200 kg ha(-1)). No significant differences in productivity, organoleptic characteristics and element concentrations were observed between the potato tubers obtained with both kinds of soil fertilization, while the tubers grown on compost amended soil showed, on average, higher K concentrations with respect to those grown on mineral fertilised soil. cDNA-AFLP (complementary DNA-AFLP) and MSAP (methylation sensitive amplified polymorphism) analyses were carried out on both leaves and tubers of one selected Cv to estimate if any transcriptome alterations or epigenetic modifications were induced by the two kinds of fertilization, however no variations were detected. Chemical and biological soil qualities (i.e., microbial respiration, FDA hydrolysis, alkaline and acid phosphatase) were assessed on soil samples at the start of the experiment and at the end of potato crop cycle. No significant differences in soil pH and limited ones, in the available fraction of some trace elements, were observed; while conductivity was much higher for the compost amended portion of the experimental field. Microbial respiration, FDA hydrolysis and acid phosphatase activities were significantly increased by compost amendment, in comparison with mineral fertilization. Finally, a sensory panel of potato Cvs detected no significant differences among qualitative descriptors and among potatoes coming from the two differently fertilized soils.

An integrated chemical and ecotoxicological assessment for the photocatalytic degradation of vancomycin.

The photocatalytic degradation of an antibiotic, vancomycin B hydrochloride (VAN-B), has been investigated in aqueous suspensions of titanium dioxide (TiO2) by monitoring the change in its concentration as well as the production of ammonia and chlorides as a function of irradiation time. The removal of 50mg L(-1) VAN-B solution yields maximum concentrations of 2.45 and 2.53 mg N-NH3 L(-1) after 120 min of photocatalytic oxidation using 0.1 and 0.2 g TiO2 L(-1), respectively. When 0.2 g TiO2 L(-1) were applied up to 87% of the stoichiometric amount of chloride was reached within 120 min of irradiation, corresponding to 0.087 mmol L(-1). A set ofbioassays (Daphnia magna, Pseudokirchneriella subcapitata and Ceriodaphnia dubia) was performed to evaluate the potential detoxification of VAN-B and its by-products of oxidation under chronic and acute tests. The toxicity of the treated VAN-B samples varied during the oxidation, due to the formation of some intermediate products more toxic than VAN-B. Despite almost total removal of VAN-B that was achieved within 120 min of irradiation, a significant increase in toxicity was observed in chronic tests proving that the chronic assays are more appropriate than acute ones to detect the impact of by-products formed during the photocatalytic degradation of antibiotics.

Strong overcrowding in dimethyl 2-(dimethylamino)terephthalate.

The molecular structure of the title compound, C(12)H(15)NO(4), has several features related to steric hindrance due to the ester and dimethylamine groups being located ortho with respect to one another. In particular, the carbonyl group of the ester is not coplanar with the ring, the amine N atom is in a pyramidal arrangement [the N atom is 0.2161 (12) A from the three C atoms to which it is bonded] and the C atom of the adjacent ester group lies 0.3784 (14) A out of the plane of the aromatic ring. The deformations found in the X-ray structure have been confirmed by ab initio quantum mechanical calculations.