Unravelling the ecotoxicological impacts of gadolinium (Gd) on Mytilus galloprovincialis embryos and sperm in seawater: A preliminary study.

As the demand for rare earth elements (REEs) continues to surge in diverse industrial and medical domains, the ecological consequences of their ubiquitous presence have garnered heightened attention. Among the REEs, gadolinium (Gd), commonly used in medical imaging contrast agents, has emerged as a pivotal concern due to its inadvertent introduction into marine ecosystems via wastewater release. This study delves into the complex ecotoxicological implications of Gd contamination, focusing on its impact on the embryonic development and sperm functionality of Mytilus galloprovincialis. The findings from this study underscore the potential hazards posed by this rare element, offering a critical perspective on the ecological risks associated with Gd. Notably, this exploratory work reveals that Gd exerts a significant embryotoxic effect at elevated concentrations, with an observed half maximal effective concentration (EC50) value of 0.026 mg/L. Additionally, Gd exposure leads to a considerable reduction in sperm motility and alters sperm morfo-kinetic parameters, especially at a concentration of 5.6 mg/L. The results highlight a dose-dependent relationship between Gd exposure and the prevalence of specific malformation types in Mytilus embryos, further providing crucial insights into the potential risks imposed by this rare earth element.

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.

Ecotoxicological assessment of waste-derived organic fertilizers and long-term monitoring of fertilized soils using a multi-matrix and multi-species approach.

The present study investigates the ecotoxicity of 7 biofertilizers, including biowaste-derived organic matrices. Real-field tests were conducted to assess the impacts of soil fertilization with sewage sludge digestate from high-solid thermophilic anaerobic digestion (HSTAD) compared to those obtained on non-amended and urea-fertilized soils. The physical-chemical and ecotoxic impact of HSTAD digestate on soil was monitored for 12 months, at 5 time points and 2 soil depths, on a maize field divided in 3 portions (non-treated, fertilized with urea, amended with digestate). The chemical and physical characteristics of the soil were previously analyzed for 3 years to provide a long-term outlook of the impacts of biofertilizer application. Seven bioindicators were utilized for direct (on whole soil) and indirect (on soil elutriates) ecotoxicological tests on fertilizers and amended soils, including plant seeds (Lepidium sativum, Sorghum saccharatum, and Sinapsis alba), the aquatic organism Daphnia magna, the alga Raphidocelis subcapitata, the luminescent bacterium Aliivibrio fischeri, and the Nematode Caenorhabditis elegans. No serious negative effects on soil fertilized with HSTAD digestate were evidenced. Conversely, bioassays rather showed positive effects, encouraging the utilization of HSTAD digestate in agriculture, considering the proper concentrations of use. The obtained data were interpolated and a test battery integrated index was generated, confirming the absence of ecotoxicological risk for the soils amended with the applied fertilizers. The long-term evolution of the physical-chemical soil characteristics (including the concentrations of potential contaminants) was similar for both HSTAD digestate and urea application as well as for non-fertilized soil, indicating no negative effects due to digestate application on land. On the contrary, digestate application improved the content of stabilized organic matter and nutrients in soil. This study proposes a more correct approach to ecotoxicity assessment of fertilized soils for biofertilizer evaluation and demonstrates the long-term safe application of HSTAD digestate on agricultural soil.

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.

Insights into the Ecotoxicology of Radicinin and (10S,11S)-(-)-epi-Pyriculol, Fungal Metabolites with Potential Application for Buffelgrass (Cenchrus ciliaris) Biocontrol.

Buffelgrass (Cenchrus ciliaris L.) is an invasive C4 perennial grass species that substantially reduces native plant diversity of the Sonoran Desert through fire promotion and resource competition. Broad-spectrum herbicides are essentially used for its control, but they have a negative environmental and ecological impact. Recently, phytotoxicity on C. ciliaris has been discovered for two metabolites produced in vitro by the phytopathogenic fungi Cochliobolus australiensis and Pyricularia grisea. They were identified as (10S,11S)-(-)-epi-pyriculol and radicinin and resulted in being potential candidates for the development of bioherbicides for buffelgrass biocontrol. They have already shown promising results, but their ecotoxicological profiles and degradability have been poorly investigated. In this study, ecotoxicological tests against representative organisms from aquatic ecosystems (Aliivibrio fischeri bacterium, Raphidocelis subcapitata alga, and Daphnia magna crustacean) revealed relatively low toxicity for these compounds, supporting further studies for their practical application. The stability of these metabolites in International Organization for Standardization (ISO) 8692:2012 culture medium under different temperatures and light conditions was also evaluated, revealing that 98.90% of radicinin degraded after 3 days in sunlight. Significant degradation percentages (59.51-73.82%) were also obtained at room temperature, 30 °C or under ultraviolet (254 nm) light exposure. On the other hand, (10S,11S)-epi-pyriculol showed more stability under all the aforementioned conditions (49.26-65.32%). The sunlight treatment was also shown to be most effective for the degradation of this metabolite. These results suggest that radicinin could provide rapid degradability when used in agrochemical formulations, whereas (10S,11S)-epi-pyriculol stands as a notably more stable compound.

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.

VT-1161-A Tetrazole for Management of Mono- and Dual-Species Biofilms.

VT-1161 is a novel tetrazole antifungal agent with high specificity for fungal CYP51 (compared to human CYP enzymes) which has been proven to have fewer adverse effects and drug-drug interaction profiles due to fewer off-target inhibitors. In this study, we evaluated the anti-biofilm potential of VT-1161 against mono- and dual-species biofilms of Candida albicans, Klebsiella pneumoniae and Staphylococcus aureus. VT-1161 inhibited planktonic growth of all three strains, with an MIC value of 2 µg mL-1 for C. albicans and 0.5 µg mL-1 for K. pneumoniae and S. aureus, and killed 99.9% of the microbial populations, indicating a cytocidal action. Additionally, VT-1161 showed an excellent anti-biofilm action, since it inhibited mono-microbial biofilms by 80% at 0.5 µg mL-1, and dual-species biofilms of C. albicans/K. pneumoniae and C. albicans/S. aureus by 90% at the same concentration. Additionally, the eradication of mature biofilms after 24 h of VT-1161 exposure was excellent, reaching 90% at 2 µg mL-1 for both mono- and dual-species biofilms. In such mixed biofilms, the use of VT-1161 was revealed to be an alternative treatment because it was able to reduce the number of cells of each species during both inhibition and eradication. Since long-term therapy is necessary for most fungal biofilm infections due to their recurrence and obstinacy, VT-1161 showed low cytotoxicity against normal human cell lines and also against the invertebrate model Caenorhabditis elegans. Considering the excellent anti-biofilm potential and its GRAS (generally recognized as safe) status, VT-1161 may find use in the prevention or therapeutic treatment of mono- or poly-microbial biofilms.

Evaluation of Rare Earth Element-Associated Hormetic Effects in Candidate Fertilizers and Livestock Feed Additives.

Rare earth elements (REEs) are recognized as emerging contaminants with implications in human and environmental health. Apart from their adverse effects, REEs have been reported as having positive effects when amended to fertilizers and livestock feed additives, thus suggesting a hormetic trend, implying a concentration-related shift from stimulation to inhibition and toxicity, with analogous trends that have been assessed for a number of xenobiotics. In view of optimizing the success of REE mixtures in stimulating crop yield and/or livestock growth or egg production, one should foresee the comparative concentration-related effects of individual REEs (e.g., Ce and La) vs. their mixtures, which may display distinct trends. The results might prompt further explorations on the use of REE mixtures vs. single REEs aimed at optimizing the preparation of fertilizers and feed additives, in view of the potential recognition of their use in agronomy and zootechny.

The Arylamidine T-2307 as a Novel Treatment for the Prevention and Eradication of Candida tropicalis Biofilms.

Candida tropicalis is an emerging pathogen with a high mortality rate due to its virulence factors, including biofilm formation, that has important repercussions on the public health system. The ability of C. tropicalis to form biofilms, which are potentially more resistant to antifungal drugs and the consequent increasing antimicrobial resistance, highlights an urgent need for the development of novel antifungal. The present study analyzed the antibiofilm capacity of the arylamidine T-2307 on two strains of Candida tropicalis. Antimicrobial activity and time-killing assays were performed to evaluate the anticandidal effects of T-2307, the antibiofilm ability on biomass inhibition and eradication was evaluated by the crystal violet (CV) method. Furthermore, in Galleria mellonella infected larvae an increased survival after pre-and post- treatment with T-2307 was observed. The MTT test was used to determine the viability of immortalized human prostate epithelial cells (PNT1A) after exposure to different concentrations of T-2307. Levels of interleukin IL-4, IL-8, IL-10 were quantified after Candida infection of PNT1A cells and treatment. Active doses of T-2307 did not affect the viability of PNT1A cells, and drug concentrations of 0.005 or 0.01 µg mL-1 inhibited the secretion of inflammatory cytokines. Taken together, these results provide new information on T-2307, indicating this drug as a new and promising alternative therapeutic option for the treatment of Candida infections.

Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (Pr3+, Eu3+, Ho3+, Tm3+).

Rare-earth elements (REEs) are in all respect a class of new contaminants that may have toxic effects on organisms and microorganisms and information on their interactions with natural ligands should be of value to predict and control their diffusion in natural environments. In the current study, we investigate interactions of tripositive cations of praseodymium, europium, holmium, and thulium with harzianic acid (H2L), a secondary metabolite produced by selected strains of fungi belonging to the Trichoderma genus. We applied the same techniques and workflow previously employed in an analogous study concerning lanthanum, neodymium, samarium, and gadolinium tripositive cations. Therefore, in the current study, HPLC-ESI-HRMS experiments, circular dichroism (CD), and UV-Vis spectrophotometric absorption data, as well as accurate pH measurements, were applied to characterize bonding interactions between harzianic acid and Pr3+, Eu3+, Ho3+, and Tm3+ cations. Problems connected to the low solubility of harzianic acid in water were overcome by employing a 0.1 M NaClO4/(CH3OH + H2O 50/50 w/w) mixed solvent. For Pr3+, Ho3+, and Tm3+, only the mono complexes PrL+, HoL+, and TmL+ were detected and their formation constant determined. Eu3+ forms almost exclusively the bis complex EuL2- for which the corresponding formation constant is reported; under our experimental conditions, the mono complex EuL+ is irrelevant. Combining the results of the present and previous studies, a picture of interactions of harzianic acid with rare-earth cations extending over 8 of the 17 REEs can be composed. In order to complement chemical information with toxicological information, a battery of bioassays was applied to evaluate the effects of praseodymium, europium, holmium, and thulium tripositive cations on a suite of bioindicators including Aliivibrio fischeri (Gram-negative bacterium), Raphidocelis subcapitata (green alga), and Daphnia magna (microcrustacean), and median effective concentration (EC50) values of Pr3+, Eu3+, Ho3+, and Tm3+ for the tested species were assessed.

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.

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.

Iridoid Glycosides Isolated from Bellardia trixago Identified as Inhibitors of Orobanche cumana Radicle Growth.

Orobanche cumana is an obligate holoparasitic plant with noxious effects in sunflower crops. Bellardia trixago is a facultative hemiparasitic plant that infects ruderal plants without noxious significance in agriculture and is known to produce a wide spectrum of bioactive metabolites. The objective of this study was to evaluate the allelopathic effects of B. trixago on the growth of O. cumana seedlings. Three different extracts using solvents of increasing polarity (n-hexane, dichloromethane and ethyl acetate) were prepared from the flowers, aerial green organs and roots of two populations, a white-flowered and a yellow-flowered population of B. trixago, both collected in southern Spain. Each extract was studied using allelopathic screenings on O. cumana which resulted in the identification of allelopathic activity of the ethyl acetate extracts against Orobanche radicles. Five iridoid glycosides were isolated together with benzoic acid from the ethyl acetate extract of aerial green organs by bio-guided purification. These compounds were identified as bartsioside, melampyroside, mussaenoside, gardoside methyl ester and aucubin. Among them, melampyroside was found to be the most abundant constituent in the extract (44.3% w/w), as well as the most phytotoxic iridoid on O. cumana radicle, showing a 72.6% inhibition of radicle growth. This activity of melampyroside was significantly high when compared with the inhibitory activity of benzoic acid (25.9%), a phenolic acid with known allelopathic activity against weeds. The ecotoxicological profile of melampyroside was evaluated using organisms representing different trophic levels of the aquatic and terrestrial ecosystems, namely producers (green freshwater algae Raphidocelis subcapitata and macrophyte Lepidium sativum), consumers (water flea Daphnia magna and nematode Caenorhabditis elegans) and decomposers (bacterium Aliivibrio fischeri). The ecotoxicity of melampyroside differed significantly depending on the test organism showing the highest toxicity to daphnia, nematodes and bacteria, and a lower toxicity to algae and macrophytes. The findings of the present study may provide useful information for the generation of green alternatives to synthetic herbicides for the control of O. cumana.

An Ecotoxicological Evaluation of Four Fungal Metabolites with Potential Application as Biocides for the Conservation of Cultural Heritage.

Biocides based on chemical synthetic compounds have been commonly used to counteract damages caused by microorganisms on stone cultural heritage. However, in the last few years, the use of commercial and traditional biocides has been banned and/or limited due to their dangerous profile for the environment, as well as human and animal health. Natural products could be used as suitable alternatives for cultural heritage purposes, as they have low toxicity and stability compared with synthetic pesticides. Even if most of the investigated solutions have already shown promising results, their efficiency, ecotoxicological, and chemical features are poorly investigated. In this manuscript, we aimed to evaluate the ecotoxicological profile of four fungal metabolites-namely, cavoxin, epi-epoformin, seiridin, and sphaeropsidone-with potential antimicrobial properties for monumental artworks. A battery of ecotoxicological tests using Aliivibrio fischeri (bacterium), Raphidocelis subcapitata (alga), Raphanus sativus L. (macrophyte), Daphnia magna (crustacean), and Caenorhabditis elegans (nematode) revealed a relative lower toxicity of these compounds, especially when compared with Preventol® and Rocima®, commercial biocides mainly used for the conservation of cultural heritage.

Interaction of the Fungal Metabolite Harzianic Acid with Rare-Earth Cations (La3+, Nd3+, Sm3+, Gd3+).

Rare-earth elements are emerging contaminants of soil and water bodies which destiny in the environment and effects on organisms is modulated by their interactions with natural ligands produced by bacteria, fungi and plants. Within this framework, coordination by harzianic acid (H2L), a Trichoderma secondary metabolite, of a selection of tripositive rare-earth cations Ln3+ (Ln3+ = La3+, Nd3+, Sm3+, and Gd3+) was investigated at 25 °C, and in a CH3OH/0.1 M NaClO4 (50/50 w/w) solvent, using mass spectrometry, circular dichroism, UV-Vis spectrophotometry, and pH measurements. Experimental data can be satisfactorily explained by assuming, for all investigated cations, the formation of a mono-complex (LnL+) and a bis-complex (LnL2-). Differences were found between the formation constants of complexes of different Ln3+ cations, which can be correlated with ionic radius. Since gadolinium is the element that raises the most concern among lanthanide elements, its effects on organisms at different levels of biological organization were explored, in the presence and absence of harzianic acid. Results of ecotoxicological tests suggest that harzianic acid can decrease gadolinium biotoxicity, presumably because of complex formation with Gd3+.

Antifungal and Antibiofilm Activity of Cyclic Temporin L Peptide Analogues against Albicans and Non-Albicans Candida Species.

Temporins are one of the largest families of antimicrobial peptides with both anti-inflammatory and antimicrobial activity. Herein, for a panel of cyclic temporin L isoform analogues, the antifungal and antibiofilm activities were determined against representative Candida strains, including C. albicans, C. glabrata, C. auris, C. parapsilosis and C. tropicalis. The outcomes indicated a significant anti-candida activity against planktonic and biofilm growth for four peptides (3, 7, 15 and 16). The absence of toxicity up to high concentrations and survival after infection were assessed in vivo by using Galleria mellonella larvae, and the correlation between conformation and cytotoxicity was investigated by fluorescence assays and circular dichroism (CD). By combining fluorescence spectroscopy, CD, dynamic light scattering, confocal and atomic force microscopy, the mode of action of four analogues was hypothesized. The results pinpointed that peptide 3 emerged as a non-toxic compound showing a potent antibiofilm activity and represents a promising compound for biomedical applications.

Comparative Toxicological Evaluation of Tattoo Inks on Two Model Organisms.

Tattooing is a technique that introduces colored substances under the skin in order to color it permanently. Decomposition products of tattoo pigments produce numerous damages for the skin and other organs. We studied the effects of a commercial red ink tattoo, PR170, on Xenopus laevis embryos and Daphnia magna nauplii using concentrations of 10, 20, and 40 mg/L. For Xenopus, we applied the FETAX protocol analyzing survival, malformations, growth, heart rate, and the expression of genes involved in the development. In D. magna, we evaluated the toxicity with an immobilization test. Moreover, we investigated the production of ROS, antioxidant enzymes, and the expression of the ATP-binding cassette in both models. Our results indicate that PR170 pigment has nanoparticle dimensions, modifies the survival and the ATP-binding cassette activity, and induces oxidative stress that probably produces the observed effects in both models. Deformed embryos were observed in Xenopus, probably due to the modification of expression of genes involved in development. The expression of pro-inflammatory cytokines was also modified in this amphibian. We think that these effects are due to the accumulation of PR170 and, in particular, to the presence of the azoic group in the chemical structure of this pigment. Further studies needed to better understand the effects of commercial tattoo inks.

Long-term multi-endpoint exposure of the microalga Raphidocelis subcapitata to lanthanum and cerium.

Significant release of rare earth elements (REEs) into the environment is mainly due to active or abandoned mining sites, but their presence is globally increasing due to their use in several industrial sectors. The effects on primary producers as Raphidocelis subcapitata are still limited. This research focused on La and Ce as the two most widespread REEs that can be currently found up to hundreds of µg/L in water and wastewater. Microalgae were exposed to La and Ce for 3 days (pH = 7.8) (short-term exposure) to derive the effective concentrations inhibiting the growth on 10% (EC10) of the exposed population. EC10 values (0.5 mg/L of La and 0.4 mg/L of Ce) were used for the 28 days long-term exposure (renewal test) to observe after 7, 14, 21, and 28 days on a multi-endpoint basis microalgae growth inhibition (GI), biomarkers of stress (reactive oxygen species (ROS), superoxide dismutase (SOD), and catalase (CAT)), and bioconcentration. Results evidenced that La and Ce EC10 increased GI (day 28) up to 38% and 28%, respectively. ROS, CAT, and SOD activities showed differential responses from day 7 to day 14, 21, and 28, suggesting, in most of the cases, that La and Ce effects were counteracted (i.e., being the values at day 28 not significantly different, p > 0.05, from the relative negative controls), except for La-related ROS activities. La and Ce significantly bioconcentrated in microalgae populations up to 2- and 5-fold (i.e., at day 28 compared to day 7), in that order. Bioconcentrated La and Ce were up to 3157 and 1232 µg/g dry weight (day 28), respectively. These results suggested that low La and Ce concentrations can be slightly toxic to R. subcapitata having the potential to be bioaccumulated and potentially transferred along the food web.

Ecotoxicity and photodegradation of Montelukast (a drug to treat asthma) in water.

The present work focuses on the ecotoxicological effects of montelukast sodium (MTL) and its photoproducts, obtained under environmentally-like conditions. Despite of the potential presence in surface waters and the common use of MTL as asthma drug, limited data has been published for its photodegradation, while no information is available for its ecotoxicity. Light-induced degradation is an effective way for drugs to degrade in aquatic environments, and MTL is highly photosensitive, even by exposure to sunlight. In this study, solar-simulated irradiation of the drug in water was investigated. The drug was quickly converted into a series of photoproducts that were spectroscopically characterized. The possible photoreaction pathways were proposed. Ecotoxicity tests were performed on parent compound and mixture of photoproducts towards two bioindicators (Raphidocelis subcapitata and Daphnia magna). Results evidenced that effects of MTL on D. magna (EC50 = 16.4 mg/L) were greater than effects on R. subcapitata (EC50 = 195.7 mg/L). Microscopy observations revealed that MTL had mainly accumulated in the gut of daphnia. Toxicity data on photolysed solutions highlighted the presence of residual toxicity in all samples, evidencing that no complete mineralization occurred. Future research should focus on monitoring of MTL concentrations in the environment and study its effects in bioaccumulation tests.

Secondary Effects of Hypochlorite Treatment on the Emerging Pollutant Candesartan: The Formation of Degradation Byproducts and Their Toxicological Profiles.

In recent years, many studies have reported the frequent detection of antihypertensive agents such as sartans (olmesartan, valsartan, irbesartan and candesartan) in the influents and effluents of wastewater treatment plants (WWTPs) and in the superficial waters of rivers and lakes in both Europe and North America. In this paper, the degradation pathway for candesartan (CAN) was investigated by simulating the chlorination process that is normally used to reduce microbial contamination in a WWTP. Twelve isolated degradation byproducts (DPs), four of which were isolated for the first time, were separated on a C-18 column by employing a gradient HPLC method, and their structures were identified by combining nuclear magnetic resonance and mass spectrometry and comparing the results with commercial standards. On the basis of these results, a mechanism of formation starting from the parent drug is proposed. The ecotoxicity of CAN and its DPs was studied by conducting a battery of ecotoxicity tests; bioassays were performed using Aliivibrio fischeri (bacterium), Daphnia magna (planktonic crustacean) and Raphidocelis subcapitata (alga). The ecotoxicity results shed new light on the increased toxicity of DPs compared with the parent compound.