Developing a Passive Dosing Method for Acute Aquatic Toxicity Tests of Cationic Surfactant Benzalkoniums (BACs).

Benzalkonium chlorides (BACs) have been of environmental concern due to their widespread use and potential harm. However, challenges arise in defining and controlling the exposure concentration (Cw) in aquatic toxicity tests involving BACs with a long alkyl chain (i.e., #C > 14). To address this, a novel passive dosing method was introduced in the 48 h-acute ecotoxicity test on Daphnia magna and compared to the conventional solvent-spiking method in terms of Cw stability and toxicity results. Among 13 sorbent materials tested for their sorption capacity, poly(ether sulfone) (PES) membrane was an optimal passive dosing reservoir, with equilibrium desorption of BACs to water achieved within 24 h. The Cw of BACs remained constant in both applied dosing methods during the test period. However, the Cw in solvent-spiking tests was lower than the nominal concentration for long-chain BACs, particularly at low exposure concentrations. Notably, the solvent-spiking tests indicated that the toxicity of BACs increased with alkyl chain length from C6 to 14, followed by a decline in toxicity from C14 to 18. In contrast, the passive dosing method displayed similar or slightly increasing toxicity levels of BACs from C14 to C18, indicating higher toxicity of C16 and C18-BACs than that inferred by the solvent spiking test. These findings emphasize the potential of applying this innovative passive dosing approach in aquatic toxicity tests to generate reliable and accurate toxicity data and support a comprehensive risk assessment of cationic surfactants.

Screening structure and predicting toxicity of pesticide adjuvants using molecular dynamics simulation and machine learning for minimizing environmental impacts.

Surfactants as synergistic agents are necessary to improve the stability and utilization of pesticides, while their use is often accompanied by unexpected release into the environment. However, there are no efficient strategies available for screening low-toxicity surfactants, and traditional toxicity studies rely on extensive experimentation which are not predictive. Herein, a commonly used agricultural adjuvant Triton X (TX) series was selected to study the function of amphipathic structure to their toxicity in zebrafish. Molecular dynamics (MD) simulations, transcriptomics, metabolomics and machine learning (ML) were used to study the toxic effects and predict the toxicity of various TX. The results showed that TX with a relatively short hydrophilic chain was highly toxic to zebrafish with LC50 of 1.526 mg/L. However, TX with a longer hydrophilic chain was more likely to damage the heart, liver and gonads of zebrafish through the arachidonic acid metabolic network, suggesting that the effect of surfactants on membrane permeability is the key to determine toxic results. Moreover, biomarkers were screened through machine learning, and other hydrophilic chain lengths were predicted to affect zebrafish heart health potentially. Our study provides an advanced adjuvants screening method to improve the bioavailability of pesticides while reducing environmental impacts.

Biomarker responsiveness in Norwegian Sea mussels, Mytilus edulis, exposed at low temperatures to aqueous fractions of crude oil alone and combined with dispersant.

Biological effects of aqueous fractions of a crude oil, alone or in combination with dispersant, were investigated in mussels, Mytilus edulis, exposed at three temperatures (5, 10 and 15 °C). Polycyclic aromatic hydrocarbons (PAHs) tissue concentrations were determined, together with genotoxicity, oxidative stress and general stress biomarkers and the Integrated Biological Response (IBR) index. The bioaccumulation of individual PAHs varied depending on the exposure temperature, with relevant bioaccumulation of phenantrene and fluoranthene at 5 °C and heavier (e.g. 5-rings) PAHs at 15 °C. The values and response profiles of each particular biomarker varied with exposure time, concentration of the oil aqueous fraction and dispersant addition, as well as with exposure temperature. Indeed, PAH bioaccumulation and biomarker responsiveness exhibited specific recognizable patterns in mussels exposed at low temperatures. Thus, genotoxicity was recorded early and transient at 5 °C and delayed but unremitting at 10-15 °C. Catalase activity presented a temperature-dependent response profile similar to the genotoxicity biomarker; however, glutathione-S-transferase responsiveness was more intricate. Lysosomal membrane stability in digestive cells decreased more markedly at 5 °C than at higher temperatures and the histological appearance of the digestive gland tissue was temperature-specific, which was interpreted as the combined effects of PAH toxicity and cold stress. It can be concluded that the profile and level of the biological effects are definitely different at low temperatures naturally occurring in the Arctic/Subarctic region (e.g. 5 °C) than at higher temperatures closer to the thermal optimum of this species (10-15 °C).

Metabolism of alcohol ethoxylates (AEs) in rat, hamster, and human hepatocytes and liver S9: a pilot study for metabolic stability, metabolic pathway, and metabolites identification in vitro and in silico.

Alcohol ethoxylates (AEs) are a well-known class of non-ionic surfactants widely used by the personal care market. The aim of this study was to evaluate and characterize the in vitro metabolism of AEs and identify metabolites. Five selected individual homologue AEs (C8EO4, C10EO5, C12EO4, C16EO8, and C18EO3) were incubated using human, rat, and hamster liver S9 fraction and cryopreserved hepatocytes. LC-MS was used to identify metabolites following the incubation of AEs by liver S9 and hepatocytes of all three species. All AEs were metabolized in these systems with a half-life ranging from 2 to 139 min. In general, incubation of AE with human liver S9 showed a shorter half-life compared to rat liver S9. While rat hepatocytes metabolized AEs faster than human hepatocytes. Both hydrophobic alkyl chain and hydrophilic EO head group groups of AEs were found to be target sites of metabolism. Metabolites were identified that show primary hydroxylation and dehydrogenation, followed by O-dealkylation (shortening of EO head groups) and glucuronidation. Additionally, the detection of whole EO groups indicates the cleavage of the ether bond between the alkyl chain and the EO groups as a minor metabolic pathway in the current testing system. Furthermore, no difference in metabolic patterns of each individual homologue AE investigated was observed, regardless of alkyl chain length or the number of EO groups. Moreover, there is an excellent agreement between the in vitro experimental data and the metabolite profile simulations using in silico approaches (OECD QSAR Toolbox). Altogether, these data indicate fast metabolism of all AEs with a qualitatively similar metabolic pathway with some quantitative differences observed in the metabolite profiles. These metabolic studies using different species can provide important reference values for further safety evaluation.

The dispersant Corexit 9500 and (dispersed) oil are lethal to coral endosymbionts.

Endosymbionts (Symbiodiniaceae) play a vital role in the health of corals. Seawater pollution can harm these endosymbionts and dispersants used during oil spill cleanup can be extremely toxic to these organisms. Here, we examined the impact of oil and a specific dispersant, Corexit-9500, on two representative endosymbionts - Symbiodinium and Cladocopium - from the Southwestern endemic coral Mussismilia braziliensis. The survival and photosynthetic potential of the endosymbionts decreased dramatically after exposure to the dispersant and oil by ~25 % after 2 h and ~50 % after 7 days. Low concentrations of dispersant (0.005 ml/l) and dispersed oil (Polycyclic Aromatic Hydrocarbons, 1132 µg/l; Total Petroleum Hydrocarbons, 595 µg/l) proved highly toxic to both Symbiodinium and Cladocopium. These levels triggered a reduction in growth rate, cell size, and cell wall thickness. After a few hours of exposure, cellular organelles were damaged or destroyed. These acute toxic effects underline the fragile nature of coral endosymbionts.

A comparative study of surfactant distribution and fate (western and eastern) Egyptian Mediterranean coasts focusing on its environmental toxicity.

One of the most difficult-to-manage new contaminants constantly released into the environment is linear alkylbenzene sulphonate (LAS), an anionic surfactant. Significant volumes of LAS are received by the Mediterranean coast of Egypt. The current study is a comprehensive assessment of the environmental fate of the LAS 1505 km off the Mediterranean coast of Egypt in the fall of 2023 in order to track its geographic spread and eventual demise in the water column. Critical analysis of LAS revealed that it is vertically distributed in various ways according to sources, uses, production amounts, and salinity levels. The vertical variation of LAS can be explained by its amphiphilic structure. A significant increase in surfactant concentration (>300 µg/L) was recorded in 66% and 43% of the total samples, ranging from 301.128 to 455.36 and from 304.556 to 486.135 for the western and eastern sides along the Egyptian Mediterranean coast, respectively. Evaluation of the average acute and chronic risk quotient (RQ) along the investigated locations revealed that fish were the most susceptible to LAS in both long and short exposure periods. The presented results also indicated significant LAS toxicity to three trophic levels (RQ values > 1). LAS toxicity to marine organisms was greater in the western than in eastern coastal regions according to acute and chronic mixture risk characterization ratios (RCRmix). The three trophic levels in the study area had the following order of acute relative contribution (RC) to LAS toxicity: fish > invertebrates > algae. The ANOVA test results showed that in both the western and eastern regions, LAS varied significantly (p < 0.05) with salinity (1.04E-60 and 5.44E-42) and depth (6.02E-65 and 1.59E-47), respectively. In addition, a significant difference was observed using the ANOVA test between the eastern and western regions of the Egyptian Mediterranean coast.

Growth and physiological responses of submerged macrophytes to linear alkylbenzene sulfonate (LAS).

The potential toxic effects of linear alkylbenzene sulfonate (LAS), widely used in commercial detergents and cleaners, on submerged macrophytes remain unclear. We conducted a two-week exposure experiment to investigate LAS toxicity on five submerged macrophytes (four native and one exotic), focusing on their growth and physiological responses. The results showed that lower concentrations of LAS (< 5 mg/L) slightly stimulated the growth of submerged macrophytes, while higher doses inhibited it. Increasing LAS concentration resulted in decreased chlorophyll content, increased MDA content and POD activity, and initially increased SOD and CAT activities before declining. Moreover, Elodea nuttallii required a higher effective concentration for growth compared to native macrophytes. These findings suggest that different species of submerged macrophytes exhibited specific responses to LAS, with high doses (exceeding 5 ∼ 10 mg/L) inhibited plant growth and physiology. However, LAS may promote the dominance of surfactant-tolerant exotic submerged macrophytes in polluted aquatic environments.

PAH bioremediation with Rhodococcus rhodochrous ATCC 21198: Impact of cell immobilization and surfactant use on PAH treatment and post-remediation toxicity.

Polycyclic aromatic hydrocarbons (PAHs) are prevalent environmental contaminants that are harmful to ecological and human health. Bioremediation is a promising technique for remediating PAHs in the environment, however bioremediation often results in the accumulation of toxic PAH metabolites. The objectives of this research were to demonstrate the cometabolic treatment of a mixture of PAHs by a pure bacterial culture, Rhodococcus rhodochrous ATCC 21198, and investigate PAH metabolites and toxicity. Additionally, the surfactant Tween ® 80 and cell immobilization techniques were used to enhance bioremediation. Total PAH removal ranged from 70-95% for fluorene, 44-89% for phenanthrene, 86-97% for anthracene, and 6.5-78% for pyrene. Maximum removal was achieved with immobilized cells in the presence of Tween ® 80. Investigation of PAH metabolites produced by 21198 revealed a complex mixture of hydroxylated compounds, quinones, and ring-fission products. Toxicity appeared to increase after bioremediation, manifesting as mortality and developmental effects in embryonic zebrafish. 21198's ability to rapidly transform PAHs of a variety of molecular structures and sizes suggests that 21198 can be a valuable microorganism for catalyzing PAH remediation. However, implementing further treatment processes to address toxic PAH metabolites should be pursued to help lower post-remediation toxicity in future studies.

Toxicity of organic solvents and surfactants to the sea urchin embryos.

A comparative toxicity of widely applied organic solvents (methanol, ethanol, n-propanol, i-propanol, n-butanol, 2-butanol, i-butanol, t-butanol, 3-methoxy-3-methylbutanol-1 (MMB), ethylene glycol, diethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, glycerol, ethyl acetate, acetonitrile, benzene, dioxane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, 2-pyrrolidone, and N-methyl-2-pyrrolidone) and surfactants (PEG 300, PEG 6000, Tween 20, Tween 80, miramistin, and Cremophor EL) was studied using a sea urchin embryo model. Sea urchin embryo morphological alterations caused by the tested chemicals were described. The tested molecules affected P. lividus embryo development in a concentration-dependent manner. The observed phenotypic anomalies ranged from developmental delay and retardation of plutei growth to formation of aberrant blastules and gastrules, cleavage alteration/arrest, and embryo mortality. Discernible morphological defects were found after embryo exposure with common pharmaceutical ingredients, such as glycerol, Tween 80, and Cremophor EL. In general, solvents were less toxic than surfactants. PEG 6000 PEG 300, DMSO, ethanol, and methanol were identified as the most tolerable compounds with minimum effective concentration (MEC) values of 3.0-7.92 mg/mL. Previously reported MEC value of Pluronic F127 (4.0 mg/mL) fell within the same concentration range. Toxic effects of methanol, ethanol, DMSO, 2-methoxyethanol, 2-ethoxyethanol, Tween 20, and Tween 80 on P. lividus embryos correlated well with their toxicity obtained using other cell and animal models. The sea urchin embryos could be considered as an appropriate test system for toxicity assessment of solvents and surfactants for their further application as solubilizers of hydrophobic molecules in conventional in vitro cell-based assays and in vivo mammalian models. Nevertheless, to avoid adverse effect of a solubilizing agent in ecotoxicological and biological experiments, the preliminary assessment of its toxicity on a chosen test model would be beneficial.

Emerging pollutants in textile wastewater: an ecotoxicological assessment focusing on surfactants.

Water and several chemicals, including dyestuffs, surfactants, acids, and salts, are required during textile dyeing processes. Surfactants are harmful to the aquatic environment and induce several negative biological effects in exposed biota. In this context, the present study aimed to assess acute effects of five surfactants, comprising anionic and nonionic classes, and other auxiliary products used in fiber dyeing processes to aquatic organisms Vibrio fischeri (bacteria) and Daphnia similis (cladocerans). The toxicities of binary surfactant mixtures containing the anionic surfactant dodecylbenzene sulfonate + nonionic fatty alcohol ethoxylate and dodecylbenzene sulfonate + nonionic alkylene oxide were also evaluated. Nonionic surfactants were more toxic than anionic compounds for both organisms. Acute nonionic toxicity ranged from 1.3 mg/L (fatty alcohol ethoxylate surfactant) to 2.6 mg/L (ethoxylate surfactant) for V. fischeri and from 1.9 mg/L (alkylene oxide surfactant) to 12.5 mg/L (alkyl aryl ethoxylated and aromatic sulfonate surfactant) for D. similis, while the anionic dodecylbenzene sulfonate EC50s were determined as 66.2 mg/L and 19.7 mg/L, respectively. Both mixtures were very toxic for the exposed organisms: the EC50 average in the anionic + fatty alcohol ethoxylate mixture was of 1.0 mg/L ± 0.11 for V. fischeri and 4.09 mg/L ± 0.69 for D. similis. While the anionic + alkylene oxide mixture, EC50 of 3.34 mg/L for D. similis and 3.60 mg/L for V. fischeri. These toxicity data suggested that the concentration addition was the best model to explain the action that is more likely to occur for mixture for the dodecylbenzene sulfonate and alkylene oxide mixtures in both organisms. Our findings also suggest that textile wastewater surfactants may interact and produce different responses in aquatic organisms, such as synergism and antagonism. Ecotoxicological assays provide relevant information concerning hazardous pollutants, which may then be adequately treated and suitably managed to reduce toxic loads, associated to suitable management plans.

Ecotoxicity of commonly used oilfield-based emulsifiers on Guinean Tilapia (Tilapia guineensis) using histopathology and behavioral alterations as protocol.

This study examined the histological aberrations in the gill and liver tissues and behavioural changes of Tilapia guineensis fingerlings exposed to lethal concentrations of used Oilfield-based emulsifiers for 96 h. Various concentrations of the surfactants were tested, ranging from 0.0 to 15.0 ml/L. The behaviour of the fish was observed throughout the experiment, and the results showed that increasing concentrations of the surfactants led to progressively abnormal behaviour, including hyperventilation and altered opercular beat frequency. These behavioural changes indicated respiratory distress and neurotoxic effects. Histological analysis revealed structural aberrations in the gill and liver tissues, with higher concentrations causing more severe damage, such as lesions, necrosis, inflammation, and cellular degeneration. This implies that surfactants released even at low concentrations are capable of inducing changes in the tissues of aquatic organisms. These findings highlight the toxic effects of the surfactants on fish health and provide biomarkers of toxicity. Future research should focus on understanding the specific mechanisms and long-term consequences of surfactant toxicity on fish genetic composition, populations, and ecosystems to implement effective conservation measures.

Surface active dicationic ionic liquids as green oil spill dispersants.

The utilization of chemical dispersants as a way of mitigating of oil spills in marine eco-system has been extensively documented worldwide. Hence, in this research we have successfully synthesized two amphiphilic asymmetric Dicaionic Ionic Liquids (DILs). The efficacy of these synthesized DILs as dispersants was assessed using the baffled flask test (BFT). The results indicated a dispersant effectiveness ranging from 47.98 % to 79.76 % for the dispersion of heavy crude oil across various temperature ranges (10-30 °C). These dispersant-to-oil ratios (DOR) were maintained at 3: 100 (V%), showcasing promising dispersant capabilities for mitigating heavy crude oil spills. Additionally, acute toxicity tests conducted on Nile tilapia and Oreochromis niloticus have demonstrated the relatively low toxicity of the IL-dispersants, with Lethal Concentration 50 (LC50) values exceeding 100 ppm after 96 h. This suggests a practically slight toxic effect on the tested fish. In summary, the newly developed IL-dispersants are considered to be conducive to environmentally benign oil spill remediation.

Prediction of freshwater ecotoxicological hazardous concentrations of major surfactants using the QSAR-ICE-SSD method.

Synthetic surfactant products are continuously released into the aquatic environment in large quantities, posing a burden on ecosystems as a "pseudo-persistent" organic pollutant. Threshold derivation for protecting aquatic ecosystems is challenging due to the various homologous components of surfactants. In this study, five commercially available products were chosen as representative major types of surfactants. Corresponding quantitative structure-activity relationships (QSAR) were screened and subsequently combined with interspecific correlation estimation (ICE) to develop species sensitivity distributions (SSDs) for each component. Then, the 5th percentile hazard concentrations (HC5s) were calculated. The results indicated that the developed QSAR-ICE models demonstrated good toxicity prediction performance. The HC5 of each component showed a negatively correlation with alkyl chain length and a positive correlation with the amount of ethylene oxide. The HC5s of surfactants correlate with variations in their charged properties. Quaternary ammonium compounds (QAC) exhibited the lowest HC5s (8.5 ± 18.3 µg/L), followed by alcohol ethoxylates (AE), linear alkylbenzene sulfonates (LAS), and alcohol ethoxylated sulfates (AES); and alkyl oxide (AO) exhibited the highest HC5s (15784.2 ± 21552.6 µg/L). For cationic surfactants, the HC5s in the invertebrates were significantly lower than those in the fish; conversely, for anionic surfactants, the opposite was true, indicating a difference in the toxic mechanisms of surfactants with different charged properties across species taxa. Additionally, among invertebrates, shellfish demonstrated heightened sensitivity to surfactants, owing to their high accumulation and low metabolism of pollutants. Salmoniformes were the most sensitive among all species, indicating the necessity of prioritizing these species for aquatic ecological conservation in surfactant-contaminated waters.

Impact of the Hydrocarbon Chain Length of Biodegradable Ester-Bonded Cationic Gemini Surfactants on Self-Assembly, In Vitro Gene Transfection, Cytotoxicity, and Antimicrobial Activity.

Gemini surfactants, due to their unique structural features and enhanced properties compared to conventional surfactants, are becoming more popular in the domain of colloid and interface science, drug delivery, and gene delivery science. This distinct class of surfactants forms a wide range of self-assembled aggregates depending on their chemical structure and environmental conditions. The present work aims to develop Gemini with three distinct chain lengths linked through the ester group and quaternary nitrogen head groups that can bind DNA molecules and ultimately serve as vectors for DNA transfection. Thus, we synthesized three distinct cationic Gemini with 12, 14, and 16 carbons in their tails and studied the effect of the hydrocarbon chain length on their physicochemical properties and biological applications. The self-assembly of these Geminis in aqueous solution was investigated by a number of techniques, including surface tension, electrical conductivity, fluorescence probe, calorimetry, dynamic light scattering, and atomic force microscopy. All three Gemini were extremely surface active and self-assembled above a very low critical micelle concentration. Calorimetric studies suggested the formation of thermodynamically favorable aggregates in an aqueous medium. Chain length dependence was observed in the size as well as the morphology of the aggregates. These Gemini ions were found to bind DNA strongly, as indicated by the high binding constant values. In vitro gene transfection studies using the RAW 264.7 cell line suggested that all three cationic Gemini had transfection efficiencies comparable to that of commercial standard turbofectamine. MTT assay was also performed for concentration selection while using these Gemini as transfection vectors. Overall, it was observed that Gemini had very little cytotoxicity within the investigated concentration range, highlighting the significance of the ester link within the structure. When compared with known antimicrobials such as kanamycin and ampicillin, all three Gemini furnished excellent antimicrobial activity in both Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) microorganisms.

Analysis of Cleaning Power Using New Cleaning Kinetics and Interfacial Science Studies on Aquatic Toxicity of Surfactants.

Studies devised through the fusion of cleaning and environmental sciences can be summarized as follows: new cleaning kinetics applying a probability density function and a surface chemical approach to the aquatic toxicity of surfactants. Cleaning power analysis using the probability density functional method combines conventional cleaning kinetics using a first-order reaction equation with a risk analysis method using a probability density function. It is possible to analyze the cleaning mechanism from the obtained parameter values. It is also possible to determine whether the interaction between two different cleaning elements corresponds to a synergistic, additive, or offsetting effect. Studies on the aquatic toxicity of surfactants have focused on the surface tension at which surfactants exhibit toxicity, changes in toxicity due to water quality, and biodegradation, and the presence of adsorbed substances have been identified.

Trisiloxane Surfactants Negatively Affect Reproductive Behaviors and Enhance Viral Replication in Honey Bees.

Trisiloxane surfactants are often applied in formulated adjuvant products to blooming crops, including almonds, exposing the managed honey bees (Apis mellifera) used for pollination of these crops and persisting in colony matrices, such as bee bread. Despite this, little is known regarding the effects of trisiloxane surfactants on important aspects of colony health, such as reproduction. In the present study, we use laboratory assays to examine how exposure to field-relevant concentrations of three trisiloxane surfactants found in commonly used adjuvant formulations affect queen oviposition rates, worker interactions with the queen, and worker susceptibility to endogenous viral pathogens. Trisiloxane surfactants were administered at 5 mg/kg in pollen supplement diet for 14 days. No effects on worker behavior or physiology could be detected, but our results demonstrate that hydroxy-capped trisiloxane surfactants can negatively affect queen oviposition and methyl-capped trisiloxane surfactants cause increased replication of Deformed Wing Virus in workers, suggesting that trisiloxane surfactant use while honey bees are foraging may negatively impact colony longevity and growth. Environ Toxicol Chem 2024;43:222-233. © 2023 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Ecological impact of surfactant Tween-80 on plankton: High-scale analyses reveal deeper hazards.

The ecological risks of surfactants have been largely neglected because of their low toxicity. Multiscale studies have indicated that even if a pollutant causes no acute toxicity in a test species, it may alter interspecific interactions and community characteristics through sublethal impacts on test organisms. Therefore, we investigated the lethal and sublethal responses of the plankton species Scenedesmus quadricauda, Chlorella vulgaris, and Daphnia magna, to surfactant Tween-80. Then, high-scale responses in grazer life-history traits and stability of the D. magna-larval damselfly system were further explored. The results showed that discernible adverse effects on the growth or survival of the three plankton species were evident only at exceptionally high concentrations (≥100 mg L-1). However, 10 mg L-1 of Tween-80 notably affected the MDA concentration in grazer species, simultaneously displaying a tendency to diminish grazer's heartbeat and swimming frequency. Furthermore, Tween-80 reduced the grazer reproductive capacity and increased its predation risk by larval damselflies, which ultimately jeopardized the stability of the D. magna-larval damselfly system at much lower concentrations (10-100 fold lower) than the individual-scale responses. This study provides evidence that high-scale traits are far more sensitive to Tween-80, compared with individual-scale traits for plankton organisms, suggesting that the ecological risks of Tween-80 demand careful reassessment. SYNOPSIS: The concentration of Tween-80 needed to induce changes in community characteristics is markedly lower than that needed to produce individual-scale consequences. Thus, high-scale analyses have broad implications for understanding the hazardous effects of surfactants compared with an individual-scale analysis.

Advanced materials - Food grade melatonin-loaded Lipid Surfactant Submicron Particles (LSSP)-environmental impacts.

Lipid-based nanoparticles (LNPs) are advanced materials (AdMa), particularly relevant for drug delivery of poorly water-soluble compounds, while also providing protection, stabilization, and controlled release of the drugs/active substances. The toxicological data available often focus on the specific applications of the LNPs-drug tested, with indication of low toxicity. However, the ecotoxicological effects of LNPs are currently unknown. In the present study, we investigated the ecotoxicity of a formulation of Lipid Surfactant Submicron Particles (LSSPs) loaded with melatonin at 1 mg/mL. The LSSPs formulation has been developed to be fully compliant with regulatory for its potential use in the market and all components are food additives. The same formulation without the thickening agent xanthan gum (stabilizer in water phase) designated as LSSP-xg, was also tested. Two soil model invertebrate species were tested in LUFA 2.2 soil: Enchytraeus crypticus (Oligochaeta) and Folsomia candida (Collembola). Effects were assessed based on the OECD standard guideline (28 days) and its extension, the longer-term exposure (56 days). Assessed endpoints were survival, reproduction, and size. LSSPs and LSSP-xg were toxic to E. crypticus and F. candida reducing their survival and reproduction in a dose-dependent way: e.g., 28-day exposure: E. crypticus: LC/EC50 = 30/15 mg LSSPs/kg soil and F. candida LC/EC50 = 55/44 mg LSSPs/kg soil, with similar values for LSSP-xg. Size was also reduced for F. candida but was the least sensitive endpoint. There were no indications that toxicity increased with longer term exposure. The results provide relevant information on ecotoxicity of a AdMa and highlights the need for awareness of the potential risks, even on products and additives usually used in food or cosmetic industry. Further information on single components and on their specific assembly is necessary for the interpretation of results, as it is not fully clear what causes the toxicity in this specific AdMa. This represents a typical challenge for AdMa hazard assessment scenario.

Biocompatible and Biodegradable Surfactants from Orange Peel for Oil Spill Remediation.

Oil spill remediation plays a vital role in mitigating the environmental impacts caused by oil spills. The chemical method is one of the widely recognized approaches in chemical surfactants. However, the most commonly used chemical surfactants are toxic and non-biodegradable. Herein, two biocompatible and biodegradable surfactants were synthesized from orange peel using the ionic liquid 1-butyl-3-methylimidazolium chloride (BMIMCl) and organic solvent dimethylacetamide (CH3CN(CH3)2) as reaction media. The acronyms SOPIL and SOPOS refer to the surfactants prepared with BMIMCl and dimethylacetamide, respectively. The surface tension, dispersant effectiveness, optical microscopy, and emulsion stability test were conducted to examine the comparative performance of the synthesized surfactants. The Baffled flask test (BFT) was carried out to determine the dispersion effectiveness. The toxicity test was performed against zebrafish (Danio rerio), whereas the closed bottle test (CBT) evaluated biodegradability. The results revealed that the critical micelle concentration (CMC) value of SOPIL was lower (8.57 mg/L) than that of SOPOS (9.42 mg/L). The dispersion effectiveness values for SOPIL and SOPOS were 69.78% and 40.30%, respectively. The acute toxicity test demonstrated that SOPIL was 'practically non-toxic' with a median lethal concentration of more than 1000 mg/L after 96 h. The biodegradation rate was recorded as higher than 60% for both surfactants within 28 days, demonstrating their readily biodegradable nature. Considering these attributes, biocompatible and biodegradable surfactants derived from orange peel emerge as a promising and sustainable alternative for oil spill remediation.

Pathogenetic role of alveolar surfactant depleted by phosgene: Biophysical mechanisms and peak inhalation exposure metrics.

In contrast to water-soluble respiratory tract irritants in their gas phase, the physicochemical properties of 'hydrophilicity' vs. 'lipophilicity' are the preponderant factors that dictate the site of major retention of the gas at the portal of entry. The lipophilic physical properties of phosgene gas facilitate retention in the alveolar region lined with amphipathic pulmonary surfactant (PS). The relationship between exposure and adverse health outcomes is complex, may vary over time, and is dependent on the biokinetics, biophysics, and pool size of PS relative to the inhaled dose of phosgene. Kinetic PS depletion is hypothesized to occur as inhalation followed by inhaled dose-dependent PS depletion. A kinetic model was developed to better understand the variables characterizing the inhaled dose rates of phosgene vs. PS pool size reconstitution. Modeling and empirical data from published evidence revealed that phosgene gas unequivocally follows a concentration x exposure (C × t) metric, independent of the frequency of exposure. The modeled and empirical data support the hypothesis that the exposure standards of phosgene are described best by a C × t time-averaged metric. Modeled data favorably duplicate expert panel-derived standards. Peak exposures within a reasonable range are of no concern.