Nanoplastic (NPl) particles are increasingly found in aquatic environments due to the long-term degradation of mismanaged plastic waste, and their uptake and accumulation in aquatic organisms are progressively reported. However, their biodistribution and spatial association with biologically relevant elements after ingestion remain poorly understood. In this study, europium-doped polystyrene NPls (Eu-doped NPls) were used as model particles to investigate their spatial distribution in Daphnia magna, a representative freshwater organism, using synchrotron-based nanoprobe X-ray fluorescence (nano-XRF). Daphnia magna neonates (<24 h old) were exposed to 5-20 mg L-1 Eu-doped NPls for 48 h and by using Eu as the tracer, their biodistribution was mapped using nano-XRF at multiple resolutions. No mortality was observed during exposure, although body length was significantly reduced relative to the control under all tested conditions (p < 0.05). Reactive oxygen species (ROS)-associated fluorescence also increased significantly at 10 and 20 mg L-1, indicating an organism-level oxidative-stress response at higher exposure concentrations. Toxicokinetic analysis revealed rapid uptake and efficient depuration, yielding a low bioconcentration factor (BCF = 0.982 L g-1). Two-dimensional nano-XRF maps showed that most Eu-associated signals were localised within gut-associated regions and spatially co-occurred with endogenous elements including Fe, Ca and K. Eu-derived signal metrics increased with external exposure concentration, with broader distribution at lower concentration and more pronounced hotspot formation at higher concentrations. ROI-based co-localisation analysis showed increasing spatial association between Eu and endogenous elements, particularly Fe, suggesting that Eu-associated signals were spatially structured within gut-associated elemental microenvironments rather than uniformly distributed. This study demonstrates that Eu-doped NPls combined with ICP-MS and synchrotron nano-XRF provide a complementary element-specific framework for linking quantitative body-burden analysis with spatially resolved biodistribution in aquatic organisms.
Titanium dioxide nanoparticles (TiO₂ NPs) are among the most widely produced engineered nanomaterials, yet a mechanistic understanding of how their physicochemical properties govern biological interactions remains incomplete. Here we present an integrated, multi-scale computational workflow for the mechanistic in silico characterization of TiO₂ NPs spanning two crystallographic polymorphs (anatase and rutile) and four morphology classes (bipyramidal, cuboctahedral, spherical and amorphous), across a systematic size series of approximately 1-3 nm. At the quantum-mechanical level, density functional theory (DFT) calculations characterize the electronic structure, surface energetics and reactive-site distribution of each nanoparticle. These intrinsic descriptors are linked to mechanistic bio-interaction endpoints through three complementary approaches: (i) molecular docking followed by molecular dynamics (MD) simulations against a curated panel of 98 proteins (97 of them human), mapping the NP-protein binding landscape for individual proteins in isolation, which informs but does not by itself determine protein-corona composition; (ii) COSMO-RS-based thermodynamic modelling of nanoparticle-lipid bilayer interactions to estimate passive membrane permeability; and (iii) explicit all-atom MD simulations of NP interactions with two model cell-membrane systems, representing human keratinocytes and the rainbow-trout gill cell line RTgill-W1. Quantitative cross-tier analysis shows that these endpoints are not redundant: docking affinity and predicted membrane permeability are statistically independent across the nanoparticles common to both tiers (Spearman ρ = +0.03, n = 6), whereas particle size correlates strongly with both docking affinity (ρ = -0.77, n = 10, p = 0.009) and permeability (ρ = -0.83, n = 6, p = 0.042). The most robust structure-activity signal is morphological: faceted particles (bipyramidal, cuboctahedral, rutile) and rounded particles (spherical, amorphous) are completely separated in predicted permeability (mean log P - 5.8 versus +1.3; Mann-Whitney U = 0, p = 0.036). A complementary nano-SAR classification model built on 61 curated literature cytotoxicity records retains predictive performance under publication- and material-grouped cross-validation (AUC-ROC 0.83 versus 0.87 for random splits) and passes y-randomization, but its applicability domain is narrow and is defined explicitly here. We present this workflow as a tool for mechanistic interpretation and early-stage hazard prioritization rather than as a validated, regulatory-grade hazard-assessment platform: protein adsorption, membrane association and changes in membrane properties are mechanistic descriptors and are not equivalent to toxicity, and the framework has not yet been externally validated against experimental data. Used with these limitations in mind, it can support the hazard-screening component of Safe-and-Sustainable-by-Design workflows, which additionally require exposure, functional performance, environmental and life-cycle assessment that are outside the scope of this study.
V2C is a type of two-dimensional transition metal carbide (MXene) with rapidly expanding applications in energy, sensor, electronic information, and biomedicine. However, compared with Ti3C2, its health risk assessment remains inconclusive, posing a potential constraint on its further application. In this study, we examined immune and hematopoietic alterations in adult mice following pulmonary exposure to V2C nanosheets (NSs) on days 1 and 7, using Ti3C2 NSs as a reference. Exposure to V2C NSs induced a sustained elevation of neutrophils in the blood, lung, and bone marrow. This response differed markedly from the transient neutrophil increase followed by monocyte-mediated resolution observed with Ti3C2 NSs. Both MXenes upregulated G-csf in lung to activate emergency granulopoiesis, associated with reduced lung granulocyte-monocyte progenitors (GMPs) but expanded bone-marrow GMPs on day 1. By day 7, this effect persisted in V2C NSs, whereas Ti3C2 NSs increased lung GMPs as G-csf returned to baseline and selectively induced Mcp-1 and modulated Il-1β, thereby promoting monocyte recruitment and regulating myelopoiesis. Compared with the in vitro high biocompatibility of Ti3C2 NSs, V2C NSs exhibited pronounced cytotoxicity and elevated reactive oxygen species. Our study implied that V2C NSs demonstrated higher pulmonary immunotoxicity via persistent, neutrophil-driven inflammation due to the different chemical composition and biological activity from Ti3C2 NSs. This emphasized the need for tailored safety evaluations in the development and application of emerging nanomaterials.
Graphene is increasingly produced and utilized in industrial applications, raising concerns regarding occupational exposure and associated health risks. While numerous toxicological studies have investigated the hazard potential of laboratory-produced graphene, relatively little is known about exposure to airborne graphene particles in actual workplace environments or the toxicity of samples collected in the workplace. In the present study, we combined occupational exposure assessment in a graphene production facility with in vitro toxicological evaluation of graphene samples produced by liquid-phase exfoliation of graphite versus particulate matter collected in the same production facility. Workplace air sampling was performed using stationary and personal samplers and particulate matter was collected for elemental carbon (EC) analysis, Raman microscopy-spectroscopy, and toxicological testing using human lung cell lines (A549 and BEAS-2B). Personal EC concentrations ranged from 3 to 484 μg/m3, with the highest exposure levels observed during graphite powder handling. Raman analysis confirmed the presence of graphene in the collected samples. Toxicological assessments showed that samples collected in the workplace did not elicit cytotoxic effects at the tested concentrations while dispersions of as-produced graphene evoked a dose-dependent loss of cell viability. Overall, this pilot study demonstrates the feasibility of combining occupational exposure measurements with toxicological testing of real-world samples and suggests that airborne materials collected during graphene production exhibit low hazard potential in human lung cells.
Parkinson's disease (PD) is characterized by progressive dopaminergic neurodegeneration driven by mitochondrial dysfunction, oxidative stress, neuroinflammation, and impaired gut-brain communication. Here, we report a biogenic selenium nanoparticle (Se-NP) platform derived from mussel tissue and demonstrate its nano-enabled neuroprotective efficacy in a rotenone-induced zebrafish model of Parkinsonian neurotoxicity. Selenium was extracted from the tissue of Perna viridis (mussel) and used for the biogenic synthesis of Se-NPs through a green reduction approach under controlled conditions. The mussel-derived Se-NPs exhibited high redox-buffering capacity, enabling efficient attenuation of rotenone-induced oxidative stress, lipid peroxidation, and nitric oxide accumulation. Se-NP treatment preserved dopaminergic neuronal architecture, reduced microglial activation, and maintained gut epithelial integrity, indicating coordinated neuro-intestinal protection. Mechanistically, Se-NPs activated NRF2-driven antioxidant signaling through upregulation of NFE2L2a and HMOX1a and suppression of KEAP1a, thereby restoring endogenous antioxidant defences. At the neurovascular interface, Se-NPs enhanced blood-brain barrier integrity by upregulating tight junction proteins Claudin-5a and ZO-1, linking redox regulation to barrier stabilization. Notably, Se-NPs restored dopaminergic gene expression, modulated inflammatory signaling pathways, and normalized gut-associated microbial markers, thereby supporting nano-mediated regulation of the gut-brain axis. Collectively, this study establishes biogenic Se-NPs as a multifunctional nanotherapeutic that integrates antioxidant signaling, neurovascular protection, and gut-brain axis modulation to counteract rotenone-induced neurodegeneration, highlighting their potential as a nano-enabled strategy for PD intervention.
Selenium is a vital trace element for human health, but its distribution in European arable soils is often deficient. Selenium nanoparticles (SeNPs) represent a promising solution for biofortification due to their slow-release properties and reduced toxicity. However, their environmental behavior is dictated by interactions with soil organic matter (SOM). This study presents a comprehensive investigation of the physicochemical behavior of green-synthesized SeNPs (using yeast and soapwort extracts, and orange juice) within complex soil matrices. Utilizing an advanced analytical toolkit, including single particle inductively coupled plasma mass spectrometry (spICP-MS/MS), asymmetric flow field-flow fractionation (AF4-DLS/MALS), and capillary electrophoresis (CE-ICP-MS/MS), we characterized nanoparticle stability, aggregation, and the formation of the “eco-corona”. HPLC-ESIMS/ MS was further employed to identify specific SOM components, such as lignins, tannins, and peptides, responsible for surface interactions. Results indicate that the interaction of nanoparticles depends on their surface modification and, therefore, on the method of synthesis. SeNPs synthesized with orange juice exhibit superior stability, while specific SOM fractions and high salinity significantly drive aggregation and dissolution. This study provides critical insights into the ligand-mediated processes that govern the lifecycle of SeNPs in agricultural systems.
Microplastics and Nanoplastics (MPs/NPs), as emerging environmental pollutants, are characterized by their resistance to degradation, high mobility, and strong adsorption capacity. They are widely distributed across global environments and enter the human body through multiple pathways, where they interfere with metabolic health. This review introduces the concept of "metabolic footprint" to systematically analyze the environmental behavior of MPs/NPs, human exposure routes, and the associations between MPs/NPs, metabolic pathways, and metabolic diseases. MPs/NPs can induce energy metabolism disorders, insulin resistance, and chronic inflammation through mechanisms including mitochondrial dysfunction, disruption of gut microbiota balance, and interference with hepatic lipid metabolism, thereby increasing the risk of metabolic diseases such as obesity, type 2 diabetes, metabolic dysfunction-associated fatty liver disease, and atherosclerosis. In addition, MPs/NPs of different particle sizes exert distinct pathological effects through size-dependent mechanisms. Furthermore, as carriers of environmental pollutants, MPs/NPs can produce synergistic toxicity. There is an urgent need to establish comprehensive monitoring systems for MPs/NPs, develop effective intervention strategies, and conduct in-depth studies on their long-term health impacts, thereby providing a scientific basis for the formulation of relevant public health policies.
Dextran-functionalized graphene oxide nanoplatelets (GONP-Dex) have demonstrated potential for use in diagnostic imaging and as MRI contrast agents, however, their toxicology on human exposure needs to be carefully assessed. To date, no study has explored their effects on human melanocytes, which are melanin-producing cells conferring multiple biological benefits in the skin, ears, eyes, hair, oral cavity, and brain. GONP-Dex (6.25-100 μg/mL) was examined for cytotoxicity on melanocytes from lightly pigmented (LP) and darkly pigmented (DP) human skin for a 48-h duration by trypan blue exclusion assay and Alamar Blue assay, while the cellular membrane integrity was tested using LDH assay. GONP-Dex impaired metabolic activity of LP and DP cells without lowering cell counts. LP and DP cells exposed to GONP-Dex showed higher cellular melanin in the absence of any alteration of cellular tyrosinase activity. However, GONP-Dex showed a concentration-dependent suppression of melanogenic differentiation; both dendrite numbers and lengths were inhibited in LP and DP cells, with a greater susceptibility in DP cells, indicative of the capacity of GONP-Dex to impair melanin export function. GONP-Dex induced oxidative stress in LP and DP cells by increasing intracellular reactive oxygen species (ROS), lowering mitochondrial membrane polarization (MMP), and augmenting nitrite production. Together, our novel results demonstrate a proof-of-principle study into the melanocytotoxic impact of GONP-Dex. Future studies to examine the cytotoxic effects of GONP-Dex using a physiological cell model consisting of melanocyte and keratinocyte coculture and a 3D skin tissue equivalent will help in further validating cytotoxicity.
Silver nanoparticles (AgNPs), widely used in consumer products, are inevitably released into aquatic environments. In the water column, AgNPs undergo physicochemical transformations, notably oxidative dissolution, releasing ionic silver (Ag+). Both nanoparticulate and ionic Ag species can be toxic to phytoplankton, primarily through bioaccumulation. However, the mechanisms governing Ag bioaccumulation remain poorly understood due to the coexistence of multiple Ag forms and particle sizes, as well as the structural diversity across phytoplankton communities. In this study, we employed a recently proposed methodology to investigate the interactions of Ag+ and AgNPs (5 and 20 nm) with two freshwater phytoplankton species exhibiting distinct cellular architectures: the green alga Chlamydomonas reinhardtii and the diatom Cyclotella meneghiniana. Bioaccumulation and adsorption kinetics varied with Ag form, particle size, and cellular architecture. Rapid Ag bioaccumulation was observed during exposure to Ag+, whereas accumulation under AgNP exposure was more gradual and sustained. Smaller nanoparticles (5 nm) resulted in higher Ag bioaccumulation in both organisms, with greater dissolution and stronger cell adsorption compared to 20 nm AgNPs. The diatom exhibited higher uptake rates and Ag association than the green alga, consistent with transmission electron microscopy (TEM) observations. AgNPs were embedded in the frustule and detected within cellular compartments of C. meneghiniana, while, in C. reinhardtii, they were mainly observed as aggregates outside the cells, associated with the cell wall and palmelloid envelope. We demonstrate that Ag bioaccumulation is strongly influenced by silver speciation, particle size, and cellular architecture, highlighting the need to integrate these factors in environmental risk assessments.
Although plastic threatens terrestrial ecosystems, the effects of micro- and nanoplastics (MNPs) combination in plants remain poorly understood and need in-depth investigations. This study investigates the effects of polyethylene MNPs (0.1% w/v; Ø 200-9900 nm) on Ocimum basilicum by exposing seeds to MNPs for 5 days (Seed Treatment; ST) or hydroponically-grown 20-day seedlings for 15 days (Plant Treatment; PT). Biometric, physiological, cytological, ultrastructural responses, oxidative stress level and antioxidant responses were analyzed. In PT, transmission electron microscopy revealed MNPs presence in xylem vessel of stem, highlighting the translocation of smaller particles to aerial parts. MNPs adsorption onto roots reduced water uptake, affecting plant metabolism. ST impaired root growth, with signs of cyto-genotoxicity and oxidative damage. PT reduced CO₂ assimilation due to stomatal limitations and altered plants biometric traits, including root length (+42.6%), root biomass (-35.2%) and leaf area. Oxidative stress increased in leaves in terms of H2O2 accumulation (+47.4%) and lipid peroxidation (+22.2%). These findings underscore the detrimental impact of MNPs on basil growth. Further research is essential to elucidate MNPs uptake and translocation mechanisms, and to assess the potential risks of MNPs contamination for plant health and ecosystem integrity.
In 2019, the REACH-registration dossier of ZnO was evaluated by the European Chemicals Agency (ECHA), which requested additional data on the fate and effects of all nanoforms present on the EU market. A testing scheme was specified, divided into two steps. First, fate data (OECD GD 29; OECD TG 318) were required for the 28 ZnO nanoforms available on the EU market at that time. In the second step, representative nanoforms were tested for their chronic toxicity to aquatic organisms using the freshwater algal growth inhibition test (OECD TG 201) and the Daphnia magna reproduction test (OECD TG 211), applying nano-specific adaptations available before OECD GD 317 was published. The objective of the testing program was to generate robust, GLP-compliant ecotoxicological data to determine whether Zn ions are the primary toxicity driver for nano ZnO or whether specific nano-related effects occur. Results indicated that in all test systems the main fraction consisted of particles and agglomerates with a hydrodynamic diameter > 200 nm, while only small amounts of dispersed (<200 nm) or dissolved (<200 nm + 3 kDa) fractions were detected of which approx. 1.6% to 2.9% were assumed to be nano. Despite particle-algae hetero-agglomeration, effective concentrations from both test systems showed good comparability between ZnO nanoforms and ionic ZnCl2, when considering natural variability within the test. Thus, findings point to ionic zinc as the main driver of toxicity, with no clear evidence for an additional nano-specific effect. Furthermore, sequential filtration measurements provided useful insights into the behaviour of ZnO nanomaterials during testing and their interactions with aquatic organisms.
Metal oxide nanoparticles (MONPs) raise growing cytotoxicity concerns, yet experimental assessment requires multiple time-consuming biological assays. We developed a leakage-free two-stage machine learning framework predicting MONP toxicity and biological endpoints from physicochemical features. In Stage 1, a stacking ensemble (ExtraTrees + GradientBoosting + RandomForest + HistGradientBoosting → LogisticRegression meta-learner) trained on 304 KONA dataset records using out-of-fold (OOF) probability generation achieved Accuracy = 0.87 and ROC-AUC = 0.91 on held-out data, and ROC-AUC = 0.76 on an independent external validation set. A three-way ablation study revealed that IC50-derived toxicity class substantially improves Stage 2 regression (ΔR2 = +0.22 for ROS; +0.12 for Membrane Damage), while out-of-fold-predicted class provides negligible improvement with toxicity classification. In Stage 2, ordinal classification (Low/Moderate/High) with literature-based thresholds replaced continuous regression. BaggingClassifier and GradientBoostingClassifier achieved AUC = 0.82-0.86 across four endpoints. Grouped permutation importance and LIME identified nanoparticle composition, surface chemistry, core size, and surface area as dominant predictors, consistent with ion dissolution and ROS-mediated mechanisms. This framework reduces experimental burden while providing interpretable, generalizable MONP cytotoxicity predictions.
Mechanical recycling and other processes involved in the end-of-life treatment of 3D-printed plastic polymers can lead to the generation of micro- and nanoplastics (MNPs). As the use of these materials continues to grow, the mechanical degradation of plastics from 3D printing may increase human exposure to MNPs, raising concerns about potential health risks for users and environmental impacts. One of the main routes of exposure to MNPs is via inhalation. For regulatory purposes, most of inhalation studies have been performed using rodents and following the OECD TG 412, however, these models do not accurately mimic the physiology of the human pulmonary system. As alternative, New Approach Methodologies (NAMs) based on human in vitro models have been used lately, providing simple and valuable, and physiologically relevant tools for research. In this work, simple in vitro models using Calu-3 and TK6 cells were exposed for 24 h (acute) and the advanced primary human epithelial MucilAir™ model was exposed for 24 h (acute) and 28 days (sub-acute, adapting the OECD TG 412) to MNPs made of polypropylene (PP), polycarbonate (PC), PP + silver nanoparticles (PP + Ag) and PC + single wall carbon nanotubes (PC + SWCNT). The results showed no significant toxicity of MNPs in acute exposures using the Calu-3 and TK6 models. In contrast, significant effects were observed along time after acute and subacute exposure of MucilAir™ to the different MNPs. These results indicate that robust in vitro models such as MucilAir™ may represent a valuable NAM for acute and sub-acute inhalation toxicity studies.
This paper critically reviews current initiatives, regulatory measures, and safety standards addressing plastic pollution, highlighting developments in Europe. While numerous policies and standards are in place, their impact is often constrained by fragmented implementation across disciplines, nations, and sectors. The urgent need for focused scientific research is especially evident in the case of nanoplastics, whose distinctive physicochemical properties and interactions with other contaminants present complex challenges for risk assessment and environmental monitoring. We explore pathways toward sustainable solutions, focusing on reducing plastic footprints and embedding Safe and Sustainable by Design (SSbD) principles into innovation and production. Data-driven Operational Research (OR) tools are presented as a means to optimize decision-making, ensuring interventions remain efficient, evidence-based, and responsive to evolving scientific insights. Equally important is the adoption of rigorous quality assurance (QA) and quality control (QC) protocols in hazard and fate studies, which are vital for producing reliable, reproducible data that can inform both science and policy.This policy analysis situates pollutants within a complex, interconnected system and introduces the exposome approach as a framework for evaluating cumulative environmental exposures over time. Embedding exposome science within the One Health paradigm offers a forward-looking strategy that bridges research, governance, and technology. Such integration fosters interdisciplinary collaboration and enables more effective pollution management. Ultimately, progress in addressing global plastic pollution depends less on new legislation and more on overcoming fragmented efforts through coordinated, cross-sector action guided by One Health perspectives.
Silver nanoparticles (NPs) are frequently deployed in medical devices due to their antimicrobial properties. We previously reported an eco-friendly process for preparing AgNPs by using a quaternary ammonium salt of hydroxyethyl cellulose (HEC) as a capping and reducing agent. Here, inspired by the Safe and Sustainable by Design framework, we conducted a comprehensive safety and efficacy assessment of AgHEC versus commercial uncoated AgNPs before and after their integration into wound dressings based on poly L-lactic acid fibers prepared by electrospinning (PLLA-Ag and PLLA-AgHEC). We demonstrated that the AgHEC formulation displayed an improved antibacterial efficacy compared to its uncoated counterpart. We also performed colloidal and dissolution studies in vitro using relevant biological media. Moreover, the toxicological evaluation using state-of-the-art porcine skin models and the clinically relevant dermal open flow microperfusion (dOFM) approach demonstrated negligible penetration of silver through both intact and disrupted skin while no evidence for elevated inflammatory immune responses was noted compared to the control. Taken together, our findings not only validate AgHEC as an alternative for wound healing applications but also establishes a robust methodological framework for the future evaluation of other nanobiomaterials.
This study examined the shear-driven fragmentation of the UV-aged (UV-A: 340 nm; 0.91 W·m-2 over 16 weeks; dose = 8.81 × 103 kJ·m-2) and unaged polyethylene microspheres (180-212 μm) in water. Scanning electron microscopy revealed that UV aging and shear mixing altered the particle surface morphology, whereas the unaged particles without shear mixing remained intact. The continuous increase in carbonyl (0.15-0.36), vinyl (0.14-0.3), and ester (0.14-0.34) values indicated a progressive photo-oxidation in the microspheres. After shear-mixing of both the UV-aged and pristine groups in the jar-tester (240 rpm; energy density 2.84 KJ/L; shear rate, Gbulk = 6.3 × 102 s-1) over different time points (30, 60, 90, and 120 min), nanoparticle tracking analysis revealed a one-magnitude higher nanoparticle concentration in UV-aged suspensions than in the pristine ones by 120 min, with mean concentrations of 2.7 × 107 and 4.5 × 106 particles mL-1, respectively. The nanoparticle release rate was six times higher in UV-aged (3556 particles·s-1) than in the pristine particles (576 particles·s-1). Nanoparticle mean size decreased to 62.7 nm from 128 nm, and to 72.3 nm from 122.6 nm for UV-aged and pristine particles, respectively. First-order exponential fits (R2 = 0.956-0.985) for particle count growth and size decay revealed that UV-aged particles fragmented 1.2 times faster, resulting in shorter doubling times and half-lives. The nanoparticle counts increased while their size decreased exponentially. UV-aging reduced the negative surface charge, while shear mixing exhibited a neutralizing effect on the particles. Shear mixing alone released nanoparticles, while pre-UV-treatment amplified the effect. This study provided a shear-kinetic framework that serves as a baseline for establishing photo-mechanical synergy in plastic degradation.
Biodegradable mulch microplastics (BMPs), such as PBAT and PLA, are widely used in agriculture but can persist in soils and carry coexisting pesticides like dinotefuran (DIN). Despite its widespread use, DIN's environmental fate and microbial toxicity remain insufficiently understood. This study explores the adsorption behavior of DIN on PBAT and PLA and assesses the toxicity of MPs‑neonicotinoid complexes. To provide a more comprehensive understanding, two structurally related neonicotinoids, imidacloprid (IMI) and clothianidin (CLO), were included as comparative references. Adsorption kinetics and isotherms were measured, along with multi-scale characterization (SEM, XRD, FT-IR, XPS, contact angle). The results were integrated with Escherichia coli (E.coli) inhibition assays to assess microbial toxicity. PBAT exhibited a rougher surface with lower crystallinity (7.8% vs 17.1%), and greater hydrophobicity (contact angle 107.7° vs 92.9°) compared to PLA. This increased hydrophobicity likely contributed to the higher adsorption capacity of PBAT for DIN, as confirmed by Langmuir isotherm fitting (Qm ≈ 15.2 mg·kg-1 for PBAT vs Qm ≈ 4.69 mg·kg-1 for PLA). FT-IR/XPS indicated hydrogen-bonding/dipole interactions acting cooperatively with hydrophobic association. Increasing CaCl2 (0-0.1 mol·L-1) enhanced adsorption while NaCl produced a biphasic response, that is low-level promotion, mid-high suppression. MPs-DIN mixtures more strongly inhibited E.coli than single exposures. These results identify BMPs as potential vectors of neonicotinoids and highlight polymer chemistry and environmental modulators in co-exposure risk assessments.
Microplastic (MP) pollution represents an emerging threat to aquatic ecosystems; yet, most studies remain restricted to isolated biomarker comparisons, without addressing how these pollutants reorganize organisms' systemic properties. In this study, we investigated the effects of naturally aged polypropylene microplastics (NAPP-MPs) - a highly abundant and environmentally relevant polymer - on adult Danio rerio, a recognized model organism in ecotoxicological studies. Fish were exposed to 4.5 mg/L of NAPP-MPs for 15 days and assessed using a biomarker panel that encompassed oxidative and nitrosative stress, antioxidant defenses, neurochemical and endocrine parameters, and digestive protease activities. We observed substantial particle bioaccumulation and consistent biochemical alterations, including increased production of reactive oxygen species, elevated levels of malondialdehyde and nitric oxide, activation of antioxidant enzymes such as superoxide dismutase and catalase, and enhancement of non-enzymatic antioxidant defenses, as measured by the DPPH method. Moreover, we detected elevated concentrations of dopamine, serotonin, and cortisol, as well as increased acetylcholinesterase activity and intensified actions of the digestive proteases trypsin and chymotrypsin. Beyond mean-level differences, we applied a multiscale analytical framework-including criticality analysis, signed networks, information theory, energy landscapes, and Bayesian causal modeling with bootstrap-which revealed that NAPP-MPs shift biochemical systems from adaptive critical regimes to less stable and fragmented states, characterized by loss of cohesion, reorganization of informational flows, and altered functional hierarchies across regulatory modules. Collectively, our results demonstrate that NAPP-MPs not only trigger discrete biochemical responses in zebrafish but also reshape the systemic architecture of homeostasis, undermining both stability and adaptive plasticity. Thus, our study advances the field by integrating innovative methodologies into MP ecotoxicology, providing a conceptual and methodological framework that broadens understanding of their risks and supports more realistic, complex environmental assessments.
Despite their huge technological interest, practical application of MXene nanomaterials is somehow hampered by their potential toxicity. In this regard, the present work showcases the design and implementation of a full in-silico methodology for the toxicological analysis of nanoparticles (NPs) of two MXenes within a human cell environment, employing cost-effective computational approaches to achieve a preliminary hazard estimation in the absence of experimental data. This study combines computational methodologies of very different nature, from Density Functional Theory (DFT) calculations for a full quantum mechanics optimization of the system of interest and thermodynamical approximations like the COSMO-RS methodology for the analysis of the behaviour in membranes, to other, simpler methods like classic electrostatic Monte-Carlo calculations for the interaction with proteins, and machine-learning based methods for the development of simpler yet accurate predictive tools for a broader use. This multi-scale workflow was applied to a compendium of NPs derived from two MXenes of interest, Ti3C2 and Cr2C, to understand the possible harm such materials could cause in the human body. As a result, an extremely low permeability and membrane-crossing potential was observed for the Ti3C2 NPs, and very weak and superficial interaction was observed for both MXenes with a library of critical human proteins. Two predictive docking energies models with R2 of 0.85 were developed, and a low toxicological potential via the considered mechanisms was concluded as a result, thus paving the way of reaching accurate toxicological predictions for a wide range of MXene nanomaterials.
