Influence of Concentration, Surface Charge, and Natural Water Components on the Transport and Adsorption of Polystyrene Nanoplastics in Sand Columns.

Information about the influence of surface charges on nanoplastics (NPLs) transport in porous media, the influence of NPL concentrations on porous media retention capacities, and changes in porous media adsorption capacities in the presence of natural water components are still scarce. In this study, laboratory column experiments are conducted to investigate the transport behavior of positively charged amidine polystyrene (PS) latex NPLs and negatively charged sulfate PS latex NPLs in quartz sand columns saturated with ultrapure water and Geneva Lake water, respectively. Results obtained for ultrapure water show that amidine PS latex NPLs have more affinity for negatively charged sand surfaces than sulfate PS latex NPLs because of the presence of attractive electrical forces. As for the Geneva Lake water, under natural conditions, both NPL types and sand are negatively charged. Therefore, the presence of repulsion forces reduces NPL's affinity for sand surfaces. The calculated adsorption capacities of sand grains for the removal of both types of NPLs from both types of water are oscillating around 0.008 and 0.004 mg g-1 for NPL concentrations of 100 and 500 mg L-1, respectively. SEM micrography shows individual NPLs or aggregates attached to the sand and confirms the limited role of the adsorption process in NPL retention. The important NPL retention, especially in the case of negatively charged NPLs, in Geneva Lake water-saturated columns is related to heteroaggregate formation and their further straining inside narrow pores. The presence of DOM and metal cations is then crucial to trigger the aggregation process and NPL retention.

Impact of a nanofiltration system on microplastic contamination in Geneva groundwater (Switzerland).

Microplastics (MPs) have been observed in the oceans, fresh waters, karstic water and remote water bodies. However, little is known on groundwater contamination, which is a natural resource of utmost importance for millions of people and is often perceived as a reliable source of water. Moreover, nanofiltration is perceived as a reliable technology to remove contaminants from water. In this study, large sample volumes of a silty-sandy gravel aquifer and the corresponding nanofiltered water were analysed for the presence of MPs (> 20 µm) using Fourier transform infrared (FTIR) microscopy. Concentration in ground water was 8 ± 7 MPs/m3 and increased to 36 ± 11 MPs/m3 in nanofiltered water. All MPs had a maximum Ferret diameter lower than 500 µm. Size distribution of MPs was towards the small size class (20-50 µm). In groundwater, 33% of MPs were detected in the smallest size class (20-50 µm) and 67% in the 50-100-µm-size class. In comparison, around 52% of MPs in nanofiltered water were observed in the 20-50 µm size class. Moreover, 33% of the MPs observed in nanofiltered water were in the 50-100 µm size class and 15% in the 100-500-µm-size class. From a chemical point of view, different plastic polymers were identified in groundwater and in nanofiltered water, such as polypropylene (PP), polyvinyl chloride (PVC), ethylene (vinyl acetate) copolymer (EVA), polyethylene (PE), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) and other polymer materials (such as polystyrene-based copolymers, vinyl-based copolymers). Fibres were observed in all samples, but only a small number of fibres (near 1%) were identified as PP synthetic fibres in nanofiltered water. Furthermore, no clear difference of fibre concentrations was observed between groundwater (232 ± 127 fibres/m3) and nanofiltered water (247 ± 118 fibres/m3). Groundwater had extremely low levels of microplastics, and although the nanofiltration effectively removes suspended particulate matter, it slightly contaminates the filtered water with MPs.

Contamination and removal efficiency of microplastics and synthetic fibres in a conventional drinking water treatment plant in Geneva, Switzerland.

Although it is known that freshwater resources are contaminated with microplastics (MPs), still limited information is known about the efficiency of large drinking water treatment plants (DWTP) to remove microplastics. Moreover, reported concentrations of MPs in drinking water variates from some units to thousands of units per litre and the sampling volumes used for MPs analysis are generally heterogeneous and limited. The present study evaluates the removal of MPs and synthetic fibres in the main DWTP of Geneva, Switzerland, by considering large sampling volumes at different time intervals. Furthermore, contrary to other studies, this DWTP does not count with a clarification process before sand filtration and coagulated water is sent directly to sand filtration. In this study a distinction is made between microplastics as fragments, films, pellets, and synthetic fibres. Raw water and effluents of each filtering mass (sand and activated carbon filtration) are analysed for the presence of MPs and synthetic fibres with sizes ≥63 µm using infrared spectroscopy. Concentrations of MPs in raw water range from 25.7 to 55.6 MPs/m3 and in treated water from 0 to 4 MPs/m3, respectively. Results show that 70 % of MPs are retained during sand filtration and total removal is equal to 97 % in treated water after activated carbon filtration. Concentration of identified synthetic fibres is low (average value of 2 synthetic fibres/m3) and constant in all steps of water treatment. Chemical composition of microplastics and synthetic fibres is found more heterogeneous in raw water than after sand filtration and activated carbon filtration, indicating the persistence of some types of plastics (like polyethylene and polyethylene terephthalate) in water treatment processes. Heterogeneities in MP concentrations are observed from one sampling campaign to another, indicating significant variations of MP concentrations in raw water.

Acute toxicity of nanoplastics on Daphnia and Gammarus neonates: Effects of surface charge, heteroaggregation, and water properties.

Despite progress in evaluation of risk assessment, knowledge gaps largely exist understanding the toxicity of nanoplastics in aquatic systems considering nanoplastics surface properties, environmental media characteristics and species ecological traits. In this study, amidine - functionalized polystyrene nanoparticles (PS-NPLs) of 20, 40, 60 and 100 nm are considered using Geneva lake water and mineral water to investigate the behavior and effects in neonate organisms of the plankton Daphnia magna and the benthos Gammarus fossarum. Key parameters including ζ-potential, z-average diameter, conductivity, polydispersity index, pH, EC50 were investigated. The results showed that the toxicity of PS-NPLs exhibited a dose-response relationship, size- and exposure condition-dependent trend. The smaller size PS-NPLs (20 and 40 nm) induced higher adverse effects than PS-NPLs of 60 and 100 nm in both water conditions and crustacean species. Moreover, PS-NPLs were found more toxic in the mineral water compared to lake water. Principal component analysis evidenced that the surface charge and aggregation behavior are the most influential toxicity of PS-NPLs factor for D. magna and Gammarus fossarum, respectively. These results highlight the relationship between PS-NPLs intrinsic properties, their transformation behavior, water properties and species-specificity in the evaluation of PS-NPLs biological effects on crustacean neonates in natural aquatic environments.

Removal efficiency and adsorption mechanisms of CeO2 nanoparticles onto granular activated carbon used in drinking water treatment plants.

The presence of NPs in drinking water resources raises a global concern on their potential risk for human health, and whether or not drinking water treatment plants are able to effectively remove NPs to prevent their ingestion by humans. In this study, we investigate the efficiency of granular activated carbon (GAC), commonly used in conventional municipal water treatment processes, for the removal of CeO2 NPs. In ultrapure water, NPs are found to have a good affinity for GAC and results indicate an increase in the adsorption capacity from 0.62 ± 0.10 to 5.05 ± 0.51 mg/g, and removal efficiency from 35 % ± 4 to 54 % ± 5 with increasing NPs concentration. Kinetic studies reveal that intraparticle diffusion is not the only rate controlling step indicating that mass transfer effect is also playing a role. Adsorption mechanisms are mainly controlled by the electrostatic attractions between the positively charged NPs and negatively charged GAC. Although electrostatic conditions in Lake Geneva water are less favorable for NPs adsorption, the adsorption capacity and removal efficiency are higher than in ultrapure water with values raising from 0.41 ± 0.17 to 7.13 ± 1.13 mg/g and 26 % ± 8 to 75 % ± 11, respectively. Furthermore, the external mass transfer process onto GAC surface is more important than for ultrapure water. NPs adsorption mechanism is explained by the presence of divalent cations and natural organic matter (NOM) which promote the formation of CeO2 NPs-NOM-divalent cation heteroaggregates increasing both adsorption and removal efficiency by cation bridging.

Retention and Transport of Nanoplastics with Different Surface Functionalities in a Sand Filtration System.

The efficiency of sand filtration was investigated in terms of the behavior of the nanoplastics (NPLs) with different surface functionalities. The initial condition concentrations of NPLs were varied, and their effects on retention and transport were investigated under a constant flow rate in saturated porous media. The behavior of NPLs in this porous system was discussed by considering Z- average size and zeta (ζ) potential measurements of each effluent. The retention efficiencies of NPLs were ranked as functionalized with amidine [A-PS]+ > with sulfate [S-PS]- > with surfactant-coated amidine [SDS-A-PS]-. The reversibility of the adsorption process was revealed by introducing surfactant into the sand filter system containing adsorbed [A-PS]+ at three different initial state concentration conditions. The deposition behavior on sand grain showed that positively charged NPLs were attached to the quartz surface, and negatively charged NPLs were attached to the edge of the clay minerals, which can be caused by electrical heterogeneities. The homoaggregates made of positively charged NPLs were more compact than those made of negatively charged NPLs and surfactant-coated NPLs. An anti-correlation was revealed, suggesting a connection between the fractal dimension (Df) of NPL aggregates and retention efficiencies. Increased Df values are associated with decreased retention efficiencies.The findings underscore the crucial influence of NPL surface properties in terms of retention efficiency and reversible adsorption in the presence of surfactants in sand filtration systems.

Embryonic exposure to selenium nanoparticles delays growth and hatching in the freshwater snail Lymnaea stagnalis.

Selenium nanoparticles (SeNPs) have been applied in the biomedical and biocidal domain which may have potential environmental risks for aquatic systems. However, the knowledge of its toxicity and the role of functionalization on aquatic invertebrates are scarce. Thus, the present study aimed to analyze the embryotoxicity of two types of SeNPs coated with Sodium carboxymethyl cellulose (CMC-SeNPs) and Chitosan (CS-SeNPs) to the freshwater snail Lymnaea stagnalis in lake water, focusing on embryonic development. The influence of surface coatings and ions release, on the embryonic development of SeNPs to freshwater snail L. stagnalis was investigated. For this end, the snails were exposed to different concentrations of SeNPs and Se ions (0.05-1 mg L-1) during 7 days and multiple endpoints were analyzed, including developmental stage frequency, morphological alterations, embryos mortality and hatching success. The results showed that both Se forms promoted the developmental delay, mortality, morphological changes, and hatching inhibition in snail embryos in a concentration-dependent manner. CMC-SeNPs are 2.6 times more embryotoxic compared to CS-SeNPs indicating the importance of surface coating on the embryotoxicity. Moreover, the results revealed that although both forms of Se inhibited the embryo development and reduced the hatching of L. stagnalis, the mode of action on the embryogenesis was different. SeNPs had a higher toxicity to snails' embryos compared to their dissolved counterparts. Despite significant dissolution, by comparing the SeNPs with their dissolved fraction, the results suggest SeNPs inhibition effect on the snail development could be caused by both SeNPs and Se4+, and SeNPs might be the major development retardation driver rather than Se ions. The present study evidenced by the first time the toxicity effects of SeNPs on the snail embryogenesis, and highlighted how SeNPs intrinsic properties influence their transformation and toxicity in environmental relevant scenarios.

Stability and surface properties of selenium nanoparticles coated with chitosan and sodium carboxymethyl cellulose.

The effect of polysaccharide coatings on the stability and release characteristics of selenium nanoparticles (SeNPs) was evaluated by comparing the characteristics of chitosan-coated SeNPs (CS-SeNPs) and sodium carboxymethyl cellulose-coated SeNPs (CMC-SeNPs). The release characteristics of SeNPs were investigated in storage conditions, gastrointestinal conditions, and free radical systems. CMC-SeNPs formed dimers or trimers, whereas CS-SeNPs were monodispersed but formed large aggregates in a pH range of 7.4-8.25. Upon 50 days of storage at 30 °C, both CMC-SeNPs and CS-SeNPs were converted to Se4+. SeNPs exhibited a lower release rate in simulated gastrointestinal conditions than in free radical systems. SeNPs release in ABTS and superoxide anion free radical systems followed the first-order and Korsmeyer-Peppas models, respectively, indicating that SeNP release is mainly governed by dissolution mechanisms. Additional studies are needed to examine the potential environmental effects and biological activity of the Se4+ released from SeNPs.

Fate and removal efficiency of polystyrene nanoplastics in a pilot drinking water treatment plant.

Occurrence of microplastics and nanoplastics in aquatic systems, as well as in water compartments used to produce drinking water have become a major concern due to their impact on the environment and public health. Nanoplastics in particular, in regard to their fate and removal efficiency in drinking water treatment plants (DWTP), which ensure water quality and supply drinking water for human consumption have been, by far, rarely investigated. This study investigates the removal efficiency of polystyrene (PS) nanoplastics in a conventional water treatment plant providing drinking water for 500'000 consumers. For that purpose, a pilot-scale DWTP, located within the main treatment plant station, reproducing at a reduced scale the different processes and conditions of the main treatment plant is used. The results show that filtration process through sand and granular activated carbon (GAC) filters in the absence of coagulation achieves an overall nanoplastic removal of 88.1%. The removal efficiency of filtration processes is mainly attributed to physical retention and adsorption mechanisms. On the other hand, it is found that coagulation process greatly improves the removal efficiency of nanoplastics with a global removal efficiency equal to 99.4%. The effective removal efficiency of sand filtration increases considerably from 54.3% to 99.2% in the presence of coagulant, indicating that most of PS nanoplastics are removed during sand filtration process. The higher removal efficiency with the addition of coagulant is related to nanoplastics surface charge reduction and aggregation thus significantly increasing their retention in the filter media.

Toxicity of selenium nanoparticles on Poterioochromonas malhamensis algae in Waris-H culture medium and Lake Geneva water: Effect of nanoparticle coating, dissolution, and aggregation.

Understanding the algal toxicity of selenium nanoparticles (SeNPs) in aquatic systems by considering SeNPs physicochemical properties and environmental media characteristics is a concern of high importance for the evaluation and prediction of risk assessment. In this study, chitosan (CS) and sodium carboxymethyl cellulose (CMC) coated SeNPs are considered using Lake Geneva water and a Waris-H cell culture medium to investigate the effect of SeNPs on the toxicity of algae Poterioochromonas malhamensis, a widespread mixotrophic flagellate. The influence of surface coating, z-average diameters, ζ-potentials, aggregation behavior, ions release, and medium properties on the toxicity of SeNPs to algae P. malhamensi was investigated. It is found that SeNPs are 5-10 times more toxic in Lake Geneva water compared to the culture medium, suggesting that the traditional algal tests in Waris-H culture medium currently underestimate the toxicity of NPs in a natural water environment. Despite significant dissolution, it is also found that SeNPs themselves are the toxicity driver, and dissolved ions have only a marginal influence on toxicity. SeNPs diameter is found a minor factor in toxicity. Based on a principal component analysis (PCA) it is found that in Lake Geneva water, the nature of the surface coating (CMC versus CS) is the most influential factor controlling the toxicity of SeNPs. In the culture medium, surface coating, ζ-potential, and aggregation are found to contribute at the same level. These results highlight the importance of considering in details both NPs intrinsic and media properties in the evaluation of NPs biological effects.

Novel multimethod approach for the determination of the colloidal stability of nanomaterials in complex environmental mixtures using a global stability index: TiO2 as case study.

A systematic study on the colloidal behavior of uncoated and polyvinylpyrrolidone (PVP) coated TiO2 engineered nanomaterials (ENMs) in simulated aqueous media is herein reported, in which conditions representative for natural waters (pH, presence of divalent electrolytes (i.e. Ca2+/Mg2+ and SO42-), of natural organic matter (NOM) and of suspended particulate matter (SPM)) were systematically varied. The colloidal stability of the different dispersions was investigated by means of Dynamic and Electrophoretic Light Scattering (DLS and ELS) and Centrifugal Separation Analysis (CSA), and a global stability index based on these three techniques was developed. The index allows to quantitatively classify the nano-based dispersions according to their colloidal stability affected by the different parameters studied. This multimethod approach clearly identifies inorganic SPM followed by divalent electrolytes as the main natural components destabilizing TiO2 ENMs upon entering in simulated natural waters, while it highlights a moderate stabilization induced by NOM, depending mainly on pH. Moreover, the PVP coating was found to attenuate the influence of these parameters on the colloidal stability. The obtained results show how the global stability index developed is influenced by the complexity of the system, suggesting the importance of combining the information gathered from all the techniques employed to better elucidate the fate and behavior of ENMs in natural surface waters.

Nanoplastics adsorption and removal efficiency by granular activated carbon used in drinking water treatment process.

In this study Granular Activated Carbon (GAC) used in drinking water treatment processes is evaluated for its capacity to adsorb and remove polystyrene (PS) nanoplastics. Batch experiments are conducted in ultrapure and surface water from Lake Geneva, currently used as drinking water resources. Equilibrium and kinetic studies are conducted to understand adsorption mechanisms and limiting factors. Our results show that in ultrapure water the adsorption and removal of PS nanoplastics are mainly due to electrostatic interactions between the positively charged nanoplastics and negatively charged GAC. It is found that the adsorption capacity increases with nanoplastic concentration with a maximum adsorption capacity of 2.20 mg/g. The adsorption kinetics follows a pseudo-second-order model and indicates that the intra-particle diffusion is not the only rate-controlling step. The Langmuir isotherm indicates that nanoplastics are adsorbed as a homogeneous monolayer onto the GAC surface with a maximum monolayer adsorption capacity of 2.15 mg/g in agreement with the experimental value. In Lake Geneva water the adsorption capacity and removal efficiency of PS nanoplastics are found three times higher than in ultrapure water and increase significantly with increasing PS nanoplastics concentration with a maximum adsorption capacity of 6.33 mg/g. This improvement in adsorption capacity is due to the presence of Dissolved Organic Matter (DOM), resulting in PS surface charge modification, presence of divalent ions making possible the adsorption of PS-DOM complexes, and, aggregation of PS nanoplastics. The kinetic pseudo-second-order and intra-particle diffusion provide a good correlation with the experimental data. In contrast, neither Langmuir nor Freundlich isotherms describe in a satisfactory way the adsorption of nanoplastics by GAC. This study reveals that GAC produced from renewable sources can be considered as a moderate adsorbent for the removal of PS nanoplastics in water treatment plants and that the presence of DOM and cationic species play a major role.

Coagulation of TiO2 , CeO2 nanoparticles, and polystyrene nanoplastics in bottled mineral and surface waters. Effect of water properties, coagulant type, and dosage.

Intensive use of engineered nanoparticles (NPs) results in their release into aquatic systems and consequently into drinking water resources. Therefore, it is important to evaluate how NPs can be effectively removed through water treatment processes, such as coagulation, to control environmental and health risks associated with NP exposure. This work investigates the effect of two conventional coagulants, polyaluminum chloride (PACl) and iron chloride (FeCl3 ), on NPs. Three bottled mineral and Lake Geneva waters, currently used as drinking water resources, were considered to get an insight into coagulation efficiency. TiO2 , CeO2 NPs, and polystyrene (PS) nanoplastics were selected, owing to their large number of applications and contrasting surface charge and aggregation behavior at environmental pH. Our findings indicate that PACl is more efficient compared with FeCl3 since lower dosages are required to coagulate all nanoparticles. On the other hand, nanoplastic coagulation is found less efficient compared with TiO2 and CeO2 NPs. This is an important outcome indicating that nanoplastic stability and dispersion state will be more pronounced and therefore more challenging to eliminate. Results highlight the key role of NP and PS nanoplastic surface charge, as well as water properties, coagulant type, and dosage on nanoparticle elimination from aquatic systems. PRACTITIONER POINTS: pH, water hardness, and NOM are playing roles in final coagulant dosage concentration. PACl is more efficient than FeCl3 in most conditions. Positively charged nanoplastics are more difficult to eliminate by coagulation. NP surface properties in bottled mineral and surface waters are controlled by pH, divalent cations, and NOM. NP surface charge and coagulation efficiency depend on water properties.

Influence of nanoplastic surface charge on eco-corona formation, aggregation and toxicity to freshwater zooplankton.

Concerns about possible environmental implications of nano- and micro-plastics are continuously raising. Hence, comprehensive understanding of their behaviour, bioaccumulation and toxicity potential is required. Nevertheless, systematic studies on their fate and possible effects in freshwaters, as well as the influence of particle-specific and environmental factors on their behaviour and impacts are still missing. The aims of the present study are thus two-fold: (i) to examine the role of the surface charge on nanoplastic stability and acute effects to freshwater zooplankton; (ii) to decipher the influence of the refractory natural organic matter (NOM) on the nanoplastic fate and effects. Amidine and carboxyl-stabilized polystyrene (PS) spheres of 200 nm diameter characterized by opposite primary surface charges and neutral buoyancy were selected as model nanoplastics. The results demonstrated that the surface functionalization of the polystyrene nanoplastics controls their aggregation behaviour. Alginate or Suwannee River humic acid (SRHA) modified significantly the surface charge of positively-charged amidine PS nanoplastic and the aggregation state, while had no significant influence on the negatively-charged carboxyl PS nanoplastic. Both amidine and carboxyl PS nanoplastics were ingested by the zooplankton and concentrated mainly in the gut of water flea Daphnia magna and larvae Thamnocephalus platyurus, and the stomach of rotifer Brachionus calyciflorus. Amidine PS nanoplastic was more toxic than carboxyl one. The toxicity decreased in the order D. magna (48 h -immobilization) > B. calyciflorus (24 h - lethality) > T. platyurus (24 h - lethality). Alginate or SRHA reduced significantly the toxicity of both amidine and carboxyl PS nanoplastics to the studied zooplankton representatives. The implications of this laboratory study findings to natural environment were discussed.

Heteroaggregation of CeO2 nanoparticles in presence of alginate and iron (III) oxide.

When manufactured nanoparticles are released to natural waters, heteroaggregation between nanoparticles and water compounds is expected to occur and play a key role in nanoparticle fate, transport and transformation. In this work, the heteroaggregation between CeO2 nanoparticles and Fe2O3 inorganic colloids, which represent the main inorganic fraction from Lake Geneva water, is studied. The heteroaggregation processes between CeO2, Fe2O3 and alginate in multiple water samples are investigated using zeta potential and z-average diameter measurements. The kinetics of heteroaggregation of individual components as well as mixtures of CeO2 nanoparticles and Fe2O3 colloids and alginate are studied using time resolved dynamic light scattering. The global attachment efficiency (αglobal) is calculated using data from kinetic experiments. αglobal for pristine CeO2 nanoparticles varied from 0.5 to 0.7 in lake and synthetic waters and is found around 1 for pristine Fe2O3 and mixture CeO2 and Fe2O3. Our findings demonstrate that heteroaggregation is highly dependent on environmental conditions and resulting electrostatic scenarios. No heteroaggregation at pH 8 between CeO2, Fe2O3 and alginate is observed in ultrapure water, because of electrostatic repulsions between negatively charged compounds. In synthetic and lake waters, the situation is opposite. Indeed, specific adsorption of divalent cations and presence of salt are found to promote heteroaggregation via cation bridging and screening effects. The kinetic experiments indicate that aggregation rate of pristine Fe2O3 is higher (89 nm/min in lake water) compared to pristine CeO2 nanoparticles (50 nm/min) and on the same level as mixture of CeO2 and Fe2O3 (96 nm/min). Low alginate concentration, 0.25 mg/L, has no effect on heteroaggregation in mixture of CeO2 and Fe2O3 in lake and synthetic waters. On the other hand, in natural water, the presence of higher alginate concentration, 2 mg/L, is found to reduce the heteroaggregation rate.

Determination of nanoparticle heteroaggregation attachment efficiencies and rates in presence of natural organic matter monomers. Monte Carlo modelling.

Understanding the transformation and transport of manufactured nanoparticles (NPs) in aquatic systems remains an important issue due to their potential hazard. Once released in aquatic systems, NPs will interact with natural compounds such as suspended inorganic particles and/or natural organic matter (NOM) and heteroaggregation will control their ultimate fate. Unfortunately, systematic experimental methods to study heteroaggregation are not straightforward and still scarce. In addition, the description of heteroaggregation rate constants and attachment efficiencies is still a matter of debate since no clear definition exists. In this work, an original cluster-cluster Monte Carlo model is developed to get an insight into heteroaggregation process descriptions. A two-component system composed of NPs and NOM fulvic acid monomers is investigated by considering several water models to cover a range of (relevant) conditions from fresh to marine waters. For that purpose, homo- and hetero- individual attachment efficiencies between NPs and NOM units are adjusted (NP-NP, NOM-NOM and NP-NOM). The influence of NP/NOM ratio, NOM-NOM homoaggregation versus heteroaggregation, and surface coating effects is studied systematically. From a quantitative point of view, aggregation rate constants as well as attachment efficiencies are calculated as a function of physical time so as to characterize the individual influence of each parameter and to allow future comparison with experimental data. Heteroaggregation processes and global attachment efficiencies corresponding to several mechanisms and depending on the evolution of heteroaggregate structures all along the simulations are defined. The calculation of attachment efficiency values is found dependent on NP/NOM concentration ratios via coating effects, by the initial set of elementary attachment efficiencies and influence of homoaggregation. Marine water represents a specific case of aggregation where all particle contacts are effective. On the other hand, in "ultrapure" and "fresh waters", a competition between homo- and heteroaggregation occurs depending on the initial attachment efficiencies therefore indicating that a subtle change in the NP surface properties as well as in the water chemistry have a significant impact on heteroaggregation processes.

Suspended particulate matter determines physical speciation of Fe, Mn, and trace metals in surface waters of Loire watershed.

This study investigates the spatiotemporal variability of major and trace elements, dissolved organic carbon (DOC), total dissolved solids (TDS), and suspended particulate matter (SPM) in surface waters of several hydrosystems of the Loire River watershed in France. In particular, this study aims to delineate the impact of the abovementioned water physicochemical parameters on natural iron and manganese physical speciation (homoaggregation/heteroaggregation) among fine colloidal and dissolved (< 10 nm), colloidal (10-450 nm) and particulate (> 450 nm) phases in Loire River watershed. Results show that the chemistry of the Loire River watershed is controlled by two end members: magmatic and metamorphic petrographic context on the upper part of the watershed; and sedimentary rocks for the middle and low part of the Loire. The percentage of particulate Fe and Mn increased downstream concurrent with the increase in SPM and major cations concentration, whereas the percentage of colloidal Fe and Mn decreased downstream. Transmission electron microscopy analyses of the colloidal and particulate fractions (from the non-filtered water sample) revealed that heteroaggregation of Fe and Mn rich natural nanoparticles and natural organic matter to the particulate phase is the dominant mechanism. The heteroaggregation controls the partitioning of Fe and Mn in the different fractions, potentially due to the increase in the ionic strength, and divalent cations concentration downstream, and SPM concentration. These findings imply that SPM concentration plays an important role in controlling the fate and behavior of Fe and Mn in various sized fractions. Graphical abstract Physical speciation by heteroaggregation of (Fe-Mn) compounds: high [SPM] → [Fe-Mn] particulate faction; low {SPM] → [Fe-Mn] colloid-dissolved fraction.

Exposure to sublethal concentrations of Co3O4 and Mn2O3 nanoparticles induced elevated metal body burden in Daphnia magna.

Despite the significant progress made in ecotoxicological research on nanoparticles (NPs), there is still very limited information available regarding the biological effects of certain types of NPs such as Co3O4 and Mn2O3. Only a couple of studies provide data on their impact on aquatic organisms whereas, alarmingly, these NPs have been proposed to have high toxicity potential. In addition, more data are needed to determine whether the adverse effects the metal NPs induce on aquatic organisms are rather due to their chemical or particulate nature. To address these open questions, the (sub)lethal effects of Co and Mn NPs in parallel with the respective soluble metal salts on Daphnia magna were studied. The aims of the current study were to i) assess the acute toxicity of Co3O4 and Mn2O3 NPs (primary size 10-30nm) to D. magna, ii) evaluate whether the acute NP exposure at sublethal concentrations influences D. magna post-exposure feeding behaviour and iii) quantify D. magna metal body burden after exposure and after the post-exposure feeding to estimate the potential of trophic transfer of metals. Flow cytometry and total reflection X-ray fluorescence spectroscopy were applied for feeding and metal body burden evaluations, respectively. CuO NPs (primary size 22-25nm) that are very toxic to D. magna were included in the study as a positive control. Since the release of metal ions is an important possibility for toxicity of metal NPs, soluble Co-, Mn- and Cu-salts were analysed in parallel. The solubilisation of Co3O4 NPs in the OECD202 assay conditions was 0.1% and Mn2O3 NPs 35%. Mn2O3 NPs also produced reactive oxygen species in abiotic conditions. However Co3O4 and Mn2O3 NPs were not acutely toxic to D. magna (48h EC50>100mg metal/L) at OECD202 assay conditions. The 48h EC50 values of soluble Co- and Mn-salts were 3.2mgCo/L and 41mgMn/L, respectively. Post-exposure feeding behaviour after 48h exposure to sublethal concentrations (≤10mg/L) of Co3O4 and Mn2O3 NPs differed from that of the unexposed (control) D. magna only at the highest exposure concentrations but was comparable to the feeding behaviour of the respective metal salt-exposed organisms. Upon 48h exposure, dose-dependent increase of D. magna total metal body burden in case of both the NPs and the soluble salts was observed. After 48h post-exposure feeding with algae C. reinhardtii (depuration): D. magna body burden remained elevated (up to 760-fold compared to the control organism) only in case of the NPs. This may indicate potential for trophic transfer of NPs/heavy metals and thus hazard for freshwater ecosystem.

Antioxidant capacities of the selenium nanoparticles stabilized by chitosan.

BACKGROUNDS: Selenium (Se) as one of the essential trace elements for human plays an important role in the oxidation reduction system. But the high toxicity of Se limits its application. In this case, the element Se with zero oxidation state (Se0) has captured our attention because of its low toxicity and excellent bioavailability. However, Se0 is very unstable and easily changes into the inactive form. By now many efforts have been done to protect its stability. And this work was conducted to explore the antioxidant capacities of the stable Se0 nanoparticles (SeNPs) stabilized using chitosan (CS) with different molecular weights (Mws) (CS-SeNPs). RESULTS: The different Mws CS-SeNPs could form uniform sphere particles with a size of about 103 nm after 30 days. The antioxidant tests of the DPPH, ABTS, and lipid peroxide models showed that these CS-SeNPs could scavenge free radicals at different levels. And the 1 month old SeNPs held the higher ABTS scavenging ability that the value could reach up to 87.45 ± 7.63% and 89.44 ± 5.03% of CS(l)-SeNPs and CS(h)-SeNPs, respectively. In the cell test using BABLC-3T3 or Caco-2, the production of the intracellular reactive oxygen species (ROS) could be inhibited in a Se concentration-dependent manner. The topical or oral administration of CS-SeNPs, particularly the Se nanoparticles stabilized with low molecular weight CS, CS(l)-SeNPs, and treated with a 30-day storage process, could efficiently protect glutathione peroxidase (GPx) activity and prevent the lipofusin formation induced by UV-radiation or D-galactose in mice, respectively. Such effects were more evident in viscera than in skin. The acute toxicity of CS(l)-SeNPs was tenfold lower than that of H2SeO3. CONCLUSIONS: Our work could demonstrate the CS-SeNPs hold a lower toxicity and a 30-day storage process could enhance the antioxidant capacities. All CS-SeNPs could penetrate the tissues and perform their antioxidant effects, especially the CS(l)-SeNPs in mice models. What's more, the antioxidant capacities of CS-SeNPs were more evident in viscera than in skin.

Effect of Surface and Salt Properties on the Ion Distribution around Spherical Nanoparticles: Monte Carlo Simulations.

Nanoparticle surface charge properties represent key parameters to predict their fate, reactivity, and complexation in natural, biological, and industrial dispersions. In this context, we present here an original approach to better understand the surface charge electrostatic properties of spherical nanoparticles (NPs). The ion distribution around one nanoparticle is investigated using Monte Carlo simulations and by adjusting a wide range of parameters including NP properties (surface charge density and site distribution), salt concentration (ionic strength and cation concentration), and salt valency (mono-, di-, and trivalent salt). A canonical Metropolis Monte Carlo method is used to reach equilibrium states and a primitive Coulomb model is applied to describe the electrostatic interactions between explicit discrete sites, counterions, and salt particles. Our results show that the presence of explicit surface charges on the NP and in solution has a strong influence on the local ion distribution and on the effective surface charge of the nanoparticles. The increase of surface charge density reduces the NP effective charge by the formation of a condensation layer around the nanoparticle. However, a limit of condensation is achieved due to steric effects and electrostatic repulsions. The presence of di- and trivalent cations is also found to strongly modify the effective charge and improve condensation state as long as electrostatic repulsion between the cations close to the surface are not so strong. At high trivalent cation concentration, the NP effective charge is greatly reduced and the local environment around the nanoparticle becomes more structured with the formation of a multi layer structure composed by anions and cations.