The adsorption and desorption behaviors of phenanthrene and pyrene onto microplastics in the aquatic environment and digestive fluids

The adsorption and desorption behaviors of Phenanthrene and Pyrene onto polyethylene (PE), polypropylene (PP), polystyrene (PS), and poly (methyl methacrylate) (PMMA) microplastics in the simulated freshwater and digestive fluids (simulated gastic fluid (SGF), simulated intestinal fluid (SIF)) were studied. The second-order kinetic model described the sorption kinetics of polycyclic aromatic hydrocarbons (PAHs), and the Langmuir model fitted the sorption isotherms of PAHs better, which indicated the surface sorption as the main mechanism. The sorption capacity was in the order of PMMA > PS > PE > PP, which may due to the specific surface area and particle size of microplastics. Various environmental conditions were considered, including pH, salinity and dissolved organic matters (DOM). Although higher salinity would bring negative effects on the adsorption of PAHs onto microplastics, the adsorption behaviors were not significantly influenced by pH and DOM. The desorption rate of PAHs from microplastics in SGF was lower than that in the SIF, with the desorption equilibrium time of 12 h in SIF. For the desorption in simulated freshwater, a secondary adsorption occurred around 3 h. Our work for the first time comparing the desorption behaviors between freshwater and two kinds of digestive fluids, indicating the negative effects of microplastics bring to aquatic organisms through digestive tracts. Further studies are needed to quantify the toxicity threshold of aquatic organisms through ingestion of microplastics combined with persistent organic pollutions.

Bioavailability of steroid hormones sorbed on microplastics for aquatic organisms through biological fluids

Florian Frédéric Vincent Breider, Yang Liu, Thibault Béranger Masset, Cécilia Laetitia Carla Siri

Many studies have reported that hydrophobic organic contaminants have the ability to sorb on microplastics in aquatic ecosystem via different mechanisms of sorption. However, a lack of studies investigating desorption of such contaminants in organism fluids has been disclaimed. The bioavailability of potential risk-compounds for aquatic organisms has to be assessed. It has been largely reported that adsorption onto microplastics is directly linked with hydrophobicity property of contaminants; the more hydrophobic the pollutant, the higher the sorption capacity. However, it is expected that the least hydrophobic molecules desorb more easily from microplastics. In our study, steroid hormones with different hydrophobicities, namely progesterone and testosterone, are used and their respective desorption from different types of microplastics is investigated in gastric and gut fluids. The idea is to discern if the ingestion of microplastics by organisms might promote desorption of potential sorbed micropollutants and therefore their bioavailability for such species. By using more complex composition of gastric and intestinal fluids separately and then sequentially, the purposes are to reproduce realistic digestive conditions and furthermore determine the organ which is the most prompt to enhance bioavailability of pollutants. Our results show that a higher desorption efficiency (58.6-73.0%, depending on plastic types) is reached in intestinal fluid than in freshwater (31.1-53.6%) or in gastric fluid (18.7-43.9%). Bile salts in intestinal fluid form micelles able to promote the solubilization of pollutants. Adsorption of pepsin onto microplastics has also been revealed, suggesting a competition between pollutant and pepsin for sorption sites and a potent reduction of pollutant solubilization. Our results indicate that progesterone daily intake via microplastics exposure is equal to 16.0μg/kg/day upon intestinal digestion, which represents about 13% of daily intake via water exposure. This observation suggests that ingestion is an additional route of exposure of pollutants and therefore emphasizes pollutants bioavailability for aquatic organisms.

2020

Adsorption of progesterone onto microplastics and its desorption in simulated gastric and intestinal fluids

Florian Frédéric Vincent Breider, Dominique Grandjean, Yang Liu, Thibault Béranger Masset, Cécilia Laetitia Carla Siri

The sorption of Hydrophobic Organic Compound (HOC) onto microplastics is relatively well reported in the literature, while their desorption remains poorly investigated, and especially in biological ﬂuids. The present study investigated the sorption and desorption of progesterone on polyethylene (PE), polypropylene (PP) and polystyrene (PS) microplastics. The sorption experiments showed that the equilibrium was reached in a few hours for all plastics. A sorption efﬁciency of 357.1 µg/g was found for PE and PS and 322.6µg/g for PP. Sorption experiments indicated that adsorption would happen certainly via surface sorption and potentially pore-ﬁlling mechanism. The desorption was carried out in Simulated Gastric Fluid (SGF) and Simulated Intestinal Fluid (SIF), whose formulations were more complex than similar models reported so far. It has been found that the desorption was higher in SIF compared to SGF, surely due to micelle formation in SIF promoting the pollutant solubilization. Sorption of pepsin onto microplastics has also been revealed, suggesting a competition between pollutant and pepsin for sorption sites and a potent reduction of pollutant solubilization. This study indicates that microplastics ingestion could be considered as as additional route of exposure of pollutants and therefore emphasizes pollutants bioavailability for aquatic organisms.

2021

Adsorption de polycarboxylates et de lignosulfonates sur poudre modèle et ciments

François Perche

Placing concrete requires much more water than the cement needs for its hydration. This results in an important porosity in the hardened concrete, which accentuates the degradation of this material. By adding small amounts of polymeric admixtures, called superplasticizers, to the fresh concrete one can significantly reduce the amount of water required to obtain the suitable workability. The plasticizing effect of superplasticizers has been studied for many years, and remains today, an ongoing field of research. This research led to a better understanding of the forces that act during the deflocculation and dispersion of cement grains induced by superplasticizers. This research work was performed within the framework of the "Superplast" European project. Its main objective has been to determine which parameters (molecular structure, induced charge, adsorption mode, molar mass) influence the plasticizing effects of superplasticizers. The results of this study will allow synthesis new polymeric admixtures with better performances than those currently available. For this study, two types of superplasticizers were selected: lignosulfonates and polycarboxylates. For each one, different samples were synthesised and characterised. For each sample, adsorption, rheological and interaction forces measurements were performed by our partners while we have performed adsorption and electroacoustic measurements on model powder suspensions. Different cement model powders were investigated and a magnesium oxide was selected. The particle size distribution and reactivity were carefully characterized. The inert model system (MgO) allowed us to study adsorption mechanisms without the complexity linked to cement hydration reactions that modify surface and solution of the suspension. Particle surface charge and pH are the two main parameters that influence the polymer adsorption and the polymer conformation. Magnesium oxide which has a high isoelectric point (around at pH 12.4) allows a surface charge similar to cement suspensions at high pH. First, we have measured the adsorption isotherms of all superplasticizers on model suspensions in NaOH (0.01M). This study allowed us to evaluate the affinity of each polymer for MgO and its adsorption plateau. These measurements showed that the lignosulfonates have a higher affinity than the polycarboxylates. They also showed that lignosulfonate adsorption is mainly influenced by their molar mass and their carboxylic group content (for similar sulfonate group content) while polycarboxylate adsorption is mainly driven by the backbone length, the side chain length and the carboxylic group content. Adsorption plateaux allowed us to calculate the surface coverage ratio and to estimate the superplasticizer conformation on the surface. Adsorption isotherms were finally measured on a Portland cement. The polymer adsorption is influenced by the same parameters as on MgO. The model system MgO is representative for the polymer adsorption on cement. In a second step, different electrolytes were added to model suspensions. This practice allowed us to study separately the effect of the main ions present in cement suspensions (Na+, Ca2+, SO42-, OH-) and to mimic the ionic composition of the aqueous phase of the cement suspension. Lignosulfonate adsorption is neither influenced by the studied ions or the pH. Only an increase of ionic strength increases the adsorbed polymer mass. Polycarboxylate adsorption is influenced by calcium and sulfate ions and by the particle surface charge. Finally, superplasticizer adsorption was studied on different cements by our partners and on a fly ash and a silica fume by ourselves. Lignosulfonate adsorption isotherms on cements showed that affinity and adsorbed polymer mass increases with the C3A content and decreases with the alkalis content. The isotherms measured on industrial by-products showed that superplasticizers adsorb on fly ash, but not on silica fume.