Among pharmaceutical products (PPs) recalcitrant to water treatments, diclofenac shows a high toxicity and remains at high concentration in natural aquatic environments. The aim of this study concerns the understanding of the adsorption mechanism of this anionic PP onto two organoclays prepared with two long-alkyl chains cationic surfactants showing different chemical nature for various experimental pH and temperature conditions. The experimental data obtained by a set of complementary techniques (X-ray diffraction, elemental analyses, gas chromatography coupled with mass spectrometry, and Fourier transform infrared spectroscopy) and the use of Langmuir, Freundlich and Dubinin-Radushkevish equation models, reveal that organoclays show a good affinity to diclofenac which is enhanced as the temperature is under 35°C and for pH above 4.5 (i.e. >pKa of diclofenac) while the chemical nature of surfactant appears to play a minor role. The thermodynamic parameters derived from the fitting procedure point out the strong electrostatic interaction with organic cations adsorbed within the interlayer space in the organoclays for the adsorption of diclofenac. This study stress out the application of organoclays for the adsorption of a recalcitrant PPs in numerous aquatic compartments that can be used as a complement with activated carbon for waste water treatment.

A sodium exchanged smectite clay mineral (Mt) was used as geo-sorbent for the adsorption of tramadol and doxepin: two pharmaceutical products (PPs) defined as emerging pollutants due to their presence at significant concentration in numerous water compartments. The adsorption isotherms for both the temperatures of 20 and 40°C and the derived data determined through the fitting procedure by using Langmuir, Freundlich and Dubinin-Radushkevich equation models explicitly pointed out that the sorption of both tramadol and doxepin is mainly driven by electrostatic interaction. The studied PPs are intercalated in a monolayer arrangement within the interlayer space through a cation exchange in stoichiometric proportion with the Na(+) cations leading to adsorbed PPs amounts that match the cation exchange capacity (CEC) of Mt. Due to their hydrophobic character, additional doxepin molecules could be adsorbed by weak molecular interaction driving to an increase of the adsorbed amount beyond the CEC at low temperature (20°C). The confinement of PPs within the interlayer space of Mt confirms the use of clay minerals as potential material for the wastewater treatment as well as it drives to an amorphous or glassy state, which can find echo in biopharmaceutical applications for a controlled release of PPs.

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Global Trimethoprim (TMP) and Sulfamethoxazole (SMX) occurrences in raw wastewaters were systematically collected from the literature (n=140 articles) in order to assess the relevance of using the SMX/TMP ratio as a marker of the main origin of wastewaters. These two antibiotics were selected due to their frequent use in association (i.e. co-trimoxazole) in a 5:1 ratio (SMX:TMP) for medication purposes, generating a unique opportunity to globally evaluate the validity of this ratio based on concentration values. Several parameters (e.g. sorption, biodegradation) may affect the theoretical SMX/TMP ratio. However, the collected data highlighted the good agreement between the theoretical ratio and the experimental one, especially in wastewater treatment plant influents and hospital effluents. Only livestock effluents displayed a very high SMX/TMP ratio, indicative of the very significant use of sulfonamide alone in this industry. Conversely, several countries displayed low SMX/TMP ratio values, highlighting local features in the human pharmacopoeia. This review provides new insights in order to develop an easy to handle and sound marker of wastewater origins (i.e. human/livestock), beyond atypical local customs.

The objective of the study was to evaluate the sorption of a pool of pharmaceutically active compounds (PhACs) onto a clay–sand filter in a dynamic sorption experiment.

International audienceThe removal of a Pharmaceutically Active Compound (PhAC) pool using a well referenced clay mineral from Wyoming (SWy-2) as geosorbent was studied for a better understanding of their environmental fate. As expected, the selected material shows its particular adsorption properties to PhAC under different experimental conditions with two main features depending on the chemical nature of the emerging micro-pollutants. Cationic PhACs, for which the driving force for their adsorption results to electrostatic interaction via the exchange with the inorganic cations of the clay mineral, are almost completely removed for all studied experimental conditions where it appears that S/L ratio plays a minor role and the only one limitation for their removal is the cation exchange capacity of the adsorbent. In contrast, anionic and neutral PhACs are adsorbed to the clay mineral surface (silanol groups on the sheet edges, inorganic cations…) through other interactional mechanisms involving ion-dipole, Van der Waals interaction, leading to a competition of the whole organic molecules where their chemical nature (electric charge, hydrophobicity) may also play for their adsorption. While the adsorption of ketoprofen, naproxen, diclofenac and salicylic acid anionic PhACs slightly increases with the increase of the S/L ratio, the removal of the neutral and the other anionic PhACs (gemfibrozil and ibuprofen) seems to be independent of that ratio and is particularly enhanced. The efficiency of the removal for a global pool of PhACs even in low S/L ratio stresses out the control of the selected natural minerals on the dynamic of PhACs in the environment

The occurrence of pharmaceutical products (PPs) within environmental compartments challenges the scientific community and water treatment operators to find suitable and practicable removal solutions. Clay minerals are among the oldest and cheapest adsorbents used for the removal of organic and inorganic pollutants. However, despite their significant adsorption properties, little is known about their potential to remove organic contaminants such as pharmaceutical products from wastewater effluents. Hence, based on the latest published articles this review aims to standardize the adsorption properties of clay minerals for the removal of PPs. Specifically, the charge state of PPs appears to play a key role in their adsorption mechanism. In order to overcome the limitations of batch experiments (i.e. idealized solutions, static conditions) and design of a field solution, the impact of external parameters on the adsorption capacities of clay minerals is reviewed. The effect of thermal treatment and acid activation of clay minerals is also assessed in order to better understand the consequences of such modifications on the adsorption properties of clay-based adsorbents. Finally, even if most authors agree on the potential of clay-based adsorbents for the removal of PPs from wastewater, there remain significant gaps in the existing literature that need to be filled, with the aim of forecasting the real potential of clay-based treatment for the removal of pharmaceutical products at industrial scale.

The occurrence of 25 drug target residues (illicit drugs or pharmaceutically active compounds) was investigated during 85 consecutive days in the influents of a wastewater treatment plant in the Region Centre-Val de Loire, France. This long tracking period allowed a better understanding of the patterns affecting the occurrence of this type of contaminants. Among them, 2 were never detected (i.e. heroin and amphetamine). Concerning illicit drugs two patterns were found. Cocaine and ecstasy median loads varied considerably between weekdays and weekend days (i.e. 18.3 and 35.9% respectively) whereas cannabis and heroin (based on 6-mono-acetylmorphine loads) loads were within the same order of magnitude with a significant statistical correlation with pharmaceuticals such as acetaminophen or ketoprofen. The consumption of selected drugs was back-calculated from the loads. Among illicit drugs the highest consumption was found for cannabis with a median consumption of 51mg·day·inhabitant (inh) whereas the median consumption for cocaine (based on benzoylecgonine loads) and ecstasy was 32 and 6mg·day·10·inh respectively. The highest consumption values of pharmaceutically active compounds (PACs) were found for acetaminophen and acetylsalicylic acid with 108.8 and 34.1mg·day·inh respectively, in good agreement with national sales data. A statistically significant weekly pattern was found for several PACs such as metoprolol and trimethoprim, but with the opposite pattern to that of illicit drugs. The variations in daily PAC loads could provide information about the mobility of people in the catchment, especially on the basis of daily taken PACs (i.e. to treat chronicle diseases).