Selective Adsorption of Organic Micro-Pollutants by Smectite Clays Revealed from Atomistic Simulations.

In this study, atomistic simulations were carried out to study the difference in the adsorption process between two similar molecules, diazepam and oxazepam, on Na+-montmorillonite. Kinetic and XRD measurements showed a contrasting adsorption mechanism of these two molecules, differing only by the presence/absence of methyl and hydroxyl groups, with a larger adsorption amount and intercalation for the oxazepam. The structural characterization of these molecules was investigated through DFT calculations and showed the vicinity of hydroxyl and carbonyl groups for only the chair conformation of oxazepam compared to the boat conformation. Classical molecular dynamics simulations of diazepam and the two forms of oxazepam on the external surface of Na+-montmorillonite highlighted the better coordination of the oxazepam-chair conformation, compared to its boat counterpart and diazepam. This has been confirmed through DFT calculations, from which a coordination energy that is greater by 10 kcal·mol-1 is observed. This strongly suggests that the experimentally observed intercalation of oxazepam occurs only in the chair form because of the strong coordination with the Na+ cation present in the Na-Mt interlayer. Classical MD simulations of the intercalated oxazepam chair molecule in the Na-Mt interlayer allowed the evaluation of the interlayer spacing d001, which was in very good agreement with the experimental XRD measurement.

New Materials and Technologies for Wastewater Treatment.

This Special Issue (SI) contains the successful submissions [...].

Trace organic contaminants within solid matrices along an anthropized watercourse: Organo-mineral controls on their spatial distribution.

Although numerous studies have determined significant contamination in terms of trace organic contaminant (TrOC) diversity and concentration, the occurrence of TrOCs within solid matrices as suspended solids and sediments flies under the radar. In this study, the occurrence of 35 TrOCs of various classes (i.e. pharmaceutical products and pesticides) was investigated in three compartments, namely dissolved phase, suspended particulate matter (SPM) and sediments, within an anthropized river in France. The sampling was performed to assess the spatial contamination dynamics and the impact of a major wastewater treatment plant (WWTP), under two contrasted hydrological conditions, i.e. base level and flood conditions. Solid samples were finely characterized (XRD, grainsize, TOC) in order to assess the impact of organic and mineral composition on the sorption extent of TrOCs. The study reveals that the clear spatial pattern of contamination in water samples, mostly generated by the effluent discharge of WWTPs, is less clear in solid matrices as the variability of the organo-mineral composition of such samples strongly impacts their favourability for sorption. Moreover, the flood event strongly impacted the sedimentary compartment, remobilizing fine and TrOC contaminated particles that were further found in suspended particulate matter. Lastly, the representativeness of contaminant diversity and concentration within the solid matrices displayed more favourable insights for SPM.

Record of trace organic contaminants in a river sediment core: From historical wastewater management to historical use.

Some trace organic contaminants (TrOCs) can be considered as ubiquitous contaminants since the 1950s, and the study of their historical distribution within river sediments allows us to better understand the temporal variation of the chemical quality of sediments, and make assumptions about the most insightful forcings impacting these distributions. In this study, the occurrence of 41 TrOCs of various classes (i.e. pharmaceutical products and pesticides) was studied in a sedimentary core sampled in a disused dock along the Seine River, France. This core covers a 60 year-long period between 1944 and 2003, and 23 TrOCs were detected at least once. Their concentrations mainly ranged between 1 and 10 ng g-1 within the core, except for tetracycline that exhibited higher concentrations (~hundreds of ng·g-1). The dating of the core, based on previous studies, enabled the characterization of the changes since 1945, potentially impacted by (i) the sewer connectivity, (ii) the upgrading of wastewater treatment technologies, (iii) historical modifications in the use of each TrOC, and (iv) the sedimentary composition. In every case the deepest occurrence of each TrOC in the core matched its market authorization date, indicating the potential of TrOC to be used as chronomarkers. This study also reveals that the recent upgrading of wastewater treatment technologies within the watershed decreased the concentrations of each TrOC, despite an increase in TrOC diversity in the most recent years.

Sulfamethoxazole/Trimethoprim ratio as a new marker in raw wastewaters: A critical review.

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.

Laponites® for the Recovery of 133Cs, 59Co, and 88Sr from Aqueous Solutions and Subsequent Storage: Impact of Grafted Silane Loads.

In this study, silylated Laponites® (LAP) were synthetized with various loads of 3-aminopropyltriethoxysilane (APTES) to evaluate their adsorption properties of 133Cs, 59Co, and 88Sr during single-solute and competitive experiments. The increase in the initial load of APTES increased the adsorbed amount of APTES in the resulted grafted clay. The characterization of LAP-APTES exhibited a covalent binding between APTES and LAP and emphasized the adsorption sites of APTES for each tested load. In comparison with raw LAP, LAP-APTES displayed significantly higher adsorption properties of Co2+, Cs+, and Sr2+. The competitive adsorption of these three contaminants provides a deeper understanding of the affinity between adsorbate and adsorbent. Therefore, Co2+ displayed a strong and specific adsorption onto LAP-APTES. Except for Cs+, the adsorption capacity was improved with increasing the load of APTES. Finally, the desorption behavior of the three contaminants was tested in saline solutions. Cs+ and Sr2+ were significantly released especially by inorganic cations displaying the same valence. Conversely, desorption of Co2+ was very low whatever the saline solution. LAP-APTES, therefore, presented suitable adsorption properties for the removal of radionuclides especially for Co2+, making this material suitable to improve the decontamination of radioactive wastewaters.

Impact of meteorological and social events on human-excreted contaminant loads in raw wastewater: From daily to weekly dynamics.

The temporal dynamics of the wastewater influent loads of 25 drug target residues (DTR, both pharmaceuticals and illicit drugs) was assessed during 84 consecutive days. This monitoring scale enables longer temporal patterns than weekday/weekend patterns to be explored. In this study, we focus on day to day variations and the potential statistical correlation of each DTR analyzed in order to better understand the potential forcings that lead to the load variation of DTRs (alone or in clusters). The weekly patterns based on the weekly loads of DTRs were also analyzed and the impact of social and meteorological events on their variations was investigated. Two cold events occurred during the monitoring period and were associated with the highest loads of analgesics and non-steroidal anti-inflammatory drugs, as well as the lowest loads of stimulants. During the Easter holidays, a significant decrease in some year-long medication as well as analgesics was found, consistent with the demographic decrease within the catchment during this period. Lastly, a good correlation between the academic calendar and the loads of stimulants was found, emphasizing the overrepresentation of students in the consumption of recreational drugs. This study furnishes new insights in order to better understand the variations in DTR loads in wastewater influents, beyond the weekday/weekend pattern and the seasonal effect. Further investigations remain necessary, especially a real-time monitoring of the population figures within the catchment in order to improve our understanding of these results.

Temporal dynamics of human-excreted pollutants in wastewater treatment plant influents: Toward a better knowledge of mass load fluctuations.

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-1·inhabitant-1 (inh) whereas the median consumption for cocaine (based on benzoylecgonine loads) and ecstasy was 32 and 6mg·day-1·103·inh-1 respectively. The highest consumption values of pharmaceutically active compounds (PACs) were found for acetaminophen and acetylsalicylic acid with 108.8 and 34.1mg·day-1·inh-1 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).

Adsorption of diclofenac onto organoclays: Effects of surfactant and environmental (pH and temperature) conditions.

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.

Adsorption mechanisms of emerging micro-pollutants with a clay mineral: Case of tramadol and doxepine pharmaceutical products.

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.