Carbon Materials Prepared from Invading Pelagic Sargassum for Supercapacitors' Electrodes.

Since 2011, substantial amounts of pelagic Sargassum algae have washed up along the Caribbean beaches and the Gulf of Mexico, leading to negative impacts on the economy and the environment of those areas. Hence, it is now crucial to develop strategies to mitigate this problem while valorizing such invasive biomass. This work deals with the successful exploitation of this pelagic Sargassum seaweed for the fabrication of carbon materials that can be used as electrodes for supercapacitors. Pelagic Sargassum precursors were simply pyrolyzed at temperatures varying from 600 to 900 °C. The resultant carbonaceous materials were then extensively characterized using different techniques, such as nitrogen adsorption for textural characterization, as well as X-ray photoelectron (XPS), Fourier transform infrared spectroscopies (FT-IR) and scanning electron microscopy (SEM), to understand their structures and functionalities. The electrochemical properties of the carbon materials were also tested for their performance as supercapacitors using cyclic voltammetry (CV), the galvanostatic method and electrochemical impedance spectroscopy analyses (EIS). We managed to have a large specific surface, i.e., 1664 m2 g-1 for biochar prepared at 800 °C (CS800). Eventually, CS800 turned out to exhibit the highest capacitance (96 F g-1) over the four samples, along with the highest specific surface (1664 m2 g-1), with specific resistance of about 0.07 Ω g -1.

In vitro and in vivo assessment of a CLD sequestration strategy in Nitisol using contrasted carbonaceous materials.

Chlordecone (Kepone) (CLD) is a highly persistent pesticide formerly used in the French West Indies. High levels of this pesticide may be found in soils and constitute a subsequent source of contamination for outdoor-reared animals due to involuntary ingestion of consistent amounts of soil. In that context, carbonaceous materials may be used to amend soil to efficiently decrease the bioavailability of such organic pollutants. The present study aims to assess the efficiency of diverse amendments of a contaminated Guadeloupe nitisol using two physiologically based approaches. A set of 5 carbonaceous materials (ORBO, DARCO, Coco CO2, Oak P1.5, Sargasso biochar) was tested and used to amend Nitisol at 2% (mass basis). Bioaccessibility assessment was performed using the Ti-PBET assay (n = 4). The relative bioavailability part involved 24 piglets randomly distributed into 6 experimental groups (n = 4). All groups were exposed during 10 days to a contaminated soil, amended or not with carbon-based matrices. A significant decrease in relative bioaccessibility and CLD concentrations in liver were observed for all amended groups in comparison to the control group, with the exception of the biochar amended soil in the bioaccessibility assay (p < 0.05). Extent of this reduction varied from 22 to more than 82% depending on the carbonaceous matrix. This decrease was particularly important for the ORBO™ activated carbon for which bioaccessibility and relative bioavailability were found lower than 10% for both methodologies.

Development and characterisation of a nanostructured hybrid material with vitamin B12 and bagasse-derived activated carbon for anaerobic chlordecone (Kepone) removal.

Intensive use of the chlorinated pesticide chlordecone from the 1970s to 1993 to prevent crop damage in banana plantations of Guadeloupe and Martinique led to diffuse pollution of soils and surface waters, affecting both fauna and human beings in the contaminated areas. Since 2001, drinking water production plants have been equipped with filters containing activated carbon that must be treated after saturation. The objective of this work is to produce a hybrid material composed of activated carbon and vitamin B12 (VB12) for the degradation of chlordecone (CLD). The preparation of such a hybrid material is carried out by non-covalent fixation to achieve an eco-friendly solution for the serious environmental problem of contamination by chlorinated pesticides. It is thus proposed to degrade CLD by a physico-chemical treatment allowing salvage of the catalyst, which is adsorbed on the carbon surface to generate less waste that is inexpedient to treat. Activated carbon (AC) is produced locally from available sugarcane bagasse subjected to phosphoric acid activation. The main characteristics of this material are a major mesoporous structure (0.91%) and a specific (BET) surface area ranging from 1000 to 1500 m2 g-1. The experimental results showed that BagP1.5 has a high adsorption capacity for VB12 due to its large surface area (1403 m2 g-1). The binding of VB12 to the bagasse-derived AC is favoured at high temperatures. The adsorption is optimal at a pH of approximately 6. The maximum adsorption capacity of VB12 on the AC, deduced from the Langmuir model, was 306 mg g-1, confirming the high affinity between the two components. The hybrid material was characterised by FTIR, Raman, X-ray fluorescence spectroscopy and SEM analysis. CLD removal by this hybrid material was faster than that by VB12 or BagP1.5 alone. The CLD degradation products were characterised by mass spectrometry.

Reduction of chlordecone environmental availability by soil amendment of biochars and activated carbons from lignocellulosic biomass.

Chlordecone (kepone or CLD) was formerly used in French West Indies as an insecticide. Despite its formal ban in 1993, high levels of this pesticide are still found in soils. As such, sequestering matrices like biochars or activated carbons (ACs) may successfully decrease the bioavailability of halogenated compounds like CLD when added to contaminated soils. The present study intends (i) to produce contrasted sequestering matrices in order to (ii) assess their respective efficiency to reduce CLD environmental availability. Hence, the work was designed following two experimental steps. The first one consisted at producing different sequestering media (biochars and ACs) via pyrolysis and distinct activation processes, using two lignocellulosic precursors (raw biomass): oak wood (Quercus ilex) and coconut shell (Cocos nucifera). The chemical activation was carried out with phosphoric acid while physical activation was done with carbon dioxide and steam. In the second step, the CLD environmental availability was assessed either in an OECD artificial soil or in an Antillean contaminated nitisol (i.e., 2.1-1µg CLD per g of soil dry matter, DM), both amended with 5 wt% of biochar or 5 wt% of AC. These both steps aim to determine CLD environmental availability reduction efficiency of these media when added (i) to a standard soil material or (ii) to a soil representative of the Antillean CLD contamination context. Textural characteristics of the derived coconut and oak biochars and ACs were determined by nitrogen adsorption at 77 K. Mixed microporous and mesoporous textures consisting of high pore volume (ranging from 0.38 cm3.g-1 to 2.00 cm3.g-1) and specific (BET) surface areas from 299.9 m2.g-1 to 1285.1 m2.g-1 were obtained. Overall, soil amendment with biochars did not limit CLD environmental availability (environmental availability assay ISO/DIS 16751 Part B). When soil was amended with ACs, a significant reduction of the environmental availability in both artificial and natural soils was observed. AC soil amendment resulted in a reduced CLD transfer by at least 65% (P < 0.001) for all lignocellulosic matrices (excepted for coconut sample activated with steam, which displayed a 47% reduction). These features confirm that both pore structure and extent of porosity are of particular importance in the retention process of CLD in aged soil. Owing to its adsorptive properties, AC amendment of CLD-contaminated soils appears as a promising approach to reduce the pollutant transfer to fauna and biota.

Evaluation of the molecular inclusion process of ß-hexachlorocyclohexane in cyclodextrins.

The present work aimed to study the guest-host complexes of ß-hexachlorocyclohexane (ß-HCH), a pesticide with high environmental stability that can cause severe health problems, with the most common cyclodextrins (α-, ß-, and γ-CDs). The formation reactions of these molecular inclusion complexes were addressed in this research. The multiple minima hypersurface methodology, quantum calculations based on density functional theory and a topological exploration of the electron density based on the quantum theory of atoms in molecules approach were used to characterize the interaction spaces of the pollutant with the three CDs. Additionally, charge distribution, charge transfer and dual descriptor analyses were employed to elucidate the driving forces involved in the formation of these molecular inclusion complexes. Three types of fundamental interactions were observed: total occlusion, partial occlusion and external interaction (non-occlusion). Finally, experiments were performed to confirm the formation of the studied complexes. The most stable complexes were obtained when γ-CD was the host molecule. The interactions between the pesticide and CDs have fundamentally dispersive natures, as was confirmed experimentally by spectroscopic results. All the obtained results suggest the possibility of using CDs for the purification and treatment of water polluted with ß-HCH.

Study of chlordecone desorption from activated carbons and subsequent dechlorination by reduced cobalamin.

Since 1972, the French departments of Guadeloupe and Martinique have intensively used organochlorinated pesticides such as chlordecone (CLD) and hexachlorocyclohexane (HCH) isomers to prevent the proliferation of banana weevil (Cosmopolite sordidus). These molecules are stable in the environment, leading to a continuous contamination of soils, water, and food chain in the banana-producing areas. In these polluted areas, water treatment plants are equipped with activated carbon (AC) filters. In order to improve treatment of CLD-contaminated waters by AC, CLD adsorption and desorption kinetic studies are carried out using different ACs produced from sugar cane bagasse as adsorbents and subsequent CLD degradation is performed using reduced vitamin B12 (VB12). A GC-MS method for CLD quantification is as well optimized. This study shows that bagasse ACs are able to capture the pollutant, leading to a CLD concentration decrease from 1 to 73 µg L-1, with an adsorption capacity of 162 µg mg-1. Adsorption capacity increase with the temperature indicates an endothermic process. Polar solvents favor CLD desorption from ACs, suggesting hydrogen bonding between CLD and surface groups of ACs, the best solvent for chemical desorption being ethanol. Subsequent degradation of CLD in ethanol is performed using vitamin B12 reduced by either 1,4-dithiotreitol (DTT) or zerovalent zinc, leading to 90% of CLD removal and to the molecule cage structure opening for formation of a pentachloroindene intermediate product, characterized by GC MS/MS. A pathway for pentachloroindene formation from CLD is proposed.