RESUMEN
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.
Asunto(s)
Clordecona , Insecticidas , Contaminantes Químicos del Agua , Adsorción , Anaerobiosis , Celulosa , Carbón Orgánico , Clordecona/análisis , Guadalupe , Humanos , Insecticidas/análisis , Martinica , Vitamina B 12RESUMEN
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.
Asunto(s)
Clordecona , Contaminantes del Suelo , Biomasa , Carbón Orgánico/análisis , Clordecona/análisis , Lignina , Suelo , Contaminantes del Suelo/análisis , Indias OccidentalesRESUMEN
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.