title: The role of sorption and biodegradation in the removal of acetaminophen, carbamazepine, caffeine, naproxen and sulfamethoxazole during soil contact: A kinetics study.
abstract: In countries like Spain, where water is a limited resource, reusing effluents from wastewater treatment plants may imply the introduction of incompletely eliminated pollutants into the environment. Therefore, this work identified the role of sorption and biodegradation in attenuating pharmaceutical compounds (acetaminophen, carbamazepine, caffeine, naproxen and sulfamethoxazole) in natural soil. It also determined which sorption and removal ("sorption+biodegradation") kinetics models describe the behaviour of these substances in the water-soil system. Presence of potential transformation products (TPs) as a result of pharmaceuticals biodegradation was also studied. To this end, serial batch-type experiments were performed with a soil:water ratio of 1:4 and an initial pharmaceutical concentration of 100μgL(-1). Despite results are dependent on soil characteristics, they revealed that, for those substances with a higher affinity to the soil used (loamy sand), sorption seems to play a key role during the first 48h of contact with soil, and gives way to biodegradation afterwards. The sorption of the pharmaceuticals studied follows a pseudo second-order kinetics. Caffeine and sulfamethoxazole displayed the fastest initial sorption velocities (h=2055 and h=228μgkg(-1)h(-1), respectively). The removal kinetics experiments, satisfactorily simulated by the first-order kinetics model, indicated the presence of potential microbial adaptation to degradation. Indeed, half-lives decreased from 1.6- to 11.7-fold with respect to initial values. The microbial capacity to degrade sulfamethoxazole could be a matter of concern if bacteria have developed resistance to this antibiotic. Caffeine, acetaminophen and sulfamethoxazole were mitigated to a greater extent, whereas the removal of naproxen and carbamazepine was more limited. The appearance of epoxy-carbamazepine and N4-acetyl-sulfamethoxazole as possible TPs of carbamazepine and sulfamethoxazole, respectively, indicated that biodegradation was incomplete and showed the capacity of soil microbes to transform these substances.
authors.affiliation: IMDEA Water, Avda Punto Com, 2, 28805 Alcalá de Henares, Madrid, Spain. Electronic address: virtudes.martinez@imdea.org.
authors.forename: Virtudes
authors.initials: V
authors.lastname: Martínez-Hernández
authors.affiliation: IMDEA Water, Avda Punto Com, 2, 28805 Alcalá de Henares, Madrid, Spain.
authors.forename: Raffaella
authors.initials: R
authors.lastname: Meffe
authors.affiliation: University of Almería, Chemistry and Physics Department, Ctra. Sacramento s/n, La Cañada de San Urbano, 04120 Almería, Spain.
authors.forename: Sonia
authors.initials: S
authors.lastname: Herrera López
authors.affiliation: IMDEA Water, Avda Punto Com, 2, 28805 Alcalá de Henares, Madrid, Spain; University of Alcalá, Geology, Geography and Environment Department, Faculty of Sciences, External Campus, Ctra. A-II km 33.6, 28871 Alcalá de Henares, Madrid, Spain.
authors.forename: Irene
authors.initials: I
authors.lastname: de Bustamante
mesh_terms: D000082:Acetaminophen / Q000032:analysis; D000327:Adsorption; D001673:Biodegradation, Environmental; D002110:Caffeine / Q000032:analysis; D002220:Carbamazepine / Q000032:analysis; D007700:Kinetics; D008956:Models, Chemical; D009288:Naproxen / Q000032:analysis; D012987:Soil; D012989:Soil Pollutants / Q000032:analysis*; D013030:Spain; D013420:Sulfamethoxazole / Q000032:analysis; D014865:Waste Disposal, Fluid / Q000379:methods*; D062065:Wastewater; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D000082:Acetaminophen; D002110:Caffeine; D002220:Carbamazepine; D009288:Naproxen; D012987:Soil; D012989:Soil Pollutants; D013420:Sulfamethoxazole; D062065:Wastewater; D014874:Water Pollutants, Chemical
keywords: Biodegradation; Kinetics; Pharmaceuticals; Soil; Sorption; Transformation products