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Detection of micropollutants, such as pharmaceuticals and industrial chemicals with endocrine disrupting potency, in ground and surface waters is of emerging concern. Within the aquatic environment, these emerging contaminants (ECs) can interact with various surfaces and biological membranes. The implication is that, provided the ECs exhibit sufficient affinity, these surfaces can modulate their fate and transport properties. Knowledge of the types of interaction with biomembranes can also help decipher their impact on the aquatic organisms. Here, we show that selected pharmaceuticals and endocrine disrupting chemicals (EDCs) – amlodipine (AMP), carbamazepine (CBZ), β-estradiol (β-ED), and 4-propylphenol (4-PP) - exhibit proclivity for the air/aqueous interface. These compounds also interact differently with a zwitterionic phospholipid membrane. The adsorption free energy for the water surface, in the order of increasing affinity, is as follows: 4-PP < AMP < β-ED~CBZ. Of the four compounds studied, 4-PP has the greatest extent of disruption of the phospholipid membrane. Our results suggest that the extent of interaction with water surface and biological membrane is dependent upon the chemical nature of these micropollutants. This fundamental study highlights the importance of interfacial chemistry on the fate and transport of emerging contaminants in natural waters.more » « less
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Surface adsorption of two commonly detected emerging contaminants, amlodipine (AMP) and carbamazepine (CBZ), onto model colloidal microplastics, natural organic matter (NOM), and fullerene nanomaterials have been investigated. It is found that AMP accumulation at these colloidal–aqueous interfaces is markedly higher than that of CBZ. Measurements of surface excess and particle zeta potential, along with pH-dependent adsorption studies, reveal a distinct influence of colloidal functional group on the adsorption properties of these pharmaceuticals. AMP shows a clear preference for a surface containing carboxylic group compared to an amine modified surface. CBZ, in contrast, exhibit a pH-dependent surface proclivity for both of these microparticles. The type of interactions and molecular differences with respect to structural rigidity and charge properties explain these observed behaviors. In this work, we also demonstrate a facile approach in fabricating uniform microspheres coated with NOM and C 60 nanoclusters. Subsequent binding studies on these surfaces show considerable adsorption on the NOM surface but a minimal uptake of CBZ by C 60 . Adsorption induced colloidal aggregation was not observed. These findings map out the extent of contaminant removal by colloids of different surface properties available in the aquatic environment. The methodology developed for the adsorption study also opens up the possibility for further investigations into colloidal–contaminant interactions.more » « less
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