Abstract

Research into the fate of pharmaceutical compounds (PCs) in the environment has focused on aspects of removal efficiency during sewage treatment, degradation in surface water and accumulation in soils and sediments. However, very little information is available on the binding interactions of pharmaceuticals with dissolved organic matter (DOM) originating from wastewater treatment. Such interactions can significantly affect the transport potential of PCs in soils by altering compound affinity for soil particle surfaces. Our primary hypothesis is that the transport potential of PCs in soils is strongly impacted by the type and strength of interaction with DOM and the stability of resulting DOM-PC complexes. The overarching goal of the proposed work is to develop a better understanding of the risk associated with introduction of PCs into the environment with treated wastewater. This goal has been achieved by elucidating the mechanisms of the interaction of selected pharmaceuticals (that have shown to be widespread wastewater contaminants) with DOM constituents; by determining the stability and fate of DOM-PC complexes introduced to soils and soil constituents; and by evaluating the potential uptake of these compounds by plants. Based on the results obtained in this study (column and batch sorption-desorption experiments), we suggest that PCs can be classified as slow-mobile compounds in SOM-rich soil layers. When these compounds pass this layer and/or are introduced into SOM-poor soils, their mobility increases significantly. Our data suggest that in semiarid soils (consisting of low SOM), PCs can potentially be transported to the groundwater in fields irrigated with reclaimed wastewater. Moreover, the higher mobility of the acid PCs (i.e., naproxen and diclofenac) in freshwater column systems suggests that their residues in soils irrigated with reclaimed wastewater can leach from the root zone and be transported to the groundwater after rain events. Our data obtained from the binding experiments of PCs with DOM demonstrate that the hydrophobic DOM fractions were more efficient at sorbing PCs than the more polar hydrophilic fractions at a pH near the pKa of the analytes. At the pH of natural semiarid water and soil systems, including that of reclaimed wastewater and biosolids, the role of the hydrophobic fractions as sorption domains is less important than the contribution of the hydrophilic fractions. We also hypothesize that the DOM fractions interact with each other at the molecular level and do not act as independent sorption domains. In summary, our data collected in the BARD project demonstrate that the sorption abilities of the DOM fractions can also significantly affect the mobility of pharmaceutical compounds in soils influenced by intensive irrigation with treated wastewater or amended with biosolids.

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