Competitive sorption experiments reveal new regression models to predict PhACs sorption on carbonaceous materials.

Sorption of hydrophobic organic contaminants onto thermally altered carbonaceous materials (TACM) constitutes a widely used technology for remediation of polluted waters. This process is typically described by sorption isotherms, with one of the most used models, the Polanyi-Dubinin-Manes (PDM) equation, including water solubility (Sw) as a normalizing factor. In case of pharmaceutical active compounds (PhACs), Sw depends on the pH of the environment due to the ionic/ionizable behavior of these chemicals, a fact frequently ignored in sorption studies of PhACs. In this work, we set the theoretical framework to include the variation of Sw with pH in the definition of the PDM model, and we applied this approach to describe the effect of ambient pH in the competitive sorption of three commonly detected PhACs (carbamazepine, ibuprofen, and sulfamethoxazole) onto three carbonaceous sorbents (biochar, powder activated carbon, and colloidal activated carbon). Changes in the ambient pH and hence in the hydrophobicity of the compounds could explain the strong variations observed in single-solute sorption and also in competitive sorption. Furthermore, Sw was used as a parameter for the linear regression model of sorption coefficients of our experiments, suggesting the incorporation of this variable as an improvement to existing approaches for prediction of PhACs sorption onto TACM.

Role of Soil Biofilms in Clogging and Fate of Pharmaceuticals: A Laboratory-Scale Column Experiment.

Contamination of groundwater with pharmaceutical active compounds (PhACs) increased over the last decades. Potential pathways of PhACs to groundwater include techniques such as irrigation, managed aquifer recharge, or bank filtration as well as natural processes such as losing streams of PhACs-loaded source waters. Usually, these systems are characterized by redox-active zones, where microorganisms grow and become immobilized by the formation of biofilms, structures that colonize the pore space and decrease the infiltration capacities, a phenomenon known as bioclogging. The goal of this work is to gain a deeper understanding of the influence of soil biofilms on hydraulic conductivity reduction and the fate of PhACs in the subsurface. For this purpose, we selected three PhACs with different physicochemical properties (carbamazepine, diclofenac, and metoprolol) and performed batch and column experiments using a natural soil, as it is and with the organic matter removed, under different biological conditions. We observed enhanced sorption and biodegradation for all PhACs in the system with higher biological activity. Bioclogging was more prevalent in the absence of organic matter. Our results differ from works using artificial porous media and thus reveal the importance of utilizing natural soils with organic matter in studies designed to assess the role of soil biofilms in bioclogging and the fate of PhACs in soils.

A high-resolution monitoring station for the in situ assessment of nitrate-related redox processes at an agricultural site.

Biogeochemical redox processes control the chemical behavior of many major and trace elements, making their comprehension crucial for predicting and protecting environmental health. Nitrogen (N) is especially susceptible to changes in soil redox conditions and affects the cycles of other redox-sensitive species. Elevated N concentrations, in nitrate form, in agricultural soils and associated freshwater ecosystems constitute a problem in many parts of the world. Although a wide variety of measures have been adopted, their assessment through concentration measurements in groundwater and surface water of the different monitoring networks has shortcomings. Nitrate, as a non-point pollutant, is subject to several processes (e.g., transformation and retardation) before it is detected, making it impossible to evaluate measurements' effectiveness reliably. Thus, we designed and constructed a monitoring station featuring commercially available products and self-manufactured components at an agricultural site for the in situ assessment of nitrate-related processes by high-resolution monitoring of hydraulic (soil water content, matric potential, groundwater head) and hydrogeochemical variables (oxidation-reduction potential and groundwater and pore water chemistry) within the vadose zone and the shallow aquifer. The monitoring station has proven to be a reliable tool. Changes over depth and time of measured variables have been identified, allowing the detection of the transient behavior of the redox reactive zone and the interpretation of ongoing denitrification processes and other redox nitrate-triggered phenomena, such as uranium roll-front and selenium accumulation at the redox interface. Measuring both geochemical and soil water variables allows for the calculation of in situ solute inputs into the groundwater and their reaction rates.