RESUMO
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.
RESUMO
In the present work, we analyzed the concentration patterns of 20 Polycyclic Aromatic Hydrocarbons (PAHs) in 25 surface sediments and 11 sediment cores from the northern part of Taihu Lake, China. Three of the cores were dated based on 137Cs activity for the deposition age of the sediment. The spatial distributions of the PAH concentrations show that the inflow rivers into Zhushan Bay and Meiliang Bay were the main pathway for PAHs and sediment input to the northern part of the lake. This results in substantially higher PAH concentrations (up to 5000â¯ng/g) and sedimentation rates (higher than the average of 3-4 mm/a) in the area close to the river outlets. In addition, results also show that PAH concentrations in the sediments considerably increased from the early 1960s, but the decreasing concentrations in the upper layers of the sediment could be attributed to the introduction of measures on environmental improvement from ca. 2000. There were both anthropogenic and biogenic origins of perylene in the lake sediments, which were distinguished based on spatial distribution patterns and also the concentration proportions of perylene to the sum of the 20 PAHs. In the cores collected close to river outlets, the concentration proportions of perylene typically range from 0.02 to 0.18 and there are significant positive linear correlations between the concentration of perylene and three anthropogenic PAHs (Benzo[a]pyrene, Benzo[e]pyrene, Pyrene), suggesting that perylene was dominated by anthropogenic input. However, the cores collected further away from the river outlets show the concentration proportions between 0.13 and 0.96, and present significant negative correlations or no correlations between perylene and the three PAHs, suggesting that perylene was mainly formed by biogenic activities. Furthermore, the different perylene sources accompanied with the location distributions imply that anthropogenic activities could inhibit its biogenic formation.