The debate on whether the nonlinear sorption of nonionic organic compounds (NOCs) by soil organic matter (SOM) is captured by nonlinear partition or adsorption has been going on for decades because the used SOM samples are complex mixtures from various precursors with varied humification degrees in natural environment. Therefore, in this study, hydrothermal method was employed to prepare humus-like substances from a sole precursor (i.e., rice straw) with various humification degrees for nonlinear sorption of 25 aromatic compounds, then to have an insight into the underlying mechanisms of the nonlinear sorption of NOCs by SOM. It was observed that the increasing humification degree of humus-like substances, i.e., decreasing in the polarity ((O + N)/C) and increasing in the aromaticity, result in the increase of isotherm nonlinearity and sorption capacity/affinity of NOCs. Sorption capacity of NOCs, obtained by isotherm fitting using Dubinin-Astakhov (DA) model and Dual-Mode (DM) model, are positively correlated with their solubility in water and octanol, indicating the nonlinear sorption could be captured by nonlinear partition mechanism. Specific interactions including hydrogen-bonding interaction and π - π interaction between aromatic structures of humus-like substances and organic molecules could be responsible for the nonlinear partition and the increase of sorption affinity with the enhancement of humification degree. These obtained correlations are valuable for understanding the underlying mechanisms of nonlinear sorption and elucidating the transport of NOCs in the environment.
Wenhao Wu,Yuan Lan,Yaxiong Zeng,Daohui Lin,Kun Yang
Organobentonites, i.e., bentonites coated with surfactants such as cetyltrimethylammonium (CTAB), are superior and low-cost sorbents for removal of organic contaminants from wastewater. Nonlinear sorption of polar organic compounds such as phenols and anilines by organobentonites were widely observed and interpreted by adsorption mechanism. However, in this study, it was observed that the nonlinear sorption of phenols and anilines by CTAB coated bentonites (CTAB-bentonites) should be attributed to nonlinear partition mechanism with the additional space limitation in CTAB-bentonites for nonlinear partitioning, rather than adsorption mechanism. This nonlinear partition mechanism is supported by that (i) organobentonites is a partition medium, identified by the linear isotherms of polycyclic aromatic hydrocarbons (PAHs) and nitrobenzenes ; (ii) sorption coefficients (log K d ), the ratio of adsorbed amount ( q e ) to equilibrium concentration ( C e ), and Dubinin-Ashtakhov (DA) model fitted sorption capacity (log Q 0 ) of organic compounds, by a given CTAB-bentonite, are positively correlated with their octanol-water distribution coefficients (log K OW ) and solubility in octanol (log S o ) respectively; (iii) log K d and log Q 0 of a given organic compound by CTAB-bentonites are positively correlated with organic carbon contents ( f oc ) of CTAB-bentonites, but not specific surface area. Specific interaction (i.e., hydrogen-bonding interaction), in addition to van der Waals force , is responsible for the nonlinear partitioning of phenols and anilines into CTAB-bentonites, because of the positively linear relationship between DA model fitted sorption affinity ( E ) and hydrogen-bonding donor parameter ( α m ) of organic compounds. These results could help the recognizing of the nonlinear sorption behaviors of organic compounds by organobentonites and promote their environmental applications in wastewater treatment .
Nonlinear sorption and isotherm nonlinearity of organic compounds by widely used porous resins such as XAD-7 are commonly interpreted as adsorption due to their large surface area. However, through displacement experiments using saturated 4-nitrophenol as the displacer, we observed that the nonlinear sorption and isotherm nonlinearity of selected organic compounds (i.e., naphthalene , nitrobenzenes , phenols and anilines) by XAD-7 was captured by a nonlinear partition mechanism rather than the adsorption mechanism. Nonlinear sorption of organic compounds by XAD-7 includes a nonlinear/displaced fraction and a linear/non-displaced fraction. A dual-mode (DM) model, including a nonlinear Dubinin-Ashtakhov (DA) model component and a linear model component, was developed to describe the nonlinear/displaced fraction and the linear/non-displaced fraction, respectively. The capacity of these two fractions are dependent on their solubility in water or octanol with positively linear relationships but not their molecular size, supporting the nonlinear partitioning mechanism. Besides van-der-waals force, hydrogen-bonding is primarily responsible for the nonlinear partitioning of phenols and anilines into XAD-7, while π-π interaction is responsible for the nonlinear partitioning of naphthalene and nitrobenzenes. The explored nonlinear partitioning mechanism for XAD-7 implies that the nonlinear sorption of organic compounds by porous resins should be recognized for their recovery and applications as sorbents .
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