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Black carbon (BC), characterized by high microporosity and high specific surface area (SSA), has been demonstrated to have substantial contributions to the sorption of hydrophobic organic chemicals in soils and sediments. Other naturally occurring organic matters provide soft and penetrable sorption domains while may cling to BC and affect its original surface properties. In this work, we studied the sorption sites of a Yangtze River sediment sample with organic carbon (OC) content of 3.3 % and the preheated sediment (combusted at 375 °C) with reduced OC content (defined as BC) of 0.4 % by gas and pyrene sorption. The SSA and microporosity of the pristine and preheated sediments were characterized by N and CO adsorption. The results suggest that the adsorption of N was hindered by amorphous organic carbon (AOC) in the pristine sediment but CO was not. Instead, the uptake of CO was higher in the presence of AOC, likely due to the partition of CO molecules into the organic matter. The pyrene adsorptions to BC in pristine and preheated sediments show a similar adsorption capacity at high concentration, suggesting that AOC of ca. 2.9 % in the pristine sediment does not reduce the accessibility to the sorption sites on BC for pyrene. [ABSTRACT FROM AUTHOR]

Sorption of pyrene and phenanthrene to model (illite and charcoal) and natural (Yangtze sediment) geosorbents were investigated by batch techniques using fluorescence spectroscopy. A higher adsorption of phenanthrene was observed with all sorbents, which is related to the better accessibility of smaller molecules to micropores in the molecular sieve sorbents. In addition, pyrene sorption in binary-solute systems with a constant initial concentration of phenanthrene (0.1 μmol L-1 or 2 μmol L-1) was studied. A 0.1 μmol L-1 concentration of phenanthrene causes no competitive effect on the pyrene sorption. A 2 μmol L-1 concentration of phenanthrene significantly suppresses the sorption of pyrene, especially in the low concentration range; nonlinearity of the pyrene sorption isotherms thus decreases. The competitive effect of 2 μmol L-1 phenanthrene on the pyrene sorption is overestimated by the ideal adsorbed solution theory (IAST) using the fitted single sorption results of both solutes. An adjustment of the IAST application by taking into account the molecular sieve effect is proposed, which notably improves the IAST prediction for the competitive effect. [ABSTRACT FROM AUTHOR]

Abstract: The effect of organic carbon (OC) and mineral surface on the sorption of polycyclic aromatic hydrocarbon (PAH) pyrene molecule to four Yangtze River sediments was investigated by sorption batch techniques using fluorescence spectroscopy. Pyrene sorption to the mineral fraction was estimated with model sorbent illite, the main clay mineral in Yangtze sediment. The Freundlich model fitted sorption to illite and to sediments was normalized to the specific surface area (SSA). Comparison of the SSA-normalized sorption capacities of illite and sediments suggests a negligible contribution of the pyrene sorption to the mineral fraction. In addition, composite models, such as the linear Langmuir model (LLM) and the linear Polanyi–Dubinin–Manes model (LPDMM) were applied for fitting the sorption of pyrene to the pristine sediments. The application of composite models allows assessing the partition of pyrene into amorphous organic carbon (AOC) and the adsorption in the porous structure of black carbon (BC). The modelling results indicate that the pyrene adsorption to the minor BC components (<0.2%) is more effective than the partition to AOC (0.5–1.3%). Besides the pristine sediments, sediments preheated at 375°C were also studied, in which the AOC fraction was removed during the preheating treatment. The modelling results with LPDMM and Polanyi–Dubinin–Manes model (PDMM) indicate a similar adsorption capacity of BC in pristine and preheated sediments, respectively. The low AOC concentrations in sediments do not diminish the BC micropore filling with pyrene. Simulation of pyrene distribution in the investigated Yangtze River sediments support the importance of the BC fraction in the PAH immobilization under environmental conditions. [Copyright &y& Elsevier]