title: In-line gas chromatographic apparatus for measuring the hydrophobic micropore volume (HMV) and contaminant transformation in mineral micropores.
abstract: Desorption of hydrophobic organic compounds from micropores is characteristically slow compared to surface adsorption and partitioning. The slow-desorbing mass of a hydrophobic probe molecule can be used to calculate the hydrophobic micropore volume (HMV) of microporous solids. A gas chromatographic apparatus is described that allows characterization of the sorbed mass with respect to the desorption rate. The method is demonstrated using a dealuminated zeolite and an aquifer sand as the model and reference sorbents, respectively, and trichloroethylene (TCE) as the probe molecule. A glass column packed with the microporous sorbent is coupled directly to a gas chromatograph that is equipped with flame ionization and electron capture detectors. Sorption and desorption of TCE on the sorbent was measured by sampling the influent and effluent of the column using a combination of switching and injection valves. For geosorbents, the HMV is quantified based on Gurvitsch's rule from the mass of TCE desorbed at a rate that is characteristic for micropores. Instrumental requirements, design considerations, hardware details, detector calibration, performance, and data analysis are discussed along with applications. The method is novel and complements traditional vacuum gravimetric and piezometric techniques, which quantify the total pore volume under vacuum conditions. The HMV is more relevant than the total micropore volume for predicting the fate and transport of organic contaminants in the subsurface. Sorption in hydrophobic micropores strongly impacts the mobility of organic contaminants, and their chemical and biological transformations. The apparatus can serve as a tool for characterizing microporous solids and investigating contaminant-solid interactions.
authors.affiliation: State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China.
authors.forename: Hefa
authors.initials: H
authors.lastname: Cheng
authors.forename: Martin
authors.initials: M
authors.lastname: Reinhard
mesh_terms: D000327:Adsorption; D002138:Calibration; D002849:Chromatography, Gas; D003627:Data Interpretation, Statistical; D006371:Helium / Q000737:chemistry; D008851:Micropore Filters; D008855:Microscopy, Electron, Scanning; D008903:Minerals / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D016062:Porosity; D013696:Temperature; D014241:Trichloroethylene / Q000737:chemistry; D017641:Zeolites / Q000737:chemistry
chemical_list: D008903:Minerals; D017641:Zeolites; D006371:Helium; D014241:Trichloroethylene; D010100:Oxygen