Retardation of organic contaminants in natural fractures in chalk.

Transport of a conservative compound and two sorbing compounds through fractured chalk was studied using flow-through columns consisting of chalk cores with a single subvertical fracture. Two types of chalk matrix were compared, an oxidized white chalk with low organic carbon content (0.2%), and a gray chalk with a higher organic carbon content (1.3%). Initial rapid breakthrough followed by a delayed approach to a relative concentration of unity for the conservative compound (2,6-difluorobenzoic acid [DFBA]) was clear evidence for diffusion into the porous chalk matrix. Matrix diffusion of DFBA was apparently much greater in the gray chalk columns than in the white chalk columns. Breakthrough curves (BTCs) of the sorbing compounds (2,4,6-tribromophenol [TBP] and ametryn [AME]) were retarded in all cases as compared to the conservative compound. Sorption retardation was far greater in the gray chalk as compared with the white chalk, in good agreement with results from batch sorption experiments. BTCs for the conservative compound were relatively nonhysteretic for both white and gray chalk columns. In contrast, BTCs for the sorbing compounds were hysteretic in all cases, demonstrating that sorption was not at equilibrium before desorption began. These experiments suggest that on a field scale, transport of contaminants through fractures in chalk and other fractured porous media will be attenuated by diffusion and sorption into the matrix.

Sorption of organic contaminants in a fractured chalk formation.

Sorption capability of bedrock components from a fractured chalk province was evaluated using ametryn, phenanthrene, m-xylene, 2,4,6-tribromophenol, and 1,2-dichloroethane. Sorption isotherms for the four aromatic compounds were nonlinear on gray (unoxidized) chalk. Over the studied solution ranges, the distribution coefficient decreased by factor of 3 for phenanthrene and m-xylene, a factor 4 for ametryn, and by an order of magnitude for 2,4,6-tribromophenol. In contrast, 1,2-dichloroethane displayed a linear isotherm. The importance of polar interactions for ametryn sorption was evaluated by normalizing sorption to an "inert" solvent, n-hexane. n-Hexane-normalized sorption of ametryn was much greater than that of phenanthrene, presumably due to ametryn participation in hydrogen bonding interactions. In sharp contrast to sorption to gray chalk, sorption to white (oxidized) chalk is 100- to 1000-fold lower at any given solution concentration. The much greater sorption on gray chalk cannot be explained by specific surface area, clay content, or organic matter content; thus, the nature of the organic matter is considered to control sorption in the chalk samples. Gray chalk sorption capacity estimates for ametryn and 2,4,6-tribromophenol are similar, which, together with evidence of competition for sorption sites, suggests that the limited capacity sorption domain for both compounds is similar.