Sorption irreversibility of 1,4‐dichlorobenzene in two natural organic matter–rich geosorbents

Hysteresis, a frequently observed phenomenon in sorption studies, is inconsistent with the key assumption of sorption reversibility in most fate and bioavailability models. Therefore, a study of the underlying causes of hysteresis is essential. Carbon-radiolabeled 1,4-dichlorobenzene (DCB) isotope tracer exchange was carried out at select points along the isotherms of DCB in a brown coal and a peat soil, holding total DCB concentration constant. Tracer exchange was performed both in the forward (sorption) and reverse (desorption) directions at the bulk sorption points and in the desorption direction at the corresponding bulk desorption points. Bulk DCB isotherms showed concentration-dependent hysteresis. However, tracer reequilibration in all cases was consistent with free exchange between sorbed and aqueous-phase molecules. These results rule out common experimental artifacts and demonstrate that sorption of bulk DCB is truly hysteretic (i.e., irreversible). The differences in rates between bulk and tracer sorption and desorption are consistent with the coupling of bulk DCB diffusion to other processes that retard equilibration, which we assign to matrix swelling or shrinking. Hysteresis is attributed to matrix deformation--specifically, to inelastic expansion and creation of voids accommodating sorbate molecules in the matrix, which leads to enhanced affinity in the desorption step. Comparing the results to previous results for naphthalene in the coal, we find that irreversible effects are similar for DCB and naphthalene in the coal but differ for DCB between the two sorbents. An explanation based on the different physical properties of these sorbents is provided. Solid-phase extraction of equilibrated DCB with Tenax revealed a highly desorption-resistant fraction. While too small to account for the observed hysteresis, this fraction may represent molecules that become trapped as the matrix collapses and simultaneously stiffens during abrupt desorption.

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