Explaining PAH desorption from sediments using Rock Eval analysis.

Here, we provide Rock Eval and black carbon (BC) characteristics and polycyclic aromatic hydrocarbon (PAH) distribution coefficients (KD) for sediments from the Danube, Elbe, Ebro, and Meuse river basins. PAH desorption kinetic parameters were determined using sequential Tenax extractions. We show that residual carbon (RC) from Rock Eval analysis is an adequate predictor of fast, slow, and very slow desorbing fractions of 4-ring PAHs. RC correlated better than BC, the latter constituting only 7% of RC. A dual domain sorption model was statistically superior to a single domain model in explaining KD for low molecular weight PAHs, whereas the opposite was observed for high molecular weight PAHs. Because particularly the 4-ring PAHs are bioavailable and relevant from a risk assessment perspective and because their fast desorbing fractions correlate best with RC, we recommend RC as a relevant characteristic for river sediments.

Modeling polychlorinated biphenyl sorption isotherms for soot and coal.

Sorption isotherms (pg-ng/L) were measured for 11 polychlorinated biphenyls (PCBs) of varying molecular planarity from aqueous solution to two carbonaceous geosorbents, anthracite coal and traffic soot. All isotherms were reasonably log-log-linear, but smooth for traffic soot and staircase-shaped for coal, to which sorption was stronger and more nonlinear. The isotherms were modeled using seven sorption models, including Freundlich, (dual) Langmuir, and Polanyi-Dubinin-Manes (PDM). PDM provided the best combination of reliability and mechanistically-interpretable parameters. The PDM normalizing factor Z appeared to correlate negatively with sorbate molecular volume, dependent on the degree of molecular planarity. The modeling results supported the hypothesis that maximum adsorption capacities (Q(max)) correlate positively with the sorbent's specific surface area. Q(max) did not decrease with increasing sorbate molecular size, and adsorption affinities clearly differed between the sorbents. Sorption was consistently stronger but not less linear for planar than for nonplanar PCBs, suggesting surface rather than pore sorption.