A simple method to determine the availability of sediment-sorbed organic contaminants was developed and validated. For 10 polycyclic aromatic hydrocarbons, 4 polychlorinated biphenyls, and 9 chlorobenzenes in 6 sediments, we measured the fraction extracted by Tenax in 6 and 30 h. These fractions were compared with the rapidly desorbing fractions determined by consecutive Tenax extraction. Extraction by Tenax for 30 h completely removed the rapidly desorbing fraction plus some part of the slowly desorbing fraction. The fraction removed after 30 h was about 1.4 times the rapidly desorbing fraction. The fraction extracted by Tenax after 6 h is about 0.5 times the rapidly desorbing fraction for chlorobenzenes (CBs)/polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). The rapidly desorbing fraction probably represents the fraction of sorbed organic compound that poses actual risks for transport to (ground) water and determines the uptake by organisms and that can be microbially degraded. Extraction by Tenax for 6 h provides an easy way to address these issues more accurately than does the measurement of total concentrations.

Pollutants in aged field sediments seem to differ from spiked sediments in their chemical and biological availability. Biphasic desorption is often used as an explanation. In the present study, desorption kinetics and partitioning of chlorobenzenes (CBs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) in long term field contaminated sediment cores and top layer sediment were measured by gas-purging. Desorption from sediment was deduced to be triphasic:  fast, slowly, and very slowly desorbing fractions were distinguished. In both the sediment core and the top layer sediment no detectable fast fractions were present for all the compounds studied, so these were estimated as upper limits from the desorption curves. This observation coincided with very high in situ distribution coefficients for several PCBs and PAHs:  10−1000 times higher than literature values for short contact time experiments. Rate constants were (3−8) × 10-3 h-1 for slow desorption and (0.16−0.5) × 10-3 h-1 for very slow desorption. In some cases only a very slowly desorbing fraction was detectable. Desorption from field contaminated sediments with extended contact times may not be readily estimated from laboratory experiments in which contaminants have contact times with the sediment in the order of weeks.

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Rate constants for adsorption and desorption of four organochlorine compounds on black carbon in a sediment were determined from measurements of the rate of removal, by gas purge, of the organochlorine compounds as single solutes from a water-sediment mixture immediately after addition of the solute to the system. The rates of removal fitted to a kinetic scheme based on Langmuir adsorption onto two types of sites in black carbon. The first-order rate constants for desorption from these sites were comparable to those for slow and very slow desorption from sediment. The time needed to reach apparent equilibrium in the experimental setup, with 10 g sediment/L water, ranged from 13 to 166 h, depending on the sorbate and the adsorption process. These short times to equilibrium suggest no need to assume rate-limiting diffusion from and to adsorption sites in this sediment. Average Gibbs free energies for adsorption of the four organochlorine compounds from the pure solid state were -10 +/- 3 and -20 +/- 3 kJ/mol for low-energy and high-energy sites, respectively, pointing to two different adsorption mechanisms.