Resistant sorption of in situ chlorobenzenes and a polychlorinated biphenyl in river Rhine suspended matter.

The desorption kinetics of in situ chlorobenzenes (dichlorobenzenes, pentachlorobenzene and hexachlorobenzene) and 2,4,4'-trichlorobiphenyl (PCB-28) were measured with a gas-purge technique for river Rhine suspended matter sampled in Lobith, The Netherlands. This suspended matter is the main source of sediment accumulation in lake Ketelmeer. In lake Ketelmeer sediment earlier observations showed that slow and very slow fractions dominate the desorption profile. For the river Rhine suspended matter, only for PCB-28 a fast desorbing fraction of around 1.6% could be detected. The observed rate constants were on the average 0.2 h(-1) for fast desorption, 0.004 h(-1) for slow desorption, and 0.00022 h(-1) for very slow desorption. These values are in agreement with previous findings for the sediment from lake Ketelmeer and with available literature data on fast, slow, and very slow desorption kinetics. The results from this study show the similarity of desorption profiles between river Rhine suspended matter, and the top layer sediment from lake Ketelmeer. This indicates that slow and very slow fractions are already present in material forming the top layer of lake Ketelmeer, and were not formed after deposition of this material in the lake. The absence of detectable fast fractions for most compounds could be caused by the absence of recent pollution of the suspended matter. But, the observations may also be explained by a rapid disappearance of compounds from the fast fraction due to a combination of a high affinity of very slow sites for these compounds, and their relatively high volatility.

A simple Tenax extraction method to determine the availability of sediment-sorbed organic compounds.

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.