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.

Anaerobic microorganisms enriched from Rhine River sediments are able to remove chlorine substituents from poly‐chlorinated dibenzo‐p‐dioxines (PCDDs). A model PCDD, 1,2,3,4‐tetrachlorodibenzo‐p‐dioxin (1,2,3,4–TeCDD) was reduc‐tively dechlorinated to both 1,2,3–and l,2,4–trichlorodibenzo‐/>‐dioxins (1,2,3–and 1,2,4–TrCDD). These compounds were further dechlorinated to 1,3–and 2,3–dichlorodibenzo‐p‐dioxins and traces of 2–monochlorodibenzo‐p‐dioxin. This is the first report in the literature of the anaerobic microbial dechlorination of PCDDs. The same enrichment culture was previously found to deSchlorinate chlorinated benzenes (CBs) and polychlorinated biphenyls (PCBs). An anaerobic culture able to remove aryl chlorines from three classes of compounds has not been reported before. The rate at which the culture dechlorinates 1,2,3,4–TeCDD (t1/2 = 15.5 d) was between those observed for CBs and PCBs. This study shows that reductive dechlorination may have an effect on PCDDs in sediments, as has been demonstrated for CBs and PCBs. The formation of metabolites with a conserved 2,3‐substitution pattern from 1,2,3,4–TeCDD indicates that dechlorination of highly chlorinated dibenzo‐p‐dioxins may result in metabolites that are potentially more toxic than the parent compounds.

No abstract

Eight sediment cores were taken from Lake Ketelmeer, a sedimentation area of the Rhine River, located in the central part of The Netherlands. Priority pollutants (eight metals, six planar and mono‐ortho polychlorinated biphenyls, seven polychlorinated dibenzo‐p‐dioxins, 10 polychlo‐rinated dibenzofurans, and eight polycyclic aromatic hydrocarbons) were determined in all or in a selected number of cores. Present‐day and historical levels of pollutants since the late 1930s were established through the use of radionuclide time tracers (137Cs, 134Cs) and area‐specific geological time markers. Postdepositional redistribution of pollutants and possible transformations were evaluated by analyzing sediment top‐layer samples that were taken in 1972. Disappearance in the anaerobic sediment was observed for several chlorinated biphenyls, dioxins, and furans, Disappearance of the chlorinated compounds may be caused by microbial dechlorination reactions in the anaerobic lake sediment. For the persistent metals and polycyclic aromatic hydrocarbons, as well as for the somewhat changed concentrations of chlorinated aromatics, trends in the concentration profiles during the last five decades are described. Rather low concentrations of almost all studied chlorinated compounds were observed in the early 1940s. These low levels were in contrast to the metal and PAH concentrations, which were already high in the late 1930s and were lowered during the second world war. For all studied compounds, maximum concentrations were found between 1955 and 1975. Cadmium and nickel levels remained high until 1980. The highly toxic 2,3,7,8‐tetrachlo‐rodibenzo‐p‐dioxin reached concentrations up to 400 ng/kg in the mid‐1960s. Recently deposited sediments showed lower pollutant levels. The levels of lead, arsenic, and all studied PAHs were the lowest observed in the past five decades.

Abstract. In sedimentation areas of polluted rivers, microbial dechlorination of chlorinated aromatics may be of great environmental significance. This reaction may take place in the deeper, anaerobic sediment layers and involves replacement of a chlorine in the pollutant molecule by hydrogen. In this study, the microbial dechlorination of hexachlorobenzene in a sedimentation area of the Rhine River is evaluated by using Rhine water pollution data, concentrations in historical sediment samples and in recent sediment cores, and the results of anaerobic laboratory incubations with Lake Ketelmeer sediment. The various data support the conclusion that microbial dechlorination of hexachlorobenzene has occurred in the anaerobic sediment. Up to 80% of the hexachlorobenzene deposited in the early 1970s has been dechlorinated. The maximum half-life of hexachlorobenzene in the sediment is found to be 7 years.Two limitations of microbially mediated dechlorination in the natural environment have become clear. In the first place, a residual concentration of about 40 pug/kg remains unaltered in the sediment or transformation rates of this fraction are at least extremely low. Secondly, the lower chlorinated benzenes that are produced from hexachlorobenzene appear to accumulate in the anaerobic sediment.