Carbon suboxide, a highly reactive intermediate from the abiotic degradation of aromatic compounds in soil.

The formation of volatile compounds during abiotic degradation processes of aromatic compounds in soil has been the subject of many experimental studies but should be examined further. In this context, the present work investigates the natural formation of carbon suboxide using the model compounds catechol and 3,5-dichlorocatechol and also a soil sample from a peat bog. The measurements were performed with a purge and trap GC/ MS system following various optimization steps. Under certain conditions, we obtained 16.7 ng of carbon suboxide from a 250 mg soil sample. We also found that the formation of carbon suboxide requires a definite activation energy and that it is rather short-lived in the natural environment. A subsequent reaction to malonic acid is expected in the presence of water. It is shown that iron-(III), hydrogen peroxide, and chloride are prerequisites for its formation. Experimental parameters for the highest yield of carbon suboxide depend on the precise molecular structure of the model compound or on the individual soil sample, respectively. The presented results point to a new degradation process for aromatic compounds in soil.

De novo formation of chloroethyne in soil.

To date, chloroethyne in the environment has been proposed to occur as a reactive intermediate during the reductive dechlorination of tri- and tetrachloroethene with zerovalent metals. Such artificial conditions might possibly be found at organohalide-contaminated sites that are surrounded by remediation barriers made of metallic iron. In this paper, it is shown that the highly reactive chloroethyne is also a product of natural processes in soil. Soil air samples from three differentterrestrial ecosystems of Northern Germany showed significant chloroethyne concentrations, besides other naturally produced monochlorinated compounds, such as chloromethane, chloroethane and chloroethene. Measured amounts range from 5 to 540 pg chloroethyne in air purged from 1 L of soil. A possible route of chloroethyne formation in soil is discussed, where chloroethyne is probably produced as a byproduct of the oxidative halogenation of aromatic compounds in soil. A series of laboratory studies, using the redox-sensitive catechol as a discrete organic model compound, showed the formation of chloroethyne when Fe3+ and hydrogen peroxide were added to the system. We therefore propose that the natural formation of chloroethyne in soil proceeds via oxidative cleavage of a quinonic system in the presence of the ubiquitous soil component chloride.