Natural abiotic formation of oxalic acid in soils: results from aromatic model compounds and soil samples.

Oxalic acid is the smallest dicarboxylic acid and plays an important role in soil processes (e.g., mineral weathering and metal detoxification in plants). We have first proven its abiotic formation in soils and investigated natural abiotic degradation processes based on the oxidation of soil organic matter, enhanced by Fe(3+) and H(2)O(2) as hydroxyl radical suppliers. Experiments with the model compound catechol and further hydroxylated benzenes were performed to examine a common degradation pathway and to presume a general formation mechanism of oxalic acid. Two soil samples were tested for the release of oxalic acid and the potential effects of various soil parameters on oxalic acid formation. Additionally, the soil samples were treated with different soil sterilization methods to prove the oxalic acid formation under abiotic soil conditions. Different series of model experiments were conducted to determine a range of factors including Fe(3+), H(2)O(2), reaction time, pH, and chloride concentration on oxalic acid formation. Under certain conditions, catechol is degraded up to 65.6% to oxalic acid referring to carbon. In serial experiments with two soil samples, oxalic acid was produced, and the obtained results are suggestive of an abiotic degradation process. In conclusion, Fenton-like conditions with low Fe(3+) concentrations and an excess of H(2)O(2) as well as acidic conditions were required for an optimal oxalic acid formation. The presence of chloride reduced oxalic acid formation.

Natural abiotic formation of furans in soil.

Furan and its derivates are a potentially important, and little studied, class of volatile organic compounds of relevance to atmospheric chemistry. The emission of these reactive compounds has been attributed previously to biomass burning processes and biogenic sources. This paper investigates the natural abiotic formation of furans in soils, induced by the oxidation of organic matter by iron(III) and hydrogen peroxide. Several model compounds like catechol, substituted catechols, and phenols as well as different organic-rich soil samples were investigated for the release of furans. The measurements were performed with a purge and trap GC/MS system and the influence of hydrogen peroxide, reaction temperature, iron(III), pH, and reaction time on furan yield was determined. The optimal reaction turnover obtained with catechol was 2.33 microg of furan from 0.36 mg of carbon. Results presented in this paper show that a cleavage of catechol into a C2- and a C4-fragment occurs, in which the C4-fragment forms furan by integrating an oxygen atom stemming from H2O2. Furthermore, phenols could be transformed into catecholic structures under these Fenton-like conditions and also display the formation of furans. In conclusion, catalytic amounts of iron(III), the presence of hydrogen peroxide, and acidic conditions can be seen as the most important parameters required for an optimized furan formation.

Natural abiotic formation of trihalomethanes in soil: results from laboratory studies and field samples.

Trihalomethanes (THM), especially trichloromethane, play an important role in photochemical processes of the lower atmosphere, but the current knowledge of the known sources and sinks of trichloromethane is still incomplete. The trichloromethane flux through the environment is estimated at approximately 660 kt year(-1) and 90% of the emissions are of natural origin. Next to offshore seawater contributing approximately 360 kt year(-1) unknown soil processes are the most prominent source (approximately 220 kt year(-1)). This paper describes a new abiotic source of trichloromethane from the terrestrial environment induced by the oxidation of organic matter by iron(III) and hydrogen peroxide in the presence of chloride. Different organic-rich soils and a series of organic substances regarded as monomeric constituents of humus were investigated for their release of trichloromethene. The influence of iron(III), hydrogen peroxide, halide, and pH on its formation was assayed. The optimal reaction turn over for the representative compound catechol was 58.4 ng of CHCl3 from 1.8 mg of carbon applying chloride and 1.55 microg of CHBr3 from 1.8 mg of carbon applying bromide; resorcin and hydroquinone displayed similar numbers. Results presented in this paper pinpoint 1,2,4,5-tetrahydroxybenzene as playing a key role as intermediate in the formation pathway of the trihalomethanes. The highest THM yields were obtained when applying the oxidized form of 1,2,4,5-tetrahydroxybenzene as THM precursor. These findings are consistent with the well-known degradation pathway starting from resorcin-like dihydroxylated compounds proceeding via further hydroxylation and after halogenation finally ending up in trihalomethanes. In conclusion, Fenton-like reaction conditions (iron(III) and hydrogen peroxide), elevated halide content and an extended reaction time can be seen as the most important parameters required for an optimal THM formation.

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.