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Organic carbon and sulphur compounds in wetland soils: insights on structure and transformation processes using K-edge XANES and NMR spectroscopy |
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| Authors: | Aleksander Jokic Elena Ponomarenko Darwin W Anderson |
| Institution: | 1 Department of Soil Science, University of Saskatchewan, Saskatoon, Saskatchewan, Canada 2 Department of Chemistry, University of Saskatchewan, Saskatoon, Saskatchewan, Canada S7N 5A8 3 Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada, S7N 0X4 4 Canadian Museum of Civilization, 100 Laurier Street, P.O. Box 3100, Station B, Hull, Quebec, Canada, J8X 4H2 5 Aquatic Ecosystems Impacts Branch, National Water Research Institute, Saskatoon, Saskatchewan, Canada, S7N 3H5 |
| Abstract: | X-ray absorption near-edge structure (XANES) and nuclear magnetic resonance (NMR) spectroscopy were used in combination to characterize organic carbon structures in a series of wetland soils in Saskatchewan, and XANES spectroscopy was also used to examine sulphur speciation in the soils. The organic C contents of most of the wetland soils are consistently higher by a factor of two to five times compared to adjacent well-drained soils. NMR analyses indicate that the organic matter in the wetland soils consists of predominantly aliphatic structures such as carbohydrates and long chain poly(methylene) units which are refractory structures found in plant waxes. The poly(methylene) structures have a significant capacity to sorb nonpolar organic molecules. The phenolic OH and carboxyl group content of the wetland soils studied is an additional significant factor in their sequestering ability for heavy metals or pesticides. Carbon XANES spectroscopy shows that the surface (∼10 nm) layer of particulate organic matter has a structure dominated by aromatic, carbohydrate and carboxylic acid-like material apparently derived from partially degraded lignin and cellulose polymers which are adsorbed onto clay minerals. The aliphatic structures remaining in this surface layer are probably recalcitrant (poly)methylene units. At a depth of ∼100 nm, the aliphatic content significantly increases suggesting the presence of more labile structures. The presence of these more labile aliphatic compounds may be due to slow decomposition rates in the wet, often cool environments present and to the protective action of the more refractory components in the surface ∼10 nm of the organic matter. Drying of the wetlands, either by draining or as a result of climate change, is likely to result in the rapid decomposition of these labile organic structures releasing carbon dioxide. Our data indicate that the preservation of the organic carbon compounds in these soils is a result of their presence as surface adsorbed layers on the soil mineral particles. The soils contain three different classes of sulphur compounds: reduced organic sulphur such as sulphides, low valent oxidized sulphur such as sulphoxides, and high valent oxidized sulphur such as sulphonate and sulphate. Of these, reduced sulphur species constitute between one-third and two-thirds of the total. Sulphonate structures comprise between a fifth and a third of the total. Sulphates exhibit a wide variation in content, and sulphoxides are either not detected or are present to a lesser extent (<5%). Drying of the wetlands would cause oxidation of sulphides to sulphates. |
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