The Molecular Composition of Humic Acids in Permafrost Peats in the European Arctic as Paleorecord of the Environmental Conditions of the Holocene

Abstract

The purpose of our research is focused on examination of the transformation regularities of molecular composition of humic acids (HAs) in the hummocky frozen peatlands of the European Arctic as a marker of climatic changes in the Holocene, and assessment of the stabilization of soil organic matter under the conditions of modern climatic warming. Histosols located in the two subzones of the European Arctic served as the research subjects. This territory is actively used for reindeer breeding, which is a vital agricultural branch in the Far North of the Russian Federation. The data obtained reveal the main trends in the formation of HAs from Arctic peatlands under different environmental conditions. Modern peat sediments (top layers) in the middle and late Holocene period formed out of bryophyte residues and contained HAs with long-chain carbohydrate and paraffin structures in their composition. These structures enlarged the dynamic radii of HA molecules, and, thus, caused high average molecular weight values. The more favorable climatic conditions of the early Holocene (the Atlantic optimum) defined the botanical composition of peat, which was dominated by tree and sedge communities with high contents of lignin components and, as a consequence, a larger share of aromatic fragments, characterized by thermo-biodynamic resistance in HAs of horizons in the lower and central profile parts. The molecules of HAs are an archive of paleoclimatic records. The Subboreal and Subatlantic climatic conditions determined the specifics of vegetation precursors and, as a result, the molecular structure of HAs in seasonally thawed layers, with a predominance of long-chain aliphatic fragments. The conversion of HAs from Histosols led to an increase in the proportion of carbon in branched and short-chain paraffinic structures with their subsequent cyclization and aromatization. The results of this process are most clearly manifested in layers formed during the Holocene I and II climatic optima. Higher biologically active temperatures of the seasonally thawed layer of soils at bare spots (without vegetation) determined the accumulation of thermodynamically more stable HA molecules with a high content of aromatic fragments. This contributed to both the stabilization of the SOM and the conservation of peatlands in general.

Keywords

• peatland
• climatic conditions
• ¹³C NMR spectroscopy
• size-exclusion chromatography
• cryogenic processes
• peat erosion