Molecular Weight Distribution of Humic Acids Isolated from Calcic Cryosol in Central Yakutia, Russia.

The transition of soils into fallow state has a significant impact on the accumulation and transformation of soil organic matter (SOM). However, the issue of SOM transformation as a result of soil transition to fallow state in cryolithozone conditions is insufficiently studied. The aim of this study is to investigate the molecular weight (MW) distribution of humic acids (HAs) isolated from soils of central Yakutia. Native, fallow and agricultural soils in the vicinity of Yakutsk city were studied. MW distributions of HA preparations were obtained on an AKTAbasic 10 UPS chromatographic system (Amersam Biosciences, Uppsala, Sweden) using a SuperdexTM 200 10/300 GL column (with cross-linked dextran gel, fractionation range for globular proteins 10-600 kDa). The data on the molecular-mass distribution of HAs of fallow and agricultural soils of Central Yakutia were obtained for the first time. According to the obtained data, it was found that the highest carbon content in the structure of HAs was observed in agricultural soils (52.56%), and is associated with soil cultivation and fertilizer application. Among the HAs of fallow soils, we note that those soils that are in the process of self-vegetation have a relatively high carbon content in the HAs (45.84%), but the highest content was observed in fallow soils used as hayfields (49.98%), indicating that the reinvolvement of agriculture in fallow soils leads to an increase in the carbon content of HAs. According to the data of the MW distribution of HAs, it was found that the highest content of a high MW fraction of HAs was recorded in native soil (18.8%); this is due to the early stages of humification and the low maturity of organic matter. The highest content of a low MW fraction of HAs was recorded in agricultural soil (73.3%); this is due to the formation of molecular complexes of a "secondary" nature, which are more stable in the environment than the primary transformation products of humification precursors. The molecular composition of the HAs of fallow soils in the process of self-overgrowing is characterized by values closer to the HAs of native soils, which indicates their transformation towards HAs of native soils. The obtained results indicate that the reinvolvement of fallow soils leads to the transformation of the molecular composition of HAs towards HAs of agricultural soils, and to an increase in the resistance of SOM to biodegradation.

Geochemical Characteristics of the Vertical Distribution of Heavy Metals in the Hummocky Peatlands of the Cryolithozone.

One of the main reservoirs depositing various classes of pollutants in high latitude regions are wetland ecosystems. Climate warming trends result in the degradation of permafrost in cryolitic peatlands, which exposes the hydrological network to risks of heavy metal (HM) ingress and its subsequent migration to the Arctic Ocean basin. The objectives included: (1) carrying out a quantitative analysis of the content of HMs and As across the profile of Histosols in background and technogenic landscapes of the Subarctic region, (2) evaluating the contribution of the anthropogenic impact to the accumulation of trace elements in the seasonally thawed layer (STL) of peat deposits, (3) discovering the effect of biogeochemical barriers on the vertical distribution of HMs and As. The analyses of elements were conducted by atom emission spectroscopy with inductively coupled plasma, atomic absorption spectroscopy and scanning electron microscopy with an energy-dispersive X-ray detecting. The study focused on the characteristics of the layer-by-layer accumulation of HMs and As in hummocky peatlands of the extreme northern taiga. It revealed the upper level of microelement accumulation to be associated with the STL as a result of aerogenic pollution. Specifically composed spheroidal microparticles found in the upper layer of peat may serve as indicators of the area polluted by power plants. The accumulation of water-soluble forms of most of the pollutants studied on the upper boundary of the permafrost layer (PL) is explained by the high mobility of elements in an acidic environment. In the STL, humic acids act as a significant sorption geochemical barrier for elements with a high stability constant value. In the PL, the accumulation of pollutants is associated with their sorption on aluminum-iron complexes and interaction with the sulfide barrier. A significant contribution of biogenic element accumulation was shown by statistical analysis.

Relating Paramagnetic Properties to Molecular Parameters of Humic Acids Isolated from Permafrost Peatlands in the European Arctic.

Free radicals (FRs) are intermediate participants in the transformation process of soil organic matter, and free radical activity is a fundamental property of humic substances. The aim of this work was to conduct a comparative study of the paramagnetic properties of humic acids (HAs) isolated from Histosols by electron paramagnetic resonance (EPR) spectroscopy. The studied Histosols are found in permafrost peatlands in four natural geographic subzones of the European Arctic (from forest tundra to northern tundra). The results obtained showed that in anaerobic conditions on the peatlands in the tundra zone, the formation of semiquinone-type radicals occurs through the reduction of quinone fragments of HAs and leads to an increase in the concentration of paramagnetic centres within HAs. PCA analysis allowed us to reveal relationships between the properties of the initial raw peat samples, the molecular composition of the isolated HAs, and their paramagnetic parameters. It was found that FR localization occurs predominantly on aromatic fragments of lignin nature, which are confined to the low molecular weight fraction of HAs. The g-factor values of the EPR spectra of HAs indicate the presence of carbon- and oxygen-centred FRs in the HA structure, with a predominance of the latter.

Complexation of lead and cadmium ions with humic acids from arctic peat soils.

Humic acids (HAs) have many significant environmental and geochemical functions in soils, bottom sediments, and aquatic environments. Their interaction with toxic heavy metal ions affects their transport and bioavailability. This study suggests that binding of heavy metal ions to HAs could potentially help to develop strategies for recovering metal-contaminated soils and groundwater. This study is aimed at investigation of sorption properties of HA preparations from peat soils based on determining the kinetic and thermodynamic parameters of the sorption processes of Cd2+ and Pb2+ ions. Based on a model experiment, the binding ability of HAs of Hemic Folic Cryic Histosol to Cd2+ and Pb2+ ions was revealed. It is shown that during the initial stage (first 20 min for Cd2+ ions and 30 min for Pb2+ ions) the kinetics of the process of sorption of metal ions by suspended HA preparations is better described by pseudo-second order equation. This indicates the chemisorption mechanism and limiting contribution of chemical reaction. The kinetics sorption process within the Boyd - Adamson - Myers model is described with high precision for both ions during the whole experiment. This indicates the intra-diffusion limitation of the sorption process. The thermodynamic characteristics (the limiting sorption capacity, constant of sorption equilibrium, Gibbs free energy change, entropy change and enthalpy change of sorption) of the sorption process of selected heavy metal ions have been calculated. It was found that the limiting specific sorption of Pb2+ ions is almost an order of magnitude higher than that of Cd2+ ions and amounts to 0.16-0.29 mmol/dm3 and 0.0078-0.034 mmol/dm3, respectively. The sorption enthalpy variance of 48.4 kJ/mol for Cd2+ ions and 22.6 kJ/mol for Pb2+ ions indicate the endothermic nature of sorption on HA solid particles. It was shown that the limiting stage of sorption for Cd2+ and Pb2+ ions is ion diffusion to the sorbent, while chemisorption itself proceeds quite quickly. Values ΔS> -10 J/(mol ∙ K) indicate a dissociative sorption mechanism for both metals, i.e. non-sorbed ions in the solution are in a more ordered state than after sorption. The negative values of the Gibbs free energy change for Cd2+ and Pb2+ ions indicate that the interaction of ions with HA preparations from peat soils is a spontaneous process with a complex mechanism involving complexation and ion exchange processes.

Molecular composition of raw peat and humic substances from permafrost peat soils of European Northeast Russia as climate change markers.

Humic substances (HSs) from the mire peat soils of the forest-tundra zone of the European northeast part of Russia have been characterized in terms of molecular composition. This was accomplished using solid-state 13C nuclear magnetic resonance (13C NMR) techniques and electron spin resonance (ESR) spectroscopy. The composition depended on the intensity of cryogenic processes in the active layer, the quality of the humification precursors (the degree of peat material transformation), and the biochemical selection of aromatic fragments during humification. Humic acids (HAs) and fulvic acids (FAs) of the peat soils showed the presence of compounds with a low extent of condensation and a low portion of aromatic fragments, which increased with depth. A higher proportion of aliphatic carbon species was found in the HAs, indicating a low degree of organic matter stabilization. Based on the data from the two types of peat soils, we suggest that particular changes in the proportion of aromatic and unoxidized aliphatic fragments on the border of the bottom of the active layer and permafrost layers can be used as markers of current climatic change.