E. V. Shamrikova

Individual organic compounds in water extracts from podzolic soils of the Komi Republic

The contents of organic compounds in water extracts from organic horizons of loamy soils with different water contents from the medium taiga zone of the Komi Republic were determined by gas-liquid chromatography and chromatography-mass spectrometry. The mass concentration of organic carbon in the extracts was in the range of 290–330 mg/dm3; the mass fraction of the carbon from the identified compounds was 0.5–1.9%. Hydrocarbons made up about 60% of the total identified compounds; acids and their derivatives composed less than 40%. Most of the acids (40–70%) were aliphatic hydroxy acids. The tendencies in the formation of different classes of organic compounds were revealed depending on the degree of the soil hydromorphism. The acid properties of the water-soluble compounds were studied by pK spectroscopy. Five groups of compounds containing acid groups with similar pKa values were revealed. The compounds containing groups with pKa < 4.0 were predominant. The increase in the surface wetting favored the formation of compounds with pKa 3.2–4.0 and 7.4–8.4.

Acidity of KCl extracts from organic horizons of podzolic soils: sources and possible equilibria.

Samples from the organic horizons of taiga podzolic soils of the Komi Republic were studied, and the possible equilibria established in the soil-KCl solution system (c = 1 mol/l) at the determination of the exchangeable acidity by the Sokolov method were examined. It was shown that the exchangeable acidity was due to aluminum(III) ions in 6% of the samples with pHKCl≤4 and due to the H+ ions formed during the dissociation of water-soluble organic acids in the other samples. A group of samples from the horizons in which Fe3+ ions could appreciably contribute to the soil acidity was discriminated.

A new method to determine the carbon content of water-soluble organic compounds in soils

The possibility to use the oxidation rate of different waters by dichromate as measured by photometry for the determination of the organic carbon content in water extracts from the organic horizons of soddy-podzolic soils (in the Republic of Komi) was confirmed. The advantages of the method proposed are discussed.

Water-soluble organic acids in cryomorphic peat soils of the southeastern Bol’shezemel’skaya tundra

The composition of the water extracts, the pH, and the weight concentrations of the total organic carbon and low-molecular-weight organic acids in seasonally thawed and perennially frozen horizons of cryomorphic peat soils have been determined. The quantitative analysis of the acids converted to trimethylsilyl derivatives has been performed by gas chromatography and chromato-mass spectroscopy. Hydroxypropanoic, propanoic, and hydroxyethanoic acids are the prevailing acids (30–50, 10–20, and 10% of the total acids, respectively). Malic, glyceric, hexadionic, trihydroxybutanoic, ribonic, and other acids have also been detected. It has been shown that the differences in the genesis of the peat deposits significantly affect the composition and content of water-soluble organic compounds in soils on the soil-profile and landscape levels.

Water-soluble low-molecular-weight organic acids in automorphic loamy soils of the tundra and taiga zones

The formation features of water-soluble low-molecular-weight organic acids (LMWOAs) in a zonal series of automorphic soils on loose silicate rocks from the middle taiga to the southern tundra (typical podzolic, gley-podzolic, and surface-gley tundra soils) were first revealed by gas chromatography mass spectrometry and gas-liquid chromatography. The content of LMWOAs varies within the range of 1–14 mg/dm3, which corresponds to 1–5% of the total carbon of the water-soluble soil organic matter. It has been shown that a subzonal feature of gley-podzolic soils in the northern taiga is the high content of LMWOAs, including primarily the strongest aliphatic hydroxyl acids. Possible mechanisms of their formation and accumulation in soils have been considered.

Variation in the acid-base parameters of automorphic loamy soils in the taiga and tundra zones of the Komi Republic

A database for the main genetic horizons of loamy automorphic soddy-podzolic, typical podzolic, gley-podzolic, and surface-gley tundra soils of the Komi Republic was developed on the basis of the available archive and literature data and unpublished results of the authors. The database included the following parameters: the pHwater and pHKCl, the exchangeable and total acidity, and the degree of SEC saturation. All the parameters were characterized by normal distribution types. The variation coefficients V for the pHwater and pHKCl were <10%. For the exchangeable and total acidities and the degree of SEC saturation, the V values varied among the soils and horizons in the range of 10–50%. The greatest differences in the acid-base properties of all the soils were revealed between the groups of organic horizons, the eluvial horizons, and the B horizon by the cluster analysis. Between the separate subtypes of podzolic soils, the maximum differences were observed in the organic and, to a lesser extent, eluvial horizons; the B horizons of the different soils in the taiga and tundra zones did not significantly differ in these terms. For the entire profiles, the highest similarity was found between the typical podzolic and gley-podzolic soils, which were more similar to the automorphic soils of the tundra zone than to soddy-podzolic soils.

Acid and mineral components determining the exchangeable acidity in mineral horizons of taiga soils of the Komi Republic

Analysis of acid components in soil-KCl suspension filtrates from the mineral horizons was performed on the basis of analytical data reported between 1958 and 2003, including the data on more than 60 soil profiles (about 300 horizons) from the taiga zone of the Komi Republic. It was shown that the acid ions Al3+, H+ (exchangeable hydrogen), and Fe3+ and the basic ion H3SiO4− are the main components determining the pH of filtrates. Groups of horizons with the predominance of specific ions were separated.

Metrological assessment of the methods for measuring the contents of acids and ion metals responsible for the exchangeable acidity of soils

Metrological characteristics—precision, trueness, and accuracy—of the results of measurements of the exchangeable acidity and its components by the potentiometric titration method were studied on the basis of multiple analyses of the soil samples with the examination of statistical data for the outliers and their correspondence to the normal distribution. Measurement errors were estimated. The applied method was certified by the Metrological Center of the Uralian Branch of the Russian Academy of Sciences (certificate no. 88-17641-094-2013) and included in the Federal Information Fund on Assurance of Measurements (FR 1.31.2013.16382).

Effect of the biota diversity on the composition of low-molecular-weight water-soluble organic compounds in southern tundra soils

Water extracts from the organic horizons of southern-tundra loamy permafrost-affected soils (a surface-gleyed tundra soil, a surface-gleyed soddy tundra soil (Haplic Stagnosols (Gelic)), and a peaty tundra soil (Histic Cryosol (Reductaquic)) and their undecomposed moss layers have been analyzed. The total weight concentration of the cations (Ca2+, Mg2+, K+, and Na+) determined by the atomic absorption method reaches 20 mg/dm3 in the organic horizons and 40–90 mg/dm3 in the undecomposed moss layers. Potassium and calcium ions dominate in all the organic horizons (80–90% of the total weight); potassium ions prevail in the mosses (about 70%). The weight concentration of carbon in the water-soluble organic compounds is 0.04–0.07 g/dm3 in the organic horizons and 0.20–0.40 g/dm3 in the undecomposed moss layers. The content of low-molecular-weight organic compounds (alcohols, carbohydrates, and acids) identified by gas chromatography and chromatomass spectrometry is 1–30 mg/dm3 in the organic horizons of the soils and 80–180 mg/dm3 in the mosses, which does not exceed 26% of the total organic carbon in the extracts.

Correlations between different acidity forms in amorphous loamy soils of the tundra and taiga zones

Pair correlation coefficients (r) between the acidity parameters for the main genetic horizons of soddy-podzolic soils (SPSs), typical podzolic soils (TPSs), gley-podzolic soils (GPSs), and tundra surfacegley soils (TSGSs) have been calculated on the basis of a previously developed database. A significant direct linear correlation has been revealed between the pHwater and pHKCl values in the organic and eluvial horizons of each soil, but the degree of correlation decreased when going from the less acidic SPSs to the more acidic soils of other taxons. This could be related to the fact that, under strongly acid conditions, extra Al3+ was dissolved in the KCl solutions from complex compounds in the organic horizons and from Al hydroxide interlayers in the soil chlorites. No significant linear correlation has been found between the exchangeable acidity (Hexch) and the activity of the [H]+ ions in the KCl extract (a(H+)KCl) calculated per unit of mass in the organic horizons of the SPSs, but it has been revealed in the organic horizons of the other soils because of the presence of the strongest organic acids in their KCl extracts. The high r values between the Hexch and a(H+)KCl in all the soils of the taiga zones have been related to the common source and composition of the acidic components. The correlation between the exchangeable and total (Htot) acidities in the organic horizons of the podzolic soils has been characterized by high r values because of the common source of the acidity: H+ and probably Al3+ ions located on the functional groups of organic acids. High r values between the Hexch and a(H+)KCl have been observed in the mineral horizons of all the soils, because the Al3+ hydroxo complexes occurring on the surface and in the interlayer spaces of the clay minerals were sources of both acidity forms.