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SOIL BIOLOGY
Changes in Mn availability and soil acidity in Albic Retisol limed with dolomite screenings of various sizes and doses: A long-term microfield experiment in the north-western Russia
Andrey Litvinovich12, Anton Lavrishchev2,
Vladimir Bure13, Vladimir Miladinovic4, and Elmira Saljnikov45
1Agrophysical Research Institute, Grazhdanskiy pr., 14, Saint Petersburg, 195220, Russian Federation
2Saint Petersburg State Agrarian University, Peterburgskoye shosse, 2, Saint Petersburg, 196601, Russian Federation
3Saint Petersburg State University, Universitetskaya nab., 7-9, Saint Petersburg, 199034, Russian Federation
institute of Soil Science, Teodora Drajzera, 7, Belgrade, 11000, Serbia 5Mitscherlich Akademie für Bodenfruchtbarkeit (MITAK), GmbH, 14641, Paulinenaue, Prof.-Mitscherlich-Alle, 1, Germany
Address correspondence and requests for materials to Anton Lavrishchev, av.lavrishchev@yandex.ru
Abstract
Citation: Litvinovich, A., Lavrishchev, A., Bure, V., Miladinovic, V., and Saljnikov, E. 2023. Changes in Mn availability and soil acidity in Albic Retisol limed with dolomite screenings of various sizes and doses: A long-term microfield experiment in the north-western Russia. Bio. Comm. 68(3): 135-144. https://doi.org/10.21638/ spbu03.2023.301
Authors' information: Andrey Litvinovich, Dr. of Sci. in Agricultural Sciences, Professor, orcid.org/0000-0002-4580-1974; Anton Lavrishchev, Dr. of Sci. in Agricultural Sciences, Associate Professor, orcid. org/0000-0003-3086-2608; Vladimir Bure, Dr. of Sci. in Technical Sciences, Professor, orcid.org/0000-0001-7018-4667; Vladimir Miladinovic, orcid.org/0000-0001-7394-0173; Elmira Saljnikov, PhD, Principal Research Fellow, orcid.org/0000-0002-6497-2066
Manuscript Editor: Evgeny Abakumov, Department of Applied Ecology, Faculty of Biology, Saint Petersburg State University, Saint Petersburg, Russia
Received: February 12, 2023;
Revised: April 12, 2023;
Accepted: May 5, 2023.
Copyright: © 2023 Litvinovich et al. This is an open-access article distributed under the terms of the License Agreement with Saint Petersburg State University, which permits to the authors unrestricted distribution, and self-archiving free of charge.
Funding: No funding information provided.
Ethics statement: This paper does not contain any studies involving human participants or animals performed by any of the authors.
Competing interests: The authors have declared that no competing interests exist.
Liming of acidic soils is associated with various processes in the soil, including the availability of nutrients for plants. The vector and extent of these changes depend, inter alia, on the type of lime material and the doses used. Particularly, excessive liming can trigger a deficiency of manganese for crops. A long-term microfield experiment (13 test years) was carried out on Albic Retisols reclaimed with the dolomite particles of various sizes as a by-product of stone processing quarries. Ten treatments including various sized dolomite particles and their combinations, as well as traditional limestone flour on the background of NPK fertilizer were studied for the changes in soil acidity indicators (exchangeable acidity, pH; hydrolytic acidity, Hy; total acidity, Htot) and manganese availability. The amount of acidic components passing into the extract of 1N KCl was insufficient to reveal a dependency between the exchangeable acidity and the content of mobile manganese in the soil of most treatments limed with dolomite particles of various sizes. However, the relationship between the content of mobile Mn in soils and the value of hydrolytic acidity was proved by paired linear regressions. Regardless of the dose and size of dolomite particles added, the soil was highly and moderately supplied with plant available manganese during the entire study period.
Keywords: Retisol, dolomite screenings, manganese, hydrolytic acidity, dependency.
Introduction
Manganese (Mn) is an important micronutrient for plant growth and development in metabolic processes in a plant cell. Mn is one of the most abundant metals in soil and comprises about 0.1 % of the Earth's crust (Emsley, 2003; Al-loway, 2008). In Albic Retisols (IUSS, 2014), the concentration of mobile manganese ranges from 0.008 to 0.4 mmol (eq)/100 g of soil. Its amount depends on many factors, including total reserves of Mn in soil, soil acidity, concentration of exchangeable hydrogen, water and air regime of soil (Behera and Shukla, 2014; Rengel, 2015), as well as particle size distribution (Nebolsin and Nebolsina, 2010; Alejandro, Höller, Meier, and Peiter, 2020).
The mobility of manganese increases from soils with an alkaline reaction to neutral and further to acidic soils (Lukin, Avramenko, and Melentsova, 2006; Behera and
Shukla, 2014; Rengel, 2015; Alejandro, Holler, Meier, and Peiter, 2020; Jatav et al., 2020). Its solubility depends on soil redox condition, pH, organic matter, clay fraction etc. Diatta et al. (2014) found that among studied four microelements the Mn was the least available to crops in the following order: Zn < Cu < Fe < Mn. The correlation coefficient between pHKCl and logMn for soils of different particle size distribution ranges from 0.10 to 0.35. In the specific conditions of an individual experiment, the closeness of the correlation between pHKCl and logMn is much more significant: R=- 0.74 - 0.80 (Nebolsin and Nebolsina, 2002). Solubility of Mn in soils generally decreases with the increasing pH due to adsorption-precipitation, i. e., oxidation-reduction reactions (Haynes and Swift, 1985; Sparks, 2003; Rengel, 2015). Although Mn belongs to the class of low toxicity for soil living organisms (Pronko et al., 2022), an excess of available manganese in the soil can lead to its actual and potential toxicity to plants, while an increase in soil pH due to liming can lead to Mn unavailability to plants (Alejandro, Holler, Meier, and Peiter, 2020; Jatav et al., 2020).
Albic Retisol is an acid soil formed on unconsolidated glacial till under percolation water regime and therefore with high rates of cation leaching (Meng et al., 2019). In particular, after liming, arable Albic Retisols quickly lose their basic cations (Litvinovich et al., 2022) and after two years there is a gradual return to the initial pH level (Shilnikov, 1991). To characterize soil acidity, a different set of intensive and extensive indicators is used. Hydro-lytic (pH-dependent) acidity is the sum of exchangeable acidity and active acidity due to H+ ions, which are released from the pH-dependent positions of the soil absorbing complex. This acidity appears at lower pH values and characterizes the entire possible spectrum of acids present in the soil. It is also determined in the extracts of hydrolytically alkaline salts (Chesworth, 2008).
The dumps of dolomite screenings from stone processing, accumulated near former and existing quarries in Leningrad region, are considered unsuitable for use in agriculture, since the size of these screenings is large and therefore considered to be of low activity. These dolomite particles have different chemical composition, density and porosity, so their dissolution rate and duration of action will vary. The dissolution rate of large dolomite particles during prolonged composting with strongly acidic Albic Retisols was studied in (Litvinovich et al., 2021). They showed that the process of dissolution of large particles of dolomite in the soil affects only the outer layers of the particles. As a result, the particles gradually decrease in volume, and the duration of the ameliorant action increases. The working hypothesis of the study was based on the fact that the fineness of grinding affects the dissolution rate of the ameliorant, and liming in general leads to a deficiency of manganese available to plants (Gupta, Macleod, and Macleod, 1973; Nebolsin and Nebolsina, 2002, 2010; Diatta et al., 2014; Ijaz et al., 2021). The tasks of this work were: 1) to reveal the
relationship between soil acidity indicators (pHKCl and Hy) and the content of mobile Mn in Albic Retisol in a long-term field experiment; and 2) to assess the ability of soil limed with dolomite particles of various sizes to meet the needs of plants for manganese in a long aftereffect.
Materials and methods
Experimental design and study site
In the microfield experiment, the effect of dolomite screening fractions from the Elizavetino deposit (Gatchin-sky District of the Leningrad Region, Fig. 1; N 59°29'33", E29°45'51") less than 0.25 mm in size (dolomite flour — DF); 0.25-1 in size (D); 1-3 (D) and 3-5 mm (D) and their combinations (Fig. 2) was studied on Albic Retisol (IUSS, 2014). Plots without the use of ameliorant and with the use of standard limestone flour (LF) added at a dose equivalent to the dolomite screenings served as controls. The doses of dolomite were calculated based on the hydrolytic acidity (Hy). The inclusion of treatments with a mixture of dolomite particles of different sizes in a deliberately overestimated doses (3, 4, and 6 Hy, plots No. 7, 8 and 9) was based on the known fact that the fineness of grinding affects the dissolution rate of the ameliorant. It was assumed that the fraction < 0.25 mm, added at a dose of
0.5.Hy, would dissolve immediately after application. The rate of dissolution of 0.25-1 mm fraction will be lower and the fraction 1-3 mm in size will have a reclamation effect at later stages of the experiment (Litvinovich et al., 2022) since particles of lime larger than 1 mm are inert and have a weak reclamation effect (Musil and Pavlicek, 2002).
The inclusion of the treatment using an overestimated dose of dolomite particles with a size of 3-5 mm (treatment No. 10) was based on the fact that with an increase in the dose of ameliorant, the effect of the fineness of grinding is levelled. The experiment was initiated in 2011 and included the following treatments:
1. Control (NPK)
2. NPK + LF (< 0.25 mm, 1 Hy)
3. NPK + D (< 0.25 mm, 1 Hy)
4. NPK + D (0.25-1 mm, 1 Hy)
5. NPK + D (1-3 mm, 1 Hy)
6. NPK + D (3-5 mm, 1 Hy)
7. NPK + D (< 0.25 mm, 0.5 Hy) 0.5 Hy) + D (1-3 mm, 2 Hy)
8. NPK + D (< 0.25 mm, 0.5 Hy) 0.5 Hy) + D (1-3 mm, 3 Hy)
9. NPK + D (< 0.25 mm, 0.5 Hy) 05 Hy) + D (1-3 mm, 5 Hy)
10. NPK + D (3-5 mm, 5 Hy),
Where, NPK fertilizer is NH4H2PO4 + NH4NO3 + KCl; LF is a limestone flour; 1Hy is a full dose of lime determined by the hydrolytic acidity; D is dolomite.
+ D (0.25-1 mm, + D (0.25-1 mm, + D (0.25-1 mm,
Fig. 2. Size partitioning of dolomite screenings form the dump.
Analytical and crop growing approaches
The methodology of the microfield experiment was as follows: vessels of 40 litres capacity without a bottom were buried into the soil to the depth of 50 cm (Fig. 3). 40 kg of soil, calcified with various fractions of dolomite screening at a full dose of Hy (8.4 t/ha), were placed in the vessels. Crops responsive for liming and with high demand for calcium and magnesium have been grown throughout the experimental years. In 2011 — rapeseed (Brassica napus, L.), in 2012 — vetch and mustard (Vicia and Sinapis alba, L.), in 2013 and 2014 — beans and mustard (Vicia fdba and Sinapis alba, L.). Since 2015, acid-tolerant timothy (Phleum pratense, L) has been included in the range of cultivated crops. In 2015, barley (Hordeum vulgare, L) with over-sowing of timothy. In 2016 and 2017, timothy was harvested twice each year, and in 2018 one harvest was carried out. Altogether, 13 experimental phases were performed and analysed. Plants were harvested in the flowering phase. The concentration of plant available manganese in the soil was established after harvesting each crop (13 determinations).
When setting up the experiment, the soil was fertilized with NPK in an amount of 48 g per vessel. In addition, before sowing the plants, NPK was used annually at a rate of 6 g per vessel. The soil exchangeable acidity (pH) in a 1 M KCl solution was determined potentiometrically, and hydrolytic acidity (Hy) was determined with the Kappen method (Kappen, 1929): 0.5 M dm-3 Ca-acetate solution adjusted to pH 8.2 was added to the soil in the ratio of 1 : 2.5. After 1 hour of shaking the suspension was filtrated and followed by titration with 0.1 M dm-3 NaOH solution. The Htotal values were calculated from the amount of alkali consumed (0.1 M dm-3 NaOH cm3 for 50 g soil). Manganese was extracted from the soil and the pHKCl of the solution was brought to 5.6 units with an ammonium acetate buffer (AAB pH 4.8). Determination of Mn was carried out on a Varian "Spectr AA 240 FS" atomic adsorption spectrophotometer by flame atomization. Hydrolytic acidity (Hy) was determined by the Kappen method using CH3COONa with pH 8.2 (Novitsky et al., 2021). The statistical differences between the treatments were described using the standard deviation, t-test and regression analyses. Empirical processing of the data was carried out according to Bure (2007).
Fig. 3. General view of the microfield experiment.
Results
The gross chemical composition of the soil was given earlier in Litvinovich et al. (2022). The physicochemi-cal characteristics of the soil were: pHKCl — 4.2; Hy — 5.6 mmol (eq)/100 g soil; humus -1.76 %; particles
< 1 mm — 21.2 %; content of exchangeable Ca and Mg -1.54 and 0.34 mmol (eq)/100 g soil, respectively. Content of plant available manganese -32 mg/kg soil. The high acidity of the studied soils is a hereditary property, mainly associated with the state of waterlogging and the history of fertilization.
The data on the dynamics of pHKCl and Hy for 13 experimental phases are given in Tables 1 and 2. The results show that the effect of dolomite particles
< 0.25 mm on soil pHKCl and Hy was recorded over 8 experimental years. The return to the initial value of pHKCi and Hy upon liming with dolomite particles 0.25-1 and 1-3 mm in size was established after 8 experimental years, while the effect of 3-5 mm fractions at a dose of 1 Hy on soil acidity indicators was traced for 7 experimental years. Table 3 shows the dynamics of plant available manganese in the soil. In the treatments using only mineral fertilizers, the concentration of mobile Mn changes in an increasing amplitude with a statistically insignificant rate.
Regardless of the treatment with liming, the maximum change in the concentration of Mn was achieved in the year of aftereffect and depended on the size of particles and the dose of dolomite application. Further, an increase in its concentration began. The effect of using particles less than 0.25; 0.25-1 mm; 1-3 and 3-5 mm at a dose of 1 Hy lasted for at least 6-7 experimental phases, and the effect of using mixtures of fractions in an amount corresponding to 3, 4 and 6 Hy doses, lasted for the entire observation period.
Linear models of the content of mobile manganese depending on pHKCl are presented in Table 4. A statistically significant change in the content of mobile manganese with a change in pHKCl value over the entire study period was established for the treatments with LF (limestone flour), dolomite particles of < 0.25; 0.25-1 and 1-3 mm in size, as well as a mixture of these fractions at a dose of 3 Hy.
The linear dependences of the mobile manganese on the pHKCl value in the treatments 1, 5, 6, 8, 9, and 10 imply that for these treatments a statistically significant change in the manganese content with a change in the pHKCl value on average was not observed over the entire interval of the experimental years.
On the contrary, paired linear regressions of the dependence of the mobile Mn on hydrolytic acidity (Hy) revealed a different trend. In this case, only in the treatment using NPK only, a significant statistical relationship between these indicators was not found, while in
all other treatments, the dependency of Mn and Hy was significant (Table 5).
Discussion
There are numerous studies showing that liming, in general, leads to a decrease in the mobility of manganese in soils (Gupta, Macleod, and Macleod, 1973; Nebolsin and Nebolsina, 2002, 2010; Litvinovich, Kovleva, and Pavlova, 2015; Litvinovich et al., 2021; Ijaz et al., 2021). The variation in the content of manganese can be associated with the level of soil acidity, where 92.4 % of the change in the content of manganese available to plants in soils occurs due to the changes in soil pH (Nebolsin and Nebolsina, 2010). In our study, the maximum decrease in the mobility of Mn was observed at pHKCl value of 6.5-7.2. This level of reaction corresponds to the formation of oxides Mn2O3 and MnO in soils with normal moisture, which have low solubility. When moist soils are limed excessively, precipitation occurs at pHKCl value of 8-9 units due to the formation of Mn(OH)2 and MnCO3 (Nebolsin and Nebolsina, 2010). Moreover, Kessick and Morgan (1975) found that at pH > 8, manganese is able to start auto-oxidation which leads to a reduction in mobility. As mentioned earlier, among three oxidation states (Mn(II), Mn(III), and Mn(IV)) crops uptake only the divalent Mn (Mn2+) (Fageria, Stone, and Moreira, 2008; Dabkowska-Naskret and Jaworska, 2013; Ijaz et al., 2021). At about neutral pH, oxidation of soluble Mn(II) to hardly soluble Mn(IV) occurs. At the lower pH values the insoluble MnO2 is reduced to the plant-available Mn2+ form through biological or chemical processes due to the presence of protons and electron-carrying reducing agents produced by plant roots, microorganisms, or through organic matter decomposition (Uren, 1981; Di-Ruggiero and Gounot, 1990; Rusin and Ehrlich, 1995).
Vondrackova et al. (2013) found no effect of dolomite and lime application on plant available concentrations of Mn. However, concentrations of acid extractable Mn slightly decreased under dolomite application and greatly decreased under lime application in the studied alluvial soils with the initial soil pH ranging from 6.5 to 7.3 which is substantially higher than the soil studied in our experiment. Under addition of CaCO3 a chemical sorption of Mn followed by precipitation of MnCO3 occurs (Bradl, 2004; Otero et al., 2009). Although the study of Vondrackova et al. (2013) lasted for 42 days of incubation experiment, this indicates once more that Mn transformations due to liming are highly sensitive in acid and very acid soils, and at a high soil pH the mobility of Mn is generally low (Adriano, 2001).
One of the objectives of this study was to establish an average (calculated) value of the change in the concentration of mobile Mn in the soil that corresponds to a decrease in pHKCl and an increase in Hy over the entire study interval. Data analysis showed that the dynamics
Table 1. Dynamics of pHKCl over 13 experimental phases
Tretment Test-year
1 2 3 4 5 6 7 8 9 10 11 12 13
1 Control (NPK)* 3.95a 3.85a 4.10a 4.00a 3.83a 3.60a 3.92a 3.40a 3.76a 3.58a 3.70a 3.70a 3.40a
2 NPK + LF (< 0.25 mm, 1 Hy) 5.32b 4.95b 4.90b 4.70b 4.34b 4.10b 4.44b 4.00b 4.13b 3.95b 4.20b 4.03ab 3.80b
3 NPK + D (< 0.25 mm, 1 Hy) 5.45b 5.12c 5.15c 4.95c 4.58c 4.22c 4.74c 4.1 Obc 4.19b 3.95b 4.30bc 3.93a 4.10b
4 NPK + D (0.25-1 mm, 1 Hy) 5.13c 5.05bc 5.32d 5.10d 4.80d 4.33d 4.90d 4.00b 4.16b 3.90b 4.40bc 4.1 Oab 3.80b
5 NPK + D (1-3 mm, 1 Hy) 4.62d 4.42d 5.00bc 4.85bc 4.40bc 4.15bc 4.58bc 3.90b 4.13b 3.98b 4.30b 4.1 Oab 3.90b
6 NPK + D (3-5 mm, 1 Hy) 4.60d 4.05e 4.40e 4.45e 4.38e 3.95e 4.26b 3.80cb 4.11b 3.95b 4.1 Od 3.90ac 3.80b
7 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 2 Hy) 5.82e 5.75f 6.1 Of 6.00f 5.63f 5.60f 6.1 Of 5.Od 5.23c 5.08c 5.70e 5.50d 5.50c
8 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 3 Hy) 5.95e 5.85f 6.30g 6.30g 5.93g 5.80g 6.40f 5.50e 5.80d 5.63d 6.20f 6.00d 5.90cd
9 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 5 Hy) 6.1 Oef 6.00fg 6.40g 6.40h 6.20h 6.1 Oh 6.63f 5.85f 6.00d 6.08e 6.40g 6.30e 6.1 Oed
10 NPK + D (3-5 mm, 5 Hy) 5.35b 4.85b 5.70h 5.65i 5.12i 5.20i 5.71 f 4.80d 5.00c 5.23c 5.70e 5.40ac 5.40cd
* The letters within a column signify a statistically significant difference as confirmed by f-test at P< 0.05 level; LF — limestone flour; NPK — mineral fertilizer; Hy — hydrolytic acidity; D — dolomite fraction.
Table 2. Dynamics of hydrolytic acidity (Hy) over 13 experimental phases, mmol (eq) 1001 g of soil
Treatments Test-year
1 2 3 4 5 6 7 8 9 10 11 12 13
1 Control (NPK)* 5.42a 5.58a 5.04a 4.52a 5.01a 5.86a 6.48a 7.52a 6.79a 6.77a 6.97a 5.35a 9.91a
2 NPK + LF (< 0.25 mm, 1 Hy) 2.65b 3.23b 3.08b 2.92b 4.35b 4.16b 4.68b 5.32bc 5.31b 5.85bc 5.10b 4.51b 7.37bc
3 NPK + D (< 0.25 mm, 1 Hy) 2.54bc 2.86c 2.76b 2.68bc 3.54c 4.14b 4.10b 5.23b 5.37b 5.32b 5.03bc 5.17a 5.82c
4 NPK + D (0.25-1 mm, 1 Hy) 3.41 d 3.09b 2.66b 2.58bc 2.94d 4.70b 4.11b 5.97bc 5.06b 5.80bc 4.74c 4.50b 4.83bc
5 NPK + D (1-3 mm, 1 Hy) 4.45e 4.25d 3.00b 3.03b 3.79c 4.40b 4.81b 5.93bc 5.26b 5.58bc 5.01 be 4.54b 4.59bc
6 NPK + D (3-5 mm, 1 Hy) 5.35a 5.34e 4.72a 3.82d 5.01a 4.70a 6.29a 7.28a 5.88cb 6.07c 5.93d 5.26a 4.63c
7 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 2 Hy) 2.16bc 2.05f 1.71c 1.30e 1.45e 1.78c 2.03c 3.39d 2.39d 3.11 d 2.24e 2.43c 1.85d
8 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 3 Hy) 2.02bc 1.90f 1.50c 1.16e 1.31e 1.55cd 1.63cd 2.56e 1.43e 2.40e 1.49f 1.32d 1.33d
9 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 5 Hy) 1.80c 1.64g 1.28c 1.01 e 0.99e 1.28cd 1.54cd 1.86e 1.46e 2.06e 1.26f 1.09d 1.23d
10 NPK + D (3-5 mm, 5 Hy) 4.17e 3.72h 3.08b 2.41 cd 3.26cd 2.75e 3.04e 3.95d 3.55f 2.84d 2.62g 2.36c 2.00d
* The letters within a column signify a statistically significant difference as confirmed by f-test at P< 0.05 level; LF — limestone flour; NPK — mineral fertilizer; Hy — hydrolytic acidity; D — dolomite fraction.
Test-year
1 2 3 4 5 6 7 8 9 10 11 12 13
1 Control (NPK)* 43.08a 22.68a 26.38a 38.55a 32.17a 30.3a 49.97a 38.86a 21.84a 19.72a 17.02a 19.99abc 23.19a
2 NPK + LF (< 0.25 mm, 1 Hy) 20.78b 8.96bc 17.83b 18.00bd 22.18b 25.1b 40.65b 44.07a 31.70bc 26.95b 20.54bc 20.57abc 30.77bc
3 NPK + D (< 0.25 mm, 1 Hy) 21.92b 8.67bc 16.40b 15.65b 16.54c 25.6b 30.95c 49.98cde 36.03b 28.95b 21.31b 25.57b 28.64ac
4 NPK + D (0.25-1 mm, 1 Hy) 29.01c 9.49c 17.13b 12.44c 14.73c 20.7c 29.00c 44.45ac 34.98b 25.76b 17.47a 21.58ab 30.49bc
5 NPK + D (1-3 mm, 1 Hy) 36.81 da 12.58d 16.55b 19.78bd 19.05bc 24.8b 31.81c 46.17ad 33.31b 25.57b 18.75ab 17.60ac 27.90ab
6 NPK + D (3-5 mm, 1 Hy) 40.94a 17.85e 23.50c 27.00e 25.10b 29.0a 40.14b 46.15ae 27.30ac 24.84a b 18.46ac 15.65c 24.19ab
7 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 2 Hy) 14.87e 7.87bf 13.85de 8.06f 7.91 d 11.9d 14.81de 31.24abg 21.37a 18.01a 10.48de 16.05ac 20.46ad
8 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 3 Hy) 15.13e 7.19f 14.53d 9.46f 8.77d 14.0d 15.45de 18.84f 11.51d 17.46a 9.29d 8.87d 13.73d
9 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 5 Hy) 15.01e 7.23f 12.48e 9.88cf 7.39d 12.5d 13.66d 11.92f 12.17d 14.88a 10.88de 9.37d 15.14d
10 NPK + D (3-5 mm, 5 Hy) 33.08dc 10.66c 14.68d 12.59c 13.58c 14.8d 21.68de 29.41 g 19.45a 16.44a 11.88e 9.66d 14.14d
LSD 4.03 1.49 1.63 2.82 4.91 3.1 7.59 8.63 5.97 5.73 2.38 6.09 7.24
* The letters within a column signify a statistically significant difference as confirmed by f-test at P< 0.05 level; LF — limestone flour; NPK — mineral fertilizer; Hy — hydrolytic acidity; D — dolomite fraction.
SOIL BIOLOGY
Table 4. Empirical dependence of the manganese concentration in Albic Retisol on the pHKCl value
No. Treatments Model equation b Significance p-value Coefficient of determination
1 control (NPK) y 11 = -25,6 + 14,7 • X Non-significant 0.3 R2 = 0.097
2 NPK + LF (1 Hy) y2.1 = 74.6 - 11.3 • x 11.3 Significant 0.056 R2 = 0.29
3 NPK + D (< 0.25 mm, 1 Hy) y3.1 = 81.2 - 12.4 • x 12.4 Significant 0.03 R2 = 0.36
4 NPK + D (0.25-1 mm, 1 Hy) y4.1 = 70.8 - 10.4 • x 10.4 Significant 0.046 R2 = 0.31
5 NPK + D (1-3 mm, 1 Hy) ys.1 = 65.7 - 9.35 • x Non-significant 0.245 R2 = 0.12
6 NPK + D (3-5 mm, 1 Hy) y6.1 = 2.28 + 6.15 • x Non-significant 0.57 R2 = 0.03
7 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 2 Hy) y7.1 = 87.7 - 12.9 • x 12.9 Significant 0.009 R2 = 0.48
8 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 3 Hy) y8.i = 40.1 - 4.6 • x Non-significant 0.26 R2 = 0.113
9 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 5 Hy) y9.1 = 13.6 - 0.31 • x Non-significant 0.94 R2 = 0.0006
10 NPK + D (3-5 mm, 5 Hy) y10.1 = 43.4 - 4.95 • x Non-significant 0.47 R2 = 0.049
Notes: b = the coefficient of the mean change in pHKCi value; LF — limestone flour; NPK — mineral fertilizer; Hy — hydrolytic acidity; D — dolomite fraction.
Table 5. Empirical dependence of the manganese concentration in Albic Retisol on the value of hydrolytic acidity (Hy)
No. Treatments Model equation b Significance p-value Coefficient of determination
1 control (NPK) y1.1 = -39,4 - 1,58 • X Non-significant 0.47 R2 = 0.047
2 NPK + LF (1 Hy) y2.1 = 6.4 + 4,19 • x 4.19 Significant 0.037 R2 = 0.338
3 NPK + D (< 0.25 mm, 1 Hy) y3.1 = -0.34 + 6.1 • x 6.1 Significant 0.009 R2 = 0.48
4 NPK + D (0.25-1 mm, 1 Hy) y4.1 = -2.4 + 6.2 • x 6.2 Significant 0.005 R2 = 0.53
5 NPK + D (1-3 mm, 1 Hy) ys.1 = -5.76 + 6.87 • x 6.87 Significant 0.02 R2 = 0.398
6 NPK + D (3-5 mm, 1 Hy) y6.1 = 0.83 + 4.97 • x 4.97 Significant 0.1 R2 = 0.225
7 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 2 Hy) y7.1 = -3.04 + 8.49 • x 8.49 Significant 0.0025 R2 = 0.58
8 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 3 Hy) y8.1 = 3.19 + 5.69 • x 5.69 Significant 0.013 R2 = 0.45
9 NPK + D (< 0.25 mm, 0.5 Hy) + D (0.25-1 mm, 0.5 Hy) + D (1-3 mm, 5 Hy) y9.1 = 6.27 - 3.84 • x 3.84 Significant 0.09 R2 = 0.235
10 NPK + D (3-5 mm, 5 Hy) y10.1 = -6.39 + 7.68 • x 7.68 Significant 0.008 R2 = 0.49
Notes: b = the coefficient of the mean change in pHKCl value; LF — limestone flour; NPK — mineral fertilizer; Hy — hydrolytic acidity; D — dolomite fraction.
of changes in the content of Mn and the dynamics of pH and Hy values were significantly nonlinear. But the use of paired linear regressions showed statistically significant outputs and made it possible to correctly assess the average variability of manganese content depending on the increase or decrease of other indicators (pH, Hy) over the entire study period. These results imply that the level of significance of the linear dependences of mobile manganese on the pHKCl among treatments implies that the value of exchangeable acidity, which characterizes the amount of acidic components passing into salt ex-
tracts from the constant positions of the soil-absorbing complex (SAC) is insufficient to reveal its interdependence with the content of mobile manganese in most of the treatments. On the contrary, paired linear regressions of the dependence of the mobile Mn on hydrolytic acidity (Hy) showed that the entire spectrum of acidic components present in the soil allows to reveal a relationship between the content of mobile manganese and Hy in all treatments with liming.
Another important issue that was raised at the start of the experiment is whether soil limed with dolomite
(especially in deliberately large doses) is capable to meet the needs of plants for manganese. According to the gradation given by Nebolsin and Nebolsina (2002), soils are subdivided into: very rich — 0.15 mmol (eq)/100 g of soil (41 mg/kg); rich — 0.08 mmol (eq)/100 g of soil (21.9 mg/kg); moderately supplied — 0.045 mmol (eq)/100 g of soil (12.3 mg/kg); poor — 0.02 mmol (eq)/100 g of soil (5 mg/kg). In the studied soil the content of plant available manganese compounds in all treatments falls within the range from very rich to medium-rich soils. Of the studied crops, mustard was the most sensitive to the content of manganese in the soil. In our study, the concentration of manganese in the limed plots significantly exceeded the lower limit of 1.62.2 mg/kg for this crop (Nebolsin and Nebolsina, 2002). Thus, the threat of manganese deficiency for plants from various biological families grown on soil reclaimed with dolomite particles has not been established.
Conclusions
• The amount of the initial soil components passing into the salt extracts (1N KCl) is not enough to reveal the relationship between the exchange acidity and the content of mobile manganese in the majority of the treatments limed with dolomite particles.
• Hydrolytic (pH-dependent) acidity allowed to reveal the relationship between the content of plant available manganese and the value of Hy in the soils of limed treatments.
• Regardless of the dose and size of dolomite particles added, the limed soil belonged to the category of highly and moderately supplied with plant available manganese throughout the entire study period.
• The relationship of Mn available to plants in limed soil requires the closest attention and further study, since due to the very high dynamism of the processes of transformation of manganese and the instability of its compounds of different valence in soils, inept human intervention can create either conditions for the manifestation of the toxicity of Mn, or its sharp deficiency as a nutrient.
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