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Article

Wood Biomass Ash (WBA) from the Heat Production Process as a Mineral Amendment for Improving Selected Soil Properties

by
Elżbieta Rolka
,
Andrzej Cezary Żołnowski
*,
Mirosław Wyszkowski
,
Weronika Zych
and
Anna Skorwider-Namiotko
Department of Agricultural and Environmental Chemistry, Faculty of Agriculture and Forestry, University of Warmia and Mazury in Olsztyn, Łódzki 4 Sq., 10-727 Olsztyn, Poland
*
Author to whom correspondence should be addressed.
Energies 2023, 16(13), 5110; https://doi.org/10.3390/en16135110
Submission received: 14 June 2023 / Revised: 29 June 2023 / Accepted: 30 June 2023 / Published: 2 July 2023
(This article belongs to the Special Issue Renewable Energy, Environmental Quality and Sustainability)
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Abstract

:
This research concerned the possibilities of the natural management of ash, which is a waste product obtained in the process of burning wood chips in a bio-heating plant. The basis of the research was a pot experiment, which was carried out in a greenhouse of the University of Warmia and Mazury in Olsztyn, Poland. This experiment dealt with the influence of increasing doses of wood biomass ash added to soil on selected soil properties. The soil used for the pot experiment was taken from the arable layer (0–25 cm) of the soil. It was characterized by acidic reaction, low salinity, and an average content of total carbon (TC). The test plant was corn. Soil analysis after plant harvest showed an increase in pH and a significant improvement of soil sorption properties, without causing an excessive increase in soil salinity. In addition, a significant increase in the content of available K, P, and Mg was observed, which at the highest dose of WBA reached: 121.9; 109.3, and 41.33 mg kg−1 of soil, respectively. The content of trace metals: iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), cadmium (Cd), lead (Pb), cobalt (Co), chrome (Cr), and nickel (Ni) in the soil was quite varied but did not exceed the permissible values for agricultural soils. The content of available forms of these trace metals at the highest dose of WBA was, respectively, 1004, 129.9, 8.70, 2.08, 5.54, 0.195, 1.47, 0.97, and 1.92 kg−1 of soil. The results confirmed the significant fertilizing potential of wood biomass ash.

1. Introduction

The growing demand for energy, the shrinking resources of fossil fuels, and the desire to reduce CO2 emissions related to the combustion process encourage the search for new sources of energy. Researchers are particularly interested in the so-called renewable energy sources (RES). According to McKendry [1] and Basu et al. [2], the use of RES has an important function in counteracting global warming. This is an important issue for sustainable development and, consequently, the replacement of fossil fuels [3]. One of the renewable energy sources is biomass [3,4], considered a neutral fuel source in terms of CO2 emissions [4]. Biomass can be used as an independent fuel or it can be co-combusted with hard coal [5]. Among other substances, wood and wood waste are used as biomass [3]. At present, biomass is one of the basic sources of renewable energy in the power industry in Poland. According to Poland’s Energy Policy, it is planned to increase the share of renewable energy to 20% by 2050 in all energy sources consumed [5]. The growing use of biomass for energy purposes generates increasing amounts of wood biomass ashes (WBAs) produced in the combustion process [6]. WBAs from thermal processes, in accordance with the Regulation of the Minister of Climate on 2 January 2020 on the catalog of waste [7], in Poland, same as in the European Union countries, are treated as waste and should be deposited on landfills. However, this solution is expensive and, in the case of WBAs, leads to the loss of valuable resources [6]. The reuse of WBAs in agriculture is an important issue related to nutrient cycling and saving mineral fertilizers [8]. In the context of the growing demand for mineral fertilizers, we must pay more attention to mineral waste with significant fertilization potential.
However, for the soil application of WBA to be a safe procedure, not only its fertilizing potential but also its possible negative impact on the soil should be considered. WBAs are characterized by a seasonal variability of properties [9] and their composition varies depending on their origin [10,11,12] and the applied combustion process technology [11]. The fertilizing potential of WBAs is the effect of the significant amounts of macronutrients that they contain [3,6,13,14], including micronutrients [13]. WBAs are generally characterized by a high content of calcium (Ca), potassium (K), phosphorus (P), sulfur (S) [12], manganese (Mn), zinc (Zn), and copper (Cu), which can suggest their suitability for agricultural use [10]. According to the literature data [9,12,14], WBAs contain relatively low quantities of harmful elements, such as arsenic (As) and lead (Pb), except for WBAs from the combustion of certain tree species, which can be a significant source of cadmium (Cd) [15] or Pb [10]. Despite the diversity of composition, WBAs share some features, such as their alkaline reaction [10,16] and low organic carbon content [10].
According to the literature, the application of WBA to soil enhances the soil’s physical properties [17] by improving its texture, reducing density, optimizing the pH value [13,14,17,18,19,20,21], and increasing the buffer capacity of the soil [13,18]. In addition, WBAs promote soil aeration [13,18], improve permeation, water retention [13,18,22], and porosity [22], and reduce soil crusting [13]. The addition of WBA to soil increases the content of organic carbon and essential nutrients for plants [22], including Mg [19,21,23], K, P, Ca [18,21,23], Na, and S [19] and micronutrients Zn [18,19], Fe, Cu, Mn [18], and B [18,23]. The use of WBA, by changing the sorption properties [24] and alkalization of soils, can reduce their content of exchangeable aluminum [10] and additionally reduce the mobility of heavy metals [13,18]. Moreover, according to some researchers [2,18], using WBAs instead of limestone for soil deacidification can reduce CO2 emissions to the atmosphere, which, although to a small extent, will limit global warming. The addition of WBA to soil improves the species composition of soil microorganisms, stimulates their activity, and consequently increases soil fertility [16]. According to Pandey and Singh [13], the adverse effects associated with the use of WBA include a decrease in the bioavailability of some nutrients under high pH values, as well as soil salinity, which may occur due to long-term use of ashes [17]. The presence of alkali metals, as well as Cl, S, and Si, in WBAs effects the lower reactivity and mobility of nutrients after WBA introduction into the soil [4]. According to Uliasz-Bocheńczyk et al. [5], WBAs are characterized by high leachability of sulfates, chlorides, chromium, and potassium, which may limit their use in agriculture. Research by Demeyer et al. [23] indicates that the use of WBAs in agriculture and forestry does not pose a significant threat to the environment provided that excessive doses of WBAs are avoided and WBAs from uncontaminated wood residues are used. According to Pandey and Singh [13], WBAs can be used on degraded soils. However, the use of WBAs should be preceded by research on their properties and the monitoring of soil conditions and crop quality [2].
Despite numerous studies on the impact of WBAs on soil properties, opinions of researchers as to the advisability of their use are still divided. Due to the variable composition of WBAs and the diverse impact on the soil, it is reasonable to research this issue. In the face of the increasing use of biomass in the energy and heating sectors, a research model must be developed that will allow WBAs to be utilized in a natural environmentally safe manner. The environmental utilization of WBAs should enable the process of transforming biomass into energy to be conducted in accordance with the principles of a circular economy. Based on the literature data and the nature of WBAs used in this research, a research hypothesis was formulated in which a positive effect of WBA was expected on selected soil properties, total carbon (TC) content, and available forms of macronutrients (P, K, and Mg), while maintaining the normative levels of conductivity (EC) and the content of trace elements in the soil, against the null hypothesis that WBA had no such effect or that WBA had a negative impact on the soil.

2. Materials and Methods

2.1. Description of the Experiment

The research was based on a pot experiment carried out in a greenhouse of the University of Warmia and Mazury, with the use of corn (Zea mays L.) as the experimental plant. In the study, the effect of increasing doses of ash from wood biomass (WBA) was assessed as the following treatments: T0 without WBA, T1 (15), T2 (30), T3 (45), T4 (60), T5 (75), and T6 (90 g of WBA pot−1) on selected soil properties. The adopted WBA treatments corresponded with 0, 5, 10, 15, 20, 25, and 30 Mg of WBA doses per area of 1 ha, respectively. The experiment was carried out in 3 replications. In total, the experiment included 21 objects. Polyethylene pots were filled with 9 kg of soil thoroughly mixed with WBA according to WBA treatments; mineral fertilizers (NPK) were applied once at a dose of 0.112 g N, 0.067 g P, and 0.134 g K kg−1 of soil for each treatment. WBA was introduced to the soil in the dry form and fertilizers were applied as liquid solutions. Nitrogen was used in the form of urea 46% N (Zakłady Chemiczne Police S.A., Szczecin, Poland), phosphorus in the form of potassium dihydrogen phosphate (EUROCHEM BGD Sp. z o.o., Tarnów, Poland), and potassium as potassium dihydrogen phosphate (EUROCHEM BGD Sp. z o.o., Tarnów, Poland) and potassium sulfate pure p.a. (PPH “POCh” SA Gliwice, Poland). Corn (Zea mays L.) of medium-early cv. LG 3252 (F/D, FAO 250) (Limagrain Polska sp. z o.o., Poznań, Poland) was sown in the pots and cultivated for 66 days. The plants were harvested in the BBCH53 phase (panicle development). After the plants were harvested, a representative soil sample was taken from each pot for further analysis.

2.2. Characteristics of the Soil Used in the Experiment

The starting soil for the research was taken from the Ap-horizon (0–25 cm) of an arable field of the Research Station in Tomaszkowo near Olsztyn (53°42′35″ N, 20°26′01″ E). The soil originating from loamy sand [25] was classified as Cambisols/brown soils according to the World Reference Base for Soil Resources (FAO/WRB) [26]. Basic soil properties are listed in Table 1.
The content of trace metals in the starting soil (Table 2) was within the limits of natural content for soils in Poland [27]; among the trace metals, Fe and Mn dominated.

2.3. Characteristics of Wood Biomass Ash Used in the Experiment

The wood biomass ash (WBA) tested in the experiment (Figure 1a) was obtained as a waste product from the combustion of mixed wood chips, with a dominant share of Scots pine (Pinus sylvestris L.), in a bio-heating plant of the Municipal Heating Energy Company in Olsztyn (MPEC Olsztyn) (Figure 1b). The bio-heating plant was put into operation in 2019 and it burns approximately 50,000 Mg of wood chips annually.
The characteristics of the WBA properties are shown in Table 3 and the content of trace metals is shown in Table 4.

2.4. Description of Analytical Methods

Raw WBA samples collected at MPEC Olsztyn were transferred to the laboratory of the Department of Agricultural and Environmental Chemistry at the UWM in Olsztyn. After drying in open air, they were crushed in a mortar for homogenization. The samples prepared in this way were analyzed.
The following properties were determined in the samples: reaction (pH), electrical conductivity (EC), sum of base cations (SBC), hydrolytic acidity (HAC), content of total carbon (TC), total nitrogen (Ntot), content of total forms of macronutrients (P, K, Mg, Ca, and Na) and their available forms (P, K, and Mg), as well as the near-total content of trace metals (Fe, Mn, Zn, Cu, Ni, Pb, Cd, Cr, and Co).
Soil analysis was performed before setting up the experiment and after its completion. In both cases, the soil samples were dried in open air, passed through a sieve with a mesh size of 2 mm, and additionally ground in a mortar.
The following properties were determined in the samples: soil reaction (pH), electrical conductivity (EC), sum of bases (SBC), hydrolytic acidity (HAC), content of total carbon (TC), total nitrogen (Ntot), and content of available forms of macronutrients (Pav, Kav, and Mgav), as well as near-total and available forms of trace metals (Fe, Mn, Zn, Cu, Ni, Pb, Cd, Cr, and Co).
In both WBA and soil samples, the pH was determined by the potentiometric method in a KCl solution with a concentration of 1 mol dm−3, using a pH 538 laboratory pH meter and a WTW electrode (WTW, Wrocław, Poland) [28]. EC conductivity method using the HANNA HI8733 conductivity meter (Hanna Instruments, Leighton Buzzard, the United Kingdom); HAC and SBC by the Kappen method [28]. Content of TC was determined on a TOC Analyzer (Shimadzu Corporation, Kyoto, Japan) with an SSM-5000A (Solid Sample Module) adapter. Ntot was assayed with the Kjeldahl distillation method after prior mineralization of ash and soil in concentrated sulfuric acid (VI) with the addition of hydrogen peroxide as a catalyst. Wet digestion of samples was performed in a speed digester K-439 digestion furnace (BÜCHI Labortechnik AG, Flawil, Switzerland) equipped with a scrubber K-415 vapor absorber (BÜCHI Labortechnik AG, Flawil, Switzerland). Nitrogen distillation was performed using a K-355 steam still (BÜCHI Labortechnik AG, Flawil, Switzerland) [29].
The content of total forms of macronutrients in WBA was determined in the same mineralized samples as for the determination of Ntot. The P content was determined spectrophotometrically using the vanadium–molybdenum method [30]. Mg content was determined with atomic absorption spectrometry (AAS); K, Ca, and Na were determined with flame atomic emission spectroscopy (FAES) on an AA240FS fast sequential atomic absorption spectrometer (Varian Inc., Mulgrave, Australia).
The content of available forms of macronutrients (P and K) in WBA and in the soil was determined by the Egner–Riehm method [31] and Mg by the Schachtschabel method [30].
The content of trace metals (forms near total) Fe, Mn, Zn, Cu, Cd, Pb, Ni, Cr, and Co in WBA and in the soil were determined after wet mineralization of the samples using a MARS 6 microwave oven (CEM Corporation, Matthews, NC, USA) in MARS Xpress Teflon vessels according to the US-EPA 3051 methodology [32,33]. Acid solutions (65% HNO3 and 38% HCl) were used in a ratio of 3:1 (v/v) for WBA and 1:3 (v/v) for soil mineralization.
The content of available forms of trace metals in the soil Fe, Mn, Zn, Cu, Cd, Pb, Ni, Cr, and Co was determined after extraction of the soil with 1 M HCl [28].
Both total and available forms of Fe, Mn, Zn, Cu, Cd, Pb, Ni, Cr, and Co were determined with the ASA method on an AA240FS fast sequential atomic absorption spectrometer (Varian Inc., Mulgrave, Australia) using standards (Fe 16596, Mn 63534, Zn 188227, Cu 38996, Cd 51994, Pb 16595, Ni 42242, Cr 02733, and Co 119785.0100) (Fluka Company, Charlotte, NC, USA).
The results were validated on the basis of the reference material CRM0120-50G (Trace Metals/Sandy Loam 2, SIGMA-ALDRICH Chemie GmbH, Schnelldorf, Germany) and CRM012-100G (Trace Metals/Fly Ash 2, SIGMA-ALDRICH Chemie GmbH, Schnelldorf, Germany).
Based on the determinations of hydrolytic acidity (HAC) and the sum of base cations (SBC), the cation exchange capacity (CEC) and base saturation (BS) of the analyzed ash and soil samples were calculated [34,35].

2.5. Description of Statistical Methods

The results were subjected to statistical analysis, which included the Pearson’s simple correlation coefficient (r), calculated using Microsoft Excel® for Microsoft 365 MSO (version 2206) (Microsoft, Redmond, WA, USA) [36]. The correlation coefficient was used to determine relationships between the examined properties. The results demonstrated the direction of the impact of increasing doses of WBA on the examined soil characteristics. The significance of the correlation coefficient (r) values was determined according to statistical tables [37]. To assess the impact of individual WBA treatments on the tested soil properties, the least significant difference test (LSD) was used by performing a one-way variance analysis ANOVA, with the help of Statistica® v. 13.3 PL software package (TIBCO Software Inc., Palo Alto, CA, USA) [38].

3. Results

3.1. Impact of WBA Application on the Selected Physicochemical Soil Properties

The results indicated a positive effect of the WBA application on the sorption properties of the soil (Table 5). In the soil analyzed after the experiment, significant positive correlations were found between the applied dose of ash and the sum of bases (SBC) (r = 0.899 **), cation exchange capacity (CEC) (r = 0.635 **), and base saturation (BS) (r = 0.978 **). This effect was observed in the whole range of WBA doses used. On the other hand, a negative correlation was shown for hydrolytic acidity (HAC) (r = −0.987 **), which resulted from the alkaline components supplied to the soil with WBA, mainly Ca and K (Table 3).
The positive effect of the WBA application to the soil was observed for the soil reaction (pH) (r = 0.980 **) (Figure 2a) and soil total carbon content (TC) (r = 0.918 **) (Figure 2b). The pH value increased from 4.26 (T0) to 5.64 (T6) due to the increased application of WBA. The TC content in the soil increased significantly after the application of WBA at doses ≥45 g pot−1 i.e., T3 and T5, except T4, where a decrease in TC content was noted. In the T0 treatment, the TC content in the soil was 5.32 g kg−1 and, with the addition of WBA (T1—T6 treatments), TC content was significantly higher and ranged from 5.50 g (T1) to 6.40 g TC kg−1 of soil (T6). The highest TC content (6.44 g kg−1 of soil) was recorded at treatment T5, where it was 1.12 g higher than the content in the control soil (T0). The use of WBA, as in the case of TC, at doses ≥45 g pot−1 (T3) resulted in a significant increase in EC (r = 0.853 **) (Figure 2c). A statistically significant increase in EC in relation to the control treatment (T0) was noted at the third dose of WBA (T3), where the EC value increased by 20 μS cm−1. The recorded increase in EC (salinity), however, did not induce any deterioration of soil properties. Even the highest EC value (74.63 μS cm−1) was within the limits defined by Cruz et al. [39], as values that characterized the majority of silty clay soils. The increase in both TC and pH values was a very beneficial effect from the environmental point of view.
The mean content of available macronutrients in the analyzed soil samples was 92.04 mg Kav, 97.49 mg Pav, and 34.59 mg Mgav kg−1 (Table 6) and was significantly positively correlated with the dose of WBA applied. The high Pearson correlation coefficients r = 0.747 **, 0.975 **, and 0.703 **, respectively, for Kav, Pav, and Mgav, indicated an evident contribution of WBA to the soil levels of nutrients. Although the correlations between the dose of WBA and the content of available components were highly significant, the statistically proven increase in the content of Kav and Mgav in the tested soils was obtained only under T5 and T6 treatments and, in the case of Pav, under T2 treatment. The most distinct increase was recorded for Kav, whose concentration in the soil under T6 treatment rose by 61% compared with the control soil (T0). The WBA applied as a soil amendment had a much smaller impact on the increase in Pav and Mgav content.
The results of the research showed numerous correlations between the content of Kav, Pav, and Mgav and the determined soil properties (Table 7). Soil reaction (pH), EC, SBC, and BS were highly significantly and positively correlated with the Kav, Pav, and Mgav content (0.585 ** > r > 0.965 **), in contrast with HAC, which was highly significantly but negatively correlated to these macronutrients (−0.958 ** > r > −0.708 **). Thus, as a result of the application of WBA to the soil, there was an increase in the available forms of the discussed macronutrients, which increased pH, EC, SBC, and BS values.

3.2. Impact of WBA Application on the Trace Metals’ Content in the Soil

WBA dosed to the soil, despite the high content of Fe, Mn, and Zn, did not lead to an unambiguous increase in the content of the total forms of these metals in the soil (Table 8). Increasing doses of WBA resulted in a significant increase in the content of total forms of Pbtot and Nitot (0.541 * > r > 0.574 *) and a highly significant increase in the content of Cdtot (r = 0.705 **). Under WBA treatment ≥45 g pot−1, i.e., T3–T6, a significant decrease in Crtot was shown. This significant impact was confirmed by the high negative Pearson correlation coefficient (r = −0.914 **) in relation to WBA treatments vs. Crtot.
The increasing doses of WBA had a different effect on the content of available forms of metals in the soil (Table 9). In this case, the WBA application resulted in a highly significant increase not only in Pbav and Niav (already after T1 application) but also in plant valuable Znav, under T4 and T5 treatment, and Cuav under T3, T5, and T6 treatments. A significant increase in the content of Coav under all WBA treatments was also shown. The significant impact of the applied WBA on the content of Pbav, Niav, Znav, Cuav, and Coav was confirmed by the high correlation coefficients, respectively, r = 0.777 **, 0.793 **, 0.678 **, 0.795 **, and 0.518 *. A very important observation in relation to the applied WBA pertained to the formation of the Cdav content. Although the content of total forms of Cdtot in the soil increased against the background of increasing WBA doses (Table 8), the content of available forms of this metal (Table 9) decreased (r = −0.696 *), especially under the influence of T5–T6 doses. In the case of Feav and Mnav, despite their high content in WBA, no significant changes were noted in the soil, regardless of the WBA treatment.
The analysis of the correlation between the total content of metals and the content of their available forms proved quite numerous, with significant relationships (Table 10). The most significant correlations were noted for the content of Cdtot, Crtot, and Pbtot. For Cdtot, significant positive correlations were found with the Znav, Cuav, Pbav, and Niav forms and to a lesser extent with Coav. On the other hand, negative correlations were shown for the forms of Cdav and Crav. In turn, Crtot showed a significant positive correlation with only Cdav and negative correlations with Znav, Cuav, Pbav, and Niav and to a lesser extent with Coav. On the other hand, Pbtot was highly significantly positively correlated only with the content of Pbav and to a lesser extent with Cuav and Niav and highly significantly negatively correlated with the content of Cdav. In the case of Cotot, Nitot, and Cutot, significant positive correlations were shown in the case of Coav and, in relation to Fetot, negative correlations with Mnav.
The change in soil properties under the increasing doses of WBA also caused numerous dependencies between the analyzed soil parameters and the content of available forms of trace metals in the soil (Table 11).
The increase in the EC value in the soil influenced the increase in the content of Znav, Cuav, Pbav, and Niav and these correlations were mainly highly significant (0.541 * < r < 0.707 **). The only negative but highly significant relationship was found between the EC value and the Crav content (r = −0.831 **). On the other hand, the increase in pH was highly significantly correlated with the content of Znav, Cuav, Pbav, and Niav (0.627 ** < r < 0.774 **) and significantly with the content of Coav (r = 0.486 *). The increase in pH was negatively related to the content of Cdav and Crav (−0.915 ** < r < −0.721 **). On the other hand, the change in sorption properties under the WBA application resulted in a positive mostly highly significant correlation between SBC, CEC, and BS and the content of Mnav, Znav, Cuav, Pbav, Niav, and Coav. Negative correlations were noted only between SBC, CEC, and Crav content, for which the r coefficient was: −0.840 ** and −0.560 *, respectively, and between BS and Crav and Cdav content (−0.936 ** < r < −0.597 **). An inverse relationship was noted for HAC. The reduced HAC value due to WBA application resulted in a negative and highly significant correlation with the content of Znav, Cuav, Pbav, and Niav (−0.782 ** < r < −0.694 **), negative and significant correlation with the content of Coav (r = −0.548 *), and positive with Cdav and Crav content (0.721 ** < r < 0.915 **). In turn, the increase in TC content in the soil was significantly positively correlated with the content of Cuav (r = 0.508 *) and Niav (r = 0.489 *) and highly significantly with Pbav (r = 0.584 **). On the other hand, there was a negative relationship between TC and the content of Cdav (r = −0.574 *) and Crav (r = −0.688).

4. Discussion

The assumed research hypothesis regarding the positive impact of WBA on soil properties was confirmed in many aspects. The results obtained in the present study confirmed the potential of WBA for soil application, as widely described in the literature [13,14,17,18,19,20,21]. First of all, a positive effect of WBA application on SBC, HAC, CEC, and BS was noted (Table 5), which was also confirmed in the research of Park et al. [21], Meller and Bilenda [24], and Ciećko et al. [40]. As in the present research, Meller and Bilenda [24] showed that fertilization with ashes caused an increase in SBC and BS and a decrease in HAC. Similarly, a three-year study by Park et al. [41] with the use of WBA showed a relative increase in the concentration of alkaline cations in the soil from 30 to 90% in relation to the control object. A more significant increase in BS in the Park et al. [41] investigation could have been caused by the length of the experiment, its nature, and the species of the cultivated plant. The beneficial and relatively long-term impact of WBA is comparable to the impact of hard coal fly ash (HCFA), the influence of which on soil properties was studied by Ciećko et al. [42]. The positive effect of WBA on the sorption properties observed in the present research and the cited studies [24,41] expressed an increase in the capacity of the sorption complex (CEC), which is not always confirmed in the literature. An example here may be the study by An and Park [21], in which the application of similar doses of WBA (5–20 Mg ha−1) did not increase the CEC.
The application of WBA to the soil, in addition to improving the structure of the sorption complex, including reduced HAC, increased the pH value of the soil, as in the studies of other authors [13,14,17,18,19,20,21,24]. The change in soil pH due to the use of WBA depends on the nature and type of soil [21]. The pH value of wood ashes (measured in H2O), found in the literature [14] ranges from 9.60 to 13.70, depending on the type of wood being burned. High pH values of ashes are often associated with high Ca content [16]. The ash used in the present research was characterized by pHKCl at the level of 10.31, which could be related to the high content of not only Ca but also K (Table 3). A similar increase in pH of a linear character was also noted by Szostek et al. [17] and Füzesi et al. [19]. On the other hand, in the study by Stankowski et al. [43], no increase in soil pH was observed, despite the more alkaline nature of that material than in the present research. This effect could have been caused by the morphological composition of the soil and its buffer properties. Light soils react much more strongly to the introduced WBA than heavy soils with greater buffering capacity. Ciesielczuk et al. [10] and Szostek et al. [17] drew attention to the potential risk associated with the excessive alkalization of soils, which may become a problem in the conditions of long-term use of ashes, especially in the case of light soils. Due to its deacidifying properties, some authors [16,44] reported the use of WBA on acidic soils, especially on medium and heavy soils [14] and agricultural and forest soils [45].
Among the positive aspects of the WBA application to the soil, an increase in the content of TC is noted in the literature [21,22]. The research conducted by Symanowicz et al. [14] indicated that the use of 1 Mg WBA ha−1 may result in an increase in soil fertility by about 160 kg of TC. WBA used in this present research was even richer in this component (Table 3), as 1 Mg of this material contained about 208 kg of TC. This quite high concentration of TC in WBA had a linear effect on the increase in the content of carbon pool in the soil against the background of increasing doses of ash (Figure 2b). In a study by Hansen et al. [46], WBA fertilization affected the biodegradability of organic matter in the soil, which consisted of enriching it with Fe and Al oxides and hydroxides while depleting quantities of carboxyl and aromatic groups. In turn, in the cited study by An and Park [21], a significant increase in the content of organic matter was observed as a result of the WBA application. According to Ciećko et al. [47], an increase in the carbon content in the soil after applying high doses of ashes (100–800 Mg ha−1 of soil) may have long-term effects, which were particularly visible in the topsoil. However, there are research results in the literature that have not confirmed the significant changes in the content of organic matter in the soil after the introduction of WBA. An example here may be the study by Stankowski et al. [43].
Apart from excessive alkalization of soils under the influence of WBA applications, some researchers have indicated a possible adverse impact of WBA on soil EC [13,22]. This problem is very important, because excessive soil salinity may deteriorate the conditions for the plant growth and plant root development. Wood ashes contain high concentrations of available alkali metal salts, hydroxides, oxides, and carbonates, especially compounds with Ca, Mg, and K, which affect the EC value of these materials [48]. The WBA used in this present study was characterized by a fairly low EC value (4.51 mS m−1) (Table 3), lower by 4.30 mS m−1 than in the ashes used in the study by Szostek et al. [17]. Despite this, in our research, in most objects with the addition of WBA (T2–T6), an increase in the EC value was noted in relation to the control soil (T0) (Figure 2c). The increase in the EC value after applying WBA has been shown in the literature already at lower doses, ranging from 0.5 to 3.0 Mg ha−1 of soil [17], as well as at ash doses similar to those adopted in this presented research, ranging from 5 to 20 Mg ha−1 [21]. The EC values obtained in our research, even after the application of the highest dose of WBA, remained much lower or very similar to the values reported in roadside soils exposed to traffic pressure and associated salinity [49,50] and the EC values were in the range of the class of unsalted soils, remaining lower than those shown in the study by Szostek et al. [17], in which significantly lower doses of WBA were applied.
For environmentally friendly utilization of ashes, the content of available K, P, and Mg forms is of great importance. WBA can be a significant source of P, comparable to the phosphorus from commercial fertilizers, which is important in the context of drastically shrinking P worldwide resources [8]. Scientific research shows that wood ash can be also a good source of K [9,12,14,18,19,22,23], P [9,12,14,18,19,21,22,23], and Mg [14,19,22,23], contributing to an increase in the content of overall forms of these metals in the soil [17]. According to Symanowicz et al. [14], a dose of 1 Mg of WBA can deliver 20 kg P, 98 kg K, and 39 kg Mg. WBA used in this present research and introduced into the soil in a dose of 1 Mg could provide approximately 6 kg of Ptot, 6 kg of Mgtot, and 17 kg of Ktot, including available forms, which would constitute approximately 2% P, 1% Mg, and 2.5% K. The doses of WBA used in this experiment resulted in a linear increase in the content of the discussed macronutrients (Table 6), which was highly significant (0.703 ** > r > 0.975 **). Similarly, Meller and Bilenda [24] and Gibczyńska et al. [51], after introducing WBA, noted positive changes in terms of increasing the content of available K, P, and Mg in the soil. Meller and Bilenda [24] showed the highest increase in the K content. In turn, Stankowski et al. [43] indicated a significant increase only in available K. It should be noted that the higher concentrations of available forms of K, P, and Mg recorded in the present research against the background of increasing doses of ash were manifested by the higher EC and pH of the soil; they also stimulated an increase in the sum of basic cations (SBC) and the degree of saturation of the soil sorption complex (BS), as indicated by the positive and highly significant correlations between these parameters (Table 7). The increase in the soil pH value and the improvement of sorption properties were also certainly associated with the high content of Ca in the ash (43.97 g kg−1), which was pointed out by Bang-Andreasen et al. [45]. These researchers emphasized that WBA was particularly suitable for acidic soils, in which it contributed to the improvement of the composition of soil microorganisms, stimulating their activity, which in turn improved the fertility of these soils. According to Symanowicz et al. [14], about 6 kg of Ca can be introduced into the soil with 1 Mg of WBA, while the amount added with the WBA used in this present study was almost 44 kg. According to Park et al. [41], WBA can provide most of the nutrients removed during harvest, with the exception of N. The N content of WBA reported by Symanowicz et al. [14] was 6 g kg−1 and was even lower in the ashes applied in our experiment, namely 4.29 g kg−1 (Table 3). Due to its low N content, WBA can be used in combination with other fertilizers [23,52].
However, it should be noted that, apart from the macronutrients that it supplies, wood ash can also be a rich source of micronutrients [18,43], among which toxic heavy metals are mentioned. The ash composition in this scope varied significantly and depended on the type of biomass [53]. According to Zając et al. [12], WBAs can be a significant source of Cd [15]. On the other hand, pine wood ash may contain excessive Pb content [10]. According to Uliasz-Bocheńczyk et al. [5], biomass ashes were characterized by high Cr leachability. Smołka-Danielowska and Jabłońska [54] added that the combustion of wood biomass in fireplaces caused increased emissions of Pb and Cd into the atmosphere, while these and other pollutants can permeate waters and soils from disposed ashes.
The content of trace metals in WBA used for this study followed a decreasing order Fe > Zn > Mn > Pb > Ni > Cr > Cu > Co > Cd and the amounts were 5684, 448.5, 237.3, 74.53, 49.95, 30.41, 26.54, 4.81, and 1.50 mg kg−1 (Table 4). A slightly different arrangement of the content of these metals in WBA was presented by Stankowski et al. [43], indicating a much higher content of Mn (9220 mg), Zn (1830 mg), and Cu (157 mg), lower Fe (829 mg), Pb (34.5 mg), and Ni (26.4 mg) than in our research, and comparable Cr content (35.2 mg kg−1). In turn, the content of metals in WBA given by Smołka-Danielowska and Jabłońska [54] was within wide ranges and, depending on the type of wood burned, equaled 18–297 mg Pb, 0.8–11.2 mg Cd, 16–878 mg Zn, 0.51–207 mg Cu, 24–76 mg Ni, and 17–66 mg Cr kg−1. The content of trace metals in the ash used in the tests did not exceed the amounts established for fertilizers and agents supporting the cultivation of plants listed in the Journal of Laws of the Republic of Poland (Regulation of the Minister of Agriculture and Rural Development) [55].
Taking into account the results of this present research and the literature data, wood ashes can be an impressive source of Fe, Mn, and Zn but, on the other hand, they can increase the content of toxic metals in the soil, e.g., Pb and Cd. In our research, a significant increase in the content of total forms of Pb, Cd, and Ni and a decrease in the content of Cr in the soil against the background of increasing doses of ash was observed (Table 8). However, Stankowski et al. [43] noted a significant increase in the content of Mn and Cu but did not show an increase in the content of Fe, Zn, Cr, Ni, or Pb in the soil with increasing ash doses. On the other hand, Szostek et al. [17] noted an increase in the content of Mn, Fe, Zn, Cu, Pb, Ni, and Cd in the soil after applying wood ash, but the increase correlated with increasing doses of ash was noted only in the case of Cu. Despite the observed increase in the content of some trace metals as a result of ash application to the soil, their content remained significantly lower than the standards set for agricultural soils specified in the Regulation of the Minister of the Environment of the Republic of Poland [56], which was also proven by the research of Stankowski et al. [43].
In addition to the total content of metals in the soil, it is important to know the quantities of available forms of these metals, which can raise toxicity to the environment. The content of available trace metals in the soil depends on various factors, including soil reaction [57,58], carbon content [59], properties of the soil sorption complex [59,60], or salinity [59]. The content of available forms of trace metals in the soil can be modified through the application of mineral substances to the soil [61,62,63]. The content of available forms of metals in the topsoil is closely correlated with the content of total forms of these metals in the soil [57,64]. In our research, WBA application resulted not only in a significant increase in the content of available forms of Zn, Cu, Ni, and Co but also Pb in the soil (Table 9). On the other hand, the content of available forms of Fe and Mn, despite their high content in WBA, did not change significantly. This may be related to the increase in the amount of total Cd and Pb content in the soil as a result of WBA application to the soil, which may reduce the mobility of Fe and Mn [34]. It was noteworthy that, along with the increase in the total Cd content, the content of its potentially available forms for plants decreased significantly. The decrease in the content of available forms of Cd against the background of increasing doses of WBA, noted in this work, may also indicate the possibility of using this material for the immobilization of Cd in soils contaminated with this metal. Analyzing the relationship between the content of available forms of Cd and soil properties (Table 11), it can be concluded that increasing the soil pH, BS, and TC content results in the formation of stronger bonds between soil components and Cd. In another study by Rolka and Wyszkowski [34], an inverse relationship was observed, i.e., as a result of the increase in the total content of Cd, the content of the available form of this metal increased, but this process took place at a lower pH value at which Cd is more mobile. An opposite situation occurred in the case of correlations between pH, BS, and TC and the content of available forms of Zn, Cu, Pb, Ni, and Co in the soil, which proved that the increase in these parameters resulted in the increased availability of these metals. While this is desirable in the case of Zn, Cu, Ni, and Co, this process must be monitored closely for toxic Pb. It should be remembered that an excess of any metal, regardless of its physiological role, may turn out to be an unfavorable event.
Different research results presented in the literature on the impact of ashes on soils and the results of the research described in this work may argue in favor of using WBA in agriculture; on the other hand, the composition of WBAs and their impact on soil properties needs continuous monitoring. Due to the low amount of N in WBA, this deficiency can be supplemented with mineral fertilizers, as was conducted in the present studies, or by combining WBAs with other waste materials, e.g., sewage sludge [65]. However, the potential use of ash from any type of biomass should be considered individually, depending on the origin of the biomass and its chemical composition [12]. Because of the variable composition of WBAs, related to the seasonality and the type of wood burned, this material requires an analysis each time before applying it to the soil. In addition, chemical monitoring of soils should be carried out and the quality of plants grown on them should be assessed.

5. Conclusions

The application of the increasing doses of WBA to the soil resulted in an increase in pH, TC content, and improvement of sorption properties, which was expressed in an increase in SBC, CEC, and BS and a decrease in HAC. An increase in the content of available forms of macronutrients (P, K, and Mg) and potentially available forms of trace metals (Zn and Cu) in the soil was observed. It should be noted that the addition of WBA to the soil also implied an increase in the EC value and the content of total forms of Pb, Cd, and Ni and a decrease in Cr. An increase in the content of available forms of Pb, Ni, and Co and a decrease in the content of available forms of Cd and Cr, particularly visible at higher doses of WBA, were observed. The results indicated a significant impact of WBA on basic soil parameters, which largely regulated the release of not only valuable macro- and micronutrients from the sorption complex but also trace metals that were unnecessary for plants. The rich composition of WBA made this waste a potentially valuable material that could play a significant role in improving soil properties.

Author Contributions

Conceptualization, E.R.; methodology, E.R. and A.S.-N.; software, E.R.; validation, E.R.; formal analysis, E.R., A.C.Ż., W.Z. and A.S.-N.; investigation, E.R., A.S.-N. and W.Z.; resources, E.R.; data curation, E.R.; writing—original draft preparation, E.R., W.Z. and A.S.-N.; writing—review and editing, E.R., A.C.Ż., M.W. and A.S.-N.; visualization, E.R.; supervision, E.R., M.W. and A.C.Ż.; project administration, E.R.; funding acquisition, E.R., A.C.Ż. and M.W. All authors have read and agreed to the published version of the manuscript.

Funding

The results presented in this paper were obtained as part of a comprehensive study financed by the University of Warmia and Mazury in Olsztyn, Faculty of Agriculture and Forestry, Department of Agricultural and Environmental Chemistry (grant no. 30.610.004-110), partially supported by the Minister of Education and Science in the range of the program entitled “Regional Initiative of Excellence” for the years 2019–2023, Project No. 010/RID/2018/19, amount of funding 12,000,000 PLN.

Data Availability Statement

Not applicable.

Acknowledgments

We acknowledge the contribution of the staff of the Department of Agricultural and Environmental Chemistry of UWM Olsztyn for their assistance in conducting the experimental work in the greenhouse and for sample preparation for lab analysis.

Conflicts of Interest

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

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Energies 16 05110 g001 550
Figure 1. (a) WBA used in research; (b) view of the Municipal Heating Energy Company in Olsztyn (MPEC Olsztyn).
Figure 1. (a) WBA used in research; (b) view of the Municipal Heating Energy Company in Olsztyn (MPEC Olsztyn).
Energies 16 05110 g001
Energies 16 05110 g002 550
Figure 2. (a) The value of soil reaction (pH), (b)total carbon (TC) content, and (c) soil electrical conductivity (EC). WBA treatments: T0 without WBA, T1 (15), T2 (30), T3 (45), T4 (60), T5 (75), and T6 (90 g of WBA pot−1); means followed by the same letter do not differ at p ≤ 0.05 by the LSD-test; n = 3; correlation coefficient (r) ** is highly significant for p = 0.01.
Figure 2. (a) The value of soil reaction (pH), (b)total carbon (TC) content, and (c) soil electrical conductivity (EC). WBA treatments: T0 without WBA, T1 (15), T2 (30), T3 (45), T4 (60), T5 (75), and T6 (90 g of WBA pot−1); means followed by the same letter do not differ at p ≤ 0.05 by the LSD-test; n = 3; correlation coefficient (r) ** is highly significant for p = 0.01.
Energies 16 05110 g002
Table
Table 1. Selected properties of the starting soil.
Table 1. Selected properties of the starting soil.
Soil PropertiesUnitValue
Sand 0.05–2.00 mm%73.92
Silt 0.002–0.05 mm%24.11
Clay ≤ 0.002 mm%2.03
Electrical conductivity (EC)µS m−151.27
Soil reaction (pHKCl)–log10 [H+]4.85
Sum of base cations (SBC)mmol(+) kg−150.67
Hydrolytic acidity (HAC)mmol(+) kg−125.50
Cation exchange capacity (CEC)mmol(+) kg−176.17
Base saturation (BS)%66.50
Total nitrogen (Ntot)g kg−10.78
Total carbon (TC)g kg−16.46
C/Nratio8.28
Phosphorus (Pav)mg kg−1194.1
Potassium (Kav)mg kg−1119.0
Magnesium (Mgav)mg kg−134.89
Table
Table 2. Content of total and available forms of trace metals (Fe, Mn, Zn, Cu, Pb, Cd, Ni, Co, and Cr) in the starting soil.
Table 2. Content of total and available forms of trace metals (Fe, Mn, Zn, Cu, Pb, Cd, Ni, Co, and Cr) in the starting soil.
Trace MetalsConcentration of Total Forms (mg kg−1)Concentration of Available Forms (Soluble in 1 M HCl) (mg kg−1)
Iron (Fe)94371000
Manganese (Mn)330.0117.8
Zinc (Zn)20.616.15
Copper (Cu)2.532.03
Lead (Pb)6.505.15
Cadmium (Cd)0.4030.188
Nickel (Ni)6.541.43
Chrome (Cr)2.060.809
Cobalt (Co)10.071.94
Table
Table 3. Selected properties of the WBA.
Table 3. Selected properties of the WBA.
WBA PropertiesUnitValue
Dry mass%80.41
Electrical conductivity (EC)mS m−14.51
Soil reaction (pHKCl)–log10 [H+]10.31
Sum of base cations (SBC)mmol(+) kg−13507
Hydrolytic acidity (HAC)mmol(+) kg−1750.0
Cation exchange capacity (CEC)mmol(+) kg−14257
Base saturation (BS)%82,38
Total nitrogen (Ntot)g kg−14.29
Total carbon (TC)g kg−1208.0
C/Nratio48.48
Phosphorus (Ptot)g kg−16.36
Potassium (Ktot)g kg−117.18
Magnesium (Mgtot)g kg−16.20
Calcium (Ca)g kg−143.97
Sodium (Na)g kg−11.36
Phosphorus (Pav)mg kg−1110.0
Potassium (Kav)mg kg−1410.0
Magnesium (Mgav)mg kg−157.00
Table
Table 4. Content of the total form heavy metals (Fe, Mn, Zn, Cu, Pb, Cd, Ni, Cr, and Co) in the WBA.
Table 4. Content of the total form heavy metals (Fe, Mn, Zn, Cu, Pb, Cd, Ni, Cr, and Co) in the WBA.
MetalFeMnZnCuPbCdNiCoCr
Unitmg kg DM−1
Value 5684237.3448.526.5474.531.5049.954.8130.41
Table
Table 5. Sorption properties (SBC, HAC, CEC, and BS) of soil after the end of the experiment.
Table 5. Sorption properties (SBC, HAC, CEC, and BS) of soil after the end of the experiment.
WBA TreatmentsSBCHACCECBS
(mmol kg soil−1)(%)
T049.33 d30.50 f79.83 c61.78 c
T158.67 a28.50 e87.17 ab67.29 a
T256.00 a26.00 d82.00 bc68.30 a
T361.33 ac24.00 c85.33 abc71.78 d
T466.67 bc21.00 a87.67 ab76.00 b
T570.67 b20.50 a91.17 a77.50 b
T672.00 b17.50 b89.50 a80.43 e
Means62.1024.0086.0971.87
r0.899 **−0.987 **0.635 **0.978 **
LSDp ≤ 0.056.311.156.482.06
SBC—sum of base cations; HAC—hydrolytic acidity; CEC—cation exchange capacity; BS—base saturation; WBA treatments: T0 without WBA, T1 (15), T2 (30), T3 (45), T4 (60), T5 (75), and T6 (90 g of WBA pot−1); means followed by the same letter do not differ p ≤ 0.05 in the LSD test within the analyzed soil properties; n = 3; correlation coefficient (r) ** is highly significant for p = 0.01.
Table
Table 6. Content of selected available forms of macronutrients in the soil after the end of the experiment.
Table 6. Content of selected available forms of macronutrients in the soil after the end of the experiment.
WBA TreatmentsKavPavMgav
(mg kg soil−1)
T075.45 a86.40 a32.77 ab
T174.75 a88.74 a32.93 ab
T283.66 ab93.42 d30.87 a
T384.13 ab97.39 b33.00 ab
T496.16 abc100.84 b34.55 ab
T5108.30 bc106.38 c36.73 b
T6121.85 c109.29 c41.33 c
Mean92.0497.4934.59
r0.747 **0.975 **0.703 **
LSDp ≤ 0.0527.953.684.17
WBA treatments: T0 without WBA, T1 (15), T2 (30), T3 (45), T4 (60), T5 (75), and T6 (90 g of WBA pot−1); means followed by the same letter do not differ at p ≤ 0.05 in the LSD test within the analyzed macronutrients; n = 3; correlation coefficient (r) ** is highly significant for p = 0.01.
Table
Table 7. Correlation between physicochemical properties and the content of available forms of macronutrients in the soil after the end of the experiment.
Table 7. Correlation between physicochemical properties and the content of available forms of macronutrients in the soil after the end of the experiment.
MacronutrientSelected Soil Properties
ECpHSBCHACCECBSTC
Kav0.793 **0.721 **0.741 **−0.751 **0.579 **0.758 **0.343 n.s.
Pav0.863 **0.965 **0.881 **−0.958 **0.630 **0.950 **0.730 **
Mgav0.682 **0.670 **0.585 **−0.708 **0.352 n.s.0.668 **0.465 *
EC—electrical conductivity; SBC—sum of base cations; HAC—hydrolytic acidity; CEC—cation exchange capacity; BS—base saturation; TC—total carbon; correlation coefficient (r) * is significant for p = 0.05; ** is highly significant for p = 0.01; n.s.—not significant; n = 21.
Table
Table 8. Content of total forms of trace metals in the soil after the termination of the experiment.
Table 8. Content of total forms of trace metals in the soil after the termination of the experiment.
WBA TreatmentsFetotMntotZntotCutotPbtotCdtotNitotCrtotCotot
(mg kg soil−1)
T09715 ab357.5 a24.01 a2.33 a5.71 a0.287 b7.14 c9.05 b8.61 b
T19770 ab334.7 a24.53 a2.80 ab7.13 bc0.373 ab8.05 c9.04 b12.53 a
T210,251 b476.8 a29.45 b2.60 ab10.56 d0.420 ab10.04 ab8.25 b12.79 a
T39302 a339.0 a24.65 a2.87 ab7.88 c0.420 ab10.94 b4.01 a13.22 a
T410,098 b450.8 a27.01 ab3.40 b6.30 ab0.487 a9.20 a4.01 a12.61 a
T59280 a321.4 a26.06 ab2.33 a9.27 e0.513 a9.12 a2.67 c10.24 c
T69882 ab349.3 a25.21 a2.60 ab10.46 d0.513 a10.20 ab2.86 ac12.07 a
Mean9757375.625.852.708.190.4319.245.7011.72
r−0.099 n.s.−0.058 n.s.0.123 n.s.0.098 n.s.0.541 *0.705 **0.574 *−0.914 **0.240 n.s.
LSDp ≤ 0.05651n.s.n.s.n.s.1.14n.s.1.021.211.31
WBA treatments: T0 without WBA, T1 (15), T2 (30), T3 (45), T4 (60), T5 (75), and T6 (90 g of WBA pot−1); means followed by the same letter do not differ at p ≤ 0.05 in the LSD test within the analyzed trace metals; n = 3; correlation coefficient (r) * is significant for p = 0.05; ** is highly significant for p = 0.01; n.s.—not significant.
Table
Table 9. Content of available forms of trace metals in the soil after the end of the experiment.
Table 9. Content of available forms of trace metals in the soil after the end of the experiment.
WBA TreatmentsFeavMnavZnavCuavPbavCdavNiavCravCoav
(mg kg soil−1)
T01014 a125.3 a7.35 a1.71 a4.73 d0.230 b1.03 b1.53 b1.53 b
T11074 a130.5 a7.32 a1.81 ab5.23 a0.222 ab1.24 a1.44 b1.94 a
T21017 a125.9 a7.32 a1.84 abc5.35 ab0.206 acd1.14 ab1.31 d1.95 a
T31032 a131.1 a8.73 ab1.91 bcd5.26 ab0.219 ab1.18 ab1.18 c1.99 a
T41011 a129.8 a9.68 b1.89 abc5.33 ab0.215 abd1.31 ac1.07 a2.03 a
T51055 a131.2 a9.60 b2.00 cd5.69 c0.198 cd1.50 c1.07 a1.91 a
T61004 a129.9 a8.70 ab2.08 c5.54 bc0.195 c1.47 c0.97 a1.92 a
Mean1030129.18.391.895.300.2121.271.221.90
r−0.1070.3180.678 **0.795 **0.777 **−0.696 **0.793 **−0.950 **0.518 *
LSDp ≤ 0.05n.s.n.s.1.310.170.280.0190.190.110.12
WBA treatments: T0 without WBA, T1 (15), T2 (30), T3 (45), T4 (60), T5 (75), and T6 (90 g of WBA pot−1); means followed by the same letter do not differ at p ≤ 0.05 in the LSD test within the analyzed trace metals; n = 3; correlation coefficient (r) * is significant for p = 0.05; ** is highly significant for p = 0.01; n.s.—not significant.
Table
Table 10. The value of Pearson’s coefficients between the content of available metals and the content of total metals in the soil.
Table 10. The value of Pearson’s coefficients between the content of available metals and the content of total metals in the soil.
Forms of Trace MetalsFetotMntotZntotCutotPbtotCdtotNitotCrtotCotot
Feav−0.222 n.s.−0.151 n.s.−0.009 n.s.0.231 n.s.−0.142 n.s.0.058 n.s.−0.276 n.s.0.025 n.s.−0.114 n.s.
Mnav−0.456 *−0.267 n.s.−0.018 n.s.0.190 n.s.0.002 n.s.0.127 n.s.0.088 n.s.−0.404 n.s.0.009 n.s.
Znav−0.204 n.s.−0.019 n.s.0.084 n.s.0.338 n.s.−0.037 n.s.0.591 **0.214 n.s.−0.788 **0.078 n.s.
Cuav−0.157 n.s.−0.205 n.s.0.073 n.s.−0.007 n.s.0.464 *0.744 **0.411 n.s.−0.713 **0.232 n.s.
Pbav−0.090 n.s.−0.032 n.s.0.296 n.s.0.122 n.s.0.611 **0.766 **0.475 *−0.647 **0.368 n.s.
Cdav−0.047 n.s.−0.070 n.s.−0.265 n.s.0.072 n.s.−0.701 **−0.655 **−0.447 n.s.0.507 *−0.122 n.s.
Niav−0.223 n.s.−0.227 n.s.0.067 n.s.0.041 n.s.0.461 *0.706 **0.282 n.s.−0.682 **0.136 n.s.
Crav0.127 n.s.−0.010 n.s.−0.147 n.s.−0.152 n.s.−0.433 n.s.−0.762 **−0.624 **0.903 **−0.305 n.s.
Coav0.070 n.s.0.222 n.s.0.300 n.s.0.515 *0.296 n.s.0.542 *0.593 **−0.460 *0.730 **
Correlation coefficient (r) * is significant for p = 0.05; ** is highly significant for p = 0.01; n.s—not significant; n = 21.
Table
Table 11. The value of Pearson’s coefficients between the content of available metals and the selected properties of the soil.
Table 11. The value of Pearson’s coefficients between the content of available metals and the selected properties of the soil.
Forms of Trace MetalsSoil Properties
ECpHSBCHACCECBSTC
Feav−0.117 n.s.−0.169 n.s.0.067 n.s.0.095 n.s.0.200 n.s.−0.022 n.s.−0.272 n.s.
Mnav0.350 n.s.0.304 n.s.0.498 *−0.327 n.s.0.549 *0.419 n.s.0.026 n.s.
Znav0.707 **0.627 **0.693 **−0.694 **0.549 *0.707 **0.330 n.s.
Cuav0.622 **0.774 **0.765 **−0.782 **0.593 **0.790 **0.508 *
Pbav0.541 *0.724 **0.744 **−0.765 **0.573 *0.791 **0.584 **
Cdav−0.410 n.s.−0.721 **−0.455 n.s.0.652 **−0.183 n.s.−0.597 **−0.574 *
Niav0.699 **0.743 **0.773 **−0.775 **0.612 **0.802 **0.489 *
Crav−0.831 **−0.915 **−0.840 **0.959 **−0.560 *−0.936 **−0.688 **
Coav0.317 n.s.0.486 *0.571 *−0.548 *0.474 *0.604 **0.351 n.s.
EC—electrical conductivity; SBC—sum of base cations; HAC—hydrolytic acidity; CEC—cation exchange capacity; BS—base saturation; TC—total carbon; correlation coefficient (r) * is significant for p = 0.05; ** is highly significant for p = 0.01; n.s—not significant; n = 21.
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Rolka, E.; Żołnowski, A.C.; Wyszkowski, M.; Zych, W.; Skorwider-Namiotko, A. Wood Biomass Ash (WBA) from the Heat Production Process as a Mineral Amendment for Improving Selected Soil Properties. Energies 2023, 16, 5110. https://doi.org/10.3390/en16135110

AMA Style

Rolka E, Żołnowski AC, Wyszkowski M, Zych W, Skorwider-Namiotko A. Wood Biomass Ash (WBA) from the Heat Production Process as a Mineral Amendment for Improving Selected Soil Properties. Energies. 2023; 16(13):5110. https://doi.org/10.3390/en16135110

Chicago/Turabian Style

Rolka, Elżbieta, Andrzej Cezary Żołnowski, Mirosław Wyszkowski, Weronika Zych, and Anna Skorwider-Namiotko. 2023. "Wood Biomass Ash (WBA) from the Heat Production Process as a Mineral Amendment for Improving Selected Soil Properties" Energies 16, no. 13: 5110. https://doi.org/10.3390/en16135110

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