1. Introduction
Due to the depletion of traditional non-renewable fossil fuels emitting large amounts of greenhouse gases, it is necessary to search for alternative environmentally friendly energy sources, with special emphasis to biomass [
1,
2]. Energy obtained from plant biomass combustion is increasingly being produced due to the necessity of transition to a low-emission economy [
3]. The combustion of biomass and other energy carriers leads to the production of ashes at the annual level of 480–500 million tons. The management of ashes should be safe for the natural environment and for the health of humans and animals. According to the European Directive 2008/98/EC, ashes are considered as solid waste; hence, almost 70% of their amounts are stored in landfills [
4]. This may cause serious damage to the natural environment, which may indirectly threaten human and animal health [
2,
5,
6]. In addition, landfilling of ashes may not be possible in the future given the EU’s circular economy policy instruments [
4]. Therefore, methods for rational management of these wastes should be developed. From the perspective of sustainable development, the most beneficial approach regarding the disposal of biomass ashes (BAs) is their return to the soil, and this solution is compatible with the circular economy idea too if proven to be economical and beneficial [
7].
BAs are a solid residue of biomass combustion. It is a complex inorganic–organic mixture with poly component, heterogeneous, and variable composition containing intimately mixed solid, liquid, and gaseous phases with different origins [
8]. BAs differ in their physical properties and chemical composition from ashes produced by burning traditional fossil fuels. Due to the higher content of potential plant nutrients than in bottom ashes, fly ashes are more suitable for soil fertilization and agricultural applications [
1,
5,
8].
The chemical composition of BAs includes major elements (>1%), minor elements (1–0.1%), and trace elements (<1%) [
8]. Fly ashes from biomass combustion and biomass itself may comprise as many as 79 different elements. Ashes from plant biomass combustion contain large amounts of macroelements and microelements necessary for plant growth and development, e.g., phosphorus, potassium, calcium, sulfur, magnesium, and others [
1,
2,
7]. In turn, the presence of various types of harmful substances, such as heavy metals, limits the possibility of using BAs for the fertilization of plants [
1,
2,
7]. Therefore, the chemical composition of ashes should be analyzed every time before using these wastes [
7,
9].
BAs were reported to affect the physical properties of soil due to their high capacity to absorb water and can change water relations in soil, improve soil porosity, and facilitate penetration of the soil by plant roots [
9,
10]. They also have an impact on physicochemical properties of soil, as they increase its pH thus producing a deacidification effect, increase the degree of saturation of the sorption complex with alkaline cations, and have diverse effects on the properties of organic matter, as widely documented in the literature [
11,
12,
13]. Additionally, BAs directly influence the abundance of plant-available nutrients in the soil, i.e., macro- and microelements, in particular K, P, Ca, Mg, Mn, Z, and Fe [
11,
12,
13,
14,
15,
16]. The biological properties of soils can be improved with the use of BAs, as the ashes exert an impact on the microbiological structure of soil and enhance the activity of soil microorganisms [
10,
11,
14,
17].
Given the diversity of their chemical composition, the impact of fly ashes from biomass combustion on the soil should be closely monitored, mainly due to their potential to cause extreme changes in soil reaction and salinity or excessive accumulation of trace elements. Such long-term changes may bring many negative effects resulting in loss of soil fertility and productivity. Therefore, the main objective of the study was to assess the short-term impact of BA fertilization on the properties of soils and soil solutions. Additionally, the suitability of BAs for fertilization of spring rape plants was assessed and their effect on the accumulation of macroelements and trace elements in this crop was compared.
4. Discussion
Ash from biomass combustion contains substantial amounts of macro- and micronutrients; hence, it can be used for fertilization of different crop species (e.g., spring wheat, maize, potatoes, legume) [
15,
24,
25,
26]. The dose of ash used in fertilization schemes for various plant species is determined primarily through analysis of the content of phosphorus and potassium. BAs may contain over 40% of calcium compounds, up to 36% of potassium compounds, and 7% of phosphorus compounds [
17]. It has also been indicated that fly ashes are more suitable for fertilization than bottom ashes, as the former contain much larger contents of macro- and microelements, although they may additionally contain larger amounts of impurities. The positive impact of biomass combustion ashes on the growth and development of various plant species has been widely documented in the literature and was also confirmed in the present study [12,15,16,25,26].
The biomass ashes used in the experiment contained large amounts of macro- and microelements (except N), and their application, starting from the dose of 1 Mg ha
−1 (D1), resulted in more efficient plant growth and development, in comparison with the control variant. It was also found that the fly ash-induced increase in the dry matter content of plants, the SPAD value, and the accumulation of basic macronutrients in the spring rape seeds was comparable to that observed in the traditional NPK fertilization variant. This indicates that biomass ashes can be used successfully as a valuable fertilizer in spring rape plant cultivation. Nevertheless, in the case of dry matter and SPAD, better results were achieved in objects D2-D4 than in variants fertilized with the lowest and highest doses (
Figure 1 and
Figure 2). The use of ashes, especially in higher doses, does not significantly improve the SPAD value and dry matter content [
24]. This could be attributed to the mineral composition of the ash, it having high concentrations of important elements but virtually no nitrogen. Furthermore, wood ash application may strongly influence the soil texture, aeration, and water holding capacity, consequently having an impact on the root growth dynamics leading to a range of possible effects on plant growth [
24,
27].
Despite the similarities in the effect of the traditional NPK and BAs on plant growth and development, these fertilizers exerted different effects on the analyzed soil properties. BAs contain high concentrations of soluble alkali metal salts, hydroxides, oxides, and carbonates, especially compounds with Ca, Mg and K, which have an impact on the pH and EC values of these fertilizers [
5]. Most BAs have a pH value ranging from 9.4 to 13.5, and the ash used in the experiment had similar values (
Table 2). BAs positively influence a number of soil properties, mainly by increasing the pH value which has been widely documented in the literature [12,14,28]. It has been emphasized that BAs can be a substitute for calcium fertilizers used for deacidification of both agricultural and forest soils [
29]. BAs present in the soil react much faster than lime and contribute to a stronger but relatively short-term increase in pH [
29]. The application of even the lowest dose of BAs in the present study resulted in an increase in the mean soil pH values. The soil reaction changed under the impact of the ashes from slightly acidic (control, NPK) to neutral (D1-D6), with the highest increase in pH achieved after the application of the highest ash dose of 3 Mg ha
−1 (D6). It has been indicated that BAs have the most pronounced effect on the pH value in soils with higher acidity and low organic matter content [
28]. As reported by Hansen et al. (2017), changes in pH in the topsoil exhibit the greatest dynamics during the first 50 days after BAs application. Noteworthy, the use of BAs may cause extreme pH fluctuations, especially in the topsoil layer (pH = 11.0–4.4). Therefore, this should be taken into account in assessment of the impact of fly ashes on pH changes and soil properties [
29].
It is assumed that changes in the chemism of soil solutions in BAs-fertilized soils are good indicators of the solubility, mobility, and availability of plant nutrients as well as soil fertility [
30,
31,
32]. The application of BAs may induce a rapid increase in the soil solution pH value, which persists for approximately two months after the fertilization [
32]. The present study showed the opposite tendency, as the most pronounced changes in the pH of the soil solution after the application of BAs were noted only at approximately 70 days after sowing the seeds (
Figure 4). This may be related to the characteristics of the ashes used in the experiment. They were derived from combustion of agricultural and forest biomass, and the compounds contained therein may have been less soluble. Changes in the pH of the soil solution as a result of the use of various waste materials, including ashes, may also be associated with changes in weather conditions, temperature, microbiological activity, as well as interactions that occur between individual compounds. Changes in the chemistry of the soil solution are also closely related to the metabolic processes of plants, mainly by substances secreted by the rhizosphere zone. It is indicated that changes in the pH of soil solutions may be associated with a decrease in the concentration of NO
3− ions, which are taken up by the roots of developing plants [
32]. Some studies also indicate that the pH of the soil solution is more dependent on the type of soil and the species of a cultivated plant species, than the type of ash, used [
32].
As indicated by Gómez-Rey and Coutinho (2012), fertilization of soil with ashes from biomass combustion, especially applied as a loose material, enhances N and P leaching, especially in the first month after application, which was not confirmed in the present study [
33]. In the initial stage of the experiment, the average concentration of NO
3− ions was much higher in the control and NPK variants, which may have been related to the release of nitrogen compounds introduced with the mineral fertilizer. The lower content of these ions in the soil solution may indicate increased uptake thereof by plant roots on the one hand, as the plants exhibited more intensive growth after the application of the ashes [
31]. On the other hand, they may indicate reduced leaching of nitrogen compounds from the soil due to the introduction of substances that block this process but do not reduce nitrogen assimilability. After application of ashes, Bielinska et al. (2009) reported extremely high content of N-NO
3− in soil, especially in a cereal cultivation variant. The authors explain this phenomenon by transformations of nitrogen, in particular by nitrification, which proceeds most intensively in aerobic conditions and in soils with a slightly acidic to neutral pH value and with a large amount of phosphorus [
34]. Similar findings concerning the concentration of NH
4+ in the soil solution were obtained in the present study. In this case, the mean concentration of NH
4+ in the soil solution at the beginning of the experiment was many times higher in the control and NPK variants. It can be concluded that the compounds contained in the ashes inhibited leaching of nitrogen compounds into the soil solution. Despite the low content of N in the ashes, the limitation of its solubility could also contribute to the higher content of N in the soil, compared to the control (
Table 5) [
24]. As there were very small changes in the content of PO
43− ions in the soil solutions, a relatively low rate of leaching of phosphorus introduced with BAs was assumed. Already on day 10 after sowing the seeds, PO
43− ions were detected in the soil solution in the control and NPK variants but not in the BA-fertilized objects. The low rate of leaching of phosphorus applied with the ashes should have resulted in an increase in its content in the soil and higher accumulation in plants. However, the content of P was significantly higher only in the object fertilized with the highest BAs dose. The seeds of plants fertilized with the highest BAs doses exhibited higher accumulation of this element in comparison with the seeds from the other experimental objects. Some portion of phosphorus may have been accumulated by other parts of the plants, but this issue was not investigated in the present study. As shown by other researchers, P derived from BAs is very poorly soluble. In turn, a large portion of soluble P is probably immobilized in soil, which does not result in increased accumulation of P by plants. It has also been demonstrated that the uptake of phosphorus supplied with BAs is much less efficient than in the case of phosphorus provided by mineral fertilizers [
28,
29,
30].
The BAs fertilization resulted in increased release of sulfur compounds into the soil solution, which resulted in high concentrations of SO
42− ions in the solution. In the final stage of the experiment, their average content in the object fertilized with the highest ash dose (D6) was as much as 2615% higher than in the control. Noteworthy, the lowest average S content was detected in the plants fertilized with the highest doses of BAs, in comparison with the other experimental objects. This may additionally confirm the high solubility of S compounds contained in ashes, which results in sulfur leaching beyond the reach of the root system and thus lower assimilability of this element. Some of the components introduced with ash to soil are dissolved, which results in an increase in their concentration in the soil solution. It is believed that Ca and Mg are present in ashes mainly as less soluble secondary minerals [
11]. Nevertheless, the results of the present study indicate relatively easy leaching of these elements, resulting in their substantial concentrations in the soil solution; this trend was found to persist throughout the experiment. The mean concentration of Ca
2+ ions before plant harvesting in the object fertilized with the highest dose of ashes (D6) was 691% higher than in the control. Despite the high concentrations of Ca
2+ in the soil solution throughout the experiment, at the end of the experiment, the content of Ca in the variants supplemented with the highest ash doses (D4–D6) was 18, 10, and 20% higher, respectively, than in the control. The application of BAs contributed to a significant increase in the content of Mg
2+ ions in the soil solution, and this effect persisted throughout the experiment. As a result of the BAs fertilization, the average Mg content at the end of the experiment was significantly higher than in the control.
It has been evidenced that Na, K, and B are present in ash as easily soluble salts, which are released from ash particles within the first two years after application [
11]. Large amounts of easily soluble salts of such elements as K and Na may be responsible for soil salinity, which should be considered in assessment of the impact of ash waste on the soil environment. If the availability of fertilizer ingredients exceeds plants’ needs, easily soluble compounds may leach out of reach of the root system, which is especially the case of potassium [
11]. The BAs fertilizer used in the experiment contained nearly 17% of K. Despite the high solubility of K, no significant increase in the concentration of K
+ ions in the soil solution was observed throughout the experiment. Due to its good solubility, K was accumulated in the spring rape seeds in a substantially larger amount than in the control and NPK treatments. Additionally, after the experiment, the average content of K in the soil treated with the highest dose of BAs was 32% higher in comparison with the control. Although the ash used in the experiment contained significantly lower content of Na than K (0.14%), a significant increase in the concentration of Na
+ ions in the soil solution was observed during the study period. Before the end of the experiment, the average concentration of Na
+ ions in the soil solution in objects D5 and D6 was 412 and 342% higher, respectively, compared to the control, and the average content of this element in the soil was approx. 70% higher. The present study also showed a higher concentration of Cl
− ions in the soil solution after the application of BAs, compared to the control and NPK variants. This higher concentration, detected throughout the experiment, was shown to be dependent on the ash doses. The Na
+ and Cl
− ions contained in the soil solution contributed to a significant increase in the salinity of soil solutions. Dynamic changes in the content of Ca
2+, Mg
2+, K
+, Na
+, and Cl
− in the soil solution between 40 and 100 days after sowing the seeds also resulted in dynamic changes in the EC values of the soil solution (
Figure 6B).
In turn, the increase in K and Na content in the analyzed soil increased the EC value, but the salinity class was unchanged by the ash fertilization. Due to the possibility of soil salinization induced by ashes, this parameter should be closely monitored.
In addition to the content of macroelements that are valuable for fertilization, BAs also contain large amounts of trace elements, some of which function as microelements while others are highly toxic to living organisms [
31]. Fe as well as Mn, Cu, and Zn were the dominant microelements present in the ash used in the experiment (
Table 2). Fe is a microelement present in BAs in the largest amounts, reaching up to 21 g kg
−1 in ashes produced from wood biomass [
29]. The use of BAs was found to increase the total content of Mn, Ni, Zn, and Cu in soil with no significant changes in the content of Cd and Pb [
29]. Similar results were obtained in the present study; however, BAs was shown to increase the amounts of macroelements to a much greater extent than those of trace elements in the analyzed soil. Unlike in the case of macroelements, the accumulation of trace elements in the seeds was significantly higher in the ash-fertilized objects than in the control and NPK variants (
Table 3 and
Table 4). The highest accumulation of the Fe, Mn, Zn, Cu, Cr, and Ni elements was detected in plants fertilized with BAs at a dose of 2.0 Mg ha
−1 (D4). Compared to the control, the average contents of these elements were higher by 263, 363, 107, 51, 1835, and 137%, respectively. It has been indicated that BAs may improve the availability of Cu and Fe in the soil as well as Pb [
16]. The soil pH value was a probable cause of the lower accumulation of Fe, Mn, Zn, Cu, Cr, and Ni in seeds of plants fertilized with doses D5 and D6. It is well-known that higher pH values reduce the solubility and mobility of most trace elements [
34,
35,
36,
37]. Reducing the mobility of these elements as a results of the increase of soil pH could have caused their greater accumulation in the root zone, which would explain their lower concentration both in the soil and in the seeds [
24]. The highest contents of Pb and Cd in the seeds were determined in the treatment with the highest doses of BAs. The Pb content in the seeds positively correlated with soil pH and K content and exhibited a negative correlation with the content of Cr in the soil. In turn, the level of Cd in the seeds was positively correlated with pH and the content of K, Ca, Mg, and Na in the soil (
Figure 5). Literature data have demonstrated that rape plants have the ability to absorb large amounts of Zn, Cu, Pb, and Cd from the soil, which are accumulated in seeds and vegetative organs. Thus, they can be used to remediate soils contaminated with such elements as Cd, Cr, Cu, Ni, Pb, and Zn [
36]. This was confirmed by studies [
38,
39] showing that the application of wood ashes resulted in hyperaccumulation of trace elements in rape plants in the following bioaccumulation order: Fe > Zn > Pb > Co > Cu > Cd > Ni.
The relatively high concentrations of Cd and Pb as well as Cr and Ni in BAs, their relative solubility, regardless of soil pH, and accumulation in spring rape seeds should be considered in assessment of the potential impact of biomass ashes on the environment [
36].