3.1. Thermophysical Properties of SRWC Biomass
The thermophysical characteristics under study, including the moisture content, ash content, volatile matter content, fixed carbon content, and the HHV of the woody biomass were significantly differentiated by all the main factors, i.e., the SRWC species, the soil enrichment procedure, the harvest rotation, and the interactions between these factors (
Table 1). The SRWC species accounted for the highest biomass moisture content variation (93.8% of the overall variance). The black locust biomass was characterized by the significantly lowest moisture content (an average of 38.89%, homogeneous group “c”) (
Table 2). The moisture contents in the willow and poplar biomasses were also significantly higher (by 27.9 and 45.3%, respectively). As regards the soil enrichment procedures, a statistical analysis showed significant differences, but all the variants under analysis fell into homogeneous groups from “a” through “ab” to “b”, and the moisture content fell within a very narrow range of 48.11 to 48.70%. The negligibly greater differences in the biomass moisture content occurred for the first two consecutive harvest rotations (5.1% and 3.2%), whereas a significantly lower moisture content in the SRWCs was noted in the third rotation (an average of 47.08%). However, it must be added that 3–5% moisture content variations are well within the seasonal variation of a species. In general, the black locust biomass was characterized by lower moisture content in all the harvest rotations (homogeneous group “f–g”) as compared to the willow biomass (homogeneous group “e–d”) and the poplar biomass (homogeneous group “a–c”). A low moisture content in the black locust biomass (an average of 40%) was also noted under Italian climatic conditions [
26]. Other studies have also demonstrated that the moisture content of black locust biomass during the harvest was usually lower (approx. 40%) compared to willow (approx. 50%) and poplar (approx. 60%) [
27]. The moisture content of poplar biomass during the harvest is usually high and accounts, in general, for over 50%, and it can occasionally even reach over 60% [
11,
28,
29,
30,
31]. However, willow biomass was generally characterized by a moisture content lower than that of poplar, with an average value of approx. 50% [
30,
32]. An even lower water content of willow biomass (an average of 48.9%) was determined in a study on 15 genotypes cultivated at two locations and harvested in two consecutive three-year harvest rotations [
22]. The cited study also found that the genotype was by far the largest contributor to the variation of this characteristic (almost 81% of the overall variance), similar to the current study’s results. It should be noted that the weather conditions during the plant harvest, and immediately before and after the harvest, also affect the biomass moisture content. Precipitation and high humidity during the harvest translate into increased moisture content of the obtained biomass. Therefore, the SRWC biomass moisture content in the literature can often vary significantly, even within the same species and cultivation technology. Nevertheless, of the three SRWC species analyzed in the current study, black locust always exhibited the lowest water content, and poplar always exhibited the highest.
The ash contents, just like the moisture contents, were most strongly determined by the SRWC species (almost 51%), followed by the harvest rotation (10%) and, to a lesser extent, by the other factors and the interactions between them (
Table 1). Of all the SRWC species under study, the lowest ash content, an average of 1.25% DM, was determined in willow biomass (
Table 2). The ash contents in the black locust and the poplar biomasses were significantly higher (by 12.0% and 33.6%, respectively). All of the applied soil enrichment procedures contributed to an increase in the ash content in SRWC biomass compared to the control plots (homogeneous group “c”), although these differences were not always statistically significant. However, for the interaction of species (A) and soil enrichment procedure (B) more varied results were obtained. Slightly greater differences in the ash content occurred for the consecutive harvest rotations, as the value of this characteristic was significantly noted in the third rotation (an average of 1.33 DM), while in the second and the first rotation this value was higher by 12.0% and 13.5%, respectively. In general, poplar biomass was characterized by a higher ash content in all harvest rotations (homogeneous group “a–c”) as compared to the willow biomass, for which the lowest value of this characteristic was noted in the third harvest rotation (1.14 DM, homogeneous group “f”). A low ash content (an average of 1.26% DM) was also noted in the biomass of 15 different willow genotypes cultivated on different sites in three-year rotations [
22]. It was emphasized, however, that the differences in the ash content between the genotypes under study were great (up to 44%). A study conducted in the USA noted even greater variation in the ash content in willow biomass (1–3% DM) [
23]. It should be added, however, that the study involved several locations and several dozen genotypes. Similar ash contents in willow biomass (1.9–3% DM) were determined in other studies [
31,
33]. For poplar, depending on the genotype, the ash content also exhibited a similar high variation (0.98–3.12% DM) [
29,
30,
31]. In another study, the ash content in four-year poplar shoots averaged 1.4% DM, ranging from 1.0 to 1.6% DM [
11]. For black locust, the ash content ranged from 0.17–2.2% DM [
34] and even exceeded 3.3% DM [
31]. Despite these large fluctuations in the SRWC ash content, it should be added that these values were still lower than the ash content of semi-woody biomass, straw, or palm kernel shells [
27,
35,
36]. However, compared to a solid fossil fuel such as hard coal, the ash content of SRWC biomass can be several times lower [
37]. This is clearly favorable, as it can translate into higher proportions of fuel energy use, and the ash remaining from biomass can be used to enrich the soil [
38].
When analyzing the volatile matter and fixed carbon contents, it was difficult to clearly indicate which factors most strongly determined these parameters. The main factors ranged between only 2.1% and 13.4%, while the interactions between them ranged from 5.5% to 16.3% (
Table 1). Therefore, it is difficult to identify the factor with the strongest effect. Willow biomass was characterized by the highest volatile matter content (an average of 78.38% DM) and the lowest fixed carbon content (an average of 20.37% DM) (
Table 2). On the other hand, the volatile matter contents in black locust and poplar biomass were only lower by 0.7%, and the fixed carbon content was higher by less than 1–2%. Moreover, the variation in these two parameters in terms of the soil enrichment procedures and the consecutive harvest rotations was small and ranged from 1% to 5%. The highest volatile matter content (an average of 79.46% DM) was noted in willow biomass in the first harvest rotation, while the highest fixed carbon content (an average of 21.44% DM) was noted in black locust biomass in the third harvest rotation. In another study, the fixed carbon and volatile matter contents in four-year poplar shoots were, on average, 18.6 and 79.4% DM, respectively [
11], while in three-year willow shoots these values amounted to 19.4 and 79.4% DM, respectively [
22]. Moreover, the cited study did not identify the factor with the clearly strongest effect on the fixed carbon and volatile matter contents, as they were determined by the harvest rotation, genotype, location, and the interactions between these factors. On the other hand, in a study conducted in Spain [
31], the volatile matter contents in black locust, poplar, and willow biomass were generally higher than in the current study and amounted to 81.33, 82.37, and 83.59% DM, respectively. Nevertheless, of all the species in that study, similar to the current study, the highest value of this characteristic was noted for willow.
Higher heating value (HHV) was most strongly determined by the SRWC species (62.6%), followed by the interaction between the species and the harvest rotation (16.6%) and, to a lesser extent, by all the other factors and their interactions (
Table 1). The poplar biomass was characterized by the significantly highest HHV with an average of 19.84 GJ Mg
−1 DM (
Table 2). The value of this characteristic for willow and black locust biomass was slightly (but significantly) lower (by 1.1% and 1.9%, respectively). As regards the soil enrichment procedures, the differences in the HHV between the plots under study were less than 0.5%. The situation was similar for consecutive harvest rotations, where a significantly higher HHV value was noted in the third rotation (an average of 19.71 GJ Mg
−1 DM), while in the second and the first rotation this value was lower by 0.5% and 0.6%, respectively. The poplar biomass was characterized by higher HHV values in all harvest rotations (homogeneous group “a–b”) as compared to willow (homogeneous group “c–d”) and black locust (homogeneous group “c–f”). In another study, four-year poplar shoots were also characterized by a high HHV value (averaging 19.60 GJ Mg
−1 DM), while in the second harvest rotation, for the UWM2 clone, it was as high as 19.9 GJ Mg
−1 DM [
11]. A lower HHV (an average of 19.53 GJ Mg
−1 DM) was noted in a study involving 15 willow genotypes sourced from two locations in the consecutive three-year harvest rotations [
22], which was consistent with the relationships demonstrated in the current study.
3.2. Elemental Composition of SRWC Biomass
The carbon (C), hydrogen (H), nitrogen (N), sulfur (S), and chlorine (Cl) contents in biomass were significantly differentiated by all the main factors, i.e., the SRWC species, soil enrichment procedure, and harvest rotation, as well as by most interactions between these factors (
Table 3). The harvest rotation accounted for the greatest percentage of the C, H, and Cl contents in the variation (83.9%, 73.3%, and 28.3%, respectively, of the overall variation), which was somewhat surprising. However, regarding the N content, the SRWC species accounted for the decidedly highest percentage (81.3%) in the variation of this characteristic. The SRWC species also contributed to the variation in the S content (20.5%), but the interaction between the species, harvest rotation, and soil enrichment procedure contributed even more (22.4%), followed by the interaction between the species and the soil enrichment procedure (10.1%).
Poplar and willow biomasses were characterized by a significantly higher C content (on average over 53.3% DM, homogeneous group “a”) as compared to the black locust biomass (
Table 4). For the soil enrichment procedures, the statistical analysis showed differences, but all the variants under analysis fell into homogeneous groups from “a” through “ab” to “b”, and the C content fell within a range of 52.69–53.41% DM. Greater differences in the C content in SRWC biomass occurred for the consecutive harvest rotations, as a significantly higher value of this characteristic was noted in the second and the third rotation (over 54.4% DM), while in the first rotation this value was lower by approx. 7.5%. This could have been affected by varied interactions and environmental conditions in consecutive years of plant cultivation. In general, the black locust biomass was characterized by a lower C content in all the harvest rotations compared to the willow and the poplar biomasses. However, in another study [
31], black locust biomass (51.51% DM) and poplar biomass (51.81% DM) were characterized by a higher C content compared to willow biomass (48.84% DM). A higher carbon content in willow biomass (amounting to an average of 52.90% DM) was determined for different genotypes, locations, and harvest rotations [
22]. Moreover, the cited study found that the location was the greatest contributor to the variation in the C content, followed by the genotype, harvest rotation, and the interaction between these factors, which was also partially confirmed by the current study.
Willow biomass was characterized by a significantly higher H content of an average of 5.97% DM (
Table 4). The value of this characteristic for the black locust and poplar biomass was slightly but significantly lower (by 0.5 and 1.2%, respectively). Of all the soil enrichment procedures applied, a significantly higher H content (an average of 6.02% DM) was noted for the control plot (C), while for the other soil enrichment variants the value of this characteristic was lower within a range of 1–3%. Greater differences in the H content in SRWC biomass occurred for the consecutive harvest rotations, as a significantly higher value of this characteristic was noted in the third rotation (over 6.31% DM), while in the first and the second rotation this value was lower (by 7.1% and 10.6%, respectively). In another study [
31], black locust biomass (6.44% DM) and poplar biomass (6.39% DM) were characterized by a higher H content compared to willow biomass (6.18% DM). Moreover, the H content in SRWC biomass in the cited study was generally higher than the current study’s results. A higher H content in willow biomass (6.23% DM) was also determined in another study [
22]. Moreover, it was found that the content of this element was most strongly determined by the interaction between the location and the genotype, followed by the genotype and the location.
Black locust biomass was characterized by a significantly higher S content with an average of 0.033% DM (
Table 4). The value of this characteristic for willow and poplar biomasses was significantly lower (by 21.2% and 24.2%, respectively). Of all the soil enrichment procedures applied, a significantly higher S content (an average of 0.032% DM) was noted for the plot on which mineral fertilization was applied (F), while for the other soil enrichment variants the value of this characteristic was lower within the range of 9–22%. However, for the interaction of species (A) and soil enrichment procedure (B) more varied results were obtained. In the second harvest rotation, the average sulfur content in SRWC biomass was 10% higher than in the first and third harvest rotations. It should be noted that black locust biomass was generally characterized by a higher S content in all harvest rotations (homogeneous group “a–ab”) compared to poplar and willow. In a study conducted in Spain [
31], black locust was characterized by a higher S content (0.05% DM) compared to poplar (0.04% DM) and willow (0.03% DM). In another study, the S content in willow biomass was mainly determined by the genotype (25%), location (18%), and the interaction between these two factors (21%) [
22], which was similar to the results of the current study. However, the average content of this element in the cited study amounted to an average of 0.032% and was, therefore, 19% higher than the average value for the willow biomass in the current study. However, the value of this characteristic for the 15 willow genotypes under study (all harvested in two three-year rotations) varied and averaged between 0.026–0.037% DM.
Black locust biomass was also characterized by significantly higher N and Cl contents averaging 0.91% and 0.032% DM (
Table 4). However, the lowest contents of these elements were noted for willow biomass, while medium contents were found for poplar biomass. The N content in poplar and willow biomass was lower by an average of 52.7% and 58.2%, respectively. However, these differences were smaller for the Cl content and amounted to 15.6% and 40.6%, respectively. The application of lignin for soil enrichment contributed to an increase in the N content in SRWC biomass (an average of 0.61% DM), while on the control plot this value was lower by 8%. It was also noted that the average nitrogen content in biomass was lower in the consecutive harvest rotations, since in the first harvest rotation it averaged 0.62% DM, while in the second and third rotations it was significantly lower (by 6.5% and 17.1%, respectively). It should be added that black locust biomass was generally characterized by a higher N content in all harvest rotations (homogeneous group “a–c”) as compared to poplar (homogeneous group “d–f”) and willow (homogeneous group “e–f”). Moreover, in a study conducted in a warmer climate [
31], the black locust biomass was characterized by higher N and Cl contents of 0.63 and 0.02% DM, respectively, compared to willow and poplar. For willow biomass, the nitrogen content was lower by 27%, and for poplar, by as much as 75%. On the other hand, the lowest chlorine content in the cited study was noted for willow biomass. In another study [
22], the average N content in willow biomass was 0.42% DM and was thus slightly higher than the value noted in the current study. However, it fell within a wider range of 0.36–0.51% DM. The average nitrogen content in poplar biomass (0.41–0.42% DM, i.e., a value similar to that obtained in the current study) was obtained in other studies [
11,
39].
3.3. Practical Implication of the Study
When SRWCs are used for energy purposes, the properties of this biomass type are very often generalized, and the biomass is regarded as a relatively homogeneous energy feedstock with similar parameters.
Table 5 presents descriptive characteristics of the entire dataset for three SRWC species cultivated in eight soil enrichment variants and harvested in three consecutive four-year rotations, therefore for a total of 216 plots. Based on the presented data, the lowest variation expressed by the variation coefficient (below 6%) was noted for such characteristics as the HHV, volatile matter, fixed carbon, and the C and H contents. However, the differences between the minimum and the maximum value for these parameters ranged from 5% to 35%. Even lower were the differences (1–8%) between the values from the upper and lower quartile for these parameters. On the other hand, the biomass moisture and ash contents were characterized by greater variation expressed by the variation coefficient (a range of 15–17%). For example, the SRWC biomass moisture content during the winter harvest was 48.38%. However, the minimum value for this parameter was only 35.05%, while the maximum value was as much as 60.03%, i.e., the difference between the minimum and the maximum value was 71%. Even greater variation was noted for the ash content, where the difference between the minimum and the maximum value was 135%. The differences between the values from the upper and lower quartile for these two parameters were lower and amounted to approx. 33%. Despite this, the contents of sulfur (28%), nitrogen, and chlorine (46% each) were characterized by decidedly higher variation coefficient values. Obviously, for these three elements, the differences between the minimum and the maximum value were greater and amounted to 310% for S, 352% for N, and 1739% for Cl, respectively. On the other hand, the differences between the lower and the upper quartile were 40%, 113%, and 52%, respectively.
Given this variation, similarities were sought between the plots studied over the 12-year period. Therefore,
Figure 1 shows a dendrogram of a hierarchical cluster analysis illustrating the mutual similarities of the biomass of the species and soil enrichment procedures under study in terms of its parameters as a solid biofuel. This analysis showed that in terms of the biomass characteristics under analysis, when cutting off 2/3 Dmax, two clusters were formed (
Figure 1a). One cluster contained the fixed carbon, S, N, and Cl contents, while the second cluster contained the other six parameters under analysis. However, when cutting off 1/3 Dmax, up to six clusters were formed. The fixed carbon content separated from S, N, and Cl, which resulted in the formation of two independent clusters. Consequently, as many as four parameters (fixed carbon, volatile matter, H, and ash contents) constituted separate clusters, while the sixth cluster comprised the moisture content, HHV, and C content. As regards the analysis of the similarities between the SRWC species and the soil enrichment procedures under study, it was found that cutting off 2/3 Dmax formed two clusters (
Figure 1b). Black locust, irrespective of the soil enrichment procedure, formed its own cluster, while poplar and willow formed another common cluster. On the other hand, when cutting off 1/3 Dmax, four clusters were formed. Black locust continued to represent a single separate cluster. Moreover, three separate clusters were formed. One of them contained most soil enrichment variants in poplar cultivation, except poplar F. The second cluster contained poplar and willow in variants F and willow in variant C, while the third cluster included all the remaining soil enrichment variants in willow cultivation.
Black locust is a species that fixes free nitrogen from the air and tolerates unfavorable habitat conditions very well, including the possibility of cultivation on land after open-cast mine reclamation [
40]. This feature is undoubtedly a great advantage of this plant, but it can increase the nitrogen content in biomass. However, the distinctiveness of black locust biomass from willow and poplar biomass is also clearly illustrated by selected descriptive statistics (
Table 6,
Table 7 and
Table 8). As regards the biomass moisture content, the median for the black locust biomass was 38%, and the maximum value was just under 43%, which is favorable in terms of the energy use of this species. However, as regards poplar and willow biomass, the moisture content median was decidedly higher (56 and 50%, respectively) than the maximum value for black locust. Moreover, the black locust biomass N content median (0.93% DM) was higher than the maximum contents of this element in willow and poplar biomass (0.52 and 0.63% DM, respectively). The median and the maximum S and Cl contents in black locust biomass were also higher than the analogous values in willow and poplar biomass. The higher N, S, and Cl contents in black locust biomass are unfavorable in terms of the use of this species for energy purposes. However, it does not mean that biomass from black locust is some kind of problem for the energy industry; rather, it indicates that this biomass is not optimum. The C content and HHV of black locust biomass were lower than the analogous values for willow and poplar biomass, even though these differences were not as great as for the above-described parameters. On the other hand, as regards SRWCs, poplar was characterized by the highest maximum values of biomass moisture, ash, and C contents, as well as the HHV. Willow was characterized by the lowest maximum ash, S, N, and Cl content values.