3.1. Initial Physio-Chemical Properties of Soil, Calciprill, and Sodium Silicate
The selected physio-chemical properties of the soil are summarized in
Table 2. It was a loamy soil (sand, silt, and clay were 48.2%, 24.2%, and 27.6%, respectively) with a bulk density of 1.20 g cm
−3. The parent material of the red-yellow sedimentary rocks explains why Bekenu series is high in total Fe (5960.7 ppm) but lower in total cation saturation, including total K (175.0 ppm), Ca (420.0 ppm), Mg (103.3 ppm), and Na (623.3 ppm), resulting in the formation of a typical acidic soil with a pH
water of 5.127 and a pH
KCl of 3.94. Because the pH of this soil was less than 5.5, it was high in exchangeable acidity (1.21 cmol
(+) kg
−1), Al
3+ (1.03 cmol
(+) kg
−1), and H
+ (0.18 cmol
(+) kg
−1) but notably, exchangeable Al
3+ of this soil exceeded the threshold of 0.8 cmol
(+) kg
−1. This suggests that the soil was saturated with Al toxicity and this explains its low available P (1.24 ppm) because of Al fixation; thus, it required the application of Calciprill and sodium silicate to increase its pH to a desirable range of 5.5 to 7 [
19]. Furthermore, it was a mineral soil, with its organic matter content of 7.24% and organic carbon content of 4.2%, because a typical mineral soil does not contain over 20% organic carbon without prolonged water saturation [
16]. The deep and well-drained profile of Bekenu series suggests the low exchangeable base cations saturation of this soil. The decreasing order of exchangeable cations is: K
+ (76.0 ppm), Mg
2+ (20.4 ppm), Ca
2+ (17.1 ppm), and Na
+ (7.84 ppm). The soil had the highest exchangeable Fe
2+ concentration (476.9 ppm) compared with other exchangeable cations because of its parent material. This high Fe
2+ can also fix P.
The selected chemical properties of the Calciprill and sodium silicate are summarized in
Table 3. Both Calciprill and sodium silicate are base amendments that can be used to increase the pH of Bekenu series (
Typic Paleudults). This is because the pH
water and pH
KCl of Calciprill were 7.77 and 7.78, respectively, whereas those of the sodium silicate were 12.96 and 12.92, respectively. The EC of sodium silicate was higher (113.17 dS m
−1) compared with that of the Calciprill (3.11 dS m
−1). Both Calciprill and sodium silicate had low exchangeable NH
4+ and available NO
3−, suggesting that additional N fertilizers will be needed to meet crop N requirements. The sodium silicate can be used to increase soil available P because of its higher P availability (10.90 ppm) compared with the soil (1.24 ppm) and Calciprill (1.18 ppm). Based on the base exchangeable cations, the Calciprill is a liming material that is made up of highly purified CaCO
3 with a determined exchangeable Ca
2+ of 9696.81 ppm, followed by exchangeable Na
+, K
+, and Mg
2+ of 1903.65 ppm, 311.69 ppm, and 104.23 ppm, respectively. Additionally, the sodium silicate is a base amendment that is mainly formed by Na
2O and SiO
2, with exchangeable Na
+ and Si concentrations of 100,749.90 ppm and 71.33%, respectively (
Table 3). According to Ma and Takahashi [
33] and Schaller et al. [
34], the Si in sodium silicate does not only increase soil pH, but it also improves soil P availability because Si has a high affinity for Fe ions. The reaction unlocks fixed P and C.
3.2. Combined Use of Calciprill and Sodium Silicate on Soil pHKCl, Exchangeable Aluminium, Iron, and Manganese Ions
Soil pH
KCl for the combined use of Calciprill and sodium silicate treatments significantly increased to the range of 7.69 to 8.21 at 40 DAI, 7.71 to 8 at 80 DAI, and 7.71 to 8.19 at 120 DAI compared with soil only (C0S0) at 40 DAI (3.73), 80 DAI (3.63), and 120 DAI (3.71) (
Table 4). The increase in soil pH
KCl was due to the significant reduction in the soil exchangeable H
+ compared with soil only (C0S0) because soil pH is inversely proportional to the concentration of soil exchangeable H
+. Additionally, this was due to the neutralization of H
+ by carbonate ions (CO
32−) released by the Calciprill into the soil solution. This resulted in the significant reduction in exchangeable acidity and H
+. One mole of CO
32− ion reacts with two moles of H
+ ions to produce carbonic acid (H
2CO
3) as an intermediate, followed by breaking down into water and carbon dioxide [
17]. The release of base cations such as K
+, Ca
2+, Mg
2+, and Na
+ from the amendments also contributed to the increase in the soil pH and immobilization of H
+. This finding is comparable to that of Cai et al. [
35] who reported that the addition of amendments with a higher base saturation to acidic soils increases their base saturation; thus, improving the immobilization of H
+ via exchange reactions between soils and amendments. The H
+ ions released during nitrification and base cation uptake by plants via ion exchange reaction can be neutralized by CaCO
3 through continued dissolution over time; thus, resulting in increased soil pH buffering capacity [
36].
Notably, the combined use of Calciprill and sodium silicate significantly reduced exchangeable Al compared with soil only (C0S0) without these amendments. At 40 DAI, 80 DAI, and 120 DAI, the exchangeable Al for the soils with the amendments ranged from 0.03 to 0.04 cmol
(+) kg
−1, 0.02 to 0.04 cmol
(+) kg
−1, and 0.03 to 0.04 cmol
(+) kg
−1, respectively. These values are below the threshold of Al toxicity at 0.8 cmol
(+) kg
−1 and those for soil only (C0S0) at 40 DAI (1.05 cmol
(+) kg
−1), 80 DAI (0.99 cmol
(+) kg
−1), and 120 DAI (1.06 cmol
(+) kg
−1) (
Table 5). These results suggest that the exchangeable Al ions had been greatly suppressed because the exchangeable Al was precipitated as insoluble Al hydroxides [
5]. Al hydrolysis to produce H ions decreases with increasing pH [
17,
37]. For example, a complete hydrolysis of one mole of Al
3+ produces three moles of H
+ to decrease soil pH. In the present study, this reaction was impeded because of the acid neutralizing ability of the Calciprill and sodium silicate.
At 40 DAI, 80 DAI, and 120 DAI, the combined use of Calciprill and sodium silicate significantly reduced exchangeable Fe
2+ and Mn
2+ compared with soil only (C0S0) (
Table 6 and
Table 7). This is because these amendments increased soil pH to facilitate exchangeable Fe
2+, reacting with OH
− to form insoluble Fe hydroxides [
17,
38]. The C3S5 treatment demonstrated the lowest exchangeable Mn
2+ at 40 DAI (2.94 ppm) and 120 DAI (2.45 ppm), suggesting that C3S5 is the most suitable combination to suppress exchangeable Mn
2+ because of the significant differences in pH
KCl. A significant increase in soil pH transforms divalent Mn into oxide fractions via oxidation to reduce exchangeable Mn
2+ [
39].
3.3. Combined Use of Calciprill and Sodium Silicate on Exchangeable Ammonium, Available Nitrate, and Available Phosphorus
At 40 DAI, exchangeable NH
4+ in the soils with Calciprill and sodium silicate (especially C3S3, C3S4, and C3S5) significantly increased and ranged from 48.57 ppm to 52.30 ppm compared with the exchangeable NH
4+ (32.22 ppm) of soil only (C0S0) (
Table 8). This was partly due to the significant increase in the soil pH following the combined use of the Calciprill and sodium silicate. According to Bikley et al. [
40], increased soil pH improves the transformation of organic N into NH
4+ through enhanced mineralization, suggesting that higher rates of Calciprill and sodium silicate can increase soil NH
4+ availability. This was possible because the amendments significantly improved the soil ECEC, thus resulting in higher soil exchangeable NH
4+ retention because of the increased number of negatively charged sites of soil. This finding is consistent with those Gasser [
41] and Avnimelech and Laher [
42], who reported that soil CEC is the most important factor that reduces NH
4+ loss through NH
3 volatilization because soils with higher CEC are able to retain exchangeable NH
4+ from being transformed by, for example, urease. Urease is the enzyme that catalyzes NH
4+ transformation to NH
3 emission. There were no significant differences among the treatments with Calciprill and sodium silicate for exchangeable NH
4+ compared with soil only (C0S0) at 80 DAI and 120 DAI (
Table 8) because both of the amendments had low exchangeable NH
4+. Thus, application of nitrogen-based fertilizers and organic materials to significantly increase soil exchangeable NH
4+ in agricultural systems which include liming programs using Calciprill and sodium silicate is essential.
At 40 DAI and 80 DAI, the combined use of Calciprill and sodium silicate significantly improved soil available NO
3− compared with soil only (C0S0) because of the increase in soil pH which improved the mineralization of organic N into inorganic NO
3− [
43]. However, it was observed that soil available NO
3− significantly increased in the soils with lower rates of Calciprill and sodium silicate, whereas exchangeable NH
4+ was significantly higher in the soils with higher application rates of Calciprill and sodium silicate (
Table 8 and
Table 9). This was partly due to the significant difference in soil pH and CaCO
3 contents among those treatments, because lower pH and CaCO
3 transformed exchangeable NH
4+ to NO
3− through nitrification [
36,
43]. Moreover, the higher soil NH
4+ retention was due to the higher soil ECEC. This contributed to lower available NO
3− because of reduced nitrification. This finding corroborates the findings of Ferguson and Pepper [
44] and MacKown and Tucker [
45], who also reported that increased soil CEC prevents exchangeable NH
4+ from being transformed into available NO
3− through nitrification. At 120 DAI, available NO
3− of the soils with and without Calciprill and sodium silicate were similar (
Table 9) because of the reduced transformation of soil exchangeable NH
4+ to available NO
3−. Some of the exchangeable NH
4+ might have been lost through NH
3 volatilization. Moreover, both of the amendments were lower in available NO
3− compared with the soil, suggesting that application of nitrogen-based fertilizers is needed to increase soil available NO
3−.
At 40 DAI, 80 DAI, and 120 DAI, the soils with the amendments significantly enhanced soil available P compared with soil only (C0S0) (
Table 10). The increase in available P availability was due to mineralization of organic P into inorganic available P, because the improved soil pH stimulated the soil microbes to decompose the organic materials in the soil to release P [
46,
47]. This was due to the increased soil pH from the initial pH
KCl of 3.94 to a pH range of 7.69 to 8.21 after applying the Calciprill and sodium silicate, because they significantly reduced exchangeable Al
3+, Fe
2+, and Mn
2+. For example, the Calciprill and sodium silicate significantly reduced soil exchangeable Al
3+ below the threshold of 0.8 cmol
(+) kg
−1 to alleviate Al and Fe toxicity [
4]. This suggests that the soil pH following the combined use of Calciprill and sodium silicate unlocked P fixed by Al, Fe, and Mn [
5,
17,
37]. Thus, the lower available P for the soil without Calciprill and sodium silicate (C0S0) was due to the reaction between P and soluble Fe, Al, and Mn ions, suggesting that soil pH is the dominant factor in controlling P availability [
38].
In addition, the increase in available P was partly due to ability of the Si to mobilize P from the exchangeable sites of the soil–Fe interaction. Schaller et al. [
34] reported that an increase in Si availability in soils correlates positively with P mobilization. Release of P from sorption sites of soil iron minerals is related to a stronger bonding affinity of Si to soil minerals compared with P. Thus, Si mobilizes P by replacing P on the soil exchangeable sites, resulting in increased P availability [
34,
48]. Moreover, the significant increase in the available P via sodium silicate application was partly due to the significant decrease in exchangeable Fe
2+ and Al
3+. Reduced exchangeable Al
3+, Fe
2+, and Mn
2+ also decreases P fixation because balanced use of Si increases soil pH to reduce re-sorption of P onto hydrolyzed Al, Fe, and Mn ions. Silicon is capable of outcompeting to prevent P from being sorbed on the surfaces of Al, Fe, and Mn minerals [
49].
It is believed that P availability is constrained by increased exchangeable cation concentrations (especially exchangeable Ca). This occurs when soil is limed above pH 7, because available P reacts with CaCO
3 to form Ca–P compounds. Phosphate solubility decreases with increasing soil pH, followed by formation of precipitated P compounds via crystallization [
7]. It was possible for P to react with Na to form soluble Na–P following application of sodium silicate, but this reaction does not significantly affect P availability [
50]. This explains why P availability reaches its maximum when the soil pH is between 6.5 and 7. At 40 DAI, 80 DAI, and 120 DAI, it was observed that available P was consistently higher in soils with the highest rates of Calciprill and sodium silicate (C3S5) compared with soil only (C0S0), although the soils with the Calciprill and sodium silicate were alkaline (
Table 10). This suggests that P fixation is significantly higher in acidic soils compared with alkaline soils [
51].
3.4. Combined Use of Calciprill and Sodium Silicate on Electrical Conductivity, Exchangeable Base Cations, and Effective Cation Exchange Capacity
At 40 DAI, 80 DAI, and 120 DAI, the soil electrical conductivity was significantly affected by combined use of Calciprill and sodium silicate compared with soil only (C0S0) (
Table 11), suggesting that the sodium silicate is salty and it must not be excessively used. According to USDA [
52], the threshold of soil electrical conductivity to impede crop growth and microorganism activities is 4.0 dS m
−1. Based on
Table 11, the EC of the combined use of Calciprill and sodium silicate did not exceed this threshold and was rather within the salinity class of non-saline (0 to 2 dS m
−1), suggesting that the application rates of Calciprill and sodium silicate used in this present study were acceptable for crop cultivation.
At 40 DAI, 80 DAI, and 120 DAI, the combined use of Calciprill and sodium silicate significantly increased exchangeable K
+, Ca
2+, Mg
2+, and Na
+ compared with C0S0 (
Figure 1,
Figure 2,
Figure 3 and
Figure 4) because the inherent contents of K
+, Ca
2+, Mg
2+, and Na
+ of the amendments increased the soil base saturation. Cai et al. [
35] reported that base saturation of soils can be increased with the addition of amendments that are high in base saturation. The soils with the highest rates of Calciprill and sodium silicate (C3S5) demonstrated the highest exchangeable K
+ availability at 40 DAI (35.33 ppm), 80 DAI (22.40 ppm), and 120 DAI (28.13 ppm) (
Figure 1), suggesting C3S5 is the most suitable combination of Calciprill and sodium silicate for exchangeable K
+ availability. At 40 DAI, 80 DAI, and 120 DAI, unlike exchangeable K
+, exchangeable Ca
2+ and Mg
2+ did not increase with the increasing rates of both amendments (
Figure 2 and
Figure 3) because of the incomplete dissolution of Calciprill, unlike sodium silicate which is highly soluble in water, although it is not high in Ca and Mg compared with the soil. Soil exchangeable Na
+ was significantly affected by the increasing amount of the sodium silicate compared with soil only (C0S0) at 40 DAI, 80 DAI, and 120 DAI (
Figure 4). This suggests that the application rates of sodium silicate can significantly influence soil exchangeable Na
+ because of its inherent Na
+ in the sodium silicate.
At 40 DAI, 80 DAI, and 120 DAI, ECEC significantly increased with the combined use of Calciprill and sodium silicate compared with soil only (C0S0) (
Table 12), and this relates to the amendments’ ability to increase soil pH. Aprile and Lorandi [
53] reported that soil CEC correlates with ECEC when soil pH is greater than 8.3 because soil exchangeable acidity is considered negligible. Sdiri et al. [
54] reported that soils that are saturated with higher CaCO
3, rather than Al
2O
3 and Fe
2O
3, have higher ECEC because of the increased number of negatively charged sites on the surface of CaCO
3. In other words, increased soil pH and surface charge on soil minerals through Calciprill application improved the soil ECEC [
55].
The effects of the combined use of Calciprill and sodium silicate on ECEC were not consistent because of the incomplete dissolution of Calciprill (
Table 12). The incomplete dissolution of Calciprill suggests that this amendment can provide more negatively charged surface area for adsorbing more exchangeable cations to increase the ECEC of the soil. This finding is comparable to that of Zhao et al. [
56] who also reported that CaCO
3 can regulate the ECEC of alkaline soils. However, with time, continued dissolution of Calciprill in the soils can reduce ECEC because CaCO
3 decomposes into exchangeable Ca
2+ and CO
32− to neutralize immobilized H
+, thus reducing negatively charged surface area for exchangeable cations adsorption [
36]. The continued dissolution of CaCO
3 increases soil pH buffering capacity. At soil pH 8, Bowman et al. [
57] reported that dissolution of CaCO
3 can significantly improve soil pH buffering capacity. Moreover, at 40 DAI, 80 DAI, and 120 DAI, with the same amount of Calciprill (C1, C2, and C3, respectively), the ECEC of the soil with the highest rate of sodium silicate (S5) was significantly higher than with the lowest rate of sodium silicate (S1), suggesting that sodium silicate can improve soil ECEC.