4.1. Total Elements and Plant Available Phosphorus
The abundance of Ca, Mg, Fe, and Al (
Table S1) indicated that the studied peatlands are minerogenic [
35]. The significant differences of these element concentrations among soil horizons and the peatland types can be associated with differences in pedogenesis and degree of peat degradation. As a result, peat degradation and leaching could be attributed to the low concentration of total Ca in relatively low soil organic matter content of the coastal peatlands [
36]. However, the higher P and K (
Table S1) concentrations at the surface than at the subsurface horizons can be explained by historical fertilizer applications. A mixture of sand and peat layers between the peat horizons explained the slight increase of the concentration of total P at the 20–40 cm soil depth of the drained forest peat (
Table S1). However, the sudden increase in the concentration of total P at the 40-60 cm soil depth of the drained percolation mire could be due to P translocation from the P-rich surface horizon. Overall, the total P content of the surface and subsurface horizons was similar to those reported from fen peatlands of Aschersleben, Saxony-Anhalt and the Trebel valley, Mecklenburg-West Pomerania [
19,
20]. The lower concentrations of K, Na, and Mn than the other elements are explained by their lower concentrations in plant biomass and losses during the partial decomposition of the peat-forming plant materials since these ions of these elements are less strongly bound than ions of the other elements. The high concentrations of Fe and Al in the peatlands can support the formation of metal bridges between humic substances and P
i complexes [
37,
38]. The high abundance of Al could be beneficial since Al-containing compounds were applied to increase P sorption in peat soils [
39]. However, the high abundance of Fe could form redox-sensitive P compounds that can be mobilized in the rewetted peatland [
15].
The values of the plant available P of the present study (
Figure 1) were higher than those reported from the different European peatlands extracted by the same method [
19]. Similar to the total P (
Table 2 and
Table S1), the plant available P decreased from the surface to subsurface horizons. This is explained by P release from peat decomposition, historical fertilization, excrement from grazing animals, and external inputs with water and atmospheric deposition. The lower concentration of plant available P at the subsurface than surface horizons and lack of significant differences at the subsurface horizons indicated that P translocation from the surface to the subsurface horizons was negligible or the leached P lost from the soil profiles. Other researchers reported the danger of P leaching from the surface to subsurface horizons of peat soils upon rewetting [
14,
40]. The disagreeing results can be attributed to variations in current land use, soil organic matter content, and predominant P species or experimental approaches, and peatland types. Overall, the plant available P extracted by double lactate in the present study was lower than those extracted by ammonium lactate and sodium bicarbonate since double lactate cannot extract P bound to organic matter.
4.2. Phosphorus Fractions
The predominance of P
o and residual P fractions with the sequential P fractionation method (
Table 1 and
Figure 2) agreed with the results of similar studies reported from peat soils of different European countries [
19,
20]. The lower concentration of P
i than P
o in the present study was not surprising since the soil organic matter contents of the studied peatlands were in the range of 42% to 75% at the surface horizons [
21]. The distribution of the H
2SO
4-P
i fraction in the peat horizons followed the distribution of mineral contents in the peat profiles [
21], which means the higher mineral content was associated with higher concentrations of H
2SO
4-P
i.
The concentration of NaOH-P
o was larger by factor two to that of the concentration of NaHCO
3-P
o at their respective horizon indicating that the major proportion of P
o existed in the moderately labile NaOH-P
o form. Rewetting peatlands with such a high P
o content is unlikely to enhance P mobilization unless the P
i is associated with the redox-sensitive elements [
41]. However, the XANES analysis indicated the presence of crystalline FePO
4, amorphous AlPO
4, and MgHPO
4 only in a few horizons in the present study (
Table 6). The higher proportions of P recovered by the sequential P fractionation from the drained than from the rewetted peatlands (
Figure 2) indicated that the P stability was higher in the rewetted peatlands. Similarly, the lower concentration of stable P fractions (H
2SO
4-P + residual-P) at the surface horizons of the drained than their respective rewetted peatlands indicated that rewetting of former drained sites could transform moderately labile P into stable P fractions.
Similar to the sequential P fractionation method, the higher concentration of P
o than P
i with the ignition (
Table 2) and NaOH-EDTA (
Table 3) methods further confirmed that P
o was the predominant P fractions in all the studied peatland types. However, the higher P
i in the ignition method (
Table 2) than in the sequential P fractionation (
Table 1) and NaOH-EDTA (
Table 3) can be attributed to differences in P recovering capacity of the different methods. The sequential P fractionation recovered 54% to 94% of total P while the NaOH-EDTA recovered 51% to 85% of total P except the subsurface horizons of percolation mires. The ignition method was assumed to recover 100% of the P
i and P
o, although some P
o compounds can be transformed to P
i by this method [
24]. The percent of total P recovered by the NaOH-EDTA was in the range of the results reported from diverse temperate and tropical peatlands [
42]. Similar to the sequential P fractionation method, the NaOH-EDTA also recovered less total P from the rewetted and subsurface horizons than drained surface horizons (
Table 1 and
Table 3) which further confirmed that rewetting increased the P stability.
Comparing the present study with nine major soil groups of 13 studies (
Table S2 and
Figure 4) clearly illustrated the quality of the Hedley sequential P fractionation in distinguishing labile to stable P fractions in weakly to highly weathered soils. The distribution of different P fractions in the rewetted peatlands of the present study (Histosol
w) (
Figure 4) related more to that of the Ferralsols indicating that P is more stable in the long-term rewetted peatlands than in the drained peatlands (Histosol
d) and some other major soil groups. Furthermore, the difference in the distribution of P fractions between the mean of three drained and three rewetted peatlands of the present study were remarkable (
Figure 4). Accordingly, the proportion of labile (21%) and moderately labile (30%) P fractions in the drained peatlands were higher than the proportions of labile (12%) and moderately labile (22%) P fractions of the rewetted peatlands (
Figure 4). This implies the stable P fractions in the drained peatlands (49%) were less than the stable P fractions in the rewetted peatlands (66%). Overall, the Hedley sequential P fractions not only reflect the influence of land uses and soil-management practices [
15,
43] but also the influence of soil genesis on P distributions and transformations [
44,
45]. For instance, the predominance of H
2SO
4-P fraction in the Fluvisol (
Figure 4) indicated the abundance of primary phosphates like apatite and P associated with Ca (28). Although most researchers have not determined this, the H
2SO
4-P fraction also contained P
o in peat soils (
Table 1). The mean proportion of P
o in the H
2SO
4-P fraction in three drained Histosols was 7% of the total P, whereas that of mean for three rewetted peatlands was 11% of total P as P
o (
Table 1). However, regardless of the abundance of P
i or P
o, the H
2SO
4-P fraction is stable and contributes less to soluble and mobile P in the short term.
The higher labile and moderately labile P fractions in the drained peatlands than that of the rewetted peatlands of the present study clearly indicated the P fractions could easily be released upon mechanical disturbance of the drained peatlands. Furthermore, not only drainage but also the current land uses and management practices could influence P transformation and distribution. Soils subjected to continuous cultivation and fertilization could be more dangerous than the drained peatlands used as grasslands. For example, the relative proportion of easily exchangeable P (AEM-P) in Luvisols, Alisols, and Histosols (
Figure 4) could more easily contribute to freshwater eutrophication than the drained peatlands of the present study. Thus, not only drainage and rewetting but also current land use and management practices, accessibility to a waterbody, and topographic position could determine whether a peatland is a sink or a source of P.
Overall, the results of the present study showed that the response of P to drainage and rewetting depend on the predominant P fractions and biogeochemistry of the studied soils in addition to management practices. For example, rewetting increased the P stability when the predominant P fraction was P
o and drainage increased P
o oxidation regardless of soil types [
59,
60]. On the other hand, long-term rewetting mineral soils increased P release and decreased the degree of P saturation [
61,
62]. However, another study reported that drainage increased the maximum P sorption capacity of Cambisol in simulated alternating drainage-rewetting experiment [
63]. Such contrasting results can be attributed to variations in the experimental approaches, anthropological factors, and topographic positions. This unequivocally indicates drainage and rewetting cycles can differently influence P dynamics in different soil types. Thus, knowing different P
o and P
i fractions and soil biogeochemistry can help to understand the influence of drainage and rewetting on P dynamics in a given soil.
4.3. Solution 31P NMR and P K-XANES
The P species identified by the solution
31P NMR analysis agreed with the results of similar studies conducted on agriculturally influenced European peat soils [
64]. The predominance of α- and β-glycerol phosphates species in the
31P NMR analysis (
Figure 3 and
Table 5) can be attributed to the hydrolysis of orthophosphate diesters during the alkaline extraction [
65]. However, in the
31P NMR analysis, the IHP was the second to the glycerol phosphates (
Table 5), indicating that P
o in the peat soils was part of structural components of the partially decomposed peats. This is not surprising since the studied peats were partially decomposed with the high C-content [
21] that was similar to that of the undecomposed plant materials. A similar study conducted on peatlands of diverse organic matter content also indicated that the IPH abundance was directly proportional to the mineral contents and inversely proportional to soil organic matter content [
42].
The lower proportion of P
o recovered by solution
31P NMR than P
o recovered by sequential P fractionation, NaOH-EDTA, and ignition methods can be attributed to the high concentration of Fe in the NaOH-EDTA extracts (
Table 4). The high Fe concentration (1.09 to 26.09 g kg
−1) recovered by the NaOH-EDTA extraction can hinder P speciation by the solution
31P NMR since Fe is known to disturb NMR spectra quality in soil and environmental samples due to line broadening and increasing signal relaxation rates [
66]. For instance, the concentration of Fe was the highest in the rewetted forest peatland where the weak signal to noise ratio made it difficult to identify the peaks of orthophosphate monoesters and diesters in this sample (
Figure 2b).
In the present study, the P
K-XANES analysis was able to distinguish P
o from P
i species; however, it failed to identify different P
o species since all P
o species were identified as if it were IHP (
Table 6). This agreed with the recent conclusion derived from a review of many previous studies where only two to five chemical species of P can be identified using one of spectroscopic techniques such as XANES and NMR [
67]. The authors also emphasized the matrix complexity of the soil and environmental samples increased the uncertainty in chemical P speciation by most of the spectroscopic techniques. However, the relative proportion of P
i species detected by the XANES analysis at the surface horizons of most sites (
Table 6) was similar to the sequential P fractionation and NaOH-EDTA methods (
Table 1 and
Table 3). This is in line with the results of previous studies that indicated XANES is more suitable for P speciation in minerals and crystalline compounds than P
o species [
67,
68,
69].
4.4. Synthesis
Among the analytical techniques used, the sequential P fractionation method clearly demonstrated the influence of drainage and rewetting on P speciation (
Figure 1,
Table 1). Although this method has not been used widely for P speciation in peat soils, two global reviews showed that the method can distinguish the impact of soil formation [
44] and different land uses and management practices on P dynamics in minerals soils of temperate, tropical, and subtropical climates [
15]. Furthermore, rewetting increased the absolute concentration and relative proportions of H
2SO
4-P and residual-P (
Table 1 and
Figure 2), which was resistant to extraction by the strong chemicals. Therefore, rewetting degraded peatlands are not an option but a must to lock up P in soil organic matter and transform labile P to stable P forms.
The results of
31P NMR and P K-XANES analyses indicated that P
o was the predominant P species; however, each of the spectroscopic analysis did not decipher the influence of long-term drainage and rewetting on P speciation. Furthermore, degradation of labile P
o species during alkaline extraction, high concentration of Fe and organic matter in the extracts were the challenges during the NMR analysis. The addition of Na
2S. 9H
2SO
4, supposed to reduce Fe concentration [
30], improved the spectra quality in samples with relatively low Fe content (
Table 4 and
Figure 2f), but it did not solve the problem for samples with the high Fe content. The high organic matter [
21] contributed to high viscosity but the recommended further diluting resulted in the disappearing of peaks from NMR spectra, especially for samples with the low P content. The XANES analysis was able to distinguish P
o and P
i but it was not sensitive enough in distinguishing the impact of drainage and rewetting on P speciation in the studied peat soils.
The abrupt change of total P from the surface (0–20 cm soil depths) to subsurface horizons (20–80 cm soil depths) (
Table S1) clearly indicated that P accumulation at the surface horizons originated from relatively recent history since intensive use of chemical P fertilizers have started in the mid-20th century in Germany and elsewhere [
70]. The significant differences in total P at the surface horizons of different peatlands can be attributed to variations in P inputs and outputs. However, the significant variations in the distribution of different P fractions could be due to biogeochemical processes in addition to P inputs and outputs to and from the soils. For instance, the distribution of P fractions can change under aerobic-anaerobic conditions [
71]. Furthermore, the relative proportion of mineral and organic matter in the horizons influenced the absolute and relative proportion of different P fractions recovered by sequential P fractionation, ignition, and NaOH-EDTA methods (
Table 1,
Table 2 and
Table 3 and
Figure 2). Differences in soil organic matter can explain the higher relative proportion of stable P fractions in the percolation mires than in the costal and drained forest peatlands (
Figure 2). The higher proportions of stable P fractions with depths also agreed with the higher soil organic matter content in the subsurface horizons of the percolation mires [
21].
Many previous studies reported that rewetting increased P solubility and mobility in soils [
13,
14,
40]. These studies, however, investigated the effect of anaerobic conditions on degraded fen peat that was previously P-enriched by fertilization. The results of the present study described systems in which new peat has been formed under the influence of longer-term rewetting. In this situation, it is plausible that P was incorporated into stable, mostly organic compounds, in the long-term rewetted peatlands.