the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Covariation of redox potential profiles and water table level in peatland sites representing different drainage regimes: implications for ecological modelling
Abstract. Reduction-oxidation (redox) reactions are ubiquitous in nature, responsible for the energy acquisition of all organisms. Redox reactions are electron transfer reactions and necessarily involve two participants: one being oxidised (electron donor) and one being reduced (electron acceptor).
Availability of terminal electron acceptors (TEAs) is a major determinant of the extent to which the carbon in OM can be oxidised in an ecosystem. This is the most important under waterlogged conditions, such as in peatlands, where diffusion of O2, the most effective common TEA, into the soil is blocked by water. Under these conditions, available alternate TEAs are used by microbiota to continue OM oxidation.
The decomposition processes in soil can be characterised by its redox state, ie. which TEA is responsible for oxidation of OM at a given time. This can in principle be measured as a voltage between the soil solution and a known reference electrode, known as the redox potential.
Current soil ecosystem models do not depict the use of alternate TEAs well. This limits their applicability for predicting soil carbon loss under different drainage regimes, and thus their usefulness for assessing best management practices for soil carbon preservation and water course protection. Water table level (WTL) is the most common determinant of the mode of decomposition in ecosystem models, implying the assumption that the redox state of a peatland ecosystem responds predictably to changes in WTL.
We conducted a two-year redox monitoring experiment in a boreal mesotrophic peatland under three drainage regimes: undrained, short-term drainage and long-term drainage. In addition, an ombrotrophic long-term drained plot was monitored. Snapshot assessments of the activities of three major metabolic enzymes, arginine deaminase, protease and urease, were also done in the mesotrophic plots, indicating differences in microbial activities between the drainage regimes.
We found that WTL was a poor temporal predictor of redox potential, but that the position of major transition zones between oxic and anoxic states as well as enzymatic activities within the peat profile were somewhat determined be the dominant WTL depth. In the undrained plots especially redox potential values reflecting oxic or suboxic conditions were often found below the WTL, whereas on the drained plots anoxia was present above the WTL. Preceding redox potential was found to affect enzymatic activities of protease and urease, but not arginine, in all measured plots.
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RC1: 'Comment on egusphere-2024-2050', Jim Boonman, 23 Sep 2024
The manuscript features the undervalued but fundamental redox potential that serves as indicator of peat mineralization processes. Besides, the redox potential is coupled to measurements of enzyme activity. The authors raise interesting hypotheses and present valuable results (although figures and tables might still be distilled better). The results are well-integrated in literature in the discussion, and conclusions are communicated clearly. Nevertheless, I believe that certain improvements should be made before publication. In particular, I have concerns regarding the methodology used to determine the Fe-reduction isopotential (and the associated hypothesis), as well as the discussion regarding bi-modality in Eh (and the answers provided to this hypothesis). Please find more specific comments in the attached file.
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RC2: 'Comment on egusphere-2024-2050', Anonymous Referee #2, 23 Dec 2024
This work provides monitoring data focused on measurements of pH-normalized oxidation-reduction potential (Eh) at four sites encompassing bogs and fens in southern Finland with different drainage histories (undrained, short-term drainage, long-term drainage). As such, the sites have a range in dominant modes of vegetation and moss types, as well as pH range. The study also measured seasonal changes in three hydrolytic enzyme activity potentials. The principal objective was to evaluate changes in water table level as a predictor of Eh. The authors explored “wavelet decomposition” to identify patterns that would inform future modelling efforts, as well as more traditional linear and non-linear models with physical parameters as independent variables (temperature, water table level). The main take-away from this analysis was that the drivers and predictors of Eh across a bog-fen continuum are complex, and while water table and temperature likely do exert some significant predictive capacity for Eh (Appendix findings, A1-A3), the wavelet analysis did not yield straightforward results. Another significant finding was that Eh was strongly correlated with some hydrolytic enzyme potentials. I note here that the authors devoted 8 figures to the wavelet analysis, and yet the more straightforward linear and non-linear model analysis was buried in the appendix. I mention this because this manuscript as written is quite long for a peer-reviewed paper (14 figures). In full disclosure, the wavelet analysis was largely outside my area of knowledge, so I will have to defer to other referees to evaluate that component. I think that with some “tidying up” this manuscript should be a valuable contribution, and I offer comments by line number in hopes they are helpful in revision.
Lines 110-115: It was interesting to see a focus on hydrolytic enzymes, given the focus on Eh. Why were no oxidative enzymes chosen? It seems this would be more relevant to ‘enzymic latch’ mentioned in discussion? I think it would be appropriate to justify that here.
Lines ~157-162; Line 185: There should be some more information about the “redox probes”. Were these calibrated in any way (run against a standard, like Zobell’s or Lights Solution). How were they conditioned? Were the pH electrodes calibrated, and how?
Table 1, Figure 13 bars: I appreciate the theoretical thermodynamic cutoff ranges for redox pairs for context, but seeing as the authors did not measure redox couples in this study, perhaps this could be removed, or put in appendix? Just a suggestion.
Line 170: Again, interesting focus on hydrolytic, given the focus on oxidation reduction potential.
Line 182: Why was 200mV added to the probe reading? The authors later state that Eh-pH was normalized using the Nernst equation; what is this “+200mV” doing?
Figure 3: It is surprising that there is not really a vertical temperature gradient.
Wavelet analysis figures: I think the captions could make these more accessible. What does the Y axis represent? I apologize for not having expertise in this area, but I suspect a large amount of the readership of this paper won’t either.
Enzyme activity tables: Please provide units and provide context in the text (results and discussion). As written, we do not know if these values are “reasonable”; are these potential activities in the pocket of prior research?
Correlation Matrix Tables: It would be helpful if the x axis could also contain labels, so the reader doesn’t have to count columns to compare r values.
Discussion: I am very interested in the analysis performed that is buried in the Appendix (A1-A3).
Lines ~325-330 : It has also been shown that meteoric inputs from rainfall can have an oxidizing effect on pore water chemistry. Please see the paper by Mitchell and Branfireun (2005) in the journal, “Ecosystems”, 8:731-747.
Line ~345: Moreover, temperature plays a critical role in the solubility of Oxygen in water (see your appendix models). It is common to see a gradual reduction in DO with the progression of the growing season in peatlands, as soils warm and respiration increases. I think a brief nod to this would be good, and this would be a good place to engage your linear and nonlinear modelling exercises.
Figures A1-A3: I would like to see perhaps XY predicted vs. observed plots; if you squint here, it actually looks like these more traditional approaches are doing fairly well at predicting Eh.
Citation: https://doi.org/10.5194/egusphere-2024-2050-RC2
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