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A mechanism of abiotic immobilization of nitrate in forest ecosystems: the ferrous wheel hypothesis
Abstract
Forest soils, rather than woody biomass, are the dominant long‐term sink for N in forest fertilization studies and, by inference, for N from atmospheric deposition. Recent evidence of significant abiotic immobilization of inorganic‐N in forest humus layers challenges a previously widely held view that microbial processes are the dominant pathways for N immobilization in soil. Understanding the plant, microbial, and abiotic mechanisms of N immobilization in forest soils has important implications for understanding current and future carbon budgets. Abiotic immobilization of nitrate is particularly perplexing because the thermodynamics of nitrate reduction in soils are not generally favorable under oxic conditions. Here we present preliminary evidence for a testable hypothesis that explains abiotic immobilization of nitrate in forest soils. Because iron (and perhaps manganese) plays a key role as a catalyst, with Fe(II) reducing nitrate and reduced forms of carbon then regenerating Fe(II), we call this ‘the ferrous wheel hypothesis’. After nitrate is reduced to nitrite, we hypothesize that nitrite reacts with dissolved organic matter through nitration and nitrosation of aromatic ring structures, thus producing dissolved organic nitrogen (DON). In addition to ignorance about mechanisms of DON production, little is known about DON dynamics in soil and its fate within ecosystems. Evidence from leaching and watershed studies suggests that DON production and consumption may be largely uncoupled from seasonal biological processes, although biological processes ultimately produce the DOC and reducing power that affect DON formation and the entire N cycle. The ferrous wheel hypothesis includes both biological and abiological processes, but the reducing power of plant‐derived organic matter may build up over seasons and years while the abiotic reduction of nitrate and reaction of organic matter with nitrite may occur in a matter of seconds after nitrate enters the soil solution.
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“The formation of complex organic macro-molecules (humus) may even be promoted when a biochar is Fe- and Mn-nanoparticle-rich (as the one used here) due to “ferrous wheel” type reactions73, alongside microbial activities2460.”
From Plant growth improvement mediated by nitrate capture in co-composted biochar (2015) · cites this paper as [73]
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“In addition, Fe oxidation coupled with denitrification via biotic and abiotic pathways is also observed in wetland soils, sediments, or anoxic microsites (Davidson et al. 2003; Straub et al. 2004; Smolders et al. 2010).”
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BackgroundAbiotic Nitrate Retention in Agroecosystems and a Forest Soil
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“Humic and fulvic acids, which are widely involved in transformation of metals and organic matters in environment [2], are among the most studied DOM fractions [3,4].”
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“…of corresponding author: jstucki@illinois.edu DOI: 10.1346/CCMN.2012.0600503 Fe(II) is thought to be able to reduce nitrate to nitrite, which then reacts rapidly to produce N2 or binds with organic substances to produce dissolved organic nitrogen (Davidson et al., 2003; Burgin and Hamilton, 2007).”
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Copper availability governs nitrous oxide accumulation in wetland soils and stream sediments
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“Autotrophic and mixotrophic denitrifiers can gain energy from mediating the reduction of 92 NO3- by inorganic electron donors that include sulfur compounds (So, S2-, S2O32), pyrite (FeS2), Fe2+, Fe0, 93 and Mn2+ (Davidson et al., 2003; Weber et al., 2006; Melton et al., 2014; Di Capua et al., 2019; Wei et al., 94 2019…”
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“Second, Davidson et al. (2003) proposed that NO3 − inputs might be chemically transformed to organic N through organic matter–iron interactions.”
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“At the same time, ferric (Fe 2+ ) reduces NO 3– to NO 2– and NO 2– , while soluble C can form complexes, i.e., the Fe 2+ wheel hypothesis of the coupled microbial mechanism of C, N, and Fe (Davidson et al. 2003).”
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“With rapid NO2 ¡ production, another fate merits revisiting, i.e., the so-called ferrous wheel hypothesis (Davidson et al. 2003).”
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“DON is mostly retained in soils even when it is present in reasonably high levels (Davidson et al. 2003). Foster (1997) estimated that DON exports from Fernow WS10 and WS4 ranged from 050% of total N exports, and averaged 23% for WS10 and 13% from WS4.”
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“Redox wheel act mutually as an electron acceptor and donator in addition to various biotic and abiotic redox-reactions (Davidson et al., 2003).”
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“However, the observed retention in the deeper soil layers may be due to abiotic reac- © 2006 NRC Canada tions with recalcitrant carbon compounds, which can be relatively common in deeper soil horizons compared with labile carbon (Qualls et al. 2002; Davidson et al. 2003).”
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“Alternatively, abiotic immobilization of NO 3 − by dissolved organic C, which takes place within a few minutes after N input, might also play a role in influencing the pulse (Davidson et al., 2003).”
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“Some prior studies elucidated that N addition was resistant to decomposition may produce microbial decomposers synthesize phenolic compound or break down litter lignin and other polyphenolic compounds into compounds that react with inorganic N to decomposition [54].”
BackgroundXiong, Y.-M., Xu, X.-L., Zeng, H., Wang, H.-M., Chen, F.-S., & Guo, D. (2015) · doi:10.3390/f6072387 · Cited by 3
Matus, F., Alvarez, E. R., Godoy, R., Iturriaga-Vásquez, P., Farías-Cea, A., Parada, J., Merino, C., Nájera, F., Mendoza, D., Jofré, I., et al. (2025) · Journal of Environmental Management · doi:10.1016/j.jenvman.2025.126311 · Cited by 2
Yoshihara, N., Iijima, M., Nishijima, M., & Iguchi, A. (2025) · Journal of Hydrology · doi:10.1016/j.jhydrol.2025.133960 · Cited by 2
Boldyrev, K. A., Kapyrin, I., Safonov, A. V., Karaseva, Y. Y., Blinov, P. D., Tyupina, E. A., & Zakharova, E. (2023) · Journal of Contaminant Hydrology · doi:10.1016/j.jconhyd.2023.104172 · Cited by 2
Cheng, H.-X., Tian, G.-M., Jia, X.-Y., Zhu, W.-Q., & Yang, J. (2012) · doi:10.5897/ajar12.1126 · Cited by 2
“Water soluble organic carbon (DOC) is recognized as the direct carbon source consumed by microorganisms, and also affects the mobility, transformation, and adsorption of soil organic and inorganic matter (Davidson et al., 2003; Hartley et al., 2010).”
BackgroundIsolating and Denitrification Activity of the Dominant Bacterium in Chaohu Wetland
Qian, J.-Z., Luo, J.-H., & Liu, Y. (2009) · International Conferences on Biomedical and Bioinformatics Engineering · doi:10.1109/icbbe.2009.5162990 · Cited by 2
“Recent study of nitrate removal by wetland has focused on different electron donors [5-7], different matrix [8], pH and temperature effect [9, 10].”
BackgroundMellert, K. H., Gensior, A., Göttlein, A., Kölling, C., & Rücker, G. (2008) · doi:10.1080/00207230701862405 · Cited by 2
“The suggestion that N retention is highly efficient in clay rich soils is sustained by current studies [52, 56, 57].”
BackgroundBiogeochemical Cycling on Land
Schlesinger, W. H., & Bernhardt, E. S. (2020) · Elsevier eBooks · doi:10.1016/b978-0-12-814608-8.00006-2 · Cited by 6
Sun, W.-J., Li, M.-D., Li, H.-M., Zheng, Y., Zhang, C.-X., Su, S.-H., & Zhang, X.-D. (2026) · Environmental Technology & Innovation · doi:10.1016/j.eti.2026.104876 · Cited by 1
Impact of Nitrogen Deposition on Carbon and Nitrogen Cycling in Peatlands Under Land‐Use Change
Deng, Y.-J., Boodoo, K. S., Knorr, K., & Glatzel, S. (2026) · Land Degradation & Development · doi:10.1002/ldr.70542 · Cited by 1
“DON-mediated N retention has been widely reported in forest ecosystems (Kreutzer et al. 2009; Šantrůčková et al. 2009; Dail et al. 2001), occurring potentially via abiotic immobilization of NH 4+ and NO 3 − (Thorn and Mikita 1992; Doane 2017; Davidson et al. 2003).”
Jesußek, A., Hansen, C., & Wilde, S. (2016) · Grundwasser · doi:10.1007/s00767-016-0337-9 · Cited by 1
From deer abundance to soil properties : a case study in the forests of Haida Gwaii
Maillard, M. (2020) · doi:10.14288/1.0388565 · Cited by 1
“123 mechanisms behind such fixation remain little known (Colman et al., 2007; Davidson et al., 2003).”
BackgroundThe Effect of Geological Media on the Denitrification of Nitrate in Subsurface Environments
Jeon, J., Lee, W.-C., Lee, S.-W., & Kim, S. (2020) · doi:10.7857/jsge.2020.25.s1.016 · Cited by 1
Wang, Q. (2017) · ERA: Education and Research Archive (University of Alberta) · doi:10.7939/r3f766m80
Bogush, A., Kim, J. K., & Campos, L. (2017) · doi:10.1180/emu-notes.17.12 · Cited by 1
“It was proposed that Fe(II) can reduce nitrate to nitrite, which converts to N 2 and/or might react with dissolved organic matter (Postma et al. , 1991; Davidson et al. , 2003; Burgin and Hamilton, 2007).”
Anaerobic Ammonium Oxidation in Groundwater Contaminated by Fertilizers
Tekin, E. (2013) · doi:10.20381/ruor-6561 · Cited by 1
Jeřábková, L. (2006) · doi:10.14288/1.0075059 · Cited by 1
Chahal, S. K., Ma, B., Lauzon, J., Nasielski, J., & Gillespie, A. W. (2026) · European Journal of Soil Science · doi:10.1111/ejss.70401
Interactive water-nitrogen effects on tissue-specific maize straw degradation in mollisols
Zhang, Q.-L., Li, X., Chen, G., & Lu, X.-R. (2026) · Industrial crops and products (Print) · doi:10.1016/j.indcrop.2026.123274
Irby, J. C., Krichels, A. H., Spasojevic, M., Jenerette, D., Hanan, E., & Homyak, P. M. (2026) · Biogeochemistry · doi:10.1007/s10533-026-01313-3
“After both 15 min and 4 h, 50 g of soil from the jars were extracted in 150 mL of 2 M KCl for subsequent measurement of NO 3– and NH 4+ concentrations and isotopic composition (Davidson et al. 2003).”
Ridgeway, J., Sulman, B., Weber, S., Juice, S. M., & Brzostek, E. (2026) · Agriculture, Ecosystems & Environment. Applied Soil Ecology · doi:10.1016/j.apsoil.2025.106585
A Lecithin Liposome Stimulates Soil Microbial Respiration and Nitrate Immobilization
Butkus, C. R., Weitzman, J. N., Mohammadzadeh, A., Dunn, P. J., Kaye, J. P., Gilbertson, L. M., Little, S. R., & Elliott, E. M. (2025) · ACS Agricultural Science & Technology · doi:10.1021/acsagscitech.5c00587 · Cited by 1
Kim, G., Joo, J., Lee, M.-J., Hong, S., Bock, J., Park, J. R., Ahn, C., & Oh, J.-M. (2018) · Journal of Korean Society of Environmental Engineers · doi:10.4491/ksee.2018.40.9.341
“또한, 각 페놀산의 적절한 불확도(uncertainty)를 고려 한 검출 가능한 페놀산 최소 농도를 추정하기 위해, 검량선 의 기울기(S) 및 표준편차(σ)를 이용해 식 (1)과 (2)를 활용 해 검출한계(limit of detection, LOD)와 정량한계(limit of quantification, LOQ)를 산출하였다.”
InfluentialStylianidis, G. P., Pantazopoulou, C., Chorianopoulou, S. N., & Bouranis, D. (2026) · Phyton · doi:10.32604/phyton.2026.085051
(2020) · Elsevier eBooks · doi:10.1016/b978-0-12-814608-8.09992-8
Productivity and carbon budgets of harvested Central Appalachian forests
Davis, S. (2007) · doi:10.33915/etd.4295
“This site-specific retention parameter also accounts for any additional nitrogen that may be acquired through microbial activity, as has been observed but poorly quantified (Davidson et al. 2003).”
Background
Metadata
- Authors
- Davidson, E. A., Chorover, J., & Dail, D. B.
- Affiliations
- Woodwell Climate Research Center (US)
- University of Arizona (US)
- University of Maine (US)
- Corresponding author
- Davidson, Eric A.
- Venue
- Global Change Biology
- Publisher
- Wiley
- Published
- 2003-02
- Volume
- 9
- Issue
- 2
- Pages
- 228-236
- ISSN
- 1354-1013 (ISSN-L)
- 1365-2486
- OpenAlex
- W2145062256
- Cited by
- 333
- References
- 65
- Citations by year
- 2026: 6 · 2025: 8 · 2024: 6 · 2023: 12 · 2022: 8 · 2021: 15 · 2020: 12 · 2019: 16 · 2018: 14 · 2017: 17 · 2016: 20 · 2015: 18 · 2014: 13 · 2013: 11 · 2012: 14
- FWCI
- 29.82
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Global Change Biology (publishedVersion)
- Funders
- National Science Foundation
- Pennsylvania State University
- Topics
- Life Sciences › Agricultural and Biological Sciences › Soil Science › Soil Carbon and Nitrogen Dynamics
- Physical Sciences › Environmental Science › Environmental Chemistry › Soil and Water Nutrient Dynamics
- Life Sciences › Agricultural and Biological Sciences › Plant Science › Plant nutrient uptake and metabolism
- Keywords
- forest soils, dissolved organic nitrogen, dissolved organic matter, nitrogen cycling, forest humus, atmospheric nitrogen deposition
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