Phosphorus (P) is an essential nutrient for sustaining life and agricultural production. Transformation of readily available P into forms that are unavailable to plants adds costs to P replenishment, which eventually translates into lower agronomic benefits and potential loss of soil P into runoff may degrade water quality. Therefore, understanding the sources and pathways of the formation of residual P pools in soils is useful information needed for the development of any technological or management efforts to minimize or inhibit the formation of such P pool and thus maximize availability to plants. In this research, we paired phosphate oxygen isotope ratios (δ18OP) with solid-state 31P NMR and quantitative XRD techniques along with general soil chemistry methods to identify the precipitation pathways of acid-extracted inorganic P (Pi) pools in an agricultural soil. Based on the comparison of isotope values of 0.5 mol L−1 NaOH-Pi, 1 mol L−1 HCl-Pi, and 10 mol L−1 HNO3-Pi pools and correlations of associated elements (Ca, Fe, and Al) in these pools, the HNO3-Pi pool appears most likely to be transformed from the NaOH-Pi pool. A narrow range of isotope values of acid-Pi pools in shallow (tilling depth) and below (where physical mixing is absent) is intriguing but likely suggests leaching of particle-bound P in deeper soils. Overall, these findings provide an improved understanding of the sources, transport, and transformation of acid-Pi pools in agricultural soils and further insights into the buildup of legacy P in soils.
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Evolution of Oxygen Isotopologues in Phosphate and Pyrophosphate during Enzyme-Catalyzed Isotopic Exchange Reactions
Inorganic pyrophosphatase (PPase) is an enzyme that catalyzes the hydrolysis of the phosphoanhydride bond in pyrophosphate (PPi) to release inorganic phosphate (Pi) and simultaneously exchange oxygen isotopes between Pi and water. Here, we quantified the exchange kinetics of oxygen isotopes between five Pi isotopologues (P18O4, P18O316O, P18O216O2, P18O16O3, and P16O4) and water using Raman spectroscopy and 31P nuclear magnetic resonance (NMR) during the PPase-catalyzed 18O–16O isotope exchange reaction in Pi-water and PPi-water systems. At a high PPi concentration (300 mM), hydrolysis of PPi by PPase was predominant, and only a small fraction of PPi (≪1%) took part in the reversible hydrolysis–condensation reaction (PPi ↔ Pi), leading to the oxygen isotope exchange between Pi and water. We demonstrated that Raman and NMR methods can be equally applied for monitoring the kinetics of the oxygen exchange between the Pi isotopologue and water. It was found that the isotope exchange determined by the spectroscopic methods was detectable as low as 0.2% 18O abundance, but the reliability below 1% was much lower. Given that high P concentrations (≥1 mM) are required in these methods, environmental application of these methods is limited to rare high P conditions in engineered and agricultural environments.
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- NSF-PAR ID:
- 10331403
- Date Published:
- Journal Name:
- ACS Earth and Space Chemistry
- ISSN:
- 2472-3452
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acsearthspacechem.2c00050
