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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.

Phytate is a dominant form of organic phosphorus (P) in the environment. Complexation and precipitation with polyvalent metal ions can stabilize phytate, thereby significantly hinder the hydrolysis by enzymes. Here, we studied the stability and hydrolyzability of environmentally relevant metal phytate complexes (Na, Ca, Mg, Cu, Zn, Al, Fe, Al/Fe, Mn, and Cd) under different pHs, presence of metal chelators, and thermal conditions. Our results show that the order of solubility of metal phytate complexes is as follows: i) for metal species: Na, Ca, Mg > Cu, Zn, Mn, Cd > Al, Fe, ii) under different pHs: pH 5.0 > pH 7.5), and iii) in the presence of chelators: EDTA> citric acid. Phytate-metal complexes are mostly resistant towards acid hydrolysis (except Al-phytate), and dry complexes are generally stable at high pressure and temperature under autoclave conditions (except Ca phytate). Inhibition of metal complex towards enzymatic hydrolysis by Aspergillus niger phytase was variable but found to be highest in Fe phytate complex. Strong chelating agents such as EDTA are insufficient for releasing metals from the complexes unless the reduction of metals (such as Fe) occurs first. The insights gained from this research are expected to contribute to the current understanding ofmore »the fate of phytate in the presence of various metals that are commonly present in agricultural soils.« less

Phosphorus (P) loss from cropland to ground and surface waters is a global concern. In cold climates (CCs), freeze–thaw cycles, snowmelt runoff events, and seasonally wet soils increase P loss potential while limiting P removal effectiveness of riparian buffer zones (RBZs) and other practices. While RBZs can help reduce particulate P transfer to streams, attenuation of dissolved P forms is more challenging. Moreover, P transport studies often focus on either cropland or RBZs exclusively rather than spanning the natural cropland–RBZ–stream gradient, defined here as the cropland–RBZ–stream continuum. Watershed P transport models and agronomic P site indices are commonly used to identify critical source areas; however, RBZ effects on P transport are usually not included. In addition, the coarse resolution of watershed P models may not capture finer-scale soil factors affecting P mobilization. It is clear that site microtopography and hydrology are closely linked and important drivers of P release and transport in overland flow. Combining light detection and ranging (LiDAR) based digital elevation models with P site indices and process-based models show promise for mapping and modeling P transport risk in cropland-RBZ areas; however, a better mechanistic understanding of processes controlling mobile P species across regions is needed. Broader predictivemore »approaches integrating soil hydro-biogeochemical processes with real-time hydroclimatic data and risk assessment tools also hold promise for improving P transport risk assessment in CCs.« less