Beyond “Redfield ratio”: Oxygen exchange between water and phosphate can provide insights into carbon dynamics in soils

Phosphorus (P) is essential for cellular metabolism. Many metabolic pathways and processes depend on it, including energy production through ATP, DNA and RNA synthesis, and protein phosphorylation during post-translational signaling adaptation.

In marine sediments and oceanic water, the stoichiometric ratio between carbon and phosphorus has been found to vary with latitude, but in algae and phytoplankton, which are responsible for primary production and CO₂ uptake from the atmosphere, this ratio is relatively constant. This constant ratio is known as the Redfield ratio and  it is often used as a constraint in modeling.

In soils, where microorganisms control nutrient cycling and consequent carbon sequestration, the C:P is more variable both in soil and microbial biomass. First, microorganisms exhibit a wide range of metabolic adaptations to environmental pressure, and the physical and mineralogical properties of the soil play a significant role in nutrient control, e.g. through sorption/desorption reactions. Due to these complexities, using nutrient ratios for modeling soil organic carbon dynamics and predicting the impact of anthropogenic influences on global changes is challenging. Is it possible to find a connection between carbon and phosphate that encompasses the "Redfield" ratio and reflects their tight link in cellular metabolism?

By examining the oxygen isotope composition in inorganic phosphate (δ¹⁸O-Pi), we can determine the extent of oxygen exchange between water and phosphate, which is controlled by biological processes. Intracellularly, this exchange occurs through phosphoryl transfer, a fundamental process in cellular phosphate cycling. 

During the last 10 years, we conducted a series of incubation experiments where we measured CO₂ respiration and δ¹⁸O in resin and microbial cytosolic phosphate in soils from different environments. These incubations were performed with waters of varying ¹⁸O isotopic composition. By analyzing δ¹⁸O in microbial cytosolic phosphate at the beginning and end of the incubation, we could measure the level of oxygen exchange between water and phosphate.

Comparing the results from these incubations, we observed a significant correlation between the percentage of oxygen exchange and the cumulative CO₂ respired during the incubation. This correlation was consistent  through different soil ages, mineralogy, phosphate levels, and incubation length. When normalizing the percentage of oxygen exchange to moles of oxygen exchanged per moles of carbon respired, it appears that for every mole of oxygen exchanged due to phosphoryl transfer, there is a nearly fixed amount of carbon respired. This suggests that the moles of oxygen exchanged through phosphoryl transfer recorded in soil microbial phosphate can provide information about metabolic carbon expenditure.

This finding would provide new insights on the link between P and C in soil microbial biomass. The controlled nature of the incubation experiments may not fully reflect the biological activity in soil environments, so it would be necessary to perform field-based incubation experiments to confirm the link between carbon respiration and phosphorus microbial cycle. This information could potentially improve our understanding of carbon dynamics and be used for further modeling purposes.