Novel Insights into Molecular Composition of Organic Phosphorus in Lake Sediments.

Organic phosphorus (Po) plays a key role in eutrophication and ecological equilibrium in lake systems. However, characterizing the composition of Po in lake sediments has been a bottleneck hindering further understanding of the biogeochemical cycle of Po. Here, multiple methods of 31P NMR spectroscopy and molecular weight (MW) ultrafiltration were combined to detect Po composition characteristics from a novel angle in ten lake sediments of China. The results showed that sediment Po mainly consisted of monoester (mono-P, 14±8.8% of the NaOH-EDTA total P on average), diester (di-P, 1.4±1.4%) and phosphonate (phos-P, 0.1±0.1%), while the abundance of Po was largely underestimated by 31P NMR methods. Some specific species of mono-P were successfully determined, and the contents of these species followed a decreasing order: inositol hexakisphosphate (IHP6) > RNA mononucleotides (RNA-mnP) > β-glycerophosphate (β-gly) > D-glucose 6-phosphate (Glu-6) > α-glycerophosphate (α-gly), which was largely dependent upon their bioreactivity. A significant relationship between MW and Po components was observed despite the great differences among sediment samples. For refractory Po components, IHP6 was mainly rich in the MW < 3 kDa while phos-P was almost only detected in the MW > 3 kDa, which largely attributed to their metal binding affinities and characteristics. The abundance of bioreactive Po species (α-gly, β-gly, Glu-6, di-P) in high MW (HMW, > 3 kDa) were all higher than that of low MW (LMW, < 3 kDa) due to microbial degradation and self-assembly. If the HMW organic molecules were biologically and chemically more reactive than its LMW counterparts, the high percentage of α-gly, β-gly, glu-6 and di-P in the HMW portion would highlights their high reactivity from the perspective of MW. These insights revealed the dynamics of the MW distribution of Po components and provide valuable information to better understand the Po composition and bioreactivity in sediments.