Influence of Citrate and Phosphate on the Adsorption of Adenosine-5′-Monophosphate at the Hematite Water Interface

Nucleic acid derived organic phosphorus (Po) is an important source of plant available P when degraded to inorganic phosphate (P(V)i). It is known that when nucleic acids or components are adsorbed on mineral surfaces, the enzymatic degradation is hindered or delayed. Thus, understanding adsorption/desorption mechanisms of nucleic acids and their derivatives are key to assess the biogeochemical pathways of Po cycling. Here we report adsorption mechanisms of adenosine-5′-monophosphate (AMP) on hematite, a common iron oxide mineral, under various solution properties using macroscopic and in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic probes. The effects of citrate, mimicking organic acids from roots exudates, and the influence of P(V)i, representing inorganic fertilizer application, were also evaluated on the release of adsorbed AMP under various solution properties. The results suggested that AMP adsorbed with the hematite surface via the phosphate moiety, N7 atom and the π electron systems of the adenine moiety. The presence of citrate significantly decreased the AMP adsorption, which was also corroborated by the negative phosphate IR bands in the results of AMP and citrate competitive adsorption experiments monitored by in situ ATR-FTIR probe. Like citrate, P(V)i also reduced AMP adsorption on hematite. Our findings suggest a potential novel pathway of nucleic acid derived Po cycling in the soil environment

Antimony (V) Adsorption at the Hematite–Water Interface: A Macroscopic and In Situ ATR-FTIR Study

The environmental mobility of antimony (Sb) is largely unexplored in geochemical environments. Iron oxide minerals are considered major sinks for Sb. Among the different oxidation states of Sb, (+) V is found more commonly in a wide redox range. Despite many adsorption studies of Sb (V) with various iron oxide minerals, detailed research on the adsorption mechanism of Sb (V) on hematite using macroscopic, spectroscopic, and surface complexation modeling is rare. Thus, the main objective of our study is to evaluate the surface complexation mechanism of Sb (V) on hematite under a range of solution properties using macroscopic, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic, and surface complexation modeling. The results indicate that the Sb (V) adsorption on hematite was highest at pH 4–6. After pH 6, the adsorption decreased sharply and became negligible above pH 9. The effect of ionic strength was negligible from pH 4 to 6. The spectroscopic results confirmed the presence of inner- and outer-sphere surface complexes at lower pH values, and only outer-sphere-type surface complex at pH 8. Surface complexation models successfully predicted the Sb (V) adsorption envelope. Our research will improve the understanding of Sb (V) mobility in iron-oxide-rich environments