Quantitative determination of redox-active carbonyls of natural dissolved organic matter

Natural dissolved organic matter (DOM) is ubiquitous in environment and plays an important role in numerous environmental processes. Although the molecular basis of the reactivity of DOM remains poorly understood due to its extreme complexity, redox-active carbonyls (aromatic ketones/aldehydes and quinones) within DOM are believed vitally important. Except the rough determination of total carbonyls (including non-redox active -COOR) based on inflexible ¹³C chemical shift range by expensive and time-consuming solid-state nuclear magnetic resonance (NMR), there is no ready method to quantify redox-active carbonyls in DOM. Here we show that after treatment with sodium borohydride (NaBH₄) by selectively eliminating redox-active carbonyls, quenched fluorescence of carbon quantum dots (CD) by DOM recovered dramatically, and displayed a good linear relationship between redox-active carbonyls detected and DOM concentration (R² ≥ 0.977), thus allowing first quantitative determination of the redox-active carbonyls of DOM. Eight DOM isolates present 0.59%-0.90% redox-active carbonyls by the current method. And this method is robust from coexisting proteins and salts. This method could provide better or equal instructive results compared with solid-state NMR for total carbonyls or electrochemical method for electron-accepting capacities (EAC). Our results provide the underlying structural basis of many important geochemical processes that mediated by DOM. We posit that this method could apply to other complex molecular systems such as the atmospheric aerosols and extracellular polymeric substances (EPS), too.