Characterization of Functional Groups in Estuarine Dissolved Organic Matter by DNP-enhanced ¹⁵ N and ¹³ C Solid-State...

Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of ¹³ C NMR spectra and generally precludes the observation of ¹⁵ N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of ¹³ C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced ¹³ C NMR spectra indicate that the ¹³ C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of ¹⁵ N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine.