Natural organic matter (NOM) is an important component in many near-surface geochemical environments, and its properties are greatly affected by the incorporation of water. Because of its importance, the macroscopic behavior and effects of water in NOM and soil organic matter (SOM) have been extensively studied using a wide range of experimental and computational methods. The molecular scale structural and dynamical behavior of water in these materials, however, is less well understood. This paper presents a variable temperature 2H NMR and XRD study of water in Suwannee River NOM and its fulvic acid (FA) and humic acid (HA) fractions that provides new insight into the dynamical behavior of structurally different types of water and exchangeable hydrogen environments in NOM. The results provide a basis for future studies of more complex natural organic materials and the interaction of organic materials with mineral surfaces. Room temperature 2H NMR spectra of samples hydrated in 2H2O and then dehydrated, distinguish 2H2O molecules that are in rapid reorientational motion (correlation times, νc > 105 Hz), 2H exchanged onto carboxylic sites of the NOM that do not undergo rapid reorientation at frequencies >∼103 Hz, and 2H exchanged onto phenolic and possibly other alcohol sites of the NOM that undergoes rapid, but anisotropic, dynamical reorientation. For samples exposed to water and not dried, the XRD results collected at temperatures from 173 to 298 K show the formation of ice-1h in samples exposed to 100% relative humidity (R.H.) but not in samples exposed to 43% R.H. 2H NMR of those samples collected at temperatures from 313 K to 173 K show the presence of multiple sites. Near room temperature, the spectra contain a narrow resonance for mobile water undergoing rapid isotropic motion, and a broader symmetrical resonance probably due to a combination of more dynamically restricted water molecules and 2H exchanged onto phenolic and alcohol functional groups undergoing rapid anisotropic motion. The 43% R.H. samples also yield a broader, quadrupole-dominated, resonance for 2H exchanged onto functional groups of the NOM. With decreasing temperature the resonances for dynamically restricted water molecules and 2H exchanged onto phenolic and alcohol functional groups become broader, reflecting a decreasing rate of exchange between the water molecules and functional groups and a decreasing rate of reorientation of the 2H2O molecules. The formation of ice-1h is directly reflected in the 2H spectra of the 100% R.H. samples as a resonance with a quadrupole coupling constant (QCC) of ∼180 kHz. For the 43% R.H. samples, there is also a broad, poorly resolved resonance with typical QCCs of ∼180 kHz for which the relative signal intensity increases with decreasing temperature. This signal represents 2H2O molecules that are not crystallized in ice-1h but have greatly reduced reorientation frequencies at low temperature and a hydrogen bonding network with hydrogen bond strengths similar to, but somewhat weaker than, ice-1h. Such molecules are also likely to be present in the 100% R.H. samples. At both R.H.s, some of the 2H2O molecules do not freeze and retain their isotropic motion down to 173 K, the lowest temperature investigated.
Bibliographical noteFunding Information:
This work was supported by the U.S. Department of Energy, Office of Basic Energy Science through grants DE-FG02-10ER16128 (Bowers, P.I.) and DE-FG02-08ER15929 (Kirkpatrick, P.I.). We thank Michael Rich, College of Engineering at Michigan State University for help in acquiring the TGA data, and Daniel Holmes of the Max T. Rogers NMR facility at Michigan State University for assistance with acquiring the NMR spectra. The X-ray diffraction work was performed in EMSL, a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research. The manuscript was greatly improved by the comments of two anonymous reviewers.
© 2018 Elsevier Ltd
- Natural organic matter