The relationship between energetics and structure in 2-, 4-, 5-, and 6-hydroxynicotinic and 5-chloro-6-hydroxynicotinic acids (2HNA, 4HNA, 5HNA, 6HNA, and 5Cl6HNA, respectively) was investigated in the solid and gaseous phases by means of a variety of experimental and computational chemistry techniques. The molecular and crystal structures of the 2HNA, 4HNA, 6HNA, and 5Cl6HNA solid forms used in this study were determined by single crystal X-ray diffraction at 293 +/- 2 K. The 2HNA, 4HNA, and 5Cl6HNA samples were monoclinic (space groups: P2(1)/n for 2HNA and P2(1)/c for 4HNA and 5Cl6HNA), and that of 6HNA was found to be triclinic (space group: P1). The 2HNA sample investigated corresponds to a new polymorphic form of this compound. The 2HNA, 4HNA, 6HNA, and 5Cl6HNA molecules crystallize as oxo tautomers exhibiting N-H and Cring=O bonds. This is also supported by the observation of bands typical of N-H and Cring=O stretching frequencies in the corresponding FT-IR spectra. The absence of these bands in the spectrum of 5HNA indicates that a hydroxy tautomer with an unprotonated N heteroatom and a Cring-OH bond is likely to be present in this case. Results of theoretical calculations carried out at the G3MP2 and CBS-QB3 levels of theory suggest that in the ideal gas phase, at 298.15 K, 2HNA favors the oxo form, 4HNA prefers the hydroxy form, and no strong dominance of one of the two tautomers exists in the case of 6HNA and 5Cl6HNA. The standard molar enthalpies of formation of 2HNA, 4HNA, 5HNA, 6HNA, and 5Cl6HNA in the crystalline state, at 298.15 K, Delta(f)H(m)(o)(cr), were determined by micro combustion calorimetry. The corresponding enthalpies of sublimation, Delta(sub)H(m)(o), were also derived from vapor pressure versus temperature measurements by the Knudsen effusion method. The obtained Delta(f)H(m)(o)(cr) and Delta(sub)H(m)(o) values led to the enthalpies of formation of 2HNA, 4HNA, 5HNA, 6HNA, and 5Cl6HNA in the gaseous phase. These were discussed together with the corresponding predictions by the B3LYP/cc-pVTZ, B3LYP/aug-cc-pVTZ, G3MP2, and CBS-QB3 methods on the basis of isodesmic or atomization reactions. The experimental "stability" order (more stable meaning a more negative Delta(f)H(m)(o)(g) value) found was 5Cl6HNA > 2HNA > 6HNA > 4HNA > 5HNA, and it was accurately captured by the CBS-QB3 and G3MP2 methods, which give 5Cl6HNA > 2HNA approximately 6HNA > 4HNA > 5HNA, irrespective of the use of isodesmic or atomization reactions. In contrast, only when well-balanced isodesmic reactions were considered did the DFT results agree with the experimental ones. The picture that emerged from the structural and energetic studies carried out in this work was also discussed in light of that typical of hydroxypyridines, which are generally regarded as the archetype systems for the study of the hydroxy <--> oxo tautomerization in N-heterocyclic compounds.

Coastal vegetated ecosystems are major organic carbon (OC) and total nitrogen (TN) sinks, but the mechanisms that regulate their spatial variability need to be better understood. Here we assessed how superficial sedimentary OC and TN within intertidal vegetated assemblages (saltmarsh and seagrass) vary along a flow gradient, which is a major driver of sediment grain size, and thus of organic matter (OM) content. A significant relationship between flow current velocity and OC and TN stocks in the seagrass was found, but not in the saltmarsh. OC and TN stocks of the saltmarsh were larger than the seagrass, even though that habitat experiences shorter hydroperiods. Mixing models revealed that OM sources also varied along the flow gradient within the seagrass, but not in the saltmarsh, showing increasing contributions of microphytobenthos (17–32%) and decreasing contributions of POM (45–35%). As well, OM sources varied vertically as microphytobenthos contribution was highest at the higher intertidal saltmarsh (48%), but not POM (39%). Macroalgae, seagrass and saltmarsh showed low contributions. Local trade-offs between flow current velocities, hydroperiod and structural complexity of vegetation must be considered, at both horizontal and vertical (elevation) spatial dimensions, for better estimates of blue carbon and nitrogen in coastal ecosystems.

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Coastal vegetated ecosystems such as saltmarshes and seagrasses are important sinks of organic carbon (OC) and total nitrogen (TN), with large global and local variability, driven by the confluence of many physical and ecological factors. Here we show that sedimentary OC and TN stocks of intertidal saltmarsh (Sporobolus maritimus) and seagrass (Zostera noltei) habitats increased between two-and fourfold along a decreasing flow velocity gradient in Ria Formosa lagoon (south Portugal). A similar twofold increase was also observed for OC and TN burial rates of S. maritimus and of almost one order of magnitude for Z. noltei. Stable isotope mixing models identify allochthonous particulate organic matter as the main source to the sedimentary pools in both habitats (39-68%). This is the second estimate of OC stocks and the first of OC burial rates in Z. noltei, a small, fast-growing species that is widely distributed in Europe (41,000 ha) and which area is presently expanding (8600 ha in 2000s). Its wide range of OC stocks (29-99 Mg ha -1 ) and burial rates (15-122 g m 2 y -1 ) observed in Ria Formosa highlight the importance of investigating the drivers of such variability to develop global blue carbon models. The TN stocks (7-11 Mg ha -1 ) and burial rates (2-4 g m -2 y -1 ) of Z. noltei were generally higher than seagrasses elsewhere. The OC and TN stocks (29-101 and 3-11 Mg ha -1 , respectively) and burial rates (19-39 and 3-5 g m -2 y -1 ) in S. maritimus saltmarshes are generally lower than those located in estuaries subjected to larger accumulation of terrestrial organic matter.