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The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known Cox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ±0.036 Cox units (±0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of −0.26 and a range from −0.45 to 0.30, corresponding to OR values of 1.08 ± 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated with the fire had an OR of 1.091 (±0.003). Fire appears to be a major factor driving the soil C pool to higher oxidation states and lower OR values. Episodic fluxes caused by disturbances like fire may have substantially different ORs from ecosystem respiration fluxes and therefore should be better quantified to reduce uncertainties associated with our understanding of the global atmospheric carbon budget.

The ratio of isotopes of carbon (13C:12C or δ13C) and nitrogen (15N:14N or δ15N) are common indicators of the flow and storage of organic matter in coastal wetland research. Effective use of these indicators requires quantification and understanding of: (1) the variability of isotope signatures of potential organic matter source materials; and (2) the influence of organic matter decomposition on isotopic signatures. While it is well-established that organic matter characteristics change during the decomposition process, there has been little direct quantification of any concurrent shifts in isotope signatures for coastal detritus. In this study, we addressed this by quantifying: (1) shifts in sample composition using solid-state 13C Nuclear Magnetic Resonance (NMR) spectroscopy; and (2) shifts in δ13C and δ15N signatures of coastal plant tissues from field litterbag experiments. We observed significant shifts in 13C NMR spectra across the course of deployment for all four plant tissues assessed (leaves of mangrove Avicennia marina; branchlets of supratidal tree Casuarina glauca; leaf wrack and roots/rhizomes of the seagrass Zostera muelleri), driven largely by the preferential loss of labile constituents and concentration of more resistant macromolecules, such as lignin and leaf waxes. While there were shifts in isotope ratios for all species, these varied in direction and magnitude among species, tissue type and isotopes. This included δ13C enrichments of up to 3.1‰ and 2.4‰ in leaves of A. marina, and branchlets of C. glauca, respectively, but δ13C depletions of up to 4.0‰ for Z. muelleri. Shifts in δ15N varied among species and tissue types, with few clear temporal patterns. Partial least squares regression analyses showed that some tissue isotope signatures can be reliably predicted on the basis of sample composition (13C NMR spectra), however, multiple inter- and intra-species variations preclude a simple explanation of isotopic signature shifts on the basis of plant-material molecular shifts alone. Further, we cannot preclude the potential influence of microbe-associated organic matter on sample composition or isotopic signatures. Our findings emphasise the importance of considering decomposition effects on stable isotope signatures in blue carbon ecosystems. Isotope approaches will remain a valuable tool in coastal ecosystem research, but require robust experimental approaches (including appropriate use of decomposed end-members or fractionation correction factors; quantification of microbial organic matter) and quantification of decomposition dynamics for specific plant tissues and environmental settings. [ABSTRACT FROM AUTHOR]

Carbon dioxide emissions and the mass loss of peat incubated in situ were measured in peat soils in the Australian Alps. The carbon chemistry of incubated peats was characterized using 13C nuclear magnetic resonance (NMR). In situ decomposition decreased as a function of increasing alkyl carbon content of the initial organic matter, providing direct evidence of the oft-cited link between substrate quality and decomposition rates. More mass loss occurred in the bog peat samples than in the dried peat samples. However, at the peat surface, the amount of CO2 emitted was not significantly different between bog peat and dried peat. Carbon inputs, and therefore the sink or source status, of these peats are yet to be quantified. [ABSTRACT FROM AUTHOR]