Ramped pyrolysis (RP) targets distinct components of soil and sedimentary organic carbon based on their thermochemical stabilities and allows the determination of the full spectrum of radiocarbon ((14)C) ages present in a soil or sediment sample. Extending the method into realms where more precise ages are needed or where smaller samples need to be measured involves better understanding of the blank contamination associated with the method. Here, we use a compiled data set of RP measurements of samples of known age to evaluate the mass of the carbon blank and its associated (14)C signature, and to assess the performance of the RP system. We estimate blank contamination during RP using two methods, the modern-dead and the isotope dilution method. Our results indicate that during one complete RP run samples are contaminated by 8.8 ± 4.4 μg (time-dependent) of modern carbon (MC, fM ∼ 1) and 4.1 ± 5.5 μg (time-independent) of dead carbon (DC, fM ∼ 0). We find that the modern-dead method provides more accurate estimates of uncertainties in blank contamination; therefore, the isotope dilution method should be used with caution when the variability of the blank is high. Additionally, we show that RP can routinely produce accurate (14)C dates with precisions ∼100 (14)C years for materials deposited in the last 10,000 years and ∼300 (14)C years for carbon with (14)C ages of up to 20,000 years.

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The emerging view of soil organic matter (SOM) persistence asserts that SOM exists as a continuum of organic material, continuously processed by the decomposer community from large biopolymers to small monomers and with increasing oxidation and solubility, protected from decomposition through mineral aggregation and adsorption. Microbial community and ecosystem dynamics regulate the exchange of both nutrients and carbon between the soil and the atmosphere through the mineralization of SOM. Because these ecosystem dynamics are driven by net energy flows, analysis of SOM bioenergetics can provide complementary constraints to SOM models as well as insight into the fundamental conundrum of why thermodynamically unstable organic matter persists in soil. Microbial substrate preference has been shown to depend on the energy status of the potential substrates in terms of energy required and energy returned. Here we propose a framework for assessing the persistence of SOM utilizing thermally determined activation energy (E a ) and energy density (ED), tested on a suite of soils that have undergone alteration in field or laboratory experiments designed to isolate persistent SOM. Comparison of these energetic parameters in this framework will determine whether a chemical or physical change during SOM decomposition resulted in a change in its environmental persistence. An expanded framework of bioenergetics changes during SOM formation, decomposition, and stabilization is proposed as persistent SOM is characterized by decreased ED and E a , relative to the bulk SOM.

Coastal wetlands store vast amounts of organic carbon, globally, and are becoming increasingly vulnerable to the effects of anthropogenic sea level rise. To understand the effect of sea level rise on organic carbon fate and preservation in this global sink, it is necessary to characterize differences in the biogeochemical stability of coastal wetland soil organic carbon (SOC). Here we use ramped pyrolysis/oxidation decomposition characteristics as proxies for SOC stability to understand the fate of carbon storage in coastal wetlands comprising the Mississippi River deltaic plain, undergoing rapid rates of local sea level rise. Soils from three wetland types (fresh, brackish, and salt marshes) along a salinity gradient were subjected to ramped pyrolysis analysis to evaluate decomposition characteristics related to thermochemical stability of SOC. At equivalent soil depths, we observed that fresh marsh SOC was more stable than brackish and salt marsh SOC. Depth, isotopic, elemental, and chemical compositions, bulk density, and water content of SOC all exhibited different relationships with SOC stability across the marsh salinity gradient, indicative of different controls on SOC stability within each marsh type. The differences in stability imply stronger preservation potential of fresh marsh soil carbon, compared to that of salt and brackish marshes. Considering projected marsh ecosystem responses to sea level rise, these observed stability differences are important in planning and implementing coastal wetland carbon-focused remediation and improving climate model feedbacks with the carbon cycle. Specifically, our results imply that ecosystem changes associated with sea level rise will initiate the accumulation of less stable carbon in coastal wetlands.

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