Characterization of the Impact of Fire on Terrestrial Organic Carbon and Its Fate in the Environment

Pyrogenic carbon (PyC) is a heterogeneous continuum of compounds resulting from incomplete combustion of organic matter. The understanding of PyC in the environment has mainly focused on high-temperature combustion by-products. However, the portion of this continuum produced at low temperatures, mainly during wildfire and prescribed burning events, is particularly labile and water-soluble. Therefore, low-temperature PyC is imperative to study during dynamic transport across environmental interfaces. This dissertation presents new characterization of low-temperature PyC at the interfaces of terrestrial, aquatic and atmospheric environments. I use biomarkers of biomass combustion, plant materials, and inorganic tracers to elucidate sources, composition, and degradation of PyC during transport within and between environmental reservoirs. In large Arctic rivers, low-temperature PyC biomarkers are present in detectable concentrations during all flow regimes. PyC export occurs predominately in the dissolved phase and is an intrinsic component of the DOC pool mobilized by hydrologic events. Around half of the low-temperature PyC exported may be remineralized during transit time from fire source to river mouth, implying a labile source of PyC to these watersheds. Phase partitioning of low-temperature PyC suggests that it sorbs to particles at levels orders of magnitude higher than what equilibrium theory would predict. The higher than expected association of these soluble components with particles may help explain the recorded presence of these biomarkers in sedimentary deposits, which have helped track historical wildfire signatures in watersheds. However, as partitioning coefficients of low-temperature PyC biomarkers are lower than those reported for high temperature PyC biomarkers, there is a higher potential for exchange with the aqueous phase and thus accessibility to microbial degradation during transport to the coastal ocean, especially during the spring freshet. In the atmosphere, low-temperature PyC biomarkers may be more labile than previously considered, with potential abiotic degradation (such as hydroxyl radical reactions) occurring on time scales relevant to atmospheric transport (days). As this could affect the composition of PyC biomarkers at depositional sites, the assumption that they are conservative in the atmosphere must be questioned. This dissertation quantifies PyC dynamics to help solidify flux and pool estimates and missing parameters in model assessments of carbon cycling

Biogeochemistry of upland to wetland soils, sediments, and surface waters across Mid-Atlantic and Great Lakes coastal interfaces

Transferable and mechanistic understanding of cross-scale interactions is necessary to predict how coastal systems respond to global change. Cohesive datasets across geographically distributed sites can be used to examine how transferable a mechanistic understanding of coastal ecosystem control points is. To address the above research objectives, data were collected by the EXploration of Coastal Hydrobiogeochemistry Across a Network of Gradients and Experiments (EXCHANGE) Consortium – a regionally distributed network of researchers that collaborated on experimental design, methodology, collection, analysis, and publication. The EXCHANGE Consortium collected samples from 52 coastal terrestrial-aquatic interfaces (TAIs) during Fall of 2021. At each TAI, samples collected include soils from across a transverse elevation gradient (i.e., coastal upland forest, transitional forest, and wetland soils), surface waters, and nearshore sediments across research sites in the Great Lakes and Mid-Atlantic regions (Chesapeake and Delaware Bays) of the continental USA. The first campaign measures surface water quality parameters, bulk geochemical parameters on water, soil, and sediment samples, and physicochemical parameters of sediment and soil

Representing the function and sensitivity of coastal interfaces in earth system models

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Ward, N. D., Megonigal, J. P., Bond-Lamberty, B., Bailey, V. L., Butman, D., Canuel, E. A., Diefenderfer, H., Ganju, N. K., Goni, M. A., Graham, E. B., Hopkinson, C. S., Khangaonkar, T., Langley, J. A., McDowell, N. G., Myers-Pigg, A. N., Neumann, R. B., Osburn, C. L., Price, R. M., Rowland, J., Sengupta, A., Simard, M., Thornton, P. E., Tzortziou, M., Vargas, R., Weisenhorn, P. B., & Windham-Myers, L. Representing the function and sensitivity of coastal interfaces in earth system models. Nature Communications, 11(1), (2020): 2458, doi:10.1038/s41467-020-16236-2.Between the land and ocean, diverse coastal ecosystems transform, store, and transport material. Across these interfaces, the dynamic exchange of energy and matter is driven by hydrological and hydrodynamic processes such as river and groundwater discharge, tides, waves, and storms. These dynamics regulate ecosystem functions and Earth’s climate, yet global models lack representation of coastal processes and related feedbacks, impeding their predictions of coastal and global responses to change. Here, we assess existing coastal monitoring networks and regional models, existing challenges in these efforts, and recommend a path towards development of global models that more robustly reflect the coastal interface.Funding for this work was provided by Pacific Northwest National Laboratory (PNNL) Laboratory Directed Research & Development (LDRD) as part of the Predicting Ecosystem Resilience through Multiscale Integrative Science (PREMIS) Initiative. PNNL is operated by Battelle for the U.S. Department of Energy under Contract DE-AC05-76RL01830. Additional support to J.P.M. was provided by the NSF-LTREB program (DEB-0950080, DEB-1457100, DEB-1557009), DOE-TES Program (DE-SC0008339), and the Smithsonian Institution. This manuscript was motivated by discussions held by co-authors during a three-day workshop at PNNL in Richland, WA: The System for Terrestrial Aquatic Research (STAR) Workshop: Terrestrial-Aquatic Research in Coastal Systems. The authors thank PNNL artist Nathan Johnson for preparing the figures in this manuscript and Terry Clark, Dr. Charlette Geffen, and Dr. Nancy Hess for their aid in organizing the STAR workshop. The authors thank all workshop participants not listed as authors for their valuable insight: Lihini Aluwihare (contributed to biogeochemistry discussions and development of concept for Fig. 3), Gautam Bisht (contributed to modeling discussion), Emmett Duffy (contributed to observational network discussions), Yilin Fang (contributed to modeling discussion), Jeremy Jones (contributed to biogeochemistry discussions), Roser Matamala (contributed to biogeochemistry discussions), James Morris (contributed to biogeochemistry discussions), Robert Twilley (contributed to biogeochemistry discussions), and Jesse Vance (contributed to observational network discussions). A full report on the workshop discussions can be found at https://www.pnnl.gov/publications/star-workshop-terrestrial-aquatic-research-coastal-systems

Riverine organic matter functional diversity increases with catchment size

A large amount of dissolved organic matter (DOM) is transported to the ocean from terrestrial inputs each year (~0.95 Pg C per year) and undergoes a series of abiotic and biotic reactions, causing a significant release of CO2. Combined, these reactions result in variable DOM characteristics (e.g., nominal oxidation state of carbon, double-bond equivalents, chemodiversity) which have demonstrated impacts on biogeochemistry and ecosystem function. Despite this importance, however, comparatively few studies focus on the drivers for DOM chemodiversity along a riverine continuum. Here, we characterized DOM within samples collected from a stream network in the Yakima River Basin using ultrahigh-resolution mass spectrometry (i.e., FTICR-MS). To link DOM chemistry to potential function, we identified putative biochemical transformations within each sample. We also used various molecular characteristics (e.g., thermodynamic favorability, degradability) to calculate a series of functional diversity metrics. We observed that the diversity of biochemical transformations increased with increasing upstream catchment area and landcover. This increase was also connected to expanding functional diversity of the molecular formula. This pattern suggests that as molecular formulas become more diverse in thermodynamics or degradability, there is increased opportunity for biochemical transformations, potentially creating a self-reinforcing cycle where transformations in turn increase diversity and diversity increase transformations. We also observed that these patterns are, in part, connected to landcover whereby the occurrence of many landcover types (e.g., agriculture, urban, forest, shrub) could expand DOM functional diversity. For example, we observed that a novel functional diversity metric measuring similarity to common freshwater molecular formulas (i.e., carboxyl-rich alicyclic molecules) was significantly related to urban coverage. These results show that DOM diversity does not decrease along stream networks, as predicted by a common conceptual model known as the River Continuum Concept, but rather are influenced by the thermodynamic and degradation potential of molecular formula within the DOM, as well as landcover patterns

Microbial inputs at the litter layer translate climate into altered organic matter properties

Plant litter chemistry is altered during decomposition but it remains unknown if these alterations, and thus the composition of residual litter, will change in response to climate. Selective microbial mineralization of litter components and the accumulation of microbial necromass can drive litter compositional change, but the extent to which these mechanisms respond to climate remains poorly understood. We addressed this knowledge gap by studying needle litter decomposition along a boreal forest climate transect. Specifically, we investigated how the composition and/or metabolism of the decomposer community varies with climate, and if that variation is associated with distinct modifications of litter chemistry during decomposition. We analyzed the composition of microbial phospholipid fatty acids (PLFA) in the litter layer and measured natural abundance δ13C-PLFA values as an integrated measure of microbial metabolisms. Changes in litter chemistry and δ13C values were measured in litterbag experiments conducted at each transect site. A warmer climate was associated with higher litter nitrogen concentrations as well as altered microbial community structure (lower fungi:bacteria ratios) and microbial metabolism (higher δ13C-PLFA). Litter in warmer transect regions accumulated less aliphatic-C (lipids, waxes) and retained more O-alkyl-C (carbohydrates), consistent with enhanced 13C-enrichment in residual litter, than in colder regions. These results suggest that chemical changes during litter decomposition will change with climate, driven primarily by indirect climate effects (e.g. greater nitrogen availability and decreased fungi:bacteria ratios) rather than direct temperature effects. A positive correlation between microbial biomass δ13C values and 13C-enrichment during decomposition suggests that change in litter chemistry is driven more by distinct microbial necromass inputs than differences in the selective removal of litter components. Our study highlights the role that microbial inputs during early litter decomposition can play in shaping surface litter contribution to soil organic matter as it responds to climate warming effects such as greater nitrogen availability.Peer reviewe

Labile pyrogenic dissolved organic carbon in major Siberian Arctic rivers: Implications for wildfire-stream metabolic linkages

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.Biomass burning produces a spectrum of thermally altered materials that releases pyrogenic carbon (PyC) to terrestrial, atmospheric, and aquatic systems. Most studies focus on the refractory end of the PyC spectrum, derived from middle- to high-temperature combustion. Low-temperature PyC is produced during wildfires and has been found to be particularly labile and water soluble. Here we find that in each of the major Siberian watersheds, low-temperature fire-derived biomarkers are present in detectable concentrations during all flow regimes of the 2004–2006 sampling period, confirming that PyC is an intrinsic component of the dissolved organic carbon (DOC) pool mobilized by hydrologic events. Gymnosperm combustion, from the southern portions of these watersheds, is the primary source of this Py-DOC input. Using first-order degradation rates and transit times of water through these rivers, about half of the total estimated flux of this material may be remineralized during transport from fire source to river mouth (20–40 days), demonstrating the input of a labile source of PyC to these watersheds