Potential bioavailability of representative pyrogenic organic matter compounds in comparison to natural dissolved organic matter pools

Pyrogenic organic matter (PyOM) from wildfires impacts river corridors globally and is widely regarded as resistant to biological degradation. Though recent work suggests PyOM may be more bioavailable than historically perceived, estimating bioavailability across its chemical spectrum remains elusive. To address this knowledge gap, we assessed potential bioavailability of representative PyOM compounds relative to ubiquitous dissolved organic matter (DOM) with a substrate-explicit model. The range of potential bioavailability of PyOM was greater than natural DOM; however, the predicted thermodynamics, metabolic rates, and carbon use efficiencies (CUEs) overlapped significantly between all OM pools. Compound type (e.g., natural versus PyOM) had approximately 6-fold less impact on predicted respiration rates than simulated carbon and oxygen limitations. Within PyOM, the metabolism of specific chemistries differed strongly between unlimited and oxygen-limited conditions – degradations of anhydrosugars, phenols, and polycyclic aromatic hydrocarbons (PAHs) were more favorable under oxygen limitation than other molecules. Notably, amino sugar-like, protein-like, and lignin-like PyOM had lower carbon use efficiencies relative to natural DOM of the same classes, indicating potential impacts in process-based model representations. Overall, our work illustrates how similar PyOM bioavailability may be to that of natural DOM in the river corridor, furthering our understanding of how PyOM may influence riverine biogeochemical cycling.</p

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

Marked isotopic variability within and between the Amazon River and marine dissolved black carbon pools

Riverine dissolved organic carbon (DOC) contains charcoal byproducts, termed black carbon (BC). To determine the significance of BC as a sink of atmospheric CO2 and reconcile budgets, the sources and fate of this large, slow-cycling and elusive carbon pool must be constrained. The Amazon River is a significant part of global BC cycling because it exports an order of magnitude more DOC, and thus dissolved BC (DBC), than any other river. We report spatially resolved DBC quantity and radiocarbon (Δ14C) measurements, paired with molecular-level characterization of dissolved organic matter from the Amazon River and tributaries during low discharge. The proportion of BC-like polycyclic aromatic structures decreases downstream, but marked spatial variability in abundance and Δ14C values of DBC molecular markers imply dynamic sources and cycling in a manner that is incongruent with bulk DOC. We estimate a flux from the Amazon River of 1.9–2.7 Tg DBC yr−1 that is composed of predominately young DBC, suggesting that loss processes of modern DBC are important

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

Linking trace gas measurements and molecular tracers of organic matter in aerosols for identification of ecosystem sources and types of wildfires in Central Siberia

Summer 2012 was one of the extreme wildfire years in Siberia. At the surface air monitoring station “ZOTTO” (60°48′N, 89°21′E, 114 m a.s.l.) in Central Siberia we observed biomass burning (BB) influence on the ongoing atmospheric measurements within more than 50 % of the time in June-July 2012 that indicates a 30 times greater wildfire signal compared to previously reported ordinary biomass burning signature for the study area. While previous studies thoroughly estimated a relative input of BB into aerosol composition (i.e. size distribution, physical and optical parameters etc.) at ZOTTO, in this paper we characterize the source apportionment of the smoke aerosols with molecular tracer techniques from large-scale wildfires occurred in 2012 in the two prevailing types of Central Siberian ecosystems: complexes of pine forests and bogs and dark coniferous forests. Wildfires in the selected ecosystems are highly differed by their combustion phase (flaming/smoldering), the type of fire (crown/ground), biomass fuel, and nature of soil that greatly determines the smoke particle composition. Anhydrosugars (levoglucosan and its isomers) and lignin phenols taken as indicators of the sources and the state of particulate matter (PM) inputs in the specific fire plumes were used as powerful tools to compare wildfires in different environmental conditions and follow the role and contribution of different sources of terrestrial organic matter in the transport of BB pollutants into the pristine atmosphere of boreal zone in Central Siberia

Discrimination in Degradability of Soil Pyrogenic Organic Matter Follows a Return-On-Energy-Investment Principle

A fundamental understanding of biodegradability is central to elucidating the role(s) of pyrogenic organic matter (PyOM) in biogeochemical cycles. Since microbial community and ecosystem dynamics are driven by net energy flows, then a quantitative assessment of energy value versus energy requirement for oxidation of PyOM should yield important insights into their biodegradability. We used bomb calorimetry, stepwise isothermal thermogravimetric analysis (<i>iso</i>TGA), and 5-year in situ bidegradation data to develop energy-biodegradability relationships for a suite of plant- and manure-derived PyOM (<i>n</i> = 10). The net energy value (Δ<i><i>E</i></i>) for PyOM was between 4.0 and 175 kJ mol^–1; with manure-derived PyOM having the highest Δ<i><i>E</i></i>. Thermal-oxidation activation energy (<i>E</i>_a) requirements ranged from 51 to 125 kJ mol^–1, with wood-derived PyOM having the highest <i>E</i>_a requirements. We propose a return-on-investment (ROI) parameter (Δ<i><i>E</i>/E</i>_a) for differentiating short-to-medium term biodegradability of PyOM and deciphering if biodegradation will most likely proceed via cometabolism (ROI < 1) or direct metabolism (ROI ≥ 1). The ROI-biodegradability relationship was sigmoidal with higher biodegradability associated with PyOM of higher ROI; indicating that microbes exhibit a higher preference for “high investment value” PyOM