Aquatic Isotope biogeochemistry

available here: https://rdcu.be/cRcuS 

Black carbon (BC) is a recalcitrant form of organic carbon (OC) produced by landscape fires. BC is an important component of the global carbon cycle because, compared to unburned biogenic OC, it is selectively conserved in terrestrial and oceanic pools. Here we show that the dissolved BC (DBC) content of dissolved OC (DOC) is twice greater in major (sub)tropical and high-latitude rivers than in major temperate rivers, with further significant differences between biomes. We estimate that rivers export 18 ± 4 Tg DBC year⁻¹ globally and that, including particulate BC fluxes, total riverine export amounts to 43 ± 15 Tg BC year⁻¹ (12 ± 5% of the OC flux). While rivers export ~1% of the OC sequestered by terrestrial vegetation, our estimates suggest that 34 ± 26% of the BC produced by landscape fires has an oceanic fate. Biogeochemical models require modification to account for the unique dynamics of BC and to predict the response of recalcitrant OC export to changing environmental conditions.

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.

Pdf available here: Springer Current Climate Change Reports

Purpose of Review: Understanding of how fire affects the carbon cycle and climate is crucial for climate change adaptation and mitigation strategies. As those are often based on Earth system model simulations, we identify recent progress and research needs that can improve the model representation of fire and its impacts.

Recent Findings: New constraints of fire effects on the carbon cycle and climate are provided by the quantification of the carbon ages and effects of vegetation types and traits. For global scale modelling the low understanding of the human-fire relationship is limiting.

Summary: ReviewRecent developments allow improvements in Earth system models with respect to the influences of vegetation on climate, peatland burning and the pyrogenic carbon cycle. Better understanding of human influences is required.

Given the impacts of fire on carbon storage and climate, thorough understanding of the effects of fire in the Earth system is crucial to support climate change mitigation and adaptation.

Wildfires and incomplete combustion of fossil fuel produce large amounts of black carbon. Black carbon production and transport are essential components of the carbon cycle. Constraining estimates of black carbon exported from land to ocean is critical, given ongoing changes in land use and climate, which affect fire occurrence and black carbon dynamics. Here, we present an inventory of the concentration and radiocarbon content (∆¹⁴C) of particulate black carbon for 18 rivers around the globe. We find that particulate black carbon accounts for about 15.8 ± 0.9% of river particulate organic carbon, and that fluxes of particulate black carbon co-vary with river-suspended sediment, indicating that particulate black carbon export is primarily controlled by erosion. River particulate black carbon is not exclusively from modern sources but is also aged in intermediate terrestrial carbon pools in several high-latitude rivers, with ages of up to 17,000 ¹⁴C years. The flux-weighted ¹⁴C average age of particulate black carbon exported to oceans is 3,700 ± 400 ¹⁴C years. We estimate that the annual global flux of particulate black carbon to the ocean is 0.017 to 0.037 Pg, accounting for 4 to 32% of the annually produced black carbon. When buried in marine sediments, particulate black carbon is sequestered to form a long-term sink for CO₂.

Dissolved organic carbon (DOC) is the largest pool of exchangeable organic carbon in the ocean. However, less than 10% of DOC has been molecularly characterised in the deep ocean to understand DOC’s recalcitrance. Here, we analyze the radiocarbon (¹⁴C) depleted, and presumably refractory, low molecular weight (LMW) DOC extracted from the North Central Pacific using atomic force microscopy (AFM) to produce the first atomic-resolution images of individual LMW DOC molecules. We evaluate surface and deep LMW DOC chemical structures in the context of its relative persistence and recalcitrance. AFM resolved planar structures with features similar to polycyclic aromatic compounds and carboxylic-rich alicyclic structures with less than five aromatic carbon rings. These compounds comprise 8% and 20% of the measurable molecules investigated in the surface and deep, respectively. Resolving the structures of individual DOC molecules represents a step forward in molecular characterisation of DOC and in understanding its long-term stability.

Humans have interacted with fire for thousands of years, yet the utilization of fossil fuels marked the beginning of a new era. Ubiquitous in the environment, pyrogenic carbon (PyC) arises from incomplete combustion of biomass and fossil fuels, forming a continuum of condensed aromatic structures. Here, we develop and evaluate ¹⁴C records for two complementary PyC molecular markers, benzene polycarboxylic acids (BPCAs) and polycyclic aromatic hydrocarbons (PAHs), preserved in aquatic sediments from a suburban and a remote catchment in the United States (U.S.) from the mid-1700s to 1998. Results show that the majority of PyC stems from local sources and is transferred to aquatic sedimentary archives on subdecadal to millennial time scales. Whereas a small portion stems from near-contemporaneous production and sedimentation, the majority of PyC (∼90%) experiences delayed transmission due to “preaging” on millennial time scales in catchment soils prior to its ultimate deposition. BPCAs (soot) and PAHs (precursors of soot) trace fossil fuel-derived PyC. Both markers parallel historical records of the consumption of fossil fuels in the U.S., yet never account for more than 19% total PyC. This study demonstrates that isotopic characterization of multiple tracers is necessary to constrain histories and inventories of PyC and that sequestration of PyC can markedly lag its production.

The questions that chemical oceanographers prioritize over the coming decades, and the methods we use to address these questions, will define our field's contribution to 21st century science. In recognition of this, the U.S. National Science Foundation and National Oceanic and Atmospheric Administration galvanized a community effort (the Chemical Oceanography MEeting: A BOttom-up Approach to Research Directions, or COME ABOARD) to synthesize bottom-up perspectives on selected areas of research in Chemical Oceanography. Representing only a small subset of the community, COME ABOARD participants did not attempt to identify targeted research directions for the field. Instead, we focused on how best to foster diverse research in Chemical Oceanography, placing emphasis on the following themes: strengthening our core chemical skillset; expanding our tools through collaboration with chemists, engineers, and computer scientists; considering new roles for large programs; enhancing interface research through interdisciplinary collaboration; and expanding ocean literacy by engaging with the public. For each theme, COME ABOARD participants reflected on the present state of Chemical Oceanography, where the community hopes to go and why, and actionable pathways to get there.

Marine dissolved organic carbon (DOC) is produced in the surface ocean though its radiocarbon (¹⁴C) age in the deep ocean is thousands of years old. Here we show that ≥10% of the DOC in the deep North Atlantic is of postbomb origin and that the ¹⁴C age of the prebomb DOC is ≥4900 ¹⁴C year, ~900 ¹⁴C year older than previous estimates. We report ¹⁴C ages of DOC in the deep South Atlantic that are intermediate between values in the North Atlantic and the Southern Ocean. Finally, we conclude that prebomb DOC ¹⁴C ages are older and a portion of deep DOC is more dynamic than previously reported.

Black carbon (BC) is a by‐product of combustion from wildfires and fossil fuels and is a slow‐cycling component of the carbon cycle. Whether BC accumulates and ages on millennial time scales in the world oceans has remained unknown. Here we quantified dissolved BC (DBC) in marine dissolved organic carbon isolated by solid phase extraction at several sites in the world ocean. We find that DBC in the Atlantic, Pacific, and Arctic oceans ranges from 1.4 to 2.6 μM in the surface and is 1.2 ± 0.1 μM in the deep Atlantic. The average ¹⁴C age of surface DBC is 4800 ± 620 ¹⁴C years and much older in a deep water sample (23,000 ± 3000 ¹⁴C years). The range of DBC structures and ¹⁴C ages indicates that DBC is not homogeneous in the ocean. We show that there are at least two distinct pools of marine DBC, a younger pool that cycles on centennial time scales and an ancient pool that cycles on >10⁵ year time scales.

Radiocarbon analysis is a powerful tool for understanding the cycling of individual components within carbon pools, such as black carbon (BC) in dissolved organic carbon (DOC). Radiocarbon (Δ¹⁴C) measurements of BC in DOC provide insight into one source of aged, recalcitrant DOC. We report a modified solid phase extraction (SPE) method to concentrate 43 ± 6% of DOC (SPE-DOC) from seawater. We used the Benzene Polycarboxylic Acid (BPCA) method to isolate BC from SPE-DOC (SPE-BC) for subsequent ¹⁴C analysis. We report SPE-BC Δ¹⁴C values, SPE-BC concentrations, and the relative BPCA distributions from Milli-Q water process blanks, two riverine reference standards, as well as a coastal and an open ocean surface water sample. The composition of BC is less aromatic in the ocean samples than those in the river standards. We find higher BC Δ¹⁴C values in the river standards (+ 148 to − 462‰) than BC in the ocean samples (− 592 to − 712‰), suggesting that BC ages within oceanic DOC. We report that BC is 4.2 ± 1.0% of SPE-DOC in the open ocean surface sample, or 1.4 ± 0.1 μM C. This work provides the methodological basis by which global BC concentrations, compositions (e.g. relative abundances of BPCA marker compounds) and ∆¹⁴C values can be assessed.

We report measurements of oceanic black carbon (BC) to determine the sources of BC to abyssal marine sediments in the northeast Pacific Ocean. We find that the average ¹⁴C age of BC is older (by 6200 ± 2200 ¹⁴C years) than that of the concurrently deposited non‐BC sedimentary organic carbon. We investigate sources of aged BC to sediments by measuring a sample of sinking particulate organic carbon (POC) and find that POC may provide the main transport mechanism of BC to sediments. We suggest that aged BC is incorporated into POC from a combination of resuspended sediments and sorption of ancient dissolved organic carbon BC onto POC. Our BC flux estimate represents ~8–16% of the global burial flux of organic carbon to abyssal sediments and constitutes a minimum long‐term removal estimate of 6–32% of biomass‐derived BC using the present day emission flux.

Extraneous carbon (Cex) added during chemical processing and isolation of black carbon (BC) in environmental matrices was quantified to assess its impact on compound specific radiocarbon analysis (CSRA). Extraneous carbon is added during the multiple steps of BC extraction, such as incomplete removal of solvents, and carbon bleed from the gas chromatographic and cation columns. We use 2 methods to evaluate the size and Δ14C values of Cex in BC in ocean sediments that require additional pretreatment using a cation column with the benzene polycarboxylic acid (BPCA) method. First, the direct method evaluates the size and Δ14C value of Cex directly from the process blank, generated by processing initially empty vials through the entire method identically to the treatment of a sample. Second, the indirect method quantifies Cex as the difference between processed and unprocessed (bulk) Δ14C values in a variety of modern and 14C-free or “dead” BC standards. Considering a suite of hypothetical marine sedimentary samples of various sizes and Δ14C values and BC Ring Trial standards, we compare both methods of corrections and find agreement between samples that are >50 μg C. Because Cex can profoundly influence the measured Δ14C value of compound specific samples, we strongly advocate the use of multiple types of process standards that match the sample size to assess Cex and investigate corrections throughout extensive sample processing.

We report results of duplicate measurements of dissolved organic carbon concentrations ([DOC] as μM) and Δ14C in seawater in order to assess the total uncertainty of reported [DOC] and Δ14C measurements via the UV oxidation method. In addition, pure International Atomic Energy Agency standards analyzed over a 4-yr period are evaluated. We find the total uncertainty of Δ14C measurements to be ±4.0. However, in samples that were thawed, subsampled, and refrozen prior to UV oxidation, the total uncertainty of Δ14C measurements is on the order of ±10. The [DOC] measurements of these samples were also higher by 1.8 ± 0.3 μM. The reason(s) for these documented increases in total [DOC] and Δ14C uncertainty are unclear. In order to minimize any effects on sample measurements, we recommend the following: 1) regular monitoring of duplicate samples, DOC standards, and diluent (Milli-Q™) water for Δ14C and [DOC] measurements; 2) thawing a sample immediately and only once prior to UV oxidation; 3) avoid the use of DOC-leachable plumbing (such as PVC pipe) in both water systems feeding and within Milli-Q systems; and 4) consider the use of DOC-free diluents (i.e. pre-UV oxidized Milli-Q or sample water).