Assessing sources and ages of organic matter supporting river and estuarine bacterial production: A multiple-isotope (D14C, d13C, and d15N) approach

We used radiocarbon (D14C) and stable isotopic (d13C, d15N) signatures of bacterial nucleic acids to estimate the sources and ages of organic matter (OM) assimilated by bacteria in the Hudson River and York River estuary. Dualisotope plots of D14C and d13C coupled with a three-source mixing model resolved the major OM sources supporting bacterial biomass production (BBP). However, overlap in the stable isotopic (d13C and d15N) values of potential source end members (i.e., terrestrial, freshwater phytoplankton, and marsh-derived) prohibited unequivocal source assignments for certain samples. In freshwater regions of the York, terrigenous material of relatively recent origin (i.e., decadal in age) accounted for the majority of OM assimilated by bacteria (49–83%). Marsh and freshwater planktonic material made up the other major source of OM, with 5–33% and 6–25% assimilated, respectively. In the mesohaline York, BBP was supported primarily by estuarine phytoplankton–derived OM during spring and summer (53–87%) and by marsh-derived OM during fall (as much as 83%). Isotopic signatures from higher salinity regions of the York suggested that BBP there was fueled predominantly by either estuarine phytoplankton-derived OM (July and November) or by material advected in from the Chesapeake Bay proper (October). In contrast to the York, BBP in the Hudson River estuary was subsidized by a greater portion (up to ;25%) of old (;24,000 yr BP) allochthonous OM, which was presumably derived from soils. These findings collectively suggest that bacterial metabolism and degradation in rivers and estuaries may profoundly alter the mean composition and age of OM during transport within these systems and before its export to the coastal ocean

Carbon budget of tidal wetlands, estuaries, and shelf waters of eastern North America

Author Posting. © American Geophysical Union, 2018. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 32 (2018): 389-416, doi:10.1002/2017GB005790.Carbon cycling in the coastal zone affects global carbon budgets and is critical for understanding the urgent issues of hypoxia, acidification, and tidal wetland loss. However, there are no regional carbon budgets spanning the three main ecosystems in coastal waters: tidal wetlands, estuaries, and shelf waters. Here we construct such a budget for eastern North America using historical data, empirical models, remote sensing algorithms, and process‐based models. Considering the net fluxes of total carbon at the domain boundaries, 59 ± 12% (± 2 standard errors) of the carbon entering is from rivers and 41 ± 12% is from the atmosphere, while 80 ± 9% of the carbon leaving is exported to the open ocean and 20 ± 9% is buried. Net lateral carbon transfers between the three main ecosystem types are comparable to fluxes at the domain boundaries. Each ecosystem type contributes substantially to exchange with the atmosphere, with CO2 uptake split evenly between tidal wetlands and shelf waters, and estuarine CO2 outgassing offsetting half of the uptake. Similarly, burial is about equal in tidal wetlands and shelf waters, while estuaries play a smaller but still substantial role. The importance of tidal wetlands and estuaries in the overall budget is remarkable given that they, respectively, make up only 2.4 and 8.9% of the study domain area. This study shows that coastal carbon budgets should explicitly include tidal wetlands, estuaries, shelf waters, and the linkages between them; ignoring any of them may produce a biased picture of coastal carbon cycling.NASA Interdisciplinary Science program Grant Number: NNX14AF93G; NASA Carbon Cycle Science Program Grant Number: NNX14AM37G; NASA Ocean Biology and Biogeochemistry Program Grant Number: NNX11AD47G; National Science Foundation's Chemical Oceanography Program Grant Number: OCE‐12605742018-10-0

Molecular transformation and degradation of refractory dissolved organic matter in the Atlantic and Southern Ocean

More than 90% of the global ocean dissolved organic carbon (DOC) is refractory, has an average age of 4,000–6,000 years and a lifespan from months to millennia. The fraction of dissolved organic matter (DOM) that is resistant to degradation is a long-term buffer in the global carbon cycle but its chemical composition, structure, and biochemical formation and degradation mechanisms are still unresolved. We have compiled the most comprehensive molecular data set of 197 Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analyses from solid-phase extracted marine DOM covering two major oceans, the Atlantic sector of the Southern Ocean and the East Atlantic Ocean (ranging from 50° N to 70° S). Molecular trends and radiocarbon dating of 34 DOM samples (comprising Δ14C values from -229 to -495‰) were combined to model an integrated degradation rate for bulk DOC resulting in a predicted age of >24 ka for the most persistent DOM fraction. First order kinetic degradation rates for 1,557 mass peaks indicate that numerous DOM molecules cycle on timescales much longer than the turnover of the bulk DOC pool (estimated residence times of >100 ka) and the range of validity of radiocarbon dating. Changes in elemental composition were determined by assigning molecular formulae to the detected mass peaks. The combination of residence times with molecular information enabled modelling of the average elemental composition of the slowest degrading fraction of the DOM pool. In our dataset, a group of 361 molecular formulae represented the most stable composition in the oceanic environment (“island of stability”). These most persistent compounds encompass only a narrow range of the elemental ratios H/C (average of 1.17 ± 0.13), and O/C (average of 0.52 ± 0.10) and molecular masses (360 ± 28 and 497 ± 51 Da). In the Weddell Sea DOC concentrations in the surface waters were low (46.3 ± 3.3 μM) while the organic radiocarbon was significantly more depleted than that of the East Atlantic, indicating average surface water DOM ages of 4,920 ± 180 a. These results are in accordance with a highly degraded DOM in the Weddell Sea surface water as also shown by the molecular degradation index IDEG obtained from FT-ICR MS data. Further, we identified 339 molecular formulae which probably contribute to an increased DOC concentration in the Southern Ocean and potentially reflect an accumulation or enhanced sequestration of refractory DOC in the Weddell Sea. These results will contribute to a better understanding of the persistent nature of marine DOM and its role as an oceanic carbon buffer in a changing climate

Quantification and molecular characterization of dissolved organic sulfur in water samples obtained during POLARSTERN cruise ANT-XXV (PS73) to the East Atlantic and the Southern Ocean

Although sulfur is an essential element for marine primary production and critical for climate processes, little is known about the oceanic pool of non-volatile dissolved organic sulfur (DOS). We present a basin-scale distribution of solid phase extractable DOS in the East Atlantic Ocean and the Atlantic sector of the Southern Ocean. While molar DOS versus dissolved organic nitrogen (DON) ratios of 0.11 ± 0.024 in Atlantic surface water resembled phytoplankton stoichiometry (S/N ~ 0.08), increasing dissolved organic carbon (DOC) versus DOS ratios and decreasing methionine-S yield demonstrated selective DOS removal and active involvement in marine biogeochemical cycles. Based on stoichiometric estimates, the minimum global inventory of marine DOS is 6.7 Pg S, exceeding all other marine organic sulfur reservoirs by an order of magnitude