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  • FT-ICR MS  (2)
  • Radiocarbon  (2)
  • Alkalinity  (1)
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  • 1
    Publication Date: 2022-05-27
    Description: Author Posting. © American Geophysical Union, 2021. 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 35(6), (2021): e2021GB006938, https://doi.org/10.1029/2021GB006938.
    Description: As climate-driven El Niño Southern Oscillation (ENSO) events are projected to increase in frequency and severity, much attention has focused on impacts regarding ecosystem productivity and carbon balance in Amazonian rainforests, with comparatively little attention given to carbon dynamics in fluvial ecosystems. In this study, we compared the wet 2012 La Niña period to the following normal hydrologic period in the Amazon River. Elevated water flux during the La Niña period was accompanied by dilution of inorganic ion concentrations. Furthermore, the La Niña period exported 2.77 Tg C yr−1 more dissolved organic carbon (DOC) than the normal period, an increase greater than the annual amount of DOC exported by the Mississippi River. Using ultra-high-resolution mass spectrometry, we detected both intra- and interannual differences in dissolved organic matter (DOM) composition, revealing that DOM exported during the dry season and the normal period was more aliphatic, whereas compounds in the wet season and following the La Niña event were more aromatic, with ramifications for its environmental role. Furthermore, as this study has the highest temporal resolution DOM compositional data for the Amazon River to-date we showed that compounds were highly correlated to a 6-month lag in Pacific temperature and pressure anomalies, suggesting that ENSO events could impact DOM composition exported to the Atlantic Ocean. Therefore, as ENSO events increase in frequency and severity into the future it seems likely that there will be downstream consequences for the fate of Amazon Basin-derived DOM concurrent with lag periods as described here.
    Description: This work was partially supported by National Science Foundation grant OCE-1464396 to Robert G. M. Spencer and funding from the Harbourton Foundation to Robert G. M. Spencer, R. Max Holmes, and Bernhard Peucker-Ehrenbrink.
    Description: 2021-12-11
    Keywords: Amazon river ; carbon cycling ; dissolved organic carbon ; dissolved organic matter ; ENSO ; FT-ICR MS
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2013. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 40 (2013): 511–516, doi:10.1002/grl.50160.
    Description: Seasonal variations in inorganic carbon chemistry and associated fluxes from the Congo River were investigated at Brazzaville-Kinshasa. Small seasonal variation in dissolved inorganic carbon (DIC) was found in contrast with discharge-correlated changes in pH, total alkalinity (TA), carbonate species, and dissolved organic carbon (DOC). DIC was almost always greater than TA due to the importance of CO2*, the sum of dissolved CO2 and carbonic acid, as a result of low pH. Organic acids in DOC contributed 11–61% of TA and had a strong titration effect on water pH and carbonate speciation. The CO2* and bicarbonate fluxes accounted for ~57% and 43% of the DIC flux, respectively. Congo River surface water released CO2 at a rate of ~109 mol m−2 yr−1. The basin-wide DIC yield was ~8.84 × 104 mol km−2 yr−1. The discharge normalized DIC flux to the ocean amounted to 3.11 × 1011 mol yr−1. The DOC titration effect on the inorganic carbon system may also be important on a global scale for regulating carbon fluxes in rivers.
    Description: This project was supported by a grant from the National Science Foundation for the Global Rivers Project (NSF 0851101).
    Description: 2013-08-14
    Keywords: Inorganic carbon ; Carbon dioxide ; Carbon fluxes ; pH ; Alkalinity ; Congo River
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/pdf
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  • 3
    Publication Date: 2022-05-26
    Description: © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Chemical Geology 466 (2017): 454-465, doi:10.1016/j.chemgeo.2017.06.034.
    Description: We present dissolved organic carbon (DOC) concentrations, particulate organic matter (POM) composition (δ13C, δ15N, ∆14C, N/C), and particulate glycerol dialkyl glycerol tetraether (GDGT) distributions from a 34-month time-series near the mouth of the Congo River. An end-member mixing model using δ13C and N/C indicates that exported POM is consistently dominated by C3 rainforest soil sources, with increasing contribution from C3 vegetation and decreasing contribution from phytoplankton at high discharge. Large C4 inputs are never observed despite covering ≈ 13 % of the catchment. Low and variable ∆14C values during 2011 [annual mean = (-148 ± 82) ‰], when discharge from left-bank tributaries located in the southern hemisphere reached record lows, likely reflect a bias toward pre-aged POM derived from the Cuvette Congolaise swamp forest. In contrast, ∆14C values were stable near -50 ‰ between January and June 2013, when left-bank discharge was highest. We suggest that headwater POM is replaced and/or diluted by C3 vegetation and pre-aged soils during transit through the Cuvette Congolaise, whereas left-bank tributaries export significantly less pre-aged material. GDGT distributions provide further evidence for seasonal and inter-annual variability in soil provenance. The cyclization of branched tetraethers and the GDGT-0 to crenarchaeol ratio are positively correlated with discharge (r ≥ 0.70; p-value ≤ 4.3×10-5) due to the incorporation of swamp-forest soils when discharge from right-bank tributaries located in the northern hemisphere is high. Both metrics reach record lows during 2013, supporting our interpretation of increased left-bank contribution at this time. We conclude that hydrologic variability is a major control of POM provenance in the Congo River Basin and that tropical wetlands can be a significant POM source despite their small geographic coverage.
    Description: J.D.H. was supported by the NSF Graduate Research Fellowship Program under grant number 2012126152; E.S. was supported by the DFG Research Center/Cluster of Excellence “The Ocean in the Earth System” at MARUM – Center for Environmental Sciences; V.V.G. was partly supported by the US National Science Foundation, grants OCE-0851015 and OCE-0928582; R.G.M.S. was partly supported by the US National Science Foundation, grants OCE-0851101, OCE-1333157, and OCE-1464396; and T.I.E. was partly supported by the Swiss National Science Foundation (SNF Grant No. 200021_140850).
    Keywords: Biomarkers ; Congo River ; GDGTs ; Particulate Organic Matter ; Radiocarbon
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 4
    Publication Date: 2022-11-04
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Voss, B., Eglinton, T., Peucker-Ehrenbrink, B., Galy, V., Lang, S., McIntyre, C., Spencer, R., Bulygina, E., Wang, Z., & Guay, K. Isotopic evidence for sources of dissolved carbon and the role of organic matter respiration in the Fraser River basin, Canada. Biogeochemistry. (2022), https://doi.org/10.1007/s10533-022-00945-5.
    Description: Sources of dissolved and particulate carbon to the Fraser River system vary significantly in space and time. Tributaries in the northern interior of the basin consistently deliver higher concentrations of dissolved organic carbon (DOC) to the main stem than other tributaries. Based on samples collected near the Fraser River mouth throughout 2013, the radiocarbon age of DOC exported from the Fraser River does not change significantly across seasons despite a spike in DOC concentration during the freshet, suggesting modulation of heterogeneous upstream chemical and isotopic signals during transit through the river basin. Dissolved inorganic carbon (DIC) concentrations are highest in the Rocky Mountain headwater region where carbonate weathering is evident, but also in tributaries with high DOC concentrations, suggesting that DOC respiration may be responsible for a significant portion of DIC in this basin. Using an isotope and major ion mass balance approach to constrain the contributions of carbonate and silicate weathering and DOC respiration, we estimate that up to 33 ± 11% of DIC is derived from DOC respiration in some parts of the Fraser River basin. Overall, these results indicate close coupling between the cycling of DOC and DIC, and that carbon is actively processed and transformed during transport through the river network.
    Description: Open Access funding provided by the MIT Libraries. This work was supported by the WHOI Academic Programs Office, the MIT EAPS Department Student Assistance Fund, and the PAOC Houghton Fund to BMV; NSF-ETBC grants OCE-0851015 to BPE, VG, and TIE and OCE-0851101 to RGMS; NSF grant EAR-1226818 to BPE; NSF grant OCE-0928582 to TIE and VG; and a WHOI Arctic Research Initiative grant to ZAW.
    Keywords: River ; Carbon isotopes ; Radiocarbon ; Weathering ; Carbon cycle
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 5
    Publication Date: 2022-10-26
    Description: Author Posting. © American Geophysical Union, 2021. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Biogeosciences 126(7), (2021): e2020JG005977, https://doi.org/10.1029/2020JG005977.
    Description: Increasing Arctic temperatures are thawing permafrost soils and liberating ancient organic matter, but the fate of this material remains unclear. Thawing of permafrost releases dissolved organic matter (DOM) into fluvial networks. Unfortunately, tracking this material in Arctic rivers such as the Kolyma River in Siberia has proven challenging due to its high biodegradability. Here, we evaluate late summer abruptly thawed yedoma permafrost dissolved organic carbon (DOC) inputs from Duvannyi Yar. We implemented ultrahigh-resolution mass spectrometry alongside ramped pyrolysis oxidation (RPO) and isotopic analyses. These approaches offer insight into DOM chemical composition and DOC radiocarbon values of thermochemical components for a permafrost thaw stream, the Kolyma River, and their biodegraded counterparts (n = 4). The highly aliphatic molecular formula found in undegraded permafrost DOM contrasted with the comparatively aliphatic-poor formula of Kolyma River DOM, represented by an 8.9% and 2.6% relative abundance, respectively, suggesting minimal inputs of undegraded permafrost DOM in the river. RPO radiocarbon fractions of Kolyma River DOC exhibited no “hidden” aged component indicative of permafrost influence. Thermostability analyses suggested that there was limited biodegraded permafrost DOC in the Kolyma River, in part determined by the formation of high-activation energy (thermally stable) biodegradation components in permafrost DOM that were lacking in the Kolyma River. A mixing model based on thermostability and radiocarbon allowed us to estimate a maximum input of between 0.8% and 7.7% of this Pleistocene-aged permafrost to the Kolyma River DOC. Ultimately, our findings highlight that export of modern terrestrial DOC currently overwhelms any permafrost DOC inputs in the Kolyma River.
    Description: This work was funded by NSF grants ANT-1203885 and PLR-1500169 to R.G.M.S. The work was also supported by the National Science Foundation Division of Chemistry through DMR-1644779 and the State of Florida.
    Description: 2022-01-09
    Keywords: Permafrost ; Dissolved organic carbon ; Dissolved organic matter ; FT-ICR MS ; Ramped pyrolysis oxidation ; Arctic
    Repository Name: Woods Hole Open Access Server
    Type: Article
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