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  • 1
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    Accessing monomers, surfactants, and the queen bee substance by acrylate cross-metathesis of long-chain alkenones (2017)
    Details
    Publication Date: 2022-05-25
    Description: Author Posting. © 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 Journal of the American Oil Chemists' Society 94 (2017): 831-840, doi: 10.1007/s11746-017-2997-8.
    Description: Polyunsaturated long-chain alkenones are a unique class of lipids biosynthesized in significant quantities (up to 20% of cell carbon) by several algae including the industrially grown marine microalgae Isochrysis. Alkenone structures are characterized by a long linear carbon-chain (35-40 carbons) with one to four trans-double bonds and terminating in a methyl or ethyl ketone. Alkenones were extracted and isolated from commercially obtained Isochrysis biomass and then subjected to cross-metathesis (CM) with methyl acrylate or acrylic acid using the Hoveyda-Grubbs metathesis initiator. Within 1 h at room temperature alkenones were consumed, however complete fragmentation (i.e. conversion to the smallest subunits by double bond cleavage) required up to 16 h. Analysis of the reaction mixture by gas chromatography and comprehensive two-dimensional gas chromatography revealed a predictable product mixture consisting primarily of long-chain (mostly C17) acids (or methyl esters from CM with methyl acrylate) and diacids (or diesters), along with smaller amounts (~5%) of the honey bee “queen substance” (E)-9-oxo-decenoic acid. Together, these compounds comprise a diverse mixture of valuable chemicals that includes surfactants, monomers, and an agriculturally relevant bee pheromone.
    Description: This work was supported by the National Science Foundation (CHE- 1151492) and through a private donation from friends of WHOI.
    Keywords: Algae ; Isochrysis ; Alkenones ; Metathesis ; Surfactants ; Polymers ; Pheromones
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 2
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    Shallow ponds are heterogeneous habitats within a temperate salt marsh ecosystem (2017)
    John Wiley & Sons
    Details
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2017. 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 122 (2017): 1371–1384, doi:10.1002/2017JG003780.
    Description: Integrating spatial heterogeneity into assessments of salt marsh biogeochemistry is becoming increasingly important because disturbances that reduce plant productivity and soil drainage may contribute to an expansion of shallow ponds. These permanently inundated and sometimes prominent landscape features can exist for decades, yet little is known about pond biogeochemistry or their role in marsh ecosystem functioning. We characterized three ponds in a temperate salt marsh (MA, USA) over alternating periods of tidal isolation and flushing, during summer and fall, by evaluating the composition of plant communities and organic matter pools and measuring surface water oxygen, temperature, and conductivity. The ponds were located in the high marsh and had similar depths, temperatures, and salinities. Despite this, they had different levels of suspended particulate, dissolved, and sediment organic matter and abundances of phytoplankton, macroalgae, and Ruppia maritima. Differences in plant communities were reflected in pond metabolism rates, which ranged from autotrophic to heterotrophic. Integrating ponds into landcover-based estimates of marsh metabolism resulted in slower rates of net production (−8.1 ± 0.3 to −15.7 ± 0.9%) and respiration (−2.9 ± 0.5 to −10.0 ± 0.4%), compared to rates based on emergent grasses alone. Seasonality had a greater effect on pond water chemistry, organic matter pools, and algal abundances than tidal connectivity. Alternating stretches of tidal isolation and flushing did not affect pond salinities or algal communities, suggesting that exchange between ponds and nearby creeks was limited. Overall, we found that ponds are heterogeneous habitats and future expansion could reduce landscape connectivity and the ability of marshes to capture and store carbon.
    Description: National Science Foundation Grant Number: OCE1233678; PIE-LTER Grant Number: OCE1238212; TIDE Grant Number: OCE1354494
    Description: 2017-12-15
    Keywords: Salt marsh ; Pond ; Organic matter ; Ecosystem functioning ; Metabolism ; Respiration
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 3
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    Soil organic carbon development and turnover in natural and disturbed salt marsh environments (2021)
    American Geophysical Union
    Details
    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 Geophysical Research Letters 48(2), (2021): e2020GL090287, https://doi.org/10.1029/2020GL090287.
    Description: Salt marsh survival with sea‐level rise (SLR) increasingly relies on soil organic carbon (SOC) accumulation and preservation. Using a novel combination of geochemical approaches, we characterized fine SOC (≤1 mm) supporting marsh elevation maintenance. Overlaying thermal reactivity, source (δ13C), and age (F14C) information demonstrates several processes contributing to soil development: marsh grass production, redeposition of eroded material, and microbial reworking. Redeposition of old carbon, likely from creekbanks, represented ∼9%–17% of shallow SOC (≤26 cm). Soils stored marsh grass‐derived compounds with a range of reactivities that were reworked over centuries‐to‐millennia. Decomposition decreases SOC thermal reactivity throughout the soil column while the decades‐long disturbance of ponding accelerated this shift in surface horizons. Empirically derived estimates of SOC turnover based on geochemical composition spanned a wide range (640–9,951 years) and have the potential to inform predictions of marsh ecosystem evolution.
    Description: This work was supported by NSF (OCE1233678) and NOAA (NA14OAR4170104 and NA14NOS4190145) grants to ACS, USGS Coastal & Marine Geology Program, and PIE‐LTER (NSF OCE1238212 and OCE1637630).
    Description: 2021-06-11
    Keywords: Carbon isotopes ; Decomposition ; Organic matter composition ; Salt marsh ; Soil organic carbon
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 4
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    Production of two highly abundant 2-methyl-branched fatty acids by blooms of the globally significant marine cyanobacteria Trichodesmium erythraeum (2021)
    American Chemical Society
    Details
    Publication Date: 2022-05-27
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Gosselin, K. M., Nelson, R. K., Spivak, A. C., Sylva, S. P., Van Mooy, B. A. S., Aeppli, C., Sharpless, C. M., O’Neil, G. W., Arrington, E. C., Reddy, C. M., & Valentine, D. L. Production of two highly abundant 2-methyl-branched fatty acids by blooms of the globally significant marine cyanobacteria Trichodesmium erythraeum. ACS Omega, 6(35), (2021): 22803–22810, https://doi.org/10.1021/acsomega.1c03196.
    Description: The bloom-forming cyanobacteria Trichodesmium contribute up to 30% to the total fixed nitrogen in the global oceans and thereby drive substantial productivity. On an expedition in the Gulf of Mexico, we observed and sampled surface slicks, some of which included dense blooms of Trichodesmium erythraeum. These bloom samples contained abundant and atypical free fatty acids, identified here as 2-methyldecanoic acid and 2-methyldodecanoic acid. The high abundance and unusual branching pattern of these compounds suggest that they may play a specific role in this globally important organism.
    Description: This work was funded with grants from the National Science Foundation grants OCE-1333148, OCE-1333162, and OCE-1756254 and the Woods Hole Oceanographic Institution (IR&D). GCxGC analysis made possible by WHOI’s Investment in Science Fund.
    Keywords: Lipids ; Alkyls ; Bacteria ; Genetics ; Chromatography
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 5
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    Time course experiment related data to validate incubation duration for methane oxidation rate measurement of the deep Santa Barbara Basin water column from September 2019 (BASIN project) (2022)
    Biological and Chemical Oceanography Data Management Office (BCO-DMO). Contact: bco-dmo-data@whoi.edu
    Details
    Publication Date: 2022-05-26
    Description: Dataset: Time Course Experiment Data
    Description: This time course experiment was performed to test if the uptake rate of 3H-CH4 is linear over the chosen incubation time (3 days) for the seawater samples. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/872687
    Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1829981, NSF Division of Ocean Sciences (NSF OCE) OCE-1830033
    Repository Name: Woods Hole Open Access Server
    Type: Dataset
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  • 6
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    Initial Methane Concentration Alteration Experiment Data of the Deep Santa Barbara Basin Water Column from October 2019 (BASIN project) (2022)
    Biological and Chemical Oceanography Data Management Office (BCO-DMO). Contact: bco-dmo-data@whoi.edu
    Details
    Publication Date: 2022-05-26
    Description: Dataset: Initial Methane Concentration Alteration Data
    Description: A methane concentration alteration experiment was performed to test the influence of methane concentration on methane oxidation rate. Together with the oxygen concentration alteration experiment, the purpose of this experiment was to test the assumption that methane oxidation in the Santa Barbara Basin deep water column follows first order kinetics. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/872652
    Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1829981, NSF Division of Ocean Sciences (NSF OCE) OCE-1830033
    Repository Name: Woods Hole Open Access Server
    Type: Dataset
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  • 7
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    Initial Oxygen Concentration Alteration Experiment Data of the Deep Santa Barbara Basin Water Column from October 2019 (BASIN project) (2022)
    Biological and Chemical Oceanography Data Management Office (BCO-DMO). Contact: bco-dmo-data@whoi.edu
    Details
    Publication Date: 2022-05-26
    Description: Dataset: Initial Oxygen Concentration Alteration Data
    Description: An oxygen concentration alteration experiment was performed to test the influence of oxygen concentration on methane oxidation rate. Together with the methane concentration alteration experiment, the purpose of this experiment was to test the assumption that methane oxidation in the Santa Barbara Basin deep water column follows first order kinetics. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/872665
    Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1829981, NSF Division of Ocean Sciences (NSF OCE) OCE-1830033
    Repository Name: Woods Hole Open Access Server
    Type: Dataset
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  • 8
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    Time series of oxygen, nitrate, methane concentrations and methane oxidation rates of the Santa Barbara Basin deep water column from 2019-2020 (BASIN project) (2022)
    Biological and Chemical Oceanography Data Management Office (BCO-DMO). Contact: bco-dmo-data@whoi.edu
    Details
    Publication Date: 2022-05-26
    Description: Dataset: Time Series Water Column Parameters
    Description: Time series of water column parameters (oxygen, nitrate, methane concentrations and methane oxidation rates) are sampled and measured to show the changes related to methane biogeochemistry during a deoxygenation and reoxygenation event in the deep Santa Barbara water column (440-583m). For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/872703
    Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1829981, NSF Division of Ocean Sciences (NSF OCE) OCE-1830033
    Repository Name: Woods Hole Open Access Server
    Type: Dataset
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  • 9
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    Salt marsh pond biogeochemistry changes hourly-to-yearly but does not scale with dimensions or geospatial position (2020)
    American Geophysical Union
    Details
    Publication Date: 2022-10-26
    Description: Author Posting. © American Geophysical Union, 2020. 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 125(10), (2020): e2020JG005664, doi:10.1029/2020JG005664.
    Description: Shallow ponds are expanding in many salt marshes with potential impacts on ecosystem functioning. Determining how pond characteristics change over time and scale with physical dimensions and other spatial predictors could facilitate incorporation of ponds into projections of ecosystem change. We evaluated scaling relationships across six differently sized ponds in three regions of the high marshes within the Plum Island Ecosystems‐Long Term Ecological Research site (MA, USA). We further characterized diel fluctuations in surface water chemistry in two ponds to understand short‐term processes that affect emergent properties (e.g., habitat suitability). Primary producers drove oxygen levels to supersaturation during the day, while nighttime respiration resulted in hypoxic to anoxic conditions. Diel swings in oxygen were mirrored by pH and resulted in successive shifts in redox‐sensitive metabolisms, as indicated by nitrate consumption at dusk followed by peaks in ammonium and then sulfide overnight. Abundances of macroalgae and Ruppia maritima correlated with whole‐pond oxygen metabolism rates, but not with surface area (SA), volume (V), or SA:V. Moreover, there were no clear patterns in primary producer abundances, surface water chemistry, or pond metabolism rates across marsh regions supplied by different tidal creeks or that differed in distance to upland borders or creekbanks. Comparisons with data from 2 years prior demonstrate that plant communities and biogeochemical processes are not in steady state. Factors contributing to variability between ponds and years are unclear but likely include infrequent tidal exchange. Temporal and spatial variability and the absence of scaling relationships complicate the integration of high marsh ponds into ecosystem biogeochemical models.
    Description: Thanks to S. McNichol, S. Jayne, E. Neel, and PIE‐LTER (NSF‐OCE1238212) for field assistance; I. Forbrich for meteorological data (Giblin & Forbrich, 2018); J. Jennings for dissolved nutrient analyses; J. Seewald for ion chromatograph access; and G. Mariotti for elevation data. C. Wilson and an anonymous reviewer provided comments that greatly improved our manuscript. A. C. S. was supported by NSF (OCE1233678), NOAA (NA14NOS4190145), and Sea Grant (NA14OAR4170104) awards, and A. D. by the MIT Undergraduate Research Opportunities Program.
    Description: 2021-03-15
    Keywords: Salt marsh ; Global change ; Biogeochemistry ; Metabolism ; Scaling ; Ecosystem function
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 10
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    Iron “ore” nothing: benthic iron fluxes from the oxygen-deficient Santa Barbara Basin enhance phytoplankton productivity in surface waters (2024)
    Copernicus Publications
    In:  EPIC3Biogeosciences, Copernicus Publications, 21(3), pp. 773-788, ISSN: 1726-4170
    Details
    Publication Date: 2024-05-23
    Description: The trace metal iron (Fe) is an essential micronutrient that controls phytoplankton productivity, which subsequently affects organic matter cycling with feedback on the cycling of macronutrients. Along the continental margin of the US West Coast, high benthic Fe release has been documented, in particular from deep anoxic basins in the Southern California Borderland. However, the influence of this Fe release on surface primary production remains poorly understood. In the present study from the Santa Barbara Basin, in situ benthic Fe fluxes were determined along a transect from shallow to deep sites in the basin. Fluxes ranged between 0.23 and 4.9mmolm-2d-1, representing some of the highest benthic Fe fluxes reported to date. To investigate the influence of benthic Fe release from the oxygen-deficient deep basin on surface phytoplankton production, we combined benthic flux measurements with numerical simulations using the Regional Ocean Modeling System coupled to the Biogeochemical Elemental Cycling (ROMS-BEC) model. For this purpose, we updated the model Fe flux parameterization to include the new benthic flux measurements from the Santa Barbara Basin. Our simulations suggest that benthic Fe fluxes enhance surface primary production, supporting a positive feedback on benthic Fe release by decreasing oxygen in bottom waters. However, a reduction in phytoplankton Fe limitation by enhanced benthic fluxes near the coast may be partially compensated for by increased nitrogen limitation further offshore, limiting the efficacy of this positive feedback.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , peerRev
    Format: application/pdf
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