Description: The dynamics of the particulate organic carbon (POC) pool in the ocean are central to the marine carbon cycle. POC is the link between surface primary production, the deep ocean, and sediments. The rate at which POC is degraded in the dark ocean can impact atmospheric CO2 concentration. Therefore, a central focus of marine organic geochemistry studies is to improve our understanding of POC distribution, composition, and cycling. The last few decades have seen improvements in analytical techniques that have greatly expanded what we can measure, both in terms of organic compound structural diversity and isotopic composition, and complementary molecular omics studies. Here we provide a brief overview of the autochthonous, allochthonous, and anthropogenic components comprising POC in the ocean. In addition, we highlight key needs for future research that will enable us to more effectively connect diverse data sources and link the identity and structural diversity of POC to its sources and transformation processes.

Description: wo commonly used proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) are the TEX86 (TetraEther indeX of 86 carbon atoms) paleothermometer for sea surface temperature reconstructions and the BIT (Branched Isoprenoid Tetraether) index for reconstructing soil organic matter input to the ocean. An initial round-robin study of two sediment extracts, in which 15 laboratories participated, showed relatively consistent TEX86 values (reproducibility ±3–4°C when translated to temperature) but a large spread in BIT measurements (reproducibility ±0.41 on a scale of 0–1). Here we report results of a second round-robin study with 35 laboratories in which three sediments, one sediment extract, and two mixtures of pure, isolated GDGTs were analyzed. The results for TEX86 and BIT index showed improvement compared to the previous round-robin study. The reproducibility, indicating interlaboratory variation, of TEX86 values ranged from 1.3 to 3.0°C when translated to temperature. These results are similar to those of other temperature proxies used in paleoceanography. Comparison of the results obtained from one of the three sediments showed that TEX86 and BIT indices are not significantly affected by interlaboratory differences in sediment extraction techniques. BIT values of the sediments and extracts were at the extremes of the index with values close to 0 or 1, and showed good reproducibility (ranging from 0.013 to 0.042). However, the measured BIT values for the two GDGT mixtures, with known molar ratios of crenarchaeol and branched GDGTs, had intermediate BIT values and showed poor reproducibility and a large overestimation of the “true” (i.e., molar-based) BIT index. The latter is likely due to, among other factors, the higher mass spectrometric response of branched GDGTs compared to crenarchaeol, which also varies among mass spectrometers. Correction for this different mass spectrometric response showed a considerable improvement in the reproducibility of BIT index measurements among laboratories, as well as a substantially improved estimation of molar-based BIT values. This suggests that standard mixtures should be used in order to obtain consistent, and molar-based, BIT values.

Description: © 2008 Author(s). This work is distributed under the Creative Commons Attribution License. The definitive version was published in Biogeosciences 5 (2008): 95-109, doi:10.5194/bg-5-95-2008

Description: Due to the low atmospheric input of phosphate into the open ocean, it is one of the key nutrients that could ultimately control primary production and carbon export into the deep ocean. The observed trend over the last 20 years has shown a decrease in the dissolved inorganic phosphate (DIP) pool in the North Pacific gyre, which has been correlated to the increase in di-nitrogen (N2) fixation rates. Following a NW-SE transect, in the Southeast Pacific during the early austral summer (BIOSOPE cruise), we present data on DIP, dissolved organic phosphate (DOP) and particulate phosphate (PP) pools along with DIP turnover times (TDIP) and N2 fixation rates. We observed a decrease in DIP concentration from the edges to the centre of the gyre. Nevertheless the DIP concentrations remained above 100 nmol L−1 and T DIP was more than 6 months in the centre of the gyre; DIP availability remained largely above the level required for phosphate limitation to occur and the absence of Trichodesmium spp and low nitrogen fixation rates were likely to be controlled by other factors such as temperature or iron availability. This contrasts with recent observations in the North Pacific Ocean at the ALOHA station and in the western Pacific Ocean at the same latitude (DIAPALIS cruises) where lower DIP concentrations (〈20 nmol L−1) and T DIP 〈50 h were measured during the summer season in the upper layer. The South Pacific gyre can be considered a High Phosphate Low Chlorophyll (HPLC) oligotrophic area, which could potentially support high N2 fixation rates and possibly carbon dioxide sequestration, if the primary ecophysiological controls, temperature and/or iron availability, were alleviated.

Description: This research was funded by the Centre National de la Recherche Scientifique (CNRS), the Institut des Sciences de l’Univers (INSU), the Centre National d’Etudes Spatiales (CNES), the European Space Agency (ESA), The National Aeronautics and Space Administration (NASA) and the Natural Sciences and Engineering Research Council of Canada (NSERC). This work is funded in part by the French Research and Education council.

Description: Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 10 (2009): Q03012, doi:10.1029/2008GC002221.

Description: Recently, two new proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) were proposed, i.e., the TEX86 proxy for sea surface temperature reconstructions and the BIT index for reconstructing soil organic matter input to the ocean. In this study, fifteen laboratories participated in a round robin study of two sediment extracts with a range of TEX86 and BIT values to test the analytical reproducibility and repeatability in analyzing these proxies. For TEX86 the repeatability, indicating intra-laboratory variation, was 0.028 and 0.017 for the two sediment extracts or ±1–2°C when translated to temperature. The reproducibility, indicating among-laboratory variation, of TEX86 measurements was substantially higher, i.e., 0.050 and 0.067 or ±3–4°C when translated to temperature. The latter values are higher than those obtained in round robin studies of Mg/Ca and U37 k′ paleothermometers, suggesting the need to primarily improve compatibility between labs. The repeatability of BIT measurements for the sediment with substantial amounts of soil organic matter input was relatively small, 0.029, but reproducibility was large, 0.410. This large variance could not be attributed to specific equipment used or a particular data treatment. We suggest that this may be caused by the large difference in the molecular weight in the GDGTs used in the BIT index, i.e., crenarchaeol versus the branched GDGTs. Potentially, this difference gives rise to variable responses in the different mass spectrometers used. Calibration using authentic standards is needed to establish compatibility between labs performing BIT measurements.

Description: Author Posting. © Inter-Research, 2009. This article is posted here by permission of Inter-Research for personal use, not for redistribution. The definitive version was published in Aquatic Microbial Ecology 54 (2009): 127-133, doi:10.3354/ame01261.

Description: Quorum sensing (QS) via acylated homoserine lactones (AHLs) was discovered in the ocean, yet AHLs are expected to be very short-lived at seawater pH due to rapid abiotic degradation. Quorum quenching, the enzymatic degradation of AHLs, is also likely. To better understand the potential for QS to regulate behaviors of marine bacteria, we investigated the degradation of a variety of AHL molecules in several types of seawater media. We did this by incubating AHLs and tracking their concentration using HPLC/electrospray-ionization mass-spectrometry (HPLC/ESI-MS). AHL concentrations decreased with time, and degradation rate coefficients were calculated by applying a first-order rate law. The rate of abiotic degradation showed strong dependence on acyl chain length and the presence of 3-oxo substitutions on the acyl chain. We found that the rate of abiotic degradation of AHLs in artificial seawater was much slower than that predicted by an oft-cited equation for non-marine media that takes only pH into account. However, AHLs degraded more rapidly in natural seawater than in artificial seawater, an observation we found to be due to quorum quenching enzyme activity. By applying calculated degradation rates in a simple steady-state calculation, we suggest that despite the observed quorum quenching activity, AHLs are likely to be viable signals in organic particles and in other microbial ‘hotpsots’ in marine environments.

Description: This work was funded by a grant from the Office of Naval Research to B.A.S.V.M. (N0014-06-1-0134), and an NSF Graduate Student Fellowship to L.H.

Description: Author Posting. © The Author(s), 2010. This is the author's version of the work. It is posted here by permission of Nature Publishing Group for personal use, not for redistribution. The definitive version was published in The ISME Journal 5 (2011): 1057–1060, doi:10.1038/ismej.2010.192.

Description: In low phosphorus (P) marine systems phytoplankton replace membrane phospholipids with non-phosphorus lipids, but it is not known how rapidly this substitution occurs. Here, when cells of the model diatom Thalassiosira pseudonana were transferred from P-replete medium to P-free medium, the phospholipid content of the cells rapidly declined within 48 h from 45±0.9% to 21±4.5% of total membrane lipids; the difference was made up by non-phosphorus lipids. Conversely, when P-limited T. pseudonana were resupplied with P, cells reduced the percentage of their total membrane lipid contributed by a non-phosphorus lipid from 43±1.5% to 7.3±0.9% within 24 h, while the contribution by phospholipids rose from 2.2±0.1% to 44±3%. This dynamic phospholipid reservoir contained sufficient P to synthesize multiple haploid genomes, suggesting that phospholipid turnover could be an important P source for cells. Field observations of phytoplankton lipid content may thus reflect short-term changes in P supply and cellular physiology, rather than simply long-term adjustment to the environment.

Description: This research was funded by NSF OCE-0646944 and OCE- 1045670 (B.V.M.), OCE-0723677 and OCE-0549794 (S.T.D.), and by the Graduate School, National Oceanography Centre, Southampton (P.M).

Description: © The Author(s), 2014. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in PLoS One 9 (2014): e112134, doi:10.1371/journal.pone.0112134.

Description: Annual Emiliania huxleyi blooms (along with other coccolithophorid species) play important roles in the global carbon and sulfur cycles. E. huxleyi blooms are routinely terminated by large, host-specific dsDNA viruses, (Emiliania huxleyi Viruses; EhVs), making these host-virus interactions a driving force behind their potential impact on global biogeochemical cycles. Given projected increases in sea surface temperature due to climate change, it is imperative to understand the effects of temperature on E. huxleyi’s susceptibility to viral infection and its production of climatically active dimethylated sulfur species (DSS). Here we demonstrate that a 3°C increase in temperature induces EhV-resistant phenotypes in three E. huxleyi strains and that successful virus infection impacts DSS pool sizes. We also examined cellular polar lipids, given their documented roles in regulating host-virus interactions in this system, and propose that alterations to membrane-bound surface receptors are responsible for the observed temperature-induced resistance. Our findings have potential implications for global biogeochemical cycles in a warming climate and for deciphering the particular mechanism(s) by which some E. huxleyi strains exhibit viral resistance.

Description: This study was supported by funding from the National Science Foundation (OCE-1061883 to KDB, BVM, and OCE-1061876 to GRD) and in part by grants from The Gordon and Betty Moore Foundation (to BVM and KDB).

Description: Author Posting. © American Geophysical Union, 2015. 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 29 (2015): 1471–1494, doi:10.1002/2014GB005037.

Description: The direct respiration of sinking organic matter by attached bacteria is often invoked as the dominant sink for settling particles in the mesopelagic ocean. However, other processes, such as enzymatic solubilization and mechanical disaggregation, also contribute to particle flux attenuation by transferring organic matter to the water column. Here we use observations from the North Atlantic Ocean, coupled to sensitivity analyses of a simple model, to assess the relative importance of particle-attached microbial respiration compared to the other processes that can degrade sinking particles. The observed carbon fluxes, bacterial production rates, and respiration by water column and particle-attached microbial communities each spanned more than an order of magnitude. Rates of substrate-specific respiration on sinking particle material ranged from 0.007 ± 0.003 to 0.173 ± 0.105 day−1. A comparison of these substrate-specific respiration rates with model results suggested sinking particle material was transferred to the water column by various biological and mechanical processes nearly 3.5 times as fast as it was directly respired. This finding, coupled with strong metabolic demand imposed by measurements of water column respiration (729.3 ± 266.0 mg C m−2 d−1, on average, over the 50 to 150 m depth interval), suggested a large fraction of the organic matter evolved from sinking particles ultimately met its fate through subsequent remineralization in the water column. At three sites, we also measured very low bacterial growth efficiencies and large discrepancies between depth-integrated mesopelagic respiration and carbon inputs.

Description: U.S. Environmental Protection Agency (EPA) STAR Grant Number: FP-91744301-0; National Science Foundation Grant Numbers OCE-1061883, EF-0424599, OCE-1155438, OCE-1059884, OCE-1031143; Gordon and Betty Moore Foundation Grant Numbers: 3301, 3789; Gordon and Betty Moore Foundation; Woods Hole Oceanographic Institution

Description: 2016-03-25

Description: © The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Limnology and Oceanography 61 (2016): 1172–1187, doi:10.1002/lno.10253.

Description: The composition of sinking particles and the mechanisms leading to their transport ultimately control how much carbon is naturally sequestered in the deep ocean by the “biological pump.” While detrital particles often contain much of the sinking carbon, sinking of intact phytoplankton cells can also contribute to carbon export, which represents a direct flux of carbon from the atmosphere to the deep ocean by circumventing the surface ocean food web. Phytoplankton that contributed to carbon flux were identified in sinking material collected by short-term sediment trap deployments conducted along a transect off the eastern shore of South America. Particulate organic carbon flux at 125 m depth did not change significantly along the transect. Instead, changes occurred in the composition and association of phytoplankton with detrital particles. The fluxes of diatoms, coccolithophores, dinoflagellates, and nano-sized cells at 125 m were unrelated to the overlying surface population abundances, indicating that functional-group specific transport mechanisms were variable across locations. The dominant export mechanism of phytoplankton at each station was putatively identified by principal component analysis and fell into one of three categories; (1) transport and sinking of individual, viable diatom cells, (2) transport by aggregates and fecal pellets, or (3) enhanced export of coccolithophores through direct settling and/or aggregation

Description: Funding for the DeepDOM cruise was provided by the National Science Foundation (NSF) grant OCE-1154320 to E. B. Kujawinski and K. Longnecker, WHOI. Partial research support was provided by NSF through grants OCE-0925284, and OCE-1316036 to S.T. Dyhrman. C.A. Durkin was supported by a Woods Hole Oceanographic Institution Devonshire Postdoctoral Scholarship.

Description: Author Posting. © The Author(s), 2018. 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 Geochimica et Cosmochimica Acta 232 (2018): 244-264, doi:10.1016/j.gca.2018.04.030.

Description: The seasonal depletion of stratospheric ozone over the Southern Hemisphere allows abnormally high doses of ultraviolet radiation (UVR) to reach surface waters of the West Antarctic Peninsula (WAP) in the austral spring, creating a natural laboratory for the study of lipid photooxidation in the shallow mixed layer of the marginal ice zone. The photooxidation of lipids under such conditions has been identified as a significant source of stress to microorganisms, and short-chain fatty acids altered by photochemical processes have been found in both marine aerosols and sinking marine particle material. However, the biogeochemical impact of lipid photooxidation has not been quantitatively compared at ecosystem scale to the many other biological and abiotic processes that can transform particulate organic matter in the surface ocean. We combined results from field experiments with diverse environmental data, including high-resolution, accurate-mass HPLC-ESI-MS analysis of lipid extracts and in situ measurements of ultraviolet irradiance, to address several unresolved questions about lipid photooxidation in the marine environment. In our experiments, we used liposomes — nonliving, cell-like aggregations of lipids — to examine the photolability of various moieties of the intact polar diacylglycerol (IP-DAG) phosphatidylcholine (PC), a structural component of membranes in a broad range of microorganisms. We observed significant rates of photooxidation only when the molecule contained the polyunsaturated fatty acid (PUFA) docosahexaenoic acid (DHA). As the DHA-containing lipid was oxidized, we observed the steady ingrowth of a diversity of oxylipins and oxidized IP-DAG; our results suggest both the intact IPDAG the degradation products were amenable to heterotrophic assimilation. To complement our experiments, we used an enhanced version of a new lipidomics discovery software package to identify the lipids in water column samples and in several diatom isolates. The galactolipid digalactosyldiacylglycerol (DGDG), the sulfolipid sulfoquinovosyldiacylglycerol (SQDG) and the phospholipids PC and phosphatidylglycerol (PG) accounted for the majority of IP-DAG in the water column particulate (≥ 0.2 μm) size fraction; between 3.4 and 5.3 % of the IP-DAG contained fatty acids that were both highly polyunsaturated (i.e., each containing ≥ 5 double bonds). Using a broadband apparent quantum yield (AQY) that accounted for direct and Type I (i.e., radical-mediated) photooxidation of PUFA-containing IP-DAG, we estimated that 0.7 ± 0.2 μmol IP-DAG m-2 d-1 (0.5 ± 0.1 mg C m-2 d-1) were oxidized by photochemical processes in the mixed layer. This rate represented 4.4 % (range, 3-21 %) of the mean bacterial production rate measured in the same waters immediately following the retreat of the sea ice. Because our liposome experiments were not designed to account for oxidation by Type II photosensitized processes that often dominate in marine phytodetritus, our rate estimates may represent a sizeable underestimate of the true rate of lipid photooxidation in the water column. While production of such diverse oxidized lipids and oxylipins has been previously observed in terrestrial plants and mammals in response to biological stressors such as disease, we show here that a similar suite of molecules can be produced via an abiotic process in the environment and that the effect can be commensurate in magnitude with other ecosystem-scale biogeochemical processes.

Description: J.R.C. acknowledges support from a U.S. Environmental Protection Agency (EPA) STAR Graduate Fellowship (Fellowship Assistance agreement FP-91744301-0). This work was also supported by U.S. National Science Foundation awards OCE-1059884 and PLR-1543328 to B.A.S.V.M., NSF award PLR- 1341479 to A. M., the Gordon and Betty Moore Foundation through grant GBMF3301 to B.A.S.V.M., and a WHOI Ocean Ventures Fund award to J.R.C.