648 research outputs found

    The molecular products and biogeochemical significance of lipid photooxidation in West Antarctic surface waters

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    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.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.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

    Pacific climate reflected in Waipuna Cave drip water hydrochemistry

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    Cave microclimate and geochemical monitoring is vitally important for correct interpretations of proxy time series from speleothems with regard to past climatic and environmental dynamics. We present results of a comprehensive cave-monitoring programme in Waipuna Cave in the North Island of New Zealand, a region that is strongly influenced by the Southern Westerlies and the El Niño–Southern Oscillation (ENSO). This study aims to characterise the response of the Waipuna Cave hydrological system to atmospheric circulation dynamics in the southwestern Pacific region in order to assure the quality of ongoing palaeo-environmental reconstructions from this cave. Drip water from 10 drip sites was collected at roughly monthly intervals for a period of ca. 3 years for isotopic (δ18O, δD, d-excess parameter, δ17O, and 17Oexcess) and elemental (Mg∕Ca and Sr∕Ca) analysis. The monitoring included spot measurements of drip rates and cave air CO2 concentration. Cave air temperature and drip rates were also continuously recorded by automatic loggers. These datasets were compared to surface air temperature, rainfall, and potential evaporation from nearby meteorological stations to test the degree of signal transfer and expression of surface environmental conditions in Waipuna Cave hydrochemistry. Based on the drip response dynamics to rainfall and other characteristics, we identified three types of discharge associated with hydrological routing in Waipuna Cave: (i) type 1 – diffuse flow, (ii) type 2 – fracture flow, and (iii) type 3 – combined flow. Drip water isotopes do not reflect seasonal variability but show higher values during severe drought. Drip water δ18O values are characterised by small variability and reflect the mean isotopic signature of precipitation, testifying to rapid and thorough homogenisation in the epikarst. Mg∕Ca and Sr∕Ca ratios in drip waters are predominantly controlled by prior calcite precipitation (PCP). Prior calcite precipitation is strongest during austral summer (December–February), reflecting drier conditions and a lack of effective infiltration, and is weakest during the wet austral winter (July–September). The Sr∕Ca ratio is particularly sensitive to ENSO conditions due to the interplay of congruent or incongruent host rock dissolution, which manifests itself in lower Sr∕Ca in above-average warmer and wetter (La Niña-like) conditions. Our microclimatic observations at Waipuna Cave provide a valuable baseline for the rigorous interpretation of speleothem proxy records aiming at reconstructing the past expression of Pacific climate modes

    Effect of crystalline disorder on quantum tunneling in the single-molecule magnet Mn12 benzoate

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    10 páginas, 9 figuras, 1 tabla.-- PACS number(s): 75.45.+j, 75.50.Xx, 75.60.Jk, 75.50.Kj.-- et al.We report a detailed study of the effects that crystalline disorder has on the magnetic relaxation and quantum tunneling of Mn12 benzoate clusters. Thanks to the absence of interstitial molecules in the crystal structure of this molecular compound, we have been able to isolate the influence of long-range crystalline disorder. For this, we compare results obtained under two extreme situations: a crystalline sample and a nearly amorphous material. The results show that crystalline disorder affects little the anisotropy, magnetic relaxation, and quantum tunneling of these materials. It follows that disorder is not a necessary ingredient for the existence of magnetic quantum tunneling. The results unveil, however, a subtle influence of crystallinity via the modification of the symmetry of dipole-dipole interactions. The faster tunneling rates measured for the amorphous material are accounted for by a narrower distribution of dipolar bias in this material, as compared with the crystalline sample.This work has been partly funded by Grants No. MAT2009-13977-C03, No. MAT2008-06542- C04, and No. CSD2007-00010 from the Spanish Ministerio de Ciencia e Innovación, and NABISUP from DGA. We acknowledge funding from Acción Integrada under Grant No. HA2006-0051 and the Network of Excellence MAGMANet. J.v.S and S.D. acknowledge the financial support of the Deutsche Forschungsgemeinschaft (DFG) and the DAAD. Ch.C. and I.I. acknowledge the Spanish Ministerio de Ciencia e Innovación.Peer reviewe

    Gene duplications are extensive and contribute significantly to the toxic proteome of nematocysts isolated from Acropora digitifera (Cnidaria: Anthozoa: Scleractinia)

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    Background: Gene duplication followed by adaptive selection is a well-accepted process leading to toxin diversification in venoms. However, emergent genomic, transcriptomic and proteomic evidence now challenges this role to be at best equivocal to other processess . Cnidaria are arguably the most ancient phylum of the extant metazoa that are venomous and such provide a definitive ancestral anchor to examine the evolution of this trait.\ud Methods: Here we compare predicted toxins from the translated genome of the coral Acropora digitifera to putative toxins revealed by proteomic analysis of soluble proteins discharged from nematocysts, to determine the extent to which gene duplications contribute to venom innovation in this reef-building coral species. A new bioinformatics tool called HHCompare was developed to detect potential gene duplications in the genomic data, which is made freely available (https://github.com/rgacesa/HHCompare).\ud Results: A total of 55 potential toxin encoding genes could be predicted from the A. digitifera genome, of which 36 (65 %) had likely arisen by gene duplication as evinced using the HHCompare tool and verified using two standard phylogeny methods. Surprisingly, only 22 % (12/55) of the potential toxin repertoire could be detected\ud following rigorous proteomic analysis, for which only half (6/12) of the toxin proteome could be accounted for as peptides encoded by the gene duplicates. Biological activities of these toxins are dominatedby putative phospholipases and toxic peptidases.\ud Conclusions: Gene expansions in A. digitifera venom are the most extensive yet described in any venomous animal, and gene duplication plays a significant role leading to toxin diversification in this coral species. Since such low numbers of toxins were detected in the proteome, it is unlikely that the venom is evolving rapidly by preydriven positive natural selection. Rather we contend that the venom has a defensive role deterring predation or\ud harm from interspecific competition and overgrowth by fouling organisms. Factors influencing translation of toxin encoding genes perhaps warrants more profound experimental consideration.United Kingdom Medical Research Council (MRC grant G82144A to R. Gacesa, D. Hranueli and P. F. Long)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP grants 2010/50174-7 to A. C. Morandini and 2011/50242-5 to A. C. Marques)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq grant 301039/2013-5 to A. C. Morandini)Universidade de São Paulo (USP grant 13.1.1502.9.8)NP-BioMar program at the Universidade de São Paul

    The solid-state photo-CIDNP effect

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    The solid-state photo-CIDNP effect is the occurrence of a non-Boltzmann nuclear spin polarization in rigid samples upon illumination. For solid-state NMR, which can detect this enhanced nuclear polarization as a strong modification of signal intensity, the effect allows for new classes of experiments. Currently, the photo- and spin-chemical machinery of various RCs is studied by photo-CIDNP MAS NMR in detail. Until now, the effect has only been observed at high magnetic fields with 13C and 15N MAS NMR and in natural photosynthetic RC preparations in which blocking of the acceptor leads to cyclic electron transfer. In terms of irreversible thermodynamics, the high-order spin structure of the initial radical pair can be considered as a transient order phenomenon emerging under non-equilibrium conditions and as a first manifestation of order in the photosynthetic process. The solid-state photo-CIDNP effect appears to be an intrinsic property of natural RCs. The conditions of its occurrence seem to be conserved in evolution. The effect may be based on the same fundamental principles as the highly optimized electron transfer. Hence, the effect may allow for guiding artificial photosynthesis
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