WHOAS at MBLWHOI Library

Influences on the oceanic biogeochemical cycling of the hybrid-type metals : cobalt, iron, and manganese

2012-02-09T21:53:21Z

Influences on the oceanic biogeochemical cycling of the hybrid-type metals : cobalt, iron, and manganese Noble, Abigail E. Trace metal cycling is one of many processes that influence ocean ecosystem dynamics. Cobalt, iron, and manganese are redox active trace metal micronutrients with oceanic distributions that are influenced by both biological and abiotic sources and sinks. Their open ocean concentrations range from picomolar to nanomolar, and their bioavailabilities can impact primary production. Understanding the biogeochemical cycling of these hybrid-type metals with an emphasis on cobalt was the focus of this thesis. This was accomplished by determining the dissolved distributions of these metals in oceanic regions that were characterized by different dominant biogeochemistries. A large subsurface plume of dissolved cobalt, iron, and manganese was found in the Eastern South Atlantic. The cause of this plume is a combination of reductive dissolution in coastal sediments, wind-driven upwelling, advection, biological uptake, and remineralization. Additional processes that are discussed as sources of metals to the regions studied during this thesis include isopycnal uplift within cold-core eddies (Hawaii), ice melt (McMurdo Sound, Antarctica), riverine input (Arctic Ocean), and winter mixing (McMurdo Sound). The biological influence on surface ocean distributions of cobalt was apparent by the observation of linear relationships between cobalt and phosphate in mid to low latitudes. The cobalt:phosphate ratios derived from these correlations changed over orders of magnitude, revealing dynamic variability in the utilization, demand, and sources of this micronutrient. Speciation studies suggest that there may be two classes of cobalt binding ligands, and that organic complexation plays an important role in preventing scavenging of cobalt in the ocean. These datasets provided a basis for comparing the biogeochemical cycles of cobalt, iron, and manganese in three oceanic regimes (Hawaii, South Atlantic, McMurdo Sound). The relative rates of scavenging for these metals show environmental variability: in the South Atlantic, cobalt, iron, and manganese were scavenged at very different rates, but in the Ross Sea, mixing and circulation over the shallow sea was fast, scavenging played a minor role, and the cycles of all three metals were coupled. Studying the distributions of these metals in biogeochemically distinct regions is a step toward a better understanding of their oceanic cycles. Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, February 2012

Evolutionary origins of the estrogen signaling system : insights from amphioxus

2012-02-09T09:30:46Z

Evolutionary origins of the estrogen signaling system : insights from amphioxus Callard, Gloria V.; Tarrant, Ann M.; Novillo, A.; Yacci, P.; Ciaccia, L.; Vajda, S.; Chuang, G.-Y.; Kozakov, D.; Greytak, S. R.; Sawyer, S.; Hoover, Cindi A.; Cotter, K. A. Classically, the estrogen signaling system has two core components: cytochrome P450 aromatase (CYP19), the enzyme complex that catalyzes the rate limiting step in estrogen biosynthesis; and estrogen receptors (ERs), ligand activated transcription factors that interact with the regulatory region of target genes to mediate the biological effects of estrogen. While the importance of estrogens for regulation of reproduction, development and physiology has been well-documented in gnathostome vertebrates, the evolutionary origins of estrogen as a hormone are still unclear. As invertebrates within the phylum Chordata, cephalochordates (e.g. the amphioxus of the genus Branchiostoma) are among the closest invertebrate relatives of the vertebrates and can provide critical insight into the evolution of vertebrate-specific molecules and pathways. To address this question, this paper briefly reviews relevant earlier studies that help to illuminate the history of the aromatase and ER genes, with a particular emphasis on insights from amphioxus and other invertebrates. We then present new analyses of amphioxus aromatase and ER sequence and function, including an in silico model of the amphioxus aromatase protein, and CYP19 gene analysis. CYP19 shares a conserved gene structure with vertebrates (9 coding exons) and moderate sequence conservation (40% amino acid identity with human CYP19). Modeling of the amphioxus aromatase substrate binding site and simulated docking of androstenedione in comparison to the human aromatase shows that the substrate binding site is conserved and predicts that androstenedione could be a substrate for amphioxus CYP19. The amphioxus ER is structurally similar to vertebrate ERs, but differs in sequence and key residues of the ligand binding domain. Consistent with results from other laboratories, amphioxus ER did not bind radiolabeled estradiol, nor did it modulate gene expression on an estrogen-responsive element (ERE) in the presence 59 of estradiol, 4-hydroxytamoxifen, diethylstilbestrol, bisphenol A or genistein. Interestingly, it has been shown that a related gene, the amphioxus “steroid receptor” (SR), can be activated by estrogens and that amphioxus ER can repress this activation. CYP19, ER and SR are all primarily expressed in gonadal tissue, suggesting an ancient paracrine/autocrinesignaling role, but it is not yet known how their expression is regulated and, if estrogen is actually synthesized in amphioxus, whether it has a role in mediating any biological effects . Functional studies are clearly needed to link emerging bioinformatics and in vitro molecular biology results with organismal physiology to develop an understanding of the evolution of estrogen signaling. Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Journal of Steroid Biochemistry and Molecular Biology 127 (2011): 176–188, doi:10.1016/j.jsbmb.2011.03.022.

Source components of the Gran Canaria (Canary Islands) shield stage magmas : evidence from olivine composition and Sr–Nd–Pb isotopes

2012-02-09T09:30:44Z

Source components of the Gran Canaria (Canary Islands) shield stage magmas : evidence from olivine composition and Sr–Nd–Pb isotopes Gurenko, Andrey A.; Hoernle, Kaj A.; Sobolev, Alexander V.; Hauff, Folkmar; Schmincke, Hans-Ulrich The Canary Island primitive basaltic magmas 31 are thought to be derived from a HIMU-type upwelling mantle containing isotopically depleted (NMORB) component and having interacted with an enriched (EM)-type component whose origin is still a subject of debate. We have studied the relationships between Ni, Mn and Ca concentrations in olivine phenocrysts (85.6-90.0 mol.% Fo, 1722-3915 ppm Ni, 1085-1552 ppm Mn, 1222-3002 ppm Ca) from the most primitive subaerial and ODP Leg 157 high-silica (picritic to olivine basaltic) lavas with their bulk rock Sr-Nd-Pb isotope compositions (87Sr/86Sr = 0.70315- 0.70331, 143Nd/144Nd = 0.51288-0.51292, 206Pb/204Pb = 19.55-19.93, 207Pb/204Pb = 15.60- 15.63, 208Pb/204Pb = 39.31-39.69). Our data point toward the presence of both a peridotitic and a pyroxenitic component in the magma source. Using the model [Sobolev et al. (2007) The amount of recycled crust in sources of mantle-derived melts. Science 316: 412-417] in which the reaction of Si-rich melts originated during partial melting of eclogite (a high pressure product of subducted oceanic crust) with ambient peridotitic mantle forms olivine-free reaction pyroxenite, we obtain an endmember composition for peridotite with 87Sr/86Sr = 0.70337, 143Nd/144Nd = 0.51291, 206Pb/204Pb = 19.36, 207Pb/204Pb = 15.61, 208Pb/204Pb = 39.07 (EM-type endmember) and pyroxenite with 87Sr/86Sr = 0.70309, 143Nd/144Nd = 0.51289, 206Pb/204Pb = 20.03, 207Pb/204Pb = 15.62, 208Pb/204Pb = 39.84 (HIMU-type endmember). Mixing of melts from these endmembers in proportions ranging from 70% peridotite and 30% pyroxenite to 28% peridotite and 72% pyroxenite can generate the compositions of the most primitive Gran Canaria shield stage lavas. Combining our results with those from the low silica rocks from the western Canary Islands [Gurenko et al. (2009) Enriched, HIMU-type peridotite and depleted recycled pyroxenite in the Canary plume: a mixed-up mantle. EPSL 277: 514-524], at least four distinct components are required. We propose that they are (1) HIMU-type pyroxenitic component (representing recycled ocean crust of intermediate age) from the plume center, (2) HIMU-type peridotitic component (ancient recycled ocean crust stirred into the ambient mantle) from the plume margin, (3) depleted, MORB-type pyroxenitic component (young recycled oceanic crust) in the upper mantle entrained by the plume, and (4) EM-type peridotitic component from the asthenosphere or lithosphere above the plume center. Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Contributions to Mineralogy and Petrology 159 (2010): 689-702, doi:10.1007/s00410-009-0448-8.

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: insights from olivine phenocrysts

2012-02-09T09:30:40Z

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: insights from olivine phenocrysts Gurenko, Andrey A.; Bindeman, Ilya N.; Chaussidon, Marc A relatively narrow range of oxygen isotopic ratios (δ18O = 5.05.4‰) is preserved in olivine of mantle xenoliths, mid-ocean ridge (MORB) and most ocean island basalts (OIB). The values in excess of this range are generally attributed either to the presence of a recycled component in the Earth’s mantle or to shallow level contamination processes. A viable way forward to trace source heterogeneity is to find a link between chemical (elemental and isotopic) composition of the earlier crystallized mineral phases (olivine) and the composition of their parental magmas, then using them to reconstruct the composition of source region. The Canary hotspot is one of a few that contains ~1-2 Ga old recycled ocean crust that can be traced to the core-mantle boundary using seismic tomography and whose origin is attributed to the mixing of at least three main isotopically distinct mantle components i.e., HIMU, DMM and EM. This work reports ion microprobe and single crystal laser fluorination oxygen isotope data of 148 olivine grains also analyzed for major and minor elements in the same spot. The olivines are from 20 samples resembling the most primitive shield stage picrite through alkali basalt to basanite series erupted on Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro, Canary Islands, for which shallow level contamination processes were not recognized. A broad range of δ18Oolivine values from 4.6 to 6.1‰ was obtained and explained by stable, long-term oxygen isotope heterogeneity of crystal cumulates present under different volcanoes. These cumulates are thought to have crystallized from mantle derived magmas uncontaminated at crustal depth, representing oxygen isotope heterogeneity of source region. A relationship between Ni×FeO/MgO and δ18Oolivine values found in one basanitic lava erupted on El Hierro, the westernmost island of the Canary Archipelago, was used to estimate oxygen isotope compositions of partial melts presumably originated from peridotite (HIMU-type component inherited its radiogenic isotope composition from ancient, ~12 Ga, recycled ocean crust) and pyroxenite (young, <1 Ga, recycled oceanic crust preserved as eclogite with depleted MORB-type isotopic signature) components of the Canary plume. The model calculations yield 5.2 and 5.9±0.3‰ for peridotite and pyroxenite derived melts, respectively, which appeared to correspond closely to the worldwide HIMU-type OIB and upper limit N-MORB δ18O values. This difference together with the broad range of δ18O variations found in the Canarian olivines cannot be explained by thermodynamic effects of oxygen isotopic fractionation and are believed to represent true variations in the mantle, due to oceanic crust and continental lithosphere recycling. Author Posting. © The Author(s), 2010. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Contributions to Mineralogy and Petrology 162 (2011): 349-363, doi:10.1007/s00410-010-0600-5.