Glacial-interglacial changes in bottom-water oxygen content on the Portuguese margin

During the last and penultimate glacial maxima, atmospheric CO2 concentrations were lower than present, possibly in part because of increased storage of respired carbon in the deep oceans. The amount of respired carbon present in a water mass can be calculated from its oxygen content through apparent oxygen utilization; the oxygen content can in turn be calculated from the carbon isotope gradient within the sediment column. Here we analyse the shells of benthic foraminifera occurring at the sediment surface and the oxic/anoxic interface on the Portuguese Margin to reconstruct the carbon isotope gradient and hence bottom-water oxygenation over the past 150,000 years. We find that bottom-water oxygen concentrations were 45 and 65 μmol kg−1 lower than present during the last and penultimate glacial maxima, respectively. We calculate that concentrations of remineralized organic carbon were at least twice as high as today during the glacial maxima. We attribute these changes to decreased ventilation linked to a reorganization of ocean circulation and a strengthened global biological pump. If the respired carbon pool was of a similar size throughout the entire glacial deep Atlantic basin, then this sink could account for 15 and 20 per cent of the glacial PCO2 drawdown during the last and penultimate glacial maxima

Iron(III)-catalyzed chlorination of activated arenes

A general and regioselective method for the chlorination of activated arenes has been developed. The transformation uses iron(III) triflimide as a powerful Lewis acid for the activation of N-chlorosuccinimide and the subsequent chlorination of a wide range of anisole, aniline, acetanilide and phenol derivatives. The reaction was utilized for the late-stage mono- and di-chlorination of a range of target compounds such as the natural product nitrofungin, the antibacterial agent chloroxylenol and the herbicide chloroxynil. The facile nature of this transformation was demonstrated with the development of one-pot tandem iron-catalyzed dihalogenation processes allowing highly regioselective formation of different carbon-halogen bonds. The synthetic utility of the resulting dihalogenated aryl compounds as building blocks was established with the synthesis of natural products and pharmaceutically relevant targets

CLEAR I: Ages and Metallicities of Quiescent Galaxies at 1.0<z<1.8\mathbf{1.0 < z < 1.8} Derived from Deep Hubble Space Telescope Grism Data

We use deep \textit{Hubble Space Telescope} spectroscopy to constrain the metallicities and (\editone{light-weighted}) ages of massive ($\log M_\ast/M_\odot\gtrsim10$) galaxies selected to have quiescent stellar populations at $1.0<z<1.8$. The data include 12--orbit depth coverage with the WFC3/G102 grism covering $\sim$ $8,000<\lambda<11,500$~\AA\, at a spectral resolution of $R\sim 210$ taken as part of the CANDELS Lyman-$\alpha$ Emission at Reionization (CLEAR) survey. At $1.0<z<1.8$, the spectra cover important stellar population features in the rest-frame optical. We simulate a suite of stellar population models at the grism resolution, fit these to the data for each galaxy, and derive posterior likelihood distributions for metallicity and age. We stack the posteriors for subgroups of galaxies in different redshift ranges that include different combinations of stellar absorption features. Our results give \editone{light-weighted ages of $t_{z \sim 1.1}= 3.2\pm 0.7$~Gyr, $t_{z \sim 1.2}= 2.2\pm 0.6$~Gyr, $t_{z\sim1.3}= 3.1\pm 0.6$~Gyr, and $t_{z\sim1.6}= 2.0 \pm 0.6$~Gyr, \editone{for galaxies at $z\sim 1.1$, 1.2, 1.3, and 1.6. This} implies that most of the massive quiescent galaxies at $168$\% of their stellar mass by a redshift of $z>2$}. The posteriors give metallicities of \editone{$Z_{z\sim1.1}=1.16 \pm 0.29$~$Z_\odot$, $Z_{z\sim1.2}=1.05 \pm 0.34$~$Z_\odot$, $Z_{z\sim1.3}=1.00 \pm 0.31$~$Z_\odot$, and $Z_{z\sim1.6}=0.95 \pm 0.39$~$Z_\odot$}. This is evidence that massive galaxies had enriched rapidly to approximately Solar metallicities as early as $z\sim3$.Comment: 32 pages, 23 figures, Resubmited to ApJ after revisions in response to referee repor

A CANDELS - 3D-HST Synergy: Resolved Star Formation Patterns at 0.7 < z < 1.5

We analyze the resolved stellar populations of 473 massive star-forming galaxies at 0.7 < z < 1.5, with multi-wavelength broad-band imaging from CANDELS and Halpha surface brightness profiles at the same kiloparsec resolution from 3D-HST. Together, this unique data set sheds light on how the assembled stellar mass is distributed within galaxies, and where new stars are being formed. We find the Halpha morphologies to resemble more closely those observed in the ACS I band than in the WFC3 H band, especially for the larger systems. We next derive a novel prescription for Halpha dust corrections, which accounts for extra extinction towards HII regions. The prescription leads to consistent SFR estimates and reproduces the observed relation between the Halpha/UV luminosity ratio and visual extinction, both on a pixel-by-pixel and on a galaxy-integrated level. We find the surface density of star formation to correlate with the surface density of assembled stellar mass for spatially resolved regions within galaxies, akin to the so-called 'main sequence of star formation' established on a galaxy-integrated level. Deviations from this relation towards lower equivalent widths are found in the inner regions of galaxies. Clumps and spiral features, on the other hand, are associated with enhanced Halpha equivalent widths, bluer colors, and higher specific star formation rates compared to the underlying disk. Their Halpha/UV luminosity ratio is lower than that of the underlying disk, suggesting the ACS clump selection preferentially picks up those regions of elevated star formation activity that are the least obscured by dust. Our analysis emphasizes that monochromatic studies of galaxy structure can be severely limited by mass-to-light ratio variations due to dust and spatially inhomogeneous star formation histories.Comment: Accepted by The Astrophysical Journal, 18 pages, 1 table, 10 figure

Online dietary intake estimation : Reproducibility and validity of the Food4Me food frequency questionnaire against a 4-day weighed food record

©Rosalind Fallaize, Hannah Forster, Anna L Macready, Marianne C Walsh, John C Mathers, Lorraine Brennan, Eileen R Gibney, Michael J Gibney, Julie A Lovegrove. Originally published in the Journal of Medical Internet Research (http://www.jmir.org), 11.08.2014. This is an open-access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work, first published in the Journal of Medical Internet Research, is properly cited. The complete bibliographic information, a link to the original publication on http://www.jmir.org/, as well as this copyright and license information must be included.Background: Advances in nutritional assessment are continuing to embrace developments in computer technology. The online Food4Me food frequency questionnaire (FFQ) was created as an electronic system for the collection of nutrient intake data. To ensure its accuracy in assessing both nutrient and food group intake, further validation against data obtained using a reliable, but independent, instrument and assessment of its reproducibility are required. Objective: The aim was to assess the reproducibility and validity of the Food4Me FFQ against a 4-day weighed food record (WFR). Methods: Reproducibility of the Food4Me FFQ was assessed using test-retest methodology by asking participants to complete the FFQ on 2 occasions 4 weeks apart. To assess the validity of the Food4Me FFQ against the 4-day WFR, half the participants were also asked to complete a 4-day WFR 1 week after the first administration of the Food4Me FFQ. Level of agreement between nutrient and food group intakes estimated by the repeated Food4Me FFQ and the Food4Me FFQ and 4-day WFR were evaluated using Bland-Altman methodology and classification into quartiles of daily intake. Crude unadjusted correlation coefficients were also calculated for nutrient and food group intakes. Results: In total, 100 people participated in the assessment of reproducibility (mean age 32, SD 12 years), and 49 of these (mean age 27, SD 8 years) also took part in the assessment of validity. Crude unadjusted correlations for repeated Food4Me FFQ ranged from .65 (vitamin D) to .90 (alcohol). The mean cross-classification into "exact agreement plus adjacent" was 92% for both nutrient and food group intakes, and Bland-Altman plots showed good agreement for energy-adjusted macronutrient intakes. Agreement between the Food4Me FFQ and 4-day WFR varied, with crude unadjusted correlations ranging from .23 (vitamin D) to .65 (protein, % total energy) for nutrient intakes and .11 (soups, sauces and miscellaneous foods) to .73 (yogurts) for food group intake. The mean cross-classification into "exact agreement plus adjacent" was 80% and 78% for nutrient and food group intake, respectively. There were no significant differences between energy intakes estimated using the Food4Me FFQ and 4-day WFR, and Bland-Altman plots showed good agreement for both energy and energy-controlled nutrient intakes. Conclusions: The results demonstrate that the online Food4Me FFQ is reproducible for assessing nutrient and food group intake and has moderate agreement with the 4-day WFR for assessing energy and energy-adjusted nutrient intakes. The Food4Me FFQ is a suitable online tool for assessing dietary intake in healthy adults.Peer reviewedFinal Published versio

A CANDELS-3d-HST Synergy: Resolved Star Formation Patterns at 0.7 less than z less than 1.5

We analyze the resolved stellar populations of 473 massive star-forming galaxies at 0.7 < z < 1.5, with multiwavelength broadband imaging from CANDELS andHalpha surface brightness profiles at the same kiloparsec resolution from 3D-HST. Together, this unique data set sheds light on how the assembled stellar mass is distributed within galaxies, and where new stars are being formed. We find the Halpha morphologies to resemble more closely those observed in the ACS I band than in the WFC3 H band, especially for the larger systems. We next derive a novel prescription for Halpha dust corrections, which accounts for extra extinction toward H II regions. The prescription leads to consistent star formation rate (SFR) estimates and reproduces the observed relation between the Halpha/UV luminosity ratio and visual extinction, on both a pixel-by-pixel and a galaxy-integrated level. We find the surface density of star formation to correlate with the surface density of assembled stellar mass for spatially resolved regions within galaxies, akin to the so-called "main sequence of star formation" established on a galaxy-integrated level. Deviations from this relation toward lower equivalent widths are found in the inner regions of galaxies. Clumps and spiral features, on the other hand, are associated with enhanced H alpha equivalent widths, bluer colors, and higher specific SFRs compared to the underlying disk. Their Halpha/UV luminosity ratio is lower than that of the underlying disk, suggesting that the ACS clump selection preferentially picks up those regions of elevated star formation activity that are the least obscured by dust. Our analysis emphasizes that monochromatic studies of galaxy structure can be severely limited by mass-to-light ratio variations due to dust and spatially inhomogeneous star formation histories