2-{(E)-[1-(2-Hydroxy­ethyl)-3,3-dimethyl-3H-indol-1-ium-2-yl]vin­yl}-6-hydroxy­meth­yl-4-nitro­phenolate dihydrate

The title merocyanine-type mol­ecule, C21H22N2O5·2H2O, crystallizes in a zwitterionic form and has an E configuration at the styryl C=C bond. The styryl part of the mol­ecule and the indolium ring are slightly twisted and form a dihedral angle of 13.4 (1)°. The 1.274 (3) Å C—O bond length in the phenolate fragment is the longest among similar mol­ecules. Hydrogen bonds between solvent water mol­ecules, two hydroxyl groups and the phenolate O atom dictate the packing arrangement of mol­ecules in the crystal and join the mol­ecules into a two-dimensional polymeric network which propagates parallel to (001). Four water mol­ecules and four hydr­oxy groups form a centrosymmetric homodromic cyclic motif of O—H⋯O hydrogen bonds. Another cyclic centrosymmetric motif is generated by four water mol­ecules and two phenolate O atoms

Crowdsourcing in the Quaternary sea level community: insights from the Pliocene

In order to establish the ‘fingerprint’ of past sea level changes, many field measurements of paleo sea level from globally distributed locations are needed. It is because this problem requires a geographically expansive database that it becomes an ideal candidate for crowdsourcing techniques. In order to crowdsource sea level data from the Mid-Pliocene Warm Period, we developed three tools: PlioWiki, RSLcalc and RSLmap. PlioWiki is a web portal, open to contributions, where investigators can share knowledge on Pliocene to Quaternary relative sea levels. RSLcalc is a standardized, ready-to-use tool for field geologists to log their own sea level field observations and, if they desire, submit new data to an open access database of relative sea level markers. RSLmap allows one to visualize and query the database built with RSLcalc on a Google Map interface. Here we describe these tools and discuss the advantages of crowdsourcing, relative to traditional approaches, for the creation of sea level databases for any time period

Planktic foraminifera shell chemistry response to seawater chemistry: Pliocene-Pleistocene seawater Mg/Ca, temperature and sea level change

Foraminifera Mg/Ca paleothermometry forms the basis of a substantial portion of ocean temperature reconstruction over the last 5 Ma. Furthermore, coupled Mg/Ca–oxygen isotope (δ18O) measurements of benthic foraminifera can constrain eustatic sea level (ESL) independent of paleo-shoreline derived approaches. However, this technique suffers from uncertainty regarding the secular variation of the Mg/Ca seawater ratio (Mg/Casw) on timescales of millions of years. Here we present coupled seawater–test Mg/Ca–temperature laboratory calibrations of Globigerinoides ruber in order to test the widely held assumptions that (1) seawater–test Mg/Ca co-vary linearly, and (2) the Mg/Ca–temperature sensitivity remains constant with changing Mg/Casw. We find a nonlinear Mg/Catest–Mg/Casw relationship and a lowering of the Mg/Ca–temperature sensitivity at lower than modern Mg/Casw from 9.0% ◦C−1 at Mg/Casw = 5.2 mol mol−1 to 7.5 ± 0.9%◦C−1 at 3.4 mol mol−1. Using our calibrations to more accurately calculate the offset between Mg/Ca and biomarker-derived paleotemperatures for four sites, we derive a Pliocene Mg/Casw ratio of ∼4.3 mol mol−1. This Mg/Casw implies Pliocene ocean temperature 0.9–1.9 ◦C higher than previously reported and, by extension, ESL ∼30 m lower compared to when one assumes that Pliocene Mg/Casw is the same as at present. Correcting existing benthic foraminifera datasets for Mg/Casw indicates that deep water source composition must have changed through time, therefore seawater oxygen isotope reconstructions relative to present day cannot be used to directly reconstruct Pliocene ESL

Reply to: Terry, J. and Goff, J. comment on “Late Cenozoic sea level and the rise of modern rimmed atolls” by Toomey et al. (2016), Palaeogeography, Palaeoclimatology, Palaeoecology 451: 73–83

This paper is not subject to U.S. copyright. The definitive version was published in Palaeogeography, Palaeoclimatology, Palaeoecology 469 (2017): 159-160, doi:10.1016/j.palaeo.2016.11.028

Late Cenozoic sea level and the rise of modern rimmed atolls

This paper is not subject to U.S. copyright. The definitive version was published in Palaeogeography, Palaeoclimatology, Palaeoecology 451 (2016): 73-83, doi:10.1016/j.palaeo.2016.03.018.Sea-level records from atolls, potentially spanning the Cenozoic, have been largely overlooked, in part because the processes that control atoll form (reef accretion, carbonate dissolution, sediment transport, vertical motion) are complex and, for many islands, unconstrained on million-year timescales. Here we combine existing observations of atoll morphology and corelog stratigraphy from Enewetak Atoll with a numerical model to (1) constrain the relative rates of subsidence, dissolution and sedimentation that have shaped modern Pacific atolls and (2) construct a record of sea level over the past 8.5 million years. Both the stratigraphy from Enewetak Atoll (constrained by a subsidence rate of ~ 20 m/Myr) and our numerical modeling results suggest that low sea levels (50–125 m below present), and presumably bi-polar glaciations, occurred throughout much of the late Miocene, preceding the warmer climate of the Pliocene, when sea level was higher than present. Carbonate dissolution through the subsequent sea-level fall that accompanied the onset of large glacial cycles in the late Pliocene, along with rapid highstand constructional reef growth, likely drove development of the rimmed atoll morphology we see today.Support for this work was provided through a Jackson School Distinguished Postdoctoral Fellowship to Michael Toomey

The Mid-Pliocene sea-level conundrum: Glacial isostasy, eustasy and dynamic topography

Determining eustatic sea level during the Mid-Pliocene warm period (~ 3.3 to 2.9 Ma) has been a central but elusive goal in the study of past warm climates. Estimates of eustatic sea level based on geologic data span a broad range; variation that we now recognize is due in part to geographically varying post-depositional displacement caused by glacial isostatic adjustment and dynamic topography. In this study, we combine field observations and glacial isostatic adjustment modeling to estimate the dynamic topography signal in three areas that are important to paleo-sea level studies of the Mid-Pliocene warm period (South Africa, West Australia and southeastern United States). We show that dynamic topography played a significant role in the post-depositional displacement of Pliocene, and even younger Pleistocene, shorelines. In this regard, we provide a robust paleo-sea level elevation data set, corrected for glacial isostatic adjustment, that can be used to evaluate predictions from mantle flow models of dynamic topography

Stability of North Atlantic water masses in face of pronounced climate variability during the Pleistocene

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 19 (2004): PA2008, doi:10.1029/2003PA000921.Geochemical profiles from the North Atlantic Ocean suggest that the vertical δ13C structure of the water column at intermediate depths did not change significantly between glacial and interglacial time over much of the Pleistocene, despite large changes in ice volume and iceberg delivery from nearby landmasses. The most anomalous δ13C profiles are from the extreme interglaciations of the late Pleistocene. This compilation of data suggests that, unlike today (an extreme interglaciation), the two primary sources of northern deep water, Norwegian-Greenland Sea and Labrador Sea/subpolar North Atlantic, had different characteristic δ13C values over most of the Pleistocene. We speculate that the current open sea ice conditions in the Norwegian-Greenland Sea are a relatively rare occurrence and that the high-δ13C deep water that forms in this region today is geologically unusual. If northern source deep waters can have highly variable δ13C, then this likelihood must be considered when inferring past circulation changes from benthic δ13C records.National Science Foundation grants OCE-0118005 and OCE-0118001, which supported MER and DWO

Late Neogene chronology: New perspectives in high-resolution stratigraphy

We present an integrated geochronology for late Neogene time (Pliocene, Pleistocene, and Holocene Epochs) based on an analysis of data from stable isotopes, magnetostratigraphy, radiochronology, and calcareous plankton biostratigraphy. Discrepancies between recently formulated astronomical chronologies and magnetochronologies for the past 6 m.y. have been resolved on the basis of new, high-precision Ar/Ar ages in the younger part of this interval, the so-called Brunhes, Matuyama, and Gauss Epochs (= Chrons C1n-C2An; 0-3.58 Ma), and revised analysis of sea floor anomalies in the Pacific Ocean in the older part, the so-called Gilbert Epoch (= Chron C2Ar-C3r; 3.58-5.89 Ma). The magneto- and astrochronologies are now concordant back to the Chron C3r/C3An boundary at 5.89 Ma. The Neogene (Miocene, Pliocene, Pleistocene, and Holocene) and Paleogene are treated here as period/system subdivisions of the Cenozoic Era/Erathem, replacements for the antiquated terms Tertiary and Quaternary. The boundary between the Miocene and Pliocene Series (Messinian/Zanclean Stages), whose global stratotype section and point (GSSP) is currently proposed to be in Sicily, is located within the reversed interval just below the Thvera (C3n.4n) Magnetic Polarity Subchronozone with an estimated age of 5.32 Ma. The Pliocene/Pleistocene boundary, whose GSSP is located at Vrica (Calabria, Italy), is located near the top of the Olduvai (C2n) Magnetic Polarity Subchronozone with an estimated age of 1.81 Ma. The 13 calcareous nannoplankton and 48 planktonic foraminiferal datum events for the Pliocene, and 12 calcareous nannoplankton and 10 planktonic foraminiferal datum events for the Pleistocene, are calibrated to the newly revised late Neogene astronomical/geomagnetic polarity time scale

On-the-fly decoding luminescence lifetimes in the microsecond region for lanthanide-encoded suspension arrays

Significant multiplexing capacity of optical time-domain coding has been recently demonstrated by tuning luminescence lifetimes of the upconversion nanoparticles called 'τ-Dots'. It provides a large dynamic range of lifetimes from microseconds to milliseconds, which allows creating large libraries of nanotags/microcarriers. However, a robust approach is required to rapidly and accurately measure the luminescence lifetimes from the relatively slow-decaying signals. Here we show a fast algorithm suitable for the microsecond region with precision closely approaching the theoretical limit and compatible with the rapid scanning cytometry technique.We exploit this approach to further extend optical time-domain multiplexing to the downconversion luminescence, using luminescence microspheres wherein lifetimes are tuned through luminescence resonance energy transfer.We demonstrate real-time discrimination of these microspheres in the rapid scanning cytometry, and apply them to the multiplexed probing of pathogen DNA strands. Our results indicate that tunable luminescence lifetimes have considerable potential in high-throughput analytical sciences. © 2014 Macmillan Publishers Limited. All rights reserved