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  • 1
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    American Meteorological Society
    In:  EPIC3Journal of Climate, American Meteorological Society, 30, pp. 4337-4350, ISSN: 0894-8755
    Publication Date: 2017-12-15
    Description: Warm water of open ocean origin on the continental shelf of the Amundsen and Bellingshausen Seas causes the highest basal melt rates reported for Antarctic ice shelves with severe consequences for the ice shelf/ice sheet dynamics. Ice shelves fringing the broad continental shelf in the Weddell and Ross Seas melt at rates orders ofmagnitude smaller. However, simulations using coupled ice–ocean models forced with the atmospheric output of the HadCM3 SRES-A1B scenario run (CO2 concentration in the atmosphere reaches 700 ppmv by the year 2100 and stays at that level for an additional 100 years) show that the circulation in the southern Weddell Sea changes during the twenty-first century. Derivatives of Circumpolar Deep Water are directed southward underneath the Filchner–Ronne Ice Shelf, warming the cavity and dramatically increasing basal melting. To find out whether the open ocean will always continue to power the melting, the authors extend their simulations, applying twentieth-century atmospheric forcing, both alone and together with prescribed basal mass flux at the end of (or during) the SRES-A1B scenario run. The results identify a tipping point in the southern Weddell Sea: once warm water flushes the ice shelf cavity a positive meltwater feedback enhances the shelf circulation and the onshore transport of open ocean heat. The process is irreversible with a recurrence to twentieth-century atmospheric forcing and can only be halted through prescribing a return to twentieth-century basal melt rates. This finding might have strong implications for the stability of the Antarctic ice sheet.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev , info:eu-repo/semantics/article
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  • 2
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 30 (2017): 3829-3852, doi:10.1175/JCLI-D-16-0479.1.
    Description: This study provides an assessment of the uncertainty in ocean surface (OS) freshwater budgets and variability using evaporation E and precipitation P from 10 atmospheric reanalyses, two combined satellite-based E − P products, and two observation-based salinity products. Three issues are examined: the uncertainty level in the OS freshwater budget in atmospheric reanalyses, the uncertainty structure and association with the global ocean wet/dry zones, and the potential of salinity in ascribing the uncertainty in E − P. The products agree on the global mean pattern but differ considerably in magnitude. The OS freshwater budgets are 129 ± 10 (8%) cm yr−1 for E, 118 ± 11 (9%) cm yr−1 for P, and 11 ± 4 (36%) cm yr−1 for E − P, where the mean and error represent the ensemble mean and one standard deviation of the ensemble spread. The E − P uncertainty exceeds the uncertainty in E and P by a factor of 4 or more. The large uncertainty is attributed to P in the tropical wet zone. Most reanalyses tend to produce a wider tropical rainband when compared to satellite products, with the exception of two recent reanalyses that implement an observation-based correction for the model-generated P over land. The disparity in the width and the extent of seasonal migrations of the tropical wet zone causes a large spread in P, implying that the tropical moist physics and the realism of tropical rainfall remain a key challenge. Satellite salinity appears feasible to evaluate the fidelity of E − P variability in three tropical areas, where the uncertainty diagnosis has a global indication.
    Description: Primary support for the study is provided by the NOAAModeling, Analysis, Predictions, and Projections (MAPP) Program’s Climate Reanalysis Task Force (CRTF) through Grant NA13OAR4310106.
    Description: 2017-11-02
    Keywords: Hydrologic cycle ; Precipitation ; Evaporation ; Salinity ; Water budget ; Reanalysis data
    Repository Name: Woods Hole Open Access Server
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  • 3
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 30 (2017): 1233-1243, doi:10.1175/JCLI-D-16-0496.1.
    Description: A downscaling approach is applied to future projection simulations from four CMIP5 global climate models to investigate the response of the tropical cyclone (TC) climatology over the North Pacific basin to global warming. Under the influence of the anthropogenic rise in greenhouse gases, TC-track density, power dissipation, and TC genesis exhibit robust increasing trends over the North Pacific, especially over the central subtropical Pacific region. The increase in North Pacific TCs is primarily manifested as increases in the intense and relatively weak TCs. Examination of storm duration also reveals that TCs over the North Pacific have longer lifetimes under global warming. Through a genesis potential index, the mechanistic contributions of various physical climate factors to the simulated change in TC genesis are explored. More frequent TC genesis under global warming is mostly attributable to the smaller vertical wind shear and greater potential intensity (primarily due to higher sea surface temperature). In contrast, the effect of the saturation deficit of the free troposphere tends to suppress TC genesis, and the change in large-scale vorticity plays a negligible role.
    Description: The authors acknowledge support from the Strategic Environmental Research and Development Program (SERDP) (RC-2336). SERDP is the environmental science and technology program of the U.S. Department of Defense (DoD) in partnership with the U.S. Department of Energy (DOE) and the U.S. Environmental Protection Agency (EPA).
    Description: 2017-08-01
    Keywords: Tropical cyclones
    Repository Name: Woods Hole Open Access Server
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  • 4
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 30 (2017): 1739-1751, doi:10.1175/JCLI-D-16-0200.1.
    Description: The Indian Ocean has sustained robust surface warming in recent decades, but the role of multidecadal variability remains unclear. Using ocean model hindcasts, characteristics of low-frequency Indian Ocean temperature variations are explored. Simulated upper-ocean temperature changes across the Indian Ocean in the hindcast are consistent with those recorded in observational products and ocean reanalyses. Indian Ocean temperatures exhibit strong warming trends since the 1950s limited to the surface and south of 30°S, while extensive subsurface cooling occurs over much of the tropical Indian Ocean. Previous work focused on diagnosing causes of these long-term trends in the Indian Ocean over the second half of the twentieth century. Instead, the temporal evolution of Indian Ocean subsurface heat content is shown here to reveal distinct multidecadal variations associated with the Pacific decadal oscillation, and the long-term trends are thus interpreted to result from aliasing of the low-frequency variability. Transmission of the multidecadal signal occurs via an oceanic pathway through the Indonesian Throughflow and is manifest across the Indian Ocean centered along 12°S as westward-propagating Rossby waves modulating thermocline and subsurface heat content variations. Resulting low-frequency changes in the eastern Indian Ocean thermocline depth are associated with decadal variations in the frequency of Indian Ocean dipole (IOD) events, with positive IOD events unusually common in the 1960s and 1990s with a relatively shallow thermocline. In contrast, the deeper thermocline depth in the 1970s and 1980s is associated with frequent negative IOD and rare positive IOD events. Changes in Pacific wind forcing in recent decades and associated rapid increases in Indian Ocean subsurface heat content can thus affect the basin’s leading mode of variability, with implications for regional climate and vulnerable societies in surrounding countries.
    Description: This research was supported by a Research Fellowship by the Alexander von Humboldt Foundation, as well as the Ocean Climate Change Institute and the Investment in Science Fund at WHOI.
    Description: 2017-08-15
    Keywords: Indian Ocean ; Ocean dynamics ; Climate variability ; Multidecadal variability ; Pacific decadal oscillation
    Repository Name: Woods Hole Open Access Server
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  • 5
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 2251-2265, doi:10.1175/JPO-D-17-0042.1.
    Description: The problem of localized dense water formation over a sloping bottom is considered for the general case in which the topography forms a closed contour. This class of problems is motivated by topography around islands or shallow shoals in which convection resulting from brine rejection or surface heat loss reaches the bottom. The focus of this study is on the large-scale circulation that is forced far from the region of surface forcing. The authors find that a cyclonic current is generated around the topography, in the opposite sense to the propagation of the dense water plume. In physical terms, this current results from the propagation of low sea surface height from the region of dense water formation anticyclonically along the topographic contours back to the formation region. This pressure gradient is then balanced by a cyclonic geostrophic flow. This basic structure is well predicted by a linear quasigeostrophic theory, a primitive equation model, and in rotating tank experiments. For sufficiently strong forcing, the anticyclonic circulation of the dense plume meets this cyclonic circulation to produce a sharp front and offshore advection of dense water at the bottom and buoyant water at the surface. This nonlinear limit is demonstrated in both the primitive equation model and in the tank experiments.
    Description: MAS was supported by the National Science Foundation under Grant OCE-1534618. Support for CC was given by the WHOI Ocean Climate Change Institute Proposal 27071273.
    Description: 2018-03-20
    Keywords: Bottom currents ; Buoyancy ; Ocean dynamics ; Density currents
    Repository Name: Woods Hole Open Access Server
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  • 6
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Atmospheric and Oceanic Technology 34 (2017): 355-373, doi:10.1175/JTECH-D-15-0226.1.
    Description: Passive longwave infrared radiometric satellite–based retrievals of sea surface temperature (SST) at instrument nadir are investigated for cold bias caused by unscreened optically thin cirrus (OTC) clouds [cloud optical depth (COD) ≤ 0.3]. Level 2 nonlinear SST (NLSST) retrievals over tropical oceans (30°S–30°N) from Moderate Resolution Imaging Spectroradiometer (MODIS) radiances collected aboard the NASA Aqua satellite (Aqua-MODIS) are collocated with cloud profiles from the Cloud–Aerosol Lidar with Orthogonal Polarization (CALIOP) instrument. OTC clouds are present in approximately 25% of tropical quality-assured (QA) Aqua-MODIS Level 2 data, representing over 99% of all contaminating cirrus found. Cold-biased NLSST (MODIS, AVHRR, and VIIRS) and triple-window (AVHRR and VIIRS only) SST retrievals are modeled based on operational algorithms using radiative transfer model simulations conducted with a hypothetical 1.5-km-thick OTC cloud placed incrementally from 10.0 to 18.0 km above mean sea level for cloud optical depths between 0.0 and 0.3. Corresponding cold bias estimates for each sensor are estimated using relative Aqua-MODIS cloud contamination frequencies as a function of cloud-top height and COD (assuming they are consistent across each platform) integrated within each corresponding modeled cold bias matrix. NLSST relative OTC cold biases, for any single observation, range from 0.33° to 0.55°C for the three sensors, with an absolute (bulk mean) bias between 0.09° and 0.14°C. Triple-window retrievals are more resilient, ranging from 0.08° to 0.14°C relative and from 0.02° to 0.04°C absolute. Cold biases are constant across the Pacific and Indian Oceans. Absolute bias is lower over the Atlantic but relative bias is higher, indicating that this issue persists globally.
    Description: Authors JWM, NJS, and JZ acknowledge the support of NASA Project NNX14AJ13G andNSF Project IIA-1355466.Author JZ also acknowledges the support of ONR N00014-16-1-2040 (Grant 11843919). Author JWM further recognizes the Naval Research Enterprise Internship Program (NREIP). Support for his NREIP fellowship came from NASA Interagency Agreement NNG15JA17P on behalf of theMicro-Pulse LidarNetwork (E. J. Welton). Authors JRC, JAC and DLW acknowledge the support of Office of Naval Research Code 322 (PE0602435). Author JRC also acknowledges the support of NASA Interagency Agreement RPO201522 on behalf of the CALIPSO Science Team (C. R. Trepte).
    Description: 2017-08-06
    Keywords: Sea surface temperature ; Cirrus clouds ; Lidars/Lidar observations ; Remote sensing ; Satellite observations
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  • 7
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 339-351, doi:10.1175/JPO-D-16-0165.1.
    Description: A novel multi-iteration statistical method for studying tracer spreading using drifter data is introduced. The approach allows for the best use of the available drifter data by making use of a simple iterative procedure, which results in the statistically probable map showing the likelihood that a tracer released at some source location would visit different geographical regions, along with the associated arrival travel times. The technique is tested using real drifter data in the North Atlantic. Two examples are considered corresponding to sources in the western and eastern North Atlantic Ocean, that is, Massachusetts Bay–like and Irish Sea–like sources, respectively. In both examples, the method worked well in estimating the statistics of the tracer transport pathways and travel times throughout the entire North Atlantic. The role of eddies versus mean flow is quantified using the same technique, and eddies are shown to significantly broaden the spread of a tracer. The sensitivity of the results to the size of the source domain is investigated and causes for this sensitivity are discussed.
    Description: This work was supported by the Grant OCE-1356630 from the National Science Foundation (NSF). Rypina also acknowledges NSF Grant OCE-1154641 and NASA Grant NNX14AH29G.
    Description: 2017-07-31
    Keywords: Atlantic Ocean ; Mass fluxes/transport ; Ocean circulation ; Trajectories ; Statistics
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  • 8
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Atmospheric and Oceanic Technology 34 (2017): 269-275, doi:10.1175/JTECH-D-11-00196.1.
    Description: A data telemetry technique for communicating over standard oceanographic sea cables that achieves a nearly 100-fold increase in bandwidth as compared to traditional systems has been recently developed and successfully used at sea on board two Research Vessel (R/V) Atlantis cruises with an 8.5-km, 0.322-in.-diameter three-conductor sea cable. The system uses commercially available modules to provide Ethernet connectivity through existing sea cables, linking serial and video underwater instrumentation to the shipboard user. The new method applies Synchronous Digital Subscriber Line (SDSL) communications technology to undersea applications, greatly increasing the opportunities to use scientific instrumentation from existing ships and sea cables at minimal cost and without modification.
    Description: This development program has been supported, in part, through research grants from the National Science Foundation (OCE 0447395), the National Aeronautics and Space Administration’s ASTEP program (NNX09AB76G), and a WHOI Green and Hiam Innovative Technology Award.
    Description: 2017-07-23
    Keywords: Instrumentation/sensors
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  • 9
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Atmospheric and Oceanic Technology 34 (2017): 309-333, doi:10.1175/JTECH-D-16-0156.1.
    Description: Doppler current profilers on autonomous underwater gliders measure water velocity relative to the moving glider over vertical ranges of O(10) m. Measurements obtained with 1-MHz Nortek acoustic Doppler dual current profilers (AD2CPs) on Spray gliders deployed off Southern California, west of the Galápagos Archipelago, and in the Gulf Stream are used to demonstrate methods of estimating absolute horizontal velocities in the upper 1000 m of the ocean. Relative velocity measurements nearest to a glider are used to infer dive-dependent flight parameters, which are then used to correct estimates of absolute vertically averaged currents to account for the accumulation of biofouling during months-long glider missions. The inverse method for combining Doppler profiler measurements of relative velocity with absolute references to estimate profiles of absolute horizontal velocity is reviewed and expanded to include additional constraints on the velocity solutions. Errors arising from both instrumental bias and decreased abundance of acoustic scatterers at depth are considered. Though demonstrated with measurements from a particular combination of platform and instrument, these techniques should be applicable to other combinations of gliders and Doppler current profilers.
    Description: Spray glider missions were supported by the National Science Foundation (OCE-1232971, OCE-1233282), the National Oceanic and Atmospheric Administration (NA10OAR4320156, NA15OAR4320071), Eastman Chemical Company, the Oceans and Climate Change Institute at WHOI, and the W. Van Alan Clark Jr. Chair for Excellence in Oceanography at WHOI. RET acknowledges additional support for analysis and publication from the National Science Foundation (OCE-1633911).
    Description: 2017-07-31
    Keywords: Currents ; Acoustic measurements/effects ; Data processing ; Data quality control ; Profilers ; Inverse methods
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  • 10
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 633-647, doi:10.1175/JPO-D-16-0089.1.
    Description: Interannual variability in the volumetric water mass distribution within the North Atlantic Subtropical Gyre is described in relation to variability in the Atlantic meridional overturning circulation. The relative roles of diabatic and adiabatic processes in the volume and heat budgets of the subtropical gyre are investigated by projecting data into temperature coordinates as volumes of water using an Argo-based climatology and an ocean state estimate (ECCO version 4). This highlights that variations in the subtropical gyre volume budget are predominantly set by transport divergence in the gyre. A strong correlation between the volume anomaly due to transport divergence and the variability of both thermocline depth and Ekman pumping over the gyre suggests that wind-driven heave drives transport anomalies at the gyre boundaries. This wind-driven heaving contributes significantly to variations in the heat content of the gyre, as do anomalies in the air–sea fluxes. The analysis presented suggests that wind forcing plays an important role in driving interannual variability in the Atlantic meridional overturning circulation and that this variability can be unraveled from spatially distributed hydrographic observations using the framework presented here.
    Description: DGE was supported by a Natural Environment Research Council studentship award at the University of Southampton. JMT’s contribution was supported by the U.S. National Science Foundation (Grant OCE-1332667). GF’s contribution was supported by the U.S. National Science Foundation through Grant OCE-0961713 and by the U.S. National Oceanic and Atmospheric Administration through Grant NA10OAR4310135. The contributions of JDZ and AJGN were supported by the NERC Grant ‘‘Climate scale analysis of air and water masses’’ (NE/ K012932/1). ACNG gratefully acknowledges support from the Leverhulme Trust, the Royal Society, and the Wolfson Foundation. LY was supported by NASA Ocean Vector Wind Science Team (OVWST) activities under Grant NNA10AO86G.
    Keywords: North Atlantic Ocean ; Atmosphere-ocean interaction ; Ekman pumping/transport ; Ocean circulation ; Water masses ; Inverse methods
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  • 11
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 1291-1305, doi:10.1175/JPO-D-16-0160.1.
    Description: Along-stream variations in the dynamics of the Antarctic Circumpolar Current (ACC) impact heat and tracer transport, regulate interbasin exchange, and influence closure of the overturning circulation. Topography is primarily responsible for generating deviations from zonal-mean properties, mainly through standing meanders associated with regions of high eddy kinetic energy. Here, an idealized channel model is used to explore the spatial distribution of energy exchange and its relationship to eddy geometry, as characterized by both eddy momentum and eddy buoyancy fluxes. Variations in energy exchange properties occur not only between standing meander and quasi-zonal jet regions, but throughout the meander itself. Both barotropic and baroclinic stability properties, as well as the magnitude of energy exchange terms, undergo abrupt changes along the path of the ACC. These transitions are captured by diagnosing eddy fluxes of energy and by adopting the eddy geometry framework. The latter, typically applied to barotropic stability properties, is applied here in the depth–along-stream plane to include information about both barotropic and baroclinic stability properties of the flow. These simulations reveal that eddy momentum fluxes, and thus barotropic instability, play a leading role in the energy budget within a standing meander. This result suggests that baroclinic instability alone cannot capture the dynamics of ACC standing meanders, a challenge for models where eddy fluxes are parameterized.
    Description: The authors all acknowledge support from NSF OCE-1235488. MKY also acknowledges support from the AMS Graduate Student Fellowship.
    Description: 2017-10-12
    Keywords: Southern Ocean ; Channel flows ; Stability ; Topographic effects ; Eddies ; Mesoscale models
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  • 12
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Atmospheric and Oceanic Technology 34 (2017): 415-427, doi:10.1175/JTECH-D-16-0069.1.
    Description: Sensors and instruments for basic oceanographic properties are becoming increasingly sophisticated, which both simplifies and complicates their use in field studies. This increased sophistication disproportionately affects smaller-scale observational efforts that are less likely to be well supported technically but which need to integrate instruments, sensors, and commonly needed peripheral devices in ways not envisioned by their manufacturers. A general-purpose hardware and software framework was developed around a widely used family of low-power microcontrollers to lessen the technical expertise and customization required to integrate sensors, instruments, and peripherals, and thus simplify such integration scenarios. Both the hardware and associated firmware development tools provide a range of features often required in such scenarios: serial data interfaces, analog inputs and outputs, logic lines and power-switching capability, nonvolatile storage of data and parameters for sampling or configuration, and serial communication interfaces to supervisory or telemetry systems. The microcontroller and additional components needed to implement this integration framework are small enough to encapsulate in standard cable splices, creating a small form factor “smart cable” that can be readily wired and programmed for a range of integration needs. An application programming library developed for this hardware provides skeleton code for functions commonly desired when integrating sensors, instruments, and peripherals. This minimizes the firmware programming expertise needed to apply this framework in many integration scenarios and thus streamlines the development of firmware for different field applications. Envisioned applications are in field programs where significant technical instrumentation expertise is unavailable or not cost effective.
    Description: Link Foundation Ocean Engineering graduate fellowship to SRL. Subsequent development effort was supported by a NASA New Investigator Award to SRL (NNX10AQ83G) and by the Woods Hole Oceanographic Institution through its Assistant Scientist Endowed Support, a Cecil H. and Ida M. Green Technology Innovation Award, and the Investment in Science Program.
    Keywords: Instrumentation/sensors
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  • 13
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Atmospheric and Oceanic Technology 33 (2016): 2373-2384, doi:10.1175/JTECH-D-16-0024.1.
    Description: A long-path methane (CH4) sensor was developed and field deployed using an 8-μm quantum cascade laser. The high optical power (40 mW) of the laser allowed for path-integrated measurements of ambient CH4 at total pathlengths from 100 to 1200 m with the use of a retroreflector. Wavelength modulation spectroscopy was used to make high-precision measurements of atmospheric pressure–broadened CH4 absorption over these long distances. An in-line reference cell with higher harmonic detection provided metrics of system stability in rapidly changing and harsh environments. The system consumed less than 100 W of power and required no consumables. The measurements intercompared favorably (typically less than 5% difference) with a commercial in situ methane sensor when accounting for the different spatiotemporal scales of the measurements. The sensor was field deployed for 2 weeks at an arctic lake to examine the robustness of the approach in harsh field environments. Short-term precision over a 458-m pathlength was 10 ppbv at 1 Hz, equivalent to a signal from a methane enhancement above background of 5 ppmv in a 1-m length. The sensor performed well in a range of harsh environmental conditions, including snow, rain, wind, and changing temperatures. These field measurements demonstrate the capabilities of the approach for use in detecting large but highly variable emissions in arctic environments.
    Description: The authors gratefully acknowledge funding for this work by MIRTHE through NSF-ERC Grant EEC-0540832. D. J. Miller acknowledges support by the National Science Foundation Graduate Research Fellowship under Grant DGE-0646086. K. Sun acknowledges support by the NASA Earth and Space Science Fellowship IIP-1263579.
    Description: 2017-05-01
    Keywords: Arctic ; North America ; Greenhouse gases ; In situ atmospheric observations ; Instrumentation/sensors ; Field experiments
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  • 14
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Bulletin of the American Meteorological Society 98 (2017): 737-752, doi:10.1175/BAMS-D-16-0057.1.
    Description: For decades oceanographers have understood the Atlantic meridional overturning circulation (AMOC) to be primarily driven by changes in the production of deep-water formation in the subpolar and subarctic North Atlantic. Indeed, current Intergovernmental Panel on Climate Change (IPCC) projections of an AMOC slowdown in the twenty-first century based on climate models are attributed to the inhibition of deep convection in the North Atlantic. However, observational evidence for this linkage has been elusive: there has been no clear demonstration of AMOC variability in response to changes in deep-water formation. The motivation for understanding this linkage is compelling, since the overturning circulation has been shown to sequester heat and anthropogenic carbon in the deep ocean. Furthermore, AMOC variability is expected to impact this sequestration as well as have consequences for regional and global climates through its effect on the poleward transport of warm water. Motivated by the need for a mechanistic understanding of the AMOC, an international community has assembled an observing system, Overturning in the Subpolar North Atlantic Program (OSNAP), to provide a continuous record of the transbasin fluxes of heat, mass, and freshwater, and to link that record to convective activity and water mass transformation at high latitudes. OSNAP, in conjunction with the Rapid Climate Change–Meridional Overturning Circulation and Heatflux Array (RAPID–MOCHA) at 26°N and other observational elements, will provide a comprehensive measure of the three-dimensional AMOC and an understanding of what drives its variability. The OSNAP observing system was fully deployed in the summer of 2014, and the first OSNAP data products are expected in the fall of 2017.
    Description: The authors gratefully acknowledge financial support from the U.S. National Science Foundation (NSF; OCE-1259102, OCE-1259103, OCE-1259618, OCE-1258823, OCE-1259210, OCE-1259398, OCE-0136215, and OCE-1005697); the U.S. National Aeronautics and Space Administration (NASA); the U.S. National Oceanic and Atmospheric Administration (NOAA); the WHOI Ocean and Climate Change Institute (OCCI), the WHOI Independent Research and Development (IRD) Program, and the WHOI Postdoctoral Scholar Program; the U.K. Natural Environment Research Council (NERC; NE/K010875/1, NE/K010700/1, R8-H12-85, FASTNEt NE/I030224/1, NE/K010972/1, NE/K012932/1, and NE/M018024/1); the European Union Seventh Framework Programme (NACLIM project, 308299 and 610055); the German Federal Ministry and Education German Research RACE Program; the Natural Sciences and Engineering Research Council of Canada (NSERC; RGPIN 227438-09, RGPIN 04357, and RG-PCC 433898); Fisheries and Oceans Canada; the National Natural Science Foundation of China (NSFC; 41521091, U1406401); the Fundamental Research Funds for the Central Universities of China; the French Research Institute for Exploitation of the Sea (IFREMER); the French National Center for Scientific Research (CNRS); the French National Institute for Earth Sciences and Astronomy (INSU); the French national program LEFE; and the French Oceanographic Fleet (TGIR FOF).
    Description: 2017-10-24
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  • 15
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 485-498, doi:10.1175/JPO-D-16-0175.1.
    Description: Dense oceanic overflows descend over the rough topography of the continental slope entraining and mixing with surrounding waters. The associated dilution dictates the fate of these currents and thus is of fundamental importance to the formation of deep water masses. The entrainment in a dense current flowing down a sloping bottom in a rotating homogeneous fluid is investigated using laboratory experiments, focusing on the influence of the bottom roughness on the flow dynamics. The roughness is idealized by an array of vertical rigid cylinders and both their spacing and height are varied as well as the inclination of the sloping bottom. The presence of the roughness is generally observed to decelerate the dense current, with a consequent reduction of the Froude number, when compared to the smooth bottom configuration. However, the dilution of the dense current due to mixing with the ambient fluid is enhanced by the roughness elements, especially for low Froude numbers. When the entrainment due to shear instability at the interface between the dense current and the ambient fluid is low, the additional turbulence and mixing arising at the bottom of the dense current due to the roughness elements strongly affects the dilution of the current. Finally, a strong dependence of the entrainment parameter on the Reynolds number is observed.
    Description: Support to C. C. was given by the National Science Foundation Project OCE- 1333174. Support to L. O. during her internship at WHOI was provided by the Lions Club ‘‘Napoli Megaride’’ and the Zoological Station Anton Dohrn through the Paolo Brancaccio fellowship (2012).
    Description: 2017-08-20
    Keywords: Density currents ; Entrainment ; Density currents ; Mixing
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  • 16
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 30 (2017): 6757-6769, doi:10.1175/JCLI-D-16-0461.1.
    Description: Arctic sea ice area (SIA) during late summer and early fall decreased substantially over the last four decades, and its decline accelerated beginning in the early 2000s. Statistical analyses of observations show that enhanced poleward moisture transport from the North Pacific to the Arctic Ocean contributed to the accelerated SIA decrease during the most recent period. As a consequence, specific humidity in the Arctic Pacific sector significantly increased along with an increase of downward longwave radiation beginning in 2002, which led to a significant acceleration in the decline of SIA in the Arctic Pacific sector. The resulting sea ice loss led to increased evaporation in the Arctic Ocean, resulting in a further increase of the specific humidity in mid-to-late fall, thus acting as a positive feedback to the sea ice loss. The overall set of processes is also found in a long control simulation of a coupled climate model.
    Description: This work was supported by the National Research Foundation of Korea Grant NRF-2009-C1AAA001-0093, funded by the Korean government (MEST), to HJL, YHK, and MOK. S-WY is supported by the Korea Meteorological Administration Research and Development Program under Grant KMIPA2015-1042. Y-OK is supported by the U.S. Department of Energy (DE-SC0014433) and National Science Foundation (OCE-1242989). WP acknowledges support from the BMBF project CLIMPRE InterDec (FKZ: 01LP1609B).
    Description: 2018-01-26
    Keywords: Pacific decadal oscillation ; Sea surface temperature ; Humidity ; Ice loss/growth
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  • 17
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Weather and Forecasting 32 (2017): 1659-1666, doi:10.1175/WAF-D-17-0076.1.
    Description: Although rip currents are a major hazard for beachgoers, the relationship between the danger to swimmers and the physical properties of rip current circulation is not well understood. Here, the relationship between statistical model estimates of hazardous rip current likelihood and in situ velocity observations is assessed. The statistical model is part of a forecasting system that is being made operational by the National Weather Service to predict rip current hazard likelihood as a function of wave conditions and water level. The temporal variability of rip current speeds (offshore-directed currents) observed on an energetic sandy beach is correlated with the hindcasted hazard likelihood for a wide range of conditions. High likelihoods and rip current speeds occurred for low water levels, nearly shore-normal wave angles, and moderate or larger wave heights. The relationship between modeled hazard likelihood and the frequency with which rip current speeds exceeded a threshold was assessed for a range of threshold speeds. The frequency of occurrence of high (threshold exceeding) rip current speeds is consistent with the modeled probability of hazard, with a maximum Brier skill score of 0.65 for a threshold speed of 0.23 m s−1, and skill scores greater than 0.60 for threshold speeds between 0.15 and 0.30 m s−1. The results suggest that rip current speed may be an effective proxy for hazard level and that speeds greater than ~0.2 m s−1 may be hazardous to swimmers.
    Description: Funding was provided by the National Science Foundation (1232910, 1332705, and 1536365), and by National Security Science and Engineering and Vannevar Bush Faculty Fellowships funded by the assistant secretary of Defense for Research and Engineering.
    Description: 2018-02-28
    Keywords: Coastlines ; Coastal flows ; Waves, oceanic ; Forecast verification/skill ; Probability forecasts/models/distribution ; Statistical forecasting
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  • 18
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 1061-1075, doi:10.1175/JPO-D-16-0248.1.
    Description: A major challenge in modeling the circulation over coral reefs is uncertainty in the drag coefficient because existing estimates span two orders of magnitude. Current and pressure measurements from five coral reefs are used to estimate drag coefficients based on depth-average flow, assuming a balance between the cross-reef pressure gradient and the bottom stress. At two sites wind stress is a significant term in the cross-reef momentum balance and is included in estimating the drag coefficient. For the five coral reef sites and a previous laboratory study, estimated drag coefficients increase as the water depth decreases consistent with open channel flow theory. For example, for a typical coral reef hydrodynamic roughness of 5 cm, observational estimates, and the theory indicate that the drag coefficient decreases from 0.4 in 20 cm of water to 0.005 in 10 m of water. Synthesis of results from the new field observations with estimates from previous field and laboratory studies indicate that coral reef drag coefficients range from 0.2 to 0.005 and hydrodynamic roughnesses generally range from 2 to 8 cm. While coral reef drag coefficients depend on factors such as physical roughness and surface waves, a substantial fraction of the scatter in estimates of coral reef drag coefficients is due to variations in water depth.
    Description: The Red Sea field program was supported by Awards USA 00002 and KSA 00011 made by KAUST to S. Lentz and J. Churchill. The Palau field program was funded by NSF Award OCE-1220529.
    Keywords: Ocean ; Currents ; Wind stress ; Boundary layer ; Sea level ; Tides
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  • 19
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 1789-1797, doi:10.1175/JPO-D-16-0240.1.
    Description: Internal solitary waves are commonly observed in the coastal ocean where they are known to contribute to mass transport and turbulent mixing. While these waves are often generated by cross-isobath barotropic tidal currents, novel observations are presented suggesting that internal solitary waves result from along-isobath tidal flows over channel-shoal bathymetry. Mooring and ship-based velocity, temperature, and salinity data were collected over a cross-channel section in a stratified estuary. The data show that Ekman forcing on along-channel tidal currents drives lateral circulation, which interacts with the stratified water over the deep channel to generate a supercritical mode-2 internal lee wave. This lee wave propagates onto the shallow shoal and evolves into a group of internal solitary waves of elevation due to nonlinear steepening. These observations highlight the potential importance of three-dimensionality on the conversion of tidal flow to internal waves in the rotating ocean.
    Description: National Science Foundation (OCE-1061609)
    Description: 2018-01-03
    Keywords: Estuaries ; Internal waves ; Solitary waves
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  • 20
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 30 (2017): 8061-8080, doi:10.1175/JCLI-D-16-0834.1.
    Description: During the southwest monsoons, the Arabian Sea (AS) develops highly energetic mesoscale variability associated with the Somali Current (SC), Great Whirl (GW), and cold filaments (CF). The resultant high-amplitude anomalies and gradients of sea surface temperature (SST) and surface currents modify the wind stress, triggering the so-called mesoscale coupled feedbacks. This study uses a high-resolution regional coupled model with a novel coupling procedure that separates spatial scales of the air–sea coupling to show that SST and surface currents are coupled to the atmosphere at distinct spatial scales, exerting distinct dynamic influences. The effect of mesoscale SST–wind interaction is manifested most strongly in wind work and Ekman pumping over the GW, primarily affecting the position of GW and the separation latitude of the SC. If this effect is suppressed, enhanced wind work and a weakened Ekman pumping dipole cause the GW to extend northeastward, delaying the SC separation by 1°. Current–wind interaction, in contrast, is related to the amount of wind energy input. When it is suppressed, especially as a result of background-scale currents, depth-integrated kinetic energy, both the mean and eddy, is significantly enhanced. Ekman pumping velocity over the GW is overly negative because of a lack of vorticity that offsets the wind stress curl, further invigorating the GW. Moreover, significant changes in time-mean SST and evaporation are generated in response to the current–wind interaction, accompanied by a noticeable southward shift in the Findlater Jet. The significant increase in moisture transport in the central AS implies that air–sea interaction mediated by the surface current is a potentially important process for simulation and prediction of the monsoon rainfall.
    Description: This work is supported by ONR (N00014-15-1-2588 and N00014-17-1-2398), NSF (OCE- 1419235), and NOAA (NA15OAR4310176).
    Description: 2018-03-08
    Keywords: Indian Ocean ; Wind stress ; Ekman pumping ; Monsoons ; Air-sea interaction ; Coupled models
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  • 21
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 30 (2017): 6611-6627, doi:10.1175/JCLI-D-16-0291.1.
    Description: The interannual fluctuations of the equatorial thermocline are usually associated with El Niño activity, but the linkage between the thermocline modes and El Niño is still under debate. In the present study, a mode function decomposition method is applied to the equatorial Pacific thermocline, and the results show that the first two dominant modes (M1 and M2) identify two distinct characteristics of the equatorial Pacific thermocline. The M1 reflects a basinwide zonally tilted thermocline related to the eastern Pacific (EP) El Niño, with shoaling (deepening) in the western (eastern) equatorial Pacific. The M2 represents the central Pacific (CP) El Niño, characterized by a V-shaped equatorial Pacific thermocline (i.e., deep in the central equatorial Pacific and shallow on both the western and eastern boundaries). Furthermore, both modes are stable and significant on the interannual time scale, and manifest as the major feature of the thermocline fluctuations associated with the two types of El Niño events. As good proxies of EP and CP El Niño events, thermocline-based indices clearly reveal the inherent characteristics of subsurface ocean responses during the evolution of El Niño events, which are characterized by the remarkable zonal eastward propagation of equatorial subsurface ocean temperature anomalies, particularly during the CP El Niño. Further analysis of the mixed layer heat budget suggests that the air–sea interactions determine the establishment and development stages of the CP El Niño, while the thermocline feedback is vital for its further development. These results highlight the key influence of equatorial Pacific thermocline fluctuations in conjunction with the air–sea interactions, on the CP El Niño.
    Description: This work is jointly supported by the Funds for Creative Research Groups of China (Grant 41521005), the Special Fund for Public Welfare Industry (GYHY201506013), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant XDA11010301), and the National Natural Science Foundation of China (Grants 41406033, 41475057, 41376024, 41676013) and the CAS/SAFEA International Partnership Program for Creative Research Teams.
    Description: 2018-01-21
    Keywords: Thermocline ; El Nino
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  • 22
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 46 (2016): 3549-3562, doi:10.1175/JPO-D-16-0140.1.
    Description: The equatorial deep jets (EDJs) are a ubiquitous feature of the equatorial oceans; in the Atlantic Ocean, they are the dominant mode of interannual variability of the zonal flow at intermediate depth. On the basis of more than 10 years of moored observations of zonal velocity at 23°W, the vertically propagating EDJs are best described as superimposed oscillations of the 13th to the 23rd baroclinic modes with a dominant oscillation period for all modes of 1650 days. This period is close to the resonance period of the respective gravest equatorial basin mode for the dominant vertical modes 16 and 17. It is argued that since the equatorial basin mode is composed of linear equatorial waves, a linear reduced-gravity model can be employed for each baroclinic mode, driven by spatially homogeneous zonal forcing oscillating with the EDJ period. The fit of the model solutions to observations at 23°W yields a basinwide reconstruction of the EDJs and the associated vertical structure of their forcing. From the resulting vertical profile of mean power input and vertical energy flux on the equator, it follows that the EDJs are locally maintained over a considerable depth range, from 500 to 2500 m, with the maximum power input and vertical energy flux at 1300 m. The strong dissipation closely ties the apparent vertical propagation of energy to the vertical distribution of power input and, together with the EDJs’ prevailing downward phase propagation, requires the phase of the forcing of the EDJs to propagate downward.
    Description: MC is grateful for support from the German Federal Ministry of Education and Research (BMBF) Miklip project through the MODINI project. RJG and PB are grateful for continuing support from the GEOMAR Helmholtz Centre for Ocean Research Kiel. This study has also been supported by the Deutsche Forschungsgemeinschaft as part of the Sonderforschungsbereich 754 “Climate-Biogeochemistry Interactions in the Tropical Ocean,” through several research cruises with R/V Meteor and R/V Maria S. Merian by the German Federal Ministry of Education and Research as part of the cooperative projects “RACE” and “SACUS” and by European Union 7th Framework Programme (FP7 2007–2013) under Grant Agreement 603521 PREFACE project. Additional support for the observations and JMT’s contributions were provided by the U.S. National Science Foundation (OCE-0850175).
    Keywords: Tropics ; Forcing ; Shallow-water equations ; Waves, oceanic ; Oscillations ; Interannual variability
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  • 23
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 1205-1220, doi:10.1175/JPO-D-16-0258.1.
    Description: The linkage among total exchange flow, entrainment, and diffusive salt flux in estuaries is derived analytically using salinity coordinates, revealing the simple but important relationship between total exchange flow and mixing. Mixing is defined and quantified in this paper as the dissipation of salinity variance. The method uses the conservation of volume and salt to quantify and distinguish the diahaline transport of volume (i.e., entrainment) and diahaline diffusive salt flux. A numerical model of the Hudson estuary is used as an example of the application of the method in a realistic estuary with a persistent but temporally variable exchange flow. A notable finding of this analysis is that the total exchange flow and diahaline salt flux are out of phase with respect to the spring–neap cycle. Total exchange flow reaches its maximum near minimum neap tide, but diahaline salt transport reaches its maximum during the maximum spring tide. This phase shift explains the strong temporal variation of stratification and estuarine salt content through the spring–neap cycle. In addition to quantifying temporal variation, the method reveals the spatial variation of total exchange flow, entrainment, and diffusive salt flux through the estuary. For instance, the analysis of the Hudson estuary indicates that diffusive salt flux is intensified in the wider cross sections. The method also provides a simple means of quantifying numerical mixing in ocean models because it provides an estimate of the total dissipation of salinity variance, which is the sum of mixing due to the turbulence closure and numerical mixing.
    Description: T. Wang was supported by the Open Research Fund of State Key Laboratory of Estuarine and Coastal Research (Grant SKLEC-KF201509), the Fundamental Research Funds for the Central Universities (Grant 2017B03514), and the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant XDA11010203). W. R. Geyer was supported by NSF Grant OCE 0926427 and ONR Grant N00014-16-1-2948. P. MacCready was supported by NSF Grant OCE-1634148.
    Description: 2017-09-14
    Keywords: Baroclinic flows ; Conservation equations ; Diapycnal mixing ; Diffusion ; Entrainment ; Mixing
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  • 24
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 30 (2017): 4965-4981, doi:10.1175/JCLI-D-16-0228.1.
    Description: To improve the understanding of storm tracks and western boundary current (WBC) interactions, surface storm tracks in 12 CMIP5 models are examined against ERA-Interim. All models capture an equatorward displacement toward the WBCs in the locations of the surface storm tracks’ maxima relative to those at 850 hPa. An estimated storm-track metric is developed to analyze the location of the surface storm track. It shows that the equatorward shift is influenced by both the lower-tropospheric instability and the baroclinicity. Basin-scale spatial correlations between models and ERA-Interim for the storm tracks, near-surface stability, SST gradient, and baroclinicity are calculated to test the ability of the GCMs’ match reanalysis. An intermodel comparison of the spatial correlations suggests that differences (relative to ERA-Interim) in the position of the storm track aloft have the strongest influence on differences in the surface storm-track position. However, in the North Atlantic, biases in the surface storm track north of the Gulf Stream are related to biases in the SST. An analysis of the strength of the storm tracks shows that most models generate a weaker storm track at the surface than 850 hPa, consistent with observations, although some outliers are found. A linear relationship exists among the models between storm-track amplitudes at 500 and 850 hPa, but not between 850 hPa and the surface. In total, the work reveals a dual role in forcing the surface storm track from aloft and from the ocean surface in CMIP5 models, with the atmosphere having the larger relative influence.
    Description: JFB was partially supported by the NOAA Climate Program Office’s Modeling, Analysis, Predictions, and Projections program (Grant NA15OAR4310094). Y-OK was supported by NSF Division of Atmospheric and Geospace Science Climate and Large-scale Dynamics Program (AGS-1355339), NASA Physical Oceanography Program (NNX13AM59G), and DOE Office of Biological and Environmental Research Regional and Global Climate Modeling Program (DE-SC0014433). RJS was supported by DOE Office of Biological and Environmental Research (DE-SC0006743) and NSF Directorate for Geosciences Division of Ocean Sciences (1419584),
    Description: 2017-10-03
    Keywords: Atmosphere-ocean interaction ; Storm tracks
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  • 25
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 1921-1939, doi:10.1175/JPO-D-16-0146.1.
    Description: The role of surface gravity waves in structuring the air–sea momentum flux is examined in the middle reaches of Chesapeake Bay. Observed wave spectra showed that wave direction in Chesapeake Bay is strongly correlated with basin geometry. Waves preferentially developed in the direction of maximum fetch, suggesting that dominant wave frequencies may be commonly and persistently misaligned with local wind forcing. Direct observations from an ultrasonic anemometer and vertical array of ADVs show that the magnitude and direction of stress changed across the air–sea interface, suggesting that a stress divergence occurred at or near the water surface. Using a numerical wave model in combination with direct flux measurements, the air–sea momentum flux was partitioned between the surface wave field and the mean flow. Results indicate that the surface wave field can store or release a significant fraction of the total momentum flux depending on the direction of the wind. When wind blew across dominant fetch axes, the generation of short gravity waves stored as much as 40% of the total wind stress. Accounting for the storage of momentum in the surface wave field closed the air–sea momentum budget. Agreement between the direction of Lagrangian shear and the direction of the stress vector in the mixed surface layer suggests that the observed directional difference was due to the combined effect of breaking waves producing downward sweeps of momentum in the direction of wave propagation and the straining of that vorticity field in a manner similar to Langmuir turbulence.
    Description: This work was supported by National Science Foundation Grants OCE-1061609 and OCE-1339032.
    Description: 2018-01-13
    Keywords: Atmosphere-ocean interaction ; Coastal flows ; Mixing ; Momentum ; Wind stress ; Wind waves
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  • 26
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 2611-2630, doi:10.1175/JPO-D-16-0259.1.
    Description: This study reports the results of large-eddy simulations of an axisymmetric turbulent buoyant plume in a stratified fluid. The configuration used is an idealized model of the plume generated by a subglacial discharge at the base of a tidewater glacier with an ambient stratification typical of Greenland fjords. The plume is discharged from a round source of various diameters and characteristic stratifications for summer and winter are considered. The classical theory for the integral parameters of a turbulent plume in a homogeneous fluid gives accurate predictions in the weakly stratified lower layer up to the pycnocline, and the plume dynamics are not sensitive to changes in the source diameter. In winter, when the stratification is similar to an idealized two-layer case, turbulent entrainment and generation of internal waves by the plume top are in agreement with the theoretical and numerical results obtained for turbulent jets in a two-layer stratification. In summer, instead, the stratification is more complex and turbulent entrainment by the plume top is significantly reduced. The subsurface layer in summer is characterized by a strong density gradient and the oscillating plume generates internal waves that might serve as an indicator of submerged plumes not penetrating to the surface.
    Description: This work was supported by Linné FLOW Centre at KTH and the Academy of Finland Centre of Excellence program (Grant 307331) (E. E.) and VR Swedish Research Council, Outstanding Young Researcher Award, Grant VR 2014-5001 (L. B.). Support to C. C. was given by the NSF Project OCE-1434041.
    Description: 2018-04-26
    Keywords: Buoyancy ; Internal waves ; Turbulence ; Jets ; Oscillations ; Large eddy simulations
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  • 27
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 2479-2498, doi:10.1175/JPO-D-16-0167.1.
    Description: The generation of trapped and radiating internal tides around Izu‐Oshima Island located off Sagami Bay, Japan, is investigated using the three-dimensional Stanford Unstructured Nonhydrostatic Terrain-following Adaptive Navier–Stokes Simulator (SUNTANS) that is validated with observations of isotherm displacements in shallow water. The model is forced by barotropic tides, which generate strong baroclinic internal tides in the study region. Model results showed that when diurnal K1 barotropic tides dominate, resonance of a trapped internal Kelvin wave leads to large-amplitude internal tides in shallow waters on the coast. This resonance produces diurnal motions that are much stronger than the semidiurnal motions. The weaker, freely propagating, semidiurnal internal tides are generated on the western side of the island, where the M2 internal tide beam angle matches the topographic slope. The internal wave energy flux due to the diurnal internal tides is much higher than that of the semidiurnal tides in the study region. Although the diurnal internal tide energy is trapped, this study shows that steepening of the Kelvin waves produces high-frequency internal tides that radiate from the island, thus acting as a mechanism to extract energy from the diurnal motions.
    Description: This study was supported by JST CREST Grant Number JPRMJCR12A6.
    Description: 2018-04-12
    Keywords: Pacific Ocean ; Internal waves ; Kelvin waves ; In situ oceanic observations ; Baroclinic models ; Ocean models
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  • 28
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Bulletin of the American Meteorological Society 98 (2017): 2429-2454, doi:10.1175/BAMS-D-16-0030.1.
    Description: Diapycnal mixing plays a primary role in the thermodynamic balance of the ocean and, consequently, in oceanic heat and carbon uptake and storage. Though observed mixing rates are on average consistent with values required by inverse models, recent attention has focused on the dramatic spatial variability, spanning several orders of magnitude, of mixing rates in both the upper and deep ocean. Away from ocean boundaries, the spatiotemporal patterns of mixing are largely driven by the geography of generation, propagation, and dissipation of internal waves, which supply much of the power for turbulent mixing. Over the last 5 years and under the auspices of U.S. Climate Variability and Predictability Program (CLIVAR), a National Science Foundation (NSF)- and National Oceanic and Atmospheric Administration (NOAA)-supported Climate Process Team has been engaged in developing, implementing, and testing dynamics-based parameterizations for internal wave–driven turbulent mixing in global ocean models. The work has primarily focused on turbulence 1) near sites of internal tide generation, 2) in the upper ocean related to wind-generated near inertial motions, 3) due to internal lee waves generated by low-frequency mesoscale flows over topography, and 4) at ocean margins. Here, we review recent progress, describe the tools developed, and discuss future directions.
    Description: We are grateful to U.S. CLIVAR for their leadership in instigating and facilitating the Climate Process Team program. We are indebted to NSF and NOAA for sponsoring the CPT series.
    Description: 2018-06-01
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  • 29
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 1873-1896, doi:10.1175/JPO-D-16-0264.1.
    Description: Midocean ridge fracture zones channel bottom waters in the eastern Brazil Basin in regions of intensified deep mixing. The mechanisms responsible for the deep turbulent mixing inside the numerous midocean fracture zones, whether affected by the local or the nonlocal canyon topography, are still subject to debate. To discriminate those mechanisms and to discern the canyon mean flow, two moorings sampled a deep canyon over and away from a sill/contraction. A 2-layer exchange flow, accelerated at the sill, transports 0.04–0.10-Sv (1 Sv ≡ 106 m3 s−1) up canyon in the deep layer. At the sill, the dissipation rate of turbulent kinetic energy ε increases as measured from microstructure profilers and as inferred from a parameterization of vertical kinetic energy. Cross-sill density and microstructure transects reveal an overflow potentially hydraulically controlled and modulated by fortnightly tides. During spring to neap tides, ε varies from O(10−9) to O(10−10) W kg−1 below 3500 m around the 2-layer interface. The detection of temperature overturns during tidal flow reversal, which almost fully opposes the deep up-canyon mean flow, confirms the canyon middepth enhancement of ε. The internal tide energy flux, particularly enhanced at the sill, compares with the lower-layer energy loss across the sill. Throughout the canyon away from the sill, near-inertial waves with downward-propagating energy dominate the internal wave field. The present study underlines the intricate pattern of the deep turbulent mixing affected by the mean flow, internal tides, and near-inertial waves.
    Description: The DoMORE project was supported by NSF under the Grant OCE-1235094.
    Description: 2018-01-13
    Keywords: Abyssal circulation ; Bottom currents/bottom water ; Diapycnal mixing
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  • 30
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    American Meteorological Society
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 2531-2543, doi:10.1175/JPO-D-17-0051.1.
    Description: Argo floats are used to investigate Labrador Sea overturning and its variability on seasonal time scales. This is the first application of Argo floats to estimate overturning in a deep-water formation region in the North Atlantic. Unlike hydrographic measurements, which are typically confined to the summer season, floats offer the advantage of collecting data in all seasons. Seasonal composite potential density and absolute geostrophic velocity sections across the mouth of the Labrador Sea assembled from float profiles and trajectories at 1000 m are used to calculate the horizontal and overturning circulations. The overturning exhibits a pronounced seasonal cycle; in depth space the overturning doubles throughout the course of the year, and in density space it triples. The largest overturning [1.2 Sv (1 Sv ≡ 106 m3 s−1) in depth space and 3.9 Sv in density space] occurs in spring and corresponds to the outflow of recently formed Labrador Sea Water. The overturning decreases through summer and reaches a minimum in winter (0.6 Sv in depth space and 1.2 Sv in density space). The robustness of the Argo seasonal overturning is supported by a comparison to an overturning estimate based on hydrographic data from the AR7W line.
    Description: NSF OCE-1459474 supported this work.
    Description: 2018-04-17
    Keywords: North Atlantic Ocean ; Meridional overturning circulation ; In situ oceanic observations ; Seasonal cycle
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  • 31
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 2631-2646, doi:10.1175/JPO-D-17-0062.1.
    Description: Data from a mooring array deployed north of Denmark Strait from September 2011 to August 2012 are used to investigate the structure and variability of the shelfbreak East Greenland Current (EGC). The shelfbreak EGC is a surface-intensified current situated just offshore of the east Greenland shelf break flowing southward through Denmark Strait. This study identified two dominant spatial modes of variability within the current: a pulsing mode and a meandering mode, both of which were most pronounced in fall and winter. A particularly energetic event in November 2011 was related to a reversal of the current for nearly a month. In addition to the seasonal signal, the current was associated with periods of enhanced eddy kinetic energy and increased variability on shorter time scales. The data indicate that the current is, for the most part, barotropically stable but subject to baroclinic instability from September to March. By contrast, in summer the current is mainly confined to the shelf break with decreased eddy kinetic energy and minimal baroclinic conversion. No other region of the Nordic Seas displays higher levels of eddy kinetic energy than the shelfbreak EGC north of Denmark Strait during fall. This appears to be due to the large velocity variability on mesoscale time scales generated by the instabilities. The mesoscale variability documented here may be a source of the variability observed at the Denmark Strait sill.
    Description: Support for this work was provided by the Norwegian Research Council under Grant Agreement 231647 (LH and KV) and the Bergen Research Foundation under Grant BFS2016REK01 (KV). Additional funding was provided by the National Science Foundation under Grants OCE-0959381 and OCE-1558742 (RP).
    Keywords: Ocean ; Arctic ; Boundary currents ; Currents ; Stability ; Oceanic variability
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  • 32
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 46 (2016): 3661-3679, doi:10.1175/JPO-D-16-0018.1.
    Description: A hydrostatic, coupled-mode, shallow-water model (CSW) is described and used to diagnose and simulate tidal dynamics in the greater Mid-Atlantic Bight region. The reduced-physics model incorporates realistic stratification and topography, internal tide forcing from a priori estimates of the surface tide, and advection terms that describe first-order interactions of internal tides with slowly varying mean flow and mean buoyancy fields and their respective shear. The model is validated via comparisons with semianalytic models and nonlinear primitive equation models in several idealized and realistic simulations that include internal tide interactions with topography and mean flows. Then, 24 simulations of internal tide generation and propagation in the greater Mid-Atlantic Bight region are used to diagnose significant internal tide interactions with the Gulf Stream. The simulations indicate that locally generated mode-one internal tides refract and/or reflect at the Gulf Stream. The redirected internal tides often reappear at the shelf break, where their onshore energy fluxes are intermittent (i.e., noncoherent with surface tide) because meanders in the Gulf Stream alter their precise location, phase, and amplitude. These results provide an explanation for anomalous onshore energy fluxes that were previously observed at the New Jersey shelf break and linked to the irregular generation of nonlinear internal waves.
    Description: We thank the National Science Foundation for support under Grant OCE-1061160 (ShelfIT) to the Massachusetts Institute of Technology (MIT) and under Grant OCE-1060430 to the Woods Hole Oceanographic Institution. PFJL and PJH also thank the Office of Naval Research for research support under Grants N00014-11-1-0701 (MURI-IODA), N00014-12-1-0944 (ONR6.2), and N00014-13-1-0518 (Multi-DA) to MIT.
    Description: 2017-06-14
    Keywords: Continental shelf/slope ; Inertia-gravity waves ; Internal waves ; Boundary currents ; Tides ; Baroclinic models
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  • 33
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 47 (2017): 85-100, doi:10.1175/JPO-D-15-0234.1.
    Description: Observations and analyses of two tidally recurring, oblique, internal hydraulic jumps at a stratified estuary mouth (Columbia River, Oregon/Washington) are presented. These hydraulic features have not previously been studied due to the challenges of both horizontally resolving the sharp gradients and temporally resolving their evolution in numerical models and traditional observation platforms. The jumps, both of which recurred during ebb, formed adjacent to two engineered lateral channel constrictions and were identified in marine radar image time series. Jump occurrence was corroborated by (i) a collocated sharp gradient in the surface currents measured via airborne along-track interferometric synthetic aperture radar and (ii) the transition from supercritical to subcritical flow in the cross-jump direction via shipborne velocity and density measurements. Using a two-layer approximation, observed jump angles at both lateral constrictions are shown to lie within the theoretical bounds given by the critical internal long-wave (Froude) angle and the arrested maximum-amplitude internal bore angle, respectively. Also, intratidal and intertidal variability of the jump angles are shown to be consistent with that expected from the two-layer model, applied to varying stratification and current speed over a range of tidal and river discharge conditions. Intratidal variability of the upchannel jump angle is similar under all observed conditions, whereas the downchannel jump angle shows an additional association with stratification and ebb velocity during the low discharge periods. The observations additionally indicate that the upchannel jump achieves a stable position that is collocated with a similarly oblique bathymetric slope.
    Description: We acknowledge the financial support of the Office of Naval Research under Awards N00014-10-1-0932 and N00014-13-1-0364.
    Description: 2017-07-04
    Keywords: Estuaries ; Baroclinic flows ; Internal waves ; Microwave observations ; Remote sensing
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  • 34
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Bulletin of the American Meteorological Society 97 (2016): 2305-2327, doi:10.1175/BAMS-D-15-00274.1.
    Description: Well-known problems trouble coupled general circulation models of the eastern Atlantic and Pacific Ocean basins. Model climates are significantly more symmetric about the equator than is observed. Model sea surface temperatures are biased warm south and southeast of the equator, and the atmosphere is too rainy within a band south of the equator. Near-coastal eastern equatorial SSTs are too warm, producing a zonal SST gradient in the Atlantic opposite in sign to that observed. The U.S. Climate Variability and Predictability Program (CLIVAR) Eastern Tropical Ocean Synthesis Working Group (WG) has pursued an updated assessment of coupled model SST biases, focusing on the surface energy balance components, on regional error sources from clouds, deep convection, winds, and ocean eddies; on the sensitivity to model resolution; and on remote impacts. Motivated by the assessment, the WG makes the following recommendations: 1) encourage identification of the specific parameterizations contributing to the biases in individual models, as these can be model dependent; 2) restrict multimodel intercomparisons to specific processes; 3) encourage development of high-resolution coupled models with a concurrent emphasis on parameterization development of finer-scale ocean and atmosphere features, including low clouds; 4) encourage further availability of all surface flux components from buoys, for longer continuous time periods, in persistently cloudy regions; and 5) focus on the eastern basin coastal oceanic upwelling regions, where further opportunities for observational–modeling synergism exist.
    Description: PZ, BK, and RM acknowledge support from NOAA Grant NA14OAR4310278, and PZ acknowledges support from NSF AGS-1233874. BM acknowledges support from the Regional and Global Climate Modeling Program of the U.S. Department of Energy’s Office of Science, Cooperative Agreement DE-FC02-97ER62402. PC acknowledges support from U.S. NSF Grants OCE-1334707 and AGS-1462127, and NOAA Grant NA11OAR4310154. PC also acknowledges support from China’s National Basic Research Priorities Programme (2013CB956204) and the Natural Science Foundation of China (41222037 and 41221063). TF acknowledges support from NSF Grant OCE-0745508 and NASA Grant NNX14AM71G. PB acknowledges support from the BMBF SACUS (03G0837A) project. TT and PB acknowledge support from the European Union Seventh Framework Programme (FP7 20072013) under Grant Agreement 603521 for the PREFACE Project. ES and ZW acknowledge support from NSF AGS-1338427, NOAA NA14OAR4310160, and NASA NNX14AM19G; and ES is grateful for further support from the National Monsoon Mission, Ministry of Earth Sciences, India.
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  • 35
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Atmospheric and Oceanic Technology 33 (2016): 2185-2203, doi:10.1175/JTECH-D-16-0095.1.
    Description: This study presents amended procedures to process and map data collected by pressure-sensor-equipped inverted echo sounders (PIESs) in western boundary current regions. The modifications to the existing methodology, applied to observations of the Kuroshio from a PIES array deployed northeast of Luzon, Philippines, consist of substituting a hydrography-based mean travel time field for the PIES-based mean field and using two distinct gravest empirical mode (GEM) lookup tables across the front that separate water masses of South China Sea and North Pacific origin. In addition, this study presents a method to use time-mean velocities from acoustic Doppler current profilers (ADCPs) to reference (or “level”) the PIES-recorded pressures in order to obtain time series of absolute geostrophic velocity. Results derived from the PIES observations processed with the hydrography-based mean field and two GEMs are compared with hydrographic profiles sampled by Seagliders during the PIES observation period and with current velocity measured concurrently by a collocated ADCP array. The updated processing scheme leads to a 41% error decrease in the determination of the thermocline depth across the current, a 22% error decrease in baroclinic current velocity shear, and a 61% error decrease in baroclinic volume transports. The absolute volume transport time series derived from the leveled PIES array compares well with that obtained directly from the ADCPs with a root-mean-square difference of 3.0 Sv (1 Sv ≡ 106 m3 s–1), which is mainly attributed to the influence of ageostrophic processes on the ADCP-measured velocities that cannot be calculated from the PIES observations.
    Description: The authors are supported by the Office of Naval Research (ONR) Departmental Research Initiative entitled Origins of the Kuroshio and Mindanao Currents (ONR Grant N00014-10-1-0397). MA was supported by ONR Grants N00014-15-12593 and N00014-16-1-2668. CL was supported by ONR Grant N00014-10-0308. SJ was supported by MOST Grants NSC 101-2611-M-002-018-MY3, MOST 103-2611-M-002-011, and MOST 105-2119-M-002-042.
    Description: 2017-04-05
    Keywords: Boundary currents ; Data processing ; In situ oceanic observations ; Inverse methods ; Optimization ; Time series
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  • 36
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Atmospheric and Oceanic Technology 34 (2017): 1713-1721, doi:10.1175/JTECH-D-16-0258.1.
    Description: Data collected with acoustic Doppler current profilers installed on CTD rosettes and lowered through the water column [lowered ADCP (LADCP) systems] are routinely used to derive full-depth profiles of ocean velocity. In addition to the uncertainties arising from random noise in the along-beam velocity measurements, LADCP-derived velocities are commonly contaminated by bias errors due to imperfectly measured instrument attitude (heading, pitch, and roll). Of particular concern are the heading measurements, because it is not usually feasible to calibrate the internal ADCP compasses with the instruments installed on a CTD rosette, away from the magnetic disturbances of the ship. Heading data from dual-headed LADCP systems, which consist of upward- and downward-pointing ADCPs installed on the same rosette, commonly indicate heading-dependent compass errors with amplitudes exceeding 10°. In an attempt to reduce LADCP velocity errors, several dozen profiles of simultaneous LADCP and magnetometer/accelerometer data were collected in the Gulf of Mexico. Agreement between the LADCP profiles and simultaneous shipboard velocity measurements improves significantly when the former are processed with external attitude measurements. Another set of LADCP profiles with external attitude data was collected in a region of the Arctic Ocean where the horizontal geomagnetic field is too weak for the ADCP compasses to work reliably. Good agreement between shipboard velocity measurements and Arctic LADCP profiles collected at magnetic dip angles exceeding and processed with external attitude measurements indicate that high-quality velocity profiles can be obtained close to the magnetic poles.
    Description: Part of this research was made possible by a grant from the Gulf of Mexico Research Initiative to support the Ecosystem Impacts of Oil and Gas Inputs to the Gulf (ECOGIG-2) research consortium. Funding for acquisition of the 2015 Arctic data was provided by NSF (1203473 and 1249133) and NOAA (NA15OAR4310155) under the NABOS-II program.
    Keywords: Ocean ; Arctic ; Algorithms ; In situ oceanic observations ; Measurements ; Profilers, oceanic
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  • 37
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Atmospheric and Oceanic Technology 34 (2017): 1679-1691, doi:10.1175/JTECH-D-16-0162.1.
    Description: For direction-finding high-frequency (HF) radar systems, the correct separation of backscattered spectral energy due to Bragg resonant waves from that due to more complex double-scattering represents a critical first step toward attaining accurate estimates of surface currents from the range-dependent radar backscatter. Existing methods to identify this “first order” region of the spectra, generally sufficient for lower-frequency radars and low-velocity or low-surface gravity wave conditions, are more likely to fail in higher-frequency systems or locations with more variable current, wave, or noise regimes, leading to elevated velocity errors. An alternative methodology is presented that uses a single and globally relevant smoothing length scale, careful pretreatment of the spectra, and marker-controlled watershed segmentation, an image processing technique, to separate areas of spectral energy due to surface currents from areas of spectral energy due to more complex scattering by the wave field or background noise present. Applied to a number of HF radar datasets with a range of operating frequencies and characteristic issues, the new methodology attains a higher percentage of successful first-order identification, particularly during complex current and wave conditions. As operational radar systems continue to expand to more systematically cover areas of high marine traffic, close approaches to ports and harbors, or offshore energy installations, use of this type of updated methodology will become increasingly important to attain accurate current estimates that serve both research and operational interests.
    Description: This analysis was supported by internal funds from the Woods Hole Oceanographic Institution.
    Description: 2018-02-11
    Keywords: Ocean circulation ; Waves, oceanic ; Data processing ; Radars/Radar observations ; Remote sensing ; Pattern detection
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  • 38
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    American Meteorological Society
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 46 (2016): 3599-3621, doi:10.1175/JPO-D-16-0085.1.
    Description: At continental margins, energetic deep-ocean eddies can transport shelf water offshore in filaments that wrap around the eddy. One example is that of Gulf Stream warm-core rings interacting with the Mid-Atlantic Bight shelf. The rate at which shelf water is exported in these filaments is a major unknown in regional budgets of volume, heat, and salt. This unknown transport is constrained using a series of idealized primitive equation numerical experiments wherein a surface-intensified anticyclonic eddy interacts with idealized shelf–slope topography. There is no shelfbreak front in these experiments, and shelf water is tracked using a passive tracer. When anticyclones interact with shelf–slope topography, they suffer apparent intrusions of shelf–slope water, resulting in a subsurface maximum in offshore transport. The simulations help construct an approximate model for the filament of exported water that originates inshore of any given isobath. This model is then used to derive an expression for the total volume of shelf–slope water transported by the eddy across that isobath. The transport scales with water depth, radius, and azimuthal velocity scale of the eddy. The resulting expression can be used with satellite-derived eddy properties to estimate approximate real-world transports ignoring the presence of a shelfbreak front. The expression assumes that the eddy’s edge is at the shelf break, a condition not always satisfied by real eddies.
    Description: The research presented here was funded by NSF Grants OCE-1059632 and OCE-1433953. Funding support from the Academic Programs Office, and WHOI is also gratefully acknowledged.
    Description: 2017-06-08
    Keywords: Continental shelf/slope ; Advection ; Dynamics ; Eddies ; Topographic effects
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  • 39
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 29 (2016): 8317-8331, doi:10.1175/JCLI-D-16-0109.1.
    Description: A simple analytic model is developed to represent the offshore decay of cold sea surface temperature (SST) signals that originate from wind-driven upwelling at a coastal boundary. The model couples an oceanic mixed layer to an atmospheric boundary layer through wind stress and air–sea heat exchange. The primary mechanism that controls SST is a balance between Ekman advection and air–sea exchange. The offshore penetration of the cold SST signal decays exponentially with a length scale that is the product of the ocean Ekman velocity and a time scale derived from the air–sea heat flux and the radiative balance in the atmospheric boundary layer. This cold SST signal imprints on the atmosphere in terms of both the boundary layer temperature and surface wind. Nonlinearities due to the feedback between SST and atmospheric wind, baroclinic instability, and thermal wind in the atmospheric boundary layer all slightly modify this linear theory. The decay scales diagnosed from two-dimensional and three-dimensional eddy-resolving numerical ocean models are in close agreement with the theory, demonstrating that the basic physics represented by the theory remain dominant even in these more complete systems. Analysis of climatological SST off the west coast of the United States also shows a decay of the cold SST anomaly with scale roughly in agreement with the theory.
    Description: MASwas supported by the Andrew W. Mellon Foundation Endowed Fund for Innovative Research and the National Science Foundation under Grant OCE-1433170 and PLR-1415489. NS was supported by the National Aeronautics and Space Administration under Grant NNX14AL83G, the Department of Energy, Office of Science Grant DE-SC0006766, and the Japan Agency for Marine-Earth Science and Technology as part of the JAMSTEC-IPRC Joint Investigations.
    Description: 2017-05-03
    Keywords: Coastal flows ; Ekman pumping/transport ; Ocean dynamics
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  • 40
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Bulletin of the American Meteorological Society 97 (2016): 1859–1884, doi:10.1175/BAMS-D-14-00197.1.
    Description: Air–Sea Interactions in the Northern Indian Ocean (ASIRI) is an international research effort (2013–17) aimed at understanding and quantifying coupled atmosphere–ocean dynamics of the Bay of Bengal (BoB) with relevance to Indian Ocean monsoons. Working collaboratively, more than 20 research institutions are acquiring field observations coupled with operational and high-resolution models to address scientific issues that have stymied the monsoon predictability. ASIRI combines new and mature observational technologies to resolve submesoscale to regional-scale currents and hydrophysical fields. These data reveal BoB’s sharp frontal features, submesoscale variability, low-salinity lenses and filaments, and shallow mixed layers, with relatively weak turbulent mixing. Observed physical features include energetic high-frequency internal waves in the southern BoB, energetic mesoscale and submesoscale features including an intrathermocline eddy in the central BoB, and a high-resolution view of the exchange along the periphery of Sri Lanka, which includes the 100-km-wide East India Coastal Current (EICC) carrying low-salinity water out of the BoB and an adjacent, broad northward flow (∼300 km wide) that carries high-salinity water into BoB during the northeast monsoon. Atmospheric boundary layer (ABL) observations during the decaying phase of the Madden–Julian oscillation (MJO) permit the study of multiscale atmospheric processes associated with non-MJO phenomena and their impacts on the marine boundary layer. Underway analyses that integrate observations and numerical simulations shed light on how air–sea interactions control the ABL and upper-ocean processes.
    Description: This work was sponsored by the U.S. Office of Naval Research (ONR) in an ONR Departmental Research Initiative (DRI), Air–Sea Interactions in Northern Indian Ocean (ASIRI), and in a Naval Research Laboratory project, Effects of Bay of Bengal Freshwater Flux on Indian Ocean Monsoon (EBOB). ASIRI–RAWI was funded under the NASCar DRI of the ONR. The Indian component of the program, Ocean Mixing and Monsoons (OMM), was supported by the Ministry of Earth Sciences of India.
    Description: 2017-04-22
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  • 41
    Publication Date: 2022-05-26
    Description: Author Posting. © American Meteorological Society, 2017. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 30 (2017): 9679-9702, doi:10.1175/JCLI-D-16-0707.1.
    Description: The North Atlantic atmospheric circulation response to the meridional shifts of the Gulf Stream (GS) path is examined using a large ensemble of high-resolution hemispheric-scale Weather Research and Forecasting Model simulations. The model is forced with a broad range of wintertime sea surface temperature (SST) anomalies derived from a lag regression on a GS index. The primary result of the model experiments, supported in part by an independent analysis of a reanalysis dataset, is that the large-scale quasi-steady North Atlantic circulation response is remarkably nonlinear about the sign and amplitude of the SST anomaly chosen over a wide range of GS shift scenarios. The nonlinear response prevails over the weak linear response and resembles the negative North Atlantic Oscillation (NAO), the leading intrinsic mode of variability in the model and the observations. Further analysis of the associated dynamics reveals that the nonlinear responses are accompanied by the shift of the North Atlantic eddy-driven jet, which is reinforced, with nearly equal importance, by the high-frequency transient eddy feedback and the low-frequency wave-breaking events. Additional sensitivity simulations confirm that the nonlinearity of the circulation response is a robust feature found over the broad parameter space encompassing not only the varied SST but also the absence/presence of tropical influence, the varying lateral boundary conditions, and the initialization scheme. The result highlights the fundamental importance of the intrinsically nonlinear transient eddy dynamics and the eddy–mean flow interactions in generating the nonlinear downstream response to the meridional shifts in the Gulf Stream.
    Description: The authors are grateful for the support from NASA (NNX13AM59G) and the NSF (AGS-1355339, OCE-1419235).
    Description: 2018-05-07
    Keywords: North Atlantic Ocean ; Blocking ; North Atlantic Oscillation ; Atmosphere-ocean interaction ; Regional models ; Climate variability
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  • 42
    Publication Date: 2017-01-01
    Print ISSN: 0065-9401
    Electronic ISSN: 1943-3646
    Topics: Geography , Geosciences , Physics
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  • 43
    Publication Date: 2017-01-01
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  • 44
    Publication Date: 2017-01-01
    Print ISSN: 0065-9401
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  • 45
    Publication Date: 2017-01-01
    Description: In situ observations of cloud properties made by airborne probes play a critical role in ice cloud research through their role in process studies, parameterization development, and evaluation of simulations and remote sensing retrievals. To determine how cloud properties vary with environmental conditions, in situ data collected during different field projects processed by different groups must be used. However, because of the diverse algorithms and codes that are used to process measurements, it can be challenging to compare the results. Therefore it is vital to understand both the limitations of specific probes and uncertainties introduced by processing algorithms. Since there is currently no universally accepted framework regarding how in situ measurements should be processed, there is a need for a general reference that describes the most commonly applied algorithms along with their strengths and weaknesses. Methods used to process data from bulk water probes, single-particle light-scattering spectrometers and cloud-imaging probes are reviewed herein, with emphasis on measurements of the ice phase. Particular attention is paid to how uncertainties, caveats, and assumptions in processing algorithms affect derived products since there is currently no consensus on the optimal way of analyzing data. Recommendations for improving the analysis and interpretation of in situ data include the following: establishment of a common reference library of individual processing algorithms, better documentation of assumptions used in these algorithms, development and maintenance of sustainable community software for processing in situ observations, and more studies that compare different algorithms with the same benchmark datasets.
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  • 46
    Publication Date: 2017-01-01
    Description: It has been known that aerosol particles act as nuclei for ice formation for over a century and a half (see Dufour). Initial attempts to understand the nature of these ice nucleating particles were optical and electron microscope inspection of inclusions at the center of a crystal (see Isono; Kumai). Only within the last few decades has instrumentation to extract ice crystals from clouds and analyze the residual material after sublimation of condensed-phase water been available (see Cziczo and Froyd). Techniques to ascertain the ice nucleating potential of atmospheric aerosols have only been in place for a similar amount of time (see DeMott et al.). In this chapter the history of measurements of ice nucleating particles, both in the field and complementary studies in the laboratory, are reviewed. Remaining uncertainties and artifacts associated with measurements are described and suggestions for future areas of improvement are made.
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  • 47
    Publication Date: 2017-01-01
    Description: The life cycle of individual (initially line shaped) contrails behind aircraft and of contrail cirrus (aged contrails mixed with other ice clouds) is described. The full contrail life cycle is covered, from ice formation for given water, heat, and particulate emissions; to changes in the jet, wake, and dispersion phases; through final sublimation or sedimentation. Contrail properties are deduced from various in situ, remote sensing, and model studies. Aerodynamically induced contrails and distrails are explained briefly. Contrails form both in clear air and inside cirrus. Young contrails consume most of the ambient ice supersaturation. Optical properties of contrails are age and humidity dependent. Contrail occurrence and radiative forcing depends on the ambient Earth–atmosphere conditions. Contrail cirrus seems to be optically thicker than assessed previously and may not only increase cirrus coverage but also thicken existing cirrus. Some observational constraints for contrail cirrus occurrence and radiative forcing are derived. Key parameters controlling contrail properties—besides aircraft and fuel properties, ambient pressure, temperature, and humidity—are the number of ice particles per flight distance surviving the wake vortex phase, the contrail depth, and particle sedimentation, wind shear, turbulence, and vertical motions controlling contrail dispersion. The climate impact of contrails depends among other things on the ratio of shortwave to longwave radiative forcing (RF) and on the efficacy with which contrail RF contributes to surface warming. Several open issues are identified, including renucleation from residuals of sublimated contrail ice particles.
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  • 48
    Publication Date: 2017-01-01
    Description: Ice-phase precipitation occurs at Earth’s surface and may include various types of pristine crystals, rimed crystals, freezing droplets, secondary crystals, aggregates, graupel, hail, or combinations of any of these. Formation of ice-phase precipitation is directly related to environmental and cloud meteorological parameters that include available moisture, temperature, and three-dimensional wind speed and turbulence, as well as processes related to nucleation, cooling rate, and microphysics. Cloud microphysical parameters in the numerical models are resolved based on various processes such as nucleation, mixing, collision and coalescence, accretion, riming, secondary ice particle generation, turbulence, and cooling processes. These processes are usually parameterized based on assumed particle size distributions and ice crystal microphysical parameters such as mass, size, and number and mass density. Microphysical algorithms in the numerical models are developed based on their need for applications. Observations of ice-phase precipitation are performed using in situ and remote sensing platforms, including radars and satellite-based systems. Because of the low density of snow particles with small ice water content, their measurements and predictions at the surface can include large uncertainties. Wind and turbulence affecting collection efficiency of the sensors, calibration issues, and sensitivity of ground-based in situ observations of snow are important challenges to assessing the snow precipitation. This chapter’s goals are to provide an overview for accurately measuring and predicting ice-phase precipitation. The processes within and below cloud that affect falling snow, as well as the known sources of error that affect understanding and prediction of these processes, are discussed.
    Print ISSN: 0065-9401
    Electronic ISSN: 1943-3646
    Topics: Geography , Geosciences , Physics
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  • 49
    Publication Date: 2017-01-01
    Description: Ice fog is a natural, outdoor cloud laboratory that provides an excellent opportunity to study ice microphysical processes. Ice crystals in fog are formed through similar pathways as those in elevated clouds; that is, cloud condensation or ice nuclei are activated in an atmosphere supersaturated with respect to liquid water or ice. The primary differences between surface and elevated ice clouds are related to the sources of water vapor, the cooling mechanisms and dynamical processes leading to supersaturation, and the microphysical characteristics of the nuclei that affect ice fog crystal physical properties. As with any fog, its presence can be a hazard for ground or airborne traffic because of poor visibility and icing. In addition, ice fog plays a role in climate change by modulating the heat and moisture budgets. Ice fog wintertime occurrence in many parts of the world can have a significant impact on the environment. Global climate models need to accurately account for the temporal and spatial microphysical and optical properties of ice fog, as do weather forecast models. The primary handicap is the lack of adequate information on nucleation processes and microphysical algorithms that accurately represent glaciation of supercooled water fog. This chapter summarizes the current understanding of ice fog formation and evolution; discusses operating principles, limitations, and uncertainties associated with the instruments used to measure ice fog microphysical properties; describes the prediction of ice fog by the numerical forecast models and physical parameterizations used in climate models; identifies the outstanding questions to be resolved; and lists recommended actions to address and solve these questions.
    Print ISSN: 0065-9401
    Electronic ISSN: 1943-3646
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  • 50
    Publication Date: 2017-01-01
    Description: State-of-the-art remote sensing techniques applicable to the investigation of ice formation and evolution are described. Ground-based and spaceborne measurements with lidar, radar, and radiometric techniques are discussed together with a global view on past and ongoing remote sensing measurement campaigns concerned with the study of ice formation and evolution. This chapter has the intention of a literature study and should illustrate the major efforts that are currently taken in the field of remote sensing of atmospheric ice. Since other chapters of this monograph mainly focus on aircraft in situ measurements, special emphasis is put on active remote sensing instruments and synergies between aircraft in situ measurements and passive remote sensing methods. The chapter concentrates on homogeneous and heterogeneous ice formation in the troposphere because this is a major topic of this monograph. Furthermore, methods that deliver direct, process-level information about ice formation are elaborated with a special emphasis on active remote sensing methods. Passive remote sensing methods are also dealt with but only in the context of synergy with aircraft in situ measurements.
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  • 51
    Publication Date: 2017-01-01
    Description: Ice particle formation in tropospheric clouds significantly changes cloud radiative and microphysical properties. Ice nucleation in the troposphere via homogeneous freezing occurs at temperatures lower than −38°C and relative humidity with respect to ice above 140%. In the absence of these conditions, ice formation can proceed via heterogeneous nucleation aided by aerosol particles known as ice nucleating particles (INPs). In this chapter, new developments in identifying the heterogeneous freezing mechanisms, atmospheric relevance, uncertainties, and unknowns about INPs are described. The change in conventional wisdom regarding the requirements of INPs as new studies discover physical and chemical properties of these particles is explained. INP sources and known reasons for their ice nucleating properties are presented. The need for more studies to systematically identify particle properties that facilitate ice nucleation is highlighted. The atmospheric relevance of long-range transport, aerosol aging, and coating studies (in the laboratory) of INPs are also presented. Possible mechanisms for processes that change the ice nucleating potential of INPs and the corresponding challenges in understanding and applying these in models are discussed. How primary ice nucleation affects total ice crystal number concentrations in clouds and the discrepancy between INP concentrations and ice crystal number concentrations are presented. Finally, limitations of parameterizing INPs and of models in representing known and unknown processes related to heterogeneous ice nucleation processes are discussed.
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  • 52
    Publication Date: 2017-01-01
    Description: The goal of this chapter is to synthesize information about what is now known about one of the three main types of clouds, cirrus, and to identify areas where more knowledge is needed. Cirrus clouds, composed of ice particles, form in the upper troposphere, where temperatures are generally below −30°C. Satellite observations show that the maximum-occurrence frequency of cirrus is near the tropics, with a large latitudinal movement seasonally. In situ measurements obtained over a wide range of cirrus types, formation mechanisms, temperatures, and geographical locations indicate that the ice water content and particle size generally decrease with decreasing temperature, whereas the ice particle concentration is nearly constant or increases slightly with decreasing temperature. High ice concentrations, sometimes observed in strong updrafts, result from homogeneous nucleation. The satellite-based and in situ measurements indicate that cirrus ice crystals typically differ from the simple, idealized geometry for smooth hexagonal shapes, indicating complexity and/or surface roughness. Their shapes significantly impact cirrus radiative properties and feedbacks to climate. Cirrus clouds, one of the most uncertain components of general circulation models (GCM), pose one of the greatest challenges in predicting the rate and geographical pattern of climate change. Improved measurements of the properties and size distributions and surface structure of small ice crystals (about 20 μm) and identifying the dominant ice nucleation process (heterogeneous versus homogeneous ice nucleation) under different cloud dynamical forcings will lead to a better representation of their properties in GCM and in modeling their current and future effects on climate.
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  • 53
    facet.materialart.
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    International Union of Crystallography (IUCr)
    In: IUCrJ
    Publication Date: 2017-09-02
    Keywords: bond-valence methodcoordination numberscrystal radiibond-valence parametersbond softness
    Electronic ISSN: 2052-2525
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  • 54
    facet.materialart.
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    International Union of Crystallography (IUCr)
    In: IUCrJ
    Publication Date: 2017-09-02
    Keywords: editorialIUCr Journals
    Electronic ISSN: 2052-2525
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  • 55
    Publication Date: 2017-09-02
    Description: Glycine is the simplest and most polymorphic amino acid, with five phases having been structurally characterized at atmospheric or high pressure. A sixth form, the elusive ζ phase, was discovered over a decade ago as a short-lived intermediate which formed as the high-pressure ∊ phase transformed to the γ form on decompression. However, its structure has remained unsolved. We now report the structure of the ζ phase, which was trapped at 100 K enabling neutron powder diffraction data to be obtained. The structure was solved using the results of a crystal structure prediction procedure based on fully ab initio energy calculations combined with a genetic algorithm for searching phase space. We show that the fate of ζ-glycine depends on its thermal history: although at room temperature it transforms back to the γ phase, warming the sample from 100 K to room temperature yielded β-glycine, the least stable of the known ambient-pressure polymorphs.
    Keywords: amino acidscrystal structure predictionpolymorphismneutron diffractionphase transitionscrystallization under non-ambient conditions
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  • 56
    Publication Date: 2017-09-02
    Description: Single-particle cryogenic electron microscopy (cryo-EM) can now yield near-atomic resolution structures of biological complexes. However, the reference-based alignment algorithms commonly used in cryo-EM suffer from reference bias, limiting their applicability (also known as the `Einstein from random noise' problem). Low-dose cryo-EM therefore requires robust and objective approaches to reveal the structural information contained in the extremely noisy data, especially when dealing with small structures. A reference-free pipeline is presented for obtaining near-atomic resolution three-dimensional reconstructions from heterogeneous (`four-dimensional') cryo-EM data sets. The methodologies integrated in this pipeline include a posteriori camera correction, movie-based full-data-set contrast transfer function determination, movie-alignment algorithms, (Fourier-space) multivariate statistical data compression and unsupervised classification, `random-startup' three-dimensional reconstructions, four-dimensional structural refinements and Fourier shell correlation criteria for evaluating anisotropic resolution. The procedures exclusively use information emerging from the data set itself, without external `starting models'. Euler-angle assignments are performed by angular reconstitution rather than by the inherently slower projection-matching approaches. The comprehensive `ABC-4D' pipeline is based on the two-dimensional reference-free `alignment by classification' (ABC) approach, where similar images in similar orientations are grouped by unsupervised classification. Some fundamental differences between X-ray crystallography versus single-particle cryo-EM data collection and data processing are discussed. The structure of the giant haemoglobin from Lumbricus terrestris at a global resolution of ∼3.8 Å is presented as an example of the use of the ABC-4D procedure.
    Keywords: alignment by classificationangular reconstitutionMSAworm haemoglobincryo-EM
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  • 57
    Publication Date: 2017-09-02
    Description: The mechanical and magnetic properties of Ni–Mn–Sb intermetallic compounds are closely related to the martensitic transformation and martensite variant organization. However, studies of these issues are very limited. Thus, a thorough crystallographic investigation of the martensitic transformation orientation relationship (OR), the transformation deformation and their impact on the variant organization of an Ni50Mn38Sb12 alloy using scanning electron microscopy/electron backscatter diffraction (SEM/EBSD) was conducted in this work. It is shown that the martensite variants are hierarchically organized into plates, each possessing four distinct twin-related variants, and the plates into plate colonies, each containing four distinct plates delimited by compatible and incompatible plate interfaces. Such a characteristic organization is produced by the martensitic transformation. It is revealed that the transformation obeys the Pitsch relation ({0{\overline 1}{\overline 1}}A // {2{\overline 2}{\overline 1}}M and 〈0{\overline 1}1〉A // 〈{\overline 1}{\overline 2}2〉M; the subscripts A and M refer to austenite and martensite, respectively). The type I twinning plane K1 of the intra-plate variants and the compatible plate interface plane correspond to the respective orientation relationship planes {0{\overline 1}{\overline 1}}A and {0{\overline 1}{\overline 1}}A of austenite. The three {0{\overline 1}{\overline 1}}A planes possessed by each pair of compatible plates, one corresponding to the compatible plate interface and the other two to the variants in the two plates, are interrelated by 60° and belong to a single 〈11{\overline 1}〉A axis zone. The {0{\overline 1}{\overline 1}}A planes representing the two pairs of compatible plates in each plate colony belong to two 〈11{\overline 1}〉A axis zones having one {0{\overline 1}{\overline 1}}A plane in common. This common plane defines the compatible plate interfaces of the two pairs of plates. The transformation strains to form the variants in the compatible plates are compatible and demonstrate an edge-to-edge character. Thus, such plates should nucleate and grow simultaneously. On the other hand, the strains to form the variants in the incompatible plates are incompatible, so they nucleate and grow separately until they meet during the transformation. The results of the present work provide comprehensive information on the martensitic transformation of Ni–Mn–Sb intermetallic compounds and its impact on martensite variant organization.
    Keywords: Ni–Mn–Sb intermetallic compoundsmartensitic transformationorientation relationshipvariant organizationelectron backscatter diffraction (EBSD)crystallography
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  • 58
    Publication Date: 2017-09-02
    Description: Based on first-principles calculations, the relationship between molecular packing and charge-transport parameters has been investigated and analysed in detail. It is found that the crystal packing forces in the flexible organic molecule 4-(1,2,2-triphenylvinyl)aniline salicylaldehyde hydrazone (A) can apparently overcome the dynamic intramolecular rotations and the intramolecular steric repulsion, effectively enhancing the molecular rigidity and decreasing the internal reorganization energy. The conducting properties of A have also been simulated within the framework of hopping models, and the calculation results show that the intrinsic electron mobility in A is much higher than the corresponding intrinsic hole mobility. These theoretical investigations provide guidance for the efficient and targeted control of the molecular packing and charge-transport properties of organic small-molecule semiconductors and conjugated polymeric materials.
    Keywords: mobilityreorganization energypacking forcesrigidityflexible moleculescharge-transport properties
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  • 59
    Publication Date: 2017-09-02
    Description: Energy materials form the central part of energy devices. An essential part of their function is the ability to reversibly host charge or energy carriers, and analysis of their phase composition and structure in real time under non-equilibrium conditions is mandatory for a full understanding of their atomic-scale functional mechanism. Real-time powder diffraction is increasingly being applied for this purpose, forming a critical step in the strategic chemical engineering of materials with improved behaviour. This topical review gives examples of real-time analysis using powder diffraction of rechargeable battery electrodes and porous sorbent materials used for the separation and storage of energy-relevant gases to demonstrate advances in the insights which can be gained into their atomic-scale function.
    Keywords: real-time studiesoperando studiespowder diffractionfunctional materialsenergy materials
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  • 60
    Publication Date: 2017-09-02
    Description: Single-particle imaging with X-ray free-electron lasers (XFELs) has the potential to provide structural information at atomic resolution for non-crystalline biomolecules. This potential exists because ultra-short intense pulses can produce interpretable diffraction data notwithstanding radiation damage. This paper explores the impact of pulse duration on the interpretability of diffraction data using comprehensive and realistic simulations of an imaging experiment at the European X-ray Free-Electron Laser. It is found that the optimal pulse duration for molecules with a few thousand atoms at 5 keV lies between 3 and 9 fs.
    Keywords: single-particle imagingX-ray free-electron laserssimulationsdiffractionscattering
    Electronic ISSN: 2052-2525
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  • 61
    Publication Date: 2017-08-11
    Description: Due to their high technological and geological relevance, silicates are one of the most studied classes of inorganic compounds. Under ambient conditions, the silicon in silicates is almost exclusively coordinated by four oxygen atoms, while high-pressure treatment normally results in an increase in the coordination from four- to sixfold. Reported here is a high-pressure single-crystal X-ray diffraction study of danburite, CaB2Si2O8, the first compound showing a step-wise transition of Si coordination from tetrahedral to octahedral through a trigonal bipyramid. Along the compression, the Si2O7 groups of danburite first transform into chains of vertice-sharing SiO5 trigonal bipyramids (danburite-II) and later into chains of edge-sharing SiO6 octahedra (danburite-III). It is suggested that the unusual formation of an SiO5 configuration is a consequence of filling up the pentacoordinated voids in the distorted hexagonal close packing of danburite-II.
    Keywords: phase transitionspolymorphismfive-coordinate silicondanburitesilicates
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  • 62
    facet.materialart.
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    International Union of Crystallography (IUCr)
    In: IUCrJ
    Publication Date: 2017-09-02
    Keywords: serial femtosecond crystallographyanomalous signaldata qualityde novo phasingXFELs
    Electronic ISSN: 2052-2525
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  • 63
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    International Union of Crystallography (IUCr)
    In: IUCrJ
    Publication Date: 2017-02-24
    Keywords: metal–organic frameworkshydrogen storagebinding affinitytailored pore geometrydispersive interactions
    Electronic ISSN: 2052-2525
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  • 64
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    International Union of Crystallography (IUCr)
    In: IUCrJ
    Publication Date: 2017-02-24
    Keywords: high-pressure barium phasesincommensurately modulated structuresBa IVbatomic density waveshost–guest structures
    Electronic ISSN: 2052-2525
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  • 65
    Publication Date: 2017-02-24
    Description: Peptidoglycan is a giant molecule that forms the cell wall that surrounds bacterial cells. It is composed of alternating N-acetylglucosamine (NAG) and N-acetylmuramic acid (NAM) residues connected by β-(1,4)-glycosidic bonds and cross-linked with short polypeptide chains. Owing to the increasing antibiotic resistance against drugs targeting peptidoglycan synthesis, studies of enzymes involved in the degradation of peptidoglycan, such as N-acetylglucosaminidases, may expose new, valuable drug targets. The scientific challenge addressed here is how lysozymes, muramidases which are likely to be the most studied enzymes ever, and bacterial N-acetylglucosaminidases discriminate between two glycosidic bonds that are different in sequence yet chemically equivalent in the same NAG-NAM polymers. In spite of more than fifty years of structural studies of lysozyme, it is still not known how the enzyme selects the bond to be cleaved. Using macromolecular crystallography, chemical synthesis and molecular modelling, this study explains how these two groups of enzymes based on an equivalent structural core exhibit a difference in selectivity. The crystal structures of Staphylococcus aureus N-acetylglucosaminidase autolysin E (AtlE) alone and in complex with fragments of peptidoglycan revealed that N-acetylglucosaminidases and muramidases approach the substrate at alternate glycosidic bond positions from opposite sides. The recognition pocket for NAM residues in the active site of N-acetylglucosaminidases may make them a suitable drug target.
    Keywords: Staphylococcus aureusautolysinssubstrate specificityN-acetylglucosaminidasemuramidaseslysozyme
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  • 66
    Publication Date: 2017-06-15
    Description: The crystal structure uniquely imparts the specific properties of a material, and thus provides the starting point for any quantitative understanding of thermoelectric properties. Cu2−xSe is an intensely studied high performing, non-toxic and cheap thermoelectric material, and here for the first time, the average structure of β-Cu2−xSe is reported based on analysis of multi-temperature single-crystal X-ray diffraction data. It consists of Se–Cu layers with additional copper between every alternate layer. The structural changes during the peculiar zT enhancing phase transition mainly consist of changes in the inter-layer distance coupled with subtle Cu migration. Just prior to the transition the structure exhibits strong negative thermal expansion due to the reordering of Cu atoms, when approached from low temperatures. The phase transition is fully reversible and group–subgroup symmetry relations are derived that relate the low-temperature β-phase to the high-temperature α-phase. Weak superstructure reflections are observed and a possible Cu ordering is proposed. The structural rearrangement may have a significant impact on the band structure and the Cu rearrangement may also be linked to an entropy increase. Both factors potentially contribute to the extraordinary zT enhancement across the phase transition.
    Keywords: thermoelectricsnegative thermal expansionproperties of solidsinorganic materials
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  • 67
    Publication Date: 2017-06-06
    Description: There has been significant recent interest in differentiating multicomponent solid forms, such as salts and cocrystals, and, where appropriate, in determining the position of the proton in the X—H...A—Y X−...H—A+—Y continuum in these systems, owing to the direct relationship of this property to the clinical, regulatory and legal requirements for an active pharmaceutical ingredient (API). In the present study, solid forms of simple cocrystals/salts were investigated by high-field (700 MHz) solid-state NMR (ssNMR) using samples with naturally abundant 15N nuclei. Four model compounds in a series of prototypical salt/cocrystal/continuum systems exhibiting {PyN...H—O—}/{PyN+—H...O−} hydrogen bonds (Py is pyridine) were selected and prepared. The crystal structures were determined at both low and room temperature using X-ray diffraction. The H-atom positions were determined by measuring the 15N—1H distances through 15N-1H dipolar interactions using two-dimensional inversely proton-detected cross polarization with variable contact-time (invCP-VC) 1H→15N→1H experiments at ultrafast (νR ≥ 60–70 kHz) magic angle spinning (MAS) frequency. It is observed that this method is sensitive enough to determine the proton position even in a continuum where an ambiguity of terminology for the solid form often arises. This work, while carried out on simple systems, has implications in the pharmaceutical industry where the salt/cocrystal/continuum condition of APIs is considered seriously.
    Keywords: saltcocrystalcontinuumnatural abundancesolid-state NMRX-ray diffraction
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  • 68
    Publication Date: 2017-06-15
    Description: The conceptual relationship between crystal reactivity, stability and metastability, solubility and morphology on the one hand and shape, charge distribution, chirality and distribution of functional groups over the molecular surfaces on the other hand is discussed, via a number of examples coming from three decades of research in the field of crystal engineering at the University of Bologna. The bottom-up preparation of mixed crystals, co-crystals and photoreactive materials starting from molecular building blocks across the borders of organic, organometallic and metalorganic chemistry is recounted.
    Keywords: cocrystalssolid solutionspolymorphismluminescencechirality
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  • 69
    Publication Date: 2017-06-15
    Description: A deep machine-learning technique based on a convolutional neural network (CNN) is introduced. It has been used for the classification of powder X-ray diffraction (XRD) patterns in terms of crystal system, extinction group and space group. About 150 000 powder XRD patterns were collected and used as input for the CNN with no handcrafted engineering involved, and thereby an appropriate CNN architecture was obtained that allowed determination of the crystal system, extinction group and space group. In sharp contrast with the traditional use of powder XRD pattern analysis, the CNN never treats powder XRD patterns as a deconvoluted and discrete peak position or as intensity data, but instead the XRD patterns are regarded as nothing but a pattern similar to a picture. The CNN interprets features that humans cannot recognize in a powder XRD pattern. As a result, accuracy levels of 81.14, 83.83 and 94.99% were achieved for the space-group, extinction-group and crystal-system classifications, respectively. The well trained CNN was then used for symmetry identification of unknown novel inorganic compounds.
    Keywords: convolutional neural network (CNN)artificial neural network (ANN)powder X-ray diffractioncrystal systeminorganic materialscomputational modellingcrystal structure predictionproperties of solids
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  • 70
    Publication Date: 2017-06-17
    Description: Microbial nitrite reductases are denitrifying enzymes that are a major component of the global nitrogen cycle. Multiple structures measured from one crystal (MSOX data) of copper nitrite reductase at 240 K, together with molecular-dynamics simulations, have revealed protein dynamics at the type 2 copper site that are significant for its catalytic properties and for the entry and exit of solvent or ligands to and from the active site. Molecular-dynamics simulations were performed using different protonation states of the key catalytic residues (AspCAT and HisCAT) involved in the nitrite-reduction mechanism of this enzyme. Taken together, the crystal structures and simulations show that the AspCAT protonation state strongly influences the active-site solvent accessibility, while the dynamics of the active-site `capping residue' (IleCAT), a determinant of ligand binding, are influenced both by temperature and by the protonation state of AspCAT. A previously unobserved conformation of IleCAT is seen in the elevated temperature series compared with 100 K structures. DFT calculations also show that the loss of a bound water ligand at the active site during the MSOX series is consistent with reduction of the type 2 Cu atom.
    Keywords: serial crystallographyhigh temperaturecatalysismolecular dynamicsdensity functional theorydenitrificationcopper nitrite reductaseradiolysissynchrotron radiation
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  • 71
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    International Union of Crystallography (IUCr)
    In: IUCrJ
    Publication Date: 2017-07-01
    Keywords: X-ray lasersXFELsbiologystructuredynamics
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  • 72
    Publication Date: 2017-07-01
    Description: Traditional synthesis of metal–organic frameworks (MOFs) involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a `solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs), rather than an organic solvent, in `ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.
    Keywords: metal–organic frameworkMOFionic liquidionothermal synthesistemplate
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  • 73
    Publication Date: 2017-07-05
    Description: For martensitic transformations the macroscopic crystal strain is directly related to the corresponding structural rearrangement at the microscopic level. In situ optical microscopy observations of the interface migration and the change in crystal shape during a displacive single crystal to single crystal transformation can contribute significantly to understanding the mechanism of the process at the atomic scale. This is illustrated for the dehydration of samarium oxalate decahydrate in a study combining optical microscopy and single-crystal X-ray diffraction.
    Keywords: thermomechanical effectssolid-state chemical reactionsmartensitic transformationstopotactic transformationsmaterials modellingphase transitionscrystal morphologyproperties of solidsoptical microscopy
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  • 74
    Publication Date: 2017-07-05
    Description: The application domain of accurate and efficient CE-B3LYP and CE-HF model energies for intermolecular interactions in molecular crystals is extended by calibration against density functional results for 1794 molecule/ion pairs extracted from 171 crystal structures. The mean absolute deviation of CE-B3LYP model energies from DFT values is a modest 2.4 kJ mol−1 for pairwise energies that span a range of 3.75 MJ mol−1. The new sets of scale factors determined by fitting to counterpoise-corrected DFT calculations result in minimal changes from previous energy values. Coupled with the use of separate polarizabilities for interactions involving monatomic ions, these model energies can now be applied with confidence to a vast number of molecular crystals. Energy frameworks have been enhanced to represent the destabilizing interactions that are important for molecules with large dipole moments and organic salts. Applications to a variety of molecular crystals are presented in detail to highlight the utility and promise of these tools.
    Keywords: CrystalExplorermodel energiesenergy frameworkscoordination compoundsopen-shell systemsintermolecular interactions
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  • 75
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    International Union of Crystallography (IUCr)
    In: IUCrJ
    Publication Date: 2017-08-04
    Description: Based on a description of bond valence as a function of valence electron density, a systematic bond softness sensitive approach to determine bond-valence parameters and related quantities such as coordination numbers is elaborated and applied to determine bond-valence parameters for 706 cation–anion pairs. While the approach is closely related to the earlier softBV parameter set, the new softNC1 parameters proposed in this work may be simpler to apply in plausibility checks of crystal structures, as they follow the first coordination shell convention. The performance of this softNC1 bond-valence parameter set is compared with that of the previously derived softBV parameter set that also factors in contributions from higher coordination shells, and with a benchmarking parameter set that has been optimized following the conventional choice of a universal value of the bond-valence parameter b. The results show that a systematic adaptation of the bond-valence parameters to the bond softness leads to a significant improvement in the bond-valence parameters, particularly for bonds involving soft anions, and is safer than individual free refinements of both R0 and b from a limited number of reference cation environments.
    Keywords: bond-valence methodcoordination numberscrystal radiibond-valence parametersbond softness
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  • 76
    Publication Date: 2017-08-09
    Description: The progress in X-ray microbeam applications using synchrotron radiation is beneficial to structure determination from macromolecular microcrystals such as small in meso crystals. However, the high intensity of microbeams causes severe radiation damage, which worsens both the statistical quality of diffraction data and their resolution, and in the worst cases results in the failure of structure determination. Even in the event of successful structure determination, site-specific damage can lead to the misinterpretation of structural features. In order to overcome this issue, technological developments in sample handling and delivery, data-collection strategy and data processing have been made. For a few crystals with dimensions of the order of 10 µm, an elegant two-step scanning strategy works well. For smaller samples, the development of a novel method to analyze multiple isomorphous microcrystals was motivated by the success of serial femtosecond crystallography with X-ray free-electron lasers. This method overcame the radiation-dose limit in diffraction data collection by using a sufficient number of crystals. Here, important technologies and the future prospects for microcrystallography are discussed.
    Keywords: protein microcrystallographymulti-point data collectionmulti-crystal data collectionserial synchrotron crystallography
    Electronic ISSN: 2052-2525
    Topics: Geosciences , Physics
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  • 77
    Publication Date: 2017-08-09
    Description: An algorithm for modelling the background for each Bragg reflection in a series of X-ray diffraction images containing Debye–Scherrer diffraction from ice in the sample is presented. The method involves the use of a global background model which is generated from the complete X-ray diffraction data set. Fitting of this model to the background pixels is then performed for each reflection independently. The algorithm uses a static background model that does not vary over the course of the scan. The greatest improvement can be expected for data where ice rings are present throughout the data set and the local background shape at the size of a spot on the detector does not exhibit large time-dependent variation. However, the algorithm has been applied to data sets whose background showed large pixel variations (variance/mean 〉 2) and has been shown to improve the results of processing for these data sets. It is shown that the use of a simple flat-background model as in traditional integration programs causes systematic bias in the background determination at ice-ring resolutions, resulting in an overestimation of reflection intensities at the peaks of the ice rings and an underestimation of reflection intensities either side of the ice ring. The new global background-model algorithm presented here corrects for this bias, resulting in a noticeable improvement in R factors following refinement.
    Keywords: protein structurerefinementX-ray crystallographyice ringsdata processingdata analysisX-ray diffractiondata qualityAUSPEXDIALS
    Electronic ISSN: 2052-2525
    Topics: Geosciences , Physics
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  • 78
    Publication Date: 2017-08-09
    Description: Small-angle X-ray scattering (SAXS) is an established technique that provides low-resolution structural information on macromolecular solutions. Recent decades have witnessed significant progress in both experimental facilities and in novel data-analysis approaches, making SAXS a mainstream method for structural biology. The technique is routinely applied to directly reconstruct low-resolution shapes of proteins and to generate atomistic models of macromolecular assemblies using hybrid approaches. Very importantly, SAXS is capable of yielding structural information on systems with size and conformational polydispersity, including highly flexible objects. In addition, utilizing high-flux synchrotron facilities, time-resolved SAXS allows analysis of kinetic processes over time ranges from microseconds to hours. Dedicated bioSAXS beamlines now offer fully automated data-collection and analysis pipelines, where analysis and modelling is conducted on the fly. This enables SAXS to be employed as a high-throughput method to rapidly screen various sample conditions and additives. The growing SAXS user community is supported by developments in data and model archiving and quality criteria. This review illustrates the latest developments in SAXS, in particular highlighting time-resolved applications aimed at flexible and evolving systems.
    Keywords: small-angle X-ray scatteringstructural modellingtime-resolved SAXS
    Electronic ISSN: 2052-2525
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  • 79
    facet.materialart.
    Unknown
    International Union of Crystallography (IUCr)
    In: IUCrJ
    Publication Date: 2017-08-09
    Description: Understanding the protein main-chain conformational space forms the basis for the modelling of protein structures and for the validation of models derived from structural biology techniques. Presented here is a novel idea for a three-dimensional distance geometry-based metric to account for the fine details of protein backbone conformations. The metrics are computed for dipeptide units, defined as blocks of Cαi−1—Oi−1—Cαi—Oi—Cαi+1 atoms, by obtaining the eigenvalues of their Euclidean distance matrices. These were computed for ∼1.3 million dipeptide units collected from nonredundant good-quality structures in the Protein Data Bank and subjected to principal component analysis. The resulting new Euclidean orthogonal three-dimensional space (DipSpace) allows a probabilistic description of protein backbone geometry. The three axes of the DipSpace describe the local extension of the dipeptide unit structure, its twist and its bend. By using a higher-dimensional metric, the method is efficient for the identification of Cα atoms in an unlikely or unusual geometrical environment, and its use for both local and overall validation of protein models is demonstrated. It is also shown, for the example of trypsin proteases, that the detection of unusual conformations that are conserved among the structures of this protein family may indicate geometrically strained residues of potentially functional importance.
    Keywords: Ramachandran plotprotein stereochemistryvalidationgeometrical straindipeptide unitdistance matrixEuclidean orthogonal three-dimensional spacetrypsin proteases
    Electronic ISSN: 2052-2525
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  • 80
    Publication Date: 2017-08-09
    Description: Serial femtosecond crystallography (SFX) using X-ray free-electron lasers (XFELs) holds enormous potential for the structure determination of proteins for which it is difficult to produce large and high-quality crystals. SFX has been applied to various systems, but rarely to proteins that have previously unknown structures. Consequently, the majority of previously obtained SFX structures have been solved by the molecular replacement method. To facilitate protein structure determination by SFX, it is essential to establish phasing methods that work efficiently for SFX. Here, selenomethionine derivatization and mercury soaking have been investigated for SFX experiments using the high-energy XFEL at the SPring-8 Angstrom Compact Free-Electron Laser (SACLA), Hyogo, Japan. Three successful cases are reported of single-wavelength anomalous diffraction (SAD) phasing using X-rays of less than 1 Å wavelength with reasonable numbers of diffraction patterns (13 000, 60 000 and 11 000). It is demonstrated that the combination of high-energy X-rays from an XFEL and commonly used heavy-atom incorporation techniques will enable routine de novo structural determination of biomacromolecules.
    Keywords: serial femtosecond crystallographySAD phasingXFELsselenomethionine derivatizationmercury soaking
    Electronic ISSN: 2052-2525
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  • 81
    Publication Date: 2017-08-09
    Description: Rieske nonheme iron oxygenases (ROs) are a well studied class of enzymes. Naphthalene 1,2-dioxygenase (NDO) is used as a model to study ROs. Previous work has shown how side-on binding of oxygen to the mononuclear iron provides this enzyme with the ability to catalyze stereospecific and regiospecific cis-dihydroxylation reactions. It has been well documented that ROs catalyze a variety of other reactions, including mono-oxygenation, desaturation, O- and N-dealkylation, sulfoxidation etc. NDO itself catalyzes a variety of these reactions. Structures of NDO in complex with a number of different substrates show that the orientation of the substrate in the active site controls not only the regiospecificity and stereospecificity, but also the type of reaction catalyzed. It is proposed that the mononuclear iron-activated dioxygen attacks the atoms of the substrate that are most proximal to it. The promiscuity of delivering two products (apparently by two different reactions) from the same substrate can be explained by the possible binding of the substrate in slightly different orientations aided by the observed flexibility of residues in the binding pocket.
    Keywords: naphthalene 1,2-dioxygenasemonooxygenationsulfoxidationdeoxygenationsubstrate orientation
    Electronic ISSN: 2052-2525
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  • 82
    Publication Date: 2017-09-27
    Description: The flagellated Gram-negative bacterium Escherichia coli is one of the most studied microorganisms. Despite extensive studies as a model prokaryotic cell, the ultrastructure of the cell envelope at the nanometre scale has not been fully elucidated. Here, a detailed structural analysis of the bacterium using a combination of small-angle X-ray and neutron scattering (SAXS and SANS, respectively) and ultra-SAXS (USAXS) methods is presented. A multiscale structural model has been derived by incorporating well established concepts in soft-matter science such as a core-shell colloid for the cell body, a multilayer membrane for the cell wall and self-avoiding polymer chains for the flagella. The structure of the cell envelope was resolved by constraining the model by five different contrasts from SAXS, and SANS at three contrast match points and full contrast. This allowed the determination of the membrane electron-density profile and the inter-membrane distances on a quantitative scale. The combination of USAXS and SAXS covers size scales from micrometres down to nanometres, enabling the structural elucidation of cells from the overall geometry down to organelles, thereby providing a powerful method for a non-invasive investigation of the ultrastructure. This approach may be applied for probing in vivo the effect of detergents, antibiotics and antimicrobial peptides on the bacterial cell wall.
    Keywords: in vivo analysisEscherichia coliultrastructuresmall-angle scattering
    Electronic ISSN: 2052-2525
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  • 83
    Publication Date: 2017-10-14
    Description: Serial synchrotron-based crystallography using intense microfocused X-ray beams, fast-framing detectors and protein microcrystals held at 300 K promises to expand the range of accessible structural targets and to increase overall structure-pipeline throughputs. To explore the nature and consequences of X-ray radiation damage under microbeam illumination, the time-, dose- and temperature-dependent evolution of crystal diffraction have been measured with maximum dose rates of 50 MGy s−1. At all temperatures and dose rates, the integrated diffraction intensity for a fixed crystal orientation shows non-exponential decays with dose. Non-exponential decays are a consequence of non-uniform illumination and the resulting spatial evolution of diffracted intensity within the illuminated crystal volume. To quantify radiation-damage lifetimes and the damage state of diffracting crystal regions, a revised diffraction-weighted dose (DWD) is defined and it is shown that for Gaussian beams the DWD becomes nearly independent of actual dose at large doses. An apparent delayed onset of radiation damage seen in some intensity–dose curves is in fact a consequence of damage. Intensity fluctuations at high dose rates may arise from the impulsive release of gaseous damage products. Accounting for these effects, data collection at the highest dose rates increases crystal radiation lifetimes near 300 K (but not at 100 K) by a factor of ∼1.5–2 compared with those observed at conventional dose rates. Improved quantification and modeling of the complex spatio-temporal evolution of protein microcrystal diffraction in intense microbeams will enable more efficient data collection, and will be essential in improving the accuracy of structure factors and structural models.
    Keywords: protein crystallographyradiation damageserial crystallographymicrocrystallographystructure determinationprotein structureX-ray crystallographystructural biologyintense X-ray microbeams
    Electronic ISSN: 2052-2525
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  • 84
    Publication Date: 2017-10-14
    Description: Temporal coherence is one of the most fundamental characteristics of light, connecting to spectral information through the Fourier transform relationship between time and frequency. Interferometers with a variable path-length difference (PLD) between the two branches have widely been employed to characterize temporal coherence properties for broad spectral regimes. Hard X-ray interferometers reported previously, however, have strict limitations in their operational photon energies, due to the specific optical layouts utilized to satisfy the stringent requirement for extreme stability of the PLD at sub-ångström scales. The work presented here characterizes the temporal coherence of hard X-ray free-electron laser (XFEL) pulses by capturing single-shot interferograms. Since the stability requirement is drastically relieved with this approach, it was possible to build a versatile hard X-ray interferometer composed of six separate optical elements to cover a wide photon energy range from 6.5 to 11.5 keV while providing a large variable delay time of up to 47 ps at 10 keV. A high visibility of up to 0.55 was observed at a photon energy of 10 keV. The visibility measurement as a function of time delay reveals a mean coherence time of 5.9 ± 0.7 fs, which agrees with that expected from the single-shot spectral information. This is the first result of characterizing the temporal coherence of XFEL pulses in the hard X-ray regime and is an important milestone towards ultra-high energy resolutions at micro-electronvolt levels in time-domain X-ray spectroscopy, which will open up new opportunities for revealing dynamic properties in diverse systems on timescales from femtoseconds to nanoseconds, associated with fluctuations from ångström to nanometre spatial scales.
    Keywords: X-ray interferometrysplit-and-delay optical systemX-ray free-electron laserstemporal coherence
    Electronic ISSN: 2052-2525
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  • 85
    Publication Date: 2017-10-14
    Description: Serial femtosecond crystallography is an emerging and promising method for determining protein structures, making use of the ultrafast and bright X-ray pulses from X-ray free-electron lasers. The upcoming X-ray laser sources will produce well above 1000 pulses per second and will pose a new challenge: how to quickly determine successful crystal hits and avoid a high-rate data deluge. Proposed here is a hit-finding scheme based on detecting photons from plasma emission after the sample has been intercepted by the X-ray laser. Plasma emission spectra are simulated for systems exposed to high-intensity femtosecond pulses, for both protein crystals and the liquid carrier systems that are used for sample delivery. The thermal radiation from the glowing plasma gives a strong background in the XUV region that depends on the intensity of the pulse, around the emission lines from light elements (carbon, nitrogen, oxygen). Sample hits can be reliably distinguished from the carrier liquid based on the characteristic emission lines from heavier elements present only in the sample, such as sulfur. For buffer systems with sulfur present, selenomethionine substitution is suggested, where the selenium emission lines could be used both as an indication of a hit and as an aid in phasing and structural reconstruction of the protein.
    Keywords: hit detectionplasma emission spectraserial femtosecond crystallographyprotein structure
    Electronic ISSN: 2052-2525
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  • 86
    Publication Date: 2017-09-27
    Description: The introduction of direct detectors and the automation of data collection in cryo-EM have led to a surge in data, creating new opportunities for advancing computational processing. In particular, on-the-fly workflows that connect data collection with three-dimensional reconstruction would be valuable for more efficient use of cryo-EM and its application as a sample-screening tool. Here, accelerated on-the-fly analysis is reported with optimized organization of the data-processing tools, image acquisition and particle alignment that make it possible to reconstruct the three-dimensional density of the 70S chlororibosome to 3.2 Å resolution within 24 h of tissue harvesting. It is also shown that it is possible to achieve even faster processing at comparable quality by imposing some limits to data use, as illustrated by a 3.7 Å resolution map that was obtained in only 80 min on a desktop computer. These on-the-fly methods can be employed as an assessment of data quality from small samples and extended to high-throughput approaches.
    Keywords: cryo-EMimage processingchlororibosome
    Electronic ISSN: 2052-2525
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  • 87
    Publication Date: 2017-09-27
    Description: X-ray free-electron lasers (XFELs) provide new opportunities for structure determination of biomolecules, viruses and nanomaterials. With unprecedented peak brilliance and ultra-short pulse duration, XFELs can tolerate higher X-ray doses by exploiting the femtosecond-scale exposure time, and can thus go beyond the resolution limits achieved with conventional X-ray diffraction imaging techniques. Using XFELs, it is possible to collect scattering information from single particles at high resolution, however particle heterogeneity and unknown orientations complicate data merging in three-dimensional space. Using the Linac Coherent Light Source (LCLS), synthetic inorganic nanocrystals with a core–shell architecture were used as a model system for proof-of-principle coherent diffractive single-particle imaging experiments. To deal with the heterogeneity of the core–shell particles, new computational methods have been developed to extract the particle size and orientation from the scattering data to assist data merging. The size distribution agrees with that obtained by electron microscopy and the merged data support a model with a core–shell architecture.
    Keywords: orientation determinationstructure heterogeneitysingle-particle scatteringnanoparticlescore–shell architectureXFELs
    Electronic ISSN: 2052-2525
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  • 88
    facet.materialart.
    Unknown
    International Union of Crystallography (IUCr)
    In: IUCrJ
    Publication Date: 2017-10-07
    Description: Understanding published research results should be through one's own eyes and include the opportunity to work with raw diffraction data to check the various decisions made in the analyses by the original authors. Today, preserving raw diffraction data is technically and organizationally viable at a growing number of data archives, both centralized and distributed, which are empowered to register data sets and obtain a preservation descriptor, typically a `digital object identifier'. This introduces an important role of preserving raw data, namely understanding where we fail in or could improve our analyses. Individual science area case studies in crystallography are provided.
    Keywords: raw diffraction datasharing raw data and its reuseopen scienceeducationcrystallographic science case studies
    Electronic ISSN: 2052-2525
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  • 89
    Publication Date: 2017-10-07
    Description: Magnetic Heusler compounds (MHCs) have recently attracted great attention since these types of material provide novel functionalities in spintronic and magneto-electronic devices. Among the MHCs, some compounds have been predicted to be spin-filter semiconductors [also called magnetic semiconductors (MSs)], spin-gapless semiconductors (SGSs) or half-metals (HMs). In this work, by means of first-principles calculations, it is demonstrated that rare earth-based equiatomic quaternary Heusler (EQH) compounds with the formula MCoVZ (M = Lu, Y; Z = Si, Ge) are new spin-filter semiconductors with total magnetic moments of 3 µB. Furthermore, under uniform strain, there are physical transitions from spin-filter semiconductor (MS) → SGS → HM for EQH compounds with the formula LuCoVZ, and from HM → SGS → MS → SGS → HM for EQH compounds with the formula YCoVZ. Remarkably, for YCoVZ EQH compounds there are not only diverse physical transitions, but also different types of spin-gapless feature that can be observed with changing lattice constants. The structural stability of these four EQH compounds is also examined from the points of view of formation energy, cohesive energy and mechanical behaviour. This work is likely to inspire consideration of rare earth-based EQH compounds for application in future spintronic and magneto-electronic devices.
    Keywords: spin-filter materialsspin-gapless semiconductorsband structuresmagnetic propertiesfirst-principles predictionsdensity functional theorymaterials modelling
    Electronic ISSN: 2052-2525
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  • 90
    Publication Date: 2017-10-10
    Description: Unravelling the interaction of biological macromolecules with ligands and substrates at high spatial and temporal resolution remains a major challenge in structural biology. The development of serial crystallography methods at X-ray free-electron lasers and subsequently at synchrotron light sources allows new approaches to tackle this challenge. Here, a new polyimide tape drive designed for mix-and-diffuse serial crystallography experiments is reported. The structure of lysozyme bound by the competitive inhibitor chitotriose was determined using this device in combination with microfluidic mixers. The electron densities obtained from mixing times of 2 and 50 s show clear binding of chitotriose to the enzyme at a high level of detail. The success of this approach shows the potential for high-throughput drug screening and even structural enzymology on short timescales at bright synchrotron light sources.
    Keywords: drug discoveryprotein structureX-ray crystallographyserial crystallographytime-resolved studieslysozyme
    Electronic ISSN: 2052-2525
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  • 91
    Publication Date: 2017-11-28
    Description: The characteristics of magnetostructural coupling play a crucial role in the magnetic field-driven behaviour of magnetofunctional alloys. The availability of magnetostructural coupling over a broad temperature range is of great significance for scientific and technological purposes. This work demonstrates that strong magnetostrucural coupling can be achieved over a wide temperature range (222 to 355 K) in Co-doped high Mn-content Mn50Ni42−xCoxSn8 (0 ≤ x ≤ 10) melt-spun ribbons. It is shown that, over a wide composition range with Co content from 3 to 9 at.%, the paramagnetic austenite first transforms into ferromagnetic austenite at TC on cooling, then the ferromagnetic austenite further transforms into a weakly magnetic martensite at TM. Such strong magnetostructural coupling enables the ribbons to exhibit field-induced inverse martensitic transformation behaviour and a large magnetocaloric effect. Under a field change of 5 T, a maximum magnetic entropy change ΔSM of 18.6 J kg−1 K−1 and an effective refrigerant capacity RCeff of up to 178 J kg−1 can be achieved, which are comparable with or even superior to those of Ni-rich Ni–Mn-based polycrystalline bulk alloys. The combination of high performance and low cost makes Mn–Ni–Co–Sn ribbons of great interest as potential candidates for magnetic refrigeration.
    Keywords: MnNi-based alloysmelt-spun ribbonsmagnetostructural couplingmagnetocaloric effect
    Electronic ISSN: 2052-2525
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  • 92
    Publication Date: 2017-11-28
    Description: Hirshfeld atom refinement (HAR) is a novel X-ray structure refinement technique that employs aspherical atomic scattering factors obtained from stockholder partitioning of a theoretically determined tailor-made static electron density. HAR overcomes many of the known limitations of independent atom modelling (IAM), such as too short element–hydrogen distances, r(X—H), or too large atomic displacement parameters (ADPs). This study probes the accuracy and precision of anisotropic hydrogen and non-hydrogen ADPs and of r(X—H) values obtained from HAR. These quantities are compared and found to agree with those obtained from (i) accurate neutron diffraction data measured at the same temperatures as the X-ray data and (ii) multipole modelling (MM), an established alternative method for interpreting X-ray diffraction data with the help of aspherical atomic scattering factors. Results are presented for three chemically different systems: the aromatic hydrocarbon rubrene (orthorhombic 5,6,11,12-tetraphenyltetracene), a co-crystal of zwitterionic betaine, imidazolium cations and picrate anions (BIPa), and the salt potassium hydrogen oxalate (KHOx). The non-hydrogen HAR-ADPs are as accurate and precise as the MM-ADPs. Both show excellent agreement with the neutron-based values and are superior to IAM-ADPs. The anisotropic hydrogen HAR-ADPs show a somewhat larger deviation from neutron-based values than the hydrogen SHADE-ADPs used in MM. Element–hydrogen bond lengths from HAR are in excellent agreement with those obtained from neutron diffraction experiments, although they are somewhat less precise. The residual density contour maps after HAR show fewer features than those after MM. Calculating the static electron density with the def2-TZVP basis set instead of the simpler def2-SVP one does not improve the refinement results significantly. All HARs were performed within the recently introduced HARt option implemented in the Olex2 program. They are easily launched inside its graphical user interface following a conventional IAM.
    Keywords: Hirshfeld atom refinementmultipole modellinganisotropic displacement parametershydrogen-atom propertiescrystallographic software
    Electronic ISSN: 2052-2525
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  • 93
    Publication Date: 2017-11-28
    Description: Direct observation and structural characterization of a kinetic product and a thermodynamic product for complexes with an NO2S2 macrocycle (L) are reported. L reacts with copper(I) iodide to give a mononuclear complex [Cu(L)]2(Cu2I4)·2CH2Cl2 (1), featuring three separate units. When cadmium(II) iodide was reacted with L, an anion-coordinated complex [Cd(L)I]2(Cd2I6)·4CH3CN (2) with a needle-type crystal shape was formed as the kinetic product. Interestingly, when the needle-type kinetic product was left undisturbed in the mother solution it gradually transformed to the pseudo-dimer complex [Cd2(L)2I2](Cd2I6) (3) with a brick-type crystal shape as the thermodynamic product. The dissolution–recrystallization process resulted in the elimination of the lattice solvent molecules (acetonitrile) in 2 and the contraction of two neighboring macrocyclic complex units [Cd(L)I]+, forming the pseudo-dimer 3 via an intermolecular Cd...I interaction between two monomers. For the entire process from kinetic to thermodynamic products, it was possible to obtain sequential photographic snapshots, single-crystal X-ray structures and powder X-ray diffraction patterns. For the copper(I) and cadmium(II) complexes, competitive NMR results agree with the solid-state data that show copper(I) has a higher affinity for L than does cadmium(II).
    Keywords: snapshotskinetic productsthermodynamic productssingle-crystal-to-single-crystal transformationscrystal engineeringmolecular crystals
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  • 94
    Publication Date: 2017-11-15
    Description: In order to develop transferable and practical avenues for the assembly of coordination complexes into architectures with specific dimensionality, a strategy utilizing ligands capable of simultaneous metal coordination and self-complementary hydrogen bonding is presented. The three ligands used, 2(1H)-pyrazinone, 4(3H)-pyrimidinone and 4(3H)-quinazolinone, consistently deliver the required synthetic vectors in a series of CdII coordination polymers, allowing for reproducible supramolecular synthesis that is insensitive to the different steric and geometric demands from potentially disruptive counterions. In all nine crystallographically characterized compounds presented here, directional intermolecular N—H...O hydrogen bonds between ligands on adjacent complex building blocks drive the assembly and orientation of discrete building blocks into largely predictable topologies. Furthermore, whether the solids are prepared from solution or through liquid-assisted grinding, the structural outcome is the same, thus emphasizing the robustness of the synthetic protocol. The details of the molecular recognition events that take place in this series of compounds have been clearly delineated and rationalized in the context of calculated molecular electrostatic potential surfaces.
    Keywords: crystal engineeringhydrogen bondselectrostatic potentialsynthonscoordination compounds
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  • 95
    Publication Date: 2017-11-15
    Description: Enantiomeric amino acids have specific physiological functions in complex biological systems. Systematic studies focusing on the solid-state properties of d-amino acids are, however, still limited. To shed light on this field, structural and spectroscopic studies of d-alanine using neutron powder diffraction, polarized Raman scattering and ab initio calculations of harmonic vibrational frequencies were carried out. Clear changes in the number of vibrational modes are observed as a function of temperature, which can be directly connected to variations of the N—D bond lengths. These results reveal dissimilarities in the structural properties of d-alanine compared with l-alanine.
    Keywords: chiralitystructure analysisconfigurational changedensity-functional-theory-based methodsphase transitionsintermolecular interactionsproperties of solidshydrogen bondingmaterials science
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  • 96
    Publication Date: 2017-11-18
    Description: Synchrotron-based X-ray structural studies of ligand-bound enzymes are powerful tools to further our understanding of reaction mechanisms. For redox enzymes, it is necessary to study both the oxidized and reduced active sites to fully elucidate the reaction, an objective that is complicated by potential X-ray photoreduction. In the presence of the substrate, this can be exploited to construct a structural movie of the events associated with catalysis. Using the newly developed approach of serial femtosecond rotation crystallography (SF-ROX), an X-ray damage-free structure of the as-isolated copper nitrite reductase (CuNiR) was visualized. The sub-10 fs X-ray pulse length from the SACLA X-ray free-electron laser allowed diffraction data to be collected to 1.6 Å resolution in a `time-frozen' state. The extremely short duration of the X-ray pulses ensures the capture of data prior to the onset of radiation-induced changes, including radiolysis. Unexpectedly, an O2 ligand was identified bound to the T2Cu in a brand-new binding mode for a diatomic ligand in CuNiRs. The observation of O2 in a time-frozen structure of the as-isolated oxidized enzyme provides long-awaited clear-cut evidence for the mode of O2 binding in CuNiRs. This provides an insight into how CuNiR from Alcaligenes xylosoxidans can function as an oxidase, reducing O2 to H2O2, or as a superoxide dismutase (SOD) since it was shown to have ∼56% of the dismutase activity of the bovine SOD enzyme some two decades ago.
    Keywords: serial femtosecond rotation crystallographyO2 bindingcopper nitrite reductase
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  • 97
    Publication Date: 2017-10-28
    Description: The limiting factor in protein crystallography is still the production of high-quality crystals. In this regard, the authors have recently introduced hexatungstotellurate(VI) (TEW) as a new crystallization additive, which proved to be successful within the liquid–liquid phase separation (LLPS) zone. Presented here are comparative crystal structure analyses revealing that protein–TEW binding not only induces and stabilizes crystal contacts, but also exhibits a significant impact on the solvent-driven crystallization entropy, which is the driving force for the crystallization process. Upon the formation of TEW-mediated protein–protein contacts, the release of water molecules from the hydration shells of both molecules, i.e. TEW and the protein, causes a reduced solvent-accessible surface area, leading to a significant gain in solvent entropy. Based on the crystal structures of aurone synthase (in the presence and absence of TEW), insights have also been provided into the formation of a metastable LLPS, which is caused by the formation of protein clusters, representing an ideal starting point in protein crystallization. The results strongly encourage the classification of TEW as a valuable crystallization additive.
    Keywords: polyoxotungstatecrystallization additivescrystal contactsliquid–liquid phase separationsolvent entropy
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  • 98
    Publication Date: 2017-10-28
    Description: The design and synthesis of mechanically responsive materials is interesting because they are potential candidates to convert thermal energy into mechanical work. Reported in this paper are thermosalient effects in a series of halogen derivatives of salinazids. The chloro derivative, with higher electronegativity and a weaker inter-halogen bond strength (Cl...Cl) exhibits an excellent thermal response, whereas the response is weaker in the iodo derivative with stronger I...I halogen bonding. 3,5-Dichlorosalinazid (Compound-A) exists in three polymorphic forms, two room-temperature polymorphs (Forms I and II) and one high-temperature modification (Form III). The transformation of Form I to Form III upon heating at 328–333 K is a reversible thermosalient transition, whereas the transformation of Form II to Form III is irreversible and non-thermosalient. 3,5-Dibromo- (Compound-B) and 3-bromo-5-chloro- (Compound-C) salinazid are both dimorphic: the Form I to Form II transition in Compound-B is irreversible, whereas Compound-C shows a reversible thermosalient effect (362–365 K). In the case of 3,5-diiodosalinazid (Compound-D) and 3,5-difluorosalinazid (Compound-E), no phase transitions or thermal effects were observed. The thermosalient behaviour of these halosalinazid molecular crystals is understood from the anisotropy in the cell parameters (an increase in the a axis and a decrease in the b and c axes upon heating) and the sudden release of accumulated strain during the phase transition. The di-halogen salinazid derivatives (chlorine to iodine) show a decrease in thermal effects with an increase in halogen-bond strength. Interestingly, Compound-B shows solid-state photochromism in its polymorphs along with the thermosalient effect, wherein Form I is cyan and Form II is light orange.
    Keywords: halogen bondshydrogen bondsmaterials sciencepolymorphismsalinazidcrystal engineeringmechanochemistrymolecular crystalsmaterials modelling
    Electronic ISSN: 2052-2525
    Topics: Geosciences , Physics
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  • 99
    Publication Date: 2017-12-23
    Description: Human carbonic anhydrase II (hCA II) is a zinc metalloenzyme that catalyzes the reversible hydration/dehydration of CO2/HCO3−. Although hCA II has been extensively studied to investigate the proton-transfer process that occurs in the active site, its underlying mechanism is still not fully understood. Here, ultrahigh-resolution crystallographic structures of hCA II cryocooled under CO2 pressures of 7.0 and 2.5 atm are presented. The structures reveal new intermediate solvent states of hCA II that provide crystallographic snapshots during the restoration of the proton-transfer water network in the active site. Specifically, a new intermediate water (WI′) is observed next to the previously observed intermediate water WI, and they are both stabilized by the five water molecules at the entrance to the active site (the entrance conduit). Based on these structures, a water network-restructuring mechanism is proposed, which takes place at the active site after the nucleophilic attack of OH− on CO2. This mechanism explains how the zinc-bound water (WZn) and W1 are replenished, which are directly responsible for the reconnection of the His64-mediated proton-transfer water network. This study provides the first `physical' glimpse of how a water reservoir flows into the hCA II active site during its catalytic activity.
    Keywords: carbonic anhydrase IIproton transferwater dynamicshigh-pressure cryocoolingactive-site solvent replenishment
    Electronic ISSN: 2052-2525
    Topics: Geosciences , Physics
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  • 100
    Publication Date: 2017-12-23
    Description: Peroxiredoxins (Prxs) are ubiquitous cysteine-based peroxidase enzymes. Recently, a new type of Prx, VvPrx3, was identified in the pathogenic bacterium Vibrio vulnificus as being important for survival in macrophages. It employs only one catalytic cysteine residue to decompose peroxides. Here, crystal structures of VvPrx3 representing its reduced and oxidized states have been determined, together with an H2O2-bound structure, at high resolution. The crystal structure representing the reduced Prx3 showed a typical dimeric interface, called the A-type interface. However, VvPrx3 forms an oligomeric interface mediated by a disulfide bond between two catalytic cysteine residues from two adjacent dimers, which differs from the doughnut-like oligomers that appear in most Prxs. Subsequent biochemical studies showed that this disulfide bond was induced by treatment with nitric oxide (NO) as well as with peroxides. Consistently, NO treatment induced expression of the prx3 gene in V. vulnificus, and VvPrx3 was crucial for the survival of bacteria in the presence of NO. Taken together, the function and mechanism of VvPrx3 in scavenging peroxides and NO stress via oligomerization are proposed. These findings contribute to the understanding of the diverse functions of Prxs during pathogenic processes at the molecular level.
    Keywords: nitric oxideperoxiredoxinscrystal structureVibrio vulnificusprotein structureX-ray crystallography
    Electronic ISSN: 2052-2525
    Topics: Geosciences , Physics
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