Physical Sciences and Mathematics Commons^™

New Far-Infrared Laser Frequencies Generated By Ch3cn, Cd3cn, 13ch3i, Cd3i, And 13cd3i, Michael Jackson

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Heterodyne techniques have been used to experimentally determine, for the first time, the frequencies for nineteen laser emissions ranging from 264 to 984 GHz. These laser emissions were generated by optically pumping either CH₃CN, CD₃CN, ¹³CH₃, CD₃I, or ¹³CD₃I with a CO₂ laser. This includes the newly discovered 566.325-μ m laser emission from optically pumped ¹³CD₃I. The fractional uncertainties with which these frequencies were experimentally determined, up to ± 5 × 10^− 7, were of sufficient accuracy to confirm or revise …

Contra-Thermodynamic Halolactonization Of Lactam-Tethered 5-Aryl-4(E)-Pentenoic Acids For The Flexible And Stereocontrolled Synthesis Of Fused Lactam-Halolactones, Timothy K. Beng, Claire Borg, Morgan J. Rodriguez

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Halolactonization of alkenoic acids enables the construction of oxygen-heterocycles via intramolecular halonium-induced nucleophilic addition. Although the literature is currently inundated with halolactonizations of 5-aryl-4(E)-pentenoic acids that predictably afford the 6-endo cyclization adducts, methods that reliably alter the innate regioselectivity bias to instead deliver the thermodynamically less favored 5-exo cyclization products are relatively rare. Here, we attempt to bridge this gap and have found mild conditions for contra-thermodynamic halolactonization of lactam-tethered 5-aryl-4(E)-pentenoic acids that lead to the formation of trans-fused lactam-γ-lactones. The natural proclivity for these 5-aryl-4(E)-pentenoic acids to undergo 6-endo cyclization is overridden and 5-exo-trig cyclization predominates. The success of …

Stereocontrolled Access To Δ-Lactone-Fused-Γ-Lactams Bearing Angular Benzylic Quaternary Stereocenters, Timothy K. Beng, Morgan J. Rodriguez, Claire Borg

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C-fused γ-lactam-lactones are resident in several bioactive molecules, including anticancer agents such as omuralide. In this embodiment, we report mild conditions for the catalytic halolactonization of lactam-tethered 5-aryl-4(E)-pentenoic acids. The use of dichloromethane as the solvent and Ph₃PS as the catalyst led to predominant 6-endo-trig cyclization and furnished the trans-fused-γ-lactam-δ-lactones. The transformation is modular, regioselective, chemoselective, and diastereoselective. The γ-lactam-δ-lactones bear angular quaternary benzylic stereocenters, which is noteworthy since the presence of a quaternary carbon in bioactive small molecules often promotes an element of conformational restriction that imparts potency, selectivity, and metabolic stability. The …

Design Of Broadband Helmholtz Resonator Arrays Using The Radiation Impedance Method, Vidhya Rajendran, Andy Piacsek, Tomás Méndez Echenagucia

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This paper describes the design process of a low-frequency sound absorptive panel composed of differently tuned Helmholtz resonators (HRs), considering size and fabrication constraints relevant for applications in the building sector. The paper focuses on cylindrical and spiral resonators with embedded necks that are thin and can achieve high absorption. the mutual interaction between the resonators was modeled based on the radiation impedance method and it plays a key component in enhancing the absorption performance of the array. The differential evolution search algorithm was used to design the resonators and modify their mutual interaction to derive the absorption performance of …

Can CP Be Less Than CV?, Yingbin Ge, Samuel L. Montgomery, Gabriel L. Borrello

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Can C_P be less than C_V? This is a fundamental question in physics, chemistry, chemical engineering, and mechanical engineering. This question hangs in the minds of many students, instructors, and researchers. The first instinct is to answer “Yes, for water between 0 and 4 °C” if one knows that water expands as temperature decreases in this temperature range. The same question is asked in several Physical Chemistry and Physics textbooks. Students are supposed to answer that water contracts when heated at below 4 °C in an isobaric process. Because work is done to the contracting water, less …

Semiotic Aggregation In Deep Learning, Bogdan Muşat, Răzvan Andonie

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Convolutional neural networks utilize a hierarchy of neural network layers. The statistical aspects of information concentration in successive layers can bring an insight into the feature abstraction process. We analyze the saliency maps of these layers from the perspective of semiotics, also known as the study of signs and sign-using behavior. In computational semiotics, this aggregation operation (known as superization) is accompanied by a decrease of spatial entropy: signs are aggregated into supersign. Using spatial entropy, we compute the information content of the saliency maps and study the superization processes which take place between successive layers of the network. In …

Herschel Gould Belt Survey Observations Of Dense Cores In The Cepheus Flare Clouds, James Di Francesco, Jared Keown, Cassandra Fallscheer, Philippe André, Bilal Ladjelate, Vera Könyves, Alexander Men'shchikov, Shaun Stephens-Whale, Quang Nguyen-Luong, Peter Martin, Sarah Sadavoy, Stefano Pezzuto, Eleonora Fiorellino, Milena Benedettini, Nicola Schneider, Sylvain Bontemps, Doris Arzoumanian, Pedro Palmeirim, Jason M. Kirk, Derek Ward-Thompson

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We present Herschel SPIRE and PACS maps of the Cepheus Flare clouds L1157, L1172, L1228, L1241, and L1251, observed by the Herschel Gould Belt Survey of nearby star-forming molecular clouds. Through modified blackbody fits to the SPIRE and PACS data, we determine typical cloud column densities of (0.5–1.0) × 10²¹ cm⁻² and typical cloud temperatures of 14–15 K. Using the getsources identification algorithm, we extract 832 dense cores from the SPIRE and PACS data at 160–500 μm. From placement in a mass versus size diagram, we consider 303 to be candidate prestellar cores, and 178 of these …

Modular Synthesis And Transition Metal-Free Alkynylation/Alkenylation Of Castagnoli–Cushmanderived N,O- And N,S-Heterocyclic Vinyl Chlorides, Timothy K. Beng, Abdikani Omar Farah, Victoria Shearer

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A modular and functional group-tolerant protocol for the transition metal-free coupling of novel N,O- and N,S-heterocyclic vinyl chlorides with terminal acetylenes and styrenes has been developed, leading to the epimerization-free synthesis of fully carbofunctionalized dihydro-1,4-oxazines/thiazines. Bicyclic morpholines have also been prepared through the interrogation of newly synthesized cross-conjugated dienes in Diels–Alder reactions. The use of environmentally benign reaction media endows the current strategy with a practical advantage.

Hot But Not Dry: Modest Changes In Water Relations For An Epiphytic Bromeliad In A Tropical Dry Deciduous Forest, Saúl Hernández-Robinson, Eric A. Graham, Olivia Hernández-González, Roberth Us-Santamaría, José Luis Simá, Fernando Arellano-Martín, José Luis Andrade

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Premise of research. Epiphytic bromeliads endure intense seasonal environmental changes in the canopy of dry tropical deciduous forests. The analysis of the physiological responses of these epiphytes to environmental changes can be useful in assessing their plasticity, vulnerability, and adaptations to such extreme habitats.

Methodology. We measured microenvironmental variables and water relations for plants of the epiphytic bromeliad Tillandsia brachycaulos in three microhabitats within the canopy of a dry tropical forest. We measured individual plants for seasonal and spatial differences in light, leaf temperature, osmotic potential, cell wall elasticity, and relative capacitance as indications of their physiological responses …

Plate Boundary Trench Retreat And Dextral Shear Drive Intracontinental Fault-Slip Histories: Neogene Dextral Faulting Across The Gabbs Valley And Gillis Ranges, Central Walker Lane, Nevada, Jeffrey Lee, Andrew K. R. Hoxey, Andrew Calvert, Peter Dubyoski

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The spatial-temporal evolution of intracontinental faults and the forces that drive their style, orientation, and timing are central to understanding tectonic processes. Intracontinental NW-striking dextral faults in the Gabbs Valley–Gillis Ranges (hereafter referred to as the GVGR), Nevada, define a structural domain known as the eastern Central Walker Lane located east of the western margin of the North American plate. To consider how changes in boundary type along the western margin of the North American plate influenced both the initiation and continued dextral fault slip to the present day in the GVGR, we combine our new detailed geologic mapping, structural …

Contact In The Unitary Fermi Gas Across The Superfluid Phase Transition, S. Jensen, Christopher N. Gilbreth, Y. Alhassid

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A quantity known as the contact is a fundamental thermodynamic property of quantum many-body systems with short-range interactions. Determination of the temperature dependence of the contact for the unitary Fermi gas of infinite scattering length has been a major challenge, with different calculations yielding qualitatively different results. Here we use finite-temperature auxiliary-field quantum Monte Carlo (AFMC) methods on the lattice within the canonical ensemble to calculate the temperature dependence of the contact for the homogeneous spin-balanced unitary Fermi gas. We extrapolate to the continuum limit for 40, 66, and 114 particles, eliminating systematic errors due to finite-range effects. We observe …

Transition Metal-Free Domino Acyl Substitution/Michael Addition Of Alkenyl Grignard Reagents To Lactam Esters: Synthesis Of Lactam-Bearing Homoallylic Ketones, Abdikani Omar Farah, Muhannad Rabah, Timothy K. Beng

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A solvent-controlled protocol for the direct and transition metal-free addition of alkenyl Grignard reagents to vicinally functionalized sp³-rich morpholinones has been developed, leading to the chemo and regioselective synthesis of lactam-bearing homoallylic ketones. The addition of lithium chloride proved to be essential. In cases where a new stereocenter is generated, the doubly branched homoallylic ketones are obtained in unexpectedly high diastereoselectivities. Efforts to extend the methodology to other heterosubstituted lactams revealed some important reactivity and selectivity differences.

Modeling Multi-Targets Sentiment Classification Via Graph Convolutional Networks And Auxiliary Relation, Ao Feng, Zhengjie Gao, Xinyu Song, Ke Ke, Tianhao Xu, Xuelei Zhang

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Existing solutions do not work well when multi-targets coexist in a sentence. The reason is that the existing solution is usually to separate multiple targets and process them separately. If the original sentence has N target, the original sentence will be repeated for N times, and only one target will be processed each time. To some extent, this approach degenerates the fine-grained sentiment classification task into the sentencelevel sentiment classification task, and the research method of processing the target separately ignores the internal relation and interaction between the targets. Based on the above considerations, we proposes to use Graph Convolutional …

Site-Selective, Catalytic, And Diastereoselective Sp3 C–H Hydroxylation And Alkoxylation Of Vicinally Functionalized Lactams, Timothy K. Beng, Victoria Shearer, Rachel Davey, Ivianne Redman

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The C–H bond functionalization of sp³ carbon centres presents a significant challenge due to the inert nature of hydrocarbons as well as the need to selectively functionalize one of the numerous aliphatic C–H bonds embodied in organic molecules. Here, we describe catalytic, diastereoselective, and site-selective sp³ C–H hydroxylation/alkoxylation protocols featuring dihydroisoquinolones, γ-, and δ-lactams, which bear vicinal stereocenters. The hydroxylation strategy utilizes oxygen, a waste-free oxidant and affords attractive fragments for potential drug discovery. Fe-catalyzed dehydrative coupling of the resulting tertiary alcohols with simple primary alcohols has led to the construction of highly versatile unsymmetrical dialkyl ethers.

Refractory Black Carbon (Rbc) Variability In A 47-Year West Antarctic Snow And Firn Core, Marquetto Luciano, Susan Kaspari, Jefferson Cardia Simões

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Black carbon (BC) is an important climate-forcing agent that affects snow albedo. In this work, we present a record of refractory black carbon (rBC) variability, measured from a 20m deep snow and firn core drilled in West Antarctica (79°55’34.600” S, 94°21’13.3”W, 2122m above sea level) during the 2014–2015 austral summer. This is the highest elevation rBC record from West Antarctica. The core was analyzed using the Single Particle Soot Photometer (SP2) coupled to a CETAC Marin-5 nebulizer. Results show a well-defined seasonality with geometric mean concentrations of 0.015 μg L^-1 for the wet season (austral summer–fall) and 0.057 μg …

Weighted Random Search For Cnn Hyperparameter Optimization, Rǎzvan Andonie, Adrian-Cǎtǎlin Florea

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Nearly all model algorithms used in machine learning use two different sets of parameters: the training parameters and the meta-parameters (hyperparameters). While the training parameters are learned during the training phase, the values of the hyperparameters have to be specified before learning starts. For a given dataset, we would like to find the optimal combination of hyperparameter values, in a reasonable amount of time. This is a challenging task because of its computational complexity. In previous work, we introduced the Weighted Random Search (WRS) method, a combination of Random Search (RS) and probabilistic greedy heuristic. In the current paper, we …

A New Early Occurrence Of Cervidae In North America From The Miocene-Pliocene Ellensburg Formation In Washington, Usa, Meaghan M. Emery-Wetherell, Joseph F. Schilter

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A new fossil cervid from the Craig’s Hill locality of the Miocene-Pliocene Ellensburg Formation in the State of Washington, USA, may be one of the oldest fossil deer yet found in North America, underlying a date of 4.9 Ma ± 0.1 Ma. This mandible fragment with m2, m3, and associated p2 has a size that does not distinguish it from Bretzia pseudalces, Odocoileus hemionus, or Capreolus constantini, and distinguishes it from Eocoileus gentryorum and Odocoileus lucasi only in having a thinner p2. A strong paraconid on the p2, and ectostylids and cingulids on the m2 and m3 link it most …

Twentieth Century Black Carbon And Dust Deposition On South Cascade Glacier, Washington State, Usa, As Reconstructed From A 158‐M‐Long Ice Core, Susan D. Kaspari, Dan Pittenger, T. M. Jenk, U. Morgenstern, M. Schwikowski, N. Buenning, L. Stott

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Light absorbing particles (LAPs) include black carbon (BC) and mineral dust and are of interest due to their positive radiative forcing and contribution to albedo reductions and snow and glacier melt. This study documents historic BC and dust deposition as well as their effect on albedo on South Cascade Glacier (SCG) in Washington State (USA) through the analysis of a 158‐m (139.5‐m water equivalent [w.e.]) ice core extracted in 1994 and spanning the period 1840–1991. Peak BC deposition occurred between 1940 and 1960, when median BC concentrations were 16 times higher than background, likely dominated by domestic coal and forest …

Geochronology Of The Middle Eocene Purple Bench Locality (Devil’S Graveyard Formation), Trans-Pecos Texas, Usa, Amy L. Atwater, Kelly D. Thomson, E. Christopher Kirk, Meaghan Emery-Wetherell, Logan Wetherell, Daniel F. Stockli

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Purple Bench is a middle Eocene fossil locality in the Devil’s Graveyard Formation of the Trans-Pecos region of West Texas. In addition to yielding a range of taxa characteristic of the Uintan North American Land Mammal Age, the Purple Bench locality is noteworthy in documenting a number of endemic species that are known only from the site. Despite the Uintan character of the mammalian fauna, the absolute age of Purple Bench is a matter of debate. This uncertainty stems from the wide interval of time encompassed by current radiometric dates bracketing the Purple Bench locality and from conflicting magnetostratigraphic correlations …

Learning In Feedforward Neural Networks Accelerated By Transfer Entropy, Adrian Moldovan, Angel Caţaron, Rǎzvan Andonie

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Current neural networks architectures are many times harder to train because of the increasing size and complexity of the used datasets. Our objective is to design more efficient training algorithms utilizing causal relationships inferred from neural networks. The transfer entropy (TE) was initially introduced as an information transfer measure used to quantify the statistical coherence between events (time series). Later, it was related to causality, even if they are not the same. There are only few papers reporting applications of causality or TE in neural networks. Our contribution is an information-theoretical method for analyzing information transfer between the nodes of …

Glacial Earthquakes And Precursory Seismicity Associated With Thwaites Glacier Calving, J. Paul Winberry, Audrey D. Huerta, Sridhar Anandakrishnan, Richhard C. Aster, Andrew A. Nyblade, Douglas A. Wiens

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We observe two (~M_S 3) long‐period (10–30 s) seismic events that originate from the terminus of Thwaites Glacier, Antarctica. Serendipitous acquisition of satellite images confirm that the seismic events were glacial earthquakes generated during the capsizing of icebergs. The glacial earthquakes were preceded by 6 days of discrete high‐frequency seismic events that can be observed at distances exceeding 250 km. The high‐frequency seismicity displays an increasing rate of occurrence, culminating in several hours of sustained tremor coeval with the long‐period events. A series of satellite images collected during this precursory time period show that the high‐frequency events and …

Mapping Crustal Shear Wave Velocity Structure And Radial Anisotropy Beneath West Antarctica Using Seismic Ambient Noise, J. P. O'Donnell, Audrey D. Huerta, J. Paul Winberry

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Using 8- to 25-s-period Rayleigh and Love wave phase velocity dispersion data extracted from seismic ambient noise, we (i) model the 3-D shear wave velocity structure of the West Antarctic crust and (ii) map variations in crustal radial anisotropy. Enhanced regional resolution is offered by the UK Antarctic Seismic Network. In the West Antarctic Rift System (WARS), a ridge of crust ∼26–30km thick extending south from Marie Byrd Land separates domains of more extended crust (∼22km thick) in the Ross and Amundsen Sea Embayments, suggesting along-strike variability in the Cenozoic evolution of the WARS. The southern margin of the WARS …

Tools For Prescreening The Most Active Sites On Ir And Rh Clusters Toward C−H Bond Cleavage Of Ethane: Nbo Charges And Wiberg Bond Indexes, Yingbin Ge, Anna Le, Gregory J. Marquino, Phuc Q. Nguyen, Kollin Trujillo, Morgan Schimelfenig, Ashley Noble

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B3LYP calculations were carried out to study the insertion of iridium (Ir) and rhodium (Rh) clusters into a C−H bond of ethane, which is often the ratelimiting step of the catalytic cycle of oxidative dehydrogenation of ethane. Our previous research on Ir catalysis correlates the diffusivity of the lowest unoccupied molecular orbital of the Ir clusters and the relative activities of the various catalytic sites. The drawback of this research is that the molecular orbital visualization is qualitative rather than quantitative. Therefore, in this study on C−H bond activation by the Ir and Rh clusters, we conducted analyses of natural …

Magnetocaloric Effect Near Room Temperature In Quintenary And Sextenary Heusler Alloys, Benjamin D. White, R. I. Barabash, O. M. Barabash, I. Jeon, M. B. Maple

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An inverse magnetocaloric effect is studied in Ni₂Mn_1+xX_1-x-type Heusler alloys. Principally known for their shape-memory properties, these alloys also exhibit significant entropy and temperature changes (ΔS and ΔT_Ad, respectively) under adiabatic conditions when a modest magnetic field is applied. We investigated the impact on magnetocaloric properties of introducing substantial chemical disorder on the X-site (X = Si, Ga, In), of replacing Ni with nonmagnetic Ag, and of replacing a small amount of Mn with Gd. While a reduction in ΔS is observed in the first two cases, we observe a significant enhancement …

Automated Morgan Keenan Classification Of Observed Stellar Spectra Collected By The Sloan Digital Sky Survey Using A Single Classifier, Michael J. Brice, Răzvan Andonie

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The classification of stellar spectra is a fundamental task in stellar astrophysics. Stellar spectra from the Sloan Digital Sky Survey are applied to standard classification methods, k-nearest neighbors and random forest, to automatically classify the spectra. Stellar spectra are high dimensional data and the dimensionality is reduced using astronomical knowledge because classifiers work in low dimensional space. These methods are utilized to classify the stellar spectra into a complete Morgan Keenan classification (spectral and luminosity) using a single classifier. The motion of stars (radial velocity) causes machine-learning complications through the feature matrix when classifying stellar spectra. Due to the nature …

Deep Open Storage And Shallow Closed Transport System For A Continental Flood Basalt Sequence Revealed With Magma Chamber Simulator, Jussi S. Heinonen, Arto V. Luttinen, Frank J. Spera, Wendy A. Bohrson

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The Magma Chamber Simulator (MCS) quantitatively models the phase equilibria, mineral chemistry, major and trace elements, and radiogenic isotopes in a multicomponent–multiphase magma + wallrock + recharge system by minimization or maximization of the appropriate thermodynamic potential for the given process. In this study, we utilize MCS to decipher the differentiation history of a continental flood basalt sequence from the Antarctic portion of the ~ 180 Ma Karoo large igneous province. Typical of many flood basalts, this suite exhibits geochemical evidence (e.g., negative initial εNd) of interaction with crustal materials. We show that isobaric assimilation-fractional crystallization models fail to …

Phase Transitions In A Symmetry-Conserving Framework, Yoram Alhassid, G. F. Bertsch, Christopher N. Gilbreth, Mika T. Mustonen

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Phase transitions are often associated with the breaking of a symmetry in the low-temperature phase described by non-vanishing values of certain order parameters. However, in finite-size systems the correlated equilibrium configuration preserves the symmetries of the underlying Hamiltonian. We discuss a method to calculate the statistical distribution of the order parameters without breaking the corresponding symmetries. The maxima of these statistical distributions mimic the phase transitions that are found in a mean-field approximation. We demonstrate the method for the case of shape transitions in atomic nuclei.

Dextral, Normal, And Sinistral Faulting Across The Eastern California Shear Zone-Mina Deflection Transition, California-Nevada, Usa, Kevin Delano, Jeffrey Lee, Rachelle Roper, Andrew Calvert

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Strike-slip faults commonly include extensional and contractional bends and stepovers, whereas rotational stepovers are less common. The Volcanic Tableland, Black Mountain, and River Spring areas (California and Nevada, USA) (hereafter referred to as the VBR region) straddle the transition from the dominantly NW-striking dextral faults that define the northwestern part

of the eastern California shear zone into a rotational stepover characterized by dominantly NE-striking sinistral faults that define the southwestern Mina deflection. New detailed geologic mapping, structural studies, and 40Ar/39Ar geochronology across the VBR region allow us to calculate Pliocene to Pleistocene fault slip rates and test predictions for the …

Seismic Observations Of Crevasse Growth Following Rain-Induced Glacier Acceleration, Haupapa/Tasman Glacier, New Zealand, Samuel Taylor-Offord, Huw Horgan, John Townend, J. Paul Winberry

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Changing rates of water input can affect both the flow of glaciers and ice sheets and their propensity to crevasse. Here we examine geodetic and seismic observations during two substantial (10–18-times background velocity) rain-induced glacier accelerations at Haupapa/Tasman Glacier, New Zealand. Changes in rain rate result in glacier acceleration and associated uplift, which propagate down-glacier. This pattern of acceleration results in a change to the strain rate field, which correlates with an order of magnitude increase in the apparent seismicity rate and an overall down-glacier migration in located seismicity. After each acceleration event the apparent seismicity rate decreases to below …

Tidal And Spatial Variability Of Flow Speed And Seismicity Near The Grounding Zone Of Beardmore Glacier, Antarctica, Jade Cooley, J. Paul Winberry, Michelle Koutnik, Howard Conway

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GPS measurements of tidal modulation of ice flow and seismicity within the grounding zone of Beardmore Glacier show that tidally induced fluctuations of horizontal flow are largest near the grounding line and decrease downstream. Seismic activity is continuous, but peaks occur on falling and rising tides. Beamforming methods reveal that most seismic events originate from two distinct locations, one on the grid-north side of the grounding zone, and one on the grid-south side. The broad pattern of deformation generated as Beardmore Glacier merges with the Ross Ice Shelf results in net extension along the grid-north side of the grounding zone …