Oxygen, pH and calcium dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH and across a range of irradiances

Presently, an incomplete mechanistic understanding of tropical reef macroalgae photosynthesis and calcification restricts predictions of how these important autotrophs will respond to global change. Therefore, we investigated the mechanistic link between inorganic carbon uptake pathways, photosynthesis and calcification in a tropical crustose coralline alga (CCA) using microsensors. We measured pH, oxygen (O2), and calcium (Ca2+) dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH (pHSW) and across a range of irradiances. Acetazolamide (AZ) was used to inhibit extracellular carbonic anhydrase (CAext), which mediates hydrolysis of HCO3-, and 4,4' diisothiocyanatostilbene-2,2'-disulphonate (DIDS) that blocks direct HCO3- uptake by anion exchange transport. Both inhibited photosynthesis, suggesting both diffusive uptake of CO2 via HCO3- hydrolysis to CO2 and direct HCO3- ion transport are important in this CCA. Surface pH was raised approximately 0.3 units at saturating irradiance, but less when CAext was inhibited. Surface pH was lower at pHSW 7.8 than pHSW 8.1 in the dark, but not in the light. The Ca2+ fluxes were large, complex and temporally variable, but revealed net Ca2+ uptake under all conditions. The temporal variability in Ca2+ dynamics was potentially related to localized dissolution during epithallial cell sloughing, a strategy of CCA to remove epiphytes. Simultaneous Ca2+ and pH dynamics suggest the presence of Ca2+/H+ exchange. Rapid light-induced H+ surface dynamics that continued after inhibition of photosynthesis revealed the presence of a light-mediated, but photosynthesis-independent, proton pump. Thus, the study indicates metabolic control of surface pH can occur in CCA through photosynthesis and light-inducible H+ pumps. Our results suggest that complex light-induced ion pumps play an important role in biological processes related to inorganic carbon uptake and calcification in CCA.

At surface behaviour of juvenile and female southern elephant seals from King George Island from expeditions JUB1996 and JUB1997

Between December 1996 and February 1997, weaned pups and postmoult female southern elephant seals (Mirounga leonina) were fitted with satellite transmitters at King George Island (South Shetlands). Of the nine adult females tracked for more than two months, three stayed in a localized area between the South Shetlands and the South Orkneys. The other six females travelled southwest along the coast of the Antarctic Peninsula up to the Bellingshausen Sea. Two of them then moved far northeast and hauled out on South Georgia in October. One female was last located north of the South Shetlands in March 1998. In total, eight females were again sighted on King George Island and six of the transmitters removed. The tracks of the weaners contrasted with those of the adults. In January, five juveniles left King George Island for the Pacific sector ranging about four weeks in the open sea west of the De Gerlache Seamounts. Three of them returned to the tip of the Antarctic Peninsula in June, of which one was last located on the Patagonian Shelf in November 1997. A computer animation was developed to visualize the animal movements in relation to the extent and concentration of sea ice. The juveniles avoided sea ice while the adults did not. The latter displayed behavioural differences in using the pack ice habitat during winter. Some females adjusted their movement patterns to the pulsating sea ice fringe in far-distant foraging areas while others ranged in closed pack ice of up to 100 %. The feeding grounds of adult female elephant seals are more closely associated with the pack ice zone than previously assumed.

Resonance fluorescence spectrum of a \Lambda-type quantum emitter close to a metallic nanoparticle

We theoretically study the resonance fluorescence spectrum of a three-level quantum emitter coupled to a spherical metallic nanoparticle. We consider the case that the quantum emitter is driven by a single laser field along one of the optical transitions. We show that the development of the spectrum depends on the relative orientation of the dipole moments of the optical transitions in relation to the metal nanoparticle. In addition, we demonstrate that the location and width of the peaks in the spectrum are strongly modified by the exciton-plasmon coupling and the laser detuning, allowing to achieve controlled strongly subnatural spectral line. A strong antibunching of the fluorescent photons along the undriven transition is also obtained. Our results may be used for creating a tunable source of photons which could be used for a probabilistic entanglement scheme in the field of quantum information processing.

Surface waves in mesh synthetic photonic lattices

Eigenmodes and dispersion curves in different configurations of synthetic photonic lattices are studied numerically. Eigenmodes localized on borders between areas with different optical potential are found. Stability of these eigenmodes against potential disturbances of different type is studied.

In-situ examination of the selective etching of an alkanethiol monolayer covered Au{111} surface

An examination of the selective etching mechanism of a 1-alkanethiol self-assembled monolayer (SAM) covered Au{111} surface using in-situ atomic force microscopy (AFM) and molecular resolution scanning tunnelling microscopy (STM) is presented. The monolayer self-assembles on a smooth Au{111} surface and typically contains nanoscale non-uniformities such as pinholes, domain boundaries and monatomic depressions. During etching in a ferri/ferrocyanide water-based etchant, selective and preferential etching occurs at SAM covered Au(111) terrace and step edges where a lower SAM packing density is observed, resulting in triangular islands being relieved. The triangular islands are commensurate with the Au(111) lattice with their long edges parallel to its [11-0] direction. Thus, SAM etching is selective and preferential attack is localized to defects and step edges at sites of high molecular density contrast.

Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius

In this paper, we use density functional theory corrected for on-site Coulomb interactions (DFT + U) and hybrid DFT (HSE06 functional) to study the defects formed when the ceria (110) surface is doped with a series of trivalent dopants, namely, Al3+, Sc3+, Y3+, and In 3+. Using the hybrid DFT HSE06 exchange-correlation functional as a benchmark, we show that doping the (110) surface with a single trivalent ion leads to formation of a localized MCe / + O O • (M = the 3+ dopant), O- hole state, confirming the description found with DFT + U. We use DFT + U to investigate the energetics of dopant compensation through formation of the 2MCe ′ +VO ̈ defect, that is, compensation of two dopants with an oxygen vacancy. In conjunction with earlier work on La-doped CeO2, we find that the stability of the compensating anion vacancy depends on the dopant ionic radius. For Al3+, which has the smallest ionic radius, and Sc3+ and In3+, with intermediate ionic radii, formation of a compensating oxygen vacancy is stable. On the other hand, the Y3+ dopant, with an ionic radius close to that of Ce4+, shows a positive anion vacancy formation energy, as does La3+, which is larger than Ce4+ (J. Phys.: Condens. Matter 2010, 20, 135004). When considering the resulting electronic structure, in Al3+ doping, oxygen hole compensation is found. However, Sc 3+, In3+, and Y3+ show the formation of a reduced Ce3+ cation and an uncompensated oxygen hole, similar to La3+. These results suggest that the ionic radius of trivalent dopants strongly influences the final defect formed when doping ceria with 3+ cations. In light of these findings, experimental investigations of these systems will be welcome.

Radium 228 and Radium 226 in surface water of the Kara Sea and Laptev Sea

The surface water in the Transpolar Drift in the Arctic Ocean has a strong signature of 228Ra. In an earlier study of 228Ra in the open Arctic we showed that the major 228Ra source had to be in the Siberian shelf seas, but only a single shelf station was published so far. Here we investigate the sources of this signal on the Siberian shelves by measurements of 228Ra and 226Ra in surface waters of the Kara and Laptev Sea, including the Ob, Yenisey and Lena estuaries. In the Ob and Lena rivers we found an indication for a very strong and unexpected removal of both isotopes in the early stage of estuarine mixing, presumably related to flocculation of organic-rich material. Whereas 226Ra behaves conservatively on the shelf, the distribution of 228Ra is governed by large inputs on the shelves, although sources are highly variable. In the Kara Sea the maximum activity was found in the Baydaratskaya Bay, where tidal resonance and low freshwater supply favour 228Ra accumulation. The Laptev Sea is a stronger source for 228Ra than the Kara Sea. Since a large part of Kara Sea water flows through the Laptev Sea, the 228Ra signal in the Transpolar Drift can be described as originating on the Laptev shelf. The combined freshwater inputs from the Eurasian shelves thus produce a common radium signature with a 228Ra/226Ra activity ratio of 4.0 at 20% river water. The radium signals of the individual Siberian rivers and shelves cannot be separated, but their signal is significantly different from the signal produced on the Canadian shelf (Smith et al., in press). In this respect, the radium tracers add to the information given by Barium. Moreover, with the 5.8 year half-life of 228Ra, they have the potential to serve as a tracer for the age of a water mass since its contact with the shelves.

Redistribution of Soil Organic Matter by Permafrost Disturbance in the Canadian High Arctic

With increased warming in the Arctic, permafrost thaw may induce localized physical disturbance of slopes. These disturbances, referred to as active layer detachments (ALDs), redistribute soil across the landscape, potentially releasing previously unavailable carbon (C). In 2007–2008, widespread ALD activity was reported at the Cape Bounty Arctic Watershed Observatory in Nunavut, Canada. Our study investigated organic matter (OM) composition in soil profiles from ALD-impacted and undisturbed areas. Solid-state 13C nuclear magnetic resonance (NMR) and solvent-extractable biomarkers were used to characterize soil OM. Throughout the disturbed upslope profile, where surface soils and vegetation had been removed, NMR revealed low O-alkyl C content and biomarker analysis revealed low concentrations of solvent-extractable compounds suggesting enhanced erosion of labile-rich OM by the ALD. In the disturbed downslope region, vegetation remained intact but displaced material from upslope produced lateral compression ridges at the surface. High O-alkyl content in the surface horizon was consistent with enrichment of carbohydrates and peptides, but low concentrations of labile biomarkers (i.e., sugars) suggested the presence of relatively unaltered labile-rich OM. Decreased O-alkyl content and biomarker concentrations below the surface contrasted with the undisturbed profile and may indicate the loss of well-established pre-ALD surface drainage with compression ridge formation. However, pre-ALD profile composition remains unknown and the observed decreases may result from nominal pre-ALD OM inputs. These results are the first to establish OM composition in ALD-impacted soil profiles, suggesting reallocation of permafrost-derived soil C to areas where degradation or erosion may contribute to increased C losses from disturbed Arctic soils.

Surface water subduction during a downwelling event in a semi-enclosed bay

The Ría de Vigo is a bay strongly influenced by upwelling-downwelling cycles along the adjacent coast of NW Iberia. Moored and ship-board observations during September 2006 showed that subduction, initially associated with an estuarine circulation, strengthened when a strong downwelling circulation, resulting from northward wind over the coastal ocean, was generated in the outer ría causing ambient waters to be advected outward in the lower layer. Incoming surface waters confined the estuarine circulation to the shallow interior and displaced isopleths downward through the water column at ∼10 m d−1. As the estuarine circulation retreated inward, strong flow convergence developed between middle and inner ria in the layer above 15 m, while divergence developed beneath. The convergence increased through the period of downwelling-favorable wind at a rate consistent with the observed isopleth displacement velocities. The coefficient of turbulent diffusion Kt, from a microstructure profiler, indicated that mixing was strong in the estuarine circulation and subsequently in the downwelling zone, where localized instabilities and temperature-salinity inversions were observed. During the downwelling, concentrations of phytoplankton, including potentially harmful species, increased, especially in the middle and inner ria, as a result of inward advection, subduction and the ability of the dinoflagellates to maintain their position in the water column by swimming. In the course of the 5 day event, the water mass of all but the innermost ría was flushed completely and replaced by waters originating in the coastally-trapped poleward flow along the Atlantic coastline.

Surface water subduction during a downwelling event in a semi-enclosed bay

The Ría de Vigo is a bay strongly influenced by upwelling-downwelling cycles along the adjacent coast of NW Iberia. Moored and ship-board observations during September 2006 showed that subduction, initially associated with an estuarine circulation, strengthened when a strong downwelling circulation, resulting from northward wind over the coastal ocean, was generated in the outer ría causing ambient waters to be advected outward in the lower layer. Incoming surface waters confined the estuarine circulation to the shallow interior and displaced isopleths downward through the water column at ∼10 m d−1. As the estuarine circulation retreated inward, strong flow convergence developed between middle and inner ria in the layer above 15 m, while divergence developed beneath. The convergence increased through the period of downwelling-favorable wind at a rate consistent with the observed isopleth displacement velocities. The coefficient of turbulent diffusion Kt, from a microstructure profiler, indicated that mixing was strong in the estuarine circulation and subsequently in the downwelling zone, where localized instabilities and temperature-salinity inversions were observed. During the downwelling, concentrations of phytoplankton, including potentially harmful species, increased, especially in the middle and inner ria, as a result of inward advection, subduction and the ability of the dinoflagellates to maintain their position in the water column by swimming. In the course of the 5 day event, the water mass of all but the innermost ría was flushed completely and replaced by waters originating in the coastally-trapped poleward flow along the Atlantic coastline.

Raman Analysis of Dilute Aqueous Samples by Localized Evaporation of Submicroliter Droplets on the Tips of Superhydrophobic Copper Wires

Raman analysis of dilute aqueous solutions is normally prevented by their low signal levels. A very general method to increase the concentration to detectable levels is to evaporate droplets of the sample to dryness, creating solid deposits which are then Raman probed. Here, superhydrophobic (SHP) wires with hydrophilic tips have been used as supports for drying droplets, which have the advantage that the residue is automatically deposited at the tip. The SHP wires were readily prepared in minutes using electroless galvanic deposition of Ag onto copper wires followed by modification with a polyfluorothiol (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanethiol, HDFT). Cutting the coated wires with a scalpel revealed hydrophilic tips which could support droplets whose maximum size was determined by the wire diameter. Typically, 230 μm wires were used to support 0.6 μL droplets. Evaporation of dilute melamine droplets gave solid deposits which could be observed by scanning electron microscopy (SEM) and Raman spectroscopy. The limit of detection for melamine using a two stage evaporation procedure was 1 × 10^-6 mol dm^-3. The physical appearance of dried droplets of sucrose and glucose showed that the samples retained significant amounts of water, even under high vacuum. Nonetheless, the Raman detection limits of sucrose and glucose were 5 × 10^-4 and 2.5 × 10^-3 mol dm^-3, respectively, which is similar to the sensitivity reported for surface-enhanced Raman spectroscopy (SERS) detection of glucose. It was also possible to quantify the two sugars in mixtures at concentrations which were similar to those found in human blood through multivariate analysis.

Breaking Waves on the Ocean Surface

Thesis (Ph.D.)--University of Washington, 2016-08

Optics-Based Quantum Information and Sensing Platforms Utilizing the Nitrogen-Vacancy Center in Diamond

Thesis (Ph.D.)--University of Washington, 2016-08

DESIGN AND APPLICATION OF WIRELESS PASSIVE MAGNETOELASTIC RESONANCE AND MAGNETOHARMONIC FORCE SENSORS

The objective of the work described in this dissertation is the development of new wireless passive force monitoring platforms for applications in the medical field, specifically monitoring lower limb prosthetics. The developed sensors consist of stress sensitive, magnetically soft amorphous metallic glass materials. The first technology is based on magnetoelastic resonance. Specifically, when exposed to an AC excitation field along with a constant DC bias field, the magnetoelastic material mechanically vibrates, and may reaches resonance if the field frequency matches the mechanical resonant frequency of the material. The presented work illustrates that an applied loading pins portions of the strip, effectively decreasing the strip length, which results in an increase in the frequency of the resonance. The developed technology is deployed in a prototype lower limb prosthetic sleeve for monitoring forces experienced by the distal end of the residuum. This work also reports on the development of a magnetoharmonic force sensor comprised of the same material. According to the Villari effect, an applied loading to the material results in a change in the permeability of the magnetic sensor which is visualized as an increase in the higher-order harmonic fields of the material. Specifically, by applying a constant low frequency AC field and sweeping the applied DC biasing field, the higher-order harmonic components of the magnetic response can be visualized. This sensor technology was also instrumented onto a lower limb prosthetic for proof of deployment; however, the magnetoharmonic sensor illustrated complications with sensor positioning and a necessity to tailor the interface mechanics between the sensing material and the surface being monitored. The novelty of these two technologies is in their wireless passive nature which allows for long term monitoring over the life time of a given device. Additionally, the developed technologies are low cost. Recommendations for future works include improving the system for real-time monitoring, useful for data collection outside of a clinical setting.

Sticking non-stick: surface and structure control of diamond-like carbon in plasma enhanced chemical vapour deposition

This short review article explores the practical use of diamond-like carbon (DLC) produced by plasma enhanced chemical vapour deposition (PECVD). Using as an example issues relating to the DLC coating of a hand-held surgical device, we draw on previous works using atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, tensiometry and electron paramagnetic resonance. Utilising data from these techniques, we examine the surface structure, substrate-film interface and thin film microstructure, such as sp2/sp3 ratio (graphitic/diamond-like bonding ratio) and sp2 clustering. We explore the variations in parameters describing these characteristics, and relate these to the final device properties such as friction, wear resistance, and diffusion barrier integrity. The material and device characteristics are linked to the initial plasma and substrate conditions.