Ionic liquids as solvents for near-infrared emitting lanthanide complexes

It is shown that ionic liquids are promising solvents for near-infrared emitting lanthanide complexes, because ionic liquids are polar non-coordinating solvents that can solubilize lanthanide complexes. Neodymium(III) tosylate, bromide, triflate and sulfonylimide complexes were dissolved in 1-alkyl-3-methylimidazolium ionic liquids that contain the same anion as the neodymium(III) complexes. Near-infrared luminescence spectra of these neodymium(III) salts were measured by direct excitation of the neodymium(III) ion. The absorption spectra show detailed crystal-field fine structure and Judd-Ofelt parameters have been determined. Intense near-infrared luminescence was observed upon ligand excitation for neodymium(III) complexes with 1,10-phenanthroline or beta-diketonate ligands. (C) 2004 Elsevier B.V. All rights reserved.

An Investigation of Compressor Map Width Enhancement and a Detailed Analysis of Inducer Flow Field

This paper describes an investigation of various shroud bleed slot configurations of a centrifugal compressor using CFD with a manual multi-block structured grid generation method. The compressor under investigation is used in a turbocharger application for a heavy duty diesel engine of approximately 400 hp. The baseline numerical model has been developed and validated against experimental performance measurements. The influence of the bleed slot flow field on a range of operating conditions between surge and choke has been analysed in detail.
The impact of the returning bleed flow on the incidence at the impeller blade leading edge due to its mixing with the main through-flow has also been studied. From the baseline geometry, a number of modifications to the bleed slot width have been proposed, and a detailed comparison of the flow characteristics performed. The impact of slot variations on the inlet incidence angle has been investigated, highlighting the improvement in surge and choked flow capability. Along with this, the influence of the bleed slot on stabilising the blade passage flow by the suction of the tip and over-tip vortex flow by the slot has been considered near surge.

Remote, subsurface detection of the algal toxin domoic acid onboard the Environmental Sample Processor: Assay development and field trials

The ability to detect harmful algal bloom (HAB) species and their toxins in real- or near real-time is a critical need for researchers studying HAB/toxin dynamics, as well as for coastal resource managers charged with monitoring bloom populations in order to mitigate their wide ranging impacts. The Environmental Sample Processor (ESP), a robotic electromechanical/fluidic system, was developed for the autonomous, subsurface application of molecular diagnostic tests and has successfully detected several HAB species using DNA probe arrays during field deployments. Since toxin production and thus the potential for public health and ecosystem effects varies considerably in natural phytoplankton populations, the concurrent detection of HAB species and their toxins onboard the ESP is essential. We describe herein the development of methods for extracting the algal toxin domoic acid (DA) from Pseudonitzschia cells (extraction efficiency >90%) and testing of samples using a competitive ELISA onboard the ESP. The assay detection limit is in the low ng/mL range (in extract), which corresponds to low ng/L levels of DA in seawater for a 0.5 L sample volume acquired by the ESP. We also report the first in situ detection of both a HAB organism (i.e., Pseudo-nitzschia) and its toxin, domoic acid, via the sequential (within 2-3 h) conduct of species- and toxin-specific assays during ESP deployments in Monterey Bay, CA, USA. Efforts are now underway to further refine the assay and conduct additional calibration exercises with the aim of obtaining more reliable, accurate estimates of bloom toxicity and thus their potential impacts. Published by Elsevier B.V.

From the UV to the static-field limit: rates and scaling laws of intense-field ionization of helium

We present high-accuracy calculations of ionization rates of helium at UV (195 nm) wavelengths. The data are obtained from full-dimensionality integrations of the helium-laser time-dependent Schrödinger equation. Comparison is made with our previously obtained data at 390 nm and 780 nm. We show that scaling laws introduced by Parker et al extend unmodified from the near-infrared limit into the UV limit. Static-field ionization rates of helium are also obtained, again from time-dependent full-dimensionality integrations of the helium Schrödinger equation. We compare the static-field ionization results with those of Scrinzi et al and Themelis et al, who also treat the full-dimensional helium atom, but with time-independent methods. Good agreement is obtained.

Relativistic channeling of a picosecond laser pulse in a near-critical preformed plasma

Relativistic self-channeling of a picosecond laser pulse in a preformed plasma near critical density has been observed both experimentally and in 3D particle-in-cell simulations. Optical probing measurements indicate the formation of a single pulsating propagation channel, typically of about 5 mu m in diameter. The computational results reveal the importance in the channel formation of relativistic electrons traveling with the light pulse and of the corresponding self-generated magnetic field.

Strong-field photodetachment of H- by few-cycle laser pulses

The recent adiabatic saddle-point method of Shearer et al. [ Phys. Rev. A 84 033409 (2011)] is applied to study strong-field photodetachment of H- by few-cycle linearly polarized laser pulses of frequencies near the two-photon detachment threshold. The behavior of the saddle points in the complex-time plane for a range of laser parameters is explored. A detailed analysis of the influence of laser intensities [(2×1011)–(6.5 × 1011) W/cm2], midinfrared laser wavelengths (1800–2700 nm), and various values of the carrier envelope phase (CEP) on (i) three-dimensional probability detachment distributions, (ii) photoangular distributions (PADs), (iii) energy spectra, and (iv) momentum distributions are presented. Examination of the probability distributions and PADs reveal main lobes and jetlike structures. Bifurcation phenomena in the probability distributions and PADs are also observed as the wavelength and intensity increase. Our simulations show that the (i) probability distributions, (ii) PADs, and (iii) energy spectra are extremely sensitive to the CEP and thus measuring such distributions provides a useful tool for determining this phase. The symmetrical properties of the electron momentum distributions are also found to be strongly correlated with the CEP and this provides an additional robust method for measuring the CEP of a laser pulse. Our calculations further show that for a three-cycle pulse inclusion of all eight saddle points is required in the evaluation of the transition amplitude to yield an accurate description of the photodetachment process. This is in contrast to recent results for a five-cycle pulse.

Dense spectrum of resonances and particle capture in a near-black-hole metric

We show that a quantum scalar particle in the gravitational field of a massive body of radius R which slightly exceeds the Schwarzschild radius rs, possesses a dense spectrum of narrow resonances. Their lifetimes and density tend to infinity in the limit R?rs. We determine the cross section of the particle capture into these resonances and show that it is equal to the absorption cross section for a Schwarzschild black hole. Thus, a nonsingular static metric acquires black-hole properties before the actual formation of a black hole.

Permafrost response to last interglacial warming: field evidence from non-glaciated Yukon and Alaska

We present stratigraphic observations from three sites in eastern Beringia - Ch'ijee's Bluff in northern Yukon and nearby exposures on the Old Crow River, the Palisades on the Yukon River in Alaska, and placer mining exposures at Thistle Creek in west-central Yukon - which provide insight into the response of permafrost to regional warming during the last interglaciation. Chronology is based on the presence of Old Crow tephra, an important regional stratigraphic marker that dates to late Marine Isotope Stage 6, supplemented by paleoecology and non-finite C ages on wood-rich organic silts. Old Crow tephra overlies several relict ice wedges at the Palisades and Thistle Creek, indicating that permafrost at these sites did not thaw completely during the last interglaciation. Prominent deposits of last interglacial wood-rich organic silt are present at multiple sites in eastern Beringia, and probably represent accumulations of reworked forest vegetation due to thaw slumping or deposition into thermokarst ponds or depressions. Consistent stratigraphic relations between these deposits, Old Crow tephra, and ice wedge pseudomorphs at our three study sites, and at least six other sites in eastern Beringia, suggest that thaw of shallow permafrost was widespread during the last interglaciation. Limited stratigraphic evidence suggests that thaw was probably on the order of meters, rather than 10s of meters. The ubiquity of shallow permafrost degradation during the last interglaciation suggests that current ground warming may foreshadow widespread near-surface thaw under even modest future warming scenarios. However, the persistence of relict pre-last interglacial ice wedges highlights the potential for the regional antiquity of discontinuous permafrost, and provides compelling field evidence for the long-term resilience of deep permafrost during sustained periods of warmer-than-present climate.

Field observation of sequestration of uranium in iron-rich sediments under sequential reduction-oxidation conditions at the DOE Oak Ridge IFRC

At the U.S. DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site, the iron content of shallow subsurface materials (i.e. weathered saprolite) is relatively high (up to 5-6% as w/w), and therefore, the forms of the iron species present plays a critical role in the long-term sequestration of uranium. A long term pilot-scale study of the bioreduction and reoxidation of uranium conducted at the ORIFRC area 3 site, adjacent to the former S-3 disposal ponds (source zone), has provided us with the opportunity to study the impact of iron species on the sequestration of U(VI). The aqueous U(VI) concentrations at the site were decreased to below the EPA MCL through the intermittent injection of ethanol as the electron donor. Previous field tests indicated that both oxygen and nitrate could oxidize the bioreduced U(IV) and cause a short-term rebound of aqueous phase uranium concentration after the oxidative agents were delivered directly to the bioreduced zone.

A field test has been conducted to examine the long-term effect of exposure of bioreduced sediments to nitrate in contaminated groundwater for more than 1,380 days at the Area 3 site. Contaminated groundwater was allowed to invade the previously bioreduced zone via the natural groundwater gradient after an extended period in which reducing conditions were maintained and the bioreduced zone was protected from the influx of upgradient contaminated groundwater. The geochemical response to the invasion of contaminated groundwater was dependent on whether the monitoring location is in the middle or the fringe of the previously bioreduced zone. In general, the nitrate concentrations in the previously bioreduced area, increased gradually from near zero to ~50-300 mM within 200 days and then stabilized. The pH declined from bioreduced levels of 6.2-6.7 to below 5.0. Uranium concentrations rebounded in all monitoring wells but at different rates. At most locations U concentrations rebounded, declined and then rebounded again. Methane gas disappeared while a significant level (20,000 to 44,000 ppmv) N2O was found in the groundwater of monitoring wells after three years of reoxidization.

The U(IV) in sediments was mainly reoxidized to U(VI) species. Based on XANES analysis, the predominate uranium in all samples after re-oxidation was similar to a uranyl nitrate form. But the U content in the sediment remained as high as that determined after bioreduction activates were completed, indicating that much of the U is still sequestrated in situ. SEM observations of surged fine sediments revealed that clusters of colloidal-sized (200-500nm) U-containing precipitates appeared to have formed in situ, regardless from sample of FW106 in non-bioactivity control area or of pre-bioreduced FW101-2 and FW102-3. Additionally, SEM-EDS and microprobe analysis, showed that the U-containing precipitates (~1% U) in FW106 are notably higher in Fe, compared to the precipitates (~1-2.5% U) from FW101-2 and FW102-3. However, XRF analysis indicated that the U content was remained as high as 2180 and 1810 mg/kg with U/Fe ratio at 0.077 and 0.055 vs 0.037 g/g, respectively in pre-bioreduced FW101-2 and FW102-3, suggesting more U sequestrated by Fe in pre-bioreduced sediments.

The influence of the magnetic field on running penumbral waves in the solar chromosphere

We use images of high spatial and temporal resolution, obtained using both ground- and space-based instrumentation, to investigate the role magnetic field inclination angles play in the propagation characteristics of running penumbral waves in the solar chromosphere. Analysis of a near-circular sunspot, close to the center of the solar disk, reveals a smooth rise in oscillatory period as a function of distance from the umbral barycenter. However, in one directional quadrant, corresponding to the north direction, a pronounced kink in the period-distance diagram is found. Utilizing a combination of the inversion of magnetic Stokes vectors and force-free field extrapolations, we attribute this behavior to the cut-off frequency imposed by the magnetic field geometry in this location. A rapid, localized inclination of the magnetic field lines in the north direction results in a faster increase in the dominant periodicity due to an accelerated reduction in the cut-off frequency. For the first time, we reveal how the spatial distribution of dominant wave periods, obtained with one of the highest resolution solar instruments currently available, directly reflects the magnetic geometry of the underlying sunspot, thus opening up a wealth of possibilities in future magnetohydrodynamic seismology studies. In addition, the intrinsic relationships we find between the underlying magnetic field geometries connecting the photosphere to the chromosphere, and the characteristics of running penumbral waves observed in the upper chromosphere, directly supports the interpretation that running penumbral wave phenomena are the chromospheric signature of upwardly propagating magneto-acoustic waves generated in the photosphere.

Dense spectrum of resonances and spin-1/2 particle capture in a near-black-hole metric

We show that a spin-1/2 particle in the gravitational field of a massive body of radius R which slightly exceeds the Schwarzschild radius rs, possesses a dense spectrum of narrow resonances. Their lifetimes and density tend to infinity in the limit R → rs. We determine the cross section of the particle capture into these resonances and show that it is equal to the spin-1/2 absorption cross section for a Schwarzschild black hole. Thus black-hole properties may emerge in a non-singular static metric prior to the formation of a black hole.

Genome Wide Association Mapping of Grain Arsenic, Copper, Molybdenum and Zinc in Rice (Oryza sativa L.) Grown at Four International Field Sites

The mineral concentrations in cereals are important for human health, especially for individuals who consume a cereal subsistence diet. A number of elements, such as zinc, are required within the diet, while some elements are toxic to humans, for example arsenic. In this study we carry out genome-wide association (GWA) mapping of grain concentrations of arsenic, copper, molybdenum and zinc in brown rice using an established rice diversity panel of,300 accessions and 36.9 k single nucleotide polymorphisms (SNPs). The study was performed across five environments: one field site in Bangladesh, one in China and two in the US, with one of the US sites repeated over two years. GWA mapping on the whole dataset and on separate subpopulations of rice revealed a large number of loci significantly associated with variation in grain arsenic, copper, molybdenum and zinc. Seventeen of these loci were detected in data obtained from grain cultivated in more than one field location, and six co-localise with previously identified quantitative trait loci. Additionally, a number of candidate genes for the uptake or transport of these elements were located near significantly associated SNPs (within 200 kb, the estimated global linkage disequilibrium previously employed in this rice panel). This analysis highlights a number of genomic regions and candidate genes for further analysis as well as the challenges faced when mapping environmentally-variable traits in a highly genetically structured diversity panel.

Electron rescattering in strong-field photodetachment of F-

We present ab initio studies of photoelectron spectra for above threshold detachment (ATD) of F- anions in short, 1300 nm and 1800 nm laser pulses. We identify and assess the importance of electron rescattering in strong-field photodetachment of a negative ion through comparison with an analytic, Keldysh-type approach, demonstrating the capability of ab-initio computation in the challenging near-IR regime. We further assess the influence of the strong electron correlation on the photodetachment.

Near-monochromatic high-harmonic radiation from relativistic laser-plasma interactions with blazed grating surfaces

Intense, femtosecond laser interactions with blazed grating targets are studied through experiment and particle-in-cell (PIC) simulations. The high harmonic spectrum produced by the laser is angularly dispersed by the grating leading to near-monochromatic spectra emitted at different angles, each dominated by a single harmonic and its integer-multiples. The spectrum emitted in the direction of the third-harmonic diffraction order is measured to contain distinct peaks at the 9th and 12th harmonics which agree well with two-dimensional PIC simulations using the same grating geometry. This confirms that surface smoothing effects do not dominate the far-field distributions for surface features with sizes on the order of the grating grooves whilst also showing this to be a viable method of producing near-monochromatic, short-pulsed extreme-ultraviolet radiation.

Pathways Project Final Report Volume 1: Field Investigation and Catchment Conceptual Models

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Executive Summary
The Pathways Project field studies were targeted at improving the understanding of contaminant transport along different hydrological pathways in Irish catchments, including their associated impacts on water quality and river ecology. The contaminants of interest were phosphorus, nitrogen and sediment. The working Pathways conceptual model included overland flow, interflow, shallow groundwater flow, and deep groundwater flow. This research informed the development of a set of Catchment Management Support Tools (CMSTs) comprising an Exploratory Tool, Catchment Characterization Tool (CCT) and Catchment Modelling Tool (CMT) as outlined in Pathways Project Final Reports Volumes 3 and 4.
In order to inform the CMST, four suitable study catchments were selected following an extensive selection process, namely the Mattock catchment, Co. Louth/Meath; Gortinlieve catchment, Co. Donegal; Nuenna catchment, Co. Kilkenny and the Glen Burn catchment, Co. Down. The Nuenna catchment is well drained as it is underlain by a regionally important karstified limestone aquifer with permeable limestone tills and gravels, while the other three catchments are underlain by poorly productive aquifers and low permeability clayey tills, and are poorly drained.
All catchments were instrumented, and groundwater, surface and near-surface water and aquatic ecology were monitored for a period of two years. Intensive water quality sampling during rainfall events was used to investigate the pathways delivering nutrients. The proportion of flow along each pathway was determined using chemical and physical hydrograph separation techniques, supported by numerical modelling.
The outcome of the field studies broadly supported the use of the initial four-pathway conceptual model used in the Pathways CMT (time-variant model). The artificial drainage network was found to be a significant contributing pathway in the poorly drained catchments, at low flows and during peak flows in wet antecedent conditions. The transition zone (TZ), i.e. the broken up weathered zone at the top of the bedrock, was also found to be an important pathway. It was observed to operate in two contrasting hydrogeological scenarios: in groundwater discharge zones the TZ can be regarded as being part of the shallow groundwater pathway, whereas in groundwater recharge zones it behaves more like interflow.
In the catchments overlying poorly productive aquifers, only a few fractures or fracture zones were found to be hydraulically active and the TZ, where present, was the main groundwater pathway. In the karstified Nuenna catchment, the springs, which are linked to conduits as well as to a diffuse fracture network, delivered the majority of the flow. These findings confirm the two-component groundwater contribution from bedrock but suggest that the size and nature of the hydraulically active fractures and the nature of the TZ are the dominant factors at the scale of a stream flow event.
Diffuse sources of nitrate were found to be typically delivered via the subsurface pathways, especially in the TZ and land drains in the poorly productive aquifer catchments, and via the bedrock groundwater in the Nuenna. Phosphorus was primarily transported via overland flow in both particulate and soluble forms. Where preferential flow paths existed in the soil and subsoil, soluble P, and to a lesser extent particulate P, were also transported via the TZ and in drains and ditches. Arable land was found to be the most important land use for
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the delivery of sediment, although channel bank and in-stream sources were the most significant in the Glen Burn catchment. Overland flow was found to be the predominant transport sediment pathway in the poorly productive catchments. These findings informed the development of the transport and attenuation equations used in the CCT and CMT. From an assessment of the relationship between physico-chemical and biological conditions, it is suggested that in the Nuenna, Glen Burn and Gortinlieve catchments, a relationship may exist between biological water quality and nitrogen concentrations, as well as with P. In the Nuenna, there was also a relationship between macroinvertebrate status and alkalinity.
Further research is recommended on the transport and delivery of phosphorus in groundwater, the transport and attenuation dynamics in the TZ in different hydrogeological settings and the relationship between macroinvertebrates and co-limiting factors. High resolution temporal and spatial sampling was found to be important for constraining the conceptual understanding of nutrient and sediment dynamics which should also be considered in future studies.