193 research outputs found
Air–snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 2: Mercury and its speciation
Atmospheric mercury depletion events (AMDEs) refer to a recurring depletion
of mercury occurring in the springtime Arctic (and Antarctic) boundary layer,
in general, concurrently with ozone depletion events (ODEs). To close some of
the knowledge gaps in the physical and chemical mechanisms of AMDEs and ODEs,
we have developed a one-dimensional model that simulates multiphase chemistry
and transport of trace constituents throughout porous snowpack and in the
overlying atmospheric boundary layer (ABL). This paper constitutes Part 2 of
the study, describing the mercury component of the model and its application
to the simulation of AMDEs. Building on model components reported in Part 1
("In-snow bromine activation and its impact on ozone"), we have developed a
chemical mechanism for the redox reactions of mercury in the gas and aqueous
phases with temperature dependent reaction rates and equilibrium constants
accounted for wherever possible. Thus the model allows us to study the
chemical and physical processes taking place during ODEs and AMDEs within a
single framework where two-way interactions between the snowpack and the
atmosphere are simulated in a detailed, process-oriented manner. Model runs
are conducted for meteorological and chemical conditions that represent the
springtime Arctic ABL characterized by the presence of "haze" (sulfate
aerosols) and the saline snowpack on sea ice. The oxidation of gaseous
elemental mercury (GEM) is initiated via reaction with Br-atom to form HgBr,
followed by competitions between its thermal decomposition and further
reactions to give thermally stable Hg(II) products. To shed light on
uncertain kinetics and mechanisms of this multi-step oxidation process, we
have tested different combinations of their rate constants based on published
laboratory and quantum mechanical studies. For some combinations of the rate
constants, the model simulates roughly linear relationships between the
gaseous mercury and ozone concentrations as observed during AMDEs/ODEs by
including the reaction HgBr + BrO and assuming its rate constant to be the
same as for the reaction HgBr + Br, while for other combinations the
results are more realistic by neglecting the reaction HgBr + BrO.
Speciation of gaseous oxidized mercury (GOM) changes significantly depending
on whether or not BrO is assumed to react with HgBr to form Hg(OBr)Br.
Similarly to ozone (reported in Part 1), GEM is depleted via bromine radical
chemistry more vigorously in the snowpack interstitial air than in the
ambient air. However, the impact of such in-snow sink of GEM is found to be
often masked by the re-emissions of GEM from the snow following the
photo-reduction of Hg(II) deposited from the atmosphere. GOM formed in the
ambient air is found to undergo fast "dry deposition" to the snowpack by
being trapped on the snow grains in the top ~1 mm layer. We
hypothesize that liquid-like layers on the surface of snow grains are
connected to create a network throughout the snowpack, thereby facilitating
the vertical diffusion of trace constituents trapped on the snow grains at
much greater rates than one would expect inside solid ice crystals.
Nonetheless, on the timescale of a week simulated in this study, the signal
of atmospheric deposition does not extend notably below the top 1 cm of the
snowpack. We propose and show that particulate-bound mercury (PBM) is
produced mainly as HgBr<sub>4</sub><sup>2−</sup> by taking up GOM into bromide-enriched
aerosols after ozone is significantly depleted in the air mass. In the
Arctic, "haze" aerosols may thus retain PBM in ozone-depleted air masses,
allowing the airborne transport of oxidized mercury from the area of its
production farther than in the form of GOM. Temperature dependence of
thermodynamic constants calculated in this study for Henry's law and
aqueous-phase halide complex formation of Hg(II) species is a critical factor
for this proposition, calling for experimental verification. The proposed
mechanism may explain observed changes in the GOM–PBM partitioning with
seasons, air temperature and the concurrent progress of ozone depletion in
the high Arctic. The net deposition of mercury to the surface snow is shown
to increase with the thickness of the turbulent ABL and to correspond well
with the column amount of BrO in the atmosphere
Developing Organizational Culture In Independently Owned Restaurants: Links To Service Quality And Customers Intentions To Return
The study developed and tested a model of organizational culture and customer service as they relate to behavioral intention to return in independently owned, casual dining restaurants. It adds to previous work on organizational culture and hospitality as they related to service quality and behavioral intentions to return by assessing two types of organizational culture, clan and market types. Results indicate that, as proposed, clan culture type is positively related to high levels of perceived service quality and to intentions to return to the restaurant; however market culture type is, as expected, negatively related to intentions to return. The findings lead to practical applications for the restaurant industry with a blueprint for practitioners to develop and improve their service delivery practices in order to generate a larger number of repeat customers
Air–snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 1: In-snow bromine activation and its impact on ozone
To provide a theoretical framework towards a better understanding of ozone
depletion events (ODEs) and atmospheric mercury depletion events (AMDEs) in
the polar boundary layer, we have developed a one-dimensional model that
simulates multiphase chemistry and transport of trace constituents from
porous snowpack and through the atmospheric boundary layer (ABL) as a unified
system. This paper constitutes Part 1 of the study, describing a general
configuration of the model and the results of simulations related to reactive
bromine release from the snowpack and ODEs during the Arctic spring. A common
set of aqueous-phase reactions describes chemistry both within the
liquid-like layer (LLL) on the grain surface of the snowpack and within
deliquesced "haze" aerosols mainly composed of sulfate in the atmosphere.
Gas-phase reactions are also represented by the same mechanism in the
atmosphere and in the snowpack interstitial air (SIA). Consequently, the
model attains the capacity of simulating interactions between chemistry and
mass transfer that become particularly intricate near the interface between
the atmosphere and the snowpack. In the SIA, reactive uptake on LLL-coated
snow grains and vertical mass transfer act simultaneously on gaseous HOBr, a
fraction of which enters from the atmosphere while another fraction is formed
via gas-phase chemistry in the SIA itself. A "bromine explosion", by which
HOBr formed in the ambient air is deposited and then converted
heterogeneously to Br<sub>2</sub>, is found to be a dominant process of reactive
bromine formation in the top 1 mm layer of the snowpack. Deeper in the
snowpack, HOBr formed within the SIA leads to an in-snow bromine explosion,
but a significant fraction of Br<sub>2</sub> is also produced via aqueous
radical chemistry in the LLL on the surface of the snow grains. These top-
and deeper-layer productions of Br<sub>2</sub> both contribute to the release of
Br<sub>2</sub> to the atmosphere, but the deeper-layer production is found to be
more important for the net outflux of reactive bromine. Although ozone is
removed via bromine chemistry, it is also among the key species that control
both the conventional and in-snow bromine explosions. On the other hand,
aqueous-phase radical chemistry initiated by photolytic OH formation in the
LLL is also a significant contributor to the in-snow source of Br<sub>2</sub>
and can operate without ozone, whereas the delivery of Br<sub>2</sub> to the
atmosphere becomes much smaller after ozone is depleted. Catalytic ozone loss
via bromine radical chemistry occurs more rapidly in the SIA than in the
ambient air, giving rise to apparent dry deposition velocities for ozone from
the air to the snow on the order of 10<sup>−3</sup> cm s<sup>−1</sup> during
daytime. Overall, however, the depletion of ozone in the system is caused
predominantly by ozone loss in the ambient air. Increasing depth of the
turbulent ABL under windy conditions will delay the buildup of reactive
bromine and the resultant loss of ozone, while leading to the higher column
amount of BrO in the atmosphere. During the Arctic spring, if moderately
saline and acidic snowpack is as prevalent as assumed in our model runs on
sea ice, the shallow, stable ABL under calm weather conditions may undergo
persistent ODEs without substantial contributions from blowing/drifting snow
and wind-pumping mechanisms, whereas the column densities of BrO in the ABL
will likely remain too low in the course of such events to be detected
unambiguously by satellite nadir measurements
Measuring scattering distributions in scanning helium microscopy
A scanning helium microscope typically utilises a thermal energy helium atom
beam, with an energy and wavelength (<100 meV, ~0.05 nm) particularly sensitive
to surface structure. An angular detector stage for a scanning helium
microscope is presented that facilitates the in-situ measurement of scattering
distributions from a sample. We begin by demonstrating typical elastic and
inelastic scattering from ordered surfaces. We then go on to show the role of
topography in diffuse scattering from disordered surfaces, observing deviations
from simple cosine scattering. In total, these studies demonstrate the wealth
of information that is encoded into the scattering distributions obtained with
the technique.Comment: 10 pages, 9 figure
Unlocking new contrast in a scanning helium microscope.
Delicate structures (such as biological samples, organic films for polymer electronics and adsorbate layers) suffer degradation under the energetic probes of traditional microscopies. Furthermore, the charged nature of these probes presents difficulties when imaging with electric or magnetic fields, or for insulating materials where the addition of a conductive coating is not desirable. Scanning helium microscopy is able to image such structures completely non-destructively by taking advantage of a neutral helium beam as a chemically, electrically and magnetically inert probe of the sample surface. Here we present scanning helium micrographs demonstrating image contrast arising from a range of mechanisms including, for the first time, chemical contrast observed from a series of metal-semiconductor interfaces. The ability of scanning helium microscopy to distinguish between materials without the risk of damage makes it ideal for investigating a wide range of systems.This research was supported under the Australian Research Councils Discovery Projects (Project No. DP08831308) funding scheme. Postgraduate research scholarships (M.B., A.F.) from the University of Newcastle gratefully acknowledged. We thank the Newcastle and Cavendish workshops, Donald MacLaren and Kane O’Donnell for technical support, insightful discussions and assistance. This work was performed in part at both the Materials and ACT nodes of the Australian National Fabrication Facility, which is a company established under the National Collaborative Research Infrastructure Strategy to provide nano- and micro-fabrication facilities for Australia’s researchers.This is the final version of the article. It was first available from NPG via http://dx.doi.org/10.1038/ncomms1018
ENERGY EFFICIENCY ANALYSIS FOR LTE-A HETEROGENEOUS CELLULAR NETWORK
Existing cellular network gives us the large network coverage as well as network capacity but in many cases it fails to achieve predicted data rates for the seamless wireless communication. Moreover there is a tremendous increase in wireless device users so the data rates and network capacity offered by conventional cellular network is not sufficient. So the effort to suppress base-stations power consumption are desperately needed and for that heterogeneous cellular network has been introduced. This paper provides the complete analysis of energy efficient wireless systems for heterogeneous cellular network as it has been pointed out to be one of the key network architectures that help to increase system capacity and reduce power consumption. Heterogeneous network with coordinated multi-point has received significant attention as a way of achieving energy efficiency and to improve the network handling capacity in heterogeneous cellular network. Usually in communication those users which are on the edge of the cells always suffer with the low data rates and low capacity. Moreover they get interference from the adjacent cells. To mitigate these problems and achieve higher energy efficiency Heterogeneous network with coordinated multi-point came out as one of the best solutions. In this paper heterogeneous network is considered with the Voronoi tessellation and between the cells coordinated multi-point technique is applied and compared with the non- coordinated multipoint scenario. Heterogeneous network is the integrated part of the beyond 4G wireless network for better energy efficiency
A synthesis of atmospheric mercury depletion event chemistry in the atmosphere and snow
It was discovered in 1995 that, during the spring time, unexpectedly low concentrations of gaseous elemental mercury (GEM) occurred in the Arctic air. This was surprising for a pollutant known to have a long residence time in the atmosphere; however conditions appeared to exist in the Arctic that promoted this depletion of mercury (Hg). This phenomenon is termed atmospheric mercury depletion events (AMDEs) and its discovery has revolutionized our understanding of the cycling of Hg in Polar Regions while stimulating a significant amount of research to understand its impact to this fragile ecosystem. Shortly after the discovery was made in Canada, AMDEs were confirmed to occur throughout the Arctic, sub-Artic and Antarctic coasts. It is now known that, through a series of photochemically initiated reactions involving halogens, GEM is converted to a more reactive species and is subsequently associated to particles in the air and/or deposited to the polar environment. AMDEs are a means by which Hg is transferred from the atmosphere to the environment that was previously unknown. In this article we review Hg research taken place in Polar Regions pertaining to AMDEs, the methods used to collect Hg in different environmental media, research results of the current understanding of AMDEs from field, laboratory and modeling work, how Hg cycles around the environment after AMDEs, gaps in our current knowledge and the future impacts that AMDEs may have on polar environments. The research presented has shown that while considerable improvements in methodology to measure Hg have been made but the main limitation remains knowing the speciation of Hg in the various media. The processes that drive AMDEs and how they occur are discussed. As well, the role that the snow pack and the sea ice play in the cycling of Hg is presented. It has been found that deposition of Hg from AMDEs occurs at marine coasts and not far inland and that a fraction of the deposited Hg does not remain in the same form in the snow. Kinetic studies undertaken have demonstrated that bromine is the major oxidant depleting Hg in the atmosphere. Modeling results demonstrate that there is a significant deposition of Hg to Polar Regions as a result of AMDEs. Models have also shown that Hg is readily transported to the Arctic from source regions, at times during springtime when this environment is actively transforming Hg from the atmosphere to the snow and ice surfaces. The presence of significant amounts of methyl Hg in snow in the Arctic surrounding AMDEs is important because this species is the link between the environment and impacts to wildlife and humans. Further, much work on methylation and demethylation processes has occurred but these processes are not yet fully understood. Recent changes in the climate and sea ice cover in Polar Regions are likely to have strong effects on the cycling of Hg in this environment; however more research is needed to understand Hg processes in order to formulate meaningful predictions of these changes
The templated growth of a chiral transition metal chalcogenide
We demonstrate that an intrinsically chiral, high Miller index surface of an achiral metal can be used to template the enantioselective growth of chiral transition metal chalcogenide films. Specifically, Cu(643)R can be used as a template for the enantioselective growth of a chiral copper telluride alloy surface. Beyond a critical alloy thickness the chiral influence of the Cu(643)R surface diminishes and an achiral surface forms. Our work demonstrates a new method of producing chiral transition metal chalcogenide surfaces, with potential applications in the study of structurally chiral topological insulators
Effect of Adjunctive Systemic Azithromycin With Periodontal Surgery in the Treatment of Chronic Periodontitis in Smokers: A Pilot Study
Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/141533/1/jper1887.pd
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