159 research outputs found
Efficiency and Technological Change in Health Care Services in Ontario
This paper presents productivity measurement results for hospital services using panel data for Ontario hospitals between 2003 and 2006. The study uses the Malmquist Productivity index (MPI) obtained through the application of Data Envelopment Analysis (DEA) which is decomposed into efficiency change (ECH), i.e., movement towards the best practice frontier and technological change (TCH), i.e., movement of the frontier itself (Färe et al. [12]). The study also uses kernel density estimation techniques for analysis of efficiency distributions of the productivity scores and their components across different types of hospitals (e.g. small /large and rural /urban) and over time. Our results suggest that in addition to average productivity it is important to examine distributions of productivity and of its components which we find differs by hospital type and over time. We find that productivity growth occurred mostly through improvement in technology and in spite of declining efficiency. The results provide useful insight into the underlying mechanisms of observed changes in overall productivity, in technological change and in technical efficiency change in this vital sector of the health care market.
Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM
We have developed the novel Aerosol Dynamics, gas- and particle-phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas-phase Master Chemical Mechanism version 3.2 (MCMv3.2), an aerosol dynamics and particle-phase chemistry module (which considers acid-catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion-limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study (1) the evaporation of liquid dioctyl phthalate (DOP) particles, (2) the slow and almost particle-size-independent evaporation of alpha-pinene ozonolysis secondary organic aerosol (SOA) particles, (3) the mass-transfer-limited uptake of ammonia (NH3) and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), and (4) the influence of chamber wall effects on the observed SOA formation in smog chambers. ADCHAM is able to capture the observed alpha-pinene SOA mass increase in the presence of NH3(g). Organic salts of ammonium and carboxylic acids predominantly form during the early stage of SOA formation. In the smog chamber experiments, these salts contribute substantially to the initial growth of the homogeneously nucleated particles. The model simulations of evaporating alpha-pinene SOA particles support the recent experimental findings that these particles have a semi-solid tar-like amorphous-phase state. ADCHAM is able to reproduce the main features of the observed slow evaporation rates if the concentration of low-volatility and viscous oligomerized SOA material at the particle surface increases upon evaporation. The evaporation rate is mainly governed by the reversible decomposition of oligomers back to monomers. Finally, we demonstrate that the mass-transfer-limited uptake of condensable organic compounds onto wall-deposited particles or directly onto the Teflon chamber walls of smog chambers can have a profound influence on the observed SOA formation. During the early stage of the SOA formation the wall-deposited particles and walls themselves serve as an SOA sink from the air to the walls. However, at the end of smog chamber experiments the semi-volatile SOA material may start to evaporate from the chamber walls. With these four model applications, we demonstrate that several poorly quantified processes (i.e. mass transport limitations within the particle phase, oligomerization, heterogeneous oxidation, organic salt formation, and chamber wall effects) can have a substantial influence on the SOA formation, lifetime, chemical and physical particle properties, and their evolution. In order to constrain the uncertainties related to these processes, future experiments are needed in which as many of the influential variables as possible are varied. ADCHAM can be a valuable model tool in the design and analysis of such experiments
Aerosol optical hygroscopicity measurements during the 2010 CARES campaign
Measurements of the effect of water uptake on particulate light extinction or scattering made at two locations during the 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES) study around Sacramento, CA are reported. The observed influence of water uptake, characterized through the dimensionless optical hygroscopicity parameter γ, is compared with calculations constrained by observed particle size distributions and size-dependent particle composition. A closure assessment has been carried out that allowed for determination of the average hygroscopic growth factors (GFs) at 85% relative humidity and the dimensionless hygroscopicity parameter κ for oxygenated organic aerosol (OA) and for supermicron particles (defined here as particles with aerodynamic diameters between 1 and 2.5 microns), yielding κ = 0.1–0.15 and 0.9–1.0, respectively. The derived range of oxygenated OA κ values are in line with previous observations. The relatively large values for supermicron particles is consistent with substantial contributions of sea-salt-containing particles in this size range. Analysis of time-dependent variations in the supermicron particle hygroscopicity suggest that atmospheric processing, specifically chloride displacement by nitrate and the accumulation of secondary organics on supermicron particles, can lead to substantial depression of the observed GF
Modeling the Size Distribution and Chemical Composition of Secondary Organic Aerosols during the Reactive Uptake of Isoprene-Derived Epoxydiols under Low-Humidity Condition
Reactive uptake of isoprene epoxydiols (IEPOX), which are isoprene oxidation products, onto acidic sulfate aerosols is recognized to be an important mechanism for the formation of isoprene-derived secondary organic aerosol (SOA). While a mechanistic understanding of IEPOX-SOA formation exists, several processes affecting their formation remain uncertain. Evaluating mechanistic IEPOX-SOA models with controlled laboratory experiments under longer atmospherically relevant time scales is critical. Here, we implement our latest understanding of IEPOX-SOA formation within a box model to simulate the measured reactive uptake of IEPOX on polydisperse ammonium bisulfate seed aerosols within an environmental Teflon chamber. The model is evaluated with single-particle measurements of size distribution, volume, density, and composition of aerosols due to IEPOX-SOA formation at time scales of hours. We find that the model can simulate the growth of particles due to IEPOX multiphase chemistry, as reflected in increases of the mean particle size and volume concentrations, and a shift of the number size distribution to larger sizes. The model also predicts the observed evolution of particle number mean diameter and total volume concentrations at the end of the experiment. We show that in addition to the self-limiting effects of IEPOX-SOA coatings, the mass accommodation coefficient of IEPOX and accounting for the molar balance between inorganic and organic sulfate are important parameters governing the modeling of the IEPOX-SOA formation. Thus, models which do not account for the molar sulfate balance and/or diffusion limitations within IEPOX-SOA coatings are likely to predict IEPOX-SOA formation too high
Chemical transformations in monoterpene-derived organic aerosol enhanced by inorganic composition
Secondary organic aerosol (SOA) is known to impact both climate and air quality, yet molecular-level composition measurements remain challenging, hampering our understanding of SOA formation and evolution. Here, we reveal the importance of underestimated reaction pathways for the (trans) formation of SOA from monoterpenes, one of the largest SOA precursors globally. Utilizing mass spectrometric techniques to achieve a comprehensive characterization of molecular-level changes in the SOA, we were able to link the appearance of high-molecular weight (HMW) organic molecules to the concentration and level of neutralization of particulate sulfate. Interestingly, this oligomerization coincided with a decrease of highly oxygenated molecules (HOMs). Our findings highlight the role of particle-phase processing, and the underestimated importance of sulfate aerosol for monoterpene-SOA formation. The observations of these processes directly in the atmosphere reveal the need to account for the formation of HMW oligomers to fully understand the physicochemical properties of organic aerosol.Peer reviewe
Pathways to Highly Oxidized Products in the Delta 3-Carene + OH System
Oxidation of the monoterpene Delta 3-carene (C10H16) is a potentially important and understudied source of atmospheric secondary organic aerosol (SOA). We present chamber-based measurements of speciated gas and particle phases during photochemical oxidation of Delta 3-carene. We find evidence of highly oxidized organic molecules (HOMs) in the gas phase and relatively low-volatility SOA dominated by C-7-C-10 species. We then use computational methods to develop the first stages of a Delta 3-carene photochemical oxidation mechanism and explain some of our measured compositions. We find that alkoxy bond scission of the cyclohexyl ring likely leads to efficient HOM formation, in line with previous studies. We also find a surprising role for the abstraction of primary hydrogens from methyl groups, which has been calculated to be rapid in the alpha-pinene system, and suggest more research is required to determine if this is more general to other systems and a feature of autoxidation. This work develops a more comprehensive view of Delta 3-carene photochemical oxidation products via measurements and lays out a suggested mechanism of oxidation via computationally derived rate coefficients.Peer reviewe
Activation of intact bacteria and bacterial fragments mixed with agar as cloud droplets and ice crystals in cloud chamber experiments
Biological particles, including bacteria and bacterial fragments, have been
of much interest due to the special ability of some to nucleate ice at
modestly supercooled temperatures. This paper presents results from a recent
study conducted on two strains of cultivated bacteria which suggest that
bacterial fragments mixed with agar, and not whole bacterial cells, serve as
cloud condensation nuclei (CCN). Due to the absence of whole bacteria cells
in droplets, they are unable to serve as ice nucleating particles (INPs) in
the immersion mode under the experimental conditions. Experiments were
conducted at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA)
cloud chamber at the Karlsruhe Institute of Technology (KIT) by injecting
bacteria-containing aerosol samples into the cloud chamber and inducing cloud
formation by expansion over a temperature range of −5 to −12 ∘C.
Cloud droplets and ice crystals were sampled through a pumped counterflow
virtual impactor inlet (PCVI) and their residuals were characterized with a
single particle mass spectrometer (miniSPLAT). The size distribution of the
overall aerosol was bimodal, with a large particle mode composed of intact
bacteria and a mode of smaller particles composed of bacterial fragments
mixed with agar that were present in higher concentrations. Results from
three expansions with two bacterial strains indicate that the cloud droplet
residuals had virtually the same size distribution as the smaller particle
size mode and had mass spectra that closely matched those of bacterial
fragments mixed with agar. The characterization of ice residuals that were
sampled through an ice-selecting PCVI (IS-PCVI) also shows that the same
particles that activate to form cloud droplets, bacteria fragments mixed with
agar, were the only particle type observed in ice residuals. These results
indicate that the unavoidable presence of agar or other growth media in
all laboratory studies conducted on cultivated bacteria can greatly
affect the results and needs to be considered when interpreting CCN and IN
activation data.</p
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Aircraft-Measured Indirect Cloud Effects from Biomass Burning Smoke in the Arctic and Subarctic
The incidence of wildfires in the Arctic and subarctic is increasing; in boreal North America, for example, the burned area is expected to increase by 200-300 over the next 50-100 years, which previous studies suggest could have a large effect on cloud microphysics, lifetime, albedo, and precipitation. However, the interactions between smoke particles and clouds remain poorly quantified due to confounding meteorological influences and remote sensing limitations. Here, we use data from several aircraft campaigns in the Arctic and subarctic to explore cloud microphysics in liquid-phase clouds influenced by biomass burning. Median cloud droplet radii in smoky clouds were 50 smaller than in background clouds. Based on the relationship between cloud droplet number (N(liq))/ and various biomass burning tracers (BBt/ across the multi-campaign dataset, we calculated the magnitude of subarctic and Arctic smoke aerosol-cloud interactions (ACI, where ACI = (1/3) x dln(N(liq))/dln(BBt)) to be 0.12 out of a maximum possible value of 0.33 that would be obtained if all aerosols were to nucleate cloud droplets. Interestingly, in a separate subarctic case study with low liquid water content (0.02 gm/ cu m) and very high aerosol concentrations (2000-3000 cu m) in the most polluted clouds, the estimated ACI value was only 0.06. In this case, competition for water vapor by the high concentration of CCN strongly limited the formation of droplets and reduced the cloud albedo effect, which highlights the importance of cloud feedbacks across scales. Using our calculated ACI values, we estimate that the smoke-driven cloud albedo effect may decrease shortwave radiative flux by 2 and 4 W/sq or more under some low and homogeneous cloud cover conditions in the subarctic, although the changes should be smaller in high surface albedo regions of the Arctic. We lastly show evidence to suggest that numerous northern latitude background Aitken particles can interact with combustion particles, perhaps impacting their properties as cloud condensation and ice nuclei. However, the influence of background particles on smoke-driven indirect effects is currently unclear
A comprehensive characterization of ice nucleation by three different types of cellulose particles immersed in water
We present the laboratory results of immersion freezing efficiencies of cellulose particles at supercooled temperature (T) conditions. Three types of chemically homogeneous cellulose samples are used as surrogates that represent supermicron and submicron ice-nucleating plant structural polymers. These samples include microcrystalline cellulose (MCC), fibrous cellulose (FC) and nanocrystalline cellulose (NCC). Our immersion freezing dataset includes data from various ice nucleation measurement techniques available at 17 different institutions, including nine dry dispersion and 11 aqueous suspension techniques. With a total of 20 methods, we performed systematic accuracy and precision analysis of measurements from all 20 measurement techniques by evaluating T-binned (1 ∘C) data over a wide T range (−36 ∘C <T<−4 ∘C). Specifically, we intercompared the geometric surface area-based ice nucleation active surface site (INAS) density data derived from our measurements as a function of T, ns,geo(T). Additionally, we also compared the ns,geo(T) values and the freezing spectral slope parameter (Δlog(ns,geo)/ΔT) from our measurements to previous literature results. Results show all three cellulose materials are reasonably ice active. The freezing efficiencies of NCC samples agree reasonably well, whereas the diversity for the other two samples spans ≈ 10 ∘C. Despite given uncertainties within each instrument technique, the overall trend of the ns,geo(T) spectrum traced by the T-binned average of measurements suggests that predominantly supermicron-sized cellulose particles (MCC and FC) generally act as more efficient ice-nucleating particles (INPs) than NCC with about 1 order of magnitude higher ns,geo(T)
Overview of the 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES)
Substantial uncertainties still exist in the scientific understanding of the possible interactions between urban and natural (biogenic) emissions in the production and transformation of atmospheric aerosol and the resulting impact on climate change. The US Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) program's Carbonaceous Aerosol and Radiative Effects Study (CARES) carried out in June 2010 in Central Valley, California, was a comprehensive effort designed to improve this understanding. The primary objective of the field study was to investigate the evolution of secondary organic and black carbon aerosols and their climate-related properties in the Sacramento urban plume as it was routinely transported into the forested Sierra Nevada foothills area. Urban aerosols and trace gases experienced significant physical and chemical transformations as they mixed with the reactive biogenic hydrocarbons emitted from the forest. Two heavily-instrumented ground sites – one within the Sacramento urban area and another about 40 km to the northeast in the foothills area – were set up to characterize the evolution of meteorological variables, trace gases, aerosol precursors, aerosol size, composition, and climate-related properties in freshly polluted and "aged" urban air. On selected days, the DOE G-1 aircraft was deployed to make similar measurements upwind and across the evolving Sacramento plume in the morning and again in the afternoon. The NASA B-200 aircraft, carrying remote sensing instruments, was also deployed to characterize the vertical and horizontal distribution of aerosols and aerosol optical properties within and around the plume. This overview provides: (a) the scientific background and motivation for the study, (b) the operational and logistical information pertinent to the execution of the study, (c) an overview of key observations and initial findings from the aircraft and ground-based sampling platforms, and (d) a roadmap of planned data analyses and focused modeling efforts that will facilitate the integration of new knowledge into improved representations of key aerosol processes and properties in climate models.United States. Dept. of Energy. Atmospheric System Research Program (Contract DE-AC06-76RLO 1830)United States. National Oceanic and Atmospheric AdministrationUnited States. National Aeronautics and Space Administration. HQ Science Mission Directorate Radiation Sciences ProgramUnited States. National Aeronautics and Space Administration. CALIPSO ProgramUnited States. Dept. of Energy. Atmospheric Radiation Measurement Program (Interagency Agreement No. DE-AI02-05ER63985
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