The formation, properties and impact of secondary organic aerosol: current and emerging issues

Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed

A parametric physical model for the intracluster medium and its use in joint SZ/X-ray analyses of galaxy clusters

We present a parameterized model of the intra-cluster medium that is suitable for jointly analysing pointed observations of the Sunyaev-Zel'dovich (SZ) effect and X-ray emission in galaxy clusters. The model is based on assumptions of hydrostatic equilibrium, the Navarro, Frenk and White (NFW) model for the dark matter, and a softened power law profile for the gas entropy. We test this entropy-based model against high and low signal-to-noise mock observations of a relaxed and recently-merged cluster from N-body/hydrodynamic simulations, using Bayesian hyper-parameters to optimise the relative statistical weighting of the mock SZ and X-ray data. We find that it accurately reproduces both the global values of the cluster temperature, total mass and gas mass fraction (fgas), as well as the radial dependencies of these quantities outside of the core (r > kpc). For reference we also provide a comparison with results from the single isothermal beta model. We confirm previous results that the single isothermal beta model can result in significant biases in derived cluster properties.Comment: Published in MNRAS. 20 pages. 9 figure

Biostack: Nontoxic Metabolite Detection from Live Tissue

Funder: ANR‐TFunder: IONOSENSEAbstract: There is increasing demand for direct in situ metabolite monitoring from cell cultures and in vivo using implantable devices. Electrochemical biosensors are commonly preferred due to their low‐cost, high sensitivity, and low complexity. Metabolite detection, however, in cultured cells or sensitive tissue is rarely shown. Commonly, glucose sensing occurs indirectly by measuring the concentration of hydrogen peroxide, which is a by‐product of the conversion of glucose by glucose oxidase. However, continuous production of hydrogen peroxide in cell media with high glucose is toxic to adjacent cells or tissue. This challenge is overcome through a novel, stacked enzyme configuration. A primary enzyme is used to provide analyte sensitivity, along with a secondary enzyme which converts H2O2 back to O2. The secondary enzyme is functionalized as the outermost layer of the device. Thus, production of H2O2 remains local to the sensor and its concentration in the extracellular environment does not increase. This “biostack” is integrated with organic electrochemical transistors to demonstrate sensors that monitor glucose concentration in cell cultures in situ. The “biostack” renders the sensors nontoxic for cells and provides highly sensitive and stable detection of metabolites

SPT-CL J0546-5345: A Massive z > 1 Galaxy Cluster Selected Via the Sunyaev-Zel'dovich Effect with the South Pole Telescope

We report the spectroscopic confirmation of SPT-CL J0546-5345 at = 1.067. To date this is the most distant cluster to be spectroscopically confirmed from the 2008 South Pole Telescope (SPT) catalog, and indeed the first z > 1 cluster discovered by the Sunyaev-Zel'dovich Effect (SZE). We identify 21 secure spectroscopic members within 0.9 Mpc of the SPT cluster position, 18 of which are quiescent, early-type galaxies. From these quiescent galaxies we obtain a velocity dispersion of 1179^{+232}_{-167} km/s, ranking SPT-CL J0546-5345 as the most dynamically massive cluster yet discovered at z > 1. Assuming that SPT-CL J0546-5345 is virialized, this implies a dynamical mass of M_200 = 1.0^{+0.6}_{-0.4} x 10^{15} Msun, in agreement with the X-ray and SZE mass measurements. Combining masses from several independent measures leads to a best-estimate mass of M_200 = (7.95 +/- 0.92) x 10^{14} Msun. The spectroscopic confirmation of SPT-CL J0546-5345, discovered in the wide-angle, mass-selected SPT cluster survey, marks the onset of the high redshift SZE-selected galaxy cluster era.Comment: ApJ, in pres

X-ray absorption spectroscopy systematics at the tungsten L-edge

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, has been interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W<sup>0</sup>(PMe<sub>3</sub>)<sub>6</sub>], [W<sup>II</sup>Cl<sub>2</sub>(PMePh<sub>2</sub>)<sub>4</sub>], [W<sup>III</sup>Cl<sub>2</sub>(dppe)<sub>2</sub>][PF<sub>6</sub>] (dppe = 1,2-bis(diphenylphosphino)ethane), [W<sup>IV</sup>Cl<sub>4</sub>(PMePh<sub>2</sub>)<sub>2</sub>], [W<sup>V</sup>(NPh)Cl<sub>3</sub>(PMe<sub>3</sub>)<sub>2</sub>], and [W<sup>VI</sup>Cl<sub>6</sub>] correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio (EBR) of the L<sub>3,2</sub>-edges and the L<sub>1</sub> rising-edge energy with metal Z<sub>eff</sub>, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W<sup>IV</sup>(mdt)<sub>2</sub>(CO)<sub>2</sub>] and [W<sup>IV</sup>(mdt)<sub>2</sub>(CN)<sub>2</sub>]<sup>2–</sup> (mdt<sup>2–</sup> = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W<sup>IV</sup> species. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: 1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Z<sub>eff</sub> in the species of interest; 2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS; 3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate the difference between formal oxidation state and metal Z<sub>eff</sub> or, as in the case of [W<sup>IV</sup>(mdt)<sub>2</sub>(CO)<sub>2</sub>], add other subtlety by modulating the redox level of other ligands in the coordination sphere

Weighing the Giants - I. Weak-lensing masses for 51 massive galaxy clusters: project overview, data analysis methods and cluster images

This is the first in a series of papers in which we measure accurate weak-lensing masses for 51 of the most X-ray luminous galaxy clusters known at redshifts 0.15<z<0.7, in order to calibrate X-ray and other mass proxies for cosmological cluster experiments. The primary aim is to improve the absolute mass calibration of cluster observables, currently the dominant systematic uncertainty for cluster count experiments. Key elements of this work are the rigorous quantification of systematic uncertainties, high-quality data reduction and photometric calibration, and the "blind" nature of the analysis to avoid confirmation bias. Our target clusters are drawn from RASS X-ray catalogs, and provide a versatile calibration sample for many aspects of cluster cosmology. We have acquired wide-field, high-quality imaging using the Subaru and CFHT telescopes for all 51 clusters, in at least three bands per cluster. For a subset of 27 clusters, we have data in at least five bands, allowing accurate photo-z estimates of lensed galaxies. In this paper, we describe the cluster sample and observations, and detail the processing of the SuprimeCam data to yield high-quality images suitable for robust weak-lensing shape measurements and precision photometry. For each cluster, we present wide-field color optical images and maps of the weak-lensing mass distribution, the optical light distribution, and the X-ray emission, providing insights into the large-scale structure in which the clusters are embedded. We measure the offsets between X-ray centroids and Brightest Cluster Galaxies in the clusters, finding these to be small in general, with a median of 20kpc. For offsets <100kpc, weak-lensing mass measurements centered on the BCGs agree well with values determined relative to the X-ray centroids; miscentering is therefore not a significant source of systematic uncertainty for our mass measurements. [abridged]Comment: 26 pages, 19 figures (Appendix C not included). Accepted after minor revisio

Using serological measures to monitor changes in malaria transmission in Vanuatu

BACKGROUND: With renewed interest in malaria elimination, island environments present unique opportunities to achieve this goal. However, as transmission decreases, monitoring and evaluation programmes need increasingly sensitive tools to assess Plasmodium falciparum and Plasmodium vivax exposure. In 2009, to assess the role of serological markers in evaluating malaria transmission, a cross-sectional seroprevalence study was carried out in Tanna and Aneityum, two of the southernmost islands of the Vanuatu archipelago, areas where malaria transmission has been variably reduced over the past few decades. METHODS: Malaria transmission was assessed using serological markers for exposure to P. falciparum and P. vivax. Filter blood spot papers were collected from 1,249 people from Tanna, and 517 people from Aneityum to assess the prevalence of antibodies to two P. falciparum antigens (MSP-119 and AMA-1) and two P. vivax antigens (MSP-119 and AMA-1). Age-specific prevalence was modelled using a simple catalytic conversion model based on maximum likelihood to generate a community seroconversion rate (SCR). RESULTS: Overall seropositivity in Tanna was 9.4%, 12.4% and 16.6% to P. falciparum MSP-119, AMA-1 and Schizont Extract respectively and 12.6% and 15.0% to P. vivax MSP-119 and AMA-1 respectively. Serological results distinguished between areas of differential dominance of either P. vivax or P. falciparum and analysis of age-stratified results showed a step in seroprevalence occurring approximately 30 years ago on both islands, indicative of a change in transmission intensity at this time. Results from Aneityum suggest that several children may have been exposed to malaria since the 2002 P. vivax epidemic. CONCLUSION: Seroepidemiology can provide key information on malaria transmission for control programmes, when parasite rates are low. As Vanuatu moves closer to malaria elimination, monitoring changes in transmission intensity and identification of residual malaria foci is paramount in order to concentrate intervention efforts

Discovery and Cosmological Implications of SPT-CL J2106-5844, the Most Massive Known Cluster at z > 1

Using the South Pole Telescope (SPT), we have discovered the most massive known galaxy cluster at z > 1, SPT-CL J2106-5844. In addition to producing a strong Sunyaev-Zel'dovich effect signal, this system is a luminous X-ray source and its numerous constituent galaxies display spatial and color clustering, all indicating the presence of a massive galaxy cluster. VLT and Magellan spectroscopy of 18 member galaxies shows that the cluster is at z = 1.132^+0.002_-0.003. Chandra observations obtained through a combined HRC-ACIS GTO program reveal an X-ray spectrum with an Fe K line redshifted by z = 1.18 +/- 0.03. These redshifts are consistent with galaxy colors in extensive optical, near-infrared, and mid-infrared imaging. SPT-CL J2106-5844 displays extreme X-ray properties for a cluster, having a core-excluded temperature of kT = 11.0^+2.6_-1.9 keV and a luminosity (within r_500) of L_X (0.5 - 2.0 keV) = (13.9 +/- 1.0) x 10^44 erg/s. The combined mass estimate from measurements of the Sunyaev-Zel'dovich effect and X-ray data is M_200 = (1.27 +/- 0.21) x 10^15 M_sun. The discovery of such a massive gravitationally collapsed system at high redshift provides an interesting laboratory for galaxy formation and evolution, and is a powerful probe of extreme perturbations of the primordial matter density field. We discuss the latter, determining that, under the assumption of LambdaCDM cosmology with only Gaussian perturbations, there is only a 7% chance of finding a galaxy cluster similar to SPT-CL J2106-5844 in the 2500 deg^2 SPT survey region, and that only one such galaxy cluster is expected in the entire sky.Comment: 10 pages, submitted to Ap

Using the ecology model to describe the impact of asthma on patterns of health care

BACKGROUND: Asthma changes both the volume and patterns of healthcare of affected people. Most studies of asthma health care utilization have been done in selected insured populations or in a single site such as the emergency department. Asthma is an ambulatory sensitive care condition making it important to understand the relationship between care in all sites across the health service spectrum. Asthma is also more common in people with fewer economic resources making it important to include people across all types of insurance and no insurance categories. The ecology of medical care model may provide a useful framework to describe the use of health services in people with asthma compared to those without asthma and identify subgroups with apparent gaps in care. METHODS: This is a case-control study using the 1999 U.S. Medical Expenditure Panel Survey. Cases are school-aged children (6 to 17 years) and young adults (18 to 44 years) with self-reported asthma. Controls are from the same age groups who have no self-reported asthma. Descriptive analyses and risk ratios are placed within the ecology of medical care model and used to describe and compare the healthcare contact of cases and controls across multiple settings. RESULTS: In 1999, the presence of asthma significantly increased the likelihood of an ambulatory care visit by 20 to 30% and more than doubled the likelihood of making one or more visits to the emergency department (ED). Yet, 18.8% of children and 14.5% of adults with asthma (over a million Americans) had no ambulatory care visits for asthma. About one in 20 to 35 people with asthma (5.2% of children and 3.6% of adults) were seen in the ED or hospital but had no prior or follow-up ambulatory care visits. These Americans were more likely to be uninsured, have no usual source of care and live in metropolitan areas. CONCLUSION: The ecology model confirmed that having asthma changes the likelihood and pattern of care for Americans. More importantly, the ecology model identified a subgroup with asthma who sought only emergent or hospital services