Aqueous phase oxidation of sulphur dioxide by ozone in cloud droplets

The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). Experiments were performed at 10 and −10 °C, on acidic (sulfuric acid) and on partially to fully neutralised (ammonium sulfate) seed aerosol. Clouds were generated by performing an adiabatic expansion – pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and −10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system can be well represented by using accepted rate constants, based on bulk measurements. To the best of our knowledge, these are the first laboratory-based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rate constants to temperatures below 0 °C is correct

Remote measurement utilizing NASA's scanning laser Doppler systems. Volume 2: Laser Doppler dust devil velocity profile measurement program

The first detailed velocity profile data on thermally induced dust vortices are presented. These dust devils will be analyzed and studied to determine their flow fields and origin in an effort to correlate this phenomena with the generation and characteristics of tornadoes. A continuing effort to increase mankind's knowledge of vortex and other meteorological phenomena will hopefully allow the prediction of tornado occurrence, their path, and perhaps eventually even lead to some technique for their destruction

Chemical aging of m-xylene secondary organic aerosol: laboratory chamber study

Secondary organic aerosol (SOA) can reside in the atmosphere for a week or more. While its initial formation from the gas-phase oxidation of volatile organic compounds tends to take place in the first few hours after emission, SOA can continue to evolve chemically over its atmospheric lifetime. Simulating this chemical aging over an extended time in the laboratory has proven to be challenging. We present here a procedure for studying SOA aging in laboratory chambers that is applied to achieve 36 h of oxidation. The formation and evolution of SOA from the photooxidation of m-xylene under low-NO_x conditions and in the presence of either neutral or acidic seed particles is studied. In SOA aging, increasing molecular functionalization leads to less volatile products and an increase in SOA mass, whereas gas- or particle-phase fragmentation chemistry results in more volatile products and a loss of SOA. The challenge is to discern from measured chamber variables the extent to which these processes are important for a given SOA system. In the experiments conducted, m-xylene SOA mass, calculated under the assumption of size-invariant particle composition, increased over the initial 12–13 h of photooxidation and decreased beyond that time, suggesting the existence of fragmentation chemistry. The oxidation of the SOA, as manifested in the O:C elemental ratio and fraction of organic ion detected at m/z 44 measured by the Aerodyne aerosol mass spectrometer, increased continuously starting after 5 h of irradiation until the 36 h termination. This behavior is consistent with an initial period in which, as the mass of SOA increases, products of higher volatility partition to the aerosol phase, followed by an aging period in which gas- and particle-phase reaction products become increasingly more oxidized. When irradiation is stopped 12.4 h into one experiment, and OH generation ceases, minimal loss of SOA is observed, indicating that the loss of SOA is either light- or OH-induced. Chemical ionization mass spectrometry measurements of low-volatility m-xylene oxidation products exhibit behavior indicative of continuous photooxidation chemistry. A condensed chemical mechanism of m-xylene oxidation under low-NO_x conditions is capable of reproducing the general behavior of gas-phase evolution observed here. Moreover, order of magnitude analysis of the mechanism suggests that gas-phase OH reaction of low volatility SOA precursors is the dominant pathway of aging in the m-xylene system although OH reaction with particle surfaces cannot be ruled out. Finally, the effect of size-dependent particle composition and size-dependent particle wall loss rates on different particle wall loss correction methods is discussed

Impact of a large wildfire on water-soluble organic aerosol in a major urban area: the 2009 Station Fire in Los Angeles County

This study examines the nature of water-soluble organic aerosol measured in Pasadena, CA, under typical conditions and under the influence of a large wildfire (the 2009 Station Fire). During non-fire periods, water-soluble organic carbon (WSOC) variability was driven by photochemical production processes and sea breeze transport, resulting in an average diurnal cycle with a maximum at 15:00 local time (up to 4.9 μg C m^(−3)). During the Station Fire, primary production was a key formation mechanism for WSOC. High concentrations of WSOC (up to 41 μg C m^(−3)) in smoke plumes advected to the site in the morning hours were tightly correlated with nitrate and chloride, numerous aerosol mass spectrometer (AMS) organic mass spectral markers, and total non-refractory organic mass. Processed residual smoke was transported to the measurement site by the sea breeze later in the day, leading to higher afternoon WSOC levels than on non-fire days. Parameters representing higher degrees of oxidation of organics, including the ratios of the organic metrics m/z 44:m/z 57 and m/z 44:m/z 43, were elevated in those air masses. Intercomparisons of relative amounts of WSOC, organics, m/z 44, and m/z 43 show that the fraction of WSOC comprising acid-oxygenates increased as a function of photochemical aging owing to the conversion of aliphatic and non-acid oxygenated organics to more acid-like organics. The contribution of water-soluble organic species to the organic mass budget (10th–90th percentile values) ranged between 27 %–72 % and 27 %–68 % during fire and non-fire periods, respectively. The seasonal incidence of wildfires in the Los Angeles Basin greatly enhances the importance of water-soluble organics, which has implications for the radiative and hygroscopic properties of the regional aerosol

Global auroral responses to magnetospheric compressions by shocks in the solar wind: Two case studies

The global auroral responses to shocks in the solar wind at Earth were studied. The z-component of the interplanetary magnetic field, Bz, is negative ahead and behind the first shock and positive for the second case. A sudden-commencement geomagnetic storm develops in each case, with maximum D sub st 190 nT. An immediate auroral response is detected at all longitudes around the auroral oval, in which auroral luminosities increase by a factor of 2 to 3 with the first samples after each sudden commencement. The time delay in obtaining the first sample varies with local time from approx. 1 to 18 mins. No other significant variations in the aurora are associated with the immediate response. Beginning approx. 30 mins after each sudden commencement, the aurora becomes active and displays significant variations in its luminosity and spatial distribution. For Bz 0 an intense substorm develops. A sun-aligned transpolar arc forms when Bz 0, appearing first at local midnight as a polar arc and then lengthening sunward from the auroral oval across the polar cap to noon at an average speed of approx. 1 km/sec

Remote measurement utilizing NASA's scanning laser Doppler systems. Volume 1. Laser Doppler wake vortex tracking at Kennedy Airport

Test operations of the Scanning Laser Doppler System (SLDS) at Kennedy International Airport (KIA) during August 1974 through June 1975 are reported. A total of 1,619 data runs was recorded with a totally operational system during normal landing operations at KIA. In addition, 53 data runs were made during cooperative flybys with the C880 for a grand total of 1672 recorded vortex tracks. Test crews were in attendance at KIA for 31 weeks, of which 25 weeks were considered operational and the other six were packing, unpacking, setup and check out. Although average activity equates to 67 recorded landing operations per week, two periods of complete runway inactivity spanned 20 days and 13 days, respectively. The operation frequency therefore averaged about 88 operations per week

Understanding our impact: Analyzing librarian involvement with systematic reviews

Objectives: On a medical campus, systematic reviews with librarian co-authors compared to reviews without librarians were published in journals with lower impact factors, although still within the comparative range. To try to determine why, discipline and authors’ publishing experience were examined. The bibliographic analysis was also expanded to see if there is a difference in the journal ranks by discipline. Methods: Search strategies were created to pull systematic reviews published in the last five years by campus authors from PubMed, Ovid MEDLINE, and Web of Science. Citations were exported and deduped using EndNote X8. The systematic reviews were grouped by whether a librarian from our campus assisted with the search or not by searching for librarians’ names in the author field. A statistically appropriate number of articles without a librarian author were randomly selected for comparison with articles that had librarian assistance. Selected articles were analyzed based on Journal Impact Factor for the year of publication, journal rank by discipline, authors’ discipline(s), and years of authors’ publication experience. Authors’ years of experience are determined by the date of their first published article. Results: Systematic reviews with the assistance of a librarian were statistically no different from those without a librarian in terms of the Journal Impact Factor or journal rank by discipline where systematic reviews were published. Years of experience significantly differed between groups, with librarians assisting most authors with 5 years or fewer of experience. The departments who utilized librarians for systematic searching the most were: General Medicine, Orthopedics, and Gastroenterology. Conclusions: This exploratory research helped evaluate who our librarians are primarily working with on systematic reviews. It also informed us that we do not have an impact on the systematic review being published in a higher impact journal based on Journal Impact Factor or rank by discipline. Our liaison efforts will focus less on the three departments listed above as they already utilize our service. Since most of the authors we assisted had 5 years of experience, we will target the campus faculty onboarding orientation

The Pasadena Aerosol Characterization Observatory (PACO): chemical and physical analysis of the Western Los Angeles basin aerosol

The Pasadena Aerosol Characterization Observatory (PACO) represents the first major aerosol characterization experiment centered in the Western/Central Los Angeles Basin. The sampling site, located on the campus of the California Institute of Technology in Pasadena, was positioned to sample a continuous afternoon influx of transported urban aerosol with a photochemical age of 1–2 h and generally free from major local contributions. Sampling spanned 5 months during the summer of 2009, which were broken into 3 regimes on the basis of distinct meteorological conditions. Regime I was characterized by a series of low pressure systems, resulting in high humidity and rainy periods with clean conditions. Regime II typified early summer meteorology, with significant morning marine layers and warm, sunny afternoons. Regime III was characterized by hot, dry conditions with little marine layer influence. Regardless of regime, organic aerosol (OA) is the most significant constituent of nonrefractory submicron Los Angeles aerosol (42, 43, and 55 % of total submicron mass in regimes I, II, and III, respectively). The overall oxidation state remains relatively constant on timescales of days to weeks (O:C = 0.44 ± 0.08, 0.55 ± 0.05, and 0.48 ± 0.08 during regimes I, II, and III, respectively), with no difference in O:C between morning and afternoon periods. Periods characterized by significant morning marine layer influence followed by photochemically favorable afternoons displayed significantly higher aerosol mass and O:C ratio, suggesting that aqueous processes may be important in the generation of secondary aerosol and oxidized organic aerosol (OOA) in Los Angeles. Online analysis of water soluble organic carbon (WSOC) indicates that water soluble organic mass (WSOM) reaches maxima near 14:00–15:00 local time (LT), but the percentage of AMS organic mass contributed by WSOM remains relatively constant throughout the day. Sulfate and nitrate reside predominantly in accumulation mode aerosol, while afternoon SOA production coincides with the appearance of a distinct fine mode dominated by organics. Particulate NH_4NO_3 and (NH_4)_2SO_4 appear to be NH_3-limited in regimes I and II, but a significant excess of particulate NH_4^+ in the hot, dry regime III suggests less SO_4^(2−) and the presence of either organic amines or NH_4^+-associated organic acids. C-ToF-AMS data were analyzed by Positive Matrix Factorization (PMF), which resolved three factors, corresponding to a hydrocarbon-like OA (HOA), semivolatile OOA (SV-OOA), and low-volatility OOA (LV-OOA). HOA appears to be a periodic plume source, while SV-OOA exhibits a strong diurnal pattern correlating with ozone. Peaks in SV-OOA concentration correspond to peaks in DMA number concentration and the appearance of a fine organic mode. LV-OOA appears to be an aged accumulation mode constituent that may be associated with aqueous-phase processing, correlating strongly with sulfate and representing the dominant background organic component. Periods characterized by high SV-OOA and LV-OOA were analyzed by filter analysis, revealing a complex mixture of species during periods dominated by SV-OOA and LV-OOA, with LV-OOA periods characterized by shorter-chain dicarboxylic acids (higher O:C ratio), as well as appreciable amounts of nitrate- and sulfate-substituted organics. Phthalic acid was ubiquitous in filter samples, suggesting that PAH photochemistry may be an important SOA pathway in Los Angeles. Aerosol composition was related to water uptake characteristics, and it is concluded that hygroscopicity is largely controlled by organic mass fraction (OMF). The hygroscopicity parameter κ averaged 0.31 ± 0.08, approaching 0.5 at low OMF and 0.1 at high OMF, with increasing OMF suppressing hygroscopic growth and increasing critical dry diameter for CCN activation (D_d). An experiment-averaged κ_(org) of 0.14 was calculated, indicating that the highly-oxidized organic fraction of aerosol in Los Angeles is appreciably more hygroscopic than previously reported in urban areas. Finally, PACO will provide context for results forthcoming from the CalNex field campaign, which involved ground sampling in Pasadena during the spring and summer of 2010

The International Covenant on Economic, Social and Cultural Rights: a perspective on its development

The International Covenant on Economic, Social and Cultural Rights entered currently has 118 States Parties and has been in force for 17 years. Over the past five years, the implementation of the Covenant has come under the supervision of the Committee on Economic, Social and Cultural Rights. Unlike its predecessort, the Sessional W orking Group, the Committee has taken its supervisory role seriously such that it has begun to develop both the substance of the Covenant and the implementation procedures. This study, based principally upon the work of the Committee on Economic, Social and Cultural Rights, discusses a number of aspects in which the substance of the Covenant and its supervision procedures may be seen to have been developed. Chapter 1 traces the roots of economic, social and cultural rights and outlines their codification in the Universal Declaration of Human Rights, and later the Covenant, following the end of the Second World War. Significant aspects of the drafting process are analysed in detail. Chapter 2 discussest he nature and scope of the State obligations under the Covenant as regards the implementation of the rights. Particular emphasis is given to the terms of article 2(1) and how they have been interpreted in the work of the Committee. Chapter 3 analyses, primarily from a theoretical standpoint, the manner and degree to which the terms of the Covenant may be given "direct effect", or in other words, relied upon directly in domestic courts. Chapters 4 to 8 address particular articles within the Covenant and considers the interpretation given to them by the Committee. Chapter 4 deals with article 2(2) (and to a lesser extent article 3) concerning non-discrimination; Chapter 5 deals with article 6 concerning the right to work; Chapter 6 deals with article 7 regarding the right to just and favourable conditions of work; Chapter 7 deals with article 8 concerning rights related to trade unions; and Chapter 8 deals with article 11 concerning the right to an adequate standard of living and, in particular, the rights to food and housing. In each case, an attempt is made to evaluate the Committee's approach to each article and assess the possibilities for future development. Chapter 9 addresses the emergence, role and working methods, of the Committee as a human rights supervisory body. Particular consideration is also given to the problems encountered and the Committee's future prospects. Chapter 10, as the concluding chapter, draws together the observations made in earlier chapters and attempts to make an evaluation of the present and future utility of the Covenant as a mechanism for the promotion and protection of economic, social and cultural rights

New insight into the evolution of the vertebrate respiratory system and the discovery of unidirectional airflow in iguana lungs

Journal ArticleThe generally accepted framework for the evolution of a key feature of the avian respiratory system, unidirectional airflow, is that it is an adaptation for efficiency of gas exchange and expanded aerobic capacities, and therefore it has historically been viewed as important to the ability of birds to fly and to maintain an endothermic metabolism. This pattern of flow has been presumed to arise from specific features of the respiratory system, such as an enclosed intrapulmonary bronchus and parabronchi. Here we show unidirectional airflow in the green iguana, a lizard with a strikingly different natural history from that of birds and lacking these anatomical features. This discovery indicates a paradigm shift is needed. The selective drivers of the trait, its date of origin, and the fundamental aerodynamic mechanisms by which unidirectional flow arises must be reassessed to be congruent with the natural history of this lineage. Unidirectional flow may serve functions other than expanded aerobic capacity; it may have been present in the ancestral diapsid; and it can occur in structurally simple lungs