Haze in the Klang Valley of Malaysia

Continuous measurements of dry aerosol light scattering (Bsp) were made at two sites in the Klang Valley of Malaysia between December 1998 and December 2000. In addition 24-h PM2.5 samples were collected on a one-day-in-six cycle and the chemical composition of the aerosol was determined. Periods of excessive haze were defined as 24-h average Bsp values greater than 150 Mm-1 and these occurred on a number of occasions, between May and September 1999, during May 2000, and between July and September 2000. The evidence for smoke being a significant contributor to aerosol during periods of excessive haze is discussed and includes features of the aerosol chemistry, the diurnal cycle of Bsp, and the coincidence of forest fires on Sumatra during the southwest (SW) monsoon period, as well as transport modelling for one week of the southwest Monsoon of 2000. The study highlights that whilst transboundary smoke is a major contributor to poor visibility in the Klang Valley, smoke from fires on Peninsular Malaysia is also a contributor, and at all times, the domestic source of secondary particle production is present

Reactive intermediates revealed in secondary organic aerosol formation from isoprene

Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX = β-IEPOX + δ-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NO_x conditions, respectively. Isoprene low-NO_x SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NO_x conditions, isoprene SOA formation occurs through oxidation of its second-generation product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NO_x SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO_2 and NO_2, respectively) could be a substantial source of “missing urban SOA” not included in current atmospheric models

Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds

A series of experiments has been conducted in the Caltech indoor smog chamber facility to investigate the water uptake properties of aerosol formed by oxidation of various organic precursors. Secondary organic aerosol (SOA) from simple and substituted cycloalkenes (C5-C8) is produced in dark ozonolysis experiments in a dry chamber (RH~5%). Biogenic SOA from monoterpenes, sesquiterpenes, and oxygenated terpenes is formed by photooxidation in a humid chamber (~50% RH). Using the hygroscopicity tandem differential mobility analyzer (HTDMA), we measure the diameter-based hygroscopic growth factor (GF) of the SOA as a function of time and relative humidity. All SOA studied is found to be slightly hygroscopic, with smaller water uptake than that of typical inorganic aerosol substances. The aerosol water uptake increases with time early in the experiments for the cycloalkene SOA, but decreases with time for the biogenic SOA. This behavior could indicate competing effects between the formation of more highly oxidized polar compounds (more hygroscopic), and formation of longer-chained oligomers (less hygroscopic). All SOA also exhibit a smooth water uptake with RH with no deliquescence or efflorescence. The water uptake curves are found to be fitted well with an empirical three-parameter functional form. The measured pure organic GF values at 85% RH are between 1.09–1.16 for SOA from ozonolysis of cycloalkenes, 1.01–1.04 for sesquiterpene photooxidation SOA, and 1.06–1.11 for the monoterpene and oxygenated terpene SOA. The GF of pure SOA (GForg) in experiments in which inorganic seed aerosol is used is determined by assuming volume-weighted water uptake (Zdanovskii-Stokes-Robinson or ''ZSR'' approach) and using the size-resolved organic mass fraction measured by the Aerodyne Aerosol Mass Spectrometer. Knowing the water content associated with the inorganic fraction yields GForg values. However, for each precursor, the GForg values computed from different HTDMA-classified diameters agree with each other to varying degrees. Lack of complete agreement may be a result of the non-idealities of the solutions that are not captured by the ZSR method. Comparing growth factors from different precursors, we find that GForg is inversely proportional to the precursor molecular weight and SOA yield, which is likely a result of the fact that higher-molecular weight precursors tend to produce larger and less hygroscopic oxidation products

Szenci Molnár Albert epigrammája a Scandell-antológiában

The composition of secondary organic aerosol (SOA) from the ozonolysis of C5−C8 cycloalkenes and α-pinene, as well as the effects of hydrocarbon precursor structure and particle-phase acidity on SOA formation, have been investigated by a series of controlled laboratory chamber experiments. A liquid chromatography−mass spectrometer and an ion trap mass spectrometer are used concurrently to identify and to quantify SOA components with molecular weights up to 1600 Da. Diacids, carbonyl-containing acids, diacid alkyl esters, and hydroxy diacids are the four major classes of low-molecular-weight (MW \u3c 250 Da) components in the SOA; together they comprise 42−83% of the total SOA mass, assuming an aerosol density of 1.4 g/cm3. In addition, oligomers (MW \u3e 250 Da) are found to be present in all SOA. Using surrogate standards, it is estimated that the mass fraction of oligomers in the total SOA is at least 10% for the cycloalkene systems (with six or more carbons) and well over 50% for the α-pinene system. Higher seed particle acidity is found to lead to more rapid oligomer formation and, ultimately, to higher SOA yields. Because oligomers are observed to form even in the absence of seed particles, organic acids produced from hydrocarbon oxidation itself may readily promote acid catalysis and oligomer formation. The distinct effects of carbon numbers, substituent groups, and isomeric structures of the precursor hydrocarbons on the composition and yield of SOA formed are also discussed

Of Kings and Criminals: Essays on Elite Violence and Economic Development

Literature on the processes that induce economic development has yielded theories emphasising the roles of institutional design, geography, gender equality and human capital. Violence, however, has largely been treated as an outcome of development rather than a contributing factor (McIlwaine 1999; Enamorado et al. 2014). On an individual level, violence is largely driven by psychological factors, but these cannot explain regional or societal disparities. Therefore, the first of three studies in this dissertation contributes to the literature by finding a causal effect of elite violence on elite human capital. The inverse relationship that is derived is an important result, since human capital encourages technological innovation and is an important driver of economic growth (see Becker 1962; Mincer 1984; Acemoglu and Dell 2010; and Barro 2001). Further, this chapter also contributes to the Great Divergence debate and shows that at its origins were rooted in violence, at least to a certain degree, from as far back as the 14th century. The second chapter’s chief contribution is that of the regicide indicator. Eisner’s (2011) idea was heavily expanded upon in this paper as we include more than 4000 rulers from across Europe between the 6th and 19th centuries and provide a wider-ranging and longer-term indicator for violence than has been available previously. Since empirical evidence of violence from before the 19th century is only available sporadically and for parts of Western Europe, the regicide indicator opens up entirely new avenues of violence research. Europe undoubtedly has the most complete and far-reaching dynastic lists of all world regions, as well as the most detailed biographical accounts of rulers from which the regicide indicator is constructed. Nevertheless, documenting rulers has been a universal phenomenon throughout history, meaning that this chapter sets a precedent which could also be followed in future studies of other world regions and perhaps even help to explain patterns of development elsewhere. This chapter then goes on to study the role of state capacity in elite violence, using ‘territorial state capacity’, following the divergent hypotheses of researchers such as Pinker (2011) and Tilly (1975). The empirical evidence shows a negative relationship between territorial state capacity and regicide, illustrating that state capacity likely had a largely pacifying role on trends and regional differences in interpersonal elite violence, at least since the High Middle Ages. Finally, as a means of providing a more rounded impression of the consequences of elite violence, and of assassinations in particular, the dissertation proceeded to investigate how shocks to political risk have caused investors to react in terms of global asset allocation since 1970. How investors allocate their holdings influences the levels of financing available to firms or national treasuries; affecting the ability of firms to grow and develop their own industries as well as the ability of governments to provide public services and to direct fiscal policy. The setting of political risk and assassinations provides an interesting conundrum, as financial doctrine dictates that investors reallocate their holdings from stocks to sovereign bonds, while governmental institutions are the source of increased risk in the aftermath of political assassinations (Markowitz 1952). The results obtained from an event analysis illustrate that investors tend to disinvest from equity following political assassinations but refrain from pursuing traditional risk-free instruments. Subsequent exchange rate depreciations likely indicate that investors prefer to move their holdings abroad, signalling that, on average, investors do not act blindly and simply follow financial doctrine. In order to make a stronger conclusion about the destination of financial flows subsequent to political assassinations, an ideal extension to this study would employ spatial methods to examine financial spillovers in conjunction with exchange rate impacts. The study also reveals that developing countries tend to experience more severe and persistent financial market effects in the aftermath of political assassinations. Because developing countries are associated with weaker institutions, investors may believe that existing political and macroeconomic policies could be threatened by the successor of an assassinated individual. Conversely, due to stronger political institutions, investors may see political assassinations in developed countries as isolated events with the continuance of existing policies guaranteed. This suggests that setting clear and long-term policy agendas may be beneficial for governments of developing countries and help to alleviate the volatility of future capital flows

Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds

A series of experiments has been conducted in the Caltech indoor smog chamber facility to investigate the water uptake properties of aerosol formed by oxidation of various organic precursors. Secondary organic aerosol (SOA) from simple and substituted cycloalkenes (C₅-C₈) is produced in dark ozonolysis experiments in a dry chamber (<i>RH</i>~5%). Biogenic SOA from monoterpenes, sesquiterpenes, and oxygenated terpenes is formed by photooxidation in a humid chamber (~50% <i>RH</i>). Using the hygroscopicity tandem differential mobility analyzer (HTDMA), we measure the diameter-based hygroscopic growth factor (<i>GF</i>) of the SOA as a function of time and relative humidity. All SOA studied is found to be slightly hygroscopic, with smaller water uptake than that of typical inorganic aerosol substances. The aerosol water uptake increases with time early in the experiments for the cycloalkene SOA, but decreases with time for the sesquiterpene SOA. This behavior could indicate competing effects between the formation of more highly oxidized polar compounds (more hygroscopic), and formation of longer-chained oligomers (less hygroscopic). All SOA also exhibit a smooth water uptake with <i>RH</i> with no deliquescence or efflorescence. The water uptake curves are found to be fitted well with an empirical three-parameter functional form. The measured pure organic <i>GF</i> values at 85% <i>RH</i> are between 1.09&ndash;1.16 for SOA from ozonolysis of cycloalkenes, 1.01&ndash;1.04 for sesquiterpene photooxidation SOA, and 1.06&ndash;1.10 for the monoterpene and oxygenated terpene SOA. The <i>GF</i> of pure SOA (<i>GF</i>_org) in experiments in which inorganic seed aerosol is used is determined by assuming volume-weighted water uptake (Zdanovskii-Stokes-Robinson or 'ZSR' approach) and using the size-resolved organic mass fraction measured by the Aerodyne Aerosol Mass Spectrometer. Knowing the water content associated with the inorganic fraction yields <i>GF</i>_org values. However, for each precursor, the <i>GF</i>_org values computed from different HTDMA-classified diameters agree with each other to varying degrees. Comparing growth factors from different precursors, we find that <i>GF</i>_org is inversely proportional to the precursor molecular weight and SOA yield, which is likely a result of the fact that higher-molecular weight precursors tend to produce larger and less hygroscopic oxidation products

Optical, physical and chemical characteristics of Australian continental aerosols: results from a field experiment

Mineral dust is one of the major components of the world's aerosol mix, having a number of impacts within the Earth system. However, the climate forcing impact of mineral dust is currently poorly constrained, with even its sign uncertain. As Australian deserts are more reddish than those in the Northern Hemisphere, it is important to better understand the physical, chemical and optical properties of this important aerosol. We have investigated the properties of Australian desert dust at a site in SW Queensland, which is strongly influenced by both dust and biomass burning aerosol. &lt;br&gt;&lt;br&gt; Three years of ground-based monitoring of spectral optical thickness has provided a statistical picture of gross aerosol properties. The aerosol optical depth data showed a clear though moderate seasonal cycle with an annual mean of 0.06 &amp;plusmn; 0.03. The Angstrom coefficient showed a stronger cycle, indicating the influence of the winter-spring burning season in Australia's north. AERONET size distributions showed a generally bimodal character, with the coarse mode assumed to be mineral dust, and the fine mode a mixture of fine dust, biomass burning and marine biogenic material. &lt;br&gt;&lt;br&gt; In November 2006 we undertook a field campaign which collected 4 sets of size-resolved aerosol samples for laboratory analysis – ion beam analysis and ion chromatography. Ion beam analysis was used to determine the elemental composition of all filter samples, although elemental ratios were considered the most reliable output. Scatter plots showed that Fe, Al and Ti were well correlated with Si, and Co reasonably well correlated with Si, with the Fe/Al ratio somewhat higher than values reported from Northern Hemisphere sites (as expected). Scatter plots for Ca, Mn and K against Si showed clear evidence of a second population, which in some cases could be identified with a particular sample day or size fraction. These data may be used to attempt to build a signature of soil in this region of the Australian interior. &lt;br&gt;&lt;br&gt; Ion chromatography was used to quantify water soluble ions for 2 of our sample sets, complementing the picture provided by ion beam analysis. The strong similarities between the MSA and SO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;2&amp;minus;&lt;/sup&gt; size distributions argue strongly for a marine origin of much of the SO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;2&amp;minus;&lt;/sup&gt;. The similarity of the Na&lt;sup&gt;+&lt;/sup&gt;, Cl&lt;sup&gt;&amp;minus;&lt;/sup&gt; and Mg&lt;sup&gt;2+&lt;/sup&gt; size distributions also argue for a marine contribution. Further, we believe that both NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt; and NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt; are the result of surface reactions with appropriate gases

Statistical characterisation of bio-aerosol background in an urban environment

In this paper we statistically characterise the bio-aerosol background in an urban environment. To do this we measure concentration levels of naturally occurring microbiological material in the atmosphere over a two month period. Naturally occurring bioaerosols can be considered as noise, as they mask the presence of signals coming from biological material of interest (such as an intentionally released biological agent). Analysis of this 'biobackground' was undertaken in the 1-10 um size range and a 3-9% contribution was found to be biological in origin - values which are in good agreement with other studies reported in the literature. A model based on the physics of turbulent mixing and dispersion was developed and validated against this analysis. The Gamma distribution (the basis of our model) is shown to comply with the scaling laws of the concentration moments of our data, which enables us to universally characterise both biological and non-biological material in the atmosphere. An application of this model is proposed to build a framework for the development of novel algorithms for bio-aerosol detection and rapid characterisation.Comment: 14 Pages, 8 Figure

Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes

The ozonolyses of six monoterpenes (α-pinene, β-pinene, 3-carene, terpinolene, α-terpinene, and myrcene), two sesquiterpenes (α-humulene and β-caryophyllene), and two oxygenated terpenes (methyl chavicol and linalool) were conducted individually in Teflon chambers to examine the gas-phase oxidation product and secondary organic aerosol (SOA) yields from these reactions. Particle size distribution and number concentration were monitored and allowed for the calculation of the SOA yield from each experiment, which ranged from 1 to 54%. A proton transfer reaction mass spectrometer (PTR-MS) was used to monitor the evolution of gas-phase products, identified by their mass to charge ratio (m/z). Several gas-phase oxidation products, formaldehyde, acetaldehyde, formic acid, acetone, acetic acid, and nopinone, were identified and calibrated. Aerosol yields, and the yields of these identified and calibrated oxidation products, as well as many higher m/z oxidation products observed with the PTR-MS, varied significantly between the different parent terpene compounds. The sum of measured oxidation products in the gas and particle phase ranged from 33 to 77% of the carbon in the reacted terpenes, suggesting there are still unmeasured products from these reactions. The observations of the higher molecular weight oxidation product ions provide evidence of previously unreported compounds and their temporal evolution in the smog chamber from multistep oxidation processes. Many of the observed ions, including m/z 111 and 113, have also been observed in ambient air above a Ponderosa pine forest canopy, and our results confirm they are consistent with products from terpene + O_3 reactions. Many of these products are stable on the timescale of our experiments and can therefore be monitored in field campaigns as evidence for ozone oxidative chemistry