Investigations of secondary organic aerosol formation in laboratory chambers

Secondary organic aerosol (SOA) is produced in the atmosphere by oxidation of volatile organic compounds. Laboratory chambers are used understand the formation mechanisms and evolution of SOA formed under controlled conditions. This thesis presents studies of SOA formed from anthropogenic and biogenic precursors and discusses the effects of chamber walls on suspended vapors and particles.

During a chamber experiment, suspended vapors and particles can interact with the chamber walls. Particle wall loss is relatively well-understood, but vapor wall losses have received little study. Vapor wall loss of 2,3-epoxy-1,4-butanediol (BEPOX) and glyoxal was identified, quantified, and found to depend on chamber age and relative humidity.

Particles reside in the atmosphere for a week or more and can evolve chemically during that time period, a process termed aging. Simulating aging in laboratory chambers has proven to be challenging. A protocol was developed to extend the duration of a chamber experiment to 36 h of oxidation and was used to evaluate aging of SOA produced from m-xylene. Total SOA mass concentration increased and then decreased with increasing photooxidation suggesting a transition from functionalization to fragmentation chemistry driven by photochemical processes. SOA oxidation, measured as the bulk particle elemental oxygen-to-carbon ratio and fraction of organic mass at m/z 44, increased continuously starting after 5 h of photooxidation.

The physical state and chemical composition of an organic aerosol affect the mixing of aerosol components and its interactions with condensing species. A laboratory chamber protocol was developed to evaluate the mixing of SOA produced sequentially from two different sources by heating the chamber to induce particle evaporation. Using this protocol, SOA produced from toluene was found to be less volatile than that produced from a-pinene. When the two types of SOA were formed sequentially, the evaporation behavior most closely represented that of SOA from the second parent hydrocarbon, suggesting that the structure of the mixed SOA particles resembles a core of SOA from the first precursor coated by a layer of SOA from the second precursor, indicative of limiting mixing.

Nonstationary response of structures and its application to earthquake engineering

This thesis presents a simplified state-variable method to solve for the nonstationary response of linear MDOF systems subjected to a modulated stationary excitation in both time and frequency domains. The resulting covariance matrix and evolutionary spectral density matrix of the response may be expressed as a product of a constant system matrix and a time-dependent matrix, the latter can be explicitly evaluated for most envelopes currently prevailing in engineering. The stationary correlation matrix of the response may be found by taking the limit of the covariance response when a unit step envelope is used. The reliability analysis can then be performed based on the first two moments of the response obtained.

The method presented facilitates obtaining explicit solutions for general linear MDOF systems and is flexible enough to be applied to different stochastic models of excitation such as the stationary models, modulated stationary models, filtered stationary models, and filtered modulated stationary models and their stochastic equivalents including the random pulse train model, filtered shot noise, and some ARMA models in earthquake engineering. This approach may also be readily incorporated into finite element codes for random vibration analysis of linear structures.

A set of explicit solutions for the response of simple linear structures subjected to modulated white noise earthquake models with four different envelopes are presented as illustration. In addition, the method has been applied to three selected topics of interest in earthquake engineering, namely, nonstationary analysis of primary-secondary systems with classical or nonclassical dampings, soil layer response and related structural reliability analysis, and the effect of the vertical components on seismic performance of structures. For all the three cases, explicit solutions are obtained, dynamic characteristics of structures are investigated, and some suggestions are given for aseismic design of structures.

Secondary Organic Aerosol Composition Studies Using Mass Spectrometry

Trace volatile organic compounds emitted by biogenic and anthropogenic sources into the atmosphere can undergo extensive photooxidation to form species with lower volatility. By equilibrium partitioning or reactive uptake, these compounds can nucleate into new aerosol particles or deposit onto already-existing particles to form secondary organic aerosol (SOA). SOA and other atmospheric particulate matter have measurable effects on global climate and public health, making understanding SOA formation a needed field of scientific inquiry. SOA formation can be done in a laboratory setting, using an environmental chamber; under these controlled conditions it is possible to generate SOA from a single parent compound and study the chemical composition of the gas and particle phases. By studying the SOA composition, it is possible to gain understanding of the chemical reactions that occur in the gas phase and particle phase, and identify potential heterogeneous processes that occur at the surface of SOA particles. In this thesis, mass spectrometric methods are used to identify qualitatively and qualitatively the chemical components of SOA derived from the photooxidation of important anthropogenic volatile organic compounds that are associated with gasoline and diesel fuels and industrial activity (C12 alkanes, toluene, and o-, m-, and p-cresols). The conditions under which SOA was generated in each system were varied to explore the effect of NO_x and inorganic seed composition on SOA chemical composition. The structure of the parent alkane was varied to investigate the effect on the functionalization and fragmentation of the resulting oxidation products. Relative humidity was varied in the alkane system as well to measure the effect of increased particle-phase water on condensed-phase reactions. In all systems, oligomeric species, resulting potentially from particle-phase and heterogeneous processes, were identified. Imines produced by reactions between (NH₄)₂SO₄ seed and carbonyl compounds were identified in all systems. Multigenerational photochemistry producing low- and extremely low-volatility organic compounds (LVOC and ELVOC) was reflected strongly in the particle-phase composition as well.

Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers

Our understanding of the processes and mechanisms by which secondary organic aerosol (SOA) is formed is derived from laboratory chamber studies. In the atmosphere, SOA formation is primarily driven by progressive photooxidation of SOA precursors, coupled with their gas-particle partitioning. In the chamber environment, SOA-forming vapors undergo multiple chemical and physical processes that involve production and removal via gas-phase reactions; partitioning onto suspended particles vs. particles deposited on the chamber wall; and direct deposition on the chamber wall. The main focus of this dissertation is to characterize the interactions of organic vapors with suspended particles and the chamber wall and explore how these intertwined processes in laboratory chambers govern SOA formation and evolution.

A Functional Group Oxidation Model (FGOM) that represents SOA formation and evolution in terms of the competition between functionalization and fragmentation, the extent of oxygen atom addition, and the change of volatility, is developed. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation.

A critical aspect of the environmental chamber is the presence of the wall, which can induce deposition of SOA-forming vapors and promote heterogeneous reactions. An experimental protocol and model framework are first developed to constrain the vapor-wall interactions. By optimal fitting the model predictions to the observed wall-induced decay profiles of 25 oxidized organic compounds, the dominant parameter governing the extent of wall deposition of a compound is identified, i.e., wall accommodation coefficient. By correlating this parameter with the molecular properties of a compound via its volatility, the wall-induced deposition rate of an organic compound can be predicted based on its carbon and oxygen numbers in the molecule.

Heterogeneous transformation of δ-hydroxycarbonyl, a major first-generation product from long-chain alkane photochemistry, is observed on the surface of particles and walls. The uniqueness of this reaction scheme is the production of substituted dihydrofuran, which is highly reactive towards ozone, OH, and NO3, thereby opening a reaction pathway that is not usually accessible to alkanes. A spectrum of highly-oxygenated products with carboxylic acid, ester, and ether functional groups is produced from the substituted dihydrofuran chemistry, thereby affecting the average oxidation state of the alkane-derived SOA.

The vapor wall loss correction is applied to several chamber-derived SOA systems generated from both anthropogenic and biogenic sources. Experimental and modeling approaches are employed to constrain the partitioning behavior of SOA-forming vapors onto suspended particles vs. chamber walls. It is demonstrated that deposition of SOA-forming vapors to the chamber wall during photooxidation experiments can lead to substantial and systematic underestimation of SOA. Therefore, it is likely that a lack of proper accounting for vapor wall losses that suppress chamber-derived SOA yields contribute substantially to the underprediction of ambient SOA concentrations in atmospheric models.

Application of algal bioassays in the determination of eutrophic power of waste water (”Conclusions” only) [Translation from: 1g.Sanita pubbl. 31 257-267, 1975]

The best evidence for establishing the level of eutrophy of a water-body is its algal production which makes it possible to identify the type and the intensity of the eutrophication according to the kind and number of algal species present: when the number of algae exceeds half a million per litre then one speaks o an ”algal bloom”. The scope of the present research aims to verify if the alga Selenastrum capricornutum can be used as a test alga under our culture conditions and to determine the eutrophic level of the secondary effluent of a modern plant for the treatment of domestic discharge and to investigate the eventual ”limiting factors”. Finally this paper aims to study the effect on the secondary effluent of tertiary treatment carried out artificially in the laboratory.

Calcareous concretions in the Levriere (tributary of the Epte, secondary tributary of the Seine, Eure department) [Translation from: Bull.Ass.fr.Etud.Quaternaire 1973(2), 79-87, 1973]

From research carried, out on a section of the Levriere, concretions (granules, nodules, which were sometimes joined together) partly covering the river ”bottom” were observed. The authors propose to make besides a petrographic examination of the calcareous precipitations and to see if their origin is connected to a biological activity, or if it is purely a case of a physical-chemical precipitation. The hydrological background of the Levriere, a small river of the Normandy Vexin, is given and conditions of the formation of the concretions studied.

Effects of injection nozzle configuration on secondary injection into supersonic flow

Gaseous nitrogen and argon were injected into a primary stream of air moving at Mach 2.56. The gases were injected at secondary to primary total pressure ratios from 3.2 to 28.6 through four different nozzles. Two nozzles, one sonic and one supersonic (M = 3.26), injected normal to the primary stream; and two sonic nozzles injected at 45° angles to the primary flow, one injecting upstream and the other downstream. Data consisted of static pressure measurements on the wall near the injector, total pressure profiles in the wake of the injectant plume, and concentration measurements downstream of the flow. Scale parameters were calculated based upon an analytical model of the flow field and their validity verified by experimental results. These scale heights were used to compare normalized wall side forces for the different nozzles and to compare the mixing of the two streams.

Shrimp disease management using bioactive marine secondary metabolites: an eco-friendly approach

Vibriosis caused by opportunistic and secondary bacterial pathogens is still a serious disease problem in aquaculture of the black tiger shrimp Penaeus monodon. Attempts were made for controlling shrimp bacterial disease using Marine Secondary Metabolites (MSMs). Findings indicated that the MSMs of seaweed Ulva fasciata and Dendrilla nigra are effective for controlling shrimp bacterial pathogens.

A new alternative for reduction of secondary flows in low pressure turbines

This paper describes a new flow mechanism for the reduction of secondary flows in Low Pressure Turbines using the benefit of contoured endwalls. The extensive application of contoured endwalls in recent years has provided a deeper understanding of the physical phenomenon that governs the reduction of secondary flows. Based on this understanding, the endwall geometry of a linear cascade of solid-thin profiles typical of Low Pressure Turbines has been redesigned. Experimental data are presented for the validation of this new solution. Based on these data, a reduction of 72% in the SKEH and 20% in the mixed-out endwall losses can be obtained. CFD simulations are also presented to illustrate the effect of the new endwall on the secondary flows. Furthermore, an explanation of the flow mechanism that governs the reduction of the SKEH and the losses is given. Copyright © 2006 by ASME.

Diversity, abundance distribution and secondary production of intertidal and subtidal benthic macrofauna of Bushehr Province with emphasis on annelida groups

The present investigation was undertaken to establish a reference situation for future use, to identify temporal and spatial composition of macrofauna and estimate some ecological indices in the sub tidal waters along the Bushehr coastal waters in Persian Gulf. Six transects were selected including Genaveh, Farakeh, Shif, Bandargah, Rostami and Asalouyeh, at each transect 3 station were sampled in depths of zero, 5 and 10 metres. Sampling was seasonally carried out by a VAN VEEN grab 0.0225 m2, during summer 2008 until spring 2009. Samples were wet sieved immediately using 0.5 mm mesh size sieves and sediment retained in the sieve was preserved in 4% buffered formalin solution. Macrofauna specimen were separated from the sediments using decantation and elutriation methods, enumerated and identified up to the Genus level. Environmental factors such as temperature. pH, and salinity were recorded in field using sensitive probs and refractometer (for salinity) and also sediment samples were taken for TOM and grain size analysis in all the stations. 5611 specimens belonging to 66 genera were collected during the present study. Polychaetes were dominant both in terms of genus number (31) and relative abundance (74 % of total macrofaunal abundance). The other dominant groups were Artheropoda, (16.1%), Molusca (2.8%), Echinodermata (1.29%) and others including Nematoda, Nemertina, Echiura and Turbellaria (5.8%). Thirty one Genera belong of 27 families of polychaeta, one genus and family of Subphylum Chlicerata,19 genera belong to 14 families of Crustacea, 8 genera belong to 6 families of Molusca, were indentified in the studied region. 1 family (Polygordidae) and 3 genera (Flabeligera, Pilargis and Polygordius) of Polychaeta, 1 family (Nymphonidae) and genus (Nymphon) of Chelicerata, 1 Family (Nematoplanidae) and genus (Nematoplana) of Turbellaria, were identified for the first time in Persian Gulf area. The result indicated that macrofauna organism have strong relationship with the grain size characteristics of the sediments they inhabit. The most surface deposit feeder specimens such as Prionospio and Cossura were found in zero meters depth of Genaveh, Farakeh, Bandargah, Rostami and Asalouyeh stations with sandy substratum, however the most burrowing deposit feeder and scavenger specimens such as Capitella and Petaloproctus were collected in 5 and 10 meter depths of stations with silty–clay substratum. The annual mean abundance, Shanon- weiner diversity and evenness of macrofauna were estimated1152.73 N/ m² , 2.72 and 0.792 respectively .The annual average biomass and secondary production were computed 1.797 gDW m² and 3.594 gDW m² y-1 .The average of water temperature, salinity, pH and oxygen concentration were recorded between 16.37-36.05 °C, 38-42 g/l, 7.89-8.76 and 4.23-8.23 mg/l, respectively during this study in 6 studied region. Among of investigated stations Asalouyeh adjacent of effluent canal of Gas and petrochemical industry sewage and Farakeh regions adjacent the Helleh estuary had the lowets and the highest community indices. The average of diversity and density in 5 meters depth stations with moderate of sand, silt and clay were slightly more than 2 other depths stations, it seems that 5 meters stations are made a transition habitats between 2 sandy and clay habitats, that can be used by 2 groups of surface and borrowing deposit feeders. Based on the data provided in this survey, the temperature variation, sediment texture, TOM, type habitat and manmade factors of Gas and petrochemical industries have had the most effect on the macrofauna community structure in the studied region during sampling periods.

Assessment of pelagic primary and secondary production in Sefidrud River estuary

Sefid-Rood River Estuary (SRE) is the most important riverine ecosystem in the south Caspian Sea along the Iranian coast lines. The aim of this study was to examine spatial and temporal variability in Phytoplankton and Zooplankton abundance and diversity in SRE. Variability of Chlorophyll a and inorganic nutrient concentration were determined during a year (November 2004– October 2005) in five sampling stations. Primary and secondry production were determined during a year. Total chlorophyll a concentration during the investigation ranged between zero to 22.8 μgl-1 and the highest levels were consistently recorded during summer and the lowest during winter with a annual mean concentration 4.48 μgl-1. Nutrient concentration was seasonally related to river flow with annual mean concentration: NO2 0.05±0.2 mgl-1, NO3 1.13±0.57 mgl-1, NH4 0.51±0.66 mgl-1, total phosphate 0.13±0.1mgl-1 and SiO2 5.68±1.91 mgl-1. Bacillariophytes, Cyanophytes, Chlorophytes, Pyrophytes and Euglenophytes were the dominant phytoplankton groups in this shallow and turbid estuary. The diversity and abundance of phytoplankton had a seasonal pattern while Diatomas and Chrysophytes were dominant throughout the year but Cyanophytes observed only during the summer. Zooplankton community structure was dominated by copepods which 68% of the total zooplankton. In the winter and summer seasons two increased in the number of zooplankton community and usually toward the sea had occurred. Zooplankton also showed a significant spatial and temporal variation. The high turbidity and temperature prime characteristics of SRE seem to be determining factors acting directly on phytoplankton and zooplankton temporal variability and nutrient fluctuations. Everywhere in this estuary nutrients appeared to be in excess of algal requirement and did not influence a phytoplankton and zooplankton composition. Also there was a positive correlation between chlorophyll a and temperature and a negative one with DIN and TP. Primary production determined in this estuary by dark and light butter method and G.P.P. 38.27±34.12 mgcm-2h-1 and N,PP 201.6±289.9 mgcm-2d-1. secondry production determined 15/128 mgc/m3/year. Everywhere in this estuary nutrients appeared to be in excess to algal requirement and did not influence in Chl. a and primary production. The most important factor influence on Chl. a was water temperature.

Blade loading and its application in the mean-line design of low pressure turbines

In order to minimize the number of iterations to a turbine design, reasonable choices of the key parameters must be made at the earliest possible opportunity. The choice of blade loading is of particular concern in the low pressure (LP) turbine of civil aero engines, where the use of high-lift blades is widespread. This paper presents an analytical mean-line design study for a repeating-stage, axial-flow Low Pressure (LP) turbine. The problem of how to measure blade loading is first addressed. The analysis demonstrates that the Zweifel coefficient [1] is not a reasonable gauge of blade loading because it inherently depends on the flow angles. A more appropriate coefficient based on blade circulation is proposed. Without a large set of turbine test data it is not possible to directly evaluate the accuracy of a particular loss correlation. The analysis therefore focuses on the efficiency trends with respect to flow coefficient, stage loading, lift coefficient and Reynolds number. Of the various loss correlations examined, those based on Ainley and Mathieson ([2], [3], [4]) do not produce realistic trends. The profile loss model of Coull and Hodson [5] and the secondary loss models of Craig and Cox [6] and Traupel [7] gave the most reasonable results. The analysis suggests that designs with the highest flow turning are the least sensitive to increases in blade loading. The increase in Reynolds number lapse with loading is also captured, achieving reasonable agreement with experiments. Copyright © 2011 by ASME.

Blade Loading and Its Application in the Mean-Line Design of Low Pressure Turbines

In order to minimize the number of iterations to a turbine design, reasonable choices of the key parameters must be made at the preliminary design stage. The choice of blade loading is of particular concern in the low pressure (LP) turbine of civil aero engines, where the use of high-lift blades is widespread. This paper considers how blade loading should be measured, compares the performance of various loss correlations, and explores the impact of blade lift on performance and lapse rates. To these ends, an analytical design study is presented for a repeating-stage, axial-flow LP turbine. It is demonstrated that the long-established Zweifel lift coefficient (Zweifel, 1945, "The Spacing of Turbomachine Blading, Especially with Large Angular Deflection" Brown Boveri Rev., 32(1), pp. 436-444) is flawed because it does not account for the blade camber. As a result the Zweifel coefficient is only meaningful for a fixed set of flow angles and cannot be used as an absolute measure of blade loading. A lift coefficient based on circulation is instead proposed that accounts for the blade curvature and is independent of the flow angles. Various existing profile and secondary loss correlations are examined for their suitability to preliminary design. A largely qualitative comparison demonstrates that the loss correlations based on Ainley and Mathieson (Ainley and Mathieson, 1957, "A Method of Performance Estimation for Axial-Flow Turbines," ARC Reports and Memoranda No. 2974; Dunham and Came, 1970, "Improvements to the Ainley-Mathieson Method of Turbine Performance Prediction," Trans. ASME: J. Eng. Gas Turbines Power, July, pp. 252-256; Kacker and Okapuu, 1982, "A Mean Line Performance Method for Axial Flow Turbine Efficiency," J. Eng. Power, 104, pp. 111-119). are not realistic, while the profile loss model of Coull and Hodson (Coull and Hodson, 2011, "Predicting the Profile Loss of High-Lift Low Pressure Turbines," J. Turbomach., 134(2), pp. 021002) and the secondary loss model of (Traupel, W, 1977, Thermische Turbomaschinen, Springer-Verlag, Berlin) are arguably the most reasonable. A quantitative comparison with multistage rig data indicates that, together, these methods over-predict lapse rates by around 30%, highlighting the need for improved loss models and a better understanding of the multistage environment. By examining the influence of blade lift across the Smith efficiency chart, the analysis demonstrates that designs with higher flow turning will tend to be less sensitive to increases in blade loading. © 2013 American Society of Mechanical Engineers.

Towards manipulation of post-biosynthetic events in secondary metabolism of plant cell cultures

Plant cell cultures have been suggested as a feasible technology for the production of a myriad of plant-derived metabolites. However, commercial application of plant cell culture has met limited success with only a handful of metabolites produced at the pilot- and commercial-scales. To improve the production of secondary metabolites in plant cell cultures, efforts have been devoted predominantly to the optimization of biosynthetic pathways by both process and genetic engineering approaches. Given that secondary metabolism includes-the synthesis. metabolism and catabolism of endogenous compounds by the specialized proteins, this review intends to draw attention to the manipulation and optimization of post-biosynthetic events that follow the formation of core metabolite structures in biosynthetic pathways. These post-biosynthetic events-the chemical and enzymatic modifications, transport, storage/secretion and catabolism/degradation have been largely unexplored in the past. Potential areas are identified where further research is needed to answer fundamental questions that have implications for advanced bioprocess design. Anthocyanin production by plant cell cultures is used as a case study for this discussion, as it presents a good example of compounds for which there are extensive research publications but still no commercial bioprocess. It is perceived that research on post-biosynthetic processes may lead to future opportunities for significant advances in commercial plant cell cultures. (C) 2002 Elsevier Science Inc. All rights reserved.