970 resultados para Organic farming -- Catalonia (Spain)
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In this article, pathways from freshwater and marine environments are described. DOM is defined operationally as all the organic compounds which pass through a filter of pore size 0.45 microm., those retained on the surface of the filter being particulate organic matter (POM). DOM can be taken up directly by animals by transfer across the body wall, but more commonly DOM is obtained from ingested food. Once ingested POM from food particles are broken down in the gut, small molecules of DOM are released for transfer across the gut wall. Some ingested particles are attacked by micro-organisms living in the gut, thereby making the DOM available to the host animal. The importance of the microbial loop is discussed, as well as aggregation processes between the fractions of DOM which are more obviously particulate in nature. (DBO)
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Changes in sustainability of aquatic ecosystems are likely to be brought about by the global warming that has been widely predicted. In this article, the effects of water temperature on water-bodies (lakes, oceans and rivers) are reviewed followed by the effects of temperature on aquatic organisms. Almost all aquatic organisms require exogenous heat before they can metabolise efficiently. An organism that is adapted to warm temperatures will have a higher rate of metabolism of food organisms and this increases feeding rate. In addition, an increase in temperature raises the metabolism of food organisms, so food quality can be altered. Where populations have a different tolerance to temperature the result is habitat partitioning. One effect of prolonged high temperature is that it causes water to evaporate readily. In the marine littoral this is not an important problem as tides will replenish water in pools. Small rain pools are found in many tropical countries during the rainy season and these become incompletely dried at intervals. The biota of such pools must have resistant stages within the life cycle that enable them to cope with periods of drying. The most important potential effects of global warming include (i) the alteration of existing coastlines, (ii) the development of more deserts on some land masses, (iii) higher productivity producing higher crop production but a greater threat of algal blooms and (iv) the processing of organic matter at surface microlayers.
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Very little research has been carried out on detrital energetics and pathways in lotic ecosystems. Most investigations have concentrated on the degradation of allochthonous plant litter by fungi, with a glance at heterotrophic bacteria associated with decaying litter. In this short review, the author describes what is known of the detrition of plant litter in lotic waters, which results from the degradative activities of colonising saprophytic fungi and bacteria, and goes on to relate this process to those invertebrates that consume coarse and/or fine particulate detritus, or dissolved organic matter that aggregates into colloidal exopolymer particles. It is clear that many of the key processes involved in the relationships between the physical, chemical, biotic and biochemical elements present in running waters are very complex and poorly understood. Those few aspects for which there are reliable models with predictive power have resulted from data collections made over periods of 20 years or more. Comprehensive research of single catchments would provide a fine opportunity to collect data over a long period.
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Isoprene (ISO),the most abundant non-methane VOC, is the major contributor to secondary organic aerosols (SOA) formation. The mechanisms involved in such transformation, however, are not fully understood. Current mechanisms, which are based on the oxidation of ISO in the gas-phase, underestimate SOA yields. The heightened awareness that ISO is only partially processed in the gas-phase has turned attention to heterogeneous processes as alternative pathways toward SOA.
During my research project, I investigated the photochemical oxidation of isoprene in bulk water. Below, I will report on the λ > 305 nm photolysis of H2O2 in dilute ISO solutions. This process yields C10H15OH species as primary products, whose formation both requires and is inhibited by O2. Several isomers of C10H15OH were resolved by reverse-phase high-performance liquid chromatography and detected as MH+ (m/z = 153) and MH+-18 (m/z = 135) signals by electrospray ionization mass spectrometry. This finding is consistent with the addition of ·OH to ISO, followed by HO-ISO· reactions with ISO (in competition with O2) leading to second generation HO(ISO)2· radicals that terminate as C10H15OH via β-H abstraction by O2.
It is not generally realized that chemistry on the surface of water cannot be deduced, extrapolated or translated to those in bulk gas and liquid phases. The water density drops a thousand-fold within a few Angstroms through the gas-liquid interfacial region and therefore hydrophobic VOCs such as ISO will likely remain in these relatively 'dry' interfacial water layers rather than proceed into bulk water. In previous experiments from our laboratory, it was found that gas-phase olefins can be protonated on the surface of pH < 4 water. This phenomenon increases the residence time of gases at the interface, an event that makes them increasingly susceptible to interaction with gaseous atmospheric oxidants such as ozone and hydroxyl radicals.
In order to test this hypothesis, I carried out experiments in which ISO(g) collides with the surface of aqueous microdroplets of various compositions. Herein I report that ISO(g) is oxidized into soluble species via Fenton chemistry on the surface of aqueous Fe(II)Cl2 solutions simultaneously exposed to H2O2(g). Monomer and oligomeric species (ISO)1-8H+ were detected via online electrospray ionization mass spectrometry (ESI-MS) on the surface of pH ~ 2 water, and were then oxidized into a suite of products whose combined yields exceed ~ 5% of (ISO)1-8H+. MS/MS analysis revealed that products mainly consisted of alcohols, ketones, epoxides and acids. Our experiments demonstrated that olefins in ambient air may be oxidized upon impact on the surface of Fe-containing aqueous acidic media, such as those of typical to tropospheric aerosols.
Related experiments involving the reaction of ISO(g) with ·OH radicals from the photolysis of dissolved H2O2 were also carried out to test the surface oxidation of ISO(g) by photolyzing H2O2(aq) at 266 nm at various pH. The products were analyzed via online electrospray ionization mass spectrometry. Similar to our Fenton experiments, we detected (ISO)1-7H+ at pH < 4, and new m/z+ = 271 and m/z- = 76 products at pH > 5.
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The economic, environmental and social benefits of more sensitive land use practices that protect or restore the natural functions of river catchments have been widely discussed. Changing land use has implications for a wide range of other biological communities. Some studies have already been undertaken on the benefits of sensitive farming at the catchment scale in England and Wales. However, there is a gap in these studies at the local scale, and particularly for upland farms from which headwaters arise. This article documents a case study relating to a successful partnership in Cumbria, UK, set within the wider context of catchment management. Whilst the case study is not highly detailed, and some costs have been described in outline only to protect confidentiality and commercial sensitivity, it provides some generic lessons and may therefore be useful in informing more sustainable policy-making. High Hullockhowe Farm near Haweswater, which was used a the case study highlighting changes in farm practise, costs and benefits, water resources and biodiversity. The authors relate the case study to wider policy implications.
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It is often difficult to define ‘water quality’ with any degree of precision. One approach is that suggested by Battarbee (1997) and is based on the extent to which individual lakes have changed compared with their natural ‘baseline’ status. Defining the base-line status of artificial lakes and reservoirs however, is, very difficult. In ecological terms, the definition of quality must include some consideration of their functional characteristics and the extent to which these characteristics are self-sustaining. The challenge of managing lakes in a sustainable way is particularly acute in semi-arid, Mediterranean countries. Here the quality of the water is strongly influenced by the unpredictability of the rainfall as well as year-to-year variations in the seasonal averages. Wise management requires profound knowledge of how these systems function. Thus a holistic approach must be adopted and the factors influencing the seasonal dynamics of the lakes quantified over a range of spatial and temporal scales. In this article, the authors describe some of the ways in which both long-term and short-term changes in the weather have influenced the seasonal and spatial dynamics of phytoplankton in El Gergal, a water supply reservoir situated in the south of Spain. The quality of the water stored in this reservoir is typically very good but surface blooms of algae commonly appear during warm, calm periods when the water level is low. El Gergal reservoir is managed by the Empresa Municipal de Abastecimiento y Saneamiento (EMASESA) and supplies water for domestic, commercial and industrial use to an area which includes the city of Seville and twelve of its surrounding towns (ca. 1.3 million inhabitants). El Gergal is the last of two reservoirs in a chain of four situated in the Rivera de Huelva basin, a tributary of the Guadalquivir river. It was commissioned by EMASESA in 1979 and since then the company has monitored its main limnological parameters on, at least, a monthly basis and used this information to improve the management of the reservoir. As a consequence of these intensive studies the physical, chemical and biological information acquired during this period makes the El Gergal database one of the most complete in Spain. In this article the authors focus on three ‘weather-related’ effects that have had a significant impact on the composition and distribution of phytoplankton in El Gergal: (i) the changes associated with severe droughts; (ii) the spatial variations produced by short-term changes in the weather; (iii) the impact of water transfers on the seasonal dynamics of the dinoflagellate Ceratium.
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Part I:
The earth's core is generally accepted to be composed primarily of iron, with an admixture of other elements. Because the outer core is observed not to transmit shear waves at seismic frequencies, it is known to be liquid or primarily liquid. A new equation of state is presented for liquid iron, in the form of parameters for the 4th order Birch-Murnaghan and Mie-Grüneisen equations of state. The parameters were constrained by a set of values for numerous properties compiled from the literature. A detailed theoretical model is used to constrain the P-T behavior of the heat capacity, based on recent advances in the understanding of the interatomic potentials for transition metals. At the reference pressure of 105 Pa and temperature of 1811 K (the normal melting point of Fe), the parameters are: ρ = 7037 kg/m3, KS0 = 110 GPa, KS' = 4.53, KS" = -.0337 GPa-1, and γ = 2.8, with γ α ρ-1.17. Comparison of the properties predicted by this model with the earth model PREM indicates that the outer core is 8 to 10 % less dense than pure liquid Fe at the same conditions. The inner core is also found to be 3 to 5% less dense than pure liquid Fe, supporting the idea of a partially molten inner core. The density deficit of the outer core implies that the elements dissolved in the liquid Fe are predominantly of lower atomic weight than Fe. Of the candidate light elements favored by researchers, only sulfur readily dissolves into Fe at low pressure, which means that this element was almost certainly concentrated in the core at early times. New melting data are presented for FeS and FeS2 which indicate that the FeS2 is the S-hearing liquidus solid phase at inner core pressures. Consideration of the requirement that the inner core boundary be observable by seismological means and the freezing behavior of solutions leads to the possibility that the outer core may contain a significant fraction of solid material. It is found that convection in the outer core is not hindered if the solid particles are entrained in the fluid flow. This model for a core of Fe and S admits temperatures in the range 3450K to 4200K at the top of the core. An all liquid Fe-S outer core would require a temperature of about 4900 K at the top of the core.
Part II.
The abundance of uses for organic compounds in the modern world results in many applications in which these materials are subjected to high pressures. This leads to the desire to be able to describe the behavior of these materials under such conditions. Unfortunately, the number of compounds is much greater than the number of experimental data available for many of the important properties. In the past, one approach that has worked well is the calculation of appropriate properties by summing the contributions from the organic functional groups making up molecules of the compounds in question. A new set of group contributions for the molar volume, volume thermal expansivity, heat capacity, and the Rao function is presented for functional groups containing C, H, and O. This set is, in most cases, limited in application to low molecular liquids. A new technique for the calculation of the pressure derivative of the bulk modulus is also presented. Comparison with data indicates that the presented technique works very well for most low molecular hydrocarbon liquids and somewhat less well for oxygen-bearing compounds. A similar comparison of previous results for polymers indicates that the existing tabulations of group contributions for this class of materials is in need of revision. There is also evidence that the Rao function contributions for polymers and low molecular compounds are somewhat different.
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The Mediterranean region is characterised by a variable climate with most of the rain falling during the winter and frequent summer droughts. Such warm, dry periods are ideal for the growth of large algal blooms that often consist of potentially toxic Cyanobacteria. This makes the management of water for human use particularly challenging in such a climate and it is important to understand how such blooms can be avoided or at least be reduced in size. PROTECH (Phytoplankton RespOnses To Environmental CHange) is a model that simulates the dynamics of different species of phytoplankton populations in lakes and reservoirs. Its distinct advantage over similar models is its ability to simulate the relative composition of the algal flora, allowing both quantitative and qualitative conclusions to be drawn e.g. whether Cyanobacteria could be a potential problem. PROTECH has been applied primarily to lakes and reservoirs in northern Europe. Recently, however, the model has been applied to water bodies in lower latitudes, including Australia to a water supply reservoir in the south of Spain, El Gergal. El Gergal is the last in a chain of reservoirs that supply water to the city of Seville. It was brought into service in April 1979 and has a maximum storage volume of 35 000 000 m3. This article summarises the application of PROTECH in order to simulate the following problems: • the effect of a large influx of Ceratium biomass into El Gergal from another reservoir • the effect of using alternative water sources instead of the Guadalquivir River (used occasionally to raise water levels in El Gergal) • the effect of installing tertiary sewage treatment on the Cala River • the effect of simulated drought conditions on phytoplankton in the reservoir.
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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 NOx 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.
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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.
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Stable isotope geochemistry is a valuable toolkit for addressing a broad range of problems in the geosciences. Recent technical advances provide information that was previously unattainable or provide unprecedented precision and accuracy. Two such techniques are site-specific stable isotope mass spectrometry and clumped isotope thermometry. In this thesis, I use site-specific isotope and clumped isotope data to explore natural gas development and carbonate reaction kinetics. In the first chapter, I develop an equilibrium thermodynamics model to calculate equilibrium constants for isotope exchange reactions in small organic molecules. This equilibrium data provides a framework for interpreting the more complex data in the later chapters. In the second chapter, I demonstrate a method for measuring site-specific carbon isotopes in propane using high-resolution gas source mass spectrometry. This method relies on the characteristic fragments created during electron ionization, in which I measure the relative isotopic enrichment of separate parts of the molecule. My technique will be applied to a range of organic compounds in the future. For the third chapter, I use this technique to explore diffusion, mixing, and other natural processes in natural gas basins. As time progresses and the mixture matures, different components like kerogen and oil contribute to the propane in a natural gas sample. Each component imparts a distinct fingerprint on the site-specific isotope distribution within propane that I can observe to understand the source composition and maturation of the basin. Finally, in Chapter Four, I study the reaction kinetics of clumped isotopes in aragonite. Despite its frequent use as a clumped isotope thermometer, the aragonite blocking temperature is not known. Using laboratory heating experiments, I determine that the aragonite clumped isotope thermometer has a blocking temperature of 50-100°C. I compare this result to natural samples from the San Juan Islands that exhibit a maximum clumped isotope temperature that matches this blocking temperature. This thesis presents a framework for measuring site-specific carbon isotopes in organic molecules and new constraints on aragonite reaction kinetics. This study represents the foundation of a future generation of geochemical tools for the study of complex geologic systems.
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The central theme of this thesis is the use of imidazolium-based organic structure directing agents (OSDAs) in microporous materials synthesis. Imidazoliums are advantageous OSDAs as they are relatively inexpensive and simple to prepare, show robust stability under microporous material synthesis conditions, have led to a wide range of products, and have many permutations in structure that can be explored. The work I present involves the use of mono-, di-, and triquaternary imidazolium-based OSDAs in a wide variety of microporous material syntheses. Much of this work was motivated by successful computational predictions (Chapter 2) that led me to continue to explore these types of OSDAs. Some of the important discoveries with these OSDAs include the following: 1) Experimental evaluation and confirmation of a computational method that predicted a new OSDA for pure-silica STW, a desired framework containing helical pores that was previously very difficult to synthesize. 2) Discovery of a number of new imidazolium OSDAs to synthesize zeolite RTH, a zeolite desired for both the methanol-to-olefins reaction as well as NOX reduction in exhaust gases. This discovery enables the use of RTH for many additional investigations as the previous OSDA used to make this framework was difficult to synthesize, such that no large scale preparations would be practical. 3) The synthesis of pure-silica RTH by topotactic condensation from a layered precursor (denoted CIT-10), that can also be pillared to make a new framework material with an expanded pore system, denoted CIT-11, that can be calcined to form a new microporous material, denoted CIT-12. CIT-10 is also interesting since it is the first layered material to contain 8 membered rings through the layers, making it potentially useful in separations if delamination methods can be developed. 4) The synthesis of a new microporous material, denoted CIT-7 (framework code CSV) that contains a 2-dimensional system of 8 and 10 membered rings with a large cage at channel intersections. This material is especially important since it can be synthesized as a pure-silica framework under low-water, fluoride-mediated synthesis conditions, and as an aluminosilicate material under hydroxide mediated conditions. 5) The synthesis of high-silica heulandite (HEU) by topotactic condensation as well as direct synthesis, demonstrating new, more hydrothermally stable compositions of a previously known framework. 6) The synthesis of germanosilicate and aluminophosphate LTA using a triquaternary OSDA. All of these materials show the diverse range of products that can be formed from OSDAs that can be prepared by straightforward syntheses and have made many of these materials accessible for the first time under facile zeolite synthesis conditions.
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This thesis is the culmination of field and laboratory studies aimed at assessing processes that affect the composition and distribution of atmospheric organic aerosol. An emphasis is placed on measurements conducted using compact and high-resolution Aerodyne Aerosol Mass Spectrometers (AMS). The first three chapters summarize results from aircraft campaigns designed to evaluate anthropogenic and biogenic impacts on marine aerosol and clouds off the coast of California. Subsequent chapters describe laboratory studies intended to evaluate gas and particle-phase mechanisms of organic aerosol oxidation.
The 2013 Nucleation in California Experiment (NiCE) was a campaign designed to study environments impacted by nucleated and/or freshly formed aerosol particles. Terrestrial biogenic aerosol with > 85% organic mass was observed to reside in the free troposphere above marine stratocumulus. This biogenic organic aerosol (BOA) originated from the Northwestern United States and was transported to the marine atmosphere during periodic cloud-clearing events. Spectra recorded by a cloud condensation nuclei counter demonstrated that BOA is CCN active. BOA enhancements at latitudes north of San Francisco, CA coincided with enhanced cloud water concentrations of organic species such as acetate and formate.
Airborne measurements conducted during the 2011 Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) were aimed at evaluating the contribution of ship emissions to the properties of marine aerosol and clouds off the coast of central California. In one study, analysis of organic aerosol mass spectra during periods of enhanced shipping activity yielded unique tracers indicative of cloud-processed ship emissions (m/z 42 and 99). The variation of their organic fraction (f42 and f99) was found to coincide with periods of heavy (f42 > 0.15; f99 > 0.04), moderate (0.05 < f42 < 0.15; 0.01 < f99 < 0.04), and negligible (f42 < 0.05; f99 < 0.01) ship influence. Application of these conditions to all measurements conducted during E-PEACE demonstrated that a large fraction of cloud droplet (72%) and dry aerosol mass (12%) sampled in the California coastal study region was heavily or moderately influenced by ship emissions. Another study investigated the chemical and physical evolution of a controlled organic plume emitted from the R/V Point Sur. Under sunny conditions, nucleated particles composed of oxidized organic compounds contributed nearly an order of magnitude more cloud condensation nuclei (CCN) than less oxidized particles formed under cloudy conditions. The processing time necessary for particles to become CCN active was short ( < 1 hr) compared to the time needed for particles to become hygroscopic at sub-saturated humidity ( > 4 hr).
Laboratory chamber experiments were also conducted to evaluate particle-phase processes influencing aerosol phase and composition. In one study, ammonium sulfate seed was coated with a layer of secondary organic aerosol (SOA) from toluene oxidation followed by a layer of SOA from α-pinene oxidation. The system exhibited different evaporative properties than ammonium sulfate seed initially coated with α-pinene SOA followed by a layer of toluene SOA. This behavior is consistent with a shell-and-core model and suggests limited mixing among different SOA types. Another study investigated the reactive uptake of isoprene epoxy diols (IEPOX) onto non-acidified aerosol. It was demonstrated that particle acidity has limited influence on organic aerosol formation onto ammonium sulfate seed, and that the chemical system is limited by the availability of nucleophiles such as sulfate.
Flow tube experiments were conducted to examine the role of iron in the reactive uptake and chemical oxidation of glycolaldehyde. Aerosol particles doped with iron and hydrogen peroxide were mixed with gas-phase glycolaldehyde and photochemically aged in a custom-built flow reactor. Compared to particles free of iron, iron-doped aerosols significantly enhanced the oxygen to carbon (O/C) ratio of accumulated organic mass. The primary oxidation mechanism is suggested to be a combination of Fenton and photo-Fenton reactions which enhance particle-phase OH radical concentrations.