Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that ...organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depression by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation.
Autoxidation is an autocatalytic free-radical chain reaction responsible for the oxidative destruction of organic molecules in biological cells, foods, plastics, petrochemicals, fuels, and the ...environment. In cellular membranes, lipid autoxidation (peroxidation) is linked with oxidative stress, age-related diseases, and cancers. The established mechanism of autoxidation proceeds via H-atom abstraction through a cyclic network of peroxy–hydroperoxide-mediated freeradical chain reactions. For a series of model unsaturated lipids, we present evidence for an autoxidation mechanism, initiated by hydroxyl radical (OH) addition to C=C bonds and propagated by chain reactions involving Criegee intermediates (CIs). This mechanism leads to unexpectedly rapid autoxidation even in the presence of water, implying that as reactive intermediates, CI could play a much more prominent role in chemistries beyond the atmosphere.
The formation of ultraviscous, glassy, and amorphous gel states in aqueous aerosol following the loss of water results in nonequilibrium dynamics due to the extended time scales for diffusive mixing. ...Existing techniques for measuring water diffusion by isotopic exchange are limited by contact of samples with the substrate, and methods applied to infer diffusion coefficients from mass transport in levitated droplets requires analysis by complex coupled differential equations to derive diffusion coefficients. We present a new technique that combines contactless levitation with aerosol optical tweezers with isotopic exchange (D2O/H2O) to measure the water diffusion coefficient over a broad range (D w ≈ 10–12–10–17 m2·s–1) in viscous organic liquids (citric acid, sucrose, and shikimic acid) and inorganic gels (magnesium sulfate, MgSO4). For the organic liquids in binary and ternary mixtures, D w depends on relative humidity and follows a simple compositional Vignes relationship. In MgSO4 droplets, water diffusivity decreases sharply with water activity and is consistent with predictions from percolation theory. These measurements show that, by combining micrometer-sized particle levitation (a contactless measurement with rapid mixing times) with an established probe of water diffusion, D w can be simply and directly quantified for amorphous and glassy states that are inaccessible to existing methods.
Organic molecules in the environment oxidatively degrade by a variety of free radical, microbial, and biogeochemical pathways. A significant pathway is heterogeneous autoxidation, in which ...degradation occurs via a network of carbon and oxygen centered free radicals. Recently, we found evidence for a new heterogeneous autoxidation mechanism of squalene that is initiated by hydroxyl (OH) radical addition to a carbon–carbon double bond and apparently propagated through pathways involving Criegee Intermediates (CI) produced from β-hydroxy peroxy radicals (β-OH-RO2•). It remains unclear, however, exactly how CI are formed from β-OH-RO2•, which could occur by a unimolecular or bimolecular pathway. Combining kinetic models and multiphase OH oxidation measurements of squalene, we evaluate the kinetic viability of three mechanistic scenarios. Scenario 1 assumes that CI are formed by the unimolecular bond scission of β-OH-RO2•, whereas Scenarios 2 and 3 test bimolecular pathways of β-OH-RO2• to yield CI. Scenario 1 best replicates the entire experimental data set, which includes effective uptake coefficients vs OH as well as the formation kinetics of the major products (i.e., aldehydes and secondary ozonides). Although the unimolecular pathway appears to be kinetically viable, future high-level theory is needed to fully explain the mechanistic relationship between CI and β-OH-RO2• in the condensed phase.
The purpose of this study is to determine the effects of low-dose radiation on fibroblast cells irradiated by spectrally and dosimetrically well-characterized soft x-rays. To achieve this, a new cell ...culture x-ray irradiation system was designed. This system generates characteristic fluorescent x-rays to irradiate the cell culture with x-rays of well-defined energies and doses. 3T3 fibroblast cells were cultured in cups with Mylar® surfaces and were irradiated for one hour with characteristic iron (Fe) K x-ray radiation at a dose rate of approximately 550 μGy/hr. Cell proliferation, total protein analysis, flow cytometry, and cell staining were performed on fibroblast cells to determine the various effects caused by the radiation. Irradiated cells demonstrated increased proliferation and protein production compared to control samples. Flow cytometry revealed that a higher percentage of irradiated cells were in the G0/G1 phase of the cell cycle compared to control counterparts, which is consistent with other low-dose studies. Cell staining results suggest that irradiated cells maintained normal cell functions after radiation exposure, as there were no qualitative differences between the images of the control and irradiated samples. The result of this study suggest that low-dose soft x-ray radiation might cause an initial pause, followed by a significant increase, in proliferation. An initial "pause" in cell proliferation could be a protective mechanism of the cells to minimize DNA damage caused by radiation exposure. The new cell irradiation system developed here allows for unprecedented control over the properties of the x-rays given to the cell cultures. This will allow for further studies on various cell types with known spectral distribution and carefully measured doses of radiation, which may help to elucidate the mechanisms behind varied cell responses to low-dose x-rays reported in the literature.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their ...relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region’s fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies.
The use of o-phthalaldehyde (OPA) in combination with a thiol reagent is a common method for detecting primary amines in amino acids, peptides, and proteins. Despite its widespread use, the exact ...reaction mechanism has been debated since the 1980s. Here, we measure the kinetics of the reaction between OPA, alanine, and a dithiol (1,4-dithiolthreitol, DTT) as a function of pH and reagent concentration. Using these new measurements and accompanying kinetic models, we find evidence that the pH dependence of the kinetics arises from both the protonation states of alanine and DTT, the hydration state of OPA, and the unproductive equilibrium with DTT, all of which are pH-dependent. These results support the mechanism originally proposed by Sternson Rational design and evaluation of improved o-phthalaldehyde-like fluorogenic reagents. Anal. Biochem. 1985, 144, 233–246 and Wong Reaction of o-phthalaldehyde with alanine and thiols: kinetics and mechanism. J. Am. Chem. Soc. 1985, 107, 6421–6422, in which the primary amine first reacts with OPA, followed by a reaction with the thiol to form the fluorescent isoindole product.
Criegee intermediates (CI), formed in alkene ozonolysis, are central for controlling the multiphase chemistry of organic molecules in both indoor and outdoor environments. Here, we examine the ...heterogeneous ozonolysis of squalene, a key species in indoor air chemistry. Aerosol mass spectrometry is used to investigate how the ozone (O3) concentration, relative humidity (RH), and particle size control reaction rates and mechanisms. Although the reaction rate is found to be independent of RH, the reaction products and particle size depend upon H2O. Under dry conditions (RH = 3%) the reaction produces high-molecular-weight secondary ozonides (SOZ), which are known skin irritants, and a modest change in particle size. Increasing the RH reduces the aerosol size by 30%, while producing mainly volatile aldehyde products, increases potential respiratory exposure. Chemical kinetics simulations link the elementary reactions steps of CI to the observed kinetics, product distributions, and changes in particle size. The simulations reveal that ozonolysis occurs near the surface and is O3-transport limited. The observed secondary ozonides are consistent with the formation of mainly secondary CI, in contrast to gas-phase ozonolysis mechanisms.
A key but poorly understood chemical process is how gas phase uptake is governed by the relative mobility of molecules at an interface of an atmospheric aerosol. Citric acid (CA), a model system for ...oxygenated organic aerosol, is used to examine how changes in viscosity, due to changing water content, govern the reactive uptake of gas phase hydroxyl radicals (OH). By comparing the reaction kinetics measured when probing the outer aerosol surface layers with measurements of the bulk particle composition, the effective OH reaction probability is observed to be a complex and non-linear function of the relative humidity (RH). At RH < 50%, the reactive decay of CA is controlled by the viscosity of the particle, where the depletion of CA and the formation of reaction products occurs over a narrow region near the aerosol interface, on the order of 8 nm at 20% RH. At RH = 50% the reaction zone increases to the particle dimensions (
∼50 nm) and at RH > 50%, the aerosol becomes aqueous and well-mixed on the timescale of the heterogeneous reaction. These results imply that in the atmosphere, the formation and dissipation of interfacial chemical gradients could be significant in viscous and semisolid aerosol and play important roles altering gas-particle partitioning and aging mechanisms (
bulk
interface).
A detailed understanding of the sources, transformations and fates of organic species in the environment is crucial because of the central roles that they play in human health, biogeochemical cycles ...and the Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here, we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state, a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of the average carbon oxidation state, using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number.