Secondary organic aerosol formation by heterogeneous reactions of aldehydes and ketones: a quantum mechanical study

Experimental studies have provided convincing evidence that aerosol-phase heterogeneous chemical reactions (possibly acid-catalyzed) are involved to some extent in the formation of secondary organic aerosol (SOA). We present a stepwise procedure to determine physical properties such as heats of formation, standard entropies, Gibbs free energies of formation, and solvation energies from quantum mechanics (QM), for various short-chain aldehydes and ketones. We show that quantum mechanical gas-phase Gibbs free energies of formation compare reasonably well with the literature values with a root-mean-square (RMS) value of 1.83 kcal/mol for the selected compounds. These QM results are then used to determine the equilibrium constants (reported as log K) of aerosol-phase chemical reactions, including hydration reactions and aldol condensation for formaldehyde, acetaldehyde, acetone, butanal, hexanal, and glyoxal. Results are in qualitatively agreement with previous studies. In addition, the QM results for glyoxal reactions are consistent with experimental observations. To our knowledge, this is the first QM study that supports observations of atmospheric particle-phase reactions. Despite the significant uncertainties in the absolute values from the QM calculations, the results are potentially useful in determining the relative thermodynamic tendency for atmospheric aerosol-phase reactions.     

Modeling aerosol formation from alpha-pinene + NOx in the presence of natural sunlight using gas-phase kinetics and gas-particle partitioning theory

A kinetic mechanism was used to link and model the gas-phase reactions and aerosol accumulation resulting from alpha-pinene reactions in the presence of sunlight, ozone (O3), and oxides of nitrogen (NOx). Reaction products and aerosol formation from the kinetic model were compared to outdoor smog chamber experiments conducted under natural sunlight in the presence of NOx and in the dark in the presence of O3. The gas-particle partitioning of semivolatile organics generated in the gas phase was treated as an equilibrium process between particle absorption and desorption. Models vs experimental aerosol yields illustrate that reasonable predictions of secondary aerosol formation are possible from both dark ozone and light NOx/alpha-pinene systems over a variety of different outdoor conditions. On average, measured gas- and particle-phase products accounted for approximately 54-72% of the reacted alpha-pinene carbon. Model predictions suggest that organic nitrates account for another approximately 25% of the reacted carbon, and most of this is in the gas phase. Measured particle-phase products accounted for 60-100% of the particle filter mass, with pinic acid and pinonic acid being the primary aerosol-phase products. In the gas phase, pinonaldehyde and pinonic acid are major products. Model simulations of these and other products show generally reasonable fits to the experimental data from the perspective of timing and concentrations. These results are very encouraging for a compound such as pinonaldehyde, since it is being formed from OH attack on alpha-pinene and is also simultaneously photolyzed and reacted with OH.     

Peroxidase-catalyzed coupling of phenol in the presence of model inorganic and organic solid phases

Peroxidase-catalyzed oxidative coupling reactions of phenol in aqueous systems variously containing silica sand, cellulose, lignin, and polymethylstyrene were investigated. These four solid phase materials represent a broad spectrum of different natural geosorbent types in terms of their physicochemical characteristics. Each solid was found to influence peroxidase-catalyzed phenol coupling, either by mitigation of enzyme inactivation, by participation in cross-coupling, or by a combination of these two activities. Mitigation of enzyme inactivation was observed for those three of the four model solids found to adsorb the enzyme effectively; i.e., cellulose, silica sand, and lignin. Two solids, polymethylstyrene and lignin, were found to participate significantly in cross-coupling reactions. It is postulated that relatively hydrophilic solids can mitigate peroxidase inactivation by forming enzyme-solid associations. Aromatic structures or unsaturated C-C bonds were found to be features of the solid-phase materials that allowed them to participate in cross-coupling. The results have important implications for process feasibility assessment and the engineering design of soil/sediment remediation systems employing enzymatic coupling schemes.     

Atmospheric photosensitized heterogeneous and multiphase reactions: from outdoors to indoors

This proposal involves direct photolysis processes occurring in the troposphere incorporating photochemical excitation and intermolecular energy transfer. The study of such processes could provide a better understanding of ·OH radical formation pathways in the atmosphere and in consequence, of a more accurate prediction of the oxidative capacity of the atmosphere. Compounds that readily absorb in the tropospheric actinic window (ionic organic complexes, PAHs, aromatic carbonyl compounds) acting as potential photosensitizers of atmospheric relevant processes are explored. The impact of hotosensitation on relevant systems which could act as powerful atmospheric reactors,that is, interface ocean-atmosphere, urban and forest surfaces and indoor air environments is also discussed.     

Products and mechanism of secondary organic aerosol formation from reactions of n-alkanes with OH radicals in the presence of NOx

Secondary organic aerosol (SOA) formation from reactions of n-alkanes with OH radicals in the presence of NOx was investigated in an environmental chamber using a thermal desorption particle beam mass spectrometer for particle analysis. SOA consisted of both first- and higher-generation products, all of which were nitrates. Major first-generation products were sigma-hydroxynitrates, while higher-generation products consisted of dinitrates, hydroxydinitrates, and substituted tetrahydrofurans containing nitrooxy, hydroxyl, and carbonyl groups. The substituted tetrahydrofurans are formed by a series of reactions in which sigma-hydroxycarbonyls isomerize to cyclic hemiacetals, which then dehydrate to form substituted dihydrofurans (unsaturated compounds) that quickly react with OH radicals to form lower volatility products. SOA yields ranged from approximately 0.5% for C8 to approximately 53% for C15, with a sharp increase from approximately 8% for C11 to approximately 50% for C13. This was probably due to an increase in the contribution of first-generation products, as well as other factors. For example, SOA formed from the C10 reaction contained no first-generation products, while for the C15 reaction SOA was approximately 40% first-generation and approximately 60% higher-generation products, respectively. First-generation sigma-hydroxycarbonyls are especially important in SOA formation, since their subsequent reactions can rapidly form low volatility compounds. In the atmosphere, substituted dihydrofurans created from sigma-hydroxycarbonyls will primarily react with O3 or NO3 radicals, thereby opening reaction pathways not normally accessible to saturated compounds.     

Box model investigation of the effect of soot particles on ozone downwind from an urban area through heterogeneous reactions

Soot can provide additional surface area where heterogeneous reactions can take place in the atmosphere. These reactions are dependent on the number of reactive sites on the soot surface rather than the soot surface area per se. A box model, MOCCA, is used to investigate the effects of introducing heterogeneous reactions on soot into air parcel passing over an urban area and traveling downwind. The model was run at two soot mass concentrations of 2 microg/m3 and 20 microg/m3 with a surface density of n-hexane and decane. Signifcant change in gasphase concentration was only observed for the higher soot concentration. Due to the noncatalytic nature of the heterogeneous reactions, soot sites are rapidly consumed, and soot site concentrations are greatly reduced shortly after emissions are turned off. Notable changes in gaseous concentrations due to the introduction of heterogeneous reactions are not observed in the urban setting. The impact of heterogeneous reactions is more evident after emissions are turned off (i.e. downwind from the urban center). These changes are minimal for the condition that used n-hexane surface density. For conditions that used decane soot, NOx concentrations showed a slight increase, with NO being higher in the daytime and NO2 at night. The maximum O3 reduction observed when using the higher soot concentration is 7 ppb, downwind of the urban center. Change in O3 concentration was less than 1 ppb when using the lower soot loading. The observed effects of heterogeneous reactions on soot decrease with time.     

SOA formation by biogenic and carbonyl compounds: data evaluation and application

The organic fraction of atmospheric aerosols affects the physical and chemical properties of the particles and their role in the climate system. Current models greatly underpredict secondary organic aerosol (SOA) mass. Based on a compilation of literature studies that address SOA formation, we discuss different parameters that affect the SOA formation efficiency of biogenic compounds (alpha-pinene, isoprene) and aliphatic aldehydes (glyoxal, hexanal, octanal, hexadienal). Applying a simple model, we find that the estimated SOA mass after one week of aerosol processing under typical atmospheric conditions is increased by a few microg m(-3) (low NO(x) conditions). Acid-catalyzed reactions can create > 50% more SOA mass than processes under neutral conditions; however, other parameters such as the concentration ratio of organics/NO(x), relative humidity, and absorbing mass are more significant. The assumption of irreversible SOA formation not limited by equilibrium in the particle phase or by depletion of the precursor leads to unrealistically high SOA masses for some of the assumptions we made (surface vs volume controlled processes).     

Semiempirical model for organic aerosol growth by acid-catalyzed heterogeneous reactions of organic carbonyls

Aerosol growth by heterogeneous reactions of diverse carbonyls in the presence and absence of acidified seed aerosols was studied in a 4 m long flow reactor (2.5 cm i.d.) and a 2-m3 indoor Teflon film chamber under darkness. The acid catalytic effects on heterogeneous aerosol production were observed for diverse carbonyls in various ranges of humidities and compositions of seed inorganic aerosols. Particle population data measured by a scanning mobility particle sizer were used to calculate organic aerosol growth. To accountforthe aerosol growth contributed by heterogeneous reactions, the increase in organic aerosol mass was normalized bythe organic mass predicted by partitioning or the square of predicted organic mass. The carbonyl heterogeneous reactions were accelerated in the presence of acid catalysts (H2SO4), leading to higher aerosol yields than in their absence. The experimental data from aerosol yields in the flow reactorwere semiempirically fitted to the model parameters to predict the organic aerosol growth. The model parameters consist of environmental characteristics and molecular structure information of organic carbonyls. Basicity constants of carbonyls were used to describe the proton affinity of carbonyls for the acid catalysts. Particle environmental factors, such as humidity, temperature, and inorganic seed composition, were expressed by excess acidity and the parameters obtained from an inorganic thermodynamic model. A stepwise regression analysis of the aerosol growth model for the experimental data revealed that either the chemical structure information of carbonyls or characteristic environmental parameters are statistically significant in the prediction of organic aerosol growth. It was concluded thatthis model approach is applicable to predict secondary organic aerosol formation by heterogeneous reaction.     

Inhibition of acrylamide formation by vitamins in model reactions and fried potato strips

The capacities of 15 vitamins in reducing the formation of acrylamide were examined. Inhibitory activities of the water-soluble vitamins were tested in both chemical models containing acrylamide precursors (asparagines and glucose) and a food model system (fried snack products), while activities of fat-soluble vitamins were examined only in the latter model. Biotin, pyridoxine, pyridoxamine, and l-ascorbic acid exerted a potent inhibitory effect (>50%) on acrylamide formation in the chemical model system. Using the food model, it was shown that water-soluble vitamins are good inhibitors of acrylamide formation. On the other hand, only weak inhibitory effects were observed with fat-soluble vitamins. Effects of pyridoxal, nicotinic acid, and l-ascorbic acid were further examined using fried potato strips. Nicotinic acid and pyridoxal inhibited acrylamide formation in fried potato strips by 51% and 34%, respectively. Thus, certain vitamins at reasonable concentrations can inhibit the formation of acrylamide.     

Preservation of inorganic arsenic species in groundwater

The objective of this research was to develop a robust preservation method for stabilizing inorganic As(IlI/V) species in synthetic and actual groundwaters. Ethylenediaminetetraacetic acid (EDTA), H2SO4, H3PO4, and EDTA-acetic acid (HAc) were evaluated in synthetic groundwater containing 3 mg/L Fe(ll) in the pH range 6.5-8.4 and Eh range -100 to +200 mV at room temperature. In the absence of strong UV light, only EDTA-HAc was found to be an effective preservative under all the experimental conditions tested. A total of 89 samples (including 16 samples in triplicate) from 55 drinking waterwells in Minnesota, California, and North Dakota were preserved with a combination of EDTA-HAc and speciated to evaluate its effectiveness for preserving inorganic arsenic species in actual groundwater samples. The preserved and field-speciated samples were repeatedly speciated and analyzed in the laboratory for up to 85 days after collection. Field-speciated As(lll) concentrations were compared with the As(lll) concentrations in the preserved samples. The results were highly correlated (slope 0.9773, R2 = 0.9986), which indicates that during sample transportation and storage the distribution of arsenic species did not change for samples preserved with EDTA-HAc.     

The effects of ascorbic acid and sorbic acid on N-nitrosamine formation in a heterogeneous model system

The effects of competitive nitrosation by ascorbic acid and sorbic acid on N-nitrosamine formation were studied in a heterogeneous protein-based model system containing a 20% non-aqueous phase. The reactions were examined at 37°C with an aqueous phase pH of 5.25. Under certain conditions ascorbic acid enhanced the nitrosation of secondary amines. The overall extent to which ascorbic acid affected N-nitrosation was found to depend on the time-scale of the reaction and also the phase in which N-nitrosamine formation occurred. Sorbic acid reduced N-nitrosation in both phases of the heterogeneous system.     

Cyanogen bromide formation from the reactions of monobromamine and dibromamine with cyanide ion

Cyanide ion (CN-) was found to reactwith monobromamine (NH2Br) and dibromamine (NHBr2) according to the reactions NH2Br + CN- + H20 --> NH3 + BrCN + OH- and NHBr2 + CN- + H20 --> NH2Br + BrCN + OH- with respective reaction rate constants of 2.63 x 10(4) M9-10 s(-1) and 1.31 x 10(8) M(-1) s(-1). These values were found to be 10(5)-10(6) times greater than those for the corresponding reactions between chloramine species and CN-. As a result, bromamines, even if present at relatively low concentrations, would tend to outcompete chloramines in reacting with CN-, and thus, the formation of BrCN would predominate that of ClCN through these reaction mechanisms. The NH2Br reaction was found to be general-acid-catalyzed. The third-order catalysis rate constants for H+, H2PO4-, HPO4(2-), H3BO3, and NH4+ correlated linearly with their corresponding acid dissociation constants, consistent with the Br?nsted-Pedersen relationship. The NHBr2 reaction did not undergo catalysis. A model was developed to predict the concentrations of bromamines over time on the basis ofthe above two reactions with CN- and bromamine formation/decomposition reactions previously reported.     

Thirdhand smoke: heterogeneous oxidation of nicotine and secondary aerosol formation in the indoor environment

Tobacco smoking is well-known as a significant source of primary indoor air pollutants. However, only recently has thirdhand smoke (THS) been recognized as a contributor to indoor pollution due to the role of indoor surfaces. Here, the effects of relative humidity (<10% RH and ～ 45% RH) and substrate (cellulose, cotton, and paper) on secondary organic aerosol (SOA) formation from nicotine-ozone-NO(x) reactions are discussed. SOA formation from the sorbed nicotine-ozone reaction ([O(3)] = 55 ppb) varied in size distribution and number, depending on RH and substrate type, indicating the role of substrate and water interactions in SOA formation. This led to SOA yields from cellulose sorbed nicotine-ozone reaction of ～ 1 and 2% for wet and dry conditions, respectively. SOA formation from nicotine-NO(x) reactions was not distinguishable from background levels. Simultaneously, cellulose sorbed nicotine-ozone reaction kinetics ([O(3)] = 55 ppb) were obtained and revealed pseudofirst-order surface rate constants of k(1) = (1 ± 0. 5) × 10(-3) and k(1) < 10(-4) min(-1) under <10% and ～ 45% RH, respectively. Given the toxicity of some of the identified products and that small particles may contribute to adverse health effects, the present study indicates that exposure to THS ozonation products may pose additional health risks.     

Enzyme catalyzed reactions and structure formation relationship in plastein reactions

α-Chymotrypsin and papain catalyzed formation of plastein from peptic hydrolyzate of soy protein is shown to take place without any change of the average molecular weight. Rheological studies of plastein in dependence of plastein reaction condition indicates that chemical reactions resulting in an increase of viscosity take place in the first minutes of the plastein reaction. After the expiration of this period structure formation processes take place lasting for 3–5 days which are not the result of α-chymotrypsin and papain catalyzed reactions.     

Transitions from functionalization to fragmentation reactions of laboratory secondary organic aerosol (SOA) generated from the OH oxidation of alkane precursors

Functionalization (oxygen addition) and fragmentation (carbon loss) reactions governing secondary organic aerosol (SOA) formation from the OH oxidation of alkane precursors were studied in a flow reactor in the absence of NO(x). SOA precursors were n-decane (n-C10), n-pentadecane (n-C15), n-heptadecane (n-C17), tricyclo[5.2.1.0(2,6)]decane (JP-10), and vapors of diesel fuel and Southern Louisiana crude oil. Aerosol mass spectra were measured with a high-resolution time-of-flight aerosol mass spectrometer, from which normalized SOA yields, hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios, and C(x)H(y)+, C(x)H(y)O+, and C(x)H(y)O(2)+ ion abundances were extracted as a function of OH exposure. Normalized SOA yield curves exhibited an increase followed by a decrease as a function of OH exposure, with maximum yields at O/C ratios ranging from 0.29 to 0.74. The decrease in SOA yield correlates with an increase in oxygen content and decrease in carbon content, consistent with transitions from functionalization to fragmentation. For a subset of alkane precursors (n-C10, n-C15, and JP-10), maximum SOA yields were estimated to be 0.39, 0.69, and 1.1. In addition, maximum SOA yields correspond with a maximum in the C(x)H(y)O+ relative abundance. Measured correlations between OH exposure, O/C ratio, and H/C ratio may enable identification of alkane precursor contributions to ambient SOA.     

大米中无机砷的生物可给性体外消化评价模型介绍

食物摄入是许多化学物质进入人体的主要渠道.只有当化学物质能够被释放进入消化液, 才能够发挥毒性作用.介绍了建立体外消化模型用于大米中无机砷生物可给性研究工作.结果显示:无机砷标准溶液能全部进入消化糜中;不同浓度的加标大米样品中无机砷的生物可给性随着加标浓度的上升而下降;现场采集的三种大米样品的无机砷的生物可给性基本一致.体外消化模型对于丰富暴露评估技术和健全风险评估制度将产生良好的影响.     

β-lactoglobulin denaturation and aggregation reactions and fouling deposit formation: a DSC study

The thermal stability of β-lactoglobulin was studied using differential scanning calorimetry (DSC) as part of a larger investigation into milk and whey fouling. Measurement of kinetics using DSC is very difficult as the resultant trace is the sum of simultaneous denaturation and aggregational enthalpies; the two processes were demonstrated by measurements at different heating rates. β-lactoglobulin denaturation proceeds via an intramolecular disulphide stabilized intermediate and is irreversible even before the denaturation temperature is reached. Denaturation and aggregational processes can be partially separated by measurements over a range of pH. The literature shows that the rate of fouling decreases as solution pH increases. However, DSC shows that the thermal stability of β-lactoglobulin decreases as pH increases, particularly above pH 6. It is hypothesised that aggregation rather than denaturation might be the critical step in the formation of fouling deposit.     

不同品种橙汁中有机酸和无机阴离子分析

采用离子色谱法对大红橙、新会橙、哈姆林橙、伏令夏橙、奥林达夏橙五个品种橙汁的有机酸及无机阴离子进行了初步测定,得出五个品种橙汁均含有奎尼酸、醋酸、苹果酸、琥珀酸、草酸、抗坏血酸、柠檬酸、异柠檬酸,并都含有氯离子、磷酸根这两种无机阴离子。根据图谱对有机酸进行定量分析发现,五种橙汁中含量最多的有机酸均为柠檬酸,但柠檬酸含量在不同品种橙汁中存在显著差异,新会橙汁中柠檬酸含量最高(8920·00mg/L)、哈姆林橙汁中柠檬酸含量最低(4142·00mg/L)。对不同品种橙汁的柠檬酸含量与异柠檬酸含量的比值进行了分析,结果表明,两种酸含量的比值在不同品种橙汁之间存在极显著差异。