Science.gov

Sample records for aerosol aqueous phase

  1. Aqueous phase processing of secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Liu, Yao; Tritscher, T.; Praplan, A. P.; Decarlo, P. F.; Temime-Roussel, B.; Quivet, E.; Marchand, N.; Dommen, J.; Baltensperger, U.; Monod, A.

    2011-07-01

    The aging of secondary organic aerosol (SOA) by photooxidation in the aqueous phase was experimentally investigated. To simulate multiphase processes, the following experiments were sequentially performed in a smog chamber and in an aqueous phase photoreactor: (1) Gas-phase photooxidation of three different volatile organic compounds (VOC): isoprene, α-pinene, and 1,3,5-trimethylbenzene (TMB) in the presence of NOx, leading to the formation of SOA which was subjected to on-line physical and chemical analysis; (2) particle-to-liquid transfer of water soluble species of SOA using filter sampling and aqueous extraction; (3) aqueous-phase photooxidation of the obtained water extracts; and (4) nebulization of the solutions for a repetition of the on-line characterization. SOA concentrations in the chamber measured with a scanning mobility particle sizer (SMPS) were higher than 200 μg m-3, as the experiments were conducted under high initial concentrations of volatile organic compounds (VOC) and NOx. The aging of SOA through aqueous phase processing was investigated by measuring the physical and chemical properties of the particles online before and after processing using a high resolution time-of-flight aerosol mass spectrometer (AMS) and a hygroscopicity tandem differential mobility analyzer (H-TDMA). It was shown that, after aqueous phase processing, the particles were significantly more hygroscopic, and contained more fragmentation ions at m/z = 44 and less ions at m/z = 43, thus showing a significant impact on SOA aging for the three different precursors. Additionally, the particles were analyzed with a thermal desorption atmospheric pressure ionization aerosol mass spectrometer (TD-API-AMS). Comparing the smog chamber SOA composition and non processed nebulized aqueous extracts with this technique revealed that sampling, extraction and/or nebulization did not significantly impact the chemical composition of SOA formed from isoprene and α-pinene, whereas it

  2. Aqueous phase processing of secondary organic aerosol from isoprene photooxidation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Monod, A.; Tritscher, T.; Praplan, A. P.; DeCarlo, P. F.; Temime-Roussel, B.; Quivet, E.; Marchand, N.; Dommen, J.; Baltensperger, U.

    2012-07-01

    Transport of reactive air masses into humid and wet areas is highly frequent in the atmosphere, making the study of aqueous phase processing of secondary organic aerosol (SOA) very relevant. We have investigated the aqueous phase processing of SOA generated from gas-phase photooxidation of isoprene using a smog chamber. The SOA collected on filters was extracted by water and subsequently oxidized in the aqueous phase either by H2O2 under dark conditions or by OH radicals in the presence of light, using a photochemical reactor. Online and offline analytical techniques including SMPS, HR-AMS, H-TDMA, TD-API-AMS, were employed for physical and chemical characterization of the chamber SOA and nebulized filter extracts. After aqueous phase processing, the particles were significantly more hygroscopic, and HR-AMS data showed higher signal intensity at m/z 44 and a lower signal intensity at m/z 43, thus showing the impact of aqueous phase processing on SOA aging, in good agreement with a few previous studies. Additional offline measurement techniques (IC-MS, APCI-MS2 and HPLC-APCI-MS) permitted the identification and quantification of sixteen individual chemical compounds before and after aqueous phase processing. Among these compounds, small organic acids (including formic, glyoxylic, glycolic, butyric, oxalic and 2,3-dihydroxymethacrylic acid (i.e. 2-methylglyceric acid)) were detected, and their concentrations significantly increased after aqueous phase processing. In particular, the aqueous phase formation of 2-methylglyceric acid and trihydroxy-3-methylbutanal was correlated with the consumption of 2,3-dihydroxy-2-methyl-propanal, and 2-methylbutane-1,2,3,4-tetrol, respectively, and an aqueous phase mechanism was proposed accordingly. Overall, the aging effect observed here was rather small compared to previous studies, and this limited effect could possibly be explained by the lower liquid phase OH concentrations employed here, and/or the development of oligomers

  3. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: chemical characterization of the products

    NASA Astrophysics Data System (ADS)

    Grgić, Irena; Kitanovski, Zoran; Kroflič, Ana; Čusak, Alen

    2014-05-01

    One of the largest primary sources of organic aerosol in the atmosphere is biomass burning (BB) (Laskin et al. 2009); in Europe its contribution to annual mean of PM10 is between 3 and 14 % (Maenhaut et al. 2012). During the process of wood burning many different products are formed via thermal degradation of wood lignin. Hardwood burning produces mainly syringol (2,6-dimetoxyphenol) derivatives, while softwood burning exclusively guaiacol (2-methoxyphenol) and its derivatives. Taking into account physical properties of methoxyphenols only, their concentrations in atmospheric waters might be underestimated. So, their aqueous phase reactions can be an additional source of SOA, especially in regions under significant influence of wood combustion. An important class of compounds formed during physical and chemical aging of the primary BBA in the atmosphere is nitrocatechols, known as strong absorbers of UV and Vis light (Claeys et al. 2012). Very recently, methyl-nitrocatechols were proposed as suitable markers for highly oxidized secondary BBA (Iinuma et al. 2010, Kitanovski et al. 2012). In the present work, the formation of SOA through aqueous phase photooxidation and nitration of guaiacol was examined. The key objective was to chemically characterize the main low-volatility products and further to check their possible presence in the urban atmospheric aerosols. The aqueous phase reactions were performed in a thermostated reactor under simulated sunlight in the presence of H2O2 and nitrite. Guaiacol reaction products were first concentrated by solid-phase extraction (SPE) and then subjected to semi-preparative liquid chromatography.The main product compounds were fractionated and isolated as pure solids and their structure was further elucidated by using nuclear magnetic resonance spectroscopy (1H, 13C and 2D NMR) and direct infusion negative ion electro-spray ionization tandem mass spectrometry (( )ESI-MS/MS). The main photonitration products of guaiacol (4

  4. Developing a stronger understanding of aerosol sources and the impact of aqueous phase processing on coastal air quality

    NASA Astrophysics Data System (ADS)

    Prather, K. A.

    2014-12-01

    Atmospheric aerosols are produced by a variety of sources including emissions from cars and trucks, wildfires, ships, dust, and sea spray and play a significant role in impacting air pollution and regional climate. The ability of an aerosol to uptake water and undergo aqueous phase processing strongly depends on composition. On-line single particle mass spectrometry can provide insight into how particle composition impacts the degree of photochemical and aging processes atmospheric aerosols undergo. In particular, specific sulfur species including sulfate, hydroxymethanesulfate (HMS), and methanesulfonic acid (MSA) can serve as indicators of when an air mass has undergone aqueous phase processing. This presentation will describe recent field studies conducted at coastal sites to demonstrate how different aerosol sources and secondary processing impact coastal air quality.

  5. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: a kinetic study

    NASA Astrophysics Data System (ADS)

    Kroflič, Ana; Grgić, Irena

    2014-05-01

    It is well known that atmospheric aerosols play a crucial role in the Earth's climate and public health (Pöschl 2005). Despite a great effort invested in the studies of secondary organic aerosol (SOA) budget, composition, and its formation mechanisms, there is still a gap between field observations and atmospheric model predictions (Heald et al. 2005, Hallquist et al. 2009, and Lim et al. 2010). The insisting uncertainties surrounding SOA formation and aging thus gained an increasing interest in atmospheric aqueous phase chemistry; they call for more complex and time consuming studies at the environmentally relevant conditions allowing confident extrapolation to desired ambient conditions. In addition to the adverse health effects of atmospheric particulate matter (PM) as such, toxicity is also attributed to nitro-aromatic and other organic compounds which have already been detected in real aerosol samples (Traversi et al. 2009). Moreover, low-volatility aromatic derivatives are believed to form at least partly in the aerosol aqueous phase and not only in the gas phase from where they partition into water droplets (Ervens et al. 2011). Two nitro derivatives of biomass burning tracer guaiacol have recently been found in winter PM10 samples from the city of Ljubljana, Slovenia, and aqueous photonitration reaction was proposed as their possible production pathway (Kitanovski et al. 2012). In this study the kinetics of guaiacol nitration in aqueous solution was investigated in the presence of H2O2 and NO2¯ upon simulated solar irradiation (Xenon lamp, 300 W). During the experiment the DURAN® flask with the reaction mixture was held in the thermostated bath and thoroughly mixed. The reaction was monitored for 44 hours at different temperatures. Guaiacol and its main nitro-products (4-nitroguaiacol, 4-NG; 6-nitroguaiacol, 6-NG; and 4,6-dinitroguaiacol, 4,6-DNG) were quantified in every aliquot, taken from the reaction mixture, by use of high pressure liquid

  6. A Systematic Evaluation of the Extent of Photochemical Processing in Different Types of Secondary Organic Aerosols in the Aqueous Phase

    NASA Astrophysics Data System (ADS)

    Romonosky, D.; Lee, H.; Epstein, S. A.; Nizkorodov, S.; Laskin, J.; Laskin, A.

    2013-12-01

    A significant fraction of atmospheric organic compounds are predominantly found in condensed phases, such as organic phase in aerosol particles or aqueous phase in cloud droplets. The oxidation of VOCs followed by the condensation of products into particles was thought to be the main mechanism of organic aerosol (OA) formation. However, in the last several years, scientists have realized that a large fraction, if not the majority of organic particles, is produced through cloud and fog photochemical processes. Many of these organic compounds are photolabile, and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of droplets (hours) and particles (days). We previously reported that compounds in secondary organic aerosol (SOA) from ozonolysis of d-limonene efficiently photodegrade in both organic (Walser et al., 2007) and aqueous phases (Bateman et al., 2011). Significant photolysis was also observed in an aqueous extract of SOA from high-NOx photooxidation of isoprene (Nguyen et al., 2012). More recent experiments studying the response to irradiation of complex aqueous mixtures (as opposed to solutions of isolated compounds) found surprising resilience to photodegradation in aqueous extracts of SOA prepared by photooxidation of alpha-pinene (Romonosky et al., unpublished). We present a systematic investigation of the extent of photochemical processing in different types of SOA from various biogenic and anthropogenic precursors. Chamber- or flowtube-generated SOA is collected on an inert substrate, extracted in a methanol/water solution (70:30), photolyzed in the aqueous solution, and the extent of change in the molecular level composition of the material is assessed with high-resolution mass spectrometry (HR-MS). The outcome of this study will be improved understanding of the role of condensed-phase photochemistry in chemical aging of aerosol particles and cloud droplets. Bateman et

  7. Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

    EPA Science Inventory

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for...

  8. Aqueous aerosol SOA formation: impact on aerosol physical properties.

    PubMed

    Woo, Joseph L; Kim, Derek D; Schwier, Allison N; Li, Ruizhi; McNeill, V Faye

    2013-01-01

    Organic chemistry in aerosol water has recently been recognized as a potentially important source of secondary organic aerosol (SOA) material. This SOA material may be surface-active, therefore potentially affecting aerosol heterogeneous activity, ice nucleation, and CCN activity. Aqueous aerosol chemistry has also been shown to be a potential source of light-absorbing products ("brown carbon"). We present results on the formation of secondary organic aerosol material in aerosol water and the associated changes in aerosol physical properties from GAMMA (Gas-Aerosol Model for Mechanism Analysis), a photochemical box model with coupled gas and detailed aqueous aerosol chemistry. The detailed aerosol composition output from GAMMA was coupled with two recently developed modules for predicting a) aerosol surface tension and b) the UV-Vis absorption spectrum of the aerosol, based on our previous laboratory observations. The simulation results suggest that the formation of oligomers and organic acids in bulk aerosol water is unlikely to perturb aerosol surface tension significantly. Isoprene-derived organosulfates are formed in high concentrations in acidic aerosols under low-NO(x) conditions, but more experimental data are needed before the potential impact of these species on aerosol surface tension may be evaluated. Adsorption of surfactants from the gas phase may further suppress aerosol surface tension. Light absorption by aqueous aerosol SOA material is driven by dark glyoxal chemistry and is highest under high-NO(x) conditions, at high relative humidity, in the early morning hours. The wavelength dependence of the predicted absorption spectra is comparable to field observations and the predicted mass absorption efficiencies suggest that aqueous aerosol chemistry can be a significant source of aerosol brown carbon under urban conditions. PMID:24601011

  9. Key parameters controlling OH-initiated formation of secondary organic aerosol in the aqueous phase (aqSOA)

    NASA Astrophysics Data System (ADS)

    Ervens, Barbara; Sorooshian, Armin; Lim, Yong B.; Turpin, Barbara J.

    2014-04-01

    Secondary organic aerosol formation in the aqueous phase of cloud droplets and aerosol particles (aqSOA) might contribute substantially to the total SOA burden and help to explain discrepancies between observed and predicted SOA properties. In order to implement aqSOA formation in models, key processes controlling formation within the multiphase system have to be identified. We explore parameters affecting phase transfer and OH(aq)-initiated aqSOA formation as a function of OH(aq) availability. Box model results suggest OH(aq)-limited photochemical aqSOA formation in cloud water even if aqueous OH(aq) sources are present. This limitation manifests itself as an apparent surface dependence of aqSOA formation. We estimate chemical OH(aq) production fluxes, necessary to establish thermodynamic equilibrium between the phases (based on Henry's law constants) for both cloud and aqueous particles. Estimates show that no (currently known) OH(aq) source in cloud water can remove this limitation, whereas in aerosol water, it might be feasible. Ambient organic mass (oxalate) measurements in stratocumulus clouds as a function of cloud drop surface area and liquid water content exhibit trends similar to model results. These findings support the use of parameterizations of cloud-aqSOA using effective droplet radius rather than liquid water volume or drop surface area. Sensitivity studies suggest that future laboratory studies should explore aqSOA yields in multiphase systems as a function of these parameters and at atmospherically relevant OH(aq) levels. Since aerosol-aqSOA formation significantly depends on OH(aq) availability, parameterizations might be less straightforward, and oxidant (OH) sources within aerosol water emerge as one of the major uncertainties in aerosol-aqSOA formation.

  10. Chemical characterization of the main secondary organic aerosol (SOA) products formed through aqueous-phase photonitration of guaiacol

    NASA Astrophysics Data System (ADS)

    Kitanovski, Z.; Čusak, A.; Grgić, I.; Claeys, M.

    2014-04-01

    Guaiacol (2-methoxyphenol) and its derivatives can be emitted into the atmosphere by thermal degradation (i.e. burning) of wood lignins. Due to its volatility, guaiacol is predominantly distributed in the atmospheric gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA) in the atmosphere. The main objectives of the present study were to chemically characterize the low-volatility SOA products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of H2O2 and nitrite. The formed guaiacol reaction products were concentrated by using solid-phase extraction (SPE) and then purified by means of semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state 1H, 13C and 2D nuclear magnetic resonance (NMR) spectroscopy and direct infusion negative ion electrospray ionization tandem mass spectrometry ((-)ESI-MS/MS). The NMR and product ion (MS2) spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG), 6-nitroguaiacol (6NG), and 4,6-dinitroguaiacol (4,6DNG). Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia) by means of HPLC/(-)ESI-MS/MS. Owing to the strong absorption of UV and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

  11. Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

    2011-12-01

    Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

  12. Fourier Transform Infrared Spectroscopy for Identification and Quantification of Organic Functional Groups in Aqueous Phase Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    George, K.; Ruthenburg, T. C.; Smith, J.; Anastasio, C.; Dillner, A. M.

    2011-12-01

    Particles in the atmosphere influence visibility, climate, and human health. Secondary organic aerosols (SOA) formed from chemical reactions in the atmosphere constitute a portion of total organic particle mass. Most research on SOA has focused on gas phase reactions; however, reactions taking place in cloud and fog drops may be significant. One group of water-soluble compounds that participate in these reactions is phenols. Phenols, emitted from biomass burning, react in the aqueous phase to form low-volatility SOA products. The products formed from these reactions are currently poorly characterized. In order to characterize laboratory-generated samples, we are developing an attenuated total reflectance-Fourier transform infrared spectroscopic (ATR-FTIR) technique to identify and quantify organic functional groups in SOA. Aqueous SOA is made in the laboratory by illuminating solutions of phenolic compounds with an oxidant. The illuminated solution is then blown to dryness in order to determine the mass of SOA produced. The dry SOA is reconstituted in water and drops of this solution are placed onto a single-reflection ATR accessory. In order to identify and quantify functional groups in the complex SOA samples, it is necessary to calibrate with compounds and mixtures of compounds containing bond types similar to those found in the laboratory-generated SOA. Initially, focus has been placed on multiple peaks located in the region between 1800 cm-1 and 800 cm-1, including peaks for C=O and C-O. We distinguish between characteristic absorbances to begin determining the organic functional group composition of the SOA samples. This ATR-FTIR technique complements information from mass spectrometry measurements and allows us to quantify organic mass for non-volatile SOA products.

  13. FT-IR quantification of the carbonyl functional group in aqueous-phase secondary organic aerosol from phenols

    NASA Astrophysics Data System (ADS)

    George, Kathryn M.; Ruthenburg, Travis C.; Smith, Jeremy; Yu, Lu; Zhang, Qi; Anastasio, Cort; Dillner, Ann M.

    2015-01-01

    Recent findings suggest that secondary organic aerosols (SOA) formed from aqueous-phase reactions of some organic species, including phenols, contribute significantly to particulate mass in the atmosphere. In this study, we employ a Fourier transform infrared (FT-IR) spectroscopic technique to identify and quantify the functional group makeup of phenolic SOA. Solutions containing an oxidant (hydroxyl radical or 3,4-dimethoxybenzaldehyde) and either one phenol (phenol, guaiacol, or syringol) or a mixture of phenols mimicking softwood or hardwood emissions were illuminated to make SOA, atomized, and collected on a filter. We produced laboratory standards of relevant organic compounds in order to develop calibrations for four functional groups: carbonyls (Cdbnd O), saturated C-H, unsaturated C-H and O-H. We analyzed the SOA samples with transmission FT-IR to identify and determine the amounts of the four functional groups. The carbonyl functional group accounts for 3-12% of the SOA sample mass in single phenolic SOA samples and 9-14% of the SOA sample mass in mixture samples. No carbonyl functional groups are present in the initial reactants. Varying amounts of each of the other functional groups are observed. Comparing carbonyls measured by FT-IR (which could include aldehydes, ketones, esters, and carboxylic acids) with eight small carboxylic acids measured by ion chromatography indicates that the acids only account for an average of 20% of the total carbonyl reported by FT-IR.

  14. SOA Formation from Glyoxal in the Aerosol Aqueous Phase: A case study from Mexico City using an explicit laboratory-based model

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Dzepina, K.; Lee-Taylor, J.; Ervens, B.; Volkamer, R.

    2012-04-01

    Glyoxal is an important contributor to secondary organic aerosol (SOA) formation via aerosol aqueous phase processing. This work takes a glyoxal-SOA model parameterization based on laboratory data and applies the box model to ambient measurements. For the Mexico City Metropolitan Area (MCMA) case study on April 9, 2003 the aerosol uptake and processing of glyoxal in aerosol water is investigated, and found able to rationalize the previously observed gas phase glyoxal imbalance (Volkamer et al., 2007) for the first time based on laboratory data. Our aerosol size distribution resolving model is constrained with time resolved distributions of aerosol chemical composition, and supports a surface limited uptake mechanism of glyoxal in Mexico City. We compare the AMS-measured OOA to SOA predictions using our glyoxal model combined with background aerosol, traditional VOC precursor (e.g., aromatics) SOA, and three parameterizations for SOA formation from S/IVOC, i.e., based on (1) Robinson et al., 2007, (2) Grieshop et al., 2009, and (3) GECKO-A (Lee-Taylor et al., 2011), which account for the bulk of SOA mass, but give very different results for the O/C ratio of predicted SOA. This presents to our knowledge the first comparison of a molecular perspective of S/IVOC ageing with empirical parameterizations. We compare the mass weighted O/C ratio from these different SOA sources to AMS-measured O/C ratios, in an attempt to use the rapidly increasing O/C to test for closure, and advance our understanding of aerosol ageing in Mexico City.

  15. Aqueous-phase photolysis of biacetyl (An α-dicarbonyl compound): A sink for biacetyl, and a source of acetic acid, peroxyacetic acid, hydrogen peroxide, and the highly oxidizing acetylperoxyl radical in aqueous aerosols, fogs, and clouds

    NASA Astrophysics Data System (ADS)

    Faust, Bruce C.; Powell, Kendall; Rao, C. Janakiram; Anastasio, Cort

    Aqueous-phase photolysis of biacetyl represents a heretofore uncharacterized sink for biacetyl and source of organic acids and peroxides to aqueous aerosols, and fog and cloud drops. The photolysis half-life of aqueous-phase biacetyl is approximately 1.0-1.6 h for a solar zenith angle of 36° (midday equinox sunlight in Durham, NC). Major products of aqueous biacetyl photolysis are acetic acid, peroxyacetic acid, and hydrogen peroxide. Pyruvic acid and methylhydroperoxide are minor photoproducts. Common atmospheric reductants (H-atom donors), such as formate, formaldehyde, glyoxal, phenol (as a model for phenolic compounds) and α- D-glucose (as a model for carbohydrates), substantially increase the quantum yields of peroxyacetic acid Formate also significantly increases the quantum yields of hydrogen peroxide. The highly oxidizing acetylperoxyl radical is proposed as a key intermediate in the photolysis of aqueous biacetyl. The sources and reactions of acetylperoxyl radicals in aqueous aerosols, fogs, and clouds should be investigated in future studies of atmospheric water-drop chemistry.

  16. Investigating the impact of aqueous-phase chemistry and wet deposition on organic aerosol formation using a molecular surrogate modeling approach.

    PubMed

    Couvidat, Florian; Sartelet, Karine; Seigneur, Christian

    2013-01-15

    A molecular surrogate representation of secondary organic aerosol (SOA) formation is used to investigate the effect of aqueous-phase (in clouds and particles) chemical processing and wet deposition on SOA atmospheric concentrations. To that end, the hydrophilic/hydrophobic organic (H(2)O) model was augmented to account for several gas/aqueous-phase equilibria and aqueous-phase processes, including the formation of oxalic, glyoxilic and pyruvic acids, the oxidation of methyl vinyl ketone (MVK) and methacrolein (MACR), the formation of tetrols and organosulfates from epoxydiols (IEPOX), and further oxidation of water-soluble SOA (aging). Among those processes, SOA chemical aging and IEPOX reactions led to the most significant increases (up to 1 μg m(-3) in some areas) in SOA concentrations in a one-month summer simulation over Europe. However, large uncertainties remain in the gas/aqueous-phase partitioning of oxalic acid, MVK, and MACR. Below-cloud scavenging of SOA precursor gases and of gas-phase SVOC was found to affect SOA concentrations by up to 20%, which suggests that it should be taken into account in air quality models.

  17. Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

    NASA Astrophysics Data System (ADS)

    Marais, E. A.; Jacob, D. J.; Jimenez, J. L.; Campuzano-Jost, P.; Day, D. A.; Hu, W.; Krechmer, J.; Zhu, L.; Kim, P. S.; Miller, C. C.; Fisher, J. A.; Travis, K.; Yu, K.; Hanisco, T. F.; Wolfe, G. M.; Arkinson, H. L.; Pye, H. O. T.; Froyd, K. D.; Liao, J.; McNeill, V. F.

    2016-02-01

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx ≡ NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease more strongly as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US Environmental Protection Agency (EPA) projects 2013-2025 decreases in anthropogenic emissions of

  18. Chemical insights, explicit chemistry, and yields of secondary organic aerosol from OH radical oxidation of methylglyoxal and glyoxal in the aqueous phase

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Tan, Y.; Turpin, B. J.

    2013-09-01

    Atmospherically abundant, volatile water-soluble organic compounds formed through gas-phase chemistry (e.g., glyoxal (C2), methylglyoxal (C3), and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs, and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH-radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud-relevant concentrations (~ 10-6 - ~ 10-3 M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are ~ 120% for glyoxal and ~ 80% for methylglyoxal. During droplet evaporation oligomerization of unreacted methylglyoxal/glyoxal that did not undergo aqueous photooxidation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (~ 10 M), the major oxidation products are oligomers formed via organic radical-radical reactions, and simulated SOA yields (by mass) are ~ 90% for both glyoxal and methylglyoxal. Non-radical reactions (e.g., with ammonium) could enhance yields.

  19. A Study on the Aqueous Formation of Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Sinclair, K.; Tsigaridis, K.

    2013-12-01

    The effect aerosols have on radiative forcing in the atmosphere is recognized as one of the largest uncertainties in the radiation budget. About 80% of organic aerosol mass in the atmosphere is estimated to be created though secondary processes. Recently, the aqueous formation of secondary organic aerosols (SOA) has become recognized as important when considering the source, transformation and radiative impacts of SOA. This work focuses on implementing a mechanism for aqueous SOA formation that can be used in atmospheric chemistry and models of all scales, from box to global. A box model containing a simplified chemical mechanism for the aqueous production of precursors of aqueous SOA (Myriokefalitakis et al. (2011) is coupled to gas-phase chemistry which uses the carbon bond mechanism (CBM) IV is presented. The model implements aqueous chemistry of soluble gases, both in-cloud and aerosol water, including organic compounds such as glyoxal and methylglyoxal, which have been shown as potentially significant sources for dissolved secondary organic aerosols. This mechanism implements aqueous phase mass transfer and molecular dissociation. The model's performance is evaluated against previous box model studies from the literature. A comparison is conducted between the detailed GAMMA model (McNeill et al., 2012), which is constrained with chamber experiments and the one developed here. The model output under different atmospheric conditions is explored and differences and sensitivities are assessed. The objective of this work is to create a robust framework for simulating aqueous phase formation of SOA and maximizing the computational efficiency of the model, while maintaining accuracy, in order to later use the exact mechanism in global climate simulations.

  20. Secondary Organic Aerosol and Brown Carbon Formation in the Sunlit Aqueous Phase: Aldehyde Photooxidation in the Presence of Ammonium Salts and Amines

    NASA Astrophysics Data System (ADS)

    De Haan, D. O.; Galloway, M. M.; Sharp, K. D.; Jiménez, N. G.

    2014-12-01

    The chemistry of water-soluble carbonyl compounds in clouds is now acknowledged as an important source of secondary organic aerosol. These reactive carbonyl compounds are oxidized to carboxylic acids and form oligomers by radical-radical reactions and by "dark reactions" with ammonium salts (AS) and/or amines. The latter class of reactions also produces light-absorbing brown carbon compounds, especially reactions involving methylglyoxal or glyoxal and amines. However, recent work has found that UV light fades the color of glyoxal + AS and methylgyloxal + AS reaction mixtures. We recently studied aldehyde-AS-amine reactions in sunlight and in control vessels at the same temperature to determine the effects of solar radiation on the aqueous-phase production of brown carbon. In sunlight, methylglyoxal reaction mixtures lost their initial color and failed to brown, indicating the photolytic loss of reactants and/or pre-brown intermediates. In many other reactions, brown products are lost to photolysis, reducing the overall browning of solutions exposed to sunlight. In other experiments, hydrogen peroxide was added to generate OH radicals by photolysis. In the presence of OH radicals, some carbonyl compound mixtures (e.g. those containing hydroxyacetone or glycolaldehyde) browned more rapidly when exposed to sunlight. This indicates the existence of uncharacterized photooxidative browning pathways involving aqueous-phase OH radicals, carbonyls, ammonium salts, and/or amine compounds.

  1. Nighttime aqueous-phase secondary organic aerosols in Los Angeles and its implication for fine particulate matter composition and oxidative potential

    NASA Astrophysics Data System (ADS)

    Saffari, Arian; Hasheminassab, Sina; Shafer, Martin M.; Schauer, James J.; Chatila, Talal A.; Sioutas, Constantinos

    2016-05-01

    Recent investigations suggest that aqueous phase oxidation of hydrophilic organic compounds can be a significant source of secondary organic aerosols (SOA) in the atmosphere. Here we investigate the possibility of nighttime aqueous phase formation of SOA in Los Angeles during winter, through examination of trends in fine particulate matter (PM2.5) carbonaceous content during two contrasting seasons. Distinctive winter and summer trends were observed for the diurnal variation of organic carbon (OC) and secondary organic carbon (SOC), with elevated levels during the nighttime in winter, suggesting an enhanced formation of SOA during that period. The nighttime ratio of SOC to OC was positively associated with the relative humidity (RH) at high RH levels (above 70%), which is when the liquid water content of the ambient aerosol would be high and could facilitate dissolution of hydrophilic primary organic compounds into the aqueous phase. Time-integrated collection and analysis of wintertime particles at three time periods of the day (morning, 6:00 a.m.-9:00 a.m.; afternoon, 11:00 a.m.-3:00 p.m.; night, 8:00 p.m.-4:00 a.m.) revealed higher levels of water soluble organic carbon (WSOC) and organic acids during the night and afternoon periods compared to the morning period, indicating that the SOA formation in winter continues throughout the nighttime. Furthermore, diurnal trends in concentrations of semi-volatile organic compounds (SVOCs) from primary emissions showed that partitioning of SVOCs from the gas to the particle phase due to the decreased nighttime temperatures cannot explain the substantial OC and SOC increase at night. The oxidative potential of the collected particles (quantified using a biological macrophage-based reactive oxygen species assay, in addition to the dithiothreitol assay) was comparable during afternoon and nighttime periods, but higher (by at least ∼30%) compared to the morning period, suggesting that SOA formation processes possibly

  2. Changes in Sulfate Aerosol Associated with Aqueous Chemistry, Heterogeneous Reactions on Aerosol and Nucleation

    NASA Astrophysics Data System (ADS)

    Penner, J. E.; Herzoa, M.

    2002-12-01

    Changes in sulfate aerosol size distribution and production rates may result from changes in the chemical pathways associated with sulfate formation. Sulfate aerosol formation is the result of homogeneous gas-phase reaction of SO2 and in-cloud oxidation of SO2 by both ozone and peroxides. In addition, sulfate may form in reactions with dust and sea-salt. Here, we examine these reactions using the GRANTOUR global aerosol-chemistry model. The sulfate formed by reaction with dust and sea salt aerosols represents approximately 5% and 4%, respectively, of total sulfate while that formed in aqueous reactions in clouds represents approximately 55%. Gas-phase production of H2 SO4 results in the nucleation of new particles which coagulate with themselves and with other aerosols. We report the increase in aerosol number concentration associated with nucleation of new particles. We also discuss the changes in the sulfate aerosol size distribution associated with these pathways in both the present-day and pre-industrial atmosphere. The consequences of including such size distribution changes for aerosol forcing are discussed.

  3. Novel insights about salting-effects and reactivity of soluble molecules in aqueous aerosols

    NASA Astrophysics Data System (ADS)

    Volkamer, Rainer

    2014-05-01

    Organic carbon in the atmosphere modifies the lifetime of climate active gases such as O3, and CH4 (oxidative capacity), and forms aerosols that affect Earth's radiation balance. Water soluble organic carbon (WSOC) molecules are well established to form secondary organic aerosol (SOA) in cloud water. However, the chemistry and rate of SOA formation in aqueous aerosol is less well known, and is typically ignored in atmospheric models. Aqueous particles provide a very different chemical environment than clouds, i.e., they are the most concentrated aqueous salt solution that can be found on Earth. As a result of high ionic strength, phase separations of inorganic and organic phases, mass transfer limitations and viscosity effects affect the chemistry in aqueous particles, which proceeds via essentially different reaction pathways than in clouds. Of particular importance in this context is the Henry's law partitioning coefficient. Laboratory experiments show activity coefficients of 1/500 for Henry's law partitioning coefficients of glyoxal in concentrated aqueous aerosol- salt solutions. This salting-in mechanism is investigated in laboratory experiments, and shown to be a major driver in the rate of secondary organic aerosol (SOA) formation from the multiphase chemistry of soluble species like glyoxal. This solicited talk will summarize and discuss new experimental findings from simulation chamber experiments, and bulk reactor experiments to assess the Setschenow salting behavior of soluble molecules in different aqueous seed types, and study the effect of anthropogenic triggers such as sulfate and ammonium for the reactivity of multiphase reactions in the aerosol aqueous phase.

  4. Organic peroxide and OH formation in aerosol and cloud water: laboratory evidence for this aqueous chemistry

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Turpin, B. J.

    2015-06-01

    Aqueous chemistry in atmospheric waters (e.g., cloud droplets or wet aerosols) is well accepted as an atmospheric pathway to produce secondary organic aerosol (SOAaq). Water-soluble organic compounds with small carbon numbers (C2-C3) are precursors for SOAaq and products include organic acids, organic sulfates, and high molecular weight compounds/oligomers. Fenton reactions and the uptake of gas-phase OH radicals are considered to be the major oxidant sources for aqueous organic chemistry. However, the sources and availability of oxidants in atmospheric waters are not well understood. The degree to which OH is produced in the aqueous phase affects the balance of radical and non-radical aqueous chemistry, the properties of the resulting aerosol, and likely its atmospheric behavior. This paper demonstrates organic peroxide formation during aqueous photooxidation of methylglyoxal using ultra high resolution Fourier Transform Ion Cyclotron Resonance electrospray ionization mass spectrometry (FTICR-MS). Organic peroxides are known to form through gas-phase oxidation of volatile organic compounds. They contribute secondary organic aerosol (SOA) formation directly by forming peroxyhemiacetals, and epoxides, and indirectly by enhancing gas-phase oxidation through OH recycling. We provide simulation results of organic peroxide/peroxyhemiacetal formation in clouds and wet aerosols and discuss organic peroxides as a source of condensed-phase OH radicals and as a contributor to aqueous SOA.

  5. Phototransformation of 4-phenoxyphenol sensitised by 4-carboxybenzophenone: Evidence of new photochemical pathways in the bulk aqueous phase and on the surface of aerosol deliquescent particles

    NASA Astrophysics Data System (ADS)

    De Laurentiis, Elisa; Socorro, Joanna; Vione, Davide; Quivet, Etienne; Brigante, Marcello; Mailhot, Gilles; Wortham, Henri; Gligorovski, Sasho

    2013-12-01

    In addition to direct photolysis, degradation of organic compounds by solar light can also occur by indirect photolysis or photo-sensitised processes. These reactions are important because they are involved in, among others, direct and indirect climate changes, adverse health effects from inhaled particles, effects on cloud chemistry and ozone production. In this work, the importance of atmospheric photo-sensitisation is evaluated in bulk aqueous solution and on the surface of aerosol deliquescent particles. Irradiation experiments in aqueous solution indicate that 4-carboxybenzophenone (CBP) is able to photosensitise the degradation of 4-phenoxyphenol (4 PP). The process takes place via the CBP triplet state (3CBP*), which has an oxidising nature. 4 PP is fluorescent, unlike the photosensitiser CBP, with two emission bands at ˜320 and ˜380 nm. However, addition of CBP to a 4 PP solution considerably decreases the intensity of 4 PP fluorescence bands and causes a very intense new band to appear at ˜420 nm. This behaviour suggests a possible interaction between CBP and 4 PP in solution, which could favour further light-induced processes. Moreover, the new band overlaps with the fluorescence spectrum of atmospheric HULIS (HUmic-LIke Substances), suggesting that supramolecular photosensitiser-substrate interactions may have a role in HULIS fluorescence properties. The interaction between CBP and 4 PP coated on silica particles (gas-solid system) was also investigated under simulated sunlight, and in the presence of variable relative humidity. The water molecules inhibit the degradation of 4 PP, induced by 3CBP* on the surface of aerosol particles, indicating that the process could be even faster on particles than in solution. We demonstrate that phenol substances adsorbed on aerosol surfaces and in bulk solution are substantially altered upon photosensitised processes.

  6. Solar Absorption by Aerosol-Bound Nitrophenols Compared to Aqueous and Gaseous Nitrophenols.

    PubMed

    Hinrichs, Ryan Z; Buczek, Pawel; Trivedi, Jal J

    2016-06-01

    Nitrophenols are well-known absorbers of near-UV/blue radiation and are considered to be a component of solar-absorbing organic aerosol material commonly labeled brown carbon. Nitrophenols have been identified in a variety of phases in earth's atmosphere, including the gaseous, aqueous, and aerosol bound, and these different environments alter their UV-vis absorption spectra, most dramatically when deprotonated forming nitrophenolates. We quantify the impact of these different absorption profiles by calculating the solar power absorbed per molecule for several nitrophenols. For instance, aqueous 2,4-dinitrophenol absorption varies dramatically over the pH range of cloud droplets with pH = 5.5 solutions absorbing three times the solar power compared to pH = 3.5 solutions. We also measured the UV-vis spectra of 2-nitrophenol adsorbed on several aerosol substrates representative of mineral dust, inorganic salts, and organic aerosol and compare these spectra to gaseous and aqueous 2-nitrophenol. 2-Nitrophenol adsorbed on mineral and chloride aerosol substrates exhibits a red-shifted absorption band (∼450-650 nm) consistent with 2-nitrophenolate and absorbs twice the solar power per molecule compared to gaseous, aqueous, and organic aerosol-bound 2-nitrophenol. We also discuss how different nitrophenol absorption profiles alter important atmospheric photolysis rate constants [e.g., J(NO2) and J(O3)] by attenuating solar flux.

  7. Longwave radiative forcing by aqueous aerosols

    SciTech Connect

    Gaffney, J.S.; Marley, N.A.

    1995-01-01

    Recently, a great deal of interest has been focused on the role of aerosols in climatic change because of their potential cooling impacts due to light scattering. Recent advances in infrared spectroscopy using cylindrical internal reflectance have allowed the longwave absorption of dissolved aerosol species and the associated liquid water to be accurately determined and evaluated. Experimental measurements using these techniques have shown that dissolved sulfate, nitrate, and numerous other aerosol species will act to cause greenhouse effects. Preliminary calculations indicate that the longwave climate forcing (i.e., heating) for sulfate aerosol will be comparable in magnitude to the cooling effect produced by light scattering. However, more detailed modeling will clearly be needed to address the impact of the longwave forcing due to aerosols as a function of atmospheric height and composition. Their work has shown that aerosol composition will be important in determining longwave forcing, while shortwave forcing will be more related to the physical size of the aerosol droplets. On the basis of these studies, it is increasingly apparent that aerosols, fogs, and clouds play a key role in determining the radiative balance of the atmosphere and in controlling regional and global climates.

  8. Laboratory evidence of organic peroxide and peroxyhemiacetal formation in the aqueous phase and implications for aqueous OH

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Turpin, B. J.

    2015-11-01

    Aqueous chemistry in atmospheric waters (e.g., cloud droplets or wet aerosols) is considered a potentially important atmospheric pathway to produce secondary organic aerosol (SOAaq). Water-soluble organic compounds with small carbon numbers (C2-C3) are precursors for SOAaq; products include organic acids, organic sulfates, and high-molecular-weight compounds/oligomers. Fenton reactions and the uptake of gas-phase OH radicals are considered to be the major oxidant sources for aqueous organic chemistry. However, the sources and availability of oxidants in atmospheric waters are not well understood. The degree to which OH is produced in the aqueous phase affects the balance of radical and non-radical aqueous chemistry, the properties of the resulting aerosol, and likely its atmospheric behavior. This paper demonstrates organic peroxide formation during aqueous photooxidation of methylglyoxal using ultra-high-resolution Fourier transform ion cyclotron resonance electrospray ionization mass spectrometry (FTICR-MS). Organic peroxides are known to form through gas-phase oxidation of volatile organic compounds. They contribute secondary organic aerosol (SOA) formation directly by forming peroxyhemiacetals and epoxides (i.e., IEPOX), and indirectly by enhancing gas-phase oxidation through OH recycling. We provide simulation results of organic peroxide/peroxyhemiacetal formation in clouds and wet aerosols and discuss organic peroxides as a source of condensed-phase OH radicals and as a contributor to aqueous SOA.

  9. Secondary Organic Aerosol Produced from Aqueous Reactions of Phenols in Fog Drops and Deliquesced Particles

    NASA Astrophysics Data System (ADS)

    Smith, J.; Anastasio, C.

    2014-12-01

    The formation and evolution of secondary organic aerosol (SOA) in atmospheric condensed phases (i.e., aqueous SOA) can proceed rapidly, but relatively little is known of the important aqueous SOA precursors or their reaction pathways. In our work we are studying the aqueous SOA formed from reactions of phenols (phenol, guaiacol, and syringol), benzene-diols (catechol, resorcinol, and hydroquinone), and phenolic carbonyls (e.g., vanillin and syringaldehyde). These species are potentially important aqueous SOA precursors because they are released in large quantities from biomass burning, have high Henry's Law constants (KH = 103 -109 M-1 atm-1) and are rapidly oxidized. To evaluate the importance of aqueous reactions of phenols as a source of SOA, we first quantified the kinetics and SOA mass yields for 11 phenols reacting via direct photodegradation, hydroxyl radical (•OH), and with an excited organic triplet state (3C*). In the second step, which is the focus of this work, we use these laboratory results in a simple model of fog chemistry using conditions during a previously reported heavy biomass burning event in Bakersfield, CA. Our calculations indicate that under aqueous aerosol conditions (i.e., a liquid water content of 100 μg m-3) the rate of aqueous SOA production (RSOA(aq)) from phenols is similar to the rate in the gas phase. In contrast, under fog/cloud conditions the aqueous RSOA from phenols is 10 times higher than the rate in the gas phase. In both of these cases aqueous RSOA is dominated by the oxidation of phenols by 3C*, followed by direct photodegradation of phenolic carbonyls, and then •OH oxidation. Our results suggest that aqueous oxidation of phenols is a significant source of SOA during fog events and also during times when deliquesced aerosols are present.

  10. Influence of aqueous chemistry on the chemical composition of fog water and interstitial aerosol in Fresno

    NASA Astrophysics Data System (ADS)

    Kim, Hwajin; Ge, Xinlei; Collier, Sonya; Xu, Jianzhong; Sun, Yele; Wang, Youliang; Herckes, Pierre; Zhang, Qi

    2015-04-01

    A measurement study was conducted in the Central Valley (Fresno) of California in January 2010, during which radiation fog events were frequently observed. Fog plays important roles in atmospheric chemistry by scavenging aerosol particles and trace gases and serving as a medium for various aqueous-phase reactions. Understanding the effects of fog on the microphysical and chemical processing of aerosol particles requires detailed information on their chemical composition. In this study, we characterized the chemical composition of fog water and interstitial aerosol particles to study the effects of fog processing on aerosol properties. Fog water samples were collected during the 2010 Fresno campaigns with a Caltech Active Strand Cloud water Collector (CASCC) while interstitial submicron aerosols were characterized in real time with an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a scanning Mobility Particle Sizer (SMPS). The fog water samples were later analyzed using the HR-ToF-AMS, ion chromatography, and a total carbon analyzer. The chemical composition and characteristics of interstitial particles during the fog events were compared to those of dissolved inorganic and organic matter in fog waters. Compared to interstitial aerosols, fog water is composed of a higher fraction of ammonium nitrate and oxygenated organics, due to aqueous formation of secondary aerosol species as well as enhanced gas-to-particle partitioning of water soluble species under water rich conditions. Sulfate is formed most efficiently in fog water although its contribution to total dissolved mass is relatively low. The HR-ToF-AMS mass spectra of organic matter in fog water (FOM) are very similar to that of oxygenated organic aerosols (OOA) derived from positive matrix factorization (PMF) of the HR-ToF-AMS spectra of ambient aerosol (r2 = 0.96), but FOM appears to contain a large fraction of acidic functional groups than OOA. FOM is also enriched of

  11. Characterizing the formation of organic layers on the surface of inorganic/aqueous aerosols by Raman spectroscopy.

    PubMed

    Buajarern, Jariya; Mitchem, Laura; Reid, Jonathan P

    2007-11-22

    We demonstrate that nonlinear Raman spectroscopy coupled with aerosol optical tweezers can be used to probe the evolving phase partitioning in mixed organic/inorganic/aqueous aerosol droplets that adopt a core-shell structure in which the aqueous phase is coated in an organic layer. Specifically, we demonstrate that the characteristic fingerprint of wavelengths at which stimulated Raman scattering is observed can be used to assess the phase behavior of multiphase decane/aqueous sodium chloride droplets. Decane is observed to form a layer on the surface of the core aqueous droplet, and from the spectroscopic signature the aqueous core size can be determined with nanometer accuracy and the thickness of the decane layer with an accuracy of +/-8 nm. Further, the presence of the organic layer is observed to reduce the rate at which water evaporates from the core of the droplet with an increasing rate of evaporation observed with diminishing layer thickness.

  12. Characterizing the formation of organic layers on the surface of inorganic/aqueous aerosols by Raman spectroscopy.

    PubMed

    Buajarern, Jariya; Mitchem, Laura; Reid, Jonathan P

    2007-11-22

    We demonstrate that nonlinear Raman spectroscopy coupled with aerosol optical tweezers can be used to probe the evolving phase partitioning in mixed organic/inorganic/aqueous aerosol droplets that adopt a core-shell structure in which the aqueous phase is coated in an organic layer. Specifically, we demonstrate that the characteristic fingerprint of wavelengths at which stimulated Raman scattering is observed can be used to assess the phase behavior of multiphase decane/aqueous sodium chloride droplets. Decane is observed to form a layer on the surface of the core aqueous droplet, and from the spectroscopic signature the aqueous core size can be determined with nanometer accuracy and the thickness of the decane layer with an accuracy of +/-8 nm. Further, the presence of the organic layer is observed to reduce the rate at which water evaporates from the core of the droplet with an increasing rate of evaporation observed with diminishing layer thickness. PMID:17958403

  13. Surface tension depression by low-solubility organic material in aqueous aerosol mimics

    NASA Astrophysics Data System (ADS)

    Schwier, Allison; Mitroo, Dhruv; McNeill, V. Faye

    2012-07-01

    Surface-active material, including long-chain fatty acids (LCFAs), comprises a significant fraction of organic aerosol mass. Surface-active species are thought to form a film at the gas-aerosol interface, with implications for aerosol heterogeneous chemistry and cloud formation. However, LCFA phase behavior and surface-bulk partitioning has not been characterized under most conditions typical of tropospheric aerosol water (i.e. acidic, high ionic content), making it challenging to predict surface film formation in aerosols. In this study, we present measurements of the surface tension of aqueous solutions containing the slightly soluble LCFAs oleic and stearic acid. The effect of varying pH, organic concentration, and inorganic salt content was tested for each system. We observe surface tension depression compared to water of up to ˜30 and 45% for aqueous solutions containing stearic or oleic acid at pH 0-8 and high inorganic salt concentrations (NaCl and (NH4)2SO4). This suggests that surface film formation is favorable for these species in atmospheric aerosols.

  14. Aqueous photooxidation of ambient Po Valley Italy air samples: Insights into secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Kirkland, J. R.; Lim, Y. B.; Sullivan, A. P.; Decesari, S.; Facchini, C.; Collett, J. L.; Keutsch, F. N.; Turpin, B. J.

    2012-12-01

    In this work, we conducted aqueous photooxidation experiments with ambient samples in order to develop insights concerning the formation of secondary organic aerosol through gas followed by aqueous chemistry (SOAaq). Water-soluble organics (e.g., glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone) are formed through gas phase oxidation of alkene and aromatic emissions of anthropogenic and biogenic origin. Their further oxidation in clouds, fogs and wet aerosols can form lower volatility products (e.g., oligomers, organic acids) that remain in the particle phase after water evaporation, thus producing SOA. The aqueous OH radical oxidation of several individual potentially important precursors has been studied in the laboratory. In this work, we used a mist-chamber apparatus to collect atmospheric mixtures of water-soluble gases from the ambient air at San Pietro Capofiume, Italy during the PEGASOS field campaign. We measured the concentration dynamics after addition of OH radicals, in order to develop new insights regarding formation of SOA through aqueous chemistry. Specifically, batch aqueous reactions were conducted with 33 ml mist-chamber samples (TOC ~ 50-100μM) and OH radicals (~10-12M) in a new low-volume aqueous reaction vessel. OH radicals were formed in-situ, continuously by H2O2 photolysis. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS +/-), and ESI-MS with IC pre-separation (IC/ESI-MS-). Reproducible formation of pyruvate and oxalate were observed both by IC and ESI-MS. These compounds are known to form from aldehyde oxidation in the aqueous phase. New insights regarding the aqueous chemistry of these "more atmospherically-realistic" experiments will be discussed.

  15. Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Volkamer, R.

    2010-09-01

    This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA) in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry for the same conditions (liquid water content, particle size). The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ∼5 μg m-3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 < pH < 7). Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend on aerosol loading or water content, which indicates a

  16. Current therapies and technological advances in aqueous aerosol drug delivery.

    PubMed

    Watts, Alan B; McConville, Jason T; Williams, Robert O

    2008-09-01

    Recent advances in aerosolization technology have led to renewed interest in pulmonary delivery of a variety of drugs. Pressurized metered dose inhalers (pMDIs) and dry powder inhalers (DPIs) have experienced success in recent years; however, many limitations are presented by formulation difficulties, inefficient delivery, and complex device designs. Simplification of the formulation process as well as adaptability of new devices has led many in the pharmaceutical industry to reconsider aerosolization in an aqueous carrier. In the acute care setting, breath-enhanced air-jet nebulizers are controlling and minimizing the amount of wasted medication, while producing a high percentage of respirable droplets. Vibrating mesh nebulizers offer advantages in higher respirable fractions (RFs) and slower velocity aerosols when compared with air-jet nebulizers. Vibrating mesh nebulizers incorporating formulation and patient adaptive components provide improvements to continuous nebulization technology by generating aerosol only when it is most likely to reach the deep lung. Novel innovations in generation of liquid aerosols are now being adapted for propellant-free pulmonary drug delivery to achieve unprecedented control over dose delivered and are leading the way for the adaptation of systemic drugs for delivery via the pulmonary route. Devices designed for the metered dose delivery of insulin, morphine, sildenafil, triptans, and various peptides are all currently under investigation for pulmonary delivery to treat nonrespiratory diseases. Although these devices are currently still in clinical testing (with the exception of the Respimat), metered dose liquid inhalers (MDLIs) have already shown superior outcomes to current pulmonary and systemic delivery methods.

  17. Phases and Phase Changes of Mixed Organic/Inorganic Model Systems of Tropospheric Aerosols

    NASA Astrophysics Data System (ADS)

    Marcolli, C.; Krieger, U. K.; Zardini, A. A.; Zobrist, B.; Zuend, A.; Luo, B. P.; Peter, T.

    2006-12-01

    Knowledge of the physical state of tropospheric aerosols is important for an adequate description of cloud formation, heterogeneous and multiphase chemistry, and the aerosol's radiative properties. We will present and discuss laboratory experiments on bulk aerosol model mixtures and micron-sized particles consisting of polyols, polyethylene glycol or dicarboxylic acids mixed with ammonium sulfate. Depending on the exact composition and relative humidity, these mixtures form liquid-one-phase or two-phase systems plus additional solid phases. Whilst the organic matter in ambient aerosols is expected to be predominantly present in the form of liquid or amorphous phases, the inorganic salts may still undergo deliquescence and efflorescence as a function of relative humidity. Moreover, they may induce phase separations into a predominantly organic and an inorganic aqueous phase. In the absence of solid phases, the water uptake and release of the investigated micron-sized particles was usually well described by the Zdanovskii-Stokes-Robinson (ZSR) approach. However, this model became inaccurate when solid phases were present. Moreover, it is not able to account for liquid-liquid phase separations due to the salting-out effects of the investigated inorganic salts. While most organics participate in liquid phases some organic substances are abundant enough in the particles to form crystalline solids that might act as ice nuclei. We show that this is the case for oxalic acid.

  18. Phase transformation and growth of hygroscopic aerosols

    SciTech Connect

    Tang, I.N.

    1995-09-01

    Ambient aerosols frequently contain large portions of hygroscopic inorganic salts such as chlorides, nitrates, and sulfates in either pure or mixed forms. Such inorganic salt aerosols exhibit the properties of deliquescence and efflorescence in air. The phase transformation from a solid particle to a saline droplet usually occurs spontaneously when the relative humidity of the atmosphere reaches a level specific to the chemical composition of the aerosol particle. Conversely, when the relative humidity decreases and becomes low enough, the saline droplet will evaporate and suddenly crystallize, expelling all its water content. The phase transformation and growth of aerosols play an important role in many atmospheric processes affecting air quality, visibility degradation, and climate changes. In this chapter, an exposition of the underlying thermodynamic principles is given, and recent advances in experimental methods utilizing single-particle levitation are discussed. In addition, pertinent and available thermodynamic data, which are needed for predicting the deliquescence properties of single and multi-component aerosols, are compiled. This chapter is useful to research scientists who are either interested in pursuing further studies of aerosol thermodynamics, or required to model the dynamic behavior of hygroscopic aerosols in a humid environment.

  19. Urban Air Pollution from Ethanol (E85) in the Presence of Aqueous Aerosols and Fog

    NASA Astrophysics Data System (ADS)

    Ginnebaugh, D. L.; Jacobson, M. Z.

    2010-12-01

    This is a study to examine the effect of ethanol (E85) versus gasoline on urban air pollution in the presence of aqueous aerosols and fog. In previous work, we analyzed the temperature-dependence of ethanol and gasoline exhaust chemistry and its impact on urban air pollution considering only gas-phase chemistry. We used the near-explicit Master Chemical Mechanism (MCM, version 3.1, LEEDS University) with the SMVGEAR II chemical ordinary differential solver to provide the speed necessary to simulate explicit chemistry. The MCM has over 13,500 organic reactions and 4,600 species. SMVGEAR II is a sparse-matrix Gear solver that reduces the computation time significantly while maintaining any specified accuracy. We found that the average ozone concentrations through the range of temperatures tested could be higher with E85 than with gasoline by up to 8 parts per billion volume (ppbv) at room temperature but much higher at cold temperatures and low sunlight (winter conditions) for a region with a high nitrogen oxide (NOx) to non-methane organic gases (NMOG) ratio. We also found that the solution to chemistry in a 3-D urban airshed model was practical. We now extend our study to include aqueous chemistry in the presence of aerosols and fog. We combine the Chemical Aqueous Phase Radical Mechanism, CAPRAM 3.0 with the MCM 3.1 and gas-particle transfer in box model calculations. CAPRAM treats aqueous phase chemistry among 390 species and 829 reactions (including 51 gas-to-aqueous phase reactions). We investigate the impact aqueous reactions have on unburned ethanol and acetaldehyde mixing ratios in the atmosphere in particular because acetaldehyde is an ozone precursor and carcinogen, and aqueous oxidation has potential to speed the conversion of unburned ethanol to acetaldehyde. Acetaldehyde also forms acetic acid in aqueous solution. Acetic acid vapor is an eye, nose, and lung irritant, so both species contribute negatively to human health. We look at the impact of aerosol

  20. Aqueous secondary organic aerosol (SOA) production from the oxidation of phenols by triplet excited state organics

    NASA Astrophysics Data System (ADS)

    Smith, J.; Yu, L.; Zhang, Q.; Anastasio, C.

    2011-12-01

    Recent literature has shown that atmospheric condensed-phase chemistry can play a significant role in the evolution of organic aerosols, including the formation of secondary organic aerosol (SOA). SOA formation from the oxidation of volatile organic compounds (VOCs) in the aqueous phase has largely focused on oxidations involving the hydroxyl radical and other oxidants, such as photochemically created triplet excited states, have not been fully investigated. Phenolic compounds are one of the primary carbon emission classes from biomass and wood combustion and have significant water solubility. Once in the aqueous phase, phenolic compounds can react with the triplet excited states of non-phenolic aromatic carbonyls (NPCs), particle-bound organics that are also emitted in large quantities from wood combustion. The oxidation of phenolic species in the condensed phase by triplet excited states can result in the production of SOA. A main goal of this study was to investigate bulk solution reaction kinetics under atmospherically relevant conditions in order to ascertain how these reactions can impact aqueous-phase SOA production. In our experiments, we studied the reactions of five phenols (phenol, guaiacol, syringol, catechol, and resorcinol) with the triplet state of 3,4-dimethoxybenzaldehyde (34-DMB) during simulated solar radiation. We have characterized the impacts of pH, ionic strength and reactant concentrations on the reaction behavior of this system. In addition, we analyzed the SOA formed using high-resolution aerosol mass spectrometry, ion chromatography, and liquid chromatography-mass spectrometry to infer the reaction mechanisms. Our evidence suggests that under atmospherically relevant conditions, triplet excited states can be the dominant oxidant of phenolics and contribute significantly to the total SOA budget.

  1. Modeling aerosol growth by aqueous chemistry in nonprecipitating stratiform cloud

    SciTech Connect

    Ovchinnikov, Mikhail; Easter, Richard C.

    2010-07-29

    A new microphysics module based on a two-dimensional (2D) joint size distribution function representing both interstitial and cloud particles is developed and applied to studying aerosol processing in non-precipitating stratocumulus clouds. The module is implemented in a three-dimensional dynamical framework of a large-eddy simulation (LES) model and in a trajectory ensemble model (TEM). Both models are used to study the modification of sulfate aerosol by the activation - aqueous chemistry - resuspension cycle in shallow marine stratocumulus clouds. The effect of particle mixing and different size-distribution representations on modeled aerosol processing are studied in a comparison of the LES and TEM simulations with the identical microphysics treatment exposes and a comparison of TEM simulations with a 2D fixed and moving bin microphysics. Particle mixing which is represented in LES and neglected in the TEM leads to the mean relative per particle dry mass change in the TEM simulations being about 30% lower than in analogous subsample of LES domain. Particles in the final LES spectrum are mixed in from different “parcels”, some of which have experienced longer in-cloud residence times than the TEM parcels, all of which originated in the subcloud layer, have. The mean relative per particle dry mass change differs by 14% between TEM simulations with fixed and moving bin microphysics. Finally, the TEM model with the moving bin microphysics is used to evaluate assumptions about liquid water mass partitioning among activated cloud condensation nuclei (CCN) of different dry sizes. These assumptions are used in large-scale models to map the bulk aqueous chemistry sulfate production, which is largely proportional to the liquid water mass, to the changes in aerosol size distribution. It is shown that the commonly used assumptions that the droplet mass is independent of CCN size or that the droplet mass is proportional to the CCN size to the third power do not perform

  2. Direct observation of aqueous secondary organic aerosol from biomass-burning emissions

    PubMed Central

    Massoli, Paola; Paglione, Marco; Giulianelli, Lara; Carbone, Claudio; Rinaldi, Matteo; Decesari, Stefano; Sandrini, Silvia; Costabile, Francesca; Gobbi, Gian Paolo; Pietrogrande, Maria Chiara; Visentin, Marco; Scotto, Fabiana; Fuzzi, Sandro; Facchini, Maria Cristina

    2016-01-01

    The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the “brown” carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1–0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4–20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate. PMID:27551086

  3. Direct observation of aqueous secondary organic aerosol from biomass-burning emissions.

    PubMed

    Gilardoni, Stefania; Massoli, Paola; Paglione, Marco; Giulianelli, Lara; Carbone, Claudio; Rinaldi, Matteo; Decesari, Stefano; Sandrini, Silvia; Costabile, Francesca; Gobbi, Gian Paolo; Pietrogrande, Maria Chiara; Visentin, Marco; Scotto, Fabiana; Fuzzi, Sandro; Facchini, Maria Cristina

    2016-09-01

    The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the "brown" carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1-0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4-20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate. PMID:27551086

  4. Direct observation of aqueous secondary organic aerosol from biomass-burning emissions

    NASA Astrophysics Data System (ADS)

    Gilardoni, Stefania; Massoli, Paola; Paglione, Marco; Giulianelli, Lara; Carbone, Claudio; Rinaldi, Matteo; Decesari, Stefano; Sandrini, Silvia; Costabile, Francesca; Gobbi, Gian Paolo; Chiara Pietrogrande, Maria; Visentin, Marco; Scotto, Fabiana; Fuzzi, Sandro; Facchini, Maria Cristina

    2016-09-01

    The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the “brown” carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1-0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4-20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate.

  5. Method for aqueous phase reactions

    DOEpatents

    Elliott, Douglas C.; Hart, Todd R.

    2000-01-01

    A method for converting liquid organic material in a mixture into a product utilizing a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional metal deposited onto the support in a second dispersed phase. The additional metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase without substantially affecting the catalytic activity, thereby increasing the life time of the catalyst.

  6. Aqueous aerosol may build up large upper tropospheric ice supersaturation

    NASA Astrophysics Data System (ADS)

    Bogdan, Anatoli; Molina, Mario J.

    2010-05-01

    Keywords: ice supersaturation, upper tropospheric cirrus clouds, freezing of aqueous aerosol. Observations often reveal enhanced and persistent upper tropospheric (UT) ice supersaturation, Si up to 100%, independently of whether cirrus ice clouds are present or not (Krämer et al., 2009; Lawson et al., 2008). However, a water activity criterion (WAC) (Koop et al., 2000) does not allow the formation of Si > ~67% by the homogeneous freezing of aqueous droplets even at the lowest atmospheric temperature of ~185 K. For aqueous aerosol the WAC predicts the existence of a so called homogeneous ice nucleation threshold which, being expressed as Si, is between ~52 and 67% in the temperature range of ~220 - 185 K. The nature of the formation of large Si remains unclear. Since water vapor is the dominant greenhouse gas it is important to know the nature of the accumulation and persistence of water vapor in the UT. We studied the freezing behavior of micrometer-scaled 3-, 4-, and 5-component droplets, which contain different weight fractions of H2O, H2SO4, HNO3, (NH4)2SO4, (NH4)HSO4, NH4NO3, and (NH4)3H(SO4)2. The study was performed between 133 and 278 K at cooling rates of 3, 0.1, and 0.05 K/min using differential scanning calorimetry (DSC) (Bogdan and Molina, 2010). The cooling rates of 0.1 and 0.05 K/min (6 and 3 K/h) are similar to the smallest reported synoptic temperature change of ~2 K/h (Carslaw et al., 1998). Using the measured freezing temperature of ice, Ti, and the thermodynamic E-AIM model of the system of H+ - NH4+ - SO42-- NO3-- H2O (Clegg et al., 1998), we calculated the corresponding clear-sky Si which would be built up immediately prior to the formation of ice cirrus clouds by the homogeneous freezing of aqueous aerosol of similar composition. We found that our calculated values of Si are both larger and smaller than the homogeneous ice nucleation threshold. For example, for the droplets of compositions of 15/10 and 20/10 wt % (NH4)3H(SO4)2/H2SO4, which

  7. Effects of precursor concentration and acidic sulfate in aqueous glyoxal-OH radical oxidation and implications for secondary organic aerosol.

    PubMed

    Tan, Yi; Perri, Mark J; Seitzinger, Sybil P; Turpin, Barbara J

    2009-11-01

    Previous experiments demonstrated that aqueous OH radical oxidation of glyoxal yields low-volatility compounds. When this chemistry takes place in clouds and fogs, followed by droplet evaporation (or if it occurs in aerosol water), the products are expected to remain partially in the particle phase, forming secondary organic aerosol (SOA). Acidic sulfate exists ubiquitously in atmospheric water and has been shown to enhance SOA formation through aerosol phase reactions. In this work, we investigate how starting concentrations of glyoxal (30-3000 microM) and the presence of acidic sulfate (0-840 microM) affect product formation in the aqueous reaction between glyoxal and OH radical. The oxalic acid yield decreased with increasing precursor concentrations, and the presence of sulfuric acid did not alter oxalic acid concentrations significantly. A dilute aqueous chemistry model successfully reproduced oxalic acid concentrations, when the experiment was performed at cloud-relevant concentrations (glyoxal <300 microM), but predictions deviated from measurements at increasing concentrations. Results elucidate similarities and differences in aqueous glyoxal chemistry in clouds and in wet aerosols. They validate for the first time the accuracy of model predictions at cloud-relevant concentrations. These results suggest that cloud processing of glyoxal could be an important source of SOA. PMID:19924930

  8. Effects of precursor concentration and acidic sulfate in aqueous glyoxal-OH radical oxidation and implications for secondary organic aerosol.

    PubMed

    Tan, Yi; Perri, Mark J; Seitzinger, Sybil P; Turpin, Barbara J

    2009-11-01

    Previous experiments demonstrated that aqueous OH radical oxidation of glyoxal yields low-volatility compounds. When this chemistry takes place in clouds and fogs, followed by droplet evaporation (or if it occurs in aerosol water), the products are expected to remain partially in the particle phase, forming secondary organic aerosol (SOA). Acidic sulfate exists ubiquitously in atmospheric water and has been shown to enhance SOA formation through aerosol phase reactions. In this work, we investigate how starting concentrations of glyoxal (30-3000 microM) and the presence of acidic sulfate (0-840 microM) affect product formation in the aqueous reaction between glyoxal and OH radical. The oxalic acid yield decreased with increasing precursor concentrations, and the presence of sulfuric acid did not alter oxalic acid concentrations significantly. A dilute aqueous chemistry model successfully reproduced oxalic acid concentrations, when the experiment was performed at cloud-relevant concentrations (glyoxal <300 microM), but predictions deviated from measurements at increasing concentrations. Results elucidate similarities and differences in aqueous glyoxal chemistry in clouds and in wet aerosols. They validate for the first time the accuracy of model predictions at cloud-relevant concentrations. These results suggest that cloud processing of glyoxal could be an important source of SOA.

  9. Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

    NASA Astrophysics Data System (ADS)

    Quan, Jiannong; Liu, Quan; Li, Xia; Gao, Yang; Jia, Xingcan; Sheng, Jiujiang; Liu, Yangang

    2015-12-01

    The effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO2), and ozone (O3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (Nratio) and S from SO2 to sulfate (Sratio) both significantly increased in haze events, suggesting enhanced conversions from NOx and SO2 to their corresponding particle phases in the late haze period. Further analysis shows that Nratio and Sratio increased with increasing RH, with Nratio and Sratio being only 0.04 and 0.03, respectively, when RH < 40%, and increasing up to 0.16 and 0.12 when RH reached 60-80%, respectively. The enhanced conversion ratios of N and S in the late haze period is likely due to heterogeneous aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of Nratio and Sratio to O3: the conversion ratios increase with decreasing O3 concentration when O3 concentration is lower than <15 ppb but increased with increasing O3 when O3 concentration is higher than 15 ppb. The results suggest that heterogeneous aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly due to high emission and low reaction rate; the occurrence of heterogeneous aqueous reactions in the late haze period, together with the accumulated high concentrations of precursor gases such as SO2 and NOx, accelerated the formation of secondary

  10. Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

    DOE PAGES

    Quan, Jiannong; Liu, Yangang; Liu, Quan; Li, Xia; Gao, Yang; Jia, Xingcan; Sheng, Jiujiang

    2015-09-30

    In this study, the effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO2), and ozone (O3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (Nratio) and S from SO2 to sulfate (Sratio) bothmore » significantly increased in haze events, suggesting enhanced conversions from NOx and SO2 to their corresponding particle phases in the late haze period. Further analysis shows that Nratio and Sratio increased with increasing RH, with Nratio and Sratio being only 0.04 and 0.03, respectively, when RH < 40%, and increasing up to 0.16 and 0.12 when RH reached 60–80%, respectively. The enhanced conversion ratios of N and S in the late haze period is likely due to heterogeneous aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of Nratio and Sratio to O3: the conversion ratios increase with decreasing O3 concentration when O3 concentration is lower than <15 ppb but increased with increasing O3 when O3 concentration is higher than 15 ppb. The results suggest that heterogeneous aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly due to high emission and low reaction rate; the occurrence of heterogeneous aqueous reactions in the late haze period, together with the accumulated high concentrations of precursor gases such as SO2 and NOx, accelerated the

  11. Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

    SciTech Connect

    Quan, Jiannong; Liu, Yangang; Liu, Quan; Li, Xia; Gao, Yang; Jia, Xingcan; Sheng, Jiujiang

    2015-09-30

    In this study, the effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO2), and ozone (O3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (Nratio) and S from SO2 to sulfate (Sratio) both significantly increased in haze events, suggesting enhanced conversions from NOx and SO2 to their corresponding particle phases in the late haze period. Further analysis shows that Nratio and Sratio increased with increasing RH, with Nratio and Sratio being only 0.04 and 0.03, respectively, when RH < 40%, and increasing up to 0.16 and 0.12 when RH reached 60–80%, respectively. The enhanced conversion ratios of N and S in the late haze period is likely due to heterogeneous aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of Nratio and Sratio to O3: the conversion ratios increase with decreasing O3 concentration when O3 concentration is lower than <15 ppb but increased with increasing O3 when O3 concentration is higher than 15 ppb. The results suggest that heterogeneous aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly

  12. A new source of methyl glyoxal in the aqueous phase

    NASA Astrophysics Data System (ADS)

    Rodigast, M.; Mutzel, A.; Schindelka, J.; Herrmann, H.

    2015-11-01

    Carbonyl compounds are ubiquitous in atmospheric multiphase system participating in gas, particle, and aqueous-phase chemistry. One important compound is methyl ethyl ketone (MEK), as it is detected in significant amounts in the gas phase as well as in cloud water, ice, and rain. Consequently, it can be expected that MEK influences the liquid phase chemistry. Therefore, the oxidation of MEK and the formation of corresponding oxidation products were investigated in the aqueous phase. Several oxidation products were identified from the oxidation with OH radicals, including 2,3-butanedione, hydroxyacetone, and methyl glyoxal. The molar yields were 29.5 % for 2,3-butanedione, 3.0 % for hydroxyacetone, and 9.5 % for methyl glyoxal. Since methyl glyoxal is often related to the formation of organics in the aqueous phase, MEK should be considered for the formation of aqueous secondary organic aerosol (aqSOA). Based on the experimentally obtained data, a reaction mechanism for the formation of methyl glyoxal has been developed and evaluated with a model study. Besides known rate constants, the model contains measured photolysis rate constants for MEK (kp = 5 × 10-5 s-1), 2,3-butanedione (kp = 9 × 10-6 s-1), methyl glyoxal (kp = 3 × 10-5 s-1), and hydroxyacetone (kp = 2 × 10-5 s-1). From the model predictions, a branching ratio of 60/40 for primary/secondary H-atom abstraction at the MEK skeleton was found. This branching ratio reproduces the experiment results very well, especially the methyl glyoxal formation, which showed excellent agreement. Overall, this study demonstrates MEK as a methyl glyoxal precursor compound for the first time.

  13. A new source of methylglyoxal in the aqueous phase

    NASA Astrophysics Data System (ADS)

    Rodigast, Maria; Mutzel, Anke; Schindelka, Janine; Herrmann, Hartmut

    2016-03-01

    Carbonyl compounds are ubiquitous in atmospheric multiphase system participating in gas, particle, and aqueous-phase chemistry. One important compound is methyl ethyl ketone (MEK), as it is detected in significant amounts in the gas phase as well as in cloud water, ice, and rain. Consequently, it can be expected that MEK influences the liquid-phase chemistry. Therefore, the oxidation of MEK and the formation of corresponding oxidation products were investigated in the aqueous phase. Several oxidation products were identified from the oxidation with OH radicals, including 2,3-butanedione, hydroxyacetone, and methylglyoxal. The molar yields were 29.5 % for 2,3-butanedione, 3.0 % for hydroxyacetone, and 9.5 % for methylglyoxal. Since methylglyoxal is often related to the formation of organics in the aqueous phase, MEK should be considered for the formation of aqueous secondary organic aerosol (aqSOA). Based on the experimentally obtained data, a reaction mechanism for the formation of methylglyoxal has been developed and evaluated with a model study. Besides known rate constants, the model contains measured photolysis rate constants for MEK (kp = 5 × 10-5 s-1), 2,3-butanedione (kp = 9 × 10-6 s-1), methylglyoxal (kp = 3 × 10-5 s-1), and hydroxyacetone (kp = 2 × 10-5 s-1). From the model predictions, a branching ratio of 60 /40 for primary/secondary H-atom abstraction at the MEK skeleton was found. This branching ratio reproduces the experiment results very well, especially the methylglyoxal formation, which showed excellent agreement. Overall, this study demonstrates MEK as a methylglyoxal precursor compound for the first time.

  14. Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols

    NASA Astrophysics Data System (ADS)

    Riedel, T. P.; Lin, Y.-H.; Zhang, Z.; Chu, K.; Thornton, J. A.; Vizuete, W.; Gold, A.; Surratt, J. D.

    2016-02-01

    Isomeric epoxydiols from isoprene photooxidation (IEPOX) have been shown to produce substantial amounts of secondary organic aerosol (SOA) mass and are therefore considered a major isoprene-derived SOA precursor. Heterogeneous reactions of IEPOX on atmospheric aerosols form various aerosol-phase components or "tracers" that contribute to the SOA mass burden. A limited number of the reaction rate constants for these acid-catalyzed aqueous-phase tracer formation reactions have been constrained through bulk laboratory measurements. We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations, and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

  15. Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols

    NASA Astrophysics Data System (ADS)

    Riedel, T. P.; Lin, Y.-H.; Zhang, Z.; Chu, K.; Thornton, J. A.; Vizuete, W.; Gold, A.; Surratt, J. D.

    2015-10-01

    Isomeric epoxydiols from isoprene photooxidation (IEPOX) have been shown to produce substantial amounts of secondary organic aerosol (SOA) mass and are therefore considered a major isoprene-derived SOA precursor. Heterogeneous reactions of IEPOX on atmospheric aerosols form various aerosol-phase components or "tracers" that contribute to the SOA mass burden. A limited number of the reaction rate constants for these acid-catalyzed aqueous-phase tracer formation reactions have been constrained through bulk laboratory measurements. We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall-losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations, and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

  16. Phase transitions and morphologies of aerosol particles

    NASA Astrophysics Data System (ADS)

    Song, M.; Marcolli, C.; Krieger, U.; Zuend, A.; Peter, T.

    2012-12-01

    Tropospheric aerosol particles consisting of complex mixtures of organic compounds, ammonium sulfate (AS) and water undergo phase transitions such as liquid-liquid phase separation (LLPS), efflorescence and deliquescence as a consequence of changes in ambient relative humidity (RH). These phase transitions in the mixed aerosol particles may lead to different particle configurations such as core-shell or partially engulfed structures. However, the physical states and morphologies of these aerosol particles are still poorly understood. In this study, we investigate the phase transitions and morphological changes of various internally mixed organics/AS/water particles with different organic-to-inorganic ratios (OIR), namely OIR = 6:1, 2:1, 1:2 and 1:6 during humidity cycles using optical microscopy and Raman spectroscopy. Particularly, we explore how the properties of different organic functional groups and the compositional complexity of the organic aerosol fraction influence the occurrence of LLPS in the relationship with the organic oxygen-to-carbon (O:C) ratios. We found that LLPS occurred for all mixtures with O:C < 0.56, for none of the mixtures with O:C > 0.80, and depended on the specific types and compositions of organic functional groups for 0.56 < O:C < 0.80. Moreover, the number of mixture components and the spread of the O:C range did not notably influence the conditions for LLPS to occur. Since in ambient aerosols O:C and OIR range typically between 0.2 and 1.0, and between 4:1 and 1:5, respectively, LLPS is expected to be a common feature of tropospheric aerosols. AS in the mixed particles effloresced between 0 and 47 %RH and deliquesced between 71 and 80 %RH during humidity cycles. Compared to a deliquescence relative humidity (DRH) of 80 % for pure AS, the DRH in the mixed particles showed slightly lower values. A strong reduction or complete inhibition of efflorescence occurred for mixtures with high OIR that did not exhibit LLPS. Both core-shell and

  17. Glyoxal processing outside clouds: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Volkamer, R.

    2010-05-01

    This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions in aqueous aerosol particles that form secondary organic aerosol (SOA). Recent laboratory results on glyoxal reactions are reviewed and a consistent set of reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds to form (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles compared to cloud droplets and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry. The application of this new module in a chemical box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the atmospheric relevance of SOA formation from glyoxal. During day time a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ~5 μg m-3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5

  18. ON-LINE ANALYSIS OF AQUEOUS AEROSOLS BY LASER DESORPTION IONIZATION. (R823980)

    EPA Science Inventory

    In this work the effects of water on the laser desorption ionization mass spectra of single aerosol particles are explored. Aqueous aerosols are produced by passing dry particles through a humid environment so that they undergo deliquescent growth. Laser desorption ionization is ...

  19. Comparison of Fe(II) Photo-Formation Characteristics Between Aqueous Humic Acid Solutions and Aqueous Extracts of Atmospheric Aerosols Collected at Okinawa Island, Japan

    NASA Astrophysics Data System (ADS)

    Saito, K.; Okada, K.; Arakaki, T.

    2007-12-01

    Photochemical cycles of Fe(III)-Fe(II) affects the oxidation and the reduction of transient species such as active oxygen species and various transition metals in the atmospheric condensed phases. Although the importance of organic ligands to iron cycling (e.g. ligand-to-metal charge transfer) is becoming clearer, the mechanism by which photochemical reduction of Fe(III) to Fe(II) are not well understood. Humic acid (HA) is considered as an important organic ligand for Fe(III) complexes in the environment. HA is a collection of organic compounds that exist in nature but whose structures are not well known. Commercially available HAs as received from the manufacturers contain trace amount of iron. Using this residual Fe, we investigated the photochemical formation of Fe(II) in aqueous HA solutions to elucidate the photochemical cycles of Fe(III)-Fe(II) in the atmospheric water drops. We purchased HAs from several different suppliers. We investigated the effects of pH and wavelengths on Fe(II) photo-formation using monochromatic radiations at 313, 334, 366, and 405 nm. Concentrations of photochemically formed Fe(II) were determined by ferrozine-HPLC technique, and the apparent quantum yields were determined based on the total absorbance of the HA solutions. Fe(II) photo-formation characteristics of the aqueous humic acid solutions purchased from different suppliers showed slightly different wavelength dependence. Furthermore, we compared Fe(II) photoformation characteristics observed in aqueous HA solutions with those in the aqueous extracts of atmospheric aerosols collected in Okinawa, Japan. The results showed that the apparent quantum yields of the aerosol extracts were 5-10 times higher than those of the HA solutions. Wavelength-dependence of Fe(II) photo-formation observed in the aqueous extracts of aerosols was similar to that seen in the aqueous HA solutions.

  20. Aqueous phase oxidation of sulphur dioxide by ozone in cloud droplets

    NASA Astrophysics Data System (ADS)

    Hoyle, C. R.; Fuchs, C.; Järvinen, E.; Saathoff, H.; Dias, A.; El Haddad, I.; Gysel, M.; Coburn, S. C.; Tröstl, J.; Bernhammer, A.-K.; Bianchi, F.; Breitenlechner, M.; Corbin, J. C.; Craven, J.; Donahue, N. M.; Duplissy, J.; Ehrhart, S.; Frege, C.; Gordon, H.; Höppel, N.; Heinritzi, M.; Kristensen, T. B.; Molteni, U.; Nichman, L.; Pinterich, T.; Prévôt, A. S. H.; Simon, M.; Slowik, J. G.; Steiner, G.; Tomé, A.; Vogel, A. L.; Volkamer, R.; Wagner, A. C.; Wagner, R.; Wexler, A. S.; Williamson, C.; Winkler, P. M.; Yan, C.; Amorim, A.; Dommen, J.; Curtius, J.; Gallagher, M. W.; Flagan, R. C.; Hansel, A.; Kirkby, J.; Kulmala, M.; Möhler, O.; Stratmann, F.; Worsnop, D.; Baltensperger, U.

    2015-12-01

    The growth of aerosol due to the aqueous phase oxidation of SO2 by O3 was measured in laboratory generated clouds created in the CLOUD chamber at CERN. Experiments were performed at 10 and -10 °C, on acidic (sulphuric acid) and on partially to fully neutralised (ammonium sulphate) seed aerosol. Clouds were generated by performing an adiabatic expansion - pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted by oxidation rates previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and -10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system are well represented by accepted rates, based on bulk measurements. To the best of our knowledge, these are the first laboratory based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rates to temperatures below 0 °C is correct.

  1. Aqueous phase oxidation of sulphur dioxide by ozone in cloud droplets

    NASA Astrophysics Data System (ADS)

    Hoyle, C. R.; Fuchs, C.; Järvinen, E.; Saathoff, H.; Dias, A.; El Haddad, I.; Gysel, M.; Coburn, S. C.; Tröstl, J.; Bernhammer, A.-K.; Bianchi, F.; Breitenlechner, M.; Corbin, J. C.; Craven, J.; Donahue, N. M.; Duplissy, J.; Ehrhart, S.; Frege, C.; Gordon, H.; Höppel, N.; Heinritzi, M.; Kristensen, T. B.; Molteni, U.; Nichman, L.; Pinterich, T.; Prévôt, A. S. H.; Simon, M.; Slowik, J. G.; Steiner, G.; Tomé, A.; Vogel, A. L.; Volkamer, R.; Wagner, A. C.; Wagner, R.; Wexler, A. S.; Williamson, C.; Winkler, P. M.; Yan, C.; Amorim, A.; Dommen, J.; Curtius, J.; Gallagher, M. W.; Flagan, R. C.; Hansel, A.; Kirkby, J.; Kulmala, M.; Möhler, O.; Stratmann, F.; Worsnop, D. R.; Baltensperger, U.

    2016-02-01

    The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). Experiments were performed at 10 and -10 °C, on acidic (sulfuric acid) and on partially to fully neutralised (ammonium sulfate) seed aerosol. Clouds were generated by performing an adiabatic expansion - pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and -10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system can be well represented by using accepted rate constants, based on bulk measurements. To the best of our knowledge, these are the first laboratory-based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rate constants to temperatures below 0 °C is correct.

  2. A Computationally Efficient Algorithm for Aerosol Phase Equilibrium

    SciTech Connect

    Zaveri, Rahul A.; Easter, Richard C.; Peters, Len K.; Wexler, Anthony S.

    2004-10-04

    Three-dimensional models of atmospheric inorganic aerosols need an accurate yet computationally efficient thermodynamic module that is repeatedly used to compute internal aerosol phase state equilibrium. In this paper, we describe the development and evaluation of a computationally efficient numerical solver called MESA (Multicomponent Equilibrium Solver for Aerosols). The unique formulation of MESA allows iteration of all the equilibrium equations simultaneously while maintaining overall mass conservation and electroneutrality in both the solid and liquid phases. MESA is unconditionally stable, shows robust convergence, and typically requires only 10 to 20 single-level iterations (where all activity coefficients and aerosol water content are updated) per internal aerosol phase equilibrium calculation. Accuracy of MESA is comparable to that of the highly accurate Aerosol Inorganics Model (AIM), which uses a rigorous Gibbs free energy minimization approach. Performance evaluation will be presented for a number of complex multicomponent mixtures commonly found in urban and marine tropospheric aerosols.

  3. The signature of aqueous phase SOA: Evidence from field and model studies

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Sorooshian, A.; Carlton, A. G.

    2012-12-01

    While over the past years great progress has been made to predict the total mass of secondary organic aerosol (SOA), many models fail to predict specific SOA properties such as degree of oxygenation (O/C ratio), size and size-resolved product distribution. These model/observation discrepancies could be (partially) explained by SOA formation processes that occur in the aqueous phase of cloud droplets and deliquesced aerosol particles. We will present results from model and field studies that clearly reveal that aqueous-phase processed organic aerosol exhibits a different 'signature' in terms of these properties that allow distinguishing the SOA sources from the more traditional SOA formation processes, i.e. condensation of low-volatility and semivolatile gas phase products into dry organic matter. Process models with detailed organic aqueous phase chemistry will be applied in order to predict small scale features such as the processing of size distributions and the formation of specific products (e.g. oxalate and related compounds). While such detail cannot be implemented in large scale applications, results from a regional model (CMAQ) that includes parameterized aqueous phase SOA production will be presented and the impact of organic cloud chemistry on a wider scale and vertical aerosol distributions will be discussed. Several recent airborne studies have shown that organic mass is produced in clouds, and cloud droplet residuals contain a higher highly-oxygenated organic fraction as compared to particles that are processed in clear-sky air. Thus, while the evidence of aqueous phase SOA is very clear in the vicinity of clouds, we will track this signature and show data from surface measurements where product, hygroscopicity and size distributions of processed aerosol still show evidence of recent aqueous phase processing. These observational data will be discussed in the context of the predicted aqueous phase SOA properties. Our results will give guidance for the

  4. Non-Aqueous Phase Liquid Calculator

    2004-02-19

    Non-Aqueous Phase Liquid or "NPAL" is a term that most environmental professionals are familiar with because NAPL has been recognized in the literature as a significant source of groundwater contamination. There are two types of NAPL: DNAPL and LNAPL. DNAPL is a ‘dense’ non-aqueous phase liquid. In this context, dense means having a density greater than water (1.0 kg/L). Trichloroethylene (TCE) and tetrachioroethylene (PCE) are examples of DNAPL compounds. A compound that is heaver thanmore » water means this type of NAPL will sink in an aquifer. Conversely, LNAPL is a ‘light’ non-aqueous phase liquid with a density less than water, and will float on top of the aquifer. Examples of LNAPL’s are benzene and toluene. LNAPL or DNAPL often manifest as a complex, multi-component mixture of organic compounds that can occur in environmental media. Complex multi-component mixtures distributed in soil pore-air, pore-water, soil particles and in free phase complicate residual saturation of single and multi component NAPL compounds in soil samples. The model output also includes estimates of the NAPL mass and volume and other physical and chemical properties that may be useful for characterization, modeling, and remedial system design and operation. The discovery of NAPL in the aquifer usually leads to a focused characterization for possible sources of NAPL in the vadose zone using a variety of innovative technologies and characterization methods. Often, the analytical data will indicated the presence of NAPL, yet, the NAPL will go unrecognized. Failure to recognize the NAPL can be attributed to the complicated processes of inter-media transfer or a general lack of knowledge about the physical characteristics of complex organic mixtures in environmental samples.« less

  5. Volatility and oxidative aging of aqueous maleic acid aerosol droplets and the dependence on relative humidity.

    PubMed

    Dennis-Smither, Benjamin J; Marshall, Frances H; Miles, Rachael E H; Preston, Thomas C; Reid, Jonathan P

    2014-07-31

    The microphysical structure and heterogeneous oxidation by ozone of single aerosol particles containing maleic acid (MA) has been studied using aerosol optical tweezers and cavity enhanced Raman spectroscopy. The evaporation rate of MA from aqueous droplets has been measured over a range of relative humidities and the pure component vapor pressure determined to be (1.7 ± 0.2) × 10(-3) Pa. Variation in the refractive index (RI) of an aqueous MA droplet with relative humidity (RH) allowed the subcooled liquid RI of MA to be estimated as 1.481 ± 0.001. Measurements of the hygroscopic growth are shown to be consistent with equilibrium model predictions from previous studies. Simultaneous measurements of the droplet composition, size, and refractive index have been made during ozonolysis at RHs in the range 50-80%, providing insight into the volatility of organic products, changes in the droplet hygroscopicity, and optical properties. Exposure of the aqueous droplets to ozone leads to the formation of products with a wide range of volatilities spanning from involatile to volatile. Reactive uptake coefficients show a weak dependence on ozone concentration, but no dependence on RH or salt concentration. The time evolving RI depends significantly on the RH at which the oxidation proceeds and can even show opposing trends; while the RI increases with ozone exposure at low relative humidity, the RI decreases when the oxidation proceeds at high relative humidity. The variations in RI are broadly consistent with a framework for predicting RIs for organic components published by Cappa et al. ( J. Geophys. Res. 2011 , 116 , D15204 ). Once oxidized, particles are shown to form amorphous phases on drying rather than crystallization, with slow evaporation kinetics of residual water. PMID:25003240

  6. Exploring Atmospheric Aqueous Chemistry (and Secondary Organic Aerosol Formation) through OH Radical Oxidation Experiments, Droplet Evaporation and Chemical Modeling

    NASA Astrophysics Data System (ADS)

    Turpin, B. J.; Kirkland, J. R.; Lim, Y. B.; Ortiz-Montalvo, D. L.; Sullivan, A.; Häkkinen, S.; Schwier, A. N.; Tan, Y.; McNeill, V. F.; Collett, J. L.; Skog, K.; Keutsch, F. N.; Sareen, N.; Carlton, A. G.; Decesari, S.; Facchini, C.

    2013-12-01

    Gas phase photochemistry fragments and oxidizes organic emissions, making water-soluble organics ubiquitous in the atmosphere. My group and others have found that several water-soluble compounds react further in the aqueous phase forming low volatility products under atmospherically-relevant conditions (i.e., in clouds, fogs and wet aerosols). Thus, secondary organic aerosol can form as a result of gas followed by aqueous chemistry (aqSOA). We have used aqueous OH radical oxidation experiments coupled with product analysis and chemical modeling to validate and refine the aqueous chemistry of glyoxal, methylglyoxal, glycolaldehyde, and acetic acid. The resulting chemical model has provided insights into the differences between oxidation chemistry in clouds and in wet aerosols. Further, we conducted droplet evaporation experiments to characterize the volatility of the products. Most recently, we have conducted aqueous OH radical oxidation experiments with ambient mixtures of water-soluble gases to identify additional atmospherically-important precursors and products. Specifically, we scrubbed water-soluble gases from the ambient air in the Po Valley, Italy using four mist chambers in parallel, operating at 25-30 L min-1. Aqueous OH radical oxidation experiments and control experiments were conducted with these mixtures (total organic carbon ≈ 100 μM-C). OH radicals (3.5E-2 μM [OH] s-1) were generated by photolyzing H2O2. Precursors and products were characterized using electrospray ionization mass spectrometry (ESI-MS), ion chromatography (IC), IC-ESI-MS, and ultra high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chemical modeling suggests that organic acids (e.g., oxalate, pyruvate, glycolate) are major products of OH radical oxidation at cloud-relevant concentrations, whereas organic radical - radical reactions result in the formation of oligomers in wet aerosols. Products of cloud chemistry and droplet evaporation have

  7. Assessing known pathways for HO2 loss in aqueous atmospheric aerosols: Regional and global impacts on tropospheric oxidants

    NASA Astrophysics Data System (ADS)

    Thornton, Joel A.; Jaeglé, Lyatt; McNeill, V. Faye

    2008-03-01

    We present a study of the potential importance of known reaction pathways for HO2 loss in atmospheric aerosols. As a baseline case, we calculate the reaction probability for HO2 loss by its self-reaction in aqueous particles. Detailed calculations assessed the effects of aerosol pH, temperature, particle size, and aqueous phase diffusion limitations on the rate of HO2 loss by this process. An algebraic parameterization of the reaction probability, γHO2, due to self-reaction is valid for aerosol pH < 6 and the existence of a homogeneous gas-phase HOx source greater than 1 × 105 molec cm-3 s-1. In this formulation γHO2 depends strongly on particle phase, size, pH and temperature; the latter causing γHO2 > 0.1 in the upper troposphere and γHO2 < 0.01 in the extra-polar lower troposphere. We contrast the self-reaction pathway with catalytic oxidation by dissolved Cu ions. Using IMPROVE network data we assess the atmospheric importance and uncertainties associated with the Cu pathway. Simulations of tropospheric chemistry were performed using the GEOS-Chem global chemical transport model with different parameterizations of γHO2. Relative to simulations where γHO2 = 0 for all aerosol types, assuming that only the aqueous-phase self-reaction proceeds on pollution and sea salt particles causes global annual mean differences in surface OH, HO2, and H2O2 of -1, -2, and +2%, respectively. These minor effects of heterogeneous loss are significantly different from a simulation assuming γHO2 = 0.2 on all particles, as is currently recommended, with implications for predictions of regional HOx levels, ozone production rates and their sensitivity to NOx.

  8. Phase behavior of DODAB aqueous solution

    SciTech Connect

    Voronov, V. P.; Kuryakov, V. N.; Muratov, A. R.

    2012-12-15

    Phase behavior of DODAB aqueous solution, prepared without sonication, was studied by adiabatic scanning calorimetry. Measurements revealed four phase transitions with the temperatures 35.2, 39.6, 44.6, and 52.4 Degree-Sign C at heating and one transition at the temperature 40.4 Degree-Sign C at cooling. The first three transitions at heating occur in unilamellar vesicles. The first and third transitions correspond to the subgel-gel and gelliquid phase transitions, corresponding enthalpy jumps are equal to 33 and 49 kJ/mol. The second transition appears after some aging and is similar to gel-ripple phase transition in a DPPC solution, with the enthalpy jump under the transition exceeding 7.4 kJ/mol. The transition occurs in unilamellar vesicles. The transition at the temperature 52.4 Degree-Sign C occurs in another subsystem of the solution, which we believe to be multilamellar vesicles. The enthalpy jump at this transition is equal to 97 kJ/mol, and data analysis suggests that this is a subgel-liquid transition. The phase transition at cooling is the liquid-gel transition in unilamellar vesicles. During the measurements, a slow evolution of the solution occurs, consisting in a change of concentrations of unilamellar and multilamellar vesicles. This transformation mainly occurs at low temperatures.

  9. Comparison of Methods for Predicting the Compositional Dependence of the Density and Refractive Index of Organic-Aqueous Aerosols.

    PubMed

    Cai, Chen; Miles, Rachael E H; Cotterell, Michael I; Marsh, Aleksandra; Rovelli, Grazia; Rickards, Andrew M J; Zhang, Yun-Hong; Reid, Jonathan P

    2016-08-25

    Representing the physicochemical properties of aerosol particles of complex composition is of crucial importance for understanding and predicting aerosol thermodynamic, kinetic, and optical properties and processes and for interpreting and comparing analysis methods. Here, we consider the representations of the density and refractive index of aqueous-organic aerosol with a particular focus on the dependence of these properties on relative humidity and water content, including an examination of the properties of solution aerosol droplets existing at supersaturated solute concentrations. Using bulk phase measurements of density and refractive index for typical organic aerosol components, we provide robust approaches for the estimation of these properties for aerosol at any intermediate composition between pure water and pure solute. Approximately 70 compounds are considered, including mono-, di- and tricarboxylic acids, alcohols, diols, nitriles, sulfoxides, amides, ethers, sugars, amino acids, aminium sulfates, and polyols. We conclude that the molar refraction mixing rule should be used to predict the refractive index of the solution using a density treatment that assumes ideal mixing or, preferably, a polynomial dependence on the square root of the mass fraction of solute, depending on the solubility limit of the organic component. Although the uncertainties in the density and refractive index predictions depend on the range of subsaturated compositional data available for each compound, typical errors for estimating the solution density and refractive index are less than ±0.1% and ±0.05%, respectively. Owing to the direct connection between molar refraction and the molecular polarizability, along with the availability of group contribution models for predicting molecular polarizability for organic species, our rigorous testing of the molar refraction mixing rule provides a route to predicting refractive indices for aqueous solutions containing organic molecules

  10. Comparison of Methods for Predicting the Compositional Dependence of the Density and Refractive Index of Organic-Aqueous Aerosols.

    PubMed

    Cai, Chen; Miles, Rachael E H; Cotterell, Michael I; Marsh, Aleksandra; Rovelli, Grazia; Rickards, Andrew M J; Zhang, Yun-Hong; Reid, Jonathan P

    2016-08-25

    Representing the physicochemical properties of aerosol particles of complex composition is of crucial importance for understanding and predicting aerosol thermodynamic, kinetic, and optical properties and processes and for interpreting and comparing analysis methods. Here, we consider the representations of the density and refractive index of aqueous-organic aerosol with a particular focus on the dependence of these properties on relative humidity and water content, including an examination of the properties of solution aerosol droplets existing at supersaturated solute concentrations. Using bulk phase measurements of density and refractive index for typical organic aerosol components, we provide robust approaches for the estimation of these properties for aerosol at any intermediate composition between pure water and pure solute. Approximately 70 compounds are considered, including mono-, di- and tricarboxylic acids, alcohols, diols, nitriles, sulfoxides, amides, ethers, sugars, amino acids, aminium sulfates, and polyols. We conclude that the molar refraction mixing rule should be used to predict the refractive index of the solution using a density treatment that assumes ideal mixing or, preferably, a polynomial dependence on the square root of the mass fraction of solute, depending on the solubility limit of the organic component. Although the uncertainties in the density and refractive index predictions depend on the range of subsaturated compositional data available for each compound, typical errors for estimating the solution density and refractive index are less than ±0.1% and ±0.05%, respectively. Owing to the direct connection between molar refraction and the molecular polarizability, along with the availability of group contribution models for predicting molecular polarizability for organic species, our rigorous testing of the molar refraction mixing rule provides a route to predicting refractive indices for aqueous solutions containing organic molecules

  11. Aqueous Oxidation of Green Leaf Volatiles as a Source of Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Richards-Henderson, N. K.; Hansel, A.; Pham, A. T.; Vempati, H. S.; Valsaraj, K. T.; Anastasio, C.

    2013-12-01

    Vegetation emits volatile oxygenated hydrocarbons - the green leaf volatiles (GLVs) - which are formed from the biochemical conversion of linoleic and linolenic acids within plant cells. Stress or damage to vegetation can significantly elevate emission fluxes of these compounds, some of which are fairly water soluble. Aqueous-phase reactions of the GLVs with photochemically generated oxidants - such as hydroxyl radical (OH), singlet oxygen (1O2) and excited triplet states of organic compounds (3C*) _ might then form low-volatility products that can act as secondary organic aerosol (SOA). In order to determine if GLVs can be a significant source of secondary organic carbon in fogwater, studies of GLVs in laboratory solutions are needed to elucidate the oxidation kinetics and the corresponding SOA mass yields. In this study we are determining the second-order rate constants, and SOA mass yields, for five GLVs (cis-3-hexen-1-ol, cis-3-hexenylacetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol) reacting with OH,1O2 and 3C*. Experiments are performed at relevant fog water pHs, temperatures, and oxidant concentrations. Rate constants are determined using a relative rate approach in which the decay of GLVs and reference compounds are monitored as function of time by HPLC. The capacity of GLVs to form aqueous SOA was determined by following the formation of their decomposition products with HPLC-UV/DAD and HPLC-ESI/MS. SOA mass yields are measured gravimetrically from laboratory solutions containing atmospherically relevant concentrations of photooxidants and GLVs, and irradiated with simulated sunlight. We will use our results to assess the potential contribution of aqueous GLV reactions as a source of SOA in cloudy or foggy atmospheres.

  12. Formation of Brown Aqueous Secondary Organic Aerosol during Multiphase Cloud Simulations using the CESAM Chamber Facility

    NASA Astrophysics Data System (ADS)

    Hawkins, L. N.; Welsh, H.; De Haan, D. O.; Doussin, J. F.; Pednekar, R.; Caponi, L.; Pangui, E.; Gratien, A.; Cazaunau, M.; Formenti, P.; Pajunoja, A.

    2015-12-01

    We investigated the formation of aqueous brown carbon (aqBrC) from methylglyoxal and methylamine in multiphase reactions using the CESAM chamber facility at the University Paris-Est Creteil. Following reaction in the chamber, droplets and particles were sampled with a Particle-Into-Liquid-Sampler (PILS), a capillary waveguide cell for UV/visible spectroscopy, and a total organic carbon analyzer (TOC). Particle size distributions were measured with a scanning mobility particle sizer and used to determine the mass absorption coefficient (a normalized absorbance measurement). Absorption spectra were recorded while aerosol or gas phase aqBrC precursors were introduced into the humid chamber. Sampling was continuous during and after cloud events. The events lasted 5-10 minutes and produced measurable brown carbon signal at 365 nm. When lights were used, absorbance at 365 nm decreased steadily indicating photobleaching of aqBrC products or preferential formation of different, non-absorbing products. Although absorptivity increases prior to cloud formation, cloud events produce sharp increased in aqBrC absorptivity. While measurable absorbance at 365 nm indicates aqBrC formation, very little absorbance was recorded beyond 450 nm indicating that the products were not as oligomerized as products observed in prior work in multi-day, bulk phase simulations.

  13. Tunable aqueous polymer-phase impregnated resins-technology-a novel approach to aqueous two-phase extraction.

    PubMed

    van Winssen, F A; Merz, J; Schembecker, G

    2014-02-14

    Aqueous Two-Phase Extraction (ATPE) represents a promising unit operation for downstream processing of biotechnological products. The technique provides several advantages such as a biocompatible environment for the extraction of sensitive and biologically active compounds. However, the tendency of some aqueous two-phase systems to form intensive and stable emulsions can lead to long phase separation times causing an increased footprint for the required mixer-settler devices or the need for additional equipment such as centrifuges. In this work, a novel approach to improve ATPE for downstream processing applications called 'Tunable Aqueous Polymer-Phase Impregnated Resins' (TAPPIR(®))-Technology is presented. The technology is based on the immobilization of one aqueous phase inside the pores of a solid support. The second aqueous phase forms the bulk liquid around the impregnated solids. Due to the immobilization of one phase, phase emulsification and phase separation of ATPE are realized in a single step. In this study, a biodegradable and sustainable aqueous two-phase system consisting of aqueous polyethylene glycol/sodiumcitrate solutions was chosen. The impregnation of different macroporous glass and ceramic solids was investigated and could be proven to be stable. Additionally, the separation of the dye Patent blue V was successfully performed with the TAPPIR(®)-Technology. Thus, the "proof of principle" of this technology is presented.

  14. Chemical characterization of the main products formed through aqueous-phase photonitration of guaiacol

    NASA Astrophysics Data System (ADS)

    Kitanovski, Z.; Čusak, A.; Grgić, I.; Claeys, M.

    2014-08-01

    Guaiacol (2-methoxyphenol) and its derivatives can be emitted into the atmosphere by thermal degradation (i.e., burning) of wood lignins. Due to its volatility, guaiacol is predominantly distributed atmospherically in the gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA) in the atmosphere. The main objectives of the present study were to chemically characterize the main products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of hydrogen peroxide and nitrite. The formed guaiacol reaction products were concentrated by solid-phase extraction and then purified with semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state proton, carbon-13 and two-dimensional nuclear magnetic resonance (NMR) spectroscopy, and direct infusion negative ion electrospray ionization tandem mass spectrometry ((-)ESI-MS/MS). The NMR and product ion (MS2) spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG), 6-nitroguaiacol (6NG), and 4,6-dinitroguaiacol (4,6DNG). Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia) by means of HPLC/(-)ESI-MS/MS. Owing to the strong absorption of ultraviolet and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

  15. Aqueous-phase story of isoprene - A mini-review and reaction with HONO

    NASA Astrophysics Data System (ADS)

    Rudziński, Krzysztof J.; Szmigielski, Rafał; Kuznietsova, Inna; Wach, Paulina; Staszek, Dorota

    2016-04-01

    Isoprene is a major biogenic hydrocarbon emitted to the atmosphere and a well-recognized player in atmospheric chemistry, formation of secondary organic aerosol and air quality. Most of the scientific work on isoprene has focused on the gas-phase and smog chamber processing while direct aqueous chemistry has escaped the major attention because physical solubility of isoprene in water is low. Therefore, this work recollects the results of genuine research carried on atmospherically relevant aqueous-phase transformations of isoprene. It clearly shows that isoprene dissolves in water and reacts in aqueous solutions with common atmospheric oxidants such as hydrogen peroxide, ozone, hydroxyl radicals, sulfate radicals and sulfite radicals. The reactions take place in the bulk of solutions or on the gas-liquid interfaces and often are acid-catalyzed and/or enhanced by light. The review is appended by an experimental study of the aqueous-phase reaction of isoprene with nitrous acid (HONO). The decay of isoprene and formation of new products are demonstrated. The tentative chemical mechanism of the reaction is suggested, which starts with slow decomposition of HONO to NO2 and NO. The aqueous chemistry of isoprene explains the formation of a few tropospheric components identified by scientists yet considered of unknown origin. The reaction of isoprene with sulfate radicals explains formation of the MW 182 organosulfate found in ambient aerosol and rainwater while the reaction of isoprene with HONO explains formation of the MW 129 and MW 229 nitroorganic compounds identified in rainwater. Thus, aqueous transformations of isoprene should not be neglected without evidence but rather considered and evaluated in modeling of atmospheric chemical processes even if alternative and apparently dominant heterogeneous pathways of isoprene transformation, dry or wet, are demonstrated.

  16. Modeling Gas-phase Glyoxal and Associated Secondary Organic Aerosol Formation in a Megacity using WRF/Chem

    NASA Astrophysics Data System (ADS)

    Wang, K.; Hodzic, A.; Barth, M. C.; Jimenez, J. L.; Volkamer, R.; Ervens, B.; Zhang, Y.

    2011-12-01

    Organic aerosol (OA) as one of a major fine particulate matter in the atmosphere plays an important role in air pollution, human health, and climate forcing. OA is composed of directly emitted primary organic aerosol and chemically produced secondary organic aerosols (SOA). Despite much recent progress in understanding SOA formation, current air quality models cannot explain the magnitude and growth of atmospheric SOA, due to high uncertainties in sources, properties, and chemical reactions of precursors and formation pathways of SOA. Recent laboratory and modeling studies showed that glyoxal may serve as an important SOA precursor in the condensed solution of inorganic or organic aerosol particles (e.g., ammonium sulfate, fulvic acid, and amino acids). In this study, the Weather Research and Forecasting model with chemistry (WRF/Chem) is modified to account for the latest observed gas-phase yields of glyoxal from various volatile organic compounds (VOCs) and the associated SOA formation in the aqueous aerosol phase. The SOA formation in the aqueous aerosol phase is implemented using two approaches. In the first approach, two simplified parameterizations are used to represent the lumped particle-phase chemical processes under dark conditions and photochemical surface uptake. In the second approach, more detailed kinetic glyoxal reactions such as reversible glyoxal uptake, dimer formation of glyoxal, and oligomerization are treated and resolved explicitly. The updated WRF/Chem is assessed over the Mexico City and the surrounding region during March 2006 using the MILAGRO campaign data. Various observations such as organic matter from Aerodyne Aerosol Mass Spectrometer and VOCs from Proton-transfer Ion Trap Mass Spectrometry were compared. The preliminary results showed that the addition of the SOA formation from glyoxal in aqueous particles brings SOA predictions into a better agreement with field observations, in particular in presence of high relative humidity

  17. Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols.

    PubMed

    McNeill, V Faye

    2015-02-01

    Over the past decade, it has become clear that aqueous chemical processes occurring in cloud droplets and wet atmospheric particles are an important source of organic atmospheric particulate matter. Reactions of water-soluble volatile (or semivolatile) organic gases (VOCs or SVOCs) in these aqueous media lead to the formation of highly oxidized organic particulate matter (secondary organic aerosol; SOA) and key tracer species, such as organosulfates. These processes are often driven by a combination of anthropogenic and biogenic emissions, and therefore their accurate representation in models is important for effective air quality management. Despite considerable progress, mechanistic understanding of some key aqueous processes is still lacking, and these pathways are incompletely represented in 3D atmospheric chemistry and air quality models. In this article, the concepts, historical context, and current state of the science of aqueous pathways of SOA formation are discussed.

  18. Phase, morphology, and hygroscopicity of mixed oleic acid/sodium chloride/water aerosol particles before and after ozonolysis.

    PubMed

    Dennis-Smither, Benjamin J; Hanford, Kate L; Kwamena, Nana-Owusua A; Miles, Rachael E H; Reid, Jonathan P

    2012-06-21

    Aerosol optical tweezers are used to probe the phase, morphology, and hygroscopicity of single aerosol particles consisting of an inorganic component, sodium chloride, and a water insoluble organic component, oleic acid. Coagulation of oleic acid aerosol with an optically trapped aqueous sodium chloride droplet leads to formation of a phase-separated particle with two partially engulfed liquid phases. The dependence of the phase and morphology of the trapped particle with variation in relative humidity (RH) is investigated by cavity enhanced Raman spectroscopy over the RH range <5% to >95%. The efflorescence and deliquescence behavior of the inorganic component is shown to be unaffected by the presence of the organic phase. Whereas efflorescence occurs promptly (<1 s), the deliquescence process requires both dissolution of the inorganic component and the adoption of an equilibrium morphology for the resulting two phase particle, occurring on a time-scale of <20 s. Comparative measurements of the hygroscopicity of mixed aqueous sodium chloride/oleic acid droplets with undoped aqueous sodium chloride droplets show that the oleic acid does not impact on the equilibration partitioning of water between the inorganic component and the gas phase or the time response of evaporation/condensation. The oxidative aging of the particles through reaction with ozone is shown to increase the hygroscopicity of the organic component.

  19. Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

    PubMed

    Smith, Jeremy D; Kinney, Haley; Anastasio, Cort

    2015-04-21

    Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

  20. Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

    NASA Astrophysics Data System (ADS)

    Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

    2012-09-01

    The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (<2%) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

  1. Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

    NASA Astrophysics Data System (ADS)

    Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

    2013-01-01

    The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

  2. Catalyst and method for aqueous phase reactions

    DOEpatents

    Elliott, Douglas C.; Hart, Todd R.

    1999-01-01

    The present invention is a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional metal deposited onto the support in a second dispersed phase. The additional metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase without substantially affecting the catalytic activity, thereby increasing the life time of the catalyst.

  3. Brown carbon formation by aqueous-phase carbonyl compound reactions with amines and ammonium sulfate.

    PubMed

    Powelson, Michelle H; Espelien, Brenna M; Hawkins, Lelia N; Galloway, Melissa M; De Haan, David O

    2014-01-21

    Reactions between small water-soluble carbonyl compounds, ammonium sulfate (AS), and/or amines were evaluated for their ability to form light-absorbing species in aqueous aerosol. Aerosol chemistry was simulated with bulk phase reactions at pH 4, 275 K, initial concentrations of 0.05 to 0.25 M, and UV-vis and fluorescence spectroscopy monitoring. Glycolaldehyde-glycine mixtures produced the most intense absorbance. In carbonyl compound reactions with AS, methylamine, or AS/glycine mixtures, product absorbance followed the order methylglyoxal > glyoxal > glycolaldehyde > hydroxyacetone. Absorbance extended into the visible, with a wavelength dependence fit by absorption Ångstrom coefficients (Å(abs)) of 2 to 11, overlapping the Å(abs) range of atmospheric, water-soluble brown carbon. Many reaction products absorbing between 300 and 400 nm were strongly fluorescent. On a per mole basis, amines are much more effective than AS at producing brown carbon. In addition, methylglyoxal and glyoxal produced more light-absorbing products in reactions with a 5:1 AS-glycine mixture than with AS or glycine alone, illustrating the importance of both organic and inorganic nitrogen in brown carbon formation. Through comparison to biomass burning aerosol, we place an upper limit on the contribution of these aqueous carbonyl-AS-amine reactions of ≤ 10% of global light absorption by brown carbon. PMID:24351110

  4. The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxy radical

    NASA Astrophysics Data System (ADS)

    Huang, D.; Zhang, X.; Chen, Z. M.; Zhao, Y.; Shen, X. L.

    2011-03-01

    Aqueous phase chemical processes of organic compounds in the atmosphere have received increasing attention, partly due to their potential contribution to the formation of secondary organic aerosol (SOA). Here, we analyzed the aqueous oxidation of isoprene in clouds and its reaction products, including carbonyl compounds and organic acids. We also performed a laboratory simulation to improve our understanding of the kinetics and mechanisms for the products of aqueous isoprene oxidation that are significant precursors of SOA; these included methacrolein (MACR), methyl vinyl ketone (MVK), methyl glyoxal (MG), and glyoxal (GL). We used a novel chemical titration method to monitor the concentration of isoprene in the aqueous phase. We used a box model to interpret the mechanistic differences between aqueous- and gas-phase OH radical-initiated isoprene oxidations. Our results were the first demonstration of the rate constant for the reaction between isoprene and OH radical in water, 3.50 (± 0.98) × 109 M-1 s-1 at 283 K. Molar yields were determined based on consumed isoprene. Of note, the ratio of the yields of MVK (18.9 ± 0.8%) to MACR (9.0 ± 1.1%) in the aqueous phase isoprene oxidation was approximately double that observed for the corresponding gas phase reaction. We hypothesized that this might be explained by a water-induced enhancement in the self-reaction of a hydroxy isoprene peroxyl radical (HOCH2C(CH3)(O2)CH = CH2) produced in the aqueous reaction. The observed yields for MG and GL were 11.4 ± 0.3% and 3.8 ± 0.1%, respectively. Model simulations indicated that several potential pathways may contribute to the formation of MG and GL. Finally, oxalic acid increased steadily throughout the course of the study, even after isoprene was consumed completely. The observed yield of oxalic acid was 26.2 ± 0.8% at 6 h. The observed carbon balance accounted for ~50% of the consumed isoprene. The presence of high-molecular-weight compounds may have accounted for a

  5. Formation of aqueous-phase α-hydroxyhydroperoxides (α-HHP): potential atmospheric impacts

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Lee, A. K. Y.; Soong, R.; Simpson, A. J.; Abbatt, J. P. D.

    2013-06-01

    The focus of this work is on quantifying the degree of the aqueous-phase formation of α-hydroxyhydroperoxides (α-HHPs) via reversible nucleophilic addition of H2O2 to aldehydes. Formation of this class of highly oxygenated organic hydroperoxides represents a poorly characterized aqueous-phase processing pathway that may lead to enhanced SOA formation and aerosol toxicity. Specifically, the equilibrium constants of α-HHP formation have been determined using proton nuclear-magnetic-resonance (1H NMR) spectroscopy and proton-transfer-reaction mass spectrometry (PTR-MS). Significant α-HHP formation was observed from formaldehyde, acetaldehyde, propionaldehyde, glycolaldehyde, glyoxylic acid, and methylglyoxal, but not from methacrolein and ketones. Low temperatures enhanced the formation of α-HHPs but slowed their formation rates. High inorganic salt concentrations shifted the equilibria toward the hydrated form of the aldehydes and slightly suppressed α-HHP formation. Using the experimental equilibrium constants, we predict the equilibrium concentration of α-HHPs to be in the μM level in cloud water, but it may also be present in the mM level in aerosol liquid water (ALW), where the concentrations of H2O2 and aldehydes can be high. Formation of α-HHPs in ALW may significantly affect the effective Henry's law constants of H2O2 and aldehydes but may not affect their gas-phase levels. The photochemistry and reactivity of this class of atmospheric species have not been studied.

  6. Formation of aqueous-phase α-hydroxyhydroperoxides (α-HHP): potential atmospheric impacts

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Lee, A. K. Y.; Soong, R.; Simpson, A. J.; Abbatt, J. P. D.

    2013-02-01

    The focus of this work is on quantifying the degree of the aqueous-phase formation of α-hydroxyhydroperoxides (α-HHPs) via reversible nucleophilic addition of H2O2 to aldehydes. Formation of this class of highly oxygenated organic hydroperoxides represents a poorly characterized aqueous-phase processing pathway that may lead to enhanced SOA formation and aerosol toxicity. Specifically, the equilibrium constants of α-HHP formation have been determined using proton nuclear resonance (1H NMR) spectroscopy and proton transfer reaction mass spectrometry (PTR-MS). Significant α-HHP formation was observed from formaldehyde, acetaldehyde, propionaldehyde, glycolaldehyde, glyoxylic acid, methylglyoxal, but not from methacrolein and ketones. Low temperatures enhanced the formation of α-HHPs but slowed their formation rates. High inorganic salt concentrations shifted the equilibria toward the hydrated form of the aldehydes and slightly suppressed α-HHP formation. Using the experimental equilibrium constants, we predict the equilibrium concentration of α-HHPs to be in the μM level in cloud water but may be present in the mM level in aerosol liquid water (ALW), where the concentrations of H2O2 and aldehydes can be high. Formation of α-HHPs in ALW may significantly affect the effective Henry's law constants of H2O2 and aldehydes but may not affect their gas-phase levels. The photochemistry and reactivity of this class of atmospheric species have not been studied.

  7. Polar Nephelometer Measurements of Aerosol Phase Functions: Calibration and Field Measurements in Hawaii and the UAE

    NASA Astrophysics Data System (ADS)

    Porter, J. N.

    2005-12-01

    A custom polar nephelometer was built to make open air aerosol phase function measurements. The system is calibrated using filtered air as well as known aerosols. Measurements of aerosol phase functions were made in Hawaii and the United Arab Emirates. Using Mie and Pollack and Cuzzi code, aerosol size distributions are inverted. Time permiting these results will be compared with aerosol size distribution measurements obtained by other techniques.

  8. Dry powders of stable protein formulations from aqueous solutions prepared using supercritical CO(2)-assisted aerosolization.

    PubMed

    Sellers, S P; Clark, G S; Sievers, R E; Carpenter, J F

    2001-06-01

    We report on the use of a new supercritical carbon dioxide-assisted aerosolization coupled with bubble drying technology to prepare stabilized, dry, finely divided powders from aqueous protein formulations. In this study, the feasibility of this new technology was tested using two model proteins, lysozyme and lactate dehydrogenase (LDH). In the absence of excipients, lysozyme was observed to undergo perturbations of secondary structure observed by solid-state infrared spectroscopy. In the presence of sucrose, this unfolding was minimized. Lysozyme did not, however, undergo irreversible loss of activity, as all lysozyme powders generated by supercritical CO(2)-assisted aerosolization (with or without excipients) regained almost complete activity on reconstitution. The more labile LDH suffered irrecoverable loss of activity on reconstituting after supercritical CO(2)-assisted aerosolization and bubble drying in the absence of carbohydrate stabilizers. LDH could be stabilized throughout the nebulization, drying, and rehydration processes with the addition of sucrose, and almost complete preservation of activity was achieved with the further addition of a surface active agent, such as Tween 20, to the aqueous formulation prior to processing.

  9. Aqueous Phase Photo-Oxidation of Succinic Acid: Changes in Hygroscopic Properties and Reaction Products

    NASA Astrophysics Data System (ADS)

    Hudson, P. K.; Ninokawa, A.; Hofstra, J.; de Lijser, P.

    2013-12-01

    Atmospheric aerosol particles have been identified as important factors in understanding climate change. The extent to which aerosols affect climate is determined, in part, by hygroscopic properties which can change as a result of atmospheric processing. Dicarboxylic acids, components of atmospheric aerosol, have a wide range of hygroscopic properties and can undergo oxidation and photolysis reactions in the atmosphere. In this study, the hygroscopic properties of succinic acid aerosol, a non-hygroscopic four carbon dicarboxylic acid, were measured with a humidified tandem differential mobility analyzer (HTDMA) and compared to reaction products resulting from the aqueous phase photo-oxidation reaction of hydrogen peroxide and succinic acid. Reaction products were determined and quantified using gas chromatography-flame ionization detection (GC-FID) and GC-mass spectrometry (GC-MS) as a function of hydrogen peroxide:succinic acid concentration ratio and photolysis time. Although reaction products include larger non-hygroscopic dicarboxylic acids (e.g. adipic acid) and smaller hygroscopic dicarboxylic acids (e.g. malonic and oxalic acids), comparison of hygroscopic growth curves to Zdanovskii-Stokes-Robinson (ZSR) predictions suggests that the hygroscopic properties of many of the product mixtures are largely independent of the hygroscopicity of the individual components. This study provides a framework for future investigations to fully understand and predict the role of chemical reactions in altering atmospheric conditions that affect climate.

  10. Control over hygroscopic growth of saline aqueous aerosol using Pluronic polymer additives.

    PubMed

    Haddrell, Allen E; Hargreaves, Graham; Davies, James F; Reid, Jonathan P

    2013-02-25

    The hygroscopic properties of an aerosol originating from a nebulizer solution can affect the extent of peripheral deposition within the respiratory tract, which in turn affects drug efficacy of drugs delivered to the lungs. Thus, the ability to tailor the degree and rate of hygroscopic growth of an aerosol produced by a nebulizer through modification of the formulation would serve to improve drug efficacy through targeted lung deposition. In this study, the kinetic and thermodynamic hygroscopic properties of sodium chloride aerosol mixed with commercially available Pluronic polymers, specifically F77 and F127, are reported using three complementary single aerosol analysis techniques, specifically aerosol optical tweezers, a double ring electrodynamic balance and a concentric cylinder electrodynamic balance. The F77 polymer is shown to have a predictable effect on the hygroscopic properties of the aerosol: the ability of the droplet to uptake water from the air depends on the solute weight percent of sodium chloride present in a linear dose dependant manner. Unlike the smaller F77, a non-linear relationship was observed for the larger molecular weight F127 polymer, with significant suppression of hygroscopic growth (>50% by mass) for solution aerosol containing even only 1 wt% of the polymer and 99 wt% sodium chloride. The suppression of growth is shown to be consistent with the formation of mixed phase aerosol particles containing hydrophilic inorganic rich domains and hydrophobic polymer rich domains that sequester some of the inorganic component, with the two phases responding to changes in relative humidity independently. This independence of coupling with the gas phase is apparent in both the equilibrium state and the kinetics of water evaporation/condensation. By starting with a saline nebulizer solution with a concentration of F127 ∼10(-2)mM, a 12% reduction in the radius of all aerosol produced at a relative humidity (RH) of 84% is possible. The

  11. Maillard Chemistry in Clouds and Aqueous Aerosol As a Source of Atmospheric Humic-Like Substances.

    PubMed

    Hawkins, Lelia N; Lemire, Amanda N; Galloway, Melissa M; Corrigan, Ashley L; Turley, Jacob J; Espelien, Brenna M; De Haan, David O

    2016-07-19

    The reported optical, physical, and chemical properties of aqueous Maillard reaction mixtures of small aldehydes (glyoxal, methylglyoxal, and glycolaldehyde) with ammonium sulfate and amines are compared with those of aqueous extracts of ambient aerosol (water-soluble organic carbon, WSOC) and the humic-like substances (HULIS) fraction of WSOC. Using a combination of new and previously published measurements, we examine fluorescence, X-ray absorbance, UV/vis, and IR spectra, complex refractive indices, (1)H and (13)C NMR spectra, thermograms, aerosol and electrospray ionization mass spectra, surface activity, and hygroscopicity. Atmospheric WSOC and HULIS encompass a range of properties, but in almost every case aqueous aldehyde-amine reaction mixtures are squarely within this range. Notable exceptions are the higher UV/visible absorbance wavelength dependence (Angström coefficients) observed for methylglyoxal reaction mixtures, the lack of surface activity of glyoxal reaction mixtures, and the higher N/C ratios of aldehyde-amine reaction products relative to atmospheric WSOC and HULIS extracts. The overall optical, physical, and chemical similarities are consistent with, but not demonstrative of, Maillard chemistry being a significant secondary source of atmospheric HULIS. However, the higher N/C ratios of aldehyde-amine reaction products limits the source strength to ≤50% of atmospheric HULIS, assuming that other sources of HULIS incorporate only negligible quantities of nitrogen.

  12. Maillard Chemistry in Clouds and Aqueous Aerosol As a Source of Atmospheric Humic-Like Substances.

    PubMed

    Hawkins, Lelia N; Lemire, Amanda N; Galloway, Melissa M; Corrigan, Ashley L; Turley, Jacob J; Espelien, Brenna M; De Haan, David O

    2016-07-19

    The reported optical, physical, and chemical properties of aqueous Maillard reaction mixtures of small aldehydes (glyoxal, methylglyoxal, and glycolaldehyde) with ammonium sulfate and amines are compared with those of aqueous extracts of ambient aerosol (water-soluble organic carbon, WSOC) and the humic-like substances (HULIS) fraction of WSOC. Using a combination of new and previously published measurements, we examine fluorescence, X-ray absorbance, UV/vis, and IR spectra, complex refractive indices, (1)H and (13)C NMR spectra, thermograms, aerosol and electrospray ionization mass spectra, surface activity, and hygroscopicity. Atmospheric WSOC and HULIS encompass a range of properties, but in almost every case aqueous aldehyde-amine reaction mixtures are squarely within this range. Notable exceptions are the higher UV/visible absorbance wavelength dependence (Angström coefficients) observed for methylglyoxal reaction mixtures, the lack of surface activity of glyoxal reaction mixtures, and the higher N/C ratios of aldehyde-amine reaction products relative to atmospheric WSOC and HULIS extracts. The overall optical, physical, and chemical similarities are consistent with, but not demonstrative of, Maillard chemistry being a significant secondary source of atmospheric HULIS. However, the higher N/C ratios of aldehyde-amine reaction products limits the source strength to ≤50% of atmospheric HULIS, assuming that other sources of HULIS incorporate only negligible quantities of nitrogen. PMID:27227348

  13. Cell Partition in Two Polymer Aqueous Phases

    NASA Technical Reports Server (NTRS)

    Brooks, D. E.

    1985-01-01

    In a reduced gravity environment the two polymer phases will not separate via density driven settling in an acceptably short length of time. It is to be expected that a certain amount of phase separation will take place, however, driven by the reduction in free energy gained when the interfacial area is reduced. This stage of separation process will therefore depend directly on the magnitude of the interfacial tension between the phases. In order to induce complete phase separation in a short time, electric field-induced separation which occurs because the droplets of one phase in the other have high electrophoretic mobilities which increase with droplet size was investigated. These mobilities are significant only in the presence of certain salts, particularly phosphates. The presence of such salts, in turn has a strong effect on the cell partition behavior in dextran-poly (ethylene glycol) (PEG) systems. The addition of the salts necessary to produce phase drop mobilities has a large effect on the interfacial tensions in the systems.

  14. Evidence of aqueous secondary organic aerosol formation from biogenic emissions in the North American Sonoran Desert

    PubMed Central

    Youn, Jong-Sang; Wang, Zhen; Wonaschütz, Anna; Arellano, Avelino; Betterton, Eric A.; Sorooshian, Armin

    2013-01-01

    This study examines the role of aqueous secondary organic aerosol formation in the North American Sonoran Desert as a result of intense solar radiation, enhanced moisture, and biogenic volatile organic compounds (BVOCs). The ratio of water-soluble organic carbon (WSOC) to organic carbon (OC) nearly doubles during the monsoon season relative to other seasons of the year. When normalized by mixing height, the WSOC enhancement during monsoon months relative to preceding dry months (May–June) exceeds that of sulfate by nearly a factor of 10. WSOC:OC and WSOC are most strongly correlated with moisture parameters, temperature, and concentrations of O3 and BVOCs. No positive relationship was identified between WSOC or WSOC:OC and anthropogenic tracers such as CO over a full year. This study points at the need for further work to understand the effect of BVOCs and moisture in altering aerosol properties in understudied desert regions. PMID:24115805

  15. Redistribution of black and brown carbon in aerosol particles undergoing liquid-liquid phase separation

    NASA Astrophysics Data System (ADS)

    Krieger, U. K.; Brunamonti, S.; Marcolli, C.; Peter, T.

    2015-12-01

    Atmospheric black carbon (BC) and to a lesser degree brown carbon is a major anthropogenic greenhouse agent, yet substantial uncertainties obstruct understanding its radiative forcing. Particularly debated is the extent of the absorption enhancement by internally compared to externally mixed BC, which critically depends on the interior morphology of the BC-containing particles. Here we suggest that a currently unaccounted morphology, optically very different from the customary core shell and volume-mixing assumptions, likely occurs in aerosol particles undergoing liquid-liquid phase separation (LLPS). Using Raman spectroscopy on micrometer-sized droplets, we show that LLPS of an organic/inorganic model system drives redistribution of BC into the outer (organic) phase of the host particle. This results in an inverted core-shell structure, in which a transparent aqueous core is surrounded by a BC-containing absorbing shell. We also study the redistribution of a model proxy for brown carbon, carminic acid, in single, levitated aqueous aerosol particles undergoing LLPS and compare the measured absorption efficiency with corresponding Mie calculations.

  16. Oxidation of Organic Compoundsin the Atmospheric Aqueous Phase: Development of a New Explicit Oxidation Mechanism

    NASA Astrophysics Data System (ADS)

    Mouchel-Vallon, C.; Bregonzio-Rozier, L.; Monod, A.; Leriche, M.; Doussin, J. F.; Chaumerliac, N. M.; Deguillaume, L.

    2014-12-01

    Current 3D models tend to underestimate the production of secondary organic aerosol (SOA) in the atmosphere (Volkamer et al., 2006). Recent studies argue that aqueous chemistry in clouds could be responsible for a significant production of SOA (Ervens et al., 2011; Carlton and Turpin, 2013) through oxidative and non-oxidative processes. Aqueous phase reactivity of organic compounds needs to be thoroughly described in models to identify organic molecules available to contribute to SOA mass. Recently, new empirical methods have been developed to allow the estimate of HO·reaction rates in the aqueous phase (Doussin and Monod, 2013, Minakata et al., 2009). These methods provide global rate constants together with branching ratios for HO·abstraction and addition on organic compounds of atmospheric interests. Current cloud chemistry mechanisms do not take the different possible pathways into account. Based on these structure-activity relationships, a new detailed aqueous phase mechanism describing the oxidation of hydrosoluble organic compounds resulting from isoprene oxidation is proposed. This new aqueous phase mechanism is coupled with the detailed gas phase mechanism MCM v3.2 (Jenkin et al., 1997; Saunders et al., 2003) through a kinetic of mass transfer parameterization for the exchange between gas phase and aqueous phase. The GROMHE SAR (Raventos-Duran et al., 2010) allows the evaluation of Henry's law constants for organic compounds. Variable photolysis in both phases using the TUV 4.5 radiative transfer model (Madronich and Flocke, 1997) is also calculated. The resulting multiphase mechanism has been implemented in a cloud chemistry model. Focusing on oxygenated compounds produced from the isoprene oxidation, sensitivity tests and comparisons with multiphase experiments performed in the framework of the CUMULUS project in the CESAM atmospheric simulation chamber (Wang et al., 2011) will be presented. Volkamer et al., GRL, 33, L17811, 2006. Carlton and Turpin

  17. Evidence of Aqueous Secondary Organic Aerosol Formation from Biogenic Emissions in the North American Sonoran Desert

    NASA Astrophysics Data System (ADS)

    Sorooshian, A.; Youn, J.; Wang, Z.; Wonaschuetz, A.; Arellano, A. F.; Betterton, E. A.

    2013-12-01

    This study examines the role of aqueous secondary organic aerosol (SOA) formation in the North American Sonoran Desert as a result of intense solar radiation, enhanced moisture, and biogenic volatile organic compounds (BVOCs). The ratio of water-soluble organic carbon (WSOC) to organic carbon (OC) nearly doubles during the monsoon season relative to other seasons of the year. When normalized by mixing height, the WSOC enhancement during monsoon months relative to preceding dry months (May - June) exceeds that of sulfate by nearly a factor of ten. WSOC:OC and WSOC are most strongly correlated with moisture parameters, temperature, and concentrations of ozone and BVOCs. No positive relationship was identified between WSOC or WSOC:OC and anthropogenic tracers such as carbon monoxide over a full year. These results are especially of significance as recent modeling studies suggest that aqueous SOA formation is geographically concentrated in the eastern United States and likely unimportant in other areas such as the Southwest.

  18. Aqueous-phase source of formic acid in clouds

    NASA Technical Reports Server (NTRS)

    Chameides, W. L.; Davis, D. D.

    1983-01-01

    The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

  19. The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Huang, D.; Zhang, X.; Chen, Z. M.; Zhao, Y.; Shen, X. L.

    2011-08-01

    Aqueous phase chemical processes of organic compounds in the atmosphere have received increasing attention, partly due to their potential contribution to the formation of secondary organic aerosol (SOA). Here, we analyzed the aqueous OH-initiated oxidation of isoprene and its reaction products including carbonyl compounds and organic acids, regarding the acidity and temperature as in-cloudy conditions. We also performed a laboratory simulation to improve our understanding of the kinetics and mechanisms for the products of aqueous isoprene oxidation that are significant precursors of SOA; these included methacrolein (MACR), methyl vinyl ketone (MVK), methyl glyoxal (MG), and glyoxal (GL). We used a novel chemical titration method to monitor the concentration of isoprene in the aqueous phase. We used a box model to interpret the mechanistic differences between aqueous and gas phase OH radical-initiated isoprene oxidations. Our results were the first demonstration of the rate constant for the reaction between isoprene and OH radical in water, 1.2 ± 0.4) × 1010 M-1 s-1 at 283 K. Molar yields were determined based on consumed isoprene. Of note, the ratio of the yields of MVK (24.1 ± 0.8 %) to MACR (10.9 ± 1.1%) in the aqueous phase isoprene oxidation was approximately double that observed for the corresponding gas phase reaction. We hypothesized that this might be explained by a water-induced enhancement in the self-reaction of a hydroxy isoprene peroxyl radical (HOCH2C(CH3)(O2)CH = CH2) produced in the aqueous reaction. The observed yields for MG and GL were 11.4 ± 0.3 % and 3.8 ± 0.1 %, respectively. Model simulations indicated that several potential pathways may contribute to the formation of MG and GL. Finally, oxalic acid increased steadily throughout the course of the study, even after isoprene was consumed completely. The observed yield of oxalic acid was 26.2 ± 0.8 % at 6 h. The observed carbon balance accounted for ~50 % of the consumed isoprene. The

  20. On-demand generation of aqueous two-phase microdroplets with reversible phase transitions

    SciTech Connect

    Boreyko, Jonathan B; Mruetusatorn, Prachya; Retterer, Scott T; Collier, Pat

    2013-01-01

    Aqueous two-phase systems contained entirely within microdroplets enable a bottom-up approach to mimicking the dynamic microcompartmentation of biomaterial that naturally occurs within the cytoplasm of cells. Here, we demonstrate the on-demand generation of femtolitre aqueous two-phase droplets within a microfluidic oil channel. Gated pressure pulses were used to generate individual, stationary two-phase microdroplets with a well-defined time zero for carrying out controlled and sequential phase transformations over time. Reversible phase transitions between single-phase, two-phase, and core-shell microgel states were obtained via evaporation-induced dehydration and on-demand water rehydration. In contrast to other microfluidic aqueous two-phase droplets, which require continuous flows and high-frequency droplet formation, our system enables the controlled isolation and reversible transformation of a single microdroplet and is expected to be useful for future studies in dynamic microcompartmentation and affinity partitioning.

  1. On-demand generation of aqueous two-phase microdroplets with reversible phase transitions

    NASA Astrophysics Data System (ADS)

    Collier, Charles

    2013-03-01

    Aqueous two-phase systems contained within microdroplets enable a bottom-up approach to mimicking the dynamic microcompartmentation of biomaterial that naturally occurs within the cytoplasm of cells. Here, we demonstrate the on-demand generation of femtolitre aqueous two-phase droplets within a microfluidic oil channel. Gated pressure pulses were used to generate individual, stationary two-phase microdroplets with a well-defined time zero for carrying out controlled and sequential phase transformations over time. Reversible phase transitions between single-phase, two-phase, and core-shell microbead states were obtained via evaporation-induced dehydration and on-demand water rehydration. In contrast to other microfluidic aqueous two-phase droplets, which require continuous flows and high-frequency droplet formation, our system enables the controlled isolation and reversible transformation of a single microdroplet and is expected to be useful for future studies in dynamic microcompartmentation and affinity partitioning.

  2. The Role of Aqueous Aerosols in the "Glyoxylate Scenario": An Experimental Approach.

    PubMed

    Marín-Yaseli, Margarita R; González-Toril, Elena; Mompeán, Cristina; Ruiz-Bermejo, Marta

    2016-08-26

    The origin of life is one of the fundamental questions in science. Eschenmoser proposed the "glyoxylate scenario", in which plausible abiotic synthesis pathways were suggested to be compatible with the constraints of prebiotic chemistry. In this proposal, the stem compound is HCN. In this work, we explore the "glyoxylate scenario" through several syntheses of HCN polymers, paying particular attention to the role of the aqueous aerosols, together with statistical methods, as a step to elucidate the synthetic problem of the origin of life. The soluble and insoluble HCN polymers synthetized were analyzed by GC-MS. We identified, for the first time, glyoxylic acid in these polymers, together with some constituents of the reductive tricarboxylic acid cycle, amino acids and several N-heterocycles. The findings presented herein, as the first global approach to the "glyoxylate scenario", give full effect to this hypothesis and prove that aqueous aerosols could play an important role in this plausible scene of the origin of life. PMID:27464613

  3. NMR Studies on the Aqueous Phase Photochemical Degradation of TNT

    SciTech Connect

    Thorn, Kevin A.; Cox, Larry G.

    2008-04-06

    Aqueous phase photochemical degradation of 2,4,6-trinitrotoluene (TNT) is an important pathway in several environments, including washout lagoon soils, impact craters from partially detonated munitions that fill with rain or groundwater, and shallow marine environments containing unexploded munitions that have corroded. Knowledge of the degradation products is necessary for compliance issues on military firing ranges and formerly used defense sites. Previous laboratory studies have indicated that UV irradiation of aqueous TNT solutions results in a multicomponent product mixture, including polymerization compounds, that has been only partially resolved by mass spectrometric analyses. This study illustrates how a combination of solid and liquid state 1H, 13C, and 15N NMR spectroscopy, including two dimensional analyses, provides complementary information on the total product mixture from aqueous photolysis of TNT, and the effect of reaction conditions. Among the degradation products detected were amine, amide, azoxy, azo, and carboxylic acid compounds.

  4. A new approach to characterise pharmaceutical aerosols: measurement of aerosol from a single dose aqueous inhaler with an optical particle counter.

    PubMed

    Kuhli, Maren; Weiss, Maximilian; Steckel, Hartwig

    2010-01-31

    An in-line sampling system with dilution units for aqueous droplet aerosols from single dose inhalers (Berodual Respimat, Boehringer Ingelheim Pharma GmbH & Co. KG, Germany) for an optical particle counter is described. The device has been designed to interface with a white light aerosol spectrometer (welas digital 2100, Palas GmbH, Germany) that allows the time-resolved measurement of highly concentrated aerosols. Performance of the sampling system with regard to the measured particle size distribution (PSD) is compared to Next Generation Impactor (NGI) and to laser diffraction measurements (Sympatec Inhaler and open bench). Optimal settings of the sampling system lead to PSDs that correspond well to those measured by the evaporation minimising NGI approach (15 L/min, cooled) and laser diffraction. The better accuracy of the new dilution unit in presence of an additional aerosol sampling filter in comparison to a previously described aerosol sampling system is shown for different settings of the sampling system. This allows a more precise quantification of the delivered drug amount which is also well correlated to the aerosol volume measured by the welas system. In addition, using time-resolved welas measurements provides insight into droplet size, evaporation and size changes of aerosol clouds delivered by liquid inhalers.

  5. A New Method for Multicomponent Activity Coefficients of Electrolytes in Aqueous Atmospheric Aerosols

    SciTech Connect

    Zaveri, Rahul A.; Easter, Richard C.; Wexler, Anthony S.

    2005-01-21

    Three-dimensional models of atmospheric inorganic aerosols need an accurate yet computationally efficient parameterization of activity coefficients of various electrolytes in multicomponent aqueous solutions. This paper describes the development and application of a new mixing rule for calculating activity coefficients of electrolytes typically found in atmospheric aerosol systems containing H+, NH4+, Na+, Ca2+ SO42-, HSO4-, NO3-, and Cl- ions. The new mixing rule, called MTEM (Multicomponent Taylor Expansion Model), estimates the mean activity coefficient of an electrolyte in a multicomponent solution based on its values in binary solutions of all the electrolytes present in the mixture at the solution water activity aw, assuming aw is equal to the ambient relative humidity. The aerosol water content is calculated using the Zdanovskii-Stokes-Robinson method. For self-consistency, most of the MTEM and Zdanovskii-Stokes-Robinson parameters are derived using the comprehensive Pitzer-Simonson-Clegg model at 298.15 K. MTEM is evaluated for several multicomponent systems representing various continental and marine aerosols, and is contrasted against the mixing rule of Kusik and Meissner and the newer approach of Metzger et al. [2002]. Predictions of MTEM are found to be generally within a factor of 0.8 to 1.25 of the comprehensive Pitzer-Simonson-Clegg model, and are shown to be significantly more accurate than predictions of the other two methods. MTEM also yields a non-iterative solution of the bisulfate ion dissociation in sulfate-rich systems – a major computational advantage over other iterative methods. CPU time requirements of MTEM relative to other methods for sulfate-poor and sulfate-rich systems are also discussed.

  6. Effects of aerosol phase and water uptake for understanding organic aerosol oxidation

    NASA Astrophysics Data System (ADS)

    Fitzgerald, C.; Gallimore, P. J.; Fuller, S.; Lee, J.; Garrascon, V.; Achakulwisut, P.; Björkegren, A.; Spring, D. R.; Pope, F. D.; Kalberer, M.

    2012-04-01

    Oxidation reactions of atmospheric organic aerosols strongly influence many important processes in the atmosphere such as aerosol-cloud interactions or heterogeneous chemistry. We present results of an experimental laboratory study with three organic model aerosol systems (maleic, arachidonic and oleic acid) investigating the effect of particle phase and humidity on the oxidative processing of the particle. Two experimental techniques are combined in this investigation. An electrodynamic balance is used to levitate single particles and assess changes in particle size and mass (due to water uptake and/or loss of volatile oxidation products) and phase (liquid or solid) during and after chemical processing with ozone. An aerosol flow tube was used to investigate the detailed chemical composition of the oxidized aerosol with offline ultra-high resolution mass spectrometry. The role of water (i.e., relative humidity) in the oxidation scheme of the three carboxylic acids is very compound specific and the particle phase has a strong effect on the particle processing. Relative humidity was observed to have a major influence on the oxidation scheme of maleic acid and arachidonic acid, whereas no dependence was observed for the oxidation of oleic acid. In both, maleic acid and arachidonic acid, an evaporation of volatile oxidation products could only be observed when the particle was exposed to high relative humidities. Maleic and arachidonic acid change their phase from liquid to solid upon oxidation or upon changes in humidity and efficient oxidative processing of the particle bulk can only occur when the particle is in liquid form. A detailed oxidation mechanism for maleic acid is presented taking the strong effects of water into account. In contrast, oleic acid is liquid under all conditions at room temperature (dry or elevated humidity, pure or oxidized particle). Thus ozone can easily diffuse into the bulk of the particle irrespective of the oxidation conditions. In

  7. Morphologies of aerosol particles consisting of two liquid phases

    NASA Astrophysics Data System (ADS)

    Song, Mijung; Marcolli, Claudia; Krieger, Ulrich; Peter, Thomas

    2013-04-01

    Recent studies have shown that liquid-liquid phase separation (LLPS) might be a common feature in mixed organic/ammonium sulfate (AS)/H2O particles. Song et al. (2012) observed that in atmospheric relevant organic/AS/H2O mixtures LLPS always occurred for organic aerosol compositions with O:C < 0.56, depended on the specific functional groups of organics in the range of 0.56 < O:C < 0.80 and never appeared for O:C > 0.80. The composition of the organic fraction and the mixing state of aerosol particles may influence deliquescence relative humidity (DRH) and efflorescence relative humidity (ERH) of inorganic salts during RH cycles and also aerosol morphology. In order to determine how the deliquescence and efflorescence of AS in mixed organic/AS/H2O particles is influenced by LLPS and to identify the corresponding morphologies of the particles, we subjected organic/AS/H2O particles deposited on a hydrophobically coated substrate to RH cycles and observed the phase transitions using optical microscopy and Raman spectroscopy. In this study, we report results from 21 organic/AS/H2O systems with O:C ranging from 0.55 - 0.85 covering aliphatic and aromatic oxidized compounds. Eight systems did not show LLPS for all investigated organic-to-inorganic ratios, nine showed core-shell morphology when present in a two-liquid-phases state and four showed both, core-shell or partially engulfed configurations depending on the organic-to-inorganic ratio. While AS in aerosol particles with complete LLPS showed almost constant values of ERH = 44 ± 4 % and DRH = 77 ± 2 %, a strong reduction or complete inhibition of efflorescence occurred for mixtures that did not exhibit LLPS. To confirm these findings, we performed supplementary experiments on levitated particles in an electrodynamic balance and compared surface and interfacial tensions of the investigated mixtures. Reference Song, M., C. Marcolli, U. K. Krieger, A. Zuend, and T. Peter (2012), Liquid-liquid phase separation in

  8. Partitioning of metals between the aqueous phase and suspended insoluble material in fog droplets.

    PubMed

    Mancinelli, Valeriana; Decesari, Stefano; Facchini, Maria Cristina; Fuzzi, Sandro; Mangani, Filippo

    2005-05-01

    This paper discusses the partitioning of metals (K, Na, Ca, Mg, Al, Cu, Fe, Pb and Zn) between the aqueous phase and the suspended insoluble material in fog samples collected in the Po Valley during two extensive fields campaigns. Metals represent on average 11% of the mass of suspended insoluble matter, while the main component is carbon (both organic carbon, OC = 35%, and black carbon, BC = 8%). The unaccounted suspended matter mass is very high, on average 46%, and is attributable to non metallic species, such as O and N and of Si. The principal metals in the insoluble suspended fraction are Fe and Al (2-5%), while the contributions of other metals (Na, Mg, Cu, Pb and Zn) are lower than 1%. Ca and K exhibited high blank values and could not be detected above blank detection limit threshold. The main components in the aqueous phase are NO3- (34%), WSOC (23%), SO4(2-) (18%) and NH4+ (19%), while trace metals and remaining cations and anions accounted for less than 1% of solute mass. The main dissolved trace metals in fog droplets are Zn, Al and Fe, while the main metallic cations are Na and Ca. Fe and Al are the only metals preferentially distributed in the suspended insoluble matter of fog droplets (partitioning ratio respectively 37% and 33%). All other metals are mostly dissolved in the aqueous phase (mean partitioning ratios of Mg, Pb, Zn, Cu and Na are 69%, 70%, 77%, 81% and 87%). These findings are in agreement with literature data on metal speciation in cloud and rain samples. The dependence of partitioning ratios on pH is investigated for the different metals, with only Al showing a clear partitioning ratio decrease with increasing pH. Conversely, the other metals show no dependence or a complex and highly variable behaviour. The partitioning ratio of iron (mean 37%) observed in the Po Valley fog samples is much higher than the water extractable iron in aerosol particles (typically 1-2 %): this fact can be explained by differences in the aerosol sources

  9. Olefin Epoxidation in Aqueous Phase Using Ionic-Liquid Catalysts.

    PubMed

    Cokoja, Mirza; Reich, Robert M; Wilhelm, Michael E; Kaposi, Marlene; Schäffer, Johannes; Morris, Danny S; Münchmeyer, Christian J; Anthofer, Michael H; Markovits, Iulius I E; Kühn, Fritz E; Herrmann, Wolfgang A; Jess, Andreas; Love, Jason B

    2016-07-21

    Hydrophobic imidazolium-based ionic liquids (IL) act as catalysts for the epoxidation of unfunctionalized olefins in water using hydrogen peroxide as oxidant. Although the catalysts are insoluble in both the substrate and in water, surprisingly, they are very well soluble in aqueous H2 O2 solution, owing to perrhenate-H2 O2 interactions. Even more remarkably, the presence of the catalyst also boosts the solubility of substrate in water. This effect is crucially dependent on the cation design. Hence, the imidazolium perrhenates enable both the transfer of hydrophobic substrate into the aqueous phase, and serve as actual catalysts, which is unprecedented. At the end of the reaction and in absence of H2 O2 the IL catalyst forms a third phase next to the lipophilic product and water and can easily be recycled.

  10. Olefin Epoxidation in Aqueous Phase Using Ionic-Liquid Catalysts.

    PubMed

    Cokoja, Mirza; Reich, Robert M; Wilhelm, Michael E; Kaposi, Marlene; Schäffer, Johannes; Morris, Danny S; Münchmeyer, Christian J; Anthofer, Michael H; Markovits, Iulius I E; Kühn, Fritz E; Herrmann, Wolfgang A; Jess, Andreas; Love, Jason B

    2016-07-21

    Hydrophobic imidazolium-based ionic liquids (IL) act as catalysts for the epoxidation of unfunctionalized olefins in water using hydrogen peroxide as oxidant. Although the catalysts are insoluble in both the substrate and in water, surprisingly, they are very well soluble in aqueous H2 O2 solution, owing to perrhenate-H2 O2 interactions. Even more remarkably, the presence of the catalyst also boosts the solubility of substrate in water. This effect is crucially dependent on the cation design. Hence, the imidazolium perrhenates enable both the transfer of hydrophobic substrate into the aqueous phase, and serve as actual catalysts, which is unprecedented. At the end of the reaction and in absence of H2 O2 the IL catalyst forms a third phase next to the lipophilic product and water and can easily be recycled. PMID:27219852

  11. Computation of Phase Equilibria, State Diagrams and Gas/Particle Partitioning of Mixed Organic-Inorganic Aerosols

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Peter, T.

    2009-04-01

    The chemical composition of organic-inorganic aerosols is linked to several processes and specific topics in the field of atmospheric aerosol science. Photochemical oxidation of organics in the gas phase lowers the volatility of semi-volatile compounds and contributes to the particulate matter by gas/particle partitioning. Heterogeneous chemistry and changes in the ambient relative humidity influence the aerosol composition as well. Molecular interactions between condensed phase species show typically non-ideal thermodynamic behavior. Liquid-liquid phase separations into a mainly polar, aqueous and a less polar, organic phase may considerably influence the gas/particle partitioning of semi-volatile organics and inorganics (Erdakos and Pankow, 2004; Chang and Pankow, 2006). Moreover, the phases present in the aerosol particles feed back on the heterogeneous, multi-phase chemistry, influence the scattering and absorption of radiation and affect the CCN ability of the particles. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy, enabling the calculation of activity coefficients. We use the group-contribution model AIOMFAC (Zuend et al., 2008) to calculate activity coefficients, chemical potentials and the total Gibbs energy of mixed organic-inorganic systems. This thermodynamic model was combined with a robust global optimization module to compute potential liquid-liquid (LLE) and vapor-liquid-liquid equilibria (VLLE) as a function of particle composition at room temperature. And related to that, the gas/particle partitioning of semi-volatile components. Furthermore, we compute the thermodynamic stability (spinodal limits) of single-phase solutions, which provides information on the process type and kinetics of a phase separation. References Chang, E. I. and Pankow, J. F.: Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part

  12. High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

    SciTech Connect

    Romonosky, Dian E.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2015-03-19

    A significant fraction of atmospheric organic compounds is predominantly found in condensed phases, such as aerosol particles and cloud droplets. Many of these compounds are photolabile and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of aqueous droplets (hours) and particles (days). This paper presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d- limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features, and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx generated SOA had more unique visual appearance, and indicated a lower extent of products overlap. Furthermore, the fraction of nitrogen containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone driven oxidation. Comparison of the SOA constituents

  13. Converting sugars to sugar alcohols by aqueous phase catalytic hydrogenation

    DOEpatents

    Elliott, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

    2003-05-27

    The present invention provides a method of converting sugars to their corresponding sugar alcohols by catalytic hydrogenation in the aqueous phase. It has been found that surprisingly superior results can be obtained by utilizing a relatively low temperature (less than 120.degree. C.), selected hydrogenation conditions, and a hydrothermally stable catalyst. These results include excellent sugar conversion to the desired sugar alcohol, in combination with long life under hydrothermal conditions.

  14. Redistribution of black carbon in aerosol particles undergoing liquid-liquid phase separation

    NASA Astrophysics Data System (ADS)

    Brunamonti, S.; Krieger, U. K.; Marcolli, C.; Peter, T.

    2015-04-01

    Atmospheric black carbon (BC) is a major anthropogenic greenhouse agent, yet substantial uncertainties obstruct understanding its radiative forcing. Particularly debated is the extent of the absorption enhancement by internally compared to externally mixed BC, which critically depends on the interior morphology of the BC-containing particles. Here we suggest that a currently unaccounted morphology, optically very different from the customary core-shell and volume-mixing assumptions, likely occurs in aerosol particles undergoing liquid-liquid phase separation (LLPS). Using Raman spectroscopy on micrometer-sized droplets, we show that LLPS of an organic/inorganic model system drives redistribution of BC into the outer (organic) phase of the host particle. This results in an inverted core-shell structure, in which a transparent aqueous core is surrounded by a BC-containing absorbing shell. Based on Mie theory calculations, we estimate that such a redistribution can increase the absorption efficiency of internally mixed BC aerosols by up to 25% compared to the core-shell approximation.

  15. Redistribution of black carbon in aerosol particles undergoing liquid-liquid phase separation

    NASA Astrophysics Data System (ADS)

    Brunamonti, Simone; Krieger, Ulrich K.; Marcolli, Claudia; Peter, Thomas

    2015-04-01

    Atmospheric black carbon (BC) is a major anthropogenic greenhouse agent, yet substantial uncertainties obstruct understanding its radiative forcing. Particularly debated is the extent of the absorption enhancement by internally compared to externally mixed BC, which critically depends on the interior morphology of the BC-containing particles. Here we suggest that a currently unaccounted morphology, optically very different from the customary core-shell and volume-mixing assumptions, likely occurs in aerosol particles undergoing liquid-liquid phase separation (LLPS). Using Raman spectroscopy on micrometer-sized droplets, we show that LLPS of an organic/inorganic model system drives redistribution of BC into the outer (organic) phase of the host particle. This results in an inverted core-shell structure, in which a transparent aqueous core is surrounded by a BC-containing absorbing shell. Based on Mie theory calculations, we estimate that such a redistribution can reduce the absorption efficiency of internally-mixed BC aerosols by up to 25% compared to the volume-mixing approximation.

  16. X-Ray Microspectroscopic Investigations of Remote Aerosol Composition and Changes in Aerosol Microstructure and Phase State upon Hydration

    NASA Astrophysics Data System (ADS)

    Andreae, M. O.; Artaxo, P.; Bechtel, M.; Förster, J. D.; Kilcoyne, A. L. D.; Krüger, M. L.; Pöhlker, C.; Saturno, J.; Weigand, M.; Wiedemann, K. T.

    2014-12-01

    Atmospheric aerosols play a crucial role in the Earth's climate system and hydrological cycle by scattering and absorbing sunlight and affecting the formation and development of clouds and precipitation. Our research focuses on aerosols in remote regions, in order to characterize the properties and sources of natural aerosol particles and the extent of human perturbations of the aerosol burden. The phase and mixing state of atmospheric aerosols, and particularly their hygroscopic response to relative humidity (RH) variations, is a central determinant of their atmospheric life cycle and impacts. We present an investigation using X-ray microspectroscopy on submicrometer aerosols under variable RH conditions, showing in situ changes in morphology, microstructure, and phase state upon humidity cycling. We applied Scanning Transmission X-ray Microscopy with Near-Edge X-ray Absorption Fine Structure spectroscopy (STXM-NEXAFS) under variable RH conditions to standard aerosols for a validation of the experimental approach and to internally mixed aerosol particles from the Amazonian rain forest collected during periods with anthropogenic pollution. The measurements were conducted at X-ray microscopes at the synchrotron facilities Advanced Light Source (ALS) in Berkeley, USA, and BESSY II in Berlin, Germany. Upon hydration, we observed substantial and reproducible changes in microstructure of the Amazonian particles (internal mixture of secondary organic material, ammoniated sulfate, and soot), which appear as mainly driven by efflorescence and recrystallization of sulfate salts. Multiple solid and liquid phases were found to coexist, especially in intermediate humidity regimes (60-80% RH). This shows that X-ray microspectroscopy under variable RH is a valuable technique to analyze the hygroscopic response of individual ambient aerosol particles. Our initial results underline that RH changes can trigger strong particle restructuring, in agreement with previous studies on

  17. Distribution of Dechlorinating Bacteria between the Aqueous and Solid Phases

    NASA Astrophysics Data System (ADS)

    Cápiro, N. L.; Hatt, J. K.; Wang, Y.; Loeffler, F. E.; Pennell, K. D.

    2010-12-01

    Microbial monitoring of aquifers relies on nucleic acid biomarker analysis, which is typically performed with biomass recovered from groundwater samples; however, it is unclear what fraction of the target population(s) is associated with groundwater (i.e., planktonic cells) or is attached to solid phases (i.e., biofilms). Understanding how the titer of target organism(s) in groundwater correlates with the true cell titers of the target organism in the aquifer (i.e., planktonic plus attached cells) is critical for a meaningful interpretation of the data, the prediction of bioremediation performance, and the implementation of site management strategies. To evaluate the distribution of active cells between resident solid phase and the aqueous phase, one-dimensional columns were packed under water-saturated conditions with Bio-Dechlor INOCULUM, a PCE-to ethene-dechlorinating bacterial consortium containing both multiple Dehalococcoides (Dhc) strains and Geobacter lovleyi strain SZ (GeoSZ). The columns were packed with two distinct solid matrices: a low organic content sandy Federal Fine Ottawa soil or Appling soil with higher organic matter content. Influent reduced mineral salts medium supplied at a groundwater pore-water velocity of 0.3 m/day contained both 10 mM lactate as electron donor and 0.33 mM PCE as electron acceptor. Routine collection of biomass from column side ports and effluent samples measured the titers of target cells in the aqueous phase and determined when steady state conditions had been reached. A second set of column experiments evaluated delivery and filtration effects by the solid matrix (i.e., Federal Fine Ottawa sand versus Appling soil) under the same conditions except that electron donor or acceptor were omitted (no growth conditions). Quantitative real-time PCR (qPCR) analysis using Dhc and GeoSZ 16S rRNA gene-targeted primer and probe sets determined the planktonic cell counts, and destructive sampling of the columns allowed measurement

  18. Interfacial Chemistry of Aqueous Sulfur/Iodide Aerosol Microdroplets in Gaseous Ozone

    NASA Astrophysics Data System (ADS)

    Enami, S.; Vecitis, C. D.; Cheng, J.; Colussi, A. J.; Hoffmann, M. R.

    2007-12-01

    The intermediates ISO3- (m/z = 207) and IS2O3- (m/z = 239) generated in aqueous (iodide - thiosulfate) microdroplets traversing dilute ozone gas plumes at atmospheric pressure are detected via online electrospray mass spectrometry within 1 ms, and their stabilities gauged by collision-induced dissociation. The simultaneous detection of anionic reactants and the S2O62-, HSO4-, IO3- and I3- products as a function of experimental conditions provides evidence of unique interfacial reaction kinetics. Although ozone reacts ~3-4 times faster with I- than S2O332- in bulk solution, only S2O32- is apparently oxidized in [I--]o/[S2O32- ]o = 10 microdroplets below [O3(g)] ~ 50 ppm. The sulfite to sulfate and iodide to triiodide and iodate oxidations in the interfacial layers of aqueous thiosulfate or mixed thiosulfate and iodide microdroplets briefly exposed to dilute O3(g) gas mixtures are also investigated. S(IV) oxidation kinetics in sodium thiosulfate solutions, where the rates are proportional to [S(IV)] [O3(g)] in the ranges investigated, correspond to a surface-specific reaction. I3-/IO3- yields based on interfacial I- losses exceed their stoichiometric limits in the presence of excess S(IV), revealing that interfacial I- is competitively replenished from the microdroplets inner layers. Present results provide unequivocal evidence of distinct interfacial chemistry in gas-aerosol reactions of atmospheric relevance.

  19. Radical mechanisms of methyl vinyl ketone oligomerization through aqueous phase OH-oxidation: on the paradoxical role of dissolved molecular oxygen

    NASA Astrophysics Data System (ADS)

    Renard, P.; Siekmann, F.; Gandolfo, A.; Socorro, J.; Salque, G.; Ravier, S.; Quivet, E.; Clément, J.-L.; Traikia, M.; Delort, A.-M.; Voisin, D.; Vuitton, V.; Thissen, R.; Monod, A.

    2013-07-01

    It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from α-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. Methyl vinyl ketone (MVK) was chosen in the present study as it is an α,β-unsaturated carbonyl that can undergo radical oligomerization in the aerosol aqueous phase. We present here experiments on the aqueous phase OH-oxidation of MVK, performed under various conditions. Using NMR and UV absorption spectroscopy, high and ultra-high resolution mass spectrometry, we show that the fast formation of oligomers up to 1800 Da is due to radical oligomerization of MVK, and 13 series of oligomers (out of a total of 26 series) are identified. The influence of atmospherically relevant parameters such as temperature, initial concentrations of MVK and dissolved oxygen are presented and discussed. In agreement with the experimental observations, we propose a chemical mechanism of OH-oxidation of MVK in the aqueous phase that proceeds via radical oligomerization of MVK on the olefin part of the molecule. This mechanism highlights in our experiments the paradoxical role of dissolved O2: while it inhibits oligomerization reactions, it contributes to produce oligomerization initiator radicals, which rapidly consume O2, thus leading to the dominance of oligomerization reactions after several minutes of reaction. These processes, together with the large range of initial concentrations investigated show the fundamental role that radical oligomerization processes likely play in polluted fogs and atmospheric aerosol.

  20. Rate constants for aqueous-phase reactions of hydroxyl radical ({center_dot}OH) with aldehydes and ketones

    SciTech Connect

    Allen, J.M.; Allen, S.K.

    1995-12-31

    A wide variety of aldehydes and ketones are formed in the troposphere by the gas-phase oxidation of hydrocarbons. These compounds are expected to readily partition into cloud, fog, and aquated aerosol drops where they can participate in a variety of aqueous-phase reactions. It has been previously demonstrated by other researchers that aqueous-phase photochemical reactions involving aromatic aldehydes and ketones may lead to the formation of hydrogen peroxide. Hydrogen peroxide is an important oxidant for S(IV) and is also an {center_dot}OH precursor. Aldehydes and ketones may also participate in other aqueous-phase reactions within atmospheric water drops including reactions with {center_dot}OH. Rate constants for reactions involving {center_dot}OH in aqueous solutions have been reported for only a limited number of tropospheric aldehydes and ketones. The authors have measured the rate constants for aqueous-phase reactions of {center_dot}OH with several tropospheric aldehydes and ketones by the technique of competition kinetics. Hydroxyl radicals were generated by continuous illumination at 313 nm of an aqueous acidified solution containing Fe(ClO{sub 4}){sub 3}, an {center_dot}OH scavenger, the aldehyde or ketone whose rate constant was to be measured, and a standard for which the rate constant for reaction with {center_dot}OH is well known. Nitrobenzene was used as the standard in all experiments. Loss of the aldehyde or ketone and the standard were monitored by HPLC. Losses attributable to direct photolysis and dark reactions were minimal.

  1. Simultaneous Separation of Manganese, Cobalt, and Nickel by the Organic-Aqueous-Aqueous Three-Phase Solvent Extraction

    NASA Astrophysics Data System (ADS)

    Shirayama, Sakae; Uda, Tetsuya

    2016-04-01

    This research outlines an organic-aqueous-aqueous three-phase solvent extraction method and proposes its use in a new metal separation process for the recycling of manganese (Mn), cobalt (Co), and nickel (Ni) from used lithium ion batteries (LIBs). The three-phase system was formed by mixing xylene organic solution, 50 pct polyethylene glycol (PEG) aqueous solution, and 1 mol L-1 sodium sulfate (Na2SO4) aqueous solution. The xylene organic solution contained 2-ethylhexylphosphonic acid (D2EHPA) as an extractant for Mn ion, and the Na2SO4 aqueous solution contained 1 mol L-1 potassium thiocyanate (KSCN) as an extractant for Co ion. Concentrations of the metal ions were varied by dissolving metal sulfates in the Na2SO4 aqueous solution. As a result of the experiments, Mn, Co, and Ni ions were distributed in the xylene organic phase, PEG-rich aqueous phase, and Na2SO4-rich aqueous phase, respectively. The separation was effective when the pH value was around 4. Numerical simulation was also conducted in order to predict the distribution of metal ions after the multi-stage counter-current extractions.

  2. A method to resolve the phase state of aerosol particles

    NASA Astrophysics Data System (ADS)

    Saukko, E.; Kuuluvainen, H.; Virtanen, A.

    2012-01-01

    The phase state of atmospheric aerosols has an impact on their chemical aging and their deliquescence and thus their ability to act as cloud condensation nuclei (CCN). The phase change of particles can be induced by the deliquescence or efflorescence of water or by chemical aging. Existing methods, such as tandem differential mobility analysis rely on the size change of particles related to the water uptake or release. To address the need to study the phase change induced by mass-preserving and nearly mass-preserving processes a new method has been developed. The method relies on the physical impaction of particles on a smooth substrate and subsequent counting of bounced particles by a condensation particle counter (CPC). The connection between the bounce probability and physical properties of particles is so far qualitative. To evaluate the performance of this method, the phase state of ammonium sulfate and levoglucosan, crystalline and amorphous solid, in the presence of water vapor was studied. The results show a marked difference in particle bouncing properties between substances - not only at the critical relative humidity level, but also on the slope of the bouncing probability with respect to humidity. This suggests that the method can be used to differentiate between amorphous and crystalline substances as well as to differentiate between liquid and solid phases.

  3. A method to resolve the phase state of aerosol particles

    NASA Astrophysics Data System (ADS)

    Saukko, E.; Kuuluvainen, H.; Virtanen, A.

    2011-10-01

    The phase state of atmospheric aerosols has impact on their chemical aging and their deliquescence and thus their ability to act as cloud condensation nuclei (CCN). The phase change of particles can be induced by the deliquescence or efflorescence of water or by chemical aging. Existing methods, such as tandem differential mobility analysis rely on the size change of particles related to the water uptake or release related to deliquescence and efflorescence. To address the need to study the phase change induced by mass-preserving and nearly mass-preserving processes a new method has been developed. The method relies on the physical impaction of particles on a smooth substrate and subsequent counting of bounced particles by condensation particle counter (CPC). The connection between the bounce probability and physical properties of particles is so far qualitative. To evaluate the performance of this method, the phase state of ammonium sulfate and levoglucosan, crystalline and amorphous solid, in the presence of water vapor was studied. The results show a marked difference in particle bouncing properties between substances - not only at the critical relative humidity level, but also on the slope of the bouncing probability with respect to humidity. This suggests that the method can be used to differentiate between amorphous and crystalline substances as well as to differentiate between liquid and solid phases.

  4. Multiphase OH oxidation kinetics of organic aerosol: The role of particle phase state and relative humidity

    NASA Astrophysics Data System (ADS)

    Slade, Jonathan H.; Knopf, Daniel A.

    2014-07-01

    Organic aerosol can exhibit different phase states in response to changes in relative humidity (RH), thereby influencing heterogeneous reaction rates with trace gas species. OH radical uptake by laboratory-generated levoglucosan and methyl-nitrocatechol particles, serving as surrogates for biomass burning aerosol, is determined as a function of RH. Increasing RH lowers the viscosity of amorphous levoglucosan aerosol particles enabling enhanced OH uptake. Conversely, OH uptake by methyl-nitrocatechol aerosol particles is suppressed at higher RH as a result of competitive coadsorption of H2O that occupies reactive sites. This is shown to have substantial impacts on organic aerosol lifetimes with respect to OH oxidation. The results emphasize the importance of organic aerosol phase state to accurately describe the multiphase chemical kinetics and thus chemical aging process in atmospheric models to better represent the evolution of organic aerosol and its role in air quality and climate.

  5. On the correlation of output rate and aerodynamic characteristics in vibrating-mesh-based aqueous aerosol delivery.

    PubMed

    Beck-Broichsitter, Moritz; Oesterheld, Nina; Knuedeler, Marie-Christine; Seeger, Werner; Schmehl, Thomas

    2014-01-30

    Aerosolization of aqueous formulations is of special interest for inhalative drug delivery, where an adequate nebulizer performance represents a prerequisite for improving pulmonary therapy. The present study investigated the interplay of output rate and aerodynamic characteristics of different excipient-based formulations and its impact on the atomization process by vibrating-mesh technology (i.e. eFlow(®)rapid). Output rate and aerodynamic characteristics were manipulated by both dynamic viscosity and conductivity of the applied formulation. Supplementation with sucrose and sodium chloride caused a decline (down to ∼0.2 g/min) and elevation (up to ∼1.0 g/min) of the nebulizer output rate, respectively. However, both excipients were capable of decreasing the aerodynamic diameter of produced aerosol droplets from >7.0 μm to values of ≤5.0 μm. Thus, the correlation of output rate and aerodynamic characteristics resulted in linear fits of opposite slopes (R(2)>0.85). Finally, the overall number of delivered aerosol droplets per time was almost constant for sucrose (≤1×10(8) droplets/s), while for sodium chloride a concentration-dependent increase was observed (up to ∼3×10(8) droplets/s). Overall, the current findings illustrated the influence of formulation parameters on the aerosolization process performed by vibrating-mesh technology. Moreover, concentration and charge distribution of aerosol populations supposedly modify the final characteristics of the delivered aerosols.

  6. Experiments and simulations of ion-enhanced interfacial chemistry on aqueous NaCl aerosols

    PubMed

    Knipping; Lakin; Foster; Jungwirth; Tobias; Gerber; Dabdub; Finlayson-Pitts

    2000-04-14

    A combination of experimental, molecular dynamics, and kinetics modeling studies is applied to a system of concentrated aqueous sodium chloride particles suspended in air at room temperature with ozone, irradiated at 254 nanometers to generate hydroxyl radicals. Measurements of the observed gaseous molecular chlorine product are explainable only if reactions at the air-water interface are dominant. Molecular dynamics simulations show the availability of substantial amounts of chloride ions for reaction at the interface, and quantum chemical calculations predict that in the gas phase chloride ions will strongly attract hydroxl radicals. Model extrapolation to the marine boundary layer yields daytime chlorine atom concentrations that are in good agreement with estimates based on field measurements of the decay of selected organics over the Southern Ocean and the North Atlantic. Thus, ion-enhanced interactions with gases at aqueous interfaces may play a more generalized and important role in the chemistry of concentrated inorganic salt solutions than was previously recognized.

  7. Fibril Formation and Phase Separation in Aqueous Cellulose Ethers

    NASA Astrophysics Data System (ADS)

    Maxwell, Amanda; Schmidt, Peter; McAllister, John; Lott, Joseph; Bates, Frank; Lodge, Timothy

    Aqueous solutions of many cellulose ethers are known to undergo thermoreversible gelation and phase separation upon heating to form turbid hydrogels, but the mechanism and resulting structures have not been well understood. Turbidity, light scattering and small-angle neutron scattering (SANS) are used to show that hydroxypropyl methylcellulose (HPMC) chains are dissolved in water below 50 °C and undergo phase separation at higher temperatures. At 70 °C, at sufficiently high concentrations in water, HPMC orders into fibrillar structures with a well-defined radius of 18 +/- 2 nm, as characterized by cryogenic transmission electron microscopy and SANS. The HPMC fibril structure is independent of concentration and heating rate. However, HPMC fibrils do not form a percolating network as readily as is seen in methylcellulose, resulting in a lower hot-gel modulus, as demonstrated by rheology.

  8. The partitioning of ketones between the gas and aqueous phases

    NASA Astrophysics Data System (ADS)

    Betterton, Eric A.

    Most ketones are not significantly hydrated; they therefore retain their chromophore and they could be photolytically degraded in solution yielding a variety of products including carboxylic acids, aldehydes and radicals. It is difficult to accurately model the partitioning of ketones between the gas phase and aqueous phase because of the lack suitable estimates of the Henry's Law constants; consequently the fate and environmental effects of ketones cannot be confidently predicted. Here we report the experimental determination of the Henry's Law constants of a series of ketones that has yielded a simple straight line equation to predict the Henry's Law constants of simple aliphatic ketones: log H ∗ =0.23Σσ ∗ + 1.51; where H ∗ is the effective Henry's Law constant (M atm -1, and Σσ ∗ is the Taft polar substituents constants. The results for 25°C are (M atm -1) CH 3COCH 3, 32; C 6H 5COCH 3, 110; CH 2ClCOCH 3, 59; CH 3COCOCH 3, 74; CF 3COCH 3, 138. Acetophenone appears to have an abnormally high H ∗. Most low molecular weight aliphatic ketones are predicted to characterized by H ∗⩾30 M atm -1 and therefore they are expected to be found in the aqueous phase at concentrations of ⩾5 - 0.5 μM (given a typical gas-phase concentration range of 1-10 ppbv). The expected rate of decomposition of ketones due to photolysis in hydrometers is briefly discussed.

  9. Glycine phases formed from frozen aqueous solutions: Revisited

    SciTech Connect

    Surovtsev, N. V.; Adichtchev, S. V.; Malinovsky, V. K.; Ogienko, A. G.; Manakov, A. Yu.; Drebushchak, V. A.; Ancharov, A. I.; Boldyreva, E. V.; Yunoshev, A. S.

    2012-08-14

    Glycine phases formed when aqueous solutions were frozen and subsequently heated under different conditions were studied by Raman scattering, x-ray diffraction, and differential scanning calorimetry (DSC) techniques. Crystallization of ice I{sub h} was observed in all the cases. On cooling at the rates of 0.5 K/min and 5 K/min, glassy glycine was formed as an intermediate phase which lived about 1 min or less only, and then transformed into {beta}-polymorph of glycine. Quench cooling of glycine solutions (15% w/w) in liquid nitrogen resulted in the formation of a mixture of crystalline water ice I{sub h} and a glassy glycine, which could be preserved at cryogenic temperatures (80 K) for an indefinitely long time. This mixture remained also quite stable for some time after heating above the cryogenic temperature. Subsequent heating under various conditions resulted in the transformation of the glycine glass into an unknown crystalline phase (glycine 'X-phase') at 209-216 K, which at 218-226 K transformed into {beta}-polymorph of glycine. The 'X-phase' was characterized by Raman spectroscopy; it could be obtained in noticeable amounts using a special preparation technique and tentatively characterized by x-ray powder diffraction (P2, a= 6.648 A, b= 25.867 A, c= 5.610 A, {beta}= 113.12 Masculine-Ordinal-Indicator ); the formation of 'X-phase' from the glycine glassy phase and its transformation into {beta}-polymorph were followed by DSC. Raman scattering technique with its power for unambiguous identification of the crystalline and glassy polymorphs without limitation on the crystallite size helped us to follow the phase transformations during quenching, heating, and annealing. The experimental findings are considered in relation to the problem of control of glycine polymorphism on crystallization.

  10. Aqueous-phase photochemical oxidation and direct photolysis of vanillin - a model compound of methoxy-phenols from biomass burning

    NASA Astrophysics Data System (ADS)

    Li, Y. J.; Huang, D. D.; Cheung, H. Y.; Lee, A. K. Y.; Chan, C. K.

    2013-10-01

    We present here experimental results on aqueous-phase (A) photochemical oxidation (with UV and OH radicals generated from H2O2 photolysis) and (B) direct photolysis (with only UV irradiation) of a methoxy-phenol, vanillin (VL), as a model compound from biomass burning. Both on-line aerosol mass spectrometric (AMS) characterization and off-line chemical analyses were performed. AMS analyses of dried atomized droplets of the bulk reacting mixtures showed that VL almost entirely evaporates during the drying process. Large amounts of organic mass remained in the particle phase after reactions under both conditions. Under condition (A), AMS measured organic mass first increased rapidly and then decreased, attributable to the formation of non-volatile products and subsequent formation of smaller and volatile products, respectively. The oxygen-to-carbon (O:C) ratio of the products reached 1.5 after about 80 min, but dropped substantially thereafter. In contrast, organic mass increased slowly under condition (B). The O:C ratio reached 1.0 after 180 min. In off-line analyses, small oxygenates were detected under condition (A), while hydroxylated products and dimers of VL were detected under condition (B). Particle hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of the reacting mixtures were found to be dependent on both organic volume fraction and the degree of oxygenation of organics. Results show that (1) aqueous-phase processes can lead to the retention of a large portion of the organic mass in the particle phase; (2) once retained, this portion of organic mass significantly changes the hygroscopicity and CCN activity of the aerosol particles; (3) intensive photochemical oxidation gave rise to an O:C ratio as high as 1.5 but the ratio decreased as further oxidation led to smaller and more volatile products; and (4) polymerization occurred with direct photolysis, resulting in high-molecular-weight products of a yellowish color. This study

  11. Aqueous-phase photochemical oxidation and direct photolysis of vanillin - a model compound of methoxy phenols from biomass burning

    NASA Astrophysics Data System (ADS)

    Li, Y. J.; Huang, D. D.; Cheung, H. Y.; Lee, A. K. Y.; Chan, C. K.

    2014-03-01

    We present here experimental results on aqueous-phase (A) photochemical oxidation (with UV and OH radicals generated from H2O2 photolysis) and (B) direct photolysis (with only UV irradiation) of a methoxy phenol, vanillin (VL), as a model compound from biomass burning. Both on-line aerosol mass spectrometric (AMS) characterization and off-line chemical analyses were performed. AMS analyses of dried atomized droplets of the bulk reacting mixtures showed that VL almost entirely evaporates during the drying process. Large amounts of organic mass remained in the particle phase after reactions under both conditions. Under condition (A), AMS measured organic mass first increased rapidly and then decreased, attributable to the formation of non-volatile products and subsequent formation of smaller and volatile products, respectively. The oxygen-to-carbon (O : C) ratio of the products reached 1.5 after about 80 min, but dropped substantially thereafter. In contrast, organic mass increased slowly under condition (B). The O : C ratio reached 1.0 after 180 min. In off-line analyses, small oxygenates were detected under condition (A), while hydroxylated products and dimers of VL were detected under condition (B). Particle hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of the reacting mixtures were found to depend on both organic volume fraction and the degree of oxygenation of organics. Results show that (1) aqueous-phase processes can lead to the retention of a large portion of the organic mass in the particle phase; (2) once retained, this portion of organic mass significantly changes the hygroscopicity and CCN activity of the aerosol particles; (3) intensive photochemical oxidation gave rise to an O : C ratio as high as 1.5 but the ratio decreased as further oxidation led to smaller and more volatile products; and (4) polymerization occurred with direct photolysis, resulting in high-molecular-weight products of a yellowish color. This study

  12. Heterogeneous oxidation of pesticides on aerosol condensed phase

    NASA Astrophysics Data System (ADS)

    Socorro, Joanna; Durand, Amandine; Temime-Roussel, Brice; Ravier, Sylvain; Gligorovski, Sasho; Wortham, Henri; Quivet, Etienne

    2015-04-01

    Pesticides are widely used all over the world. It is known that they exhibit adverse health effects and environmental risks due to their physico-chemical properties and their extensive use which is growing every year. They are distributed in the atmosphere, an important vector of dissemination, over long distances away from the target area. The partitioning of pesticides between the gas and particulate phases influences their atmospheric fate. Most of the pesticides are semi-volatile compounds, emphasizing the importance of assessing their heterogeneous reactivity towards atmospheric oxidants. These reactions are important because they are involved in, among others, direct and indirect climate changes, adverse health effects from inhaled particles, effects on cloud chemistry and ozone production. In this work, the importance of atmospheric degradation of pesticides is evaluated on the surface of aerosol deliquescent particles. The photolysis processing and heterogeneous reactivity towards O3 and OH, was evaluated of eight commonly used pesticides (cyprodinil, deltamethrin, difenoconazole, fipronil, oxadiazon, pendimethalin, permethrin, tetraconazole) adsorbed on silica particles. Silicate particles are present in air-borne mineral dust in atmospheric aerosols, and heterogeneous reactions can be different in the presence of these mineral particles. Depending on their origin and conditioning, aerosol particles containing pesticides can have complex and highly porous microstructures, which are influenced by electric charge effects and interaction with water vapour. Therefore, the kinetic experiments and consecutive product studies were performed at atmospherically relevant relative humidity (RH) of 55 %. The identification of surface bound products was performed using GC-(QqQ)-MS/MS and LC-(Q-ToF)-MS/MS and the gas-phase products were on-line monitored by PTR-ToF-MS. Based on the detected and identified reaction products, it was observed that water plays a crucial

  13. Transfer Kinetics at the Aqueous/Non-Aqueous Phase Liquid Interface. A Statistical Mechanic Approach

    NASA Astrophysics Data System (ADS)

    Doss, S. K.; Ezzedine, S.; Ezzedine, S.; Ziagos, J. P.; Hoffman, F.; Gelinas, R. J.

    2001-05-01

    Many modeling efforts in the literature use a first-order, linear-driving-force model to represent the chemical dissolution process at the non-aqueous/aqueous phase liquid (NAPL/APL) interface. In other words, NAPL to APL phase flux is assumed to be equal to the difference between the solubility limit and the "bulk aqueous solution" concentrations times a mass transfer coefficient. Under such assumptions, a few questions are raised: where, in relation to a region of pure NAPL, does the "bulk aqueous solution" regime begin and how does it behave? The answers are assumed to be associated with an arbitrary, predetermined boundary layer, which separates the NAPL from the surrounding solution. The mass transfer rate is considered to be, primarily, limited by diffusion of the component through the boundary layer. In fact, compositional models of interphase mass transfer usually assume that a local equilibrium is reached between phases. Representing mass flux as a rate-limiting process is equivalent to assuming diffusion through a stationary boundary layer with an instantaneous local equilibrium and linear concentration profile. Some environmental researchers have enjoyed success explaining their data using chemical engineering-based correlations. Correlations are strongly dependent on the experimental conditions employed. A universally applicable theory for NAPL dissolution in natural systems does not exist. These correlations are usually expressed in terms of the modified Sherwood number as a function of Reynolds, Peclet, and Schmidt numbers. The Sherwood number may be interpreted as the ratio between the grain size and the thickness of the Nernst stagnant film. In the present study, we show that transfer kinetics at the NAPL/APL interface under equilibrium conditions disagree with approaches based on the Nernst stagnant film concept. It is unclear whether local equilibrium assumptions used in current models are suitable for all situations.A statistical mechanic

  14. Size distribution and scattering phase function of aerosol particles retrieved from sky brightness measurements

    NASA Technical Reports Server (NTRS)

    Kaufman, Y. J.; Gitelson, A.; Karnieli, A.; Ganor, E. (Editor); Fraser, R. S.; Nakajima, T.; Mattoo, S.; Holben, B. N.

    1994-01-01

    Ground-based measurements of the solar transmission and sky radiance in a horizontal plane through the Sun are taken in several geographical regions and aerosol types: dust in a desert transition zone in Israel, sulfate particles in Eastern and Western Europe, tropical aerosol in Brazil, and mixed continental/maritime aerosol in California. Stratospheric aerosol was introduced after the eruption of Mount Pinatubo in June 1991. Therefore measurements taken before the eruption are used to analyze the properties of tropospheric aerosol; measurements from 1992 are also used to detect the particle size and concentration of stratospheric aerosol. The measurements are used to retrieve the size distribution and the scattering phase function at large scattering angles of the undisturbed aerosol particles. The retrieved properties represent an average on the entire atmospheric column. A comparison between the retrieved phase function for a scattering angle of 120 deg, with phase function predicted from the retrieved size distribution, is used to test the assumption of particle homogeneity and sphericity in radiative transfer models (Mie theory). The effect was found to be small (20% +/- 15%). For the stratospheric aerosol (sulfates), as expected, the phase function was very well predicted using the Mie theory. A model with a power law distribution, based on the spectral dependence of the optical thickness, alpha, cannot estimate accurately the phase function (up to 50% error for lambda = 0.87 microns). Before the Pinatubo eruption the ratio between the volumes of sulfate and coarse particles was very well correlated with alpha. The Pinatubo stratospheric aerosol destroyed this correlation. The aerosol optical properties are compared with analysis of the size, shape, and composition of the individual particles by electron microscopy of in situ samples. The measured volume size distribution before the injection of stratospheric aerosol consistently show two modes, sulfate

  15. Photochemistry of aqueous pyruvic acid.

    PubMed

    Griffith, Elizabeth C; Carpenter, Barry K; Shoemaker, Richard K; Vaida, Veronica

    2013-07-16

    The study of organic chemistry in atmospheric aerosols and cloud formation is of interest in predictions of air quality and climate change. It is now known that aqueous phase chemistry is important in the formation of secondary organic aerosols. Here, the photoreactivity of pyruvic acid (PA; CH3COCOOH) is investigated in aqueous environments characteristic of atmospheric aerosols. PA is currently used as a proxy for α-dicarbonyls in atmospheric models and is abundant in both the gas phase and the aqueous phase (atmospheric aerosols, fog, and clouds) in the atmosphere. The photoreactivity of PA in these phases, however, is very different, thus prompting the need for a mechanistic understanding of its reactivity in different environments. Although the decarboxylation of aqueous phase PA through UV excitation has been studied for many years, its mechanism and products remain controversial. In this work, photolysis of aqueous PA is shown to produce acetoin (CH3CHOHCOCH3), lactic acid (CH3CHOHCOOH), acetic acid (CH3COOH), and oligomers, illustrating the progression from a three-carbon molecule to four-carbon and even six-carbon molecules through direct photolysis. These products are detected using vibrational and electronic spectroscopy, NMR, and MS, and a reaction mechanism is presented accounting for all products detected. The relevance of sunlight-initiated PA chemistry in aqueous environments is then discussed in the context of processes occurring on atmospheric aerosols.

  16. A numerical study of aerosol influence on mixed-phase stratiform clouds through modulation of the liquid phase

    NASA Astrophysics Data System (ADS)

    de Boer, G.; Hashino, T.; Tripoli, G. J.; Eloranta, E. W.

    2013-02-01

    Numerical simulations were carried out in a high-resolution two-dimensional framework to increase our understanding of aerosol indirect effects in mixed-phase stratiform clouds. Aerosol characteristics explored include insoluble particle type, soluble mass fraction, influence of aerosol-induced freezing point depression and influence of aerosol number concentration. Simulations were analyzed with a focus on the processes related to liquid phase microphysics, and ice formation was limited to droplet freezing. Of the aerosol properties investigated, aerosol insoluble mass type and its associated freezing efficiency was found to be most relevant to cloud lifetime. Secondary effects from aerosol soluble mass fraction and number concentration also alter cloud characteristics and lifetime. These alterations occur via various mechanisms, including changes to the amount of nucleated ice, influence on liquid phase precipitation and ice riming rates, and changes to liquid droplet nucleation and growth rates. Alteration of the aerosol properties in simulations with identical initial and boundary conditions results in large variability in simulated cloud thickness and lifetime, ranging from rapid and complete glaciation of liquid to the production of long-lived, thick stratiform mixed-phase cloud.

  17. Aqueous processing of alumina and phase behavior of polymeric additives

    NASA Astrophysics Data System (ADS)

    Sundlof, Brian Richard

    Microstructures observed when dextran sulfate and PEG were added to an aqueous alumina suspension resulted from polymeric phase separation. A suspension can be processed outside the phase separating region, followed by induced phase separation via changes in suspension pH, electrolyte level, and temperature. The processing method can be used to control pore size, shape and connectivity. The dispersion of aqueous suspensions of two alpha-aluminas was investigated. APA-0.5 was of high purity, and A-16 S.G. had MgO added as a sintering aid and contained other impurities (e.g., Na2O). The rheology of the alumina suspensions was manipulated via electrostatic (HCl H2SO 4, NaOH, and NH4OH) and electrosteric stabilization (Na- and NH4-PMAA, Na- and NH4-PAA, citric acid neutralized to a pH of ˜9.0, sodium silicate, sodium hexa-metaphosphate, and sodium carbonate). Rheological phenomena correlated with zeta-potential measurements, the dissociation behavior of the polyelectrolytes, and powder surface chemistry. A method was developed to measure the critical coagulation concentration (CCC) of stabilized suspensions. A critical double layer thickness ( d = ˜0.96 run) was calculated as a function of the electrolyte concentration and valence of the counter-ion, using a capacitance model. CCC estimations using the critical d value agreed with experimental observations. Microstructure development was dependent upon the disperant used during processing. Bulk density, and linear shrinkage measurements were used to evaluate the densification process of pellets slip cast then fired to 1000°C, 1200°C, 1400°C, or 1600°C. SEM micrographs of pellets fired to 1400°C, polished, then thermally etched, display variations in morphology and grain size. The presence of sodium resulted in abnormal grain growth, organics inhibited grain growth, and the inorganic dispersants severely inhibited grain growth. Polymeric interactions were observed using microscopy and light scattering in aqueous

  18. Metastable states in calcium phosphate - aqueous phase equilibrations

    NASA Astrophysics Data System (ADS)

    Driessens, F. C. M.; Verbeeck, R. M. H.

    1981-05-01

    A critical evaluation of the literature reveals that during equilibration of well crystallized hydroxyapatite in aqueous solutions metastable states can occur. They are characterized by a persistent supersaturation with respect to hydroxyapatite and a systematical dependence of the ion activity product of this compound on the solution composition. For products synthesized by thermal treatment it is known that they are transformed into oxyhydroxyapatite so that the theoretical solubility behaviour could be predicted from the extrapolated value of the free energy of oxyapatite at room temperature: the negative logarithm of the ionic product for hydroxyapatite should become close to that of oxyapatite during equilibration. The discrepancy with experimental data is probably due to the formation of thin layers seeming dicalcium phosphate dihydrate, octocalcium phosphate or defective hydroxyapatite as coatings on the apatite crystals. This is derived from the apparent Ca/P ratio of the solubility controlling phase. According to chemical potential plots this apparent Ca/P ratio can have values close to 1, 1.33, 1.50 or 1.67. The aqueous solutions are clearly undersaturated with respect to the more acidic calcium phosphates so that the coatings must deviate from the compositions of these compounds in their pure state. The formation of these metastable states during equilibration of oxyhydroxyapatites is compared with others occuring during precipitation and crystal growth of calcium phosphates. A model is proposed which explains the observations qualitatively.

  19. Thermoseparating aqueous two-phase systems: Recent trends and mechanisms.

    PubMed

    Leong, Yoong Kit; Lan, John Chi-Wei; Loh, Hwei-San; Ling, Tau Chuan; Ooi, Chien Wei; Show, Pau Loke

    2016-02-01

    Having the benefits of being environmentally friendly, providing a mild environment for bioseparation, and scalability, aqueous two-phase systems (ATPSs) have increasingly caught the attention of industry and researchers for their application in the isolation and recovery of bioproducts. The limitations of conventional ATPSs give rise to the development of temperature-induced ATPSs that have distinctive thermoseparating properties and easy recyclability. This review starts with a brief introduction to thermoseparating ATPSs, including its history, unique characteristics and advantages, and lastly, key factors that influence partitioning. The underlying mechanism of temperature-induced ATPSs is covered together with a summary of recent applications. Thermoseparating ATPSs have been proven as a solution to the demand for economically favorable and environmentally friendly industrial-scale bioextraction and purification techniques. PMID:26447739

  20. Sources of secondary organic aerosols in the Pearl River Delta region in fall: Contributions from the aqueous reactive uptake of dicarbonyls

    NASA Astrophysics Data System (ADS)

    Li, Nan; Fu, Tzung-May; Cao, Junji; Lee, Shuncheng; Huang, Xiao-Feng; He, Ling-Yan; Ho, Kin-Fai; Fu, Joshua S.; Lam, Yun-Fat

    2013-09-01

    We used the regional air quality model CMAQ to simulate organic aerosol (OA) concentrations over the Pearl River Delta region (PRD) and compared model results to measurements. Our goals were (1) to evaluate the potential contribution of the aqueous reactive uptake of dicarbonyls (glyoxal and methylglyoxal) as a source of secondary organic aerosol (SOA) in an urban environment, and (2) to quantify the sources of SOA in the PRD in fall. We improved the representation of dicarbonyl gas phase chemistry in CMAQ, as well as added SOA formation via the irreversible uptake of dicarbonyls by aqueous aerosols and cloud droplets, characterized by a reactive uptake coefficient γ = 2.9 × 10-3 based on laboratory studies. Our model results were compared to aerosol mass spectrometry (AMS) measurements in Shenzhen during a photochemical smog event in fall 2009. Including the new dicarbonyl SOA source in CMAQ led to an increase in the simulated mean SOA concentration at the sampling site from 4.1 μg m-3 to 9.0 μg m-3 during the smog event, in better agreement with the mean observed oxygenated OA (OOA) concentration (8.0 μg m-3). The simulated SOA reproduced the variability of observed OOA (r = 0.89). Moreover, simulated dicarbonyl SOA was highly correlated with simulated sulfate (r = 0.72), consistent with the observed high correlation between OOA and sulfate (r = 0.84). Including the dicarbonyl SOA source also increased the mean simulated concentrations of total OA from 8.2 μg m-3 to 13.1 μg m-3, closer to the mean observed OA concentration (16.5 μg m-3). The remaining difference between the observed and simulated OA was largely due to impacts from episodic biomass burning emissions, but the model did not capture this variability. We concluded that, for the PRD in fall and outside of major biomass burning events, 75% of the total SOA was biogenic. Isoprene was the most important precursor, accounting for 41% of the total SOA. Aromatics accounted for 13% of the total SOA

  1. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-07-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  2. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-01-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic aerosols (BA), for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2) and malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment, except for ω-oxooctanoic acid (ωC8) that showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids dominates their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  3. Dynamic equilibrium dissolution of complex nonaqueous phase liquid mixtures into the aqueous phase.

    PubMed

    Schluep, Mathias; Gälli, René; Imboden, Dieter M; Zeyer, Josef

    2002-07-01

    Human health risks posed by hazardous substances seeping from a pool of nonaqueous phase liquids (NAPLs) into groundwater change over time because the more soluble compounds such as benzene, toluene, ethylbenzene, and xylene (BTEX) dissolve faster into the aqueous phase than less soluble compounds such as polycyclic aromatic hydrocarbons (PAH). Long-term dissolution from diesel fuel into the aqueous phase was determined experimentally in a continuous flow-through system using the slow-stirring method. The data obtained are interpreted using a dynamic equilibrium dissolution model based on Raoult's law. The predicted temporal development of aqueous concentrations are in good agreement with the experimental results. When a compound in the NAPL approaches complete depletion, a tailing behavior is observed, which is assigned to nonequilibrium effects, such as mass transfer limitations in the NAPL phase. The model predicted an increase of the mean molar mass of the diesel fuel of 1.5% over the entire experimental period. It should be noted that, if the dissolution process were to proceed further, the change in the mean molar mass could become significant and render the simple model inaccurate. Yet the simple model supports the assessment of initial action after a contamination event as well as the planning of long-term remedial strategies. PMID:12109733

  4. Dynamic equilibrium dissolution of complex nonaqueous phase liquid mixtures into the aqueous phase.

    PubMed

    Schluep, Mathias; Gälli, René; Imboden, Dieter M; Zeyer, Josef

    2002-07-01

    Human health risks posed by hazardous substances seeping from a pool of nonaqueous phase liquids (NAPLs) into groundwater change over time because the more soluble compounds such as benzene, toluene, ethylbenzene, and xylene (BTEX) dissolve faster into the aqueous phase than less soluble compounds such as polycyclic aromatic hydrocarbons (PAH). Long-term dissolution from diesel fuel into the aqueous phase was determined experimentally in a continuous flow-through system using the slow-stirring method. The data obtained are interpreted using a dynamic equilibrium dissolution model based on Raoult's law. The predicted temporal development of aqueous concentrations are in good agreement with the experimental results. When a compound in the NAPL approaches complete depletion, a tailing behavior is observed, which is assigned to nonequilibrium effects, such as mass transfer limitations in the NAPL phase. The model predicted an increase of the mean molar mass of the diesel fuel of 1.5% over the entire experimental period. It should be noted that, if the dissolution process were to proceed further, the change in the mean molar mass could become significant and render the simple model inaccurate. Yet the simple model supports the assessment of initial action after a contamination event as well as the planning of long-term remedial strategies.

  5. Improvement and further development in CESM/CAM5: gas-phase chemistry and inorganic aerosol treatments

    NASA Astrophysics Data System (ADS)

    He, J.; Zhang, Y.

    2014-09-01

    Gas-phase chemistry and subsequent gas-to-particle conversion processes such as new particle formation, condensation, and thermodynamic partitioning have large impacts on air quality, climate, and public health through influencing the amounts and distributions of gaseous precursors and secondary aerosols. Their roles in global air quality and climate are examined in this work using the Community Earth System Model version 1.0.5 (CESM1.0.5) with the Community Atmosphere Model version 5.1 (CAM5.1) (referred to as CESM1.0.5/CAM5.1). CAM5.1 includes a simple chemistry that is coupled with a 7-mode prognostic Modal Aerosol Model (MAM7). MAM7 includes classical homogenous nucleation (binary and ternary) and activation nucleation (empirical first-order power law) parameterizations, and a highly simplified inorganic aerosol thermodynamics treatment that only simulates particulate-phase sulfate and ammonium. In this work, a new gas-phase chemistry mechanism based on the 2005 Carbon Bond Mechanism for Global Extension (CB05_GE) and several advanced inorganic aerosol treatments for condensation of volatile species, ion-mediated nucleation (IMN), and explicit inorganic aerosol thermodynamics for sulfate, ammonium, nitrate, sodium, and chloride have been incorporated into CESM/CAM5.1-MAM7. Compared to the simple gas-phase chemistry, CB05_GE can predict many more gaseous species, and thus could improve model performance for PM2.5, PM10, PM components, and some PM gaseous precursors such as SO2 and NH3 in several regions as well as aerosol optical depth (AOD) and cloud properties (e.g., cloud fraction (CF), cloud droplet number concentration (CDNC), and shortwave cloud forcing, SWCF) on the global scale. The modified condensation and aqueous-phase chemistry could further improve the prediction of additional variables such as HNO3, NO2, and O3 in some regions, and new particle formation rate (J) and AOD on the global scale. IMN can improve the prediction of secondary PM2

  6. Light Absorption by Secondary Organic Aerosol Produced from Aqueous Reaction of Phenols with an Organic Excited Triplet State and Hydroxyl Radical

    NASA Astrophysics Data System (ADS)

    Smith, J.; Yu, L.; George, K.; Ruthenburg, T. C.; Dillner, A. M.; Zhang, Q.; Anastasio, C.

    2012-12-01

    Although reactions in atmospheric condensed phases can form and transform secondary organic aerosol (SOA), these reactions are not well represented in many air quality models. Previous experiments have focused on hydroxyl radical-mediated oxidation of low molecular weight precursors such as gyloxal and methylglyoxal. In our work we are examining aqueous SOA formed from phenols, which are emitted from biomass burning and formed from the oxidation of anthropogenic aromatics such as benzene and toluene. In this work we examine aqueous SOA production from oxidation of three phenols (phenol, guaiacol, syringol) and three benzene-diols (catechol, resorcinol, 1,4-hydroquinone) by hydroxyl radical (OH) and the triplet excited state of 3,4-dimethoxybenzaldehyde (DMB). Our focus is on light absorption by the reaction products, which we characterized by measuring UV-Vis spectra and calculating mass absorption coefficients. To understand the elemental and molecular composition of the SOA, we also analyzed the samples with high resolution mass spectrometry and infrared spectroscopy. Our results indicate that aqueous oxidation of phenols and benzene-diols via OH and triplet excited states efficiently produce SOA that is highly absorbing in the UV-A wavelengths, consists of both small and large molecular weight products, and is highly oxidized.

  7. Bulk, surface, and gas-phase limited water transport in aerosol.

    PubMed

    Davies, James F; Haddrell, Allen E; Miles, Rachael E H; Bull, Craig R; Reid, Jonathan P

    2012-11-15

    The influence of solute species on mass transfer to and from aqueous aerosol droplets is investigated using an electrodynamic balance coupled with light scattering techniques. In particular, we explore the limitations imposed on water evaporation by slow bulk phase diffusion and by the formation of surface organic films. Measurements of evaporation from ionic salt solutions, specifically sodium chloride and ammonium sulfate, are compared with predictions from an analytical model framework, highlighting the uncertainties associated with quantifying gas diffusional transport. The influence of low solubility organic acids on mass transfer is reported and compared to both model predictions and previous work. The limiting value of the evaporation coefficient that can be resolved by this approach, when uncertainties in key thermophysical quantities are accounted for, is estimated. The limitation of slow bulk phase diffusion on the evaporation rate is investigated for gel and glass states formed during the evaporation of magnesium sulfate and sucrose droplets, respectively. Finally, the effect of surfactants on evaporation has been probed, with soluble surfactants (such as sodium dodecyl sulfate) leading to little or no retardation of evaporation through slowing of surface layer kinetics. PMID:23095147

  8. Aqueous glyoxal photooxidation in the presence of inorganic nitrogen: A potential source of organic nitrogen in aerosols and wet deposition

    NASA Astrophysics Data System (ADS)

    Kirkland, J. R.; Tan, Y.; Altieri, K. E.; Seitzinger, S.; Turpin, B. J.

    2010-12-01

    The sources of organic nitrogen in aerosols and atmospheric wet deposition are poorly understood, yet are important when assessing potential anthropogenic impacts on global nitrogen budgets. Nitrogen-containing organics are formed through gas phase photochemistry (e.g., involving NOx and isoprene). Imidazoles have been reported to form during smog chamber experiments involving glyoxal and ammonium sulfate seed particles. We hypothesize that nitrogen-containing organic compounds also form during cloud processing of water-soluble organic gases. Specifically, in this work we examine the possibility that organic nitrogen forms from GLY and inorganic nitrogen (NO3- or NH4+) at conditions found in daytime liquid clouds. We conducted batch aqueous reactions of GLY (1 mM) and OH radical (~10^-12 M) with and without nitric acid (1.7 mM) and ammonium sulfate (0.84 mM). OH radical was formed from the continuous photolysis of H2O2. Products were analyzed by ion chromatography (IC) and electrospray ionization mass spectrometry with pre-separation by IC (IC/ESI-MS). The addition of ammonium or nitrate had little effect on the concentrations of major system species (i.e., oxalate, glycolate) in the presence and absence of OH radical. Concentrations of inorganic nitrate and sulfate showed no significant change throughout light and dark experiments. ESI mass spectra with and without pre-separation by IC and ultra high resolution Fourier transform ion cyclotron resonance mass spectral analysis of samples will be examined and any evidence of organic nitrogen products will be discussed.

  9. A numerical study of aerosol influence on mixed-phase stratiform clouds through modulation of the liquid phase

    NASA Astrophysics Data System (ADS)

    de Boer, G.; Hashino, T.; Tripoli, G. J.; Eloranta, E. W.

    2012-08-01

    Numerical simulations were carried out in a high-resolution two dimensional framework to increase our understanding of aerosol indirect effects in mixed-phase stratiform clouds. Aerosol characteristics explored include insoluble particle type, soluble mass fraction, the influence of aerosol-induced freezing point depression and the influence of aerosol number concentration. These experiments were completed with an emphasis on the liquid phase, with droplet freezing the mechanism for ice production. Of the aerosol properties investigated, aerosol insoluble mass type and its associated freezing efficiency was found to be most relevant to cloud lifetime. Secondary effects from aerosol soluble mass fraction and number concentration also alter cloud characteristics and lifetime. These alterations occur via various mechanisms, including changes to the amount of nucleated ice, influence on liquid phase precipitation and ice riming rates, and changes to liquid droplet growth rates. Simulation of the same environment leads to large variability of cloud thickness and lifetime, ranging from rapid and complete glaciation of the cloud to the production of a long-lived, thick stratiform mixed-phase cloud. In the end, these processes are summarized into a diagram that includes internal feedback loops that act within the cloud system.

  10. Direct Aqueous Photochemistry of Isoprene High-NOx Secondary Organic Aerosol

    SciTech Connect

    Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2012-05-17

    Secondary organic aerosol (SOA) generated from the high-NOx photooxidation of isoprene was dissolved in water and irradiated with {lambda} > 290 nm light to simulate direct photolytic processing of organics in atmospheric water droplets. High-resolution mass spectrometry was used to characterize the composition at four time intervals (0, 1, 2, and 4 h). Photolysis resulted in the decomposition of high molecular weight (MW) oligomers, reducing the average length of organics by 2 carbon units. Approximately 65% by count of SOA molecules decomposed during photolysis, accompanied by the formation of new products. An average of 30 % of the organic mass was modified after 4 h of direct photolysis. In contrast, only a small fraction of the mass (<2 %), belonging primarily to organic nitrates, decomposed in the absence of irradiation by hydrolysis. We observed a statistically-significant increase in average O/C, decrease in H/C, and increase in N/C ratios resulting from photolysis. Furthermore, the concentration of aromatic compounds increased significantly during photolysis. Approximately 10 % of photodegraded compounds and 50 % of the photoproducts contain nitrogen. Organic nitrates and multifunctional oligomers were identified as compounds degraded by photolysis. Low-MW 0N (compounds with 0 nitrogen atoms in their structure) and 2N compounds were the dominant photoproducts. Fragmentation experiments using tandem mass spectrometry (MSn, n = 2-3) indicate that the 2N products are likely heterocyclic/aromatic and are tentatively identified as furoxans. Although the exact mechanism is unclear, these 2N heterocyclic compounds are produced by reactions between photochemically-formed aqueous NOx species and SOA organics.

  11. Aqueous Two Phase System Assisted Self-Assembled PLGA Microparticles

    NASA Astrophysics Data System (ADS)

    Yeredla, Nitish; Kojima, Taisuke; Yang, Yi; Takayama, Shuichi; Kanapathipillai, Mathumai

    2016-06-01

    Here, we produce poly(lactide-co-glycolide) (PLGA) based microparticles with varying morphologies, and temperature responsive properties utilizing a Pluronic F127/dextran aqueous two-phase system (ATPS) assisted self-assembly. The PLGA polymer, when emulsified in Pluronic F127/dextran ATPS, forms unique microparticle structures due to ATPS guided-self assembly. Depending on the PLGA concentration, the particles either formed a core-shell or a composite microparticle structure. The microparticles facilitate the simultaneous incorporation of both hydrophobic and hydrophilic molecules, due to their amphiphilic macromolecule composition. Further, due to the lower critical solution temperature (LCST) properties of Pluronic F127, the particles exhibit temperature responsiveness. The ATPS based microparticle formation demonstrated in this study, serves as a novel platform for PLGA/polymer based tunable micro/nano particle and polymersome development. The unique properties may be useful in applications such as theranostics, synthesis of complex structure particles, bioreaction/mineralization at the two-phase interface, and bioseparations.

  12. Aqueous Two Phase System Assisted Self-Assembled PLGA Microparticles

    PubMed Central

    Yeredla, Nitish; Kojima, Taisuke; Yang, Yi; Takayama, Shuichi; Kanapathipillai, Mathumai

    2016-01-01

    Here, we produce poly(lactide-co-glycolide) (PLGA) based microparticles with varying morphologies, and temperature responsive properties utilizing a Pluronic F127/dextran aqueous two-phase system (ATPS) assisted self-assembly. The PLGA polymer, when emulsified in Pluronic F127/dextran ATPS, forms unique microparticle structures due to ATPS guided-self assembly. Depending on the PLGA concentration, the particles either formed a core-shell or a composite microparticle structure. The microparticles facilitate the simultaneous incorporation of both hydrophobic and hydrophilic molecules, due to their amphiphilic macromolecule composition. Further, due to the lower critical solution temperature (LCST) properties of Pluronic F127, the particles exhibit temperature responsiveness. The ATPS based microparticle formation demonstrated in this study, serves as a novel platform for PLGA/polymer based tunable micro/nano particle and polymersome development. The unique properties may be useful in applications such as theranostics, synthesis of complex structure particles, bioreaction/mineralization at the two-phase interface, and bioseparations. PMID:27279329

  13. Structure and phase behavior of aqueous methylcellulose solutions

    NASA Astrophysics Data System (ADS)

    McAllister, John; Schmidt, Peter; Lodge, Timothy; Bates, Frank

    2015-03-01

    Cellulose ethers (CE) constitute a multi-billion dollar industry, and have found end uses in a broad array of applications from construction materials, food products, personal care products, and pharmaceuticals for more than 80 years. Methylcellulose (MC, with the trade name METHOCEL™) is a CE in which there is a partial substitution of -OH groups with -OCH3 groups. This results in a polymer that is water-soluble at low temperatures, and aqueous solutions of MC display gelation and phase separation at higher temperatures. The nature of MC gelation has been debated for many years, and this project has made significant advances in the understanding of the solution properties of CEs. We have characterized a fibrillar structure of MC gels by cryogenic transmission electron microscopy (cryo-TEM) and small angle neutron scattering (SANS). Using light scattering, turbidity measurements, and dynamic mechanical spectroscopy (DMS) we report that MC microphase separates by nucleation and growth of fibril aggregates, and is a different process from LCST phase separation.

  14. Sequential electrolytic oxidation and reduction of aqueous phase energetic compounds.

    PubMed

    Gilbert, David M; Sale, Tom C

    2005-12-01

    Contamination of soils and groundwater with energetic compounds has been documented at many former ammunition manufacturing plants and ranges. Recent research at Colorado State University (CSU) has demonstrated the potential utility of electrolytic degradation of organic compounds using an electrolytic permeable reactive barrier (e-barrier). In principle, an electrolytic approach to degrade aqueous energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) or 2,4,6-trinitrotoluene (TNT) can overcome limitations of management strategies that involve solely oxidation or reduction, through sequential oxidation-reduction or reduction-oxidation. The objective of this proof-of-concept research was to evaluate transformation of aqueous phase RDX and TNT in flow-through electrolytic reactors. Laboratory experiments were conducted using six identical column reactors containing porous media and expanded titanium-mixed-metal-oxide electrodes. Three columns tested TNT transformation and three tested RDXtransformation. Electrode sequence was varied between columns and one column for each contaminant acted as a no-voltage control. Over 97% of TNT and 93% of RDX was transformed in the reactors under sequential oxidation-reduction. Significant accumulation of known degradation intermediates was not observed under sequential oxidation-reduction. Removal of approximately 90% of TNT and 40% of RDX was observed under sequential reduction-oxidation. Power requirements on the order of 3 W/m2 were measured during the experiment. This suggests that an in-situ electrolytic approach may be cost-practical for managing groundwater contaminated with explosive compounds.

  15. The Two-Column Aerosol Project: Phase I—Overview and impact of elevated aerosol layers on aerosol optical depth

    NASA Astrophysics Data System (ADS)

    Berg, Larry K.; Fast, Jerome D.; Barnard, James C.; Burton, Sharon P.; Cairns, Brian; Chand, Duli; Comstock, Jennifer M.; Dunagan, Stephen; Ferrare, Richard A.; Flynn, Connor J.; Hair, Johnathan W.; Hostetler, Chris A.; Hubbe, John; Jefferson, Anne; Johnson, Roy; Kassianov, Evgueni I.; Kluzek, Celine D.; Kollias, Pavlos; Lamer, Katia; Lantz, Kathleen; Mei, Fan; Miller, Mark A.; Michalsky, Joseph; Ortega, Ivan; Pekour, Mikhail; Rogers, Ray R.; Russell, Philip B.; Redemann, Jens; Sedlacek, Arthur J.; Segal-Rosenheimer, Michal; Schmid, Beat; Shilling, John E.; Shinozuka, Yohei; Springston, Stephen R.; Tomlinson, Jason M.; Tyrrell, Megan; Wilson, Jacqueline M.; Volkamer, Rainer; Zelenyuk, Alla; Berkowitz, Carl M.

    2016-01-01

    The Two-Column Aerosol Project (TCAP), conducted from June 2012 through June 2013, was a unique study designed to provide a comprehensive data set that can be used to investigate a number of important climate science questions, including those related to aerosol mixing state and aerosol radiative forcing. The study was designed to sample the atmosphere between and within two atmospheric columns; one fixed near the coast of North America (over Cape Cod, MA) and a second moveable column over the Atlantic Ocean several hundred kilometers from the coast. The U.S. Department of Energy's (DOE) Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) was deployed at the base of the Cape Cod column, and the ARM Aerial Facility was utilized for the summer and winter intensive observation periods. One important finding from TCAP is that four of six nearly cloud-free flight days had aerosol layers aloft in both the Cape Cod and maritime columns that were detected using the nadir pointing second-generation NASA high-spectral resolution lidar (HSRL-2). These layers contributed up to 60% of the total observed aerosol optical depth (AOD). Many of these layers were also intercepted by the aircraft configured for in situ sampling, and the aerosol in the layers was found to have increased amounts of biomass burning material and nitrate compared to aerosol found near the surface. In addition, while there was a great deal of spatial and day-to-day variability in the aerosol chemical composition and optical properties, no systematic differences between the two columns were observed.

  16. Aqueous-phase behavior of natural glycolipid biosurfactant mannosylerythritol lipid A: sponge, cubic, and lamellar phases.

    PubMed

    Imura, Tomohiro; Hikosaka, Yusuke; Worakitkanchanakul, Wannasiri; Sakai, Hideki; Abe, Masahiko; Konishi, Masaaki; Minamikawa, Hiroyuki; Kitamoto, Dai

    2007-02-13

    The aqueous-phase behavior of mannosylerythritol lipid A (MEL-A), which is a glycolipid biosurfactant produced from vegetable oils by yeast strains of the genus Pseudozyma, was investigated using polarized optical microscopy, small-angle X-ray scattering (SAXS), and differential scanning calorimetry (DSC). MEL-A was found to self-assemble into a variety of distinctive lyotropic liquid crystals including sponge (L3), bicontinuous cubic (V2), and lamella (Lalpha) phases. On the basis of SAXS measurements, we determined the structure of the liquid crystals. The estimated lattice constant for Lalpha was 3.58 nm. DSC measurement revealed that the phase transition enthalpies from the liquid crystal to the fluid isotropic phase were in the range of 0.22-0.44 kJ/mol. Although the present MEL-A phase diagram closely resembled that obtained from relatively hydrophobic poly(oxyethylene) or fluorinated surfactants, the MEL-A L3 region was spread considerably over a wide temperature range (20-65 degrees C) compared to L3 of those surfactants: this is probably due to the unique structure which is molecularly engineered by microorganisms. In this paper, we clarify the aqueous phase diagram of the natural glycolipid biosurfactant MEL-A, and we suggest that the obtained lyotropic crystals are potentially useful as novel nanostructured biomaterials. PMID:17279642

  17. Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

    DOE PAGES

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; George, Katheryn M.; Anastasio, Cort; Laskin, Julia; Dillner, Ann M.; Zhang, Qi

    2016-04-13

    Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as amore » function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to  ∼  2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values

  18. Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Laskin, A.; George, K. M.; Anastasio, C.; Laskin, J.; Dillner, A. M.; Zhang, Q.

    2015-10-01

    Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants - the triplet excited state of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ∼ 2 h irradiation under midday, winter solstice sunlight in northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated open-ring molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures C*) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C* values is observed

  19. Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

    NASA Astrophysics Data System (ADS)

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; George, Katheryn M.; Anastasio, Cort; Laskin, Julia; Dillner, Ann M.; Zhang, Qi

    2016-04-01

    Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants - the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ˜ 2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed

  20. Improvement and further development in CESM/CAM5: gas-phase chemistry and inorganic aerosol treatments

    NASA Astrophysics Data System (ADS)

    He, J.; Zhang, Y.

    2013-10-01

    Gas-phase chemistry and subsequent gas-to-particle conversion processes such as new particle formation, condensation, and thermodynamic partitioning have large impacts on air quality, climate, and public health through influencing the amounts and distributions of gaseous precursors and secondary aerosols. Their roles in global air quality and climate are examined in this work using the Community Earth System Model version 1.0.5 (CESM1.0.5) with the Community Atmosphere Model version 5.1 (CAM5.1) (referred to as CESM1.0.5/CAM5.1). CAM5.1 includes a simple chemistry that is coupled with a 7-mode prognostic Modal Aerosol Model (MAM7). MAM7 includes classical homogenous nucleation (binary and ternary) and activation nucleation (empirical first-order power law) parameterizations, and a highly-simplified inorganic aerosol thermodynamics treatment that only simulates sulfate (SO42-) and ammonium (NH4+). In this work, a new gas-phase chemistry mechanism based on the 2005 Carbon Bond Mechanism for Global Extension (CB05_GE) and several advanced inorganic aerosol treatments for condensation of volatile species, ion-mediated nucleation (IMN), and explicit inorganic aerosol thermodynamics have been incorporated into CESM/CAM5.1-MAM7. Comparing to the simple gas-phase chemistry, CB05_GE can predict many more gaseous species, and improve model performance for PM2.5, PM10, PM2.5 components, and some PM gaseous precursors such as SO2 and NH3 in several regions, as well as aerosol optical depth (AOD) and cloud properties (e.g., cloud fraction (CF), cloud droplet number concentration (CDNC), and shortwave cloud forcing (SWCF)) on globe. The modified condensation and aqueous-phase chemistry further improves the predictions of additional variables such as HNO3, NO2, and O3 in some regions, and new particle formation rate (J) and AOD over globe. IMN can improve the predictions of secondary PM2.5 components, PM2.5, and PM10 over Europe, as well as AOD and CDNC over globe. The explicit

  1. Downstream antibody purification using aqueous two-phase extraction.

    PubMed

    Mao, Lisong Nathan; Rogers, Jameson K; Westoby, Matthew; Conley, Lynn; Pieracci, John

    2010-01-01

    The extraction of antibodies using a polyethylene glycol (PEG)-citrate aqueous two-phase system (ATPS) was investigated. Studies using purified monoclonal antibody (mAb) identified operating ranges for successful phase formation and factors that significantly affected antibody partitioning. The separation of antibody and host cell protein (HCP) from clarified cell culture media was examined using statistical design of experiments (DOE). The partitioning of antibody was nearly complete over the entire range of the operating space examined. A model of the HCP partitioning was generated in which both NaCl and citrate concentrations were identified as significant factors. To achieve the highest purity, the partitioning of HCP from cell culture fluid into the product containing phase was minimized using a Steepest Descent algorithm. An optimal ATPS consisting of 14.0% (w/w) PEG, 8.4% (w/w) citrate, and 7.2% (w/w) NaCl at pH 7.2 resulted in a product yield of 89%, an approximate 7.6-fold reduction in HCP levels relative to the clarified cell culture fluid before extraction and an overall purity of 70%. A system consisting of 15% (w/w) PEG, 8% (w/w) citrate, and 15% (w/w) NaCl at pH 5.5 reduced product-related impurities (aggregates and low molecular product fragments) from ∼40% to less than 0.5% while achieving 95% product recovery. At the experimental conditions that were optimized in the batch mode, a scale-up model for the use of counter-current extraction technology was developed to identify potential improvements in purity and recovery that could be realized in the continuous operational mode. PMID:20853347

  2. Development of tropine-salt aqueous two-phase systems and removal of hydrophilic ionic liquids from aqueous solution.

    PubMed

    Wu, Haoran; Yao, Shun; Qian, Guofei; Song, Hang

    2016-08-26

    A novel aqueous two-phase systems (ATPS) composed of a small molecule organic compound tropine and an organic or inorganic salt aqueous solution has been developed for the first time. The phase behavior of tropine-salt ATPS was systemically investigated and the phase equilibrium data were measured in different temperatures and concentrations and correlated by the Merchuk equation with satisfactory results. The detection of the conductivity and particle size proved the formation of micelle in the process of forming tropine-salt ATPS. The separation application of the ATPS was assessed with the removal of hydrophilic benzothiazolium-based ionic liquids (ILs) from aqueous solution. The result showed that ILs were effectively extracted into the top tropine-rich phase. Finally, ILs in the top tropine-rich phase were further separated by the means of adsorption-desorption with DM301 macroporous resin and ethanol. The method of novel tropine-salt ATPS combined with adsorption-desorption is demonstrated a promising alternative thought and approach for the removal or recovery of hydrophilic compounds from aqueous media and also could provide a potential application for bio-separation. PMID:27485150

  3. Reactions of important OVOCs with hydrogen peroxide and ozone in the tropospheric aqueous phase

    NASA Astrophysics Data System (ADS)

    Schöne, Luisa; Weller, Christian; Herrmann, Hartmut

    2013-04-01

    Besides research on the microphysics of cloud droplets and similar aqueous systems in the troposphere, the chemistry of volatile organic compounds (VOCs) from anthropogenic and biogenic sources cannot be neglected for the understanding of tropospheric processes such as the organic particle mass formation. Emissions of biogenic volatile organic compounds (BVOCs) can exceed those of VOCs from anthropogenic sources by a factor of 10[1]. Oxidation products of BVOCs like glyoxal, methylglyoxal, glycolate, glyoxylate and pyruvate, glycolaldehyde, and the unsaturated compounds methacrolein and methyl vinyl ketone are known precursors for less volatile organic substances found in secondary organic aerosols[2,3]. Yet, the main decomposition of these substances is believed to occur via radical reactions. However, Tilgner and Herrmann[2] showed evidence that the turnovers by non-radical reactions with H2O2 or ozone and some non-oxidative organic accretion reactions may even exceed those from the most reactive species in the lower troposphere, the hydroxyl radical OH. This work investigated the reactivities of the atmospheric relevant oxidation products including pyruvic acid and glyoxylic acid towards O3 and H2O2 in the aqueous phase. Furthermore, pH effects were studied by measuring the kinetics of both the protonated and deprotonated forms. The measurements were performed using a UV/VIS-spectrometer (conventional and in addition a Stopped Flow technique) and capillary electrophoresis. In some cases the results indicate higher turnovers of H2O2 and ozone reactions compared to interactions with atmospheric radicals. The experimental data obtained will be presented and their implications for atmospheric multiphase chemistry are discussed. [1] Guenther et al., 1995, Journal of Geophysical Research - Atmosphere, 100(D5), 8873-8892. [2] Tilgner and Herrmann, 2010, Atmospheric Environment, 44, 5415-5422. [3] van Pinxteren et al., 2005, Atmospheric Environment, 39, 4305-4320.

  4. How Is the Oxidative Capacity of the Cloud Aqueous Phase Modified By Bacteria?

    NASA Astrophysics Data System (ADS)

    Deguillaume, L.; Mouchel-Vallon, C.; Passananti, M.; Wirgot, N.; Joly, M.; Sancelme, M.; Bianco, A.; Cartier, N.; Brigante, M.; Mailhot, G.; Delort, A. M.; Chaumerliac, N. M.

    2014-12-01

    The aqueous phase photochemical reactions of constituents present in atmospheric water like H2O2, NO3-, NO2- and Fe(III) aqua-complexes or organic complexes can form radicals such as the hydroxyl radical HO within the water drop. However, the literature lacks of data precising the rate of HO formation and the relative contribution of the photochemical sources of HO. The production of radicals in cloud aqueous phase drives the oxidative capacity of the cloud medium and the efficiency of organic matter oxidation. The oxidation of organic compounds is suspected to lead to oxygenated species that could contribute to secondary organic aerosol (SOA) mass (Ervens et al., 2011). In current cloud chemistry models, HO concentrations strongly depend on the organic and iron amount. For high concentrations of organic compounds, this radical is efficiently consumed during the day due to the oxidation process. When iron concentrations are typical from continental cloud, the photolysis of Fe(III) complexes and the Fenton reaction drive the HO concentrations in the cloud models. The concept of biocatalysed reactions contributing to atmospheric chemistry as an alternative route to photochemistry is quite new (Vaïtilingom et al., 2013); it emerged from the recent discovery of metabolically active microorganisms in clouds. Microorganisms are well-known to degrade organic matter but they could also interact with oxidant species such as H2O2 (or their precursors) thanks to their oxidative and nitrosative stress metabolism that will act directly on these species and on their interactions with iron (metalloproteins and siderophores). For the moment, biological impact on radical chemistry within cloud has not been yet considered in cloud chemistry models. Bacterial activity will be introduced as catalysts in a multiphase cloud chemistry model using degradation rates measured in the laboratory. For example, biodegradation rates of the oxidants H2O2 by model bacteria will be tested in the

  5. Non-aqueous phase liquid spreading during soil vapor extraction

    PubMed Central

    Kneafsey, Timothy J.; Hunt, James R.

    2010-01-01

    Many non-aqueous phase liquids (NAPLs) are expected to spread at the air – water interface, particularly under non-equilibrium conditions. In the vadose zone, this spreading should increase the surface area for mass transfer and the efficiency of volatile NAPL recovery by soil vapor extraction (SVE). Observations of spreading on water wet surfaces led to a conceptual model of oil spreading vertically above a NAPL pool in the vadose zone. Analysis of this model predicts that spreading can enhance the SVE contaminant recovery compared to conditions where the liquid does not spread. Experiments were conducted with spreading volatile oils hexane and heptane in wet porous media and capillary tubes, where spreading was observed at the scale of centimeters. Within porous medium columns up to a meter in height containing stagnant gas, spreading was less than ten centimeters and did not contribute significantly to hexane volatilization. Water film thinning and oil film pinning may have prevented significant oil film spreading, and thus did not enhance SVE at the scale of a meter. The experiments performed indicate that volatile oil spreading at the field scale is unlikely to contribute significantly to the efficiency of SVE. PMID:14734243

  6. Heteroaggregation of graphene oxide with minerals in aqueous phase.

    PubMed

    Zhao, Jian; Liu, Feifei; Wang, Zhenyu; Cao, Xuesong; Xing, Baoshan

    2015-03-01

    Upon release into waters, sediments, and soils, graphene oxide (GO) may interact with fine mineral particles. We investigated the heteroaggregation of GO with different minerals, including montmorillonite, kaolinite, and goethite, in aqueous phase. GO significantly enhanced the dispersion of positively charged goethite (>50%) via heteroaggregation, while there was no interaction between GO and negatively charged montmorillonite or kaolinite. Electrostatic attraction was the dominant force in the GO-goethite heteroaggregation (pH 4.0-8.5), and the dissolved Fe ions (<0.16 mg/L) from goethite were unable to destabilize GO suspension. The GO-goethite heteroaggregation was further quantitatively investigated through GO adsorption study. All adsorption isotherms of GO at different solution pH (4.0 and 6.5) followed the Linear model. The apparent intercept (1.0-6.9 mg/g) was observed for all the adsorption isotherms, indicating that this fraction of adsorbed GO was difficult to desorb from goethite (defined here as irreversible adsorption) under the tested conditions. Desorption hysteresis was observed, which could be explained by the formation of multilayered GO-goethite complex with high configurational stability. These findings are useful for understanding the interaction of GO with mineral surfaces, and potential fate and toxicity of GO under natural conditions in aquatic environments, as well as in soils and sediments. PMID:25614925

  7. Heteroaggregation of graphene oxide with minerals in aqueous phase.

    PubMed

    Zhao, Jian; Liu, Feifei; Wang, Zhenyu; Cao, Xuesong; Xing, Baoshan

    2015-03-01

    Upon release into waters, sediments, and soils, graphene oxide (GO) may interact with fine mineral particles. We investigated the heteroaggregation of GO with different minerals, including montmorillonite, kaolinite, and goethite, in aqueous phase. GO significantly enhanced the dispersion of positively charged goethite (>50%) via heteroaggregation, while there was no interaction between GO and negatively charged montmorillonite or kaolinite. Electrostatic attraction was the dominant force in the GO-goethite heteroaggregation (pH 4.0-8.5), and the dissolved Fe ions (<0.16 mg/L) from goethite were unable to destabilize GO suspension. The GO-goethite heteroaggregation was further quantitatively investigated through GO adsorption study. All adsorption isotherms of GO at different solution pH (4.0 and 6.5) followed the Linear model. The apparent intercept (1.0-6.9 mg/g) was observed for all the adsorption isotherms, indicating that this fraction of adsorbed GO was difficult to desorb from goethite (defined here as irreversible adsorption) under the tested conditions. Desorption hysteresis was observed, which could be explained by the formation of multilayered GO-goethite complex with high configurational stability. These findings are useful for understanding the interaction of GO with mineral surfaces, and potential fate and toxicity of GO under natural conditions in aquatic environments, as well as in soils and sediments.

  8. Temperature- and pH-dependent aqueous-phase kinetics of the reactions of glyoxal and methylglyoxal with atmospheric amines and ammonium sulfate

    NASA Astrophysics Data System (ADS)

    Sedehi, Nahzaneen; Takano, Hiromi; Blasic, Vanessa A.; Sullivan, Kristin A.; De Haan, David O.

    2013-10-01

    Reactions of glyoxal (Glx) and methylglyoxal (MG) with primary amines and ammonium salts may produce brown carbon and N-containing oligomers in aqueous aerosol. 1H NMR monitoring of reactant losses and product appearance in bulk aqueous reactions were used to derive rate constants and quantify competing reaction pathways as a function of pH and temperature. Glx + ammonium sulfate (AS) and amine reactions generate products containing C-N bonds, with rates depending directly on pH: rate = (70 ± 60) M-1 s-1fAld [Glx]totfAm [Am]tot, where fAld is the fraction of aldehyde with a dehydrated aldehyde functional group, and fAm is the fraction of amine or ammonia that is deprotonated at a given pH. MG + amine reactions generate mostly aldol condensation products and exhibit less pH dependence: rate = 10[(0.36 ± 0.06) × pH - (3.6 ± 0.3)] M-1 s-1fAld [MG]tot [Am]tot. Aldehyde + AS reactions are less temperature-dependent (Ea = 18 ± 8 kJ mol-1) than corresponding amine reactions (Ea = 50 ± 11 kJ mol-1). Using aerosol concentrations of [OH] = 10-12 M, [amine]tot = [AS] = 0.1 M, fGlx = 0.046 and fMG = 0.09, we estimate that OH radical reactions are normally the major aerosol-phase sink for both dicarbonyl compounds. However, reactions with AS and amines together can account for up to 12 and 45% of daytime aerosol-phase glyoxal and methylglyoxal reactivity, respectively, in marine aerosol at pH 5.5. Reactions with AS and amines become less important in acidic or non-marine aerosol, but may still be significant atmospheric sources of brown carbon, imidazoles, and nitrogen-containing oligomers.

  9. Ice Phase Transitions by Atmospheric Aerosol Particles of Varied Composition

    NASA Astrophysics Data System (ADS)

    DeMott, P. J.; Prenni, A. J.; Archuleta, C. A.; Kreidenweis, S. M.; Cziczo, D. J.; Murphy, D. M.; Thomson, D. S.

    2001-12-01

    This paper describes laboratory and field study measurements of water uptake and ice nucleation by surrogate and real atmospheric aerosol particles. Laboratory measurements of water uptake are made using a humidified tandem differential mobility analyzer (HTDMA) and a cloud condensation nucleus (CCN) instrument operating at 20 to 30 \\deg C. Measurements of ice nucleation are made using a continuous flow ice-thermal diffusion chamber (CFDC) operated to -60 \\deg C for relevance toward understanding cirrus cloud formation. Extending earlier laboratory studies of single composition aerosols, we are investigating water uptake and ice nucleation rates and mechanisms by mixed aerosols of various types, including sulfate-nitrate, sulfate-organic, mineral oxide-sulfate and black carbon-sulfate types. Methodologies will be described and results will be summarized. Field measurements are planned to study heterogeneous and homogeneous ice nucleation by free tropospheric aerosols at a high altitude laboratory. The field study will include measurements of the compositions of aerosols that activate ice formation by homogeneous and heterogeneous ice nucleation mechanisms. This aspect of the study will be facilitated by interfacing the CFDC to the PALMS (Particle Analysis by Laser Mass Spectrometry) instrument. This combined instrument system was tested in the laboratory to quantify sampling efficiencies and validate specificity for sampling ice nucleus aerosol particles. Initial field data, if available at conference time, will be compared and contrasted with the results obtained for laboratory surrogate particles.

  10. Global Impacts of Gas-Phase Chemistry-Aerosol Interactions on Direct Radiative Forcing by Anthropogenic Aerosols and Ozone

    NASA Technical Reports Server (NTRS)

    Liao, Hong; Seinfeld, John H.

    2005-01-01

    We present here a first global modeling study on the influence of gas-phase chemistry/aerosol interactions on estimates of anthropogenic forcing by tropospheric O3 and aerosols. Concentrations of gas-phase species and sulfate, nitrate, ammonium, black carbon, primary organic carbon, secondary organic carbon, sea salt, and mineral dust aerosols in the preindustrial, present-day, and year 2100 (IPCC SRES A2) atmospheres are simulated online in the Goddard Institute for Space Studies general circulation model II' (GISS GCM II'). With fully coupled chemistry and aerosols, the preindustrial, presentday, and year 2100 global burdens of tropospheric ozone are predicted to be 190, 319, and 519 Tg, respectively. The burdens of sulfate, nitrate, black carbon, and organic carbon are predicted respectively to be 0.32. 0.18, 0.01, 0.33 Tg in preindustrial time, 1.40, 0.48, 0.23, 1.60 Tg in presentday, and 1.37, 1.97, 0.54, 3.31 Tg in year 2100. Anthropogenic O3 is predicted to have a globally and annually averaged present-day forcing of +0.22 W m(sup -2) and year 2100 forcing of +0.57 W m(sup -2) at the top of the atmosphere (TOA). Net anthropogenic TOA forcing by internally mixed sulfate, nitrate, organic carbon, and black carbon aerosols is estimated to be virtually zero in the present-day and +0.34 W m(sup -2) in year 2100, whereas it is predicted to be -0.39 W m(sup -2) in present-day and -0.61 W m(sup -2) in year 2100 if the aerosols are externally mixed. Heterogeneous reactions are shown to be important in affecting anthropogenic forcing. When reactions of N2O5, NO3, NO2, and HO2 on aerosols are accounted for, TOA anthropogenic O3 forcing is less by 20-45% in present-day and by 20-32% in year 2100 at mid to high latitudes in the Northern Hemisphere, as compared with values predicted in the absence of heterogeneous gas aerosol reactions. Mineral dust uptake of HNO3 and O3 is shown to have practically no influence on anthropogenic O3 forcing. Heterogeneous reactions of N2Os

  11. Enzymatic hydrolysis in an aqueous organic two-phase system using centrifugal partition chromatography.

    PubMed

    Krause, J; Oeldorf, T; Schembecker, G; Merz, J

    2015-04-24

    Multi-phase reaction systems, mostly aqueous organic systems, are used in enzyme catalysis to convert hydrophobic substrates which are almost insoluble in aqueous media. In this study, a Centrifugal Partition Chromatograph is used as a compact device for enzymatic multi-phase reaction that combines efficient substrate supply to the aqueous phase and separation of both phases in one apparatus. A process design procedure to systematically select the aqueous and organic phase to achieve stable and efficient reaction rates and operation conditions in Centrifugal Partition Chromatography for efficient mixing and separation of the phases is presented. The procedure is applied to the hydrolysis of 4-nitrophenyl palmitate with a lipase derived from Candida rugosa. It was found that the hydrolysis rate of 4-nitrophenyl palmitate was two times higher in Centrifugal Partition Chromatography than in comparable stirred tank reactor experiments. PMID:25773726

  12. Enzymatic hydrolysis in an aqueous organic two-phase system using centrifugal partition chromatography.

    PubMed

    Krause, J; Oeldorf, T; Schembecker, G; Merz, J

    2015-04-24

    Multi-phase reaction systems, mostly aqueous organic systems, are used in enzyme catalysis to convert hydrophobic substrates which are almost insoluble in aqueous media. In this study, a Centrifugal Partition Chromatograph is used as a compact device for enzymatic multi-phase reaction that combines efficient substrate supply to the aqueous phase and separation of both phases in one apparatus. A process design procedure to systematically select the aqueous and organic phase to achieve stable and efficient reaction rates and operation conditions in Centrifugal Partition Chromatography for efficient mixing and separation of the phases is presented. The procedure is applied to the hydrolysis of 4-nitrophenyl palmitate with a lipase derived from Candida rugosa. It was found that the hydrolysis rate of 4-nitrophenyl palmitate was two times higher in Centrifugal Partition Chromatography than in comparable stirred tank reactor experiments.

  13. Purification of hyperthermophilic archaeal amylolytic enzyme (MJA1) using thermoseparating aqueous two-phase systems.

    PubMed

    Li, Mian; Peeples, Tonya L

    2004-07-25

    Purification of a recombinant, thermostable alpha-amylase (MJA1) from the hyperthermophile, Methanococcus jannaschii, was investigated in the ethylene oxide-propylene oxide random copolymer (PEO-PPO)/(NH(4))(2)SO(4), and poly(ethylene glycol) (PEG)/(NH(4))(2)SO(4) aqueous two-phase systems. MJA1 partitioned in the top polymer-rich phase, while the remainder of proteins partitioned in the bottom salt-rich phase. It was found that enzyme recovery of up to 90% with a purification factor of 3.31 was achieved using a single aqueous two-phase extraction step. In addition, the partition behavior of pure amyloglucosidase in polymer/salt aqueous two-phase systems was also evaluated. All of the studied enzymes partitioned unevenly in these polymer/salt systems. This work is the first reported application of thermoseparating polymer aqueous two-phase systems for the purification of extremophile enzymes. PMID:15177162

  14. Hydrogen production by aqueous phase reforming of light oxygenated hydrocarbons

    NASA Astrophysics Data System (ADS)

    Shabaker, John William

    Aqueous phase reforming (APR) of renewable oxygenated hydrocarbons (e.g., methanol, ethylene glycol, glycerol, sorbitol, glucose) is a promising new technology for the catalytic production of high-purity hydrogen for fuel cells and chemical processing. Supported Pt catalysts are effective catalysts for stable and rapid H2 production at temperatures near 500 K (H 2 turnover frequencies near 10 min-1). Inexpensive Raney Ni-based catalysts have been developed using a combination of fundamental and high-throughput studies that have similar catalytic properties as Pt-based materials. Promotion of Raney Ni with Sn by controlled surface reaction of organometallic tin compounds is necessary to control formation of thermodynamically-favorable alkane byproducts. Detailed characterization by Mossbauer spectroscopy, electron microscopy, adsorption studies, and x-ray photoelectron spectroscopy (XPS/ESCA) has shown that NiSn alloys are formed during heat treatment, and may be responsible for enhanced stability and selectivity for hydrogen production. Detailed kinetic studies led to the development of a kinetic mechanism for the APR reaction on Pt and NiSn catalysts, in which the oxygenate decomposes through C--H and O--H cleavage, followed by C--C cleavage and water gas shift of the CO intermediate. The rate limiting step on Pt surfaces is the initial dehydrogenation, while C--C cleavage appears rate limiting over NiSn catalysts. Tin promotion of Raney Ni catalysts suppresses C--O bond scission reactions that lead to alkane formation without inhibiting fast C--C and C--H cleavage steps that are necessary for high rates of reforming. A window of operating temperature, pressure, and reactor residence time has been identified for use of the inexpensive NiSn catalysts as a Pt substitute. Concentrated feed stocks and aggressive pretreatments have been found to counteract catalyst deactivation by sintering in the hydrothermal APR environment and allow stable, long-term production of H

  15. Secondary Organic Aerosol formation from the gas-phase reaction of catechol with ozone

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, C.; Tomas, A.; Guilloteau, A.; Henry, F.; Ledoux, F.; Visez, N.; Riffault, V.; Wenger, J. C.; Bedjanian, Y.; Foulon, V.

    2009-04-01

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers (at the LPCA in France and at the CRAC in Ireland). Aerosol production was monitored using a scanning mobility particle sizer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm-3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The aerosol yields determined in the LPCA and CRAC smog chambers were comparable and were also in accordance with those determined in a previous study performed in EUPHORE (EUropean PHOto REactor, Spain).

  16. Infrared spectroscopy and phase behavior of n-butane aerosols and thin films at cryogenic temperatures.

    PubMed

    Lang, E Kathrin; Knox, Kerry J; Momose, Takamasa; Signorell, Ruth

    2013-11-21

    Spectroscopic studies of two phase transitions of solid n-butane aerosol droplets performed under conditions representative of those in the lower atmosphere of Titan are presented. Pure n-butane aerosols and mixed ensembles of n-butane/acetylene, n-butane/carbon dioxide and n-butane/water aerosols were generated in a bath gas cooling cell at 78 K and their phase transition dynamics monitored using infrared extinction spectroscopy. For pure n-butane aerosols the volume and surface nucleation constants were found to range from JV = 10(12) -10(14) cm(-3) s(-1) and JS = 10(13) -10(15) cm(-2) s(-1), respectively, for the first observed transition, and JV = 10(9) -10(11) cm(-3) s(-1) and JS = 10(11) -10(13) cm(-2) s(-1) for the second observed transition. The phases of the n-butane aerosols were determined by comparing their spectroscopic signatures with spectra collected from thin films of liquid and solid n-butane. The first observed transition was from an amorphous-annealed phase into the metastable crystalline phase II of n-butane. The second transition was from the metastable crystalline phase II into the crystalline phase III. The effect of the presence of a second aerosol substance (acetylene, carbon dioxide or water) was examined; while this accelerated the first phase transition, it did not directly influence the rate of the second phase transition. The kinetic studies might be important for the understanding of cloud formation on Titan, while the spectral data provided, which include the first reported spectrum of liquid n-butane close to the melting point, are expected to be of use for remote sensing applications. PMID:23668828

  17. Solid-phase supported profluorescent nitroxide probe for the determination of aerosol-borne reactive oxygen species.

    PubMed

    Sleiman, Mohamad; Destaillats, Hugo; Gundel, Lara A

    2013-11-15

    Reactive oxygen species (ROS) and free radicals play important roles in the chemical transformation and adverse health effects of environmental aerosols. This work presents a simple and sensitive method for sampling and analysis of ROS using a packed column coated with a profluorescent nitroxide scavenger, proxyl fluorescamine (PF). Quantification was performed by extraction and analysis using HPLC with fluorescence detection. For comparison, the conventional method of collecting aerosols into dichlorofluorescin (DCFH) aqueous solution was used as a reference. The method was successfully applied to the determination of ROS in a model secondary organic aerosol (SOA) system generated by ozonolysis of nicotine, as well as in secondhand tobacco smoke (SHS). ROS concentrations between 50-565 nmol m(-3) were detected in fresh SOA and SHS samples. After SHS aging for 22 h, 13-18% of the initial ROS mass remained, suggesting the presence of persistent ROS. The new method offers better stability and reproducibility along with sensitivity comparable to that of DCFH (method detection limit of 3.2 and 1.4 nmol m(-3) of equivalent H2O2 for PF and DCFH respectively). The PF probe was stable during storage at room temperature and not reactive with ozone or NOx, whereas DCFH in the particle-collecting liquid system was strongly influenced by ozone and NOx interferences. This case study provides a good basis for employing solid-phase supported PF for field measurement of specific ROS in other combustion systems (i.e. biomass burning, candles, and diesel exhaust) and environmental aerosols. PMID:24148512

  18. Kinetic study of esterification of sulfuric acid with alcohols in aerosol bulk phase

    NASA Astrophysics Data System (ADS)

    Li, J.; Jang, M.

    2013-09-01

    In this study, we hypothesize that the formation of organosulfates through the reactions between sulfuric acid and alcohols in the aerosol bulk phase is more efficient than that in solution chemistry. To prove this hypothesis, the kinetics of the organosulfate formation was investigated for both aliphatic alcohol with single OH group (e.g., 1-heptanol) and the multialcohols ranging from semivolatiles (e.g., hydrated-glyoxal and glycerol) to nonvolatiles (e.g., sucrose) using analytical techniques directly monitoring aerosol bulk phase. Both the forward (k1) and the backward (k-1) reaction rate constants of organosulfate formation via the particle phase esterification of 1-heptanol with sulfuric acid were estimated using a Fourier Transform Infrared (FTIR) spectrometer equipped with a flow chamber under varying humidities. Both k1 and k-1 are in orders of 10-3 L mol-1 min-1, which are three orders of magnitude higher than the reported values obtained in solution chemistry. The formation of organosulfate in the H2SO4 aerosol internally mixed with multialcohols was studied by measuring the proton concentration of the aerosol collected on the filter using a newly developed Colorimetry integrated with a Reflectance UV-Visible spectrometer (C-RUV). The formation of organosulfate significantly decreases aerosol acidity due to the transformation of H2SO4 into dialkylsulfates. The forward reaction rate constants for the dialkylsulfate formation in the multialcohol-H2SO4 aerosols were also three orders of magnitude greater than the reported values in solution chemistry. The water content (MH2O) in the multialcohol-H2SO4 particle was monitored using the FTIR spectrometer. A large reduction of MH2O accords with the high yield of organosulfate in aerosol. Based on this study, we conclude that organosulfate formation in atmospheric aerosol, where both alcohols and sulfuric acid are found together, is significant.

  19. Radical mechanisms of methyl vinyl ketone oligomerization through aqueous phase OH-oxidation: on the paradoxical role of dissolved molecular oxygen

    NASA Astrophysics Data System (ADS)

    Renard, P.; Siekmann, F.; Gandolfo, A.; Socorro, J.; Salque, G.; Ravier, S.; Quivet, E.; Clément, J.-L.; Traikia, M.; Delort, A.-M.; Voisin, D.; Thissen, R.; Monod, A.

    2013-01-01

    It is now accepted that one of the important pathways of Secondary Organic Aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the liquid phase chemical mechanisms leading to macromolecules are still not well understood. For α-dicarbonyl precursors, such as methylglyoxal and glyoxal, radical reactions through OH-oxidation produce oligomers, irreversibly and faster than accretion reactions. Methyl vinyl ketone (MVK) was chosen in the present study as it is an α, β-unsaturated carbonyl that can undergo such reaction pathways in the aqueous phase and forms even high molecular weight oligomers. We present here experiments on the aqueous phase OH-oxidation of MVK, performed under atmospheric relevant conditions. Using NMR and UV absorption spectroscopy, high and ultra-high resolution mass spectrometry, we show that the fast formation of oligomers up to 1800 Da is due to radical oligomerization of MVK, and 13 series of oligomers (out of a total of 26 series) are identified. The influence of atmospherically relevant parameters such as temperature, initial concentrations of MVK and dissolved oxygen are presented and discussed. In agreement with the experimental observations, we propose a chemical mechanism of OH-oxidation of MVK in the aqueous phase that proceeds via radical oligomerization of MVK on the olefin part of the molecule. This mechanism highlights the paradoxical role of dissolved O2: while it inhibits oligomerization reactions, it contributes to produce oligomerization initiator radicals, which rapidly consume O2, thus leading to the supremacy of oligomerization reactions after several minutes of reaction. These processes, together with the large ranges of initial concentrations investigated (60-656 μM of dissolved O2 and 0.2-20 mM of MVK) show the fundamental role that O2 likely plays in atmospheric organic aerosol.

  20. Phase-contrast helium-3 MRI of aerosol deposition in human airways.

    PubMed

    Sarracanie, Mathieu; Grebenkov, Denis; Sandeau, Julien; Coulibaly, Soulé; Martin, Andrew R; Hill, Kyle; Pérez Sánchez, José Manuel; Fodil, Redouane; Martin, Lionel; Durand, Emmanuel; Caillibotte, Georges; Isabey, Daniel; Darrasse, Luc; Bittoun, Jacques; Maître, Xavier

    2015-02-01

    One of the key challenges in the study of health-related aerosols is predicting and monitoring sites of particle deposition in the respiratory tract. The potential health risks of ambient exposure to environmental or workplace aerosols and the beneficial effects of medical aerosols are strongly influenced by the site of aerosol deposition along the respiratory tract. Nuclear medicine is the only current modality that combines quantification and regional localization of aerosol deposition, and this technique remains limited by its spatial and temporal resolutions and by patient exposure to radiation. Recent work in MRI has shed light on techniques to quantify micro-sized magnetic particles in living bodies by the measurement of associated static magnetic field variations. With regard to lung MRI, hyperpolarized helium-3 may be used as a tracer gas to compensate for the lack of MR signal in the airways, so as to allow assessment of pulmonary function and morphology. The extrathoracic region of the human respiratory system plays a critical role in determining aerosol deposition patterns, as it acts as a filter upstream from the lungs. In the present work, aerosol deposition in a mouth-throat phantom was measured using helium-3 MRI and compared with single-photon emission computed tomography. By providing high sensitivity with high spatial and temporal resolutions, phase-contrast helium-3 MRI offers new insights for the study of particle transport and deposition.

  1. Single-particle measurements of phase partitioning between primary and secondary organic aerosols.

    PubMed

    Robinson, Ellis Shipley; Donahue, Neil M; Ahern, Adam T; Ye, Qing; Lipsky, Eric

    2016-07-18

    Organic aerosols provide a measure of complexity in the urban atmosphere. This is because the aerosols start as an external mixture, with many populations from varied local sources, that all interact with each other, with background aerosols, and with condensing vapors from secondary organic aerosol formation. The externally mixed particle populations start to evolve immediately after emission because the organic molecules constituting the particles also form thermodynamic mixtures - solutions - in which a large fraction of the constituents are semi-volatile. The external mixtures are thus well out of thermodynamic equilibrium, with very different activities for many constituents, and yet also have the capacity to relax toward equilibrium via gas-phase exchange of semi-volatile vapors. Here we describe experiments employing quantitative single-particle mass spectrometry designed to explore the extent to which various primary organic aerosol particle populations can interact with each other or with secondary organic aerosols representative of background aerosol populations. These methods allow us to determine when these populations will and when they will not mix with each other, and then to constrain the timescales for that mixing.

  2. Influence of aqueous phase emulsifiers on lipid oxidation in water-in-walnut oil emulsions.

    PubMed

    Yi, Jianhua; Zhu, Zhenbao; McClements, D Julian; Decker, Eric A

    2014-03-01

    Effects of selected aqueous phase emulsifiers on lipid oxidative stability of water-in-walnut oil (W/O) emulsions stabilized by polyglycerol polyricinoleate (PGPR) were evaluated. The formation of primary oxidation products (lipid hydroperoxides) and secondary oxidation products (headspace hexanal) increased with increasing dodecyltrimethylammonium bromide (DTAB) concentration (0.1-0.2 wt % of emulsions). In contrast, the addition of sodium dodecyl sulfate (SDS) in the aqueous phase reduced lipid hydroperoxide and hexanal formation. In addition, the presence of Tween 20 in the aqueous phase did not significantly influence lipid oxidation rates in W/O emulsions compared to the control (without Tween 20). Whey protein isolate (WPI) was observed to inhibit lipid oxidation in the W/O emulsions (0.05-0.2 wt % of emulsions). Aqueous phase pH had an important impact on the antioxidant capability of WPI, with higher pH improving its ability to inhibit lipid oxidation. The combination of WPI and DTAB in the aqueous phase suppressed the prooxidant effect of DTAB. The combination of WPI and SDS resulted in improved antioxidant activity, with inhibition being greater at pH 7.0 than at pH 3.0. These results suggest that the oxidative stability of W/O emulsions could be improved by the use of suitable emulsifiers in the aqueous phase.

  3. Polarized Imaging Nephelometer for Field and Aircraft Measurements of Aerosol Phase Function

    NASA Astrophysics Data System (ADS)

    Dolgos, G.; Martins, J.

    2012-12-01

    Aerosols have a significant impact on the radiative balance and water cycle of our planet through influencing atmospheric radiation. Remote sensing of aerosols relies on scattering phase matrix information to retrieve aerosol properties with frequent global coverage. At the Laboratory for Aerosols, Clouds and Optics (LACO) at the University of Maryland, Baltimore County we developed a new technique to directly measure the aerosol phase function and the degree of linear polarization of the scattered light (two elements of the phase matrix). We designed and built a portable instrument called the Polarized Imaging Nephelometer (PI-Neph). The PI-Neph successfully participated in dozens of flights of the NASA Development and Evaluation of satellite ValidatiOn Tools by Experimenters (DEVOTE) project and the Deep Convective Clouds and Chemistry (DC3) project. The ambient aerosol enters the PI-Neph through an inlet and the sample is illuminated by laser light (wavelength of 532 nm); the scattered light is imaged by a stationary wide field of view camera in the scattering angle range of 2° to 178°. (In some cases stray light limited the scattering angle range to 3° to 176°). The PI-Neph measurement of phase function and the AERONET (AErosol RObotic NETwork) retrievals have already been compared in some cases when the aircraft spiraled over AERONET sites, for example at NASA's Wallops Flight Facility, on October 18 2011, as shown in Figure 1. The differences between the PI-Neph and the AERONET retrievals can be attributed to differences between the ambient size distribution and the one sampled inside the aircraft. The data that is resolved with respect to scattering angle is used to compute the volume scattering coefficient. The above mentioned October 18 flight data showed good agreement between the PI-Neph measurements of volume scattering coefficient and the parallel TSI integrating nephelometer measurements. On average the TSI measurements were 1.02 times the PI

  4. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation.

    PubMed

    Shiraiwa, Manabu; Yee, Lindsay D; Schilling, Katherine A; Loza, Christine L; Craven, Jill S; Zuend, Andreas; Ziemann, Paul J; Seinfeld, John H

    2013-07-16

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

  5. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation.

    PubMed

    Shiraiwa, Manabu; Yee, Lindsay D; Schilling, Katherine A; Loza, Christine L; Craven, Jill S; Zuend, Andreas; Ziemann, Paul J; Seinfeld, John H

    2013-07-16

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process. PMID:23818634

  6. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

    PubMed Central

    Shiraiwa, Manabu; Yee, Lindsay D.; Schilling, Katherine A.; Loza, Christine L.; Craven, Jill S.; Zuend, Andreas; Ziemann, Paul J.; Seinfeld, John H.

    2013-01-01

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process. PMID:23818634

  7. Amorphous and crystalline aerosol particles interacting with water vapor: conceptual framework and experimental evidence for restructuring, phase transitions and kinetic limitations

    NASA Astrophysics Data System (ADS)

    Mikhailov, E.; Vlasenko, S.; Martin, S. T.; Koop, T.; Pöschl, U.

    2009-12-01

    Interactions with water are crucial for the properties, transformation and climate effects of atmospheric aerosols. Here we present a conceptual framework for the interaction of amorphous aerosol particles with water vapor, outlining characteristic features and differences in comparison to crystalline particles. We used a hygroscopicity tandem differential mobility analyzer (H-TDMA) to characterize the hydration and dehydration of crystalline ammonium sulfate, amorphous oxalic acid and amorphous levoglucosan particles (diameter ~100 nm, relative humidity 5-95% at 298 K). The experimental data and accompanying Köhler model calculations provide new insights into particle microstructure, surface adsorption, bulk absorption, phase transitions and hygroscopic growth. The results of these and related investigations lead to the following conclusions: (1) Many organic substances, including carboxylic acids, carbohydrates and proteins, tend to form amorphous rather than crystalline phases upon drying of aqueous solution droplets. Depending on viscosity and microstructure, the amorphous phases can be classified as glasses, rubbers, gels or viscous liquids. (2) Amorphous organic substances tend to absorb water vapor and undergo gradual deliquescence and hygroscopic growth at lower relative humidity than their crystalline counterparts. (3) In the course of hydration and dehydration, certain organic substances can form rubber- or gel-like structures (supramolecular networks) and undergo transitions between swollen and collapsed network structures. (4) Organic gels or (semi-)solid amorphous shells (glassy, rubbery, ultra-viscous) with low molecular diffusivity can kinetically limit the uptake and release of water and may influence the hygroscopic growth and activation of aerosol particles as cloud condensation nuclei (CCN) and ice nuclei (IN). Moreover, (semi-)solid amorphous phases may influence the uptake of gaseous photo-oxidants and the chemical transformation and aging of

  8. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    DOE PAGES

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-12-23

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenatedmore » molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

  9. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    DOE PAGES

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-08-19

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (·OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified,more » including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than ·OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

  10. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    SciTech Connect

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; Anastasio, Cort N.; Laskin, Julia; Zhang, Qi

    2014-01-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), desorption electrospray ionization mass spectrometry (DESIMS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O/C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than •OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O/C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  11. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-08-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants - the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (\\centerdot OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than \\centerdot OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  12. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-12-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants - the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  13. Development of Recombinant Human Growth Hormone (rhGH) sustained-release microspheres by a low temperature aqueous phase/aqueous phase emulsion method.

    PubMed

    Kang, Jian; Wu, Fei; Cai, Yunpeng; Xu, Mingxin; He, Mu; Yuan, Weien

    2014-10-01

    A novel method has been developed to protect Recombinant Human Growth Hormone (rhGH) in poly (lactic-co-glycolic acid) (PLGA) microspheres using an aqueous phase/aqueous phase emulsion and S/O/W multi-emulsion method. This method develops a novel rhGH sustained-release system, which is based on the combination of rhGH-loaded dextran microparticles and PLGA microspheres. The process to fabricate rhGH-loaded dextran microparticles involves an aqueous phase/aqueous phase emulsion system formed at the reduced temperature. RhGH was first dissolved in water together with dextran and polyethylene glycol, followed by stirring at the speed of 2000 rpm for 20-30s at 0°C, and then a freezing process could enable the dextran phase to separate from the continuous PEG phase and rhGH could preferentially be loaded with dextran. The sample after freezing and phase separation was then lyophilized to powder and washed with dichloromethane to remove the PEG. Once loaded in the dextran microparticles (1-4 μm in diameter), rhGH gained resistance to interface tensions and was encapsulated into PLGA microspheres without aggregation thereafter. RhGH released from PLGA microspheres was in a sustained manner with minimal burst and maximally reduced incomplete release in vitro. Single subcutaneous injection of rhGH-loaded PLGA microspheres to rats resulted in a stable plasma concentration for 30 days avoiding the drug concentration fluctuations after multiple injections of protein solutions. In a hypophysectomized rat model, the IGF-1 and bodyweight results showed that there were higher than the levels obtained for the sustained release formulation by W/O/W for 40 days. These results suggest that the microsphere delivery system had the potential to be an injectable depot for sustained-release of the biocompatible protein of rhGH.

  14. Initiation of the ice phase by marine biogenic surfaces in supersaturated gas and supercooled aqueous phases.

    PubMed

    Alpert, Peter A; Aller, Josephine Y; Knopf, Daniel A

    2011-11-28

    Biogenic particles have the potential to affect the formation of ice crystals in the atmosphere with subsequent consequences for the hydrological cycle and climate. We present laboratory observations of heterogeneous ice nucleation in immersion and deposition modes under atmospherically relevant conditions initiated by Nannochloris atomus and Emiliania huxleyi, marine phytoplankton with structurally and chemically distinct cell walls. Temperatures at which freezing, melting, and water uptake occur are observed using optical microscopy. The intact and fragmented unarmoured cells of N. atomus in aqueous NaCl droplets enhance ice nucleation by 10-20 K over the homogeneous freezing limit and can be described by a modified water activity based ice nucleation approach. E. huxleyi cells covered by calcite plates do not enhance droplet freezing temperatures. Both species nucleate ice in the deposition mode at an ice saturation ratio, S(ice), as low as ~1.2 and below 240 K, however, for each, different nucleation modes occur at warmer temperatures. These observations show that markedly different biogenic surfaces have both comparable and contrasting effects on ice nucleation behaviour depending on the presence of the aqueous phase and the extent of supercooling and water vapour supersaturation. We derive heterogeneous ice nucleation rate coefficients, J(het), and cumulative ice nuclei spectra, K, for quantification and analysis using time-dependent and time-independent approaches, respectively. Contact angles, α, derived from J(het)via immersion freezing depend on T, a(w), and S(ice). For deposition freezing, α can be described as a function of S(ice) only. The different approaches yield different predictions of atmospheric ice crystal numbers primarily due to the time evolution allowed for the time-dependent approach with implications for the evolution of mixed-phase and ice clouds.

  15. Surrogate/spent fuel sabotage aerosol ratio testing:phase 1 summary and results.

    SciTech Connect

    Vigil, Manuel Gilbert; Sorenson, Ken Bryce; Lange, F. , Germany); Nolte, O. (Fraunhofer Institut fur Toxikologie und Experimentelle Medizin, Germany); Koch, W. (Fraunhofer Institut fur Toxikologie und Experimentelle Medizin, Germany); Dickey, Roy R.; Yoshimura, Richard Hiroyuki; Molecke, Martin Alan; Autrusson, Bruno (Institut de Radioprotection et de Surete Nucleaire , France); Young, F. I.; Pretzsch, Gunter Guido (Gesellschaft fur Anlagen- und reaktorsicherheit , Germany)

    2005-10-01

    This multinational test program is quantifying the aerosol particulates produced when a high energy density device (HEDD) impacts surrogate material and actual spent fuel test rodlets. The experimental work, performed in four consecutive test phases, has been in progress for several years. The overall program provides needed data that are relevant to some sabotage scenarios in relation to spent fuel transport and storage casks, and associated risk assessments. This program also provides significant political benefits in international cooperation for nuclear security related evaluations. The spent fuel sabotage--aerosol test program is coordinated with the international Working Group for Sabotage Concerns of Transport and Storage Casks (WGSTSC), and supported by both the U.S. Department of Energy and Nuclear Regulatory Commission. This report summarizes the preliminary, Phase 1 work performed in 2001 and 2002 at Sandia National Laboratories and the Fraunhofer Institute, Germany, and documents the experimental results obtained, observations, and preliminary interpretations. Phase 1 testing included: performance quantifications of the HEDD devices; characterization of the HEDD or conical shaped charge (CSC) jet properties with multiple tests; refinement of the aerosol particle collection apparatus being used; and, CSC jet-aerosol tests using leaded glass plates and glass pellets, serving as representative brittle materials. Phase 1 testing was quite important for the design and performance of the following Phase 2 test program and test apparatus.

  16. Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM

    SciTech Connect

    Roldin, P.; Eriksson, A. C.; Nordin, E. Z.; Hermansson, E.; Mogensen, Ditte; Rusanen, A.; Boy, Michael; Swietlicki, E.; Svenningsson, Birgitta; Zelenyuk, Alla; Pagels, J.

    2014-08-11

    We have developed the novel Aerosol Dynamics, gas- and particle- phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: 1) the mass transfer limited uptake of ammonia (NH3) and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), 2) the slow and almost particle size independent evaporation of α-pinene secondary organic aerosol (SOA) particles, and 3) the influence of chamber wall effects on the observed SOA formation in smog chambers.

  17. Nickel/ruthenium catalyst and method for aqueous phase reactions

    DOEpatents

    Elliott, Douglas C.; Sealock, John L.

    1998-01-01

    A method of hydrogenation using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions.

  18. Surrogate/spent fuel sabotage : aerosol ratio test program and Phase 2 test results.

    SciTech Connect

    Borek, Theodore Thaddeus III; Thompson, N. Slater; Sorenson, Ken Bryce; Hibbs, R.S.; Nolte, Oliver; Molecke, Martin Alan; Autrusson, Bruno; Young, F. I.; Koch, Wolfgang; Brochard, Didier; Pretzsch, Gunter Guido; Lange, Florentin

    2004-05-01

    A multinational test program is in progress to quantify the aerosol particulates produced when a high energy density device, HEDD, impacts surrogate material and actual spent fuel test rodlets. This program provides needed data that are relevant to some sabotage scenarios in relation to spent fuel transport and storage casks, and associated risk assessments; the program also provides significant political benefits in international cooperation. We are quantifying the spent fuel ratio, SFR, the ratio of the aerosol particles released from HEDD-impacted actual spent fuel to the aerosol particles produced from surrogate materials, measured under closely matched test conditions. In addition, we are measuring the amounts, nuclide content, size distribution of the released aerosol materials, and enhanced sorption of volatile fission product nuclides onto specific aerosol particle size fractions. These data are crucial for predicting radiological impacts. This document includes a thorough description of the test program, including the current, detailed test plan, concept and design, plus a description of all test components, and requirements for future components and related nuclear facility needs. It also serves as a program status report as of the end of FY 2003. All available test results, observations, and analyses - primarily for surrogate material Phase 2 tests using cerium oxide sintered ceramic pellets are included. This spent fuel sabotage - aerosol test program is coordinated with the international Working Group for Sabotage Concerns of Transport and Storage Casks, WGSTSC, and supported by both the U.S. Department of Energy and Nuclear Regulatory Commission.

  19. Estimating the importance of multi-phase processing on secondary organic aerosol based on a functional-group resolving volatility basis set approach

    NASA Astrophysics Data System (ADS)

    Knote, C. J.; Hodzic, A.; Aumont, B.; Madronich, S.

    2014-12-01

    Traditional understanding views secondary organic aerosol (SOA) formation in the atmosphere as continuous gas-phase oxidation of precursors such as isoprene, aromatics or alkanes. Recent research found that these oxidation products are also highly water soluble. It is further understood that the liquid-phase of cloud droplets as well as deliquesced particles could mediate SOA formation through chemistry in the aqueous-phase. While the effect of multi-phase processing has been studied in detailed for specific compounds like glyoxal or methylglyoxal, an integrated approach that considers the large number of individual compounds has been missing due to the complexity involved. In our work we explore the effects of multi-phase processing on secondary organic aerosol from an explicit modeling perspective.Volatility and solubility determine in which phase a given molecule will be found under given atmospheric conditions. Volatility has already been used to simplify the description of SOA formation in the gas-phase in what became known as the Volatility Basis Set approach (VBS). Compounds contributing to SOA formation are grouped by volatility and then treated as a whole. A number of studies extended the VBS by adding a second dimension like oxygen to carbon ratio or the mean oxidation state. In our work we use functional groups as second dimension.Using explicit oxidation chemistry modeling (GECKO-A) we derive SOA yields as well as their composition in terms of functional groups for commonly used precursors. We then investigate the effect of simply partitioning functional-group specific organic mass into cloud droplets and deliquesced aerosol based on their estimated solubility. Finally we apply simple chemistry in the aqueous-phase and relate changes in functional groups to changes in volatility and subsequent changes in partitioning between gas- and aerosol-phase.In our presentation we will explore the sensitivites of the multi-phase system in a box model setting with

  20. Organic component vapor pressures and hygroscopicities of aqueous aerosol measured by optical tweezers.

    PubMed

    Cai, Chen; Stewart, David J; Reid, Jonathan P; Zhang, Yun-hong; Ohm, Peter; Dutcher, Cari S; Clegg, Simon L

    2015-01-29

    Measurements of the hygroscopic response of aerosol and the particle-to-gas partitioning of semivolatile organic compounds are crucial for providing more accurate descriptions of the compositional and size distributions of atmospheric aerosol. Concurrent measurements of particle size and composition (inferred from refractive index) are reported here using optical tweezers to isolate and probe individual aerosol droplets over extended timeframes. The measurements are shown to allow accurate retrievals of component vapor pressures and hygroscopic response through examining correlated variations in size and composition for binary droplets containing water and a single organic component. Measurements are reported for a homologous series of dicarboxylic acids, maleic acid, citric acid, glycerol, or 1,2,6-hexanetriol. An assessment of the inherent uncertainties in such measurements when measuring only particle size is provided to confirm the value of such a correlational approach. We also show that the method of molar refraction provides an accurate characterization of the compositional dependence of the refractive index of the solutions. In this method, the density of the pure liquid solute is the largest uncertainty and must be either known or inferred from subsaturated measurements with an error of <±2.5% to discriminate between different thermodynamic treatments.

  1. Radiative Forcing of the Direct Aerosol Effect from AeroCom Phase II Simulations

    NASA Technical Reports Server (NTRS)

    Myhre, G.; Samset, B. H.; Schulz, M.; Balkanski, Y.; Bauer, S.; Berntsen, T. K.; Bian, H.; Bellouin, N.; Chin, M.; Diehl, T.; Easter, R. C.; Feichter, J.; Ghan, S. J.; Hauglustaine, D.; Iversen, T.; Kinne, S.; Kirkevag, A.; Lamarque, J.-F.; Lin, G.; Liu, X.; Lund, M. T.; Luo, G.; Ma, X.; vanNoije, T.; Penner, J. E.; Rasch, P. J.; Ruiz, A.; Seland, O.; Skeie, R. B.; Stier, P.; Takemura, T.; Tsigaridis, K.; Wang, P.; Wang, Z.; Xu, L.; Yu, H.; Yu, F.; Yoon, J. -H.; Zhang, K.; Zhang, H.; Zhou, C.

    2013-01-01

    We report on the AeroCom Phase II direct aerosol effect (DAE) experiment where 16 detailed global aerosol models have been used to simulate the changes in the aerosol distribution over the industrial era. All 16 models have estimated the radiative forcing (RF) of the anthropogenic DAE, and have taken into account anthropogenic sulphate, black carbon (BC) and organic aerosols (OA) from fossil fuel, biofuel, and biomass burning emissions. In addition several models have simulated the DAE of anthropogenic nitrate and anthropogenic influenced secondary organic aerosols (SOA). The model simulated all-sky RF of the DAE from total anthropogenic aerosols has a range from -0.58 to -0.02 W m(sup-2), with a mean of -0.27 W m(sup-2 for the 16 models. Several models did not include nitrate or SOA and modifying the estimate by accounting for this with information slightly strengthens the mean. Modifying the model estimates for missing aerosol components and for the time period 1750 to 2010 results in a mean RF for the DAE of -0.35 W m(sup-2). Compared to AeroCom Phase I (Schulz et al., 2006) we find very similar spreads in both total DAE and aerosol component RF. However, the RF of the total DAE is stronger negative and RF from BC from fossil fuel and biofuel emissions are stronger positive in the present study than in the previous AeroCom study.We find a tendency for models having a strong (positive) BC RF to also have strong (negative) sulphate or OA RF. This relationship leads to smaller uncertainty in the total RF of the DAE compared to the RF of the sum of the individual aerosol components. The spread in results for the individual aerosol components is substantial, and can be divided into diversities in burden, mass extinction coefficient (MEC), and normalized RF with respect to AOD. We find that these three factors give similar contributions to the spread in results

  2. Radiative forcing of the direct aerosol effect from AeroCom Phase II simulations

    SciTech Connect

    Myhre, G.; Samset, B. H.; Schulz, M.; Balkanski, Y.; Bauer, S.; Berntsen, T. K.; Bian, H.; Bellouin, N.; Chin, M.; Diehl, T.; Easter, R. C.; Feichter, J.; Ghan, S. J.; Hauglustaine, D.; Iversen, T.; Kinne, S.; Kirkevåg, A.; Lamarque, J. -F.; Lin, G.; Liu, X.; Lund, M. T.; Luo, G.; Ma, X.; van Noije, T.; Penner, J. E.; Rasch, P. J.; Ruiz, A.; Seland, Ø.; Skeie, R. B.; Stier, P.; Takemura, T.; Tsigaridis, K.; Wang, P.; Wang, Z.; Xu, L.; Yu, H.; Yu, F.; Yoon, J. -H.; Zhang, K.; Zhang, H.; Zhou, C.

    2013-01-01

    We report on the AeroCom Phase II direct aerosol effect (DAE) experiment where 16 detailed global aerosol models have been used to simulate the changes in the aerosol distribution over the industrial era. All 16 models have estimated the radiative forcing (RF) of the anthropogenic DAE, and have taken into account anthropogenic sulphate, black carbon (BC) and organic aerosols (OA) from fossil fuel, biofuel, and biomass burning emissions. In addition several models have simulated the DAE of anthropogenic nitrate and anthropogenic influenced secondary organic aerosols (SOA). The model simulated all-sky RF of the DAE from total anthropogenic aerosols has a range from -0.58 to -0.02 Wm-2, with a mean of -0.27 Wm-2 for the 16 models. Several models did not include nitrate or SOA and modifying the estimate by accounting for this with information from the other AeroCom models reduces the range and slightly strengthens the mean. Modifying the model estimates for missing aerosol components and for the time period 1750 to 2010 results in a mean RF for the DAE of -0.35 Wm-2. Compared to AeroCom Phase I (Schulz et al., 2006) we find very similar spreads in both total DAE and aerosol component RF. However, the RF of the total DAE is stronger negative and RF from BC from fossil fuel and biofuel emissions are stronger positive in the present study than in the previous AeroCom study. We find a tendency for models having a strong (positive) BC RF to also have strong (negative) sulphate or OA RF. This relationship leads to smaller uncertainty in the total RF of the DAE compared to the RF of the sum of the individual aerosol components. The spread in results for the individual aerosol components is substantial, and can be divided into diversities in burden, mass extinction coefficient (MEC), and normalized RF with respect to AOD. We find that these three factors give similar contributions to the spread in results.

  3. Aqueous phase removal of nitrogen from nitrogen compounds

    DOEpatents

    Fassbender, Alex G.

    1993-01-01

    A method is disclosed for denitrification of compounds containing nitrogen present in aqueous waste streams. The method comprises the steps of (1) identifying the types of nitrogen compounds present in a waste stream, (2) determining the concentrations of nitrogen compounds, (3) balancing oxidized and reduced form of nitrogen by adding a reactant, and (4) heating the mixture to a predetermined reaction temperature from about 300.degree. C. to about 600.degree. C., thereby resulting in less harmful nitrogen and oxygen gas, hydroxides, alcohols, and hydrocarbons.

  4. Rapid aqueous phase SO2 oxidation in winter fog in the Indo-Gangetic Plain

    NASA Astrophysics Data System (ADS)

    Sachan, Himanshu; Sarkar, Chinmoy; Sinha, Baerbel

    2013-04-01

    Sulphate and sulphur dioxide play an important role in environmental chemistry and climate. The majority of anthropogenic sulphur is released directly as SO2, and a significant fraction of biogenic and natural sulphur emissions are also either directly released as SO2 or oxidised to SO2 in the atmosphere (e.g. H2S, OCS, DMS). Around 50% of global atmospheric sulphur dioxide is then oxidised to sulphate, while the rest is lost through dry and wet deposition. The pathway by which SO2 is oxidised to sulphate is critical in determining the climate forcing and environmental effects of sulphate. Gas-phase oxidation of SO2 by OH radicals or criegee intermediates produces H2SO4 (g), which plays an important role in controlling new particle formation in the troposphere and also modifies the surface properties of hydrophobic particles such as soot and mineral dust. Heterogeneous oxidation of SO2 is considered to occur primarily in cloud droplets, although oxidation on sea salt aerosols and mineral dust surfaces are considered to be regionally important. Heterogeneous oxidation leads to the formation of fewer and larger particles with shorter atmospheric lifetime. The major oxidation pathways which are considered to contribute to sulphate formation in the aqueous phase are oxidation by H2O2 and oxidation by O3 and the lifetime of SO2 with respect to all known loss processes combined is considered to be 1-2 days. Here we report measurements of SO2 measurements from IISER Mohali - Ambient Air Quality Station (30.67°N, 76.73°E), a station located at a suburban site in the Indo Gangetic Basin (IGB) during wintertime (10th Dec. 2011 to 29th Feb. 2012). We use a strong point source of SO2 with known SO2/CO emission ratio (brick kiln) located 6.5 km east of our measurement site to estimate the loss rate of SO2 in wintertime fog in the IGB. We consider the transport from the source to the receptor site to be Lagrangian and use the measured CO concentration at the receptors site to

  5. Nickel/ruthenium catalyst and method for aqueous phase reactions

    DOEpatents

    Elliott, D.C.; Sealock, J.L.

    1998-09-29

    A method of hydrogenation is described using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions. 2 figs.

  6. Reaction Kinetics of Ethylene Glycol Reforming over Platinum in the Vapor versus Aqueous Phases

    SciTech Connect

    Kandoi, Shampa; Greeley, Jeffrey P.; Simonetti, Dante A.; Shabaker, John; Dumesic, James A.; Mavrikakis, Manos

    2010-08-12

    First-principles, periodic, density functional theory (DFT) calculations are carried out on Pt(111) to investigate the structure and energetics of dehydrogenated ethylene glycol species and transition states for the cleavage of C-H/O-H and C-C bonds. Additionally, reaction kinetics studies are carried out for the vapor phase reforming of ethylene glycol (C2H6O2) over Pt/Al2O3 at various temperatures, pressures, and feed concentrations. These results are compared to data for aqueous phase reforming of ethylene glycol on this Pt catalyst, as reported in a previous publication (Shabaker, J. W.; et al. J. Catal. 2003, 215, 344). Microkinetic models were developed to describe the reaction kinetics data obtained for both the vapor-phase and aqueous-phase reforming processes. The results suggest that C-C bond scission in ethylene glycol occurs at an intermediate value of x (3 or 4) in C2HxO2. It is also found that similar values of kinetic parameters can be used to describe the vapor and aqueous phase reforming data, suggesting that the vapor phase chemistry of this reaction over platinum is similar to that in the aqueous phase over platinum.

  7. Reaction kinetics of ethylene glycol reforming over platinum in the vapor versus aqueous phases

    SciTech Connect

    Kandoi, Shampa; Greeley, Jeff; Simonetti, Dante; Shabaker, John; Dumesic, James A.; Mavrikakis, Manos

    2010-08-12

    First-principles, periodic, density functional theory (DFT) calculations are carried out on Pt(111) to investigate the structure and energetics of dehydrogenated ethylene glycol species and transition states for the cleavage of C–H/O–H and C–C bonds. Additionally, reaction kinetics studies are carried out for the vapor phase reforming of ethylene glycol (C₂H₆O₂) over Pt/Al₂O₃ at various temperatures, pressures, and feed concentrations. These results are compared to data for aqueous phase reforming of ethylene glycol on this Pt catalyst, as reported in a previous publication (Shabaker, J. W.; et al. J. Catal. 2003, 215, 344). Microkinetic models were developed to describe the reaction kinetics data obtained for both the vapor-phase and aqueous-phase reforming processes. The results suggest that C–C bond scission in ethylene glycol occurs at an intermediate value of x (3 or 4) in C₂HxO₂. It is also found that similar values of kinetic parameters can be used to describe the vapor and aqueous phase reforming data, suggesting that the vapor phase chemistry of this reaction over platinum is similar to that in the aqueous phase over platinum.

  8. Liquid-phase dehydration of aqueous ethanol-gasoline mixtures

    SciTech Connect

    Fanta, G.F.; Burr, R.C.; Orton, W.L.; Doane, W.M.

    1980-11-07

    Two-phase mixtures of gasoline, water, and ethanol were dehydrated with both starch and saponified starch-g-polyacrylonitrile (HSPAN). Whereas starch absorbed ethanol as well as water, HSPAN selectively absorbed the water component, allowing ethanol to dissolve in the gasoline phase.

  9. Plutonium silicate alteration phases produced by aqueous corrosion of borosilicate glass.

    SciTech Connect

    Fortner, J. A.; Mertz, C. J.; Bakel, A. J.; Finch, R. J.; Chamerlain, D. B.

    1999-11-22

    Borosilicate glasses loaded with {approx}10 wt % plutonium were found to produce plutonium-silicate alteration phases upon aqueous corrosion under a range of conditions. The phases observed were generally rich in lanthanide (Ln) elements and were related to the lanthanide orthosilicate phases of the monoclinic Ln{sub 2}SiO{sub 5} type. The composition of the phases was variable regarding [Ln]/[Pu] ratio, depending upon type of corrosion test and on the location within the alteration layer. The formation of these phases likely has implications for the incorporation of plutonium into silicate alteration phases during corrosion of titanate ceramics, high-level waste glasses, and spent nuclear fuel.

  10. Preparative crystallization of a single chain antibody using an aqueous two-phase system.

    PubMed

    Huettmann, Hauke; Berkemeyer, Matthias; Buchinger, Wolfgang; Jungbauer, Alois

    2014-11-01

    A simultaneous crystallization and aqueous two-phase extraction of a single chain antibody was developed, demonstrating process integration. The process conditions were designed to form an aqueous two-phase system, and to favor crystallization, using sodium sulfate and PEG-2000. At sufficiently high concentrations of PEG, a second phase was generated in which the protein crystallization occurred simultaneously. The single chain antibody crystals were partitioned to the top, polyethylene glycol-rich phase. The crystal nucleation took place in the sodium sulfate-rich phase and at the phase boundary, whereas crystal growth was progressing mainly in the polyethylene glycol-rich phase. The crystals in the polyethylene glycol-rich phase grew to a size of >50 µm. Additionally, polyethylene glycol acted as an anti-solvent, thus, it influenced the crystallization yield. A phase diagram with an undersaturation zone, crystallization area, and amorphous precipitation zone was established. Only small differences in polyethylene glycol concentration caused significant shifts of the crystallization yield. An increase of the polyethylene glycol content from 2% (w/v) to 4% (w/v) increased the yield from approximately 63-87%, respectively. Our results show that crystallization in aqueous two-phase systems is an opportunity to foster process integration.

  11. Droplet formation and shrinking in aqueous two-phase systems using a membrane emulsification method

    PubMed Central

    Breisig, Hans; Wessling, Matthias

    2015-01-01

    Using a membrane emulsification method based on porous hollow-fiber membranes in combination with an aqueous two-phase system (ATPS), we are able to produce “water-in-water” droplets with narrow-dispersed size distributions. The equilibrium phases of the aqueous two-phase system polyethylene glycol-dipotassium hydrogen phosphate are used for this purpose. The droplet diameter of a given fluid system is determined by the flow rates of the continuous and disperse phase as well as the hollow fiber dimensions. When diluting the disperse phase and thus moving the ATPS system out of equilibrium, the droplet size can be further reduced in comparison to the equilibrium case. Generally, droplets formed with this method have diameters 20%–60% larger than the inner hollow fiber diameter. The new strategy of diluting the disperse phase allows the production of droplet diameter below the inner diameter of the membrane. PMID:26339321

  12. Modeling immersion freezing with aerosol-dependent prognostic ice nuclei in Arctic mixed-phase clouds

    NASA Astrophysics Data System (ADS)

    Paukert, M.; Hoose, C.

    2014-07-01

    While recent laboratory experiments have thoroughly quantified the ice nucleation efficiency of different aerosol species, the resulting ice nucleation parameterizations have not yet been extensively evaluated in models on different scales. Here the implementation of an immersion freezing parameterization based on laboratory measurements of the ice nucleation active surface site density of mineral dust and ice nucleation active bacteria, accounting for nucleation scavenging of ice nuclei, into a cloud-resolving model with two-moment cloud microphysics is presented. We simulated an Arctic mixed-phase stratocumulus cloud observed during Flight 31 of the Indirect and Semi-Direct Aerosol Campaign near Barrow, Alaska. Through different feedback cycles, the persistence of the cloud strongly depends on the ice number concentration. It is attempted to bring the observed cloud properties, assumptions on aerosol concentration, and composition and ice formation parameterized as a function of these aerosol properties into agreement. Depending on the aerosol concentration and on the ice crystal properties, the simulated clouds are classified as growing, dissipating, and quasi-stable. In comparison to the default ice nucleation scheme, the new scheme requires higher aerosol concentrations to maintain a quasi-stable cloud. The simulations suggest that in the temperature range of this specific case, mineral dust can only contribute to a minor part of the ice formation. The importance of ice nucleation active bacteria and possibly other ice formation modes than immersion freezing remains poorly constrained in the considered case, since knowledge on local variations in the emissions of ice nucleation active organic aerosols in the Arctic is scarce.

  13. Influence of particle-phase state on the hygroscopic behavior of mixed organic-inorganic aerosols

    NASA Astrophysics Data System (ADS)

    Hodas, N.; Zuend, A.; Mui, W.; Flagan, R. C.; Seinfeld, J. H.

    2015-05-01

    Recent work has demonstrated that organic and mixed organic-inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle-phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic-inorganic aerosol systems with physical states ranging from well-mixed liquids to phase-separated particles to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40 to 90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids; (2) forcing a single phase but accounting for non-ideal interactions through activity coefficient calculations; and (3) a Zdanovskii-Stokes-Robinson-like calculation in which complete separation of the inorganic and organic components is assumed at all RH values, with water uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid-liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF

  14. Influence of particle phase state on the hygroscopic behavior of mixed organic-inorganic aerosols

    NASA Astrophysics Data System (ADS)

    Hodas, N.; Zuend, A.; Mui, W.; Flagan, R. C.; Seinfeld, J. H.

    2014-12-01

    Recent work has demonstrated that organic and mixed organic-inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic-inorganic aerosol systems with physical states ranging from well-mixed liquids, to phase-separated particles, to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40-90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids, (2) forcing a single phase, but accounting for non-ideal interactions through activity coefficient calculations, and (3) a Zdanovskii-Stokes-Robinson-like calculation in which complete separation between the inorganic and organic components is assumed at all RH values, with water-uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid-liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF

  15. Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US

    NASA Astrophysics Data System (ADS)

    Pajunoja, Aki; Hu, Weiwei; Leong, Yu J.; Taylor, Nathan F.; Miettinen, Pasi; Palm, Brett B.; Mikkonen, Santtu; Collins, Don R.; Jimenez, Jose L.; Virtanen, Annele

    2016-09-01

    During the summer 2013 Southern Aerosol and Oxidant Study (SOAS) field campaign in a rural site in the southeastern United States, the effect of hygroscopicity and composition on the phase state of atmospheric aerosol particles dominated by the organic fraction was studied. The analysis is based on hygroscopicity measurements by a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA), physical phase state investigations by an Aerosol Bounce Instrument (ABI) and composition measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). To study the effect of atmospheric aging on these properties, an OH-radical oxidation flow reactor (OFR) was used to simulate longer atmospheric aging times of up to 3 weeks. Hygroscopicity and bounce behavior of the particles had a clear relationship showing higher bounce at elevated relative humidity (RH) values for less hygroscopic particles, which agrees well with earlier laboratory studies. Additional OH oxidation of the aerosol particles in the OFR increased the O : C and the hygroscopicity resulting in liquefying of the particles at lower RH values. At the highest OH exposures, the inorganic fraction starts to dominate the bounce process due to production of inorganics and concurrent loss of organics in the OFR. Our results indicate that at typical ambient RH and temperature, organic-dominated particles stay mostly liquid in the atmospheric conditions in the southeastern US, but they often turn semisolid when dried below ˜ 50 % RH in the sampling inlets. While the liquid phase state suggests solution behavior and equilibrium partitioning for the SOA particles in ambient air, the possible phase change in the drying process highlights the importance of thoroughly considered sampling techniques of SOA particles.

  16. Measurements of the HO2 uptake coefficient onto aqueous salt and organic aerosols and interpretation using the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB)

    NASA Astrophysics Data System (ADS)

    Matthews, P. S. J.; Berkemeier, T.; George, I. J.; Whalley, L. K.; Moon, D. R.; Ammann, M.; Baeza-Romero, M. T.; Poeschl, U.; Shiraiwa, M.; Heard, D. E.

    2014-12-01

    HO2 is closely coupled with OH which is responsible for the majority of the oxidation in the troposphere. Therefore, it is important to be able to accurately predict OH and HO2 concentrations. However, many studies have reported a large discrepancy between HO2 radical concentrations measured during field campaigns and predicted by constrained box models using detailed chemical mechanisms (1,2). However, there have been very few laboratory studies (3,4) on HO2 uptake by aerosols and the rates and mechanism is still uncertain. The HO2 uptake coefficients were measured for deliquesced ammonium nitrate and sodium chloride aerosols and copper doped sucrose aerosols. The measurements were performed using an aerosol flow tube coupled to a Fluorescence Assay by Gas Expansion (FAGE) detector. By either placing the HO2 injector in set positions and varying the aerosol concentration or by moving it along the flow tube at given aerosol concentrations, uptake coefficients could be measured. The aerosols were generated using an atomiser and the total aerosol surface area was measured using a SMPS. Larger uptake coefficients were measured at shorter times and lower HO2 concentrations for aqueous salt aerosols. The time dependence was able to be modelled by the KM-SUB model (5) as the HO2 concentration decreases along the flow tube and the HO2 uptake mechanism is known to be a second order reaction. Measurements have shown that at higher HO2 concentrations there was also more H2O2 exiting the injector which could convert back to HO2 if trace amounts of metals are present within the aerosol via Fenton reactions. Preliminary results have shown that the inclusion of a Fenton-like reaction within the KM-SUB model has the potential to explain the apparent HO2 concentration dependence. Finally, the KM-SUB model has been used to demonstrate that the increase in uptake coefficient observed when increasing the relative humidity for copper doped sucrose aerosols could be explained by an

  17. A Mechanism for the Aqueous Phase Production of Alkyl Nitrates

    NASA Astrophysics Data System (ADS)

    Dahl, E. E.; Saltzman, E. S.; DeBruyn, W. J.

    2002-05-01

    Measurements of alkyl nitrates in the surface ocean and marine boundary layer indicate that there is an oceanic source of alkyl nitrates to the marine troposphere. Alkyl nitrates make up a portion of the total reactive nitrogen in the troposphere. They can contribute significantly to the NOx budget in the remote marine atmosphere, affecting regional ozone formation. The origin of the alkyl nitrate in the surface ocean is unknown. One possible mechanism for aqueous alkyl nitrate formation is the reaction of alkyl peroxy radicals with NO (ROO + NO -> RONO2). Peroxy radicals and NO have been observed in seawater at levels that make this a viable reaction (Blough 1997) (Zafiriou and McFarland 1981). In this project, steady state irradiations of nitrite and alkane solutions were used to determine the yield of alkyl nitrates from this reaction. The yield for ethyl nitrate has been determined to be 101+/-12% and 102+/-8% total yield for propyl nitrates (n-propyl and iso-propyl) with no evident temperature dependence between 5 and 30° C. Alkyl nitrates were also generated by the irradiation of natural seawater and nitrite-spiked seawater. These results indicate that the proposed mechanism may be a viable source of alkyl nitrates in surface waters.

  18. Improving liquid-crystal-based biosensing in aqueous phases.

    PubMed

    Iglesias, Wilder; Abbott, Nicholas L; Mann, Elizabeth K; Jákli, Antal

    2012-12-01

    Liquid crystal (LC)-based biological sensors permit the study of aqueous biological samples without the need for the labeling of biological species with fluorescent dyes (which can be laborious and change the properties of the biological sample under study). To date, studies of LC-based biosensors have explored only a narrow range of the liquid crystal/alignment layer combinations essential to their operation. Here, we report a study of the role of LC elastic constants and the surface anchoring energy in determining the sensitivity of LC-based biosensors. By investigating a mixture of rod-shape and bent-shape mesogens, and three different alignment layers, we were able to widen the useful detection range of a LC-based sensor by providing an almost-linear mapping of effective birefringence with anionic surfactant concentrations between 0.05 mM and 1 mM (model target analyte). These studies pave the way for optimization of LC-based biosensors and reveal the importance of the choice of both the LC material and the alignment layer in determining sensor properties. PMID:23157269

  19. IMPROVING LIQUID CRYSTAL-BASED BIOSENSING IN AQUEOUS PHASES

    PubMed Central

    Iglesias, Wilder; Abbott, Nicholas L.; Mann, Elizabeth K.; Jákli, Antal

    2012-01-01

    Liquid crystal (LC)-based biological sensors permit the study of aqueous biological samples without the need for the labeling of biological species with fluorescent dyes (which can be laborious and change the properties of the biological sample under study). To date, studies of LC-based biosensors have explored only a narrow range of the liquid crystal/alignment layer combinations essential to their operation. Here we report a study of the role of LC elastic constants and the surface anchoring energy in determining the sensitivity of LC-based biosensors. By investigating a mixture of rod-shape and bent-shape mesogens, and three different alignment layers, we were able to widen the useful detection range of a LC-based sensor by providing an almost linear mapping of effective birefringence with concentration between 0.05 and 1mM of an anionic surfactant (model target analyte). These studies pave the way for optimization of LC-based biosensors and reveal the importance of the choice of both the LC material and the alignment layer in determining sensor properties. PMID:23157269

  20. The effect of phase partitioning of semivolatile compounds on the measured CCN activity of aerosol particles

    NASA Astrophysics Data System (ADS)

    Romakkaniemi, S.; Jaatinen, A.; Laaksonen, A.; Nenes, A.; Raatikainen, T.

    2013-09-01

    The effect of inorganic semivolatile aerosol compounds on the CCN activity of aerosol particles was studied by using a computational model for a DMT-CCN counter, a cloud parcel model for condensation kinetics and experiments to quantify the modelled results. Concentrations of water vapour and semivolatiles as well as aerosol trajectories in the CCN column were calculated by a computational fluid dynamics model. These trajectories and vapour concentrations were then used as an input for the cloud parcel model to simulate mass transfer kinetics of water and semivolatiles between aerosol particles and the gas phase. Two different questions were studied: (1) how big fraction of semivolatiles is evaporated from particles before activation in the CCN counter? (2) How much the CCN activity can be increased due to condensation of semivolatiles prior to the maximum water supersaturation in the case of high semivolatile concentration in the gas phase? The results show that, to increase the CCN activity of aerosol particles, a very high gas phase concentration (as compared to typical ambient conditions) is needed. We used nitric acid as a test compound. A concentration of several ppb or higher is needed for measurable effect. In the case of particle evaporation, we used ammonium nitrate as a test compound and found that it partially evaporates before maximum supersaturation is reached in the CCN counter, thus causing an underestimation of CCN activity. The effect of evaporation is clearly visible in all supersaturations, leading to an underestimation of the critical dry diameter by 10 to 15 nanometres in the case of ammonium nitrate particles in different supersaturations. This result was also confirmed by measurements in supersaturations between 0.1 and 0.7%.

  1. AN INVESTIGATION OF THE RELATIONSHIP BETWEEN GAS-PHASE AND AEROSOL-BORNE HYDROPEROXIDES IN URBAN AIR. (R827352)

    EPA Science Inventory

    Simultaneous measurements of hydroperoxides in both the gas- and the aerosol-phase have been made for the first time. In addition, hydroperoxide levels in the ‘coarse’ (>PM2) and ‘fine’ (PM2) aerosol modes have been characteriz...

  2. Stratospheric aerosol properties and their effects on infrared radiation.

    NASA Technical Reports Server (NTRS)

    Remsberg, E. E.

    1973-01-01

    This paper presents a stratospheric aerosol model and infers its effects on terrestrial radiation. Composition of the aerosol is assumed to be concentrated sulfuric acid. An appropriate size distribution has been determined from available size distribution measurements of other investigators. Aerosols composed of concentrated sulfuric acid emit energy in the atmospheric window region of the infrared spectrum, 8-13 microns. Laboratory measurements of optical constant data obtained at room temperature are presented for 75 and 90% aqueous sulfuric acid. Calculations of an aerosol extinction coefficient are then performed by using the above data. Effects of changes in aerosol phase and temperature are discussed but not resolved.

  3. Aqueous-phase oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Product identification from methyl jasmonate and methyl salicylate oxidation

    NASA Astrophysics Data System (ADS)

    Hansel, Amie K.; Ehrenhauser, Franz S.; Richards-Henderson, Nicole K.; Anastasio, Cort; Valsaraj, Kalliat T.

    2015-02-01

    Green leaf volatiles (GLVs) are a group of biogenic volatile organic compounds (BVOCs) released into the atmosphere by vegetation. BVOCs produce secondary organic aerosol (SOA) via gas-phase reactions, but little is known of their aqueous-phase oxidation as a source of SOA. GLVs can partition into atmospheric water phases, e.g., fog, mist, dew or rain, and be oxidized by hydroxyl radicals (˙OH). These reactions in the liquid phase also lead to products that have higher molecular weights, increased polarity, and lower vapor pressures, ultimately forming SOA after evaporation of the droplet. To examine this process, we investigated the aqueous, ˙OH-mediated oxidation of methyl jasmonate (MeJa) and methyl salicylate (MeSa), two GLVs that produce aqueous-phase SOA. High performance liquid chromatography/electrospray ionization mass spectrometry (HPLC-ESI-MS) was used to monitor product formation. The oxidation products identified exhibit higher molecular mass than their parent GLV due to either dimerization or the addition of oxygen and hydroxyl functional groups. The proposed structures of potential products are based on mechanistic considerations combined with the HPLC/ESI-MS data. Based on the structures, the vapor pressure and the Henry's law constant were estimated with multiple methods (SPARC, SIMPOL, MPBPVP, Bond and Group Estimations). The estimated vapor pressures of the products identified are significantly (up to 7 orders of magnitude) lower than those of the associated parent compounds, and therefore, the GLV oxidation products may remain as SOA after evaporation of the water droplet. The contribution of the identified oxidation products to SOA formation is estimated based on measured HPLC-ESI/MS responses relative to previous aqueous SOA mass yield measurements.

  4. Carbonate Complexation of Mn2+ in Aqueous Phase

    PubMed Central

    Dasgupta, Jyotishman; Tyryshkin, Alexei M.; Kozlov, Yuri N.; Klimov, Vyacheslav V.; Dismukes, G. Charles

    2008-01-01

    The chemical speciation of Mn2+ within cells is critical for its transport, availability and redox properties. Herein we investigate the redox behavior and complexation equilibria of Mn2+ in aqueous solutions of bicarbonate by voltametry and electron paramagnetic resonance (EPR) spectroscopy, and discuss the implications for the uptake of Mn2+ by mangano-cluster enzymes like photosystem II (PSII). Both the electrochemical reduction of Mn2+ to Mn0 at an Hg electrode and EPR (in the absence of a polarizing electrode), revealed formation of 1:1 and 1:2 Mn-(bi)carbonate complexes as a function of Mn2+ and bicarbonate concentrations. Pulsed EPR spectroscopy, including ENDOR, ESEEM and 2D-HYSCORE, were used to probe the hyperfine couplings to 1H and 13C nuclei of the ligand(s) bound to Mn2+. For the 1:2 complex the complete 13C hyperfine tensor for one of the (bi)carbonate ligands was determined and it was established that this ligand coordinates to Mn2+ in bidentate mode with 13C-Mn distance of 2.85 ± 0.1 Å. The second (bi)carbonate ligand in the 1:2 complex coordinates possibly in monodentate mode, which is structurally less defined, and its 13C signal is broad and unobservable. 1H ENDOR reveals that 1-2 water ligands are lost upon binding of one bicarbonate ion in the 1:1 complex while 3-4 water ligands are lost upon forming the 1:2 complex. Thus, we deduce that the dominant species above 0.1 M bicarbonate concentration is the 1:2 complex, [Mn(CO3)(HCO3)(OH2)3]-. PMID:16526753

  5. Inorganic Components of Atmospheric Aerosols

    NASA Astrophysics Data System (ADS)

    Wexler, Anthony Stein

    The inorganic components comprise 15% to 50% of the mass of atmospheric aerosols. For about the past 10 years the mass of these components was predicted assuming thermodynamic equilibrium between the volatile aerosol -phase inorganic species NH_4NO _3 and NH_4Cl and their gas-phase counterparts NH_3, HNO_3, and HCl. In this thesis I examine this assumption and prove that (1) the time scales for equilibration between the gas and aerosol phases are often too long for equilibrium to hold, and (2) even when equilibrium holds, transport considerations often govern the size distribution of these aerosol components. Water can comprise a significant portion of atmospheric aerosols under conditions of high relative humidity, whereas under conditions of sufficiently low relative humidity atmospheric aerosols tend to be dry. The deliquescence point is the relative humidity where the aerosol goes from a solid dry phase to an aqueous or mixed solid-aqueous phase. In this thesis I derive the temperature dependence of the deliquescence point and prove that in multicomponent solutions the deliquescence point is lower than for corresponding single component solutions. These theories of the transport, thermodynamic, and deliquescent properties of atmospheric aerosols are integrated into an aerosol inorganics model, AIM. The predictions of AIM compare well to fundamental thermodynamic measurements. Comparison of the prediction of AIM to those of other aerosol equilibrium models shows substantial disagreement in the predicted water content at lower relative humidities. The disagreement is due the improved treatment in AIM of the deliquescence properties of multicomponent solutions. In the summer and fall of 1987 the California Air Resources Board conducted the Southern California Air Quality Study, SCAQS, during which atmospheric aerosols were measured in Los Angeles. The size and composition of the aerosol and the concentrations of their gas phase counterparts were measured. When the

  6. Development and evaluation of the aerosol dynamics and gas phase chemistry model ADCHEM

    NASA Astrophysics Data System (ADS)

    Roldin, P.; Swietlicki, E.; Schurgers, G.; Arneth, A.; Lehtinen, K. E. J.; Boy, M.; Kulmala, M.

    2011-06-01

    The aim of this work was to develop a model suited for detailed studies of aerosol dynamics, gas and particle phase chemistry within urban plumes, from local scale (1 × 1 km2) to regional scale. This article describes and evaluates the trajectory model for Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer (ADCHEM). The model treats both vertical and horizontal dispersion perpendicular to an air mass trajectory (2-space dimensions). The Lagrangian approach enables a more detailed representation of the aerosol dynamics, gas and particle phase chemistry and a finer spatial and temporal resolution compared to that of available regional 3D-CTMs. These features make it among others well suited for urban plume studies. The aerosol dynamics model includes Brownian coagulation, dry deposition, wet deposition, in-cloud processing, condensation, evaporation, primary particle emissions and homogeneous nucleation. The organic mass partitioning was either modeled with a 2-dimensional volatility basis set (2D-VBS) or with the traditional two-product model approach. In ADCHEM these models consider the diffusion limited and particle size dependent condensation and evaporation of 110 and 40 different organic compounds respectively. The gas phase chemistry model calculates the gas phase concentrations of 61 different species, using 130 different chemical reactions. Daily isoprene and monoterpene emissions from European forests were simulated separately with the vegetation model LPJ-GUESS, and included as input to ADCHEM. ADCHEM was used to simulate the ageing of the urban plumes from the city of Malmö in southern Sweden (280 000 inhabitants). Several sensitivity tests were performed concerning the number of size bins, size structure method, aerosol dynamic processes, vertical and horizontal mixing, coupled or uncoupled condensation and the secondary organic aerosol formation. The simulations show that the full-stationary size structure gives accurate results

  7. Development and evaluation of the aerosol dynamic and gas phase chemistry model ADCHEM

    NASA Astrophysics Data System (ADS)

    Roldin, P.; Swietlicki, E.; Schurgers, G.; Arneth, A.; Lehtinen, K. E. J.; Boy, M.; Kulmala, M.

    2010-08-01

    The aim of this work was to develop a model ideally suited for detailed studies on aerosol dynamics, gas and particle phase chemistry within urban plumes, from local scale (1×1 km2) to regional or global scale. This article describes and evaluates the trajectory model for Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer (ADCHEM), which has been developed and used at Lund University since 2007. The model treats both vertical and horizontal dispersion perpendicular to an air mass trajectory (2-space dimensions), which is not treated in Lagrangian box-models (0-space dimensions). The Lagrangian approach enables a more detailed representation of the aerosol dynamics, gas and particle phase chemistry and a finer spatial and temporal resolution compared to that of available regional 3D-CTMs. These features make it among others ideally suited for urban plume studies. The aerosol dynamics model includes Brownian coagulation, dry deposition, wet deposition, in-cloud processing, condensation, evaporation, primary particle emissions and homogeneous nucleation. The gas phase chemistry model calculates the gas phase concentrations of 63 different species, using 119 different chemical reactions. Daily isoprene and monoterpene emissions from European forests were simulated separately with the vegetation model LPJ-GUESS, and included as input to ADCHEM. ADCHEM was used to simulate the ageing of the urban plumes from the city of Malmö in Southern Sweden (280 000 inhabitants). Several sensitivity tests were performed concerning the number of size bins, size structure method, coupled or uncoupled condensation, the volatility basis set (VBS) or traditional 2-product model for secondary organic aerosol formation, different aerosol dynamic processes and vertical and horizontal mixing. The simulations show that the full-stationary size structure gives accurate results with little numerical diffusion when more than 50 size bins are used between 1.5 and 2500 nm

  8. Label-Free Direct Visual Analysis of Hydrolytic Enzyme Activity Using Aqueous Two-Phase System Droplet Phase Transitions

    PubMed Central

    2015-01-01

    Dextran hydrolysis-mediated conversion of polyethylene glycol (PEG)-dextran (DEX) aqueous two-phase system droplets to a single phase was used to directly visualize Dextranase activity. DEX droplets were formed either by manual micropipetting or within a continuous PEG phase by computer controlled actuation of an orifice connecting rounded channels formed by backside diffused light lithography. The time required for the two-phase to one-phase transition was dependent on the Dextranase concentration, pH of the medium, and temperature. The apparent Michaelis constants for Dextranase were estimated based on previously reported catalytic constants, the binodal polymer concentration curves for PEG-DEX phase transition for each temperature, and pH condition. The combination of a microfluidic droplet system and phase transition observation provides a new method for label-free direct measurement of enzyme activity. PMID:24654925

  9. Mass spectrometry of interfacial layers during fast aqueous aerosol/ozone gas reactions of atmospheric interest

    NASA Astrophysics Data System (ADS)

    Enami, S.; Vecitis, C. D.; Cheng, J.; Hoffmann, M. R.; Colussi, A. J.

    2008-04-01

    The oxidations of sulfite and iodide in the interfacial layers of aqueous microdroplets exposed to O 3(g) for 1 ms are investigated by online mass spectrometry of the electrostatically ejected anions. S(IV) oxidation losses in Na 2SO 3 microdroplets are proportional to [S(IV)] [O 3(g)] up to ˜90% conversion. I - is more abundant than HSO3- in the interfacial layers of equimolar (Na 2SO 3 + NaI) microdroplets and ˜3 times more reactive than HSO3- toward O 3(aq) in bulk solution, but it is converted withminimalloss to I3- and IO3- plus a persistent ISO3- intermediate. These observations reveal unanticipated interfacial gradients, reactivity patterns and transport phenomena that had not been taken into account in previous treatments of fast gas-liquid reactions.

  10. Crystallization and immersion freezing ability of oxalic and succinic acid in multicomponent aqueous organic aerosol particles

    NASA Astrophysics Data System (ADS)

    Wagner, Robert; Höhler, Kristina; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin

    2015-04-01

    This study reports on heterogeneous ice nucleation efficiency of immersed oxalic and succinic acid crystals in the temperature range from 245 to 215 K, as investigated with expansion cooling experiments using suspended particles. In contrast to previous laboratory work with emulsified solution droplets where the precipitation of solid inclusions required a preceding freezing/evaporation cycle, we show that immersed solids readily form by homogeneous crystallization within aqueous solution droplets of multicomponent organic mixtures, which have noneutonic compositions with an excess of oxalic or succinic acid. Whereas succinic acid crystals did not act as heterogeneous ice nuclei, immersion freezing by oxalic acid dihydrate crystals led to a reduction of the ice saturation ratio at freezing onset by 0.066-0.072 compared to homogeneous freezing, which is by a factor of 2 higher than previously reported laboratory data. These observations emphasize the importance of oxalic acid in heterogeneous ice nucleation.

  11. A Chain of Modeling Tools For Gas and Aqueous Phase Chemstry

    NASA Astrophysics Data System (ADS)

    Audiffren, N.; Djouad, R.; Sportisse, B.

    Atmospheric chemistry is characterized by the use of large set of chemical species and reactions. Handling with the set of data required for the definition of the model is a quite difficult task. We prsent in this short article a preprocessor for diphasic models (gas phase and aqueous phase in cloud droplets) named SPACK. The main interest of SPACK is the automatic generation of lumped species related to fast equilibria. We also developped a linear tangent model using the automatic differentiation tool named ODYSSEE in order to perform a sensitivity analysis of an atmospheric multi- phase mechanism based on RADM2 kinetic scheme.Local sensitivity coefficients are computed for two different scenarii. We focus in this study on the sensitivity of the ozone,NOx,HOx, system with respect to some aqueous phase reactions and we inves- tigate the influence of the reduction in the photolysis rates in the area below the cloud region.

  12. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

    PubMed

    Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

    2014-12-01

    Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur. PMID:25368975

  13. “Towards building better linkages between aqueous phase chemistry and microphysics in CMAQ”

    EPA Science Inventory

    Currently, CMAQ’s aqueous phase chemistry routine (AQCHEM-base) assumes Henry’s Law equilibrium and employs a forward Euler method to solve a small set of oxidation equations, considering the additional processes of aitken scavenging and wet deposition in series and e...

  14. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

    PubMed

    Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

    2014-12-01

    Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

  15. Aqueous-phase hydrogenation of acetic acid over transition metal catalysts

    SciTech Connect

    Olcay, Hakan; Xu, Lijun; Xu, Ye; Huber, George

    2010-01-01

    Catalytic hydrogenation of acetic acid to ethanol has been carried out in aqueous phase on several metals, with ruthenium being the most active and selective. DFT calculations suggest that the initial CO bond scission yielding acetyl is the key step and that the intrinsic reactivity of the metals accounts for the observed activity.

  16. Climate missing links: Aqueous greenhouse species in clouds, fogs and aerosols

    SciTech Connect

    Gaffney, J.S.; Marley, N.A.; Cunningham, M.M.

    1991-11-01

    Recently, there has been considerable interest regarding possible greenhouse effects due to combustion and energy-related pollution. This concern has been due to the release and secondary production of greenhouse gases such as carbon dioxide, freons, methane, nitrous oxide, and ozone. These gases can absorb infrared radiation as it comes back from the heated ground and therefore effectively trap the infrared radiation in the troposphere, leading to climatic change. Beyond these gases, clouds, aerosols, and fogs may also play important roles in affecting, the radiation balance by scattering incoming radiation. This work describes the measurement of water soluble infrared absorbers that are known to be derived from pollution. Polluted precipitation is likely to be an important contributor to radiation balance that is currently being neglected. Pollutants characterized include sulfate, nitrate, formate, acetate, oxalate, phenol, p-nitrophenol, ammonium, carbonate, bicarbonate, formaldehyde (dihydroxy methane), methanol, and ethanol. Band positions and band strengths have been determined. These species show measurable infrared absorption bands in the atmospheric window regions (i.e., 900--1600 cm{sup {minus}1}). These data are discussed with regard to the reported discrepancies in the radiatively important water infrared absorption region commonly referred to as the ``foreign broadened continuum.``

  17. PHASE BEHAVIOR OF LIGHT GASES IN HYDROGEN AND AQUEOUS SOLVENTS

    SciTech Connect

    KHALED A.M. GASEM; ROBERT L. ROBINSON, JR.

    1999-03-31

    Under previous support from the US Department of Energy, an experimental facility has been established and operated to measure valuable vapor-liquid equilibrium data for systems of interest in the production and processing of coal fluids. To facilitate the development and testing of models for prediction of the phase behavior for such systems, we have acquired substantial amounts of data on the equilibrium phase compositions for binary mixtures of heavy hydrocarbon solvents with a variety of supercritical solutes, including hydrogen, methane, ethane, carbon monoxide, and carbon dioxide. The present project focuses on measuring the phase behavior of light gases and water in Fischer-Tropsch (F-T) type solvents at conditions encountered in indirect liquefaction processes and evaluating and developing theoretically-based correlating frameworks to predict the phase behavior of such systems. Specific goals of the proposed work include (a) developing a state-of-the-art experimental facility to permit highly accurate measurements of equilibrium phase compositions (solubilities) of challenging F-T systems, (b) measuring these properties for systematically-selected binary, ternary and molten F-T wax mixtures to provide critically needed input data for correlation development, (c) developing and testing models suitable for describing the phase behavior of such mixtures, and (d) presenting the modeling results in generalized, practical formats suitable for use in process engineering calculations. During the present reporting period, the solubilities of hydrogen in n-hexane, carbon monoxide in cyclohexane, and nitrogen in phenanthrene and pyrene were measured using a static equilibrium cell over the temperature range from 344.3 to 433.2 K and pressures to 22.8 MPa. The uncertainty in these new solubility measurements is estimated to be less than 0.001 in mole fraction. The data were analyzed using the Peng-Robinson (PR) equation of state (EOS). In general, the PR EOS represents

  18. Liquid-liquid phase separation in aerosol particles: imaging at the nanometer scale.

    PubMed

    O'Brien, Rachel E; Wang, Bingbing; Kelly, Stephen T; Lundt, Nils; You, Yuan; Bertram, Allan K; Leone, Stephen R; Laskin, Alexander; Gilles, Mary K

    2015-04-21

    Atmospheric aerosols can undergo phase transitions including liquid-liquid phase separation (LLPS) while responding to changes in the ambient relative humidity (RH). Here, we report results of chemical imaging experiments using environmental scanning electron microscopy (ESEM) and scanning transmission X-ray microscopy (STXM) to investigate the LLPS of micrometer-sized particles undergoing a full hydration-dehydration cycle. Internally mixed particles composed of ammonium sulfate (AS) and either: limonene secondary organic carbon (LSOC), α, 4-dihydroxy-3-methoxybenzeneaceticacid (HMMA), or polyethylene glycol (PEG-400) were studied. Events of LLPS were observed for all samples with both techniques. Chemical imaging with STXM showed that both LSOC/AS and HMMA/AS particles were never homogeneously mixed for all measured RH's above the deliquescence point and that the majority of the organic component was located in the outer phase. The outer phase composition was estimated as 65:35 organic: inorganic in LSOC/AS and as 50:50 organic: inorganic for HMMA/AS. PEG-400/AS particles showed fully homogeneous mixtures at high RH and phase separated below 89-92% RH with an estimated 70:30% organic to inorganic mix in the outer phase. These two chemical imaging techniques are well suited for in situ analysis of the hygroscopic behavior, phase separation, and surface composition of collected ambient aerosol particles.

  19. Chemical Reactivity of alpha-Pinene-derived Products in the Aqueous Phase: Implications on the Fate of Organic Nitrates

    NASA Astrophysics Data System (ADS)

    Rindelaub, J. D.; Hostetler, M. A.; Lipton, M. A.; Shepson, P. B.

    2014-12-01

    The production of organic nitrates has significant atmospheric importance due to the impact on regional air quality by influencing NOx lifetimes and ozone formation. Additionally, these low volatility compounds readily partition into the particle phase and are important contributors to secondary organic aerosol. Once in the aerosol phase, organic nitrates undergo further chemical reactions that govern their fate in the atmosphere and, consequently, their impact on air quality. Recent research indicates that the presence of water on aerosol particles has a major impact on the reactivity of organic nitrates and that condensed phase hydrolysis leads to the destruction of organic nitrate species, depending on structure. Despite this knowledge, the chemical mechanisms, products, product reactivity and volatility are still uncertain, negatively impacting our understanding of aerosol phase processing and the contribution to air quality. To further understand the atmospheric impact of aerosol phase hydrolysis, we analyzed both condensed phase hydrolysis reactions involving alpha-pinene-derived standards and alpha-pinene photochemical chamber reaction filter samples, using a suite of spectroscopic and mass spectrometric techniques. We were able to measure the pH-dependent hydrolysis rate constants for several types of organic nitrates and identify specific reaction products. The chemistry involved exhibits a strong dependence on pH, providing important mechanistic clues. The results of this study will significantly contribute to our knowledge of aerosol phase chemistry and the impact on regional air quality with respect to the fate of organic nitrate species.

  20. Condensed-Phase Photochemical Processes in Titan's Aerosols and Surface: The Role of Longer Wavelength Photochemistry

    NASA Technical Reports Server (NTRS)

    Gudipati, Murthy S.; Jacovi, Ronen; Lignell, Antti; Couturier, Isabelle

    2011-01-01

    We will discuss photochemical properties of Titan's organic molecules in the condensed phase as solid aerosols or surface material, from small linear polyyenes (polyacetylenes and polycyanoacetylenes) such as C2H2, C4N2, HC5N, etc. In particular we will focus on photochemistry caused by longer wavelength UV-VIS photons (greater than 250 nm) photons that make it through Titan's atmosphere to the haze region (approximately 100 km) and on to the surface of Titan.

  1. A Robust Computational Method for Coupled Liquid-liquid Phase Separation and Gas-particle Partitioning Predictions of Multicomponent Aerosols

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Di Stefano, A.

    2014-12-01

    Providing efficient and reliable model predictions for the partitioning of atmospheric aerosol components between different phases (gas, liquids, solids) is a challenging problem. The partitioning of water, various semivolatile organic components, inorganic acids, bases, and salts, depends simultaneously on the chemical properties and interaction effects among all constituents of a gas + aerosol system. The effects of hygroscopic particle growth on the water contents and physical states of potentially two or more liquid and/or solid aerosol phases in turn may significantly affect multiphase chemistry, the direct effect of aerosols on climate, and the ability of specific particles to act as cloud condensation or ice nuclei. Considering the presence of a liquid-liquid phase separation in aerosol particles, which typically leads to one phase being enriched in rather hydrophobic compounds and the other phase enriched in water and dissolved electrolytes, adds a high degree of complexity to the goal of predicting the gas-particle partitioning of all components. Coupled gas-particle partitioning and phase separation methods are required to correctly account for the phase behaviour of aerosols exposed to varying environmental conditions, such as changes to relative humidity. We present new theoretical insights and a substantially improved algorithm for the reliable prediction of gas-particle partitioning at thermodynamic equilibrium based on the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. We introduce a new approach for the accurate prediction of the phase distribution of multiple inorganic ions between two liquid phases, constrained by charge balance, and the coupling of the liquid-liquid equilibrium model to a robust gas-particle partitioning algorithm. Such coupled models are useful for exploring the range of environmental conditions leading to complete or incomplete miscibility of aerosol constituents which will affect

  2. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Yee, L. D.; Schilling, K.; Loza, C. L.; Craven, J. S.; Zuend, A.; Ziemann, P. J.; Seinfeld, J.

    2013-12-01

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosol (SOA). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multi-generation gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a mid-experiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. The results of the current work have a number of implications for SOA models. While the dynamics of an aerosol size distribution reflects the mechanism of growth, we demonstrate here that it provides a key constraint in interpreting laboratory and ambient SOA formation. This work, although carried out specifically for the long chain alkane, dodecane, is expected to be widely applicable to other major classes of SOA precursors. SOA consists of a myriad of organic compounds containing various functional groups, which can generally undergo heterogeneous/multiphase reactions forming low-volatility products such as oligomers and other high molecular mass compounds. If particle-phase chemistry is indeed

  3. Interactions of Gas-Phase Nitric/Nitrous Acids and Primary Organic Aerosol in the Atmosphere of Houston, TX

    NASA Astrophysics Data System (ADS)

    Ziemba, L. D.; Griffin, R. J.; Dibb, J. E.; Anderson, C. H.; Whitlow, S. I.; Lefer, B. L.; Flynn, J.; Rappenglück, B.

    2007-12-01

    Concentrations of aerosol and gas-phase pollutants were measured on the roof of an 18-story building during the Texas Air Quality Study II Radical and Aerosol Measurement Project (TRAMP) from August 15 through September 28, 2006. Aerosol measurements included size-resolved, non-refractory mass concentrations of ammonium, nitrate, sulfate, chloride, and organic aerosol in submicron particles using an Aerodyne quadrupole aerosol mass spectrometer (Q-AMS). Particulate water-soluble organic carbon (PWSOC) was quantified using a mist chamber/total organic carbon analysis system. Concentration data for gas-phase pollutants included those for nitric acid (HNO3), nitrous acid (HONO), and hydrochloric acid (HCl) collected using a mist chamber/ion chromatographic technique, oxides of nitrogen (NOx) collected using a chemiluminescent method, and carbon monoxide (CO) collected using an infrared gas correlation wheel instrument. Coincident increases in nitrate and organic aerosol mass concentrations were observed on many occasions throughout the measurement campaign, most frequently during the morning rush hour. Based on the lack of organic aerosol processing (defined by the ratio of m/z = 44/57 in the Q-AMS spectra), strong correlation with NOx and CO, and a lack of significant increase in PWSOC concentration, the spikes in organic aerosol were likely associated with primary organic aerosol (POA). During these events, gas-phase HNO3 concentration decreases were observed simultaneously with increases in gas-phase HONO concentrations. These data likely indicate uptake of HNO3 and subsequent heterogeneous conversion to HONO involving POA. Preliminary calculations show that HNO3 partitioning could account for the majority of the observed HONO and aerosol nitrate concentrations during these events. Q-AMS chloride and HCl data also indicate uptake of chloride by particles during these events. This phenomenon was also observed during the night, but these nocturnal events were less

  4. What controls the vertical distribution of aerosol? Relationships between process sensitivity in HadGEM3-UKCA and inter-model variation from AeroCom Phase II

    NASA Astrophysics Data System (ADS)

    Kipling, Z.; Stier, P.; Johnson, C. E.; Mann, G. W.; Bellouin, N.; Bauer, S. E.; Bergman, T.; Chin, M.; Diehl, T.; Ghan, S. J.; Iversen, T.; Kirkevåg, A.; Kokkola, H.; Liu, X.; Luo, G.; van Noije, T.; Pringle, K. J.; von Salzen, K.; Schulz, M.; Seland, Ø.; Skeie, R. B.; Takemura, T.; Tsigaridis, K.; Zhang, K.

    2015-09-01

    The vertical profile of aerosol is important for its radiative effects, but weakly constrained by observations on the global scale, and highly variable among different models. To investigate the controlling factors, we investigate the effects of individual processes in one particular model (HadGEM3-UKCA), and compare the resulting diversity of aerosol vertical profiles with the inter-model diversity from the AeroCom Phase II control experiment. In this way we show that (in this model at least) the vertical profile is controlled by a relatively small number of processes, although these vary among aerosol components and particle sizes. We also show that sufficiently coarse variations in these processes can produce a similar diversity to that among different models in terms of the global mean profile and zonal-mean vertical position. However, there are features of certain models' profiles that cannot be reproduced, suggesting the influence of further structural differences between models. Convective transport is found to be very important in controlling the vertical profile of all aerosol components by mass. In-cloud scavenging is very important for all except mineral dust. Growth by condensation is important for sulphate and carbonaceous aerosol (along with aqueous oxidation for the former and ageing by soluble material for the latter). The vertical extent of biomass-burning emissions into the free troposphere is also important for the profile of carbonaceous aerosol. Boundary-layer mixing plays a dominant role for sea-salt and mineral dust, which are emitted only from the surface. Dry deposition and below-cloud scavenging are important for the profile of mineral dust only. In this model, the microphysical processes of nucleation, condensation and coagulation dominate the vertical profile of the smallest particles by number, while the profiles of larger particles are controlled by the same processes as the component mass profiles, plus the size distribution of

  5. What Controls the Vertical Distribution of Aerosol? Relationships Between Process Sensitivity in HadGEM3-UKCA and Inter-Model Variation from AeroCom Phase II

    NASA Technical Reports Server (NTRS)

    Kipling, Zak; Stier, Philip; Johnson, Colin E.; Mann, Graham W.; Bellouin, Nicolas; Bauer, Susanne E.; Bergman, Tommi; Chin, Mian; Diehl, Thomas; Ghan, Steven J.; Tsigaridis, Kostas

    2016-01-01

    The vertical profile of aerosol is important for its radiative effects, but weakly constrained by observations on the global scale, and highly variable among different models. To investigate the controlling factors in one particular model, we investigate the effects of individual processes in HadGEM3-UKCA and compare the resulting diversity of aerosol vertical profiles with the inter-model diversity from the AeroCom Phase II control experiment. In this way we show that (in this model at least) the vertical profile is controlled by a relatively small number of processes, although these vary among aerosol components and particle sizes. We also show that sufficiently coarse variations in these processes can produce a similar diversity to that among different models in terms of the global-mean profile and, to a lesser extent, the zonal-mean vertical position. However, there are features of certain models' profiles that cannot be reproduced, suggesting the influence of further structural differences between models. In HadGEM3-UKCA, convective transport is found to be very important in controlling the vertical profile of all aerosol components by mass. In-cloud scavenging is very important for all except mineral dust. Growth by condensation is important for sulfate and carbonaceous aerosol (along with aqueous oxidation for the former and ageing by soluble material for the latter). The vertical extent of biomass-burning emissions into the free troposphere is also important for the profile of carbonaceous aerosol. Boundary-layer mixing plays a dominant role for sea salt and mineral dust, which are emitted only from the surface. Dry deposition and below-cloud scavenging are important for the profile of mineral dust only. In this model, the microphysical processes of nucleation, condensation and coagulation dominate the vertical profile of the smallest particles by number (e.g. total CN >3 nm), while the profiles of larger particles (e.g. CN>100 nm) are controlled by the

  6. What controls the vertical distribution of aerosol? Relationships between process sensitivity in HadGEM3-UKCA and inter-model variation from AeroCom Phase II

    NASA Astrophysics Data System (ADS)

    Kipling, Zak; Stier, Philip; Johnson, Colin E.; Mann, Graham W.; Bellouin, Nicolas; Bauer, Susanne E.; Bergman, Tommi; Chin, Mian; Diehl, Thomas; Ghan, Steven J.; Iversen, Trond; Kirkevåg, Alf; Kokkola, Harri; Liu, Xiaohong; Luo, Gan; van Noije, Twan; Pringle, Kirsty J.; von Salzen, Knut; Schulz, Michael; Seland, Øyvind; Skeie, Ragnhild B.; Takemura, Toshihiko; Tsigaridis, Kostas; Zhang, Kai

    2016-02-01

    The vertical profile of aerosol is important for its radiative effects, but weakly constrained by observations on the global scale, and highly variable among different models. To investigate the controlling factors in one particular model, we investigate the effects of individual processes in HadGEM3-UKCA and compare the resulting diversity of aerosol vertical profiles with the inter-model diversity from the AeroCom Phase II control experiment. In this way we show that (in this model at least) the vertical profile is controlled by a relatively small number of processes, although these vary among aerosol components and particle sizes. We also show that sufficiently coarse variations in these processes can produce a similar diversity to that among different models in terms of the global-mean profile and, to a lesser extent, the zonal-mean vertical position. However, there are features of certain models' profiles that cannot be reproduced, suggesting the influence of further structural differences between models. In HadGEM3-UKCA, convective transport is found to be very important in controlling the vertical profile of all aerosol components by mass. In-cloud scavenging is very important for all except mineral dust. Growth by condensation is important for sulfate and carbonaceous aerosol (along with aqueous oxidation for the former and ageing by soluble material for the latter). The vertical extent of biomass-burning emissions into the free troposphere is also important for the profile of carbonaceous aerosol. Boundary-layer mixing plays a dominant role for sea salt and mineral dust, which are emitted only from the surface. Dry deposition and below-cloud scavenging are important for the profile of mineral dust only. In this model, the microphysical processes of nucleation, condensation and coagulation dominate the vertical profile of the smallest particles by number (e.g. total CN > 3 nm), while the profiles of larger particles (e.g. CN > 100 nm) are controlled by the

  7. Aqueous Two-Phase Systems formed by Biocompatible and Biodegradable Polysaccharides and Acetonitrile

    PubMed Central

    de Brito Cardoso, Gustavo; Souza, Isabela Nascimento; Pereira, Matheus M.; Freire, Mara G.; Soares, Cleide Mara Faria; Lima, Álvaro Silva

    2015-01-01

    In this work, it is shown that novel aqueous two-phase systems can be formed by the combination of acetonitrile and polysaccharides, namely dextran. Several ternary phase diagrams were determined at 25 °C for the systems composed of water + acetonitrile + dextran. The effect of the dextran molecular weight (6,000, 40,000 and 100,000 g.mol−1) was ascertained toward their ability to undergo liquid-liquid demixing. An increase in the dextran molecular weight favors the phase separation. Furthermore, the effect of temperature (25, 35 and 45 °C) was evaluated for the system constituted by the dextran of higher molecular weight. Lower temperatures are favorable for phase separation since lower amounts of dextran and acetonitrile are required for the creation of aqueous two-phase systems. In general, acetonitrile is enriched in the top phase while dextran is majorly concentrated in the bottom phase. The applicability of this new type of two-phase systems as liquid-liquid extraction approaches was also evaluated by the study of the partition behavior of a well-known antioxidant – vanillin - and used here as a model biomolecule. The optimized conditions led to an extraction efficiency of vanillin of 95% at the acetonitrile-rich phase. PMID:25729320

  8. Microevaporators with accumulators for the screening of phase diagrams of aqueous solutions

    NASA Astrophysics Data System (ADS)

    Moreau, P.; Dehmoune, J.; Salmon, J.-B.; Leng, J.

    2009-07-01

    We design near-autonomous microfluidic devices for concentrating aqueous solutions steadily over days in a very controlled manner. We combine suction pumps that drive the solution and concentrate it steadily, with a nanoliter-sized storage pool where the solute accumulates. The fine balance between advection and diffusion in the pump and diffusion alone in the accumulation pool yields several filling regimes. One of them is universal as being steady and independent of the solute itself. It results a specific equivalence between time and concentration, which we use to build the phase quantitative diagram of a ternary aqueous solution on nanoliter scale.

  9. Application of integral-equation theory to aqueous two-phase partitioning systems

    SciTech Connect

    Haynes, C.A.; Benitez, F.J.; Blanch, H.W.; Prausnitz, J.M. )

    1993-09-01

    A molecular-thermodynamic model is developed for representing thermodynamic properties of aqueous two-phase systems containing polymers, electrolytes, and proteins. The model is based on McMillan-Mayer solution theory and the generalized mean-spherical approximation to account for electrostatic forces between unlike ions. The Boublik-Mansoori equation of state for hard-sphere mixtures is coupled with the osmotic virial expansion truncated after the second-virial terms to account for short-range forces between molecules. Osmotic second virial coefficients are reported from low-angle laser-light scattering (LALLS) data for binary and ternary aqueous solutions containing polymers and proteins. Ion-polymer specific-interaction coefficients are determined from osmotic-pressure data for aqueous solutions containing a water-soluble polymer and an alkali chloride, phosphate or sulfate salt. When coupled with LALLS and osmotic-pressure data reported here, the model is used to predict liquid-liquid equilibria, protein partition coefficients, and electrostatic potentials between phases for both polymer-polymer and polymer-salt aqueous two-phase systems. For bovine serum albumin, lysozyme, and [alpha]-chymotrypsin, predicted partition coefficients are in excellent agreement with experiment.

  10. Biodegradation of multiple aromatic solutes from non-aqueous phase liquids

    SciTech Connect

    Johansen, P.; Ramaswami A.; Basile, F.

    1995-12-31

    Multi-component dense non-aqueous phase liquids (DNAPLs) act as long-term sources of subsurface contamination, slowly releasing organic pollutants into soil and groundwater. This study evaluates the potential for biological stabilization of the pollution source region containing a separate organic phase liquid (NAPL). Biostabilization refers to the process by which aqueous contaminant concentrations may be controlled without complete microbial destruction of the NAPL mass. Very little is known about the concurrent dissolution and degradation of multiple organic substrates from complex NAPLs, such as coal tar, creosote, PCB congeners and mixtures of waste solvents. In this study, biodegradation experiments are being conducted with a model multi-component NAPL to evaluate the rate of depletion of three target polycyclic aromatic hydrocarbon (PAH) compounds from the NAPL source. Dissolved aqueous-phase PAH concentrations, as well as the time-scale for depletion of the target PAH constituents from the NAPL due to microbial activity, are being monitored. These experiments will offer insights on the potential for minimizing aqueous plume development and generating a stable post-degradation NAPL residue through biostabilization.

  11. Reforming and decomposition of glucose in an aqueous phase

    NASA Technical Reports Server (NTRS)

    Amin, S.; Reid, R. C.; Modell, M.

    1975-01-01

    Exploratory experiments have been carried out to study the decomposition of glucose, a typical carbohydrate, in a high temperature-high pressure water reactor. The objective of the study was to examine the feasibility of such a process to decompose cellulosic waste materials in long-term space missions. At temperatures below the critical point of water, glucose decomposed to form liquid products and char. Little gas was noted with or without reforming catalysts present. The rate of the primary glucose reaction increased significantly with temperature. Partial identification of the liquid phase was made and the C:H:O ratios determined for both the liquid and solid products. One of the more interesting results from this study was the finding that when glucose was injected into a reactor held at the critical temperature (and pressure) of water, no solid products formed. Gas production increased, but the majority of the carbon was found in soluble furans (and furan derivatives). This significant result is now being investigated further.

  12. Structural and optical properties of solid-phase singlet oxygen photosensitizers based on fullerene aqueous suspensions

    NASA Astrophysics Data System (ADS)

    Belousova, I. M.; Belousov, V. P.; Kiselev, V. M.; Murav'eva, T. D.; Kislyakov, I. M.; Sirotkin, A. K.; Starodubtsev, A. M.; Kris'ko, T. K.; Bagrov, I. V.; Ermakov, A. V.

    2008-11-01

    The relationship between the structural and photosensitizing properties of solid-phase particles of fullerene C60 in aqueous suspensions is studied using the methods of absorption spectroscopy, electron spin resonance spectroscopy (ESR), X-ray diffraction, and spectrophotometry of solutions of singlet oxygen chemical traps—histidine in combination with p-nitrosodimethylaniline. Two new variants are proposed for obtaining aqueous suspensions of particles of solid-phase fullerene whose structures are disordered and whose degrees of amorphization are 67 and 40%, respectively. It is shown that an increase in the disorder of the structure of particles in suspensions and a decrease in their average size facilitate an increase in the formation efficiency of singlet oxygen by solid-phase fullerene presumably due to an in increase in the concentration of surface localized excitons.

  13. Influence of interface stabilisers and surrounding aqueous phases on nematic liquid crystal shells.

    PubMed

    Noh, JungHyun; Reguengo De Sousa, Kevin; Lagerwall, Jan P F

    2016-01-14

    We investigate the nematic-isotropic (N-I) transition in shells of the liquid crystal 5CB, surrounded by aqueous phases that conventionally are considered to be immiscible with 5CB. The aqueous phases contain either sodium dodecyl sulfate (SDS) or polyvinyl alcohol (PVA) as stabiliser, the former additionally promoting homeotropic director alignment. For all shell configurations we find a depression of the clearing point compared to pure 5CB, indicating that a non-negligible fraction of the constituents of the surrounding phases enter the shell, predominantly water. In hybrid-aligned shells, with planar outer and homeotropic inner boundary (or vice versa), the N-I transition splits into two steps, with a consequent three-step textural transformation. We explain this as a result of the order-enhancing effect of a monolayer of radially aligned SDS molecules adsorbed at the homeotropic interface. PMID:26512764

  14. Relationship between solution structure and phase behavior: a neutron scattering study of concentrated aqueous hexamethylenetetramine solutions.

    PubMed

    Burton, R C; Ferrari, E S; Davey, R J; Finney, J L; Bowron, D T

    2009-04-30

    The water-hexamethylenetetramine system displays features of significant interest in the context of phase equilibria in molecular materials. First, it is possible to crystallize two solid phases depending on temperature, both hexahydrate and anhydrous forms. Second, saturated aqueous solutions in equilibrium with these forms exhibit a negative dependence of solubility (retrograde) on temperature. In this contribution, neutron scattering experiments (with isotopic substitution) of concentrated aqueous hexamethylenetetramine solutions combined with empirical potential structure refinement (EPSR) were used to investigate the time-averaged atomistic details of this system. Through the derivation of radial distribution functions, quantitative details emerge of the solution coordination, its relationship to the nature of the solid phases, and of the underlying cause of the solubility behavior of this molecule.

  15. Medical costs and adherence in patients receiving aqueous versus pressurized aerosol formulations of intranasal corticosteroids.

    PubMed

    Hankin, Cheryl S; Cox, Linda; Lang, David; Bronstone, Amy; Wang, Zhaohui; Lepore, Mark S; Buck, Philip O

    2012-01-01

    Intranasal corticosteroid (INS) formulations have different sensory attributes that influence patient preferences, and thereby possibly adherence and health outcomes. This study compares health care use and costs and medication adherence in matched cohorts of patients with allergic rhinitis (AR) using a chlorofluorocarbon-propelled pressurized metered-dose inhaler (pMDI) or aqueous intranasal corticosteroid (A-INS). Florida Medicaid retrospective claims analysis was performed of enrollees aged ≥12 years with at least 1 year of continuous enrollment before their initial AR diagnosis, 1 year for continuous enrollment before their index INS claim, and 18 months of continuous enrollment after their index INS claim during which they received either pMDI or A-INS. pMDI and A-INS patients were matched 1:2 using propensity scores. Nonparametric analyses compared outcomes between matched cohorts at 6, 12, and 18 months of follow-up. A total of 585 patients were matched (pMDI = 195, A-INS = 390). pMDI patients were more adherent to INS, as reflected in their higher median medication possession ratio (53.2% versus 32.7%; p < 0.0001) and fewer median days between fills (73 days versus 111 days; p = 0.0003). Significantly lower median per patient pharmacy fills (34.0 versus 50.5; p < 0.05) and costs ($1282 versus $2178; p < 0.01) were observed among pMDI patients versus A-INS patients 18 months after INS initiation and were maintained when analyses excluded INS fills. Adherence to INS and health care utilization and costs following INS initiation for AR differed by type of formulation received. Our findings suggest patient preferences for INS sensory attributes can drive adherence and affect disease control, and ultimately impact health care costs. PMID:22737709

  16. Modified cavity attenuated phase shift (CAPS) method for airborne aerosol light extinction measurement

    NASA Astrophysics Data System (ADS)

    Perim de Faria, Julia; Bundke, Ulrich; Freedman, Andrew; Petzold, Andreas

    2015-04-01

    Monitoring the direct impact of aerosol particles on climate requires the consideration of at least two major factors: the aerosol single-scattering albedo, defined as the relation between the amount of energy scattered and extinguished by an ensemble of aerosol particles; and the aerosol optical depth, calculated from the integral of the particle extinction coefficient over the thickness of the measured aerosol layer. Remote sensing networks for measuring these aerosol parameters on a regular basis are well in place (e.g., AERONET, ACTRIS), whereas the regular in situ measurement of vertical profiles of atmospheric aerosol optical properties remains still an important challenge in quantifying climate change. The European Research Infrastructure IAGOS (In-service Aircraft for a Global Observing System; www.iagos.org) responds to the increasing requests for long-term, routine in situ observational data by using commercial passenger aircraft as measurement platform. However, scientific instrumentation for the measurement of atmospheric constituents requires major modifications before being deployable aboard in-service passenger aircraft. Recently, a compact and robust family of optical instruments based on the cavity attenuated phase shift (CAPS) technique has become available for measuring aerosol light extinction. In particular, the CAPS PMex particle optical extinction monitor has demonstrated sensitivity of less than 2 Mm-1 in 1 second sampling period; with a 60 s averaging time, a detection limit of less than 0.3 Mm-1 can be achieved. While this technique was successfully deployed for ground-based atmospheric measurements under various conditions, its suitability for operation aboard aircraft in the free and upper free troposphere still has to be demonstrated. Here, we report on the modifications of a CAPS PMex instrument for measuring aerosol light extinction on aircraft, and subsequent laboratory tests for evaluating the modified instrument prototype: (1) In a

  17. Role of the aerosol phase state in ammonia/amines exchange reactions.

    PubMed

    Chan, Lap P; Chan, Chak K

    2013-06-01

    The exchange reaction of ammonia in (NH4)2SO4 with an amine and the corresponding reverse reaction of amines in aminium sulfates with ammonia were investigated using an electrodynamic balance coupled with a Raman spectrometer. The temporal changes in particle mass, chemical composition, and phase state were simultaneously monitored. When the salt particles were in an aqueous state at elevated relative humidities (RHs), the exchange of ammonia/amine vapors in the particle phase was reversible. The exchange rates of aqueous particles were in general higher than those of their corresponding solid counterparts. An aqueous phase was essential for the effective displacement of ammonia and amines. Aminium salts in different phase states and with different evaporation characteristics showed remarkably different reaction behaviors in ammonia vapor. The less compact amorphous aminium sulfate solids were more susceptible to ammonia exchange than the crystalline solids. The aminium salts in a liquid state exhibited substantial amine evaporation at <3% RH and formed acidic bisulfate. Under ammonia exposure, these acidic aminium droplets underwent both neutralization and displacement reactions. Stable solid salts containing ammonium, aminium, sulfate, and bisulfate were formed and hindered further reactions. The result suggests that ambient aminium sulfates may be acidic. Overall, the phase states of the ammonium and aminium salt particles crucially determine the heterogeneous reaction rates and final product properties and identities. PMID:23668831

  18. A 1-dodecanethiol-based phase transfer protocol for the highly efficient extraction of noble metal ions from aqueous phase.

    PubMed

    Chen, Dong; Cui, Penglei; Cao, Hongbin; Yang, Jun

    2015-03-01

    A 1-dodecanethiol-based phase-transfer protocol is developed for the extraction of noble metal ions from aqueous solution to a hydrocarbon phase, which calls for first mixing the aqueous metal ion solution with an ethanolic solution of 1-dodecanethiol, and then extracting the coordination compounds formed between noble metal ions and 1-dodecanethiol into a non-polar organic solvent. A number of characterization techniques, including inductively coupled plasma atomic emission spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis demonstrate that this protocol could be applied to extract a wide variety of noble metal ions from water to dichloromethane with an efficiency of >96%, and has high selectivity for the separation of the noble metal ions from other transition metals. It is therefore an attractive alternative for the extraction of noble metals from water, soil, or waste printed circuit boards.

  19. Optical phase curves as diagnostics for aerosol composition in exoplanetary atmospheres

    NASA Astrophysics Data System (ADS)

    Oreshenko, Maria; Heng, Kevin; Demory, Brice-Olivier

    2016-04-01

    Optical phase curves have become one of the common probes of exoplanetary atmospheres, but the information they encode has not been fully elucidated. Building on a diverse body of work, we upgrade the Flexible Modelling System to include scattering in the two-stream, dual-band approximation and generate plausible, three-dimensional structures of irradiated atmospheres to study the radiative effects of aerosols or condensates. In the optical, we treat the scattering of starlight using a generalization of Beer's law that allows for a finite Bond albedo to be prescribed. In the infrared, we implement the two-stream solutions and include scattering via an infrared scattering parameter. We present a suite of four-parameter general circulation models for Kepler-7b and demonstrate that its climatology is expected to be robust to variations in optical and infrared scattering. The westward and eastward shifts of the optical and infrared phase curves, respectively, are shown to be robust outcomes of the simulations. Assuming micron-sized particles and a simplified treatment of local brightness, we further show that the peak offset of the optical phase curve is sensitive to the composition of the aerosols or condensates. However, to within the measurement uncertainties, we cannot distinguish between aerosols made of silicates (enstatite or forsterite), iron, corundum or titanium oxide, based on a comparison to the measured peak offset (41° ± 12°) of the optical phase curve of Kepler-7b. Measuring high-precision optical phase curves will provide important constraints on the atmospheres of cloudy exoplanets and reduce degeneracies in interpreting their infrared spectra.

  20. High-resolution mass spectrometry and molecular characterization of aqueous photochemistry products of common types of secondary organic aerosols.

    PubMed

    Romonosky, Dian E; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A

    2015-03-19

    This work presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d-limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow-tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx-generated SOA had more unique visual appearance and indicated a lower extent of product overlap. Furthermore, the fraction of nitrogen-containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone-driven oxidation. Comparison of the SOA constituents before and after photolysis showed the tendency to reduce the average number of atoms in the SOA compounds without a significant effect on the overall O/C and H/C ratios. SOA prepared by OH/NOx photooxidation of 1,3,5-trimethylbenzene and guaiacol were more resilient to photolysis despite being the most light-absorbing. The composition of SOA prepared by ozonolysis of

  1. High-resolution mass spectrometry and molecular characterization of aqueous photochemistry products of common types of secondary organic aerosols.

    PubMed

    Romonosky, Dian E; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A

    2015-03-19

    This work presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d-limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow-tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx-generated SOA had more unique visual appearance and indicated a lower extent of product overlap. Furthermore, the fraction of nitrogen-containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone-driven oxidation. Comparison of the SOA constituents before and after photolysis showed the tendency to reduce the average number of atoms in the SOA compounds without a significant effect on the overall O/C and H/C ratios. SOA prepared by OH/NOx photooxidation of 1,3,5-trimethylbenzene and guaiacol were more resilient to photolysis despite being the most light-absorbing. The composition of SOA prepared by ozonolysis of

  2. Reacto-Diffusive Length of N2O5 in Aqueous Sulfate- and Chloride-Containing Aerosol Particles.

    PubMed

    Gaston, Cassandra J; Thornton, Joel A

    2016-02-25

    Heterogeneous reactions of dinitrogen pentoxide (N2O5) on aerosol particles impact air quality and climate, yet aspects of the relevant physical chemistry remain unresolved. One important consideration is the competing effects of diffusion and the rate of chemical reaction within the particle, which determines the length that N2O5 travels within a particle before reacting, referred to as the reacto-diffusive length (l). Large values of l imply a dependence of the reactive uptake efficiency of N2O5, i.e., γ(N2O5), on particle size. We present measurements of the size dependence of γ(N2O5) on aqueous sodium chloride, ammonium sulfate, and ammonium bisulfate particles. γ(N2O5) on ammonium sulfate and ammonium bisulfate particles ranged from 0.016 ± 0.005 to 0.036 ± 0.001 as the surface-area-weighted particle radius increased from 39 to 127 nm, resulting in an estimated l of 32 ± 6 nm. In contrast, γ(N2O5) on sodium chloride particles was independent of particle size, suggesting a near-surface reaction dominated the uptake of N2O5. Differences in the reactivity of the N2O5 intermediate, NO2(+), with water and chloride can explain the observed dependencies. These results allow for parameterizations in atmospheric models to determine a more robust population mean value of γ(N2O5) that accounts for the distribution of particle sizes.

  3. Slow growth of the Rayleigh-Plateau instability in aqueous two phase systems

    PubMed Central

    Geschiere, Sam D.; Ziemecka, Iwona; van Steijn, Volkert; Koper, Ger J. M.; Esch, Jan H. van; Kreutzer, Michiel T.

    2012-01-01

    This paper studies the Rayleigh-Plateau instability for co-flowing immiscible aqueous polymer solutions in a microfluidic channel. Careful vibration-free experiments with controlled actuation of the flow allowed direct measurement of the growth rate of this instability. Experiments for the well-known aqueous two phase system (ATPS, or aqueous biphasic systems) of dextran and polyethylene glycol solutions exhibited a growth rate of 1 s−1, which was more than an order of magnitude slower than an analogous experiment with two immiscible Newtonian fluids with viscosities and interfacial tension that closely matched the ATPS experiment. Viscoelastic effects and adhesion to the walls were ruled out as explanations for the observed behavior. The results are remarkable because all current theory suggests that such dilute polymer solutions should break up faster, not slower, than the analogous Newtonian case. Microfluidic uses of aqueous two phase systems include separation of labile biomolecules but have hitherto be limited because of the difficulty in making droplets. The results of this work teach how to design devices for biological microfluidic ATPS platforms. PMID:22536307

  4. Liquid-liquid phase separation in aerosol particles: Imaging at the Nanometer Scale

    SciTech Connect

    O'Brien, Rachel; Wang, Bingbing; Kelly, Stephen T.; Lundt, Nils; You, Yuan; Bertram, Allan K.; Leone, Stephen R.; Laskin, Alexander; Gilles, Mary K.

    2015-04-21

    Atmospheric aerosols can undergo phase transitions including liquid-liquid phase separation (LLPS) while responding to changes in the ambient relative humidity (RH). Here, we report results of chemical imaging experiments using environmental scanning electron microscopy (ESEM) and scanning transmission x-ray microscopy (STXM) to investigate the LLPS of micron sized particles undergoing a full hydration-dehydration cycle. Internally mixed particles composed of ammonium sulfate (AS) and either: limonene secondary organic carbon (LSOC), a, 4-dihydroxy-3-methoxybenzeneaceticacid (HMMA), or polyethylene glycol (PEG-400) were studied. Events of LLPS with apparent core-shell particle morphology were observed for all samples with both techniques. Chemical imaging with STXM showed that both LSOC/AS and HMMA/AS particles were never homogeneously mixed for all measured RH’s above the deliquescence point and that the majority of the organic component was located in the shell. The shell composition was estimated as 65:35 organic: inorganic in LSOC/AS and as 50:50 organic: inorganic for HMMA/AS. PEG-400/AS particles showed fully homogeneous mixtures at high RH and phase separated below 89-92% RH with an estimated 50:50% organic to inorganic mix in the shell. These two chemical imaging techniques are well suited for in-situ analysis of the hygroscopic behavior, phase separation, and surface composition of collected ambient aerosol particles.

  5. First-principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase

    SciTech Connect

    Yoon, Yeohoon; Rousseau, Roger J.; Weber, Robert S.; Mei, Donghai; Lercher, Johannes A.

    2014-07-23

    The effects of aqueous phase on the reactivity of phenol hydrogenation over Pt and Ni catalysts were investigated using density functional theory based ab initio molecular dynamics (AIMD) calculations. The adsorption of phenol and the first hydrogenation steps via three carbon positions (ortho, meta and para) with respect to the phenolic OH group were studied in both vacuum and liquid phase conditions. To gain insight into how the aqueous phase affects the metal catalyst surface, increasing water environments including singly adsorbed water molecule, mono- (9 water molecules), double layers (24 water molecules), and the bulk liquid water which (52 water molecules) on the Pt(111) and the Ni(111) surfaces were modeled. Compared to the vacuum/metal interfaces, AIMD simulation results suggest that the aqueous Pt(111) and Ni(111) interfaces have a lower metal work function in the order of 0.8 - 0.9 eV, thus, making the metals in aqueous phase stronger reducing agents and poorer oxidizing agents. Phenol adsorption from the aqueous phase is found to be slightly weaker that from the vapor phase. The first hydrogenation step of phenol at the ortho position of the phenolic ring is slightly favored over the other two positions. The polarization induced by the surrounding water molecules and the solvation effect play important roles in stabilizing the transition states associated with phenol hydrogenation by lowering the barriers of 0.1 - 0.4 eV. The detailed discussion on the basis of the interfacial electrostatics from the current study is very useful to understand the nature of a broader class of metal catalyzed reactions in liquid solution phase. This work was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences and Office of Energy Efficiency and Renewable Energy. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing

  6. Metallic and semiconducting carbon nanotubes separation using an aqueous two-phase separation technique: a review.

    PubMed

    Tang, Malcolm S Y; Ng, Eng-Poh; Juan, Joon Ching; Ooi, Chien Wei; Ling, Tau Chuan; Woon, Kai Lin; Show, Pau Loke

    2016-08-19

    It is known that carbon nanotubes show desirable physical and chemical properties with a wide array of potential applications. Nonetheless, their potential has been hampered by the difficulties in acquiring high purity, chiral-specific tubes. Considerable advancement has been made in terms of the purification of carbon nanotubes, for instance chemical oxidation, physical separation, and myriad combinations of physical and chemical methods. The aqueous two-phase separation technique has recently been demonstrated to be able to sort carbon nanotubes based on their chirality. The technique requires low cost polymers and salt, and is able to sort the tubes based on their diameter as well as metallicity. In this review, we aim to provide a review that could stimulate innovative thought on the progress of a carbon nanotubes sorting method using the aqueous two-phase separation method, and present possible future work and an outlook that could enhance the methodology. PMID:27396920

  7. Method and device for removing a non-aqueous phase liquid from a groundwater system

    DOEpatents

    Looney, Brian B.; Rossabi, Joseph; Riha, Brian D.

    2002-01-01

    A device for removing a non-aqueous phase liquid from a groundwater system includes a generally cylindrical push-rod defining an internal recess therein. The push-rod includes first and second end portions and an external liquid collection surface. A liquid collection member is detachably connected to the push-rod at one of the first and second end portions thereof. The method of the present invention for removing a non-aqueous phase liquid from a contaminated groundwater system includes providing a lance including an external hydrophobic liquid collection surface, an internal recess, and a collection chamber at the bottom end thereof. The lance is extended into the groundwater system such that the top end thereof remains above the ground surface. The liquid is then allowed to collect on the liquid collection surface, and flow downwardly by gravity into the collection chamber to be pumped upwardly through the internal recess in the lance.

  8. Polyphenolic flavanols as scavengers of aqueous phase radicals and as chain-breaking antioxidants.

    PubMed

    Salah, N; Miller, N J; Paganga, G; Tijburg, L; Bolwell, G P; Rice-Evans, C

    1995-10-01

    The purpose of this investigation was to establish the relative antioxidant activities in vitro of the flavanolic polyphenols, the catechins, and catechin-gallate esters. The relative antioxidant potentials were measured against radicals generated in the aqueous phase and against propagating lipid peroxyl radicals. The results show that in the aqueous phase their order of effectiveness as radical scavengers is epicatechin gallate (ECG) > epigallocatechin gallate (EGCG) > epigallocatechin (EGC) > gallic acid (GA) > epicatechin congruent to catechin; against propagating lipid peroxyl radical species, epicatechin and catechin are as effective as ECG and EGCG, the least efficacious being EGC and GA. This is consistent with their relative abilities to protect against consumption of LDL alpha-tocopherol. The results are discussed in the context of the most relevant antioxidant constituents of green tea extracts.

  9. Metallic and semiconducting carbon nanotubes separation using an aqueous two-phase separation technique: a review

    NASA Astrophysics Data System (ADS)

    Tang, Malcolm S. Y.; Ng, Eng-Poh; Juan, Joon Ching; Ooi, Chien Wei; Ling, Tau Chuan; Woon, Kai Lin; Loke Show, Pau

    2016-08-01

    It is known that carbon nanotubes show desirable physical and chemical properties with a wide array of potential applications. Nonetheless, their potential has been hampered by the difficulties in acquiring high purity, chiral-specific tubes. Considerable advancement has been made in terms of the purification of carbon nanotubes, for instance chemical oxidation, physical separation, and myriad combinations of physical and chemical methods. The aqueous two-phase separation technique has recently been demonstrated to be able to sort carbon nanotubes based on their chirality. The technique requires low cost polymers and salt, and is able to sort the tubes based on their diameter as well as metallicity. In this review, we aim to provide a review that could stimulate innovative thought on the progress of a carbon nanotubes sorting method using the aqueous two-phase separation method, and present possible future work and an outlook that could enhance the methodology.

  10. Heterogeneous Catalytic Conversion of Biobased Chemicals into Liquid Fuels in the Aqueous Phase.

    PubMed

    Wu, Kejing; Wu, Yulong; Chen, Yu; Chen, Hao; Wang, Jianlong; Yang, Mingde

    2016-06-22

    Different biobased chemicals are produced during the conversion of biomass into fuels through various feasible technologies (e.g., hydrolysis, hydrothermal liquefaction, and pyrolysis). The challenge of transforming these biobased chemicals with high hydrophilicity is ascribed to the high water content of the feedstock and the inevitable formation of water. Therefore, aqueous-phase processing is an interesting technology for the heterogeneous catalytic conversion of biobased chemicals. Different reactions, such as dehydration, isomerization, aldol condensation, ketonization, and hydrogenation, are applied for the conversion of sugars, furfural/hydroxymethylfurfural, acids, phenolics, and so on over heterogeneous catalysts. The activity, stability, and reusability of the heterogeneous catalysts in water are summarized, and deactivation processes and several strategies are introduced to improve the stability of heterogeneous catalysts in the aqueous phase. PMID:27158985

  11. Columnar Aerosol Single-Scattering Albedo and Phase Function Retrieved from Sky Radiance Over the Ocean: Measurements of African Dust

    NASA Technical Reports Server (NTRS)

    Cattrall, Christopher; Carder, Kendall L.; Gordon, Howard R.

    2001-01-01

    The single-scattering albedo and phase function of African mineral dust are retrieved from ground-based measurements of sky radiance collected in the Florida Keys. The retrieval algorithm employs the radiative transfer equation to solve by iteration for these two properties which best reproduce the observed sky radiance using an assumed aerosol vertical structure and measured aerosol optical depth. Thus, no assumptions regarding particle size, shape, or composition are required. The single-scattering albedo, presented at fourteen wavelengths between 380 and 870 nm, displays a spectral shape expected of iron-bearing minerals but is much higher than current dust models allow. This indicates the absorption of light by mineral dust is significantly overestimated in climate studies. Uncertainty in the retrieved albedo is less than 0.02 due to the small uncertainty in the solar-reflectance-based calibration (12.2%) method employed. The phase function retrieved at 860 nm is very robust under simulations of expected experimental errors, indicating retrieved phase functions at this wavelength may be confidently used to describe aerosol scattering characteristics. The phase function retrieved at 443 nm is very sensitive to expected experimental errors and should not be used to describe aerosol scattering. Radiative forcing by aerosol is the greatest source of uncertainty in current climate models. These results will help reduce uncertainty in the absorption of light by mineral dust. Assessment of the radiative impact of aerosol species is a key component to NASA's Earth System Enterprise.

  12. Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

    DOEpatents

    Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

    2001-01-01

    An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

  13. Improvement of peak shape in aqueous normal phase analysis of anionic metabolites.

    PubMed

    Pesek, Joseph J; Matyska, Maria T; Fischer, Steven M

    2011-12-01

    The problem of poor peak shape for multiply charged negative-ion analytes under aqueous normal phase (ANP) conditions is investigated. Because less than adequate efficiency and symmetry can occur with a variety of mobile phases, gradients and additives, and to varying degrees depending on the instrument, sources other than solute/stationary phase interactions are more likely the cause. Since it is known that many of these compounds can interact strongly with metal ions, addition of a chelating agent to the mobile phase and/or the sample solvent was tested. In particular, ethylenediaminetetraacetic acid (EDTA) is a compound that forms strong complexes with most di-and tri-valent metal ions and can be used to verify whether trace amounts of these species are the source of the problem. In addition, the retention of a number of anionic compounds was measured at various concentrations of ammonium acetate and formate with EDTA in the mobile phase. PMID:22009714

  14. Drowning-out crystallisation of sodium sulphate using aqueous two-phase systems.

    PubMed

    Taboada, M E; Graber, T A; Asenjo, J A; Andrews, B A

    2000-06-23

    A novel method to obtain crystals of pure, anhydrous salt, using aqueous two-phase systems was studied. A concentrated salt solution is mixed with polyethylene glycol (PEG), upon which three phases are formed: salt crystals, a PEG-rich liquid and a salt-rich liquid. After removal of the solid salt, a two-phase system is obtained. Both liquid phases are recycled, allowing the design of a continuous process, which could be exploited industrially. The phase diagram of the system water-Na2SO4-PEG 3350 at 28 degrees C was used. Several process alternatives are proposed and their economic potential is discussed. The process steps needed to produce sodium sulphate crystals include mixing, crystallisation, settling and, optionally, evaporation of water. The yield of sodium sulphate increases dramatically if an evaporation step is used. PMID:10942277

  15. Representing effects of aqueous phase reactions in shallow cumuli in global models

    NASA Astrophysics Data System (ADS)

    Nie, Ji; Kuang, Zhiming; Jacob, Daniel J.; Guo, Jiahua

    2016-05-01

    Aqueous phase reactions are important, sometimes dominant (e.g., for SO2), pathways for the oxidation of air pollutants at the local and/or global scale. In many current chemical transport models (CTMs), the transport and aqueous reactions of chemical species are treated as split processes, and the subgrid-scale heterogeneity between cloudy and environmental air is not considered. Here using large eddy simulation (LES) with idealized aqueous reactions mimicking the oxidation of surface-originated SO2 by H2O2 in shallow cumuli, we show that the eddy diffusivity mass flux (EDMF) approach with a bulk plume can represent those processes quite well when entrainment/detrainment rates and eddy diffusivity are diagnosed using a conservative thermodynamic variable such as total water content. The reason is that a typical aqueous reaction such as SO2 aqueous oxidation is relatively slow compared to the in-cloud residence time of air parcels in shallow cumuli. As a result, the surface-originated SO2 is well correlated with and behaves like conservative thermodynamic variables that also have sources at the surface. Experiments with various reaction rate constants and relative abundances of SO2 and H2O2 indicate that when the reaction timescale approaches the in-cloud residence time of air parcels, the errors of the bulk plume approach start to increase. Treating chemical tracer transport and aqueous reaction as split processes leads to significant errors, especially when the reaction is fast compared to the in-cloud residence time. Overall, the EDMF approach shows large improvement over the CTM-like treatments in matching the LES results.

  16. The Lampedusa supersite of ChArMex: observing aerosol-radiation interactions and gas phase chemistry in the Mediterranean

    NASA Astrophysics Data System (ADS)

    Formenti, Paola; di Sarra, Alcide Giorgio

    2014-05-01

    Within the frame of the ADRIMED (Aerosol Direct Radiative Impact in the regional climate in the MEDiterranean region) project of the Chemistry-Aerosol Mediterranean experiment (ChArMex), the ENEA Laboratory for Climate Study "Roberto Sarao" (WMO/GAW/NDACC) on the Island of Lampedusa (35°31'N, 12°37°E) has been augmented to one of the supersites of the first phase of the Special Observing Period 1 by the measurements of the in situ properties of aerosols and trace gases by the of the PortablE Gas and Aerosol Sampling Units (PEGASUS) mobile station. The ground-based measurements have been completed by several coordinated overpasses of the ATR-42 and the F20 of SAFIRE. In this paper we present the first highlights of operations, which took place between June 6 and July 8 2013. Insights on the data provide with an unprecedented characterisation of the physico-chemical and properties aerosols and gas phase chemistry on air masses of various origins (pollution, marine, mineral dust, …..). The effect of aerosols on radiation fields is ascertained by coupling ground-based and aircraft measurements during dedicated overpasses providing with measurements of upwelling and downwelling shortwave and longwave radiation fluxes together with the properties of the aerosol load resolved on the column. Coordination with CALIPSO overpasses will also be explored.

  17. Hindered gas-phase partitioning of trichloroethylene from aqueous cyclodextrin systems: implications for treatment and analysis.

    PubMed

    Kashiyama, N; Boving, T B

    2004-08-15

    Chemically enhanced flushing has shown great promise for attenuating subsurface nonaqueous phase liquid (NAPL) contamination. One particular chemically enhanced remediation technology is cyclodextrin enhanced flushing (CDEF). CDEF has been demonstrated as a viable alternative to conventional and innovative remediation methods. However, the presence of cyclodextrin (CD) in solution complicates the treatment and analysis of volatile organic compounds, such as trichloroethylene (TCE). The principal reason for the complications is the presence of TCE in three compartments instead of two, i.e., the aqueous solution, the vapor phase, and complexed inside the soluble CD molecule. Aqueous TCE-CD systems were examined at various concentration and temperature conditions and their respective Henry's law constants were measured. The presence of CD significantly decreased Henry's law constant of TCE. On the basis of these results, a quantitative model was developed to predict the additional effort that becomes necessary when air-stripping TCE from CDEF flushing solution. The modeling results demonstrate that the presence of CD requires significantly higher gas flow rates or longer residence times of the flushing solution inside an air stripper. Similarly, current gas chromatographic purge-and-trap methods for TCE analysis in CD solution appear to underestimate the aqueous phase TCE concentration if the CD concentration of the sample is not accounted for. Although this model was developed specifically for CD-TCE systems, it is likely that these results have implications for other VOCs and other solubilization enhancing agents, such as surfactants or cosolvents.

  18. Hydrothermal upgrading of algae paste: Inorganics and recycling potential in the aqueous phase.

    PubMed

    Patel, Bhavish; Guo, Miao; Chong, Chinglih; Sarudin, Syazwani Hj Mat; Hellgardt, Klaus

    2016-10-15

    Hydrothermal Liquefaction (HTL) for algal biomass conversion is a promising technology capable of producing high yields of biocrude as well as partitioning even higher quantity of nutrients in the aqueous phase. To assess the feasibility of utilizing the aqueous phase, HTL of Nannochloropsis sp. was carried out in the temperature range of 275 to 350°C and Residence Times (RT) ranging between 5 and 60min The effect of reaction conditions on the NO3(-),PO4(3-),SO4(2-),Cl(-),Na(+),andK(+) ions as well as Chemical Oxygen Demand (COD) and pH was investigated with view of recycling the aqueous phase for either cultivation or energy generation via Anaerobic Digestion (AD), quantified via Lifecycle Assessment (LCA). It addition to substantial nutrient partitioning at short RT, an increase in alkalinity to almost pH10 and decrease in COD at longer RT was observed. The LCA investigation found reaction conditions of 275°C/30min and 350°C/10min to be most suitable for nutrient and energy recovery but both processing routes offer environmental benefit at all reaction conditions, however recycling for cultivation has marginally better environmental credentials compared to AD.

  19. Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen.

    PubMed

    Zakzeski, Joseph; Weckhuysen, Bert M

    2011-03-21

    The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant β-O-4 linkages and, to a lesser extent, the 5-5' carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10-15% depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin. PMID:21246746

  20. Hydrothermal upgrading of algae paste: Inorganics and recycling potential in the aqueous phase.

    PubMed

    Patel, Bhavish; Guo, Miao; Chong, Chinglih; Sarudin, Syazwani Hj Mat; Hellgardt, Klaus

    2016-10-15

    Hydrothermal Liquefaction (HTL) for algal biomass conversion is a promising technology capable of producing high yields of biocrude as well as partitioning even higher quantity of nutrients in the aqueous phase. To assess the feasibility of utilizing the aqueous phase, HTL of Nannochloropsis sp. was carried out in the temperature range of 275 to 350°C and Residence Times (RT) ranging between 5 and 60min The effect of reaction conditions on the NO3(-),PO4(3-),SO4(2-),Cl(-),Na(+),andK(+) ions as well as Chemical Oxygen Demand (COD) and pH was investigated with view of recycling the aqueous phase for either cultivation or energy generation via Anaerobic Digestion (AD), quantified via Lifecycle Assessment (LCA). It addition to substantial nutrient partitioning at short RT, an increase in alkalinity to almost pH10 and decrease in COD at longer RT was observed. The LCA investigation found reaction conditions of 275°C/30min and 350°C/10min to be most suitable for nutrient and energy recovery but both processing routes offer environmental benefit at all reaction conditions, however recycling for cultivation has marginally better environmental credentials compared to AD. PMID:27318079

  1. Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen.

    PubMed

    Zakzeski, Joseph; Weckhuysen, Bert M

    2011-03-21

    The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant β-O-4 linkages and, to a lesser extent, the 5-5' carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10-15% depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin.

  2. Interfacial Tension Effect on Cell Partition in Aqueous Two-Phase Systems.

    PubMed

    Atefi, Ehsan; Joshi, Ramila; Mann, Jay Adin; Tavana, Hossein

    2015-09-30

    Aqueous two-phase systems (ATPS) provide a mild environment for the partition and separation of cells. We report a combined experimental and theoretical study on the effect of interfacial tension of polymeric ATPS on the partitioning of cells between two phases and their interface. Two-phase systems are generated using polyethylene glycol and dextran of specific properties as phase-forming polymers and culture media as the solvent component. Ultralow interfacial tensions of the solutions are precisely measured using an axisymmetric drop shape analysis method. Partition experiments show that two-phase systems with an interfacial tension of 30 μJ/m(2) result in distribution of majority of cells to the bottom dextran phase. An increase in the interfacial tension results in a distribution of cells toward the interface. An independent cancer cell spheroid formation assay confirms these observations: a drop of the dextran phase containing cancer cells is dispensed into the immersion polyethylene glycol phase to form a cell-containing drop. Only at very small interfacial tensions do cells remain within the drop to aggregate into a spheroid. We perform a thermodynamic modeling of cell partition to determine variations of free energy associated with displacement of cells in ATPS with respect to the ultralow interfacial tensions. This modeling corroborates with the experimental results and demonstrates that at the smallest interfacial tension of 30 μJ/m(2), the free energy is a minimum with cells in the bottom phase. Increasing the interfacial tension shifts the minimum energy and partition of cells toward the interfacial region of the two aqueous phases. Examining differences in the partition behavior and minimum free energy modeling of A431.H9 cancer cells and mouse embryonic stem cells shows that the surface properties of cells further modulate partition in ATPS. This combined approach provides a fundamental understanding of interfacial tension role on cell partition in

  3. Interfacial Tension Effect on Cell Partition in Aqueous Two-Phase Systems.

    PubMed

    Atefi, Ehsan; Joshi, Ramila; Mann, Jay Adin; Tavana, Hossein

    2015-09-30

    Aqueous two-phase systems (ATPS) provide a mild environment for the partition and separation of cells. We report a combined experimental and theoretical study on the effect of interfacial tension of polymeric ATPS on the partitioning of cells between two phases and their interface. Two-phase systems are generated using polyethylene glycol and dextran of specific properties as phase-forming polymers and culture media as the solvent component. Ultralow interfacial tensions of the solutions are precisely measured using an axisymmetric drop shape analysis method. Partition experiments show that two-phase systems with an interfacial tension of 30 μJ/m(2) result in distribution of majority of cells to the bottom dextran phase. An increase in the interfacial tension results in a distribution of cells toward the interface. An independent cancer cell spheroid formation assay confirms these observations: a drop of the dextran phase containing cancer cells is dispensed into the immersion polyethylene glycol phase to form a cell-containing drop. Only at very small interfacial tensions do cells remain within the drop to aggregate into a spheroid. We perform a thermodynamic modeling of cell partition to determine variations of free energy associated with displacement of cells in ATPS with respect to the ultralow interfacial tensions. This modeling corroborates with the experimental results and demonstrates that at the smallest interfacial tension of 30 μJ/m(2), the free energy is a minimum with cells in the bottom phase. Increasing the interfacial tension shifts the minimum energy and partition of cells toward the interfacial region of the two aqueous phases. Examining differences in the partition behavior and minimum free energy modeling of A431.H9 cancer cells and mouse embryonic stem cells shows that the surface properties of cells further modulate partition in ATPS. This combined approach provides a fundamental understanding of interfacial tension role on cell partition in

  4. Charged aerosol detection to characterize components of dispersed-phase formulations.

    PubMed

    Fox, Christopher B; Sivananthan, Sandra J; Mikasa, Traci J T; Lin, Susan; Parker, Sarah C

    2013-11-01

    Colloidal formulations based on biocompatible phospholipids, emulsifiers, and oils are employed in a wide range of applications including medicine, food, and cosmetics. However, characterization of these dispersed-phase components may be difficult to analyze by traditional HPLC with UV, visible, or fluorescence detection modalities due to lack of chromophores or fluorophores. Charged aerosol detection (CAD) is increasingly used for analysis of dispersed-phase components due to its broad applicability and high sensitivity for non-chromophore containing components found in many colloidal systems, such as lipid-based molecules. In this review, we summarize the recent applications of CAD reported in the literature as well as our own laboratory for the analysis of widely used components of dispersed-phase systems. In particular, we discuss the advantages and disadvantages of CAD compared to other HPLC detection methods, as well as the various sample preparation methods suitable for colloidal formulations prior to HPLC-CAD analysis. PMID:23855968

  5. Sponge Phases and Nanoparticle Dispersions in Aqueous Mixtures of Mono- and Diglycerides.

    PubMed

    Valldeperas, Maria; Wiśniewska, Małgorzata; Ram-On, Maor; Kesselman, Ellina; Danino, Dganit; Nylander, Tommy; Barauskas, Justas

    2016-08-30

    The lipid liquid crystalline sponge phase (L3) has the advantages that it is a nanoscopically bicontinuous bilayer network able to accommodate large amounts of water and it is easy to manipulate due to its fluidity. This paper reports on the detailed characterization of L3 phases with water channels large enough to encapsulate bioactive macromolecules such as proteins. The aqueous phase behavior of a novel lipid mixture system, consisting of diglycerol monooleate (DGMO), and a mixture of mono-, di- and triglycerides (Capmul GMO-50) was studied. In addition, sponge-like nanoparticles (NPs) stabilized by Polysorbate 80 (P80) were prepared based on the DGMO/GMO-50 system, and their structure was correlated with the phase behavior of the corresponding bulk system. These NPs were characterized by dynamic light scattering (DLS), cryo-transmission electron microscopy (Cryo-TEM) and small angle X-ray scattering (SAXS) to determine their size, shape, and inner structure as a function of the DGMO/GMO-50 ratio. In addition, the effect of P80 as stabilizer was investigated. We found that the NPs have aqueous pores with diameters up to 13 nm, similar to the ones in the bulk phase. PMID:27482838

  6. Development of a correlation for aqueous-vapor phase mass transfer in porous media

    NASA Astrophysics Data System (ADS)

    Szatkowski, Andrew; Imhoff, Paul T.; Miller, Cass T.

    1995-03-01

    In many situations vapor-phase extraction procedures (e.g., soil venting, air sparging, and bioventing) may be suitable methods for remediating porous media contaminated by volatile organic compounds. This has led to increased study of operative processes in these systems, including aqueous-vapor phase mass transfer. Past work has shown the importance of the flow regime on this process, but a quantitative estimate of mass-transfer coefficients is lacking, especially for systems not confounded by uncertainties involving interfacial area between the phases. An experimental investigation was conducted to isolate the resistance to aqueous-vapor phase mass transfer at the phase boundary, using an ideal porous medium system. Mass-transfer coefficients were measured for toluene for a wide range of Reynolds numbers. An empirical model was fit to the data in dimensionless form. The mass-transfer model was coupled with an available interfacial area model, yielding a dimensionless expression for the mass-transfer rate coefficient. This expression was used to compare results from this work to three other experimental studies reported in the literature. These comparisons showed that for experiments where infiltrating water flowed uniformly within the porous medium, the predicted mass-transfer coefficients were within a factor of 5 of the measured coefficients. Mass transfer was significantly slower than the rate predicted, using the results from this work, in experiments where infiltrating water flowed nonuniformly.

  7. Purification of Active Myrosinase from Plants by Aqueous Two-Phase Counter-Current Chromatography

    PubMed Central

    Wade, Kristina L.; Ito, Yoichiro; Ramarathnam, Aarthi; Holtzclaw, W. David; Fahey, Jed W.

    2014-01-01

    Introduction Myrosinase (thioglucoside glucohydrolase; E.C. 3.2.1.147), is a plant enzyme of increasing interest and importance to the biomedical community. Myrosinase catalyses the formation of isothiocyanates such as sulforaphane (frombroccoli) and 4-(α-l-rhamnopyranosyloxy)benzyl isothiocyanate (from moringa), which are potent inducers of the cytoprotective phase-2 response in humans, by hydrolysis of their abundant glucosinolate (β-thioglucoside N-hydroxysulphate) precursors. Objective To develop an aqueous two-phase counter-current chromatography (CCC) system for the rapid, three-step purification of catalytically active myrosinase. Methods A high-concentration potassium phosphate and polyethylene glycol biphasic aqueous two-phase system (ATPS) is used with a newly developed CCC configuration that utilises spiral-wound, flat-twisted tubing (with an ovoid cross-section). Results Making the initial crude plant extract directly in the ATPS and injecting only the lower phase permitted highly selective partitioning of the myrosinase complex before a short chromatography on a spiral disk CCC. Optimum phase retention and separation of myrosinase from other plant proteins afforded a 60-fold purification. Conclusion Catalytically active myrosinase is purified from 3-day broccoli sprouts, 7-day daikon sprouts, mustard seeds and the leaves of field-grown moringa trees, in a CCC system that is predictably scalable. PMID:25130502

  8. Sponge Phases and Nanoparticle Dispersions in Aqueous Mixtures of Mono- and Diglycerides.

    PubMed

    Valldeperas, Maria; Wiśniewska, Małgorzata; Ram-On, Maor; Kesselman, Ellina; Danino, Dganit; Nylander, Tommy; Barauskas, Justas

    2016-08-30

    The lipid liquid crystalline sponge phase (L3) has the advantages that it is a nanoscopically bicontinuous bilayer network able to accommodate large amounts of water and it is easy to manipulate due to its fluidity. This paper reports on the detailed characterization of L3 phases with water channels large enough to encapsulate bioactive macromolecules such as proteins. The aqueous phase behavior of a novel lipid mixture system, consisting of diglycerol monooleate (DGMO), and a mixture of mono-, di- and triglycerides (Capmul GMO-50) was studied. In addition, sponge-like nanoparticles (NPs) stabilized by Polysorbate 80 (P80) were prepared based on the DGMO/GMO-50 system, and their structure was correlated with the phase behavior of the corresponding bulk system. These NPs were characterized by dynamic light scattering (DLS), cryo-transmission electron microscopy (Cryo-TEM) and small angle X-ray scattering (SAXS) to determine their size, shape, and inner structure as a function of the DGMO/GMO-50 ratio. In addition, the effect of P80 as stabilizer was investigated. We found that the NPs have aqueous pores with diameters up to 13 nm, similar to the ones in the bulk phase.

  9. Improvement of NOx Removal Efficiency Assisted by Aqueous-Phase Reaction in Corona Discharge

    NASA Astrophysics Data System (ADS)

    Daito, Shigeo; Tochikubo, Fumiyoshi; Watanabe, Tsuneo

    2000-08-01

    The influence of water vapor and water droplets on the removal efficiency of nitrogen oxide is investigated in the pulsed positive corona discharge in atmospheric pressure air-based gas with a small amount of NO@. The removal rates of both NO and NO2 are improved by feeding water vapor into the discharge reactor since NO2 is transformed into HNO3 by reaction with OH. Feeding water droplets, particularly alkaline water droplets, gives a better NO and NO2 removal efficiency than feeding water vapor. This might be explained by the rapid dissolution of the generated HNO3 into water droplets. Numerical modelling by means of a rate equation is carried out to investigate the dynamic process of gas phase and aqueous phase, and the aqueous-phase reaction in water droplets. The results suggest that gas-phase HNO3 dissolves in water droplets within short time (˜0.1 s). Therefore, the efficient transformation of NOx into gas-phase HNO3 is a key process in the improvement of NOx removal efficiency. Suppressing hydrogen ion concentration in water droplets by adding NH3 or feeding alkaline water droplets improves the dissolution rate of NO2.

  10. Retrieval of the columnar aerosol phase function and single-scattering albedo from sky radiance over the ocean - Simulations

    NASA Technical Reports Server (NTRS)

    Wang, Menghua; Gordon, Howard R.

    1993-01-01

    Based on the fact that the part of downward radiance that depends on the optical properties of the aerosol in the atmosphere can be extracted from the measured sky radiance, a new scheme for retrieval of the aerosol phase function and the single-scattering albedo over the ocean is developed. This retrieval algorithm is tested with simulations for several cases. It is found that the retrieved aerosol phase function and the single-scattering albedo are virtually error-free if the vertical structure of the atmosphere is known and if the sky radiance and the aerosol optical thickness can be measured accurately. The robustness of the algorithm in realistic situations, in which the measurements are contaminated by calibration errors or noise, is examined. It is found that the retrieved value of omega(0) is usually in error by less than about 10 percent, and the phase function is accurately retrieved for theta less than about 90 deg. However, as the aerosol optical thickness becomes small, e.g., less than about 0.1, errors in the sky radiance measurement can lead to serious problems with the retrieval algorithm, especially in the blue. The use of the retrieval scheme should be limited to the red and near IR when the aerosol optical thickness is small.

  11. Cavity Attenuated Phase Shift (CAPS) Method for Airborne Aerosol Light Extinction Measurement: Instrument Validation and First Results from Field Deployment

    NASA Astrophysics Data System (ADS)

    Petzold, A.; Perim de Faria, J.; Berg, M.; Bundke, U.; Freedman, A.

    2015-12-01

    Monitoring the direct impact of aerosol particles on climate requires the continuous measurement of aerosol optical parameters like the aerosol extinction coefficient on a regular basis. Remote sensing and ground-based networks are well in place (e.g., AERONET, ACTRIS), whereas the regular in situ measurement of vertical profiles of atmospheric aerosol optical properties remains still an important challenge in quantifying climate change. The European Research Infrastructure IAGOS (In-service Aircraft for a Global Observing System; www.iagos.org) responds to the increasing requests for long-term, routine in situ observational data by using commercial passenger aircraft as measurement platform. However, scientific instrumentation for the measurement of atmospheric constituents requires major modifications before being deployable aboard in-service passenger aircraft. Recently, a compact and robust family of optical instruments based on the cavity attenuated phase shift (CAPS) technique has become available for measuring aerosol light extinction. While this technique was successfully deployed for ground-based atmospheric measurements under various conditions, its suitability for operation aboard aircraft in the free and upper free troposphere still has to be demonstrated. In this work, the modifications of a CAPS PMex instrument for measuring aerosol light extinction on aircraft, the results from subsequent laboratory tests for evaluating the modified instrument prototype, and first results from a field deployment aboard a research aircraft will be covered. In laboratory studies, the instrument showed excellent agreement (deviation < 5%) with theoretical values calculated from Rayleigh scattering cross-sections, when operated on pressurized air and CO2 at ambient and low pressure (~200 hPa). For monodisperse and polydisperse aerosols, reference aerosol extinction coefficients were calculated from measured size distributions and agreed with the CAPS PMex instrument

  12. Low-temperature aqueous-phase reforming of ethanol on bimetallic PdZn catalysts

    SciTech Connect

    Xiong, Haifeng; DelaRiva, Andrew; Wang, Yong; Dayte, Abhaya

    2015-01-01

    Bimetallic PdZn catalysts supported on carbon black (CB) and carbon nanotubes (CNTs) were found to be selective for CO-free H-2 production from ethanol at low temperature (250 degrees C). On Pd, the H-2 yield was low (similar to 0.3 mol H-2/mol ethanol reacted) and the CH4/CO2 ratio was high (similar to 1.7). Addition of Zn to Pd formed the intermetallic PdZn beta phase (atomic ratio of Zn to Pd is 1) with increased H-2 yield (similar to 1.9 mol H-2/mol ethanol reacted) and CH4/CO2 ratio of <1. The higher H-2 yield and low CH4 formation was related to the improved dehydrogenation activity of the L1(0) PdZn beta phase. The TOF increased with particle size and the CNTs provided the most active and selective catalysts, which may be ascribed to pore-confinement effects. Furthermore, no significant changes in either the supports or the PdZn beta particles was found after aqueous-phase reforming (APR) indicating that the metal nanoparticles and the carbon support are hydrothermally stable in the aqueous phase at elevated temperatures and pressures (>200 degrees C, 65 bar). No CO was detected for all the catalysts performed in aqueous-phase reaction, indicating that both monometallic Pd and bimetallic PdZn catalysts have high water-gas shift activity during APR. However, the yield of H-2 is considerably lower than the theoretical value of 6 H-2 per mole ethanol which is due to the presence of oxygenated products and methane on the PdZn catalysts.

  13. Reactive Transport in Porous Media: Pore-scale Mass Exchange between Aqueous Phase and Biofilms

    NASA Astrophysics Data System (ADS)

    Hassanizadeh, S.; Qin, C.

    2013-12-01

    In the presence of water and necessary nutrients, biofilms can grow on soil grain surfaces. They occupy void pore spaces blocking water flow. As a result, some hydrodynamic properties of porous media like porosity and permeability will be reduced. This ultimately leads to a condition known as bioclogging. Also, biofilms can degrade certain compounds. So, the features of bioclogging and biodegradation in porous media with biofilms have given rise to a broad range of environmental and engineering applications, such as bioremediation, biobarriers, microbial enhanced oil recovery, and protection of steel corrosion. To date, a number of macroscale and pore-scale models for describing biodegradation in porous media with biofilms are available in the literature. At the macro scale, to simplify numerical implementation, a ';one-equation' model is normally preferred. In this approach, only the solute concentration in aqueous phase is modeled associated with the consumption of solute in biofilms. Because the solute concentration in biofilms is different from that in aqueous phase, an effectiveness factor may be used in Monod kinetics for relating reaction rate within biofilms to the solute concentration in aqueous phase. Notice that this approach has its validity domains like local equilibrium and reaction-rate limited consumption. Another approach to modeling biodegradation is referred to as a ';two-equation' model, in which one needs to simultaneously track the solute concentrations in both aqueous phase and biofilms. In addition, the two concentrations may be related by a first-order kinetic mass exchange model. This first-rate exchange model is normally represented by a constant mas exchange coefficient multiplied by the concentration difference in the two domains. Here, one may question if complex advection-diffusion-reaction processes can be represented just by a constant mass exchange coefficient. In addition, the kinetic model of mass exchange between aqueous phase

  14. Distribution of selected halogenated organic compounds among suspended particulate, colloid, and aqueous phases in the Mississippi River and major tributaries

    USGS Publications Warehouse

    Rostad, C.E.; Daniel, S.R.

    2007-01-01

    Suspended particulate, colloid, and aqueous phases were separated and analyzed to determine spatial variation of specific organic compound transport associated with each phase in a dynamic river system. Sixteen sites along the Mississippi River and its major tributaries were sampled at low-flow conditions to maximize the possibility of equilibrium. Across the solubility range studied, the proportion transported by each phase depended on the compound solubility, with more water-soluble compounds (dacthal, trifluralin) transported predominantly in the aqueous phase and less-water soluble compounds (polychlorinated biphenyls, chlordane-related compounds) transported predominantly in the particulate and colloid phases. ?? 2007 Springer Science+Business Media, LLC.

  15. Relative hydrophobicity between the phases and partition of cytochrome-c in glycine ionic liquids aqueous two-phase systems.

    PubMed

    Wu, Changzeng; Wang, Jianji; Li, Zhiyong; Jing, Jun; Wang, Huiyong

    2013-08-30

    In this work, glycine ionic liquids tetramethylammonium glycine ([N1111][Gly]), tetraethylammonium glycine ([N2222][Gly]), tetra-n-butylammonium glycine ([N4444][Gly]), tetra-n-butylphosphonium glycine ([P4444][Gly]) and tetra-n-pentylammonium glycine ([N5555][Gly]) were synthesized and used to prepare aqueous two-phase systems (ATPSs) in the presence of K2HPO4. Binodal curves of such ATPSs and partition coefficients of a series of dinitrophenylated (DNP) amino acids in these ATPSs were determined at 298.15K to understand the effect of cationic structure of the ionic liquids on the phase-forming ability of glycine ionic liquids, relative hydrophobicity between the phases in the ionic liquids ATPSs, and polarity of the ionic liquids-rich phases. With the attempt to correlate the relative hydrophobicity of the phases in the ATPSs with their extraction capability for proteins, partition coefficients of cytochrome-c in the ATPSs were also determined. It was shown that partition coefficients of cytochrome-c were in the range from 2.83 to 20.7 under the studied pH conditions. Then, hydrophobic interactions between cytochrome-c and the ionic liquid are suggested to be the main driving force for the preferential partition of cytochrome-c in the glycine ionic liquid-rich phases of the ATPSs. Result derived from polarity of the ionic liquids-rich phases supports this mechanism.

  16. Gas phase emissions from cooking processes and their secondary aerosol production potential

    NASA Astrophysics Data System (ADS)

    Klein, Felix; Platt, Stephen; Bruns, Emily; Termime-roussel, Brice; Detournay, Anais; Mohr, Claudia; Crippa, Monica; Slowik, Jay; Marchand, Nicolas; Baltensperger, Urs; Prevot, Andre; El Haddad, Imad

    2014-05-01

    -ToF-MS) were used to quantify OA and VOC emissions, respectively. SOA production potential of the different emissions was quantified by introducing them into the PSI mobile smog chamber and a potential aerosol chamber (PAM) where they were photochemically aged. The measurements of primary emissions suggest that the COA factor identified in ambient atmospheric aerosols is mostly related to fat release from frying with vegetable oils or grilling fatty-meats. In contrast, vegetable cooking (boiling and frying) was associated with significant VOC emissions. The VOC emissions from frying consist mainly of aldehydes which are formed through breaking of fatty acids. Gas phase composition, emission factors and SAPP from all these processes will be presented. This work was supported by the Swiss National Science Foundation as well as the Swiss Federal Office for the Environment. The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement n.° 290605 (COFUND: PSI-FELLOW). J. Allan et al, Atmos. Chem. Phys. 10, 647-668 (2010) X.-F. Huang et al, Atmos. Chem. Phys. 10, 8933-8945 (2010) Y.-L. Sun et al, Atmos. Chem. Phys. 11, 1581-1602 (2011)

  17. Aerosol Inflluence on Ice Nucleation via the Immersion Mode in Mixed-Phase Arctic Stratiform Clouds

    NASA Astrophysics Data System (ADS)

    de Boer, G.; Hashino, T.; Tripoli, G. J.; Eloranta, E. W.

    2009-12-01

    Mixed-phase stratiform clouds are commonly observed at high latitudes (e.g. Shupe et al., 2006; de Boer et al., 2009a). Herman and Goody (1976), as well as Curry et al. (1996) present summaries of Arctic cloud climatologies that show low altitude stratus frequencies of up to 70% during transitional seasons. In addition to their frequent occurrence, these clouds have significant impacts on the near-surface atmospheric radiative budget, with estimates of wintertime reductions in net surface cooling of 40-50 Wm-2 (Curry et al., 1996) due predominantly to liquid in the mixed-phase layer. Both observational and modeling studies (e.g. Harrington et al., 1999; Jiang et al., 2000; Shupe et al., 2008; Klein et al., 2008) show a strong connection between the amount of ice present and the lifetime of the liquid portion of the cloud layer. This is thought to occur via the Bergeron-Findeissen mechanism (Pruppacher and Klett, 1997) in which ice grows at the expense of liquid due to its lower saturation vapor pressure. Unfortunately, the mechanisms by which ice is nucleated within these mixed-phase layers are not yet fully understood, and therefore an accurate depiction of this process for mixed-phase stratiform clouds has not yet been characterized. The nucleation mechanisms that are active in a given environment are sensitive to aerosol properties. Insoluble particles are typically good nuclei for ice particle formation, while soluble particles are typically better at nucleating water droplets. Aerosol observations from the Arctic often show mixed aerosol particles that feature both soluble and insoluble mass (Leaitch et al., 1984). Soluble mass fractions for these particles have been shown to be high, with estimates of 60-80% and are often made up of sulfates (Zhou et al., 2001; Bigg and Leck, 2001). It is believed that a significant portion of this sulfate mass comes from dimethyl sulfide (DMS) production in the Arctic Ocean and subsequent atmospheric oxidation. Since these

  18. Ionic liquids for aqueous two-phase extraction and stabilization of enzymes.

    PubMed

    Dreyer, Susanne; Kragl, Udo

    2008-04-15

    The ionic liquid (IL) Ammoeng110 contains cations with oligoethyleneglycol units and was found to be highly effective for the formation of aqueous two-phase systems (ATPS) that can be used for the biocompatible purification of active enzymes. Above critical concentrations of the IL and an inorganic salt in aqueous solution, phase separation takes place resulting in the formation of an IL-enriched upper and a salt-enriched lower phase. For the optimization of the composition of IL-based ATPS with regard to the extraction of catalytically active enzymes, the Box-Wilson method of experimental design was successfully applied; IL-based ATPS proved to be suitable for the purification and stabilization of two different alcohol dehydrogenases (from Lactobacillus brevis and a thermophilic bacterium). Both enzymes were enriched in the IL-containing upper phase resulting in an increase of specific activity by a factor of 2 and 4 respectively. Furthermore, the presence of IL within the system provided the opportunity to combine the extraction process with the performance of enzyme-catalyzed reactions. The IL was found to exhibit a stability improving effect on both enzymes and a solubility enhancing effect on hydrophobic substrates. Thus the conversion and volumetric productivity of ADH catalyzed reduction of acetophenone could be increased significantly. PMID:18023057

  19. Cell separation by an aqueous two-phase system in a microfluidic device.

    PubMed

    Tsukamoto, Masatoshi; Taira, Shu; Yamamura, Shohei; Morita, Yasutaka; Nagatani, Naoki; Takamura, Yuzuru; Tamiya, Eiichi

    2009-10-01

    We generated an aqueous two-phase laminar flow in a microfluidic chip and used the system to isolate leukocyte and erythrocyte cells from whole blood cells. The microfluidic system reduced the effect of gravity in the aqueous two-phase system (ATPS). Poly(ethylene glycol) (PEG) and dextran (Dex) solutions were used as the two phases, and the independent flow rates of the solutions were both 2 microL/min. When hydrophobic and hydrophilic polystyrene beads were introduced into the microfluidic device, the hydrophilic beads moved to the Dex layer and the hydrophobic beads to the interface between the two phases. In the case of living cells, Jurkat cells and erythrocytes moved more efficiently to the PEG and Dex layers, respectively, than they move in a conventional ATPS. When whole blood cells were inserted into the microfluidic chip, leukocytes could be separated from erythrocytes because erythrocytes moved to the Dex layer while leukocytes remained outside of this layer in the microfluidic system. The reported microfluidic chip for the whole blood cell separation can effectively be integrated into a Micro Total Analysis System designed for cell-based clinical, forensic, and environmental analyses.

  20. Cosolutes effects on aqueous two-phase systems equilibrium formation studied by physical approaches.

    PubMed

    Bertoluzzo, M Guadalupe; Rigatuso, Rubén; Farruggia, Beatriz; Nerli, Bibiana; Picó, Guillermo

    2007-10-01

    The effect of urea and sodium salts of monovalent halides on the aqueous polyethyleneglycol solution and binodal diagrams of polyethyleneglycol-potassium phosphate (polyethyleneglycol of molecular mass 1500, 4000, 6000 and 8000) were studied using different physical approaches. The effect of these solutes on the binodal diagram for polyethyleneglycol-potassium phosphate was also investigated. The cosolutes affected in a significant manner the water structured around the ethylene chain of polyethyleneglycol inducing a lost of this. The equilibrium curves for the aqueous two-phase systems were fitting very well by a sigmoidal function with two parameters, which are closely related with the cosolute structure making or breaking capacity on the water ordered. PMID:17580111

  1. Integrating phase and composition of secondary organic aerosol from the ozonolysis of α-pinene

    PubMed Central

    Kidd, Carla; Perraud, Véronique; Wingen, Lisa M.; Finlayson-Pitts, Barbara J.

    2014-01-01

    Airborne particles are important for public health, visibility, and climate. Predicting their concentrations, effects, and responses to control strategies requires accurate models of their formation and growth in air. This is challenging, as a large fraction is formed by complex reactions of volatile organic compounds, generating secondary organic aerosol (SOA), which grows to sizes important for visibility, climate, and deposition in the lung. Growth of SOA is particularly sensitive to the phase/viscosity of the particles and remains poorly understood. We report studies using a custom-designed impactor with a germanium crystal as the impaction surface to study SOA formed from the ozonolysis of α-pinene at relative humidities (RHs) up to 87% at 297 ± 2 K (which corresponds to a maximum RH of 70–86% inside the impactor). The impaction patterns provide insight into changes in phase/viscosity as a function of RH. Attenuated total reflectance-Fourier transform infrared spectroscopy and aerosol mass spectrometry provide simultaneous information on composition changes with RH. The results show that as the RH at which the SOA is formed increases, there is a decrease in viscosity, accompanied by an increasing contribution from carboxylic acids and a decreasing contribution from higher molecular mass products. In contrast, SOA that is formed dry and subsequently humidified remains solid to high RH. The results of these studies have significant implications for modeling the growth, aging, and ultimately, lifetime of SOA in the atmosphere. PMID:24821796

  2. Formation of Secondary Particulate Matter by Reactions of Gas Phase Hexanal with Sulfate Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Zhang, J.

    2003-12-01

    The formation of secondary particulate matter from the atmospheric oxidation of organic compounds can significantly contribute to the particulate burden, but the formation of organic secondary particulate matter is poorly understood. One way of producing organic secondary particulate matter is the oxidation of hydrocarbons with seven or more carbon atoms to get products with low vapor pressure. However, several recent reports suggest that relatively low molecular weight carbonyls can enter the particle phase by undergoing heterogeneous reactions. This may be a very important mechanism for the formation of organic secondary particulate matter. Atmospheric aldehydes are important carbonyls in the gas phase, which form via the oxidation of hydrocarbons emitted from anthropogenic and biogenic sources. In this poster, we report the results on particle growth by the heterogeneous reactions of hexanal. A 5 L Continuous Stirred Tank Reactor (CSTR) is set up to conduct the reactions in the presence of seed aerosol particles of deliquesced ammonia bisulfate. Hexanal is added into CSTR by syringe pump, meanwhile the concentrations of hexanal are monitored with High Pressure Liquid Chromatograph (HPLC 1050). A differential Mobility Analyzer (TSI 3071) set to an appropriate voltage is employed to obtain monodisperse aerosols, and another DMA associated with a Condensation Nuclear Counter (TSI 7610) is used to measure the secondary particle size distribution by the reaction in CSTR. This permits the sensitive determination of particle growth due to the heterogeneous reaction, very little growth occurs when hexanal added alone. Results for the simultaneous addition of hexanal and alcohols will also be presented.

  3. Improving the treatment of non-aqueous phase TCE in low permeability zones with permanganate.

    PubMed

    Chokejaroenrat, Chanat; Comfort, Steve; Sakulthaew, Chainarong; Dvorak, Bruce

    2014-03-15

    Treating dense non-aqueous phase liquids (DNAPLs) embedded in low permeability zones (LPZs) is a particularly challenging issue for injection-based remedial treatments. Our objective was to improve the sweeping efficiency of permanganate (MnO4(-)) into LPZs to treat high concentrations of TCE. This was accomplished by conducting transport experiments that quantified the penetration of various permanganate flooding solutions into a LPZ that was spiked with non-aqueous phase (14)C-TCE. The treatments we evaluated included permanganate paired with: (i) a shear-thinning polymer (xanthan); (ii) stabilization aids that minimized MnO2 rind formation and (iii) a phase-transfer catalyst. In addition, we quantified the ability of these flooding solutions to improve TCE destruction under batch conditions by developing miniature LPZ cylinders that were spiked with (14)C-TCE. Transport experiments showed that MnO4(-) alone was inefficient in penetrating the LPZ and reacting with non-aqueous phase TCE, due to a distinct and large MnO2 rind that inhibited the TCE from further oxidant contact. By including xanthan with MnO4(-), the sweeping efficiency increased (90%) but rind formation was still evident. By including the stabilization aid, sodium hexametaphosphate (SHMP) with xanthan, permanganate penetrated 100% of the LPZ, no rind was observed, and the percentage of TCE oxidized increased. Batch experiments using LPZ cylinders allowed longer contact times between the flooding solutions and the DNAPL and results showed that SHMP+MnO4(-) improved TCE destruction by ∼16% over MnO4(-) alone (56.5% vs. 40.1%). These results support combining permanganate with SHMP or SHMP and xanthan as a means of treating high concentrations of TCE in low permeable zones.

  4. Gas- and aerosol-phase chemistry of nitrogen oxides (NOy) in a pine forest (BEACHON-RoMBAS 2011)

    NASA Astrophysics Data System (ADS)

    Fry, J.; Draper, D.; Zarzana, K. J.; Brown, S. S.; Dube, B.; Wagner, N.; Cohen, R. C.; Palm, B. B.; Ortega, A. M.; Campuzano Jost, P.; Day, D. A.; Jimenez, J. L.; Brune, W. H.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.

    2011-12-01

    Ambient measurements of NOy (NO2, peroxy- and alkyl-nitrates, and the gas/aerosol partitioning of the latter) and Potential Aerosol Mass measurements of NO3-initiated secondary organic aerosol formation in a 16 L flow-through reactor were made during the BEACHON-RoMBAS field campaign in U.S. Forest Service Manitou Forest Observatory, Colorado (July/August 2011). A cavity ringdown spectrometer (CRDS) is used to monitor NO3 and N2O5 , Thermal Desorption - Laser Induced Fluorescence (TD-LIF) is used to detect the NOy species as NO2; an Aerodyne Aerosol Mass Spectrometer (AMS) monitors chemical composition of aerosol; Proton Transfer Reaction Mass Spectrometry (PTR-TOF-MS) monitors the gas-phase organic compounds; and a thermal converter/chemiluminescent NO/NOx/NH3 analyzer monitors gas-phase inorganic nitrogen compounds. In the PAM measurements, a calibrated flow of NO3 is supplied to the reactor from a temperature-controlled N2O5 trap. With this suite of measurements we seek to elucidate the role of nitrate in biogenic SOA formation, as well as the fate of pollution emissions in a forest environment. We observe significant concentrations of ambient alkyl- and peroxynitrates, despite the remote forest location, and find evidence in PAM measurements that formation of these compounds is linked to organic aerosol production.

  5. Evaluation of the aerosol vertical distribution in global aerosol models through comparison against CALIOP measurements: AeroCom phase II results

    NASA Astrophysics Data System (ADS)

    Koffi, Brigitte; Schulz, Michael; Bréon, François-Marie; Dentener, Frank; Steensen, Birthe Marie; Griesfeller, Jan; Winker, David; Balkanski, Yves; Bauer, Susanne E.; Bellouin, Nicolas; Berntsen, Terje; Bian, Huisheng; Chin, Mian; Diehl, Thomas; Easter, Richard; Ghan, Steven; Hauglustaine, Didier A.; Iversen, Trond; Kirkevâg, Alf; Liu, Xiaohong; Lohmann, Ulrike; Myhre, Gunnar; Rasch, Phil; Seland, Åyvind; Skeie, Ragnhild B.; Steenrod, Stephen D.; Stier, Philip; Tackett, Jason; Takemura, Toshihiko; Tsigaridis, Kostas; Vuolo, Maria Raffaella; Yoon, Jinho; Zhang, Kai

    2016-06-01

    The ability of 11 models in simulating the aerosol vertical distribution from regional to global scales, as part of the second phase of the AeroCom model intercomparison initiative (AeroCom II), is assessed and compared to results of the first phase. The evaluation is performed using a global monthly gridded data set of aerosol extinction profiles built for this purpose from the CALIOP (Cloud-Aerosol Lidar with Orthogonal Polarization) Layer Product 3.01. Results over 12 subcontinental regions show that five models improved, whereas three degraded in reproducing the interregional variability in Zα0-6 km, the mean extinction height diagnostic, as computed from the CALIOP aerosol profiles over the 0-6 km altitude range for each studied region and season. While the models' performance remains highly variable, the simulation of the timing of the Zα0-6 km peak season has also improved for all but two models from AeroCom Phase I to Phase II. The biases in Zα0-6 km are smaller in all regions except Central Atlantic, East Asia, and North and South Africa. Most of the models now underestimate Zα0-6 km over land, notably in the dust and biomass burning regions in Asia and Africa. At global scale, the AeroCom II models better reproduce the Zα0-6 km latitudinal variability over ocean than over land. Hypotheses for the performance and evolution of the individual models and for the intermodel diversity are discussed. We also provide an analysis of the CALIOP limitations and uncertainties contributing to the differences between the simulations and observations.

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

    NASA Astrophysics Data System (ADS)

    Lee, Anita; Goldstein, Allen H.; Keywood, Melita D.; Gao, Song; Varutbangkul, Varuntida; Bahreini, Roya; Ng, Nga L.; Flagan, Richard C.; Seinfeld, John H.

    2006-04-01

    The ozonolyses of six monoterpenes (α-pinene, β-pinene, 3-carene, terpinolene, α-terpinene, and myrcene), two sesquiterpenes (α-humulene and β-caryophyllene), and two oxygenated terpenes (methyl chavicol and linalool) were conducted individually in Teflon chambers to examine the gas-phase oxidation product and secondary organic aerosol (SOA) yields from these reactions. Particle size distribution and number concentration were monitored and allowed for the calculation of the SOA yield from each experiment, which ranged from 1 to 54%. A proton transfer reaction mass spectrometer (PTR-MS) was used to monitor the evolution of gas-phase products, identified by their mass to charge ratio (m/z). Several gas-phase oxidation products, formaldehyde, acetaldehyde, formic acid, acetone, acetic acid, and nopinone, were identified and calibrated. Aerosol yields, and the yields of these identified and calibrated oxidation products, as well as many higher m/z oxidation products observed with the PTR-MS, varied significantly between the different parent terpene compounds. The sum of measured oxidation products in the gas and particle phase ranged from 33 to 77% of the carbon in the reacted terpenes, suggesting there are still unmeasured products from these reactions. The observations of the higher molecular weight oxidation product ions provide evidence of previously unreported compounds and their temporal evolution in the smog chamber from multistep oxidation processes. Many of the observed ions, including m/z 111 and 113, have also been observed in ambient air above a Ponderosa pine forest canopy, and our results confirm they are consistent with products from terpene + O3 reactions. Many of these products are stable on the timescale of our experiments and can therefore be monitored in field campaigns as evidence for ozone oxidative chemistry.

  7. Rapid RNA exchange in aqueous two-phase system and coacervate droplets.

    PubMed

    Jia, Tony Z; Hentrich, Christian; Szostak, Jack W

    2014-02-01

    Compartmentalization in a prebiotic setting is an important aspect of early cell formation and is crucial for the development of an artificial protocell system that effectively couples genotype and phenotype. Aqueous two-phase systems (ATPSs) and complex coacervates are phase separation phenomena that lead to the selective partitioning of biomolecules and have recently been proposed as membrane-free protocell models. We show in this study through fluorescence recovery after photobleaching (FRAP) microscopy that despite the ability of such systems to effectively concentrate RNA, there is a high rate of RNA exchange between phases in dextran/polyethylene glycol ATPS and ATP/poly-L-lysine coacervate droplets. In contrast to fatty acid vesicles, these systems would not allow effective segregation and consequent evolution of RNA, thus rendering these systems ineffective as model protocells.

  8. Rapid RNA Exchange in Aqueous Two-Phase System and Coacervate Droplets

    NASA Astrophysics Data System (ADS)

    Jia, Tony Z.; Hentrich, Christian; Szostak, Jack W.

    2014-02-01

    Compartmentalization in a prebiotic setting is an important aspect of early cell formation and is crucial for the development of an artificial protocell system that effectively couples genotype and phenotype. Aqueous two-phase systems (ATPSs) and complex coacervates are phase separation phenomena that lead to the selective partitioning of biomolecules and have recently been proposed as membrane-free protocell models. We show in this study through fluorescence recovery after photobleaching (FRAP) microscopy that despite the ability of such systems to effectively concentrate RNA, there is a high rate of RNA exchange between phases in dextran/polyethylene glycol ATPS and ATP/poly-L-lysine coacervate droplets. In contrast to fatty acid vesicles, these systems would not allow effective segregation and consequent evolution of RNA, thus rendering these systems ineffective as model protocells.

  9. Rapid RNA exchange in aqueous two-phase system and coacervate droplets.

    PubMed

    Jia, Tony Z; Hentrich, Christian; Szostak, Jack W

    2014-02-01

    Compartmentalization in a prebiotic setting is an important aspect of early cell formation and is crucial for the development of an artificial protocell system that effectively couples genotype and phenotype. Aqueous two-phase systems (ATPSs) and complex coacervates are phase separation phenomena that lead to the selective partitioning of biomolecules and have recently been proposed as membrane-free protocell models. We show in this study through fluorescence recovery after photobleaching (FRAP) microscopy that despite the ability of such systems to effectively concentrate RNA, there is a high rate of RNA exchange between phases in dextran/polyethylene glycol ATPS and ATP/poly-L-lysine coacervate droplets. In contrast to fatty acid vesicles, these systems would not allow effective segregation and consequent evolution of RNA, thus rendering these systems ineffective as model protocells. PMID:24577897

  10. NMR signal analysis to characterize solid, aqueous, and lipid phases in baked cakes.

    PubMed

    Le Grand, F; Cambert, M; Mariette, F

    2007-12-26

    Proton mobility was studied in molecular fractions of some model systems and of cake using a 1H nuclear magnetic resonance (NMR) relaxation technique. For cake, five spin-spin relaxation times (T2) were obtained from transverse relaxation curves: T2 (1) approximately 20 micros, T2 (2) approximately 0.2 ms, T2 (3) approximately 3 ms, T2 (4) approximately 50 ms, and T2 (2) approximately 165 ms. The faster component was attributed to the solid phase, components 2 and 3 were associated with the aqueous phase, and the two slowest components were linked to the lipid phase. After cooking, the crust contained more fat but less water than the center part of the cake. The amount of gelatinized starch was lower in the crust, and water was more mobile due to less interaction with macromolecules. This preliminary study revealed different effects of storage on the center and crust.

  11. Liquid crystalline phases and their dispersions in aqueous mixtures of glycerol monooleate and glyceryl monooleyl ether.

    PubMed

    Popescu, Georgeta; Barauskas, Justas; Nylander, Tommy; Tiberg, Fredrik

    2007-01-16

    The aqueous phase behavior of mixtures of 1-glycerol monooleate (GMO) and its ether analogue, 1-glyceryl monooleyl ether (GME) has been investigated by a combination of polarized microscopy, X-ray diffraction, and NMR techniques. Three phase diagrams of the ternary GMO/GME/water system have been constructed at 25, 40, and 55 degrees C. The results demonstrate that the increasing amount of GME favors the formation of the reversed phases, evidenced by the transformation of the lamellar and bicontinuous cubic liquid crystalline phases of the binary GMO/water system into reversed micellar or reversed hexagonal phases. For a particular liquid crystalline phase, increasing the GME content has no effect on the structural characteristics and hydration properties, thus suggesting ideal mixing with GMO. Investigations of dispersed nanoparticle samples using shear and a polymeric stabilizer, Pluronic F127, show the possibility of forming two different kinds of bicontinuous cubic phase nanoparticles by simply changing the GMO/GME ratio. Also NMR self-diffusion measurements confirm that the block copolymer, Pluronic F127, used to facilitate dispersion formation, is associated with nanoparticles and provides steric stabilization.

  12. Mapping the Complex Phase Behaviors of Aqueous Mixtures of κ-Carrageenan and Type B Gelatin.

    PubMed

    Cao, Yiping; Wang, Lu; Zhang, Ke; Fang, Yapeng; Nishinari, Katsuyoshi; Phillips, Glyn O

    2015-07-30

    We report a detailed and complete phase diagram for an aqueous mixture of oppositely charged gelling biopolymers, type B gelatin and κ-carrageenan (KC) at pH 7.0. The phase diagram is studied in the ionic strength-temperature coordinate by means of turbidity, rheological and differential scanning calorimetric measurements, and macroscopic phase compositional analysis. Seven phase regions are identified, including (I) compatible region, (II) electrostatically induced associative phase separation (EIAPS) region, (III) hydrogen bonding induced associative phase separation (HBIAPS) region, (IV) coexistence of EIAPS and HBIAPS, (V) segregative phase separation (SPS) region, (VI) coexistence of HBIAPS and SPS, and (VII) SPS trapped by gelation. The HBIAPS reported for the first time here is attributed to the extensive hydrogen bonding formation between gelatin and KC above their conformational transition temperatures, as probed by addition of urea and methylene blue as well as by 2D (1)H-(1)H NOESY NMR. NaCl is found to have dual effects on HBIAPS. The electrostatic complexation at lower ionic strength facilitates the formation of hydrogen bonds between gelatin and KC and hence the HBIAPS. It is believed that the local structural arrangement of gelatin molecules or the change in local solvent environment prior to triple helix formation during cooling enables the formation of hydrogen bonds with KC.

  13. Glass-liquid phase separation in highly supersaturated aqueous solutions of telaprevir.

    PubMed

    Mosquera-Giraldo, Laura I; Taylor, Lynne S

    2015-02-01

    Amorphous solid dispersions are of great current interest because they can improve the delivery of poorly water-soluble compounds. It has been recently noted that the highly supersaturated solutions generated by dissolution of some ASDs can undergo a phase transition to a colloidal, disordered, drug-rich phase when the concentration exceeds the "amorphous solubility" of the drug. The purpose of this study was to investigate the phase behavior of supersaturated solutions of telaprevir, which is formulated as an amorphous solid dispersion in the commercial product. Different analytical techniques including proton nuclear magnetic resonance spectroscopy (NMR), ultraviolet spectroscopy (UV), fluorescence spectroscopy and flux measurements were used to evaluate the properties of aqueous supersaturated solutions of telaprevir. It was found that highly supersaturated solutions of telaprevir underwent glass-liquid phase separation (GLPS) when the concentration exceeded 90 μg/mL, forming a water-saturated colloidal, amorphous drug-rich phase with a glass transition temperature of 52 °C. From flux measurements, it was observed that the "free" drug concentration reached a maximum at the concentration where GLPS occurred, and did not increase further as the concentration was increased. This phase behavior, which results in a precipitate and a metastable equilibrium between a supersaturated solution and a drug-rich phase, is obviously important in the context of evaluating amorphous solid dispersion formulations and their crystallization routes.

  14. Demixing of aqueous polymer two-phase systems in low gravity

    NASA Technical Reports Server (NTRS)

    Bamberger, S.; Harris, J. M.; Baird, J. K.; Boyce, J.; Vanalstine, J. M.; Snyder, R. S.; Brooks, D. E.

    1986-01-01

    When polymers such as dextran and poly(ethylene glycol) are mixed in aqueous solution biphasic systems often form. On Earth the emulsion formed by mixing the phases rapidly demixes because of phase density differences. Biological materials can be purified by selective partitioning between the phases. In the case of cells and other particulates the efficiency of these separations appears to be somewhat compromised by the demixing process. To modify this process and to evaluate the potential of two-phase partitioning in space, experiments on the effects of gravity on phase emulsion demixing were undertaken. The behavior of phase systems with essentially identical phase densities was studied at one-g and during low-g parabolic aircraft maneuvers. The results indicate the demixing can occur rather rapidly in space, although more slowly than on Earth. The demixing process was examined from a theoretical standpoint by applying the theory of Ostwald ripening. This theory predicts demizing rates many orders of magnitude lower than observed. Other possible demixing mechanisms are considered.

  15. Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases

    SciTech Connect

    He, Jiayue; Lu, Lu; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

    2014-03-01

    Catalytic pathways for the cleavage of ether bonds in benzyl phenyl ether (BPE) in liquid phase using Ni- and zeolite-based catalysts are explored. In the absence of catalysts, the C-O bond is selectively cleaved in water by hydrolysis, forming phenol and benzyl alcohol as intermediates, followed by alkylation. The hydronium ions catalyzing the reactions are provided by the dissociation of water at 523 K. Upon addition of HZSM-5, rates of hydrolysis and alkylation are markedly increased in relation to proton concentrations. In the presence of Ni/SiO2, the selective hydrogenolysis dominates for cleaving the Caliphatic-O bond. Catalyzed by the dual-functional Ni/HZSM-5, hydrogenolysis occurs as the major route rather than hydrolysis (minor route). In apolar undecane, the non-catalytic thermal pyrolysis route dominates. Hydrogenolysis of BPE appears to be the major reaction pathway in undecane in the presence of Ni/SiO2 or Ni/HZSM-5, almost completely suppressing radical reactions. Density functional theory (DFT) calculations strongly support the proposed C-O bond cleavage mechanisms on BPE in aqueous and apolar phases. These calculations show that BPE is initially protonated and subsequently hydrolyzed in the aqueous phase. Finally, DFT calculations suggest that the radical reactions in non-polar solvents lead to primary benzyl and phenoxy radicals in undecane, which leads to heavier condensation products as long as metals are absent for providing dissociated hydrogen.

  16. Novel Displacement Agents for Aqueous 2-Phase Extraction Can Be Estimated Based on Hybrid Shortcut Calculations.

    PubMed

    Kress, Christian; Sadowski, Gabriele; Brandenbusch, Christoph

    2016-10-01

    The purification of therapeutic proteins is a challenging task with immediate need for optimization. Besides other techniques, aqueous 2-phase extraction (ATPE) of proteins has been shown to be a promising alternative to cost-intensive state-of-the-art chromatographic protein purification. Most likely, to enable a selective extraction, protein partitioning has to be influenced using a displacement agent to isolate the target protein from the impurities. In this work, a new displacement agent (lithium bromide [LiBr]) allowing for the selective separation of the target protein IgG from human serum albumin (represents the impurity) within a citrate-polyethylene glycol (PEG) ATPS is presented. In order to characterize the displacement suitability of LiBr on IgG, the mutual influence of LiBr and the phase formers on the aqueous 2-phase system (ATPS) and partitioning is investigated. Using osmotic virial coefficients (B22 and B23) accessible by composition gradient multiangle light-scattering measurements, the precipitating effect of LiBr on both proteins and an estimation of both protein partition coefficients is estimated. The stabilizing effect of LiBr on both proteins was estimated based on B22 and experimentally validated within the citrate-PEG ATPS. Our approach contributes to an efficient implementation of ATPE within the downstream processing development of therapeutic proteins. PMID:27449229

  17. Distribution of organohalide-respiring bacteria between solid and aqueous phases.

    PubMed

    Cápiro, Natalie L; Wang, Yonggang; Hatt, Janet K; Lebrón, Carmen A; Pennell, Kurt D; Löffler, Frank E

    2014-09-16

    Contemporary microbial monitoring of aquifers relies on groundwater samples to enumerate nonattached cells of interest. One-dimensional column studies quantified the distribution of bacterial cells in solid and the aqueous phases as a function of microbial species, growth substrate availability and porous medium (i.e., Appling soil versus Federal Fine Ottawa sand with 0.75% and 0.01% [w/w] organic carbon, respectively). Without supplied growth substrates, effluent from columns inoculated with the tetrachloroethene- (PCE-) to-ethene-dechlorinating bacterial consortium BDI-SZ containing Dehalococcoides mccartyi (Dhc) strains and Geobacter lovleyi strain SZ (GeoSZ), or inoculated with Anaeromyxobacter dehalogenans strain W (AdehalW), captured 94-96, 81-99, and 73-84% of the Dhc, GeoSZ, and AdehalW cells, respectively. Cell retention was organism-specific and increased in the order Dhc < GeoSZ < AdehalW. When amended with 10 mM lactate and 0.11 mM PCE, aqueous samples accounted for 1.3-27 and 0.02-22% of the total Dhc and GeoSZ biomass, respectively. In Appling soil, up to three orders-of-magnitude more cells were associated with the solid phase, and attachment rate coefficients (katt) were consistently greater compared to Federal Fine sand. Cell-solid interaction energies ranged from -2.5 to 787 kT and were consistent with organism-specific deposition behavior, where GeoSZ and AdehalW exhibited greater attachment than Dhc cells. The observed disparities in microbial cell distributions between the aqueous and solid phases imply that groundwater analysis can underestimate the total cell abundance in the aquifer by orders-of-magnitude under conditions of growth and in porous media with elevated organic carbon content. The implications of these findings for monitoring chlorinated solvent sites are discussed. PMID:25105899

  18. High-yield isolation of extracellular vesicles using aqueous two-phase system.

    PubMed

    Shin, Hyunwoo; Han, Chungmin; Labuz, Joseph M; Kim, Jiyoon; Kim, Jongmin; Cho, Siwoo; Gho, Yong Song; Takayama, Shuichi; Park, Jaesung

    2015-01-01

    Extracellular vesicles (EVs) such as exosomes and microvesicles released from cells are potential biomarkers for blood-based diagnostic applications. To exploit EVs as diagnostic biomarkers, an effective pre-analytical process is necessary. However, recent studies performed with blood-borne EVs have been hindered by the lack of effective purification strategies. In this study, an efficient EV isolation method was developed by using polyethylene glycol/dextran aqueous two phase system (ATPS). This method provides high EV recovery efficiency (~70%) in a short time (~15 min). Consequently, it can significantly increase the diagnostic applicability of EVs. PMID:26271727

  19. Biosorption of fluoride from aqueous phase onto algal Spirogyra IO1 and evaluation of adsorption kinetics.

    PubMed

    Venkata Mohan, S; Ramanaiah, S V; Rajkumar, B; Sarma, P N

    2007-03-01

    Non-viable algal Spirogyra IO1 was studied for its fluoride sorption potential in batch studies. The results demonstrated the ability of the biosorbent for fluoride removal. The sorption interaction of fluoride on to non-viable algal species obeyed the pseudo-first-order rate equation. The intraparticle diffusion of fluoride molecules within the Spirogyra was identified to be the rate-limiting step. It was also found that the adsorption isotherm followed the rearranged Langmuir isotherm adsorption model. Fluoride sorption was dependent on the aqueous phase pH and the fluoride uptake was greater at lower pH.

  20. The partitioning of Staphylococcus epidermidis in aqueous two-phase systems.

    PubMed

    Bruce, D L; Fisher, D; Hart, C A

    1987-09-01

    The surface properties of two isolates of Staphylococcus epidermis were compared by cell partitioning in aqueous two-phase systems. Strain K805 was isolated from the cerebrospinal fluid of a child with a shunt infection and strain 1105 was obtained from human faeces and not known to have caused infection. Strain K805 was significantly more negatively charged than strain 1105 but there was no significant difference in hydrophobicity when cultures were grown for 18 h. However, prolonged incubation of strain K805 caused the production of extracellular slime and a marked increase in surface hydrophobicity. Both strains showed enhanced growth in biphasic cultures. PMID:2443705

  1. Phase equilibria in a system of aqueous arginine with an octane solution of sulfonic acid

    NASA Astrophysics Data System (ADS)

    Kuvaeva, Z. I.; Koval'chuk, I. V.; Vodop'yanova, L. A.; Soldatov, V. S.

    2013-05-01

    The extraction of arginine (Arg) from aqueous salt (0.1 M NaCl) solutions with a sulfo extractant in a wide range of pH values and amino acid concentrations was studied. The 0.1 M solution of dinonylnaphthalenesulfonic acid (HD) in octane was used as an extractant. The degree of extraction was found to be high at pH 0.8-9.0. This can be explained by the effect of additional intermolecular interactions in the extractant phase involving the guanidine group of Arg.

  2. Partition of volatile compounds in pea globulin-maltodextrin aqueous two-phase system.

    PubMed

    Nguyen, Thanh Dat; Lafarge, Céline; Murat, Chloé; Mession, Jean-Luc; Cayot, Nathalie; Saurel, Rémi

    2014-12-01

    This study is based on the assumption that the off-flavour of pea proteins might be decreased using the retention of volatile compounds by a mixture with another biopolymer. The partition of volatile compounds in an aqueous system containing pea protein and maltodextrins was followed under thermodynamic incompatibility conditions. Firstly, the phase diagram of the system was established. Then, the partition of aroma compounds between the phase rich in protein and the phase rich in maltodextrin was measured by SPME-GC-MS. There was a transfer of volatile compounds during phase separation. Variations of pH were also used to vary the retention of volatile compounds by proteins. The concentration of volatile compounds in protein solution at pH 2.4 was higher than at pH 7.2. It was possible to increase the transfer of volatile compounds from the phase rich in protein to the phase rich in maltodextrin using the effect of pH on protein denaturation.

  3. A theory of electrophoresis of emulsion drops in aqueous two-phase polymer systems

    NASA Technical Reports Server (NTRS)

    Levine, S.

    1982-01-01

    An electrophoresis study has been carried out in an emulsion formed from an electrically neutral aqueous mixture of dextran and polyethylene glycol equilibrated at sufficient concentrations in the presence of electrolytes. Electrophoresis of a drop of one phase suspended in the other is observed, and the direction of the drop's motion is reversed when the disperse phase and the continuous phase are interchanged. In the presence of sulfate, phosphate, or citrate ions, an electrostatic potential difference of the order of a few mV exists between the two phases. The potential implied by the direction of the electrophoretic motion is opposite to the Donnan potential observed between the two phases. The mobility of an emulsion drop increases with the drop radius and depends on ion concentration. These results are explained in terms of a model postulating an electric dipole layer associated with a mixture of oriented polymer molecules at the surface of a drop, with a potential difference between the interiors of the two phases resulting from the unequal ion distribution.

  4. Aerosol-induced lung injuries observed by synchrotron radiation X-ray phase-contrast imaging technique

    NASA Astrophysics Data System (ADS)

    Yue, Weisheng; Zhang, Guilin; Liu, Ping; Sun, Jianqi; Hwu, Yeukuang; Je, Jung Ho; Tan, Mingguang; Li, Yan

    2007-09-01

    Adverse health effects are associated with the inhalation of a variety of atmospheric particles. To study the lung injuries caused by aerosol PM2.5, synchrotron radiation (SR) X-ray phase-contrast imaging technique was used. Nude mice were inoculated with PM2.5 samples collected from suburban area (JD), industrial area (BS) and traffic tunnel (DPQ) of Shanghai. From X-ray phase-contrast images of lung tissues, apart from blood vessels and structures of alveoli, even hemorrhage spots of several microns caused by the inflammation were clearly observed. The studies showed that the PM2.5 samples collected from the traffic tunnel (DPQ) produced higher level of lung injury, followed by the aerosol samples collected from industrial area (BS) and suburban area (JD). Our studies also helped us to understand the process of lung injuries caused by aerosol particles.

  5. Aerosol and gas-phase characteristics in relation to meteorology: Case studies in populated arid settings

    NASA Astrophysics Data System (ADS)

    Crosbie, Ewan Colin

    Atmospheric aerosols and trace gases are a highly relevant component of the climate system affecting atmospheric radiative transfer and the hydrologic cycle. In arid and semi-arid regions, where cloud cover is often low and precipitation is generally scarce and sporadic, the driving processes accounting for the production, loss and transport of atmospheric constituents are often distinctly different from other climates. In arid regions, the same circulation dynamics that suppress cloud formation can be responsible for creating strong subsidence inversions, which cap atmospheric mixing and trap pollutants close to the surface, often placing populated arid regions high on global rankings of air pollution concerns. In addition, low soil moisture can encourage wind-blown dust emissions, which can be a significant fraction of the total aerosol loading in both coarse and fine modes on a mass basis. Three distinct focus regions are investigated over varying time scales, using a diverse set of techniques, and with wide-ranging primary goals. 1) the Tehran metropolitan area in Iran over a ten-year period from 2000-2009, 2) Tucson, Arizona over 2012-2014 with three intensive monitoring periods during summer 2014 and winter 2015 and 3) the San Joaquin Valley in California during the NASA DISCOVER-AQ campaign during Jan-Feb 2013. However, in all cases, local and regional scale meteorology play a significant role in controlling the spatiotemporal variability in trace gas and aerosol concentrations. Particular emphasis is placed on understanding transport pathways due to the local wind patterns and the importance of key meteorological parameters such as temperature, humidity and solar radiation on controlling production and loss mechanisms. While low in magnitude, the precipitation pattern is still an important sink mechanism that modulates gas phase and particle abundances in all three regions, either through scavenging or by promoting vertical mixing. The reported measurements

  6. Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

    NASA Astrophysics Data System (ADS)

    Beardsley, Ross L.; Jang, Myoseon

    2016-05-01

    The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+], mol L-1) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of photooxidation products and sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (eight groups) and aerosol phase reactivity (six groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid-catalyzed reactions and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx (VOC - volatile organic compound). The model is validated using isoprene photooxidation experiments performed in the dual, outdoor University of Florida Atmospheric PHotochemical Outdoor Reactor (UF APHOR) chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total organic mass formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H

  7. Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

    NASA Astrophysics Data System (ADS)

    Beardsley, R. L.; Jang, M.

    2015-11-01

    The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+]) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of the photooxidation products and the sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (8 groups) and aerosol phase reactivity (6 groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid catalyzed reactions, and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx. The model is validated using isoprene photooxidation experiments performed in the dual, outdoor UF APHOR chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total OM formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC, and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H+] but is dynamically related to all three parameters. For VOC / NOx > 10, with increasing NOx both experimental and

  8. Quantification of colloidal and aqueous element transfer in soils: The dual-phase mass balance model

    USGS Publications Warehouse

    Bern, Carleton R.; Thompson, Aaron; Chadwick, Oliver A.

    2015-01-01

    Mass balance models have become standard tools for characterizing element gains and losses and volumetric change during weathering and soil development. However, they rely on the assumption of complete immobility for an index element such as Ti or Zr. Here we describe a dual-phase mass balance model that eliminates the need for an assumption of immobility and in the process quantifies the contribution of aqueous versus colloidal element transfer. In the model, the high field strength elements Ti and Zr are assumed to be mobile only as suspended solids (colloids) and can therefore be used to distinguish elemental redistribution via colloids from redistribution via dissolved aqueous solutes. Calculations are based upon element concentrations in soil, parent material, and colloids dispersed from soil in the laboratory. We illustrate the utility of this model using a catena in South Africa. Traditional mass balance models systematically distort elemental gains and losses and changes in soil volume in this catena due to significant redistribution of Zr-bearing colloids. Applying the dual-phase model accounts for this colloidal redistribution and we find that the process accounts for a substantial portion of the major element (e.g., Al, Fe and Si) loss from eluvial soil. In addition, we find that in illuvial soils along this catena, gains of colloidal material significantly offset aqueous elemental loss. In other settings, processes such as accumulation of exogenous dust can mimic the geochemical effects of colloid redistribution and we suggest strategies for distinguishing between the two. The movement of clays and colloidal material is a major process in weathering and pedogenesis; the mass balance model presented here is a tool for quantifying effects of that process over time scales of soil development.

  9. Nickel(II) Oxide Solubility and Phase Stability in High Temperature Aqueous Solutions

    SciTech Connect

    S.E. Ziemniak; M.A. Goyette

    2003-03-17

    A platinum-lined, flowing autoclave facility was used to investigate the solubility behavior of nickel(II) oxide (NiO) in deoxygenated ammonium and sodium hydroxide solutions between 21 and 315 C. Solubilities were found to vary between 0.4 and 400 nanomolal (nm). The measured nickel ion solubilities were interpreted via a Ni(II) ion hydroxo- and amino-complexing model and thermodynamic functions for these equilibria were obtained from a least-squares analysis of the data. Two solid phase transformations were observed: at temperatures below 149 C, the activity of Ni(II) ions in aqueous solution was controlled by a hydrous Ni(II) oxide (theophrastite) solid phase rather than anhydrous NiO (bunsenite); above 247 C, Ni(II) activities were controlled by cubic rather than rhombohedral bunsenite.

  10. Nickel (II) Oxide Solubility and Phase Stability in High Temperature Aqueous Solutions

    SciTech Connect

    SE Ziemniak; MA Goyette

    2004-06-17

    A platinum-lined, flowing autoclave facility was used to investigate the solubility behavior of nickel(II) oxide (NiO) in deoxygenated ammonium and sodium hydroxide solutions between 21 and 315 C. Solubilities were found to vary between 0.4 and 400 nmol kg{sup -1}. The measured nickel ion solubilities were interpreted via a Ni(II) ion hydroxo-and amino-complexing model and thermodynamic functions for these equilibria were obtained from a least-squares analysis of the data. Two solid phase transformations were observed: at temperatures below 149 C, the activity of Ni(II) ions in aqueous solution was controlled by a hydrous Ni(II) oxide (theophrastite) solid phase rather than anhydrous NiO (bunsenite); above 247 C, Ni(II) activities were controlled by cubic rather than rhombohedral bunsenite.

  11. Ionic liquid-based aqueous two-phase system extraction of sulfonamides in milk.

    PubMed

    Shao, Mingyuan; Zhang, Xuli; Li, Na; Shi, Jiayuan; Zhang, Huijie; Wang, Zhibing; Zhang, Hanqi; Yu, Aimin; Yu, Yong

    2014-06-15

    A simple method for the determination of six sulfonamides (SAs) in milk samples was developed. 1-Butyl-3-methylimidazolium tetrafluoroborate and trisodium citrate dihydrate were used to form aqueous two-phase system. The aqueous two phase system was applied to the extraction of the SAs and the determination of the analytes was performed by high-performance liquid chromatography. To achieve optimum extraction performance, several experimental parameters, including the type and the amount of salt, the type and amount of ionic liquid, ultrasonic time and pH of sample solution, were investigated and optimized. Under the optimal experimental conditions, good linearity was observed in the range of 8.55-1036.36ngmL(-1). The limits of detection and quantification were in the range of 2.04-2.84 and 6.73-9.37ngmL(-1), respectively. The present method was successfully applied to the determination of SAs in milk samples, and the recoveries of analytes were in the range of 72.32-108.96% with relative standard deviations ranging from 0.56 to 12.20%. The results showed that the present method was rapid, feasible and environmentally friendly. PMID:24854709

  12. Anti-Adhesive Behaviors between Solid Hydrate and Liquid Aqueous Phase Induced by Hydrophobic Silica Nanoparticles.

    PubMed

    Min, Juwon; Baek, Seungjun; Somasundaran, P; Lee, Jae W

    2016-09-20

    This study introduces an "anti-adhesive force" at the interface of solid hydrate and liquid solution phases. The force was induced by the presence of hydrophobic silica nanoparticles or one of the common anti-agglomerants (AAs), sorbitan monolaurate (Span 20), at the interface. The anti-adhesive force, which is defined as the maximum pushing force that does not induce the formation of a capillary bridge between the cyclopentane (CP) hydrate particle and the aqueous solution, was measured using a microbalance. Both hydrophobic silica nanoparticles and Span 20 can inhibit adhesion between the CP hydrate probe and the aqueous phase because silica nanoparticles have an aggregative property at the interface, and Span 20 enables the hydrate surface to be wetted with oil. Adding water-soluble sodium dodecyl sulfate (SDS) to the nanoparticle system cannot affect the aggregative property or the distribution of silica nanoparticles at the interface and, thus, cannot change the anti-adhesive effect. However, the combined system of Span 20 and SDS dramatically reduces the interfacial tension: emulsion drops were formed at the interface without any energy input and were adsorbed on the CP hydrate surface, which can cause the growth of hydrate particles. Silica nanoparticles have a good anti-adhesive performance with a relatively smaller dosage and are less influenced by the presence of molecular surfactants; consequently, these nanoparticles may have a good potential for hydrate inhibition as AAs. PMID:27564571

  13. Hydrogen production through aqueous-phase reforming of ethylene glycol in a washcoated microchannel.

    PubMed

    D'Angelo, M Fernanda Neira; Ordomsky, Vitaly; Paunovic, Violeta; van der Schaaf, John; Schouten, Jaap C; Nijhuis, T Alexander

    2013-09-01

    Aqueous-phase reforming (APR) of biocarbohydrates is conducted in a catalytically stable washcoated microreactor where multiphase hydrogen removal enhances hydrogen efficiency. Single microchannel experiments are conducted following a simplified model based on the microreactor concept. A coating method to deposit a Pt-based catalyst on the microchannel walls is selected and optimized. APR reactivity tests are performed by using ethylene glycol as the model compound. Optimum results are achieved with a static washcoating technique; a highly uniform and well adhered 5 μm layer is deposited on the walls of a 320 μm internal diameter (ID) microchannel in one single step. During APR of ethylene glycol, the catalyst layer exhibits high stability over 10 days after limited initial deactivation. The microchannel presents higher conversion and selectivity to hydrogen than a fixed-bed reactor. The benefits of using a microreactor for APR can be further enhanced by utilizing increased Pt loadings, higher reaction temperatures, and larger carbohydrates (e.g., glucose). The use of microtechnology for aqueous-phase reforming will allow for a great reduction in the reformer size, thus rendering it promising for distributed hydrogen production. PMID:23592593

  14. Effect of high pressure homogenization on aqueous phase solvent extraction of lipids from Nannochloris Oculata microalgae

    SciTech Connect

    Samarasinghe, Nalin; Fernando, Sandun; Faulkner, William B.

    2012-12-01

    The ability to extract lipids from high-moisture Nannochloris Oculata algal biomass disrupted with high pressure homogenization was investigated. During the first phase, the effect of high pressure homogenization (system pressure and number of passes) on disrupting aqueous algae (of different concentrations and degree of stress) was investigated. Secondly, the effect of degree of cell wall disruption on the amount of lipids extracted with three solvents, namely: hexane, dichloromethane and chloroform, were compared. Studies reveled that high pressure homogenization is effective on cell disruption while the amount of system pressure being the most significant factor affecting the degree of cell breakage. Although the number of passes had some impact, the level of disruption seemed to level-off after a certain number of passes. The study revealed that slightly polar solvents (such as chloroform and dichloromethane) performed better in aqueous-phase lipid extractions as compared to hexane. Also, it was revealed that it was not necessary to disrupt the algal cells completely to achieve appreciable levels of lipid yields. In fact, conditions that exerted only 20% of the cells to completely disrupt, allowed sufficient damage to liberate most of the lipids contained in the remainder of the cells.

  15. Effect of high pressure homogenization on aqueous phase solvent extraction of lipids from Nannochloris Oculata microalgae

    DOE PAGES

    Samarasinghe, Nalin; Fernando, Sandun; Faulkner, William B.

    2012-12-01

    The ability to extract lipids from high-moisture Nannochloris Oculata algal biomass disrupted with high pressure homogenization was investigated. During the first phase, the effect of high pressure homogenization (system pressure and number of passes) on disrupting aqueous algae (of different concentrations and degree of stress) was investigated. Secondly, the effect of degree of cell wall disruption on the amount of lipids extracted with three solvents, namely: hexane, dichloromethane and chloroform, were compared. Studies reveled that high pressure homogenization is effective on cell disruption while the amount of system pressure being the most significant factor affecting the degree of cell breakage.more » Although the number of passes had some impact, the level of disruption seemed to level-off after a certain number of passes. The study revealed that slightly polar solvents (such as chloroform and dichloromethane) performed better in aqueous-phase lipid extractions as compared to hexane. Also, it was revealed that it was not necessary to disrupt the algal cells completely to achieve appreciable levels of lipid yields. In fact, conditions that exerted only 20% of the cells to completely disrupt, allowed sufficient damage to liberate most of the lipids contained in the remainder of the cells.« less

  16. Aqueous and Gas Phase Sorption Properties of Mercury in Burned Soils

    NASA Astrophysics Data System (ADS)

    Jay, J.; Ferreira, M.; Burke, M.; Hogue, T.

    2008-12-01

    Wildfires are a common occurrence in the Mediterranean climate of Southern California. Many studies have focused on the post-fire physical impacts however; there is a lack of studies on the potential for post-fire metal transport, in particular mercury (Hg). Inorganic Hg contamination is present even in pristine areas due to atmospheric deposition, which can be microbially transformed to methylmercury (a bioaccumulative neurotoxin) in aquatic systems. In order to model the transport of mercury in burned soils, we need to understand the sorption properties of mercury in soils exposed to fire. To test the hypothesis that burned soils have different sorption properties than unburned ones, we have collected samples of unburned soils, and burned them in a controlled setting at different temperatures to simulate several fire intensities. Then, we applied traditional aqueous sorption techniques to determine the binding properties of mercury to each burned soil. Experimental data were fitted with FITEQL to derive constants for sorption reactions, which were in agreement with values observed in literature. Since Southern California does not receive much rain, most of the atmospheric mercury deposition is in form of dry deposition. Thus, we have designed and applied a novel sorption technique to determine the binding of mercury in the gas phase to the burned soils. Trends in sorption affinity and capacity with burning temperature are discussed, as well as a comparison between aqueous and gas phase sorption properties is made.

  17. Aqueous phase adsorption of different sized molecules on activated carbon fibers: Effect of textural properties.

    PubMed

    Prajapati, Yogendra N; Bhaduri, Bhaskar; Joshi, Harish C; Srivastava, Anurag; Verma, Nishith

    2016-07-01

    The effect that the textural properties of rayon-based activated carbon fibers (ACFs), such as the BET surface area and pore size distribution (PSD), have on the adsorption of differently sized molecules, namely, brilliant yellow (BY), methyl orange (MO) and phenol (PH), was investigated in the aqueous phase. ACF samples with different BET areas and PSDs were produced by steam-activating carbonized fibers for different activation times (0.25, 0.5, and 1 h). The samples activated for 0.25 h were predominantly microporous, whereas those activated for relatively longer times contained hierarchical micro-mesopores. The adsorption capacities of the ACFs for the adsorbate increased with increasing BET surface area and pore volume, and ranged from 51 to 1306 mg/g depending on the textural properties of the ACFs and adsorbate size. The adsorption capacities of the hierarchical ACF samples followed the order BY > MO > PH. Interestingly, the number of molecules adsorbed by the ACFs followed the reverse order: PH > MO > BY. This anomaly was attributed to the increasing molecular weight of the PH, MO and BY molecules. The equilibrium adsorption data were described using the Langmuir isotherm. This study shows that suitable textural modifications to ACFs are required for the efficient aqueous phase removal of an adsorbate. PMID:27107386

  18. Aqueous phase adsorption of different sized molecules on activated carbon fibers: Effect of textural properties.

    PubMed

    Prajapati, Yogendra N; Bhaduri, Bhaskar; Joshi, Harish C; Srivastava, Anurag; Verma, Nishith

    2016-07-01

    The effect that the textural properties of rayon-based activated carbon fibers (ACFs), such as the BET surface area and pore size distribution (PSD), have on the adsorption of differently sized molecules, namely, brilliant yellow (BY), methyl orange (MO) and phenol (PH), was investigated in the aqueous phase. ACF samples with different BET areas and PSDs were produced by steam-activating carbonized fibers for different activation times (0.25, 0.5, and 1 h). The samples activated for 0.25 h were predominantly microporous, whereas those activated for relatively longer times contained hierarchical micro-mesopores. The adsorption capacities of the ACFs for the adsorbate increased with increasing BET surface area and pore volume, and ranged from 51 to 1306 mg/g depending on the textural properties of the ACFs and adsorbate size. The adsorption capacities of the hierarchical ACF samples followed the order BY > MO > PH. Interestingly, the number of molecules adsorbed by the ACFs followed the reverse order: PH > MO > BY. This anomaly was attributed to the increasing molecular weight of the PH, MO and BY molecules. The equilibrium adsorption data were described using the Langmuir isotherm. This study shows that suitable textural modifications to ACFs are required for the efficient aqueous phase removal of an adsorbate.

  19. Characterizing Mass Transfer of a Complex Non-aqueous Phase Liquid

    NASA Astrophysics Data System (ADS)

    McColl, C. M.; Johnson, G. R.; Brusseau, M. L.

    2004-12-01

    A series of laboratory experiments were conducted with a multiple-component, non-aqueous phase liquid (NAPL) collected from the Picillo Farm Superfund Site. Physical property analysis and compositional analysis were performed to provide initial information about the NAPL. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the elution behavior, mass-transfer dynamics, and mass recovery of five selected target compounds present in the NAPL mixture. Initial elution behavior of all target components appeared to be ideal, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch equilibrium experiment and those estimated using Raoult's law based calculations incorporating NAPL composition data. Air-stripping of columns containing a pool of NAPL and no porous media revealed that removal of 1,2-DCB appeared to be limited by the molecular diffusion of the compound to the NAPL-air interface. Air-stripping of NAPL distributed relatively uniformly as a residual phase within a sandy porous medium exhibited ideal behavior.

  20. Scalable recovery of plasmid DNA based on aqueous two-phase separation.

    PubMed

    Frerix, Andreas; Müller, Markus; Kula, Maria-Regina; Hubbuch, Jürgen

    2005-08-01

    Future developments in gene therapy and DNA vaccination depend on cost-effective large-scale production of pharmaceutical-grade pDNA (plasmid DNA). Given the large amount of impurities present in the feedstock, purification processes that have high specificity and capacity at a moderate cost are required. In the present study, we describe a non-chromatographic procedure based on aqueous two-phase extraction allowing a fast and simply scalable capture step. PEG [poly(ethylene glycol)] in combination with potassium citrate or potassium phosphate was tested as phase component for extraction. By increasing either PEG or salt concentration, the partitioning of nucleic acids changed from bottom to top phase. Phase systems with a composition of 15% PEG 800 and 20% potassium phosphate at pH 7.0 showed a strong partitioning of pDNA to the bottom phase, linked to a clear decrease in open circular pDNA, while proteins, genomic DNA and RNA remain at the top or at the interphase. A great advantage of the current process is that the complete procedure of lysis, precipitation, clarification and extraction can be performed in a single vessel. The number of denatured and sheared genomic DNAs in a spiking experiment was found to be depleted by more than 99%. PMID:15612880

  1. Alkyl-bis(imidazolium) salts: a new amphiphile platform that forms thermotropic and non-aqueous lyotropic bicontinuous cubic phases

    SciTech Connect

    Robertson, LA; Schenkel, MR; Wiesenauer, BR; Gin, DL

    2013-01-01

    New ionic amphiphiles with a hexyl-bridged bis(imidazolium) headgroup; Br-, BF4-, or Tf2N- anions; and a long n-alkyl tail can form thermotropic bicontinuous cubic liquid crystal phases in neat form and/or lyotropic bicontinuous cubic phases with several non-aqueous solvents or water.

  2. Aqueous-phase behavior and vesicle formation of natural glycolipid biosurfactant, mannosylerythritol lipid-B.

    PubMed

    Worakitkanchanakul, Wannasiri; Imura, Tomohiro; Fukuoka, Tokuma; Morita, Tomotake; Sakai, Hideki; Abe, Masahiko; Rujiravanit, Ratana; Chavadej, Sumaeth; Minamikawa, Hiroyuki; Kitamoto, Dai

    2008-08-01

    Mannosylerythritol lipids (MELs) are one of the most promising glycolipid biosurfactants produced by yeast strains of the genus Pseudozyma. In this study, the aqueous-phase behavior of a new monoacetyl MEL derivative, 1-O-beta-(2',3'-di-O-alka(e)noyl-6'-O-acetyl-d-mannopyranosyl)-d-erythritol (MEL-B), was investigated using polarized optical microscopy, small-angle X-ray scattering (SAXS), confocal laser scanning microscopy (CLSM), and differential scanning calorimetry (DSC). The present MEL-B was found to self-assemble into a lamellar (L(alpha)) phase over remarkably wide concentration and temperature ranges. According to SAXS measurement, the interlayer spacing (d) was estimated to be almost constant (about 4.7 nm) at the low MEL-B concentration (phase is in equilibrium with the excess water phase (L(alpha)+W). On the other hand, at high MEL-B concentration (>60 wt.%) region, the d-spacing gradually decreased to 3.1 nm with an increase in the MEL-B concentration. The thermal stability of the liquid crystalline phase was investigated by DSC measurement. The obtained L(alpha) phase was found to be stable up to 95 degrees C below a MEL-B concentration of 85 wt.%; then, the melting temperature of the liquid crystalline phase dramatically decreased with an increase in MEL-B concentration (above 85 wt.%). Furthermore, we found relatively large vesicles (1-5 microm) at the low MEL-B concentration using CLSM observation. The trapped volume of the obtained MEL-B vesicle was estimated to be about 0.42 microL/mumol by glucose dialysis method. These results suggest that the natural glycolipid biosurfactant, the newly found MEL-B, would be useful in various fields of applications as an L(alpha) phase- and/or vesicle-forming lipid. PMID:18456469

  3. Heterogeneous ice nucleation and phase transition of viscous α-pinene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Ignatius, Karoliina; Kristensen, Thomas B.; Järvinen, Emma; Nichman, Leonid; Fuchs, Claudia; Gordon, Hamish; Herenz, Paul; Hoyle, Christopher R.; Duplissy, Jonathan; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Gallagher, Martin W.; Kirkby, Jasper; Kulmala, Markku; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin; Virtanen, Annele; Stratmann, Frank

    2016-04-01

    There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate deposition ice nucleation and thus influence cirrus cloud properties. Global model simulations of monoterpene SOA particles suggest that viscous biogenic SOA are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle (INP) budget. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles at the CLOUD (Cosmics Leaving OUtdoor Droplets) experiment at CERN (Ignatius et al., 2015, Järvinen et al., 2015). In the CLOUD chamber, the SOA particles were produced from the ozone initiated oxidation of α-pinene at temperatures in the range from -38 to -10° C at 5-15 % relative humidity with respect to water (RHw) to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. As the RHw was increased to between 35 % at -10° C and 80 % at -38° C, a transition to spherical shape was observed with a new in-situ optical method. This transition confirms previous modelling of the viscosity transition conditions. The ice nucleation ability of SOA particles was investigated with a new continuous flow diffusion chamber SPIN (Spectrometer for Ice Nuclei) for different SOA particle sizes. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA in the deposition mode for ice saturation ratios between 1.3 and 1.4, significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between -36.5 and -38.3° C ranged from 6 to 20 % and did not depend on the particle surface area. References Ignatius, K. et al., Heterogeneous ice

  4. Chemistry in the clouds: the role of aerosols in atmospheric chemistry.

    PubMed

    Reid, Jonathan P; Sayer, Robert M

    2002-01-01

    Ever since the discovery of the ozone hole over the Antarctic and the recognition of the damaging effects of acid rain, the role of atmospheric aerosol particles in determining the chemical balance of the atmosphere has received much attention. Aerosol particles produced in combustion can also have a deleterious effect on human health. In this article we review the chemistry that can occur on aerosol particles, particularly on aqueous based aerosols in the troposphere. The sources, transformation and loss mechanisms of atmospheric aerosol will be discussed. In particular, we will focus on the role of chemical transformation on aerosol particles in promoting reactions that would otherwise be too slow in the homogeneous atmospheric gas phase. Heterogeneous reaction mechanisms of some key chemical reactions will be described. Recent observations of a high organic content of tropospheric aerosol particles will be described and a model of organic coated aerosols will be reviewed.

  5. Aqueous Two-Phase System (ATPS) Containing Gemini (12-3-12,2Br-)and SDS 1: Phase Diagram and Properties of ATPS

    SciTech Connect

    Shang, Yazhuo; Liu, Honglai; Hu, Ying; Prausnitz, John M.

    2005-07-21

    Two phases coexist in an aqueous system that contains the two surfactants cationic gemini 12-3-12,2Br- and anionic SDS. An aqueous two-phase system (ATPS) is formed in a narrow region of the ternary phase diagram different from that of traditional aqueous cationic-anionic surfactant systems. In that region, the molar ratio of gemini to SDS varies with the total concentration of surfactants. ATPS not only has higher stability but also has longer phase separation time for the new systems than that of the traditional system. Furthermore, the optical properties of ATPS are different at different total concentrations. All of these experimental observations can be attributed to the unique properties of gemini surfactant and the synergy between the cationic gemini surfactant and the anionic surfactant SDS.

  6. Rapid Formation of Molecular Bromine from Deliquesced NaBr Aerosol in the Presence of Ozone and UV Light

    EPA Science Inventory

    The formation of gas-phase bromine from aqueous sodium bromide aerosols is investigated through a combination of chamber experiments and chemical kinetics modeling. Experiments show that Br2(g) is produced rapidly from deliquesced NaBr aerosols in the presence of OH radicals prod...

  7. Proton transfer from the inactive gas-phase nicotine structure to the bioactive aqueous-phase structure.

    PubMed

    Gaigeot, Marie-Pierre; Cimas, Alvaro; Seydou, Mahamadou; Kim, Ju-Young; Lee, Sungyul; Schermann, Jean-Pierre

    2010-12-29

    The role of water in the structural change of nicotine from its inactive form in the gas phase to its bioactive form in aqueous solution has been investigated by two complementary theoretical approaches, i.e., geometry optimizations and molecular dynamics. Structures of the lowest-energy nicotineH(+)-(H(2)O)(n) complexes protonated either on the pyridine (inactive form) or pyrrolidine (active form) ring have been calculated, as well as the free-energy barriers for the proton-transfer tautomerization between the two cycles. These structures show chains of 2-4 water molecules bridging the two protonation sites. The room-temperature free-energy barrier to tautomerization along the minimum-energy path from the pyridine to the pyrrolidine cycle drops rapidly when the number of water molecules increases from 0 to 4, but still remains rather high (16 kJ/mol with four water molecules), indicating that the proton transfer is a rather difficult and rare event. We compare results obtained through this explicit water molecule approach to those obtained by means of continuum methods. Car-Parrinello molecular dynamics (CPMD) simulations of the proton-transfer process in bulk with explicit water molecules have been conducted at room temperature. No spontaneous proton transfers have been observed during the dynamics, and biased CPMD simulations have therefore been performed in order to measure the free-energy profile of the proton transfer in the aqueous phase and to reveal the proton-transfer mechanism through water bridges. The MD bias involves pulling the proton from the pyridine ring to the surrounding bulk. Dynamics show that this triggers the tautomerization toward the pyrrolidine ring, proceeding without energy barrier. The proton transfer is extremely fast, and protonation of the pyrrolidine ring was achieved within 0.5 ps. CPMD simulations confirmed the pivotal role played by the water molecules that bridge the two protonation sites of nicotine within the bulk of the

  8. Preconcentration of aqueous dyes through phase-transfer liquid-phase microextraction with a room-temperature ionic liquid.

    PubMed

    Chen, Hsiu-Liang; Chang, Shuo-Kai; Lee, Chia-Ying; Chuang, Li-Lin; Wei, Guor-Tzo

    2012-09-12

    In this study, we employed the room-temperature ionic liquid [bmim][PF(6)] as both ion-pair agent and an extractant in the phase-transfer liquid-phase microextraction (PTLPME) of aqueous dyes. In the PTLPME method, a dye solution was added to the extraction solution, comprising a small amount of [bmim][PF(6)] in a relatively large amount of CH(2)Cl(2), which serves as the disperser solvent to an extraction solution. Following extraction, CH(2)Cl(2) was evaporated from the extractant, resulting in the extracted dyes being concentrated in a small volume of the ionic liquid phase to increase the enrichment factor. The enrichment factors of for the dye Methylene Blue, Neutral Red, and Methyl Red were approximately 500, 550 and 400, respectively; their detection limits were 0.014, 0.43, and 0.02 μg L(-1), respectively, with relative standard deviations of 4.72%, 4.20%, and 6.10%, respectively.

  9. Fundamental thermochemical properties of amino acids: gas-phase and aqueous acidities and gas-phase heats of formation.

    PubMed

    Stover, Michele L; Jackson, Virgil E; Matus, Myrna H; Adams, Margaret A; Cassady, Carolyn J; Dixon, David A

    2012-03-01

    The gas-phase acidities of the 20 L-amino acids have been predicted at the composite G3(MP2) level. A broad range of structures of the neutral and anion were studied to determine the lowest energy conformer. Excellent agreement is found with the available experimental gas-phase deprotonation enthalpies, and the calculated values are within experimental error. We predict that tyrosine is deprotonated at the CO(2)H site. Cysteine is predicted to be deprotonated at the SH but the proton on the CO(2)H is shared with the S(-) site. Self-consistent reaction field (SCRF) calculations with the COSMO parametrization were used to predict the pK(a)'s of the non-zwitterion form in aqueous solution. The differences in the non-zwitterion pK(a) values were used to estimate the free energy difference between the zwitterion and nonzwitterion forms in solution. The heats of formation of the neutral compounds were calculated from atomization energies and isodesmic reactions to provide the first reliable set of these values in the gas phase. Further calculations were performed on five rare amino acids to predict their heats of formation, acidities, and pK(a) values.

  10. A new description of Titan's aerosol optical properties from the analysis of VIMS Emission Phase Function observations

    NASA Astrophysics Data System (ADS)

    Rodriguez, Sebastien; Maltagliati, Luca; Sotin, Christophe; Rannou, Pascal; Bézard, Bruno; Cornet, Thomas

    2016-10-01

    The Huygens probe gave unprecedented information on the properties of Titan's aerosols (vertical distribution, opacity as a function of wavelength, phase function, single scattering albedo) by in-situ measurements (Tomasko et al. 2008). Being the only existing in-situ atmospheric probing for Titan, this aerosol model currently is the reference for many Titan studies (e.g. by being applied as physical input in radiative transfer models of the atmosphere). Recently a reanalysis of the DISR dataset, corroborated by data from the Downward-Looking Visible Spectrometer (DLVS), was carried out by the same group (Doose et al. 2016), leading to significant changes to the indications given by Tomasko et al. (2008).Here we present the analysis of the Emission Phase Function observation (EPF) performed by VIMS during the Cassini flyby T88 (November 2012). An EPF observes the same spot on the surface (and thus the same atmosphere) with the same emergence angle but with different incidence angles. In this way, our EPF allows, for the first time, to have direct information on the phase function of Titan's aerosols, as well as on other important physical parameters of the aerosols as the behavior of their extinction as a function of wavelength and the single scattering albedo (also as a function of wavelength) for the whole VIMS range (0.8-5.2 μm). The T88 EPF is composed of 25 VIMS datacubes spanning a scattering angle range approximately from 0°to 70°.We used the radiative transfer model described in Hirtzig et al. (2013) as baseline, updated with improved methane (+ related isotopes) spectroscopy. By changing the aerosol description in the model, we found the combination of aerosol optical parameters that fits best a constant aerosol column density over the whole set of the VIMS datacubes. We confirmed that the new results from Doose et al. (2016) do improve the fit for what concerns the vertical profile and the extinction as a function of wavelength. However, a different

  11. A new description of Titan's aerosol optical properties from the analysis of VIMS Emission Phase Function observations

    NASA Astrophysics Data System (ADS)

    Maltagliati, Luca; Rodriguez, Sebastien; Sotin, Christophe; Rannou, Pascal; Bezard, Bruno; Cornet, Thomas

    2016-06-01

    The Huygens probe gave unprecedented information on the properties of Titan's aerosols (vertical distribution, opacity as a function of wavelength, phase function, single scattering albedo) by in-situ measurements (Tomasko et al. 2008). Being the only existing in-situ atmospheric probing for Titan, this aerosol model currently is the reference for many Titan studies (e.g. by being applied as physical input in radiative transfer models of the atmosphere). Recently a reanalysis of the DISR dataset, corroborated by data from the Downward-Looking Visible Spectrometer (DLVS), was carried out by the same group (Doose et al. 2016), leading to significant changes to the indications given by Tomasko et al. (2008). Here we present the analysis of the Emission Phase Function observation (EPF) performed by VIMS during the Cassini flyby T88 (November 2012). An EPF observes the same spot on the surface (and thus the same atmosphere) with the same emergence angle but with different incidence angles. In this way, our EPF allows, for the first time, to have direct information on the phase function of Titan's aerosols, as well as on other important physical parameters of the aerosols as the behavior of their extinction as a function of wavelength and the single scattering albedo (also as a function of wavelength) for the whole VIMS range (0.8-5.2 µm). The T88 EPF is composed of 25 VIMS datacubes spanning a scattering angle range approximately from 0°to 70°. We used the radiative transfer model described in Hirtzig et al. (2013) as baseline, updated with improved methane (+ related isotopes) spectroscopy. By changing the aerosol description in the model, we found the combination of aerosol optical parameters that fits best a constant aerosol column density over the whole set of the VIMS datacubes. We confirmed that the new results from Doose et al. (2016) do improve the fit for what concerns the vertical profile and the extinction as a function of wavelength. However, a different

  12. Aqueous nitrite ion determination by selective reduction and gas phase nitric oxide chemiluminescence

    NASA Technical Reports Server (NTRS)

    Dunham, A. J.; Barkley, R. M.; Sievers, R. E.; Clarkson, T. W. (Principal Investigator)

    1995-01-01

    An improved method of flow injection analysis for aqueous nitrite ion exploits the sensitivity and selectivity of the nitric oxide (NO) chemilluminescence detector. Trace analysis of nitrite ion in a small sample (5-160 microL) is accomplished by conversion of nitrite ion to NO by aqueous iodide in acid. The resulting NO is transported to the gas phase through a semipermeable membrane and subsequently detected by monitoring the photoemission of the reaction between NO and ozone (O3). Chemiluminescence detection is selective for measurement of NO, and, since the detection occurs in the gas-phase, neither sample coloration nor turbidity interfere. The detection limit for a 100-microL sample is 0.04 ppb of nitrite ion. The precision at the 10 ppb level is 2% relative standard deviation, and 60-180 samples can be analyzed per hour. Samples of human saliva and food extracts were analyzed; the results from a standard colorimetric measurement are compared with those from the new chemiluminescence method in order to further validate the latter method. A high degree of selectivity is obtained due to the three discriminating steps in the process: (1) the nitrite ion to NO conversion conditions are virtually specific for nitrite ion, (2) only volatile products of the conversion will be swept to the gas phase (avoiding turbidity or color in spectrophotometric methods), and (3) the NO chemiluminescence detector selectively detects the emission from the NO + O3 reaction. The method is free of interferences, offers detection limits of low parts per billion of nitrite ion, and allows the analysis of up to 180 microL-sized samples per hour, with little sample preparation and no chromatographic separation. Much smaller samples can be analyzed by this method than in previously reported batch analysis methods, which typically require 5 mL or more of sample and often need chromatographic separations as well.

  13. Effective extraction of elastase from Bacillus sp. fermentation broth using aqueous two-phase system*

    PubMed Central

    Xu, Ying; He, Guo-qing; Li, Jing-jun

    2005-01-01

    This paper presents the evaluation of an aqueous two-phase system (ATPS) for extracting elastase produced by Bacillus sp. EL31410. The elastase and cell partition behavio r in polyethylene glycol (PEG)/salt systems was investigated. The suitable system for elastase extraction was PEG/KH2PO4-K2HPO4, in which elastase is mainly partitioned into the PEG-rich phase, while the cells remained in the other phase. The influence of defined system parameters (e.g. PEG molecular mass, pH, NaCl addition) on the partitioning behavior of elastase is described. The concentration of phase forming components, PEG and KH2PO4-K2HPO4, was optimized for elastase recovery by means of response surface methodology, and it was found that they greatly influenced extraction recovery. The optimal ATPS was 23.1% (w/w) PEG 2 000 and 11.7% (w/w) KH2PO4-K2HPO4. The predicted recovery was about 89.5%, so this process is suggested to be a rapid and convenient method for elastase extraction. PMID:16252343

  14. Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multi-layer model ADCHAM

    NASA Astrophysics Data System (ADS)

    Roldin, P.; Eriksson, A. C.; Nordin, E. Z.; Hermansson, E.; Mogensen, D.; Rusanen, A.; Boy, M.; Swietlicki, E.; Svenningsson, B.; Zelenyuk, A.; Pagels, J.

    2014-01-01

    We have developed the novel Aerosol Dynamics, gas- and particle-phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: (1) the mass transfer limited uptake of ammonia (NH3) and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), (2) the slow and almost particle size independent evaporation of α-pinene secondary organic aerosol (SOA) particles, and (3) the influence of chamber wall effects on the observed SOA formation in smog chambers. ADCHAM is able to capture the observed α-pinene SOA mass increase in the presence of NH3(g). Organic salts of ammonium and carboxylic acids predominantly form during the early stage of SOA formation. These salts contribute substantially to the initial growth of the homogeneously nucleated particles. The model simulations of evaporating α-pinene SOA particles support the recent experimental findings that these particles have a semi-solid tar like amorphous phase state. ADCHAM is able to reproduce the main features of the observed slow evaporation rates if low-volatility and viscous oligomerized SOA material accumulates in the particle surface layer upon evaporation. The evaporation rate is mainly governed by the reversible decomposition of oligomers back to monomers. Finally, we demonstrate that the mass transfer limited uptake of condensable organic compounds onto wall deposited particles or directly onto the Teflon chamber walls of smog chambers can have profound influence on the

  15. Unusual liquid-liquid phase transition in aqueous mixtures of a well-known dendrimer.

    PubMed

    da Costa, Viviana C P; Annunziata, Onofrio

    2015-11-21

    Liquid-liquid phase separation (LLPS) has been extensively investigated for polymer and protein solutions due to its importance in mixture thermodynamics, separation science and self-assembly processes. However, to date, no experimental studies have been reported on LLPS of dendrimer solutions. Here, it is shown that LLPS of aqueous solutions containing a hydroxyl-functionalized poly(amido amine) dendrimer of fourth generation is induced in the presence of sodium sulfate. Both the LLPS temperature and salt-dendrimer partitioning between the two coexisting phases at constant temperature were measured. Interestingly, our experiments show that LLPS switches from being induced by cooling to being induced by heating as the salt concentration increases. The two coexisting phases also show opposite temperature response. Thus, this phase transition exhibits a simultaneous lower and upper critical solution temperature-type behavior. Dynamic light-scattering and dye-binding experiments indicate that no appreciable conformational change occurs as the salt concentration increases. To explain the observed phase behavior, a thermodynamic model based on two parameters was developed. The first parameter, which describes dendrimer-dendrimer interaction energy, was determined by isothermal titration calorimetry. The second parameter describes the salt salting-out strength. By varying the salting-out parameter, it is shown that the model achieves agreement not only with the location of the experimental binodal at 25 °C but also with the slope of this curve around the critical point. The proposed model also predicts that the unusual temperature behavior of this phase transition can be described as the net result of two thermodynamic factors with opposite temperature responses: salt thermodynamic non-ideality and salting-out strength.

  16. Unusual liquid-liquid phase transition in aqueous mixtures of a well-known dendrimer.

    PubMed

    da Costa, Viviana C P; Annunziata, Onofrio

    2015-11-21

    Liquid-liquid phase separation (LLPS) has been extensively investigated for polymer and protein solutions due to its importance in mixture thermodynamics, separation science and self-assembly processes. However, to date, no experimental studies have been reported on LLPS of dendrimer solutions. Here, it is shown that LLPS of aqueous solutions containing a hydroxyl-functionalized poly(amido amine) dendrimer of fourth generation is induced in the presence of sodium sulfate. Both the LLPS temperature and salt-dendrimer partitioning between the two coexisting phases at constant temperature were measured. Interestingly, our experiments show that LLPS switches from being induced by cooling to being induced by heating as the salt concentration increases. The two coexisting phases also show opposite temperature response. Thus, this phase transition exhibits a simultaneous lower and upper critical solution temperature-type behavior. Dynamic light-scattering and dye-binding experiments indicate that no appreciable conformational change occurs as the salt concentration increases. To explain the observed phase behavior, a thermodynamic model based on two parameters was developed. The first parameter, which describes dendrimer-dendrimer interaction energy, was determined by isothermal titration calorimetry. The second parameter describes the salt salting-out strength. By varying the salting-out parameter, it is shown that the model achieves agreement not only with the location of the experimental binodal at 25 °C but also with the slope of this curve around the critical point. The proposed model also predicts that the unusual temperature behavior of this phase transition can be described as the net result of two thermodynamic factors with opposite temperature responses: salt thermodynamic non-ideality and salting-out strength. PMID:26451401

  17. Sonochemical preparation of copper sulfides with different phases in aqueous solutions

    SciTech Connect

    Kristl, Matjaž; Hojnik, Nuša; Gyergyek, Sašo; Drofenik, Miha

    2013-03-15

    Highlights: ► Sonochemical preparation of copper sulfides in aqueous solutions is reported. ► CuS and Cu{sub 2}S nanoparticles with crystallite sizes between 7 and 18 nm were obtained. ► Crystallite size can be changed using different complexing agents. ► Thermal behavior was studied by TG and XRD measurements. - Abstract: There is a growing interest in the synthesis of nanostructured copper sulfides due to their ability to form compounds with various stoichiometries. We report a sonochemical route for the preparation of copper sulfides with different compositions in aqueous solutions, using different, general and convenient copper sources such as copper acetate, copper hydroxide or basic copper carbonate and thiourea or thioacetamide as sulfur precursors under ambient air. Phase analysis, purity and morphology of the products were studied by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results revealed that nanoparticles of covellite, CuS, with crystallite sizes between 7 and 18 nm can be obtained by using different precursors and complexing agents and that chalcocite, Cu{sub 2}S, can also be prepared sonochemically.

  18. Resonance Raman Spectroscopy of Single-Wall Carbon Nanotubes Separated via Aqueous Two-Phase Extraction

    NASA Astrophysics Data System (ADS)

    Simpson, J. R.; Fagan, J. A.; Hight Walker, A. R.

    2014-03-01

    We report Resonance Raman Spectroscopy (RRS) measurements of single-wall carbon nanotube (SWCNT) samples dispersed in aqueous solutions via surfactant wrapping and separated using aqueous two-phase extraction (ATPE) into chirality-enriched semiconducting and metallic SWCNT species. ATPE provides a rapid, robust, and remarkably tunable separation technique that allows isolation of high-purity, individual SWCNT chiralities via modification of the surfactant environment. We report RRS measurements of individual SWCNT species of various chiral index including, armchair and zigzag metals. Raman provides a powerful technique to quantify the metallic SWCNTs in ATPE fractions separated for metallicity. We measure Raman spectra over a wide range of excitation wavelengths from 457 nm to 850 nm using a series of discrete and continuously tunable laser sources coupled to a triple-grating spectrometer with a liquid-nitrogen-cooled detector. The spectra reveal Raman-active vibrational modes, including the low-frequency radial breathing mode (RBM) and higher-order modes. SWCNT chiral vectors are determined from the Raman spectra, specifically the RBM frequencies and corresponding energy excitation profiles, together with input from theoretical models.

  19. Resonance Raman Spectroscopy of Single-Wall Carbon Nanotubes Separated via Aqueous Two-Phase Extraction

    NASA Astrophysics Data System (ADS)

    Simpson, J. R.; Fagan, J. A.; Hight Walker, A. R.

    2015-03-01

    We report resonance Raman Spectroscopy measurements of single-wall carbon nanotube (SWCNT) samples dispersed in aqueous solutions via surfactant wrapping and separated using aqueous two-phase extraction (ATPE) into chirality-enriched semiconducting and metallic SWCNT species. ATPE provides a rapid, robust, and remarkably tunable separation technique that allows isolation of high-purity, individual SWCNT chiralities via modification of the surfactant environment. We report RRS measurements of individual SWCNT species of various chiral index including, semiconductors, armchair and zigzag metals. Raman provides a powerful technique to quantify the metallic SWCNTs in ATPE fractions separated for metallicity. We measure Raman spectra over a wide range of excitation wavelengths from (457 to 850) nm using a series of discrete and continuously tunable laser sources coupled to a triple-grating spectrometer. The spectra reveal Raman-active vibrational modes, including the low-frequency radial breathing mode (RBM) and higher-order modes. SWCNT chiral vectors are determined from Raman spectra, specifically the RBM frequencies and corresponding energy excitation profiles, together with input from theoretical models.

  20. Aqueous phase hydration and hydrate acidity of perfluoroalkyl and n:2 fluorotelomer aldehydes.

    PubMed

    Rayne, Sierra; Forest, Kaya

    2016-01-01

    The SPARC software program and comparative density functional theory (DFT) calculations were used to investigate the aqueous phase hydration equilibrium constants (Khyd) of perfluoroalkyl aldehydes (PFAlds) and n:2 fluorotelomer aldehydes (FTAlds). Both classes are degradation products of known industrial compounds and environmental contaminants such as fluorotelomer alcohols, iodides, acrylates, phosphate esters, and other derivatives, as well as hydrofluorocarbons and hydrochlorofluorocarbons. Prior studies have generally failed to consider the hydration, and subsequent potential hydrate acidity, of these compounds, resulting in incomplete and erroneous predictions as to their environmental behavior. In the current work, DFT calculations suggest that all PFAlds will be dominantly present as the hydrated form in aqueous solution. Both SPARC and DFT calculations suggest that FTAlds will not likely be substantially hydrated in aquatic systems or in vivo. PFAld hydrates are expected to have pKa values in the range of phenols (ca. 9 to 10), whereas n:2 FTAld hydrates are expected to have pKa values ca. 2 to 3 units higher (ca. 12 to 13). In order to avoid spurious modeling predictions and a fundamental misunderstanding of their fate, the molecular and/or dissociated hydrate forms of PFAlds and FTAlds need to be explicitly considered in environmental, toxicological, and waste treatment investigations. The results of the current study will facilitate a more complete examination of the environmental fate of PFAlds and FTAlds. PMID:26980678

  1. Bioaugmentation for treatment of dense non-aqueous phase liquid in fractured sandstone blocks.

    PubMed

    Schaefer, Charles E; Towne, Rachael M; Vainberg, Simon; McCray, John E; Steffan, Robert J

    2010-07-01

    Laboratory experiments were performed in discretely fractured sandstone blocks to evaluate the use of bioaugmentation to treat residual dense non-aqueous phase liquid (DNAPL) tetrachloroethene (PCE). Significant dechlorination of PCE and growth of Dehalococcoides spp. (DHC) occurred within the fractures. DNAPL dissolution was enhanced during bioaugmentation by up to a factor of approximately 3.5, with dissolved PCE concentrations at or near aqueous solubility. The extent of dechlorination and DNAPL dissolution enhancement were dependent upon the fracture characteristics, residence time in the fractures, and dissolved concentration of PCE. No relationship was observed between planktonic DHC concentrations exiting the fracture and the observed extents of PCE dechlorination and DNAPL dissolution. Measured planktonic DHC concentrations exiting the fracture increased with increasing flow rate and bioaugmentation dosage, suggesting that these parameters may be important for distribution of DHC to treat dissolved chlorinated ethenes migrating downgradient of the DNAPL source. Bioaugmentation dosage, for the DHC dosages and conditions studied, did not have a measurable impact on DNAPL dissolution or dechlorination within the fractures themselves. Overall, these results indicate that bioaugmentation may be a viable remedial option for treating DNAPL sources in bedrock.

  2. A theory of the chain melting phase transition of aqueous phospholipid dispersions.

    PubMed Central

    Jacobs, R E; Hudson, B; Andersen, H C

    1975-01-01

    A model for the chain melting phase transition in dilute aqueous phospholipid bilayer dispersions is presented. This model includes interactions between head groups, between hydrocarbon chains, and within the chains. The head groups are modeled as hard disks which are constrained to lie on a two-dimensional surface separating the aqueous and hydrocarbon regions. The chain statistics problem is treated in an approximate manner using an approach motivated by scaled particle theory to describe the inter-chain steric repulsions in a mathematically tractable way. In this approach the whole system interacts with any given chain through an average lateral pressure which is proportional to the hard disk pressure. Following Nagle, we assume that the steric repulsions between chains and between head groups and the trans-gauche rotation energies are the dominant interactions in determining the transition and we describe the effect of the other interactions with a mean field approximation. Using the known transition temperature of a series of 1,2-diacyl phosphatidyl cholines to adjust two parameters in the theory, the model gives enthalpy and area changes that are in quite reasonable agreement with experiment. Moreover, the curvature observed in the plot of the transition temperature against acyl chain length is reproduced. PMID:1060080

  3. Prediction of contaminant persistence in aqueous phase: a quantum chemical approach.

    PubMed

    Blotevogel, Jens; Mayeno, Arthur N; Sale, Tom C; Borch, Thomas

    2011-03-15

    At contaminated field sites where active remediation measures are not feasible, monitored natural attenuation is sometimes the only alternative for surface water or groundwater decontamination. However, due to slow degradation rates of some contaminants under natural conditions, attenuation processes and their performance assessment can take several years to decades to complete. Here, we apply quantum chemical calculations to predict contaminant persistence in the aqueous phase. For the test compound hexamethylphosphoramide (HMPA), P-N bond hydrolysis is the only thermodynamically favorable reaction that may lead to its degradation under reducing conditions. Through calculation of aqueous Gibbs free energies of activation for all potential reaction mechanisms, it is predicted that HMPA hydrolyzes via an acid-catalyzed mechanism at pH < 8.2, and an uncatalyzed mechanism at pH 8.2-8.5. The estimated half-lives of thousands to hundreds of thousands of years over the groundwater-typical pH range of 6.0 to 8.5 indicate that HMPA will be persistent in the absence of suitable oxidants. At pH 0, where the hydrolysis reaction is rapid enough to enable measurement, the experimentally determined rate constant and half-life are in excellent agreement with the predicted values. Since the quantum chemical methodology described herein can be applied to virtually any contaminant or reaction of interest, it is especially valuable for the prediction of persistence when slow reaction rates impede experimental investigations and appropriate QSARs are unavailable.

  4. The effect of surfactant and solid phase concentration on drug aggregates in model aerosol propellent suspensions.

    PubMed

    Bower, C; Washington, C; Purewal, T S

    1996-04-01

    The effect of increasing solid phase concentration on the morphology and flocculation rate of model aerosol suspensions has been investigated. Suspensions of micronized salbutamol sulphate and lactose in trichlorotrifluoroethane (P113) were studied under conditions of increasing shear stress. By use of image analysis techniques, measurement of aggregate size, fractal dimension and rate of aggregation was performed. The effect of the surfactant sorbitan monooleate on morphology and flocculation rate was also studied. Increased solid phase concentration caused an increase in the rate of aggregation and average aggregate size at a given value of shear stress. Surfactant addition retarded the aggregation rate, and caused a shift from a diffusion-limited cluster aggregation to a reaction-limited cluster aggregation mechanism. The aggregate profiles showed a corresponding change from rugged and crenellated without surfactant, to increasingly smooth and Euclidian with increasing surfactant concentration. The morphological changes were characterized by a decrease in the average boundary fractal dimension which also correlated well with the corresponding reduction in aggregation rate.

  5. Interference of salts used on aqueous two-phase systems on the quantification of total proteins.

    PubMed

    Golunski, Simone Maria; Sala, Luisa; Silva, Marceli Fernandes; Dallago, Rogério Marcos; Mulinari, Jéssica; Mossi, Altemir José; Brandelli, Adriano; Kalil, Susana Juliano; Di Luccio, Marco; Treichel, Helen

    2016-02-01

    In this study the interference of potassium phosphate, sodium citrate, sodium chloride and sodium nitrate salts on protein quantification by Bradford's method was assessed. Potassium phosphate and sodium citrate salts are commonly used in aqueous two-phase systems for enzyme purification. Results showed that the presence of potassium phosphate and sodium citrate salts increase the absorbance of the samples, when compared with the samples without any salt. The increase in absorptivity of the solution induces errors on protein quantification, which are propagated to the calculations of specific enzyme activity and consequently on purification factor. The presence of sodium chloride and sodium nitrate practically did not affect the absorbance of inulinase, probably the metals present in the enzyme extract did not interact with the added salts.

  6. Purification of aloe polysaccharides by using aqueous two-phase extraction with desalination.

    PubMed

    Xing, Jian-Min; Li, Fen-Fang

    2009-01-01

    A PEG6000/(NH4)2SO4 aqueous two-phase system was chosen as the separation system. The effects of NaCl, Gu(SCN)2 and pH on the partitioning of aloe polysaccharide and bovine serum albumin (BSA) were studied. The result shows that the recovery of aloe polysaccharide was decreased with the increase in pH and the recovery of protein was not changed; NaCl and Gu(SCN)2 can change the partitioning behaviour of the BSA. The separation of BSA and aloe polysaccharides was also carried out. Then, the aloe polysaccharides were obtained by using ultrafiltration membrane. The composition of the polysaccharides was analysed by gas chromatography. The results show that mannose is mainly monosaccharide, and it only contains a few glucose.

  7. Characterization of aqueous phase from the hydrothermal liquefaction of Chlorella pyrenoidosa.

    PubMed

    Gai, Chao; Zhang, Yuanhui; Chen, Wan-Ting; Zhou, Yan; Schideman, Lance; Zhang, Peng; Tommaso, Giovana; Kuo, Chih-Ting; Dong, Yuping

    2015-05-01

    This study investigated the characteristics of aqueous phase from hydrothermal liquefaction of low-lipid microalgae Chlorella pyrenoidosa. The interactions of operating conditions, including reaction temperature, retention time and total solid ratio were evaluated by response surface methodology. The chemical oxygen demand, total nitrogen and total phosphorus were selected as indicators of the property of AP. Results indicated that total solid ratio was found to be the dominant factor affecting the nutrient recovery efficiencies of AP. Based on energy recovery, GC-MS indicated that the AP at two optimized operating conditions (280 °C, 60 min, 35 wt.% and 300 °C, 60 min, 25 wt.%) were observed to have a higher concentration of organic acids (10.35% and 8.34%) while the sample (260 °C, 30 min, 35 wt.%) was observed to have the highest concentration of N&O-heterocyclic compounds (36.16%).

  8. Advection dispersion mass transport associated with a non-aqueous-phase liquid pool

    NASA Astrophysics Data System (ADS)

    Fyrillas, Marios M.

    2000-06-01

    The two-dimensional problem of advection dispersion associated with a non-aqueous-phase liquid (NAPL) pool is addressed using the boundary element method. The problem is appropriately posed with an inhomogeneous boundary condition taking into consideration the presence of the pool and the impermeable layer. We derive a Fredholm integral equation of the first kind for the concentration gradient along the pool location and compute the average mass transfer coefficient numerically using the boundary-element method. Numerical results are in agreement with asymptotic analytical solutions obtained for the cases of small and large Péclet number (Pex). The asymptotic solution for small Pex, which is obtained by applying a novel perturbation technique to the integral equation, is used to de-singularize the integral equation. Results predicted by this analysis are in good agreement with experimentally determined overall mass transfer coefficients.

  9. Aqueous phase reforming of glycerol over Ni-based catalysts for hydrogen production.

    PubMed

    Cho, Su Hyun; Moon, Dong Ju

    2011-08-01

    Aqueous phase reforming of glycerol over Ni-based catalysts for hydrogen production was carried out at 225 degrees C, 23 bar and LHSV = 4 h(-1). The Ni-based catalyst was prepared by an incipient wetness impregnation method. The catalysts before and after the reaction were characterized by N2 physisorption, CO chemisorption, XRD, TPR, SEM and TEM techniques. It was found that Ni(20 wt%)-Co(3 wt%)/gamma-Al2O3 catalyst showed higher glycerol conversion and hydrogen selectivity than Ni(20 wt%)/gamma-Al2O3 catalyst. There are no major changes in Ni particles after the reaction over Ni-Co/gamma-Al2O3 catalyst. The results suggest that the Ni-Co/gamma-Al2O3 catalyst can be applied to the hydrogen production system using APR of glycerol. PMID:22103184

  10. Volumetric monitoring of aqueous two phase system droplets using time-lapse optical coherence tomography

    NASA Astrophysics Data System (ADS)

    Lee, J.; Bathany, C.; Ahn, Y.; Takayama, S.; Jung, W.

    2016-02-01

    We present a volumetric monitoring method to observe the morphological changes of aqueous two phase system (ATPS) droplets in a microfluidic system. Our method is based on time-lapse optical coherence tomography (OCT) which allows the study of the dynamics of ATPS droplets while visualizing their 3D structures and providing quantitative information on the droplets. In this study, we monitored the process of rehydration and deformation of an ATPS droplet in a microfluidic system and quantified the changes of its volume and velocity under both static and dynamic fluid conditions. Our results indicate that time-lapse OCT is a very promising tool to evaluate the unprecedented features of droplet-based microfluidics.

  11. Interference of salts used on aqueous two-phase systems on the quantification of total proteins.

    PubMed

    Golunski, Simone Maria; Sala, Luisa; Silva, Marceli Fernandes; Dallago, Rogério Marcos; Mulinari, Jéssica; Mossi, Altemir José; Brandelli, Adriano; Kalil, Susana Juliano; Di Luccio, Marco; Treichel, Helen

    2016-02-01

    In this study the interference of potassium phosphate, sodium citrate, sodium chloride and sodium nitrate salts on protein quantification by Bradford's method was assessed. Potassium phosphate and sodium citrate salts are commonly used in aqueous two-phase systems for enzyme purification. Results showed that the presence of potassium phosphate and sodium citrate salts increase the absorbance of the samples, when compared with the samples without any salt. The increase in absorptivity of the solution induces errors on protein quantification, which are propagated to the calculations of specific enzyme activity and consequently on purification factor. The presence of sodium chloride and sodium nitrate practically did not affect the absorbance of inulinase, probably the metals present in the enzyme extract did not interact with the added salts. PMID:26616454

  12. Bromelain purification through unconventional aqueous two-phase system (PEG/ammonium sulphate).

    PubMed

    Coelho, D F; Silveira, E; Pessoa Junior, A; Tambourgi, E B

    2013-02-01

    This paper focuses on the feasibility of unconventional aqueous two-phase systems for bromelain purification from pineapple processing waste. The main difference in comparison with conventional systems is the integration of the liquid-liquid extraction technique with fractional precipitation, which can decrease the protein content with no loss of biological activity by removing of unwanted molecules. The analysis of the results was based on the response surface methodology and revealed that the use of the desirability optimisation methodology (DOM) was necessary to achieve higher purification factor values and greater bromelain recovery. The use of DOM yielded an 11.80-fold purification factor and 66.38 % biological activity recovery using poly(ethylene glycol) (PEG) with a molar mass of 4,000, 10.86 % PEG concentration (m/m) and 36.21 % saturation of ammonium sulphate.

  13. Evaporation kinetics of aqueous acetic acid droplets: effects of soluble organic aerosol components on the mechanism of water evaporation.

    PubMed

    Duffey, Kaitlin C; Shih, Orion; Wong, Nolan L; Drisdell, Walter S; Saykally, Richard J; Cohen, Ronald C

    2013-07-28

    The presence of organic surfactants in atmospheric aerosol may lead to a depression of cloud droplet growth and evaporation rates affecting the radiative properties and lifetime of clouds. Both the magnitude and mechanism of this effect, however, remain poorly constrained. We have used Raman thermometry measurements of freely evaporating micro-droplets to determine evaporation coefficients for several concentrations of acetic acid, which is ubiquitous in atmospheric aerosol and has been shown to adsorb strongly to the air-water interface. We find no suppression of the evaporation kinetics over the concentration range studied (1-5 M). The evaporation coefficient determined for 2 M acetic acid is 0.53 ± 0.12, indistinguishable from that of pure water (0.62 ± 0.09).

  14. Online Investigation of Aqueous-Phase Electrochemical Reactions by Desorption Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Lu, Mei; Liu, Yong; Helmy, Roy; Martin, Gary E.; Dewald, Howard D.; Chen, Hao

    2015-08-01

    Electrochemistry (EC) combined with mass spectrometry (MS) is a powerful tool for elucidation of electrochemical reaction mechanisms. However, direct online analysis of electrochemical reaction in aqueous phase was rarely explored. This paper presents the online investigation of several electrochemical reactions with biological relevance in the aqueous phase, such as nitrosothiol reduction, carbohydrate oxidation, and carbamazepine oxidation using desorption electrospray ionization mass spectrometry (DESI-MS). It was found that electroreduction of nitrosothiols [e.g., nitrosylated insulin B (13-23)] leads to free thiols by loss of NO, as confirmed by online MS analysis for the first time. The characteristic mass shift of 29 Da and the reduced intensity provide a quick way to identify nitrosylated species. Equally importantly, upon collision-induced dissociation (CID), the reduced peptide ion produces more fragment ions than its nitrosylated precursor ion (presumably the backbone fragmentation cannot compete with the facile NO loss for the precursor ion), thus facilitating peptide sequencing. In the case of saccharide oxidation, it was found that glucose undergoes electro-oxidation to produce gluconic acid at alkaline pH, but not at neutral and acidic pHs. Such a pH-dependent electrochemical behavior was also observed for disaccharides such as maltose and cellobiose. Upon electrochemical oxidation, carbamazepine was found to undergo ring contraction and amide bond cleavage, which parallels the oxidative metabolism observed for this drug in leucocytes. The mechanistic information of these redox reactions revealed by EC/DESI-MS would be of value in nitroso-proteome research and carbohydrate/drug metabolic studies.

  15. Confounding effects of aqueous-phase impinger chemistry on apparent oxidation of mercury in flue gases.

    PubMed

    Cauch, Brydger; Silcox, Geoffrey D; Lighty, JoAnn S; Wendt, Jost O L; Fry, Andrew; Senior, Constance L

    2008-04-01

    Gas-phase reactions between elemental mercury and chlorine are a possible pathway to producing oxidized mercury species such as mercuric chloride in combustion systems. This study examines the effect of the chemistry of a commonly used sample conditioning system on apparent and actual levels of mercury oxidation in a methane-fired, 0.3 kW, quartz-lined reactor in which gas composition (HCl, Cl2, NOx, SO2) and quench rate were varied. The sample conditioning system included two impingers in parallel: one containing an aqueous solution of KCl to trap HgCl2, and one containing an aqueous solution of SnCl2 to reduce HgCl2 to elemental mercury (Hg0). Gas-phase concentrations of Cl2 as low as 1.5 ppmv were sufficient to oxidize a significant fraction of the elemental mercury in the KCl impinger via the hypochlorite ion. Furthermore, these low, but interfering levels of Cl2 appeared to persist in flue gases from several doped rapidly mixed flames with varied post flame temperature quench rates. The addition of 0.5 wt% sodium thiosulfate to the KCl solution completely prevented the oxidation from occurring in the impinger. The addition of thiosulfate did not inhibit the KCl impinger's ability to capture HgCl2. The effectiveness of the thiosulfate was unchanged by NO or SO2. These results bring into question laboratory scale experimental data on mercury oxidation where wet chemistry was used to partition metallic and oxidized mercury without the presence of sufficient levels of SO2.

  16. Confounding effects of aqueous-phase impinger chemistry on apparent oxidation of mercury in flue gases

    SciTech Connect

    Brydger Cauch; Geoffrey D. Silcox; Joann S. Lighty; Jost O.L. Wendt; Andrew Fry; Constance L. Senior

    2008-04-01

    Gas-phase reactions between elemental mercury and chlorine are a possible pathway to producing oxidized mercury species such as mercuric chloride in combustion systems. This study examines the effect of the chemistry of a commonly used sample conditioning system on apparent and actual levels of mercury oxidation in a methane-fired, 0.3 kW, quartz-lined reactor in which gas composition (HCl, Cl{sub 2}, NOx, SO{sub 2}) and quench rate were varied. The sample conditioning system included two impingers in parallel: one containing an aqueous solution of KCl to trap HgCl{sub 2}, and one containing an aqueous solution of SnCl{sub 2} to reduce HgCl{sub 2} to elemental mercury (Hg{sup 0}). Gas-phase concentrations of Cl{sub 2} as low as 1.5 ppmv were sufficient to oxidize a significant fraction of the elemental mercury in the KCl impinger via the hypochlorite ion. Furthermore, these low, but interfering levels of Cl{sub 2} appeared to persist in flue gases from several doped rapidly mixed flames with varied post flame temperature quench rates. The addition of 0.5 wt% sodium thiosulfate to the KCl solution completely prevented the oxidation from occurring in the impinger. The addition of thiosulfate did not inhibit the KCl impinger's ability to capture HgCl{sub 2}. The effectiveness of the thiosulfate was unchanged by NO or SO{sub 2}. These results bring into question laboratory scale experimental data on mercury oxidation where wet chemistry was used to partition metallic and oxidized mercury without the presence of sufficient levels of SO{sub 2}. 23 refs., 5 figs., 1 tab.

  17. Optimizing photo-Fenton like process for the removal of diesel fuel from the aqueous phase

    PubMed Central

    2014-01-01

    Background In recent years, pollution of soil and groundwater caused by fuel leakage from old underground storage tanks, oil extraction process, refineries, fuel distribution terminals, improper disposal and also spills during transferring has been reported. Diesel fuel has created many problems for water resources. The main objectives of this research were focused on assessing the feasibility of using photo-Fenton like method using nano zero-valent iron (nZVI/UV/H2O2) in removing total petroleum hydrocarbons (TPH) and determining the optimal conditions using Taguchi method. Results The influence of different parameters including the initial concentration of TPH (0.1-1 mg/L), H2O2 concentration (5-20 mmole/L), nZVI concentration (10-100 mg/L), pH (3-9), and reaction time (15-120 min) on TPH reduction rate in diesel fuel were investigated. The variance analysis suggests that the optimal conditions for TPH reduction rate from diesel fuel in the aqueous phase are as follows: the initial TPH concentration equals to 0.7 mg/L, nZVI concentration 20 mg/L, H2O2 concentration equals to 5 mmol/L, pH 3, and the reaction time of 60 min and degree of significance for the study parameters are 7.643, 9.33, 13.318, 15.185 and 6.588%, respectively. The predicted removal rate in the optimal conditions was 95.8% and confirmed by data obtained in this study which was between 95-100%. Conclusion In conclusion, photo-Fenton like process using nZVI process may enhance the rate of diesel degradation in polluted water and could be used as a pretreatment step for the biological removal of TPH from diesel fuel in the aqueous phase. PMID:24955242

  18. Online Investigation of Aqueous-Phase Electrochemical Reactions by Desorption Electrospray Ionization Mass Spectrometry.

    PubMed

    Lu, Mei; Liu, Yong; Helmy, Roy; Martin, Gary E; Dewald, Howard D; Chen, Hao

    2015-10-01

    Electrochemistry (EC) combined with mass spectrometry (MS) is a powerful tool for elucidation of electrochemical reaction mechanisms. However, direct online analysis of electrochemical reaction in aqueous phase was rarely explored. This paper presents the online investigation of several electrochemical reactions with biological relevance in the aqueous phase, such as nitrosothiol reduction, carbohydrate oxidation, and carbamazepine oxidation using desorption electrospray ionization mass spectrometry (DESI-MS). It was found that electroreduction of nitrosothiols [e.g., nitrosylated insulin B (13-23)] leads to free thiols by loss of NO, as confirmed by online MS analysis for the first time. The characteristic mass shift of 29 Da and the reduced intensity provide a quick way to identify nitrosylated species. Equally importantly, upon collision-induced dissociation (CID), the reduced peptide ion produces more fragment ions than its nitrosylated precursor ion (presumably the backbone fragmentation cannot compete with the facile NO loss for the precursor ion), thus facilitating peptide sequencing. In the case of saccharide oxidation, it was found that glucose undergoes electro-oxidation to produce gluconic acid at alkaline pH, but not at neutral and acidic pHs. Such a pH-dependent electrochemical behavior was also observed for disaccharides such as maltose and cellobiose. Upon electrochemical oxidation, carbamazepine was found to undergo ring contraction and amide bond cleavage, which parallels the oxidative metabolism observed for this drug in leucocytes. The mechanistic information of these redox reactions revealed by EC/DESI-MS would be of value in nitroso-proteome research and carbohydrate/drug metabolic studies.

  19. Protein sorption and recovery by hydrogels using principles of aqueous two-phase extraction.

    PubMed

    Gehrke, S H; Vaid, N R; McBride, J F

    1998-05-20

    Use of the thermodynamic principles of aqueous two-phase extraction (ATPE) to drive protein into a crosslinked gel is developed as a protein isolation and separation technique, and as a protein loading technique for drug delivery applications. A PEG/dextran gel system was chosen as a model system because PEG/dextran systems are widely used in aqueous two-phase extraction and dextran gels (Sephadex(R)) are common chromatographic media. The effects of polymer concentrations and molecular weights, salts, and pH on the partitioning of ovalbumin matched ATPE heuristics and data trends. Gel partition coefficients (Cgel/Csolution) increased with increasing PEG molecular weight and concentration and decreasing dextran concentration (increased gel swelling). The addition of PEG to the buffer solution yielded partition coefficients more than an order of magnitude greater than those obtained in systems with buffer alone, or added salt. A combined salt/PEG system yielded an additional order of magnitude increase. For example, when ovalbumin solution (2.3 mg/mL) was equilibrated with Sephadex(R) G-50 at pH 6.75, the partition coefficients were 0.13 in buffer, 0.11 in buffer with 0.22M KI, 2.3 in 12 wt% PEG-10,000 and 32.0 in 12 wt% PEG-10, 000 with 0.22M KI. The effect of anions and cations as well as ionic strength and pH on the partitioning of ovalbumin also matched ATPE heuristics. Using the heuristics established above, partition coefficients as high as 80 for bovine serum albumin and protein recoveries over 90% were achieved. In addition, the wide range of partition coefficients that were obtained for different proteins suggests the potential of the technique for separating proteins. Also, ovalbumin sorption capacities in dextran were as high as 450 mg/g dry polymer, and the sorption isotherms were linear over a broad protein concentration range.

  20. Nanoconfinement of pyrene in mesostructured silica nanoparticles for trace detection of TNT in the aqueous phase

    NASA Astrophysics Data System (ADS)

    Beyazkilic, Pinar; Yildirim, Adem; Bayindir, Mehmet

    2014-11-01

    This article describes the preparation of pyrene confined mesostructured silica nanoparticles for the trace detection of trinitrotoluene (TNT) in the aqueous phase. Pyrene confined mesostructured silica nanoparticles were prepared using a facile one-pot method where pyrene molecules were first encapsulated in the hydrophobic parts of cetyltrimethylammonium micelles and then silica polymerized around these micelles. The resulting hybrid particles have sizes of around 75 nm with fairly good size distribution. Also, they are highly dispersible and colloidally stable in water. More importantly, they exhibit bright and highly stable pyrene excimer emission. We demonstrated that excimer emission of the particles exhibits a rapid, sensitive and visual quenching response against TNT. The detection limit for TNT was determined to be 12 nM. Furthermore, excimer emission of pyrene shows significantly high selectivity for TNT.This article describes the preparation of pyrene confined mesostructured silica nanoparticles for the trace detection of trinitrotoluene (TNT) in the aqueous phase. Pyrene confined mesostructured silica nanoparticles were prepared using a facile one-pot method where pyrene molecules were first encapsulated in the hydrophobic parts of cetyltrimethylammonium micelles and then silica polymerized around these micelles. The resulting hybrid particles have sizes of around 75 nm with fairly good size distribution. Also, they are highly dispersible and colloidally stable in water. More importantly, they exhibit bright and highly stable pyrene excimer emission. We demonstrated that excimer emission of the particles exhibits a rapid, sensitive and visual quenching response against TNT. The detection limit for TNT was determined to be 12 nM. Furthermore, excimer emission of pyrene shows significantly high selectivity for TNT. Electronic supplementary information (ESI) available: Additional figures. See DOI: 10.1039/c4nr05514d

  1. Gas-phase removal of biofilms from various surfaces using carbon dioxide aerosols.

    PubMed

    Cha, Minju; Hong, Seongkyeol; Kang, Min-Yeong; Lee, Jin-Won; Jang, Jaesung

    2012-01-01

    The present study evaluated the removal of Escherichia coli XL1-blue biofilms using periodic jets of carbon dioxide aerosols (a mixture of solid and gaseous CO(2)) with nitrogen gas. The aerosols were generated by the adiabatic expansion of high-pressure CO(2) gas through a nozzle and used to remove air-dried biofilms. The areas of the biofilms were measured from scanning electron micrographs before and after applying the aerosols. The removal efficiency of the aerosol treatment was measured with various air-drying times of the biofilms before the treatment, surface materials, and durations of CO(2) aerosols in each 8-s aerosol-nitrogen cleaning cycle. Nearly 100% of the fresh biofilms were removed from the various surfaces very reliably within 90 s. This technique can be useful for removing unsaturated biofilms on solid surfaces and has potential applications for cleaning bio-contaminated surfaces.

  2. Directing carbon nanotubes from aqueous phase to o/w interface for heavy metal uptaking.

    PubMed

    Gao, Lili; Yin, Huayi; Mao, Xuhui; Zhu, Hua; Xiao, Wei; Wang, Dihua

    2015-09-01

    Separation and reuse of dispersed nanoparticles are major obstacles to the extensive application of nano-sized absorbents in wastewater treatment. Herein, we demonstrate the capability of directing acid-oxidized carbon nanotubes (CNTs) as the transfer vehicles of heavy metal ions from simulated wastewater. The heavy metal-loaded CNTs can be readily separated from the aqueous phase via the aggregation process at an oil/water (o/w) interface. The minimum surfactant amount to achieve 99 % transfer ratio (Tr) of 100 mg/L CNTs from water phase to o/w interface was ∼0.01 mM. The adsorption experiments showed that the removal efficiency of the divalent lead ions increased with an increase in CNT mass, and the subsequent addition of cetyltrimethylammonium bromide (CTAB) surfactant did not negatively impact the removal of soluble divalent lead species (Pb(II)). In a wide region of pH and ionic strength, both the decontamination of Pb(II) and the transfer of CNTs from water phase to o/w interface can be accomplished successively. The method presented in this study may be developed as a generic one for collecting or recycling the pollutant-loaded nano-sized absorbents.

  3. Directing carbon nanotubes from aqueous phase to o/w interface for heavy metal uptaking.

    PubMed

    Gao, Lili; Yin, Huayi; Mao, Xuhui; Zhu, Hua; Xiao, Wei; Wang, Dihua

    2015-09-01

    Separation and reuse of dispersed nanoparticles are major obstacles to the extensive application of nano-sized absorbents in wastewater treatment. Herein, we demonstrate the capability of directing acid-oxidized carbon nanotubes (CNTs) as the transfer vehicles of heavy metal ions from simulated wastewater. The heavy metal-loaded CNTs can be readily separated from the aqueous phase via the aggregation process at an oil/water (o/w) interface. The minimum surfactant amount to achieve 99 % transfer ratio (Tr) of 100 mg/L CNTs from water phase to o/w interface was ∼0.01 mM. The adsorption experiments showed that the removal efficiency of the divalent lead ions increased with an increase in CNT mass, and the subsequent addition of cetyltrimethylammonium bromide (CTAB) surfactant did not negatively impact the removal of soluble divalent lead species (Pb(II)). In a wide region of pH and ionic strength, both the decontamination of Pb(II) and the transfer of CNTs from water phase to o/w interface can be accomplished successively. The method presented in this study may be developed as a generic one for collecting or recycling the pollutant-loaded nano-sized absorbents. PMID:25966885

  4. Molecular features determining different partitioning patterns of papain and bromelain in aqueous two-phase systems.

    PubMed

    Rocha, Maria Victoria; Nerli, Bibiana Beatriz

    2013-10-01

    The partitioning patterns of papain (PAP) and bromelain (BR), two well-known cysteine-proteases, in polyethyleneglycol/sodium citrate aqueous two-phase systems (ATPSs) were determined. Polyethyleneglycols of different molecular weight (600, 1000, 2000, 4600 and 8000) were assayed. Thermodynamic characterization of partitioning process, spectroscopy measurements and computational calculations of protein surface properties were also carried out in order to explain their differential partitioning behavior. PAP was observed to be displaced to the salt-enriched phase in all the assayed systems with partition coefficients (KpPAP) values between 0.2 and 0.9, while BR exhibited a high affinity for the polymer phase in systems formed by PEGs of low molecular weight (600 and 1000) with partition coefficients (KpBR) values close to 3. KpBR values resulted higher than KpPAP in all the cases. This difference could be assigned neither to the charge nor to the size of the partitioned biomolecules since PAP and BR possess similar molecular weight (23,000) and isoelectric point (9.60). The presence of highly exposed tryptophans and positively charged residues (Lys, Arg and His) in BR molecule would be responsible for a charge transfer interaction between PEG and the protein and, therefore, the uneven distribution of BR in these systems.

  5. Optimization of pancreatic trypsin extraction in PEG/citrate aqueous two-phase systems.

    PubMed

    Pérez, Rocío L; Loureiro, Dana B; Nerli, Bibiana B; Tubio, Gisela

    2015-02-01

    Enzyme extraction using aqueous two-phase systems (ATPS) has been increasingly used as a primary recovery technique which integrates the clarification, concentration and partial purification of important biomolecules from their natural source in a single step. The goal of this work was to optimize the extraction of trypsin from pancreas homogenate with polyethylene glycol and sodium citrate (PEG/NaCit) ATPS by using the tools of experimental design. The variables NaCl concentration - added inert salt -, the top/bottom phase volume ratio - Vr - and the biomass loaded into the system - in percentage - were selected as the main factors in the trypsin extraction. The yield (%) and the purification factor of trypsin were considered the responses to be optimized. The central composite design and the response surface analysis proved to be suitable tools for a quick and efficient study. As a result, the optimal extraction conditions in PEG3350/NaCit system were 3.34% wt/wt for NaCl concentration, a biomass load which represented 9.30% wt/wt of the total ATPS mass and 6.37 top/bottom volume ratio giving a purification factor of 2.55 and a yield of 99.7% in top phase.

  6. A novel procedure for phase separation in dispersive liquid-liquid microextraction based on solidification of the aqueous phase.

    PubMed

    March, J G; Cerdà, V

    2016-08-15

    In this paper, an alternative for handling the organic phase after a dispersive liquid-liquid microextraction using organic solvents lighter than water is presented. It is based on solidification (at -18°C) of the aqueous phase obtained after centrifugation, and the decantation, collection and analysis of the liquid organic layer. The extraction of nicotine in toluene, and its determination in eggplant samples was conducted as a proof of concept. The study has been carried out using standards prepared in water and the formation of the dispersion was assisted by sonication. The organic extract was analysed using gas chromatography coupled to mass spectrometry. Satisfactory analytical figures of merit as: limit of detection (0.4µgL(-1), 2ngg(-1) wet sample), limit of quantification (1.2µgL(-1), 6.5ngg(-1) wet sample), within-day precision (RSD=7%), and linearity interval (up to 384µgL(-1) nicotine) were achieved. It constituted a contribution to the handling of organic extracts after microextraction processes. PMID:27260454

  7. Design of a microfluidic platform for monoclonal antibody extraction using an aqueous two-phase system.

    PubMed

    Silva, D F C; Azevedo, A M; Fernandes, P; Chu, V; Conde, J P; Aires-Barros, M R

    2012-08-01

    The use of monoclonal antibodies (mAbs) in medical treatments and in laboratory techniques has a very important impact in the battle against many diseases, namely in the treatment of cancer, autoimmune diseases and neural disorders. Thus these biopharmaceuticals have become increasingly important, reinforcing the demand for efficient, scalable and cost-effective techniques for providing pure antibodies. Aqueous two-phase systems (ATPS) have shown potential for downstream processing of mAbs. In this work, an ATPS in a microfluidic platform was designed and tested for mAbs extraction. The system demonstrated the potential to be an effective tool to accelerate bioprocess design and optimization. The partition of immunoglobulin G (IgG) tagged with fluorescein isothiocyanate (FITC) in an ATPS of polyethylene-glycol (PEG)/phosphate buffer with NaCl was investigated using a PDMS microfluidic device fabricated using soft lithography techniques. Different structures were tested with different values of microchannel length (3.14-16.8 cm) and flow rates of the salt (1-2 μL/min) and PEG-rich phases (0.2-0.5 μL/min). A stable interphase between the phases was obtained and the phenomena of diffusion and of partition of the IgG from the salt-rich phase to the PEG-rich phase were measured by fluorescence microscopy. Process simulation allowed the modeling of the IgG diffusion and partitioning behavior observed in the microstructure. The reduction to the microscale does not greatly affect the antibody extraction yield when compared with macroscale results, but it does reduce the operation time, demonstrating the potentiality of this approach to process optimization. PMID:22742897

  8. Ion Partitioning at the liquid/vapor interface of a multi-component alkali halidesolution: A model for aqueous sea salt aerosols

    SciTech Connect

    Ghosal, Sutapa; Brown, Matthew A.; Bluhm, Hendrik; Krisch, Maria J.; Salmeron, Miquel; Jungwirth, Pavel; Hemminger, John C.

    2008-12-22

    The chemistry of Br species associated with sea salt ice and aerosols has been implicated in the episodes of ozone depletion reported at Arctic sunrise. However, Br{sup -} is only a minor component in sea salt, which has a Br{sup -}/Cl{sup -} molar ratio of {approx}0.0015. Sea salt is a complex mixture of many different species, with NaCl as the primary component. In recent years experimental and theoretical studies have reported enhancement of the large, more polarizable halide ion at the liquid/vapor interface of corresponding aqueous alkali halide solutions. The proposed enhancement is likely to influence the availability of sea salt Br{sup -} for heterogeneous reactions such as those involved in the ozone depletion episodes. We report here ambient pressure x-ray photoelectron spectroscopy studies and molecular dynamics simulations showing direct evidence of Br{sup -} enhancement at the interface of an aqueous NaCl solution doped with bromide. The experiments were carried out on samples with Br{sup -}/Cl{sup -} ratios in the range 0.1% to 10%, the latter being also the ratio for which simulations were carried out. This is the first direct measurement of interfacial enhancement of Br{sup -} in a multi-component solution with particular relevance to sea salt chemistry.

  9. Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures

    NASA Astrophysics Data System (ADS)

    Kanno, H.; Kajiwara, K.; Miyata, K.

    2010-05-01

    Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for TH (homogeneous ice nucleation temperature) and Tm (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the TH curve for a DMSO solution of R =20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at Pc2=˜200 MPa and at Tc2<-100 °C (Pc2: pressure of SCP, Tc2: temperature of SCP). The presence of two TH peaks for DMSO solutions (R =15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R ≤15) at high pressures and low temperatures (<-90 °C). The pressure dependence of the two TH curves for DMSO solutions of R =10 and 12 indicates that the two phase-separated components in the DMSO solution of R =10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

  10. Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures.

    PubMed

    Kanno, H; Kajiwara, K; Miyata, K

    2010-05-21

    Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for T(H) (homogeneous ice nucleation temperature) and T(m) (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the T(H) curve for a DMSO solution of R=20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at P(c2)= approximately 200 MPa and at T(c2)<-100 degrees C (P(c2): pressure of SCP, T(c2): temperature of SCP). The presence of two T(H) peaks for DMSO solutions (R=15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (Rphase-separated components in the DMSO solution of R=10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

  11. Low-abundant protein extraction from complex protein sample using a novel continuous aqueous two-phase systems device.

    PubMed

    Vázquez-Villegas, Patricia; Espitia-Saloma, Edith; Rito-Palomares, Marco; Aguilar, Oscar

    2013-01-01

    The present work describes the application of a novel continuous aqueous two-phase system prototype for the recovery of biomolecules. The prototype is an alternative platform for protein recovery and α-amylase from soybean extracts was used as a model system. The system was selected as an example of low-abundant protein present in complex mixtures. Compared with batch systems, continuous operation in this prototype seems to increase partition coefficient with higher recovery efficiencies. Processing time is reduced at least three times in the continuous system when compared to batch mode, while hold up (volumetric quantity of the opposing phase in a determined phase sample) decreases with decreasing phases flow. Furthermore, similar partition coefficient (Kp > 4) with a higher top phase enzyme recovery (81%) is also obtained in this system probably due to better contact surface between phases, compared with that obtained in batch (79%). A continuous aqueous two-phase system process with purification factor 40-fold higher than batch experiments was achieved. These preliminary results exhibit the potential of continuous systems for the recovery of low-abundant proteins from complex mixtures. The promising performance of this prototype can raise the attention of the industry for the adoption of aqueous two-phase system processes.

  12. Aqueous two-phase partition applied to the isolation of plasma membranes and Golgi apparatus from cultured mammalian cells

    NASA Technical Reports Server (NTRS)

    Morre, D. M.; Morre, D. J.

    2000-01-01

    Partitioning in dextran-poly(ethylene)glycol (PEG) aqueous-aqueous phase systems represents a mature technology with many applications to separations of cells and to the preparation of membranes from mammalian cells. Most applications to membrane isolation and purification have focused on plasma membranes, plasma membrane domains and separation of right side-out and inside-out plasma membrane vesicles. The method exploits a combination of membrane properties, including charge and hydrophobicity. Purification is based upon differential distributions of the constituents in a sample between the two principal compartments of the two phases (upper and lower) and at the interface. The order of affinity of animal cell membranes for the upper phase is: endoplasmic reticulum aqueous two-phase partition with other procedures to obtain a more highly purified preparation. A procedure is described for preparation of Golgi apparatus from transformed mammalian cells that combines aqueous two-phase partition and centrifugation. Also described is a periodic NADH oxidase, a new enzyme marker for right side-out plasma membrane vesicles not requiring detergent disruptions for measurement of activity.

  13. THE EFFECT OF METASTABLE EQUILIBRIUM STATES ON THE PARTITIONING OF NITRATE BETWEEN THE GAS AND AEROSOL PHASES. (R826371C005)

    EPA Science Inventory

    With the aid of three atmospheric aerosol equilibrium models, we quantify the effect of metastable equilibrium states (efflorescence branch) in comparison to stable (deliquescence branch) on the partitioning of total nitrate between the gas and aerosol phases. On average, effl...

  14. An observational approach for determining aerosol surface radiative forcing: Results from the first field phase of INDOEX

    NASA Astrophysics Data System (ADS)

    Conant, William C.

    2000-06-01

    This paper presents one of the few quantitative estimates of surface aerosol forcing made directly from surface irradiance observations. The method described within yields estimates of the forcing accurate to 20%. The study was conducted from February to March 1998 at the Kaashidhoo Climate Observatory (KCO) during the First Field Phase of the Indian Ocean Experiment (INDOEX-FFP). For the 400-700 nm region studied here, the forcing is -7.6±1.5 W m-2. The data are obtained from two photodiode radiometers measuring global and diffuse irradiance in five channels in the visible and ultraviolet. The instruments were chosen, calibrated, and deployed specifically for a precise measurement of aerosol forcing. The angular, spectral, and absolute response characteristics of the instruments are determined in the laboratory and used to calibrate the data, as described here. The accuracy in the calibrated data is 2.4% for the global irradiance and 1.8% for the diffuse irradiance. Direct aerosol forcing is obtained from the measured aerosol forcing efficiency, which is determined by two methods: hybrid and differential. The hybrid method uses a radiative transfer model to subtract out the contribution from the aerosol-free atmosphere. The differential method assumes that changes in 400-700 nm solar flux are forced by changes in aerosol optical depth. By using flux changes, the differential method is not sensitive to the small calibration uncertainties, and is independent of model assumptions about the single-scatter properties of the aerosol. For this soot-laden marine region south of India, a 0.1 change in aerosol optical depth produces a -4.0±0.8 W m-2; change in the 400-700 nm surface flux; 55% of this forcing is observed in the 400-540 nm region. The global and diffuse data agree to within 5 W m-2 of results calculated by a Monte Carlo radiative transfer model. The model assumes an aerosol consistent with the spectral optical depth, lidar vertical profiles, and surface

  15. Phase behavior of ABC-type triple-hydrophilic block copolymers in aqueous solutions.

    PubMed

    Zheng, Lingfei; Wu, Jianqi; Wang, Zheng; Yin, Yuhua; Jiang, Run; Li, Baohui

    2016-07-01

    The phase behavior of symmetric ABC triple-hydrophilic triblock copolymers in concentrated aqueous solutions is investigated using a simulated annealing technique. Two typical cases, in which the hydrophilicity of the middle B-block is either stronger or weaker than that of the end A- and C-blocks, are studied. In these two cases, a variety of phase diagrams are constructed as a function of the volume fraction of the B-block and the copolymer concentration ([Formula: see text] for both non-frustrated and frustrated copolymers. Structures, such as two-color alternatingly packed cylinders or gyroid, and lamellae-in-lamellae etc. that do not occur in the melt system, are obtained in solutions. Rich phase transition sequences, especially re-entrant phase transitions involving complex continuous networks of alternating gyroid and alternating diamond are observed for a given copolymer with decreasing [Formula: see text] . The difference in hydrophilicity among different blocks can result in inhomogeneous distribution of solvent molecules in the morphology, and with the decrease of [Formula: see text] , the distribution of solvent molecules presents a non-monotonic variation. This results in a non-monotonic variation of the effective volume fraction of each domain with the decrease of [Formula: see text] , which induces the re-entrant phase transitions. The presence of a good solvent for all the blocks can cause changes in the effective segregation strengths between different blocks and also in chain conformations, hence can alter the bulk phases and results in the occurrence of new structures and phase transitions. Especially, structures having A-C interfaces or A-C mixed domains can be obtained even in the non-frustrated copolymer systems, and structures obtained in the frustrated systems may be similar to those obtained in the non-frustrated systems. The window of the alternating gyroid structures may occupy a large part of the phase diagram for non

  16. Analysis of partitioning of organic compounds and proteins in aqueous polyethylene glycol-sodium sulfate aqueous two-phase systems in terms of solute-solvent interactions.

    PubMed

    da Silva, Nuno R; Ferreira, Luisa A; Madeira, Pedro P; Teixeira, José A; Uversky, Vladimir N; Zaslavsky, Boris Y

    2015-10-01

    Partition behavior of nine small organic compounds and six proteins was examined in poly(ethylene glycol)-8000-sodium sulfate aqueous two-phase systems containing 0.5M osmolyte (sorbitol, sucrose, trehalose, TMAO) and poly(ethylene glycol)-10000-sodium sulfate system, all in 0.01M sodium phosphate buffer, pH 6.8. The differences between the solvent properties of the coexisting phases (solvent dipolarity/polarizability, hydrogen bond donor acidity, and hydrogen bond acceptor basicity) were characterized with solvatochromic dyes using the solvatochromic comparison method. Differences between the electrostatic properties of the phases were determined by analysis of partitioning of sodium salts of dinitrophenylated (DNP-) amino acids with aliphatic alkyl side-chain. It was found out that the partition coefficient of all compounds examined (including proteins) may be described in terms of solute-solvent interactions. The results obtained in the study show that solute-solvent interactions of nonionic organic compounds and proteins in polyethylene glycol-sodium sulfate aqueous two-phase system differ from those in polyethylene glycol-dextran system. PMID:26342872

  17. Evaporation kinetics and phase of laboratory and ambient secondary organic aerosol.

    PubMed

    Vaden, Timothy D; Imre, Dan; Beránek, Josef; Shrivastava, Manish; Zelenyuk, Alla

    2011-02-01

    Field measurements of secondary organic aerosol (SOA) find significantly higher mass loads than predicted by models, sparking intense effort focused on finding additional SOA sources but leaving the fundamental assumptions used by models unchallenged. Current air-quality models use absorptive partitioning theory assuming SOA particles are liquid droplets, forming instantaneous reversible equilibrium with gas phase. Further, they ignore the effects of adsorption of spectator organic species during SOA formation on SOA properties and fate. Using accurate and highly sensitive experimental approach for studying evaporation kinetics of size-selected single SOA particles, we characterized room-temperature evaporation kinetics of laboratory-generated α-pinene SOA and ambient atmospheric SOA. We found that even when gas phase organics are removed, it takes ∼24 h for pure α-pinene SOA particles to evaporate 75% of their mass, which is in sharp contrast to the ∼10 min time scale predicted by current kinetic models. Adsorption of "spectator" organic vapors during SOA formation, and aging of these coated SOA particles, dramatically reduced the evaporation rate, and in some cases nearly stopped it. Ambient SOA was found to exhibit evaporation behavior very similar to that of laboratory-generated coated and aged SOA. For all cases studied in this work, SOA evaporation behavior is nearly size-independent and does not follow the evaporation kinetics of liquid droplets, in sharp contrast with model assumptions. The findings about SOA phase, evaporation rates, and the importance of spectator gases and aging all indicate that there is need to reformulate the way SOA formation and evaporation are treated by models.

  18. Interference of some aqueous two-phase system phase-forming components in protein determination by the Bradford method.

    PubMed

    Silvério, Sara C; Moreira, Sérgio; Milagres, Adriane M F; Macedo, Eugénia A; Teixeira, José A; Mussatto, Solange I

    2012-02-15

    The interference of some specific aqueous two-phase system (ATPS) phase-forming components in bovine serum albumin (BSA) determination by the Bradford method was investigated. For this purpose, calibration curves were obtained for BSA in the presence of different concentrations of salts and polymers. A total of 19 salts [Na₂SO₄, (NH₄)₂SO₄, MgSO₄, LiSO₄, Na₂HPO₄, sodium phosphate buffer (pH 7.0), NaH₂PO₄, K₂HPO₄, potassium phosphate buffer (pH 7.0), KH₂PO₄, C₆H₈O₇, Na₃C₆H₅O₇, KCHO₂, NaCHO₂, NaCO₃, NaHCO₃, C₂H₄O₂, sodium acetate buffer (pH 4.5), and NaC₂H₃O₂] and 7 polymers [PEG 4000, PEG 8000, PEG 20000, UCON 3900, Ficoll 70000, PES 100000, and PVP 40000] were tested, and each calibration curve was compared with the one obtained for BSA in water. Some concentrations of salts and polymers had considerable effect in the BSA calibration curve. Carbonate salts were responsible for the highest salt interference, whereas citric and acetic acids did not produce interference even in the maximum concentration level tested (5 wt%). Among the polymers, UCON gave the highest interference, whereas Ficoll did not produce interference when used in concentrations up to 10 wt%. It was concluded that a convenient dilution of the samples prior to the protein quantification is needed to ensure no significant interference from ATPS phase-forming constituents.

  19. Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

    NASA Astrophysics Data System (ADS)

    Harris, E.; Sinha, B.; Hoppe, P.; Crowley, J. N.; Ono, S.; Foley, S.

    2011-08-01

    The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemistry of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007) - ((4±5)×10-5) T(°C). The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq=(1.0167±0.0019) - ((8.7±3.5) ×10-5) T(°C). The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilbria of S(IV) in solution, and there was no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.989±0.0043) at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes, and will be particularly useful to determine the importance of the transition-metal catalysed oxidation pathway.

  20. Aqueous phase oligomerization of α,β-unsaturated carbonyls and acids investigated using ion mobility spectrometry coupled to mass spectrometry (IMS-MS)

    NASA Astrophysics Data System (ADS)

    Renard, Pascal; Tlili, Sabrine; Ravier, Sylvain; Quivet, Etienne; Monod, Anne

    2016-04-01

    One of the current essential issues to unravel our ability to forecast future climate change and air quality, implies a better understanding of natural processes leading to secondary organic aerosol (SOA) formation, and in particular the formation and fate of oligomers. The difficulty in characterizing macromolecules is to discern between large oxygenated molecules from series of oligomers containing repeated small monomers of diverse structures. In the present study, taking advantage from previously established radical vinyl oligomerization of methyl vinylketone (MVK) in the aqueous phase, where relatively simple oligomers containing up to 14 monomers were observed, we have investigated the same reactivity on several other unsaturated water soluble organic compounds (UWSOCs) and on a few mixtures of these precursor compounds. The technique used to characterize the formed oligomers was a traveling wave ion mobility spectrometry coupled to a hybrid quadrupole - time of flight mass spectrometer (IMS-MS) fitted with an electrospray source and ultra-high performance liquid chromatography (UPLC). The technique allows for an additional separation, especially for large ions, containing long carbon chains. We have shown the efficiency of the IMS-mass spectrometry technique to detect oligomers derived from MVK photooxidation in the aqueous phase. The results were then compared to other oligomers, derived from ten other individual biogenic UWSOCs. The technique allowed distinguishing between different oligomers arising from different precursors. It also clearly showed that compounds bearing a non-conjugated unsaturation did not provide oligomerization. Finally, it was shown that the IMS-mass spectrometry technique, applied to mixtures of unsaturated conjugated precursors, exhibited the ability of these precursors to co-oligomerize, i.e. forming only one complex oligomer system bearing monomers of different structures. The results are discussed in terms of atmospheric

  1. Near-highway aerosol and gas-phase measurements in a high-diesel environment

    NASA Astrophysics Data System (ADS)

    DeWitt, H. L.; Hellebust, S.; Temime-Roussel, B.; Ravier, S.; Polo, L.; Jacob, V.; Buisson, C.; Charron, A.; André, M.; Pasquier, A.; Besombes, J. L.; Jaffrezo, J. L.; Wortham, H.; Marchand, N.

    2015-04-01

    Diesel-powered passenger cars currently outnumber gasoline-powered cars in many countries, particularly in Europe. In France, diesel cars represented 61% of light duty vehicles in 2011 and this percentage is still increasing (French Environment and Energy Management Agency, ADEME). As part of the September 2011 joint PM-DRIVE (Particulate Matter - DiRect and Indirect on-road Vehicular Emissions) and MOCOPO (Measuring and mOdeling traffic COngestion and POllution) field campaign, the concentration and high-resolution chemical composition of aerosols and volatile organic carbon species were measured adjacent to a major urban highway south of Grenoble, France. Alongside these atmospheric measurements, detailed traffic data were collected from nearby traffic cameras and loop detectors, which allowed the vehicle type, traffic concentration, and traffic speed to be quantified. Six aerosol age and source profiles were resolved using the positive matrix factorization model on real-time high-resolution aerosol mass spectra. These six aerosol source/age categories included a hydrocarbon-like organic aerosol (HOA) commonly associated with primary vehicular emissions, a nitrogen-containing aerosol with a diurnal pattern similar to that of HOA, oxidized organic aerosol (OOA), and biomass burning aerosol. While quantitatively separating the influence of diesel from that of gasoline proved impossible, a low HOA : black carbon ratio, similar to that measured in other high-diesel environments, and high levels of NOx, also indicative of diesel emissions, were observed. Although the measurement site was located next to a large source of primary emissions, which are typically found to have low oxygen incorporation, OOA was found to comprise the majority of the measured organic aerosol, and isotopic analysis showed that the measured OOA contained mainly modern carbon, not fossil-derived carbon. Thus, even in this heavily vehicular-emission-impacted environment, photochemical processes

  2. [Phase transfer catalyzed bioconversion of penicillin G to 6-APA by immobilized penicillin acylase in recyclable aqueous two-phase systems with light/pH sensitive copolymers].

    PubMed

    Jin, Ke-ming; Cao, Xue-jun; Su, Jin; Ma, Li; Zhuang, Ying-ping; Chu, Ju; Zhang, Si-liang

    2008-03-01

    Immobilized penicillin acylase was used for bioconversion of penicillin PG into 6-APA in aqueous two-phase systems consisting of a light-sensitive polymer PNBC and a pH-sensitive polymer PADB. Partition coefficients of 6-APA was found to be about 5.78 in the presence of 1% NaCl. Enzyme kinetics showed that the reaction reached equilibrium at roughly 7 h. The 6-APA mole yields were 85.3% (pH 7.8, 20 degrees C), with about 20% increment as compared with the reaction of single aqueous phase buffer. The partition coefficient of PG (Na) varied scarcely, while that of the product, 6-APA and phenylacetic acid (PA) significantly varied due to Donnan effect of the phase systems and hydrophobicity of the products. The variation of the partition coefficients of the products also affected the bioconversion yield of the products. In the aqueous two-phase systems, the substrate, PG, the products of 6-APA and PA were biased in the top phase, while immobilized penicillin acylase at completely partitioned at the bottom. The substrate and PG entered the bottom phase, where it was catalyzed into 6-APA and PA and entered the top phase. Inhibition of the substrate and products was removed to result in improvement of the product yield, and the immobilized enzyme showed higher efficiency than the immobilized cells and occupied smaller volume. Compared with the free enzyme, immobilized enzyme had greater stability, longer life-time, and was completely partitioned in the bottom phase and recycle. Bioconversion in two-phase systems using immobilized penicillin acylase showed outstanding advantage. The light-sensitive copolymer forming aqueous two-phase systems could be recovered by laser radiation at 488 nm or filtered 450 nm light, while pH-sensitive polymer PADB could be recovered at the isoelectric point (pH 4.1). The recovery of the two copolymers was between 95% and 99%.

  3. Recovery of crocins from saffron stigmas (Crocus sativus) in aqueous two-phase systems.

    PubMed

    Montalvo-Hernández, Bertha; Rito-Palomares, Marco; Benavides, Jorge

    2012-05-01

    Crocins are carotenoid derivates that have recently attracted the interest of the scientific community due to their nutraceutical properties. Saffron (dry Crocus sativus stigmas) is one of the main known sources of crocins. In this study the potential use of aqueous two-phase system (ATPS) for the extraction of crocins from C. sativus stigmas was evaluated. The partitioning behavior of crocins in different types of ATPS (polymer-polymer, polymer-salt, alcohol-salt and ionic liquid-salt) was evaluated. Ethanol-potassium phosphate ATPS were selected based on their high top phase recovery yield and low cost of system constituents. The evaluation and optimization of system parameters rendered conditions (V(R)=3.2, ethanol 19.8% (w/w), potassium phosphate 16.5% (w/w), TLL of 25% (w/w), 0.1M NaCl and 2% (w/w) of sample load) under which more than 75% of total crocins were recovered in the top (ethanol rich) phase, whereas the wasted stigmas accumulated in the bottom phase. Lastly, a comparison between an optimized solid-liquid extraction using ethanol:water as solvent and ATPS was conducted demonstrating that similar yields are achieved with both strategies (76.89 ± 18% and 79.27 ± 1.6%, respectively). However, ATPS rendered a higher extraction selectivity of 1.3 ± 0.04 mg of crocins for each mg of phenolic compound, whereas ethanolic extraction showed a selectivity of 0.87 ± 0.01. The results reported herein demonstrate the potential application of ATPS, particularly ethanol-potassium phosphate systems, for the recovery of crocins from C. sativus stigmas. PMID:22463999

  4. Recovery of crocins from saffron stigmas (Crocus sativus) in aqueous two-phase systems.

    PubMed

    Montalvo-Hernández, Bertha; Rito-Palomares, Marco; Benavides, Jorge

    2012-05-01

    Crocins are carotenoid derivates that have recently attracted the interest of the scientific community due to their nutraceutical properties. Saffron (dry Crocus sativus stigmas) is one of the main known sources of crocins. In this study the potential use of aqueous two-phase system (ATPS) for the extraction of crocins from C. sativus stigmas was evaluated. The partitioning behavior of crocins in different types of ATPS (polymer-polymer, polymer-salt, alcohol-salt and ionic liquid-salt) was evaluated. Ethanol-potassium phosphate ATPS were selected based on their high top phase recovery yield and low cost of system constituents. The evaluation and optimization of system parameters rendered conditions (V(R)=3.2, ethanol 19.8% (w/w), potassium phosphate 16.5% (w/w), TLL of 25% (w/w), 0.1M NaCl and 2% (w/w) of sample load) under which more than 75% of total crocins were recovered in the top (ethanol rich) phase, whereas the wasted stigmas accumulated in the bottom phase. Lastly, a comparison between an optimized solid-liquid extraction using ethanol:water as solvent and ATPS was conducted demonstrating that similar yields are achieved with both strategies (76.89 ± 18% and 79.27 ± 1.6%, respectively). However, ATPS rendered a higher extraction selectivity of 1.3 ± 0.04 mg of crocins for each mg of phenolic compound, whereas ethanolic extraction showed a selectivity of 0.87 ± 0.01. The results reported herein demonstrate the potential application of ATPS, particularly ethanol-potassium phosphate systems, for the recovery of crocins from C. sativus stigmas.

  5. A resolution approach of racemic phenylalanine with aqueous two-phase systems of chiral tropine ionic liquids.

    PubMed

    Wu, Haoran; Yao, Shun; Qian, Guofei; Yao, Tian; Song, Hang

    2015-10-30

    Aqueous two-phase systems (ATPS) based on tropine type chiral ionic liquids and inorganic salt solution were designed and prepared for the enantiomeric separation of racemic phenylalanine. The phase behavior of IL-based ATPS was comprehensive investigated, and phase equilibrium data were correlated by Merchuk equation. Various factors were also systematically investigated for their influence on separation efficiency. Under the appropriate conditions (0.13g/g [C8Tropine]pro, 35mg/g Cu(Ac)2, 20mg/g d,l-phenylalanine, 0.51g/g H2O and 0.30g/g K2HPO4), the enantiomeric excess value of phenylalanine in solid phase (mainly containing l-enantiomer) was 65%. Finally, the interaction mechanism was studied via 1D and 2D NMR. The results indicate that d-enantiomer of phenylalanine interacts more strongly with chiral ILs and Cu(2+) based on the chiral ion-pairs space coordination mechanism, which makes it tend to remain in the top IL-rich phase. By contrast, l-enantiomer is transferred into the solid phase. Above chiral ionic liquids aqueous two-phase systems have demonstrated obvious resolution to racemic phenylalanine and could be promising alterative resolution approach for racemic amino acids in aqueous circumstance.

  6. Theoretical prediction of phase relations among aqueous solutions and minerals: Salton Sea geothermal system

    NASA Astrophysics Data System (ADS)

    Bird, Dennis K.; Norton, Denis L.

    1981-09-01

    Thermodynamic calculations of compositional relations among aqueous solutions and minerals in the system Na2O-K2O-CaO-MgO-Fe2O3 Al2O3-SiO2-H2O-CO2 HCl at pressures and temperatures corresponding to liquid-vapor equilibrium of H2O permit quantitative description and interpretation of phase relations among rock forming minerals and aqueous solutions in magma-hydrothermal systems. The extensive data base on the Salton Sea geothermal system provides an exemplary case for predicting the chemical characteristics of geothermal fluids associated with metasomatic mineral zones observed in deep drillhole samples. Near the Elmore No. 1 well aqueous species activity ratios of {aNa+}/{aH+} and {aK+}/{aH+} vary several tenths of a log unit with increasing depth and temperature from ∼ 0.6 km and ∼250°C to ∼ 2.2 km and ∼350°C, whereas {aCa2+}/{a2H+} decreases ∼ 2 orders of magnitude for a comparable range in depth and temperature. The fugacity of CO2 gas is ∼1.5-6 bars at ≲ 310°C. Calculated values of aSio2(aq), {aNa+}/{aK+}, {aCa2+}/{aMg2+} and fCO2(g), in the fluid phase coexisting with observed mineralogic phase relations are in remarkably close agreement with measured solute concentrations in geothermal fluids produced from deep drillholes near the Salton Sea. Hydrolysis reactions representing observed phase relations and written with alkali and alkaline earth cations as products have negative standard molal enthalpies (ΔH0P,T,r) and volumes (ΔV0P,T,r) of reactions; consequently, {aNa+}/{aH+}, {aK+}/{aH+}, {aCa2+}/{a2H+}, and {aMg2+}/{a2H+} decrease with increasing temperature at constant pressure, but increase with increasing pressure at constant temperature. An approximate linear relationship exists among these activity ratios and the reciprocal of absolute temperatures because ΔH0P,T,r varies only slightly with increasing temperature at ≲ 250 to 300°C. However, at ≳300°C, ΔH0P,T,r and ΔV0P,T,R decrease dramatically as a consequence of extrema in

  7. Aqueous two phase system based on ionic liquid for isolation of quinine from human plasma sample.

    PubMed

    Flieger, J; Czajkowska-Żelazko, A

    2015-01-01

    Aqueous two phase system was applied for selective extraction of quinine from human plasma. Bi-phase was constructed from ionic liquid: butyl-methyl-imidazolium chloride after addition kosmotropic salts K₃PO₄ or KH₂PO₄. Quinine was determined in plasma samples after drinking of tonic containing quinine. Determination was performed by HPLC on 5-μm Zorbax SB-CN column and eluent containing 40% acetonitrile (v/v), 20 mM phosphate buffer at pH 3 and 40 mM NaPF₆ using external standard method. The spectrophotometric detection was set λ=214 nm. Selective fluorescence detection was performed at excitation of 325 nm and emission of 375 nm. Proposed strategy provides suitable sample purification and gives extraction yields in the range of 89-106%. The determination coefficient (R(2)) has a value ≥0.997 in the range of 50-800 ng/ml quinine concentration. The limit of quantification was set at 27.9 ng/ml and the detection limit was found to be 8.4 ng/ml under fluorescence detection. PMID:25053040

  8. Zinc(II) oxide solubility and phase behavior in aqueous sodium phosphate solutions at elevated temperatures

    SciTech Connect

    Ziemniak, S.E.; Jones, M.E.; Combs, K.E.S.

    1990-02-01

    A platinum-lined, flowing autoclave facility is used to investigate the solubility/phase behavior of zinc(II) oxide in aqueous sodium phosphate solutions at temperatures between 290 and 560 K. ZnO solubilities are observed to increase continuously with temperature and phosphate concentration. At higher phosphate concentrations, a solid phase transformation to NaZnPO{sub 4} is observed. NaZnPO{sub 4} solubilities are retrograde with temperature. The measured solubility behavior is examined via a Zn(II) ion hydrolysis/complexing model and thermodynamic functions for the hydrolysis/complexing reaction equilibria are obtained from a least-squares analysis of the data. The existence of two new zinc(II) ion complexes is reported for the first time: Zn(OH){sub 2}(HPO{sub 4}){sup 2{minus}} and Zn(OH){sub 3}(H{sub 2}PO{sub 4}){sup 2{minus}}. A summary of thermochemical properties for species in the systems ZnO-H{sub 2}O and ZnO-Na{sub 2}O-P{sub 2}O{sub 5}-H{sub 2}O is also provided. 21 refs., 10 figs., 7 tabs.

  9. Aqueous two phase system based on ionic liquid for isolation of quinine from human plasma sample.

    PubMed

    Flieger, J; Czajkowska-Żelazko, A

    2015-01-01

    Aqueous two phase system was applied for selective extraction of quinine from human plasma. Bi-phase was constructed from ionic liquid: butyl-methyl-imidazolium chloride after addition kosmotropic salts K₃PO₄ or KH₂PO₄. Quinine was determined in plasma samples after drinking of tonic containing quinine. Determination was performed by HPLC on 5-μm Zorbax SB-CN column and eluent containing 40% acetonitrile (v/v), 20 mM phosphate buffer at pH 3 and 40 mM NaPF₆ using external standard method. The spectrophotometric detection was set λ=214 nm. Selective fluorescence detection was performed at excitation of 325 nm and emission of 375 nm. Proposed strategy provides suitable sample purification and gives extraction yields in the range of 89-106%. The determination coefficient (R(2)) has a value ≥0.997 in the range of 50-800 ng/ml quinine concentration. The limit of quantification was set at 27.9 ng/ml and the detection limit was found to be 8.4 ng/ml under fluorescence detection.

  10. Evolution of phase and morphology of titanium dioxide induced from peroxo titanate complex aqueous solution.

    PubMed

    Chang, Jeong Ah; Vithal, Muga; Baek, In Chan; Seok, Sang Il

    2010-01-01

    We demonstrate the growth of anatase TiO2 in nanospheres and rutile TiO2 in nanorods, by the hydrolysis of titanium tetraisopropoxide (TTIP) in the presence of hydrogen peroxide at 100 degrees C using sol-gel method. X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), scanning electron microscopy (SEM), and surface area measurement techniques are used to characterize the phase and shape developments of TiO2 obtained from peroxo titanate complex in an aqueous solution at 100 degrees C. Peroxo titanate complexes were prepared by a reaction of titanium hydroxide, formed by hydrolysis of titanium tetraisopropoxide (TTIP), and different amounts of hydrogen peroxide (H2O2). TEM and XRD investigations reveal that the size of spheres (anatase) and rods (rutile) are about 8 nm (diameter) and about 13 x 29 nm approximately 20 x 75 nm (width x length) respectively. The influence of molar ratio of H2O2/TTIP on the phase and morphology of TiO2 is presented. A mixture of anatase spheres and short rutile rods are formed at low H2O2/TTIP ratio while predominantly rutile a quit long rods are formed at higher H2O2/TTIP ratio. PMID:20352827

  11. Desulfurization of dibenzothiophene by a newly isolated Corynebacterium sp. ZD-1 in aqueous phase.

    PubMed

    Wang, Miao-Dong; Li, Wei; Wang, Da-Hui; Shi, Yao

    2004-01-01

    Sulfur emission through fuel combustion is a global problem because it is a major cause of acid rain. Crud oil contains many heterocyclic organic sulfur compounds, among which dibenzothiophene (DBT) and DBTs bearing alkyl substitutions usually are representative compounds. A strain was isolated from refinery sludge and identified as Corynebacterium ZD-1. The behavior of DBT degradation by ZD-1 in aqueous phase was investigated. Corynebacterium ZD-1 could metabolize DBT to 2-hydroxybiphenyl(2-HBP) as the dead-end metabolite through a sulfur-specific pathway. In shake flask culture, ZD-1 had its maximal desulfurization activity in the late exponential growth phase and the specific production rate of 2-HBP was about 0.14 (mmol x kg dry cell(-1) x min(-1), mmol x KDC(-1) x min(-1)). Active resting cells for desulfurization should be prepared only in this period. 2-HBP inhibited the growth of strain ZD-1, the production of DBT degradation enzymes, and the activity of enzymes. Sulfate inhibited the production of dibenzothiophene (DBT) degradation enzymes but had no effect on the enzymes' activity. The production rates of 2-HBP at lower cell densities were higher and the maximum amount conversion of DBT to 2-HBP (0.067 mmol/L) after 8 h was gained at 9.2 g dry cell/L rather higher cell density. The results indicated that this newly isolated strain could be a promising biocatalyst for DBT desulfurization.

  12. Towards stable catalysts for aqueous phase conversion of ethylene glycol for renewable hydrogen.

    PubMed

    Koichumanova, Kamila; Vikla, Anna Kaisa K; de Vlieger, Dennis J M; Seshan, K; Mojet, Barbara L; Lefferts, Leon

    2013-09-01

    Aqueous-phase reforming of ethylene glycol over alumina-supported Pt-based catalysts is reported. Performance of the catalysts is investigated by conducting kinetics and in situ attenuated total reflectance (ATR)-IR spectroscopic analysis. Pt/γ-Al2 O3 is unstable under APR conditions (270 °C, 90 bar) and undergoes phase transformation to boehmite [AlO(OH)]. This conversion of alumina is studied in situ by using ATR-IR spectroscopy; transition into boehmite proceeds even at milder conditions (210 °C, 40 bar). Pt/γ-Al2 O3 deactivates irreversibly because the Pt surface area decreases owing to an increasing metal particle size and coverage with boehmite. However, Pt supported on boehmite itself shows stable activity. Surprisingly, the rate of formation of hydrogen per Pt surface atom is significantly higher on boehmite compared to an alumina-supported catalyst. This observation seems correlated to both increased concentration of surface OH groups as well as to enhanced oxidation of Pt when comparing Pt/γ-Al2 O3 with Pt/AlO(OH).

  13. Containment and recovery of a light non-aqueous phase liquid plume at a woodtreating facility

    SciTech Connect

    Crouse, D.; Powell, G.; Hawthorn, S.; Weinstock, S.

    1997-12-31

    A woodtreating site in Montana used a formulation (product) of 5 percent pentachlorophenol and 95 percent diesel fuel as a carrier liquid to pressure treat lumber. Through years of operations approximately 378,500 liters of this light non-aqueous phase liquid (LNAPL) product spilled onto the ground and soaked into the groundwater. A plume of this LNAPL product flowed in a northerly direction toward a stream located approximately 410 meters from the pressure treatment building. A 271-meter long high density polyethylene (HDPE) containment cutoff barrier wall was installed 15 meters from the stream to capture, contain, and prevent the product from migrating off site. This barrier was extended to a depth of 3.7 meters below ground surface and allowed the groundwater to flow beneath it. Ten product recovery wells, each with a dual-phase pumping system, were installed within the plume, and a groundwater model was completed to indicate how the plume would be contained by generating a cone of influence at each recovery well. The model indicated that the recovery wells and cutoff barrier wall would contain the plume and prevent further migration. To date, nearly 3{1/2} year`s later, approximately 106,000 liters of product have been recovered.

  14. Determination of aqueous two phase system binodal curves using a microfluidic device.

    PubMed

    Silva, D F C; Azevedo, A M; Fernandes, P; Chu, V; Conde, J P; Aires-Barros, M R

    2014-11-28

    Aqueous two phase systems (ATPS) offer great potential for selective separation of a wide range of biomolecules by exploring differences in solubility in each of the two phases. However, their use has been greatly hindered due to poor theoretical understanding of the principles behind ATPS formation and the empirical and time-consuming techniques used for the determination of optimal extraction parameters including the binodal curves. In this work, characteristic ATPS binodal curves were determined by a novel technique in which the formation of an ATPS system is measured in a microfluidic device. Two solutions containing separate ATPS solution precursors were loaded into the side inlets of a three inlet microfluidic channel while milli-Q water was loaded into the middle inlet. By varying the flow rates of the three solutions, a wide range of concentrations inside the microchannel could be rapidly tested using limited volumes. Using optical microscopy, depending on the concentrations inside the microchannel, three different states could be observed at the end of the microchannel (i) the presence of an interface; (ii) no presence of an interface; or (iii) the presence of an unstable interface. The binodal curve was calculated using the points corresponding to unstable interfaces and compared to binodal curves obtained through the standard turbidometric titration method for both PEG/salt and PEG/dextran systems. PMID:25454135

  15. Heterogeneous oxidation of nitrite anion by gas-phase ozone in an aqueous droplet levitated by laser tweezers (optical trap): is there any evidence for enhanced surface reaction?

    PubMed

    Hunt, Oliver R; Ward, Andrew D; King, Martin D

    2015-01-28

    The oxidation of nitrite anion within an aqueous atmospheric droplet may be a sink for HONO in the lower atmosphere. An optical trap with Raman spectroscopy is used to demonstrate that the oxidation of aqueous nitrite anion in levitated, micron sized, aqueous droplets by gas-phase ozone is consistent with bulk aqueous-phase kinetics and diffusion. There is no evidence of an enhanced or retarded reaction at the droplet surface at the concentrations used in the experiment or likely to be found in the atmosphere. The oxidation of nitrite in an aqueous droplet by gas-phase ozone does not cause the droplet to hydrodynamically change in size and demonstrates use of an optical trap as a wall-less reactor to measuring aqueous-phase rate coefficients.

  16. In-situ measurements of scattering phase functions of stratospheric aerosol particles in Alaska during July 1979

    NASA Technical Reports Server (NTRS)

    Grams, G. W.

    1981-01-01

    A laser nephelometer developed for airborne measurements of polar scattering diagrams of atmospheric aerosols was flown on the NCAR Sabreliner aircraft to obtain data on light-scattering parameters for stratospheric aerosol particles over Alaska during July 1979. Observed values of the angular variation of scattered-light intensity were compared with those calculated for different values of the asymmetry parameter g in the Henyey-Greenstein phase function. The observations indicate that, for the time and location of the experiments, the Henyey-Greenstein phase function could be used to calculate polar scattering diagrams to within experimental errors for an asymmetry parameter value of 0.49 plus or minus 0.07.

  17. Regional Air Quality Model Application of the Aqueous-Phase Photo Reduction of Atmospheric Oxidized Mercury by Dicarboxylic Acids

    EPA Science Inventory

    In most ecosystems, atmospheric deposition is the primary input of mercury. The total wet deposition of mercury in atmospheric chemistry models is sensitive to parameterization of the aqueous-phase reduction of divalent oxidized mercury (Hg2+). However, most atmospheric chemistry...

  18. Evaluation of the particle measurement programme (PMP) protocol to remove the vehicles' exhaust aerosol volatile phase.

    PubMed

    Giechaskiel, B; Chirico, R; Decarlo, P F; Clairotte, M; Adam, T; Martini, G; Heringa, M F; Richter, R; Prevot, A S H; Baltensperger, U; Astorga, C

    2010-10-01

    European regulation for Euro 5/6 light duty emissions introduced the measurement of non-volatile particles with diameter >23 nm. The volatile phase is removed by using a heated dilution stage (150 degrees C) and a heated tube (at 300-400 degrees C). We investigated experimentally the removal efficiency for volatile species of the specific protocol by conducting measurements with two Euro 3 diesel light duty vehicles, a Euro 2 moped, and a Euro III heavy duty vehicle with the system's heaters on and off. The particle number distributions were measured with a Scanning Mobility Particle Sizer (SMPS) and a Fast Mobility Particle Sizer (FMPS). An Aerosol Mass Spectrometer (AMS) was used to identify the non-refractory chemical composition of the particles. A Multi-Angle Absorption Photometer (MAAP) was used to measure the black carbon concentration. The results showed that the condensed material in the accumulation mode (defined here as particles in the diameter range of approximately 50-500 nm) was removed with an efficiency of 50-90%. The (volatile) nucleation mode was also completely evaporated or was decreased to sizes <23 nm; thus these particles wouldn't be counted from the particle counter, indicating the robustness of the protocol.

  19. Evaluation of the particle measurement programme (PMP) protocol to remove the vehicles' exhaust aerosol volatile phase.

    PubMed

    Giechaskiel, B; Chirico, R; Decarlo, P F; Clairotte, M; Adam, T; Martini, G; Heringa, M F; Richter, R; Prevot, A S H; Baltensperger, U; Astorga, C

    2010-10-01

    European regulation for Euro 5/6 light duty emissions introduced the measurement of non-volatile particles with diameter >23 nm. The volatile phase is removed by using a heated dilution stage (150 degrees C) and a heated tube (at 300-400 degrees C). We investigated experimentally the removal efficiency for volatile species of the specific protocol by conducting measurements with two Euro 3 diesel light duty vehicles, a Euro 2 moped, and a Euro III heavy duty vehicle with the system's heaters on and off. The particle number distributions were measured with a Scanning Mobility Particle Sizer (SMPS) and a Fast Mobility Particle Sizer (FMPS). An Aerosol Mass Spectrometer (AMS) was used to identify the non-refractory chemical composition of the particles. A Multi-Angle Absorption Photometer (MAAP) was used to measure the black carbon concentration. The results showed that the condensed material in the accumulation mode (defined here as particles in the diameter range of approximately 50-500 nm) was removed with an efficiency of 50-90%. The (volatile) nucleation mode was also completely evaporated or was decreased to sizes <23 nm; thus these particles wouldn't be counted from the particle counter, indicating the robustness of the protocol. PMID:20692024

  20. Is the HO4- anion a key species in the aqueous-phase decomposition of ozone?

    PubMed

    Anglada, Josep M; Torrent-Sucarrat, Miquel; Ruiz-Lopez, Manuel F; Martins-Costa, Marilia

    2012-10-15

    The role of the HO(4)(-) anion in atmospheric chemistry and biology is a matter of debate, because it can be formed from, or be in equilibrium with, key species such as O(3) + HO(-) or HO(2) + O(2) (-). The determination of the stability of HO(4)(-) in water therefore has the greatest relevance for better understanding the mechanism associated with oxidative cascades in aqueous solution. However, experiments are difficult to perform because of the short-lived character of this species, and in this work we have employed DFT, CCSD(T) complete basis set (CBS), MRCI/aug-cc-pVTZ, and combined quantum mechanics/molecular mechanics (QM/MM) calculations to investigate this topic. We show that the HO(4)(-) anion has a planar structure in the gas phase, with a very large HOO-OO bond length (1.823 Å). In contrast, HO(4)(-) adopts a nonplanar configuration in aqueous solution, with huge geometrical changes (up to 0.232 Å for the HOO-OO bond length) with a very small energy cost. The formation of the HO(4)(-) anion is predicted to be endergonic by 5.53±1.44 and 2.14±0.37 kcal mol(-1) with respect to the O(3) + HO(-) and HO(2) + O(2)(-) channels, respectively. Moreover, the combination of theoretical calculations with experimental free energies of solvation has allowed us to obtain accurate free energies for the main reactions involved in the aqueous decomposition of ozone. Thus, the oxygen transfer reaction (O(3) + OH(-) → HO(2) + O(2)(-)) is endergonic by 3.39±1.80 kcal mol(-1), the electron transfer process (O(3) + O(2)(-) → O(3)(-) + O(2)) is exergonic by 31.53±1.05 kcal mol(-1), supporting the chain-carrier role of the superoxide ion, and the reaction O(3) + HO(2)(-) → OH + O(2)(-) + O(2) is exergonic by 12.78±1.15 kcal mol(-1), which is consistent with the fact that the addition of small amounts of HO(2)(-) (through H(2)O(2)) accelerates ozone decomposition in water. The combination of our results with previously reported thermokinetic data provides some

  1. NASA's Atmospheric Effects of Aviation Project: Results of the August 1999 Aerosol Measurement Intercomparison Workshop, Laboratory Phase

    NASA Technical Reports Server (NTRS)

    Cofer, W. Randy, III; Anderson, Bruce E.; Connors, V. S.; Wey, C. C.; Sanders, T.; Twohy, C.; Brock, C. A.; Winstead, E. L.; Pui, D.; Chen, Da-Ren

    2001-01-01

    During August 1-14, 1999, NASA's Atmospheric Effects of Aviation Project (AEAP) convened a workshop at the NASA Langley Research Center to try to determine why such a wide variation in aerosol emissions indices and chemical and physical properties have been reported by various independent AEAP-supported research teams trying to characterize the exhaust emissions of subsonic commercial aircraft. This workshop was divided into two phases, a laboratory phase and a field phase. The laboratory phase consisted of supplying known particle number densities (concentrations) and particle size distributions to a common manifold for the participating research teams to sample and analyze. The field phase was conducted on an aircraft run-up pad. Participating teams actually sampled aircraft exhaust generated by a Langley T-38 Talon aircraft at 1 and 9 m behind the engine at engine powers ranging from 48 to 100 percent. Results from the laboratory phase of this intercomparison workshop are reported in this paper.

  2. Effect of Protonation on the Solution and Phase Behavior of Aqueous Sodium Myristate.

    PubMed

    Wen; Franses

    2000-11-01

    Aqueous sodium myristate solutions have been shown to have unusually low dynamic tensions (1-10 mN/m) under pulsating area conditions. These solutions have no sharp solubility limit, evidently because they are protonated (or "hydrolyzed") to form the much less soluble myristic acid and acid soaps. With no added electrolytes, the protonation fraction is 1% or less. The apparent protonation equilibrium "constant" increases with increasing concentration, indicating strong solution nonidealities, in addition to micellization. This protonation seems to affect the solution and phase behavior of aqueous sodium myristate strongly, as evidenced by the effect of added NaOH. Ion-selective electrodes (for Na(+) and H(+)) and conductimetry indicate that at 25 degrees C dissolved surfactant concentrations keep increasing well after dispersed particles are observed (2 mM). A cmc of about 4.5 mM, micelles of aggregation number n=70 and counterion binding parameter beta=0.7 are inferred from these techniques. The cmc of sodium myristate increases slightly with temperature from 25 to 45 degrees C. FTIR analysis of the filtered particles indicates that the dispersed particles are mainly acid soaps for concentrations less than 6 mM. With 10 mM NaOH, the particles observed above 2 mM consist mostly of sodium myristate. From both conductivity and IR data, the solubility of sodium myristate in water at 25 degrees C is estimated to be about 6 mM, and as expected, it increases with increasing temperature and decreases with increasing sodium ion concentration. Copyright 2000 Academic Press.

  3. A Novel Aqueous Two Phase System Composed of Surfactant and Xylitol for the Purification of Lipase from Pumpkin (Cucurbita moschata) Seeds and Recycling of Phase Components.

    PubMed

    Amid, Mehrnoush; Manap, Mohd Yazid; Hussin, Muhaini; Mustafa, Shuhaimi

    2015-06-17

    Lipase is one of the more important enzymes used in various industries such as the food, detergent, pharmaceutical, textile, and pulp and paper sectors. A novel aqueous two-phase system composed of surfactant and xylitol was employed for the first time to purify lipase from Cucurbita moschata. The influence of different parameters such as type and concentration of surfactants, and the composition of the surfactant/xylitol mixtures on the partitioning behavior and recovery of lipase was investigated. Moreover, the effect of system pH and crude load on the degree of purification and yield of the purified lipase were studied. The results indicated that the lipase was partitioned into the top surfactant rich phase while the impurities partitioned into the bottom xylitol-rich phase using an aqueous two phase system composed of 24% (w/w) Triton X-100 and 20% (w/w) xylitol, at 56.2% of tie line length (TLL), (TTL is one of the important parameters in this study and it is determined from a bimodal curve in which the tie-line connects two nodes on the bimodal, that represent concentration of phase components in the top and bottom phases) and a crude load of 25% (w/w) at pH 8.0. Recovery and recycling of components was also measured in each successive step process. The enzyme was successfully recovered by the proposed method with a high purification factor of 16.4 and yield of 97.4% while over 97% of the phase components were also recovered and recycled. This study demonstrated that the proposed novel aqueous two phase system method is more efficient and economical than the traditional aqueous two phase system method for the purification and recovery of the valuable enzyme lipase.

  4. A Novel Aqueous Two Phase System Composed of Surfactant and Xylitol for the Purification of Lipase from Pumpkin (Cucurbita moschata) Seeds and Recycling of Phase Components.

    PubMed

    Amid, Mehrnoush; Manap, Mohd Yazid; Hussin, Muhaini; Mustafa, Shuhaimi

    2015-01-01

    Lipase is one of the more important enzymes used in various industries such as the food, detergent, pharmaceutical, textile, and pulp and paper sectors. A novel aqueous two-phase system composed of surfactant and xylitol was employed for the first time to purify lipase from Cucurbita moschata. The influence of different parameters such as type and concentration of surfactants, and the composition of the surfactant/xylitol mixtures on the partitioning behavior and recovery of lipase was investigated. Moreover, the effect of system pH and crude load on the degree of purification and yield of the purified lipase were studied. The results indicated that the lipase was partitioned into the top surfactant rich phase while the impurities partitioned into the bottom xylitol-rich phase using an aqueous two phase system composed of 24% (w/w) Triton X-100 and 20% (w/w) xylitol, at 56.2% of tie line length (TLL), (TTL is one of the important parameters in this study and it is determined from a bimodal curve in which the tie-line connects two nodes on the bimodal, that represent concentration of phase components in the top and bottom phases) and a crude load of 25% (w/w) at pH 8.0. Recovery and recycling of components was also measured in each successive step process. The enzyme was successfully recovered by the proposed method with a high purification factor of 16.4 and yield of 97.4% while over 97% of the phase components were also recovered and recycled. This study demonstrated that the proposed novel aqueous two phase system method is more efficient and economical than the traditional aqueous two phase system method for the purification and recovery of the valuable enzyme lipase. PMID:26091076

  5. Design of a new multi-phase experimental simulation chamber for atmospheric photosmog, aerosol and cloud chemistry research

    NASA Astrophysics Data System (ADS)

    Wang, J.; Doussin, J.-F.; Perrier, S.; Perraudin, E.; Katrib, Y.; Pangui, E.; Picquet-Varrault, B.

    2011-01-01

    A new simulation chamber has been built at the Interuniversitary Laboratory of Atmospheric Systems (LISA). The CESAM chamber (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) is designed to allow research in multiphase atmospheric (photo-)chemistry which involves both gas phase and condensed phase processes including aerosol and cloud chemistry. CESAM has the potential to carry out variable temperature and pressure experiments under a very realistic artificial solar irradiation. It consists of a 4.2 m3 stainless steel vessel equipped with three high pressure xenon arc lamps which provides a controlled and steady environment. Initial characterization results, all carried out at 290-297 K under dry conditions, concerning lighting homogeneity, mixing efficiency, ozone lifetime, radical sources, NOy wall reactivity, particle loss rates, background PM, aerosol formation and cloud generation are given. Photolysis frequencies of NO2 and O3 related to chamber radiation system were found equal to (4.2 × 10-3 s-1) for JNO2 and (1.4 × 10-5 s-1) for J O1D which is comparable to the solar radiation in the boundary layer. An auxiliary mechanism describing NOy wall reactions has been developed. Its inclusion in the Master Chemical Mechanism allowed us to adequately model the results of experiments on the photo-oxidation of propene-NOx-air mixtures. Aerosol yields for the α-pinene + O3 system chosen as a reference were determined and found in good agreement with previous studies. Particle lifetime in the chamber ranges from 10 h to 4 days depending on particle size distribution which indicates that the chamber can provide high quality data on aerosol aging processes and their effects. Being evacuable, it is possible to generate in this new chamber clouds by fast expansion or saturation with or without the presence of pre-existing particles, which will provide a multiphase environment for aerosol-droplet interaction.

  6. Design of a new multi-phase experimental simulation chamber for atmospheric photosmog, aerosol and cloud chemistry research

    NASA Astrophysics Data System (ADS)

    Wang, J.; Doussin, J. F.; Perrier, S.; Perraudin, E.; Katrib, Y.; Pangui, E.; Picquet-Varrault, B.

    2011-11-01

    A new simulation chamber has been built at the Interuniversitary Laboratory of Atmospheric Systems (LISA). The CESAM chamber (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) is designed to allow research in multiphase atmospheric (photo-) chemistry which involves both gas phase and condensed phase processes including aerosol and cloud chemistry. CESAM has the potential to carry out variable temperature and pressure experiments under a very realistic artificial solar irradiation. It consists of a 4.2 m3 stainless steel vessel equipped with three high pressure xenon arc lamps which provides a controlled and steady environment. Initial characterization results, all carried out at 290-297 K under dry conditions, concerning lighting homogeneity, mixing efficiency, ozone lifetime, radical sources, NOy wall reactivity, particle loss rates, background PM, aerosol formation and cloud generation are given. Photolysis frequencies of NO2 and O3 related to chamber radiation system were found equal to (4.2 × 10-3 s-1) for JNO2 and (1.4 × 10-5 s-1) for JO1D which is comparable to the solar radiation in the boundary layer. An auxiliary mechanism describing NOy wall reactions has been developed. Its inclusion in the Master Chemical Mechanism allowed us to adequately model the results of experiments on the photo-oxidation of propene-NOx-Air mixtures. Aerosol yields for the α-pinene + O3 system chosen as a reference were determined and found in good agreement with previous studies. Particle lifetime in the chamber ranges from 10 h to 4 days depending on particle size distribution which indicates that the chamber can provide high quality data on aerosol aging processes and their effects. Being evacuable, it is possible to generate in this new chamber clouds by fast expansion or saturation with or without the presence of pre-existing particles, which will provide a multiphase environment for aerosol-droplet interaction.

  7. Self-assembly and phase behavior of germanium oxide nanoparticles in basic aqueous solutions.

    PubMed

    Rimer, Jeffrey D; Roth, Daniel D; Vlachos, Dionisios G; Lobo, Raul F

    2007-02-27

    We show that germania nanoparticle self-assembly in basic aqueous solutions occurs at a critical aggregation concentration (CAC) corresponding to a 1:1 GeO2/OH- molar ratio. A combination of pH, conductivity, and small-angle X-ray scattering (SAXS) measurements was used to monitor the effect of incremental additions of germanium (IV) ethoxide to basic solutions of sodium hydroxide or tetraalkylammonium cations. Plots of pH versus total germania concentration at varying alkalinities generated a phase diagram with three distinct regions. The diagram was analyzed with a thermodynamic model based on the chemical equilibria of germania speciation and dissociation. The model, which uses the GeO-H dissociation constant (pK = 7.1) as the single fitting parameter, quantitatively captures trends in the CAC and pH. SAXS patterns reveal that the germania nanoparticles have either a cubic or a spherical geometry of dimension approximately 1 nm that is independent of solution pH and cation. On the basis of these and other literature findings, we propose that the germania nanoparticle structure is that of the cubic octamer (double four-membered ring, Ge8O12(OH)8), which is common among condensed GeO2 materials and building units in [Ge,Si]-zeolites. Comparisons between germania and silica solutions show distinct differences in their phase behavior and nanoparticle structure. The results presented here, in combination with previous studies of siliceous solutions, provide a framework for ongoing studies of combined germania-silica phase behavior, which is part of an overarching effort to understand the influence of heteroatoms in the growth and structure direction of zeolites.

  8. Laboratory studies on the OH-initiated oxidation of acetone in the aqueous phase

    NASA Astrophysics Data System (ADS)

    Schaefer, T.; Herrmann, H.

    2010-07-01

    Small organic compounds, such as acetone and its oxidation products, are emitted by a variety of natural and anthropogenic sources in the atmosphere. The degradation or transformation of these compounds can occur in the gas phase and in the liquid phase (cloud droplets, fog, rain or hygroscopic particles) of the troposphere. A special role plays the OH radical, which is one of the most reactive radicals in the atmosphere. To study the OH radical reaction towards small organic compounds in the aqueous phase, a thermostated laser photolysis long path absorption set-up was used. The OH radicals were generated directly in the reaction cell by the photolysis of hydrogen peroxide (H2O2) at ? = 248 nm and monitored using the thiocyanate reference system. Furthermore, the objective of this work is to identify and characterize the various transient species formed in the OH radical reaction. In order to characterize the optical properties of the formed transient compounds (e.g. organic peroxy radicals) a laser photolysis long path absorption apparatus coupled with a CCD-camera / grating combination is used. With this technique time resolved spectra (at different delay times after the excimer laser pulse) of the reactants and products can be recorded. Within this contribution organic peroxy radical spectra of the following parent carbonyl compounds (a) acetone, (b) hydroxyacetone and (c) methylglyoxal will be presented, discussed and compared with literature data. The optical characterization of the formed transient compound is necessary to measure rate constants of elementary reaction steps in the degradation process of the small organic compounds. .

  9. Measurement of Gas and Aerosol Phase Absorption Spectra across the Visible and Near-IR Using Supercontinuum Photoacoustic Spectroscopy.

    PubMed

    Radney, James G; Zangmeister, Christopher D

    2015-07-21

    We demonstrate a method to measure the absorption spectra of gas and aerosol species across the visible and near-IR (500 to 840 nm) using a photoacoustic (PA) spectrometer and a pulsed supercontinuum laser source. Measurements of gas phase absorption spectra were demonstrated using H2O(g) as a function of relative humidity (RH). The measured absorption intensities and peak shapes were able to be quantified and compared to spectra calculated using the 2012 High Resolution Transmission (HITRAN2012) database. Size and mass selected nigrosin aerosol was used to measure absorption spectra across the visible and near-IR. Spectra were measured as a function of aerosol size/mass and show good agreement to Mie theory calculations. Lastly, we measured the broadband absorption spectrum of flame generated soot aerosol at 5% and 70% RH. For the high RH case, we are able to quantifiably separate the soot and water absorption contributions. For soot, we observe an enhancement in the mass specific absorption cross section ranging from 1.5 at 500 nm (p < 0.01) to 1.2 at 840 nm (p < 0.2) and a concomitant increase in the absorption Ångström exponent from 1.2 ± 0.4 (5% RH) to 1.6 ± 0.3 (70% RH). PMID:26098142

  10. Secondary Organic Aerosol formation from the gas-phase ozonolysis of 3-methylcatechol and 4-methylcatechol

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, Cécile; Foulon, Valentine; Laréal, Michel; Cassez, Andy; Zhao, Weixiong

    2010-05-01

    Secondary Organic Aerosol (SOA) formation during the ozonolysis of 3-methylcatechol (3-methyl-1,2-dihydroxybenzene) and 4-methylcatechol (3-methyl-1,2-dihydroxybenzene) was investigated using a simulation chamber (8 m3) at atmospheric pressure, room temperature (294 ± 2 K) and low relative humidity (5-10%). The initial mixing ratios were as follows (in ppb): 3-methylcatechol (194-1059), 4-methylcatechol (204-1188) and ozone (93-531). The ozone and methylcatechol concentrations were followed by UV photometry and GC-FID (Gas Chromatography - Flame ionization detector), respectively and the aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer). The SOA yields (Y) were determined as the ratio of the suspended aerosol mass corrected for wall losses (Mo) to the total reacted methylcatechol concentrations assuming a particle density of 1.4 g cm-3. The aerosol formation yield increases as the initial methylcatechol concentration increases, and leads to aerosol yields ranging from 32% to 67% and from 30% to 64% for 3-methylcatechol and 4-methylcatechol, respectively. Y is a strong function of Mo and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. These data are comparable to those published in a recent study on secondary organic aerosol formation from catechol ozonolysis. To our knowledge, this work represents the first investigation of SOA formation from the ozone reaction with methylcatechols.

  11. Evolution of organic aerosol mass spectra upon heating: implications for OA phase and partitioning behavior

    SciTech Connect

    UC Davis; Cappa, Christopher D.; Wilson, Kevin R.

    2010-10-28

    Vacuum Ultraviolet (VUV) photoionization mass spectrometry has been used to measure the evolution of chemical composition for two distinct organic aerosol types as they are passed through a thermodenuder at different temperatures. The two organic aerosol types considered are primary lubricating oil (LO) aerosol and secondary aerosol from the alpha-pinene + O3 reaction (alphaP). The evolution of the VUV mass spectra for the two aerosol types with temperature are observed to differ dramatically. For LO particles, the spectra exhibit distinct changes with temperature in which the lower m/z peaks, corresponding to compounds with higher vapor pressures, disappear more rapidly than the high m/z peaks. In contrast, the alphaP aerosol spectrum is essentially unchanged by temperature even though the particles experience significant mass loss due to evaporation. The variations in the LO spectra are found to be quantitatively in agreement with expectations from absorptive partitioning theory whereas the alphaP spectra suggest that the evaporation of alphaP derived aerosol appears to not be governed by partitioning theory. We postulate that this difference arises from the alphaP particles existing as in a glassy state instead of having the expected liquid-like behavior. To reconcile these observations with decades of aerosol growth measurements, which indicate that OA formation is described by equilibrium partitioning, we present a conceptual model wherein the secondary OA is formed and then rapidly converted from an absorbing form to a non-absorbing form. The results suggest that although OA growth may be describable by equilibrium partitioning theory, the properties of organic aerosol once formed may differ significantly from the properties determined in the equilibrium framework.

  12. Effects of Temperature, Oxygen Level, Ionic Strength, and pH on the Reaction of Benzene with Hydroxyl Radicals at the Air-Water Interface in Comparison to the Bulk Aqueous Phase.

    PubMed

    Heath, Aubrey A; Valsaraj, Kalliat T

    2015-08-01

    Atmospheric aerosols (e.g., fog droplets) are complex, multiphase mediums. Depending on location, time of day, and/or air mass source, there can be considerable variability within these droplets, relating to temperature, pH, and ionic strength. Due to the droplets' inherently small size, the reactions that occur within these droplets are determined by bulk aqueous phase and air-water interfacial conditions. In this study, the reaction of benzene and hydroxyl radicals is examined kinetically in a thin-film flow-tube reactor. By varying the aqueous volume (e.g., film thickness) along the length of the reactor, both bulk and interfacial reaction rates are measured from a single system. Temperature, pH, and ionic strength are varied to model conditions typical of fog events. Oxygen-poor conditions are measured to study oxygen's overall effect on the reaction pathway. Initial rate activation energies and the bulk aqueous phase and interfacial contributions to the overall rate constant are also obtained. PMID:26158391

  13. Effects of Temperature, Oxygen Level, Ionic Strength, and pH on the Reaction of Benzene with Hydroxyl Radicals at the Air-Water Interface in Comparison to the Bulk Aqueous Phase.

    PubMed

    Heath, Aubrey A; Valsaraj, Kalliat T

    2015-08-01

    Atmospheric aerosols (e.g., fog droplets) are complex, multiphase mediums. Depending on location, time of day, and/or air mass source, there can be considerable variability within these droplets, relating to temperature, pH, and ionic strength. Due to the droplets' inherently small size, the reactions that occur within these droplets are determined by bulk aqueous phase and air-water interfacial conditions. In this study, the reaction of benzene and hydroxyl radicals is examined kinetically in a thin-film flow-tube reactor. By varying the aqueous volume (e.g., film thickness) along the length of the reactor, both bulk and interfacial reaction rates are measured from a single system. Temperature, pH, and ionic strength are varied to model conditions typical of fog events. Oxygen-poor conditions are measured to study oxygen's overall effect on the reaction pathway. Initial rate activation energies and the bulk aqueous phase and interfacial contributions to the overall rate constant are also obtained.

  14. Rotavirus-like particles primary recovery from insect cells in aqueous two-phase systems.

    PubMed

    Benavides, Jorge; Mena, Jimmy A; Cisneros-Ruiz, Mayra; Ramírez, Octavio T; Palomares, Laura A; Rito-Palomares, Marco

    2006-09-14

    Virus-like particles have a wide range of applications, including vaccination, gene therapy, and even as nanomaterials. Their successful utilization depends on the availability of selective and scalable methods of product recovery and purification that integrate effectively with upstream operations. In this work, a strategy based on aqueous two phase system (ATPS) was developed for the recovery of double-layered rotavirus-like particles (dlRLP) produced by the insect cell-baculovirus expression system. Polyethylene glycol (PEG) molecular mass, PEG and salt concentrations, and volume ratio (Vr, volume of top phase/volume of bottom phase) were evaluated in order to determine the conditions where dlRLP and contaminants concentrated to opposite phases. Two-stage ATPS consisting of PEG 400-phosphate with a Vr of 13.0 and a tie-line length (TLL) of 35% (w/w) at pH 7.0 provided the best conditions for processing highly concentrated crude extract from disrupted cells (dlRLP concentration of 5 microg/mL). In such conditions intracellular dlRLP accumulated in the top phase (recovery of 90%), whereas cell debris remained in the interface. Furthermore, dlRLP from culture supernatants accumulated preferentially in the interface (recovery of 82%) using ATPS with a Vr of 1.0, pH of 7.0, PEG 3350 (10.1%, w/w) and phosphate (10.9%, w/w). The purity of dlRLP from culture supernatant increased up to 55 times after ATPS. The use of ATPS resulted in a recovery process that produced dlRLP with a purity between 6 and 11% and an overall product yield of 85% (w/w), considering purification from intracellular and extracellular dlRLP. Overall, the strategy proposed in this study is simpler than traditional methods for recovering dlRLP, and represents a scalable and economically viable alternative for production processes of vaccines against rotavirus infection with significant scope for generic commercial application.

  15. An investigation of the factors influencing the detection sensitivity of cavity enhanced Raman scattering for probing aqueous binary aerosol droplets.

    PubMed

    Symes, Rachel; Gilham, Richard J J; Sayer, Robert M; Reid, Jonathan P

    2005-04-01

    Stimulated Raman scattering (SRS) from single aerosol droplets can be observed at extremely low laser threshold intensities at wavelengths commensurate with whispering gallery modes. Although droplet size can routinely be determined from the ensuing cavity enhanced Raman scattering (CERS) fingerprint, determining droplet composition is a considerably more challenging measurement. We present here an examination of the factors that influence and limit the detection sensitivity of CERS in quantifying the concentrations of sulfate and nitrate in water droplets, 20-50 microm in radius. In particular, we consider the variation in nitrate and sulfate SRS signal with variation in species concentration, probe laser intensity and droplet size. We illustrate that the band contour of the OH stretching band can be used as a relative measure of the internal light intensity circulating within the droplet and experimentally investigate how the threshold condition for SRS is achieved.

  16. Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM

    NASA Astrophysics Data System (ADS)

    Roldin, P.; Eriksson, A. C.; Nordin, E. Z.; Hermansson, E.; Mogensen, D.; Rusanen, A.; Boy, M.; Swietlicki, E.; Svenningsson, B.; Zelenyuk, A.; Pagels, J.

    2014-08-01

    We have developed the novel Aerosol Dynamics, gas- and particle-phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas-phase Master Chemical Mechanism version 3.2 (MCMv3.2), an aerosol dynamics and particle-phase chemistry module (which considers acid-catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion-limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study (1) the evaporation of liquid dioctyl phthalate (DOP) particles, (2) the slow and almost particle-size-independent evaporation of α-pinene ozonolysis secondary organic aerosol (SOA) particles, (3) the mass-transfer-limited uptake of ammonia (NH3) and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), and (4) the influence of chamber wall effects on the observed SOA formation in smog chambers. ADCHAM is able to capture the observed α-pinene SOA mass increase in the presence of NH3(g). Organic salts of ammonium and carboxylic acids predominantly form during the early stage of SOA formation. In the smog chamber experiments, these salts contribute substantially to the initial growth of the homogeneously nucleated particles. The model simulations of evaporating α-pinene SOA particles support the recent experimental findings that these particles have a semi-solid tar-like amorphous-phase state. ADCHAM is able to reproduce the main features of the observed slow evaporation rates if the concentration of low-volatility and viscous oligomerized SOA material at the particle surface increases upon evaporation. The evaporation rate is mainly governed by the reversible decomposition of oligomers back to monomers. Finally, we demonstrate that the mass-transfer-limited uptake of condensable organic compounds

  17. Aqueous phase synthesis of copper nanoparticles: a link between heavy metal resistance and nanoparticle synthesis ability in bacterial systems.

    PubMed

    Ramanathan, Rajesh; Field, Matthew R; O'Mullane, Anthony P; Smooker, Peter M; Bhargava, Suresh K; Bansal, Vipul

    2013-03-21

    We demonstrate aqueous phase biosynthesis of phase-pure metallic copper nanoparticles (CuNPs) using a silver resistant bacterium Morganella morganii. This is particularly important considering that there has been no report that demonstrates biosynthesis and stabilization of pure copper nanoparticles in the aqueous phase. Electrochemical analysis of bacterial cells exposed to Cu(2+) ions provides new insights into the mechanistic aspect of Cu(2+) ion reduction within the bacterial cell and indicates a strong link between the silver and copper resistance machinery of bacteria in the context of metal ion reduction. The outcomes of this study take us a step closer towards designing rational strategies for biosynthesis of different metal nanoparticles using microorganisms.

  18. Preparation of the multienzyme system gramicidin S-synthetase 2 with an aqueous three-phase system.

    PubMed

    Kirchner, A; Simonis, M; von Döhren, H

    1987-06-19

    The distribution of gramicidin S-synthetase activity from disrupted cells suspended in aqueous two- and three-phase systems was investigated. An optimized three-phase system containing 5% dextran, 8% Ficoll, 11% PEG and 6.7% disrupted cells was found to be effective in extracting gramicidin S-synthetase activity. The activity yield achieved was higher in comparison to other preparation methods, and the subsequent purification steps were greatly facilitated. The time needed for the preparation of the labile gramicidin S-synthetase was considerably reduced. The combination of the aqueous phase extraction with chromatographic methods yielded 19 mg gramicidin S-synthetase 2 in essentially pure form from 30 g (wet weight) of cells.

  19. Improvement of extraction capability of magnetic molecularly imprinted polymer beads in aqueous media via dual-phase solvent system.

    PubMed

    Hu, Yuling; Liu, Ruijin; Zhang, Yi; Li, Gongke

    2009-08-15

    In this study, a novel and simple dual-phase solvent system for the improvement of extraction capability of magnetic molecularly imprinted polymer (MIP) beads in aqueous sample was proposed. The method integrated MIP extraction and micro-liquid-liquid extraction (micro-LLE) into only one step. A magnetic MIP beads using atrazine as template was synthesized, and was applied to aqueous media by adding micro-volume of n-hexane to form a co-extraction system. The magnetic MIP beads preferred to suspend in the organic phase, which shielded them from the disturbance of water molecule. The target analytes in the water sample was extracted into the organic phase by micro-LLE and then further bound to the solid-phase of magnetic MIP beads. The beads specificity was significantly improved with the imprinting efficiency of template increasing from 0.5 to 4.4, as compared with that in pure aqueous media. The extraction capacity, equilibration process and cross-selectivity of the MIP dual-phase solvent extraction system were investigated. The proposed method coupled with high-performance liquid chromatography was applied to the analysis of atrazine, simazine, propazine, simetryn, prometryne, ametryn and terbutryn in complicated sample such as tomato, strawberry juice and milk. The method is selective, sensitive and low organic solvent-consuming, and has potential to broaden the range of MIP application in biological and environmental sample.

  20. Aqueous phase synthesis of copper nanoparticles: a link between heavy metal resistance and nanoparticle synthesis ability in bacterial systems

    NASA Astrophysics Data System (ADS)

    Ramanathan, Rajesh; Field, Matthew R.; O'Mullane, Anthony P.; Smooker, Peter M.; Bhargava, Suresh K.; Bansal, Vipul

    2013